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Application of multi-element geochemical methods to identify sediment sources and trace the transport… Christie, Tara Michelle 1998

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APPLICATION OF MULTI-ELEMENT GEOCHEMICAL METHODS TO IDENTIFY SEDIMENT SOURCES AND TRACE THE TRANSPORT OF SEDIMENT IN SMALL (S4) STREAMS BEFORE AND AFTER WATERSHED DISTURBANCE B y T a r a M i c h e l l e Chr is t ie B A S c - U n i v e r s i t y o f B r i t i s h C o l u m b i a , 1996. A T H E S I S S U B M I T T E D I N P A R T I A L F U L F I L L M E N T O F T H E R E Q U I R E M E N T S F O R T H E D E G R E E O F M A S T E R O F A P P L I E D S C I E N C E i n T H E F A C U L T Y O F G R A D U A T E S T U D I E S Department o f E a r t h and O c e a n Sciences W e accept this thesis as c o n f o r m i n g to the required standard T H E U N I V E R S I T Y O F B R I T I S H C O L U M B I A December , 1998 ©Tara M i c h e l l e Chr is t ie , 1998 In presenting this thesis in partial fulfilment of the requirements for an advanced degree at the University of British Columbia, I agree that the Library shall make it freely available for reference and study. I further agree that permission for extensive copying of this thesis for scholarly purposes may be granted by the head of my department or by his or her representatives. It is understood that copying or publication of this thesis for financial gain shall not be allowed without my written permission. Department of £arT~U a»d Dr^:^ <>;<?^r^ The University of British Columbia Vancouver, Canada DE-6 (2/88) A B S T R A C T Although it is well-established that background geochemical patterns in stream sediments generally depend on drainage basin geology, little is known of the effects of watershed disturbance on such patterns. Here we report the effects of forestry activities on sediment geochemistry on the Interior Plateau of British Columbia. Samples of sediment were collected from six small streams in 1996, before logging, and in 1997, after clear-cutting. Samples were sieved to - 0.212 mm in grain size and analyzed by multi-element ICP after both a strong acid and a total decomposition. Fie ld and analytical duplicates, and samples from unlogged control sites were used to estimate variations not associated with logging activities. Results show that prior to logging, each stream had a distinct multi-element geochemical signature related to drainage basin geology. There was no overall effect of logging on these signatures within or downstream of the cut-blocks - probably because unlogged buffer zones along the stream channels prevented the development of new sediment sources. Logging roads did, however, cause local changes of sediment geochemistry in two ways: i i 1. C o n s t r u c t i o n o f stream crossings and roadside ditches created n e w sources o f sediment supply to the streams. A l t h o u g h o f l o c a l o r i g i n , the n e w l y exposed and eroding surf ic ia l materials contained m o r e f ine-grained material and had mult i -e lement geochemica l signatures that differed s igni f icant ly f r o m the mature f l u v i a l sediments found i n the stream channel before l o g g i n g . Input o f the n e w material resulted i n geochemica l anomalies that extended several hundred metres downstream f r o m the source. In this study C o , M g and N i were found to have the largest concentration differences between sediment sources and sediments, and hence to gave the longest anomalous dispers ion trains. 2. A b r a s i o n o f z i n c f r o m ga lvanized culverts resulted i n z i n c anomalies , w i t h concentrations >200 p p m . These anomalies also extended several hundred meters downstream and persisted for at least f ive years after instal lat ion o f culverts. T h e effects o f l o g g i n g roads o n sediment geochemistry thus relate to the creation o f n e w sources o f l o c a l sediment, as w e l l as, to the introduct ion o f exotic materials into the stream. N o geochemica l response c o u l d be attributed to the clear-cut forest b l o c k . S u c h changes might develop eventual ly i f s o i l eros ion increases or i f changes to the groundwater regime m o d i f y input o f d i s s o l v e d elements to the stream channel . iii TABLE OF CONTENTS A B S T R A C T i i LIST OF T A B L E S v i i LIST O F F I G U R E S x i i LIST OF P L A T E S xv A C K N O W L E D G M E N T S x v i i Chapter 1: I N T R O D U C T I O N 1 1.1 Forest Practices Code of British Columbia 2 1.2 Controls on trace elements: lithological and non-lithological 4 1.3 Effects of fluvial processes on stream sediment geochemistry 8 1.4 Using geochemistry to trace sediment from point sources 10 1.5 Related studies 17 1.6 Summary and study obj ectives 19 Chapter 2: S T U D Y L O C A T I O N A N D PROJECT L A Y O U T 21 2.1 Location, physiography, and access 23 2.2 Bedrock geology 25 2.3 Quaternary geology and surficial materials 31 2.4 Climate 42 2.5 Soils 43 2.6 Vegetation 44 2.7 Study streams, B1-B6 45 2.8 Logging practices in the Baptiste Creek Watershed 48 2.9 Climate and hydro logical changes due to forest harvesting 60 2.10 Summary 66 Chapter 3: S A M P L I N G A N D A N A L Y T I C A L M E T H O D S 68 3.1 Sample site selection, sample collection and identification of sediment sources 68 3.2 Sample preparation 76 3.2.1 Preparation of 3-5 kg samples 76 3.2.2 Preparation of 20 kg samples 81 3.2.3 Heavy mineral separations 82 3.3 Moda l analysis using the Rietveld method and X-ray powder diffraction 83 3.4 Geochemical analyses methods 84 3.5 Summary of sampling and analytical methods 89 iv Chapter 4: D A T A Q U A L I T Y E V A L U A T I O N 90 4.1 A c c u r a c y o f geochemica l results 91 4.2 P r e c i s i o n o f geochemica l results 91 4.2.1 A n a l y t i c a l p r e c i s i o n and temporal var iab i l i ty i n analyt ica l prec is ion: lab duplicates 98 4.2.2 W i t h i n site var iat ion: f i e l d duplicates 106 4.3 W i t h i n site var iat ion compared to between site var ia t ion 109 4.4 D i s c u s s i o n o f data qual i ty I l l 4.5 D a t a qual i ty summary 113 Chapter 5: T E X T U R E , M I N E R A L O G Y A N D G E O C H E M I C A L A B U N D A N C E S P R I O R T O L O G G I N G 114 5.1 Resul ts 114 5.1.1 Texture and minera logy 114 5.1.2 G e o c h e m i s t r y 119 5.2 D i s c u s s i o n 132 5.3 S u m m a r y 136 Chapter 6: C H A N G E S I N C O N T R O L S T R E A M S , P O S T H A R V E S T I N G E F F E C T S A N D N E W S E D I M E N T S O U R C E S 137 6.1 Changes i n control sites between 1996 and 1997 137 6.2 Post harvest ing effects 138 6.3 N e w sediment sources, S S I - S S 6 150 6.3.1 P h y s i c a l descriptions o f n e w sediment sources S S 1 - S S 6 150 6.3.2 Texture and m i n e r a l o g y o f n e w sediment sources 160 6.3.3 G e o c h e m i s t r y o f new sediment sources and its appl icat ion to source-sediment tracing 163 6.4 D i s c u s s i o n 184 6.5 S u m m a r y o f post-harvesting effects and n e w sediment sources 186 Chapter 7: D I S C U S S I O N , L O N G T E R M E F F E C T S , R E C O M M E N D A T I O N S A N D C O N C L U S I O N S 187 7.1 L o n g term effects o f l o g g i n g 188 7.2 A p p l i c a t i o n s and impl icat ions 189 7.3 R e c o m m e n d a t i o n s and future projects 190 7.4 S u m m a r y o f methodology 192 7.5 C o n c l u s i o n s 194 R E F E R E N C E S 195 A P P E N D I C E S 202 A P P E N D I X A 203 T e r r a i n M a p ledgend: l o n g vers ion 203 S a m p l e locat ion maps 208 A P P E N D I X B 216 A c c u a r c y - X - Y p l o t s 216 Q u a l i t y contro l data - duplicates 227 A P P E N D I X C 265 R a w stream sediment geochemical results for each stream for each m e t h o d for 1996 and 1997 A P P E N D I X D 2 9 0 T e x t u r a l data f r o m stream sediments 2 9 0 M i n e r a l o g y data f r o m R i e t v e l d 302 Inter-element correlations 303 A P P E N D I X E 310 G e o c h e m i s t r y o f sediment sources 310 T e x t u r a l data f r o m sediment sources 314 R i e t v e l d data for sediment sources 316 vi LIST O F T A B L E S Table 1.1.1 Stream class i f icat ion and speci f ied m i n i m u m R i p a r i a n M a n a g e m e n t A r e a s and R i p a r i a n Reserve Zones slope distances for stream r ipar ian classes i n the Forest Practices C o d e o f B r i t i s h C o l u m b i a 5 Table 1.2.1 Trace element substitution capacity 7 Table 2.3.1 Sediment sources i n Baptiste Creek Watershed; pre- logging point sources o n l y 4 0 Table 2.3.2 Part ic le size analysis for selected samples o f t i l l m a t r i x 41 Table 2.3.3 A v e r a g e grain size distr ibut ion for 5 k g t i l l samples taken f r o m B 5 41 T a b l e 2.7.1 P h y s i c a l characteristics o f the s ix study watersheds 46 Table 2.8.1 Forest types and l o g g i n g act iv i ty for the s ix study watersheds. 51 Table 2.9.1 Changes i n suspended sediment concentrations i n the first year after harvest for b o t h treatments '. 63 Table 2.9.2 Changes i n snowmelt discharge the first year after harvest for both treatments 64 T a b l e 3.4.1 D e t e c t i o n l i m i t s for geochemical analysis w i t h var ious digest ion techniques at C h e m e x L a b s . L t d 87 Table 4.1.1 A c c u r a c y o f geochemical analysis us ing total and aqua reg ia digestions i n 1996 and 1997 for certi f ied reference standards L K S D - 1 , L K S D - 3 , S T S D - 1 , S T S D - 2 , S T S D - 3 , a n d S T S D - 4 94 Table 4.1.2 A c c u r a c y o f geochemical analysis u s i n g total and aqua regia digestions i n 1996 and 1997 for cert i f ied reference standards L K S D - 1 , L K S D - 3 , S T S D - 1 , S T S D - 2 , S T S D - 3 , a n d S T S D - 4 95 Table 4.2.1 S u m m a r y o f T h o m p s o n - H o w a r t h analyt ical and f i e l d p r e c i s i o n results for lab and f ie ld duplicates 104 T a b l e 4.2.2 S u m m a r y o f T h o m p s o n - H o w a r t h p r e c i s i o n results o f the same sample submitted i n subsequent years 105 T a b l e 4.3.1 S u m m a r y o f F-tests for w i t h i n versus between f i e l d duplicate variances 110 T a b l e 5.1.1 M i n e r a l s ident i f ied w i t h i n stream sediment f r o m creeks B 1 - B 6 117 T a b l e 5.1.2 A v e r a g e percentages o f minerals i n sediments f r o m streams B 1 - B 5 determined b y X R D (Rietveld) o n the - 5 3 u m size fraction 118 Table 5.1.3 Concentrat ions o f elements i n heavy minerals , paramagnetic M i n e r a l s and l ight fractions w i t h i n the 53-212 u m size fractions and w i t h i n the - 5 3 u m size fract ion 120 vii Table 5.1.4 S u m m a r y o f average carbon concentrations f r o m s a m p l i n g and analysis i n 1996 and 1997 121 Table 5.1.5 S u m m a r y o f average concentrations o f elements i n streams f r o m s a m p l i n g and analysis after total d igest ion i n 1996 122 Table 5.1.6 S u m m a r y o f average concentrations o f elements i n streams from s a m p l i n g and analysis after aqua regia digest ion i n 1996. 123 Table 5.1.7 G e o c h e m i c a l trends a long streams i n 1996 data 125 Table 5.1.8 Inter-element correlations ident i f ied i n 1996 geochemica l results from total digest ion at the 99.9 % s ignif icance l e v e l 129 Table 5.1.9 Inter-element correlations ident i f ied i n 1996 geochemica l results from aqua regia digest ion at the 99.9 % s igni f icance l e v e l 130 Table 5.1.10 S u m m a r y o f s ignif icant inter-element correlations w i t h r > 0.7 and at the 9 9 . 9 % signif icance leve l from 1996 geochemica l results 131 Table 5.2.1 R a n g e o f abundance o f trace elements i n soi ls and sediments 133 Table 6.1.1 S u m m a r y o f average concentrations o f elements i n streams from 1997 total analyses 139 Table 6.1.2 S u m m a r y o f average concentrations o f elements i n creeks from 1997 aqua regia analyses 140 Table 6.1.3 S u m m a r y o f p r e c i s i o n obtained from s a m p l i n g the same sites i n 1996 and i n 1997 and analyzed i n each year 142 Table 6.3.1 Properties o f n e w sediment sources created w i t h i n the Baptiste watershed as a result o f winter l o g g i n g 151 T a b l e 6.3.2 A v e r a g e grain size d is tr ibut ion o f stream sediments from B 2 - B 5 and sediment sources S S 1 - S S 6 , b y percent weight 161 Table 6.3.3 A v e r a g e percentages o f minerals from sediment sources S S 3 , S S 4 , S S 5 and S S 6 o n streams B 2 to B 5 determined b y X R D (Rietve ld) o n - 5 3 u m size fractions 162 Table 6.3.4 M e a n concentrations o f elements from sediment sources S S 1-SS6 from aqua regia analyses 164 Table 6.3.5 M e a n concentrations o f elements from sediment sources S S 1-SS6 from total analyses 165 Table 6.3.6 G e o c h e m i c a l contrast: rations o f the m e a n concentration o f an element w i t h i n the sediment source to the m e a n concentration i n sediment upstream 166 Table 6.3.7 T-tests for concentration o f elements w i t h i n sediment sources compared to the concentrations o f elements upstream o f sediment sources 167 Table 6.3.8 E lements w h i c h were ident i f ied i n both t-tests and ratios as potent ia l ly useful i n ident i f ing sediment inputs to s m a l l tributary streams to Baptiste Creek after l o g g i n g 168 Table 6.3.9 Percentage o f n e w sediment contributed downstream from S S 4 o n stream B 2 and from S S 5 o n stream B 3 183 viii Table A l T e r r a i n map legend: l o n g v e r s i o n ( f rom Col le t t and R y d e r , 1997) 202 Table B1 .1 -3 A n a l y t i c a l duplicates - total digest ion 1996 227 Table B2.1-5 A n a l y t i c a l duplicates - total digest ion 1997 230 Table B 3 . 1 - 3 A n a l y t i c a l duplicates - aqua regia digest ion 1996 2 3 4 Table B 4 . 1 - 5 A n a l y t i c a l duplicates - aqua regia digest ion 1997 238 Table B 5 . 1 - 2 Y e a r to year analyt ical duplicates - total d igest ion 243 Table B 6 . 1 - 5 Y e a r to year analyt ical duplicates - aqua regia digest ion 245 Table B7 .1 -3 F i e l d duplicates - total digest ion 1996 250 T a b l e B 8 . 1 - 5 F i e l d duplicates - total digest ion 1997 253 T a b l e B 9 . 1 -3 F i e l d duplicates - aqua r e g i a digest ion 1996 258 Table B 1 0 . 1 - 4 F i e l d duplicates - aqua regia digest ion 1997 261 Table C1.1 1996 G e o c h e m i c a l data for stream sediment f r o m B 1 after total d igest ion and carbon data 265 Table C 1 . 2 1996 G e o c h e m i c a l data for stream sediment f r o m B 2 after total d igest ion and carbon data 266 T a b l e C l .3 1996 G e o c h e m i c a l data for stream sediment f r o m B 3 after total d igest ion and carbon data 267 Table C 1 . 4 1996 G e o c h e m i c a l data for stream sediment f r o m B 4 after total digest ion and carbon data 268 Table C1 .5 1996 G e o c h e m i c a l data for stream sediment f r o m B 5 after total d igest ion and carbon data 269 Table C 1 . 6 1996 G e o c h e m i c a l data for stream sediment f r o m B 6 after total d igest ion and carbon data 270 Table C 2 . 1 1996 G e o c h e m i c a l data for stream sediment f r o m B l after aqua reg ia digest ion 271 Table C 2 . 2 1996 G e o c h e m i c a l data for stream sediment f r o m B 2 after aqua regia digest ion 272 T a b l e C 2 . 3 1996 G e o c h e m i c a l data for stream sediment f r o m B 3 after aqua reg ia digest ion 273 Table C 2 . 4 1996 G e o c h e m i c a l data for stream sediment f r o m B 4 after aqua regia digest ion 274 Table C 2 . 5 1996 G e o c h e m i c a l data for stream sediment f r o m B 5 after aqua regia digest ion 275 Table C 2 . 6 1996 G e o c h e m i c a l data for stream sediment f r o m B 6 after aqua regia digest ion 276 Table C3 .1 1997 G e o c h e m i c a l data for stream sediment f r o m B l after total d igest ion and carbon data 277 Table C 3 . 2 1997 G e o c h e m i c a l data for stream sediment f r o m B 2 after total d igest ion and carbon data 278 Table C 3 . 3 1997 G e o c h e m i c a l data for stream sediment f r o m B 3 after total digest ion a n d carbon data 2 7 9 Table C 3 . 4 1997 G e o c h e m i c a l data for stream sediment f r o m B 4 after total d igest ion and carbon data 2 8 0 ix Table C 3 . 5 1997 G e o c h e m i c a l data for stream sediment from B 5 after total d igest ion and carbon data 281 Table C 3 . 6 1997 G e o c h e m i c a l data for stream sediment from B 6 after total digest ion and carbon data 282 Table C4.1 1997 G e o c h e m i c a l data for stream sediment from B l after aqua regia digest ion 283 Table C 4 . 2 1997 G e o c h e m i c a l data for stream sediment from B 2 after aqua reg ia digest ion 2 8 4 T a b l e C 4 . 3 1997 G e o c h e m i c a l data for stream sediment from B 3 after aqua regia digest ion 285 Table C 4 . 4 1997 G e o c h e m i c a l data for stream sediment from B 4 after aqua regia digest ion 286 Table C 4 . 5 1997 G e o c h e m i c a l data for stream sediment from B 5 after aqua regia digest ion 287 Table C 4 . 6 1997 G e o c h e m i c a l data for stream sediment from B 6 after aqua regia digest ion 288 Table C 5 S u m m a r y table o f geochemica l results after h y d r o x y l a m i n e H y d r o c h l o r i d e digest ion 289 Table D l . l T e x t u r a l data for stream sediments from stream B l i n 1996. 2 9 0 Table D 1 . 2 T e x t u r a l data for stream sediments from stream B 2 i n 1996. 291 Table D 1 . 3 T e x t u r a l data for stream sediments from stream B 3 i n 1996. 292 Table D 1 . 4 Textura l data for stream sediments from stream B 4 i n 1996. 293 Table D 1 . 5 Textura l data for stream sediments from stream B 5 i n 1996. 294 Table D 1 . 6 T e x t u r a l data for stream sediments from stream B 6 i n 1996. 295 Table D 2 . 1 T e x t u r a l data for stream sediments from stream B l i n 1997. 296 T a b l e D 2 . 2 T e x t u r a l data for stream sediments from stream B 2 i n 1997. 297 T a b l e D 2 . 3 Textura l data for stream sediments from stream B 3 i n 1997. 298 Table D 2 . 4 T e x t u r a l data for stream sediments from stream B 4 i n 1997. 299 Table D 2 . 5 T e x t u r a l data for stream sediments from stream B 5 i n 1997. 300 Table D 2 . 6 Textura l data for stream sediments from stream B 6 i n 1997. 301 Table D 3 R a w R i e t v e l d results for stream sediment for streams B l - B 5. 302 Table D 4 . 1 S u m m a r y table o f s ignif icant inter-element correlations from streams B 1 - B 5 303 T a b l e D 4 . 2 Signi f icant inter-element correlations for stream B 6 304 Table D 4 . 3 S igni f icant inter-element correlations for stream B l 305 Table D 4 . 4 S igni f icant inter-element correlations for stream B 2 306 Table D 4 . 5 S igni f icant inter-element correlations for stream B 3 307 Table D 4 . 6 Signi f icant inter-element correlations for stream B 4 308 Table D 4 . 7 S igni f icant inter-element correlations for stream B 5 309 Table E l . l 1997 geochemical data from sediment sources 1-3 o n stream B 5 after total digest ion and carbon data 310 T a b l e E l . 2 1997 geochemica l data from sediment sources 4-6 o n streams B 4 , B 3 and B 2 after total digest ion and carbon data 311 Table E 2 . 1 1997 geochemical data from sediment sources 1-3 o n stream B 5 after aqua regia digest ion 312 x Table E 2 . 2 1997 geochemica l data f r o m sediment sources 4-6 o n streams B 4 , B 3 and B 2 after aqua reg ia digest ion 313 Table E 3 . 1 T e x t u r a l data f r o m sediment sources 1-3 o n stream B 5 314 Table E 3 . 2 T e x t u r a l data f r o m sediment sources 4-6 o n streams B 4 , B 3 a n d B 2 315 Table E 4 R a w R i e t v e l d results for sediment sources 3-6 o n streams B 2 - B 5 316 xi LIST OF FIGURES F i g u r e 1.4.1 D e f i n i t i o n o f parameters used i n H a w k e s ' d i l u t i o n m o d e l , equation 1-1 13 F i g u r e 2.0.1 Study area locat ion map 22 F i g u r e 2.0.2 L o c a t i o n map o f streams B 1 - B 5 i n the Baptiste watershed. . . . 24 F i g u r e 2.2.1 B e d r o c k geology map 26 F i g u r e 2.2.2 B e d r o c k geology o f the Baptiste watershed 29 F i g u r e 2.3.1 Pattern o f ice f l o w directions as deduced f r o m d r u m l i n s , g lac ia l grooves, crag and ta i l and striations 32 F i g u r e 2.3.2 G e o m o r p h o l o g i c a l map o f the Baptiste C r e e k watershed 33 F i g u r e 2.3.3 P o r t i o n o f terrain map for streams B 1 - B 6 , i n the Bapt iste watershed 35 F i g u r e 2.3.4 P o r t i o n o f interpretive map for streams B 1 - B 6 , i n the Bapt iste watershed 37 F i g u r e 2.9.1 L o c a l c l imate , and fifteen minute average discharge for a l l three study streams i n the spring o f 1996 and 1997. A l s o , measured and predicted average d a i l y discharge for B 3 and B 5 watersheds for the first spring after harvest 61 F i g u r e 3.1.1 Bapt iste watershed 1996 sample locations 69 F i g u r e 3.1.2 Bapt iste watershed 1997 sample locations 70 F i g u r e 3.1.3 L o c a t i o n o f sediment sources i n the Baptiste watershed 75 F i g u r e 3.2.1 S u m m a r y f l o w chart o f s a m p l i n g and analyt ica l methods for 3-5 k g samples 77 F i g u r e 3.2.2 S u m m a r y f l o w chart o f s a m p l i n g and analyt ical methods for 2 0 k g samples 78 F i g u r e 3.4.1 C o m p a r i s o n o f results returned b y the three digest ion methods for C o i n 1996 85 F i g u r e 3.4.2 C o m p a r i s o n o f results returned b y the three digest ion methods for Z n i n 1996 86 F i g u r e 4.1.1 A c c u r a c y o f geochemical results for M n f r o m total and aqua regia digestions for cert i f ied standards analyzed i n 1996 and 1997 92 F i g u r e 4.1.2 A c c u r a c y o f geochemical results for Z n f r o m total and aqua regia digestions for cert i f ied standards analyzed i n 1996 and 1997 93 F i g u r e 4.2.1 P r e c i s i o n o f C o , N i , and Z n at the 95 % confidence l e v e l determined b y the standard T h o m p s o n - H o w a r t h (1978) method for 1997 geochemical results f r o m total d igest ion for A ) laboratory duplicates and B ) f ie ld duplicates 99 xi i F i g u r e 4.2.2 P r e c i s i o n o f A l , F e , and M g at the 95 % confidence l e v e l determined b y the standard T h o m p s o n - H o w a r t h (1978) m e t h o d for 1997 geochemical results f r o m total d igest ion for A ) laboratory duplicates and B ) f i e l d duplicates 100 F i g u r e 4.2.3 C o m p a r i s o n o f geochemical results f r o m aqua regia digestions for laboratory and f ie ld duplicate samples f r o m 1997 for N i . . . . 101 F i g u r e 4.2.4 C o m p a r i s o n o f geochemical results f r o m aqua regia digestions ' for laboratory and f ie ld duplicate samples f r o m 1997 for Z n . . . 102 F i g u r e 4.2.5 C o m p a r i s o n o f geochemical results f r o m aqua reg ia digestions for laboratory and f i e l d duplicate samples f r o m 1997 for C u . . . . 103 F i g u r e 4.2.6 P l o t o f samples i n order o f sample preparation for C u , M g and Z n to check for systematic errors and contaminat ion 107 F i g u r e 4.2.6 P l o t o f samples i n order o f analysis for C u , M g and Z n to check for systematic errors and contaminat ion 108 F i g u r e 5.1.1 A v e r a g e c u m m u l a t i v e grain size distr ibutions, b y weight , o f stream sediments f r o m creeks B 1 - B 6 and f r o m t i l l sample from sediment sources 115 F i g u r e 5.1.2 G e o c h e m i c a l trends a long streams i n 1996 data 126 F i g u r e 5.1.3 G e o c h e m i c a l trends, i n 1996 data, s h o w i n g the decrease o f the trace elements C o , C r , M g , and N i f r o m the northeast, B 6 to southwest, B 5 127 F i g u r e 5.1.4 G e o c h e m i c a l trends, i n 1996 data, s h o w i n g the decrease o f the trace elements A l , B a , P , and S r from the northeast, B 6 to southwest, B 5 128 F i g u r e 6.1.1 C o m p a r i s o n o f results for B a , C o and C r from undisturbed sites i n 1996 and 1997 141 F i g u r e 6.2.1 C o m p a r i s o n o f results from aqua regia digest ion for samples from 1996 and 1997 for M g 146 F i g u r e 6.2.2 C o m p a r i s o n o f results from aqua regia digest ion for samples from 1996 and 1997 for M n 147 F i g u r e 6.2.3 C o m p a r i s o n o f results from aqua regia digest ion for samples from 1996 and 1997 for N i 148 F i g u r e 6.2.3 C o m p a r i s o n o f results from aqua regia digest ion for samples from 1996 and 1997 for Z n 149 F i g u r e 6.3.1 P r o f i l e o f stream B 4 s h o w i n g the var iat ion i n M g concentrations from samples taken i n 1996 and 1997 169 F i g u r e 6.3.2 P r o f i l e o f stream B 4 s h o w i n g the var iat ion i n N i concentrations from samples taken i n 1996 and 1997 170 F i g u r e 6.3.3 P r o f i l e o f C o , M g , and N i concentrations above and b e l o w S S 4 o n B 4 171 F i g u r e 6.3.4 P r o f i l e o f C o , M g , and N i concentrations above and b e l o w S S 5 o n B 3 172 F i g u r e 6.3.5 P r o f i l e o f B 2 s h o w i n g the var iat ion i n N i concentrations a long stream i n 1996 and 1997 174 xiii F i g u r e 6.3.6 P r o f i l e o f B 3 s h o w i n g the var iat ion i n Z n concentrations a long stream i n 1996 and 1997 175 F i g u r e 6.3.7 P r o f i l e o f B 5 s h o w i n g the var iat ion i n Z n concentrations a long stream i n 1996 and 1997 176 F i g u r e 6.3.8 P r o f i l e o f B 4 s h o w i n g the var iat ion i n Z n concentrations a long stream i n 1996 and 1997 177 F i g u r e 6.3.9 P r o f i l e o f B 2 s h o w i n g the var iat ion i n Z n concentrations a long stream i n 1996 and 1997 178 F i g u r e 6.3.10 P r o f i l e o f B l s h o w i n g the var iat ion i n Z n concentrations a long stream i n 1996 and 1997 179 F i g u r e 6.3.11 G e o c h e m i c a l trends a long B l for C a , K , and M g 181 F i g u r e 6.3.12 G e o c h e m i c a l trends a long B l for P , T i , and V 182 F i g u r e A l 1996 S a m p l e locations o n creek B l 208 F i g u r e A 2 1996 S a m p l e locations o n creeks B 2 and B 3 2 0 9 F i g u r e A 3 1996 S a m p l e locations o n creek B 4 210 F i g u r e A 4 1996 S a m p l e locations o n creek B 5 211 F i g u r e A 5 1997 S a m p l e locations o n creek B l 212 F i g u r e A 6 1997 S a m p l e locations o n creeks B 2 and B 3 213 F i g u r e A 7 1997 S a m p l e locations o n creek B 4 214 F i g u r e A 8 1997 S a m p l e locations o n creek B 5 215 F i g u r e B 1 A c c u r a c y o f geochemical results for B a 216 F i g u r e B 2 A c c u r a c y o f geochemical results for C r 217 F i g u r e B 3 A c c u r a c y o f geochemical results for C o 218 F i g u r e B 4 A c c u r a c y o f geochemical results for C u 219 F i g u r e B 5 A c c u r a c y o f geochemical results for F e 2 2 0 F i g u r e B 6 A c c u r a c y o f geochemica l results for M n 221 F i g u r e B 7 A c c u r a c y o f geochemica l results for N i 2 2 2 F i g u r e B 8 A c c u r a c y o f geochemical results for P b 223 F i g u r e B 9 A c c u r a c y o f geochemical results for Sr 224 F i g u r e B 1 0 A c c u r a c y o f geochemica l results for V 225 F i g u r e B l l A c c u r a c y o f geochemica l results for Z n 226 xiv LIST OF PLATES Plate 2.8.1: V i e w o f the l o w e r p o r t i o n o f cut b l o c k 220-23 after cutt ing, y a r d i n g and r e m o v a l o f trees i n N o v e m b e r 1996 (top). V i e w o f a t y p i c a l active landing , w i t h numerous s k i d trai ls , i n the upper p o r t i o n o f cut b l o c k 220-23 (bottom) 49 Plate 2.8.2: Photos o f cut b l o c k 244-22 after harvesting. Stream B 5 was logged w i t h the aggressive r ipar ian treatment; compare w i t h the conservative riparian treatment o f cut b l o c k 220-23 o f Plate 2.8.4. Photos courtesy o f P . B e a u d r y 52 Plate 2.8.3: V i e w o f cut b l o c k 220-23 before (top) and after (bottom) clear cut l o g g i n g 54 Plate 2.8.4: Photos o f cut b l o c k 220-23 after harvesting. Streams B 1 , B 2 and B 3 were logged w i t h the conservative riparian treatment; compare w i t h aggressive riparian treatment a long stream B 5 o f cut b l o c k 244-22 seen i n Plate 2.8.1. C u t b l o c k 244-22 can be seen i n the background. Photos courtesy o f P . B e a u d r y 55 Plate 2.8.5: E q u i p m e n t used i n harvesting. Fel ler-buncher used to cut and p i l e trees (top) and l o w ground pressure, tracked skidder used to y a r d logs d o w n to landings f r o m the upper port ions o f the cut b l o c k s (bottom) 56 Plate 2.8.6: C o n s t r u c t i o n o f semi-permanent haul road to the b o t t o m o f cut b l o c k 244-22 to stream B 5 i n N o v e m b e r 1996. C o n s t r u c t i o n o f stream crossing at B 3 (top) and m i d w a y between B 3 and B 4 (bottom). F i l l material is water saturated l o c a l t i l l and bedrock 58 Plate 2.8.7: A e r i a l v i e w o f j u n c t i o n o f m a i n h a u l road w i t h n e w l y constructed, semi-permanent h a u l road to cut b l o c k 244-22 to stream B 5 (top). N o t e the large pits where debris and snow was b u r i e d d u r i n g winter road construct ion (bottom) 59 Plate 3.1.1: T y p i c a l sample sites: side bar o n stream B 2 (top) and bar b e h i n d large organic debris o n stream B l (bottom) 72 Plate 3.1.2: T y p i c a l sample sites o n B 5 , top cut b l o c k (right) and w i t h i n the cutb lock (left) 73 Plate 3.1.3: S a m p l i n g equipment used i n the f ie ld (top) and s a m p l i n g procedure (bottom) 74 Plate 6.2.1: L o c a l t i l l mater ia l is h i g h l y erosive. S k i d tra i l i n cut b l o c k 220-23 shows extensive g u l l y i n g and erosion(top) despite seeding i n the spr ing o f 1997. S k i d tra i l i n cut b l o c k 244-22 is h i g h l y water saturated (bottom) 144 XV Plate 6.2.2: T y p i c a l stream crossing at sediment source S S I o n stream B 5 (top) and an aerial v i e w o f the stream cross ing (bottom) 145 Plate 6.3.1: V i e w s o f sediment source S S 2 o n stream B 5 152 Plate 6.3.2: V i e w o f g u l l i e d s k i d trails i n cut b l o c k 244-22 ( B 5 ) w i t h sediment source S S 2 i n the center (top). F i n e sediment f r o m road r u n o f f deposited o n surface o f gravel at sediment source S S 3 , o n B 5 (bottom) 154 Plate 6.3.3: P o r t i o n o f the semi-permanent h a u l road to cut b l o c k 244-22, where r u n o f f f r o m the road enters B 5 , sediment source S S 3 (top). V i e w o f debris and cut b l o c k near S S 3 taken f r o m the h a u l road (bottom) 155 Plate 6.3.4: A e r i a l v i e w o f sediment source S S 6 o n stream B 2 (top) and f r o m the ground (bottom). N o t e the locat ion o f the l a n d i n g , seen i n the f o l l o w i n g three plates. T h e s k i d trai l i n the foreground is the h i g h l y g u l l i e d tra i l seen i n plate 6.3.2 156 Plate 6.3.5: G u l l y i n g o f l a n d i n g at sediment source S S 6 o n stream B 2 (top) and one o f f ive streams o f fine sediment generated i n the l a n d i n g and leading to stream B 2 (bottom) 157 Plate 6.3.6: Further g u l l y i n g o f landing at sediment source S S 6 o n stream B 2 (right) and one o f f ive streams o f fine sediment generated i n the l a n d i n g and leading to stream B 2 (left) 158 Plate 6.3.7: Sediment generated f r o m source S S 6 w h i c h forms channels through the underbrush to where it enters stream B 2 (right) and (left) 159 XVI ACKNOWLEDGMENTS T h i s project was made poss ible b y two years o f funding f r o m Forest R e n e w a l B r i t i s h C o l u m b i a , through the Science C o u n c i l o f B r i t i s h C o l u m b i a , to W . K . Fletcher. A N a t i o n a l Research C o u n c i l scholarship for the durat ion o f this research further assisted the author. C o l l a b o r a t i o n w i t h members o f the Stuart-Takla F ish-Forestry Interaction P r o g r a m ( S T F F I P ) was informat ive and benef ic ia l to this research. Spec ia l thanks to Steve M a c d o n a l d , E a r l i n M a c l s s a k , and H e r b Herunter from the Department o f F isher ies and Oceans; Pierre B e a u d r y from the M i n i s t r y o f Forests ( formerly) ; and A l a n Gottesfe ld from the U n i v e r s i t y o f N o r t h e r n B r i t i s h C o l u m b i a . C a n a d i a n Forest Products L i m i t e d ( C A N F O R ) is an active partner i n S T F F I P and I a m grateful to them for p r o v i d i n g r o o m and board and fuel d u r i n g f ie ldwork. I n particular, G r e g Pearson and W i l l L a f l e n at C A N F O R p r o v i d e d valuable i n f o r m a t i o n and assistance. Thanks to m y f ie ld assistants K a r e n T h o m s o n (1996) and N i c o l e F i e l d - D y t e (1997). S p e c i a l thanks to M e l i s s a Spencer, w h o spent eight months over the two years, m o n o t o n o u s l y s iev ing, d r y i n g and w e i g h i n g samples. T h a n k s also to N i c o l e F i e l d - D y t e and E u n i c e C h a n g for their assistance i n the laboratory. E . P a n i and M . Raudsepp p r o v i d e d m o d a l analyses us ing the R i e t v e l d method w i t h X - r a y p o w d e r dif fract ion data. Thanks to m y committee members M . Raudsepp, A . J . S i n c l a i r and W . K . Fletcher. T h a n k s for y o u r support, inspirat ion and encouragement throughout this project. xvii CHAPTER 1 INTRODUCTION It is w e l l k n o w n i n the forest industry that disturbances associated w i t h l o g g i n g have the potential to increase sediment loads i n streams. In extreme situations, increased sediment loads m a y have deleterious effects o n water qual i ty and f ish habitat. T h i s leads to questions about where sediment comes f r o m , h o w m u c h sediment is contributed b y var ious sources and the degree o f in-channel sediment transport and/or storage. In this w o r k , I investigate the possible appl icat ion o f the natural geochemica l f ingerprint o f sediment sources determined w i t h mult i -e lement geochemica l methods, and address some o f these questions. A l t h o u g h a l o g i c a l extension o f w e l l - k n o w n and w i d e l y appl ied geochemica l methods, this technique has not p r e v i o u s l y been used for this purpose. D e v e l o p m e n t o f such a capabi l i ty w o u l d be benef ic ia l i n sensitive areas, i n m o n i t o r i n g the effects o f fine textured sediments result ing f r o m forestry activit ies, or other causes o f watershed disturbance. H e r e mult i -e lement geochemical analyses w i t h i n s ix s m a l l streams, B 1 - B 6 , i n the northern interior o f B r i t i s h C o l u m b i a are used to: (i) detect changes i n sediment geochemistry before and after clear-cut l o g g i n g ; ( i i ) identi fy the sources o f sediment w i t h i n a watershed; and ( i i i ) trace the transport o f sediment f r o m these sources as it moves a long the stream channel. Systematic s a m p l i n g o f stream sediments was done i n 1996, before l o g g i n g , and again i n 1997 after logg ing . 1 Before d iscuss ing the des ign and results o f this invest igat ion, it is important to g ive some b a c k g r o u n d o n the Forest Practices C o d e o f B r i t i s h C o l u m b i a , controls o n trace element abundance, the effects o f f l u v i a l processes o n sediment geochemistry and the applications o f geochemistry and related studies. 1. 1 Forest Practices Code of British Columbia T h e Forest Practices C o d e ( F P C ) o f B r i t i s h C o l u m b i a establishes standards o f management and p l a n n i n g for forestry activities i n the P r o v i n c e . T h e code came into effect o n June 15, 1995, and consists o f three components: the L e g i s l a t i v e A c t (Prov ince o f B r i t i s h C o l u m b i a , 1996a), the regulations a c c o m p a n y i n g the act (Prov ince o f B r i t i s h C o l u m b i a , 1996b), and management guidebooks. T h e guidebooks are meant to accommodate resource management objectives w h i l e p r o v i d i n g the f l e x i b i l i t y to a l l o w for site specif ic management prescriptions. T h e p r o v i s i o n s o f the guidebooks become lega l ly enforceable w h e n they are used i n p l a n n i n g , prescriptions and contracts. O n e o f the important issues addressed i n the F P C is m i n i m i z i n g the amount o f sediment generated f r o m forestry activit ies w h i c h reaches streams. T o o m u c h fine sediment deposited or incorporated into s p a w n i n g gravels can disrupt the product ion o f organisms basic to the f o o d c h a i n or prevent successful emergence o f fry ( B r o w n , 1991). F P C guidebooks w h i c h address the p r o b l e m o f erosion and deposi t ion o f fine textured sediment inc lude: Interior Watershed Assessment Procedure (Prov ince o f B r i t i s h C o l u m b i a et al., 1995c), 2 Coastal Watershed Assessment Procedure (Prov ince o f B r i t i s h C o l u m b i a et al, 1995a), C o m m u n i t y Watersheds (Prov ince o f B r i t i s h C o l u m b i a et al,, 1996b), C h a n n e l Assessment Procedure (Province o f B r i t i s h C o l u m b i a et al., 1996a), R i p a r i a n M a n a g e m e n t A r e a (Province o f B r i t i s h C o l u m b i a et al., 1995d), and G u l l y Assessment Procedure (Province o f B r i t i s h C o l u m b i a et ai, 1995b). R i p a r i a n areas are the tracts o f l a n d adjacent to the banks o f streams, lakes and wetlands. T h e y inc lude the zone adjacent to a stream dominated b y continuous h i g h moisture content and the adjacent u p l a n d vegetation that exerts an inf luence o n it. Streamside vegetation stabil izes stream banks, regulates stream temperature, and provides large and s m a l l w o o d y debris and important nutrients to the stream. R i p a r i a n areas are considered essential and sensitive components o f the forest ecosystem; however, they often contain some o f the highest qual i ty and most sought after t imber resources. W i t h i n the F P C , r ipar ian areas are protected b y establ ishing two zones, the R i p a r i a n M a n a g e m e n t A r e a ( R M A ) and the R i p a r i a n Reserve Z o n e ( R R Z ) , w h i c h are set distances f r o m stream channels, lakes and wetlands. S p e c i a l constraints are appl ied o n forest practices w i t h i n the R M A , w h i l e the R R Z , i m m e d i a t e l y adjacent to the stream, lake or wet land, is protected f r o m harvesting. T h e objective o f the R M A is to m i n i m i z e or prevent impacts o f forestry activit ies on: stream channels, aquatic ecosystems, water qual i ty , b iodivers i ty , product iv i ty , w i l d l i f e habitat and vegetation o f a l l r ipar ian areas (Province o f B r i t i s h C o l u m b i a et al, 1995d). T h e R M A and R M Z distances are determined b y c lass i fy ing the streams as S1-S6, based o n three factors: the presence o f f i sh , the occurrence i n a c o m m u n i t y watershed, and the average 3 channel w i d t h (Table 1.1.1). R R Z s are usual ly o n l y established a l o n g f i sh bear ing streams w i d e r than 1.5 m . W h e n a R R Z is not required w i t h i n an R M A , the a i m is to: (1) retain sufficient vegetation a long streams to m a i n t a i n shade and reduce bank m i c r o c l i m a t e changes; (2) m a i n t a i n the stabil i ty o f the natural channel and banks; and (3) m a i n t a i n important w i l d l i f e and r ipar ian ecosystem attributes. L o g g i n g activit ies w i t h i n a R M A conta ining a R R Z should leave sufficient trees to m i n i m i z e w i n d t h r o w potential w i t h i n the R R Z and retain sufficient w i l d l i f e trees, h i d i n g and resting cover, nesting sites, structural diversi ty , coarse w o o d y debris and natural r ipar ian f o o d sources (Prov ince o f B r i t i s h C o l u m b i a et al, 1995d). Stream crossings are permitted as l o n g as they are constructed w i t h culverts and w i t h m i n i m a l disturbance. W h e n stream cross ing cause disturbance to the stream banks, a r m o r i n g and re-establishment o f streamside vegetation is required. F a l l i n g and y a r d i n g activit ies must be conducted to m i n i m i z e disturbance w i t h i n a R M A (parallel or away f r o m streams) and y a r d i n g o f logs across a stream m a y o n l y occur o n S5 and S6 streams. 1.2 Controls on trace element abundance: lithological and non-lithological T h e p r i m a r y controls o n the abundance and dis tr ibut ion o f trace elements w i t h i n stream sediment are the l i thologies o f the parent bedrock or sediment source, and the tendency o f trace elements to substitute into the component m i n e r a l phases o f the source. Subst i tut ion is control led b y the i o n i c charge (ox idat ion state), the i o n i c radius o f the trace element and the coordinat ion number, relative to the element w i t h i n the 4 Table 1.1.1: Steam c lass i f icat ion and specif ied m i n i m u m R i p a r i a n M a n a g e m e n t A r e a s ( R M A ) and R i p a r i a n Reserve Zones ( R R Z ) slope distances for stream riparian classes as speci f ied i n the Forest Practices C o d e o f B r i t i s h C o l u m b i a ( P r o v i n c e o f B r i t i s h C o l u m b i a et a/.,1995d) Average Channel Reserve zone Management zone Total RMA Riparian class width (m) width (m) width (m) width (m) SI (large rivers) SI (except large rivers) >= 100 0 100 100 >2() 50 20 70 S2 >5<=20 30 20 50 S4 1.5<=5 1 5 20 o 20 30 40 30 S5 >3 0 30 30 S6 <=3 0 20 20 Fish stream or community watershed Not fish stream and not in community watershed 5 m i n e r a l structure for w h i c h it w i l l substitute (Table 1.2.1). Trace elements c o m m o n l y substitute for the major elements C a , F e and M g i n m i n e r a l structures according to these pr inc ip les . T h e amount o f substitution m a y vary f r o m traces to s m a l l percentages depending o n the condit ions under w h i c h the m i n e r a l was f o r m e d ( L e v i n s o n , 1974). Furthermore, l i t h o l o g y controls the release o f trace elements into secondary weathering products, such as c lays, due to the suscept ibi l i ty o f different minerals to weathering. N o n - l i t h o l o g i c a l controls inc lude secondary trapping o f trace elements b y oxides and hydroxides (Fe, M n , A l ) , organic matter (particulate, d i s s o l v e d and coatings) and clays (most ly f r o m weathering), and the enrichment o f trace elements due to h y d r a u l i c processes result ing i n heavy m i n e r a l accumulat ion. O x i d e s , organic matter and clays, due to their h i g h surface areas, h i g h cation-exchange capacities, and h i g h surface charges, act as sources and s inks o f trace elements. H o r o w i t z and E l r i c k (1987) ranked the importance o f n o n - l i t h o l o g i c a l controls o n trace element abundance f r o m freshwater sediments: A m o r p h o u s F e oxides > total extractable F e > total organic C > reactive F e > c l a y minerals > total extractable M n > M n oxides H o w e v e r , the relative importance o f a particular secondary contro l for trace elements is a funct ion o f p H , E h , c l imate, trace element ava i lab i l i ty and the a v a i l a b i l i t y and capacity o f the contro l w i t h i n i n d i v i d u a l streams or regions. T h e abundance o f 6 T a b l e 1.2.1: Trace element substitution capacity. Trace elements c a n substitute for major elements o f s i m i l a r i o n i c radius and charge i n m a n y c o m m o n minera ls (Shannon, 1976, L e v i n s o n , 1974, Deer , H o w i e and Z u s s m a n , 1966). Element C o m m o n oxidation states Ionic radius o f M 2 + (in Angstroms) Elements for which can substitute C o m m o n minerals i n which substitution may occur Trace elements v i C o 2+, 3+ 0.745,0.61 F e 2 + , M g amphibole, olivine, pyroxene, magnetite, micas v i C u 2+, 1+ 0.73, 0.77 F e 2 + , M g amphibole, pyroxene, magnetite, micas v i N i 2+ 0.69 F e + 2 , M g amphibole,olivine, pyroxene, feldspars, micas viiip b 2+ 1.29 C a feldspars, calcite, amphibole v i M n 2+, 4+, 7+ 0.83, 0.53, 0.46 Ca, F e + 2 , M g amphibole, calcite, micas, olivine, plagioclase, pyroxene, garnet v i Z n 2+ 0.74 Ca, F e 2 + amphibole, calcite, pyroxene, micas M a j o r elements v i i i C a 2+ 1.12 - -v i M g 2+ 0.72 - -v i F e 2+, 3+ 0.78, 0.645 - -7 organic matter, the proport ion o f F e and M n precipitates, the degree o f heavy m i n e r a l accumulat ion, changes i n p H and other variables m a y account for variat ions i n background concentration o f elements o n the stream bed. 1.3 Effects offluvial processes on stream sediment geochemistry W h e n " n e w " sediment enters a stream, f r o m a bank or r u n o f f erosion, or as a result o f sporadic mass wast ing events (landslides and debris f lows) , f l u v i a l processes b e g i n to m o d i f y its texture and geochemical c o m p o s i t i o n . T h e p o r t i o n o f the " n e w " sediment i n the fine sand-si l t-clay (finer than 0.1 m m ) fraction tends to be entrained and f lushed f r o m the stream b e d i n suspension. Entrainment o f mater ia l - 0.1 m m occurs as soon as b e d l o a d transport starts ( B a g n o l d , 1973). W i t h i n the m e d i u m to coarse sand-sized range, the l ight m i n e r a l fractions also tend to be swept away i n suspension dur ing h i g h discharge events, w h i l e heavy minerals i n the sand-sized range are concentrated selectively. T h e coarsest bedload sediments are o n l y m o b i l i z e d and m o v e d i n traction a long the stream bottom dur ing h i g h stream discharge levels. Processes concentrating heavy minerals are thus most effective and consistent i n the fine to m e d i u m sand-sized fractions (Fletcher et al., 1987; Fletcher and L o h , 1996a; Fletcher, 1996). T h e frequency and relative speed w i t h w h i c h sediment m o v e s a l o n g and is r e m o v e d f r o m the stream channel is dependent on: the grain size o f the sediment, the frequency 8 and magnitude o f stream discharge events (cl imate and f l o w regime), and the stratigraphic p o s i t i o n o f sediments (trapping). Concentrat ion o f heavy minera ls occurs where stream energy, w i d t h , ve loc i ty , b e d roughness, and gradient favor the w i n n o w i n g o f l ight minerals f r o m the b e d (Paopongsawan and Fletcher , 1993). H e a v y minerals have l o w e r net transport rates and longer residence t imes i n streams than l ighter sediments; consequently, they accumulate i n drainage basins over l o n g t ime scales ( H o u , 1997). Elements that are the p r i n c i p a l constituents o f heavy minera ls become enriched i n sediments o n the stream bed. E x a m p l e s inc lude: S n i n cassiterite, M g i n garnet, M g (Fe) i n magnetite and detrital A u (S l inger land, 1984; S l i n g e r l a n d and S m i t h , 1986; D a y and Fletcher, 1991; Fletcher, 1996a; Fletcher, 1996). Converse ly , abundances o f fine sediment and elements associated w i t h l ight minerals are indicat ive o f a stream to w h i c h more sediment is added than the stream has the capabi l i ty to remove. Paopongsawan and Fletcher (1993) and Fletcher (1996) observed that the addi t ion o f a b n o r m a l l y large quantities o f s i l t -c lay f r o m increased s o i l eros ion i n a t ropica l catchment changed the texture o f stream sediments f r o m clean sandy gravels to b i m o d a l sandy gravels. T h e addi t ion o f fine sediment m a y change the natural geochemica l patterns o f a stream established b y f l u v i a l processes. F o r example , Paopongsawan and Fletcher, 1993 found that the a d d i t i o n o f fines resulted i n the d i l u t i o n o f heavy m i n e r a l ( A u ) related patterns. T h e geochemica l i m p l i c a t i o n s o f these f l u v i a l processes o n elements m o r e u n i f o r m l y distributed i n the sediments (e.g. base metals) should also be considered. U n l e s s these 9 elements b e c o m e trapped w i t h i n secondary weathering products (e.g., F e - M n oxides and hydroxides , c l a y minerals) , they are most l i k e l y to be contained w i t h i n the silt-c lay fractions o f the sediment and to be f lushed f r o m the stream bed. Concentrat ion o f these elements are therefore l i k e l y to decrease as fines are f lushed f r o m the stream bed and sediments become depleted i n these elements relative to the soi ls (Fletcher a n d L o h , 1996a). F l u v i a l processes m o d i f y and systematical ly change the l i t h o l o g y , geochemistry and grain-size d is tr ibut ion o f sediments w i t h i n a stream. T h e sand-si l t-clay size fraction contains the sizes o f grains that are i n i t i a l l y deposited, m o b i l i z e d , and r e m o v e d f r o m the stream bed, as w e l l as the sizes o f grains i n w h i c h the accumulat ion o f heavy minerals most c o m m o n l y occurs. T h e effects o f heavy m i n e r a l accumulat ion and the r e m o v a l o f fines w o u l d not be as apparent i n a coarser or f iner s ized fraction. A d d i t i o n a l l y , the sand-si l t-clay fraction tends to be enriched i n trace elements f rom the products o f weathering, secondary oxides and clays. Therefore, analysis o f the m e d i u m sand-si l t-clay (-0.212 m m ) fraction w i t h trace element geochemistry should be a sensitive m e t h o d to identi fy and trace n e w sources o f sediment. 1.4 Using geochemistry to trace sediment from point sources G e o c h e m i s t r y tradit ional ly has been e m p l o y e d as a m i n e r a l explorat ion too l b y u t i l i z i n g one or more c h e m i c a l properties o f a natural mater ia l ( so i l , sediment, water, 10 rock, drift, vegetation) to trace anomalies upstream to their source. T h i s research seeks the opposite scenario: to trace sediments downstream f r o m their source to the point where their concentration is reduced to b a c k g r o u n d levels b y d i l u t i o n . Stream-sediment surveys, due to their re lat ively l o w cost and ease o f c o l l e c t i o n , have become one o f the most important and w i d e l y used applicat ions o f geochemistry. T h e interpretation o f stream-sediment s a m p l i n g is a ided b y the development o f landscape geochemical m o d e l s for different c l i m a t i c regions w i t h different rates and sources o f sediment supply. Ideal ly , a stream sediment sample is a composi te o f sediments w h i c h is representative o f the products o f weathering and erosion der ived f r o m the catchment b a s i n and funneled into and a long the stream channel (Fletcher, 1997). It is general ly accepted that the c o m p o s i t i o n o f sediments represents a long-term average, w h i c h is re lat ively stable w h e n compared w i t h the c o m p o s i t i o n o f stream waters (Rose, H a w k e s and W e b b , 1979). H o w e v e r , it is important to recognize that geochemistry m a y vary between discharge events, between seasons and between years. T e m p o r a l v a r i a b i l i t y has been documented b y var ious researchers. F letcher and L o h (1996a) found that S n i n bedload c o u l d vary b y more than an order o f magnitude i n less than four hours dur ing a s ingle discharge event. R i d g e w a y and M i d o b a t u (1991) found increases i n elements associated w i t h heavy minerals after the t a i l o f a c y c l o n e h a d passed, w h i l e Fletcher and D a y (1989) found order-of-magnitude variations i n A u concentrations between seasons. H o w e v e r , i n explorat ion programs these temporal geochemica l variations i n stream sediments are usual ly considered n e g l i g i b l e for most elements 11 and most c l imates, w h e n compared to o v e r a l l var iat ion i n geochemistry across a region. I n a tradit ional approach to interpretation o f geochemica l data, sediments w o u l d be c lass i f ied according to their bedrock source, and b a c k g r o u n d and threshold values determined for each geo log ica l unit (Fletcher, 1997) Stream-sediment geochemistry can then be used to identi fy anomalous dispers ion trains, and f o l l o w them upstream to their source. U s u a l l y , this i n v o l v e s ident i fy ing anomalous concentrations o f one or m o r e elements and f o l l o w i n g them upstream to the m a x i m u m concentration, w h i c h is considered to be closest to the source or the anomaly cut-off. F r o m these concepts, H a w k e s (1976) proposed the f o l l o w i n g a n o m a l y d i l u t i o n m o d e l (Figure 1.4.1) as a guide to the design and interpretation o f explorat ion stream sediment surveys: MeJ^ = A a ( M e a - M e , ) + M e , (1-1) where: A,,,, A a are the areal extent o f the deposit and the area above the s a m p l i n g site, respectively, and M e m , M e a and M ^ are the concentrations o f the deposit, the anomalous sample site and background, respectively. H o w e v e r , i f the drainage area is re lat ively large compared to the size o f the deposit, then the deposit can be considered a point source. T h e term A ^ M e , then becomes s m a l l relative to the other terms and can be considered negl ig ib le . T h e d i l u t i o n m o d e l then reduces to the f o r m : 12 Downstream direct ion Figure 1.4.1: Definition of parameters used in Hawkes' dilution model, equation 1-1 (From Hou, 1997 after Hawkes, 1976). 13 M e m A m = A a ( M e a - M e b ) (1-2) T h i s equation generates a smooth hyperbol ic decay curve for the anomalous dispers ion train d o w n - b a s i n f r o m the cut-off point where the quantity ( M e a - M e , ) is a measure o f the strength o f the anomaly over background ( H a w k e s , 1976). T h i s m o d e l is idea l ized and depends o n s ix p r i m a r y assumptions: u n i f o r m rate o f erosion, u n i f o r m geochemica l background, no feedback between water and sediment, no s a m p l i n g error, a s ingle anomalous source, and no contaminat ion ( H a w k e s , 1976). T h e theory provides a conceptual m o d e l for the type o f d i l u t i o n pattern to be expected downstream from any point source o f a different geochemical c o m p o s i t i o n than surrounding b a c k g r o u n d sediment sources. I f the element i n the point source has a higher concentrat ion than the background, the concentration o f the element should increase i m m e d i a t e l y downstream o f the source. T h e n the concentrat ion o f the element should decrease m o v i n g downstream, f o l l o w i n g the h y p e r b o l i c decay curve, as the drainage area increases and the sediment from the source becomes di luted. H o w e v e r , w h i l e conceptual ly reasonable, this part icular m o d e l cannot be appl ied direct ly to most point sources, such as landslides, stream crossings, or m i n i n g effluent/sediment, because they are episodic processes w h i c h occur sporadica l ly and irregularly . H a w k e s ' m o d e l requires that erosion occurs at a u n i f o r m rate and that no feedback occurs between sediment and water. 14 Attempts to determine the provenance o f fine sediment w i t h i n r ivers have f o l l o w e d two m a i n approaches. T h e first has been to p h y s i c a l l y measure properties o f sediment sources b y tradit ional f ie ld techniques and then apply models or p h y s i c a l reasoning (sediment budgets) to estimate the contr ibut ion f r o m each sediment source (e.g. D i e t r i c h and D u n n e , 1978; Jordan and S laymaker , 1991). T h e f i e l d techniques often i n v o l v e measur ing erosion and g u l l y i n g w i t h erosion p ins and prof i lometers . S o m e researchers (e.g., D u i j s i n g s , 1985 and Stott et al. 1987) have attempted to l o o k at the impacts o f forestry activities between forested and unforested basins from sediment transfer calculat ions based o n bedload and suspended sediment measurements. H o w e v e r , they found that the interactions between sediment del ivery , sediment storage, sediment r e m o b i l i z a t i o n and c l i m a t i c controls (rainfall) were too c o m p l e x for analysis u s i n g current sediment transfer models . T h e second research approach is to examine one or m o r e diagnostic/dist inctive properties o f the sediment source to determine a " f ingerpr int" for the source w h i c h can be used to identi fy the materials from the source w i t h i n suspended sediment i n -channel . D i a g n o s t i c properties w h i c h have been used i n c l u d e sediment c o l o r ( G r i m s h a w and L e w i n , 1980; Imeson et al, 1984), s o i l properties/chemistry (Peart and W a l l i n g , 1986, 1988; W a l l i n g and W o o d w a r d , 1993; Peart, 1995), magnet ic minerals ( O l d f i e l d et al, 1979; W a l l i n g et al, 1993; C a i t c h e o n , 1995), and radionucl ides (Peart and W a l l i n g , 1986,1988; W a l l i n g and W o o d w a r d , 1992; W a l l i n g et al, 1993; H e and O w e n s , 1995). 15 Peart and W a l l i n g (1986) used several s o i l properties (P , N, C , and M n concentrations) to m a k e quantitative estimates o f the relative contr ibut ion to a stream f r o m various sources o f sediment. T h e y proposed a s i m p l e m i x i n g m o d e l that can be used to estimate the amount o f material der ived f r o m a sediment source at any point downstream: P s = 100 x ( C 2 - C,) / (C„-C,) ( F o r C , < C s s ) P s = 100 x {1- (C2 - C s s ) / ( C r C J } ( F o r C , > C s s ) Where: P s = Percentage o f sediment f r o m sediment source C s s = Concentrat ion representative o f sediment source C 2 = Concentrat ion at a site downstream o f the sediment source C , = Concentrat ion representative o f the stream before introduct ion o f sediment. ( M a y also use the concentration i m m e d i a t e l y upstream o f the sediment source). H o u (1997) appl ied this m i x i n g m o d e l w h e n consider ing the effect o f sediment f r o m a landsl ide o n the concentrations o f elements ( A l , B a , M g , N a ) i n sediments o f h i g h and l o w energy sites downstream. H o u and Fletcher (1996) found that the effect o f the sediment source c o u l d be traced g e o c h e m i c a l l y at least 2.5 k m downstream. Peart (1995) and W a l l i n g et al. (1993) have further used m i x i n g m o d e l s i n mult i-parameter approaches to f ingerprint sources o f suspended sediment. H o w e v e r , w i t h the except ion o f H o u (1997), there has been no invest igat ion into the appl icat ion o f m u l t i -element geochemistry to trace sediment sources o n the stream bed. M u l t i - e l e m e n t geochemistry provides concentrations for 20-32 elements, o f w h i c h there are c o n c e i v a b l y a sufficient number to d is t inguish the sediment source f r o m the natural stream sediments ("f ingerprint") . A c c o r d i n g l y , mult i -e lement geochemistry m a y be a 16 relat ively s i m p l e and inexpensive means to provide data for the appl icat ion o f m u l t i -parameter m i x i n g models to trace sediment. 1.5 Related Studies T h e greatest environmental impacts result ing from l o g g i n g activit ies w i t h the most s o i l disturbance and subsequent erosion have been s h o w n to result from 1) the construct ion o f stream crossings, 2) construct ion o f roads and landings adjacent to streams, and 3) y a r d i n g o f logs ( B r o w n , 1991). T h e p r i m a r y source o f sediment from l o g g i n g activit ies i n the P a c i f i c Northwest is the roads used to access forest stands, rather than the t imber management activities ( M e g a h a n and K e t c h e s o n , 1996). B r o w n (1991) s h o w e d that w h e n trees are harvested w i t h methods that do not create s o i l disturbance, the turbidi ty and suspended sediment concentrations i n streams do not change. R o a d construct ion has been associated w i t h a number o f effects o n h y d r o l o g i c and geomorphic processes, i n c l u d i n g changes i n rates o f surface erosion (increases) ( R e i d and D u n n e , 1984), t i m i n g and magnitude (increases) o f peak stream discharge (Beaudry, 1998; H o r n b e c k et al. 1993), suspended sediment concentrations (increases) ( M e g a h a n et al, 1986; Beaudry , 1998; D o u g l a s et al, 1992), channel m o r p h o l o g y ( B i l b y et al, 1989), and increases i n the occurrence o f landsl ides ( F a n n i n et al, 1997). R o a d construction increases the length o f ephemeral channels b y p r o v i d i n g n e w routes for surface r u n o f f (Douglas et al, 1992; D u n c a n et al, 1987). 17 R o a d s i d e r i l l s and gul l ies f r o m steep cut and f i l l slopes supply sediment to streams (Douglas et al, 1992). I n t ropica l M a l a y s i a n streams, l o g g i n g disturbance was found to l o w e r geochemica l b a c k g r o u n d values for some elements (Fletcher and M u d a s , i n prep.). F letcher and M u d a s ( in prep.) proposed that the lowered background was due to deep t ropica l weathering and leaching o f residual soils w h i c h had depleted concentrations o f elements i n the regol i th compared to the parent bedrock. Thus , the fine materials f r o m regol i th added to streams were already depleted i n trace elements, result ing i n the lowered b a c k g r o u n d concentrations observed. Further, the c o m p l e x patterns i n background concentrations were found to be related to both the nature o f the sediment source (bedrock or regol i th dominated) and subsequent m o d i f i c a t i o n b y f l u v i a l processes (concentration o f heavy minerals and r e m o v a l o f fines). T h e y found that greater than 8 0 % o f the var iat ion i n trace element concentrations result ing f r o m these processes c o u l d be accounted for i n regression equations b y us ing T i as a surrogate for concentration o f magnetite and heavy minerals , and K as a surrogate for the content o f O . 0 5 3 m m fines. Other researchers have also examined the effects o f sediment inputs o n natural geochemica l patterns w i t h i n streams. Paopongsawan and Fletcher (1993) found that increased sediment f r o m erosion o f agricultural areas i n H u a i H i n L a e p i n northeastern T h a i l a n d , led to the d i l u t i o n o f a A u anomaly b y barren silt and c lay to concentrations b e l o w the detection l i m i t (5 ppb) o f convent ional fire assay-atomic 18 absorption methods. In B r i t i s h C o l u m b i a , H o u and Fletcher (1995) e x a m i n e d the effect o f sediment inputs f r o m landslides o n A u anomalies i n stream sediments. T h e y found that fine mater ia l f r o m nearby landslides can result i n the ident i f i cat ion o f false anomaly cut-of f points that can be misinterpreted to indicate that the landsl ide is the source o f the A u entering the stream. These examples a l l suggest that the addi t ion o f m o r e sediment to a stream m a y di lute or even el iminate geochemica l anomalies that under natural condit ions result f r o m the preferential accumulat ion o f heavy minerals . 1.6 Summary and study objectives T h e impact o f fine textured sediment generated f r o m forestry activit ies o n f ish , water resources, other organisms and domestic water supplies has been o f g r o w i n g concern. D e t e r m i n i n g h o w m u c h sediment is h a r m f u l , where sediment comes f r o m and w h i c h activit ies release harmful quantities o f sediment have been major research questions. Trace element geochemistry o f the fine sediment s ized fractions m a y be a part icular ly sensitive method o f tracing the movement o f sediment f r o m its source. M i x i n g models u t i l i z i n g geochemical data f r o m analysis o f fine sediment m a y be useful i n e x a m i n i n g the effects f r o m inputs o f fine sediment o n s m a l l streams due to forestry activit ies. 19 T h e objectives o f this study are: 1. Determine i f mult i -e lement geochemistry can be used to detect changes i n sediment geochemistry before and after logg ing . 2. A p p l y mult i -e lement geochemistry to identi fy the sources o f sediment w i t h i n a watershed and define a unique geochemica l f ingerprint for each source. 3. Determine i f mult i -e lement geochemistry can be used to trace the transport o f sediment f r o m these sources as it moves a long the stream channel . 4. Present a generalized methodology b y w h i c h geochemistry can be appl ied to trace sediment in-channel f r o m sediment sources. 5. Present appl icat ions o f these technique and areas for further research. 20 CHAPTER 2 STUDY LOCATION AND PROJECT LAYOUT T h e study area was selected because o f the weal th o f m u l t i - d i s c i p l i n a r y i n f o r m a t i o n avai lable f r o m other researchers i n the Stuart-Takla F ishery-Forestry Interaction P r o g r a m ( S T F F I P ) . T h e research areas are located north o f Fort St. James, i n north-central B r i t i s h C o l u m b i a (Figure 2.0.1). S T F F I P includes members f r o m the M i n i s t r y o f Forests ( M O F ) , M i n i s t r y o f Fisheries and Oceans ( D F O ) , the Sc ience C o u n c i l o f Canada, C a n a d i a n Forest Products ( C A N F O R ) , and several researchers f r o m T h e U n i v e r s i t y o f B r i t i s h C o l u m b i a , T h e U n i v e r s i t y o f N o r t h e r n B r i t i s h C o l u m b i a and T h e U n i v e r s i t y o f A l b e r t a . F u n d i n g for most o f the projects comes f r o m Forest R e n e w a l B r i t i s h C o l u m b i a , the Science C o u n c i l o f Canada, and Federa l and P r o v i n c i a l M i n i s t r i e s . T h e research components o f S T F F I P were designed to develop an understanding o f the ecosystem processes that affect stream p r o d u c t i o n and forest outputs w i t h i n f ive large watersheds over m u l t i p l e years. P h y s i c a l measurements inc lude suspended sediment, bedload, stream temperatures, h y d r o l o g y , groundwater (piezometr ic levels), organic debris, solar radiat ion, and, i n f i sh bearing streams, the number o f returning sockeye s a l m o n and the s u r v i v a l rates o f fry. T h e objective o f the p r o g r a m is to l i n k these p h y s i c a l factors w i t h b i o l o g i c a l outcomes or effects. 21 Figure 2.0.1: Study area location map, NTS 93 K/14 at latitude 54° 52'N and longitude 125° 23'W. Baptiste Creek is within the square. Digital base map from British Columbia Ministry of Energy and Mines, (1998). 22 Spec i f i ca l ly , the Baptiste Creek drainage, located just north o f T r e m b l e r lake (Figure 2.0.1), was selected for this research p r o g r a m because the schedul ing o f harvest ing i n the winter o f 1996-97 a l l o w e d for pre- and post- l o g g i n g s a m p l i n g . A l s o , Baptiste p r o v i d e d the opportunity to study four streams that w o u l d be affected b y the l o g g i n g o f the two cut b l o c k s , and two watersheds that w o u l d r e m a i n undisturbed to act as controls (Figure 2.0.2). 2.1 Location, physiography, and access Baptiste Creek is located o n the N e c h a k o Plateau i n the northern interior o f B r i t i s h C o l u m b i a at latitude 5 4 ° 5 2 ' N and longitude 1 2 5 ° 2 3 ' W (Figure 2.0.1) (Trembleur L a k e 1:50,000 map sheet ( N T S 93-K/14)) . T h e N e c h a k o Plateau is b o u n d e d to the north b y the H o g e m Ranges o f the O m i n e c a M o u n t a i n s and the Fraser B a s i n L o w l a n d s to the east (Col lett and R y d e r , 1997). T h e plateau surface l ies between 1200 and 1550 m (4000 to 5000 ft) e levation ( H o l l a n d , 1976) and is c o m p r i s e d m o s t l y o f expanses o f flat or gently r o l l i n g country. H o w e v e r , i n the study area the plateau is interrupted b y a s m a l l northwest trending m o u n t a i n range, w i t h M o u n t S i d n e y W i l l i a m s direct ly to the north (Figure 2.0.2). W h i l e port ions o f the plateau r e m a i n un-dissected, others are i n c i s e d to the leve l o f the Fraser R i v e r and its tributaries. Baptiste C r e e k f lows northeast and is a tributary o f M i d d l e R i v e r , w h i c h is part o f the T a k l a L a k e - Fraser R i v e r drainage to the south. T h e study streams are located i n the southwestern headwaters o f the Baptiste watershed, just north o f 23 Figure 2.0.2: Location map of streams B1-B5 in the Baptiste Watershed (NB stream B6 is off the map to the NE) and proposed cut blocks (220)-23 and (244)-22.Note the location of the newly constructed semi-permenant haul road to cut block 220-23, shown in red. 24 T r e m b l e u r L a k e . C u t b l o c k s were pos i t ioned to a l l o w for s a m p l i n g above, b e l o w and w i t h i n areas harvested o n the four streams w h i c h w o u l d be affected. T h e upper portions o f the streams and the two unharvested streams were to be used as controls to m o n i t o r changes i n unaffected areas. T h e study area is located w i t h i n the F o r t St. James Forest D i s t r i c t and is accessible from Fort St. James b y 200 ki lometers o f active forest service roads. D r i v i n g t ime from Ft . St. James to Baptiste Creek is approximately four hours. 2.2 Bedrock geology T h e N e c h a k o Plateau, north o f F o r t St. James, B . C , was o r i g i n a l l y m a p p e d b y A r m s t r o n g at a scale o f 1:253:440 i n 1949 (Figure 2.2.1). Seven m a i n geo log ica l units were ident i f ied i n the region: the T a k l a G r o u p (6), the T o p l e y Intrusions ( 5 A & 5 B ) , the Tachek G r o u p (8), part o f the H a z e l t o n G r o u p (7), the O m i n e c a Intrusions (9), the C a c h e C r e e k G r o u p ( 2 A ) , and the Trembleur Intrusions ( 4 A & 4 B ) . T h e regional geology, part icular ly that to the west o f the study area, is described, as it is from these rock units that the g l a c i a l deposits o f the study area were derived. Clasts from these v a r y i n g l i thogies were found i n the stream sediments. T h e study area is under la in b y serpentinized peridotite and dunite o f the T r e m b l e u r Intrusions (Col let t and R y d e r , 1997) (Figure 2.2.2), and the south-east p o r t i o n o f the Bapt is te Creek 25 26 Legend to accompany Figure 2.2.1 (Armstrong, 1949). TERTIARY O L I G O C E N E O R L A T E R E W Q W C Q G R O U * } ISA, rr.mniy t,0mfOuimr and amytftiaUnidaJ b&s&tl., ond&niZet ; ' l i ™ ! ISO, trwhytji^ mod vntfaefefe ftwa, a>fcw*, -antf S/MR: mar*' j in- otd**r tfvm ISA E O C E N E O R O L I G O C E N E c /Tc/ww, r u/>v imrvu(ot*t, mmor ri-jcjf^ TRIASSIC AND JURASSIC U P P E R T R 1 A S S 4 C A N D L A T E R TAKLA GROUP AtKh4ttfG sVtd tusw/fk:' /Tow?*, tvtYs, fifwy-int* &cjgJom&rvie&; mttrrtwJded ewnpAprmratie, W rcw ( o / o m « r # o - , **ier /(mtr^f.orw (ijpper Tin* PERMIAN (?) AND/ OR LATER P O S T - M I D D L E P E R M I A N , P R E - U P P E R J U R A S S I C >^ T O P t E r I N T R U S I O N S ' • j S A , •"' <jr\ifX}dk'r;te 13 CongtammMm, •.-wwJston©, srrf n.h«;«?(- minor fufT P O S T - M I D D L E P E R M I A N , P R E - U P P E R T R I A S S H C (Ti T H t M S L E U R I N T R U S I O N S CRETACEOUS AND TERTIARY U P P E R C R E T A C E O U S O R L A T E R "j t Z A , ,w •iftotf, t r-nofyft', .trul r+iyofif.O; inrt>r% vttat^d t p R f l A P j j j B . ,-t,yr.htv, .i&rtif?, aruhnute, txusatt; minor L.;. i J -*-'.vr'«/ ((/*//: ,'»frt t-'-i-rc *.+s; r-iav .'*•> nartty or c.tr-r-i} of S#TK* (/(>• .'«a 14 U P P E R C R E T A C E O U S A N D P A L E O C E N E * U S T U T C R O U P i tt ! ' • •ftijtornn»rat.f. urutte, tjr*zvwr*cice, and tuff JURASStC OR CRETACEOUS U P P E R J U R A S S I C ff O R L O W E R C R E T A C E O U S USLJkA FORMATION: cf>rtglttfrmrat»; minor •wrwte*or»*? oT^ci shul**; may t>*r partly yottrnjer U P P E R J U R A S S I C O R L O W E R C R E T A C E O U S O M 1 N E C A I M H U S I O N 5 Q . [ Giy*rKxiioriT€-r quartz diortte, diorits-, mirror j grwntte, nyvnito, gahbrOf anrf f^ y/SCKttsrWti* y JURASSIC AND (?l CRETACEOUS 0 N TACHEft G R O U P Andmvte and andbgifci! hroc*^  fottRRft and rt\voitt# PART OP M A Z E L T O * CSRCJUP Anttegit.*, trachyte, b—fo " ^ d r*?MrrW hfrs&t m A A, pur i 4 B , ;..v<-rxtrtdaUte, durtitet m i n e r /»y7v*OTn/C*? w i d KirrtzenTjnizwrt and &.tf*atixfid oa-unntieritft •roarKnite, minor peridot, it* and ffst*^ M r p J n t f h f t N K d finer ttu?M tee-d Axjurwx&rjCs. Mmy hte in pari f^o(tt~Trw«tk: 0 0 N PENNSYLVANIA* (7) AND PERMtAN C A C H E C R E E K . G R O U P AtieSe&ttk} flows, tufSf antf frrwoohsK wjfc/j ??<>n«r faasK..- intruBK/t?s ((jrt'.er\(itnrn*e); chfct^iT.e- <md homttiwtrte eeh&tm; minor &ryiitit&, and tima&ton*-. M$y n-iciudft iromp Vnkla snex»/J *yx^ fcs(4) I aA. / t f - f cor ; chert, argil cf%jarTiriie,t argil ft t**, r- to 0> lirrreittxirrfj m i f k i r ..w> f^rfwi-wraeip arid ffrftywK4t<t>; rrt+tt*fT>r/r~ptu>a**d minor f.tmrt ood frfrwwtone. /7^>^/ic»ri o/ ' S B f/.' JBA-ivot tn/v.ivrt; ,'-«.•>( /; in fMtri xtfdrr t/w»r.- 1,-arts* W O L V E R I N E C O M P L E X t j u i * r e ^ - i e « , M f « « . ' ' IttrmmtotiVi • minor fjrtei9v and ne&rnot'tv. f-YoJ**£>(y ftwtam rr#<:*>mi>ris*n ror*» MINERAL Chromium Cr Co*/ . C C(*pp**r. • . . Cu GoW An tcsad Fb M&gne&ir& M« Mang&rt&ae Mn A//*?rcury Molybdenum Mo Ph&stphnrus. .' P Stiver Ag 7>n - , , 8n Tungsten W Vanmltum V Ztna Zn Heavily drift-cxjv&r&tJ w>?w • /v;fl'!:;;'"v'** f'autt ar fmtlt rone •• Antiatin&t *Kci& , — —— Synclinal &cvf& — Fossil locality iJF) Mineral OQCHJrT0nCG * F^rovinci&l highway RofKl and buildings —t ; — Rond rK>t well travelled _ — — — Trail or wittier road Church * School • Fast Office • Tnangut&tian station A Land District boundary • — Forest Reserve boundary . . . . . . Indian Ref)er\'e boundary Range line — Lake and Btream (position approximate) <-^ -"^ -r Marsh — j * : ' : * ^ Contours (interval 500 feet) , • • • SjEggSs Contours (position approximate) Height in feet above mean sea-level HSO 27 watershed is under la in b y rocks o f the C a c h e Creek G r o u p (grey cherts, argi l l i te , slate and m i n o r andesite (greenstone), and l imestone) (Col let t and R y d e r , 1997). T h e T r e m b l e u r Intrusions consist o f M e s o z o i c ultrabasic rocks i n c l u d i n g a serpentinized peridotite-dunite bathol i th u n d e r l y i n g M o u n t S y d n e y W i l l i a m s and several serpentinized periodite-dunite s i l l s outcropping between M o u n t S y d n e y W i l l i a m s and T s i t u s u l M o u n t a i n ( A r m s t r o n g , 1965) (Figure 2.2.1). H y d r o t h e r m a l alteration o f approximate ly 10 % o f the serpentinized peridotite has weakened the rock and increased its susceptibi l i ty to erosion. G l a c i a l scour ing o f this hydrothermal ly altered bedrock has resulted i n pockets o f c l a y - r i c h t i l l s w i t h i n the area (Col let t and R y d e r , 1997). T h i s unit hosts several chromite deposits, w h i c h i n the p r o x i m i t y o f the study area are: the T i l d e s l e y Creek deposit, the M o u n t S y d n e y W i l l i a m s Depos i t , the V a n D e c a r Creek D e p o s i t and the Ts i tusut l M o u n t a i n D e p o s i t ( A r m s t r o n g , 1965). T h e largest deposit closest to the study area is the M o u n t S y d n e y W i l l i a m s D e p o s i t w i t h m i n e r a l i z a t i o n w h i c h averages 3 - 5 % chromite ( A r m s t r o n g , 1965). O n the north slope o f M o u n t S y d n e y W i l l i a m s an asbestos deposit o f chrysot i le has also been located. W h i l e the asbestos is o f p o o r c o m m e r c i a l qual i ty , the w h o l e zone contains approximate ly 5 % asbestos ( A r m s t r o n g , 1965). T h e C a c h e Creek G r o u p is c o m p r i s e d o f a th ick assemblage o f P e r m i a n and P e n n s y l v a n i a n interbedded sedimentary and v o l c a n i c rocks. W e s t o f the study area, the C a c h e C r e e k G r o u p ( 2 A ) consists o f r i b b o n chert, argi l laceous quartzite, argi l l i te , 28 Geology Legend 4a Amphibolite; peridotite; serpentine; serpentinized peridotite and dunite; alteration products 1 Grey chert, argillite, and slate; minor andesite (greenstone) and limestone. Heavily drift-covered area Z. o 2. f t> 8 Scale (km) s> Study area boundary Lake Contour interval 500 feet Figure 2.2.2: Bedrock geology of the Baptiste Watershed (Collett and Ryder, 1997, after Armstrong, 1949). 29 slate, greenstones, l imestone, m i n o r conglomerate and greywacke, metamorphosed equivalents, and s m a l l bodies o f T r e m b l e u r intrusions ( A r m s t r o n g , 1965). T h e T a k l a G r o u p consists o f an apparently conformable succession o f interbedded v o l c a n i c and lesser sedimentary rocks ranging i n age f r o m U p p e r T r i a s s i c to U p p e r Jurassic ( A r m s t r o n g , 1965). T h i s group includes andesitic and basalt ic f lows , tuffs, breccias, agglomerates, interbedded shales, greywackes, conglomerates and l imestones. T h e T o p l e y Intrusions are a group o f ac id ic intrusive rocks o f pre-Jurassic A g e c o m p o s e d o f granite and granodiorite ( 5 A ) and syenite ( 5 B ) . Granites range f r o m very coarse pegmatit ic rock to f ine-grained p i n k granite and grey or grey-green granite and granodiorite ( A r m s t r o n g , 1965). T h e T a c h e k G r o u p is c o m p o s e d o f andesite and andesite brecc ia , basalt, and rhyol i te . T h e most characteristic member o f this group is a green or purple eruptive andesite brecc ia that weathers to a m u c h l ighter shade. B r e c c i a fragments are p r i m a r i l y andesite, but fragments o f rhyol i te , chert, granite and feldspar also occur. H a z e l t o n G r o u p rocks consist o f andesite, trachyte, basalt, and related breccias. These v o l c a n i c rocks consist o f andesitic and, to a lesser extent, basaltic, daci t ic , trachytic , and r h y o l i t i c f lows, and andesite breccias. T h e y are usual ly mass ive and pale to dark green, but m a y also be red, grey, purple , b l a c k and i n the case o f the rhyol i tes , 30 salmon-pink (Armstrong, 1965). Hazelton Group volcanics are largely altered to limonite, chlorite, and epidote. The Omineca Intrusions are composed of numerous bodies of intrusive rocks believed to be of Upper Jurassic or Lower Cretaceous age. They range in size from small sills and dykes to batholiths, and in composition from granite to pyroxenite, with granodiorite predominating. East of the study area the stock is composed of medium-grained, grey equigranular granodiorite in the center, grading into grey-green diorite at its borders (Armstrong, 1965). 2.3 Quaternary Geology and Surficial Materials Landforms and surfical materials within the Baptiste watershed are largely a result of the Fraser Glaciation (Beaudry, 1998), the last of the Pleistocene glaciations, that reached its maximum 15,000 years B .P . The area was completely covered during the Fraser Glaciation with the exceptions of high peaks, such as the peak o f Mount Sidney Will iams. The terrain and surrounding ridges show the effects of ice abrasion and glacial deposits. Collett and Ryder (1997) and Plouffe (1997) found that glacial direction indicators, including crag and tails features, drumlinoid bedrock ridges and parallel bedrock lineations, indicated ice flow in northeasterly to easterly directions across the study area (Figures 2.3.1 and 2.3.2). Terrain within Baptiste is generally bedrock-controlled, with gentle to moderate slopes (Collett and Ryder, 1997). 31 Figure 2.3.1: Pattern of ice flow directions as deduced from drumlins, glacial grooves, crag and tail and striations. A n arrow is used where the direction o f ice movement is known. Terrain above 1000 m is shaded with a dense stipple. (Plouffe, 1997a) The study area is indicated by a square. 32 33 T h e Baptiste v a l l e y is a hanging v a l l e y to the T a k l a trough, that once was o c c u p i e d b y a large southeastward f l o w i n g glacier and n o w holds T a k l a L a k e and the M i d d l e R i v e r (Col let t and R y d e r , 1997). Ice f l o w i n g through Baptiste V a l l e y coalesced w i t h the m a i n T a k l a glacier (Col let t and R y d e r , 1997). D e g l a c i a t i o n i n the Bapt iste v a l l e y is thought to have been characterized b y stagnant ice and m e l t i n g b y d o w n w a s t i n g , rather than g l a c i a l retreat. G l a c i a l meltwater channels i n surf ical materials (t i l l ) and bedrock are abundant o n the v a l l e y sides and f loor and can be easi ly ident i f ied o n airphotos. B e l o w the study area, Baptiste Creek is a l o w gradient stream i n a bedrock contro l led canyon, w h i c h was further deepened b y postglacia l f l u v i a l erosion. T w o s m a l l lakes, " U p p e r " and " L o w e r " Baptiste L a k e s , are located b e l o w the study streams. " U p p e r " Baptiste L a k e is i m m e d i a t e l y b e l o w and acts as a sediment trap for the s ix study streams (Figure 2.3.2). N e a r its confluence w i t h the M i d d l e R i v e r , the Bapt iste watershed has an area o f th ick g l a c i o f l u v i a l and glaciolacustrine deposits (about 85 m above the M i d d l e R i v e r ) . T h e glacialacustrine deposits have been dissected b y Baptiste C r e e k and are strongly g u l l i e d (Col lett and R y d e r , 1997). T e r r a i n m a p p i n g i n the Baptiste Creek watershed, b y J . M . R y d e r and Associates for the T a k l a F ishery-Forestry Interaction P r o g r a m , generated surf ical mater ia l , slope stabil i ty, eros ion potential and sediment source maps (Col let t and R y d e r , 1997). Port ions o f these maps s h o w i n g the study area are i n c l u d e d (Figures 2.3.3 and 2.3.4)(a complete standard terrain legend can be found i n A p p e n d i x A ) . T e r r a i n 34 0 250 500 750 meters Figure 2.3.3: Portion of terrain map for streams B1-B6 within the Baptiste Watershed at terrain survey intensity level (TSIL) C (from Collett and Ryder, 1997). An abridged legend is on the following page. The full legend can be found in Appendix A. 35 Legend to accompany terrain map o f Figure 2.3.3. F u l l legend can be found i n Appendix A (Collett and Ryder, 1997). Map Symbol: Texture Surficial material Soil drainge class 0-5 Polygon Number Process Surface expression Slope steepness class (2) Texture c clay z silt s sand m mud P pebbles k cobbles f fines e fibric g gravel b boulders r rubble a blocks u mesic h humic (3) Materials A Anthropogenic material C Colluvium D Weathered bedrock E Eolian material F Fluvial sediments FA "Active" fluvial sediments FG Glaciofluvial sediments M Till R Bedrock U Undifferentiated materials WG Glaciomarine sediments 0 Organic sediments 1 Ice L Lacustrine sediments LG Glaciolacustrine sediments W Marine sediments (6) Soils drainage classes r rapidly drained w well drained m mod. well drained i imperf. drained p poorly drained v very pooly drained Where two drainage classes are shown: if the symbols are separated by a dash, e.g. "w-i", then all intermediate classes are present; if the symbols are not separated, e.g., "wi", then no intermediate classes are present (4) Surface Expression a moderate slope(s) b blanket c cone f fan h hummocky j gentle slope(s) k moderate steep slope m rolling topograpy p plain r ridges s steep slope(s) a blocks t terrace(s) u undulatory topography v veneer w mantle of variable thickness (5) Geological Processes R Rapid mass movement R" Rapid m.m: initiation zone Rb Rapid m.m.: rockfall Rd Rapid m.m.: debris flows Rr Rapid m.m.: rockslides Rs Rapid m.m.: debris slides F Failing F" Slow m.m., initiation zone Fg Rock creeps Fm Slump in bedrock A Avalanches V Gullying E Glacial meltwater channels L Seepage (7) Slope steepness classes Class 1 2 3 4 5 Degrees 0-3 4-15 16-26 27-35 over 35 % 0-5 5-27 27-49 49-70 over 70 Definite boundary Indefinite boundary Assumed or arbitrary boundary 36 0 250 500 750 meters Figure 2.3.4: Portion of interpretive map for streams B1-B6 within the Baptiste Watershed at terrain survey intensity level (TSIL) C (from Collett and Ryder, 1997). An abridged legend is on the following page. The full legend can be found in Appendix A. 37 Legend to accompany terrain map of Figure 2.3.4. F u l l legend can be found in Appendix A (Collett and Ryder, 1997). Map Svmbol: 126 Polygon Number 0-5 Slope steepness class Slope stability class I VL Erosion potential rating 2 Potential for sediment delivery (7) Slope steepness classes Class 1 2 3 4 5 Degrees 0-3 4-15 16-26 27-35 over 35 % 0-5 5-27 27-49 49-70 over 70 (8) Slope stability classes I II III IV V No significant problems exist. There is a very low likelihood of landslides following timber harvesting or road construction. Minor slumping is expected along road cuts, especially for one or two years following construction. Minor stability problems can develop. Timber harvesting should not significantly reduce terrain stability. There is a low likelihood of landslide initiation following timber harvesting. Minor slumping is expected along road cuts, especially for one or two years following construction. There is a low likelihood of landslide initiation following road building. A field inspection by a terrain specialist is usually not required. Expected to contain areas with a moderate likelihood of landslide initiation following timber harvesting or road construction. Wet season construction will significantly increase the potential for road-related landslides. A field inspection of these areas is to be made by a qualified terrain specialist prior to any development, to assess the stability of the affected areas. Expected to contain areas with a moderate likelihood of landslide initiation following timber harvesting. A field inspection of these areas is to be made by a qualified terrain specialist prior to any development, to assess the stability of the affected area. (9) Surface Erosion Potential Ratings Code Class Name Interpretations Erosion unlikely. Minor erosion of ditches and disturbed soils likely. V L Very low potential L Low potential M Moderate potential Erosion moderately likely where water is channeled down ditches and onto disturbed areas. H High potential Major problems very likely on steep slopes and highly erodible soils. VH Very high potential Severe problems of surface and gully erosion. Erosion concerns take precedence over timber harvesting. Sediment transfer ratings Sediment transfer class Management interpretations It is very unlikely that landslides or erosion in this polygon will result in sediment input to a stream. 1 Very low potential 2 Low potential Low likelihood that landslides or erosion in this polygon will result in sediment input to a stream. 3 Moderate potential Moderate likelihood that landslides and/or erosion in this polygon will result in sediment input to a stream. 4 High potential High likelihood that landslides and/or erosion in this polygon will result in sediment input to a stream. 5 Very high potential It is very likely that landslides and/or erosion in this polygon will result in sediment input to a stream. 38 sensitive to degradation b y mass m o v e m e n t and/or erosion, sediment sources and sections o f roads w h i c h act as sediment sources w i t h i n the Baptiste watershed, were also ident i f ied p r i o r to harvesting (Table 2.3.1). H o w e v e r , none o f the sediment sources ident i f ied are located i n the study area or affect the watersheds o f the s ix study streams. E x p o s e d inact ive gul l ies are evident i n some areas (especial ly cutblock 244-22). T h e cut b l o c k s a l l l ie i n terrain o f var iable steepness w i t h slope classes 2 (3-15°) and 3 (15-26°) and stabil i ty classes II and III ( l o w to moderate), w i t h a few areas o f class I V (high) (Figure 2.3.4). T h e potential for surface erosion ranges f r o m m e d i u m to h i g h for the area. T h e predominant surf ic ia l material i n the study area is a h i g h l y cohesive and consol idated sand-si l ty basal t i l l . T i l l occurs as a veneer ( M v ) less than 1 m thick over bedrock outcrops, convex slopes, spurs and the crests o f s m a l l h i l l s . T h i c k e r blankets o f t i l l (> 1 meter thick) cover depressions at the base o f slopes, and f i l l concavit ies . Col le t t and R y d e r (1997) observed that the texture o f the basal t i l l throughout the Baptiste watershed was fa i r ly u n i f o r m . T h e results o f laboratory grain size analysis (Table 2.3.2) b y Col le t t and R y d e r (1997) ident i f ied the m a t r i x texture as predominate ly s i l ty sand to c layey s i l ty sand, w i t h a m i n i m u m o f 17 % clay. T h e t i l l is c o m p r i s e d o f 30 % angular to subangular clasts, w h i c h are m o s t l y pebbles (2 - 64 m m ) and cobbles (64 - 256 m m ) , w i t h a few boulders (>256 m m ) . T a b l e 2.3.3 shows the results o f grain size analysis f r o m two t i l l samples taken from B 5 . 39 s > < a o > > > »- X en 43 eg d 3 £ <2 x « £ I E « "2 CL w w 2 s a C-L (A « x " £ S 6 « "2 4? — •g x § £ •a <= £ » "2 > o 7 T •£ S •a xi S x> ~ x> ~ <u S3 v w :^ o. w ex u CL w | i a -= ^ p — CN > 6 'B Cd) — CN © —: *W1 mp Tip Tip slu slu slu slu 40 T a b l e 2.3.2: Part ic le size analysis for selected samples o f t i l l m a t r i x (Collett and Ryder, 1997). T i l l sample % sand % silt % clay (0.063-2.0 mm) (0.004-0.063 mm) (<0.004mm) A 5 56 19 25 A 2 4 47 36 17 A l l l 48 34 18 T a b l e 2.3.3: A v e r a g e grain size distr ibut ion for 5 k g t i l l samples taken f r o m creek B 5 . N o t e size fractions greater than 11 m m are p r o b a b l y under-represented due to s m a l l sample size and are therefore not i n c l u d e d i n the table. Size Fraction M e a n percentage Standard (mm) by weight deviation (%) 11 - 2 38.4 1.6 2 - 0 . 8 5 7.8 0.4 0.85 - 0.425 7.0 0.6 0.425 - 0.212 8.7 0.3 < 0.212 38.1 0.8 41 The texture of the till makes it highly susceptible to erosion. There is a low proportion of clasts in the till matrix, which means that when a till surface is exposed to rain and runoff, it forms gullies and is unlikely to develop armouring. Armouring occurs when the fines are washed away, leaving a gravelly surface layer which acts to reduce erosion of rills, gullies, and ditches (Collett and Ryder, 1997). Another concern is that the high consolidation of the till makes it impermeable, and poor drainage and weathering may lead to slumps in roadcuts and open slope failures in clearcuts. These till properties make it a poor material to use for road construction and problematic to disturb during harvesting activities. Collett and Ryder (1997) recommended minimizing the length and height of roadcuts, avoiding road construction on steep slopes and seeding exposed tills immediately. 2.4 Climate The study area, on the northern end of the interior plateau of British Columbia, has a moist, cool temperate climate. Mean annual precipitation ranges from 450 to 550 mm/year (Valentine et al., 1986; Environment Canada, 1998), with snowfall accounting for >50 % of this precipitation. The mean annual temperature is 3.9° C, with a mean annual July temperature of 14° C and a mean January temperature of -10.5° C. Snowmelt usually begins in May after several days of temperatures above 0°C (Beaudry, 1998). The spring freshet produces the highest stream discharges. 42 2.5 Soils Soi l s i n the study area are d o m i n a n t l y gray luv iso ls , w i t h m i n o r humo-ferr ic podzols . These soi ls underl ie m u c h o f the north-central interior o f B r i t i s h C o l u m b i a where there is h i g h t imber p r o d u c t i v i t y and extensive l o g g i n g act iv i ty (Va lent ine et al., 1986). G r a y luv iso ls over l ie the m e d i u m to fine textured t i l l s o f m a n y o f the plateau slopes o f B r i t i s h C o l u m b i a . T h e bot tom h o r i z o n o f these soi ls tends to accumulate c lay, as the u n d e r l y i n g dense basal t i l l restricts water percolat ion. Consequent ly , these soi ls are t y p i c a l l y saturated i n the spring (Valent ine et al., 1986). I n the F o r t St. James area, luv iso ls general ly occur i n the 600-1100 m elevation range, w h i l e podzols occur i n the 900-1400 m range. P o d z o l s have very t h i n organic-minera l layers o v e r l y i n g grey, leached, i r o n and a l u m i n a r i c h B horizons. P o d z o l s are often found o n steep, c o l l u v i a l slopes. I n undisturbed forests, these soi ls are protected b y l i v i n g vegetation and b y a layer o f plant litter. T h e y generally have very h i g h inf i l t rat ion capacities, far i n excess o f usual ra infa l l intensities and therefore surface r u n o f f and r i l l and g u l l y erosion rarely occur. H o w e v e r , w h e n these soi ls are unprotected, raindrop splash m a y c l o g large pores o n the s o i l surface, d ivert ing r a i n , w h i c h w o u l d n o r m a l l y infiltrate into surface runoff. In the P a c i f i c Northwest , where forests often receive over 2.54 m o f r a i n i n less than s ix months, raindrop impact has a h i g h potential for eroding s o i l unprotected b y vegetation or litter ( B r o w n , 1991). M e c h a n i c a l c o m p a c t i o n o f s o i l b y l o g g i n g 43 equipment m a y further reduce inf i l t rat ion and produce surface runoff. W h e n c o m b i n e d w i t h vegetation r e m o v a l , mechanica l c o m p a c t i o n can produce some extremely h i g h erosion rates. W i t h i n the study area the s o i l temperature class is m a i n l y c o l d cryoboreal (mean annual s o i l temperature 2-8 ° C ) and the moisture regime is s u b h u m i d . T h e g r o w i n g season w i t h i n this s o i l class is 120-180 days (days w i t h temperatures o f 5° C or higher) (Valent ine et al, 1986). 2.6 Vegetation T h e area is w i t h i n the sub-boreal spruce b i o g e o c l i m a t i c zone (elevation range 330-1100 m ) and at higher elevations the Subalpine, E n g l e m a n n Spruce zone (elevation range 950-1550 m ) . T h e sub-boreal spruce zone is c o m p o s e d o f u p l a n d coniferous forest, p r i m a r i l y whi te spruce and lodgepole p ine , w i t h deciduous, t r e m b l i n g aspen. T h e E n g l e m a n Spruce Z o n e is characterized b y E n g l e m a n spruce (P icea engelmannii) and subalpine f ir or A l p i n e f ir ( A b i e s lasiocarpa). L o d g e p o l e p ine (Pinus contorta) is c o m m o n over large areas after fires, especia l ly i n drier regions (Valent ine et ai., 1986). W i t h i n this zone c o m m o n shrubs are m o u n t a i n alder ( A l n u s incana), oak fern ( G y m n o c a r p i u m dryopteris) , S i t k a valer ian, and false hel lebore (Valent ine et al, 1986). W i t h i n the study area, the dominant t imber trees are A l p i n e fir , W h i t e spruce and L o d g e p o l e pine, w i t h m i n o r amounts o f W e s t e r n B a l s a m . T h e 44 understory is c o m m o n l y composed o f m o u n t a i n ash, alder, j u n i p e r , d e v i l ' s c lub , w i l d rose, s t inging nettles, soopoo- la l ia (soapberry), b l u e b u n c h wheat grass, and pine grass. 2.7 Study Streams B1-B6 T h e study streams a l l have north and northwest aspects (Figure 2.3.3), w i t h elevations ranging f r o m 978-1399 m above mean sea leve l (Table 2.7.1). Stream gradients range f r o m gentle slopes (3.6° - 13°) near their confluence w i t h " u p p e r " Bapt is te L a k e (except B 6 w h i c h f lows into " l o w e r " Baptiste L a k e ) to steeper slopes (10°-25°) i n the headwaters. T h e study streams a l l dra in the same geolog ica l unit . B a n k f u l l widths range f r o m 1.1 to 2.9 m and A u g u s t channel widths ranged f r o m 0.55 to 1.2 m . T h e s ix study streams w i t h i n Baptiste are a l l perennial streams, w i t h some ephemeral channels i n upper reaches. p H o f the stream water ranges f r o m 7.6-8.4. B e d f o r m s i n the study streams inc lude fa i r ly continuous r i f f le -pool sequences, w i t h bars and point bars. R i f f l e s are formed b y large organic debris ( L O D ) , such as fal len trees, boulders and accumulat ions o f rocks , and roots. R e l a t i v e l y fine sediment accumulates i n the deep pools ( 1 0 - 5 0 cm) b e h i n d the dams formed b y fa l len trees. B a n k s are c o m p o s e d o f re lat ively unweathered t i l l over la in b y t h i n deposits o f stream gravel , and are m o s t l y moss covered and inactive. G r a v e l bars and large boulders w i t h i n some reaches also are moss covered, indicat ing that they have not been 45 u o oo 'S .2 o oo s c u o 1 1 1 CD — bD CD cd C « ed I > Xi o 1 3 CD C CJ) § . cd X I 2 « CD — -g to tuo <u R CD co C . J J <u h a TI S « s „, CD CD w G O cd > CD IS CD (30 O CD CD N |O0 CD ed •J3 CD « 1 o ^ o o +•' <, *^ a o R O ""O R O '"O * 0 fi fi fi fi fi cd cd cd c3 W [ f l « « « Cfi I I I I I I 4 ^ 4 ^ 4 ^ & & 00 OO 00 00 oo oo cd cd CO CO cd cd cd cd co co cd cd C N i n m m o T—< C N C N C N 1 m i C l oo c n ed pq PQ co PQ m PQ ON oo CT\ ^ ^ C N _ , VD m oo c i . i n i n v q ^ O © O O C l CN m r- C N j^-i—i <—i I N r~ «—« o /~*. e*-> o C l o o <n 00 r-- o ON ON r o C N o C N CN i—1 C N *—• ON o o o o o ON o •ST o o Cl C N Cl C l C l C N '—1 '—1 1—' o o o o eds oo 00 oo oo oo oo Os as ON as OS OS ^ oo ° 5? " 2 tN m "cf i n * 0 PQ PQ PQ CO PQ ON as CD -o C^ O U 6 o c CD +-> o a c o CD 2 OO -46 recently m o b i l i z e d . Streams B 1 - B 5 discharge into a s w a m p y area surrounding " u p p e r " Baptiste L a k e , where the channel gradients become l o w (1 - 2°) , w i t h deep pools and organic-r ich sediments. Stream channels i n the headwaters are p o o r l y developed w i t h m a n y s m a l l tributaries and seepage areas. Dense underbrush (particularly profuse d e v i l ' s c lub) and large w i n d f a l l often obscure the stream. A l s o , i n the steeper headwaters the channel f lows through and under b l o c k y , moss covered bedrock and bouldery c o l l u v i u m . T h e channel often disappears beneath b l o c k y c o l l u v i u m for short distances and elevation steps o f pools and riffles become re lat ively large. Sediment w i t h i n the pools is p o o r l y developed, angular to subangular sandy gravels, w i t h a h i g h percentage o f organic debris. Sediment transport patterns i n s m a l l forested streams o f the P a c i f i c N o r t h w e s t show that as discharge increases dur ing a storm suspended sediment increases r a p i d l y and peaks p r i o r to or at the t ime o f peak discharge (Paustian and Beschta , 1979). Suspended sediment concentrations then tend to decl ine r a p i d l y , f a l l i n g faster than the stream discharge. S i m i l a r l y , bedload transport changes over the course o f a s torm, but bedload general ly peaks after suspended sediment and discharge p e a k ( B r o w n , 1991). W i t h i n the Baptiste watershed, the major sediment-moving events occur d u r i n g the spring freshet w h e n winter snow accumulat ion melts r a p i d l y causing large increases i n streamflow that m o b i l i z e sediment. Measurement o f bedload o n streams adjacent to 47 Baptiste ( O ' N e i l and F o r f a r Creeks) , suggest that >90 % o f the b e d l o a d transport occurs d u r i n g the n i v a l f lood. A n addit ional 9 % o f the bedload m o v e m e n t can be attributed to convect ive storms o n top o f the d e c l i n i n g n i v a l f lows. O n l y 1 % o f the bedload m o v e m e n t results f r o m f a l l and winter precipi tat ion events (Gottesfeld, Pers. C o m m . ) . U n l i k e Forfar and O ' N e i l creeks, disturbance o f sediments b y sockeye s a l m o n s p a w n i n g is not a factor i n Baptiste Creek. 2.8 Logging practices in the Baptiste Creek watershed W i t h i n Baptiste , two cutblocks, 220-23 o f 53 ha. and 244-22 o f 54 ha. , were harvested (Figure 2.0.2) T h e cutt ing prescriptions w i t h i n the Baptiste drainage were designed to meet and exceed the guidel ines set b y F P C , w h i l e also meet ing the needs o f the researchers f r o m S T F F I P . H o w e v e r , the l o g g i n g methods, i n c l u d i n g the equipment used, were t y p i c a l for cutblocks o n comparable slopes and w i t h s i m i l a r surf ic ia l materials. Researchers, i n c l u d i n g the author, were present to observe that " s p e c i a l " practices were not u t i l i z e d i n l o g g i n g that m i g h t bias the experimental results (Plate 2.8.1). T h e harvesting o f the two experimental b l o c k s was part o f a larger contract to harvest a l l o f C A N F O R ' s forest leases i n the area, w h i c h was awarded to K & D L o g g i n g o f Fort . St. James, B . C . W i t h i n the Bapt iste watershed, s ix streams ( B 1 - B 6 ) were selected for research. S m a l l first and second order (S4 and S6) streams were selected as these are the least 48 Plate 2.8.1: V i e w o f the lower port ion o f cut b l o c k 244-22 after cut t ing , y a r d i n g and r e m o v a l o f trees i n N o v e m b e r 1996 (top). V i e w o f a t y p i c a l act ive l a n d i n g , w i t h numerous s k i d trai ls , i n the upper p o r t i o n o f cut b l o c k 244-22 (bottom). 49 protected b y the F P C . Streams B 4 and B 6 were to r e m a i n as experimental contro l streams. T h e streams selected i n Baptiste are actual ly c lass i f ied as S6 streams (non f ish bearing; < 3 m wide) b y the F P C , but were treated as S 4 streams ( f ish bearing; < 1.5 m w i d e ) at the request o f various S T F F I P researchers. T h u s , 30 m R M A s and 5 m machine-free buffer zones were established a long the streams. T w o different cutt ing prescriptions and riparian management strategies were used for the two cutblocks to facilitate streamflow, sediment and suspended sediment studies. O n e treatment was termed "aggressive", w i t h the objective o f l e a v i n g o n l y a l i m i t e d number o f trees adjacent to the stream and effectively r e m o v i n g a l l o f the forest cover. T h e "conservat ive" treatment a i m e d to m a i n t a i n at least 10 m o f forest cover o n either side o f the streambank, w i t h a l l trees retained i n this area. A v a i l a b l e i n f o r m a t i o n o f forest types, l o g g i n g act iv i ty and experimental treatments for each o f the watersheds is presented i n T a b l e 2.8.1. C u t b l o c k 220-23 (stream B 5 ) was treated "aggress ive ly" w i t h a l l merchantable t imber w i t h i n the R M A taken (Plate 2.8.2). Merchantable t imber is def ined as >15 c m for p ine and >20 c m for spruce and balsam. Trees w i t h i n the 5 m machine-free buffer zones were fe l led w i t h a fel ler-buncher w h i c h c o u l d direct and f a l l the trees f r o m outside o f the 5 m zone. W h e r e this was not possible , trees were fe l led b y convent ional h a n d methods and yarded. Nei ther harvesting nor y a r d i n g equipment trespassed w i t h i n the 5 m buffer. Three stream crossings w i t h culverts were 50 ..2 P . & <d 12 £ c cu CU s i la o in c ITS •s cd "s U bO ed is P ed • S G I73 cu CO 4*! o o o G T3 cu co cu 43 13 P ed u Cd r j i ;s 0 s* cu <D <u <u > .> .> rjj . ^ d tu) M cu CU CO CO G a O O o o r: cu bfl O o o o O T3 (D O 00 1 T3 p _ bO v o O O 13 U bO (50 O <U bO bO O § t3 T3 <D u b o bO bO o bo O 13 p3 3 3 m -<cf K oo m t N e n « V ) K1 00 ON OO M r H ( S i n i n v o \ o h i n • i i VO VO "O i n r o oo 00 00 PQ -^r _r 03 PQ i — i t N m -st i n v o CQ pq PQ 05 PQ pq o s o R K a X a s bo cj 00 a CJ o I ,CU ^5 pq CU .2 43 co !? cd „ u P G ia cu T3 1 •8 •4—> § 43 o > o a i-i co OS & s O o m n -£? cu "o - cu cu ed p 43 c 4 3 a o 43 o l-c & g fe -e 43 .§ ^ 6 ^ p a £ c o T3 £3 ^ CU CJ C+H cu CU > co ec3 co r « « cu ll , o CO C o P cd T3 o cd ^ 00 3 bO P. (U « g ° •H C*H co C _ M p C P £ § I u t N •)-; <b A 3 > e co cd ^5 co b ^ -S a j- " bO .O (3 ed ^  O _^  6 |j 51 Plate 2.8.2: Photos o f cut b l o c k 220-23 after harvesting. Stream B 5 was l o g g e d w i t h the aggressive r ipar ian treatment; compare w i t h the conservative r i p a r i a n treatment o f cut b l o c k 244-22 o f Plate 2.8.4. Photos courtesy o f P . B e a u d r y . 52 constructed a long B 5 , w i t h numerous landings (areas where trees are p i l e d after harvesting and yarding , and later loaded onto trucks for r e m o v a l from the cutblock) . In cutblock 244-22 (streams B l , B 2 and B 3 ) R M A s were harvested m o r e "conservat ive ly" , w i t h t imber >30 c m r e m o v e d and f u l l retention i n d i f f icu l t access or steep g u l l y areas (Plates 2.8.3 and 2.8.4). N o machinery was to c o m e w i t h i n 2 0 m o f the streambanks and f u l l retention was maintained for approximate ly 2 0 0 m i n a p o r t i o n o f the B 3 watershed where the terrain is steep and r o c k y . H o w e v e r , i n upper B 2 , where the stream channel was p o o r l y def ined and obscured b y th ick brush, the machine-free buffer zone was not strictly observed. T h e cutblocks were harvested between N o v e m b e r 1996 and January 1997. F o u r hundred and twenty truck loads (18,900 m 3 ) o f t imber resulted from cutblock 220-23 and 585 truck loads o f t imber (26,400 m 3 ) resulted from cutblock 244-22. N i n e t y percent o f the f e l l i n g was executed w i t h a tracked fel ler-buncher (Plate 2.8.5), w h i l e ten percent o f the trees, part icular ly trees i n steep areas or w i t h r ipar ian management areas were fe l led b y hand. A tracked-grapple skidder (Plate 2.8.5) was used to drag ninety percent o f the trees a long s k i d trails to landings or to the side o f h a u l roads where the logs were sorted and stacked p r i o r to l o a d i n g onto trucks. W h i l e tracked-skidders were designed to have l o w ground pressure, winter observat ion o f l o g g i n g revealed that i n steeper areas the grapple skidders broke through snow cover to disturb shrubs and ground cover beneath. I n some steeper areas, such as o n the south side o f B 3 and upper B l , m u l t i p l e s k i d trails were u t i l i z e d to m i n i m i z e ground 53 Plate 2.8.3: V i e w o f cut b l o c k 244-22 before (top) and after (bottom) clear cut l o g g i n g . 54 Plate 2.8.4: Photos o f cut b l o c k 244-22 after harvest ing. Streams B l , B 2 and B 3 were l o g g e d w i t h the conservative r ipar ian treatment; compare w i t h aggressive r i p a r i a n treatment a long stream B 5 o f cut b l o c k 220-23 seen i n Plate 2.8.2. C u t b l o c k 220-23 can be seen i n the background. Photos courtesy o f P. B e a u d r y . 55 Plate 2 8 5- E q u i p m e n t used i n harvesting. Fel ler-buncher used to cut and p i l e trees (top) and l o w g r o u n d pressure, tracked skidder used to y a r d logs d o w n to landings f r o m the upper port ions o f the cut b l o c k s (bottom). 56 disturbance w h e n s k i d trails became too soft for skidders to c l i m b . W h e n s k i d d i n g d o w n h i l l , grapple skidders often d i d not f o l l o w designated s k i d trai ls; however , the snow cover appears to have protected the ground cover. T e n percent o f the logs were l ine sk idded b y cable. B u c k i n g o f trees was p r i m a r i l y done w i t h a tracked-processor, w i t h h a l f o f the b u c k i n g occurr ing at landings and h a l f o c c u r r i n g at roadsides. A semi-permanent haul road to cut b l o c k 220-23 ( B 5 ) was constructed i n N o v e m b e r 1996 (Figure 2.0.2) and i n v o l v e d instal lat ion o f three semi-permanent stream crossings o n B 3 , B 4 and B 5 . T h e t i l l materials used were very soft and wet, and the road was constructed w i t h a tracked, l o w ground-pressure backhoe (Plate 2.8.6). L o w temperatures at the t ime o f construction froze the road materials, a l l o w i n g equipment and h a u l trucks temporary use o f the road dur ing the winter . A large quantity o f the w o o d y debris created b y r e m o v i n g and harvesting the trees a long the access road right o f w a y (12 m w i d e ) was bur ied w i t h i n and beneath the road. B y the summer o f 1997, the materials c o v e r i n g the large b u r i a l pits at the b e g i n n i n g o f the h a u l r o a d between B 2 and B 3 had begun to subside and f i l l w i t h water (Plate 2.8.7). S n o w and debris w h i c h was incorporated and bur ied w h e n the road was constructed has subsequently melted-out, l eav ing depressions i n some areas o f the road. There are large tension cracks present a long the edges o f the road surface, indicat ing that there is the potential for failures o f the road f i l l material . T h e h a u l road into B 5 is scheduled to become a winter h a u l road for cut b l o c k s i n the south-eastern part o f the Baptiste . W i t h the 57 Plate 2.8.6: C o n s t r u c t i o n o f semi-permanent h a u l road to the b o t t o m o f cut b l o c k 220-23 to stream B 5 i n N o v e m b e r 1996. Construct ion o f stream cross ing at B 3 (top) and m i d w a y between B 3 and B 4 (bottom). F i l l material is saturated l o c a l t i l l and bedrock. 58 Plate 2.8.7: A e r i a l v i e w o f j u n c t i o n o f m a i n h a u l r o a d w i t h n e w l y constructed, s e m i -permanent h a u l road to cut b l o c k 220-23 to stream B 5 (top). N o t e the large pits where debris and snow was buried dur ing winter road construct ion (bottom). 59 exception o f this semi-permenant road, a l l other roads w i t h i n cutblocks were c lass i f ied as de-activated and were seeded w i t h grass i n the spr ing o f 1997. A substantial amount o f w i n d f a l l i n the spring and summer o f 1997, required that a salvage operation be m o b i l i z e d i n the summer o f 1997 result ing i n considerable disturbance to the seeded s k i d trails i n cutblock 220-23. 2.9 Climatic and hydrological changes due to forest harvesting A s part o f S T F F I P , the c l i m a t i c and h y d r o l o g i c a l changes i n s m a l l streams due to forest harvesting were investigated i n the Baptiste watershed. F i v e automated m o n i t o r i n g stations were instal led b y P. B e a u d r y to measure streamflow, suspended sediment, water temperature, air temperature and ra infa l l . Three contro l stations were instal led above cutblocks ( B 3 & B 5 ) and o n undisturbed streams ( B 4 ) . T w o stations were instal led b e l o w l o g g i n g disturbance ( B 5 and B 3 ) . S n o w f a l l w i t h i n each watershed was also measured before and after logg ing . Results s h o w e d that w h i l e annual ra infa l l regimes were s i m i l a r between 1996 and 1997, s n o w f a l l i n 1997 was considerably greater than 1996. T h e water equivalent snowpack was 24 % greater o n M a y 1, 1997 than o n M a y 1, 1996 (Figure 2.9.1 A ) . In 1996 snowmelt started o n M a y 13, w h i l e i n 1997 snowmelt occurred d u r i n g the entire 60 A) Figure 2.9.1: A) Local climate at the Baptiste study streams - spring 1996 and 1997; B) Fifteen minute average discharge for the three study streams-spring 1996-1997; C) Measured and Predicted average daily discharge for B3 and B5 watersheds for the first spring after harvest (Beaudry, 1998). 61 first week o f M a y (Beaudry, 1998). T h e early onset o f snowmelt was noted i n streamflow hydrographs (Figure 2 .9 .2B) where the hydrograph began to rise 13 days earlier i n 1997 than i n 1996. Peak melt rates were m u c h higher i n 1997 than 1996; for B 4 , 0.175 m V compared to 0.09 m V for 1996. T h e snowmelt r u n o f f p e r i o d was also substantial ly longer i n 1997, last ing 33 days, w h i l e i n 1996 it lasted o n l y 24 days (Beaudry , 1998). A l l three streams showed s i m i l a r suspended sediment concentrations transported throughout the snowmelt per iod. Suspended sediment increased s igni f icant ly w i t h the start o f snowmelt and d isp layed a dist inct d iurnal pattern, w i t h m a x i m u m sediment concentrations at midnight . T h e increase i n discharge i n 1997 also resulted i n a s i m i l a r increase i n the total amount o f suspended sediment transported (Table 2.9.1). In the first year after harvest, there were signif icant changes i n h y d r o l o g y i n b o t h o f the harvested streams ( B 3 and B 5 ) . These changes i n c l u d e d increases i n the average B 5 pre-peak f lows (32.9 % ) and B 3 post-peak f lows (17.6%). A v e r a g e B 3 peak f lows decreased b y 1 2 % (Table 2.9.2) (Beaudry, 1998). W e m p l e et al. (1996) f o u n d s i m i l a r changes i n hydrographs f r o m streams where forest harvest ing and r o a d construct ion occurred and attributed them to extensions o f the drainage network. B e a u d r y (1998) attributes the differences observed i n post-harvest discharge o n B 3 and B 5 w i t h i n the Baptiste watershed to three factors: the treatment effect, watershed slope and the first season after harvest. 62 CD o co CD XI l i CD <a cd cd1 u >> CD | •+-» cd g o C o o 00 Os OS 3 cd CD PQ o to T3 CD CD O .§ 6 CD co T3 CD C CD o. co 3 co CD § X ! o Os CN CD PQ ^ V? a oo oo H T3 CD 6 a a oo G oo in PQ *-> CO §3 m 1 § T3 £ oo .s ^ - oo s 00 o oo T 3 H PH CO PQ o 6 0O t - H cn Os cn t-~ so © CN 0O t-; CN t~ CN CS OO m os + © co ^ CN cd CD . . cd V CD P OH IS u i -*-» CO O PH 63 T3 u OJ OO s 43 o oo o •NT in cj CM cB CJ <L> CO r-co in < CO CN < 6, T—< fc d O CJ bo o 43 o •a CJ I " S I r Iin CO W CO 1) |43 |T3 I CO CO a T3 CJ ro PQ (3 CJ to CO bo o S3 m 43 ^ o w — S cf ^ fi fi £ fi CJ bo ^ CO O 43 CJ CO c |m co <u fi ro CM ° i <! vo n «N fc -o <^  ^ VO ^ in ^ co £ in g (N o H o d ° d vo vo i—i in tN o o d d CJ M * 8 .fi * a, 3 w • .*-» CO O CM 64 T h e treatment type (the l o g g i n g 4 0 % o f the watershed and the reduct ion o f the r ipar ian area around B 5 ) m a y account for the large increase i n early snowmelt runoff. T h e reduct ion o f forest canopy cover increases the amount o f snow a c c u m u l a t i o n and increases the amount o f energy (advected and sensible heat) avai lable for m e l t i n g snow; therefore, result ing i n increased f lows. T h e r ipar ian area, i n c l u d i n g the stream surface, channel banks, vegetation and zones o f restricted c o n d u c t i v i t y (road crossings) are an important source o f p e a k f l o w r u n o f f (Beaudry, 1998). T h e slope o f the two treated watersheds m a y also part ia l ly account for the observed differences. W h i l e b o t h watersheds are north facing, B 5 has a considerably shal lower slope than B 3 ( 5 % for B 5 versus 26 % for B 3 ) . Thus , B 5 is exposed to a greater proport ion o f solar radiat ion, w h i c h is the largest component o f snowmelt energy. T h e f ina l factor, the occurrence i n the first season after harvest, is s ignif icant because the harvest ing o f these cut b l o c k s occurred i n the winter . A t the t ime o f harvest ing there was a 1.5 m snowpack. L o g g i n g left an insulat ing blanket o f debris (branches, needles, and cones) over a 1.2 m snowpack. T h i s debris was subsequently covered b y m o r e s n o w f a l l . T h e insulat ing effect o f the debris blanket c o m b i n e d w i t h the effect o f the slope and the r ipar ian treatments is thought to e x p l a i n the reduct ion i n early f lows and the increase i n late f lows (delayed snowmelt) i n B 3 (Beaudry , 1998). 65 In summary, the r e m o v a l o f a substantial proport ion o f forest cover from watersheds i n central B r i t i s h C o l u m b i a has been s h o w n to result i n s ignif icant increases i n spring r u n o f f (Beaudry , 1998). T h e aggressive l o g g i n g treatment ( B 5 ) increased peak suspended sediment concentrations b y a factor o f 2.2, w h i l e the conservative buffer treatment increased peak concentrations b y a factor o f 1.8 (Beaudry , 1998). T h e m a i n sources o f increased suspended sediment from forest harvesting practices, w h e n harvesting ( fa l l ing , yarding) procedures do not cause s o i l or stream disturbances, were found to be the stream crossings, and the roads, trails and landings adjacent to the stream (Beaudry, 1998). A n o t h e r suspected source o f increased suspended sediment is l o g g i n g debris causing mini -debr is j a m s and altering stream channel paths. 2.10 Summary T h e study area selected represents a t y p i c a l watershed i n the north-central interior o f B r i t i s h C o l u m b i a . S u r f i c i a l materials, c l imate, soi ls , vegetation, and streams are t y p i c a l o f the h i g h l y product ive forested regions o f B r i t i s h C o l u m b i a . T h e Baptiste watershed p r o v i d e d s ix study streams d r a i n i n g the same l i t h o l o g i c a l unit . F o u r o f the streams w o u l d be affected b y forest harvesting activities w h i l e two w o u l d r e m a i n as unlogged controls. L o g g i n g o f two experimental cutblocks was undertaken w i t h t y p i c a l methods, one cut b l o c k be ing logged aggressively w h i l e the other was logged 66 conservatively. Changes i n h y d r o l o g y and suspended sediment were noted o n the two harvested streams b e i n g monitored. Peak suspended sediment concentrations were noted to increase b y a factor o f 2.2 o n the aggressively treated stream, and b y a factor o f 1.8 o n the conservat ively treated stream (Beaudry, 1997). 67 CHAPTER 3 SAMPLING AND ANALYTICAL METHODS F i e l d w o r k was undertaken i n the Baptiste Creek drainage bas in , south o f T a k l a L a k e , i n A u g u s t 1996 and A u g u s t 1997. I n 1996 sediment samples were co l lected f r o m six s m a l l (S4-equivalent) streams (Figure 2.0.2), four o f w h i c h were to be logged i n 1997 and two that were to r e m a i n unlogged as controls. F i e l d w o r k was conducted f r o m J u l y 31 to A u g u s t 16, 1996 and f r o m A u g u s t 12 to 27, 1997 b y the author w i t h a f ie ld assistant. In both years, laboratory w o r k was done f r o m September to D e c e m b e r w i t h the help o f one laboratory assistant i n 1996 and two laboratory assistants i n 1997. 3.1 Sample site selection, sample collection and identification of sediment sources In 1996, samples were col lected f r o m the two control streams and f r o m above, b e l o w and w i t h i n proposed cut-blocks o f the four streams w h i c h w o u l d be affected b y the l o g g i n g (Figure 3.1.1). I n 1997, where possible , the same sites as 1996 were re-sampled (Figure 3.1.2). A d d i t i o n a l sites were sampled to f i l l i n and to replace sites lost to r o a d construct ion and to channel disturbance (e.g. top o f B 2 ) , and due to th ick growth o f d e v i l s ' c lub and st inging nettles obscur ing sample sites. D e t a i l e d sample site locat ion maps for each creek for 1996 and 1997 can be found i n A p p e n d i x A . S a m p l i n g o f the s ix study streams was done o n foot and samples were p a c k e d to 68 ft s .2 a CQ OS a 2 * wo ca « fe o PQ H Z J 3 PQ o CJ & -3-i ^ oo M E ro oo 1 1 I 1 » <§ a> 'g I B * * TJ C i i 1 / 1 3 bQ bl •g & J2P & I a i - d o o CN CN 69 o o CD s C O CU CN ^ WD * « CD O cn N O PQ c3 [T1 <D C CD PQ £ o • o w h4 o PQ o _o C Q T 3 O OH Oh oo u IT cn m & cu> o-03 oo 8 3 O ro ^ CO a 8 ^ c S M a so so •4H & 60 O . J"H M •Z B * 2 O O X cd m Q CN CN W oo T3 cu oo 70 nearby roads. R o a d access was g o o d and was i m p r o v e d i n 1997, w i t h s k i d trails w i t h i n the cut b l o c k s and a n e w l y constructed semi-permanent h a u l road to the base o f B 5 . H o w e v e r , the haul road to B 5 has been c lass i f ied for winter use o n l y and was too water saturated for vehic les i n the summer o f 1997. S a m p l e sites were selected o n active gravel bars to ensure that samples were representative o f sediment recently m o b i l i z e d w i t h i n the stream. S a m p l i n g o f sediments potent ia l ly contaminated b y col lapsed bank mater ia l or l o c a l soi ls were avoided. T y p i c a l sample sites are s h o w n i n Plates 3.1.1 and 3.1.2 S a m p l i n g procedures i n both years i n v o l v e d f ie ld screening to obta in approximate ly 3-5 k g o f m i n u s 11 m m sediment f r o m s m a l l , active gravel bars. T h e p lus 11 m m and m i n u s 11 m m fractions were w e i g h e d i n the f ie ld , the w i d t h o f the stream measured, and the site and streambed photographed. S a m p l i n g procedures and equipment are s h o w n i n Plate 3.1.3. A t approximate ly twenty percent o f the sites, a duplicate sample was taken to study in-site var iabi l i ty . I n 1996, a total o f 124 3-5 k g samples were col lected w i t h 22 f ie ld duplicates, w h i l e 159 were col lected i n 1997 w i t h 47 f ie ld duplicates. L a r g e r (20 kg) samples were col lected at 12 sites i n 1996, and 13 sites i n 1997, for m o r e detai led size d is tr ibut ion and m i n e r a l o g y studies. S i x new sources o f sediment were identi f ied 1997. These developed as a result o f land disturbance f r o m l o g g i n g act iv i ty and road b u i l d i n g (Figure 3.1.3). T o characterize the c o m p o s i t i o n o f this " n e w " sediment, s ix to eleven samples o f the mater ia l used to 71 72 73 74 75 construct the crossings were col lected f r o m each sediment source and from gul l ies d r a i n i n g the road. Sediment sources w i l l be more f u l l y described i n Chapter 7. A l l o f the samples were packaged and shipped to U B C for further preparation and analysis. 3.2 Sample preparation Samples were prepared b y s iev ing and d r y i n g i n the laboratory at the U n i v e r s i t y o f B r i t i s h C o l u m b i a . T h e 3-5 k g samples and the 2 0 k g samples were each prepared differently; s u m m a r y f l o w charts for sample preparation and analysis for the 3-5 k g and 2 0 k g samples are s h o w n i n Figures 3.2.1 and 3.2.2, respectively. 3.2.1 Preparation of 3-5 kg samples T h e 3-5 k g samples were wet s ieved i n the laboratory through a stack o f four stainless steel A S T M sieves result ing i n the f o l l o w i n g f ive size fractions: <0.212 m m , 0.212 -0.425 m m , 0.425 - 0 . 8 5 m m , 0.85 - 2 m m , 2 - 1 1 m m . T h e m i n u s 0.212 m m material from each sample and w a s h water were retained i n pai ls (2 to 3) to a l l o w for the fine suspended material to settle out. C l e a n water was used to sieve rather than rec irculat ing water w i t h a p u m p , as it was considerably faster to sieve and samples 76 F I E L D O r i g i n a l Samples 124 samples in 1996 and 159 samples in 1997 Wet Sieve in the field + 11 mm - 11 mm Discard 3-5 kg L A B 0 R A T O R Y Wet Sieve + 2 mm 0.850-2 mm 0.425 - 0.850 mm 0.212-0.425 mm 0.106 -0.212 mm I Weigh Store Figure 3.2.1: Summary flow chart of sampling and analytical methods in the field and the laboratory for the 3-5 kg samples. 77 F I E L D Original Samples 12 samples in 1996 and 13 samples in 1997 W e t Sieve i n the f i e l d + 11 m m - 1 1 m m Discard - 2 0 k g L A B O R A T O R Y C o n i n g and Quarter ing 10 k g - 1 0 k g W e t S ieve + 2 m m 0 . 8 5 0 - 2 m m 0.425 - 0.850 m m 0.212 - 0.425 m m 0.106 - 0.212 m m 0.053 - 0 . 1 0 6 m m - 0.053 m m Store D r y & W e i g h 0 . 1 0 6 - 0 . 2 1 2 m m Store H e a v y M i n e r a l Separation M e t h y l e n e Iodide S . G . - 3.3 S . G . < 3 . 3 S . G . > 3.3 W e i g h W e i g h Store M a g n e t i c P i s t o n magnetic fraction non-magnet ic fract ion W e i g h i i W e i g h Store Store F i g u r e 3.2.2: S u m m a r y f l o w chart o f s a m p l i n g and analyt ica l methods i n the f ie ld and the laboratory for the 2 0 k g samples 78 were s ieved m o r e consistently. T h e -0.212 m m size fraction was a l l o w e d to sit u n t i l the sediment h a d settled and the water was clear. A p u m p was used to remove clear water from the pai ls without disturbing settled material at the b o t t o m and to reduce the amount o f heavy l i f t ing required. T h e sediment was then scraped and r insed into glass d r y i n g trays. M a t e r i a l i n different pai ls f r o m the same sample was r e c o m b i n e d after d r y i n g . E a c h o f the f ive sediment size fractions were oven-dr ied i n glass trays at approximate ly 150°-200°C and w e i g h e d p r i o r to storage i n plast ic sample bags. G r a i n size distr ibutions for textural analysis (Sect ion 5.1) were calculated for percentages b y dry weight i n each size fraction. O v e n - d r y i n g and w e i g h i n g p r o v i d e d dry weights for the size fractions < 11 m m . T h e total dry weight o f < 11 m m material i n each sample, M s (Totai<iimm-dry)> is equal to the s u m o f the dry weights o f the other f ive s ize fractions ( M s ( d i y ) i for i = l - 5 ) . H o w e v e r , to characterize the in-s i tu grain size dis tr ibut ion o f stream sediment the amount material coarser than 11 m m was also considered. W e i g h i n g i n the f ie ld p r o v i d e d estimates o f total wet weights ( M s ( t o t a l . w e t ) ) for each o f the samples (equal to the s u m o f the > 11 m m size fraction ( M s ( + l l m m . w e t ) ) and the < 1 1 m m size fraction ( M s ( . u „ . „ , , ) ) ) . T h e percentage b y mass o f mater ia l > 11 m m , for each sample, is then estimated b y the ca lculat ion: P > llmm = 100 X M s ( + l l m m . w e t ) / M s ( t 0 [ a l . w e t ) 79 Thus , to inc lude the > 1 1 m m size fraction i n the grain size d is tr ibut ion, a s i m p l e proport ion o f the total wet and dry weights for b o t h the > 1 1 m m and < 1 1 m m size fractions can be used. T h e n , for any size fraction, i , the percentage o f sediment b y dry weight can be g i v e n by: P i (<11mm) — 1 00 X [MS(dry)i X MS(_] ] m m . wet)] / [MS (TotaKl lmm-dry) X MS(total . wet)] T h e r a w gra in size distr ibut ion data f r o m the f ie ld and laboratory and the calculated percentages, b y mass, for each size fraction w i t h i n the samples can be found i n Tables D I .1-D2.6, i n A p p e n d i x D . S i e v i n g , w e i g h i n g and d r y i n g began i n September and was completed i n D e c e m b e r i n both 1996 and 1997. A s discussed i n section 1.3, the - 0 . 2 1 2 m m size fraction, fine sand-si lt-clay, was selected for analysis as it contains the size fractions w h i c h w i l l best y i e l d in format ion o n the processes o n the stream bed after addi t ion o f n e w sediment. In both years, the - 0.212 m m was disaggregated b y crushing w i t h a large stainless steel r o l l i n g p i n pr ior to the spl i t t ing o f samples. A sub-sample o f approximate ly 5 grams was taken from each sample and placed, r a n d o m l y , i n numbered v ia ls . T h i s was done such that the order o f sample preparation and geochemica l analysis w o u l d be distinct. T h e potential for systematic errors or contaminat ion occurr ing dur ing these procedures c o u l d then be considered i n subsequent qual i ty control steps (Fletcher, 1987). D u p l i c a t e sub-samples were taken from samples at this stage and were r a n d o m l y inc luded i n the sample set. These 80 samples are referred to as laboratory duplicates and can be used i n qual i ty contro l as a measure o f the total amount o f v a r i a b i l i t y due to laboratory and analyt ica l procedures. A total o f 22 laboratory duplicates were i n c l u d e d i n the 1996 sample batch and a total o f 37 laboratory duplicates were i n c l u d e d i n 1997. I n b o t h years, C A N M E T cert i f ied reference standards were also i n c l u d e d i n r a n d o m l y numbered v ia ls w i t h i n the sample batches to p r o v i d e i n f o r m a t i o n o n the accuracy o f the data and o n differences i n the accuracy and p r e c i s i o n between 1996 and 1997. A l s o , i n 1997, sub-samples f r o m the 1996 samples were i n c l u d e d to examine the v a r i a b i l i t y o f laboratory results between 1996 and 1997. 3.2.2 Preparation of 20 kg samples Preparat ion o f the 2 0 k g samples i n v o l v e d c o n i n g and quartering the samples to reduce the sample weight to 10 k g , f o l l o w e d b y wet s iev ing i n the laboratory to y i e l d the f o l l o w i n g size fractions: <0.053 m m , 0.053 - 0.106 m m , 0.106 - 0.212 m m , 0.212 - 0.425 m m , 0.425 - 2 m m , and 2 - 1 1 m m . T h e m i n u s 0.053 m m mater ia l was a l l o w e d to settle i n pai ls before d r y i n g . F o r the 2 0 k g samples, grain size distributions were also calculated for the percentages b y weight i n each size fraction u s i n g the same formulas described for the 3-5 k g samples. T h e 2 0 k g samples were also w e i g h e d i n the f ie ld i n > 11 m m size fract ion and < 11 m m size fractions. Laboratory s iev ing resulted i n dry weights for 81 the f o l l o w i n g s ix size fractions: 0.053 m m , 0.053 - 0.106 m m , 0.106 - 0.212 m m , 0.212 - 0.425 m m , 0.425 - 2 m m , 2 - 1 1 m m . F o r any sediment size fraction, i , the percentage b y weight , can be determined w i t h the same formulae as for the 3-5 k g samples. 3.2.3 Heavy mineral separations Selected samples f r o m the 0.106 - 0.212 m m size fraction f r o m the 2 0 k g samples and f r o m the 0.053 - 0.212 m m size fraction from 3-5 k g samples were used for heavy m i n e r a l separations w i t h methylene iodide ( C H 2 I 2 ) ( S . G . = 3.3). (Note: the 3-5 k g samples selected for heavy m i n e r a l separations were further wet s ieved, after sub-samples h a d been r e m o v e d for geochemica l analysis, through a - 0.053 m m sieve and dr ied p r i o r to separation). Samples were separated into two port ions: those w i t h specif ic gravi ty greater than 3.3 (heavy minerals) and those w i t h speci f ic gravi ty less than 3.3 ( l ight minerals) . T h e weight percentage o f heavy minerals and l ight minerals w i t h i n the size fraction o f each sample was then calculated i n the same manner as ca lculat ing the weight percentages o f sediment (Sect ion 3.2.1). A hand-held p is ton magnet was then used to remove the magnetic minerals , p r i m a r i l y magnetite. T h e weight percentage o f magnetite i n the sample was then determined. 82 3.3 Modal analysis using the Rietveld method and X-ray powder diffraction data T h e m i n e r a l o g i c a l invest igat ion and result ing data presented i n this section was p r o v i d e d b y M . Raudsepp and E . P a n i (Pers. C o m m . , 1998), f r o m T h e U n i v e r s i t y o f B r i t i s h C o l u m b i a . M i n e r a l o g y was determined w i t h step-scan X - r a y p o w d e r di f fract ion ( X R D ) for 14 samples w i t h two duplicates o f stream sediment - 0.053 m m , and for 10 samples w i t h two duplicates f r o m sediment sources. T h e grain size d is tr ibut ion o f unground samples ranges f r o m 1-53 u m , therefore, g r i n d i n g to achieve a gra in size less than 15 u m , w i t h the majori ty o f the particles less than 5 u m , was necessary p r i o r to X R D . Step-scan p o w d e r di f fract ion data were col lected w i t h a CuKoc radiat ion o n a Siemans D 5 0 0 0 diffractometer equipped w i t h a B r a g g -Bentano goniometer. A l o n g fine-focus C u X - r a y tube was operated at 4 0 k V and 30 m A . Several samples were r u n w i t h different step sizes and step count ing t imes to determine the o p t i m u m condit ions for data co l lec t ion. F i n a l data were col lected over the range 3-70°26 w i t h a step size o f 0.02°20 and count ing t imes o f 2s/step. Phases were ident i f ied u s i n g the International Centre for D i f f r a c t i o n D a t a , database and Siemans search-match software. T h e R i e t v e l d rmethod was used for m o d a l analysis (Raudsepp et al., i n press). T w o batches o f samples were submitted for R i e t v e l d analysis: (1) samples f r o m stream sediments f r o m B 1 - B 5 , and (2) samples f r o m sediment sources 83 3.4 Geochemical analyses methods Sub-samples taken f r o m m i n u s 0.212 m m size fraction were submitted to a c o m m e r c i a l laboratory, C h e m e x L a b s L t d . o f N o r t h V a n c o u v e r , B . C . , for m u l t i -element analysis us ing two d e c o m p o s i t i o n procedures: total d e c o m p o s i t i o n w i t h H C 1 0 4 - H F - H N O j and a strong ac id attack w i t h aqua regia ( H C 1 - H N 0 3 ) . A h y d r o x y l a m i n e hydrochlor ide leach was also used i n 1996 but was not repeated i n 1997 because results were found to be very s i m i l a r to those obtained w i t h aqua regia (Figure 3.4.1 for C o and F i g u r e 3.4.2 for Z n ) . T o t a l carbon was also determined for samples i n b o t h 1996 and 1997. A total o f 200 samples were submitted to C h e m e x i n D e c e m b e r 1996 and 290 samples i n January 1998. R a w geochemica l results w i t h sample locations can be found i n A p p e n d i x A . T a b l e 3.4.1 shows detection l i m i t s and upper l i m i t s for each o f the analyt ical methods for the procedures used at C h e m e x . F o l l o w i n g is a b r i e f descr ipt ion o f each o f the three digest ion procedures. T h e total d igest ion uses a m i x t u r e o f hot concentrated ni tr ic ( H N 0 3 ) , perchlor ic (HCIO4) and h y d r o f l u o r i c ( H F ) acids. F o r complete sample d isso lut ion, the digest ion is taken to dryness and the residue is then re-dissolved i n h y d r o c h l o r i c ac id . Sample analysis for total element concentrations are then determined i n a di lute h y d r o c h l o r i c a c i d matr ix . A 0.5 g sub-sample is digested and then analyzed w i t h i n d u c t i v e l y -coupled p l a s m a atomic e m i s s i o n spectroscopy ( I C P - A E S ) . Spectral interferences are corrected for i n the results. A t C h e m e x this technique, the T - 2 4 package, gives 84 p 1-u •S -8 regia >xalarr )cniori 1 aqua 2 aqua o o n o 90 £ Q 0^ c o • —I l-t +-* c o C o o 00 c X3 c 03 a •a -a a b o-.S O | fe cn O T3 fl O •S -o s ^ 03 • a cu 03 3 c? cn C O U I I u X3 C O C 03 s 00 ctf 8 U 2 6 13 o3 cu C>0 •fl x +-< o >> U 5 « £ CU i — i CU T 3CU E 3 t-i CU tA xi -»-> * J I <2 i- cu CM T 5 ° 'C a o o 2 5 P s & o * CU £ 3 CO g C CU CU 1 g o c _o co u 00 o o 1-i r CU c 1 CS m at « CU X 00 "P 03 I 4= cu 03 ( U l d d ) UOIIIM J U . U U 0 3 03 85 (uidd) uoimj|ii3.>uo.i 117 86 T a b l e 3.4.1 : Detec t ion l i m i t s for geochemica l analysis w i t h var ious digest ion techniques at C h e m e x L a b s L t d . B l a n k s indicate elements for w h i c h the digest ion m e t h o d does not w o r k . Total Aqua regia Hydroxylamine Element Symbol (24 element ICP-AES) (32 element-ICP-AES) hydrochloride Detection Upper Detection Upper Detection Upper Limit Limit Limit Limit Limit Limit Aluminum A l 0.01% 15% 0.01% 15% 0.01% 15% Silver Ag 0.5 ppm 0.02% 0.2 ppm 0.01% 0.2 ppm 0.01% Arsenic As 2 ppm 1% 2 ppm 1% Barium Ba 10 ppm 1% 10 ppm 1% 10 ppm 1% Beryllium Be 0.5 ppm 0.01% 0.5 ppm 0.01% 0.5 ppm 0.01% Bismuth Bi 2 ppm 1% 2 ppm 1% 2 ppm 1% Calcium Ca 0.01% 15% 0.10% 15% 0.01% 15% Cadmium Cd 0.5 ppm 0.05% 0.5 ppm 0.01% 0.5 ppm 0.01% Cobalt Co 1 ppm 1% lppm 1% lppm 1% Chromium Cr 1 ppm 1% 1 ppm 1% 1 ppm 1% Copper Cu 1 ppm 1% 1 ppm 1% 1 ppm 1% Iron Fe 0.01% 15% 0.01% 15% 0.01% 15% Gallium Ga 10 ppm 1% 10 ppm 1% Potassium K 0.10% 10% 0.01% 10% Lanthanum La 10 ppm 1% 10 ppm 1% Magnesium Mg 0.01% 15% 0.01% 15% 0.01% 15% Manganese Mn 5 ppm 1% 5 ppm 1% 5 ppm 1% Molybdenum Mo 1 ppm 1% 1 ppm 1% 1 ppm 1% Sodium Na 0.01% 10% 0.01% 5% 0.01% 5% Nickel Ni 1 ppm 1% 1 ppm 1% 1 ppm 1% Phosphorous P 10 ppm 10 ppm 10 ppm 1% 10 ppm 1% Lead Pb 2 ppm 1% 2 ppm 1% 2 ppm 1% Antimony Sb 2 ppm 1% 2 ppm 1% Scandium Sc 1 ppm 1% 1 ppm 1% Strontium Sr 1 ppm 1% 1 ppm 1% 1 ppm 1% Titanium Ti 0.01% 10% 0.01% 5% 0.01% 5% Thallium Tl 10 ppm 1% 10 ppm 1% Uranium U 10 ppm 1% 10 ppm 1% Vanadium V 1 ppm 1% 1 ppm 1% 1 ppm 1% Tungsten w 10 ppm 1% 10 ppm 1% 10 ppm 1% Zinc Zn 2 ppm 1% 2 ppm 1% 2 ppm 1% Mercury Hg 1 ppm 1% 1 ppm 1% 87 concentrations for 24 elements i n c l u d i n g a l l o f the major elements (except s i l i con) as w e l l as most important trace elements. Aqua regia is a strong d e c o m p o s i t i o n u s i n g a 3:1 mixture o f h y d r o c h l o r i c and ni tr ic acids p r o d u c i n g the active agents n i t r o s y l chlor ide ( N O C 1 ) and chlor ine ( C l 2 ) i n the f o l l o w i n g react ion (Fletcher, 1987): 3 H C 1 + H N O 3 = 2 H 2 0 + N O C 1 + C l 2 Strong decomposi t ions release most elements except those retained i n crystal lattices o f si l icates, w h i c h are resistant to decomposi t ion. T h i s digest ion is near-complete for most base metals ( C u , C d , M n , P b , etc.), but is o n l y " p a r t i a l " for most major and m i n o r elements ( G i l l , 1997). C h e m e x ut i l izes a 1.0 g sub-sample to analyze for 32 elements w i t h i n d u c t i v e l y - c o u p l e d p l a s m a atomic e m i s s i o n spectroscopy ( I C P - A E S ) . In the weak decomposi t ion , h y d r o x y l a m i n e hydrochlor ide so lut ion ( 0 . 2 5 M N H 2 O H « H C l - 0 . 2 5 M HC1) is used as a reducing agent to dissolve elements associated w i t h i r o n and manganese ox ide coatings that develop o n m i n e r a l grains d u r i n g weathering and transport through the f l u v i a l system ( C h a o , 1972; C h a o , 1984; F o n e s c a and da S i l v a , 1998). Thus , the digest ion is p o s s i b l y incomplete for a l l elements. A t C h e m e x , this procedure y ie lds part ial concentrations for 32 elements. 88 T o determine total carbon, samples are combusted i n a L e c o i n d u c t i o n furnace to o x i d i z e the carbon i n the sample to carbon d i o x i d e . T h e amount o f carbon d i o x i d e produced is then measured b y an infrared detector and converted to y i e l d the total amount o f carbon i n the sample. In M a r c h 1998, another batch o f 2 0 samples was sent to C h e m e x for analysis w i t h aqua regia d igest ion i n an attempt to determine: (1) the source o f unusual v a r i a b i l i t y i n copper concentrations between f ie ld duplicates (Chapter 5) and (2) the source (and grain size) o f elevated z i n c concentrations (Chapter 7). T h i s batch was c o m p r i s e d o f sub-samples f r o m : (i) 0.053 m m size fraction f r o m the 20 k g samples, ( i i) 0.106 -0.212 m m heavy minerals ( S . G . > 3.3) o f the 0.053 - 0.212 m m size fract ion, ( i i i ) 0.106 - 0.212 m m l ight minerals ( S . G . <3.3) o f the 0.053 - 0.212 m m size fraction, and ( iv) the magnet ic fractions o f the 0.053 - 0.212 m m size fract ion f r o m 3-5 k g •A samples. 3.5 Summary of sampling and analytical methods T h e objective o f sediment s a m p l i n g , sample preparation and analysis was to establish a database descr ib ing the textural , m i n e r a l o g i c a l and geochemica l characteristics o f the study streams and sediment sources. Before further u t i l i z i n g the data an assessment o f the qual i ty control p r o g r a m i m p l e m e n t e d i n the f i e l d and laboratory is considered i n the next chapter. 89 C H A P T E R 4 D A T A Q U A L I T Y E V A L U A T I O N A qual i ty contro l program is an essential component o f any geochemica l survey. T h e two p r i m a r y components to m o n i t o r i n data qual i ty control are accuracy and prec is ion. A c c u r a c y is the closeness o f a result to the true or accepted value, and is dependent o n b o t h r a n d o m and systematic errors (Fletcher, 1981). P r e c i s i o n is a measure o f the repeatabil ity o f a result and is a measure o f the r a n d o m error (Fletcher, 1981). T h e objective o f the qual i ty control program is to identi fy systematic errors and contaminat ion at any stage f r o m sample c o l l e c t i o n to report ing o f analyt ica l results and to be able to quantify the total amount o f error associated w i t h the data. W i t h i n this study, an extensive qual i ty control p r o g r a m was designed p r i o r to s a m p l i n g and was implemented i n the field and laboratory. B o t h accuracy and p r e c i s i o n were m o n i t o r e d ; however, prec is ion w i t h i n and between sample batches (sampl ing years) was considered to be the most cr i t i ca l to ensure that results between batches were comparable. A n o t h e r important part o f data qual i ty contro l w i t h i n this study was to ensure that l o c a l var iat ion o f concentrations o n the streambed was not greater than the o v e r a l l var iat ion a long and a m o n g streams. 90 4.1 Accuracy of geochemical results A c c u r a c y was m o n i t o r e d b y the insert ion o f C A N M E T lake and stream sediment analyt ical standards ( L K S D - 1 , L K S D - 2 , S T S D - 1 , S T S D - 2 , S T S D - 3 , S T S D - 4 ) ( L y n c h , 1990). Samples f r o m each o f these s ix standards were r a n d o m l y inserted i n the sample batches i n both 1996 and 1997. F o r most elements, accuracy is w i t h i n ± 2 0 % o f accepted values for both the total and strong decomposi t ions (for example, F igures 4.1.1 and 4.1.2 for M n and Z n , respectively). T a b l e 4.1.1 and T a b l e 4.1.2 show the accepted values and standard deviations compared w i t h the analyt ica l results f r o m b o t h 1996 and 1997. A c c e p t e d concentrations are not avai lable for a l l elements reported b y each o f the digest ion methods. 4.2 Precision of geochemical results Estimates o f p r e c i s i o n can be made b y us ing cumulat ive variances to account for a l l o f the sources o f var iabi l i ty , f r o m r a n d o m errors to errors i n analysis. T h e total v a r i a b i l i t y ( S 2 (total)) can be used as an estimate o f the p r e c i s i o n o f any result, for an i n d i v i d u a l element, w i t h i n this geochemical data set. T h e total v a r i a b i l i t y o f geochemica l data f r o m a single sample and an analyt ical batch includes var ia t ion due to analysis , w i t h i n site var iat ion and r a n d o m errors. T h i s can be theoret ical ly 91 Figure 4.1.1: Accuracy of geochemical results from total and aqua regia digestions for standards analysed in 1996 and 1997 for Mn. The solid line represents the x=y line and the dashed lines are +/- 20 %. 92 1000 a "3 § 100 "3 u s A 1997 -total • 1996 - total • 1997 - aqua regia • 1996 - aqua regia 10 -f 10 100 Accepted concentration of standard (ppm) 1000 Figure 4.1.2: Accuracy of geochemical results from total and aqua regia digestions for standards analysed in 1996 and 1997 for Zn. The solid line represents the x=y line and the dashed lines are +/- 20 %. 93 u frl S 3 > ro a. 3 u - 3 8 5 < ro 2 « a. 3 u "3 . 8 > l< J ° I, 3 Ji a. 3 o > < I eg 00 o r o r o t in NO ^ co r o ro NO CN r o V"i >n ON m •^ J- r o r o •sj- r o NO i n r o m •sj- m m NO o\ m r o r o -^ J- r o NO ON ro r~ CN t— *o ON oo r— <N in ON m ON NO NO r o r o ON £J ^ ^ OO NO „ OO ON ON T j - ON r o CN O 0 0 O NO r o — i C N — — — ON "3- "3-O OS NO ro T — ( N r o - * Q Q Q Q Q Q Y\ Y\ 00 00 00 00 H H H H 00 00 00 00 r - r o cs oo NO r o r o r o T r o vo O ON CN TJ- ro m t M m r n i o co r o CN r o CN m NO r o oo vo r o r o r o — ' "d - ON CN ro m CS r o ro ro oo ro m m cs m ro r o cs m ro 0\ i n N - 0 0 O O — m cs v-> r o ro ^ in cs NO " CN N ^ ^ « - r o ^ <s r o •* Q Q Q Q Q Q Y\ r\ oo oo oo oo ^ ^ H H H H J 00 00 00 00 £ fr 00 ro £ u CX 3 < S fri loo -° & co a 3 " " 3 8 > !< > X CJ O . 3 « " 3 r - cs NO — ' ^ i n CS N O r o r o ON 0 0 " 3 " ON CN 0 0 >— f CS -sf r o CS r o m m NO NO m VO C-~ "cf r o O O —• cs <n ro r o o o o m h (N! ON O O r o -*r r o — ' cs — r^ ^ § 2 2 2 o o NO <n r o cs t-O O r o oo II o c s o o o o m vo r o cs as © r-~ m ro — CS — NO m \f co ^) ON r- •* m oo NO m — oo i n N O ON i n ON CS ro co ^J" r o r o >— CS i n r o o d o o o o cs — iri H * co _ rM rr, Q Q Q Q Q Q Y\ ri oo oo oo oo U U H H H H i-l J 00 00 00 00 o <n oo r-~ NO NO t^- cs cs m oo o *o —• m cs cs — ro ^ - ro cs oo m ro •cf cs cs o o m o m ro ON oo cs O NO ro cs ' 1 r o cs 0 o o ° ^ R ^ ^ ^ o o o © o r o r o CS ro CS -CT — — — o o O o cs ro o CS NO cs ro CS m ro CS NO oq NO CO ro 0 0 CO ro ro ro CS ON m r o ro cs cs CO ro ro cs ro CS CO O d d d d i n i n NO r o ro ro CN 7 ^ ^ (N n t Q Q Q Q a Q Yi Yi oo oo oo oo U id H H i~ H iJ J oo oo oo oo 94 r -ON ON V O O N O S CO U O N O N V O O N O N > aid «3 Jl K 3 O N O N V O O N O N fe ra a, 3 o > r3 <L) s 00 t ts 00 00 N cc H t VO I f l O l CA CO i— i <—i CN •—i 0 0 CO N t OO M © CO V O CN O N O N r o -H <-< CN <-H CN ^ VO CN 1 — 1 r H <-H CN oo v o TJ- r -r o >n r - o o CO > H M CN - H O N 00 O N CO V O i n TJ- oo o CN o ON vo CN "-i m t--TJ- r - oo ON CN ON >n r o i n o oo o O CN 00 r H TJ- vo in oo o\ o m o v o oo o * o o v o r - CN c o v o TJ- r n CN 00 CN VO ' t OO CN CO vo TJ- — i n r o r o r o r o CN ON m v o o v o 0O N f l VO i f rt T <7 r H cN ro Q Q Q Q Q Q Y\ 00 00 00 00 H H " 00 00 00 00 VO VO CN O VO CN vo r o TJ - CN O N ON CN r H r n CN >-i « ^ N t 0O v o r o m CN oo oo CN r H r n CN r H —i o oo i n r n oo r - ON m vo CN CN CO CO VO r n Ov 00 Cn r H r H CN r H OO r H O N r H - r j - p-j - H u-) r o i n m i n ON CN r - oo oo m r H IT) r j - I/-) CO CO r H r j - fs| (-^  r H r H r H CN r H U O I > 00 r H r H CN m - r t i n v o i n • r f CN oo CN o CN VO CN CN VO r H 00 T j - © CN 00 CN v o CN r o v o co r H in TJ- r - in TJ-T f v o T}- v o ON r o oo CN r o v o r o — i '7 «V r H CN CO T j -Q O Q Q Q Q Y\ Y\ oo oo oo oo J i - l oo oo oo oo m § 9 i B n b y oo & O N O N VO ON Ov CHI-O _H-H T3 fco a, 3 te O N O N co 8 CO a-v o O N O N fe & &« 3 v IS o > CJ t CO 00 oo CN co ro r ro r~ r- ON ON TJ- O CN CN -H T t CN TJ-v o m CN i n m ON m r j - o • r f TJ-CN CN r n T J - CN r o CO CN CN VO CN O i n TJ- - r j - v o m vo o o o o o o m TJ- o r o m CN CN r H T j - {SI co o o oo v o CO v o o o r o v o o o ro oo TJ- vo o o V O CO m i n o o V O O N m T t H CO in TJ-o o CO T j -v o m "7 <7 r H cN ro Q Q Q Q Q Q Y\ Y\ 00 00 00 00 r J rJ H H H H 00 00 00 oo cS 95 s i m p l i f i e d into the f o l l o w i n g statistical f o r m for any geochemica l s a m p l i n g p r o g r a m (Gri f f i ths , 1967): S 2 (total) = S 2 ( w i t h i n site) + S 2 (analytical) + S 2 (sample preparation) + S 2 (random) (4-1) where: S 2 ( w i t h i n site) - the natural variation/fluctuation o f an element w i t h i n the sample m e d i u m and i n c l u d i n g errors due to s m a l l scale features such as h y d r a u l i c effects causing l o c a l sort ing (lateral and vert ical) , l i t h o l o g i c a l inhomogeneity , and deposit ional stratif ication. S 2 (analytical) - the variance due to sample preparation and analysis S 2 (random) - encompasses a l l r a n d o m errors H o w e v e r , w i t h i n this study there are also temporal components to consider, as samples were col lected, prepared and analyzed i n two different years. V a r i a b i l i t y due to changes i n sample c o l l e c t i o n procedures are assumed to be n e g l i g i b l e , as sample sites were selected, re-vis i ted and sampled b y the same person and w i t h the same criteria i n 1996 and 1997. There is also the potential for temporal changes i n the natural geochemica l signature, w h i c h w i l l be considered i n Chapter 5. T h u s , the equation for total var iat ion m a y be m o d i f i e d as f o l l o w s to variat ions due to temporal changes: 96 S 2 (total) = S 2 (analyt ical + analyt ical temporal changes) + S 2 (sample preparation + temporal changes i n sample p r e p a r a t i o n ) + S 2 ( w i t h i n site + temporal changes w i t h i n site) + S 2 (random) (4-2) where: S 2 ( a n a l y t i c a l analyt ica l temporal changes) - the var iat ion due to analysis and any change i n analysis w i t h t ime S 2 (sample preparation + temporal changes i n sample preparation) - the var iat ion i n sample preparation and any changes i n sample preparation w i t h t ime (temporal component assumed negl ig ib le) S 2 ( w i t h i n site) - the natural variation/fluctuation o f an element w i t h i n the sample m e d i u m and i n c l u d i n g errors due to s m a l l scale features such as h y d r a u l i c effects causing l o c a l sorting (lateral and vert ical) , l i t h o l o g i c a l inhomogeneity , and deposi t ional stratif ication and the change i n the natural var iat ion over t ime. S 2 (random) - encompasses a l l r a n d o m errors T h e qual i ty contro l program was designed so that the v a r i a b i l i t y due to analysis and the total v a r i a b i l i t y (nested var iab i l i ty due to natural v a r i a b i l i t y w i t h i n site, analysis , sample preparation, s a m p l i n g and r a n d o m error) were measured b y insert ing duplicates at var ious stages. T h e analyt ical variance can be determined f r o m laboratory duplicates, and any temporal var iat ion i n analyses between sample batches i n 1996 and i n 1997 can be determined f r o m samples re-submitted for analysis i n 1997. F i e l d duplicates can be used to quantify total var iat ion i n samples. It is 97 important to real ize that errors i n the geochemical data are nested and that the f ina l data includes error f r o m a l l o f the aforementioned sources o f error. 4.2.1 Analytical Precision and temporal variability in analytical precision: Laboratory duplicates A n a l y t i c a l p r e c i s i o n was m o n i t o r e d b y the r a n d o m insert ion o f analyt ica l duplicates i n sample batches i n b o t h 1996 and 1997. In addit ion, i n 1997 r a n d o m l y selected samples f r o m 1996 were resubmitted for analysis. R a w data for laboratory duplicate pairs and for duplicates o f 1996 samples re-submitted i n 1997 can be found i n A p p e n d i x B . P r e c i s i o n , at the 95 % confidence leve l , was evaluated graphica l ly b y the T h o m p s o n - H o w a r t h m e t h o d ( T h o m p s o n and H o w a r t h , 1978) u s i n g the 9 0 t h percenti le contro l l ine and evaluating each element i n d i v i d u a l l y for each digest ion method. T h o m p s o n - H o w a r t h plots (Figures 4.2.1 A and 4 . 2 . 2 A ) and X - Y contro l plots (Figures 4.2.3 - 4.2.5) were generated for a l l elements from each d e c o m p o s i t i o n technique ( A p p e n d i x B ) . A n a l y t i c a l (laboratory) p r e c i s i o n is general ly better than ± 2 0 % for most elements f r o m the two decomposi t ions (aqua regia and total) i n b o t h 1996 and 1997 (Table 4.2.1). E x c e p t i o n s to this are elements such as P b that are at or near their analyt ical detection l i m i t (Table 4.2.1). F o r samples re-analyzed over the two-year p e r i o d laboratory p r e c i s i o n decreases to better than ± 25 % for most elements (Table 4.2.2). 98 A ) 1997 laboratory duplicates 1000 S a cs o I I •8 100 10 •P = +A •P = +A 1 5 % 2 0 % 10 B ) 1997 field duplicates 100 Mean concentration (ppm) 1000 1000 i I § 1 C/3 100 10 •P = + / -15% •P = +/ -20% 10 100 Mean concentration (ppm) 1000 Figure 4.2.1: Precision o f Co, N i and Z n at the 95 % Confidence level determined by the standard Thompson-Howarth (1978) method for geochemcial results from total digestion for A ) lab duplicates in 1997 and B) field duplicates in 1997. The diagonal lines are control lines calculated at the 90th percentile. 99 B) 1997 field duplicates 10 N ' C O > u -a I 0.1 0.01 •P = +/-5% •P = +/-10% •P = +/-15% Al 10 Mean concentration (%) Figure 4.2.2: Precision of Al, Fe and Mg at the 95 % Confidence level determined by the standard Thompson-Howarth (1978) method for geochemcial results from total digestion for A) lab duplicates in 1997 and B) field duplicates in 1997. The diagonal lines are control lines calculated at the 90th percentile. 100 Figure 4.2.3: Comparison of geochemical results from aqua regiadigestions for lab and field duplicate samples from 1997 for Ni. The solid line represents the x=y line and the dashed lines are +/- 20 %. 101 Figure 4.2.4: Comparison of geochemical results from aqua regia digestions for lab and field duplicate samples from 1997 for Zn. The solid line represents the x=y line and the dashed lines are +/- 20 %. 102 1000 a a i 100 a = 10 10 * 97 lab duplicates • 97 field duplicates 100 Original sample (ppm) 1000 Figure 4.2.5: Comparison of geochemical results from aqua regia digestions for lab and field duplicate samples from 1997 for Cu. The solid line represents the x=y line and the dashed lines are +/- 20 %. 103 1 fe K H T d CO S3 o c 3 o o co co S3 cd 43 CD P "2 o Ti (3 T3 o CD C c .2 .2 t3 6 'S O cd a fi > * & g ^ _2 £ « c ^ « a S T d 6 .2 w i s • rH r--ON ca cd S3 ft £ 13, •S SS 2 g cd cu • 2 ^ 3 IO T j 'o C cu • ' H .-£» ° * O IS hn - H ^ ,2 2 S 3 ^ .—I CD cd > CU -*-» CO S3 o •4-> cd O cd > Id o o « g T d 0 a & o >; ( J O . * ! 1 ^  •§ 5 m 00 CU (H cd > 3 ts I CU bo' ^ > S ° \ 3 cu 60 CU H cd cr cu OO (3 .2 cu - H Q c cu 6 cu W ON ON P H "8 NO ON ON c .2 ~ u -is Q c cu s cu W o j ^ i n o o i n o i n o o o o o ^ i n o o o O m A m A o m A i n i n o o j S i n i n i n i n o i n 0 , o in in t tN N i n m o m i n o i n o o i n o in m o O CN CN tN CN ° 2 S !2 A ~ c n ~ O m m ^ m C N - £ o o o o C N c n C N • — i in o m o C N cn C N cn g 6 >= 5 ft ° r * « S ft fto C N 2 O ft ft ft rH © rH p, p, ft ft ft © rn o ft ft rH rH rH O O O m rH © ft ftH ft ft o X C N r n O r H C N r-j co cd ed O I H 3 cu k> J5 rO rH OH 00 H r> ^ O O i n i n i n o o o o ^ o o l n O O o O ^ o o o o S m o m o o m i n S o o i n i n " 0 r H r H ( N C N A ' r H r H r - 1 c n r H r - ( r - l , A 1 r H C N r H r H ^ O O O O O m i n o o o i n m in A O O m O O m o O H H H is n S i n o i n o i n i n i n S i n o m m rH P T r - H ftftftrHrHrH ftrH ft O ^ O ft ft ft © O O ftO ft1* o ' 2 © ' ^ H ' - H ' - H © © © i ^ © ' ^ 5 s e ^ ft ft rH ft ft O r-V ^ s e, ft ftl ft ft| rH C N r - j c d c d O r V H ' 3 e u . > * ? Cd -jr. r< £ W H > c N 1 0 4 Table 4.2.2 Summary of Thompson-Howarth precision results for the same sample submitted in the subsequent year. Precision values at the 95 % confidence level. Total digestion Aqua regia digestion Element Precision Element Precision A l 10 A l 25 B a 10 A s 30 C a 15 B a 25 C o 25 C a 25 Cr 25 C o 15 C u 25 C r 25 Fe 10 C u 25 K 15 Fe 10 M g 25 K 30 M n 10 M g 15 N a 15 M n 15 N i 25 N i 25 P 15 P 10 Sr 15 Sr 30 T i 25 T i 30 V 25 V 30 Z n 25 Z n 15 105 Samples were submitted to C h e m e x i n a different sequence to that i n w h i c h they were col lected or prepared. Samples were re-ordered i n the sequence o f preparation and analysis to l o o k for any systematic changes i n concentration due to systematic errors or contaminat ion (Figures 4.2.6 and 4.2.7). There were no trends i n concentration, for any element, w h e n samples are arranged i n order o f preparation, or analysis. T h i s indicates that there were no systematic errors or contaminat ion introduced d u r i n g sample preparation or analysis i n either o f the two sample batches. 4.2.2 Within- site variation: field duplicates V a r i a t i o n w i t h i n sample sites was considered b y c o l l e c t i o n o f f i e l d duplicates taken w i t h i n a few meters o f each other o n the stream bed. It is important to reca l l that the var iat ion i n f ie ld duplicates is also an indicat ion o f the var iat ion due to a l l other sources o f error. R a w data for f ie ld duplicate pairs can be found i n A p p e n d i x B . P r e c i s i o n for f i e l d duplicates was determined b y T h o m p s o n - H o w a r f h plots (Figures 4.2. I B and 4 . 2 . 2 B ) for a l l elements f r o m each d e c o m p o s i t i o n technique. X - Y control plots were also generated (Figure 4.2.3 - 4.2.5) ( A p p e n d i x B ) . W i t h a few exceptions, results o f f i e l d v a r i a b i l i t y l ie w i t h i n ± 25 % l i m i t s o f the d iagonal l ine o f equal values, ranging f r o m ± 1 0 % to > 50 % for different elements. N o t e that i n a l l cases, the p r e c i s i o n i n the f ie ld is greater than or equal to the laboratory (analytical) p r e c i s i o n (Table 4.2.1). A n obvious exception to the general ly reasonable p r e c i s i o n is C u , w h i c h shows an unusual ly large amount (> 5 0 % ) o f within-s i te var ia t ion (Table 106 0 20 40 60 80 100 120 140 160 Order of sample preparation 3 _ . 0 _| , , , , , , , 1 0 20 40 60 80 100 120 140 160 Order of sample preparation 300 -j 250 -0 20 40 60 80 100 120 140 160 Order of sample preparation Figure 4.2.6: Plot of samples in order of sample preparation for Cu, Mg, and Zn to check for systematic errors and contamination. 107 20 40 60 80 100 120 140 160 Order of analysis 20 40 60 80 100 120 140 160 Order of analysis 300 2-5 150 20 40 60 80 100 Order of analysis 120 140 160 Figure 4.2.7: Plot of samples in order of analysis for Cu, Mg, and Zn to check for systematic errors and contamination. 108 4.2.1, F i g u r e 4.2.5) i n both 1996 and 1997. N o t e that C u does not show a large amount o f var iat ion i n laboratory duplicates, indicat ing that the v a r i a b i l i t y does not arise due to analysis. 4.3 Within-site variation compared to between-site variation It was important to establish that c o m p o s i t i o n a l differences between sites and between streams are real rather than r a n d o m l o c a l variations. T h i s was a c c o m p l i s h e d b y c o m p a r i n g elemental concentrations o f f ie ld duplicates to the o v e r a l l var iat ion i n elemental concentration o f the streams. A series o f A n a l y s i s o f V a r i a n c e ( A N O V A ) F-tests (Table 4.3.1) was used to test that the within-s i te var iat ion ( a w s ) is s igni f icant ly less than the between-site var iat ion (rj b s ). T h e n u l l hypothesis ( H 0 ) for these A N O V A F-tests is that there is no difference between the variances ( o b s 2 = o w s 2 ) : the alternate hypothesis is that the between-site var iat ion is greater than the w i t h i n -site var ia t ion ( a b s 2 > r j w s 2 ) (Cass, 1973). N o t i c e that for most elements the F values are m u c h greater than the cr i t i ca l F values, m e a n i n g that the n u l l hypothesis (equal variances) is rejected and the alternate hypothesis (between-site v a r i a b i l i t y greater than the within-s i te var iabi l i ty) is accepted. T h e strength o f the F values indicates that the within-s i te v a r i a b i l i t y is substantially less than overa l l v a r i a b i l i t y a long streams. Therefore, c o m p o s i t i o n a l differences a long and between streams ident i f ied i n the geochemica l data can be considered real , rather than due to r a n d o m l o c a l variations. 109 T a b l e 4.3.1: S igni f icance o f A N O V A F-tests for wi th in-s i te ( f ie ld duplicates) versus between-site variances at the 0.05 s igni f icance leve l . 1996 1997 Element Total Aqua regia Total A q u a regia A l X X X X X X A s - X X - X X X B a X X X X X X X X X C a X X X X X X X X X X X C o X X X X X X C r X X X X X X X X X X X X C u X X X Fe X X X X X X K X X X X X X X X X X X X M g X X X X X X X X X X X X M n X X X X X X N a X - X X X N i X X X X X X X X X X X X P X X X X X X X X Pb X X X X Sr X X X X X X X X X T i X X X X X X X X X V X X X X X Z n X X X X X X C-total X X X X X X = F > Fcrit ical X X = F > 5 x Fcrit ical X X X = F > 10 x Fcrit ical - = not determined blank = F not signifcant 110 4.4 Discussion of Data Quality In order for geochemica l results to y i e l d meaningfu l i n f o r m a t i o n o n trends or anomalies, the natural var iat ion must be s igni f icant ly larger than the accumulated var iat ion due to s a m p l i n g , sample preparation, analysis and r a n d o m error. A n a l y t i c a l (laboratory) prec is ion is w i t h i n ± 2 0 % for most elements (except those at or near their detection l imits) for b o t h d e c o m p o s i t i o n techniques i n both years (Table 4.2.1). L a b o r a t o r y p r e c i s i o n decreases to approximately ± 25 % for most elements for samples re-analyzed over the two-year p e r i o d (Table 4.2.2). F i e l d var iat ion or var ia t ion w i t h i n a site o n the stream b e d is w i t h i n ± 25 % for most elements a l though there is a considerable range o f f ie ld v a r i a b i l i t y (± 10 % to > 50 % ) (Table 4.2.1), for most elements an error term o f ± 25 % can be used to account for v a r i a b i l i t y f r o m a l l sources. E lements w i t h total v a r i a b i l i t y higher than ± 25 % w i l l not be used i n cons ider ing the effects o f l o g g i n g disturbance. C o p p e r shows unexpectedly h i g h (> 5 0 % ) within-s i te var iat ion i n b o t h 1996 and 1997 (Table 4.2.1, F i g u r e 4.2.5), w h i l e s i m i l a r v a r i a b i l i t y is not apparent i n laboratory duplicates. T h e cause o f this a b n o r m a l l y h i g h l o c a l v a r i a b i l i t y for copper is not understood. H o w e v e r , laboratory or other sources o f contaminat ion have been e l iminated b y l o o k i n g for systematic errors or contaminat ion b y re-ordering samples 111 into the sequences i n w h i c h they were sampled, prepared and analyzed. N o n e o f the equipment used i n any o f these procedures contained copper. H i g h l y variable copper concentrations were apparent o n a l l s ix o f the study streams and were not o b v i o u s l y related to any anthropogenic source o f contamination. T h e copper v a r i a b i l i t y was also noted i n f i e l d duplicate samples f r o m both 1996 and 1997, and samples submitted for re-analysis c o n f i r m e d the i n i t i a l analyses. Further analyses and heavy m i n e r a l separations suggest that the anomalous ly h i g h and variable copper concentrations were l i k e l y due to a m i n e r a l occurr ing w i t h i n the - 0.053 m m size fraction. T h e results o f these analyses w i l l be presented i n Chapter 5, T a b l e 5.1.3. N e i t h e r the heavy or l ight minera ls , f r o m heavy m i n e r a l separations, o f the 0.053 - 0.106 m m or the 0.053 - 0.212 m m size fractions shows the h i g h amount o f v a r i a b i l i t y i n copper concentrations. W h i l e the m i n e r a l o g i c a l source o f the copper has not been determined, copper m a y be present as a trace element w i t h i n m a f i c minera ls o f the -0.053 m m size fraction (e.g., magnetite, pyroxene, o l i v i n e , chlori te , epidote, hornblende, and/or amphibole) . 112 4.5 Data quality summary T h e data qual i ty control p r o g r a m was used to estimate accuracy and p r e c i s i o n o f analyt ica l results. P r e c i s i o n was determined independently for 1) laboratory procedures w i t h i n a single year, 2) laboratory procedures between successive years, and 3) i n d i v i d u a l sites i n a single year. V a r i a t i o n w i t h i n sites was c o m p a r e d to var iat ion between sites and the overa l l v a r i a b i l i t y a long the stream, to c o n f i r m that trends between and a long streams were not r a n d o m variations. It was c o n c l u d e d that for most elements the data qual i ty was adequate to a l l o w trends i n the geochemistry a long streams to be ident i f ied and to compare changes i n stream sediment c o m p o s i t i o n f r o m disturbed and undisturbed sites. E lements w i t h p o o r data qual i ty are easi ly ident i f ied and were not i n c l u d e d i n comparat ive analysis (e.g. A s , C u and P b ) . 113 CHAPTER 5 TEXTURE, MINERALOGY, AND GEOCHEMICAL ABUNDANCES PRIOR TO LOGGING Work in 1996 resulted in a comprehensive baseline database of the texture, mineralogy, geochemical abundance and spatial distribution of elements within the six study streams. The geochemical effects of the 1997 winter logging of B l , B 2 , B3 and B5 drainage basins could then be evaluated and compared with this baseline database. Geochemical trends along and between streams and inter-element correlations were identified in the 1996 data: these define the natural geochemical fingerprint of each of the streams. 5.1 Results 5.1.1 Texture and mineralogy The stream sediments are poorly sorted with rounded to sub-angular clasts. Average cumulative grain size distribution curves are similar for all streams (Figure 5.1.1), with a median grain size ( D 5 0 ) of ~ 4.5 mm (granule - pebble sized). Local tills have a median grain size (D 5 0 ) of ~ 0.6 mm (coarse sand size). On average, stream sediments contain 6%, by weight, finer than 0.212 mm, while tills contain 38%. Sediments are thus much coarser than tills. 114 o © U 8 q ; J3UIJ 3 § B J U 3 3 J 3J 115 Histograms o f average grain size distributions show a sl ight f i n i n g o f stream sediments downstream. H o w e v e r , there is considerable textural v a r i a b i l i t y between i n d i v i d u a l sample sites and there are too few samples to statist ical ly substantiate this observation. Clasts w i t h i n stream sediments inc lude a w i d e variety o f l i thologies , der ived p r i m a r i l y f r o m t i l l , i n c l u d i n g : serpentinite, serpentinized peridotite and dunite, chert, andesite, rhyol i te , breccia , tuffs, granodiorite, granite, quartz and others (Sect ion 2.2). C o m m o n minerals identi f ied b y hand-lens f r o m sediment samples are s h o w n i n Table 5.1.1. T h e p r i m a r y m a f i c and ultramafic minerals are: o l i v i n e , chlor i te , serpentinite, amphibole , pyroxene, epidote, talc and biotite. A n a l y s i s o f selected samples o f the - 0.053 m m size fraction w i t h the R i e t v e l d m e t h o d and p o w d e r X - r a y di f fract ion data, was used to m o r e quantitat ively define the minera logy . W i t h i n sediments o f this size fraction, the eight p r i m a r y minerals ident i f ied and their weighted average w i t h i n - 0.053 m m sediments are: quartz (28 % ) , p lagioclase (24 % ) , muscovi te (12 % ) , c l inochlore (chlorite) (11 % ) , pargasite (amphibole) (5.5 % ) , talc (5 % ) , m i c r o c l i n e (Potass ium feldspar) (4 % ) , and epidote (3 % ) (Table 5.1.2). There are sl ight increases i n quartz ( 2 6 % - 3 6 % ) and plagioclase (26-29 % ) concentrations f r o m B l to B 5 , w h i l e chlorite shows a corresponding decrease (14.5-8.9 % ) i n concentration. 116 T a b l e 5.1.1: M i n e r a l s ident i f ied w i t h i n stream sediments f r o m creeks B l - B 6 M i n e r a l C h e m i c a l F o r m u l a S . G . Light Minerals. S . G . < 3.3 Serpentine (l izardite) ( M g , F e ) 3 S i 2 0 5 ( O H ) 4 2.2 M i c r o c l i n e K A l S i 3 0 8 2.5-2.6 A l b i t e N a A l S i 3 0 8 2.62 Quartz S i 0 2 2.65 Plagioc lase N a [ A l S i 3 0 8 ] C a { A l 2 S i 2 O g ] 2.62-2.76 T a l c M g 3 ( S i O 1 0 ) ( O H ) 2 2.7-2.8 C h l o r i t e ( C l i n o c h l o r e ) ( M g , F e ) 3 ( S i A l ) 4 O 1 0 ( O H ) 2 ( M g , F e ) 3 ( O H ) 6 2.6-2.9 A n k e r i t e C a ( F e , M g , M n ) ( C 0 3 ) 2 2.9-3 M u s c o v i t e K A l 2 ( A l S i 3 O 1 0 ) ( O H ) 2 2.7-3.1 Apat i te ( O H , F ) C a 5 ( P 0 4 , C 0 3 ) 3 ( F , O H , C l ) 3.1-3.2 K a o l i n i t e A l 2 ( S i 2 0 5 ) ( O H ) 4 2.6-2.7 A c t i n o l i t e C a 2 ( M g , F e ) 5 S i 8 0 2 2 ( O H ) 2 3.0-3.2 H o r n b l e n d e (pargasite) N a C a 2 F e 4 ( A l , F e ) A l 2 S i 6 0 2 2 ( O H ) 2 3.2 (amphibole) Heaw Minerals. S . G . > 3.3 T r e m o l i t e CajMgsSigO^COIiOj 3-3.3 E p i d o t e C a 2 ( F e , A l ) A l 2 [ 0 | O H | S i 0 4 | S i 2 0 7 ] 3.3-3.5 Titanite (sphene) C a T i O ( S i O ) 4 3.4-3.5 A l l a n i t e ( C a , C e ) 3 ( F e 2 + , F e 3 + ) A l 2 0 ( S i 0 4 ) ( S i 2 0 7 ) ( O H ) 3.5-4.2 F e - C r - A l - M g - sp ine l ( M g , F e , Z n , M n ) A l 2 0 4 3.6-4 R u t i l e T i 0 2 4.2-4.3 I lmenite F e T i 0 3 4.7 M o n a z i t e (Ce) ( C e , L a , Y , T h ) ( P 0 4 S i 0 4 ) 5.0-5.3 Paramagnetic (potentialtv) O l i v i n e ( M g , F e ) 2 S i 0 4 3.3-4.4 Pyroxene (subcalcic) C a ( M g , F e ) S i 2 0 6 3.3-3.6 Magnet i te F e 3 0 4 5.18 117 T a b l e 5.1.2: A v e r a g e percentages o f minerals i n sediments f r o m streams B 1 - B 5 determined b y X R D (Rietveld) o n - 0.053 m m size fractions. B l B 2 B 3 B 4 B 5 W e i g h t e d n=6 n=3 n=3 n = l n=2 M e a n Quartz 25.7 30.2 31.9 32.3 35.6 27.7 P lagioc lase 25.5 26.2 26.3 22.6 28.9 24.4 M u s c o v i t e 13.3 14.2 11.3 ^ 12.9 11.4 12.0 C l i n o c h l o r e (chlorite) 14.5 10.1 10.4 8.6 8.9 10.9 Pargasite 6.3 5.3 5.8 6.1 5.2 5.5 T a l c 5.6 5.0 7.3 6.8 1.3 5.0 M i c r o c l i n e (k-spar) 5.0 4.5 3.5 1.7 4.7 4.1 E p i d o t e 2.5 2.6 2.7 4.7 3.4 2.7 C o r u n d u m * 1.7 1.9 0.9 4.4 0.6 1.5 * Contamination resulting from the grinding procedure 118 Results o f geochemical analysis o f the heavy m i n e r a l fract ion (specif ic gravi ty ( S . G . > 3.3), the paramagnetic fraction ( S . G . > 3.3), and the l ight fractions ( S . G . < 3.3) are presented i n T a b l e 5.1.3. T h e heavy m i n e r a l fractions, p r i m a r i l y m a f i c minera ls , have re lat ive ly h i g h concentrations o f C a , C o , C r , M n , N i , P b , Sr, T i , V , W , and Z n , w h i l e the l ight fractions, p r i m a r i l y felsic minerals , have re lat ively h i g h concentrations o f A l , B a , C a , C d , C u , K , N a , P , and Sr. T h e paramagnetic fract ion is p r i m a r i l y magnetite, but it also contains a few grains o f o l i v i n e and pyroxene and some felsic m i n e r a l fragments attached to these minerals . T h i s fraction has re lat ive ly h i g h concentrations o f C r , C o , F e , M n , N i , T i , V , and Z n . W i t h i n the - 0.053 m m size fract ion, notice that the C u concentrat ion is 288 p p m , w h i c h is considerably greater than the C u concentrations i n the heavy (37 p p m ) , paramagnetic (20 p p m ) or l ight m i n e r a l (50 p p m ) fractions. A v e r a g e total carbon i n sediment f r o m each stream ranged f r o m 2.8 % to 5.2 % , w i t h a weighted m e a n o f 3.5 % (Table 5.1.4). T h e concentration o f carbon i n sediments appears to decrease downstream o n a l l s ix streams. 5.1.2 Geochemistry A n a l y t i c a l results o f samples col lected i n 1996 after total and aqua regia digestions are presented i n Tables 5.1.5 and 5.1.6; results o f the 1996 h y d r o x y l a m i n e 119 T a b l e 5.1.3: Concentrat ions o f elements i n heavy minera ls , paramagnetic, and l ight fractions w i t h i n the 0.053-0.212 m m size fractions and w i t h i n the -0.053 m m size fraction. Size fraction analysed 0.053-0.212 mm - 0.053 mm Heavy Minerals S.G. > 3.3 n=17 Magnetic n=3 Light fractions n=16 n=5 A l % 4.5 0.9 6.4 6.4 Fe % 16 >25 3 4 Mg % 1.58 1.44 1.77 2.67 Ca % 6.7 0.94 1.80 1.64 Na % 0.09 <0.01 2.46 1.66 K % 0.04 0.01 1.14 1.01 Ti % 2.55 2.48 0.36 0.43 Ba ppm 82 67 648 654 Be ppm 0.12 0.37 0.50 0.60 Cd ppm <0.5 <0.5 0.67 0.5 Co ppm 36 118 16 33 Cr ppm 438-3110 * >10000 144 298 Cu ppm 37 20 50 288 Mn ppm 3479 3147 951 2046 Ni ppm 158 808 129 341 P ppm 341 473 492 922 Pb ppm 21 15 10 13 Sr ppm 478 54 300 219 V ppm 626 1563 122 138 W ppm 17 10 <10 <10 Zn ppm 200 685 107 309 * Note that within the heavy minerals, Cr concentrations are presented as a range of concentrations due to highly variable amounts of Cr within samples. 120 T a b l e 5.1.4: S u m m a r y o f average carbon concentrations f r o m 1996 and 1997 analyses. 1996 1997 Stream n m e a n std. dev. n m e a n std. dev. B 6 6 2.82 0.60 5 3.77 1.08 B l 24 2.86 1.87 26 3.19 2.12 B 2 14 3.01 1.06 30 2.81 1.68 B 3 2 0 3.75 2.18 33 3.29 2.48 B 4 17 3.14 3.19 22 2.86 3.01 B 5 18 5.24 3.02 43 3.35 3.3 W e i g h t e d m e a n for a l l streams 3.5 2.1 3.2 2.3 121 T a b l e 5.1.5: S u m m a r y o f average concentrations o f elements i n streams B 1 - B 6 f r o m 1996 total analyses. B 6 B l B 2 B 3 B 4 B 5 n=6 n=24 n=14 n=20 n=17 n=18 A l % 5.83 6.19 6.18 5.99 6.30 6.61 Fe % 4.38 4.53 3.89 3.70 4.01 3.86 M g % 3.64 2.92 2.13 2.04 1.76 1.29 C a % 1.55 1.87 1.83 1.79 1.85 1.92 N a % 1.77 1.88 1.90 1.81 1.90 1.74 K % 0.87 0.94 0.94 0.91 1.02 1.02 T i % 0.40 0.53 0.42 0.40 0.44 0.40 B a ppm 542 544 568 561 618 664 C d ppm 1.50 0.56 0.50 0.50 0.80 1.93 C o ppm 34 31 26 23 23 21 C r ppm 598 381 257 240 214 126 C u ppm 203 136 81 131 130 161 M n ppm 1649 1310 1343 1286 1426 2589 M o ppm 1.00 1.20 1.25 1.14 1.54 2.13 N i ppm 445 377 303 186 164 92 P ppm 726 862 721 673 827 1024 Pb ppm 5.20 8.56 4.59 5.41 5.75 6.71 Sr ppm 222 211 240 229 247 257 V ppm 128 141 135 131 143 130 Z n ppm 93 112 119 108 127 143 122 T a b l e 5.1.6: S u m m a r y o f average concentrations o f elements i n streams B 1 - B 6 , f r o m 1996 aqua regia analyses. ment B 6 B l B 2 B 3 B 4 B 5 n=6 n=24 n=14 n=20 n=17 n=18 A l % 1.72 2.02 1.66 1.72 1.75 2.26 Fe % 3.80 3.89 3.30 3.16 3.50 3.41 M g % 2.16 1.82 1.22 1.17 1.12 0.88 C a % 0.41 0.58 0.61 0.63 0.68 1.00 K % 0.05 0.14 0.08 0.07 0.09 0.09 T i % 0.10 0.15 0.11 0.11 0.12 0.10 A s ppm 20.0 14.9 37.3 15.2 8.5 7.5 B a ppm 116 118 96 114 120 175 C d ppm 1.00 0.84 0.70 0.86 1.00 2.12 C o ppm 25.6 25.2 19.8 18.2 18.9 17.4 C r ppm 303 224 153 141 134 76 C u ppm 201 133 80 134 132 162 M n ppm 1433 1071 1138 1115 1226 2431 M o ppm 1.00 1.06 1.08 1.50 2.47 N i ppm 290 314 260 137 134 82 P ppm 536 712 567 533 674 779 Pb ppm 6.00 10.16 3.65 5.53 6.24 6.89 Sc ppm 6.20 6.24 5.88 5.83 6.47 6.61 Sr ppm 27.6 30.3 36.5 34.2 39.4 77.5 V ppm 59.0 69.7 63.5 63.4 70.5 62.4 Z n ppm 80 102 111 104 123 136 123 h y d r o c h l o r i d e analyses can be found i n A p p e n d i x C . C o m p o s i t i o n a l trends w i t h i n these results were identi f ied both w i t h i n streams and between streams. A l o n g streams there are wel l -def ined c o m p o s i t i o n a l changes, w i t h some elements increasing and others decreasing i n concentration downstream (Table 5.1.7 and F i g u r e 5.1.2 for B a , N i and M g ) . Streams B 3 and B 4 show s i m i l a r c o m p o s i t i o n a l trends, w i t h decreases i n B a , M g , N i and C and increases i n T i downstream. T w o distinct c o m p o s i t i o n a l trends between streams are revealed i n b o x and w h i s k e r plots o f some elements. Concentrations o f C o , C r , M g and N i decrease i n sequence f r o m stream B 6 through streams B l , B 2 , B 3 , B 4 and B 5 (i.e., from northeast to southwest across the region) (Figure 5.1.3), whereas A l , B a , P and Sr show the opposite trend (Figure 5.1.4). These trends are also apparent i n the tables o f average concentrations (Tables 5.1.5 and 5.1.6). Further examinat ion o f the geochemical data ident i f ied some h i g h l y s ignif icant inter-element correlations. Tables 5.1.8 and 5.1.9 show correlat ion coefficient ( r ) values greater than 0.7. These correlations are statistically s ignif icant at the 9 9 . 9 % confidence l e v e l o n a l l s ix study streams. A s u m m a r y o f inter-element correlations o c c u r i n g i n four or more streams can be found i n Table 5.1.10. B a - K , C a - S r , C o - M g and F e - V are correlated i n a l l s ix streams, and A l - B a , A l - K , A l - M g , M g - N i and T i - V are correlated i n five streams. T o t a l carbon (surrogate for organic carbon) is negat ively correlated w i t h N a and K i n four study streams. 124 T a b l e 5.1.7 G e o c h e m i c a l trends a long streams i n 1996 data. Dashes indicate elements for w h i c h trends were obscured b y contaminat ion (Zn) or b y a b n o r m a l l y h i g h l o c a l v a r i a b i l i t y ( C u ) . Change in elemental concentration downstream Creek B l , B2 B3 B4 B5 B6 A l decrease increase Fe increase increase Mg increase decrease decrease increase Ca decrease Na K decrease Ti increase increase As decrease Ba decrease decrease increase Co increase Cr decrease increase Cu . . . . . Mn decrease Ni decrease decrease decrease P Sr V increase Zn . . . . . Carbon decrease decrease decrease decrease decrease decrease 125 800 200 400 600 Distance upstream (m) 800 1000 300 ? a a. m 200 "S c o I 100 • Q c o o 1000 Distance upstream (m) 2000 1.75 O) 5 "5 c o 1.25 0.75 0.25 500 1000 1500 Distance upstream (m) 2000 2500 Figure 5.1.2: Geochemical trends along streams in 1996 data. A : Increase in N i upstream on B 2 , B 3 and B4, B: increase upstream in B a on B3 and B5 and a decrease upstream on B 5 , C: Increase in M g concentration upstream on B3 and B 4 and a decrease on B5. 126 N W SE B6 B1 B2 B3 B4 B5 B6 Bl B2 B3 B4 B5 B6 B i : B2 83i B4 B5 Creeks B6 B1 B2 B3 B4 B5 Oeeks F i g u r e 5.1.3: G e o c h e m i c a l trends i n 1996 data s h o w i n g the decrease o f the trace elements C o , C r , M g and N i f r o m the northeast ( B 6 ) to the southwest ( B 5 ) . These elements are thought to be associated w i t h a decrease i n m a f i c minera ls . 127 NW SE 800 700: E M 600 CO B6 B1 B2 B3 B4 B5 500 400 T 1 T J L J L T T _L 1 J JL B6 B'1 B2 B3 B4 35 2000 1500 h | 1C00 r-5001-300 B6 B1 B2 B3 B4 B5 Creeks 250 h "E: St 200 h 150 h 100 JL db _L I J J I J _ B6 B1 B2 B3 B4 B5 Creeks F i g u r e 5.1.4: G e o c h e m i c a l trends i n 1996 data s h o w i n g the increase o f the trace elements A l , B a , P and S r f r o m the northeast ( B 6 ) to the southwest (B5) .These elements are thought to be associated w i t h an increase i n fels ic minera ls . 128 T a b l e 5.1.8 Inter-element correlations ident i f ied i n 1996 geochemica l results from total d igest ion at the 9 9 . 9 % signif icance leve l . Refer to A p p e n d i x D for complete correlat ion matrices for each creek. Ek Coi :ments r - values Number of streams related B6 B l B2 B3 B4 B5 Ba K 0.80 0.86 0.87 0.98 0.91 0.82 6 A l Ba 0.87 0.87 0.92 0.84 0.92 5 A l K 0.83 0.83 0.93 0.84 0.88 5 Co Mg 0.84 0.77 0.90 0.91 0.73 5 Ti V 0.95 0.90 0.93 0.96 0.92 5 A l Na 0.88 0.74 0.88 0.87 4 A l Sr 0.69 0.74 0.86 0.81 4 A l V 0.93 0.89 0.75 0.86 4 Cr Mg 0.88 0.93 0.86 0.70 4 Fe V 0.78 0.88 0.73 0.92 4 K Carbon -0.78 -0.72 -0.67 -0.77 4 K Sr 0.81 0.76 .0.91 0.72 4 Na Carbon -0.93 -0.78 -0.81 -0.84 4 Na Sr 0.87 0.96 0.97 0.96 4 A l Ca 0.84 0.84 -0.87 3 A l Mg 0.93 -0.71 0.90 3 Ba Fe 0.89 0.70 0.87 3 Ba Mg 0.81 -0.80 0.89 3 Ba Na 0.70 0.85 0.69 3 Ba •V 0.73 0.73 0.74 3 Ca Ti 0.93 0.82 0.75 3 Co Cr 0.74 0.86 0.79 3 Co Ni 0.95 0.78 0.83 3 Fe Ti 0.77 0.91 0.73 3 K Na 0.76 0.87 0.80 3 K Ti 0.74 0.76 0.69 3 K V 0.75 0.76 0.81 3 Na P -0.69 -0.85 -0.82 3 Na Ti 0.76 0.86 0.90 3 P Carbon 0.69 0.91 0.87 3 P Ti -0.74 -0.72 -0.72 3 Sr Carbon -0.95 -0.70 -0.73 3 Sr Ti 0.87 0.88 0.92 3 Sr V 0.83 0.72 0.88 3 V Carbon -0.82 -0.72 -0.82 3 129 Table 5.1.9: Inter-element correlations identified i n 1996 geochemical results from aqua regia digestion at the 9 9 . 9 % significance level.Refer to A p p e n d i x D for complete correlation matrices for each creek. Elements Correlated r - values Number of streams B6 B l B2 B3 B4 B5 Ca Sr 0.95 0.73 0.85 0.72 0.96 0.96 6 Co M g 0.91 0.83 0.84 0.84 0.87 0.87 6 Fe V 0.86 0.86 0.85 0.78 0.71 0.87 6 A l Ba 0.91 0.75 0.78 0.91 0.95 5 A l K 0.97 0.89 0.73 0.99 0.95 5 A l M g 0.97 0.84 0.82 0.61 0.86 5 M g N i 0.85 0.72 0.93 0.73 0.75 5 A l Sc 0.93 0.71 0.97 0.96 4 Ba K 0.88 0.77 0.89 0.92 4 Ba N i 0.97 -0.72 0.90 0.97 4 Co Cr 0.86 0.90 0.87 0.71 4 Co Fe 0.69 0.76 0.77 0.77 4 Co N i 0.93 0.74 0.85 0.66 4 Cr Fe 0.91 0.80 0.72 0.92 4 Cr M g 0.89 0.88 0.96 0.88 4 Fe M g 0.84 0.84 0.79 0.94 4 K Sr 0.87 0.70 0.83 0.84 4 M g Sc 0.98 0.73 0.89 0.88 4 N i Sc 0.87 0.89 0.92 0.88 4 T i V 0.83 0.85 0.77 0.66 4 A l Fe 0.76 0.87 0.82 3 A l N i 0.91 0.90 0.95 3 A l P 0.87 0.94 0.79 3 A l Zn 0.77 0.77 0.82 3 Ba C a 0.91 0.81 0.84 3 Ba Sc 0.92 0.92 0.89 3 B a Sr 0.85 0.79 0.79 3 Ca P 0.73 0.95 0.69 3 Co Sc 0.95 0.76 0.68 3 Cr N i 0.82 0.91 0.76 3 Cr Sc 0.83 0.81 0.82 3 Cr V 0.92 0.73 0.85 3 Fe K 0.70 0.89 0.78 3 Fe Sc 0.81 0.74 0.82 3 Fe T i 0.70 0.91 0.66 3 K M g 0.91 0.78 0.89 3 K N i 0.93 0.89 0.91 3 K P 0.86 0.97 0.78 3 K Sc 0.88 0.96 0.94 3 P Sr 0.70 0.92 0.78 3 P Zn 0.95 0.73 0.73 3 130 Table 5.1.10: Summary o f significant interelement correlations with r > 0.7 and at the 99.9 % significance level from 1996 geochemical results o f total (T) and aqua regia ( A R ) digetions. A l l Correlations shown have r values greater than 0.7, significance levels for correlations vary between creeks. Refer to Tables 5.1.8 and 5.1.9 for r values. Negative correlations are in brackets. Number o f streams in which correlations are highly significant 6 5 4 Elements Digestion Elements Digestion Elements Digestion correlated Method correlated Method correlated Method Ba - K T C a - Sr A R C o - M g A R Fe - V A R A l - B a A R , T A l K A R , T A l - M g A R C o - M g T M g N i A R T i V T A l - N a T A l - Sc A R A l - Sr T A l - V T B a - K A R B a - N i A R C o - C r A R C o - Fe A R C o - N i A R C r - Fe A R C r - M g A R , T Fe - M g A R Fe - V T K - Sr A R , T M g - Sc A R N a - Sr T N i - Sc A R T i - V A R (K - Carbon) (Na - Carbon) 131 5.2 Discussion T h e comprehensive database generated i n 1996 ident i f ied geochemica l patterns w i t h i n and between streams. These patterns can be considered real , insofar as evaluat ion o f the data qual i ty (Chapter 4) has c o n f i r m e d that c o m p o s i t i o n a l differences between sites and between streams are s igni f icant ly greater than variations within-s i te . Results o f geochemical analysis are also w i t h i n the " n o r m a l " range o f abundances expected i n stream sediments (Table 5.2.1, L e v i n s o n , 1974; Tables 5.1.5 and 5.1.6). N o g e o c h e m i c a l l y abnormal sources o f sediment were ident i f ied w i t h i n the drainage basins pr ior to l o g g i n g activity. A l l o f the study streams d r a i n the same bedrock unit (serpentinzed peridotite and dunite). H o w e v e r , t i l l is p r o b a b l y the m a i n material contr ibut ing to the sediments, as clasts are der ived f r o m a w i d e variety o f l i thologies . M a n y o f the geochemica l patterns observed between and w i t h i n streams can be attributed to l i t h o l o g i c a l - m i n e r a l o g i c a l factors. T h e part i t ioning o f trace elements between the l ight fractions, paramagnetic fractions and heavy m i n e r a l fractions can be understood b y cons ider ing trace element substitution (Table 5.1.3; T a b l e 1.2.1). T h e paramagnetic fraction, p r i m a r i l y c o m p o s e d o f magnetite ( F e 3 0 4 ) , contains re lat ively h i g h concentrations o f C r , C o , F e , M n , N i , T i , V and Z n - a l l elements that can substitute into the crystal structure o f magnetite. These elements m a y also substitute for F e and M g i n o l i v i n e and pyroxene. W i t h i n the heavy m i n e r a l fractions, C o , C r , M n , N i , T i , V , and Z n were ident i f ied as h a v i n g re lat ively h i g h concentrations. These 132 Table 5.2.1: Range of abundance of trace elements i n soils and sediments (modified from Levinson, 1974). Element Units Range of concentration A l Ti % % 0.5 - 10 0.1 - > 1 As Ba Co Cr Cu Mn M o Ni Pb Sb Sr V W Zn ppm ppm ppm ppm ppm ppm ppm ppm ppm ppm ppm ppm ppm ppm 1 100 1 5 2 100 0.2 5 2 1 50 20 10 - 900 10 - 300 50 3000 40 1000 100 5000 8 500 200 10 1000 500 133 elements c o m m o n l y substitute into m a f i c minerals o f the heavy m i n e r a l fraction, such as o l i v i n e , pyroxene, amphibole , tremolite, epidote and i lmenite . T h e h i g h concentration o f Sr w i t h i n the heavy minerals l i k e l y reflects substitution i n minerals such as titanite, rut i le or monazite . T h e l ight fractions are p r i m a r i l y c o m p r i s e d o f felsic minera ls and have re lat ive ly h i g h concentrations o f A l , B a , C a , C d , C u , K , N a , P and Sr. Trace elements, such as C u , M g , N i , V and Z n , substitute into ferromagnesian minerals such as chlorite, talc, biotite and serpentine, ident i f ied i n the l ight fractions ( S . G . < 3.3). B a s e d o n these m i n e r a l o g i c a l - g e o c h e m i c a l associations, the persistent correlations between C o - M g , C r - M g , C o - N i and M g - N i are l i k e l y a funct ion o f the abundance o f ferromagnesian minerals and the ratios o f trace element substitution therein. S i m i l a r l y , the abundance o f a lumino-s i l icate minerals and trace element substitution w i t h i n these minerals accounts for the correlations between A l - K , A l - T i and A l - B a . Trends i n sediment c o m p o s i t i o n a long streams then l i k e l y reflect variat ions i n the c o m p o s i t i o n o f sur f ic ia l materials ( p r i m a r i l y t i l l s) and l o c a l bedrock, together w i t h changes i n m i n e r a l abundance result ing from weathering and sediment transport (Table 5.1.7). F o r example, streams B 3 and B 4 show s i m i l a r c o m p o s i t i o n a l changes a long stream (Table 5.1.7; F i g u r e 5.1.2). T h i s is p r o b a b l y because b o t h streams have s i m i l a r f l u v i a l processes (gradient and topography) and s i m i l a r sediment sources (surf ic ia l materials and bedrock) (Table 2.7.1). E lements that show c o m p o s i t i o n a l trends a long streams are not o b v i o u s l y related to specif ic trace element controls , 134 i n c l u d i n g : (1) the abundance o f fines, (2 ) F e or M n (surrogates for F e - M n oxides) , or (3) carbon concentrations. A c r o s s the region, f r o m the northeast through to the southwest, two dist inct c o m p o s i t i o n a l trends were identi f ied. Concentrat ions o f C o , C r , M g and N i were seen to increase, w h i l e A l , B a , P and Sr decreased, i n sequence f r o m stream B 6 through streams B l , B 2 , B 3 , B 4 and B 5 (Figures 5.1.2 and 5.1.3). T h e C o , C r , M g and N i associat ion is characteristic o f ultramafic rocks , whereas the A l , B a , P and S r associat ion is m o r e t y p i c a l o f felsic rocks. S i m i l a r l y , m o d a l analysis w i t h R i e t v e l d ident i f ied an increase i n felsic minerals (quartz and plagioclase) and a decrease i n maf ic minerals (chlorite) f r o m B l to B 5 (Table 5.1.2). T i l l s i n the southwest, surrounding B 5 , B 4 , B 3 , contain m o r e clasts der ived f r o m the chert, argi l l i te , andesite and l imestone bedrock to the west, whereas t i l l s i n the northeast are der ived f r o m the amphibol i te , peridotite, serpentine, serpentinized peridotite and dunite bedrock units u n d e r l y i n g the study area (Figures 2.2.1 and 2.2.2). Changes i n the c o m p o s i t i o n o f stream sediments across the study area are, thus, consistent w i t h g l a c i a l smearing and changing composi t ions o f the t i l l as the glacier crossed different bedrock units f r o m west to east. A l l o f the aforementioned geochemical trends, inter-element correlations and temporal v a r i a b i l i t y i n geochemistry are specif ic to these s ix study streams i n the Baptiste watershed. W h i l e results m a y be s i m i l a r i n nearby watersheds w i t h i n the same c l i m a t i c regime, each stream w i l l have its o w n unique geochemica l patterns. 135 5.3 Summary From the foregoing, it is apparent that sediment of the six streams have distinct natural, multi-element geochemical signatures that can be related to the lithology and mineralogy of the geological units present in each drainage basin. While these are the primary controls on trace element abundance, sediment texture and sediment transport processes may also be important. 136 CHAPTER 6 CHANGES IN CONTROL STREAMS, POST-HARVESTING EFFECTS AND NEW SEDIMENT SOURCES Results presented i n this chapter are used to: (i) evaluate the changes i n contro l sites over the study per iod; ( i i ) detect changes i n sediment geochemistry before and after clear-cut l o g g i n g ; ( i i i ) identi fy sources o f sediment i n the watersheds; and ( iv) attempt to trace the transport o f sediment f r o m these sources as it moves a l o n g the stream channels. 6.1 Changes in control sites between 1996 and 1997 H a v i n g deduced that undisturbed stream sediments have unique natural , m u l t i -element geochemica l signatures, the temporal v a r i a b i l i t y o f these signatures can be considered. Year-to-year variations i n stream sediment geochemistry were evaluated b y re-sampl ing i n 1997, 1996 control sites undisturbed b y l o g g i n g or r o a d construct ion activit ies. T h i s i n c l u d e d samples o n the control streams B 6 and B 4 , above stream crossings, and sample sites o n B l , B 2 , B 3 , and B 5 , w h i c h were above the cutblocks . S a m p l i n g was undertaken at the same t ime o f year (August) i n b o t h 1996 and i n 1997 i n an attempt to m i n i m i z e any seasonal changes i n geochemistry. There were no changes apparent i n the minera logy , texture or organics content f r o m 137 undisturbed sample sites over the year ( A p p e n d i x D ; Table 5.1.4). T h e 1997 geochemica l analyses can be compared w i t h the results f r o m 1996 (Tables 6.1.1 and 6.1.2 versus Tables 5.1.5 and 5.1.6). Year-to-year v a r i a b i l i t y was then evaluated us ing X - Y plots o f the sites sampled and analyzed i n both 1996 and 1997 ( E x a m p l e for B a , C o , C r i n F i g u r e 6.1.1 w h i c h are s i m i l a r to most other elements) and results o f T h o m p s o n - H o w a r t h p r e c i s i o n charts (Table 6.1.3). T h e v a r i a b i l i t y (= within-s i te year-to-year v a r i a b i l i t y + analyt ical var iab i l i ty between and w i t h i n years + r a n d o m var iabi l i ty) f r o m 1996 to 1997 i n control sites is t y p i c a l l y about 2 5 % , except for elements near their detection l i m i t s , such as P b , and for C u w h i c h shows an unusual amount o f var iab i l i ty . T h i s leve l o f v a r i a b i l i t y between contro l sites sampled and analyzed over the per iod , is no greater than the analyt ical v a r i a b i l i t y over the p e r i o d (± 25 % ) (Table 4.2.2) and o n l y s l ight ly greater than the v a r i a b i l i t y between sample sites o n the stream b e d i n a single year (± 2 0 % ) (Table 4.2.1). These results suggest that for most elements there is no signif icant temporal change i n geochemistry over this one-year p e r i o d i n areas unaffected b y the l o g g i n g . 6.2 Post-harvesting effects H a r v e s t i n g o f the two cut-blocks required the construct ion o f temporary w i t h i n - b l o c k roads and six stream crossings. T h e temporary w i t h i n - b l o c k roads were bui l t o f h i g h l y 138 T a b l e 6.1.1: S u m m a r y o f average concentrations o f elements f r o m 1997 total analyses. B6 Bl B2 B3 B4 B5 n=5 n=26 n=19 n=26 n=18 n=20 A l % 5.65 6.30 6.51 6.41 6.60 6.84 Fe % 4.02 4.46 3.75 3.86 3.90 3.79 M g % 3.81 3.12 2.18 2.33 2.03 1.48 C a % 1.37 1.79 1.69 1.70 1.67 1.67 N a % 1.7 1.9 2.1 2.0 2.0 2.1 K % 0.84 1.00 1.11 1.05 1.14 1.16 T i % 0.38 0.56 0.43 0.44 0.44 0.44 B a ppm 516 534 627 611 661 688 C o ppm 35 28 22 24 22 18 C r ppm 542 357 214 240 200 131 C u ppm 247 100 85 77 78 113 M n ppm 2069 1227 1446 1383 1289 1635 N i ppm 528 418 283 224 196 108 P ppm 754 903 744 716 820 909 Pb ppm 4.2 5.9 5.1 4.4 6.2 5.9 Sr ppm 220 231 274 256 273 290 V ppm 123 148 139 143 145 135 W ppm 10 10 10 10 10 10 Z n ppm 118 115 107 129 134 174 139 T a b l e 6.1.2: S u m m a r y o f average concentrations o f elements i n creeks f r o m 1997 aqua regia analyses. Element B6 Bl B2 B3 B4 B5 n=5 n=26 n=19 n=26 n=18 n=20 A l % 1.8 2.1 1.7 1.8 1.7 2.0 Fe % 3.87 3.94 3.23 3.40 3.43 3.35 M g % 2.19 1.90 1.25 1.34 1.28 0.96 C a % 0.44 0.61 0.66 0.63 0.66 0.79 K % 0.06 0.17 0.08 0.08 0.09 0.09 T i % 0.09 0.16 0.11 0.12 0.12 0.11 A s ppm 22 12 30 14 10 10 B a ppm 144 122 111 121 124 141 C o ppm 29 25 19 21 19 16 C r ppm 266 203 125 139 122 74 C u ppm 268 105 85 76 76 112 M n ppm 2040 1030 1282 1214 1105 1479 M o ppm 324 313 213 151 142 81 N i ppm 624 745 612 572 665 713 P ppm 6.8 6.6 4.6 4.7 5.9 4.9 Pb ppm 26 30 37 34 38 60 V ppm 54 65 55 60 59 56 Z n ppm 109 106 97 118 125 162 140 1000 i 1996 sample (ppm) Figure 6.1.1: Comparison o f results for Ba , C o and C r from undisturbed sites sampled in 1996 and 1997. These elements are presented as examples, but results were similar for other elements which were above detection limits. The solid line represents the x=y line and thedashed lines are +/- 20 % 141 T a b l e 6.1.3: S u m m a r y o f p r e c i s i o n obtained f r o m s a m p l i n g the same sites i n 1996 and 1997 and analysed i n each year. These p r e c i s i o n values represent a l l sources o f error, l o c a l v a r i a b i l i t y w i t h i n site, v a r i a b i l i t y due to sample preparation, analyt ica l var ia t ion w i t h i n and between years and r a n d o m var iat ion. Est imated b y the m e t h o d o f T h o m p s o n and H o w a r t h (1978) at the 95 % confidence leve l . Total digestion Aqua regia digestion Element Precision (%) Element Precision (%) A l 10 A l 20 B a 10 A s >50 C a 15 B a 25 C o 25 C a 25 C r 20 C o 20 C u >50 C r 25 Fe 15 C u >50 K 15 Fe 15 M g 20 K 30 M n 35 M g 20 N a 20 M n 40 N i 30 N i 25 P 20 P 20 Pb >50 Pb >50 Sr 20 Sr 30 T i 25 T i 35 V 20 V 30 Z n 25 Z n 25 142 erosive t i l l s , w h i c h have subsequently undergone erosion and g u l l y i n g despite reseeding i n the summer o f 1997 (Plate 6.2.1). M o s t o f the result ing sediment is col lected i n ditches and depressions around the n e w roads and does not reach streams. T h e n e w sediment sources ident i f ied were a l l located at stream crossings where culverts had been instal led (Figure 3.1.3). A t y p i c a l road cross ing w i t h a culvert instal led is s h o w n i n Plate 6.2.2. T w o different cutt ing prescriptions were appl ied to the cut b l o c k s , as descr ibed i n Sect ion 2.8. Stream B 5 was harvested aggressively, w h i l e B l , B 2 , B 3 and B 4 were to be harvested conservatively . H o w e v e r , o n the upper p o r t i o n o f B 2 , the R M A was complete ly logged, and tracks from l o g g i n g equipment and fal len debris (branches, needles, brush) changed the locat ion o f the stream channel . A s a result, very few o f these sample locations from 1996 c o u l d be exactly relocated and sampled i n 1997. T h e effects o f harvesting o n stream sediment texture, m i n e r a l o g y and geochemistry were evaluated b y c o m p a r i n g the overa l l changes i n contro l sites over the study p e r i o d to those w i t h i n and b e l o w cut b l o c k s (exc luding samples i m m e d i a t e l y b e l o w sediment sources). T h i s was done b y c o m p a r i n g X - Y plots o f 1996 and 1997 samples from contro l sites and affected sites ( w i t h i n and b e l o w cut b l o c k s ) , and plots o f geochemistry and texture a long stream (Figures 6.2.1-6.2.4 for M g , M n , N i and Z n ) . F o r elements w i t h analyt ical prec is ion w i t h i n tolerable l i m i t s , ( e x c l u d i n g elements w i t h concentrations b e l o w detection l i m i t s and C u ) , the o v e r a l l v a r i a b i l i t y is w i t h i n ± 30 % . T h i s is w i t h i n the range o f overa l l var iab i l i ty i n s a m p l i n g and analysis over 143 Plate 6.2.1: L o c a l t i l l material is h i g h l y erosive. S k i d tra i l i n cut b l o c k 2 4 4 - 2 2 shows extensive g u l l y i n g and erosion (top) despite seeding i n the spr ing o f 1997. S k i d tra i l i n cut b l o c k 220-23 is h i g h l y water saturated (bottom). 144 0.1 1 10 1996 sample (ppm) A same site in 1996 and 1997 • samples below cut blocks • samples within cut blocks Figure 6.2.1: Comparison o f geochemical results from aqua regia digestions for samples from 1996 and 1997 for M g . The sol id line represents the x=y line and the dashed lines are +/- 20 %. Samples from below cut blocks which are within the dashed oval are from below sediment sources. 146 100 1000 10000 1996 sample (ppm) * same site in 1996 and 1997 • samples below cut blocks • samples within cut blocks Figure 6.2.2: Comparison o f geochemical results from aqua regia digestions for samples from 1996 and 1997 for M n . The solid line represents the x=y line and the dashed lines are +/- 20 %. Samples from below cut blocks which are within the dashed oval are from below sediment sources. 147 10 -F— 1 1 10 100 1000 1996 sample (ppm) A same site in 1996 and 1997 • samples below cut blocks • samples within cut blocks Figure 6.2.3: Comparison o f geochemical results from aqua regia digestions for samples from 1996 and 1997 for N i . The solid line represents the x=y line and the dashed lines are +/- 20 %. Samples from below cut blocks which are within the dashed oval are from below sediment sources. 148 1000 • J • 100 10 10 100 1996 sample (ppm) 1000 * same site in 1996 and 1997 • samples below cut blocks • samples within cut blocks Figure 6.2.4: Comparison o f geochemical results from aqua regia digestions for samples from 1996 and 1997 for Zn. The solid line represents the x=y line and the dashed lines are +/- 20 %. Samples from below cut blocks which are within the dashed oval are from below sediment sources. 149 the two-year p e r i o d (Table 6.1.3). Thus , there is no apparent or measurable systematic change i n texture or geochemical c o m p o s i t i o n i n logged streams, that is greater than corresponding changes i n control streams over the p e r i o d o f the study. H o w e v e r , samples b e l o w cut b l o c k s are also b e l o w the n e w sediment sources. W h e n samples i m m e d i a t e l y b e l o w the sediment sources are identi f ied o n the X - Y plots , several elements, i n c l u d i n g C o , M g , M n , N i and Z n , show changes related to n e w sediment sources. These changes are h ighl ighted o n Figures 6.2.1-6.2.4. T h i s is most notable, and was first ident i f ied, o n the X - Y plot for Z n (Figure 6.2.4). T h e effects o f sediment sources w i l l be considered i n the next section. These results indicate that i n the absence o f a specif ic sediment source there were no measurable textural , m i n e r a l o g i c a l or geochemical changes i n stream sediments f rom areas w h i c h were logged w i t h either the conservative or the aggressive treatment. 6.3 New sediment sources SSI- SS6 6.3.1 Physical descriptions of new sediment sources SS1-SS6 T h e s ix sediment sources identi f ied a l l occur at n e w l y constructed stream crossings; their properties are l isted i n Table 6.3.1. Sources S S I , S S 2 and S S 6 are located at temporary crossings for roads w i t h i n cut b l o c k s , w h i c h have since been deactivated (Plate 6.3.1; Plate 6.2.2). B o t h S S I and S S 2 are t y p i c a l , w i t h i n cut-b lock stream 150 fe S3 o fi CO CD M CS CO cd T3 CD .fi co M . CU cu . S ^ £ § O CN CN CO M o o CN CN 3 <D •s CU o CQ cu o fi* o cn I a cu CO cu o CO CU CU P H o CO NO CU fi o o O N O N *—I N O O N O S 00 fi 'oh oo o <+-< O 6 0 fi 13 | 8 oo (L) CO o s cn ca a tre o CO c f i 6 0 fi •c CU S fi" CU cu cn o cu H <H-I O CO u , cu CU 7 3 •i I C<-l O -fi "2 •£3 cd T 3 O • M 1-1 »—1 03 fi •c 0 cu CO -4-* 03 ro: g CU C M 0 O - M - M c cu C cd S T3 c cct cu O a 1 M S CU CO *Q cU > O c fi cu ucu 53 5 3 T3 o cu co 0 0 cd cu fi C/J *K CO CO CO CO 2 2 cu cu cu cu fi fi >s >, >•> >s M M M - O co O O co O g o g g u * S ^ S S ^ cu cu - M - M CO cct M CU CU CU - M H - » CO CO cu 6 0 cu cu 6 0 . .:. .is •fi 'fi u 'fi o 0 33 o 8 c3 M M O O cu cu fi - M C cu cu fi C cd cd cu cu ll-p a. 1 fi 0 S cu CO CO CU M O a. S cu o o 0 o o £ t-- NO 00 - s i - r-» !Q !Q !Q 1^  -jjj NO NO N£> CN ro m NO in m 10 T}- co cN CQ PQ CQ PQ CQ CQ 1 5 1 152 crossings, 6.5 m w i d e w i t h approximately 1-2.5 m o f f i l l (Plate 6.3.2). Sources S S 3 , S S 4 and S S 5 , o n l o w e r B 5 , B 4 and B 3 , respectively, resulted f r o m the construct ion o f the semi-permanent h a u l road, to be used for subsequent cut-blocks. S S 4 and S S 5 were t y p i c a l culverted stream crossings. O f these s ix sediment sources, S S 3 o n B 5 and S S 6 o n B 2 showed evidence o f the most disturbance. Sediment source S S 3 (Plates 6.3.2 and 6.3.3) at the lowermost stream cross ing o n B 5 was ident i f ied i n the f ie ld as a substantial contributor o f fine sediment to B 5 . Channels o f eroded sediment f r o m side gul l ies and from the large l a n d i n g i m m e d i a t e l y above this stream crossing fed direct ly into stream B 5 . B e a u d r y (1998) was present i n the spring d u r i n g snowmelt , and reported that the l a n d i n g mel ted early i n the season, generating a large amount o f surface r u n o f f that transported sediment d o w n the road surface and into B 5 . Further, B e a u d r y (1998) noted elevated suspended sediment readings at the f lume b e l o w this sediment source (SS3) o n B 5 (Table 2.9.1). A t sediment source S S 6 o n stream B 2 (Plates 6.3.4 and 6.3.5), the culvert used i n the road cross ing was damaged d u r i n g harvesting and was therefore r e m o v e d i m m e d i a t e l y after c o m p l e t i o n o f l o g g i n g . A backhoe was used to excavate the culvert and re-contour the stream channel . H o w e v e r , considerable g u l l y i n g from the adjacent landing to this cross ing resulted i n fine sediment be ing channeled into B 2 . These channels o f sediment, 0.5-1 m w i d e , cut through the vegetation i n the R M A to del iver sediment to the stream 50-75 m downstream from the sediment source (Plates 6.3.5-6.3.7). 153 \ Plate 6.3.2: V i e w o f gu l l i ed s k i d trails i n cut b l o c k 220-23 (B5) w i t h sediment source S S 2 i n the center (top). F i n e sediment f rom road r u n o f f deposited o n surface o f gravel at sediment source S S 3 o n B5 (bottom). 154 Plate 6.3.3: Portion of the semi-permanent haul road to cut block 220-23, where runoff from the road enters B 5 , sediment source SS3 (top). V i e w o f debris and cut block near SS3 taken from the haul road (bottom). 155 Plate 6.3.4: A e r i a l v i e w o f sediment source S S 6 o n stream B 2 (top) and f r o m the ground (bottom). N o t e the locat ion o f the l a n d i n g seen i n the f o l l o w i n g three plates. T h e s k i d t ra i l i n the foreground is the h i g h l y g u l l i e d trai l seen i n Plate 6.3.2. 156 Plate 6.3.5: G u l l y i n g o f landing at sediment source S S 6 o n stream B 2 (top) a n d one o f f ive streams o f fine sediment generated i n the l a n d i n g and leading to stream B 2 (bottom). 157 158 159 6.3.2 Texture and mineralogy of new sediment sources Comparisons of the grain size distributions for streams B2-B5 with sediment sources SS1-SS6 shows that sediment sources contain 3 to 13 times more fine material (- 0.212 mm), than stream sediments (Table 6.3.2). Notice that the sediment sources have similar grain size distributions to local tills (Table 2.3.3). While there is a significant difference in the grain size distribution of stream sediments and sediment sources, there were no obvious or significant textural changes in stream sediments immediately downstream of sediment sources. A l l o f the f i l l material used to construct stream crossings was composed of local t i l l o and bedrock. The t i l l is composed of a clay-silt-sand matrix and a large variety of clasts including: serpentinized peridotite, dunite, rhyolite, andesite, chert, quartz, granodiorite, greenstone, conglomerate, and others (Figure 2.2.1). Analysis of the -0.053 mm size fraction of sediment sources identified the primary minerals in decreasing order of abundance to be: quartz, oligoclase, muscovite, clinochlore (chlorite), paragasite (hornblende), talc and serpentintes (lizardite and ankerite) (Table 6.3.3). 160 o w 00 cn CD P O (D CO M CCt fl n-j CD ^ 5 ° co VO PQ o d ' £ CO a co co C CD CD g s PQ 2 i I CO co co fl tEJ -s CD ccj CD J3 co CD SP CD • l l <D T-t |_! W CD <U r j CO OH § <u 00 CD fi.fi j~J t 0 o co PH CD co ™ tl 1 8 O CD ^ CD § CD 43 N H « CD •a .2? S CD ft ao CD cd 60 CD 4-> > C > CD ^ O CN CD H v>3 oN cn 0 0 0 0 | | 0 0 c CN vo O0 || 0 0 C 0 0 0 0 § <=> 0 0 ^ 0 0 || 0 0 c cd (D oo m r~-oo || oo c 00 ^ 1 0 rH 0 0 V 0 0 1 S ON Cd i CD II oo ^  c o -4-» o cd i-CD g •~ g oo o q n m vi vo n O CN ON O CN I/) CN — H *"f o co in -^ r io CN O cn oo oo ON cn in CN O o cn cn 0 \ r—I OS T~~ — CN —i in i-H ON O O T}* m rH 0 0 rH rH O m | I A CN CN 0 0 o o o O 0 O rn > 0 O O t~; o cn r-^  in in t~ cn Tf vo cn oo vo ON ON CN cn ^ vo CN CN m rH o cn CN r-; © oo -rf in H cn r-; rn oo © K ^ vo \f m cn CN tN CN oo vo oo ON in o rn oo iri CN rH •*t in ON ON oo "st in oo cn cn CN o vo »-H ON cn r-~ od cn oo » n rH rH CN in rH CN CN 1 m in CN CN o V 161 T a b l e 6.3.3: A v e r a g e percentages o f minerals f r o m sediment sources S S 3 , S S 4 , S S 5 , and S S 6 o n streams B 2 - B 5 determined b y X R D (Rietve ld) o n -0.053 m m size fractions. SS6 SS5 SS4 SS3 W e i g h t e d B 2 B 3 B 4 B 5 M e a n n = l n=5 n=3 n=2 n = l l Quartz 23 33 34 38 32 O l i g o c l a s e 2 0 31 31 33 29 M u s c o v i t e 18 14 15 15 15 C l i n o c h l o r e (chlorite) 20 9 9 7 11 Pargasite 4 5 4 3 4 T a l c 9 5 5 3 5 L i z a r d i t e 4 3 n/a A n k e r i t e 0.7 0.9 0.8 n/a C o r u n d u m * 6 2 2 1 3 * Contamination resulting from the grinding procedure 162 6.3.3 Geochemistry of new sediment sources and its application to source-sediment tracing T h e geochemica l f ingerprints o f the sediment sources determined b y aqua regia and total digestions are s u m m a r i z e d i n Tables 6.3.4 and 6.3.5, respectively. H a v i n g established the c o m p o s i t i o n o f stream sediments and source sediment, elements w h i c h m a y be useful as tracers can be identi f ied. T o evaluate an element as a source-sediment tracer it has been assumed that the greater the c o m p o s i t i o n a l difference between stream sediments and a n e w source, the greater the potentia l value o f an element as a tracer. C o m p o s i t i o n a l differences between sediment and sources were therefore evaluated for: (i) the geochemical contrast (ratio) between the concentration o f the element w i t h i n a sediment source and stream sediments taken above the source (Table 6.3.6); and ( i i) b y testing mean values o f the sediment and source for signif icant differences (Table 6.3.7). B a , C a , C r , F e , M n , N i , P , Sr, and T i pass both tests for at least one stream and are therefore possible tracers (Table 6.3.8). A s an example, plots o f M g and N i a long stream B 4 are s h o w n i n F igures 6 . 3 . l a n d 6.3.2. In these plots , the inf luence o f the i n f l u x o f n e w material o n sediment c o m p o s i t i o n is c lear ly apparent i n increased M g and N i concentrations i n sediments i m m e d i a t e l y downstream from the sediment source. B e l o w sediment sources S S 4 and S S 5 , o n streams B 4 and B 3 , respectively, s i m i l a r increases i n C o , M g and N i concentrations are apparent (Figures 6.3.3 and 6.3.4). 163 fi o • I—I 4-» CO CD SP •3 S '5b CD (-H ccS I CO 'to "3 3 a NO 0 0 0 0 0 0 0 0 co CD I O CO a •3 CD co fi CD 13 o co fi O '3 J3 fi CD O fi o o CD Tt CO NO CD T3 C £ ' f i « •§ n) > +-» a i .(/) -u 8 3 fi 5 00 0 0 •O fl ts o .8 'fi « '3 CS > H-» CL> 00 -g fl — S 1 5 a : « 1 GO T 3 § op £ PH *o fl -S 'fi fl -2 00 - Q c3 NO T3 C ti o T3 'fi « 'S ca > 00 T3 9 ^ CN Tt" T-H © CN CN ON NO CO 00 CO NO NO OO HO CN ON CN CO CO T-H o O T-H CO T-H CO Tf NO T-H O d d d d d d CN CN o CN CO ON oo CO CO CN ON NO NO CN CN CN NO © •—I O T-H T-H NO »—4 CN CO m oo T-H CO T-H d d d NO NO oo ON CN o NO © NO © Tt- NO © CN NO Tt- oo © Ti-T-H o ON TI- i n CN oo CO c n ro 00 d 00 d T-H oo T-H o t-- oo r » o T-H © OO oo © T-H CN CN q NO Tr m T-H T-H T-H CN CN ro CD 00 ro Tf CO NO 0\ CO CN CO d d © 00 NO O TJ" CN ON CN CN Tf © SO 00 SO © ON © oo SO Tf ro T-H T-H o O © T-H i n CN Tl- T-H T-H T-H cn d d T-H d d © -H d CN T-H CN 00 o CO CN oo © ON SO o NO m oo ON © NO op NO T-H T-H CN CN CO c n SO ro c n © CN ro ^ d d © T-H T-H T-H so CN NO NO NO r- CN HO NO CN r~ TI- Tf ro Tj- O o o CN CN CN T-H © '—I T-H ro Tf-d d d d d NO ro T-H © CN NO co CN ON O ro © NO ON © T-H 00 CO r~ T-H ro <5 ON m © CO CN CO T-H NO OO oo SO SO SO c n oo CN ro d d © >/-> ON NO T-H d TT CN O oo CN SO CO CN © © oo CN ro o T-H © © T-H CN NO T-H T-H CN d d d d d © © ON •* CO oo 00 © IT) TT r~ SO ON CN © oo <N Tf NO CN ON CO © T-H T-H T—t SO SO © cn T-H Tf c n oo c n ^ co d d d © © NO CN NO NO T-H r~ CN m SO SO r- Ti- TT CO TT o o © © CN CN T-H © T-H T-H ro Tf d d d d © © CO d <N NO CO CN ON ro © NO ON © T-H oo CO SO ro T-H sq ON © CN CO T-H SO 00 oo so NO Tl- NO m oo CN co d d © © OS SO T-H © v O \C sO -^O \C 0s 0s 2 T — U M cd .j < P H S U * H g S S S S S S S 6 6 S P H P H O H P H O H P H P H O H P H O H O H co « o 3 £ s o M ^ C N? u 164 T3 *H ro •O a co B OO 60 OO c CO u s T3 *H n) 1 3 C C N S OO oo OO a a u 2 S 3 43 o 00 00 "3 13 H O 1 5 oo -g > <L> T3 o o o CO CN Tf ,—i p "3" m rH O CN co VO "—1 o © CO VO CN in CO m CN ~ o d d d o o d o ' 1 r—I ON rH VO t ^ rH tN m CO o i n o oo i n oo r - CN i n © co CN CN o oo co ON 00 CN oo oo CN Tf CN co TT ON VO ON CN rH IT) rH O p ON 00 00 CN CN CO CN o r-1 o © TT co CO vd ^ in CN rH © © © © © © © VO VO ON TT CN i n 00 o 00 i n TT NO CO CN rH CN rH © 00 vo , — i rH ON rH rH ON rH CN CN O CN vd i n CO o co oo rH vo r-» m CN o VO 00 y—t CO i n i n VO i n o r - r - i n rH O vo VO ON r-l o ON i n o co © ON CN ^ © © © d © o © o CN 1 1 rH rH ON VO i n o O VO VO ON m o vd co CN rH CN rH © o VO VO o ON r-- VO CN CO oo 00 CN © CN 00 CN VO i n oo VO TT r - CN co od ON VO co m CN m ON m o CN oo r~ VO O CN CN O m CN co r-< r~1 CO o p CO CN 1 — 1 co VO OO ON d O o d o © © CN "~' CO o m ON CN VO i n OO i n VO CN CO rH CO vd CO rH rH CN rH © o r- o rn CN CN O rH rH T | - m o o CN VO CN ^ 2 ON vo i n co ; rH CO © 00 • oo ON o CN r- CN ON CN CN m vd NO O O O O O O O TT vo vd co ON o o i n VO VO CN TT vd CO rH rH CN rH o o O r H C N v o c N c o r ^ m c o ON CN o ON o CN rH i n o i n o d o d d d d d •<cf oo m co o CO ON 0O CN O co CN O i n vo vo vo CN O CO CO CN CN vo l> r^  CN rH o rH -d- VO CN co i n oo oo oo rH r- CN \0 \fl \0 \0 \0 \0 \0 QN QN. Q \ QN Q \ Q \ Q \ < 2 O ? * H ^ ~ S r-i S S 6 S S S S S S 6 C H C ^ C U O H P H O H O H O H C U C H C H C H C H C H C H Q - C H C H C ^ O . 3 £ « 165 T a b l e 6.3.6: G e o c h e m i c a l contrast: ratios o f the m e a n concentrat ion o f an element w i t h i n the sediment source to the m e a n concentration i n sediments upstream. O n l y ratios <= 0.9 and >= 1.1 are shown. Ratio SS6 / B2 SS5 / B3 SS4 / B4 SSI / B5 Total Digestion A l 1.1 Ba 1.1 1.12 Ca 0.9 0.86 0.87 0.72 Co 0.9 1.16 Cr 0.8 1.14 Fe K 1.2 1.11 1.10 Mg 0.9 1.19 1.33 Mn 0.3 0.62 0.63 0.41 Na 1.2 1.15 Ni 0.4 1.44 P 0.9 1.10 1.24 0.76 Sr 1.2 Ti 1.1 V Zn 0.9 1.13 Aqua Regia A l 0.9 1.14 1.11 As 0.2 1.42 1.29 3.38 Ba 0.7 1.14 0.83 Ca 0.7 0.89 0.51 Co 0.9 1.12 Cr 0.8 1.17 1.31 Fe 0.9 1.11 K 1.1 1.26 1.16 Mg 0.9 1.31 1.55 Mn 0.2 0.56 0.57 0.36 Ni 0.3 1.14 1.58 P 0.9 1.15 1.28 0.84 Sr 0.7 1.11 2.05 Ti 1.2 1.14 0.60 V 1.51 Zn 0.8 0.86 1.12 C 0.3 0.39 0.72 1.18 166 T a b l e 6.3.7: t-tests for concentration o f elements w i t h i n the sediment sources compared to the concentration o f elements upstream o f sediment sources. O n l y values s ignif icant at the 0.05 leve l are shown. A signif icant pos i t ive t-statistic indicates that the sediment source has a l o w e r concentration than the sediment immediately upstream; a negative t-statistic indicates that concentration of element is greater in the sediment source than upstream. Stream SS6 - B2 SS5 - B3 SS4 - B4 SSI - B5-1 Total Digestion Al Ba -5.89 -2.85 Ca 3.71 8.23 2.99 9.15 Co Cr 2.54 2.99 Fe K -9.14 -2.68 -2.95 Mg Mn 6.26 -2.76 4.38 Na -5.8 -2.6 Ni 4.81 P 4.24 -3.35 -3.56 2.75 Sr -4.15 Ti -3.47 Zn 3.84 Aqua Regia Digestion Al 3.3 As 5.39 Ba 5.9 -2.55 Ca 7.39 4.05 Co Cr 2.58 -2.41 Fe 2.35 K Mg Mn 6.5 -2.94 3.57 2.58 Ni 5.13 P 2.42 -3.38 -2.66 Sr 4.06 2.91 Ti -2.7 -3.59 Zn 5.62 Carbon 8.71 3.1 167 T a b l e 6.3.8: E lements w h i c h are ident i f ied i n both t-tests and ratios as potent ia l ly useful to identi fy sediment inputs o f s m a l l tributary creeks to Bapt iste C r e e k after logg ing . Creek Total Digestion A q u a regia digestion B 2 Cr , K , M n , N a , N i , P, Sr, T i , C B a , Ca, Cr , Fe, M n , N i , Sr, T i B 3 C a , M n M n B 4 C a , P M n , P B 5 Ca, P, C Ca,Sr ,Ti 168 o o o o o o o 00 Q o o o NO o © i n o o o o r o o o C N O o s I a s CU u B S3 OO oo o 1) X ) T 3 > o I ON ON ,g -a NO ON ON CU "5. £ C*H (3 O J CU O C o o CO c o 'C CO > Si) c 'I o .a i/> -«t CQ OO (+_ O JO E o ro NO g I o 3 E co CA! Tf Vi 3 O a CL> s CO c/3 C M o e o c 8 a o u CU s o o o o o ON O o 00 © o t-o o E i CU S o o O o TT © o 8 o o CU w c s .2 a o o TT © in ci o o o ITi o © C N o m o o © (uidd) I N O0 CU X ) T 3 C C3 CU > O •8 O s ON C T3 NO ON ON c CU t/j CU o c*a c o I CU o c o o a c o > cu X c '% cn CQ 1 cn O u tC o CN ro NO I 170 200 180 I 160 -I 140-I 8 120 -f 100-u 80 60 a) Cobalt Flow Direction r — 1997 samples 1996 samples 1" Material from sediment source SS4 • Average concentration of material from sediment source SS4 50 100 150 200 D i s t a n c e u p s t r e a m (m) 250 300 350 3.5 3 2.5 b) Magnesium Flow Direction 8 1.5 If 1 0.5 — 50 100 150 200 D i s t a n c e u p s t r e a m (m) 250 300 350 350 -, 300 I & 250 J 200 100 50 c) Nickel Flow Direction 0 100 150 200 250 D i s t a n c e u p s t r e a m (m) 300 350 Figure 6.3.3: Profile o f C o , M g , and N i concentration above and below sediment source SS4 on stream B 4 . 171 b) Magnesium 300 350 400 Distance upstream (m) 500 250 a 200 a. s 150 H c) Nickel < Flow Direction 50 150 200 250 300 350 Distance upstream (m) 400 450 500 Figure 6.3.4: Profile o f C o , M g , and N i concentration above and below sediment source SS5 on creek B 3 . 172 T h e s ignal f r o m S S 6 o n B 2 was more c o m p l e x , as sediment entered the stream i n s m a l l channels over a distance o f 75 m (e.g., F i g u r e 6.3.5 for N i ) . T h e elements A s , F e , N a and S r showed s i m i l a r patterns b e l o w S S 6 o n B 2 . A s sediments o n B 5 were inf luenced b y three sediment sources, a strong s ignal from the effects o f the sediment source w o u l d be expected. W h i l e C o , C r , M g and N i show increases i n concentration s i m i l a r to B 3 and B 4 , there are insufficient samples between and b e l o w the sediment sources to f o r m conclusions. S a m p l i n g was truncated where the stream enters the s w a m p surrounding " U p p e r " Baptiste L a k e , 120 meters b e l o w S S 3 . Z n was not ident i f ied as a tracer but gives a strongly anomalous s ignal (>200 p p m ) b e l o w n e w sources o f sediment despite these sources not h a v i n g elevated concentrations o f Z n (Figures 6.3.6-6.3.9). E x a m i n a t i o n o f the 1996 data shows there is a s i m i l a r increase i n z i n c concentrations b e l o w roads constructed across streams B l , B 2 , B 3 and B 4 i n 1992 (Figures 6.3.6-6.3.10). Further geochemica l analysis ident i f ied the occurrence o f elevated z i n c concentrations w i t h i n the - 0.053 m m size fraction w i t h an average concentration o f 309 p p m (range 92-612 p p m ) i n the - 0.053 m m size fraction, w h i l e the 0.053 - 0.212 m m size fractions o f the l ight and heavy minerals returned average concentrations o f 175 p p m and 250 p p m , respectively. T h e average concentrat ion o f Z n was highest i n the paramagnetic m i n e r a l fraction, w i t h an average concentrat ion o f 680 p p m . Results from b e l o w the culvert-road cross ing o n B l , constructed i n 1992 from l o c a l t i l l , s h o w e d notable increases i n some elements ( A l , C a , C o , F e , K , M g , N i , P , T i , V , 173 o o I 1 1 1 1 1 1 1 1 (_ o O Q O O O O O O O O o o o o o o o o o o s o o r - - ' o > n ' n - f n t N — > (uitld) uouexjuaauo j 174 i 1 r © © © O m © f l CN CN (uidd) u/ 175 © © i n CN O © © O O © © 5 © © «/-) Tr- cn CN —c (nidd) oz 176 o o 177 178 o o oo (uidd) uy 179 and Z n ) i m m e d i a t e l y b e l o w the road cross ing (Figures 6.3.11 and 6.3.12). A n apparent shift i n concentration downstream i n 1997, relative to 1996, was also noted. Af ter cons ider ing w h i c h elements c o u l d best be used as source-sediment tracers, the f o l l o w i n g m i x i n g m o d e l , presented i n Sect ion 1.4, was used to estimate the amount o f material der ived f r o m the n e w sources o f sediment and incorporated i n the - 0.212 m m size fract ion at v a r y i n g distances downstream: P s = Percentage o f sediment f r o m sediment source C s s = Concentrat ion representative o f sediment source (mean or m a x i m u m ) C 2 = Concentrat ion at a site downstream o f the sediment source i n 1997 C , = Concentrat ion o f the stream at the same site as C 2 before introduct ion o f sediment. ( F o r elements where the analyt ical p r e c i s i o n between years is less than 20 % , the concentration o f the sample at site C 2 is used, otherwise an average o f samples (2-4) above the sediment source is used. F o r example, concentrations o f both M g and N i increased i n sediments f r o m stream B 4 downstream f r o m Source 4 (Figures 6.3.1 - 6.3.3). B a s e d o n calculat ions for both elements, the amount o f material added to the sediments averages r o u g h l y 5 0 % close to the source to less than 1 3 % at a distance o f 117 m downstream (Table 6.3.9). S i m i l a r trends are v i s i b l e o n B 3 for the elements C o , M g and N i , where calculat ions estimate an average m i n i m u m o f 31 % o f n e w sediment added at 82 m f r o m the sediment source, decreasing to 2 % at a distance o f 191 m f r o m the sediment source. P , = 1 0 0 x ( C 2 - C 1 ) / ( C I g - C 1 ) P s = 1 0 0 x { l - ( C 2 - C J / ( C r C J ( F o r C , < C J ( F o r C , > C s s ) W h e r e 180 Figure 6.3.11: Geochemical trends along B l . Arrow indicates the position of the road crossing constructed i n 1992. Note the increase in Ca, K , and M g below the road crossing. 181 0 -I 1 1 1 1 1 1 1 1 — 0 200 400 600 800 1000 1200 1400 1600 Distance upstream (m) 50 4 1 1 1 1 1 1 1 1 — 0 200 400 600 800 1000 1200 1400 1600 Distance upstream (m) Figure 6.2.12: Geochemical trends along B l . Arrow indicates the position of the road crossing constructed in 1992. Note the increase in P, T i , and V below the road crossing. 182 T a b l e 6.3.9 Percentage o f n e w sediment contributed downstream f r o m S S 4 o n stream B 4 based o n M g and N i concentrations and f r o m S S 5 o n B 3 for C o , M g , and N i . T h e m e a n amount o f sediment is calculated u s i n g the m e a n concentrat ion o f the sediment source, w h i l e the m i n i m u m amount o f sediment contributed is calculated u s i n g the m a x i m u m concentrat ion o f the sediment source. N e w sediment (%) downstream from Source SS4. Distance (m): 13 43 87 117 M e a n amount o f sediment contributed M g 49 46 23 9 N i 54 35 25 13 M i n i m u m amount o f sediment contributed M g 15 16 8 3 N i 19 11 9 5 N e w sediment (%) downstream from Source SS5. Distance (m): 82 106 167 191 M i n i m u m amount o f sediment contributed C o 37 37 16 5 M g 29 11 21 3 N i 29 19 8 -1 183 6.4 Discussion N e w sediment sources were a l l related to n e w roads and their adjacent landings at stream crossings. W h i l e sediments f r o m these n e w sources conta in greater percentages o f fines than stream sediments, no apparent textural changes occurred i n the streams i m m e d i a t e l y downstream o f sources i n the first year. T h i s indicates that most o f the very-f ine source-sediment m i g h t have been entrained and r e m o v e d f r o m the stream b e d (Table 6.3.2). T h i s also is consistent w i t h the increased suspended sediment y ie lds measured b e l o w S S 3 o n B 5 b y B e a u d r y (1998) (Sect ion 2.9). Source-sediments were determined to have distinct, but variable, geochemica l f ingerprints compared w i t h stream sediments (Tables 6.3.4 and 6.3.5). V a r i a t i o n i n the c o m p o s i t i o n o f source-sediments l i k e l y results f r o m variations i n the m i n e r a l o g i c a l c o m p o s i t i o n o f the n e w l y exposed l o c a l t i l l (part icularly its f ine-grained matr ix and bedrock. T h e inf luence o f n e w source-sediment o n stream sediment composi t ions was evident i n one or m o r e elements at a l l o f the sources. Tracers o f the source-sediment were ident i f ied as those w i t h the greatest contrast between source and stream sediments (ratios and t-tests). Tracers are therefore unique for each sediment source o n each stream. Concentrat ions o f tracer elements a l l o w e d for estimates o f the quantities o f source-sediment contributed at various distances downstream (Table 6.3.9). G e o c h e m i c a l changes b e l o w the sources, i n the absence o f textural changes, indicate that f l u v i a l processes m o d i f y the signatures o f both the source-sediments and the pre-184 exist ing, natural stream sediments. W h i l e the b u l k o f the fines (< 0.10 m m ) f r o m the source-sediments m a y have been entrained f r o m the stream b e d and carr ied o f f to the swamp/lake b e l o w , some o f these fines l i k e l y exchanged w i t h natural f ine material o f the stream trapped w i t h i n the interstices between larger sediments. Coarser source-sediment (greater than coarse silt) remained o n the b e d m i x i n g w i t h and replac ing the natural sediments. A s w o u l d be expected, this resulted i n geochemica l changes to the background concentrations o f stream sediments. F o r example, concentrations were found to increase b y as m u c h as 50 p p m for C o , 1 % for M g and 150 p p m for N i , one year after disturbance (Figures 6.3.1-6.3.4). These increases i n b a c k g r o u n d concentrations can be attributed to inputs o f sediment der ived f r o m re lat ive ly unweathered l o c a l t i l l s and m a f i c bedrock, that have re lat ively h i g h abundances o f these trace elements (often associated w i t h heavy minerals) . C o n t i n u e d erosion f r o m cutblocks , roads and landings or mass wast ing events might further increase background concentrations. Converse ly , Fletcher and M u d a s ( i n prep.) found that sediment inputs f r o m h e a v i l y leached regol i th i n M a l a y s i a l o w e r e d b a c k g r o u n d concentrations i n streams. T h e results also ident i f ied anomalous Z n concentrations b e l o w the stream crossings (Figures 6.3.6-6.3.10) w h i c h c o u l d not be attributed to Z n concentrations i n source-sediments. T h e most l i k e l y source o f the elevated Z n concentrations is the abrasion o f particulate z i n c oxides f r o m the r o u g h surfaces o f newly- ins ta l led culverts, part icular ly d u r i n g periods o f h i g h stream discharge w h e n clasts are m o b i l i z e d and transported through the culvert. A less l i k e l y explanation is the d i s s o l u t i o n o f Z n ions 185 f r o m the surface o f the ga lvanized culvert , w h i c h are then precipitated or absorbed o n sediments b e l o w the culvert. T h e h i g h Z n concentrations were found to occur i n the - 0.053 m m size fraction, w h i c h supports b o t h o f these scenarios. E l e v a t e d concentration o f Z n i n the paramagnetic fraction is thought to be due to the substitution o f Z n for F e i n magnetite and is not considered a l i k e l y explanat ion for the elevated Z n concentrations i n sediments. 6.5 Summary of post-harvesting effects and new sediment sources Increased sediment loads from the erosion o f roads, ditches and adjacent l o g landings at stream crossings m o d i f y the natural geochemical patterns w i t h i n the stream. It is c lear ly poss ible to use geochemical methods to trace the n e w source-sediment o n the bed o f a stream. Results w i l l be best for large singular events rather than frequent recurrent events where the stream does not have sufficient t ime to restore its natural b a c k g r o u n d concentrations. 186 CHAPTER 7 DISCUSSION, LONG-TERM EFFECTS, RECOMMENDATIONS AND CONCLUSIONS Results obtained i n 1996 p r i o r to disturbance b y l o g g i n g show that sediments f r o m each stream have their o w n distinct mult i-e lement geochemica l signature that can be related to the l i t h o l o g y and m i n e r a l o g y o f the geologica l units present i n each drainage basin. S a m p l i n g and re-sampl ing undisturbed contro l sites i n 1996 and 1997 suggests that this geochemica l f ingerprint remains reasonably stable w i t h levels o f year-to-year var iat ion be ing comparable to total wi thin-s i te var iat ion i n a s ingle year. G i v e n that sediments o f undisturbed streams have stable geochemica l f ingerprints, it becomes poss ib le to detect and trace input o f any new, g e o c h e m i c a l l y dist inct material f r o m the result ing changes downstream i n stream sediment c o m p o s i t i o n . Elements most suited to this purpose w i l l be those h a v i n g the greatest and most consistent geochemica l contrast between the natural sediment and the n e w sediment source(s) and w h i c h are contained i n the minerals and size fractions that are preferential ly eroded (Sect ion 1.3). T h e elements w h i c h are the most useful w i l l depend o n g e o l o g i c a l and other factors, and hence, w i l l v a r y from stream to stream and area to area. H o w e v e r , out o f a suite o f 30 or more elements that can be determined for ~$10 per sample b y c o m m e r c i a l laboratories ( I C P ) , it seems l i k e l y that one or m o r e suitable elements c o u l d usual ly be found. 187 7.1 Long-term effects of logging T h i s research presents o n l y the first year post-harvesting results for streams B 1 - B 6 , w i t h some inferred effects f r o m road construction f ive years earlier o n B l ; the l o n g -term effects are u n k n o w n . T h e most l i k e l y outcome is that erosion and sediment input into streams w i l l gradual ly d i m i n i s h , as the point source areas re-vegetate and exposed surfaces become armoured. T h i s might lead to a gradual return to " n o r m a l " geochemistry i n streams. H o w e v e r , i f cont inued erosion f r o m roads and adjacent landings persists, or i f larger sediment sources develop, such as f r o m mass wast ing , the stream geochemistry w i l l continue to be inf luenced b y these sources. In the l o n g term, the natural texture o f the stream c o u l d also change i f the quantity o f source-sediment input exceeds the capacity o f the stream to remove the fines (e.g. Fletcher, 1996). Perhaps over a longer p e r i o d o f t ime there might be geochemical changes due to the r e m o v a l o f tree cover, not related to specif ic sediment sources but due to changes i n the groundwater regime m o d i f y i n g the input o f d isso lved elements to the stream. 7.2 Applications and implications These techniques m a y be appl ied to trace sediments introduced into streams f rom: (1) any in-stream construct ion w o r k (roads, culverts, bridges, etc.) or sites subject to 188 active erosion; (2) mass movements (e.g., f r o m landsl ides; H o u and Fletcher , 1996); (3) effluent or tai l ings disposal i n streams; and (4) other sources o f contaminat ion. T h e m i n i n g and forestry industries and their regulating agencies m a y have specif ic applications i n t racking and quanti fy ing sediments generated f r o m anthropogenic sources w h i c h contaminate or w h i c h m a y be h a r m f u l to the aquatic environment, such as Z n f r o m culverts. These techniques, i n general, w i l l be most effective where the source has a geochemical f ingerprint distinct f r o m that o f the o r i g i n a l sediment and for large singular events rather than smal ler recurrent events. A t present this technique has been developed to the point where it m a y identi fy the changes to b a c k g r o u n d concentrations result ing f r o m source-sediment inputs, and trace the disturbance a long-stream to the point where the effects become un-detectable o n account o f d i l u t i o n . It is not poss ible to precise ly quantify the amount o f source-sediment added to the stream. T h e effects w h i c h source-sediment has o n b a c k g r o u n d concentrations vary depending o n the nature o f the sediment source (trace element abundance, bedrock geology, sur f ic ia l materials) , c l imate, and sedimentologica l processes o c c u r r i n g w i t h i n the stream. Further, the magnitude o f Z n contaminat ion f r o m culverts found i n this research (200-500 p p m o f Z n ) exempli f ies the importance o f consider ing potent ia l ly u n k n o w n and unexpected contaminat ion f r o m any anthropogenic sources and a v o i d i n g sites w h i c h m a y be adversely affected b y this contamination. F i e l d observation records w i l l also 189 help d u r i n g interpretation o f geochemica l data to e l iminate spurious data f r o m sites that are potenita l ly affected b y sediment inputs or other sources o f contaminat ion. 7.3 Recommendations and future projects Ideally, this research w o u l d be f o l l o w e d up, i n 5 or 10 year intervals , to m o n i t o r the recovery o f the stream to its pre- logging state and/or to m o n i t o r any long-term geochemica l changes w h i c h m a y be occur ing . T h i s w o u l d i n v o l v e re-sampl ing sites b e l o w the sources and a l i m i t e d number o f control sites above sources. Because the Baptiste lakes act as sediment traps b e l o w the logged areas, there is no opportunity to l o o k at impacts i n the l o w e r reaches o f the drainage basin. T h e magnitude o f the disturbance is , however , re lat ively s m a l l and u n l i k e l y to be detectable over a great distance. H o w e v e r , lake cores from " U p p e r " Baptiste L a k e m a y be useful i n p r o v i d i n g i n f o r m a t i o n o n changes i n sediment y i e l d from the study streams. C o r i n g w o u l d p r o v i d e a pre- logging record, as w e l l as any post-disturbance changes. T h e techniques developed and u t i l i z e d i n this study c o u l d be further developed o n a longer stream h a v i n g variat ions i n h y d r o l o g y and stream gradients and w i t h a strong n e w sediment source. A n ideal s ituation might be a starting placer m i n e , o n a p r e v i o u s l y u n m i n e d stream, where sediment discharges to the stream are permitted. 190 Research c o u l d further be enhanced b y co l laborat ion w i t h a sedimentologist . Measurements o f increases i n suspended and total sediment, as w e l l as gra in size data, before and after disturbance w o u l d help to understand w h i c h size fractions o f the source-sediment are entrained and r e m o v e d and w h i c h size fractions r e m a i n o n the stream bed. T h u s , the size fraction to analyze i n order to obtain the m a x i m u m effects f r o m the source-sediment c o u l d be refined. Al ternate ly , this c o u l d be a c c o m p l i s h e d e m p i r i c a l l y b y g e o c h e m i c a l l y analys ing different size fractions and c o m p a r i n g the results. A l s o , the geochemica l patterns from sediment sources i n different c l i m a t i c regimes and from different source materials should be investigated. Further research should be undertaken to determine the source and extent o f the z i n c contaminat ion and its potential inf luence o n the chemistry and aquatic f o o d c h a i n o f s m a l l streams. In addi t ion to future research projects, recommendations can also be made to reduce the impact o f l o g g i n g o n s m a l l streams. Results show that clear-cut l o g g i n g w i t h the prescriptions used, i n this reg ion (terrain, c l imate, stream size, etc.), i n itself, has a very l o w impact o n stream sediments; the effect c o u l d be even less i f eros ion from roads, landings and stream crossings is control led. T h i s research leads to two pract ical recommendat ions to i m p r o v e current l o g g i n g practices. F i r s t , the locat ion selected for stream crossings and landings should be careful ly considered to m i n i m i z e the amount o f disturbance and result ing impacts from erosion. W h e n possible , landings bui l t 191 adjacent to streams should not have r u n o f f f r o m the exposed and compacted surface directed into the stream. W h e r e erosion and r u n o f f f r o m landings and r o a d surfaces is l i k e l y , r u n o f f c o u l d be directed into natural depressions or constructed pits w h i c h w o u l d act as settl ing ponds to col lect sediment. T h e second r e c o m m e n d a t i o n is to select the best l o c a l l y avai lable material for road f i l l , part icular ly near streams and for construct ion o f stream crossings. M a t e r i a l w h i c h is not h i g h l y erosive and w h i c h does not conta in h i g h percentages o f fines w o u l d be preferred. B e d r o c k , for example , m a y have less effect than us ing t i l l s . I n Baptiste , bedrock c o u l d easi ly have been m e c h a n i c a l l y excavated f r o m outcrops adjacent to roads for the construct ion o f stream crossings. 7.4 Summary of methodology (i). Sampling requires c o l l e c t i o n o f representative samples o f suspected sediment sources, and f r o m the stream i m m e d i a t e l y above and b e l o w the sediment source. Ideal ly , sediment samples w o u l d be col lected before disturbance to p r o v i d e baseline data. H o w e v e r , this m a y not be necessary p r o v i d e d undisturbed sediments are avai lable i m m e d i a t e l y upstream o f a n e w sources o f sediment. T h e n u m b e r o f samples required and the s a m p l i n g interval downstream f r o m the source w i l l depend o n the size o f the source and the size o f the stream and drainage bas in . Care should be taken to col lect sediments, consist ing o f a few k g o f mater ia l f i e l d screened to remove pebbles, from s i m i l a r active f l u v i a l environments ( i n this study, from s m a l l bars). 192 (i i) Sample preparation and analysis: C h o i c e o f the size fract ion to analyze is not cr i t i ca l p r o v i d e d it is suff ic iently f ine-grained that a 0.5 g analyt ica l sub-sample w i l l g ive reasonably consistent results w i t h r a n d o m var iat ion not exceeding ~± 2 5 % at the 9 5 % confidence level . H e r e this was achieved w i t h the - 0.212 m m size fraction, consist ing o f m e d i u m sand and finer material . Because the m e t h o d o l o g y relies o n c o m p a r i s o n o f relative concentrations o f a suite o f elements the m e t h o d o f sample d e c o m p o s i t i o n is not c r i t i c a l but must be consistent. Satisfactory results were achieved w i t h b o t h a total ( H C 1 0 4 - H F - H N 0 3 ) and a (s l ight ly less cost ly) strong a c i d attack w i t h aqua regia ( H C 1 - H N 0 3 ) . T h e implementat ion o f a qual i ty control program to m o n i t o r r a n d o m s a m p l i n g and laboratory errors is essential. T h i s i n v o l v e s c o l l e c t i o n and analysis o f f i e l d duplicates. Results are then assessed us ing standard T h o m p s o n and H o w a r t h (1976) plots . (iii) Interpretation: Suitable tracer elements are those that m a x i m i z e the geochemica l contrast between undisturbed sediments and n e w sources o f sediment, and can be evaluated u s i n g ratios and t-tests o f means. S i m p l e d i l u t i o n m o d e l s can then be used to estimate the amount o f n e w material incorporated into the sediments downstream f r o m sediment sources. A l t h o u g h the m e t h o d is conceptual ly s imple , o p t i m u m design and interpretation o f a sediment tracer p r o g r a m involves decisions that are best made b y an appl ied 193 geochemist or geoscientist w i t h geochemical expertise. T h e mutl i -e lement i n d u c t i v e l y c o u p l e d p l a s m a packages offered b y c o m m e r c i a l laboratories are a convenient method o f h a v i n g samples analyzed. 7.5 Conclusions T h i s research presents a m e t h o d o l o g y to use mult i -e lement geochemistry to identi fy sediment w i t h i n a channel f r o m a part icular source and to track the sediment downstream. These techniques c o u l d have a broad range o f scienti f ic and industr ia l appl icat ions, each o f w h i c h w o u l d be designed to take into account l o c a l c l imate , h y d r o l o g y and geology. 194 REFERENCES A r m s t r o n g , J . E . , 1949. F o r t St. James, B . C . , M a p 9 0 7 A . In: B r i t i s h C o l u m b i a . 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(1) TERRAIN UNIT SYMBOLS Simple Terrain Units: e.g., texture—>gFt - J<—process surficial material / \ surface expression Note: Two or three letters may be used to describe any characteristic other than surficial material, or letters may be omitted if information is lacking. Composite Units: Two or three groups of letters are used to indicate that two or three kinds of terrain are present within a map unit. e.g., Mv • Rs indicates that "Mv" and "Rs" are of roughly equal extent Mv/Rs indicates that "Mv" is more extensive than "Rs" (about 2/1 or 3/2) Mv//Rs indicates that "Mv" is much more extensive than "Rs" (about 3/1 or 4/1) Stratiqraphic Units: Groups of letters are arranged one above the other where one or more kinds of surficial material overlie a different material or bedrock: e.g., My indicates that "Mv" overlies "Rr". Rr /My indicates that "Rr" is partially buried by "Mv" Rr (2) MATERIALS A Anthropogenic materials Artificial materials, and materials modified by human actions such that their original physical appearance and properties have been drastically altered. C Colluvium Products of gravitational slope movements; materials derived from local bedrock and major deposits derived from drift; includes talus and landslide deposits. D Weathered bedrock Bedrock modified in situ by mechanical and chemical weathering. E Eolian sediments Sand and silt transported and deposited by wind; includes loess. F Fluvial materials Sands and gravels transported and deposited by streams and rivers; floodplains, terraces and alluvial fans. F A "Active" fluvial materials Active deposition zone on modern floodplains and fans; active channel zone. 203 (2) MATERIALS cont'd F G Glaciofluvial materials Sands and gravels transported and deposited by meltwater streams; includes kames, eskers and outwash plains. 1 Ice Permanent snow and ice; glaciers. L Lacustrine sediments Fine sand, silt and clay deposited in lakes. L G Glaciolacustrine sediments Fine sand, silt and clay deposited in ice-dammed lakes. M Till Material deposited by glaciers without modification by flowing water. Typically consists of a mixture of pebbles, cobbles and boulders in a matrix of sand, silt and clay; diamicton. M' Ablation till Material accumulated on top of a melting glacier; coarse textured and less consolidated than basal till. 0 Organic materials Material resulting from the accumulation of decaying vegetative matter; . includes peat and organic soils. R Bedrock Outcrops, and bedrock within a few centimetres of the surface. U Undifferentiated materials Different surficial materials in such close proximity that they cannot be separated at the scale of the mapping. V Volcanic materials Unconsolidated pyroclastic sediments. W Marine sediments Sediments deposited by settling and gravity flows in brackish or marine waters, and beach sands and gravels. W G Glaciomarine sediments Sediments laid down in marine waters in close proximity to glacier ice. (3) TEXTURE c clay < 2um k cobbles 64 - 256 mm z silt 62.5 - 2um b boulders > 256 mm s sand 2 mm - 62.5um a blocks angular boulders p pebbles 2 - 64 mm Common Clastic Terms f fines any or all of c, z, and fine s d mixed fragments pebbles and larger clasts in a matrix of fines 9 gravel any or both of p and k r rubble angular gravel x angular fragments mix of both r and a m mud mix of both c and $ Y shells shell or shell fragments Organic Terms e fibric u mesic h humic 204 (4) SURFACE EXPRESSION a moderate slope(s) predominantly planar slopes; 15-26° (27-49%) b blanket material > 1 -2m thick with topography derived from underlying bedrock (which may not be mapped) or surficial material c cone a fan-shaped surface that is a sector of a cone; slopes 15° (27%) and steeper d depression enclosed depressions f fan a fan-shaped surface that is a sector of a cone; slopes 3-15° (5-27%) h hummocky steep-sided hillocks and hollows; many slopes 15° (27%) and steeper j gentle slope(s) predominantly planar slopes; 3-15° (5-27%) k moderately steep slope predominantly planar slopes; 26-35° (49-70%) m rolling topography linear rises and depressions; < 15° (27%) P plain 0-3° (0-5%) r ridges linear rises and depressions with many slopes 15° (27%) and steeper s steep slope(s) slopes steeper than 35° (70%) t terrace(s) stepped topography and benchlands u undulating topography hillocks and hollows; slopes predominantly <15° (27%) V veneer material < 1-2m thick with topography derived from underlying bedrock (may not be mapped) or surficial material; may include outcrops of underlying material w variable thickness material of variable thickness with topography derived from underlying bedrock (may not be mapped) or surficial material X thin veneer a subset of v (veneer), where there is a dominance of surficial materials about 10-25 centimeters thick 205 (5) GEOLOGICAL PROCESSES AND MASS MOVEMENT SUB-CLASSES A Avalanches Slopes modified by frequent snow avalanches. Af Avalanches: major tracks In zones of coniferous forest: broad avalanche track(s) occupied by predominantly shrubby, deciduous vegetation. Am Avalanches: minor tracks Similar to above, but generally narrower than the height of adjacent trees. Aw Avalanches: mixed Includes both major and minor avalanche tracks. Ao Avalanches: old tracks Clearly visible on air photos, but less well defined than active tracks because they are partly or completely occupied by young conifers. B Braiding channel Channel zone with many diverging and rejoining channels; channels are laterally unstable. C Cryoturbation Heaving and churning of soil and surficial materials due to frost action. D Deflation Removal of sand and silt particles by wind action. E Glacial meltwater channels Areas crossed by meltwater channels that are too small or too numerous to map individually. F Failing Slope experiencing slow mass movement, such as sliding or slumping. H Kettled Area includes numerous small depressions and/or lakes where buried blocks of ice melted. 1 Irregularly sinuous channel Channel displays irregular turns and bends. J Anastamosing channel Channels diverge and converge around semi-permanent islands. K Karst processes Solution of carbonates (limestone, dolomite) resulting in development of collapse and subsidence features. L Surface seepage Zones of active seepage often found along the base of slope positions. M Meandering channel Channel characterized by regular turns and bends. N Nivation Surface modified by hollows developed around semi-permanent snowbanks. P Piping Subsurface erosion of silty sediments by flowing water resulting in the formation of underground conduits. R Rapid mass movement Slope or parts of slope affected by processes such as debris flows, debris slides and avalanches, and rockfall. S Solifluction Slope modified by slow downslope movement of seasonally unfrozen regolith. U Inundated Areas submerged in standing water from a seasonally high watertable. V Gullying Slope affected by gully erosion. W Washing Winnowing of fines by flowing water resulting in development of lag deposits. X Permafrost processes Processes related to the presence of permafrost; permafrost aggradation and degradation. z Periglacial processes Solifluction, nivation and cryoturbation occurring together in a single terrain unit. 206 Mass Movement Sub-Classes -F" Slow m.m. (initiation zone) -Fx Slump-earthflow -Fc Soil creep -R" Rapid m. m. (initiation zone) -Fe Earthflow -Rb Rockfall -Fg Rock creep -Rd Debris flow -Fi Lateral spread in surficial materials -Rf Debris fall -Fk Tension cracks -Rr Rockslide -Fm Slump in bedrock -Rs Debris slide -Fp Lateral spread in bedrock -Rt Debris torrent -Fu Slump in surficial material (6) SOIL DRAINAGE CLASSES r rapidly drained water is removed from the soil rapidly in relation to supply w well drained . water is removed from the soil readily but not rapidly m moderately well drained water is removed from the soil somewhat slowly in relation to supply i imperfectly drained water is removed from the soil sufficiently slowly in relation to supply to keep the soil wet for a significant part of the growing season P poorly drained water is removed so slowly in relation to supply that the soil remains wet for a comparatively large part of the time the soil is not frozen V very poorly drained water is removed from the soil so slowly that the water table remains at or on the surface for the greater part of the time the soil is not frozen Where two drainage classes are shown: if the symbols are separated by a comma, e.g., "w,i", then no intermediate classes are present; if the symbols are separated by a dash, e.g., "w-i", then all intermediate classes are present. (7) SLOPE CLASSES 1 0-3° (0-5%) 3 15-26° (27-49%) 5 >35° (>70%) 2 3-15° (5-27%) 4 26-35° (49-70%) (8) ON-SITE SYMBOLS AND BOUNDARY LINES Boundary lines: definite boundary indefinite assumed or arbitrary study area boundary boundary boundary © A 1 0 ground inspection site A A8 visual inspection site Glacial Features Mass Movement and Erosion Features Crag and tail „ Scar of recent larger slide r^~r~^^j Striatinns . Scar of old larger slide ^ ^  ^ n Esker -yy > > > 7 Scar of recent small slide s~\ Kettle holes (large, small) rg) Scar of old small slide ^ -^ Glacial meltwater channels (large, small) Recent debris flow ? Tension cracks % j -207 00 c o a) *-» "35 a> a E (0 00 co CD CD a) V -3 D) ii < o • O # - i3 C3 o CQ a w o o "•4—» CD cn CD 3H >H 'in CD a, 0 3 fl Q to "E, -*i G O on CD t M CD c cn g on °6 i s ao orj ^! o o CN CN 208 G • •3 c5 O w § o pq o o 00 CU OH ^ 0 0 co m oo oo co CD 1 o co g oo =8 a* ^ wa a M M g a a DO & ^ e M H S C O PQ pq oo 3 Q O O T3 CN CN © OO 210 o J ffl W ty) t/3 0 0 a u ^ oo S £ & o g co S) - I b ^  ^  c J - ^ a oo oo £ PH 0 0 ft ^ CU u VH 3 O co C CD o o -a CN CN CD 0 0 211 o o w § O PP 00 u OH o ^ • ^  in M 6 0 OH ^ 6 0 6 0 ',3 OH 6 0 O. ^ — * a m Q CN CN OQ W 3 O cn d T3 CO C/2 212 213 214 215 Accepted concentration of standard (ppm) gure B 1 : A c c u r a c y o f geochemical results f r o m total and aqua regia digestions for standards analysed i n 1996 and 1997 for the element B a . T h e solid line represents the x=y line and the dashed lines are +/- 20 %. 216 gure B 2 : Accuracy of geochemical results from total and aqua regia digestions for standards analysed in 1996 and 1997 for the element Cr. The solid line represents the x=y line and the dashed lines are +/- 20 %. 217 gure B3: Accuracy of geochemical results from total and aqua regia digestions for standards analysed in 1996 and 1997 for the element Co. The solid line represents the x=y line and the dashed lines are +/- 20 %. 218 ure B4: A c c u r a c y o f geochemical results f r o m total and aqua reg ia digestions for standards analysed i n 1996 and 1997 for the element C u . T h e solid line represents the x=y line and the dashed lines are +/- 20 %. 219 F i g u r e B5: A c c u r a c y o f geochemical results f r o m total and aqua regia digestions for standards analysed i n 1996 and 1997 for the element F e . T h e solid line represents the x=y line and the dashed lines are +/- 20 %. 220 Accepted concentration of standard (ppm) F i g u r e B 6 : A c c u r a c y o f geochemica l results f r o m total and aqua reg ia digestions for standards analysed i n 1996 and 1997 for the element M n . T h e solid line represents the x=y line and the dashed lines are +/- 20 %. 221 gure B7: A c c u r a c y o f geochemical results f r o m total and aqua regia digestions for standards analysed i n 1996 and 1997 for the element N i . T h e solid line represents the x=y line and the dashed lines are +/- 20 %. 222 F i g u r e B 8 : A c c u r a c y o f geochemica l results f r o m total and aqua reg ia digestions for standards analysed i n 1996 and 1997 for the element P b . T h e solid line represents the x=y line and the dashed lines are +/- 20 %. 223 Accepted concentration of standard (ppm) Figure B 9 : Accuracy of geochemical results from total and aqua regia digestions for standards analysed in 1996 and 1997 for the element Sr. The solid line represents the x=y line and the dashed lines are +/- 20 %. 224 F i g u r e B I O A c c u r a c y o f geochemica l results f r o m total and aqua reg ia digestions for standards analysed i n 1996 and 1997 for the element V . T h e solid line represents the x=y line and the dashed lines are +/- 20 %. 225 gure B l 1: A c c u r a c y o f geochemical results f r o m total and aqua regia digestions for standards analysed i n 1996 and 1997 for the element Z n . T h e solid line represents the x=y line and the dashed lines are +/- 20 %. 226 •c o 3 J a . o 1-5 IS 1-5 ONOOONOOoocoinooooON'rj-cnvocn>oooooooinoo r~rHt-~cnv©ooNOinONin'ri-rHoot'--vo©r--ino ,\© vi in N ft H m - H r- CN c-~ oo vo io O CN ON O VO TJ- O <—i o m oo r- r- —c VO 00 i oo m ON CN CN CN CN —i CN 00 cn CN CN rH Tf cn CN CN •rf in CN CN oo oo OT^ ,nt-HOrro\r---c<-i'-<vor<-)'ninTtrHU-)CN O O N f t c n r ~ O f M - H r H ^ f i n o v v o o s i n r n < - i o o H rHrnCNCNmCNCNCNrHCNCnCN-H—lrHCN cnOCNOONCNCNr-mrHcnooocNONVOmco o s o \ r - - o c n O ' r | - ' - H o o o < n o T r o s r - - c N - - o o CNmCNCNmCNCNrHrHrnCnCN'-HrHrHCN 00C~rH00'rl-CN>n'-HOrHCN00 00-rf'-H rHrHCNCNCNCNmCNCNCNCNCNCNCNCN C CN *rj" rH CN CN r^voTtot^cninrHoocNrHino \ooor--r<-)oo rHrHCNCOCNCNcnCNrHCNCNCNCNCNCN-HCNCN o v t ^ r H t ^ i n i n T r r ^ c N C N c « r H t ^ t - - f - - c N r ^ c N h c j c e c c h i q c f l q o q r - ; O N C o v q ^ t s : o o i n i y - i r t x f r H a \ 0 \ t - ~ c N v o r n o o r ~ o \ o o o \ C N c < - i v o i n r H rH rH rH CN rH rH rH rH rH rH rH rH rH rH rH rH rH o © © © © © © © © © © © © © © © o © © © t m VO t-- 00 CN Ov ON rH m 00 rH co VO o rH •rf vo r-- VO VO VO <n m VO >n •n m m >n >n >n vo r> >n © © © © © © © © © © © © © © © © © © © © © CN in r- ON m cn © m ON oo VO VO VD cn rH vo oo CN 00 VO VO >n in in in VO in m in VO in in m m in in ON P-cn CN oo © ON vd vd rncNincNrHNor-r-VOCNrHCn^inrH-H-N O vd vd vd vd vd vd m ON r-- VO oo oo oo in ON ON vd in in in in oo ON oo oo CN m r— ^ in T *~. °°. vd 'I vo vo vo in ON cn ON ON rn rn rn in oo vd vd vo NO in Tf rn CN cn ON CN m in vd °°. °°. P ^ "t in in vo vo NO 227 5 * 1-5 |HH ^ I-a IS §•1 1-5 I. a i f 00 © CN CN © cn 00 00 t-H T-H 00 T-H so CN Tf CN ON T-H oo © 00 CN cn r- © m Os ON CN cn T-H OS m cn oo © ON T-H <n cn CN cn T—< CN cn CN CN T-H cn CN r- cn cn CN cn © Os cn ON ON NO cn in CN CN Tf cn CN Tf oo © NO NO Ti- cn oo © NO OO OO T-H Tf oo T-H NO cn oo T-H cn T-H >n cn CN cn T-H CN CN cn CN T-H Tf 00 CN T-H en oq NO cn NO m cn NO CN 00 Tf oo oo m cn T-H t-; 00 OS T-H cn oo T-H © cn NO NO in © NO 00 CN T-H CN CN CN T-H T-H T-H CN T-H cn CO CN oo oo NO Tt Tf NO oo oo Tf r-; NO in CN in cn oo SO T-H NO © r- cn 00 OS © T-H © co in T—* lO in NO ON T-H T-H CN CN T-H CN CN CN cn © © © © © © in m m cn m © © © m in m © in CN Tf CN Tf NO © in in T-H cn Tf ON OS © © © in T-H T-H Tf CN f» CN CN T-H cn Tt T-H © cn cn os T—t ON Tf © r~ OS cn CN cn T-H CN T-H T-H T-H Tf © o cn © cn © © © cn >n © © © © in in in © © cn cn cn © © Tf ON ON NO CN OS © m cn oo T-H T-H T-H m  © OS oo T-H T-H ON Tf cn T—H © CN Tf OS T-H oo Tf © NO ON T-H cn Tf T-H T-H T-H Tf cn NO CN CN NO CN r- CN cn in ON ON 00 cn cn oo oo oo Tf ON © TT © VO NO cn Tf cn NO Tf oo cn r-- cn CN CN CN T-H T-H T-H CN CN T-H CN CN CN T-H T-H T-H CN cn cn CN Tf 00 00 oo NO SO CN oo cn oo oo cn in in m 00 Tf ON Tf T—H ON OS m CN ON ON Tt; cn NO Tf cn in i-; cn CN in © CN CN CN T-H T-H CN CN CN oo CN ON Os cn NO NO 00 00 NO cn cn Tf in ON in Tf Os © T-H T-H ON © © Os © Os ON ON CN 00 00 00 oo OS © 00 T-H © ©' T-H o © ©' T-H ©' © © © © © © m m Tf NO CN CN m 00 00 OO NO CN T-H ON c-~ SO CN CN ON © © oo ON ON OO ON 00 ON ON © 00 ON oo OS © Os o T-H © © © © © © © ©' © ©* ©' © ' © ©' T-H © CN CN cn Tf so (N _H oo CN CN m oo oo CN m ON _i ON t-; T-H CN CN Tf CN ON oq T-H Tf ON cn so oq ON oo in CN cn Tf cn cn cn Tf cn cn Tf cn cn cn cn cn cn cn in CN Tf ON CN T-H cn Tf ON Tf cn oq t-; cn oo 00 00 Tf NO CN ON CN T-H 00 Os © © ON cn cn t-; © © Tf '-^  cn Tf cn CN Tf Tf cn cn Tf Tf cn cn Tf Tf cn cn CN cn °. Tf 228 I N & CU .s 60 •c o 1-5 loo IP* CH ' OH ( 00 •g V O C N V O C N © T T V O V O O O O O v O i O r H T j - ^ f o O O N O O C N C N O O C N O O V O o O O T f C N o o r H o o r ~ - o o o o o \ o o N o CN VO oo VO o CN VO VO CN © VO CN o Tr 0 0 0 0 oo O Tf vo K0 rH CN rH o O ON oo CN CN p~ rH OO 00 oo o r~ r- o rH rH rH rH rH rH CN VD r- IO VD VO oo VO oo Tr VO ro CN CO oo CO m VO co ro rH rH co TT CN CN Tr VO m TT rH CN CO CO rH CN CN rH rH rH rH rH rH rH rH rH rH rH TT CO VO o CN o\ OO in VO l-H VO OO r» in VD o p~ tN ro rH in CN CO m in Tf ro CO rH CN CN CO oo rH oo in ro CN OO Ov CN in Tf in VO oo VO oo 00 oo ro TT ro co Tr TT ro ro TT in in TT ro CO o ro ro CO ro CO © © d d d d O O d d d d d d d d d O d ON < r- TT CO in CN CO TT in uo ON 0 0 NO ON oo Ti-ro TT ro CO m •* ro o m m Tr CO ro ro ro ro ro ro ed © d d d d d d d d d d d d O d d d d T—1 TT CN oo o ro ro co TT ON VO f- ro CN oo ro CN TI- TT ON oo vo CN o CN CN oo 00 VO 00 ON rH o ON VO m CN CS CN CN CN CN CN CN CN CN CN CN CN rH CN CN rH CN CN CN 1/0 oo TT VO VO oo O ro oo in TT o ON ON TT f- rH ON ro CO oo VO VO rH OS ro CN r» oo VO ON ON O ON ON uo in ro CN CN (N CN CN CN rH CN CN CN CN CN rH CN rH rH CN CN CN oo TT Tr TT oo VO VO 0 0 VD CN TT oo TT Tr CN VD VO CN VO VO Tf TT TT VO oo TT TT TT VO CN TT CN TT CN •<* TT CN - VO o o o O o o o © © © © © © © © © © © © © 00 ON o Tr" m rH ON VO oo m in Tr oo ro oo TT co r-oo o ON CN VO vo oo r-- r- VO vo CN in vo oo VO © r-o o o O o O O © © © © © © © O © © © © © TT rH ON ro o VO © rH t- in in © TT vo in VO © VO VO oo rH oo rH r- VO oo r- VO vo CN VD VD vo oo VO o oo 229 Table B 2 . 1 : Analytical Duplicates (Lab Duplicates) submitted for analysis in 1997 with Total Digestion (T24) . A l Ba Ca Co % ppm % ppm inal duplicate original duplicate original duplicate original duplicate 6.52 6.22 620 640 1.64 1.62 22 23 5.85 6.09 560 580 1.57 1.6 16 18 6.41 6.36 610 610 1.67 1.63 15 15 6.38 6.64 530 580 1.63 1.68 28 32 5.68 5.54 540 500 1.37 1.41 42 37 6.22 6.21 670 650 2.06 2.09 14 14 7.1 7.33 710 750 1.69 1.42 25 19 7.25 7.27 740 780 1.26 1.31 16 18 7.06 7.53 720 780 1.26 1.3 18 20 6.86 7.18 700 710 1.73 1.74 18 17 6.81 7.3 710 750 1.66 1.79 19 20 7.05 7.09 700 700 1.66 1.71 18 19 6.4 6.65 630 670 1.71 1.77 19 18 6.82 6.72 690 670 1.77 1.69 22 23 6.48 6.79 650 660 1.64 1.76 20 20 6.79 6.49 660 610 1.85 1.76 24 23 6.63 6.38 630 620 1.79 1.86 21 24 5.61 5.4 480 460 1.67 1.78 26 26 5.78 5.58 500 480 1.72 1.65 28 27 6.05 6.2 510 550 1.53 1.57 24 26 6.14 6.14 540 540 1.66 1.68 31 31 6.43 6.65 600 650 1.97 1.78 22 23 6.77 6.69 630 610 1.94 1.88 22 22 6.27 6.63 600 630 1.74 1.76 27 25 6.45 6.64 600 650 1.74 1.68 20 24 6.89 6.71 660 630 1.69 1.64 24 23 7.38 7.12 760 740 1.51 1.5 20 21 6.85 6.74 710 680 1.65 1.57 24 24 6.18 5.98 580 550 1.73 1.66 24 22 6.33 6.33 550 540 1.73 1.71 29 27 6.77 6.87 700 670 1.61 1.64 25 23 6.45 6.38 560 530 1.69 1.68 32 31 5.39 5.4 460 470 1.7 1.71 24 24 6.35 6.57 560 590 1.38 1.52 27 28 6.24 6.38 560 590 1.4 1.38 26 28 7.26 7.37 560 540 2.02 1.98 28 27 6.59 6.39 530 510 2.07 2 32 31 230 Table B2.2: Analytical Duplicates (Lab Duplicates) submitted for analysis in 1997 with Total Digestion (T24). Cr Cu Fe K ppm ppm % % original duplicate original duplicate original duplicate original duplicate 214 217 79 80 3.63 3.74 1.11 1.04 155 160 75 78 3.24 3.36 0.92 0.96 135 137 67 60 3.19 3.12 1.09 1.09 300 292 82 92 4.26 4.68 1.05 1.08 647 644 375 301 4.28 4.11 0.81 0.83 90 90 66 70 3.32 3.36 1.02 1 146 129 192 74 4.48 4.09 1.2 1.26 108 116 81 80 4.05 4.23 1.28 1.26 112 120 86 96 4 4.32 1.19 1.23 113 115 113 116 3.79 3.83 1.23 1.23 115 121 69 73 3.82 4.12 1.09 1.2 147 164 155 158 4.18 4.33 1.13 1.13 167 164 71 78 3.56 3.72 1.06 1.12 176 174 51 50 3.78 3.69 1.18 1.15 188 198 69 63 3.93 3.97 1.1 1.17 187 175 117 108 4.29 3.97 1.05 1.03 202 199 67 69 3.83 3.78 1.11 1.02 282 301 65 62 3.67 3.55 0.79 0.75 301 295 57 54 3.83 3.66 0.84 0.83 301 306 58 60 3.94 4.14 0.89 0.9 319 333 60 56 3.94 3.97 0.92 0.9 236 221 52 63 3.69 3,94 1.03 1.09 306 278 56 53 4.29 4 1.14 1.09 266 272 106 102 3.71 3.93 1.02 1.11 226 230 70 90 3.6 3.9 1.09 1.1 262 230 85 80 3.93 3.77 1.16 1.14 150 156 64 59 4.17 3.94 1.36 1.32 270 265 70 70 4.09 3.98 1.24 1.22 245 228 91 86 3.95 3.73 0.96 0.92 316 313 58 59 4.22 4.18 0.99 1.02 273 248 103 102 4.41 4.29 1.14 1.15 274 294 78 75 4.83 4.74 1.05 1.07 359 315 78 75 4.07 3.9 0.81 0.79 275 329 77 72 3.92 4.13 0.91 0.97 283 283 72 77 3.97 4.08 0.93 0.95 218 219 93 95 6.17 6.21 1.57 1.6 459 443 298 286 4.93 4.88 0.98 0.97 231 Table B2.3: Analytical Duplicates (Lab Duplicates) submitted for analysis in 1997 with Total Digestion (T24). Mg Mn Na Ni % ppm % ppm rial duplicate original duplicate original duplicate original duplicate 2.2 2.13 1415 1440 1.95 1.84 213 209 1.85 1.87 1390 1440 1.57 1.63 143 145 1.54 1.48 1145 1075 2.14 2.18 99 96 2.91 3.05 1190 1305 2.03 2.12 378 410 4.19 4.16 3210 2710 1.62 1.67 622 573 1.09 1.11 5830 6010 1.76 1.71 83 88 1.72 1.46 2110 1305 1.9 2.18 104 100 1.35 1.32 1065 1080 2.24 2.38 77 75 1.25 1.31 1580 1690 2.13 2.22 91 96 1.39 1.42 1725 1765 2.03 2.07 91 89 1.4 1.52 2550 2670 1.67 1.86 103 114 1.65 1.73 1205 1225 1.79 1.9 147 160 1.52 1.61 1225 1300 2.18 2.26 111 114 1.94 1.9 1335 1340 2.23 2.16 160 159 1.9 1.96 1295 1260 1.95 2.17 162 157 1.94 1.87 2150 1980 1.62 1.55 329 311 1.96 1.87 1650 1625 2.14 1.99 164 156 2.92 2.74 1315 1215 1.6 1.56 354 334 3.23 3.08 1280 1220 1.61 1.6 380 356 2.9 2.98 815 860 1.72 1.71 321 325 2.95 2.91 1685 1640 1.83 1.81 343 327 1.93 2.11 1360 1645 2.12 2.14 154 183 2.21 2.13 1515 1465 2.23 2.08 181 176 2.43 2.63 1390 1415 1.93 2.12 220 236 2.14 2.25 1290 1500 2.12 2.03 185 204 2.5 2.44 1310 1255 2.22 2.18 248 237 1.83 1.76 1045 990 2.29 2.32 127 123 2.98 2.96 975 940 2.08 2.01 268 268 2.48 2.43 2490 2390 1.69 1.63 445 440 2.94 2.95 1185 1165 1.87 1.87 649 638 2.43 2.43 1270 1220 1.96 2 236 227 3 2.99 1320 1250 1.98 1.95 397 386 3.02 2.91 910 905 1.4 1.43 385 360 2.82 2.87 1325 1295 1.71 1.86 606 597 2.73 2.82 1190 1230 1.75 1.73 577 608 3.15 3.2 . 1195 1190 2.36 2.34 225 231 3.28 3.22 1545 1445 2.15 2.05 428 421 232 Table B2.4: Analytical Duplicates (Lab Duplicates) submitted for analysis in 1997 with Total Digestion (T24). P Pb Sr T i ppm ppm ppm • % inal duplicate original duplicate original duplicate original duplicate 830 840 4 10 263 252 0.43 0.4 800 830 6 6 212 222 0.36 0.37 650 620 4 6 284 284 0.42 0.41 920 1030 2 4 222 225 0.58 0.6 800 700 8 2 214 224 0.37 0.39 1150 1170 6 6 299 295 0.35 0.36 970 800 16 4 272 287 0.5 0.46 890 960 8 8 279 284 0.48 0.48 720 760 6 8 267 278 0.45 0.46 1010 990 6 4 302 301 0.42 0.42 1040 1120 6 6 260 275 0.38 0.42 1040 1070 6 4 268 280 0.42 0.43 730 750 4 6 300 306 0.45 0.48 700 710 6 8 306 290 0.45 0.42 730 710 4 6 258 291 0.42 0.47 1190 1120 6 4 224 214 0.44 0.42 650 670 4 4 278 263 0.5 0.44 640 620 6 1 205 200 0.38 0.35 710 660 8 4 209 204 0.37 0.35 720 740 4 4 214 217 0.4 0.4 580 560 4 8 222 232 0.4 0.4 710 770 1 4 295 291 0.45 0.45 750 730 4 6 302 285 0.55 0.51 670 670 4 6 257 286 0.43 0.48 640 710 4 6 289 271 0.47 0.46 730 700 4 2 285 274 0.47 0.45 810 800 4 4 287 279 0.49 0.47 780 760 4 6 271 251 0.45 0.42 900 880 6 6 235 225 0.38 0.36 620 600 6 6 239 239 0.45 0.45 1010 950 6 6 254 268 0.44 0.46 1120 1050 8 4 196 195 0.62 0.65 920 890 6 6 186 189 0.36 0.35 900 880 8 6 223 251 0.4 0.45 910 960 4 6 228 229 0.38 0.38 2080 2060 1 1 190 187 1.15 1.15 950 930 4 4 259 245 0.74 0.74 233 Table B2.5: Analytical Duplicates (Lab Duplicates) submitted for analysis in 1997 with Total Digestion (T24). V Zn ppm ppm original duplicate original duplicate 137 132 174 172 119 123 108 112 129 131 90 86 139 138 106 116 127 126 154 138 121 121 144 148 161 143 156 154 143 145 162 168 138 144 176 192 137 132 148 142 129 140 144 158 138 143 380 392 140 149 134 140 152 147 128 128 143 152 124 120 151 143 136 132 159 149 100 98 130 123 80 76 128 123 88 84 137 139 96 98 144 143 94 94 142 145 122 148 167 152 142 136 135 151 250 266 147 146 202 240 146 143 238 224 153 144 110 108 146 144 110 108 129 125 114 110 150 151 110 110 147 150 146 136 135 137 128 124 132 125 106 98 131 142 114 114 128 130 108 112 154 152 138 138 173 169 140 138 234 Is I ( 00 J o S J ta . c IU > CM 1-3 J m 1 ao o 1-5 o I 1-5 J cct s 1 60 cn T-H m P- cn ON NO © NO NO cn © CN OO ON NO 00 NO in ON m r- o NO NO 00 © Tf NO ON m m NO 00 Tf P- T - H r~-T - H T - H ON cn Tf T - H Tf ON oo CN m ON cn in CN © NO © p~ CN p-o ON m oo © NO NO oo T - H cn NO ON m NO 00 oo CN P~ T - H p-T - H Tf P- ON o ON cn ON in NO Tf Tf cn cn ON ON P- OS © 00 NO P^  o © P- © ON ON T - H T - H Tf in 00 m Tf in p- Tf T—1 T - H CN T - H T - H CN T - H T - H oo in m cn © OO in NO Tf NO m m cn cn CN ON Tf ON p- P- oo O ON T - H p- © CN © T - H © CN NO © Tf Tf m P~ NO T - H T - H CN T - H T - H T - H CN T - H CN CN ON CN in ON CN 00 P- in P- P- 00 © © 00 CN NO © © CN CN T - H T - H CN CN CN CN CN O ON Tf NO © ON P- ON in 00 00 P- © cn NO in © © CN — H T - H CN CN T - H T—< T - H CN T—H CN CN T—H CN CN CN oo T - H P- Tf m m Tf NO CN in CN CN cn p- CN NO m 00 Tf © in oo in in p~ © in Tf in ©' P- r- m m cn P- © NO © o o ©' © © ©' © © © © ©' ©' ©' ©' ON NO ON Tf p- in T - H oo Tf CN p- cn ON ON CN P-; p- cn CO T-1 ©° 00 m in 00 T - H NO in m Tf NO p- m Tf CN ©' ON p-© o © © © T - H © © © © o © © © — " ' © ©' o o o o © © © © © © © © © © © © © © © © CN cn o Tf T - H T—t T - H P- © p- oo © m cn p- ON P- Tf CN CN CN T - H T - H T - H T - H T - H T - H T - H - H CN T - H o O o o © © © © © © © © © © © © © © © © T - H CN © NO T - H T—< T - H 00 T - H p~ 00 © cn cn 00 00 >n CN © <N CN T - H T - H T - H T - H T - H T - H T - H CN T - H NO CN o NO © CN © Tf oo NO Tf NO Tf NO CN © oo oo CN © CN CN CN CN T—H Tf NO m CN CN o NO o NO 00 Tf Tf 00 © 00 NO CN 00 CN CN CN T—H © CN CN cn T - H T - H T - H T - H CN cn p- p- T - H CN CN Tf P- cn P- ON ON ON CN cn NO NO CN cn m T - H NO cn ON cn Tf ON ON oq P-; T - H >n CN cn NO cn oq P-; NO P- oq P-; P-; CN CN NO in m Tf ON NO P- Tf Tf cn Tf N© ON r- Tf Tf cn 00 ON oq in Tf O T - H ON P-; CN oq T - H cn T - H ON ON ON Tf NO NO oq -< CN T - H CN T - H CN -* T - H T - H T - H — 1 CN 235 J 60 J U NP 1-5 ;g.| 1-5 1-5 _ VO Tf CO ro O VO rH p- ro ON vo ON Ti- vo VO CN VO ON ro oo ro ro ro ro ro in ro CN ro CN TT ro ro ro ON VO 00 CO ON ON. ro O CN TT co ro Tr ON in oo rH oo © P~ ro CN CN 00 ro -3- ro ro ro in TT CO CN CN ro TT ro ro oo m qo TT O O O O O O © © O © © © © © © © © © © © TT O oo 1—4 CN TT VO ON rH © O p- VO ro r- ON rH CN © VO OO TT vo rf TT TT oo VO VO VO in in VO Tf m P~ P~ oo P~ o o © O o © © © © © © © © © © © © © © © TT p- CN m oo oo ON p- © © rH oo © rH ON ro TT © ON m VO oo in VO co TT TT oo p- vo VO in in VO TT in OO P- P- P-rH CN r- ON VO © oo VO ON ro vo © m © © oo TJ vo r- O VO ON VO © © © ON NO P- VO p- CN in rH vo vo ON ro rH rH CN CN CN CN H ro Tr rH VO OO VO P- Tf ON rH CN rH p~ in © CN © © m © P~ VO r-ro ON vo o VO © © © VO p- in in rH © ON VO m oo TT ro rH CN CN CN rH CN rH ro in O © in o in © © in © © m in © © in © © © o © p- CN m ro rH CN TT ON ON VO vo CN oo m VO ro TT o ro CN p- VO oo CN r- ON r~ rH © 00 oo rH ro ON oo ON TT ON rH CN TT rH rH m ro m O m m m m m in in © © © m in m in © m © m O ON VO in ON ON vo in © © © rH VO vo vo rH co vo P~ m p- TT oo CO VO oo p- CN CN oo ON rH CN oo ON oo oo p~ P- CN TT rH rH TT rH CN o\ VO ON CN m 00 CN m ON TT CN vq CN ro ON ON CN oo TT CO 00 o CN ro CO © ON oo ON rH CN ro CN rH VO p- © CN d rH rH © © © rH ' © © I—« m rs ON co CO TT vo ro TT ON VO rH P- CO Tr in ON oo CN CN TT ro © rH oo oo rH ro TT VO p- © CN , — ' d d rH rH rH © © rH rH © © rH p- p- ON VO VO P- TT P- VO P~ p- ON p- p- P- p- oo CN oo o o o O o © © H © © © © © © © o © © rH © © d d d © © © © © © © © © © © © © © © p- rH p- ON p- P- VO TT rH VO vo p- oo ON ON VO VO P- CN ON o o o O o © © o © © © © © © © © © rH © © d d d © © © © © © © © © © © © © © in TT TT rH CO P- oo ro Tr VO m m CN vq in oo P~ oo co in P-; ON TT TT © rH © CN in CN TT CO CO ro in oo P-; rH_ ro CN CN co ro ro ro CO ro ro ro ro CO CO CN CN ro ro OV oq p- CN 00 ro ON CN ON ro ON ON r- oo oo oo TT CN ro oo CN © ro ro © CN vq in TT ro rH ro in CN TT vq in in ro ro ro ro ro ro ro CO co CO CO ro ro ro CN CN ro ro 236 til 1-5 © CN CN Tf os so r- os OOCNOONOOOCNNONOOOSOTfTf fN fN Tf Tf CN SO SO Tf so Tf O O r- o r- r- t-» o fN so Os T - H O Tf CN r-O so Tf 00 ON ON CN © Tf 00 CN o CN o co • r-OOOSOT-HOSOOOOOsOsOOOSOcOV - lTfU - lSOSOOS soio'nw^r~sosoininsor-~sosoiosor-~Tfioso'o osmoosor— mr-OTfTfTfoooooooor-u-)sow^^sosoinsor--oor--u_iininsoso co o Tf IT) U-) SO so so T—< 00 T—< OS T - « © T - H © d o d o ' o ' o o ' o Os Os r-o o o T - C m T - H T - H r— CN T-H T-H T-H T-H © T-H T-H © d c J c J d d d d d Tf T - H T-C T - l o d d T—i CN OO Os d ~! <=>. °. © © © OSSOTfUOTfT-HOOOSCOCO O O ^ H ^ H T - H T ^ O O T - H T ^ © ON T - C CN © T ^ T - . © 0 © 0 © © © 0 © © © 0 © 0 237 Table B4.1: Analytical Duplicates (Lab Duplicates) submitted for analysis in 1997 with aqua regia digestion (G32). A l As Ba Ca % ppm ppm % original duplicate original duplicate original duplicate original duplicate 1.75 2.48 20 14 120 170 0.69 0.93 1.49 2.28 28 32 110 160 0.68 0.99 1.46 1.48 18 18 110 100 0.59 0.56 2.12 2.27 16 4 130 130 0.59 0.73 1.74 1.69 24 26 140 150 0.46 0.41 2.17 1.91 6 8 200 190 1.45 1.41 2.29 2.18 8 16 150 130 0.8 0.54 1.88 2.6 6 10 130 150 0.35 0.55 2.24 2.57 22 26 160 180 0.41 0.47 2.19 2.32 8 1 150 140 0.95 0.96 2.43 2.6 6 1 190 200 1.07 1.1 2.66 2.33 8 10 190 170 0.93 0.82 1.68 1.6 2 6 110 100 0.74 0.69 1.46 1.6 6 6 100 110 0.58 0.64 1.73 1.64 16 12 110 100 0.68 0.62 2.5 2.45 1 10 200 210 1.08 1.08 1.68 1.71 6 8 120 120 0.58 0.6 2.07 2.01 14 22 140 130 0.86 0.79 1.92 2.21 20 12 120 120 0.76 0.81 1.86 1.98 16 18 120 120 0.62 0.65 2.06 1.93 16 14 120 130 0.56 0.58 1.42 1.74 18 12 90 120 0.48 0.67 1.39 1.65 12 20 90 100 0.49 0.6 1.86 1.47 14 16 120 100 0.55 0.46 1.54 1.5 10 6 110 100 0.52 0.5 1.64 1.69 16 12 110 110 0.49 0.52 1.85 1.79 2 8 120 120 0.53 0.51 1.69 1.79 26 24 110 110 0.6 0.57 2.18 2.12 64 66 160 150 0.9 0.91 1.81 2.01 62 70 70 80 0.55 0.57 2.33 2.04 22 22 140 120 0.76 0.64 2.69 2.42 6 8 160 140 0.87 0.79 1.89 2.01 20 18 130 120 0.97 0.99 2.45 2.18 14 6 160 140 0.5 0.45 2.06 2.03 10 10 140 150 0.43 0.4 3.51 3.36 1 10 210 200 1.05 1.05 1.95 2.25 2 1 100 110 0.58 0.56 238 Table B4.2: Analytical Duplicates (Lab Duplicates) submitted for analysis in 1997 with aqua regia digestion (G32). Co Cr Cu Fe ppm ppm ppm % original duplicate original duplicate original duplicate original duplicate 20 22 132 156 77 106 3.2 3.85 13 17 79 101 68 88 2.44 3.27 13 13 73 74 62 56 2.73 2.61 27 28 173 185 88 88 3.95 4.12 33 32 309 288 345 336 3.97 3.98 15 14 56 49 72 81 3.16 2.91 22 18 87 73 198 66 3.93 3.51 15 18 60 72 74 97 3.6 4.39 18 18 69 73 87 100 3.89 4.08 16 16 65 64 113 113 3.41 3.42 17 18 69 71 67 73 3.47 3.58 18 16 92 82 173 153 3.84 3.54 17 18 96 94 77 84 3.24 3.42 19 18 105 112 46 48 3.13 3.22 17 16 117 103 65 65 3.44 3.27 21 22 118 119 111 109 3.56 3.69 21 21 105 110 68 66 3.28 3.44 23 23 198 189 71 64 3.54 3.37 23 24 193 207 58 58 3.3 3.51 19 19 180 184 54 58 3.47 3.47 26 26 199 191 59 61 3.41 3.63 18 17 116 138 48 55 3.14 3.54 16 19 138 147 41 53 3.5 3.73 26 21 156 136 122 92 3.48 2.99 19 19 130 122 73 75 3.31 2.99 20 20 133 144 73 76 3.09 3.22 17 17 85 85 58 57 3.34 3.34 19 21 154 165 64 66 3.22 3.41 20 20 155 156 92 95 3.43 3.59 23 24 186 207 58 59 3.54 3.7 21 19 160 151 106 97 4.03 3.68 28 29 197 188 88 75 4.6 4.5 21 21 212 220 78 81 3.67 3.74 26 23 200 177 83 72 3.71 3.4 24 23 174 169 73 75 3.44 3.47 25 25 158 152 96 95 5.99 6.08 26 27 234 243 273 296 4.35 4.35 2 3 9 Table B4.3 : Analyt ical Duplicates (Lab Duplicates) submitted for analysis in 1997 with aqua regia digestion (G32). K M g M n N i % % ppm ppm original duplicate original duplicate original duplicate original duplicate 0.08 0.14 1.24 1.52 1265 1490 143 180 0.06 0.08 1 1.4 1145 1465 93 113 0.06 0.05 0.96 0.93 955 870 70 66 0.21 0.22 1.9 2.06 1060 1100 297 308 0.06 0.05 2.42 2.31 2780 2810 371 360 0.09 0.08 0.81 0.69 6220 6680 76 76 0.11 0.07 1.2 0.91 1940 1095 82 75 0.06 0.11 0.81 1.03 850 1020 56 69 0.08 0.1 0.82 0.91 1480 1575 74 78 0.1 0.09 0.96 0.98 1605 1605 69 71 0.11 0.11 0.99 1.07 2410 2460 87 88 0.11 0.1 1.15 1.04 1070 990 117 105 0.1 0.08 1.05 1.08 1115 1130 87 92 0.07 0.08 1.22 1.25 1055 1115 111 115 0.09 0.08 1.18 1.12 1090 1085 112 106 0.17 0.15 1.29 1.28 1815 1870 247 256 0.07 0.08 1.08 1.08 1595 1540 106 105 0.07 0.07 1.61 1.5 1260 1190 255 225 0.07 0.07 1.57 1.69 1150 1145 236 241 0.06 0.07 1.29 1.37 645 665 173 183 0.06 0.06 1.45 1.47 1475 1555 216 215 0.06 0.09 1.1 1.28 1200 1340 99 118 0.06 0.07 1.09 1.23 1010 1215 100 117 0.08 0.06 1.79 1.62 1410 1135 175 162 0.07 0.07 1.32 1.35 1115 1135 128 133 0.07 0.07 1.45 1.51 995 1020 156 163 0.1 0.1 1.11 1.07 825 780 84 81 0.09 0.1 1.59 1.65 760 750 168 173 0.1 0.09 1.46 1.47 2350 2390 360 364 0.07 0.07 1.52 1.57 970 980 513 548 0.12 0.09 1.46 1.34 1065 1040 157 147 0.31 0.28 2.19 2.08 1215 1105 326 293 0.08 0.09 1.56 1.69 765 805 249 254 0.09 0.07 1.93 1.77 1265 1130 516 455 0.08 0.07 1.79 1.77 1000 1030 454 462 0.95 0.92 2.63 2.58 1055 1035 180 176 0.15 0.15 1.98 2.05 1115 1155 310 322 240 Table B4.4: Analytical Duplicates (Lab Duplicates) submitted for analysis i n 1997 with aqua regia digestion (G32). P Pb Sr T i ppm ppm ppm % original duplicate original duplicate original duplicate original duplicate 690 780 6 12 33 62 0.1 0.13 550 680 4 10 28 42 0.05 0.08 530 480 4 2 30 29 0.1 0.1 810 820 4 4 24 35 0.11 0.18 590 580 2 8 29 22 0.1 0.08 950 870 2 6 107 106 0.09 0.04 790 620 20 4 59 46 0.14 0.12 780 870 8 8 24 52 0.12 0.16 640 640 8 6 33 42 0.13 0.14 790 770 6 2 73 76 0.11 0.1 800 840 2 2 80 86 0.09 0.1 810 710 4 6 76 68 0.1 0.08 620 670 1 6 52 45 0.15 0.14 550 570 6 6 33 40 0.12 0.13 590 580 1 6 38 34 0.13 0.11 810 870 4 4 54 49 0.11 0.09 560 570 8 8 27 30 0.11 0.13 520 490 2 4 40 36 0.11 0.1 530 540 4 1 34 37 0.09 0.1 480 500 6 1 27 33 0.08 0.09 420 430 2 1 29 30 0.1 0.11 580 570 8 6 26 46 0.1 0.15 560 590 2 1 27 37 0.12 0.14 580 530 12 2 30 25 0.12 0.1 540 530 6 6 26 28 0.12 0.11 550 570 6 4 27 26 0.11 0.12 650 660 2 6 33 30 0.13 0.12 650 650 2 6 34 31 0.11 0.12 710 740 8 8 50 49 0.1 0.1 490 500 4 6 33 36 0.13 0.12 710 690 4 6 49 38 0.13 0.11 900 920 10 6 42 30 0.2 0.19 730 700 10 6 34 41 0.09 0.1 730 660 2 6 36 30 0.12 0.11 700 700 6 4 29 27 0.09 0.08 830 1730 1 1 43 33 0.21 0.37 750 730 2 1 28 27 0.21 0.2 241 Table B4.5: Analytical Duplicates (Lab Duplicates) submitted for analysis i n 1997 with aqua regia digestion (G32). V Zn ppm ppm original duplicate original duplicate 52 70 162 202 41 50 94 114 48 47 76 76 62 68 98 106 56 52 134 126 51 41 152 144 70 57 148 140 53 73 140 174 57 65 168 188 53 53 128 134 57 58 138 144 59 52 386 348 64 63 134 138 59 63 116 118 60 52 114 110 68 67 118 118 60 65 88 88 63 60 78 70 55 58 80 80 57 60 80 86 65 65 86 86 53 69 118 132 67 72 106 128 56 52 300 250 57 55 198 206 52 56 202 210 56 55 92 88 51 53 94 92 58 56 110 114 62 65 102 106 67 59 132 126 75 71 128 114 54 61 92 98 62 56 114 102 54 52 100 100 96 93 132 136 82 79 120 126 242 IV O CA O N las los las I SO Os OS E S I id ION N O O N O N lea N O N O T-H CN N O co 00 Tf CN N O m m m in m CO 00 00 O N in in N O in ro P - in N O CO ro" N O N O in P - ; O N CN m ON CO co co in P - ; p-_ N O Tf P - ; oq oq N O N O © •-; CN P ^ ro CN CN CN CN T - H CN CN CN © r- _ m p- oo N O m oq _ N O Tf oo O N m p~ m CN N O Tf CN co P ~ P~- oo CN Tf m oo Tf O N © P - ; N O T - H co CN © CN Tf in Tf in oq oq T - H CN N O O N CN T - H © oq © CN co © CN co ro" CN CO CN T - H ro CN T - H —* T - H T - H T - H —* CO CN T - H —* CN Tf ro ^ CN 30 Tf Tf O N Tf 00 00 CN p- Tf N O N O p- p- T - H N O N O in in oq O N O N in CN O N Tf CN CN O N ON 00 00 00 O N 00 © O N O N © 00 00 O N T-H 00 © O N O N © 00 00 oq O N N O in ©' © ©• ©' ©' © ©' © ©' —< © ©' © rt ©' ©' © © © rt ©" rt T - H H O oo N O O N p- N O CN O N CN CO O N O N oo CN N O N O CN Tf O N N O ro P - CN Tf O N ro p © O N © ON O N © O N T - H © © © ON O N O N © © T-H^ T - H © © 00 oq © O N Tf CO T - H © T - H ©" © © ' " H T - H © ©' © T—H —"' T—t © T - H ' O N O N O N N O ON 00 O N Tf O N Tf Tf in 00 00 00 Tf P - ; 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CO O N rH © i n vq 00 in rH O N 00 oo vq oo Tf in CN CS CN CN CN rH TT rH rH CN T 1 rs CN CS n in m © © m O © © m © © o m i n i n i n © © © © © © i n © © © © © © CO CO ON Tf vo m Tf © i n © rH 00 rH rH CO rH © Tf r- 00 00 CO Tf © V O Tf rH rH rH ON oo CO vo rH oo O N Tf © © ro Tf Tf rH ro Tf Tf CN CN oo vo ro Tf O N m ro TT ro CN TT | n © i n o © i n © © © © © m i n i n © © © © © i n i n o © © © i n © © © i n K t c « o c A ^ o v l n H o m t v 1 • ^ M C * N t l l o ^ N t n H N t l » C N | m ^ ^ M c ^ o - H r o c > v o r o r ^ c S 0 0 r H T f r H © c s c O T f © r O T f i n T f T f © r - ^ N O r O T f © r O T f ^H^H ^ H ^ H ^ H ^ H l i - N f N l C S r H r H r H r H r H r H r H r H r H r H r H C S r H ^ H C O r H C S r H 244 Table B6.1: Analytical Duplicates submitted for analysis in 1997 and in 1996 with aqua regia digestion (G32). A l As Ba Ca % ppm ppm % 1997 1996 1997 1996 1997 1996 1997 1996 3.33 3.33 6 8 180 170 1.13 1.07 2.12 2.02 16 6 130 120 0.59 0.61 2.27 2.02 4 6 130 120 0.73 0.61 1.91 2.14 18 18 110 130 0.42 0.46 1.7 1.43 14 12 110 100 0.66 0.53 1.58 1.6 22 22 100 100 0.48 0.47 1.61 1.65 82 88 100 100 0.67 0.63 2.03 1.94 80 72 80 80 0.64 0.59 1.92 1.73 6 1 170 150 1.54 1.22 2.12 1.68 10 1 150 120 0.91 0.7 2.2 2.35 6 4 180 190 0.81 0.84 1.46 1.45 18 20 110 100 0.59 0.6 1.48 1.45 18 20 100 100 0.56 0.6 1.85 1.85 22 16 120 140 0.71 0.74 1.49 2.04 28 36 110 160 0.68 0.89 2.28 2.04 32 36 160 160 0.99 0.89 2.01 1.96 26 14 110 110 0.57 0.57 1.81 2.12 8 6 150 170 0.74 0.81 2.08 2.24 2 8 170 180 1.11 1.11 1.45 1.55 14 12 100 100 0.48 0.55 1.75 1.89 20 22 120 120 0.69 0.73 2.48 1.89 14 22 170 120 0.93 0.73 1.5 1.56 26 22 120 110 0.37 0.39 1.69 1.9 26 22 120 130 0.39 0.47 0.41 0.43 30 32 70 70 5.11 5.3 2.02 1.98 22 28 170 160 0.7 0.65 1.08 1.25 18 16 250 250 1.42 1.53 3.44 3.84 36 24 100 110 1.1 1.23 1.85 1.8 26 26 590 610 1.3 1.24 1.32 1.26 10 12 940 1060 1.21 1.11 245 Table B6.2: Analyt ical Duplicates submitted for analysis in 1997 and in 1996 with Total Digestion (T24). Co Cr Cu Fe ppm ppm ppm % 1997 1996 1997 1996 1997 1996 1997 1996 28 28 182 192 135 138 5.82 5.8 27 27 173 193 88 71 3.95 3.9 28 27 185 193 88 71 4.12 3.9 22 22 182 211 97 95 3.62 3.85 16 15 117 103 73 64 3.57 3.18 26 28 193 205 92 95 3.22 3.3 17 17 143 167 93 86 3.54 3.4 24 23 187 203 100 86 3.98 3.57 13 11 50 49 156 127 2.69 2.48 15 15 62 54 82 72 3.02 2.68 20 20 73 82 327 314 3.43 3.54 13 14 73 85 62 54 2.73 2.8 13 14 74 85 56 54 2.61 2.8 15 16 87 97 85 85 3.07 3.18 13 16 79 103 68 81 2.44 3.07 17 16 101 103 88 81 3.27 3.07 22 21 202 218 72 69 3.36 3.32 23 25 145 183 110 115 3.33 3.51 16 17 97 106 184 182 3.17 3.23 18 17 102 128 91 80 2.96 3.29 20 20 132 161 77 77 3.2 3.52 22 20 156 161 106 77 3.85 3.52 26 26 270 302 107 105 3.69 3.63 26 28 270 351 210 224 3.8 4.22 6 6 11 11 37 40 1.5 1.58 25 26 51 53 33 29 3.35 3.19 12 13 24 28 31 32 3.12 3.35 16 16 49 54 42 44 3.86 4.23 14 13 32 33 38 33 3.36 3.24 11 9 33 35 66 65 2.83 2.74 246 Table B6.3 : Analyt ical Duplicates submitted for analysis in 1997 and in 1996 with Total Digestion (T24). K M g M n N i % % ppm ppm 1997 1996 1997 1996 1997 1996 1997 1996 0.71 0.72 2.53 2.57 1020 1010 261 239 0.21 0.18 1.9 1.83 1060 940 378 313 0.22 0.18 2.06 1.83 1100 940 410 313 0.07 0.07 1.7 1.8 775 835 508 427 0.09 0.06 1.1 0.93 1610 1490 149 149 0.06 0.07 1.65 1.6 1145 1110 408 363 0.06 0.07 1.28 1.22 1625 1495 395 350 0.08 0.09 1.57 1.41 1065 965 650 535 0.07 0.06 0.69 0.63 6270 4830 87 65 0.11 0.07 0.9 0.74 2040 1765 80 65 0.08 0.1 0.93 0.92 2380 2310 111 96 0.06 0.07 0.96 0.89 955 865 99 83 0.05 0.07 0.93 0.89 870 865 96 83 0.07 0.08 1.13 1.1 1170 1230 106 98 0.06 0.09 1 1.23 1145 1355 143 134 0.08 0.09 1.4 1.23 H 1465 1355 145 134 0.06 0.07 1.45 1.43 910 895 343 312 0.11 0.12 1.36 1.43 1210 1280 275 109 0.13 0.14 1.05 1.06 1260 1255 284 243 0.06 0.07 1.05 1.04 1280 1165 162 138 0.08 0.09 1.24 1.27 1265 1255 213 141 0.14 0.09 1.52 1.27 1490 1255 209 141 0.04 0.05 2.1 2.09 1780 1670 536 446 0.05 0.06 2.07 2.28 1605 1675 508 456 0.04 0.04 0.53 0.55 340 350 17 19 0.28 0.26 0.9 0.85 1230 1170 52 48 0.06 0.08 0.71 0.78 3090 3230 26 24 0.17 0.21 1.29 1.36 675 760 61 49 0.15 0.14 0.87 0.81 2380 2270 34 32 0.1 0.1 0.78 0.71 1215 1120 34 28 2 4 7 Table B6.4: Analyt ical Duplicates submitted for analysis in 1997 and in 1996 with Total Digestion (T24). p ppm Pb ppm Sr ppm Ti % 1997 1996 1997 1996 1997 1996 1997 1996 1660 1720 14 14 36 36 0.37 0.36 920 920 4 4 24 29 0.11 0.15 1030 920 4 4 35 29 0.18 0.15 830 780 10 8 28 32 0.11 0.12 650 740 4 6 40 29 . 0.14 0.09 680 710 4 6 28 25 0.11 0.11 660 720 6 2 36 37 0.1 0.11 630 660 6 6 41 38 0.13 0.13 1220 1130 4 2 103 87 0.05 0.07 910 890 4 4 75 53 0.13 0.09 880 940 10 8 67 71 0.09 0.11 650 600 4 6 30 33 0.1 0.12 620 600 2 6 29 33 0.1 0.12 660 720 1 8 36 41 0.11 0.13 800 860 4 6 28 40 0.05 0.08 830 860 10 6 42 40 0.08 0.08 590 660 6 6 29 32 0.09 0.1 810 710 4 6 38 47 0.09 0.11 1220 1200 2 6 51 53 0.06 0.06 640 650 8 2 23 33 0.1 0.14 830 730 6 2 33 42 0.1 0.12 840 730 12 2 62 42 0.13 0.12 640 650 6 2 19 25 0.09 0.1 710 730 2 10 23 32 0.08 0.11 650 670 64 68 60 63 0.04 0.04 990 1010 22 24 36 34 0.12 0.1 1530 1530 28 30 27 31 0.03 0.04 1390 1320 62 62 156 162 0.09 0.11 1440 1600 40 38 74 71 0.05 0.05 900 920 12 12 73 69 0.09 0.08 248 Table B6.5: Analytical Duplicates submitted for analysis in 1997 and in 1996 with Total Digestion (T24). V Zn ppm ppm 1997 1996 1997 1996 88 93 136 132 62 71 98 92 68 71 106 92 59 66 98 92 65 57 88 80 55 58 76 74 56 62 94 88 67 68 106 94 43 43 144 120 61 50 120 104 54 64 134 134 48 58 76 76 47 58 76 76 55 66 90 90 41 56 94 104 50 56 114 104 59 65 76 74 57 69 98 104 54 60 104 100 52 71 142 138 52 66 162 172 70 66 202 172 51 62 70 72 48 65 76 80 18 19 266 262 51 52 136 134 39 47 142 152 51 58 220 224 54 58 196 188 53 55 92 84 249 *3 &| ca o I C3 .3 60 •c o 1-5 "3 &| J t3 J ca 6 , 5? ca .s ca .9, 60 •c o 1-3 I f ca .3 60 •c o ca .a 'g en vo rH rn OS ON ON Tf in ON m VO m © ON © CN o 00 CN r-» 00 00 m en CN o r» 00 00 in ON CN ON © Tf oo m en Tf en rH rH e'- f- r-- Tf in oo o VO in CS Tf in in oo CN in f- VO en en ON ON ON VO vn rH 00 Tf 00 oo r- VO Tf 00 ON © r-i rH CN rH CN CN Ov Tl- cn r> en in r- o VO in VO cn en VO CS CN rH rH in rH VO VO CO oo oo O CN cn o rH CN VO in ON CS VO Tf 00 00 ON VO 00 cn en CN en Tf CN en in en CN CN rH rH CN CN r- en O O f- in in VO 00 en vo 00 vn r-- Tf ON CS © rH Ov CN vn i—i o Tf Tf CN rn en Tf rH r- 00 oo en © Tf cn m en Tf en CN cn Tf rH rH m CN rH rH CN CN CS Ti- Ov oo en o en rH rs o Tf CS ON CN r- CN 00 ON CN en VO in en CN CN en en CN en en CN CS CS rH CS rH cn CN CN CN CN CN CS Ti- © o m r- © r- in Tf OO © r- © m © CN en Tf en es en en en CS CN en rH CS CN CN en CN CN CN CN CN CS Tf Tf r~ vo ON CS rH CN ON en Tf oo VO oo CN C-; r-- rH Tf VO in vq vq oq as o in oq oq [-; vq oq oq rH ON ON t-; CN CN en Tf r- TJ- m en Tf Tf Tf cn oq CS oo vo ON r— CS VO en VO 1-; vq vq oo oq ON. ON Tf r-; rH oq f- oq ON oq oq o o o o O o o o o o o © © © © © © © © © © vo o 00 m r> rn rH o VO rH 00 rH ON 00 vo CN in vo rH en © vo in in Tt VO m in m VO r- in m m VO VO vo VO VO VO o o o o o o o o o o o © © © © © © © © © © Tf r- oo en oo CS o o r» CS rH © CS CS CN VO Tf Tf CN © m in in in Tf VO in in in e'- (-- r- VO VO in VO VO vo VO VO VO oo oo in Ov Tf m m r- rH en r- VO ON in oo oo ON m ON Tf CN CS TJ- in en Tf oq rH oq oo oo en © rn CS Tf m in vo © CN vd vd vd in vd in vd vn vd vd vd vd vd vd vd vd vd vd VO in vo in rH oo oo CN Tf CS VO CS rH rH rH en t-- r- Tf 00 in r-CN CN en oo en m oq en O r-- © rH cn as vd r~- r~- m en en ON vd vd vd in in vd in vd vd vd vd vd in vd vd vd vd vd in 2 5 0 te 6 , j ca N? O T3 .S3 . 0 0 1-5 i f u ca y 1-5 ca o 1-5 . ca •9 60 •c o ca CJ f 1-6 1.1 60 •c o o OO Tf m o oo Os CO o ON Tf Tf CO OO m OS SO CN CN OO ON f- NO CO o Os m CN ro oo ON o CN oo o OS in T—t O in NO m co Tf Tf Tf CO r- CO T-H co T-H CN Tf ro 00 ON 00 00 Tf o in o 00 00 00 r- NO ON o O SO CN ON T-H NO no 00 00 in o CN NO T—t Os Tf Os 00 00 o CO T-H CN r~- 00 ro ro Tf CO ro SO CO -H CN T-H T-H T—H Tf o\ m CO so CN 00 Tf Tf m m Tf Tf CN m CN CN oo T—t m Os r~ oq ON SO co ON ON in oq r- O c- ON p CN p oq in T—t ^ ~ I—1 T—t CN CN CN T-H T—t cs ON OS oo CN m CN Tf SO Tf oo r- OS ON ON CN O ON oq r- ro p oq p Os NO NO oq ON NO oq O p CN T—t ON sq CN T—t T—t T—t CN CN T-H T-H T-H CN CN CN CN T-H m in in 1/0 m o in in o in m m o m m m o O o o o ON NO m CO SO NO O OS OS m T-H CN T-H CO CN ON m T-H Tf CN ON ro CN CN CN CN r-~ Tf CO o Tf ON CO CN CN NO in oo in O in in in in O o o o o o in in o o m o in o o ro T-H r- NO r- NO CO o co 00 in t-- 00 so m T-H CN 00 m CO SO T—t ON T—i m m CN o CN r- m T—t NO CO Tf ON CO T-H CO CN T-H oo T-H T—t T—1 CN CN T—t T-H T-H T-H T-H T-H 00 00 Tf CO 00 NO r- ON Tf CN m OS 00 in CO in CO p NO IT) *•*. ON OS CN T—t O Tf so CO CN CO sq in .Os CN —; ro CN CN CO CN CO T-H CN CN T-H CO NO Os ON Os T-H m m ro CN Os CO m oo NO oo CN SO CO m NO CO 00 oq ON ON co T ^ co CO NO in sq O sq NO O r-; CN CN CN CN CN CN T-H CN CN T-H CN CO m NO CN CN co oo oo Tf co NO NO NO CN m ro oo m Tf ON OS OS oo T ^ oo oo OS p p OS ON OS OS T-H p p ON d d d d d d d d T—t d d d d d d Tf ON CO SO Tf CN oo ON T—t T-H co CO NO NO m CN 00 ON NO ON 00 ON 00 p 00 00 T-H p p oq p T-H p T ^ . O ON 00 d d d d d d d d d CO NO ro SO so SO oo Tf Tf SO Os Tf CO Tf CO oq SO CN ON t-- ON Tf T~t r-; T—1 co p CN co sq Tf o T-H CO T-H CN ON Tf CO Tf Tf co Tf in CO Tf Tf Tf CO co Tf Tf Tf Tf Tf CO ON T—t Tf CN r-~ ON T-H 00 CN NO 00 Tf in Tf CO Tf Tf oo NO CO © NO CN ON co oo Tf T-H ON CN Tf co ON T-H o Tf Tf ON Tf Tf Tf Tf CO CO Tf CO Tf CO Tf CO CO Tf Tf Tf CO ro 251 o 3 •o a S N & .s 60 •c o o "a, c -a > a O H 03 .a 60 •c o oo P H P. PH - H P H PH Hi P H i f . ca 3 60 •c o cd o ,1 ca O I' o VO Tf C N 00 VO 00 © NO o C N NO oo N© NO © NO VO oo Tf © rH rH © © ON ON ON Tf in Tf m oo ON ON © r- Tf oo ON rH rH rH rH o NO C S NO 00 C N © C N 00 NO C N Tf Tf Tf Tf © © NO © C N C N o C S rH ON ON ON ON C N cn Tf Tf ON ON ON ON p- C O C O m cn © H rH rH rH in V I NO ON 00 00 C O Tf C O ON r- © C N in 00 rH O O in oo Tf ro C S ro co CN) ro ro NO Tf C O ro C N in Tf C O Tf in in ro © rH rH rH rH rH rH rH rH rH rH rH rH rH ON oo oo r- Tf cc oo Tf Tf C N r- rH ON co cn NO C N Tf rH m 00 C N C N ro m C S ro ro m C O C O ro C O C N C O in m Tf cn ro C N TI- NO NO Tf C S NO Tf C N oo Tf © NO C N NO NO Tf C N oo NO NO Tf C N C S Tf oo oo Tf NO Tf rs NO NO © © NO Tf NO NO Tf NO NO Tf oo ro rH rH O © © © © © © © © © o © © © © © © © © © © m Tf NO NO Tf rs C N O O Tf C N ro © NO © in O O ON C O Tf oo oo 00 o\ r-- NO ON C O ON © NO NO NO r- 00 NO NO rH rH © © © © © © © © © © © © © © © © © © © © © C S in NO rH in ON oo oo m C N t-- t-- C N oo r—i rH Tf m oo ro © ON r- oo ON in oo © © © NO NO r- r- t-- r- NO oo ON TJ- N© NO Tf C N N© Tf C N 00 Tf © NO C N NO NO Tf C N oo NO NO Tf C N rH C S Tf oo 00 Tf NO Tf C N vo NO © © NO Tf NO NO Tf NO NO Tf oo ro rH © © © © © © © © © © © © © © © © © © © © © in Tf NO NO Tf C N C N oo Tf C N co © rH NO © m oo ON ro Tf oo 00 00 ON NO ON C O ON © NO NO NO oo r- NO NO © © © © O © © © © © © © © © © © © © © © © rs m NO in ON 00 O O in C N C S 00 rH rH Tf m 00 C O © ON. r-» oo ON t-» 00 © © © NO r- NO r- NO oo ON 252 Table B8.1: Field duplicates sampled and submitted for analysis in 1997 with total digestion (T24). A l Ba Ca Co % ppm % ppm original duplicate original duplicate original duplicate original duplicate 6.51 6.54 680 650 1.63 1.66 24 24 6.64 6.63 650 630 1.68 1.76 24 25 6.69 6.65 610 650 1.88 1.78 22 23 6.36 6.18 620 600 1.73 1.62 21 22 6.66 6.51 650 640 1.69 1.67 23 24 6.18 6.33 540 540 1.74 1.71 25 27 6.17 6.1 530 540 1.83 1.98 29 28 5.98 5.98 590 580 1.73 1.74 26 24 6.46 6.3 630 600 1.76 1.83 20 20 6.26 6.18 590 600 1.85 1.77 21 21 6.65 6.39 670 620 1.72 1.65 23 20 6.67 6.29 640 600 1.74 1.8 23 22 6.14 5.74 540 530 1.68 1.62 31 29 6.31 5.99 570 550 1.79 1.77 28 26 6.5 6.06 650 630 1.78 1.69 21 26 6.38 6.38 620 620 1.86 1.79 24 20 6.89 6.65 680 620 1.66 1.66 24 21 6.6 6.29 680 610 1.59 1.56 32 26 6.47 6.49 640 720 1.71 1.66 21 25 6.82 6.44 680 630 1.81 1.73 22 20 5.61 5.89 500 500 1.45 1.53 29 31 5.64 5.55 540 480 1.19 1.48 36 30 5.54 5.79 500 530 1.41 1.38 37 39 6.54 6.79 700 660 1.68 1.76 20 20 6.9 7.18 690 740 1.65 1.59 21 21 6.72 6.69 670 680 1.69 1.78 23 23 7.02 6.9 580 580 1.97 1.88 28 30 6.39 6.45 510 520 2 1.97 31 30 7.37 7.09 540 530 1.98 1.94 27 30 6.26 6.5 530 570 1.55 1.61 26 30 6.18 6.32 570 570 1.36 1.44 28 29 5.87 6.04 510 510 1.83 1.84 25 28 5.34 5.75 470 500 1.86 1.93 29 26 5.97 6.08 490 510 2.14 2.18 27 27 6.38 6.24 530 540 1.68 1.57 31 29 6.58 6.37 580 570 1.98 1.82 34 27 5.93 6.15 510 540 1.82 1.71 25 25 6.99 6.9 690 690 1.72 1.68 23 20 6.86 6.84 670 680 1.66 1.7 18 18 7.09 7.42 700 710 1.71 1.69 19 18 7.16 7.4 710 750 1.82 1.76 19 23 6.8 6.71 630 640 1.88 1.87 18 16 7.3 7.73 750 750 1.79 1.89 20 21 7.18 7.2 710 740 1.74 1.7 17 20 7.28 6.38 710 670 1.88 1.89 19 21 6.21 6 650 580 2.09 2.17 14 13 5.83 5.96 540 530 2.32 2.29 15 15 253 Table B8.2: Field duplicates sampled and submitted for analysis in 1997 with total digestion (T24). Cr Cu Fe K ppm ppm % % original duplicate original duplicate original duplicate original duplicate 203 240 60 74 3.93 4.06 1.15 1.1 230 272 90 102 3.9 3.93 1.1 1.11 278 221 53 63 4 3.94 1.09 1.09 256 202 80 153 3.83 3.66 1.1 1.05 203 209 77 138 3.76 3.57 1.15 1.1 289 313 58 59 3.91 4.18 1 1.02 307 319 80 79 4.02 4.06 1.01 1 264 244 59 93 4.15 4.03 0.93 0.94 193 195 52 59 3.5 3.51 1.09 1.01 221 235 163 67 3.78 3.72 1.01 0.96 173 165 74 77 3.59 3.38 1.14 1:11 218 220 63 60 3.69 3.7 1.16 1.08 333 283 56 68 3.97 3.63 0.9 0.85 270 265 71 172 3.8 3.65 0.98 0.94 204 184 85 60 3.78 3.64 1.08 1.06 199 175 69 131 3.78 3.69 1.02 1.05 192 175 68 54 4.22 3.72 1.16 1.14 291 212 121 88 4.33 3.83 1.15 1.09 227 243 96 71 4.02 4.16 1.11 1.08 216 183 70 51 4.05 3.64 1.16 1.07 485 586 180 144 3.96 4.34 0.81 0.88 368 674 134 153 3.79 4.1 0.82 0.81 644 528 301 201 4.11 4.36 0.83 0.83 166 198 58 63 3.81 3.97 1.17 1.17 170 171 65 65 3.93 4.14 1.21 1.3 174 188 50 50 3.69 3.73 1.15 1.15 298 292 147 90 5.2 5.14 1.26 1.24 443 390 286 81 4.88 4.6 0.97 0.98 219 243 95 108 6.21 6.41 1.6 1.61 296 324 145 201 3.97 4.24 0.96 0.96 273 317 90 110 3.95 4.12 0.9 0.95 409 356 91 76 4.06 3.89 0.91 0.94 345 329 95 74 3.83 3.98 0.78 0.86 589 607 81 91 4.56 4.57 0.87 0.9 294 360 75 82 4.74 4.34 1.07 0.99 399 357 126 150 4.98 4.28 0.98 0.97 405 350 83 106 3.88 3.78 0.92 0.96 210 199 185 187 4.21 4.13 1.11 1.13 155 190 240 88 3.98 4.13 1.1 1.12 164 165 158 343 4.33 4.45 1.13 1.22 139 145 186 186 4.16 4.24 1.15 1.17 150 130 60 94 3.93 3.79 1.17 1.14 121 132 73 267 4.12 4.7 1.2 1.21 115 116 116 76 3.83 3.78 1.23 1.26 128 120 99 218 4.52 3.66 1.14 0.99 90 89 70 63 3.36 2.95 1 0.96 111 123 227 144 3.06 3.26 0.95 0.96 2 5 4 Table B8.3: Field duplicates sampled and submitted for analysis in 1997 with Total Digestion (T24). Mg Mn Na Ni % ppm % ppm original duplicate original duplicate original duplicate original duplicate 1.94 2.21 1615 1470 2.05 2.04 166 176 2.25 2.63 1500 1415 2.03 2.12 204 236 2.13 2.11 1465 1645 2.08 2.14 176 183 2.02 2.05 1335 1390 2.13 2.03 159 174 2.12 2.06 1650 1715 2.22 2.19 177 172 2.68 2.95 1190 1165 1.87 1.87 601 638 2.83 2.71 1280 1195 1.83 1.85 823 803 2.5 2.42 4460 3650 1.65 1.68 520 477 1.81 1.74 1620 1360 2.06 2 165 148 2.24 2.18 2410 2800 1.9 1.84 265 275 1.97 1.84 2470 1915 2.11 2.14 197 165 2.07 1.98 1720 1345 2.21 2.1 170 165 2.91 2.73 1640 1610 1.81 1.71 327 314 2.7 2.46 1840 1515 1.88 1.85 287 263 1.95 1.92 2340 2070 2.02 1.98 189 190 1.87 1.76 1625 1455 1.99 2.11 156 144 2.07 1.94 1325 1225 2.1 2.13 174 157 2.6 2.23 1490 1160 1.9 1.68 320 286 2.07 2.3 1635 3440 2.09 1.93 178 217 2.08 1.82 2490 2070 2.16 2.08 210 172 3.57 3.8 1085 1285 1.71 1.88 431 471 3.47 3.55 2130 1715 1.55 1.66 524 484 4.16 4.15 2710 2320 1.67 1.71 573 581 1.66 1.96 1195 1260 2.25 2.17 121 157 1.88 1.88 1360 1105 2.16 2.28 143 142 1.9 1.83 1340 1320 2.16 2.33 159 153 3.1 3.22 1065 1155 2.28 2.25 339 370 3.22 3.23 1445 1305 2.05 2.12 421 390 3.2 3.32 1190 1230 2.34 2.33 231 250 2.88 2.97 1100 1505 1.92 1.88 524 574 2.86 2.96 1175 1410 1.7 1.77 578 585 2.84 3.13 970 1190 1.92 1.93 308 381 3.14 3.02 1340 1055 1.43 1.57 444 399 3.18 3.33 1315 1385 1.9 1.97 353 375 2.99 3.13 1250 1120 1.95 1.92 386 446 3.51 3.01 1545 1170 1.98 1.99 449 393 3.11 3.19 1320 1335 1.88 1.95 389 407 1.95 1.92 1590 1230 1.85 1.95 200 181 1.74 1.77 1125 1195 1.84 1.95 146 146 1.73 1.68 1225 1180 1.9 1.97 160 131 1.61 1.62 1845 2480 1.96 1.9 117 129 1.4 1.35 1590 1500 2.27 2.18 71 69 1.52 1.6 2670 2710 1.86 1.71 114 132 1.42 1.48 1765 2330 2.07 2.1 89 102 1.55 1.34 1590 2980 1.7 1.45 118 125 1.11 0.98 6010 4680 1.71 1.71 88 79 1.11 1.16 3050 2490 1.71 1.75 80 84 255 Table B8.4: Field duplicates sampled and submitted for analysis in 1997 with Total Digestion (T24). P Pb Sr T i ppm ppm ppm % original duplicate original duplicate original duplicate original duplicate 700 680 6 6 278 273 0.46 0.46 710 670 6 6 271 286 0.46 0.48 730 770 6 4 285 291 0.51 0.45 740 720 6 8 286 258 0.45 0.4 750 750 6 4 290 282 0.45 0.42 600 600 4 6 244 239 0.42 0.45 590 620 6 4 247 252 0.44 0.44 880 870 2 6 230 227 0.38 0.36 660 620 4 4 284 270 0.45 0.43 790 790 4 6 259 252 0.43 0.4 800 740 6 6 281 277 0.4 0.41 780 810 6 4 299 286 0.47 0.46 560 620 8 4 232 210 0.4 0.37 640 660 6 6 247 240 0.42 0.39 720 670 8 4 277 267 0.47 0.44 670 630 4 6 263 281 0.44 0.45 730 630 6 1 262 272 0.47 0.47 840 960 6 4 253 225 0.43 0.36 660 750 4 6 276 252 0.46 0.43 740 680 6 6 291 280 0.47 0.44 690 730 4 4 227 249 0.37 0.46 830 720 8 8 205 232 0.34 0.44 700 810 2 4 224 225 0.39 0.37 740 710 8 6 292 291 0.46 0.47 760 750 6 6 285 297 0.47 0.51 710 730 8 6 290 316 0.42 0.47 1180 1260 4 4 255 235 0.8 0.8 930 930 4 4 245 237 0.74 0.71 2060 1960 1 1 187 174 1.15 1.19 830 830 6 4 238 243 0.41 0.45 950 880 10 6 215 234 0.36 0.42 640 650 6 2 252 247 0.48 0.49 950 960 6 4 189 209 0.35 0.38 560 580 8 4 252 267 0.56 0.59 1050 850 4 4 195 222 0.65 0.46 750 710 6 8 247 257 0.55 0.48 640 630 6 2 244 242 0.48 0.44 960 930 6 8 281 284 0.43 0.42 930 890 6 4 269 283 0.4 0.44 1070 1060 4 4 280 286 0.43 0.47 930 1030 6 8 282 283 0.45 0.46 780 780 6 4 314 312 0.52 0.48 1120 1320 6 6 275 282 0.42 0.45 990 1000 4 6 301 301 0.42 0.42 1130 1140 6 8 273 255 0.42 0.35 1170 1200 6 4 295 293 0.36 0.34 1270 1230 4 6 313 300 0.39 0.42 256 Table B8.5: Field duplicates sampled and submitted for analysis in 1997 with Total Digestion (T24). V Zn ppm ppm original duplicate original duplicate 151 154 448 456 146 151 240 266 152 145 136 148 143 135 140 140 142 136 142 154 141 151 104 110 147 145 100 102 138 130 118 114 140 135 96 86 139 134 108 106 132 128 122 108 144 143 98 98 143 133 94 94 146 130 98 96 152 147 108 100 149 143 98 92 153 148 110 96 151 133 116 114 151 146 94 104 155 148 110 94 119 137 100 108 111 135 104 108 126 126 138 118 146 152 138 120 154 161 154 134 147 147 128 148 165 160 118 152 169 156 138 130 152 159 138 150 132 145 118 116 125 131 118 114 149 151 90 86 124 130 102 94 172 182 98 102 137 138 124 116 173 152 118 104 148 140 104 98 139 138 370 260 135 143 362 328 143 154 392 188 150 150 228 210 156 148 104 110 140 147 158 208 132 135 142 148 144 125 216 268 121 110 148 136 123 133 146 166 2 5 7 ON co CN ONC>o©T-HNOTfONCNaNl^ONCNi(OCNTfoOTfi----cocNCN c^r^NONocNC^NON©r~oooo©ooTfcnt---cN'-'coTfr-^ H H ( N | M H H fN T-H N - H r t r t r H r t r t t N I-a 9 60 •c o TfcN©©fNi^Tfooc>r t ioc> i> -cor - - co t^ t^TfT -Hoo c>0©Tfc0CNiOcON©r---aN00O0N©c/-N00T-<.-H©Tf00 H (S N M H H (S T ^ r s 1 _ T - H . - , T - . T - H T - H ( N roOTj -Nor- r -NOTfor- r -~NOTr N N N M H t N N - I C N - H — i , - H ON NO ON t-~ O O ON —i CN T-H T-H CN <N rN I U & 1-5 CN .9 , 60| G o O N i r i T t r f c c - H - t c o r-HCNCNCNr-HCNCN—< o c N v o r - N O T T O t o N o o o r - o o N o C N C N T - I T - H T - H C N C N C N T - H T - H T - H . - H C N CO ON NO LO ON Tf NO o d d o m r-d d CO t CO Tt" TT O © —i t-~r-HCNNONO"OTj-OOIOCOCONO r^-ONlOQlOlONONOlOWOlOTt-o d d c S d d c s c i o c i c s . ca . o u ^ 1-5 NO - H CN N O N O • — l O O r - N O O N N O O N J - J N O L O O O N O , - ; d d © © © mTf-NOON-HONCNONTt-Tl-Nor-NoiooominTrNo^ d d d d d d d d d o I CO o o o o o o o o o o o o o o o o o o o o o CO'-HCNTfONt^OCNcONO^OOCNCN'O'-HOO'-HO'O . ca c 1-5 . ca 9 60 •c o o o o O CN CO o o o o CO O NO ON o o o o o o o o O O Tf ON CN Tf CN V) 1 I f~vj fN) ' ' T—t T-H T-H T-H o o o o o o ON ON ON T-H CN ca u f l If. 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N N o c N c s r ^ o o c > O N N o r - - . o o o o N o i n f ^ T t - c o O N T r > r ) N O N n N o r ^ N © N o o O T r N O N O N o i r > i n r - ~ N © N o i > o o N O N o i n l> s. 1-5 ca .a . •S" o c o c o r - - c o c N - H m O N i / - i — I C N C O N O O O O NONONONONONOr -^NONOr- NONONONOl>-ON i>- O NO NO 00 oo co T1-m NO in T)- m oo o o o o o o o o o o o o o o o © o rtr-HTf—icNCOCNm-HCNOO-HCNCNCN »—t *-H CN O *-H O »-H *—1 T-H ' 1-5 r-H •— IOOCN-HOOOO-H^HONCNCO'-HCN '— I * N H a i - H r - H * - H © * - H » — 1 » — < 0 » — < I - H © I - H T — 1 » - H * - H * - H . - H I - H » - H T - H © it?1 o CN CO •—lONro — o o O N O o o o m o s o o O N c o c o c N o o c o m c o O O c o c N c O T i - c o c o c N O N C X)inr - - C N c o c o c o c o T ) - c o c o c o r o PHI §.1 ca .a 00 •a o c>i^co i^i^cx5Trco^TfNoc^^Tfini^i^cNONr-^r-~ CNCNcOCOCOCOCNt^C )OC»t^cOTrcOCOTfrOrOCNrOCN NO •° a I OH PH 1 PH NONONOTtNOOONONONOOOTl-NOTj-NOOOOONOTfNOO ca o %l 1-5 ca .a . c o C N O O O N O T ^ O O C N O O T T CO -H NooooooNoooNOTrooTj-NOTi-o CO o o o o o o o o o o o o o o o o o o o o o ^ r r c « T r - H T } - o r - - ' - H ^ H N o o N C N c o T r c N O o o N o ^ H ^ N O N © i n r ^ N o i n c » o o O N i ^ i ^ r f i n T r > n N o r - - i n i n N O N o \ ^ PH PH 1-5 . ca '•I, •c o o o o o o o o o o o o o o o o o o o o o o C^NOONCWONOOTfOOONTrcO'^-ONOTf^HOONCNCOO inNoinNoinTft^Not^oooo in in in in r^NoiriiiONONo 260 Table B10.1: Field duplicates sampled and submitted for analysis in 1997 with aqua regia digestion (G32). Al As Ua Ca Co % ppm ppm % ppm original duplicate original duplicate original duplicate original duplicate original duplicate 1.72 1.6 12 10 11U 100 0.64 0.59 22 22 1.5 1.47 6 16 100 100 0.5 0.46 19 21 1.65 1.74 20 12 100 120 0.6 0.67 19 17 1.57 1.62 16 10 100 110 0.59 0.61 18 19 1.57 1.52 22 12 110 110 0.54 0.59 20 20 1.77 2.01 60 70 80 80 0.59 0.57 22 24 1.74 1.86 68 68 70 80 0.72 0.9 25 23 2.04 2 90 86 170 150 0.93 0.91 22 21 1.64 1.72 12 16 130 120 0.68 0.63 18 18 1.76 1.98 34 44 130 150 0.77 0.86 17 20 1.79 1.58 16 24 140 110 0.76 0.65 20 18 1.42 1.5 14 18 110 110 0.52 0.62 19 19 1.93 1.85 14 20 130 130 0.58 0.64 26 25 1.86 2.16 18 16 120 130 0.71 0.9 24 24 1.9 1.63 14 12 150 140 0.73 0.62 20 19 1.71 1.83 8 6 120 120 0.6 0.74 21 20 1.87 1.57 8 12 120 100 0.66 0.5 20 20 1.94 2.03 10 6 150 160 0.69 0.81 26 23 1.51 1.84 10 10 120 190 0.51 0.65 17 22 1.75 1.8 10 8 140 130 0.69 0.71 18 19 1.72 1.51 26 22 120 100 0.38 0.36 24 22 2.03 1.52 20 16 160 100 0.49 0.41 31 24 1.69 1.96 26 28 150 150 0.41 0.5 32 32 2.06 1.64 4 12 120 100 0.79 0.62 19 16 1.7 1.63 12 12 110 100 0.61 0.51 20 18 1.6 1.58 6 10 110 110 0.64 0.64 18 19 2.34 2.34 14 8 120 130 0.63 0.6 26 25 2.25 2.36 1 16 110 110 0.56 0.58 27 28 3.36 3.53 10 10 200 210 1.05 0.92 25 29 1.93 1.92 14 12 120 130 0.4 0.38 22 26 2.06 2.14 12 14 150 150 0.42 0.45 22 26 1.69 1.47 12 16 100 90 0.58 0.49 22 23 1.85 2.05 16 20 120 130 1.05 1.08 24 20 1.84 1.46 10 12 90 90 0.66 0.46 23 22 2.42 2.15 8 20 140 130 0.79 0.6 29 25 1.91 1.6 14 12 110 100 0.51 0.45 28 22 1.63 1.62 14 12 100 110 0.53 0.49 21 21 2.46 2.36 4 12 170 170 0.91 0.86 20 20 2.27 2.38 12 1 160 170 0.85 0.85 17 17 2.33 2.42 10 10 170 180 0.82 0.79 16 16 2.45 2.67 2 8 180 210 0.88 0.92 19 19 1.5 1.64 6 4 90 100 0.61 0.73 16 16 2.6 2.94 1 16 200 210 1.1 1.21 18 18 2.32 2.25 1 8 140 160 0.96 0.93 16 18 2.84 2.86 8 1 200 240 1.2 1.43 18 21 1.91 1.91 8 2 190 160 1.41 1.5 14 12 1.78 1.81 1 2 130 120 1.46 1.43 14 14 261 Table B10.2: F i e l d duplicates sampled and submitted for analysis i n 1997 with aqua regia digestion (G32). Cr Cu Fe K M g ppm ppm % % °A > inal duplicate original duplicate original duplicate original duplicate original duplicate 129 131 61 II j . b i 3.8 U.09 0.08 1.33 1.51 122 136 75 92 2.99 2.99 0.07 0.06 1.35 1.62 147 138 53 55 3.73 3.54 0.07 0.09 1.23 1.28 123 124 85 164 3.37 3.33 0.08 0.08 1.27 1.31 115 119 79 137 3.1 3.22 0.07 0.07 1.23 1.28 180 207 61 59 3.52 3.7 0.07 0.07 1.42 1.57 180 187 78 81 3.43 3.55 0.08 0.1 1.51 1.49 163 155 61 95 3.8 3.73 0.09 0.09 1.49 1.45 104 104 48 63 3.05 3.2 0.07 0.07 1.06 1.11 119 137 176 70 3.19 3.48 0.07 0.08 1.23 1.33 110 96 73 78 3.09 2.83 0.08 0.07 1.22 1.11 102 112 53 58 3.07 3.22 0.07 0.08 1.11 1.15 191 181 61 70 3.63 3.2 0.06 0.07 1.47 1.45 161 172 72 207 3.25 3.63 0.07 0.1 1.36 1.45 114 101 94 70 3.32 3.03 0.09 0.08 1.22 1.12 110 114 66 156 3.44 3.66 0.08 0.09 1.08 1.16 115 96 60 52 3.63 3.19 0.09 0.07 1.19 1.07 181 140 108 83 3.63 3.45 0.12 0.12 1.51 1.29 118 152 94 72 3.24 3.56 0.08 0.09 1.1 1.33 126 127 66 54 3.24 3.46 0.09 0.09 1.14 1.16 231 228 224 152 3.79 3.4 0.05 0.04 2.02 1.87 234 266 141 138 3.56 3.53 0.07 0.05 2.18 1.95 288 301 336 216 3.98 4.08 0.05 0.07 2.31 2.48 108 103 72 65 3.86 3.27 0.12 0.08 1.25 1.12 98 92 69 60 3.47 3.37 0.08 0.08 1.15 1.1 112 104 48 47 3.22 3.17 0.08 0.08 1.25 1.19 180 161 147 86 4.52 4.22 0.37 0.36 2.09 2.07 243 224 296 88 4.35 4.2 0.15 0.17 2.05 2.17 152 161 95 105 6.08 6.18 0.92 0.97 2.58 2.64 175 180 159 200 3.53 3.54 0.07 0.07 1.76 1.72 174 199 88 111 3.42 3.78 0.07 0.08 1.85 1.94 213 187 119 69 3.61 3.11 0.08 0.06 1.69 1.49 203 213 100 76 3.37 3.53 0.08 0.09 1.66 1.63 287 222 98 104 4.36 3.51 0.07 0.05 1.87 1.58 188 231 75 87 4.5 4.03 0.28 0.16 2.08 2 214 190 126 137 4 3.44 0.08 0.06 2 1.63 207 197 86 103 3.36 3.14 0.06 0.06 1.66 1.58 125 112 169 207 3.83 3.91 0.12 0.1 1.43 1.33 95 105 249 91 3.77 3.76 0.1 0.11 1.22 1.26 82 86 153 333 3.54 3.98 0.1 0.09 1.04 1.05 83 91 199 176 3.78 3.88 0.11 0.13 1.1 1.13 63 67 54 96 3.38 3.58 0.07 0.07 0.85 . 0.9 71 74 73 259 3.58 3.94 0.11 0.11 1.07 1.04 64 70 113 73 3.42 3.4 0.09 0.1 0.98 1.01 85 78 98 236 4.23 3.56 0.12 0.14 1.09 1.05 49 49 81 65 2.91 2.55 0.08 0.07 0.69 0.69 68 66 210 137 2.69 2.96 0.08 0.07 0.67 0.73 262 Table B10.3: F ie ld duplicates sampled and submitted for analysis in 1997 with aqua regia digestion (G32). M n N i T l>b Sr ppm ppm ppm ppm ppm original duplicate original duplicate original duplicate original duplicate original duplicate 148b 1340 122 129 590 600 4 6 41 33 1135 1135 133 162 530 530 6 2 28 25 1215 1340 117 118 590 570 1 6 37 46 1175 1270 106 117 630 610 6 4 35 35 1545 1555 133 117 620 620 8 1 32 34 1030 980 498 548 480 500 6 6 36 36 1055 990 679 701 490 530 6 8 39 51 4550 3520 428 378 730 710 1 6 49 49 1405 1365 115 115 520 530 6 6 32 31 2430 2820 191 219 610 680 1 6 39 46 2300 1825 139 116 640 610 2 2 42 36 1405 1135 104 111 620 660 2 6 28 33 1555 1465 215 200 430 460 1 2 30 33 1770 1490 188 201 540 540 6 8 35 48 2410 2040 143 132 570 550 2 8 39 31 1540 1370 105 117 570 520 8 6 30 43 1055 1040 110 99 530 540 4 8 36 24 1215 1000 209 201 610 790 4 12 39 37 1375 3140 115 148 520 590 4 2 28 39 2270 2060 142 133 550 570 6 6 38 42 1025 1060 251 266 610 550 6 2 22 23 2080 1415 353 280 660 520 6 2 32 25 2810 2260 360 360 580 640 8 1 22 32 1120 1085 101 106 680 580 2 6 59 34 1270 885 105 89 640 610 6 6 35 32 1115 1160 115 107 570 590 6 2 40 43 815 900 262 263 1020 980 8 1 28 27 1155 1095 322 317 730 770 1 4 27 25 1035 1055 176 187 1730 1620 1 1 33 28 945 1295 404 435 670 670 8 10 24 22 990 1240 456 470 720 700 10 10 29 29 805 920 242 230 570 530 8 6 34 23 1195 905 300 277 690 720 10 4 40 45 1030 1135 270 251 530 460 6 6 41 23 1105 975 293 338 920 720 6 10 30 28 1235 830 322 269 590 520 8 10 29 25 1115 1125 271 269 540 520 6 6 28 23 1340 1115 152 144 680 730 2 6 76 68 970 1045 115 116 730 660 4 2 65 71 990 965 105 92 710 790 6 8 68 57 1710 2180 93 100 720 710 1 4 70 76 1310 1355 51 56 630 680 6 4 37 51 2460 2480 88 96 840 950 2 8 86 97 1605 2160 71 78 770 810 2 6 76 70 1415 2970 93 104 870 890 4 8 93 111 6680 4740 76 68 870 930 6 4 106 103 2780 2300 61 68 880 900 2 6 102 89 263 Table B10.4: F i e l d duplicates sampled and submitted for analysis in 1997 with aqua regia digestion (G32). f l v Zn % ppm ppm original duplicate original duplicate original duplicate U.14 U . U 67 62 458 4/6 0.11 0.1 55 52 206 250 0.14 0.15 72 69 128 132 0.13 0.12 59 57 134 138 0.11 0.12 53 56 136 154 0.12 0.12 63 65 96 106 0.13 0.14 60 68 92 94 0.1 0.11 59 59 116 108 0.12 0.11 57 54 80 84 0.08 0.12 49 61 100 108 0.11 0.1 55 49 114 98 0.11 0.12 56 57 80 80 0.11 0.11 65 61 86 88 0.11 0.13 61 69 90 98 0.13 0.1 63 54 102 90 0.13 0.15 65 71 88 90 0.14 0.1 65 58 92 84 0.12 0.08 66 59 100 100 0.1 0.12 54 64 76 94 0.12 0.13 60 69 96 94 0.07 0.08 46 51 104 92 0.09 0.09 53 58 100 88 0.08 0.1 52 56 126 114 0.17 0.11 72 52 148 110 0.12 0.12 58 55 156 118 0.13 0.14 63 60 118 140 0.23 0.21 75 67 102 132 0.2 0.22 79 71 126 128 0.37 0.38 93 94 136 132 0.09 0.09 54 57 104 98 0.09 0.11 53 58 106 102 0.14 0.09 67 54 90 68 0.08 0.09 56 60 92 86 0.18 0.11 86 66 90 88 0.19 0.14 71 61 114 104 0.14 0.11 69 61 100 88 0.12 0.11 62 55 96 84 0.12 0.11 67 61 342 276 0.1 0.12 58 66 362 332 0.08 0.09 52 58 348 164 0.12 0.12 63 71 228 192 0.12 0.14 63 69 86 106 0.1 0.08 58 57 144 182 0.1 0.12 53 56 134 134 0.11 0.1 62 60 212 276 0.04 0.06 41 44 144 130 0.08 0.09 56 59 130 150 264 •I IO i a l> p. 13 S * T p. . 6 0 2 |3 16 . 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NO i n Tf 00 ON T - H f i f i f i f i Tf T - H CN i n r - f l oo oo oo oo oo d d d © © Os Tf T - H ON t> T - H •rd- T - H f i f i Tf Tf o Tf p- CN ,_ oo f l o T—H © ~ T - H CN Tf f l m oo p- p- Tf oo so o © Tf Tf f i SO so v© Os SO CN © P"-CN f ) f l Tf f l m OS CN SO Tf r-t Tf f l Tf © © O © © o Tf © Tf © i n m m m m Tf ,_ p- Tf NO sq sq oq i n i n i n i n i n i n f> oo OS 00 f i Tf T - H OS CN f l f l CN f i Tf m NO 00 00 00 00 oo CN CN CN CN CN 288 Table C 5 : S u m m a r y o f average concentrations o f elements i n creeks f r o m 1996 s a m p l i n g and analyt ica l results after digest ion w i t h h y d r o x y l a m i n e h y d r o c h l o r i d e . B6 B l B2 B3 B4 B5 mean Ag ppm 0.20 0.20 0.20 0.40 0.26 0.25 A l % 0.77 0.88 0.80 0.80 0.81 1.14 0.89 As ppm 7.60 6.00 15.38 2.89 2.75 3.00 6.00 Ba ppm 104 100 84 97 104 160 109 Be ppm Bi ppm Ca % 0.23 0.41 0.48 0.46 0.53 0.91 0.56 Cd ppm 0.50 0.54 0.62 0.53 0.74 2.33 0.95 Co ppm 18.8 18.2 16.0 13.6 14.8 14.1 15.3 Cr ppm 50 44 29 27 26 21 29 Cu ppm 186 120 63 108 112 118 104 Fe % 1.91 1.87 1.64 1.57 1.73 1.93 1.75 Ga ppm Hg ppm K % 0.01 0.06 0.03 0.03 0.04 0.04 0.04 La ppm Mg % 0.97 0.84 0.60 0.58 0.54 0.43 0.60 Mn ppm 1321 908 1124 1006 1136 2590 1353 Mo ppm Na % Ni ppm 186 240 246 96 98 57 148 P ppm 368 565 431 350 522 514 476 Pb ppm 4.40 9.84 4.75 4.67 5.18 6.00 6.09 Sb ppm Sc ppm Sr ppm 14 18 23 19 24 67 30 Ti % TI ppm U ppm V ppm 19 25 22 23 26 27 24 W ppm Zn ppm 56 72 94 81 99 106 90 2 8 9 .s? l-£> 1) ao ca -+-» s o fc! | -»-» o . 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cn vq cn © CN Tf T-H co •—\ c o oq r--CN T—H CN T-H CN CN T—H T-H T-H r - H r - H r - H csi T-H T-H r H r H r H csi T—H T-H f N CO ft ft CU CU © © © © © o © o CJ © © © © © © CJ I* © © © © © © © © © Tf Tf Tf Tf Tf Tf Tf Tf OO oo 00 00 00 00 Tf Tf Tf Tf Tf Tf Tf Tf Tf Ov Os OS OS OS OS OS OS O Tf Tf Tf Tf Tf Tf o CN CN CN CN CN CN CN CN CN 00 00 H H B B CU cu © r ^ CN co Tf CO SO Ps E CN r o Tf c n VO Ps E VO ps 00 OS © T-H CN CO Tf Tf Tf Tf Tf Tf Tf Tf Tf cn cn cn cn cn m CN CN CN CN CO r o c o r o CO m CO c o co c o c-o CO r o T3 CU c o CO r o r o r o c o cu CO CO r o CO c o CO c o r o r o 00 00 312 1^  J 60 03 ICQ o ci CD I 00 f—' oo CN Tf VO o vo VO oo O CN oo CN CN vo o O 00 VO Tf Tf CN o E T—t O oo OS Ov o r- r- o O oo o Ov oo Ov Os oo r- O r- r- OS fr rH T—t T—t TT T—t T—t rH VO c n cn o CN © en o r- T—t Tf T—t en CN o Tf cn oo Tf Ov CN CN E vo cn cn VO VO cn >n cn r- cn i n >n m vo VO cn Tf VO c n i n VO PH PH m rt en CN Tf cn Tf Tf rt VO CN rH CN T—t en Tf CN rt VO Tf T—t Tf * — i d T T T T T—t rT T T ""I T - T - 1 T T d rH T T T—t T—t T T TT T—t d T -0S- d o o © o o o o o o o o o o o o o o o t—t Ov CN CN Ov o Ov en r- CN rt 00 VO T—t Tf en o o rt m Tf cn o E Tf m en en Tf m c n CN c n cn en c n en en c n Tf en en m Tf CN Tf PH PH o oo o O vo vo Tf Tf Tf Tf oo oo vo CN oo T—t vo vo oo VO VO VO s »-H rH PH PH O o o o O o o o o o o o o o o o o o o o o o S cn r- t- Ov Ov CN en en CN cn Ov cn m o Tf T—t VO Os 00 OV VO Ov r H p. vo r- VO OO cn VO vo vo VO m vo vo vo m VO VO VO r~- cn i n i n PH 1—' t-» VO VO Tf m m rt rt Ov Ov rt cn en T—t Tf r- rt cn VO r- m CO E rt« Ov © Tf 00 r- o Ov CN Tf rt 00 r- Tf CN cn 00 r- Os vo vo oo PH rH rH c n rH r l rH T - H T—t H T—t T—t T—t T—t rH T—t PH >n cn >n m o m cn o O o o m o o m cn o cn cn o o O E cn Tf oo T—t ov CN CN rH en Tf CN T—t cn m Tf c n oo rH vo p~ r- OS PH Ov VO vo P- 00 00 00 00 O Ov 00 00 r- 00 m oo c- cn cn cn m oo T—t >n rt c n Tf en VO p- CN CN <n CN m cn Ov en rt p- m oo CN i n r o CN T—t r^  en oq vo CN CN CN vq rt vq vq CN CN vq q OS T - ; OS oo oq T H T T T—t rH T—t T T T—t T T T—t T—t rH rH d "~' d d *-' CM Ov oo o\ rH oo oo Ov Tf Ov T—t OO rH oo m OS vo T—t o o o d d o o O rH o d d d o d d o T * o o d 0S- d d d d d d d d d d d o d d ,_ Tf cn en oo CN CN VO oo rH cn Tf rt CN i n cn Tf r-- Tf m oo OO Tf i n c~- oq Tf en T " , Tf Tf T - ; en Tf Tf en vq en CN Tf oo f- oq c n en r n en en cn en en en en en c n en CN CN CO rH r» cn Tf Ov rt r- cn m T—t o Ov Ov vo oo r- en r-~ o CN rt VO rH E Ov cn >n Os vo cn m Tf vo r- Tf vo vo Tf 00 r- cn m oo cn Tf VO PH PH f—1 00 o vo c n rt o c n OO CN vo CN vo cn CN VO Os cn rt en Os CO rt E CN OV T—t CN r- m o OV CN en rH m VO Tf en i n oo oo OS r~ r-PH rH T—t CN T—t T—t T—t rH T—t T—t rH rH * - H T—t T—t T—t PH <-H OV >n 00 00 Tf r- 00 i-» o CN r- CN rt Ov o CN cn vo en Tf Tf E H rt rH CN CN CN T—t rH CN CN r l CN CN rH CN CN T—t rH T—t rH rH CN PH PH rH Tf cn cn Ov Ov oo VO Tf cn T—t r- r-- CN i n rH Tf i n T—t i n Os r- cn © cn VO cn Tf Tf cn VO vo f- cn o VO vo m m P-_ VO Tf vq o - d d d d d d d d d d d d d d d d d d d d <—< o o o o o o o o o o o o o o o o o © o o o o E m CN Tf CN CN en T—t o cn cn cn o T—t en rH © CN rH Tf © Ov CN PH rH PH rH VO Tf O0 O VO CN CN 00 vo oo Tf Tf Tf Tf VO oo oo CN CN CN vo VO E rH »—. rH T—t CN rH CN rH rH CN CN T—t CN T—t T—t rH PH PH r- Tf Ov Ov Ov rt cn Tf Tf e'- en rt Ov en 00 VO Ov rt m r-~ Tf OS OS t-- rt cn vq vq T—t en oq Ov Ov c - cn q cn Tf rt o N •V rH rt rH rH CN rH r ( CN CN rH rH T—t rH H r i ri T—t CN ri T—t Tf VO CJ % - r t - r t 3 cu CU CU CU w r- r- r- r- U *^  Tf Tf Tf Tf Tf Tf Tf u 00 00 00 oo oo oo oo oo oo oo oo a VO VO VO VO T—t »-H rH rH rH rH Ov Ov Ov OS OS Os Os Os OS Ov OS cn o rH rH rH rH o en en en c n en en O cn m cn cn m cn cn m cn cn cn S 00 cc 00 o +H c B S CU cu CU E rH CN en Tf E o rH Tf m r- oo E cn Tf m VO r- 00 OS o rH CN r o * o O o o T—t rt i - H rH rH rH rH Tf Tf Tf Tf Tf Tf Tf cn m cn cn CN CN CN CN "V cu CN CN CN CN CN CN CN "O cu CN CN CN CN CN CN CN CN CN CN CN 00 oo CZ) 313 N O M ' t ' - ^ o q P l ^ P c n i n T f c N C N v d r - ^ d o\ o V l l t l T f i n s t m C l v O C n T f n vq q H ( N r H in" f O i n cn T f cn t ^ v n m t N v q N O v t ^ H M r - M i n V r i r i v t ' d n m i o p j i n v O i N i i i ' t q q v q t N n r n o q v t v O v d i / i v d v r i i n i n ' v d r-, m vq ^ ov oo m 2 oo" 2 CN i n T t v q v n v q q c v i n ^in'vo'vn'vovdvoiri r- p - T f vd oi © 9 - o q r-^  ai T f r H O CN — r H rt . P -vd p - - v q i n v q e N P - ; T f O \ v d v d p ^ v o p ^ P ^ o d i n H IN CA oo K vd o ^ o rt 1 r H • H i n ov oo r-^  oo ^ r- f". -t vo vq O CN CN 0 0 >n oq H CN oq P - oq Ov vq e n vq i n r H CN T f CN T f oo P-^  Ov OV T f r H CN vd 0 0 OV p-^  rt i n OV vd CN vd OO T f c d CN CN c n CN c n T f T f CN m c n r H c n c n c n e n c n T f T f r H T f o d e n O O O O O O O O O O O O O O O O O O O O O O O I fi s § rt -tfc cu cj l_ 9 O 00 H-» e cu O O O O O O O O T f T f T f T f T f T f T f T f O v O v O v O v O v O v O v O v O r H c N e n T f i n v o p -T f T f T f T f T f T f T f T f r n e n e n m e n r n e n e n C M <u u 1-9 o H— e CU O O O O O O 0 0 0 0 0 0 0 0 0 0 0 0 T f T f T f T f T f T f C N c n T f m v o p -m m m i n m i n cn cn cn cn cn cn cn cu u s-9 O t/2 H-» c OJ O O O O O O O O O T f T f T f T f T f T f T f T f T f C N C N C N C N C N C N C N C N C N v o r - o o o v O r H C N e n T f c N c N c N c N e n e n e n m e n cncncnmcncncncnm 314 o V Os sq en T f q a H I N t-; H ' so cn « i y i p i r » i r i d cn CN N H in u i N » i » i O ' © Os © i n © CN vo os o o o \ r - o o r ^ ' i n i o i o O ' H — t ^ t H ^ M c o i i o i n i N t 00 —< —< sq © r~ o i od os CO T f ° ° . - i t CN 00 M i n ® t s (s od T j - o o o o o s O ' H O s T r . . V s d i n i n ' i n s d s o ' r t H ' J i c i o ^ m r -2 od rs 1 © CN CN • 00 so OS t-s so so Os i n ^ m r - . m t i n m ' . i i n s d i n o d o d s d c N - - J 2 c N - 2 * H <N (V, T f OS _ 2 2 < 5 i d ° « s i n CN r -P-* r~ 00 CN SO v o ^ ' I i S ' ^ r N ' ^ c N ^ : r-s oq os sq © T t od © oq oq os CN oq © i n r- - T t CN f i - H CN f l m CN CN T t CN CN l s - i n q c o » - H C ? s l / - ) T ) . 0 0 o q c N c N r ^ c n ' c n c n r ^ - - - r o ' © f . f ) f ) i n s o m i r i 0 0 , r ) — CM f ) © r-H d © © © f i m © © i n T t CN © © © © © © © o o o o f i m o o o o o © ' © ' © © ' © © © © © © © • eg o l l C/3 ca u is CO a o T t ft 0) u L . 9 e CO 4-1 s eu f s p - r - r~-SO so so so 1 r H CN f l T t © © © © CN CN CN CN T t T t T t T t T t T t T t r H r H r H r H r - H r - H r - H f l f l f l f l f l f l f l © - H co T t cn r-- 00 CN CN CN CN CN CN CN 1 o o o o o o o o o o o o o o o o o o o o o o O s O S O s O s O s O s O s O s O s O S O s c n c n c n c n c n c n c n c n c n c n i n f i T t c n s o r - - o o o s © - H C N f i T t T t T f T t T t T t T t c n c n c n c n C N C N C N C N C N C N C N C N C N C N C N 315 CO CD I CO 0 3 o I <+-. o co -*-» CO u CD "3 3^ .c B CO Q CO CD O 13 o CD "3 CD co 6 o <h CO CD CO CO l - l 3 co K "3 CD s s a •8 <N ON ON Pi i OO ON ON • oo ON OO I rt i 0 0 ON p -rt i oo ON C-i l 0 0 ON 3 I rt CN oo ON T f T f c n CN NO T f oq CN r-CN CN T f ON m t - ; P» 0 0 p -NO CN B5-3 ON c n CN c n c n r—t NO c n CN © © © CN p - c n oq CN NO c n CN NO p -p -T j " ON oq p -T f c n p - T f T f c n B3-2 CN c n © c n i n c n 1—1 © CN CN c n i > i n c n CN ON NO © ON T f 0 0 oq 0 0 P-; ON NO P- i n ON B3-2 c n c n ON CN CN CN c n i n © ON CO o T f ON c n c n T f m oo p -oo p -i n oo NO CN i n OO o B4-2 T f c n © c n c n ON T f T f © CN VI oo ON T f ON p -oo oo NO 0 0 CN T f oq T f CN © NO © T f CN CN CN ON ON T f od NO ©' CN B2-T f o p -p^ ON CN CN oq CN ON ON c n NO 0 0 NO ON o © m i n 0 0 T f B4-2 c n CN c n c n P-^  T f T f c n CN CN c n c n c n p -m T f © p -© r-~ CN © p -oo T f P- © ON NO c n B3-2 p -c n CN c n c n T f T f © © i—i CN 8B OS T f r—1 © T f oq ON © oo NO P-oq OO i n © oo CN T f c n ©' c n NO 0 0 T f T f T—t © © CN B4-o c n ON ON NO CN c n NO © T f CN ON i n © p -0 0 T f c n B3-2 © c n © c n i n od i n NO ©' T—t CN p -T f r-p~- © CN c n CN 0 0 i n c n i n m T f p -CN CN CN B5-3 NO c n c n c n i n r-^  CN c n © © CN T f o m c n c n CN NO T f p» i n NO m i n 0 0 m © T f NO i n P-T f B3-2 T—t c n c n c n 0 0 T f T f CN c n CN CN r-- T f ON T f i n m oq oo T f m © i n © ON © CN © OO ON B3 -2 c n c n © c n c n ©' 1—1 T f T f c n © CD •a o o CD C3 O o u O O O Cfl O O O & ? 3 a S -3 •a ! o CD c3 CD N J 3 -J < 316 

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