Parsimonious Model for Simulating Total Mercury and Methylmercury in Boreal Streams Based on Riparian Flow Paths and Seasonality.

The complexity of mercury (Hg) biogeochemistry has made it difficult to model surface water concentrations of both total Hg (THg) and especially methylmercury (MeHg), the species of Hg having the highest potential for bioaccumulation. To simulate THg and MeHg variation in low-order streams, we have adapted a conceptual modeling framework where a continuum of lateral flows through riparian soils determines streamflow concentrations. The model was applied to seven forest catchments located in two boreal regions in Sweden spanning a range of climatic, soil, and forest management conditions. Discharge, and simulated riparian soil water concentrations profiles, represented by two calibrated parameters, were able to explain much of the variability of THg and MeHg concentrations in the streams issuing from the catchments (Nash Sutcliffe (NS) up to 0.54 for THg and 0.58 for MeHg). Model performance for all catchments was improved (NS up to 0.76 for THg and 0.85 for MeHg) by adding two to four parameters to represent seasonality in riparian soil water THg and MeHg concentrations profiles. These results are consistent with the hypothesis that riparian flow-pathways and seasonality in riparian soil concentrations are the major controls on temporal variation of THg and MeHg concentrations in low-order streams.

Half a century of changing mercury levels in Swedish freshwater fish.

The variability of mercury (Hg) levels in Swedish freshwater fish during almost 50 years was assessed based on a compilation of 44 927 observations from 2881 waters. To obtain comparable values, individual Hg concentrations of fish from any species and of any size were normalized to correspond to a standard 1-kg pike [median: 0.69 mg kg⁻¹ wet weight (ww), mean ± SD: 0.84 ± 0.67 mg kg⁻¹ ww]. The EU Environmental Quality Standard of 0.02 mg kg⁻¹ was exceeded in all waters, while the guideline set by FAO/WHO for Hg levels in fish used for human consumption (0.5-1.0 mg kg⁻¹) was exceeded in 52.5 % of Swedish waters after 2000. Different trend analysis approaches indicated an overall long-term decline of at least 20 % during 1965-2012 but trends did not follow any consistent regional pattern. During the latest decade (2003-2012), however, a spatial gradient has emerged with decreasing trends predominating in southwestern Sweden.

Impact of forestry on total and methyl-mercury in surface waters: distinguishing effects of logging and site preparation.

Forestry operations can increase the export of mercury (both total and methyl) to surface waters. However, little is known about the relative contribution of different forestry practices. We address this question using a paired-catchment study that distinguishes the effects of site preparation from the antecedent logging. Runoff water from three catchments, two harvested and one untreated control, was sampled biweekly during one year prior to logging, two years after logging, and three years after site preparation. The logging alone did not significantly increase the concentrations of either total or methyl-mercury in runoff, but export increased by 50-70% in one of the harvested catchments as a consequence of increased runoff volume. The combined effects of logging and site preparation increased total and methyl-mercury concentrations by 30-50% relative to preharvest conditions in both treated catchments. The more pronounced concentration effect after site preparation compared to logging could be related to site preparation being conducted during summer. This caused more soil disturbance than logging, which was done during winter with snow covering the ground. The results suggest that the cumulative impact of forest harvest on catchment mercury outputs depends on when and how forestry operations are implemented.

Dynamic modelling of the long term behaviour of cadmium, lead and mercury in Swiss forest soils using CHUM-AM.

The applicability of the dynamic soil model CHUM-AM was tested to simulate concentrations of Cd, Pb and Hg in five Swiss forest soils. Soil cores of up to 50 cm depth were sampled and separated into two defined soil layers. Soil leachates were collected below the litter by zero-tension lysimeters and at 15 and 50 cm soil depths by tension lysimeters over two years. The concentrations of Cd, Pb and Hg in the solid phase and soil solution were measured by ICP-MS (Cd, Pb) or CV-AFS (Hg). Measured metal concentrations were compared with modelled concentrations using CHUM-AM. Additionally we ran the model with three different deposition scenarios (current deposition; maximum acceptable deposition according to the Swiss ordinance on Air Pollution Control; critical loads according to CLRTAP) to predict metal concentrations in the soils for the next 1000 years. Assuming current loads concentrations of Cd and Pb showed varying trends (increasing/decreasing) between the soils. Soils rich in organic carbon or with a high pH value showed increasing trends in Cd and Pb concentrations whereas the concentrations in the other soils decreased. In contrast Hg concentrations are predicted to further increase in all soils. Critical limits for Pb and Hg will partly be exceeded by current loads or by the critical loads proposed by the CLRTAP but the critical limits for Cd will rarely be reached within the next 1000 years. In contrast, maximal acceptable deposition will partly lead to concentrations above the critical limits for Pb in soils within the next 400 years, whereas the acceptable deposition of Cd will not lead to concentrations above the proposed critical limits. In conclusion the CHUM-AM model is able to accurately simulate heavy metal (Cd, Pb and Hg) concentrations in Swiss forest soils of various soil properties.

Eight boreal wetlands as sources and sinks for methyl mercury in relation to soil acidity, C/N ratio, and small-scale flooding.

Four years of catchment export and wetland input-output mass balances are reported for inorganic Hg (Hg(inorg)), methyl mercury (MeHg), dissolved organic carbon (DOC), and sulfate in eight Swedish boreal wetlands. All wetlands had a history of artificial drainage and seven were subjected to small-scale flooding during the complete study period (two sites) or the two last years (five sites). We used an approach in which specific runoff data determined at hydrological stations situated at a distance from the studied sites were used in the calculation of water and element budgets. All wetlands except one were significant sinks for Hg(inorg). Seven wetlands were consistent sources of MeHg and one (an Alnus glutinosa swamp) was a significant sink. The pattern of MeHg yields was in good agreement with previously determined methylation and demethylation rates in the wetland soils of this study, with a maximum MeHg yield obtained in wetlands with an intermediate soil acidity (pH ∼5.0) and C/N ratio (∼20). We hypothesize that an increased nutrient status from poor to intermediate conditions promotes methylation over demethylation, whereas a further increase in nutrient status and trophy to meso- and eutrophic conditions promotes demethylation over methylation. Small-scale flooding showed no or moderate changes in MeHg yield, maintaining differences among wetlands related to nutrient status.

Mercury concentrations in landlocked Arctic char (Salvelinus alpinus) from the Canadian Arctic. Part I: insights from trophic relationships in 18 lakes.

Concentrations of mercury (Hg) have increased slowly in landlocked Arctic char over a 10- to 15-year period in the Arctic. Fluxes of Hg to sediments also show increases in most Arctic lakes. Correlation of Hg with trophic level (TL) was used to investigate and compare biomagnification of Hg in food webs from lakes in the Canadian Arctic sampled from 2002 to 2007. Concentrations of Hg (total Hg and methylmercury [MeHg]) in food webs were compared across longitudinal and latitudinal gradients in relation to delta(13)C and delta(15)N in periphyton, zooplankton, benthic invertebrates, and Arctic char of varying size-classes. Trophic magnification factors (TMFs) were calculated for the food web in each lake and related to available physical and chemical characteristics of the lakes. The relative content of MeHg increased with trophic level from 4.3 to 12.2% in periphyton, 41 to 79% in zooplankton, 59 to 72% in insects, and 74 to 100% in juvenile and adult char. The delta(13)C signatures of adult char indicated coupling with benthic invertebrates. Cannibalism among char lengthened the food chain. Biomagnification was confirmed in all 18 lakes, with TMFs ranging from 3.5 +/- 1.1 to 64.3 +/- 0.8. Results indicate that TMFs and food chain length (FCL) are key factors in explaining interlake variability in biomagnification of [Hg] among different lakes.

Mercury concentrations in landlocked Arctic char (Salvelinus alpinus) from the Canadian Arctic. Part II: influence of lake biotic and abiotic characteristics on geographic trends in 27 populations.

Among-lake variation in mercury (Hg) concentrations in landlocked Arctic char was examined in 27 char populations from remote lakes across the Canadian Arctic. A total of 520 landlocked Arctic char were collected from 27 lakes, as well as sediments and surface water from a subset of lakes in 1999, 2002, and 2005 to 2007. Size, length, age, and trophic position (delta(15)N) of individual char were determined and relationships with total Hg (THg) concentrations investigated, to identify a common covariate for adjustment using analysis of covariance (ANCOVA). A subset of 216 char from 24 populations was used for spatial comparison, after length-adjustment. The influence of trophic position and food web length and abiotic characteristics such as location, geomorphology, lake area, catchment area, catchment-to-lake area ratio of the lakes on adjusted THg concentrations in char muscle tissue were then evaluated. Arctic char from Amituk Lake (Cornwallis Island) had the highest Hg concentrations (1.31 microg/g wet wt), while Tessisoak Lake (Labrador, 0.07 microg/g wet wt) had the lowest. Concentrations of THg were positively correlated with size, delta(15)N, and age, respectively, in 88, 71, and 58% of 24 char populations. Length and delta(15)N were correlated in 67% of 24 char populations. Food chain length did not explain the differences in length-adjusted THg concentrations in char. No relationships between adjusted THg concentrations in char and latitude or longitude were found, however, THg concentrations in char showed a positive correlation with catchment-to-lake area ratio. Furthermore, we conclude that inputs from the surrounding environment may influence THg concentrations, and will ultimately affect THg concentrations in char as a result of predicted climate-driven changes that may occur in Arctic lake watersheds.

Elevated concentrations of methyl mercury in streams after forest clear-cut: a consequence of mobilization from soil or new methylation?

Concentrations of inorganic, mercuric mercury (Hg(II)), methyl mercury (MeHg) and ancillary chemistry measured in first-order streams draining 0-4 (N = 20) and 4-10 (N = 27) year-old clear-cuts of former Norway Spruce Picea abies (Karst.) forest stands were compared with concentrations in streams draining >70 year-old Norway Spruce reference stands (N = 10). Concentrations of MeHg, and ratios of MeHg TOC(-1) and Hg(II) TOC(-1), were significantly (p < 0.01) elevated in 0-4 year-old clear-cuts, as compared to references. The only ancillary variable showing a significant elevation for 0-4 year-old clear-cuts was Mn (p < 0.02). The 4-10 year-old clear-cuts showed intermediate concentrations with nonsignificant differences as compared to references. pH, nitrate, sulfate, Ca, Fe, TOC, TON, and the aromaticity of TOC (SUVA(254 nm)) showed nonsignificant differences between clear-cut age classes and references. Assuming that MeHg and Hg(II) are mobilized from soil to stream to a similar relative extent as a consequence of clear-cutting, a calculation showed that (1)/(6) of the elevated MeHg concentration was due to enhanced mobilization from soil and (5)/(6) was due to new methylation of Hg(II) 0-4 years after clear-cut. New methylation after clear-cut is suggested to be stimulated by an increased availability of electron donors for methylating bacteria, as a consequence of degradation of logging residue ("slash") and soil organic matter. A subdivision of sites situated above and below the highest postglacial coastline (HC) revealed a significant elevation of MeHg, MeHg TOC(-1) and Hg(II) TOC(-1) (p < 0.05) beyond their references in 0-4 year-old clear-cuts above (but not below) the HC. This suggests that postglacial deposits of FeS(s) and FeS(2)(s) were not an important factor for elevation of MeHg after clear-cut.

Forest harvest increases runoff most during low flows in two boreal streams.

To understand how forest harvest influences the aquatic environment, it is essential to determine the changes in the flow regime. This paper presents changes in the hydrological regime during the first 2 y after harvest in two catchments of the Balsjö Catchment Study in Sweden. The changes were judged relative to a reference catchment, calibrated during an 18-mo pretreatment period starting in September 2004. From August 2006 through March 2008, there was an average of 35% more runoff from the harvested catchments relative to the reference. The flow increased most during the growing seasons and at base flows (<1 mm d(-1); 58-99% increase), followed by dormant season and intermediate flows (30-43%). No significant changes were observed during the highest flows (over 5 mm d(-1)), except for the spring flood a few weeks after harvest, which was delayed and attenuated. Large relative changes in low flow may influence the ecosystem by altering the aquatic habitat.

The effects of forest harvest operations on mercury and methylmercury in two boreal streams: relatively small changes in the first two years prior to site preparation.

Forest harvest is hypothesized to increase the mercury (Hg) load in aquatic ecosystems. The Balsjö paired catchment study examined the outputs of methylmercury (MeHg) and total mercury (Hg(tot)) from two boreal catchments during the 2 y following forest harvest but prior to site preparation. This enabled us to separate the effect of the two operations that followed best management practices. Hg(tot) concentrations increased by approximately 15%, and fluxes by 20-30%. The MeHg concentrations and fluxes either declined or increased by up to 60%, depending on whether annual MeHg peaks during summer low flows were considered to have been influenced by forest harvest. The lack of a severalfold increase in Hg outputs after forest harvest, as reported from other sites, may be the result of minimal soil disturbance during the winter forest harvest operations. If so, there may be a greater Hg response after soil scarification to prepare for planting.

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.

Influence of liming on metal sequestration in lake sediments over recent decades.

Sediment profiles from five limed and six reference softwater lakes included in Swedish monitoring programmes were subjected to multi-element analysis to investigate the influence of lime treatment since 1977 on the sequestration of metals in lake sediments. We hypothesised that liming causes increased sedimentation of elements for which the mobility is primarily controlled by pH, e.g. Al, Cd, Co, Ni and Zn, whereas elements that are less influenced by pH fluctuations, e.g. Hg and Pb, are not affected by lime treatment. Further, we introduce a normalisation of metal concentrations with respect to Cu concentration in order to separate the effects of lime treatment from those related to temporal trends in airborne metal deposition or short-term variations in environmental conditions. This approach is shown to emphasise the effect of liming on the sediment accumulation of metals, thus separating it from other sources of variability. We found that liming causes increased sequestration of Al, As, Cd, Co, Fe, Mn, Ni and Zn, in the case of As and Co probably at least partly caused by an increased adsorption to Al, Fe and Mn oxyhydroxides. On the other hand, no influence of lime treatment could be demonstrated for Hg, Pb, Cr, V and P, despite an increase of pH by about two units.

Impact of soil properties on critical concentrations of cadmium, lead, copper, zinc, and mercury in soil and soil solution in view of ecotoxicological effects.

Risk assessment for metals in terrestrial ecosystems, including assessments of critical loads, requires appropriate critical limits for metal concentrations in soil and soil solution. This chapter presents an overview of methodologies used to derive critical (i) reactive and total metal concentrations in soils and (ii) free metal ion and total metal concentrations in soil solution for Cd, Pb, Cu, Zn, and Hg, taking into account the effect of soil properties related to ecotoxicological effects. Most emphasis is given to the derivation of critical free and total metal concentrations in soil solution, using available NOEC soil data and transfer functions relating solid-phase and dissolved metal concentrations. This approach is based on the assumption that impacts on test organisms (plants, microorganisms, and soil invertebrates) are mainly related to the soil solution concentration (activity) and not to the soil solid-phase content. Critical Cd, Pb, Cu, Zn, and Hg concentrations in soil solution vary with pH and DOC level. The results obtained are generally comparable to those derived for surface waters based on impacts to aquatic organisms. Critical soil metal concentrations, related to the derived soil solution limits, can be described as a function of pH and organic matter and clay content, and varying about one order of magnitude between different soil types.

Fish mercury increase in Lago Manso, a new hydroelectric reservoir in tropical Brazil.

It has been frequently demonstrated that mercury (Hg) concentrations in fish rise in newly constructed hydroelectric reservoirs in the Northern Hemisphere. In the present work, we studied whether similar effects take place also in a tropical upland reservoir during impoundment and discuss possible causes and implications. Total Hg concentrations in fish and several soil and water parameters were determined before and after flooding at Rio Manso hydroelectric power plant in western Brazil. The Hg concentrations in soil and sediment were within the background levels in the region (22-35 ng g(-1) dry weight). There was a strong positive correlation between Hg and carbon and sulphur in sediment. Predatory fish had total Hg concentrations ranging between 70 and 210 ng g(-1) f.w. 7 years before flooding and between 72 and 755 ng g(-1) f.w. during flooding, but increased to between 216 and 938 ng g(-1) f.w. in the piscivorous and carnivorous species Pseudoplatystoma fasciatum, cachara, and Salminus brasiliensis, dourado, 3 years after flooding. At the same time, concentrations of organic carbon in the water increased and oxygen concentrations decreased, indicating increased decomposition and anoxia as contributing to the increased Hg concentrations in fish. The present fish Hg concentrations in commonly consumed piscivorous species are a threat to the health of the population dependent on fishing in the dam and downstream river for sustenance. Mercury exposure can be reduced by following fish consumption recommendations until fish Hg concentrations decrease to a safe level.

500 years of mercury production: global annual inventory by region until 2000 and associated emissions.

Since pre-industrial times, anthropogenic emissions of Hg have at least doubled global atmospheric Hg deposition rates. In order to minimize environmental and human health effects, efforts have been made to reduce Hg emissions from industries and power plants, while less attention has been paid to Hg mining. This paper is a compilation of available data on primary Hg production and associated emissions with regional and annual resolution since colonial times. Globally, approximately one million tons of metallic Hg has been extracted from cinnabar and other ores during the past five centuries, half already before 1925. Roughly half has been used for mining of gold and silver, but the annual Hg production peaked during a short period of recent industrial uses. Comparison with total historic Hg deposition from global anthropogenic emissions (0.1-0.2 Mtons) suggests that only a few percent of all mined Hg have escaped to the atmosphere thus far. While production of primary Hg has changed dramatically over time and among mines, the global production has always been dominant in the region of the mercuriferous belt between the western Mediterranean and central Asia, but appears to be shifting to the east. Roughly half of the registered Hg has been extracted in Europe, where Spanish mines alone have contributed one third of the world's mined Hg. Approximately one fourth has been mined in the Americas, and most of the remaining registered Hg in Asia. However, the Asian figures may be largely underestimated. Presently, the dominant Hg mines are in Almadén in Spain (236 t of Hg produced in 2000), Khaydarkan in Kyrgyzstan (550 t), Algeria (estimated 240 t) and China (ca. 200 t). Mercury by-production from mining of other metals (e.g. copper, zinc, gold, silver) in 2000 includes 48 t from Peru, 45 t from Finland and at least 15 t from the USA. Since 1970, the recorded production of primary Hg has been reduced by almost an order of magnitude to approximately 2000 t in the year 2000. Mining is thus still of similar magnitude as all current anthropogenic Hg emissions to the atmosphere, and mined Hg may account for more than one third of these emissions. Also before use, mercury is emitted from Hg mines locally during the mining and refining processes and from mining waste. Global direct emissions to the atmosphere amount to 10-30 t per year currently (up to 10 at Almadén alone), and probably exceed 10000 t historically. Termination of Hg mining will reduce associated local emissions to the atmosphere and biosphere. Since several economically viable Hg-free alternatives exist for practically all applications of Hg, the production and use of Hg can be further reduced and all primary production of Hg other than by-production terminated.

Critical levels of atmospheric pollution: criteria and concepts for operational modelling of mercury in forest and lake ecosystems.

Mercury (Hg) is regarded as a major environmental concern in many regions, traditionally because of high concentrations in freshwater fish, and now also because of potential toxic effects on soil microflora. The predominant source of Hg in most watersheds is atmospheric deposition, which has increased 2- to >20-fold over the past centuries. A promising approach for supporting current European efforts to limit transboundary air pollution is the development of emission-exposure-effect relationships, with the aim of determining the critical level of atmospheric pollution (CLAP, cf. critical load) causing harm or concern in sensitive elements of the environment. This requires a quantification of slow ecosystem dynamics from short-term collections of data. Aiming at an operational tool for assessing the past and future metal contamination of terrestrial and aquatic ecosystems, we present a simple and flexible modelling concept, including ways of minimizing requirements for computation and data collection, focusing on the exposure of biota in forest soils and lakes to Hg. Issues related to the complexity of Hg biogeochemistry are addressed by (1) a model design that allows independent validation of each model unit with readily available data, (2) a process- and scale-independent model formulation based on concentration ratios and transfer factors without requiring loads and mass balance, and (3) an equilibration concept that accounts for relevant dynamics in ecosystems without long-term data collection or advanced calculations. Based on data accumulated in Sweden over the past decades, we present a model to determine the CLAP-Hg from standardized values of region- or site-specific synoptic concentrations in four key matrices of boreal watersheds: precipitation (atmospheric source), large lacustrine fish (aquatic receptor and vector), organic soil layers (terrestrial receptor proxy and temporary reservoir), as well as new and old lake sediments (archives of response dynamics). Key dynamics in watersheds are accounted for by quantifying current states of equilibration in both soils and lakes based on comparison of contamination factors in sediment cores. Future steady-state concentrations in soils and fish in single watersheds or entire regions are then determined by corresponding projection of survey data. A regional-scale application to southern Sweden suggests that the response of environmental Hg levels to changes in atmospheric Hg pollution is delayed by centuries and initially not proportional among receptors (atmosphere >> soils not equal sediments>fish; clearwater lakes >> humic lakes). This has implications for the interpretation of common survey data as well as for the implementation of pollution control strategies. Near Hg emission sources, the pollution of organic soils and clearwater lakes deserves attention. Critical receptors, however, even in remote areas, are humic waters, in which biotic Hg levels are naturally high, most likely to increase further, and at high long-term risk of exceeding the current levels of concern:

Modelling the dynamics of fish contamination by Chernobyl radiocaesium: an analytical solution based on potassium mass balance.

After the sudden fallout from the Chernobyl nuclear accident in 1986, activities and bioaccumulation factors of radiocaesium ((137)Cs, (134)Cs) fluctuated strongly over several years before reaching quasi-equilibrium, with patterns significantly differing among organisms. To model these dynamic relaxation processes based on ecological mechanisms we developed mass balance equations for (137)Cs in an aquatic food chain on the following basis: (a). potassium acts as a biogeochemical analogue ("carrier") of caesium; (b). the concentration of potassium in fish and other animals is effectively constant; (c). the main source of potassium in freshwater fish is the dietary uptake. The model is applicable to linear food chains of any number of trophic levels, while solutions evaluated here include the following food chain compartments: water, invertebrates (fish food), non-piscivorous fish, and piscivorous fish. The activity concentration in the water, which is considered as the secondary source of (137)Cs, is described by multi-component first-order decay function, although two components (fast and slow) are often sufficient to provide agreement with empirical data. In every compartment the turnover rate of caesium is considered as a constant over time. The analytical solution of the model equations describes the (137)Cs activity concentration in every compartment as a series of exponential functions, of which some are derived from the source pattern, and the others determined by the (137)Cs turnover rate in each food chain compartment. The model was tested with post-Chernobyl data from several long-term studies in lakes and provided a reasonable description of important radioecological aspects.