Chemical alteration of tephra in the depositional environment: theoretical stability modelling

The study of the chemical stability of vitreous material in aqueous media is well‐established. There has to date been little consideration of the implications of variations in the chemical durability of tephra in Quaternary tephrochronology. Chemical alteration can take the form of cationic leaching from the matrix, or complete destruction of the silica network, either of which could constrain the ability to chemically identify distal tephra. Here we apply established models of vitreous durability to the published chemical analyses of a large number of Icelandic tephras in order to predict their relative durabilities under equivalent conditions. This suggests that some important tephras have relatively poor chemical stability, and that rhyolitic tephras are, in general, more stable than basaltic. We conclude that tephras should be expected to show predictable differential chemical stability in the post‐depositional environment. Copyright © 2003 John Wiley & Sons, Ltd.     

Deciphering polymetamorphic episodes in high-grade metamorphic orogens: Constraints from PbSL, Sm/Nd and Lu/Hf garnet dating of low- to high-grade metasedimentary rocks from the Kaoko belt (Namibia)

Three dating techniques for metamorphic minerals using the Sm–Nd, Lu–Hf and Pb isotope systems are combined and interpreted in context with detailed petrologic data from crustal segments in NW Namibia. The combination of isochron ages using these different approaches is a valuable tool to testify for the validity of metamorphic mineral dating. Here, PbSL, Lu–Hf and Sm–Nd garnet ages obtained on low- to medium-grade metasedimentary rocks from the Central Kaoko Zone of the Neoproterozoic Kaoko belt (NW Namibia) indicate that these samples were metamorphosed at around 550–560 Ma. On the other hand, granulite facies metasedimentary rocks from the Western Kaoko Zone underwent two phases of high-grade metamorphism, one at ca. 660–625 Ma and another at ca. 550 Ma providing substantial evidence that the 660–625 Ma-event was indeed a major tectonothermal episode in the Kaoko belt. Our age data suggest that interpreting metamorphic ages by applying a single dating method only is not reliable enough when studying complex metamorphic systems. However, a combination of all three dating techniques used here provides a reliable basis for geochronological age interpretation.     

土壤聚合物对几种重金属离子固化效果的研究

土壤聚合物是一种新型的无机聚合物,其分子链由Si、O、Al等以共价键或离子键连接而成,形成网络结构,对重金属有较强的固定作用.本文试图利用土壤聚合物固化铜、锌、铅三种重金属离子,实现资源化利用.实验以固化体抗压强度和浸出毒性作为性能表征量,结果表明:土壤聚合物对不同重金属的固化有各自的极限浓度,Cu2 、Zn2 、Pb2 的理想固化量分别为0.9%、1%、2%;若固化过程中添加一定量的高炉矿渣,则可以提高固化体的抗压强度.本文通过土壤聚合物固化体SEM分析,从固化体微观结构的形态来阐述土壤聚合物宏观上的优越表现.     

Problems with biogenic silica measurement in marginal seas

Surface sediment samples from the Bohai, Yellow Sea, and the Pacific were used to assess biogenic silica (BSi) content and to study uncertainties in BSi measurements. The contents of BSi in the Bohai and Yellow Sea are all less than 1%. The dissolution of BSi in sediments from the Bohai and Yellow Sea is very important to maintain high levels of silicate in the water column. The non-biogenic silica from clay minerals has an obvious effect on BSi of sediment samples in the Bohai and Yellow Sea with low BSi and high clay minerals. The solid to solution ratio was found to have a great influence on BSi measurement, which can induce uncertainties up to 75%. The effect of loss by sorption and centrifugation is negligible. Interlaboratory comparison of techniques for BSi measurement by the wet alkaline extraction technique of Mortlock and Froelich [Deep-Sea Res. 36 (1989) 1415-1426] with clay correction was suggested to give no significant differences. However, differences in sediment compositions and reagent to sample ratio may limit the application of the wet alkaline extraction method.     

Sources and biogeochemical cycling of particulate selenium in the San Francisco Bay estuary

As part of a study of estuarine selenium cycling, we measured the concentration, chemical form (speciation), and distribution of particulate selenium under various river flow conditions in the North San Francisco Bay (from the Golden Gate to the Sacramento and San Joaquin Rivers). We also conducted laboratory studies on the accumulation of selenium by phytoplankton, the critical first step in the transformation of dissolved to particulate selenium. Total particulate selenium concentration in the North SF Bay was relatively constant between high and low flow periods, ranging spatially from 0.05 to 0.35 nmol l⁻¹ and comprising between 5 and 12% of the total water column selenium inventory. Mean concentrations were generally highest in the Carquinez Strait–Suisun Bay region (salinity 0–17) and lowest in Central Bay. However, selenium content of suspended particles varied with river flow, with higher content during low flow (9.76 ± 4.17 nmol g⁻¹; mean ± sd; n = 67) compared to high flow (7.10 ± 4.24 nmol g⁻¹; n = 39). Speciation analyses showed that most particulate selenium is organic selenide (45 ± 27%), with a smaller proportion (typically <30%) of adsorbed selenite + selenate and a varying proportion (35 ± 28%) of elemental selenium. Based on the amount of elemental selenium in the seston (total suspended material), we calculate that resuspension of estuarine sediments could contribute 29–100% of particulate selenium in the water column. While selenium content of SF Bay seston (>0.4 μm) is relatively unenriched compared to phytoplankton (13.6–155 nmol g⁻¹ dry weight) on a mass basis, when normalized to carbon or nitrogen, seston contains a similar selenium concentration to SF Bay sediments or phytoplankton cultures. SF Bay seston is thus comprised of selenium-rich phytoplankton and phyto-detritus, but also inorganic clay mineral particles that effectively “dilute” total particulate selenium. Selenium concentrations in algal cultures (11 species) exposed to 90 nmol l⁻¹ selenite show relatively large differences in selenium accumulation, with the diatoms, chlorophytes and cryptophytes generally having lower selenium cell content (3.8 ± 2.7 × 10⁻⁹ nmol selenium cell⁻¹) compared to the dinoflagellates (193 ± 73 × 10⁻⁹ nmol selenium cell⁻¹). Because phytoplankton are such a rich (but variable) source of selenium, their dynamics could have a profound effect on the particulate selenium inventory in the North SF Bay.     

成都经济区天降水与下渗水元素地球化学特征及土壤元素输入输出通量

论文研究了成都经济区天降水和下渗水中元素含量、在农田耕层中的输入输出通量及其影响因素.研究表明,研究区雨水中含有大量SO2-4、NO-3等酸性物质,雨水中SO2-4 >NO-3>Cl-.雨水中Ca2 和NH 4含量最高,且NH 4>Ca2 >K >Na >Mg2 .雨水的pH与阴、阳离子摩尔浓度差值具有显著相关性.下渗水中以Ca2 为主要阳离子,且Ca2 >Na >Mg2 >K >NH 4;HCO-3为主要阴离子,且HCO-3>NO-3>SO2-4>Cl->F-,下渗水pH与阳、阴离子摩尔浓度差值具有显著相关性.不同地区雨水中Pb>As>Cd>Se>Hg,下渗水中Pb>As>Se>Cd>Hg,因此,Cd、Pb、Se和Hg等元素累积在耕层中,而As则被下渗水携带迁移出耕层进入地下水.由降雨输入土壤中的Cd通量均大于下渗水输出Cd的通量,局部地区As下渗通量高于雨水输入通量的5.45～13.16倍.土壤中元素的下渗比与土壤质地、pH有关.     

An electrochemical study of pyrite oxidation in the presence of carbon coatings in cyanide medium

The anodic and cathodic behaviour of pyrite with clay and different carbon coatings of activated carbon, graphite and carbonaceous matter in cyanide medium was investigated using the potentiodynamic method. The presence of clay coating did not change the polarisation curve appearance for either the anodic oxidation of pyrite or the cathodic reduction of oxygen or the potential of the current plateau, but only decreased the plateau current especially at a higher coating thickness. The presence of the carbon coatings marginally shifted the rest potential for pyrite to a more anodic position and slightly changed the polarisation curve appearance for pyrite oxidation. The current density for pyrite oxidation largely increased in the presence of the carbon coatings, the potential at the plateau shifted to more cathodic positions, and the plateau width became smaller. These effects became more noticeable at a higher coating thickness. The activated carbon, graphite and carbonaceous matter coatings performed similarly in affecting pyrite oxidation at a similar thickness. The carbon coatings significantly increased the limiting current densities for oxygen reduction on pyrite, and the limiting current plateau became steeper at a higher coating thickness. The carbon coatings increased the limiting current density for oxygen reduction to a similar extent at a low coating thickness, but increased to varied extents at a higher coating thickness. The carbon coatings also greatly increased the cathodic current density for gold reduction on pyrite. The enhancement of pyrite oxidation and oxygen or gold reduction on pyrite by the carbon coatings was likely attributed to the electrochemical interaction between pyrite and the carbon materials with electron-rich surfaces and high conductivity. The presence of the carbon coatings significantly increased the oxidation of pyrite in aerated cyanide solutions and the preg-robbing of pyrite especially at a higher coating thickness.     

Selenium contamination in the Colorado River Basin, western USA： Remediation by leaching and nanof＇dtration membranes

Selenium （Se） is an essential micronutrient to biota, but can become a potent toxicant at elevated concentrations. The natural sources and chemical properties of Se species make the boundary between deficiency and toxicity narrow for some biota, with both phenomena common around the globe. Large areas of farmland in the Colorado River Basin （CRB） generate salinized drainage water with Se concentrations much higher than 5 μg/L, the U.S. Environmental Protection Agency chronic water-quality criterion for the protection of aquatic life. We have carried out detailed field and laboratory studies to investigate Se geochemistry and remediation in two of these areas： the Middle Green River Basin, Utah and the Salton Sea Basin, California, located respectively in the Upper and Lower CRB. Results from these and other studies show that approximately 90% of the dissolved Se in the Colorado River and its tributaries originally is derived from the Upper Cretaceous Mancos Shale and equivalent pyritic marine units that outcrop in the Upper CRB. Selenium is mobilized commonly by biogeochemical oxidation of this pyritic shale and is concentrated mainly as selenate （SeO4^2-） in soils and agricultural drainage water of dry climates by evaporation. Minor （0%-5%） amounts of Se are present as the selenite species （HSeO3^-） and （SEO3^2-）, but these species and the more reduced species, elemental Se （SeO） and selenide （Se^2-）, have much lower solubility and/or have high sorptive affinity towards organic matter, clay minerals and iron oxyhydroxides. The concentration of dissolved Se （-2.5 μg/L） and salinity in the Lower Colorado River water are among the highest of the world major rivers. Because of low precipitation （7 cm/a） and extreme evapotranspiration （-1.8 m/a） rates in the Salton Sea Basin, California, Se values in irrigation water imported from the Colorado River increase to 〉300 μg/L in drainage wastewater. Removal of Se from contaminated wastewater by nanofiltration membranes was demonstrated in laboratory and pilot-scale field experiments.     

Impact of Changes in Redox Conditions on Leaching of Some Elements from MSW Fly Ash

Abstract. Oxidation and reduction processes can influence extent of leaching of elements from solid waste. Three samples of municipal solid waste combustion fly ash were subjected to oxidizing and reducing conditions in order to evaluate leaching of elements in the Milli-Q water and fly ash (liquid to solid ratio, 100) mixtures. Although the oxidizing and reducing conditions were applied for 6 hours only, elements like Cs, Li, Mg, Sb, Tl and V leached more under oxidizing condition than under reducing condition in the case of all three ash samples. Cadmium, Pb and Zn leached more from all samples under reducing condition than under oxidizing condition. Leaching of other elements like Al, Ba, Cr, Cu, Ni and Rb was inconsistent with oxidizing or reducing conditions and varied from sample to sample, suggesting that factors other than redox may be more important in controlling leaching of these elements. Strong acid neutralization capacity of the fly ash samples let the pH vary within a narrow range, and thus severely limited the extent of leaching during the course of the experiment. Lead and Zn were the most sensitive while K and Na were the least sensitive to changes in redox conditions.