Development and validation of a liquid chromatography-tandem mass spectrometry (LC-MS/MS) method including 25 novel synthetic opioids in hair and subsequent analysis of a Swiss opioid consumer cohort.

Major public health concern is raised by the evidence that common drugs like heroin are now frequently laced or replaced with highly potent novel synthetic opioids (NSOs). The objective of this study was to explore the prevalence and patterns of NSOs in a cohort of Swiss opioid users by hair analysis. Hair analysis is considered an ideal tool for retrospective consumption monitoring. Hair samples from 439 opioid users in Zurich were analyzed. Study inclusion required a previous positive hair test result for heroin metabolites, oxycodone, fentanyl, methadone, or tramadol. The samples were extracted with a two-step extraction procedure, followed by a targeted LC-MS/MS (QTRAP® 6500+) analysis in multiple reaction monitoring mode for a total of 25 NSOs. The method underwent full validation and demonstrated good selectivity and sensitivity with limits of detection (LOD) as low as 0.1 pg/mg. The analyzed sample cohort demonstrated a positivity rate for NSOs of 2.5%, including the following NSOs: butyrylfentanyl, acrylfentanyl, furanylfentanyl, methoxyacetylfentanyl, ocfentanil, U-47700, isobutyrylfentanyl and benzylfentanyl. Furthermore, we were able to identify specific consumption patterns among drug users. The results indicate that hair analysis is a valuable tool for investigating the prevalence of NSOs in drug-using populations, which seems to be low in the case of Swiss opioid users. Nevertheless, the results highlight the need for sensitive analytical detection methods in forensic toxicology to identify and monitor substance distribution in different populations.

Biotransformation of short-chain chlorinated paraffins (SCCPs) with LinA2: A HCH and HBCD converting bacterial dehydrohalogenase.

Short-chain chlorinated paraffins (SCCPs) are polyhalogenated hydrocarbons as are hexachlorocyclohexanes (HCHs) and hexabromocyclododecanes (HBCDs). They all have been classified as persistent organic pollutants (POPs) under the UN Stockholm Convention. Per se such compounds are transformed slowly in the environment, transported over long distances and accumulate in biota. Several Sphingomonadacea strains isolated from HCH dump sites have evolved to express enzymes that can transform HCHs and HBCDs. We hypothesized that LinA2, a dehydrohalogenase expressed in such bacteria, may also transform CPs to chlorinated olefins (COs). Three mixtures of penta- to deca-chlorinated undecanes (C11), dodecanes (C12) and tridecanes (C13) were exposed to LinA2. High-resolution full-scan mass spectra (R∼8'000) of CPs and COs were obtained applying a soft ionization method, enhancing chloride-adduct [M+Cl]- formation. A mathematical deconvolution procedure was used to separate interfering spectra to verify that LinA2 indeed catalyzed the conversion of CPs to COs. About 20-40% of the material was transformed in 24 h, about 50-70% was converted in 200 h. A bimodal first-order kinetic model could describe transformations of reactive and persistent CPs. Under the given conditions reactive CPs (τ1/2 = 1.4-6.9 h) were converted 30 to 190-times faster than the persistent ones (τ1/2 = 150-260 h). Proportions of persistent isomers (pp) varied from 60 to 80%. Lower chlorinated homologues contained higher proportions of persistent isomers. In conclusion, SCCP mixtures contain both, material that is readily converted by LinA2, and persistent material that is not or only slowly transformed.

Environmental Risks of Medium-Chain Chlorinated Paraffins (MCCPs): A Review.

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.

Profiling wines in China for the biogenic amines: A nationwide survey and pharmacokinetic fate modelling.

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.

Transformation of chlorinated paraffins to olefins during metal work and thermal exposure - Deconvolution of mass spectra and kinetics.

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 (kapp) increased up to 0.17, 0.29 and 0.46 h-1 for penta-, hexa- and heptachloro-tridecanes exposed at 220 °C. Respective half-life times (τ1/2) decreased from 4.0 to 2.4 and 1.5 h. Thus, higher chlorinated paraffins degrade faster than lower chlorinated ones. In conclusion, exposure of CPs during metal drilling and thermal treatment induced HCl losses and CO formation. It is expected that CPs and COs are co-released from such processes. Full-scan mass spectra and subsequent deconvolution of interfered signals is a promising approach to tackle the CP/CO problem, in case of insufficient mass resolution.

Import, use, and emissions of PCBs in Switzerland from 1930 to 2100.

Polychlorinated biphenyls (PCBs) are persistent organic compounds that are ubiquitously found in the environment. Their use and manufacture were restricted or banned in many countries in the 1970-1980s, however, they still persist in the antroposphere, the environment and in biota worldwide today. Conventions like the Convention on Long-range Transboundary Air Pollution encourage or bind the member parties to annually submit emission inventories of regulated air pollutants. Unfortunately, several member states have not yet reported PCB emissions. The identification and quantification of stocks and emissions sources is, however, an important precondition to handle and remove the remaining reservoirs of PCBs and, thus, to be able to reduce emissions and subsequently environmental exposure. Here, we estimate past, present, and future emissions of PCBs to air in Switzerland and provide emission factors for all relevant emission categories. Switzerland hereby represents a typical developed industrial country, and most of the assumptions and parameters presented here can be used to calculate PCB emission also for other countries. PCB emissions to air are calculated using a dynamic mass flow and emissions model for Switzerland, which is run for the years 1930-2100. The results point out the importance of the use of PCBs in open applications, which have largely been previously overlooked. Additionally, we show that PCBs will persist in applications during the coming decades with ongoing emissions. Especially the use of PCBs in open applications will cause Swiss emissions to remain above 100 kg PCB per year, even after the year 2030. Our developed model is available in Excel/VBA and can be downloaded with this article.

Understanding and Predicting the Fate of Semivolatile Organic Pesticides in a Glacier-Fed Lake Using a Multimedia Chemical Fate Model.

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.

Dynamic Transgenerational Fate of Polychlorinated Biphenyls and Dioxins/Furans in Lactating Cows and Their Offspring.

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.

Quantifying Short-Chain Chlorinated Paraffin Congener Groups.

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.

Deconvolution of Mass Spectral Interferences of Chlorinated Alkanes and Their Thermal Degradation Products: Chlorinated Alkenes.

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 (Cl5-Cl9). Deconvolution of mass patterns allowed quantifying fractions of interfering CPs and CP-enes. After exposure to 220 °C for 2, 4, 8, and 24 h, fractions of CP-enes within the respective interfering clusters increased from 0-3% at 0 h up to 37-44% after 24 h. It was shown that thermolysis of CPs follows first-order kinetics. The presented deconvolution method allows CP degradation studies with mass resolution lower than 20000 and is therefore a good alternative when higher resolution is not available.

Medium-Chain Chlorinated Paraffins (CPs) Dominate in Australian Sewage Sludge.

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 (<57-1421 ng/g dw) were detected in the Australian sewage sludge, which were comparable with the LCCPs concentrations (116-960 ng/g dw). This is the first time that CPs were reported in Australian sewage sludge. The results of this study gives a first impression on the distribution of the SCCPs, MCCPs, and LCCPs in Australia wastewater treatment plants (WWTPs).

Inversion Approach to Validate Mercury Emissions Based on Background Air Monitoring at the High Altitude Research Station Jungfraujoch (3580 m).

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.

Temporal trends of chlorinated paraffins and polychlorinated biphenyls in Swiss soils.

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.

Occurrence and concentrations of isothiazolinones in detergents and cosmetics in Switzerland.

BACKGROUND: 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 4.3­10, 3.5­279, 3.8­186 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. 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.

Global production, use, and emission volumes of short-chain chlorinated paraffins - A minimum scenario.

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.

Deconvolution of Soft Ionization Mass Spectra of Chlorinated Paraffins To Resolve Congener Groups.

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.

A Temperate Alpine Glacier as a Reservoir of Polychlorinated Biphenyls: Model Results of Incorporation, Transport, and Release.

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.

Ten years after entry into force of the Stockholm Convention: What do air monitoring data tell about its effectiveness?

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.

What determines PCB concentrations in soils in rural and urban areas? Insights from a multi-media fate model for Switzerland as a case study.

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.