Field controlled experiments of mercury accumulation in crops from air and soil

Field open top chambers (OTCs) and soil mercury (Hg) enriched experiments were employed to study the influence of Hg concentrations in air and soil on the Hg accumulation in the organs of maize (Zea mays L.) and wheat (Triticum aestivum L.). Results showed that Hg concentrations in foliages were correlated significantly (p < 0.05) with air Hg concentrations but insignificantly correlated with soil Hg concentrations, indicating that Hg in crop foliages was mainly from air. Hg concentrations in roots were generally correlated with soil Hg concentrations (p < 0.05) but insignificantly correlated with air Hg concentrations, indicating that Hg in crop roots was mainly from soil. No significant correlations were found between Hg concentrations in stems and those in air and soil. However, Hg concentrations in upper stems were usually higher than those in bottom stems, implying air Hg might have stronger influence than soil Hg on stem Hg accumulation.     

Large-scale spatial variation in mercury concentrations in cattle in NW Spain

Mercury (Hg) is a highly toxic environmental contaminant and man-made emissions account for between a quarter and a third of total atmospheric levels. Point discharges, particularly coal-burning power stations, are major sources of atmospheric Hg and can result in marked spatial variation in mercury deposition and subsequent uptake by biota. The aims of this study were to quantify the extent to which major point and diffuse sources of atmospheric Hg emissions affected accumulation of Hg by biota throughout Galicia and Asturias, two of the major regions in northwest Spain. We did this by relating renal Hg concentrations in locally reared cattle (n=284) to the proximity of animals to point and diffuse sources of Hg emissions. Mercury residues in calf kidneys ranged between non-detected and 89.4 g/kg wet weight. Point discharges from coal-fired power plants in Galicia had the most dominant impact on Hg accumulation by calves in Galicia, affecting animals throughout the region and explaining some two-thirds of the variation in renal residues between animals located directly downwind from the plants. The effects of more diffuse emission sources on Hg accumulation in calves were not distinguishable in Galicia but were detected in cattle from neighbouring Asturias. The impact of both point and diffuse sources in elevating environmental levels of bioavailable Hg and subsequent accumulation by cattle extended to approximately 140-200 km downwind from source.     

Mercury accumulation in grass and forb species as a function of atmospheric carbon dioxide concentrations and mercury exposures in air and soil

The goal of this study was to investigate the potential for atmospheric Hg degrees uptake by grassland species as a function of different air and soil Hg exposures, and to specifically test how increasing atmospheric CO(2) concentrations may influence foliar Hg concentrations. Four common tallgrass prairie species were germinated and grown for 7 months in environmentally controlled chambers using two different atmospheric elemental mercury (Hg major; 3.7+/-2.0 and 10.2+/-3.5 ng m(-3)), soil Hg (<0.01 and 0.15+/-0.08 micro g g(-1)), and atmospheric carbon dioxide (CO(2)) (390+/-18, 598+/-22 micro mol mol(-1)) exposures. Species used included two C4 grasses and two C3 forbs. Elevated CO(2) concentrations led to lower foliar Hg concentrations in plants exposed to low (i.e., ambient) air Hg degrees concentrations, but no CO(2) effect was apparent at higher air Hg degrees exposure. The observed CO(2) effect suggests that leaf Hg uptake might be controlled by leaf physiological processes such as stomatal conductance which is typically reduced under elevated CO(2). Foliar tissue exposed to elevated air Hg degrees concentrations had higher concentrations than those exposed to low air Hg degrees , but only when also exposed to elevated CO(2). The relationships for foliar Hg concentrations at different atmospheric CO(2) and Hg degrees exposures indicate that these species may have a limited capacity for Hg storage; at ambient CO(2) concentrations all Hg absorption sites in leaves may have been saturated while at elevated CO(2) when stomatal conductance was reduced saturation may have been reached only at higher concentrations of atmospheric Hg degrees . Foliar Hg concentrations were not correlated to soil Hg exposures, except for one of the four species (Rudbeckia hirta). Higher soil Hg concentrations resulted in high root Hg concentrations and considerably increased the percentage of total plant Hg allocated to roots. The large shifts in Hg allocation patterns-notably under soil conditions only slightly above natural background levels-indicate a potentially strong role of plants in belowground Hg transformation and cycling processes.     

Electrochemical behaviors of sulfhydryl compounds in the presence of elemental mercury

In the expression of bioaccumulated elemental mercury (Hg 0) toxicity, the first Hg 0 oxidation step is crucial. Therefore, to clarify the mechanism underlying the interactions of sulfhydryl (SH) compounds and Hg 0 in the present study, we analyzed the oxidation of reduced glutathione (GSH) and L-cysteine (Cys) in the presence of Hg 0 in aqueous solution by cyclic voltammetry (CV). Production of Hg2+ in the reaction mixture was found to increase along with a decrease in free SH residues. CV showed that the oxidation of Cys increased after a 4-h incubation in the presence of Hg(0), but the oxidation of Cys after a 24-h incubation was suppressed. Conversely, GSH oxidation increased with incubation time in the absence of Hg(0). In the presence of Hg(0), the oxidation of GSH was suppressed. The different reactivities of Cys and GSH with Hg(0) may arise from differences in their oxidation/reduction potentials and pH. The important SH compound interactions with Hg(0) oxidation were as follows: (i) oxidation of Hg(0) to form either mercurous ion (Hg+) or mercuric ion (Hg2+) which both form stable complexes in aqueous solution as Hg I (RS) or Hg II(RS)2; (ii) catalyzed oxidation of SH compounds in the presence of Hg 0; and (iii) suppression of the oxidation of SH compounds due to the reduced concentration of free SH compounds through the binding of SH compounds with Hg+ or Hg2+ The present results demonstrate the chemical reaction processes by which Hg 0 dissolves in aqueous solution in the presence of SH compounds, and contribute to our understanding of SH compounds in non-enzymatic Hg 0 oxidation in vivo.     

Order-of-magnitude increase of Hg in Norwegian peat profiles since the outset of industrial activity in Europe

Peat cores from six ombrotrophic bogs at different latitudes in Norway (58 degrees N-69 degrees N) were analysed for Hg by atomic fluorescence spectrometry. In all cases a smooth decrease of Hg with depth was observed down to 15-20 cm. At greater depths Hg showed a relatively constant level of the order of 10% of that in the peat surface layer. In the surface peat Hg concentrations exhibit moderate variation with latitude. The pre-industrial levels of Hg in the peat correspond to a net annual Hg accumulation of 0.3-0.9 microgm(-2). The Hg accumulation over the last 100 years is about 15 times higher on average than the pre-industrial level. The present work supports the view that a major part of the present atmospheric Hg in the Northern Hemisphere is of anthropogenic origin. It is speculated that the comparatively high Hg contemporary accumulation rates observed at the And?ya bog on 69 degrees N may be related to the Arctic springtime depletion of Hg.     

Mercury conversion processes in Amazon soils evaluated by thermodesorption analysis

This paper reports on the speciation study and the Hg redox behavior in Amazon soils not influenced by gold mining and collected near Manaus, AM, Brazil. The samples were incubated by adding Hg(0) and HgCl₂ to dry soil. Solid phase Hg speciation analysis was carried out using a Hg thermodesorption technique with the aim of distinguishing elemental Hg(0) from Hg(II) binding forms. In the first case, we observed the conversion of Hg(0) to Hg(II) binding forms in the range of 28–68% and a correlation between the percent of oxidation and OM content. Samples incubated with Hg(II) showed the formation of Hg(I) and/or Hg(0) in the range of 19–69%. The lowest values corresponded to the samples with the lowest clay contents. The kinetics of conversion of Hg(0) as well as HgCl₂ were roughly fitted to the two first order reactions, a fast one and a slow one. It was not possible to evaluate differences between sampling sites and types of soils, but the mean half-life of the first order reaction obtained by the addition of Hg(II) was slower (t_1/2 = 365 d) than the one obtained by the addition of Hg(0) (t_1/2 = 148 d). Previous studies have shown the predominance of organically bound Hg in these samples. Thus, the kinetic difference between Hg oxidation and reduction in combination with the efficient retention processes by OM may explain the high background values found in Amazon soils.     

Mercury speciation and mobility in mine wastes from mercury mines in China

Mercury (Hg) speciation and mobility were determined in calcines and waste rocks collected from 9 Hg mines in China. Total Hg (THg) concentrations in the mine wastes varied widely in different Hg mines (with a range of 0.369 to 2,620 mg kg^?1). Cinnabar is the dominant form of Hg in the mine wastes. However, Hg²⁺ and Hg⁰ concentrations in the calcines were significantly higher than these in the waste rocks, which suggested the retorting can produce large amounts of by-product Hg compounds. The THg and Hg⁰ concentrations in certain mine wastes exceeded soil guidelines recommended by US Environmental Protection Agency; while total soluble Hg concentrations of leachates in certain mine wastes exceeded National Surface Water Quality Standard of China. Mine wastes are important Hg pollution sources to the aquatic ecosystem and atmosphere.     

Bioaccumulation and physiological effects of mercury in Sesbania drummondii

The accumulation of mercury and its effect on growth, photosynthesis and antioxidative responses were studied in Sesbania drummondii seedlings. Mercury concentration in shoots as well as in the roots increased with increasing Hg concentrations in the growth solution. The accumulation of Hg was more in roots than shoots. At 100 mg l-1 Hg concentration, shoots accumulated 998 mg Hg kg -1 dry weight (dw) while roots accumulated 41,403 mg Hg kg-1 dw. Seedlings growth was not significantly affected at lower concentrations of Hg. A concentration of 100 mg l-1 Hg inhibited growth by 36.8%, with respect to control. Photosynthetic activity was assessed by measuring chlorophyll a fluorescence by determination of Fv/Fm and Fv/Fo values. Photosynthetic integrity was not affected up to 50 mg l-1 Hg concentration, however, concentrations higher than 50 mg l-1 affected photosynthetic integrity. Sesbania responded to Hg induced oxidative stress by modulating non-enzymatic antioxidants [glutathione (GSH) and non-protein thiols (NPSH)] and enzymatic antioxidants: superoxide dismutase (SOD), ascorbate peroxidase (APX) and glutathione reductase (GR). Glutathione content and GSH/GSSG ratio increased up to a concentration of 50 mg l-1 while slight down at 100 mg l-1 Hg. The content of NPSH significantly increased with increasing Hg concentrations in the growth medium. The activities of antioxidative enzymes, SOD, APX and GR followed the same trends as antioxidants first increased up to a concentration of 50 mg l-1 Hg and then slight decreased. The results of present study suggest that Sesbania plants were able to accumulate and tolerate Hg induced stress using an effective antioxidative defense mechanisms.     

Gas-phase mercury reduction to measure total mercury in the flue gas of a coal-fired boiler

Gaseous elemental and total (elemental + oxidized) mercury (Hg) in the flue gas from a coal-fired boiler was measured by a modified ultraviolet (UV) spectrometer. Challenges to Hg measurement were the spectral interferences from other flue gas components and that UV measures only elemental Hg. To eliminate interference from flue gas components, a cartridge filled with gold-coated sand removed elemental Hg from a flue gas sample. The Hg-free flue gas was the reference gas, eliminating the spectral interferences. To measure total Hg by UV, oxidized Hg underwent a gas-phase, thermal-reduction in a quartz cell heated to 750 degrees C. Simultaneously, hydrogen was added to flash react with the oxygen present forming water vapor and preventing Hg re-oxidation as it exits the cell. Hg concentration results are in parts per billion by volume Hg at the flue gas oxygen concentration. The modified Hg analyzer and the Ontario Hydro method concurrently measured Hg at a field test site. Measurements were made at a 700-MW steam turbine plant with scrubber units and selective catalytic reduction. The flue gas sampled downstream of the selective catalytic reduction contained 2100 ppm SO2 and 75 ppm NOx. Total Hg measured by the Hg analyzer was within 20% of the Ontario Hydro results.     

Mercury in soils of three agricultural experimental stations with long-term fertilization in China

Mercury (Hg) in the agricultural ecosystem is a global concern because of its high potential toxicity. The objectives of this study were to determine the concentration and distribution of Hg in soils from three long-term experimental stations, i.e., Taoyuan (TY) and Qiyang (QY) in Hunan Province and Fengqiu (FQ) in Henan Province of China, and thus to assess the possible food and health risk of long-term applications of fertilizers. Soil samples at each site were collected from different fertilization plots and also from soil profiles with depths 0-100 cm. There were significant differences in soil Hg concentrations in 0-20 cm (A) or 20-40 cm (B) horizon among the three experimental stations. QY station showed significantly higher Hg concentrations than TY and FQ stations. However, there were no significant differences in soil Hg concentrations between A and B horizons at each station. It was concluded that the soil Hg concentrations at the three sites were mainly controlled by the parent materials. Moreover, chemical fertilizer, especially phosphorous fertilizers, could influence the soil Hg concentrations to some extent at the station with lower soil Hg concentrations, for example, at TY station. There were minimal amounts of Hg resulting from applications of the other chemical fertilizers and organic manure, and thus the fertilization had very low risk to the food security of the agro-ecosystems in the terms of Hg inputs and contamination.     

Diel variations in photoinduced oxidation of Hg0 in freshwater

Experiments have been conducted to determine diel variations in photoinduced Hg0 oxidation in lake water under natural Hg0(aq) concentrations. Pseudo-first-order rates of photooxidation (k') were calculated for water freshly collected in a Canadian Shield lake, Lake Croche (45 degrees 56' N, 74 degrees 00' W), at different periods of the day and subsequently incubated in the dark. Hg0 oxidation rates ranged from 0.02 to 0.07 h(-1), increasing from sunrise to noon and then decreasing throughout the remainder of the day. These changes paralleled those in sunlight intensity integrated over 1 h preceding water collection, and suggested that the water freshly collected in daylight was rich in photochemically produced Hg0 oxidants. It was also estimated that under intense solar radiation, even if oxidation rates reached a peak, reduction of Hg(II) was the prevalent redox process. Inversely, Hg0 oxidation overcame DGM production during the night or at periods of weaker light intensity. Overall, these findings explain the decreases in the DGM pool generally observed overnight. They also support previous reports that, during summer days, volatilization of Hg0 from water represent an important step in the Hg cycle in freshwater systems.     

Mercury concentrations and air/soil fluxes in Wuchuan mercury mining district,Guizhou province,China

Wuchuan Hg mine, located in the Circum-Pacific Global Mercuriferous Belt, is one of the important Hg production centers in Guizhou province, China. Soil Hg concentrations in this area are elevated by 2–4 orders of magnitude compared to the national background value in soil which is 0.038 μg g⁻¹. In situ air Hg concentrations and air/soil Hg fluxes were measured at five sampling sites in Wuchuan Hg mining area (WMMA) from 19 to 26 December 2003 and from 18 to 25 December 2004. The results showed that air Hg concentrations were 2–4 orders of magnitude higher than those observed in background areas in Europe and North America due to a large amount of Hg emission from artisanal Hg smelting activities. The average in situ Hg fluxes at site Laohugou, Jiaoyan, Luoxi, Sankeng and Huanglong were −5493, 124, −924, −13 and 140 ng m⁻² h⁻¹, respectively. Diurnal pattern of Hg flux was not found and a number of negative Hg fluxes were observed in our sampling campaigns. The correlations between Hg fluxes and meteorological parameters such as solar irradiation, air temperature, soil temperature and relative humidity and air Hg concentrations were investigated. The commonly observed significant correlations between Hg fluxes and meteorological parameters observed in many previous studies were not obtained in WMMA. However, significantly negative correlations between Hg flux and air Hg concentration were observed at all sites. Our study demonstrated that highly elevated air Hg concentrations could suppress Hg emission processes even from Hg-enriched soil. At specific conditions in WMMA, air Hg concentrations play a dominant role in controlling Hg emission from soil.     

Control of mercury emissions from a municipal solid waste incinerator in Japan

The control of Hg emissions from a municipal solid waste incinerator (MSWI) is very important, because more than 78% of municipal solid waste (MSW) is incinerated. The Hg content of coal used in utility boilers is relatively low in Japan. In this study, recent trends in the Hg content of MSW in Japan and activated carbon (AC) injection as a control technology of Hg emission from an MSWI are discussed. The effect of AC injection on Hg removal from flue gas in an MSWI was investigated by pilot-scale experiments using a bag filter (BF). The injection of AC increases the Hg reduction ratio by 20-30% compared with cases without AC injection. The Hg reduction ratio increases as the flue gas temperature decreases. The Hg reduction ratio is closely related to the inlet Hg concentration and was expressed with a Langmuir-type adsorption isotherm.     

Issues related to solution chemistry in mercury sampling impingers

Analysis of Hg speciation in combustion flue gases is often accomplished in standardized sampling trains in which the sample is passed sequentially through a series of aqueous solutions to capture and separate oxidized Hg (Hg2+) and elemental Hg (Hg0). Such methods include the Ontario Hydro (OH) and the Alkaline Mercury Speciation (AMS) methods, which were investigated in the laboratory to determine whether the presence of Cl2 and other common flue gas species can bias the partitioning of Hg0 to front impingers intended to isolate Hg2+ species. Using only a single impinger to represent the front three impingers for each method, it was found that as little as 1-ppm Cl2 in a simulated flue gas mixture led to a bias of approximately 10-20% of Hg0 misreported as Hg2+ for both the OH and the AMS methods. Experiments using 100-ppm Cl2 led to a similar bias in the OH method, but to a 30-60% bias in the AMS method. These false readings are shown to be due to liquid-phase chemistry in the impinger solutions, and not necessarily to the gas-phase reactions between Cl2 and Hg as previously proposed. The pertinent solution chemistry causing the interference involves the hypochlorite ion (OCl-), which oxidizes Hg0 to soluble Hg2+. Addition of sodium thiosulfate (Na2S2O3) to the front impinger solutions eliminates this false positive measurement of Hg2+ by selectively reacting with the OCl- ion. In general, the presence of SO2 also mitigates this interference in the same way, and so this bias is not likely to be a factor for Hg speciation measurements from actual coal combustion flue gases. It might, however, be a problem for those few combustor flue gas measurements and research studies where Cl2 is present without appreciable amounts of SO2.     

Mercury contamination in vicinity of secondary copper smelters in Fuyang, Zhejiang Province, China: Levels and contamination in topsoils

In the present study, we aim to investigate the extent of soil contamination by Hg, particularly by anthropogenic Hg, and tentatively estimate the total Hg (Hg_T) accumulation in topsoils (0-15 cm) in Fuyang, Zhejiang Province—a secondary Cu smelter of China. The results show that the levels of soil Hg in the vicinity of the smelters have been substantially elevated following local smelting activities. The spatial distribution of soil Hg in this area reveals a rapid decrease as the distance from the smelter reaches 1.5 km, which is probably due to the quick deposition process of particulate Hg and reactive gaseous Hg emitted from the smelters. The total accumulation of Hg_T in the topsoils of the study area of 10.9 km² is approximately 365-561 kg and of which 346-543 kg might be contributed by anthropogenic emission alone with an annual emission of 17.3-27.2 kg Hg to the topsoils.     

Control of Mercury Emissions from a Municipal Solid Waste Incinerator in Japan

Abstract

The control of Hg emissions from a municipal solid waste incinerator (MSWI) is very important, because more than 78% of municipal solid waste (MSW) is incinerated. The Hg content of coal used in utility boilers is relatively low in Japan. In this study, recent trends in the Hg content of MSW in Japan and activated carbon (AC) injection as a control technology of Hg emission from an MSWI are discussed. The effect of AC injection on Hg removal from flue gas in an MSWI was investigated by pilot-scale experiments using a bag filter (BF). The injection of AC increases the Hg reduction ratio by 20–30% compared with cases without AC injection. The Hg reduction ratio increases as the flue gas temperature decreases. The Hg reduction ratio is closely related to the inlet Hg concentration and was expressed with a Langmuir-type adsorption isotherm.     

Specific accumulation of mercury and selenium in seabirds

Total mercury (T-Hg), methyl mercury (MeHg) and selenium (Se) concentrations were determined to elucidate the relationship between Hg and Se levels in the liver of 10 seabird species. Highest concentrations of T-Hg (mean 267 microg/g dry wt), MeHg (mean 25.5 microg/g dry wt) and Se (mean 113 microg/g dry wt) were in the liver of black-footed albatross (Diomedea nigripes). An equivalent molar ratio of 1:1 between T-Hg and Se was found in the liver of individuals which contain over 100 microg Hg/g. However, such a relationship was unclear in other individuals which had relatively low Hg levels. This suggests that Se plays a role in Hg detoxification for those individuals with high Hg. In seabird tissues, Hg and Se levels should be a most important factor determining the relationship between Hg and Se, and fluctuation of Hg burden through molting and the species-specific demethylation capacity would also influence their relationships.     

Assessing anthropogenic sources of mercury in soil in Wanshan Hg mining area, Guizhou, China

Long-term mining and smelting activities brought a series of environmental issues into soils in Wanshan mercury (Hg) mining area (WMMA), Guizhou, China. Several studies have been published on the concentrations of Hg in local soils, but a comprehensive assessment of the mass of Hg in soil induced by anthropogenic activities, as presented in this paper, has not been previously conducted. Three districts of WMMA were chosen as the study areas. We summarized previous published data and sampled 14 typical soil profiles to analyze the spatial and vertical distributions of Hg in soil in the study areas. The regional geologic background, direct and indirect Hg deposition, and Hg-polluted irrigation water were considered as the main sources of Hg contaminations in local soils. Furthermore, the enrichment factor (EF) method was applied to assess the extent of anthropogenic input of Hg to soil. Titanium (Ti) was chosen to be the reference element to calculate the EF. Generally, the elevated values of EF were observed in the upper soil layers and close to mine wastes. The total budget of Hg in soil contributed from anthropogenic sources was estimated to be 1,227 t in arable soil and 75 t in natural soil. Our data showed that arable soil was the major sink of anthropogenic Hg in the study area.     

A comprehensive investigation and assessment of mercury in intertidal sediment in continental coast of Shanghai

The aims of this paper were to survey the total Hg levels and distribution character in intertidal sediment in continental coast of Shanghai, and identify the environment factors that might influence the sediment Hg concentrations, and to assess the pollution degree and potential ecological risk of Hg in sediment. Eighty-eight surface sediment samples and 18 sediment cores were collected for Hg contamination analysis. Physicochemical properties including Eh, particle size, content of total organic carbon (TOC), and acid volatile sulfide (AVS) were also measured. Index of geo-accumulation (I _geo) and potential ecological risk index were used respectively to assess the pollution levels and the ecological risk of sediment Hg. The average of total Hg concentrations in surface sediments was 107.4?±?90.9 ng/g with the range from 0 to 465.9 ng/g. Higher Hg concentrations were generally found in surface sediments near sewage outfalls and the mouth of rivers. Total Hg concentrations were significantly correlated with TOC (p?<?0.05) both in surface (r?=?0.24) and core (r?=?0.29) sediments, but not with the other environment factors (Eh, AVS, and particle size). Geo-accumulation index indicated that Hg contamination in intertidal sediments was generally at none to moderate degree, while potential ecological risk index demonstrated that the risk caused by Hg were at moderate to considerable level. Intertidal sediment in continental coast of Shanghai has generally been contaminated by Hg, and it might pose moderate to considerable risk to the local ecosystem. The Hg contamination is related more to the coastal pollution sources and complicated hydrodynamic and sedimentary conditions than the other environment factors studied.     

Mercury in Precipitation at an Urbanized Coastal Zone of the Baltic Sea (Poland)

Wet deposition is an important source of metals to the sea. The temporal variability of Hg concentrations in precipitation, and the impact of air masses of different origins over the Polish coastal zone were assessed. Samples of precipitation were collected (August 2008–May 2009) at an urbanized coastal station in Poland. Hg analyses were conducted using CVAFS. These were the first measurements of Hg concentration in precipitation obtained in the Polish coastal zone. Since Poland was identified as the biggest emitter of Hg to the Baltic, these data are very important. In the heating and non-heating season, Hg concentrations in precipitation were similar. Hg wet deposition flux dominated in summer, when the production of biomass in the aquatic system was able to actively adsorb Hg. Input of metal to the sea was attributed to regional and distant sources. Maritime air masses, through transformation of Hg(0), were an essential vector of mercury in precipitation.