Ian T. Cousins

Perfluoroalkyl and polyfluoroalkyl substances in the environment: Terminology, classification, and origins

The primary aim of this article is to provide an overview of perfluoroalkyl and polyfluoroalkyl substances (PFASs) detected in the environment, wildlife, and humans, and recommend clear, specific, and descriptive terminology, names, and acronyms for PFASs. The overarching objective is to unify and harmonize communication on PFASs by offering terminology for use by the global scientific, regulatory, and industrial communities. A particular emphasis is placed on long-chain perfluoroalkyl acids, substances related to the long-chain perfluoroalkyl acids, and substances intended as alternatives to the use of the long-chain perfluoroalkyl acids or their precursors. First, we define PFASs, classify them into various families, and recommend a pragmatic set of common names and acronyms for both the families and their individual members. Terminology related to fluorinated polymers is an important aspect of our classification. Second, we provide a brief description of the 2 main production processes, electrochemical fluorination and telomerization, used for introducing perfluoroalkyl moieties into organic compounds, and we specify the types of byproducts (isomers and homologues) likely to arise in these processes. Third, we show how the principal families of PFASs are interrelated as industrial, environmental, or metabolic precursors or transformation products of one another. We pay particular attention to those PFASs that have the potential to be converted, by abiotic or biotic environmental processes or by human metabolism, into long-chain perfluoroalkyl carboxylic or sulfonic acids, which are currently the focus of regulatory action. The Supplemental Data lists 42 families and subfamilies of PFASs and 268 selected individual compounds, providing recommended names and acronyms, and structural formulas, as well as Chemical Abstracts Service registry numbers. Integr Environ Assess Manag 2011;7:513–541.

Estimating consumer exposure to PFOS and PFOA.

Perfluorinated compounds have been used for more than 50 years as process aids, surfactants, and for surface protection. This study is a comprehensive assessment of consumer exposure to perfluorooctane sulfonate (PFOS) and perfluorooctanoic acid (PFOA) from a variety of environmental and product-related sources. To identify relevant pathways leading to consumer exposure to PFOS and PFOA a scenario-based approach has been applied. Scenarios represent realistic situations where age- and gender-specific exposure occurs in the everyday life of consumers. We find that North American and European consumers are likely to experience ubiquitous and long-term uptake doses of PFOS and PFOA in the range of 3 to 220 ng per kg body weight per day (ng/kg(bw)/day) and 1 to 130 ng/kg(bw)/day, respectively. The greatest portion of the chronic exposure to PFOS and PFOA is likely to result from the intake of contaminated foods, including drinking water. Consumer products cause a minor portion of the consumer exposure to PFOS and PFOA. Of these, it is mainly impregnation sprays, treated carpets in homes, and coated food contact materials that may lead to consumer exposure to PFOS and PFOA. Children tend to experience higher total uptake doses (on a body weight basis) than teenagers and adults because of higher relative uptake via food consumption and hand-to-mouth transfer of chemical from treated carpets and ingestion of dust. The uptake estimates based on scenarios are within the range of values derived from blood serum data by applying a one-compartment pharmacokinetic model.

Assessing the environmental fate of chemicals of emerging concern: a case study of the polybrominated diphenyl ethers

It is suggested that assessments of chemicals of emerging concern can be rationally structured around a multistage process in which fate and risk are evaluated with increasing accuracy as new data become available. An initial tentative and approximate assessment of fate and risk can identify key data gaps and justify and direct further investigations, which progressively improve the reliability of the assessment. This approach is demonstrated for a class of chemicals, the polybrominated diphenyl ethers (PBDEs), which is of increasing concern, but about which there is presently a lack of comprehensive data on properties, sources, fate and effects. Specifically, 20 PBDE congeners are investigated using the suggested approach and research needs are identified.

Biodegradation of microcystin-LR by indigenous mixed bacterial populations

Abstract Microcystin-LR is a potent mammalian toxin which is known to have been responsible for the deaths of domesticated animals, and consequently there is concern as to its environmental fate. In laboratory experiments conducted using low levels (10 μg l −1 ) of microcystin-LR in reservoir water, primary biodegradation of the toxin was shown to occur in less than 1 week. An experiment designed to ascertain the degree of mineralisation of microcystin-LR, using natural microbial populations under aerobic conditions, showed that the peptide ring appears to be fairly resistant to biodegradation, as the degree of mineralisation was not high. However, as the toxicity of microcystin-LR is critically dependent on the orientation of the peptide ring with respect to the “Adda” (the β-amino acid which is unique to the blue-green algal toxins) side-chain, and it appears that this side chain is affected during biodegradation, it seems likely that a reduction in toxicity occurs.

A review of the processes involved in the exchange of semi-volatile organic compounds (SVOC) across the air–soil interface

The exchange of semi-volatile organic compounds (SVOC) across the air–soil interface is one of the most important processes determining the environmental fate and human exposure of these compounds. The main processes contributing to air–soil exchange of SVOC are dry deposition (both by vapour adsorption and in association with particles), wet deposition (by precipitation scavenging of vapour- and particle-sorbed chemicals) and volatilisation from the soil. These processes are reviewed and evaluated and theoretical approaches to describe them are presented. Suggestions for further research are highlighted. The review focuses on persistent, non-ionic organics (such as PCB, PAH and PCDD/F).

Global emission inventories for C4-C14 perfluoroalkyl carboxylic acid (PFCA) homologues from 1951 to 2030, Part I: production and emissions from quantifiable sources.

We quantify global emissions of C4-C14 perfluoroalkyl carboxylic acid (PFCA) homologues during the life-cycle of products based on perfluorooctanoic acid (PFOA), perfluorononanoic acid (PFNA), perfluorooctane sulfonyl fluoride (POSF), and fluorotelomer compounds. We estimate emissions of 2610-21400 tonnes of C4-C14 PFCAs in the period from 1951 to 2015, and project 20-6420 tonnes to be emitted from 2016 to 2030. The global annual emissions steadily increased in the period 1951-2002, followed by a decrease and then another increase in the period 2002-2012. Releases from fluoropolymer production contributed most to historical PFCA emissions (e.g. 55-83% in 1951-2002). Since 2002, there has been a geographical shift of industrial sources (particularly fluoropolymer production sites) from North America, Europe and Japan to emerging Asian economies, especially China. Sources differ between PFCA homologues, sometimes considerably, and the relative contributions of each source change over time. For example, whereas 98-100% of historical (1951-2002) PFOA emissions are attributed to direct releases during the life-cycle of products containing PFOA as ingredients or impurities, a much higher historical contribution from PFCA precursor degradation is estimated for some other homologues (e.g. 9-78% for PFDA). We address the uncertainties of the PFCA emissions by defining a lower and a higher emission scenario, which differ by approximately a factor of eight.

A Multimedia Assessment of the Environmental Fate of Bisphenol A

A comprehensive multimedia assessment of the environmental fate of bisphenol A (BPA) is presented. Components of the assessment include an evaluation of relevant partitioning and reactive properties, estimation of discharge quantities in the U.S. and the European Union (E.U.) resulting in conservative and realistic emission scenarios, and a review of monitoring data. Evaluative assessments of chemical fate using the Equilibrium Criterion (EQC) model are described from which it is concluded that the low volatility of BPA will result in negligible presence in the atmosphere. It is relatively rapidly degraded in the environment with half-lives in water and soil of about 4.5 days and less than 1 day in air, and with an overall half-life of 4.5 to 4.7 days, depending on the medium of release. The degradation rate in water is such that it may be transported some hundreds of kilometres in rivers, but long-range transport potential in air is negligible. Its low bioconcentration factor is consistent with rapid metabolism in fish (half-life less than 1 day). The estimated concentrations were generally consistent with the monitoring data, with the exception of sediment-water concentration ratios. Several hypotheses for the apparent nonequilibrium sediment-water partitioning are presented.

Measuring and modelling the vertical distribution of semi-volatile organic compounds in soils. I : PCB and PAH soil core data

Soil cores were collected from undisturbed soils at four locations in the UK and analysed for PCBs, PAHs and soil organic carbon. In all four soil cores ΣPCB and ΣPAH concentrations peaked at or just below the soil surface and declined with depth. Statistically significant correlations were obtained between compound concentrations and organic carbon content in all four soil cores. PAH and PCB homologue profiles at different soil depths and horizons provided information on transport of the compounds in the soils. Fairly constant homologue profiles with depth in the cores suggested that bioturbation may be an important soil transport process for PCBs and PAHs.

Strategies for including vegetation compartments in multimedia models.

The incentives for including vegetation compartments in multimedia Level I, II and III fugacity calculations are discussed and equations and parameters for undertaking the calculations suggested. Model outputs with and without vegetation compartments are compared for 12 non-ionic organic chemicals with a wide variety of physical-chemical properties. Inclusion of vegetation compartments is shown to have a significant effect on two classes of chemicals: (1) those that are taken up by atmospheric deposition and (2) those that are taken up by transpiration through the plant roots. It is suggested that uptake from the atmosphere is important for chemicals with logK(OA) greater than 6 and a logK(AW) of greater than -6. Plant uptake by transpiration is important for chemicals with logK(OW) less than 2.5 and a logK(AW) of less than -1. At logK(OA) > 9 atmospheric uptake is dominated by particle-bound deposition and the importance of partitioning to vegetation is largely dependent on the relative magnitude of the particle deposition velocities to soil and vegetation. These property ranges can be used to determine if a chemical will significantly partition to vegetation. If the chemical falls outside the property ranges of the two classes it will probably be unnecessary to include vegetation in models for assessing environmental fate. The amount of chemical predicted to partition to vegetation compartments in the model is shown to be highly sensitive to certain model assumptions. Further experimental research is recommended to obtain more reliable equations describing equilibrium partitioning and uptake/depuration kinetics.

Air-soil exchange of semi-volatile organic compounds (SOCs) in the UK

Abstract This paper describes (1) a field experiment in which the air–soil exchanges of a range of polychlorinated biphenyls (PCBs) and polycyclic aromatic hydrocarbons (PAHs) were measured and (2) the use of the fugacity quotient concept to provide information on the equilibrium partitioning of PCBs, PAHs and polychlorinated dibenzo- p -dioxins (PCDDs) between the air and soil in the UK. In the field experiment aluminium foil trays containing thin layers (∼5 mm) of spiked and unspiked soil were placed under custom-built shelters at a meteorological station and exposed to outdoor air for periods of up to 9 months (281 days). Soil and air samples were taken periodically throughout the 9-month period and analysed for PCBs and PAHs. The results from the experiment showed that the PCBs and PAHs in the soils were moving towards equilibrium partitioning conditions. Statisitically significant losses of the majority of PCB/PAH compounds occurred in the spiked soils. Volatilisation was hypothesised to be the dominant loss mechanism. The PCBs in the unspiked soils were close to equilibrium with the air at the start of the experiment and there was, therefore, little change in their concentrations during the 9 months of exposure. For the PAHs there was also only a small change in the concentrations in the unspiked soils during the experiment, although there was a statistically significant loss of acenaphthene, fluorene and phenanthrene. Soil/air fugacity quotients were calculated using the air and soil concentrations measured in the field experiment and also using our database of UK air and soil survey data. The calculated soil/air fugacity quotients, together with the findings of the field experiment, indicate that the soil and air are close to equilibrium for PCBs. However, this study provides evidence that the soil may now be a source of some lighter weight PAHs to the atmosphere, whereas it appears to be still acting as a long-term sink for the heavier weight PAHs and the PCDDs.