控制灌溉对稻田CH4和N2O综合排放及温室效应的影响

采用静态箱-气象色谱法对控制灌溉稻田CH₄和N₂O排放进行了观测,研究控制灌溉模式对稻田CH₄和N₂O排放的影响,并对其温室效应进行了评估。结果表明,控制灌溉稻田CH₄排放通量明显低于淹水灌溉稻田,且主要集中在分蘖前期和中期,全生育期CH₄排放量比淹水灌溉稻田减少73.2%～85.0%。控制灌溉稻田N₂O排放通量在水稻全生育期大部分时间都要大于淹水灌溉稻田,稻季N₂O排放量分别为106.65 mg/m2和96.40 mg/m2,控灌稻田较淹灌稻田增加了10.6%。控制灌溉稻田稻季排放CH₄和N₂O的全球增温潜势(GWPs)为726 kg/hm2,较淹水灌溉稻田减少了59.1%。控制灌溉模式能显著降低CH₄和N₂O综合排放的全球增温潜势。     

疏勒河上游多年冻土区植物生长季主要温室气体排放观测

选取青藏高原东北部疏勒河上游多年冻土区的高寒草甸样地为研究对象, 对2011年植物生长季(6-10月)主要温室气体(CO₂、 CH₄CH₄和CO₂)的排放进行了观测. 结果显示: 疏勒河上游多年冻土区高寒草甸地表CO₂、 CH₄和N₂O排放速率范围分别为7.58~418.60 mg·m^-2·h^-1, -0.20~0.14 mg·m^-2·h^-1和-27.22~39.98 μg·m^-2·h^-1. 0~10 cm土壤温度、 含水量和盐分与CO₂和CH₄排放速率显著相关, 但与N₂O排放速率无显著相关. 日均排放速率显示, CO₂和N₂O在整个观测期均表现为排放; CH₄在植物返青期和生长旺盛期表现为排放, 在枯黄期伴随表层土壤发生日冻融循环时为吸收. 从9月30日12:00-10月6日14:40, 表层0~10 cm土壤经历了3次日冻融循环, CO₂和N₂O日均排放速率分别由冻融前的60.73 mg·m^-2·h^-1和9.91 μg·m^-2·h^-1提高到122.33 mg·m^-2·h^-1和11.70 μg·m^-2·h^-1. 土壤温度、 含水量和盐分是影响CO₂和CH₄排放的重要因子, 表层土壤冻融交替作用可提高地表CO₂和N₂O的排放速率.     

冈底斯西段罗布真浅成低温热液型金银矿的成矿流体演化:来自流体包裹体、H-O同位素的证据

西藏昂仁县罗布真金银矿位于冈底斯成矿带西段,其大地构造位置属于南拉萨微陆块,矿体受北西西的断裂构造控制,呈脉状、透镜状产于始新世帕那组火山岩中。按照矿石工业类型分类,矿石类型可分为角砾岩型、石英脉型和蚀变岩型等三类,主要金银矿石矿物为自然金和碲银矿等。矿区广泛繁育不同特征的热液脉体,通过系统的野外观测以及全面的岩相学研究,依据矿物共生组合、脉体切穿关系及蚀变特征,将热液脉体从早到晚划分为石英-黄铁矿阶段(S1)的石英-黄铁矿大脉、玉髓华石英-金-多金属硫化物阶段(S2)的石英-金属硫化物网脉、石英-碳酸盐矿物阶段(S3)的石英-方解石细脉。罗布真金银矿床热液脉体主要发育气液两相流体包裹体(富液两相包裹体、富气两相包裹体)和含子矿物(碳酸盐矿物)三相流体包裹体。本文在野外地质调查的基础上,对不同成矿阶段的石英脉进行了流体包裹体的岩相学观测、显微测温、成分分析以及H-O同位素测试。S1阶段流体包裹体的形成温度集中在310~330 ℃,盐度(w(NaCl_eq))集中在5.0%~10.1%,密度介于0.60~0.80 g/cm³;S2阶段流体包裹体的形成温度集中在240~280 ℃,盐度介于3.0%~7.0%,密度介于0.70~0.90 g/cm³;S3阶段流体包裹体的形成温度集中在121~215 ℃,盐度集中在1.0%~5.0%,密度集中在0.85~1.00 g/cm³。拉曼分析表明,罗布真金银矿的流体包裹体成分以H₂O为主,并含有少量的CO₂、N₂、CH₄等气体及方解石子晶。各热液脉体石英中流体包裹体的δ${{\text{D}}_{{{\text{H}}_{2}}\text{O},\text{V-SMOW}}}$值的变化范围为-106.1‰~-97.5‰,δ¹⁸${{\text{O}}_{{{\text{H}}_{2}}\text{O},\text{V-SMOW}}}$值的变化范围为-7.33‰~-7.13‰,展示其成矿流体主要源自火山岩围岩中的循环地下水,在早阶段还有少量岩浆水的加入。成矿流体在岩浆作用驱动下,沿着断裂从深部封闭体系运移到浅部的开放体系,迅速突破临界状态减压沸腾并产生相分离导致金属硫化物沉淀,形成矿化。随着含矿热液成矿物质及金属硫化物的大量析出,流体温度、盐度迅速降低,金属矿物成矿作用随之结束。罗布真金银矿床的成矿流体为中低温、低盐度、中低密度并含有少量CO₂、N₂、CH₄等气体的流体,具有典型的浅成低温热液矿床成矿流体的特征。     

基于摩擦与变形耗能的滚石切向恢复系数影响因素

切向恢复系数是滚石碰撞回弹的重要控制参数,目前的理论公式不能完全反映其作用机制,这是滚石动力学研究的一个难点问题.为此,根据滚石不同的回弹状态,提出基于入射角度变化的切向力模型;进一步,以切向接触理论和动能定理为基础,考虑碰撞过程中切向的摩擦耗能与变形耗能,推导了切向恢复系数的理论公式;最后研究入射速度、入射角、被撞击物体的变形模量对切向恢复系数的影响.结果表明:滚动回弹的切向恢复系数主要受切向变形量的影响;滑动回弹时,入射速度对切向恢复系数的影响参数为\begin{document}$ {v}^{\frac{1}{20}} $\end{document},切向恢复系数随着其增加而缓慢减少;入射角度对切向恢复系数的影响参数为$ \frac{\mathrm{c}\mathrm{o}{\mathrm{s}}^{\frac{1}{20}}{\beta }_{i}}{\mathrm{t}\mathrm{a}\mathrm{n}{\beta }_{i}} $,切向恢复系数随其增加而增大;被撞击物体的变形模量对切向恢复系数的影响参数为$ {E}_{2}^{-\frac{5}{8}} $,切向恢复系数随其增加而增加.基于摩擦与变形耗能的切向恢复系数计算公式为滚石的碰撞回弹过程提供了新的计算模型.      

二元气体等温吸附实验及其对煤层甲烷开发的意义

分别进行了CH₄-CO₂和CH₄-N₂二元混合气体的等温吸附实验, 并且分析了二元气体在吸附过程中各组分浓度的变化规律.结果表明, 在CH₄-N₂二元气体的吸附过程中, 吸附相中CH₄组分的相对浓度逐渐增加, N₂组分的相对浓度逐渐减少.在CO₂-CH₄二元气体的吸附过程中, 吸附相中CO₂组分的相对浓度逐渐增加, CH₄组分的相对浓度逐渐减少.实验结果证实了CO₂在与CH₄的竞争吸附中占据优势, 而N₂在与CH₄的竞争吸附中处于劣势.注入CO₂比注入N₂可以更有效地置换或驱替煤层甲烷, 提高煤层甲烷的采收率.      

基于DFT方法的注热蒸汽开采CH4吸附机理

为探究不同煤阶煤吸附CH₄和H₂O吸附机理,采用量子化学方法中的密度泛函理论（DFT）,在B3LYP/6-31G基组上计算了不同煤阶煤的大分子稳定构型及煤分别吸附CH₄、H₂O及CH₄与H₂O共存条件下的吸附能和电荷转移情况。研究结果表明:煤吸附CH₄为物理吸附,随着煤阶升高,煤吸附CH₄能力增强;吸附H₂O时以氢键形式作用,其中煤中含氧官能团为氢键供体,H₂O中-OH为氢键受体,随着煤阶升高,吸附H₂O能力减弱;当H₂O与CH₄共存时,H₂O抢占CH₄吸附位,导致煤优先吸附H₂O,使吸附态CH₄减少,游离态CH₄增多。从分子水平完善了煤吸附甲烷和H₂O的吸附机理,为注热蒸汽开发煤层气奠定了吸附理论基础。      

湘西北张家界市李家铜矿流体包裹体地球化学特征

湘西北地区是著名的铅锌矿、锰矿产出地,为完善该地区成矿序列,对张家界市李家铜矿成矿期的石英、方解石、重晶石进行了流体包裹体均一温度、盐度、气相成分、群体液相成分和氢氧同位素测定。结果表明: 包裹体均一温度为146~282 ℃,流体盐度为0.71%~15.86%(NaCl),成矿流体气相成分含少量的CH₄和H₂,包裹体液相成分中离子以Ca²⁺、Mg²⁺、Na⁺、$SO_{4}^{2-}$及Cl^-为主,氧同位素δ¹⁸O_矿物值范围为11.6‰~17‰,氢同位素δD值范围为-54.7‰~-76.2‰。经计算,成矿压力为1.02~66.17 MPa,成矿深度为0.1~6.57 km。成矿热液为层控型热卤水,成矿时间自震旦纪陡山沱期一直持续到志留纪文洛克期。     

武汉市第四系浅层地下水环境背景值研究

为查明武汉市第四系浅层地下水环境背景值,以2014年采集的21件浅层地下水样品水质分析数据为依据,利用Grubbs检验法剔除异常数据,采用Shapiro-Wilk检验法进行概率分布类型检验,计算该市地下水中的K⁺+Na⁺、Ca²⁺、Mg²⁺、F^-、Cl^-、S$O^{2-}_{4}$、HC$O^{-}_{3}$、N$H^{+}_{4}$、TDS和总硬度主要成分的环境背景值。结果表明: 研究区地下水主要成分的分布类型以正态分布为主,对数正态分布较少,无偏态分布类型; 与20世纪90年代江汉平原东部地区相比,本次计算获得的地下水背景值阳离子中Ca²⁺相对减少,K⁺+Na⁺、Mg²⁺均相对增加,但变化幅度较小; 除HC$O^{-}_{3}$增加外,其余阴离子均减少,且变化幅度较大。地下水化学成分的变化主要与北部山区岩石风化溶解和地下水径流、氧化还原条件有关。     

东营凹陷史112区块沙三中亚段深水重力流体系精细刻画及在开发中的意义

深水重力流作为一种重要的、特殊类型的沉积体系,自发现以来就得到了学术界的广泛关注,并在油气勘探中日益受到重视。东营凹陷古近系沙三中段发育深水重力流体系,综合地震、岩心、测录井等资料,对郝家油田史112区块深水重力流体系的沉积类型、特征及在不同层序中的发育演化进行了精细刻画,总结了该区重力流沉积模式,为开发区储层预测提供重要参考。研究表明,本区深水重力流体系发育于三级层序的高位域,从下至上可划分出4个四级层序(SQQ^1-4),主要发育滑塌沉积、碎屑流沉积和浊流沉积3种成因类型,可识别出12种岩相组合。四级层序$\mathrm{SQQ}_{3}^{2}$时期重力流规模较小,$\mathrm{SQQ}_{3}^{3}$时期随着东营三角洲向湖盆中心推进,重力流规模扩大。滑塌沉积主要发育在三角洲前缘或前三角洲斜坡根部,在滑塌沉积前方形成碎屑流沉积,碎屑流向前搬运的过程中,逐渐转化成浊流沉积。三角洲前缘及前三角洲的浊流和碎屑流是开发井区进一步寻找储层的有利部位。     

硼同位素分馏的实验理论认识和矿床地球化学研究进展

硼是一种中等挥发性元素,具有¹¹B和¹⁰B两个稳定同位素。两个同位素间高达10%的相对质量差使其在地质过程中引起高达-70‰至+75‰的硼同位素变化。硼在自然界主要与氧键合形成三配位(BO₃)和四配位(BO₄)结构,因而¹¹B和¹⁰B间同位素分馏主要受控于三配体(BO₃)和四面体(BO₄)间配分。本文综述了低温和高温地质过程的硼同位素分馏的理论和实验研究进展。在溶液中B(OH)₃和${B(OH)^{-}_{4}}$间硼同位素分馏受pH和热力学p-T条件控制,实验和理论表征获得常温常压条件下的B(OH)₃和$B(OH)^{-}_{4}$间同位素分馏系数(α_3-4)变化范围为1.019 4至1.033 3。低温条件下矿物(如碳酸盐、黏土矿物(蒙脱石和伊利石)、针铁矿、水锰矿、硼酸盐)与溶液间硼同位素分馏行为除了受p-T-pH影响外,矿物表面吸附引起的分馏效应十分显著。在中高温过程(蒙脱石伊利石化、富硼电气石和白云母矿物与热液流体,以及硅酸盐熔体与流体)中硼同位素分馏行为受到硼配位构型、化学成分以及物理化学条件的控制。随着硼同位素分馏机理研究的深入以及越来越完善的地质储库硼同位素端员特征表征,硼同位素地球化学指标可以灵敏示踪成矿物质来源、探究成矿作用与成因模式和重建成矿过程物理化学条件。目前矿床硼同位素地球化学研究的难点在于实现不同赋存相(如流体、矿物和熔体)中硼配位键合结构和硼同位素组成的精细化表征。     

云南祥云县王家庄碱性温泉水化学特征与成因分析

位于云南省祥云县刘厂镇的王家庄温泉水样YMD10-1(王家热水井)与YMD10-2(聚龙温泉宾馆热水井)的矿化度为1.49~1.65 g/L,主要阳离子为Na^+,主要阴离子为HCO3^-,水化学类型均为HCO3-Na型。YMD10-1和YMD10-2的p H值野外测定数据分别为10.8和7,因YMD10-2暴露于空气使其pCO2较高导致其p H野外观测值偏低;实验室p H测定值分别为8和7.6,主要受到pCO2差异影响导致水中碳酸组分发生变化而改变了其p H值。水样的δ^2H-δ^18O数据显示温泉的补给来源为大气降水。利用Si O2温标估算了温泉的地下热储温度为89~92℃。利用226Ra-222Rn法估算出YMD10-1的热水年龄为446.84 a,YMD10-2的热水年龄为319.56 a。估算的地下热水的循环深度为3 808~3 898 m,利用δ^2H和δ^18O估算热水补给高程为2 845~2 865 m,补给区为周边的山区。地下水获得大气降水入渗补给后,经历深循环并获得深部热流加热,沿断裂带上升穿透浅部第四系出露地表。温泉显示碱性是由于长石与水和CO2发生反应,产生大量的HCO3^-,HCO3^-在溶液中有可能水解消耗H^+产生OH^-。王家庄温泉被当地人们用来晒制土碱,与热水Na^+和碳酸的含量高有关。     

An experimental study of Ti and Zr partitioning among zircon, rutile, and granitic melt

In order to evaluate the effect of trace and minor elements (e.g., P, Y, and the REEs) on the high-temperature solubility of Ti in zircon (zrc), we conducted 31 experiments on a series of synthetic and natural granitic compositions [enriched in TiO₂ and ZrO₂; Al/(Na + K) molar ~1.2] at a pressure of 10 kbar and temperatures of ~1,400 to 1,200 °C. Thirty of the experiments produced zircon-saturated glasses, of which 22 are also saturated in rutile (rt). In seven experiments, quenched glasses coexist with quartz (qtz). SiO₂ contents of the quenched liquids range from 68.5 to 82.3 wt% (volatile free), and water concentrations are 0.4–7.0 wt%. TiO₂ contents of the rutile-saturated quenched melts are positively correlated with run temperature. Glass ZrO₂ concentrations (0.2–1.2 wt%; volatile free) also show a broad positive correlation with run temperature and, at a given T, are strongly correlated with the parameter (Na + K + 2Ca)/(Si·Al) (all in cation fractions). Mole fraction of ZrO₂ in rutile $ \left( {\mathop X\nolimits_{{{\text{ZrO}}_{ 2} }}^{\text{rt}} } \right) $ in the quartz-saturated runs coupled with other 10-kbar qtz-saturated experimental data from the literature (total temperature range of ~1,400 to 675 °C) yields the following temperature-dependent expression: $ {\text{ln}}\left( {\mathop X\nolimits_{{{\text{ZrO}}_{ 2} }}^{\text{rt}} } \right) + {\text{ln}}\left( {a_{{{\text{SiO}}_{2} }} } \right) = 2.638(149) - 9969(190)/T({\text{K}}) $ , where silica activity $ a_{{{\text{SiO}}_{2} }} $ in either the coexisting silica polymorph or a silica-undersaturated melt is referenced to α-quartz at the P and T of each experiment and the best-fit coefficients and their uncertainties (values in parentheses) reflect uncertainties in T and $ \mathop X\nolimits_{{{\text{ZrO}}_{2} }}^{\text{rt}} $ . NanoSIMS measurements of Ti in zircon overgrowths in the experiments yield values of ~100 to 800 ppm; Ti concentrations in zircon are positively correlated with temperature. Coupled with values for $ a_{{{\text{SiO}}_{2} }} $ and $ a_{{{\text{TiO}}_{2} }} $ for each experiment, zircon Ti concentrations (ppm) can be related to temperature over the range of ~1,400 to 1,200 °C by the expression: $ \ln \left( {\text{Ti ppm}} \right)^{\text{zrc}} + \ln \left( {a_{{{\text{SiO}}_{2} }} } \right) - \ln \left( {a_{{{\text{TiO}}_{2} }} } \right) = 13.84\left( {71} \right) - 12590\left( {1124} \right)/T\left( {\text{K}} \right) $ . After accounting for differences in $ a_{{{\text{SiO}}_{2} }} $ and $ a_{{{\text{TiO}}_{2} }} $ , Ti contents of zircon from experiments run with bulk compositions based on the natural granite overlap with the concentrations measured on zircon from experiments using the synthetic bulk compositions. Coupled with data from the literature, this suggests that at T ≥ 1,100 °C, natural levels of minor and trace elements in “granitic” melts do not appear to influence the solubility of Ti in zircon. Whether this is true at magmatic temperatures of crustal hydrous silica-rich liquids (e.g., 800–700 °C) remains to be demonstrated. Finally, measured $ D_{\text{Ti}}^{{{\text{zrc}}/{\text{melt}}}} $ values (calculated on a weight basis) from the experiments presented here are 0.007–0.01, relatively independent of temperature, and broadly consistent with values determined from natural zircon and silica-rich glass pairs.     

洛美沙星和诺氟沙星对水中生物反硝化过程的影响模拟试验

近年来水环境中硝酸盐污染与抗生素污染的现象引起了人们的广泛关注,但目前复合抗生素污染对反硝化过程产生的影响并不明确。本研究以水环境中检出率较高的诺氟沙星和洛美沙星为代表进行模拟实验,探究ng级的两种抗生素复合对反硝化过程的影响。硝氮和亚硝氮的降解情况表明,实验浓度条件下,洛美沙星、诺氟沙星单用与二者联用对水环境中的反硝化过程存在不同的抑制作用。洛美沙星单用前期轻微促进反硝化,后期表现抑制作用,而诺氟沙星单用始终表现出抑制作用;洛美沙星和诺氟沙星联用抑制作用小于诺氟沙星单用,联用表现为拮抗作用。各体系的抑制作用大小为诺氟沙星>诺氟沙星+洛美沙星>洛美沙星。该模拟试验条件虽与实际条件有所差异,但在一定程度上表明抗生素联用表现出拮抗作用与反硝化体系内微生物数量、活性,反硝化酶活性,反硝化菌优势物种Achromobacter xylosoxidans、Acinetobacter baumannii、Pseudomonas sp.KY及功能基因nosZ和aac的丰度的变化有关。抗生素加入反硝化体系后会产生持续的影响,随反应时间的增加,反硝化菌逐渐适应有低浓度抗生素存在的环境,喹诺酮类抗生素耐药基因数量增加,微生物的耐药性增强,反硝化菌在数量和活性、反硝化酶活性及微生物群落层面均有回升趋势。     

A multi-isotope approach for understanding sources of water,carbon and sulfur in natural springs of the Central Appalachian region

Natural springs have been reliable sources of domestic water and have allowed for the development of recreational facilities and resorts in the Central Appalachians. The structural history of this area is complex and it is unknown whether these natural springs receive significant recharge from modern precipitation or whether they discharge old water recharged over geological times scales. The main objective of this study was to use stable isotopes of water ( $\delta^{18} {\text{O}}_{{{\text{H}}_{2} {\text{O}}}}$ and $\delta^{2} {\text{H}}_{{{\text{H}}_{2} {\text{O}}}}$ ), dissolved inorganic carbon ( $\delta^{13} {\text{C}}_{\text{DIC}}$ ) and dissolved sulfate ( $\delta^{34} {\text{S}}_{{{\text{SO}}_{4} }}$ and $\delta^{18} {\text{O}}_{{{\text{SO}}_{4} }}$ ) to delineate sources of water, carbon and sulfur in several natural springs of the region. Our preliminary isotope data indicate that all springs are being recharged by modern precipitation. The oxygen isotope composition indicates that waters in thermal springs did not encounter the high temperatures required for O isotope exchange between the water and silicate/carbonate minerals, and/or the residence time of water in the aquifers was short due to high flow rates. The carbon isotopic composition of dissolved inorganic carbon and sulfur/oxygen isotopic composition of dissolved sulfate provide evidence of low-temperature water–rock interactions and various biogeochemical transformations these waters have undergone along their flow path.     

Zinc isotope fractionation under vaporization processes and in aqueous solutions

Equilibrium Zn isotope fractionation was investigated using first-principles quantum chemistry methods at the B3LYP/6-311G* level. The volume variable cluster model method was used to calculate isotope fractionation factors of sphalerite, smithsonite, calcite, anorthite, forsterite, and enstatite. The water-droplet method was used to calculate Zn isotope fractionation factors of Zn²⁺-bearing aqueous species; their reduced partition function ratio factors decreased in the order \(\left[ {{\text{Zn}}\left( {{\text{H}}_{2} {\text{O}}} \right)_{6} } \right]^{2 + } > \left[ {{\text{ZnCl}}\left( {{\text{H}}_{2} {\text{O}}} \right)_{5} } \right]^{ + } > \left[ {{\text{ZnCl}}_{2} \left( {{\text{H}}_{2} {\text{O}}} \right)_{4} } \right] > \left[ {{\text{ZnCl}}_{3} \left( {{\text{H}}_{2} {\text{O}}} \right)_{2} } \right]^{ - } > {\text{ZnCl}}_{4} ]^{2 - }\). Gaseous ZnCl₂ was also calculated for vaporization processes. Kinetic isotope fractionation of diffusional processes in a vacuum was directly calculated using formulas provided by Richter and co-workers. Our calculations show that in addition to the kinetic isotope effect of diffusional processes, equilibrium isotope fractionation also contributed nontrivially to observed Zn isotope fractionation of vaporization processes. The calculated net Zn isotope fractionation of vaporization processes was 7–7.5‰, with ZnCl₂ as the gaseous species. This matches experimental observations of the range of Zn isotope distribution of lunar samples. Therefore, vaporization processes may be the cause of the large distribution of Zn isotope signals found on the Moon. However, we cannot further distinguish the origin of such vaporization processes; it might be due either to igneous rock melting in meteorite bombardments or to a giant impact event. Furthermore, isotope fractionation between Zn-bearing aqueous species and minerals that we have provided helps explain Zn isotope data in the fields of ore deposits and petrology.     

Weathering Processes in the Min Jiang: Major Elements, {}^{87}{\text{Sr/}}{}^{86}{\text{Sr}},\;\delta {}^{34}{\text{S}}_{{\text{SO}}_{\text{4}} } ,\;{\text{and}}\;\delta {}^{18}{\text{O}}_{{\text{SO}}_{\text{4}} }

We investigated the dissolved major elements, $ {}^{87}{\text{Sr/}}{}^{86}{\text{Sr}},\;\delta {}^{34}{\text{S}}_{{\text{SO}}_{\text{4}} } ,\;{\text{and}}\;\delta {}^{18}{\text{O}}_{{\text{SO}}_{\text{4}} } $ composition of the Min Jiang, a headwater tributary of the Chang Jiang (Yangtze River). A forward calculation method was applied to quantify the relative contribution to the dissolved load from rain, evaporite, carbonate, and silicate reservoirs. Input from carbonate weathering dominated the major element composition (58–93%) and that from silicate weathering ranged from 2 to 18% in unperturbed Min Jiang watersheds. Most samples were supersaturated with respect to calcite, and the CO₂ partial pressures were similar to or up to ～5 times higher than atmospheric levels. The Sr concentrations in our samples were low (1.3–2.5 μM) with isotopic composition ranging from 0.7108 to 0.7127, suggesting some contribution from felsic silicates. The Si/(Na^* + K) ratios ranged from 0.5 to 2.5, which indicate low to moderate silicate weathering intensity. The $ \delta {}^{34}{\text{S}}_{{\text{SO}}_{\text{4}} } \;{\text{and}}\;\delta {}^{18}{\text{O}}_{{\text{SO}}_{\text{4}} } $ for five select samples showed that the source of dissolved sulfate was combustion of locally consumed coal. The silicate weathering rates were 23–181 × 10³ mol/km²/year, and the CO₂ consumption rates were 31–246 × 10³ mol/km²/year, which are moderate on a global basis. Upon testing various climatic and geomorphic factors for correlation with the CO₂ consumption rate, the best correlation coefficients found were with water temperature (r ² = 0.284, p = 0.009), water discharge (r ² = 0.253, p = 0.014), and relief (r ² = 0.230, p = 0.019).     

Impact of land use change on groundwater quality in a typical karst watershed of southwest China: a case study of the Xiaojiang watershed,Yunnan Province

The impact of land-use change on the quality of groundwater in the Xiaotjiang watershed, China was assessed for the period 1982–2004. Groundwater samples were collected from 30 monitoring points across the watershed, and were representative of the various changes, determined by remote sensing and geographical information systems. The results indicate that 610 km² (60% of the total watershed area) were subject to land-use change during the period. The most important changes were the conversion of 135 km² of forested land to cultivated land, and 211 km² of unused land to cultivated land. The main impact was ascribed to diffuse pollution from fertilizers applied to newly cultivated land, and from building development. Overall the groundwater pH value was significantly increased, as were the concentrations of ions , , , , and Cl⁻ in groundwater whilst the concentrations of Ca²⁺ and declined. More precisely, in the regions where forested land and unused land were converted into cultivated land, the pH value and the concentrations of Mg²⁺, , , , , Cl⁻ increased whilst the concentrations of Ca²⁺ and declined. However in the region where cultivated land was converted into construction land, the pH value and the concentrations of Ca²⁺, Mg²⁺, , , , , , Cl⁻ increased.

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Résumé  L’impact des changements de l’utilisation du territoire sur la qualité de l’eau souterraine dans le bassin versant de Xiaojiang, en Chine, a été évalué de 1982 à 2004. Des échantillons d’eau souterraine ont été récoltés à partir de 30 points d’observation éparpillés sur le bassin, représentant les divers changements déterminés par télédétection et système d’information géographique. Les résultats indiquent que 610 km² (soit 60% de la surface du bassin) ont été sujets à des modifications de l’utilisation du territoire sur cette période. Les changements les plus importants furent la conversion de 135 km² de forêt et 211 km² de terres inutilisées en terres cultivées. Le principal impact est attribué à la pollution diffuse des engrais utilisés en agriculture et pour les batiments. De manière générale le pH de l’eau souterraine a augmenté significativement, ainsi que les concentrations des ions , , , , et Cl⁻, tandis que les concentration en Ca²⁺ et ont diminué. Plus précisément dans les régions transformées en terres cultivées, la valeur du pH et les concentrations en Mg²⁺, , , , , Cl⁻ ont augmenté tandis que les concentrations en Ca²⁺ et ont diminué. Toutefois dans les régions cultivées converties en zones de construction, le pH et les concentrations en Ca²⁺, Mg²⁺, , , , , , Cl⁻ ont augmenté.

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Resumen  El impacto del cambio en uso de la tierra en la calidad del agua en la cuenca Xiaojiang, China fue evaluado para el periodo 1982–2004. Muestras de agua subterránea fueron tomadas de 30 puntos de monitoreo a través de la cuenca, y fueron representativas de los múltiples cambios, determinados por sensores remotos y sistemas de información geográfica. Los resultados indican que 610 km² (60% del área total de la cuenca) estaban sujetos a cambios de uso de la tierra durante el periodo estudiado. Los cambios más importantes fueron la conversión de 135 km² de bosques a tierra cultivada, y 211 km² de tierra sin uso (ociosa) a tierra cultivada. El impacto principal fue causado por contaminación difusa de fertilizantes aplicados a la tierra recientemente cultivada, y a desarrollo de construcciones. En general el pH en agua subterránea creció significantemente, al igual que las concentraciones de los iones , , , , y Cl⁻ en agua subterránea mientras que las concentraciones de Ca²⁺ y decrecieron. Mas precisamente, en las regiones donde bosque y tierra ociosa fueron convertidas en tierra cultivada, el valor de pH y las concentraciones de Mg²⁺, , , , , Cl⁻ crecieron mientras las concentraciones de Ca²⁺ y decrecieron. Sin embargo en la región donde tierra cultivada fue convertida en construcciones, el valor de pH y las concentraciones de Ca²⁺, Mg²⁺, , , , , , Cl⁻ crecieron.

     

The Hydrolysis of Al(III) in NaCl solutions: A Model for M(II), M(III), and M(IV) Ions

Understanding the identity and stability of the hydrolysis products of metals is required in order to predict their behavior in natural aquatic systems. Despite this need, the hydrolysis constants of many metals are only known over a limited range of temperature and ionic strengths. In this paper, we show that the hydrolysis constants of 31 metals [i.e. Mn(II), Cr(III), U(IV), Pu(IV)] are nearly linearly related to the values for Al(III) over a wide range of temperatures and ionic strengths. These linear correlations allow one to make reasonable estimates for the hydrolysis constants of +2, +3, and +4 metals from 0 to 300°C in dilute solutions and 0 to 100°C to 5 m in NaCl solutions. These correlations in pure water are related to the differences between the free energies of the free ion and complexes being almost equal $$ \Updelta {\text{G}}^\circ \left( {{\text{Al}}^{3 + } } \right) - \Updelta {\text{G}}^\circ \left( {{\text{Al}}\left( {\text{OH}} \right)_{j}^{{\left( {3 - j} \right)}} } \right) \cong \Updelta {\text{G}}^\circ \left( {{\text{M}}^{n + } } \right) - \Updelta {\text{G}}^\circ \left( {{\text{M}}\left( {\text{OH}} \right)_{j}^{{\left( {n - j} \right)}} } \right) $$ The correlation at higher temperatures is a result of a similar relationship between the enthalpies of the free ions and complexes $$ \Updelta {\text{H}}^\circ \left( {{\text{Al}}^{3 + } } \right) - \Updelta {\text{H}}^\circ \left( {{\text{Al}}\left( {\text{OH}} \right)_{j}^{3 - j} } \right) \cong \Updelta {\text{H}}^\circ \left( {{\text{M}}^{n + } } \right) - \Updelta {\text{H}}^\circ \left( {{\text{M}}\left( {\text{OH}} \right)_{j}^{n - j} } \right) $$ The correlations at higher ionic strengths are the result of the ratio of the activity coefficients for Al(III) being almost equal to that of the metal. $$ \gamma \left( {{\text{M}}^{n + } } \right)/\gamma \left( {{\text{M}}\left( {\text{OH}} \right)_{j}^{n - j} } \right) \cong \gamma \left( {{\text{Al}}^{3 + } } \right)/\gamma \left( {{\text{Al}}\left( {\text{OH}} \right)_{j}^{3 - j} } \right) $$ The results of this study should be useful in examining the speciation of metals as a function of pH in natural waters (e.g. hydrothermal fresh waters and NaCl brines).     

(Ca,Mg)2Si2O6 clinopyroxenes: A solution model based on nonconvergent site-disorder

Experiments at high pressure and temperature indicate that excess Ca may be dissolved in diopside. If the (Ca, Mg)₂Si₂O₆ clinopyroxene solution extends to more Ca-rich compositions than CaMgSi₂O₆, macroscopic regular solution models cannot strictly be applied to this system. A nonconvergent site-disorder model, such as that proposed by Thompson (1969, 1970), may be more appropriate. We have modified Thompson's model to include asymmetric excess parameters and have used a linear least-squares technique to fit the available experimental data for Ca-Mg orthopyroxene-clinopyroxene equilibria and Fe-free pigeonite stability to this model. The model expressions for equilibrium conditions \(\mu _{{\text{Mg}}_{\text{2}} {\text{Si}}_{\text{2}} {\text{O}}_{\text{6}} }^{{\text{opx}}} = \mu _{{\text{Mg}}_{\text{2}} {\text{Si}}_{\text{2}} {\text{O}}_{\text{6}} }^{{\text{cpx}}} \) (reaction A) and \(\mu _{{\text{Ca}}_{\text{2}} {\text{Si}}_{\text{2}} {\text{O}}_{\text{6}} }^{{\text{opx}}} = \mu _{{\text{Ca}}_{\text{2}} {\text{Si}}_{\text{2}} {\text{O}}_{\text{6}} }^{{\text{cpx}}} \) (reaction B) are given by: 1 $$\begin{gathered} \Delta \mu _{\text{A}}^{\text{O}} = {\text{RT 1n}}\left[ {\frac{{(X_{{\text{Mg}}}^{{\text{opx}}} )^2 }}{{X_{{\text{Mg}}}^{{\text{M1}}} \cdot X_{{\text{Mg}}}^{{\text{M2}}} }}} \right] - \frac{1}{2}\{ W_{21} [2(X_{{\text{Ca}}}^{{\text{M2}}} )^3 - (X_{{\text{Ca}}}^{{\text{M2}}} ] \hfill \\ {\text{ + 2W}}_{{\text{22}}} [X_{{\text{Ca}}}^{{\text{M2}}} )^2 - (X_{{\text{Ca}}}^{{\text{M2}}} )^3 + \Delta {\text{G}}_{\text{*}}^{\text{0}} (X_{{\text{Ca}}}^{{\text{M1}}} \cdot X_{{\text{Ca}}}^{{\text{M2}}} )\} \hfill \\ {\text{ + W}}^{{\text{opx}}} (X_{{\text{Wo}}}^{{\text{opx}}} )^2 \hfill \\ \Delta \mu _{\text{B}}^{\text{O}} = {\text{RT 1n}}\left[ {\frac{{(X_{{\text{Ca}}}^{{\text{opx}}} )^2 }}{{X_{{\text{Ca}}}^{{\text{M1}}} \cdot X_{{\text{Ca}}}^{{\text{M2}}} }}} \right] - \frac{1}{2}\{ 2W_{21} [2(X_{{\text{Mg}}}^{{\text{M2}}} )^2 - (X_{{\text{Mg}}}^{{\text{M2}}} )^3 ] \hfill \\ {\text{ + W}}_{{\text{22}}} [2(X_{{\text{Mg}}}^{{\text{M2}}} )^3 - (X_{{\text{Mg}}}^{{\text{M2}}} )^2 + \Delta {\text{G}}_{\text{*}}^{\text{0}} (X_{{\text{Mg}}}^{{\text{M1}}} \cdot X_{{\text{Mg}}}^{{\text{M2}}} )\} \hfill \\ {\text{ + W}}^{{\text{opx}}} (X_{{\text{En}}}^{{\text{opx}}} )^2 \hfill \\ \hfill \\ \end{gathered} $$ where 1 $$\begin{gathered} \Delta \mu _{\text{A}}^{\text{O}} = 2.953 + 0.0602{\text{P}} - 0.00179{\text{T}} \hfill \\ \Delta \mu _{\text{B}}^{\text{O}} = 24.64 + 0.958{\text{P}} - (0.0286){\text{T}} \hfill \\ {\text{W}}_{{\text{21}}} = 47.12 + 0.273{\text{P}} \hfill \\ {\text{W}}_{{\text{22}}} = 66.11 + ( - 0.249){\text{P}} \hfill \\ {\text{W}}^{{\text{opx}}} = 40 \hfill \\ \Delta {\text{G}}_*^0 = 155{\text{ (all values are in kJ/gfw)}}{\text{.}} \hfill \\ \end{gathered} $$ . Site occupancies in clinopyroxene were determined from the internal equilibrium condition 1 $$\begin{gathered} \Delta G_{\text{E}}^{\text{O}} = - {\text{RT 1n}}\left[ {\frac{{X_{{\text{Ca}}}^{{\text{M1}}} \cdot X_{{\text{Mg}}}^{{\text{M2}}} }}{{X_{{\text{Ca}}}^{{\text{M2}}} \cdot X_{{\text{Mg}}}^{{\text{M1}}} }}} \right] + \tfrac{1}{2}[(2{\text{W}}_{{\text{21}}} - {\text{W}}_{{\text{22}}} )(2{\text{X}}_{{\text{Ca}}}^{{\text{M2}}} - 1) \hfill \\ {\text{ + }}\Delta G_*^0 (X_{{\text{Ca}}}^{{\text{M1}}} - X_{{\text{Ca}}}^{{\text{M2}}} ) + \tfrac{3}{2}(2{\text{W}}_{{\text{21}}} - {\text{W}}_{{\text{22}}} ) \hfill \\ {\text{ (1}} - 2X_{{\text{Ca}}}^{{\text{M1}}} )(X_{{\text{Ca}}}^{{\text{M1}}} + \tfrac{1}{2})] \hfill \\ \end{gathered} $$ where δG _E ⁰ =153+0.023T+1.2P. The predicted concentrations of Ca on the clinopyroxene Ml site are low enough to be compatible with crystallographic studies. Temperatures calculated from the model for coexisting ortho- and clinopyroxene pairs fit the experimental data to within 10° in most cases; the worst discrepancy is 30°. Phase relations for clinopyroxene, orthopyroxene and pigeonite are successfully described by this model at temperatures up to 1,600° C and pressures from 0.001 to 40 kbar. Predicted enthalpies of solution agree well with the calorimetric measurements of Newton et al. (1979). The nonconvergent site disorder model affords good approximations to both the free energy and enthalpy of clinopyroxenes, and, therefore, the configurational entropy as well. This approach may provide an example for Febearing pyroxenes in which cation site exchange has an even more profound effect on the thermodynamic properties.