An approach to assess potential environmental mercury release, food web bioaccumulation, and human dietary methylmercury uptake from decommissioning offshore oil and gas infrastructure.

Subsea pipelines carrying well fluids from hydrocarbon fields accumulate mercury. If the pipelines (after cleaning and flushing) are abandoned in situ, their degradation may release residual mercury into the environment. To justify pipeline abandonment, decommissioning plans include environmental risk assessments to determine the potential risk of environmental mercury. These risks are informed by environmental quality guideline values (EQGVs) governing concentrations in sediment or water above which mercury toxicity may occur. However, these guidelines may not consider e.g., the bioaccumulation potential of methylated mercury. Therefore, EQGVs may not protect humans from exposure if applied as the sole basis for risk assessments. This paper outlines a process to assess the EQGVs' protectiveness from mercury bioaccumulation, providing preliminary insights to questions including how to (1) determine pipeline threshold concentrations, (2) model marine mercury bioaccumulation, and (3) determine exceedance of the methylmercury tolerable weekly intake (TWI) for humans. The approach is demonstrated with a generic example using simplifications to describe mercury behaviour and a model food web. In this example, release scenarios equivalent to the EQGVs resulted in increased marine organism mercury tissue concentrations by 0-33 %, with human dietary methylmercury intake increasing 0-21 %. This suggests that existing guidelines may not be protective of biomagnification in all circumstances. The outlined approach could inform environmental risk assessments for asset-specific release scenarios but must be parameterised to reflect local environmental conditions when tailored to local factors.

Threshold values for the protection of marine ecosystems from NORM in subsea oil and gas infrastructure.

This modelling study uses the ERICA Tool and Bateman's equation to derive sediment threshold values for radiation protection of the marine environment relevant to NORM-contaminated products (radium-contaminated scales, 210Pb films and 210Po films) found in subsea oil and gas infrastructure. Threshold values are calculated as the activity concentration of the NORM-contaminated products' head of chain radionuclide (i.e., 226Ra + 228Ra, 210Pb, or 210Po) that will increase radiation dose rates in sediments by 10 µGy/h to the most exposed organism at a given release time. The minimum threshold value (corresponding to peak radiation dose rates from the ingrowth of progeny) were for radium-contaminated scales, 0.009 Bq/g of 226Ra, 0.029 Bq/g of 228Ra (in the absence of 226Ra) or 0.14 Bq/g of 228Ra (in the presence of 226Ra), followed by 0.015 Bq/g for 210Pb films, and 1.6 Bq/g for 210Po films. These may be used as default threshold values. Added activity concentrations of the NORM-contaminated products to marine sediments below these threshold values implies a low radiological risk to organisms while exceedances imply that further investigation is necessary. Using contaminated product specific parameterisations, such as Kd values derived for Ra from a BaSO4 matrix in seawater, could greatly affect threshold values. Strong consideration should be given to deriving such data as part of specific radiological risk assessments for these products.

Radiological risk assessment to marine biota from exposure to NORM from a decommissioned offshore oil and gas pipeline.

Scale residues can accumulate on the interior surfaces of subsea petroleum pipes and may incorporate naturally occurring radioactive materials (NORM). The persistent nature of 'NORM scale' may result in a radiological dose to the organisms living on or near intact pipelines. Following a scenario of in-situ decommissioning of a subsea pipeline, marine organisms occupying the exteriors or interiors of petroleum structures may have close contact with the scale or other NORM-associated contaminated substances and suffer subsequent radiological effects. This case study used radiological dose modelling software, including the ERICA Tool (v2.0), MicroShield® Pro and mathematical equations, to estimate the likely radiological doses and risks of effects from NORM-contaminated scale to marine biota from a decommissioned offshore oil and gas pipeline. Using activity concentrations of NORM (226Ra, 210Po, 210Pb, 228Ra, 228Th) from a subsea pipeline from Australia, environmental realistic exposure scenarios including radiological exposures from both an intact pipe (external only; accounting for radiation shielding by a cylindrical carbon steel pipe) and a decommissioned pipeline with corrosive breakthrough (resulting in both internal and external radiological exposure) were simulated to estimate doses to model marine organisms. Predicted dose rates for both the external only exposure (ranging from 26 µGy/h to 33 µGy/h) and a corroded pipeline (ranging from 300 µGy/h to 16,000 µGy/h) exceeded screening levels for radiological doses to environmental receptors. The study highlighted the importance of using scale-specific solubility data (i.e., Kd) values for individual NORM radionuclides for ERICA assessments. This study provides an approach for conducting marine organism dose assessments for NORM-contaminated subsea pipelines and highlights scientific gaps required to undertake risk assessments necessary to inform infrastructure decommissioning planning.

Current understanding of the ecological risk of mercury from subsea oil and gas infrastructure to marine ecosystems.

Many oil and gas fields are nearing production cessation and will require decommissioning, with the preferred method being complete infrastructure removal in most jurisdictions. However, decommissioning in situ, leaving some disused components in place, is an option that may be agreed to by the regulators and reservoir titleholders in some circumstances. To understand this option's viability, the environmental impacts and risks of any residual contaminants assessed. Mercury, a contaminant of concern, is naturally present in hydrocarbon reservoirs, may contaminate offshore processing and transmission infrastructure, and can biomagnify in marine ecosystems. Mercury's impact is dependent on its speciation, concentration, and the exposure duration. However, research characterising and quantifying the amount of mercury in offshore infrastructure and the efficacy of decontamination is limited. This review describes the formation of mercury-contaminated products within oil and gas infrastructure, expected exposure pathways after environmental release, possible impacts, and key research gaps regarding the ecological risk of in situ decommissioned contaminated infrastructure. Suggestions are made to overcome these gaps, improving the in situ mercury quantification in infrastructure, understanding environmental controls on, and forecasting of, mercury methylation and bioaccumulation, and the cumulative impacts of multiple stressors within decommissioned infrastructures.

Current understanding and research needs for ecological risk assessments of naturally occurring radioactive materials (NORM) in subsea oil and gas pipelines.

Thousands of offshore oil and gas facilities are coming to the end of their life in jurisdictions worldwide and will require decommissioning. In-situ decommissioning, where the subsea components of that infrastructure are left in the marine environment following the end of its productive life, has been proposed as an option that delivers net benefits, including from: ecological benefits from the establishment of artificial reefs, economic benefits from associated fisheries, reduced costs and improved human safety outcomes for operators. However, potential negative impacts, such as the ecological risk of residual contaminants, are not well understood. Naturally occurring radioactive materials (NORM) are a class of contaminants found in some oil and gas infrastructure (e.g. pipelines) and includes radionuclides of uranium, thorium, radium, radon, lead, and polonium. NORM are ubiquitous in oil and gas reservoirs around the world and may form contamination products including scales and sludges in subsea infrastructure due to their chemistries and the physical processes of oil and gas extraction. The risk that NORM from these sources pose to marine ecosystems is not yet understood meaning that decisions made about decommissioning may not deliver the best outcomes for environments. In this review, we consider the life of NORM-contamination products in oil and gas systems, their expected exposure pathways in the marine environment, and possible ecological impacts following release. These are accompanied by the key research priorities that need to better describe risk associated with decommissioning options.

Effect of Dissolved Organic Matter Concentration and Source on the Chronic Toxicity of Copper and Nickel Mixtures to Chlorella sp.

There have been limited studies on the effects of toxicity-modifying factors, such as dissolved organic matter (DOM), on the toxicity of metal mixtures to aquatic biota. The present study investigated the effects of DOM concentration (low, 2.8 ± 0.1 mg C/L; high, 11 ± 1.0 mg C/L) and DOM source (predominantly terrestrial or microbial) on the chronic toxicity of copper (Cu) and nickel (Ni) binary mixtures to the green freshwater microalga Chlorella sp. This was assessed by using a full factorial design of 72-h growth inhibition bioassays. Measured algal growth rate was compared with growth predicted by the concentration addition and independent action reference models. Model predictions were based on concentrations of dissolved metals, labile metals (measured by diffusive gradients in thin films [DGT]), and calculated free metal ions (determined by the Windermere Humic Aqueous Model). Copper/Ni mixture toxicity was synergistic to Chlorella sp. in the absence of added DOM, with evidence of metal concentration-dependent toxicity at low effect concentrations. As DOM concentration increased, the mixture interaction changed from synergism to noninteraction or antagonism depending on the metal speciation method used. The DOM source had no significant effect on mixture interaction when based on dissolved and free metal ion concentrations but was significantly different when based on DGT-labile metal concentrations. Ratio-dependent mixture interaction was observed in all treatments, with increased deviation from the reference model predictions as the mixture changed from Ni- to Cu-dominated. The present study demonstrated that both DOM concentration and source can significantly change metal mixture toxicity interactions and that these interactions can be interpreted differently depending on the metal speciation method used. Environ Toxicol Chem 2021;40:1908-1918. © 2021 SETAC.

Speciation of nickel and its toxicity to Chlorella sp. in the presence of three distinct dissolved organic matter (DOM).

Nickel is often a metal of interest in regulatory settings given its increasing prevalence in disturbed freshwaters and as a known toxicant to fish and algae. Dissolved organic matter (DOM) is a toxicity modifying factor for nickel and a ubiquitous water physicochemical parameter. This study investigated the effect of DOM concentration and source on the chronic toxicity of nickel to Chlorella sp. using three DOM at two concentrations (3.1 ± 1.8 and 12 ± 1.3 mg C/L). Nickel toxicity to Chlorella sp. was not strongly influenced by DOM concentration. In the absence of DOM, the 72-h EC50 for Chlorella sp. was 120 µg Ni/L. In the low DOM treatment, nickel toxicity was either unchanged or slightly increased (87-140 µg Ni/L) and unchanged or slightly decreased in the high DOM treatment (130-240 µg Ni/L). DOM source also had little effect on nickel toxicity, the largest differences in nickel toxicity occurring in the high DOM treatment. Labile nickel (measured by diffusive gradients in thin-films, DGT) followed strong linear relationships with dissolved nickel (R2 > 0.97). DOM concentration and source had limited effect on DGT-labile nickel. DGT-labile nickel decreased with increasing DOM concentration for only one of the three DOM. Modelled labile nickel concentrations (expressed as maximum dynamic concentrations, cdynmax) largely agreed with DGT-labile nickel and suggested that toxicity is explained by free Ni2+ concentrations. This study confirms that nickel toxicity is largely unaffected by DOM concentration or source and that both measured (DGT) and modelled (cdynmax and free Ni2+) nickel concentrations can explain nickel toxicity.

Exposure to metals and semivolatile organic compounds in Australian fire stations.

Firefighting is an occupation with exposure to a wide range of chemicals by means of inhalation, ingestion or dermal contact. Although advancements in personal protective clothing and equipment have reduced the risks for acute exposure during fire suppression operations, chronic exposure may still be present at elevated levels in fire stations. The aim of this study was to assess chemicals in air and on surfaces in fire stations, compare this with other indoor environments, and use this data to estimate firefighter exposure within the fire station. Fifteen Australian fire stations were selected for chemical exposure assessment by means of 135 active air monitors, 60 passive air monitors, and 918 wipe samples. These samples were collected from the interior and exterior of fire stations, from personal protective clothing and equipment, and from within the cabins of vehicles. Chemicals analysed included polycyclic aromatic hydrocarbons, volatile organic compounds, metals, and diesel particulate matter. Specific chemicals were detected from within each class of chemicals, with metals being most frequently detected. Statistical analysis by means of Pearson's Correlations and threshold tests were used to consider the source of exposure, and a collective addition risk quotient calculation was used to determine firefighter exposure. The presence of metals in fire stations was compared with findings from global indoor dust measurements. Concentrations across firefighter ensemble, inside vehicle cabins, and within fire stations for chromium (39.5-493 µg/m2), lead (46.7-619 µg/m2), copper (594-3440 µg/m2), zinc (11100-20900 µg/m2), nickel (28.6-2469 µg/m2) and manganese (73.0-997 µg/m2) were in most instances orders of magnitude higher when compared with concentrations measured in homes and offices. Our study suggests that the elevated concentrations are associated with the transfer of chemicals from fire suppression operations. Due to this elevated concentration of chemicals, firefighters may face increased exposure, and in turn increased risk of adverse health effects. Data suggest that exposure may be mitigated by means of increased laundering frequency and increased decontamination at the scene of the fire.

Geochemical and ecotoxicological assessment of iron- and steel-making slags for potential use in environmental applications.

Prior to the productive use of iron- and steel-making slags as environmental amendments, a risk assessment supported by material characterization concomitant with leaching and ecotoxicological testing is necessary. Five iron- and steel-making slags were characterized geochemically, and the leachability of their elemental constituents was assessed. The toxicity of slag leachate to microalgae (Chlorella sp.), cladocerans (Ceriodaphnia dubia), and bacteria (Vibrio fischeri) was related to elemental composition. Slag leachates with the highest concentrations of dissolved elements were the most toxic (10% effective concentration [EC10] ∼1%), whereas those with the lowest concentrations of elements were the least toxic (EC10 63-85%). It was not possible to determine which elements caused the observed toxicity; however, comparisons with contaminant guidelines and published toxicity data identified several elements of potential environmental concern. Low to moderate activities were measured for radionuclides in the U and Th decay chains in slags. Based on these data, some of the slags examined herein are potentially suitable for use as environmental amendments following ≥10 times dilution to ameliorate potential toxic effects because of leachate pH.