Octanol-water Partition Coefficient Log Research Articles

Characterization of The Permeation Properties of Membrane Filters and Sorption Properties of Sorbents Used for Polar Organic Chemical Integrative Samplers.

Polar organic chemical integrative samplers (POCIS) are promising devices for measuring the time-weighted average concentrations of hydrophilic compounds in aquatic environments. However, the mechanisms underlying compound uptake by POCIS remain unclear. We investigated the permeation kinetics of polyethersulfone and polytetrafluoroethylene membrane filters, and the sorption kinetics of Oasis HLB (Waters), Envi-Carb (Supelco), and Oasis WAX (Waters) sorbents. The log octanol-water partition coefficient (KOW) values of the 19 targeted compounds ranged from -0.55 to 6.0. The overall mass-transfer coefficients were negatively correlated with KOW, indicating that interactions between hydrophobic compounds and the membrane inhibit permeation. The sorption rate coefficient showed no correlation with KOW and depended on the type of sorbent used. These results imply that the uptake of highly hydrophilic compounds by POCIS is determined by both the membrane and the sorbent kinetics; however, membrane kinetics dominate the uptake of hydrophobic compounds. Environ Toxicol Chem 2024;43:2115-2121. © 2024 SETAC.

In Vitro Biological Activities of Hesperidin-Related Compounds with Different Solubility

The biological activities of hesperidin-related compounds, such as hesperetin laurate (HTL), hesperetin (HT), hesperidin (HD), and hesperidin glucoside (HDG), were investigated in vitro. The compounds showed different hydrophobicities, and the octanol–water partition coefficient log P were 7.28 ± 0.06 for HTL, 2.59 ± 0.04 for HT, 2.13 ± 0.03 for HD, and −3.45 ± 0.06 for HDG, respectively. In the DPPH assay and β-carotene bleaching assay to determine antioxidant capacity, all compounds tested showed antioxidant activity in a concentration-dependent manner, although to varying degrees. HTL and HT showed similarly high activities compared to HD or HDG. HD and HDG did not show a significant difference despite the difference in solubility between the two. Cytotoxicity was high; in the order of hydrophobicity—HTL > HT > HD > HDL in keratinocyte HaCaT cells. All compounds tested showed reducing effects on cellular inflammatory mediators and cytokines induced by UV irradiation. However, HTL and HT effectively reduced nitric oxide (NO), tumor necrosis factor α (TNF-α), and interleukin-6 (IL-6) levels compared to HD and HDG. The inhibitory effects of hesperidin-related compounds on skin-resident microorganisms were evaluated by measuring minimum inhibitory concentration (MIC). HTL showed the highest inhibitory effects against Staphylococcus aureus, Cutibacterium acnes, Candida albicans, and Malassezia furfur, followed by HT, while HD and HDF showed little effect. In conclusion, the hydrophobicity of hesperidin-related compounds was estimated to be important for biological activity in vitro, as was the presence or absence of the sugar moiety.

Development of High Surface Area Organosilicate Nanoparticulate Thin Films for Use in Sensing Hydrophobic Compounds in Sediment and Water.

The scope of this study was to apply advances in materials science, specifically the use of organosilicate nanoparticles as a high surface area platform for passive sampling of chemicals or pre-concentration for active sensing in multiple-phase complex environmental media. We have developed a novel nanoporous organosilicate (NPO) film as an extraction phase and proof of concept for application in adsorbing hydrophobic compounds in water and sediment. We characterized the NPO film properties and provided optimization for synthesis and coatings in order to apply the technology in environmental media. NPO films in this study had a very high surface area, up to 1325 m2/g due to the high level of mesoporosity in the film. The potential application of the NPO film as a sorbent phase for sensors or passive samplers was evaluated using a model hydrophobic chemical, polychlorinated biphenyls (PCB), in water and sediment. Sorption of PCB to this porous high surface area nanoparticle platform was highly correlated with the bioavailable fraction of PCB measured using whole sediment chemistry, porewater chemistry determined by solid-phase microextraction fiber methods, and the Lumbriculus variegatus bioaccumulation bioassay. The surface-modified NPO films in this study were found to highly sorb chemicals with a log octanol-water partition coefficient (Kow) greater than four; however, surface modification of these particles would be required for application to other chemicals.

Investigation of the Dispersed-Phase Distribution of Organochlorine Pesticides, Polychlorinated Biphenyls and Polycyclic Aromatic Hydrocarbons in Natural Water Systems

The article analyzes the patterns of the dispersed-phase distribution of organic ecotoxicants, namely organochlorine pesticides (OCPs), polychlorinated biphenyls (PCBs), and polycyclic aromatic hydrocarbons (PAHs), in natural water systems. The relationship between the dispersed-phase distribution of individual OCPs, PCBs, and PAHs and the logarithm of the octanol-water partition coefficient log Ko/w (hydrophobicity coefficient) was established. It was shown that the water-soluble part of individual organic ecotoxicants decreases with an increase in their hydrophobicity coefficient. Eight of the given eleven correlations are clear, significant and reliable. The influence of the characteristics of the water system on the dispersed-phase distribution of organic ecotoxicants was also investigated. It was shown that the total water-soluble part of OCPs, PCBs, and PAHs decreases with an increase in the chemical oxygen demand (COD), biological oxygen demand (BOD), and the total concentration of heavy metals (Cr, Ni, Cu, Mn, Zn, Cd, Pb). Four of the nine relevant correlations are clear, significant, and reliable.

Highly-Selective Analytical Strategy for 90 Pesticides and Metabolites Residues in Fish and Shrimp Samples.

The analysis of pesticide residues in aquatic products is challenging due to low residue levels and the complex matrix interference. In this study, we developed a simple, fast method for the trace analysis of 90 pesticides and metabolites in aquatic products. The analytes covered a wide polarity range with log Kow (log octanol-water partition coefficient) ranging from -1.2 to 6.37. Grass carp (Ctenopharyngodon idellus) and prawn (Penaeus chinensis) samples were chosen to validate the quantification method. The samples were extracted by 0.2% formic-acetonitrile, cleaned by solid-phase extraction (PRiME HLB), and analyzed by high performance liquid chromatography-tandem mass spectrometry. The results showed good linearities for the analytes and were observed in the range of 0.05-50 μg/L. The recoveries of the method were within 50.4-118.6%, with the relative standard deviations being lower than 20%. The limits of quantifications (LOQs) of the method were in the range of 0.05-5.0 μg/kg, which were superior to values compared with other research. The developed method was applied to detect pesticide residues in prawn samples from eastern coastal areas of China. Three herbicide residues of diuron, prometryn, and atrazine were detected in prawn samples. The method was sensitive and efficient, which is of significance in expanding the screening scope and improving the quantitative analysis efficiency in aquatic products.

Development of a New Polar Organic Chemical Integrative Sampler for 1,4-dioxane Using Silicone Membrane as a Diffusion Barrier.

Efficient monitoring methods must be developed for 1,4-dioxane, which is suspected to be carcinogenic to humans and is highly mobile in aquatic environments. In this regard, polar organic chemical integrative samplers (POCIS) have been utilized extensively as passive samplers for determining time-weighted average concentrations of hydrophilic organic compounds. However, POCIS are difficult to apply to extremely hydrophilic known organic compounds with negative log octanol-water partition coefficient (Kow ) values due to their limited kinetic sampling time. Using an activated carbon-based sorbent with a high adsorption capacity and a bilayer of silicone and polyethersulfone membranes that inhibit mass transfer to the sorbent, we developed a POCIS device to measure 1,4-dioxane (log Kow -0.27) in the present study. Permeation and field calibration tests demonstrated that the use of silicone membranes effectively reduces the water-to-sorbent mass transfer rate. The sampling rate and kinetic sampling period determined by field calibration tests were 1.4 ml day-1 and >14 days, respectively. Finally, the developed POCIS device was applied to a landfill treatment plant to determine the 1,4-dioxane concentrations. Environ Toxicol Chem 2023;42:296-302. © 2022 SETAC.

Modeling Time-Dependent Aquatic Toxicity of Hydrocarbons: Role of Organism Weight, Temperature, and Substance Hydrophobicity.

Oil spill exposures are highly dynamic and are not comparable to laboratory exposures used in standard toxicity tests. Toxicokinetic-toxicodynamic (TKTD) models allow translation of effects observed in the laboratory to the field. To improve TKTD model calibration, new and previously published data from 148 tests were analyzed to estimate rates characterizing the time course of toxicity for 10 fish and 42 invertebrate species across 37 hydrocarbons. A key parameter in the TKTD model is the first-order rate that incorporates passive elimination, biotransformation, and damage repair processes. The results indicated that temperature (4-26 °C), organism size (0.0001-10 g), and substance log octanol-water partition coefficient (2-6) had limited influence on this parameter, which exhibited a 5th to 95th percentile range of 0.2-2.5 day-1 (median 0.7 day-1 ). A species sensitivity distribution approach is proposed to quantify the variability of this parameter across taxa, with further studies needed for aliphatic hydrocarbons and plant species. Study findings allow existing oil spill models to be refined to improve effect predictions. Environ Toxicol Chem 2022;41:3070-3083. © 2022 ExxonMobil Biomedical Science Inc. Environmental Toxicology and Chemistry published by Wiley Periodicals LLC on behalf of SETAC.

Distribution characteristics of photoinitiators and their flux estimation from the Pearl River Delta to the coastal waters of the South China Sea

Photoinitiators (PIs) are widely used in industrial polymerization processes. It has been reported that PIs are ubiquitous in indoor environments and that humans are exposed to PIs, but the occurrence of PIs in natural environments are rarely known. In the present study, 25 PIs, including 9 benzophenones (BZPs), 8 amine co-initiators (ACIs), 4 thioxanthones (TXs) and 4 phosphine oxides (POs), were analyzed in water and sediment samples collected from eight riverine outlets of the Pearl River Delta (PRD). Eighteen, 14, and 14 of the 25 target PIs were detected in water, suspended particulate matter (SPM) and sediment samples, respectively. The total concentrations of PIs in water, SPM, and sediment were in the ranges of 2.88‒96.1 ng/L, 9.25‒923 ng/g dry weight (dw), and 3.79‒56.9 ng/g dw, with geometric mean concentration (GM) of 10.8 ng/L, 48.6 ng/g dw, and 17.1 ng/g dw, respectively. A significant linear regression was observed between the log partitioning coefficients (Kd) values of PIs and their log octanol water partition coefficient (Kow) values (R2 = 0.535, p < 0.05). The annual riverine input of PIs to the coastal waters of the South China Sea via eight main outlets of the PRD was estimated to be 4.12 × 103 kg/year, and the ∑BZPs, ∑ACIs, ∑TXs and ∑POs contributed to 1.96 × 103, 1.24 × 103, 89.6 and 830 kg/year, respectively. This is the first report of a systematic description of the occurrence characteristics of PIs exposure in water, SPM, and sediment. The environmental fate and risks of PIs in aquatic environments need further investigations.

Percutaneous absorption and exposure risk assessment of organophosphate esters in children’s toys

The percutaneous penetration and exposure risk of organophosphate esters (OPEs) from children’s toys remains largely unknown. Percutaneous penetration of OPEs was evaluated by EPISkin™ model. Chlorinated OPEs (Cl-OPEs) and alkyl OPEs, except tris(2-ethylhexyl) phosphate, exhibited a fast absorption rate and good dermal penetration ability with cumulative absorptions of 57.6–127 % of dosed OPEs. Cumulative absorptions of OPEs through skin cells were inversely associated with their molecular weight and log octanol-water partition coefficient. Additionally, a quantitative structure-activity relationship model indicated that topological charge and steric features of OPEs were closely related to the transdermal permeability of these chemicals. With the clarification of the factors affecting the transdermal penetration of OPEs, the level and exposure risk of OPEs in actual toys were studied. The summation of 18 OPE concentrations in 199 toy samples collected from China ranged from 6.82 to 228,254 ng/g, of which Cl-OPEs presented the highest concentration. Concentrations of OPEs in toys exhibited clear type differences. Daily exposure to OPEs via dermal, hand-to-mouth contact, and mouthing was evaluated, and dermal contact was a significant route for children’s exposure to OPEs. Hazard quotients for noncarcinogenic risk assessment were below 1, indicating that the health risk of OPEs via toys was relatively low.

Reduction of pesticide residues in Chrysanthemum morifolium by nonthermal plasma-activated water and impact on its quality

This study investigated the efficiency of plasma-activated water (PAW) on the reduction of pesticides, namely, metribuzin and metobromuron, and the effect of PAW treatment on the quality of fresh chrysanthemums. The reduction efficiencies reached 74.3% for metribuzin and 38.2% for metobromuron after 240 s of PAW treatment. Compared with reverse osmosis (RO) water, PAW achieved significantly higher pesticide reductions because of its higher acidity, enhanced oxidizing ability, and increased formation of reactive species. Moreover, when compared with metobromuron, metribuzin was reduced more efficiently irrespective of the RO water or PAW treatments because of its higher water solubility, lower log octanol-water partition coefficient, and more oxidizable chemical structure. Additionally, the PAW treatment did not cause adverse changes to the chrysanthemums’ color, total flavonoid content, radical scavenging, or metal chelating activities, but it did cause a slight decrease in the chrysanthemums’ aroma compounds and total reducing power. This study successfully demonstrated the effectiveness of PAW for reducing pesticides in herbal flowers like chrysanthemums and reveals PAW’s promising potential to treat foods with non-smooth surfaces.

Occurrence, partition behavior, source and ecological risk assessment of nitro-PAHs in the sediment and water of Taige Canal, China

Nitrated polycyclic aromatic hydrocarbons (NPAHs) are widespread organic pollutants that possess carcinogenic and mutagenic properties, so they may pose a risk to the environment and human health. In this study, the concentrations of 15 NPAHs and 16 polycyclic aromatic hydrocarbons (PAHs) in 30 surface water samples and 26 sediment samples were measured in 2018 from the Taige Canal, one of the main rivers flowing into Taihu Lake, China. The total NPAH concentrations in water and sediment ranged from 14.7 to 235 ng/L and 22.9 to 96.5 ng/g dw, respectively. 9-nitrophenanthrene (nd–76.3 ng/L) was the dominant compound in surface water, while 2+3-nitrofluoranthene (1.73–18.1 ng/g dw) dominated in sediment. Among PAHs, concentration ranging from 1,097 to 2,981 ng/L and 1,089 to 4,489 ng/g dw in surface water and sediment, respectively. There was a strong positive correlation between the log octanol-water partition coefficient (Kow) and log sediment-water partition coefficient due to hydrophobic interaction. The fugacity fraction value increased with the decrease of log Kow, and chrysene was transferred from water into sediment. The residual NPAHs in surface water and sediment of the Taige Canal have partial correlation. Diesel engine and coal combustion emissions were probably the principal sources of NPAHs in surface water and sediment. The results of ecological risk assessment showed that some NPAHs in water (e.g, 1-nitropyrene and 6-nitrochrysene) and sediment (e.g., 2-nitrobiphenyl, 5-nitroacenaphthene, 9-nitrophenanthrene and 2+3-nitrofluoranthene) had moderate ecological risks, which should be of concern.

Percutaneous penetration and dermal exposure risk assessment of chlorinated paraffins

The widespread occurrence of chlorinated paraffins (CPs) in environmental matrices has resulted in a high frequency exposure to CPs via dermal contact. To quantitatively estimate percutaneous penetration of CPs, Episkin® human skin equivalents (HSE) was applied as an in vitro model to evaluate the mechanism of percutaneous penetration of CPs. The co-exposure of CPs mixtures to HSE showed that about 11.7% and 10.2% of short-chain CPs (SCCPs) and medium-chain CPs (MCCPs) could penetrate the HSE and enter the receptor fluid, while no long-chain CPs (LCCPs) (C>17) were able to penetrate the HSE during the 36-h assay period. The experimentally obtained permeability coefficient (Kp) values for CPs were significantly (p < 0.01) negatively correlated with their log octanol–water partition coefficient (log Kow). Furthermore, 24 participants were recruited to assess direct human dermal exposure to CPs in China with the total CPs collected onto hand wipes and forehead wipes being 96,600 and 30,400 ng/person, respectively. The proportion of total SCCPs and MCCPs intake via dermal penetration (skin area investigated in this study) accounting for 2.0% of the total intake of CPs. Considering the total skin surface of human body is around 20 times of the area studied, the total intake of CPs through dermal penetration could be a significant exposure pathway.

In Vitro Screening of 21 Bisphenol A Replacement Alternatives: Compared with Bisphenol A, the Majority of Alternatives Are More Cytotoxic and Dysregulate More Genes in Avian Hepatocytes.

An avian in vitro screening approach was used to determine the effects of 21 bisphenol A (BPA) alternatives. Cytotoxicity and dysregulation of genes associated with estrogen response and other toxicologically relevant pathways evoked by these alternatives were compared with BPA. Most of the BPA alternatives (15/21) were equally or more cytotoxic than BPA in chicken embryonic hepatocytes; variability in cell viability was associated with chemical structure and the log octanol-water partition coefficient (logP) values. A negative linear relationship (r 2 = 0.745; p = 0.49-07 ; n = 18) was observed between logP and the log median lethal concentration (logLC50) values. The least cytotoxic BPA alternatives elicited the greatest gene dysregulation and, overall, most of the alternatives altered more genes than BPA (measured with a custom polymerase chain reaction array). This overall approach shows promise for use as a screen for hazard-based prioritization of BPA replacement alternatives and to ideally identify those that may be less harmful and/or require additional toxicity testing.Environ Toxicol Chem 2021;40:2026-2033. © 2021 Her Majesty the Queen in Right of Canada Environmental Toxicology and Chemistry © 2021 SETAC. Reproduced with the permission of the Minister of Environment and Climate Change Canada.

Assessing the Toxicity of Individual Aromatic Compounds and Mixtures to American Lobster (Homarus americanus) Larvae Using a Passive Dosing System.

Aquatic exposures to aromatic compounds (ACs) may be important contributors to biological effects of oil spills. The present study examined the acute toxicity of 11 ACs and 3 binary AC mixtures on stage 1 American lobster larvae using a passive dosing test design. The ACs investigated covered a range of classes and log octanol–water partition coefficient values (K OW; 2.5–5.5). Silicone O‐rings were used to partition ACs into seawater and maintain stable exposures. Exposed lobster larvae were assessed for mobility and survival at 3, 6, 12, 24, 36, and 48 h. Fluorometry and gas chromatography‐mass spectrometry measurements confirmed well‐defined substance exposures. Expressing lethality in terms of chemical activities yielded values between 0.01 and 0.1, consistent with a baseline mode of action. Analysis of time‐dependent median lethal/effect concentration (L/EC50) values were used to determine incipient values. An expected linear relationship between the incipient log L/EC50 and log K OW was fit to the empirical toxicity data to derive critical target lipid body burdens for immobilization and lethality endpoints. These values indicate that American lobster larvae fall on the sensitive end of the acute species sensitivity distribution. We used AC toxicity data to successfully predict toxicity of binary mixtures assuming additive toxicity. The observed time‐dependent toxicity was inversely related to log K OW and occurred more quickly than reported previously. The results contribute to improving models for predicting oil spill impacts on American lobster larvae populations. Environ Toxicol Chem 2021;40:1379–1388. © 2021 The Authors. Environmental Toxicology and Chemistry published by Wiley Periodicals LLC on behalf of SETAC.

Possibilities of poly(methyl methacrylate) as a passive sampler for determination of bioavailable concentrations in seawater.

Solvent-treated poly(methyl methacrylate) (PMMA) was recently introduced as a passive sampler for determining bioavailable concentrations, i.e., freely dissolved concentrations. However, the much knowledge required to obtain accurate bioavailable concentrations using the thus treated PMMA, applied in a marine environment, is still lacking. In this study, uptake experiments with PMMA after solvent treatment were conducted to investigate its uptake capacity and the effects of water temperature and salinity on the PMMA-water partition coefficient (KPMMA-W) for polycyclic aromatic hydrocarbons (PAHs). Thus, PMMA passive samplers preloaded with performance reference compounds were exposed to seawater to first estimate the deployment time and then to confirm if the PMMA could give the residual concentrations of PAH in mussel. The less hydrophobic PAHs (log octanol-water partition coefficient<5.5) had higher uptake capacity of PMMA-uptake was increased by a factor of up to 10. Whereas for these PAHs the KPMMA-W values and seawater temperature showed a parabolic relationship, the effect of salinity on KPMMA-W was not observed. The less hydrophobic PAH concentrations in seawater can be measured using the PMMA passive sampler over a period of about three weeks. For the PAHs detected in both PMMA and mussel, the PAH concentrations in mussel predicted from PMMA were found to be within one order of magnitude of the measured concentrations. This, therefore, suggests that solvent-treated PMMA could be used as a passive sampler to provide information on bioavailable concentrations for less hydrophobic PAHs.

Percutaneous Penetration and Metabolism of Plasticizers by Skin Cells and Its Implication in Dermal Exposure to Plasticizers by Skin Wipes.

Numerous studies focused on the human exposure to plasticizers via dermal contact; however, the percutaneous penetration of plasticizers was seldom considered in exposure assessment. In the present study, skin wipes of palms, back-of-hands, and forehead were collected from 114 participants (ages: 18-27). There was no significant difference between the levels of phthalates from palms and back-of-hand, while all phthalates collected from the forehead were significantly higher than those from palms and back-of-hand (p < 0.001); di(2-ethylhexyl)phthalate levels were substantially higher than other detected phthalates followed by di(n-butyl)phthalate and di(isobutyl)phthalate (DiBP), and for alternative plasticizers, bis-2-ethylhexyl terephthalate levels were substantially higher than acetyltributyl citrate and bis-2-ethylhexyladipate. Skin permeation and metabolism of phthalates was assessed using human skin equivalent models. The permeability coefficient (kp) values of phthalates were significantly negatively correlated with their log octanol-water partition coefficient (log Kow), while a significantly positive correlation was found between the log Kow and the cumulative amounts of phthalates in the cells. The proportion of phthalate intake via dermal exposure to skin wipes ranges from 1.3% (for dimethyl phthalate) to 8.6% (for DiBP) and suggests that dermal absorption is a significant route for adult phthalate exposure.

Role of stable hydrogen isotope variations in water for drug dissolution managing

Abstract In the present work, we provide the results of defining by utilizing Laser diffraction spectroscopy, the kinetic isotopic effect of solvent and constant of dissolution rate κ, s−1 of аn active pharmaceutical ingredient (API) in water with a different content of a stable 2 1 H _2^1{\rm{H}} isotope on the basis of the laws of first-order kinetics. This approach is based on the analysis of the light scattering profile that occurs when the particles of the dispersion phase in the aquatic environment are covered with a collimated laser beam. For the first time, the dependence of the rate of dissolution is demonstrated not only on the properties of the pharmaceutical substance itself (water solubility mg/ml, octanol–water partition coefficient log P oct/water, topological polar surface area, Abraham solvation parameters, the lattice type), but also on the properties of the solvent, depending on the content of stable hydrogen isotope. We show that the rate constant of dissolution of a sparingly hydrophobic substance moxifloxacin hydrochloride (MF · HCl) in the Mili-Q water is: k=1.20±0.14∙10−2 s−1 at 293.15 K, while in deuterium depleted water, it is k=4.24±0.4∙10−2 s−1. Consequently, we have established the development of the normal kinetic isotopic effect (kH/kD &gt;1) of the solvent. This effect can be explained both by the positions of the difference in the vibrational energy of zero levels in the initial and transition states, and from the position of water clusters giving volumetric effects of salvation, depending on the ratio D/H. The study of kinetic isotopic effects is a method that gives an indication of the mechanism of reactions and the nature of the transition state. The effect of increasing the dissolution of the API, as a function of the D/H ratio, we have discovered, can be used in the chemical and pharmaceutical industries in the study of API properties and in the drug production through improvement in soluble and pharmacokinetic characteristics.

In Situ Investigation of Performance Reference Compound-Based Estimates of PCB Equilibrated Passive Sampler Concentrations and Cfree in the Marine Water Column.

Low-density polyethylene sheets are used as passive samplers for aquatic environmental monitoring to measure the freely dissolved concentration (Cfree ) of hydrophobic organic contaminants (HOCs). Freely dissolved HOCs in water will partition into the polyethylene until a thermodynamic equilibrium is achieved; that is, the HOC's activity in the passive sampler is the same as its activity in the surrounding environment. One way to evaluate the equilibrium status or estimate the uptake kinetics is by using performance reference compounds (PRCs). A fractional equilibrium (feq ) can be determined for target HOCs, under the assumption that PRC desorption from the passive sampler occurs at the same rate as for the unlabeled target HOCs. However, few investigations have evaluated how effectively and accurately PRCs estimate target contaminant Cfree under in situ conditions. In the present study, polyethylene passive samplers were preloaded with 6 13 C-labeled polychlorinated biphenyls (PCBs) as PRCs; deployed in New Bedford Harbor, Massachusetts, USA; and collected after 30-, 56-, 99-, and 129-d deployments. Using this unique temporal sampling design, PRC results from each deployment were fit to a diffusion model to estimate the Cfree of 27 PCB congeners and compare the results between the different deployment times. Smaller PCBs had variable concentrations over the 4 deployments, whereas mid-molecular weight PCBs had consistent Cfree measurements for all deployments (relative standard deviation <20%). High-molecular weight PCBs had the largest Cfree estimates after 30 d; these estimates and their standard deviations decreased with longer deployment times. These findings suggest that when targeting PCBs with more than 6 chlorines or contaminants with a log octanol-water partition coefficient ≥6.5, a deployment time longer than 30 d may be prudent. Environ Toxicol Chem 2020;39:1165-1173. © 2020 SETAC.

Phthalate esters in biota, air and water in an agricultural area of western China, with emphasis on bioaccumulation and human exposure

Phthalate esters (PAEs) have been shown to be ubiquitous in abiotic and biotic environmental compartments; however, information about bioaccumulation behavior and human exposure, both via environmental exposure and the diet, are limited. Herein, we report the concentrations and composition profiles of phthalate esters (PAEs) in biological samples, river water, indoor air, and outdoor air samples collected from an agricultural site in western China. Dibutyl phthalate (DNBP) occupied a relatively high abundance in biological samples, discrepant with the environmental samples in which di-(2-ethylhexyl) phthalate (DEHP) was the dominant congener. Significant correlations (P < 0.05) were observed between the biota and river water samples, indicating that river water heavily influenced PAE accumulation in biological samples. The mean log Bioaccumulation Factors (BAFs) varied from 0.91 to 2.96, which implies that most PAE congeners are not likely to accumulate in organisms. No obvious trends were observed between log octanol-water partition coefficient (KOW) and log BAF values, nor between log octanol-air partition coefficient (KOW) and biota-air accumulation factors (BAAFs). Nevertheless, the calculated log air-water partitioning factors (AWPFs) of diethyl phthalate (DEP), dimethyl phthalate (DMP), and butyl benzyl phthalate (BBP) were similar to predicted values whereas those for diisobutyl phthalate (DIBP), DNBP and DEHP were significantly higher. The estimated daily intakes of PAEs via food ingestion and environmental exposure were 15, 9.4 and 1.2 ng/kg-bw/day in toddlers, children and adults, respectively, laying at the low end of the reported data and well below the reference dose.

Effects of limonene, n-decane and n-decanol on growth and membrane fatty acid composition of the microalga Botryococcus braunii

Botryococcus braunii is a promising microalga for the production of biofuels and other chemicals because of its high content of internal lipids and external hydrocarbons. However, due to the very thick cell wall of B. braunii, traditional chemical/physical downstream processing very often is not as effective as expected and requires high amounts of energy. In this cases, the application of two-phase aqueous-organic solvent systems could be an alternative to cultivate microalgae allowing for a simultaneous extraction of the valuable compounds without significant negative effects on cell growth. Two-phase systems have been applied before, however, there are no studies so far on the mechanisms used by microalgae to survive in contact with solvents present as a second-phase. In this study, the effects of the solvents limonene, n-decane and n-decanol on growth of the microalga B. braunii as well as the adaptive cell response in terms of their phospholipid fatty acid contents were analized. A concentration-dependent negative effect of all three solvents on cell growth was observed. Effects were accompanied by changes of the membrane fatty acid composition of the alga as manifested by a decrease of the unsaturation . In addition, an association was found between the solvent hydrophobicity (given as log octanol–water partition coefficient (text {P}_{O-W}) values) and their toxic effects, whereby n-decanol and n-decane emerged as the most and least toxic solvent respectively. Among the tested solvents, the latter promises to be the most suitable for a two-phase extraction system.