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.

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.

Influence of exposure and toxicokinetics on measures of aquatic toxicity for organic contaminants: a case study review.

This theoretical and case study review of dynamic exposures of aquatic organisms to organic contaminants examines variables important for interpreting exposure and therefore toxicity. The timing and magnitude of the absorbed dose change when the dynamics of exposure change. Thus, the dose metric for interpreting toxic responses observed during such exposure conditions is generally limited to the specific experiment and cannot be extrapolated to either other experiments with different exposure dynamics or to field exposures where exposure dynamics usually are different. This is particularly true for mixture exposures, for which the concentration and composition and, therefore, the timing and magnitude of exposure to individual components of different potency and potentially different mechanisms of action can vary. Aquatic toxicology needs studies that develop temporal thresholds for absorbed toxicant doses to allow for better extrapolation between conditions of dynamic exposure. Improved experimental designs are required that include high-quality temporal measures of both the exposure and the absorbed dose to allow better interpretation of data. For the short term, initial water concentration can be considered a conservative measure of exposure, although the extent to which this is true cannot be estimated specifically unless the dynamics of exposure as well as the toxicokinetics of the chemicals in the exposure scenario for the organism of interest are known. A better, but still limited, metric for interpreting the exposure and, therefore, toxicity is the peak absorbed dose, although this neglects toxicodynamics, requires appropriate temporal measures of accumulated dose to determine the peak concentration, and requires temporal thresholds for critical body residue for each component of the mixture.

A Perspective on the Toxicity of Low Concentrations of Petroleum-Derived Polycyclic Aromatic Hydrocarbons to Early Life Stages of Herring and Salmon.

This article presents a critical review of two groups of studies that reported adverse effects to salmon and herring eggs and fry from exposure to 1 µg/L or less of aqueous total polycyclic aromatic hydrocarbons (TPAH), as weathered oil, and a more toxic aqueous extract of "very weathered oil." Exposure media were prepared by continuously flowing water up through vertical columns containing gravel oiled at different concentrations of Prudhoe Bay crude oil. Uncontrolled variables associated with the use of the oiled gravel columns included time- and treatment-dependent variations in the PAH concentration and composition in the exposure water, unexplored toxicity from other oil constituents/degradation products, potential toxicity from bacterial and fungal activity, oil droplets as a potential contaminant source, inherent differences between control and exposed embryo populations, and water flow rate differences. Based on a review of the evidence from published project reports, peer-reviewed publications, chemistry data in a public database, and unpublished reports and laboratory records, the reviewed studies did not establish consistent dose (concentration) response or causality and thus do not demonstrate that dissolved PAH alone from the weathered oil resulted in the claimed effects on fish embryos at low µg/L TPAH concentrations. Accordingly, these studies should not be relied on for management decision-making, when assessing the risk of very low-level PAH exposures to early life stages of fish.

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.

Evaluating the aquatic toxicity of complex organic chemical mixtures: lessons learned from polycyclic aromatic hydrocarbon and petroleum hydrocarbon case studies.

Experimental designs for evaluating complex mixture toxicity in aquatic environments can be highly variable and, if not appropriate, can produce and have produced data that are difficult or impossible to interpret accurately. We build on and synthesize recent critical reviews of mixture toxicity using lessons learned from 4 case studies, ranging from binary to more complex mixtures of primarily polycyclic aromatic hydrocarbons and petroleum hydrocarbons, to provide guidance for evaluating the aquatic toxicity of complex mixtures of organic chemicals. Two fundamental requirements include establishing a dose-response relationship and determining the causative agent (or agents) of any observed toxicity. Meeting these 2 requirements involves ensuring appropriate exposure conditions and measurement endpoints, considering modifying factors (e.g., test conditions, test organism life stages and feeding behavior, chemical transformations, mixture dilutions, sorbing phases), and correctly interpreting dose-response relationships. Specific recommendations are provided.

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.

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.

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.

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.

Potential for sea otter exposure to remnants of buried oil from the Exxon Valdez oil spill.

A study was conducted in 2005 and 2006 to examine the hypothesis that sea otters (Enhydra lutris) continue to be exposed to residues of subsurface oil (SSO) while foraging on shorelines in the northern Knight Island (NKI) area of Prince William Sound, Alaska more than 17 years after the Exxon Valdez oil spill. Forty-three shoreline segments, whose oiling history has been documented by prior surveys, were surveyed. These included all shoreline segments reported by a 2003 NOAA random site survey to contain SSO residues in NKI. Sites were surveyed for the presence and location of otter foraging pits. Only one of 29 SSO sites surveyed was identified as an otter foraging site. Most buried SSO residues are confined to tide elevations above +0.8 m above mean lower low water (MLLW), above the range of intertidal clam habitat. More than 99% of documented intertidal otter pits at all sites surveyed are in the lower intertidal zone (-0.2 to +0.8 m above MLLW), the zone of highest clam abundance. The spatial separation of the otter pits from the locations of SSO residues, both with regard to tidal elevation and lateral separation on the study sites, coupled with the lack of evidence of intertidal otter foraging at SSO sites indicates a low likelihood of exposure of foraging otters to SSO on the shores of the NKI area.

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.

Oil well produced water discharges to the North Sea. Part I: comparison of deployed mussels (Mytilus edulis), semi-permeable membrane devices, and the DREAM model predictions to estimate the dispersion of polycyclic aromatic hydrocarbons.

The oil companies operating in the Norwegian sector of the North Sea have conducted field studies since the mid-1990s to monitor produced water discharges to the ocean. These studies have been used to refine monitoring methods, and to develop and validate a dispersion and impact assessment model. This paper summarizes monitoring data from surveys conducted in two major oil and gas production areas, and compares the results to concentrations of polycyclic aromatic hydrocarbons (PAH) in surface waters predicted by the dose-related risk and effect assessment model (DREAM). Blue mussels and semi-permeable membrane devices (SPMDs) were deployed in the Ekofisk and Tampen Regions and analyzed for more than 50 PAH. PAH concentrations in ambient seawater were estimated based on the mussels and SPMD concentrations, and compared to model predictions. Surface water total PAH concentrations ranged from 25 to 350 ng/L within 1 km of the platform discharges and reached background levels of 4-8 ng/L within 5-10 km of the discharge; a 100,000-fold dilution of the PAH in the discharge water. The PAH concentrations in surface water, predicted by three methods, compared well for the Ekofisk Region. The model predicted higher concentrations than the field-based methods for parts of the Tampen Region; particularly the most tidally influenced areas. Tidally-mediated fluctuations in PAH concentrations in surface water must be considered because they affect the estimation of PAH concentrations from mussel and SPMD residue data, and the predictions by the DREAM model. Predictions using mussels, SPMDs, and modeling support and complement each other; all are valuable tools for estimating the fate and impact of chemical contaminants in produced water that are discharged to the ocean.