Equilibrium Partitioning Model Research Articles

Structure-Activity Relationship of Lower Chlorinated Biphenyls and Their Human-Relevant Metabolites for Astrocyte Toxicity.

Exposure to polychlorinated biphenyls (PCBs) is associated with developmental neurotoxicity and neurodegenerative disorders; however, the underlying mechanisms of pathogenesis are unknown. Existing literature has focused mainly on using neurons as a model system to study mechanisms of PCB-mediated neurotoxicity, overlooking the role of glial cells, such as astrocytes. As normal brain function is largely astrocyte-dependent, we hypothesize that astrocytes play an important role in PCB-mediated injury to neurons. We assessed the toxicity of two commercial PCB mixtures, Aroclor 1016 and Aroclor 1254, and a non-Aroclor PCB mixture found in residential air called the Cabinet mixture, all of which contain lower chlorinated PCBs (LC-PCBs) found in indoor and outdoor air. We further assessed the toxicity of five abundant airborne LC-PCBs and their corresponding human-relevant metabolites in vitro models of astrocytes, namely, the C6 cell line and primary astrocytes isolated from Sprague-Dawley rats and C57BL/6 mice. PCB52 and its human-relevant hydroxylated and sulfated metabolites were found to be the most toxic compounds. No significant sex-dependent cell viability differences were observed in rat primary astrocytes. Based on the equilibrium partitioning model, it was predicted that the partitioning of LC-PCBs and their corresponding metabolites in biotic and abiotic compartments of the cell culture system is structure-dependent and that the observed toxicity is consistent with this prediction. This study, for the first time, shows that astrocytes are sensitive targets of LC-PCBs and their human-relevant metabolites and that further research to identify mechanistic targets of PCB exposure in glial cells is necessary.

In Situ Equilibrium Polyethylene Passive Sampling of Soil Gas VOC Concentrations: Modeling, Parameter Determinations, and Laboratory Testing.

The use of low-density polyethylene (PE) sheets as equilibrium passive soil gas samplers to quantify volatile organic compounds (VOCs) such as benzene, toluene, ethylbenzene, and xylenes, and chlorinated solvents (e.g., trichloroethene and tetrachloroethene) in unsaturated subsurface environments was evaluated via modeling and benchtop testing. Two methods were devised to quantify such VOCs in PE. Key chemical properties, including PE-water (KPEw) and PE-air (KPEa) partition coefficients and diffusivities in the PE (Dpe), were determined. These KPEw, KPEa, and Dpe values were consistent with extrapolations of data based on larger compounds. Using these parameter values, field equilibration times of less than 1 day were estimated for such VOCs when using 70-100 μm thick PE sheets. Further, benchtop batch tests carried out in jars filled with VOC-contaminated soils, after 1 or 2 days, showed concentrations in soil air deduced from PE that were consistent with concentrations deduced by analyzing either water or headspace gases recovered from the same tests. Thus, PE-based measurements may overcome inaccuracies from using total soil concentrations and equilibrium partitioning models that may overestimate vapor phase concentrations up to 2 orders of magnitude.

Kinetic partitioning of major-minor cations between olivine and Hawaiian tholeiitic basalt under variable undercooling and cooling rate conditions

In order to elucidate the kinetic partitioning of cations between olivine and basalt, we performed undercooling (−ΔT) and cooling rate (CR) experiments at atmospheric pressure and QFM-2 buffer. Starting from the superliquidus temperature of 1250 °C, a Hawaiian tholeiitic basalt was cooled at the rates of 4 (CR4), 20 (CR20), and 60 (CR60) °C/h to the final target temperatures of 1175 °C (−ΔT = 35 °C; −ΔT35) and 1125 °C (−ΔT = 85 °C; −ΔT85). Results show that polyhedral olivine morphologies are obtained at -ΔT35, whereas strong disequilibrium skeletal and/or dendritic textures form at -ΔT85. The amount of forsterite in olivine decreases from to 85% to 78% with increasing both -ΔT and CR. A diffusive boundary layer also develops in the melt next to the olivine surface and its composition becomes progressively enriched in Ca, owing to its incompatible behavior with the lattice site. Residual melts are progressively depleted in silica and enriched in alkali from CR4 to CR60, but silica-rich melts are observed with increasing -ΔT. In terms of Fe2+-Mg exchange, olivines obtained at -ΔT35 are always in equilibrium with the diffusive boundary layer, comprising both the interface melt next to the olivine surface and the far-field melt where all chemical gradients cease. At -ΔT85, however, the Fe2+-Mg exchange indicates two distinct equilibration stages between olivine core and far-field melt, and between olivine rim and interface melt. Partition coefficients (Kd) of Mg, Fe, Mn, Ca, and Cr calculated at the olivine-melt interface preferentially change as a function of -ΔT rather than CR. From -ΔT35 to -ΔT85, KdMg, KdFe, KdMn, and KdCr remarkably increase, whereas the opposite applies to KdCa. Through the application of equilibrium partitioning models, we found that Mg, Fe, Mn, and Ca are incorporated into the olivine lattice site at near-equilibrium proportions. This generally good agreement with modeling data demonstrates that diffusive mass transport of cations in our experiments occurred under the conditions of local equilibrium at the olivine surface. In contrast, marked deviations from the expected equilibrium are found for KCr in response to the major influence of crystal field stabilization energy on cation incorporation.

In-situ and ex-situ measurement of hydrophobic organic contaminants in soil air based on passive sampling: PAH exchange kinetics, non-equilibrium correction and comparison with traditional estimations

It is a great challenge to accurately estimate chemical activity of hydrophobic organic contaminants in field soils. Ex-situ and in-situ determinations were developed for this purpose based on low-density polyethylene (LDPE) passive sampling and non-equilibrium correction by release of performance reference compounds (PRCs) previously spiked to the samplers. This work investigated kinetic processes of target contaminants’ uptake into and PRCs’ release from the sampler in an ex-situ soil suspension incubated for 100 days. A close agreement of kinetic parameters for pyrene’s (target) uptake into and deuterated pyrene’s (PRC) release from LDPE indicated their similar exchange kinetics. Three kinetic models were developed to correct uptake of target compounds in non-equilibrium conditions via release processes of PRCs. The second-order kinetic model was recommended for ex-situ measurements. The PRC-based non-equilibrium corrections were further applied to in-situ static passive sampling from several weeks to months in a PAH-contaminated field site. Two-weeks’ deployments were sufficient for quantifying lighter PAHs (logKOA < 8.0), but not recommended to accurately estimate heavier PAHs (logKOA > 9.0), even if over four months. Concentration estimates from the in-situ and ex-situ passive samplings were comparable in order of magnitude with traditional estimation from equilibrium partitioning models considering both organic and black carbon fractions.

Study of Secondary Organic Aerosol Formation from Chlorine Radical-Initiated Oxidation of Volatile Organic Compounds in a Polluted Atmosphere Using a 3D Chemical Transport Model.

The impact of chlorine (Cl) chemistry on the formation of secondary organic aerosol (SOA) during a severe wintertime air pollution episode is investigated in this study. The Community Multiscale Air Quality (CMAQ) model v5.0.1 with a modified SAPRC-11 gas-phase mechanism and heterogeneous reactions for reactive chlorine species is updated to include the formation of chlorine radical (Cl•)-initiated SOA (Cl-SOA) from aromatic compounds, terpenes, and isoprene. Reported SOA yield data on Cl-SOA formation from environmental chamber studies are used to derive the mass yield and volatility data for the two-product equilibrium-partitioning model. The heterogeneous reaction of particulate chloride (pCl-) leads to a significant increase in the Cl• and hydroxyl radical (OH) concentrations throughout the domain. Monthly Cl-SOA concentrations range from 0.7 to 3.0 μg m-3, with increasing anthropogenic Cl emissions leading to higher Cl-SOA concentrations. Indirectly, this also leads to an increase of monthly SOA by up to 2.5-3.0 g μm-3 from the traditional OH oxidation pathways as well as the surface uptake of glyoxal and methylglyoxal. Increased OH concentrations, however, do not always lead to higher overall SOA concentrations in the entire domain. High OH reduces the lifetime of glyoxal/methylglyoxal (GLY/MGLY), making them less available to form SOA. In the Sichuan Basin (SCB) and part of Southwest China where high O3 concentrations meet high pCl emissions, a higher Cl•/OH ratio leads to net O3 loss from the Cl• + O3 reaction, thus reducing SOA formation from the O3 oxidation of volatile organic compounds (VOCs). Also, the competition between Cl• and OH for VOCs could lead to lower overall SOA because the molar yields of the semivolatile products in Cl-VOC reactions are lower than their OH + VOC reaction counterparts. When Cl• concentrations are further increased with higher emissions of Cl, precursor gases can be depleted and become the limiting factor in SOA formation. This study reveals the direct and indirect impacts of chlorine chemistry on SOA in polluted winter conditions, which are greatly affected by the Cl emissions, the ambient O3 level, and the availability of SOA precursors.

Molecular Characterization of the Surface Excess Charge Layer in Droplets.

The surface excess charge layer (SECL) in droplets has often been associated with distinct chemistry. We examine the effect of the nature of ions in the composition and structure of SECL by using molecular dynamics. We find that in the presence of simple ions the thickness of SECL is invariant not only with respect to droplet size but also with respect to the nature of the ions. In the presence of simple ions, this layer has a thickness of ∼1.5-1.7 nm but in the presence of macroions it may extend to ∼2.0 nm. The proportion of ions contained in SECL depends on the nature of the ions and the droplet size. For the same droplet size, I- and model H3O+ ions show considerably higher concentration than Na+ and Cl- ions. We identify the maximum ion concentration region, which, in nanodrops, may partially overlap with SECL. As the relative shape fluctuations decrease when microdrop size is approached, the overlap between SECL and maximum ion concentration region increases. We suggest the extension of the bilayer droplet structure assumed in the equilibrium partitioning model of Enke to include the maximum ion concentration region that may not coincide with SECL in nanodrops. We compute the ion concentrations in SECL, which are those that should enter the kinetic equation in the ion-evaporation mechanism, instead of the overall drop ion concentration that has been used.

Remediation criteria for gasworks-impacted sediments: Assessing the effects of legacy hydrocarbons and more recent metal contamination

Historical contamination of sediments from industries that commenced before environmental regulations were commonplace is prevalent in many large cities. This contamination is frequently overlain and mixed with more recent urban contamination. The remediation of contaminated sites is often a very expensive exercise and the final remediation criteria often reflect a trade-off between protecting human and ecological health and the finances of those deemed responsible for the site clean-up. In this study, we describe an assessment of estuarine sediments impacted historically by contamination from a gasworks site. The major historical sediment contaminants included polycyclic aromatic hydrocarbons (PAHs) and other petroleum-related hydrocarbons (TRHs). Elevated concentrations of metals exist throughout the city region due to historical pollution and ongoing urban stormwater discharges. Equilibrium partitioning models were used to consider the influence on the bioavailability of PAHs of both natural sedimentary organic carbon and forms of black carbon (pyrogenic carbon - coal tars, charcoal). The strongest predictor of the observed sublethal toxicity to amphipod and copepod reproduction was a combination of total PAHs and metals (primarily Cu, Pb and Zn). Total PAHs was the strongest predicting variable for toxicity to organism survival. While high total PAH concentrations were attributed to the former gas works, high background concentrations of metals existed throughout much of this region of the estuary. Thus, without remediation at the estuary-scale, resuspension of the surrounding sediments by tidal currents and boat movements is predicted to re-contaminate remediated areas with sediments that may continue to cause chronic toxicity due to metals. The assessment indicated that remedial actions that remove or isolate sediments that caused toxicity to benthic organism survival would lead to significant improvements in ecosystem health, but toxicity to organism reproduction may remain at similar levels that exist throughout much of this region of the estuary due to high metal concentrations.

Influence of Co-Dosed Lipids from Biota Extracts on the Availability of Chemicals in In Vitro Cell-Based Bioassays.

Extraction of chemicals from biota leads to co-extraction of lipids. When dosing such extracts into in vitro bioassays, co-dosed lipids act as an additional phase that can reduce the bioavailability of the chemicals and the apparent sensitivity of the assay. Equilibrium partitioning between medium, cells, and co-dosed lipids was described with an existing equilibrium partitioning model for cell-based bioassays extended by an additional lipid phase. We experimentally investigated the influence of co-dosed lipids on the effects elicited by four test chemicals of different hydrophobicity in two bioassays, indicative of the aryl hydrocarbon receptor and oxidative stress response (AREc32). The partitioning model explained the effect of the test chemicals in the presence of spiked triolein within a factor of 0.33–5.83 between the measured and predicted effect concentration (EC). We applied the model to marine mammal blubber extracted with silicone. Extracts dosed in the AREc32 bioassay showed a linear increase of apparent EC with increasing lipid fraction. The partitioning model was used to interpret the role of the co-extracted lipid. A quantitative lipid correction of bioassay results in the presence of co-dosed lipids was possible for known compounds and defined mixtures, while we could only estimate a range for mixtures of unknown chemicals.

Review of Polycyclic Aromatic Hydrocarbons (PAHs) Sediment Quality Guidelines for the Protection of Benthic Life.

ABSTRACTPolycyclic aromatic hydrocarbons (PAHs) in sediments can pose harm to the benthic community. Numerous sediment quality guidelines (SQGs) for the protection of benthic life are available to assess the risk of individual PAHs and PAH mixtures in sediments. Sediment quality guidelines are derived using empirical or mechanistic approaches. Empirically based guidelines are derived using databases of paired sediment chemistry and biological responses and relating sediment concentration to the frequency of an adverse response. Mechanistically based SQGs are derived by considering the inherent aqueous toxicity of the chemical to different biota coupled with site‐specific sediment characteristics (i.e., organic C) known to influence PAH bioavailability. Additionally, SQGs are derived to be either protective or predictive of adverse effects in benthic organisms. The objective of this critical review was to evaluate SQGs for use in screening‐level risk assessments to identify sediments that may pose a risk to the benthic community. SQGs for PAHs were compiled and compared, and performance evaluated for predicting the presence and absence of toxicity using an extensive field data set. Furthermore, a 2‐carbon equilibrium partitioning model and direct measurement of porewater via passive sampling were evaluated for improved performance in higher tiered risk assessments. Recommendations for the use of SQGs in screening evaluations, enhancements to current approaches, and opportunities to refine site risk estimate assessments using passive sampling measurements are discussed. Integr Environ Assess Manag 2019;15:505–518. © 2019 SETAC

Mass accommodation coefficients of fresh and aged biomass-burning emissions

ABSTRACTMost chemical transport models treat the partitioning of semi-volatile organic compounds (SVOCs) with the assumption of instantaneous thermodynamic equilibrium. However, the mass accommodation coefficients, α, of biomass-burning organic aerosol (BBOA) are largely unconstrained. During the FLAME-IV campaign, we thermally perturbed aged and fresh BBOA with a variable residence time thermodenuder and measured the resulting change in particle mass concentration to restore equilibrium. We used this equilibration profile to retrieve an effective α for components of BBOA that dictated this profile and found that the mass accommodation coefficients lie within the range 0.1 ≪ α ⩽ 1. A simple plume dilution model shows a maximum of only a 7% difference between a dynamical and an instantaneous equilibrium partitioning model using our best-estimate value for α. This supports continued use of the equilibrium assumption to treat partitioning of biomass-burning emissions in chemical-transport models.Copyright © ...

Modeling Exposure in the Tox21 in Vitro Bioassays.

High-throughput in vitro bioassays are becoming increasingly important in the risk characterization of anthropogenic chemicals. Large databases gather nominal effect concentrations (Cnom) for diverse modes of action. However, the biologically effective concentration can substantially deviate due to differences in chemical partitioning. In this study, we modeled freely dissolved (Cfree), cellular (Ccell), and membrane concentrations (Cmem) in the Tox21 GeneBLAzer bioassays for a set of neutral and ionogenic organic chemicals covering a large physicochemical space. Cells and medium constituents were experimentally characterized for their lipid and protein content, and partition constants were either collected from the literature or predicted by mechanistic models. The chemicals exhibited multifaceted partitioning to proteins and lipids with distribution ratios spanning over 8 orders of magnitude. Modeled Cfree deviated over 5 orders of magnitude from Cnom and can be compared to in vivo effect data, environmental concentrations, and the unbound fraction in plasma, which is needed for the in vitro to in vivo extrapolation. Ccell was relatively constant for chemicals with membrane lipid-water distribution ratios of 1000 or higher and proportional to Cnom. Representing a sum parameter for exposure that integrates the entire dose from intracellular partitioning, Ccell is particularly suitable for the effect characterization of chemicals with multiple target sites and the calculation of their relative effect potencies. Effective membrane concentrations indicated that the specific effects of very hydrophobic chemicals in multiple bioassays are occurring at concentrations close to baseline toxicity. The equilibrium partitioning model including all relevant system parameters and a generic bioassay setup is attached as an excel workbook to this paper and can readily be applied to diverse in vitro bioassays.

Biodegradation testing of chemicals with high Henry's constants – Separating mass and effective concentration reveals higher rate constants

During simulation-type biodegradation tests, volatile chemicals will continuously partition between water phase and headspace. This study addressed how (1) this partitioning affects test results and (2) can be accounted for by combining equilibrium partition and dynamic biodegradation models. An aqueous mixture of 9 (semi)volatile chemicals was first generated using passive dosing and then diluted with environmental surface water producing concentrations in the ng/L to μg/L range. After incubation for 2 h to 4 weeks, automated Headspace Solid Phase Microextraction (HS-SPME) was applied directly on the test systems to measure substrate depletion by biodegradation relatively to abiotic controls. HS-SPME was also applied to determine air to water partitioning ratios. Biodegradation rate constants relating to the chemical in the water phase, kwater, were generally a factor 1 to 11 times higher than biodegradation rate constants relating to the total mass of chemical in the test system, ksystem, with one exceptional factor of 72 times for a long chain alkane. True water phase degradation rate constants were found (i) more appropriate for risk assessment than test system rate constants, (ii) to facilitate extrapolation to other air-water systems and (iii) to be better defined input parameters for aquatic exposure and fate models.

Bioavailability of polycyclic aromatic hydrocarbons (PAHs) and Environmental Risk (ER) Assessment: The case of the Ogbese river, Nigeria

Pollution from PAHs in porewater and surficial sediments of the rapidly contaminated Ogbese River, Ondo State, Nigeria was investigated. Samples were extracted using Hexane/methylene chloride mixture and the complex PAH mixtures were analyzed by gas chromatography-mass spectrometry. There was greater influence of sediment fine particles (R2=0.978) in partitioning of PAHs over other factors. Total concentration of PAHs in the sediments and porewater ranged 14.45 μg g−1 to 26.78 μg g−1 (n=8, dry weight) and 6.25 μg L−1 to 13.93 μg L−1 (n=8) respectively. The measured partition coefficients (i.e., Koc values) of the individual PAHs between sediment organic matter (SOM) and porewater across all locations ranged from 5.027 (±0.157 SD) to 5.074 (±0.169 SD). The correlation in log Koc (observed vs predicted) for high molecular weight/low molecular weight-PAHs suggests variability in specific interactions and unequal partition efficiencies with SOM under natural condition. Based on equilibrium partitioning and narcosis model, three PAHs {benzo(b)fluoranthene, benzo(a)pyrene and dibenz(a,h)anthracene }has toxic unit (TU) values of concern. These results represent a baseline report for future monitoring programs of PAHs.

Ambient Gas-Particle Partitioning of Tracers for Biogenic Oxidation.

Exchange of atmospheric organic compounds between gas and particle phases is important in the production and chemistry of particle-phase mass but is poorly understood due to a lack of simultaneous measurements in both phases of individual compounds. Measurements of particle- and gas-phase organic compounds are reported here for the southeastern United States and central Amazonia. Polyols formed from isoprene oxidation contribute 8% and 15% on average to particle-phase organic mass at these sites but are also observed to have substantial gas-phase concentrations contrary to many models that treat these compounds as nonvolatile. The results of the present study show that the gas-particle partitioning of approximately 100 known and newly observed oxidation products is not well explained by environmental factors (e.g., temperature). Compounds having high vapor pressures have higher particle fractions than expected from absorptive equilibrium partitioning models. These observations support the conclusion that many commonly measured biogenic oxidation products may be bound in low-volatility mass (e.g., accretion products, inorganic-organic adducts) that decomposes to individual compounds on analysis. However, the nature and extent of any such bonding remains uncertain. Similar conclusions are reach for both study locations, and average particle fractions for a given compound are consistent within ∼25% across measurement sites.

Persistent Organohalogens in Paired Fish Fillet and Eggs: Implications for Fish Consumption Advisories.

Fish consumption is associated with both health benefits from high-quality proteins, minerals, vitamins, and fatty acids and risks from contaminants in fish. Fish consumption advisories are issued by many government agencies to keep exposure to contaminants at a safe level. Such advisories are typically based on fillets and neglect consumption of other fish parts such as eggs by certain subpopulations. To evaluate potential for dietary exposure to toxic organic chemicals via fish eggs, we analyzed polybrominated diphenyl ethers (PBDEs), polychlorinated naphthalenes (PCNs), dioxin-like polychlorinated biphenyls (dlPCBs), and polychlorinated dibenzodioxins/furans (PCDD/Fs) in paired fillet and eggs of fish from a tributary to Lake Ontario, one of the North American Great Lakes. All wet weight based concentrations in fish eggs were statistically higher than in the paired fillet samples. In fish eggs, concentrations of Σ14PBDEs, Σ14PCNs, and Σ12dlPCBs were 41-118, 0.3-1.7, and 30-128 ng/g wet weight (ww), respectively; Σ3PCDD/Fs and total (dlPCB+ PCDD/Fs) toxic equivalents (TEQs) were 4-22 and 9-54 pg/g ww, respectively. In fillet samples, Σ14PBDEs, Σ14PCNs, and Σ12dlPCBs were 4-116, 0.05-0.66, and 6-85 ng/g, respectively; Σ3PCDD/Fs and TEQs were 2-10 and 3.4-31 pg/g ww, respectively. In contrast, the fillets had higher lipid normalized concentrations than the paired egg samples, suggesting that these chemicals did not reach equilibrium between the fillets and eggs. Accordingly, measured concentrations in eggs or empirical relationship with fillet rather than prediction from equilibrium partitioning model should be used to evaluate contaminant exposure via consumption of fish eggs. For fatty fish from the lower Great Lakes area, we suggest one fillet meal be reduced from the advised fish consumption frequency for consumptions of 207 ± 37, 39 ± 2, 105 ± 51, and 119 ± 9 g fish eggs of brown trout, Chinook salmon, Coho salmon, and rainbow trout, respectively.

Assessment of metal toxicity and development of sediment quality guidelines using the equilibrium partitioning model for the Three Gorges Reservoir, China.

The impoundment of the Three Gorges Reservoir (TGR) in China influences the quality of the water supply. Surface sediment samples from the TGR mainstream and three tributaries were collected. Acid volatile sulfide (AVS), simultaneously extractable metals (SEMs), and the fraction of organic carbon (f(oc)) were used to assess the toxicity of heavy metals. Sediment quality guidelines (SQGs) were established using the equilibrium partitioning approach. The results showed that the surface sediments were found to be oxic or suboxic. AVS concentrations in sediments were relatively low, below SEM concentrations. The [SEM] - [AVS] model indicated that all sediments possibly have adverse effects on aquatic life. However, ([SEM] - [AVS])/f(oc) predicted no adverse biological effects in some areas of the Meixi and Caotang Rivers, while adverse effects to aquatic life were uncertain for the other sediments. The partitioning coefficients, water quality criteria, and residual metals in the sediments were the main factors influencing the SQGs for the TGR, while the metals bound to AVS had a negligible effect. The normalized TGR SQGs were all much higher than the existing standards except for cadmium and copper. The differences might be attributed to the approaches used for derivation of SQGs and the physical and chemical characteristics of the sediments.

Using soil-specific partition coefficients to improve accuracy of the new South African guideline for contaminated land

Contaminated land in South Africa is regulated through the National Environmental Management Waste Act (Act 59 of 2008) (NEMWA) and the National Norms and Standards for the Remediation of Contaminated Land and Soil Quality (NSCLA) (GN R.331 of 2014). These standards were obtained from the Framework for the Management of Contaminated Land. A soil screening value (SSV1) for the protection of groundwater resources is proposed which is based on a 2-phase (stage) equilibrium partitioning and dilution model which includes a dilution factor and partitioning coefficient (Kd), converting the water quality guideline to a total soil screening value. The appropriateness of the screening values has been questioned because of the uncertainties surrounding the Kd values used by the Framework. This paper investigates the Kd values of Cu, Pb, and V for selected South African diagnostic soil horizons to evaluate the reliability of the current Kd values used by the Framework during Phase 1 screening. The Kd values of Cu for the 10 horizons ranged between 13 and 19 044 l∙kg -1 , all exceeding the value of 10 l∙kg -1 provided by the Framework. For Pb the values ranged from 25 to >252 294 l∙kg -1 as compared to the Framework’s 100 l∙kg -1 . Similarly, the Kd value of 200 l∙kg -1 for V recommended by the Framework is higher than the measured Kd value of 15 to 173 l∙kg -1 for all 10 diagnostic horizons. This study demonstrated that the observed wide Kd value ranges for each element were related to the variation in basic soil properties such as soil pH, organic carbon, clay, Fe, and Al content. Therefore, the Kd values for Cu, Pb, and V currently used by the Framework are not representative of typical South African diagnostic soil horizons. Linear regression models were developed for the prediction of Cu, Pb, and V Kd values from measured soil properties, which could be used to generate soil-specific Kd values. Keywords : Kd value, contaminated land, NEMWA, screening value, risk, soil

Extension and validation of the target lipid model for deriving predicted no-effect concentrations for soils and sediments.

Substance risk assessments require estimation of predicted no-effect concentrations (PNECs) in soil and sediment. The present study applies the target lipid model (TLM) and equilibrium partitioning (EqP) model to toxicity data to evaluate the extrapolation of the TLM-derived aquatic PNECs to these compartments. This extrapolation assumes that the sensitivity of aquatic species is similar to that of terrestrial and benthic species. The acute species sensitivity distribution, expressed in terms of species-specific critical target lipid body burdens, was computed using the TLM-EqP framework and found to span a similar range as the aquatic organism species sensitivity distribution but with a slightly lower median value (less than 2 times). The species sensitivity distribution for acute-to-chronic ratios also exhibited a similar range and distribution across species, suggesting similar mechanisms of action. This hypothesis was further tested by comparing empirical soil/sediment chronic effect levels to the calculated PNEC derived using TLM-EqP. The results showed that 95% of the compiled chronic effects data fell above the PNEC, confirming an adequate protection level. These findings support the conclusion that TLM-derived aquatic PNECs can be successfully extrapolated to derive credible PNECs for soil and sediment compartments.

What protein charging (and supercharging) reveal about the mechanism of electrospray ionization.

Understanding the charging mechanism of electrospray ionization is central to overcoming shortcomings such as ion suppression or limited dynamic range, and explaining phenomena such as supercharging. Towards that end, we explore what accumulated observations reveal about the mechanism of electrospray. We introduce the idea of an intermediate region for electrospray ionization (and other ionization methods) to account for the facts that solution charge state distributions (CSDs) do not correlate with those observed by ESI-MS (the latter bear more charge) and that gas phase reactions can reduce, but not increase, the extent of charging. This region incorporates properties (e.g., basicities) intermediate between solution and gas phase. Assuming that droplet species polarize within the high electric field leads to equations describing ion emission resembling those from the equilibrium partitioning model. The equations predict many trends successfully, including CSD shifts to higher m/z for concentrated analytes and shifts to lower m/z for sprays employing smaller emitter opening diameters. From this view, a single mechanism can be formulated to explain how reagents that promote analyte charging ("supercharging") such as m-NBA, sulfolane, and 3-nitrobenzonitrile increase analyte charge from "denaturing" and "native" solvent systems. It is suggested that additives' Brønsted basicities are inversely correlated to their ability to shift CSDs to lower m/z in positive ESI, as are Brønsted acidities for negative ESI. Because supercharging agents reduce an analyte's solution ionization, excess spray charge is bestowed on evaporating ions carrying fewer opposing charges. Brønsted basicity (or acidity) determines how much ESI charge is lost to the agent (unavailable to evaporating analyte).

Validating the use of performance reference compounds in passive samplers to assess porewater concentrations in sediment beds.

Hydrophobic organic compounds (HOCs) like polycyclic aromatic hydrocarbons (PAHs) and polychlorinated biphenyls (PCBs) tend to accumulate in sediment beds when they are released into aquatic environments. Due to this buildup of HOCs in the sediment, the highest water concentrations are often in the pore water. Passive samplers can be used in the field (i.e., in situ) to measure freely dissolved porewater concentrations if target contaminants diffusing through the sediment and into the sampler exhibit the same diffusive retardation factors as performance reference compounds (PRCs) that are diffusing out of the sampler and into the sediment. To test this assumption, polyethylene (PE) passive samplers were placed in an organic- and black- carbon-rich sediment bed in the laboratory with samplers removed every 30 days for 4 months. The concentrations of target contaminants in the PE at each time point, corrected using measures of the losses of PRCs, were in good agreement with separately measured equilibrium concentrations in a well-mixed system. Concentrations in the PE passive samplers, normalized by their polyethylene-water partition coefficients, were also in good agreement with directly measured porewater concentrations. Finally, PE-deduced porewater concentrations were compared with the traditional equilibrium partitioning models and showed that considering sorption to only organic carbon substantially overestimated porewater concentrations. However, predictions improved greatly if sorption to black carbon was also considered.