Assessing petroleum contamination in parts of the Niger Delta based on a sub-catchment delineated field assessment.

The Niger Delta in Nigeria is a complex and heavily contaminated area with over 150,000 interconnected contaminated sites. This intricate issue is compounded by the region's strong hydrological processes and high-energy environment, necessitating a science-based approach for effective contamination assessment and management. This study introduces the concept of sub-catchment contamination assessment and management, providing an overarching perspective rather than addressing each site individually. A description of the sub-catchment delineation process using the digital elevation model data from an impacted area within the Delta is provided. Additionally, the contamination status from the delineated sub-catchment is reported. Sediment, surface water and groundwater samples from the sub-catchment were analyzed for total petroleum hydrocarbons (TPH) and polycyclic aromatic hydrocarbons (PAHs), respectively. Surface sediment TPH concentrations ranged from 129 to 20,600 mg/kg, with subsurface (2-m depth) concentrations from 15.5 to 729 mg/kg. PAHs in surface and subsurface sediment reached 9.55 mg/kg and 0.46 mg/kg, respectively. Surface water exhibited TPH concentrations from 10 to 620 mg/L, while PAHs ranged from below detection limits to 1 mg/L. Groundwater TPH concentrations spanned 3 to 473 mg/L, with total PAHs varying from below detection limits to 0.28 mg/L. These elevated TPH and PAH levels indicate extensive petroleum contamination in the investigated sediment and water environment. Along with severe impacts on large areas of mangroves and wetlands, comparison of TPH and PAH concentrations with sediment and water quality criteria found 54 to 100% of stations demonstrated exceedances, suggesting adverse biological effects on aquatic and sediment biota are likely occurring.

Passive Sampling-Based versus Conventional-Based Metrics for Evaluating Remediation Efficacy at Contaminated Sediment Sites: A Review.

Passive sampling devices (PSDs) are increasingly used at contaminated sites to improve the characterization of contaminant transport and assessment of ecological and human health risk at sediment sites and to evaluate the effectiveness of remedial actions. The use of PSDs after full-scale remediation remains limited, however, in favor of evaluation based on conventional metrics, such as bulk sediment concentrations or bioaccumulation. This review has three overall aims: (1) identify sites where PSDs have been used to support cleanup efforts, (2) assess how PSD-derived remedial end points compare to conventional metrics, and (3) perform broad semiquantitative and selective quantitative concurrence analyses to evaluate the magnitude of agreement between metrics. Contaminated sediment remedies evaluated included capping, in situ amendment, dredging and monitored natural recovery (MNR). We identify and discuss 102 sites globally where PSDs were used to determine remedial efficacy resulting in over 130 peer-reviewed scientific publications and numerous technical reports and conference proceedings. The most common conventional metrics assessed alongside PSDs in the peer-reviewed literature were bioaccumulation (39%), bulk sediments (40%), toxicity (14%), porewater grab samples (16%), and water column grab samples (16%), while about 25% of studies used PSDs as the sole metric. In a semiquantitative concurrence analysis, the PSD-based metrics agreed with conventional metrics in about 68% of remedy assessments. A more quantitative analysis of reductions in bioaccumulation after remediation (i.e., remediation was successful) showed that decreases in uptake into PSDs agreed with decreases in bioaccumulation (within a factor of 2) 61% of the time. Given the relatively good agreement between conventional and PSD-based metrics, we propose several practices and areas for further study to enhance the utilization of PSDs throughout the remediation of contaminated sediment sites.

Effect of Activated Carbon in Thin Sand Caps Challenged with Ongoing PCB Inputs from Sediment Deposition: PCB Uptake in Clams (Mercenaria mercenaria) and Passive Samplers.

Ongoing inputs, in the form of sediment deposition along with associated dissolved contaminants, have challenged the assessment of cap performance at contaminated sediment sites. To address this issue, thin 2-3 cm layer sand caps amended with activated carbon (AC) were investigated for the remediation of polychlorinated biphenyl (PCB) contaminated marine sediments using 90-day mesocosms. All treatments were challenged with (1) ongoing clean or marker-PCB-spiked sediment inputs and (2) bioturbation. Bioaccumulation in hard clams (filter feeding near the cap-water interface) was evaluated to best understand cap effectiveness, relative to sheepshead minnows (confined to the surface water) and sandworms (which burrowed through the caps). All caps (sand and AC amended sand) provided isolation of native bedded PCBs (i.e., PCBs sourced from the bed), reducing uptake in organisms. Total PCB bioaccumulation in clams indicated that AC addition to the cap provided no benefit with spiked influx, or some benefit (56% reduction) with clean influx. Spiked input PCBs, when added to the depositional input sediment, were consistently detected in clams and passive samplers, with and without AC in the cap. PCB uptake by passive samplers located in the caps did not reflect the performance of the remedy, as defined by clam bioaccumulation. However, PCB uptake by passive samplers in the overlying water reasonably represented clam bioaccumulation results.

Evaluating Polymeric Sampling as a Tool for Predicting the Bioaccumulation of Polychlorinated Biphenyls by Fish and Shellfish.

Recent research has shown that polymeric sampling data generally can predict the bioaccumulation of hydrophobic organic contaminants by benthic and sessile invertebrates. Based on literature data, this review evaluated polymeric sampling as a tool for predicting the bioaccumulation of polychlorinated biphenyls (PCBs) by pelagic and mobile fish and shellfish. Lipid-normalized concentrations (CL) were linked to corresponding equilibrium polymer concentrations (CP) to evaluate the (1) correlation between CL and CP, (2) accuracy when using CP as surrogates for CL, (3) effects of experimental variables on these results, and (4) implications associated with this approach. Generally, strong positive log-log linear correlations existed between CL and CP, meaning that increasing bioaccumulation was well-reflected by increasing polymer accumulation. Further, the majority of the regression lines, as well as individual CL to CP ratios, were within a factor of 10 from the hypothetical 1:1 relationship, suggesting that polymers accumulated concentrations comparable to body residues in fish and shellfish. Interestingly, overall stronger correlations and lower CL to CP ratios resulted when CP were based on sediment compared to water column-deployed samplers. These findings provide a tool for environmental managers when assessing and managing risk associated with PCB-contaminated sediments and waters in protecting vulnerable fish and shellfish species.

Fate and Transformation of Graphene Oxide in Estuarine and Marine Waters.

The possibility of graphene oxide (GO) exposure to the environment has spurred several studies investigating the fate of this nanoparticle (NP). However, there is currently little or no data on the fate of GO in estuarine and marine waters. This study investigated the aggregation, sedimentation, and transformation of GO in saline waters, considering the roles of salinity (0-50 ‰), light (visible light and solar irradiation), and aging, among others. The attachment efficiency of GO reached unity at 1.33 ‰. The sedimentation rate of GO increased with salinity up to 10 ‰ after which it decreased due to formation of ramified GO agglomerates and media density. On the basis of the sedimentation rate determined at 30 ‰ (0.121 m/d), the residence time of GO agglomerates in the euphotic zone of typical open oceans will exceed 500 days. Aging in the presence of visible light increased the relative abundance of the GO's aromatic (C-C/C=C) fraction, reducing the NP. Reduction of GO in visible light was confirmed via UV-vis and Raman spectroscopic techniques. Reduction of GO was faster under solar irradiation. This study demonstrates that when introduced into saline waters, GO will undergo a range of transformations affecting its fate and potential effects to aquatic organisms.

Detection and Quantification of Graphene-Family Nanomaterials in the Environment.

An increase in production of commercial products containing graphene-family nanomaterials (GFNs) has led to concern over their release into the environment. The fate and potential ecotoxicological effects of GFNs in the environment are currently unclear, partially due to the limited analytical methods for GFN measurements. In this review, the unique properties of GFNs that are useful for their detection and quantification are discussed. The capacity of several classes of techniques to identify and/or quantify GFNs in different environmental matrices (water, soil, sediment, and organisms), after environmental transformations, and after release from a polymer matrix of a product is evaluated. Extraction and strategies to combine methods for more accurate discrimination of GFNs from environmental interferences as well as from other carbonaceous nanomaterials are recommended. Overall, a comprehensive review of the techniques available to detect and quantify GFNs are systematically presented to inform the state of the science, guide researchers in their selection of the best technique for the system under investigation, and enable further development of GFN metrology in environmental matrices. Two case studies are described to provide practical examples of choosing which techniques to utilize for detection or quantification of GFNs in specific scenarios. Because the available quantitative techniques are somewhat limited, more research is required to distinguish GFNs from other carbonaceous materials and improve the accuracy and detection limits of GFNs at more environmentally relevant concentrations.

Advancing the Use of Passive Sampling in Risk Assessment and Management of Sediments Contaminated with Hydrophobic Organic Chemicals: Results of an International Ex Situ Passive Sampling Interlaboratory Comparison.

This work presents the results of an international interlaboratory comparison on ex situ passive sampling in sediments. The main objectives were to map the state of the science in passively sampling sediments, identify sources of variability, provide recommendations and practical guidance for standardized passive sampling, and advance the use of passive sampling in regulatory decision making by increasing confidence in the use of the technique. The study was performed by a consortium of 11 laboratories and included experiments with 14 passive sampling formats on 3 sediments for 25 target chemicals (PAHs and PCBs). The resulting overall interlaboratory variability was large (a factor of ∼10), but standardization of methods halved this variability. The remaining variability was primarily due to factors not related to passive sampling itself, i.e., sediment heterogeneity and analytical chemistry. Excluding the latter source of variability, by performing all analyses in one laboratory, showed that passive sampling results can have a high precision and a very low intermethod variability (

A comprehensive framework for evaluating the environmental health and safety implications of engineered nanomaterials.

Engineered nanomaterials (ENM) are a growing aspect of the global economy, and their safe and sustainable development, use, and eventual disposal requires the capability to forecast and avoid potential problems. This review provides a framework to evaluate the health and safety implications of ENM releases into the environment, including purposeful releases such as for antimicrobial sprays or nano-enabled pesticides, and inadvertent releases as a consequence of other intended applications. Considerations encompass product life cycles, environmental media, exposed populations, and possible adverse outcomes. This framework is presented as a series of compartmental flow diagrams that serve as a basis to help derive future quantitative predictive models, guide research, and support development of tools for making risk-based decisions. After use, ENM are not expected to remain in their original form due to reactivity and/or propensity for hetero-agglomeration in environmental media. Therefore, emphasis is placed on characterizing ENM as they occur in environmental or biological matrices. In addition, predicting the activity of ENM in the environment is difficult due to the multiple dynamic interactions between the physical/chemical aspects of ENM and similarly complex environmental conditions. Others have proposed the use of simple predictive functional assays as an intermediate step to address the challenge of using physical/chemical properties to predict environmental fate and behavior of ENM. The nodes and interactions of the framework presented here reflect phase transitions that could be targets for development of such assays to estimate kinetic reaction rates and simplify model predictions. Application, refinement, and demonstration of this framework, along with an associated knowledgebase that includes targeted functional assay data, will allow better de novo predictions of potential exposures and adverse outcomes.

Aggregation, Sedimentation, Dissolution, and Bioavailability of Quantum Dots in Estuarine Systems.

To understand their fate and transport in estuarine systems, the aggregation, sedimentation, and dissolution of CdSe quantum dots (QDs) in seawater were investigated. Hydrodynamic size increased from 40 to 60 nm to >1 mm within 1 h in seawater, and the aggregates were highly polydispersed. Their sedimentation rates in seawater were measured to be 4-10 mm/day. Humic acid (HA), further increased their size and polydispersity, and slowed sedimentation. Light increased their dissolution and release of dissolved Cd. The ZnS shell also slowed release of Cd ions. With sufficient light, HA increased the dissolution of QDs, while with low light, HA alone did not change their dissolution. The benthic zone in estuarine systems is the most probable long-term destination of QDs due to aggregation and sedimentation. The bioavailability of was evaluated using the mysid Americamysis bahia. The 7-day LC50s of particulate and dissolved QDs were 290 and 23 µg (total Cd)/L, respectively. For mysids, the acute toxicity appears to be from Cd ions; however, research on the effects of QDs should be conducted with other organisms where QDs may be lodged in critical tissues such as gills or filtering apparatus and Cd ions may be released and delivered directly to those tissues.

Cross Validation of Two Partitioning-Based Sampling Approaches in Mesocosms Containing PCB Contaminated Field Sediment, Biota, and Activated Carbon Amendment.

The Gold Standard for determining freely dissolved concentrations (Cfree) of hydrophobic organic compounds in sediment interstitial water would be in situ deployment combined with equilibrium sampling, which is generally difficult to achieve. In the present study, ex situ equilibrium sampling with multiple thicknesses of silicone and in situ pre-equilibrium sampling with low density polyethylene (LDPE) loaded with performance reference compounds were applied independently to measure polychlorinated biphenyls (PCBs) in mesocosms with (1) New Bedford Harbor sediment (MA, U.S.A.), (2) sediment and biota, and (3) activated carbon amended sediment and biota. The aim was to cross validate the two different sampling approaches. Around 100 PCB congeners were quantified in the two sampling polymers, and the results confirmed the good precision of both methods and were in overall good agreement with recently published LDPE to silicone partition ratios. Further, the methods yielded Cfree in good agreement for all three experiments. The average ratio between Cfree determined by the two methods was factor 1.4 ± 0.3 (range: 0.6-2.0), and the results thus cross-validated the two sampling approaches. For future investigations, specific aims and requirements in terms of application, data treatment, and data quality requirements should dictate the selection of the most appropriate partitioning-based sampling approach.

Evaluating the Relationship between Equilibrium Passive Sampler Uptake and Aquatic Organism Bioaccumulation.

This Critcal Review evaluates passive sampler uptake of hydrophobic organic contaminants (HOCs) in water column and interstitial water exposures as a surrogate for organism bioaccumulation. Fifty-seven studies were found where both passive sampler uptake and organism bioaccumulation were measured and 19 of these investigations provided direct comparisons relating passive sampler uptake and organism bioaccumulation. Polymers compared included low-density polyethylene (LDPE), polyoxymethylene (POM), and polydimethylsiloxane (PDMS), and organisms ranged from polychaetes and oligochaetes to bivalves, aquatic insects, and gastropods. Regression equations correlating bioaccumulation (CL) and passive sampler uptake (CPS) were used to assess the strength of observed relationships. Passive sampling based concentrations resulted in log-log predictive relationships, most of which were within one to 2 orders of magnitude of measured bioaccumulation. Mean coefficients of determination (r2) for LDPE, PDMS, and POM were 0.68, 0.76, and 0.58, respectively. For the available raw, untransformed data, the mean ratio of CL and CPS was 10.8 ± 18.4 (n = 609). Using passive sampling as a surrogate for organism bioaccumulation is viable when biomonitoring organisms are not available. Passive sampling based estimates of bioaccumulation provide useful information for making informed decisions about the bioavailability of HOCs.

Passive Sampling in Regulatory Chemical Monitoring of Nonpolar Organic Compounds in the Aquatic Environment.

We reviewed compliance monitoring requirements in the European Union, the United States, and the Oslo-Paris Convention for the protection of the marine environment of the North-East Atlantic, and evaluated if these are met by passive sampling methods for nonpolar compounds. The strengths and shortcomings of passive sampling are assessed for water, sediments, and biota. Passive water sampling is a suitable technique for measuring concentrations of freely dissolved compounds. This method yields results that are incompatible with the EU's quality standard definition in terms of total concentrations in water, but this definition has little scientific basis. Insufficient quality control is a present weakness of passive sampling in water. Laboratory performance studies and the development of standardized methods are needed to improve data quality and to encourage the use of passive sampling by commercial laboratories and monitoring agencies. Successful prediction of bioaccumulation based on passive sampling is well documented for organisms at the lower trophic levels, but requires more research for higher levels. Despite the existence of several knowledge gaps, passive sampling presently is the best available technology for chemical monitoring of nonpolar organic compounds. Key issues to be addressed by scientists and environmental managers are outlined.

Calculating the diffusive flux of persistent organic pollutants between sediments and the water column on the Palos Verdes shelf superfund site using polymeric passive samplers.

Passive samplers were deployed to the seafloor at a marine Superfund site on the Palos Verdes Shelf, California, USA, and used to determine water concentrations of persistent organic pollutants (POPs) in the surface sediments and near-bottom water. A model of Fickian diffusion across a thin water boundary layer at the sediment-water interface was used to calculate flux of contaminants due to molecular diffusion. Concentrations at four stations were used to calculate the flux of DDE, DDD, DDMU, and selected PCB congeners from sediments to the water column. Three passive sampling materials were compared: PE strips, POM strips, and SPME fibers. Performance reference compounds (PRCs) were used with PE and POM to correct for incomplete equilibration, and the resulting POP concentrations, determined by each material, agreed within 1 order of magnitude. SPME fibers, without PRC corrections, produced values that were generally much lower (1 to 2 orders of magnitude) than those measured using PE and POM, indicating that SPME may not have been fully equilibrated with waters being sampled. In addition, diffusive fluxes measured using PE strips at stations outside of a pilot remedial sand cap area were similar to those measured at a station inside the capped area: 240 to 260 ng cm(-2) y(-1) for p,p'-DDE. The largest diffusive fluxes of POPs were calculated at station 8C, the site where the highest sediment concentrations have been measured in the past, 1100 ng cm(-2) y(-1) for p,p'-DDE.

Toxicity, bioaccumulation, and biotransformation of silver nanoparticles in marine organisms.

The toxicity, bioaccumulation, and biotransformation of citrate and polyvinylpyrrolidone (PVP) coated silver nanoparticles (NPs) (AgNP-citrate and AgNP-PVP) in marine organisms via marine sediment exposure was investigated. Results from 7-d sediment toxicity tests indicate that AgNP-citrate and AgNP-PVP did not exhibit toxicity to the amphipod (Ampelisca abdita) and mysid (Americamysis bahia) at ≤75 mg/kg dry wt. A 28-d bioaccumulation study showed that Ag was significantly accumulated in the marine polychaete Nereis virens (N. virens) in the AgNP-citrate, AgNP-PVP and a conventional salt (AgNO3) treatments. Synchrotron X-ray absorption spectroscopy (XAS) results showed the distribution of Ag species in marine sediments amended with AgNP-citrate, AgNP-PVP, and AgNO3 was AgCl (50­65%) > Ag2S (32­42%) > Ag metal (Ag0) (3­11%). In N virens, AgCl (25­59%) and Ag2S (10­31%) generally decreased and, Ag metal (32­44%) increased, relative to the sediments. The patterns of speciation in the worm were different depending upon the coating of the AgNP and both types of AgNPs were different than the AgNO3 salt. These results show that the AgNP surface capping agents influenced Ag uptake, biotransformation, and/or excretion. To our knowledge, this is the first demonstration of the bioaccumulation and speciation of AgNPs in a marine organism (N. virens).

Assessing organic contaminant fluxes from contaminated sediments following dam removal in an urbanized river.

In this study, methods and approaches were developed and tested to assess changes in contaminant fluxes resulting from dam removal in a riverine system. Sediment traps and passive samplers were deployed to measure particulate and dissolved polycyclic aromatic hydrocarbons (PAHs) and polychlorinated biphenyls (PCBs) in the water column prior to and following removal of a small, low-head dam in the Pawtuxet River, an urbanized river located in Cranston, RI, USA. During the study, concentrations of particulate and dissolved PAHs ranged from 21.5 to 103 µg/g and from 68 to 164 ng/L, respectively. Overall, temporal trends of PAHs showed no increases in either dissolved or particulate phases following removal of the dam. Dissolved concentrations of PCBs were very low, remaining below 1.72 ng/L at all sites. Particulate PCB concentrations across sites and time showed slightly greater variability, ranging from 80 to 469 ng/g, but with no indication that dam removal influenced any increases. Particulate PAHs and PCBs were sampled continuously at the site located below the dam and did not show sustained increases in concentration resulting from dam removal. The employment of passive sampling technology and sediment traps was highly effective in monitoring the concentrations and flux of contaminants moving through the river system. Variations in river flow had no effect on the concentration of contaminants in the dissolved or particulate phases, but did influence the flux rate of contaminants exiting the river. Overall, dam removal did not cause measurable sediment disturbance or increase the concentration or fluxes of dissolved or particulate PAHs and PCBs. This is due in large part to low volumes of impounded sediment residing above the dam and highly armored sediments in the river channel, which limited erosion. Results from this study will be used to improve methods and approaches that assess the short- and long-term impacts ecological restoration activities such as dam removal have on the release and transport of sediment-bound contaminants.

The distribution of sediment microplastics assemblages is driven by location and hydrodynamics, not sediment characteristics, in the Gulf of Maine, USA.

Microplastics (MP) are found in marine sediments across the globe, but we are just beginning to understand their spatial distribution and assemblages. In this study, we quantified MP in Gulf of Maine, USA sediments. MP were extracted from 20 sediment samples, followed by polymer identification using Raman spectroscopy. We detected 27 polymer types and 1929 MP kg-1 wet sediment, on average. Statistical analyses showed that habitat, hydrodynamics, and station proximity were more important drivers of MP assemblages than land use or sediment characteristics. Stations closer to one another were more similar in their MP assemblages, tidal rivers had higher numbers of unique plastic polymers than open water or embayment stations, and stations closer to shore had higher numbers of MP. There was little evidence of relationships between MP assemblages and land use, sediment texture, total organic carbon, or contaminants.

Quantitative thermodynamic exposure assessment of PCBs available to sandworms (Alitta virens) in activated carbon remediated sediment during ongoing sediment deposition.

Marine mesoscale studies with sandworms (Alitta virens) were conducted to isolate important processes governing the exposure and bioaccumulation of polychlorinated biphenyls (PCBs) at contaminated sediment sites. Ex situ equilibrium sampling with silicone-coated jars, and in situ passive sampling with low-density polyethylene (LDPE) were used to determine the performance of an activated carbon (AC) amendment remedy applied to the bed sediment. A quantitative thermodynamic exposure assessment ('QTEA') was performed, showing that PCB concentrations in polymers at equilibrium with the surficial sediment were suited to measure and assess the remedy effectiveness with regard to PCB bioaccumulation in worms. In practice, monitoring the performance of sediment remedies should utilize a consistent and predictive form of polymeric sampling of the sediment. The present study found that ex situ equilibrium sampling of the surficial sediment was the most useful for understanding changes in bioaccumulation potential as a result of the applied remedy, during bioturbation and ongoing sediment and contaminant influx processes. The ultrathin silicone coatings of the ex situ sampling provided fast equilibration of PCBs between the sediment interstitial water and the polymer, and the multiple coating thicknesses were applied to confirm equilibrium and the absence of surface sorption artifacts. Overall, ex situ equilibrium sampling of surficial sediment could fit into existing frameworks as a robust and cost-effective tool for contaminated sediment site assessment.

Application of low-density polyethylene (LDPE) passive samplers for monitoring PAHs in groundwater.

Equilibrium passive sampling continues to find increasing use for performing in situ assessments and monitoring of hydrophobic organic compounds (HOCs). Although this method has been successfully used in several field studies including open surface waters and sediments, comparatively, their use in groundwater has been very limited. In this study, low-density polyethylene (LDPE) passive samplers were deployed for 80 days in three groundwater wells contaminated with polycyclic aromatic hydrocarbons (PAHs). Prior to deployment, LDPE was loaded with performance reference compounds (PRCs) consisting of deuterated PAHs and their release used to ascertain system equilibrium. Within the 80-day deployment period, LDPE-groundwater equilibrium was confirmed for PAHs with molecular weights (MWs) in the range of 178 to 228 (i.e. anthracene, chrysene). Measured freely dissolved concentrations (Cw) were between one to three orders of magnitude lower than the total filtered concentrations (Ctotal) in the studied wells. The sum of PAHs (ΣPAHs) measured based on Cw and Ctotal were 2.05, 0.07 and 29.2 µg L-1 and 197, 59.7 and 1010 µg L-1, at wells 1, 2 and 3, respectively. A separate dataset, comprising long-term (2010 to 2022) concentrations of PAHs in total (i.e., unfiltered) groundwater, is also presented to provide insight into PAH contamination levels at the assessed groundwater wells based on conventional measurement. Estimated in situ LDPE daily clearance volumes (2.34 to 27.56 Ld-1) for the target analytes were far less than the daily turnover of ground water (144 to 348 Ld-1) encountered in the wells eliminating the possibility of depletive sampling of the groundwater by the passive samplers. These results represent the first published study on the practical application of equilibrium passive sampling using LDPE for monitoring and quantitatively assessing PAHs in groundwater. Also, this work demonstrates that LDPEs are a useful tool for measuring the Cw of PAHs in groundwater, a critical contaminant in many ecological and human health risk assessments.

Sediment Toxicity Tests: A Critical Review of Their use in Environmental Regulations.

Sediments are an integral component of aquatic systems, linking multiple water uses, functions, and services. Contamination of sediments by chemicals is a worldwide problem, with many jurisdictions trying to prevent future pollution (prospective) and manage existing contamination (retrospective). The present review assesses the implementation of sediment toxicity testing in environmental regulations globally. Currently, the incorporation of sediment toxicity testing in regulations is most common in the European Union (EU), North America, and Australasian regions, with some expansion in Asia and non-EU Europe. Employing sediment toxicity testing in prospective assessments (i.e., before chemicals are allowed on the market) is most advanced and harmonized with pesticides. In the retrospective assessment of environmental risks (i.e., chemicals already contaminating sediments), regulatory sediment toxicity testing practices are applied inconsistently on the global scale. International harmonization of sediment toxicity tests is considered an asset and has been successful through the widespread adoption and deployment of Organisation for Economic Co-operation and Development guidelines. On the other hand, retrospective sediment assessments benefit from incorporating regional species and protocols. Currently used toxicity testing species are diverse, with temperate species being applied most often, whereas test protocols are insufficiently flexible to appropriately address the range of environmental contaminants, including nanomaterials, highly hydrophobic contaminants, and ionized chemicals. The ever-increasing and -changing pressures placed on aquatic resources are a challenge for protection and management efforts, calling for continuous sediment toxicity test method improvement to insure effective use in regulatory frameworks. Future developments should focus on including more subtle and specific toxicity endpoints (e.g., incorporating bioavailability-based in vitro tests) and genomic techniques, extending sediment toxicity testing from single to multispecies approaches, and providing a better link with ecological protection goals. Environ Toxicol Chem 2024;43:1697-1716. © 2024 The Authors. Environmental Toxicology and Chemistry published by Wiley Periodicals LLC on behalf of SETAC.

Combined temperature and salinity effects on the passive sampling of PAHs with an assessment of impacts to petroleum toxicity.

In equilibrium-based passive sampling applications, the accuracy of estimating freely dissolved concentration (Cfree) of hydrophobic organic compounds (HOCs) relies on the passive sampler-water partition coefficient (KPS-W) values applied. The vast majority of KPS-W are generated under standard conditions: 20 °C in deionized or freshwater. Few empirically derived values are available for non-standard conditions. In this study, polyethylene (PE)-water partitioning coefficients (KPE-W) were experimentally determined for 15 polycyclic aromatic hydrocarbons (PAHs, comprising 9 parent and 6 alkylated compounds) under three different temperature (10, 20, 30 °C) and salinity (0, 18 and 36‰) regimes, the KPE-W values were found to correlate strongly with a variety of molecular parameters (e.g., octanol-water partition coefficients (KOW), molecular weight (MW) and molecular volume (MVOL)). The effects of temperature and salinity on the magnitude of KPE-W were found to be substantial. For temperature, the values range between -0.005 and -0.023 log units per °C; these values indicate that every 10 °C rise in temperature would potentially decrease the KPE-W by a factor of between 0.4 to 1.6. For salinity, the values range from 0.0028 to 0.0057 log units per unit ‰, indicating that an 18‰ increase in salinity would likely increase the KPE-W by a factor of between 0.28 and 0.82. Moreover, temperature and salinity were shown to be independent of each other and non-interacting. Temperature effects were chemical-specific and moderately dependent on hydrophobicity (expressed as the KOW), whereas salinity effects were independent of hydrophobicity. We also assessed the combined impact of temperature and salinity, which showed increasing effects with the hydrophobicity of the PAHs studied. Based on the results, KPE-W values adjusted for site-specific temperature and salinity can be calculated. The impact of applying such site-specific values was demonstrated using a PE-based field monitoring dataset for PAHs from coastal waters of Grand Isle (LA, USA) collected during the 2010 Deepwater Horizon oil spill. When KPE-W values were adjusted to 10 °C and 30 °C, the final freely dissolved concentrations (Cfree) decreased or increased depending on the adjustment. Use of the results of this investigation allow for adjusting existing PE-based datasets to site-specific conditions resulting in more accurate Cfree values for estimating exposure and adverse ecological effects.