Updated trends for atmospheric mercury in the Arctic: 1995-2018.

The Arctic region forms a unique environment with specific physical, chemical, and biological processes affecting mercury (Hg) cycles and limited anthropogenic Hg sources. However, historic global emissions and long range atmospheric transport has led to elevated Hg in Arctic wildlife and waterways. Continuous atmospheric Hg measurements, spanning 20 years, and increased monitoring sites has allowed a more comprehensive understanding of how Arctic atmospheric mercury is changing over time. Time-series trend analysis of TGM (Total Gaseous Mercury) in air was performed from 10 circumpolar air monitoring stations, comprising of high-Arctic, and sub-Arctic sites. GOM (gaseous oxidised mercury) and PHg (particulate bound mercury) measurements were also available at 2 high-Arctic sites. Seasonal mean TGM for sub-Arctic sites were lowest during fall ranging from 1.1 ng m-3 Hyytiälä to 1.3 ng m-3, Little Fox Lake. Mean TGM concentrations at high-Arctic sites showed the greatest variability, with highest daily means in spring ranging between 4.2 ng m-3 at Amderma and 2.4 ng m-3 at Zeppelin, largely driven by local chemistry. Annual TGM trend analysis was negative for 8 of the 10 sites. High-Arctic seasonal TGM trends saw smallest decline during summer. Fall trends ranged from -0.8% to -2.6% yr-1. Across the sub-Arctic sites spring showed the largest significant decreases, ranging between -7.7% to -0.36% yr-1, while fall generally had no significant trends. High-Arctic speciation of GOM and PHg at Alert and Zeppelin showed that the timing and composition of atmospheric mercury deposition events are shifting. Alert GOM trends are increasing throughout the year, while PHg trends decreased or not significant. Zeppelin saw the opposite, moving towards increasing PHg and decreasing GOM. Atmospheric mercury trends over the last 20 years indicate that Hg concentrations are decreasing across the Arctic, though not uniformly. This is potentially driven by environmental change, such as plant productivity and sea ice dynamics.

The presence of mercury and other trace metals in surface soils in the Norwegian Arctic.

Svalbard is an important study area for investigating the long-range transport of mercury (Hg) and other trace elements to the Arctic. Few studies have focused on their concentrations in Arctic soils. With ongoing climate change leading to thawing permafrost ground the soil compartment is of increasing importance in the Arctic. In this study, elemental composition and soil organic matter (SOM) content of surface and mineral soils in Svalbard are presented. The aim is to provide new data on soils in the Arctic and to gain more knowledge about the role of the soil in the biogeochemical cycle of mercury (Hg). Concentrations are reported for Al, As, Cd, Cr, Cu, Fe, Hg, Mn, Ni, Pb, S and Zn. Samples were taken in Adventdalen and in the area near Ny-Ålesund. We obtained a mean Hg concentration of 0.111 ± 0.036 µg/g in surface soils (range 0.041-0.254 µg/g). Hg levels in mineral soils (mean: 0.025 ± 0.013 µg/g; range: 0.004-0.060 µg/g) were substantially lower than in the corresponding surface soils. Hg strongly accumulates in the surface soil layer (upper 3 cm) and is associated with SOM (surface soil: 59 ± 14%). Hg concentrations in the surface soil were slightly lower than those in the humus layer in mainland Norway and were comparable to levels in soils elsewhere in the Arctic. An inverse association of Hg was found with elements attributed to the mineral soil, indicating that Hg is predominantly derived from atmospheric deposition.

Essential and non-essential elements in natural vegetation in southern Norway: contribution from different sources.

Concentrations of essential and non-essential elements in five widespread species of natural boreal vegetation were studied with respect to seasonal variation and contribution from different sources. The plant species included in the study were Betula pubescens, Sorbus aucuparia, Vaccinium myrtillus, Vaccinium uliginosum, Calluna vulgaris and Deschampsia flexuosa. Concentrations of elements essential to plants remained essentially constant or decreased slightly throughout the growing season. Concentrations of most non-essential elements increased or tended to increase on a dry mass basis from June to July as well as from July to September. The increasing trend for these elements was observed for all species except C. vulgaris. Principal component analysis (PCA) of the material indicated a common source for many of the non-essential elements; Sc, Ti, V, Ga, As, Y, Sb, lanthanides, Pb, Bi, and U, i.e. both elements presumably of geogenic origin and elements associated with trans-boundary air pollution. Uptake by plant roots appeared to be the main source of nutrient elements as well as some non-essential elements.

Toxic and essential elements changed in black-legged kittiwakes (Rissa tridactyla) during their stay in an Arctic breeding area.

Seasonal fluctuations in mercury (Hg), cadmium (Cd), zinc (Zn), copper (Cu) and selenium (Se) concentrations were studied in black-legged kittiwakes (Rissa tridactyla) from Kongsfjorden, Svalbard (79°57'N, 12°12'E). Element concentrations were determined in muscle and liver tissue in kittiwakes collected in May, July and October 2007. Stable isotopes of carbon (δ(13)C) and nitrogen (δ(15)N) were analysed in muscle tissue to calculate trophic position (TP) and examine the possible influence of carbon source on element accumulation. Metallothionein (MT) concentrations in liver, as well as Hg and Cd concentration in size-fractionated liver supernatant were determined to evaluate the association between elements and MT. Mercury concentrations declined from May through July to October in both tissues, while concentrations of Cd were similar in May and July and lower in October. A decline in TP between May and July, indicating a shift from fish-based diet towards an invertebrate-based diet explains the declining Hg concentration. The low Hg and Cd concentrations in October may be a result of an increased elimination, probably related to moulting. Selenium decreased in the same manner as Hg in liver and muscle, possibly related to the formation of Se-Hg complexes. Zinc and Cu did not fluctuate in muscle tissue, whereas hepatic Zn concentrations where highest in May. Hepatic Zn concentrations were higher in females compared to males in May, possibly related to egg production. Hepatic MT concentrations were lower in October compared to July, following the same trend as Hg and Cd. Cadmium was predominantly bound to the MT fraction of proteins in liver tissue, whereas Hg was associated with the larger proteins, indicating that MT was not sequestering Hg in the kittiwakes.

Effect of diet, location and sampling year on bioaccumulation of mercury, selenium and cadmium in pelagic feeding seabirds in Svalbard.

Hepatic concentrations of mercury (Hg), selenium (Se) and cadmium (Cd) were determined in black-legged kittiwakes (Rissa tridactyla) and little auks (Alle alle) from two fjords in Svalbard (Kongsfjorden; 78°57'N, 12°12'E and Liefdefjorden; 79°37'N, 13°20'E). The inflow of Arctic and Atlantic water differs between the two fjords, potentially affecting element accumulation. Trophic positions (TP) were derived from stable nitrogen isotope ratios (δ(15)N), and stable carbon isotope ratios (δ(13)C) were assessed to evaluate the terrestrial influence on element accumulation. Mercury, Cd, TP and δ(13)C varied significantly between locations and years in both species. Trophic position and feeding habits explained Hg and Cd accumulation in kittiwakes, but not in little auks. Biomagnification of Hg and Cd were found in the food webs of both the Atlantic and the Arctic fjord, and no inter-fjord differences were detected. The δ(13)C were higher in the seabirds from Kongsfjorden than in Liefdefjorden, but this did not explain variations in element accumulation. Selenium concentrations were not influenced by Hg accumulation in kittiwakes, indicating baseline levels of Se in this species. In contrast, correlations between Hg and Se and lower Se:Hg ratios in little auks from Kongsfjorden than in Liefdefjorden indicate a more pronounced influence of Se-Hg complex formation in little auks feeding in Atlantic waters.

Acute and sub-lethal response to mercury in Arctic and boreal calanoid copepods.

Acute lethal toxicity, expressed as LC50 values, is a widely used parameter in risk assessment of chemicals, and has been proposed as a tool to assess differences in species sensitivities to chemicals between climatic regions. Arctic Calanus glacialis and boreal Calanus finmarchicus were exposed to mercury (Hg(2+)) under natural environmental conditions including sea temperatures of 2° and 10°C, respectively. Acute lethal toxicity (96 h LC50) and sub-lethal molecular response (GST expression; in this article gene expression is used as a synonym of gene transcription, although it is acknowledged that gene expression is also regulated, e.g., at translation and protein stability level) were studied. The acute lethal toxicity was monitored for 96 h using seven different Hg concentrations. The sub-lethal experiment was set up on the basis of nominal LC50 values for each species using concentrations equivalent to 50, 5 and 0.5% of their 96 h LC50 value. No significant differences were found in acute lethal toxicity between the two species. The sub-lethal molecular response revealed large differences both in response time and the fold induction of GST, where the Arctic species responded both faster and with higher mRNA levels of GST after 48 h exposure. Under the natural exposure conditions applied in the present study, the Arctic species C. glacialis may potentially be more susceptible to mercury exposure on the sub-lethal level.

Mercury in molar excess of selenium interferes with thyroid hormone function in free-ranging freshwater fish.

Thyroid hormones (THs) are essential for cellular metabolism, somatic growth and development, and reproduction. Mercury (Hg) entering aquatic systems and accumulated as highly toxic methylmercury (MeHg) represents a threat to wildlife and human health. Selenium (Se) is an essential element critical for TH activation and regulation. In organisms, binding of Hg in a Se-Hg complex results in a detoxification of Hg. However, formation of Se-Hg complexes also affects Se bioavailability, disrupting functions of Se-dependent enzymes, such as TH deiodinases, which convert thyroxine (T4) to the physiologically active TH, triiodothyronine (T3). The main aim of the present study was to investigate how tissue Se:Hg molar ratios, tissue levels of Se and Hg, and other potential TH disruptive contaminants (metals and organic chemical compounds) affect plasma TH levels in free-ranging brown trout, Salmo trutta , from Lake Mjøsa (a Se-deprived lake) and Lake Losna (a reference lake), Norway. Among the wide range of potential TH disruptive pollutants investigated, tissue Se:Hg molar ratios in muscle and liver were the most significant predictors of plasma TH levels in the trout. Moreover, lower plasma levels of the biological active hormone, T3, in the Lake Mjøsa trout co-occurred with their low Se:Hg molar ratios. This suggests that Se availability is impaired by Hg and results in altered selenoenzyme activities and loss of optimal control of TH balance in free-ranging freshwater fish.

Three decades of atmospheric metal deposition in Norway as evident from analysis of moss samples.

Monitoring of atmospheric deposition of metals in Norway on a nationwide scale using samples of terrestrial moss started in 1977 and has been repeated every 5 years. This has facilitated a detailed record of temporal and spatial trends of metal deposition all over the country as a supplement to measurements based on bulk deposition sampling on a small number of sites. Pb, Zn, Cd, As, Sb, V, Sn, Mo, and Bi all show highest deposition in the far south due to trans-boundary pollution from other parts of Europe, but the contribution from long-range atmospheric transport to metal deposition has decreased substantially over the years. The distributions of Fe, Ni, Cu, Cr, and Co are more affected by local sources, but a decreasing time trend is also evident for these elements. Se is mainly derived from processes in the marine environment. Deposition of metals from Cu-Ni smelters in Russia situated close to the Norwegian border has shown a steadily increasing trend over the time period concerned.

Selenium moderates mercury toxicity in free-ranging freshwater fish.

Due to the extremely high affinity of selenium (Se) to mercury (Hg), Se sequesters Hg and reduces its biological availability in organisms. However the converse is also true. Hg sequesters Se, causing Hg to inhibit the formation of Se dependent enzymes while supplemental Se supports their continued synthesis. Hence, whether or not toxic effects accompany exposure to Hg depends upon the tissue Se:Hg molar ratio of the organism. The main objective of the present study was to investigate how levels of Hg and Se affected metallothionein (MT) induction in free-ranging brown trout, Salmo trutta, from Lake Mjøsa, Norway (a Se depauperate lake). MT is proposed as a sensitive biomarker of potential detrimental effects induced by metals such as Hg. Emphasis was addressed to elucidate if increased tissue Se:Hg molar ratios and Se levels affected the demands for MT in the trout. The Se:Hg molar ratio followed by tissue Se levels were most successful for assessing the relationship between metal exposure and MT levels in the trout. Thus, Hg in molar excess over Se was a stronger inducer of MT synthesis than tissue Hg levels in the trout, supporting the assumption that Se has a prominent protective effect against Hg toxicity. Measuring Hg in animals may therefore provide an inadequate reflection of the potential health risks to humans and wildlife if the protective effects of Se are not considered.

Characterisation of individual aerosol particles on moss surfaces: implications for source apportionment.

The size, morphology and chemical composition of 8405 particles on moss surfaces (Hylocomium splendens) was investigated by scanning electron microscopy and energy-dispersive X-ray microanalysis. Two moss samples from three locations in Southern Norway (Algård, Birkeland, Neslandsvatn) and two sampling years (1977 and 2005) each were selected leading to a total of 12 samples investigated. At all three locations, particle deposition decreased substantially with time. The major particle groups encountered include silicates, iron-rich silicates, metal oxides/hydroxides, iron oxides/hydroxides, carbonates, carbon-rich particles, silicate fly ashes, iron-rich silicate fly ashes, and iron oxide fly ashes. Between 1977 and 2005, the relative number abundance of the three fly ash groups decreased substantially from approximately 30-60% to 10-18% for the small particles (equivalent projected area diameter <1 microm), and from 10-35% to 2-9% for large particles with diameters ≥1 microm. This decrease of fly ash particles with time was overlooked in previous papers on atmospheric input of pollutants into ecosystems in Southern Norway. In general, the presence of fly ash particles is ignored in most source apportionment studies based on bulk chemical analysis. Consequently, the geogenic component (crustal component) derived from principal component analysis is overestimated systematically, as it has a similar chemical composition as the fly ash particles. The high abundance of fly ashes demonstrates the need to complement source apportionment based on bulk chemistry by scanning electron microscopy in order to avoid misclassification of this important anthropogenic aerosol component.

Decline in atmospheric mercury deposition in London.

Bulk atmospheric deposition samples were continuously collected using a standard IVL-type mercury (Hg) bulk deposition collector from January 1999 to December 2005 in order to monitor Hg deposition in London. The volume-weighted annual Hg concentrations in deposition gradually declined from 76.0 ng L(-1) in 1999 to 43.8 ng L(-1) in 2005. Correspondingly, Hg fluxes in deposition declined from 45.3 microg m(-2) yr(-1) in 1999 to 15.0 microg m(-2) yr(-1) in 2005. However, this decline in Hg deposition does not agree with trends in UK Hg emissions which are relatively stable over the sampling period. Comparison with contemporaneous data collected at Lochnagar, a remote site in Scotland, suggests that the high Hg concentrations in London deposition are likely to be due to local or regional sources. Surface sediments taken from lakes across London show that the environment has been heavily contaminated by Hg and suggest that Hg re-emission from depositional sinks (e.g. soils, water bodies) may be an important source to London's atmosphere, thereby delaying response to the major reductions in direct emissions to the atmosphere since the 1970s.

Atmospheric mercury depletion event study in Ny-Alesund (Svalbard) in spring 2005. Deposition and transformation of Hg in surface snow during springtime.

A field campaign was conducted in Ny-Alesund (78 degrees 54'N, 11 degrees 53'E), Svalbard (Norway) during April and May 2005. An Atmospheric Mercury (Hg) Depletion Event (AMDE) was observed from the morning of April 24 until the evening of April 27. Transport of already Hg and ozone (O3) depleted air masses could explain this observed depletion. Due to a snowfall event during the AMDE, surface snow Hg concentrations increased two fold. Hg deposition took place over a short period of time corresponding to 3-4 days. More than 80% of the deposited Hg was estimated to be reemitted back to the atmosphere in the days following the event. During the campaign, we observed night and day variations in surface snow Hg concentrations, which may be the result of gaseous elemental mercury (GEM) oxidation to divalent Hg at the snow/air interface by daylight surface snow chemistry. Finally, a decrease in the reactive Hg (HgR) fraction of total Hg (HgT) in the surface snow was observed during spring. We postulate that the transformation of HgR to a more stable form may occur in Arctic snow during spring.

Mercury in the atmosphere, snow and melt water ponds in the North Atlantic Ocean during Arctic summer.

Atmospheric mercury speciation measurements were performed during a 10 week Arctic summer expedition in the North Atlantic Ocean onboard the German research vessel RV Polarstern between June 15 and August 29, 2004. This expedition covered large areas of the North Atlantic and Arctic Oceans between latitudes 54 degrees N and 85 degrees N and longitudes 16 degrees W and 16 degrees E. Gaseous elemental mercury (GEM), reactive gaseous mercury (RGM) and mercury associated with particles (Hg-P) were measured during this study. In addition, total mercury in surface snow and meltwater ponds located on sea ice floes was measured. GEM showed a homogeneous distribution over the open North Atlantic Ocean (median 1.53 +/- 0.12 ng/m3), which is in contrast to the higher concentrations of GEM observed over sea ice (median 1.82 +/- 0.24 ng/m3). It is hypothesized that this results from either (re-) emission of mercury contained in snow and ice surfaces that was previously deposited during atmospheric mercury depletion events (AMDE) in the spring or evasion from the ocean due to increased reduction potential at high latitudes during Arctic summer. Measured concentrations of total mercury in surface snow and meltwater ponds were low (all samples <10 ng/L), indicating that marginal accumulation of mercury occurs in these environmental compartments. Results also reveal low concentrations of RGM and Hg-P without a significant diurnal variability. These results indicate that the production and deposition of these reactive mercury species do not significantly contribute to the atmospheric mercury cycle in the North Atlantic Ocean during the Arctic summer.

Atmospheric mercury in Norway: contributions from different sources.

The environmental loadings of national Norwegian mercury emissions compared to the loadings of atmospheric long range transported mercury have been estimated using national emission data and EMEP model data. The results indicate that atmospheric long-range transport to Norway is somewhat larger than the national Norwegian emissions of mercury. Atmospheric deposition of mercury has been studied using data from Norwegian monitoring programs on mercury in precipitation, mosses, natural surface soils, and lake sediments. Precipitation data show no significant time trend during 1990-2002, whereas moss samples show similar concentrations from 1985 to 1995, but a 30% decrease from 1995 to 2000. Concentrations of mercury in peat cores and reference sediments indicate that the current mercury levels measured in surface sediments, surface soils and mosses at background sites in Norway are substantially affected by long-range atmospheric transport.

Springtime depletion of mercury in the European Arctic as observed at Svalbard.

This study was carried out to see whether the geographical extent of the mercury depletion events (MDEs), first seen at Alert in the Canadian High Arctic, is also covering Svalbard. Another goal was to determine the main reaction products from the MDE and their fate. Gaseous elemental mercury (GEM), total particulate mercury (TPM), reactive gaseous mercury (RGM) and total mercury in surface snow have been measured at the Zeppelin mountain during 2000. GEM has been measured with a high time resolution automatic monitor (Tekran 2537A) based on CV-AFS, TPM was sampled/measured using high volume samplers/CV-AFS and RGM was sampled with annular denuders and measured by CV-AFS (Gardis Hg-monitor). During spring of 2000, in the three-month period following polar sunrise, there were several episodic depletions in GEM concentration correlating well with the depletion of surface ozone. Measurements of RGM and TPM showed higher concentrations of these mercury species during the depletion period than during the rest of the year. Total mercury in surface snow showed a distinct increase from the polar night to the Arctic spring. MDEs are caused by the specific chemical and physical conditions observed in the Arctic during spring. GEM is oxidised and converted to more reactive forms (RGM and/or TPM), which have considerably higher deposition velocities than elemental mercury, leading to an overall enhanced deposition flux of mercury.