Seabird guano is an efficient conveyer of persistent organic pollutants (POPs) to Arctic lake ecosystems.

Migratory seabirds have been linked to localized "hotspots" of contamination in remote Arctic lakes. One of these lakes is Lake Ellasjøen on Bjørnøya in the Barents Sea. Here we provide quantitative evidence demonstrating that even relatively small populations of certain seabird species can lead to major impacts for ecosystems. In the present example, seabird guano accounts for approximately 14% of the contaminant inventory of the Lake Ellasjøen catchment area, approximately 80% of the contaminant inventory of the lake itself, and is approximately thirty times more efficient as a contaminant transport pathway compared to atmospheric long-range transport. We have further shown that this biological transport mechanism is an important contaminant exposure route for ecosystems, responsible for POPs levels in freshwater fish that are an order of magnitude higher than those in Arctic top predators. Given the worldwide presence of seabird colonies in coastal marine areas where resources are also harvested by humans, this biological transport pathway may be a greater source of dietary contamination than is currently recognized with consequent risks for human health.

Brominated flame retardants and other organobromines in Norwegian predatory bird eggs.

A set of 62 unhatched eggs was collected from six different predatory bird species throughout Norway after incubation period was completed. They were analysed for PBDE, PBB, TBBP A and naturally occurring halogenated compounds. BDE 47, 99 and 153 were the dominating congeners, with species dependent PBDE patterns. BDE 153 was observed as the most abundant congener in eggs of peregrine falcon, golden eagle and merlin. The highest PBDE level (sum of nine congeners) was found in eggs of white-tailed sea eagle with up to 800ng/gww (median sumPBDE: 184ng/gww), followed by eggs of peregrine falcon and osprey (median sumPBDE: 155 and 105ng/gww, respectively). Golden eagle eggs showed the lowest concentration of all species (median sumPBDE: 3ng/gww). The levels in the peregrine falcon are similar to those found earlier in the Baltic region [Lindberg, P., Sellstrom, U., Haggberg, L., de Wit, C.A., 2004. Higher brominated diphenyl ethers and hexabromocyclododecane found in eggs of peregrine falcons (Falco peregrinus) breeding in Sweden. Environmental Science & Technology. 38 (1), 93-96]. The differences between species are not fully explainable, due to lack of data from the major food species. BB 101 and 153 were found in eggs of all investigated bird species. Especially in samples of white-tailed sea eagle, peregrine falcon and goshawk additional unknown penta- and hexabrominated biphenyls were detected. TBBP A was detected in all of eight eggs analysed sampled from four different bird of prey species. The naturally occurring halogenated compounds Q1, the dibromotrichloro monoterpene MHC-1, and 2,4,6-tribromoanisole (TBA) were detected in all of seven analysed samples except for one peregrine falcon egg.

Rapid changes in PCB and OC pesticide concentrations in arctic snow.

The short-term fate of polychlorinated biphenyl (PCB) and organochlorine (OC) pesticides in the surface snowpack was investigated by taking consecutive air and snow samples over a 12 day period at Tromsø in the Norwegian Arctic. A wide range in PCB and OC pesticide concentrations was observed in snow and was attributed to the systematic decrease in concentrations that occurred over the study period. For example, sigmaPCB concentrations ranged from 2500 to 300 pg L(-1) (meltwater) with a rapid decrease observed during the first 96 h. Rates of decline (ks) conformed to first-order kinetics, with similar rates observed for all compounds measured in this study (k5 = 0.01 +/- 0.001 h(-1)). Because the particle bound fraction accounted for <10% of the individual PCB and OC burden in the snow, then the fraction lost may be accounted for by desorption, following notable increases in snow density (and presumably, decreases in snow surface area). The fraction of chemical present in the fresh snow (phis) was found to be exponentially related to changes in snow density (deltarho). Relatively small increases in p following snowfall result in a large loss of sorbed chemical, presumably due to decreases in snow surface area. Later sampling of the same snow layer, but buried under fresh snowfall, revealed a notable increase in both PCB and OC concentrations. This would indicate a possible downward migration of these chemicals from the fresh snow into deeper snow layers, suggesting that re-emission of desorbed chemical from the interstitial pore spaces to the overlying atmosphere may be complicated by this process.

Polychlorinated naphthalenes in air and snow in the Norwegian Arctic: a local source or an Eastern Arctic phenomenon?

PCNs were measured in air and snow during separate field campaigns at Ny-Alesund (April 2001) and Tromsø (February/March 2003) in the Norwegian Arctic. Air concentrations ranged from 27 to 48 and 9 to 47 pg sigmaPCN m(-3) for Ny-Alesund (n=6) and Tromsø (n=10), respectively. These concentrations (including the tri-chlorinated naphthalenes) greatly exceeded concentrations previously measured in the Canadian Arctic, but did fall within the upper range of concentrations observed over the eastern Arctic Ocean and regional seas. Local sources appear to be affecting concentrations observed at both sites, with the presence of several hexa-chlorinated naphthalenes at Tromsø probably attributed to local/regional sources. Use of air mass back trajectories at Tromsø revealed that background air concentrations in the Norwegian Arctic are likely to range between <9 and 20 pg sigmaPCN m(-3) and that contemporary concentrations derived close to potential sources (i.e. arctic towns) may equal or exceed those of PCBs. The mean concentration in surface snow was 350 and 240 pg sigmaPCN L(-1) (meltwater) (or 0.014 and 0.01 pg g(-1) (snow)) at Ny-Alesund and Tromsø, respectively. The wide variation in concentrations observed between fresh snowfalls could be explained by different snow densities (as a surrogate of snow surface area), rather than attributed to varying air concentrations. A statistically significant inverse relationship was found between snow density and concentrations of tri- to penta-chlorinated homologues and compliments similar findings for the polychlorinated biphenyls (PCBs). This suggests that the vapour-sorbed quantity changes rapidly with snow ageing/compaction; with implications for the fate of these chemicals in the Arctic.

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.

Synthetic musks in the environment. Part 2: Enantioselective transformation of the polycyclic musk fragrances HHCB, AHTN, AHDI, and ATII in freshwater fish.

A method for the enantioselective separation of the chiral polycyclic musks HHCB, AHTN, AHDI, and ATII is presented. Eighteen fish samples (rudd, tench, crucian carp, eel) and one pooled zebra mussel sample from the pond of a municipal sewage treatment plant were investigated with regard to their concentrations and the enantiomeric ratios (ERs) of polycyclic musks. In addition, three water samples taken at the effluent of the sewage plant, as well as two water samples and two series of semipermeable membrane devices (SPMDs) consisting of six samples each from the pond were included in the present study. This comprehensive data set allowed a reliable evaluation of species-dependent metabolization processes. The pattern of the polycyclic musks in the chromatograms obtained by enantioselective gas chromatography seems to be typical of each species, like a fingerprint. The highest deviations from the racemic ER were found for trans-HHCB and trans-ATII in crucian carp with values of or below 0.1. Calculations showed that enantioselective transformation seems to be the most important process, resulting in the observed lower concentrations in crucian carp compared to tench. Consequences for a risk assessment are discussed.

Environmental fate of chlorinated bornanes estimated by theoretical descriptors.

Theoretical molecular descriptors have been calculated for 36 polychlorinated bornanes, the majority compound class of the insecticide Toxaphene. The results demonstrate that thermodynamic stability by the use of molecular structural energies can be used as a general parameter for persistence. Since these descriptors agree well with polychlorinated bornanes found in the environment, these compounds should be included as important indicator compounds in future trace analytical investigations of polychlorinated bornanes and also within experimental metabolism studies to investigate potential toxic metabolites. Reactivity descriptors such as electronaffinity, hardness, LUMO location and atomic charges may guide to potential chemical reactions like the dechlorination of polychlorinated bornanes in reductive environment. Further it is advised to use these descriptors and other new potential ones in combination with experimental degradation and toxicology studies to explore the relationship between molecular structure and biological effects of chlorobornanes.

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.

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.

Synthetic musks in environmental samples: indicator compounds with relevant properties for environmental monitoring.

Synthetic musks (nitro and polycyclic musks) are a group of chemicals offering a wide range of important properties for environmental monitoring programs. They are produced as odorous chemicals and added to a wide variety of perfumes, toiletry products and other household products. As such, they are directly applied in cosmetic products or in washed textiles to the human body in considerable concentrations and accumulate owing to dermal resorption. In addition, synthetic musks also enter the environment via waste water treatment. Several polycyclic musks are chiral. By using chiral gas chromatographic methods, it is possible to determine the enantiomeric ratio and assess their bioavailability. Although an comprehensive quality assurance program must be followed during the analysis of synthetic musks in environmental samples, the determination of these compounds is not very demanding and can be carried out by a standard analytical laboratory specialising in trace analysis of organic pollutants. Owing to the pheromone-like behavior of some synthetic musks, the induction of receptors in olfactory systems should be investigated. For HHCB (1,3,4,6,7,8-hexahydro-4,6,6,7,8,8-hexamethylcyclopenta[g]-2-benzopyran, e.g., Galaxolide), three-dimensional structural similarities with androstenone (5 alpha-androst-16-en-3-one), a mammalian steroid pheromone, were found, which support the hypothesis of HHCB as an artificial pheromone. Owing to their environmental abundance, their relation to human activities and their potential for pheromone-like environmental behavior, synthetic musks are especially valuable as future indicator chemicals for environmental monitoring.

Enantioselective and nonenantioselective degradation of organic pollutants in the marine ecosystem.

Enantiomeric ratios of 11 chiral environmental pollutants determined in different compartments of the marine ecosystem by chiral capillary gas chromatography and chiral high-performance liquid chromatography allow discrimination between the following processes: enantioselective decomposition of both enantiomers with different velocities by marine microorganisms (alpha-HCH, beta-PCCH, gamma-PCCH); enantioselective decomposition of one enantiomer only by marine microorganisms (DCPP); enantioselective decomposition by enzymatic processes in marine biota (alpha-HCH, beta-PCCH, trans-chlordane, cis-chlordane, octachlordane MC4, octachlordane MC5, octachlordane MC7, oxychlordane, heptachlor epoxide); enantioselective active transport through the "blood-brain barrier" (alpha-HCH); nonenantioselective photochemical degradation (alpha-HCH, beta-PCCH).

Chromatographic separation of marine organic pollutants.

A review and discussion of the chromatographic separation of marine organic pollutants is given, including sampling and clean-up procedures, fractionation and enrichment of marine pollutants, capillary gas chromatography (cGC) and high-performance liquid chromatography applying both classical and chiral stationary phases. The potential of multi-dimensional cGC for the analysis of marine organic trace pollutants is discussed for polychlorinated biphenyls (PCBs). The chromatographic separation of coplanar PCBs and of the enantiomers of chiral pollutants provides a further insight into the toxic potential of these marine organic pollutants.