Mobility Of Mercury Research Articles

Mercury isotope variations between bioavailable mercury fractions and total mercury in mercury contaminated soil in Wanshan Mercury Mine, SW China

In this study, a comparison of the mobility of soil mercury with two different extractable treatments (water-treated and (NH4)2S2O3-treated) was carried out in soil samples collected from Wanshan Mercury Mine (WSMM), Guizhou, SW China. Substantially higher levels of mobilized Hg were found in (NH4)2S2O3-extracted (1.22 to 2.41μgg−1) compared to the water-extracted soil samples (0.05 to 0.49μgg−1). To understand the geochemical behavior of Hg during Hg mobilization, and to identify the potential hazard of Hg in soil, Hg isotope compositions of total Hg, water-soluble Hg and (NH4)2S2O3-extractable Hg in WSMM soil were measured by using multiple collectors coupled plasma mass spectrometer (MC-ICP-MS). A large variation of mass-dependent fractionation (MDF) of Hg was observed (δ202Hg of −0.29–1.59‰) between the extractable Hg species and the total Hg in soil. Mass independent fractionation (MIF) in Δ199Hg ranged from −0.07 to 0.07‰, which were statistically insignificant. The experimental data (δ202Hg values) revealed that water-soluble (δ202Hg=0.70±0.13‰, n=8) and (NH4)2S2O3-extractable (δ202Hg=1.28±0.25‰, n=8) Hg species were enriched in heavier Hg isotopes by 0.72‰ and 1.30‰ relative to total Hg in soil samples, respectively. The results suggest that the bioavailable fraction of Hg in soil possesses heavier Hg isotope values than total Hg in soil. To understand mercury isotope fractionation in the biogeochemical cycling processes in soil, it is of importance to measure Hg isotope compositions of different Hg species.

Biogeochemical factors affecting mercury methylation rate in two contaminated floodplain soils

Abstract. An automated biogeochemical microcosm system allowing controlled variation of redox potential (EH) in soil suspensions was used to assess the effect of various factors on the mobility of mercury (Hg) as well as on the methylation of Hg in two contaminated floodplain soils with different Hg concentrations (approximately 5 mg Hg kg−1 and >30 mg Hg kg–1). The experiment was conducted under stepwise variation from reducing (approximately −350 mV at pH 5) to oxidizing conditions (approximately 600 mV at pH 5). Results of phospholipid fatty acids (PLFA) analysis indicate the occurrence of sulfate reducing bacteria (SRB) such as Desulfobacter species (10Me16:0, cy17:0, 10Me18:0, cy19:0) or Desulfovibrio species (18:2ω6,9), which are considered to promote Hg methylation. The products of the methylation process are lipophilic, highly toxic methyl mercury species such as the monomethyl mercury ion [MeHg+], which is named as MeHg here. The ln(MeHg/Hgt) ratio is assumed to reflect the net production of monomethyl mercury normalized to total dissolved Hg (Hgt) concentration. This ratio increases with rising dissolved organic carbon (DOC) to Hgt ratio (ln(DOC/Hgt) ratio) (R2 = 0.39, p<0.0001, n= 63) whereas the relation between ln(MeHg/Hgt ratio and lnDOC is weaker (R2 = 0.09; p<0.05; n = 63). In conclusion, the DOC/Hgt ratio might be a more important factor for the Hg net methylation than DOC alone in the current study. Redox variations seem to affect the biogeochemical behavior of dissolved inorganic Hg species and MeHg indirectly through related changes in DOC, sulfur cycle, and microbial community structure whereas EH and pH values, as well as concentration of dissolved Fe3+/Fe2+ and Cl– seem to play subordinate roles in Hg mobilization and methylation under our experimental conditions.

Mercury mobility and availability in highly contaminated solid wastes from a chlor-alkali plant

This article suggests an approach of sustainable development in Cuba based on the environmental impact assessment of mercurial sludge generated by a chlor-alkali Cuban plant. It consists of a study of mercury mobility and availability in the sludge samples using sequential extraction procedure. High values of total mercury content (2320 ± 40 mg/kg) in the sludge sample as well as in the toxicity characteristic leaching procedure (TCLP) extract (0.46 ± 0.02 mg/l) were obtained. The highest Hg concentration (52.2 ± 1.5%) was found in the mobile fraction (F1 + F2) indicating a high risk of Hg mobilisation by the presence of water-soluble and exchangeable mercury compounds such as HgCl2, HgSO4 and HgO. The water-soluble fraction (F1) accounts for the 13.7 ± 0.8% of total Hg representing a significant environmental risk due to its easy availability in environmental weathering conditions. The mercury fractionation analyses clearly demonstrate that the chlor-alkali Cuban plant does not represent a sustainable technology from environmental point of view. Furthermore, this study highlights the presence of a wide range of mercury compounds which represents a significant parameter for developing a sustainable technology to treat the mercurial sludge generated by the chlor-alkali Cuban plant.

Electrokinetics at liquid/liquid interfaces

AbstractElectrokinetic effects at liquid/liquid interfaces have received considerably less attention than at solid/liquid interfaces. Because liquid/liquid interfaces are generally mobile, one might expect electrokinetic effects over a liquid/liquid interface to be faster than over an equivalent solid surface. The earliest predictions for the electrophoretic mobility of charged mercury drops – distinct approaches by Frumkin, along with Levich, and Booth – differed by $O(a/ {\lambda }_{D} )$, where $a$ is the radius of the drop and ${\lambda }_{D} $ is the Debye length. Seeking to reconcile this rather striking discrepancy, Levine & O’Brien showed double-layer polarization to be the key ingredient. Without a physical mechanism by which electrokinetic effects are enhanced, however, it is difficult to know how general the enhancement is – whether it holds only for liquid metal surfaces, or more generally, for all liquid/liquid surfaces. By considering a series of systems in which a planar metal strip is coated with either a liquid metal or liquid dielectric, we show that the central physical mechanism behind the enhancement predicted by Frumkin is the presence of an unmatched electrical stress upon the electrolyte/liquid interface, which establishes a Marangoni stress on the droplet surface and drives it into motion. The source of the unbalanced electrokinetic stress on a liquid metal surface is clear – metals represent equipotential surfaces, so no field exists to drive an equal and opposite force on the surface charge. This might suggest that liquid metals represent a unique system, since dielectric liquids can support finite electric fields, which might be expected to exert an electrical stress on the surface charge that balances the electric stress. We demonstrate, however, that electrical and osmotic stresses on relaxed double layers internal to dielectric liquids precisely cancel, so that internal electrokinetic stresses generally vanish in closed, ideally polarizable liquids. The enhancement predicted by Frumkin for liquid mercury drops can thus be expected quite generally over ideally polarizable liquid drops. We then reconsider the electrophoretic mobility of spherical drops, and reconcile the approaches of Frumkin and Booth: Booth’s neglect of double-layer polarization leads to a standard electro-osmotic flow, without the enhancement, and Frumkin’s neglect of the detailed double-layer dynamics leads to the enhanced electrocapillary motion, but does not capture the (sub-dominant) electrophoretic motion. Finally, we show that, while the electrokinetic flow over electrodes coated with thin liquid films is $O(d/ {\lambda }_{D} )$ faster than over solid/liquid interfaces, the Dukhin number, $\mathit{Du}$, which reflects the importance of surface conduction to bulk conduction, generally increases by a smaller amount [$O(d/ L)$], where $d$ is the thickness of film and $L$ is the length of the electrode. This suggests that liquid/liquid interfaces may be utilized to enhance electrokinetic velocities in microfluidic devices, while delaying the onset of high-$\mathit{Du}$ electrokinetic suppression.

Atlantic mercury emission determined from continuous analysis of the elemental mercury sea-air concentration difference within transects between 50°N and 50°S

[1] Mercury in the environment deserves serious concern because of the mobility of volatile elemental mercury (Hg0) in the atmosphere, in combination with the harmful effect of Hg compounds on human health and the ecosystem. A major source of global atmospheric mercury is presumed to be oceanic Hg0 emission. However, available Hg0 surface water data to reliably estimate the ocean's mercury emissions are sparse. In this study, high-resolution surface water and air measurements of Hg0 were carried out between Europe and South Africa in November 2008 and between South America and Europe in April–May 2009. On each cruise a strong enrichment of Hg0 in tropical surface water was determined that apparently followed the seasonal shift of the Intertropical Convergence Zone (ITCZ). A combination of a high Hg0 production rate constant and the actual low wind speeds, which prevented emission, probably caused the accumulation of Hg0 in surface waters of the ITCZ. Hg0 emissions in the tropics were significant only if wind speed variability on a monthly scale was considered, in which case the observed significant decline of total Hg in tropical surface waters during the northern winter could be explained. In the midlatitudes, increased autumn Hg0 emissions were calculated for November in the Northern Hemisphere and for May in the Southern Hemisphere; conversely, emissions were low during both the northern and the southern spring. Mercury removal from surface waters by Hg0 emission and sinking particles was comparable to its supply through wet and dry deposition.

Electrokinetic remediation: The use of mercury speciation for feasibility studies applied to a contaminated soil from Almadén

We have chosen the BCR (Bureau Communautaire de Référence) sequential extraction procedure as a speciation analysis to determine the mobility of mercury in the contaminated soil of the Almadén (Spain) mining district. This soil has a high mercury concentration (1000 mg kg −1) in some areas. In previous works, the relationship between the weak-acid soluble fraction and the amount of contaminant recoverable by acid-enhanced electrokinetic remediation (EKR) was shown. In this study, after testing that this relationship is maintained, we test if similar relationships with chelating agents could be established. Recently, several chelating agents were tried and iodide was shown to be quite efficient for the removal of mercury. Thus we have carried out iodide-enhanced EKR experiments at the lab (16 g of soil) and semi-pilot (2 kg) scales. From these experiments it can be concluded that the amount of mercury recoverable by this technique is similar to the one recovered in the batch extraction experiments. Thus, this is another evidence that this kind of experiments can be used for the feasibility studies of the remediation technique. It is also shown that, although the removal efficiency is similar to the one obtained previously for in situ flushing, the time required to achieve this efficiency would be several orders of magnitude shorter for this soil. Nevertheless, the residual Hg present in the weak-acid soluble fraction of the speciation analysis of the soil after the EKR treatment increases with respect to the original contaminated soil, indicating a possible increase of the risks associated to the contaminated site. Therefore, a second EKR treatment is applied to the same soil, this time using acid-enhanced EKR. It is shown that, although almost no Hg was recovered with this technique for the original soil, an important amount can be recovered after the first treatment (iodide-enhanced EKR). Also it is shown that the design and operation of this second technique should be studied carefully due to the rather complex chemistry of the species involved.

Mobility and contamination assessment of mercury in coal fly ash, atmospheric deposition, and soil collected from Tianjin, China

Samples of class F coal fly ash (levels I, II, and III), slag, coal, atmospheric deposition, and soils collected from Tianjin, China, were analyzed using U.S. Environmental Protection Agency (U.S. EPA) Method 3052 and a sequential extraction procedure, to investigate the pollution status and mobility of Hg. The results showed that total mercury (HgT) concentrations were higher in level I fly ash (0.304 µg/g) than in level II and level III fly ash and slag (0.142, 0.147, and 0.052 µg/g, respectively). Total Hg in the atmospheric deposition was higher during the heating season (0.264 µg/g) than the nonheating season (0.135 µg/g). Total Hg contents were higher in suburban area soils than in rural and agricultural areas. High HgT concentrations in suburban area soils may be a result of the deposition of Hg associated with particles emitted from coal-fired power plants. Mercury in fly ash primarily existed as elemental Hg, which accounted for 90.1, 85.3, and 90.6% of HgT in levels I, II, and III fly ash, respectively. Mercury in the deposition existed primarily as sulfide Hg, which accounted for 73.8% (heating season) and 74.1% (nonheating season) of HgT. However, Hg in soils existed primarily as sulfide Hg, organo-chelated Hg and elemental Hg, which accounted for 37.8 to 50.0%, 31.7 to 41.8%, and 13.0 to 23.9% of HgT, respectively. The percentage of elemental Hg in HgT occurred in the order fly ash > atmospheric deposition > soils, whereas organo-chelated Hg and sulfide Hg occurred in the opposite order. The present approach can provide a window for understanding and tracing the source of Hg in the environment in Tianjin and the risk associated with Hg bioaccessibility.

Arsenic and Mercury mobility in brazilian sediments from the São Francisco River Basin

Os sedimentos possuem propriedades de acumulacao de poluentes e a determinacao de elementos toxicos nessas amostras permite avaliar o seu ciclo geoquimico. Arsenio e mercurio foram determinados em 28 amostras de sedimento da Bacia do Rio Sao Francisco, Minas Gerais, Brasil, por geracao de hidretos acoplada a espectrometria de absorcao atomica (HG AAS). Foram empregados procedimentos de digestao pseudo-total empregando HCl:HNO3 (3:1 v/v) e extracao parcial com HCl 1 mol L-1. Realizou-se ainda a determinacao de Hg nas amostras solidas, utilizando-se um analisador direto de mercurio. Observou-se que 46% das amostras apresentaram concentracoes de As acima do limite de nivel 1 estabelecido pela Resolucao 344/2004 do CONAMA e que 14% excederam o limite de nivel 1 para Hg. As amostras com altas concentracoes de Hg foram tambem analisadas por termodessorcao acoplada a espectrometria de absorcao atomica (TDAAS) para especiacao e os termogramas apontaram somente a presenca da especie Hg(II)

Distribution and mobility of mercury in soils of a gold mining region, Cuyuni river basin, Venezuela

An extensive and remote gold mining region located in the East of Venezuela has been studied with the aim of assessing the distribution and mobility of mercury in soil and the level of Hg pollution at artisanal gold mining sites. To do so, soils and pond sediments were sampled at sites not subject to anthropological influence, as well as in areas affected by gold mining activities. Total Hg in regionally distributed soils ranged between 0.02mgkg−1 and 0.40mgkg−1, with a median value of 0.11mgkg−1, which is slightly higher than soil Hg worldwide, possibly indicating long-term atmospheric input or more recent local atmospheric input, in addition to minor lithogenic sources. A reference Hg concentration of 0.33mgkg−1 is proposed for the detection of mining affected soils in this region. Critical total Hg concentrations were found in the surrounding soils of pollutant sources, such as milling-amalgamation sites, where soil Hg contents ranged from 0.16mgkg−1 to 542mgkg−1 with an average of 26.89mgkg−1, which also showed high levels of elemental Hg, but quite low soluble+exchangeable Hg fraction (0.02–4.90mgkg−1), suggesting low Hg soil mobility and bioavailability, as confirmed by soil column leaching tests. The vertical distribution of Hg through the soil profiles, as well as variations in soil Hg contents with distance from the pollution source, and Hg in pond mining sediments were also analysed.

Distribution, accumulation and mobility of mercury in superficial sediment samples from Tianjin, northern China

Seventeen sediment samples at three representative sites (the Yuqiao Reservoir, the Haihe River and the Haihe River Estuary) in Tianjin, northern China, were analyzed to investigate the pollution status, accumulation and mobility of mercury (Hg). The results show that the Haihe River has to be considered as moderate to strongly contaminated with Hg (2 < mean I(geo) = 2.35 < 3), where total Hg contents were ca. 3 to 24 orders of magnitude greater than the regional background value. The sediments collected near a coal-fired power plant in an urban area were found to have very high Hg concentrations, which were significantly related to Hg emissions from coal-fired utility boilers. In the Yuqiao Reservoir, the surface sediments have to be considered as unpolluted with Hg (mean I(geo) = -0.05 < 0) and the Haihe River Estuary sediments have to be considered as unpolluted to moderately polluted with Hg (0 < mean I(geo) = 0.18 < 1). Sediment-bound Hg in the Yuqiao Reservoir and the Haihe River Estuary was found to be predominantly associated with the organo-chelated phase of the sediment (38.3% and 50.5%, respectively). However, unlike the Yuqiao Reservoir and the Haihe River Estuary, Hg in the Haihe River sediments existed mainly as sulfide Hg and elemental Hg, which accounted for 54.2% and 30.7% of total Hg, respectively. The availability of this element seemed restricted. The majority of Hg contamination in the Haihe River sediments had been attributed to historic and modern atmospheric deposition and Hg released from the Haihe River sediments didn't seem to be an important pollutant pathway into the Haihe River Estuary. The results provide new insights into Hg contamination in this region.

Does anoxia affect mercury cycling at the sediment–water interface in the Gulf of Trieste (northern Adriatic Sea)? Incubation experiments using benthic flux chambers

Abstract Coastal areas in the northernmost part of the Adriatic Sea (Gulf of Trieste and the adjacent Grado Lagoon) are characterized by high levels of Hg, both in sediments and in the water column, mainly originating from the suspended material inflowing through the Isonzo/Soca River system, draining the Idrija (NW Slovenia) mining district, into the Gulf of Trieste. Hypoxic and anoxic conditions at the sediment–water interface (SWI) are frequently observed in the Gulf of Trieste and in the lagoon, due to strong late summer water stratification and high organic matter input. Mercury mobility at the SWI was investigated at three sampling points located in the Gulf of Trieste (AA1, CZ) and in the Grado Lagoon (BAR). Experiments were conducted under laboratory conditions at in situ temperature, using a dark flux chamber simulating an oxic–anoxic transition. Temporal variations of dissolved Hg and methylmercury (MeHg) as well as O2, NH 4 + , NO 3 - + NO 2 - , PO 4 3 - , H2S, dissolved Fe and Mn, dissolved inorganic C (DIC) and dissolved organic C (DOC) were monitored simultaneously. Benthic Hg fluxes were higher under anoxic conditions than in the oxic phase of the experiment. Methyl Hg release was less noticeable (low or absent) in the oxic phase, probably due to similar methylation and demethylation rates, but high in the anoxic phase of the experiment. The MeHg flux was linked to SO4 reduction and dissolution of Fe (and Mn) oxyhydroxides, and formation of sulphides. Re-oxygenation was studied at sampling point CZ, where concentrations of MeHg and Hg dropped rapidly probably due to re-adsorption onto Fe (Mn) oxyhydroxides and enhanced demethylation. Sediments, especially during anoxic events, should be, hence, considered as a primary source of MeHg for the water column in the northern Adriatic coastal areas.

Extractability and mobility of mercury from agricultural soils surrounding industrial and mining contaminated areas

This study focussed on a comparison of the extractability of mercury in soils with two different contamination sources (a chlor-alkali plant and mining activities) and on the evaluation of the influence of specific soil properties on the behaviour of the contaminant. The method applied here did not target the identification of individual species, but instead provided information concerning the mobility of mercury species in soil. Mercury fractions were classified as mobile, semi-mobile and non-mobile. The fractionation study revealed that in all samples mercury was mainly present in the semi-mobile phase (between 63% and 97%). The highest mercury mobility (2.7 mg kg −1) was found in soils from the industrial area. Mining soils exhibited higher percentage of non-mobile mercury, up to 35%, due to their elevated sulfur content. Results of factor analysis indicate that the presence of mercury in the mobile phase could be related to manganese and aluminium soil contents. A positive relation between mercury in the semi-mobile fraction and the aluminium content was also observed. By contrary, organic matter and sulfur contents contributed to mercury retention in the soil matrix reducing the mobility of the metal. Despite known limitations of sequential extraction procedures, the methodology applied in this study for the fractionation of mercury in contaminated soil samples provided relevant information on mercury’s relative mobility.

XANES speciation of mercury in three mining districts – Almadén, Asturias (Spain), Idria (Slovenia)

The mobility, bioavailability and toxicity of mercury in the environment strongly depend on the chemical species in which it is present in soil, sediments, water or air. In mining districts, differences in mobility and bioavailability of mercury mainly arise from the different type of mineralization and ore processing. In this work, synchrotron-based X-ray absorption near-edge spectroscopy (XANES) has been taken advantage of to study the speciation of mercury in geological samples from three of the largest European mercury mining districts: Almadén (Spain), Idria (Slovenia) and Asturias (Spain). XANES has been complemented with a single extraction protocol for the determination of Hg mobility. Ore, calcines, dump material, soil, sediment and suspended particles from the three sites have been considered in the study. In the three sites, rather insoluble sulfide compounds (cinnabar and metacinnabar) were found to predominate. Minor amounts of more soluble mercury compounds (chlorides and sulfates) were also identified in some samples. Single extraction procedures have put forward a strong dependence of the mobility with the concentration of chlorides and sulfates. Differences in efficiency of roasting furnaces from the three sites have been found.

Assessment of the pollution potential of mercury contaminated biosolids

Environmental context. The re-use of biosolids (sewage sludge) is becoming increasingly popular especially for land applications as soil improvers, fertilisers and composts. However, some biosolids are contaminated with toxic heavy metals and mercury is arguably of the highest environmental and public health concern. Studies on mobility, availability and emissions of mercury from biosolids were carried out to assess the biosolids potential for contamination of the environment and to evaluate applicable techniques for a future remediation. Abstract. Biosolids from Melbourne Water’s Western Treatment Plant (WTP) in Australia contain elevated levels of mercury. Consequently, monitoring programs are crucial in order to assess localised impacts to the environment and on humans immediately surrounding the boundaries of the WTP. Dry biosolids were surveyed for Hg, other heavy metals, cations, soluble anions, sulfur and phosphorus. Mercury concentrations were found to vary between 3.5 and 8.4 mg kg–1 Hg, indicating that biosolids from some locations were above the safety level (5 mg kg–1 Hg) for land applications. High concentrations of soluble anions and cations revealed elevated salinity levels. The biosolids with the highest Hg concentration were further studied to assess their potential for Hg remediation. The results obtained by a sequential extraction procedure showed that 59.01% of the total mercury was complexed with organic ligands. In addition, the influence of air temperature, water content and irradiation on the emission of gaseous elemental mercury from biosolids was studied. Light exposure and water addition were the main factors affecting this emission with flux values up to 132 ng m–2 h–1.

Mercury Redox Chemistry in the Negro River Basin, Amazon: The Role of Organic Matter and Solar Light

Pristine water bodies in the Negro River basin, Brazilian Amazon, show relatively high concentrations of mercury. These waters are characterized by acidic pH, low concentrations of suspended solids, and high amounts of dissolved organic matter and are exposed to intense solar radiation throughout the year. This unique environment creates a very dynamic redox chemistry affecting the mobility of mercury due to the formation of the dissolved elemental species (Hg0). It has been shown that in this so-called black water, labile organic matter from flooded forest is the major scavenger of photogenerated H2O2. In the absence of hydrogen peroxide, these black waters lose their ability to oxidize Hg0 to Hg2+, thus increasing Hg0 evasion across the water/atmosphere interface, with average night time values of 3.80 pmol m−2 h−1. When the dry period starts, labile organic matter inputs gradually diminish, allowing the increasing concentration of H2O2 to re-establish oxidative water conditions, inhibiting the metal flux across the water/atmosphere interface and contributing to mercury accumulation in the water column.

Mercury in Biomass Feedstock and Combustion Residuals

An exploratory survey of the mercury content of some common California biomass feedstocks shows that the concentrations are well below EPA toxicity levels with representative feedstock concentrations of 20 ppb for rice straw, 28 ppb for wheat straw, and 32 ppb for whole-tree wood chips. The temporal variability for rice straw (17-20 ppb) is near the analytical uncertainty (∼2 ppb). Saline-irrigated feedstock does not contain greatly higher mercury contents (17-38 ppb) compared to normally irrigated feedstock. Water leaching has likewise no detectable effects on mercury mobility, despite an up to 30% increase in the Hg concentrations attributable to mass losses during leaching. Combustion at temperatures of at least 575°C results in complete volatilization of mercury leaving solid ash and slag residuals with mercury contents at or near the lower limit of detection (5 ppb). The mercury strongly concentrated in fly ash can reach concentrations up to 40 times (<1,166 ppb) the corresponding fuel concentrations.

Fractions and leaching characteristics of mercury in coal

A huge amount of coal is always stored in open spaces in coal-fired power plants before combustion. Mercury released from coal by rain or flowing water is an environmental risk and can cause contamination of the soil around the storage area. To better understand mercury pollution and to control mercury emission before combustion, it is necessary to determine the mobility and leaching characteristics of mercury from coal. In this study, we collected ten coal samples from one coal-fired power plant and proposed a sequential extraction procedure to get five fractions of mercury for evaluation. Elemental Hg was found as the most dominant fraction, and sulfate Hg was shown to be the second largest fraction. The mercury in the organic and the soluble fractions were not the major fractions, but they should still be considered because of their high mobility.

Mercury Adsorption‐Desorption and Transport in Soils

Kinetic sorption and column miscible displacement transport experiments were performed to quantify the extent of retention/release and the mobility of mercury in different soils. Results indicated that adsorption of mercury was rapid and highly nonlinear with sorption capacities having the following sequence: Sharkey clay > Olivier loam > Windsor sand. Mercury adsorption by all soils was strongly irreversible where the amounts released or desorbed were often less than 1% of that applied. Moreover, the removal of soil organic matter resulted in a decrease of mercury adsorption in all soils. Adsorption was described with limited success using a nonlinear (Freundlich) model. Results from the transport experiments indicated that the mobility of mercury was highly retarded, with extremely low concentrations of mercury in column effluents. Furthermore, mercury breakthrough curves exhibited erratic patterns with ill-distinguished peaks. Therefore, mercury is best regarded as strongly retained and highly "immobile" in the soils investigated. This is most likely due to highly stable complex formation (irreversible forms) and strong binding to high-affinity sites. In a column packed with reference sand material, a symmetric breakthrough curve was obtained where the recovery of mercury in the leachate was only 17.3% of that applied. Mercury retention by the reference sand was likely due to adsorption by quartz and metal-oxides.

Enhanced Uptake and Modified Distribution of Mercury(II) by Fulvic Acid on the Muscovite (001) Surface

Evidence is increasing for the mobility and bioavailability of aqueous mercury(II) species being related to the interactions of mercury with dissolved organic matter (DOM). Here, we assess the relative roles of the mineral surface and DOM in controlling mercury(II) uptake at the muscovite (001)-solution interface using interface-specific X-ray reflectivity combined with element-specific resonant anomalous X-ray reflectivity. Experiments were performed with single crystals of muscovite and solutions of 100 mg/kg Elliott Soil Fulvic Acid II and 0.5-1 x 10(-3) mol/kg Hg(NO3)2 at pH 2-12 Mercury(II) adsorbed from a 1 x 10(-3) mol/kg Hg(II) solution at pH 2 without fulvic acid (FA) as inner- and outer-sphere complexes that compensated 55(4)% of the permanent negative charge of the muscovite surface. The remaining charge presumably was compensated by hydronium. The enhanced uptake of Hg(II) (compensating 128% of the muscovite surface charge) and FA (43% more adsorbed compared to the amount from a similar solution without Hg), along with a broader distribution of Hg(II) at the interface, occurred by adsorption from a premixed solution of 1 x 10(-3) mol/kg Hg(NO3)2 and 100 mg/kg FA at pH 2. Adsorption of Hg(II) and FA, likely as complexes, decreased significantly as pH increased from 3.7 to 12 in solutions of 0.5 x 10(-3) mol/kg Hg(NO3)2 and 100 mg/kg FA. Preadsorbed FA molecules provide different binding environments and stability for Hg(II) than dissolved FA, which may be attributed to conformational differences, fractionation, or kinetic effects in the presence of the mineral surface, at least at these relatively high concentrations of aqueous Hg(II).

Precipitation of Mercuric Sulfide Nanoparticles in NOM-Containing Water: Implications for the Natural Environment

Speciation of mercury(II) in the aquatic environment and coordination to natural organic matter (NOM) and sulfides governs the bioavailability and mobility of mercury in water and sediment. While previous studies on aqueous Hg(II) speciation have focused on competitive binding of dissolved species, the purpose of this study was to explore the potential for HgS nanoparticles that coprecipitate with NOM in solution. Dynamic light scattering was used to monitor the size of HgS colloids growing over time. The results indicated that humic substances decreased observed growth rates of particles and stabilized aggregates smaller than 0.2 microm for at least 8 h. Thiol-containing organic acids such as cysteine and thioglycolate also decreased growth of HgS particles. Growth rates were also monitored as a function of monovalent electrolyte concentration, humic type, and humic concentration. HgS particles that formed in the presence of humics and thiolates were able to pass through conventional filters (<0.2 micro/m) and appeared to consist of aggregates of nanocrystals in TEM images. Furthermore, 96% of HgS aggregates were removed from aqueous suspension when exposed to octanol, indicating that the particles could be incorrectly identified as dissolved complexes (e.g., HgS(0)(aq)) in bioavailability models. Hg speciation calculations were conducted to consider lower Hg concentrations observed in sediment porewater. While the calculations depended on Hg binding constants that can vary by orders of magnitude, the results indicated that HgS(s) could be oversaturated in filtered porewater, particularly at low dissolved sulfide levels (micromolar or lower). These insights suggest that nanoparticulate HgS can exist in surface waters and porewater of contaminated sediments as a result of kinetically hindered aggregation/precipitation reactions. Further studies are neededto addressthe importance of nanoscale HgS particles for governing the reactivity and bioavailability of mercury in the environment.