Open Collections

UBC Theses and Dissertations

UBC Theses Logo

UBC Theses and Dissertations

Distribution of sulphur, iron, copper and zinc in modern marine sediments of Mud Bay, Crescent Beach,… Northcote, Kenneth Eugene 1961

Your browser doesn't seem to have a PDF viewer, please download the PDF to view this item.

Item Metadata

Download

Media
831-UBC_1961_A6_7 N6 D4.pdf [ 3.03MB ]
Metadata
JSON: 831-1.0053035.json
JSON-LD: 831-1.0053035-ld.json
RDF/XML (Pretty): 831-1.0053035-rdf.xml
RDF/JSON: 831-1.0053035-rdf.json
Turtle: 831-1.0053035-turtle.txt
N-Triples: 831-1.0053035-rdf-ntriples.txt
Original Record: 831-1.0053035-source.json
Full Text
831-1.0053035-fulltext.txt
Citation
831-1.0053035.ris

Full Text

DISTRIBUTION OF SULPHUR, IRON, COPPER AND ZINC IN MODERN MARINE SEDIMENTS OF MUD BAY, CRESCENT BEACH, B.C. by KENNETH EUGENE NORTHCOTE B.A., The University of B r i t i s h Columbia, 1953 A THESIS SUBMITTED IN PARTIAL FULFILMENT OF THE REQUIREMENTS FOR THE DEGREE OF MASTER OF SCIENCE i n the Department of Geology We accept this thesis as conforming to the required standard THE UNIVERSITY OF BRITISH COLUMBIA A p r i l , 1961 I n p r e s e n t i n g t h i s t h e s i s i n p a r t i a l f u l f i 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 an advanced degree a t 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 , I agree t h a t t h e L i b r a r y s h a l l make i t f r e e l y a v a i l a b l e f o r r e f e r e n c e and s t u d y . I f u r t h e r agree t h a t p e r m i s s i o n f o r e x t e n s i v e c o p y i n g o f t h i s t h e s i s f o r s c h o l a r l y purposes may be g r a n t e d by t h e Head o f my Department o r by h i s r e p r e s e n t a t i v e s . I t i s u n d e r s t o o d t h a t c o p y i n g o r p u b l i c a t i o n o f t h i s t h e s i s f o r f i n a n c i a l g a i n s h a l l not be a l l o w e d w i t h o u t my w r i t t e n permission-. The U n i v e r s i t y o f B r i t i s h Columbia, Vancouver $, Canada. Department o f ABSTRACT The purpose of t h i s thesis was to investigate the pattern of d i s t r i b u t i o n of some elements i n the t i d a l f l a t environment at Mud Bay near Crescent Beach, B.C. Samples of sediment were collected i n a regular pattern over the bay. Quantitative chemical analyses of the samples were made for acid-soluble copper, zinc, lead, and molybdenum. The same samples were analysed spectrochemically for iron and sulphur. The re s u l t s of the analyses were plotted on base maps and contoured. It was found that there was a d e f i n i t e pattern of sedimentation. Because of the shallow depth of water at high tide and the bay's sheltered aspect, deposition of f i n e r -grained material occurred near shore. In s l i g h t l y deeper and more exposed parts of the bay fine-grained material was winnowed leaving coarse-grained sediment. Most of the elements showed a d e f i n i t e pattern of d i s t r i b u t i o n . Sulphur, copper, and zinc showed a tendency to concentrate i n finer-grained materials. Iron, i n the form of magnetite, was deposited with coarser-grained materials near r i v e r mouths and exposed parts of the bay. Lead values were too low to permit con-clusions regarding i t s d i s t r i b u t i o n . Molybdenum concentrations were below the detection l e v e l of the method of chemical analysis. No attempt was made to determine the form i n which the elements were present nor to determine the reason for their concentration other than to suggest the most obvious p o s s i b i l i t i e s . ACKNOWLEDGEMENTS The author wishes to express his gratitude to Dr. W.H. White with whom the idea originated for th i s project and who supervised a l l stages of i t s progress. Special thanks i s extended to Dr. R.E.Delavault for the intere s t he has shown and the advice given during analysis of the samples. Mr. A.H. Bullman and Mr. R.G.Butters taught the author the procedures for chemical and X-Ray spectro-chemical analysis of the samples. S h i r l e y Anne Northcote, the author's wife and co-worker, assisted with c o l l e c t i o n of the samples, drafting of the maps and with s e c r e t a r i a l duties during preparation of the th e s i s . It was through interest shown by Dr. H.V.Warren and his e f f o r t s on the author's behalf that a large part of the expense of thi s thesis was paid by receipt of the A.M.E. Kania Memorial Scholarship. TABLE OF CONTENTS Page CHAPTER I. STATEMENT OF THE PROBLEM 1 CHAPTER II. PHYSIOGRAPHY MD GEOLOGY 3 GENERAL CONDITIONS 3 PHYSIOGRAPHY AND GEOLOGY OF CRESCENT BEACH AREA . . 4 Surface Geology 5 Source of Metals and Sulphur 7 CHAPTER I I I . SAMPLING PROCEDURE 9 CHAPTER IV. SEDIMENTATION 11 DISTRIBUTION 11 COMPOSITION OF THE SEDIMENTS OF MUD BAY 14 CHAPTER V. ANALYTICAL PROCEDURE 15 PROBLEMS OF CONTAMINATION 15 Contamination i n the Laboratory 15 Inter-sample Contamination 15 SULPHUR ANALYSIS 16 Accuracy of Sulphur Analyses . 18 Reproducibility of Sulphur Analysis 18 IRON ANALYSIS 20 Reproducibility of Iron Analysis 21 COPPER ANALYSIS . 21 Reproducibility of Copper Analysis 22 ZINC ANALYSIS 23 Reproducibility of Zinc Analysis 24 LEAD ANALYSIS 24 MOLYBDENUM ANALYSIS 25 CHAPTER VI. RESULTS 26 SULPHUR 26 IRON ' . 27 COPPER 28 ZINC 29 LEAD 30 MOLYBDENUM 30 ORGANIC MATERIAL 31 CHAPTER VII. DISCUSSION 32 SEDIMENTATION 32 SULPHUR . . 7 32 IRON 33 COPPER 34 ZINC 36 LEAD 37 CHAPTER VIII. CONCLUSIONS 38 TABLE OF CONTENTS Page SELECTED BIBLIOGRAPHY 39 APPENDICES APPENDIX A. SAMPLE ANALYSES 40 APPENDIX B. MEAN VARIATION OF ANALYSES 43 APPENDIX C. TABLE OF FORMATIONS 44 CHAPTER I. STATEMENT OF THE PROBLEM There has been much discussion and speculation during the past few years concerning the apparent concentration and orderly zoning, with respect to the former shorelines, ex-hibi t e d by certain elements i n some ore deposits that may be of syngenetic o r i g i n (Garlick, 1953; White, 1954). The purpose of thi s thesis was to determine i f copper, z i n c , lead, molybdenum, iron and sulphur had a random or zonal d i s t r i -bution with respect to shorelines or r i v e r mouths i n recent sediments of a l i t t o r a l , t i d a l f l a t environment of deposition. The reasons for any such concentrations and the form i n which the elements occur l i e s beyond the scope of thi s t h e s i s . Mud Bay, at Crescent Beach, B.C., i s the s i t e of present-day t i d a l f l a t deposition of unconsolidated, i n t e r -bedded, and intermixed mud, s i l t , and sand. There i s no obvious source of heavy metals and sulphur to cause t h e i r deposition i n large amounts i n the sediments of Mud Bay. It was suggested that i f favourable conditions exist at Mud Bay that would produce large concentrations of heavy metals and s u l -phur from a source r i c h i n these elements then a smaller con-centration might occur from a source poorer i n these same elements. There would have to be, however, a s u f f i c i e n t con-centration of metals being transported into the bay to allow a "saturation" and deposition under favorable conditions. A method of analysis i s required of s u f f i c i e n t s e n s i t i v i t y to measure copper, zi n c , sulphur, i r o n , lead, and molybdenum i n t h e i r small background concentrations. S i g n i f i c a n t i n -creases i n concentration would then be detected. Mud Bay was chosen as a model for this type of research because of i t s ready a c c e s s i b i l i t y and because i t exhibits the desired environment of deposition. The bottom sediments were e a s i l y sampled because of the shallow depth of water at high t i d e . CHAPTER I I . PHYSIOGRAPHY AND GEOLOGY GENERAL CONDITIONS Mud Bay, on the east side of Boundary Bay, i s 4 miles north of the B r i t i s h Columbia - Washington border, 1% miles west of Highway # 9 9 and immediately north of the v i l l a g e of Crescent Beach, B.C. Access to the north, or Colebrook, side of Mud Bay was gained by access roads through private property to a dyke at the edge of the bay. On the south side, access was gained to the bay from Blackie Spit at Crescent Beach. Mud Bay consists of approximately four square miles of mud f l a t s of very low r e l i e f , cut only by the meandering r i v e r channels of the Serpentine and Nicomekl Rivers and a small stream which enters the bay from the north. The mud f l a t s slope gently seaward to a depth of about 12 feet below high water l e v e l at the junction of the Nicomekl and Serpentine Rivers. Mud Bay becomes completely submerged by a 10-foot t i d e , and i t i s possible to row a small boat back and f o r t h across the bay on an 11-foot to 12-foot t i d e . The marshy areas at the edges of the bay are completely covered during the high winter tides i n excess of"13 feet. The Serpentine and Nicomekl Rivers enter Mud Bay at i t s northeast and southeast sides, respectively. The Nicomekl River has a yearly average discharge of 115 c f s . 4 A maximum o f 9 8 5 c f s . was recorded December 9 t h , 1 9 5 6 and a minimum o f 5 c f s on November 16, 1 9 5 5 and February 3 » 1 9 5 6 . 1 No data were a v a i l a b l e f o r the r a t e of flow o f the S e r p e n t i n e R i v e r but i t appears to be somewhat l e s s than from the Nicomekl R i v e r . During an incoming h i g h w i n t e r t i d e the flow o f r i v e r water i s reversed f o r at l e a s t a m i l e - a n d - a - h a l f up the r i v e r s and d u r i n g outgoing t i d e s the Nicomekl R i v e r flows seaward w i t h s u f f i c i e n t v e l o c i t y to make rowing a g a i n s t i t d i f f i c u l t i n the narrow reaches. PHYSIOGRAPHY AND GEOLOGY OF CRESCENT BEACH AREA Department o f Mines and T e c h n i c a l Surveys Paper # 5 7 - 5 e n t i t l e d " S u r f i c i a l Geology of the New Westminster Map Area, B r i t i s h Columbia" by J.E.Armstrong i s the o n l y source of good p u b l i s h e d Information p e r t a i n i n g to the geology o f the area surrounding Mud Bay. Mud Bay, and the a r e a a d j a c e n t , forms a s m a l l p a r t o f the C o a s t a l Trough which i s c a l l e d the F r a s e r Lowland (Armstrong, 1 9 5 7 , p . 2 ) . The Mud Bay a r e a i n c l u d e s p a r t of the broad F r a s e r V a l l e y d e l t a to the n o r t h and low h i l l s o f 3 0 0 to 3 5 0 f e e t e l e v a t i o n to the n o r t h e a s t , e a s t , and south between which l i e the v a l l e y s of the S e r p e n t i n e and Nicomekl R i v e r s . 1 Data were ob t a i n e d from B.C. Game Commission, F i s h e r i e s Research group. Measurements were made at the edge o f the t i d a l i n f l u e n c e . 5 The headwaters of the Nicomekl River a r i s e on Fern Ridge and flow northerly to the v i c i n i t y of Langley where the r i v e r changes i t s d i r e c t i o n to westerly and flows to the southeast side of Mud Bay. The headwaters of the Serpentine River a r i s e between the Surrey and North Langley Highlands and flow i n a southerly d i r e c t i o n . At a point about 4 miles up-stream from the r i v e r mouth, d i r e c t i o n of flow changes to westerly to the northeast side of Mud Bay. The lower portion of the Nicomekl and Serpentine Rivers occupy the north and south sides, respectively, of the same broad v a l l e y . The v a l l e y s occupied by the Nicomekl and Serpentine r i v e r are not believed to be formed by stream erosion but are thought to be former embayments of the sea (Armstrong, 1957, p.3). Surface Geology The exposed sediments of the Mud Bay area are a l l of Pleistocene and Recent age. The broad, f l a t t e r portions of the Nicomekl-Serpentine Valley and that part of the Fraser Delta l y i n g to the north of Mud Bay consist of part of the S a l i s h group of Post-Glacial sediments composed of: (1) Fraser Floodplain deposits and ( 2 ) Richmond Delta deposits. Here the S a l i s h group i s composed of lowland peat and variable thicknesses of s i l t y clay, clayey s i l t , and sandy s i l t . The S a l i s h group i s s t i l l i n the process of formation. The uplands of Surrey, North Langley, and Crescent Beach expose on their flanks the following formations (Armstrong, 1 9 5 7 , ) : 2 (3) Nicomekl " s i l t " ; of deltaic and floodplain origin consisting of sand, s i l t , and gravel. (4) Colebrook gravel; of deltaic, channel and floodplain origin, composed of gravel and sand. ( 5 ) Surrey t i l l ; of glacial origin, composed of sandy to s i l t y t i l l and minor st r a t i f i e d d r i f t . (6) Cloverdale sediments; of marine origin, com-posed of s i l t y clay, clayey s i l t , s i l t and clay with minor sand and gravel. ( 7 ) Sunnyside sand; of l i t t o r a l and beach origin, composed of medium to coarse sand resting on Cloverdale sediments. The tops of the Surrey, North Langley and Crescent Beach uplands consist primarily of: (8) Newton Stony clay; of glacio-marine origin, composed of stony, clayey s i l t , poorly sorted t i l l - l i k e mixtures, minor clayey s i l t , s i l t y clay and sand. Fern Ridge, lying to the south and southeast of Langley, ex-poses Cloverdale and Sunnyside sands on i t s flanks as do the 2 See Appendix C, Table of Formations. 7 uplands of Surrey, North Langley and Crescent Beach. Fern Ridge, however, exposes sediments on i t s top which d i f f e r from those of the other uplands and are described as follows (Armstrong, 1957, figure 1 ) : (9) Whatcom deposits; of glacio-marine o r i g i n , approximating the Newton stony clay i n composition. (10) Abbotsford outwash; composed of gla c i o -f l u v i a l deposits which consist of recessional outwash sand and gravel. The source of the bulk of the sediments deposited i n Mud Bay are from within the drainage area of the Serpentine and Nicomekl Rivers and from fine detritus carried by long-shore d r i f t , at periods of high tid e and favourable wind d i r e c t i o n , from the more exposed portion of Boundary Bay to the west. Minor amounts of detrit u s are contributed by the small stream entering the north side of Mud Bay and r e l a t i v e l y i n s i g n i f i c a n t amounts by material washed o f f the banks of the bay. The material making up the sediments of Mud Bay i s probably almost e n t i r e l y composed of debris derived from the formations of Pleistocene and Recent age l i s t e d above and i n the Table of Formations of Appendix C. Source of Metals and Sulphur Possible sources of metals and sulphur are as follows, 8 the f i r s t two probably being the mort important: (1) S u r f i c i a l sedimentary deposits. (2) Ocean water and ocean borne sediments. (3) Cultural sources, on Serpentine-Wicomekl Valley farms. CHAPTER III. SAMPLING PROCEDURE A grid was set up by locating azimuth l i n e s about 1000 feet apart and by c o l l e c t i n g samples along these l i n e s at int e r v a l s of approximately 1000 feet. Sampling was done from a row boat which was kept on the north-south l i n e by a l i n e of s i t e and by signals from an assistant on shore. When the loc a t i o n of the station was i n doubt checks were made by compass resection. The distance from shore was measured with an a r t i l l e r y range finder. Such sample locations are not precise but are believed to be accurate within 50 yards. It was not always possible to row prec i s e l y on the north-south l i n e . The accuracy of the range finder decreases with the square of the distance so that the location of stations farther from shore may be i n greater error. However, for purposes of th i s t h e s i s , i t i s f e l t that the stations were located with s u f f i c i e n t accuracy (see Map #1, Sample Locations). Sampling was done during the period from September 16th to December 5 t h , I960 by means of a corer 8 feet i n length. The corer consists of an aluminum tube of 1 inch inside diameter f i t t e d with a s t e e l cutting edge and a graduated wooden dowel plunger with a leather and aluminum packer to draw i n and eject the core. Duplicate samples were taken at each st a t i o n . The cores were ejected from the corer into separate polyethyline bags and l a b e l l e d . 10 The samples were then taken to the laboratory, trans-ferred to clean aluminum plates and dried i n a Fisher e l e c t r i c oven at 105°C. During the drying process portions of the samples, especially the f i n e r f r a c t i o n s , consolidated. The lumps of sample were broken up and the grains separated i n an agate mortar, care being taken not to crush the constituent grains. The samples were then passed through a 200 mesh screen. The+200 and -200 fractions were weighed and stored separately in l a b e l l e d polyetheline bags. The -200 f r a c t i o n (less than 0.74 mm) represents a grain size s l i g h t l y larger than the upper size l i m i t of s i l t (E.W. Lane, 1947, p.937). The coarse f r a c t i o n was not used for analysis. The f i n e f r a c t i o n of each sample was analysed for extractable copper, z i n c , lead and molybdenum using quanti-t a t i v e methods of chemical analysis. An X-ray spectrochemical analysis of the f i n e f r a c t i o n was made to determine the t o t a l amount of iron and sulphur. The results of the chemical and X-ray spectrochemical analyses were then plotted on base maps of scale 1 inch to 1000 feet and were contoured at appropriate i n t e r v a l s . CHAPTER IV. SEDIMENTATION DISTRIBUTION Map #2 shows a marked concentration of f i n e r s e d i -ment, of 75 and 80% -200 mesh si z e , around most of the shore-l i n e of Mud Bay. To the southwest, i n the more exposed and deeper portions of the bay, the concentration of fine-grained material decreases to less than 20$. At the mouth of the Nicomekl River, and at the north flank of Blackie S p i t , at Crescent Beach, the concentration of sediment of -200 mesh size may be as low as 1 to 3$. Several "ridges" of coarse material are evident crossing the mud f l a t s i n east and/or northeast d i r e c t i o n s . The most conspicuous "ridge", i n two branches, leads to the mouth of the Serpentine River. Others may represent former channels crossing the mud f l a t s . The mud f l a t s have very s l i g h t r e l i e f , the maximum being only 3 or 4 feet with the exception of the deeper r i v e r channels. The slope from the shore to the edge of the mud f l a t s i s very gentle but steepens at i t s outer edge. The bottom depths, at high t i d e , vary along the north-south l i n e s from 1 or 2 feet at the north shore to a maximum of 6 feet, with the exception of r i v e r channels, at the south ends of the l i n e s . The area adjacent to the shoreline of Mud Bay i s one of l i t t l e deposition and reworking of the sediments. Evidence for this was found when tracks made from an i n i t i a l attempt to walk across the flats were s t i l l visible two weeks later. The tracks had been covered by tides at least once a day. The near-shore portions of Mud Bay are covered with water only during periods of flood tides in excess of 9 feet, thus making possible only intermittent deposition near shore. The small flow of water from the Serpentine and Nicomekl Rivers suggest a relatively small amount of material is brought into the bay from the land. Probably of greater significance would be the amount of material that i s moved along the shore at periods of high tide by restricted current and wave action with deposition of fine material occurring in the very sheltered and shallow waters of Mud Bay. Mud Bay is sheltered from the direction of the pre-vailing \\rinds that veer from southeast to southwest. Because of i t s sheltered condition and very shallow depth even at high tide, there is l i t t l e opportunity for near-shore wave action to rework the sediments. The finer-grained fraction is not differentially removed, leaving coarser-grained materials behind as has happened in the deeper and more exposed part of the mud flats farther from shore. To seaward the sediments are submerged for longer periods of time to sufficient depth for wave action to become effective as a sorting agent. Map #2 shows the distribution of sediments that occurs under the conditions outlined above. 13 It should be noted that Map #2 gives only an approxi-mation of the s i z e - d i s t r i b u t i o n of sediment i n Mud Bay. It was obvious that there i s some interbedding of coarse-grained and fine-grained sediments i n parts of the bay. The sampling corer passed much more eas i l y through the finer-grained than coarser-grained material. A casual Inspection of the core for interbedding was often misleading because the fine-grained material tended to smear over the coarser-grained. The percent fine-grained versus coarse-grained material i s dependent on the length of core where interbedding occurs. It was not possible to sample to exactly the same depth at every station. The lengths of the core recovered ranged from 2 inches to greater than 18 inches, the average length being 8 inches. When about 8 inches of core was drawn into the core b a r r e l the f r i c t i o n of the core against the inside of the barrel was s u f f i c i e n t to cause further sediment to be pushed aside as the barr e l was forced downwards. The concentration of finer-grained material would be s l i g h t l y greater than shown on the map because of a tendency to lose f i n e r material during the seiving process. As no estimates were made of the r e l a t i v e losses of fine-grained and coarse-grained material, the r e s u l t i n g percent -200 mesh size probably i s somewhat low. 14 COMPOSITION OF THE SEDIMENTS OF MUD BAY A binocular microscopic examination of the 200 mesh f r a c t i o n of a few of the samples indicates they consist c h i e f l y of angular quartz grains, and some feldspar fragments that show cleavage and multiple twinning. Fragments of plutonic rock, scattered grains of altered mica, (muscovite), and magnetite are also present. S h e l l fragments of present-day molluscs and crustaceans occur i n many samples. The fine-grained f r a c t i o n appears to contain the same minerals. No clay minerals were recognized and i f present must be i n very small amounts. The bulk of the clay-size materials pro-bably consists of rock flo u r of g l a c i a l o r i g i n . Microscopic examination of grain thin sections pre-pared from the coarse f r a c t i o n of a few samples were made to confirm the binocular microscopic examination. The samples were found to consist c h i e f l y of angular quartz grains and fragments of plutonic rock. Smaller amounts of multiple-twinned and untwinned feldspar were present. The rock frag-ments were composed mainly of feldspar and quartz with musco-v i t e , ( s e r i c i t e ) , epidote, and c h l o r i t e ( c h l o r i t i z e d b i o t i t e ) . Composite fragments also present are composed c h i e f l y of minute grains of quartz. Some composite fragments are com-posed of feldspar with s e r i c i t e and c h l o r i t e . CHAPTER V. ANALYTICAL PROCEDURE PROBLEMS OF CONTAMINATION Contamination i n the Laboratory The main source of contamination i s laboratory equipment, p a r t i c u l a r l y the set of screens used on thi s pro-j e c t . These screens were used by a number of other students for projects including seiving sediment from other areas and for s i z i n g samples of high-grade ore. There are also other sources of contamination in the laboratory such as paint p a r t i c l e s , tap water, and dust. With care these can be con-t r o l l e d . Samples were re-analysed when contamination was suspected and/or when values were anomalously high. Laboratory contamination could be almost eliminated i f a complete set of laboratory equipment, including stainless s t e e l screens, were used exclusively for the project. Inter-sample Contamination Inter-sample contamination could occur during the coring process by incomplete cleaning of the core barrel be-tween samples. The core barrel was cleaned thoroughly between each s t a t i o n and the f i r s t core cut at each station was d i s -carded. The second and t h i r d cores at each station were re-tained for analysis. 16 Inter-sample contamination may occur also during the seiving process. The same screens were used for a l l samples, screens being c a r e f u l l y cleaned before each sample was seived. It i s not possible to get the screens absolutely clean as there v / i l l always be some extremely small grains adhering to the screen and rim as well as larger fragments stuck i n the screen openings. Some contamination from this source was un-avoidable and i s recognized as contributing to error i n the f i n a l a n a l y t i c a l r e s u l t s . However, i f one considers the r e l a t i v e l y large quantity of material that passes through the screen for each sample (15 to 50 grams); the small concen-trations of the elements present i n even the richest sample; and the rather small difference i n concentration between them, th i s source of error becomes p r a c t i c a l l y n e g l i g i b l e . SULPHUR ANALYSIS The fine-grained f r a c t i o n of each sample was analysed for sulphur spectrochemically using an X-ray fluorescent spectrometer with s p e c i a l adaptations for elements of low atomic number. These special adaptations include (Molloy, Kerr, I960): (1) ammonium dihydrogen phosphate c r y s t a l , (2) helium gas for the instrument path, (3) methane-argon gas (P 10) and a ( 4 ) l i n e a r amplifier for the flow proportional counter. The instrument settings were as follows; X-ray unit 50 KV and 20 ina Flow proportional counter 1400 V Baseline 10 V Window 4 V Time constant 4 sec Scale factor 100 Count duration 30 sec Sulphur was determined using a peak-to-background count method and a c a l i b r a t i o n curve prepared from synthetic standards. At least two counts were taken for peak and background with the i r average value being used. The standards were prepared by adding native sulphur i n increments of 0 .5$ to one of the samples u n t i l counts were obtained for x plus 0% to x plus 3$ sulphur, where "x" i s the amount of sulphur o r i g i n a l l y present i n the sample. A c a l i b r a t i o n chart was prepared by p l o t t i n g sulphur content as the ordinates and number of counts peak-to-background i n 30 seconds as abcissa. The increase i n the number of counts for a given increase i n sulphur content i s l i n e a r . It was possible, therefore, to project the c a l i -bration curve back to the ordinate for zero counts peak-to-background corresponding to 0% t o t a l sulphur and r e c a l i b r a t e the ordinate for percent t o t a l sulphur. Figure #1 i s the re s u l t i n g c a l i b r a t i o n curve for sulphur. Values were then obtained for the percent t o t a l sulphur for each sample from th i s c a l i b r a t i o n curve. Percent sulphur content was plotted 18 and contoured on Map #3. This shows the sulphur d i s t r i b u t i o n i n Mud Bay and represents t o t a l sulphur less that l o s t i n the form of R^S gas. Accuracy of the Sulphur Analysis Sulphur i n the form of B^S gas i s not included i n the analysis because i t i s lo s t from the samples during coring and during their preparation for analysis. The spectro-chemical analyses for sulphur, because of the loss of H 2S, do not represent the t o t a l sulphur content of the sediments. The method of comparing the r e l a t i v e number of counts from peak-to-background i s not as accurate as the method of comparison of the areas which l i e under the K«<peak for sulphur. More accurate, but more time consuming, methods could have been used, but were not warranted because of the unknown amount of loss of H2S gas. Reproducibility of the Sulphur Analysis Figure #2 (a),(b), and (c) shows graphically the r e p r o d u c i b i l i t y of the X-Ray spectrochemical method for sulphur. Figure #2(a) i s the sulphur K^curve for sample #31. Figure #2(b) i s the same curve for a d i f f e r e n t portion of sample #31 and Figure #2(c) i s a re-run of #2(b). The res u l t s indicate that the r e p r o d u c i b i l i t y of separate portions of the same 1 9 sample f a l l s within the s t a t i s t i c a l v a r i a t i o n obtained by rerunning the same portion of a sample. However i f many such tests were made the above statement might not be proven v a l i d . It was found also that the difference i n the number of counts obtained from a crushed and uncrushed sample appear to f a l l within the v a r i a t i o n of the number of counts obtained for a given sample and would not appreciably af f e c t the o v e r a l l pattern of concentration. A crushed portion of sample #43 gave a decrease i n the number of peak-to-background counts as compared to the uncrushed sample. The difference between the two peak-to-background counts was 2 3 5 for the crushed and 2 5 0 for the uncrushed sample. A difference i n background counts caused the discrepancy. The peak counts for both were approximately the same, the difference i n the two readings represent about 0.05% sulphur. However, i f a great number of samples were tested i n the above manner i t might be found that crushing could s i g n i f i c a n t l y a l t e r the value of the peak counts. 3 Sample Background counts Peak counts Difference #43 uncrushed 1 7 7 427 2 5 0 # 4 3 crushed 1 9 6 2 3 5 231 Discrepancy 1 5 counts 20 IRON ANALYSIS The samples were analysed for iron by using an X-Ray fluorescent spectrometer with a lithium f l u o r i d e c r y s t a l . A similar procedure to that of sulphur was used. The iron content Is proportional to the difference i n the number of counts i n a 15-second period between the iron K-^peak and the background. A c a l i b r a t i o n curve was made from standards. These standards were prepared by taking a sample low i n iron and adding Fe20^ to i t i n 0.5$ Fe increments from x plus 0% to x plus 2.5$ Fe; where "x" i s the amount of Fe present i n the o r i g i n a l sample. There i s a l i n e a r relationship between the i r o n concentration and the number of counts obtained. As for sulphur, i t was possible to ca l i b r a t e the ordinate for t o t a l iron content by projecting the c a l i b r a t i o n curve back to the ordinate for zero counts. Figure #3 i s the re s u l t i n g c a l i b r a t i o n curve for iro n . Instrumentation was as follows: X-Ray unit 40 W/ and 20 ma Threshold 15.5 V Flow proportional counter 9 0 0 V Time constant 2 sec Scale factor 12800 L i F analysing c r y s t a l The values plotted and contoured on Map #4 represent the t o t a l concentration of ir o n at each station. 21 Reproducibility of Iron Analysis Figure #4(a) and (b) i l l u s t r a t e s graphically the excellent r e p r o d u c i b i l i t y of results for iron by using d i f f e r e n t portions of the same sample. This test was repeated several times with excellent r e p r o d u c i b i l i t y . Figure #4(a) and (c) shows graphically the increase i n the peak height observed when the sample i s f i n e l y crushed i n an agate mortar. Using the method of the difference i n the number of counts peak-to-background, i t was found that the peak counts were sub s t a n t i a l l y increased by grinding the coarser-grained samples thus making a s i g n i f i c a n t increase i n the t o t a l iron detected i n the coarser samples. For t h i s reason a l l the samples were f i n e l y ground i n an agate mortar before analysis. COPPER ANALYSIS The fine-grained f r a c t i o n of each sample was analysed for copper by the quantitative method devised by R.E. Delavault (Warren and Delavault, 1949). The procedure i s b r i e f l y as follows: Two grams of minus 200 mesh sample, previously heated for 3 hours at 1150° F i n a Heavy Duty E l e c t r i c Furnace, were digested at b o i l i n g point for t h i r t y minutes i n 30 ml 1 N H2SO4 then made up to 40 mis with d i s t i l l e d water (Warren, Delavault, 1956). A 5 ml aliquot of the clear f l u i d was evaporated to dryness after 1 ml of 20$ hydroxylamine hydro-22 chloride solution was added. Two drops of 3 N HCL were added to the residue and the residue was washed into a "shaking cy l i n d e r " with d i s t i l l e d H 20 and made up to 10 ml. Approx-imately 5 mg of ascorbic acid added and afte r checking the a c i d i t y , the solution was t i t r a t e d to a greyend point with "dithizone" dissolved i n CC14 (60 mg/1). The results of the analyses were plotted and contoured on Map #!?• The values plotted on Map #5 represent the amount of copper which was soluble i n H2SO4 and i s a f r a c t i o n of the t o t a l amount of copper present. Reproducibility of Copper Analysis The f i r s t t h i r t y analyses for copper are l i k e l y to be less accurate than the remainder because the author was unfamiliar with the a n a l y t i c a l method. For this reason the f i r s t t h i r t y samples were re-analysed for copper and z i n c . The r e s u l t s of the analyses are l i s t e d i n Appendix B. At f i r s t glance these results are extremely discouraging. The mean v a r i a t i o n for copper content i s 12 ppm which i s higher than was expected. The v a r i a t i o n of low values, of course, i s much less than 12 ppm, whereas, with higher concentrations the variations are much higher than 12 ppm. It i s worthy of note that the repeat analyses for copper gave consistently higher values. If the second set of analyses were plotted on the map instead of the f i r s t the observed concentrations on Map #5 would be more pronounced. Therefore, i n spite of the 23 fact that the v a r i a t i o n i n results i s larger than desired, the o v e r a l l pattern obtained for the d i s t r i b u t i o n of copper i s considered v a l i d . ZINC ANALYSIS The samples were also analysed chemically for zinc according to the procedure devised by R.E.Delavault, (Warren, Delavault, 1949). A 1 ml aliquot of the clear solution from the "shaking cy l i n d e r " used i n the copper analysis was trans-ferred to a second "shaking cylinder". One ml of 20$ hydro-xylamine hydrochloride solution and 0 .5 ml of acetate buffer were added. The pH of the solution was checked with congo red paper to ensure the solution was basic. The solution was then t i t r a t e d to a grey end point with "dithizone" dissolved i n C C I 4 as for the copper determination. A standard of known zinc content prepared and t i t r a t e d to an end point was used i n calcul a t i n g the amount of zinc i n the samples. The r e s u l t s of the analyses were plotted on Map #6. The value plotted for zinc represents the amount of zinc which was soluble i n H2SO4 and i s only a f r a c t i o n of the t o t a l amount of z i n c . 24 Reproducibility of Zinc Analysis The f i r s t t h i r t y samples, which are l i k e l y to be greatest i n error, were re-analysed for zinc to check the r e p r o d u c i b i l i t y of the laboratory technique and the method of ana l y s i s . The results are tabulated i n Appendix B. The mean va r i a t i o n i s about 13 ppm with the variations i n the lower concentrations somewhat less and i n higher concentrations somewhat more. Most of the repeat analyses are lower than the i n i t i a l analyses. The r e p r o d u c i b i l i t y of the analyses was much poorer than was hoped. However, the v a r i a t i o n obtained does not appear to be s u f f i c i e n t to a l t e r appreciably the o v e r a l l pattern of the zinc concentrations shown on Map #6. LEAD ANALYSIS The fine-grained f r a c t i o n of each sample was analysed for lead using the quantitative chemical method developed by R.E. Delavault (Warren, Delavault, 1961 i n press). A 5 ml aliquot of the clear f l u i d from the 40 ml H 2S0 4 digested sample was transferred to a "shaking cylinder". Approximately 5 nig of ascorbic acid was added with 1 ml c i t r a t e solution and a s u f f i c i e n t number of drops of ammonia to ensure a pH of 8.5 - 9.0. Then 0 .5 ml of cyanide solution was added and, using a burette, 0 .5 ml of dithizone dissolved i n chloroform was added and colors compared to a set of standards. Samples higher i n lead required addition of more 25 dithizone u n t i l they could be matched to one of the standards. The re s u l t s of the lead analyses are l i s t e d i n Appendix A. Lead values were too low and the range too small to warrant p l o t t i n g and contouring on a map. The value l i s t e d i n Appendix A for lead represents the amount of lead soluble i n H 2 S O 4 , which i s an unknown f r a c t i o n of the t o t a l lead content. MOLYBDENUM ANALYSIS The samples were analysed for molybdenum using another method of analysis devised by R.E.Delavault (Warren, Delavault, 1953). Another 5 ml aliquot from the 40 ml fi^SO^ digested sample for each station was transferred to a test tube where 1.5 mis of the cyanate solution and 1 ml of stannous chloride were added then 0.5 ml of isopropyl ether was added then polyethyline corks were inserted. The test tubes were i n -verted and shaken vigorously then allowed to set with cork end up. The presence of molybdenum causes an amber color-ation i n the ether. The concentration of molybdenum was below the l e v e l of detection i n the sediments of Mud Bay. 26 CHAPTER VI. RESULTS The results of the analyses show a d e f i n i t e pattern of sedimentation and an orderly d i s t r i b u t i o n of sulphur, i r o n , copper, and zinc i n Mud Bay. No conclusions could be drax^n regarding d i s t r i b u t i o n of lead and molybdenum. The pattern of sedimentation and the d i s t r i b u t i o n of metals and sulphur are discussed i n the following sections. SULPHUR The sulphur content of the sediments of Mud Bay range from less than 0 .5$ to greater than 2 . 0 $ , with most values f a l l i n g between 0 .5$ and 1 .0$. Map #3 shows that the higher concentrations of sulphur occur near the shoreline especially i n the east and northeast sides of the bay. The values de-crease with distance from shore, the lowest values occurring i n the areas showing the highest percentage of coarser-grained materials. In general, the d i s t r i b u t i o n of sulphur r e f l e c t s f a i r l y c l o s e l y the size d i s t r i b u t i o n of the sediments. A close comparison of Map #2 and #3 reveals many places where fine-grained sediments have lower values than those which are s l i g h t l y coarser-grained. The form of the sulphur i n the Mud Bay sediments i s not known. The sulphur determined does not include the H2S gas l o s t during the process of sampling, drying, and seiving. 27 The smell of H^ S was comparatively strong in the finer-grained sediments or muds near shore. The total sulphur content of a l l samples is probably somewhat higher as a result of loss of B>>S gas, such loss being greater near shore where the smell of H2S was most noticeable. Therefore the contrast between sulphur values near shore and off shore would be even more pronounced than appears on Map #3. IRON Map #4 gives the results of the sample analyses for iron. The values for iron range between 1.5$ and 3.8$, with most of the values f a l l i n g between 2 and 3$. Unlike the distribution of sulphur, iron shows no marked concentration along the shoreline. If Map #4, Percent Iron, is compared to Map #2, Percent Sediment Less than 200 Mesh, i t is apparent that iron is relatively concentrated in the coarser-grained sediment. Magnetite is present in the samples, which probably accounts for most of the iron. Magnetite, deposited at the river mouths with the relatively coarse-grained material, as a result of decrease of current velocity, probably accounts for the main iron pattern on Map #4. The high iron content at station #81 also could be explained in part in the same way because this station is approximately at the point where the Serpentine River enters the bay at periods of low tide. 28 The concentration at station #81 and at station #60 at the northwest side of the bay may be the result of winnowing action of waves and currents removing finer-grained material leaving coarser-grained material r e l a t i v e l y r i c h i n magnetite. These stations are beyond the approximate edge of the sheltered and shallower part of the bay where finer-grained material i s r e l a t i v e l y abundant. It i s not possible to explain, i n this way, the high iron content at stations #11 and #106, at the north side of the bay. Sample #106 appeared to be streaked with reddish-brown iron oxide, possibly oxidized rubbish d i s -carded i n the bay. The high concentration of iron at s t a t i o n #11 remains unexplained. It should be noted that the t o t a l range i n iron content i s comparatively small. COPPER Map #5, Concentration of Copper i n Parts Per M i l l i o n , shows extremely well-marked concentrations of copper i n the finer-grained sediments and near the mouths of the r i v e r s . Values of copper greater than 20 ppm are considered anomalous. Higher concentrations of copper are not r e s t r i c t e d to the finer-grained sediments but occur even i n the area of coarsest grain-size at the mouth of the Nicomekl River. Scattered, anomalous values occur i n oyster beds near the center of the bay. The d i s t r i b u t i o n of copper may depend to some extent upon the r a t i o of s a l t and fresh water i n and near the r i v e r mouths. Again, the presence of bacteria that can p r e c i p i t a t e copper might a f f e c t the copper pattern. Thus, i t cannot be concluded that grain-size of sediment, proximity to shores and r i v e r mouths, organic content, or sulphur content are the only factors a f f e c t i n g the d i s t r i b u t i o n of copper. ZINC Map #6, Zinc Concentration i n Parts Per M i l l i o n , has values ranging from as low as 18 ppm to a high of 109 ppm. Zinc values greater than 6 0 ppm are considered anomalous. The highest values show some tendency to concentrate close to the shoreline. An exception i s the i s o l a t e d high value at st a t i o n #56 near the middle of the west side of Mud Bay. As both samples taken at t h i s station gave high zinc values the anomaly i s apparently v a l i d . A second and larger zone of anomalous values occurs i n the v i c i n i t y of station #3 north of the center of the bay. Three stations located on t h i s anomaly suggest that i t too i s v a l i d . Comparing Map #5 for copper with Map #6 for zinc i t w i l l be apparent that the highest copper value i s a few ppm higher than the highest zinc value. The lowest zinc value i s a few ppm higher than the lowest copper value. The o v e r a l l concentration of zinc i n Mud Bay i s somewhat higher than the o v e r a l l concentration of copper. The higher zinc values extend farther out into the bay. Possibly t h i s r e f l e c t s the greater s o l u b i l i t y of z i n c . Copper, on the other hand, appears to be much more concentrated near 3 0 snore. The r a t i o copper:zinc are shown on Map # 7 . Most of the stations have r a t i o less than unity. The r a t i o show a tendency to increase shoreward. An exception i s the area of s l i g h t l y higher copper i n the center of the bay where there are oyster beds. LEAD Lead content of Mud Bay i s small, generally less than 1 or 2 ppm. Stations #44 and # 4 5 , however, give values of 20 and 7 ppm, respectively. These values are d i f f i c u l t to explain by contamination because two sets of samples were processed separately, the second a few weeks af t e r the f i r s t . The o v e r a l l concentration of lead i s so low that v a l i d conclusions cannot be made regarding i t s d i s t r i b u t i o n i n Mud Bay. The s l i g h t l y higher values occur with finer-grained sediments whereas values less than 1 ppm show some tendency to occur where the sediment i s coarser-grained. MOLYBDENUM Molybdenum concentrations were below the l e v e l of detection i n Mud Bay. ORGANIC MATERIAL The d i s t r i b u t i o n of organic material i n the sediment of Mud Bay was not determined. However, i t i s probable that non-living organic material, because of i t s low s p e c i f i c gravity, would tend to accumulate with the finer-grained sediments. CHAPTER V I I . DISCUSSION SEDIMENTATION Mud Bay i s an environment of slow, t i d a l f l a t deposition. Deposition of sediment can take place only at the time of high tide when the bottom i s covered for only short periods of time. The sources of sediment are formations of Pleistocene and Recent Age i n the drainage areas of the Serpentine and Nicomekl Rivers and, because of the bay's sheltered aspect, sediment may be brought from the west by longshore currents. The pattern of sedimentation i n Mud Bay i s the re-verse of the normal pattern of coarse-grained materials near shore and finer-grained farther from shore. The finer-grained material i s concentrated near shore i n the shallower portion of the bay and coarser material i s deposited farther away from shore and i n more exposed parts of the bay where wave action and long shore currents are s u f f i c i e n t l y active to winnow the fine-grained material. SULPHUR Sulphur shows a pronounced concentration near shore with the finer-grained sediments and non-living organic material. The odor of H 2 S was most noticeable i n the finer-grained sedi-ments, therefore, sulphur probably would show an even more 33 pronounced concentration i n the f i n e r near-shore sediments had H2S been included i n the analyses. The source of the sulphur i n the sediments of Mud Bay i s probably from ocean water and partly from sulphur i n organic material which derived i t s sulphur from the ocean. Ocean water contains 0 . 0 8 8 $ sulphur i n the rea d i l y accessible form of SO4 , as compared to 0 . 0 5 2 $ sulphur i n magmatic 4 rocks i n the less accessible form of sulphide compounds (Goldschmidt, 1954, p. 523-53D. The form i n which the sulphur occurs i n the sediments i s not known. H2S can be formed by reduction of sulphate to sulphide by heterotropic bacteria and by decomposition of proteins (Goldschmidt, 1954, p. 529). Sulphur also could be i n the form of free sulphur produced by oxidation of H2S by sulphur bacteria. Goldschmidt points out that the above pro-cess occurs i n t i d a l f l a t s and i n shallow bays where x^ater movement i s r e s t r i c t e d and organic material i s abundant. The presence of bacteria also may play an important role i n the pr e c i p i t a t i o n of sulphides of various metals. IRON Iron has a tendency to concentrate i n the coarser-4 T.M. Goldschmidt, 1 9 5 4 , c i t e d from F.W.Clarke and H.S.Washington, 1 9 2 4 . 5 Goldschmidt, V.M., 1 9 5 4 , cited from ZoBell, 1939. grained sediments near the mouths of r i v e r s and i n the more exposed parts of the bay. The samples contain abundant magne-t i t e which probably accounts for most of the iron. It i s believed that magnetite, a mineral of high s p e c i f i c gravity, would be concentrated with the coarser-grained materials as indicated by the d i s t r i b u t i o n of iron on Map #3. The magnetite probably i s derived from the formations within the source-area of the sediments of Mud Bay. It seems unl i k e l y that 2 or 3% iron could be derived from ocean water, which has an iron content of only 0.001 ppm (Goldschmidt, 1954, p. 6 6 4 ) . Iron, therefore, i s considered of allogenic rather than diagenic o r i g i n . A small amount of iron i n the sediments could be present i n the form of h y d r o t r o i l i t e , FeS.nH20, which forms i n an environment poor i n oxygen and r i c h i n organic material (Goldschmidt, 1 9 5 4 , p. 530). Rankama and Sahama, (1950, p. 6 7 2 - 6 7 6 ) , discuss other means of iron deposition i n water such as gels of marine oxidates derived from weathering solutions of continental o r i g i n . Some of the iron may be con-centrated by such processes, but allogenic magnetite appears to be the dominant form of iron i n Mud Bay. COPPER The amount of copper i n the sediment of Mud Bay shows a tendency to increase i n the area of finer-grained sediments that have a noticeable H2S odor and i n areas adjacent to the mouths of r i v e r s . The copper values on Map #5 are the values 35 of soluble copper and represent fractions of the total amount of copper present. The form of the copper at Mud Bay is not known. Goldschmidt suggests that copper ions are carried by mud particles in rivers to the ocean where a number of possi-b i l i t i e s arise. He emphasizes the a f f i n i t y of organic material for copper. Copper may be assimilated by living organisms or the presence of SO^"^ and organic matter may lead to bacterial formation of H2S and the deposition of copper as a sulphide (Goldschmidt, 1954, p. 185, 182-183). The Permian shale at Mansfeld, Kupfershiefer, with a copper content of 2.9$, was cited as an example of marine deposition of copper under re-ducing conditions in sulphide bearing mud from stagnant, anaerobic, bottom waters (Goldschmidt, 1954, p. 185). The immediate source of copper could be from river water, ocean water, and/or organic material. G.A.Riley found in the Mississippi estuary that the highest copper values occurred in waters of relatively low salinity. His analyses indicated that copper was speedily removed from sea water, probably by organic material. The range of dissolved copper was 0.001 to 0.015 ppm in fresh water (Goldschmidt, 1954 p.186). The average copper content of ocean water is a subject of debate. Earlier values given by Sverdrup, Johnson, and Fleming are of the order 0.001 to 0.01 ppm, whereas Wattenburg in 1943 gives much lower values ranging from 0.0002 to 0.001 ppm (Goldschmidt, 1954, p. 186). 36 ZINC Zinc shows a tendency to concentrate i n the f i n e r sediment. Higher concentrations of zinc extend farther out into the bay than similar copper concentrations. The zinc values plotted on Map #6 represent soluble zinc extractable by "digestion" i n R^SO^ and i s only a f r a c t i o n of the t o t a l . zinc present. The form of the zinc i n the sediments at Mud Bay i s unknown. Like copper, zinc may be concentrated i n consider-able amounts i n the form of sulphides under reducing conditions. At Mansfeld, i n the Kupfershiefer, the highest zinc values occur where sulphur i s present but not i n the form of H2S produced by decaying organisms. Hence, at Mansfeld, the beds r i c h i n zinc do not coincide with the copper-rich beds (Rankama and Sahama, 1 9 5 0 , p. 7 1 3 ) . This p e c u l i a r i t y of zinc could account i n part for the differences i n the patterns of copper and zinc at Mud Bay. The average concentration of zinc i n sea water has not been d e f i n i t e l y established. Analyses prior to 194-3 indicated a high concentration of zinc i n sea water, but Wattenburg gives an average concentration of only 0 . 0 0 0 5 ppm zinc (Goldschmidt, 1954, p 2 6 5 ) . Possible sources of zinc at Mud Bay are (1) r i v e r waters, ( 2 ) ocean water, ( 3 ) organic material, and (4) water-borne clay p a r t i c l e s . It i s not known which possible source contributes the most zinc at Mud Bay. 37 LEAD The concentration of lead i n the sediments of Mud Bay-i s much too low to permit conclusions to be drawn regarding i t s d i s t r i b u t i o n . There i s a tendency for the s l i g h t l y higher values to occur i n the finer-grained near shore. Goldschmidt suggests that lead could be precipitated as a sulphide i n a manner similar to copper i n a reducing environment i n the presence of H9S (Goldschmidt, 1954, p.403). CHAPTER v i i i . CONCLUSIONS It i s concluded from th i s study that copper, z i n c , i r o n , and sulphur have r a t i o n a l rather than random patterns of d i s t r i b u t i o n i n the modern sediment of Mud Bay. The reasons for the existence of such patterns presently are un-known. Many questions remain concerning the form, source, and mode of deposition of these elements. In view of the modern trend to accept syngenetic hypotheses for many base-metal deposits i n sedimentary rocks, i t seems imperative that the mechanisms of such genetic theories be rigorously investigated. Further research into such matters would spread widely through f i e l d s of geo-chemistry, bacteriology, and zoology. Among other l i n e s of research i t would include study of the following: (1) Average and seasonal v a r i a t i o n of trace element content of r i v e r s , sediments, and marine waters. (2) Methods of analysis that give the t o t a l amount of elements that are chemically available for formation of ore minerals. (3) D i s t r i b u t i o n of organic materials i n the sediments and their effects on the deposition of trace elements. (4) Bacteria and t h e i r effects on the deposition of trace elements. SELECTED BIBLIOGRAPHY Armstrong, J . E . " S u r f i c i a l Geology of New Westminster Map-Area , B r i t i s h Columbia". Geol . Surv. Canada. Paper.-5Z-5' G a r l i c k , W.G. "Reflections on Prospecting and Ore Genesis i n Northern Rhodesia". B u l l . J n s t n . Min^ M e t a l l . No. 563, Oct . 1953, P 9-20. Goldschmidt, V . M . Geochemistry, ed. M u i r , Oxford (Clarendon) 1954. Lane, E.W. (et a l ) "Report on the Subcommittee on Sediment Terminology". Trans . Am. Geophys. Union, V o l . 28:6, p 936^ 938". Mol loy , M.W., K e r r , P . F . "X-ray Spectrochemical Ana lys i s : An A p p l i c a t i o n to Certa in Light Elements i n Clay Minerals and Volcanic Glass". Am. M i n e r a l . , V o l . 45:9&10 p 911-936. Rankama, K . , Sahama T h . G . , Geochemistry, Chicago, 1950. Warren, H . V . , De lavaul t , R . E . "Further Studies i n B i o -geochemistry". Geol . Soc. Am. B u l l . , V o l . 60, P 531-559. Warren, H . V . , De lavaul t , R . E . "Preliminary Studies of Biogeochemistry of Molybdenum". Trans. Royal Soc. Canada, Series 3, Sect . 4, 1953. p 71-75. Warren, H . V . , De lavaul t , R . E . "Soils i n Geochemical Pros-pect ing". West. Miner O i l Rev . , V o l . 29:12, p 36-42. Warren, H . V . , De lavaul t , R . E . Observations on Biogeo-chemistry of Lead". Trans. Royal Soc. Canada, i n press , 1961. White, W . S . , Wright, J . C . "The White Pine Copper Deposit , Ontonagon county, Michigan". Econ. G e o l . , V o l . 49:7 p 675-716. APPENDIX A SAMPLE•ANALYSES No - 2 0 0 $ Cu ppm Zn ppm Cu/Zn Pb ppm Mo ppm s% Fe$ 1 61 56 1 0 0 . 5 6 1 ^ 1 1 . 0 0 2 . 4 7 2 36 1 9 1 0 1 . 1 9 1 * 1 . 7 5 1 . 5 4 3 34 17 1 0 0 . 1 7 1 <1 . 8 5 2 . 4 9 4 12 14 51 . 2 8 1 <-i . 7 3 2 . 6 7 5 4 6 27 95 . 2 8 <•! * 1 .65 2 . 4 9 6 65 48 4 9 1 1 <1 . 8 0 2 . 4 9 7 51 1 4 6 9 . 2 0 1 <1 . 4 5 2.50 8 36 15 8 6 . 1 7 1 <1 . 7 1 2 . 3 7 9 23 26 51 .51 1 * 1 . 7 6 2 . 5 6 1 0 2 0 34 52 . 6 6 <1 ^ 1 . 8 5 2 .52 11 53 27 52 .52 *1 <1 1 . 1 2 2 . 8 1 1 2 4 9 9 78 . 1 2 2 * 1 . 6 6 2 .52 13 34 5 4 3 . 2 2 2 ^1 . 8 3 2 . 5 5 14 27 9 6 0 .15 1 * 1 . 7 9 2 . 5 8 15 27 9 6 0 .15 1 - 4 . 5 6 2 . 4 8 16 23 1 1 4 3 .26 1 - a . 4 5 2 .52 17 59 11 4 3 .26 1 <L .70 2 . 3 3 18 66 11 6 0 . 1 8 1 <1 .62 2 . 3 7 1 9 32 1 2 60 . 2 0 1 <1 . 8 0 2 . 7 8 2 0 52 29 4 3 . 6 7 1 "1 . 8 3 2 . 5 6 21 6 0 15 4 3 . 3 5 1 <1 . 8 7 2 . 5 4 22 47 15 .29 1 * 1 . 9 3 2 . 5 9 23 42 3 3 ^ 50& . 6 6 2 * 1 . 9 5 2 . 8 1 2 4 51 4 1 * 8 1 .51 2 ^ 1 . 8 8 2 . 5 6 25 4 6 24 4 3 . 5 3 * 1 1 . 0 0 2 . 6 3 26 56 34 60 . 5 7 1 - 1 . 7 6 2 .70 27 68 35 6 0 . 5 8 1 - 1 .92 2 . 8 1 28 6 1 31 77 . 4 0 2 - 1 . 7 3 2 . 4 8 29 4 9 31 52 . 6 0 - 1 .70 2 . 5 6 30 4 9 35 77 . 4 5 2 - a . 8 4 2.50 31 70 8 2 6 9 1 . 2 0 <1 *1 1 . 1 0 2.50 32 4 4 29 70 . 4 1 2 * i . 8 9 2 . 8 3 33 4 5 56 1 0 4 . 5 4 2 - l . 9 0 2 . 5 6 34 55 11 4 4 .25 1 ^ i . 9 6 2 . 6 4 35 70 15 70 . 2 2 2 - l 2 . 0 9 3 . 7 4 36 72 9 52 . 1 7 2 ^ i 2 . 1 1 2 .70 37 50 16 78 .20 2 ^ i . 9 9 2 . 8 2 38 72 16 .23 1 < L 1.24 2 . 7 6 39 75 18 5 6 j . .32 2 - l 1 . 1 0 2 . 7 7 4 0 6 9 20 7 2 A .29 2 - l 1 .29 3.25 4 1 75 24 6 1 . 3 9 2 - l . 9 1 2 . 9 5 42 32 36 52 . 6 9 1 - l . 5 9 2 . 7 6 4 3 52 13 .25 1 * - l . 5 6 2 . 5 8 4 4 18 15 5 8 & .26 ^ i . 6 3 2 . 5 8 4 5 39 7 52 . 1 3 7& - l . 6 6 2.50 A Indicates a re-analysis using the duplicate set of samples 41 No -200$ Cu ppm Zn ppm Cu/Zn Pb ppm Mo ppm 3$ Fe% 46 20 15 70 .21 3* *1 .63 2 .51 47 26 7 35 .20 2& <1 .71 2.48 48 10 1 3 35 .37 !* -=1 . 5 4 2.58 49 71 11 52 .21 3$ <1 .60 2 .57 50 68 24 61 .39 2H <1 .91 2.64 51 14 18 52 .35 1 •<1 .70 2 . 8 3 52 29 16 35 .46 2 -=1 .48 2 . 3 8 53 12 27 35 .77 1 *1 . 8 3 3 . 1 0 54 20 9 35 .26 1 -1 .66 2.58 55 20 16 35* .46 - c l *1 . 5 0 2.58 56 30 29 .24 1 -1 .66 2.43 57 31 9 . 35 .39 1 *1 .68 2.61 58 23 13 35 .37 1 *1 . 5 5 2.49 59 2 3 11 4 4 . 2 5 1 «1 . 8 3 2.93 60 16 44 52 .85 1 •<1 .46 2.93 61 26 20 4 4 .46 1 *1 .85 2 . 9 0 62 63 10 31 . 3 2 1 -1 . 8 7 2 . 6 8 63 3 17 24 . 7 1 1 -=1 . 2 5 2.73 64 10 17 37 .46 2 ~1 . 5 7 2 .52 65 14 1 5 31 .48 -el *1 .59 2.46 6 6 21 8 31 . 2 6 <1 *1 .58 2 .30 67 12 1 3 24 . 5 4 1 <1 . 5 7 2 . 54 68 8 18 31 . 5 8 1 -1 .56 2.82 69 15 14 24 .58 - c l <1 . 5 4 2.73 7 0 1 5 23 43 . 5 4 1 .64 2 . 5 2 71 14 8 . 2 6 ^1 •*1 .58 2 . 4 5 7 2 6 2\ 39* .59 *1 . 5 0 2 .75 73 6 33* .69 <1 <1 . 6 2 3.87 74 3 65* . 4 5 1 <1 .92 3.13 75 1 55 1.34 <-\ -<1 .36 3.20 76 7 55 . 5 1 *1 <1 .56 2.81 77 9 37 .84 <*1 -*1 . 6 2 2.81 78 7 2 5 * 39 .64 *1 -cl .56 2 . 8 3 79 19 25 .24 ^1 <1 . 7 0 2.60 80 16 10* .40 <L *1 .61 2.78 81 11 29A 48* .60 «-l <1 .56 3.01 82 4 40 a 80* . 5 0 -<1 <1 . 3 1 2.87 8 3 8 15 31 . 5 0 <L *1 .48 2.76 84 10 13 25 . 5 2 -=1 *1 .34 2 .50 85 26 7 18 .39 <1 <\ . 7 5 2.49 86 1 3 1 0 18 .56 -*1 <.\ .41 2 .70 87 8 15 18 . 8 3 *1 <L .40 2.95 88 14 14 31 . 4 5 <1 «1 .47 2.65 89 15 27 56& .48 -=1 -=1 .67 2.66 90 8 21 37 . 5 7 <1 *1 . 7 0 2.77 91 4 29 58 . 5 0 4 *1 . 3 8 2.99 & Indicates a re-analysis using the duplicate set of samples No -200$ Cu ppm Zn ppm Cu/Zn Pb ppm Mo ppm Sfo Fe% 92 12 43 75* .57 2 <.! .33 2.53 93 67 12 51 .24 2 *1 1.16 2.30 94 51 36 87 .41 2 *1 .71 2.88 95 41 15 65 .23 3 -el .47 2.61 96 18 51 65 .79 2 *1 .72 2.56 97 6 55 65 .85 1 <1 .46 2.96 98 5 38 87 .67 1 «a .53 2.64 99 13 23 80 .29 2 *1 .38 2.23 100 42 13 94 .14 1 <-l 1.14 2.44 101 60 57 80 .71 2 -*1 1.15 2.46 102 60 58 80 .73 4 <1 .97 2.46 103 62 40 65 .62 1 *1 1.15 2.44 104 3 51 80 .64 2 "1 .63 2.83 105 54 42 58 .73 2 -cl .78 2.40 106 51 37 72 .51 2 *1 1.18 2.84 107 64 45 80 .56 2 «1 .77 2.19 108 53 70 58 1.21 1 «1 1.45 2.61 109 65 57 80 .71 4 <1 1.35 2.93 110 70 102 65 1.57 1 <cl 1.21 2.46 111 77 46 109 .42 2 *1 .88 2.5 112 80 122 101 1.20 4 -=1 1.17 2.63 113 58 46 58 .79 1 <L 1.16 2.09 ft Indicates a re-analysis using the duplicate set of samples APPENDIX B MEAN VARIATION OF ANALYSES No. Cu #1 Cu #2 Varia- Zn #1 Zn #2 Varia-tion t i o n 1 5 6 91 3 5 100 76 24 2 19 35 16 101 85 16 3 17 3 1 14 100 59 41 4 14 2 3 9 5 1 59 8 5 2 7 31 4 95 76 19 6 not repeated 7 14 19 5 69 59 10 8 1 5 2 3 8 86 59 17 9 26 3 5 9 5 1 5 0 1 10 34 76 42 5 2 59 7 11 2 7 5 1 24 5 2 67 1 5 12 9 12 3 78 59 19 13 5 16 11 43 59 1 6 14 9 12 4 6 0 42 18 1 5 9 14 5 60 5 0 10 16 11 18 7 43 5 0 7 1 7 11 12 1 43 5 0 7 18 11 14 3 60 42 18 19 12 18 6 60 5 0 1 0 20 2 9 39 10 43 59 1 6 21 1 5 2 3 8 43 42 1 22 1 5 2 3 8 5 2 5 0 2 2 3 33 39 6 93 5 0 43 24 14 41 2 7 81 5 0 31 2 5 24 33 9 43 59 1 6 2 6 34 65 3 1 60 59 1 2 7 35 49 14 6 0 59 1 28 3 1 45 14 77 67 10 2 9 3 1 33 2 5 2 67 1 5 3 0 35 39 4 77 59 18 3 1 82 113 31 69 76 7 Mean Varia t i o n 1 2 ppm Mean Variation 1 3 ppm APPENDIX C TABLE OF FORMATIONS' GROUP GLACIO- -GLACIO- .GLACIO-GLACIAL FLUVIAL LACUSTRINE MARINE OFF SHORE • SHORE •ESTUARINE AND DELTAIC - CHANNEL MD FLOODPLAIN SALISH JPostglacial recent SUMAS Post-Vashon glacial-valley • ice (CAPILANO) VASHON Last ice-sheet glaciation Surrey t i l l ( 5 ) SEMIAMU Glaciation Abbotsford Outwash (10) Whatcom Glacio-marine(9) Newton Stony Clay(8) Cloverdale Sunny-side Sediments Sand (6) " (7) Richmond Delta (2) EROSIONAL INTERVAL t Fraser Floodplain (1) QUADRA I n t e r t i l l SEYMOUR Glaciation EROSIONAL INTERVAL Colebrook Gravel(4) and Nicomekl S i l t (3) k Taken from J.E.Armstrong, 19579 Figure 1 (2) corresponds to number in text P E R C E N T SULPHUR C A L I B R A T I O N C U R V E F O R IRON P A G E 2 0 ( a ) 20 e 59-REPRODUCIBILITY OF IRON ANALYSES Figure 4 a IRON KoC PEAK, SAMPLE 106 B Figure 4b IRON K<C PEAK, SAMPLE 106 C Figure 4c IRON K=C PEAK, SAMPLE 106 F CRUSHED LEI m Hi & F(6.M. PAGE 21(a) REPRODUCIBILITY OF IRON ANALYSES Figure 4 a IRON K°C PEAK, SAMPLE 106 B Figure 4b IRON K«=c PEAK , SAMPLE 106 C Figure 4 c IRON K<=C PEAK, SAMPLE 106 F CRUSHED PAGE 21(a) C A L I B R A T I O N C U R V E F O R S U L P H U R 3%4 cc 3 COUNTS PEAK TO BACKGROUND IN 30 SEC. FIGURE I P A G E 17(a) C A L I B R A T I O N C U R V E F O R I R O N C O U N T S P E A K TO BACKGROUND IN 15 S E C . F IGURE 3 P A G E 2 0 ( a ) 

Cite

Citation Scheme:

        

Citations by CSL (citeproc-js)

Usage Statistics

Share

Embed

Customize your widget with the following options, then copy and paste the code below into the HTML of your page to embed this item in your website.
                        
                            <div id="ubcOpenCollectionsWidgetDisplay">
                            <script id="ubcOpenCollectionsWidget"
                            src="{[{embed.src}]}"
                            data-item="{[{embed.item}]}"
                            data-collection="{[{embed.collection}]}"
                            data-metadata="{[{embed.showMetadata}]}"
                            data-width="{[{embed.width}]}"
                            async >
                            </script>
                            </div>
                        
                    
IIIF logo Our image viewer uses the IIIF 2.0 standard. To load this item in other compatible viewers, use this url:
http://iiif.library.ubc.ca/presentation/dsp.831.1-0053035/manifest

Comment

Related Items