Organic Carbon Partition Coefficient Research Articles

Characteristics, prediction, and risk assessment of phthalates, organophosphate esters, and polycyclic aromatic hydrocarbons in vegetables from plastic greenhouses of Northeast China.

We investigated the contaminations of phthalates (PAEs), organophosphate esters (OPEs), and polycyclic aromatic hydrocarbons (PAHs) in the vegetables and their corresponding soils from 26 plastic greenhouses of Northeast China. PAEs, OPEs, and PAHs in the edible portion of vegetables were in the range of 2620-21800, 115-852, and 32.4-602 ng/g, while the levels of these chemicals in the greenhouse soils were 5770-18800, 196-935, and 109-1600 ng/g, respectively. PAEs are the main organic pollutants in greenhouses, which were 1-2 orders of magnitude higher than that of OPEs and PAHs. Leafy vegetables showed the highest contamination level, which is ∼1-3 times that of root and fruit vegetables. Bioaccumulation factors (BAFs) of chemicals are significantly negatively correlated with their physicochemical properties, e.g., octanol-water partition coefficient and organic carbon partition coefficient. The partition-limited model can accurately predict the contamination level of greenhouse vegetables to a certain extent based on the chemical's concentration in the corresponding soil. We assessed the hazard quotients of target compounds through daily intake of greenhouse vegetables, and found a low risk for di(2-ethylhexyl) phthalate. This research emphasized the potential dietary exposure risks caused by greenhouse leafy vegetables, and proposed a method for evaluating the risk of greenhouse vegetables through soil monitoring.

Groundwater Leaching Potential of Pesticides: A Historic Review and Critical Analysis

AbstractWe evaluated the main leaching indices that have been used for decades for the protection of groundwater against contamination by pesticides. We describe the index classifications in detail and discuss their advantages and limitations relative to their prediction value. Most of the indices have similarities in the types of parameters they use. Some of the similarities are basic physicochemical properties of the pesticides such as their water solubility and their organic carbon partition coefficient, as well as characteristics such as environmental persistence in the soil and some soil characteristics. It is very difficult to maintain a simple index with high predictive power. However, comparisons are allowed by many indices among different active ingredients before pesticides are classified according to the risk of being groundwater contaminants. In contrast, limitations are the scarce inclusion of pesticide byproducts in the ground, lack of prediction capacity for polar pesticides, and lack of prediction of the vulnerability of groundwater to being contaminated by pesticides. Despite the limitations of such approaches, they are of great utility, particularly for protection of groundwater from pesticide contamination when little information is available, which is the case in most developing countries and in countries with economies in transition. Caution is recommended in the analysis of information generated by these approximations, which ideally should be validated experimentally in the different application scenarios and the needs for pesticide assessment based on local information. Environ Toxicol Chem 2024;00:1–14. © 2024 SETAC

Evaluation of soil pesticide leaching to groundwater using undisturbed lysimeter: development of the pesticide groundwater leaching scoring system (PLS).

Groundwater pesticide safety management is essential for providing consistently safe water for humans, but such management is limited globally. In this study, we developed an accurate and convenient exposure assessment method for the safety management of pesticides in groundwater by conducting a lysimeter experiment to evaluate the leaching of 11 pesticides into groundwater. During the experimental period, flutoalanil and oxadiazon had the highest cumulative leaching amounts, 603.7 and 83.5ng, respectively. Comparative analysis of existing groundwater exposure prediction indices, including the GUS, LEACH, modified LEACH, Hornsby index, and GLI showed no correlations with the measured data (p > 0.05). To enhance the accuracy of the assessment method, we used lysimeter data and principal component analysis to determine the main factors affecting groundwater leaching, and developed the "pesticide groundwater leaching scoring system" (PLS). The soil and water half-life, which had the greatest positive impact on groundwater leaching, was set as a 10-point indicator, whereas log P was set as a 1-point indicator. In contrast, solubility in water was determined as a 5-point indicator, and organic carbon partition coefficient and vapor pressure were determined as 2.5-point indicators owing to their negative relationship. The correlation coefficient was 0.670, indicating a significant correlation with the lysimeter data (p < 0.05). Using our scoring system, we ranked 376 pesticides. As an exposure assessment method developed using actual data, the PLS is expected to be applicable to groundwater safety management.

Spatiotemporal dynamics and modeling of thiacloprid in paddy multimedia systems with the effect of wetting-drying cycles

The widespread presence of thiacloprid (THI), a neonicotinoid, raises concerns for human health and the aquatic environment due to its persistence, toxicity, and bioaccumulation. The fate of THI in paddy multimedia systems is mainly governed by irrigation practices, but the potential impacts remain poorly documented. This study investigated the effects of water management practices on THI spatiotemporal dynamics in paddy multimedia systems by combining soil column experiments and a non-steady-state multimedia model. The results indicated the wetting-drying cycle (WDC) irrigation reduced THI occurrences in environmental phases (i.e., soil, interstitial water, and overlying water) and accelerated the THI loss through the THI aerobic degradation process. THI occurrences in the soil and water phases decreased from 18.8% for conventional flooding (CF) treatment to 9.2% for severe wetting-drying cycle (SW) treatment after 29 days, while the half-lives shortened from 11.1 days to 7.3 days, respectively. Meanwhile, the WDC decreased THI outflow from leakage water, which reduced the THI risk of leaching. There was no significant difference in THI plant uptake and volatilization between CF and WDC treatments. The mean proportions of THI fate in paddy multimedia systems followed the order: THI degradation (57.7%), outflow from leakage water (25.5%), occurrence in soil (12.4%), plant uptake (3.4%), occurrence in interstitial water (0.7%), occurrence in overlying water (0.3%), volatilization (<0.1%) after 29 days. The sensitivity analysis identified the soil organic carbon partition coefficient (KOC) as the most sensitive parameter affecting THI's fate. In addition, the topsoil layers of 0–4 cm were the main sink of THI, holding 67% of THI occurrence in the soil phase. The THI occurrence in interstitial water was distributed evenly throughout the soil profile. These findings made beneficial theoretical supplements and provided valuable empirical evidence for water management practices to reduce the THI ecological risk.

The seasonality of the concentration of endocrine phenolic compounds in the matter attached to the surface of microplastics

Rapid biofilm formation on microplastic (MP) surfaces in marine environments and the tendency of hydrophobic pollutants to bioaccumulate may increase the exposure of organisms to ingested plastics and transport pollutants far from their sources. The role of the matter attached to MPs (MaM) in the interactions between MPs and other pollutants in marine environments is poorly understood. This paper studies pollutant sorption in MaM for three phenolic endocrine-disrupting chemicals (EDCs): bisphenol A (BPA), 4-tert-octylphenol (4-t-OP), and 4-nonylphenol (4-NP). Polypropylene (PP), expanded polystyrene (EPS), and polylactide (PLA) MPs were exposed to an environment conducive to biofouling (Vistula Lagoon, Baltic Sea) for four weeks in summer, spring, and winter. The concentrations of EDCs in MaM and the suspended particulate matter (SPM) were similar and were 2–3 orders of magnitude higher than those in water and sediment. The type and morphology of the polymers were less significant for determining the concentrations of EDCs in MaM than the season. The concentrations were higher in the growing season than in winter. EDCs increased linearly with the increase in particulate organic carbon. The relationships between organic carbon partition coefficients and octanol/water partition coefficients indicate that hydrophobic partitioning into organic matter was the dominant mechanism of 4-t-OP and 4-NP binding in MaM and in SPM. For BPA, additional sorption mechanisms seem to be significant. In addition to the direct sorption from ambient water, the binding of phytoplankton-derived particles, most probably via attachment to extracellular polymeric substances, appears to be a source of EDCs in MPs. Rough estimates showed that the largest load of particulate matter and EDCs was attached to expanded polystyrene. This study suggests that the potential negative impacts of MPs on the environment are seasonal and that low-density porous plastics can be particularly effective carriers of large EDC loads.

Model-Assisted Interpretation of 4,4'-Methylene Dianiline Adsorption on Soils at Micromolar Concentrations.

Adsorption kinetics and isotherms were determined for 4,4'-methylene dianiline (MDA) on five diverse soils at nominal concentrations of 0.01-1.0 mg L-1 (nominal soil loading 0.1-40 μg gs -1 ). The data were used to model the adsorption process based on the two-step mechanism that is characteristic of the adsorption of aromatic amines, consisting of a physical equilibrium between the aqueous phase and the soil organic matter and a chemical reaction between the adsorbed MDA and reactive sites in the soil organic matter. Generic parameters were determined that enabled application of the model to other soils, which was checked against previously published data for MDA adsorption. At the low concentrations evaluated, the adsorption process took place almost exclusively in the organic matter without the need to account for a separate ion exchange process with the soil mineral fraction. Physical adsorption was found to be mainly dependent on the protonation state of MDA and increased with decreasing pH of the soils. Because of the chemical reaction taking place, adsorption equilibrium constants (organic-carbon partition coefficient [KOC ]) normalized to the organic carbon content in the soil gradually increased with time; and it was demonstrated that, at steady-state conditions, values of log KOC > 3.5 can be expected for most any soil at conservatively estimated potential environmental MDA concentrations. Environ Toxicol Chem 2023;42:2580-2588. © 2023 SETAC.

Sorption desorption behaviour of Imidacloprid in agricultural soils of Deccan plateau of Southern India: kinetics and thermodynamic analysis

ABSTRACT Soil sorption has a significant impact on the fate and behaviour of agrochemicals in soil and water. The current study attempts to investigate the sorption desorption behaviour of Imidacloprid, a neonicotinoid insecticide, in three different types of black cotton soils (BC-1, BC-2, BC-3) and red soil (RS) of Southern India using batch equilibrium technique under two different temperature conditions (273/300K). The data revealed that the Freundlich model provided the best explanation for the observed adsorption isotherms. BC-2 soil had higher adsorption coefficient (Kf) value, followed by BC-3, BC-1, and RS. Clay content, cation exchange capacity (CEC) and specific surface area (SSA) all had a positive correlation with Kf value, indicating that they are responsible for Imidacloprid adsorption in the soil. The change in enthalpy (ΔH°) value was found to be negative in all of the investigated soils, indicating that the sorption process was spontaneous and exothermic, and that hydrogen bonding may be responsible for sorption. The low value of Kf and organic carbon partition coefficient (Koc) indicates that Imidacloprid is mobile in black cotton and red soils and has potential to contaminate groundwater resources.

Target Lipid Model and Empirical Organic Carbon Partition Coefficients Predict Sediment Toxicity of Polychlorinated Biphenyls to Benthic Invertebrates.

Quantifying causal exposure-response relationships for polychlorinated biphenyl (PCB) toxicity to benthic invertebrates can be an important component of contaminated sediment assessments, informing cleanup decisions and natural resource injury determinations. Building on prior analyses, we demonstrate that the target lipid model accurately predicts aquatic toxicity of PCBs to invertebrates, providing a means to account for effects of PCB mixture composition on the toxicity of bioavailable PCBs. We also incorporate updated data on PCB partitioning between particles and interstitial water in field-collected sediments, to better account for effects of PCB mixture composition on PCB bioavailability. To validate the resulting model, we compare its predictions with sediment toxicity data from spiked sediment toxicity tests and a variety of recent case studies from sites where PCBs are the primary sediment contaminant. The updated model should provide a useful tool for both screening-level and in-depth risk analyses for PCBs in sediment, and it should aid in diagnosing potential contributing factors at sites where sediment toxicity and benthic community impairment are observed. Environ Toxicol Chem 2023;42:1134-1151. © 2023 SETAC.

Use of the Solid By-Product of Anaerobic Digestion of Biomass to Remove Anthropogenic Organic Pollutants with Endocrine Disruptive Activity

Anaerobic digestion of biomass has increasing implementation for bioenergy production. The solid by-product of this technology, i.e., the digestate, has relevant potential in agricultural and environmental applications. This study explored the capacity of a digestate from mixed feedstock to remove from water four endocrine-disrupting chemicals, namely the pesticides metribuzin (MET) and boscalid (BOS) and the xenoestrogens bisphenol A (BPA) and 4-tert-octylphenol (OP). The surface micromorphology and functional groups of the digestate were investigated using scanning electron microscopy (SEM) and Fourier-transform infrared (FTIR) spectroscopy, respectively. Results of sorption kinetics showed that all compounds reached the steady state in a few hours according to a pseudo-first-order model in the cases of MET and OP, a pseudo-second-order model for BOS and both models in the case of BPA. Data of adsorption isotherms were fitted to the Henry, Freundlich, Langmuir and Temkin equations. The adsorption of MET preferentially followed the non-linear Freundlich model, whereas the adsorption of the other compounds was properly described by both the linear and Freundlich models. The organic carbon partition coefficients, KOC, were 170, 1066, 256 and 2180 L kg−1 for MET, BOS, BPA and OP, respectively. The desorption of BOS, BPA and OP was slow and incomplete, indicating a phenomenon of hysteresis. In conclusion, the digestate showed a remarkable efficiency in the removal of the compounds, especially those with high hydrophobicity, thus behaving as a promising biosorbent for environmental remediation.

Source, Partition and Ecological Risk of Polycyclic Aromatic Hydrocarbons in Karst Underground River Environment, Southern China

As the main source of drinking water in the karst areas of southern China, underground rivers play an important supporting role in local economic and social development. However, due to the special aquifer structure in the karst areas of southern China, polycyclic aromatic hydrocarbons (PAHs) can easily enter the water environment of underground rivers and cause serious pollution, which will affect the water quality safety. In this study, Qing-shui Spring underground river in Nanning city was selected as a representative of the typical underground river in southern China, and the pollution characteristics, source analysis, ecological risk assessment and diffusion law of PAHs were studied. The results showed that the total concentration of PAHs in groundwater and surface sediments was in the range of 282.42–464.88 ng/L and 400.14–1194.69 ng/g, respectively, and the overall concentrations of PAHs were below the moderate pollution level. Pollutant discharge and physical and chemical properties of PAHs caused the concentrations of PAHs to decrease gradually from upstream to downstream, but the proportion of high-cyclic PAHs increased gradually. According to the source analysis results of the ratio method, PAHs sources in groundwater were mainly biomass combustion sources in the upstream, oil sources in the middle and mixed sources in the downstream. Sediment and groundwater had some differences. The middle and upper reaches were the source of biomass combustion, while the middle and lower reaches were the mixed source. The ecological risk assessment results showed that the ecological risk of groundwater was at a moderate level, while the ecological risk of sediment was at a low level. Benzo[a]anthracene (BaA) and benzo[b]fluoranthene (BbF) in groundwater and acenaphthylene (Acy) and fluoranthene (Flu) in sediment should be monitored intensively. Appropriate control measures should be put in place to prevent further pollution. Partition coefficients varied from 0.73 to 3.85 L/g in the sediment–water interface, increasing with the rise of PAH compounds. All of the organic carbon partition coefficients (Koc) in the sediment–water interface were higher than predicate values based on the typical model of equilibrium distribution; this indicated that PAHs were strongly adsorbed in the sediment. The linear free energy relationship coefficient between the Koc value and the n-octanol-water partition coefficient (Kow) was 0.85 but the slope was lower than 1, indicating that sediment in the Qing-shui Spring underground river had weak lipophilic characteristics and adsorption ability for PAHs. The results can provide a reference for the risk assessment and pollution control of PAHs in the karst underground rivers in South China.

Acute Polychlorinated Biphenyl Benthic Invertebrate Toxicity Testing to Support the 2017 Chronic Dose-Response Sediment Injury Model.

As managers and decision makers evaluate pollutant risk, it is critical that we are able to measure an assessment of the injury. Often, these estimates are difficult to determine for benthic organisms, so in 2017 a chronic polychlorinated biphenyl (PCB) sediment dose-response model to predict benthic invertebrate injury was proposed. Given both natural resource trustee and consultant questions following publication concerning that the aqueous chronic toxicity testing data used in the 2017 model development were primarily from the 1970s and 1980s, this follow-up short communication is meant to provide the user some additional data that are more recent. With the advances in analytical and quantitative environmental chemistry (i.e., better detection limits and congener separation), we chose to complete acute aquatic toxicity testing using 3 estuarine invertebrates and lethal endpoints (20 and 50% lethal concentrations). This acute testing was selected because chronic aquatic testing for PCBs outside of the data used in the 2017 study was not available to us. The aquatic results used in the present study were changed to sediment using equilibrium partitioning, as done in the 2017 chronic model, after using the same organic-carbon partition coefficient and total organic carbon for our equilibrium partitioning (EqP)-measured calculations. Based on these acute aquatic toxicity results and a general acute-to-chronic injury concentration ratio of approximately 10, we found that the 2017 model was valid and, hence, that a 1.0 µg/g chronic PCB sediment criterion is a reasonable estimation of potential benthic invertebrate injury. This was followed by spiked sediment tests where percent acute sediment injury was compared to the EqP-derived chronic value and the results from 2017; modest agreement is shown. Environ Toxicol Chem 2021;40:1188-1193. Published 2020. This article is a U.S. Government work and is in the public domain in the USA.

Influence of physicochemical factors on environmental availability and distribution of semiochemicals that affect Varroa destructor and phylogenetically close organisms: classification by VHWOC PCA-clustering

Varroa destructor parasites Apis mellifera larvae following the interception of the semiochemicals involved in bee communication; thus, the semiochemical availability and distribution pathways take place within different physicochemical environments. The structure of 172 molecules with semiochemical activity on Varroa destructor was used to compute the representative physicochemical descriptors of the thermodynamic partition among different physicochemical environments: vapor pressure (V), Henry's coefficient (H), water solubility constant (W), octanol-water partition coefficient (O) and organic carbon partition coefficient (C); VHWOC. The principal component analysis (PCA) and hierarchical clustering of VHWOC descriptors allowed us to establish the trend in availability and distribution of the semiochemicals resulting in a 4 classes model of physicochemical environments: Class 1, Soluble/Volatile; Class 2, Soluble; Class 3, Contact; Class 4, Adsorbed/Volatile. Our results suggest that semiochemicals can transit between different thermodynamic equilibrium phases depending on environment conditions. The classification prediction of the model was tested on 6 new molecules obtained from ketonic extracts of L5 Apis mellifera drone larvae; locating them in class 4, which was consistent with their molecular structure. This study can be the starting point for the design of synthetic semiochemicals or for the control of Varroa destructor. In addition, the method can be used in the analysis of other semiochemical groups.

Simulating the Fate of Perfluorooctane Sulfonate (PFOS) in Environmental Multimedia of Dalian Area

Clarifying the fate of pollutants is of great significance for their pollution control and ecological risk assessments. In the present study, a level Ⅲ fugacity model was constructed to investigate the distribution and fate of perfluorooctane sulfonate (PFOS) in environmental multimedia of Dalian. The results showed that the simulated concentrations of PFOS in atmosphere, water, soil and sediment were 5.10 pg·m-3, 22.60 ng·L-1, 2.25 μg·kg-1 and 0.34 μg·kg-1, respectively, which were consistent with the measured values. The main transfer routes of PFOS between media were from atmosphere to soil and from soil to water. Meanwhile, water and soil were identified to be main sinks of PFOS in Dalian area. The primary sources of PFOS in the area were the advection inputs in atmosphere and water, and the advection output of PFOS in atmosphere was the primary outlet from Dalian. Sensitivity analysis showed that the main parameters affecting the model output were the organic carbon partition coefficient, solubility, advection inputs in atmosphere and water, and the runoff velocity of water in soil and temperature. The results of uncertain analysis indicated that the change of the overall parameters had greatest impact on the result in water and least impact on that in sediment. This study simulated the transfer and fate of PFOS in the environmental multimedia of Dalian well, which could provide a scientific basis for its pollution control and ecological risk assessment.

Predicting dissolved organic carbon partition and distribution coefficients of neutral and ionizable organic chemicals

Estimating KDOC (dissolved organic carbon/water partition coefficient) and DDOC (dissolved organic carbon/water distribution coefficient) of neutral and ionizable organic chemicals is a crucial task for assessing mobility, modelling transport, environmental fate of a variety of chemicals and for evaluating their bioavailability in terrestrial and aquatic environments. A critical literature search of reliability-selected KDOC and DDOC values was performed to setup novel predictive relationships for KDOC and DDOC of neutral and ionizable organic chemicals. This goal was pursued by using: 1) LSER (linear solvation energy relationship) models to predict KDOC for neutral chemicals using Abraham solute parameters calculated for different DOC sources (all DOC sources together, soil porewater, surface water, wastewater and Aldrich humic acid (HA)); 2) linear regressions for predicting DDOC of organic acids from the octanol/water partition coefficient (Log KOW or Log P) and the dissociation constant (pKa), accounting separately for the contribution of the neutral and ionic fraction. The proposed models predicted Log KDOC and DDOC values within a root mean square deviation (RMSD) generally smaller than 0.3 log units.

Simulation of the Migration and Release Characteristics of Organophosphate Esters in Fluctuation Zone Soil of the Three Gorges Reservoir During Flooding

In this study, we investigated the effects of organophosphate ester (OPE) concentrations, temperature, soil organic matter, and microorganisms on the migration and release of several common OPEs from fluctuation zone soil in the Three Gorges Reservoir (TGR) to the overlying water by simulation experiments in the lab. The results indicate that the release of OPEs is determined based on their concentrations in the soil. The release of OPEs from soil to the overlying water decreases with increasing organic matter content, which indicates that the presence of organic matter could inhibit the migration of OPEs. However, the inhibition of the release of OPEs of organic matter is not significantly enhanced when the organic content (dry weight) is greater than 30 g·kg-1. The average migration amount of OPEs is 1077.3 ng·mL-1 at 27℃, which was higher than that at 7℃, indicating that high temperature promotes the release of OPEs. The effect of microorganisms is not notable. Chlorine-based OPEs including Tris(2-chloroethyl) phosphate (TCEP), Tris(1-chloro-2-propyl) phosphate (TCPP), and Tris(1,3-Dichloro-2-Propyl) phosphate (TDCP) are the main monomers in the overlying water, mainly because both the Octanol-Water Partition Coefficient (Kow) and Organic Carbon Partition Coefficient (Koc) of chlorine-based OPEs are lower than that of alkane-based OPEs and aromatic-based OPEs. Thus, chlorine-based OPEs are more easily dissolved in water and are not easily adsorbed by organic matter in the soil. Therefore, chlorine-based OPEs are more likely to migrate from the soil and to be released into the overlying water than other OPEs and become the main OPE monomers in the overlying water of the TGR.

A comparison of equilibrium and kinetic passive sampling for the monitoring of aquatic organic contaminants in German rivers

The performances of an equilibrium and a kinetic passive sampler for monitoring a range of organic contaminants (Log KOW from −0.03 to 6.26) were evaluated in the effluent of a wastewater treatment plant, the receiving river Saar as well as the river Mosel in Germany. The polar organic chemical integrative sampler (POCIS) and a new mixed polymer sampler (MPS) were selected as kinetic and equilibrium passive samplers, respectively. Concentrations were described in terms of a time-weighted average concentration (CTWA) from the POCIS measurements and as an equilibrium concentration from the MPS (CEquil-MPS) and POCIS membrane (CEquil-PES) analyses. Twenty-seven compounds could be detected, including eight priority substances of the EU Water Framework Directive. Both sampler types detected a similar range of compounds in the low ng/L to μg/L range, with a high proportion of pharmaceuticals being detected at all sampling sites. To account for uncertainty in the POCIS sampling rates, a range in CTWA was estimated by applying low and high sampling rates. For the compounds that were detected in the POCIS this range was within a factor of 3.5. Interestingly, the MPS extracts showed lower ionisation artefacts than the POCIS extracts during the LC-MS/MS analysis. Finally, total water concentrations (CTotal) were estimated from the dissolved concentrations, literature organic carbon partition coefficients (KOC) and the total organic carbon levels measured in the rivers. For the compounds in this study, negligible differences between CTotal and the passive sampler-derived dissolved concentrations were found with a maximum difference of 15% for diclofenac. Overall, this study demonstrated that the parallel application of kinetic and equilibrium passive samplers can improve the description of water quality.

Critical Review: DNA Aptasensors, Are They Ready for Monitoring Organic Pollutants in Natural and Treated Water Sources?

There is a growing need to monitor anthropogenic organic contaminants detected in water sources. DNA aptamers are synthetic single-stranded oligonucleotides, selected to bind to target contaminants with favorable selectivity and sensitivity. These aptamers can be functionalized and are used with a variety of sensing platforms to develop sensors, or aptasensors. In this critical review, we (1) identify the state-of-the-art in DNA aptamer selection, (2) evaluate target and aptamer properties that make for sensitive and selective binding and sensing, (3) determine strengths and weaknesses of alternative sensing platforms, and (4) assess the potential for aptasensors to quantify environmentally relevant concentrations of organic contaminants in water. Among a suite of target and aptamer properties, binding affinity is either directly (e.g., organic carbon partition coefficient) or inversely (e.g., polar surface area) correlated to properties that indicate greater target hydrophobicity results in the strongest binding aptamers, and binding affinity is correlated to aptasensor limits of detection. Electrochemical-based aptasensors show the greatest sensitivity, which is similar to ELISA-based methods. Only a handful of aptasensors can detect organic pollutants at environmentally relevant concentrations, and interference from structurally similar analogs commonly present in natural waters is a yet-to-be overcome challenge. These findings lead to recommendations to improve aptasensor performance.

Applying no-depletion equilibrium sampling and full-depletion bioaccessibility extraction to 35 historically polycyclic aromatic hydrocarbon contaminated soils

Assessing the bioaccessibility of organic pollutants in contaminated soils is considered a complement to measurements of total concentrations in risk assessment and legislation. Consequently, methods for its quantification require validation with historically contaminated soils. In this study, 35 such soils were obtained from various locations in Switzerland and Cuba. They were exposed to different pollution sources (e.g., pyrogenic and petrogenic) at various distance (i.e., urban to rural) and were subject to different land use (e.g., urban gardening and forest). Passive equilibrium sampling with polyoxymethylene was used to determine freely dissolved concentrations (Cfree) of polycyclic aromatic hydrocarbons (PAHs), while sorptive bioaccessibility extraction (SBE) with silicone rods was used to determine the bioaccessible PAH concentrations (Cbioacc) of these soils.The organic carbon partition coefficients of the soils were highest for skeet soils, followed by traffic, urban garden and rural soils. Lowest values were obtained from soil exposed to petrogenic sources. Applicability of SBE to quantify Cbioacc was restricted by silicone rod sorption capacity, as expressed quantitatively by the Sorption Capacity Ratio (SCR); particularly for soils with very high KD. The source of contamination determined bioaccessible fractions (fbioacc). The smallest fbioacc were obtained with skeet soils (15%), followed by the pyrogenically influenced soils, rural soils, and finally, the petrogenically contaminated soil (71%). In conclusion, we present the potential and limitations of the SBE method to quantify bioaccessibility in real soils. These results can be used for additional development of this and similar bioaccessibility methods to guarantee sufficient sorption capacity to obtain reliable results.

A model for predicting organic compounds concentration change in water associated with horizontal hydraulic fracturing

Horizontal drilling and hydraulic fracturing are technologies designed to increase natural gas flow and to improve productivity in low permeability formations. During this drilling operation, tons of flowback and produced water, which contain several organic compounds, return to the surface with a potential risk of influencing the surrounding environment and human health. In order to conduct predictive risk assessments a mathematical model is needed to evaluate organic compound behaviour along the water transportation process as well as concentration changes over time throughout the operational life cycle. A comprehensive model, which fits the experimental data, combining an Organic Matter Transport Dynamic Model with a Two-Compartment First-order Rate Constant (TFRC) Model has been established to quantify the organic compounds concentrations. This algorithm model incorporates two transportation rates, fast and slow. The results show that the higher the value of the organic carbon partition coefficient (koc) in chemicals, the later the maximum concentration in water will be reached. The maximum concentration percentage would reach up to 90% of the available concentration of each compound in shale formation (whose origin may be associated to drilling fluid, connate water and/or rock matrix) over a sufficiently long period of time. This model could serve as a contribution to enhance monitoring strategy, increase benefits out of optimizing health risk assessment for local residents and provide initial baseline data to further operations.

Meta-analysis of pesticide sorption in subsoil.

Models used to assess leaching risks generally use organic carbon partition coefficient (kOC ) values derived from batch experiments on topsoil samples to estimate pesticide sorption in subsoils of much smaller organic carbon contents. This can introduce significant errors in leaching risk calculations, because inorganic sorbents can play an important role for sorption in subsoil. The objectives of the present study were therefore to summarize the available literature data on pesticide sorption in subsoils and to test whether a simple alternative model could improve on the standard kOC approach used in risk assessment models for pesticide leaching. This model describes the sorption constant as a power law function of the organic carbon content. A database with the results of batch sorption experiments was collated from published studies that emphasized measurements in subsoils. This database contains 1029 data entries from 36 published studies with data for 29 active substances (11 nonionic compounds, 10 weak acids, 6 weak bases, one cation, and one zwitterion). The results show that whereas the constant kOC model proved to be an adequate model for 17 of the 63 individual datasets, the power law model gave acceptable fits (p < 0.05) for 60 of these cases. The exponent in the power law model varied over a wide range, from slightly negative to near unity. It also differed significantly (p = 0.015) for ionized and nonionized compounds, with median values of 0.25 and 0.55, respectively. It is concluded that the power law model could be used to parameterize subsoil sorption in regulatory leaching models, because it has widespread applicability and is simple enough for this purpose. Suitable ways of incorporating this approach in risk assessment procedures are discussed. Environ Toxicol Chem 2018;37:755-761. © 2017 SETAC.