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1.
This contribution reports our preliminary work to determine Cu isotope ratios for various granite rocks and examine the Cu isotope systematics within granite suites. A chemical procedure, modified from Maréchal [Maréchal, C.N., Télouk, P. and Albarède, F., 1999. Precise analysis of copper and zinc isotopic compositions by plasma-source mass spectrometry. Chemical Geology, 156(1–4): 251–273.], was used to separate Cu from rock matrix. Quantitative recovery (100.6 ± 1.6%), with a low total procedural blank (2.65 ± 0.66 ng) for Cu, has been achieved, allowing Cu isotopic measurements on samples with as little as 10 ppm Cu. The Cu isotope ratios (δ65Cu relative to NIST SRM 976) of 32 rock samples, ranging from mafic to felsic compositions, from 3 batholiths (2 I-type, 1 S-type) from the Lachlan Fold Belt in southeastern Australia, vary from ? 0.46‰ to 1.51‰. Most of them cluster around zero, with mean values for the I-type and S-type granites of 0.03 ± 0.15‰ and ? 0.03 ± 0.42‰ (2 sigma) respectively. These data, together with Cu isotope ratios of two loess samples, provide preliminary evidence that the baseline Cu isotopic composition of the crystalline part of upper continental crust is close to zero. The tight clustering of Cu isotope ratios of rocks from the I-type suites suggests that high-temperature magmatic processes do not produce significant Cu isotope fractionation. However, two granites with abnormally heavy Cu isotope signatures (up to 1.51‰) appears to be the result of localized hydrothermal alteration. Measurable variation in Cu isotopic composition of the S-type granite may reflect isotopic heterogeneity in the sedimentary source region as a result of redox processes or may be due to hydrothermal overprinting. Thus, Cu isotope geochemistry may be a useful tracer for studying hydrothermal alteration and source heterogeneity of granitic rocks.  相似文献   

2.
《Applied Geochemistry》2006,21(5):766-781
A method for determining compound-specific Cl isotopic compositions (δ37Cl) was developed for tetrachloroethene (PCE), trichloroethene (TCE), cis-dichloroethene (cis-DCE), trans-dichloroethene (trans-DCE) and 1,1-dichloroethene (1,1-DCE). The isotope ratio mass spectrometry (IRMS) used in this study has nine collectors, including two for m/z 50 and 52 (CH3Cl) and two for m/z 94 and 96 (CH3Br). The development of this method is based on the fact that fragments with mass ratios of 94/96, 95/97 and 96/98 are produced from PCE, TCE and DCE isomers during ion bombardment in the source of a mass spectrometer. Using continuous flow isotope ratio mass spectrometry coupled with gas chromatography (GC–CF-IRMS), it is possible to separate these compounds on-line and directly measure the Cl isotopic ratios of the fragments with the specific mass ratios.Both pure phase and aqueous samples were used for Cl isotopic analysis. For pure phase samples, a vapour phase of the chlorinated ethenes was injected directly into the GC, whereas the solid phase micro extraction (SPME) method was used to extract these compounds from aqueous solutions. The precisions of this analytical technique were ±0.12‰ (1σ, n = 30), ±0.06‰ (1σ, n = 30), and ±0.08‰ (1σ, n = 15) for PCE, TCE and DCE isomers, respectively. The limits of quantification (LOQ) for analyzing Cl isotopic composition in aqueous solutions were 20, 5, and 5 μg/L for PCE, TCE and DCE isomers, respectively. This corresponds to 6–9 nano-mole of Cl, which is approximately 80 times lower than the most sensitive existing method. Compared to methods previously available, this new development offers the following advantages: (1) The much lower LOQ make it possible to extract these compounds directly from aqueous solutions using SPME without pre-concentration; (2) The linking of a GC with an IRMS eliminates off-line separation; and (3) Because the fragments used for isotopic ratio measurement are produced during ion bombardment in the mass spectrometer, there is no need to convert chlorinated ethenes to methyl chloride. As a result, this technique greatly enhances the efficiency for isotopic analysis by eliminating procedures for pre-concentration, off-line separation and sample preparation. In addition, it also reduces the potential for isotopic fractionation introduced during these procedures.Compound-specific Cl stable isotope analysis can be used as a tool to study the sources of organic contaminants in groundwater and their behaviour in the subsurface environments. It may also assist in understanding processes such as transport, mixing, and degradation reactions.  相似文献   

3.
The stable carbon isotopic compositions of light hydrocarbon gases adsorbed in near-surface soil and sediments from the Saurashtra basin were characterized for their origin and maturity. Saurashtra is considered geologically prospective for oil and gas reserves; however, a major part of the basin is covered by the Deccan Traps, hindering the exploration of Mesozoic hydrocarbon targets. Surface geochemical prospecting, based on micro-seepage of hydrocarbons from subsurface accumulations, could be advantageous in such areas. In light of this, 150 soil samples were collected from the northwestern part of Saurashtra, around the Jamnagar area, where a thick sedimentary sequence of about 2–3 km exists under 1–1.5 km of Deccan basalt. The concentration of acid desorbed alkane gases from soil samples was found to vary (in ppb) as: methane (C1) = 3–518; ethane (C2) = 0–430; propane (C3) = 0–331; i-butane (iC4) = 0–297; n-butane (nC4) = 2–116; i-pentane (iC5) = 0–31 and n-pentane (nC5) = 0–23, respectively.Fifteen samples with high concentrations of alkane gases were measured for their δ13C1; δ13C2 and δ13C3 compositions using gas chromatography–combustion-isotope ratio mass spectrometry (GC–C-IRMS). The values for methane varied from ? 27 to ? 45.4‰, ethane from ? 20.9 to ? 27.6‰, and propane from ? 20.4 to ? 29.1‰ versus the Vienna PeeDee Belemnite (VPDB). The carbon isotope ratio distribution pattern represents isotopic characteristics pertaining to hydrocarbon gases derived from thermogenic sources. Comparisons of carbon isotopic signatures and compositional variations with the standard carbon isotopic models suggest that hydrocarbon gases found in the shallow depths of the study area are not of bacterial origin but are formed thermally from deeply buried organic matter, likely to be mainly a terrestrial source rock with a partial contribution from a marine source. These gases may have migrated to the near-surface environment, where they represent an admixture of thermally generated hydrocarbon gases from mixed sources and maturity. The maturity scale (δ13C versus Log Ro %) applied to the surface sediment samples of the Jamnagar area indicated the source material to be capable of generating oil and gas. The detection of thermogenic alkane gases in near-surface sediments offers the possibility of hydrocarbons at depth in Saurashtra.  相似文献   

4.
Although oil cracking has been documented as one of the important sources of gas in many overmature marine sedimentary basins, the chemical and carbon isotopic signatures of gases of this origin are still open to question. In this study a Cambrian crude oil from the central Tarim basin, along with its main separated fractions (saturates, aromatics and asphaltenes), were pyrolyzed in sealed gold tubes to investigate how generated gases vary in chemical and carbon isotopic composition and how this variation would influence the genetic interpretation of oil cracking gas. The results indicate that the gases from cracking of aromatics and asphaltenes are much drier and more enriched in 13C than the gases from the cracking of saturates and crude oil at the same level of thermal maturity. In the experimental run of 20 °C/h, the dryness index of the gases (defined as the volume percentage of C1 in C1–5) from the cracking of saturates ranges from 26.2–90.6% with the methane carbon isotope change ranging from −54.8‰ to −35.5‰, whereas the dryness index is never lower than 60.6% for the gases from the cracking of aromatics with methane carbon isotope ranging from −39.9‰ to −32.2‰. Correspondingly, experimental data for the four samples plot in different areas in diagrams designed to distinguish oil cracking gas from kerogen cracking gas, such as ln(C2/C3) vs. δ13C2–δ13C3 and δ13C1 vs. δ13C2–δ13C3, indicating compositional variability of crude oil could assert an important influence in these diagrams. Therefore it is prudent to bring other geological constraints into consideration to avoid misinterpretation.The kinetic parameters for the bulk generation of C1–5 gas and the methane carbon isotope fractionation extrapolated to geological conditions of 2 °C/Ma and an initial temperature of 50 °C show that the temperatures of C1–5 gas generation from the aromatics and asphaltenes are lower than those from the saturates and crude oil due to their lower activation energies and frequency factors. Generation of C1–5 gases from the aromatics is modeled to be initiated about 122 °C whereas the initiation temperature for the saturates sample is 176 °C. Below 189 °C (EasyRo = 1.8%), the yields of C1–5 gases follow the order: aromatics > asphaltenes > crude oil > saturates. At similar thermal maturity levels, the methane carbon isotopic compositions are significantly different for the four samples, with an order of 13C enrichment: aromatics > asphaltenes > crude oil > saturates, however the difference in methane carbon isotopes becomes smaller with increasing temperature. This indicates that methane carbon isotopic values can be significantly different for gases cracked from oils that are compositionally diverse, especially in the early stage of methane generation.  相似文献   

5.
We report an optimized method for extracting neodymium (Nd) from fossil fish teeth with a single-stage column (125 µl stem volume; LN Resin, Eichrom Industries, Darien Illinois) for isotopic analysis by multi-collector inductively coupled mass spectrometry (MC-ICMPS). Three reference materials (basalt: BCR-2, BHVO-2; phosphate: fossil bone composite) and splits of fossil fish teeth samples previously processed with existing two-stage column methods were processed using the single-stage column method. 143Nd/144Nd values of reference materials agree within error with published values, and the values for fish teeth correspond with sample splits processed with two-stage columns. Precision to ± ～ 0.23 εNd was achieved for 30 ng Nd samples of reference materials, and Nd isotope measurements of fossil fish tooth sample replicates as small as 7 ng Nd were reproducible within long term instrumental uncertainty. We demonstrate the utility of the new method with the first high resolution Nd isotope record spanning the ～ 40.0 Ma middle Eocene Climatic Optimum, which shows an excursion of 0.65 εNd during the peak warming at the study site (Ocean Drilling Program Leg 119, Site 738; 30 kyr sample spacing from 40.3 to 39.6 Ma). LN Resin is already used in standard methods for separating Nd, and Nd isotopes are routinely measured by MC-ICPMS with high efficiency inlet systems. Our innovation is a single, small volume LN Resin column for Nd separation. The streamlined approach results in a 10× increase in sample throughput.  相似文献   

6.
Although the effects of biodegradation on the composition and physical properties of crude oil have been well studied, effects of in-reservoir petroleum biodegradation on molecular and isotopic compositions of crude oils are not yet clearly understood. The Alberta Basin, in western Canada, is one of the world’s largest petroleum accumulations and constitutes an ideal example of a natural suite of sequentially biodegraded oils. The basin hosts moderately to severely biodegraded petroleum, regionally distributed and in single, more or less continuous, oil columns. In this study, a series of oil samples from the Alberta heavy oil and oil sands provinces, with varying degrees of biodegradation, were analyzed to assess the impact of progressive biodegradation on the molecular and C, H, N, and S isotopic compositions of oils. The results of the molecular characterization of the hydrocarbon fraction of the studied oils show that the oils have suffered biodegradation levels from 2 to 10+ (toward the Alberta–Saskatchewan border) on the Peters and Moldowan scale of biodegradation (abbreviated PM 2 to PM 10) and from tens to hundreds on the Manco scale. Within single reservoirs, increasing biodegradation was observed from top to bottom of the oil columns at all sites studied. The whole oil stable isotopic compositions of the samples varied in the ranges δ13C = −31.2‰ to −29.0‰, δ2H = −147‰ to −133‰, δ15N = 0.3–4.7‰ and δ34S = 0.4–6.4‰. The maximum differences between δ values of samples (Δ) within single oil columns were Δ13C = 1.4‰, Δ2H = 7‰, Δ15N = 1.7‰ and Δ34S = 1.0‰. Regional variations in the isotopic compositions of oil samples from different wells (averaged values from top to bottom) were 1.2‰ for δ13C, 12‰ for δ2H, 4.1‰ for δ15N and 5.5‰ for δ34S and hence generally significantly larger variations were seen than variations observed within single oil columns, especially for N and S. It appears that even severe levels of biodegradation do not cause observable systematic variations in carbon, nitrogen or sulfur isotope composition of whole oils. This indicates that sulfur and nitrogen isotopic compositions may be used in very degraded oils as indicators for oil charge from different source rock facies.  相似文献   

7.
《Chemical Geology》2006,225(1-2):137-155
Carbon stable isotopes from carbonate minerals (mainly dolomite) from six wells from the Lower Triassic Sherwood Sandstones of the Corrib Gas Field, Slyne Basin, west of Ireland, allow stratigraphic correlation. The results also provide information on palaeoenvironmental change during the deposition of these continental redbed sedimentary rocks. The Triassic reservoir rocks have been buried to > 4000 m and heated to > 165 °C and now contain methane-rich gas. Although the oxygen isotopic signal has been at least partially reset during burial and heating, a primary carbon isotopic signal appears to have survived diagenesis. The carbon isotope ratio varies from − 3.2‰ to + 2.1‰. All six wells show similar stratigraphic changes when all the carbon isotope data are plotted relative to a major playa horizon. δ13C increases from about − 3‰ at the base of the Sherwood to about + 2‰ 170 m above the base. δ13C then decreases to about − 2‰ for the next 70 m and remains steady for the following 50 m. The top 20 m of the Sherwood contains carbonate with a δ13C values decreasing to about − 3‰. The occurrence of a stratigraphically-correlatable carbon isotope pattern implies that the primary evolution signal has been preserved. The change in δ13C correlates with indicators of aridity and biological stress such that the highest δ13C values are in sedimentary rocks deposited in a playa lake (arid times); these rocks contain the greatest quantity of dolomite cement. Conversely, the lowest δ13C values correspond to sedimentary rocks deposited from well-developed rivers (relatively humid times) from the lowest quantity of dolomite cement. The same carbon isotope evolution has been found in another well in the Slyne basin and in Belgium, suggesting that the palaeoenvironmental isotope signal in the Triassic sedimentary rocks of the Corrib Field may have a regional significance.  相似文献   

8.
Lithium isotope signatures of whole rock pegmatite samples and mineral separates from the rare element-bearing Little Nahanni Pegmatite Group, NWT, and whole rock samples from nearby granitic intrusions were measured. Correlation of the Li isotopic values from the pegmatite dikes with whole rock trace element geochemistry, mineralogy and primary textural evidence reflect mechanisms of Li isotopic fractionation during pegmatite formation. The heavier δ7Li signatures within the broad range measured from whole rock LNPG samples (? 0.94‰ to + 11.36‰) are related to the consolidation of the final ~ 15% melt fraction of a volatile-rich peraluminous magma in the late stages of magmatic fractionation. Rock-forming minerals (quartz, albite, spodumene and mica) display δ7Li signatures that indicate consolidation of the dikes under variable, non-equilibrium conditions. Lithium isotope signatures of relatively cool, highly evolved peraluminous magmas reflect the build-up of fluxes (e.g., H2O and F) and provide a qualitative assessment of the state of mineral/melt chemical equilibrium.  相似文献   

9.
Ancient cave systems in the Northern Calcareous Alps, today located well above the timberline at altitudes of 2400–2500 m, host U-rich speleothems that preserved growth layers on the microscopic scale of presumably annual origin. Two flowstone samples were dated to 2.019 + 0.037/?0.069 Ma and 1.730 + 0.032/?0.068 Ma, respectively, using U–Pb isochron techniques. These ages are corroborated by the Late Pliocene to Early Pleistocene pollen spectrum extracted from one of the samples. We use a multiproxy approach and exploit laminated speleothem sequences to tie high-resolution stable isotope data to a floating lamina-counted chronology. O isotope values of growth intervals when calcite deposition was close to isotopic equilibrium are low compared to modern and Holocene speleothems from other alpine caves and are inconsistent with the current altitudinal setting of the caves. A vegetated but geomorphologically stable alpine catchment (i.e. ～2000 m asl., no (peri)glacial processes) combined with a deep-seated cave (the thickness of the vadose zone might have exceeded 1000 m) is required in order to reconcile the isotopic data with the pollen record and the petrographic evidence. Furthermore, the data can be used to constrain the rate for Quaternary rock-uplift to ≤0.8 mm/annum for this frontal part of the European Alps. Collectively, the data suggest that these speleothems formed both during interglacials (MIS 59 or 61) and interglacial–glacial transitions (MIS 75/74 or 77/76), but the seasonal precipitation pattern was arguably markedly different from today's. Provided that the highly regular microscopic laminae are indeed annual, lamina counts suggest a minimum length of ca 6 ka for interglacials during the earliest Pleistocene.  相似文献   

10.
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   

11.
《Gondwana Research》2014,26(4):1348-1356
The Early Toarcian Oceanic Anoxic Event (OAE) in the Early Jurassic Period is associated with a major negative carbon isotope excursion (CIE), mass extinction, marine transgression and global warming. The Toarcian OAE is thought to have been caused by flood basalt magmatism, and may have been a trigger for mass extinction. However, these proposed causes of the Toarcian OAE and associated biotic crisis are not adequately resolved by a precise chronology. The duration of the Toarcian OAE has been estimated to be anywhere from ~ 0.12 to ~ 0.9 Myr, most recently 0.74 to 3.26 Myr from U–Pb dating. The CIE associated with the Toarcian OAE has a similar pattern at numerous localities, and there is evidence that the marine carbon isotope variations recorded astronomical forcing signals. Here we estimate a duration of ~ 620 kyr for the main negative CIE, ~ 860 kyr for the polymorphum zone and > 1.58 Myr for the levisoni zone based on 405-kyr astronomical eccentricity tuning of the marine section at Peniche (Portugal). This 405-kyr tuned series provides a ~ 2.5 Myr continuous high-resolution chronology through the Early Toarcian. There are 6, or possibly 7 short eccentricity cycles in the main CIE interval at Peniche. To confirm this astronomically based estimate, we analyzed three other sections at Yorkshire (UK), Dotternhausen (Germany), and Valdorbia (Italy) from marine carbon isotopic series. These four stratigraphic sections from Early Jurassic western Tethys record the Toarcian OAE with ~ 6 prominent carbon isotope cycles in the CIE that span a 600 ± 100 kyr duration. The Peniche 405-kyr tuned series indicates that the pre- and post-CIE intervals experienced strong precession–eccentricity-forced climate change, whereas the CIE interval is marked by dominant obliquity forcing. These dramatic and abrupt changes in astronomical response in the carbon isotopes point to fundamental shifting in the Early Toarcian paleoclimate system that was directly linked to the global carbon cycle.  相似文献   

12.
Studies of sulfur and lead isotopic compositions in hydrothermal deposits are an important tool to determine the source and processes of both sulfur and lead, and to understand the origin of hydrothermal ore deposits. Here, the sulfur and lead isotopic compositions of sulfide minerals have been studied for different hydrothermal fields in the East Pacific Rise (EPR), Mid-Atlantic Ridge (MAR), Central Indian Ridge (CIR), Southwest Indian Ridge (SWIR), and North Fiji Basin (NFB). The sulfur isotopic compositions of the studied sulfide samples are variable (δ34S 0.0 to 9.6‰, avg. δ34S 4.7‰; n = 60), being close to the associated igneous rocks (~ 0‰ for, e.g., basalt, serpentinized peridotite), which may reflect the S in the sulfide samples is derived mainly from the associated igneous rocks, and a relatively small proportion (< 36%) of seawater sulfur incorporated into these sulfides during mixing between seawater (δ34S 21‰) and hydrothermal fluid. In contrast for a mixed origin for the source of S, the majority of the lead isotopic compositions (206Pb/204Pb 17.541 ± 0.004 to 19.268 ± 0.001, 207Pb/204Pb 15.451 ± 0.001 to 15.684 ± 0.001, 208Pb/204Pb 37.557 ± 0.008 to 38.988 ± 0.002, n = 21) of the sulfides possess a basaltic Pb isotopic composition, suggesting that the lead in the massive sulfide is mainly leached from local basaltic rocks that host the sub-seafloor hydrothermal systems in sediment-free mid-ocean ridges and mature back-arc basins. Furthermore, sulfide minerals in the super-fast and fast spreading mid-ocean ridges (MORs) exhibit less spread in their the δ34S values compared to sulfides from super-slow, and slow spreading MORs, which is most easily explained as a lesser degree of fluid-rock interaction and hydrothermal fluid-seawater mixing during hydrothermal ore-forming process. Additionally, the S and Pb isotope compositions of sulfides are controlled by the fluid processes for forming seafloor massive sulfide deposits. We demonstrate that the variable sulfur and lead isotopic compositions exhibit a relationship with the sulfur and lead sources, fluid–rock interaction, and fluid–seawater mixing.  相似文献   

13.
Stable isotopes of injected CO2 act as useful tracers in carbon capture and storage (CCS) because the CO2 itself is the carrier of the tracer signal and remains unaffected by sorption or partitioning effects. At the Ketzin pilot site (Germany), carbon stable isotope composition (δ13C) of injected CO2 at the injection well was analyzed over a time period of 4 months. Occurring isotope variances resulted from the injection of CO2 from two different sources (an oil refinery and a natural gas-reservoir). The two gases differed in their carbon isotope composition by more than 27‰. In order to find identifiable patterns of these variances in the reservoir, more than 250 CO2-samples were collected and analyzed for their carbon isotope ratios at an observation well 100 m distant from the injection well. An isotope ratio mass spectrometer connected to a modified Thermo Gasbench system allowed quick and cost effective isotope analyses of a high number of CO2 gas specimens. CO2 gas from the oil refinery (δ13C = −30.9‰, source A) was most frequently injected and dominated the reservoir δ13C values at the injection site. Sporadic injection of the CO2 from the natural gas-reservoir (δ13C = −3.5‰, source B) caused isotope shifts of up to +5‰ at the injection well. These variances provided a potential ideal tracer for CO2 migration behavior. Based on these findings, tracer input signals that were injected during the last 2 years of injection could be reconstructed with the aid of an isotope mixing model and CO2 delivery schedules. However, in contrast to the injection well, δ13C values at the observation well showed no variances and a constant value of −28.5‰ was measured at 600 m depth. This is in disagreement with signals that would be expected if the input signals from the injection would arrive at the observation well. The lack of isotope signals at the observation well suggests that parts of the reservoir are filled with CO2 that is immobilized.  相似文献   

14.
Carbon isotope compositions for the 20 standard amino acids are calculated using high-level molecular orbital and density functional theory methods. In agreement with measurements of the isotopic compositions of amino acids in a cyanobacterium [Macko, S.A., Fogel, M.L., Hare, P.E., Hoering, T.C., 1987. Isotope fractionation of nitrogen and carbon in the synthesis of amino acids by microorganisms. Chemical Geology 65, 79–92] the calculations give heavy signatures for aspartic acid + asparagine, serine, glutamine + glutamic acid and light signatures for leucine and isoleucine. The relative intramolecular enrichment of 13C in carboxyl groups is often much less than measured [Abelson, P.H., Hoering, T.C., 1961. Carbon isotope fractionation in formation of amino acids by photosynthetic organisms. Proceedings of the National Academy of Sciences, USA 47, 623–632]. Fractionations predicted from density functional calculations often differ by several per mil from those predicted from molecular orbital calculations.  相似文献   

15.
Far-from equilibrium, steady state forsterite dissolution rates were measured at pH ∼3 and 25 °C in aqueous solutions containing 0.1 m/kg NaCl and up to 0.1 mol/kg of 13 distinct dissolved organic ligands in mixed-flow reactors. The organic ligands considered in this study include those common in Earth surface environments and those considered as potential catalysts for use in CO2 sequestration efforts: acetate, oxalate, citrate, EDTA4−, glutamate, gluconate, malonate, aspartate, tartrate, malate, alginate, salycilate and humate. The presence of up to 0.1 mol/kg of each organic ligand altered forsterite dissolution rates less than 0.2 log units, which is the estimated uncertainty of the measured rates. Results obtained in this study, therefore, suggest that the presence of aqueous organic anions negligibly affects forsterite far-from equilibrium dissolution rates in most natural environments, and indicate that forsterite carbonation may not be appreciably accelerated by organic ligand catalysis.  相似文献   

16.
Lead concentrations and stable lead isotopes (204Pb, 206Pb, 207Pb, 208Pb) were measured in forest moss samples (Pleurozium schreberi or Scleropodium purum) collected at 273 sites across the Czech Republic during 2010. Continuously decreasing median Pb concentrations in moss were documented over the last two decades: 1995: 11 mg/kg, 2000: 5.66 mg/kg, 2005: 4.94 mg/kg and 2010: 2.85 mg/kg. Several local anomalies have decreased in scale, the overall regional distribution patterns remained, however, the same. The regional Pb isotope ratio distributions show that the ratios show little variation for a large central part of the country and provide the large-scale background isotope ratios for the Czech Republic of about 204Pb/206Pb = 0.0550, 206Pb/207Pb = 1.167, 206Pb/208Pb = 0.478 and 207Pb/208Pb = 0.409 for 2010. This background Pb isotope ratio signal in moss has been locally (900–7500 km2) modified by specific Pb isotopic ratio signals caused by deposition of Pb emissions from known local anthropogenic Pb emission sources, such as industrial combustion of local coal, and a variety of industrial enterprises (metallurgical, engineering and glass works). At some sites where mining of uranium and polymetallic ores took place the moss samples show also a locally specific Pb isotope signal. The in terms of area affected largest deviations in the Pb-isotope ratios, e.g., in the Bohemian Massif, may be due to the input of geogenic dust.  相似文献   

17.
《Quaternary Science Reviews》1999,18(4-5):501-513
Terrestrial stable isotope records (13C/12C, 18O/16O, and D/H ratios) of late Quaternary paleoclimates in the eastern Mediterranean region are reviewed. Significant paleoclimatic reconstructions come from a variety of isotopic studies. Paleogroundwaters, although they cannot be accurately dated, show oxygen and hydrogen isotopic compositions highly depleted in heavier isotopes compared to modern meteoric waters in arid regions of southern Israel, Sinai and northeastern Africa and attest to a major difference in climatic regime some time in the Pleistocene. Th-U dating of land snails showing a similar 18O depletion indicates ages of 100,000 yr and ≥300,000 yr for this climatic regime in the Negev Desert of southern Israel. Carbon isotope records of organic matter have not been studied extensively in the region, except for the record of Holocene land snails in the Negev. These document a southward shift in pure C3 plant communities in the middle and early Holocene relative to their present distribution and indicate wetter conditions at those times. An oxygen isotope curve for the Holocene, reflecting changes in the isotopic composition of precipitation, has been established from analysis of carbonate materials—land snail shells and speleothems. The curve indicates a depletion of ca. 2‰ in 18O centered around 7000 cal yr bp, with modern levels being reached by 5000 cal yr bp. Carbon isotope analysis of soil carbonates in paleosols developed in loess in the Negev show the existence of dramatic north–south climatic gradients at the times of formation of the soils (ca. 13,000, 28,000, and ≥37,000 14C yr bp), as occur also today due to the waning influence of Mediterranean to the south. Some isotopic methods, widely used in other regions, have received little or no attention in the eastern Mediterranean region. These include oxygen and hydrogen isotopes in wood, phosphate oxygen and organic carbon in bones and teeth, and carbon in soil organic matter.  相似文献   

18.
The study presents copper (Cu) isotope data of mineral separates of chalcopyrite from four drill core samples in the Miocene Dabu porphyry Cu-Mo deposit formed in a post-collisional setting in the Gangdese porphyry copper belt, southern Tibet. Copper isotope values in hypogene chalcopyrite range from –1.48‰ to +1.12‰, displaying a large variation of up to 2.60‰, which demonstrates Cu isotope fractionation at high-temperature during hydrothermal evolution. The majority of measured chalcopyrite isotopic compositions show a gradual increasing trend from –1.48‰ to +1.12‰ with the increase of drilling depth from 130m to 483m, as the alteration assemblages change from potassic to phyllic. Similarly, the other δ65Cu values (δ65Cu = ((65Cu/63Cu)sample/(65Cu/63Cu)standard − 1) × 1000) of the chalcopyrite show a gradual increasing trend from −1.48‰ to +0.59‰ with the decrease of drilling depth from 130 m to 57 m, as the alteration assemblages change from potassic, phyllic, through argillic to relatively fresh. These observations suggest a genetic link between Cu isotope variation and silicate alteration assemblages formed at different temperatures, indicative of a Rayleigh precipitation process resulting in the large variation of δ65Cu values at Dabu. In general, samples closest to the center of hydrothermal system dominated by high-temperature potassic alteration are isotopically lighter, whereas samples dominated by low-temperature phyllic alteration peripheral to the center are isotopically heavier. The predicted flow pathways of hydrothermal fluids are from No. 0 to No. 3 exploration line, and the lightest δ65Cu values are the most proximal to the hydrothermal source. Finally, we propose that the northwest side of the No. 0 exploration line has high potential for hosting undiscovered orebodies. The pattern of Cu isotope variation in conjunction with the features of silicate alteration in porphyry system can be used to trace the hydrothermal flow direction and to guide mineral exploration.  相似文献   

19.
Olivine, clinopyroxene and orthopyroxene in variably metasomatised peridotite xenoliths from three lithospheric mantle sections beneath the East African Rift in Tanzania (Lashaine, Olmani, Labait) show systematic differences in their average Li concentrations (2.4 ppm, 2.0 ppm and 1.5 ppm, respectively) and intermineral isotopic fractionations, with olivine being heaviest (δ7Li = + 2.3 to + 13.9‰, average + 5.0‰), followed by orthopyroxene (? 4.1 to + 6.5‰, average + 0.8‰) and clinopyroxene (? 6.7 to + 4.1‰, average ? 1.6‰). These features are ascribed to the effects of kinetic Li isotope fractionation combined with different Li diffusivities in mantle minerals.Two main mechanisms likely generate diffusion-driven kinetic Li isotope fractionation in mantle xenoliths (1) Li diffusion from grain boundary melt into minerals during recent metasomatism or entrainment in the host magma and (2) subsolidus intermineral Li-redistribution. The latter can produce both isotopically light (Li-addition) and heavy (Li-loss) minerals and may occur in response to changes in pressure and/or temperature.Modelling shows that non-mantle-like δ7Li in clinopyroxene (< + 2‰), combined with apparent equilibrium olivine-clinopyroxene elemental partitioning in most peridotite xenoliths from all three Tanzanian localities probably reflects incipient Li addition during interaction with the host magma. Low δ7Li (< ? 3‰), combined with high Li concentrations (> 3 ppm) in some clinopyroxene may require very recent (minutes) Li ingress from a Li-rich melt (100s of ppm) having mantle-like δ7Li. This might happen during late fragmentation of some mantle xenoliths caused by a volatile- (and Li-) rich component exsolved from the host basalt. In contrast, high Li concentrations (> 2 ppm) and δ7Li (> 4‰) in olivine from many Labait and Olmani samples are attributed to an older, pre-entrainment enrichment event during which isotopic equilibrium was attained and whose signature was not corrupted during xenolith entrainment. Low Li concentrations and mantle-like isotopic composition of olivine from most Lashaine xenoliths indicate limited metasomatic Li addition.Thus, Li concentrations and isotope compositions of mantle peridotites worldwide may reflect two processes, with olivine mainly preserving a signature of depletion in refractory samples (low Li contents and δ7Li) or of older (precursory) melt addition in metasomatised samples (high Li contents and δ7Li), while non mantle-like, low δ7Li in almost all clinopyroxene can be due to Li ingress during transport in the host magma and/or slow cooling, if the samples were erupted in lavas. In Tanzania, the peridotites experienced rift-related heating prior to entrainment and were quenched upon eruption, so Li ingress is the most likely process responsible for the isotopically light clinopyroxene here.  相似文献   

20.
Determination of the emplacement ages and initial isotopic composition of kimberlite by conventional isotopic methods using bulk rock samples is unreliable as these rocks usually contain diverse clasts of crustal- and mantle-derived materials and can be subject to post-intrusion sub-aerial alteration. In this study, 8 samples from 5 kimberlites in southern Africa and twelve samples from 7 kimberlites from Somerset Island, Canada have been selected for in situ perovskite U–Pb isotopic age determination and Nd isotopic analysis by laser ablation using thin sections and mineral separates. These fresh perovskites occur as primary groundmass minerals with grain-sizes of 10–100 μm. They were formed during the early stage of magmatic crystallization, and record data for the least contaminated or contamination-free kimberlitic magma. U–Pb isotopic data indicate that the majority of the southern Africa kimberlites investigated were emplaced during the Cretaceous with ages of 88 ± 3 to 97 ± 6 Ma, although one sample yielded an Early Paleozoic age of 515 ± 6 Ma. Twelve samples from Somerset Island yielded ages ranging from 93 ± 4 Ma to 108 ± 5 Ma and are contemporaneous with other Cretaceous kimberlite magmatism in central Canada (103–94 Ma). Although whole-rock compositions of the kimberlites from southern Africa have a large range of εNd(t) values (? 0.5 to + 5.1), the analysed perovskites show a more limited range of + 1.2 to + 3.1. Perovskites from Somerset Island have εNd(t) values of ? 0.2 to + 1.4. These values are lower than that of depleted asthenospheric mantle, suggesting that kimberlites might be derived from the lower mantle. This study shows that in situ U–Pb and Nd isotopic analysis of perovskite by laser ablation is both rapid and economic, and serves as a powerful tool for the determination of the emplacement age and potential source of kimberlite magmas.  相似文献   

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