Search

The main objective of this study was to model the contribution of shelf sediments in the Arctic Ocean to the total mass of neutral organic contaminants accumulated in the Arctic environment using a standardized emission scenario for sets of hypothetical chemicals and realistic emission estimates (1930-2100) for polychlorinated biphenyl congener 153 (PCB-l53). Shelf sediments in the Arctic Ocean are shown to be important reservoirs for neutral organic chemicals across a wide range of partitioning properties, increasing the total mass in the surface compartments of the Arctic environment by up to 3.5-fold compared to simulations excluding this compartment. The relative change in total mass for hydro-phobic organic chemicals with log air-water partition coefficients ≥0 was greater than for chemicals with-properties similar to typical POPs. The long-term simulation of PCB-153 generated modeled concentrations in shelf sediments in reasonable agreement with available monitoring data and illustrate that the relative importance of shelf sediments in the Arctic Ocean for influencing surface ocean concentrations (and therefore exposure via the pelagic food web) is most pronounced once primary emissions are exhausted and secondary sources dominate. Additional monitoring and modeling work to better characterize the role of shelf sediments for contaminant fate is recommended. [ABSTRACT FROM AUTHOR]

A mechanistic mass balance bioconcentration model is developed and parameterized for ionogenic organic chemicals (IOCs) in fish and evaluated against a compilation of empirical bioconcentration factors (BCFs). The model is subsequently applied to a set of perfluoroalkyl acids. Key aspects of model development include revised methods to estimate the chemical absorption efficiency of IOCs at the respiratory surface ( EW) and the use of distribution ratios to characterize the overall sorption capacity of the organism. Membrane-water distribution ratios ( DMW) are used to characterize sorption to phospholipids instead of only considering the octanol-water distribution ratio ( DOW). Modeled BCFs are well correlated with the observations (e.g., r2 = 0.68 and 0.75 for organic acids and bases, respectively) and accurate to within a factor of three on average. Model prediction errors appear to be largely the result of uncertainties in the biotransformation rate constant ( kM) estimates and the generic approaches for estimating sorption capacity (e.g., DMW). Model performance for the set of perfluoroalkyl acids considered is highly dependent on the input parameters describing hydrophobicity (i.e., log KOW of the neutral form). The model applications broadly support the hypothesis that phospholipids contribute substantially to the sorption capacity of fish, particularly for compounds that exhibit a high degree of ionization at biologically relevant pH. Additional empirical data on biotransformation and sorption to phospholipids and subsequent incorporation into property estimation approaches (e.g., kM, DMW) are priorities with respect to improving model performance. Environ. Toxicol. Chem. 2013;32:115-128. © 2012 SETAC [ABSTRACT FROM AUTHOR]

The purpose of Annex E in the Stockholm Convention (SC) on Persistent Organic Pollutants (POPs) is to assess whether a chemical is likely, as a result of its long-range environmental transport, to lead to significant adverse human health or environmental effects, such that global action is warranted. To date, risk profiles for nominated POPs have not consistently selected assessment endpoints or completed mandated risk characterizations. An assessment endpoint hierarchy is proposed to facilitate risk characterization for the implementation of the SC. The framework is illustrated for a nominated POP, hexabromocyclododecane (HBCD), using three risk estimation methods. Based on current monitoring and toxicity data, the screening-level results indicate that humans and ecological receptors in remote regions such as the Arctic are unlikely to experience significant adverse effects (i.e., low risk) due to long-range environmental transport of HBCD. The results for birds are more uncertain than the results for fish and mammals due to the paucity of avian toxicity data. Risk characterization results for HBCD and for some listed POPs are compared to illustrate how the proposed methods can further assist decision-making and chemical management. [ABSTRACT FROM AUTHOR]

Submerged aquatic vegetation can act as both a mitigating factor (e.g., reducing downstream impacts of pesticides following runoff/spray drift) and mobilizing factor (e.g., remobilization of contaminants from sediments) influencing the fate and distribution of organic contaminants in the environment. Consequently, there has been wide scientific and regulatory interest in assessing the role of these plants in different contamination scenarios. Mechanistic models describing the environmental fate of contaminants in submerged aquatic vegetation are useful tools for interpreting laboratory and field measurements in addition to providing valuable information to risk assessors. In this study, we developed a fugacity-based model to investigate the influence of particle deposition to plant surfaces on the fate and distribution of two substances in small ponds. The main motivation for conducting this study was to address the fact that the potential contribution of this process is not typically considered by many types of models describing contaminant dynamics in submerged aquatic vegetation. For the hydrophobic substance included in this evaluation (lambda-cyhalothrin), model performance was greatly improved by including this process. The model was also applied in a generic context to compare the importance of particle deposition versus direct water uptake as a function of chemical properties (log K0w) and concentration of suspended solids in the water column. The generic application demonstrated that contaminant mass transfer is dominated by particle deposition for chemicals with log K0w greater than approximately 5.5-6 across a wide range of suspended solid concentrations and can be important even for low log K0w substances in some circumstances. Further empirical and modeling studies are recommended to explore this process more comprehensively. [ABSTRACT FROM AUTHOR]

Multimedia environmental fate models are useful tools to investigate the long-term impacts of remediation measures designed to alleviate potential ecological and human health concerns in contaminated areas. Estimating and communicating the uncertainties associated with the model simulations is a critical task for demonstrating the transparency and reliability of the results. The Extended Fourier Amplitude Sensitivity Test (Extended FAST) method for sensitivity analysis and Bayesian Markov chain Monte Carlo (MCMC) method for uncertainty analysis and model calibration have several advantages over methods typically applied for multimedia environmental fate models. Most importantly, the simulation results and their uncertainties can be anchored to the available observations and their uncertainties. We apply these techniques for simulating the historical fate of polychiorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs) in the Grenland fjords, Norway, and for predicting the effects of different contaminated sediment remediation (capping) scenarios on the future levels of PCDD/Fs in cod and crab therein. The remediation scenario simulations show that a significant remediation effect can first be seen when significant portions of the contaminated sediment areas are cleaned up, and that increase in capping area leads to both earlier achievement of good fjord status and narrower uncertainty in the predicted timing for this. [ABSTRACT FROM AUTHOR]

The extent to which chemicals bioaccumulate in aquatic and terrestrial organisms represents a fundamental consideration for chemicals management efforts intended to protect public health and the environment from pollution and waste. Many chemicals, including most pharmaceuticals and personal care products (PPCPs), are ionizable across environmentally relevant pH gradients, which can affect their fate in aquatic and terrestrial systems. Existing mathematical models describe the accumulation of neutral organic chemicals and weak acids and bases in both fish and plants. Further model development is hampered, however, by a lack of mechanistic insights for PPCPs that are predominantly or permanently ionized. Targeted experiments across environmentally realistic conditions are needed to address the following questions: (1) What are the partitioning and sorption behaviors of strongly ionizing chemicals among species? (2) How does membrane permeability of ions influence bioaccumulation of PPCPs? (3) To what extent are salts and associated complexes with PPCPs influencing bioaccumulation? (4) How do biotransformation and other elimination processes vary within and among species? (5) Are bioaccumulation modeling efforts currently focused on chemicals and species with key data gaps and risk profiles? Answering these questions promises to address key sources of uncertainty for bioaccumulation modeling of ionizable PPCPs and related contaminants. Environ Toxicol Chem 2024;43:502-512. © 2022 The Authors. Environmental Toxicology and Chemistry published by Wiley Periodicals LLC on behalf of SETAC., (© 2022 The Authors. Environmental Toxicology and Chemistry published by Wiley Periodicals LLC on behalf of SETAC.)

Surfactants are a class of chemicals released in large quantities to water, and therefore bioconcentration in fish is an important component of their safety assessment. Their structural diversity, which encompasses nonionic, anionic, cationic and zwitterionic molecules with a broad range of lipophilicity, makes their evaluation challenging. A strong influence of environmental pH adds a further layer of complexity to their bioconcentration assessment. Here we present a framework that penetrates this complexity. Using simple equations derived from current understanding of the relevant underlying processes, we plot the key bioconcentration parameters (uptake rate constant, elimination rate constant and bioconcentration factor) as a function of its membrane lipid/water distribution ratio and the neutral fraction of the chemical in water at pH 8.1 and at pH 6.1. On this chemical space plot, we indicate boundaries at which four resistance terms (perfusion with water, transcellular, paracellular, and perfusion with blood) limit transport of surfactants across the gills. We then show that the bioconcentration parameters predicted by this framework align well with in vivo measurements of anionic, cationic and nonionic surfactants in fish. In doing so, we demonstrate how the framework can be used to explore expected differences in bioconcentration behavior within a given sub-class of surfactants, to assess how pH will influence bioconcentration, to identify the underlying processes governing bioconcentration of a particular surfactant, and to discover knowledge gaps that require further research. This framework for amphiphilic chemicals may function as a template for improved understanding of the accumulation potential of other ionizable chemicals of environmental concern, such as pharmaceuticals or dyes.

Fish bioconcentration factors (BCFs) are commonly used in chemical hazard and risk assessment. For neutral organic chemicals BCFs are positively correlated with the octanol-water partition ratio ( K OW ), but K OW is not a reliable parameter for surfactants. Membrane lipid-water distribution ratios ( D MLW ) can be accurately measured for all kinds of surfactants, using phospholipid-based sorbents. This study first demonstrates that D MLW values for ionic surfactants are more than 100 000 times higher than the partition ratio to fish-oil, representing neutral storage lipid. A non-ionic alcohol ethoxylate surfactant showed almost equal affinity for both lipid types. Accordingly, a baseline screening BCF value for surfactants (BCF baseline ) can be approximated for ionic surfactants by multiplying D MLW by the phospholipid fraction in tissue, and for non-ionic surfactants by multiplying D MLW by the total lipid fraction. We measured D MLW values for surfactant structures, including linear and branched alkylbenzenesulfonates, an alkylsulfoacetate and an alkylethersulfate, bis(2-ethylhexyl)-surfactants ( e.g. , docusate), zwitterionic alkylbetaines and alkylamine-oxides, and a polyprotic diamine. Together with sixty previously published D MLW values for surfactants, structure-activity relationships were derived to elucidate the influence of surfactant specific molecular features on D MLW . For 23 surfactant types, we established the alkyl chain length at which BCF baseline would exceed the EU REACH bioaccumulation (B) threshold of 2000 L kg -1 , and would therefore require higher tier assessments to further refine the BCF estimate. Finally, the derived BCF baseline are compared with measured literature in vivo BCF data where available, suggesting that refinements, most notably reliable estimates of biotransformation rates, are needed for most surfactant types.

The objective of the present study was to review the current knowledge regarding the bioaccumulation potential of ionizable organic compounds (IOCs), with a focus on the availability of empirical data for fish. Aspects of the bioaccumulation potential of IOCs in fish that can be characterized relatively well include the pH dependence of gill uptake and elimination, uptake in the gut, and sorption to phospholipids (membrane-water partitioning). Key challenges include the lack of empirical data for biotransformation and binding in plasma. Fish possess a diverse array of proteins that may transport IOCs across cell membranes. Except in a few cases, however, the significance of this transport for uptake and accumulation of environmental contaminants is unknown. Two case studies are presented. The first describes modeled effects of pH and biotransformation on the bioconcentration of organic acids and bases, while the second employs an updated model to investigate factors responsible for accumulation of perfluorinated alkyl acids. The perfluorinated alkyl acid case study is notable insofar as it illustrates the likely importance of membrane transporters in the kidney and highlights the potential value of read-across approaches. Recognizing the current need to perform bioaccumulation hazard assessments and ecological and exposure risk assessment for IOCs, the authors provide a tiered strategy that progresses (as needed) from conservative assumptions (models and associated data) to more sophisticated models requiring chemical-specific information. Environ Toxicol Chem 2017;36:882-897. © 2016 SETAC., (© 2016 SETAC.)

Elevated concentrations of various industrial-use Persistent Organic Pollutants (POPs), such as polychlorinated biphenyls (PCBs), have been reported in some developing areas in subtropical and tropical regions known to be destinations of e-waste. We used a recent inventory of the global generation and exports of e-waste to develop various global scale emission scenarios for industrial-use organic contaminants (IUOCs). For representative IUOCs (RIUOCs), only hypothetical emissions via passive volatilization from e-waste were considered whereas for PCBs, historical emissions throughout the chemical life-cycle (i.e., manufacturing, use, disposal) were included. The environmental transport and fate of RIUOCs and PCBs were then simulated using the BETR Global 2.0 model. Export of e-waste is expected to increase and sustain global emissions beyond the baseline scenario, which assumes no export. A comparison between model predictions and observations for PCBs in selected recipient regions generally suggests a better agreement when exports are accounted for. This study may be the first to integrate the global transport of IUOCs in waste with their long-range transport in air and water. The results call for integrated chemical management strategies on a global scale.