陆生蜗牛壳体碳酸盐团簇同位素组成及其古气候意义

碳酸盐团簇同位素是国际上新近开发的地质温度计,可以精确重建过去的温度变化。蜗牛壳体化石是研究古气候的理想载体,其种属组合和碳、氧同位素组成分析提供了丰富的气候环境信息。在此基础上,蜗牛壳体团簇同位素分析势必会为古温度定量重建提供强有力手段。然而,相关研究却开展得较少,值得我们投入更多的精力去推动该领域的发展。本研究首先介绍了碳酸盐团簇同位素及其制备和分析方法,以便古气候研究者对新兴研究手段有所了解。然后,对蜗牛壳体团簇同位素的研究历史与现状进行了梳理,指出了研究中尚存的不解问题,并对未来的研究进行了展望。总之,尽管野外采集蜗牛的团簇同位素温度系统地高于生长季温度,但二者之间存在较好的线性关系,所以蜗牛壳体团簇同位素可以用来重建蜗牛生长季节的环境温度。然而,在相同地点蜗牛壳体团簇同位素存在种属差异（如华蜗牛团簇同位素温度比巴蜗牛高3℃左右）,所以精确重建古温度需要建立属一级蜗牛壳体团簇同位素-温度转换方程。同时,通过团簇同位素温度和蜗牛壳体δ¹⁸O计算出的蜗牛体液δ¹⁸O可以反映降水的氧同位素信息,是研究古水文循环的重要指标。黄土地层中蜗牛壳体化石团簇同位素研究显示我国北方末次冰期的夏季温度要比现代低7~10℃左右。虽然该温度变幅有待进一步研究确证,但它们至少为冰期-间冰期温度变化提供了独立证据和有用参考。鉴于显口多点螺（Punctum orphana）化石在黄土地层中连续赋存且最可能被广泛用于古温度重建研究,我们未来可优先建立该种属蜗牛的团簇同位素-温度转换方程。

     

陆生蜗牛壳体高分辨率的稳定氧同位素记录与季节的干湿变化

季节变化是气候系统的基本特征,然而受研究材料和方法所限,陆相沉积序列中难以获得古气候的季节变化信息。文章选择兰州地区,在旱季和雨季分别采集两个现生条华蜗牛（Cathaica fasciola）,通过沿壳体生长轴高分辨率取样分析,发现兰州地区旱季生长的蜗牛壳体稳定氧同位素组成（δ¹⁸O）整体偏正、雨季生长的壳体显著偏负,单个壳体内部δ¹⁸O的波动幅度捕获了季节干湿变化信号。综合现代观测、黄土高原其他地区记录、通量平衡模式等证据,提出蜗牛壳体δ¹⁸O旱季偏正,主要受蒸发效应和温度影响,蒸发效应可能更为重要;蜗牛壳体δ¹⁸O雨季偏负,主要受降水氧同位素组成和温度影响。蜗牛壳体高分辨率的稳定氧同位素研究在揭示亚洲古季风季节干湿变化方面有巨大应用潜力,系统的现代过程研究是推动该方法进一步发展的关键所在。

     

Flux balance models for the oxygen and carbon isotope compositions of land snail shells

A simple flux balance model with a diffusive, evaporative boundary layer indicates that the time constant (characteristic time) for approach to oxygen isotope steady state in the body fluid of land snails is ∼19 min or less. These comparatively short times support an assumption that the snail’s aragonitic shell is commonly precipitated from a body fluid that is at, or near, isotopic steady state. The model indicates that the steady-state δ¹⁸O value of snail shell carbonate depends upon the temperature, relative humidity, δ¹⁸O of the input liquid water, and δ¹⁸O of ambient water vapor. Model shell δ¹⁸O values were calculated for the warm, wet months corresponding to times of snail activity at some European sites. Linear regression of these predicted values against published, measured values yielded the expression: δ¹⁸O_calc = 0.93(±0.13) δ¹⁸O_meas −0.9(±0.2), with r² = 0.65. As indicated by the value of r², there is scatter in the relationship, but the slope and intercept are close to one and zero, respectively, which lends credence to the model. Therefore, temporal or spatial changes recorded in the δ¹⁸O values of land snail shells appear to be selectively seasonal—commonly the warm, wet months—and include the effects of relative humidity.For carbon, the time constant for approach to isotopic steady state in the bicarbonate dissolved in the body fluid of land snails is predicted to be ∼16 min or less. New and published δ¹³C measurements of aragonite shell and associated organic matter exhibit an overall correlation, but with considerable scatter. As noted by previous workers, ¹³C-rich dietary “limestone” may account for some of the scatter. Additional scatter, according to the model presented herein, could arise from changes in the proportion of total oxidized carbon that is expelled by the snail as bicarbonate dissolved in body fluid (i.e., effects of relative changes in metabolic rates). These results affirm the need for caution in the interpretation of δ¹³C values of land snail aragonite shells solely in terms of dietary proportions of C₃ and C₄ plants.     

Oxygen isotope fractionation during the dolomitization of calcium carbonate

The oxygen isotope fractionation accompanying the hydrothermal dolomitization of CaCO₃ between 252 and 295°C has been investigated. Dolomitization (which occurs via the crystallization of one or more intermediate magnesian calcite phases) is characterised by a progressive lowering in δ⁸O, which smoothly correlates with the change in the Mg/(Mg + Ca) and the $\text{Sr}\text{(Mg + Ca)}$ ratios and with the sequential phase formation. The data support the proposals of Katz and Matthews (1977) that (a) all reaction occurs by solution and reprecipitation, (b) intermediate phases and dolomite form sequentially and (c) the intermediate phases form within limited solution zones surrounding the dissolving precursor. Calculated volumes of the solution zone for the aragonite → low magnesian calcite transformation are within the range 3.7–6.7 × 10^?5 liters (out of 5 × 10^?3 liters, the volume of the bulk solution used in the present study), and agree well with those calculated from strontium and magnesium partitioning data. Dolomite precipitates in apparent isotopic equilibrium with the bulk solution. The temperature dependence of the fractionation is defined by the equation 1000 Inα_D-H2O = 3.06 × 10⁶T^?2 ? 3.24 Dolomite-water fractionations from this equation are significantly lower than those obtained by extrapolation of the Northrop And Clayton (1966) calibration. The reaction zone model can be applied to explain near zero dolomite-calcite oxygen isotope fractionations reported by Epsteinet al. (1964).     

Oxygen isotope partitioning between phosphate and carbonate in mammalian apatite

The oxygen isotope compositions of phosphate and structural carbonate in mammalian enamel and bone apatite are linked to that of body water at constant body temperature near 37°C, but the isotope systematics of oxygen in structural carbonate are not well understood. Using coupled measurements of the oxygen isotope composition of structural carbonate and phosphate from horse tooth enamel, the apparent oxygen isotope fractionation factor between structural carbonate and body water is estimated to be 1.0263 ± 0.0014. These estimates provide a quantitative basis for using the oxygen isotope composition of structural carbonate in mammalian biogenic apatite for ecological, climatological, and physiological reconstruction.     

Oxygen and carbon stable isotopes of modern land snail shells as environmental indicators from a low-latitude oceanic island

Land snails provide a unique opportunity to study terrestrial paleoenvironments because their shells, which are generally highly abundant and well-preserved in the fossil record, contain a temporal record of environmental change in the form of isotope codes. To evaluate the utility of this approach for a low-latitude oceanic setting, 207 modern shells of 18 species of land snail were analyzed for their oxygen and carbon isotope composition along a north and south facing altitudinal gradient (10-2160 m a.s.l.) in Tenerife Island (∼28°N) of the Canary Archipelago.Shells collected at each locality showed a relatively large range in isotope composition which was greater along the south facing transect (drier and hotter), suggesting that the variance in shell isotope values may be related to water-stress. Although pooled isotope values did not generally show strong relationships with environmental variables (i.e., altitude, temperature and precipitation), mean isotope values were strongly associated with some climatic factors when grouped by site. The mean δ¹⁸O value of the shell (δ¹⁸O_shell) by site displayed a negative correlation with elevation, which is consistent with the positive relationship observed between temperature and the δ¹⁸O value of rain (δ¹⁸O_rain). Calculated δ¹⁸O values of the snail body water (δ¹⁸O_body) derived from observed temperatures and δ¹⁸O_shell values (using the equation of Grossman and Ku [Grossman E. L. and Ku T. L. (1986) Oxygen and carbon isotope fractionation in biogenic aragonite. Chem. Geol. (Isotope Geosci. Sec.)59, 59-74]) displayed a trend with respect to altitude that was similar to measured and hypothetical δ¹⁸O values for local rain water. The calculated δ¹⁸O_body values from the shell declined 0.17‰ (VSMOW) per 100 m, which is consistent with the “altitude effect” observed for tropical rains in Western Africa, and it correlated negatively with rainfall amount. Accordingly, lower δ¹⁸O_shell values indicate lower temperatures, lower δ¹⁸O_rain values and possibly, higher rainfall totals. A positive correlation between the mean δ¹³C values of shells (δ¹³C_shell) and plants by site suggests that shells potentially record information about the surrounding vegetation. The δ¹³C_shell values varied between −15.7 and −0.6‰ (VPDB), indicating that snails consumed C₃ and C₄/CAM plants, where more negative δ¹³C_shell values probably reflects the preferential consumption of C₃ plants which are favored under wetter conditions. Individuals with more positive δ¹³C_shell values consumed a larger percentage of C₄ plants (other potential factors such as carbonate ingestion or atmospheric CO₂ contribution were unlikely) that were more common at lower elevations of the hotter and drier south facing transect. The relatively wide range of shell isotope values within a single site requires the analysis of numerous shells for meaningful paleoclimatic studies. Although small differences were observed in isotope composition among snail species collected at a single sampling site, they were not significant, suggesting that isotope signatures extracted from multi-taxa snail data sets may be used to infer environmental conditions over a broad range of habitats.     

Oxygen isotope measurements of individual unmelted Antarctic micrometeorites

We present oxygen isotope measurements of 28 unmelted Antarctic micrometeorites measuring 150-250 μm (long axis) collected in the South Pole water well. The micrometeorites were all unmelted and classified as either fine-grained, scoriaceous, coarse-grained or composite (a mix of two other classes). Spot analyses were made of each micrometeorite type using an ion microprobe. The oxygen isotope values were measured relative to standard mean ocean water (SMOW) and range from δ¹⁸O = 3‰ to 60‰ and δ¹⁷O = −1‰ to 32‰, falling along the terrestrial fractionation line (TFL) within 2σ errors. Several analytical spots (comprising multiple phases) were made on each particle. Variability in the oxygen isotope ratios was observed among micrometeorite types, between micrometeorites of the same type and between analytical spots on a single micrometeorite indicating that micrometeorites are isotopically heterogeneous. In general, the lowest isotope values are associated with the coarse-grained micrometeorites whereas most of the fine-grained and scoriaceous micrometeorites have an average δ¹⁸O ? 22‰, suggesting that the matrix in micrometeorites is isotopically heavier than the anhydrous silicate phases. The oxygen isotope values for the coarse-grained micrometeorites, composed mainly of anhydrous phases, do not lie along the carbonaceous chondrite anhydrous mineral (CCAM) line, as observed for olivines, pyroxenes and some kinds of chondrules in carbonaceous chondrites, suggesting that coarse-grained MMs are not related to chondrules, as previously thought. Our measurements span the same range as values found for melted micrometeorites in other studies. Although four of the micrometeorites have oxygen isotope values lying along the TFL, close to the region where the bulk CI carbonaceous chondrites are found, 21 particles have very enriched ¹⁷O and ¹⁸O values that have not been reported in previous analyses of chondrite matrix material, suggesting that they could be a new type of Solar System object. The parent bodies of the micrometeorites with higher ¹⁸O values may be thermal metamorphosed carbonaceous asteroids that have not been found as meteorites either because they are friable asteroids that produce small particles rather than rocks upon collision with other bodies, or because the rocks they produce are too friable to survive atmospheric entry.     

Early‐middle Holocene land snail shell stable isotope record from Grotta di Latronico 3 (southern Italy)

This paper compares stable isotope (δ¹⁸O and δ¹³C) records of early–middle Holocene land snail shells from the archaeological deposits of Grotta di Latronico 3 (LTR3; southern Italy) with modern shell isotopic data. No substantial interspecific variability was observed in shell δ¹⁸O (δ¹⁸Os) of modern specimens (Pomatias elegans, Cornu aspersum, Eobania vermiculata, Helix ligata and Marmorana fuscolabiata). In contrast, interspecific shell δ¹³C (δ¹³Cs) variability was significant, probably due to different feeding behaviour among species. The δ¹⁸Os values of living land snails suggest that species hibernate for a long period during colder months, so that the signal of ¹⁸O‐depleted winter rainfall in their δ¹⁸Os is lost. This suggests that δ¹⁸Os and δ¹³Cs values of Pomatias elegans from this archaeological succession provide valuable clues for seasonal (spring–autumn) climatic conditions during the early–middle Holocene. The δ¹⁸Os values of fossil specimens are significantly lower than in modern shells and in agreement with other palaeoclimatic records, suggesting a substantial increase of precipitation and/or persistent changes in air mass source trajectories over this region between ca. 8.8 cal ka BP and 6.2–6.7 ka ago. The δ¹³Cs trend suggests a transition from a slightly ¹³C‐enriched to a ¹³C‐depleted diet between early and middle Holocene compared to present conditions. We postulate that this δ¹³Cs trend might reflect changes in the C3 vegetation community, potentially combined with other environmental factors such as regional moisture increase and the progressive decrease of atmospheric CO₂ concentration. Copyright © 2010 John Wiley & Sons, Ltd.     

Oxygen and carbon isotope composition of structural carbonate in weathering apatites from laterites, southern Brazil and western Senegal

The oxygen (δ¹⁸O_c) and carbon (δ¹³C_c) isotope compositions of the structural carbonate group (CO₃) in apatites from lateritic profiles were investigated. The weathering profiles, located in southern Brazil and in western Senegal, are developed on three different types of apatite-rich parent rock: carbonatite, metamorphosed marine phosphorite and sedimentary marine phosphorite. The parent rock apatites are of magmatic, hydrothermal, metamorphic and sedimentary origins. The in situ formation of apatite of weathering origin in the profiles is well documented petrographically and geochemically.The overall range of measured δ¹⁸O_c and δ¹³C_c values of apatites of weathering origin (22 to 27 SMOW for δ¹⁸O_c and −15 to −10 PDB for δ¹³C_c) is much smaller than the range of measured and/or published isotope compositions of parent rock apatites (4–35 for δ¹⁸O_c and −11 to +1 for δ¹³C_c). In any profile, the apatites of weathering origin can exhibit lower, similar or higher δ¹⁸O_c values than parent rock apatites. In contrast, their δ¹³C_c values are systematically and significantly lower than those of the parent rock apatites. Apatites formed as a result of weathering in laterites can therefore be readily distinguished from apatites of other origin on the basis of their isotope composition.Assuming that apatite CO₃ fractionates O in a way similar to calcite CO₃, the structural carbonate group of the apatites of weathering origin appears to form in approximate isotopic equilibrium with the weathering solutions. The very low δ¹³C_c values exhibited by these apatites indicate that the dominant sources of dissolved CO₂ in the soil water are organic. The isotope composition of structural carbonate in apatite of weathering origin in lateritic profiles may provide useful information for paleoenvironmental studies.     

Oxygen, carbon, and strontium isotope geochemistry of diamond-bearing carbonate rocks from Kumdy-Kol, Kokchetav Massif, Kazakhstan

Diamond-bearing carbonate rocks from Kumdy-Kol, Kokchetav massif, Kazakhstan, were strongly altered by fluids flowing through fractures and infiltrating along grain boundaries during exhumation. Alteration includes retrogradation of high-grade silicate assemblages by hydrous minerals, replacement of diamond by graphite and of dolomite by calcite. Diamond-bearing carbonate rocks are among the most intensely altered isotopically with δ¹⁸O_VSMOW values as low as +9‰, δ¹³C_VPDB=−9‰, and ⁸⁷Sr/⁸⁶Sr as high as 0.8050. Evidence of isotopic equilibration between coexisting dolomite and high-Mg calcite during ultrahigh-pressure metamorphism (UHPM) is preserved only rarely in samples isolated from infiltrating fluids by distance from fractures. Isotopic heterogeneity and isotopic disequilibrium are widespread on a hand-specimen scale. Because of this lack of homogeneity, bulk analyses cannot provide definitive measurements of ¹³C/¹²C fractionation between coexisting diamond and carbonate. Our study adequately documents alteration on a scale commensurate with observed vein structures. But, testing the hypothesis of metamorphic origin of microdiamonds has not fully succeeded because our analytical spatial resolution, limited to 0.5 mm, is not small enough to measure individual dolomite inclusions or individual diamond crystals.     

干旱化对成土碳酸盐碳同位素组成的影响

土壤碳酸盐的碳同位素组成可以作为古环境变化的指标.本文对黄土高原地区S1以来成土碳酸盐和红粘土中碳酸盐的碳同位素进行了研究.根据渭南、吉县、长武和会宁4个剖面末次间冰期以来土壤碳酸盐的碳同位素分析结果,探讨了不同气候条件下成土碳酸盐碳同位素组成的特征及其环境意义,指出气候的干湿程度可能是影响黄土地区成土碳酸盐δ13C值的主要原因;西峰红粘土序列碳酸盐的碳同位素记录表明,δ13C值在4.0Ma B.P.前后有一个明显增加的趋势,反映了我国西北地区上新世干旱化的发展,可能与青藏高原在这一时期发生较大规模的隆升有关.     

碳酸盐中碳、氧同位素快速制样装置研制

介绍一种碳酸盐中碳、氧同位素快速制样装置。实验证明,该装置具有真空度好、使用方便、无污染、制样效率高、成本低的优点,所生成的二氧化碳具有高纯、分析结果准确、可靠等特点,完全能满足碳酸盐中碳、氧同位素分析的制样要求。     

Oxygen isotope geochemistry of pyroclastic clinopyroxene monitors carbonate contributions to Roman-type ultrapotassic magmas

The oxygen isotope geochemistry and chemical composition of clinopyroxene crystals from Alban Hills pyroclastic deposits constrain the petrological evolution of ultrapotassic Roman-type rocks. Volcanic eruptions in the 560–35 ka time interval produced thick pyroclastic deposits bearing clinopyroxene phenocrysts with recurrent chemical characteristics. Clinopyroxenes vary from Si–Mg-rich to Al–Fe-rich with no compositional break, indicating that they were derived from a continuous process of crystal fractionation. Based on the ¹⁸O and trace element data no primitive samples were recovered: monomineralic clinopyroxene cumulates set the oxygen isotope composition of primary magmas in the range of uncontaminated mantle rocks (5.5), but their REE composition resulted from extensive crystal fractionation. Departing from these mantle-like ¹⁸O_Cpx values the effects of crustal contamination of clinopyroxene O-isotope composition were identified and used to monitor chemical variations in the parental magma. ¹⁸O values in Si–Mg-rich clinopyroxene are slightly higher than typical mantle values (5.9–6.2), and the low REE contents are representative of early stages of magmatic differentiation. ¹⁸O values as high as 8.2 are associated with Al–Fe³⁺-rich clinopyroxene showing high REE contents. These ¹⁸O values are characteristic of crystals formed during the late magmatic stages of each main eruptive phase. Geochemical modelling of ¹⁸O values vs. trace element contents indicates that these ultrapotassic magmas were derived from fractional crystallization plus assimilation of limited amounts of carbonate wall rocks starting from a primary melt, and from interaction with CO₂ derived from country rocks during crystal fractionation.     

Re-evaluation of linearity and precision of Gas Bench II-IRMS system and potential implications for carbon and oxygen isotope measurements on small-sized carbonate samples

In this study, the δ^13C and δ^18O values were systematically measured on NBS-18, NBS-19 and IAEA-CO-1 with different sample sizes, with the objective to examine the stability and reproducibility of previously developed linearity correction strategy especially for small-sized samples （e.g. 〈50 μg）. Firstly, the δ^13C and δ^18O values of NBS-19 standards （6-10 samples per run） with sample sizes scattered below -100 μg were determined in three different runs. The logarithmic regressions were performed on the plots of δ-values vs. peak area （sample size） for each run and the correction was applied using peak area of the first peak. Results show that two of the three data sets have almost the same regressive equations for both δ^13C and δ^18O values. The maximum difference in δ^13C values calculated by three equations when sample size varies between -10 and -100 μg is better than 0.15‰, compared with the maximum 0.82‰ for δ^18O values. Since alteration of phosphoric acids could not influence carbon isotope, the 〈0.15‰ difference in calculated δ^13C values should reflect the stability of mass spectrometer conditions. In contrast, the large difference in regressive equations for δ^18O values may be attributed to changed oxygen isotope in phosphoric acids due to exchange with atmosphere through time. It means that standards with sample sizes properly distributed should be arranged in every run for subsequent linearity correction of δ^18O values of small-sized samples （e.g. marine ostracode）.     

Stable chlorine and carbon isotope measurements of selected chlorinated organic solvents

Stable Cl and C isotope ratio results for 3 selected chlorinated solvents, perchloroethylene (PCE), trichloroethylene (TCE) and 1,1,1-trichloroethane (TCA) provided by 4 different manufacturers are presented. The isotope ratio for all compounds range between −3.5 and +6.0‰ forδ³⁷Cl and from −37.2 to −23.3%. forδ¹³C. The greatest³⁷Cl difference between manufacturers is observed in the TCE samples which showδ³⁷CI values of −2.5%o for PPG, +2.43‰ for ICI and +4.4‰ for DOW. TCAs show a smaller range (−2.4 to +2.0‰), while the TCEs have slightly different³⁷Cl contents. The¹³C data show the most distinctδ¹³C values for PCEs (−23.3 for DOW, −24.1 for Vulcan, −33.8 for PPG and −37.2‰ for ICI) while both TCEs and TCAs show a smallerδ¹³C range, but still distinct differences. These preliminary data suggest that each manufacturer and solvent type may have distinctiveδ⁶³⁷Cl andδ¹³C values. These results show that by using a combination of³⁷Cl and¹³C, there is a potential to indicate a specific source of chlorinated solvents, as well as an ability to delineate contamination episodes caused by these compounds in groundwaters.     

Oxygen and carbon isotope geochemistry of the Krivoy rog iron formation,Ukranian SSR

Oxygen and carbon isotope analyses of samples from three mines in the Krivoy Rog iron formation, Ukranian SSR, are reported here. Maximum and minimum quartz-magnetite fractionation values ($\text{Δ}{}_{\mathrm{<mtext>QM</mtext>}}$) and inferred temperature range in degrees centrigrade for each mine are:

     

17.

Preservation of the shell matrix protein dermatopontin in 1500 year old land snail fossils from the Bonin islands     

Isao Sarashina  Yoshiki Kunitomo  Minoru Iijima  Satoshi Chiba  Kazuyoshi Endo   《Organic Geochemistry》2008,39(12):1742

Organic molecules such as proteins can be preserved in certain fossils. The bulk properties of fossil proteins of both vertebrates and invertebrates have been studied for over half a century. Named proteins have so far been identified, however, only in vertebrate fossils, such as collagen from mammoth bones. Using immunological assays, we examined 1500 year old fossils of the extinct land snail Mandarina luhuana from the Bonin islands for the presence of dermatopontin, a molluscan shell matrix protein. First, we examined the shell microstructure and mineralogy of the fossil shells using scanning electron microscopy (SEM) and powder X-ray diffraction (XRD) in order to estimate the extent of diagenetic alteration. The results suggest that the original microstructure and mineralogy of the shells are preserved. Antiserum raised against the Type-1 dermatopontin fragment of the living land snail Euhadra brandtii showed significant immunological reactivity with the extracts from the fossil shells of M. luhuana. Immunological binding curves drawn for the shell extracts of extant M. aureola and the extinct M. luhuana confirmed the presence of dermatopontin in the fossil shells and provided an estimate that about 75–98% of the original dermatopontin was lost from the M. luhuana fossils. This is the first report of a named protein being identified in invertebrate fossils.     

18.

Compositional differences in enstatite chondrites based on carbon and nitrogen stable isotope measurements     

Monica M. Grady  I. P. Wright  L. P. Carr  C. T. Pillinger 《Geochimica et cosmochimica acta》1986,50(12):2799-2813

Carbon and nitrogen abundance and isotopic compositions, from four EH4, one EH5, five EL6 chondrites and one aubrite, were determined by using stepped pyrolysis (N only) and combustion (N and C) extractions in attempts to distinguish the components present. Carbon contents range from 0.15 to 0.70 wt%, with no systematic relationship between carbon content and meteorite group or petrologic type. Whole-rock δ¹³C values range from −28.5 to −4.1 %., Most C occurs as graphite and when temperature steps above 700°C are considered, there is a difference between EH4,5 (δ¹³C = −9.1 to -5.8%.) and EL6 chondrites (δ¹³C = −6.7 to +4.2%.). Carbon in Bustee aubrite is isotopically lighter (δ¹³C = −24%.) than in any enstatite chondrite.

Nitrogen occurs as osbornite, sinoite and in isostructural substitution for oxygen in silicate lattice sites. Nitrogen abundances and isotopic compositions are more variable than C, due to the heterogenous distribution of N-bearing minerals. Three EL6's containing osbornite have higher N concentrations than other type 6 enstatite chondrites. Sinoite, where present, is depleted in ¹⁵N relative to osbornite. Nitrogen in the Bustee aubrite has a similar abundance and δ¹⁵N value to those of EL6's, again dominated by the presence of osbornite.

In addition to the refractory C-and N-bearing minerals there is also organic material (largely terrestrial contamination) and evidence for at least two “exotic” components. The first is a host for Xe (HL) and is characterized by δ¹³C <-−47%. and δ¹⁵N ≤−73%., whereas the second is less well-defined, but is marked by δ¹⁵N = +269%.     

19.

Reformulated O correction of mass spectrometric stable isotope measurements in carbon dioxide and a critical appraisal of historic ‘absolute’ carbon and oxygen isotope ratios     

Jan Kaiser 《Geochimica et cosmochimica acta》2008,72(5):1312-1334

Mass-spectrometric stable isotope measurements of CO₂ use molecular ion currents at mass-to-charge ratios m/z 44, 45 and 46 to derive the elemental isotope ratios n(¹³C)/n(¹²C) and n(¹⁸O)/n(¹⁶O), abbreviated ¹³C/¹²C and ¹⁸O/¹⁶O, relative to a reference. The ion currents have to be corrected for the contribution of ¹⁷O-bearing isotopologues, the so-called ‘¹⁷O correction’. The magnitude of this correction depends on the calibrated isotope ratios of the reference. Isotope ratio calibrations are difficult and are therefore a matter of debate. Here, I provide a comprehensive evaluation of the existing ¹³C/¹²C (¹³R), ¹⁷O/¹⁶O (¹⁷R) and ¹⁸O/¹⁶O (¹⁸R) calibrations of the reference material Vienna Standard Mean Ocean Water (VSMOW) and CO₂ generated from the reference material Vienna Pee Dee Belemnite (VPDB) by reaction with 100% H₃PO₄ at 25 °C (VPDB-CO₂). I find , ¹⁸R_VSMOW/10⁻⁶ = 2005.20 ± 0.45, ¹³R_VPDB-CO2/10^-6= 11124 ± 45, and ¹⁸R_VPDB-CO2/10^-6=2088.37±0.90. I also rephrase the calculation scheme for the ¹⁷O correction completely in terms of relative isotope ratio differences (δ values). This reveals that only ratios of isotope ratios (namely, ¹⁷R/¹³R and ¹³R¹⁷R/¹⁸R) are required for the ¹⁷O correction. These can be, and have been, measured on conventional stable isotope mass spectrometers. I then show that the remaining error for these ratios of isotope ratios can lead to significant uncertainty in the derived relative ¹³C/¹²C difference, but not for¹⁸O/¹⁶O. Even though inter-laboratory differences can be corrected for by a common ‘ratio assumption set’ and/or normalisation, the ultimate accuracy of the ¹⁷O correction is hereby limited. Errors of similar magnitude can be introduced by the assumed mass-dependent relationship between ¹⁷O/¹⁶O and ¹⁸O/¹⁶O isotope ratios. For highest accuracy in the ¹³C/¹²C ratio, independent triple oxygen isotope measurements are required. Finally, I propose an experiment that allows direct measurement of ¹³R¹⁷R/¹⁸R.     

20.

Oxygen,hydrogen and carbon isotope studies of the franciscan formation,Coast Ranges,California     

Mordeckai Magaritz  Hugh P Taylor 《Geochimica et cosmochimica acta》1976,40(2):215-234

Analyses of 230 Franciscan rock and mineral samples, including the San Luis Obispo ophiolite, show that metamorphism produces no change in the δ¹⁸O of the graywackes (+11 to +14), but that igneous rocks become enriched in ¹⁸O by 2–6% and the cherts depleted by 5–10%. The shales are of two types, a high-¹⁸O type (+16 to +20) associated with chert and a low-¹⁸O type isotopically and mineralogically similar to the graywackes. The vein quartz (δ = + 15 to + 20) is invariably richer in ¹⁸O than the host rock quartz and in most of the rocks the δ¹⁸O of the clastic quartz is similar to the δ¹⁸O of the whole rock. Mineral assemblages are typically not in isotopic equilibrium. Although the δ¹⁸O values are very uniform (+13 to +16). the δ¹³C of vein aragonite and calcite is widely variable (0 to ? 14), implying that a major source of the carbon is oxidized organic material. The δD values of 83 igneous and sedimentary rocks are -45 to -80, exceptions are the Fe-rich minerals howieite and deerite, which have δD = ?100. All of these samples could have equilibrated with H₂O having δD ≈ +10 to ?20 and δ¹⁸O ≈ ?3 to +8. assuming temperatures of 100–300°C. However, the serpentines (δD ≈ ?85 to ?110) and the vein minerals (δD = ?23 to ?55) are exceptions. The vein minerals are 10–20%, richer in deuterium than the adjacent wall rocks; they formed from a relatively D-rich metamorphic water, typically at lower temperatures than did their host rocks. The isotopic compositions of the other Franciscan rocks were affected by three distinct events: (1) hydrothermal alteration of the ophiolite complexes and volcanic rocks as a result of submarine igneous activity at a spreading center or in an island-arc environment; (2) low-temperature, high-pressure regional metamorphism and diagenesis; and (3) a late-stage, very low temperature (<100°C) alteration of the ultramafic bodies by meteoric ground waters, producing lizardite-chrysotile serpentine. In the first two cases, the pore fluid involved in the alteration of the Franciscan rocks was sea water. However, this water became somewhat depleted in D and enriched in ¹⁸O during blueschist metamorphism, evolving to values of δD ≈ ? 20 and δ¹⁸O ≈ + 6 to + 8 at the highest grades. Except for one graywacke sample, the meteoric waters that affected the serpentinites did not significantly change the $\text{D}\text{H}$ ratios of the OH-bearing minerals in any other Franciscan rock.The δ¹⁸O values of orogenic andesites are too low for such magmas to have formed by direct partial melting of Franciscan-type materials in a subduction zone. Andesites either form in some other fashion, or the melts must undergo thorough isotopic exchange with the upper mantle. The great Cordilleran granodiorite-tonalite batholiths, however, are much richer in ¹⁸O and may well have formed by large-scale melting or assimilation of Franciscan-type rocks. The range of δD values of Franciscantype rocks is identical to the ?50 to ?80 range shown by most igneous rocks. This suggests that ‘primary magmatic H₂O’ throughout the world may be derived mainly by partial melting of Franciscantype materials, or by dehydration of such rocks in the deeper parts of a Benioff zone.     

Mine	$\text{Δ}{}_{\mathrm{<mtext>QM</mtext>}}$	Corresponding temperature
Sevgok	9.4 to 14.2	475° to 320°C
Ugok	10.0 to 12.7	450° to 355°C
Annovsky	10.5 to 12.6	430° to 360°C

Preservation of the shell matrix protein dermatopontin in 1500 year old land snail fossils from the Bonin islands

Organic molecules such as proteins can be preserved in certain fossils. The bulk properties of fossil proteins of both vertebrates and invertebrates have been studied for over half a century. Named proteins have so far been identified, however, only in vertebrate fossils, such as collagen from mammoth bones. Using immunological assays, we examined 1500 year old fossils of the extinct land snail Mandarina luhuana from the Bonin islands for the presence of dermatopontin, a molluscan shell matrix protein. First, we examined the shell microstructure and mineralogy of the fossil shells using scanning electron microscopy (SEM) and powder X-ray diffraction (XRD) in order to estimate the extent of diagenetic alteration. The results suggest that the original microstructure and mineralogy of the shells are preserved. Antiserum raised against the Type-1 dermatopontin fragment of the living land snail Euhadra brandtii showed significant immunological reactivity with the extracts from the fossil shells of M. luhuana. Immunological binding curves drawn for the shell extracts of extant M. aureola and the extinct M. luhuana confirmed the presence of dermatopontin in the fossil shells and provided an estimate that about 75–98% of the original dermatopontin was lost from the M. luhuana fossils. This is the first report of a named protein being identified in invertebrate fossils.     

Compositional differences in enstatite chondrites based on carbon and nitrogen stable isotope measurements

Carbon and nitrogen abundance and isotopic compositions, from four EH4, one EH5, five EL6 chondrites and one aubrite, were determined by using stepped pyrolysis (N only) and combustion (N and C) extractions in attempts to distinguish the components present. Carbon contents range from 0.15 to 0.70 wt%, with no systematic relationship between carbon content and meteorite group or petrologic type. Whole-rock δ¹³C values range from −28.5 to −4.1 %., Most C occurs as graphite and when temperature steps above 700°C are considered, there is a difference between EH4,5 (δ¹³C = −9.1 to -5.8%.) and EL6 chondrites (δ¹³C = −6.7 to +4.2%.). Carbon in Bustee aubrite is isotopically lighter (δ¹³C = −24%.) than in any enstatite chondrite.

Nitrogen occurs as osbornite, sinoite and in isostructural substitution for oxygen in silicate lattice sites. Nitrogen abundances and isotopic compositions are more variable than C, due to the heterogenous distribution of N-bearing minerals. Three EL6's containing osbornite have higher N concentrations than other type 6 enstatite chondrites. Sinoite, where present, is depleted in ¹⁵N relative to osbornite. Nitrogen in the Bustee aubrite has a similar abundance and δ¹⁵N value to those of EL6's, again dominated by the presence of osbornite.

In addition to the refractory C-and N-bearing minerals there is also organic material (largely terrestrial contamination) and evidence for at least two “exotic” components. The first is a host for Xe (HL) and is characterized by δ¹³C <-−47%. and δ¹⁵N ≤−73%., whereas the second is less well-defined, but is marked by δ¹⁵N = +269%.     

Reformulated O correction of mass spectrometric stable isotope measurements in carbon dioxide and a critical appraisal of historic ‘absolute’ carbon and oxygen isotope ratios

Mass-spectrometric stable isotope measurements of CO₂ use molecular ion currents at mass-to-charge ratios m/z 44, 45 and 46 to derive the elemental isotope ratios n(¹³C)/n(¹²C) and n(¹⁸O)/n(¹⁶O), abbreviated ¹³C/¹²C and ¹⁸O/¹⁶O, relative to a reference. The ion currents have to be corrected for the contribution of ¹⁷O-bearing isotopologues, the so-called ‘¹⁷O correction’. The magnitude of this correction depends on the calibrated isotope ratios of the reference. Isotope ratio calibrations are difficult and are therefore a matter of debate. Here, I provide a comprehensive evaluation of the existing ¹³C/¹²C (¹³R), ¹⁷O/¹⁶O (¹⁷R) and ¹⁸O/¹⁶O (¹⁸R) calibrations of the reference material Vienna Standard Mean Ocean Water (VSMOW) and CO₂ generated from the reference material Vienna Pee Dee Belemnite (VPDB) by reaction with 100% H₃PO₄ at 25 °C (VPDB-CO₂). I find , ¹⁸R_VSMOW/10⁻⁶ = 2005.20 ± 0.45, ¹³R_VPDB-CO2/10^-6= 11124 ± 45, and ¹⁸R_VPDB-CO2/10^-6=2088.37±0.90. I also rephrase the calculation scheme for the ¹⁷O correction completely in terms of relative isotope ratio differences (δ values). This reveals that only ratios of isotope ratios (namely, ¹⁷R/¹³R and ¹³R¹⁷R/¹⁸R) are required for the ¹⁷O correction. These can be, and have been, measured on conventional stable isotope mass spectrometers. I then show that the remaining error for these ratios of isotope ratios can lead to significant uncertainty in the derived relative ¹³C/¹²C difference, but not for¹⁸O/¹⁶O. Even though inter-laboratory differences can be corrected for by a common ‘ratio assumption set’ and/or normalisation, the ultimate accuracy of the ¹⁷O correction is hereby limited. Errors of similar magnitude can be introduced by the assumed mass-dependent relationship between ¹⁷O/¹⁶O and ¹⁸O/¹⁶O isotope ratios. For highest accuracy in the ¹³C/¹²C ratio, independent triple oxygen isotope measurements are required. Finally, I propose an experiment that allows direct measurement of ¹³R¹⁷R/¹⁸R.     

Oxygen,hydrogen and carbon isotope studies of the franciscan formation,Coast Ranges,California

Analyses of 230 Franciscan rock and mineral samples, including the San Luis Obispo ophiolite, show that metamorphism produces no change in the δ¹⁸O of the graywackes (+11 to +14), but that igneous rocks become enriched in ¹⁸O by 2–6% and the cherts depleted by 5–10%. The shales are of two types, a high-¹⁸O type (+16 to +20) associated with chert and a low-¹⁸O type isotopically and mineralogically similar to the graywackes. The vein quartz (δ = + 15 to + 20) is invariably richer in ¹⁸O than the host rock quartz and in most of the rocks the δ¹⁸O of the clastic quartz is similar to the δ¹⁸O of the whole rock. Mineral assemblages are typically not in isotopic equilibrium. Although the δ¹⁸O values are very uniform (+13 to +16). the δ¹³C of vein aragonite and calcite is widely variable (0 to ? 14), implying that a major source of the carbon is oxidized organic material. The δD values of 83 igneous and sedimentary rocks are -45 to -80, exceptions are the Fe-rich minerals howieite and deerite, which have δD = ?100. All of these samples could have equilibrated with H₂O having δD ≈ +10 to ?20 and δ¹⁸O ≈ ?3 to +8. assuming temperatures of 100–300°C. However, the serpentines (δD ≈ ?85 to ?110) and the vein minerals (δD = ?23 to ?55) are exceptions. The vein minerals are 10–20%, richer in deuterium than the adjacent wall rocks; they formed from a relatively D-rich metamorphic water, typically at lower temperatures than did their host rocks. The isotopic compositions of the other Franciscan rocks were affected by three distinct events: (1) hydrothermal alteration of the ophiolite complexes and volcanic rocks as a result of submarine igneous activity at a spreading center or in an island-arc environment; (2) low-temperature, high-pressure regional metamorphism and diagenesis; and (3) a late-stage, very low temperature (<100°C) alteration of the ultramafic bodies by meteoric ground waters, producing lizardite-chrysotile serpentine. In the first two cases, the pore fluid involved in the alteration of the Franciscan rocks was sea water. However, this water became somewhat depleted in D and enriched in ¹⁸O during blueschist metamorphism, evolving to values of δD ≈ ? 20 and δ¹⁸O ≈ + 6 to + 8 at the highest grades. Except for one graywacke sample, the meteoric waters that affected the serpentinites did not significantly change the $\text{D}\text{H}$ ratios of the OH-bearing minerals in any other Franciscan rock.The δ¹⁸O values of orogenic andesites are too low for such magmas to have formed by direct partial melting of Franciscan-type materials in a subduction zone. Andesites either form in some other fashion, or the melts must undergo thorough isotopic exchange with the upper mantle. The great Cordilleran granodiorite-tonalite batholiths, however, are much richer in ¹⁸O and may well have formed by large-scale melting or assimilation of Franciscan-type rocks. The range of δD values of Franciscantype rocks is identical to the ?50 to ?80 range shown by most igneous rocks. This suggests that ‘primary magmatic H₂O’ throughout the world may be derived mainly by partial melting of Franciscantype materials, or by dehydration of such rocks in the deeper parts of a Benioff zone.