Oxygen isotope ratios in magnetite core-and-mantle structures

In a polymetamorphic, felsic, biotite-bearing gneiss, biotite has reacted to form magnetite and microcline. The resulting structure is a magnetite core surrounded by a mantle of feldspar and quartz normally not exceeding 20mm in diameter. Measurements of oxygen isotope ratios disclose disequilibrium between mantle microcline and mantle quartz and also between mantle and matrix minerals of the same species. A clustering of temperature estimates from the oxygen isotope distribution between magnetite and quartz and between magnetite and microcline in the interval 550 to 600°C suggests an approach to oxygen isotope equilibrium. No signs of a re-equilibriation of the reacting biotite can be found.     

Isotopic composition of cellulose from aquatic organisms

The stable isotopic ratios of oxygen, carbon and the non-exchangeable carbon-bound hydrogen of cellulose from marine plants (algae and higher vascular forms) and animals (tunicates) collected in their natural habitats and from freshwater vascular plants grown in the laboratory under controlled conditions were determined.The δ¹⁸Ovalues of cellulose from all the plants and animals were 27 ±3% more positive than the δ¹⁸O values of the waters in which the organisms grew. Temperature had little or no influence on this relationship for three species of freshwater vascular plants that were analyzed. The relationship between the δ¹⁸O values of cellulose and the water used in its synthesis is probably established by the isotopic fractionation that occurs during the hydration of carbonyl groups of the intermediates involved in cellulose synthesis.The δD values of the non-exchangeable hydrogen of cellulose (determined by analyzing cellulose nitrate) from different organisms that grew in the same environment differed by large amounts. This difference ranged up to 200‰ for different species of algae collected at a single site: the corresponding difference for different species of tunicates and vascular plants was 60 and 20‰ respectively. The δD values of cellulose nitrate from different species of freshwater vascular plants grown in water of constant temperature and isotopic composition differed by as much as 60‰ The relationship between the δD values of the carbon-bound hydrogen of cellulose and the water used in its synthesis displayed a significant temperature dependence for four species of freshwater vascular plants that were analyzed. The δD values of cellulose nitrate prepared from different parts of one of the plants grown under constant conditions differed by 40‰ Hydrogen isotopic fractionation during cellulose synthesis appears to be more variable among different species and displays a larger temperature dependence than was suggested by previous studies.     

Oxygen and silicon isotope ratios of the Luna 20 soil

The δ O¹⁸ and δ Si³⁰ analyses of the Luna 20 soil sample are +6.18 and +0.22, respectively, relative to the SMOW and Rose Quartz standards. However, an anomalous δ O¹⁸ value of +8.13 was obtained on one aliquot of the Luna 20 sample. Possible reasons for this apparently erroneous result are discussed.     

The oxygen and carbon isotope composition of Carboniferous fossil components: sea-water effects

The aragonitic molluscs and lime-mud of the Pennsylvanian Buckhorn asphalt (Deese Group) of southern Oklahoma precipitated calcium carbonate in oxygen and carbon isotopic equilibrium with ambient sea-water. In addition, δ¹⁸O values indicate that the pelecypods precipitated their shells during the warmer months of the year. The coiled nautiloids probably precipitated their shells in the warm surface water and throughout the year. For the orthocone nautiloids, the δ¹⁸O values suggest that they precipitated their shells in deeper/cooler water. The low-Mg calcite brachiopods of the Mississippian Lake Valley Formation of New Mexico precipitated shells in oxygen and carbon isotopic equilibrium with ambient sea-water. The δ¹⁸O and δ¹³C values of the Buckhorn and Lake Valley faunas, in conjunction with other published results, suggest that Carboniferous sea-water was, on a average, depleted in δ¹⁸O by 1·5 ± 2‰, PDB, relative to Recent sea-water. However, the δ¹³C value of +2.6 ± 2‰, PDB, for average Carboniferous sea-water is similar to that of Recent ocean water. Early diagenetic alteration of metastable carbonates probably occurs in a meteoric-sea-water mixing zone. In this zone the oxygen and carbon isotopic compositions of these components are increased by about 2-4‰, PDB over their marine composition.     

Oxygen isotope ratios of cellulose-derived phenylglucosazone: An improved paleoclimate indicator of environmental water and relative humidity

Oxygen atoms within fossil wood provide high-resolution records of climate change, particularly for the Quaternary. However, current analysis methods of fossil cellulose do not differentiate between different positions of the oxygen atoms. Here, we propose a refinement to tree-cellulose paleoclimatology modeling, using the cellulose-derived compound phenylglucosazone as the isotopic substrate. Stem samples from trees were collected at northern latitudes as low as 24°37′N and as high as 69°00′N. We extracted stem water and cellulose from each stem sample and analyzed them for their ¹⁸O content. In addition, we derived the cellulose to phenylglucosazone, a compound which lacks the oxygen attached to the second carbon of the cellulose-glucose moieties. Oxygen isotope analysis of phenylglucosazone allowed us to calculate the ¹⁸O content of the oxygen attached to the second carbon of the cellulose-glucose moieties. By way of these analyses, we tested two hypotheses: first, that the ¹⁸O content of the oxygen attached to second carbon will more closely reflect the ¹⁸O content of the stem water, and will not resemble the ¹⁸O content of either cellulose or its derivative phenylglucosazone. Second, tree-ring models that incorporate the variable oxygen isotope fractionation shown here and elsewhere are more accurate than those that do not. Our first hypothesis was rejected on the basis that the oxygen isotope ratios of the oxygen attached to the second carbon of the glucose moieties had a noisy isotopic signal with a large standard deviation and gave the poorest correlation with the oxygen isotope ratios of stem water. Related to this isotopic noise, we observed that the correlation between oxygen isotope ratios of phenylglucosazone with both stem water and relative humidity were higher than those observed for cellulose. Our hypothesis about tree-ring models which account for changes in the oxygen isotopic fractionation during cellulose synthesis was consistent only for the ¹⁸O content of phenylglucosazone. We showed that the tree-ring model based on the ¹⁸O content of phenylglucosazone was an improvement over existing models that are based on whole cellulose. Additionally, this approach may be used in other cellulose based archives such as peat deposits and lacustrine sediments.     

Oxygen and hydrogen isotope ratios in freshwater chert as indicators of ancient climate and hydrologic regime

The oxygen and hydrogen isotopic composition of Eocene and Miocene freshwater cherts in the western United States records regional climatic variation in the Cenozoic. Here, we present isotopic measurements of 47 freshwater cherts of Eocene and Miocene age from the Great Basin of the western United States at two different sites and interpret them in light of regional climatic and tectonic history. The large range of δ¹⁸O of terrestrial cherts measured in this study, from 11.2‰ to 31.2‰ (SMOW: Standard Mean Ocean), is shown to be primarily the result of variations in δ¹⁸O of surface water. The following trends and patterns are recognized within this range of δ¹⁸O values. First, in Cenozoic rocks of northern Nevada, chert δ¹⁸O records the same shift observed in authigenic calcite between the Eocene and Miocene that has been attributed to regional surface uplift. The consistent covariation of proxies suggests that chert reliably records and retains a signal of ancient meteoric water isotopic composition, even though our analyses show that chert formed from warmer waters (40°C) than coexisting calcite (20°C). Second, there is a strong positive correlation between δ¹⁸O and δD in Eocene age chert from Elko, Nevada and Salina, Utah that suggests large changes in lake water isotopic composition due to evaporation. Evaporative effects on lake water isotopic composition, rather than surface temperature, exert the primary control on the isotopic composition of chert, accounting for 10‰ of the 16‰ range in δ¹⁸O measured in Eocene cherts. From authigenic mineral data, we calculate a range in isotopic composition of Eocene precipitation in the north-central Great Basin of −10 to −14‰ for δ¹⁸O and −70 to −100‰ for δD, which is in agreement with previous estimates for Eocene basins of the western United States. Due to its resistance to alteration and record of variations in both δ¹⁸O and δD of water, chert has the potential to corroborate and constrain the cause of variations in isotope stratigraphies.     

Oxygen isotope composition of syngenetic inclusions in diamond from the Finsch Mine,RSA

Oxygen isotope data have been obtained for silicate inclusions in diamonds, and similar associated minerals in peridotitic and eclogitic xenoliths from the Finsch kimberlite by laser-fluorination. Oxygen isotope analyses of syngenetic inclusions weighing 20–400 μg have been obtained by laser heating in the presence of ClF₃. ¹⁸O/¹⁶O ratios are determined on oxygen converted to CO₂ over hot graphite and, for samples weighing less than 750 μg (producing <12 μmoles O₂) enhanced CO production in the graphite reactor causes a systematic shift in both δ¹³C and δ¹⁸O that varies as a function of sample weight. A “pressure effect” correction procedure, based on the magnitude of δ¹³C (CO₂) depletion relative to δ¹³C (graphite), is used to obtain corrected δ¹⁸O values for inclusions with an accuracy estimated to be ±0.3‰ for samples weighing 40 μg.Syngenetic inclusions in host diamonds with similar δ¹³C values (−8.4‰ to −2.7‰) have oxygen isotope compositions that vary significantly, with a clear distinction between inclusions of peridotitic (+4.6‰ to +5.6‰) and eclogitic paragenesis (+5.7‰ to +8.0‰). The mean δ¹⁸O composition of olivine inclusions is indistinguishable from that of typical peridotitic mantle (5.25 ± 0.22‰) whereas syngenetic purple garnet inclusions possess relatively low δ¹⁸O values (5.00 ± 0.33‰). Reversed oxygen isotope fractionation between olivine and garnet in both diamond inclusions and diamondiferous peridotite xenoliths suggests that garnet preserves subtle isotopic disequilibrium related to genesis of Cr-rich garnet and/or exchange with the diamond-forming fluid. Garnet in eclogite xenoliths in kimberlite show a range of δ¹⁸O values from +2.3‰ to +7.3‰ but garnets in diamondiferous eclogites and as inclusions in diamond all have values >4.7‰.     

Oxygen isotope composition of diatoms from sediments of Lake Kotokel (Buryatia)

This is a summary of new oxygen isotope record of diatoms from Lake Kotokel sediments, with implications for responses of the lake system and its environment to global change over the past 46 kyr. Fossil diatoms in all samples are free from visible contamination signatures and contain no more than 2.5% Al₂O3, which ensures reliable reconstructions. The 5¹⁸O values in diatoms vary between + 23.7 and + 31.2%c over the record. The results present mainly diatom assemblages of summer blooming periods, except for the time span between 36 and 32 kyr, when the isotopic signal records mainly a shift from summer to spring blooming conditions. Possible water temperature changes only partly explain the changes in the isotopic record. The observed isotopic patterns are produced mainly by isotope changes in lake water in response to variations in air temperature, hydrology, and atmospheric circulation in the region. During Marine Isotope Stage (MIS) 2 (Last Glacial maximum), high 5¹⁸Od_iatom resulted from rapid evaporation and low fluvial inputs. The high 5¹⁸Od_iatom values of about + 29 to + 30%c during the first half of MIS 1 (Holocene interglacial) suggest an increased share of summer rainfalls associated with southern/southeastern air transport. The 5¹⁸Odi_atom decrease to + 24%c during the second half of MIS 1 is due to the overall hemispheric cooling and increased moisture supply to the area by the Atlantic air masses. The record of Lake Kotokel sediments provides an example of complex interplay among several climatic/environmental controls of 5¹⁸O_diatom during the Late Pleistocene and the Holocene.     

Isotopic composition of silicon in meteorites

Samples of bulk meteorites show only mass-dependent fractionation of silicon isotopes. No isotopic anomalies were found. The variation of the ratios ²⁹Si/²⁸Si and ³⁰Si/²⁸Si over the meteorite classes is small; 1%. per mass unit difference. The average Si isotopic composition for each class of meteorites is identical, within analytical uncertainties. This is quite unlike O, whose anomalous isotopic abundances in bulk samples differentiate among the classes of meteorites. The overlapping abundance ranges of Si isotopes among many classes of meteorites suggest closed-system behavior for this element prior to meteorite accretion and allow calculation of an average solar system Si isotope composition.     

Sulfur isotope ratios of Icelandic rocks

Sulfur isotope ratios have been determined in 27 selected volcanic rocks from Iceland together with their whole rock chemistry. The ³⁴S of analyzed basalts ranges from –2.0 to +0.4 with an average value of –0.8 Tholeiitic and alkaline rocks exhibit little difference in ³⁴S values but the intermediate and acid rocks analyzed have higher ³⁴S values up to +4.2 It is suggested that the overall variation in sulfur isotope composition of the basalts is caused by degassing. The small range of the ³⁴S values and its similarity to other oceanic and continental basalts, suggest that the depleted mantle is homogeneous in its sulfur isotope composition. The ³⁴S of the depleted mantle is estimated to be within the range for undegassed oceanic basalts, –0.5 to +1.0     

Oxygen and strontium isotope ratios in some ejecta from the Alban Hills volcanic area,Roman comagmatic region

CaSO₄ has been investigated at room temperature over the pressure range of 0 to 160 kbar. A reversible, sluggish transition that occurs at about 20 kbar with a volume change of about 4% has been confirmed. The x-ray powder data collected at pressure can be indexed on the monoclinic monazite structure cell (P2₁/n) which is considered to be the most likely model structure for the new HP CaSO₄ phase. The transition is largely distortional and involves rotation and displacement, but essentially preserves the chains of edge shared CaO₈₍₉₎ and SO₄ polyhedra found in the orthorhombic anhydrite (Bbmm) structure.     

Carbon isotope fractionation in wood during carbonization

A significant uncertainty exists as to whether δ¹³C values in charcoal meaningfully represent the stable isotopic content of the original material, with studies suggesting variable responses to both natural and laboratory heating. An extensive study was undertaken using fully homogenised samples of wood taken from Eucalyptus spp., Quercus robur and Pinus radiata. The results demonstrate that the duration of heating had no tangible effect on the final composition of the charred material, with the δ¹³C and carbon content of wood fixed after 30 min of heating. Furthermore, all three wood types become progressively depleted in ¹³C with increasing temperature. The results demonstrate that even at temperatures commonly reached in natural fires (<450 °C) isotopic fractionation of up to 1.3‰ can take place indicating that the absolute values obtained from charcoal extracted for paleoenvironmental reconstruction must be interpreted with caution.     

Isotopic composition of hydration water in gypsum

The isotopic composition of the hydration water of gypsum is a sensitive diagnostic tool for specifying the mechanisms of its formation, either from an evaporating brine, by hydration of anhydriate or in situ formation in surface or groundwaters through oxidation of sulfides. Primarily, gypsum is formed in isotopic equilibrium with the mother brine; later, exchange of water occurs rapidly under humid conditions by means of a mechanism of recrystallization of gypsum or through diffusion of water into the intact crystal. Under arid conditions, however, the primary isotopic record has been preserved, in some instances, since the Pleistocene.     

Isotopic composition of strontium in Indian kimberlites

Strontium isotopic studies on twenty three whole rock kimberlites from two petrographic provinces in India show variation of initial ${}^{87}\text{Sr}{}^{86}\text{Sr}$ ratios from 0.7027 to 0.7102. The variation is unrelated to the degree of alteration. Between the micaceous and basaltic varieties there is some overlap in the Sr isotopic ratios. Leaching experiments on whole rock samples showed more highly radiogenic Sr in leaches compared to the bulk samples.In two diatremes, the initial ${}^{87}\text{Sr}{}^{86}\text{Sr}$ ratios show a positive correlation with $\text{Rb}\text{Sr}$ which is believed to reflect a source event earlier than the formation of the kimberlites. The observed Sr isotopic data can be caused by (i) melting of a heterogeneous source or (ii) disequilibrium partial melting in the source region. In the former case, variable isotopic composition would be a necessary consequence of melting in small subsystems.     

Isotopic composition of thermal waters in Chukotka

Twenty three groups of thermomineral springs in eastern Chukotka with the discharge temperature of 2 to 97°C and mineralization of 1.47 to 37.14 g/l are studied and compared with surface freshwater from their localities. The δD and δ¹⁸O values in surface waters vary from ?121.4 to ?89.5‰ and from ?16.4 to ?11.1‰, respectively, while respective values in thermomineral waters range from ?134.2 to ?92.5‰ and from ?17.6 to ?10.5‰. The δD value in surface waters decreases from the east to west, i.e., toward interior areas of the peninsula. Hydrothermal springs most depleted in deuterium (δD < ?120‰) are localized in the geodynamically active Kolyuchinskaya-Mechigmen Depression. According to the proposed formation model of Chukotka thermomineral waters, their observed chemical and isotopic characteristics could result from the mixing (in different proportions) of surface waters with the deep-sourced isotopically light mineralized component (δD ≈ ?138‰, δ¹⁸O ≈ ?19‰, M = 9.5?14.7 g/l). The latter originates most likely from subpermafrost waters subjected to slight cryogenic metamorphism.     

Oxygen isotope composition of kaolinite rocks as an indicator of different stages of their lithogenesis

Doklady Earth Sciences -     

多接收器等离子体质谱法Zn同位素比值的高精度测定

详细报道了Zn同位素比值的多接收器等离子体质谱(MC-ICP-MS)高精度测定方法,包括:MC-ICP-MS Zn同位素测量过程中的质量歧视校正、同质异位素干扰评估、基质效应调查和同位素测量的长期重现性检验.研究表明,在测定条件下,运用标样一样品交叉法能有效地进行仪器质量歧视校正.同质异位素干扰的评估通过3种方式进行,即:在高分辨状态下同质异位数干扰信号的直接测定,低分辨状态下Zn同位素原始数据间相关关系的检验和低分辨下浓度梯度效应研究.结果表明,在低分辨模式下,尽管66Zn、67Zn、68Zn的同质异位素干扰信号很小,但的确存在,要获得准确同位素比值,必须使标样和样品的浓度在合适的范围内匹配.在基质效应方面,主要考察Fe对Zn同位素比值测定的影响.结果表明,当溶液中Fe/Zn(质量比)不大于0.2时,Fe对Zn同位素比值测定无影响.重复性测定中,δ66ZnGSB-Romil=6.96‰±0.11‰(2sd),δ67ZnGSB-Romil=10.4‰±0.20‰(2sd),δ68ZnGSB-Romil=13.8‰±0.22‰(2sd),达到国际同类实验室先进水准.运用所建立的方法,对地质岩石成分分析国家标准物质GBW 07270(闪锌矿)进行了Zn同位素平均成分测定为:δ66Zn=6.71‰±0.03‰(20),δ67Zn=10.08‰±0.05‰(20),δ68Zn=13.37‰±0.07‰(2σ).     

Assessing meteoric water composition and relative humidity fromO andH in wood cellulose: paleoclimatic implications for southern Ontario, Canada

An empirical model is presented that derives the initial isotopic composition of water used by terrestrial plants and the relative humidity that prevailed during photosynthesis from the isotopic composition of oxygen and carbon-bound hydrogen in the plant cellulose. The model uses fixed values for the fractionation factors that describe the evapotranspirative isotopic enrichment of leaf waters and the biochemical fractionations occurring during cellulose synthesis. When applied to cellulose extracted from fossil plant matter, the model can be used to generate quantitative estimates of the temperature and moisture regimes of the past. The application of the model is demonstrated by consideration of δ¹⁸O and δ²H results on cellulose from fossil wood collected at Brampton, Ontario.The Brampton data yield records of systematic changes in the temperature and moisture regimes of the eastern Great Lakes region over the past 11 500 a. Both mean annual temperature and photosynthetic humidity increased substantially from values much lower than the present at the end of the Wisconsin Stage, to values higher than the present in the mid-Holocene. The phase relation of the paleotemperature and paleohumidity curves engenders differentiation of the climatic history at Brampton into four characteristic zones: (I) a period of ameliorating climate predominantly much colder and drier than now, lasting until about 7400 B.P.; (II) an “early Hypsithermal” period of warm and dry conditions, that transformed after 6000 a B.P. into (III) the “main Hypsithermal” time of warmth and pronounced moistness. Subsequent climatic detrioration led to establishment of (IV) cool, moist conditions like the present sometime within the last few thousand years.     

Calcium isotope ratios in animal and human bone

Calcium isotopes in tissues are thought to be influenced by an individual’s diet, reflecting parameters such as trophic level and dairy consumption, but this has not been carefully assessed. We report the calcium isotope ratios (δ^44/42Ca) of modern and archaeological animal and human bone (n = 216). Modern sheep raised at the same location show 0.14 ± 0.08‰ higher δ^44/42Ca in females than in males, which we attribute to lactation by the ewes. In the archaeological bone samples the calcium isotope ratios of the herbivorous fauna vary by location. At a single site, the archaeological fauna do not show a trophic level effect. Humans have lower δ^44/42Ca than the mean site fauna by 0.22 ± 0.22‰, and the humans have a greater δ^44/42Ca range than the animals. No effect of sex or age on the calcium isotope ratios was found, and intra-individual skeletal δ^44/42Ca variability is negligible. We rule out dairy consumption as the main cause of the lower human δ^44/42Ca, based on results from sites pre-dating animal domestication and dairy availability, and suggest instead that individual physiology and calcium intake may be important in determining bone calcium isotope ratios.