Flotation Separation of Trace Elements from Alkaline-Earth Matrices by Co(III) Hexamethylenedithiocarbamate before ICP-AES Determination

A method for the selective separation of Ag, Cd, Cr, Cu, Ni, Pb and Zn in traces from solutions of calcite (CaCO₃), dolomite (CaMg(CO₃)₂) and gypsum (CaSO₄.2H₂O) before their determination by inductively coupled plasma-atomic emission spectrometry (ICP-AES) is presented. The expected interferences of Ca and Mg on intensities of trace analytes were removed by collecting the elements of interest with cobalt(III) hexamethylenedithiocar-bamate, Co(HMDTC)₃. The flotation of aqueous solutions (1 l) of calcite, dolomite and gypsum was performed at pH 6.0, by 1.5 mg l⁻¹ Co and 0.6 mmol l⁻¹ HMDTC⁻. To minimise the effect of the reaction between Ca/Mg, which restrains the function of the surfactant, careful selection of the most suitable foaming reagent was necessary. The accuracy of the method was established by analysing natural alkaline-earth minerals by the standard addition method as well as using the dolomite reference materials GBW 07114 and GSJ JDo-1. The ICP-AES limits of detection following flotation on different minerals were found to be 0.080 μg g⁻¹ for Cd, 0.105 μg g⁻¹ for Ag, 0.142 μg g⁻¹ for Cu, 0.195 μg g⁻¹ for Cr, 0.212 μg g⁻¹ for Ni, 0.235 μg g⁻¹ for Zn and 0.450 μg g⁻¹ for Pb.     

芙蓉锡矿方解石稀土元素地球化学特征及其对成矿流体来源的指示

方解石是芙蓉锡矿田重要的脉石矿物。根据芙蓉矿田白蜡水矿区和狗头岭矿区不同产状(云英岩型、蚀变岩体型和构造蚀变带-矽卡岩型)矿石中方解石稀土元素地球化学特征研究表明:两矿区成矿期热液方解石具有两种稀土模式,LREE(轻稀土元素)富集型和相对平坦型。其中,蚀变岩体型方解石所具有的相对平坦型稀土模式代表了LREE带出后残余热液的稀土模式特征,而云英岩型和构造蚀变带—矽卡岩型方解石的LREE富集型稀土模式与骑田岭新鲜花岗岩类似,表明成矿过程中没有LREE明显带出的迹象,残余热液继承了岩浆期后热液的特征。成矿流体来源于骑田岭花岗岩岩浆期后热液。     

微生物对碳酸盐岩的风化作用

微生物-矿物相互作用可以促进许多表生生物地球化学反应过程,是表生地球化学研究的重要内容。通过综合岩石表面的微生物类群及其地质作用,分析碳酸盐岩微生物风化的各种现象,特别是微观尺度上的各种形态,阐述碳酸盐岩的微生物风化机制与风化产物,笔者提出微生物对碳酸盐岩风化的4种途径:(1)通过微生物在岩石表面和缝隙中生长,导致岩石表层发生生物溶蚀、生物磨蚀和生物钻孔作用,加速岩石风化进程;(2)微生物群体形成的钻孔网络可以增强岩石化学溶蚀的有效表面积并导致其表面强度减弱而促进机械侵蚀作用,微生物对周围岩石颗粒胶结结构的破坏、疏松作用也会导致岩石矿物颗粒的分解;(3)微生物的持水作用,微生物分泌的有机酸以及微生物呼吸所释放的CO2对岩表水分的酸化过程亦加速岩石矿物的分解;(4)微生物生长过程中从岩石内摄取营养元素和产生复杂的有机配体,能促进矿物元素的释放。文中提出在开展微生物对碳酸盐岩风化过程和机理研究的基础上,有必要引入微生物生物技术来综合开发本地低品位含钾磷矿产资源,加速岩溶地区山地土壤的形成与演化。     

An Overview of Dissolved and Suspended Matter Fluxes in the Loire River Basin: Natural and Anthropogenic Inputs

The spatial and temporal distributions of major elements were investigated in the surface waters and in associated suspended matter at two sites of the upper Loire basin (Orleans and Brehemont) between 1995 and 1998.According to geochemical and isotopic patterns, the dissolved load appears to result from a process of mixing rainwater inputs, weathering processes of carbonate and silicate bedrock, and agricultural and urban inputs. Natural inputs influence 60% of water chemical composition at both sites. Annual dissolved fluxes were estimated to be 1300 10³ t/y at Orleans and 1620 10³ t/y at Brehemont. Major elements are transported mainly in the dissolved fraction. After correcting for atmospheric and anthropogenic inputs, the silicate specific export rate was calculated to be 11 t/y/km² throughout the basin and the carbonate specific export rate to be from 47 t/y/km² at Orleans to 23 t/y/km² at Brehemont.The suspended load appears to result from at least two particle reservoirs: a silicate reservoir and a carbonate reservoir. The silicate reservoir has a detrital origin, mainly during periods of high flow, while the carbonate reservoir has a detrital origin during periods of high flow and an authigenic origin during periods of low flow. Of the total annual flow of suspended matter, this authigenic material represents 16% at Orleans, 25% at Brehemont and 37% in the fluvial part of the estuary. After correcting authigenic inputs, the specific export rate due to mechanical weathering was estimated to be 8 t/y/km² throughout the Loire basin.     

Diurnal Variations of Hydrochemistry in a Travertine-depositing Stream at Baishuitai, Yunnan, SW China

Diurnal variations of hydrochemistry were monitored at a spring and two pools in a travertine-depositing stream at Baishuitai, Yunnan, SW China. Water temperature, pH and specific conductivity were measured in intervals of 5 and 30 min for periods of 1 to 2 days. From these data the concentrations of Ca²⁺, HCO₃⁻, calcite saturation index, and CO₂ partial pressure were derived. The measurements in the spring of the stream did not show any diurnal variations in the chemical composition of the water. Diurnal variations, however, were observed in the water of the two travertine pools downstream. In one of them, a rise in temperature (thus more CO₂ degassing) during day time and consumption of CO₂ due to photosynthesis of submerged aquatic plants accelerated deposition of calcite, whereas in the other pool, where aquatic plants flourished and grew out of the water (so photosynthesis was taking place in the atmosphere), the authors suggest that temperature-dependent root respiration underwater took place, which dominated until noon. Consequently, due to the release of CO₂ by the root respiration into water, which dominated CO₂ production by degassing induced by temperature increase, the increased dissolution of calcite was observed. This is the first time anywhere at least in China that the effect of root respiration on diurnal hydrochemical variations has been observed. The finding has implications for sampling strategy within travertine-depositing streams and other similar environments with stagnant water bodies such as estuaries, lakes, reservoirs, pools and wetlands, where aquatic plants may flourish and grow out of water.     

Disseminated ‘jigsaw piece’ dolomite in Upper Jurassic shelf sandstones,Central North Sea: an example of cement growth during bioturbation?

Unusual textural and chemical characteristics of disseminated dolomite in Upper Jurassic shelf sediments of the North Sea have provided the basis for a proposed new interpretation of early diagenetic dolomite authigenesis in highly bioturbated marine sandstones. The dolomite is present throughout the Franklin Sandstone Formation of the Franklin and Elgin Fields as discrete, non‐ferroan, generally unzoned, subhedral to highly anhedral ‘jigsaw piece’ crystals. These are of a similar size to the detrital silicate grains and typically account for ≈5% of the rock volume. The dolomite crystals are never seen to form polycrystalline aggregates or concretions, or ever to envelop the adjacent silicate grains. They are uniformly dispersed throughout the sandstones, irrespective of detrital grain size or clay content. Dolomite authigenesis predated all the other significant diagenetic events visible in thin section. The dolomite is overgrown by late diagenetic ankerite, and bulk samples display stable isotope compositions that lie on a mixing trend between these components. Extrapolation of this trend suggests that the dolomite has near‐marine δ¹⁸O values and low, positive δ¹³C values. The unusual textural and chemical characteristics of this dolomite can all be reconciled if it formed in the near‐surface zone of active bioturbation. Sea water provided a plentiful reservoir of Mg and a pore fluid of regionally consistent δ¹⁸O. Labile bioclastic debris (e.g. aragonite, Mg‐calcite) supplied isotopically positive carbon to the pore fluids during shallow‐burial dissolution. Such dissolution took place in response to the ambient ‘calcite sea’ conditions, but may have been catalysed by organic matter oxidation reactions. Bioturbation not only ensured that the dissolving carbonate was dispersed throughout the sandstones, but also prohibited coalescence of the dolomite crystals and consequent cementation of the grain framework. Continued exchange of Mg²⁺ and Ca²⁺ with the sea‐water reservoir maintained a sufficient Mg/Ca ratio for dolomite (rather than calcite) to form. Irregular crystal shapes resulted from dissolution, of both the dolomite and the enclosed fine calcitic shell debris, before ankerite precipitation during deep‐burial diagenesis.     

方解石脉双晶纹方法在工程勘察中的应用

在工程区基岩被第四纪土、江水等覆盖的情况下，如何充分利用好获得的钻孔岩芯来分析断层的发育和活动性情况就显得非常重要。为此，地基勘察中引入一种显微构造分析方法，即方解石脉双晶纹分析方法。方解石脉双晶纹能解决断层的活动期次、每一期次的强度、断层应力场、断层性质、断层活动时的环境条件和最后一次活动的时代等问题。由于方解石脉双晶纹发育的广泛性，使之具有推广价值。     

湘南多金属矿床方解石形态及表面微形貌的研究

对湘南多金属成矿区方解石的研究表明，产于钨矿床中的方解石以层状晶体发育为特征，晶体形态主要为｛０００１｝和｛０１２｝＋｛１０１０｝，晶体表面具有菱形生长阶梯；产于铅锌矿床中的方解石一般不出现层解石，晶体形态主要为｛２１３１｝，｛０１１２｝＋｛１０１０｝和｛０００１｝＋｛１０１０｝＋｛０１１２｝，晶体表面平行纹发育；远矿正常灰岩内方解石晶体形态主要为｛４０４１｝。     

海水化学演化对生物矿化的影响综述

显生宙非骨屑碳酸盐矿物经历了文石海和方解石海的交替,主要造礁生物和沉积物生产者的骨骼矿物与非骨屑碳酸盐矿物具有同步变化的趋势。这种长期的变化趋势可以用海水化学Mg/Ca摩尔比的变化来解释。流体包裹体、同位素和微量元素等证据也证实了海水化学在地质历史中经历过剧烈的变化。虽然生物诱导矿化和生物控制矿化的相对重要性一直存在争议,但古生物地层记录和人工海水养殖实验结果都表明,海水化学演化对生物矿化有重要的影响,体现在造礁生物群落的兴衰、生物起源时对骨骼矿物类型的选择以及微生物碳酸盐岩在地质历史中的分布等。这些为研究前寒武纪海水化学演化、古气候和古环境的重建、同位素地层对比以及碳酸盐的沉积和成岩等问题提供了新的思路。     

鄂尔多斯盆地东南部延长组储层成岩体系研究

鄂尔多斯盆地东南部延长组具有丰富的油气资源,储集层为一套致密低渗透砂岩,油气的富集与致密低渗透背景下的高效储层有关。通过铸体薄片、背散射、扫描电镜及能谱分析,结合孔、渗测定,认为:①延长组高效储层的形成与绿泥石环边有密切关系,绿泥石环边的出现是三角洲前缘沉积环境、富黑云母的长石砂岩和咸—微咸水的湖泊水体在空间上耦合的产物;②绿泥石环边抵消了一部分埋藏过程中上覆地层的机械压实作用,减缓了由于压实作用而引起的原生孔隙的减低,而且有抑制石英次生加大的作用;③同生期形成的方解石可以使颗粒呈嵌晶接触,形成致密层,但是这部分方解石量小且分布不均匀;④自生石英在纵向上变化明显,封闭体系中形成的SiO2由于绿泥石环边的抑制作用,以雏晶的形式产出;而半封闭体系中形成的SiO2可向上发生运移,在绿泥石环边不连续或欠发育的层段以加大边的形式产出。通过成岩体系研究,可以明确高效储层的形成机理,指导岩性油气藏的勘探。