The phytochelatin transporters AtABCC1 and AtABCC2 mediate tolerance to cadmium and mercury.

Heavy metals such as cadmium (Cd) and mercury (Hg) are toxic pollutants that are detrimental to living organisms. Plants employ a two-step mechanism to detoxify toxic ions. First, phytochelatins bind to the toxic ion, and then the metal-phytochelatin complex is sequestered in the vacuole. Two ABCC-type transporters, AtABCC1 and AtABCC2, that play a key role in arsenic detoxification, have recently been identified in Arabidopsis thaliana. However, it is unclear whether these transporters are also implicated in phytochelatin-dependent detoxification of other heavy metals such as Cd(II) and Hg(II). Here, we show that atabcc1 single or atabcc1 atabcc2 double knockout mutants exhibit a hypersensitive phenotype in the presence of Cd(II) and Hg(II). Microscopic analysis using a Cd-sensitive probe revealed that Cd is mostly located in the cytosol of protoplasts of the double mutant, whereas it occurs mainly in the vacuole of wild-type cells. This suggests that the two ABCC transporters are important for vacuolar sequestration of Cd. Heterologous expression of the transporters in Saccharomyces cerevisiae confirmed their role in heavy metal tolerance. Over-expression of AtABCC1 in Arabidopsis resulted in enhanced Cd(II) tolerance and accumulation. Together, these results demonstrate that AtABCC1 and AtABCC2 are important vacuolar transporters that confer tolerance to cadmium and mercury, in addition to their role in arsenic detoxification. These transporters provide useful tools for genetic engineering of plants with enhanced metal tolerance and accumulation, which are desirable characteristics for phytoremediation.

Gas-phase elemental mercury removal in a simulated combustion flue gas using TiO2 with fluorescent light.

UNLABELLED: A previously proposed technology incorporating TiO2 into common household fluorescent lighting was further tested for its Hg0 removal capability in a simulated flue-gas system. The flue gas is simulated by the addition of O2, SO2, HCl, NO, H2O, and Hg0, which are frequently found in combustion facilities such as waste incinerators and coal-fired power plants. In the O2 + N2 + Hg0 environment, a Hg0 removal efficiency (etaHg) greater than 95% was achieved. Despite the tendency for etaHg to decrease with increasing SO2 and HCl, no significant drop was observed at the tested level (SO2: 5-300 ppm, HCl: 30-120 ppm(v)). In terms of NO and moisture, a significant negative effect on etaHg was observed for both factors. NO eliminated the OH radical on the TiO2 surface, whereas water vapor caused either the occupation of active sites available to Hg0 or the reduction of Hg0 by free electron. However, the negative effect of NO was minimized (etaHg > 90%) by increasing the residence time in the photochemical reactor. The moisture effect can be avoided by installing a water trap before the flue gas enters the Hg0 removal system. IMPLICATIONS: This paper reports a novel technology for a removal of gas-phase elemental mercury (Hg0) from a simulated flue gas using TiO2-coated glass beads under a low-cost, easily maintainable household fluorescent light instead of ultraviolet (UV) light. In this study, the effects of individual chemical species (O2, SO2, HCl, NO, and water vapor) on the performance of the proposed technology for Hg0 removal are investigated. The result suggests that the proposed technology can be highly effective, even in real combustion environments such as waste incinerators and coal-fired power plants.

Stabilization and solidification of elemental mercury for safe disposal and/or long-term storage.

A simple and highly effective stabilization/solidification (S/S) technology of elemental mercury using only sulfur with paraffin is introduced. First, elemental mercury is mixed with an excess of sulfur powder and heated to 60 degrees C for 30 min until elemental mercury is converted into mercuric sulfide (HgS black, metacinnabar) (Step 1). Then, metacinnabar with additional sulfur is poured into liquid paraffin (Step 2). Finally, the mixture is melted at 140 degrees C and settles to the bottom of the vessel where it cools and solidifies under the layer of liquid paraffin (Step 3). The proposed S/S method with sodium sulfide nonahydrate (Na2S x 9H2O) as an additive is also tested for comparison. The average toxicity characteristic leaching procedure test values are 6.72 microg/L (no additive) and 3.18 microg/L (with additive). Theses concentrations are well below the Universal Treatment Standard (25 microg/L). Effective diffusion coefficient evaluated from accelerated leach test and average headspace concentration of Hg vapor after 18 hr are 3.62 x 10(-15) cm2/sec, 0.55 mg/m3 (no additive) and 5.86 x 10(-13) cm2/sec, 0.25 mg/m3 (with additive).

Photocatalytic oxidation of gas-phase elemental mercury by nanotitanosilicate fibers.

Photocatalytic fibers were generated from the continuous evaporation of titanium tetraisopropoxide with tetraethyl orthosilicate through a flame burner. The morphology, the crystal form, and the components of the nanotitanosilicate fibers were analyzed by Raman spectroscopy, Field emission-scanning electron microscope, X-ray diffraction, and Brunauer-Emmett-Teller surface area analysis. The nanotitanosilicates prepared by three different carrier gases (air, N(2), and Ar) were tested for their photocatalytic ability to remove/oxidize gas-phase elemental mercury. Under UV black light, the Hg(0) capture efficiencies were 78%, 86%, and 85% for air, N(2), and Ar, respectively. For air, the value was close to 90%, even under household fluorescent light. The Hg(0) capture efficiency by nanotitanosilcate was measured under fluorescent light, UV black light, and sunlight.

Mercury recovery from mercury-containing wastes using a vacuum thermal desorption system.

Mercury (Hg)-containing waste from various industrial facilities is commonly treated by incineration or stabilization/solidification and retained in a landfill at a managed site. However, when highly concentrated Hg waste is treated using these methods, Hg is released into the atmosphere and soil environment. To eliminate these risks, Hg recovery technology using thermal treatment has been developed and commercialized to recover Hg from Hg-containing waste for safe disposal. Therefore, we developed Hg recovery equipment to treat Hg-containing waste under a vacuum of 6.67kPa (abs) at 400°C and recover the Hg. In addition, the dust generated from the waste was separated by controlling the temperature of the dust filtration unit to 230°C. Additionally, water and Hg vapors were condensed in a condensation unit. The Hg removal rate after waste treatment was 96.75%, and the Hg recovery rate as elemental Hg was 75.23%.

Application of a sorbent trap system to gas-phase elemental and oxidized mercury analysis.

A sorbent trap that utilizes activated carbon (AC) as the solid trapping medium is a new technology for measuring total mercury (Hg) emissions from combustion facilities. In this study, sorbent trap technology was further developed, improved and evaluated at the laboratory scale. AC was impregnated with 5% aqua regia to enhance its Hg adsorption capacity. Sorbent traps spiked with an Hg standard solution were found to be reproducibly prepared and highly stable. The effect of the Hg concentration on the spiking efficiency was further investigated. The adsorption of elemental and oxidized Hg by the sorbent trap was studied under various experimental conditions (temperature, flow rate and inlet Hg concentration). The Hg concentration of the flue gas effluent from the sorbent trap was measured. In addition, the concentration of Hg adsorbed on the AC was determined by digesting the used AC with an acid according to US EPA method 3052 and then analyzing it with cold vapor atomic absorption spectrometry. Furthermore, the gas-phase Hg emissions from a combustion source were measured using the sorbent trap according to US EPA method 30B. The results showed that the sorbent trap could be used for Hg concentrations between 10.0 and 40.0 µg m(-3) and flow rates between 0.5 and 1.0 lpm with adsorption efficiencies greater than 90%.

Pilot-test of the calcium sodium phosphate (CNP) process for the stabilization/solidification of various mercury-contaminated wastes.

A pilot-scale calcium sodium phosphate (CNP) plant was designed and manufactured to examine the performance of recently developed stabilization/solidification (S/S) technology. Hg-contaminated wastes samples generated via various industrial processes in Korea, including municipal, industrial, and medical waste incineration, wastewater treatment, and lime production, were collected and treated using the pilot-scale CNP plant. S/S samples were fabricated according to various operating conditions, including waste type, the dose of the stabilization reagent (Na2S), and the waste loading ratio. Although the performances (Hg leaching value and compressive strength) were reduced as the waste loading ratio increased, most of the S/S samples exhibited Hg leaching values that were below the universal treatment standard limit of 25 µg L(-1) and compressive strengths that exceeded the criterion of 3.45 MPa.

Stabilization/solidification of mercury-contaminated waste ash using calcium sodium phosphate (CNP) and magnesium potassium phosphate (MKP) processes.

This study examined the stabilization and solidification (S/S) of mercury (Hg)-contaminated waste ash generated from an industrial waste incinerator using chemically bonded phosphate ceramic (CBPC) technology. A magnesium potassium phosphate (MKP; MgKPO4 · 6H2O) ceramic, fabricated from MgO and KH2PO4, and a calcium sodium phosphate (CNP; CaNaPO4) ceramic, fabricated from CaO and Na2HPO4, were used as solidification binders in the CBPC process, and Na2S or FeS was added to each solidification binder to stabilize the Hg-contaminated waste ash. The S/S processes were conducted under various operating conditions (based on the solidification binder and stabilization reagent, stabilization reagent dosage, and waste loading ratio), and the performance characteristics of the S/S sample under each operating condition were compared, including the Hg leaching value and compressive strength. The Hg leaching value of untreated Hg-contaminated waste ash was 231.3 µg/L, whereas the S/S samples treated using the MKP and CNP processes exhibited Hg leaching values below the universal treatment standard (UTS) limit (25 µg/L). Although the compressive strengths of the S/S samples decreased as the sulfide dosage and waste loading ratio were increased, most of the S/S samples fabricated by the MKP and CNP processes exhibited good mechanical properties.

Preparation of quality control materials for the determination of mercury in rice.

This study was performed to determine the feasibility of using Hg-spiked rice as a quality control material for Hg content analyses. Rice was coated with halogen compounds prior to the addition of Hg to increase the homogeneity and stability, both of which are important factors in the development of reference materials (RMs), relative to currently available RMs. The coating materials CCl4, CH2CHCH2Br, and CH3I were used to generate Hg-spiked rice RMs at the desired Hg concentrations. The coating materials were tested to determine the extent to which they were able to affect the adsorption of Hg onto the rice. The in-lab prepared Hg-spiked rice RMs using proposed RM production method exhibited good homogeneity (within- and between-bottle) and stability (short- and long-term) with respect to the evaluated coating materials, storage temperature (20°C or 40°C), and storage periods (from 0 days up to 24 months).

Simple and accessible analytical methods for the determination of mercury in soil and coal samples.

Simple and accessible analytical methods compared to conventional methods such as US EPA Method 7471B and ASTM-D6414 for the determination of mercury (Hg) in soil and coal samples are proposed. The new methods are consisted of fewer steps without the Hg oxidizing step consequently eliminating a step necessary to reduce excess oxidant. In the proposed methods, a Hg extraction is an inexpensive and accessible step utilizing a disposable test tube and a heating block instead of an expensive autoclave vessel and a specially-designed microwave. Also, a common laboratory vacuum filtration was used for the extracts instead of centrifugation. As for the optimal conditions, first, best acids for extracting Hg from soil and coal samples was investigated using certified reference materials (CRMs). Among common laboratory acids (HCl, HNO3, H2SO4, and aqua regia), aqua regia was most effective for the soil CRM whereas HNO3 was for the coal CRM. Next, the optimal heating temperature and time for Hg extraction were evaluated. The most effective Hg extraction was obtained at 120°C for 30min for soil CRM and at 70°C for 90min for coal CRM. Further tests using selected CRMs showed that all the measured values were within the allowable certification range. Finally, actual soil and coal samples were analyzed using the new methods and the US EPA Method 7473. The relative standard deviation values of 1.71-6.55% for soil and 0.97-12.11% for coal samples were obtained proving that the proposed methods were not only simple and accessible but also accurate.

Mercury leaching characteristics of waste treatment residues generated from various sources in Korea.

In this study, mercury (Hg) leaching characteristics of the waste treatment residues (fly ash, bottom ash, sludge, and phosphor powder) generated from various sources (municipal, industrial, medical waste incinerators, sewage sludge incinerator, oil refinery, coal-fired power plant, steel manufacturing plant, fluorescent lamp recycler, and cement kiln) in Korea were investigated. First, both Hg content analysis and toxicity characteristic leaching procedure (TCLP) testing was conducted for 31 collected residue samples. The Hg content analysis showed that fly ash from waste incinerators contained more Hg than the other residue samples. However, the TCLP values of fly ash samples with similar Hg content varied widely based on the residue type. Fly ash samples with low and high Hg leaching ratios (RL) were further analyzed to identify the major factors that influence the Hg leaching potential. Buffering capacity of the low-RL fly ash was higher than that of the high-RL fly ash. The Hg speciation results suggest that the low-RL fly ashes consisted primarily of low-solubility Hg compounds (Hg2Cl2, Hg(0) or HgS), whereas the high-RL fly ashes contain more than 20% high-solubility Hg compounds (HgCl2 or HgSO4).