TRACE ELEMENTS AND BACKGRGUND GAMMA LEVELS IN. FISH NEAR THE WESTERN SHGRE OF LAKE ERIE Thesis for the Degree of M. S. MICHIGAN STATE UNIVERSITY FRED WILLIAM GOTTSCHALK 1974 1 “1..-; , _ L If” n .4 n y .1. 1,: t' . fm<_.I--.-.1n 11;. (, 1 ' . er IIIIIIILIIIIIIIIIIIIIIIIIIII 3 12 3 00647 3957 I'HESIS ~‘Jfl".~vt. \_. _ ABSTRACT TRACE ELEMENTS AND BACKGROUND GAMMA LEVELS IN FISH NEAR THE WESTERN SHORE OF LAKE ERIE By Fred William Gottschalk Fish collected from Lake Erie in the vicinity of the proposed discharge from Fermi II, a nuclear powered electric generating station, were analyzed for concentrations of stable trace elements and radio- isotopes. Stable elements studied were Cs, Co, Fe, Mn, Sr, and Zn. 13% 137 h Radioisotope analyses were conducted for Cs, Cs, 57Co, 5 65 Mn, and Zn. Samples were collected from April 1973 to December 1973. Data collected in this study constitute part of the preoperational study of the radioecological impact of the discharge from Fermi II on the aquatic environment. Samples were collected by experimental gill nets and trawling at five stations located in the study area. Analysis of variance and Student, Neuman, Keuls Multiple Range Tests were used to analyze differences in stable and radioisotope concentrations between stations and between feeding habits. Spatial distribution of stable elements appeared to follow the Swan Creek plume to some extent. Bottom feeding fish had significantly higher concentrations of stable iron, manganese, strontium and zinc than'piscivores. The only man-made radioisotope present in high enough concentra— tions to detect was 137CS, but it did not significantly (0: a .OSI vary spatially, trophically, or temporally. TRACE EIEMENTS AND BACKGROUND GAMMA LEVELS IN FISH NEAR THE WESTERN SHORE OF LAKE ERIE Fred William Gottschalk A THESIS submitted to Michigan State University in partial fulfillment of the requirements for the degree of MASTER OF SCIENCE Department of Fisheries and Wildlife 1971+ ACKNOWLEDGEMENTS I wish to express appreciation to my graduate committee, Dr. R. A. Cole, Dr. F. M. D'Itri, Dr. E. W. Roelofs, and especially Dr. N. R. Kevern, Chairman. Thanks to fellow graduate students, D. Brege and P. Shaffer, for help in the field, and J. Seelye for suggestions on analytical methodology. Thanks are due to the Detroit Edison Company for providing financial support and use of their equipment and facilities. For her patience and encouragement during my graduate study, I am grateful to my wife, Kathy. ii TABLE OF INTRODUCTION . . . . . . . . . DESCRIPTION OF THE STUDY.AREA . METHODS AND MATERIALS . . . . . Field Procedures . . . . . Laboratory Procedures . . RESULTS 0 O 0 O O O O O O O O 0 Stable Analysis . . . . . ce S ium O O O O O O O O O O CObalt O O O O O O 0 O O 0 Iron 0 O O O O O O O O O O mngane se 0 O I O O 0 O O Strontium, . . . . . . . . Zinc . . . . . Distribution of Radioisotope Analysis . . DISCUSSION . . . . . . . . . . SWY I O O O O O O O O O O 0 CONCLUSIONS . . . . . . . . . . LITERATURE CITED . . . . . . . APPENDIX A . . . . . . . . . . iii Stable Element CONTENTS in Page Number 10 Al A3 LIST OF TABLES Mean annual water quality parameters (mg/liter) among the lake stations. Summary of method for nitric acid digestion of fish samples to determine concentrations of Cs, Co, Fe, Mn, and Zn. Summary of method used to prepare fish samples for Sr analysis. Operating conditions for analysis by atomic absorp- tion and flame emission. Summary of method used to prepare fish samples for radioisotope analysis. Percent of radioisotope recovered from fish chunks after ashing at A5000. Multiple range analysis of mean annual concentra- tions of stable isotopes in.three trophic levels of fish. Distribution of stable elements in carp (ug/g). Analysis of variance to test differences in 13703 concentrations due to feeding habits. Trace element concentrations in fresh water fish (ug/g wet weight) Assigned trophic habits of fish species collected from the study area. Mean concentrations (E :l S.E.) of stable isotopes in whole fish samples taken from the study area on 3 April 1973. Mean concentrations (E :l S.E.) of stable isotopes in whole fish samples taken from the study area on 7 June 1973. iv 11 ll 1h 20 28 3o 35 A5 50 51 List of Tables - Cont'd. Number All A5 A6 A7 A8 A9 A10 All A12 A13 AllI A15 Mean concentrations (i :_l S.E.) of stable isotopes in whole fish samples taken from the study area on 7 August 1973. Mean concentrations (i :_l S.E.) of stable isotopes in'Whole fish samples taken from the study area on 1% September 1973. Mean concentrations (i :_l S.E.) of stable isotopes in whole fish samples taken from the study area on 7 November 1973. Mean concentrations (E :_l S.E.) of stable isotopes in Whole fish samples taken from the study area on 8 December 1973. Multiple range analysis of mean stable isotope con- centrations in bottom feeding fish from the study area 3 April 1973. Multiple range analysis of mean stable isotope con- centrations in.bottom feeding fish from the study area 7 June 1973. Multiple range analysis of mean stable isotope con- centrations in bottom feeding fish from the study area 7 August 1973. Multiple range analysis of mean stable isotope con- centrations in bottom feeding fish from the study area 1% September 1973. Multiple range analysis of mean stable isotope con- centrations in bottom feeding fish from the study area 7 November 1973. Multiple range analysis of mean stable isotope con- centrations in bottom feeding fish from the study ‘area 8 December 1973. Multiple range analysis of mean stable isotope con- centrations in.planktivorous fish from the study area 3 April 1973. Multiple range analysis of mean stable isotope con- centrations in planktivorous fish from the study area 6 June 1973. Page 52 53 5h 55 56 57 58 59 6o 61 62 63 List of Tables - Cont'd. Number A16 A17 A18 A19 A20 A23 A2h A25 A26 Multiple range analysis of mean stable isotope con- centrations in planktivorous fish from.the study area 7.August 1973. Multiple range analysis of mean stable isotope con- centrations in.planktivorous fish from the study area 1h September 1973. Multiple range analysis of mean stable isotope con- centrations in planktivorous fish from the study area 11 November 1973. Multiple range analysis of mean stable isotope con— centrations in planktivorous fish from the study area 8 December 1973. Multiple range analysis of mean stable isotope con- centrations in piscivorous fish from the study area 7 June 1973. Multiple range analysis of mean stable isotope con- centrations in.piscivorous fish from the study area 7 November 1973. Multiple range analysis of mean stable isotope con- centrations in piscivorous fish from the study area 8 December 1973. Multiple range analysis of mean stable isotope con- centrations in bottom feeding fish from 3 April 1973 through 8 December l973. Multiple range analysis of mean stable isotope con- centrations in.planktivorous fish from 3 April 1973 through 8 December 1973. Multiple range analysis of mean stable isotope con- centrations in piscivorous fish from 3 April 1973 through 8 December 1973. 13 Concentration (pCi/g) of 7Cs (i :_l S.E.) in.whole fish. vi Page 6% 65 66 67 68 69 7O 71 72 73 7h Number LIST OF FIGURES Map of the study area in relation to western Lake Erie. Map of the study area including positions of the sampling stations. Cesium concentrations (mean i’l standard error) in piscivores, planktivores and bottom feeders collected from the lake stations (F2-F5). Concentrations (mean :1 standard error) of Co, Fe, Mn, Sr, and Zn in bottom feeders collected from the lake stations (F2-F5). Concentrations (mean :1 standard error) of Co, Fe, Mn, Sr, and Zn in.planktivores collected from the lake stations (F2-F5). Concentrations (mean :1 standard error of Co, Fe, Mn, Sr, and Zn in piscivores collected from the lake stations (F2-F5). 1 Concentrations (mean :1 standard error) of 37Cs in bottom feeders collected from the lake stations (F2-F5). 1 Concentrations (mean :1 standard error) of 3703 in planktivores collected from the lake stations (F2- F5). Concentrations (mean :1 standard error) of 137Cs in piscivores collected from the lake stations (F2- F5). vii 1? l8 19 31 33 INTRODUCTION The increasing number of nuclear, electric-generating plants poses a potential hazard to aquatic environments receiving the cooling waters from these installations. Bioaccumulation by aquatic organisms has been demonstrated for some of the radioisotopes associated with nuclear’power plants. Fish in the vicinity of the receiving waters may accumulate sufficient amounts of the radioisotopes to present a health hazard to humans who consume them. The Detroit Edison Company is constructing a nuclear powered electric-generating plant, Fermi II, on the western shore of Lake Erie, approximately seven miles north of MDnroe, Michigan. Fission products from the nuclear reaction or radioisotopes induced by the neutron activation of stable isotopes in the vicinity of the nuclear reaction may be contained in the plant's effluent. The present study was undertaken to provide information on the aquatic distribution of stable cesium, cobalt, iron, manganese, strontium, and zinc, which are the counterparts of radioisotopes, in the vicinity of Fermi II. The distribution of stable isotopes was assessed to predict the fate of radioisotopes that may be released based on the specific activity hypothesis offered by the National Academy of Sciences (1960). A second objective was to establish data on the distribution and levels of man-made radioisotopes in.the aquatic environment near the plant site. With this background information, it should be possible to determine the amount of radioactivity that the plant is contributing to the aquatic environment. The specific purpose of this study was to determine preoperational and Spatial variation in concentrations of stable elements and radio- isotopes in fish captured from the study area. Fish were separated into three groups, according to their major feeding habits, to deter- mine if stable or radioisotope concentrations varied with the gross trophic differences. DESCRIPTION OF THE STUDY AREA The study area (Figures 1 and 2) is located.between.Point aux Peaux and Point Mouillee in the near shore area of Lake Erie's western basin. Also included in the area is Swan Creek, a small stream that enters the lake about A km north of Point aux Peaux. Fermi II is being constructed approximately midway between.Point aux Peaux and the mouth of Swan Creek. The plant effluent will enter the lake somewhere between the plant and the mouth of Swan Creek. The western basin of Lake Erie is shallow. It has a mean depth of 7.h m, a maximum depth of 20.h m, representing less than 13% of the total lake's surface area, and including 5% of the lake's volume. Minimum.possible flushing time for the western basin is about 60 days. The bottom of the basin is made up of 58% soft gray mud, 17% sand, 12% sand and mud, 7% gravel, 3% bedrock, and 3% clay (Verber, 1957). Sand and gravel are common near shore and mud predominates in the deeper water (Hartman, 1973). Langlois (195%) considered the western basin to be the most valuable spawning and nursery grounds for most species found in the lake. The relatively warm waters in this area coupled with the extensive shoal areas provide ideal fishing grounds for many species of fish. Maximum depth in the study area is 6 m. Bottom sediments in this area range from coarse sand to mud. High turbidities in the area are associated with the wind generated turbulence and high plankton 3 Figure 1. Map of the study area in relation to western Lake Erie. DEYIOIT RIVER ‘39 e ,, m“ ”EE‘EV'»~” / TOLEDO $ $23 O 9/0 r“ I K m Figure 2. Map of the study area including positions of the sampling stations. (Stations F1, F2, and F3 are fixed. Stations FA and F5 are along a moveable transect). SWAN CREEK XI: 3 p. PERM, LAKE ERIE POINT AUX PEAU :21 FISH STATION 1km densities (Beeton, 1961). Secchi-disc readings were low throughout the sampling period; never more than 1.5 meters. Temporary stratifica- tion of the western basin occurs during summer (Britt, 1955), but because of the shallowness of the basin, it is usually well mixed. Dissolved oxygen is usually near 80% saturation in the bottom waters of the basin. Major currents in the basin move south to southwest (Hartley gt_§1,, 1966). These currents are caused primarily by the Detroit River which enters the lake about 11 km north of the study area. About 99% of the flow into the western.basin comes from the Detroit and Maumee Rivers. As the flow from these rivers meet in the southwest part of the basin, a large eddy is formed. This eddy causes the western shore water to be influenced most by industrial and municipal wastes entering primarily via the large rivers (FWPCA, 1968). water chemistry of the study area is presented in Table l. The impact of Swan Creek on the lake is measureable only near the mouth of the creek. Conductivity studies made during the sampling period revealed that the water from Swan Creek had thoroughly mixed with the lake water within 1 km of the creek's mouth. Station F1 (Figure 2) was located in Swan Creek about 1 km from the creek's mouth. The depth at this location ranged from 1.5 to 2.0 m. Sediment was composed mostly of silt. Station F2 was located in the lake about 0.5 km north of the mouth of Swan Creek and 0.25 km from shore. Average water depth at this station was about 2 m, although, for short periods the depth was increased by l m due to seiches. In 1973, seiches were most frequent during the spring. The sediment was composed mostly of sand. Table 1. Mean annual water quality parameters (mg/liter) among the lake stations. Suspended Organic Total Total Total Solids Carbon Chloride Nitrogen Phosphorus Mean 19.1 h.8 17.0 1.2 0.08 Range 12.h-32.5 h.3—5.7 12.6-20.8 0.8-1.u 0.06-0.11 Station F3 was located about 2 km north of the mouth of Swan Creek and 0.75 km from shore. Average water depth at this station was about 2 m. Sediments were composed of fine sand and scattered boulders. Station FA was located about 0.5 km south of the mouth of Swan Creek and about 0.25 km from shore. Water depth was about 2 m. Sediment composition varied from silt to sand depending on weather conditions prior to sampling. Station F5 was located about 1.5 km south of the mouth of Swan Creek and 1.25 km offshore. Water depth was about A m. Fine sand and silt composed the sediments in this area. METHODS AND MATERIALS Field Procedures Fish samples were collected from five locations (Figure 2) at six-week intervals When conditions permitted. Sampling stations were located in Swan Creek and along two transects that radiated from the mouth of Swan Creek. One transect was fixed along the axis of the prevailing plume of Swan Creek after entering the lake. The other transect was moveable, with its position determined.by the plume direction of Swan Creek on the day of sampling. When the plume was in.the direction of the prevailing current, the moveable transect was established.perpendicular to the fixed transect. This sampling scheme was designed to allow use of the discharge from Swan Creek to simulate the plant's discharge. Fish were collected using a 5-m otter trawl with 2.5-cm stretched mesh netting in the wings and 6-mm stretch mesh netting in the cod end. On days when trawling failed to produce enough biomass for analysis, or a boat capable of pulling the trawl was unavailable, experimental gill nets were set overnight. The gill nets had 1.3, 2.5, 3.8, and 6.3-cm square mesh netting and an overall length of 30.5 m. When fish samples were brought back to shore they were sorted into three trophic categories (bottom feeders, planktivores or piscivores), determined.by random stomach samples and from the 9 lO literature. After being sorted into feeding types, the fish were placed in plastic bags and frozen for transport to the laboratory. Laboratory Procedures In the laboratory the fish were kept frozen until analyzed. Contents of the gut were included in the analysis of fish collected on A April 1973 and 7 June 1973. Fish collected during the remainder of the year had the gut contents washed out prior to analysis. Samples collected on A April 1973 and 7 June 1973 were cut into strips on.a bandsaw, then ground 3 separate times to Obtain a homo- geneous mixture. Fish collected after 7 June 1973, after initially being sorted into broad trophic categories, were divided into three groups as similar as possible in numbers, species compositions, and size of the individual fish. In this manner, variations among groups of individual fish became identifiable. Triplicate sets of lO-g subsamples were taken from the ground tissue for analysis of stable Cs, Co, Fe, Mn, and Zn as outlined in Table 2. Strontium was analyzed as summarized in Table 3. Analyses of stable Co, Fe, Mn, and Zn were accomplished using a Jarrell-Ash 82-800 series atomic absorption spectrophotometer. Stable isotopes of Cs and Sr were determined by flame emission spectroscopy on the same instrument (Table A). Radioisotope analysis was accomplished.by freeze-drying triplicate subsamples (200 g) of the ground fish. This was done to prevent loss due to splattering'When these samples were ashed in a muffle furnace at h5OOC The ash was transferred to a glass counting vial for gamma analysis. A summary of the method is given in Table 5. 11 Table 2. Summary of method for nitric acid digestion of fish samples to determine concentrations of Cs, Co, Fe, Mn, and Zn. lO. Grind whole fish in meat grinder to obtain a homogeneous mixture. Place 10 g, wet weight, of ground fish into boiling-flask. Add 50 ml concentrated HNO3 to a'boiling-flask. Allow oxidation to proceed 1 hour with no heat applied. Reflux the solution approximately h hours, until nitrous oxide fumes are no longer visible. Distill off excess acid and water until about 5 m1 of acid are left in boiling-flask. Add 80 ml distilled water. Reflux with stopcock open for h-6 hours. .Allow to cool and remove from flask by rinsing into 100 ml volumetric flask with distilled water. Dilute solution to 100 ml with distilled water. Table 3. Summary of method used to prepare fish samples for Sr analysis. Transfer 9 ml of final solution.produced from the technique described in Table 2 to l-oz. nalgene bottle. Add 1 ml 12.5% lanthanum chloride solution to each sample. Analyze samples by flame emission spectroscopy. 12 Table A. Operating conditions for analysis by atomic absorption and flame emission. Resonance Line Sensitivity Absorption Element AO mg/liter or Emission Cs 8521 0.03 Emission Co 2&07 0.2 Absorption Fe 2h83 0.1 Absorption Mn 2795 0.06 Absorption Sr A607 0.15 Emission Zn 2139 0.03 Absorption lTable based on Elwell and Gidley (1967), and data supplied by Jarrell- Ash Division, Fischer Scientific Company. Table 5. Summary of method used to prepare fish samples for radio- isotope analysis. 1. Place 200 g, wet weight, of frozen ground fish in 1.5 cm3 pieces into a freeze-dryer flask and freeze-dry sample 2% hours. 2. Transfer freeze-dried sample to crucible and place in muffle furnace at 10300 for h hours. 3. Increase temperature 50°C every A hours. A. Allow sample to remain in muffle furnace at A5OOC for 6-8 hours. 5. Weigh ash after it has cooled to room temperature. 6. Transfer ash to vial for radioisotope analysis. 13 The dry ashing method used in.this study has been used.by Nelson (1969) for preparation of biological samples for cesium analysis. A study was made to determine how much volatilization occurred during ashing at ASOOC. Radioisotopes were placed on chunks (about 1.5 cm3) of fish and the chunks were analyzed in a gamma counter. The chunks were then freeze-dried and ashed at ASOOC for 12 hours and analyzed again in the gamma counter to determine how much, if any, of the radioisotope was lost. The results obtained (Table 6) are in agree- ment with those of Blincoe (1962), Martin and Blanchard (1969) and Meranger and Somers (1968). Samples used for radioisotope analysis were counted for 500 minutes with a Nuclear Chicago, 512 multichannel spectrophotometer coupled to a 3 inch, well type NaI(Tl) crystal detector and equipped 'with an automatic sample changer. The data were punched on.paper tapes and activities were determined using a modified least squares analysis computer program originally devised.by Brooks gt Q1, (1970). Statistical tests performed on the data included analysis of variance to evaluate differences both spatially and temporally. When a mean was found to be significantly different, a multiple range test (Student, Neuman, Keuls) was performed to determine which means were significantly different. All values were tested at the 0.05 level. variation of the mean is denoted by one standard error. 1h Table 6. Percent of radioisotope recovered from fish chunks after ashing at A500C. No. of Percent Recovery Standard Isotope Samples After.Ashing at ASOOC Error l3th 5 90.09 0.0191 9%o A 9975 00a5 51“Mn u 90.35 0.0118 65Zn 3 100.00 0.0000 RESULTS Stable Analysis A total of 170 composite samples of fish were analyzed for stable Cs, Co, Fe, Mn, Sr and Zn. There were discernible differences in the concentrations of some of the elements in fish with different feeding habits, in fish collected from different stations, and in fish collected on different dates. Figure 3 graphically illustrates the concentrations of Cs in the three feeding groups collected from the lake stations (F2-F5). Figures h-6 illustrates the concentrations of Co, Fe, Mn, Sr and Zn in bottom feeders, planktivores, and.piscivores collected from these stations. A one-way analysis of variance was used to test: (1) The differ- ence in concentrations of stable elements in fish collected from five sampling locations on each date and over the entire sampling period; (2) The difference in concentrations of stable elements throughout the sampling period; and (3) Concentrations in whole fish of the three different trophic habits. Results were tested at the 0.05 level. Table 7 gives the results of a multiple range test performed on the annual mean concentrations of the stable isotopes in the three trophic levels of fish. The results of multiple range tests performed on the stable element data obtained on each date of collection is included in the appendix. 15 16 Figure 3. Cesium concentrations (mean :1 standard error) in.piscivores, planktivores and bottom feeders collected from the lake stations (F2-F5). Cesium Concentrations Piscivores 1— or g 1 2 o 1 L n 1 1 1 1 1 A M .l J A S 0 N D 12 . PIa nktrvores or \ c» c P e L 1 l l L I l i A M J J A S O N D fie...§___v "Q/ 9 b Bottom feeders _ 31- hr- )P 17 Figure I-I. Concentrations (mean :1 standard error) of Co 0, Fe V, Mn 0, Sr 0 and Zn v in bottom feeders collected from the lake stations (F2-F5). 18 Figure 5. Concentrations (mean :1 standard error) of Co , Fe V , Mn 0 , Sr 0 and Zn v in planktivores collected from the lake stations (F2-F5). A ”(I I woourIIolxxdrosr 5 O 3 2 . 2% firm 520.160 so mcozotcmocoo 90 IO 70 Time 19 Figure 6. Concentrations (mean :1 standard error) of Co 0, Fe V , Mn 13, Sr 0 and Zn V in piscivores collected from the lake stations (F2-F5). 1201 MI 90! nor 70 H 7 '1 o mcozozcoocoo .0 2O Table 7. Multiple range analysis of mean annual concentrations of stable isotopes in three trophic levels of fish. Cs Feeding Type Planktivores Piscivores Bottom Feeders Concentration 5.6 7.6 8.2 Co Feeding Type Bottom Feeders Planktivores Piscivores Toncentration 0.52 0.68 0.73 Fe Feeding Type Piscivores Planktivores Bottom Feeders Concentration 32.67 h2.58 72.67 Mn Feeding Type Piscivores Bottom Feeders Planktivores Concentration 1.06 2.3A 2.A8 Sr Feeding Type Planktivores Piscivores Bottom Feeders Concentration 2.56 2.57 A.8A Zn Feeding Type Planktivores Piscivores Bottom Feeders Concentration 26.00 26.92 81.83 103 in ng/g; Co, Fe, Mn, Sr, Zn in ug/g. 21 Cesium Mean annual cesium concentrations were not significantly different among the three trophic levels. Bottom feeders appeared to have slightly greater concentrations of stable cesium (8.2 ng/g) than planktivores (5.6 ng/g) or piscivores (7.1 ng/g). No spatial.pattern could be detected for cesium concentrations of the three feeding types. Although the bottom feeders collected from Swan Creek in.November and December appeared to have the greatest cesium concentrations, the difference was not significant (« = 0.05). Seasonal fluctuations in levels of cesium in fish were not statistically significant, but an apparent trend could be seen in bottom feeders and planktivores. Cesium levels tended to increase in these two feeding groups from 3 April until a peak was reached on 1A September after which time a gradual decrease was observed in November and December. Cesium concentrations in.piscivores remained relatively constant throughout the study, decreasing only slightly in.November and December (Figure 3). Cobalt Cobalt concentrations did not differ significantly between the three trophic habits. There did.appear to be some trophic differences, with cobalt present in lowest amounts in bottom.feeders and greatest amounts in.piscivores. The mean annual concentration of cobalt in bottom feeders, planktivores and piscivores collected from the lake stations were 0.52, 0.68, and 0.73 ug/g, respectively. Bottom feeding fish collected in Swan Creek (Station Fl) had .greater concentrations of cobalt than those collected from the lake 22 stations on five of the six sampling dates. Although concentrations were usually greater in Siren Creek, the difference was not always significant. Bottom feeders collected from Stations F2 and F11 contained slightly greater amounts of cobalt than fish with similar feeding habits collected from Stations F3 and F5, but the annual differences were not statistically significant. Planktivorous fish captured at Stations F1 and F2 had greater cobalt concentrations than those collected from Stations F3-F5. No pattern could be detected for cobalt concentrations in piscivorous flab in relation to the location where they were collected. The annual trend of cobalt concentrations in bottom feeders was one of continuously decreasing amounts throughout the sampling period. Samples collected on 3.April averaged 0.98 ug/g cobalt, which was significantly greater than samples collected during the remainder of the study. .Amounts of cobalt in planktivores and.piscivores collected on 3 April.were also greater than at any other time during the study. Concentrations declined by 7 June and increased somewhat on 7 August, after which time they decreased through theremainder of the year in planktivores and piscivores. Iron Iron concentrations were consistently greater (p'< .05) in bottom feeding fish than in.planktivores and piscivores (Table 7). The annual mean concentration of iron in bottom feeders was 1.7 and 2.2 times higher than in.planktivores and piscivores, respectively. 23 The concentration of iron, spatially distributed within the study area, appears to be greatest in fish collected from Swan Creek, although the difference was not always significant. Fish in all three feeding categories had greatest concentrations of iron at Station Fl. Bottom feeders and.planktivores collected from Stations FA and F5 generally exhibited lower iron concentrations than those fish collected from Stations F2 and F3. Piscivorous fish collected at Station FLI- appeared to have higher concentrations of iron than.piscivorous fish collected from the other lake stations, although these differences in iron concentrations were not statistically significant. Seasonal fluctuations in the levels of iron detected in the fish followed the same general pattern in each of the three feeding types (Figures h-6). Concentrations in fish collected on 3.April were significantly below concentrations recorded for fish collected on 7 June for each of the three categories of fish. On 7 August concen- trations of iron in bottom feeders and.piscivores still were significantly above concentrations that were recorded for 3 April. The concentrations of iron in these two feeding types were not significantly different from levels reported for 7 June although levels had increased in bottom feeders by 22.5 ug/g and decreased in piscivores by 0.16 ug/g. Amounts of iron in planktivores had decreased significantly between 7 June and 7 August by 19.3 ug/g. On 111 September iron concentrations had declined significantly in.bottom feeders and piscivores, after which time no significant changes were recorded during the remainder of the sampling period which terminated on 8 December 1973. Planktivores collected on 1h September showed 2h intermediate concentrations of iron between the high recorded on 7 June and the decreased amount reported on 7.August. Samples collected on 7 Nevember and 8 December showed a gradual decrease of iron in.planktivores. Manganese The annual averages of manganese in.bottom feeders and.plankti- vores were not Significantly different, but both were Significantly greater than in piscivores (Table 7). Manganese concentrations were about 2.25 times greater in bottom feeders and planktivores than in piscivores. Manganese also seems to be higher in fish collected from Swan Creek than from the lake stations, although an analysis of variance did not Show any significant differences between any of the stations. All fish tended to have highest concentrations when collected from station Fl, moderate concentrations at stations F2 and F3, low to moderate concentrations at station FA, and bottom feeders and pisci- vores had high concentrations at station F5 where planktivores had low concentrations. Bottom feeding fish had annual fluctuations of manganese concen- trations that generally followed the same pattern as iron. Concen- trations appeared to increase steadily from 3 April, when.a mean concentration of 2.07 ug/g was detected, through 6 August when a high of 3.65 ug/g was recorded. 0n 1h September a significant decrease of 1.97 ug/g manganese had occurred in bottom feeders after which time no significant change in manganese concentrations was observed throughout the study period. In planktivores and piscivores, levels 25 increased slightly in June in both feeding types, and again in November in.planktivores. Strontium Mean concentrations of strontium.were greatest in bottom feeders, being Significantly above levels found in.planktivores and piscivores which were not Significantly different from one another. The mean annual concentration of strontium was 1.9 times higher in bottom feeders than.the other feeding types. Spatial distribution of strontium appears to have concentrations greatest in fish collected in Swan Creek for planktivores and pisci- vores, with bottom feeders having Similar concentrations throughout the study area. There was no difference in concentrations of strontium in.planktivores collected from the four lake stations. Moderate concentrations were found in.piscivores collected at stations FA and F5, while those collected at stations F2 and F3 had low concentrations in relation to the other stations. The lowest concentrations of strontium in bottom feeders were recorded on 3 April when a value of 2.75 ug/g was recorded. By June, strontium concentrations had increased slightly. On 8 August strontium concentrations had increased significantly to a mean level of 6.h2 ug/g and remained relatively unchanged until 7 November when the mean concentration had decreased.by about 1 ug/g from its summer high. Concentrations in December showed a slight decrease from November. Strontium concentrations in.planktivores and piscivores did not change Significantly during the sampling period. Amounts of strontium had increased Slightly in planktivores and piscivores by the middle of the 26 summer but had declined again.by September in piscivores and by November in planktivores. Zinc Average amounts of zinc in bottom feeders on each sampling date varied between 68.96 ug/g and 100.93 ug/g fresh weight, and all were higher than the amounts in the other feeding types. The annual average of zinc was significantly greater in bottom feeders than in planktivores and.piscivores. Statistical analysis showed no significant differences in spatial zinc concentration in all three feeding types. Planktivores collected from the lake stations had zinc concentrations that were less than those found in.planktivores collected from station Fl (Swan Creek). No trend could be seen for spatial zinc concentrations in bottom feeders or piscivores. Zinc concentrations in the three feeding types followed the same pattern observed for iron and manganese. Significant increases were detected in planktivores and piscivores from 3 April through 7 June. During this time zinc levels had decreased slightly in bottom feeders. 0n 6 August, significant increases were detected in all feeding types compared to 3 April concentrations. Samples collected on 1A September showed significant decreases in zinc in each feeding type. November and December samples showed little change in zinc concentrations from the September collection. 27 Distribution of Stable Elements in Fish An analysis was performed to determine the distribution of trace elements in various components of fish. Carp were chosen for this analysis because they consistently appeared in samples and because they are used for food when caught by commercial and sport fishermen. An analysis was accomplished by cutting the frozen fish in.half longitudinally on a band saw with a stainless steel blade. One half of the fish was processed in the same manner as whole fish samples were, as described in Tables 2 and 3. The other half of the fish was divided into four components: (1) flesh; (2) viscera; (3) Skin and scales; and (h) Slime. Table 8 gives the results of this analysis. Cesium was below limits of detectability for all components measured. Cobalt could only be detected in the whole fish. Highest concentra- tions of strontium were found associated with the skin and scales. Most of the zinc appeared to be associated with viscera, the skin, and scales. The results of this study are in agreement with those of Ting (1971) who worked with the distribution of Fe, Mn, Sr and Zn in fish. Mean stomach volume was determined for age IV carp, which was the most frequently captured age class along the western shore of Lake Erie at Monroe (Parkhurst, 1971). This was done in an attempt to establish the maximum influence of gut contents on analysis of whole fish without removing the gut contents (3 April and 7 June). 'The mean stomach volume for age IV carp was 20.25 ml. If the gut of an age IV carp was full of sediment when analyzed, the maximum amount of trace elements associated with the gut contents would be: Co, h88 ug; Fe, 676 ug; Mn, 1098 ug; Sr, 3090 ug; and Zn, 6159 ug (Anonymous, 1973). 28 Table 8. Distribution of stable elements in carp (ug/g). Body Parts CS Co Fe Mn Sr Zn 1 Whole Fishl < 0.03 < 0.2 33.50 < 0.06 11.89 126.12 2 Whole Fish < 0.03 0.h6 66.00 1.25 5.h9 11h.98 l Flesh < 0.03 0.39 11.13 < 0.06 < 0.15 h6.28 2 Flesh < 0.03 0.h8 2h.07 < 0.06 1.75 32.69 1 Visceral < 0.03 < 0.2 39.02 2.08 < 0.15 126.26 2 Visceral < 0.03 < 0.2 173.07 5.2h < 0.15 117.08 IX) 1 Skin and Scales < 0.03 < 0. 20.33 1.85 10.72 119.96 2 Skin and Scales < 0.03 < 0. ID 35.93 2.uu 9.25 78.77 I\) l Slime < 0.03 < 0. h20.hh lh.89 3.71 61.51 ID 2 Slime < 0.03 < 0. 387.05 17.63 5.59 33.92 1 Cut contents removed. 29 Average weight of an age IV carp from the Monroe area was 1108 g (Parkhurst, 1971). It is possible that bottom feeders collected during the first two sampling dates may have had sufficient amounts of trace elements in their guts to influence the stable analysis. Radioisotope.Analysis Radioecological monitoring of fish during the study period showed most radioisotopes of concern (l3uCS, 57Co, 5th and 65Zn) to be below the limits of detectability. Only 137Cs was present in high enough amounts to determine baseline concentrations in fish from the study area. The naturally occurring radioisotope of potassium, hOK,'was also measurable in fish. Over 23% of the total gamma activity in fish was 137CS activities found in the due to the presence of hoK. A list of three trophic levels of fish at each station throughout the study period is included in the appendix. The results of an analysis of variance (Table 9) revealed no significant difference, at the 0.05 confidence level, among trophic habits. The annual mean concentration of 13705 was 0.019, 0.021 and 0.038 pCi/g for planktivores, bottom feeders and piscivores, respec- tively. No significant differences were detected in spatial distribution 1 or seasonal variation (Figures 7, 8 and S9) of 3705 in any of the feeding groups studied. 30 137 Table 9. Analysis of variance to test differences in CS concentrations due to feeding habits. Source d.f. S.S. M.S. F F 0.95 Between feeding types 2 0.0013 0.0007 2.333 ns 3.68 Within feeding types 15 0. 00112 0. 0003 31 1 Figure 7. Concentrations (mean :1 standard error) of 37Cs in bottom feeders collected from the lake stations (F2-F5). 10 1N 1o Is .I 1 LA 11 r q Ila in F q 0 a. .0. 2 fl 2 u 1 2 n n 2 m H O V M H. .41 u m... I m C; 33 9on @203 33:0 < out: Time 32 Figure 8. Concentrations (mean : 1 standard error) of 137Cs in planktivores collected from the lake stations (F2-F5). q- r I. q A 1 Trrcrrl L L Trr.rri l L w, c 1 0 N. 0 J: 6 N J 2 2 I G 9 I 7 a 5 4 M 2 I 0 3 2 2 a 1 2 2 2 2 2 2 II ul II cl II cl cl II C? 33 9.0:. 9 53 3 _seo< cosMVP 33 1 Figure 9. Concentrations (mean :1 standard error) of 37Cs in piscivores collected from the lake stations (F2-F5). r j, 30 I 27 5 4 3 . 2 2 2 fl fl .0. W ts uozmrowxozon. >:>zo<. m ohms 7 ‘ I6 I4 d— IO DISCUSSION In general, concentrations of the trace elements in fish captured within the study area are typical of fresh water fish reported from other studies conducted around the world and exhibit no extreme characteristics. Trace element concentrations in fish have been reported by Bowen (1966), Chapman 23.2i: (1968), Copeland §t_§13 (1973), Lucas §t_§13 (1970), Mathis and Cummings (1971) and the Michigan Department of Natural Resources (1972). Table 10 compares the results of this study with those from other locations in the Great Lakes and other fresh water environments. Mean concentrations of cobalt, iron and zinc were slightly higher than values reported by COpeland gt 31. (1973) for Lake Michigan fish; however, iron and zinc values found in this study were within the range reported by Copeland gp_g1. (1973). cobalt levels reported in this study are slightly greater than levels reported in the literature. The mean for fish of all feeding habits was 0.6h ug/g in.this study, whereas the Michigan Department of Natural Resources found a mean of 0.1% ug/g for cobalt in fish throughout the state. Copeland gt E1. (1973) found a mean of 0.11 ug/g and a range of 0.02 - 0.AA ug/g in Lake Michigan fish. The higher concentrations of Co found in this study may be real and result from cobalt entering the study area from the Detroit River. Cobalt is used for making alloys, as a pigment in glass and china, and as a binder in the tungsten carbide tool industry 3h 35 o.ma mo.m m:.m -- immramv o.am o.oa o.m mm.se ca .1 -- 1- -- Am.mm-s.mv s.s 0.: .. mm.m um mm.o -- -1 .. Ao.sr:.av 6.: mm.o mo.o ma.a as -- om.» om.m .. Ammarm.mv 6.6: 6.0m o.m Hm.m: ea :H.o oa.o oa.o wmo.o Ass.-mo.v Ha.o no.6 no.0 :m.o oo -- -- u- -- Aso.-soo.v wmo.o No.6 -- soo.o no ”Namav endomo>fionsonoov Ansono>wsnoov Abboww Ammmww kmmmwv Amwmav Ambmav ssmwmmfiz mwofleeSWmewvmfimpmz “Mowm UGMMSWMU swwdwmu smeom umwwwmm .Apnmflms nos mxmsv Swap hopes emoam ow mo0fipmnpsooooo poosoao mocha .oa manna 36 (Sax, 1968). The apparent difference in cobalt levels may be the result of different analytical methods (atomic absorption and neutron activation), yielding the wide range of values reported by various investigators. Fish collected in Swan Creek usually had.higher concentrations of trace elements than fish collected from the lake stations. The distribution of the elements spatially within the study area appears to be divided into two distinct areas: (1) Swan Creek and (2) the lake stations. Swan Creek usually exhibits higher concentrations of trace elements in the water and sediments than the lake stations (Anonymous, 1973). This is probably caused.by surface runoff from the surrounding agricultural land. .Although fish movements have not been determined in the study area, it appears from the data collected during this study that most of the fish collected at Swan Creek have spent considerable time there, enough to accumulate greater amounts of trace elements than fish collected in.the lake. Some of the fish species collected in Swan Creek were not captured at any other station (Table A-l), so it was assumed that these species were either permanent residents of the creek or spent considerably more time in the creek than in the lake during the sample period. Spatial distribution in the lake appeared to follow the Swan Creek.plume to some extent. Station F2 fish often had.higher concen- trations than fish from other lake stations, although the difference in concentrations was seldom statistically significant. It is expected that fish in the lake are mobile and integrate the conditions found 'within the study area. 37 AS stated earlier, iron and manganese were found to be concentrated nearly 1000 times more in slime than in Whole fish. These two elements showed a greater tendency to be present in large amounts in fish captured in Swan Creek than in those collected from the lake. Because these metals are present in relatively high concentrations in the Slime, they may reflect spatial distribution.more quickly than.the other elements studied. These elements apparently'have to be ingested to result in significant bioaccumulation. Since most fish do not feed constantly, concentrations of Cs, Co, Sr, or Zn may not reflect as accurately as Fe and Mn.where a fish has been spatially. This would seem to apply especially to fish with great amounts of slime (carp, pike and goldfish). A.problem frequently encountered during the study was the inability to detect differences in trace metal concentrations between feeding types. The differences probably would.have been more readily detected had not all the species with similar feeding habits been.pooled together, and had a much larger sample of fish been obtained on each collecting date so that each species was well represented for statistical analysis. Some of the species collected were always found to have the same feeding habits. Random.stomach analyses of shiners showed that all sizes captured were consistently feeding on.plankton. Yellow perch were less consistent in their feeding habits. Young perch, age 0 - III, generally fed on plankton but older perch were found with both plankton and crayfish in their stomachs. Since only 3 perch stomachs were found to contain crayfish, all.perch were considered planktivores. This may have resulted in some perch that were primarily bottom feeders being grouped with the planktivores. Price (1963) concluded that Lake Erie yellow perch feed on any form of animal life available. 38 Fresh water drum.were another species that did not exhibit one specific feeding habit. Random stomach samples indicated that drum feed.primarily on.bottom materials, but often these fish were observed chasing minnows. This species has been reported to feed on crayfish, scuds, worms, and minnows in Iowa waters (Harlan and Speaker, 1956). Price (1963) found that drum in Lake Erie exhibit a general diet with respect to the food organisms available to them. Worms, leeches, zooplankton and fiSh were frequently found to be included in the drum's diet. It should be noted.that there does not appear to be a stepwise increase in concentrations of trace elements as one moves up the food chain. Fish which primarily fed on organisms that live on.the mud or mudawater interface had significantly higher concentrations of iron, manganese, strontium and zinc than piscivores. This same trend was observed by Mathis and Cummings (1971) for fish of the Middle Illinois River and Eyman (1972) in.a hyper-eutrophic lake in southern Michigan. A correlation analysis was performed to determine if either size or species composition could be related to trace element concentrations. The results of this analysis yielded R values that were rejected at the 0.05 confidence level. It was concluded that neither of these factors alone significantly influenced stable trace element concentra- tions. Since species were pooled with others of generally similar feeding habits, the error terms obtained are relatively large in some instances and may mask some differences that exist among species within feeding categories. 39 It is likely that specific differences do exist which cannot be identified through analyses based on.pooled samples. Specific differ- ences could have been identified only through intensive sampling of each species which was likely to be important in the study area at all times or during certain seasons. Since it could not be easily predicted.prior to sampling which of the species would be important and.because statistically adequate sampling of all the species present was not feasible at this early stage of the study, a pooled sample approach based on feeding categories became the elected option. From this study the important species were catalogued so that select species can now be identified for more intensive study. The fact that a significant difference (a z 0.05) appeared among the three feeding categories, using pooled samples in which great intraspecific and interspecific variability is incorporated, supports the rejection of the hypothesis that no difference exists among trophic categories. In future studies the trophic category most likely to indicate dangerous accumulations of radioisotopes in fish, the bottom feeders, can.be selected for more intensive study. SUMMARY Concentrations of the trace elements in fish captured within.the study area generally are similar to values reported for fresh water fish of the world and exhibit no unusual variation. Trophic differences were detected for concentrations of Fe, Mn, Sr and Zn. .All of which were most concentrated in bottom feeders. Significant seasonal fluctuations in concentration occurred in fish populations for each element studied except Cs. a) Co was present in highest concentrations in.April, then decreased throughout the remainder of the study. b) Fe concentrations were highest in June and August. c) Mn.and Zn concentrations increased through August and decreased significantly by September. d) Bottom feeders comprised the only feeding type that exhibited seasonal differences in Sr concentrations, which reached maximum levels in August and September. Fish collected from Swan Creek usually had.higher concentrations of trace elements than fiSh collected from the lake stations. The only radioisotope present in high enough concentrations to determine baseline concentrations in fish was 137Cs. At the intensity of sampling there was no measurable difference in 137Cs concentrations seasonally, spatially 0r trophically. ho CONCLUSIONS The effluent from Fermi 11 may contain radioisotopes produced either by fission or neutron activation. Bioaccumulation of the stable isotopes, which are the counterparts of these radioisotopes, has been reported by Chapman §£_§1, (1968). The increase in radio- isotope concentrations in fish, due to the plant's discharge into Lake Erie, will.probably be insignificant, even in the case of an accidental short-term high-radioisotope level release. Most of the radioisotopes entering aquatic environments become associated with the sediments within a short time (Brungs, 1967). Considering the relative amounts of water, sediments and fish in the study area, it is apparent that the amount of fish is insignifi- cant in comparison to the amounts of'water and sediments. A problem may arise if fish are attracted to the warm.water discharge in the colder months, thus increasing their exposure to any radioisotopes. Because large numbers of yellOW'perch spawn.in the study area, they may be particularly attracted to the discharge. hl LITERATURE CITED Anonymous. 1973. Ecological evaluation of the fate of radioisotopes from Fermi II nuclear power plant in western lake Erie. Early preoperational studies. Department of Fisheries and Wildlife and Institute of Water Research, Michigan State University, East Lansing. 70 p. Beeton, A. M. 1961. Environmental changes in lake Erie. Trans. Amer. Fish. Soc. 90: 153-159. Blincoe, C. 1962. Ashing procedures for determination of cesium in plant and animal tissues. Analytical Chemistry 311 (6): 715-716. Bowen, H. J. M. 1966. Trace elements in biochemistry. Academic Press, New York. 2111 p. Britt, N. W. 1955. Stratification in western Lake Erie in summer of 1953; effects on the Hexagenia (Ephemeroptera) population. Ecology 36: 239-2lI-1I. Brooks, A. A., A. Hume and B. J. Handley. 1970. RESAP -- A program for the least squares analysis of gamma spectra involving inter- mixed standard samples. Union Carbide Corp. , Nuclear Division, Oak Ridge, Tenn. Brungs, W. A. , Jr. 1967. Distribution of cobalt 60, zinc 65, strontium 85 and cesium 137 in a freshwater pond. U. S. Dept. Health, Educ. and Welfare, Public Health Serv. Publ. No. 999-RH-2lr. 52 p. Chapman, W., H. Fisher and M. Pratt. 1968. Concentration factors of chemical elements in edible aquatic organisms. UCRL-5056lt. Lawrence Radiation laboratory, Univ. of Calif. , Livermore, Calif. Copeland, R. A., R. H. Beethe and W. W. Prater. 1973. Trace element distributions in Lake Michigan fish: A baseline study with calculations of concentration factors and equilibrium radio- isotope distributions. Environ. Res. Group, Inc., Ann Arbor, Mich. Special Report No. l. 139 p. Elwell, W. T. and J. A. F. Gidley. 1967. Atomic-absorption spectro- photometry. Pergamon Press, London. 139 p. Eyman, L. Dean. 1972. Cesium-137 and stable cesium in a hypercutrophic lake. Ph.D. Thesis. Mich. State Univ. 98 p. 112 h3 FWPCA. 1968. Lake Erie environmental summary 1963-611. United States Dept. of the Interior. Great Lakes Region, Cleveland Program Office . 170 p. Harlan, J. R. and E. B. Speaker. 1956. Iowa fish and fishing. 3rd ed. State of Iowa. 377 p. Hartley, R. P., C. E. Herdendorf and M. Keller. 1966. Synoptic water sampling survey in the western basin of Lake Erie. Univ. Mich., Great Lakes Res. Div., Pub. 15: 301-322. Hartman, W. L. 1973. Effects of exploitation, environmental changes, and new species on the fish habits and resources of Lake Erie. U. S. Bureau of Sport Fisheries and Wildlife, Tech. Report No. 22. Langlois, T. H. 19511. The western end of lake Erie and its ecology. J. W. Edwards Pub1., Ann Arbor, Michigan. Lucas, H. F., D. N. Edington and P. J. Colby. 1970. Concentrations of trace elements in Great lakes fishes. J. of Fish. Res. Bd. of Canada 27: 677-68h. Martin, A. and R. L. Blanchard. 1969. The thermal volatilisation of cesium-137, polonium-210 and lead-210 from in vivo labled samples. Analyst 911 (6) : hid-14116 . Mathis, B. J. and T. F. Cummings. 1971. Distribution of selected metals in bottom sediments, water, clams, tubificid annelids and fishes of the Middle Illinois River. Univ. of 111., Water Res. Center, WRC Res. Report No. ’41. Meranger, J. C. and E. Somers. 1968. Determination of the heavy metal content of sea foods by atomic absorption spectrophotometry. Bull. of Environ. Contamination and Toxicology 3(6): 360-365. Michigan Department of Natural Resources. 1972. Heavy metals in surface waters, sediments and fish in Michigan. Michigan Water Resources Comm., Bureau of Water Mgmt. , Dept. of Nat. Res., State of Michigan. 58 p. National Academy of Sciences - National Research Council. 1960. The biological effects of atomic radiation. Summary Report, Report A/Ac. 82/GL-358. Nelson, D. J. 1969. Cesium-cesium-l37 and potassium concentrations in white crappie and other Clinch River fish, pp. 2110-2118. In: Symposium on Radioecology, D. J. Nelson and F. C. Evans (EdsT). AEC CON-670503. CFSTI, Springfield, Va. Parkhurst, B. R. 1971. The distribution and growth of the fish populations along the western Shore of Lake Eric at Monroe, Michigan during 1970. M.S. Thesis. Mich. State Univ. 71 p. AA Price, J. W. 1963. Food habits of some Lake Erie fishes. Bull. Ohio State Biological Surv. 11(1): 89 p. Sax, N. I. 1968. Dangerous properties of industrial materials. Reinhold Co., New York. 1251 p. Ting, R. Y. 1971. Distribution of Zn, Fe, Mn and Sr in marine fishes of different feeding habits, pp. 709-720. In: Third National Symposium on Radioecology, D. J. Nelson (EdTT. AEC cow-710501-132. Oak Ridge, Tenn. Verber, J. L. 1957. Bottom deposits of western Lake Erie. Ohio Div. Shore Erosion, Tech. Publ. No. A. A p. 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Mn Co Fe Zn Sr Cs Feeding Habit station ug/s us/s ug/g us/g ug/g ng/s Bottom Feeders 1 1.78:_ 1.85:. 39.60:, 88.u5:_ 2.87: 7.h:_ 0.10 0.18 h.03 h.h9 0.71 1.3 2 1.35: 1.25:_ no.93: 95.55: 2.99: 5.3: 0.23 0.18 3.75 5.03 0.85 1.8 3 1.h3: 1.11:. 39.31:, 96.29:_ 2.71:_ 7.7: 0.h2 0.08 13.28 5.66 0.26 2.3 1+ 1.92: 0.90: 72.60: 88.72: 3.1M: 7.0: 0.11 0.13 10.h5 15.u6 0.18 3.3 5 3.56:_ 0.56+ 22.39:_ 37.85:.v 2.15:. 5.9: 0.h5 0.25 2.06 3.26 0.63 1.h Planktivores 2 2.92: 1.30+ M77: 211.31: 2.13: 1+2: 0.h5 0.29 9.67 1.50 0.1M 1.6 3 2.01;: 0.75: 36.89: 30.91: 2.10: 5.3: 0.09 0.07 h.76 3.0% 0.h2 1.9 h 1.85: 0.90+ 19.8h:_ 36.h2:_ 2.4h:_ h.8: 0.h6 0.29 2.66 2.17 0.10 2.2 5 2.55: 1.h1+ 27.57: 23.07: 2.19:_ 3.2: 0.51 0.26 1.83 h.h9 0.1h 1.0 Piscivores 2 l.’+5: 1.55: 19.08: 18.61;: 2.15: 7.8: 0.65 0.8h 3.65 5.23 0.11 2.6 Table A-3 . 51 fish samples taken from-the study area on 7 June 1973. Mean concentrations (3:- +1 S.E.) of stable isotopes in whole Mn Co Fe Zn Sr Cs Feeding Habit Station us/s ug/g ug/g ug;/s us/g ns/g Bottom Feeders 1 3.h2:_ 0.97:_ 118.05:’ 52.08: 2.73:_ 8.0: 0.10 0.10 3.10 0.9h 0.28 3.2 2 2.87: 0.50: 11h.l+8: 71.02: 2.98: 7.2: 0.6h 0.08 6.17 .31 0.31 3.9 3 3.18:_ 0.29:, 99.10:, 67.55:, 3.97:, 9.7: 0.07 0.07 3.86 1.00 0.81 1.6 1+ 2.1m: 1.01;: 66.68: 66.55: 3.01: 6.2: 0.hh 0.07 n.32 5.28 0.38 3.2 5 2.98:_ 0.50: 138.37:_ 70.71:. 3.h1:. 8.h:_ 0.23 0.06 10.h7 1.28 0.16 1.8 Planktivores 2 3.13: 0.93:. 6h.16:. u2.2t: 2.15:, h.7_ 0.55 0.30 3.90 n.18 0.20 1.5 1+ 2.85: 0.97: 53.20: 36.66: 2.15: 11.11: 0.27 0.07 5.65 2.6h 0.30 0.8 5 1.76: 0.30: 115.90: 39.13: 2.11;: 5.1+: 0.18 0.03 2.1% 2.11 0.29 1.9 Piscivores 2 1.35: 0.50:. h2.79: 37.2h:_ 2.00: 6.8: 0.118 0.07 3.11 111:3 0.20 2.0 u 1.31:. 0.6u:_ h3.90:_ 32.u6:_ 2.16:_ 8.9: 0.23 0.27 3.70 3.h3 0.21 h.7 5 2.26:_ 1.21: 87.27:. 5h.32:. 2.18: 8.3: 0.21 0.16 9.h2 1.68 0.28 2.3 Table A-h. 52 Mean concentrations (1? +1 S.E.) of stable isotopes in whole fish samples taken from-the study area on 7 August 1973. Mn Co Fe Zn Sr Cs Feeding Habit Station us/s us/s us/s us/s us/s ns/g Bottom Feeders 1 2.79: 1.01+ 100.07:' 68.02: 7.h0:_ 9.3: 0.55 0.07 5.99 6.06 0.10 2.1 2 3.66:' 0.56:_ 108.97:. 100.93: 5.96: 8.0: 0.13 0.10 1.58 6.13 0 19 h.7 3 3.65: 0.33:: 127.03:. 100.31:' 6.25: 9.9: 0.0M 0.04 3.11 2.h0 0.19 h.3 1+ 2.76: 0.67: 97.00: 100.01: 5.20: 7.3: 0.25 0.1M 3.75 2.u0 0.28 2.0 5 h.53: 0.53: 175.61:. 100.19: 8.25:_ 9.7: 0.35 0.09 19.u8 10.h6 1.70 3.6 Planktivores 1 5.98: 0.78: 151.h0: hh.83: 5.85:_ 5.1: 0.99 0.21 9.62 .60 0.33 .0 2 2.h7: 0.99:_ 35.11:. F3.hn: 3.98:_ 1.9: 0.52 0.16 3.92 3.h8 0.67 1.1 3 2.62: 0.70: 3h.77: 39.38:, 3.33: 5-7: 0.07 0.10 1.21 .117 0.02 1.5 1+ 291+: 0.85: 311.33: 39.61: 3.71).: 5.3: 0.19 0.0% 3.33 3.h3 0.18 2.6 5 1.6h:_ 0.89: 36.52: 33.93: 1.66:_ 6.1: 0.13 0.16 6.03' 2.05 0.12 1.9 Piscivores 2 1.1%: 0.83: 57.83:_ 56.67:_ 3.71: 7.8: 0.20 0.02 2.h9 2.83 0.08 1.7 n-. 42“.. ' fl!” . “ — “If 241i RWY-Kl.“ “5E.— ‘a-‘nvi'. I L: - k < " HA}- pizmmamm$rm7r “fiftil’r'fi'élr‘f'f'c‘v'g‘iifii? r. .25.. ._ -. ~ . -—---— ' ' Table.A-5. 53 Mean concentrations (§ +1 S.E.) of stable isotopes in whole fish samples taken from—the study area on it September 1973. Mn Co Fe Zn Sr Cs Feeding Habit station ug/g ug/g ug/g ug/g ug/g ng/g Bottom Feeders 1 3.62:_ 0.69: 137.83: 76.37:_ 7.65: 9.1: 0.3% 0.01 6.29 5.15 0.51 h.0 2 1.62: 0.u7:_ h6.33:. 9u.0u:. 6.80: 9.7: 0.13 0.13 2.96 1.32 0.39 3.7 3 1.112: 0.36: 61+.50: 82.36: 6.39: 11A: 0.11 0.07 16.21 7.13 0.82 3.1 u 2.08: 0.h1: 52.10:_ 80.31:_ 6.7h:. 15.h:’ 0.18 0.03 0.h7 3.52 0.82 u.u 5 1.58: O.h7: 66.00:_ 82.51:. 5.h9:_ 11.9: 0.07 0.08 0.50 1.85 0.17 5.3 Planktivores 2 1.92:_ 0.70:_ M2.80: 16.22: 2.68:. 6.3: 0.18 0.18 2.93 1.30 0.h1 3.h 3 2.01:3 0.72: 51.00: 18.39: 1.79: 7.7: 0.u8 0.08 20.52 3.16 0.22 1.3 u 2.02: 0.63: 50.77: 16.01: 11.56: 9.2: 0.03 0.13 0.66 0.h2 0.15 u.8 Piscivores 2 0.6%: 0.75: 25-75: 19.1h:' 2'371. 8'4: 0.12 0.03 1.25 2.1h 0.06 3.0 Table.A-6. 5% Mean concentrations (i +1 S.E.) of stable isotopes in.whole fish samples taken fromfthe study area on 7 November 1973. Mn Co Fe Zn Sr Cs Feeding Habit Station ug/g us/g ug/g ug/g ug/g ng/g Bottom Feeders 1 1.16:’ 0.63:_ 6u.51:’ 8h.03: 5.28: 9.5: 0.u2 0.08 9.32 7.11 0.16 1.3 2 1.39: 0.31: 50.17: 79.37:_ 6.20: 5.7: 0.21 0.0h 1.03 2.87 1.18 1.1 1+ 3.27: 0.36: 1.733: 90.10: 1+.57: 7.3: 0.h5 0.07 6.02 6.01 0.23 2.2 Planktivores 2 1. 98: 0. 50: 37.13: 17.06: 1. 20: h . 9: 0.13 0.10 1.72 0.26 0.12 0.8 3 h.08:_ 0.u0:_ h8.01: 17.27:_ 1.26:. 7.1: 0.17 0.03 2.27 0.19 0.06 2.6 h 2.59:, 0.17: 52.u6: 17.84: 3.30:. 7.5: 0.32 0.05 7.85 1.60 0.10 3.0 5 2.22: 0.32:_ 36.13:. 16.h5:_ 2.11:. 5.h:_ 0.50 0.01; 1.71 1.17 0.28 1.6 Piscivores 1 h.75:. 0.37: 22.29: 33.h3:_ 6.26:_ 6.1: 0.72 0.11 0.h9 3.15 0.u9 2.3 3 0.88: 0.29: 1h.87: 13.03:_ 2.25:_ 7.7: 0.19 0.08 0.99 0.65 0.h7 3.1 u 0.56: 0.22: 17.83: 10.77:. 2.87:’ 7.5: 0.06 0.08 2.h7 0.09 0.22 2.8 Table A-7. 55 Mean concentrations (1? +1 S.E.) of stable isotopes in whole fish samples taken from—the study area on 8 December 1973. Mn ' Co Fe Zn Sr Cs Feeding Habit Station ug/g ug/g ug/g ug/g ug/g ng/g Bottom Feeders 1 2.149: 0.55: 62.118: 81+.32: 5.98: 8.3: 0.30 0.09 7.1M 4.83 1.01 2.7 2 1.97:_ 0.u0: 53.2h:_ 88.91:_ 5.hu:_ 7.0: 0.13 0.10 9.01 n.00 0.30 h.h 3 1.66: 0.21: 1+6.33: 76.93: 5.08+ 5.3: 0.19 0.03 8.90 n.52 0.16 1.3 5 1.71:_ 0.35:’ h5.29:’ 77.01:} h.81:_ 5.8: 0.32 0.05 6.35 1.77 0.22 1.0 Planktivores 1 2.18:_ 0.33: 38.h2:_ 2h.11: 3.72:_ 5.u: 0.09 0.01 7.11 _ 1.38 0.22 1.0 2 3.82: 0.38: h5.90: 15.23: 2.99: 5.9: 0.11 0.08 3.51 1.02 0.h0 1.2 3 2.69:_ 0.30: M3.1h:l 15.h6:_ 2.5u:_ 1.7: 0.70 0.01 5.76 0.98 0.31 0.9 h 2.u9+ 0.2h:. M9.91:, 15.88: 2.17+ h.1: 0.21" 0.09 8.u3 0.2M 0.07 1.5 5 1.81+ 0.20: 31.62: 13.69: 2.08: 6.3: 0.h2" 0.08 n.78 0.81 0.2a h.0 Piscivores 1 n.0u: 0.36:, 22.03:, 28.h1:_ 5.31:. 6.6_ 0.18 0.02 0.39 2.06 0.51 2.7 2 1.03: 0.18: 15.h0: 17.02: 2.h6:’ 5.1: 0.29 0.0% 0.78 0.98 0.13 1.7 h 0.75+ 0.22:_ 17.61: 10.9h:y 2 72__ 6.h: 0.17" 0.01 1.22 0.h0 0.15 2.5 56 Table A-8. Multiple range analysis of mean stable isotope concentra- tions in bottom feeding fish from the study area 3 April 1973.1 Co Station V IV III II I Mean 0.56 0.90 1.11 1.25 1.85 Cs Station II V IV I III Mean 5.3 5.9 7.0 7.h 7.7 Fe Station V III I II IV Mean 22.39 39.31 39.60 h0.39 72.60 Mn Station II III I V IV Mean 1.35 1.u3 1.78 1.92 3.56 Sr Station V III I II IV Mean 2.15 2.71 2.87 2.98 3.1h Zn Station V I IV II III Mean 37.85 88.h5 88.72 95.55 96.29- 1 Co, Fe, Mn, Sr, Zn in ug/g; Cs in ng/g. 57 Table A-9. Multiple range analysis of mean stable isotope concentra— tionslin.bottom feeding fish from the study area 7 June 1973- C0 Station III II V I IV Mean 0.29 0.50 0.50 0.97 1.0% CS Station IV II I V III Mean 6.2 7.2 8.0 8.h 9.7 Fe Station IV III II I V Mean 66.68 99.10 11h.h8 118.05 138.37 Mn Station IV II V III I Mean 2.h0 2.87 2.98 3.18 3.h2 Sr Station I II IV V III Mean 2.73 2.98 3.01 3.h1 3.97 Zn Station I IV III V II Mean 52.08 66.55 67.55 70.71 71.02 l . . Co, Fe, Mn, Sr, Zn in ug/g; CS in ng/g. 58 Table A-lO. Multiple range analysis of mean stable isotope concentra- tionslin'bottom feeding fish from the study area 7.August 1973- CO Station III V II IV I Mean 0.33 0.53 0.56 0.67 1.01 CS Station IV II I V III Mean 7.3 8.0 9.3 9.7 9.9 Fe Station IV I II III V Mean 97.00 100.07 108.97 127.03 175.61 Mn Station IV I III II V Mean 2:76 2.79 3.65 3.66 n.53 Sr Station IV II III I V Mean 5.20 5.96 6.25 7.h0 8.25 Zn . Station I IV V III II Mean 68.02 100.01 100.19 100.31 100.93 1 Co, Fe, Mn, Sr, Zn in ug/g; Cs in ng/g. 59 Table A-ll. Multiple range analysis of mean stable isotope concentra- tions in bottom feeding fish from the study area 1% September 1973.1 C0 Station III IV II V I Mean 0.36 0.1+1 0.117 0.117 0.69 Cs Station I II III V IV Mean 9.1 9.7 11.14 11.9 15.11 Fe Station II IV III V I Mean h6.33 52.10 6h.50 66.00 137.83 Mn Station III V II IV I Mean luh2 1.58 1.62 2.08 3.62 Sr Station V III IV II I Mean 5.119 6.39 6.711 6.80 7.65 Zn Station I IV III V II Mean 76.37 80.31 82. 36 82 .51 9h .01: 1 Co, Fe, Mn, Sr, Zn in ug/g; Cs in ng/g. 6O Table A-l2. Multiple range analysis of mean stable isotope concentra- tionslin.bottom feeding fish from the study area 7 November 1973. C0 Station III V I Mean 0.31 0.36 0.63 Cs Station II IV I Mean 507 7’3 9‘5 Fe Station IV II I Mean 117.33 50.17 6h .51 Mn Station IV II I Mean : _16 1.39 3.27 Sr Station IV I II Nban h.57 5.28 6.20 Zn Station II I IV Mean 79.37 8h .03 90.10 1 Co, Fe, Mn, Sr, Zn in ug/g; CS in ng/g. 61 Table A-13. Multiple range analysis of mean stable isotope concentra— tions in bottom feeding fish from the study area 8 December 1973.1 C0 Station III V II I Mean 0.21 0.35 0.2.0 0.55 Cs Station III V II I Mean 5.3 5:8 7.0 8.3 Fe Station V III II I Mean 115 .29 116. 33 53 .2h 62 .h8 Mn Station III V II I Mean 1.66 1.77 1.97 219 Sr Station V III II I Mean 11.81 5.08 5.1m 5.98 Zn Station III V I II Mean 76.93 77.01 8h.32 88:91 1 Co, Fe, Mn, Sr, Zn in ug/g; Cs in ng/g. 62 Table A-lh. Multiple range analysis of mean stable isotope concentra- tions in.planktivorous fish from the study area 3 April 1973- C0 Station III IV II V Mean 0.75 0.90 1.30 1.h1 CS Station V II IV III Mean 3.2 h.2 h.8 5.3 Fe Station IV V III II Mean 19.8h 27.57 36.89 uh.77 Mn Station IV III V II Mean 1.85 2.0M 2.55 2.92 Sr Station III II V IV Mean 2.09 2.13 2.19 2.hh Zn Station V II III IV Mean 23.07_ 2h.31 30.91 36.h2 1 Co, Fe, Mn, Sr, Zn in ug/g; Cs in ng/g. 63 Table A-15. Multiple range analysis of mean stable isotope concentra- tions in.planktivorous fish from the study area 6 June 1973. Co Station V IV II Mean 0.30 0.93 0.97 Cs Station IV II V Mean %.% %.7 5.% Fe Station V IV II Mean %5.90 53.20 6%.16 Mn Station V IV II Mean 1.76 2.85 3.13 Sr Station V IV II Mean 2.1% 2.15 2.15 Zn Station IV V II Mean 36.66 39.13 h2.2% 1 00, Fe, Mn, Sr, Zn in.ug/g; Cs in ng/g. Table A-16. Multiple range analysis of mean stable isotope concentra- tionslin.planktivorous fish from the study area 7.August 1973. C0 Station III I IV V II Mean 0.70 0.78 0.85, 0.89 0.99 CS Station II I IV III V Mean h.9 5.1 5.3 5.7 6.1 Fe Station IV III II V I Mean 3%.33 3h.7 35.1 36.5 151.% Mn Station V II III IV I Mean 1.6% 2.%7 2.62 2.9% 5.98 Sr Station V III IV II I Mean 1.66 3.33 3.8h 3.98 5.85 Zn Station V III IV II I Mean 33:93 39.38 39.61 M3.%% %%.83 1 Co, Fe, Mn, Sr, Zn in ug/g; Cs in ng/g. 65 Table A-l7. Multiple range analysis of mean stable isotope concentra- tionslin.planktivorous fish from the study area 1h September 1973. C0 Station IV II III Mean 0.63 0. 70 0.72 Cs Station II III IV Mean 6.3 7.7 9.2 Fe Station II IV III Mean %2 . 80 50. 77 5% .00 Mn Station II IV III Mean 1. 92 2.02 2.0% Sr Station III II IV Mean 1.79 2.68 h.56 Zn Station IV II III Mean 16.01 16.22 18.39 1 Co, Fe, Mn, Sr, Zn in.ug/g; Cs in ng/g. Table A-18. Multiple range analysis of mean stable isotope concentra- tionslin.p1anktivorous fish from the study area 11 November 1973. Co Station V III IV II Mean 0.32 0.%0 0.%7 0.50 Cs Station II V III IV Mean h.9 5.h 7.1 7.5 Fe Station V II III IV Mean 36.13 37 . 13 %8 . 01 52 .l+6 Mn Station II V IV III Mean 1.98 2.22 2.59 h.08 Sr Station II III V IV Mean 1.203 11261 2.h37 3.302 Zn Station V III II IV Mean 16.55 16.91 17.06 17.85 1 Co, Fe, Mn, Sr, Zn in ug/g; Cs in ng/g. 67 Table A-l9. Multiple range analysis of mean stable isotope concentra- tionslin,planktivorous fish from the study area 8 December 1973- C0 Station V IV III I II Mean .20 .2% .30 .33 .3% Cs Station IV III I II V Mean h.l h.7 5.h 5.9 6.3 Fe Station V I III II IV Mean 31.62 38.%2 %3.1% %5.90 19.91 Mn Station V I IV III II Mean 1.81 2.18 2.%9_7 2.69 3.82 Sr Station V IV III II I Mean 2.08 2.17 2.5h 2.99 3.72 Zn Station V II III IV I Mean 13.69 15 .23 15 .16 15 .88 2% . 11 1 Co, Fe, Mn, Sr, Zn in ug/g; Cs in ng/g. Table A-20. Multiple range analysis of mean stable isotope concentra- 68 l tions in piscivorous fish from the study area 7 June 1973. C0 Station II IV V Nban 0.50 0.6h 1.21 Cs Station II V IV Mean 6.8 8.3 8.9 Fe Station II IV V Mean h2.79 h3.90 87.27 Mn Station IV II V Mean 1.31 1.35 2.26 Sr Station II IV V Mean 2.00 2.16 2.18 Zn Station IV II V Mean 32.h6 37.2h 5h.32 1 Co, Fe, Mn, Sr, Zn in ug/g; Cs in ng/g. 69 Table A-2l. Multiple range analysis of mean stable isotope concentra- tionslin.piscivorous fish from the study area 7 November 1973. C0 Station IV III I Mean 0.22 0.29 0.37 Cs Station I IV III Mean 6.1 7.5 7.7 Fe Station III IV I Mean 1%. 87 17. 83 22.29 Mn Station IV III I Mean 0.56 0.88 %.75 Sr Station III IV I Mean 2.25_ 2.87 6.26 Zn Station IV III I Mean 10 :77 13.03 33.%3 1 Co, Fe, Mn, Sr, Zn in ug/g; Cs in.ng/g. 7O Table A-22. Multiple range analysis of mean stable isotope concentra- tionslin.piscivorous fish from the study area 8 December 1973- Co Station II IV I Mean 0.18 0.22 0.36 Cs Station II IV I Mean 5.1 6.% 6.7 Fe Station II IV I Mean 15 .%0 17.61 22.03 Mn Station IV II I Mean 0.75 1.03 h.0h Sr Station II IV I Mean 2.%6 2.72 5.31 Zn Station IV II I Mean 10 3% 17.02 28.%1 1 Co, Fe, Mn, Sr, Zn in ug/g; Cs in ng/g. 71 Table A-23. Multiple range analysis of mean stable isotope concentra- tions in.bottom feeding fish from 3 April 1973 through 8 December 1973.1 C0 2 Date 3 E F D C B A Concentration 0:31 0.32 O.h3 0.52 0.58 0.98 Cs Date F A E B C A Concentration 6.6 6.7 7.5 7.9 8.8 11.5 Fe Date A F E D B C Concentration %3.81 %8.29 5%.11 57.23 10%.66 127.15 Mn Date D F E A B C Concentration 1.68 1.80 1.92 2.07 2.86 3.65 Sr Date A B F E D C Concentration 2.75 3.3M 5.18 5.38 6.29 6.%2 Zn Date B A F E D C Concentration 68 96 79.60 80.95 8%.6h 8%.81 100.36 1 lake stations only. 2A F H II 3 Co, Fe, Mn, Sr, Zn in ug/g; Cs in ng/g. 3 April; B = 7 June; C = 7 August; D = 1h September; E = 7 November; 8 December. Table A-2h. Multiple range analysis of mean stable isotope concentra- tions in planktivorous fish from 3 April 1973 through 8 December 1973.1 C0 2 Date F E D B C A Concentration3 0.27 0.%2 0.68 0.73 0.86 1.09 Cs Date A B F C E D Concentration %.% %.8 5.3 5.% 6.2 7.7 Fe Date A C F E D B Concentration 32.27 35.16 %2.6% %3.28 %9.19 5%.%2 Mn Date D A C B F E Concentration 1.99 2.3% 2.h2 2.58 2.70 2.72 Sr Date E B A F D C Concentration 2.05 2.16 2.26 2.h5 3.01 3.18 Zn Date F D E A C B Concentration 15.06 16.87 17.06 28.68 39.09 39.3% 1 Lake stations only. 2A F II II 3 Co, Fe, Mn, Sr, Zn in.ng/g; Cs in ng/g. 3 April; B = 7 June; C = 7 August; D = 1h September; E = 7 November; 8 December. Table A-25. Multiple range analysis of mean.stable isotope concentra- tions in.piscivorous fish from 3 April 1973 through 8 December 1973.1 Co Date2 F E D B C A Concentration3 0.20 0.26 0.75, 0.78 0.83 1.55 Cs Date F E A C B D Concentration 5.8 7.6 7.8 7.8 8.0 8.h Fe Date E F A D C B Concentration 16.35 16.51 19.08 25,75 57.83 57.99 Mn Date D E F C A B Concentration 0.6% 0.72 0.89: 1.1% 1.%5 1.6% Sr Date A B D E F C Concentration 2.15 2.18 2.37 2.55 2.59 3.71 Zn Date E F A D B C Concentration 11.90 13.98 18.6% 19.1% %1.3% 56.67 1 Lake stat ions only . 2A F 3 April; B = 7 June; 0 = 7 August; D = 1h September; E e 7 November; 8 December. 3Co, Fe, Mn, Sr, Zn in ug/g; Cs in ng/g. 7h 80.0 + 08.0 80.0 H 80.0 02 80.0 H 08.0 000.0 H :80 000.0 H 08.0 m 80.0 H .80 80.0 H 08.0 80.0 H 80.0 80.0 H :80 80.0 H 80.0 80.0 H H80 in 80 80.0 H H80 000.0 H 18.0 000.0 H 80.0 02 80.0 H e80 m 80.0 H 08.0 80.0 H 08.0 08.0 H 08.0 80.0 H 08.0 80.0 H 80.0 80.0 H :80 0 000.0 H .680 oz 02 80.0 H 08.0 02 02 H afloeafiafla .80 oz 80.0 H >80 08.0 H 08.0 000.0 H 08.0 000.0 H 18.0 0 02 80.0 H 50.0 80.0 .... e80 80.0 H 80.0 80.0 H :80 80.0 H 1.8.0 .4 H80 H 08.0 0% 80.0 H 08.0 80.0 H 08.0 80.0 H 08.0 80.0 H 08.0 0 8m 80.0 H 08.0 000.0 H 08.0 80.0 H 08.0 80.0 H 80.0 80.0 H 18.0 m 80.0 H e80 H80 80.0 H 08.0 80.0 H 08.0 80.0 H 08.0 80.0 H H80 H 08008 goeeom 8888 0 808002 a nopaoeaom fl emanate 1. case a fines. m 8330 on? 888a .88 0803 an Amie HH m0 001.0 .8 A383 88030880 .004. 088. 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