Keith A. Maruya

Distribution and sources of polycyclic aromatic hydrocarbons in sediments from Kyeonggi Bay, Korea

Abstract Sixty-six sediment samples were collected from Kyeonggi Bay, Korea, in December 1995 and analysed for a suite of 2–6 ring polycyclic aromatic hydrocarbons (PAHs). Sediments were collected in the Han River estuary, Incheon Harbour, from nearshore locations adjacent to large industrial complexes south of Incheon, and along transects toward the open sea. Concentrations of PAHs (9.1–1400 ng g −1 dry wt with an average of 120 ng g −1 ) were positively correlated with organic carbon (OC) content and negatively correlated with mean sediment grain size. The highest PAH concentrations were in samples from inner Incheon Harbour basins; these levels decreased within a short distance from these heavily industrialised waterways. The sources of PAHs were determined to be primarily combustion in nature based on the distribution of alkylated homologs to parent compounds. Overall, sediment PAHs in Kyeonggi Bay were lower than those in the United States and Europe. The potential for biological effects due to PAHs alone is expected to be low based on comparisons of individual and ΣPAH concentrations with effects-based and equilibrium partitioning-based sediment quality guidelines/criteria.

Organic and organometallic compounds in estuarine sediments from the Gulf of Mexico (1993-1994)

Sediment samples from 281 estuarine sites in the Gulf of Mexico were collected in 1993–1994 and analyzed for several classes of organic and organometallic compounds as part of the Environmental Monitoring and Assessment Program of the United States Environmental Protection Agency. Polynuclear aromatic hydrocarbons (PAHs) were the contaminant class found most frequently and in the highest concentrations; the sum of 24 congeners (ΣPAHs) ranged from <5 ng g−1 to 15.500 ng g−1 (dry wt basis). A low percentage of samples (3.9%) exceeded 2000 ng g−1 ΣPAHs, and only six samples (2.1%) exceeded 4000 ng g−1, a level above which adverse biological effects may be expected to occur. Less than 4% of sediments exceeded 20 ng g−1 for the sum of 20 polychlorinated biphenyls (ΣPCBs) and only four samples (1.4%) exceeded 20 ng g−1 for the sum of several organochlorine pesticides (ΣOCPs). A sample from Freeport Harbor, Texas, contained 4230 ng g−1 ΣPAHs, 322 ng g−1 ΣPCBs, and 49.6 ng g−1 ΣOCPs. Tributyltin exceeded 100 ng g−1 in only four samples, all of which were from stations in Corpus Christi Bay or Galveston Bay in Texas. The detection of a suite of organophosphate pesticides was very rare and did not exceed 15 ng g−1. Sediments from the tidally influenced section of the Mississippi River in Louisiana contained low to moderate levels of all classes of organic compounds. The most contaminated sites were in urban estuaries (e.g., Corpus Christi, Galveston, and Pensacola (Florida bays), underscoring the need to concentrate future monitoring and assessment efforts at the regional and local level.

Geographic specificity of Aroclor 1268 in bottlenose dolphins (Tursiops truncatus) frequenting the Turtle/Brunswick River Estuary, Georgia (USA)

Coastal marine resources are at risk from anthropogenic contaminants, including legacy persistent organic pollutants (POPs) with half-lives of decades or more. To determine if polychlorinated biphenyl (PCB) signatures can be used to distinguish among local populations of inshore bottlenose dolphins (Tursiops truncatus) along the southeastern U.S. coast, blubber from free-ranging and stranded animals were collected along the Georgia coast in 2004 and analyzed for PCB congeners using gas chromatography with electron capture and negative chemical ionization mass spectrometric detection (GC-ECD and GC-NCI-MS). Mean total PCB concentrations (77+/-34 microg/g lipid) were more than 10 fold higher and congener distributions were highly enriched in Cl(7)-Cl(10) homologs in free-ranging animals from the Turtle/Brunswick River estuary (TBRE) compared with strandings samples from Savannah area estuaries 90 km to the north. Using principal components analysis (PCA), the Aroclor 1268 signature associated with TBRE animals was distinct from that observed in Savannah area animals, and also from those in animals biopsied in other southeastern U.S estuaries. Moreover, PCB signatures in dolphin blubber closely resembled those in local preferred prey fish species, strengthening the hypothesis that inshore T. truncatus populations exhibit long-term fidelity to specific estuaries and making them excellent sentinels for assessing the impact of stressors on coastal ecosystem health.

Polychlorinated biphenyls and toxaphene in preferred prey fish of coastal southeastern U.S. bottlenose dolphins (Tursiops truncatus)

Legacy organochlorine (OC) contaminants continue to pose a potential risk to ecological and human health in coastal aquatic ecosystems of the southeastern United States. Polychlorinated biphenyls (PCBs) and toxaphene (TOX) were analyzed by gas chromatography with electron capture detection and negative chemical ionization mass spectrometry in 77 composites of four inshore fish species commonly preyed upon by bottlenose dolphins (Tursiops truncatus) from estuaries near Savannah, Georgia (SAV), Brunswick, Georgia (BRN), and Jacksonville, Florida (JAX), USA. Whereas seasonal and species-specific differences were minimal, differences among mean total PCB concentrations (sigmaPCBs) by estuary (42.0 +/- 48.3, 1.59 +/- 1.24, and 0.281 +/- 0.075 microg/g lipid for BRN, JAX, and SAV, respectively) were highly significant. This estuary-specific trend also held true for mean total toxaphene concentrations (sigmaTOX): 49 +/- 100 (BRN), 1.2 +/- 0.52 (JAX), and 0.40 +/- 0.19 microg/g lipid (SAV). Congener profiles of PCBs also were found to be significantly different among estuaries, with BRN and (to a lesser extent) JAX samples enriched with highly chlorinated homologs associated with Aroclor 1268, a legacy OC linked to a historical point source in Brunswick. The observed spatial heterogeneity in OC concentrations and PCB congener profiles suggests that contaminated fish from Brunswick pose the greatest risk to ecological and human health via biomagnification and seafood consumption; highly chlorinated PCBs (and possibly toxaphene) are transported in a southerly, alongshore direction; and the uniqueness of Aroclor 1268 underscores its utility as a signature proxy in future regional ecotoxicological studies.

Anaerobic transformation of compounds of technical toxaphene. 2. Fate of compounds lacking geminal chlorine atoms.

The major toxaphene metabolites in sediment and soils (2-exo,3-endo,6-exo,8,9,10-hexachlorobornane [B6-923] and 2-endo,3-exo,5-endo,6-exo,8,9,10-heptachlorobornane [B7-1001]) were incubated with the isolated gram-negative bacterium Dehalospirillum multivorans. Within 14 d, biotransformation of B7-1001 was nearly quantitative, resulting in two penta- and six hexachlorobornanes, as well as one unsaturated hexachloro compound of technical toxaphene. The major transformation product (approximately 50% of all metabolites) was identified as 2-exo,3-endo,5-exo,8,9,10-hexachlorobornane (B6-903). Abiotic dehydrochlorination of B7-1001 with methanolic KOH resulted in the formation and subsequent identification of the lone unsaturated compound as 2,5-endo,6-exo,8,9,10-hexachloroborn-2-ene. Thus, dehydrochlorination was found to be a minor process of the anaerobic transformation of toxaphene. Biotransformation of 70% of amended B6-923 within 14 d demonstrated that reductive dechlorination was not exclusively associated with geminal Cl atoms, as previously suggested. Three pentachlorobornanes were identified as transformation products, one of which was identical with a transformation product of B7-1001. This commonality unequivocally proves this metabolite to be 2-exo,3-endo,8,9,10-pentachlorobornane. Fifteen previously unknown metabolites of B6-923, B7-1001, and other toxaphene compounds identified in this study were detected in sediment from Lake Ontario (Canada), underscoring the importance of microbial toxaphene transformation in natural, aquatic environments.

Di- and tribromoindoles in the common oyster (Crassostrea virginica)

The sources/origins, fate and impacts of naturally occurring organobromine compounds in the marine environment are largely unknown. Soft tissue composites of the common oyster (Crassostrea virginica) collected from coastal Georgia (USA) were analyzed for organobromines by gas chromatography. Three simple bromoindoles (BIs)--two dibromo- and one tribromo congener--were detected and their molecular formulas elucidated by electron and negative chemical ionization GC-MS. Semi-quantitative estimates of BI concentrations in these samples using GC-ECD indicated that oysters sampled in November 1999 contained 5-10 times more BIs than those sampled in August 2000 and March 2001. Although their bromine substitution patterns are presently unknown, this first ever report of bromoindoles in C. virginica, a prolific and important commercial and ecological species, underscores its potential utility as a bioindicator of organobromines in the coastal marine environment.

Residues of Toxaphene in Finfish and Shellfish from Terry and Dupree Creeks, Georgia, U.S.A.

To better characterize human health risks associated with potentially contaminated seafood, 56 composite samples of edible tissue of several finfish and shellfish species were analyzed for residues of toxaphene using gas chromatography with electron capture and negative ion mass spectrometric detection (GC-ECD and GC-ECNI-MS). Toxaphene in these samples, collected in 1997 near a former toxaphene plant in Brunswick, Georgia, were previously reported as non-detectable using non-selective techniques. Estimated total toxaphene concentrations (ΣTOX) ranged from less than 0.01 to 26 μ g−1 on a wet tissue basis. Smaller, bottom dwelling finfish such as croaker, mullet, and spot exhibited the highest ΣTOX (0.76–26 μg g−1), larger predatory fish including seatrout contained intermediate levels (0.08–4.4 μg g−1), and shellfish (blue crab and shrimp) contained the lowest levels (<0.01 to 0.27 μg g−1). For a given species, samples from the site furthest from the toxaphene plant had lower ΣTOX than samples from the other 3 sites. On a congener specific basis, levels ranged from <0.0025 to 3.5 μg g−1. Congener distributions were, in general, dominated by 2-exo, 3-endo, 6-exo,8,9,10-hexachlorobornane (Hx-Sed) and 2-endo,3-exo,5-endo,6-exo,8,9,10-heptachlorobornane (Hp-Sed), breakdown products of Cl8−Cl10 toxaphene homologs. Other prominent congeners confirmed by GC-ECNI-MS included Parlar numbers 26, 40/41, 42, 44, 50, 62, and 63, as well as several unidentified Cl6−Cl9 homologs. Minor differences in congener distribution among species and sampling locations suggested that exposure regimes and/or intrinsic biotransformation capabilities were not uniform. These results indicate that toxaphene residues were detectable in all species surveyed and at concentrations higher than estimated previously.

Dehalogenation of 2,6-dibromobiphenyl and 2,3,4,5,6-pentachlorobiphenyl in contaminated estuarine sediment

Estuarine sediments from a USEPA Superfund site in coastal Georgia were extensively contaminated with Aroclor 1268, a mixture of highly chlorinated polychlorinated biphenyls used by a former chlor-alkali plant. Batch slurries of contaminated sediment were incubated for 1 yr with amendments of 2,6-dibromobiphenyl (26-BB) and 2,3,4,5,6-pentachlorobiphenyl (23456-CB) under anaerobic, sulfate-reducing conditions and different pH (5.5-7.5). Organic extracts of slurry sub-samples in a time series were analyzed by congener-specific GC-MS. Dechlorination of 23456-CB was pH dependent and occurred via two routes with the sequential loss of (1) meta and para chlorines and (2) para, ortho, and meta chlorines. Quantitative dehalogenation of 26-BB was observed at all pH. Supplementation of nonachlorobiphenyls (as primers) did not induce dechlorination of native Aroclor 1268 nor of the primers themselves. While contaminated estuarine sediments possess microbial consortia with diverse dehalogenating activities, lack of dechlorination of Aroclor 1268 and spiked nonachlorobiphenyl congeners suggests a bioavailability limitation or enzyme-substrate incompatibilities.

Residues of toxaphene decrease in estuarine fish after removal of contaminated sediments

To determine if toxaphene residues in edible fish tissue decreased after removal of contaminated sediments from an estuarine site in 1999, 51 composite samples representing six finfish species were collected in 2001 and analyzed using gas chromatography with electron capture and negative ion mass spectrometric detection. The grand mean total toxaphene residue concentration on a wet weight basis (ΣTOXwet) was 1,400 ± 3,500 ng g−1 (range: < 18 to 18,000 ng g−1) and was positively correlated with extractable lipid. On a lipid basis, the mean ΣTOXlip was 26 ± 33 μg g1, which decreased with increasing distance from the study site. Although benthically-oriented species, such as spot (Leiostomus xanthurus) and striped mullet (Mugil cephalus), exhibited higher mean ΣTOXwet than those of higher trophic level fish, mean ΣTOXlip were not significantly different among species. The grand mean ΣTOX for 2001 was 3.8 (wet) and 2.6 (lipid) times less than corresponding preremedial action (1997) concentrations, suggesting that bioavailable toxaphene residues in this system have been reduced. Forage species, such as croaker (Micropogonias undulatus), mullet, and spot, preferentially accumulate toxaphene residues in this system and may serve as vectors of organochlorine contaminants in the estuarine and coastal ocean food web.