Sin-Lam Chan

Neoplastic and other diseases in fish in relation to toxic chemicals: an overview☆

Field studies were conducted over a 5-year period in Puget Sound to investigate etiological relationships between prevalences of hepatic neoplasms in bottom-dwelling marine fish, with emphasis on English sole (Parophrys vetulus), and concentrations of toxic chemicals in sediments and bottom fish. Statistically significant correlations were found between prevalences of hepatic neoplasms and (1) sediment concentrations of aromatic hydrocarbons, and (2) concentrations of metabolites of aromatic compounds in the bile. A significant difference was also found between the concentrations of N-oxyl derivatives of nitrogen heterocycles (free radicals) in liver microsomes of English sole with liver lesions compared to sole without liver lesions. These N-oxyl free radicals were apparently metabolically derived from complex suites of nitrogen heterocycles present in Puget Sound environments. Recent evidence suggests that aromatic free radicals (possibly derivatives of aromatic hydrocarbons) may also be bound to hepatic DNA isolated from English sole with liver neoplasms collected in several polluted areas of Puget Sound. Such evidence for xenobiotic-DNA interactions has thus far not been obtained for fish from reference areas and for lesion-free fish from polluted areas. Various laboratory studies designed to evaluate the etiology of the liver neoplasms have also yielded evidence that is consistent with the view that high molecular weight aromatic hydrocarbons play a significant role in the etiology of hepatic tumors in the bottom-dwelling fish. Associations between chemical exposures and diseases in other marine species from southern California and Boston Harbor are also discussed. Similar relationships between liver and skin neoplasms in selected bottom feeding fresh water species and sediment-associated chemicals are also presented.

High-performance liquid chromatographic method for isolating organic contaminants from tissue and sediment extracts

Interest in the assessment of the anthropogenic contamination of the marine environment has accelerated in recent years. Existing methods to analyze environmental samples (e.g., sediments or tissues) for trace amounts of organic contaminants such as aromatic hydrocarbons and chlorinated compounds are tedious and costly. We report a rapid, efficient high-performance liquid chromatography (HPLC) procedure which uses a size-exclusion column to separate the analytes of interest from interfering compounds in the sample matrix. Analytical results from the HPLC method were, in general, comparable to a gravity-column method which had been used for several years. The HPLC method had several other advantages: improved precision; the ability to monitor chromatographic conditions; the potential for automating analyses; and reduced consumption of solvents and other materials.

Screening for planar chlorobiphenyl congeners in tissues of marine biota by high-performance liquid chromatography with photodiode array detection

A rapid method has been developed to screen for planar chlorobiphenyl (CB) congeners, as well as certain other CBs and DDTs, in tissue samples from marine biota. The analytes were extracted from tissue matrices with 1:1 hexane/pentane (v/v) and interfering compounds were separated from the CBs on a gravity-flow column packed with acidic, basic and neutral silica gel eluted with 1:1 hexane/methylene chloride (v/v). Subsequently, the planar CB congeners were resolved from the DDTs and other CBs by HPLC on Cosmosil PYE analytical columns cooled to 9 degrees C and were measured by an ultraviolet (UV) photodiode array (PDA) detector. Two important advantages of PDA over conventional UV detection were the ability to identify individual analytes by comparing their UV spectra to those of reference standards and the ability to establish the spectral homogeneity (purity) of the analytes by comparing spectra within a peak to the apex spectrum. The HPLC/PDA method was tested with tissue samples from fish, shellfish and marine mammals; concentrations of certain CBs and DDTs in samples determined by screening compared favorably with those in the same samples analyzed by a comprehensive method (e.g., gas chromatography/high resolution mass spectrometry). However, the HPLC/PDA method was about an order of magnitude less sensitive than determinations by comprehensive methods.

Status, correlations and temporal trends of chemical contaminants in fish and sediment from selected sites on the Pacific Coast of the USA

Abstract The National Benthic Surveillance Project (NBSP), a component of NOAAs National Status and Trends Program, monitored sediment and bottomfish for chlorinated hydrocarbon pesticides (CHs), PCBs and polycyclic aromatic hydrocarbons (PAHs) at selected urban and nonurban sites along the west coast of the USA from 1984 to 1993. This project successfully generated an extensive data set to evaluate the recent status and trends of environmental quality in coastal waters. This article summarizes and interprets the status of selected PAHs, PCBs and CHs in surficial sediments and selected species of bottom-feeding fish for 50 sites in Alaska, Washington, Oregon and California for the first 7 years (1984–1990) of the NBSE. The highest concentrations of most sediment-associated organic contaminants were present in the most highly urbanized areas, and many of the organic contaminants were bioaccumulated by indigenous marine fish species. The concentrations of PAHs and CHs in sediments generally correlated with levels of these compounds or their derivatives in bottom-dwelling fish. Assessment of trends in the concentrations of chlordanes, dieldrin, DDTs, PAHs and PCBs for the 7 year period from 1984–1990 suggest that, since the mid-1980s, concentrations of the persistent CHs, such as PCBs and DDTs in sediment and fish, show no consistent temporal trends, whereas levels of PAHs, which are nonpoint source contaminants, showed consistent increases at both nonurban and urban near-coastal sites.

Chemical contaminants in harbor porpoise (Phocoena phocoena) from the North Atlantic coast: Tissue concentrations and intra- and inter-organ distribution

Concentrations of chlorinated hydrocarbons (CHs), such as polychlorinated biphenyls (PCBs), were measured in subsamples taken from different anatomical locations of blubber and liver of three apparently healthy harbor porpoises (Phocoena phocoena) incidentally caught in a gill-net fishery along the northwest Atlantic coast; selected elements (e.g., mercury) were measured in subsamples of liver. The vertical distribution (skin to muscle) of contaminants within blubber was also determined. Additionally, the concentrations of CHs and elements were determined in individual samples of brain, lung, kidney, and testis to assess how the disposition of toxic chemicals may be dependent on the physiological characteristics of a specific organ. Statistical analyses of the results showed that the anatomical location of the blubber or liver sample had no significant effect on concentrations of either CHs in blubber and liver, or of selected elements in liver. However, there were statistical differences between strata of blubber (skin to muscle) for the concentrations of CHs. As expected, the results showed that the CH concentrations, based on wet weight, were considerably higher in the blubber than in the other tissues; however, the concentrations of CHs in the different tissues were more comparable when values were based on total lipid weight with the exception of the brain where lipid normalized concentrations were lower than in all other tissues: This low relative accumulation of lipophilic contaminants in the brain tissue may be due to the presence of the blood-brain barrier, or due to a lower proportion of neutral lipids, such as triglycerides, as analysis for percent lipid and for the proportion of specific lipid classes showed.

Analyses for petroleum-related contaminants in marine fish and sediments following the Gulf oil spill

Abstract Approximately 1 year after Kuwaiti crude oil was spilled and burned during the Gulf War, scientists on board the NOAA R/V Mt Mitchell sampled sediment and biota in the Gulf to look for evidence of petroleum contamination. Subtidal sediments and fish bile were analysed for petroleum-related aromatic compounds (ACs) on board the Mt Mitchell using cost-effective and rapid high-performance liquid chromatographic (HPLC) screening methods. Parent ACs and their alkyl homologs were measured in sediments. However, because fish extensively metabolize ACs in their livers to form polar metabolites that are concentrated in bile for excretion, metabolites of ACs were measured in bile. HPLC screening analyses found ACs in many of the sediment and fish bile samples collected. The results of HPLC screening were confirmed in selected samples by gas chromatography/mass spectrometry (GC/MS) analyses that identified petroleum-related ACs (e.g., alkyl phenanthrenes or dibenzothiophenes) in sediments and their metabolites in bile.

A method for analysis of butyltin species and measurement of butyltins in sediment and English sole livers from Puget Sound

Abstract A method for the determination of tetra-, tri-, di- and monobutyltin in marine sediments and in tissues from English sole was developed. The method utilized dichloromethane/tropolone extraction of the butyltins, derivatization with hexylmagnesium bromide, and a silica/alumina column cleanup prior to gas chromatographic/mass spectrometric (GC/MS) analysis. A number of quality assurance measures were incorporated in the method. Mean recoveries of the surrogate spike tripentyltin from sediment and tissue reference materials ranged from 96% to 110%. The method was applied to sediments and livers of English sole collected in Puget Sound, Washington state. Total butyltin concentrations in sediments ranged from 1000 ng/g were found in some sediments. Butyltins were also determined in livers from English sole captured at sites where sediments were contaminated with butyltins. Dibutyltin (at concentrations up to 870 ng/g dry weight as Sn) was the predominant butyltin species found in the livers.

Uptake of aromatic and chlorinated hydrocarbons by juvenile chinook salmon (Oncorhynchus tshawytscha) in an urban estuary

A study was conducted to assess the potential for uptake of toxic chemicals by down-stream migrant salmon in an urban estuary. Juvenile chinook salmon (Oncorhynchus tshawytscha) were collected from the Duwamish Waterway (located in Seattle, Washington) and from the Nisqually River (a reference site). The mean concentrations of aromatic hydrocarbons and polychlorinated biphenyls (PCBs) in the stomach contents (food organisms) of salmon from the Duwamish Waterway were approximately 650 times and 4 times, respectively, higher than those in salmon from the Nisqually River. Similarly, the mean concentration of bile metabolites of aromatic compounds which fluoresce at benzo[a]pyrene wavelengths was 24 times higher in the urban salmon compared to the reference salmon, whereas the mean concentration of PCBs in liver of urban salmon was 3 times higher than that in reference salmon. The study clearly demonstrated that, during their residency in this urban estuary, juvenile chinook salmon bioaccumulate substantial levels of toxic chemicals. The possible effects of these chemical exposures on the health and survival of this species are not presently known.

Rapid high-performance liquid chromatographic methods that screen for aromatic compounds in environmental samples

Abstract In order to monitor the quality of coastal waters that provide habitats for living marine resources, samples of sediment and biota must be analyzed to assess the degree and distribution of anthropogenic contamination. Analytical time and costs can be greatly reduced by first employing methods that screen for contaminants before selecting samples for rigorous analyses. In this paper, we review the applications of rapid high-performance liquid chromatographic (HPLC) methods to screen for aromatic compounds in sediment, bile and tissue samples. These methods have been used to assess damage to natural resources after the Exxon Valdez oil spill. In addition, the bile screening method has also been used to evaluate contaminants in fish sampled for a national monitoring program. The rapid screening of sediment or bile provides an estimate of contaminant concentrations that can then be confirmed in selected samples by more complicated and expensive analyses by gas chromatography/3-mass spectrometry (GC-MS). Furthermore, HPLC and GC-MS chromatographic patterns from sediment and bile can provide information about the source of contamination, e.g., crude oil, diesel fuel or pyrogenic contaminants. We also discuss the important role screening methods will play in the future in assessing the quality of aquatic habitats, the safety of seafood, and other important issues related to anthropogenic contamination.

Chemical contaminants in gray whales (Eschrichtius robustus) stranded along the west coast of North America.

The concentrations of selected chlorinated hydrocarbons (e.g. PCBs, DDTs, DDEs, chlordanes) and essential (e.g. zinc, selenium, copper) and toxic (e.g. mercury, lead, arsenic) elements were measured in tissues and stomach contents from 22 gray whales (Eschrichtius robustus) stranded between 1988 and 1991 at sites from the relatively pristine areas of Kodiak Island, AK, to more urbanized areas in Puget Sound, WA, and San Francisco Bay, CA. The majority of animals were stranded at sites on the Washington outer coast and in Puget Sound. The gray whale has the unique feeding strategy among Mysticeti of filtering sediments to feed on benthic (bottom dwelling) invertebrates. Thus, the wide geographical distribution of the stranded whales allowed (1) an initial assessment of whether concentrations of chemical contaminants in these whales exhibited region specific differences and (2) whether toxic chemicals that accumulate in sediments may have contributed to the mortality and stranding of gray whales near the more polluted urban areas. Analyses for chlorinated hydrocarbons in blubber from 22 animals showed no apparent significant differences among stranding sites. The concentrations of sigma PCBs and sigma DDEs in blubber, for example, ranged from 120 to 10,000 and 9 to 2100 p.p.b. (ng/g) wet weight, respectively. Additionally, analyses of chlorinated hydrocarbons and selected elements in liver (n = 10) also showed no apparent significant differences between whales stranded in Puget Sound and whales stranded at more pristine sites (Alaska, Washington outer coast and Strait of Juan de Fuca and Strait of Georgia). For example, the concentrations of sigma PCBs and sigma DDEs in liver ranged from 79 to 1600 and 7 to 280 p.p.b., respectively, and the concentrations of the toxic elements, mercury and lead ranged from 9 to 120 and 20 to 270 p.p.b., respectively. Analyses of stomach contents revealed low concentrations of chlorinated hydrocarbons, but high concentrations (wet weight) of aluminum (1,700,000 +/- 450,000 p.p.b.), iron (320,000 +/- 250,000 p.p.b.), manganese (23,000 +/- 15,000 p.p.b.), and chromium (3400 +/- 1300 p.p.b.), but no significant differences were observed between whales stranded in Puget Sound compared to whales stranded at the more pristine sites. The relative proportions of these elements in stomach contents of stranded whales were similar to the relative proportions in sediments, which is consistent with a geological source of these elements from the ingestion of sediment during feeding. Thus, overall, the concentrations of anthropogenic chemicals in stranded gray whales showed little relation to the levels of chemical contaminants at the stranding sites.(ABSTRACT TRUNCATED AT 400 WORDS)