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 vari-ability 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

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 RosaMassif (4455mabove sea level). The firn core encompasses the years 1997e2007. Firn core sections were analyzed by liquid chromatographyetandem mass spectrometry (PFASs) and gas chromatographyemass spectrometry (PBDEs). We detected 12 PFASs and 8 PBDEs in the firn samples. Perfluorobutanoic acid (PFBA; 0.3e1.8 ng L1) and perfluorooctanoic acid (PFOA; 0.2e0.6 ng L1) were the major PFASs while BDE 99 (<MQLe4.5 ng L1) and BDE 47 (n.d.e2.6 ng L1) were the major PBDEs. This study demonstrates the occurrence of PFASs and PBDEs in the European Alps and provides the first evidence that PFASs compositions may be changing to PFBA-dominated composition

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

Abstract 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)

Spatial patterns and temporal trends of trace elements in mosses from 1990 to 2020 in Germany

Abstract Background The accumulation of trace elements in mosses is used as an indirect measure of atmospheric deposition and an important complement to the techniques used to monitor the Geneva Air Pollution Convention. The aim of this paper is to quantify and map temporal and spatial trends of metal enrichment in mosses collected in Germany in 1990, 1995, 2000, 2005, 2015 and 2020. Collection and chemical analysis of the moss samples were carried out according to international guidelines. Results The analysis shows that since 1990, the median concentrations of As, Cd, Cu, Ni, Pb and Sb in the mosses have been decreasing significantly, with the with the highest decline of Pb (− 86%). This trend reversed in 2000 and 2005 and between 2015 and 2020 by increases in the concentrations of some trace elements. In the 2000 Moss Survey, higher concentrations were measured for Cd, Cu, Ni and Sb than in 2015, ranging from + 26% (Cu) to + 165% (Ni). For As and Pb, no significant changes can be observed in 2020 compared to 2015. The increase in metal concentrations in the mosses over the last five years does not correspond to the corresponding trends in reported metal emissions in Germany (2015–2020). In contrast, the long-term trends of the As, Cd, Cu, Ni and Pb concentrations measured in the mosses showed good overall correspondence with the emission trends in Germany (1990–2020). The long-term trends of the moss data are mostly weaker than those of the emission data. The spatial patterns of the temporal trends were mapped and discussed for As, Cd, Cu, Ni, Pb and Sb. Conclusions The study shows that for valid monitoring of atmospheric deposition, it is not enough to consider only emission data or the modelled deposition derived from these data. In this respect, the study provides one of many necessary contributions to the discussion on the extent to which analytes of current monitoring programmes are still relevant and up-to-date and whether there are new substances that are also relevant or even more relevant than existing analytes and to what extent this should be taken into account in designing future environmental monitoring

Influence of the Canopy Drip Effect on the Accumulation of Atmospheric Metal and Nitrogen Deposition in Mosses

Wet, dry, and occult atmospheric deposition may be modified by vegetation canopies. The aim of this study was to verify canopy drip effect studies conducted in 2012, in 2013, and in 2015/2016. For this purpose, 26 moss samples were taken at each of eight monitoring sites of the European Moss Survey 2020/2021 in Germany from a corresponding number of subplots, each representing the site categories &ldquo;under tree canopy&rdquo; and adjacent &ldquo;open land&rdquo;. The sampling, as well as the chemical analyses, of 12 metals (Al, As, Cd, Cr, Cu, Fe, Hg, Pb, Ni, Sb, V, Zn) and nitrogen (N) and the recording of sample- and site-describing metadata were conducted according to the ICP Vegetation experimental protocol. The results demonstrate an overall higher metal and nitrogen accumulation in moss samples of &ldquo;canopy&rdquo; sites compared to neighboring &ldquo;open land sites&rdquo; (grassland, heath). The ratios between the &ldquo;canopy&rdquo; and &ldquo;open land&rdquo; sites of 1.18 to 1.69 and significant correlations of r &gt; 0.8 in case of five elements agree well with corresponding values from samplings in 2012, 2013, and 2015/2016. These results should be used for modeling atmospheric deposition aiming at more realistic results. With regard to the question of whether, and to what extent, moss samples should preferably be taken from &ldquo;open land&rdquo; or &ldquo;canopy&rdquo; sites, the following can be concluded: The recommendations of ICP Vegetation with regard to the minimum distance to be maintained from trees and shrubs should not be interpreted to mean that &ldquo;open&rdquo; sites are fundamentally more suitable for moss sampling in Germany than, for example, clearings in forests. The mostly higher variability of the measured values compared to the &ldquo;canopy&rdquo; sites rather suggests that in the open country a much higher number of influencing factors could be significant for the element accumulation in mosses in addition to the background pollution through atmospheric deposition. This is also supported by the fact that the metal contents in the moss samples of the &ldquo;open&rdquo; sites can clearly exceed those of the neighboring &ldquo;canopy&rdquo; sites in individual cases. With regard to &ldquo;open&rdquo; land, grassland sites seem to be less suitable for moss sampling than bog and heathland sites. In grassland, moss occurrences are often sparser and/or cut short by meadow mowing, so that the removal of three-year shoots on grassland, as recommended by ICP Vegetation, must be replaced in places by one-year shoots. The comparatively higher state dynamics of grassland sites also make the resampling of moss at previously sampled sites more difficult

Chemicals of emerging concern in marine specimens of the German Environmental Specimen Bank

Background Descriptor 8 of the Marine Strategy Framework Directive (MSFD) (Directive 2008/56/EC) addresses the good environmental status with regard to pollution of marine waters by chemical contaminants. Commission decision (EU) 2017/848 lays down the criteria and methodological standards on good environmental status of marine waters. Member States, in regional or subregional cooperation, shall establish lists of relevant contaminants beside those already covered by the Water Framework Directive (WFD). To provide information on emerging contaminants in marine biota, the German Environmental Specimen Bank (ESB) has compiled data of blue mussels and eelpouts from coastal sites in the North and Baltic Seas. Substances identified by the International Council for the Exploration of the Sea (ICES) as of emerging concern for the marine environment have been used as a starting point. Results and conclusions The study presents data of 19 emerging flame retardants and degradation products, 40 per- and polyfluoroalkyl substances (PFAS) and three cyclic volatile methylsiloxanes (cVMS). Among the emerging flame retardants, only Dec 602 was detected in all samples of 2015. Dec 604, Cl10-antiDP, 1,5-DPMA, EH-TBB, PBEB, TBP-AE, BATE, BTBPE and HBBz were constantly < limit of quantification (LOQ). Time trends were barely detected. Legacy PBDE still dominates in most samples. PFAS concentrations were usually higher in samples from the North Sea sites compared to samples from the Baltic Sea. PFOS dominated in most samples. Increasing trends over time were detected for PFNA, PFDA and PFDoDA at the Baltic Sea site and for PFDA at one North Sea site. Concentrations of the cVMS D4, D5 and D6 were below the detection limit at the ESB sampling sites. Based on the results, it should be considered to include the emerging flame retardants DP and Dec 602 and the long-chain perfluoroalkyl substances PFNA, PFDA, PFUnDA and PFDoDA in a regular monitoring in the North and Baltic Seas

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 dry weight (dw)) followed by DPTE (91-1540 pg/g dw), BDE209 (<156-461 pg/g dw), and BDE47 (<27-505 pg/g dw) or DP (31-122 pg/g 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