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Persistent organic pollutants (POPs) are entrained within glaciers globally, reemerging in many alpine ecosystems. Despite available data on POP flux from glaciers, a study of human health risk caused by POPs released in glacial meltwater has never been attempted. Glaciers in the European Alps house the largest known quantity of POPs in the Northern Hemisphere, presenting an opportunity for identification of potential risk in an endmember scenario case study. With methodology developed by the US Environmental Protection Agency (EPA), we provide a regional screening level human risk analysis of one class of POPs, polychlorinated-biphenyls (PCB) that have been measured in melt waters from the Silvretta Glacier in the Swiss Alps. Our model suggests the potential for both cancer and non-cancer impacts in residents with lifetime exposure to current levels of PCB in glacial meltwater and average consumption of local fish. For residents with an abbreviated 30-year exposure timeframe, the risk for cancer and non-cancer impacts is low. Populations that consume higher quantities of local fish are predicted to be at a greater risk, with risk to lifetime consumers higher by an order of magnitude. Based on the results of our screening study, we suggest that local government move to the next step within the risk assessment framework: local monitoring and management. Within the Alps, other glacial watersheds of a similar size and latitude may see comparable risk and our model framework can be adapted for further implementation therein.

The paper describes the first three deaths reported in Europe involved in isotonitazene consumption, a potent benzimidazole derivate opioid consumed in the recreational drug scene. Isotonitazene powder and purity determination was performed on the sample collected in the first death scene by NMR, HRMS, GC-FTIR, ATR-FTIR and GC-MS. Isotonitazene purity was determined by GC-MS analysis and proton NMR, and was defined to be above 95 % and 98 %, respectively. Quantification of isotonitazene in biological samples was performed using a targeted analysis based on SPE extraction and ultra-high performance liquid chromatography tandem mass spectrometry. The isotonitazene median concentration in femoral whole blood was 1.20ng/mL. Isotonitazene concentration in hair was similar or even lower compared to that seen in fentanyl abusers. Isotonitazene distribution in tissues converges in the brain, lungs and heart, respectively. Surprisingly, isotonitazene concentration in liver is the lowest measured for all tissues and fluids analyzed. Based on circumstantial evidence, autopsy findings and the results of the toxicological analysis, the medical examiner concluded that the cause of all three deaths was an acute intoxication with isotonitazene. Since isotonitazene toxic concentration levels are very low, the consumption of this new psychoactive drug is a real hazard for human health.

Biogenic amines (BAs), a class of nitrogenous compounds that are frequently detected in wine, pose adverse effects to humans. However, with the largest red wine consumption in the world, little is known about national profiles correlating BAs in wines to toxicological/health risks in China. In this study, we conducted a nationwide survey of commercially available wines for the occurrence of BAs. Our sampling campaign covered >90% of wine brands (n = 456) in China in a three year span (2014–2016). The target BAs included tryptamine, phenylethylamine, putrescine, cadaverine, histamine, tyramine, spermidine and spermine. In order to quantitatively characterize the potential risk and/or support regulatory decision-making, chronic and acute BA exposure scenarios were developed and simulated with a physiologically based pharmacokinetic model. The model described the fate and transport of BAs within human body using physical descriptions of relevant processes. These results provided baseline data that are needed for the risk assessment of dietary uptake of BAs and evaluating winemaking processes by food safety authorities.

We report on two farms in Switzerland heavily contaminated by polychlorinated biphenyls (PCBs) and dioxins (PCDD/Fs), occurring in the first case from diffuse sources and in the second case from PCB-containing wall paint. Extensive measurements of PCBs and PCDD/Fs on site (soil, forage, and paint) and in cattle (blood, fat, and milk) allowed validation of our novel dynamic toxicokinetic model, which includes the transfer of contaminants from the mother cows to their suckling calf and the uptake of soil by grazing cattle. We show that for calves, the mother milk is the main uptake route of contaminants. For both cows and calves, ingestion of contaminated soil, although often overlooked, is an appreciable uptake path. The remediation of the contaminated stable lead to a 2-3 fold reduction of the PCB levels in animals within one year. The transfer of animals to an uncontaminated mountain site during summer proved to be an effective decontamination procedure with up to 50% reduction of the levels within three months. Our study calls for a rapid removal of PCB-containing materials in animal husbandry farms and shows that the diffuse contamination of soils will remain a source for PCBs and PCDD/Fs in our food chain for decades to come.

Chlorinated paraffins (CPs) are high production volume chemicals and ubiquitous environmental contaminants. CPs are produced and used as complex mixtures of polychlorinated n-alkanes containing thousands of isomers, leading to demanding analytical challenges. Due to their high degree of chlorination, CPs have highly complex isotopic mass patterns that often overlap, even when applying high resolution mass spectrometry. This is further complicated in the presence of degradation products such as chlorinated alkenes (CP-enes). CP-enes are formed by dehydrochlorination of CPs and are expected thermal degradation products in some applications of CPs, for example, as metal working fluids. A mathematical method is presented that allows deconvolution of the strongly interfered measured isotope clusters into linear combinations of isotope clusters of CPs and CP-enes. The analytical method applied was direct liquid injection into an atmospheric pressure chemical ionization source, followed by quadrupole time-of-flight mass spectrometry (APCI-qTOF-MS), operated in full scan negative ion mode. The mathematical deconvolution method was successfully applied to a thermally aged polychlorinated tridecane formulation (Cl

To simultaneously quantify and profile the complex mixture of short-, median-, and long-chain CPs (SCCPs, MCCPs, and LCCPs) in Australian sewage sludge, we applied and further validated a recently developed novel instrumental technique, using quadrupole time-of-flight high resolution mass spectrometry running in the negative atmospheric pressure chemical ionization mode (APCI-qTOF-HRMS). Without using an analytical column the cleaned extracts were directly injected into the qTOF-HRMS followed by quantification of the CPs by a mathematical algorithm. The recoveries of the four SCCP, MCCP and LCCP-spiked sewage sludge samples ranged from 86 to 123%. This APCI-qTOF-HRMS method is a fast and promising technique for routinely measuring SCCPs, MCCPs, and LCCPs in sewage sludge. Australian sewage sludge was dominated by MCCPs with concentrations ranging from 542 to 3645 ng/g dry weight (dw). Lower SCCPs concentrations (

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.

SummaryBackground In recent years, the frequency of contact allergy to isothiazolinones has increased alarmingly in Europe, but only limited data are available on concentrations of isothiazolinones in consumer products. Objectives To examine the current frequency of isothiazolinones [methylisothiazolinone (MI), methylchloroisothiazolinone (MCI), benzisothiazolinone (BIT), and octylisothiazolinone (OIT)] in a wide array of detergents and cosmetics relevant for the Swiss population. Methods By means of a market survey, the occurrence of isothiazolinones was investigated in 1948 consumer products. Of these, 88 products were analysed by liquid chromatography–high-resolution mass spectrometry after ultrasonic extraction. Results Only 7.6% of all cosmetics contained isothiazolinones, but the prevalence in detergents was much higher (42.9%). The measured concentration ranges in detergents were 4.3–10, 3.5–279, 3.8–186 and 7.9 ppm (one product only) for MI, MCI, BIT, and OIT, respectively. For cosmetics, these were 1.3–133 and 4.8 ppm (one product only) for MI and MCI, respectively. Conclusions Our study has shown that high concentrations of isothiazolinones (including MI) can be found in a large variety of products, in particular in detergents. Therefore, the safe use of these preservatives should be re-evaluated by including detergents in the exposure assessment.

In previous studies, the incorporation of polychlorinated biphenyls (PCBs) has been quantified in the accumulation areas of Alpine glaciers. Here, we introduce a model framework that quantifies mass fluxes of PCBs in glaciers and apply it to the Silvretta glacier (Switzerland). The models include PCB incorporation into the entire surface of the glacier, downhill transport with the flow of the glacier ice, and chemical fate in the glacial lake. The models are run for the years 1900-2100 and validated by comparing modeled and measured PCB concentrations in an ice core, a lake sediment core, and the glacial streamwater. The incorporation and release fluxes, as well as the storage of PCBs in the glacier increase until the 1980s and decrease thereafter. After a temporary increase in the 2000s, the future PCB release and the PCB concentrations in the glacial stream are estimated to be small but persistent throughout the 21st century. This study quantifies all relevant PCB fluxes in and from a temperate Alpine glacier over two centuries, and concludes that Alpine glaciers are a small secondary source of PCBs, but that the aftermath of environmental pollution by persistent and toxic chemicals can endure for decades.

This study is part of our investigations about the release of persistent organic pollutants from melting Alpine glaciers and the relevance of the glaciers as secondary sources of legacy pollutants. Here, we studied the melt-related release of polychlorinated biphenyls (PCBs) in proglacial lakes and glacier streams of the catchment of the Silvretta glacier, located in the Swiss Alps. To explore a spatial and temporal distribution of chemicals in glacier melt, we combined two approaches: (1) analysing a sediment record as an archive of past remobilization and (2) passive water sampling to capture the current release of PCBs during melt period. In addition, we determined PCBs in a non-glacier-fed stream as a reference for the background pollutant level in the area. The PCBs in the sediment core from the Silvretta lake generally complied with trends of PCB emissions into the environment. Elevated concentrations during the most recent ten years, comparable in level with times of the highest atmospheric input, were attributed to accelerated melting of the glacier. This interpretation is supported by the detected PCB fractionation pattern towards heavier, less volatile congeners, and by increased activity concentrations of the radioactive tracer (137)Cs in this part of the sediment core. In contrast, PCB concentrations were not elevated in the stream water, since no significant difference between pollutant concentrations in the glacier-fed and the non-glacier-fed streams was detected. In stream water, no current decrease of the PCBs with distance from the glacier was observed. Thus, according to our data, an influence of PCBs release due to accelerated glacier melt was only detected in the proglacial lake, but not in the other compartments of the Silvretta catchment.

In Alpine regions, glaciers act as environmental archives and can accumulate significant amounts of atmospherically derived pollutants. Due to the current climate-warming-induced accelerated melting, these pollutants are being released at correspondingly higher rates. To examine the effect of melting on the redistribution of legacy pollutants in Alpine glaciers, we analyzed polychlorinated biphenyls in an ice core from the temperate Silvretta glacier, located in eastern Switzerland. This glacier is affected by surface melting in summer. As a result, liquid water percolates down and particles are enriched in the current annual surface layer. Dating the ice core was a challenge because meltwater percolation also affects the traditionally used parameters. Instead, we counted annual layers of particulate black carbon in the ice core, adding the years with negative glacier mass balance, that is, years with melting and subsequent loss of the entire annual snow accumulation. The analyzed samples cover the time period 1930-2011. The concentration of indicator PCBs (iPCBs) in the Silvretta ice core follows the emission history, peaking in the 1970s (2.5 ng/L). High PCB values in the 1990s and 1930s are attributed to meltwater-induced relocation within the glacier. The total iPCB load at the Silvretta ice core site is 5 ng/cm(2). A significant amount of the total PCB burden in the Silvretta glacier has been released to the environment.

International audience; Chlorinated paraffins (CPs) are high production volume chemicals and ubiquitous environmental pollutants. In particular, data about the environmental fate of medium-chain (MCCPs, C14-C17) and long-chain (LCCPs, C->= 18) CPs are urgently needed. Their analysis requires elaborate analytical methods and representative analytical standards. Complex mixtures that contain CPs of different carbon chain lengths and degrees of chlorination are currently used for quantification but are impractical when chain length distributions substantially differ between samples and standards. Single-chain CP mixtures of only one carbon chain length but varying degrees of chlorination are more suitable for accurate quantification but are not available for MCCPs and LCCPs. Such standards are useful for homologue pattern deconvolution and response factor calculations. Toxicity and transformation studies on MCCPs and LCCPs are scarce. Respective studies would also benefit from less complex CP standards, e.g., single-chain mixtures or even constitutionally defined CPs. Currently available analytical standards are inadequate for the demanding task of quantifying MCCPs and LCCPs. Improved standards are required. This review provides an overview of the available analytical CP materials, discusses their advantages and disadvantages for accurate CP analysis, and gives a recommendation for improvements. Recommendations for improved analytical standards include (A) complex CP mixtures that better resemble technical CP mixtures, (B) single-chain CP mixtures of different carbon chain lengths (C-10-C-30) and varying degrees of chlorination (40-70 wt%Cl), (C) constitutionally defined CPs with representative chlorination patterns, and (D) isotopically labeled CP isomers that represent a broad range of CPs.

International audience; Chlorinated paraffins are industrial chemicals that can be subdivided into short-chain (SCCP), medium chain (MCCP), and long-chain (LCCP) chlorinated paraffins. The global production volumes of MCCPs are nowadays suspected to be much higher than those of S- and LCCPs, and the few available studies on the environmental occurrence of chlorinated paraffins report often higher MCCP concentrations than S- or LCCP concentrations in the environment. The present review focuses, therefore, on MCCPs specifically and provides a literature overview and a data analysis of the production volumes, PBT properties (persistence, bioaccumulation potential, and toxicity), and the worldwide measured concentrations of MCCP in environmental samples, biota, and humans. Furthermore, we include our own measurements of technical CP formulations from China, the major global producing country, to estimate the global production amounts of MCCPs. The key findings from this review are that (1) MCCPs are toxic to the aquatic environment, and the available data suggest that they are also persistent; (2) available time trends for MCCPs in soil, biota, and most of the sediment cores show increasing time trends over the last years to decades; and (3) MCCP concentrations in sediment close to local sources exceed toxicity thresholds (i.e., the PNEC). Our study shows that overall, MCCPs are of growing concern, and regulatory actions Should be considered seriously.

International audience; Chlorinated paraffins (CPs) are high production volume chemicals. Their analysis is demanding and becomes even more challenging in presence of CP transformation products. Chlorinated olefins (COs) are expected thermal CP transformation products that are present in technical CP products and in the environment. Thus, a specific analysis of CPs and COs is important. Commonly, CPs are analysed by gas chromatography electron capture negative ionisation mass spectrometry (GC-ECNI-MS). It was shown that GC-ECNI-MS suffers from in-source formation of COs. Further, selected ion monitoring can lead to false quantification of COs as CPs. Alternative methods based on liquid chromatography and soft ionisation techniques can solve the CP/CO problem. Non-interfered CP data is inevitable for CP transformation studies and non-biased degradation kinetics. Data about CP transformation is urgently needed, but respective studies are challenging. In here, we provided an analytical guide to deal with severe mass interferences of CPs and their transformation products. (C) 2018 Elsevier B.V. All rights reserved.

Consumer exposure to leave-on cosmetics and personal care products (C&PCPs) ingredients of low or moderate volatility is often assumed to occur primarily via dermal absorption. In reality they may volatilize from skin and represent a significant source for inhalation exposure. Often, evaporation rates of pure substances from inert surfaces are used as a surrogate for evaporation from more complex product matrices. Also the influence of partitioning to skin is neglected and the resulting inaccuracies are not known. In this paper we describe a novel approach for measuring chemical evaporation rates from C&PCPs under realistic consumer exposure conditions. Series of experiments were carried out in a custom-made ventilated chamber fitted with a vapor trap to study the disposition of a volatile cosmetic ingredient, decamethylcyclopentasiloxane (D5), after its topical application on either aluminum foil or porcine skin in vitro. Single doses were applied neat and in commercial deodorant and face cream formulations at normal room (23 °C) and skin temperature (32 °C). The condition-specific evaporation rates were determined as the chemical mass loss per unit surface area at different time intervals over 1–1.25 h post-dose. Product weight loss was monitored gravimetrically and the residual D5 concentrations were analyzed with GC/FID. The release of D5 from exposed surfaces of aluminum occurred very fast with mean rates of 0.029 mg cm−2 min−1 and 0.060 mg cm−2 min−1 at 23 °C and 32 °C, respectively. Statistical analysis of experimental data confirmed a significant effect of cosmetic formulations on the evaporation of D5 with the largest effect (2-fold decrease of the evaporation rate) observed for the neat face cream pair at 32 °C. The developed approach explicitly considers the initial penetration and evaporation of a substance from the Stratum Corneum and has the potential for application in dermal exposure modeling, product emission tests and the formulation of C&PCPs. Keywords: Volatilization, Cosmetic ingredients, Formulation effect, Porcine skin, Stratum Corneum

Significant knowledge gaps exist regarding the fate and transport of persistent organic pollutants like dichlorodiphenyltrichloroethane (DDT) in tropical environments. In Brazil, indoor residual spraying with DDT to combat malaria and leishmaniasis began in the 1950s and was banned in 1998. Nonetheless, high concentrations of DDT and its metabolites were recently detected in human breast milk in the community of Lake Puruzinho in the Brazilian Amazon. In this work, we couple analysis of soils and sediments from 2005 to 2014 at Puruzinho with a novel dynamic floodplain model to investigate the movement and distribution of DDT and its transformation products (dichlorodiphenyldichloroethylene (DDE) and dichlorodiphenyldichloroethane (DDD)) and implications for human exposure. The model results are in good agreement with the accumulation pattern observed in the measurements, in which DDT, DDE, and DDD (collectively, DDX) accumulate primarily in upland soils and sediments. However, a significant increase was observed in DDX concentrations in soil samples from 2005 to 2014, coupled with a decrease of DDT/DDE ratios, which do not agree with model results assuming a post-ban regime. These observations strongly suggest recent use. We used the model to investigate possible re-emissions after the ban through two scenarios: one assuming DDT use for IRS and the other assuming use against termites and leishmaniasis. Median DDX concentrations and p,p'-DDT/p,p'-DDE ratios from both of these scenarios agreed with measurements in soils, suggesting that the soil parameterization in our model was appropriate. Measured DDX concentrations in sediments were between the two re-emission scenarios. Therefore, both soil and sediment comparisons suggest re-emissions indeed occurred between 2005 and 2014, but additional measurements would be needed to better understand the actual re-emission patterns. Monte Carlo analysis revealed model predictions for sediments were very sensitive to highly uncertain parameters associated with DDT degradation and partitioning. With this model as a tool for understanding inter-media cycling, additional research to refine these parameters would improve our understanding of DDX fate and transport in tropical sediments.

Between 60% and 80% of all marine litter is plastic. Leachate from plastics has previously been shown to cause acute toxicity in the freshwater species Daphnia magna. Here, we present an initial screening of the marine environmental hazard properties of leachates from weathering plastics to the marine harpacticoid copepod [Crustacea] Nitocra spinipes. Twenty-one plastic products made of different polymeric materials were leached and irradiated with artificial sunlight. Eight of the twenty-one plastics (38%) produced leachates that caused acute toxicity. Differences in toxicity were seen for different plastic products, and depending on the duration of irradiation. There was no consistent trend in how toxicity of leachate from plastics changed as a function of irradiation time. Leachate from four plastics became significantly more toxic after irradiation, two became significantly less toxic and two did not change significantly. Analysis of leachates from polyvinyl chloride (PVC) by liquid chromatography coupled to a full-scan high-resolution mass spectrometer showed that the leachates were a mixture of substances, but did not show evidence of degradation of the polymer backbone. This screening study demonstrates that leachates from different plastics differ in toxicity to N. spinipes and that the toxicity varies under simulated weathering., Chemosphere, 132, ISSN:0045-6535, ISSN:1879-1298

Ambient air concentrations of polychlorinated biphenyls (PCBs) in Zurich, Switzerland, are reported for the years 2011-2013. These measurements reveal a distinct seasonal trend with PCB concentrations in air during the summer that were three to five times higher than in the winter. We used a long-term dynamic multimedia model to analyze the seasonal trend and to back-calculate urban emissions of PCBs. In contrast to previous short-term studies that considered time periods of several days to months to extrapolate annual emissions, the use of long-term field data and the corresponding model reduces the uncertainty in these extrapolations. Comparison with measured PCB concentrations in air shows that our model is able to reproduce seasonal trends of the six indicator PCBs (iPCBs). The good agreement of the model results with measurements over a time period of three years provides confidence in model outputs and allows us to estimate the total annual PCB emissions of Zurich (86 μg capita(-1) d(-1)). The resulting summer emissions are nine times higher than emissions during winter. Interestingly, this factor corresponds to the expected increase in PCB volatilization due to the effect of temperature on vapor pressure. This finding implies that PCBs in Zurich are probably released mainly by volatilization from sources that are directly exposed to ambient air temperature (i.e., outdoor sources). The derived emissions are in accordance with previous studies performed at the same location and are also in agreement with an existing emission inventory.

Polybrominated diphenyl ethers (PBDEs) have been widely used as flame retardants but they are of concern and are currently being phased-out because of their environmentally hazardous properties and their potential to cause adverse health effects. We analyzed PBDEs in Zurich, Switzerland, and applied a multi-media environmental fate model to back-calculate the rate of PBDE emission to air. PBDE concentrations in ambient air were measured in summer 2010 and winter 2011 in the city center of Zurich. Concentrations were higher in summer (sum PBDEs 118-591 pg m(-3)) than in winter (sum PBDEs 17-151 pg m(-3)), and are on the upper end of concentrations reported in literature for urban sites with no point sources of PBDEs. The emissions derived from our measurements (summer: 53-165 μg capita(-1) d(-1), winter: 25-112 μg capita(-1) d(-1)) and extrapolated to annual emissions for Switzerland (114-406 kg a(-1)) lie in the middle of ranges reported on the basis of substance flow analyses and emission inventories. The difference between summer and winter emissions is small compared to the difference that would be expected from the temperature dependence of PBDE vapor pressure, which would be consistent with emissions occurring to a large extent from flame-proofed materials located indoors under nearly constant temperature conditions and/or emissions to air occurring by suspension of particles containing PBDEs. Compared to previous studies in Switzerland, concentrations and emissions of PBDEs appear to have increased during the last five years with an increasing contribution of decabromodiphenyl ether, despite the addition of PBDEs to national and international regulations.

Northern Hemisphere alpine glaciers have been identified as a point of concentration and reemergence of legacy organochlorine pollutants (OCPs). In this review, we compile a selection of published literature combining long-range, global atmospheric transport and distribution-based compartmental environmental flux models, as well as data from glacial meltwater, ice core, crevasse and proglacial lake sediment studies. Regional studies of ice and meltwater in alpine glaciers of the northern latitudes show similarities in sample deposition profiles and concentration due to chemical atmospheric residence time, precipitation type and glacier flow rates. In glaciated locations near areas of extensive OCPs use, such as the Swiss and Italian Alps, glacier sample concentrations are higher, while in areas more distant from use, including Arctic nations, OCPs concentrations in glaciers are significantly lower. Our review identifies alpine glaciers co-located with regions characterized by OCPs use as a significant organochlorine pollutant distribution source, secondary in timing and location to direct deposition, with subsequent bioaccumulation and potential human risk impacts.

Melting glaciers release previously ice-entrapped chemicals to the surrounding environment. As glacier melting accelerates under future climate warming, chemical release may also increase. This study investigated the behavior of semivolatile pesticides over the course of one year and predicted their behavior under two future climate change scenarios. Pesticides were quantified in air, lake water, glacial meltwater, and streamwater in the catchment of Lake Brewster, an alpine glacier-fed lake located in the Southern Alps of New Zealand. Two historic-use pesticides (endosulfan I and hexachlorobenzene) and three current-use pesticides (dacthal, triallate, and chlorpyrifos) were frequently found in both air and water samples from the catchment. Regression analysis indicated that the pesticide concentrations in glacial meltwater and lake water were strongly correlated. A multimedia environmental fate model was developed for these five chemicals in Brewster Lake. Modeling results indicated that seasonal lake ice cover melt, and varying contributions of input from glacial melt and streamwater, created pulses in pesticide concentrations in lake water. Under future climate scenarios, the concentration pulse was altered and glacial melt made a greater contribution (as mass flux) to pesticide input in the lake water.

Chlorinated paraffins (CPs) are high production volume chemicals widely used as additives in metal working fluids. Thereby, CPs are exposed to hot metal surfaces which may induce degradation processes. We hypothesized that the elimination of hydrochloric acid would transform CPs into chlorinated olefins (COs). Mass spectrometry is widely used to detect CPs, mostly in the selected ion monitoring mode (SIM) evaluating 2-3 ions at mass resolutions R 20'000. This approach is not suited to detected COs, because their mass spectra strongly overlap with CPs. We applied a mathematical deconvolution method based on full-scan MS data to separate interfered CP/CO spectra. Metal drilling indeed induced HCl-losses. CO proportions in exposed mixtures of chlorotridecanes increased. Thermal exposure of chlorotridecanes at 160, 180, 200 and 220 °C also induced dehydrohalogenation reactions and CO proportions also increased. Deconvolution of respective mass spectra is needed to study the CP transformation kinetics without bias from CO interferences. Apparent first-order rate constants (k

Accurate quantification of short-chain chlorinated paraffins (SCCPs) poses an exceptional challenge to analytical chemists. SCCPs are complex mixtures of chlorinated alkanes with variable chain length and chlorination level; congeners with a fixed chain length (n) and number of chlorines (m) are referred to as a "congener group" CnClm. Recently, we resolved individual CnClm by mathematically deconvolving soft ionization high-resolution mass spectra of SCCP mixtures. Here we extend the method to quantifying CnClm by introducing CnClm specific response factors (RFs) that are calculated from 17 SCCP chain-length standards with a single carbon chain length and variable chlorination level. The signal pattern of each standard is measured on APCI-QTOF-MS. RFs of each CnClm are obtained by pairwise optimization of the normal distribution's fit to the signal patterns of the 17 chain-length standards. The method was verified by quantifying SCCP technical mixtures and spiked environmental samples with accuracies of 82-123% and 76-109%, respectively. The absolute differences between calculated and manufacturer-reported chlorination degrees were -0.9 to 1.0%Cl for SCCP mixtures of 49-71%Cl. The quantification method has been replicated with ECNI magnetic sector MS and ECNI-Q-Orbitrap-MS. CnClm concentrations determined with the three instruments were highly correlated (R2 > 0.90) with each other.

The reduction of emissions of mercury is a declared aim of the Minamata Convention, a UN treaty designed to protect human health and the environment from adverse effects of mercury. To assess the effectiveness of the convention in the future, better constraints about the current mercury emissions is a premise. In our study, we applied a top-down approach to quantify mercury emissions on the basis of atmospheric mercury measurements conducted at the remote high altitude monitoring station Jungfraujoch, Switzerland. We established the source-receptor relationships and by the means of atmospheric inversion we were able to quantify spatially resolved European emissions of 89 ± 14 t/a for elemental mercury. Our European emission estimate is 17% higher than the bottom-up emission inventory, which is within stated uncertainties. However, some regions with unexpectedly high emissions were identified. Stationary combustion, in particular in coal-fired power plants, is found to be the main responsible sector for increased emission estimates. Our top-down approach, based on measurements, provides an independent constraint on mercury emissions, helps to improve and refine reported emission inventories, and can serve for continued assessment of future changes in emissions independent from bottom-up inventories.

We present a highly time-resolved historical record of polychlorinated biphenyls (PCBs) from an Alpine ice core (Fiescherhorn glacier, Switzerland). Introduced in the 1940s, PCBs were widely used industrial chemicals. Because of their persistence they are still found in the environment, long after their production phase-out. The Fiescherhorn ice core record covers the entire time period of industrial use of PCBs, that is, 1940-2002. The total concentration of six PCBs varies from 0.5 to 5 ng L(-1) and reveals a temporal trend, with an 8-fold increase from the early 1940s to the peak value in the 1970s. The level in 2002 is comparable to the concentration in the 1940s, when PCBs were introduced into the market. The time trend of PCBs associated with the particulate fraction closely follows the trend found in the dissolved fraction, but the absolute values are a factor of 10 lower. In addition to changing emissions, fluctuations in the PCB record were explained by variabilty in convective transport and postdepositional processes such as surface melting. Concentrations of PCBs are in agreement with data from seasonal snow samples in the Alps, but are a factor of 100 higher than concentrations measured in the Arctic. Contrasting time trends and congener patterns between the Alpine and Arctic region indicate the importance of atmospheric transport and postdepositional effects.

In previous work, Alpine glaciers have been identified as a secondary source of persistent organic pollutants (POPs). However, detailed understanding of the processes organic chemicals undergo in a glacial system was missing. Here, we present results from a chemical fate model describing deposition and incorporation of polychlorinated biphenyls (PCBs) into an Alpine glacier (Fiescherhorn, Switzerland) and an Arctic glacier (Lomonosovfonna, Norway). To understand PCB fate and dynamics, we investigate the interaction of deposition, sorption to ice and particles in the atmosphere and within the glacier, revolatilization, diffusion and degradation, and discuss the effects of these processes on the fate of individual PCB congeners. The model is able to reproduce measured absolute concentrations in the two glaciers for most PCB congeners. While the model generally predicts concentration profiles peaking in the 1970s, in the measurements, this behavior can only be seen for higher-chlorinated PCB congeners on Fiescherhorn glacier. We suspect seasonal melt processes are disturbing the concentration profiles of the lower-chlorinated PCB congeners. While a lower-chlorinated PCB congener is mainly deposited by dry deposition and almost completely revolatilized after deposition, a higher-chlorinated PCB congener is predominantly transferred to the glacier surface by wet deposition and then is incorporated into the glacier ice. The incorporated amounts of PCBs are higher on the Alpine glacier than on the Arctic glacier due to the higher precipitation rate and aerosol particle concentration on the former. Future studies should include the effects of seasonal melt processes, calculate the quantities of PCBs incorporated into the entire glacier surface, and estimate the quantity of chemicals released from glaciers to determine the importance of glaciers as a secondary source of organic chemicals to remote aquatic ecosystems.

Organic ultraviolet (UV) filters are a group of compounds designed to absorb UV radiation and hence protect our skin against UV-induced damage. Apart from traditional sunscreens, they can be found in many other categories of personal care products (PCPs). These include skin care, facial makeup and lip care products, which are often used simultaneously, and on a regular basis. The frequency of occurrence as well as concentrations of organic UV filters contained in PCPs change over time. Furthermore, in Switzerland the exact UV filter concentrations are confidential. To date, only limited data are available for the levels of organic UV filters in PCPs, and these data refer mainly to sunscreens. In this paper, we provide an up-to-date frequency of occurrence and concentrations of organic UV filters in PCPs, including for the first time PCPs used in everyday life. A total of 116 PCPs was selected on the basis of a product-use questionnaire and distributed among seven PCP categories: lip care products, lipsticks, face creams, liquid makeup foundations, aftershaves, hand creams, and sunscreens. Concentrations of 22 organic UV filters were measured in the selected PCPs. The most frequently occurring UV filters were butyl methoxydibenzoylmethane (BMBM) detected in 82 products (71%), ethylhexyl methoxycinnamate (EHMC) in 59 products (51%) and octocrylene (OCT) in 50 products (43%). BMBM, EHMC and OCT concentrations averaged 2.6%, 4.0%, and 6.0%, respectively. Overall, UV filter concentrations in PCPs applied regularly throughout the year can be as high as those in sunscreens that are primarily used for sun protection and hence applied only on selected days. PCPs that are used on a regular basis, and often simultaneously, thus represent an important and, as yet, unquantified source of UV filter exposure. This study provides essential information for aggregate exposure assessments that combine data on concentrations of individual UV filters widely used in a variety of PCP categories.

This article provides an overview of concentrations of persistent organic pollutants (POPs) in ambient air on a global scale, including recent measurements and an extensive compilation of literature data. In this study, passive air samplers (PASs) were successfully employed to assess concentrations of POPs in ambient air from Africa, Latin America, the Caribbean, and the Pacific Islands. The project aimed to extend the knowledge on environmental contamination by POPs in these regions, where the currently available data are still limited to a few monitoring studies. The ambient air concentrations of PCB in Africa were relatively high when compared to other regions. Waste, in particular electronic waste, exported to Africa from industrialized countries may be a possible source of PCB in Africa, where PCB have never been extensively used or produced. For DDTs, the wide range of concentrations and particularly high levels in some countries of Africa and the Pacific Islands reflect the use of DDT for malaria control in these regions. For PCDD/PCDF, concentrations in Africa and Latin America are similar to or even higher than in Europe, probably due to unfavorable combustion practices of chlorine-containing materials. The data support the needs for further monitoring in developing countries and countries with economies in transition, and action to reduce environmental contamination by, and human exposure to, hazardous chemicals.

Persistent organic pollutants (POPs), such as polychlorinated biphenyls (PCBs), are ubiquitous environmental contaminants that have been targeted by national regulations since the 1970-1980s, followed in 2004 by the worldwide regulation under the Stockholm Convention on POPs. However, concerns are growing regarding the emergence of additional POP-like substances, such as chlorinated paraffins (CPs), which have particularly large production volumes. Whereas short-chain CPs (SCCPs) have recently been restricted in Europe and are currently under evaluation for inclusion into the Stockholm Convention, medium-chain CPs (MCCPs) have received little attention. On the one hand, temporal trends of CPs in the environment have hardly been investigated. On the other hand, the effectiveness of the Stockholm Convention on environmental levels of PCBs is still a matter of debate. Here, we reconstructed temporal trends of SCCPs, MCCPs, and PCBs in archived soil samples from six sampling sites in Switzerland, covering the period 1989-2014 (respectively 1988-2013 for one site). Concentrations of SCCPs have decreased in soil since 1994, which indicates positive effects of the reduction of production of SCCPs in Europe and the increasingly stringent regulation. However, the decline in soil is slow with a halving time of 18 years. Concentrations of MCCPs have continuously increased in soil over the entire period 1989-2014, with a doubling between 2009 and 2014. The concentrations of MCCPs have surpassed those of SCCPs, showing their relevance today, partly as replacements for SCCPs. Soil concentrations of PCBs peaked in 1999, i.e. three decades later than worldwide production and use of PCBs, but earlier than the entry into force of the Stockholm Convention. PCBs follow a decline in soil with a halving time of approx. 8 years. This study shows the usefulness of sample archives for the reconstruction and interpretation of time trends of persistent environmental contaminants.

We describe and illustrate a three-step data-processing approach that enables individual congener groups of chlorinated paraffins (CPs) to be resolved in mass spectra obtained from either of two soft ionization methods: electron capture negative ionization mass spectrometry (ECNI-MS) or atmospheric pressure chemical ionization mass spectrometry (APCI-MS). In the first step, general fragmentation pathways of CPs are deduced from analysis of mass spectra of individual CP congeners. In the second step, all possible fragment ions in the general fragmentation pathways of CPs with 10 to 20 carbon atoms are enumerated and compared to mass spectra of CP mixture standards, and a deconvolution algorithm is applied to identify fragment ions that are actually observed. In the third step, isotope permutations of the observed fragment ions are calculated and used to identify isobaric overlaps, so that mass intensities of individual CP congener groups can be deconvolved from the unresolved isobaric ion signal intensities in mass spectra. For a specific instrument, the three steps only need to be done once to enable deconvolution of CPs in unknown samples. This approach enables congener group-level resolution of CP mixtures in environmental samples, and it opens up the possibility for quantification of congener groups.

In recent years, the frequency of contact allergy to isothiazolinones has increased alarmingly in Europe, but only limited data are available on concentrations of isothiazolinones in consumer products.To examine the current frequency of isothiazolinones [methylisothiazolinone (MI), methylchloroisothiazolinone (MCI), benzisothiazolinone (BIT), and octylisothiazolinone (OIT)] in a wide array of detergents and cosmetics relevant for the Swiss population.By means of a market survey, the occurrence of isothiazolinones was investigated in 1948 consumer products. Of these, 88 products were analysed by liquid chromatography-high-resolution mass spectrometry after ultrasonic extraction.Only 7.6% of all cosmetics contained isothiazolinones, but the prevalence in detergents was much higher (42.9%). The measured concentration ranges in detergents were 4.3–10, 3.5–279, 3.8–186 and 7.9 ppm (one product only) for MCI, MI, BIT, and OIT, respectively [corrected]. For cosmetics, these were 1.3-133 and 4.8 ppm (one product only) for MI and MCI, respectively.Our study has shown that high concentrations of isothiazolinones (including MI) can be found in a large variety of products, in particular in detergents. Therefore, the safe use of these preservatives should be re-evaluated by including detergents in the exposure assessment.

Polychlorinated biphenyls (PCBs) are banned worldwide under the Stockholm Convention on Persistent Organic Pollutants. However, PCBs are still emitted in appreciable amounts from remaining primary sources in urban areas or landfills and are ubiquitous environmental contaminants, inter alia in soil and air. Concentrations of PCBs have been measured in various media by numerous studies worldwide. However, monitoring data do not always provide quantitative information about transport processes between different media, deposition fluxes to ground, or distribution of PCBs between environmental compartments. Also future trends in environmental contamination by PCBs cannot be predicted from monitoring data, but such information is highly relevant for decision-makers. Here, we present a new regionally resolved dynamic multimedia mass balance model for Switzerland to investigate the origin of PCBs in air and to investigate their long-term fate and mass balance in the environment. The model was validated with existing field data for PCBs. We find that advective inflow of PCBs from outside Switzerland into the atmospheric boundary layer is responsible for 80% of PCBs present in air in Switzerland, whereas Swiss emissions cause the remaining 20%. Furthermore, we show that the atmospheric deposition of the higher-chlorinated PCBs is dominated by particle-bound deposition, whereas the deposition of the lower-chlorinated PCBs is a combination of particle-bound and gaseous deposition. The volume fraction of particles in air is in both cases an important factor driving the deposition of PCBs to ground and, thus, contributing to the higher concentrations of PCBs generally observed in populated and polluted areas. Regional emissions influence the deposition fluxes only to a limited extent. We also find that secondary emissions from environmental reservoirs do not exceed primary emissions for all PCB congeners until at least 2036. Finally, we use our model to evaluate the effect of chemical regulation on future environmental contamination by PCBs.

Passive air samplers were deployed at 23 sites across the city of Zurich, Switzerland to investigate the spatial distribution of polychlorinated biphenyls (PCBs) in air. Concentrations of the six indicator PCBs (iPCBs) in air ranged from 54 to 3160 pg·m(-3) in the two sampling campaigns (spring 2011 and spring 2013). Measurements at two sampling sites were significantly higher than the median in both years, because of the proximity to primary PCB sources. Concentrations at most other stations were in a narrow range, suggesting that atmospheric PCB concentrations in Zurich are mainly caused by a high number of rather small sources. A correlation of iPCB concentrations in air with the number of buildings constructed between 1955 and 1975 in the surrounding areas of the sampling sites was observed. This demonstrates that PCB-containing building materials, such as joint sealants, influence PCB levels in urban air. Additionally, atmospheric iPCB concentrations were measured in the surrounding of a housing complex with PCB-contaminated joint sealants. Using a Gaussian diffusion model, annual iPCB emissions of 110-190 g were calculated for this housing complex. This appreciable amount released by a single building points out that more efforts are required to further eliminate remaining PCB stocks.

We present results from a chemical fate model quantifying incorporation of polychlorinated biphenyls (PCBs) into the Silvretta glacier, a temperate Alpine glacier located in Switzerland. Temperate glaciers, in contrast to cold glaciers, are glaciers where melt processes are prevalent. Incorporation of PCBs into cold glaciers has been quantified in previous studies. However, the fate of PCBs in temperate glaciers has never been investigated. In the model, we include melt processes, inducing elution of water-soluble substances and, conversely, enrichment of particles and particle-bound chemicals. The model is validated by comparing modeled and measured PCB concentrations in an ice core collected in the Silvretta accumulation area. We quantify PCB incorporation between 1900 and 2010, and discuss the fate of six PCB congeners. PCB concentrations in the ice core peak in the period of high PCB emissions, as well as in years with strong melt. While for lower-chlorinated PCB congeners revolatilization is important, for higher-chlorinated congeners, the main processes are storage in glacier ice and removal by particle runoff. This study gives insight into PCB fate and dynamics and reveals the effect of snow accumulation and melt processes on the fate of semivolatile organic chemicals in a temperate Alpine glacier.

Recently, increasing concentrations of persistent organic pollutants (POPs) have been observed in the sediment of glacier-fed Lake Oberaar, Switzerland. Melting glaciers have been suggested as a secondary source of POPs released to Alpine lakes. Here we further investigate whether climate warming may accelerate the release of POPs previously deposited to Alpine glaciers ("glacier hypothesis"). To test this hypothesis, a dynamic multimedia mass balance model is developed for the catchment area of Lake Oberaar and is applied to polychlorinated biphenyls (PCBs), polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs), and dichlorodiphenyl trichloroethane (DDT). This lake model is combined with two other models. The first is a dynamic multimedia mass balance model parametrized for the Swiss lowlands that is used to calculate (on the basis of historical emission data) the atmospheric concentrations that are an advective input into the model of the lake catchment. The second is a flow model of Oberaar Glacier that determines the residence time of persistent chemicals in the glacier after their deposition to the glacier surface. According to results from these three models in combination, the release of POPs by the glacier is currently increasing and accounts for the observed increase in concentrations in the lake sediment. The models indicate that approximately half of the amount of PCBs, PCDD/Fs, and DDT initially incorporated into the glacier ice is still stored in the glacier. Under the assumption that the climate is warming, accelerated release of POPs is to be expected for the future; in a model run where no climate warming is assumed, the period of time required for release of the same amount of chemicals is longer by several decades than in the scenario with a changing climate.

Schadstoffmessungen in den Sedimenten von Seen ermoglichen es, die Eintragsgeschichte von Chemikalien zu rekonstruieren. In Gletscherseen steigt die Konzentration persistenter organischer Schadstoffe, die langst verboten sind.

Chronology of brominated fame retardants (BFRs), a class of currentlywidely used chemicals, was compared to the respective historical profiles of legacy organochlorine compounds in three dated sediment cores from a prealpine lake (Lake Thun, Switzerland). Concentrations of polybrominated diphenyl ethers (PBDEs) and hexabromocyclododecanes (HBCDs) started to increase in the 1980s-1990s. In the more recent sediment layers, PBDEs still had steady or increasing concentrations, whereas for HBCDs one sediment core revealed a decreasing trend. In contrast to the contemporary BFRs, concentrations of legacy organochlorines, such as polychlorinated biphenyls (PCBs), polychlorinated naphthalenes (PCNs), and dichlorodiphenyl trichloroethane (DDT), peaked in deeper sediment layers deposited some decades ago. Measurements of atmospheric deposition and evaluation of wastewater discharges pointtoward deposition on the lake surface as a relevant input pathway and wastewater as a minor source of POPs in Lake Thun. The effect of the environmental awareness and the regulations taken in the 1970s to reduce environmental pollution of organochlorines is well reflected in the analyzed sediment cores. The sediment burden closely follows estimated time trends of consumption and emission of PCBs and DDT. The current residues in sediment of BFRs are still lower than the historical peak levels of organochlorines. However, current atmospheric deposition of BFRs is similar to deposition of PCBs. Considering the high amount of BFRs presently stocked in the anthroposphere in flame proofed materials, further measures to reduce emissions during BFRs life cycle are recommended to prevent high environmental pollution as it occurred for the organochlorine compounds.

A dated sediment core from Lake Thun covering the last 120 years was analyzed to get an overview of the historical trend of the chlorinated paraffin (CP) and polychlorinated biphenyl (PCB) deposition, because CPs and PCBs have/had similar applications as plasticizers and flame retardants. Total CP concentrations (sum of short chain (SCCP), medium chain (MCCP), and long chain CPs (LCCP)) showed a steep increase in the 1980s and a more-or-less stable level of 50 ng g(-1) dry weight (dw) since then. The concentration-time profile is in good agreement with the available information on global production data. The quantification of higher chlorinated SCCPs using electron capture negative ionization low resolution mass spectrometry (ECNI-LRMS) revealed an increase in recent years. In addition, the degree of chlorination of SCCPs has strongly increased during the past 40 years, which may indicate its use as an additive for plastics, paints, and coatings. Furthermore, PCBs were analyzed in dated sediment slices. The PCB concentrations (sum of the six indicator congeners) peaked around 1969 (18 ng g(-1) dw) and decreased to 1.3 ng g(-1) dw in the surface layer corresponding to 2004. The peak level of CPs exceeded those of PCBs by about a factor of 3.

More than a decade ago, the Stockholm Convention on Persistent Organic Pollutants (POPs), one of the multilateral environmental agreements administered by the United Nations Environment Programme (UNEP), entered into force. The objective of this Convention is to protect human health and the environment by controlling the releases of POPs. According to its Article 16, the effectiveness of the Stockholm Convention shall be evaluated using comparable monitoring data on the presence of POPs as well as their regional and global environmental transport. Here, we present a time series analysis on atmospheric POP concentrations from 15 monitoring stations in North America and Europe that provide long-term data and have started operations between 1990 and 2003. We systematically searched for temporal trends and significant structural changes in temporal trends that might result from the provisions of the Stockholm Convention. We find that such structural changes do occur, but they are related mostly to effects of national regulations enforced prior to the implementation of the Stockholm Convention, rather than to the enforcement of the provisions laid out in the Convention. One example is that concentrations of polychlorinated biphenyls, many of which started to decrease rapidly during the 1990s. Also effects of chemical transport and fate, for instance the re-volatilization of POPs from secondary sources, are thought to be a cause of some of the observed structural changes. We conclude that a decade of air monitoring data has not been sufficient for detecting general and statistically significant effects of the Stockholm Convention. Based on these lessons, we present recommendations for the future operation of existing monitoring programs and advocate for a stricter enforcement of the provisions of the Stockholm Convention, in the current absence of proof for its effectiveness.

Semi-volatile organic compounds (SVOCs) can be particle-bound or in the gas phase in the atmosphere, depending on the (temperature dependent) gas-particle partitioning of the chemicals and the fraction of particles in air. Several studies linked gas-particle partitioning of SVOCs in the atmosphere directly to the gaseous/particle-bound deposition of these chemicals, i.e. in cases of compounds occurring mainly in the gas phase, the deposition was also assumed to be mainly in gaseous form. In this study, we apply a multi-media fate model to point out that gas-particle partitioning of SVOCs in air and gaseous/particle-bound deposition of SVOCs are driven by different mechanism and, thus, cannot be deduced from each other. We apply our calculations to polychlorinated biphenyls (PCBs), as model SVOCs. We show that the fraction of particle-bound deposition to deciduous forest is 1.5-190 times higher in winter and between 5 and 1000 times higher in summer than the particle-bound fraction of these chemicals in air. The fraction of particle-bound deposition to coniferous forest is 1.5-172 times higher in winter and between 5 and 1000 times higher in summer than the particle-bound fraction of PCBs in air. In addition to the fractions of particle-bound SVOCs in air and particle-bound deposition, we recalculated particle-bound and gaseous deposition velocities to coniferous and deciduous forest for PCBs. The deposition velocities obtained for dry gaseous deposition (

Chlorinated paraffins (CPs) are high production volume chemicals, but data about their environmental fate are scarce. CP mixtures composed of thousands of isomers represent a major challenge for quantification at low levels in environmental samples. Here, we present a novel analytical method for analysis of short-chain, medium-chain, and long-chain CPs in a single injection, that also yields information about congener group pattern. Our detection method is based on direct injection into an atmospheric pressure chemical ionization source operated in negative ion mode under chlorine-enhanced conditions, followed by quadrupole time-of-flight high-resolution mass spectrometry (APCI-qTOF-HRMS) operated in full-scan mode. A mathematical algorithm is applied to deconvolute the CP patterns in the analyzed samples into a linear combination of patterns of technical CP mixtures and to quantify CPs using technical mixtures as external calibration standards. For CP mixtures with known composition, the new method provided concentrations that were within a factor of 1.2 of the target value. Accuracies for CPs spiked to sediment and fish extracts were between 91% and 123%. Concentrations determined in unspiked field samples were within a factor of 5 for short-chain CPs and a factor of 16 for medium-chain CPs of results obtained with an independent method based on gas chromatography/electron capture negative ionization high-resolution mass spectrometry (GC/ECNI-HRMS). The presented APCI-qTOF-HRMS pattern deconvolution method is an interesting alternative for CP analysis in environmental samples. It is particularly sensitive for medium- and long-chain CPs and has the advantage of being extremely fast (instrumental analysis time, less than 1 min).

The review article "Emergence and fate of cyclic volatile polydimethylsiloxanes (D4, D5) in municipal waste streams: Release mechanisms, partitioning and persistence in air, water, soil and sediments" by Surita and Tansel covers a relevant topic, but there are several serious issues with this paper. The inappropriate handling of data gathered from various sources has resulted in a flawed dataset. In addition, the authors performed several erroneous or meaningless calculations with the data. Their dataset leads to incorrect and misleading interpretations and should not be used.

One of the critical properties that define persistent organic pollutants (POPs) is a tendency toward wide-scale distribution in the environment. Atmospheric transport is one of the mechanisms through which this distribution occurs. Due to long-range atmospheric transport, POPs have been found in some of the most remote regions on Earth, including the Arctic, the Antarctic, and in high mountains. The latitudinal and long-term distribution of POPs on a global scale is controlled by a combination of thermodynamic temperature-driven processes, kinetically controlled advective phase-transfer reactions, and the degradation or transformation of POPs in environmental media. In addition to these processes, local and regional meteorology can greatly affect the distribution of POPs in mountains. From both a scientific and regulatory standpoint, it is often important to determine the geographic and emission sources of POPs. A number of approaches for identifying the sources of POPs in remote ecosystems are described herein.

Studies of the effects of changes in iron (Fe) redox status on cation exchange capacity (CEC) and other physical and chemical properties of clays have typically focused on purified clays or clay fractions, but little attention has been given to systems with mixed mineralogy, which is more typical of natural soils. The objective of this study was to measure and establish any correlation between changes in CEC and Fe mineralogy that occurs in a mixed-mineral clay system undergoing chemical reduction. The clay fraction (SE1089) of a soil containing a mixture of smectite, kaolinite, and Fe oxide was investigated using variable-temperature Mossbauer spectroscopy, chemical analyses, and reductive dissolution in CBD media. This study revealed that in the unreduced clay fraction half of the total Fe was structural iron (FeStr) in the smectite and half was in goethite. The goethite particles were estimated to be 9 nm in mean crystal diameter (MCD) and to contain 9% Al substituted isomorphously for Fe. An evolution of the different Fe pools and changes in CEC of the mixture were observed. The CEC of SE1089 smectite fraction sharply increased upon reduction, similar to the SWa-1 reference clay, even though the FeStr content of SE1089 is much less. Results revealed a correlation of the increase in CEC with FeStr reduction and oxide dissolution, giving a direct connection between the total coating content and the rate of dissolution. For this reason, dissolution kinetics appears to be a key factor in understanding the control of CEC by iron coated material. In particular, in natural media governed by bacterial activity, different dissolution kinetics are expected.