Halomethoxybenzenes in air of the Nordic region.

Halomethoxybenzenes (HMBs) are a group of compounds with natural and anthropogenic origins. Here we extend a 2002-2015 survey of bromoanisoles (BAs) in the air and precipitation at Råö on the Swedish west coast and Pallas in Subarctic Finland. New BAs data are reported for 2018 and 2019 and chlorinated HMBs are included for these and some previous years: drosophilin A methyl ether (DAME: 1,2,4,5-tetrachloro-3,6-dimethoxybenzene), tetrachloroveratrole (TeCV: 1,2,3,4-tetrachloro-5,6-dimethoxybenzene), and pentachloroanisole (PeCA). The order of abundance of HMBs at Råö was ΣBAs > DAME > TeCV > PeCA, whereas at Pallas the order of abundance was DAME > ΣBAs > TeCA > PeCA. The lower abundance of BAs at Pallas reflects its inland location, away from direct marine influence. Clausius-Clapeyron (CC) plots of log partial pressure (Pair)/Pa versus 1/T suggested distant transport at both sites for PeCA and local exchange for DAME and TeCV. BAs were dominated by distant transport at Pallas and by both local and distant sources at Råö. Relationships between air and precipitation concentrations were examined by scavenging ratios, SR = (ng m-3)precip/(ng m-3)air. SRs were higher at Pallas than Råö due to greater Henry's law partitioning of gaseous compounds into precipitation at colder temperatures. DAME is produced by terrestrial fungi. We screened 19 fungal species from Swedish forests and found seven of them contained 0.01-3.8 mg DAME per kg fresh weight. We suggest that the volatilization of DAME from fungi and forest litter containing fungal mycelia may contribute to atmospheric levels at both sites.

Polycyclic Aromatic Hydrocarbons Not Declining in Arctic Air Despite Global Emission Reduction.

Two decades of atmospheric measurements of polycyclic aromatic hydrocarbons (PAHs) were conducted at three Arctic sites, i.e., Alert, Canada; Zeppelin, Svalbard; and Pallas, Finland. PAH concentrations decrease with increasing latitude in the order of Pallas > Zeppelin > Alert. Forest fire was identified as an important contributing source. Three representative PAHs, phenanthrene (PHE), pyrene (PYR), and benzo[ a]pyrene (BaP) were selected for the assessment of their long-term trends. Significant decline of these PAHs was not observed contradicting the expected decline due to PAH emission reductions. A global 3-D transport model was employed to simulate the concentrations of these three PAHs at the three sites. The model predicted that warming in the Arctic would cause the air concentrations of PHE and PYR to increase in the Arctic atmosphere, while that of BaP, which tends to be particle-bound, is less affected by temperature. The expected decline due to the reduction of global PAH emissions is offset by the increment of volatilization caused by warming. This work shows that this phenomenon may affect the environmental occurrence of other anthropogenic substances, such as more volatile flame retardants and pesticides.

Polychlorinated biphenyls (PCBs) as sentinels for the elucidation of Arctic environmental change processes: a comprehensive review combined with ArcRisk project results.

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.

Emerging pollutants in the EU: 10 years of NORMAN in support of environmental policies and regulations.

In 2005, the European Commission funded the NORMAN project to promote a permanent network of reference laboratories and research centers, including academia, industry, standardization bodies, and NGOs. Since then, NORMAN has (i) facilitated a more rapid and wide-scope exchange of data on the occurrence and effects of contaminants of emerging concern (CECs), (ii) improved data quality and comparability via validation and harmonization of common sampling and measurement methods (chemical and biological), (iii) provided more transparent information and monitoring data on CECs, and (iv) established an independent and competent forum for the technical/scientific debate on issues related to emerging substances. NORMAN plays a significant role as an independent organization at the interface between science and policy, with the advantage of speaking to the European Commission and other public institutions with the "bigger voice" of more than 70 members from 20 countries. This article provides a summary of the first 10 years of the NORMAN network. It takes stock of the work done so far and outlines NORMAN's vision for a Europe-wide collaboration on CECs and sustainable links from research to policy-making. It contains an overview of the state of play in prioritizing and monitoring emerging substances with reference to several innovative technologies and monitoring approaches. It provides the point of view of the NORMAN network on a burning issue-the regulation of CECs-and presents the positions of various stakeholders in the field (DG ENV, EEA, ECHA, and national agencies) who participated in the NORMAN workshop in October 2016. The main messages and conclusions from the round table discussions are briefly presented.

Pharmaceuticals and personal care products (PPCPs) in Arctic environments: indicator contaminants for assessing local and remote anthropogenic sources in a pristine ecosystem in change.

A first review on occurrence and distribution of pharmaceuticals and personal care products (PPCPs) is presented. The literature survey conducted here was initiated by the current Assessment of the Arctic Monitoring and Assessment Programme (AMAP). This first review on the occurrence and environmental profile of PPCPs in the Arctic identified the presence of 110 related substances in the Arctic environment based on the reports from scientific publications, national and regional assessments and surveys, as well as academic research studies (i.e., PhD theses). PPCP residues were reported in virtually all environmental compartments from coastal seawater to high trophic level biota. For Arctic environments, domestic and municipal wastes as well as sewage are identified as primary release sources. However, the absence of modern waste water treatment plants (WWTPs), even in larger settlements in the Arctic, is resulting in relatively high release rates for selected PPCPs into the receiving Arctic (mainly) aquatic environment. Pharmaceuticals are designed with specific biochemical functions as a part of an integrated therapeutically procedure. This biochemical effect may cause unwanted environmental toxicological effects on non-target organisms when the compound is released into the environment. In the Arctic environments, pharmaceutical residues are released into low to very low ambient temperatures mainly into aqueous environments. Low biodegradability and, thus, prolonged residence time must be expected for the majority of the pharmaceuticals entering the aquatic system. The environmental toxicological consequence of the continuous PPCP release is, thus, expected to be different in the Arctic compared to the temperate regions of the globe. Exposure risks for Arctic human populations due to consumption of contaminated local fish and invertebrates or through exposure to resistant microbial communities cannot be excluded. However, the scientific results reported and summarized here, published in 23 relevant papers and reports (see Table S1 and following references), must still be considered as indication only. Comprehensive environmental studies on the fate, environmental toxicology, and distribution profiles of pharmaceuticals applied in high volumes and released into the Nordic environment under cold Northern climate conditions should be given high priority by national and international authorities.

Atmospheric Transport and Deposition of Bromoanisoles Along a Temperate to Arctic Gradient.

Bromoanisoles (BAs) arise from O-methylation of bromophenols, produced by marine algae and invertebrates. BAs undergo sea-air exchange and are transported over the oceans. Here we report 2,4-DiBA and 2,4,6-TriBA in air and deposition on the Swedish west coast (Råö) and the interior of arctic Finland (Pallas). Results are discussed in perspective with previous measurements in the northern Baltic region in 2011-2013. BAs in air decreased from south to north in the order Råö > northern Baltic > Pallas. Geometric mean concentrations at Pallas increased significantly (p < 0.05) between 2002 and 2015 for 2,4-DiBA but not for 2,4,6-TriBA. The logarithm of BA partial pressures correlated significantly to reciprocal air temperature at the coastal station Råö and over the Baltic, but only weakly (2,4-DiBA) or not significantly (2,4,6-TriBA) at inland Pallas. Deposition fluxes of BAs were similar at both sites despite lower air concentrations at Pallas, due to greater precipitation scavenging at lower temperatures. Proportions of the two BAs in air and deposition were related to Henry's law partitioning and source regions. Precipitation concentrations were 10-40% of those in surface water of Bothnian Bay, northern Baltic Sea. BAs deposited in the bay catchment likely enter rivers and provide an unexpected source to northern estuaries. BAs may be precursors to higher molecular weight compounds identified by others in Swedish inland lakes.

An expanded conceptual framework for solution-focused management of chemical pollution in European waters.

BACKGROUND: This paper describes a conceptual framework for solutions-focused management of chemical contaminants built on novel and systematic approaches for identifying, quantifying and reducing risks of these substances. METHODS: The conceptual framework was developed in interaction with stakeholders representing relevant authorities and organisations responsible for managing environmental quality of water bodies. Stakeholder needs were compiled via a survey and dialogue. The content of the conceptual framework was thereafter developed with inputs from relevant scientific disciplines. RESULTS: The conceptual framework consists of four access points: Chemicals, Environment, Abatement and Society, representing different aspects and approaches to engaging in the issue of chemical contamination of surface waters. It widens the scope for assessment and management of chemicals in comparison to a traditional (mostly) perchemical risk assessment approaches by including abatement- and societal approaches as optional solutions. The solution-focused approach implies an identification of abatement- and policy options upfront in the risk assessment process. The conceptual framework was designed for use in current and future chemical pollution assessments for the aquatic environment, including the specific challenges encountered in prioritising individual chemicals and mixtures, and is applicable for the development of approaches for safe chemical management in a broader sense. The four access points of the conceptual framework are interlinked by four key topics representing the main scientific challenges that need to be addressed, i.e.: identifying and prioritising hazardous chemicals at different scales; selecting relevant and efficient abatement options; providing regulatory support for chemicals management; predicting and prioritising future chemical risks. The conceptual framework aligns current challenges in the safe production and use of chemicals. The current state of knowledge and implementation of these challenges is described. CONCLUSIONS: The use of the conceptual framework, and addressing the challenges, is intended to support: (1) forwarding sustainable use of chemicals, (2) identification of pollutants of priority concern for cost-effective management, (3) the selection of optimal abatement options and (4) the development and use of optimised legal and policy instruments.

Temporal trends of Persistent Organic Pollutants (POPs) in arctic air: 20 years of monitoring under the Arctic Monitoring and Assessment Programme (AMAP).

Temporal trends of Persistent Organic Pollutants (POPs) measured in Arctic air are essential in understanding long-range transport to remote regions and to evaluate the effectiveness of national and international chemical control initiatives, such as the Stockholm Convention (SC) on POPs. Long-term air monitoring of POPs is conducted under the Arctic Monitoring and Assessment Programme (AMAP) at four Arctic stations: Alert, Canada; Stórhöfði, Iceland; Zeppelin, Svalbard; and Pallas, Finland, since the 1990s using high volume air samplers. Temporal trends observed for POPs in Arctic air are summarized in this study. Most POPs listed for control under the SC, e.g. polychlorinated biphenyls (PCBs), dichlorodiphenyltrichloroethanes (DDTs) and chlordanes, are declining slowly in Arctic air, reflecting the reduction of primary emissions during the last two decades and increasing importance of secondary emissions. Slow declining trends also signifies their persistence and slow degradation under the Arctic environment, such that they are still detectable after being banned for decades in many countries. Some POPs, e.g. hexachlorobenzene (HCB) and lighter PCBs, showed increasing trends at specific locations, which may be attributable to warming in the region and continued primary emissions at source. Polybrominated diphenyl ethers (PBDEs) do not decline in air at Canada's Alert station but are declining in European Arctic air, which may be due to influence of local sources at Alert and the much higher historical usage of PBDEs in North America. Arctic air samples are screened for chemicals of emerging concern to provide information regarding their environmental persistence (P) and long-range transport potential (LRTP), which are important criteria for classification as a POP under SC. The AMAP network provides consistent and comparable air monitoring data of POPs for trend development and acts as a bridge between national monitoring programs and SC's Global Monitoring Plan (GMP).

Atmospheric pathways of chlorinated pesticides and natural bromoanisoles in the northern Baltic Sea and its catchment.

Long-range atmospheric transport is a major pathway for delivering persistent organic pollutants to the oceans. Atmospheric deposition and volatilization of chlorinated pesticides and algae-produced bromoanisoles (BAs) were estimated for Bothnian Bay, northern Baltic Sea, based on air and water concentrations measured in 2011-2012. Pesticide fluxes were estimated using monthly air and water temperatures and assuming 4 months ice cover when no exchange occurs. Fluxes were predicted to increase by about 50 % under a 2069-2099 prediction scenario of higher temperatures and no ice. Total atmospheric loadings to Bothnian Bay and its catchment were derived from air-sea gas exchange and "bulk" (precipitation + dry particle) deposition, resulting in net gains of 53 and 46 kg year(-1) for endosulfans and hexachlorocyclohexanes, respectively, and net loss of 10 kg year(-1) for chlordanes. Volatilization of BAs releases bromine to the atmosphere and may limit their residence time in Bothnian Bay. This initial study provides baseline information for future investigations of climate change on biogeochemical cycles in the northern Baltic Sea and its catchment.

Comprehensive mass flow analysis of Swedish sludge contaminants.

A screening of metals, persistent organic pollutants, pharmaceuticals and personal care products (PPCPs), and other organic contaminants in sludge from seven Swedish sewage treatment plants (STPs) was performed in this study. This extensive screening provides information on mass flows of 282 compounds used in the Swedish society to sewage sludge. It reveals constant relative contaminant concentrations (ng mg kg(-1) d.w.), except for some pesticides and perfluorinated compounds, indicating that these originate from broad usage and diffuse dispersion rather than (industrial) point sources. There was a five order of magnitude difference in the sum concentrations of the most and least abundant species (metals and polychlorinated dibenzo-p-dioxins and -furans, respectively). Lower total concentrations were found in sludge from STPs processing primarily food industry or household sewage. Proportions of the amounts used (in Sweden) found in sludge were lower for compounds that are present in consumer goods or are diffusely dispersed into the environment (0.01-1% recovered in sludge) than for compounds used as detergents or PPCPs (17-63%). In some cases, the recovery seemed to be affected by evaporation (e.g. octamethylcyclotetrasiloxane) or biotransformation (e.g. adipates) losses, while polychlorinated alkanes and brominated diphenyl ethers were recovered to disproportionately high degree (ca. 4%); likely due to incomplete statistics for imported goods.

Prioritizing organic chemicals for long-term air monitoring by using empirical monitoring data--application to data from the Swedish screening program.

This paper illustrates a step-by-step approach for evaluating chemical monitoring data in air and deposition and for prioritizing chemicals to be included in long-term air monitoring programs. The usability of the method is shown by application to data generated within the Swedish screening program. The suggested prioritization approach uses a novel methodology by combining empirical data on occurrence in air and deposition with publicly available quantitative structure activity relationship estimation tools that predict atmospheric persistence and bioaccumulation. A selection tree is presented, which may be used by regulatory bodies to prioritize chemicals for long-term air monitoring. A final ranking list is presented proposing a prioritization order for inclusion in monitoring programs. Based on the suggested strategy, the chemicals identified as most relevant to include in Swedish long-term monitoring programs were short-chain chlorinated paraffins(C10-C13), perfluorooctane sulfonate, octachlorostyrene, hexabromocyclododecane, hexachlorobenzene, pentachloroanisole, decamethylcyclopentasiloxane, octamethylcyclotetrasiloxane, pentachlorobenzene, 1,2,3,4-tetrachlorobenzene, hexachlorobutadiene, dodecamethylcyclohexasiloxane, perfluorodecane sulfonate, 1,2,4,5-tetrachlorobenzene, and pentabromophenol.

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.

Is levoglucosan a suitable quantitative tracer for wood burning? Comparison with receptor modeling on trace elements in Lycksele, Sweden.

Particle emissions from residential wood combustion in small communities in Northern Sweden can sometimes increase the ambient particle concentrations to levels comparable to densely trafficked streets in the center of large cities. The reason for this is the combination of increased need for domestic heating during periods of low temperatures, leading to higher emission rates, and stable meteorological conditions. In this work, the authors compare two different approaches to quantify the wood combustion contribution to fine particles in Northern Sweden: a multivariate source-receptor analysis on inorganic compounds followed by multiple linear regression (MLR) of fine particle concentrations and levoglucosan used as a tracer. From the receptor model, it can be seen that residential wood combustion corresponds with 70% of modeled particle mass. Smaller contributions are also seen from local nonexhaust traffic particles, road dust, and brake wear (each contributing 14%). Of the mass, 1.5% is explained by long-distance transported particles, and 2% derives from a regional source deriving from either oil combustion or smelter activities. In samples collected in ambient air, a significant linear correlation was found between wood burning particles and levoglucosan. The levoglucosan fraction in the ambient fine particulate matter attributed to wood burning according to the multivariate analysis ranged from < 2% to 50%. This is much higher than the fraction found in the emission from the boilers expected to be responsible for most emissions at this site (between 3% and 6%). A laboratory emission study of wood and pellet boilers gave 0.3% wt to 22% wt levoglucosan to particle mass, indicating that the levoglucosan fraction may be highly dependent on combustion conditions, making it uncertain to use it as a quantitative tracer under real-world burning conditions. Thus, quantitative estimates of wood burning contributions will be very uncertain using solely levoglucosan as a tracer.

Seasonal and long-term trends in atmospheric PAH concentrations: evidence and implications.

Atmospheric monitoring data for selected polynuclear aromatic hydrocarbons (PAHs) were compiled from remote, rural and urban locations in the UK, Sweden, Finland and Arctic Canada. The objective was to examine the seasonal and temporal trends, to shed light on the factors which exert a dominant influence over ambient PAH levels. Urban centres in the UK have concentrations 1-2 orders of magnitude higher than in rural Europe and up to 3 orders of magnitude higher than Arctic Canada. Interpretation of the data suggests that proximity to primary sources 'drives' PAH air concentrations. Seasonality, with winter (W) > summer (S), was apparent for most compounds at most sites; high molecular weight compounds (e.g. benzo[a]pyrene) showed this most clearly and consistently. Some low molecular weight compounds (e.g. phenanthrene) sometimes displayed S>W seasonality at some rural locations. Strong W>S seasonality is linked to seasonally-dependent sources which are greater in winter. This implicates inefficient combustion processes, notably the diffusive domestic burning of wood and coal. However, sometimes seasonality can also be strongly influenced by broad changes in meteorology and air mass origin (e.g. in the Canadian Arctic). The datasets examined here suggest a downward trend for many PAHs at some sites, but this is not apparent for all sites and compounds. The inherent noise in ambient air monitoring data makes it difficult to derive unambiguous evidence of underlying declines, to confirm the effectiveness of international source reduction measures.

Evaluation of sequentially-coupled POP fluxes estimated from simultaneous measurements in multiple compartments of an air-water-sediment system.

Bulk atmospheric deposition fluxes, air-water exchange fluxes, particle settling fluxes out of the upper water column, sediment trap fluxes in deep waters, and sediment burial fluxes of polychlorinated biphenyls (PCBs) and polycyclic aromatic hydrocarbons (PAHs) were simultaneously measured in the Koster Fjord, eastern Skagerak, on the Swedish west coast. The aim of the study was to compare the magnitude and direction of the compound fluxes in the system in order to diagnose key fate processes. The PCB and PAH fluxes via net atmospheric deposition, settling particles out of the surface and through deep waters, as well as into the accreting underlying sediments were shown to be remarkably similar, agreeing within a factor of a few for any given target compound. Fluxes of all PCB and PAH target compounds remained fairly constant with water column depth. Thus there was no evidence for net desorption from sinking particles. The net unidirectional and near balancing of vertical fluxes suggests a net transport of PCBs and PAHs from the atmosphere to the continental shelf sediments in the Koster Fjord, which is consistent with the hypothesis that the shelf sediments are important sinks for these compounds.

The environmental occurrence of hexabromocyclododecane in Sweden.

The brominated flame retardant hexabromocyclododecane (HBCD) is extensively used in Europe, but data on the environmental concentrations of this chemical are scarce. A first screening has been performed concerning the environmental occurrence of HBCD in Sweden, a country where the chemical is not produced and the current industrial use is very limited. Possible emission sources were identified through a systematic analysis of the use in a life cycle perspective. In addition to a few point sources, diffuse emissions from polymeric products are possible. Measurements have been performed close to certain possible point sources, in the urban environment and in remote regions, and included air, deposition, water, soil, sediments, sludge, biota and foodstuffs. HBCD was detected in all media analysed and in all environments. The relatively high concentrations detected in herring and foodstuffs provide evidence for bioaccumulation of HBCD. The presence of HBCD in remote background air implies that HBCD has potential for long-range atmospheric transport. There are also some indications that diffuse emissions of HBCD occur in the urban environment.

Chlordane enantiomers and temporal trends of chlordane isomers in arctic air.

A 14-year data set (1984-1998) for chlordane compounds in arctic airwas examined to discern temporal trends. trans-Chlordane (TC), cis-chlordane (CC), and trans-nonachlor (TN) declined significantly (p < 0.001-0.02), with apparent times for 50% reduction of 4.9-9.7 y. The isomer fraction of TC = (TC/(TC + CC) also declined significantly (p < 0.001 -0.014) over the same time period. The enantiomeric composition of TC and CC was determined in air samples collected at arctic stations in Canada (1993-1996), Russia (1994), and Finland (1998), and a temperate station on the Swedish west coast (1998). Enantiomer fractions, EF = (+)/[(+) + (-)], were significantly different from measured EFs of racemic standards (0.498-0.501) at all stations for TC (p < 0.001) and two stations for CC (p < 0.001 to <0.05). These observations suggest changing source composition of chlordane in arctic air, with a greater proportion of weathered residues in recent years, possibly derived from soils. Identification of nonracemic (mean EFs = 0.662-0.703) heptachlor exo-epoxide (HEPX) at the four air stations further exemplifies contributions of soil emissions to long-range transport of chlordane-related compounds.