In Situ Passive Sampling to Monitor Long Term Cap Effectiveness at a Tidally Influenced Shoreline.

Polydimethylsiloxane solid-phase microextraction passive samplers were used to evaluate long-term performance of a sand/gravel cap placed in 2005 in a tidally influenced shoreline in Puget Sound to reduce polycyclic aromatic hydrocarbon (PAH) transport into overlying surface water. Sampling in both 2010 and 2018 measured porewater concentrations of <1 ng/L total PAHs in the cap layer. d-PAH performance reference compounds were used to evaluate the extent of equilibration of the contaminants onto the samplers and to estimate net upwelling velocities through a mass-transfer model. The upwelling velocities were used to predict long-term migration of selected PAHs through the cap, showing that the cap is expected to continue being effective at limiting exposure of contaminants at the cap−water interface.

Characterization of Miscellaneous Effluent Discharges from a Mobile Offshore Drilling Unit to the Marine Environment.

A study was performed to evaluate the potential biological impacts from 8 different miscellaneous discharges from an oil and gas mobile offshore drilling unit (MODU) including deck drainage, desalination unit waste, boiler blowdown, fire control system test water, noncontact cooling water, and bilge water. Samples were evaluated for toxicity using a rapid (<1 h) initial screening test (echinoderm [Dendraster excentricus] fertilization test), and if toxicity was found, further testing was conducted using 3 chronic whole-effluent toxicity tests. This additional testing included the embryo larval development 72-h echinoderm (D. excentricus); 7-d mysid (Americamysis bahia) survival, growth, and fecundity invertebrate test; and 7-d topsmelt (Atherinops affinis) survival and growth fish test. Toxicity identification evaluations were performed on 3 discharges that consistently elicited a toxic response during whole-effluent toxicity testing. To place the results of the toxicity testing into the context of environmental risk, the spatial extent of potential biological effects was investigated using the CORMIX mixing zone model. The output of the modeling indicated that discharge of selected effluents did not result in concentrations, or duration of exposure, that would elicit toxic effects to organisms living in the surrounding environment. The present study provides a comprehensive data set that was used to characterize potential toxicity and environmental risk of MODU "miscellaneous discharges" which could help inform future risk assessments of these discharges. Environ Toxicol Chem 2019;38:2811-2823. © 2019 SETAC.

Upper-Rim Monofunctionalisation in the Synthesis of Triazole- and Disulfide-Linked Multicalix[4]- and -[6]arenes.

Covalently linked multiple calixarenes are valued in supramolecular chemistry. This work reports an easy and versatile synthetic route to covalently linked double and triple calix[4]arene and calix[6]arenes by a novel DMF-controlled selective alkylation of a convenient and readily available upper-rim dimethylaminomethyl-substituted tetrahydroxy and hexahydroxy calix[4]arene and -[6]arenes. Synthetic routes to upper-rim functionalised redox active disulfide-linked double-, tetra- and peptidohybrid-calixarenes employing either redox chemistry (CH2 SH) or thiolates (CH2 S- ) are also opened up from the same key starting material.

Current practices and knowledge supporting oil spill risk assessment in the Arctic.

Oil spill response (OSR) in the Arctic marine environment conducted as part of operational planning and preparedness supporting exploration and development is most successful when knowledge of the ecosystem is readily available and applicable in an oil spill risk assessment framework. OSR strategies supporting decision-making during the critical period after a spill event should be explicit about the environmental resources potentially at risk and the efficacy of OSR countermeasures that best protect sensitive and valued resources. At present, there are 6 prominent methods for spill impact mitigation assessment (SIMA) in the Arctic aimed at supporting OSR and operational planning and preparedness; each method examines spill scenarios and identifies response strategies best suited to overcome the unique challenges posed by polar ecosystems and to minimize potential long-term environmental consequences. The different methods are grounded in classical environmental risk assessment and the net environmental benefit analysis (NEBA) approach that emerged in the 1990s after the Exxon Valdez oil spill. The different approaches share 5 primary assessment elements (oil physical and chemical properties, fate and transport, exposure, effects and consequence analysis). This paper highlights how the different Arctic methods reflect this common risk assessment framework and share a common need for oil spill science relevant to Arctic ecosystems. An online literature navigation portal, developed as part of the 5-year Arctic Oil Spill Response Technologies Joint Industry Programme, complements the different approaches currently used in the Arctic by capturing the rapidly expanding body of scientific knowledge useful to evaluating exposure, vulnerability and recovery of the Arctic ecosystem after an oil spill.

Relative sensitivity of Arctic species to physically and chemically dispersed oil determined from three hydrocarbon measures of aquatic toxicity.

The risks to Arctic species from oil releases is a global concern, but their sensitivity to chemically dispersed oil has not been assessed using a curated and standardized dataset from spiked declining tests. Species sensitivity to dispersed oil was determined by their position within species sensitivity distributions (SSDs) using three measures of hydrocarbon toxicity: total petroleum hydrocarbons (TPH), polycyclic aromatic hydrocarbon (PAHs), and naphthalenes. Comparisons of SSDs with Arctic/sub-Arctic versus non-Arctic species, and across SSDs of compositionally similar oils, showed that Arctic and non-Arctic species have comparable sensitivities even with the variability introduced by combining data across studies and oils. Regardless of hydrocarbon measure, hazard concentrations across SSDs were protective of sensitive Arctic species. While the sensitivities of Arctic species to oil exposures resemble those of commonly tested species, PAH-based toxicity data are needed for a greater species diversity including sensitive Arctic species.

The acute toxicity of chemically and physically dispersed crude oil to key Arctic species under Arctic conditions during the open water season.

The acute toxicity of physically and chemically dispersed crude oil and the dispersant Corexit 9500 were evaluated for key Arctic species. The copepod Calanus glacialis, juvenile Arctic cod (Boreogadus saida), and larval sculpin (Myoxocephalus sp.) were tested under conditions representative of the Beaufort and Chukchi Seas during the ice-free season. The toxicity of 3 water-accommodated fractions (WAF) of Alaska North Slope crude oil was examined with spiked, declining exposures. A dispersant-only test was conducted with the copepod C. glacialis. Each preparation with oil (WAF, breaking wave WAF [BWWAF], and chemically enhanced WAF [CEWAF]) produced distinct suites of hydrocarbon constituents; the total concentrations of oil were lowest in WAF and highest in CEWAF preparations. The relative sensitivity for the different species and age classes was similar within each WAF type. Median lethal concentration values based on total petroleum hydrocarbons ranged from 1.6 mg/L to 4.0 mg/L for WAF and BWWAF treatments and from 22 mg/L to 62 mg/L for CEWAF. For Corexit 9500 exposures, median lethal concentration values ranged from 17 mg/L to 50 mg/L. The differences in the relative toxicity among the accommodated fractions indicated that the majority of petroleum hydrocarbons in the CEWAF are in less acutely toxic forms than the components that dominate the WAF or BWWAF. Further evaluation showed that the parent polycyclic aromatic hydrocarbon compounds, specifically naphthalene, were highly correlated to acute toxicity.