Extraction of arsenate and arsenite species from soils and sediments

The primary objective of this study was to develop a simple method that can be used to extract the more readily mobilizable and bioavailable arsenic species from soil and sediment while at the same time minimizing the transformation between (AsIII) and (AsV), the two most commonly found arsenic species in the environment. Several extraction strategies were evaluated using phosphate as extractant in combination with either ethylenediaminetetraacetic acid (EDTA), hydroxylamine hydrochloride (NH2OH.HCl), or sodium diethyldithiocarbamate trihydrate (NaDDC). The addition of EDTA in the phosphate solution did not prevent AsIII from oxidation. While promising results were shown when 1% NH2OH.HCl was added, conversion of AsIII began to occur with extended extraction time (> 12 h). Good results were achieved using 10 mM phosphate and 0.5% NaDDC where AsIII oxidation was clearly minimized. The combined phosphate and NaDDC solution was applied to several soil and sediment samples. AsIII spiked was quantitatively recovered in all soil types tested.     

Efficacy of indigenous soil microbes in arsenic mitigation from contaminated alluvial soil of India

Selected arsenic-volatilizing indigenous soil bacteria were isolated and their ability to form volatile arsenicals from toxic inorganic arsenic was assessed. Approximately 37 % of AsIII (under aerobic conditions) and 30 % AsV (under anaerobic conditions) were volatilized by new bacterial isolates in 3 days. In contrast to genetically modified organism, indigenous soil bacteria was capable of removing 16 % of arsenic from contaminated soil during 60 days incubation period while applied with a low-cost organic nutrient supplement (farm yard manure).     

Uptake and translocation of arsenite by Pteris vittata L.: effects of glycerol, antimonite and silver

AsIII uptake in living cells is through aquaglyceroporin transporters, but it is unknown in arsenic-hyperaccumulator Pteris vittata. We investigated the effects of AsIII analogs glycerol and antimonite (SbIII) at 0-100 mM and aquaporin inhibitor AgNO₃ at 0-0.1 mM on the uptake of 0.1 mM AsIII or AsV by P. vittata over 1-2 h. Glycerol or SbIII didn’t impact AsIII or AsV uptake by P. vittata (p < 0.05), with As concentrations in the fronds and roots being 4.4-6.3 and 3.9-6.2 mg/kg. However, 0.01 mM AgNO₃ reduced As concentrations in the fronds and roots by 64% and 58%. Hence, AsIII uptake in P. vittata might be via an aquaporin transporter different from glycerol and SbIII transporters. Further as AsIII analogs and aquaporin inhibitor had no impact on AsV uptake, AsIII and AsV were likely taken up by different transporters in P. vittata. Our results imply a different AsIII transporter in P. vittata from other plants.     

Interaction of As and Sb in the hyperaccumulator <Emphasis Type="Italic">Pteris vittata</Emphasis> L.: changes in As and Sb speciation by XANES

Arsenic (As) and antimony (Sb) are chemical analogs that display similar characteristics in the environment. The As hyperaccumulator Pteris vittata L. is a potential As–Sb co-accumulating species. However, when this plant is exposed to different As and Sb speciation, the associated accumulating mechanisms and subsequent assimilation processes of As and Sb remain unclear. A 2-week hydroponic experiment was conducted by exposing P. vittata to single AsIII, AsV, SbIII, and SbV or the co-existence of AsIII and SbIII and AsV and SbV. P. vittata could co-accumulate As and Sb in the pinna (>1000 mg kg^?1) with high translocation (>1) of As and Sb from the root to the pinna. P. vittata displayed apparent preference to the trivalent speciation of As and Sb than to the pentavalent speciation. Under the single exposure of AsIII or SbIII, the pinna concentration of As and Sb was 84 and 765 % higher than that under the single exposure of AsV or SbV, respectively. Despite the provided As speciation, the main speciation of As in the root was AsV, whereas the main speciation of As in the pinna was AsIII. The Sb in the roots comprised SbV and SbIII when exposed to SbV but was exclusively SbIII when exposed to SbIII. The Sb in the pinna was a mixture of SbV and SbIII regardless of the provided Sb speciation. Compared with the single exposure of As, the co-existence of As and Sb increased the As concentration in the pinna of P. vittata by 50–66 %, accompanied by a significant increase in the AsIII percentage in the root. Compared with the single exposure of Sb, the co-existence of Sb and As also increased the Sb concentration in the pinna by 51–100 %, but no significant change in Sb speciation was found in P. vittata.     

Arsenic speciation, and arsenic and phosphate distribution in arsenic hyperaccumulator Pteris vittata L. and non-hyperaccumulator Pteris ensiformis L

This study examined the roles of arsenic translocation and reduction, and P distribution in arsenic detoxification of Pteris vittata L. (Chinese Brake fern), an arsenic hyperaccumulator and Pteris ensiformis L. (Slender Brake fern), a non-arsenic hyperaccumulator. After growing in 20% Hoagland solution containing 0, 133 or 267 microM of sodium arsenate for 1, 5 or 10 d, the plants were separated into fronds, rhizomes, and roots. They were analyzed for biomass, and concentrations of arsenate (AsV), arsenite (AsIII) and phosphorus. Arsenic in the fronds of P. vittata was up to 20 times greater than that of P. ensiformis, yet showing no toxicity symptoms as did in P. ensiformis. While arsenic was concentrated primarily in the fronds of P. vittata as arsenite it was mainly concentrated in the roots of P. ensiformis as arsenate. Arsenic reduction in the plants took longer than 1-d. P. vittata maintained greater P in the roots while P. ensiformis in the fronds. The high arsenic tolerance of the hyperaccumulator P. vittata may be attributed to its ability to effectively reduce arsenate to arsenite in the fronds, translocate arsenic from the roots to fronds, and maintain a greater ratio of P/As in the roots.     

Enhanced mobilization of arsenic and heavy metals from mine tailings by humic acid

Arsenic and heavy metal mobilization from mine tailings is an issue of concern as it might pose potential groundwater or ecological risks. Increasing attention recently has been focused on the effects of natural organic matter on the mobility behavior of the toxicants in the environment. Column experiments were carried out in this research study to evaluate the feasibility of using humic acid (HA) to mobilize arsenic and heavy metals (i.e., Cu, Pb and Zn) from an oxidized Pb-Zn mine tailings sample collected from Bathurst, New Brunswick, Canada. Capillary electrophoresis analyses indicated that arsenate [As(V)] was the only extractable arsenic species in the mine tailings and the addition of HA at pH 11 did not incur the oxidation-reduction or methylation reactions of arsenic. A 0.1% HA solution with an initial pH adjusted to 11 was selected as the flushing solution, while distilled water (initial pH adjusted to 11) was used as the control to account for the mobilization of arsenic and the heavy metals by physical mixing and the effect of pH. It was found that the HA could significantly enhance the mobilization of arsenic and heavy metals simultaneously from the mine tailings. After a 70-pore-volume-flushing, the mobilization of arsenic, copper, lead and zinc reached 97, 35, 838 and 224 mg kg(-1), respectively. The mobilization of arsenic and the heavy metals was found to be positively correlated with the mobilization of Fe in the presence of the HA. Moreover, the mobilization of arsenic was also correlated well with that of the heavy metals. The mobilization of co-existing metals to some extent might enhance arsenic mobilization in the presence of the HA by helping incorporate it into soluble aqueous organic complexes through metal-bridging mechanisms. Use of HA in arsenic and heavy metal remediation may be developed as an environmentally benign and possible effective remedial option to reduce and avoid further contamination.     

A review of toxicity and mechanisms of individual and mixtures of heavy metals in the environment

The rational for the study was to review the literature on the toxicity and corresponding mechanisms associated with lead (Pb), mercury (Hg), cadmium (Cd), and arsenic (As), individually and as mixtures, in the environment. Heavy metals are ubiquitous and generally persist in the environment, enabling them to biomagnify in the food chain. Living systems most often interact with a cocktail of heavy metals in the environment. Heavy metal exposure to biological systems may lead to oxidation stress which may induce DNA damage, protein modification, lipid peroxidation, and others. In this review, the major mechanism associated with toxicities of individual metals was the generation of reactive oxygen species (ROS). Additionally, toxicities were expressed through depletion of glutathione and bonding to sulfhydryl groups of proteins. Interestingly, a metal like Pb becomes toxic to organisms through the depletion of antioxidants while Cd indirectly generates ROS by its ability to replace iron and copper. ROS generated through exposure to arsenic were associated with many modes of action, and heavy metal mixtures were found to have varied effects on organisms. Many models based on concentration addition (CA) and independent action (IA) have been introduced to help predict toxicities and mechanisms associated with metal mixtures. An integrated model which combines CA and IA was further proposed for evaluating toxicities of non-interactive mixtures. In cases where there are molecular interactions, the toxicogenomic approach was used to predict toxicities. The high-throughput toxicogenomics combines studies in genetics, genome-scale expression, cell and tissue expression, metabolite profiling, and bioinformatics.     

Arsenic concentration in topsoil of central Chile is associated with aberrant methylation of P53 gene in human blood cells: a cross-sectional study

Gene expression can be modified in people who are chronically exposed to high concentrations of heavy metals. The soil surrounding the Ventanas Industrial Complex, located on the coastal zone of Puchuncaví and Quintero townships (Chile), contain heavy metal concentrations (As, Cu, Pb, Zn, among others) that far exceed international standards. The aim of this study was to determine the potential association of the heavy metals in soils, especially arsenic, with the status of methylation of four tumor suppressor genes in permanent residents in those townships. To study the methylation status in genes p53, p16, APC, and RASSF1A, we took blood samples from adults living in areas near the industrial complex for at least 5 years and compared it to blood samples from adults living in areas with normal heavy metal concentrations of soils. Results indicated that inhabitants of an area with high levels of heavy metals in soil have a significantly higher proportion of methylation in the promoter region of the p53 tumor suppressor gene compared with control areas (p-value: 0.0035). This is the first study to consider associations between heavy metal exposure in humans and aberrant DNA methylation in Chile. Our results suggest more research to support consistent decision-making on processes of environmental remediation or prevention of exposure.

     

Effects of heavy metals on growth and arsenic accumulation in the arsenic hyperaccumulator Pteris vittata L

The effects of Cd, Ni, Pb, and Zn on arsenic accumulation by the arsenic hyperaccumulator Pteris vittata were investigated in a greenhouse study. P. vittata was grown for 8 weeks in an arsenic-contaminated soil (131 mg As kg(-1)), which was spiked with 50 or 200 mg kg(-1) Cd, Ni, Pb, or Zn (as nitrates). P. vittata was effective in taking up arsenic (up to 4100 mg kg(-1)) and transporting it to the fronds, but little of the metals. Arsenic bioconcentration factors ranged from 14 to 36 and transfer factors ranged from 16 to 56 in the presence of the metals, both of which were reduced with increasing metal concentration. Fern biomass increased as much as 12 times compared to the original dry weight after 8 weeks of growth (up to 19 g per plant). Greater concentrations of Cd, Ni, and Pb resulted in greater catalase activity in the plant. Most of the arsenic in the plant was present as arsenite, the reduced form, indicating little impact of the metals on plant arsenic reduction. This research demonstrates the capability of P. vittata in hyperaccumulating arsenic from soils in the presence of heavy metals.     

Bioremediation of cadmium contaminated soil using symbiosis between leguminous plant and recombinant rhizobia with the MTL4 and the PCS genes

Cadmium contamination in rice grains is one of the important issues in Asian countries. We have developed a novel bio-remediation system based on the symbiosis between leguminous plant and genetically engineered rhizobia. We designed two types of recombinant rhizobia, carrying two genes, synthetic tetrameric metallothionein (MTL4) and cDNA encoding phytochelatin synthase from Arabidopsis thaliana (AtPCS). The MTL4 and AtPCS genes were transferred to Mesorhizobium huakuii subsp. rengei B3, which can infect and form nodules on Chinese milk vetch, Astragalus sinicus. The two genes were fused to the nolB or nifH promoter, which generated nodule specific expression of these genes in strain B3. The two recombinant strains, B3(pMPnolBMTL4nifHPCS) and B3::nifHMTL4(pMPnifHPCS), showed 25 and 12-fold increase in Cd concentration, in the free-living cells, respectively. When these recombinant strains established the symbiotic relationship with A. sinicus, the symbionts increased Cd accumulation in nodules by two-fold in hydroponic culture. The expression of the both MTL4 and AtPCS genes showed additive effect on cadmium accumulation in nodules. We also applied these recombinant bacteria to rice paddy soil polluted with Cd (1mgkg(-1) dry weight soil). The accumulation of Cd increased not only in nodules but also in the roots of A. sinicus infected by the recombinant rhizobia. The accumulation of Cd in the plant roots infected by B3(pMPnolBMTL4nifHPCS) achieved three-fold than that by the wild-type B3. After two months of cultivation of the symbiont, a maximum of 9% of Cd in paddy soil was removed. Thus, the symbiosis will be useful in phytoremediation for heavy metals.     

Arsenic tolerances in rice (Oryza sativa) have a predominant role in transcriptional regulation of a set of genes including sulphur assimilation pathway and antioxidant system

World wide arsenic (As) contamination of rice has raised much concern as it is the staple crop for millions. Four most commonly cultivated rice cultivars, Triguna, IR-36, PNR-519 and IET-4786, of the West Bengal region were taken for a hydroponic study to examine the effect of arsenate (As^V) and arsenite (As^III) on growth response, expression of genes and antioxidants vis-à-vis As accumulation. The rice genotypes responded differentially under As^V and As^III stress in terms of gene expression and antioxidant defences. Some of the transporters were up-regulated in all rice cultivars at lower doses of As species, except IET-4786. Phytochelatin synthase, GST and γ-ECS showed considerable variation in their expression pattern in all genotypes, however in IET-4786 they were generally down-regulated in higher As^III stress. Similarly, most of antioxidants such as superoxide dismutase (SOD), ascorbate peroxidase (APX), guaiacol peroxidase (GPX), catalase (CAT), monodehydroascorbate reductase (MDHAR) and dehydroascorbate reductase (DHAR) increased significantly in Triguna, IR-36 and PNR-519 and decreased in IET-4786. Our study suggests that Triguna, IR-36 and PNR-519 are tolerant rice cultivars accumulating higher arsenic; however IET-4786 is susceptible to As-stress and accumulates less arsenic than other cultivars.     

Occurrence of arsenic in brown rice and its relationship to soil properties from Hainan Island, China

The acquaintance of arsenic concentrations in rice grain is vital in risk assessment. In this study, we determined the concentration of arsenic in 282 brown rice grains sampled from Hainan Island, China, and discussed its possible relationships to the considered soil properties. Arsenic concentrations in the rice grain from Hainan Island varied from 5 to 309 μg/kg, with a mean (92 μg/kg) lower than most published data from other countries/regions and the maximum contaminant level (MCL) for As_i in rice. The result of correlation analysis between grain and soil properties showed that grain As concentrations correlated significantly to soil arsenic speciation, organic matter and soil P contents and could be best predicted by humic acid bound and Fe-Mn oxides bound As fractions. Grain arsenic rises steeply at soil As concentrations lower than 3.6 mg/kg and gently at higher concentrations.     

Effects of alkaline and bioorganic amendments on cadmium,lead, zinc,and nutrient accumulation in brown rice and grain yield in acidic paddy fields contaminated with a mixture of heavy metals

Paddy soils and rice (Oryza sativa L.) contaminated by mixed heavy metals have given rise to great concern. Field experiments were conducted over two cultivation seasons to study the effects of steel slag (SS), fly ash (FA), limestone (LS), bioorganic fertilizer (BF), and the combination of SS and BF (SSBF) on rice grain yield, Cd, Pb, and Zn and nutrient accumulation in brown rice, bioavailability of Cd, Pb, and Zn in soil as well as soil properties (pH and catalase), at two acidic paddy fields contaminated with mixed heavy metals (Cd, Pb, and Zn). Compared to the controls, SS, LS, and SSBF at both low and high additions significantly elevated soil pH over both cultivation seasons. The high treatments of SS and SSBF markedly increased grain yields, the accumulation of P and Ca in brown rice and soil catalase activities in the first cultivation season. The most striking result was from SS application (4.0 t ha^?1) that consistently and significantly reduced the soil bioavailability of Cd, Pb, and Zn by 38.5–91.2 % and the concentrations of Cd and Pb in brown rice by 20.9–50.9 % in the two soils over both cultivation seasons. LS addition (4.0 t ha^?1) also markedly reduced the bioavailable Cd, Pb, and Zn in soil and the Cd concentrations in brown rice. BF remobilized soil Cd and Pb leading to more accumulation of these metals in brown rice. The results showed that steel slag was most effective in the remediation of acidic paddy soils contaminated with mixed heavy metals.     

Heavy-metal pollution and arseniasis in Hetao region, China

In the Hetao region in northern China drinking water has become toxic due to the presence of arsenic (As) and other heavy metals in soil and water. The 7 counties in this region cover approx. 6100 km2, and in all 180,000 people are suffering from the toxic effects of contaminated drinking water. However, very few studies have been carried out in the region on the possible source of this arsenic. This paper is based on studies of the distribution of heavy metals in soil and groundwater. Results show that the average content of As is 0.483 microg g(-1) in groundwater and 13.74 microg g(-1) in soil. These levels are higher than the drinking water standard of 0.05 microg g(-1) recommended by the World Health Organization in 1984, and for the local background level in soil (5.20 microg g(-1)). This heavy-metal content in water and soil decreases gradually with increasing distance from the contaminated area, which fronts the Yin Mountains. The ratios of the Pb and Sr isotope contents in water are closely related to the ratios found in the water of the regions' mining area, and the ratios in soil correspond to the content of As in groundwater and soil in the area where pathological changes have been detected. Results suggest that the contaminants originate in the ore deposit zone fronting Yin mountains in the upper reaches of the Hetao Region.     

A remediation strategy based on active phytoremediation followed by natural attenuation in a soil contaminated by pyrite waste

Phytoremediation of metal-polluted soils can be promoted by the proper use of soil amendments and agricultural practices. A 4-year phytoremediation programme was applied to a site affected by the toxic spill of pyrite residue at Aznalcóllar (Spain) in 1998, contaminated with heavy metals (Zn, Cu, Pb, Cd) and arsenic. This consisted of active phytoremediation, using organic amendments (cow manure and compost) and lime and growing two successive crops of Brassica juncea (L.) Czern., followed by natural attenuation without further intervention. Changes in soil pH, extractable metal and As concentrations, organic carbon content and microbial biomass was evaluated. The initial oxidation of metal sulphides from pyrite residues released soluble metals and reduced soil pH to extremely acidic values (mean 4.1, range 2.0-7.0). The addition of lime (up to 64 t ha(-1)) increased soil pH to adequate values for plant growth, resulting in a significant decrease in DTPA-extractable metal concentrations in all plots. The natural attenuation phase showed also a decrease in extractable metals. Organic treatments increased the soil total organic carbon, which led to higher values of microbial biomass (11.6, 15.2 and 14.9 g kg(-1) TOC and 123, 170 and 275 microg g(-1) biomass-C in control, compost and manure plots, respectively). Active phytoremediation followed by natural attenuation, was effective for remediation of this pyrite-polluted soil.     

Periphyton as monitors for heavy metal pollution in the Calcasieu River estuary

The levels of copper, lead, chromium, zinc, cadmium, arsenic and silver were determined in periphyton specimens obtained with a diatometer collector. Stations selected were along three important bayous of the Calcasieu River system. Distributions of some metals in the organisms were similar to those found in sediment from the same locations, while other metals appeared to be similar to water concentrations. Concentration ratios of periphyton over sediment greatly exceeded one for the metals chromium, zinc, cadmium, arsenic and silver. The concentrations of heavy metals in the periphyton appeared to yield more information about pollutants than either water or sediment samples collected at the periphyton stations.     

The fate and transport of arsenic species in the aquatic ecosystem: a case study on Bestari Jaya,Peninsular Malaysia

The field of arsenic pollution research has grown rapidly in recent years. Arsenic constitutes a broad range of elements from the Earth’s crust and is released into the environment from both anthropogenic and natural sources due to its relative mobility under different redox conditions. The toxicity of arsenic is described in its inorganic form, as inorganic arsenic compounds can leach into different environments. Sampling was carried out in the Bestari Jaya catchment while using a land use map to locate the site, and experiments were conducted via sequential extraction and inductively coupled plasma optical emission spectroscopy to quantify proportions of arsenic in the sediment samples. The results show that metals in sediments of nonresidual fractions, which are more likely to be likely released into aquatic environments, are more plentiful than the residual sediment fractions. These findings support the mobility of heavy metals and especially arsenic through sediment layers, which can facilitate remediation in environments heavily polluted with heavy metals.     

Effect of arsenic on photosynthesis, growth and yield of five widely cultivated rice (Oryza sativa L.) varieties in Bangladesh

A glass house experiment was conducted to investigate the effect of soil arsenic on photosynthetic pigments, chlorophyll-a and -b, and their correlations with rice yield and growth. The experiment was designed with three replications of six arsenic treatments viz. control, 10, 20, 30, 60, 90 mg of As kg(-1) soil. Arsenic concentration in initial soil, to which the above mentioned concentrations of arsenic were added, was 6.44+/-0.24 mg kg(-1). Both chlorophyll-a and -b contents in rice leaf decreased significantly (p<0.05) with the increase of soil arsenic concentrations. No rice plant survived up to maturity stage in soil treated with 60 and 90 mg of As kg(-1). The highest chlorophyll-a and -b contents were observed in control treatment (2.62+/-0.24 and 2.07+/-0.14 mg g(-1) were the average values of chlorophyll-a and -b, respectively of the five rice varieties) while 1.50+/-0.20 and 1.04+/-0.08 mg g(-1) (average of five rice varieties) of chlorophyll-a and -b, respectively were the lowest. The content of photosynthetic pigments in these five rice varieties did not differ significantly (p>0.05) from each other in control treatment though they differed significantly (p<0.05) from each other in 30 mg of As kg(-1) soil treatment. Among the five rice varieties, chlorophyll content in BRRI dhan 35 was found to be mostly affected with the increase of soil arsenic concentration while BRRI hybrid dhan 1 was least affected. Well correlations were observed between chlorophyll content and rice growth and yield suggesting that arsenic toxicity affects the photosynthesis which ultimately results in the reduction of rice growth and yield.