n ^ GEOGRAPHIC DISTRIBUTION OF MERCURY IN ASIATIC CLAMS, CORBICULA FLUMENEA, •i FROM THE NORTH FORK HOLSTON RIVER, VIRGINIA
CHESAPEAKE BAY
U.S. Fish and Wildlife Service JANUARY 1993
AKO UUI GEOGRAPHIC DISTRIBUTION OF MBRCORY
IN ASIATIC CLAMS, CORBICPLA FLUMINEA.
FROM THE NORTH FORK HOLSTON RIVER, VIRGINIA
U.S. Fish and Wildlife Service Environmental Contaminants Division Virginia Field Office White Marsh, VA 23183
Prepared by: Louis D. Seivard David A. Stilwell Stephen O. Rice and Kenneth R. Seeley
Under the Supervision of:
Karen L. Mayne, Supervisor Virginia Field Office and
John P. Wolflin, Supervisor Chesapeake Bay Field Office
• 1993
flR300J50 TABLE OP CONTENTS
LIST OF TABLES ...... ii
LIST OF FIGURES ...... iii
ABSTRACT ...... iv
EXECUTIVE SUMMARY ...... v
INTRODUCTION ...... 1
MATERIALS AND METHODS ...... 5
RESULTS AND DISCUSSION ...... 7
CONCLUSIONS AND RECOMMENDATIONS ...... 9
LITERATURE CITED ...... 15
APPENDIX A LABORATORY QUALITY CONTROL INFORMATION AND ANALYTICAL METHODS .... A-l
AR300I5 LIST OF TABLES
PAGE Table 1. Historic and recent records of Federally listed species and candidate species in the North Fork Holston River, Virginia ...... 3
Table 2. Mercury concentrations in Asiatic clams, Corbicula fluminea, from the North Fork Holston River, Virginia, June 1990 ...... 10
Table 3. Summary statistics for methylmercury concentrations in Asiatic clams, Corbicula fluminea from the North Fork Holston River, June 1990...... 11
Table 4. Summary statistics for total mercury concentrations in Asiatic clams, Corbicula fluminea from the North Fork Holston River, June 1990...... 12
AR300152 LIST OF FIGURES
Figure 1. Sampling sites for Asiatic clams, Corbicula fluminea. North Fork Holston River, June 1990 ......
Figure 2. Total mercury and methylraercury concentrations in Asiatic clams, Corbicula fluminea from the North Fork Holston River ...... 13 Figure 3. Comparisons among sites for methylmercury concentrations in the Asiatic clam, Corbicula fluminea. from the North Fork Holston River, June 1990 ...... 14
Figure 4. Comparisons among sites for total mercury concentrations in the Asiatic clam, Corbicula fluminea from the North Fork Holston River, June 1990 ...... 14
^8300153 ABSTRACT
Title: Geographic distribution of mercury in Asiatic clams, Corbieula fluminea, from the North Fork Holston River, Virginia Abstract: A study was conducted quantifying mercury concentrations in the Asiatic clam, Corbicula fluminea, from the North Fork Holston River, Virginia. The purpose of this study was to determine the downstream extent of mercury contamination in aquatic biota caused by a former chlor-alkali processing plant that has been designated as a Superfund Site under the Comprehensive Environmental Response, Compensation and Liability Act (CERCLA). Results of this study would be useful in determining the limits of the riverine area that should be considered for assessment and remediation of this Superfund Site under the CERCLA process. c. fluminea were collected from one upstream (reference) site and eight sites downstream of the Superfund Site. Tissue samples from these clams were analyzed for total mercury and methylmercury. Results of these analyses show statistically significant elevations of mercury in clams from all downstream sites when compared to the upstream reference site, with the furthest site downstream being 75.2 miles below the Superfund site. Since remedial investigations conducted by the Olin Corporation have only extended 23 miles'; downstream of the Superfund Site, it is recommended that future Superfund activities define the full geographic extent of mercury contamination in the Holston River system.
Key words: Environmental Contamination, Mercury, Corbicula fluminea, Asiatic clam, North Fork Holston River, Virginia, Tenessee.
iv
AR3QOI5U EXECUTIVE SUMMARY
The North Fork Holston River is located in southwest Virginia and northeast Tennessee and comprises one of the headwater systems of the Tennessee River basin. Natural salt deposits located near the river at Saltville, Virginia have been used since the late 1800s for the production of soda ash (sodium carbonate). In 1950, production of chlorine gas and sodium hydroxide by the chlor-alkali process was begun on this site. Operation of this facility continued for 21 years. During this period an estimated 2,000 tons of salt and as much as 75 pounds of mercury were lost daily as waste. The mercury was either discharged directly to the river, or was deposited on plant grounds or in settling ponds. Although soils on the original plant site have been remediated, the settling ponds continue to discharge mercury into the North Fork Holston River to this day.
Mercury concentrations in fish downstream of the chlor-alkali plant exceeded the Food and Drug Administrations action level for human consumption, resulting in the 1970 enactment of a fishing ban in Virginia and Tennessee waters. In 1982, this site was included on the National Priorities List to be addressed under the Comprehensive Environmental Response, Compensation and Liability Act (CERCLA) of 1980. It is now identified as the Saltville Superfund Site. As part of the CERCLA process, a Sampling and Analytical Plan was submitted and approved by the U.S. Environmental Protection Agency (EPA}~ in 1989. This document limited the study area to a downstream limit of 30 miles below the Superfund Site. The U.S. Fish and Wildlife Service is concerned that this geographic limit does not adequately consider contaminant impacts to the lower portion of the river.
The purpose of this study was to:
1. To determine whether mercury contamination from the Saltville Superfund Site extends beyond the bounds of the 30 mile study reach by measuring mercury body burdens in the Asiatic clams, Corbieula fluminea. 2. To establish baseline data to compare future sampling and document trends in the river.
3. To determine if information exists to correlate Corbicula fluminea body burden data to deleterious physiological and reproductive effects in unionid mussel species.
Corbicula fluminea were collected at nine sites at approximately 10 mile intervals, from a reference site 1.7 miles upstream of the Superfund Site to a location 75.2 miles downstream near the Virginia/Tennessee state border, c. fluminea tissue was analyzed for both total mercury and methyImercury. statistically significant differences in mercury levels were observed between the upstream reference and all other sites. Concentrations of total mercury at the furthest downstream site, located 75.2 miles downstream of the Saltville Superfund Site, were over 8 times higher than levels at the reference site. Mean methyImercury concentrations at the furthest downstream site were 0.679 ppm dry weight, over 6 times control levels.
AR300I55 Results of this study demonstrate that elevated levels of total and methyIraercury are found in the North Fork Holston River biota at least 75.2 miles downstream of the Saltville Superfund Site. Thus, it is very likely that remedial investigations carried out by the Olin Corporation in the North Fork Holston River have not fully quantified the extent of mercury contamination there, as these studies were limited to a downstream distance from the site of only 23 miles. It is recommended that future CERCLA activities define the full geographic extent and levels of mercury contamination in the Holston River- system.
vo.
AR300I56 INTRODUCTION The North Fork Holston River is located in southwest Virginia and northeast Tennessee. In 1894, the Mathieson Alkali Works began production of soda ash utilizing naturally occurring salt deposits located in the Town of Saltville in Smyth County, Virginia. In 1950, the Mathieson Chemical Company facility began producing chlorine gas and sodium hydroxide by the electrolytic chlor- alkali process, which used a mercury cell as a cathode. Olin Corporation merged with Mathieson Chemical in 1954 and took over operation of the facility. The plant ceased operation in 1972 (U.S.E.P.A. 1987; Young-Morgan 1990). In the final 21 years of plant operation, about 2000 tons of salt and as much as 75 pounds of mercury were lost daily to the soils and settling ponds at the plant site, and the North Fork Holston River (Anonymous 1983; Powell 1983; Sheehan et al. 1989). This chronic contamination resulted in the extirpation of over 30 species of freshwater mussels, a ban on the consumption of fish from this river in both Virginia and Tennessee waters, and degradation of the sport fishery and aquatic ecosystem in the North Fork Holston River (Young- Morgan 1990). Growing concern over the environmental and public health effects of mercury •*" pollution in the mid-1960s led to a site investigation of the Olin Corporation facility. High levels of mercury in fish tissue and sediments in the North Fork Holston River were discovered. After this problem was discovered, Olin made process design modifications to their facility to reduce mercury discharges into the river to approximately 113 grams per day. In 1970, the Virginia State Water Control Board adopted a Total Dissolved Solids Standard of 500 (mg/1) which Olin was unable to meet. The Saltville plant was closed in 1972 partially as a result of this standard (U.S.E.P.A. 1987). In response to evidence that fish tissue mercury concentrations exceeded Food and Drug Administration (FDA) levels of acceptable human health risk, the Commonwealth of Virginia enacted a fishing ban in 1970 that encompassed the entire North Fork Holston River from the Olin discharge point to the Tennessee border. This was subsequently modified to a fish consumption ban. The state of Tennessee also enacted a fish consumption ban covering the 6.2 miles of the river from the Virginia state line to the confluence with the South Fork Holston River. Both bans remain in effect in 1992 (Denton 1990; VWCB 1990). In 1978, an interagency task force consisting of EFA, the Tennessee Valley Authority (TVA), and concerned agencies of Tennessee and Virginia was formed to define and address human health and environmental problems associated with contamination from the Olin facility. In 1982, the site was listed on the National Priorities List to be addressed under the Comprehensive Environmental Response, Compensation and Liability Act (CERCLA) of 1980 (EPA 1987). In 1983, under the direction of the interagency task force, Olin diverted a 1300 foot section of the river, removed contaminated sediments from 1000 feet of river bed, and sealed the river's bedrock. In addition, rip-rap was installed along river banks to prevent erosion of contaminated soil, and diversion ditches were constructed around the settling .lagoons to prevent
AR300I57 surface runoff from entering these contaminated areas areas during storm events.
On September 15, 1988, a consent agreement was signed between Olin Corporation and EPA that outlined plans for further problem identification and remedial activities to be implemented under CERCLA. As part of this agreement, a series of detailed documents were to be produced which would specify how the extent of the contamination would be defined, what risks and impacts to human health and the environment exist, and options for remediation of these impacts.
In October 1989, Olin Corporation submitted the Remedial Investigation/ Feasibility Study and accompanying Sampling and Analytical Plan. Despite extensive evidence that contamination from the site has migrated downstream to the entire length of the North Fork Holston River (Bailey 1974; Denton 1990), the sampling area addressed in this plan was given a downstream limit of 30 miles below the discharge. The Draft Risk Assessment document of July 1991 also was limited to this area (river mile 80.8 to river mile 53) and did not adequately consider effects to the lower portion of the river.
Study Area
, ! **? The North Fork Holston River headwaters originate from springs and creeks in * mountainous Bland County, Virginia. The drainage area includes 188,810 hectares of agricultural and forest land (Hill et al. 1980). Elevation ranges from 2,500 feet near the headwaters to 1200 feet near its confluence with the South Fork Holston River. The river begins as a shallow, cold, clear mountain stream and becomes a deeper, slower, cool-water river along its 112 mile route (Bailey 1974). The river bed is characterized by a gravel and rocky bottom with many pool and riffle areas (Hill et al. 1974). The average flow near Saltville for the previous 71 years of record is 299 cubic feet per second (cfs) (U.S. Geological Survey 1990). The flow in the river near its confluence with the South Fork Holston River is approximately three times this amount (Hill et al. 1974). The North Fork Holston River contains substantial sporting, recreational, and biological resources. A noteworthy smallmouth bass fishery exists in the river at this time (Ingram 1990), and the river is a popular location for canoeing, swimming, and boating.
Historical d*ta indicate that the North Fork Holston River provided habitat for a divers*, assemblage of endemic freshwater mussel species (Family Unionidae). Surveys completed in the early 1900s recorded 16 species at Saltville and 37 species downstream (Young-Morgan 1990). The Tennessee Valley Authority surveys, conducted between 1972 and 1975, found no species of mussels within 70 miles downstream of Saltville (Young-Morgan 1990). Records indicate that the river now or at one time supported six species of Federally endangered mussels and two species of Federally threatened fish. The system also provides habitat for seven species that are candidates for listing under the Federal Endangered Species Act. These include three mussels, two amphibians, the spiny riversnail and a fish (Table 1).
AR300I58 Table 1. Historic and recent records of Federally listed species and candidate species in the North Fork Holston River, Virginia.
Scientific NMm
Fish
Cvprinella monacha Spotfin Chub Threatened Noturug flavipjnnis Yellowfin Madtom Threatened Percina macrocephala Longhead Darter Candidate (C2) Snails
12 fluvialia Spiny Riversnail Candidate (Cl) Mussels
Bpioblaama torulosa Green-Blossom Pearly Endangered qubernaculum Mussel Fusconaia cor Shiny Pigtoe Endangered Fusconaia cuneolus Fine-Rayed Pigtoe Endangered Lemiox rimosus Birdwing Pearlymussel Endangered Peoias fabula Little-winged Endangered Pearlymussel Villosa trabalis Cumberland Bean Endangered Bpioblasma capaaeformia Oyster Mussel Candidate (C2) Lexincrtonia dolabelloides Slabside Pearlymussel Candidate (C2) Pleurobema oviforme Tennessee Clubahell Candidate (C2) Amphibians Aneides aeneus Green Salamander Candidate (C2) Crvptobranchus alleganiensis Hellbender Candidate (C2)
Source: Virginia Department of Conservation and Recreation, Division of Natural Heritage
AR300I59 Study Objectives
The objectives of this study were to: 1) determine the geographical '(downstream) extent of mercury contamination in Corbicula fluminea. 2) establish baseline data to compare with future sampling results and to document trends in the river, and 3) determine if information exists to correlate Corbicula fluroinea body burden data to deleterious physiological and reproductive effects in unionid species.
AR300I6Q MATERIALS AND METHODS Sampling Methods
Nine sampling sites in the North Fork Holston River were selected at approximately 10 mile intervals from a point 1.7 miles above the Saltville Superfund Site discharge point to a location near the Virginia/Tennessee state border at river mile 7.6 (with River Mile 0 being the confluence of the North Fork Holston River with the South Fork Holston River). The site above the Superfund Site, Site 1, was selected as a reference site. These sites are presented graphically in Figure 1.
Corbicula fluminea were collected at these nine sites during the period June 26-28, 1990 by visual observation with a diving mask or view box and hand picking. Approximately 350 clams were collected at each site to yield the required tissue sample sizes for chemical analysis. Organisms were placed on ice and returned to the Virginia Field office. Clam tissue was separated from shell material with a chemically cleaned stainless steel scalpel and placed into chemically cleaned glass containers. Three 15 gram aliquots of tissue were prepared for each site and frozen. Frozen samples were shipped to the analytical laboratory in dry ice.
Analysis Each composite sample of clam tissue was analyzed for total mercury and methyImercury. Percent moisture was determined, and wet weight values were calculated and reported for comparison to other published values. Chemical analysis was performed by Brooks Rand, LTD. Environmental Sciences Division, Seattle, Washington. Analytical techniques used by this facility are checked and approved by the U.S. Fish and Wildlife Service's Patuxent Analytical Control Facility, which is responsible for quality assurance/quality control for the U.S. Fish and Wildlife Service. Quality control analyses included triplicate analysis, analysis of National Bureau of Standards Tuna samples, blanks, and spike recoveries. Analytical methods and quality control data are presented in Appendix A.
Statistical Methods
Data were statistically examined using the Toxstat Version 3.0 software package developed by the Fish Physiology and Toxicology Laboratory, University Of Wyoming. Chi-square and Shapiro Wilke's tests were used to determine if data were distributed normally. Homogeneity of variance in the data was determined using Bartlett's and Hartley's tests. These test were performed because normality and homogeneity of variance in the data must be established prior to analysis of variance (ANOVA). Significant differences between the sample sites and between the upstream reference site and each downstream site were determined using one-way ANOVA and the Tukey method of multiple comparisons.
AR30QI61 Figure 1. Sampling sites for Asiatic clams, Corbieula fluminea. in the North^ Fork Holston River, June 1990.
AR300162 RESULTS AND DISCUSSION
Table 2 presents the results of the analysis of each site's Corbicula tissue samples for total mercury and methyImercury in both wet weight and dry weight. Summary statistics for methylmercury and total mercury at each site are presented in Tables 3 and 4, respectively. Site means for total mercury and methylmercury are graphically represented in Figure 2. comparison of the mean total mercury concentration (in dry weight) at the reference site (Site 1) to those at Site 2 immediately below the Saltville Superfund Site at river mile 79.9 showed a dramatic increase. Mean total mercury concentration increased by a factor of over 18 from 0.18 parts per million (ppm) at the site 1 to 3.341 ppm at Site 2. Total mercury concentrations continued to rise slightly and peaked at Site 3 (3.461 ppm). Concentrations declined sharply over the next two sites (river miles 60.2, 51.3) and then rose slightly at river mile 39.7 (Site 6). A gradual decline was observed over the next three sites. The total mercury concentration in clams at the downstream most site (river mile 7.6) remained over 8 times higher than the reference site concentration (1.465 ppm).
Methylmercury concentrations also showed an increase of nearly a factor of 1.0 from Site 1 (0.11 ppm) to Site 2 (0.974 ppm). However, the distribution "| pattern of methylmercury differed from total mercury. While methylmercury concentrations in clams also reached a maximum at Site 3 (river mile 69.9), , concentrations downstream remained elevated and showed less variation than was seen with total mercury. The decline in methylmercury concentration was more subtle and gradual, with Site 9 showing a concentration of 0.679 ppm, or 70% of the concentration at Site 3. Methylmercury concentrations at Site 9 (river mile 7.6) were over 6 times the reference site values.
ANOVA was performed to test the hypothesis that observed differences between sample sites were the direct result of their downstream distance from the Superfund site, as and not to random variability. ANOVA rejected the null hypothesis that mercury levels in clams at all sites were equal at the 0.05 probability level (this is essentially the level of probability at which one can be at least 95% certain that between-site differences are caused by distance from the Superfund site). This was true for both total mercury and methylmercury data sets. Relationships between individual sites were examined using the Tukey method of multiple comparisons. This test compared mercury levels at each site to that of every otlMr site in order to determine whether mercury concentration values are significantly different at the 0.05 probability level. Results of this test are presented graphically in Figures 3 and 4. All sites showed statistically significant differences from the reference site for both total mercury and methylmercury. Total mercury data for Sites 2 and 3 were significantly different from all other sites. These sites had the highest total mercury and methylmercury concentrations. Sites 7, 8, and 9 were not significantly different from each other, indicating that total mercury concentrations declined over the first 30 miles downstream and then remained essentially equal throughout the remainder of the study area.
aR300i63 Methylmercury concentrations below the discharge point remained elevated throughout the study area and showed few significant differences between sites. Sites 2 and 3 (river mile 79.9 and 69.9) were significantly different from Site 9 (river mile 7.6), but no other differences between any of the non- reference sites were significant. This indicates that methylmercury concentrations remain at elevated levels throughout the lower 62.3 miles of the study area. Use of c. fluroinea as a bioindicator organism has been suggested by several researchers. It is suited for this use because of its wide distribution, occurrence in large numbers, and ease of collection (Graney et al. 1983). Unfortunately, little information exists correlating Corbicula body burden data to levels of contaminants which would cause damage to aquatic communities or individual species (Neves 1987). Although considerable evidence exists describing past and present biological impairment to this river system, such as dramatic reductions in mussel populations and diversity, it is difficult to establish a cause and effect relationship between mercury levels and this impairment.
Other studies have reported mercury levels in C. fluminea with which values from this study can be compared. Total mercury (wet weight) in £. fluminea in the New River at Glen Lyn, Virginia was reported to be 0.01 ppm (Rodger et a£. 1977). These samples were collected upstream of a power plant discharge point in a river with no known mercury contamination. The mean wet weight value at Site 9 (0.148 ppm) in the North Fork Holston River is over 14 times larger than the reported New River value. C. fluminea collected from the relatively unpolluted Apalachicola River in Florida were reported to contain 0.03 ppm total mercury on a wet weight basis (Winger et al. 1984). Galindo et al. (1988) sampled c.. fluminea in a group of waterbodies in the Mexicali Valley, Baja California, Mexico. This region is contaminated with mercury from geothermal electric generation activities. Dry weight tissue concentrations ranged from 0.02 to 0.32 ppm dry weight. All reported values from these studies were below the mean concentration at the North Fork Holston River Site 9.
AR300I6U CONCLUSIONS AND RECOMMENDATIONS
Comparisons to both the upstream reference site and literature values describing other rivers indicate that both total mercury and methylmercury levels in th« Asiatic clam, Corbieula fluminea in the North Fork Holston River in Virginia are significantly above reference levels throughout the study area. The study area includes 75.2 miles of the river below the Saltville Superfund Site (located at river mile 82.8). Since elevated mercury levels were discovered throughout the entire range of this study area, additional sampling will be required to determine the full extent of contamination in the remaining 7.6 miles of the North Fork Holston River as well as in the mainstem Holston River in Tennessee.
Since the Olin Corporation has been identified as the party responsible for creating the Saltville Superfund Site, they are fully responsible for determining the extent of contamination caused by their site, as well as the impacts associated with this contamination. Environmental assessments conducted by the Olin Corporation in the North Fork Holston River have only focused on the impacts of mercury 23 miles downstream of their Saltville site. The data obtained in this study clearly indicate that mercury contamination in the river has extended well beyond this distance. It is incumbent on the Olin Corporation to fully define the extent of mercury contamination in both the -~i North Fork and mainstem Holston Rivers, and to adequately define the ecological impacts associated with this contamination. This responsibility includes expanding their ecological investigations to a point downstream in the Holston River system where mercury levels are no longer elevated above reference levels, and to demonstrate conclusively whether or not these elevated mercury levels represent a threat to the aquatic biota in the contaminated portion of the river system.
3R300I65 Table 2. Mercury concentrations in Asiatic clams, Corbicula fluminea, from the North Fork Holston River, Virginia, June 1990.
SITE RIVER MILE MBTHYLMERCURV* TOTAL MERCURY*
1 84.2' 0.110 ± 0.030 0.179 ± 0.016
2 79.9 0.973 t 0.073 3.341 ± 0.339
3 69.9 0.989 ± 0.026 3.461 ± 0.171
4 60.2 0.773 ± 0.102 2.654 ± 0.035
5 51.3 Or764 ± 0.106 1.793 ± 0.122
6 39.7 0.859 ± 0.859 2.383 ± 0.186
7 30.1 0.846 ± 0.121 1.937 ± 0.160 -
8 22.8 0.823 ± 0.090 1.885 ± 0.114
9 7.6 0.679 ± 0.023 1.465 ± 0.104
"Concentrations are given in parts per million, dry weight. Values shown represent the mean concentration for three samples ± standard deviation.
10
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O^B O ?m. m * fS» oO Uo foa w a™ •jHj fa a js -I 4J 4J H ^10 z0 01 a « "*"o> " N J3 _ U 4J , g SS MMCNOiffitNrir-Heoio * SO > |J •••>••••> co Q) 0) rj a HcNrnri-invor-ooa* 2 •B9> H CO 12 AR300I68 Figure 2. Total mercury and methylmercury concentrations in Corbieuia fluminea from the North Fork Holston R'iver. Bars represent the standard deviation of mercury contamination (n=3). 00 \ \ \ \ / f \ -J\, 'Ct- CO CN (}Lj6{8M Ajp mdd) uojiBJjuaouoo 13 HR3QOI69 Figure 3. Comparisons among sites for methylmercury concentrations in the Asiatic clam, Corbieula fluminea. from the North Fork Holston River, June 1990. SITES SITES RIVER MILE MEAN 19548 7623 1 Reference 0.110 \ 9 7.6 0.679 * \ 5 51.3 0.764 * • \ 4 60.2 0.773 * . . \ 8 22.8 0.823 * . . . \ 7 30.1 0.846 * ....\ 6 39.7 0.859 * . \ 2 79.9 0.974 * * • • \ 3 69.9 0.989 * * . . . . . \ * » significant difference (p=0.05) . = no significant difference Figure 4. Comparisons among sites for total mercury concentrations in the Asiatic clam, Corbicula fluminea. from the North Fork Holston River, June 1990. •• SITES SITE RIVER MILE MEAN 195876423 1 Reference 0.180 \ 9 7.6 1.465 * \ 5 51.3 1.793 * . \ 8 22.8 1.885 * . . \ 7 30.1 1.937 * . . . \ 6 39.7 2.383 * * * . . \ 4 60.2 2.654 * * * * * . \ 2 79.9 3.341 *******\ 3 69.9 3.461 *******.\ * 3 significant difference (p-0.05) . =* no significant difference 14 AR300I70 LITERATURE CITED Anonymous, 1983. Quicksilver cleanup. Tennessee Valley Authority-Impact. 6:5-7. Bailey, D.s. 1974. The occurrence of mercury in the fish and sediments of the North Fork of the Holston River. Virginia State Water Control Board. Basic Data Bulletin 41. Richmond, VA. Denton, G. 1990. The status of water quality in Tennessee, 1990 305(b) report. Tennessee Department of Health and Environment, Division of Water Pollution Control. Nashville, TN. Galindo, E.A., Munoz, G.F. and Flores, A.A. 1988. Mercury in freshwater fish and clams from the Cerro Prieto geothermal field of Baja California, Mexico. Bull. Environ. Contain. Toxicol. 41:201-207. Graney, R.L. Jr., Cherry, D.S. and Cairns, J. Jr. 1983. Heavy metal indicator potential of the Asiatic clam (Corbicula fluminea) in artificial stream systems. Hydrobiologia 102:81-88. Hill, D.M., Taylor, E.A., and Saylor, C.F. 1974. Status of faunal recovery^ in the North Fork Holston River, Tennessee and Virginia. Proceedings * 28th Annual Conference Southeast Association Game and Fish Commission. Hill, D.M., Taylor, E.A., and Saylor, C.F. 1980. Assessment of the status of fish and benthic macroinvertebrate communities in the North Fork Holston River. Division of Water Resources, Office of Natural Resources, Tennessee Valley Authority. Norris, TN. Ingram, B. 1990. It's time to return to the North Fork of the Holston. Virginia Wildlife, January, pp 8-11. Neves, R.J. 1987. Recent die-off of freshwater mussels in the United States: An overview. Proceedings of the Workshop on Die-Offs of Freshwater Mussels in the United States. Davenport, IA. Powell, G.V.N. 1983. Industrial effluent as a source of mercury contamination in terrestrial riparian vertebrates. Environ. Pollut. 5:51-57. Rodger, J.H. Jr., Cherry, D.S., Dickson, K.L. and Cairns, J. Jr. 1977. Invasion, population dynamics and elemental accumulation of Corbicula fluminea in the New River at Glen Lyn, Virginia. Proceedings, First International Corbicula Symposium. Texas Christian University. Fort Worth, TX. Sheehan, R.J., Neves, R.J., and Kitchel, H.E., 1989. Fate of freshwater mussels transplanted to formerly polluted reaches of the Clinch and North Fork Holston River, Virginia. J. Freshwater Ecology 5:139-149. 15 AR3QOI7I U.S.E.P.A. 1987. Record of decision, remedial alternative selection. Saltville Waste Disposal Site. Saltville, Virginia. Philadelphia, PA. U.S. Geological Survey. 1990. Water resources data-Virginia, Water Year 1990. Water-Data Report VA-90-1. Richmond, VA. Virginia Water Control'Board. 1990. Virginia water quality assessment, 305(b) report to EPA and Congress. Information Bulletin 579. Richmond, VA. Winger P.V., Sieckman, C., May, T.W. and Johnson, W.W. 1984. Residues of organochlorine insecticides, polychlorinated biphenyls, and heavy metals in biota from Apalachicola River, Florida, 1978. J. Assoc. off. Anal. Chem. 67:325-333. Young-Morgan and Associates, Inc. 1990. Assessment of mussel communities in the North Fork Holston River. Young-Morgan and Associates Inc. Abingdon, VA. 16 AR3QOI7? APPENDIX A Laboratory Quality Control Information and Analytical Methods A-l U. S. FISH AND WILDLIFE SERVICE PATUXENT ANALYTICAL CONTROL FACILITY QUALITY ASSURANCE REPORT HE: 6381 REGION: 5 REGIONAL ID: NR016-90-R5 THE ANALYSES CN THE ABOVE MENTIONED SAMPLES WERE PERFORMED AT: BROOKS RAND, IHD. ENvTRONMENTAL SCIENCES DIVISION 3950 SIXTH AVENUE NORTHWEST SEATTLE, WASHINGTON 98107 AFTER A THOROUGH REVIEW OF THE REPORT ISSUED BY THE LABORATORY, I REPORT THE FOLLOWING OBSERVATIONS AND CONCLUSIONS: THE ACCURACY, AS MEASURED BY SPIKE RECOVERY AND REFERENCE MATERIAL % ANALYSIS, WAS GENERALLY ACCEPTABLE. - 1 THE PRECISION, AS MEASURED BY REPLICATE SAMPLE ANALYSIS, APPEARS TO BE ACCEPTABLE. THE RESULTS LISTED IN THE REPORT ARE ON A WET WEIGHT BASIS. EVALUATION OF THE QUALITY OF THE METHYL MERCURY ANALYSES HAS BEEN EASED SOLELY ON THE INTERNAL QUALITY ASSURANCE PROGRAM OF THE REPORTING LABORATORY. WE HAVE CONDUCTED NO INDEPENDENT TESTS OF THEIR ABILITY TO PERFORM THIS ANALYSES. ( L~tT^ tf- }£-" ASSURANCE OFFICER DATE ANALYTICAL REPORT INTEGRITY FORM Catalog #: (o 3fr I Lab: "R 0 c O K £ . Region: >3 W ~ "K<\^c! VJ Initial QA/QC Review -- Report Correct '• DATE ' INITIALS ' PROBLEMS/ACTION - • \ ^-U-Ho ec $#fe c Tku; » AJL^ - &fc _, • . . •» \' • • ' f • • : • - _ '• • • «fl300)75. SAMPLE INTEGRITY REPORT . CATALOG f b'~(r} PURCHASE ORDER # T fi'5'fOO~6 -&$f£ LAS Original I of samples to be shipped c*O< ^—"/1 03, Actual # of samples received £* ' DATE: FROM: Arrival date: initial sample shipment ______final sample shipment * 3 Avc^u^ /f/%> ^cu^itj General sample condition Comments: ^y I^JAII ASPECTS CORRECT (i.e. purchase order matches' the catalog which /matches the samples received) Samples will now enter laboratory queue. /OR |~|PROBLEMS EXIST, the following is required • Action Item Comments , Amend Purchase Order Modify Catalog Resolve Sample Problem ' Please return this form to Patuxent Analytical Control Facility'Ys1 soon as Vn • information can be provided. • - CO OOOOrHOt-<^-IOOOOOOOOOOOOOOOOOOO (U 3 t< 1-o1 a 0) S CO f« -H >1 OT 0«) 0) 1—4 a cn •H ooooooooooooooooooooooooooo n} cn t-H £ z JJ o 0) cn 3 O oooooooebooooooooooooooooooo a z >i a fro o n n J 77 co S>n O U U I / / n_ i m (U ^u 4J ,-H to -wH O§. 0) CO 3 >, CO 1-1 I-H -CD «J O n} r-t „ C -H O • » 3 «H -HO •« EH -H rn n >1 r-l ts jj n. A at 4J -U 1X1 The asiatic clams were thawed in their sample bottles before homogenizing. Then, within a class 100 laminar flow hood fitted with a gold filter for gaseous Hg-removal, they were finely minced by hand, using an acid-rinsed stainless steel scalpel, according to established clean techniques. The cutting board and all tools were rinsed between samples with deionized water. For dry weights, a sample of approximately 5.0 g was accurately weighted into weigh boats and dried at 105 C until there was no change in weight. For total mercury, a sample of approximately 1.5 g was accurately weighed into acid-cleaned scintillation vials where it was digested with hot refluxing 70/30 v/v nitric sulfuric acidsf It was then diluted to volume with 1% bromine monochlor'ide iif deionized water. A 100 uL aliquot of this digestate was reduced^ by stannous chloride, purged onto gold and analyzed by cold vapor atomic fluorescence detection (CVAFS). For methylmercury, an approximately 1.0 g sample was weighed accurately into an acid-cleaned teflon vial and digested with 25% KOH in methanol. The samples were placed in a 70 C oven for an hour to dissolve the tissue. A 25 uL aliquot of the digestate was analyzed by aqueous phase ethylation and cold vappr atomic fluorescence detection. &R3QOI79