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Polychlorinated biphenyls (PCBs) can be used as chemical sentinels for the assessment of anthropogenic influences on Arctic environmental change. We present an overview of studies on PCBs in the Arctic and combine these with the findings from ArcRisk-a major European Union-funded project aimed at examining the effects of climate change on the transport of contaminants to and their behaviour of in the Arctic-to provide a case study on the behaviour and impact of PCBs over time in the Arctic. PCBs in the Arctic have shown declining trends in the environment over the last few decades. Atmospheric long-range transport from secondary and primary sources is the major input of PCBs to the Arctic region. Modelling of the atmospheric PCB composition and behaviour showed some increases in environmental concentrations in a warmer Arctic, but the general decline in PCB levels is still the most prominent feature. 'Within-Arctic' processing of PCBs will be affected by climate change-related processes such as changing wet deposition. These in turn will influence biological exposure and uptake of PCBs. The pan-Arctic rivers draining large Arctic/sub-Arctic catchments provide a significant source of PCBs to the Arctic Ocean, although changes in hydrology/sediment transport combined with a changing marine environment remain areas of uncertainty with regard to PCB fate. Indirect effects of climate change on human exposure, such as a changing diet will influence and possibly reduce PCB exposure for indigenous peoples. Body burdens of PCBs have declined since the 1980s and are predicted to decline further.

The occurrence of PPCPs in macroalgae, barnacle and fish samples from contaminated coastal waters of the Saudi Red Sea is reported. Solvent extraction followed by solid phase extraction was applied to isolate the compounds, and their quantification was carried out by high performance liquid chromatography-tandem mass spectrometry. Atenolol, ranitidine, chlorpheniramine, DEET, and atrazine were detected in one or more macroalgae at

The photochemical fate of 16 pharmaceuticals and personal care products (PPCPs) found in the environment has been studied under controlled laboratory conditions applying a sunlight simulator. Aqueous samples containing PPCPs at environmentally relevant concentrations were extracted by solid-phase extraction (SPE) after irradiation. The exposed extracts were subsequently analysed by liquid chromatography combined with triple quadrupole mass spectrometry (HPLC-MS/MS) for studying the kinetics of photolytic transformations. Almost all exposed PPCPs appeared to react with a half-life time (τ 1/2 ) of less than 30 min. For ranitidine, sulfamethoxazole, diclofenac, warfarin, sulfamethoxazole and ciprofloxacin, τ 1/2 was found to be even less than 5 min. The structures of major photolysis products were determined using quadrupole-time-of-flight mass spectrometry (QToF) and spectroscopic data reported in the literature. For diclofenac, the transformation products carbazol-1-yl-acidic acid and 8-chloro-9H-carbazol-1-yl-acetic acid were identified based on the mass/charge ratio of protonated ions and their fragmentation pattern in negative electrospray ionization (ESI - -QTOF). Irradiation of carbamazepine resulted in three known products: acridine, carbamazepine-10,11-epoxide, and 10,11-dihydro-10,11-dihydroxy-carbamazepine, whereas acetaminophen was photolytically transformed to 1-(2-amino-5 hydroxyphenyl) ethenone. These photochemical products were subsequently identified in seawater or fish samples collected at sites exposed to wastewater effluents on the Saudi Arabian coast of the Red Sea.

The occurrence of selected pharmaceuticals and personal care products (PPCPs) and the pesticide atrazine were investigated in seawater samples collected from stations located at effluent dominated sites in the Saudi Arabian coastal waters of the Red Sea. PPCPs were analysed using solid phase extraction (SPE) followed by high performance liquid chromatography - tandem mass spectrometry (HPLC-MS/MS). A multi component method for the ultra-trace level quantification of 13 target PPCPs in Seawater was developed and validated for the here performed study. The method procedure is described in detail in the supplementary material section. 26 samples from 7 distinct locations (2 directly influenced by continuous sewage release) were chosen for the sampling of surface seawater. Based upon local sales information, 25 target substances (20 PPCPs, 4 pesticides and 1 stimulant) were chosen for the here reported method development. Thirteen PPCPs were detected and quantified in a total of 26 seawater samples. Metformin, diclofenac, acetaminophen, and caffeine were identified as the most abundant PPCPs, detected in maximum concentration higher than 3 μg/L (upper quantification limit for the here developed method). Concentrations were in the range of 7- >3000 (metformin), 3000 ng/L (caffeine). The contribution of direct sewage release on the PPCP levels detected was obvious, the target PPCPs were detected in the Al-Arbaeen and Al-Shabab coastal lagoons in high concentrations due to the low water exchange with the open sea and still ongoing sewage releases in the lagoons. Also, substantial amounts of antibiotics were detected in all samples. Levels and distribution profile of the detected PPCPs revealed high level release rates and give raise to concern on potential environmental risks associated with the here document long term exposure on the fragile coastal marine environment of the region but particularly in the nearby protected coral reef environment outside the harbour region of Jeddah., (Copyright © 2017 Elsevier Ltd. All rights reserved.)

Perfluorinated alkylated substances (PFASs) are today considered persistent, toxic, and bioaccumulative contaminants. Perfluorooctansulfonate (PFOS) and perfluorooctanoic acid (PFOA) are currently listed as priority substances under the UNEP global convention for the regulation of POPs. A previous study reported higher levels of PFASs in pine needles near ski areas. Their application as stain repellents in modern outdoor clothes and in ski waxes is assumed to be a potential source. Pine trees (Pinus mugo in Slovakia and Pinus sylvestris in Norway) were chosen for sampling in ski resorts. Relative distributions, overall concentrations, trend estimates, elevation patterns, and distance from primary sources were assessed. PFOA was the predominant PFAS constituent in pine needles from Slovakia (8-93%). In Norway, the most-abundant PFAS was perfluorobutanoic acid (PFBA: 3-66%). A difference in product composition (particularly in ski waxes) and differences in Norwegian and Slovakian regulations are considered to be the primary reason for these differences. Open application of PFOA in industry and products has been banned in Norway since 2011. The replacement of PFOA with short-chain substitutes is thus considered the reason for the observed pattern differences in the analyzed pine needles. Regular monitoring and screening programs are recommended.

Concentration and enantiomeric fractions (EFs) of chiral chlorinated pesticides (α-hexachlorocyclohexane (α-HCH), trans-, cis- and oxychlordane) were determined in Arctic zooplankton, mainly Calanus spp. collected in the period 2007-11 from Svalbard fjords and open pack-ice. The temporal and spatial enantiomer distribution varied considerably for all species and chiral pesticides investigated. An overall enantiomeric excess of (+)-oxychlordane (EF 0.53-0.86) were observed. Cis-chlordane was close to racemic (EF 0.46-0.55), while EF for trans-chlordane varied between 0.29 and 0.55, and between 0.38 and 0.59 for α-HCH. The biodegradation potential for trans-chlordane was higher compared to cis-chlordane. The comprehensive statistical evaluation of the data set revealed that the EF distribution of α-HCH was affected by ice cover to a higher extent compared to cis-chlordane. Potential impact from benthic processes on EFs in zooplankton is an interesting feature and should be further investigated. Enantiomeric selective analyses may be a suitable tool for investigations of climate change related influences on Arctic ecosystems., (Copyright © 2014 Elsevier Ltd. All rights reserved.)

In this study, contamination levels were determined for polychlorinated biphenyls (PCBs), polybrominated diphenyl ethers (PBDEs) and perfluorinated alkylated substances (PFASs) in traditional Greenland seafood items, such as raw and smoked fish fillet (salmon and halibut), whale and seal meat and narwhal mattak (skin and blubber). The daily intake of PCBs, PBDEs and PFASs through traditional seafood items in Greenland was assessed. Based on the presented levels of contaminants, in combination with earlier food intake studies, suggests that the daily exposure was below the tolerable daily intake threshold for all compounds. BDE-47 was the only PBDE-congener detected in all food items, except in smoked halibut. The levels of BDE-47 varied from < LOD in smoked halibut up to 18 ng/g lw in narwhal mattak and 21 ng/g lw in whale beef. ∑PCB were lowest in smoked halibut (37 ng/g lw) and highest in narwhal mattak with 1,146 ng/g lw. Perfluorooctane sulfonate (PFOS) was the most common of the PFASs. However, ΣPFASs were below detection limits in most fish fillet samples, and varied from 2.9 ng/g ww in whale beef to 13.5 ng/g ww in seal beef. The present study shows that the exclusion from the diet of local food items such as intestines and blubber have a strong positive effect for the reduction of POPs levels in food, without a reducing the health benefits of traditional food intake considerably.

Enantiomeric fractions (EF) are today considered a powerful tool to elucidate selective uptake processes of chiral contaminants in biota. In this study, concentration levels and EF were determined by gas chromatograph-mass spectrometer (GC/MS) for α-hexachlorocyclohexane (α-HCH) and trans-, cis-, and oxychlordane in selected Greenlandic traditional food items, collected at the local market in Nuuk in 2010. The food items selected were raw and smoked fish (salmon and halibut, n = 6), whale meat (n = 8), seal meat (n = 2) and narwhal mattak (skin and blubber, n = 6). The EF were nonracemic (≠0.5) for all samples except for α-HCH in narwhal, trans-chlordane in whale and smoked salmon, and cis- and oxychlordane in seal. The EF for α-HCH were significant for all fish samples, but not for mammalian samples. Data indicate that different uptake and/or transformation mechanisms may be responsible for nonracemic distributions of chiral pesticides in mammals and fish species analyzed. There were no general enantiomer-selective transformation/accumulation trends found for chlordanes. Data indicate that enantiomer-specific properties are an important prerequisite for interaction of chiral contaminant with internal metabolic processes. However, marked differences within these groups were identified. The EF in ringed seals were racemic for most of the analyzed pesticides (i.e., chlordanes). However, narwhal were characterized by nonracemic EF for all chiral pesticides analyzed. Median levels of α-HCH ranged from 2 to 24 ng/g lw and from 15.1 to 626.6 ng/g lw for trans-nonachlor, with lowest levels observed in smoked salmon and highest levels in narwhal mattak. This study confirmed that concentration levels of analyzed pesticides in the investigated food items were below the tolerable daily intake (TDI) threshold.

The effect of climate change on the global distribution and fate of persistent organic pollutants (POPs) is of growing interest to both scientists and policy makers alike. The impact of warmer temperatures and the resulting changes to earth system processes on chemical fate are, however, unclear, although there are a growing number of studies that are beginning to examine these impacts and changes in a quantitative way. In this review, we examine broad areas where changes are occurring or are likely to occur with regard to the environmental cycling and fate of chemical contaminants. For this purpose we are examining scientific information from long-term monitoring data with particular emphasis on the Arctic, to show apparent changes in chemical patterns and behaviour. In addition, we examine evidence of changing chemical processes for a number of environmental compartments and indirect effects of climate change on contaminant emissions and behaviour. We also recommend areas of research to address knowledge gaps. In general, our findings indicate that the indirect consequences of climate change (i.e. shifts in agriculture, resource exploitation opportunities, etc.) will have a more marked impact on contaminants distribution and fate than direct climate change.

A pilot study is presented evaluating selected chlorinated pesticides as chemical tracers for water masses in a sub-Arctic fjord system (Godthåbsfjord, western Greenland). Polyoxymethylene (POM) based passive water samplers were deployed during summer-autumn 2010. The levels of the analysed chlorinated pesticides in the fjord surface waters were found to be low compared to earlier studies. α-Hexachlorocyclohexane (α-HCH) and hexachlorobenzene (HCB) were the predominant contaminants. However, these two compounds have higher levels in oceanic water compared to freshwater influenced fjord waters. These chemicals can thus be considered as indicators for direct atmospheric long-range transport, while the organochlorine pesticides like trans-, cis-chlordane, trans-nonachlor and oxychlordane that are detected in the inner parts of the fjord are indicators for potential freshwater sources such as rivers and glacial meltwater runoff (secondary sources). The average values were 50 pg L(-1) for HCB and 11 pg L(-1) for α-HCH. These concentrations are comparable to levels in fjords in Svalbard (Norwegian Arctic), but lower than in open and/or ice covered oceans in the Canadian Arctic. Two air samplers were deployed for the identification of direct atmospheric contributions. Local contamination sources do not contribute significantly. The study demonstrated the value of passive water sampling devices for comprehensive hydrological characterization of Arctic coastal waters.

Antibiotics are released into the environment in a variety of ways: via wastewater effluent as a result of incomplete metabolism in the body after use in human therapy, as runoff after use in agriculture, through improper disposal by private households or hospitals or through insufficient removal by water treatment plants. Unlike in most European countries, in Arctic regions effluents are not suitably treated prior to their release into the aquatic environment. Also, many of the scattered human settlements in remote regions of the Arctic do not possess sewage treatment facilities and pharmaceutical residues therefore enter the aqueous environment untreated. Only limited data are available on the biodegradation of antibiotics under Arctic conditions. However, such information is needed to estimate the potential harm of antibiotics for the environment. Pen-G is used in this study since it is a widely prescribed antibiotic compound whose environmental properties have not yet been investigated in detail. Thus, for a very first assessment, the OECD approved biodegradation Zahn-Wellens test (ZWT, OECD 302 B) was used to study biodegradation and non-biotic elimination of the antibiotic Benzyl-penicillin (Pen-G) at different temperatures (5°C, 12.5°C and 20°C). The testing period was extended from the OECD standard of 28-42d. In addition to dissolved organic carbon (DOC), Pen-G levels and major transformation products were recorded continuously by LC-ion-trap-MS/MS. DOC monitoring revealed considerable temperature dependence for the degradation process of Pen-G. DOC loss was slowest at 5°C and considerably faster at 12.5°C and 20°C. In the initial step of degradation it was found that Pen-G was hydrolyzed. This hydrolyzed Pen-G was subsequently further degraded by decarboxylation, the result of which was 2-(5,5-dimethyl-1,3-thiazolidin-2-yl)-2-(2-phenylacetamido)acetic acid. Furthermore, direct elimination of 2-phenyl-acetaldehyde from the hydrolyzed and decarboxylated Pen-G also led to the formation of 2-[amino(carboxy)methyl]-5,5-dimethyl-1,3-thiazolidone-4-carboxylic acid. Since biodegradation slows down considerably at a low temperature, the resulting transformation products had considerably longer residence times at 5°C compared to higher temperature conditions within the 42-d experiment. The results presented here clearly demonstrate that a risk assessment for pharmaceuticals present in low ambient temperature environments (i.e. the Arctic) cannot be based on test results obtained under standard laboratory conditions (i.e. 20°C ambient temperatures)., (Crown Copyright © 2010. Published by Elsevier Ltd. All rights reserved.)

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., (Crown Copyright 2009. Published by Elsevier B.V. All rights reserved.)

The aromatic hydrocarbons benzene, toluene and C2-benzenes (ethyl benzene and m,p,o-xylene) (BTEX) were measured during a 2-month monitoring campaign in 2007 in the Arctic town of Longyearbyen (Spitsbergen, Svalbard). Reflecting the remoteness of the location, very low mixing ratios were observed during night and in windy conditions. In late spring (April-May), however, the high frequency of guided snowmobile tours resulted in "rush-hour" maximum values of more than 10 ppb of BTEX. These concentration levels are comparable to those in European towns and are caused predominately by the outdated 2-stroke engines, which are still used by approximately 30% of the snowmobiles in Longyearbyen. During summer, peak events were about a factor of 100 lower compared to those during the snowmobile season. Emissions in summer were mainly caused by diesel-fueled heavy duty vehicles (HDVs), permanently used for coal transport from the adjacent coal mines. The documented high BTEX mixing ratios from snowmobiles in the Arctic provide an obvious incentive to change the regulation practice to a cleaner engine technology.

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.

A first medium term monitoring of atmospheric transport and distribution for persistent organic pollutants (POPs) in Bjørnøya (Bear island) air samples has been performed in the period between week 51/1999 and week 28/2003. A total of 50 single compounds consisting of polychlorinated biphenyls (33 congeners), hexachlorobenzene (HCB), hexachlorocyclohexane isomers (alpha-, beta-, gamma-HCH), alpha-endosulfan, cyclodiene pesticides (chlordanes, nonachlor-isomers, oxy-chlordane, heptachlor and chlordane) as well as dichlorodiphenyltrichloroethane (DDT) derivatives were analysed and quantified. Atmospheric transport of POPs was identified as an important contamination source for the island. PCBs, HCB and HCH isomers were the predominant POP groups, contributing with 70-90% to the overall POP burden quantified in the Bjørnøya air samples. The highest concentration levels for a single compound were found for HCB (25-35 pg m(-3)). However, the sum of 33 PCB congeners was found to be in the same concentration range (annual means between 15 and 30 pg m(-3)). Cyclodiene pesticides, DDT derivatives and alpha-endosulfan were identified as minor contaminants. Several atmospheric long-range transport episodes were identified and characterised. Indications for industrial emissions as well as agricultural sources were found for the respective atmospheric transport episodes. A first simple statistical correlation assessment showed that for long-range transport of pollution, the local meteorological situation is not as important as the air mass properties integrated over the time period of the transport event. The local weather situation, on the other hand, is important when investigating deposition rates and up-take/accumulation properties in the local ecosystem. Based upon chemical data interpretation, valuable information about the influence of primary and secondary sources on the air mass contamination with chlorinated insecticides (e.g., HCHs) was found and discussed. The interdisciplinary interpretation of contaminant data using statistical methods, chemical analysis, meteorological modelling and classical meteorological information for a comprehensive evaluation of atmospheric long range transport into the European Arctic (Bjørnøya) has proven to be a highly versatile tool not only for atmospheric scientists but also with strong potential for regulatory purposes.

The primary goal for the study presented here was the preparation and characterisation of enantiomeric pure chlorobornane standards (Toxaphene). In this context, we partially modeled the procedure for Polychloropinene production in the former USSR. The initial reaction was ionic addition of hydrogen chloride to (1S)-alpha-pinene resulting predominantly in (1S)-2-endo-chlorobornane. Further photochlorination gave mixtures of chlorinated terpenes with different average content of Cl per molecule. The resulting mixtures were separated on a silica-gel column and a number of known hepta to decachlorobornanes were identified in fractions with the help of NMR and GC (using electron capture and mass spectrometric detection)--but in very unusual ratios as compared to the technical Toxaphene mixture formerly produced by Hercules (USA). Also several previously unknown congeners were isolated or detected. Three of the isolated congeners were obtained in crystalline state and X-ray crystallography showed their enantiomeric purity.

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.

Weekly high-volume air samples were collected between 2000 and 2003 at six Arctic sites, i.e., Alert, Kinngait, and Little Fox Lake (LFL) in Canada, Point Barrow in Alaska, Valkarkai in Russia, and Zeppelin in Norway. Hexachlorocyclohexanes (HCHs) and hexachlorobenzene (HCB) were quantified in all samples. Comparison showed that alpha-HCH and HCB were homogeneously distributed in the circumpolar atmosphere and uniform throughout the seasons. However, significantly higher atmospheric concentrations of alpha-HCH and HCB and strongertemperature dependence of alpha-HCH and gamma-HCH were found at LFL in Yukon (YK), which is unique among the sites by virtue of its high altitude and low latitude, resulting in higher precipitation rates and summer temperatures. Strong temperature dependence of alpha- and gamma-HCH at this location suggests that secondary emissions, i.e., re-evaporation from surfaces, were more important at this site than others. It is hypothesized that a higher precipitation rate at LFL facilitated the transfer of alpha-HCH from the atmosphere to surface media when technical HCH was still in use worldwide. On the other hand, higher temperature at LFL enhanced reevaporation to the atmosphere after the global ban of technical HCH. In contrast to alpha-HCH and HCB, larger spatial and seasonal differences were seen for gamma-HCH (a currently used pesticide), which likely reflect the influence of different primary contaminant sources on different Arctic locations. Fugacity ratios suggest a net deposition potential of HCB from air to seawater, whereas seawater/air exchange direction of alpha-HCH varies in the circumpolar environment.

An analytical method for quantification of the selective serotonin reuptake inhibitors (SSRIs) citalopram, sertraline, paroxetine, fluoxetine and fluvoxamine in sewage influents and effluents from selected sewage treatment plants (STPs) has been developed and validated. This quantification method is based on solid phase extraction of 2.5L samples, followed by liquid-liquid extraction for further sample clean up in order to minimize matrix effects during subsequent quantification. The samples were analysed on a high performance liquid chromatograph coupled to a triple quadrupole mass spectrometric detector using 0.1% ammonia in acetonitrile/water as mobile phase, with positive electrospray ionisation and multiple reaction monitoring for detection and quantification. 1-[3-(10,11-dihydro-5H-dibenzo[a,d]cyclohepten-5-ylidene)propyl]-pyrrolidine (N-7084) was used as internal standard for quantification. The recovery rates of the SSRIs ranged between 54 and 84%, and the method limit of quantification (MLQ) was between 120 and 290 pg/L for the target compounds. Samples were collected in July 2005 from three different STPs and a pump station in Tromsø, Northern Norway. Two of the STPs serve the University hospital and its psychiatric department, respectively, in addition to domestic sewage. SSRIs were detected in all samples collected. The concentrations varied greatly from below the MLQ to several hundreds ng/L. Concentrations in influents were higher compared to filtered effluents, indicating that SSRIs adsorb to particulate matter, are degraded by microorganisms, or degraded in other ways during the filtration process. However, more samples should be analysed before general conclusions can be drawn.

Persistent organic pollutants (POPs), and their transformation products, are the most investigated organic environmental contaminants within the past five decades. Organochlorines have been found in virtually all environmental compartments on the globe. Severe environmental implications have been shown to be associated with the presence of the POP group of contaminants in the environment. However, in the late 1990s, Canadian scientists first pinpointed the implication of POPs for high-altitude environments in a comprehensive way (Blais et al., 1998, Nature 395, 585-588). Under certain meteorological and geographic conditions, high-altitude environments can serve as "cold condensers" for atmospheric POP loadings. Subsequent investigations in high-altitude environments in Asia, Europe, and North and South America have confirmed suspicions that high-altitude mountainous regions have the potential to serve as focus regions for POPs and even for nonpersistent, medium-lived contaminants, such as "currently used pesticides", due to cold condensation and deposition in high altitudes. Although the presence and the altitude-dependent increase of POP levels in mountainous regions are confirmed by many international studies, the ecotoxicological consequences still remain largely unknown. At present, only a few studies have been published describing the biological effects in high-altitude environments due to increased POP exposure. Therefore, in this early stage of the international research effort on the ecotoxicological risk evaluation of persistent contaminants in high-altitude, pristine ecosystems, the present review intends to summarize the current state of research on POPs in high-altitude environments and draw preliminary conclusions on possible consequences of the presence of POPs in mountainous ecosystems based on currently available information from alpine and related Arctic environments.

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.

Levels of selected sparsely investigated persistent organic pollutants (POPs) have been measured in organisms from two Arctic lakes on Bjørnøya (Bear Island). Elevated levels of chlorobornanes (CHBs) (up to 46.7 ng/g wet weight=ww), polybrominated diphenyl ethers (PBDEs) (up to 27.2 ng/g ww), polybrominated biphenyls (PBBs) (up to 1.1 ng/g ww) and polychlorinated naphthalenes (PCNs, only 4 congeners) (up to 62.7 pg/g ww), were measured in biota from Lake Ellasjøen. In Lake Øyangen, located only 5 km north of Ellasjøen, levels of these contaminants were significantly lower. delta(15)N-values were 7-10 per thousand higher in organisms from Ellasjøen as compared to Øyangen. This is attributed to biological inputs related to seabird activities. The present study illustrates that contaminants such as CHBs, brominated flame retardants and PCNs accumulate in the Ellasjøen food web in a manner similar to PCBs and conventional organochlorine pesticides. Transport mechanisms that control PCB and DDT distributions, i.e. atmospheric long-range transport and biotransport by seabirds, are also relevant for the contaminants investigated in the present study.

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.

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.

Selected pharmaceuticals, among them analgesics, ss-blockers and anti-depressants as well as caffeine, the anti-bacterial triclosan and the insect repellent N,N-diethyl-3-toluamide (DEET) were determined in different sewage samples (sewage treatment plants, hospital effluents) from Tromsø/Norway and in seawater from Tromsø-Sound, into which the sewage is discharged. While caffeine, triclosan, ibuprofen and its major metabolites hydroxy- and carboxy-ibuprofen were present in all sewage samples, additional pharmaceuticals were observed in sewage containing hospital effluents. Concentrations were in the range of 20-293 microg/l (caffeine), 0.2-2.4 microg/l (triclosan) and 0.1-20 microg/l (sum ibuprofen + metabolites). In seawater, only caffeine (7-87 ng/l), DEET (0.4-13 ng/l) and ibuprofen + metabolites (sum concentration < LOQ-7.7 ng/l) were detected. Ibuprofen and its metabolites hydroxy- and carboxy-ibuprofen were quantified individually by use of the respective reference compounds. Relative amounts of the three compounds were determined in different types of water showing characteristic patterns, with hydroxy-ibuprofen being the major component in sewage whereas carboxy-ibuprofen was dominant in seawater samples. The patterns which were compared to those observed in similar samples from Germany indicated different transformation behaviour under limnic and marine conditions.

Seven polymeric solid-phase extraction (SPE) sorbents were evaluated with regard to their ability to extract acidic, neutral and basic pharmaceuticals and estrogens simultaneously from water at neutral pH. Highest recoveries (70-100%) for the majority of the analytes were obtained with styrene-methacrylate and styrene-N-vinylpyrrolidone co-polymers. The latter one (Oasis HLB) was chosen for further refinement of an extraction method for the quantitative determination of acidic and neutral drugs in surface water samples at detection limits below 1 ng/l. A sequential elution protocol was applied for clean-up and separation of the extracted analytes into fractions suitable for further compound specific processing. The neutral analytes as well as the acidic compounds after derivatisation were quantified by GC-MS. Caffeine, ibuprofen, its metabolites and diclofenac were detected in river water samples in the 1-100 ng/l range.

The performance of three different types of mass spectrometers (MS) coupled to high performance liquid chromatography (HPLC) was compared for trace analysis of perfluoroalkylated substances (PFAS) and fluorotelomer alcohols (FTOHs). Ion trap MS in the full scan and product ion MS2 mode, time-of-flight (TOF) high resolution MS and quadrupole MS in the selected ion mode as well as triple quadrupole tandem MS were tested. Electrospray ionisation in the negative ion mode [ESI-] was best suited for all instruments and compounds. PFAS could only be separated by a buffered mobile phase, but the presence of buffer suppressed the ionisation of FTOHs. Therefore, two independent chromatographic methods were developed for the two compound classes. Mass spectra and product ion spectra obtained by in-source and collision induced dissociation fragmentation are discussed including ion adduct formation. Product ion yields of PFAS were only in the range of 0.3 to 12%, independent from the applied MS instrument. Ion trap MS2 gave product ion yields of 20 to 62% for FTOHs, whereas only 4.1 to 5.8% were obtained by triple quadrupole tandem MS. Ion trap MS was best suited for qualitative analysis and structure elucidation of branched isomeric structures of PFAS. Providing typical detection limits of 5 ng injected in MS2 mode, it was not sensitive enough for selective trace amount quantification. TOF high resolution MS was the only technique combining high selectivity and excellent sensitivity for PFAS analysis (detection limits of 2 to 10 pg), but lacked the possibility of MS-MS. Triple quadrupole tandem MS was the method of choice for quantification of FTOHs with detection limits in the low pg range. It is also well suited for the determination of PFAS, though its detection limits of 10 to 100 pg in tandem MS mode are about one order of magnitude higher than for TOF MS.

The separation properties of different chromatographic methods regarding the enantioselective separation of axially chiral (atropisomeric) polybrominated biphenyls (PBB) were studied. For this purpose, the technical hexabromobiphenyl product Firemaster BP-6 was characterised by gas-chromatography coupled to electron capture detection (GC/ECD) and electron-capture negative ion mass spectrometry (GC/ECNI-MS) as well as by liquid chromatographic fractionating on active carbon and celite. Twelve individual PBBs including potential atropisomeric PBBs were isolated from Firemaster BP-6 by reversed-phase high-performance liquid chromatography (HPLC) on three serially coupled octadecylsilane columns. Six of the 12 isolated PBBs (three tri-ortho and di-ortho substituted PBBs, respectively) were separated into atropisomers on a HPLC column containing permethylated beta-cyclodextrin on silica. Moreover, the temperature dependency of the enantiomer separations is discussed. Gas chromatographic enantiomer separation of PBBs is a very demanding task due to high elution temperatures. However, the atropisomers of one tri-ortho substituted PBB congener (PBB 149) could be resolved on a column coated with randomly modified heptakis(6-O-tert.-butyldimethylsilyl-2,3-di-O-methyl)-beta-cyclodextrin in OV 1701.

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.

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.

Short-chain polychlorinated alkanes (sPCAs) have been measured in freshwater fish samples from different lakes all over Norway and from the Norwegian Arctic. The analyses were performed with high-resolution GC coupled to high-resolution MS in electron capture negative ion mode. The species investigated were trout, Arctic char, and burbot (Lota lota). Muscle tissue in the lake trout and Arctic char, and liver in burbot, were selected for analyses because of their high lipid content. SigmasPCA concentration ranged from 108 to 3700 ng/g fat. The highest value was found in the south of Norway near an industrial area.

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.

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.

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.

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.

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).

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.