Mapping spatial and temporal trends of atmospheric deposition of nitrogen at the landscape level in Germany 2005, 2015 and 2020 and their comparison with emission data.

Mosses are particularly suitable for recording the accumulation of atmospheric substance inputs in large areas at relatively many locations. In Europe, this has been done every five years since 1990 as part of the European Moss Survey. In this framework, mosses were collected at up to 7312 sites in up to 34 countries and chemically analyzed for metals (since 1990), nitrogen (since 2005), persistent organic pollutants (since 2010) and microplastic (since 2015). The present investigation aimed at determining the nitrogen accumulated in three-year-old shoots from mosses collected in Germany in 2020 by quality-controlled sampling and chemical analysis according to the European Moss Survey Protocol (ICP Vegetation 2020). The spatial structure of the measurement values was analyzed by means of Variogram Analysis, and the respective function was used for Kriging-Interpolation. In addition to mapping the nitrogen values according to the international classification, maps based on 10 percentile classes were calculated. Maps for the Moss Survey 2020 data were compared with respective maps produced from the 2005 and 2015 Moss Survey data. Trends in Germany-wide nitrogen medians over the past three campaigns (2005, 2015 and 2020) show that nitrogen medians decreased by -2 % between 2005 and 2015 and increased by +8 % between 2015 and 2020. These differences are not significant and do not match the emission trends. Therefore, emission register data needs to be controlled by monitoring nitrogen deposition with technical and biological samplers and deposition modelling.

Polychlorinated biphenyls (PCB) and polychlorinated dibenzo-para-dioxins and dibenzofurans (PCDD/F) in ambient air and deposition in the German background.

PCDD/Fs (17 congeners and Σ tetra -to octachloro homologues) and 209 PCBs were investigated in monthly samples of ambient air (gas + particle phase) and atmospheric deposition at two background monitoring sites in Germany in 2018/19. In atmospheric deposition samples, PCDD/F congeners as well as certain PCBs were frequently below the method quantification limits whereas values for PCDD/F homologue groups could be quantified more often. Annual deposition averages for individual PCDD/Fs were between <0.1 µg/m2d and 6.7 µg/m2d. Averages for Σ TeCDD/F to OCDD/F homologue totals in deposition were about 11 pg/m2d and 19 pg/m2d. Total PCB deposition rates were about 1900 pg/m2d and 1550 pg/m2d. PCDD/F + PCB-deposition rates were below 1 pg WHO2005-TEQ/m2d on average. In ambient air, both substance groups were frequently observed. Annual concentration averages for individual PCDD/F were between 0.1 fg/m³ and 50 fg/m³. Average values for Σ TeCDD/F to OCDD/F homologue totals in ambient air were 283 fg/m³ and 162 fg/m³. Total PCB concentrations were about 50 pg/m³ at both sites. PCDD/F + PCB-TEQ values were lower than 5 fg WHO2005-TEQ/m³ on average. Besides the frequently studied dioxin-like PCBs and six indicator PCBs, the analysis of the 209 PCBs (166 separated PCB-peaks) enabled the identification and evaluation of additional PCBs that might be of environmental concern. Of 166 PCBs or PCB-coelutions, up to 144 were quantified in air samples and up to 94 in atmospheric deposition samples. In ambient air, some of these PCBs were observed at levels similar to or exceeding those of the six indicator PCBs. Important additional PCBs in ambient air were PCB 5 + 8, PCB 11, PCB 17, PCB 18, PCB 20 + 33, PCB 31, PCB 43 + 49, PCB 44, PCB 47 + 48 + 65 + 75, PCB 93 + 95 + 98 + 102, PCB 139 + 149, and PCB 151. The presence of these PCBs in atmospheric samples implies that by analysing only selected PCBs potentially important contaminants are overlooked.

Global intercomparison of polyurethane foam passive air samplers evaluating sources of variability in SVOC measurements.

Polyurethane foam passive air samplers (PUF-PAS) are the most common type of passive air sampler used for a range of semi-volatile organic compounds (SVOCs), including regulated persistent organic pollutants (POPs) and polycyclic aromatic hydrocarbons (PAHs), and emerging contaminants (e.g., novel flame retardants, phthalates, current-use pesticides). Data from PUF-PAS are key indicators of effectiveness of global regulatory actions on SVOCs, such as the Global Monitoring Plan of the Stockholm Convention on Persistent Organic Pollutants. While most PUF-PAS use similar double-dome metal shielding, there is no standardized dome size, shape, or deployment configuration, with many different PUF-PAS designs used in regional and global monitoring. Yet, no information is available on the comparability of data from studies using different PUF-PAS designs. We brought together 12 types of PUF-PAS used by different research groups around the world and deployed them in a multi-part intercomparison to evaluate the variability in reported concentrations introduced by different elements of PAS monitoring. PUF-PAS were deployed for 3 months in outdoor air in Kjeller, Norway in 2015-2016 in three phases to capture (1) the influence of sampler design on data comparability, (2) the influence of analytical variability when samplers are analyzed at different laboratories, and (3) the overall variability in global monitoring data introduced by differences in sampler configurations and analytical methods. Results indicate that while differences in sampler design (in particular, the spacing between the upper and lower sampler bowls) account for up to 50 % differences in masses collected by samplers, the variability introduced by analysis in different laboratories far exceeds this amount, resulting in differences spanning orders of magnitude for POPs and PAHs. The high level of variability due to analysis in different laboratories indicates that current SVOC air sampling data (i.e., not just for PUF-PAS but likely also for active air sampling) are not directly comparable between laboratories/monitoring programs. To support on-going efforts to mobilize more SVOC data to contribute to effectiveness evaluation, intercalibration exercises to account for uncertainties in air sampling, repeated at regular intervals, must be established to ensure analytical comparability and avoid biases in global-scale assessments of SVOCs in air caused by differences in laboratory performance.

Long-term trends of airborne halogenated flame retardants (HFRs) by means of tree leaf and shoot analyses.

The historical air pollution with halogenated flame retardants (HFRs) in Germany was assessed by investigating tree leaf and shoot samples which have been archived in the German environmental specimen bank. Samples covered the period from 1985 to 2016. 43 HFRs comprising polybrominated diphenyl ethers as well as emerging brominated and chlorinated compounds such as Dechlorane Plus, DBDPE, or DPTE, were analysed in 115 samples from ten sub sites originating from six areas characterised by different land uses, including urban as well as a background site. HFRs were observed in each sample showing the widespread distribution of HFRs in Germany in tree leaves and shoots as bioindicators of past and present atmospheric pollution. Analytes observed at elevated concentrations were BDE 209, DBDPE and DPTE. Observed HFR-levels differed between analytes as well as sampling locations, particularly prior to the year 2000. They were typically highest at conurbation areas. Concentrations at the background site often belonged to the lowest ones observed, however, lowest values were not exclusively found there. The quantification frequencies appeared to decrease from the past to most recent samples. With few exceptions, atmospheric pollution of both, legacy and emerging HFRs, decreased significantly.

Organohalogen compounds of emerging concern in Baltic Sea biota: Levels, biomagnification potential and comparisons with legacy contaminants.

While new chemicals have replaced major toxic legacy contaminants such as polychlorinated biphenyls (PCBs) and dichlorodiphenyltrichloroethane (DDT), knowledge of their current levels and biomagnification potential in Baltic Sea biota is lacking. Therefore, a suite of chemicals of emerging concern, including organophosphate esters (OPEs), short-chain, medium-chain and long-chain chlorinated paraffins (SCCPs, MCCPs, LCCPs), halogenated flame retardants (HFRs), and per- and polyfluoroalkyl substances (PFAS), were analysed in blue mussel (Mytilus edulis), viviparous eelpout (Zoarces viviparus), Atlantic herring (Clupea harengus), grey seal (Halichoerus grypus), harbor seal (Phoca vitulina), harbor porpoise (Phocoena phocoena), common eider (Somateria mollissima), common guillemot (Uria aalge) and white-tailed eagle (Haliaeetus albicilla) from the Baltic Proper, sampled between 2006 and 2016. Results were benchmarked with existing data for legacy contaminants. The mean concentrations for ΣOPEs ranged from 57 to 550 ng g-1 lipid weight (lw), for ΣCPs from 110 to 640 ng g-1 lw for ΣHFRs from 0.42 to 80 ng g-1 lw, and for ΣPFAS from 1.1 to 450 ng g-1 wet weight. Perfluoro-4-ethylcyclohexanesulfonate (PFECHS) was detected in most species. Levels of OPEs, CPs and HFRs were generally similar or higher than those of polybrominated diphenyl ethers (PBDEs) and/or hexabromocyclododecane (HBCDD). OPE, CP and HFR concentrations were also similar to PCBs and DDTs in blue mussel, viviparous eelpout and Atlantic herring. In marine mammals and birds, PCB and DDT concentrations remained orders of magnitude higher than those of OPEs, CPs, HFRs and PFAS. Predator-prey ratios for individual OPEs (0.28-3.9) and CPs (0.40-5.0) were similar or somewhat lower than those seen for BDE-47 (5.0-29) and HBCDD (2.4-13). Ratios for individual HFRs (0.010-37) and PFAS (0.15-47) were, however, of the same order of magnitude as seen for p,p'-DDE (4.7-66) and CB-153 (31-190), indicating biomagnification potential for many of the emerging contaminants. Lack of toxicity data, including for complex mixtures, makes it difficult to assess the risks emerging contaminants pose. Their occurence and biomagnification potential should trigger risk management measures, particularly for MCCPs, HFRs and PFAS.

Recent findings of halogenated flame retardants (HFR) in the German and Polar environment.

To get an overview about distribution, levels and temporal trends of polybrominated diphenyl ethers (PBDE) and halogenated flame retardants (HFR) of emerging concern, different types of environmental samples archived in the German Environment Specimen Bank as well as fish filet samples from the Arctic (n = 13) and Antarctica (n = 5) were analysed for 43 substances (24 PBDE, 19 HFR) using a multi-column clean-up and GC-API-MS/MS or GC-MS. Sample types were herring gull egg (n = 3), blue mussel (n = 3) and eelpout filet (n = 3) from the German North- and Baltic Sea, bream filet (n = 7), zebra mussel (n = 6) and suspended particulate matter (SPM, n = 7) from German freshwater ecosystems as well as tree leaves (n = 9)/shoots (n = 10), soil (n = 4), earthworm (n = 4) and deer liver (n = 7) as representatives of German terrestrial ecosystems. PBDE and emerging HFR were present in each investigated matrices from Germany and Polar regions showing their widespread distribution. The presence in Arctic and Antarctic fish samples confirms their long-range transport potential. Average concentrations of total emerging HFR were highest in SPM (26 ng g-1 dry weight (dw)), zebra mussel (10 ng g-1 dw) and herring gull egg (2.6 ng g-1 dw). Lowest levels were measured in fish filet samples from Antarctica (0.02 ng g-1 dw). Average total PBDE concentrations were highest in bream filet (154 ng g-1), herring gull egg (61 ng g-1 dw), SPM (21 ng g-1 dw), and zebra mussel 18 (ng g-1) and lowest in deer liver (0.04 ng g-1 dw). The patterns of non-fauna terrestrial samples (leaves, shoots, soil) as well as SPM were dominated by DBDPE and BDE209. Elevated proportions of DPTE and in most cases the absence of DBDPE characterized all fauna samples with the exception of Polar samples. Overall, emerging HFR appeared to be less bioaccumulative than PBDE. Temporal trends were generally decreasing with few exceptions such as DBDPE.

(Persistent) Organic pollutants in Germany: results from a pilot study within the 2015 moss survey.

BACKGROUND: Since 1990, every 5 years, moss sampling is conducted within the European moss monitoring programme to assess the atmospheric deposition of airborne pollutants. Besides many other countries, Germany takes regularly part at these evaluations. Within the European moss monitoring 2015, more than 400 moss samples across Germany were taken according to a harmonized methodology for the assessment heavy metal and nitrogen input. In a pilot programme, eight of these sites were chosen for additional investigations on a broad range of organic contaminants to evaluate their accumulation in moss and thereby their presence in atmospheric deposition in Germany. Target compound classes comprised polycyclic aromatic hydrocarbons (PAH), polychlorinated dibenzodioxins and -furans (PCDD/F), dioxin-like and non-dioxin-like polychlorinated biphenyls (dl-PCB, ndl-PCB), polyfluorinated alkyl substances, classical flame retardants as well as emerging chlorinated and brominated flame retardants. In total, 120 target compounds were analysed. For some analytes, comparisons of accumulation in moss and tree leave samples were possible. RESULTS: Except for certain flame retardants, PFAS, and ndl-PCB, substances of all other compound classes could be quantified in moss samples of all sites. Concentrations were highest for PAH (40-268 ng g-1) followed by emerging flame retardants (0.5-7.7 ng g-1), polybrominated diphenyl ethers (PBDE; 0.3-3.7 ng g-1), hexabromocyclododecane (HBCD; 0.3-1.2 ng g-1), dl-PCB (0.04-0.4 ng g-1) and PCDD/F (0.008-0.06 ng g-1). CONCLUSIONS: Results show the widespread atmospheric distribution and deposition of organic contaminants across Germany as well as the suitability of moss as bioaccumulation monitor for most of these compound classes. Compared to nearby tree leaf samples, accumulation potential of moss appeared to be higher for pollutants of high octanol-air partition coefficient (KOA) and octanol-water partition coefficient (KOW).

Halogenated flame retardants in tree samples applied as bioindicators for atmospheric pollution.

Coniferous shoots and deciduous tree leaf samples from 10 sites in Germany were taken in 2015 or 2016 within the German Environmental Specimen Bank sampling program and analysed for 24 polybrominated biphenyl ethers (PBDEs) and 19 additional halogenated flame retardants (HFRs). At one site, additional historic samples dating back till 2003 were also investigated. Samples were Soxhlet-extracted, cleaned-up by a non-destructive multi-step procedure involving gel permeation chromatography, and detected by GC-API-MS/MS as well as GC-MS. Besides PBDEs as classical HFRs, emerging HFRs such as Dechlorane Plus, DPTE, DBDPE, or ATE were region-wide observed demonstrating their widespread occurrence in the atmosphere. Highest concentrations in recent samples were found for DBDPE (<230-2760 pg g-1 dry weight (dw)) followed by DPTE (91-1540 pg g-1 dw), BDE209 (<156-461 pg g-1 dw), and BDE47 (<27-505 pg g-1 dw) or DP (31-122 pg g-1 dw). The overall uniform and widespread distribution as well as similar HFR levels and composition profiles observed in recent conifer shoots and corresponding deciduous tree leaves from the same area indicate a prolonged medium to long-range transport as sources. Furthermore, it is demonstrated that both tree types are generally suitable bioindicators for atmospheric pollution with HFRs, although accumulation may vary depending on HFR properties and accumulation period. The historic samples showed decreasing PBDE levels whereas no clear trend could be observed for other investigated HFRs at this site.

Determination of halogenated flame retardants by GC-API-MS/MS and GC-EI-MS: a multi-compound multi-matrix method.

The extensive application of halogenated flame retardants has led to their widespread distribution in the environment. Recently, concerns emerged regarding their potential persistence, (bio)accumulation, and/or toxicity. Particularly halogenated flame retardants based on norbornene structures, like Dechlorane Plus as well as other brominated PBDE replacements, generically called emerging, novel, or alternative flame retardants, are in the focus of interest. A comprehensive analytical method for the determination of 21 halogenated flame retardants (HFRs) of different substance classes (dechloranes, brominated aromates, brominated ethers, cyclic BFR) in a broad variety of matrices (tree leaves, fish fillet, birds eggs, suspended particles) was developed in order to assess their environmental levels as well as temporal trends, especially for the use within environmental specimen banks (ESBs). In addition to the alternative HFRs, a set of 24 PBDEs were measured in the same samples, however using GC-EI-MS for detection. Samples were extracted using accelerated solvent extraction (ASE) with dichloromethane:hexane (exception: soxhlet extraction for suspended particles) followed by a multi column clean-up. Quantification was performed by API-GC-MS/MS as a modern, gentle, and sensitive technique for simultaneous detection of compounds throughout a wide range of masses and fragmentation characteristics (exception: PBDE detection using GC-EI-MS). With the exception of BDE 209, instrumental precisions of target compounds ranged from 1% to 16 % (at levels of 2 pg injection-1 for HFR, 20 pg injection-1 for DBDPE, 7-36 pg injection-1 for PBDEs). Interday precisions of the entire analytical method including extraction and clean-up were mostly below 25% for all validation matrices at spiked levels of 100 pg sample-1 for HFR (DBDPE: 1000 pg sample-1) and 1200-6000 pg sample-1 for PBDEs. The majority of analytes were investigated with expanded measurement uncertainties of less than 50%. Graphical abstract A new approach to HFR analysis in multiple environmental matrices.

Neutral polyfluorinated compounds in indoor air in Germany--the LUPE 4 study.

Perfluoroalkyl- and polyfluoroalkyl-substances (PFAS) have been detected in many types of environmental media and biota including humans. We determined volatile PFAS, including fluorotelomer alcohols (FTOHs), fluorotelomer acrylates (FTACs), perfluorooctane sulfonamides (FOSAs), and perfluorooctane sulfonamidoethanols (FOSEs), in indoor air of residences and schools in Germany. FTOHs, FTACs, FOSEs, and FOSAs were quantified with median levels in schools (in residences) of 11,783pg/m(3) (13,198pg/m(3)), 737pg/m(3) (450pg/m(3)), 130pg/m(3) (278pg/m(3)), and 243pg/m(3) (110pg/m(3)), respectively. Using our data and previously published results in a simplified model based on the medians and 95th percentiles, the "typical" and "high" daily non-dietary exposures were calculated to be 4.2ng/kg body weight (9.9ng/kgb.w.) for Σ-FTOHs and 0.1ng/kgb.w. (0.8ng/kgb.w.) for Σ-FOSEs/FOSAs in children. Inhalation was the dominant intake pathway for FTOHs; however, dust ingestion contributed significantly to the total intake of FOSEs/FOSAs. In organisms, 8:2 FTOH is degraded to perfluorooctanoate (PFOA). Assuming that 1% of 8:2 FTOH is converted to PFOA, 8:2 FTOH exposure in Germany has a negligible contribution to the total daily PFOA exposure, which is mainly driven by dietary intake.

Temporal variations of perfluoroalkyl substances and polybrominated diphenyl ethers in alpine snow.

The occurrence and temporal variation of 18 perfluoroalkyl substances (PFASs) and 8 polybrominated diphenyl ethers (PBDEs) in the European Alps was investigated in a 10 m shallow firn core from Colle Gnifetti in the Monte Rosa Massif (4455 m above sea level). The firn core encompasses the years 1997-2007. Firn core sections were analyzed by liquid chromatography-tandem mass spectrometry (PFASs) and gas chromatography-mass spectrometry (PBDEs). We detected 12 PFASs and 8 PBDEs in the firn samples. Perfluorobutanoic acid (PFBA; 0.3-1.8 ng L(-1)) and perfluorooctanoic acid (PFOA; 0.2-0.6 ng L(-1)) were the major PFASs while BDE 99 (

Ombrotrophic peat bogs are not suited as natural archives to investigate the historical atmospheric deposition of perfluoroalkyl substances.

As ombrotrophic peat bogs receive only atmospheric input of contaminants, they have been identified as suitable natural archives for investigating historical depositions of airborne pollutants. To elucidate their suitability for determining the historical atmospheric contamination with perfluoroalkyl substances (PFAS), two peat cores were sampled at Mer Bleue, a bog located close to Ottawa, Canada. Peat cores were segmented, dried, and analyzed in duplicate for 25 PFASs (5 perfluororalkyl sulfonates (PFSAs), 13 perfluoroalkyl carboxylates (PFCAs), 7 perfluororalkyl sulfonamido substances). Peat samples were extracted by ultrasonication, cleaned up using a QuEChERS method, and PFASs were measured by HPLC-MS/MS. Twelve PFCAs and PFSAs were detected regularly in peat samples with perfluorooctane sulfonate (85-655 ng kg(-1)), perfluorooctanoate (150-390 ng kg(-1)), and perfluorononanoate (45-320 ng kg(-1)) at highest concentrations. Because of post depositional relocation processes within the peat cores, true or unbiased deposition fluxes (i.e., not affected by post depositional changes) could not be calculated. Apparent or biased deposition rates (i.e., affected by post depositional changes) were lower than measured/calculated deposition rates for similar urban or near-urban sites. Compared to PFAS production, PFAS concentration and deposition maxima were shifted about 30 years toward the past and some analytes were detected even in the oldest segments from the beginning of the 20th century. This was attributed to PFAS mobility in the peat profile. Considerable differences were observed between both peat cores and different PFASs. Overall, this study demonstrates that ombrotrophic bogs are not suited natural archives to provide authentic and reliable temporal trend data of historical atmospheric PFAS deposition.

Waste water treatment plants as sources of polyfluorinated compounds, polybrominated diphenyl ethers and musk fragrances to ambient air.

To investigate waste water treatment plants (WWTPs) as sources of polyfluorinated compounds (PFCs), polybrominated diphenyl ethers (PBDEs) and synthetic musk fragrances to the atmosphere, air samples were simultaneously taken at two WWTPs and two reference sites using high volume samplers. Contaminants were accumulated on glass fiber filters and PUF/XAD-2/PUF cartridges, extracted compound-dependent by MTBE/acetone, methanol, or hexane/acetone and detected by GC-MS or HPLC-MS/MS. Total (gas+particle phase) concentrations ranged from 97 to 1004 pg m(-3) (neutral PFCs),

Polyfluorinated compounds in residential and nonresidential indoor air.

Indoor air concentrations of fifteen volatile per- and polyfluorinated compounds (PFCs) (five fluorotelomer alcohols (FTOHs), three fluorotelomer acrylates (FTAs), three perfluorinated sulfonamido ethanols (FASEs), and three perfluorinated sulfonamides (FASAs)) were determined in residential and nonresidential indoor air environments. Air samples were taken with passive samplers, consisting of XAD-4 impregnated polyurethane foam (PUF) disks in steel housings. Impregnated PUF disks were extracted by fluidized bed extraction (FBE) using methyl-tert-butyl ether/acetone (1:1) and analyzed by gas chromatography-mass spectrometry. Total PFC indoor air concentrations ranged from 8.2 to 458 ng m(-3). Individual PFC concentrations were between 42 pg m(-3) (6:2 FTA) and 209 ng m(-3) (8:2 FTOH). Concentrations of total FTOHs, FTAs, and FASAs + FASEs ranged from 0.2 to 152 ng m(-3) (FTAs), from 3.3 to 307 ng m(-3) (FTOHs), and from 4.4 to 148 ng m(-3) (FASAs + FASEs). Most elevated individual, group, and total PFC concentrations were detected in two stores selling outdoor equipment, one furniture shop, and one carpet shop. Indoor air concentrations were several orders of magnitude higher than published outdoor air concentrations indicating indoor air environments as sources for PFCs to the atmosphere. Concentrations were used to estimate human exposure to investigated PFCs.

Wet deposition of poly- and perfluorinated compounds in Northern Germany.

Twenty precipitation samples were taken concurrently with air samples at a northern German monitoring site over a period of 7 months in 2007 and 2008. Thirty four poly- and perfluorinated compounds (PFC) were determined in rain water samples by solid phase extraction and HPLC-MS/MS analysis. Seventeen compounds were detected in rain water with SigmaPFC concentrations ranging from 1.6 ng L(-1) to 48.6 ng L(-1). Perfluorooctanoate (PFOA) and perfluorobutanate (PFBA) were the compounds that were usually observed in highest concentrations. Calculated SigmaPFC deposition rates were between 2 and 91 ng m(-2) d(-1). These findings indicate that particle phase PFC are deposited from the atmosphere by precipitation. A relationship between PFC wet deposition and air concentration may be established via precipitation amounts. Trajectory analysis revealed that PFC concentration and deposition estimates in precipitation can only be explained if a detailed air mass history is considered.

Polyfluorinated compounds in the atmosphere of the Atlantic and Southern Oceans: evidence for a global distribution.

High volume air samples taken onboard several research vessels in the Atlantic Ocean, the Southern Ocean, and the Baltic Sea as well as at one land-based site close to Hamburg, Germany, in 2007 and 2008 were analyzed for per- and polyfluorinated organic compounds (PFCs). A set of neutral, volatile PFCs such as fluorotelomer alcohols (FTOH) or perfluoroalkyl sulfonamides and ionic nonvolatile PFCs like perfluorinated carboxylates (PFCA) and sulfonates (PFSA) were collected on PUF/XAD-2/PUF cartridges and glass fiber filters and determined using GC-MS and HPLC-MS/MS. PFCs were detected in all air samples, even in Antarctic regions, and occurred predominantly in the gas phase. Total gas-phase concentrations of ship-based samples ranged from 4.5 pg m(-3) in the Southern Ocean to 335 pg m(-3) in European source regions. Concentrations of 8:2 FTOH, the analyte that was usually observed in highest concentrations, were between 1.8 and 130 pg m(-3). PFC concentrations decreased from continental regions toward marine regions and from Central Europe toward the Arctic and Antarctica. Southern hemispheric concentrations of individual PFCs were significantly lower than those of the northern hemisphere. On the basis of this data set, marine background PFC concentrations and atmospheric residence times were calculated. This study gives further evidence that volatile PFCs undergo atmospheric long-range transportto remote regions and may contribute to their contamination with persistent PFCA and PFSA.

Annual time series of air concentrations of polyfluorinated compounds.

Per- and polyfluorinated organic compounds (PFC) in air were determined in samples taken at two sites in the vicinity of Hamburg, Germany, over a period of 14 months. PUF/XAD-2/PUF cartridges and glass fiber filters were applied for the collection of airborne PFC. A set of volatile, neutral PFCs such as fluorotelomer alcohols (FTOH) or perfluorinated sulfonamides and ionic, nonvolatile PFC like perfluorinated carboxylates and sulfonates were determined using GC-MS and HPLC-MS/MS. Backward trajectory analysis was performed to elucidate the origin of the air mass parcels sampled. PFCs were predominantly detected in the gas phase. A fluctuating baseline presenting north German background levels and singular events of high concentrations were characteristic for the time series of all analytes and both locations. The origin of sampled air was the driving parameter influencing the PFC levels. Elevated PFC concentrations occurred in air arriving from industrialized and populated regions west and southwest of Hamburg. Maximum individual PFC concentrations reached 600 pg m(-3) (8:2 FTOH) in the gas phase and 13 pg m(-3) (perfluorooctane sulfonate) in the particle phase. The class of FTOH clearly dominated the gas-phase substance spectrum. The compound that was detected in highest concentrations was 8:2 FTOH. Individual gas-phase PFC concentrations were higher in summer than in winter. Temperature-dependent emissions of volatile and semi-volatile PFCs from diffuse sources to the gas phase are presumed to be responsible for this observation.

Optimized method avoiding solvent-induced response enhancement in the analysis of volatile and semi-volatile polyfluorinated alkylated compounds using gas chromatography-mass spectrometry.

A method for the analysis of airborne (semi-)volatile polyfluorinated alkyl substances (PFASs) was optimized to avoid solvent-induced response enhancements as observed using ethyl acetate as extraction solvent (recoveries up to 300%, likely due to acetic acid as impurity). Of nine solvents tested, only the use of acetone, dichloromethane, methyl tert-butyl ether, and acetone:petroleum ether (1:1, v/v) resulted in recoveries below 100% and acetone:methyl tert-butyl ether (1:1, v/v) was chosen as suited extraction solvent. An appropriate GC capillary column and the application of mass-labelled internal standards appeared to be essential for these analyses. Instrumental limits of detection of <0.2 pg (dimethylperfluoroocatanesulfonamide, ethyl-[(2)H(5)]perfluorooctanesulfonamide, methyl-[(2)H(3)]perfluorooctanesulfonamide) to 8.2 pg (perfluorooctanesulfonamide) and LOQ of 0.4 pg (dimethylperfluoroocatanesulfonamide, ethyl-[(2)H(5)]perfluorooctanesulfonamide, methyl-[(2)H(3)]perfluorooctanesulfonamide) to 16.4 pg (perfluorooctanesulfonamide) were determined.

Source apportionment of organic pollutants of a highway-traffic-influenced urban area in Bayreuth (Germany) using biomarker and stable carbon isotope signatures.

Traffic- and urban-influenced areas are prone to enhanced pollution with products of incomplete combustion of fossil fuels and biomass such as black carbon or polycyclic aromatic hydrocarbons (PAHs). Black carbon is composed of aromatic and graphitic structures and may act as a carrier for pollutants such as PAHs and heavy metals. However, little is known about possible contributions of traffic-derived black carbon to the black carbon inventory in soils. Similar uncertainties exist regarding the contribution of different pollutant sources to total PAH and black carbon contents. Therefore, the objective of this study was to quantify the importance of traffic pollution to black carbon and PAH inventories in soils. PAH contamination of soils adjacent to a major German highway in the urban area of Bayreuth with about 50,000 vehicles per day was in the same order of magnitude compared to highway-close soils reported in other studies. Using molecular (black carbon and PAHs) and compound-specific stable carbon isotope evidence (PAHs) it was demonstrated that this contamination originated not only from automobile exhausts, here primarily diesel, but also from tire abrasion and tailpipe soot which significantly contributed to the traffic-caused black carbon and PAH contamination. Low molecular weight PAHs were more widely transported than their heavy molecular counterparts (local distillation), whereas highway-traffic-caused black carbon contamination was distributed to at least 30 m from the highway. On the other hand, urban fire exhausts were distributed more homogeneously among the urban area.

Long-term change of polycyclic aromatic hydrocarbon deposition to peatlands of eastern Canada.

To date, studies about historic PAH (polycyclic aromatic hydrocarbons) deposition at a regional scale have rarely been published. To address this research gap, we sampled 17 ombrotrophic peatlands across eastern Canada. The peat cores from hollows were dated with 210Pb for the period of about 1850-2000 and analyzed fortheir PAH concentration, so PAH deposition could be reconstructed. Peat samples were extracted by accelerated solvent extraction (ASE). The extracts were purified by column chromatography with aluminum oxide and silica gel. PAH were measured by gas chromatography-tandem mass spectrometry (GC-MS/MS). Overall reconstructed deposition rates of sigma-11 PAH ranged from 4 to 1432 microg m(-2) year(-1). Three different long-term trends in PAH deposition could be distinguished: sites with two separated periods of maximum PAH deposition, sites with one period of maximum PAH deposition, and sites with no clearly separated period of maximum PAH deposition. Increasing PAH depositions were caused by rapid industrialization accompanied by extensive use of fossil fuels; decreasing PAH depositions were caused by substitution of these fuels and movements of PAH emitting industry to different regions. At all sites either phenanthrene (20-60%) or benzo[b+k]fluoranthene (10-40%) was the predominant PAH. Detailed analysis of three bogs suggested that combustion of coal and vehicle exhausts mainly contributed to the peat PAH burden. The temporal trends of PAH deposition indicated that increases in the PAH deposition rates followed the industrial development in Canada, particularly in the periods 1880-1910 and 1940-1960. Recent abatement efforts were reflected in decreased PAH deposition rates to about 15% of the maximum.