Polycyclic aromatic hydrocarbon sources related to biomarker levels in fish from Prince William Sound and the Gulf of Alaska

Seafloor sediments in Prince William Sound (PWS) and the eastern Gulf of Alaska (GOA) have a substantial regional hydrocarbon background from natural sources including oil seeps and eroding sedimentary rocks along the eastern GOA coast. Polycyclic aromatic hydrocarbons (PAH) from that background appear to be bioavailable to fish. Fish collected from PWS and the GOA in a 1999--2000 biomarker study (bile fluorescent aromatic contaminants and liver ethoxyresorufin O-deethylase) show evidence of exposure to low levels of PAH at all categories of sites sampled. Seafloor sediments at fish sampling sites in the GOA east of PWS and at three PWS site categories (nonspill path, spill path oiled, and spill path not oiled) contain hydrocarbons from four principal sources: regional background, combustion products, residues from the 1989 Exxon Valdez oil spill (EVOS), and Monterey (CA) petroleum residues. GOA sediments between PWS and Yakutat Bay, approximately 350 km to the east, are dominated by regional petrogenic background hydrocarbons (total PAH (TPAH) range approximately 60-3400 ng/g) that are the probable cause of low biomarker levels measured in halibut from this area. PWS sediments contain varying proportions of regional background, combustion products, Monterey residues, and EVOS residues at some spill path sites. Rockfish caught in PWS embayments in 1999 have liver EROD activities that correlate positively with the pyrogenic PAH indicator ratio (FI+Py)/C24Ph. Although traces (<5-100 ng/g TPAH) of EVOS residues were detected in seafloor sediments at some nearshore spill path sites, biomarker levels in fish from those sites are not elevated relative to other sites in PWS.     

Biomarkers in fish from Prince William Sound and the Gulf of Alaska: 1999-2000

To test the hypothesis that biomarker levels in fish collected at Prince William Sound (PWS) sites impacted by the 1989 Exxon Valdez oil spill were higher than those collected at unimpacted sites, a 1999-2000 study collected five fish species and associated benthic sediments from 21 sites in PWS and the eastern Gulf of Alaska (GOA). PWS sites were divided in three oiling categories based upon 1989 shoreline assessments: nonspill path (NSP), spill path oiled (SPO), and spill path not oiled (SPNO). Rockfish (N = 177), rock sole (N = 30), and kelp greenling (N = 49) were collected at near-shore locations (approximately 50-500 m from shore); Pacific halibut (N = 131) and Pacific cod (N = 81) were collected further offshore (approximately 500-7000 m). Fish were assayed for bile fluorescent aromatic contaminants (FAC) and cytochrome P4501A (CYP1A) levels measured as liver ethoxyresorufin O-deethylase (EROD) activity and by immunohistochemistry (IHC) of various tissues. For all species studied at all sites, bile FAC concentrations and CYP1A levels were low and in the same range for fish collected at PWS SPO and SPNO sites relative to NSP sites in PWS and the GOA. Consequently, the hypothesis is rejected for the species studied. The bile FAC results further indicate a pervasive exposure of fish at all sites, including those in the GOA far removed from the effects of the spill, to low levels of polycyclic aromatic hydrocarbons. Analysis of the benthic sediments indicates that the probable sources of this exposure are petrogenic hydrocarbons derived from natural oil seeps and eroding sedimentary rocks in the eastern GOA.     

Sorption of polycyclic aromatic hydrocarbons to oil contaminated sediment: unresolved complex?

Oil is ubiquitous in aquatic sediments and may affect partitioning and bioavailability of hydrophobic organic chemicals (HOCs). In contrast to other sedimentary hydrophobic carbon phases (natural organic matter, soot-like materials), oil residues have hardly received any attention as far as it concerns effects on HOC sorption. This paper describes experimental work dealing with such effects of oil on polycyclic aromatic hydrocarbon (PAH) sorption to sediments. Three different oils were spiked to a marine sediment in concentrations between 0 and 100 g/kg. Sediment-water distribution coefficients (Kd) for six deuterated PAHs were then determined either directly after spiking the oil or after a semi-natural weathering process in the lab (lasting for more than 2 yr). Resulting Kd values demonstrated sorption-reducing (competitive) effects at relatively low oil concentrations and sorption-enhancing effects at high oil concentrations. The latter effects only occurred above a certain threshold [i.e., ca. 15% (w/w) of oil on a sedimentary organic carbon basis] marking the oil concentration at which the hydrocarbon mixture presumably starts forming separate phases. Assuming a two-domain (organic carbon + oil) distribution model, oil-water distribution coefficients (K(oil)) for PAHs were estimated. For fresh oils, log K(oil) values appeared to be very similar for different types of oils, proportional to log K(OW) values and indistinguishable from log K(OC) values. For weathered oils, K(oil) values were also rather independent of the type of oil, but the affinity of low molecular weight PAHs for weathered oil residues appeared to be extremely high, even higher than values reported for most types of soot. Because affinities of high molecular weight PAHs for oils had not changed upon weathering, sorption of all PAHs studied (comprising a log K(OW) range of 4.6-6.9) to the weathered oil residues appeared to be more or less constant (averaged log K(oil) = 7.0 +/- 0.24). These results demonstrate that it is crucial to take the presence of oil and its weathering state into account when assessing the actual fate of PAHs in aquatic environments.     

Development of an immunoassay for the determination of polyaromatic hydrocarbons in plasma samples from oiled seabirds

External exposure assessment of oiled seabirds is undertaken by assessment of the percentage oil coverage of the plumage. Nondestructive monitoring of the toxic fraction of petroleum oils and diesels (polyaromatic hydrocarbons, PAHs) which enters the general circulation (internal exposure burden) of oiled seabirds is rarely undertaken. This is because the traditionally used chromatographic methods for plasma PAH analysis require larger sample volumes than those that can be safely collected from smaller species, such as guillemots (Uria aalge). Furthermore, these methods are not a cost-effective or practical approach for analysis of large numbers of birds in a short time period as part of an oil spill response in wildlife rehabilitation centers. This study describes the modification and validation of a commercially available PAH immunoassay (cRaPID PAH) to enable high-throughput, cost-effective, simple, and rapid determination of total PAH concentrations in 50 microL volumes of plasma. The limit of detection of the assay was 0.1 ng/mL as benzo-apyrene (BaP) equivalents with a working range of 0.120 ng/mL. As further validation of the immunoassay, PAHs were determined by GC-MS. GC-MS data were significantly positively correlated with corresponding immunoassay data for the same birds (r2 = 0.976, p < 0.001). The plasma PAH concentrations of 40 oiled guillemots stranded on U.K. shores were determined using the assay to demonstrate its usefulness for biomonitoring studies. The mean ,PAH concentration observed was 1.05 +/- 0.67 ppm (range 0.02-2.40 ppm as BaP equivalents). The modifications to the cRaPID PAH kit in this study enable nondestructive, high-throughput, semiquantitative determination of PAH concentrations in plasma samples suitable for exposure assessment of oiled seabirds during oil spill response and rehabilitation.     

Molecular and stable carbon isotopic source identification of oil residues and oiled bird feathers sampled along the Atlantic Coast of France after the Erika oil spill

The Erika tanker broke in two close to the Atlantic coast of France on December 12, 1999. On December 25th, some heavy fuel oil released by the tanker came ashore along the French Atlantic Coast. Some oil residues and oiled bird feathers were collected all along the Atlantic Shoreline of France after the wreck of the Erika tanker. The aim of this study was to differentiate oil residues and oiled bird feathers related to the Erika oil spill from the ones resulting from the numerous tar ball incidents which had occurred after the Erika oil spill. Alkane and PAH quantification of oil residues allowed differentiation of the samples collected on the north part of the Atlantic Coast from those collected on the south part of the Atlantic shoreline. All oiled birds appear to have been contaminated by the Erika oil. Samples collected on the south part of the Atlantic Coast contain a different molecular fingerprint compared to the Erika oil indicating that they are not related to the Erika oil spill. Bulk and molecular 13C/12C ratio measurements were performed in order to check the discriminative feature and the stability of the isotopic approach. Bulk stable carbon isotopic composition has been shown to be a valuable screening correlation tool as it confirms the link of samples collected in the north part of the Atlantic Coast with the Erika oil spill. All the samples collected along the south part of the Atlantic Shoreline exhibit 13C-enriched bulk isotopic compositions compared to Erika oil. Molecular isotopic composition of saturated hydrocarbons and of phenanthrene compounds also allows unambiguous differentiation of samples related to the Erika oil spill from those due to tar ball incidents. Over the long-term, when molecular distribution will have been modified by the different processes affecting oil in the marine environment, molecular isotopic composition should then be of particular help for Erika oil residues identification.     

Enhancement of orimulsion biodegradation through the addition of natural marine carbon substrates

Orimulsion is a bitumen-based heavy fuel that is a less expensive alternative to traditional fuel oils. However, because its density is intermediate between that of freshwater and seawater, in the event of a spill, the fuel could strand in the sediments. Previous work indicated that only 0.6-2.7% of the bitumen would degrade in long incubations of marine sediments. We added various natural carbon substrates to stimulate the degradation of bitumen by native populations of benthic bacteria. The concentration and carbon isotopic signature of the respired carbon dioxide was measured to partition the substrates that supported bacterial respiration. We found that the addition of seagrass and pinfish stimulated the degradation of bitumen by as much as 2-9-fold relative to incubations without these substrates. Biodegradation of bitumen may be enhanced by the addition of natural marine carbon substrates and may be a useful approach for bioremediation. Preadaptation of the bacteria to bitumen did not significantly enhance their ability to degrade it.     

Dual (C, H) isotope fractionation in anaerobic low molecular weight (poly)aromatic hydrocarbon (PAH) degradation: potential for field studies and mechanistic implications

Anaerobic polycyclic aromatic hydrocarbon (PAH) degradation is a key process for natural attenuation of oil spills and contaminated aquifers. Assessments by stable isotope fractionation, however, have largely been limited to monoaromatic hydrocarbons. Here, we report on measured hydrogen isotope fractionation during strictly anaerobic degradation of the PAH naphthalene. Remarkable large hydrogen isotopic enrichment factors contrasted with much smaller values for carbon: ε(H) = -100‰ ± 15‰, ε(C) = -5.0‰ ± 1.0‰ (enrichment culture N47); ε(H) = -73‰ ± 11‰, ε(C) = -0.7‰ ± 0.3‰ (pure culture NaphS2). This reveals a considerable potential of hydrogen isotope analysis to assess anaerobic degradation of PAHs. Furthermore, we investigated the conclusiveness of dual isotope fractionation to characterize anaerobic aromatics degradation. C and H isotope fractionation during benzene degradation (ε(C) = -2.5‰ ± 0.2‰; ε(H) = -55‰ ± 4‰ (sulfate-reducing strain BPL); ε(C) = -3.0‰ ± 0.5‰; ε(H) = -56‰ ± 8‰ (iron-reducing strain BF)) resulted in dual isotope slopes (Λ = 20 ± 2; 17 ± 1) similar to those reported for nitrate-reducers. This breaks apart the current picture that anaerobic benzene degradation by facultative anaerobes (denitrifiers) can be distinguished from that of strict anaerobes (sulfate-reducers, fermenters) based on the stable isotope enrichment factors.     

Chlorine and carbon isotopes fractionation during volatilization and diffusive transport of trichloroethene in the unsaturated zone

To apply compound-specific isotope methods to the evaluation of the origin and fate of organic contaminants in the unsaturated subsurface, the effect of physicochemical processes on isotope ratios needs to be known. The main objective of this study is to quantify chlorine and carbon isotope fractionation during NAPL-vapor equilibration, air-water partitioning, and diffusion of trichloroethene (TCE) and combinations of these effects during vaporization in porous media. Isotope fractionation is larger during NAPL-vapor equilibration than air-water partitioning. During NAPL-vapor equilibration, carbon, and chlorine isotope ratios evolve in opposite directions although both elements are present in the same bond, with a normal isotope effect for chlorine (ε(Cl) = -0.39 ± 0.03‰) and an inverse effect for carbon (ε(C) = +0.75 ± 0.04‰). During diffusion-controlled vaporization in a sand column, no significant carbon isotope fractionation is observed (ε(C) = +0.10 ± 0.05‰), whereas fairly strong chlorine isotope fractionation occurs (ε(Cl) = -1.39 ± 0.06‰) considering the molecular weight of TCE. In case of carbon, the inverse isotope fractionation associated with NAPL-vapor equilibration and normal diffusion isotope fractionation cancel, whereas for chlorine both processes are accompanied by normal isotope fractionation and hence they cumulate. A source of contamination that aged might thus show a shift toward heavier chlorine isotope ratios.     

Biomarkers of PAH exposure in an intertidal fish species from Prince William Sound, Alaska: 2004-2005

Polycyclic aromatic hydrocarbon (PAH) exposure biomarkers were measured in high cockscomb prickleback (Anoplarchus purpurescens) fish collected from both previously oiled and unoiled shore in Prince William Sound (PWS), Alaska, to test the hypothesis that fish living in the nearshore environment of the sound were no longer being exposed to PAH from the Exxon Valdez oil spill. Pricklebacks spend their entire lives in the intertidal zone of rocky shores with short-term movements during feeding and breeding restricted to an area of about 15 meters in diameter. Fish were assayed for the PAH exposure biomarkers, bile fluorescent aromatic compounds (FAC), and liver ethoxyresorufin O-deethylase (EROD) activity (a measure of cytochrome P450 1A (CYP1A) monooxygenase activity). Bile FAC concentrations and EROD activities were low and not significantly different in fish from previously oiled and unoiled sites. The similar low EROD activity and bile FAC concentrations in fish from oiled and unoiled shores, supports the hypothesis that these low-level biomarker responses were not caused by exposure of the fish to residues of the spilled oil.     

Resolving the origin of the petrogenic hydrocarbon background in Prince William Sound, Alaska

The dominant sources of the petrogenic hydrocarbon background in benthic sediments of Prince William Sound, AK (PWS), site of the 1989 Exxon-Valdez oil spill, are eroding Tertiary shales and residues of natural oil seepage. Mass balance considerations and statistical analyses of hydrocarbon fingerprints independently indicate that coal contributes generally less than 1% of the polycyclic aromatic hydrocarbons (PAH) and chemical biomarkers in this background. This is environmentally significant because of presumed differences in the bioavailability of PAH in coal, seep oil residues, and shales. Coal particles are present in PWS sediments, but their PAH and chemical biomarker contributions are overwhelmed by those of seep oil residues and organic particles from shales of low-to-high thermally maturity. In the late Tertiary or early Quaternary, the currently exposed and eroding shale formations were heated into the oil-generation window and, consequently, are now relatively rich in extractable PAH and chemical biomarkers. The exposed and eroding coals in the area, in contrast, experienced long hot burial and are now thermally overmature with respect to oil generation. The concentrations of thermally sensitive PAH and biomarker compounds in PWS sediments are not consistent with a mature coal origin but are consistent with the low-to-high maturity shales and seep oils in the area.     

Oil biodegradation and bioremediation: a tale of the two worst spills in U.S. history

The devastating environmental impacts of the Exxon Valdez spill in 1989 and its media notoriety made it a frequent comparison to the BP Deepwater Horizon spill in the popular press in 2010, even though the nature of the two spills and the environments impacted were vastly different. Fortunately, unlike higher organisms that are adversely impacted by oil spills, microorganisms are able to consume petroleum hydrocarbons. These oil degrading indigenous microorganisms played a significant role in reducing the overall environmental impact of both the Exxon Valdez and BP Deepwater Horizon oil spills.     

Sorption of the herbicide dichlobenil and the metabolite 2,6-dichlorobenzamide on soils and aquifer sediments

The worldwide used herbicide dichlobenil (2,6-dichlorobenzonitrile) has resulted in widespread presence of its metabolite 2,6-dichlorobenzamide (BAM) in pore- and groundwater. To evaluate the transport of these compounds we studied the sorption of dichlobenil and BAM in 22 sediment samples of clayey till, sand, and limestone including sediments exhibiting varying oxidation states. Dichlobenil sorbed to all investigated sediments, with a high sorption in topsoils (Kd = 7.4-17.4 L kg(-1)) and clayey till sediments (Kd = 2.7-126 L kg(-1)). The sorption of the polar metabolite BAM was much lower than the sorption of dichlobenil but followed the same tendency with the highest sorption in the topsoils (Kd = 0.24-0.66 L kg(-1)) and in the clayey till sediments (Kd = 0.10-0.93 L kg(-1)). The sorption of both compounds was significantly higher (2-47 times) in the unoxidized (reduced) clayey till than in the weathered (oxidized) clayey till. Such a difference in sorption capacity could neither be explained by a higher organic carbon content, sorption to clay minerals, differences in clay mineralogy, nor by blocking of reactive surface sites on clay minerals by iron oxides. However, by removing an average of 81% of the organic carbon from the reduced clayey till with H2O2, the sorption decreased on average 50%. Therefore, most of the sorption capacity in the reduced clayey till was related to organic carbon, which indicates that sorption processes are affected by changes in organic compound composition due to weathering.     

Chemical fingerprinting of petroleum biomarkers using time warping and PCA

A new method for chemical fingerprinting of petroleum biomakers is described. The method consists of GC-MS analysis, preprocessing of GC-MS chromatograms, and principal component analysis (PCA) of selected regions. The preprocessing consists of baseline removal by derivatization, normalization, and alignment using correlation optimized warping. The method was applied to chromatograms of m/z 217 (tricyclic and tetracyclic steranes) of oil spill samples and source oils. Oil spill samples collected from the coastal environment in the weeks after the Baltic Carrier oil spill were clustered in principal components 1 to 4 with oil samples from the tank of the Baltic Carrier (source oil). The discriminative power of PCA was enhanced by deselecting the most uncertain variables or scaling them according to their uncertainty, using a weighted least squares criterion. The four principal components were interpreted as follows: boiling point range (PC1), clay content (PC2), carbon number distribution of sterols in the source rock (PC3), and thermal maturity of the oil (PC4). In summary, the method allows for analyses of chromatograms using a fast and objective procedure and with more comprehensive data usage compared to other fingerprinting methods.     

Characterization, weathering, and application of sesquiterpanes to source identification of spilled lighter petroleum products

Biomarkers have become increasingly important for identifying the source of spilled oil, due to their specificity and high resistance to biodegradation. The biomarkers most commonly used in forensic investigations are the high molecular weight (MW) tri- and pentacyclic terpanes and steranes. For lighter petroleum products such as jet fuels and diesels, the refining processes remove most high MW biomarkers from the original crude oil feedstock. The smaller bicyclic sesquiterpanes, however, are concentrated in these products. Sesquiterpanes are ubiquitous components of crude oils and ancient sediments. Examination of GC-MS chromatograms of these bicyclic biomarkers using their characteristic fragment ions (m/z 123, 179, 193, and 207) provides a highly diagnostic means for identifying spilled oil, particularly for lighter refined product samples that are difficult to identify by current techniques. In this work, sesquiterpanes in crude oils and petroleum products are identified and characterized, distributions of sesquiterpanes in oils and refined products are compared, the effects of evaporative weathering on sesquiterpane distributions are examined, and a methodology using diagnostic indices of sesquiterpanes is developed for oil correlation and differentiation. Finally, two case studies are presented to illustrate the unique utility of sesquiterpanes for fingerprinting and identifying unknown diesel spills.     

Effect of different carbon substrates on nitrate stable isotope fractionation during microbial denitrification

In batch experiments, we studied the isotope fractionation in N and O of dissolved nitrate during dentrification. Denitrifying strains Thauera aromatica and "Aromatoleum aromaticum strain EbN1" were grown under strictly anaerobic conditions with acetate, benzoate, and toluene as carbon sources. (18)O-labeled water and (18)O-labeled nitrite were added to the microcosm experiments to study the effect of putative backward reactions of nitrite to nitrate on the stable isotope fractionation. We found no evidence for a reverse reaction. Significant variations of the stable isotope enrichment factor ε were observed depending on the type of carbon source used. For toluene (ε(15)N, -18.1 ± 0.6‰ to -7.3 ± 1.4‰; ε(18)O, -16.5 ± 0.6‰ to -16.1 ± 1.5‰) and benzoate (ε(15)N, -18.9 ± 1.3‰; ε(18)O, -15.9 ± 1.1‰) less negative isotope enrichment factors were calculated compared to those derived from acetate (ε(15)N, -23.5 ± 1.9‰ to -22.1 ± 0.8‰; ε(18)O, -23.7 ± 1.8‰ to -19.9 ± 0.8‰). The observed isotope effects did not depend on the growth kinetics which were similar for the three types of electron donors. We suggest that different carbon sources change the observed isotope enrichment factors by changing the relative kinetics of nitrate transport across the cell wall compared to the kinetics of the intracellular nitrate reduction step of microbial denitrification.     

Polyaromatic hydrocarbon and PAH metabolite burdens in oiled common guillemots (Uria aalge) stranded on the east coast of England (2001 -2002)

Aside from the physical effects of oiling (e.g., hypothermia, dehydration, emaciation), chronic toxicity of polycyclic aromatic hydrocarbons (PAHs) contamination is an important factor influencing long-term recovery of oiled sea birds following an oil spill. Monitoring PAH exposure can help identify populations at risk from toxic effects of PAHs for further study and/or protection. This is the first studyto quantify PAH and metabolite tissue burdens in sea birds directly oiled following oil spills. PAHs and hydroxylated PAHs were quantified in liver samples from oiled Common Guillemots (Uria aalge) stranded along the East Coast of England using gas chromatography-mass spectroscopy (GC-MS). Mean parent and metabolite PAH concentrations were 0.25+/-0.09 (range 0.04-0.97) and 0.52+/-0.14 (range 0.05-1.48) microg/g (wet wt.), respectively. The main source of PAH exposure was via ingestion of crude oil during preening, resulting in PAH uptake and tissue contamination beyond levels expected from exposure via the food chain. PAH composition corresponded with number of benzene rings in each compound and was typical of contamination from petrogenic sources; pentacyclic < tri- and tetracyclic < tricyclic < dicyclic PAHs. The occurrence of PAH metabolites detected in liver samples also provided evidence of the presence and stereoselectivity of hepatic microsomal CYP1A1 in common guillemots.     

Determination of microbial carbon sources in petroleum contaminated sediments using molecular 14C analysis

Understanding microbial carbon sources is fundamental to elucidating the role of microbial communities in carbon cycling and in the biodegradation of organic contaminants. Because the majority of anthropogenic contaminants are either directly or indirectly derived from fossil fuels that are devoid of 14C, radiocarbon can be used as a natural inverse tracer of contaminant carbon in the contemporary environment. Here, 14C analysis of individual microbial phospholipid fatty acids (PLFA) was used to characterize the carbon sources utilized bythe active microbial community in salt marsh sediments contaminated by the Florida oil spill of 1969 in Wild Harbor, West Falmouth, MA. A specific goal was to determine whether this community is actively degrading petroleum residues that persist in these sediments. The delta14C values of microbial PLFA in all sediment horizons (contaminated and noncontaminated) matched the delta14C of the total sedimentary organic carbon after petroleum removal, indicating that no measurable metabolism of petroleum residues was occurring. This result agrees with ancillary data such as the delta13C content and distribution of PLFA, and the residual hydrocarbon composition determined by comprehensive two-dimensional gas chromatography (GCxGC) analysis. We hypothesize that microbes have chosen to respire the natural organic matter rather than the residual petroleum hydrocarbons because the former is more labile. Future efforts directed at determining indices of microbial degradation of petroleum hydrocarbons should consider competition with natural organic matter.     

Genotoxicity and endocrine-disruption potentials of sediment near an oil spill site: two years after the Hebei Spirit oil spill

The Hebei Spirit oil spill episode (December 7, 2007) has affected the western coastal area of South Korea; however, there is limited information on the potential toxicity of the oil spill to the ecosystem or humans. The potential toxicity of sediments collected from the affected area (n = 22) 2 years after the spill was evaluated. Acute lethal toxicity tests using Vibrio fischeri and Moina macrocopa and tests for genotoxicity and alteration of steroidogenesis using chicken DT40 cells and H295R cells, respectively, were conducted. Both crude and weathered oil extracts were evaluated in order to link the observed toxicity in the sediment extracts to the oil spill. Whereas toxicity to bacteria and daphnids was observed in only two elutriate samples, 10 of the 22 sediment extracts showed genotoxic potential in DT40 cells. The mechanisms of genotoxicity involved nucleotide excision repair (XPA(-/)), homologous recombination (RAD54(-/-)), and translesion synthesis pathways (REV3(-/-)). In addition, nine sediment extracts caused significantly greater production of E2 in H295R cells, and significant up-regulation of CYP19, CYP11B2, and 3βHSD2 by sediment extracts was observed. The pattern of toxicities observed in both crude and weathered oil samples was similar to that observed in the sediment extracts. The genotoxicicity and endocrine-disruption potential of the sediment extracts suggest a need for long-term followup for such toxicity in humans and wildlife in this area.     

Cellular physiological assessment of bivalves after chronic exposure to spilled Exxon Valdez crude oil using a novel molecular diagnostic biotechnology

The objective of this study was to determine the cellular physiological status of the bivalves Mya arenaria and Mytilus trossulus in an area experiencing a 10-yr chronic exposure of spilled Exxon Valdez crude oil in Prince William Sound. Bivalves were collected from well-characterized oiled and unoiled sites. We used a novel biotechnology (Environmental Cellular Diagnostic System) to determine (i) if bivalves were physiologically stressed, (ii) the nature of the altered physiological state, and (iii) whether the bivalves were responding to an exposure of polyaromatic hydrocarbons (PAH). Molecular diagnostic analysis indicated that bivalves at the oiled site were experiencing both oxidative and xenobiotic stress, resulting in increased protein turnover and chaperone activity. Bivalves from the impacted area were responding specifically to a PAH-xenobiotic exposure and accumulating protein-PAH adducts. Finally, species-specific responses were observed that could be related to the habitat preferences of each species. We conclude that bivalves inhabiting a site impacted by crude oil from the 1989 Exxon Valdez spill showed clear indications of cellular physiological stress.     

Measurement of emissions from air pollution sources. 4. C1-C27 organic compounds from cooking with seed oils

The emission rates of gas-phase, semivolatile, and particle-phase organic compounds ranging in carbon number from C1 to C27 were measured from institutional-scale food cooking operations that employ seed oils. Two cooking methods and three types of seed oils were examined: vegetables stir-fried in soybean oil, vegetables stir-fried in canola oil, and potatoes deep fried in hydrogenated soybean oil. The emission rates of 99 organic compounds were quantified, and these include n-alkanes, branched alkanes, alkenes, n-alkanoic acids, n-alkenoic acids, carbonyls, aromatics, polycyclic aromatic hydrocarbons (PAH), and lactones. Carbonyls and fatty acids (n-alkanoic and n-alkenoic acids) make up a significant portion of the organic compounds emitted from all three seed oil cooking procedures. The compositional differences in the organic compound emissions between the different cooking operations are consistent with the differences in the organic composition of the various cooking oils used. The distribution of the n-alkanoic acids between the gas and particle phases was found to be in good agreement with gas/particle partitioning theory. The relative importance of emissions from commercial deep frying operations to the total emissions of C16 and C18 n-alkanoic acids in the Los Angeles urban area was estimated using the available information and is estimated to account for approximately 7% of the total primary emissions of these acids. Additional emissions of these n-alkanoic acids from stir-frying and grill frying operations are expected. Estimates also indicate that seed oil cooking may make up a significant fraction of the emissions of lighter n-alkanoic acids such as nonanoic acid.