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1.
The elemental shell chemistry of two freshwater snails, Viviparus diluvianus (Kunth) and Valvata piscinalis (Müller) was studied for palaeoenvironmental purposes. The shells were collected from lake sediments from five Holsteinian (Marine Isotope Stage 11) sites in eastern Poland (Ossówka, Hrud II, Roskosz, Ortel Królewski and Szymanowo) and analysed for Ca, Mg, Sr, Mn and Fe. The Fe/Mn molar ratio was used as a redox indicator, with lower values (and high Mn concentrations) pointing to suboxic conditions. These occurred in the beginning of the Taxus zone and during the transition between the Taxus and Pinus‐Larix zones at Ortel Królewski, and in the Holsteinian thermal maximum (CarpinusAbies zone) at Roskosz Lake. Strongly reducing conditions, indicated by increased Fe and Fe/Mn values, prevailed at Ortel Królewski palaeolake in the middle of the Taxus zone, in the Pinus‐Larix zone and in the upper part of the Roskosz sequence. Indicators of anoxia correlate with eutrophic conditions, enhanced productivity and oxygen consumption due to organic matter decay. The most distinct environmental changes in the records are comparable to other central and northern European records and to the main climatic oscillations during the Holsteinian, inferred from palynological, malacological and isotopic data.  相似文献   

2.
Travertine deposits in western Turkey are very well‐exposed in the area of Kocaba?, in the eastern part of the Denizli Basin. The palaeoclimatic significance of these travertines is discussed using U/Th dates, stable isotope data and palynological evidence. The Kocaba? travertine occurrences are characterized by successions of depositional terraces associated with palaeosols and karstic features. The travertines have been classified into eight lithotypes and one erosional horizon, namely: laminated, coated bubble, reed, paper‐thin raft, intraclasts, micritic travertine with gastropods, extra‐formational pebbles and a palaeosol layer. The analysed travertines mostly formed between 181 ka and 80 ka (Middle to Late Pleistocene) during a series of climatic changes including glacial and interglacial intervals; their δ13C and δ18O values indicate that the depositional waters were mainly of basinal thermal origin, occasionally mixed with surficial meteoric water. Palynological results obtained from the palaeosols showed an abundance of non‐arboreal percentage and xerophytic plants (Oleaceae and Quercus evergreen type) indicating that a drought occurred. Marine Isotope Stage 6 is represented by grassland species but Marine Isotope Stage 5 is represented by Pinaceae–Pinus and Abies, Quercus and Oleaceae. Uranium/thorium analyses of the Kocaba? travertines show that deposition began in Marine Isotope Stage 6 (glacial) and continued to Marine Isotope Stage 4 (glacial), but mostly occurred in Marine Isotope Stage 5 (interglacial). The travertine deposition continued to ca 80 ka in the south‐west of the study area, in one particular depression depositional system. Palaeoenvironmental indicators suggest that the travertine depositional evolution was probably controlled by fault‐related movements that influenced groundwater flow. Good correlation of the stable isotope values and dates of deposition of the travertines and palynological data of palaeosols in the Kocaba? travertines serve as a starting point for further palaeoclimate studies in south‐west Turkey. Additionally, the study can be compared with other regional palaeoclimate archives.  相似文献   

3.
Palaeotemperature estimates from the oxygen‐isotope compositions of belemnites have been hampered by not knowing ancient seawater isotope compositions well enough. We have tackled this problem using Mg/Ca as a proxy for temperature and here, we present a ~2 Ma record of paired Mg/Ca and δ18O measurements of Jurassic (Early Pliensbachian) belemnites from the Asturian basin as a palaeo‐proxy of seawater oxygen‐isotope composition. From the combined use of the two approaches, we suggest a δ18Ow composition of about ?0.1‰ for the Jamesoni–Ibex zones. This value may have been increased by about 0.6‰ during the Davoei Zone due to the effect of waters with a different δ18Ow composition. These findings illustrate the inaccuracy of using a globally homogeneous ice‐free value of δ18Ow = ?1‰ for δ18Ocarb‐based palaeotemperature reconstructions. Our data suggest that previous palaeotemperatures calculated in the region from δ18O values of belemnites may have been underestimated as the seawater oxygen isotopic composition could have been higher.  相似文献   

4.
We present in this article a rapid method for B extraction, purification and accurate B concentration and δ11B measurements by ID‐ICP‐MS and MC‐ICP‐MS, respectively, in different vegetation samples (bark, wood and tree leaves). We developed a rapid three‐step procedure including (1) microwave digestion, (2) cation exchange chromatography and (3) microsublimation. The entire procedure can be performed in a single working day and has shown to allow full B recovery yield and a measurement repeatability as low as 0.36‰ (± 2s) for isotope ratios. Uncertainties mostly originate from the cation exchange step but are independent of the nature of the vegetation sample. For δ11B determination by MC‐ICP‐MS, the effect of chemical impurities in the loading sample solution has shown to be critical if the dissolved load exceeds 5 μg g?1 of total salts or 25 μg g?1 of DOC. Our results also demonstrate that the acid concentration in the sample loading solution can also induce critical isotopic bias by MC‐ICP‐MS if chemistry of the rinsing‐, bracketing calibrator‐ and sample solutions is not thoroughly adjusted. We applied this method to provide a series of δ11B values of vegetal reference materials (NIST SRM 1570a = 25.74 ± 0.21‰; NIST 1547 = 40.12 ± 0.21‰; B2273 = 4.56 ± 0.15‰; BCR 060 = ?8.72 ± 0.16‰; NCS DC73349 = 16.43 ± 0.12‰).  相似文献   

5.
《Applied Geochemistry》2005,20(3):519-527
Pleistocene vegetation history on the Chinese Loess Plateau has been traditionally investigated using palynological methods, and questions remain regarding whether an extensive broadleaf deciduous forest ever developed on the loess table under favorable climatic conditions. The authors have employed a C isotope approach to address this question by comparing δ13C values in soil organic matter from different loess ecological domains with known source vegetation to the C isotope values obtained from a paleosol section that can be dated back to 130 ka. The C isotopic compositions of modern soils from the loess table and the loess–desert transition gave δ13C values of −24.5‰ to −18.2‰ and −25.7‰ to −20.7‰, respectively. These C isotopic ratios are consistent with the standing modern vegetation that is dominated by a mixture of C3 and C4 plants and can be distinguished from that in the patchy forest areas where exclusive C3 trees yield a narrow δ13C value range from −26.9‰ to −25‰ (average −26.1‰). Obtained δ13C compositions from paleosols and loess sediments in the Lantian and the Luochuan profiles vary from −24‰ to −16.9‰, indicating a grass-dominated steppe with shifting C3 and C4 contributions controlled mainly by paleoclimatic changes during the late Pleistocene. The present results suggest no extensive forest coverage on the loess table during the past 130 ka even under the most suitable conditions for forest development. This conclusion supports the explanation of natural causes for the development of only patchy forests on the modern loess table and provides critical historical information toward the vegetation restoration project that is currently underway on the Chinese Loess Plateau.  相似文献   

6.
In this study, the accuracy and the precision corresponding to Li isotopic measurements of low level samples such as marine and coastal carbonates are estimated. To this end, a total of fifty‐four analyses of a Li‐pure reference material (Li7‐N) at concentrations ranging from 1 to 6 ng ml?1 were first performed. The average δ7Li values obtained for solutions with and without chemical purification were 30.3 ± 0.4‰ (2s,= 19) and 30.2 ± 0.4‰ (2s,= 36), respectively. These results show that the chosen Li chemical extraction and purification procedure did not induce any significant isotope bias. Two available carbonate reference materials (JCt‐1 and JCp‐1) were analysed, yielding mean δ7Li values of 18.0 ± 0.27‰ (2s,= 6) and 18.8 ± 1.8‰ (2s,= 9), respectively. Small powder aliquots (< 15 mg) of JCp‐1 displayed significant isotope heterogeneity and we therefore advise favouring JCt‐1 for interlaboratory comparisons. The second part of this study concerns the determination of δ7Li value for biogenic carbonate samples. We performed a total of twenty‐nine analyses of seven different tropical coral species grown under controlled and similar conditions (24.0 ± 0.1 °C). Our sample treatment prior to Li extraction involved removal of organic matter before complete dissolution in diluted HCl. Our results show (a) a constant δ7Li within each skeleton and between the different species (δ7Li = 17.3 ± 0.7‰), and (b) a Li isotope fractionation of ?2‰ compared with inorganic aragonite grown under similar conditions. Comparison with literature data suggests a significant difference between samples living in aquaria and those grown in natural conditions. Finally, we investigate ancient (fossil) carbonate material and foraminifera extracted from marine sedimentary records. Different leaching procedures were tested using various HCl molarities. Results indicate that carbonate preferential dissolution must be carried out at an acid molarity < 0.18 mol l?1. Possible contamination from silicate minerals can be verified using the Al/Ca ratio, but the threshold value strongly depends on the carbonate δ7Li value. When the silicate/carbonate ratio is high in the sediment sample (typically > 2), contamination from silicates cannot be avoided, even at low HCl molarity (? 0.1 mol l?1). Finally, bulk carbonate and foraminifera extracted from the same core sample exhibited significant discrepancies: δ7Li values of foraminifera were more reproducible but were significantly lower. They were also associated with lower Sr/Ca and higher Mn/Ca ratios, suggesting a higher sensitivity to diagenesis, although specific vital effects cannot be fully ruled out.  相似文献   

7.
As a result of the scarcity of isotopic reference waters for daily use, a new secondary isotopic reference material for international distribution has been prepared from ice‐core water from the Amundsen–Scott South Pole Station. This isotopic reference material, designated as USGS49, was filtered, homogenised, loaded into glass ampoules, sealed with a torch, autoclaved to eliminate biological activity and measured by dual‐inlet isotope‐ratio mass spectrometry. The δ2H and δ18O values of USGS49 are ?394.7 ± 0.4 and ?50.55 ± 0.04 mUr (where mUr = 0.001 = ‰), respectively, relative to VSMOW, on scales normalised such that the δ2H and δ18O values of SLAP reference water are, respectively, ?428 and ?55.5 mUr. Each uncertainty is an estimated expanded uncertainty (= 2uc) about the reference value that provides an interval that has about a 95% probability of encompassing the true value. This isotopic reference material is intended as one of two isotopic reference waters for daily normalisation of stable hydrogen and oxygen isotopic analysis of water with an isotope‐ratio mass spectrometer or a laser absorption spectrometer. It is available by the case of 144 glass ampoules or as a set of sixteen glass ampoules containing 5 ml of water in each ampoule.  相似文献   

8.
Ice core from Greenland was melted, filtered, homogenised, loaded into glass ampoules, sealed, autoclaved to eliminate biological activity, and calibrated by dual‐inlet isotope‐ratio mass spectrometry. This isotopic reference material (RM), USGS46, is intended as one of two secondary isotopic reference waters for daily normalisation of stable hydrogen (δ2H) and stable oxygen (δ18O) isotopic analysis of water with a mass spectrometer or a laser absorption spectrometer. The measured δ2H and δ18O values of this reference water were ?235.8 ± 0.7‰ and ?29.80 ± 0.03‰, respectively, relative to VSMOW on scales normalised such that the δ2H and δ18O values of SLAP reference water are, respectively, ?428 and ?55.5‰. Each uncertainty is an estimated expanded uncertainty (= 2uc) about the reference value that provides an interval that has about a 95‐percent probability of encompassing the true value. This reference water is available in cases containing 144 glass ampoules that are filled with either 4 ml or 5 ml of water per ampoule.  相似文献   

9.
Stable isotopes and element compositions of the fine‐grained matrix were measured for IODP Expedition 307 Hole U1317E drilled from the summit of Challenger Mound in Porcupine Seabight, northeast Atlantic, to explore the palaeoceanographic and palaeoclimatic background to development of the deep‐water coral mound. The 155 m long mound section was divided into two units by an unconformity at 23.6 mbsf: Unit M1 (2.6–1.7 Ma) and Unit M2 (1.0–0.5 Ma). Results from 519 specimens show a difference in δ13C value between Unit M1 (?0.6‰ to ?5.0‰) and Unit M2 (?1.0‰ to 1.0‰), but such a distinct difference was not seen in δ18O values (1.0‰–2.5‰), CaCO3 content (40–60 wt%), Sr/Ca ratio (2.0–8.0 mmol mol?1), and Mg/Ca ratio (10.0–20.0 mmol mol?1) through the mound. Positive δ18O and negative δ13C shifts at the mound base are consistent with the oceanographic changes in the northeast Atlantic at the beginning of the Quaternary. The positive δ13C regression in Unit M2 suggests a linkage to the mid Pleistocene intensified glaciation in the Northern Hemisphere. Warm Mediterranean Upper Core Water of Mediterranean Outflow Water, Eastern North Atlantic Water and cold Labrador Sea Water of North Atlantic Deep Water are key oceanographic features that cause spikes and shifts in stable isotope and element composition. However, the stable isotope values of the sediment matrix could not primarily record the glacial–interglacial eustatic/temperature change, but indirectly indicate current regimes of the intermediate oceanic layer where the coral mound grew. Similarly, elemental ratios and CaCO3 content may not represent the productivity and temperature of surface sea water, respectively, but superpose the fractions from both surface and bottom water. It is concluded that palaeoceanographic change coupled to the Pleistocene glacial/interglacial cycles is a key control on the geochemical stratigraphy of the matrix sediments of the carbonate mound developed in Porcupine Seabight. Copyright © 2011 John Wiley & Sons, Ltd.  相似文献   

10.
Stable isotope composition of syngenetic and epigenetic ice wedges, radiocarbon age, and pollen spectra of the surrounding deposits were studied during long term investigations at the "Belyi Klyuch" site on the first(6-8 m height) terrace of the Chara River(720 m.a.s.l.) in northern Transbaikalia to assess climatic conditions during ice-wedge formation. It was revealed that Holocene ice wedges had been formed from 10 to 7.5 ka 14 C BP. The isotope composition(δ~(18)O, δ~2 H) of relict ice wedges is the lightest and amounts-23‰ and-185‰, correspondingly. The isotopic compositions of ice lenses from sandy loam above ice wedges are-15.7‰, and-133‰; of small ice wedge in peat and sand are-15.3‰ and-117.9‰, accordingly.Interpretation of the ice wedge isotope composition has yielded that mean winter temperatures during cold stages of Holocene optimum were lower than today, during warm stages they were close to modern ones. During the coldest stages of Holocene optimum the total annual freezing index varied from-5100 to-5700 ℃ degree days, i.e. 300-600 ℃ degree days colder than during extremely severe modern winters. The total annual thawing index varied from 1300 to 1800 ℃ degree days, which was slightly higher than modern ones.  相似文献   

11.
Previous research has shown that Cu and Fe isotopes are fractionated by dissolution and precipitation reactions driven by changing redox conditions. In this study, Cu isotope composition (65Cu/63Cu ratios) was studied in profiles through sulphide-bearing tailings at the former Cu mine at Laver and in a pilot-scale test cell at the Kristineberg mine, both in northern Sweden. The profile at Kristineberg was also analysed for Fe isotope composition (56Fe/54Fe ratios). At both sites sulphide oxidation resulted in an enrichment of the lighter Cu isotope in the oxidised zone of the tailings compared to the original isotope ratio, probably due to preferential losses of the heavier Cu isotope into the liquid phase during oxidation of sulphides. In a zone with secondary enrichment of Cu, located just below the oxidation front at Laver, δ65Cu (compared to ERM-AE633) was as low as −4.35 ± 0.02‰, which can be compared to the original value of 1.31 ± 0.03‰ in the unoxidised tailings. Precipitation of covellite in the secondary Cu enrichment zone explains this fractionation. The Fe isotopic composition in the Kristineberg profile is similar in the oxidised zone and in the unoxidised zone, with average δ56Fe values (relative to the IRMM-014) of −0.58 ± 0.06‰ and −0.49 ± 0.05‰, respectively. At the well-defined oxidation front, δ56Fe was less negative, −0.24 ± 0.01‰. Processes such as Fe(II)–Fe(III) equilibrium and precipitation of Fe-(oxy)hydroxides at the oxidation front are assumed to cause this Fe isotope fractionation. This field study provides additional support for the importance of redox processes for the isotopic composition of Cu and Fe in natural systems.  相似文献   

12.
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 Δ26Mgomphacite‐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 Δ56Feomphacite‐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.  相似文献   

13.
Molybdenum isotopes are increasingly widely applied in Earth Sciences. They are primarily used to investigate the oxygenation of Earth's ocean and atmosphere. However, more and more fields of application are being developed, such as magmatic and hydrothermal processes, planetary sciences or the tracking of environmental pollution. Here, we present a proposal for a unifying presentation of Mo isotope ratios in the studies of mass‐dependent isotope fractionation. We suggest that the δ98/95Mo of the NIST SRM 3134 be defined as +0.25‰. The rationale is that the vast majority of published data are presented relative to reference materials that are similar, but not identical, and that are all slightly lighter than NIST SRM 3134. Our proposed data presentation allows a direct first‐order comparison of almost all old data with future work while referring to an international measurement standard. In particular, canonical δ98/95Mo values such as +2.3‰ for seawater and ?0.7‰ for marine Fe–Mn precipitates can be kept for discussion. As recent publications show that the ocean molybdenum isotope signature is homogeneous, the IAPSO ocean water standard or any other open ocean water sample is suggested as a secondary measurement standard, with a defined δ98/95Mo value of +2.34 ± 0.10‰ (2s).  相似文献   

14.
Stable isotope and trace element analyses of 230 Jurassic (Pliensbachian–Toarcian) samples from northern Spain have been performed to test the use of geochemical variations in fossils (belemnites and brachiopods) and whole‐rock hemipelagic carbonates as palaeoceanographic indicators. Although the succession analysed (Reinosa area, westernmost Basque–Cantabrian Basin) has been subject to severe thermal alteration during burial diagenesis, the samples appear to be well preserved. The degree of diagenetic alteration of the samples has been assessed through the application of integrated petrographic, chemical and cathodoluminescence analyses. It is demonstrated that brachiopods and whole‐rock carbonates, although widely used for palaeoceanic studies, do not retain their primary marine geochemical composition after burial diagenesis. In contrast, there is strong evidence that belemnite rostra preserve original isotopic values despite pervasive diagenesis of the host rock. Well‐preserved belemnite shells (non‐luminescent to slightly luminescent) typically show stable isotope values of +4·3‰ to –0·7‰δ13C, +0·7‰ to –3·2‰δ18O, and trace element contents of <32 μg g–1 Mn, <250 μg g–1 Fe, >950 μg g–1 Sr and Sr/Mn ratios >80. This study suggests that the degree to which diagenesis has affected the preservation of an original isotopic composition may differ for different low‐Mg calcite fossil shells and hemipelagic bulk carbonates, behaviour that should be considered when marine isotopic signatures from other ancient carbonate rocks are investigated. Multiple non‐luminescent contemporaneous belemnite samples passed the petrographic and geochemical tests to be considered as palaeoceanic recorders, yet their δ13C and δ18O values exhibited moderate scatter. Such variability is likely to be related to the palaeoecological behaviour of belemnites and/or high‐frequency secular variations in sea‐water chemistry superimposed on the long‐term isotopic trend. A pronounced positive carbon‐isotope excursion (up to +4·3‰) is documented in the early Toarcian serpentinus biozone, which correlates with the Toarcian δ13C maximum reported in other European and Tethyan regions.  相似文献   

15.
《Applied Geochemistry》2000,15(2):157-169
Ground-water chemistry and the stable C isotope composition (δ13CDIC) of dissolved inorganic C (DIC) were measured in a sand aquifer contaminated with JP–4 fuel hydrocarbons. Results show that ground water in the upgradient zone was characterized by DIC content of 14–20 mg C/L and δ13CDIC values of −11.3‰ to −13.0‰. The contaminant source zone was characterized by an increase in DIC content (12.5 mg C/L to 54 mg C/L), Ca, and alkalinity, with a significant depletion of 13C in δ13CDIC (−11.9‰ to −19.2‰). The source zone of the contaminant plume was also characterized by elevated levels of aromatic hydrocarbons (0 μg/L to 1490 μg/L) and microbial metabolites (aromatic acids, 0 μg/L to 2277 μg/L), non-detectable dissolved O2, NO3 and SO4. Phospholipid ester-linked fatty acid analyses suggest the presence of viable SO4-reducing bacteria in ground water at the time of sampling. The ground-water chemistry and stable C isotope composition of ground-water DIC are interpreted using a chemical reaction model involving rainwater recharge, contributions of CO2 from soil gas and biodegradation of hydrocarbons, and carbonate dissolution. The major-ion chemistry and δ13CDIC were reconciled, and the model predictions were in good agreement with field measurements. It was concluded that stable C isotope measurements, combined with other biogeochemical measures can be a useful tool to monitor the dominant terminal electron-accepting processes in contaminated aquifers and to identify mineralogical, hydrological, and microbiological factors that affect δ13C of dissolved inorganic C.  相似文献   

16.
An in situ measurement method for simultaneous determination of carbon and nitrogen isotope ratios in organic matter was developed by secondary ion mass spectrometry with a spatial resolution of ~ 12 μm. Secondary ion intensities of 12C?2, 12C13C?, 12C14N? and 12C15N? were simultaneously measured by three Faraday cups and one electron multiplier. Ions of 12C2H? were measured to monitor hydride interferences and to correct for mass bias. The analytical precisions of δ13C and δ15N values of a reference material (UWLA‐1 anthracite) were 0.16‰ and 0.56‰, respectively (2s). A negative correlation was observed between the mass bias of carbon and 12C2H?/12C?2 ratios of examined reference materials. In contrast, there was no correlation between mass bias and hydrogen concentration for nitrogen. The δ13CVPDB and δ15NAir values of twenty‐two individual globules of organic matter, found in carbonate rock of the 1878 Ma Gunflint Formation, were determined by the new procedure, ranging from ?33.8‰ to ?33.3‰ and +4.2‰ to 5.8‰, respectively. Means of δ13CVPDB and δ15NAir values, ?33.5 ± 0.25‰ and +5.2 ± 0.81‰, are consistent with reported values from bulk sample analysis within analytical precision.  相似文献   

17.
We studied calcite and rhodochrosite from exploratory drill cores (TH‐4 and TH‐6) near the Toyoha deposit, southwestern Hokkaido, Japan, from the aspect of stable isotope geochemistry, together with measuring the homogenization temperatures of fluid inclusions. The alteration observed in the drill cores is classified into four zones: ore mineralized zone, mixed‐layer minerals zone, kaolin minerals zone, and propylitic zone. Calcite is widespread in all the zones except for the kaolin minerals zone. The occurrence of rhodochrosite is restricted in the ore mineralized zone associated with Fe, Mn‐rich chlorite and sulfides, the mineral assemblage of which is basically equivalent to that in the Toyoha veins. The measured δ18OSMOW and δ13CPDB values of calcite scatter in the relatively narrow ranges from ?2 to 5‰ and from ?9 to ?5‰, respectively; those of rhodochrosite from 3 to 9‰ and from ?9 to ?5‰, excluding some data with large deviations. The variation of the isotopic compositions with temperature and depth could be explained by a mixing process between a heated surface meteoric water (100°C δ18O =?12‰, δ13C =?10‰) and a deep high temperature water (300°C, δ18O =?5‰, δ13C =?4‰). Boiling was less effective in isotopic fractionation than that of mixing. The plots of δ18O and δ13C indicate that the carbonates precipitated from H2CO3‐dominated fluids under the conditions of pH = 6–7 and T = 200–300°C. The sequential precipitation from calcite to rhodochrosite in a vein brought about the disequilibrium isotopic fractionation between the two minerals. The hydrothermal fluids circulated during the precipitation of carbonates in TH‐4 and TH‐6 are similar in origin to the ore‐forming fluids pertaining to the formation of veins in the Toyoha deposit.  相似文献   

18.
A HF‐free sample preparation method was used to purify silicon in twelve geological RMs. Silicon isotope compositions were determined using a Neptune instrument multi‐collector‐ICP‐MS in high‐resolution mode, which allowed separation of the silicon isotope plateaus from their interferences. A 1 μg g‐1 Mg spike was added to each sample and standard solution for online mass bias drift correction. δ30Si and δ29Si values are expressed in per mil (‰), relative to the NIST SRM 8546 (NBS‐28) international isotopic RM. The total variation of δ30Si in the geological reference samples analysed in this study ranged from ‐0.13‰ to ‐0.29‰. Comparison with δ29Si values shows that these isotopic fractionations were mass dependent. IRMM‐17 yielded a δ30Si value of ‐1.41 ± 0.07‰ (2s, n = 12) in agreement with previous data. The long‐term reproducibility for natural samples obtained on BHVO‐2 yielded δ30Si = ‐0.27 ± 0.08‰ (2s, n = 42) on a 12 month time scale. An in‐house Si reference sample was produced to check for the long‐term reproducibility of a mono‐elemental sample solution; this yielded a comparable uncertainty of ± 0.07‰ (2s, n = 24) over 5 months.  相似文献   

19.
Uranium-series dated stalagmites from Oman indicate that pluvial conditions prevailed from 6.3 to 10.5, 78 to 82, 120 to 130, 180 to 200 and 300 to 330 kyr B.P.; all of these periods coincide with peak interglacials. Oxygen (δ18O) and hydrogen (δD) isotope ratios of speleothem calcite and fluid inclusions reveal the source of moisture and provide information on the amount of precipitation, respectively. δ18O and δD values of stalagmites deposited during peak interglacials vary between ?8 and ?4 ‰ (VPDB) and ?53 and ?20‰ (Vienna Standard Mean Ocean Water [VSMOW]) respectively, whereas modern stalagmites range from ?2.6 to ?1.1‰ in δ18O (VPDB) and ?7.6 and ?3.3‰ in δD (VSMOW), respectively. The growth and isotopic records indicate that during peak interglacial periods, the limit of the monsoon rainfall was shifted far north of its present location and each pluvial period was coinciding with an interglacial stage of the marine oxygen isotope record.  相似文献   

20.
The Bleiberg Pb-Zn deposit in the Drau Range is the type locality of Alpine-type carbonate-hosted Pb-Zn deposits. Its origin has been the subject of on-going controversy with two contrasting genetic models proposed: (1) the SEDEX model, with ore forming contemporaneously with sedimentation of the Triassic host rocks at about 220 Ma vs. (2) the epigenetic MVT model, with ores forming after host rock sedimentation at about 200 Ma or later. Both models assume that, on a deposit or even district scale, a fixed paragenetic sequence of ore minerals can be established. The results of our detailed petrographic, chemical and sulfur isotope study of two key ore-samples from two major ore horizons in the Wetterstein Formation at Bleiberg (EHK02 Erzkalk horizon and Blb17 Maxer Bänke horizon) demonstrate that there is no fixed paragenetic sequence of ore minerals. Small-scale non-systematic variations are recorded in textures, sphalerite chemistry and δ34S. In each sample, texturally different sphalerite types (colloform schalenblende, fine- and coarse-grained crystalline sphalerite) co-occur on a millimeter to centimeter scale. These sphalerites represent multiple mineralization stages/pulses since they differ in their trace element inventory and in their δ34S. Nonetheless, there is some correspondence of sphalerite micro-textures, sulfur isotope and chemical composition between the two samples, with microcrystalline colloform schalenblende being Fe-rich, having high Fe/Cd (15 and 9, respectively) and a light sulfur isotope composition (δ34S −26.0 to −16.2‰). Cadmium-rich and Fe-poor sphalerite in both samples has relatively heavier sulfur isotope composition: in sample EHK02 this sphalerite has Fe/Cd of ∼0.5 and δ34S from −6.6 to −4.6‰; in sample Blb17 Fe/Cd is ∼0.1 and δ34S ranges from −15.0 to −1.5‰. Barite, which is restricted to sample EHK02, has δ34S ≈ 17‰. The large variations in δ34S recorded on the mm to cm-scale is consistent with variable contributions of reduced sulfur from two different sulfur reservoirs. The dominant reservoir with δ34S values <−20‰ likely results from local bacteriogenic sulfate reduction (BSR), whereas the second reservoir, with δ34S about −5‰ suggests a hydrothermal source likely linked with thermochemical sulfate reduction (TSR). Based on this small- to micro-scale study, no simple, deposit-wide paragenetic and sulfur isotope evolution with time can be established. In the Erzkalk ore (sample EHK02) an earlier Pb-Zn-Ba stage, characterized by heavy sulfur isotope values, is succeeded by a light δ34S-dominated Zn-Pb-F stage. In contrast, the several mineralization pulses identified in the stratiform Zn-Pb-F Maxer Bänke ore (sample Blb17) define a broad trend to heavier sulfur isotope values with time. The interaction documented in these samples between two sulfur reservoirs is considered a key mechanism of ore formation.  相似文献   

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