XANES analysis of the mechanisms of arsenic removal in biological iron and manganese treatment unit

Biological iron and manganese removal utilizing indigenous iron and manganese oxidizing bacteria （IRB hereafter） in groundwater can also be applied to arsenic removal according to our pilot-scale test. The arsenic removal probably occurred through sorption and complexation of arsenic to iron and manganese oxides formed by enzymic action of IRB. We investigated the chemical properties of iron and manganese oxides in IRB floc and the valence state of arsenic sorbed to the floc to clarify the mechanisms of the arsenic [especially As （Ⅲ）] removal. The floc samples were collected from two drinking water plants using IRB （Jyoyo and Yamatokoriyama, Japan）, and our pilot - scale test site where arsenic and iron removal using IRB is under way （Mukoh, Japan）. The Jyoyo and Yamatokoriyama IRB floc samples were subjected to As （Ⅲ） and As（Ⅴ） sorption experiments. The elemental composition of the floc samples was measured. XANES spectra were collected on As, Fe and Mn K-edges at synchrotron radiation facility Spring 8 （Hyogo, Japan）. FT-IR and the X-ray diffraction spectra of the samples were also obtained. The IRB floc contained ca. 35 % Fe, 0.3%-3.5% Mn and 2%-6% P. The samples were highly amorphous and contained ferrihidrites and hydrated iron phosphate. According to XANES analyses of IRB, As associated with IRB was in ＋5 valence state when As （Ⅲ） （or As （Ⅴ）） was added in laboratory sorption test, Fe in ＋3 valence state, and Mn a mixture of＋3 and ＋4 valence states. Small shift was observed in the XANES spectra of IRB on As K-edge as the equilibration time of the sorption experiment was increased. Gradual oxidation of a small amount of As （Ⅲ） associated with IRB or change in arsenic binding with sorption site were the probable mechanism.     

Synergistic effect of combining sulfate reducing bacteria and zerovalent iron permeable reactive barriers on the treatment of groundwater rich in uranium, sulfate and heavy metals

Uranium processing and mining activities that generate many contaminants, such as high concentrations of U （VI）, sulfate and heavy metals （Zn, Cu, Ni, etc）, may pose a serious threat to the groundwater resources. In recent years, considerable research has been conducted respectively on two kinds of permeable reactive barriers （PRB）, including zerovalent iron （ZVI） and sulfate reducing bacteria （SRB）, for in-situ removal of these pollutants from groundwater. However, little investigation has been carried out on the potential benefits of bioaugmenting ZVI barriers to enhance the elimination of the pollutants by combining ZVI with SRB systems. The main goal of this study was to conduct batch and column experiments to determine whether the combination of SRB and ZVI can function synergistically and accelerate the rate of pollutant removal. The results of anaerobic batch experiments demonstrated that although the integrated ZVI/PRB system itself has no ability to reduce and remove sulfate directly, SRB can utilize hydrogen gas produced during the slow process of ZVI corrosion as an electron donor to raise biomass yields significantly and accelerate reductive sulfate removal. In particular, ferrous cations produced as the byproduct of ZVI corrosion process reacted with hydrogen sulfide from sulfate reduction and formed iron-bearing sulfide precipitates, which can stimulate the growth of SRB and promote sulfate removal activity by eliminating the biotoxicity of hydrogen sulfide. It was also shown that secondary mineral products （pyrite/ferrous sulfide） formed as a consequence of microbial sulfate reduction and ZVI corrosion process can enhance the microbial precipitation of soluble U （VI） as insoluble uraninite（uranium dioxide）.     

Analysis of the effect of geology, soil properties, and land use on groundwater quality using multivariate statistical and GIS methods

The regional survey of groundwater used as a small water supply system was performed to know the effect of geology, soil properties and land use on groundwater quality at Nonsan City, Korea. A total of 126 groundwater samples were collected and analyzed at the study area. The multivariate statistical methods, principal components analysis and discriminant analysis, and GIS technique were used for the quantitative interpretation of groundwater quality. The study area is mainly composed of Precambrian gneiss, Jurassic granite, and Cretaceous volcanics, and metasedimentary rocks of the Ogcheon zone. The land use was grouped as paddy, upland, grassland, resident, point source, industrial area, and water system. The soil properties were classified as 4 major groups, Entisols, Alfisols, Inceptisols, and Ultisols, by the degree of development, and reclassified as 11 subgroups. The modified and simplified geologic map, soil map, and land use map were made by using ARCGIS soft-ware. The area of geology, soil property, and land use affecting the groundwater quality for each well were also calculated by ARCGIS soft-ware to acquire the quantitative parameters for multivariate statistical analysis. The monitoring results of groundwater in the study area showed that 13%-21% of the groundwater samples exceeded the portable water guideline and the main causes were turbidity, bacteria, arsenic and nitrate-N. The spatial distribution of each component showed the close relationship between groundwater quality and geology reflecting the topography, land use.     

Boron isotopic geochemistry of karst groundwater in Guiyang City, China

Boron has two stable isotopes （^10B and ^11B） with relative abundances of about 20% and 80%, respectively. Boron isotopic ratios in natural materials show a huge range of variations, from -70‰ to ＋60‰, when expressed with the classical δ^11B notation. Most of these isotopic variations occur at the surface of the Earth. Hence, boron isotopic composition can be used as a sensitive tracer in geochemical study, for instance, to identify the different sources of contamination and factors controlling the salinity of groundwater. During the last decade, boron isotopes have been used to discriminate between the influences of seawater intrusion and anthropogenic discharge. But few of those researches can precisely identify the different sources of contamination. We measured the boron concentrations and boron isotopic ratios of groundwater samples collected in Guiyang City, as well as the major ions. The results indicate that the major ion composition of the groundwater in the investigated area is mainly controlled by the interactions between water and the dominant rock i.e. carbonates. All the water compositions are characterized by high concentrations of Ca^2＋, Mg^2＋, HCO3^-, SO4^2-, and NO3^-, which are the dominant contaminants. Both dissolved boron concentrations and isotopic ratios show large variations among the ground waters, from 2 μg/L to 90 μg/L and from -6‰ to ＋26‰, respectively. The boron concentrations and isotopic ratios indicate that the river across the studied city has been seriously contaminated by urban discharge. Boron concentrations of fiver water samples varied from 20 μg/L to 140 μg/L, with an average δ^11B value of ＋2.0‰. Using boron isotopic compositions and different geochemical indices allowed us to clearly identify and distinguish the two major sources of contamination, agricultural activity and urban wastewater. Both of the two sources are characterized by high boron concentrations but their boron isotopic compositions significantly differ.     

The effect of acid deposition on base cation cycling in a karstic-forested catchment： Evidence from strontium isotopes

Bedrock weathering and atmospheric deposition are the two primary sources of base cations （K^＋, Na^＋, Ca^2＋ and Mg^2＋） to forest ecosystems. Therefore, the key problem is to understand the relative inputs from these two sources and the cycling in the ecosystem. This study focuses on the effects of acid deposition on cation cycling in a small-forested karstic catchment in Guizhou Province. Sr isotope ratios were used as a tracer for understanding the transport process between the different cation pools： rock, soil, surface water, atmospheric deposition and plant. The samples of wet deposition, total deposition, throughfall, surface and ground waters, vegetation, and soil were monthly collected. The exchangeable Sr^2＋ and Ca^2＋ in soil samples were extracted by using 1 M ammonium acetate. The leaf-tissue samples were ashed at 550℃, and the residue was digested in ultrapure HClO4 and HNO3. All water samples were filtrated through 0.45 μm aperture filter paper. Base cation concentrations and Sr isotopic composition were analyzed for all the samples. The results show that acid deposition （average pH 4.9） frequently occurred in the studied region. Cation abundance follows an increasing manner from rainwater, throughfall, to surface water or ground water samples, suggesting that acid deposition at first eiuviates Ca^2＋ , Mg^2＋ and Sr^2＋ from leaf, then the exchangeable cations from soil, and at last cations accumulate in surface water or ground water.     

Hydrogeochemical controls on surface and groundwater chemistry in naturally acidic, porphyry-related mineralized areas, southern Rocky Mountains

In southern Rocky Mountains, catchments characterized by acidic, metalliferous waters that are relatively unaffected by human activity usually occur within areas that have active or historical mining activity. The US Geological Survey has utilized these mineralized but unmined catchments to constrain geochemical processes that control the surface- and ground-water chemistry associated with near surface acid weathering as well as to estimate premining conditions. Study areas include the upper Animas River watershed, Lake City, Mt. Emmons, and Montezuma in Colorado and Questa in New Mexico. Although host-rock lithologies range from Precambrian gneisses to Cretaceous sedimentary units to Tertiary volcanic complexes, mineralization is Tertiary in age and associated with intermediate to felsic composition, porphyritic plutons. Pyrite is ubiquitous. Variability of metal concentrations in water is caused by two main factors： mineralogy and hydrology. Parameters that potentially affect water chemistry include： host-rock lithology, intensity of hydrothermal alteration, sulfide mineralogy and chemistry, gangue mineralogy, length of flow path, precipitation, evaporation, and redox conditions. Springs and headwater streams have pH values as low as 2.5, sulfate up to 3700 mg/L and high dissolved metal concentrations （for example： Al up to 170 mg/L; Fe up to 250 mg/L; Cu up to 3.5 mg/L and Zn up to 14 mg/L）. With the exception of evaporative waters, the lowest pH values and highest Fe and Al concentrations occur in water draining the most intense hydrothermally altered areas consisting of the mineral assemblage quartz-sericite-pyrite. Stream beds tend to be coated with iron floc, and some reaches are underlain by ferricrete. When iron-rich ground water interacts with oxygenated waters in the stream or hyporheic zone, ferrous iron is oxidized to ferric iron, which is less soluble, leading to the precipitation of iron oxyhydroxides.     

深部找铀及湘南-桂北地区深部找铀潜景分析

概述了国内外深部找矿的研究成果,指出深部找矿是当今发展的趋势。国内外重大矿产的成功发掘,其深度均在千米以上,铀矿化垂向分布深度可达4 km以上。综合介绍了国内外勘查深大矿床的特点和条件,认为岩石-构造条件是深部矿化定位的重要因素,复式岩体、成矿系统的垂向变化、构造地球物理-地球化学异常模型是深部找矿的关键依据。综述了中国南方湘南—桂北地区深部找铀的有利地质构造条件和潜力,成矿流体是该区铀矿化的根源,白垩—第三纪重大地质事件是该区深部铀成矿的重要前提,重大地质事件引发的NE-NNE,NW向深大断裂及断陷盆地是铀矿化赋存的重要场所和勘查靶区。在已知铀矿田、成矿带勘查范围基础上,在该区进行深部探索将会获得重大突破。探讨了湘南—桂北地区深部找铀的勘查思路和方法。