Martin Schlabach

Ambient air levels and atmospheric long-range transport of persistent organochlorines to Signy Island, Antarctica

Levels of persistent organic pollutants (POPs), such as polychlorinated biphenyls and pesticides have been determined in ambient air at Signy Island, Antarctica, over a period of 17 weeks. Mean concentrations for single polychlorinated biphenyls (0.02–17 pg/m3), for chlordanes (0.04–0.9 pg/m3), DDT compounds (0.07–0.40 pg/m3) and γ-hexachlorocyclohexane (HCH, 22 pg/m3) were comparable to those in Arctic air. However, α-HCH levels were approximately one order of magnitude lower. Compared to the Arctic, differences were also observed in the concentration ratios of α-/γ-HCH and chlordane compounds. Two possible atmospheric long-range transport episodes from South America were found by comparing 10-day back trajectories with observed concentration changes. The lower limits of determination (LOD) were mainly governed by the field blanks. They were satisfactory for the most volatile PCBs. However, many concentrations for DDT and chlordane compounds were below the LODs (range 0.1–1 pg/m3) or even the instrumental detection limit (0.01–0.03 pg/m3).

Investigation on Per- and Polyfluorinated Compounds in Paired Samples of House Dust and Indoor Air from Norwegian Homes

Per- and polyfluorinated compounds (PFCs) have been found to be ubiquitously distributed in human populations, however the sources of human exposure are not fully characterized. A wide range of PFCs were determined in paired samples of indoor air and dust from 41 Norwegian households. Up to 18 ionic and 9 neutral PFCs were detected. The concentrations found are comparable to or lower than what has previously been reported in North America, Europe, and Asia. The highest median concentrations in dust were observed for perfluorohexanoic acid (28 ng/g), perfluorononanoic acid (23 ng/g), perfluorododecanoic acid (19 ng/g), and perfluorooctanoic acid (18 ng/g). However, perfluoroalkyl sulfonic acids (PFSAs) were also frequently detected. Fluortelomer alcohols were the most prominent compounds found in indoor air, with median concentrations for 8:2 fluortelomer alcohol, 10:2 fluortelomer alcohol, and 6:2 fluortelomer alcohol of 5173, 2822, and 933 pg/m(3) air, respectively. All perfluoroalkyl sulfonamides and sulfonamidoethanols (FOSA/FOSEs) were detected in more than 40% of the air samples. For the first time, significant positive correlations (p < 0.05) between PFSAs in house dust and FOSA/FOSEs in the indoor air have been shown, supporting the hypothesis that FOSA/FOSEs may be transformed to PFSAs. Further, we found the age of the residence to be a predictor of PFC concentrations in both indoor air and house dust. These results are important for estimating the exposure to PFCs from the indoor environment and for characterization of exposure pathways.

Contaminants in Svalbard polar bear samples archived since 1967 and possible population level effects

Blood plasma samples were collected in 1967 from 32 polar bears (Ursus maritimus) in eastern Svalbard. These samples were stored frozen until 2001 and then analyzed for 33 polychlorinated biphenyls (PCB), two toxaphene congeners, DDTs, chlordanes (CHL), hexachlorobenzene, hexachlorocyclohexanes (HCHs), and polybrominated flame retardants (biphenyls and diphenyl ethers). The 1967 pollutant levels were compared with values from 1993 to 1994 for adult females and adult males to obtain insights into the historical development of pollution in the Norwegian Arctic. Differences in the OC levels measured between 1967 and 1993-1994 ranged from a decrease (PCB 187 and p,p-DDE) to unchanged in both sexes (PCBs 105, 118, 209, and HCH) to an increase in females (PCBs 99, 128, and CHL), to increases in both sexes (PCBs 138, 153, 156, 157, 170, 180, 194, and 206). The maximum change was a nine-fold increase in PCB 157 in adult females. Changes from 1967 to 1993-1994 in contaminant pattern expressed relative to PCB 153 could be explained by a combination of selective metabolism and accumulation of organochlorines in polar bears and temporal changes in the contaminant mixture being transported to the Arctic. Harvest of polar bears in Svalbard ended in 1973 and it appears that most pollutant levels were increasing at the same time that the population was expected to recover from over-harvest. The mean age of adult females in the Svalbard population was similar to other populations where pollution levels are lower but harvest is intense. Females with cubs-of-the-year > or =16 years old are uncommon in the population for unknown reasons. The impacts of contaminants on the Svalbard polar bear population are inconclusive but there are suggestions of contaminant-related population level effects that could have resulted from reproductive impairment of females, lower survival rates of cubs, or increased mortality of reproductive females.

Gas chromatographic determination of synthetic musk compounds in Norwegian air samples

A new method is described for the simultaneous analysis of nitro and polycyclic musks in air samples. Additional considerations are given to the aspects of sample preparation and blank problems. For the first time concentration levels of synthetic musks in selected Norwegian air samples were determined. In a preliminary investigation using ambient air samples prepared for the determination of persistent organic pollutants, musk xylene concentrations were between 8 and 19 pg/m3. A new sample preparation for the simultaneous analysis of polycyclic and nitro musks is presented. Both GC-electron impact (EI) MS and GC-negative ion chemical ionisation (NICI) MS were compared as detection methods. GC–EI-MS is to be preferred for the determination of synthetic musks since GC–NICI-MS is not sensitive enough for the determination for polycyclic musks. Blank problems occurred which have to be carefully considered during the whole work-up procedure. One indoor air sample was taken in the laboratory where the clean-up of the samples took place to evaluate laboratory air contamination. A concentration for 1,3,4,6,7,8-hexahydro-4,6,6,7,8,8-hexamethyl-cyclo[g]-2-benzopyrane of 2470 pg/m3 was found using gas chromatographic separation coupled with mass spectrometric detection in the electron impact mode (GC–low-resolution EI-MS). A set of four ambient air samples taken nearby the institute facilities was analysed for both nitro and polycyclic musks. For polycyclic musks, concentrations up to 130 pg/m3 (GC–EI-MS) were determined and for musk xylene a concentration maximum in ambient air samples 54 pg/m3 (low resolution EI-MS) was found. Critical considerations about laboratory contamination, clean-up and analysis of ambient air samples are given.

Ambient air levels of persistent organochlorines in spring 1992 at Spitsbergen and the Norwegian mainland : comparison with 1984 results and quality control measures

Abstract Ambient air levels of polychlorinated pesticides such as hexachlorocyclohexanes (HCH) and chlordanes as well as polychlorinated biphenyls and hexachlorobenzene were determined at NyA˚lesund (Spitsbergen) and at three stations on the Norwegian mainland in spring 1992. The analytical method based on quantification by negative ion chemical ionization mass spectrometry was considerably improved compared to the last measuring campaign in 1984. Furthermore, a congener-specific quantification of PCB was included, and a comprehensive quality assurance system was introduced to control the reliability of the method in the sub-pg to pg/m 3 range. It consisted of frequent blank determinations, calculation of recovery rates for each sample, and additional quantification of selected samples by an independent method (high resolution mass spectrometry). Agreement between the average concentrations of both methods was generally within 2–20%, depending on the concentration range. For most compounds, the field blank was about a factor of 10 lower than the lowest measured value. Significant long-range transport episodes for γ-HCH, but not for α-HCH, were observed in spring 1992. Back trajectories identified different parts of Europe as source areas. A concentration gradient was found for PCB, with concentrations more than 10 times higher in southern Norway. Compared to 1982–1984, the data of 1992 indicate a decrease in α-HCH and chlordane levels and possibly an increase in γ-HCH.

Occurrence and Seasonality of Cyclic Volatile Methyl Siloxanes in Arctic Air

Cyclic volatile methyl siloxanes (cVMS) are present in technical applications and personal care products. They are predicted to undergo long-range atmospheric transport, but measurements of cVMS in remote areas remain scarce. An active air sampling method for decamethylcyclopentasiloxane (D5) was further evaluated to include hexamethylcyclotrisiloxane (D3), octamethylcyclotetrasiloxane (D4), and dodecamethylcyclohexasiloxane (D6). Air samples were collected at the Zeppelin observatory in the remote Arctic (79° N, 12° E) with an average sampling time of 81 ± 23 h in late summer (August-October) and 25 ± 10 h in early winter (November-December) 2011. The average concentrations of D5 and D6 in late summer were 0.73 ± 0.31 and 0.23 ± 0.17 ng/m(3), respectively, and 2.94 ± 0.46 and 0.45 ± 0.18 ng/m(3) in early winter, respectively. Detection of D5 and D6 in the Arctic atmosphere confirms their long-range atmospheric transport. The D5 measurements agreed well with predictions from a Eulerian atmospheric chemistry-transport model, and seasonal variability was explained by the seasonality in the OH radical concentrations. These results extend our understanding of the atmospheric fate of D5 to high latitudes, but question the levels of D3 and D4 that have previously been measured at Zeppelin with passive air samplers.

Determination of Q1, an unknown organochlorine contaminant, in human milk, Antarctic air, and further environmental samples

Q1, an organochlorine component with the molecular formula C(9)H(3)Cl(7)N(2) and of unknown origin was recently identified in seal blubber samples from the Namibian coast (southwest of Africa) and the Antarctic. In these samples, Q1 was more abundant than PCBs and on the level of DDT residues. Furthermore, Q1 was more abundant in seals from the Antarctic than the Arctic. To prove this assumption, gas chromatography-electron-capture negative ion mass spectrometry (GC/ECNI-MS), which is sensitive and selective for Q1, allowed for screening of traces of Q1 even in samples with particularly high levels of other organochlorine contaminants. Q1 was isolated by high-performance liquid chromatography (HPLC) from a skua liver sample. A 1:1 mixture with trans-nonachlor in electron-capture detectors (ECDs) was used to determine the relative response factor with ECNI-MS. The ECNI-MS response of Q1 turned out to be 4.5 times higher than that of trans-nonachlor in an ECD. With GC/ECNI-MS in the selected ion-monitoring mode, four Antarctic and four Arctic air samples were investigated for the presence of Q1. In the Antarctic air samples, Q1 levels ranged from 0.7 to 0.9 fg/m(3). In Arctic air samples, however, Q1 was below the detection limit (<0.06 fg/m(3) or 60 ag/m(3)). We also report on high Q1 levels in selected human milk samples (12-230 microg/kg lipid) and, therefore, suggested that the unknown Q1 is an environmental compound whose origin and distribution should be investigated in detail. Our data confirm that Q1 is a bioaccumulative natural organochlorine product. Detection of a highly chlorinated natural organochlorine compound in air and human milk is novel.

Sources and pathways of persistent polychlorinated pollutants to remote areas of the North Atlantic and levels in the marine food chain: a research update

A summary is given of research conducted by our laboratory since 1991 on the dispersion and pathways of persistent organochlorines (POCs) to remote regions of the Northern North Atlantic. This review includes data not previously published and an overall interpretation of our results. Levels of polychlorinated dibenzo-p-dioxins, dibenzofurans, biphenyls and pesticides in marine mammals and sediments from these areas are presented and discussed. Special attention is given to the levels of polychlorinated bornanes (toxaphene), to date the most heavily used insecticide worldwide. Finally, temporal trends are presented.

Per- and polyfluorinated compounds in house dust and indoor air from northern Norway – A pilot study

Polyfluorinated compounds (PFCs) are an extremely versatile class of compounds and are used in a variety of consumer applications and products. Recent studies have suggested that PFCs in indoor air and dust could act as sources of human exposure and outdoor air contamination. This study presents method development and analysis of a wide range of PFCs in dust and air using active sampling techniques with commercially available sampling equipment (forensic nozzles with filter housings for dust collection and polyurethane foam (PUF)-XAD(2)-PUF sandwich-tubes for air sampling) using both liquid and gas chromatography mass spectrometry. The developed method was validated and tested for applicability to analyze dust and air samples at both low and high concentrations (0.5 ng and 25 ng per analyte per air sample, respectively). Samples from private households and an office building were analyzed to explore differences in distribution patterns and concentrations. Perfluorooctane sulfonate, perfluorodecane sulfonate, perfluoroheptanoate, perfluorooctanoate and perfluorononanoate were observed in all samples of dust from private households, in the range from 1 to 80.1 ng g(-1). Fluorotelomer alcohols (FTOHs) were the predominant PFCs in indoor air samples with ∑FTOHs ranging between 4.7 and 17.9 ng m(-3). The concentrations found in the present study are generally lower than those previously reported. This variation may be due to differences associated with geographical locations and lifestyles. However, use of different sampling techniques and strategies among studies can introduce large variations in PFC concentration found, making direct comparisons challenging.

Spatial patterns of polybrominated diphenyl ethers (PBDEs) in mosses, herbivores and a carnivore from the Norwegian terrestrial biota

The widespread occurrence of polybrominated diphenyl ethers (PBDEs) in the environment has attracted considerable attention, leading to concerns about the extent and magnitude of wildlife and human exposure. In this work, we focus on the occurrence and fate of PBDEs in a Norwegian air-plant-herbivore-carnivore system. Specifically, we have analysed for PBDEs in moss, livers from various terrestrial herbivores (moose, grouse, and European roe deer) and, for the first time, livers from the top predator lynx. The samples were collected from different sites and time periods (1990-2004) to identify possible spatial and temporal trends in contaminant levels and patterns. The general finding was that PBDEs were found in all (biotic) samples, although at lower concentrations than previously observed in mammals from the marine environment. The PBDE levels in the herbivores ranged from less than 0.5 ng/g lipid weight to 9.4 ng/g lipid weight as the highest. The median PBDE concentration in lynx was approximately one order of magnitude higher than in the herbivores. In the lynx samples there was a predominance of BDE-153 whereas BDE-47 and 99 dominated in the herbivores. This probably reflects different bioaccumulation properties or metabolic transformation processes of the BDE-congeners, and food choice. Levels of PBDEs in both moss and herbivores showed a general decline towards the northern parts of Norway. No clear temporal trends were observed. The PBDE levels observed in this study were low and are probably of limited toxicological significance.