Guidance on the Application of Polyurethane Foam Disk Passive Air Samplers for Measuring Nonane and Short-Chain Chlorinated Paraffins in Air: Results from a Screening Study in Urban Air.

This study provides guidance on using polyurethane foam-based passive air samplers (PUF-PASs) for atmospheric nonane chlorinated paraffins (C9-CPs) and short-chain CPs (SCCPs) and reports SCCP concentrations in air in the Greater Toronto Area (GTA), Canada. We estimated the partition coefficients between PUF and air (KPUF-A) and between octanol and air (KOA) for C9-CP and SCCP congeners using the COSMO-RS method, so that PUF disk uptake profiles for each formula group could be calculated. We then measured SCCP concentrations in PUF disk samples collected from distinct source sectors in urban air across the GTA. Concentrations in samplers were used to calculate C9-CP and SCCP concentrations in air and the PUF disk uptake profiles revealed that time-weighted linear phase sampling was possible for congeners having log KOA values greater than 8.5. The highest SCCP concentrations, with an annual average concentration of 35.3 ng/m3, were measured at the industrial site, whereas lower but comparable SCCP concentrations were found in residential and background sites, with annual averages of 7.73 and 10.5 ng/m3, respectively. No consistent seasonal variation in SCCP concentrations was found in the six distinct source sectors. Direct measurements of KPUF-A and KOA values as a function of temperature could be used to increase accuracy in future studies.

Novel Bayesian Method to Derive Final Adjusted Values of Physicochemical Properties: Application to 74 Compounds.

Accurate values of physicochemical properties are essential for screening semivolatile organic compounds for human and environmental hazard and risk. In silico approaches for estimation are widely used, but the accuracy of these and measured values can be difficult to ascertain. Final adjusted values (FAVs) harmonize literature-reported measurements to ensure consistency and minimize uncertainty. We propose a workflow, including a novel Bayesian approach, for estimating FAVs that combines measurements using direct and indirect methods and in silico values. The workflow was applied to 74 compounds across nine classes to generate recommended FAVs (FAVRs). Estimates generated by in silico methods (OPERA, COSMOtherm, EPI Suite, SPARC, and polyparameter linear free energy relationships (pp-LFER) models) differed by orders of magnitude for some properties and compounds and performed systematically worse for larger, more polar compounds. COSMOtherm and OPERA generally performed well with low bias although no single in silico method performed best across all compound classes and properties. Indirect measurement methods produced highly accurate and precise estimates compared with direct measurement methods. Our Bayesian method harmonized measured and in silico estimated physicochemical properties without introducing observable biases. We thus recommend use of the FAVRs presented here and that the proposed Bayesian workflow be used to generate FAVRs for SVOCs beyond those in this study.

Indoor Dust/Air Partitioning: Evidence for Kinetic Delay in Equilibration for Low-Volatility SVOCs.

Effective modeling of semivolatile organic chemical (SVOC) partitioning between air and indoor dust is investigated by calculating partition ratios for selected SVOCs between air and n-octanol as well as 8 other oligomers similar in chemical structure to common components of household dust. COSMO-RS solvation theory was used to calculate air-oligomer partition ratios, which were converted to estimates for KOA (octanol-air) and Kdust-air. The results are compared with reported monitored partition ratios with good agreement for the more volatile SVOCs of vapor pressure (VP) exceeding 10-5 Pa and corresponding calculated log Kdust-air (m3 g-1) of <5.5 or unitless log KOA of <11.5. For less volatile SVOCs, reported values of KDA are significantly lower than predicted, with the deviation increasing with decrease in VP. This effect is attributed to a kinetic delay in which characteristic times for equilibration exceed the dust-air contact time, and equilibrium is not achieved. It is hoped that the approach of computing partition ratios of SVOCs using oligomers selected on the basis of likely dust sources and compositions may improve the estimation of indoor human exposure to SVOCs present in air and dust and assist in exploiting dust samples to monitor and evaluate the fate and exposure of organic chemicals used indoors.

Kinetic Delay in Partitioning and Parallel Particle Pathways: Underappreciated Aspects of Environmental Transport.

We outline the general conditions under which chemicals of high hydrophobicity or, more generally, high partition ratios (HPRs) in water or air, may experience unexpectedly long kinetic delays in approaching equilibrium conditions with organic media. Such a "hydrophobic delay" in the case of K OW or an "aerophobic" delay in the case of KOA may be misinterpreted as being caused by a change in partitioning behavior or mechanism, resulting in development of nonlinear regression models describing intermedia partitioning. In fact, the partitioning is fundamentally linear but is distorted by a kinetic delay in partitioning. To illustrate this concept, we first compile the fundamental equations describing the diffusive equilibration processes, including a complementary transport mechanism termed a parallel particle pathway (PPP). Such a mechanism may occur simultaneously, shortening the HPR delay and complicating interpretation. Second, we describe five examples in which the HPR delay explains the observed and occasionally difficult-to-interpret environmental behavior of chemicals, namely studies of air-aerosol partitioning, chemical accumulation in indoor dust and surfaces, air-vegetation partitioning, internal transport in organisms, and fish bioaccumulation and toxicity. We believe that the general HPR delay and PPP issues deserve exposure as a commonly occurring and often underappreciated process.

COSMO-RS solute partition ratios for solvent mixtures of unknown composition: Henry's law constants as descriptors for mixture sigma profiles.

Henry's law constants (H) for selected probe molecules have been used as descriptors to estimate the COSMO-RS sigma profiles of solvents and solvent mixtures. Henry's law constants were calculated with COSMOtherm for small sets of probe molecules in 155 organic solvents (training set), and these constants subsequently used as descriptors to model the solvent sigma profiles with 61 multiple linear regression (MLR) equations. Subsequent input into COSMOtherm of weighted basis molecule solvent mixtures whose sigma profiles closely matched those modelled for the training set solvents allowed estimation of air-solvent and water-solvent partition ratios for solutes in solvents and solvent mixtures without input of the solvent or solvent mixture identity. The best performing model had 16 descriptors and gave both a training and test set average root-mean square error (RMSE) of 0.008 and an average relative square error (RSE) of 0.07. Partition ratios (K) were then generated for a test set of 251 additional organic solute molecules in solvent/water media where solvents were test set compounds and H constants for the same probe molecules were used as descriptors. The best performing sigma profile model yielded log K RMSE values ranging from 0.17 to 0.92. Finally, this approach was applied to several mixtures ranging from simple binary mixtures to two mixtures considered to be of unknown or variable composition, complex reaction productions or biological materials (UVCBs), namely gasoline and an essential oil mixture. Mixture/water partition ratios were estimated for 251 solutes giving log K RMSE values ranging from 0.24 to 0.88.

Medium- and long-chain chlorinated paraffins in air: A review of levels, physicochemical properties, and analytical considerations.

Chlorinated paraffins (CPs) are synthetic chemicals that are produced at high volumes and have a global presence. CPs are generally divided into three groups based on their carbon chain lengths: short-chain CPs (SCCPs, C10-13), medium-chain CPs (MCCPs, C14-17), and long-chain CPs (LCCPs, C≥18). SCCPs have been formally recognized as persistent organic pollutants (POPs) and have been listed under the Stockholm Convention on POPs. Concerns about increases in MCCP and LCCP production as replacements for SCCP products are rising, given their similar properties to SCCPs and the fact that they remain relatively understudied with only a few reported measurements in air. Passive air samplers with polyurethane foam disks (PUF-PAS), which have been successfully applied to SCCPs, provide an opportunity to expand the existing body of data on MCCP and LCCP air concentrations, as they are inexpensive and require little maintenance. The uptake of MCCPs and LCCPs by PUF disk samplers is characterized in this paper based on newly derived PUF-air partitioning coefficients using COSMOtherm. The ability of PUF disk samplers to capture both gas-phase and particle fractions is important because MCCPs and LCCPs have reduced volatility compared to SCCPs and therefore are mainly associated with particulate matter in air. In addition, due to their use as additives in plastics and rubber products, they are associated with micro- and nanoplastics, which are considered to be potential vectors for the long-range atmospheric transport (LRAT) of these chemicals. The review has highlighted other limitations to reporting of MCCPs and LCCPs in air, including the lack of suitable analytical standards and the requirement for advanced analytical methods to detect and resolve these complex mixtures. Overall, this review indicates that further research is needed in many areas for medium- and long-chain chlorinated paraffins in order to better understand their occurrence, transport and fate in air.

FTIR matrix-isolation study of the reaction products of vanadium atoms with propene: observation of allylvanadium hydride as a precursor to sacrificial hydrogenation of propene.

Vanadium atoms have been reacted with different partial pressures of propene in Ar under matrix-isolation conditions, and the products have been observed using Fourier transform infrared (FTIR) spectroscopy. Under dilute propene in Ar conditions, new features are observed in the IR spectra corresponding to a C-H insertion product, identified here as H-V-(η(3)-allyl). Use of d(3)-propene (CD(3)-CH═CH(2)) demonstrates that the initial V-atom insertion occurs at the methyl group of the propene molecule, and DFT calculations have been used to support the identity of the initial product. Upon increasing the partial pressure of propene, additional features corresponding to propane (C(3)H(8)) are observed, with the hydrogen-atom source for the observed hydrogenation demonstrated to be additional propene units. Analysis of a systematic increase in the partial pressure of propene in the system demonstrates that the yield of propane correlates with the decrease of the allyl product, demonstrating the H-V(allyl) species as a reactive intermediate in the overall hydrogenation process. An overall mechanism is proposed to rationalize the formation of the insertion product and ultimately the products of hydrogenation, which agrees with previous gas-phase and matrix-isolation work involving propene and the related system, ethene.

Environmental modelling of hexamethoxymethylmelamine, its transformation products, and precursor compounds: An emerging family of contaminants from tire wear.

Hexamethoxymethylmelamine (HMMM) is a polymer crosslinking agent used commercially to manufacture tires. HMMM is a ubiquitous contaminant in urban surface waters due to its presence in tire-wear particles and its tendency to be transported into receiving waters during rain events through road runoff. It has recently been determined that this chemical readily transforms into numerous other compounds, several of which have also been detected in the aquatic environment. However, there is limited knowledge about the fate and distribution of HMMM and its likely transformation products and precursor compounds. COSMO-RS solvation theory was used to estimate the physico-chemical properties of HMMM and 24 related derivatives, including their aqueous solubility, various partitioning properties, vapour pressure, and melting point. Using these properties as inputs to the Equilibrium Criterion (EQC) fugacity-based multimedia model, three different emission scenarios were modeled. Overall, these compounds were predicted to readily partition into aqueous media, with distributions in water increasing with the loss of methoxymethyl groups. In addition, the persistence of the transformation products of HMMM was predicted to decline with the extent of these transformations. The EQC model predictions indicate that these compounds are subject to overland transport into surface waters. This study provides insights into the fate and behaviour of HMMM and its transformation compounds and contributes to the growing literature on the hazards of organic chemicals derived from tire wear.

Property Estimation of Per- and Polyfluoroalkyl Substances: A Comparative Assessment of Estimation Methods.

To accurately predict the environmental fate of per- and polyfluoroalkyl substances (PFAS), high-quality physicochemical property data are required. Because such data are often not available from experiments, assessment of the accuracy of existing property estimation models is essential. The quality of predicted physicochemical property data for a set of 25 PFAS was examined using COSMOtherm, EPI Suite, the estimation models accessible through the US Environmental Protection Agency's CompTox Chemicals Dashboard, and Linear Solvation Energy Relationships (LSERs) available through the UFZ-LSER Database. The results showed that COSMOtherm made the most accurate acid dissociation constant and air-water partition ratio estimates compared with literature data. The OPEn structure-activity/property Relationship App (OPERA; developed through the CompTox Chemicals Dashboard) estimates of vapor pressure and dry octanol-air partition ratios were the most accurate compared with other models of interest. Wet octanol-water partition ratios were comparably predicted by OPERA and EPI Suite, and the organic carbon soil coefficient and solubility were well predicted by OPERA and COSMOtherm. Acid dissociation of the perfluoroalkyl acids has a significant impact on their physicochemical properties, and corrections for ionization were included where applicable. Environ Toxicol Chem 2020;39:775-786. © 2020 SETAC.

A perspective on the role of fugacity and activity for evaluating the PBT properties of organic chemicals and providing a multi-media synoptic indicator of environmental contamination.

The hazard and risk from organic chemicals present in the environment are routinely evaluated using P (persistence), B (bioaccumulation) and T (toxicity) criteria. We present a perspective on how models based on the equilibrium criteria of fugacity and chemical activity can contribute to all three evaluations, thus providing a consistent and seamless assessment process. Persistence and its closely related, but fundamentally different property, chemical residence time can be determined from degradation half-lives (typically obtained from monitoring data) and multi-media mass balance models describing chemical fate and transport in real or evaluative environments. Bioaccumulation is driven by equilibrium partitioning processes that can be estimated from fugacity models treating uptake by respiration and diet in single organisms and in food webs, most commonly for aquatic systems for which confirmatory monitoring data can be obtained. Biomagnification is readily evaluated both experimentally and as a fugacity (or activity) increase from prey to predator. Toxicokinetic evaluations of chemical uptake and disposition in a variety of organisms, including humans, can be obtained using fugacity- and physiologically-based pharmacokinetic models. Toxicodynamic processes of chemical interactions with organisms leading to adverse toxic outcomes are less obviously amenable to fugacity assessment with the notable exception of baseline toxicity (narcosis), the most common mode of action of commercial chemicals. It is shown that a range of fugacities can be defined and correlated for specific species thus enabling direct comparison of fugacities estimated or monitored in the environment with fugacities resulting in baseline toxicity. Finally, it is shown that fugacity and activity can serve as multi-media metrics of chemical contamination in ecosystems, thus enabling identification of specific regions and species at greatest risk in a pictorial format that is readily understandable to scientific and regulatory communities and to the general public.

QSPRs for Molecular Diffusion Coefficients in Polymeric Passive Samplers: A Comparison of Simple Molecular and Quantum-mechanical Sigma-moment Descriptors.

Linear quantitative structure-property relationships (QSPRs) for the prediction of diffusion coefficients (log Dp ) were developed for organic contaminants in two common passive sampler materials, polydimethylsiloxane (PDMS) and low-density polyethylene (LDPE). Literature data was compiled for both PDMS and LDPE resulting in final data sets of 196 and 79 compounds, respectively. Data sets contained compounds with log Dp values that ranged over about 5 log units and 3 log units for PDMS and LDPE, respectively. The quality of log Dp prediction using either simple molecular descriptors or quantum-chemical based COSMO-RS sigma moment descriptors was compared for both materials. For PDMS, the sigma moment descriptor QSPR had the best predictivity with a correlation coefficient of R2 =0.85 and root mean square error (RMSE) of 0.36 for log Dp . The molecular descriptor QSPR resulted in a correlation coefficient of R2 =0.78 and RMSE of 0.45 for log Dp . For LDPE, the molecular descriptor QSPR had the best predictivity, with the final correlation coefficient of R2 =0.86 and RMSE of 0.21 for log Dp . The sigma moment descriptor QSPR resulted in a correlation coefficient of R2 =0.66 and RMSE of 0.33 for log Dp . The purely electronic structure-based sigma moments are therefore shown to be a viable option for descriptors compared to the more commonly used molecular descriptors for organic contaminants in PDMS. The significance of the descriptors in each QSPR is discussed.

Estimating the Mass of Chemicals Associated with Ocean Plastic Pollution to Inform Mitigation Efforts.

Plastic pollution in the marine environment is well documented. What remains less recognized and understood are the chemicals associated with it. Plastics enter the ocean with unreacted monomers, oligomers, and additives, which can leach over time. Moreover, plastics sorb organic and inorganic chemicals from surrounding seawater, for example, polychlorinated biphenyls (PCBs) and metals. Thus, interception and cleanup of plastics reduces the amount of chemical contaminants entering or reentering the oceans and removes those already present. Here, we estimate 1) the mass of selected chemical additives entering the global oceans with common plastic debris items, and 2) the mass of sorbed chemicals (using PCBs as a case study) associated with microplastics in selected locations. We estimate the mass of additives that entered the oceans in 2015 as constituents of 7 common plastic debris items (bottles, bottle caps, expanded polystyrene (EPS) containers, cutlery, grocery bags, food wrappers, and straws or stirrers). We calculate that approximately 190 tonnes (t) of 20 chemical additives entered the oceans with these items in 2015. We also estimate the mass of PCBs associated with microplastics in 2 coastal (Hong Kong and Hawaii) and 2 open ocean (North Pacific and South Atlantic gyres) locations, as comparative case studies. We find that the mass of chemicals is related to the mass of plastics in a location, with greater mass of PCBs closer to the source (i.e., land), where there is more plastic per unit area compared to the open ocean. We estimate approximately 85 000 times more PCBs associated with plastics in an average 4.5-km stretch of beach in Hong Kong than from the same size transect in the North Pacific gyre. In conclusion, continuing efforts for plastic interception and cleanup on shorelines effectively reduces the amount of plastic-related chemicals entering and/or reentering the marine environment. Integr Environ Assess Manag 2019;15:596-606. © 2019 SETAC.

FTIR analysis of dimethyl ether decomposition products following charge transfer ionization with Ar+ under matrix isolation conditions.

Fourier transform infrared spectroscopic analysis has been performed on argon matrices formed following electron bombardment of argon/dimethyl ether mixtures. Products consistent with the ionization and subsequent fragmentation of dimethyl ether cation have been observed. Following ionization of dimethyl ether, fragmentation occurs that is consistent with ionization energy greater than 15 eV due to efficient charge transfer from dimethyl ether to Ar(+) as the major ionization process. Major products observed in the infrared spectra are methane, formaldehyde, HCO(*), CO, and Ar(2)H(+). These products are consistent with the known fragmentation of photoionized dimethyl ether in a 15-16 eV ionization energy range. However, the observation of dehydrogenated products is consistent with additional abstraction of hydrogen from proximally located species isolated within the matrix. Analogous experiments employing CD(3)OCH(3) give similar results, and the observed isotopically substituted products are consistent with the proposed fragmentation pathways.

Bioconcentration, bioaccumulation, biomagnification and trophic magnification: a modelling perspective.

We present a modelling perspective on quantifying metrics of bio-uptake of organic chemicals in fish. The models can be in concentration, partition ratio, rate constant (CKk) format or fugacity, Z and D value (fZD) format that are shown to be exactly equivalent, each having it merits. For most purposes a simple, parameter-parsimonious one compartment steady-state model containing some 13 parameters is adequate for obtaining an appreciation of the uptake equilibria and kinetics for scientific and regulatory purposes. Such a model is first applied to the bioaccumulation of a series of hypothetical, non-biotransforming chemicals with log KOW (octanol-water partition ratio) values of 4 to 8 in 10 g fish ranging in lipid contents to deduce wet-weight and lipid normalized concentrations, bioaccumulation and biomagnification factors. The sensitivity of biomagnification factors to relative lipid contents is discussed. Second, a hypothetical 5 species linear food chain is simulated to evaluate trophic magnification factors (TMFs) showing the critical roles of KOW and biotransformation rate. It is shown that lipid normalization of concentrations is most insightful for less hydrophobic chemicals (log KOW < 5) when bio-uptake is largely controlled by respiratory intake and equilibrium (equi-fugacity) is approached. For more hydrophobic chemicals when dietary uptake kinetics dominate, wet weight concentrations and BMFs are more insightful. Finally, a preferred strategy is proposed to advance the science of bioaccumulation using a combination of well-designed ecosystem monitoring, laboratory determinations and modelling to confirm that the perceived state of the science contained in the models is consistent with observations.

Oligomeric models for estimation of polydimethylsiloxane-water partition ratios with COSMO-RS theory: impact of the combinatorial term on absolute error.

A series of 12 oligomeric models for polydimethylsiloxane (PDMS) were evaluated for their effectiveness in estimating the PDMS-water partition ratio, KPDMS-w. Models ranging in size and complexity from the -Si(CH3)2-O- model previously published by Goss in 2011 to octadeca-methyloctasiloxane (CH3-(Si(CH3)2-O-)8CH3) were assessed based on their RMS error with 253 experimental measurements of log KPDMS-w from six published works. The lowest RMS error for log KPDMS-w (0.40 in log K) was obtained with the cyclic oligomer, decamethyl-cyclo-penta-siloxane (D5), (-Si(CH3)2-O-)5, with the mixing-entropy associated combinatorial term included in the chemical potential calculation. The presence or absence of terminal methyl groups on linear oligomer models is shown to have significant impact only for oligomers containing 1 or 2 -Si(CH3)2-O- units. Removal of the combinatorial term resulted in a significant increase in the RMS error for most models, with the smallest increase associated with the largest oligomer studied. The importance of inclusion of the combinatorial term in the chemical potential for liquid oligomer models is discussed.

Approaches for estimating PUF-air partitions coefficient for semi-volatile organic compounds: A critical comparison.

Partition coefficients between polyurethane foam (PUF) and air (KPUF-Air) are important when using PUF as a passive air sampler for semi-volatile organic compounds (SVOCs) and when considering the fate of SVOCs indoors where PUF is a common material. Here, KPUF-Air for selected SVOCs was estimated using published methods, since measured data are unavailable for most of these compounds. Estimates of KPUF-Air were within one order of magnitude for SVOCs having values of log octanol-air partition coefficient (KOA) of 5, but differed by nearly three orders of magnitude for SVOCs with log KOA of 12. Of all the methods, the correlation developed using experimental measurements gave the lowest estimates for the high KOA compounds, likely because the compounds did not reach equilibrium throughout the PUF sample. The surface area/volume ratio of the PUF sample was shown to influence the observed correlation, a reflection of the equilibration status of the PUF. For quantitative comparison, the poly parameter linear free energy relationship (pp-LFER) model of Kamprad and Goss (2007) was used here as a "surrogate" standard. The correlations developed with vapor pressure and KOA produced estimates that were closest to those obtained using the pp-LFER model. COSMO-RS theory, in which intimate and unimpeded contact is assumed between the compound in air and PUF molecules, gave lower estimates for low KOA compounds, but good average agreement for high KOA compounds. When used in modeling applications, the selection of the method for estimating KPUF-Air should reflect the configuration of the products containing PUF and the model assumptions regarding compound homogeneity within the PUF.

Characterization of polyurethane foam (PUF) and sorbent impregnated PUF (SIP) disk passive air samplers for measuring organophosphate flame retardants.

This study aimed to characterize the uptake of organophosphate esters (OPEs) by polyurethane foam (PUF) and sorbent-impregnated polyurethane foam (SIP) disk passive air samplers (PAS). Atmospheric OPE concentrations were monitored with high-volume active air samplers (HV-AAS) that were co-deployed with passive air samplers. Samples were analyzed for tris(2-chloroisopropyl) phosphate (TCIPP), tri(phenyl) phosphate (TPhP), tris(2-chloroethyl) phosphate (TCEP), and tris(2,3-dichloropropyl) phosphate (TDCIPP). The mean concentration of ∑OPEs in air was 2650 pg/m3 for the HV-AAS. Sampling rates and the passive sampler medium (PSM)-air partition coefficient (KPSM-Air) were calculated for individual OPEs. The average calculated sampling rates (R) for the four OPEs were 3.6 ± 1.2 and 4.2 ± 2.0 m3/day for the PUF and SIP disks, respectively, and within the range of the recommended default value of 4 ± 2 m3/day. Since most of the OPEs remained in the linear uptake phase during the study, COSMO-RS solvation theory and an oligomer-based model were used to estimate KPUF-Air for the OPEs. The estimated values of log KPUF-Air were 7.45 (TCIPP), 9.35 (TPhP), 8.44 (TCEP), and 9.67 (TDCIPP). Finally, four configurations of the PUF and SIP disks were tested by adjusting the distance of the gap opening between the upper and lower domes of the sampler housing: i.e. 2 cm, 1 cm, no gap and 1 cm overlap. The sampling rate did not differ significantly between these four configurations (p < 0.05).

The chemical exposure toxicity space (CETS) model: Displaying exposure time, aqueous and organic concentration, activity, and onset of toxicity.

A 1-compartment toxicokinetic model is used to characterize the chemical exposure toxicity space (CETS), providing a novel graphic tool that can aid in the design of aquatic toxicity tests for fish and for interpreting their results. The graph depicts the solution to the differential equation describing the uptake kinetics of a chemical by a modeled fish under conventional bioassay conditions. The model relates the exposure concentration in the water to a dimensionless time and the onset of toxicity as determined by an estimated or assumed critical body residue or incipient lethal aqueous concentration. These concentration graphs are specific to each chemical and exposure and organism parameters and clearly demonstrate differences in toxicity between chemicals and how factors such as hydrophobicity influence the toxic endpoint. The CETS plots can also be used to assess bioconcentration test conditions to ensure that concentrations are well below toxic levels. Illustrative applications are presented using a recent set of high-quality toxicity data. Conversion of concentrations to chemical activities in the plots enables results for different baseline toxicants to be superimposed. For chemicals that have different modes of toxic action, the increased toxicity then becomes apparent. Implications for design and interpretation of aquatic toxicity tests are discussed. The model, and pictorial visualization of the time-course of aquatic toxicity tests, may contribute to improvements in test design, implementation, and interpretation, and to reduced animal usage. Environ Toxicol Chem 2017;36:1389-1396. © 2016 The Authors. Environmental Toxicology and Chemistry Published by Wiley Periodicals, Inc. on behalf of SETAC.

Direct and indirect effects of different types of microplastics on freshwater prey (Corbicula fluminea) and their predator (Acipenser transmontanus).

We examined whether environmentally relevant concentrations of different types of microplastics, with or without PCBs, directly affect freshwater prey and indirectly affect their predators. Asian clams (Corbicula fluminea) were exposed to environmentally relevant concentrations of polyethylene terephthalate (PET), polyethylene, polyvinylchloride (PVC) or polystyrene with and without polychlorinated biphenyls (PCBs) for 28 days. Their predators, white sturgeon (Acipenser transmontanus), were exposed to clams from each treatment for 28 days. In both species, we examined bioaccumulation of PCBs and effects (i.e., immunohistochemistry, histology, behavior, condition, mortality) across several levels of biological organization. PCBs were not detected in prey or predator, and thus differences in bioaccumulation of PCBs among polymers and biomagnification in predators could not be measured. One of the main objectives of this study was to test the hypothesis that bioaccumulation of PCBs would differ among polymer types. Because we could not answer this question experimentally, a bioaccumulation model was run and predicted that concentrations of PCBs in clams exposed to polyethylene and polystyrene would be greater than PET and PVC. Observed effects, although subtle, seemed to be due to microplastics rather than PCBs alone. For example, histopathology showed tubular dilation in clams exposed to microplastics with PCBs, with only mild effects in clams exposed to PCBs alone.

Characterizing PUF disk passive air samplers for alkyl-substituted PAHs: Measured and modelled PUF-AIR partition coefficients with COSMO-RS.

Isomers of alkyl-substituted polycyclic aromatic hydrocarbons (PAHs) and dibenzothiophenes are modelled with COSMO-RS theory to determine the effectiveness and accuracy of this approach for estimation of isomer-specific partition coefficients between air and polyurethane foam (PUF), i.e., KPUF-AIR. Isomer-specific equilibrium partitioning coefficients for a series of 23 unsubstituted and isomeric alkyl-substituted PAHs and dibenzothiophenes were measured at 22 °C. This data was used to determine the accuracy of estimated values using COSMO-RS, which is isomer specific, and the Global Atmospheric Passive Sampling (GAPS) template approach, which treats all alkyl-substitutions as a single species of a given side-chain carbon number. A recently developed oligomer-based model for PUF was employed, which consisted of a 1:1 condensed pair of 2,4-toluene-diisocyanide and glycerol. The COSMO-RS approach resulted in a significant reduction in the RMS error associated with simple PAHs and dibenzothiophene compared with the GAPS template approach. When used with alkylated PAHs and dibenzothiophenes grouped into carbon-number categories, the GAPS template approach gave lower RMS error (0.72) compared to the COSMO-RS result (0.87) when the latter estimates were averaged within the carbon-number-based categories. When the isomer-specific experimental results were used, the COSMO-RS approach resulted in a 21% reduction in RMS error with respect to the GAPS template approach, with a 0.57 RMS error for all alkylated PAHs and dibenzothiophenes studied. The results demonstrate that COSMO-RS theory is effective in generating isomer-specific PUF-air partition coefficients, supporting the application of PUF-based passive samplers for monitoring and research studies of polycyclic aromatic compounds (PACs) in air.