Carbon Isotopic Profile Across the Bilara Group Rocks of Trans-Aravalli Marwar Supergroup in Western India: Implications for Neoproterozoic — Cambrian Transition

The rocks of Marwar Supergroup in the trans-Aravalli sector in western India are presumed to span the time interval between Neoproterozoic and early Cambrian. This, predominantly unfossiliferous, marine sedimentary sequence is characterized by a lower arenaceous facies (Jodhpur Group), middle carbonate facies (Bilara Group) and upper argillaceous— arenaceous facies (Nagaur Group) rocks. The sedimentation has been essentially in a shallow basin, described either as the fore-land slope of the rising Aravalli mountains or a sag-basin which developed and evolved due to subsidence of the updomed crust during Neoproterozoic Malani magmatism that failed to open rifts. The carbon isotopic profile for the Bilara Group carbonate rocks in the lower part shows marked oscillations and broadly negative δ¹³C character with negative anomalies as low as <−4.3‰_PDB, observed near the base of Dhanapa Formation (lower unit) and <−6.5‰_PDB in the overlying Gotan Formation (middle unit). The upper part of the profile shows a gradual positive shift. The carbon isotopic signatures of the Bilara Group rocks can be correlated with the end-Neoproterozoic — early Cambrian (Vendian — Tommotian) carbon isotopic evolution curve. Extremely low δ¹³C values indicate the glaciation related cold climatic postulates of the end-Neoproterozoic, followed by the warmer climatic conditions as indicated by the positive shift. The carbon isotopic data for Gotan Formation carbonates, at variance with the globally observed δ¹³C trends for early Tertiary, do not support the recently proposed Tertiary age for the Bilara Group.     

Cambrian trace fossils of the Cruziana ichnofacies from the Bikaner-Nagaur Basin,north western Indian Craton

The Marwar Supergroup of the Bikaner-Nagaur Basin is composed of sediments deposited from the late Neoproterozoic (Ediacaran) to Upper Cambrian. The Nagaur Sandstone Formation of the Nagaur Group (uppermost division of the Marwar Supergroup) preserves trace fossils significant for establishing Early Cambrian biostratigraphic zones and depositional facies. Fifteen ichnospecies (and eight ichnogenera) identified in the Nagaur Sandstone Formation include “Treptichnus” pedum, Cruziana cf. tenella, Cruziana isp., Diplichnites ispp. A, B, and C, Gyrophyllites isp., Lockeia isp., Merostomichnites isp., Monomorphichnus gregarius isp. nov., Monomorphichnus isp., Planolites isp., Psammichnites isp., Rusophycus bikanerus isp. nov., Rusophycus cf. carbonarius, Rusophycus isp. and radial trace fossils.These trace fossils belong to ethological categories pascichnia, repichnia, cubichnia, and fodinichnia and represent arthropod and worm-like burrowing biota. The assemblage and a regional comparison with contemporaneous trace fossils in the eastern Gondwanan realm suggest that the sequence in the study area belongs to the Cruziana tenella Ichnozone and to Stage 2 (upper part of Terreneuvian), however the Middle Cambrian is not excluded. The trace fossil assemblage belongs to the archetypal Cruziana ichnofacies. Cross bedded sandstone, mud cracks and rainprints in the ichniferous strata of the Nagaur Sandstone Formation indicate deposition in an intertidal sand flat with channels that was exposed episodically.     

Geochemical and stable isotopic evolution of the Guarani Aquifer System in the state of São Paulo, Brazil

The purpose of this report is to explain geochemical and stable isotopes trends in the Brazilian unit of the Guarani Aquifer System (Botucatu and Piramboia aquifers) in S?o Paulo State, Brazil. Trends of dissolved species concentrations and geochemical modeling indicated a significant role of cation exchange and dissolution of carbonates in downgradient evolution of groundwater chemistry. Loss of calcium by the exchange for sodium drives dissolution of carbonates and results in Na–HCO₃ type of groundwater. The cation-exchange front moves downgradient at probably much slower rate compared to the velocity of groundwater flow and at present is located near to the cities of Sert?ozinho and águas de Santa Barbara (wells PZ-34 and PZ-148, respectively) in a shallow confined area, 50–70 km from the recharge zone. Part of the sodium probably enters the Guarani Aquifer System. together with chloride and sulfate from the underlying Piramboia Formation by diffusion related to the dissolution of evaporates like halite and gypsum. High concentrations of fluorine (up to 13.3 mg/L) can be explained by dissolution of mineral fluoride also driven by cation exchange. However, it is unclear if the dissolution takes place directly in the Guarani Aquifer System or in the overlying basaltic Serra Geral Formation. There is depletion in δ ²H and δ ¹⁸O values in groundwater downgradient. Values of δ ¹³C(DIC) are enriched downgradient, indicating dissolution of calcite under closed system conditions. Values of δ ¹³C(DIC) in deep geothermal wells are very high (>–6.0‰) and probably indicate isotopic exchange with carbonates with δ ¹³C about –3.0‰. Future work should be based on evaluation of vertical fluxes and potential for penetration of contamination to the Guarani Aquifer System. Electronic Publication     

Stable isotope characterisation of co-existing carbonates from the Holocene Gallocanta lake (NE Spain): palaeolimnological implications

The sedimentary succession of Gallocanta lake, a closed saline lake located in the Iberian Range (NE Spain), documents two successive lacustrine stages: (1) brackish lake stage and (2) shallow saline lake stage. The saline stage corresponds to the present-day situation in which the lake water properties are mainly controlled by a strongly negative annual water balance. The carbonates of the brackish lake stage have relatively constant δ¹⁸O values, however, they are rather high (δ¹⁸O_Do = 2.4‰ and δ¹⁸O_Cc = 4.5‰ mean values) suggesting a hydrologically closed lake with a long residence time of the waters. δ¹⁸O values of carbonates from the saline stage vary greatly, and are lighter than in the previous stage (δ¹⁸O_Do = 0.5‰, δ¹⁸O_Cc = −0.7‰, δ¹⁸O_Mgs = −2.3‰ mean values). These carbonates also precipitated in a hydrologically closed lake, but in equilibrium with a lake water of more variable isotopic composition. The δ¹³C values for carbonates of both stages reflect a mixing of different pools of carbon, but during saline stage δ¹³C values have been more controlled by the equilibrium of the lake waters with atmospheric CO₂. During the current stage, calcite and dolomite precipitate in Gallocanta lake mainly during spring and summer, although dolomite precipitation is more favoured towards the summer. Magnesite precipitates at the beginning of autumn, when the first rainfall re-dissolves the saline surface crust, producing saline waters with a high Mg²⁺ content. The isotopic composition of lake waters sampled in 2005 are far higher than those calculated from the carbonates. It is considered that this could be due to two factors: either because there have not been many extremely dry years (like the year 2005) during the development of the lake, or because the physical and chemical characteristics of the lake waters in such conditions are not appropriate for the development of these minerals.     

Cold seep deposits of Beauvoisin (Oxfordian; southeastern France) and Marmorito (Miocene; northern Italy): microbially induced authigenic carbonates

The relation of two well-known ancient carbonate deposits to hydrocarbon seepage was confirmed by this study. Archaea are found to be associated with the formation of Oxfordian seep carbonates from Beauvoisin and with a Miocene limestone from Marmorito ("tube-worm limestone"). Carbonates formed due to a mediation by archaea exhibit extremely positive or extremely negative δ¹³C_carbonate values, respectively. Highly positive values (+15‰) reflect the use of ¹³C-enriched CO₂ produced by methanogenesis. Low δ¹³C values of the Marmorito carbonates (–30‰) indicate the oxidation of seepage-derived hydrocarbons. Likewise, the δ¹³C content of specific tail-to-tail linked isoprenoids, biomarkers for archaea, was found to be strikingly depleted in these samples (as low as –115‰). The isotopic signatures corroborate that archaea were involved in the cycling of seepage-derived organic carbon at the ancient localities. Another Miocene limestone ("Marmorito limestone") shows a strong imprint of methanotrophic bacteria as indicated by δ¹³C values of carbonate as low as –40‰ and biomarker evidence. Epifluorescence microscopy and field-emission scanning electron microscopy revealed that bacterial biofilms were involved in carbonate aggregation. In addition to lucinid bivalves previously reported from both localities, we infer that sponges from Beauvoisin and tube worms from Marmorito depended on chemosynthesis as well. Low δ¹³C values of nodules related to sponge taphonomy (–27‰) indicate that sponges might have been linked to an enhanced hydrocarbon oxidation. Tube worm fossils from Marmorito closely resemble chemosynthetic pogonophoran tube worms from Recent cold seeps and are embedded in isotopically light carbonate (δ¹³C –30‰). Received: 13 October 1998 / Accepted: 5 February 1999     

Spatial distribution characteristics of stable carbon isotope compositions in desert plant Reaumuria soongorica (Pall.) Maxim

In order to investigate the distribution characteristics of stable carbon isotope ratios (δ ¹³C) in the desert plant Reaumuria soongorica, the δ ¹³C values of leaves were measured in 407 individuals of 21 populations. Soil physicochemical properties including soil water content, soil total dissolved solids, soil total nitrogen, soil total phosphorus and soil organic content were also analyzed in order to survey the major factors influencing δ ¹³C values on spatial variation. Leaves and soil samples were simultaneously collected from the ten major distribution areas in Northwest China at altitudes from 394 m to 1 987 m above sea level, at latitudes from 36°10′N to 44°33′N, and at longitudes from 81°43′E to 106°37′E. These ten areas include Shihezi, Baicheng, Yiwu areas in Xinjiang Uygur Autonomous Region; Anxi, Zhangye, Baiyin, Lanzhou areas in Gansu Province; Shapotou, Yinchuan areas in Ningxia Hui Autonomous Region; and Alashan County in Inner Mongolia Autonomous Region. The results show that the δ ¹³C value of R. soongorica ranges from −22.77‰ to −29.85‰ with an average of −26.52‰. Foliar d13C values in R. soongorica are not significantly correlated with altitude, latitude or longitude, and a spatial distribution trend of d13C values of R. soongorica is not obvious on a large scale. However, when d13C values of two R. soongorica populations under the same climate conditions are compared, δ ¹³C values increase obviously from east to west and from north to south. As none of the soil total dissolved solids, soil total nitrogen, soil total phosphorus, and soil organic content shows a uniform trend from east to west and from north to south, we suppose that the small-scaled spatial distribution pattern of δ ¹³C values of R. soongorica is mainly controlled by the soil water content. Translated from Quaternary Sciences, 2006, 26(6): 947–954 [译自: 第四纪研究]     

The variations of stable-carbon isotope ratios in Qilian juniper in northwestern China

This is the first study of δ¹³C values that considers elevational influences of the Qilian mountains of China. The δ¹³C values of different parts of the Qilian juniper (Sabina przewalskii Kom.) at different elevations of the Qilian mountains, China, were measured. Relatively constant differences in δ¹³C values existed between the tree leaves and the trunk wood. No strong dependency of δ¹³C values on elevation was found. The temporal changes of wood δ¹³C values with directions, elevations and height in the tree showed general similarity. These results suggest that the isotopic effects of environmental factors expressed initially at the site of photosynthesis, i.e., the leaves could be contained in the trunks of a tree. Regardless of elevation, direction or height in the tree, wood δ¹³C values have been decreasing during the past 60 years. A composite 600-year δ¹³C chronology developed from four trees showed that δ¹³C values remain relatively constant before 1800. After 1800 AD, however, δ¹³C values became significantly more negative. The trend in wood δ¹³C values was consistent with that obtained for δ¹³C values in atmospheric CO₂. The results showed that for Qilian juniper, tree-ring δ¹³C chronology could be established to ascertain fluctuations of the atmospheric δ¹³C.     

Reconstructing the History of eastern and Central Florida Bay using mollusk-shell isotope records

Stable isotopic ratios of carbon and oxygen (δ¹³C and δ¹⁸O) from mollusk shells reflect the water quality characteristics of Florida Bay and can be used to characterize the great temporal variability of the bay. Values of δ¹⁸O are directly influenced by temperature and evaporation and may be related to salinity, δ¹³C values of δ¹³C are sensitive to organic and inorganic sources of carbon and are influenced by productivity. Analyses of eight mollusk species from five short-core localities across Florida Bay show large ranges in the values of δ¹³C and δ¹⁸O, and reflect the variation of the bay over decades. Samples from southwester Florida Bay have distinct δ¹³C values relative to samples collected in northeastern Florida Bay, and intermediate localities have intermediate values.¹³C values of δ¹³C grade from marine in the southwest bay to more estuarine in the northeast. Long cores (>1m), with excellent chronologies were analyzed from central and eastern Florida Bay. Preliminary analyses ofBrachiodontes exustus andTransenella spp. from the cores showed that both δ¹³C and δ¹⁸O changed during the first part of the twentieth century. After a century of relative stability during the 1800s, δ¹³C decreased between about 1910 and 1940, then stabilized at these new values for the next five decades. The magnitude of the reduction in δ¹³C values increased toward the northeast. Using a carbon budget model, reduced δ¹³C values are interpreted as resulting from decreased circulation in the bay, probably associated with decreased freshwater flow into the Bay. Mollusk shell δ¹⁸O values display several negative excursions during the 1800s, suggesting that the bay was less evaporitic than during the twentieth century. The isotope records indicate a fundamental change took place in Florida Bay circulation early in the twentieth century. The timing of the change links it to railroad building and early drainage efforts in South Florida rather than to flood control and water management measures initiated after World War II.     

Hydrogeochemistry,environmental isotopes and the origin of the Hamamayagi-Ladik thermal spring (Samsun,Turkey)

Hamamayagi thermal spring (HTS) is located along the North Anatolian Fault Zone. The thermal spring has a temperature of 36°C, with total dissolved solids ranging from 485.6 to 508.5 mg/L. Hard, brittle, and gray limestones Permian aged are the reservoir rocks of the HTS. δ¹⁸O–δ²H isotope ratios clearly indicate a meteoric origin for the waters. The δ³⁴S value of sulfate in the thermal water is nearly 4.1‰ and implies a diagenetic environment characterized by reduced sulfur compounds. The δ¹³C ratio for dissolved inorganic carbonate in the HTS lies between −1.78 and −1.62‰, showing that it originates from the dissolution of fresh-water carbonates. Quartz geothermometry suggests a reservoir temperature of 52–85°C for the Hamamayagi geothermal field, but chalcedony geothermometers suggest reservoir temperatures between 30 and 53°C.     

Isotopic and sedimentological clues to productivity change in Late Riphean Sea: A case study from two intracratonic basins of India

Enriched¹³C/¹²C ratios with δ¹³C ∼3%0 (w.r.t PDB) of two Late Riphean (∼ 700-610 Ma) intracratonic carbonate successions viz., Bhander Limestone of Vindhyan Basin and Raipur Limestone of Chattisgarh Basin suggest higher organic productivity during this period. This view is supported by sedimentological evidence of higher biohermal growth and consequent increase in depositional relief in the low gradient ramp settings inferred for these basins. Oxygen isotope analysis of these carbonates show distinct segregation between enriched deeper water carbonate mudstone and depleted shallow water stromatolite facies that received fresh water influx. This shows that facies-specific analyses can be useful in understanding the depositional setting of these sediments.     

Salinization properties of a shallow groundwater in a coastal reclaimed area,Yeonggwang, Korea

The need for more agricultural or residential land has encouraged reclamation at the coastal areas of Korea since 1200 ad (approximately). The groundwaters of these reclaimed areas could be expected to reveal hydrogeochemical properties different from those of areas directly affected by seawater intrusion. The purpose of this study, therefore, was to examine the salinization of shallow groundwater in a coastal reclaimed area and to identify the effect of land reclamation on groundwater quality. Major cations and anions, iodide, total organic carbon, δD, δ ¹⁸O and δ ¹³C were measured to assist the hydrogeochemical analysis. Chloride, δD and δ ¹⁸O data clearly show that the Na–Cl type water results from mixing of groundwater with seawater. In particular, the δD and δ ¹⁸O of Ca+Mg–Cl+NO₃ type groundwaters are close to the meteoric water line, but Na–Cl type waters enriched in chloride are ¹⁸O-enriched with respect to the meteoric water line. Meanwhile, carbon isotopic data and I/Cl ratios strongly suggest that there are various sources of salinity. The δ ¹³C values of Na–Cl type groundwaters are generally similar to those of Ca+Mg–Cl+NO₃ type waters, which are depleted in ¹³C with respect to seawater. I/Cl ratios of Na–Cl type groundwater are 10–100 times higher than that of seawater. Because the reclamation has incorporated a large amount of organic matter, it provides optimum conditions for the occurrence of redox processes in the groundwater system. Therefore, the salinization of groundwater in the study area seems to be controlled not only by saltwater intrusion but also by other effects, such as those caused by residual salts and organic matter in the reclaimed sediments.     

Geochemical characteristics of sediment pore water from Site XS-01 in the Xisha trough of South China Sea and their significance for gas hydrate occurrence

Gas hydrate is a recently-found new source of energy that mostly exists in marine sediments. In recent years, we have conducted gas hydrate exploration in the South China Sea. The Xisha trough, one of the promising target areas for gas hydrate, is located in the northern margin of the South China Sea, adjacent to several large oil and gas fields. The Xisha trough extends 420 km long with the water depth of 1 500 m in the west part and 3 400 m in the east part and deposits thick sediments with organic matter content of 0.41%–1.02%. Previous studies on topographical features, geological P-T conditions, structural geology, sedimentary geology and geophysical bottom simulating reflectors (BSR) in the Xisha trough suggest that this area is favorable for the formation and accumulation of gas hydrate. In this paper, we present geochemical analyses for the sediment and pore water from a piston core at Site XS-01 in the Xisha trough. Seven pore water samples were analyzed for their anion (Cl⁻, SO₄ ²⁻, Br⁻, I⁻) contents, cation (Na, K, Ca, Mg) contents and trace element (Li, B, Sr, Ba, Rb, Mn) contents. Eight sediment samples were analyzed for stable carbon and oxygen isotopic compositions. A number of geochemical anomalies such as anions (e.g. Cl⁻, SO₄ ²⁻), cations (e.g. Ca, Mg) and trace elements (e.g. Sr, Ba, B) were found in this study. For example, the concentrations of Cl⁻ and SO₄ ²⁻ in pore water show a decreasing trend with depth. The estimated sulfate/methane interface (SMI) is only 18 m, which is quite similar to the SMI value of 23 m in the ODP164 Leg 997 at Blake Ridge. The Ca, Mg and Sr concentrations of pore water also decrease with depth, but concentrations of Ba, and Mg/Ca and Sr/Ca ratios increase with depth. These geochemical anomalies are quite similar to those found in gas hydrate locations in the world such as the Blake Ridge and may be related to the formation and dissociation of gas hydrates. The salt exclusion effect during the gas hydrate formation will cause an increase in major ion concentrations in the pore waters that diffused upward such as Cl. The anaerobic methane oxidation (AMO) may lead to the change of SO₄ ²⁻ and other cations such as Ca, Mg, Sr and Ba in pore water. Low δ ¹³C value of authigenic carbonates is a good indicator for gas hydrate occurrence. However, the bulk sediment samples we analyzed all show normal δ ¹³C values similar to biogenic marine carbonates, and this may also suggest that no gas hydrate-related authigenic carbonates exist or their amount is so small that they are not detectable by using this bulk analytical method. In conclusion, we suggest that the Site XS-01 in the Xisha trough of the northern margin of the South China Sea is a potential target for further gas hydrate exploration. Translated from Quaternary Sciences, 2006, 26(3): 442–448 [译自: 第四纪研究]     

Characterization of C‐isotope variability in the Delhi Supergroup,northwestern India and the Mesoproterozoic ocean

Marine carbonate rocks of the Delhi Supergroup of northwestern India show little deviation in whole‐rock δ ¹³Ccarb and δ ¹⁸Ocarb values, which generally are around 0 and –10‰ respectively. These narrow ranges and almost constant δ ¹³Ccarb values persist despite close sampling through long sections. The data suggest that the global rate of organic carbon burial was probably constant during deposition of the Delhi Supergroup. The nearly invariant C isotopic profile of the Delhi Supergroup is similar to C isotopic profiles of Mesoproterozoic carbonates older than 1.3 Ga, as reported from different parts of world. Carbonate units on the western margin of the Delhi Supergroup however, have on average moderately positive δ ¹³C values (from 2 to +4.96‰). These high δ ¹³C carbonates may represent the Mesoproterozoic–Neoproterozoic transition (from ～1.25 to ～0.85 Ga), a period characterized by high positive δ ¹³C values globally.     

The Gumeshevo skarn-porphyry copper deposits in the Central Urals,Russia: Evolution of the ore-magmatic system as deduced from isotope geochemistry (Sr,Nd, C,O, H)

The Early Devonian Gumeshevo deposit is one of the largest ore objects pertaining to the dioritic model of the porphyry copper system paragenetically related to the low-K quartz diorite island-arc complex. The (⁸⁷Sr/⁸⁶Sr)_t and (ɛ_Nd)_t of quartz diorite calculated for t = 390 Ma are 0.7038–0.7045 and 5.0–5.1, respectively, testifying to a large contribution of the mantle component to the composition of this rock. The contents of typomorphic trace elements (ppm) are as follows: 30–48 REE sum, 5–10 Rb, 9–15 Y, and 1–2 Nb. The REE pattern is devoid of Eu anomaly. Endoskarn of low-temperature and highly oxidized amphibole-epidote-garnet facies is surrounded by the outer epidosite zone. Widespread retrograde metasomatism is expressed in replacement of exoskarn and marble with silicate (chlorite, talc, tremolite)-magnetite-quartz-carbonate mineral assemblage. The ⁸⁷Sr/⁸⁶Sr ratios of epidote in endoskarn and carbonate in retrograde metasomatic rocks (0.7054–0.7058 and 0.7053–0.7065, respectively) are intermediate between the Sr isotope ratios of quartz dioritic rocks and marble (⁸⁷Sr/⁸⁶Sr = 0.70784 ± 2). Isotopic parameters of the fluid equilibrated with silicates of skarn and retrograde metasomatic rocks replacing exoskarn at 400°C are δ¹⁸O = +7.4 to +8.5‰ and δD = −49 to −61‰ (relative to SMOW). The δ¹³C and δ¹⁸O of carbonates in retrograde metasomatic rocks after marble are −5.3 to +0.6 (relative to PDB) and +13.0 to +20.2% (relative to SMOW), respectively. Sulfidation completes metasomatism, nonuniformly superimposed on all metasomatic rocks and marbles with formation of orebodies, including massive sulfide ore. The δ³⁴S of sulfides is 0 to 2‰ (relative to CDT);⁸⁷Sr/⁸⁶Sr of calcite from the late calcite-pyrite assemblage replacing marble is 0.704134 ± 6. The δ¹³C and ⁸⁷Sr/⁸⁶Sr of postore veined carbonates correlate positively (r = 0.98; n = 6). The regression line extends to the marble field. Its opposite end corresponds to magmatic (in terms of Bowman, 1998b) calcite with minimal δ¹³C, δ¹⁸O, and ⁸⁷Sr/⁸⁶Sr values (−6.9 ‰, +6.7‰, and 0.70378 ± 4, respectively). The aforementioned isotopic data show that magmatic fluid was supplied during all stages of mineral formation and interacted with marble and other rocks, changing its Sr, C, and O isotopic compositions. This confirms the earlier established redistribution of major elements and REE in the process of metasomatism. A contribution of meteoric and metamorphic water is often established in quartz from postore veins.     

Transmission of <Emphasis Type="Italic">δ</Emphasis><Superscript>13</Superscript>C signals and its paleoclimatic implications in Liangfeng Cave system of Guizhou Province,SW China

A series of samples, including vegetation, soil organic matter, soil waters, spring, bedrock, pool water, drip waters (upper-drip waters and ground-drip waters) and their corresponding speleothems were collected at Liangfeng Cave (LFC) system of Guizhou Province, southwest of China, respectively, from 2003 to 2004 year, then their stable carbon isotopes were measured and analyzed. Results reveal that vegetation is C₃ type in LFC system; cave overlying δ ¹³C signals, including values and variations, could be transmitted to drip water (speleothem); speleothem δ ¹³C mainly shows a biogenic δ ¹³C value character (soil CO₂ from plant respiration and decay); and there are remarkable seasonal variations of δ ¹³C values for drip water TDIC (speleothem), which are lighter at least 2.0‰ in the rainy seasons than in the dry ones. So, it could be feasible to reconstruct high-resolution changes of paleoecology and paleoclimate by using speleothem δ ¹³C values.     

The relation of seasonal pattern in stable carbon compositions to meteorological variables in the leaves of <Emphasis Type="Italic">Sabina</Emphasis><Emphasis Type="Italic">przewalskii</Emphasis> Kom. and <Emphasis Type="Italic">Sabina chinensis</Emphasis> (Lin.) Ant.

The seasonal variation of foliar δ¹³C values in Sabina przewalskii Kom. and Sabina chinensis (Lin.) Ant. was measured. The relationships between foliar δ¹³C values and branch δ¹³C values as well as environmental factors (monthly total precipitation, monthly average air temperature, monthly average soil temperature, monthly total solar duration, relative humidity, atmospheric pressure, vapor pressure, wind speed and potential evaporation) were investigated. The results showed that the foliar δ¹³C values were negatively correlated with air pressure, and positively correlated with air temperature, precipitation, vapor pressure, potential evaporation, solar duration, wind speed and soil temperature. No significant relationship between δ¹³C values and relative humidity was detected. This demonstrates that the foliar δ¹³C of Sabina is a successful empirical indictor of these meteorological factors within the usual range of C₃ whole-leaf δ¹³C values. Furthermore, the δ¹³C signature of leaf tissue is similar to that of wood tissue and the responses of δ¹³C values in S. przewalskii Kom. to environmental factors are also relatively stronger than that of S. chinensis (Lin.) Ant. These results provided strong evidence that it is feasible to extract climatic information from tree-ring δ¹³C series and S. przewalskii Kom. is a dendroclimatologically promising tree species.     

13C/12C composition, a novel parameter to study the downward migration of paper sludge in soils?

δ ¹³C values of crop and forest soils were measured 8 years after disposal of paper sewage sludge. The carbon transfer from paper sludge downward to the first humic layer is evidenced by a ¹³C-enrichnient of up to + 5.6‰ due to the input of ¹³C-enriched sludge carbonates. ¹³C/¹²C composition is thus a novel, sensitive parameter to follow the downward transfer of paper sludge carbon.     

Geochemical properties of Neoproterozoic “cap dolomites” in the Patom paleobasin and problem of their genesis

The characteristic feature of many Upper Neoproterozoic glacial sequences is their “cap carbonates” (CC) resting without visible unconformity upon glaciogenic diamictites. Such an unusual association, peculiar structures and textures, and negative δ¹³C values (approximately −4 ± 2‰) that are atypical of marine carbonates provoked long debates about the nature of these carbonates, which play an important role in the Snowball Earth hypothesis. According to this hypothesis, the Earth was entirely covered by ice during large-scale glaciations, and CC accumulation was related to the global change in geochemical processes. In this work, we discuss data on the chemical and isotopic (C, O, Sr) compositions of CCs, which overlie glacial sediments of the Nichatka and Bol’shoi Patom formations accumulated in different parts of the Neoproterozoic Patom paleobasin (Central Siberia). High concentrations of Fe (up to 6400 ppm), Mn (2320 ppm), and radiogenic Sr (⁸⁷Sr/⁸⁶Sr₀ up to 0.7172) established in CCs indicates a strong influence of the continental flow. Extraordinary Snowball Earth conditions are not necessary for the accumulation of these rocks, geochemical and sedimentological properties of which may be explained by the discharge of thawing waters into partly or completely isolated near-glacier basin, their intermittent freezing, and/or washout of “frozen” carbonates from the surface of thawing glaciers. The peculiar thin-laminated texture of CC may be related to seasonal processes of climatic cycles. They were accumulated in the course of general (relatively long-term) depletion of the atmosphere and hydrosphere in ¹³C, which has nothing to do with the CC formation as a specific type of carbonate sediments. Amplitude and duration of the negative δ¹³C excursion in carbonates associated with the Lower Vendian glacial sediments (665–635 Ma) are appreciably lower than the negative anomaly in rocks of the Zhuya Group that likely correspond to the Shuram-Vonoka Event (∼560−580 Ma ago), which probably marks the crucial point in the Precambrian deglaciation: mass destabilization of methane hydrates and degradation of the Early Vendian psychrosphere in oceans.     

Prograde and retrograde fluid-rock interaction in calc-silicates northwest of the Idaho batholith: stable isotopic evidence

Carbon and oxygen isotopic analyses of silicate and carbonate minerals indicate that isotopic compositions in metasediments of the Wallace Formation (Belt Supergroup) exposed northwest of the Idaho batholith have been affected by both prograde and retrograde fluid-rock interaction. Silicates retain isotopic fractionations that reflect equilibration at peak metamorphic temperatures. In contrast, calcite oxygen isotopic compositions range from δ¹⁸O(Calcite)=+2.3 to +18.6‰ SMOW (standard mean oceanic water) and indicate that some calcites have exchanged with low-δ¹⁸O meteorichydrothermal fluids. Values of Δ¹⁸O (Quartz-Calcite) as large as +15.5 clearly indicate that the isotopic depletion of these calcites postdates the peak of regional metamorphism. Carbon isotopic compositions of ¹⁸O-depleted calcites are not significantly shifted relative to δ¹³C values in undepleted calcites, suggesting that the retrograde fluid was carbon-poor. Petrographically, retrograde fluid-rock interaction is associated with the occurrence of fine-grained, highly-luminescent calcite overgrowths on less-luminescent, metamorphic calcites, slight to moderate argillic alteration, and pseudomorphing of scapolite porphyroblasts by fine-grained albite. Retrograde isotopic depletions may be related to shallow meteoric-hydrothermal fluid flow developed around the Idaho batholith after intrusion and rapid uplift of the terrane. Peak metamorphic isotopic compositions in the Wallace Formation reflect mineralogically heterogeneous protolith compositions and isotopic fractionation due to devolatilization and/or infiltration. Variability in oxygen isotopic compositions on the order of 4–6‰ within the same rock type can be attributed to the combined effects of inherited isotopic compositions and isotopic shifts resulting from prograde devolatilization. Isotopic and compositional heterogeneity on the scale of mm to m precludes generalization of isotopic gradients on a regional scale. The isotopic data presented here, and metamorphic fluid compositions determined in previous studies, are best reconciled with heterogeneous bulk compositions, dominantly channelized prograde and retrograde fluid flow, and locally low fluid-rock ratios.     

Isotopic constraints on fluid evolution and precipitation mechanisms for the Boléo Cu–Co–Zn district, Mexico

Stable and radiogenic isotope composition of stratiform Cu–Co–Zn mineralization and associated sedimentary rocks within the Boléo district of the Miocene Santa Rosalía basin, Baja California Sur, constrains the evolution of seawater and hydrothermal fluids and the mechanisms responsible for sulfide and oxide deposition. Stable isotope geochemistry of limestone and evaporite units indicates a strong paleogeographic influence on the chemistry of the water column. Near-shore limestone at the base of the Boléo Formation is characterized by modified marine carbon (δ ¹³C_PDB=−6.0 to +4.4‰) and oxygen (δ ¹⁸O_SMOW=+19.5 to +26.2‰) isotope composition due to the influx of ¹³C- and ¹⁸O-depleted fluvial water. Sulfate sulfur isotope composition (δ ³⁴S_CDT=+17.21 to +22.3‰ and δ ¹⁸O_SMOW=+10.7 to +13.1‰) for basal evaporite and claystone facies are similar to Miocene seawater. Strontium isotopes are less radiogenic than expected for Miocene seawater due to interaction with volcanic rocks. Low S/C ratios, high Mn contents and sedimentological evidence indicate the basin water column was oxidizing. The oxygenated basin restricted sulfide precipitation to within the sedimentary pile by replacement of early diagenetic framboidal pyrite and pore-space filling by Cu–Co–Zn sulfides to produce disseminated sulfides. Quartz–Mn oxide oxygen isotope geothermometry constrains mineralization temperature between 18 and 118°C. Sulfur isotopes indicate the following sources of sulfide: (1) bacterial sulfate reduction within the sedimentary pile produced negative δ ³⁴S values (<−20‰) in framboidal pyrite; and (2) bacterial sulfate reduction at high temperature (80–118°C) within the sedimentary pile during the infiltration of the metal-bearing brines produced Cu–Co–Zn sulfides with negative, but close to 0‰, δ ³⁴S values. Isotope modeling of fluid-rock reaction and fluid mixing indicates: (1) sedimentary and marine carbonates (δ ¹³C=−11.6 to −3.2‰ and δ ¹⁸O=+19.0 to +21.8‰) precipitated from basin seawater/pore water that variably mixed with isotopically depleted meteoric waters; and (2) hydrothermal calcite (δ ¹³C=−7.9 to +4.3‰ and δ ¹⁸O=+22.1 to +25.8‰) formed by dissolution and replacement of authigenic marine calcite by downward-infiltrating metalliferous brine and brine-sediment exchange, that prior to reaction with calcite, had mixed with isotopically depleted pore water. The downward infiltration of metalliferous brine is inferred from lateral and stratigraphic metal distributions and from the concentration of Cu sulfides along the upper contact of pyrite-bearing laminae. The co-existence and textural relationships among framboidal pyrite, base metal sulfides, carbonate and Mn–Fe oxides (including magnetite) within mineralized units are consistent with carbonate replacement and high-temperature bacterial reduction within the sedimentary pile occurring simultaneously below a seawater column under predominantly oxygenated conditions.