Resolving the unresolved complex mixture in petroleum-contaminated sediments

Comprehensive two-dimensional gas chromatography (GC x GC) was used to investigate the chemical composition of the unresolved complex mixture (UCM) of hydrocarbons in petroleum-contaminated marine sediments. The UCM hydrocarbons were extracted and separated with silica and silver-impregnated silica gel chromatography to yield four fractions (branched alkanes and cycloalkanes, monoaromatics, naphthalenes, and multi-ring PAHs) prior to GC x GC analysis. GC x GC separations used a poly-(dimethylsiloxane) stationary phase for volatility selectivity on the first dimension and a 14% cyanopropylphenyl polysiloxane phase for polarity selectivity on the second dimension to fully resolve monoaromatic, naphthalene, and multi-ring PAH compounds from the UCM. A chiral gamma-cyclodextrin phase was used for shape selectivity on the second GC x GC dimension to resolve individual branched alkanes and cycloalkanes in the saturates fraction of the UCM. The ability of GC x GC to resolve thousands of individual chemical components from the UCM will facilitate an understanding of the sources, weathering, and toxicity of UCM hydrocarbons.     

Spatial variations and chronologies of aliphatic hydrocarbons in Lake Michigan sediments

Four sediment cores were collected in fine-grained depositional areas of the southern basin of Lake Michigan. Spatial variations of aliphatic hydrocarbons in surficial sediments were consistent with a lakeward movement of riverine sediments in a series of resuspension-settling cycles in which an unresolved complex mixture (UCM) of hydrocarbons associated with dense sediments is deposited in nearshore areas, fine-grained sediments of terrestrial origin accumulate in the deep basin, and planktonic hydrocarbons are depleted by microbial degradation during transport to the deep basin. The rate of accumulation of the UCM (a marker of petroleum residues) in deep basin sediments has increased by more than an order of magnitude since 1880, from 60 microg m(-2) x a(-1) to approximately 960 microg m(-2) x a(-1) in 1980. Crude estimates of the atmospheric loading of the UCM (1100 microg m(-2) x a(-1)) indicate that accumulations in deep-basin sediments might be supported by atmospheric deposition. Agreement was poor between the atmospheric flux of the terrestrial n-alkanes (sigmaC25, C27, C29, C31) to the deep basin (3200 microg m(-2) x a(-1)) and the sediment accumulation rate (660 microg m(-2) x a(-1)). Understanding of atmospheric fluxes, estimated from the very few available data, would be improved by more frequent measurement of the levels of aliphatic hydrocarbons in air and precipitation and a better knowledge of the particle deposition velocities and precipitation scavenging coefficients.     

Sources, vertical fluxes, and accumulation of aliphatic hydrocarbons in coastal sediments of the Río de la Plata Estuary, Argentina

Settling particles and underlying sediments collected at 1, 2.5 and 4 km off the metropolitan Buenos Aires coast were analyzed to evaluate the sources and accumulation of resolved (RES), unresolved (UCM), and biomarker aliphatic hydrocarbons. Sedimentary aliphatic concentrations (RES 0.11-14 microg x g(-1); UCM 0.1-800 microg x g(-1)) included variability associated with north-south gradients and an exponential offshore reduction. Highest concentrations were registered close to Buenos Aires port and sewer, compared to cleaner northern stations and southward sites affected by a seaward residue transport. Sediment traps deployed in the sewer area revealed large hydrocarbon (38 and 319 mg x m(-2) x day(-1), RES and UCM) and total organic carbon fluxes (29 +/- 26 g x m(-2) x day(-1). The composition of RES and hopanes evaluated by principal component analysis indicated a consistent offshore gradient defined bythe relative contribution of lower vs higher molecular weight components. Distant sites showed decreasing proportions of petrogenic n-C(17-26) alkanes, isoprenoids, and C(20-27) terpanes and relative enrichment of n-C(27,29,31,33) terrestrial plant alkanes and C(31-33) homohopanes. Sediment hydrocarbon profiles showed an average 2-fold reduction down to 20 cm depth with preferential removal of lower molecular weight components and enrichment of n-C(23-35) alkanes and hopanes. Sediment inventories and trap depositional fluxes indicate the accumulation of 5800-9700 tons of aliphatic hydrocarbons in the top 0-5 cm sediments with a strong interfacial alteration and selective preservation of refractory components: n-C(13-22) (1.0%) < isoprenoids (3.2%) < n-C(23-35) (6.1%) < hopanes (47%) approximately UCM (50%), compared to intermediate stability of organic carbon (12%) and quantitative preservation of polychlorinated biphenyls (PCBs) (91%).     

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.     

Disentangling oil weathering using GC x GC. 2. Mass transfer calculations

Hydrocarbon mass transfers to the atmosphere and water column drive the early weathering of oil spills and also control the chemical exposures of many coastal wildlife species. However, in the field, mass transfer rates of individual hydrocarbons to air and water are often uncertain. In the Part 1 companion to this paper, we used comprehensive two-dimensional gas chromatography (GC x GC) to identify distinct signatures of evaporation and dissolution encoded in the compositional evolution of weathered oils. In Part 2, we further investigate patterns of mass removal in GC x GC chromatograms using a mass transfer model. The model was tailored to conditions at a contaminated beach on Buzzards Bay, MA, after the 2003 Bouchard 120 oil spill. The model was applied to all resolved hydrocarbon compounds in the C11-C24 boiling range, based on their GC x GC-estimated vapor pressures and aqueous solubilities. With no fitted parameters, the model successfully predicted GC x GC chromatogram patterns of mass removal associated with evaporation, water-washing, and diffusion-limited transport. This enabled a critical field evaluation of the mass transfer model and also allowed mass apportionment estimates of hundreds of individual hydrocarbon compounds to air and water. Ultimately, this method should improve assessments of wildlife exposures to oil spill hydrocarbons.     

Analysis of nonylphenol isomers in a technical mixture and in water by comprehensive two-dimensional gas chromatography-mass spectrometry

Nonylphenol (NP) is a degradation product of nonylphenol polyethoxylate surfactants and has been reported to occur in water and sediments from urban areas. Technical NP is composed of several structural isomers, and conventional gas chromatography-mass spectrometry techniques have tentatively identified up to 22 components. Isolation and characterization of individual isomers in a technical NP mixture is important, because of the differences in estrogenic and bioaccumulation potential among the isomers. In this study, comprehensive two-dimensional gas chromatography (GC x GC) combined with mass spectrometry (MS) enabled tentative identification of 102 components of NP from a technical mixture. GC x GC-MS was also used to quantify two NP isomers in river water samples. This is the first study to use GC x GC-MS to characterize NP isomers in technical mixtures and for quantitative analysis of NP in river waters.     

Synthetic musk fragrances in Lake Erie and Lake Ontario sediment cores

Two sediment cores collected from Lake Ontario and Lake Erie were sectioned, dated, and analyzed for five polycyclic musk fragrances and two nitro musk fragrances. The polycyclic musk fragrances were HHCB (Galaxolide), AHTN (Tonalide), ATII (Traseolide), ADBI (Celestolide), and AHMI (Phantolide). The nitro musk fragrances were musk ketone and musk xylene. Chemical analysis was performed by gas chromatography/mass spectrometry (GC/MS), and results from Lake Erie were confirmed using gas chromatography/triple-quadrupole mass spectrometry (GC/MS/MS). The chemical signals observed at the two sampling locations were different from each other primarily because of large differences in the sedimentation rates at the two sampling locations. HHCB was detected in the Lake Erie core whereas six compounds were detected in the Lake Ontario core. Using measured fragrance and 210Pb activity, the burden of synthetic musk fragrances estimated from these sediment cores is 1900 kg in Lake Erie and 18 000 kg in Lake Ontario. The input of these compounds to the lakes is increasing. The HHCB accumulation rates in Lake Erie for 1979-2003 and 1990-2003 correspond to doubling times of 16 +/- 4 and 8 +/- 2 years, respectively. The results reflect current U.S. production trends for the sum of all fragrance compounds.     

Isotopic constraints on the fate of petroleum residues sequestered in salt marsh sediments

To provide a new perspective on the fate of petroleum in the marine environment, we utilized variations in the natural abundance of radiocarbon (14C) to detect and quantify petroleum residues that have persisted in Wild Harbor sediments, West Falmouth, MA, for more than 30 years. The 5730-yr half-life of 14C makes this isotope ideal for the detection of fossil-fuel-derived contaminants (14C free) within different fractions of natural organic matter (modern 14C content) in environmental matrixes. Samples of both contaminated and uncontaminated sediments were sequentially treated, first by solvent extraction, followed by saponification, and then acid hydrolysis. Radiocarbon analysis of the sediment residues and select extracts was performed to probe for the presence of fossil fuel contaminants and/or their metabolites in different pools of sedimentary organic matter. Our results indicate that the majority of fossil carbon is solvent-extractable and has not been incorporated in the insoluble organic matter in sediment. Unextracted sediments contaminated with petroleum contain significantly less 14C than extracted sediments, and isotope mass balance calculations suggest that up to approximately 9% of the total organic carbon (TOC) in the petroleum contaminated sediment horizons is derived from solvent-extractable petroleum. These estimates are similar to values calculated when the total quantities of oil (measured by gas chromatography with flame ionization detector (GC-FID)) are compared to TOC content (determined by elemental analysis). These results pave the way for applications of this isotopic approach to more complex environmental systems where the fate of contaminants is less certain.     

豆渣石油醚萃取物的FT-IR和GC/MS分析

为了解豆渣中小分子物质的赋存形态,本研究用石油醚作溶剂在索式萃取器中对豆渣进行了萃取,并采用傅里叶转换红外光谱仪(FT-IR)和气相色谱/质谱联用仪(GC/MS)对所得石油醚萃取物进行分析,同时用FT-IR对原料豆渣和萃余残渣也进行了分析。结果表明:实验连续萃取5 h,所得石油醚萃取物为淡黄色油状物,萃取率为10.7%;原料和萃余残渣的红外谱图峰形相近,但各吸收峰的吸收强度有所不同,而石油醚萃取物与原料和萃余残渣的红外谱图有明显的差别;石油醚萃取物中共检测到35种GC/MS可识别小分子有机化合物,主要分为烷烃、烯烃、芳香烃、醛、酸、酯及其它类物质7种类别;其中,酯类化合物相对含量为最多,高达61.79%。该研究在开发豆渣的高附加值利用方面具有重要的基础理论意义。     

Secondary organic aerosol formation from intermediate-volatility organic compounds: cyclic, linear, and branched alkanes

Intermediate volatility organic compounds (IVOCs) are an important class of secondary organic aerosol (SOA) precursors that have not been traditionally included in chemical transport models. A challenge is that the vast majority of IVOCs cannot be speciated using traditional gas chromatography-based techniques; instead they are classified as an unresolved complex mixture (UCM) that is presumably made up of a complex mixture of branched and cyclic alkanes. To better understand SOA formation from IVOCs, a series of smog chamber experiments was conducted with different alkanes, including cyclic, branched, and linear compounds. The experiments focused on freshly formed SOA from hydroxyl (OH) radical-initiated reactions under high-NO(x) conditions at typical atmospheric organic aerosol concentrations (C(OA)). SOA yields from cyclic alkanes were comparable to yields from linear alkanes three to four carbons larger in size. For alkanes with equivalent carbon numbers, branched alkanes had the lowest SOA mass yields, ranging between 0.05 and 0.08 at a C(OA) of 15 μg m(-3). The SOA yield of branched alkanes also depends on the methyl branch position on the carbon backbone. High-resolution aerosol mass spectrometer data indicate that the SOA oxygen-to-carbon ratios were largely controlled by the carbon number of the precursor compound. Depending on the precursor size, the mass spectrum of SOA produced from IVOCs is similar to the semivolatile-oxygenated and hydrocarbon-like organic aerosol factors derived from ambient data. Using the new yield data, we estimated SOA formation potential from diesel exhaust and predict the contribution from UCM vapors to be nearly four times larger than the contribution from single-ring aromatics and comparable to that of polycyclic aromatic hydrocarbons after several hours of oxidation at typical atmospheric conditions. Therefore, SOA from IVOCs may be an important contributor to urban OA and should be included in SOA models; the yield data presented in this study are suitable for such use.     

Sequestration of nonylphenol in sediment from Bohai Bay, North China

The ubiquity of nonylphenol (NP) in aquatic environments has been well documented, and the long-term fate of NP in sediments is a concern from the viewpoint of risk assessment due to its endocrine-disrupting effects. This paper reports on the assessment of long-term fate of NP in marine sediments by determining extractable and nonextractable fractions of NP in surface sediments and a sediment core from Bohai Bay, North China. The extractable fraction was operationally defined as the fraction of NP that was extracted with a solvent mixture of methanol/methylene chloride, and the nonextractable fraction was the portion of NP that can be released from the sediments by alkaline hydrolyzing after the initial solvent extraction. The total concentrations (extractable and nonextractable) of NP were 3.4-34.3 ng/g dw in the surface sediments and 2.2-17.7 ng/g dw in the sediment core. Depending on the sedimentation time, the percentage of nonextractable NP relative to the total NP in the core ranged from 38 to 99%. Based on the relationship between the percentage of nonextractable NP in sediments and sedimentation time, the sequestration rate of NP in the sediment core from Bohai Bay was estimated to be 0.94% x a(-1). These results have important implications in understanding the geochemical fate of NP in sediments.     

Disentangling oil weathering using GC x GC. 1. chromatogram analysis

Historically, the thousands of compounds found in oils constituted an "unresolved complex mixture" that frustrated efforts to analyze oil weathering. Moreover, different weathering processes inflict rich and diverse signatures of compositional change in oil, and conventional methods do not effectively decode this elaborate record. Using comprehensive two-dimensional gas chromatography (GC x GC), we can separate thousands of hydrocarbon components and simultaneously estimate their chemical properties. We investigated 13 weathered field samples collected from the Bouchard 120 heavy fuel oil spill in Buzzards Bay, Massachusetts in 2003. We first mapped hydrocarbon vapor pressures and aqueous solubilities onto the compositional space explored by GC x GC chromatograms of weathered samples. Then we developed methods to quantitatively decouple mass loss patterns associated with evaporation and dissolution. The compositional complexity of oil, traditionally considered an obstacle, was now an advantage. We exploited the large inventory of chemical information encoded in oil to robustly differentiate signatures of mass transfer to air and water. With this new approach, we can evaluate mass transfer models (the Part 2 companion to this paper) and more properly account for evaporation, dissolution, and degradation of oil in the environment.     

Characterization and FATE of PAH-contaminated sediments at the Wyckoff/Eagle Harbor Superfund Site

Eagle Harbor, a shallow marine embayment of Bainbridge Island, WA approximately 10 miles west of Seattle, WA), was formerly the site of the Wyckoff wood-treatment facility. The facility used large quantities of creosote in its wood-treating processes from the early 1900s to 1988. Historical creosote seepage into the harbor resulted in substantial accumulation of polycyclic aromatic hydrocarbon (PAH) contamination in the harbor sediments over time. This investigation focused on the distribution and fate of the PAH-contaminated harbor sediments. Analyses of 10 sediment cores using total petroleum hydrocarbon (TPH) fingerprinting, the distribution of 50 PAH analytes, and sediment age dating revealed the contributions of three distinct sources of PAHs to sediment contamination in the harbor during various periods over the past 100 years; namely, creosote, urban runoff, and natural background. Surface sediments (upper 20-30 cm) in the cores closestto the Wyckoff wood-treatment facility and southeast of an existing cap were dominated by urban runoff and weathered creosote; the deeper sediments (> 30 cm) were heavily contaminated with relatively unweathered creosote and some pure-phase creosote. Cores located the furthest from the area of contamination, in the center of the harbor, were dominated by urban runoff, showed no signs of creosote contamination, and had much lower PAH and TPH concentrations than those adjacent to the facility. In the four cores in the center of the Harbor, farthest from the former Wyckoff facility, PAH concentrations increased significantly (p < 0.01) with proximity to the northern shore of the harbor, which is more heavily developed than the southern shore and is where all automobile traffic enters and exits the island through the Bainbridge Island ferry terminal. Deeper portions of these cores were contaminated primarily with natural background PAHs, likely representing preurbanization sediments. Sedimentation rates ranged from 0.54 to 1.10 gm/ cm2 in the four cores located in the middle of the harbor, and for the single nearshore core that could be used to calculate sedimentation rates. Recognition that urban runoff has been a fairly consistent and ongoing source of PAHs to the harbor's sediments for the past 50-70 years may influence future sediment management decisions for this site with respect to long-term monitoring of surface sediments to assess cap performance. The results provided information on the ability of Eagle Harbor sediments to recover under natural conditions, identified the occurrence of creosote-derived PAH weathering in off-cap surface sediments, and distinguished between these distinct PAH sources in the harbor (creosote, urban runoff, and natural background).     

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.     

Historical trends in mercury sedimentation and mixing in the Strait of Georgia, Canada

Seventeen sediment cores collected in the Strait of Georgia reveal a history of mercury contamination that began in the 1860s and include episodic contamination during World War II and in the late 1960s. Surface sediment mercury concentrations ranged from 60 to 420 ng/g dry weight and the current fluxes to sediments are estimated at 5-181 ng cm(-2) a(-1). In one location in Port Moody Arm, a Hg spill seems to have sufficiently poisoned the sediments to eliminate biomixing for about 20 years. Although the surface concentration of Hg is likely to decrease at all stations in coming years, sites in the industrialized Vancouver Harbor and Port Moody Arm will continue to be sufficiently contaminated to endanger benthic organisms. Variations in sedimentation and mixing rates among sites result in surface sediment Hg concentration patterns that do not reflect accurately the distribution of Hg flux. In particular, the concentration of Hg in sediments near the mouth of the Fraser River is low, despite the high Hg load of that river, because of dilution by other particles. A preliminary Hg budget indicates that most of the Hg enters the Strait of Georgia via the Fraser River (2090 kg a(-1)), and that, while burial in Strait of Georgia sediments is a major sink (1800 kg a(-1)), there may be a significant outflow of Hg through Juan de Fuca Strait (approximately 3400 kg a(-1)).     

Comparative evaluation of background anthropogenic hydrocarbons in surficial sediments from nine urban waterways

Anthropogenic hydrocarbons in surficial urban sediments derived from nonpoint sources (e.g., stormwater runoff, surface runoff, direct atmospheric deposition, and small but persistent discharges) are the principal characteristics of "urban background". Establishing the character and concentration of urban background helps determine the incremental impacts from point sources and develop successful remedial strategies. In this study, we compared the nature and amount of total extractable hydrocarbons (THC) and polycyclic aromatic hydrocarbons (PAHs), including alkylated PAHs, within 280 surficial (mostly 0-10 cm) sediments from nine, well-studied urban waterways on the East and West U.S. Coasts. These 280 sediments were predominantly impacted by urban background. All the sediments were analyzed by consistent preparation and analytical methods and met consistent data quality objectives, thereby minimizing variations attributable to methodology. The data demonstrate that the anthropogenic hydrocarbons comprising urban background from all locations exhibit a generally consistent nature, dominated by (1) a variably shaped unresolved complex mixture (UCM) within the residual (C20+) range and (2) a variable distribution of resolved 4- to 6-ring nonalkylated (parent) PAHs, mostly dominated by fluoranthene and pyrene (and exhibiting a FL/PY ratio of 0.9 +/- 0.2). The variable nature of both the THC and PAH distributions testifies that, while there is a general consistency to urban background, there are definite differences between (and even within) different urban settings. This indicates thatthere is no single "representative" urban background THC or PAH signature. The greatest mass of THC is reasonably attributable to heavy petroleum(s) comprising the UCM, whereas the greatest mass of PAHs is reasonably attributable to combustion-derived particulate matter. The mean concentration of THC attributable to urban background was 415 mg/kg (dry wt). The concentration of EPA 16-Priority Pollutant PAHs was less than 20 000 microg/kg (dry wt) in 96% of the sediments studied. Thus, sediments containing significantly more than 20000 microg/kg of the EPA 16 Priority Pollutant PAHs (or more the 30000 microg/kg of 43 parent and alkylated PAHs) should be suspected to contain PAHs not entirely attributable to urban background, unless site- or regional-specific survey data supports a different urban background concentration profile.     

Level and degradation of Deepwater Horizon spilled oil in coastal marsh sediments and pore-water

This research investigates the level and degradation of oil at ten selected Gulf saltmarsh sites months after the 2010 BP Macondo-1 well oil spill. Very high levels (10-28%) of organic carbon within the heavily oiled sediments are clearly distinguished from those in pristine sediments (<3%). Dissolved organic carbon in contaminated pore-waters, ranging up to hundreds of mg/kg, are 1 to 2 orders of magnitude higher than those at pristine sites. Heavily oiled sediments are characterized by very high sulfide concentrations (up to 80 mg/kg) and abundance of sulfate reducing bacteria. Geochemical biomarkers and stable carbon isotope analyses fingerprint the presence of oils in sediments. Ratios of selected parameters calculated from the gas chromatograph spectra are in a remarkable narrow range among spilled oils and initial BP crude. At oiled sites dominated by C(4) plants, δ(13)C values of sediments (-20.8 ± 2.0‰) have been shifted significantly lower compared to marsh plants (-14.8 ± 0.6‰) due to the inflow of isotopically lighter oil (-27 ± 0.2‰). Our results show that (1) lighter compounds of oil are quickly degraded by microbes while the heavier fractions of oil still remain and (2) higher inputs of organic matter from the oil spill enhance the key microbial processes associated with sulfate reducing bacteria.     

运用顶空固相微萃取技术分析宣威火腿中的挥发性化合物

采用固相微萃取结合气相色谱 /质谱分析方法对宣威火腿中的挥发性化合物进行了提取和分析。试验结果表明 ,固相微萃取的时间和温度影响提取挥发性化合物的效果 ,试验选取 60℃、60min为提取条件 ,萃取物经气谱 /质谱分析 ,共鉴定出 72种化合物 ,其中烃类 2 8种、醛类 7种、醇类 4种、酸类 10种、酯类 5种、酮类 3种、杂环化合物 14种、酚类 1种。     

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.     

Evidence for the migration of steroidal estrogens through river bed sediments

Estrogenic substances discharged from wastewater treatment plants have been detected in surface sediments of receiving waters, but little is known of their vertical migration through buried sediments and their potential to contaminate subsurface waters. The vertical profiles of estrogenic chemicals were investigated in sediment cores at an alluvial freshwater site (Ditchling) and a clay-rich estuarine site (Lewes), both of which are downstream of wastewater discharges into the River Ouse (Sussex, U.K.). Estrone (E1) was the predominant estrogen detected in surface and buried sediments at both sites and was detected in undisturbed clay sediments > 120 years old. Profiles of E1 at Ditchling were characterized by a prominent subsurface peak of E1 at the alluvium/clay interface (-15 cm) at a concentration (28.8 +/- 6.0 ng/g of dry wt) that was 9-fold higher than in the surface sediment. In contrast, a steady downcore decline in E1 concentrations was observed in the clay-rich Lewes core. This work provides the first in situ evidence of estrogen migration through river bed sediments and reveals that movement of estrogens through unconsolidated sediment can result in penetration to the underlying substrata and therefore the potential for groundwater contamination.