A comparative study on arsenic and humic substances in alluvial aquifers of Bengal delta plain (NW Bangladesh), Chianan plain (SW Taiwan) and Lanyang plain (NE Taiwan): implication of arsenic mobilization mechanisms

Humic substances in groundwater and aquifer sediments from the arsenicosis and Blackfoot disease (BFD) affected areas in Bangladesh (Bengal delta plain) and Taiwan (Lanyang plain and Chianan plain) were characterized using fluorescence spectrophotometry and Fourier transform infrared (FT-IR) spectroscopy. The results demonstrate that the mean concentration of As and relative intensity of fluorescent humic substances are higher in the Chianan plain groundwater than those in the Lanyang plain and Bengal delta plain groundwater. The mean As concentrations in Bengal delta plain, Chianan plain, and Lanyang plain are 50.65 μg/l (2.8–170.8 μg/l, n = 20), 393 μg/l (9–704 μg/l, n = 5), and 104.5 μg/l (2.51–543 μg/l, n = 6), respectively. Average concentrations and relative fluorescent intensity of humic substances in groundwater are 25.381 QSU (quinine standard unit) and 17.78 in the Bengal delta plain, 184.032 QSU and 128.41 in the Chianan plain, and 77.56 QSU and 53.43 in the Lanyang plain. Moreover, FT-IR analysis shows that the humic substances extracted from the Chianan plain groundwater contain phenolic, alkanes, aromatic ring and amine groups, which tend to form metal carbon bonds with As and other trace elements. By contrast, the spectra show that humic substances are largely absent from sediments and groundwater in the Bengal delta plain and Lanyang plain. The data suggest that the reductive dissolution of As-adsorbed Mn oxyhydroxides is the most probable mechanism for mobilization of As in the Bengal delta plain. However, in the Chianan plain and Lanyang plain, microbially mediated reductive dissolution of As-adsorbed amorphous/crystalline Fe oxyhydroxides in organic-rich sediments is the primary mechanism for releasing As to groundwater. High levels of As and humic substances possibly play a critical role in causing the unique BFD in the Chianan plain of SW Taiwan.     

Geochemical and microbial effects on the mobilization of arsenic in mine tailing soils

Arsenic (As) contamination has become a serious environmental problem in many countries. We have performed batch-type leaching experiments on mine tailing soils collected from three abandoned mine areas in South Korea with the objective of evaluating the effect of indigenous bacterial activity on As mobilization. The analysis of physicochemical properties and mineralogical compositions of the samples indicated that the secondary minerals or phases formed as a result of the oxidation or alteration of primary minerals were associated with the labile and bioleachable fractions of As. Compared to simulated abiotic processes using sterilization, the indigenous bacteria activated using a carbon source were able to enhance the dissolution of As under both aerobic and anaerobic conditions. The bacterial dissolution of iron (Fe) and manganese (Mn) was found to occur simultaneously with the dissolution of As, suggesting that the main bacterial mechanism was via the dissimilatory reduction of Fe(III), Mn(IV), and As(V). An anaerobic environment was more favorable for the prominent dissolution of As in the tailing soils. These results indicate that the mobilization of As can be enhanced in the oxygen-depleted part of the tailing dump, particularly with the infiltration of organic substrates. The difference in the degree of As lixiviation between the three tailing soils was found to be related to the bioavailability of As as well as the original biomass in the tailing soils.     

中国饮水型砷中毒区的水化学环境与砷中毒关系

中国各饮水型砷中毒区的水化学特点受沉积环境和气候因素所控制,砷中毒的流行和发病程度与其地下水的水化学环境、水中砷的形态和价态有密切联系。在实地考察监测和对台湾、新疆、内蒙古、山西、吉林饮水型砷中毒病区环境和地下水水化学特征总结的基础上,系统分析了饮水水源中总As、As(III)、甲基胂、腐植酸与砷中毒的关系,揭示了不同病区病情差异的原因。研究表明,除台湾外,各砷中毒区均分布在干旱半干旱区;各病区多分布在沉积盆地中心或平原内相对低洼的地带,饮用的地下水均取自中新生代地层;砷中毒病情不仅与总砷含量有明显的剂量-效应关系,还与As(III)和甲基胂的浓度直接相关。台湾、内蒙古和山西病区地下水为富含有机质的复杂还原环境,水中不仅As(III)含量高,且检出有机物、腐植酸和甲基胂,新疆和吉林病区地下水为以无机砷中As(V)为主的氧化环境,吉林病区未检测出甲基胂,这是新疆与吉林病区患病率较低的主要原因。研究成果可为区域防病改水、砷中毒的预报提供重要技术支撑。     

Use of metal-reducing bacteria for bioremediation of soil contaminated with mixed organic and inorganic pollutants

Mixed contamination by organic and inorganic compounds in soil is a serious problem for remediation. Most laboratory studies and field-scale trials focused on individual contaminant in the past. For concurrent bioremediation by biodegradation and bioleaching processes, we tested metal-reducing microorganism, Geobacter metallireducens. In order to prove the feasibility of the coupled process, multiple-contaminated soil was prepared. Mineralogical analyses have shown the existence of labile forms of As(V) as amorphous and/or weakly sorbed phases in the secondary Fe oxides. In the biotic experiment using G. metallireducens, biodegradation of toluene and bioleaching of As by bacteria were observed simultaneously. Bacteria accelerated the degradation rate of toluene with reductive dissolution of Fe and co-dissolution of As. Although there have been many studies showing each individual process, we have shown here that the idea of concurrent microbial reaction is feasible. However, for the practical use as a remediation technology, more details and multilateral evaluations are required in future studies.     

Use of metal-reducing bacteria for bioremediation of soil contaminated with mixed organic and inorganic pollutants

Mixed contamination by organic and inorganic compounds in soil is a serious problem for remediation. Most laboratory studies and field-scale trials focused on individual contaminant in the past. For concurrent bioremediation by biodegradation and bioleaching processes, we tested metal-reducing microorganism, Geobacter metallireducens. In order to prove the feasibility of the coupled process, multiple-contaminated soil was prepared. Mineralogical analyses have shown the existence of labile forms of As(V) as amorphous and/or weakly sorbed phases in the secondary Fe oxides. In the biotic experiment using G. metallireducens, biodegradation of toluene and bioleaching of As by bacteria were observed simultaneously. Bacteria accelerated the degradation rate of toluene with reductive dissolution of Fe and co-dissolution of As. Although there have been many studies showing each individual process, we have shown here that the idea of concurrent microbial reaction is feasible. However, for the practical use as a remediation technology, more details and multilateral evaluations are required in future studies.

     

Use of metal-reducing bacteria for bioremediation of soil contaminated with mixed organic and inorganic pollutants

Mixed contamination by organic and inorganic compounds in soil is a serious problem for remediation. Most laboratory studies and field-scale trials focused on individual contaminant in the past. For concurrent bioremediation by biodegradation and bioleaching processes, we tested metal-reducing microorganism, Geobacter metallireducens. In order to prove the feasibility of the coupled process, multiple-contaminated soil was prepared. Mineralogical analyses have shown the existence of labile forms of As(V) as amorphous and/or weakly sorbed phases in the secondary Fe oxides. In the biotic experiment using G. metallireducens, biodegradation of toluene and bioleaching of As by bacteria were observed simultaneously. Bacteria accelerated the degradation rate of toluene with reductive dissolution of Fe and co-dissolution of As. Although there have been many studies showing each individual process, we have shown here that the idea of concurrent microbial reaction is feasible. However, for the practical use as a remediation technology, more details and multilateral evaluations are required in future studies.     

Advances in Fe(III) bioreduction and its application prospect for groundwater remediation: A review

Microbial Fe(III) reduction is closely related to the fate of pollutants. Bioavailability of crystalline Fe(III) oxide is restricted due to thermodynamics. Amorphous Fe(III) (hydro)oxides are more bioavailable. Enrichment and incubation of Fe(III) reducing bacteria are significant. Microbial Fe(III) reduction is a significant driving force for the biogeochemical cycles of C, O, P, S, N, and dominates the natural bio-purification of contaminants in groundwater (e.g., petroleum hydrocarbons, chlorinated ethane, and chromium). In this review, the mechanisms and environmental significance of Fe(III) (hydro)oxides bioreduction are summarized. Compared with crystalline Fe(III) (hydro)oxides, amorphous Fe(III) (hydro)oxides are more bioavailable. Ligand and electron shuttle both play an important role in microbial Fe(III) reduction. The restrictive factors of Fe(III) (hydro)oxides bioreduction should be further investigated to reveal the characteristics and mechanisms of the process. It will improve the bioavailability of crystalline Fe(III) (hydro)oxides and accelerate the anaerobic oxidation efficiency of the reduction state pollutants. Furthermore, the approach to extract, culture, and incubate the functional Fe(III) reducing bacteria from actual complicated environment, and applying it to the bioremediation of organic, ammonia, and heavy metals contaminated groundwater will become a research topic in the future. There are a broad application prospects of Fe(III) (hydro)oxides bioreduction to groundwater bioremediation, which includes the in situ injection and permeable reactive barriers and the innovative Kariz wells system. The study provides an important reference for the treatment of reduced pollutants in contaminated groundwater.     

Abiotic subsurface behaviors of As(V) with Fe(II)

Subsurface geochemical behavior of As(V) with Fe(II) was studied under strict anoxic conditions. Abiotic reduction of As(V) (0.1 mM) to As(III) by aqueous Fe(II) and sorbed Fe(II) in pH range 5.0-7.0 and Fe(II)(aq) concentration (0.6-1.2 mM) was investigated along with the effect of As(V) on the oxidation of Fe(II) by dissolved oxygen (DO). Although the reduction was thermodynamically feasible for homogeneous chemical conditions, practically no As(V) reduction by aqueous Fe(II) was observed. Similarly, no sorbed As(V) reduction was observed under the heterogeneous experimental conditions by sorbed Fe(II) onto synthetic iron oxide (hematite, α-Fe?O?). Experimental results on Fe(II) oxidation by DO in the presence of 0.1 mM As(V) showed a significantly slower Fe(II) oxidation, which might be due to the formation of Fe(II)-As(V) complex in the aqueous phase. The results of this study demonstrate that As(V) is relatively stable in the presence of Fe(II) under subsurface environment and interfere the oxidation of Fe(II).     

Sources,spatial variation,and speciation of heavy metals in sediments of the Tamagawa River in Central Japan

Subsurface geochemical behavior of As(V) with Fe(II) was studied under strict anoxic conditions. Abiotic reduction of As(V) (0.1 mM) to As(III) by aqueous Fe(II) and sorbed Fe(II) in pH range 5.0–7.0 and Fe(II)_aq concentration (0.6–1.2 mM) was investigated along with the effect of As(V) on the oxidation of Fe(II) by dissolved oxygen (DO). Although the reduction was thermodynamically feasible for homogeneous chemical conditions, practically no As(V) reduction by aqueous Fe(II) was observed. Similarly, no sorbed As(V) reduction was observed under the heterogeneous experimental conditions by sorbed Fe(II) onto synthetic iron oxide (hematite, α-Fe₂O₃). Experimental results on Fe(II) oxidation by DO in the presence of 0.1 mM As(V) showed a significantly slower Fe(II) oxidation, which might be due to the formation of Fe(II)–As(V) complex in the aqueous phase. The results of this study demonstrate that As(V) is relatively stable in the presence of Fe(II) under subsurface environment and interfere the oxidation of Fe(II).     

Removal of arsenic by Acidothiobacillus ferrooxidans bacteria in bench scale fixed-bed bioreactor system

In the present study arsenic contaminated simulated water and groundwater was treated by the combination of biological oxidation of tri-valent arsenite [As (III)] to penta-valent arsenate [As (V)] in presence of Acidothiobacillus ferrooxidans bacteria and its removal by adsorptive filtration in a bioreactor system. This method includes the immobilisation of A.ferrooxidans on Granulated Activated Carbon (GAC) capable of oxidising ferrous [Fe (II)] to ferric [Fe (III)]. The Fe (III) significantly converts the As (III) to As (V) and ultimately removed greater than 95% by the bed of GAC, limestone, and sand. The significant influence of Fe (II) concentration (0.1–1.5?gL^?1), flowrate (0.06–0.18?Lh^?1), and initial As (III) concentration (100–1000?µgL^?1) on the arsenic removal efficiency was investigated. The simulated water sample containing the different concentration of As (III) and other ions was used in the study. The removal of other co-existing ions present in contaminated water was also investigated in column study. The concentration of arsenic was found to be <10?µgL^?1 which is below Maximum Contaminant Level (MCL) as per WHO in treated water. The results confirmed that the present system including adsorptive-filtration was successfully used for the treatment of contaminated water containing As (III) ions.     

Effect of biogeochemical interactions on bioaccessibility of arsenic in soils of a former smelter site in Republic of Korea

The total concentration-based regulations for soil remediation do not consider the possible changes in bioaccessibility of remaining arsenic (As) in soils due to biogeochemical interactions after remediation. This study used As-contaminated soil and pore water samples that were collected from the rice paddy and forest/farmland located in the vicinity of a former smelter site in Republic of Korea to elucidate the changes in As bioaccessibility due to biogeochemical interactions. Bioaccessibility and chemical forms of As in soils were determined by using an in vitro method and sequential extraction, respectively, and soil microbial community was evaluated. Bioaccessibility of As in the rice paddy soil samples was higher than that in the forest/farmland soil samples. This could be attributed to relatively higher dependence of bioaccessible As in the rice paddy soils on the soil concentration of iron (Fe), aluminum, or manganese, which could lead to greater changes in bioaccessible As via reductive dissolution. The strong linear relationship (R ² = 0.90, p value ≤0.001) between the pore water As and Fe concentrations, and the greater portion of bacterial species related to reductive dissolution of Fe oxides in the rice paddies can support the higher As bioaccessibility promoted by reductive dissolution. Therefore, it is necessary to consider the potential changes in the bioaccessible As due to biogeochemical interactions in remediation of As-contaminated soils, particularly when soils are likely to be reused under reductive dissolution-promoting conditions (e.g., flooded conditions).     

Arsenic and chromate removal from water by iron chips—Effects of anions

The purpose of this study is to estimate the removal efficiency of As and Cr (VI) by one kind of industrial waste — iron chips, as well as to estimate the effects of typical inorganic anions (sulfate, phosphate, and nitrate), and typical organic anions (citrate, oxalate, and humate) on As or Cr (VI) removal. The results showed that 98% of As (V) and 92% of As (III) could be removed from aqueous phase by the iron chips within 60 min. Compared with As species, Cr (VI) was removed much more rapidly and efficiently with 97% of Cr (VI) being removed within 25 min. The removal efficiency for arsenic was in the order: As (III) (sulfate), As (III) (nitrate) or As (III), As (III) (humate), As (III) (oxalate), As (III) (citrate), As (III) (phosphate), and for chromate was in the order: Cr (VI) (sulfate), Cr (VI) (phosphate) or Cr (VI) (nitrate) or Cr (VI) (oxalate), Cr (VI), Cr (VI) (citrate), Cr (VI) (humate). In all the treatments, pH level increased with time except for As (III), the removal of which was either without anions or in the presence of humate or nitrate.     

大同盆地富砷地下水的水化学与地球化学研究

为弄清大同盆地地下水中影响砷的迁移、富集的主要地球化学与生物地球化学过程,为区域供水安全提供指导作用,针对高砷地下水系统开展了水文地球化学与含水层沉积物全岩地球化学研究;并在此基础上探讨了研究区高砷地下水成因。结果表明,研究区高砷地下水为偏碱性、强还原环境,砷含量为0.31～452μg·L-1,主要以砷酸盐形式存在,地下水中砷与三价铁的浓度有显著的相关性。高砷含水层沉积物中有机质、铁与砷含量表现出显著相关性。以上结果说明,碱性还原环境有利于地下水中砷的富集;微生物参与下,沉积物相有机质的氧化和Fe氧化物/氢氧化物的还原过程是本区高砷地下水形成的主控因素。     

Iron oxidation-reduction and its impacts on cadmium bioavailability in paddy soils: a review

Redox conditions in paddy soils may vary as they are submerged and drained during rice growth. This change may bring about reductive dissolution of iron (Fe) oxides and subsequent formation of secondary Fe-bearing minerals in rice paddies. The mobility and bioavailability of metal contaminants such as cadmium (Cd) in paddy soils are closely related to the chemical behaviors of Fe. Therefore, in this paper, advances in the study of paddy Fe redox transformations and their effects on Cd availability to rice are briefly reviewed. Current concepts presented in this review include the forms of Fe in paddy soils, the reactions involved in Fe oxidation-reduction, chemical factors affecting Fe redox processes, Cd availability to rice and the impacts of Fe transformation on Cd uptake and translocation in rice. Prospects for future research in this area are also discussed.     

不同pH下低分子量有机酸对黄壤中铝活化的影响

用一次平衡的方法研究了不同pH下低分子量有机酸对黄壤中铝活化的影响.结果表明,低分子量有机酸体系可以通过质子和有机酸阴离子两个因素促进黄壤中铝的活化.当pH>4.3时,有机酸通过络合作用促进铝溶解的大小顺序为:柠檬酸>草酸>水杨酸>乳酸,与有机酸和铝形成络合物的稳定常数大小一致.有机酸阴离子可以通过自身的吸附增加土壤交换态铝的量,但质子作用对黄壤交换态铝的活化比有机酸阴离子的吸附起着更为重要的作用,随pH值的降低这种趋势更加明显.有机酸对交换态铝的活化作用随pH值的降低而增加.低分子量有机酸活化的铝主要分布在土壤表面的交换位上,但在柠檬酸和草酸体系中,当pH值分别大于4.40和4.55时,活化铝主要分布在土壤溶液中.     

Geophysical investigations for evaluation of environmental pollution in a mine tailings area

Sulfide-containing mill wastes of the Komsomolsk ore processing plant situated in the Kemerovo region (Russia) were examined in 2013–2015. Multipurpose studies of the mine tailings determined the composition of waste, pore water, mine drainages, and affected groundwater. Electrical resistivity tomography was used to trace the geoelectric zoning of the waste samples. Layers with low resistivity indicated areas with pore spaces filled with highly mineralized solutions with Fe, Cu, Zn, Cd, As, and Sb at total concentrations of up to 50 g/L. Anomalous zones can be specified as ‘geochemical barriers’ – specific layers where the mobility of the elements is reduced due to pH conditions, redox potential, and Fe(III) hydroxide precipitation. The zones of increased conductivity in oxidized mine tailings indicated local areas with high acid production potential and coexisting acidic pore solution. In non-oxidized tailings, high conductivity of the mineral skeleton was observed. There was a migration of drainage outside the tailings, its direction monitored by geophysical data. Chemical analysis confirmed that the concentrations of As in groundwater samples were higher than the maximum permissible concentration.     

Arsenic species in the well water and sediments of the blackfoot disease area in Taiwan

The blackfoot disease (BFD) observed in southwestern Taiwan is due to drinking high arsenic concentrations in well water. This paper presents some results concerning the distributions of arsenic species in water and sediments collected in the BFD (well, river and coastal) area and the background (lake and ocean) area for comparison. The results show that the concentrations of arsenate (870 ± 26 ug/L) and arsenite (70.2 ± 2.6 ug/ L) in well waters, and the contents of arsenic (1640 ug/g) with high percentage of easily reducible (Fe and Mn oxides, 91.7%) and exchangeable and carbonate (4.6%) phases in well sediments were much higher than those in river, lake and coastal samples. Low arsenic (3.46–31.8 ug/g) with high percentages (73.8–97.3%) of detritus and minerals phase with low percentages (0.4–9.8%) of total carbonate and exchangeable phases were found in the river and coastal samples in the BFD area as well as the lake and ocean samples in background area. It might suggest that the higher concentrations of toxic As(III) in well water and arsenic with higher values of easily reducible, carbonate and exchangeable phases in the well sediments, combined with the higher values of dissolved organic carbon, humic and fulvic acids and aromatic carbon as well as the higher fluorescence indensity in the well water are the key factors to cause the BFD in Taiwan.     

Mobilization of arsenic in groundwater of Bangladesh: evidence from an incubation study

The extensive extraction of arsenic (As)-contaminated groundwaters for drinking, household and agricultural purposes represents a serious health concern in many districts of Bangladesh. This laboratory-based incubation study investigated the sources and mechanisms of As mobilization in these groundwaters. Several incubation studies were carried out using sediments collected from the Bangladesh aquifer that were supplemented, or not, with different nutrients, followed by an analysis of the sediment suspensions for pH, ORP (oxidation-reduction potential), EC (electrical conductivity) and As and Fe(ΙΙ) concentrations. In the substrate-amended sediment suspensions incubated under anaerobic environment, there was a mobilization of As (maximum: 50–67 μg/l) and Fe(ΙΙ) (maximum: 182 μg/l), while the ORP value decreased immediately and drastically (as much as −468 mV to −560 mV) within 5–6 days. In the sediment suspensions incubated under control and aerobic conditions, no significant As mobilization occurred. The simultaneous mobilization of As and Fe(ΙΙ) from sediments is a strong indication that their mobilization resulted from the reduction of Fe oxyhydroxide by the enhanced activity of indigenous bacteria present in the sediments; this phenomenon also provides insights on the mobilization mechanism of As in groundwater. The concentrations of As in the sediments used in the incubation studies were strongly linked to the gradients of redox potential development that was stimulated by the quantity of organic nutrient (glucose) used. The penetration of surface-derived organic matter into the shallow aquifer may stimulate the activity of microbial communities, thereby leading to a reduction of iron oxyhydroxide and As release.     

Long-term geochemical evolution of acidic mine wastes under anaerobic conditions

A nearly 5-year anaerobic incubation experiment was conducted to observe the geochemical evolution of an acidic mine waste. Long-term storage of the mine waste under strict anaerobic conditions caused marked increase in aqueous sulfur, while aqueous iron showed no remarkable change. Co-existing oxidation and reduction of elemental sulfur appeared to play a central role in controlling the evolutionary trends of aqueous sulfur and iron. Addition of organic matter increased the aqueous Fe concentration, possibly due to enhanced iron mobilization by microbial iron reduction and increased iron solubility by forming organically complexed Fe species. Further addition of CaCO₃ resulted in immobilization of aqueous iron and sulfur due to elevated pH and gypsum formation. The chemical behaviors of environmentally significant metals were markedly affected by the added organic matter; Al, Cr, Cu, Ni and Zn tended to be immobilized probably due to elevated pH and complexation with insoluble organic molecules, while As and Pb tended to be mobilized. Jarosite exhibited high stability after nearly 5 years of anaerobic incubation and even under circumneutral pH conditions. Long-term weathering of aluminosilicate through acid attack raised pH, while continuous reaction between the added CaCO₃ and mine waste-borne stored acid decreased pH.     

Arsenic speciation and mobility in surface water at Lucky Shot Gold Mine, Alaska

Historical mining in Alaska has created a legacy of approximately 6,830 abandoned mine sites which include adits, tailing piles and contaminated land that continue to impact surface and groundwater quality through run-off and leaching of potentially toxic metals, especially arsenic (As). One such site is the Lucky Shot Gold Mine in Hatcher Pass, south-central Alaska, which operated from 1920 until 1942, mining gold-bearing quartz veins hosted in a Cretaceous tonalite intrusion. Arsenopyrite (FeAsS) and pyrite (FeS₂) present in the quartz veins contribute to elevated As levels in water draining, abandoned mine adits. As future underground mining at Lucky Shot may further adversely impact water quality, baseline geochemical studies were undertaken to assess As mobility in the vicinity of the mine adits. Water samples were collected from streams, adits and boreholes around the mine and analysed for major and minor elements using inductively coupled plasma-mass spectrometry (ICP-MS) and for anions by ion chromatography (IC). Arsenic species separation was performed in the field to determine the ratio of inorganic As(III)/As(V) using anion-exchange chromatography, following established methods. It was determined that water draining the adits had elevated levels of As roughly seventy times the United States Environmental Protection Agency Drinking Water Standard of 10?μg?L^?1, although this was rapidly diluted downstream in Craigie Creek to <2?μg?L^?1. Adit and surface water pH was circum-neutral and displayed no characteristics of acid mine drainage. Despite being well oxygenated, As(III) is the dominant As species in adit water, accounting for close to 100?% of total As. The proportion of As(V) increases downstream of the adits, as some As(III) is oxidized, but the speciation enhances arsenic mobility at the site. The δ¹⁸O measurements indicate that the water in the system has a short residence time as it is very similar to meteoric water, supporting the observation that the predominance of As(III) in adit water results from the lack of thermodynamical equilibrium being attained and preferential absorbance of As(V).