Temporal and dimensional distribution of sulfate-reducing bacteria （SRB） groups and quantity in the sediments of Lake Erhai

The purpose of the thesis is to analyze the temporal and dimensional distribution of sulfate-reducing bacteria （SRB） groups and quantity in Lake Erhai. In April and September 2005, two sediment cores were collected from Lake Erhai. SRB groups were analyzed by PCR with six-groups primers designed according to the specific 16SrDNA sequence. FISH （fluorescence in-situ hybridization） was established with the oligonucleotide probe （SRB385） and utilized to analyze SRB quantity in the sediments. The results showed that in the sediments of Lake Erhai four SRB groups were detected except Desulfobacterium and Desulfobacter, meanwhile Desulfovibrio-Desulfomicrobium were detected only in autumn; different SRB groups had different temporal and dimensional distribution, and each group in autumn is distributed more widely than in spring; FISH used to count SRB in the sediments of fresh lake was set up successfully; the analysis of correlation between the sediment＇s depth and SRB quantity had statistical meaning （P〈0.05） . The result showed that SRB quantity showed a decreasing trend with increasing depth. Through the analysis of randomized block designed analysis of variance, the difference in SRB quantity between spring and autumn also had statistical meaning （P〈0.001）, which revealed SRB quantity in autumn was larger than in spring; the result of FISH showed that there were some SRB in the deeper sediments in which no above-mentioned six SRB groups were detected by PCR. SRB groups in the sediments of Lake Erhai were rich, and the quantities of SRB groups in autumn were larger than in spring; possibly there were uncultivable SRB groups in the sediments of Lake Erhai.     

Geochemistry of porewater and sulfate-reducing bacteria in sediment cores from the Chianan Plain, Taiwan

High concentrations of arsenic and humic substances in groundwater from the southwestern coastal plain of Taiwan were well known for their probable relationships with black-foot disease. In order to realize the relationships between the concentrations of humic substances and arsenic in this area, 24 well water samples were analyzed. After filtered through 0.45 μm glass fiber membrane in the field, samples were kept in the dark at 4℃ and then separated into six fractions with varying range of molecular weight （〈0.5, 0.5-1, 1-5, 5-10, 10-50 and 〉50 k Da） by ultrafiltration apparatus （Molecular/Por Stirred Cell system） in the lab. Concentrations of humic substances were measured by fluorescence spectrometer （HITACHI F-2000, ex=370, em=445） and arsenic by FIAS-AA （Perkin Elmer AAnalyst 100, FIAS-400）. On average, only 6.2% of the total arsenic in water existed in the fraction of 〉0.5 k Da. and the others were complexed with humic substances （including humic acid and fulvic acid）. The results demonstrated a distinct positive correlation between the concentrations of humic substances and arsenic.     

Environmental geohydrochemistry and health of the high altitude population in Ladakh

Background： Radiographic signs of Pneumoconiosis found in farming Ladakhi despite absences of mines and industries were believed to be due to exposure to frequent dust storms and domestic fire pollutions. Seasonal Koilonychia （spoon nail） occurring predominantly in farming women in absences of iron deficiency anaemia was thought to arise from exposure to water made alkaline by weathering of hornblende minerals. The relation of these health conditions to environmental geohydrochemistry is postulated as the source of irrigation water in the affected population originates from glaciers in trans-Himalaya range of sedimentary geology and steep landscape favouring flushing of silica/silicate containing silts. Methods and results： Survey in two central Ladakh villages revealed radiographic evidence of silicosis in all middle aged women and half in middle aged men. In a large-scale study of 3105 subjects aged over 30 years from three villages; 101 （22.5%） of the 449 radiographed showed signs of pneumoconiosis （ILO 1980 criteria） including eggshell calcification of hilar gland and progressive massive fibrosis. Indoor dust analyzed using Philips 400T electron microscope with energy dispersive analysis system attached showed SiO2 levels upto 53.27% with particle size of 0.5 to 5.0 microns and the concentration during cooking period in the worst affected area was 7.495 mg/m^3. Microscopy and histopathology from the subject was characteristic of pneumoconiosis. Analysis of the inorganic dust in the lung showed 40.2% muscovite, 37.3% quartz with the extracted dust wt 147.9 mg/gm of dry tissue. Prevalence of chronic cough with chronic phlegm and percentage of villagers with FEV1/FVC ratio of less than 65% rose with age. Of 70 subjects studied 19 women and 2 men had Koilonychia with incidence being highest in summer. Absence of seasonal Koilonychia in villages fed by water derived from northern mountain range glaciers with mainly igneous geology supports our hypothesis.     

The ＂CO2-rich gas vents＂ of Mt. Amiata volcano （Tuscany, Central Italy）： Geochemistry,genetic mechanism and hazard evaluation

Mt. Amiata （Southern Tuscany, Central Italy） is an extinct Quaternary volcano located in an area still marked by high heat-flow that is caused by deep seated （6-10 km） hot masses related to Pliocene magmatic activity. The anomalous geothermal gradient gives rise, within the Mesozoic limestone formation （Tuscan series）, to geothermal systems that fed the Ca-SO4 thermal springs characterizing this area. Besides of thermal fluids, several cold, dry CO2-rich gas emissions seep out on the NE flank of the volcano. These gas vents mostly consist of large sub-circular craters at variable depth and diameter （5-15 m and 10-50 m, respectively）, and represent a serious hazard for the local population, as testified by the several asphyxia casualties that have been repeatedly occurred within these morphological depressions. In this work, the chemical and isotopic compositions of the Mt. Amiata ＂CO2-rich gas vents＂ and the estimation of both the CO2 flux from the soil and the CO2 distribution in air of their surroundings, has been carried out in order to： （1） assess the origin of gases, （2） recognize the mechanism of formation for these gas emissions and their relationship with local tectonics, and （3） to evaluate the CO2 hazard in the high flux emanations. The chemical composition of the gases is largely dominated by CO2 （up to 98 % by vol） and shows relatively high concentrations of N2, CH4 and H2S （up to 1.1%, 0.9% and 3.9 % by vol, respectively）. These features, coupled with the carbon and nitrogen isotopic signatures, suggest that the origin of the main gas compounds may be related to the contribution of deep （i.e., thermometamorphic processes on carbonate formations for CO2） and shallow （i.e. thermal decomposition of organic material for CH4, N2 and H2S） sources.     

Association between multi-level inorganic arsenic exposure from drinking water and skin lesions in Inner Mongolia, China

Arsenic is one of the most important single-substance toxicants in the environment. In Inner Mongolia of China, 300000 residents are believed to drink water containing 〉50 μg/L. Skin lesions have been known as the most common consequences resulting from chronic exposure to arsenic. To clarify the prevalence of arsenic-induced skin lesions, it is important to assess the impact of this problem on the target population, and to make future planning. We evaluated the association between multi-level inorganic arsenic exposure from drinking water and skin lesions in an arsenic-affected area in Inner Mongolia, China. 109 and 32 subjects fi＇om high-level arsenic-affected （〉5 μg/L） village and low-level （≤50 μg/L） village were recruited and had detailed physical examination with special emphasis on arsenic-related skin lesions. Arsenic exposure was measured for each participant with As concentration of primary well and the duration of using the well was recorded. Arsenic-induced skin lesions including keratosis, pigmentation, and/or leucomelanosis were diagnosed in 56 and 3 subjects in the two villages, respectively. Logistic regression was conducted to calculate prevalence-odd ratios of skin lesions by levels of arsenic exposure with adjustment of sex, age group, smoking and duration of exposure. A consistent dose-response relationship between arsenic exposure level and skin lesion risk was observed.     

Geochemistry of soils derived from black shale, central Hunan, China

The black shale formed under anoxic conditions usually contains high concentrations of many metals. Weathering of such black shale might cause the emission of many metals. Moreover, soils derived from black shale （SBS） are believed to be affected by black shale weathering. In recent years, many studies such as Lee et al. （2002）, Woo et al. （2002）, Fang et al. （2002）, Pasava et al. （2003）, and Peng et al. （2004） have approached the heavy metal contaminations of SBS, but systematical geochemical study is rare. Presently, the SBS and its corresponding black shales （CBS） were both sampled from central Hunan （China）, and analyzed for a large number of elements, using an Elan6000 ICP-MS/AES machine at Guangzhou Institute of Geochemistry, CAS. In this paper, some preliminary results are reported. The analytical results show that the SBS in central Hunan contains very high concentrations of heavy metals such as Co, Cu, Hg, Mo, Pb, Zn, U, Th, Sb, T1, Cd, Cr, Sc, V, Sn, As, Se, and Ni.     

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）.