Octanol-water Partition Constants Research Articles

Evaluation of GC-EI&CI-TOFMS for Nontarget Analysis of Industrial Wastewater Using Hydrophilic-Lipophilic-Balanced SPME.

The evaluation of nontarget analysis (NTA) techniques for the monitoring of wastewater is important as wastewater is an anthropogenic pollution source for aquatic ecosystems and a threat to human and environmental health. This study presents the proof-of-concept NTA of industrial wastewater samples. A prototype hydrophilic-lipophilic-balanced (HLB) SPME and gas chromatography interfaced with time-of-flight high-resolution mass spectrometry (GC-TOFMS) with electron ionization (EI) and chemical ionization (CI) in parallel are employed. The HLB-SPME consists of a poly(divinylbenzene-co-N-vinylpyrrolidone) structure, allowing the extraction of hydrophilic as well as lipophilic substances. As the combination of parallel CI and EI data provides a comprehensive data set as a unique feature, this study is strongly focused on the compound identification procedure and confidence reporting of exemplary substances. Furthermore, the use of three different CI reagent ions, including [N2H]+/[N4H]+, [H3O]+, and [NH4]+, enables a broad range of analytes to be ionized in terms of selectivity and softness. The complementary information provided by EI and CI data allows a level 3 identification or higher in 69% of cases. The polarity coverage based on the physicochemical properties of the analytes (such as volatility, water solubility, hydrophilicity, and lipophilicity) was visualized by using Henry's law and octanol-water partitioning constants. In conclusion, the presented approach is shown to be valuable for water analysis and allows enhanced and accelerated compound identification compared to utilizing only one type of ionization.

Some theoretical considerations on an empirical hydrophobicity index in reversed-phase liquid chromatography

This study is analyzing the chromatographic hydrophobicity index (denoted by HIV) in reversed-phase liquid chromatography based on the linear dependence of the logarithm of experimental retention factor (log k) on the content of the organic component from mobile phase (retention function). In the literature HIV is given by the ratio between the logarithm of the extrapolated retention factor for water as mobile phase (log kw) and the slope (S) of the linear equation describing the dependence of log k on the organic solvent fraction () from mobile phase composition. The paper demonstrates that the parameter HIV is related to the extrapolated values of the retention factor for the extreme compositions of the mobile phase, namely to 100% aqueous component (log kw) and 100% organic component (log korg), respectively. A new empirical hydrophobicity descriptor (denoted by HIL) is proposed as an alternative to HIV, which is related only to slope S as a square root of (1 + S2). Some examples and correlations are discussed and compared using retention data acquired for different HPLC columns and mobile phase compositions, showing that HIL correlates better than HIV with octanol-water partition constant (log Kow) of studied solutes.

Correlation of solvent strength parameter with two molecular descriptors in reversed-phase liquid chromatography

A new hydrophobicity index has been previously developed and reported (Rev. Roum. Chim., 2023, submitted). The new index is based only on the solvent strength parameter (S) that describes the linear dependences (log k = log kw - S) between the logarithm of the retention factor (k) and volume fraction of the organic modifier in mobile phase () in an HPLC separation. The correlations between the new hydrophobicity index and octanol-water partition constant (log Kow) were evaluated and reported in present study for a set of 20 solutes by using seven C18 HPLC columns and two organic modifiers, typically utilized in reversed-phase HPLC applications (acetonitrile and methanol). All the correlations were good, showing values above 0.85. Correlations between the extrapolated values of retention factor to zero percent of the organic modifier in mobile phase, log kw, and log Kow showed also good determination coefficients R2, unlike an older hydrophobicity index based on the ratio between log kw and S, which was generally characterized by lower R2 than 0.8 for acetonitrile and 0.7 for methanol.

Determination of descriptors for the principal flavor compounds of the cinnamons of commerce by gas chromatography and liquid-liquid partition

Descriptors for fourteen semivolatile organic compounds associated with the authenticity, botanical origin, and flavor potential of the cinnamons of commerce were determined using the Solver method and experimental retention factors determined by gas chromatography at several temperatures on a minimum of seven selectivity-selected, open-tubular columns and liquid-liquid partition constants in up to twenty totally organic biphasic systems. The six descriptors that encode the solvation properties of the compounds were used to predict water-gas, octanol-gas, and octanol-water partition constants commonly employed to assess environmental distribution properties. For octanol-water partition constants, log KOW, the predicted partition constants exhibited an average absolute deviation of 0.12 for log KOW experimental – log KOW predicted (n = 14). Soil-water, soil-air, urban aerosol-air, skin-water permeation, and non-specific toxicity to the fathead minnow were predicted for the same compounds to assess their potential environmental impact. The product terms of the solvation parameter model provide a useful insight into the contribution of individual intermolecular interactions to the distribution properties of the cinnamon compounds and their environmental impact.

The effect of descriptor database selection on the physicochemical characterization and prediction of water-air, octanol-air and octanol-water partition constants using the solvation parameter model

The distribution of neutral compounds in biphasic separation systems can be described by the solvation parameter model using six solute properties, or descriptors. These descriptors (McGowan's characteristic volume, excess molar refraction, dipolarity/polarizability, hydrogen-bond acidity and basicity, and the gas-liquid partition constant on n-hexadecane at 298.15 K) are curated in two publicly accessible databases for hundreds (WSU compound descriptor database) or thousands (Abraham compound descriptor database). These databases were developed independently using different approaches resulting in descriptor values that vary for many compounds. Previously, it was shown that the two descriptor databases are not interchangeable, and the WSU descriptor database consistently demonstrated improved model performance for chromatographic systems where the uncertainty in the dependent variable was minimized by suitable quality control and calibration procedures. In this report we wish to evaluate whether the same conclusions are true for models with a dependent variable containing significant measurement uncertainty. To evaluate this hypothesis, we assembled databases for water-air, octanol-air, and octanol-water partition constants reported by multiple laboratories using various measurement methods. It was found that database selection has little effect on model quality or model predictive capability but significantly affects the assignment of the contribution of individual intermolecular interactions to the dependent variable. The latter information is database specific, and a quantitative comparison of system constants should be restricted to models using the same compound descriptor database.

Partitioning of Antioxidants in Edible Oil-Water Binary Systems and in Oil-in-Water Emulsions.

In recent years, partitioning of antioxidants in oil-water two-phase systems has received great interest because of their potential in the downstream processing of biomolecules, their benefits in health, and because partition constant values between water and model organic solvents are closely related to important biological and pharmaceutical properties such as bioavailability, passive transport, membrane permeability, and metabolism. Partitioning is also of general interest in the oil industry. Edible oils such as olive oil contain a variety of bioactive components that, depending on their partition constants, end up in an aqueous phase when extracted from olive fruits. Frequently, waste waters are subsequently discarded, but their recovery would allow for obtaining extracts with antioxidant and/or biological activities, adding commercial value to the wastes and, at the same time, would allow for minimizing environmental risks. Thus, given the importance of partitioning antioxidants, in this manuscript, we review the background theory necessary to derive the relevant equations necessary to describe, quantitatively, the partitioning of antioxidants (and, in general, other drugs) and the common methods for determining their partition constants in both binary (PWOIL) and multiphasic systems composed with edible oils. We also include some discussion on the usefulness (or not) of extrapolating the widely employed octanol-water partition constant (PWOCT) values to predict PWOIL values as well as on the effects of acidity and temperature on their distributions. Finally, there is a brief section discussing the importance of partitioning in lipidic oil-in-water emulsions, where two partition constants, that between the oil-interfacial, POI, and that between aqueous-interfacial, PwI, regions, which are needed to describe the partitioning of antioxidants, and whose values cannot be predicted from the PWOIL or the PWOCT ones.

Water-sediment partitioning of flumequine and florfenicol, two antibiotics used in salmon aquaculture in Chile

The water-sediment partitioning of flumequine and florfenicol, two antibiotics used in salmon aquaculture is a critical driver of their fate and environmental impact. Batch experiments, were carried out using pure water or seawater, with or without sediment, and at summer and winter temperatures of Chilean fjords. Log Kd (partition between water and sediment) of florfenicol in seawater varied from 0.62 ± 0.69 to 0.67 ± 0.13, and Log KOC (partition between water and organic fraction of sediment) from 2.15± 0.29 to 2.19 ± 0.13. Difference between KOC and the octanol-water partition constant (KOW) showed that for florfenicol, adsorption onto the surface of particles was more significant than the absorption driven by hydrophobicity whilst hydrophobic absorption was a major driver of flumequine sorption. Flumequine Log Kd (0.92 ± 0.25 to 1.36 ± 0.10) and Log KOC (from 2.44 ± 0.25 to 2.89 ± 0.10) demonstrated its greater affinity than florfenicol to particles and potential accumulation into marine sediments.

Kinetics of Equilibrium Passive Sampling of Organic Chemicals with Polymers in Diverse Mammalian Tissues.

Equilibrium passive sampling employing polydimethylsiloxane (PDMS) as a sampling phase can be used for the extraction of complex mixtures of organic chemicals from lipid-rich biota. We extended the method to lean tissues and more hydrophilic chemicals by implementing a mass-balance model for partitioning between lipids, proteins, and water in tissues and by accelerating uptake kinetics with a custom-built stirrer that effectively decreased time to equilibrium to less than 8 days even for a homogenized liver tissue with an only 4% lipid content. The partition constants log Klipid/PDMS between tissues and PDMS were derived from measured concentration in PDMS and the mass-balance model and were very similar for 40 neutral chemicals with octanol-water partition constants 1.4 < log Kow < 8.7, that is, log Klipid/PDMS of 1.26 (95% CI, 1.13-1.39) for the adipose tissue, 1.16 (1.00-1.33) for the liver, and 0.58 (0.42-0.73) for the brain. This conversion factor can be applied to interpret chemical analysis and in vitro bioassays after additionally accounting for a small fraction of coextracted lipids of <0.7% of the PDMS weight. PDMS is more widely applicable for passive sampling of mammalian tissues than previously thought, both, in terms of diversity of chemicals and the range of lipid contents of tissues and, therefore, an ideal method for human biomonitoring to be combined with in vitro bioassays.

Polyacrylate–water partitioning of biocidal compounds: Enhancing the understanding of biocide partitioning between render and water

In recent years, the application of polymer-based renders and paints for façade coatings of buildings has risen enormously due to the increased mounting of thermal insulation systems. These materials are commonly equipped with biocides – algaecides, fungicides, and bactericides – to protect the materials from biological deterioration. However, the biocides need to be present in the water phase in order to be active and, hence, they are flushed of the material by rain water.In order to increase the knowledge about the partitioning of biocides from render into the water phase, partition constants between the polymer – in this case polyacrylate – and water were studied using glass fibre filters coated with polyacrylate. The polyacrylate–water partition constants (logKAcW) of ten biocides used in construction material varied between 1.66 (isoproturon) and 3.57 (dichloro-N-octylisothiazolinone). The correlation of the polyacrylate–water partition constants with the octanol–water partition constants is significant, but the polyacrylate–water partition constants were predominantly below octanol–water partition constants (Kow). The comparison with render-water distribution constants showed that estimating the leaching of biocides from render based on polymer–water partitioning is a useful and practical tool.

Retention Behavior of Some Compounds Containing Polar Functional Groups on Perfluorophenyl Silica-Based Stationary Phase

A retention study on perfluorophenyl silica-based stationary phase was undertaken for some organic compounds containing different polar functionalities. The dependence of the retention factor on the content of organic modifier (acetonitrile, or methanol) in mobile phase was fitted by polynomial equations. The only exception was observed for adenine, which showed a sigmoidal dependence for the retention factor versus organic modifier content. The extrapolated values of retention factor for water as mobile phase (log kw) from these dependences were well correlated with octanol–water partition constants (log Kow), excepting the values for hexachlorocyclohexane isomers and adenine. Temperature dependences of the retention factor obeyed the van’t Hoff equation with thermodynamic parameters similar to those obtained in reversed phase on C8 or C18 stationary phases, excepting two statines whose dependences of ln k on the reciprocal value of absolute column temperature were nonlinear. Again, adenine had an atypical behavior with decrease in the retention factor with the increase in column temperature, due to possible tautomeric equilibria of this compound in presence of water, in accordance with theoretical models reported by literature. Charge modeling with MarvinSketch package program revealed charged centers from analyte molecule that could interact differently with charge centers from stationary phase.

Applications of High-Resolution Electrospray Ionization Mass Spectrometry to Measurements of Average Oxygen to Carbon Ratios in Secondary Organic Aerosols

The applicability of high-resolution electrospray ionization mass spectrometry (HR ESI-MS) to measurements of the average oxygen to carbon ratio (O/C) in secondary organic aerosols (SOAs) was investigated. Solutions with known average O/C containing up to 10 standard compounds representative of low-molecular-weight SOA constituents were analyzed and the corresponding electrospray ionization efficiencies were quantified. The assumption of equal ionization efficiency commonly used in estimating O/C ratios of SOAs was found to be reasonably accurate. We found that the accuracy of the measured O/C ratios increases by averaging the values obtained from both the posive and negative modes. A correlation was found between the ratio of the ionization efficiencies in the positive (+) and negative (-) ESI modes and the octanol-water partition constant and, more importantly, the compound's O/C. To demonstrate the utility of this correlation for estimating average O/C values of unknown mixtures, we analyzed the ESI (+) and ESI (-) data for SOAs produced by oxidation of limonene and isoprene and compared them online to O/C measurements using an aerosol mass spectrometer (AMS). This work demonstrates that the accuracy of the HR ESI-MS method is comparable to that of the AMS with the added benefit of molecular identification of the aerosol constituents.

Congener-specific organic carbon-normalized soil and sediment-water partitioning coefficients for the C1 through C8 perfluoroalkyl carboxylic and sulfonic acids

Organic carbon-normalized soil and sediment-water partitioning coefficients (Koc) were estimated for all C1 through C8 perfluoroalkyl carboxylic (PFCA) and sulfonic (PFSA) acid congeners. The limited experimental Koc data set for the straight chain C7 through C10 PFCAs and C8 and C10 PFSAs was correlated to SPARC and ALOGPS computationally estimated octanol-water partitioning/distribution constants and used to predict Koc values for both branched and linear C1 through C8 isomers. Branched and linear congeners in this homologue range are generally expected to have Koc values > 1, leading to their accumulation in organic matter on sediments and soils, retardation during ground and pore water flow, and the preferential association with dissolved organic matter in aquatic systems. Both increasing perfluoroalkyl chain length and linearity increase Koc values with substantial intra- and inter-homologue variation and interhomologue mixing. Variability in Koc values among the PFCA and PFSA congeners will likely lead to an enrichment of more linear and longer-chain isomers in organic matter fractions, resulting in aqueous phases fractionated towards shorter-chain branched congeners. The expected magnitude of fractionation will require inclusion in source apportionment models and risk assessments. A comparison of representative established quantitative structure property relationships for estimating Koc values from octanol-water partitioning constants suggests that these equilibrium partitioning frameworks may be applicable towards modeling PFCA and PFSA environmental fate processes.

Congener specific organic carbon normalized soil and sediment-water partitioning coefficients for the C1 through C8 perfluoroalkyl carboxylic and sulfonic acids

Organic carbon normalized soil and sediment-water partitioning coefficients (K~oc~) were estimated for all C~1~ through C~8~ perfluoroalkyl carboxylic (PFCA) and sulfonic (PFSA) acid congeners. The limited experimental K~oc~ dataset for the straight chain C~7~ through C~10~ PFCAs and C~8~ and C~10~ PFSAs was correlated to SPARC and ALOGPS computationally estimated octanol-water partitioning / distribution constants and used to predict K~oc~ values for both branched and linear C~1~ through C~8~ isomers. Branched and linear congeners in this homologue range are generally expected to have K~oc~ values >1, leading to their accumulation in organic matter on sediments and soils, retardation during ground and pore water flow, and the preferential association with dissolved organic matter in aquatic systems. Both increasing perfluoroalkyl chain length and linearity increase K~oc~ values with substantial intra- and inter-homologue variation and interhomologue mixing. Variability in K~oc~ values among the PFCA and PFSA congeners will likely lead to an enrichment of more linear and longer chain isomers in organic matter fractions, resulting in aqueous phases fractionated towards shorter chain branched congeners. The expected magnitude of fractionation will require inclusion in source apportionment models and risk assessments. A comparison of representative established quantitative structure property relationships for estimating K~oc~ values from octanol-water partitioning constants suggests that these equilibrium partitioning frameworks may be applicable towards modeling PFCA and PFSA environmental fate processes.

Congener specific organic carbon normalized soil and sediment-water partitioning coefficients for the C~1~ through C~8~ perfluoroalkyl carboxylic and sulfonic acids

AbstractOrganic carbon normalized soil and sediment-water partitioning coefficients (K~oc~) were estimated for all C~1~ through C~8~ perfluoroalkyl carboxylic (PFCA) and sulfonic (PFSA) acid congeners. The limited experimental K~oc~ dataset for the straight chain C~7~ through C~10~ PFCAs and C~8~ and C~10~ PFSAs was correlated to SPARC and ALOGPS computationally estimated octanol-water partitioning / distribution constants and used to predict K~oc~ values for both branched and linear C~1~ through C~8~ isomers. Branched and linear congeners in this homologue range are generally expected to have K~oc~ values &gt;1, leading to their accumulation in organic matter on sediments and soils, retardation during ground and pore water flow, and the preferential association with dissolved organic matter in aquatic systems. Both increasing perfluoroalkyl chain length and linearity increase K~oc~ values with substantial intra- and inter-homologue variation and interhomologue mixing. Variability in K~oc~ values among the PFCA and PFSA congeners will likely lead to an enrichment of more linear and longer chain isomers in organic matter fractions, resulting in aqueous phases fractionated towards shorter chain branched congeners. The expected magnitude of fractionation will require inclusion in source apportionment models and risk assessments. A comparison of representative established quantitative structure property relationships for estimating K~oc~ values from octanol-water partitioning constants suggests that these equilibrium partitioning frameworks may be applicable towards modeling PFCA and PFSA environmental fate processes.

A comparative assessment of octanol-water partitioning and distribution constant estimation methods for perfluoroalkyl carboxylates and sulfonates

AbstractNew experimental data is available in the literature regarding the octanol-water distribution behavior of representative straight chain perfluoroalkyl carboxylate (PFCA) and sulfonate (PFSA) congeners. The current study provides the first investigation into the predictive ability of various software programs for estimating the corresponding octanol-water partitioning (log P) and distribution (log D) constants of PFCAs and PFSAs. Wide predictive variation was found within and between the various methods. Several programs were able to accurately estimate the log P/D fragmental contributions of a -CF~2~- group for PFCAs, as well as the associated Gibbs free energies for partitioning into octanol from water due to the hydrophobic character of the perfluoroalkyl chain (Δ~hydrophobic~G~ow~). Only the SPARC log D method accurately predicted the electrostatic contributions of the carboxylate head group (Δ~electrostatic~G~ow~) towards octanol-water partitioning for PFCAs. Similar log D values and organic carbon normalized sediment-water partitioning coefficients (K~oc~) for PFCAs and PFSAs having equivalent perfluoroalkyl chain lengths suggests potentially equivalent Δ~electrostatic~G~ow~ and Δ~hydrophobic~G~ow~ contributions towards lipophilic partitioning for these two contaminant classes at near neutral pH values, regardless of head group identity. In contrast, there are potentially different Δ~electrostatic~G~ow~ and Δ~hydrophobic~G~ow~ contributions towards proteinophilic partitioning under biologically relevant conditions.

A comparative assessment of octanol-water partitioning and distribution constant estimation methods for perfluoroalkyl carboxylates and sulfonates

AbstractNew experimental data is available in the literature regarding the octanol-water distribution behavior of representative straight chain perfluoroalkyl carboxylate (PFCA) and sulfonate (PFSA) congeners. The current study provides the first investigation into the predictive ability of various software programs for estimating the corresponding octanol-water partitioning (log P) and distribution (log D) constants of PFCAs and PFSAs. Wide predictive variation was found within and between the various methods. Several programs were able to accurately estimate the log P/D fragmental contributions of a -CF~2~- group for PFCAs, as well as the associated Gibbs free energies for partitioning into octanol from water due to the hydrophobic character of the perfluoroalkyl chain (Δ~hydrophobic~G~ow~). Only the SPARC log D method accurately predicted the electrostatic contributions of the carboxylate head group (Δ~electrostatic~G~ow~) towards octanol-water partitioning for PFCAs. Similar log D values and organic carbon normalized sediment-water partitioning coefficients (K~oc~) for PFCAs and PFSAs having equivalent perfluoroalkyl chain lengths suggests potentially equivalent Δ~electrostatic~G~ow~ and Δ~hydrophobic~G~ow~ contributions towards lipophilic partitioning for these two contaminant classes, regardless of head group identity. In contrast, there are potentially different Δ~electrostatic~G~ow~ and Δ~hydrophobic~G~ow~ contributions towards proteinophilic partitioning.

An assessment of organic solvent based equilibrium partitioning methods for predicting the bioconcentration behavior of perfluorinated sulfonic acids, carboxylic acids, and sulfonamides

AbstractSPARC, KOWWIN, and ALOGPS octanol-water partitioning (log K~ow~) and distribution (log D) constants were calculated for all C~1~ through C~8~ and the straight chain C~9~ through C~15~ perfluoroalkyl sulfonic acids (PFSAs) and carboxylic acids (PFCAs). Application of five established models for estimating bioconcentration factors (BCFs) were applied to the PFSA and PFCA log K~ow~ and log D data and compared to available field and laboratory BCF data. Wide variability was observed between the methods for estimating log K~ow~ and log D values, ranging up to several log units for particular congeners, and which was further compounded by additional variability introduced by the different BCF equations applied. With the exception of n-perfluorooctanecarboxylic acid (n-PFOA), whose experimental BCF was poorly modeled by all approaches, the experimental BCF values of the other PFSA and PFCA congeners were reasonably approximated by the ALOGPS log P values in combination with any of the five log K~ow~ based BCF equations. The SPARC and KOWWIN log K~ow~ and log D values provided generally less accurate BCF estimates regardless of the BCF equation applied. However, the SPARC K~ow~ values did provide BCF estimates for PFSA congeners with errors &lt;0.3 log units using any of the five BCF equations. Model lipophilic and proteinophilic solvent based distribution constant calculations for the PFSA and PFCA congeners with experimental BCFs exhibited similar relationships with their corresponding BCF values. For longer chain PFCA and PFSA congeners, increasing hydrophobicity of the perfluoroalkyl chain appears to be driving corresponding increases in BCF values. Perfluorooalkyl sulfonamides are expected to display similar chain length and branching pattern influences on BCFs, but no experimental data are currently available upon which to validate the estimated values which range widely between the various approaches by up to 10 log units. The amidic proton acidity on primary and secondary perfluoroalkyl sulfonamides will play a significant role in the partitioning of these compounds with both abiotic and biotic organic matter, and will need to be taken into account when assessing their environmental and biological fate.

Equilibrium partitioning behavior of naphthalene and phenanthrene with axenic microplantlets of the temperate green seaweed Acrosiphonia coalita

The partitioning behavior of the polycyclic aromatic hydrocarbon (PAH) compounds naphthalene and phenanthrene with the temperate green seaweed Acrosiphonia coalita was characterized. The uptake and partitioning experiments were designed to prevent PAH volatilization, and the PAH concentration was measured in both the seawater liquid medium and in the algal biomass. Axenic microplantlets of A. coalita were used in all experiments to eliminate the possibility of microbial PAH biotransformation. Gas chromatography/mass spectrometry analysis did not reveal any putative metabolites of phenanthrene oxidative biotransformation in either the seawater medium or the algal biomass, but did show that dissolved organic matter from algal biomass constituents were in the liquid medium. The algal biomass grew by 30% over the 114 h duration of the partitioning experiments, suggesting PAH compounds did not harm the organism. Both living and heat-killed microplantlets partitioned PAH compounds into the biomass. Naphthalene and phenanthrene reversibly partitioned into the lipid fraction of the algal biomass with equilibrium partitioning constants of 0.130 ± 0.007 and 1.58 ± 0.03 L g −1 dry cell mass, respectively, which scaled proportionally to their octanol–water partitioning constants. The PAH material balance for the partitioning process closed between 86% and 100% for naphthalene adsorption and phenanthrene desorption, but closed at 52% for phenanthrene adsorption. To account for the loss, it was proposed that phenanthrene interacted with dissolved organic matter released by the living algal biomass. This study has provided fundamental information needed to assess how seaweeds can play a role in the bioaccumulation and bioremediation of PAH compounds in the marine environment.

Congener specific organic carbon normalized soil and sediment-water partitioning coefficients for the C1 through C8 perfluorinated alkylsulfonic and alkylcarboxylic acids

AbstractOrganic carbon normalized soil and sediment-water partitioning (Koc) coefficients were estimated for all C1 through C8 perfluorinated alkylsulfonic acid (PFSA) and alkylcarboxylic acids (PFCA) congeners. The limited experimental Koc dataset for the straight chain C7 through C10 PFCAs and C8 and C10 PFSAs was correlated to SPARC and ALOGPS computationally estimated octanol-water partitioning constants and used to predict Koc values for both branched and linear C1 through C8 isomers. All branched and linear congeners in this homologue range are expected to have Koc values&gt;1, leading to their accumulation in organic matter on sediments and soils, retardation during ground and pore water flow, and the preferential association with dissolved organic matter in aquatic systems. Both increasing perfluoroalkyl chain length and linearity increase Koc values with substantial intra- and inter-homologue variation and interhomologue mixing. Variability in Koc values among the PFCA and PFSA congeners will likely lead to an enrichment of more linear and longer chain isomers in organic matter fractions, resulting in aqueous phases fractionated towards shorter chain branched congeners. The expected magnitude of fractionation will require inclusion in source apportionment models and risk assessments. A comparison of representative established quantitative structure property relationships for estimated Koc values from octanol-water partitioning constants suggests that equilibrium partitioning frameworks may be applicable towards modeling PFCA and PFSA environmental fate processes and warrants further study using other partitioning coefficients for which suitable experimental data is available.

Polyethylene Devices: Passive Samplers for Measuring Dissolved Hydrophobic Organic Compounds in Aquatic Environments

We demonstrate the use of polyethylene devices (PEDs) for assessing hydrophobic organic compounds (HOCs) in aquatic environments. Like semipermeable membrane devices (SPMDs) and solid-phase microextraction (SPME), PEDs passively accumulate HOCs in proportion to their freely dissolved concentrations. Polyethylene-water partition constants (K(PEW)S) were measured in the laboratory for eight polycyclic aromatic hydrocarbons (PAHs), five polychlorinated biphenyls (PCBs), and one polychlorinated dibenzop-dioxin (PCDD), and these were found to correlate with octanol-water partition constants (K(OW)s; log K(PEW) = 1.13 log K(OW) - 0.86, R2 = 0.89). Temperature and salinity dependencies of K(PEW) values for the HOCs tested were well predicted with excess enthalpies of solution in water and Setschenow constants, respectively. We also showed that standards, impregnated in the PED before deployment, can be used to correct for incomplete equilibrations. Using PEDs, we measured phenanthrene and pyrene at ng/L concentrations and 2,2',5,5'-tetrachlorobiphenyl at pg/L concentrations in Boston Harbor seawater, consistent with our findings using traditional procedures. PEDs are cheap and robust samplers, competent to accomplish in situ, time-averaged passive sampling with fast equilibration times (approximately days) and simplified laboratory analyses.