高砷地下水中溶解性有机碳和无机碳稳定同位素特征

随着稳定同位素分析技术的逐步完善,碳稳定同位素被广泛应用于地球化学领域。高砷地下水砷的生物地球化学循环是目前环境化学研究热点之一。分析概括了碳稳定同位素应用于地下水领域的研究现状,介绍了地下水中有机碳和无机碳稳定同位素的前处理方法以及测试技术。在此基础上,选取了内蒙古河套平原具有代表性的高砷地下水进行氧化还原敏感组分、碳稳定同位素的测定与分析。结果表明,As分布极不均匀,其含量为1.24~387 μg/L。地下水溶解性有机碳(DOC)含量相对较高,与溶解性无机碳(DIC)浓度基本呈正相关。δ¹³C_DIC相对δ¹³C_DOC较富集¹³C;δ¹³C_DIC-δ¹³C_DOC与δ¹³C_DIC之间具有显著的正相关关系;表明δ¹³C_DIC值越贫化,δ¹³C_DIC-δ¹³C_DOC越小,地下水中来源于有机物氧化分解的无机碳越多,进一步说明有机碳的氧化分解在无机碳稳定同位素贫化过程中起主要作用。此外,δ¹³C_DIC-δ¹³C_DOC与As浓度呈一定的负相关关系;表明有机物的微生物降解对砷的富集具有明显的促进作用。微生物可利用的碳源增加,促进异养微生物的代谢,并消耗氧气,最终形成有利于地下水As富集的还原环境。     

Petro-tectonic Imprints in the Sapphirine Granulites from Anantagiri, Eastern Ghats Mobile Belt, India

Sapphirine granulite occurring as lenses in charnockite at Anantagiri,Eastern Ghat, India, displays an array of minerals which developedunder different P-T-X conditions. Reaction textures in conjunctionwith mineral chemical data attest to several Fe-Mg continuousreactions, such as

1. spinel+rutile+quartz+MgFe_–1=sapphirine+ilmenite
2. cordierite=sapphirine+quartz+MgFe_–1
3. sapphirine+quartz=orthopyroxene+sillimanite+MgFe_–1
4. orthopyroxene+sapphirine+quartz=garnet+MgFe_–1
5. orthopyroxene+sillimanite=garnet+quartz+MgFe_–1
6. orthopyroxene+sillimanite+quartz+MgFe_–1=cordierite.

Calculated positions of the reaction curves in P-T space, togetherwith discrete P-T points obtained through geothermobarometryin sapphirine granulite and the closely associated charnockiteand mafic granulite, define an anticlockwise P-T trajectory.This comprises a high-T/P prograde metamorphic path which culminatedin a pressure regime of 8?3 kb above 950?C, a nearly isobariccooling (IBC) path (from 950?C, 8?3 kb, to 675?C, 7?5kb) anda terminal decompressive path (from 7?5 to 4?5 kb). Spinel,quartz, high-Mg cordierite, and sapphirine were stabilized duringthe prograde high-T/P metamorphism, followed by the developmentof orthopyroxene, sillimanite, and garnet during the IBC. Retrogradelow-Mg cordierite appeared as a consequence of decompressionin the sapphirine granulite. Deformational structures, reportedfrom the Eastern Ghat granulites, and the available geochronologicaldata indicate that prograde metamorphism could have occurredat 30001?00 and 2500?100 Ma during a compressive orogeny thatwas associated with high heat influx through mafic magmatism. IBC ensued from P_max and was thus a direct consequence of progrademetamorphism. However, in the absence of sufficient study onthe spatial variation in P-T paths and the strain historiesin relation to time, the linkage between IBC and isothermaldecompression (ITD) has remained obscure. A prolonged IBC followedby ITD could be the consequence of one extensional mechanismwhich had an insufficient acceleration at the early stage, orITD separately could be caused by an unrelated extensional tectonism.The complex cooled nearly isobarically from 2500 Ma. It sufferedrapid decompression accompanied by anorthosite and alkalinemagmatism at 1400–1000 Ma.     

Petrology of the Udayagiri anorthosite complex, Eastern Ghats Belt, India

The Eastern Ghats Belt (EGB), characterised by pervasive Grenvillian granulite facies metamorphism, is the host to several 950–1000 Ma old massif-type anorthosite complexes. The present work describes one such complex near Udayagiri from the northern margin of the EGB, reported for the first time as “Udayagiri anorthosite complex” (UAC). The ‘massif type’ UAC comprises mainly of anorthosite, leuconorite-olivine leuconorite and norite in the decreasing order of areal extent. Mineralogically, these rocks dominantly consist of cumulates of moderately calcic plagioclase (～An_50–60), moderately magnesian intercumulus olivine (X_Mg: ～0.6) and orthopyroxene (X_Mg: 0.47 to 0.70). Metamorphic garnet (Alm: ～50 mol%) is also common in these rocks. Anorthosite and leuconorite of the UAC exhibit a moderate ‘+ve’ Eu anomaly. Norite occurs locally as schlierens and is relatively rich in Fe, P, Rb, Sr, Th, Nb, Ta, Y and REE which could be a residual melt product. These rocks exhibit both relict magmatic mineralogy and textures with a metamorphic impress manifested by the development of multilayered corona involving olivine, orthopyroxene, garnet, phlogopite, ilmenite and plagioclase during cooling of the pluton. The corona development is a result of combination of significant magmatic and metamorphic reactions which have the potential to provide important clues for deciphering the magmatic and metamorphic evolution of such plutons in ambient granulite facies conditions.     

Ultrapotassic Rocks along Late Ductile Shear Zones from the Eastern Ghats Belt,India

Ultrapotassic rock is reported for the first time from the polycyclic Eastern Ghats belt, India, near Borra, Visakhapatnam district, Andhra Pradesh. The rock, consisting of leucite, kalsilite, Khyphen;feldspar, graphite, apatite together with diopside, meionite and phlogopite, occurs as thin vein and veinlets in diopsidite, in close spatial association with a granulite facies carbonate ensemble of massive dolomitic carbonate rock and calc silicate granulite. It was emplaced in the midhyphen;crust along late ductile shear zones. Subsequent to its emplacement, the ultrapotassic melt with liquidus leucite interacted with the granulite wall rock, incorporating at least 40% of the crustal components mainly as Si, Al, Mg and Ca. After necessary correction of the crustal contaminant, the recalculated K₂O/Na₂O ratio of ∼12 (molar) and K₂O/Al₂O₃ ratio of ∼1 (molar) in the bulk rock composition indicates that the Borra ultrapotassic melt has a lamproitic affinity. However, it is significantly modified as well, particularly being impoverished in mafic liquidus phases and depleted in incompatible (excepting Rb, Th and U) and compatible trace elements, compared to an average lamproite. Leucite later underwent subsolidus decomposition to Khyphen;feldspar + kalsilite intergrowths. The emplacement of the ultrapotassic melt posthyphen;dates an early ultra high temperature metamorphism and also the 1000 Ma Grenvillian metamorphism in the Eastern Ghats Belt and is possibly of Panhyphen;African age. The extensive Khyphen;feldspathisation in the Eastern Ghats belt could also be linked with this ultrapotassic melt.     

柴达木盆地新生代以来的气候变化研究:来自碳氧同位素的证据

青藏高原北缘柴达木盆地内部始新世—更新世的碳酸盐中的碳、氧同位素分析结果显示了几次与区域性气候变化和构造运动相关的地质事件,包括青藏高原形成和隆升。新生代厚层的湖相-陆相沉积物记录了在中新世时气候以干旱条件为主。红三旱剖面中出现了两个较短1 Ma到3 Ma的δ13C变化周期。通过稳定同位素的研究可以识别出4个明显的构造事件:(1)上干柴沟组晚期δ13C和δ18O出现明显的增加,反映周边山脉的隆升;(2)上干柴沟组和下油砂山组界限处δ13C和δ18O的剧减,反映了整个柴达木盆地的总体抬升和喜马拉雅山在24 Ma左右的隆起;(3)19~18 Ma同位素数据出现的正异常峰值应该和阿尔金山的强烈隆起有关,同时盆地相对沉降,地貌高差增大,气候变得干旱;(4)12 Ma的明显负异常反映了整个柴达木盆地的海拔又一次增高,而盆地本身相对沉降周边山脉隆升。     

淮南煤田张集煤矿煤层中稳定有机碳同位素分布特征

通过对淮南煤田张集煤矿9个煤层的33个煤样稳定有机碳同位素的分析,研究了碳同位素值(δ13C)在煤层中的分布特征和变化趋势.研究表明:张集煤矿煤的δ13C值范围为-23.44‰-25.37‰,平均-24.18‰,不同煤层的δ13C值范围不同,为煤层识别和对比提供了新的依据;自下而上由4-1煤至11-2煤层碳同位素均值呈波动变化,在6煤和9-1煤处分别达到极小值和极大值,这种差异反应了不同煤层的成煤植物生长时期古环境的变化,特别是大气中CO2和温度的变化,与沉积环境也存在着相关性.     

Petrology of gedrite-bearing rocks in mid-crustal ductile shear zones from the Eastern Ghats Belt, India

A suite of metapelitic, basic and quartzofeldspathic rocks intruded by enderbitic gneiss from the southernmost tip of the Eastern Ghats Belt, India, and metamorphosed at c. 750–800  °C, 6  kbar, were subjected to repeated ductile shear deformation, hydration, cooling and accompanying alkali metasomatism along narrow shear zones. Gedrite-bearing assemblages developed in the shear zones traversing metapelitic rocks. Interpretation of the reaction textures in an appropriate P–T  grid in the system FMASH, an isothermal–isobaric μ _H2O– μ _Na2O grid in the system NFMASH, and geothermobarometric data suggest a complex evolutionary history for the gedrite-bearing parageneses. Initially, gedrite-bearing assemblages were produced due to increase in μ _Na2O at nearly constant but high μ _H2O accompanying cooling. Gedrite was partially destabilized to orthopyroxene+albite due to progressively increasing μ _Na2O. During further cooling and at increased μ _H2O a second generation of gedrite appeared in the rocks.     

A HFSE- and REE-enriched ferrodiorite suite from the Bolangir Anorthosite Complex, Eastern Ghats Belt, India

The massif-type anorthosite complex at Bolangir in the northern part of the Eastern Ghats belt occurs in a milieu of predominantly supracrustal granulite-grade rocks. The massif is separated from the host gneisses by coarse-grained garnetiferous granitoid gneisses which are interpreted as coeval crustallyderived melts. Melanocratic ferrodiorite rocks occur at the immediate contact with the anorthosite massif which they intrude in cross-cutting dikes and sheets. The emplacement age of the anorthosite diapir and the associated igneous suites is deemed to be pre-D₂. Recrystallization of the igneous assemblages of the ferrodiorite suite (750–800°C, 7–8kbar, ) during a period of near-isobaric cooling from the igneous crystallization stage to the regionalP-T regime led to extensive development of coronitic garnet at the interface of plagioclase phenocrysts with the mafic matrix assemblage (opx + fay + cpx + ilm ± amph, bio). Abundant accessory phases are zircon, apatite and thorite. The mafic phases have extremely ferrous compositions (X_Fe gar: 0.93-0.87, fay: 0.90-0.87, opx: 0.80-0.60, cpx: 0.70-0.47, amph: 0.81-0.71) reflecting the low Mg-number (16-8) of the rocks. Compared to worldwide occurrences of similar rocks, the Bolangir ferrodiorites (SiO₂ 36–58 wt.%, FeO*: 39-10 wt.%) are characterized by exceptionally high concentrations of HFSE and REE (TiO₂: 4.8-1.0 wt.%, P₂O₅: 1.7-0.5 wt.%, Zr: 5900-1300 ppm, Y: 240-80 ppm, La: 540-100 ppm, Ce: 1100-200 ppm, Yb: 22-10 ppm, Th: 195-65 ppm). Well defined linear variation trends for major and trace elements reflect progressive plagioclase accumulation towards the felsic members of the suite. The ferrodiorites are interpreted to represent residual liquids of anorthosite crystallization which after segregation and extraction from the ascending diapir became enriched in HFSE and REE through selective assimilation of accessory phases (zircon, monazite, apatite) from crustal felsic melts. Ferromonzodioritic rock presumably formed through hybridization between the ferrodiorite and overlying felsic melts.     

Temporal Variability in the Concentration and Stable Carbon Isotope Composition of Dissolved Inorganic and Organic Carbon in Two Montana,USA Rivers

Here we report diel (24 h) and seasonal differences in the concentration and stable carbon isotope composition of dissolved inorganic (DIC) and organic carbon (DOC) in the Clark Fork (CFR) and Big Hole (BHR) Rivers of southwestern Montana, USA. In the CFR, DIC concentration decreased during the daytime and increased at night while DOC showed an inverse temporal relationship; increasing in the daytime most likely due to release of organic photosynthates and decreasing overnight due to heterotrophic consumption. The stable isotope composition of DIC (δ¹³C-DIC) became enriched during the day and depleted over night and the δ¹³C-DOC displayed the inverse temporal pattern. Additionally, the night time molar rate of decrease in the concentration of DOC was up to two orders of magnitude smaller than the rate of increase in the concentration of DIC indicating that oxidation of DOC was responsible for only a small part of the increase in inorganic carbon. In the BHR, in two successive years (late summer 2006 & 2007), the DIC displayed little diel concentration change, however, the δ¹³C-DIC did show a more typical diel pattern characteristic of the influences of photosynthesis and respiration indicating that the isotopic composition of DIC can change while the concentration stays relatively constant. During 2006, a sharp night time increase in DOC was measured; opposite to the result observed in the CFR and may be related to the night time increase in flow and pH also observed in that year. This night time increase in DOC, flow, and pH was not observed 1 year later at approximately the same time of year. An in-stream mesocosm chamber used during 2006 showed that the night time increase in pH and DOC did not occur in water that was isolated from upstream or hyporheic contributions. This result suggests that a “pulse” of high DOC and pH water was advected to the sampling site in the BHR in 2006 and a model is proposed to explain this temporal pattern.     

Stability of fluorite and titanite in a calc-silicate rock from the Vizianagaram area, Eastern Ghats Belt, India

In the Vizianagaram area (E 83°29.442′; N 18°5.418′) of the Eastern Ghats Belt, India, a suite of graphite‐bearing calc‐silicate granulites, veined by syenitic rocks, developed wollastonite‐rich veins at 6–7 kbar and > 850 °C. During subsequent near‐isobaric cooling wollastonite was replaced by calcite + quartz and a graphic intergrowth of fluorite + quartz ± clinopyroxene. Titanite with variable Al and F contents is present throughout the rock. Combining the compositional variation of titanite and recent experimental data, it is demonstrated that the mineral assemblage, the composition of coexisting fluids and the mobility of Al exert a far greater control on the composition of titanite than pressure, temperature or the whole rock composition. Thermodynamically computed isothermal–isobaric logf_O2– logf_CO2 and logf_F2– logf_O2 grids in the systems Ca–Fe–Si–O–F (CISOF; calcite‐free) and Ca–Fe–Si–O–F–C–H (CISOFV; calcite‐present) demonstrate the influence of bulk rock and fluid compositions on the stability of the fluorite‐bearing assemblages in diverse geological environments and resolve the problem of the stability of titanite in fayalite + fluorite‐bearing rocks in the Adirondacks. The mineralogy of the studied rocks and the topological constraints tightly fix the logf_O2, logf_F2 and logf_CO2 at ?15.8, ?30.6 and 4.1, respectively, at 6.5 kbar and c. 730 °C. Because of the similarity in the P–T conditions, the compositions of pore fluids in the fluorite‐bearing assemblages of the Adirondacks and the Eastern Ghats Belt have been compared.     

Ultrahigh-Temperature Metamorphism in Madurai Granulites, Southern India: Evidence from Carbon Isotope Thermometry

Ultrahigh-temperature (UHT) metamorphism in the Madurai Block of the southern Indian granulite terrain has been verified using the calcite-graphite isotope exchange thermometer. Carbon isotope thermometry has been applied to marbles from a locality near the reported occurrence of sapphirine granulites that have yielded temperature estimates of around 1000 degrees C. The delta(13)C and delta(18)O values of calcite are homogenous, implying equilibration of the isotopes during metamorphism. However, the delta(13)C values of single graphite crystals show variations in the order of 1 per thousand within a hand specimen. Detailed isotopic zonation studies indicate that graphite preserves either the time-integrated crystal growth history or reequilibrium fractionation during its cooling history. The graphite cores preserve higher delta(13)C values than the rims. The fractionation between calcite and graphite cores gives the highest metamorphic temperature of about 1060 degrees C, which matches the petrologically inferred temperature estimates in the high-magnesian pelites. The fractionation between graphite rims and calcite suggests a temperature of around 750 degrees C, which is interpreted to reflect retrograde cooling. This event is also observed in the sapphirine granulites. Calcite-graphite thermometry thus provides a useful tool to define UHT metamorphism in granulite terrains.     

Stable Carbon Isotope Biogeochemistry and Anthropogenic Impacts on Karst Ground Water, Zunyi, Southwest China

Natural and anthropogenic impacts on karst ground water, Zunyi, Southwest China, are discussed using the stable isotope composition of dissolved inorganic carbon and particulate organic carbon, together with carbon species contents and water chemistry. The waters can be mainly characterized as HCO₃–Ca type, HCO₃ · SO₄–Ca type, or HCO₃ · SO₄–Ca · Mg type, according to mass balance considerations. It is found that the average δ¹³C_DIC values of ground waters are higher in winter (low-flow season) than in summer (high-flow season). Lower contents of dissolved inorganic carbon (DIC) and lower values of δ¹³C_DIC in summer than in winter, indicate that local rain events in summer and a longer residence time of water in winter play an important role in the evolution of ground water carbon in karst flow systems; therefore, soil CO₂ makes a larger contribution to the DIC in summer than in winter. The range of δ¹³C_DIC values indicate that dissolved inorganic carbon is mainly controlled by the rate of carbonate dissolution. The concentrations of dissolved organic carbon and particulate organic carbon in most ground water samples are lower than 2.0 mg C L⁻¹ and 0.5 mg C L⁻¹, respectively, but some waters have slightly higher contents of organic carbon. The waters with high organic carbon contents are generally located in the urban area where lower δ¹³C_DIC values suggest that urbanization has had an effect on the ground water biogeochemistry and might threaten the water quality.     

Alkaline Magmatism Versus Collision Tectonics in the Eastern Ghats Belt, India: Constraints from Structural Studies in the Koraput Complex

Linear domains of deformed alkaline rocks and carbonatites have recently been identified as representing sites of ancient suture zones. In peninsular India, the western margin of the Proterozoic Eastern Ghats Belt (EGB) is characterized by a series of alkaline plutons that are aligned close to the contact with the Archaean Craton. Most of the complexes were deformed and metamorphosed during a subsequent orogenic event. Unlike other plutons in the belt, the alkaline complex at Koraput reportedly escaped deformation and granulite facies metamorphism forming an anomalous entity within the zone. Multiply-deformed country rocks hosting this complex underwent syn-D_1CR granulite facies metamorphism followed by D_2CR thrusting, with pervasive shearing along a NE-SW trending foliation. A second granulite facies event followed localized D_3CR shearing. Within the Koraput Complex, strain partitioning was responsible for preserving igneous textures in the gabbroic core, but aligned magmatic amphibole needles and plagioclase laths occasionally define a S_1AC fabric. Along the margins, S_1AC is rotated parallel to a NE-trending, east-dipping S_2AC fabric in the gabbro, fringing syenodiorite and nepheline syenite bands. Locally, D_3AC shearing follows D_2AC deformation; S_2AC and S_3AC parallel S_2CR and S_3CR in the country rocks. High-grade metamorphism represented by recrystallization of amphibole and plagioclase, and breakdown of amphibole and biotite to garnet, pyroxene and K-feldspar in the complex follows D_3AC. Unlike earlier reports, therefore, the Koraput body is also deformed and metamorphosed. The aligned alkaline complexes in the EGB probably represent deformed alkaline rocks and carbonatites formed by rifting related to an earlier episode of continental break-up that were deformed during subsequent juxtaposition of the EGB with the Archaean Craton. This supports the contention that the western margin of the EGB and its contact with the Archaean Craton is a suture zone related to the Indo-Antarctica collision event.     

Emplacement History of Pasupugallu Gabbro Pluton, Eastern Ghats Belt, India: a Structural Study

Structural mapping of the Pasupugallu pluton, an elliptical intrusive gabbro-anorthosite body, emplaced into the western contact zone between the Eastern Ghats Mobile Belt and the Archaean East Dharwar Craton, along the east coast of India, reveals concentric, helicoidal and inward dipping magmatic and/or tectonic foliations. We identify a <1 km-wide structural aureole characterized by pronounced deflection of regional structures into margin parallel direction, mylonitic foliations with S-C fabrics, sigmoidal clasts, moderately plunging stretching lineations, non-cylindrical intrafolial folds, and stretched elliptical mafic enclaves in the aureole rocks. Our results suggest that the pluton emplacement is syn-tectonic with respect to the regional ductile deformation associated with the terrane boundary shear zone at the western margin of the Eastern Ghats. We present a tectonic model for the emplacement of the pluton invoking shear-related ductile deformation, rotation and a minor component of lateral expansion of magma. The intrusive activity (1450-800 Ma) along the western margin of the Eastern Ghats can be correlated with the significant event of recurring mafic, alkaline and granitic magmatism throughout the global Grenvillian orogens associated with the continent-continent collision tectonics possibly related to the amalgamation and the breakup of the supercontinent Rodinia.     

Exsolution textures in orthopyroxene in aluminous granulites as indicators of UHT metamorphism: New evidence from the Eastern Ghats Belt, India

Highly aluminous orthopyroxene, coexisting with sapphirine, cordierite, sillimanite, quartz and garnet in various combinations, constitute granoblastic mosaic peak metamorphic assemblages in aluminous granulites from three localities in the Eastern Ghats Belt, India. Orthopyroxene contains four types of intergrowths: (a) involving sapphirine with or without cordierite, (b) involving spinel, but without sapphirine, (c) involving cordierite, but without sapphirine and spinel, and (d) involving garnet, without sapphirine, spinel or cordierite. On the basis of textural and compositional data, origin of the intergrowths is ascribed to breakdown of Mg-Tschermak component, locally also involving Fe- and Ti-Tschermak. An attempt is made to compute the “pre-breakdown” compositions of orthopyroxene by image analysis, which shows maximum Al₂O₃ content of 13.4 wt.% in the pristine orthopyroxene. Geothermometry, phase equilibria consideration and application of existing experimental data on alumina solubility in orthopyroxene coexisting with sapphirine and quartz, collectively indicate extreme thermal conditions of metamorphism (> 1000 °C) for the studied assemblages. This re-affirms the notion that Al₂O₃ solubility in orthopyroxene is the most powerful indicator of UHT metamorphism (Harley, S.L., 2004. Extending our understanding of ultrahigh temperature crustal metamorphism. J. Mineral. Petrol. Sci. 99, 140–158). The intergrowths are considered to have formed due to cooling from the thermal peak spanning a temperature range of approximately 150 °C. Appearance of diverse types of intergrowths is probably related to subtle differences in bulk composition, particularly Fe:Mg ratios.     

Structure of the Nagavali Shear Zone,Eastern Ghats Mobile Belt,India: Correlation in the East Gondwana Reconstruction

Interpretation of satellite data in combination with regional field traverses, delineating the major structural features such as the Nagavali and Vamsadhara Shear Zones and associated fold patterns, provides a synoptic picture of the regional tectonic framework of the central part of the Eastern Ghats Mobile Belt. The complex geology of the study area can broadly be grouped into three distinct deformational events. D₁ fabrics represented by near flat-lying gneissic foliations, paralleling the lithological banding are best preserved in low strain domains and are related to Middle to late Archaean thrusting (3000-2600 Ma). The second deformational event D₂ is characterized by the development of shear zones and associated mylonitic fabrics and magmatism probably during 1450-850 Ma. The Pan-African thermal (500-550 Ma) overprint is restricted to shear zones in the form of reworking. Regionally, the central part of the Eastern Ghats Mobile Belt can be divided into five distinct structural domains based on structural geometry of folds, foliations and lineations. A three-dimensional block diagram of the Nagavali and Vamsadhara Shear Zones involving fold-thrust tectonics associated with westward thrusting is presented here. A correlation of Pan-African Shear Zones in adjacent continents wrapping around the Archaean Dharwar Craton in the reconstruction of Rodinia and East Gondwana supercontinent suggests an east-west convergence.