The long-range transport (LRT) of organic chemicals in the environment is reviewed, with particular focus on the role of environmental fate and transport models and the relationship between model ...results and field data. Results from generic multimedia box models, spatially resolved multimedia box models, and atmospheric transport models are highlighted, including conceptual investigations of cold-trap effect and global fractionation as well as results for particular chemicals, such as hexachlorocyclohexanes, DDT, polychlorinated biphenyls, perfluoroocctanoic acid, and polybrominated diphenyl ethers. Comparison of model results to field data shows that in many cases environmental fate models provide a good description of the distribution dynamics observed in the field, with deviations between measured and modeled concentrations around a factor of five. Sorption to atmospheric aerosols as a key process influencing the LRT of semivolatile organic chemicals (SOCs) is discussed, and the need for more measurements of the aerosol-air partitioning of SOCs and of the reactivity of particle-bound chemicals is pointed out. Key findings from field campaigns measuring legacy persistent organic pollutants (POPs) as well as new POPs are summarized. Finally, the relationship between science and politics in the field of POPs is addressed. Research into the LRT of organic chemicals has always occurred in interaction with political activities aiming to reduce the emissions of POPs. Since the late 1990s, the Stockholm Convention and the Aarhus Protocol on POPs have formed an important political context for research concerning POPs; the implementation of these international treaties creates a demand for ongoing research into the LRT of organic chemicals.
It is hypothesized that environmental contamination by per- and polyfluoroalkyl substances (PFAS) defines a separate planetary boundary and that this boundary has been exceeded. This hypothesis is ...tested by comparing the levels of four selected perfluoroalkyl acids (PFAAs) (i.e., perfluorooctanesulfonic acid (PFOS), perfluorooctanoic acid (PFOA), perfluorohexanesulfonic acid (PFHxS), and perfluorononanoic acid (PFNA)) in various global environmental media (i.e., rainwater, soils, and surface waters) with recently proposed guideline levels. On the basis of the four PFAAs considered, it is concluded that (1) levels of PFOA and PFOS in rainwater often greatly exceed US Environmental Protection Agency (EPA) Lifetime Drinking Water Health Advisory levels and the sum of the aforementioned four PFAAs (Σ4 PFAS) in rainwater is often above Danish drinking water limit values also based on Σ4 PFAS; (2) levels of PFOS in rainwater are often above Environmental Quality Standard for Inland European Union Surface Water; and (3) atmospheric deposition also leads to global soils being ubiquitously contaminated and to be often above proposed Dutch guideline values. It is, therefore, concluded that the global spread of these four PFAAs in the atmosphere has led to the planetary boundary for chemical pollution being exceeded. Levels of PFAAs in atmospheric deposition are especially poorly reversible because of the high persistence of PFAAs and their ability to continuously cycle in the hydrosphere, including on sea spray aerosols emitted from the oceans. Because of the poor reversibility of environmental exposure to PFAS and their associated effects, it is vitally important that PFAS uses and emissions are rapidly restricted.
Short-chain chlorinated paraffins (SCCPs) show high persistence, bioaccumulation potential, and toxicity (PBT properties). Consequently, restrictions on production and use have been enforced in ...several countries/regions. The Stockholm Convention on Persistent Organic Pollutants recognized the PBT properties and long-range transport potential of SCCPs in 2015 and is now evaluating a possible global phase-out or restrictions. In this context, it is relevant to know which countries are producing/using SCCPs and in which amounts, and which applications contribute most to their environmental emissions. To provide a first comprehensive overview, we review and integrate all publicly available data on the global production and use of both chlorinated paraffins (CPs) as a whole and specifically SCCPs. Considerable amount of data on production/use of CPs and SCCPs are missing. Based on the available data and reported emission factors, we estimate the past and current worldwide SCCP emissions from individual applications. Using the available data as a minimum scenario, we conclude: (i) SCCP production and use is increasing, with the current worldwide production volume being 165,000t/year at least, whereas the global production of total CPs exceeds 1milliont/year. (ii) The worldwide release of SCCPs from their production and use to air, surface water, and soil between 1935 and 2012 has been in the range of 1690–41,400t, 1660–105,000t, and 9460–81,000t, respectively. (iii) The SCCP manufacture and use in PVC, the use in metal working applications and sealants/adhesives, and the use in plastics and rubber contribute most to the emissions to air, surface water, and soil. Thus, the decrease in the environmental emissions of SCCPs requires reduction of SCCP use in (almost) all applications. (iv) Emissions due to the disposal of waste SCCPs cannot be accurately estimated, because relevant information is missing. Instead, we conduct a scenario analysis to provide some insights into it.
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•Current worldwide SCCP production is at least 165,000t/year.•Global total CP production is exceeding 1milliont/year today.•Future emissions arising from SCCP-containing products are substantial.•A decrease in the emissions of SCCPs requires a reduction of SCCP uses in almost all relevant applications.
Per- and polyfluoroalkyl substances (PFAS) are of concern because of their high persistence (or that of their degradation products) and their impacts on human and environmental health that are known ...or can be deduced from some well-studied PFAS. Currently, many different PFAS (on the order of several thousands) are used in a wide range of applications, and there is no comprehensive source of information on the many individual substances and their functions in different applications. Here we provide a broad overview of many use categories where PFAS have been employed and for which function; we also specify which PFAS have been used and discuss the magnitude of the uses. Despite being non-exhaustive, our study clearly demonstrates that PFAS are used in almost all industry branches and many consumer products. In total, more than 200 use categories and subcategories are identified for more than 1400 individual PFAS. In addition to well-known categories such as textile impregnation, fire-fighting foam, and electroplating, the identified use categories also include many categories not described in the scientific literature, including PFAS in ammunition, climbing ropes, guitar strings, artificial turf, and soil remediation. We further discuss several use categories that may be prioritised for finding PFAS-free alternatives. Besides the detailed description of use categories, the present study also provides a list of the identified PFAS per use category, including their exact masses for future analytical studies aiming to identify additional PFAS.
Pharmaceuticals, personal care products (PPCPs), and artificial sweeteners (ASWs) are contaminants of emerging concern commonly found in the aquatic environments. In India, studies reporting ...environmental occurrence of these contaminants are scarce. In this study, we investigated the occurrence and distribution of 15 PPCPs and five ASWs in the river and groundwater (used untreated as drinking water) at several sites along the Ganges River. Based on the measured groundwater concentrations, we estimated the life-long human health risk from exposure to PPCPs through drinking. In addition, we estimated the risk of exposure to PPCPs and ASWs in the river water for aquatic organisms. The sum of detected PPCPs in the river water ranged between 54.7-826 ng/L, with higher concentrations in the severely anthropogenically influenced middle and lower reaches of the Ganges. The highest concentration among the PPCPs in the river water was of caffeine (743 ng/L). The sum of detected ASWs in river water ranged between 0.2–102 ng/L. Similar to PPCPs, the sum of ASWs in the river water was higher in the middle and lower reaches of the Ganges. In groundwater, the sum of detected PPCPs ranged between 34–293 ng/L, whereas of ASWs ranged between 0.5-25 ng/L. Negligible risk for humans was estimated from PPCPs in the drinking groundwater sources along the Ganges River, whereas moderate risks to PPCPs and ASWs (namely: caffeine, sulfamethoxazole, triclocarban, triclosan, and sucralose) were estimated for aquatic organisms in the Ganges River.
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•PPCPs and ASWs were measured in the river and groundwater along the Ganges River.•PPCPs and ASWs were generally high in the middle and lower reaches of the Ganges.•Detected PPCPs and ASWs in groundwater did not appear to pose human health risk.•Their presence in the water resources can be interpreted as a sign of local wastewater pollution.
Phthalates are a class of compounds that have been extensively used as plasticizers in different applications. Several phthalates have been recognized as substances of very high concern (SVHCs) in ...the EU, because of their toxicity for reproduction. However, high amounts of other phthalates are still produced and imported in the European Economic Area. In China and the US, recent studies show increasing concentrations of several phthalates in the air and in human urine, respectively. The understanding of phthalate absorption, distribution, metabolism, and elimination ('pharmacokinetics') in the organism is still limited. Specifically, phthalate partitioning among tissues is insufficiently understood. Here, we estimate partition coefficient (PC) values for different phthalates by using five algorithms and compare them to experimental (in-vivo and in-vitro) PC values. In addition, we review all pharmacokinetic steps for phthalates in human and rat, based on data from 133 peer-reviewed publications. We analyze the factors that determine phthalate partitioning and pharmacokinetics. Four processes are particularly relevant to phthalate distribution: protein binding, ionization, passive partitioning, and metabolism in different tissues. The interplay of these processes needs to be better represented in methods for determining the PC values of phthalates. The hydrophobicity of phthalates affects all pharmacokinetic steps. The exposure route has an influence on specific steps of phthalate pharmacokinetics but generally does not affect the pattern of metabolites in urine. The age of the organism has an influence on phthalate metabolism. More studies on the protein-bound fraction of phthalates in plasma and pharmacokinetic studies following inhalation and dermal exposure are desirable.
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.
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•A global emission inventory for individual C4–C14 PFCA homologues is developed.•Emissions from PFOA-, PFNA-, POSF- and fluorotelomer-based products are quantified.•The relative contribution of each source is homologue- and time-dependent.•The majority of industrial PFCA sources are now based in Asia, especially China.
Long-chain perfluoroalkyl carboxylic acids (PFCAs) and perfluoroalkane sulfonic acids (PFSAs) are persistent, bioaccumulative, and toxic contaminants that are globally present in the environment, ...wildlife and humans. Phase-out actions and use restrictions to reduce the environmental release of long-chain PFCAs, PFSAs and their precursors have been taken since 2000. In particular, long-chain poly- and perfluoroalkyl substances (PFASs) are being replaced with shorter-chain homologues or other fluorinated or non-fluorinated alternatives. A key question is: are these alternatives, particularly the structurally similar fluorinated alternatives, less hazardous to humans and the environment than the substances they replace? Several fluorinated alternatives including perfluoroether carboxylic acids (PFECAs) and perfluoroether sulfonic acids (PFESAs) have been recently identified. However, the scarcity of experimental data prevents hazard and risk assessments for these substances. In this study, we use state-of-the-art in silico tools to estimate key properties of these newly identified fluorinated alternatives. i COSMOtherm and SPARC are used to estimate physicochemical properties. The US EPA EPISuite software package is used to predict degradation half-lives in air, water and soil. ii In combination with estimated chemical properties, a fugacity-based multimedia mass-balance unit-world model – the OECD Overall Persistence (POV) and Long-Range Transport Potential (LRTP) Screening Tool – is used to assess the likely environmental fate of these alternatives. Even though the fluorinated alternatives contain some structural differences, their physicochemical properties are not significantly different from those of their predecessors. Furthermore, most of the alternatives are estimated to be similarly persistent and mobile in the environment as the long-chain PFASs. The models therefore predict that the fluorinated alternatives will become globally distributed in the environment similar to their predecessors. Although such in silico methods are coupled with uncertainties, this preliminary assessment provides enough cause for concern to warrant experimental work to better determine the properties of these fluorinated alternatives.
•COSMOtherm and SPARC are used to estimate physicochemical properties.•The properties of PFECAs and PFESAs are similar to PFCAs and PFSAs, respectively.•The OECD Tool is used to estimate the environmental fate.•Many fluorinated alternatives have similar environmental fate to legacy PFASs.•Urgently needed experimental studies are highlighted.
Mercury is a pollutant of global concern. To protect human health and environment from mercury pollution, the Minamata Convention on mercury entered into force in 2017.
To support a future ...effectiveness evaluation of the convention, this study assesses worldwide and regional time trends of total mercury levels in human blood and breast milk across different population sub-groups in the last half-century prior to entry-into-force of the Minamata Convention. This study also provides an overview of the epidemiological literature showing evidence of associations between mercury exposure (in terms of total mercury levels in whole blood, cord blood, and breast milk) and human health.
We searched electronic databases to identify articles published prior to June 14, 2017 and reported total mercury levels in any of three biological matrices (whole blood, cord blood, or breast milk) and/or associations with human health. Temporal trends of total mercury levels in the selected biological matrices across different population sub-groups were estimated using a linear fit of the log-transformed data. In parallel, statistical methods were employed to assess any possible effect of sources of inhomogeneity (i.e. study and population characteristics such as age, sex, ethnicity, source of exposure, sampling period, and geographical region) in the collected studies. Furthermore, a summary of significant and relevant associations between mercury exposure and human health conditions in children and adults was prepared.
We found significant declines in total mercury levels in whole blood, cord blood, and breast milk between 1966 and 2015. A regional overview of total mercury levels in whole blood, cord blood, and breast milk suggests the highest levels in South America, followed by Africa or Asia whereas the population groups from Europe or North America displayed the lowest levels of total mercury in the selected biological matrices. We observed conclusive consistent associations of mercury exposure with selected health conditions, especially neurodevelopment and neurotoxicity in children and adults. For several other health conditions, reported findings in the collected studies do not support conclusive associations. We also found that several studies demonstrated significant associations between mercury exposure below the USEPA reference level and various health conditions.
This study provides a worldwide and regional overview of trends in total mercury levels in human blood and breast milk and associated health risks prior to entry-into-force of the Minamata Convention and calls for further epidemiological investigations from across the globe to fully understand the health implications of mercury exposure.
•Mercury (Hg) exposure overview prior to the Minamata Convention is provided.•Total Hg levels in blood and breast milk have significantly declined since 1960s.•Total Hg blood and breast milk levels were found the highest in South America.•Health effects of Hg exposure were conclusive only for certain health conditions.•Further epidemiological studies are needed to comprehend health effects of Hg.
Grouping strategies are needed for per- and polyfluoroalkyl substances (PFAS), in part, because it would be time and resource intensive to test and evaluate the more than 4700 PFAS on the global ...market on a chemical-by-chemical basis. In this paper we review various grouping strategies that could be used to inform actions on these chemicals and outline the motivations, advantages and disadvantages for each. Grouping strategies are subdivided into (1) those based on the intrinsic properties of the PFAS (e.g. persistence, bioaccumulation potential, toxicity, mobility, molecular size) and (2) those that inform risk assessment through estimation of cumulative exposure and/or effects. The most precautionary grouping approach of those reviewed within this article suggests phasing out PFAS based on their high persistence alone (the so-called "P-sufficient" approach). The least precautionary grouping approach reviewed advocates only grouping PFAS for risk assessment that have the same toxicological effects, modes and mechanisms of action, and elimination kinetics, which would need to be well documented across different PFAS. It is recognised that, given jurisdictional differences in chemical assessment philosophies and methodologies, no one strategy will be generally acceptable. The guiding question we apply to the reviewed grouping strategies is: grouping for what purpose? The motivation behind the grouping (e.g. determining use in products vs. setting guideline levels for contaminated environments) may lead to different grouping decisions. This assessment provides the necessary context for grouping strategies such that they can be adopted as they are, or built on further, to protect human and environmental health from potential PFAS-related effects.
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