Effects of polynuclear aromatic hydrocarbons on fishes and shellfish: An overview of research in virginia

This paper discusses the following topics related to polynuclear aromatic hydrocarbon pollution in estuaries: (1) the use of oysters (Crassostrea virginica), hard clams (Mercenaria mercenaria) and brackish water clams (Rangia cuneata) in residue monitoring; (2) the effects of elevated PAH residues on oyster condition; (3) three years of field studies relating PAH sediment contamination to abnormalities in fishes; and (4) laboratory bioassays for effects and bioconcentration modeling. Oysters, hard clams and Rangia have been shown, from 3 years of field studies, to be good monitors of pollution inputs as one proceeds along salinity gradients from 25‰ to 0·5‰. Effects of increased body burdens of PAHs are shown by a lowering of the oysters' condition index, as measured by lipid levels. Fishes inhabiting the Elizabeth River, VA, which is highly contaminated with PAHs, have abnormalities (cataracts, skin lesions, abnormal fins, etc.). These abnormalities have higher incidence in regions of the river where the sediments are more heavily contaminated. Laboratory studies utilizing contaminated sediments have reproduced some of the abnormalities observed in the field. Bioconcentration of PAHs from sediments has been studied with oysters and hard clams. Oysters generally accumulate three times the body burdens of clams exposed to the same suspensions. A faster depuration rate (k₂) for clams appears to be responsible for the higher equilibrium body burden of oysters.     

沉积物中多环芳烃在海岸带水域自然环境中的衰减研究

本文在现场情况下，研究了自然条件下受污染海岸带沉积物中的7种多环芳烃（Polynuclear Aromatic Hydrocarbons，简称PAHs）的解吸动力学行为。结果表明，7种PAHs）的解吸动力学行为。结果表明，7种PAHs的解吸动力学行为可以用二元模型模拟。文中并将所得数据与文献报道的数据进行了比较。     

Responses of the mixed function oxidase system of some bivalve and gastropod molluscs to exposure to polynuclear aromatic and other hydrocarbons

Bivalve and gastropod molluscs readily accumulate polynuclear aromatic (PNAH) and other hydrocarbons from the environment and are widely used in environmental monitoring programmes.¹ The response of the cytochrome P-450 monooxygenase or mixed function oxidase (MFO) system to organic xenobiotics is of interest from the comparative viewpoint and in biological effects monitoring.² We have studied the bivalves Mytilus edulis (mussel) and Cardium edule (cockle) and the gastropod Littorina littorea (periwinkle) exposed to hydrocarbons, experimentally or naturally in the field. The general trend of response in digestive gland microsomes was an increase in cytochrome P-450 content and NADPH-cytochrome c reductase (NADPH-CYTCRED) activity but no increase in benzo[a]pyrene hydrolyase (BPH) activity. Sex and seasonal interactions were evident. We conclude that aspects of the responses may be peculiar to the Mollusc and that NADPH-CTYCRED possibly offers potential for this phylogenetic group as a specific indicator of biological impact by organic pollution.     

The effects of dissolved organic matter on the aqueous partitioning of polynuclear aromatic hydrocarbons

The partitioning of six polynuclear aromatic hydrocarbons into aqueous solutions containing dissolved organic matter from various coastal environments was investigated by liquid chromatography. Specific hydrocarbon-organic matter interactions were observed. The greatest interactions occurred with the very low solubility hydrocarbons and with organic matter of terrestrial origin. Ultrafiltration experiments suggested that it was the relatively high (greater than approximately 500) molecular weight organic matter that was interacting with the hydrocarbons.     

The effects of temperature and salinity on the aqueous solubility of polynuclear aromatic hydrocarbons

The aqueous solubilities of phenanthrene, anthracene, 2-methylanthracene, 2-ethylanthracene, 1,2-benzanthracene, and benzo(a)pyrene were determined at temperatures ranging from 3.7 to 25.3°C and salinities ranging from 0 to 36.7‰. With the exception of 1,2-benzanthracene, the hydrocarbons experienced salting-out. Their solubilities were insensitive to small changes in salinity and very sensitive to small changes in temperature. On the other hand, 1,2-benzanthracene experienced salting-in, and its solubility was sensitive to small changes in salinity. Potential environmental implications of the data are discussed.     

(Laser-excited) Shpol'skii fluorometry: applications in marine environmental analysis of polynuclear aromatic hydrocarbons

Shpol'skii spectroscopy is a technique that can be employed to obtain highly resolved spectral signatures of molecules. The high-resolution spectra are obtained by using n-alkanes as solvents that form neat crystalline matrices at low temperatures. The specificity and sensitivity of the Shpol'skii method can be further improved by application of selective laser excitation. Summarizing, Shpol'skii spectra show the highly specific fingerprinting properties of IR spectra, but at the same time have the inherently high sensitivity of fluorescence techniques.In this paper attention will be given to principles and general experimental aspects of the Shpol'skii technique. Furthermore, some applications in environmental analysis will be discussed in more detail: (1) the qualitative determination of polycyclic aromatic hydrocarbons (PAH) in suspended matter collected in estuarine water; (2) the quantitative determination of PAH in NRCC sediment reference material SES-1; and (3) the application of laser-excited Shpol'skii spectroscopy for the qualitative determination of PAH in crude extracts of biotic samples. It is shown that the Shpol'skii technique can be used successfully as an independent reference method for both qualitative and quantitative checks of conventionally used determination methods. Because of the high selectivity of the low-temperature method, PAH can be quantitatively determined without any sample clean-up, even in extremely complex biotic samples.     

Concentrations of unsubstituted polynuclear aromatic hydrocarbons in bay mussels (Mytilus edulis) from Oregon, USA

Concentrations of fifteen unsubstituted polynuclear aromatic hydrocarbons (PNAH) were measured in Mytilus edulis from two sites in Yaquina Bay, Oregon, USA, during 1979–1980. There were significant differences in PNAH levels between the two populations. The average total concentration in mussels inhabiting the more industrialized bayfront was 986·2 μg/kg compared with 273·9 μg/kg in mussels from a more remote site across the bay. Substantial differences were found in the concentrations of different PNAH in M. edulis examined during this study. The smaller more water soluble, compounds were concentrated to one or two orders of magnitude above the larger, less soluble PNAH.     

Exposure of pink salmon embryos to dissolved polynuclear aromatic hydrocarbons delays development,prolonging vulnerability to mechanical damage

Exposure to dissolved polynuclear aromatic hydrocarbons (PAHs) from crude oil delays pink salmon (Oncorhynchus gorbuscha) embryo development, thus prolonging their susceptibility to mechanical damage (shock). Exposure also caused mortality, edema, and anemia consistent with previous studies. Hatching and yolk consumption were delayed, indicating the rate of embryonic development was slowed by PAH exposure. The net result was that exposed embryos were more susceptible to shock than normal, unexposed embryos. Susceptibility to shock was protracted by 4–6 d for more than a month in embryos exposed to exponentially declining, dissolved PAH concentrations in water passed through oiled rock; the initial total PAH concentration was 22.4 μg L⁻¹ and the geometric mean concentration was 4.5 μg L⁻¹ over the first 20 d. Protracted susceptibility to shock caused by exposure to PAHs dissolved from oil could potentially increase the reported incidence of mortality in oiled stream systems, such as those in Prince William Sound after the Exxon Valdez oil spill, if observers fail to discriminate between direct mortality and shock-induced mortality.     

Biotransformation of polycyclic aromatic hydrocarbons in marine polychaetes

Deposit-feeding polychaetes constitute the dominant macrofauna in marine environments that tend to be depositional centers for organic matter and contaminants. Polychaetes are known to accumulate polycyclic aromatic hydrocarbons (PAHs) from both particulate and dissolved phases but less is known about the mechanisms underlying elimination of accumulated PAHs. An important pathway of elimination is through biotransformation which results in increased aqueous solubility of the otherwise hydrophobic PAHs. Biotransformation in marine polychaetes proceeds in a two phased process similar to those well studied in vertebrates, phase I enzymes belonging to the Cytochrome P450 (CYP) enzyme family, along with a few phase II enzymes have been identified in marine polychaetes. In this review we aim at highlighting advances in the mechanistic understanding of PAH biotransformation in marine polychaetes by including data obtained using analytical chemistry and molecular techniques. In marine polychaetes induction of CYP enzyme activity after exposure to PAHs and the mechanism behind this is currently not well established. Conflicting results regarding the inducibility of CYP enzymes from polychaetes have led to the suggestion that induction in polychaetes is mediated through a different mechanistic pathway, which is corroborated by the apparent lack of an AhR homologous in marine polychaetes. Also, none of the currently identified CYP genes from marine polychaetes are isoforms of those regulated by the AhR in vertebrates. Relatively few studies of phase II enzymes in marine polychaetes are currently available and most of these studies have not measured the activity of specific phase II enzymes and identified phase II metabolites but used an extraction technique only allowing determination of the overall amount of phase II metabolites. Studies in insects and various marine invertebrates suggest that in invertebrates, enzymes in the important phase II enzyme family, UDP-glucuronosyl transferases primarily use glucoside as co-substrate as opposed to the vertebrate cosubstrate glucuronic acid. Recent studies in marine polychaetes have however identified glucuronidation of PAHs indicating no mechanistic difference in co-substrate preference among UDP-glucuronosyl transferases between vertebrates and marine polychaetes but it might suggest a mechanistic difference between marine polychaetes and insects.     

Lysosomal responses to a polynuclear aromatic hydrocarbon in a marine snail: Effects of exposure to phenanthrene and recovery

Certain specific aspects of cellular structure-linked functions can be used as rapid and sensitive indicators of cellular responses to environmental stimuli such as chemical contaminants.¹ It is possible to observe structural-functional alterations in lysosomal membrane stability in the cells of some marine organisms at an early stage of such a response to cell injury,^1,2 thus providing an early-warning signal of a potentially deleterious environmental situation. In order to further investigate lysosomal membrane disturbances, mechanisms of injury and capacity for cellular regeneration, the marine snail Littorina littorea was exposed to phenanthrene, which was used as an environmentally widespread and representative polynuclear aromatic hydrocarbon. Lysosomal membrane stability was measured using cytochemical determination of hydrolase latency,² and lysosomal lipofuscin was measured as a possible indicator of enhanced lipid peroxidative damage.³     

多环芳烃化合物对栉孔扇贝组织芳烃羟化酶活力的影响

研究了苯并(a)芘(B[a]P)、苯并(k)荧蒽(B[k]F)以及两者的混合物对栉孔扇贝(Chlamys farreri)鳃丝和消化盲囊芳烃羟化酶(AHH)活力的影响。结果表明,多环芳烃化合物(PAHs)对栉孔扇贝鳃丝和消化盲囊AHH活力具有显著的诱导作用(P<0.05),并且呈现了明显的时间、剂量效应特征。B[a]P和B[k]F混合物处理组鳃丝和消化盲囊的AHH活力在实验期间呈现先升高后稳定趋势,B[a]P处理组则表现峰值变化,然后呈下降趋势。消化盲囊各处理组AHH活力显著高于鳃丝。作者认为可以采用消化盲囊的AHH活力来反映周围环境PAHs的污染,并应以最大饱和浓度为标准。3种PAHs中B[a]P的毒性最强,PAHs对栉孔扇贝的毒性大小与PAHs的组成有关,不能以不同种类单一PAHs毒性的总和来代表PAHs混合物的毒性。     

Immune inhibition in marine mussels by polycyclic aromatic hydrocarbons

Polycyclic aromatic pollutants produced by a range of industrial processes and the combustion of fossil fuels. They eventually enter the marine environment, and are bioaccumulated in the tissues of sessile, filter-feeding bivalves, causing a variety of sublethal effects. Few studies, however, have examined immune inhibition in molluscs by these xenobiotics. Here, the immunotoxic effects of PAHs were investigated in marine mussels (Mytilus edulis) by means of in vivo exposure experiments. Animals were exposed to a PAH cocktail of anthracene, fluoranthene and phenanthrene for 2 or 4 weeks. The haemolymph was then extracted, and phagocytosis and lysosomal neutral red retention assays performed to examine the effects of PAHs on particle uptake by haemocytes and lysosome integrity, respectively. PAHs were found to inhibit phagocytosis and damage lysosomes. It is hypothesized that PAHs exert their toxicity directly on the lysosomes. A possible consequence of such lysosomal damage will be immune impairment in mussels leading to reduced resistance to infectious diseases.     

Observation of abnormal solubility behavior of aromatic hydrocarbons in seawater

The Setschenow and McDevit—Long equations are applied to aromatic hydrocarbons in seawater by using solute surface area and recently available solubility data to evaluate the Setschenow constant. It is demonstrated that this approach avoids a previously encountered problem with the McDevit-Long equation while also pointing out fundamental theoretical discrepancies. Compounds that do not fit the presented semi-empirical relationship are of interest as they may exhibit abnormal partitioning behavior in seawater. Using this approach it is suggested that 1,2-benzanthracene and benzo(a)pyrene exhibit abnormal solution behavior in seawater.     

Sorption of Polycyclic aromatic hydrocarbons by natural estuarine colloids

The sorptive behaviour of natural estuarine colloids was investigated with benzene, naphthalene and anthracene. The equilibrium sorption isotherms were linear. Freundlich partition coefficients normalized to the organic content of the colloids for benzene, naphthalene, and anthracene were 920, 4060 and 510000, respectively. These values are at least an order of magnitude higher than those reported for corresponding soil/sediment systems. This suggests that hydrophobic compounds are more strongly bound to estuarine colloidal organic material.The effect of pH on sorption waas also studied. A significant decrease in sorption was observed when the ambient pH (8·01) of natural water was decreased by a factor of 2. The experimentally determined K_oc values were regressed against the water solubilities of PAHs and compared with a corresponding predictine relationship developed for a soil/sediment system. Such information greatly facilitates prediction of PAH phase partitioning in natural waters.     

Fugacity analysis of polycyclic aromatic hydrocarbons between microplastics and seawater

Recently, the accumulation of plastic debris in the marine environment has become a great concern worldwide. Although plastics are biologically and chemically inert, plastic debris has been suspected of causing adverse effects on ecosystems due to the increase in reactivity by size reduction and/or micropollutants associated with plastics. Because of the high sorption capacity of microplastics toward organic micropollutants, it is suspected that microplastics may play roles in the distribution and fate of micropollutants. In order to quantitatively evaluate the “net flow” of environmental contaminants in water-plastic-organism systems, a fugacity analysis was conducted using concentrations of polycyclic aromatic hydrocarbons (PAHs) in open oceans and in polyethylene as a representative material of plastic debris. Ratio of fugacity in polyethylene to that in seawater showed a decreasing trend with increasing partition coefficient between polyethylene and seawater (K_PE/sw). This indicates that phase equilibrium between polyethylene and seawater is not attained for higher molecular weight PAHs. Disequilibrium of high molecular weight PAHs suggests that transfer from seawater to plastic debris is thermodynamically driven and the role of plastic debris as a vector to transfer them to living organisms would be minimal. However, additives may slowly migrate from plastics into the environment causing potentially serious effects on ecosystems.     

Polycyclic aromatic hydrocarbons in recent sediments from a subtropical estuary in Brazil

The scope of this work was to evaluate the levels of polycyclic aromatic hydrocarbons (PAHs) and their possible sources in two shallow sediment cores from an estuarine area located in the south region of Brazil, the Guaratuba Bay. The estuary is encompassed by an Environmental Protection Area (EPA) of 1306 km², which is still considered to be pristine, despite recent urban growth. To assess levels of 14 selected PAHs in the sediments, among those listed as “priority pollutants” by the US Environmental Protection Agency, the cores were divided in several sections, followed by extraction, clean-up, fractionation and subsequent analysis using HPLC coupled to a fluorescence detector. Among the PAHs detected, phenanthrene and fluoranthene showed the highest concentrations. PAHs with more than four rings were usually present in low concentrations or were undetectable. To assist in the identification of possible sources, the ratios An/(An + Phe) and Flt/(Flt + Py) (anthracene to anthracene plus phenanthrene and fluoranthene to fluoranthene plus pyrene) and a PCA model were also used. Total concentrations of PAHs ranged between 1.5 and 3130 ng/g (mean 495) dry weight for the core collected in the inner part of the estuary, and between 78.5 and 3270 ng/g (mean 899) dry weight for the other core, collected in the outer part. Compared to values found in other studies in coastal zones along South American eastern margin, this area can be considered to range from low polluted to moderately polluted. From the data, it was also possible to conclude that there is predominance of petroleum sources, and essentially close to the more urbanised areas. Combustion sources have only minor contribution and are episodic, when compared to the latter.     

九龙江口红树林区底栖动物体内的多环芳烃

2001年8月和11月在九龙江口红树林区采集了6种底栖动物,测定了它们体内16种多环芳烃的含量.紫游螺(Neritina [Dostia] violacea)、黑口滨螺(Littoraria melanostoma)、可口革囊星虫(Phascolosoma esculenta)、弹涂鱼(Periophthalmus cantonensis)、查加拟蟹守螺(Cerithideadj adjariensis)、孔虾虎鱼(Trypauchen vagina)对沉积物中多环芳烃的富集系数均小于1.弹涂鱼和黑口滨螺体内多环芳烃的含量有随沉积物中多环芳烃含量的增加而增加的趋势,但它们的富集系数却有随沉积物中多环芳烃含量增加而减少的趋势.弹涂鱼、黑口滨螺、查加拟蟹守螺和可口革囊星虫体内多环芳烃主要由二环多环芳烃组成,紫游螺和孔虾虎鱼体内分别是四环和五环多环芳烃比例最高.     

The effect of salinity on the microbial mineralization of two polycyclic aromatic hydrocarbons in estuarine sediments

Sediments from the lower Hudson River estuary and two other coastal environments were examined experimentally for their ability to mineralize (convert to CO₂) the polycyclic aromatic hydrocarbons (PAHs) naphthalene and anthracene over a range of salinities. Routine assays employed 1:1 (vol fresh sed:vol water) sediment slurrys in order to overcome natural variability in mineralization rates among replicates. Mineralization rates were stimulated by about 2·5 fold, compared to unslurried controls, while the coefficient of variation fell from 13% to 3·5%.Rates of naphthalene mineralization in surface sediments from along the mainstem of the Hudson River (salinities from 2 to 27%) ranged from 0·011 to 1·5 nmol cm⁻³ day⁻¹ (pool turnover [T_n] from 60 to 2040 days) with no discernible trends along the estuarine gradient. For two stations examined experimentally (mile point 5, salinity 23%; mile point 26, salinity 5%), microbial assemblages appeared acclimated to broad salinity variations as alter rates of mineralization compared to controls.Sediments from two upstream marshes of the Hudson (mile points 36 and 45) showed rates of naphthalene mineralization from 0·007 to 0·15 nmol cm⁻³ day⁻¹ (T_n from 14 to 368 days), while sediments from a third marsh in freshwater (mile point 76) had high rates (66 nmol cm⁻³ day⁻¹; T_n 40 days). For the two upstream marsh stations which rarely experienced salt intrusion, there was a substantial decrease in mineralization of naphthalene and anthracene with increasing salinity.Consistently high rates of naphthalene mineralization (780 to 1600 nmol cm⁻³ day⁻¹; T_n 5 to 6 days) were observed in petroleum contaminated sediments from Port Jefferson Harbor (PJH) on the north shore of Long Island. PJH has a relatively constant salinity regime (about 27%) and imposed decreases in salinity effected decreases in rates of naphthalene and anthracene mineralization. Lowest rates of naphthalene mineralization (0·003 to 0·004 nmol cm⁻³ day⁻¹; T_n from 714 days to 833 days) were found in sediments from two stations in the relatively pristine Carmans River estuary on the south shore of Long Island.The ability of increases or decreases in salinity to affect the rate of model PAH mineralization appeared to be dependent on the natural variation in the salinity regime from which a sample was obtained. Data from all the environments studied indicated a strong positive correlation between PAH concentration and the rates of mineralization of naphthalene. Rates of PAH mineralization in all environments examined appear to be primarily controlled by the extent of pollutant loading and not by natural variations in the salinity regime.     

长江口外沉积物中多环芳烃结构类型的分布

本文采用色谱—质谱—质谱—计算机系统技术,分析了长江口外两个表层沉积物中多环芳烃组分,并探讨了其有机质的来源和地球化学特征。     

粤东柘林湾表层沉积物中的多环芳烃

近岸海域是绝大数污染物的最终归宿,其中多环芳烃(PAHs)的污染目前已成为国内外环境问题的焦点之一[1~3].20世纪80年代以来,国内外对河口湾、港湾、近岸海域等海洋环境中PAHs的含量、组成、分布、归趋及来源等做了大量的调查[4~15].比如,中国科学院广州地化所对珠三角水域和厦门大学对厦门港一带均做了大量的工作,结果发现表层沉积物中16种优控PAHs总量在珠江口达到156~9220 ng/g,闽江口为175~817ng/g,厦门西港则在196~675 ng/g之间,证明我国东南沿海主要河口及港湾沉积物中的PAHs污染已经达到中等水平[13~15].