Poly- and per-fluoroalkyl substances (PFAS) and volatile methyl siloxanes (VMS) were monitored at 21 sites in the Global Atmospheric Passive Sampling (GAPS) Network. Atmospheric concentrations previously reported from 2009 were compared to concentrations measured at these sites in 2013 and 2015, to assess trends over 7 years of monitoring. Concentrations of the fluorotelomer alcohols (FTOHs) and fluorinated sulfonamides and sulfonamidoethanols (FOSAs and FOSEs) were stable at these sites from 2009 to 2015 with no significant difference (p > 0.05) in concentrations. Elevated concentrations of all the neutral PFAS were detected at the urban sites as compared to the polar/background sites. The perfluorosulfonic acids (PFSAs), meanwhile, saw a significant increase (p < 0.001) in concentrations from 2009 to 2015. The perfluorocarboxylic acids (PFCAs) had elevated concentrations in 2015, however, the difference was not statistically significant (p > 0.05). Concentrations of the PFSAs and the PFCAs were similar at all location types, showing the global reach of these persistent compounds. Concentrations of the cyclic VMS (cVMS) were at least an order of magnitude higher than the linear VMS (lVMS) and the PFAS. Octamethylcyclotetrasiloxane (D4), decamethylcyclopentasiloxane (D5) and dodecamethylcyclohexasiloxane (D6) saw a weak significant increase in concentrations from 2009 to 2013 (p < 0.05), however, hexamethylcyclotrisiloxane (D3) had a strong significant decrease in concentrations from 2009 to 2015 (p < 0.01).

Short chain perfluoroalkyl acids (PFAAs) have been developed since 2002 by the major manufacturers to replace the conventional C8 and higher homologues, with much of the world production shifted to China in recent years. In this study, we conducted a continuous monitoring program over the period 2011–2014 with seasonal monitoring in 2013 for PFAAs emitted from two rapidly developing fluorochemical industry parks located in the Daling River Basin, Northern China. The trend of PFAA contamination was identified, dominated by perfluorobutane sulfonic acid (PFBS), perfluorobutanoic acid (PFBA) and perfluorooctanoic acid (PFOA), with the maximum concentrations of 3.78 μg/L, 3.70 μg/L, and 1.95 μg/L, respectively. Seasonal monitoring uncovered the occasional emission of perfluorooctane sulfonic acid (PFOS). Construction trends of new facilities and associated manufacturing capacity of the main products were also analyzed to assess correlations with PFAA emissions. An assessment of the data over the period 2011–2014 found a positive correlation with fluorocarbon alcohol (FCA) production and emission of PFAAs. Groundwater and tap water around the main source indicated that the dominant PFAAs had different diffusion behaviors. PFBS levels were higher in surface water, while PFBA was dominant in groundwater and tap water, with PFOA levels being higher in downstream groundwater. Considering the continuous expansion and development of fluorochemical industry in the Daling River Basin, this study will provide abundant information on the effectiveness of risk assessment and management.

The aim of this study was to determine how dietary exposure to PFAAs has changed over the period when major production changes occurred. Archived samples (1999–2010) of eggs, milk and farmed rainbow trout were analyzed by ultra performance liquid chromatography coupled to tandem mass spectrometry. Statistically significant decreasing trends were observed for concentrations of perfluorooctane sulfonic acid (PFOS) and perfluorohexane sulfonic acid (PFHxS) in fish (p < 0.002 and p < 0.032, respectively) and eggs (p < 0.001 for both compounds). Concentrations of PFOS in fish and eggs decreased by a factor of 10 and 40, respectively. In eggs there was also a statistically significant decreasing trend in concentrations of perfluorooctanoic acid (PFOA). The results of this study demonstrate that PFAA concentrations in food items from agricultural food chains and aquatic food chains close to sources respond rapidly to changes in environmental emissions. Implications for the overall understanding of human exposure are discussed.

The effect of atmospheric nitrogen deposition on the species richness of acid grasslands was investigated by combining data from a large Danish monitoring program with a large European data set, where a significant non-linear negative effect of nitrogen deposition had been demonstrated (Stevens et al., 2010). The nitrogen deposition range in Denmark is relatively small and when only considering the Danish data a non-significant decrease in the species richness with nitrogen deposition was observed. However, when both data sets were combined, then the conclusion of the European survey was further corroborated by the results of the Danish monitoring. Furthermore, by combining the two data sets a more comprehensive picture of the threats to the biodiversity of acid grasslands emerge; i.e., species richness in remnant patches of acid grassland in intensively cultivated agricultural landscapes is under influence not only from nitrogen deposition, but also from current and historical land use.

Electron transfer capacities (ETC) of humic-like acids (HLA) and their effects on dechlorination are dependent on their redox-active properties. Aging and minerals can affect the chemical compositions and structures of HLA. However, the underlying mechanism and the impacts on the dechlorination capacities of HLA are poorly understood. We investigated how redox properties change in association with the intrinsic chemical natures and exterior minerals of the HLA extracted from landfilled solid wastes. Furthermore, the ETC of the landfill-derived HLA could be strengthened by increasing landfill age and demineralization, thereby facilitating the dechlorination of pentachlorophenol (PCP). The HLA molecules started to polymerize aromatic macromolecules during landfilling, leading to an increase in ETC and dechlorination capacities. Macromolecular HLA were dissociated to smaller molecules and exposed more aromatic and carboxyl groups when separated from minerals, which enhanced the ETC and the dechlorination abilities of the HLA. Microbial-mediated dechlorination was an effective way to degrade PCP, and almost 80% of the PCP was transformed after 40 days of demineralized HLA and Shewanella oneidensis MR-1 incubation. The demineralization and aging further facilitated the microbial-mediated PCP dechlorination. The findings provide a scientific base for improving in-situ bioremediation of chlorinated compound-contaminated soils using freshly synthesized HLA.

Aluminum dialkyl phosphinates (ADPs) are a class of promising phosphorus-containing flame retardants, but their environmental fate is not well understood. Sorption and transport behaviors of ADPs, and their hydrolysates dialkyl phosphinic acids (DPAs) were studied by batch and column experiments. ADPs are less mobile in soil columns with more than half (>52.6%) of ADPs retained in the soil and residues in the topmost 2-cm layer account for more than 57% of total residues. Dissolution and dispersion of fine grain ADPs were responsible for the transport of ADPs. Sorption DPAs (logKₒc) was significantly related to the lipophilicity of DPAs (logD) (p < 0.05). Soil pH and clay content were the dominant factors governing the sorption and transport of DPAs in soils, indicating the importance of electrostatic interactions. The retardation factors (R) of DPAs derived from leaching experiments were pH-dependent with larger R values in the acidic soil (pH = 4.0) where anionic and neutral species of DPAs coexisted. Both physical and chemical non-equilibrium convection-dispersion equations (CDE) yield appropriate modeling for DPAs transport. In most cases, R values estimated from column tests differed from those derived from the batch experiments, which might be attributed to non-equilibrium sorption processes in dynamic conditions.

Organic matter, as an electron donor, plays a vital role in As mobilization mediated by microorganisms during reductive dissolution of Fe/Mn oxides in shallow aquifers. However, the specific types and sources of organic matter involved in biogeochemical processes accelerating As mobilization are still controversial. Both sediment and groundwater samples were collected at different depths from aquifers of the Hetao Basin, a typical inland basin hosting high As groundwater. Sedimentary lipids and their compound-specific carbon isotope ratios were analyzed to evaluate characteristics and sources of organic matter. Results show that sedimentary As were well correlated with Fe and Mn oxides, suggesting that As exist as Fe/Mn oxide bound forms. Groundwater As far exceeded the drinking water guide value of 10 μg/L. Moreover, As concentrations in shallow groundwater were relatively higher. Lipids in clay were mainly originated from terrestrial higher plants, while that in fine sand samples were derived from terrestrial higher plants, microorganism and petroleum. Shallow fine sand samples were also characterized by evident in-situ biodegradation. Compound-specific carbon isotope compositions of sedimentary lipids showed that short-chain n-alkanes and n-alkanoic acids had more positive δ13C values compared to long-chain compounds, especially in shallow fine sand samples. δ13CTOC were also low in shallow fine sand samples. These results jointly indicate that these lipids in shallow fine sand samples acted as carbon source for indigenous microorganism and the short-chain components were particularly more vulnerable to biodegradation, which may contribute to high As concentrations in shallow groundwater. The new findings provide the first evidence that short chain length n-alkyl compounds afforded a source of potential electron donors for microbially mediated As mobilization process in the shallow aquifers.

Experimental work was undertaken to test whether gaseous perfluorooctanoic acid (PFOA) sorbs to glass fibre filters (GFFs) during air sampling, causing an incorrect measure of the gas-particle equilibrium distribution. Furthermore, tests were performed to investigate whether deactivation by siliconisation prevents sorption of gaseous PFOA to filter materials. An apparatus was constructed to closely simulate a high-volume air sampler, although with additional features allowing introduction of gaseous test compounds into an air stream stripped from particles. The set-up enabled investigation of the sorption of gaseous test compounds to filter media, eliminating any contribution from particles. Experiments were performed under ambient outdoor air conditions at environmentally relevant analyte concentrations. The results demonstrate that gaseous PFOA sorbs to GFFs, but that breakthrough of gaseous PFOA on the GFFs occurs at trace-level loadings. This indicates that during high volume air sampling, filters do not quantitatively capture all the PFOA in the sampled air. Experiments with siliconised GFFs showed that this filter pre-treatment reduced the sorption of gaseous PFOA, but that sorption still occurred at environmentally relevant air concentrations. We conclude that deactivation of GFFs does not allow for the separation of gaseous and particle bound perfluorinated carboxylic acids (PFCAs) during active air sampling. Consequently, the well-recognised theory that PFCAs do not prevail as gaseous species in the atmosphere may be based on biased measurements. Caution should be taken to ensure that this artefact will not bias the conclusions of future field studies.

To investigate the residues, compositions, distributions and potential ecological risks of perfluoroalkyl acids (PFAAs), water samples were collected seasonally between August 2011 and November 2012 from 20 sites in Lake Chaohu and its tributary rivers. The mean concentration of total PFAAs (TPFAAs) was 14.46 ± 6.84 ng/L. PFOA was the predominant contaminant (8.62 ± 4.40 ng/L), followed by PFBA (2.04 ± 1.16 ng/L) and PFHxA (1.23 ± 1.50 ng/L). The TPFAAs concentrations peaked in August 2012 in each area, except for the western river. The opposite spatial trends were found for PFOA and PFOS in both the lake and river areas. Except for PFOS and PFUdA, the levels of TPFAAs and PFAAs were significantly related to the composition of fluorescent dissolved organic matter (FDOM) but not related to total DOM expressed by dissolved organic carbon (DOC). The risk of PFOS determined by a species sensitivity distribution model was notably above that of PFOA.

Midge larvae (Chironomus riparius) were exposed to sediments from a deposition sampled at a site along the Rhône River (France) downstream of an industrial site releasing various perfluorinated chemicals. This sediment is characterized by high concentrations of perfluoroundecanoic acid (PFUnA) and perfluorotridecanoic acid (PFTrDA) and a low perfluorooctane sulfonate (PFOS) concentration. Concentrations of 23 perfluoroalkyl compounds, including C4–C14 carboxylate acids, C4–C10 sulfonates, and seven precursors, were analyzed in overlying and pore water, sediment, and larvae. Midge larvae accumulated carboxylate acids (C11–C14), PFOS, and two precursors (perfluorooctane sulfonamide: FOSA and 6:2 fluorotelomer sulfonic acid, 6:2 FTSA). These substances accumulated mainly during the fourth instar larvae exponential growth phase. Accumulation of 6:2 FTSA, PFUnA, and PFOS occured via trophic and tegumentary routes. Other compounds mainly accumulated from food. Kinetics followed a partition model, from which uptake and elimination constants were derived.