Petrowatch: Petroleum hydrocarbons,synthetic organic compounds,and heavy metals in mussels from the Monterey Bay area of central California

Mussel Watch techniques were used to measure the concentrations of petroleum hydrocarbons, synthetic organic hydrocarbons, and trace metals in a preliminary study of the Monterey Bay area in central California. Resident mussels were found to have higher-than-expected petroleum hydrocarbon body burdens in Carmel Bay, an area thought to be relatively contaminant free. A ‘hot spot’ of PCB 1254 and pp′DDE was measured at Año Nueuvo Island, a site previously recognized because of elevated levels of mercury in mussels. PCB 1254 concentrations at Año Nuevo Island were high in relation to the remainder of coastal United States and Baja California, reflecting entrainment of this compound at a biologically active area. The Monterey Harbor Jetty location showed the highest contamination levels for zinc and lead. In fact, this location has the second highest lead concentrations in mussels for the California coast. Biological cycling of certain compounds (PCB, DDT and mercury) in remote locations such as Año Nuevo Island, is hypothesized as a mechanism for these elevated concentrations in mussels. Levels of other synthetic organic hydrocarbons were generally low, with chlordanes showing higher concentrations in the more urbanized locations of the study area, i.e. the Monterey Harbor Jetty.     

Application of the Mussel Watch concept in studies of the distribution of hydrocarbons in the coastal zone of the Ebro Delta

The Mussel Watch concept was applied in a study of man-induced chemical changes in the Ebro Delta on the Catalonian coast to obtain a preliminary assessment of the distribution of synthetic organic compounds, petroleum and biogenic hydrocarbons in the local coastal zone. Mussels, oysters and clams were selected as the indicator organisms. Levels of petroleum accumulated by mussels were generally high, in the order of 100–800 μg^?1 dry weight, equivalent to those in mussels in the most polluted harbours and bays of California. The relative distributions of the steranes and pentacyclic triterpanes in the mussels were significantly different from those found in petroleum from a local field, indicating that local petroleum was not contributing to the present contamination. The composition of biogenic compounds was variable, probably reflecting differences in the composition of local plankton communities, PCB levels were high in relation to current levels in mussels from US sites, reflecting continuing PCB use in Spain. The Delta appears to be a point source of a number of organochlorine compounds, including HCB, the DDT compounds, endrin and γ-chlordane. Levels of the DDT compound o,p′-DDD, a pharmacologically active substance, were unexpectedly high; identification was confirmed by GS/MS. Many unidentified peaks were present on EC chromatograms, indicating a more complex pattern of contamination than might be suggested by printed summaries of data.     

Sources and distribution of aliphatic and polyaromatic hydrocarbons in sediments of Jiaozhou Bay, Qingdao, China

The composition and distribution of aliphatic (n-alkanes) and polyaromatic hydrocarbons (PAHs) were measured for the surface sediments collected at 25 sites from Jiaozhou Bay, Qingdao, China. Total n-alkanes and PAH concentrations ranged from 0.5 to 8.2 microg/gdw and 0.02 to 2.2 microg/gdw, respectively, and the distribution of both n-alkanes and PAHs showed large spatial variations in the bay. The distribution of PAHs in the sediments was predominated by the three or more ring compounds. High hydrocarbon levels were generally found in the areas associated with high anthropogenic impact and port activities in the bay. The calculated hydrocarbon indexes suggest that petroleum contamination was the main source of n-alkanes, while both pyrolytic and petrogenic sources contributed PAHs to the surface sediments of Jiaozhou Bay. In comparison to other polluted coastal sediments, the level of contamination from both aliphatic hydrocarbons and PAHs in Jiaozhou Bay sediments is relatively low at the present time.     

Assessment of tributyltin contamination in a shipyard area using a mussel transplantation approach

Mussels (Mytilus galloprovincialis) were transplanted to seven stations around a large shipyard for 126 days to evaluate tributyltin (TBT) contamination. Although the application of TBT-based paints to ships is totally banned in Korea, butyltin compounds were found to accumulate in mussels following transplantation. Concentrations of TBT and total butyltins in transplanted mussels near the shipyard were in the range of 40-350 ng Sn/g and 74-530 ng Sn/g on a dry weight basis, respectively. Obviously, low TBT concentrations (6.0-53 ng Sn/gdw) were determined in mussels at four stations outside the shipyard. A negative gradient of TBT concentrations and TBT portion to total butyltin concentrations were found in both the surface water and transplanted mussels according to distance from the shipyard. In addition, TBT concentrations in surface water and transplanted mussels showed significant correlation (r(2) = 0.71; p < 0.001). These results indicate that the shipyard still releases fresh TBT into surrounding waters even after TBT regulation in Korea, and mussel transplantation is useful in evaluating TBT contamination in shipyard area.     

Hydrocarbon contamination in sediments from urban stormwater runoff

This investigation showed that urban stormwater runoff provides a significant amount of petrogenic material to receiving waters and sediments. A characteristic hydrocarbon ‘fingerprint’ for sediments and particulate matter in the Hillsborough Reservoir, Hillsborough River and upper Hillsborough Bay was provided. Determination of source material for petroleum contamination in stormwater runoff and river sediment indicated that crankcase oil was a primary contributor to sediment hydrocarbon contamination. A comparison of sediment hydrocarbons with hydrocarbons from stormwater runoff showed that the most probable source of crankcase oil-like petrochemicals found in sediment was the stormwater runoff.A comparison of hydrocarbon composition in suspended particulate matter with that of accumulated bottom sediments in the reservoir, river and bay, during a non-storm period and rising tide showed no resuspension and upriver transport of petroleum contaminated bay sediment. No special influence of the bay upon the lower river was observed relative to hydrocarbon tracers, indicating that most contaminated sediment transport was downriver during storm events. Additional studies should be performed over various tidal cycles and storm events incorporating sediment cores, sediment grain size analysis and hydrocarbon characterization at more closely spaced stations near the river mouth to address adequately the question of specific hydrocarbon pollution sources, rate of petroleum influx and persistence of petrochemical contaminants in the sediment.     

Relationships between tissue concentrations of chlorinated hydrocarbons (polychlorinated biphenyls and chlorinated pesticides) and antioxidative responses of marine mussels,Perna viridis

Marine mussels, Perna viridis, were transplanted from a reference site to various polluted sites around Hong Kong. After 30 d of exposure, antioxidative responses in the gills and hepatopancreas and tissue concentrations of chlorinated hydrocarbons [polychlorinated biphenyls (PCBs) and chlorinated pesticides (CPs)] were determined for individual mussels. Glutathione S transferase (GST) and glutathione (GSH) were positively correlated with tissue PCB concentrations. Only one of the enzymatic antioxidants, glutathione peroxidase (GPx), showed significant response to tissue PCB. No significant correlation was found between tissue concentrations of chlorinated hydrocarbons and other enzymatic antioxidants (superoxide dismutase (SOD), catalase (CAT), glutathione reductase (GR) and NADPH DT-diaphorase (DT-d). Oxidative stress, measured as thiobarbituric acid reactive substances, was correlated with chlorinated pesticide concentrations in tissues. This study demonstrated a correlation between GST/GSH and chlorinated hydrocarbons. The apparent lack of correlation between trace organic pollutants and some of the enzymatic antioxidants may be due to the inhibitory effects caused by these chemicals. The above results suggest that more investigations are needed before these enzymes can be used as biomarkers.     

Relationships between tissue concentrations of chlorinated hydrocarbons (polychlorinated biphenyls and chlorinated pesticides) and antioxidative responses of marine mussels, Perna viridis

Marine mussels, Perna viridis, were transplanted from a reference site to various polluted sites around Hong Kong. After 30 d of exposure, antioxidative responses in the gills and hepatopancreas and tissue concentrations of chlorinated hydrocarbons [polychlorinated biphenyls (PCBs) and chlorinated pesticides (CPs)] were determined for individual mussels. Glutathione S transferase (GST) and glutathione (GSH) were positively correlated with tissue PCB concentrations. Only one of the enzymatic antioxidants, glutathione peroxidase (GPx), showed significant response to tissue PCB. No significant correlation was found between tissue concentrations of chlorinated hydrocarbons and other enzymatic antioxidants (superoxide dismutase (SOD), catalase (CAT), glutathione reductase (GR) and NADPH DT-diaphorase (DT-d). Oxidative stress, measured as thiobarbituric acid reactive substances, was correlated with chlorinated pesticide concentrations in tissues. This study demonstrated a correlation between GST/GSH and chlorinated hydrocarbons. The apparent lack of correlation between trace organic pollutants and some of the enzymatic antioxidants may be due to the inhibitory effects caused by these chemicals. The above results suggest that more investigations are needed before these enzymes can be used as biomarkers.     

Evaluation of the mussel Perna perna as a biomonitor of polycyclic aromatic hydrocarbon (PAH) exposure and effects

The mussel Perna perna was used to monitor and assess areas suspected of oil contamination by transplanting animals from unimpacted to impacted sites and vice versa. The deployment lasted for three months during which total PAH were measured in seawater samples collected every 15 days. PAH concentrations were determined in mussel tissue monthly. The lysosomal neutral red assay and the condition index were used as biomarkers of the adverse biological effects. The PAH concentration in mussels at unimpacted sites, prior to deployment was ca. 100 microg kg(-1) but increased to 300 microg kg(-1) after three months at the contaminated site. Mussels transplanted to the uncontaminated site showed a decrease from 380 to 80 microg kg(-1). Significant changes in lysosomal stability occurred within one month of the beginning of the transposition; in contrast condition indexes were not correlated with the observed changes in PAH concentration.     

Comparative petroleum hydrocarbons levels and biochemical responses in mussels from hydrothermal vents (Bathymodiolus azoricus) and coastal environments (Mytilus galloprovincialis)

Aliphatic hydrocarbons and PAHs in the whole soft tissues of Bathymodiolus azoricus from three Mid-Atlantic Ridge hydrothermal vents (Menez-Gwen, Lucky Strike and Rainbow), and Mytilus galloprovincialis from three contaminated coastal sites in South Portugal were analysed, and its effects on the digestive gland microsomes mixed-function oxygenase system (MFO) were assessed. Aliphatic hydrocarbons levels were present in the same magnitude in both coastal and hydrothermal environments, while the UCM (unresolved complex mixture) for coastal mussels were higher than in vent mussels. In general, significantly higher PAHs concentrations were found in coastal mussels, compared to B. azoricus where low molecular weight PAHs (2-3 rings) represented the majority of PAHs contrarily to what was observed in M. galloprovincialis. The MFO components were present in both mussel species, and were detected in vent mussels for the first time. However this system seems to have different roles in species from these contrasting environments. In coastal mussels MFO responded to hydrocarbon contamination while response in hydrothermal organisms appeared to be related mainly to endogenous factors.     

Asia-Pacific mussel watch: monitoring contamination of persistent organochlorine compounds in coastal waters of Asian countries

Contamination of persistent organochlorines (OCs) such as PCBs (polychlorinated biphenyls), DDT and its metabolites (DDTs), HCH (hexachlorocyclohexane) isomers (HCHs), chlordane compounds (CHLs), and HCB (hexachlorobenzene) were examined in mussels collected from coastal waters of Asian countries such as Cambodia, China, Hong Kong, India, Indonesia, Japan, Korea, Malaysia, Philippines, Far East Russia, Singapore, and Vietnam in 1994, 1997, 1998, 1999, and 2001 to elucidate the contamination status, distribution and possible pollution sources and to assess the risks on aquatic organisms and human. OCs were detected in all mussels collected from all the sampling sites investigated. Considerable residue levels of p,p(')-DDT and alpha-HCH were found in mussels and the concentrations of DDTs and HCHs found in mussels from Asian developing countries were higher than those in developed nations suggesting present usage of DDTs and HCHs along the coastal waters of Asian developing countries. On the other hand, lower concentrations of PCBs detected in mussels from Asian developing countries than those in developed countries indicate that PCBs contamination in mussels is strongly related to industrial and activities. To our knowledge, this is a first comprehensive report on monitoring OCs pollution in the Asia-Pacific region.     

Distribution of hydrocarbons in the oyster,Pinctada margaratifera,along the coast of Kuwait

Concentrations of total hydrocarbons within the boiling point range of the alkanes n-C₁₄ and n-C₃₂ were determined in oysters, Pinctada margaratifera, from coastal waters of Kuwait. Levels of petroleum-derived hydrocarbons were highest in an area adjacent to the major oil loading facilities. Whether the use of dispersants to treat minor spills increases levels of incorporation of petroleum compounds into the food webs could not be concluded from the data of this study. Levels of total petroleum-type hydrocarbons in the oysters at this site were equivalent to those in mussels, Mytilus sp., from harbours, bays and urban coastal areas of California. The Kuwaiti oysters lacked a C₂₈ pentacyclic triterpane that was present in extracts of mussels from southern California that had been recently exposed to a minor spill or to a natural seepage. Levels of DDE and PCB were comparable to those in relatively unpolluted areas of North America.     

Bioaccumulation factors of chlorinated hydrocarbons between mussels and seawater

The bioaccumulation of PCB and DDT compounds by mussels, Mytilus spp., from ambient seawater was determined by measuring concentrations of these chlorinated hydrocarbons in both mussels and seawater at four sites on the Mediterranean coast of France and two sites in California. Bioaccumulation factors were found to vary over an order of magnitude. Ratios of the concentrations of PCB in mussels, consisting predominantly of pentachloro-and hexachlorobiphenyls, to concentrations in ambient seawater ranged between 69 000 and 690 000; the corresponding ratios of concentrations of p,p′-DDE or p,p′-DDT ranged from 40 000 to 690 000. Although mussels appear to be appropriate and convenient indicator organisms of local chlorinated hydrocarbon contamination levels, the factors contributing to this variance must be determined before mussels are widely used in global monitoring programmes.     

Molecular and stable carbon isotopic characterization of PAH contaminants at McMurdo Station, Antarctica

The molecular and stable carbon isotopic compositions of contaminant polycyclic aromatic hydrocarbons (PAHs) at McMurdo Station, Antarctica were analyzed in samples collected from land and sub-tidal area. PAHs in the study areas were characterized by high amounts of naphthalene and alkylated naphthalenes from petroleum products introduced by human activities in the area. Principal component analysis (PCA) of PAH composition data identified multiple sources of PAH contamination in the study area. Compositional assignments of origins were confirmed using compound specific stable carbon isotopic analysis.     

Petroleum and PAH contamination of the Black Sea

Concern has been expressed regarding the extent of contamination of the Black Sea. Analyses of coastal sediments taken from throughout the region indicate, however, that levels of petroleum hydrocarbons (2-300 microg g(-1) dry wt total hydrocarbons) are generally comparable to those encountered in the Mediterranean and are lower than concentrations reported for highly contaminated areas such as the Gulf, Hong Kong, Taiwan and New York Bight. Highest concentrations of total hydrocarbons (>100 microg g(-1) dry wt) were associated with discharges from Odessa, Sochi and the River Danube. Chronic/degraded petroleum was the major contributor at these sites. Samples from the Ukrainian coastline were comparatively clean (<10 microg g(-1) dry wt total hydrocarbons). Major contributions of fresh oil (as indicated by sigma n-C14-34) occur through the River Danube. Concerning total PAH, concentrations (7-638 ng g(-1) dry wt) compare to relatively unpolluted locations in the Mediterranean and are much lower than levels reported for polluted UK estuaries (e.g. Mersey, Tyne, Thames). Both pyrolytic and petrogenic PAH are present in most samples, although petroleum derived PAH are dominant at Sochi and pyrolytic sources are prevalent in the Bosphorus region. The absence of a correlation between total hydrocarbons and PAH (R2 = 0.04) indicates different primary sources for the two.     

Polycyclic aromatic hydrocarbons in sediments,mussels and crustacea around a former gasworks site in Shoreham-by-Sea,UK

Concentrations of polycyclic aromatic hydrocarbons have been determined in sediments, mussels and crustacea in the vicinity of a former gasworks site by Shoreham Harbour, UK. Very high concentrations of PAH were found in the substrate, an ash-like material deposited on the former gasworks site, which exhibited a profile consistent with the major source of contamination being coal or coke tar produced during the period of gas production at the site. Elevated PAH concentrations were also found in mussels both from the beach below the former gasworks site, and from sites further to the east in Portslade and Hove. The significance of these concentrations were assessed using an approach which involved the calculation of benzo[a]pyrene equivalent conoentrations (BaPEs), summing concentrations of individual PAH on the basis of their comparative potency as carcinogens. BaPE ranged from values of, or close to, zero for crustacea, to 336 microg kg(-1) wet weight in mussels from Southwick Beach. The contaminated mussels are not exploited commercially but may be taken by casual gatherers, and notices have been posted to warn potential consumers.     

Comparative petroleum hydrocarbons levels and biochemical responses in mussels from hydrothermal vents (Bathymodiolus azoricus) and coastal environments (Mytilus galloprovincialis)

Aliphatic hydrocarbons and PAHs in the whole soft tissues of Bathymodiolus azoricus from three Mid-Atlantic Ridge hydrothermal vents (Menez-Gwen, Lucky Strike and Rainbow), and Mytilus galloprovincialis from three contaminated coastal sites in South Portugal were analysed, and its effects on the digestive gland microsomes mixed-function oxygenase system (MFO) were assessed.Aliphatic hydrocarbons levels were present in the same magnitude in both coastal and hydrothermal environments, while the UCM (unresolved complex mixture) for coastal mussels were higher than in vent mussels. In general, significantly higher PAHs concentrations were found in coastal mussels, compared to B. azoricus where low molecular weight PAHs (2–3 rings) represented the majority of PAHs contrarily to what was observed in M. galloprovincialis. The MFO components were present in both mussel species, and were detected in vent mussels for the first time. However this system seems to have different roles in species from these contrasting environments. In coastal mussels MFO responded to hydrocarbon contamination while response in hydrothermal organisms appeared to be related mainly to endogenous factors.     

Comparative petroleum hydrocarbons levels and biochemical responses in mussels from hydrothermal vents (Bathymodiolus azoricus) and coastal environments (Mytilus galloprovincialis)

Aliphatic hydrocarbons and PAHs in the whole soft tissues of Bathymodiolus azoricus from three Mid-Atlantic Ridge hydrothermal vents (Menez-Gwen, Lucky Strike and Rainbow), and Mytilus galloprovincialis from three contaminated coastal sites in South Portugal were analysed, and its effects on the digestive gland microsomes mixed-function oxygenase system (MFO) were assessed.Aliphatic hydrocarbons levels were present in the same magnitude in both coastal and hydrothermal environments, while the UCM (unresolved complex mixture) for coastal mussels were higher than in vent mussels. In general, significantly higher PAHs concentrations were found in coastal mussels, compared to B. azoricus where low molecular weight PAHs (2–3 rings) represented the majority of PAHs contrarily to what was observed in M. galloprovincialis. The MFO components were present in both mussel species, and were detected in vent mussels for the first time. However this system seems to have different roles in species from these contrasting environments. In coastal mussels MFO responded to hydrocarbon contamination while response in hydrothermal organisms appeared to be related mainly to endogenous factors.     

Interpretation of Gas Chromatographic Data in Subsurface Hydrocarbon Investigations

Capillary column gas chromatography (GC) is extremely useful in investigations of subsurface contamination by petroleum hydrocarbons. Fluid samples collected from observation wells are evaluated by GC methods to detect and analyze petroleum hydrocarbons in dissolved and liquid phases. The presence, types and concentrations of many petroleum-derived hydrocarbons dissolved in ground water can be determined. GC analysis can also be used to determine the composition of liquid hydrocarbon products, including gasoline, distillates and heavier oils. The degree of degradation of sampled liquid hydrocarbon product can be estimated from GC information, and this information can be helpful in estimating the length of time the product has been in the subsurface. Determination of the hydrocarbon source and migration path can be made from GC analysis of fluid samples collected at two or more locations.
This paper is intended to demonstrate interpretative techniques that can be used by hydrogeologists to facilitate the detection, identification and mitigation of subsurface hydrocarbons.     

Levels of PCBs and DDTs in mussels from the N.W. Mediterranean

The concentration of synthetic chlorinated hydrocarbons has been monitored in mussels collected on the north-west Mediterranean coast. DDT and PCB contamination is widespread in this region and the results suggest that the mussels are directly exposed to DDT. Seasonal changes in fat content of the mussels and the (unknown) rates of chlorinated hydrocarbon accumulation and excretion make the detailed interpretation of data difficult and limit the value of mussels as bio-indicators of pollution.     

The usefulness of transplantation studies in monitoring of metals in the marine environment: South African experience

Due to their close proximity to the point sources of pollution, estuaries and harbours are exposed to metals. Mussels are used worldwide to monitor marine pollution due to their ability to take up contaminants and the ease of transplantation. Mussels were collected from two reference sites and transplanted in Richards Bay Harbour (2006 and 2010) and in three harbours. Transplanted and resident mussels were removed after 6 weeks exposure and metal concentrations were analysed using ICP-MS techniques. Transplanted mussels had higher metal concentrations than the resident mussels. This was attributed to regulation of metals by the resident mussels. Metal regulation was greater in mussels that are continuously submerged as opposed to those that undergo tidal influences. For monitoring it is essential that the reference population for transplantation is considered carefully as upwelling events in the pristine reference location results in significant increases in metal bioaccumulation.