Effects of offshore oil exploration and development in the Alaskan Beaufort Sea: Long-term patterns of hydrocarbons in sediments.

The United States Bureau of Ocean Energy Management (BOEM) has sponsored 4 major monitoring projects in the oil and gas development area of the Alaskan Beaufort Sea since the 1980s, the last being the Arctic Nearshore Impact Monitoring in the Development Area III (ANIMIDA III) Project (2014-2017). These studies were conducted to better understand the physical, chemical, and biological environments and how oil and gas activities may impact them. This paper focuses on monitoring sediment hydrocarbon chemistry. The projects included measuring polycyclic aromatic hydrocarbons (PAHs), n-alkanes and isoprenoids (SHCs), and sterane/triterpene (S/T) geochemical biomarkers and determining their distribution, possible sources, and environmental significance in the sediments of the Beaufort Sea and rivers emptying into it. Concentrations of hydrocarbons in sediments were variable on both spatial and temporal scales; surface sediment concentrations of total PAHs (TPAHs), the class of hydrocarbons of greatest environmental interest, averaged between 300 and 700 µg/kg in different years of monitoring between 1985 and 2015. The concentrations were similar to those measured in other marine regions of Alaska where oil activities have not occurred. Sediment TPAH concentrations were below sediment quality guidelines values, indicating a low risk of harm to benthic marine communities. The hydrocarbons in the Beaufort Sea sediments are primarily from non-oil petrogenic and biogenic sources, with small amounts of pyrogenic hydrocarbons. Most of the hydrocarbons are carried to the Beaufort Sea in coastal erosion and river inputs of hydrocarbon-rich materials, such as peat and shale. The majority of the Beaufort Sea Development Area, including near production facilities, contains uncontaminated sediments with only a few small areas near (<100 m) some exploratory wells where petroleum hydrocarbon concentrations are above regional background. Integr Environ Assess Manag 2019;15:224-236. © 2019 SETAC.

Effects of offshore oil exploration and development in the Alaskan Beaufort Sea: A three-decade record for sediment metals.

Impacts from oil exploration, development, and production in the Beaufort Sea, Alaska, USA are assessed using concentrations of metals in sediments collected during 2014 to 2015, combined with a large data set for 1985 to 2006. Concentrations of 7 (1980s) or 17 (1999-2015) metals in 423 surface sediments from 134 stations, plus 563 samples from 30 cores were highly variable, primarily as a function of sediment granulometry with naturally greater metals concentrations in fine-grained, Al-rich sediment. Metals versus Al correlation plots were used to normalize metals concentrations and identify values significantly above background. Barium, Cr, Cu, Hg, and Pb concentrations were above background, but variable, within 250 m of some offshore sites where drilling occurred between 1981 and 2001; these areas totaled <6 km2 of 11 000 km2 in the total lease area. Random and fixed sampling along the coastal Beaufort Sea from 1985 to 2015 yielded 40 positive anomalies for metals in surface sediments (∼0.8% of 5082 data points). About 85% of the anomalies were from developed areas. Half the anomalies were for the 5 metals found enhanced near drilling sites. No metals concentrations, except As, exceeded accepted sediment quality criteria. Interannual shifts in metals values for surface sediments at inner shelf sites were common and linked to storm-induced transitions in granulometry; however, metal-to-Al ratios were uniform during these shifts. Sediment cores generally recorded centuries of background values, except for As, Fe, and Mn. These 3 metals were naturally enriched in sediments from deeper water (>100 m) via diagenetic remobilization at sediment depths of 5 to 15 cm, upward diffusion, and precipitation in surface oxic layers. Minimal evidence for anthropogenic inputs of metals, except near some exploratory drilling sites, is consistent with extraction of most oil from land or barrier islands in the Alaskan Arctic and restricted offshore activity to date. Integr Environ Assess Manag 2019;15:209-223. © 2018 SETAC.

Species sensitivity distributions for suspended clays, sediment burial, and grain size change in the marine environment.

Assessment of the environmental risk of discharges, containing both chemicals and suspended solids (e.g., drilling discharges to the marine environment), requires an evaluation of the effects of both toxic and nontoxic pollutants. To date, a structured evaluation scheme that can be used for prognostic risk assessments for nontoxic stress is lacking. In the present study we challenge this lack of information by the development of marine species sensitivity distributions (SSDs) for three nontoxic stressors: suspended clays, burial by sediment, and change in sediment grain size. Through a literature study, effect levels were obtained for suspended clays, as well as for burial of biota. Information on the species preference range for median grain size was used to assess the sensitivity of marine species to changes in grain size. The 50% hazardous concentrations (HC50) for suspended barite and bentonite based on 50% effect concentrations (EC50s) were 3,010 and 1,830 mg/L, respectively. For burial the 50% hazardous level (HL50) was 5.4 cm. For change in median grain size, two SSDs were constructed; one for reducing and one for increasing the median grain size. The HL50 for reducing the median grain size was 17.8 mum. For increasing the median grain size this value was 305 mum. The SSDs have been constructed by using information related to offshore oil- and gas-related activities. Nevertheless, the results of the present study may have broader implications. The hypothesis of the present study is that the SSD methodology developed for the evaluation of toxic stress can also be applied to evaluate nontoxic stressors, facilitating the incorporation of nontoxic stressors in prognostic risk assessment tools.

Bioavailability of polycyclic aromatic hydrocarbons from buried shoreline oil residues thirteen years after the Exxon Valdez oil spill: a multispecies assessment.

Seven taxa of intertidal plants and animals were sampled at 17 shoreline sites in Prince William Sound ([PWS]; AK, USA), that were heavily oiled in 1989 by the Exxon Valdez oil spill (EVOS) to determine if polycyclic aromatic hydrocarbons (PAH) from buried oil in intertidal sediments are sufficiently bioavailable to intertidal prey organisms that they might pose a health risk to populations of birds and wildlife that forage on the shore. Buried residues of EVOS oil are present in upper and middle intertidal sediments at 16 sites. Lower intertidal (0 m) sediments contain little oil. Much of the PAH in lower intertidal sediments are from combustion sources. Mean tissue total PAH (TPAH) concentrations in intertidal clams, mussels, and worms from oiled sites range from 24 to 36 ng/g (parts per billion) dry weight; sea lettuce, whelks, hermit crabs, and intertidal fish contain lower concentrations. Concentrations of TPAH are similar or slightly lower in biota from unoiled reference sites. The low EVOS PAH concentrations detected in intertidal biota at oiled shoreline sites indicate that the PAH from EVOS oil buried in intertidal sediments at these sites have a low bioavailability to intertidal plants and animals. Individual sea otters or shorebirds that consumed a diet of intertidal clams and mussels exclusively from the 17 oiled shores in 2002 were at low risk of significant health problems. The low concentrations of EVOS PAH found in some intertidal organisms at some oiled shoreline sites in PWS do not represent a health risk to populations of marine birds and mammals that forage in the intertidal zone.

Toxicity of weathered Exxon Valdez crude oil to pink salmon embryos.

Research was conducted at the University of Idaho (Moscow, ID, USA) on the toxicity of weathered Exxon Valdez crude oil to embryos of pink salmon from 2001 to 2003 for the purpose of comparing these data with those from the National Oceanic and Atmospheric Administration Fisheries Laboratory at Auke Bay (AK, USA). Mortality reported at Auke Bay for embryos chronically exposed to very low concentrations of aqueous solutions of weathered oil, measured as dissolved polycyclic aromatic hydrocarbons (PAHs), was inconsistent with that in other published research. Using the Auke Bay experimental design, we found that toxicity is not evident in pink salmon embryos until chronic exposure to laboratory weathered and naturally weathered oil concentrations exceeding 1,500 and 2,250 ppm, respectively, representing a total PAH tissue burden in excess of 7,100 ppb. Effluent hydrocarbons also drop well below concentrations sufficient to cause harm over the time frame of a few weeks, regardless of oiling level. Resolution of differences with Auke Bay involved the source of contributing hydrocarbons. The experimental design did not exclude dispersed oil droplets from the aqueous solution; thus, toxicity was not limited to the dissolved hydrocarbon fraction. The implications of the present results are discussed regarding the toxic risk of weathered oil to pink salmon embryos in streams of Prince William Sound (AK, USA).

Oil well produced water discharges to the North Sea. Part II: comparison of deployed mussels (Mytilus edulis) and the DREAM model to predict ecological risk.

Large volumes of water often are produced with oil and gas from offshore platforms. The produced water is separated from the oil and gas and either reinjected into a deep formation or discharged to the ocean. The Norwegian oil and gas industry advocates ecological risk assessment as the basis for managing produced water discharges to the North Sea. In this paper, we compare estimates of ecological risks to water-column communities based on data on hydrocarbon residues in soft tissues of blue mussels deployed for a month near offshore platforms and based on predictions of the Dose related Risk and Effect Assessment Model (DREAM). The study was performed near produced water discharges to the Tampen and Ekofisk Regions of the Norwegian Sector of the North Sea. Because polycyclic aromatic hydrocarbons (PAH) are considered the most important contributors to the ecological hazard posed by produced water discharges, comparisons made here focus on this group of compounds. The mussel approach is based on predicted environmental concentrations (PECs) of individual PAH, estimated from PAH residues in mussels following deployment for a month near several produced water discharges, and predicted no effects concentrations (PNECs) based on a K(ow) regression model. In the DREAM method, PECs for three PAH fractions are estimated in the three-dimensional area around produced water discharge with the DREAM model. PNECs for each fraction are based on the chronic toxicity of a representative PAH from each fraction divided by an assessment factor to account for uncertainty in the chronic value. The mussel method gives much lower estimates of ecological risk than the DREAM method. The differences are caused by the much lower PNECs used in DREAM than derived from the regression model, and by the lower concentrations of aqueous PAH predicted by DREAM than estimated from PAH residues in mussel tissues. However, the two methods rank stations at different distances from produced water discharges in the same order and both identify 2- and 3-ring PAHs as the main contributors to the ecological risk of produced water discharges. Neither method identifies a significant ecological risk of PAH in the upper water column of the oil fields. The DREAM model may produce an overly conservative estimate of ecological risk of produced water discharges to the North Sea.

A hierarchical approach measures the aerial extent and concentration levels of PAH-contaminated shoreline sediments at historic industrial sites in Prince William Sound, Alaska.

A field study was conducted in 2003 to estimate the areal distribution and concentrations of polycyclic aromatic hydrocarbons (PAH) in intertidal sediments at sites of past human and industrial activity (HA sites) in Prince William Sound (PWS), Alaska, the site of the 1989 Exxon Valdez oil spill. More than 50 HA sites, primarily in western PWS, were identified through analysis of historic records and prior field studies, and nine sites were selected for detailed surveys. The areal assessment process consisted of seven steps: (1) identify site from historic records and field surveys; (2) locate visual evidence of surface oil/tar at a site; (3) prepare a site map and lay out a sampling grid over the entire site with 10-m grid spacing; (4) excavate pits to 50 cm depth on the grid; (5) perform a field colorimetric test to estimate total PAH (TPAH) in sediments from the wall of each pit and record the results in the ranges <1 ppm; 1-10 ppm; >10 ppm TPAH; (6) expand grid size if necessary if elevated PAH levels are detected colorimetrically; (7) select 20 samples from each site for same-day shipboard PAH analysis by immunoassay (SDI RaPID PAH) and, based on these results, select sediment samples from each site for full PAH analysis in the laboratory to identify PAH sources. A total of 416 pits were dug at the nine sites. Nine acres of sediments with TPAH >2500 ppb dry wt. were mapped at the nine sites. TPAH concentrations obtained by immunochemical analysis of 181 samples from the nine sites ranged from 20 to 1,320,000 ppb (wet wt.). The contaminants are mixtures of petroleum products (2-3 ring PAH) and combustion products (4-6 ring PAH) unrelated to the 1989 Exxon Valdez oil spill. Mussels and clams collected at these sites have elevated levels of PAH that are compositionally similar to the PAH in the sediments. These findings indicate that at least a portion of the sediment PAH is bioavailable. The PAH sources at these historic industrial sites are chronic. They include relict fuel oil tanks and works located above and within the intertidal zone, with contamination at some locations extending into nearshore sub-tidal sediments. This study shows how a hierarchical approach can be used to quickly and successfully map, quantify, and subsequently, identify sources of PAH in shoreline sediments.

Mussels document loss of bioavailable polycyclic aromatic hydrocarbons and the return to baseline conditions for oiled shorelines in Prince William Sound, Alaska.

Polycyclic aromatic hydrocarbons (PAH) were measured in mussels (Mytilus trossulus) collected between 1990 and 2002 from 11 sites on the shores of Prince William Sound (PWS), Alaska, that were heavily oiled by the 1989 Exxon Valdez oil spill (EVOS). This study, utilizing the methods of the NOAA Status and Trends Mussel Watch Program, found that concentrations of PAH released from spill remnants have decreased dramatically with time and by 2002 were at or near the range of total PAH (TPAH) of 3-355 ng/g dry weight obtained for mussels from unoiled reference sites in PWS. Time-series TPAH data indicate a mean TPAH half-life in mussel tissues of 2.4 years with a range from 1.4 to 5.3, yielding an annual mean loss of bioaccumulated TPAH of 25%. The petroleum-derived TPAH fraction in mussel tissues has decreased with time, reflecting the decreasing release of EVOS residues in shoreline sediments. These results show that PAH from EVOS residues that remain buried in shoreline sediments after the early 1990s are in a form and at locations that have a low accessibility to mussels living in the intertidal zone.

Comparison of mussels and semi-permeable membrane devices as intertidal monitors of polycyclic aromatic hydrocarbons at oil spill sites.

Side-by-side comparisons of polycyclic aromatic hydrocarbon (PAH) concentrations in resident blue mussels (Mytilus trossulus) and in semi-permeable membrane devices (SPMDs) were made at four sites in Prince William Sound, Alaska. SPMDs were deployed for approximately 30 days on the surface of the beach sediment at three tidal elevations on each shore and in 0.5 m deep open pits in the middle intertidal zone. Total PAH (TPAH) concentrations in mussels and in SPMDs were correlated, but the PAH compositions were different. The lower molecular weight PAH were relatively more abundant in the SPMDs than in the mussels at oiled and HA sites. TPAH concentrations in SPMDs deployed in pits and mussels collected adjacent to those pits at oiled sites were higher than in SPMDs and mussels from non-pitted SPMD locations approximately 3-15 m from the pits. Pitting released buried oil making its PAH bioavailable. SPMDs deployed in the supratidal zone (+4.0 m tidal elevation) were exposed to atmospheric contaminants for a large fraction of the deployment time and accumulated primarily pyrogenic (combustion-sourced) PAH from the atmosphere. The SPMD strips supplied by the manufacturer contained significant amounts (approximately 125 ng/strip) of primarily alkylated 2-3 ring PAH. These blank levels make SPMDs unsuitable for shoreline assessments when environmental PAH concentrations are low. Consequently, where available, mussels are recommended for use in assessments of the bioavailability of buried oil residues sequestered in intertidal sediments following an oil spill. Mussels are the preferred monitoring tool when the assessments involve food-chain effects. At locations where the absence of mussels necessitates the use of SPMDs or other passive sampling devices, their limitations need to be carefully considered in the interpretation of results.

Polycyclic aromatic hydrocarbon levels in mussels from Prince William Sound, Alaska, USA, document the return to baseline conditions.

Bioavailable hydrocarbons in the Exxon Valdez oil spill zone in Prince William Sound (PWS; AK, USA) shorelines were at or near background levels in 2002, as indicated by low concentrations of polycyclic aromatic hydrocarbons (PAHs) in mussels (Mytilus trossulus) collected from sites throughout PWS. Total PAH (TPAH) minus parent naphthalene concentrations in mussels collected in 1998 to 2002 from sites oiled in 1989 were at or near reference-site values. Both oiled and reference sites included locations associated with past human and industrial activity (HA). Inclusion of the unoiled HA sites in the range of reference sites that define prespill conditions is consistent with federal regulations. For the period from 1998 to 2002, the geometric mean of TPAH concentrations for 218 mussel samples collected from 72 sites, including four HA sites that had been heavily oiled in 1989, is 54 ng/g dry weight (range, 2-1,190 ng/g). The maximum mussel TPAH concentrations are equivalent to a weathered-oil exposure dose to intertidal foragers that is one to three orders of magnitude less than the doses shown to cause sublethal effects in surrogate species. The geometric mean of TPAH concentrations for mussel samples from 28 locations not oiled in 1989 and unaffected by human use (NHA sites) is 28 ng/g (range, 3-355 ng/g), whereas the geometric mean of TPAH concentrations for mussel samples from 14 locations not oiled in 1989 and affected by human use (HA sites) is 106 ng/g (range, 2-12,056 ng/g). The range of data for the unoiled HA and NHA sites defines the background of bioavailable PAHs to mussels on western PWS shorelines that would have prevailed if the oil spill had not occurred. The low PAH concentrations in mussels from sites known to have subsurface oil residues demonstrates the low bioavailability of these spill remnants and, thus, are a low additional risk to foraging wildlife. The present study shows continuous exposure from four- to six-ring PAHs originating at HA sites in western PWS. At low concentrations, these PAHs are known to cause adverse biological effects. However, in the context of PWS, oiled and HA sites represent a small percentage (approximately 0.1-0.2%) of the total PWS shoreline.

Hydrocarbon composition and toxicity of sediments following the Exxon Valdez oil spill in Prince William Sound, Alaska, USA.

An 1-year study of the 1989 Exxon Valdez oil spill found that spill residues on the oiled shorelines rapidly lost toxicity through weathering. After 1990, toxicity of sediments remained at only a few heavily oiled, isolated locations in Prince William Sound (AK, USA), as measured by a standard amphipod bioassay using Rhepoxynius abronius. Data from 648 sediment samples taken during the 1990 to 1993 period were statistically analyzed to determine the relationship between the total concentration of 39 parent and methyl-substituted polycyclic aromatic hydrocarbons (defined as total polycyclic aromatic hydrocarbons [TPAH]) and amphipod mortality and the effect of oil weathering on toxicity. A logistic regression model yielded estimates of the lower threshold, LC10 (lethal concentration to 10% of the population), and LC50 (median lethal concentration) values of 2,600, 4,100, and 10,750 ng/g TPAH (dry wt), respectively. Estimates of the threshold and LC50 values in this field study relate well to corresponding sediment quality guideline (SQG) values reported in the literature. For sediment TPAH concentrations >2,600 ng/g, samples with high mortality values (>90%) had relatively high fractions of naphthalenes and those with low mortality (<20%) had relatively high fractions of chrysenes. By 1999, the median sediment TPAH concentration of 117 ng/g for the post-1989 worst-case sites studied were well below the 2,600 ng/g toxicity threshold value, confirming the lack of potential for long-term toxic effects. Analysis of biological community structure parameters for sediment samples taken concurrently found that species richness and Shannon diversity decreased with increasing TPAH above the 2,600 ng/g threshold, demonstrating a correspondence between sediment bioassay results and biological community effects in the field. The low probability of exposure to toxic concentrations of weathered spill residues at the worst-case sites sampled in this study is consistent with the rapid overall recovery of shoreline biota observed in 1990 to 1991.

The importance of both potency and mechanism in dose-response analysis: an example from exposure of Pacific herring (Clupea pallasi) embryos to low concentrations of weathered crude oil.

This paper reanalyzes data from an earlier study that used effluents from oiled-gravel columns to assess the toxicity of aqueous fractions of weathered crude oil to Pacific herring embryos and larvae. This reanalysis has implications for future similar investigations, including the observance of two distinct dose-response curves for lethal and sublethal endpoints for different exposures in the same experiment, and the need to consider both potency and slope of dose-response curves for components of a toxicant mixture that shows potentially different toxicity mechanisms/causation. Contrary to conclusions of the original study, the aqueous concentration data cannot support the hypothesis that polycyclic aromatic hydrocarbons (PAHs) were the sole cause of toxicity and that oil toxicity increased with weathering. Confounding issues associated with the oiled gravel columns include changes in the concentration and composition of chemicals in exposure water, which interfere with the production of reliable and reproducible results relevant to the field.

Bioaccumulation of petroleum hydrocarbons in arctic amphipods in the oil development area of the Alaskan Beaufort Sea.

An objective of a multiyear monitoring program, sponsored by the US Department of the Interior, Bureau of Ocean Energy Management was to examine temporal and spatial changes in chemical and biological characteristics of the Arctic marine environment resulting from offshore oil exploration and development activities in the development area of the Alaskan Beaufort Sea. To determine if petroleum hydrocarbons from offshore oil operations are entering the Beaufort Sea food web, we measured concentrations of hydrocarbons in tissues of amphipods, Anonyx nugax, sediments, Northstar crude oil, and coastal peat, collected between 1999 and 2006 throughout the development area. Mean concentrations of polycyclic aromatic hydrocarbons (PAH), saturated hydrocarbons (SHC), and sterane and triterpane petroleum biomarkers (StTr) were not significantly different in amphipods near the Northstar oil production facility, before and after it came on line in 2001, and in amphipods from elsewhere in the study area. Forensic analysis of the profiles (relative composition and concentrations) of the 3 hydrocarbon classes revealed that hydrocarbon compositions were different in amphipods, surface sediments where the amphipods were collected, Northstar crude oil, and peat from the deltas of 4 North Slope rivers. Amphipods and sediments contained a mixture of petrogenic, pyrogenic, and biogenic PAH. The SHC in amphipods were dominated by pristane derived from zooplankton, indicating that the SHC were primarily from the amphipod diet of zooplankton detritus. The petroleum biomarker StTr profiles did not resemble those in Northstar crude oil. The forensic analysis revealed that hydrocarbons in amphipod tissues were not from oil production at Northstar. Hydrocarbons in amphipod tissues were primarily from their diet and from river runoff and coastal erosion of natural diagenic and fossil terrestrial materials, including seep oils, kerogens, and peat. Offshore oil and gas exploration and development do not appear to be causing an increase in petroleum hydrocarbon contamination of the Beaufort Sea food web.

Quantitative Assessment of Current Risks to Harlequin Ducks in Prince William Sound, Alaska, from the Exxon Valdez Oil Spill.

Harlequin Ducks (Histrionicus histrionicus) were adversely affected by the Exxon Valdez oil spill (EVOS) in Prince William Sound (PWS), Alaska, and some have suggested effects continue two decades later. We present an ecological risk assessment evaluating quantitatively whether PWS seaducks continue to be at-risk from polycyclic aromatic hydrocarbons (PAHs) in residual Exxon Valdez oil. Potential pathways for PAH exposures are identified for initially oiled and never-oiled reference sites. Some potential pathways are implausible (e.g., a seaduck excavating subsurface oil residues), whereas other pathways warrant quantification. We used data on PAH concentrations in PWS prey species, sediments, and seawater collected during 2001-2008 to develop a stochastic individual-based model projecting assimilated doses to seaducks. We simulated exposures to 500,000 individuals in each of eight age/gender classes, capturing the variability within a population of seaducks living in PWS. Doses to the maximum-exposed individuals are ∼400-4,000 times lower than chronic toxicity reference values established using USEPA protocols for seaducks. These exposures are so low that no individual-level effects are plausible, even within a simulated population that is orders-of-magnitude larger than exists in PWS. We conclude that toxicological risks to PWS seaducks from residual Exxon Valdez oil two decades later are essentially non-existent.

Exposure of sea otters and harlequin ducks in Prince William Sound, Alaska, USA, to shoreline oil residues 20 years after the Exxon Valdez oil spill.

We assessed whether sea otters and harlequin ducks in an area of western Prince William Sound, Alaska, USA (PWS), oiled by the 1989 Exxon Valdez oil spill (EVOS), are exposed to polycyclic aromatic hydrocarbons (PAH) from oil residues 20 years after the spill. Spilled oil has persisted in PWS for two decades as surface oil residues (SOR) and subsurface oil residues (SSOR) on the shore. The rare SOR are located primarily on the upper shore as inert, nonhazardous asphaltic deposits, and SSOR are confined to widely scattered locations as small patches under a boulder/cobble veneer, primarily on the middle and upper shore, in forms and locations that preclude physical contact by wildlife and diminish bioavailability. Sea otters and harlequin ducks consume benthic invertebrates that they collect by diving to the bottom in the intertidal and subtidal zones. Sea otters also dig intertidal and subtidal pits in search of clams. The three plausible exposure pathways are through the water, in oil-contaminated prey, or by direct contact with SSOR during foraging. Concentrations of PAH in near-shore water off oiled shores in 2002 to 2005 were at background levels (<0.05 ng/L). Median concentrations of PAH in five intertidal prey species on oiled shores in 2002 to 2008 range from 4.0 to 34 ng/g dry weight, indistinguishable from background concentrations. Subsurface oil residues are restricted to locations on the shore and substrate types, where large clams do not occur and where sea otters do not dig foraging pits. Therefore, that sea otters and harlequin ducks continue to be exposed to environmentally significant amounts of PAH from EVOS 20 years after the spill is not plausible.

Estimation of bioavailability of metals from drilling mud barite.

Drilling mud and associated drill cuttings are the largest volume wastes associated with drilling of oil and gas wells and often are discharged to the ocean from offshore drilling platforms. Barite (BaSO4) often is added as a weighting agent to drilling muds to counteract pressure in the geologic formations being drilled, preventing a blowout. Some commercial drilling mud barites contain elevated (compared to marine sediments) concentrations of several metals. The metals, if bioavailable, may harm the local marine ecosystem. The bioavailable fraction of metals is the fraction that dissolves from the nearly insoluble, solid barite into seawater or sediment porewater. Barite-seawater and barite-porewater distribution coefficients (Kd) were calculated for determining the predicted environmental concentration (PEC; the bioavailable fraction) of metals from drilling mud barite in the water column and sediments, respectively. Values for Kdbarite-seawater and Kdbarite-porewater were calculated for barium, cadmium, chromium, copper, mercury, lead, and zinc in different grades of barite. Log Kdbarite-seawater values were higher (solubility was lower) for metals in the produced water plume than log Kdbarite-porewater values for metals in sediments. The most soluble metals were cadmium and zinc and the least soluble were mercury and copper. Log Kd values can be used with data on concentrations of metals in barite and of barite in the drilling mud-cuttings plume and in bottom sediments to calculate PECseawater and PECsediment.

Distribution and weathering of crude oil residues on shorelines 18 years after the Exxon Valdez spill.

In 2007, a systematic study was conducted to evaluate the form and location of residues of oil buried on Prince William Sound (PWS) shorelines, 18 years after the 1989 Exxon Valdez Oil Spill (EVOS). We took 678 sediment samples from 22 sites that were most heavily oiled in 1989 and known to contain the heaviest subsurface oil (SSO) deposits based on multiple studies conducted since 2001. An additional 66 samples were taken from two sites, both heavily oiled in 1989 and known to be active otter foraging sites. All samples were analyzed for total extractable hydrocarbons (TEH), and 25% were also analyzed for saturated and aromatic hydrocarbon weathering parameters. Over 90% of the samples from all sites contained light or no SSO at all. Of samples containing SSO, 81% showed total polycyclic aromatic hydrocarbon (TPAH) losses greater than 70%, relative to cargo oil, with most having >80% loss. Samples with SSO were observed in isolated patches sequestered by surface boulder and cobble armoring. Samples showing lowest TPAH loss correlated strongly with higher elevations in the intertidal zones. Of the 17 atypical, less-weathered samples having less than 70% loss of TPAH (>30% remaining), only two were found sequestered in the lower intertidal zone, both at a single site. Most of the EVOS oil in PWS has been eliminated due to natural weathering. Some isolated SSO residues remain because they are sequestered and only slowly affected by natural weathering processes that normally would bring about their rapid removal. Even where SSO patches remain, most are highly weathered, sporadically distributed at a small number of sites, and widely separated from biologically productive lower intertidal zones where most foraging by wildlife occurs.