Experimental Determination of Air/Water Partition Coefficients for 21 Per- and Polyfluoroalkyl Substances Reveals Variable Performance of Property Prediction Models.

Per- and polyfluoroalkyl substances (PFAS) are a group of chemicals of high environmental concern. However, reliable data for the air/water partition coefficients (Kaw), which are required for fate, exposure, and risk analysis, are available for only a few PFAS. In this study, Kaw values at 25 °C were determined for 21 neutral PFAS by using the hexadecane/air/water thermodynamic cycle. Hexadecane/water partition coefficients (KHxd/w) were measured with batch partition, shared-headspace, and/or modified variable phase ratio headspace methods and were divided by hexadecane/air partition coefficients (KHxd/air) to obtain Kaw values over 7 orders of magnitude (10-4.9 to 102.3). Comparison to predicted Kaw values by four models showed that the quantum chemically based COSMOtherm model stood out for accuracy with a root-mean-squared error (RMSE) of 0.42 log units, as compared to HenryWin, OPERA, and the linear solvation energy relationship with predicted descriptors (RMSE, 1.28-2.23). The results indicate the advantage of a theoretical model over empirical models for a data-poor class like PFAS and the importance of experimentally filling data gaps in the chemical domain of environmental interest. Kaw values for 222 neutral (or neutral species of) PFAS were predicted using COSMOtherm as current best estimates for practical and regulatory use.

Volatility and Nonspecific van der Waals Interaction Properties of Per- and Polyfluoroalkyl Substances (PFAS): Evaluation Using Hexadecane/Air Partition Coefficients.

Per- and polyfluoroalkyl substances (PFAS) form weak van der Waals (vdW) interactions, which render this class of chemicals more volatile than nonfluorinated analogues. Here, the hexadecane/air partition coefficient (KHxd/air) values at 25 °C, as an index of vdW interaction strength and volatility, were determined for 64 neutral PFAS using the variable phase ratio headspace and gas chromatographic retention methods. Log KHxd/air values increased linearly with increasing number of CF2 units, and the increase in log KHxd/air value per CF2 was smaller than that per CH2. Comparison of PFAS sharing the same perfluoroalkyl chain length but with different functional groups demonstrated that KHxd/air was highest for the N-alkyl perfluoroalkanesulfonamidethanols and lowest for the perfluoroalkanes and that the size of the nonfluorinated structure determines the difference in KHxd/air between PFAS groups. Two models, the quantum chemistry-based COSMOtherm model and an iterative fragment selection quantitative structure-property relationship (IFS-QSPR) model, accurately predicted the log KHxd/air values of the PFAS with root-mean-square errors of 0.55 and 0.35, respectively. COSMOtherm showed minor systematic errors for all PFAS, whereas IFS-QSPR exhibited large errors for a few PFAS groups that were outside the model applicability domain. The present data set will be useful as a benchmark of the volatilities of the various PFAS and for predicting other partition coefficient values of PFAS.

Predicting Partition Coefficients of Short-Chain Chlorinated Paraffin Congeners by COSMO-RS-Trained Fragment Contribution Models.

Chlorinated paraffins (CPs) are highly complex mixtures of polychlorinated n-alkanes with differing chain lengths and chlorination patterns. Knowledge on physicochemical properties of individual congeners is limited but needed to understand their environmental fate and potential risks. This work used a sophisticated but time-demanding quantum chemically based method COSMO-RS and a fast-running fragment contribution approach to enable prediction of partition coefficients for a large number of short-chain chlorinated paraffin (SCCP) congeners. Fragment contribution models (FCMs) were developed using molecular fragments with a length of up to C4 in CP molecules as explanatory variables and COSMO-RS-calculated partition coefficients as training data. The resulting FCMs could quickly provide COSMO-RS predictions for octanol-water (Kow), air-water (Kaw), and octanol-air (Koa) partition coefficients of SCCP congeners with an accuracy of 0.1-0.3 log units root-mean-squared errors. The FCM predictions for Kow agreed with experimental values for individual constitutional isomers within 1 log unit. The distribution of partition coefficients for each SCCP congener group was computed, which successfully reproduced experimental log Kow ranges of industrial CP mixtures. As an application of the developed FCMs, the predicted Kaw and Koa were plotted to evaluate the bioaccumulation potential of each SCCP congener group.

Mechanisms of Neutral and Anionic Surfactant Sorption to Solid-Phase Microextraction Fibers.

Octanol-water partitioning (Kow) is considered a key parameter for hydrophobicity and is often applied in the prediction of the environmental fate and exposure of neutral organic compounds. However, surfactants can create difficulties in the determination of Kow because of emulsification of both water and octanol phases. Moreover, not only is sorption behavior of ionic surfactants related to hydrophobicity, but also other interactions are relevant in sorption processes. A different approach to develop parameters that can be applied in predictive modeling of the fate of surfactants in the environment is therefore required. Distribution between solid-phase microextraction (SPME) fibers and water was used in this study to measure the affinity of surfactants to a hydrophobic phase. Fiber-water sorption coefficients of alcohol ethoxylates, alkyl carboxylates, alkyl sulfates, and alkyl sulfonates were determined at pH 7 by equilibration of the test analytes between fiber and water. Distribution between fiber and water of anionic compounds with pKa ∼ 5 (i.e., alkyl carboxylates) was dominated by the neutral fraction. Anionic surfactants with pKa ≤ 2 (i.e., alkyl sulfates and alkyl sulfonates) showed strong nonlinear distribution to the fiber. The fiber-water sorption coefficients for alcohol ethoxylates and alkyl sulfates showed a linear trend with bioconcentration factors from the literature. Fiber-water sorption coefficients are promising as a parameter to study the effects of hydrophobicity and other potential interactions on sorption behavior of neutral and anionic surfactants.

Plastics in the marine environment: the dark side of a modern gift.

Plastics are cheap, strong, and durable and offer considerable benefits to humanity. They potentially can enhance the benefits that both medical and scientific technology will bestow to humankind. However, it has now been several decades since the use of plastics exploded, and we have evidence that our current approach to production, use, transport and disposal of plastic materials has caused, and is still causing serious effects on wildlife, and is not sustainable. Because of frequent inappropriate waste management practices, or irresponsible human behavior, large masses of plastic items have been released into the environment, and thereby have entered the world's oceans. Moreover, this process continues, and in some places is even increasing. Most plastic debris that now exists in the marine environment originated from ocean-based sources such as the fishing industry. Plastics accumulate in coastal areas, at the ocean surface and on the seabed. Because 70% of all plastics are known to eventually sink, it is suspected that ever increasing amounts of plastic items are accumulating in seabed sediments. Plastics do not biodegrade, although, under the influence of solar UV radiations, plastics do degrade and fragment into small particles, termed microplastics. Our oceans eventually serve as a sink for these small plastic particles and in one estimate, it is thought that 200,000 microplastics per km(2) of the ocean's surface commonly exist. The impact of plastic debris has been studied since the beginning of the 1960's. To date, more than 267 species in the marine environment are known to have been affected by plastic entanglement or ingestion. Marine mammals are among those species that are most affected by entanglement in plastic debris. By contrast, marine birds suffer the most from ingestion of plastics. Organisms can also be seriously absorbed by floating plastic debris, or the contaminants may derive from plastic additives that are leached to the environment. Recent studies emphasize the important role of microplastics as they are easily ingestible by small organisms, such as plankton species, and form a pathway for contaminants to enter the food web. Contaminants leached from plastics tend to bioaccumulate in those organisms that absorb them, and chemical concentrations are often higher at higher trophic levels. This causes a threat to the basis of every food web and can have serious and far-reaching effects, even on nonmarine species such as polar bears and humans, who consume marine-grown food. Therefore, resolving the plastic debris problem is important to human kind for two reasons: we are both creator, and victim of the plastic pollution problem. Solutions to the plastic debris problem can only be achieved through a combination of actions. Such actions include the following: Legislation against marine pollution by plastics must be enforced, recycling must be accentuated, alternatives (biodegradable) to current plastic products must be found, and clean-up of debris must proceed, if the marine plastic pollution problem is to eventually be resolved. Governments cannot accomplish this task on their own, and will need help and initiative from the public. Moreover, resolving this long-standing problem will require time, money, and energy from many individuals now living and those of future generations, if a safer and cleaner marine environment is to be achieved.

Direct measurements and modeling of congener group specific vapor pressure for chlorinated paraffins.

Chlorinated Paraffins (CPs) are a complex group of manmade chemicals detected widely in the environment. To predict their environmental fate and effects, it is important to understand their physical-chemical properties including vapor pressure. In this study, the first direct measurements of the vapor pressure for CP congener groups (C10-16Cl4-11) are presented. Vapor pressure was measured above three industrial CP mixtures with different congener distributions between 20 and 50 °C using a gas saturation method. The measured saturated vapor pressure (P∗) decreased with increasing carbon chain length and Cl content. ΔHvap ranged between 73 and 122 kJ mol-1, consistent with data from the literature and model prediction. The experimental log P∗ at 25 °C agreed well with predictions from an empirical regression model in the literature (R2 = 0.97; RSME = 0.25) and with those predicted from the COSMO-RS-trained fragment contribution model (R2 = 0.95; RSME = 0.35). A new empirical model was calibrated with the P∗ data for 35 congener groups measured in this study. Predicted log P∗ values correlate well with field-measured gas/particle partition coefficients and may therefore be used for estimating the environmental fate and pathways of a broad range of CPs in the environment.

Congener-specific partition properties of chlorinated paraffins evaluated with COSMOtherm and gas chromatographic retention indices.

Chlorinated Paraffins (CPs) are high volume production chemicals and have been found in various organisms including humans and in environmental samples from remote regions. It is thus of great importance to understand the physical-chemical properties of CPs. In this study, gas chromatographic (GC) retention indexes (RIs) of 25 CP congeners were measured on various polar and nonpolar columns to investigate the relationships between the molecular structure and the partition properties. Retention measurements show that analytical standards of individual CPs often contain several stereoisomers. RI values show that chlorination pattern have a large influence on the polarity of CPs. Single Cl substitutions (-CHCl-, -CH2Cl) generally increase polarity of CPs. However, many consecutive -CHCl- units (e.g., 1,2,3,4,5,6-C11Cl6) increase polarity less than expected from the total number of -CHCl- units. Polyparameter linear free energy relationship descriptors show that polarity difference between CP congeners can be explained by the H-bond donating properties of CPs. RI values of CP congeners were predicted using the quantum chemically based prediction tool COSMOthermX. Predicted RI values correlate well with the experimental data (R2, 0.975-0.995), indicating that COSMOthermX can be used to accurately predict the retention of CP congeners on GC columns.

Fragment-based approach to calculate hydrophobicity of anionic and nonionic surfactants derived from chromatographic retention on a C18 stationary phase.

To predict the fate and potential effects of organic contaminants, information about their hydrophobicity is required. However, common parameters to describe the hydrophobicity of organic compounds (e.g., octanol-water partition constant [KOW ]) proved to be inadequate for ionic and nonionic surfactants because of their surface-active properties. As an alternative approach to determine their hydrophobicity, the aim of the present study was therefore to measure the retention of a wide range of surfactants on a C18 stationary phase. Capacity factors in pure water (k'0 ) increased linearly with increasing number of carbon atoms in the surfactant structure. Fragment contribution values were determined for each structural unit with multilinear regression, and the results were consistent with the expected influence of these fragments on the hydrophobicity of surfactants. Capacity factors of reference compounds and log KOW values from the literature were used to estimate log KOW values for surfactants (log KOWHPLC). These log KOWHPLC values were also compared to log KOW values calculated with 4 computational programs: KOWWIN, Marvin calculator, SPARC, and COSMOThermX. In conclusion, capacity factors from a C18 stationary phase are found to better reflect hydrophobicity of surfactants than their KOW values. Environ Toxicol Chem 2017;36:329-336. © 2016 The Authors. Environmental Toxicology and Chemistry Published by Wiley Periodicals, Inc. on behalf of SETAC.