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The distribution of zinc and copper in Georgia Strait, British Columbia : effects of the Fraser River… Thomas, David Joseph 1975

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THE DISTRIBUTION OF ZINC AND COPPER IN GEORGIA STRAIT, BRITISH COLUMBIA: EFFECTS OF THE FRASER RIVER AND SEDIMENT-EXCHANGE REACTIONS by DAVID JOSEPH THOMAS B . S c , Queen'sUniversity at Kingston, 1972 A THESIS SUBMITTED IN PARTIAL FULFILMENT OF THE REQUIREMENTS FOR THE DEGREE OF MASTER OF SCIENCE in the Department of Chemistry and the Ins t i tu te of Oceanography We accept th i s thesis as conforming to the requirexLstandard THE UNIVERSITY OF BRITISH COLUMBIA February, 1975 In present ing th is thes is in p a r t i a l fu l f i lment of the requirements for an advanced degree at the Un ivers i ty of B r i t i s h Columbia, I agree that the L ibrary sha l l make it f ree ly ava i l ab le for reference and study. I fur ther agree that permission for extensive copying of th is thes is for scho la r ly purposes may be granted by the Head of my Department or by h is representa t ives . It is understood that copying or pub l i ca t ion of th is thes is fo r f inanc ia l gain sha l l not be allowed without my wr i t ten permission. Department of ?Va?./Z^o The Univers i ty of B r i t i s h Columbia Vancouver 8, Canada Date ^ A ^ C ~? /?5~ i i ABSTRACT The d i s t r i b u t i o n of d i ssolved and par t i cu la te copper and zinc was studied at a ser ies of s tat ions in Georgia S t r a i t between May 1973 and May 1974. Large time-dependent f luctua-tions in the concentrations of both metals were observed which appeared to be re la ted to the discharge of the Fraser River . Although there i s i n s u f f i c i e n t data at present to explain many of the deta i led features of the d i s t r i b u t i o n s , most of the large scale features can apparently be re l a ted to a release of copper and zinc from r iver-borne sediment as i t passes from fresh to s a l t water. Laboratory experiments performed on Fraser River sediment and a rough estimation of the zinc and copper budgets in Georgia S t r a i t are consistent with th i s hypothesis . The tendency of copper and zinc concentrations to covary sug-gests that the i r d i s t r i b u t i o n s are cont ro l l ed by s imi la r pro-cesses. Thus, the ava i lab le evidence suggests that the ob-served dissolved metal d i s t r i b u t i o n s are large ly the re su l t of complicated mixing patterns superimposed on the effects o^f"^ — sediment-exchange reactions and the s inking of sediment p a r t i c l e s . i i i TABLE OF CONTENTS Page ABSTRACT i i LIST OF TABLES v LIST OF FIGURES v i ACKNOWLEDGEMENTS v i i i 1. INTRODUCTION 1 1.1 Georgia S t r a i t : Geographical Set t ing 2 1.2 Freshwater Budget 5 1.3 C i r c u l a t i o n and T i d a l Ef fects in Georgia S t r a i t 7 2, METHODS 10 2.1 Sampling 10 2.2 A n a l y t i c a l 14 2.2.1 Seawater analys is for dissolved zinc and copper 14 2.2.1.1 F i l t r a t i o n procedure 14 2.2.1.2 E x t r a c t i o n procedure 14 2 .2 .1 .3 Determination of zinc and copper 17 2.2.1.4 Prec i s ion . . . 18 2.2.2 Suspended sediment analys is 19 2.2.3 Bottom sediment analys i s 19 2.2.3.1 Copper and zinc dissolved in i n t e r s t i t i a l waters 19 2.2.3.2 0. IN; HC1. extractable copper and zinc in sediments 19 i v Page 3. RESULTS . 21 3.1 Experimental . 21 3.1.1 The desorption of copper and zinc from Fraser River sediment 21 3.1.2 Fraser River sediment: adsorption isotherm 2 6 3.1.3 Ef fect of f i l t e r pore s ize on the estimation of d i ssolved zinc and copper 2 7 3.2 F i e l d 32 3.2.1 Dissolved zinc and copper 32 3.2.2 Par t i cu la te zinc and copper 46 3.2.3 I n t e r s t i t i a l and sediment copper and zinc 48 3.2.4 S a l i n i t y . 48 4. DISCUSSION 54 5. SUMMARY 66 BIBLIOGRAPHY 6 8 APPENDIX A. Georgia S t r a i t s ta t ion pos i t ions 72 APPENDIX B. A n a l y t i c a l data . 73 B . l Seawater analyses 73 B.2 Zinc and copper in Georgia S t r a i t sediment in te r -s t i t i a l waters 108 B.3 0.1 N HC1 extractable zinc and copper in Georgia S t r a i t sediment 109 B.4 Fraser River water analyses 110 V LIST OF TABLES Table Page 1.1 Dimensional and hydrologic parameters of Georgia S t r a i t 4 2.1 Cruise numbers, dates and stat ions sampled 10 2.2 Prec i s ion of AAS analyses 18 3.1 Desorption of zinc and copper from Fraser River sediment on treatment with seawater 22 3.2 Estimation of t o t a l desorbable zinc and copper from Fraser River sediment 23 3.3 (a) Fraser River sediment adsorption data: F i t to Freundlieh isotherm equation 28 (b) I r r e v e r s i b i l i t y of adsorption 28 3.4 The effect of f i l t r a t i o n with 0.45 pm and 0.20 um pore s ize f i l t e r s on di s so lved and sus-pended values 31 v i LIST OF FIGURES Figure Page 1.1 Location map of the study area 3 2.1 Georgia S t r a i t s t a t ion locat ions 11 2.2 Fraser River sampling locat ions 13 3.1 The ef fect of s a l i n i t y on the desorption of zinc from Fraser River sediment 24 5.2 The ef fect of s a l i n i t y on the desorption of cop-per from Fraser River sediment 25 3.3 Freundlich adsorption isotherm of Fraser River sediment for copper and zinc 29 3.4 Relat ionship between zinc and copper adsorbed or desorbed and the re s idua l concentrations of those metals in so lut ion 30 3.5 D i s t r i b u t i o n of d i s so lved zinc and copper at 1 metre during August 1973 34 3.6 D i s t r i b u t i o n of d i s so lved zinc and copper at 3 metres during August 1973 35 3.7 D i s t r i b u t i o n of d i s so lved zinc and copper along sect ion CD during August 1973 36 3.8 D i s t r i b u t i o n of d i s so lved zinc and copper at 1 metre during September 1973 37 3.9 D i s t r i b u t i o n of d i ssolved zinc and copper at 3 metres during September 1973 39 3.10 D i s t r i b u t i o n of d i ssolved zinc and copper along sect ion CD during September 1973 40 3.11 D i s t r i b u t i o n of d i s so lved zinc and copper along sect ion AB during August 1973 41 3.12 D i s t r i b u t i o n of d i s so lved zinc and copper along sect ion AB during September 1973 42 3.13 Var i a t ion of d i s so lved zinc and copper at s ta t ion 3 between May 1973 and May 1974 . . . 44 v i i Figure Page 3.14 Var i a t ion of d i ssolved zinc and copper at s ta t ion 12 between July 19 73 and January 1974 45 3.15 D i s t r i b u t i o n of p a r t i c u l a t e z i n c and copper at • 1 metre during August 1973 47 3.16 D i s t r i b u t i o n of s a l i n i t y at (a) 1 metre during August 19 73 and (b) r metre;-, during September 1973 50 3.17 Var i a t ion of T, S ° / o o , ^ t at s ta t ion 3 between May 1973 and May 1974 51 3.18 Var i a t ion of s a l i n i t y at s ta t ion 12 between July 1973 and January 1974 52 4.1 Comparison of suspended sediment load and d i s -charge of Fraser River at Hope, B . C . , with dissolved zinc and copper at depth less than 20 metres at s t a t ion .3 f o r f t h e per iod May 1973 to May 1974 55 4.2 V a r i a t i o n of s a l i n i t y , d i s s o l v e d zinc and copper, and par t i cu l a te zinc and copper at 1 metre along section AB during August 1973 58 4.3 Var i a t ion of s a l i n i t y , d issolved zinc and cop-per , and par t i cu la te zinc and copper at 3 metres along sect ion CD and i t s extension into the Fraser River during August 1973 . 60 4.4 Relat ionship between dissolved metal and p a r t i -culate metal for stat ions near the Fraser River mouth between May and September 1973 61 4.5 Relat ionship between s a l i n i t y and dis so lved zinc and copper at depths less than 20 metres and depths greater than 20 metres for sta-tions near the Fraser River mouth between May and September 1973 62 v i i i ACKNOWLEDGEMENTS It i s a pleasure to acknowledge my grat i tude to my research supervisor , Dr. E . V . G r i l l for his pat ience, guid-ance and advice at each stage in the preparation of th i s thes i s . I would also l i k e to express my appreciat ion to others who helped: To Mr. W.B. Moody III for assistance with sample c o l l e c t i o n at sea; To Mr. F .A. Whitney for technica l ass i s tance; and To Carolyn for her pat ience , support, and e spec i a l ly her sense of humour. 1 1. INTRODUCTION Trace elements are extremely react ive const i tuents of seawater which are involved in both the geochemical and b io-chemical cycles of the oceans. Both zinc and copper, which have average concentrations in seawater of 5" and 3 pg/1 res-pec t ive ly (Ri ley and Chester, 1971) , are e s s en t i a l micronu-t r i e n t s to a l l marine organisms. Thus, i f the concentrations of these metals are too low they cannot be a s s imi la ted i n s u f f i c i e n t amounts to sustain e s s e n t i a l l i f e processes; how-ever, at high concentrations they may become t o x i c . The waters of Georgia S t r a i t and the Fraser River have not been the subject of d e t a i l e d trace element analyses in the past . To ta l z inc and copper have been determined in the Fraser R i v e r , but no attempt was made to d i f f e r e n t i a t e between d i s so lved and p a r t i c u l a t e phases (Benedict et a l , 1974; H a l l et a l , 1974). Georgia S t r a i t sediments have been studied i n terms of ca t ion exchange capacity (Mathews and Shepard, 1962; Pharo, 1972) but few data are ava i l ab le on trace elements or on.the changes occurr ing in the trace e le-ment content of sediment on passage from freshwater to s a l t -water. Kharkar, ej: a_l. (1968) have shown that seawater tends to desorb a number of trace metals from various so l ids that commonly occur i n suspension in r i v e r water; however, the resu l t s have l i m i t e d u t i l i t y because of the large devia t ion 2 of the laboratory condit ions from true f i e l d condi t ions . In-vest igat ions of soluble-adsorbed zinc and copper e q u i l i b r i a in natura l waters (O'Connor and Renn, 1964; Nakhshina and Feldman, 1971) suffer the same c r i t i c i s m . The changes occur-r ing in the major c a t ion ic composition of c lay mineral suites subsequent to passage from freshwater to saltwater have been studied by many invest igators inc luding Whitehouse (1958), C a r r o l l and Star iey (1960), Dobbins et a l . (1970), K e l l e r (1970), and Sharma (1970). Although these studies do not concern trace elements, they do i l l u s t r a t e some of the chemi-ca l c h a r a c t e r i s t i c s of sediment-seawater in te rac t ions . Enrichment of zinc and copper might be expected in the Fraser River-Georgia S t r a i t area of B r i t i s h Columbia as the r e su l t of the i r desorptive release from suspended r i v e r part-i c l e s as they move from freshwater into saltwater. The object-ives of this study were to describe the s p a t i a l and temporal var ia t ions in the d i s t r i b u t i o n s of d i s so lved and par t i cu l a te copper and zinc in Georgia S t r a i t and determine i f they could be re la ted to Fraser River runoff and sediment load. 1.1 Georgia S t r a i t : Geographical Sett ing Georgia S t r a i t i s the submerged port ion of the Georgia Depression (Holland, 1964) which extends along the coast of B r i t i s h Columbia between Vancouver Island and the mainland (Figure 1.1). The long axis of the f jord extends in a north-westerly d i r e c t i o n from the Gulf Islands in the south to 4 Quadra Is land in the nor th , a distance of approximately 225 ki lometres . The waters of Georgia S t r a i t are connected to the P a c i f i c Ocean in the south by means of the S t r a i t of Juan de Fuca, and in the north through numerous narrow channels. The bottom topography of the S t r a i t varies consider-ably. In the region of the Fraser River d e l t a , a smooth fan of sediments extends almost completely across the S t r a i t , while in the north the S t r a i t i s character ized by steep-sided ridges which separate deep, f l a t - f l o o r e d bas ins . The p r i n c i p a l d i -mensional and hydrologic parameters of Georgia S t r a i t are l i s t e d in Table 1.1. TABLE 1.1 PRINCIPAL DIMENSIONAL AND HYDROLOGIC PARAMETERS OF GEORGIA STRAIT (AFTER WALDICHUK, 1957) Length 225 km Average width 33 km Surface area 6900 km2 Mean depth 156 m Maximum depth . 421 m Mean volume 1025 km3 Mean t i d a l range 3.6 m Total runoff/year 145 km3 Total d i rec t p r e c i p i t a t i o n / y e a r 9.6 km3 S i l l depth (south) 6 8 m 5 Detai led information on the dimensions, structure and geology of the S t r a i t of Georgia i s found in Mathews and Murray (1966) , T i f f i n (1969) and Waldichuk (1957). During the present study, sampling was conducted only in the port ion adjacent to the mouth of the Fraser River ; that i s , between Boundary Passage and the northern t ip of Texada Island (Figure 1.1). 1. 2 The Freshwater Budget By f a r , the largest source of freshwater for Georgia S t r a i t i s from stream runoff . In contrast to other B .C. f jo rds , the input of freshwater comes mainly from the sides rather than the head of the i n l e t . Although numerous r ive r s discharge into Georgia S t r a i t , the Fraser R iver , which has a drainage area of more than 90,000 mi^ upstream from New Westminster, i s e a s i l y the most important, contr ibut ing some 801 of the t o t a l runoff (Mathews and Murray, 1966). The great bulk of th i s runoff is derived from snowmelt. The delta area i s comprised of three main r i v e r mouths, the greatest volume of water entering the S t r a i t v i a the South Arm. The North Arm passes approximately 10-15% and Canoe Pass contributes a r e l a t i v e l y i n s i g n i f i c a n t amount (Mathews and Murray, 1966). Associated with the discharge of the freshwater from a l l sources i s the transport of s i g n i f i c a n t amounts of both organic and inorganic suspended matter. The organic f r ac t ion i s made 6 up c h i e f l y of woodchips, sawdust, l i v i n g and dead microorganisms and products r e s u l t i n g from the decomposition of these mater-i a l s , while the inorganic f rac t ion i s c h i e f l y oxides, carbon-ates, s i l i c a t e s , and clays in sand, s i l t , and c l a y - s i z e d p a r t i c l e s '(Vancouver and D i s t r i c t s Jo int Sewerage and Drainage Board (1953), Mathews and Murray (1966)). Perhaps the most s t r i k i n g aspect of the Fraser R iver ' s flow i s i t s large seasonal v a r i a t i o n . Stream flow at the de l ta i s estimated at 700 to 1400 m 3/sec in January, February and March, r i s i n g r ap id ly to over 17,000 m 3/sec in June and then dec l in ing i r r e g u l a r l y to low flow rates the fol lowing win-ter (Mathews and Murray 1966). The suspended sediment load shows even more pronounced seasonal changes, increas ing from about 900 to 3200 tons/day at low runoff to between 540,000 and 810,000 tons/day during the freshet ( I v i d d , 1953). Measurements at New Westminster i n -dicate that the actual sediment concentration varies from about 18 mg/1 to over 300 mg/1 (Johnston 1921). No r e l i a b l e estimate of bedload has yet been made. The suspended sediment load experiences a cont inua l ly changing s a l i n i t y as i t moves through the Fraser River estuary. Cameron and Pr i tehard (1960) define an estuary as " a semi-enclosed C Q a s s l t a ! l body of water having a free connection to the open sea and within which seawater i s measurably d i lu ted with freshwater der iv ing from land drainage". Under this broad d e f i n i t i o n , a l l of Georgia S t r a i t i s e s s en t i a l l y an estuary. The part of the estuary nearest to the Fraser River most re-sembles a s a l t wedge estuary in Stommel's (19S3) c l a s s i f i c a -t i o n , while the rest of the S t r a i t may be considered a highly s t r a t i f i e d f j o r d type estuary. The extent to which the saline water intrudes from Georgia S t r a i t as a wedge below the r i v e r water depends on the magnitude of the r i v e r discharge. Dur-ing the freshet, the s a l t wedge r a r e l y extends upstream be-neath the r i v e r water farther than Steveston, but during low runoff, water of s a l i n i t y 15°/00 may extend as far upstream as Annacis Island (Johnston, 1921; Hodgins, 1974). A r e l a -t i v e l y well-defined saltwater-freshwater interface exists along the leading edge of the outflowing r i v e r water and at the boundary with the s a l t wedge. Waldichuk (1967) indicated that the sharp surface t r a n s i t i o n zone between the fresh, turbid water of the Fraser River and the sa l i n e , clear water of Georgia S t r a i t occurs at a s a l i n i t y of about 15^/00. This t r a n s i t i o n zone i s located at Sand Heads during low runoff and moves progressively westward as the intensity of the r i v e r flow increases. 1.3 Ci r c u l a t i o n and Tid a l E f f e c t s in Georgia S t r a i t T u l l y (1952, 1957) has discussed the general features of c i r c u l a t i o n in Georgia S t r a i t . It i s seen as an arm of the sea into which the Fraser River discharges, forming a brackish upper zone (0-30 metres) which entrains saltwater as i t moves p e r s i s t e n t l y seaward. The loss of saltwater i n the upper zone i s compensated by an inflow of seawater through the lower zone. The outflow and inflow are dynamically 8 interdependent, an increase i n r i v e r flow tending to decrease the s a l i n i t y but simultaneously causing an inflow of seawater which r e s i s t s t h i s tendency (Pickard, 1963). For lack of un-derstanding of coupling, the t i d a l o s c i l l a t i o n s are considered as independent phenomena superimposed on the c i r c u l a t i o n . Tully (1952) also indicated that brackish waters are present in the southern channels during ebb tide. However, Waldichuk (1957) found that freshwater tends to be refluxed in th i s area to an extent which could not be p r e c i s e l y defined. Overall, the tides have a very strong influence on the c i r c u l a t i o n of the brackish surface water formed at the r i v e r mouth and on the transport of the suspended sediment that i t contains, which results in a very complicated d i s t r i b u t i o n of clay and s i l t - s i z e d p a r t i c l e s in the S t r a i t of Georgia. Dur-ing the flooding tide, brackish water and suspended sediment are car r i e d rapidly northward along the mainland shore. River discharge i s intermittent, causing the formation of cloud-like pools of brackish waters which tend to move independently under the influence of the wind and l o c a l currents. As a r e s u l t , there are large fluctuations in the temperature, s a l i n i t y and dissolved oxygen content within the waters of upper layers near the r i v e r mouth. During the ebb tide the westward movement of r i v e r water is less r e s t r i c t e d ; as a r e s u l t , freshwater flow extends from the r i v e r mouths toward Active Pass. However, a e r i a l photo-graphs indicate that some northward movement of s i l t y water along the mainland coast i s possible at this time (Pharo, 1972; Tabata, 1972). 9 F l o o d i n g t i d a l c u r r e n t s are g e n e r a l l y stronger and of longer d u r a t i o n on the e a s t e r n s i d e of the s t r a i t than on the western s i d e , while the reverse i s true f o r ebbing t i d e s . T h i s combined t i d a l flow, together w i t h l o c a l wind c o n d i t i o n s and the i n f l u e n c e s of topography tends to produce a general a n t i - c l o c k w i s e water c i r c u l a t i o n p a t t e r n w i t h i n the S t r a i t ; but departures from t h i s are common (Crean, 1969) . Both T u l l y (1957) and Waldichuk (1957) i n t e r p r e t e d s a l i n i t y , temperature and d e n s i t y d i s t r i b u t i o n s i n the S t r a i t to imply a downward t r a n s f e r of upper zone water duri n g the summer p e r i o d . The waters of the c e n t r a l b a s i n are n e a r l y homogeneous i n January, but are r e p l a c e d s h o r t l y afterwards with Juan de Fuca water. 10 2. METHODS 2.1 Samp l i n g A l l sampling, with the exception of freshwater samples, was performed during the period May 19 73 to May 19 74 from the oceanographic research vessel CSS Vector. Water and sediment samples were obtained from a series of stat ions in the S t r a i t as indicated in Figure 2 » 1 . Table 2.1 l i s t s the cruise num-bers, cruise dates and the stat ions sampled. TABLE 2.1 CRUISE NUMBERS, CRUISE DATES AND STATIONS SAMPLED CRUISE :" • DATE STATIONS SAMPLED 73/21 May 28, 1973 3 73/28 Ju ly 18-19, 1973 1, 3, 5.7, 12 73/30 • August 1-3, 19 7 3 1, 2, 3, 4, 5, 5.7, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16 73/31 August 15-16, 1973 3, 5.7, 12 73/35 September 4.-6, 1973 2^  3^  4^  5^ 5« 5y 6, 7, .8, 9, 10, 11, 12, 13, 14, 15, 16 73/46 November 14-16, 1973 3, 5.5, 5.7, 6, 12, 14, 16 74/1 January 7-9, 1974 3, 5 .5 , 6, 12, 14, 16 74/15 A p r i l 30, 1974 3, 5.5 F i g u r e 2.1 Georgia S t r a i t s t a t i o n l o c a t i o n s 12 Water samples were c o l l e c t e d in 1.2 £ polypropylene NIO bot-t l e s . The trace metal samples (500 ml) were f i l t e r e d , a c i d i -f i ed and stored in polypropylene bot t les at 5 ° C immediately af ter c o l l e c t i o n . Sediment samples were c o l l e c t e d with a gravity corer (10 cm i . d . ) constructed of PVC and having a s ta in le s s s teel sediment cu t te r . Once r e t r i e v e d , the core was extruded and the sediment from the 0-2, 5-7 and 10-12 cm depth layers transferred to polyethylene bags for storage at 5 ° C . A l l equipment for processing and s tor ing samples on shipboard was cleaned p r i o r to each cruise by washing with hot 6 N HC1 and r i n s i n g with deionized water several times. Samples of Fraser River water and mud were c o l l e c t e d on three occasions (August 29th 1973, November 10th 1973 and January 16th 1974) at four loca t ions : Johnson Slough, Aggassiz, Mis s ion , and Fort Langley (Figure 2.2) . The r i v e r water samples were c o l l e c t e d at the surface d i r e c t l y into 500- ml polypropylene bott les and f i l t e r e d upon return to the labor-atory. After a c i d i f i c a t i o n , they were then stored at 5 ° C . On the average, several months passed between the time of sampling and the time of ana lys i s . It i s not bel ieved that any s i g n i f i c a n t changes occurred in the copper and zinc contents of the water during th i s time since, the storage con-d i t ions were s imi la r to those used by Erickson (1973), who observed no change over several weeks. A c i d i f i c a t i o n prob-ably prevents adsorption of the metals onto the container 13 Figure 2.2 Fraser River sampling locat ions 14 walls during storage (Robertson, 1968). 2.2 A n a l y t i c a l 2.2.1 Seawater Analys i s for Dissolved Cu and Zn 2.2.1.1 F i l t r a t i o n Procedure Immediately a f ter c o l l e c t i o n , the 500 ml seawater sam-ples were f i l t e r e d through Gelman Me t r i ce 1 GA6 membrane f i l -ters (0.45 um average pore diameter) which had been soaked for at least 30 minutes in a 5% so lut ion of KH2PO4 to leach out any metals present on the f i l t e r s . F i l t e r i n g was achie-7 ved under reduced pressure using a M i l l i p o r e f i l t e r uni t f i t -ted into a 1 - l i t r e polypropylene f i l t e r - f l a s k . A l l parts of the f i l t r a t i o n set-up were washed by f i l t e r i n g about 50 ml deionized water and discarding i t . The f i r s t 50 ml of seawater were also discarded before the remainder of the sample was f i l t e r e d . After f i l t r a t i o n , the remaining 450 ml of seawater was transferred into a 500 ml polypropylene sample bot t l e and enough 6 N HC1 added to br ing the pH of the so lut ion to about 2 .0 . The f i l t e r s were stored in P e t r i dishes for subsequent analysis of p a r t i c u l a t e matter. 2.2.1.2 Extrac t ion Procedure Because of the low leve l s of copper and zinc in the samples i t was necessary to preconcentrate the metals before analys i s by atomic absorption spectrophotometry. Several solvent extract ion systems have been described (cf Joyner 15 and Healy 1967; Spencer and Brevier 1970) in th i s connection. Chelation of copper and zinc with sodium diethyldithiocarbamate (NaDDC) followed by extract ion with isoamylacetate (IAA), back extract ion into an aqueous phase, reformation of the metal diethyldithiocarbamates and extract ion into methyliso-butylketone (MIBK) was employed here. The advantages of t h i s procedure are i t s speed, the s t a b i l i t y of zinc and copper chelates of NaDDC over several hours (Nix and Goodwin 1970), and the presence of high and stable absorbances due to the exce l lent combustion charac te r i s t i c s of MIBK in an a i r / acetylene flame. In order to minimize contamination, a l l glassware was ca re fu l ly cleaned with 6 N HC1 and then r insed with d i s t i l l e d water, acetone and f i n a l l y deionized water before use. Reagent So lut ions : NaDDC, 21; 2.0 g of Fisher ACS diethyldi thiocarbamic ac id t r ihydra te , sodium s a l t , were dissolved in 98 g deionized water. The r e s u l t i n g so lut ion was extracted at least twice with 5 ml portions of GCI4.Solution prepared for each use. Na C i t ra te Buffer , 1.3 M: 191 g Baker Analyzed sodium c i t r a t e dihydrate were dissolved in deionized water and d i l u t e d to 500 ml. This so lut ion was extracted with 2 ml .2%.;NaDDC .and 10 ?inl'- CCI4. u n t i l - a l l ' the tmetals -we re r^,#md.ve d. T r i s Buffer , 1.0 M: 60.6 g of Baker Analyzed Primary Standard Grade Tris-hydroxymethylaminomethane were dissolved in de-ionized water and d i l u t e d to 500 ml. Extracted as Na C i t ra te above. 16 IAA and MIBK: r e d i s t i l l e d before use. Copper Stock Solution, 100 ppm: Baker reagent grade copper metal dissolved in n i t r i c acid. Zinc Stock Solution, 100 ppm: Baker reagent grade zinc metal dissolved in hydrochlorrc acid. After transferring the 450 ml sample of a c i d i f i e d seawater to a 500-ml Erlenmeyer flask, the pH was adjusted to 8.0-8.5 with 6N NH4OH using a pH meter, and then 5 ml of 1.3M Na Ci t r a t e , 5 ml of 1% NaDDC and 20 ml IAA added. The solution was then s t i r r e d with a magnetic s t i r r e r for 20 minutes and, after allowing 5 minutes for phase separation, the IAA phase transferred to a 125 ml polypropylene separa-tory funnel using a pipette equipped with a rubber suction bulb. The sample was then extracted tivo more times with 10 ml of IAA, mixing each time for 20 minutes and allowing 5 minutes for phase separation. To the combined IAA extracts, 2 ml of Cl2 _water (available CI2 greater than or equal to 0.51) that was 1% in HC1 was ..added and the mixture was shaken for one minute. After phase separation, the aqueous f r a c t i o n was transferred to a 25-ml glass-stoppered graduated cylinder and a few ml of deionized water added to the separatory funnel to wash out the residual drops of back extract retained in the stem. The organic phase was then shaken with 5 ml de-ionized water for 30 seconds and the aqueous phase combined with that in the graduated cylinder as before. The contents of the cylinder were then diluted to 20 ml and transferred 17 to a dry acid-washed one-ounce polypropylene b o t t l e . The IAA phase should show a strong yellow colourat ion due to the pre-, sence of excess C I 2 . I f not the C l2 -water back extract ion was repeated to prevent the p o s s i b i l i t y of incomplete re-covery of a l l the complexed metals. Reagent blanks were prepared by executing the ent i re extract ion procedure on 450 ml of deionized water. One blank was prepared for every 9 seawater samples and each time any of the reagents was renewed. 2 .2 .1 .3 Determination of Copper and Zinc Both copper and zinc were determined using a Techtron Model AA-4 Atomic Absorption Spectrophotometer operating with an a i r /acety lene flame and Techtron AB-51 10-cm burner. The absorption measurements were made at 324.8 nm and 213.9 nm for copper and z i n c , r e spec t ive ly . Zinc was determined by a sp i ra t ing some of the aque-ous concentrate d i r e c t l y into the flame. Af ter correc t ing for background absorption using a deuterium lamp and for the absorption due to the reagent blank, the amount of zinc pre-sent was determined by comparison to a set of aqueous stan-dards. The standards were prepared by d i l u t i n g the stock zinc so lut ion with deionized water to give solutions contain-ing 0.4, 0.6 and 0.8 ug Zn/ml. The c a l i b r a t i o n curve was l i n e a r . Analys i s for copper was made fol lowing an addi t iona l concentration step. A 15-ml a l iquot of the 20-ml concentrate 18 was pipetted into a 25-ml graduated cy l inder along with 1 ml of IM T r i s buf fer , enough 6N NH4OH to br ing the pH to 8-8.5 and 1 ml of 1% NaDDC. Then the copper was extracted into 2.0 ml of MIBK by shaking the samples for one minute. Five min-utes was allowed for phase separation and then the organic phase was aspirated into the flame. After correc t ing the measured absorbance for that of the reagent blank, the copper concentration' was determined by comparison to a set of stan-dards containing 0.4, 0.6, and 0.8 pg Cu/ml that had been ex-tracted into MIBK. The c a l i b r a t i o n curve was l i n e a r . 2 .2 .1.4 Precis ion Ten samples, each containing 25 pg/1 of copper and z inc , were prepared with deionized water and subjected to procedures 2.2.1.2 and 2 .2 .1 .5 . The resul t s are shown in Table 2j2. TABLE 2.2 PRECISION OF AAS ANALYSES Sample Zn Found pg/1 Cu Found pg/1 1 25.2 24.0 2 25.0 24.5 3 22.1 25.1 4 24.4 25.6 5 22.8 25.2 6 25.5 - 24.1 7 22.5 25. 7 8 21.0 22.4 9 22.7 25.0 10 25.0 25 t6 Mean 25.2 25.7 Recovery - 92.81 94. 8% 19 It follows then, that the r e l a t i v e standard deviat ions for copper and zinc (at the 25 pg/1 l eve l ) are 3.3% and 51 re spec t ive ly . Employing a series of metal-spiked seawater samples ( s tat ion 12 seawater spiked to increase zinc concen-trat ions by 1, 2, 3, 4 and 5 pg/1 and copper concentrations by .1, .2, .3, .4 and .5 pg/1) recoveries for zinc and copper were determined to be, r e s p e c t i v e l y , 98% and 99%. No attempt was made to adjust the data for these incomplete recover ies . 2.2.2 Suspended Sediment Analys i s The f i l t e r s stored in P e t r i dishes were transferred to 100-ml beakers and heated together with a mixture of 2.0 ml HNO3 and 0.5 ml HCIO4 u n t i l evolut ion of HCIO4 fumes. After washing the remains of this digest into a 25-ml gradu-ated cy l inder and d i l u t i n g to 20 ml, the zinc and copper con-centrations were determined by AAS as above for seawater. 2.2.3 Sediment Sample Analys i s 2.2.3.1 Copper and Zinc Dissolved in I n t e r s t i t i a l Waters The sediment i n t e r s t i t i a l waters were extracted using the a l l - p l a s t i c , gas-operated sediment squeezer described by Reeburgh (1969) operated at a N2 pressure of 30 p s i g . The i n t e r s t i t i a l water extract was then analyzed for d i s so lved copper and zinc as out l ined in 2.2.1.3. 2.2.3.2 0.1N HC1 Extractable Zinc and Copper in Sediment Leaching solutions that have been used extensively by s o i l s c i e n t i s t s to determine exchangeable metals (Jackson 20 1958; Dewis and Fre i tes 1970; Hesse, 1971) unnecessari ly complicate the leachate due to the presence of an overwhelm-ing proportion of foreign and, often, i n t e r f e r i n g ions . The u t i l i t y of the re su l t s obtained with such solutions has also been ser ious ly questioned (Hesse, 1971). A O.lN HC1 leach was chosen to assess the adsorbed copper and zinc content of the sediment because of the reported non-destructive ef fects of this so lut ion on most clay minerals (Grim, 1968), and be-cause the so lut ion obtained i s r e l a t i v e l y free of a n a l y t i c a l complicat ions . Af ter a i r dry ing , the sample cakes were broken up by hand (pebbles, i f any, being rejected) and dry seived through nylon plankton net t ing with an average mesh opening of 50 um. A 1-g sample of this sediment was then shaken together with 50 ml O.lN HC1 for 15 minutes in a separatory funnel . After f i l t e r i n g through a 0.45 pm pore size Gelman Metr ice l GA-6 membrane f i l t e r , the f i l t r a t e was d i l u t e d to 75 ml with r inse water and i t s copper and zinc content determined as out l ined in 2 .2 .1 .3 . 21 3. RESULTS 3.1 Experimental To examine the exchange of copper and zinc between Fraser River sediment and fresh and seawater, the fol lowing experiments were conducted. 3.1.1 The desorption of Copper and Zinc from Fraser  River sediment by seawater The effect of incremental changes in s a l i n i t y on ex-changeable copper and zinc was determined by e q u i l i b r a t i n g seawater of varying s a l i n i t y with 1. . 0 g of Fraser River sedi-ment. Nakhshina and Feldman (1971), who studied the k i n e t i c s of binding of copper and zinc by bottom oozes, found that e q u i l i -brat ion was achieved af ter about 2 h. Seawater from s ta t ion 12 (73/46, 100 m, 30 0/00, /Jn++J = 5.5 pg/l>/.Cu++7 = 0.7 pg /1 ) was d i l u t e d with de ioni-zed water to obtain 0.5-JL samples with 0, 5 , 10, 15, 20, 25 , and 30 0/00 s a l i n i t y . A i r dr ied Fraser River sediment, c o l -lected at the Langley Ferry Terminal in January, 19 74, was d i -vided into 1.0-g samples using a s o i l test sample s p l i t t e r , and one of these added to each of the s a l i n i t y samples in a 1-l i t r e glass erlenmeyer f lask . Each sample was then s t i r r e d at room temperature (ca 2 0 ° C ) with a magnetic s t i r r e r for 2.0 h. F i n a l l y , i t was f i l t e r e d through a 0.45 pm pore size Gelman membrane f i l t e r and the f i l t r a t e analyzed for copper TABLE 3.1 DESORPTION OF ZINC AND COPPER FROM FRASER RIVER SEDIMENT ON TREATMENT WITH SEAWATER S a l i n i t y 0/00 Zn in S o l n pg/500 ml Zn Contr ibut ion from seawater pg Zn released Cu in S o l n pg/500 ml Cu Contribution from seawater pg Cu released 0 12. 2 0.0 12.2 3.4 0.0 3.4 5 33. 0 0. 45 32.5 11.6 0.05 11. 5 10 62.6 0.9 61. 7 23.8 0.11 23.7 15 88.9 1. 35 87.5 29.5 0.17 29.3 20 96. 8 1.8 95.0 30.3 0.22 30.1 25 98.9 2.25 96.6 33.5 0.29 33.2 30 104.6 2. 75 101.9 34.9 0.35 34.5 t s J 2 3 and zinc by procedure 2 .2 .1 .3 , The resul t s are summarized in Table 3.1 and Figures 3.1 and 3.2. It i s apparent from these data that the amount of copper and zinc released by the sedi-ment increases with increas ing s a l i n i t y . The greatest change in concentration occurs for both metals between 5 and 10 0/00. To estimate the to t a l desorbable copper and z inc , 0.2 of wet Fraser River sediment (dry weight, 0.15 g) was placed into 500 ml of u n f i l t e r e d Georgia S t r a i t seawater (74/;l, sta-t ion 3, 50 m, 29.5 0/00) and s t i r r e d for 1 h. Af ter f i l t r a -t i o n , the sediment was washed into a second 500-ml sample of seawater and the process repeated. The background concentra-t ions of copper and zinc were determined in three samples of the Georgia S t r a i t seawater. Table 3.2 summarizes the resul t s TABLE 3.2 ESTIMATION OF TOTAL DESORBABLE ZINC .AND COPPER FROM FRASER RIVER SEDIMENT Zinc Copper Seawater Background* 4.7 ug/500 ml 1.5 pg/500 ml Amt. released after f i r s t e q u i l i b r a t i o n * 9.2 ug/.15 g, . sediment 2.9 ug/.15 g. } sediment Amt. released after sec-ond e q u i l i b r a t i o n * 2.8 ug/,.15 g • sediment .8 ug/.15 g;x sediment Total metal released per gram dry sediment 90 ug 2 7 pg * Average of 3 separate determinations + Average of 5 separate determinations F i g u r e 3 . 1 The e f f e c t of s a l i n i t y on the d e s o r p t i o n of z i n c from F r a s e r R iver sediment 25 F i g u r e 3.2 The e f f e c t of s a l i n i t y on the d e s o r p t i o n of copper from F r a s e r R i v e r sediment 26 3.1.2 Fraser River Sediment: Adsorption Isotherm The measurement o£ the adsorption isotherm for Fraser River sediment i s useful in determining: (1) the capacity of the sediment to remove copper and zinc from solution and, thus, evaluating the ri v e r ' s environmental quality; (2) i f there i s any s i m i l a r i t y between the exchange reactions in the CU++-H2O- sediment and Zn++-H2O-sediment systems; (3) i f there i s any adsorption hysteresis. Into 500-ml acid-washed glass Erlenmeyer flasks were placed 400 ml deionized water and enough of the 100 mg/1 metal stock solutions to prepare a series of samples having, respect-i v e l y , zinc concentrations of 10, 20, 30, 40, 50, 60 and 70 pg/1 and copper concentrations of 5, 10, 15, 20, 25, 30 and 35 pg/1. Each solution was prepared in duplicate at a pH of 8.0. After adding 0.5 g a i r - d r i e d Fraser River sediment, the solu-tions were shaken for 48 h on a shaker table at 5°C; then they were f i l t e r e d and the f i l t r a t e s from one of the duplicate sets analyzed for dissolved copper and zinc. The sediment in the second set was transferred from the solution with which i t had come into equilibrium to that having the next lower metal con-centration ( i . e . , the sediment from flask X was placed into the f i l t r a t e of fl a s k X - l , e t c . ) . - The flask containing the highest concentration of copper and zinc, which was not used in this f i n a l test, was analyzed without further treatment so as to obtain a measure of the v a r i a b i l i t y between the duplicate sets of samples. 27 After 48 h shaking at 5 ° C , these solut ions were again f i l t e r e d and the f i l t r a t e s analyzed for copper and z inc . Table 3.2 gives the resul t s of the experiment. Because of i t s successful app l i ca t ion to s i m i l a r systems by previous workers (Bachmann, 1961; O'Connor, 1964; Nakhshina and Feldman, 1971), an attempt was made to f i t the data to the Freundl ich isotherm equation: 2L - KC n 1 m where x/m is the weight of solute adsorbed per gram of adsorbent, C i s the equ i l ibr ium solute concentration and K and n are empir-i c a l l y evaluated constants. The resul t s appear in Figure 3.3 and Table 3.3(a). The experimental values for K and n are , res-p e c t i v e l y , 9.8 and 0.70 for zinc and 8.5 and 0.54 for copper. Figure 3.4 and Table 3.3(b) indicate that , during desorp-t i o n , both systems displayed a measureable i r r e v e r s i b i l i t y . The behaviour has been observed in other clay systems invo lv ing ion f i xa t ion (Cody, 1971). 3.1.3 Ef fec t of f i l t e r pore s ize on the estimation of  d i s so lved zinc and, copper A l l zinc and copper passing through a 0.45 um membrane f i l t e r was considered to be d i s so lved , fol lowing the d e f i n i t i o n of "d i s so lved" that i s most commonly applied in natura l water ana lys i s . During the course of the experiments with f i n e l y d iv ided Fraser River sediment, i t became c lear that 0.45 um pore s ize f i l t e r s were not successful in trapping a l l of the suspended p a r t i c l e s . The extent to which f i l t e r s with a 0.2 pm TABLE 3.3 (a) FRASER RIVER SEDIMENT ADSORPTION DATA: FIT TO FREUNDLICH ISOTHERM EQUATION Zinc Adsorption Copper Adsorption I n i t i a l Equilibrium Adsorbed X log x log c I n i t i a l Equilibrium Adsorbed X log X log c Cone, p-g/1 Cone,CyUg/l- Zn,x(pg) m m Cone pg/1 Cone,c,pg/1 Cu,x(pg) m m 10 0. 8 3. 7 7.4 0.8692 -0.0969 5 .2 1.9 3.8 0.5798 -0.6990 20 1.7 7.3 10.6 1.1644 +0.2304 10 .8 3.7 7.4 0.8692 -0.0969 30 2.9 10. 8 21.6 1.3345 0.4624 15 1.8 5.3 10.6 1.0253 +0.2553 40 4.5 14.2 2°8.4 1.4533 0.6532 20 3.6 6.6 13.2 1.1206 0. 5563 50 6.4 17.8 35.6 1.5502 0.8062 25 3.7 8.5 17.0 1.2304 0.6294 60 8.0 20.8 41.6 1.6191 0.9031 30 4.8 10.1 20.2 1.3054 0.6812 70 9.6 24.2 48.4 1.6848 0.9823 35 6.6 11. 3 22.6 1.3541 0>8195 70 9.4 35 6.6 (b) IRREVERSIBILITY OF ADSORPTION Zinc Desorption Copper Desoa rption I n i t i a l Cone. Final Cone. Equilibrium Adsorbed I n i t i a l Cone. Final Cone. Equilibrium Adsorbed ug/1 pg Pg/1 Hg/1 pg 8.0 8.9 23.8 4.8 5.1 11.2 6.4 7.0 20.6 3. 7 3.9 10. 0 -4'.-5 5.2 17.5 3.6 3.2 8.7 2.9 3.4 14.0 1.8 2.2 6.2 1. 7 2.1 10.6 0.8 1.4 5.1 0.8 1. 5 7.1 0.2 0.7 3.5 OO 29 ' I 1 I , . . . . . . . - . i . r . . . » . . . i . .. I I . . - r . . . . i . . , J u f . . u . , " - T • • 1 - ' 8 —6 —4 —2 0 '2 «4 -6 «8 1-0 (b) '«3 « Figure 3.3 The Freundl ich adsorption isotherm ( 5 ° C , pH = 7.0) for zinc (a) and copper (b) on a i r - d r i e d Fraser River sediment. The value of x/m in diagram (a) i s 9.8 CO.70 and in diagram (b) 8.5 CO.94 pg/g. 2 5 n 2<H < ^5• a Ul oi 10" O m O < ~T 3 4 -1 1 0 6 RESIDUAL C O N C E N T R A T I O N » g / l 8 Figure 3.4 Relat ionship between the quantity of zinc and copper adsorbed (—- — - — --—) or desorbed (— 1 ) by Fraser River sediment and the res idua l concentrations of those metals in so lut ion c 31 pore size are more e f f i c i e n t than those with a 0.45 urn pore size in removing suspended sediment was therefore examined. Water samples c o l l e c t e d at the mouth of the Fraser River in A p r i l 1974 were s p l i t into two sets , one being f i l t e r e d through the 0.45 pm and the other through the 0.20 pm pore d ia-meter f i l t e r s . The f i l t r a t e s and residues were then analyzed for copper and z inc . The resul t s are given in Table 3.4. TABLE 3.4 THE EFFECT FILTERS ON OF FILTRATION DISSOLVED AND WITH 0.'45 pm AND 0.2 0 um SUSPENDED METAL VALUE PORE SIZE Sample Dissc jived Zinc Par t i cu la te Zinc U.45 um u.^o um u.45 um U. 20 ym 1 13.6 7.9 8.1 11.3 2 10. 3 7.7 9.6 11.9 3 11. 2 8.3 9.0 11.3 4 10.9 8.0 9.8 10.6 5 .11.3 7.9 8.4 12.4 6 11.0 8.4 8.1 11.6 Dissolved Copper Par t i cu la te Copper 0.45 um 0.20 um ! 0.45 um 0.2 0 um 1 4.1 2.4 2.0 ———_—r 3. 7 2 3.8 2.6 2.2 3.7 3 4.4 2.5 2.1 3.7 4 4.0 2.2 2.3 3.5 5 4.5 2.5 1.7 3.9 6 4.2 2.4 1.9 3.2 32 C l e a r l y , the use of 0.45 pm has the ef fect of increas-ing the measured "d i s so lved" port ion at the expense of the par t i cu la te f r a c t i o n . The magnitude of th i s ef fect at each s tat ion during the year i s impossible to predic t with the a v a i l -able data. One would expect, however, that the measured values would tend to be enhanced more near the r i v e r mouth than at points removed from i t . 3.2 F i e l d The resul t s of a l l f i e l d observations are l i s t e d in the Appendices. In general , d i s so lved and p a r t i c u l a t e copper and zinc concentrations were found to vary with season, depth and distance from the Fraser River mouth. The highest concentra-tions were observed in ear ly summer, the lowest in ear ly winter. I n t e r s t i t i a l and sediment copper and zinc tended to decrease as distance from the r i v e r mouth increased. To f a c i l i t a t e des-c r i p t i o n , the study area has been divided into the two sectors , A and B, shown in Figure 2.1. 3.2.1 Dissolved Copper and Zinc On the cruise made in Ju ly 1973, only some stat ions located in the immediate v i c i n i t y of the r i v e r mouth were sampled. The highest d i ssolved copper and zinc values observed at that time occurred in the upper 30 m, with concentrations in the underlying waters generally decreasing e r r a t i c a l l y with increas-ing depth. Within the surface waters, concentrations tended to increase away from the r i v e r mouth. 33 On the fol lowing c r u i s e , made in early August, the d i s-solved copper values in the 1-m surface samples ranged between 0.23 and 4.97 pg/1 (Figure 3.5). Concentrations were again minimal at the s tat ions nearest the r i v e r mouth and, after i n -creasing towards the middle of sector A and reaching the i r highest values at approximately the point marking the maximum v i s i b l e extension of the cloud of muddy r i v e r water, they then decreased again at the more norther ly s ta t ions . Dissolved z i n c , which ranged between 1.9 and 18.3 ug/1, had a 1-metre surface d i s t r i b u t i o n that was general ly s imi la r to that of copper, ex-cept that r e l a t i v e l y high concentrations were observed at the southern l i m i t of the study area at s ta t ion 1 and r in the middle of sector B at s ta t ion 15. At 3 metres (Figure 3.6) , low zinc values were again observed at the s ta t ion near the r i v e r mouth; however, there was a per s i s tent concentration gradient d irected northeaster ly across sector A not evident at 1 metre and, in a d d i t i o n , much higher concentrations at s tat ions 2 and 3. When the d i s t r i b u t i o n s along sect ion CD of Figure 2.1 are examined (Figure 5.7) , i t i s evident that in ear ly August the bulk of Georgia S t r a i t had zinc and copper values lower than 8.0 and 1.5 ug/1, r e spec t ive ly . Samples with higher con-centrat ions were confined l a rge ly to the upper 75 metres of the water column at s tat ions near the r i v e r mouth and also at sta-tions 15 and 16 near the northern boundary of the study area. Figure 3.8 shows the September 1973 d i s t r i b u t i o n s at 1 metre.Compared to August, copper concentrations (.38 to 1.90 pg/1) 34 (b) Figure 3.5 D i s t r i b u t i o n of d i s so lved zinc (a) and copper (b) at 1 metre during August 1973. Bracketed numbers re fer to i so-p le th values in pg/1 36 (a) (b) Figure 3.7 D i s t r i b u t i o n of dissolved zinc (a) and copper (b) along section CD during August 1973. The dots i n -dicate sample depths. 37 (b) Figure 3.8 D i s t r i b u t i o n of dissolved zinc (a) and copper (b) at 1 metre during September 1973. Bracketed numbers refer to i s o -pletii values in ug/1 38 had increased s l i g h t l y near the r i v e r mouth and decreased fur-ther out in the S t r a i t , lessening the concentration gradient subs tant i a l ly . Except for s ta t ion 1, where the concentration decreased from 18.3 to 3.9 ug/1, zinc values throughout sector A had, for the most p a r t , increased from the i r August l e v e l s , reaching a maximum of 10.1 pg/1 at s ta t ion 12. However, aside from s tat ion 16, concentrations in sector B had increased. At 3 metres(Figure 3.9) , d i s solved zinc was marginally higher than at 1 metre with a s imi l a r tendency toward a maximum at s ta t ion 12. Copper values showed a p a r a l l e l trend, and, in both cases, s tat ions 1 and 2 no longer had the conspicuously high dissolved metal concentrations observed during the e a r l i e r c ru i se s . The v e r t i c a l d i s t r i b u t i o n s along section CD (Figure 3.10) in September d i f fe red markedly from those in August. The highest copper and zinc values were no longer located at the surface near the r i v e r mouth; instead they had been sh i f ted to the in te r -mediate and deep waters in the middle of sector A , where water character ized by dissolved zinc greater than 15 pg/1 and copper greater than 1.5 pg/1 was found at s t a t ion 12 from about 50 to 300 metres and at s ta t ion 14 below 300 metres. Comparison of Figures 3.11 and 3.12, a cross-sect ion p a r a l l e l to the del ta front (Section AB of Figure 2.1) indicates that water high in d i s so lved copper and zinc had also spreadnorthward and to a greater depth between August and September 1973. Between September and November, the v e r t i c a l and l a t -e ra l concentration differences that had previously exis ted in (b) Figure 3.9 D i s t r i b u t i o n of d i s so lved zinc (a) and copper (b) at 3-metres during September 1973. Bracketed numbers re fer to i so-p le th values in pg/1. (b) Figure 3.10 D i s t r i b u t i o n of d i s s o l v e d z i n c (a) and copper (b) along s e c t i o n CD d u r i n g September 1973. The dots i n d i c a t e sample depths. 41 (b) Figure 3.11 D i s t r i b u t i o n of d i s so lved zinc (a) and copper (b) along sect ion AB during August 1973. The dots indica te sample depths. (a) (b) Figure 3.12 D i s t r i b u t i o n of d i s so lved zinc (a) and copper (b) along sect ion AB during September 1973. The dots indicate sample depths. 43 sector A were l a rge ly e l iminated , leaving the waters highly homogeneous with respect to both di s so lved copper, which ranged between 0.4 and 0.6 ug/1, and dissolved z inc , which ranged from 4 to 6 ug/1. By contras t , in sector B, concen-trat ions were more v a r i a b l e , the 1-metre surface waters hav-ing zinc leve l s of 10-15 pg/1 and copper greater than 0.65 pg/1. Genera l ly , the amount of dissolved metals decreased with depth and increased away from the r i v e r mouth. The concentration leve l s in January 1974, when the r i v e r runoff was at a minimum, were on average only s l i g h t l y lower than those of November. However, by May 1974, as the ear ly stages of the freshet redeveloped, metal l eve l s again began to increase s i g n i f i c a n t l y near the r i v e r mouth. The dissolved copper and zinc var ia t ions at s t a t ion 3 between May 1973 and May 1974 are represented in Figure 3.13. In e i ther case, there was a concentration increase fol lowing June which was evident to a depth of 150 metres in Ju ly . Then in late August or ear ly September there was a s ig -n i f i c a n t decrease, beginning at around 50 metres, which pro-gressed with time u n t i l i t became c h a r a c t e r i s t i c of the bulk of the water column, a condit ion which pers i s ted u n t i l i t ap-parently began to break down again in A p r i l of the fol lowing year. The dissolved copper and zinc var ia t ions at s tat ion 12 between July 1973 and January 1974 are represented in Figure 3.14. Again, the concentration of both metals increased with (a) (b) Figure 3.13 V a r i a t i o n of d i s so lved zinc (a) and copper (b) at s t a t ion 3 bet-ween May 1973 and May 1974. The dots indicate sample depths. Figure 3.14 V a r i a t i o n of d i s so lved zinc (a) and copper '(b) at s tat ion 12 between Ju ly 1973 and January 1974. The dots indicate sample depths. 46 time; however, in contrast to s ta t ion 3, maximal values did not occur u n t i l August. Between October and November, a sharp de-crease occurred in the concentrations of both metals that , again, lagged behind the same event at s tat ion 3. Dissolved copper and zinc concentrations in the Fraser River decreased upstream, and were highest in January 1974 and lowest in August 1973. The maximum zinc and copper concentra-tions measured were 3.8 and 0.44 ug/1, r e spec t ive ly . 3.2.2 Par t i cu la te Copper and Zinc The most conspicuous feature of the pa r t i cu l a te copper and zinc d i s t r ibu t ions in Georgia S t r a i t was that they were •••ap-proximately the inverse of those observed in the case of the dissolved metals; that i s , the i r values tended to increase near the r i v e r mouth and to diminish away from i t . The hor i zonta l d i s t r i b u t i o n s observed at 1 metre during August are shown in Figure 3.15. Zinc varied from 1.9 ug/1 at the stations nearest the r i v e r to 1.5 ug/1 at s ta t ion 12. Much lower values were observed in sector B and north of the r i v e r at s tat ion 5.7. Copper, which ranged between 1.0 and 1.4 pg/1, had a s imi l a r d i s t r i b u t i o n , although the d i s cont inu i ty between sectors A and B was more apparent than in the case of z inc . The par t i cu la te metal concentrations at a depth of 3 metres were s l i g h t l y higher; however, the d i s t r i b u t i o n pattern was e s s en t i a l l y the same. On successive c ru i se s , the amount of pa r t i cu l a te copper and zinc f i r s t decreased and then, after passing through a 47 (b) Figure 3.15 D i s t r i b u t i o n of p a r t i c u l a t e zinc (a) and copper (b) at 1 metre during August 19 7 3. Bracketed numbers re-fer to i s o p l e t h values in pg/1. 48 minimum in January, increased again to higher values in May. In general , f luctuat ions in d i s so lved metals c l o s e l y p a r a l l e l e d changes in par t i cu la te metals. 3.2.3 I n t e r s t i t i a l and Sediment Copper and Zinc The amounts of copper and zinc dissolved in the in ter -s t i t i a l waters were highest at s ta t ion 3, decreasing consid-erably toward s ta t ion 14. The analys i s of a core t y p i c a l l y showed a decrease i n dissolved copper and zinc with depth along the core. At a given s t a t i o n , there was a lso a v a r i a t i o n with time that was approximately in phase with changes in r i v e r dis-charge. Zinc ranged from 12.8 to 116 ug/1, and copper from 2.9 to 20.8 pg/1. The largest values normally occurred in muds that were discoloured by the presence of i ron and mangan-ese oxides. The sediment copper and z inc 'va lues f luctuated both with respect to depth and time in patterns that l a rge ly p a r a l l e l those described for the i n t e r s t i t i a l waters. 3.2.4 S a l i n i ty As was the case with both dissolved and par t i cu la te copper and z inc , the most noticeable var ia t ions in s a l i n i t y occurred in the upper few tens of metres during the summer months, with the steepest gradients occurring in the waters adjacent to the r i v e r mouth. In August, the 1-metre surface s a l i n i t y ranged from 16 0/00 of f the r i v e r mouth to 26 0/00 in the northern part of the study area. Water below 30 metres var ied only between 49 29.5 and 31 0/00, i t s s a l i n i t y invariably increasing with i n -creasing depth. A closer look at the d i s t r i b u t i o n pattern of s a l i n i t y at 1 metre in August (Figure 3.16(a)) reveals a pat-tern similar to that for dissolved copper and zinc (Figure 3.5), in that there are lobes of less saline water that protrude out into the S t r a i t away from the r i v e r mouth. Such a d i s t r i b u -tion pattern was again observed in September (Figure 3.15(b)), when the s a l i n i t i e s at 1 metre had increased to between 21-27 0/00; however, below 30 metres, values remained between 29.5 and 31 0/00. During the winter, the lowest s a l i n i t y waters (26 0/00) were confined to the immediate v i c i n i t y of the Fraser River mouth. In sector B, where s a l i n i t i e s at 1 metre ranged from 27-29 0/00, nearly complete l a t e r a l homogeneity existed. Below 30 metres, values seldom dropped below 30 0/00 or exceeded 31 0/00. In winter, the v e r t i c a l s a l i n i t y s t r a t i f i c a t i o n was less intense than in summer, but a strong halocline again de-veloped, p a r t i c u l a r l y near the r i v e r mouth, when the surface s a l i n i t i e s began to decrease in May 1974. Figure 3.17, which i l l u s t r a t e s the time variation of T, s a l i n i t y and <r t at station 3 over the period from May 1973 to May 1974, indicates that the abrupt change in dissolved metal content observed in late August (Figure 3.12) correlates c l o s e l y with an intrusion of colder, more saline water of higher den-s i t y . The effects of this intrusion were also observed in September and October 1973 at station 12 (Figure 3.18), where 50 Figure 3.16 D i s t r i b u t i o n of s a l i n i t y at 1 metre during August 1973 (a) and September 1973 (b) . Bracketed numbers re fer to i sop le th values . F i g u r e 3 . 1 7 V a r i a t i o n of T ( o c ) , S a l i n i t y ( 0 / 0 0 ) and at (gir/cm 3) at s t a t i o n 3 between May 1 9 7 3 and May 1 9 7 4 Figure 3.18 V a r i a t i o n of s a l i n i t y (0/00) at s t a t ion 12 between Ju ly 1973 and January 1974 5 3 there again i vas an i n c r e a s e i n s a l i n i t y which c o i n c i d e d w i t h decreases i n d i s s o l v e d copper and z i n c c o n c e n t r a t i o n s . 54 4. DISCUSSION The data indicate that there were large time depend-ent changes in dissolved copper and zinc in Georgia S t r a i t that were apparently re la ted to Fraser River discharge. F ig -ure 4.1 compares the v a r i a t i o n of suspended sediment and run-off at Hope, B .C. (unpublished data,Water Survey of Canada), with the dissolved zinc and dissolved copper values observed in the upper 20 metres at s ta t ion 3 for the per iod May 1973 to May 1974. In general , the maxima and minima in runoff cor-respond with maxima and minima in the dissolved metal values. The lack of a more exact correspondence poss ibly re su l t s from a f a i l u r e of the d i s so lved metal measurements to coincide with the extremes in runoff . The fact that comparison i s being made with the runoff at Hope rather than at the r i v e r mouth i s probably unimportant since they w i l l tend to peak at both points at roughly the same time. At s ta t ion 3, the largest changes in dissolved metals occurred during Ju ly and August (Figure 3.13), when there was a marked progressive thickening of the water layer having high metal concentrat ions. The same phenomenon occurred at s ta t ion 12 but only fol lowing a time lag , as i f due to some factor connected with the runoff that gradually radiated outward from the r i v e r mouth. The dissolved metal values in the r i v e r upstream from the influence of the saltwater wedge seldom exceeded 3 ug/1 for zinc and 0.4pg/l for copper, concentrations which are low 55 co o E x 1 ^  — CO U »-« »• *" B 400-] g> o X 30CH 200-100-o 200 150 100-50-30 H I Sediment ischarge A i i /\ 4\\ \lo\ \\\ E o cn TJ > E u 2 r 6 c M TJ « M —r-A ~r-N i D I M M o •40 •30 •20 10 0 L 0 h2 Figure 4.1 Compariaon of suspended sediment load and runoff of Fraser River at Hope, B .C. with d i s so lved zinc and copper values at sta-t ion 3 for tiie period May 1973 to May 1974. The metal values are the resu l t of integrat-ing values in the top 20 metres. 56 in comparison to those observed i n the S t r a i t d u r i n g the p e r i o d of h i g h r u n o f f . The anomalously high metal values i n Georgia S t r a i t t h a t appear to be r e l a t e d to the r u n o f f peak, thus, are c l e a r l y not a t t r i b u t a b l e to the d i s s o l v e d f r a c t i o n of the r i v e r load. However, as shown e x p e r i m e n t a l l y , (Table 3.2), sediment c o l l e c t e d from the r i v e r c o n t a i n s a l a r g e amount of copper and zin c which i s r e a d i l y d i s p l a c e d from a d s o r p t i o n s i t e s by sea-water i o n s . Assuming that the suspended sediment behaves s i -m i l a r l y , l a r g e amounts of metals should t h e r e f o r e be r e l e a s e d as s a l t and f r e s h waters are mixed o f f the r i v e r mouth, p a r t i -c u l a r l y during the p e r i o d of maximum r u n o f f when the suspended r i v e r l o a d i s g r e a t e s t . The above hypothesis can be v a l i d only i f the amount of desorbable metal d i s c h a r g e d i n t o the S t r a i t d u r i n g the course of the s p r i n g f r e s h e t i s s u f f i c i e n t to account f o r the observed d i s s o l v e d metal anomalies. The t o t a l amount of metal t h a t t h i s would r e q u i r e can be estimated from the observed concen-t r a t i o n changes i n the S t r a i t assuming that l o s s e s due to out-flow through Boundary Pass and r e a d s o r p t i o n or p r e c i p i t a t i o n r e a c t i o n s are n e g l i g i b l e . ' T h i s f i g u r e can then be c o n t r a s t e d with the p o t e n t i a l supply of desorbable metals assuming t h a t the only source of sediment i s the F r a s e r River suspended l o a d and that t h i s m a t e r i a l has the same metal-exchange c h a r a c t e r -i s t i c s as t h a t examined i n the l a b o r a t o r y experiments. On the b a s i s of winter values of 5 ug/1 and .5 pg/1 f o r z i n c and copper, r e s p e c t i v e l y , the i n c r e a s e s i n d i s s o l v e d 57 metal concentrations in the S t ra i t during the freshet amount to approximately 4 pg/1 for zinc and 1 pg/1 for copper. From Figure 3.7, i t can be estimated that only about 10% of the volume of the S t r a i t was affected to this extent. It fo l lows , then, that about 400 metric tons of zinc and 100 metric tons of copper are required to account for the observed increases . According to the experiments performed on Fraser River mud, approximately 90 pg Zn and 2 7 pg Cu per gram of sediment can be released on contact with seawater. On integra t ing the amount of suspended sediment discharged during May, June and Ju ly , when 90% of the annual sediment transport occurs, the amounts of zinc and copper that p o t e n t i a l l y could be desorbed are ca lcu la ted to be 2000 metric tons zinc and 600 metric tons copper. Accord ing ly , the amount of desorbable metal being dis charged i s c l e a r l y adequate to account for the observed con-centrat ion increases . Beside the above evidence, there are, in a d d i t i o n , sympathetic var ia t ions among d i f ferent ivater propert ies in the southern S t r a i t that are consistent with the notion that the r i v e r ' s suspended load i s the primary source of the sea-sonal zinc and copper f luc tua t ions . An example i s i l l u s t r a t e d by Figure 4.2, which shows how s a l i n i t y , and dissolved and par t i cu la te copper and zinc varied at 1 metre during August between stat ions 1-6, across the de l ta f ront . It i s evident that , as the s a l i n i t y increased on e i ther flank of the out-flowing r iver-generated low s a l i n i t y water, the d i s so lved Figure 4.2 V a r i a t i o n of s a l i n i t y , d i s so lved zinc and copper and p a r t i c u l a t e zinc and copper at 1 metre along sect ion AB in August 11)73 59 metal values increased while the suspended metal values de-creased. This could be interpreted as showing that , as r i v e r water was being mixed h o r i z o n t a l l y into more sa l ine waters the dissolved metal phase was increas ing at the expense of the par t i cu la te phase, as might be expected i f the metals are de-r i v e d by desorption from suspended r i v e r s o l i d s . Figure 4.3 reveals how the same quant i t ies var ied at 1 metre during August along sect ion CD and i t s extension into the freshwater of the Fraser River . Despite a close corres-pondence at s ta t ion 3, d i s so lved metal concentrations were no longer re la ted in a simple manner to s a l i n i t y and par t i cu la te metals as they appeared to be in Figure 4.2,which i s perhaps a r e f l e c t i o n of the complicated surface mixing in Georgia S t r a i t . A broader perspective of how dissolved and suspended copper and zinc values var ied with respect to each other i s provided by Figure 4.4, which represents data for the upper 20 metres from the s tat ions located near the r i v e r mouth dur-ing the summer. C l e a r l y , there wasoa strong tendency for high dissolved metal concentrations to be associated with waters of low p a r t i c u l a t e metal content both in the cases of copper and z inc . In Figure 4 .5 , the re la t ionsh ip between the s a l i n i t y and dis so lved metal content of the upper 20 metres is con-trasted with that for the samples from below 20 metres, the data again being those co l l ec ted during the summer of 1973 60 26-^  o 18-c N 3H ° 2-\ cn *=.2-0-a 1-5-u o o K>-"5 u o cu 16 S t a t i o n Number 15 14 13 12 9 3 R S » 1 6 H N 1 2 --a « 8-4H ~ H o CL 3H u I 2-o • H Figure 4.3 V a r i a t i o n of s a l i n i t y , d i s s o l v e d z i n c and copper and p a r t i c u l a t e z i n c and copper at 1 metre along s e c t i o n CD and i t s e x t e n s i o n i n t o the F r a s e r R i v e r d u r i n g August 1973 1-0 2-0 3-0 4-0 Particulate Zn » g / l a) A A A A A A A A A A A A * A A A A A * A A A A A A 0-5 1-0 Part iculate Cu p g / | V 5 —1 2-0 (b) Fi g u r e 4 . 4 R e l a t i o n s h i p between d i s s o l v e d metal and p a r t i c u l a t e metal Tor z i n c (a) and copper ( b ) . Data p o i n t s r e p r e -sent samples obtained near the r i v e r mouth d u r i n g the f r e s h e t 02 201 15H 5 l 3 3-4 : 2 M • • o 1 n D D • • • o ° • B ° 1 . ° a ° n • • a • • • • ° • • • "«"» a . • 1 ' T - ™ 1 ' I - • 15 2 0 2 5 3 0 ( a) S a l i n i t y % o S i a • a P n a o • a oi) • • • Q ° ' ° ° • ° ° ° O # • " , » • O O ' O 0 0 • • O • • • • 5 a° • a o M • » o P • a o a o • o o o o • a o •»•' o o „ ° • a • • , • 1 • • 1 - - - I — I HS 1 5 2 0 25 3 0 S a l i n i t y % * (b) Figure 4.5 Relat ionship between s a l i n i t y and d i s -solved zinc (a) and copper (b) for the upper 20 metres (a) and remainder ( • ) of the water column for s ta t ions near the Fraser River mouth during the 1973 freshe t 63 at stations off the r i v e r mouth. It i s evident that low metal values are generally associated with either low or high s a l i n i -t i e s , while the highest values occur at intermediate s a l i n i t i e s . This suggests, f i r s t l y , that the high s a l i n i t y waters advected into Georgia S t r a i t through Boundary Pass are not themselves the source of the anomalously high metal concentrations. Se-condly, in concurrence with the desorption hypothesis, i t sug-gests the increase i n dissolved metal values and the mixing of r i v e r with saline waters are related phenomena. Figures 3.11 and 3.12 indicate that there was a down-ward and northward movement of high metal values along section AB between August and September 1973. Because v e r t i c a l mixing cannot account for the downward flux of dissolved metal, i t can be in f e r r e d that, as the sediment p a r t i c l e s were transported northward by the general counter-clockwise surface c i r c u l a t i o n and sank under the influence of gravity into more saline waters, metals were desorbed. The amount desorbed at a p a r t i c u l a r loca-tion w i l l vary depending on the concentration, size d i s t r i b u -t i o n , physical properties and previous history of the suspended p a r t i c l e s and the seawater concentration of zinc and copper, s a l i n i t y and water pH (Cody, 1971; Hahn and Stumm, 1970). The data also indicate that there was a decrease in the metal content in the bottom sediments of Georgia S t r a i t with increasing distance from the r i v e r mouth. The sharp decrease in metal values in August-September can best be understood in terms of a replacement of water at that time. Figures 3.13, 3.17, 3.14, and 3.18 show that, co-incident with the decrease in metal values at station 3, there 64 was an increase in s a l i n i t y and density; and that, af t e r a time lag, the same events occurred at station 12. Unlike the general features discussed above, the de-t a i l e d features of the metal d i s t r i b u t i o n s evident in the various diagrams are v i r t u a l l y impossible to account for at present because they are the re s u l t of the action of various time and space-dependent factors which cannot be properly defined using available information. These include (1) the eff e c t s of water c i r c u l a t i o n and mixing on the d i s t r i b u t i o n of sinking sediment p a r t i c l e s , (2) the effects of b i o l o g i c a l communities in removing trace metals from solution as well as the e f f e c t of biogenous materials as adsorbents (Riley and Skirrow, 1965), and (3) the adsorption of metals by hydro-genous phases such as iron and manganese oxides (Krauskopf, 1958). In addition, the exchange process is a function of pH and temperature - the amount adsorbed increasing with i n -creasing pH and decreasing temperature - although in Georgia S t r a i t , pH effects should dominate. Furthermore, inadequacies in the sampling programme and the a n a l y t i c a l methods severely r e s t r i c t a more detailed analysis of the metal d i s t r i b u t i o n data. In addition to the fact that there was an i n s u f f i c i e n t number of samples c o l l e c t e d during the beginning stages of the freshet, the observed d i s -t r i b u t i o n patterns - p a r t i c u l a r l y those pertaining to the sur-face layer (e.g. Figures 3.5, 3.6, etc.) - w i l l tend to be 65 d i s t o r t e d because i t required up to 3 days to sample a l l sta-tions. Although some of the extreme values obtained may be the r e s u l t of contamination, the persistence of the observed trends indicates that the large-scale time-dependent concen-trat i o n variations are r e a l . However, i t i s possible that some of the small-scale variations observed in the metal dis-tributions could be related to a n a l y t i c a l v a r i a b i l i t y or to the i n a b i l i t y of 0.45 um pore diameter f i l t e r s to trap a l l the suspended phase, thus allowing some pa r t i c u l a t e metal contribution to the dissolved metal values. The magnitude of t h i s f i l t e r e f f e c t i s d i f f i c u l t to assess because of the v a r i a b i l i t y in composition and d i s t r i b u t i o n of sinking sedi-ment but would presumably be most important near the r i v e r mouth during the freshet. 66-67 5. SUMMARY Although i t appears that the enrichment of Georgia S t r a i t waters with d i s s o l v e d copper and z i n c d u r i n g May, June, J u l y and August i s mainly the r e s u l t of d e s o r p t i o n of these metals from F r a s e r R i v e r suspended mineral phases, many aspects of the observed d i s t r i b u t i o n s are ap p a r e n t l y r e g u l a t e d by the c i r c u l a t i o n w i t h i n the S t r a i t . The annual v a r i a t i o n s of copper and z i n c - which may be as much as an order of magnitude -both i n the s u r f a c e waters and v e r t i c a l p r o f i l e s , f o l l o w gen-e r a l l y s i m i l a r p a t t e r n s . High metal v a l u e s were observed to spread out from the r i v e r mouth and into.deeper water through the summer months, u n t i l , d u r i n g September, the hig h metal content waters were swept out by the intrusion-:,;, of waters of a lower metal content from the southern channels. 68 BIBLIOGRAPHY Bachmann, R.W., 1963. 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A P P E N D I C E S 72 APPENDIX A GEORGIA STRAIGHT STATION POSITIONS Station Number North Latitude West Longitude (Figure 1.1) 1 4 8 ° 5 0 . 1 » 122057.4' 2 4 8 ° 5 5 . 8 ' 1 2 3 ° 1 9 . 0 ' 3 4 9 ° 0 1 . 3 ' 1 2 3 ° 1 8 . 5 ' 4 4 9 ° 0 5 . 6 ' 123023.0' 5 49011.4' 1 2 3 ° 2 3 . 0 ' 5.5 4 9 ° 1 4 . 0 ' 1 2 3 ° 2 2 . 5 ' 5.7 4 9 ° 1 8 . 8 ' 1 2 3 ° 1 9 . 1 » 6 4 9 ° 1 8 . 8 ' 1 2 3 ° 2 3 . 0 ' 7 4 9 ° 1 5 . 8 ' 1 2 3 ° 3 0 . 8 ' 8 4 9 ° 1 1 . 4 ' 125 o30.8' 9 4 9 ° 1 1 . 4 ' 1 2 3 ° 3 9 . 7 ' 10 4 9 ° 1 4 . 8 ' 1 2 3 ° 3 5 . 9 ' 11 49017.5' 1 2 3 ° 3 8 . 0 ' 12 4 9 ° 1 6 . 6 * 1 2 3 ° 4 8 . 4 ' 13 4 9 ° 2 1 . 8 * 1 2 4 ° 0 9 . 0 ' 14 4 9 ° 2 6 . 0 » 1 2 4 ° 2 7 . 5 ' 15 4 9 ° 3 4 . 0 ' 1 2 4 ° 3 3 . 5 ' 16 4 9 ° 4 8 . 8 ' 1 2 4 0 4 7 . 0 » A P P E N D I X B B . l Seawater Analyses C R U I S E 73/21 D A T E 18 May, 1973 S T A T I O N 3 • D e p t h m T e m p e ratu re ° C S a l i n i t y % o D i s s o l v e d 02 • m l / | D i s s o l v e d Zn M9/l Dissolved C u **9/l Particulate Zn M 9 / I Par t icu la te C u Wt Par t icu la tes p. p.m. ' 1 ° 14. 11 5.7 2.3 1.7 0.50 10 8. 79 5.5 0.61 .5 0.33 . . . . 20 8.49 5.8 0.58 .4 0.21 30 7. 95 6.0 0.53 .2 0.23 . . . . 40 8.40 3.4 0.50 .3 0.18- - - — -55 8. 31 6.3 0.48 .2 0.19 . . . . 70 8.41 8.6 0.50 . 1 0.2 5 80 8.20 1.8 0.46 .1 0.19 _ _ _ 90 8.40 3.2 1.0 .4 0.30 _ _ _ _ _ 102 5.0 0.71 . .6 0.63 C R U I S E 73/28 D A T E 18 Ju ly , 1973 S T A T I O N 1 • D e p t h T e m p e r a t u r e m oc Sa U n i t y % o Di s s o 1 v e d 0 2 • m l / | D i s s o l v e d Zn Dissolved Cu M9 / l A»9/l Particulate Zn M9/1 Par t icu la te C u M 9 / I Wl Par t i cu la tes p. p.m. . 1 13. 51 26.069 12.2 3.61 . 3 .12 3 12.48 2 7.112 6.6 3.86 .3 . 14 10 11.57 28.015 8.4 4.44 N.D. * 2 0.13 2 0 11.21 28.520 8.3 5.29 •5 N.D. 30 10. 89 28.886 12.2 5.69 - - - - - - -. 4 0 10. 74 29.131 11.4 4.13 50 9.97 29.973 10.9 2.2 5 75 9. 82 30.160 11.6 1.50 . . . . 100 9 .17 31.031 - - - - 6.6 2.34 125 9. 03 31.113 9.0 2.38 . . 5 .20 150 9. 09 31.119 5.6 1.66 — • — 175 9. 05 31.1,17 8.3 2.95 200 8.97 31.204 * 5.8 N.D. Not >> 3.88 Detected 1.0 .56 36.40 C R U I S E 73/28 D A T E 19 J u l y , 1973 S T A T I O N . 3 • D e p t h T e m p e r a t u r e m oc S a l i n i t y % o O i sso1ved 02 • m l / | D i s s o l v e d Zn M9/l Dissolved C u M9/I Particulate Zn MQ/l Par t icu la te Cu M9/I Wt Par t icu la tes p. P.m. 1 16. 00 16.615 5.6 1.58 2.5 . 36 " ' 3 14. 31 23. 024 10.1 2.40 1.2 .10 22.50 10 12.47 27.208 9.0 1. 73 1.3 .12 20 10.97 28.250 13.0 2.63 .4 .04 . 30 10.6 8 2 8.88 7 18.8 3. 30 .4 N . D . • _ _ _ _ 40 10.33 29.399 11.0 3.08 _____ 50 10.02 29.739 ; _ ' 10.1 1.90 - _ . _ 75 9.59 30.131. •' 11.6 2. 00 — — _ _ _ _ 100 9.42 30.52 2 10. 8 1.65 . 2 N . D . 19.86 12 5 9.22 30.846 4.6 2. 78 - - - -il-50 8.94 30.968 4.7 2.03 — - - • • 160 8. 86 30.9 74 4.0 0. 89 . 8 .31 30.70 CRUISE 73/28 D A T E 19 Ju ly , 1973 STATION . 5. 7 • D e p t h T e m p e r a t u r e rn oc S a l i n i t y °'oo Di s s o 1 v e d 02 • m l / | D i s s o l v e d Zn M 9 / l Dissolved Cu Particulate Zn Ma/I Par t icu la te Cu MS/I Wl Par t icu la tes P-P.rn. 1 14. 69 21.435 11.0 2.48 1.5 . 88 35. 80 3 13.98 26.854 15.5 4.26 .4 .16 41.71 10 12.52 27.522 12.0 . 1.59 • 8 .17 2 8.48 2 0 11.98 27.976 17.0 1.97 .2 .26 30 10.58 28.979 10.1 1.34 .5 .20 • 40 9.68 29.365 12.8 1.02 50 9.42 29.531 8.7 1.2 5 60 9.18. 29.730 12. 6 1. 72 70 9. 30 29.910 5.6 . 95 80 9.07 30.307 11.4 2.10 ' 90 8.9 7 30.307 5.8 1.21 • 100 8. 86 30.356 11. 0 1.21 .1 N.D. 110 8. 75 30 .46 8 7.5 1.27 120 8.57 30.613 5.4 1.72 CRUISE 75/28 D A T E 19 Ju ly , 1973 STATION r (a) 5.7 Cont 'd (b) 12 • D e p t h m T e m p e r a t u r e ° C S a 1 Inily % o D i s s o 1 v e d 0 2 • m l / | D i s s o l v e d Zn M 9 / l Dissolved C u Atg/i Particulate Zn Par t icu la te Cu M 9 / 1 Wt Par t icu la tes p. p.m. 130 8.52 30.660 7.7 1.21 140 8.44 30.663 8.9 3.05 .1 N.D. 150 8. 78 30.824 9.9 1.46 .3 .20 1 17.14 25.481 12.6 2.03 1.9 1.00 33.27 5 16.99 25.529 12.3 2.40 -1.2 .41 2 9.09 10 13.36 27.146 _ _ - _ 9.9 1.73 1.6 .22 20 10.39 28.952 10.1 2 . 2 5 . .1 .24 30 9.14 29.623 11.0 1.50 . 7 . 30 CRUISE 73/30 D A T E 1 August, 1973 STATION . ( a) 1 (b) 2 .(c) 3 • D e p t h m r e m p e r a t u re oc Sa 1 Inity %o D i s s o l v e d 0 2 • m l / | D i s s o l v e d Zn M 9 / l Dissolved Cu Particulate Zn Par t icu la te Cu r * S / l Wt P a r t i c u U t . e S p. p.m. (a) 1 11.05 29.687 18. 3 3, 81 .5 .02 48.65 10.85 29.724 17.2 3.63 .6 .07 46.10 30 10.27 29.979 12.5 • 2.95 80 9.88 30.229 14.4 4.24 130 9. 74 30.333 20.5 2.90 - i - _ • 180 9.43 30.653 21.7 3.82 203 9. 38 30.786 5.2 1.9 8 (b) 1 17.41 21.873 5.1 1.10 2.4 .44 3 12.76 26.574 19.6 1. 71 1.2 .09 36.58 Cc) 1 11.02 16.474 6. 42 9.2 . 50 1.9 1.42 3 10.00 16.92 8 6.41 22.2 . 50 2.4 1.17 36.81 10 9.18 28. 472 5.03 8.0 1.27 2.0 . 82 29.00 30 9.10 29.134 4. 73 20.3 2. 70 1.2 .56 19.34 CRUISE 73/30 D A T E 1 August, 1973 S T A T I O N . ( a) 3 c on t ' d (b) 4 (c) 5 (d) 5.7 • D e p t h m Temper a tu re o c S a 1 Inily ° ' o o D i s s o l v e d 0 2 • m l / l D i s s o l v e d Zn M9/l Dissolved Cu Particulate Zn M9/1 Par t icu la te Cu MS/I Wt Par t icu la tes p. p.m. (a) • s o 8. 76 29.660 4.43 8.0 1.27 .8 .18 100 8.53 30.521 4.12 11.5 2. 10 .4 .23 21.48 150 •8.49 30. 828 4.05 10.7 1.40 .16 22.66 175 4.07 6.5 .39 188 4.02 8.4 .77 .1.1 .06 18.14 (b). 1 18.91 12.826 1.9 0.23. 3.2 1.28 _ _ _ _ 3 18.1.1 17.010 4.2 3.37 2.8 .13 (c) 1 19.00 16.496 3.1 0.66 3.2 .64 32.93 3 18.38 15.969 4.6 0.66 2.2 1.06 31.84 (d) 1 18.95 16.530 7.15 8.6 1.10 1.3 .56 _ _ _ _ 3 18.19. 17.153 6.99 2.7 1.38 2.6 .26 10 12. 14 26.444 5.15 6.5 1.22 1.8 .31 CRUISE 73/30 D A T E 1 August, 1973 1 STATION f (a) 5.7 Cont'd (b) 7 (c) 8 (d) 9 — (a) • D e p t h m T e m p e r a t u re OC Sa 1 Inity % o D i s s o 1 v e d 0 2 • m l / | D i s s o l v e d Zn Dissolved Cu M9/I Particulate Zn M9 / I Par t icu la te C u M9/I Wt Par t i cu la tes p. p.m. 30 10.53 28.916 4. 76 8.8 1.27 .8 .20 50 8.91 29.781 4.41 11.5 1.92 . 7 .20 100 •9.00 30.529 4.08 4.6 1.92 .3 .20 150 8.91 30.791 4.05 4.7 0.62 .4 .16 160 , :8.67 30.892 3.98 5.2 0.71 .4 .14 162 8. 80 : 30.882 3.91 5.4 0 . 55 .5 . 08 (by 1 18. 59 2 2.533 6.9 1.70 1.1 .48 21.44 3 18. 40 22.781 7.3 2.87 1.7 .51 12.80 (c) 1 18. 89 2 5.0 70 6.8 . 38 1.0 1. 06 . . . _ .3 l'8. 56 25.134 12.0 .99 1.0 . 39 (d) . 1 18.71 25.059 6.3 2.55 1.5 . 89 _ _ _ _ 3 16. 35 25.909 8.2 . 83 1.3 .54 CRUISE 73/30 D A T E 1 August, 1973 STATION . (a) 10 (b) 11 (c) 12 • D e p t h T e m p e r a t u re m oc S a 1 in i ty % o D i s s o l v e d 02 D i s s o l v e d Zn Dissolved Cu M9/l ^9/1 Particulate Zn Par t icu la te C u MB/ I Wt Par t icu la tes p. P.m. (a) 1 18.89 25.070 8.8 4.9 7 1.4 1.00 3 18.56 25.134 . 6 . 9 r 3.9 7 1.4 1.06 ( b ) 1 • 18.71 25.059 8.8 2.10 0 . 8 .76 3 16.35 25.909 3. 8 1.49 5.1 .25 (cj 1 2 4.79 4 6. 36 5.7 1.71 1.5 .98 21. 86 3 24.811 6. 38 8.0 2.43 •1.0 .62 14.97 10. 2 7,687 6.98 11.5 2.26 1.0 . 58 12.40 30 29.459 . 4 . 4 5 6.1 1. 88 0.2 .56 22.10 100 ----- 30.45 8 4.08 6.4 1. 50 . 150 30.734 4.22 200 ". 6.77 0.94 300 30.907 4.11 4.3 0.56 400 415 -----31.019 31.041 5.90 3.86 8.3 7.3 1. 70 . 55 0.7 0.9 .24 .16 . 2 5.80 21.67 CRUISE 73/30 D A T E 2 August, 19 73 STATION f (a) 13 (tO 14 (c) 15 • D e p t h T e m p e r a t u r e m oc Sa 1 Inity % 0 Di s s o l v e d 0 2 • m l / | D i s s o l v e d Zn M9/l Dissolved C u M9/I Particulate Zn Par t icu la te Cu MB/ I Wl Par t icu la tes P-p.m. 17. 35 17.33 26.035 26.0 33 6.0 4.9 .41 .72 .4 .4 .07 .10 1. 17.11 26.537 7.6 .41 .5 .05 3 17.10 26.539 6.3 .54 . 3 N.D. 10 16. 05 26.844 5.7 .30 • 2 N.D. 150 - - - . 6.0 1.39 .4 N.D. 250 6.5 .87 .6 .16 300 8.27 30.887 6.5 .65 1.0 .06 315 8.2 8 30.89 3 11.5 . 86 1.0 .11 334 ' 8.27 30.904 8. 7 .89 1.8 .37 30.00 1 17.47 26.520 - - - - 15.2 1.83 .9 .19 3 8.19 26.550 17.4 10.02 .7 .12 CO CRUISE 73/30 D A T E 2 August, 1973 STATION , 16 • D e p t h T e m p e r a t u r e S a l i n i t y D i s s o l v e d 02 O i s s o l v e d Z n Dissolved Cu Particulate Zn Par t icu la te Cu m . ° C 0 / o o • ^ g / | / i g / l yUg/ ! fXQ/\ 1 15.98 26. 386 8. 1 .96 1.0 . 15 3 15.97 26. 374 8.0 2.43 1. 0 .23 10 12 . 13 28. 265 10 . 7 2 . 26 . 7 . 80 50 8. 77 29 . 774 8. 8 1. 88 . 8 . 52 100 8.18 30.190 7. 7 1.00 .5 .33 200 8. 18 30.668 215 8. 19 30.684 8.2 .51 .9 . 34 CRUISE 73/31 D A T E 15 August, 1973 STATION r 5 - 7 • D e p t h m f e m p e r a l u r e ° C S a U n i t y % o D i s s o l v e d 02 • m l / | D i s s o l v e d Zn MQ/l D i s s o l v e d C u .U9 / I P a r t i c u l a t e Z n M9/I P a r t i c u l a t e C u Me/l Wt P a r t i c u l a t e s p. P . m . . 1 17.08 24.059 6.65 4.0 .87 .7 .94 '• 3 16.95 25.379 6. 82 , 5 . 7 1.03 1.9 .41 10 14.88 2 7.2 39 6.81 4.1 1.07/ 2.-0 .54 38.91 20 10. 70 28. 811 4. 72 4.0 .79 .9 .87 30 10.16 29.121 4.69 40 9.64 29.397 4.42 . . . _ 50 9.24 29.637 4.29 6.5 .51 .1 N.D. 60 9. 09 29.752 4.29 — . . 70 9.15 2 9.89 6 4.17 . . _ _ _ _ 80 8.9 3 30.137 4.21 . _ _ _ _ 90 8, 86 30.255 4.12 . ' _ _ _ _ 100 8.98 30.378 4.25 8.4 .75 .1 N.D. - . _ . 12 5 8. 89 30.69 3 4.02 . — . _ _ _ _ 146 8. 85 30.913 3.90 5.4 . 75 .2 .04 17.3P CRUISE 73/3} D A T E 16 August, 1973 STATION f 3 • D e p t h T e m p e r atu te m oc Sa U n i t y %o Di s s o l v e d 0 2 • m l / | D i s s o l v e d Zn M9/l Dissolved C u M9/I Particulate Zn M9/1 Par t icu la te C u Me/i Wt Par t icu la tes p. p.m. 1 16.81 21.358 6.68 3.5 .99 2.7 .96 13.02 3 16. 49 23.106 6.7 3 6.8 .73 2.5 1.02 21.65 10 13.13 27.693 5.75 6.1 .47 1.4 . 83 20 10.66 29.120 4.59 7.2 . 59 1.1 .26 8.40 30 10.46 29.494 4. 39 - - - - - • 40 9. 85 29.765 4.25 50 9.57 29.974 4.20 1.1 .47 .9 .22 9.36 75 9.57 30.390 4.0 3 100 9.62 30.628 . 3.89 6.8 . 86 .5 .44 150 8.73 30.867 4.10 4.3 1. 86 .1 .10 17. 31 160 8.82 30.924 3.99 1.6 1,98 .2 .13 170 8. 81 30.9 60 3.92 2.0 2; 02 .2 .37 19.84 180 8.94 31.115 3.85 1.9 1. 79 195 9.11 31.192 3.90 1.3 1.30 CRUISE 73/31 D A T E 16 August, 1975 STATION . 12 • D e p t h T e m p e r a t u r e m oc Sa 1 in i ty % 0 D i s s o l v e d 02 • m l / l D i s s o l v e d Zn M9/l Dissolved C u Particulate Zn M9/I Par t icu la te C u M S / I Wt Par t icu la tes P. P.m. 1 16. 41 26.995 6.42 7.5 .67 1.0 .46 18.12 3 12.99 26.994 6.42 8.0 .81 1.0 .59 25.86 10 11. 88 28.401 6.5 7 9.1 .90 .9 .41 26.58 20 9.57 29.450 4.49 7.5 . 79 .9 .22 25.70 30 9.0 7 29.746 4. 51 10.8 1.62 . 7 .29 • 25.95 .50 8.64 29.989 4.51 — — - _ _ . 75 8.41 50.262 4.26 — _ . 100 8. 73 50.545 4. 10 11.6 1. 55 1.9 .11 21. 00 150 8. 77 50.755 4.12 2 00 8.6 7 50.861 4.10 15.1 .99 1.6 .17 21. 76 250 8. 56 50.910 4.05 • 300 8. 52 50.949 4.0 7 10.6 1.06 1.7 . 52 28.31 350 8.91 51.069 5. 85 6.4 . 79 1.0 .40 400 414 8. 89 8. 95 51.214 51.225 5.85 5.75 8.8 5.1 . .99 .55 .9 .8 .19 .12 20.08 C R U I S E 73/35 D A T E 4 September, 1973 S T A T I O N . ( a ) 1 ( b y 2 ( c ) 3 • D e p t h T e m p e ra tu re m ° C S a l i n i t y % o D i s s o 1 v e d 0 2 • m l / | D i s s o l v e d Zn M9/i Dissolved C u M9/I Particulate Zn M9/1 Par t icu la te C u M9/I • -Wt Par t icu la tes P. P.rn. 1 16. 89 20.545 6. 60 3.9 . 38 1.0 .67 3 16. 42 20.545 6.64 7.2 .84 1.2 .63 10 11.29 22.139 4.87 21.6 1.68 .4 .13 - - - -30 10.43 28.685 4.28 _ _ _ _ 100 9.90 29.575 3.93 8.0 _ _ _ _ _ _ _ _ _ 200 9.09 30.675 5.53 7.8 .68 .8 .18 — — 210 8.99 31.682 3.49 5.4 .54 . 8 .21 _ _ _ _ 219 31.966 3.41 - - - -1 17.12 2 3.59,7 • 5.1 1.91 3.0 .11 6. 36 3 1,6. 2 0 22.572 4 - 7 .91 2.1 .77 17.40 1 14.76 21.787 6. 59 8.8 .43 3.0 . 32 12.31 3 22.008 6. 35 10.5 1.45 1. 3 .49 20. 79 10 10. 86 28.852 4.51 10.6 .76 .9 .41 17.90 CRUISE 73/35 D A T E 5 September, 1973 1 STATION . 3 cont 'd (b). 4 (c) 5 • D e p t h m T e m p e r a t u re oc Sa 1 Inity ° ' o o D i s s o l v e d • m l / | 0 2 D i s s o l v e d Zn M ° / l Dissolved C u ."9/1 Particulate Zn M ° / l Par t icu la te C u Wi Par t icu la tes p. p.m. 20 9.54 29.475 4.09 9.0 .69 1.0 . 36 24.75 .'••50 9.53 30.049 3. 90 2.1 .84 •9 .52 7.02 75 10.11 30.416 3.90 — — _ _ _ _ 100 9. 95 30.605 3.86 • 8 . 7 . .91 .9 .72 25.58 125 9.80 30.752 3. 78 . . _ _ . _ 150 9.83 30.783 3. 76 9.6 1. 06 .8 .48 28.41 . 170 9.62 30.871 3. 71 1.5 .53 .5 . 80 180 9.50 30. 884 •' 3.69 4.2 .1.14 1.8 .96 24.95 • 184 ' 30.878 3.87 11.6 .99 1 17., 12 2 3.59 7 4.6 .45.- 2.6 1.60 _ .. _ _ 3 16.2 0 22.572 10.0 .82 1.3 1.02 21.46 1 . 15.24 22.917 - ; 7.2 . 75".. 2.7 1.19 - _ _ _ 3 10 13.97 10.6 7 24.981 28.621 6.4 > 12.6 .55 .9 8: 1.6 .8 1.17 .62 51.89 CRUISE 73/35 D A T E s September, 1973 STATION ... (a) 5.5 Cb) 6 • D e p l h m T e m p e r a t u r e o C S a U n i t y %o D i s s o l v e d O j • m l / | D i s s o l v e d Zn M9/l D i s s o l v e d C u M9/I P a r t i c u l a t e Z n M9/1 P a r t i c u l a t e C u M B / I Wt P a r t i c u l a t e s p. p . m . 1 13.97 23.662 6.29 8.3 .63 1.5 1. 50 19.35 3 24.804 6.01 4.5 .67 2.0 "1.23 10 i 0 . 8 3 28.224 4.49 5 .3 .59 2.2 1.14 ; 2 0 9. 71 29.401 4.10 17.3 .47 1.3 1.23 49.31 30 .9 .15 29.691 4.05 - - - -50 9.04 30.011 4.01 9.4 1.07 .7 0.44 100 9.57 30.587 3.83 10. 8 1. 75 . .5 0.13 150 9.22 30.794 - 3. 82 ' 200 8. 84 30.883 3.9 8 — — - - - -2 30 8.94 30.984 3.69 9.4 . 79 .3 0.32 _ ' 240 '8.98 31.017 3.70 5.3 . 55 - — _ 247 31.029 3.58 9.5 1.01 1 14.01 2 4. 72 8 6.43 7.8 1.19 2.4 .33 11.53 3 12.52 26.942 5.67 10.2 2.2 5 2.1 .11 26.44 CRUISE 73/35 D A T E 5 September, 1973 STATION . (a) .6 cont 'd (b) 5.7 • D e p t h m T e m p e r a t u re oc Sa U n i t y % o D i s s o l v e d 0 2 • m l / l D i s s o l v e d Zn M9/l Dissolved C u Particulate Zn M9/I Par t icu la te C u M9/I Wt Par t i cu la tes p.p.m. 10 ' 6.89 28.631 4.55 17.8 1.34 .7 .41 2 0 9.39 29.493 4.28 4.5 .74 .7 .79 30 29.794 3.83 - — -50 8. 76 30 .020 3.84 9.1 1.66 .2 .06 10 0 9. 32 30.602 3.74 150 9.55 1 30.804 3.55 9.9 1. 75 .3 .93 _ _ _ _ _ 160 1 9. 05 30.764 30.731 3.68 3. 74 170 8. 76 13.7 1.96 . 8 .30 — « _ . . . 180 8.61 30.749 3.65 11.1 1.81 190 8. 59 30.792 3.76 • .6 1. 75 254 31.028 3.51 9.5 1.01 1.2 0.54 1 13. 7 7 23.526 6.38 15.3 1.34 .8 .28 49.06 3 13.53 23.705 6.31 12.3 .94 . 7 1.10 54. 73 10 10.67 2 8. 52 8 .4.51 9.5 , .17 1.0 1.42 30.01 ".-CRUISE 73/35 D A T E 5 September, 19 75 1 STATION , Ca) 5.7 Cont'd Cb) 7 (c) 8 . — • D e p t h m T e m p e r a t u r e ° C S a l i n i t y % o D i s s o l v e d 02 • m l / i D i s s o l v e d Zn M9/l Dissolved C u 9^/1 Particulate Zn M9/1 Par t icu la te Cu Ms/I Wt Par t i cu la tes p. P.m. Ca) • 20 30 8.90 20.711 29.894 4.05 5.94 9. 0 .10., 1.1 .04 19. 1Q 50 9.95 30.325 5.87 5.5 .15 75 10.02 50.525 5.85 - - - -100 9.90 30.614 5. 80 7.4 .2 7/ • 0 N.D. •.. 12 5 9.90 50.685 5.55 140 9. 86 30.678 5.75 12.5 1.42 .8 50.40 153 50.82 5' 4.04 10.5 1.14 1.7 .66 46. 90 Cb) 1 15.40 27. 012 ' 9.4 .71 .9 1.55 2 6.59 3 15.42 27.022 9.2 .. 80 1.2 .78 Cc) 1 17.59 2 4.6.91 7.6 . 50 1.0 1.44 24.80 3 16.22 24.875 9.4 .50 2.0 . 89 CRUISE 73/35 D A T E 5 September, 1973 STATION ; (a) 9 (b) 12 • D e p t h T e m p e r a t u r e m oc S a U n i t y % o D i s s o l v e d 0 2 • m l / | D i s s o l v e d Zn M9/l Dissolved C u r«9/l Particulate Zn M9/I Par t icu la te C u M9/I Wt Par t icu la tes p. p.m. 1 16.53 26.491 10.0 . 78i .8 .97 3 26.546 9.2 .52^ . 5 .66 1 16.27 25.838 6.60 10.1 . 52"" .5 .20 17.30 3 16.17 2 5.85 5 ,6.60 10.5 ,95r .6 .37 . . . . 10 14.46 27.919 6.91 • - - _ _ 2 0 10.21 29.210 4.26 16.0 1.17 .3 .19 23. 34 30 9.83 29.344 4.23 19.4 1.48 .4 .20 2 3.52 50 9.26 29.630 4.05 . . . . _ _ _, _ 75 8. 81 30.042 ' 3.96 18.5 1. 70 .2 .17 20.64 100 .9. 32 30.471 3. 72 — — 150 9.19 30.881 5.77 15.3 1. 31 .2 .15 20.40 200 8.76 30.899 3.51 - - _ _ ' 250 8. 86 30.985 3. 75 22.8 2.49 . 1 N.D. 7.36 : 300 8.67 30.989 3.86 > - - - - -CRUISE 73/35 D A T E 6 September, 1973 STATION Ca). 12 cont 'd (b) 13 '(c) 14 D e p t h m T e m p e r a t u r e oc S a l i n i t y D i s s o l v e d 02 • m l / i D i s s o l v e d Zn M9/l Dissolved C u .ug/ l Particulate Zn Par t icu la te C u M8/I Wl Par t icu la tes p. p.m. 350 370 380 39 0 400 407 8. 80 8. 88 8.91 8.9 0 8.90 31.072 31.113 31.129 31.138 31.15 3 31.173 3. 74 3. 59 3.59 3.65 3.62 3.56 7.1 6.8 6.5 4.9 4.6 1.41 1.22 1.22 1.07 .79 .1 .1 .1 .6 .1.20 .11 .23 .17 1 15.21 2 7. 070 3.8 . 55 1.5 . 82 3 15.22 2 7. 096 4.1 .4.0 1.8 .79 1 14.98 27.625 6.4 7 6.0 .53 . 1.0 .37 3 14.9 7 27.634 6.38 11.6 1.60 . 7 .38 10 14.89 2 7.65 8 6. 39 6.0 1.38 .8 .37 20 10.36 29.183 4. 49 30 9.84 29.453 4.15 * • — — 29.40 29.32 32.54 27.86 CRUISE 73/35 D A T E 6 September, 1973 STATION f (a) 14 cont !d (b) 15 (c) 16 • D e p t h m T e m p e r a t u r e o c S a 1 int I y % o Di sso1ved 02 • m l / | D i s s o l v e d Zn M9/l Dissolved Cu Particulate Zn MB/1 Par t icu la te C u MB/ I Wl Par t i cu la tes p. p.m. • 50 9.44 29.625 4.15 5.4 .63 75 8. 80 29.958 3.55 100 8. 61 30.334 3. 78 5.4 .67 200 6.0 .75 300 8. 3 1.67 - - _ - ' . 32 0 7.8 1.01 . 1 N.D. 21. 70 330 17.3 1.59 N.D. N.D. 19.40 34 3 31.026 3. 70 14.0 1.62 .3 .07 29.32 1 13.43 28.018 8.0 .63 1.6 1.25 31.56 3 13.42 28.014 6.0 .55 .4 .11 26.40 1 15. 22 2 7.209 6.55 14. 0 1.47 .1 .02 3 8.57 2 7.203 6. 54 18.6 2.29 .6 .38 20 11.40 2 8.76 3 4.8 3 8.0 .59 .6 .26 CRUISE STATION 73/35 16 cont 'd D A T E 6 September , 1973 • D e p t h m T e m p e r a t u r e oc Sa U n i t y % o O i s s o l v e d 0 2 • m l / | D i s s o l v e d Zn M9/l Dissolved Cu M9/I Particulate Zn M9/1 Par t icu la te C u M9/I Wt Par t icu la tes P- P. 01. • 30 9 .61 29. 562 4. 20 9. 1 .40 50 9 .17 29. 7770 3. 96 7. 3 .47 100 8 .43 30. 441 3. 84 13. 8 .99 150 8 .43 30. 659 3. 78 5. 8 .68 200 8 .43 30. 698 3. 82 10. 2 .95 210 8 .43 30 . 698 3. 92 15. 0 1.27 •3 .11 . 249 30. 725 3. 94 13. 4 .79 .5 .17 _ - - * VC C R U I S E 73/46 S T A T I O N D e p t h ' T e m p e r a t u r e ° C S a l i n i t y D A T E 15 November, 1973 D i s s o l v e d 02 • m l / l 1 8.65 29.045 6.03 3 8.66 29.046 5.47 10 8.69 29.581 4.92 20 8. 88 50 8. 83 30.246 4.20 50 8. 75 30.328 4.42 75 8. 70 30.462 4.43 100 8.62 30.634 4. 33 125 8.67 30.744 4.24 150 8. 78 30.880 160 8. 82 30.947 3.9 0 170 8. 87 30.98 8 3. 81 180 8.88 31.051 3.77 186 31.016 3.76 D i s s o l v e d Zn M 9 / l 3.9 4.7 2.9 4.5 4.0 3. 7 D i s s o l v e d C u M 9 / I . 38 .61 .61 .68 .31 . 38 P a r t i c u l a t e Zn M9/1 1.0 .7 1.0 .2 . 5 2.0 P a r t i c u l a t e C u M 9 / I . 86 . 86 .67 .18 .20 . 39 Wt P a r t i c u l a t e s P- P.Hi . 14.60 15.27 11.82 21.62 27.36 29.44 C R U 1 S E 73/46  STATION (a) 5.5 (b) D e p t h . T e m p e r a t u r e S a l i n i t y m . ° C % o ) 1 8.03 26.120 3 10.10 26.111 10 8.36 27.109 20 8.82 28.673 30 9.12 29.831 50 9.12 30.131 100 9.12 30.637 150 9.92 30.818 200 8.85 31.001 2 30 8.9 7 31.114 240 8.93 31.137 248 31.163 1 8.12 26.617 3 8.16 26.945 6.22 6.23 5.82 5.48 4.14 3.68 3.92 4.-0 8 3.49 3.80 3.80 3.48 1.4 1.0 2.3 4.4 6.4 5.1 3.7 .57 . 58 .61 1. 75 .84 .76 1.14 5.7 5.7 5.2 1.5 1.1 1.6 2.1 1.81 1. 77 1.29 .01 N.D. 26.4 0 2 5.70 20. 50 59.42 6.15 6.15 1.2 . 7 .51 .22 5.4 4.0 2.29 1. 76 14. 81 21.60 CRUISE 73/46 D A T E 15 November, 1973 STATION C a) 6 cont 'd (b) 5.7 Depth tn T e m p e r a t u re ° C Sa 1 Inity % o Di s s o 1 v e d 0 2 • m l / | D i s s o l v e d Zn M9/l Dissolved C u M9/I 10 ' 8 . 2 4 28.157 6.02 " 1.2 20 8.58 29.815 5.51 30 9.22 30.190 4.08 ' 50 9.15 30.725 3.51 4.4 1. 52 100 9.29 30.891 3.541 150 9.16 30.891 3.48 5.2 1.14 160 9.18 30.898 3.48 170 9.14 30.931 3.48 3. 7 . 76 1.80 ' 9.12 30.954 3.52 184 26.622 3.50 3.5 .61 1 7.87 24.629 6.46 1.4 • 3.1' 3 7. 89 24.592 6.41 6.9 1.68 10 8.13 24.960 5. 81 7.8 1.45 20 8. 32 27. 072 5.93 Particulate Zn P a r t l c u l a t e C u Wt Par t icu la tes A*9/1 M9/I p. P. m. . 81 .8 . 31 .8 .29 .4 .09 .5 1.2 1.0 .4 .10 1.18 .45 .22 vo oo CRUISE D A T E 73/46 STATION ( a) 5.7 c o n t ' d (b) 12 Depth 15 November, 1973 30 50 75 100 125 145 152 1 3 10 20 30 50 75 T e m p e r a t u r e OC 9.18 9. 19 9.25 9.26 9.21 9.06 8. 32 8. 34 8.42 8.65 8. 79 9.05 9.25 S a l i n i t y ° ' o o D i s s o1v e d 0 2 • m l / | 29.584 4. 34 30.342 3.50 30.570 5.66' 30.659 3.65 30.785 3. 69 30.868 3.78 30.916 3.82 2.8. 386 6 ..12 28.392 6.11 28.524 6.07 28.891 5.87 30.617 5.21 30.395 5.54 29.171 5.48 D i s s o l v e d Zn 5.7 6.8 6.J7 6.0 Dissolved Cu Aig/ i 1.22 .76 .45 .55 ID ID CRUISE 7 3 / 4 6 D A T E November, 1 9 7 3 STATION ( a) 12 cont'd (b) 1 4 D e p t h . T e m p e r a t u r e S a l i n i t y D i s s o l v e d O , OC m l / l D i s s o l v e d Zn Dissolved Cu Particulate Zn Par t icu la te Cu Wt Par t icu la tes 1 0 0 9 . 3 9 5 0 . 1 7 1 5 . 6 1 5 . 5 . 6 9 . 2 . 2 6 P-P-Ol. 1 5 . 4 9 I S O 9 . 2 1 3 0 . 8 8 5 5 . 5 9 _ . - . - . _ _ _ _ _ 1 7 5 9 . 1 1 5 0 . 0 1 8 5 . 5 0 - - _ _ •*-_._•_• 2 0 0 9 . 0 6 5 1 . 0 6 6 5 . 4 8 5 . 6 . 7 2 . 2 . 5 1 1 1 . 2 2 2 5 0 9 . 0 2 5 1 . 1 6 0 5 . 4 6 — . . . . 3 0 0 9 . 0 9 5 1 . 2 5 9 5 . 4 0 4 . 6 . 4 8 . 1 N.D. 1 6 . 2 1 3 5 0 9 . 0 . 6 5 1 . 5 0 5 5 . 5 5 — - _ — - — — . . . . . 3 7 0 9 . 0 6 5 1 . 5 2 9 5 . 3 0 . . _ _ _ _ _ _ _ 5 8 0 9 . 0 5 5 1 . 5 4 0 5 . 2 7 _ _ _ _ _ _ _ _ 3 9 0 9 . 0 6 5 1 . 5 4 2 5 . 2 6 _ _ _ _ 4 0 0 . 9 . 0 3 5 1 . 5 5 0 5 . 2 5 4 . 4 . 5 5 . 8 . 1 8 2 0 . 7 0 4 1 9 5 1 . 5 6 5 5 . 2 2 4 . 1 1 . 8 5 . 8 . 1 9 2 5 . 0 9 1 8 . 4 1 2 8 . 6 8 6 - - - - 1 5 . 6 1 . 5 5 . 2 . 0 2 1 0 . 4 6 3 8 . 3 9 2 8 . 6 8 5 . . . - 1 3 . 9 . 9 2 . 1 . 0 6 1 1 . 1 1 C R U I S E 73/45 D A T E 15 November, 1973 S T A T I O N ( a) 1 4 cont 'd (b) 16 10 100 330 337 1 3 10 20 30 50 100 150 200 220 233 T e m p e r a t u r e ° C 8. 38 9.17 8. 93 8.26 8. 36 8. 34 8. 36 8. 48 8.69 8. 96 9.11 9. 05 8. 99 Sa U n i t y 28.683 30.609 31.2 56 31.2 51 28.615 28.669 28.733 28.840 28.951 .30.614 30.901. 30.919 30.926 31.251 D i s s o l v e d O , • m l / | 6.23 6.18 6.21 5/81 5. 89 4.50 3.22 3.43 3.46 3.43 3. 58 D i s s o l v e d Zn M9/l 10.3 6.3 4.7 8.3 16.6 5.1 7.3 Dissolved Cu M9/I 1. 07 .68 . 38 . 70 1.08 . 53 . 53 Particulate Zn M9/1 1.1 .9 . 1 . 1 .7 1.4 1.3 Par t icu la te C u Me/l .28 .36 N.D. .04 .21 .46 . 39 Wt Par t icu la tes p. P.m. 18. 30 19.36 6.6 •4.5 .61 .49 1.0 . 7 . 30 .63 CRUISE 74/1 STATION (a) 3 (b) 6 Depth T e m p e r a t u r e OC 3 10 20 30 SO 75 100 12 5 150 160 170 180 1 Sa Uni ty D A T E 7 January, 1974 D i s s o l v e d 0 2 D i s s o l v e d Zn Dissolved C u m | / ' M9/l *»9 / l Particulate Zn M9/1 Par t icu la te Cu M9/I Wt Par t icu la tes P-P.Ol. 5. 43 27.069 6.92 3.1 .51 • 8 .17 . 22.77 7.13 2 8.572 6. 0:5 1.4 .53 .8 .21 35.26 8. 99 29.214 5.89 7. 42 29.409 5.83 7. 49 29.5 78 5.89 2.4 .44 1.1 '. 38 32.81 7.57 29.665 5. 75 8.10 29.992 5.14 4.1 .31 .2 .12 23.02 8.2 7 30.240 4/8 7 9. 01 .. 30.383 4.59 5.!4 .. 93 .2 .14 18.73 8. 75 30.674 30.859 4.05 3.,65 - - - - — — 8. 92 30.8 76 3.61 4.3 . 82 .6 .38 20. 80 4.24 25.629 6.8 7 4.5 7 25.953 7.01 5.2 .56 1.5 .51 CRUISE 74/1 D A T E STATION ( a) 6 cont 'd (b) 12 7 January, 1974 10 20 30 50 100 150 160 170 220 3 10 20 30 50 5. 84 7. 34 8. 00 8.20 8.28 8. 79 8. 54 8.67 5. 44 5.51 8.98 7. 71 8.10 29.431 28.442 29.332 2 9.65 3 30.059 30.616 30.081 30.199 30.976 27.703 27.878 28.437 28.935 29.501 6. 43 5.69 5.25 4.53 4. 39 3. 84 5.00 4.64 3.45 6.93 6.93 6. 47 5. 5. 11 3.4 5.4 10.3 5.1 1.9 6.0 ,6 .6 1.0 . 52 .41 .86 1.8 .4 .4 .5 .1.05 .12 .12 . 50 .14 Wt Particulates P- p.ra-10. 5Q 52 . 55 16.56 5.7 .65 .5 .09 14.10 CRUISE 74/1 D A T E STATION (a) 12 cont 'd (b) 14 7 January, 1974 75 8.45 30.171 4. 76 100 8.70 30.42 5 4.26 5.5 .67 .1 N .D. 18. 06 150 8. 81 30.606 4.10 . - -175 8.91 30.798 3.78 4.9 .70 .2 .06 17. 93 200 8.92 30.914 3.44 _ _ _ _ _ 250 9. 00 3-1. 038 3. 39 4.7 .17 .1 .06 19.51 300 9. 00 31.126 3. 34 _ — . _ _ — _ 350 31.198 3.15 . . . _ _ _ _ _ 400 9.05 .31.204 4.3 .61 .4 .22 19.14 3 5. 41 28.212 6.96 6.8 . 71 5.1 1.00 39.42 10 5. 58 28.182 6.96 5.6 .61 4.7 . 86 • 20 6. 00 28.313 6. 72 _ _ _ _ 30 6.99 28.732 6.15 _ _ _ _ _ _ _ _ 50 7. 98 29.380 5.2 7 w — • _ CRUISE 7 4 / 1 D A T E 8 January, 19 74 STATION 14 cont'd D e p t h m T e m p e r a t u re ° C S a 1 Inity % o D i s s o l v e d 0 2 • m l / | D i s s o l v e d Zn Ata/i Dissolved Cu M9/I Particulate Zn Ma/1 Par t icu la te Cu Me/l Wt Par t icu la tes p. p.m. 75 8.32 29.847 4.53 100 8.60 30 .2 76 4.40 1.7 .55 .2 N.D. 200 8.97 31.169 3.13 : . 300 8.96 30.945 3. 43 . . . . 320 8.9 7 31.130 3.19 330 8.95 31.167 3.11 4.5 .51 .1 . 08 332 31.164 3. 05 , 4.0 .48 .1 .10 _ _ _ CRUISE 74/15 STATION (a) 3 (b) 5.5 D e p t h . T e m p e r a t u r e S a l i n i t y m °c %0 1 10.27 19.945 3 9.2 7 21.671 i o 8. 72 25.986 2 0 7. 74 28.580 50 7.55 29.505 100 7.72 29.884 150 8.83 30.209 170 8.12 30.355 180 8. 36 .30.514 184 30.522 1 10.63 12.372 3 9. 49 24.718 10 8.84 27.468 20 7.90 28.371 D A T E 29 A p r i l , 1974 Di s s o Ived 02 • m l / | D i s s o l v e d Zn M9/i Dissolved C u Particulate Zn M9/1 Par t icu la te Cu Mo/I Wt Par t icu la tes P-P.ITI. 7. 29 5.9 1.39 1.7 . 50 13.10 7. 31 6.3 1. 72 1.7 .31 19. 05 7. 44 10.9 1.91 1.1 .17 2 7.10 5.56 8.1 .61 1.5 1.22 5. 09 6.3 .50 . .4 .08 5.93 4.5 , 50 .4 N.D. 5.16 3.0 1. 01 4.59 4.8 0. 70 4.11 5.3 0.36 4.08 5.6 0.83 8.17 3.2 .68 4.0 1. 19 17.13 9.30 7.2 1.5 8 1.8 .07 24. 03 8. 39 6.4 1.70 2.3 . 15 36. 28 6. 32 6.6 1. 73 . 7 .48 23.87 30 7.63 50 7.55 100 7.63 2 00 8.5 3 230 8. 64 240 8.71 28.770 5.94 29.017 5.70 29.806 5.46 30.5 79 3.86 30.760 3.37 30.782 3.35 30 A p r i l , 1974 Dissolved Zn ,"9/l Dissolved Cu M9/I Particulate Zn M9/1 Particulate Cu MB/I Wt Particulates P-P.m. 6.4 1. 75 1.0 N.D. 9.8 1.12 .8 N.D. 8.2 1.20 .6 N.D. 8.8 . 89 .5 .04 7.4 . 76 .5 .09 5.2 .76 .4 N.D. B.2 Zinc and copper in Georgia S t r a i t sediment i n t e r s t i t i a l waters T A T I O N 3 12 14 C R U I S E ~"""~-~^Metal Sample Zn Cu Zn Cu Zn C u 0-2 cm 9 7.1 12.10 43.4 7.81 42.7 8.23 73/30 5-7 63.0 7. 85 31. 0 5.34 31.0 6.57 10-1 2 40.2 8. 13 18.8 3. 62 26.7 4.90 0-2 119.1 10.22 41.0 8.11 23.5 2.85 73/31 5-7 62.1 8.70 36.2 8.26 20.2 4.2 3 10-12 57.6 9.68 20.1 4. 37 19. 7 3.88 0-2 113. 0 20. 81 68.7 7.93 31.2 7. 01 73/35 5-7 85. 5 17..47 45.8 5.80 34. 8 .6.18 10-12 52.0 7.42 20.9 .4. 00 2 0.1 3.92 0-2 26. 7 7.3.3 18. 3 4.16 19.6 5.31 73/46 5-7 39.6 7. 09 30.2 5.29 14.8 3. 02 • 10-12 ' 37. 5 7.61 12. 8 6.18 19.1 2. 87 B.3 0.1N ITC1 extractable zinc and copper i n Georgia S t r a i t sediment T A T I O N 3 1 2 14 C R U I S E — - - . M e t a l S a m p l e ^ " - " - ^ ^ Zn Cu Z n Cu Zn Cu 0 -2 em 113.0 14. 83 6 4.7 12.22 48.6 5. 88 73 /30 5-7 94.6 14. 06 47.2 10.47 40. 7 9.9 0 10-12 61.9 6.22 28.3 11. 06 20.9 5.10 0 - 2 139.0 19. 30 59. 3 7.45 35.1 5.93 73/31 5 - 7 90.8 16.40 52.9 14. 71 29.2 4.80 10-12 88.2 . 9.21 29.0 7.90 24.6 3. 62 0 - 2 162.1 17.91 102 . 7 15.12 44.4 11.91 73/35 5 - 7 108. 4 12.66 53.1 10. 89 47.5 9. 78 1 0 - 1 2 78. 6 13.08 32.3 7.23 31.6 3.39 0 - 2 40. 5 15. 72 20.3 7.56 27.8 7.61 7 3 / 4 6 5 - 7 56.1 16.08 43.6 9.62 21.2 6.20 10-1 2 65.6 15. 31 30.9 11. 38 2 5.6 5. 36 110 B.4 Fraser R i v e r Water Analyses Sampling Locations (Figure 2.2) 1. Johnson Slough (5 mi west of Aggassiz on Hwy. 7) 2. A g g a s s i z (at bridge over Fraser River) 3. M i s s i o n C i t y • A 5 W t u r n o f f on Hwy. 7 4. F o r t Langley F e r r y Terminal (south bank of F r a s e r River) Sampling Times A. August 29, 1973 B. November 10, 19 7 3 C. January 16, 1974 D i s s o l v e d z i n c and copper i n pg/1 Time L o c a t i o n . A B C Zn Cu Zn Cu Zn Cu 1 1.9 0.15 2.0 0.18 2 1.4 0. 06 1.8 0.07 1.8 0.08 3 1.5 0.30 2.0 0. 32 1.6 0 .33 4 3. 0 0.2.4 3. 1 0.44 3.8 0.33 

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