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11.
Effects of speciation on equilibrium fractionations and rates of oxygen isotope exchange between (PO4)aq and H2O 总被引：1，自引：0，他引：1
The effects of phosphate speciation on both rates of isotopic exchange and oxygen isotope equilibrium fractionation factors between aqueous phosphate and water were examined over the temperature range 70 to 180°C. Exchange between phosphate and water is much faster at low pH than at high pH, an observation that is similar to what has been observed in the analogous sulfate-water system. Oxygen isotope fractionations between protonated species like H3PO4 and H2PO4− that are dominant at relatively low pH and species like PO43− and ion pairs like KHPO4− that are dominant at relatively high pH, range between 5 and 8‰ at the temperatures of the experiments. In aqueous phosphate systems at equilibrium, 18O/16O ratios increase with increasing degree of protonation of phosphate. This effect can be explained in part by the relative magnitudes of the dissociation constants of the protonated species. Under equilibrium conditions, carbonate in solution or in solid phases concentrates 18O relative to orthophosphate in solution or in solid phases at all temperatures, supporting the traditional view that biogenic phosphate is precipitated in near oxygen isotope equilibrium with body/ambient aqueous fluids with no attendant vital effects. 相似文献
12.
The variations of environmental conditions (T°, pH, δ13CDIC, [DIC], δ18O, Mg/Ca, and Sr/Ca) of ostracod habitats were examined to determine the controls of environmental parameters on the chemical and isotopic composition of ostracod valves. Results of a one-year monitoring of environmental parameters at five sites, with depths of between 2 and 70 m, in Lake Geneva indicate that in littoral to sub-littoral zones (2, 5, and 13 m), the chemical composition of bottom water varies seasonally in concert with changes in temperature and photosynthetic activity. An increase of temperature and photosynthetic activity leads to an increase in δ13C values of DIC and to precipitation of authigenic calcite, which results in a concomitant increase of Mg/Ca and Sr/Ca ratios of water. In deeper sites (33 and 70 m), the composition of bottom water remains constant throughout the year and isotopic values and trace element contents are similar to those of deep water within the lake. The chemical composition of interstitial pore water also does not reflect seasonal variations but is controlled by calcite dissolution, aerobic respiration, anaerobic respiration with reduction of sulphate and/or nitrate, and methanogenesis that may occur in the sediment pores. Relative influence of each of these factors on the pore water geochemistry depends on sediment thickness and texture, oxygen content in bottom as well as pore water. Variations of chemical compositions of the ostracod valves of this study vary according to the specific ecology of the ostracod species analysed, that is its life-cycle and its (micro-)habitat. Littoral species have compositions that are related to the seasonal variations of temperature, δ13C values of DIC, and of Mg/Ca and Sr/Ca ratios of water. In contrast, the compositions of profundal species are largely controlled by variations of pore fluids along sediment depth profiles according to the specific depth preference of the species. The control on the geochemistry of sub-littoral species is a combination of controls for the littoral and profundal species as well as the specific ecology of the species. 相似文献
13.
The Hutti gold mine is located in a high-angle, NNW–SSE-trending shear zone system, which hosts nine discrete auriferous shear zones (reefs). On a clockwise, retrograde PT path two separate stages of deformation/metamorphism (D2/M2 and D3/M3) occurred synchronous with two distinct stages of gold mineralization, both of which were associated with different fluid types. Stage 1 mineralization developed during D2/M2, where the amphibolite host rocks were altered by a metamorphic fluid with a $ {{\delta }^{{18}}}{{O}_{{{{H}_2}O}}} $ of 7.5–10.1?‰, rich in K, S, As, and Au at pressure and temperature conditions of around 3 kbar and 530?+?20/?30°C, respectively. The stage 1 auriferous shear zones are enveloped by a zoned alteration consisting of a distal biotite–chlorite and proximal biotite–plagioclase assemblage. Subsequently, D2/M2 was overprinted by D3/M3 deformation and metamorphism at 300–400°C and <2 kbar that formed the stage 2 mineralization. The stage 2 mineralizing fluid which originated from outside the greenstone belt (δ18Ofluid of 3.2–6.8?‰) was rich in Si, Au, and W. This mineralization stage is distinct by the emplacement of laminated quartz veins central to the shear zone, containing locally visible gold at concentrations of up to 1 kg Au/t. The laminated quartz veins are surrounded by a millimeter-scale chlorite2–K-feldspar alteration halo, which replaced the stage 1 biotite–plagioclase assemblage. The oxygen isotopic composition of the stage 2 fluid suggests a mixture of a magmatic fluid with an oxygen isotopic composition in the range of 6 to 10?‰ and an isotopically light formation fluid that resulted from fluid–rock interaction in the greenstone pile. The two fluid fluxes at stages 1 and 2 both contributed to the overall gold mineralization; however, it was the second fluid pulse, which gave the Hutti mine its status as the largest gold mine in India. The metamorphic evolution was thereby important for the first stage, whereas the second stage was controlled by tectonism and intrusion of the high-heat production Yellagatti granite that re-established the fluid plumbing and mineralizing system. 相似文献
14.
S.?SindernEmail author F.?M.?Meyer M.?J.?L?gering J.?Kolb T.?Vennemann J.?Schwarzbauer 《International Journal of Earth Sciences》2012,101(1):87-108
Quartz–carbonate–chlorite veins were studied in borehole samples of the RWTH-1 well in Aachen. Veins formed in Devonian rocks
in the footwall of the Aachen thrust during Variscan deformation and associated fluid flow. Primary fluid inclusions indicate
subsolvus unmixing of a homogenous H2O–CO2–CH4–(N2)–Na–(K)–Cl fluid into a H2O–Na–(K)–Cl solution and a vapour-rich CO2–(H2O, CH4, N2) fluid. The aqueous end-member composition resembles that of metamorphic fluids of the Variscan front zone with salinities
ranging from 4 to 7% NaCl equiv. and maximum homogenisation temperatures of close to 400°C. Pressure estimates indicate a
burial depth between 4,500 and 8,000 m at geothermal gradients between 50 and 75°C/26 MPa, but pressure decrease to sublithostatic
conditions is also indicated, probably as a consequence of fracture opening during episodic seismic activity. A second fluid
system, mainly preserved in pseudo-secondary and secondary fluid inclusions, is characterised by fluid temperatures between
200 and 250°C and salinities of <5% NaCl equiv. Bulk stable isotope analyses of fluids released from vein quartz, calcite,
and dolomite by decrepitation yielded δDH2O values from −89 to −113 ‰, δ13CCH4 from −26.9 to −28.9‰ (VPDB) and δ13CCO2 from −12.8 to −23.3‰ (VPDB). The low δD and δ13C range of the fluids is considered to be due to interaction with cracked hydrocarbons. The second fluid influx caused partial
isotope exchange and disequilibrium. It is envisaged that an initial short lived flux of hot metamorphic fluids expelled from
the epizonal metamorphic domains of the Stavelot–Venn massif. The metamorphic fluid was focused along major thrust faults
of the Variscan front zone such as the Aachen thrust. A second fluid influx was introduced from formation waters in the footwall
of the Aachen thrust as a consequence of progressive deformation. Mixing of the cooler and lower salinity formation water
with the hot metamorphic fluid during episodic fluid trapping resulted in an evolving range of physicochemical fluid inclusion
characteristics. 相似文献
15.
B.?LacroixEmail author D.?Charpentier M.?Buatier T.?Vennemann P.?Labaume T.?Adatte A.?Travé M.?Dubois 《Contributions to Mineralogy and Petrology》2012,163(6):1083-1102
The chemical and isotopic compositions of clay minerals such as illite and chlorite are commonly used to quantify diagenetic and low-grade metamorphic conditions, an approach that is also used in the present study of the Monte Perdido thrust fault from the South Pyrenean fold-and-thrust belt. The Monte Perdido thrust fault is a shallow thrust juxtaposing upper Cretaceous–Paleocene platform carbonates and Lower Eocene marls and turbidites from the Jaca basin. The core zone of the fault, about 6 m thick, consists of intensely deformed clay-bearing rocks bounded by major shear surfaces. Illite and chlorite are the main hydrous minerals in the fault zone. Illite is oriented along cleavage planes while chlorite formed along shear veins (<50 μm in thickness). Authigenic chlorite provides essential information about the origin of fluids and their temperature. δ18O and δD values of newly formed chlorite support equilibration with sedimentary interstitial water, directly derived from the local hanging wall and footwall during deformation. Given the absence of large-scale fluid flow, the mineralization observed in the thrust faults records the P–T conditions of thrust activity. Temperatures of chlorite formation of about 240°C are obtained via two independent methods: chlorite compositional thermometers and oxygen isotope fractionation between cogenetic chlorite and quartz. Burial depth conditions of 7 km are determined for the Monte Perdido thrust reactivation, coupling calculated temperature and fluid inclusion isochores. The present study demonstrates that both isotopic and thermodynamic methods applied to clay minerals formed in thrust fault are useful to help constrain diagenetic and low-grade metamorphic conditions. 相似文献
16.
David P. Stenger Stephen E. Kesler Torsten Vennemann 《Journal of Geochemical Exploration》1998,63(2):105-121
This study was undertaken to determine whether wallrocks around the Twin Creeks Carlin-type gold deposits exhibit oxygen isotope haloes similar to those found around other types of hydrothermal deposits. Mineralization at Twin Creeks is hosted by Ordovician Sequence shales containing some carbonate minerals and by Pennsylvanian–Permian Etchart Formation limestone. Analysis of orthophosphate-soluble carbonate from these rocks shows that oxygen isotope haloes are detectable in Ordovician Sequence shales but not in Etchart Formation limestone. The soluble fraction of Ordovician Sequence shales at Twin Creeks has δ18O values of 12 to 24‰ and δ13C values of 0 to −10‰. Most samples fall along a poorly defined trend that extends from δ18O of about 24‰ and δ13C values of about 0, which are typical of unaltered limestones, toward lower values for both isotope systems, which are typical of rocks that have undergone alteration by hydrothermal fluids. Plots of these values along two sections through the ore body show that δ18O values of wallrocks are lowest in the ore zone and increase outward, forming a halo several hundred meters in size. In the same plots, δ13C values of the wallrocks do not show systematic spatial variations. The soluble fraction of Etchart Formation limestones at Twin Creeks have δ18O values of 25 to 5‰ and δ13C values of 4 to −10‰, but do not show any systematic spatial variation relative to mineralization at the scale of our samples. Failure of the Etchart Formation samples to show detectable haloes is probably related to deposition of post-ore carbonate minerals or lower ore fluid : rock ratios. Material balance calculations used to model the isotopic composition of average Ordovician Sequence shales indicate that changes in temperature and water : rock ratio were probably not sufficient to account for the wide range of isotope compositions observed in these rocks. The most likely additional factor contributing to this range of values was a change in the composition of the altering fluid, probably by mixing of the ore fluid with surrounding meteoric water. These results suggest that Carlin-type gold deposits are surrounded by haloes of low δ18O values, but that detection of these haloes could be complicated by local compositional variations and post-ore modification of the wallrocks. 相似文献
17.
Summary Crystallization temperatures of the oceanic carbonatites of Fuerteventura, Canary Islands, have been determined from oxygen isotope fractionations between calcite, silicate minerals (feldspar, pyroxene, biotite, and zircon) and magnetite. The measured fractionations have been interpreted in the light of late stage interactions with meteoric and/or magmatic water. Cathodoluminescence characteristics were investigated for the carbonatite minerals in order to determine the extent of alteration and to select unaltered samples. Oxygen isotope fractionations of minerals of unaltered samples yield crystallization temperatures between 450 and 960°C (average 710°C). The highest temperature is obtained from pyroxene–calcite pairs. The above range is in agreement with other carbonatite thermometric studies.This is the first study that provides oxygen isotope data coupled with a CL study on carbonatite-related zircon. The CL pictures revealed that the zircon is broken and altered in the carbonatites and in associated syenites. Regarding geological field evidences of syenite–carbonatite relationship and the close agreement of published zircon U/Pb and whole rock and biotite K/Ar and Ar–Ar age data, the most probable process is early zircon crystallization from the syenite magma and late-stage reworking during magma evolution and carbonatite segregation. The oxygen isotope fractionations between zircon and other carbonatite minerals (calcite and pyroxene) support the assumption that the zircon would correspond to the early crystallization of syenite–carbonatite magmas. 相似文献
18.
The stable carbon and oxygen isotope compositions of fossil ostracods are powerful tools to estimate past environmental and climatic conditions. The basis for such interpretations is that the calcite of the valves reflects the isotopic composition of water and its temperature of formation. However, calcite of ostracods is known not to form in isotopic equilibrium with water and different species may have different offsets from inorganic precipitates of calcite formed under the same conditions. To estimate the fractionation during ostracod valve calcification, the oxygen and carbon isotope compositions of 15 species living in Lake Geneva were related to their autoecology and the environmental parameters measured during their growth. The results indicate that: (1) Oxygen isotope fractionation is similar for all species of Candoninae with an enrichment in 18O of more than 3‰ relative to equilibrium values for inorganic calcite. Oxygen isotope fractionation for Cytheroidea is less discriminative relative to the heavy oxygen, with enrichments in 18O for these species of 1.7 to 2.3‰. Oxygen isotope fractionations for Cyprididae are in-between those of Candoninae and Cytheroidea. The difference in oxygen isotope fractionation between ostracods and inorganic calcite has been interpreted as resulting from a vital effect. (2) Comparison with previous work suggests that oxygen isotope fractionation may depend on the total and relative ion content of water. (3) Carbon isotope compositions of ostracod valves are generally in equilibrium with DIC. The specimens’ δ13C values are mainly controlled by seasonal variations in δ13CDIC of bottom water or variation thereof in sediment pore water. (4) Incomplete valve calcification has an effect on carbon and oxygen isotope compositions of ostracod valves. Preferential incorporation of at the beginning of valve calcification may explain this effect. (5) Results presented here as well as results from synthetic carbonate growth indicate that different growth rates or low pH within the calcification site cannot be the cause of oxygen isotope ‘vital effects’ in ostracods. Two mechanisms that might enrich the 18O of ostracod valves are deprotonation of that may also contribute to valve calcification, and effects comparable to salt effects with high concentrations of Ca and/or Mg within the calcification site that may also cause a higher temperature dependency of oxygen isotope fractionation. 相似文献
19.
Rare earth elements (REE), while not essential for the physiologic functions of animals, are ingested and incorporated in ppb concentrations in bones and teeth. Nd isotope compositions of modern bones of animals from isotopically distinct habitats demonstrate that the 143Nd/144Nd of the apatite can be used as a fingerprint for bedrock geology or ambient water mass. This potentially allows the provenance and migration of extant vertebrates to be traced, similar to the use of Sr isotopes. Although REE may be enriched by up to 5 orders of magnitude during diagenesis and recrystallization of bone apatite, in vivo143Nd/144Nd may be preserved in the inner cortex of fossil bones or enamel. However, tracking the provenance of ancient or extinct vertebrates is possible only for well-preserved archeological and paleontological skeletal remains with in vivo-like Nd contents at the ppb-level. Intra-bone and -tooth REE analysis can be used to screen for appropriate areas. Large intra-bone Nd concentration gradients of 101-103 are often measured. Nd concentrations in the inner bone cortex increase over timescales of millions of years, while bone rims may be enriched over millenial timescales. Nevertheless, εNd values are often similar within one εNd unit within a single bone. Larger intra-bone differences in specimens may either reflect a partial preservation of in vivo values or changing εNd values of the diagenetic fluid during fossilization. However, most fossil specimens and the outer rims of bones will record taphonomic 143Nd/144Nd incorporated post mortem during diagenesis. Unlike REE patterns, 143Nd/144Nd are not biased by fractionation processes during REE-uptake into the apatite crystal lattice, hence the εNd value is an important tracer for taphonomy and reworking. Bones and teeth from autochthonous fossil assemblages have small variations of ±1 εNd unit only. In contrast, fossil bones and teeth from over 20 different marine and terrestrial fossil sites have a total range of εNd values from -13.0 to 4.9 (n = 80), often matching the composition of the embedding sediment. This implies that the surrounding sediment is the source of Nd in the fossil bones and that the specimens of this study seem not to have been reworked. Differences in εNd values between skeletal remains and embedding sediment may either indicate reworking of fossils and/or a REE-uptake from a diagenetic fluid with non-sediment derived εNd values. The latter often applies to fossil shark teeth, which may preserve paleo-seawater values. Complementary to εNd values, 87Sr/86Sr can help to further constrain the fossil provenance and reworking. 相似文献
20.
Whole rock trace element and isotopic compositions of different HP–LT metamorphic rocks of the Ile de Groix were analysed to characterise geochemical fingerprints during subduction and exhumation in a late Palaeozoic HP metamorphic terrain. Massive metabasites of hydrothermally altered enriched mid-ocean ridge basalt (E-MORB) origin are in association with banded metabasic rocks of volcano-sedimentary origin and metapelites. Fluid-rock interactions that likely occurred during seafloor hydrothermal alteration and early subduction metasomatism increased δ18O values, as well as K2O, Na2O, MgO, and LILE contents and decreased CaO contents of metabasites. Most metabasites have retained their early-subduction and pre-HP trace element and isotopic composition, even for rocks metamorphosed to lower eclogite-facies P–T conditions. Micaschists also preserved apparent pelitic protolith trace element values and oxygen isotopic compositions. During retrograde metamorphism related to the exhumation, metabasites were rehydrated by fluids in equilibrium with the host rock compositions, which were likely derived from the basic rocks. This style of fluid–rock interaction formed a greenschist facies mineral assemblage. Metabasites that underwent pervasive alteration by seafloor hydrothermal and metasomatism processes prior to peak metamorphism, show greater effects of retrogression and albitisation, probably because they were richer in H2O and Na2O. The variety of metamorphic assemblages on the Ile de Groix is thus directly related to the pre-HP rock composition. The extent of retrogression in the western part of the Ile de Groix primarily reflects stronger metasomatic intensities than in the eastern part. 相似文献