The thermal expansion and crystal structure of mirabilite (Na<Subscript>2</Subscript>SO<Subscript>4</Subscript>·10D<Subscript>2</Subscript>O) from 4.2 to 300 K,determined by time-of-flight neutron powder diffraction

We have collected high resolution neutron powder diffraction patterns from Na₂SO₄·10D₂O over the temperature range 4.2–300 K following rapid quenching in liquid nitrogen, and over a series of slow warming and cooling cycles. The crystal is monoclinic, space-group P2₁/c (Z = 4) with a = 11.44214(4) Å, b = 10.34276(4) Å, c = 12.75486(6) Å, β = 107.847(1)°, and V = 1436.794(8) Å³ at 4.2 K (slowly cooled), and a = 11.51472(6) Å, b = 10.36495(6) Å, c = 12.84651(7) Å, β = 107.7543(1)°, V = 1460.20(1) Å³ at 300 K. Structures were refined to R _P (Rietveld powder residual, \( R_{P} = {{\sum {\left| {I_{\text{obs}} - I_{\text{calc}} } \right|} } \mathord{\left/ {\vphantom {{\sum {\left| {I_{\text{obs}} - I_{\text{calc}} } \right|} } {\sum {I_{\text{obs}} } }}} \right. \kern-\nulldelimiterspace} {\sum {I_{\text{obs}} } }} \)) better than 2.5% at 4.2 K (quenched and slow cooled), 150 and 300 K. The sulfate disorder observed previously by Levy and Lisensky (Acta Cryst B34:3502–3510, 1978) was not present in our specimen, but we did observe changes with temperature in deuteron occupancies of the orientationally disordered water molecules coordinated to Na. The temperature dependence of the unit-cell volume from 4.2 to 300 K is well represented by a simple polynomial of the form V = ? 4.143(1) × 10^?7 T ³ + 0.00047(2) T² ? 0.027(2) T + 1437.0(1) Å³ (R ² = 99.98%). The coefficient of volume thermal expansion, α _V , is positive above 40 K, and displays a similar magnitude and temperature dependence to α _V in deuterated epsomite and meridianiite. The relationship between the magnitude and orientation of the principal axes of the thermal expansion tensor and the main structural elements are discussed; freezing in of deuteron disorder in the quenched specimen affects the thermal expansion, manifested most obviously as a change in the behaviour of the unit-cell parameter β.     

Coincident negative shifts in sulfur and carbon isotope compositions prior to the end-Permian mass extinction at Shangsi Section of Guangyuan, South China

Sulfur isotope composition of carbonate-associated sulfate (δ³⁴S_CAS) and carbon isotope composition of carbonate (δ¹³C_carb) were jointly investigated on the Late Permian rocks at Shangsi Section, Guanyuan, Northeast Sichuan, South China. Both δ³⁴S_CAS and δ¹³C_carb show gradual decline trends in Late Permian strata, inferring the occurrence of the long-term variation of marine environmental conditions. Associated with the long-term variation are the two coincident negative shifts in δ³⁴S_CAS and δ¹³C_carb, with one occurring at the boundary between Middle Permian Maokou Formation and Late Permian Wujiaping Formation and another at Middle Dalong Formation. Of significance is the second shift which clearly predates the regression and the biotic crisis at the end of Permian at Shangsi Section, providing evidence that a catastrophic event occurred prior to the biotic crisis. The frequent volcanisms indicated by the volcanic rocks or fragments, and the upwelling are proposed to cause the second negative excursion. An abrupt extreme negative δ³⁴S_CAS (ca. −20‰) associated with a low relative concentration of CAS and total organic carbon without large change in δ¹³C_carb is found at the end of the second shift, which might arise from the short-term oxygenation of bottom waters and sediments that resulted from the abrupt sea level drop.     

Fe~(2+)活化过硫酸盐在石油污染土壤中修复实验研究

硫酸根自由基的高级氧化技术以高效率、污染少等优点被广泛用于环境污染治理。本文以实际石油污染土壤为对象,运用该体系对土壤进行修复研究,分别从Na_2S_2O_8/Fe~(2+)摩尔比、体系pH值、Na_2S_2O_8/Fe~(2+)投加量等方面开展了实验研究。实验表明:当Na_2S_2O_8/Fe2+摩尔比为2∶3时,石油污染物的降解效果最好,体系的pH值对降解效果影响不大,1 g土壤中浓度为0.1 mol/L的过硫酸钠和硫酸亚铁溶液的最佳加入量为2 m L、3 m L时,对土壤的降解效果最为明显,故每吨污染土壤的添加量大约为2×10~6m L、3×10~6m L。     

热化学硫酸盐还原作用(TSR)与贵州汞(金锑)矿床成因机制再探讨——从黔东锰矿古天然气渗漏沉积成矿理论得到的启示

受黔东地区南华纪锰矿的古天然气渗漏成矿理论启示,在研究贵州典型汞矿成矿作用的地球化学机理的基础上,本文将热化学硫酸盐还原反应(TSR)引入成矿过程。提出富含汞(包括气态汞)、还原硫、Cl^-的含矿—运矿流体与含汞围岩相互作用,进一步论证推断深部油气藏的圈闭体系和围岩都可能是汞的重要来源。在较高温度条件下,有油气(烃类)参与的硫酸盐热化学还原作用是还原硫(H_2S、HS^-、S^2-)的主要来源,而油气(烃类)在成矿作用中发挥了还原剂的重要作用。含矿的热流体(藏)渗漏或者喷溢,同时又溶解流经围岩中以辰砂、单质汞等形式存在的汞,转变为可溶解的汞—硫配合物而运移,在系统从封闭转为开放的构造作用下,气体组分逸失,在还原硫浓度m(S^2-)降低、Eh升高、pH降低、压力和温度降低以及盐度降低等物理化学条件下成矿。类比研究显示,贵州一些金、锑等金属矿床具有与此类汞矿床类似的成矿机理。故20世纪80年代以来的这类(汞、金、锑)金属矿床的沉积—改造成因及作者提出的相关地球化学机理应当加以适当修正。     

细粒硫酸钠盐渍土盐冻胀特性试验研究

为探究温度与硫酸钠含量对细粒硫酸钠盐渍土盐冻胀率及盐胀占比的影响,取兰州黄土作为素土人工配盐,用平衡公式进行理论推导,并设计了室内试验对其进行验证。结果表明：当压实度为92%、含水率为最优含水率16.8%时,随着含盐量的升高,细粒硫酸钠盐渍土的冻结温度随硫酸钠含量的增大而降低,且随着温度的降低,盐胀率的变化趋势与盐冻胀率基本一致。在冻结温度以下至-5 ℃盐胀发展速度最快,在-5 ℃以下盐胀率增长很小;在压实度为92%、含水率为最优含水率16.8%条件下,在硫酸钠含量不变时,温度越低,盐胀占比越大;温度不变时,硫酸钠含量越高,盐胀占比越大,在冻结温度以上盐胀占比为100%,但当温度降至-3~-4 ℃时盐胀占比降到50%,在-10 ℃以下盐胀占比基本保持不变。     

Microbial Geochemical Characteristics of the Coalbed Methane in the Shizhuangnan Block of Qinshui Basin,North China and their Geological Implications

Methanogens and sulfate reducing bacteria were detected by the 16SrRNA sequencing of coalbed methane(CBM)co-produced water in the south of the Qinshui Basin,which is indicative of the presence of secondary biological gas in the south of this basin,in contradiction to the previous understanding of thermogenic gas.This work systematically collected water samples from the CBM wells in the Shizhuangnan Block and analyzed the microbial geochemical characteristics from the aspects of water ions,hydrogen and oxygen isotopes,dissolved inorganic carbon and microbial diversity.It is shown that the Shizhuangnan Block has a nearly SN-trending monoclinic structure,and the elevation of coal seam decreases gradually from the east to west.Because of the water blocking effect of Sitou fault in the west,the precipitation flowed from the east to west,and gradually transited to stagnant flow area.The concentration variation of some ions such as Na~+,K~+,Ca~(2+),Mg~(2+),Cl~-,HCO~-_3 and total dissolved solids(TDS)suggest the variation of redox condition in the coal reservoir water.The 16SrDNA sequencing analysis of the collected water samples detected the presence of methanogens and sulfate reduction bacteria.The presence of methane production zone and sulfate methane transition zone(SMTZ)was identified.The effect of methanogens in the methane production zone leads to an increase in the methane concentration,resulting in a high gas content in the study area.In the SMTZ,most methane is consumed by anaerobic oxidation due to high sulfate concentrations.     

广东官田含铜碲黄铁矿矿床中的硫盐矿物及矿床成因

对广东官田黄铁矿矿床研究过程中，在该区首次发现多种硫盐矿物，文章对硫盐矿物进行了系统阐述，对矿石组构、主、微量元素特征，矿化期，次进行了研究。通过硫、氢氧同位素、流体包裹体成分等几方面的研究，进而探讨矿床成因，研究认为，矿床的形成以火山－岩浆期后气液为主，并有大气降水混合中－低温热液交代脉状矿床。     

Rb2SO4-CH3OH-H2O三元体系30℃及50℃平衡溶解度的研究

采用半微量相平衡装置 ,测定Rb2 SO4 CH3OH H2 O三元体系 3 0℃和 5 0℃的等温平衡溶解度。用TPD软件 (三角相图绘图软件 )绘制了相图。在这两个温度下液相为甲醇—水溶液 ,平衡固相皆为无水Rb2 SO4 。同时给出溶解度关系式 ,讨论了甲醇对Rb2 SO4 的盐析作用     

Free tropospheric reservoir of natural sulfate

¹⁰Be is used as a spike of the natural background atmospheric aerosol to calculate the global flux of sulfur (F_S) into the free troposphere. The sulfate and¹⁰Be concentrations determined in polar snow are compared. On the basis of an annual¹⁰Be production rate of 1.21 10⁶ at.cm^-2, a very low figure of 2.9 Tg S a^-1 is calculated for F_S, which suggests that most of the sulfur emitted at ground level remains in the boundary layer. The role of OCS in the upper tropospheric sulfur budget is reviewed. It is also shown that cataclysmic volcanic eruptions may disturb considerably for 1–2 years this vast background tropospheric sulfur reservoir.     

稀散金属化合物热力学性质的研究Ⅱ:HCl-In2(SO4)3-H2O体系

在HCl In2 (SO4) 3 H2 O体系中 ,溶液表观总离子强度恒定为I=0 2、0 4、0 6、0 8、1 0、1 5mol·kg-1,硫酸铟在溶液中的表观离子强度分数恒定为yB =0 0 0、0 1 0、0 2 0、0 3 0、0 5 0和 0 70条件下 ,应用经典的电动势方法测定无液体接界电池 (A)在 2 78 1 5～ 3 1 8 1 5K温度范围内的电动势 :Pt,H2 (1 0 1 3 2 5kPa) |HCl(mA) ,In2 (SO4) 3 (mB) ,H2 O|AgCl Ag (A)根据测得电池 (A)的电动势数据 ,考虑到该体系存在硫酸的二级解离 ,应用数学迭代方法确定平衡体系氢离子的浓度 ,进而确定了混合溶液中HCl的活度系数γA。结果表明 ,HCl的活度系数服从扩展的Harned规则。