Biota: sediment partitioning of aluminium smelter related PAHs and pulp mill related diterpenes by intertidal clams at Kitimat, British Columbia

The question of polycyclic aromatic hydrocarbon (PAH) bioavailability and its relationship to specific PAH sources with different PAH binding characteristics is an important one, because bioavailability drives PAH accumulation in biota and ultimately the biochemical responses to the PAH contaminants. The industrial harbour at Kitimat (British Columbia, Canada) provides an ideal location to study the bioavailability and bioaccumulation of sediment hydrocarbons to low trophic level biota. Samples of soft shell clams (Mya arenaria) and intertidal sediment collected from multiple sites over six years at various distances from an aluminium smelter and a pulp and paper mill were analysed for 106 PAHs, plant diterpenes and other aromatic fraction hydrocarbons. Interpretation using PAH source ratios and multivariate data analysis reveals six principal hydrocarbon sources: PAHs in coke, pitch and emissions from anode combustion from the aluminium smelter, vascular plant terpenes and aromatised terpenes from the pulp and paper mill, petroleum PAHs from shipping and other anthropogenic activities and PAHs from natural plant detritus. Harbour sediments predominantly contain either pitch or pyrogenic PAHs from the smelter, while clams predominantly contain plant derived PAHs and diterpenes from the adjacent pulp mill. PAHs from the smelter have low bioavailability to clams (Biota-Sediment Accumulation Factors; BSAFs <1 for pitch and coke; <10 for anode combustion, decreasing to ∼0.1 for the mass 300 and 302 PAHs), possibly due to binding to pitch or soot carbon matrices. Decreases in PAH isomer ratios between sediments and clams likely reflect a combination of variation in uptake kinetics of petroleum PAHs and compound specific metabolism, with the importance of petroleum PAHs decreasing with increasing molecular weight. Plant derived compounds exhibit little natural bioaccumulation at reference sites, but unsaturated and aromatised diterpenes released from resins by industrial pulping processes are readily accumulated by the clams (BSAFs >500). Thus while most of the smelter associated PAHs in sediments may not be bioavailable to benthic organisms, the plant terpenes (including retene, totarol, ferruginol, manool, dehydroabietane and other plant terpenes that form the chemical defence mechanism of conifers) released by pulp mills are bioavailable and possess demonstrated toxic properties. The large scale release of plant terpenes by some of the many pulp mills located in British Columbia and elsewhere represents a largely undocumented risk to aquatic biota.     

Seasonal differences in the physiology of Carcinus maenas (Crustacea: Decapoda) from estuaries with varying levels of anthropogenic contamination

This study reports the seasonal variability in aspects of the physiology of the shore crab Carcinus maenas from three estuaries in South-west England, each with varying anthropogenic inputs: Avon Estuary (‘relatively low’ impact), Yealm Estuary (‘intermediate’ impact) and Plym Estuary (‘relatively high’ impact). Crabs collected over 12 months from the Avon had a significantly ‘lower’ physiological condition in winter and spring compared to summer and autumn; in particular, haemocyte phagocytic capability (a general indicator of immune function) was significantly higher in winter and spring compared to summer and autumn, and total haemolymph antioxidant status (an indicator of oxidative stress) was significantly lower in winter compared to the remainder of the year. Potentially, shore crabs may be more susceptible to the effects of contaminant exposure, such as increased immunotoxicity (thus, reduction of immune function) and/or oxyradicals (or reactive oxygen species) exposure) especially in seasons of increased susceptibility i.e. summer/autumn (lower phagocytic capability) and winter (lowest antioxidant function). As the Avon was taken to represent the ‘reference’ site, this pattern is considered to reflect the ‘normal’ seasonal variability in shore crab physiology. Shore crab physiological condition from the ‘relatively high’ impact estuary (Plym) revealed increased cellular viability and antioxidant status in autumn and winter compared with that of the ‘standard’ pattern (Avon) However, crabs from the intermediate impact estuary (Yealm) only demonstrated significant physiological differences in summer as shown by a lower cellular viability. All crabs had been exposed to PAHs (confirmed by the presence of PAH metabolites in their urine) which may account for the observed differences in shore crab physiology. In conclusion, to aid understanding of the potential contaminant impacts on biota it is imperative that the ’normal’ seasonal variability of physiological condition be established. Biological effects-based monitoring studies should therefore be employed seasonally to potentially highlight ‘windows of sensitivity’ to contaminant impact.     

DISTRIBUTION AND COMPOSITION OF PAHs IN SURFACE WATERS, POREWATER AND SEDIMENTS FROM XIAMEN WESTERN BAY

Xiamen Western Bay‘s water and sedimem quality were studied by detemaining thelevels of sixteen polycyclic amrrmtic hydrocarbons PAHs in water, porewater and sediment samples from nine locations in the bay. Total PAH concentrations varied from 106 to 945 ng/1 in water, below detectionto 3548 ng/1 in porewater, and 247 to 480 ng/g dry weight in surface sediments. PAHs levels in porewaterwere higher than those in surface water, due to the preference of these hydrophobic compounds for sedimentary phase instead of water. Such a concentration gradient implies a potential flux of pollutants fromsediments to overlying water. The PAils levels in sediments were one to several orders of magnitude lowerthan those in 1993, suggesting their decreased input in recent years and possible degradation with time.     

DISTRIBUTION AND COMPOSITION OF PAHs IN SURFACE WATERS, POREWATER AND SEDIMENTS FROM XIAMEN WESTERN BAY

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Optimization of Minimal Salt Medium for Efficient Phenanthrene Biodegradation by Mycoplana sp. MVMB2 Isolated from Petroleum Contaminated Soil Using Factorial Design Experiments

This study presents the degradation of phenanthrene by Mycoplana sp. MVMB2 isolated from petroleum contaminated soil and the media optimization by factorial design experiments. The Plackett–Burman design was used to evaluate the effects of eight variables (potassium dihydrogen phosphate, disodium hydrogen phosphate, magnesium sulfate, calcium chloride, ferrous sulfate, glucose, inoculum concentration, and phenanthrene concentration) on phenanthrene degradation. Based on the results, the critical medium components having significant influence on the degradation were found to be disodium hydrogen phosphate, magnesium sulfate, ferrous sulfate, and phenanthrene. Furthermore, these four variables were used as central composite design parameters. The optimum minimal salt medium composition obtained by conventional and factorial design experiments for the degradation of phenanthrene by Mycoplana sp. MVMB2 at pH 6.5 and 30°C were found to be, potassium 2.5 g/L dihydrogen phosphate, 0.3505 g/L disodium hydrogen phosphate, 0.5501 g/L magnesium sulfate, 0.02 g/L calcium chloride, 0.0261 g/L ferrous sulfate, 0.6756 g/L phenanthrene, 0.5 g/L glucose, 0.5 g/L ammonium sulfate, and inoculum 5% v/v. The phenanthrene degradation was confirmed by analyzing the metabolites formed.     

Long term monitoring for oil in the Exxon Valdez spill region

In the aftermath of the 1989 Exxon Valdez oil spill, a Long Term Environmental Monitoring Program (LTEMP) has been regularly sampling mussels (and some sediments) for polycyclic aromatic and saturated hydrocarbons (PAH and SHC) at sites in Port Valdez, Prince William Sound, and the nearby Gulf of Alaska region. After 1999, a decreasing trend appears in total PAH (TPAH) in tissues at all sites with current values below 100 ng/g dry weight (many below 50 ng/g). Currently, most samples reflect a predominantly dissolved-phase signal. This new low in TPAH likely represents ambient background levels. Synchrony in TPAH time-series and similarities in the hydrocarbon signatures portray regional-scale dynamics. The five inner Prince William Sound sites show similar composition and fluctuations that are different from the three Gulf of Alaska sites. The two Port Valdez sites represent a unique third region primarily influenced by the treated ballast water discharge from the Alyeska Marine Terminal. Prince William Sound has reverted to a stable environment of extremely low level contamination in which local perturbations are easily detected.     

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.     

Effects of abnormally high heat stress on petroleum in reservoir——An example from the Tazhong 18 Well in the Tarim Basin

An igneous intrusion of 94m thick was discovered intruding into the Silurian sandstone from Tazhong 18 Well. The petroleum previously preserved in the Silurian sandstone reservoir was altered into black carbonaceous bitumen by abnormally high heat stress induced by the igneous intrusion. The reflec-tance of the carbonaceous bitumen reaches as high as 3.54%, indicating that the bitumen had evolved into a high thermal evolution level. Similar to the Silurian samples from the neighboring Tazhong 11, Tazhong 12, Tazhong 45 and Tazhong 47 wells, the distribution of C27, C28 and C29 steranes of the car-bonaceous bitumen is still "V" -shaped and can still be employed as an efficient parameter in oil source correlation. The "V" -shaped distribution indicates that the hydrocarbons from the Tazhong 18 and the neighboring wells were all generated from the Middle-Upper Ordovician hydrocarbon source rocks. However, the oil source correlation parameters associated with and terpanes had been changed greatly by the high heat stress and can no longer be used in oil source correlation. The δ 13C values of the pe-troleum from the neighboring wells are between -32.53‰ and -33.37‰, coincident with those of the Paleozoic marine petroleum in the Tarim Basin. However, the δ 13C values of the carbonaceous bitumen from the Tazhong 18 Well are between -27.18‰ and -29.26‰, isotopically much heavier than the pe-troleum from the neighboring wells. The content of light hydrocarbons (nC14-nC20) of the saturated hydrocarbon fraction in the carbonaceous bitumen is extremely higher than the content of heavy hy-drocarbons. The light/heavy hydrocarbon ratios (ΣnC21-/ΣnC22 ) are between 4.56 and 39.17. In the saturated fraction, the even numbered hydrocarbons are predominant to the odd numbered, and the OEP (Odd to Even Predominance) values are between 0.22 and 0.49. However, the content of light hy-drocarbons in the petroleum from the neighboring wells is relatively low and the content of the even numbered hydrocarbons is almost equal to that of the odd numbered. Compared with the samples from the neighboring wells, the abundance of non-alkylated aromatic hydrocarbons, such as phenanthrenes, and polycyclic aromatic hydrocarbons (PAHs), such as fluoranthane, pyrene, benzo[a]anthracene and benzofluoranthene, are relatively high.     

Emission of fine organic aerosol from traditional charcoal broiling in China

The indoor PM_2.5 aerosol samples for charcoal broiling source under Chinese traditional charbroiling and the ambient fine aerosols samples (PM_2.5) were collected in Beijing to investigate the characteristics of the charcoal broiling source and its impact on the fine organic aerosols in the atmosphere. The concentrations of 20 species of the trace organic compounds, including polycyclic aromatic hydrocarbons (PAHs), fatty acids, levoglucosan, and cholesterol in PM_2.5 were identified and quantified by GC/MS. The total PAHs and fatty acids emitted from charcoal broiling to PM_2.5 were 8.97 and 87,000 ng mg⁻¹ respectively. The concentrations of the light molecular weight (LMW) 3- and 4-ring PAHs were much higher than those of the high molecular weight (HMW) 5- and 6-ring PAHs. Fatty acids were the most abundant species in source profile, accounting for over 90% of all identified organic compounds. More polyunsaturated fatty acid (linoleic acids) than the saturated fatty acid (stearic acids) emitted in the cooking. Charcoal broiling is a minor source of PAHs compared to the source of biomass burning. Comparing the ratios of levoglucosan/fatty acid and levoglucosan/cholesterol in the charcoal broiling samples to the ambient samples, it is evident that meat cooking is an important source of fatty acids, but a less important source of cholesterol. Cooking, as one of the source of fine organic particles, plus other anthropogenic sources would be related to the formation of the severe haze occurred and spread over the urban atmosphere in most of the cities of China in the past several years.     

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.