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.     

Speciation analysis and significance of ecological geochemistry

Different species of one element have different activities, so it has different effects on environment and human health. To analyze qualitatively and quantitatively the speciation of a special element in sample, which is the important basis for appraising the toxicity and studying the rule of transfer and translation of elements. Since the 1970＇s, the scheme of sequential extraction has already been used at many laboratories both at home and abroard, to get the information about heavy metals＇ activity in polluted soils. Because this method has the experimental nature, many schemes of problem has taken place, the absence of consistency of these sequential extraction have been formed. Thus the complexity of the schemes, the lack of selectivity of reagent, the lack of quality control, the result mainly related to the extraction scheme used, and so on. In the face of these problems, the study of experimental methods of sequential extraction on three different soils, sediment in Dongting Lake, soil in Jiangsu Province and loess in Shanxi Province was made. Reference materials of heavy metal speciation following sequential extraction in soil and sediment had been developed. Nowadays two kinds of sequential extraction methods which are widely used are BCR （three steps） and improved Tessier methods （seven steps）. Based on three steps of BCR, water-soluble speciation and the residual speciation were increased in our research. BCR701 was determined eight times at different laboratories using BCR three steps. The results showed that determined data obtained eight times were identical to the standard value, and it is indicated that this method has good reproducibility. The stability and homogeneity experiments indicated that the preparation of three types of candidates accorded with our requirements. Eight laboratories had afforded the determined values of 12 heavy metal elements （Cu, Pb, Zn, Mn, Co, Ni, Cd, Cr, Mo, As, Sb, Hg, Se et al.） using BCR three steps. Also, these three candidates afforded the determined values by seven steps, and 12 laboratories had participated.     

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.     

金、银等成矿元素的构造地球化学行为

扬子与华夏地块间发育一条近东西向展布的巨型板块缝合带—华南中部复合混杂岩带,由北东向、近东西向、北北东向三组方位的次级韧性剪切带分支、复合成“网格状”构造阵列。对其次级北东向剪切带(进贤—婺源韧性剪切带)进行的构造地球化学剖面研究发现从剪切带边部至中心,随着剪切程度的逐渐增强,金、铜元素含量逐渐增高,锌元素含量逐渐降低,铅、银元素含量变化不明显、略有降低的趋势;金元素有两个峰值点,一个出现在韧性剪切最强的糜棱岩中,另一个出现在叠加于早期韧性剪切糜棱岩化岩石之上的晚期脆性破裂张性构造角砾岩中,说明韧性剪切及叠加在韧性剪切之上的脆性破裂均有利于金的富集成矿,从而为赣东北地区寻找金矿指明了方向,并为金的成矿构造地球化学理论研究积累了新的素材。