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PUBLIC HEALTH ASSESSMENT

TERRY CREEK DREDGE SPOIL AREAS/HERCULES OUTFALL SITE
BRUNSWICK, GLYNN COUNTY, GEORGIA


APPENDICES

APPENDIX A: FIGURES

The outer boundary is the Brunswick/Glynn County Community Based Environmental Protection Project (CBEP) boundary. The inner circle is the area around the Terry Creek Dredge Spoil Area,site number 5. The map is from the CBEP document catalog showing potentially hazardous waste sites
Figure 1. The outer boundary is the Brunswick/Glynn County Community Based Environmental Protection Project (CBEP) boundary. The inner circle is the area around the Terry Creek Dredge Spoil Area,site number 5. The map is from the CBEP document catalog showing potentially hazardous waste sites

Demographic Statistics
Figure 2. Demographic Statistics

Terry Creek Investigation Areas
Figure 3. Terry Creek Investigation Areas

Site Map
Figure 4. Site Map


APPENDIX B: ENVIRONMENTAL DATA

Table 1. TOXAPHENE IN SOIL
September 1995 - February 1996 Data

Location Depth Concentration (ppm) No. Of samples
    CLP Pesticide Analysis USEPA Toxaphene Task Force Analysis  
range average range average
Area 1: Main Dredge Spoil 0 to 6" 18-240 96 23-120 60 3
Approx. 4' BGS 100-430 297 3.2-330 178 3
Area 2: Near Riverside 0 to 6" 0.89-11 6.5 ND-6.3 4 3
Approx. 4' BGS 4.5-23 10.9 0.59-56 19.6 3
Area 3: Terry Creek Drive 0 to 6" 2.2-9.3
ND-0.49
5.8
0.19*
0.68-2.2
---
1.4
---
2
13†
Approx. 4' BGS ND-1.9 0.7* --- --- 3
* One-half the minimum quantitation limit was used to calculate the average for those samples with toxaphene below the detection limit.

† Composite samples rather than grab; soil was mixed from 3 close locations.

--- No Analysis ND = not detected BGS = Below Ground Surface

Data from the 7/12/96 Expanded Site Inspection.


Table 2. TOXAPHENE IN MUMMICHOG / KILLIFISH (Fundulus heteroclitus)
Terry Creek, Brunswick, GA

Range (ppm) Average (ppm) No. Of Samples Year* Reference
50.5 -80.7 62 5 1970-71 (Manning R. GA DNR, Personal communication, September 8, 1997)
Not reported 40 4 1970-71 (23)
Not reported 10 9 1971-72 (23)
3.4- 217 50 4
(4 duplicates)
Sept/Oct 1972 (23)
1.9- 27 JN 7 JN 11 Mar 1997 (25)
* Toxaphene concentrations in effluent from Hercules were highest in the early 1970s, prior to construction of a waste water treatment plant in 1972.

JN = A reasonable indication that organic constituents similar to some of those found in toxaphene are present in the sample, but the proof is insufficient to identify positively the compound as toxaphene.

ppm = parts per million


Table 3. TOXAPHENE IN EASTERN OYSTERS (Crassostrea Virginica)
Terry Creek, Brunswick, GA

Range (ppm ) Average (ppm) No. Of Samples Year* Reference
4.7- 54 13.4 16 1967-70 (24)
1.1- 5.6 2.63 14 Mar-June 1971 (30)
Not reported 6 18 1970-71 (23)
Not reported 1.8 14 1971-72 (23)
0.94- 1.8 1.3 8 Sept/Oct 1972 (23)
* Toxaphene concentrations in effluent from Hercules were highest in the early 1970s, prior to construction of a waste water treatment plant in 1972.

65 samples of oysters collected at St. Simons Island from 1967 through 1972 contained toxaphene ranging from 0.6 to 7.5 ppm (average 1.7 ppm), ref. (24).

ppm = parts per million


Table 4A. CONTAMINANTS IN FINFISH (mullet, sea trout, drum, etc)
Terry Creek site, Brunswick, GA, 1997

Contaminant Range of detected concentrations (ppm ) No. Of Composite Samples with detectable concentrations/total number of composites analyzed % of composites containing the contaminant
PCB 1268 0.04 - 0.18 27/38 71.1
Mercury 0.11 - 0.31 11/38 28.9
Arsenic 3.0 - 3.3 2/38 5.3
Toxaphene <0.1- <1.0* 36/38 95% or greater†
Toxaphene 1.6 JN - 3.9 JN 4/4 possibly 100%
*Method detection limits ranged from 0.1 to 1 ppm. The chromatograms did not have the characteristic peaks shown on Hercules standard toxaphene chromatogram for technical grade toxaphene (The state considers toxaphene to be present if the retention times and peak ratios in the latter half of the chromatogram match an analytical standard of toxaphene). Still, substances, also referred to as "clutter" were found in the fish samples that were not found elsewhere. These could be related to the toxaphene.

†A consultant interpreting this same data concluded that toxaphene was present below 1 ppm in most finfish samples.

JN =A reasonable indication that organic constituents similar to some of those found in toxaphene are present in the sample, but proof is insufficient to identify positively the compound as toxaphene.

ppm = parts per million


Table 4B. CONTAMINANTS IN SHELLFISH (shrimp and crab)
Terry Creek site, Brunswick, GA , April 1997

Contaminant Range of detected concentrations (ppm) No. of composite samples with detectable concentrations/total number of composites analyzed % of composites containing the contaminant
PCB 1268 not detected* 0/21 0
Mercury 0.11-0.27 4/21 19
Arsenic 3.0 - 5.2 13/21 61.9
Toxaphene not detected† 0/21 0
* at a method detection limit of 0.03 ppm

† at method detection limits of 0.1 and 0.2 ppm

ppm = parts per million


Table 5. TOXAPHENE IN OFF-SITE SEAFOOD
Spotted Seatrout

Location Tissue Type Total Toxaphene (ppb), [mean +SD]
    wet wt. Lipid wt.
Dubignons Creek* Ova 56+ 5.6 780+ 77
Purvis Creek† Liver 60+ 12 780+ 160
  Liver 39+ 16 520+ 210
  Liver 66+ 15 660+ 150
  Ova 46+ 0.22 1,040+ 5
  Ova 51+ 5.1 610+ 61
Skidaway River Ova <10 <700
*This report also contains data on Atlantic croaker, southern flounder, and red drum from Dubignons Creek.

†Whole grass shrimp and the whole body of striped mullet fingerlings from Purvis Creek were also analyzed and found to contain <10 ppb toxaphene on a wet weight basis.



APPENDIX C: PATHWAY TABLES

Table 6. POTENTIAL ENVIRONMENTAL PATHWAYS FOR EXPOSURE TO TOXAPHENE AT OR NEAR THE TERRY CREEK DREDGE SPOIL AREAS/HERCULES OUTFALL SITE

Pathway Name Point of Exposure Route of Exposure Exposed Population Estimated Exposed Population
Air Near the Terry Creek site Inhalation Nearby residents <5,000
Sediment Terry or Dupree Creeks and their associated wetlands Ingestion Creek users: people fishing or using creeks for recreation. <1,000
Soil Nearby residential areas Ingestion Small children ingesting dirt or people working in the soil such as gardeners. <100
Produce from gardens Terry Creek Mobile Home Park or near Riverside Development Ingestion Gardeners and others eating produce grown in contaminated areas. <10
Surface water Terry or Dupree Creeks Absorption through skin contact Historically, swimmers or others who recreationally used the creeks <1,000
Groundwater Shallow private well use, if any Ingestion Terry Creek Road residents using the community well <30


Table 7. COMPLETED ENVIRONMENTAL PATHWAY FOR EXPOSURE TO TOXAPHENE AT THE TERRY CREEK DREDGE SPOIL AREAS/HERCULES OUTFALL SITE

Pathway Name

Point of Exposure

Route of Exposure

Exposed Population

Estimated Exposed Population

Seafood

Terry/Dupree Creeks

Ingestion

People eating contaminated fish from Terry/ Dupree Creek Area.

<10,000



APPENDIX D: ANALYTICAL PROBLEMS AND REQUEST FOR TECHNICAL ASSISTANCE

April 1997 Seafood Data- example of analytical uncertainties

In April 1997 the GA EPD collected 59 composites of seafood (38 finfish such as mullet, sea trout, drum and 21 shellfish, crab and shrimp) from four areas in Terry/Dupree Creeks which were analyzed for metals, mercury, PCBs, and toxaphene28. The GA EPD qualitatively described the toxaphene concentrations as below various detection limits such as 1.0, 0.5, or 0.2 ppm, depending on the cleanliness of the toxaphene component peaks on the complex chromatograms. The chromatograms for fish samples were sorted into three groups according to the crowding of toxaphene component peaks: (1) excessive clutter, (2) clutter, and (3) relatively clean.

The profile of toxaphene components in the April 1997 seafood chromatograms differed from the Hercules reference standard as well as reference standards of toxaphene from commercial sources28. The chromatograms of toxaphene from foodfish did not have the characteristic pattern of peaks shown on the Hercules standard toxaphene chromatogram for technical grade toxaphene. State officials indicate a match for toxaphene if the retention times and peak ratios in the latter half of the chromatogram match an analytical standard of toxaphene. They concluded that toxaphene was not detected. Nonetheless, there were substances, also referred to as "clutter" in the fish samples, that are not found elsewhere and could be related to (i.e., have same retention times as) the toxaphene components. No specific compounds were confirmed (identifiable) from these analyses. The method detection limits (MDL) for toxaphene varied from 0.1 to 1 ppm in finfish samples because of interferences from this clutter (Table 4A). The clutter was not seen in the crab samples and the GA EPD concluded that the crabs were "clean."

Approximately 70% of the fish composites in the April 1997 data set contained PCB (Aroclor 1268) in low concentrations (0.04 to 0.18 ppm ) 28. PCBs were not detected in shellfish (crabs and shrimps); and oysters were not sampled. Approximately 30% of the fish samples contained mercury ranging from 0.11 to 0.31 ppm. Arsenic in shellfish was about 3 to 5 ppm (Table 4B). The state has requested some speciation of the arsenic to determine whether a toxic form is present.

In February 1998, ATSDR requested expert assistance in estimating the total toxaphene concentrations in recent seafood samples (April 1997 data). In addition to the complex composition of technical grade toxaphene, the toxaphene compositions in fish differ from the reference standards. There is also a wide range in the relative portions of gas chromatographic peaks among various toxaphene reference standards. The method used to calculate total toxaphene from chromatograms also affects the estimated concentrations. A sample of toxaphene standard (methanol solution) from Ultra Scientific at a prepared concentration of 5.00 ppm was accurately estimated as 5.19 ppm, based on total areas of all component peaks in the chromatogram32. But the estimated concentration was as low as 1.42 ppm, based on combined areas of seven component peaks in latter half of the chromatogram 32. The choice of the these peaks was subjective. Additionally, the resolution of the toxaphene components in the 1997 methods was incomplete, and the interference of other organohalogens cannot be completely eliminated using electron capture detection. These uncertainties make the estimation of total toxaphene level in fish difficult. The help of experts working in this field was therefore requested in order to make an estimation of the toxaphene concentrations based on the available data set from April 1997. This request and ATSDR's concerns are elaborated in this appendix. ATSDR will continue to evaluate toxaphene monitoring data as it becomes available and, hopefully, analyzed with more advanced methodology. USEPA is currently conducting toxaphene research in environmental samples.

Toxaphene Analytical Methods

The concentrations reported in this health assessment were calculated or estimated using various methods and modifications thereof. The method for the 1995 through 1997 data sets, analyzed by the state, was Gas Chromatography with Electron Capture Detection (GC-ECD). The toxaphene analytical methodology, as determined by the USEPA Toxaphene Task Force, was the USEPA SW-846 Method 8080, with some modifications. This method is basically gas chromatography. Toxaphene is quantitated using 4 to 6 major peaks on the "back-half" of the chromatogram and by measuring peak height45. As of 1998, the majority of the data have not been confirmed with GC/MS (Gas Chromatography/Mass Spectrometry) technology. New refinements in methods for estimating the concentration of total toxaphene and major components remain to be undertaken.

The 1993 International Toxaphene Workshop recommended that total chlorobornanes (polychlorinated camphene) be reported using existing methods such as electron capture negative ion mass spectrometry (GC-ECNIMS) as well as individual congeners (components)46. GC-ECD was judged suitable for quantitation of PCC in biologic materials with well-defined peaks at high concentrations. Yet the value of this method is limited because the sensitivity is much less than that of ECNIMS.

Request for assistance

Note: This request was sent to Dr. M.A. Saleh at Texas Southern University, Houston, Texas.

Subject: Toxaphene level in fish: GC-ECD data review

Purpose: The health assessors working on the Terry Creek Dredge Spoil Areas/ Hercules Outfall site in Brunswick, Georgia ask for expert help to review gas chromatographic data of total toxaphene levels in fish samples. ATSDR needs estimates of toxaphene concentrations in fish in order to determine if we should recommend actions to reduce exposure through seafood consumption.

Background: Hercules, Inc. produced toxaphene, a chlorinated-hydrocarbon pesticide, as its principal product from 1948 through December 1980. Hercules released large volumes of waste water containing toxaphene (reportedly approximately 200-300 pounds of toxaphene per day) from a waste water discharge point at the confluence of Dupree and Terry Creeks until 1972.

USEPA and the Georgia Environmental Protection Division (GA EPD) collected seafood samples from Terry and Dupree Creeks in February and March 1997. They analyzed the samples with gas chromatography using an electron capture detector (ECD). There was some indication that organic constituents similar to those found in toxaphene were detected in fish (they used a JN qualifier: J meaning an estimate and N meaning presumptive indication of the presence of toxaphene but no proof).

In April 1997, the GA EPD collected composites of seafood in Terry/Dupree Creeks. They analyzed for metals, mercury, PCBs, and toxaphene. The seafood chromatograms did not have the characteristic peaks that are shown on Hercules standard toxaphene chromatogram for technical grade toxaphene (the State is calling a match for toxaphene if the retention times and peak ratios in the latter half of the chromatogram match an analytical standard of toxaphene). GA EPD qualitatively described the concentrations as under 1.0 ppm or other detection limits. Basically, they considered the toxaphene concentrations undetectable.

Besides the complex composition of technical grade toxaphene, the toxaphene compositions in fish differ from that of reference standards. Additionally the resolution of the toxaphene components in the chromatograms was incomplete and the interference of other pesticides cannot be eliminated completely using electron capture detection. These uncertainties make the determination of the toxaphene level in fish difficult. Therefore, we need the help of experts working in this field to make a best estimation of the toxaphene concentrations based on the most recent data set of April 1997. The data set contains chromatograms of seafood samples with retention times and area counts for major peaks as well as a reference standard for toxaphene.

The task will determine :

1. Define toxaphene in fish. What are the acceptable ways to estimate toxaphene concentrations in fish? Should the peaks in the sample be in the same proportion or ratios as Hercules reference standard to be counted as toxaphene? Did environmental degradation and partitioning such as selective uptake and retention by fish shift the profile to earlier eluting components of toxaphene (Should the reference standard be the technical grade toxaphene or another standard?). Should the total area of a section of the chromatogram be used, or the area under several representative peaks (if so, which ones?), or both?

2. Determine whether the toxaphene concentrations in the April 1997 data set of seafood samples are high enough to be estimated. If so, what are the best estimates of total toxaphene concentration in these samples?

3. Suggest a definitive method for determining the toxaphene concentrations in seafood caught near the Hercules plant and reducing uncertainty (for example, specify the chlorobornanes in the chromatograms, etc.).


APPENDIX E: TECHNICAL ASSISTANCE REPORT ON TOXAPHENE LEVELS IN FISH

Terry Creek Dredge Spoil Areas/Hercules Outfall Site
Toxaphene Levels in Fish: GC-ECD Data Review

Introduction

The Georgia Environmental Protection Division (GAEPD) collected fish samples in April 1997 from creeks near the Terry Creek Dredge Spoil Areas/Hercules Outfall site. GAEPD estimated total toxaphene levels using gas chromatographic-electron capture detector (GC-ECD) methods. The Agency for Toxic Substances and Disease Registry requested that their contractor Eastern Research Group, Inc. (ERG) provide technical support in evaluating and interpreting the results of this effort.

Mahmoud Saleh, Ph.D., under a consulting agreement to ERG, reviewed, evaluated, and provided his interpretation of the GC-ECD data. Dr. Saleh provided the following information, which is detailed in this report:

  • Background on toxaphene and its prevalence in the environment

  • Results of the GC-ECD data review

  • Recommended methods for estimating toxaphene concentrations in fish

Background

Toxaphene's chemistry is well developed. Toxaphene is a complex mixture of chlorinated bornane, bornenes, and related terpenes. More than 200 isomers of toxaphene have been detected. Of those, 20 have been isolated and identified, and the molecular weights and molecular formulas of the remaining major components are known. Toxaphene samples manufactured by Hercules, Inc., from 1949 to 1975 were extremely similar in GC-ECD but significantly different from other samples maufactured in the United States and abroad (Saleh, 1991).

Although most uses of toxaphene were banned in 1982, toxaphene residues have been documented recently throughout the biosphere, as well as in human milk. Toxaphene's global persistence contradicts previous beliefs that toxaphene biodegrades easily. From 1982 to 1984, toxaphene was reported to be among the most frequently occurring residues in total dietary foods. Toxaphene was also found 48 times based on two food consumption surveys, and at a frequency level higher than dichlorodiphenyltrichloroethane (DDT), dichlorophenoxyacetic acid (DCPA), pentachloroaniline, and methoxychlor (Gunderson, 1988).

Toxaphene is relatively persistent in aquatic environments (e.g., sediments) where it is used. In some Canadian lakes, for example, toxaphene was found in toxic concentrations up to 5 years after toxaphene applications were used for fish control. Lockhart et al. (1992) showed that the organochlorine at highest concentration in Arctic freshwater is alpha-hexachlorocyclohexane (HCH), while toxaphene, polychlorinated biphenyls (PCBs), and chlordane are generally at highest concentrations in the fish. In a study by Newsome and Andrews (1993), toxaphene was the most abundant organochlorine pesticide in trout.

The biomagnification of the DDT and its metabolites, PCBs, and toxaphene was investigated in the epibenthic Mysis relicta (mysid), the benthic Pontoporeia hoyi (amphipod), plankton, particulate flux, surficial sediments, and Myxocephalus thompsoni (deepwater sculpin) in southeastern Lake Michigan. DDT was the most strongly biomagnified compound, increasing 28.7 times in average concentration from plankton to fish. PCBs increased 12.9 times in average concentration from plankton to fish, while the concentration of toxaphene increased by an average factor of 4.7. Particle flux was composed of lower chlorinated PCB homologues (average chlorine number = 3.8) than were the biota (4.5-5.0) and the sediments (4.6), possibly reflecting strong influences from atmospheric deposition and/or zooplankton digestion. The percent of higher chlorinated PCB homologues (5 and 6 chlorine atoms per PCB molecule) increased from 54 to 56% of the total PCBs in plankton and M. relicta and to 61 and 74% in P. hoyi and M. thompsoni, respectively. P. hoyi contained higher concentrations of DDT residues, PCBs, and toxaphene than did M. relicta, possibly reflecting differences in habitat (benthic versus epibenthic) and diet (detritus versus plankton) (Evans et al., 1991).

Based on estimates of average area biomass and contaminant concentrations, offshore Lake Michigan P. hoyi populations contain approximately 9.5 times as much total DDT, 12 times as much PCB, and 15 times as much toxaphene as do the offshore M. relicta populations. Thus, P. hoyi may represent a greater reservoir for contaminant storage and subsequent recylcing in offshore Lake Michigan than do M. relicta. Vetter et al. (1983) studied organochlorine levels (PCBs, DDT and its metabolites, lindane and its isomers, hexachlorobenzene (HCB), chlordane, and toxaphene) in the blubber of Northern Hemisphere marine mammals. They detected differences in the levels as well as the ratios of organochlorine compounds in different species of marine mammals living in the same region. For example, the blubber of harbor seals (Phoca vitulina) accumulated significantly lower levels of lindane, HCB, toxaphene, and DDT and its metabolites than did the blubber of harbor porpoises (Phocoena phocoena). Compared to such elementary differences in the organochlorine patterns, the influences of age and sex on the results was minimal.

Researchers used migration to explain the varying ratios of contaminants in harbor porpoises. The sedentary harbor seals showed constant PCB/DDT ratios. In fact, the harbor seals' sedentariness allowed researchers to identify even local sources of contaminants. Careful evaluation of the organochlorine levels and ratios in marine mammals made it possible to monitor the transport of PCBs from the European continent to the European Arctic regions.

Results of the GC-ECD Data Review

The GAEPD examined and evaluated 250 gas chromatograms, representing 57 fish samples for total toxaphene levels using EPA Method 8080 and florisil cleanup EPA Method 3620. A review of the analytical data revealed that methods were impletemented accurately and that acceptable recovery and QA/QC citeria, as specified in EPA Methods 8080 and 3620, were applied.

The method used, however, relies only on GC-ECD retention times to identify the toxaphene congeners. This approach may present problems associated with interferences from PCBs and other chlorinated pesticides. This method is designed to identify toxaphene peaks in standard Hercules toxaphene reference samples. Toxaphene, however, is known to be slightly dechlorinated as a result of environmental degradation and biomagnification, which alters the shape of the gas chromatogram and, when relying only on retention times, makes interpreting toxaphene residue more difficult.

In reviewing and interpreting the chromatograms, Dr. Saleh relied upon the appearance of selected peaks as pattern recognition for confirming the presence of toxaphene and/or its metabolites and degradation products in the samples. Eleven peaks were selected based on the Hercules toxaphene GC pattern shown in Saleh and Casida (1977). These peaks are shown in the first panel of Figure 1. These peaks are common in all Hercules toxaphene samples as well as in degraded or metabolized toxaphene (Saleh and Casida, 1978). Relative toxaphene concentrations may be estimated by summing these peaks.

Conclusions

Based on the concentrations reported in the 1997 report, all samples can be classified into one of the five following groups:

Group Toxaphene Concentration (parts per million [ppm])
1 Less than 0.1
2 0.1 to 0.2
3 0.2 to 0.3
4 0.3 to 0.5
5 0.5 to 1.0

Tables 1 though 5 present the toxaphene concentrations in fish samples collected in creeks near the Terry Creek Dredge Spoil Areas/Hercules Outfall site. Footnotes indicate those cases in which reported concentrations differ from concentrations estimated by Dr. Saleh in this data evaluation.

Based on the chromatograms reviewed, the toxaphene values reported in the 1997 data set were acceptable overall. In a few cases, however, review of the chromatogram peaks revealed higher toxaphene levels than the reported values. Specifically, samples AB68802, AB68814, AB68815, and AB68817 (see Table 1) can be estimated to contain 0.1 to 0.2 ppm. Sample AB70210 (see Table 2) may contain 0.2 to 0.3 ppm, and sample AB70211 (se Table 2) should be reported at 0.3 to 0.5 ppm. In contrast, sample AB68803 (see Table 5), which was reported to contain about 1 ppm of toxaphene, can be estimated to contain only 0.1 ppm or less.

Recommended Methods for Estimating Toxaphene Concentrations in Fish

The following list presents the strengths and weaknesses of available methodologies for quantifying toxaphene levels in fish.

  1. Estimating toxaphene levels in fish based on GC-ECD methods and using retention times as the only criteria for identifying toxaphene components is not the most accurate and conclusive method. Other methods, specifically those with confirmation techniques, are recommended alternatives. GC/MS-SIM (m/e 159) (gas chromatography/mass spectrography-single ion monitoring) (Saleh, 1987) and GC-NCI-SIM (gas chromatography-negative chemical ionization-single ion monitoring) have been shown to be highly reliable and highly sensitive in detecting toxaphene and its degradation and metabolite products.

  2. If GC-ECD is the only technique available to measure toxaphene, reasonable accuracy can be obtained by (a) adjusting the sample size so that major toxaphene peaks are 10 to 30% of full-scale deflection (FSD), (b) injecting a toxaphene standard that is estimated to be +10 ng of the sample, (c) constructing the baseline of standard toxaphene between its extremities, and (d) constructing the baseline under the sample using the distances of the peak troughs to baseline on the standard as a guide. This procedure is complicated by the fact that the relative heights and widths of the peaks of the sample will probably not be identical to those of the standard. A toxaphene standard that has been passed through a florisil column will show shorter retention times for some peaks and enlargements for others.

  3. When qualified by GC-ECD and GC-NCI-SIM, commercially available standards of toxaphene show different detector responses, depending primarily on the percentage of chlorine in the mixtures. To obtain accurate results, toxaphene residues in environmental samples should be quantified using a standard with a similar or nearly similar detector response. If this is not possible, any standard may be used, but the results of the samples must be corrected afterwards. When different integration methods are compared, the best results appear when as many single-peak areas are integrated as possible. Quantification by integrating the bulge formed by raising the baseline, which can be observed in many gas chromatograms of toxaphene standards, should be avoided because this bulge results from the degradation of chlorobornanes under high temperatures. The extent of this bulge depends both on temperature and the percentage of chlorine. The latter is generally lower in the samples as a result of transformation processes under environmental conditions. Therefore, integration of the bulge or the whole area leads to lower results.

  4. Onuska and Terry (1989) and Andrews et al. (1996) described an analytical method that permits the determination of parts per billion (ppb) toxaphene levels in fish tissues. Interferences from biogenic and xenobiotic substances are reduced even with low-resolution mass spectrometry. The methodology has a low susceptibility to false positive determinations, which could result from the presence of a wide variety of contaminants. The method is based on the measurement of a signal representative of the toxaphene residue (m/z 158.9) relative to a known amount of an internal standard 37C1-labeled compound. A modular approach to toxaphene enrichment has permitted a moderately simple procedure, significantly reducing analytical time requirements and the number of sample manipulations and making the procedure amenable to automation. Intra- and interlaboratory studies demonstrated the reliability and accuracy of the procedure. The methodology, which has been validated, showed a detection limit of 1 ppb of total toxaphene. Toxaphene recovery from fish at concentrations between 0.1 and 10 µg/g (or ppm) is 84 +12%.

  5. Mammalian toxicity of toxaphene and its degradation products is attributed to the inhibition of the chloride channel of the g-aminobutyric acid (GABA) receptor, which is unaffected by PCBs, chlordanes, mirex, and DDT and its metabolites. Therefore, the GABA radioreceptor assay may provide a more realistic estimation of toxaphene toxic residue in fish in the presence of other chlorinated compounds (Saleh & Blancato, 1993).

References

Andrews, P., K. Headrick, J.C. Pilon, F. Bryce, and Iverson. 1996. Capillary GC-ECD and ENCI GCMS characterization of toxaphene residues in primate tissues. Chemosphere. 32:6, 1043-53.

Evans, M.S., G.E. Noguchi, and Rice. 1991. The biomagnification of polychlorinated biphenyls, toxaphene and DDT compounds in a Lake Michigan Offshore Food Web. Arch. Environ. Contam. Toxicol. 20:87-93.

Gunderson, E.L. 1988. FDA total diet study, April 1982-1984, dietary intakes of pesticides, selected elements and other chemicals. J. Assoc. Office Anal Chem. 771:1200-1209.

Lockhart, W.L., R. Wagemann, B. Tracey, D. Sutherland, and D.J. Thomas. 1992. Presence and implications of chemical contaminants in the fresh waters of the Canadian Arctic. Sci Total Environ, 122:1-2. 165-245.

Newsome, W.H. and P. Andrews. 1993. Organochlorine pesticides and polychlorinated biphenyl congeners in commercial fish from the Great Lakes. J AOAC Int. 76:4, 707-710.

Onuska, F.I. and K.A. Terry. 1989. Quantitative high-resolution gas chromatography and mass spectrometry of toxaphene residues in fish samples. J Chromatogr. 471: 161-171.

Saleh, M.A. and J.E. Casida. 1977. Consistency of toxaphene composition analyzed by open tubular column gas-liquid chromatography. J Agric. Food Chem. 25: 63-68.

Saleh, M.A. and J.E. Casida. 1979. Toxaphene composition, structure-toxicity relations and metabolism. In Advances in Pesticides Science, Part 3, Geissbuhler (ed). Pergamon Press, Oxford and NY. pp. 562-566.

Saleh, M.A. 1987. Negative ion chemical ionization mass spectrometry in toxaphene. In: Application of New Mass Spectrometry Techniques in Pesticide Chemistry. Rosen, J.D. (ed.) John Wiley & Sons, New York. 4: 34-41.

Saleh, M.A. 1991. Toxaphene chemistry, biochemistry, toxicity, and environmental fate. Rev. Environ Contam Toxicol. 118: 1-85.

Saleh, M.A. and J.N. Blancato. 1993. Gamma-aminobutyric-acid radioreceptor assay: A confirmatory quantitative assay for toxaphene in environmental and biological samples. Chemosphere. 27:10, 1907-1914.

Vetter, W., B. Luckas, G. Heidemann, and K. Skirnisson. 1996. Organochlorine residues in marine mammals from the Northern Hemisphere—A consideration of the composition of organochlorine residues in the blubber of marine mammals. Sci Total Environ. 186:1-2, 29-39.

Gas chromatograms of standard toxaphene and represented fish samples of the Terry Creek Area
Figure 1. Gas chromatograms of standard toxaphene and represented fish samples of the Terry Creek Area

Figure 1 continued
Figure 1. Continued


Table 1. Samples with toxaphene levels less than 0.1 ppm

Sample Type Sample Number Location Reported Value ppm
Blue Crab AB68799 Dupree Creek <0.1
AB68801 <0.1
AB68802 <0.1*
Shrimp AB68814 <0.1*
AB68815 <0.1*
Crab AB68816 Terry Creek at Bridge <0.1
AB68817 <0.1*
AB68820 <0.1
Shrimp AB68824 Lower Terry Creek <0.1
AB68837 <0.1
AB68847 <0.1
Blue Crab AB68856 <0.1
AB68858 <0.1
AB68859 <0.1
B. Drum AB70218 (A) Lanier <0.1
Blue Crab AB70219 <0.1
AB70220 <0.1
AB70221 <0.1
Shrimp AB70222 <0.1
R. Drum AB70223 <0.1

*True values may be higher than the reported value (e.g., >0.1 <0.2 ppm).


Table 2. Samples with toxaphene levels from 0.1 to 0.2 ppm

Sample Type Sample Number Location Reported Value ppm
Shrimp AB68936 Terry Creek at Bridge <0.2
Yellow Tail AB70209 Lanier <0.2
AB70210 <0.2*
AB70211 <0.2**
S. Seatrout AB70213 <0.2

*True values may be higher than the reported value (e.g., >0.2 <0.3 ppm).
**True values may be higher than the reported value (e.g., >0.3 <0.5 ppm).


Table 3. Samples with toxaphene levels from 0.2 to 0.3 ppm

Sample Type Sample Number Location Reported Value ppm
R. Drum AB68807 Dupree Creek <0.3
S. Seatrout AB70214 Lanier <0.3
Mullet AB70216 <0.3


Table 4. Samples with Toxaphene levels from 0.3 to 0.5 ppm

Sample Type Sample Number Location Reported Value ppm
Mullet AB68780 Dupree Creek <0.5
AB68781 <0.5
AB68785 <0.5
Spot AB68789 <0.5
Spot AB68794 Lower Terry Creek <0.5
Croaker AB68804 Dupree Creek <0.5
Whiting AB68810 <0.5
S. Seatrout AB68860 Lower Terry Creek <0.5
AB68865 Terry Creek at Bridge <0.5
AB68866 <0.5
Red Drum AB68867 <0.5
Spot AB70206 (A) Lanier <0.5
AB70208 <0.5
S. Seatrout AB70212 <0.5
Mullet AB70215 <0.5
AB70217 <0.5


Table 5. Samples with toxaphene levels from 0.5 to 1.0 ppm

Sample Type Sample Number Location Reported Value ppm
Spot AB68787 Dupree Creek <1.0
  AB68792 <1.0
Spot AB68796 Lower Terry Creek <1.0
Flounder AB68803 Dupree Creek ~ 1.0*
Croaker AB68805 <1.0
S. Seatrout AB68813 <1.0
Mullet AB68862 Terry Creek at Bridge <1.0
AB68863 <1.0
AB68864 <1.0
Croaker AB68868 <1.0
AB68869 <1.0
Spot AB68870 <1.0
AB70207 (A) Lanier <1.0

*Concentration estimated to contain <0.1 ppm



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