Mercury mobility in a salt marsh colonised by Halimione portulacoides

The present study intends to increase the knowledge on the mobility of mercury in a salt marsh colonised by Halimione portulacoides. Mercury distribution in the sediment layers and its incorporation into the plant biomass were assessed, as well as the potential export of mercury from the contaminated area to the adjacent environment. Mercury pools in the sediments ranged from 560 to 943 mg m(-2) and are largely associated with the solid fraction, with just a small amount being associated with the pore waters. Estimated diffusive fluxes of reactive mercury ranged from 1.3 to 103 ng m(-2) d(-1). Despite the above ground biomass values being comparatively higher than below ground biomass values, the mercury pools were much higher in the root system (0.06-0.16 mg m(-2) and 29-102 mg m(-2), respectively). The annual bioaccumulation of mercury in above ground tissues was estimated in 0.11 mg m(-2) y(-1), while in below ground biomass the values were higher (7 2mg m(-2) y(-1)). The turnover rates of H. portulacoides biomass suggest higher mercury mobility within the plant rhizosphere. Taking into account the pools of mercury in above ground biomass, the export of mercury by macro-detritus following the "outwelling hypothesis" is not significant for the mercury balance in the studied ecosystem. The mercury accumulated in the below ground part of the plant is quite mobile, being able to return to the sediment pool throughout the mineralisation process.     

Mercury removal from incineration flue gas by organic and inorganic adsorbents

Experiments were performed to investigate various adsorbents for their mercury removal capabilities from incineration flue gases. Four different materials were tested; Zeolite, Bentonite, activated carbon (AC), and wood char. Real incineration off-gas and in-lab simulated combustion flue gases (N2 + Hg) were used. Three cylindrical-shaped sorbent columns with 5 cm in diameter and 20 cm in length were used. The gas flow rate was fixed at 660 l/h at all times. Concentrations of NO, CO, O2, CO2, SO2, H2O, HCl, and mercury were continuously monitored. Mercury removal efficiencies of natural Zeolite and Bentonite were found to be much lower than those of the referenced AC. Amount of Hg removed were 9.2 and 7.4 microg/g of Zeolite and Bentonite, respectively. Removal efficiencies of each layer consisted of inorganic adsorbents were no higher than 7%. No significant improvement was observed with sulfur impregnation onto the inorganic adsorbents. Organic adsorbents (wood char and AC) showed much higher mercury removal efficiencies than those of inorganic ones (Zeolite and Bentonite). Mercury removal efficiency of wood char reached over 95% in the first layer, showing almost same effectiveness as AC which currently may be the most effective adsorbents for mercury. Amount of mercury captured by wood char was approximately 0.6 mg/g of wood char, close to the amount captured by AC tested in this study. Hence, wood char, made from the waste woods through a gasification process, should be considered as a possible alternative to relatively expensive AC.     

Investigation of selective catalytic reduction impact on mercury speciation under simulated NOx emission control conditions

Selective catalytic reduction (SCR) technology increasingly is being applied for controlling emissions of nitrogen oxides (NOx) from coal-fired boilers. Some recent field and pilot studies suggest that the operation of SCR could affect the chemical form of mercury (Hg) in coal combustion flue gases. The speciation of Hg is an important factor influencing the control and environmental fate of Hg emissions from coal combustion. The vanadium and titanium oxides, used commonly in the vanadia-titania SCR catalyst for catalytic NOx reduction, promote the formation of oxidized mercury (Hg2+). The work reported in this paper focuses on the impact of SCR on elemental mercury (Hg0) oxidation. Bench-scale experiments were conducted to investigate Hg0 oxidation in the presence of simulated coal combustion flue gases and under SCR reaction conditions. Flue gas mixtures with different concentrations of hydrogen chloride (HCl) and sulfur dioxide (SO2) for simulating the combustion of bituminous coals and subbituminous coals were tested in these experiments. The effects of HCl and SO2 in the flue gases on Hg0 oxidation under SCR reaction conditions were studied. It was observed that HCl is the most critical flue gas component that causes conversion of Hg0 to Hg2+ under SCR reaction conditions. The importance of HCl for Hg0 oxidation found in the present study provides the scientific basis for the apparent coal-type dependence observed for Hg0 oxidation occurring across the SCR reactors in the field.     

Mercury oxidation promoted by a selective catalytic reduction catalyst under simulated Powder River Basin coal combustion conditions

A bench-scale reactor consisting of a natural gas burner and an electrically heated reactor housing a selective catalytic reduction (SCR) catalyst was constructed for studying elemental mercury (Hg(o)) oxidation under SCR conditions. A low sulfur Powder River Basin (PRB) subbituminous coal combustion fly ash was injected into the entrained-flow reactor along with sulfur dioxide (SO2), nitrogen oxides (NOx), hydrogen chloride (HCl), and trace Hg(o). Concentrations of Hg(o) and total mercury (Hg) upstream and downstream of the SCR catalyst were measured using a Hg monitor. The effects of HCl concentration, SCR operating temperature, catalyst space velocity, and feed rate of PRB fly ash on Hg(o) oxidation were evaluated. It was observed that HCl provides the source of chlorine for Hg(o) oxidation under simulated PRB coal-fired SCR conditions. The decrease in Hg mass balance closure across the catalyst with decreasing HCl concentration suggests that transient Hg capture on the SCR catalyst occurred during the short test exposure periods and that the outlet speciation observed may not be representative of steady-state operation at longer exposure times. Increasing the space velocity and operating temperature of the SCR led to less Hg(o) oxidized. Introduction of PRB coal fly ash resulted in slightly decreased outlet oxidized mercury (Hg2+) as a percentage of total inlet Hg and correspondingly resulted in an incremental increase in Hg capture. The injection of ammonia (NH3) for NOx reduction by SCR was found to have a strong effect to decrease Hg oxidation. The observations suggest that Hg(o) oxidation may occur near the exit region of commercial SCR reactors. Passage of flue gas through SCR systems without NH3 injection, such as during the low-ozone season, may also impact Hg speciation and capture in the flue gas.     

Sorption studies of heavy metal ions on a novel chelating resin and its application in the stripping of mercury (II)

A chelating resin containing a stable thiol group was synthesised, using polystyrene as the starting material. The resin is stable towards conc. HCl, 0.1M HNO(3) and 0.1M NaOH. The resin shows affinity towards Ag(+), Hg(2+), Bi(3+), Pb(2+), Cu(2+), Zn(2+) and Cd(2+). Extraction of these metal ions as a function of pH, kinetics of exchange and breakthrough capacities is evaluated. The selectivity of the resin for the metal ions is in the order Ag(+) > Hg2+ > Cu2+ > Pb2+ > Cd2+ > Zn2+. The equilibrium constants for exchange and kinetics of exchange are favourable for the recovery of mercury from lean sources. Application of the resin in the stripping of mercury from chlor-alkali plant affluent, and in the enrichment of mercury from seawater, have been investigated. Mercury sorbed resin can be regenerated using 5% thiourea in 0.1M HCl.     

Studies of mercury pollution in a lake due to a thermometer factory situated in a tourist resort: Kodaikkanal, India

Kodaikkanal, India, suffered mercury contamination due to emissions and waste from a thermometer factory. Kodai Lake is situated to the north of the factory. The present study determined mercury in waters, sediment and fish samples and compared the values with those from two other lakes, Berijam and Kukkal. Total mercury (Hg(T)) of 356-465 ng l(-1), and 50 ng l(-1) of mercury in methyl mercury form were seen in Kodai waters while Berijam and Kukkal waters showed significantly lower values. Kodai sediment showed 276-350 mg/kg Hg(T) with about 6% methyl mercury. Berijam and Kukkal sediments showed Hg(T) of 189-226 mg/kg and 85-91 mg/kg and lower methylation at 3-4% and 2%, respectively. Hg(T) in fish from Kodai lake ranged from 120 to 290 mg/kg. The results show that pollution of the lake has taken place due to mercury emissions by the factory.     

Mercury speciation in Pacific coastal rainwater,Monterey Bay,California

We measured mercury speciation in coastal rainwater samples from Monterey Bay, California in 2007–2008 to investigate the source of monomethylmercury (MMHg) in rainwater and determine the relative importance of wet atmospheric deposition of MMHg to coastal waters compared to other sources on the central Pacific coast. Total mercury (HgT) ranged from 10 to 88 pM, with a sample mean ± standard deviation of 33 ± 22 pM (volume-weighted average 29 pM). MMHg concentrations ranged from 0.12 to 2.3 pM with a sample mean of 0.7 ± 0.5 pM (volume-weighted average 0.68 pM). Reactive mercury (HgR) concentrations ranged from 0.87 to 47 pM, sample mean 7.8 ± 8.3 pM (volume-weighted average 6.1 pM). Acetate concentration in rainwater, measured in a subset of samples, ranged from 0.34 to 3.1 μM, and averaged 1.6 ± 0.9 μM (volume-weighted average 1.3 μM). Dimethylmercury (DMHg) concentrations were below the limit of detection in air (<0.01 ng m^?3) and rainwater (<0.05 pM). Despite previous suggestions that DMHg in upwelled ocean waters is a potential source of MMHg in coastal rainwater, MMHg in rain was not related to coastal upwelling seasons or surface water DMHg concentrations. Instead, a multiple linear regression analysis demonstrated that MMHg concentrations were positively and significantly correlated (p = 0.002, adjusted R² = 0.88) with those of acetate and HgR. These data appear to support previous suggestions that the aqueous phase methylation of Hg(II) by acetate may be the source of MMHg in rainwater, but imply that acetate concentrations in rainwater play a more important role relative to HgR than previously hypothesized. However, the calculated chemical speciation of Hg(II) in rainwater and the minimal predicted complexation of Hg(II) by acetate suggest that the aqueous phase methylation of Hg(II) by acetate is unlikely to account for the MMHg found in precipitation, or that the mechanism of this reaction in the atmosphere differs from that previously reported (Gardfeldt et al., 2003).     

Wetland influence on mercury fate and transport in a temperate forested watershed

The transport and fate of mercury (Hg) was studied in two forest wetlands; a riparian peatland and an abandoned beaver meadow. The proportion of total mercury (THg) that was methyl mercury (% MeHg) increased from 2% to 6% from the upland inlets to the outlet of the wetlands. During the growing season, MeHg concentrations were approximately three times higher (0.27ng/L) than values during the non-growing season (0.10ng/L). Transport of Hg species was facilitated by DOC production as indicated by significant positive relations with THg and MeHg. Elevated concentrations of MeHg and % MeHg (as high as 70%) were found in pore waters of the riparian and beaver meadow wetlands. Groundwater interaction with the stream was limited at the riparian peatland due to the low hydraulic conductivity of the peat. The annual fluxes of THg and MeHg at the outlet of the watershed were 2.3 and 0.092microg/m2-year respectively.     

Mercury cycling in surface water, pore water and sediments of Mugu Lagoon, CA, USA

Mugu Lagoon is an estuary in southern California, listed as impaired for mercury. In 2005, we examined mercury cycling at ten sites within at most four habitats. In surface water (unfiltered and filtered) and pore water, the concentration of total mercury was correlated with methylmercury levels (R2=0.29, 0.26, 0.27, respectively, p<0.05), in contrast to sediments, where organic matter and reduced iron levels were most correlated with methylmercury content (R2=0.37, 0.26, respectively, p<0.05). Interestingly, levels for percent methylmercury of total mercury in sediments were higher than typical values for estuarine sediments (average 5.4%, range 0.024-38%, n=59), while pore water methylmercury Kd values were also high (average 3.1, range 2.0-4.2l kg(-1), n=39), and the estimated methylmercury flux from sediments was low (average 1.7, range 0.14-5.3ng m(-2) day(-1), n=19). Mercury levels in predatory fish tissue at Mugu are >0.3ppm, suggesting biogeochemical controls on methylmercury mobility do not completely mitigate methylmercury uptake through the food web.     

LP/LIF study of the formation and consumption of mercury (I) chloride: kinetics of mercury chlorination

The laser photolysis/laser induced fluorescence (LP/LIF) technique has been applied to studies of gas-phase mercury (Hg) chlorination. Mercury (I) chloride (HgCl) was been detected via LIF at 272 nm from reactions of elemental Hg with Cl atoms generated from the 193 nm photolysis of carbon tetrachloride. While the formation of HgCl was too fast to be observed on millisecond time scales, the kinetics of the consumption of HgCl have been determined at temperatures characteristic of post-combustion conditions. Rate coefficients and Arrhenius parameters for the reaction of HgCl with Cl2, HCl and Cl atoms were determined. The reaction of HgCl with Cl2 was the fastest reaction studied, while the reaction of HgCl with HCl was the only reaction to show any measurable temperature dependence. Estimates of the rate coefficient for the reaction Hg + Cl --> HgCl were determined using a modeling approach. Comparisons of these new measurements with model predictions are discussed.     

A study of gas-phase mercury speciation using detailed chemical kinetics.

Mercury speciation in combustion-generated flue gas was modeled using a detailed chemical mechanism consisting of 60 reactions and 21 species. This speciation model accounts for the chlorination and oxidation of key flue-gas components, including elemental mercury (Hg0). Results indicated that the performance of the model is very sensitive to temperature. Starting with pure HCl, for lower reactor temperatures (less than approximately 630 degrees C), the model produced only trace amounts of atomic and molecular chlorine (Cl and Cl2), leading to a drastic underprediction of Hg chlorination compared with experimental data. For higher reactor temperatures, model predictions were in good accord with experimental data. For conditions that produce an excess of Cl and Cl2 relative to Hg, chlorination of Hg is determined by the competing influences of the initiation step, Hg + Cl = HgCl, and the Cl recombination reaction, 2Cl = Cl2. If the Cl recombination reaction is faster, Hg chlorination will eventually be dictated by the slower pathway Hg + Cl2 = HgCl2.     

Stabilization of mercury-containing wastes using sulfide

This paper summarizes the findings of our studies on mercury stabilization using sulfide. Primary stabilization variables such as stabilization pH and sulfide/mercury molar ratio were tested. Mercury stabilization effectiveness was evaluated using the Toxicity Characteristic Leaching Procedure (TCLP) and the constant pH leaching tests. The influence of interfering ions on mercury immobilization was also tested. The experimental results indicate that the sulfide-induced treatment technology is an effective way to minimize mercury leaching. It was found that the most effective mercury stabilization occurs at pH 6 combined with a sulfide/mercury molar ratio of 1. The combined use of increased dosage of sulfide and ferrous ions ([S]/[Hg]=2 and [Fe]/[Hg]=3 at pH=6) can significantly reduce interferences by chloride and/or phosphate during sulfide-induced mercury immobilization. The sulfide-treated waste stabilization efficiency reached 98%, even with exposure of the wastes to high pH leachants.     

Influence of HCl on oxidation of gaseous elemental mercury by dielectric barrier discharge process

The influence of HCl on the oxidation of gaseous elemental mercury (Hg0) has been investigated using a dielectric barrier discharge (DBD) plasma process, where the temperature of the plasma reactor and the composition of gas mixtures of HCl, H2O, NO, and O2 in N2 balance have been varied. We observe that Cl atoms and Cl2 molecules, created by the DBD process, play important roles in the oxidation of Hg0 to HgCl2. The addition of H2O to the gas mixture of HCl in N2 accelerates the oxidation of Hg0, although no appreciable effect of H2O alone on the oxidation of Hg0 has been observed. The increase of the reaction temperature in the presence of HCl results in the reduction of Hg0 oxidation efficiency probably due to the deterioration of the heterogeneous chemical reaction of Hg0 with chlorinated species on the reactor wall. The presence of NO shows an inhibitory effect on the oxidation of Hg0 under DBD of 16% O2 in N2, indicating that NO acts as an O and O3 scavenger. At the composition of Hg0 (280 microg m(-3)), HCl (25 ppm), NO (204 ppm), O2 (16%) and N2 (balance) and temperature 90 degrees C, we obtain the nearly complete oxidation of Hg0 at a specific energy density of 8 J l(-1). These results lead us to suggest that the DBD process can be viable for the treatment of mercury released from coal-fired power plants.     

Mercury in European Blushers, Amanita rubescens, mushrooms and topsoils: bioconcentration potential and intake assessment

Total mercury content has been determined in fruiting bodies of European Blushers and topsoils collected from 11 sites across Poland in 2006-2008. Mercury analysis was carried out using a validated analytical method and cold-vapour atomic absorption (CV-AAS). The European Blusher effectively accumulated mercury in fruiting bodies. The mean values of total mercury in caps of European Blushers from background (uncontaminated) areas were from 0.22 to 1.0 (0.067-3.2) and in stipes from 0.16 to 0.65 (0.071-2.7) μg/g dry weight. In topsoil beneath to fruiting bodies, the median Hg concentration at 10 sites in Northern Poland varied between 0.030 and 0.072 (0.0096-0.19) μg/g dw, and in one site in Southern Poland was 0.20 (0.079-0.34) μg/g dw. Data on Hg in European Blushers from different countries were reviewed. The mean concentrations of total Hg in caps of European Blushers from two "pristine" sites in northern part of Poland were ～1.0 μg/g dw. A meal made with 300-500 g of fresh caps of European Blushers collected at such sites (assuming 90% water content in caps) can result in Hg intake of 0.0003-0.0005 mg Hg/kg bm (assuming a 60 kg bm), which is a dose equipotent to a new provisional tolerable weekly intake (PTWI) value set for inorganic Hg.     

Mercury in European Blushers,Amanita rubescens,mushrooms and topsoils: Bioconcentration potential and intake assessment

Total mercury content has been determined in fruiting bodies of European Blushers and topsoils collected from 11 sites across Poland in 2006-2008. Mercury analysis was carried out using a validated analytical method and cold-vapour atomic absorption (CV-AAS). The European Blusher effectively accumulated mercury in fruiting bodies. The mean values of total mercury in caps of European Blushers from background (uncontaminated) areas were from 0.22 to 1.0 (0.067-3.2) and in stipes from 0.16 to 0.65 (0.071-2.7) μg/g dry weight. In topsoil beneath to fruiting bodies, the median Hg concentration at 10 sites in Northern Poland varied between 0.030 and 0.072 (0.0096–0.19) μg/g dw, and in one site in Southern Poland was 0.20 (0.079–0.34) μg/g dw. Data on Hg in European Blushers from different countries were reviewed. The mean concentrations of total Hg in caps of European Blushers from two “pristine” sites in northern part of Poland were ～1.0 μg/g dw. A meal made with 300–500 g of fresh caps of European Blushers collected at such sites (assuming 90% water content in caps) can result in Hg intake of 0.0003–0.0005 mg Hg/kg bm (assuming a 60 kg bm), which is a dose equipotent to a new provisional tolerable weekly intake (PTWI) value set for inorganic Hg.     

Geothermal power plants at Mt. Amiata (Tuscany-Italy): mercury and hydrogen sulphide deposition revealed by vegetation

At Mt. Amiata (Italy) geothermal energy is used, since 1969, to generate electricity in five plants with a nominal capacity of 88 MW. Anomalous levels of mercury characterise geothermal fluids of Mt. Amiata, an area renowned for its vast cinnabar deposits and for the mercury production carried out in the past. Mercury emission rates range from 300 to 400 g/h, or 3-4 g/h per MW electrical installed capacity. These emissions are coupled with a release of 7-8 kg/(h MW) of hydrogen sulphide (H2S). Mercury is discharged as Hg0 gaseous species and reaches the atmosphere with the non-condensable gas fraction. In this fraction, CO, is the major component (94-98%), H2S is around 1% and mercury concentration is as high as 1-10 mg/Nm3. Leaves of a spontaneous grass (Avena sterilis), at the end of the vegetative cycle, were used as mercury bioconcentrators to map deposition near geothermal power plants and to calculate the corresponding average levels of Hg0 in the air. Direct measurements of mercury and hydrogen sulphide vapours in the air reached by power plant emissions showed a ratio of about 1-2000. This ratio was applied to calculate average levels of hydrogen sulphide starting from mercury deposition mapping: typical concentrations of mercury and hydrogen sulphide were of the order of 10-20 ng/m3 and 20-40 microg/m3, respectively.     

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 exposure in the freshwater tilapia Oreochromis niloticus

Mercury (Hg) can be strongly accumulated and biomagnified along aquatic food chain, but the exposure pathway remains little studied. In this study, we quantified the uptake and elimination of both inorganic mercury [as Hg(II)] and methylmercury (as MeHg) in an important farmed freshwater fish, the tilapia Oreochromis niloticus, using ²⁰³Hg radiotracer technique. The dissolved uptake rates of both mercury species increased linearly with Hg concentration (tested at ng/L levels), and the uptake rate constant of MeHg was 4 times higher than that of Hg(II). Dissolved uptake of mercury was highly dependent on the water pH and dissolved organic carbon concentration. The dietborne assimilation efficiency of MeHg was 3.7-7.2 times higher than that of Hg(II), while the efflux rate constant of MeHg was 7.1 times lower. The biokinetic modeling results showed that MeHg was the greater contributor to the overall mercury bioaccumulation and dietary exposure was the predominant pathway.     

Mercury loss from soils following conversion from forest to pasture in Rondônia, Western Amazon, Brazil

This work reports on the effect of land use change on Hg distribution in Amazon soils. It provides a comparison among Hg concentrations and distribution along soil profiles under different land use categories; primary tropical forest, slashed forest prior to burning, a 1-year silviculture plot planted after 4 years of forest removal and a 5-year-old pasture plot. Mercury concentrations were highest in deeper (60-80 cm) layers in all four plots. Forest soils showed the highest Hg concentrations, ranging from 128 ngg(-1) at the soil surface to 150 ngg(-1) at 60-80 cm of depth. Lower concentrations were found in pasture soils, ranging from 69 ngg(-1) at the topsoil to 135 ngg(-1) at 60-80 cm of depth. Slashed and silviculture soils showed intermediate concentrations. Differences among plots of different soil-use categories decreased with soil depth, being non-significant below 60 cm of depth. Mercury burdens were only statistically significantly different between pasture and forest soils at the topsoil, due to the large variability of concentrations. Consequently, estimated Hg losses were only significant between these two land use categories, and only for the surface layers. Estimated Hg loss due to forest conversion to pasture ranged from 8.5 mgm(-2) to 18.5 mgm(-2), for the first 20 cm of the soil profile. Mercury loss was comparable to loss rates estimated for other Amazon sites and seems to be directly related to Hg concentrations present in soils.     

Mercury in two fish species from the Paraná river floodplain, Paraná, Brazil

Total mercury concentrations were measured in dorsal muscle tissue of two edible fish species, Prochilodus scrofa 'curimba' and Pseudoplatystoma corruscans 'pintado', respectively detritivorous and carnivorous. Fish species were sampled monthly between February 1993 and January 1994 and bimonthly between April 1994 and February 1995 in three subsystems of Paraná river' system (Ivinhema River/Lake Patos; Baía River/Lake Guaraná and Paraná River/Cortado Channel), between Paraná and Mato Grosso do Sul. Total mercury was determined by HNO3/H2SO4/V2O5 digestion, SnCl2 reduction, and vapour generation method analysis (CGCH 900), adapted to Atomic Absorption Spectrometer (CGAA 7000 ABC). The mean mercury concentrations varied from 82.0 to 310.5 ng g(-1) and from 68 to 294.4 ng g(-1) in 'curimbas' and 'pintados', respectively. Mercury level increases in sexually mature 'curimbas'. Mercury values detected do not exceed the prevailing criteria for issuance of fish consumption advisories (< 500 ng g(-1)).