Walter M. Jarman

Passive water sampling via semipermfable membrane devices (SPMDS) in concert with bivalves in the Sacramento/San Joaquin River Delta

Freshwater clams (Corbicula fluminea) and the Huckins et al. (1) semi-permeable membrane sampling device (SPMD) were simultaneously deployed at three sites on the Sacramento and San Joaquin rivers in 1990. Both clams and the SPMDs were analyzed for sequestered pesticides and polychlorinated biphenyls (PCBs) by gas chromatography with electron capture detection (GC/ECD). Polychlorinated dibenzo-p-dioxins (PCDDs), dibenzofurans (PCDFs) and non-ortho PCBs were quantified by high resolution mass spectrometry (MS). In general, levels of organochlorine compounds were approximately 1.6 times higher in clams on a wet weight basis than in the SPMDs, and trends in accumulation were similar except where biofouling of the SPMD membranes decreased uptake rates. Comparisons between the normalized, average levels of PCDDs accumulated showed that while octachlorodibenzo-p-dioxin (OCDD) was most prevalent in both clams and SPMDs, much higher levels of 2,3,7,8 TCDD were found in the SPMDs than in the clams; 2,3,7,8 TCDD was 32% of the profile relative to the OCDD level for the SPMDs and <1% of the clam OCDD level. PCB levels showed the clams primarily accumulated hexachlorinated PCBs while the pentachlorinated and tetrachlorinated congeners were higher in the SPMDs. Differences in profiles for homologous series among the PCBs reveal that some congeners, especially those with 2,4,5 substitution, are more likely to bioaccumulate than those with lower chlorination or adjacent unsubstituted sites. GC/MS chromatograms indicate the SPMDs also sequestered several polyaromatic hydrocarbons. GC/ECD chromatograms indicate the presence of several unidentified, early eluting compounds in the SPMDs.

The deep-sea as a final global sink of semivolatile persistent organic pollutants? Part I: PCBs in surface and deep-sea dwelling fish of the north and south Atlantic and the Monterey Bay Canyon (California).

The understanding of the global environmental multiphase distribution of persistent organic pollutants (POPs) as a result of the physico-chemical properties of the respective compounds is well established. We have analysed the results of a vertical transport of POPs from upper water layers (0-200 m) to the deepwater region (> 800 m) in terms of the contamination of the biophase in both water layers. The contents of persistent organochlorine compounds like polychlorinated biphenyls (PCBs) in fish living in the upper water layers of the North Atlantic and the South Atlantic, and at the continental shelf of California (Marine Sanctuary Monterey Bay and its deep-sea Canyon) are compared to the levels in deep-sea or bottom dwelling fish within the same geographic area. The deep-sea biota show significantly higher burdens as compared to surface-living species of the same region. There are also indications for recycling processes of POPs--in this case the PCBs--in the biophase of the abyss as well. It can be concluded that the bio- and geo phase of the deep-sea may act similarly as the upper horizons of forest and grasslands on the continents as an ultimate global sink for POPs in the marine environment.

Characterization of multixenobiotic/multidrug transport in the gills of the mussel Mytilus californianus and identification of environmental substrates

Most studies on resistance of organisms to xenobiotics have focused on mechanisms which metabolize the compound to some other hopefully nontoxic derivative. Another defense mechanism has recently been described in which a multixenobiotic transport protein exports moderately hydrophobic compounds from the cells, thus reducing their accumulation in the cells. In this study we describe a simple fluorescent dye assay to measure multixenobiotic transport activity in the gills of the mussel Mytilus californianus. The assay is also used to identify potential substrates or inhibitors of the transport mechanism by their ability to inhibit dye transport from the cells (resulting in their increased fluorescence). Several moderately hydrophobic pesticides including DCPA or dacthal, chlorbenside, pentachlorophenol, and CDEC or sulfallate do inhibit dye efflux from gill cells indicating that they are substrates or inhibitors, but the more hydrophobic xenobiotics DDT, DDD, DDE, and Aroclor 1254 do not, indicating that they are not substrates. We also confirm by direct chemical analysis that DCPA is exported from the cell by the multixenobiotic defense mechanism; DCPA levels in mussel gills are enhanced when an inhibitor of the transporter is present. M. californianus gills also have a protein of 170 kDa that is immunologically related to the mammalian multidrug transport protein (responsible for multidrug resistance, a phenomenon similar to the multixenobiotic defense mechanism). M. californianus and other marine organisms may use multixenobiotic transport to reduce the accumulation of potentially harmful environmental xenobiotics in their cells. The implications of these results for biomonitoring studies, such as the Mussel Watch Program, are discussed.

Levels of organochlorine compounds, including PCDDS and PCDFS, in the blubber of cetaceans from the west coast of North America

Abstract Levels of organochlorine compounds (PCDD, PCDF, PCB and organochlorine pesticides) were determined in cetaceans collected from the west coast of North America between 1986 and 1989. The samples included gray whale (Eschrichtius robustus), killer whale (Orcinus orca), false killer whale (Pseudorca crassidens), Rissos dolphin (Grampus griseus) and Dalls porpoise (Phocoenoides dalli) collected in British Columbia, and harbour porpoises (Phocoena phocoena) collected in British Columbia and central California. TCDD and TCDF levels ranged from 1 to 8 ng kg−1 and 2.0 to 109 ng kg−1, respectively. The highest levels of PCDDs were found in the harbour porpoises; the levels of 1,2,3,6,7,8-HxCDD in the samples from Victoria, Campbell River and Qualicum River were 128, 128 and 62 ng kg−1, respectively. Five other 2,3,7,8-substituted dioxins and dibenzofurans were detected in the cetaceans at levels ranging from 1 to 10 ng kg−1. In addition to the 2,3,7,8-substituted congeners, several non 2,3,7,8-substituted congeners were detected. The patterns of the PCDDs and PCDFs in the British Columbia porpoises were consistent with implication of chlorophenols as the source of the PCDDs and PCDFs, which were either present in wood chips used in bleached kraft paper mills, or came from direct contamination by chlorophenols. No PCDDs or PCDFs were detected in the California samples. One false killer whale sample had exceptionally high levels of DDT compounds (1700 mg kg−1 DDE, 120 mg kg−1 DDT and 40 mg kg−1 o,p′-DDT) and Toxaphene (89 mg kg−1). PCB levels in the cetaceans were highest in the false and killer whales (22 to 46 mg kg−1 GM), and lowest in the Rissos dolphin (1.7 mg kg−1). Levels of DDE in the British Columbia harbour porpoises were 6.0 mg kg−1, and probably reflect the accumulation of global background levels of DDE.

The deep-sea as a final global sink of semivolatile persistent organic pollutants? Part II: organochlorine pesticides in surface and deep-sea dwelling fish of the North and South Atlantic and the Monterey Bay Canyon (California).

The understanding of the global environmental multiphase distribution of persistent organic pollutants (POPs) as a result of the physico-chemical properties of the respective compounds is well established. We have analysed the results of a vertical transport of POPs from surface water to deepwater in terms of the contamination of the biota living in the respective environmental compartments. Samples were taken from the North and the South Atlantic and from the uprising water region of the continental shelf of California (Marine Sanctuary Monterey Bay and its Canyon). The contents of persistent organochlorine pesticides (DDTs, chlordanes, toxaphenes, HCHs, and HCB) in surface-living fish are compared to those in deepwater fish of the same geographic area. The deepwater biota show significantly higher burdens as compared to surface-living species of the same region. There are also indications for recycling processes of POPs of the class of organochlorine pesticides in the biophase of the abyss as well. It can be concluded that the bio- and geophase of the deep-sea may act as an ultimate global sink for persistent semivolatile contaminants in the marine environment like the soil on the continents.

Surveillance for previously unmonitored organic contaminants in the San Francisco Estuary

The San Francisco Estuary Regional Monitoring Program initiated surveillance monitoring to identify previously unmonitored synthetic organic contaminants in the San Francisco Estuary. Organic extracts of water samples were analyzed using gas chromatography-mass spectrometry in full scan mode. The major contaminant classes identified in the samples were fire retardants, pesticides, personal care product ingredients, and plasticizers. Evidence from the literature suggests that some of these contaminants can persist in the environment, induce toxicity, and accumulate in marine biota and in higher food chain consumers. The major sources of these contaminants into the marine environment are the discharge of municipal and industrial wastewater effluents, urban stormwater, and agricultural runoff. As a proactive effort, it is suggested that surveillance studies be used routinely in monitoring programs to identify and prevent potential problem contaminants from harming the marine environment.

Organochlorine and polychlorinated biphenyl levels in pinniped milk from the Arctic, the Antarctic, California and Australia

Abstract This study presents levels of organochlorines and polychlorinated biphenyls in pinniped milk samples collected from four geographical regions. These regions include the Arctic, the Antarctic, California and Australia. Twenty milk samples from five species of pinnipeds were analyzed for organochlorines and polychlorinated biphenyls. Analyzes were carried out by high resolution gas chromatography/electron capture (HRGC/ECD) and high resolution gas chromatography/low resolution mass spectrometry (GC-MS). All samples had detectable levels of p,p′-DDE(DDE) with geometric mean (geom. mean) values ranging from 12 ug/kg in Antarctic fur seals to 1400 ug/kg in California sea lions. Geom. mean values reported for DDE in northern hemisphere pinniped milk ranged between 14 and 118 times larger than values reported for southern hemisphere pinniped milk. In addition every sample contained detectable levels of PCBs; the primary congeners reported include 99, 118, 153, 138, 180, and 187. Geom. mean values reported for the sum of these six congeners range from 6.78 ug/kg in Antarctic fur seals up to 360 ug/kg in northern elephant seals from California. Pinniped milk samples from California contained the highest overall levels of organochlorines and polychlorinated biphenyls. DDT (and metabolites), chlordane compounds, and dieldrin were also detected in most samples with a wide range of levels reported.

Trace metals in seabirds, Steller sea lion, and forage fish and zooplankton from central California

We studied concentrations of the trace metals, aluminum (Al), chromium (Cr), iron (Fe), copper (Cu), zinc (Zn), arsenic (As), selenium (Se), silver (Ag), cadmium (Cd), and mercury (Hg), in krill (Euphausia pacifica and Thysanoessa spinifera), two species of fish (short-bellied rockfish Sebastes jordani and northern anchovy Engraulis mordax), four species of marine bird (Common Murre Uria aalge, Brandts Cormorant Phalacrocorax penicillatus, Rhinoceros Auklet Cerorhinca monocerata, and Pigeon Guillemot Cepphus columba) and a pinniped, (Steller sea lion Eumetopias jubatus) from the Gulf of the Farallones, central California in 1993. Geometric mean levels of some trace elements in Steller sea lions were elevated (Cu, 91.0 mg/kg dry weight; Hg, 19.0 mg/kg; Se, 4.1 mg/kg). Levels of Hg in Pigeon Guillemot (3.5 mg/kg) were also elevated. Mercury increased whereas Pb decreased with increasing trophic level in the Gulf of the Farallones food web. Selenium levels were highest for krill and sea lions, and intermediate for fish and birds occupying mid trophic levels. Results indicate little to relatively high trace metal contamination of upper trophic level marine wildlife in the central California coastal marine ecosystem.

Identification of tris(chlorophenyl)methanol in blubber of harbor seals from Puget Sound

Abstract A compound detected in extracts of blubber of harbor seals, Phoca vitulina , found dead in Puget Sound in the north-western United States over the period 1972–1982 was identified as tris (chlorophenyl)methanol from its mass spectral characteristics and by synthesis. Concentrations in harbor seal blubber ranged from 23 to 750 ng/g of the lipid weight and showed no evident changes over the time interval of the study. Concentrations were highly correlated with those of most of the other organochlorines detected in the harbor seal extracts, indicating a similar pattern of uptake and accumulation. The compound is used in the manufacture of optically active polymers, which appear to be a plausible source.

Man-made chemicals found in remote areas of the world: the experimental definition for POPs.

Members of the United Nations Economic Commission for Europe (UN-ECE) signed a legally binding protocol on persistent organic pollutants (POPs) in February 1998 under the Convention on Long-Range Transboundary Air Pollution. A treaty that intends to control the production, import, export, disposal and use of toxic chemicals that persist for decades in the environment has been formally signed at a conference in May 2001 in Stockholm. The 2001 POP treaty, like the 1998 LRTAP POP protocol, contains a provision on adding further chemicals to the initial group of twelve or fifteen. The occurrence of a compound or a group of compounds in so called remote and pristine areas, e.g. in the Artic or in the Southern Hemisphere, proves its stability under the chemical and biological conditions of the environment. Compounds identified in this way, in samples taken primarily in very remote regions of the planet, are classified by their environmental fate and global distribution as persistent organic pollutants (POPs), regardless of any political assessments.