俯冲带中大理岩与榴辉岩的Mg-Fe-C-O同位素迁移

碳酸盐岩和碳酸盐化岩石是俯冲带中碳的主要地质载体.俯冲-折返的超高压变质岩记录了俯冲隧道中流体-岩石的相互作用与元素迁移,是研究地球内部元素循环的重要媒介.本文采集了大别造山带罗家岭互层状产出的大理岩和榴辉岩,建立了横跨岩性界面的矿物组成、显微结构和Mg-Fe-C-O同位素剖面.大理岩中主要组成矿物为白云石,其次为方解...     

伊犁蒙其古尔铀矿床含矿层砂岩中黄铁矿形成机制及对铀成矿的指示意义

蒙其古尔铀矿床为伊犁盆地南缘大型层间氧化带砂岩型铀矿床,为查明该矿床含矿层中黄铁矿成因及其形成机制,探讨微生物参与铀成矿过程。文章对含矿层砂岩中黄铁矿与铀矿物矿物学特征、黄铁矿S同位素与碳酸盐胶结物的C-O同位素开展细致研究。研究表明:①蒙其古尔铀矿床中铀主要以铀矿物与吸附铀形式存在,吸附铀主要为有机质吸附铀,铀矿物以沥青铀矿为主,多与黄铁矿、炭屑共生;②蒙其古尔铀矿床含矿层砂岩中黄铁矿主要以自形晶、草莓状和不规则状集合体产出,多与沥青铀矿、碳酸盐胶结物共生,其中黄铁矿S同位素(δ~(34)S_(V-CDT)=-68.4‰～22.1‰)与碳酸盐胶结物的C-O同位素(δ~(13)C_(V-PDB)=-10.2‰～-7.4‰,δ~(18)O_(V-PDB)=-9.6‰～-5.8‰)分析表明黄铁矿具有细菌硫酸盐还原(BSR)与有机物热解2种成因,并探讨了这2种不同成因黄铁矿的形成机制。③结合前人研究成果,认为硫酸盐还原菌(SRB)参与蒙其古尔铀矿床铀成矿过程,以间接还原方式为主,在有机质、黏土矿物与颗粒表面吸附U(Ⅵ)的基础上,通过硫酸盐还原菌(SRB)还原SO_4~(2-)产生的H_2S将U(Ⅵ)被还原成U(Ⅳ),形成铀矿物。     

Geochemistry of Flooded Underground Mine Workings Influenced by Bacterial Sulfate Reduction

Unlike the majority of the water in the flooded mine complex of Butte Montana, which includes the highly acidic Berkeley pit lake, groundwater in the flooded West Camp underground mine workings has a circum-neutral pH and contains at least 8 μM aqueous sulfide. This article examines the geochemistry and stable isotope composition of this unusual H₂S-rich mine water, and also discusses problems related to the colorimetric analysis of sulfide in waters that contain FeS_(aq) cluster compounds. The West Camp mine pool is maintained at a constant elevation by continuous pumping, with discharge water that contains elevated Mn (90 μM), Fe (16 μM), and As (1.3 μM) but otherwise low metal concentrations. Dissolved inorganic carbon in the mine water is in chemical and isotopic equilibrium with rhodochrosite in the mineralized veins. The mine water is under-saturated with mackinawite and amorphous FeS, but is supersaturated with Cu- and Zn-sulfides. However, voltammetry studies show that much of the dissolved sulfide and ferrous iron are present as FeS_(aq) cluster molecules: as a result, the free concentration of the West Camp water is poorly constrained. Concentrations of dissolved sulfide determined by colorimetry were lower than gravimetric assays obtained by AgNO₃ addition, implying that the FeS_(aq) clusters are not completely extracted by the Methylene Blue reagent. In contrast, the clusters are quantitatively extracted as Ag₂S after addition of AgNO₃. Isotopic analysis of co-existing aqueous sulfide and sulfate confirms that the sulfide was produced by sulfate-reducing bacteria (SRB). The H₂S-rich mine water is not confined to the immediate vicinity of the extraction well, but is also present in flooded mine shafts up to 3 km away, and in samples bailed from mine shafts at depths up to 300 m below static water level. This illustrates that SRB are well established throughout the southwestern portion of the extensive (>15 km³) Butte flooded mine complex.     

陆相咸化湖泊沉积硫酸盐岩硫同位素组成及其地质意义

现代海洋中的硫酸盐矿物和海水硫酸盐本身常有相似的硫同位素组成,因而可根据现代蒸发岩的硫酸盐同位素来判断古环境。据李任伟［１］引用Ｈｏｌｓｅｒ和Ｋａｐｌａｎ及格里年科的资料报道,海相蒸发岩及其所反映的古海洋硫酸盐的硫同位素组成只在较狭窄的范围内变化,现...     

硫和氧同位素示踪黄河及支流河水硫酸盐来源

为了准确识别河水硫酸盐受自然风化和人为活动影响的过程,做好地表水资源管理,选择黄河小浪底水库以下干流和支流河水为主要研究对象,分期采集河水样品,采用硫酸盐硫和氧同位素,结合水化学组成及潜在硫酸盐来源硫和氧同位素范围,判定黄河及支流河水硫酸盐的来源及混入比例。结果表明:① 研究区黄河河水硫酸盐主要来源于第四纪黄土中易溶硫酸盐,干流河水SO₄2-含量均值为2.23 mmol/L,δ34S_SO4和δ18O_SO4均值分别为+8.9‰和+10.4‰;② 研究区沁河丰水期河水硫酸盐24%来源于大气降水,61%来源于土壤硫酸盐溶解,15%来自于石膏溶解;平水期河水硫酸盐39%来源于大气降水,36%来源于土壤硫酸盐溶解,25%来源于石膏溶解。沁河河水SO₄2-含量均值为2.44 mmol/L,δ34S_SO4和δ18O_SO4均值分别为+9.8‰和+9.7‰;③ 研究区洛河河水硫酸盐受生活污水影响较大,伊河河水硫酸盐受到土壤硫酸盐溶解和化学肥料溶解的共同影响,伊洛河河水SO₄2-含量均值为1.27 mmol/L,δ34S_SO4和δ18O_SO4均值分别为+10.4‰和+6.5‰。蒸发盐类矿物溶解以及土壤硫酸盐溶解等自然风化过程是控制区域河水硫酸盐来源的重要过程,人为活动对伊洛河河水硫酸盐的贡献不容忽视。     

Evaluating new fault-controlled hydrothermal dolomitization models: Insights from the Cambrian Dolomite,Western Canadian Sedimentary Basin

Fault-controlled hydrothermal dolomitization in tectonically complex basins can occur at any depth and from different fluid compositions, including ‘deep-seated’, ‘crustal’ or ‘basinal’ brines. Nevertheless, many studies have failed to identify the actual source of these fluids, resulting in a gap in our knowledge on the likely source of magnesium of hydrothermal dolomitization. With development of new concepts in hydrothermal dolomitization, the study aims in particular to test the hypothesis that dolomitizing fluids were sourced from either seawater, ultramafic carbonation or a mixture between the two by utilizing the Cambrian Mount Whyte Formation as an example. Here, the large-scale dolostone bodies are fabric-destructive with a range of crystal fabrics, including euhedral replacement (RD1) and anhedral replacement (RD2). Since dolomite is cross-cut by low amplitude stylolites, dolomitization is interpreted to have occurred shortly after deposition, at a very shallow depth (<1 km). At this time, there would have been sufficient porosity in the mudstones for extensive dolomitization to occur, and the necessary high heat flows and faulting associated with Cambrian rifting to transfer hot brines into the near surface. While the δ¹⁸O_water and ⁸⁷Sr/⁸⁶Sr ratios values of RD1 are comparable with Cambrian seawater, RD2 shows higher values in both parameters. Therefore, although aspects of the fluid geochemistry are consistent with dolomitization from seawater, very high fluid temperature and salinity could be suggestive of mixing with another, hydrothermal fluid. The very hot temperature, positive Eu anomaly, enriched metal concentrations, and cogenetic relation with quartz could indicate that hot brines were at least partially sourced from ultramafic rocks, potentially as a result of interaction between the underlying Proterozoic serpentinites and CO₂-rich fluids. This study highlights that large-scale hydrothermal dolostone bodies can form at shallow burial depths via mixing during fluid pulses, providing a potential explanation for the mass balance problem often associated with their genesis.     

采用SDS研究泥蚶血红蛋白(Tg-HbⅡ)具有过氧化物酶及抗菌活性的结构基础

泥蚶血红蛋白(Tg-HbⅡ)除了具有携氧功能外,还具有过氧化物酶活性和抗菌活性。本文采用分光光度法、光谱法和分子对接等技术研究了十二烷基硫酸钠(SDS)对Tg-HbⅡ的结构、过氧化物酶活性及抗菌活性的影响,以探讨Tg-HbⅡ具有过氧化物酶活性及抗菌活性的结构基础。研究结果显示,SDS的疏水烷基长链可嵌入到Tg-HbⅡ血红素口袋内部,与近端His104形成氢键,断裂血红素铁与His104的配位键,使Tg-HbⅡ的Soret带吸收峰降低并发生位移;此外,SDS还可与血红素口袋中的氨基酸形成疏水相互作用,改变血红素口袋原有结构,使得部分疏水氨基酸暴露,导致外源荧光强度增强,最大发射波长红移。SDS可以抑制Tg-HbⅡ的过氧化物酶活性,当SDS浓度为2 mmol•L^–1时,Tg-HbⅡ的酶活性仅为原来的20%,在琼脂扩散实验中失去对枯草芽孢杆菌的抗菌活性。以上结果表明,SDS通过破坏血红素口袋的内部结构抑制Tg-HbⅡ的过氧化物酶活性,使其失去抗菌活性,血红素疏水口袋是Tg-HbⅡ具有过氧化物酶活性和抗菌活性的关键结构。本研究为进一步研究Tg-HbⅡ的抗菌机理奠定基础。     

Peroxymonosulfate Improves the Activity and Stability of Manganese Oxide for Oxidation of Arsenite to Arsenate

Manganese oxide has been widely investigated for oxidation of arsenite (As(III)) to arsenate (As(V)) due to its high redox potential; however, it becomes extremely unstable after reuse. Here, As(III) oxidation activity and stability of manganese oxide in the presence of peroxymonosulfate (PMS) is investigated. Batch experimental results reveal that manganese oxide/PMS exhibits high catalytic activity for As(III) oxidation compared to manganese oxide or PMS alone. Addition of PMS to manganese oxide not only reveals long‐term stability for As(III) oxidation, but also shows high As(III) oxidation activity in the presence of coexisting ions such as As(V) and phosphate. Quenching tests reveal that As(III) oxidation in the manganese oxide/PMS system is attributed to activation of PMS by manganese oxide at different oxidation states (Mn(III) and Mn(IV)), and the generation of sulfate radicals that are responsible for As(III) oxidation.     

新型抗水氯氧镁水泥防渗渠在自然环境的水化产物、相转变规律及其对强度的影响

氯氧镁水泥(Magnesium oxychloride cement, MOC)具有快凝、早强、高强、防火和不腐蚀玻璃纤维等优点,非常适合于制作玻璃纤维增强薄壁制品,在农业灌溉工程中具有良好的应用前景。采用XRD和TOPAS分析了新型抗水氯氧镁水泥制成内蒙古防渗渠的物相组成,探讨了氯氧镁水泥制品在自然环境的水化产物与相转变规律、以及相组成对强度的影响。结果表明,在水分缺少的条件下,氯氧镁水泥的水化产物主要为5Mg(OH)_2·MgCl_2·8H_2O(5·1·8)和Mg(OH)_2;在水分充足的条件下,水化产物主要为Mg(OH)_2和5·1·8,碳化产物为碳化氯氧化镁Mg(OH)_2·MgCl_2·2MgCO_3·6H_2O(1·1·2·6)和水菱镁矿4MgCO_3·Mg(OH)_2·4H_2O(4·1·4)。水化产物对强度有促进作用,而碳化产物会降低强度。通过10年的工程环境考验,证明新型氯氧镁水泥制品在环境中能够保持主要强度相5·1·8的稳定性,具有良好的长期力学性能。     

硫酸盐渍土含水率单次递减条件下的盐胀特性

为探究硫酸盐渍土在含水率递减下的盐胀特性,通过自主设计的试验装置,在室内开展了11组含水率单次递减下的盐胀试验,共历时2 868 h。结果表明：在含水率单次递减下硫酸盐渍土的起胀含盐量约为1.2%。含盐量<1.2%时,土体干缩,干缩量与含盐量近似呈下凸的二次抛物线规律,且干缩峰值含盐量约为0.5%;含盐量≥1.2%时,土体膨胀,且盐胀率与含盐量近似呈线性增大规律。盐胀敏感含水率区间受含盐量影响很小,含盐量从1.5%增至4.0%,盐胀敏感含水率区间基本稳定。此外,含水率递减速率与含盐量呈负相关规律,同一含盐量的硫酸盐渍土,其含水率的递减速率随含水率的降低亦减慢。基于以上试验结果,进一步开展了4组单次降温下的盐胀对比试验,结果表明：含盐量升高时,起胀温度区间逐渐升高,盐胀敏感温度区间的区间范围逐渐扩大。单次降温下的盐胀率均高于含水率单次递减下的盐胀率,且随着含盐量的升高两试验条件下的盐胀率差值趋于一常数。研究结果对西北地区高含盐量的残余型硫酸盐渍土地基的盐胀性评价具有重要指导意义。