Polycyclic aromatic hydrocarbons in the Jurassic–Cretaceous Tetori Group,central Japan

Primary data on the organic geochemistry of the Tetori Group provide basic information about depositional environments and thermal maturation of organic matter through two geological sections in the Hokuriku region, central Japan. The thermal maturity of organic matter was evaluated by the methylphenanthrene index‐1. The maturity progressively increases stratigraphically down through the Izumi section in Fukui Prefecture. The estimated vitrinite reflectance equivalent is <1.35% near the top of the section, gradually increasing to >2.0% near the base. The thermal maturation process can account for stratigraphic changes in abundance of PAHs through this section. However, the occasional occurrence of coronene in the middle of the Izumi section is attributed to possible paleo‐wildfires that supplied more coronene to the depositional site. The stratigraphic distribution of PAHs through the Tateyama section, Toyama Prefecture, also can be explained by the same scenario as envisaged for the Izumi section, but weathering and/or other secondary factors may have partly modified primary signals for this section. Polycyclic aromatic sulfur compounds were observed in nearly all samples from both sections, even in samples for which a freshwater paleoenvironment is surmised. Most plausibly, some reduced sulfur was re‐oxidized to elemental sulfur, which persisted in the sediments and may have contributed to the formation of aromatic sulfur compounds. Hence, polycyclic aromatic sulfur compounds do not provide an index to separate marine environments from the freshwater settings for the Tetori Group.     

Semipermeable membrane devices link site-specific contaminants to effects: PART II - A comparison of lingering Exxon Valdez oil with other potential sources of CYP1A inducers in Prince William Sound, Alaska

We deployed semipermeable membrane devices (SPMDs) on beaches for 28 days at 53 sites in Prince William Sound (PWS), Alaska, to evaluate the induction potential from suspected sources of cytochrome P450 1A (CYP1A)-inducing contaminants. Sites were selected to assess known point sources, or were chosen randomly to evaluate the region-wide sources. After deployment, SPMD extracts were analyzed chemically for persistent organic pollutants (POPs) and polycyclic aromatic hydrocarbons (PAH). These results were compared with hepatic CYP1A enzyme activity of juvenile rainbow trout injected with the same extracts prior to clean-up for the chemical analyses. Increased CYP1A activity was strongly associated with PAH concentrations in extracts, especially chrysene homologues but was not associated with POPs. The only apparent sources of chrysene homologues were lingering oil from Exxon Valdez, asphalt and bunker fuels released from storage tanks during the 1964 Alaska earthquake, creosote leaching from numerous pilings at one site, and PAH-contaminated sediments at Cordova Harbor. Our results indicate that PWS is remarkably free of pollution from PAH when nearby sources are absent as well as from pesticides and PCBs generally.     

The Geochemical Effects of Microbial Humic Substances Reduction

As part of a study on microbial redox alteration of humic substances we investigated the potential effect of this metabolism on the fate of heavy metals and hydrocarbons as a result of conformational alteration of the humic molecular structure due to microbial reduction. Our studies indicate that the microbial reduction of humic acids (HA) results in significant morphological and geochemical alterations. X‐ray microscopy analysis indicate that the conformational structure of the humic colloids is altered as a result of the redox change. In the reduced state, the HA appeared as small dense particles, on reoxidation, large loose aggregates were formed. In addition, spectrofluorometric studies indicated that the binding capacity of the HA for naphthalene was decreased by 10% when the HA was reduced. Similarly, the reduced HA yielded higher surface tension values at all concentrations tested which is indicative of a more hydrophilic and less hydrophobic solute. On reoxidation, the surface tension values reverted back to values similar to those obtained for the untreated oxidized HA. These data indicate that the hydrophobicity of the HA is altered on biological reduction of the HA and that this alteration is reversible. In contrast the reduced HA demonstrated a 15% higher affinity for heavy metals such as divalent cobalt than the oxidized HA. In addition to increasing the binding capacity of HA for heavy metals, the reduction of the HA also decreased the bioavailability and toxicity of bound heavy metals such as chromium. When incubated in the presence of Cr(III) and HA, cells of Escherichia coli grew much more rapidly in the presence of the reduced HA suggesting that the higher metal binding capacity of the reduced humic substances resulted in a removal of the Cr(III) from solution and hence reduced its bioavailability and toxicity. These studies demonstrate that HA redox state and reduction of humic acids by microorganisms can have a significant effect on the molecular morphology and binding constants of HA for heavy metals and hydrocarbons and also directly affects the bioavailability of these compounds in the environment.     

Internal recycling of particle reactive organic chemicals in the Chesapeake Bay water column

Hydrophobic organic contaminants (HOCs) may be used as tracers of particle dynamics in aquatic systems. Internal cycling of polychlorinated biphenyls (PCBs) and polycyclic aromatic hydrocarbons (PAHs) were studied in the mesohaline Chesapeake Bay to assess the role of resuspension in maintaining particle and contaminant inventories in the water column, and to compare settling and suspended particle characteristics. Direct measurements of sediment resuspension and settling conducted in conjunction with one of the sediment trap deployments indicate reasonable agreement between measurements of particle flux using the two different methods. Organic carbon and PCB concentrations in settling solids collected in near-surface sediment traps were remarkably lower than concentrations in suspended particles collected by filtration during the trap deployments, but higher PAH concentrations were found in the settling particles. The different behaviors of PAHs and PCBs in the settling particles are due to their different source types and association to different types of particles. Sediment trap collections in near bottom waters were dominated by resuspension. Resuspension fluxes of HOCs measured 2 m above the bay bottom were as high as 2.5 μg/m² day for total PCBs and 15 μg/m² day for fluoranthene, and were 25 and 10 times higher than their settling fluxes from surface waters, respectively. HOC concentrations in the near bottom traps varied much less between trap deployments than HOC concentrations in the surface traps, indicating that the chemical composition of the resuspended particles collected in the near bottom traps was more time-averaged by repeated resuspension than the surface particles.     

On the reactive uptake of gaseous PAH molecules by micron-sized atmospheric water droplets

A falling droplet reactor was used to study the heterogeneous oxidation of gaseous PAH molecules adsorbed on a 92 μm diameter water droplet by ozone. The dynamic partition constant for the PAH between the droplet and air and the first-order surface rate constant was measured. The increase in uptake with ozone concentration was due to increased mass transfer via surface reaction of co-adsorbed ozone and PAH. The surface rate constant was rationalized through the Langmuir–Hinshelwood mechanism. The rate constant was smaller for phenanthrene than naphthalene. The main reaction products identified in the aqueous phase indicated the peroxidic route for surface reaction of ozone with PAH. The heterogeneous reaction rate of ozone with adsorbed phenanthrene at the air–water interface of a 92-μm droplet was estimated to be 9300 times larger than the homogeneous reaction of ozone with phenanthrene in the gas phase and it was 76 times larger than the homogeneous oxidation by hydroxyl radical in the gas phase. For naphthalene that is more volatile, however, the homogeneous reaction with hydroxyl was more important. Increased organic carbon added to the droplet increased both the partition constant for phenanthrene and surface reaction with ozone. The partition constant for a droplet formed from actual fog water was much larger than for pure distilled water.     

Increased zooplankton PAH concentrations across hydrographic fronts in the East China Sea

The Changjiang has transported large quantities of polycyclic aromatic hydrocarbons (PAHs) to the East China Sea (ECS), but information of these pollutants in zooplankton is limited. To understand PAHs pollution in zooplankton in the ECS, total concentrations of PAHs in zooplankton from surface waters were measured. Values of PAHs ranged from 2 to 3500 ng m⁻³ in the ECS, with highest PAHs levels located at the salinity front between the Changjiang Diluted Water (CDW) and the mid-shelf waters. In contrast, concentrations of zooplankton PAHs in the mid-shelf and outer-shelf waters were significantly lower (2–23 ng m⁻³) than those in the CDW. These results demonstrate that PAHs are conspicuously accumulated in zooplankton at the salinity front between the CDW and the mid-shelf waters. These higher levels of PAHs in zooplankton at the salinity front may be further biomagnified in marine organisms of higher trophic levels through their feeding activities.     

Comparative molecular analysis of bacterial communities inhabiting pristine and polluted with polycyclic aromatic hydrocarbons Black Sea coastal sediments

Molecular analysis was applied to characterize bacterial community structure in sediment samples collected from pristine site and oil-polluted Black Sea harbor. Amplified Ribosomal DNA Restriction Analysis (ARDRA) revealed a high similarity in the restriction patterns of both samples thus not demonstrating the effect of the pollutant on the structure of the bacterial communities. Constructed 16S rRNA gene libraries gave more detailed assessment of members. Results showed that α- and γ-Proteobacteria were dominant in the oil polluted site, whereas the pristine site was characterized by prevalence of Actinobacteria. The biodegradative potential of the adapted bacterial community in the oil-polluted sediments was demonstrated by the presence of the aromatic ring hydroxylating dioxygenase genes.     

Hypoxia does not promote naphthalene bioaccumulation in the brown shrimp, Penaeus aztecus

Since increased ventilation is known to be a common strategy used by aquatic animals to cope with hypoxia, we tested in present study the hypothesis that hypoxia can promote the bioaccumulation of naphthalene, a representative polycyclic aromatic hydrocarbon (PAH), in Penaeus aztecus, a penaeid shrimp subject to hypoxia and PAH contamination in the northern Gulf of Mexico. For each of the two naphthalene concentrations, five groups of shrimps were, respectively, subjected to five different conditions, namely, clean seawater under normoxia, seawater containing acetone under normoxia and hypoxia, and seawater containing 10 or 250 μg/L naphthalene under normoxia and hypoxia. Our results suggest that hypoxia does not significantly alter naphthalene bioaccumulation in either the gills or the hepatopancreas of P. aztecus. The absence of a promoting effect of hypoxia on naphthalene bioaccumulation is attributed to the increased disposition of naphthalene when the shrimps are subjected to hypoxia.     

Composition of the water accommodated fractions as a function of exposure times and temperatures

The water accommodated fractions (WAFs) of nine oils in seawater have been studied. The oils range from light condensate to heavy crude, and include one highly biodegraded oil and one very wax rich oil. This study has identified large variations in the chemical composition of WAFs, depending on oil type, temperature, and mixing time. Experiments at different temperatures (2-13 °C) showed that it takes longer time to reach equilibrium at the lowest temperatures, and that this varies for the different oil types. Oils with higher pour point (wax rich oils) need a longer time to establish WAF in equilibrium than oils with lower pour points (naphthenic oils). At 13 °C a mixing time of 48 h, as recommended in standard procedures, seems to be sufficient for asphalthenic and paraffinic oils. The results demonstrated that for WAF prepared from an unknown oil, or at lower temperatures, different mixing times should be tested. Since the WAF often is used in toxicity testing, the toxicity might be underestimated if the mixing time is too short.     

Effects of abnormally high heat stress on petroleum in reservoir

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 reflectance 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 carbonaceous 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 petroleum 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 petroleum 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 hydrocarbons. 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 hydrocarbons 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. Supported by the National Key Basic Research and Development Project (Grant No. 2005CB422103)