同位素地球化学、岩石地球化学——密坑山锡矿同位素年代学研究的启示

密坑山锡矿田位于江西省会昌县西南约40km处。该区为一晚中生代破火山，火山岩为上侏罗统鸡笼嶂组流纹质凝灰熔岩及火山碎屑岩，火山口周围环状及放射状断裂发育，火山口中心为浅成相的密坑山似斑状钾长花岗岩中央岩株侵入体所充填。上世纪80年代以来，在该岩体与流纹质凝灰熔岩的内外接触带相继发现了岩背、淘锡坝、苦竹岽、矿背、上湾等一批大、中型锡多金属矿床或矿点，表明这一岩体对成矿具有重要的制约作用。     

Speciation of adsorbed arsenate on the surface of hydrous iron oxide

Adsorption of arsenate on hydrous iron oxide is an important process controlling geochemical cycling of arsenic in environment as well as the fate of arsenic-bearing mining wastes. The widely accepted view on the mechanism of adsorption is that arsenate is adsorbed via bidentate binuclear inner-sphere complexation. In this study, we characterized the arsenate-hydrous iron oxide sorption solids synthesized at pH=3-8 using Fourier transformed infrared spectroscopy （FTIR） and X-ray diffraction （XRD）. It has been determined that poorly crystalline ferric arsenate developed on the surface of iron oxide when arsenate was sorbed at acidic pH, while at alkaline pH the adsorption of arsenate was via bidentate complexation.     

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.     

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.     

Geochemistry of recent hydrothermal systems of Mendeleev Volcano （Kuril Islands） and surrounding waters

On the Kuril Islands there are 85 volcanoes, 39 of which are active. Hot springs and mud pots are wide spread in this area and have significant inputs on the chemical composition of the surrounding surface waters and environment. We present results of trace elements as well as data on H, O, S, and He isotope ratios for hydrothermal systems of the Mendeleev Volcano （Kunashir Island） and surrounding surface waters. Water and gas samples were taken from springs and holes as well as creeks and the Lesnaya River. Among the thermal water types, three main groups can be distinguished. The first group includes the waters, in which SO4^- ion predominant. The water temperature on the surface reaches 97℃, and TDS varies from a few g/L to 7 g/L. These waters are acid to superacid with pH values ranging 0.6 to 2.3. The second group is sodium-chloride waters. A maximum TDS is 14.2 g/L. The waters are neutral or alkaline; pH varies from 6.9 to 8.2. The third group is the sodium-chloride-sulfate-bicarbonate water. The Stolbovskie springs, located in the periphery of the Mendeleev Volcano are representative of this type. The pH of these waters is close to neutral. TDS is 1.9 g/L. They are rather the derivatives of sodium-chloride waters arisen from dilution of them by subsurface waters. The Kuslyi Creek and Lesnaya River are located near the Mendeleev Volcano. The most acid springs discharge into the Kislyi Creek as a result pH of this creek being 2.5, and contents of most elements rather high. For example, the contents of dissolved solids of Si, Fe, Al, Mn, Zn, in waters of the Kislaya Creek are 22.1, 8.1, 6.2, 1.29, and 0.28 mg/L, and correspondently. The water of the Lesnaya River, （Before the Kislyi Creek, pH is about 8 with TDS 102 mg/L, but after the Kuslyi Creek, pH decreases and the concentrations of chemical elements increase. Debit of the Kislayi Creek in summer season is about 370 L/sec. It means that every day only this small creek inputs in the Lesnay River about 706 kg of Si;     

Attenuation of aqueous metal transport at two natural acid rock drainage occurrences in the Yukon Territory, Canada

Naturally acidic drainage associated with pyritic black shale has been observed in many locations in the Yukon Territory. While not necessarily linked to known mineral deposits, most of these natural acid rock drainage occurrences show elevated dissolved concentrations of trace elements, especially zinc, nickel, copper, cadmium and arsenic. Based on field observations, microbial investigation, chemical analyses and geochemical modeling, the fate and transport of potentially deleterious elements at two natural acid drainage occurrences with slightly different settings are examined. The Macintosh Creek is a small, acidic stream （pH 2.98-3.40）, 2 km long, located in the Macmillan Pass area of east-central Yukon amidst known sedimentary exhalative massive sulfide mineralization but remains undisturbed by exploration activities. Its trace metal content is apparently derived from groundwater discharges, which gave as much as 5.0, 2.5, 0.7, 0.13 and 0.03 mg/L ofZn, Ni, Cu and As, respectively. Interaction and sorption reactions with algal mats, biofilms and iron oxyhydroxides appear to be the dominant mechanisms attenuating aqueous contaminant transport along the stream. Cryogenic precipitation further consolidates the ferricrete formation and reduces the mobility of the sorbed metals. The tributaries of the Engineering Creek along the Dempster Highway in northern Yukon drain through a series of dolomite, phyllite, argillite, limestone, black shale, sandstone and conglomerate with no known concentration of mineralization. In this area, the water chemistry fully reflects the local geology with acidic streams invariably associated with black shale occurrences. Groundwater seeps in the headwaters area of the km-180 Creek completely enclosed in black shale gave pH 3.0 and as much as 148, 39, 2.9 and 9.1 mg/L of Zn, Ni, Cu and As, respectively. Sorption with iron oxyhydroxide and organic matter appear to dominate the attenuation of contaminant transport along the stream. However, once entered into carbonate-dominated terrains, secondary carbonate minerals exercise additional geochemical control on the local water chemistry as a result of neutralization.     

Naturally acidic and metalliferous waters at unmined volcanogenic massive sulfide deposits in the Bonnifield mining district, Alaska Range, east-central Alaska

The Bonnifield district hosts 26 tmmined volcanogenic massive sulfide （VMS） occurrences. Environmental geochemical samples of water and stream sediment were collected at several occurrences, concentrating on the two best-exposed and largest deposits, Red Mountain （RM） and Sheep Creek （SC）. Limited samples were also collected at the poorly exposed WTF deposit. The deposits are Late Devonian to Early Mississippian, and are hosted by felsic metavolcanic and carbonaceous schist members of the Totatlanika Schist or Keevy Peak Fm. Spring and stream waters at RM and SC have pH values commonly 〈3.5 （as low as 2.4 at RM and 2.5 at SC）, high conductivity （up to 11000 μS/cm）, and very high （Is to 100s mg/L） dissolved contents of Al, Cd, Co, Cu, Fe, Ni, and Pb. Waters at RM are characterized by extremely high REE contents （summed REE median 3200 μg/L, n=33）. At both RM and SC, pyrite oxidation and dissolution produce low pH waters that interact with and dissolve bedrock minerals, resulting in acidic, metal-laden, naturally degraded streams that are mostly devoid of aquatic life. Ferricrete is common. In contrast, WTF barely produces a surficial environmental footprint, mostly due to topography and relief. RM and SC are well exposed in the areas of relatively high relief, and both exhibit extensive areas of quartz-sericite-pyrite-alteration. While WTF shares many of the same deposit-and alteration characteristics, it is concealed by tundra in a large, nearly flat area. Surface water at WTF is absent and outcrops are sparse. Even though WTF is roughly the same size as Red Mountain （both around 3 million tonnes） and has similar base- and precious-metal grades, the surficial geochemical manifestation of WTF is minimal. However, exposure through mining of the altered, mineralized rock at WTF potentially could initiate the same processes of pyrite oxidation, acid generation, and mineral dissolution that are observed naturally at RM and SC.