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.     

Possibility of degradation of phenylarsonic acid in the presence of ferrihydrite

Although inorganic species are predominant in natural systems, but there are many kinds of organoarsenic species such as methylated and phenylated arsenic compounds. Phenylarsonic acid （PA） is a degradation product of organoarsenics used for chemical warfare agents, which has been detected in well water at the disposal site of the agents in Japan. There are few reports studying behavior of PA in soil. In this study, PA was adsorbed onto ferrihydrite and its chemical forms were determined using high performance liquid chromatography connected to inductivity-coupled plasma mass spectrometry （HPLC-ICP-MS）. 100 mg/kg of PA was mixed with 0.03 g of 2-line ferrihydrite. For each suspension, pH was adjusted by HNO3 or NaOH. Each sample was incubated for more than 19 hours and the final pH was measured. After filtration, the chemical form of arsenic in the filtrate was measured using HPLC-ICP-MS. In addition, ferrihydrite separated by filtration was dissolved by 3 ml of 0.5 M HCI and the arsenic species in the solution was detected by HPLC-ICP-MS （column： Tosoh TSKgel SuperlC-AP, eluent： 0.01 M HNO3）. It was verified that PA is not degraded by heating in 0.5 M HCl solution. At pH 3.1, any arsenic compounds were not detected from the solution, because almost all arsenic species were adsorbed onto ferrihydrite at lower pH. At pH= 12, however, 7%-10% of inorganic arsenic was detected in the solution. In solid phase, there are some problems to determine the precise ratio of inorganic and organic species. When the solution includes Fe ion at 0.01 M level, the retention time of arsenic species drifted compared to those in standard solution, which makes it difficult to determine precisely the arsenic species adsorbed on ferrihydrite. Therefore, more study is needed to determine the ratio of inorganic and organic species in the system.     

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.     

Treatment of high fluoride concentration wastewater by layered double hydroxides： Mechanism studies

An appropriate concentration of fluoride in drinking water is required to prevent dental cavities, but long-term ingestion of water that contains more than a suitable level of fluoride can cause bone disease and mottling of the teeth. Fluoride ions can be found in wastewater from the fluoride chemical industry, as well as the semiconductor, metal processing, fertilizer, and glass-manufacturing industries. The discharge standard for fluoride in industrial wastewater in China is 10 mg/L. Efficient treatment of fluoride-containing wastewater is therefore of major concern in China, following the rapid development of the fluoride chemical industry. Several methods have been used to remove fluoride from water, such as adsorption, chemical precipitation, electrodialysis, ion exchange and electrochemical processes. Layered double hydroxides （LDHs） are anionic clays with high anion exchange capacities which are effective adsorbents for removal of a variety of anionic pollutants. LDHs have been studied as potential adsorbents for removing toxic anionic species such as CrO4^2-, TcO4^-, SeO3^2-, pesticides, and anionic surfactants from aqueous systems. One of the main attractions of using LDHs for fluoride removal, is that unlike other chemical treatment methods, no chemical sludge should be produced. In the present study, an attempt was made to investigate the mechanism of fluoride removal by LDHs under different conditions using batch methods. In addition, the release of fluoride adsorbed on LDHs by treatment with an aqueous solution of Na2CO3 was studied. The residual fluoride was found to be 10 mg/L in a solution with an initial concentration of 1000 mg/L, which meets the discharge standard for fluoride in industrial wastewater in China.     

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.