Roland Kallenborn

Atmospheric monitoring of organic pollutants in the Arctic under the Arctic Monitoring and Assessment Programme (AMAP): 1993-2006.

Continuous and comparable atmospheric monitoring programs to study the transport and occurrence of persistent organic pollutants (POPs) in the atmosphere of remote regions is essential to better understand the global movement of these chemicals and to evaluate the effectiveness of international control measures. Key results from four main Arctic research stations, Alert (Canada), Pallas (Finland), Storhofdi (Iceland) and Zeppelin (Svalbard/Norway), where long-term monitoring have been carried out since the early 1990s, are summarized. We have also included a discussion of main results from various Arctic satellite stations in Canada, Russia, US (Alaska) and Greenland which have been operational for shorter time periods. Using the Digital Filtration temporal trend development technique, it was found that while some POPs showed more or less consistent declines during the 1990s, this reduction is less apparent in recent years at some sites. In contrast, polybrominated diphenyl ethers (PBDEs) were still found to be increasing by 2005 at Alert with doubling times of 3.5 years in the case of deca-BDE. Levels and patterns of most POPs in Arctic air are also showing spatial variability, which is typically explained by differences in proximity to suspected key source regions and long-range atmospheric transport potentials. Furthermore, increase in worldwide usage of certain pesticides, e.g. chlorothalonil and quintozene, which are contaminated with hexachlorobenzene (HCB), may result in an increase in Arctic air concentration of HCB. The results combined also indicate that both temporal and spatial patterns of POPs in Arctic air may be affected by various processes driven by climate change, such as reduced ice cover, increasing seawater temperatures and an increase in biomass burning in boreal regions as exemplified by the data from the Zeppelin and Alert stations. Further research and continued air monitoring are needed to better understand these processes and its future impact on the Arctic environment.

Arctic Alpine ecosystems and people in a changing environment

Arctic-Alpine Ecosystems and People in a Changing Environment - Introduction.- Integrated aspects of environmental change: Climate change, UV radiation and long range transport of pollutants.- An environment at risk: Arctic indigenous peoples, local livelihoods and climate change.- Climate change and ecosystem response.- Climate variation in the European sector of the Arctic: Observations and scenarios.- Impact of climate change on arctic and alpine lakes: Effects on phenology and community dynamics.- Changes in growing season in Fennoscandia 1982-1999.- Northern climates and woody plant distribution.- Topographic complexity and terrestrial biotic response to high-latitude climate change: Variance is as important as the mean.- The flow of Atlantic water to the Nordic Seas and Arctic Ocean.- Climate variability and possible effects on arctic food chains: The role of Calanus.- Adjustment to reality: Social responses to climate changes in Greenland.- UV radiation and biological effects.- Factors, trends and scenarios of UV radiation in arctic-alpine environments.- Effects of enhanced UV-B radiation and epidermal UV screening in arctic and alpine plants.- Effects of UV radiation in arctic and alpine freshwater ecosystems.- Climate control of biological UV exposure in polar and alpine aquatic ecosystems.- Effects of UV radiation on seaweeds.- Climate and ozone change effects on UV-radiation and health risks.- Long range pollutants transport and ecological impacts.- Contaminants, global change and cold regions.- Modeling of long-range transport of contaminants from potential sources in the Arctic Ocean by water and sea ice.- Long-term atmospheric contaminant monitoring for the elucidation of airborne transport processes into polar regions.- Levels and effects of persistent organic pollutants in arctic animals.- Arctic health problems and environmental challenges in Greenland.

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).

Occurrence of selective serotonin reuptake inhibitors in sewage and receiving waters at Spitsbergen and in Norway

A method for the determination of five selective serotonin reuptake inhibitors (citalopram, sertraline, fluoxetine, fluvoxamine and paroxetine) and four of their metabolites (desmethylcitalopram, didesmethylcitalopram, norfluoxetine and desmethylsertraline) in seawater and sewage influents and effluents, has been developed and validated. The method is based on a three-phase hollow-fibre supported liquid phase microextraction of 1.1L samples, followed by high performance liquid chromatography with electrospray ionization and mass spectrometric detection. The detection limits varied between 17 pg/L (citalopram) and 618 ng/L (desmethylsertraline), and the quantification limits between 57 pg/L (citalopram) and 4.1 ng/L (desmethylsertraline). Sampling was done from February to August in 2007 on three different locations with dissimilarities concerning waste water treatment procedures. No significant difference in SSRI cleansing efficiency between merely sieving (Langnes STP, Tromsø) and a more advanced sewage treatment (VEAS STP, Oslo) was seen. All the investigated compounds are present in all waste water samples from these STPs, and a total concentration of SSRIs and metabolites up to 840 ng/L has been found. Untreated sewage samples have been collected in the small town Longyearbyen at Spitsbergen. Despite few inhabitants (2000), it was still possible to find traces of SSRIs in the waste water. In Tromsø and Longyearbyen the waste water is discharged into the sea, therefore seawater samples have been collected close to the outlets. The results show higher concentrations of SSRIs outside Longyearbyen than Tromsø, possibly due to the stronger tidal currents around Tromsø. However, the concentrations are quite low, not exceeding total concentrations of 3 ng/L.

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.

Organochlorines in egg samples from Norwegian birds of prey: Congener-, isomer- and enantiomer specific considerations

The content of chlorinated persistent organic pollutants was determined in a total of 44 egg samples from 8 different raptor species collected throughout Norway in the period 1991-1997. The content of 8 chlorinated bornanes, 9 chlorinated pesticides, and 15 polychlorinated biphenyl congeners (PCB) were determined. The highest average concentrations for PCB were found for eggs from White-tailed Sea Eagle and Peregrine Falcon (average sum PCB concentration: 8.9 and 9.1 microg/g wet weight (w.w.), respectively). Merlin and Sparrowhawk eggs were the highest contaminated with chlorinated pesticides (average sum pesticide concentration: 3.0 and 4.3 microg/g w.w.). For the first time, the content of chlorobornanes was determined in Norwegian birds of prey eggs. However, only minor contamination compared to PCBs and conventional chlorinated pesticides was found. The highest sum concentration was determined for White-tailed Sea Eagle eggs (0.09 microg/g w.w.). No chlorobornane contamination was found in Osprey and Merlin eggs. No spatial and regional specific trends or pattern distribution were found for organochlorine contamination in the egg samples analysed. In order to gain information about enantiomer specific bioaccumulation and biotransformation capacity of the organism, enantioselective analyses was performed for the chiral contaminants trans-chlordane, oxy-chlordane and the chlorobornane B9-1679 (Parlar #50). Indications for species-dependent deviation from the racemic distribution (enantiomeric ratio = 1) were found. Peregrine Falcon and Merlin eggs were characterised with an extremely high enantiomeric excess of the (-)-trans-chlordane (enantiomeric ratio (ER) <0.01). For Golden Eagle, Goshawk and Sparrowhawk eggs, the ERs were between 0.1 and 0.22 demonstrating also here that the (-)-trans-chlordane was the most abundant enantiomer. For the distribution of oxy-chlordane and B9-1679 enantiomers no species-dependent differences were found. For all species the ER values between 0.3 and 0.8 were determined. Thus, also for oxy-chlordane and B9-1679, the (-)-enantiomers are the most dominating stereoisomers in the birds of prey eggs analysed.

Sources and transport of persistent pollutants to the Arctic.

During the last two decades the importance of long-range transport as a contaminant source for the pristine Arctic regions has been proven. Models are developed in order to predict spatial, seasonal and structural dependent patterns in the distribution of antropogenic pollutants. The most accepted theory today describes the transport of semi-volatile persistent organic pollutants as a temperature and weather dependent repeated deposition and remobilization process between the atmosphere and the ocean and land surface, with a final deposition in the cold northern region. Results also indicate possible new local sources of pesticides in the European Arctic in addition to the long-range transport from more temperate areas.

Temporal Trends in Atmospheric Heavy Metal and Organochlorine Concentrations at Zeppelin, Svalbard

Abstract As a part of the national Norwegian monitoring program, long-term surveys of contaminants have been carried out at the Zeppelin atmospheric research station (Ny-Ålesund, Svalbard ) since the early 1990s. In the present study, all obtained data have been summarized and analyzed in order to review possible temporal trends for selected atmospheric contaminants at Svalbard. The following heavy metals were determined in aerosols: Pb, Cd, Hg, Cu, Zn, Cr, Ni, Co, Mn, V, and As. Only Ni showed a decreasing trend in the concentrations over the past decade. Organochlorine compounds in combined gaseous phase and aerosol samples evaluated were the following: α-HCH (hexachlorocyclohexane), γ-HCH, HCB (hexachlorobenzene), and sum-DDT (dichlorodiphenyltrichloroethane). Only those organochlorines exhibiting significant statistically confirmed temporal trends were chosen for the present comparison. Thus, although polychlorinated biphenyls (PCBs) as well as chlordanes are routinely monitored at the Zeppelin station, they were not considered for the here presented report because no clear trends were determined. Therefore all, but sum-DDT showed significant decreasing trends, correlating well with the national and international governmental regulations.

Enantiomer selective separation of toxaphene congeners isolated from seal blubber and obtained by synthesis

Abstract Stationary phases based on dimethyl-t-butylsilylated heptakis(2,3,6-tri-O-methyl)-β-cyclodextrin diluted with different polysiloxanes were developed for the enantiomer separation of chiral toxaphene congeners by high resolution gas chromatography (HRGC). They allowed to determine the enantiomer ratio of an octa- and nonachloro congener isolated from seal blubber. The found ratios of 1,024 and 1,059 were very close to those of the racemates and indicate that enantiomer selective metabolisation is not significant in seals. Furthermore, the enantiomer separation of 11 racemic toxaphene congeners obtained by synthesis was also performed. Two of them had the same retention times as the isolated congeners on 3 or 5 stationary phases, respectively, and similar negative ion chemical ionisation mass spectra. First attempts are made to explain differences in the observed enantiomer separations by the steric structure of the congeners. In addition, general aspects and difficulties of enantiomer selective separations by HRGC are discussed.

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.