Jianxu Wang

Remediation of mercury contaminated sites – A review

Environmental contamination caused by mercury is a serious problem worldwide. Coal combustion, mercury and gold mining activities and industrial activities have led to an increase in the mercury concentration in soil. The objective of this paper is to present an up-to-date understanding of the available techniques for the remediation of soil contaminated with mercury through considering: mercury contamination in soil, mercury speciation in soil; mercury toxicity to humans, plants and microorganisms, and remediation options. This paper describes the commonly employed and emerging techniques for mercury remediation, namely: stabilization/solidification (S/S), immobilization, vitrification, thermal desorption, nanotechnology, soil washing, electro-remediation, phytostabilization, phytoextraction and phytovolatilization.

Localization and speciation of mercury in brown rice with implications for pan-Asian public health.

Cultivation of paddy rice for human consumption is a dominant agricultural activity throughout Asia. High levels of mercury (Hg) in rice grain pose a potential threat to human health, although the extent of risk is dependent on the chemical speciation of Hg inside the grain. We have investigated the speciation and localization of Hg in three fractions of rice grain (hull, bran, and white rice) collected from a Hg-contaminated region in China. On a mass basis, the majority of inorganic mercury (IHg) in a rice grain is found in hull and bran. However, the majority of the more toxic species methyl mercury (MeHg) is found in edible white rice. Our data show that during grain processing, most of the IHg (∼78%) is eliminated, but the majority of the MeHg remains in the food product (∼80%). Synchrotron radiation microscopic X-ray fluorescence (SR-μXRF) mapping shows strong localization of Hg at the surface of brown rice grains, corresponding to the pericarp and aleurone layer. We infer that this Hg is predominantly IHg absorbed from the atmosphere. Based on X-ray absorption near-edge spectroscopy (XANES) data we propose that IHg in bran is primarily bound to cysteine, and is associated with phytochelatins. Consequently, IHg is largely immobile and restricted to the outer layers of rice grain. MeHg in bran is primarily bound to cysteine and is associated with proteins. However, this MeHg-cysteine association behaves like a mobile nutrient and is actively transported to the endosperm during seed ripening. Concentration of MeHg-cysteine in white rice has implications for public health. There is growing evidence for Hg contamination of rice throughout Asia due to point and diffuse sources of Hg pollution. The magnitude of the associated risk must be quantified through better understanding of the localization and speciation of mercury in rice. Our work makes an effort to contribute to this understanding.

Implications of mercury speciation in thiosulfate treated plants.

Mercury uptake was induced in two cultivars of Brassica juncea under field conditions using thiosulfate. Analysis was conducted to better understand the mechanism of uptake, speciation of mercury in plants, and redistribution of mercury in the soil. Plant mercury and sulfur concentrations were increased after thiosulfate treatment, and a linear correlation between mercury and sulfur was observed. Mercury may be absorbed and transported in plants as the Hg-thiosulfate complex. The majority of mercury in treated plant tissues (two cultivars) was bound to sulfur in a form similar to β-HgS (66-94%). Remaining mercury was present in forms similar to Hg-cysteine (1-10%) and Hg-dicysteine (8-28%). The formation of β-HgS may relate to the transport and assimilation of sulfate in plant tissues. Mercury-thiosulfate complex could decompose to mercuric and sulfate ions in the presence of free protons inside the plasma membrane, while sulfide ions would be produced by the assimilation of sulfate. The concomitant presence of mercuric ions and S(2-) would precipitate β-HgS. The mercury concentration in the rhizosphere decreased in the treated relative to the nontreated soil. The iron/manganese oxide and organic-bound fractions of soil mercury were transformed to more bioavailable forms (soluble and exchangeable and specifically sorbed) and taken up by plants.

Mercury distribution in the soil–plant–air system at the Wanshan mercury mining district in Guizhou, Southwest China

The level of mercury bioaccumulation in wild plants; the distribution of bioavailable Hg, elemental Hg, and total Hg in soil; and the concentration of total gaseous Hg (TGM) in ambient air was studied at three different mining sites (SiKeng [SK], WuKeng [WK], and GouXi [GX]) in the Wanshan mercury mining district of China. Results of the present study showed that the distribution of soil total Hg, elemental Hg, bioavailable Hg, and TGM varies across the three mining sites. Higher soil total Hg (29.4-1,972.3 mg/kg) and elemental Hg (19.03-443.8 mg/kg) concentrations were recorded for plots SK and WK than for plot GX. Bioavailable Hg was lower at plot SK and GX (SK, 3-12 ng/g; GX, 9-14 ng/g) than at plot WK (11-1,063 ng/g), although the TGM concentration in the ambient air was significantly higher for plot GX (52,723 ng/m(3) ) relative to WK (106 ng/m(3) ) and SK (43 ng/m(3)). Mercury in sampled herbage was elevated and ranged from 0.8 to 4.75 mg/kg (SK), from 2.17 to 34.38 mg/kg (WK), and from 47.45 to 136.5 mg/kg (GX). Many of the sampled plants are used as fodder or for medicinal purposes. High shoot Hg concentrations may therefore pose an unacceptable human health risk. Statistical analysis of the recorded data showed that the Hg concentration in plant shoots was positively correlated with TGM and that the Hg concentration in roots was positively correlated with the bioavailable Hg concentration in the soil. The bioaccumulation factor (BAF) in the present study was defined with reference to the concentration of bioavailable Hg in the soil (Hg([root]) /Hg([bioavail])). Three plant species, Macleaya cordata L., Achillea millefolium L., and Pteris vittata L., showed enhanced accumulation of Hg and therefore may have potential for use in the phytoremediation of soils of the Wanshan mining area.

Thiosulphate-induced mercury accumulation by plants: metal uptake and transformation of mercury fractionation in soil - results from a field study

AimsThe thiosulphate induced accumulation of mercury by the three plants Brassica juncea var.LDZY, Brassica juncea var.ASKYC and Brassica napus var. ZYYC and the transformation of mercury fractionation in the rhizosphere of each plant was investigated in the field.MethodsExperimental farmland was divided into control and thiosulphate plots. Each plot was divided into three subplots with each planted with one of the plants. After harvesting, the mercury concentration in plants, mercury fractionation in rhizosphere soil before and after phytoextraction, and the vertical distribution of bioavailable mercury in bulk soil profiles was analyzed.ResultsThe cultivar B. juncea var.LDZY accumulated a higher amount of mercury in shoots than the other two plants. Thiosulphate treatment promoted an increase in the concentration of metal in plants and a transformation of Fe/Mn oxide-bound and organic-bound mercury (potential bioavailable fractions) into soluble and exchangeable and specifically-sorbed fractions in the rhizosphere. The observed increase in bioavailable rhizosphere mercury concentration was restricted to the root zone; mercury did not move down the soil profile as a function of thiosulphate application to soil.ConclusionsThiosulphate-induced phytoextraction has the potential to manage environmental risk of mercury in soil by decreasing the concentration of mercury associated with potential bioavailable fraction that can be accumulated by crop plants.

Effect of cropping systems on heavy metal distribution and mercury fractionation in the Wanshan mining district, China: Implications for environmental management

The authors studied the concentration of heavy metals and mercury fractionation in contaminated soil in 2 agricultural land use systems (paddy rice and dry land) at the Wanshan mercury mine in China. The average concentrations of chromium, lead, copper, nickel, and zinc were generally lower in paddy rice soil relative to corn field soil. Soil under corn field production was slightly contaminated with lead (22-100 mg/kg), copper (31-64 mg/kg), and nickel (22-76 mg/kg) and moderately contaminated with zinc (112-635 mg/kg). In both soils, correlation of these metals with the titanium concentration in the soil indicates a geogenic origin for each metal (lead, r = 0.48; copper, r = 0.63; nickel, r = 0.47; zinc, r = 0.48). The mercury and antimony concentration in soil was high under both cropping systems, and future remediation efforts should consider the potential environmental risk presented by these metals. The concentration of bioavailable mercury in soil ranged from 0.3 ng/g to 11 ng/g across the 2 cropping systems. The majority of mercury (>80%) was associated with organic matter and the residual fraction. However, soil under paddy rice production exhibited a significantly lower concentration of Fe/Mn oxide-bound mercury than that under corn field production. This may be a function of the reduction of Fe/Mn oxides in the paddy rice soil, with the subsequent release of adsorbed metals to the soil solution. Sequential change from corn field to paddy rice production, as practiced in Wanshan, should therefore be avoided. Mercury adsorbed to Fe/Mn oxides in corn field soil potentially could be released into the soil solution and be made available for biomethylation under the flooded water management conditions of a rice paddy.

Biogenesis of Mercury–Sulfur Nanoparticles in Plant Leaves from Atmospheric Gaseous Mercury

Plant leaves serve both as a sink for gaseous elemental mercury (Hg) from the atmosphere and a source of toxic mercury to terrestrial ecosystems. Litterfall is the primary deposition pathway of atmospheric Hg to vegetated soils, yet the chemical form of this major Hg input remains elusive. We report the first observation of in vivo formation of mercury sulfur nanoparticles in intact leaves of 22 native plants from six different species across two sampling areas from China. The plants grew naturally in soils from a mercury sulfide mining and retorting region at ambient-air gaseous-Hg concentrations ranging from 131 ± 19 to 636 ± 186 ng m-3 and had foliar Hg concentration between 1.9 and 31.1 ng Hg mg-1 dry weight (ppm). High energy resolution X-ray absorption near-edge structure (HR-XANES) spectroscopy shows that up to 57% of the acquired Hg is nanoparticulate, and the remainder speciated as a bis-thiolate complex (Hg(SR)2). The fractional amount of nanoparticulate Hg is not correlated with Hg concentration. Variation likely depends on leaf age, plant physiology, and natural variability. Nanoparticulate Hg atoms are bonded to four sulfide or thiolate sulfur atoms arranged in a metacinnabar-type (β-HgS) coordination environment. The nanometer dimension of the mercury-sulfur clusters outmatches the known binding capacity of plant metalloproteins. These findings give rise to challenging questions on their exact nature, how they form, and their biogeochemical reactivity and fate in litterfall, whether this mercury pool is recycled or stored in soils. This study provides new evidence that metacinnabar-type nanoparticles are widespread in oxygenated environments.

The use of calcium carbonate-enriched clay minerals and diammonium phosphate as novel immobilization agents for mercury remediation: Spectral investigations and field applications

We used calcium carbonate-enriched clay minerals (CECM) and diammonium phosphate (DAP) as immobilization agents for mercury (Hg) immobilization. The effects of CECM, DAP, or both in different amounts and ratios, as well as pH and initial Hg concentrations, on Hg removal from solutions were investigated. The removal mechanism was revealed using transmission electron microscope with energy-dispersive X-ray (TEM-EDX) spectroscopy, and extended X-ray absorption fine structure spectroscopy (EXAFS). The performance of CECM and DAP under field conditions was also studied. The results showed that application of CECM and DAP at a ratio of 50:1 (w/w) removed over 90% of Hg from solutions containing 1.8 μM Hg2+, which was 9- or 2.6-fold higher than solely DAP (<10%) or CECM (34%<), respectively. Mercury removal by CECM and DAP was weakly affected by pH values between 4 and 10, and their maximum Hg removal capacity was 37 mg g-1. Both TEM-EDX and EXAFS results showed that the precipitate of Hg with phosphorus-associated minerals might be the primary mechanism of Hg removal by CECM and DAP. Results from the field trial showed that application of CECM and DAP decreased soil bioavailable Hg contents, but did not affect contents of organic matter bound Hg or residual Hg fractions, as compared with control and initial soils. Application of CECM and DAP resulted in dramatic reductions (40%-53%) of Hg in the edible tissues of Brassica chinensis and Raphanus raphanistrum in comparison to the non-treated control. We conclude that CECM and DAP offer a promising method for in situ remediation of Hg-contaminated farmlands in southwest of China.

Potentially toxic elements in saltmarsh sediments and common reed (Phragmites australis) of Burullus coastal lagoon at North Nile Delta, Egypt: A survey and risk assessment

Burullus lagoon is the second largest lake in Egypt. However, there has never been a comprehensive survey which studied nineteen potentially toxic elements in sediments and plants and evaluated the associated potential risk. Thus, we aimed to study the total and potentially available content of As, Al, Cd, Co, Cr, Cu, Fe, Hg, Mn, Mo, Ni, Sb, Se, Sn, Tl, V, and Zn in the sediments and common reed (Phragmites australis) at thirty two sites along the entire lagoon and connected drains. Contamination Factor (CF), Pollution Load Index (PLI), Geo-accumulation Index (Igeo), and Enrichment Factor (EF) were calculated to assess the grade of contamination. Element accumulation factor (AF) and bio-concentration ratio (BCR) were also calculated. Aluminum showed the highest median (mg kg-1) total content (41,200), followed by Fe (30,300), Mn (704.7), V (82.0), Zn (75.5), Cr (51.2), Cu (47.8), Ni (44.3), As (31.9), Tl (24.6), Co (21.4), Se (20.3), Sb (17.6), Sn (15.6), Mo (11.3), and Hg (16.6 μg kg-1). Values of the EF, CF, and Igeo showed that the sediments were heavily contaminated with As, Sb, Se, Tl, Mo, Sn, Co, Ni, and Cu. The drained sediment had significantly higher values of total and potentially available element content than the lagoon sediments. Sediments of the middle and western area showed significantly higher contents of total and available elements than the eastern section. The BCR and AF values indicate that the studied plant is efficient in taking up high amounts of Zn, Fe, As, Sn, Tl, Ni, Mo, Mn; then Co, Cu, and V. The results exhibit a dramatic contamination at certain sites of the lagoon, and the studied PTEs have a predominant role in contamination-related ecological risk. Further investigations concerning redox-induced mobilization of PTEs in sediments, the risk of fish contamination and the potential health hazards are highly recommended.

Thiosulphate-induced phytoextraction of mercury in Brassica juncea: Spectroscopic investigations to define a mechanism for Hg uptake

Thiosulphate is extensively used to enhance mercury (Hg) phytoextraction due to its efficient in prompting plant Hg uptake. However, the mechanism by which thiosulphate promotes Hg uptake is poorly understood. We determined the concentrations of Hg and potassium (K), and their spatial distribution, in the tissues of Brassica juncea grown in Hg-contaminated soils treated by thiosulphate and compared this to a non-treated soil (control). The spatial distribution of Hg and K was characterized using micro-X ray fluorescence spectroscopy. The subcellular localization and speciation of Hg in the root of plant treated by thiosulphate were elucidated using Transmission electron microscope coupled energy-dispersive X-ray (TEM-EDX) spectroscopy. Thiosulphate increased significantly the Hg concentration in the roots (mainly in the epidermis and xylem) and shoots (mainly in the vascular bundles), while Hg was accumulated in the root (mainly in the epidermis) of the control plant. Thiosulphate promoted the movement of Hg from the epidermis to the xylem of roots, with subsequent loading into the stem via vascular bundles. Thiosulphate decreased the K concentration in plant tissues, relative to the control plant, and we propose this is due to leakage of electrolyte from roots via increased plasma membrane permeability as a consequence of physiological damage caused by the added thiosulphate. Mercury was distributed mainly at the extracellular space in the roots and was shown by TEM-EDX to be predominately amorphous nano-clusters of HgS. We conclude that thiosulphate-promoted Hg accumulation in the plant may happen through increased plasma membrane permeability, a changed pathway of Hg movement within plants, and extracellular co-transportation of Hg-S complexes in the roots. Our results may underpin the ongoing development of phytomanagement as an environmental strategy for Hg contaminated soils around the world.