Computational material flow analysis for thousands of chemicals of emerging concern in European waters.

Knowledge of exposure to a wide range of chemicals, and the spatio-temporal variability thereof, is urgently needed in the context of protecting and restoring aquatic ecosystems. This paper discusses a computational material flow analysis to predict the occurrence of thousands of man-made organic chemicals on a European scale, based on a novel temporally and spatially resolved modelling framework. The goal was to increase understanding of pressures by emerging chemicals and to complement surface water monitoring data. The ambition was to provide a first step towards a "real-life" mixture exposure situation accounting for as many chemicals as possible. Comparison of simulated concentrations and chemical monitoring data for 226 substance/basin combinations showed that the simulated concentrations were accurate on average. For 65% and 90% of substance/basin combinations the error was within one and two orders of magnitude respectively. An analysis of the relative importance of uncertainties revealed that inaccuracies in use volume or use type information contributed most to the error for individual substances. To resolve this, we suggest better registration of use types of industrial chemicals, investigation of presence/absence of industrial chemicals in wastewater and runoff samples and more scientific information exchange.

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.

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.

Towards the review of the European Union Water Framework Directive: Recommendations for more efficient assessment and management of chemical contamination in European surface water resources.

Water is a vital resource for natural ecosystems and human life, and assuring a high quality of water and protecting it from chemical contamination is a major societal goal in the European Union. The Water Framework Directive (WFD) and its daughter directives are the major body of legislation for the protection and sustainable use of European freshwater resources. The practical implementation of the WFD with regard to chemical pollution has faced some challenges. In support of the upcoming WFD review in 2019 the research project SOLUTIONS and the European monitoring network NORMAN has analyzed these challenges, evaluated the state-of-the-art of the science and suggested possible solutions. We give 10 recommendations to improve monitoring and to strengthen comprehensive prioritization, to foster consistent assessment and to support solution-oriented management of surface waters. The integration of effect-based tools, the application of passive sampling for bioaccumulative chemicals and an integrated strategy for prioritization of contaminants, accounting for knowledge gaps, are seen as important approaches to advance monitoring. Including all relevant chemical contaminants in more holistic "chemical status" assessment, using effect-based trigger values to address priority mixtures of chemicals, to better consider historical burdens accumulated in sediments and to use models to fill data gaps are recommended for a consistent assessment of contamination. Solution-oriented management should apply a tiered approach in investigative monitoring to identify toxicity drivers, strengthen consistent legislative frameworks and apply solutions-oriented approaches that explore risk reduction scenarios before and along with risk assessment.

Atmospheric mercury concentrations observed at ground-based monitoring sites globally distributed in the framework of the GMOS network.

Long-term monitoring of data of ambient mercury (Hg) on a global scale to assess its emission, transport, atmospheric chemistry, and deposition processes is vital to understanding the impact of Hg pollution on the environment. The Global Mercury Observation System (GMOS) project was funded by the European Commission (http://www.gmos.eu) and started in November 2010 with the overall goal to develop a coordinated global observing system to monitor Hg on a global scale, including a large network of ground-based monitoring stations, ad hoc periodic oceanographic cruises and measurement flights in the lower and upper troposphere as well as in the lower stratosphere. To date, more than 40 ground-based monitoring sites constitute the global network covering many regions where little to no observational data were available before GMOS. This work presents atmospheric Hg concentrations recorded worldwide in the framework of the GMOS project (2010-2015), analyzing Hg measurement results in terms of temporal trends, seasonality and comparability within the network. Major findings highlighted in this paper include a clear gradient of Hg concentrations between the Northern and Southern hemispheres, confirming that the gradient observed is mostly driven by local and regional sources, which can be anthropogenic, natural or a combination of both.

Future water quality monitoring--adapting tools to deal with mixtures of pollutants in water resource management.

Environmental quality monitoring of water resources is challenged with providing the basis for safeguarding the environment against adverse biological effects of anthropogenic chemical contamination from diffuse and point sources. While current regulatory efforts focus on monitoring and assessing a few legacy chemicals, many more anthropogenic chemicals can be detected simultaneously in our aquatic resources. However, exposure to chemical mixtures does not necessarily translate into adverse biological effects nor clearly shows whether mitigation measures are needed. Thus, the question which mixtures are present and which have associated combined effects becomes central for defining adequate monitoring and assessment strategies. Here we describe the vision of the international, EU-funded project SOLUTIONS, where three routes are explored to link the occurrence of chemical mixtures at specific sites to the assessment of adverse biological combination effects. First of all, multi-residue target and non-target screening techniques covering a broader range of anticipated chemicals co-occurring in the environment are being developed. By improving sensitivity and detection limits for known bioactive compounds of concern, new analytical chemistry data for multiple components can be obtained and used to characterise priority mixtures. This information on chemical occurrence will be used to predict mixture toxicity and to derive combined effect estimates suitable for advancing environmental quality standards. Secondly, bioanalytical tools will be explored to provide aggregate bioactivity measures integrating all components that produce common (adverse) outcomes even for mixtures of varying compositions. The ambition is to provide comprehensive arrays of effect-based tools and trait-based field observations that link multiple chemical exposures to various environmental protection goals more directly and to provide improved in situ observations for impact assessment of mixtures. Thirdly, effect-directed analysis (EDA) will be applied to identify major drivers of mixture toxicity. Refinements of EDA include the use of statistical approaches with monitoring information for guidance of experimental EDA studies. These three approaches will be explored using case studies at the Danube and Rhine river basins as well as rivers of the Iberian Peninsula. The synthesis of findings will be organised to provide guidance for future solution-oriented environmental monitoring and explore more systematic ways to assess mixture exposures and combination effects in future water quality monitoring.

The SOLUTIONS project: challenges and responses for present and future emerging pollutants in land and water resources management.

SOLUTIONS (2013 to 2018) is a European Union Seventh Framework Programme Project (EU-FP7). The project aims to deliver a conceptual framework to support the evidence-based development of environmental policies with regard to water quality. SOLUTIONS will develop the tools for the identification, prioritisation and assessment of those water contaminants that may pose a risk to ecosystems and human health. To this end, a new generation of chemical and effect-based monitoring tools is developed and integrated with a full set of exposure, effect and risk assessment models. SOLUTIONS attempts to address legacy, present and future contamination by integrating monitoring and modelling based approaches with scenarios on future developments in society, economy and technology and thus in contamination. The project follows a solutions-oriented approach by addressing major problems of water and chemicals management and by assessing abatement options. SOLUTIONS takes advantage of the access to the infrastructure necessary to investigate the large basins of the Danube and Rhine as well as relevant Mediterranean basins as case studies, and puts major efforts on stakeholder dialogue and support. Particularly, the EU Water Framework Directive (WFD) Common Implementation Strategy (CIS) working groups, International River Commissions, and water works associations are directly supported with consistent guidance for the early detection, identification, prioritisation, and abatement of chemicals in the water cycle. SOLUTIONS will give a specific emphasis on concepts and tools for the impact and risk assessment of complex mixtures of emerging pollutants, their metabolites and transformation products. Analytical and effect-based screening tools will be applied together with ecological assessment tools for the identification of toxicants and their impacts. The SOLUTIONS approach is expected to provide transparent and evidence-based candidates or River Basin Specific Pollutants in the case study basins and to assist future review of priority pollutants under the WFD as well as potential abatement options.

Winter peaks of methylmercury in deposition to a remote Scottish mountain lake.

Depositional records of methylmercury (MeHg) are rare, especially for remote and mountainous areas. Our data from Lochnagar, a mountain lake in Scotland, covering a 7-year period from 2001-2008, show an unusual seasonal pattern in that elevated MeHg concentrations occur each winter while concentrations each summer fall below the limit of detection. To our knowledge this is the first time this seasonal pattern has been reported. Peak concentrations at the site in October 2006 (1.2 ng L(-1)) are amongst the highest reported depositional values in the literature. As the soils and lakes in the region are frozen or snow covered for much of each winter, we consider possible sources of this winter deposited MeHg to be either aqueous phase methylation in the atmosphere or marine evasion. However, the factor driving this seasonal pattern is likely to be scavenging by snow, as elevated concentrations in deposition coincide with periods of snowfall at the site. If this mechanism is correct, then predicted impacts of climate change, which will reduce annual snowfall at the site by between 50% and 100% by 2080, will effectively eliminate this input source. However, other climate-influenced inputs of mercury, such as remobilisation from catchment soils, are likely to increase and negate any benefit.

Climate induced thermocline change has an effect on the methyl mercury cycle in small boreal lakes.

We conducted a whole-lake experiment by manipulating the stratification pattern (thermocline depth) of a small polyhumic, boreal lake (Halsjärvi) in southern Finland and studying the impacts on lake mercury chemistry. The experimental lake was compared to a nearby reference site (Valkea-Kotinen Lake). During the first phase of the experiment the thermocline of Halsjärvi was lowered in order to simulate the estimated increase in wind speed and in total lake heat content (high-change climate scenario). The rate of methyl mercury (MeHg) production during summer stagnation (May-August) was calculated from water profiles before the treatment (2004), during treatment (2005, 2006) and after treatment (2007). We also calculated fluxes of MeHg from the epilimnion and from the hypolimnion to the sediments using sediment traps. Experimental mixing with a submerged propeller caused a 1.5-2 m deepening of the thermocline and oxycline. Methyl mercury production occurred mostly in the oxygen free layers in both lakes. In the experimental lake there was no net increase in MeHg during the experiment and following year; whereas the reference lake showed net production for all years. We conclude that the new exposed epilimnetic sediments caused by a lowering of the thermocline were a major sink for MeHg in the epilimnion. The results demonstrate that in-lake MeHg production can be manipulated in small lakes with anoxic hypolimnia during summer. The climate change induced changes in small boreal lakes most probably affect methyl mercury production and depend on the lake characteristics and stratification pattern. The results support the hypothesis that possible oxygen related changes caused by climate change are more important than possible temperature changes in small polyhumic lakes with regularly occurring oxygen deficiency in the hypolimnion.

An assessment of costs and benefits associated with mercury emission reductions from major anthropogenic sources.

Several measures are available for reducing mercury emissions; however, these measures differ with regard to emission control efficiency, cost, and environmental benefits obtained through their implementation. Measures that include the application of technology, such as technology to remove mercury from flue gases in electric power plants, waste incinerators, and smelters, are rather expensive compared with nontechnological measures. In general, dedicated mercury removal is considerably more expensive than a co-benefit strategy, using air pollution control equipment originally designed to limit emissions of criterion pollutants, such as particulate matter, sulfur dioxide, or oxides of nitrogen. Substantial benefits can be achieved globally by introducing mercury emission reduction measures because they reduce human and wildlife exposure to methyl mercury. Although the reduction potential is greatest with the technological measures, technological and nontechnological solutions for mercury emissions and exposure reductions can be carried out in parallel.

The effects of forestry on Hg bioaccumulation in nemoral/boreal waters and recommendations for good silvicultural practice.

Mercury (Hg) levels are alarmingly high in fish from lakes across Fennoscandia and northern North America. The few published studies on the ways in which silviculture practices influence this problem indicate that forest operations increase Hg in downstream aquatic ecosystems. From these studies, we estimate that between one-tenth and one-quarter of the Hg in the fish of high-latitude, managed forest landscapes can be attributed to harvesting. Forestry, however, did not create the elevated Hg levels in the soils, and waterborne Hg/MeHg concentrations downstream from harvested areas are similar to those from wetlands. Given the current understanding of the way in which silviculture impacts Hg cycling, most of the recommendations for good forest practice in Sweden appear to be appropriate for high-latitude regions, e.g., leaving riparian buffer zones, as well as reducing disturbance at stream crossings and in moist areas. The recommendation to restore wetlands and reduce drainage, however, will likely increase Hg/MeHg loadings to aquatic ecosystems.

Recovery of mercury-contaminated fisheries.

In this paper, we synthesize available information on the links between changes in ecosystem loading of inorganic mercury (Hg) and levels of methylmercury (MeHg) in fish. Although it is widely hypothesized that increased Hg load to aquatic ecosystems leads to increases in MeHg in fish, there is limited quantitative data to test this hypothesis. Here we examine the available evidence from a range of sources: studies of ecosystems contaminated by industrial discharges, observations of fish MeHg responses to changes in atmospheric load, studies over space and environmental gradients, and experimental manipulations. A summary of the current understanding of the main processes involved in the transport and transformation from Hg load to MeHg in fish is provided. The role of Hg loading is discussed in context with other factors affecting Hg cycling and bioaccumulation in relation to timing and magnitude of response in fish MeHg. The main conclusion drawn is that changes in Hg loading (increase or decrease) will yield a response in fish MeHg but that the timing and magnitude of the response will vary depending of ecosystem-specific variables and the form of the Hg loaded.

Intercomparison study of atmospheric mercury models: 2. Modelling results vs. long-term observations and comparison of country deposition budgets.

Five regional scale models with a horizontal domain covering the European continent and its surrounding seas, two hemispheric and one global scale model participated in the atmospheric Hg modelling intercomparison study. The models were compared between each other and with available measurements from 11 monitoring stations of the EMEP measurement network. Because only a very limited number of long-term measurement records of Hg were available, significant attention was given to the intercomparison of modelling results. Monthly and annually averaged values of Hg concentrations and depositions as well as items of the Hg deposition budgets for individual European countries were compared. The models demonstrated good agreement (within +/-20%) between annual modelled and observed values of gaseous elemental Hg. Modelled values of Hg wet deposition in Western and Central Europe agreed with the observations within +/-45%. The probability to predict wet depositions within a factor of 2 with regard to measurements was 50-70% for all the models. The scattering of modelling results for dry depositions of Hg was more significant (up to +/-50% at the annual scale and even higher for monthly data). Contribution of dry deposition to the total Hg deposition was estimated at 20-30% with elevated dry deposition fluxes during summer time. The participating models agree in their predictions of transboundary pollution for individual countries within +/-60% at the monthly scale and within +/-30% at the annual scale. For the cases investigated, all the models predict that the major part of national anthropogenic Hg emissions is transported outside the country territory.

Intercomparison study of atmospheric mercury models: 1. Comparison of models with short-term measurements.

Five regional scale models with a horizontal domain covering the European continent and its surrounding seas, one hemispheric and one global scale model participated in an atmospheric mercury modelling intercomparison study. Model-predicted concentrations in ambient air were compared against mercury species observed at four monitoring stations in Central and Northern Europe and a station on the Irish west coast. The modelled concentrations of total particulate mercury (TPM) were generally consistent with the measurements at all sites. The models exhibited significant ability to simulate concentrations of gaseous elemental mercury (GEM), but some of the short-duration peaks at the Central European stations could not be consistently reproduced. Possible reasons for these discrepancies include (1) errors in the anthropogenic emissions inventory utilized; (2) coarse spatial resolution of the models; and (3) uncertainty of natural and re-emitted mercury sources. The largest discrepancies between measurements and modelled concentrations were found for reactive gaseous mercury (RGM). For these models, the uncertainty in predicting short-term (two-week episode) variations of mercury species in air can be characterized by the following overall statistics: 90% of the results for TGM are within a factor of 1.35 of the measurements; for TPM, 90% are within a factor of 2.5; and for RGM, 90% are within a factor of 10.

Urinary mercury in people living near point sources of mercury emissions.

As part of the European Mercury Emissions from Chlor Alkali Plants (EMECAP) project, we tested the hypothesis that contamination of ambient air with mercury around chlor alkali plants using mercury cells would increase the internal dose of mercury in people living close to the plants. Mercury in urine (U-Hg) was determined in 225 individuals living near a Swedish or an Italian chlor alkali plant, and in 256 age- and sex-matched individuals from two reference areas. Other factors possibly affecting mercury exposure were examined. Emissions and concentrations of total gaseous mercury (TGM) around the plants were measured and modeled. No increase in U-Hg could be demonstrated in the populations living close to the plants. This was the case also when the comparison was restricted to subjects with no dental amalgam and low fish consumption. The emissions of mercury to air doubled the background level, but contributed only about 2 ng/m(3) to long-term averages in the residential areas. The median U-Hg levels in subjects with dental amalgam were 1.2 microg/g creatinine (micro/gC) in Italy and 0.6 microg/gC in Sweden. In individuals without dental amalgam, the medians were 0.9 microg/gC and 0.2 microg/gC, respectively. The number of amalgam fillings, as well as chewing, fish consumption, and female sex were associated with higher U-Hg. The difference between the countries is probably due to higher fish consumption in Italy, demethylated methyl mercury (MeHg) being partly excreted in urine. Post hoc power calculations showed that if the background mercury exposure is low it may be possible to demonstrate an increase in U-Hg of as little as about 10 ng/m(3) as a contribution to ambient mercury from a point source.

Modeling recovery of Swedish ecosystems from acidification.

Dynamic models complement existing time series of observations and static critical load calculations by simulating past and future development of chemistry in forest and lake ecosystems. They are used for dynamic assessment of the acidification and to produce target load functions, that describe what combinations of nitrogen and sulfur emission reductions are needed to achieve a chemical or biological criterion in a given target year. The Swedish approach has been to apply the dynamic acidification models MAGIC, to 133 lakes unaffected by agriculture and SAFE, to 645 productive forest sites. While the long-term goal is to protect 95% of the area, implementation of the Gothenburg protocol will protect approximately 75% of forest soils in the long term. After 2030, recovery will be very slow and involve only a limited geographical area. If there had been no emission reductions after 1980, 87% of the forest area would have unwanted soil status in the long term. In 1990, approximately 17% of all Swedish lakes unaffected by agriculture received an acidifying deposition above critical load. This fraction will decrease to 10% in 2010 after implementation of the Gothenburg protocol. The acidified lakes of Sweden will recover faster than the soils. According to the MAGIC model the median pre-industrial ANC of 107 microeq L(-1) in acid sensitive lakes decreased to about 60 microeq L(-1) at the peak of the acidification (1975-1990) and increases to 80 microeq L(-1) by 2010. Further increases were small, only 2 microeq L(-1) between 2010 and 2040. Protecting 95% of the lakes will require further emission reductions below the Gothenburg protocol levels. More than 7000 lakes are limed regularly in Sweden and it is unlikely that this practice can be discontinued in the near future without adverse effects on lake chemistry and biology.

Economic assessment of the negative impacts of ozone on crop yields and forest production. A case study of the estate Ostads Säteri in southwestern Sweden.

Ground level ozone concentrations, in combination with the prevailing climate, at the estate Ostads Säteri in southwestern Sweden were estimated to reduce the yield of wheat and potato ranging between 5% and 10%. Occasionally, in years with the highest ozone concentrations and/or climatic conditions favoring high rates of ozone uptake to the leaves, yield loss levels above 10% may occur. Based on simple extrapolation, these ozone-induced reductions of crop yields at Ostads Säteri represent a potential total annual yield loss in Sweden in the range of 24.5 million Euro for wheat and 7.3 million Euro for potato, respectively. A simulation of forest growth at Ostad Säteri predicted that prevailing mean ozone exposure during 1993-2003 had the potential to reduce forest growth by 2.2% and the economic return of forest production by 2.6%. Using this value for extrapolation to the national level, the potential annual economic loss for Sweden due to negative impacts of ozone on forest production would be in the range of 56 million Euro (2004 prices).

Forestry practices increase mercury and methyl mercury output from boreal forest catchments.

We observed significant increases in the runoff output of total mercury (TotHg) and methyl mercury (MeHg) from a small spruce forest catchment (0.071 km2) after clear-cutting and soil treatment. Here we show that forest regeneration practices may act as an important additional source of TotHg and MeHg to forest lakes. TotHg and MeHg in runoff from two small forested catchments were monitored during the period 1994 to 2001. In the autumn of 1997, one of the catchments was clear-cut Soil preparation (mounding) was carried out in the autumn of 1998 and replanting in the summer of 1999. During the 3 years after the silvicultural treatment, medians of monthly flow-weighted TotHg and MeHg concentrations (12.02 ng L(-1) and 0.35 ng L(-1), respectively) and output loads (0.80-0.97 g km(-2) a(-1) and 0.011-0.036 g km(-2) a(-1), respectively) increased significantly compared to the 3 years calibration period (8.13 ng L(-1) and 0.15 ng 1(-1); 2.0-5.3 g km(-2) a(-1) and 0.11-0.16 g km(-2) a(-1), respectively). These results indicate that clear-cutting and/or soil treatment significantly increases the mobility of TotHg and MeHg accumulated in forest soil and may thus be an important factor for the total input of Hg to boreal freshwater ecosystems.

Atmospheric mercury near a chlor-alkali plant in Sweden.

Atmospheric mercury species/fractions were measured near a chlor-alkali plant in Sweden during August 28 to September 4, 2001. The concentration of total gaseous mercury in the plume from the plant was measured using TEKRAN and GARDIS instruments. Gaseous elemental mercury was measured using a light detection and ranging (LIDAR) technique. From vertical LIDAR sweeps through the plume from the chlor-alkali plant mercury emission rates could be calculated. The concentrations of reactive gaseous mercury (RGM) in the plume and also inside the cell house were measured using annular KCl coated denuders. The RGM emission constitutes 0.5-1.0% of the total mercury emitted from the plant. The mercury concentration adsorbed on particles was measured as well as the mercury flux from soil. The data presented also include an intercomparison showing an excellent agreement between TEKRAN/GARDIS and LIDAR gaseous mercury measurements.