Intragrain oxygen isotope zoning in titanite by SIMS: Cooling rates and fluid infiltration along the Carthage‐Colton Mylonite Zone,Adirondack Mountains,NY, USA

Oxygen isotopes are an attractive target for zoning studies because of the ubiquity of oxygen‐bearing minerals and the dependence of mineral ¹⁸O/¹⁶O ratios on temperature and fluid composition. In this study, subtle intragrain oxygen isotope zoning in titanite is resolved at the 10‐μm scale by secondary ion mass spectrometry. The patterns of δ¹⁸O zoning differ depending on microstructural context of individual grains and reflect multiple processes, including diffusive oxygen exchange, partial recrystallization, grain‐size reduction, and grain growth. Using the chronological framework provided by structural relations, these processes can be related to specific events during the Grenville orogeny. Titanite was sampled from two outcrops within the Carthage‐Colton Mylonite Zone (CCMZ), a long‐lived shear zone that ultimately accommodated exhumation of the Adirondack Highlands from beneath the Adirondack Lowlands during the Ottawan phase (1090–1020 Ma) of the Grenville orogeny. Titanite is hosted in the Diana metasyenite complex, which preserves three sequentially developed fabrics: an early NW‐dipping protomylonitic fabric (S₁) is crosscut by near‐vertical ultramylonitic shear zones (S₂), which are locally reoriented by a NNW‐dipping mylonitic fabric (S₃). Texturally early titanite (pre‐S₂) shows diffusion‐dominated δ¹⁸O zoning that records cooling from peak Ottawan, granulite‐facies conditions. Numerical diffusion models in the program Fast Grain Boundary yield good fits to observed δ¹⁸O profiles for cooling rates of 50 ± 20 °C Ma^?1, which are considerably faster than the 1–5 °C Ma^?1 cooling rates previously inferred for the Adirondack Highlands from regional thermochronology. High cooling rates are consistent with an episode of rapid shearing and exhumation along the CCMZ during gravitational collapse of the Ottawan orogen at c. 1050 Ma. Texturally later titanite (syn‐S₂) has higher overall δ¹⁸O and shows a transition from diffusion‐dominated to recrystallization‐dominated δ¹⁸O zoning, indicating infiltration of elevated‐δ¹⁸O fluids along S₂ shear zones and continued shearing below the blocking temperature for oxygen (~≤500 °C for grain sizes at the study site). The texturally latest titanite (post‐S₃) has growth‐dominated δ¹⁸O zoning, consistent with porphyroblastic grain growth following cessation of shearing along the Harrisville segment of the CCMZ.     

Differing controls on river‐ and lake‐water hydrogen and oxygen isotopic values in the western United States

Surface water oxygen and hydrogen isotopic values are commonly used as proxies of precipitation isotopic values to track modern hydrologic processes while proxies of water isotopic values preserved in lake and river sediments are used for paleoclimate and paleoaltimetry studies. Previous work has been able to explain variability in USA river‐water and meteoric‐precipitation oxygen isotope variability with geographic variables. These studies show that in the western United States, river‐water isotopic values are depleted relative to precipitation values. In comparison, the controls on lake‐water isotopic values are not well constrained. It has been documented that western United States lake‐water input values, unlike river water, reflect the monthly weighted mean isotopic value of precipitation. To understand the differing controls on lake‐ and river‐water isotopic values in the western United States, we examine the seasonal distribution of precipitation, evaporation and snowmelt across a range of seasonality regimes. We generate new predictive equations based on easily measured factors for western United States lake‐water, which are able to explain 69–63% of the variability in lake‐water hydrogen and oxygen isotopic values. In addition to the geographic factors that can explain river and precipitation values, lake‐water isotopic values need factors related to local hydrologic and climatic characteristics to explain variability. Study results suggest that the spring snowmelt runs off the landscape via rivers and streams, depleting river and stream‐water isotopic values. By contrast, lakes receive seasonal contributions of precipitation in proportion to the seasonal fraction of total annual precipitation within their watershed. Climate change may alter the ratio of snow to rain fall, affecting water resource partitioning between rivers and lakes and by implication of groundwater. Paleolimnological studies must account for the multiple drivers of water isotopic values; likewise, studies based on the isotopic composition of fossil material need to distinguish between species that are associated with rivers versus lakes. Copyright © 2010 John Wiley & Sons, Ltd.     

Root‐related rhodochrosite and concretionary siderite formation in oxygen‐deficient conditions induced by a ground‐water table rise

Sedimentological, mineralogical, stable carbon and oxygen isotope determinations and biomarker analyses were performed on siderite concretions occurring in terrestrial silts to understand their formation and to characterize the sedimentary and diagenetic conditions favouring their growth. High δ¹³C values (6·4‰ on average) indicate that siderite precipitated in an anoxic environment where bacterial methanogenesis operated. The development of anoxic conditions during shallow burial was induced by a change in sedimentary environment from flood plain to swamp, related to a rise of the ground‐water table. Large amounts of decaying plant debris led to efficient oxygen consumption within the pore‐water in the peat. Oxygen depletion, in combination with a decrease in sedimentation rate, promoted anoxic diagenetic conditions under the swamp and favoured abundant siderite precipitation. This shows how a change in sedimentary conditions can have a profound impact on the early‐diagenetic environment and carbonate authigenesis. The concretions contain numerous rhizoliths; they are cemented with calcium‐rhodochrosite, a feature which has not been reported before. The rhodochrosite cement has negative δ¹³C values (?16·5‰ on average) and precipitated in suboxic conditions due to microbial degradation of roots coupled to manganese reduction. The exceptional preservation of the epidermis/exodermis and xylem vessels of former root tissues indicates that the rhodochrosite formed shortly after the death of a root in water‐logged sediments. Rhodochrosite precipitated during the initial stages of concretionary growth in suboxic microenvironments within roots, while siderite cementation occurred simultaneously around them in anoxic conditions. These suboxic microenvironments developed because oxygen was transported from the overlying oxygenated soil into sediments saturated with anoxic water via roots acting as permeable conduits. This model explains how separate generations of carbonate cements having different mineralogy and isotopic compositions, which would conventionally be regarded as cements precipitated sequentially in different diagenetic zones during gradual burial, can form simultaneously in shallow burial settings where strong redox gradients exist around vertically oriented permeable root structures.     

Iron isotopic systematics of UHP eclogites respond to oxidizing fluid during exhumation

The iron stable isotope compositions (δ⁵⁶Fe) and iron valence states of ultrahigh‐pressure eclogites from Bixiling in the Dabie orogen belt, China, were measured to trace the changes of geochemical conditions during vertical transportation of earth materials, for example, oxygen fugacity. The bulk Fe³⁺/ΣFe ratios of retrograde eclogites, determined by Mössbauer spectroscopy, are consistently higher than those of fresh eclogites, suggesting oxidation during retrograde metamorphism and fluid infiltration. The studied eclogites (five samples) display limited mid‐ocean ridge basalts (MORB)‐like (~0.10‰) δ⁵⁶Fe values, which are indistinguishable from their protoliths, that is, gabbro cumulates formed through differentiation of mantle‐derived basaltic magma. This suggests that Fe isotope fractionation during continental subduction is limited. Garnet separates display limited δ⁵⁶Fe variation ranging from ?0.08 ± 0.07 ‰ to 0.02 ± 0.07‰, whereas coexisting omphacite displays a large variation of δ⁵⁶Fe values from 0.15 ± 0.07‰ to 0.47 ± 0.07‰. Omphacite also has highly variable Fe³⁺/ΣFe ratios from 0.367 ± 0.025 to 0.598 ± 0.024, indicating modification after peak metamorphism. Omphacite from retrograde eclogites has elevated Fe³⁺/ΣFe ratios (0.54–0.60) compared to that from fresh eclogites (~0.37), whereas garnet displays a narrow range of ferric iron content with Fe³⁺/ΣFe ratios from 0.039 ± 0.013 to 0.065 ± 0.022. The homogenous δ⁵⁶Fe values and Fe³⁺/ΣFe ratios of garnet suggest that it survived the retrograde metamorphism and preserved its Fe‐isotopic features and ferric contents of peak metamorphism. Because of similar diffusion rates of Fe and Mg in garnet and omphacite, and constant Δ²⁶Mg_{omphacite‐garnet} values (1.14 ± 0.04‰), equilibrium iron isotope fractionation between garnet and omphacite was probably achieved during peak metamorphism. Elevated Fe³⁺/ΣFe ratios of omphacite from retrograde eclogites and variant Δ⁵⁶Fe_{omphacite‐garnet} values of the studied eclogites (0.13 ± 0.10‰ to 0.48 ± 0.10‰) indicate that oxidized geofluid infiltration resulted in the elevation of δ⁵⁶Fe values of omphacite during retrograde metamorphism.     

广西栗木钨锡铌钽矿区流体包裹体及氢氧同位素研究

本文通过对广西栗木矿区金竹源矿床和水溪庙矿床的流体包裹体研究,得出该矿区流体包裹体主要有两相H_2O-NaCl和H_2O-NaCl-CO_2两种类型。显微测温结果表明:两相H_2O-NaCl型流体包裹体均一温度主要集中于181.9~258.8℃,盐度w(Na Cleq)主要集中于4.01%~6.87%,密度0.690~0.988 g/cm3;H_2O-NaCl-CO_2型流体包裹体均一温度为178.5~331.1℃,主要集中在两个温度段,分别为高-中温段(265.3~315.5℃)和中-低温段(202.3~264.1℃),盐度w(NaCleq)主要集中在0.21%~5.05%,密度为0.678~0.886 g/cm3。栗木矿区成矿流体有两个温度集中段,且具有低盐度、低密度的特征。氢氧同位素研究结果表明:金竹源矿床钨锡铌钽矿化花岗岩石英δD值为-73.6‰~-62.8‰,δ~(18)OV-SMOW值为7.5‰~8.9‰,计算得δ~(18)OH2O值为6.00‰~7.40‰;水溪庙矿床钨锡铌钽矿化花岗岩石英δD值为-73.8‰~-58.3‰,δ~(18)OV-SMOW值为11.0‰~13.2‰,计算得δ~(18)OH2O值为9.50‰~11.70‰,水溪庙矿床含钨锡石英脉石英δD值为-75.3‰~-56.6‰,δ~(18)OV-SMOW值为11.8‰~14.1‰,计算得δ~(18)OH2O值为2.20‰~4.50‰。栗木矿区钨锡铌钽矿化花岗岩成矿流体来源于岩浆水,含钨锡石英脉成矿流体来源于岩浆水和大气降水的混合流体。     

相对湿度和PM2.5浓度对大气能见度的影响研究:基于小时资料的多站对比分析

为了全面分析浙江省不同区域能见度变化基本特征及影响机理,基于杭州、宁波、温州3个国家基本气象站2013-2014年逐时能见度观测资料,比较分析了3市能见度变化的基本特征。发现3市不同等级能见度出现频率基本一致,随着能见度等级的提高,出现频率逐渐降低;从能见度的日变化来看,07时（北京时）前后最低,之后缓慢上升,14-15时达到最高,随后逐渐下降;全年有两个能见度较低时段,分别出现在12月-次年2月和5-6月;总体而言,宁波能见度最优,杭州和温州大体相当。功率谱分析结果表明,3市能见度均有显著的日周期,高频波段呈现出多个显著谱峰,低频波段存在若干显著谱峰。进一步开展机理分析,发现相对湿度和PM_2.5浓度是调制大气能见度的关键因子,相对湿度增大、PM_2.5浓度升高导致能见度降低。在同一相对湿度等级下,初始阶段能见度随PM_2.5浓度的升高迅速降低,到达“拐点”之后降低速率趋于缓慢。在同一PM_2.5浓度水平下,相对湿度越大,能见度越低,说明水汽对能见度也有重要影响。基于相对湿度和PM_2.5浓度两个因子,采用非线性拟合方案构建了大气能见度定量统计模型,总体而言模型拟合效果较好。最后针对研究中存在的不足和未来值得进一步发掘的科学问题进行了讨论。     

中国中东部冬季霾日的形成与东亚冬季风和大气湿度的关系

利用1961-2013年中国地面台站长期观测资料和同期NCEP/NCAR再分析资料,以华北、江淮和华南为研究区,分析了中国中东部冬季霾日的形成与东亚冬季风以及大气湿度的关系。结果表明:(1)冬季霾日与东亚冬季风强度成显著的负相关。首先,东亚冬季风强度的减弱使得地面风速减小,进而导致冬季霾日增多。其中,华北7-8 m/s最大风速日数和江淮6-8 m/s最大风速日数的减少,及华南≤2 m/s最大风速日数的增多对各区冬季霾日的增多作用较大。其次,东亚冬季风减弱引起冬季气温的持续升高,易导致冬季霾日的增多,这在华北地区较之在江淮和华南更为明显。(2)由于气候变暖,冬季气温升高,使得近地面相对湿度减小。在江淮和华南地区,冬季霾日的增多与近地面相对湿度的减小显著相关,而在华北地区这种相关较弱。(3)冬季气温升高也有利于大气层结稳定度的增强,3个区域冬季霾日的增多均与大气层结稳定度的增强显著相关,特别是与对流层中低层(850-500 hPa)大气饱和度的降低显著相关。(4)冬季霾日数变化与区域水汽输送关系密切。其中,华北地区的冬季霾日数与水汽总收入成显著正相关,江淮地区与纬向水汽收入成显著正相关,与经向水汽收入成显著负相关,华南地区与经向水汽收入成显著负相关。     

无锡梅雨期湿沉降综合分析

利用2008—2014年梅雨期间酸雨观测资料及2014年6月16—27日降水个例加密采样资料,结合大气污染物资料分析了近7 a无锡梅雨期酸雨特征,研究降水过程中空气污染物、p H值、电导率的变化及降水对污染物的清除作用。结果表明:无锡市梅雨期酸雨年平均p H值呈现逐年递增趋势。降水过程中,颗粒物质量浓度显著降低;气体浓度变化受其自身日变化及排放源影响大于雨水的清除作用;样品的p H值、K值每个过程变化并不一致,K值变化与颗粒物质量浓度变化大致保持一致。降水、风对颗粒物质量浓度影响大于对气体浓度的影响。长时间连续降水时,降水对颗粒污染物的清除存在极限。小时雨量在0~0.5 mm时,降水对颗粒物浓度做负清除,其值反而略有增加;小时雨量在0.6~5.0 mm时,降水对颗粒物质量浓度做正清除;小时雨量达到5.1 mm及以上时,对PM_(2.5)和PM_(2.5-10)做正清除,对PM_(10)做负清除。降水对SO_2有稀释清除作用;对NO_2的稀释作用取决于其开始浓度值;对CO、O_3的清除作用不显著。     

同化FY3B/IRAS资料对GRAPES分析场影响诊断

GRAPES(Globe and Regional Assimilation and Prediction System)变分系统能够同化常规资料和非常规卫星资料,这些被同化的资料究竟对同化系统得到的分析场有何影响,目前国内外尚未见相关的研究文献。为此,首次采用基于信息熵信号自由度思想,诊断风云三号B星(FY3B)红外分光计(Infrared Atmospheric Sounder,IRAS)资料对GRAPES分析场的影响。诊断过程中,采用数值逼近方法,统计2012年12月24日18时到2013年1月22日00时共114个时次IRAS资料对GRAPES分析场影响,结果表明,IRAS中高层通道亮温资料对GRAPES分析场影响比地表通道20观测亮温的影响大,地表通道8和9观测亮温对分析场影响较大。前24个GRAPES变分同化时次每个时次IRAS通道亮温对分析场影响的贡献率分析结果显示,高层通道和H_2O通道贡献率较大。个例分析结果表明,在同化探空资料基础上加入IRAS资料后,温度和湿度增量场变化幅度较大,表明IRAS资料对分析场有降温和增湿作用。     

从平衡-封闭-静态转向非平衡-开放-动力学研究-热液矿床成因的若干新概念概述

热液金属矿床成因研究过程中,观测与实验始终是密切结合的。上世纪70年代,平衡热力学的实验数据的快速积累,使人们用热力学理论计算可以预测和反演矿石和岩石的成因。但是,没有矿物-水溶液的反应速率数据,又没有与流体力学的结合,搞清楚矿石成因是困难的。七、八十年代,开始研究矿物与水溶液的反应动力学实验。科学家们开始瞄准了从平衡-封闭-静态转向非平衡-开放-动力学研究的这个大方向。1992年我们建立地球化学动力学开放研究实验室。研究高温高压矿物与水反应速率,发现固液的开放体系的自组织现象。实验发现温度影响矿物的各个元素反应速率改变,发现在跨越水临界态时矿物与水反应速率涨落、在近临界的气-液两相不混溶区一些金属进入气相、超临界流体的氧化作用及特别的溶剂性能影响矿物溶解性质。实验证实:临界态区流体与矿石成因有关。水岩相互作用的反应动力学实验温度从低温到550度,揭示矿石的金属来源、迁移、金属与蚀变分带机制。一大批大于300度的矿物与水反应动力学实验在国际界是少有报道的。九十年代,超高压的科学发展,与同步辐射光源的技术进步的结合,使固体地球科学又迈向了地球深内部。我们发展了高温高压流体性质的原位直测(测量850℃水溶液)红外谱,发现深部流体的新性质:气液两相流体的新结构,在临界温度区(300~400℃),水分子氢键网络的破坏受压力影响不大(23MPa~3GPa),同时,出现水的高电导率。研发新仪器为开放-流动-非平衡的反应动力学实验与极端条件下物质性质的直接观测结合,在科学前沿领域开辟了创新道路。