Stable isotopes in mineralogy

Stable isotope fractionations between minerals are functions of the fundamental vibrational frequencies of the minerals and therefore bear on several topics of mineralogical interest. Isotopic compositions of the elements H, C, O, Si, and S can now be determined routinely in almost any mineral. A summary has been made of both published and new results of laboratory investigations, analyses of natural materials, and theoretical considerations which bear on the importance of temperature, pressure, chemical composition and crystal structure to the isotopic properties of minerals. It is shown that stable isotope studies can sometimes provide evidence for elucidating details of crystal structure and can be a powerful tool for use in tracing the reaction paths of mineralogical reactions.     

Stable chlorine isotopes in Phanerozoic evaporites

Modern seawater has a uniform δ³⁷Cl value (0.0‰), with an exception in the upper current of the Bosphorus (0.4‰). Marine halite ranging in age from Cambrian to Miocene has δ³⁷Cl values of 0.0 ± 0.9‰, with most of the data in the range 0.0 ± 0.5‰. Mean δ³⁷Cl values differ measurably between basins, with no evident relationship to basin size or to age. Smaller evaporite bodies have the largest δ³⁷Cl ranges. Potash facies halite has mean δ³⁷Cl values lower than those of halite facies salt in the East Siberia and Zechstein basins. The bulk δ³⁷Cl of bedded halite preserving sedimentary textures cannot be shifted measurably after deposition under plausible natural conditions. During the Phanerozoic, a detectable change in the δ³⁷Cl values of the oceans is unlikely as a result of Cl fluxes to and from the mantle and evaporites. In halite, the values of δ³⁷Cl that cannot be explained by fractionation occurring on crystallization are best explained by the addition of non-marine Cl with δ³⁷Cl ≠ 0.0‰ to evaporite brine.     

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。

     

Late Weichselian ostracod assemblages from the southern Kattegat, Scandinavia: a palaeoenvironmental study

The ostracods in three vibro cores (representing the time between c . 13000 and 12000 BP) from southern Kattegat were studied to further elucidate palaeoenvironmental conditjons in an area interpreted to be influenced by a Late Weichselian drainage of the Baltic Ice Lake via the Öresund Strait. This time represents an extremely important phase of the deglaciation of the northern hemisphere. It is characterized by rapid climatic change and enormous amounts of meltwater that are drained into the ocean. The ostracod assemblages identified are characterized by a peculiar mixture of marine (arctic and temperate) and freshwater species believed to characterize environments ranging from the tidal zone of an outer estuary (or delta) to fully marine sublittoral conditions in a subarctic climate. Dominant species display autochthonous population structures typical of in situ elements of such environments. Indications of very shallow conditions are, however, difficult to reconcile with palaeobathymetrical inferences from earlier studies of shore-level displacements. It is, therefore, possible that the present assemblages are mainly death assemblages deposited offshore by postmortem meltwater discharge. Rare pre-Quaternary ostracods similar to Mesozoic species previously reported from the Öresund Strait (drill holes) and the Swedish west coast may have been redeposited by outflowing meltwater.     

无定河流域碳氮稳定同位素研究

对黄河中游一条很有特点的高悬沙支流--无定河流域进行了碳氮稳定同位素调查,发现该流域植被的碳氮同位素组成分布范围很广,碳同位素组成呈现出明显的双峰特征,说明该流域生态系统属于C3和C4混合植被类型.植物的氮同位素组成与碳同位素组成之间并不存在相关关系.沿河沉积物中的碳氮同位素组成之间存在有弱负相关性.河水悬浮体中碳氮同位素组成显示出良好的负相关关系,反映出该河悬浮体中主要有2种物质来源以及具保守性的物理混合特征.根据无定河流域植被、土壤、沉积物的碳同位素调查结果,估算出该河流颗粒有机质中C3植物碳的贡献可占75%～80%.河水悬浮体中有机质的控制性来源是中下游陆地侵蚀物质,同样也反映了流域植被的同位素特征,C3植物碳的贡献占优势.初步的研究结果已经证明,在研究河流中生源要素的输送通量与降水及径流过程之间的关系和河流物质与陆地生态环境变化之间的关系时碳氮稳定同位素示踪应该是十分有效的手段.     

Stable isotopes and archaeological geology: the Carrara marble,northern Italy

The principal marble quarries of Italy for the past 2000 years have been those of Carrara. In Roman times, the marble was exported all over the ancient world. Renaissance quarries were opened up in Seravezza; both the Seravezza and the Carrara quarries have been exploited until today. The correct identification of Carrara marble has always been a problem because it was traded so widely in Roman times and was later used to fabricate broken or lost pieces of classical statuary. Many types of geochemical analysis have been tried in order to find distinctive signatures for the recognition of classical marbles, including trace elements, ESR spectroscopy of Mn, thermoluminescence, and stable isotopic ratios. To date, the most promising has been isotopic ratio analysis of oxygen and carbon.In this study, stable isotopic signatures were investigated as a means for distinguishing: (1) the principal quarry areas of the Carrara Commune: Fossacava, Miseglia, and Torano, and the Seravezza Commune; (2) or merely the largely classical quarries of Carrara from the Renaissance quarries of Seravezza; (3) and, most important, the Carrara quarries from other quarries of Greece, Turkey, Italy, and Tunisia in the classical marble data base.Discriminant analysis (DA) of the isotopic analyses showed that the three quarry areas of a Carrara could not be told apart but that they could be told easily from Seravezza. In addition, a “mineralized” Carrara quarry at Mandria, with buff to yellow rather than white marble, was also distinctive. DA also suggests that Carrara can be told from those quarries with which it is presently confused: Paros, in the Aegean Sea; Marmara, in Turkey; and Pentelikon, near Athens.Sr isotopic analysis showed a range in the Carrara and other marbles of Hettangian (Lower Jurassic) age from 0.70778 to 0.70810 which is very different from values found in Paros and Pentelikon. This suggests that Sr might make a good third discriminator for classical marble.     

Stable sulfur isotopes in the water column of the Cariaco Basin

Previous geochemical and microbiological studies in the Cariaco Basin indicate intense elemental cycling and a dynamic microbial loop near the oxic-anoxic interface. We obtained detailed distributions of sulfur isotopes of total dissolved sulfide and sulfate as part of the on-going CARIACO time series project to explore the critical pathways at the level of individual sulfur species. Isotopic patterns of sulfate (δ³⁴S_SO4) and sulfide (δ³⁴S_H2S) were similar to trends observed in the Black Sea water column: δ³⁴S_H2S and δ³⁴S_SO4 were constant in the deep anoxic water (varying within 0.6‰ for sulfide and 0.3‰ for sulfate), with sulfide roughly 54‰ depleted in ³⁴S relative to sulfate. Near the oxic-anoxic interface, however, the δ³⁴S_H2S value was ∼3‰ heavier than that in the deep water, which may reflect sulfide oxidation and/or a change in fractionation during in situ sulfide production through sulfate reduction (SR). δ³⁴S_H2S and Δ³³S_H2S data near the oxic-anoxic interface did not provide unequivocal evidence to support the important role of sulfur-intermediate disproportionation suggested by previous studies. Repeated observation of minimum δ³⁴S_SO4 values near the interface suggests ‘readdition’ of ³⁴S-depleted sulfate during sulfide oxidation. A slight increase in δ³⁴S_SO4 values with depth extended over the water column may indicate a reservoir effect associated with removal of ³⁴S-depleted sulfur during sulfide production through SR. Our δ³⁴S_H2S and Δ³³S_H2S data also do not show a clear role for sulfur-intermediate disproportionation in the deep anoxic water column. We interpret the large difference in δ³⁴S between sulfate and sulfide as reflecting fractionations during SR in the Cariaco deep waters that are larger than those generally observed in culturing studies.     

Stable chlorine isotopes in arid non-marine basins: Instances and possible fractionation mechanisms

Stable chlorine isotopes are useful geochemical tracers in processes involving the formation and evolution of evaporitic halite. Halite and dissolved chloride in groundwater that has interacted with halite in arid non-marine basins has a δ³⁷Cl range of 0 ± 3‰, far greater than the range for marine evaporites. Basins characterized by high positive (+1 to +3‰), near-0‰, and negative (−0.3 to −2.6‰) are documented. Halite in weathered crusts of sedimentary rocks has δ³⁷Cl values as high as +5.6‰. Salt-excluding halophyte plants excrete salt with a δ³⁷Cl range of −2.1 to −0.8‰. Differentiated rock chloride sources exist, e.g. in granitoid micas, but cannot provide sufficient chloride to account for the observed data. Single-pass application of known fractionating mechanisms, equilibrium salt-crystal interaction and disequilibrium diffusive transport, cannot account for the large ranges of δ³⁷Cl. Cumulative fractionation as a result of multiple wetting-drying cycles in vadose playas that produce halite crusts can produce observed positive δ³⁷Cl values in hundreds to thousands of cycles. Diffusive isotope fractionation as a result of multiple wetting-drying cycles operating at a spatial scale of 1–10 cm can produce high δ³⁷Cl values in residual halite. Chloride in rainwater is subject to complex fractionation, but develops negative δ³⁷Cl values in certain situations; such may explain halite deposits with bulk negative δ³⁷Cl values. Future field studies will benefit from a better understanding of hydrology and rainwater chemistry, and systematic collection of data for both Cl and Br.     

Stable lead isotopes as tracers of groundwater pollution in the water supply for a small village

High lead (Pb) concentration has been measured in the incoming water to the water supply for a small Swedish village since the 1990s. There are several sources of the contamination and the objective of this study was to identify these by analysis of Pb isotopes. Lead has four stable isotopes in nature (²⁰⁴Pb, ²⁰⁶Pb, ²⁰⁷Pb, ²⁰⁸Pb) and the relative proportions of these vary according to their geological source. The study showed that two anthropogenic sources of Pb, a glassworks deposit and a highway, had similar Pb isotope ratios and thus it was not possible to separate them. However, the very high Pb concentration in the glassworks deposit suggested that this is the main source of the very high concentrations observed occasionally in low flow conditions. The soil in the recharge area of the most important well for the water supply had elevated Pb concentrations compared with background values in soils. Moreover, the Pb ratios in this soil differed from those in the anthropogenic sources. Several sites of mineralisation or natural enrichment have been identified in outcrops about 14?km northwest of the site and several anomalies in Pb exist in the glacial till. The conclusion was that Pb originating from the soil in the recharge area generally dominates and leads to Pb concentrations in water of 1?C2???g?L^?1. However, at higher concentrations, e.g. around 10???g?L^?1, water transported in cracks and fissure from the glassworks deposit becomes more important.     

Stable isotopes in a stalagmite from NW Sweden document environmental changes over the past 4000 years

Sundqvist, H. S., Holmgren, K., Moberg, A., Spötl, C. & Mangini, A. 2009: Stable isotopes in a stalagmite from NW Sweden document environmental changes over the past 4000 years. Boreas, 10.1111/j.1502‐3885.2009.00099.x. ISSN 0300‐9483. This study of a 4000‐year‐old stalagmite from Korallgrottan in northwestern Sweden highlights the potentials and challenges when using stable isotopes in stalagmites as climate proxies, as well as the fact that the relationship between climate and proxy may change through time. Both the oxygen and the carbon isotopes display an overall trend of enrichment together with decreasing growth rates over the time period covered by the stalagmite, which is considered a generally cooling period according to current palaeoclimate understanding. The stable isotope records show enriched isotopic values during the, for Scandinavia, comparatively cold period AD 1300–1700 and depleted values during the warmer period AD 800–1000. The indication of a negative relationship between measured δ¹⁸O and surface temperature concurs with earlier reported stalagmite records from regions with a seasonal snow cover and is further supported by the fact that the stalagmite δ¹⁸O record shows general similarities with both regional and hemispheric temperature reconstructions available for the past 500 and 2000 years, respectively. Compared with a stable isotope record of lacustrine carbonates from northern Sweden, however, shifting correlations over time between the two records indicate that a local hydrological change may have taken place at Korallgrottan, or at the lake, compared with around 1000 years ago. The earlier part of the stalagmite δ¹⁸O might thus be influenced, to some extent, by another process than the later part, which means that a negative relationship between δ¹⁸O and surface temperature might not hold for the entire 4000‐year‐old record.     

Stable hydrogen isotopes in iron oxides—isotope effects associated with the dehydration of a natural goethite

The dehydration of a natural goethite to hematite is accompanied by a systematic hydrogen isotope fractionation. Closed system dehydration at, and below, 250°C results in a significantly greater degree of isotopic fractionation than does open system dehydration. This relationship is apparently reversed at 300°C. Both processes produce a progressive decrease in the $\text{D}\text{H}$ ratio of the mineral hydrogen with increasing degree of dehydration. At temperatures of 160°C to 250°C the closed system mineralvapor fractionation factor is independent of temperature, while above 250°C, it varies strongly with temperature. The mineral-vapor fractionation factor associated with open system dehydration appears to be independent of temperature over the interval 160°C to 300°C. The closed system $\text{D}\text{H}$ fractionation suggests that natural goethite undergoing dehydration in the presence of water can isotopically exchange with that water.CO₂ loss from goethite during dehydration is correlated with the loss of H₂O. The CO₃ is thought to be present in carbonates which exist as impurities in the goethite. Loss of both H₂O and CO₂ appears to be diffusion-controlled.     

Lithium isotopes in the system Qz-Ms-fluid:An experimental study

The fractionation of lithium isotopes among quartz, muscovite, and a chloride-bearing aqueous fluid has been investigated experimentally at 400°-500°C and 50-100 MPa. Experiments were performed for 15-60 days in cold seal vessels with natural mineral specimens. Lithium was introduced primarily through the fluid, which also contained KCl and HCl. In most runs, the fluid was prepared with the L-SVEC standard (δ⁷Li = 0) and was 1 M in total chloride with K/Li/H = 100/10/1. In two experiments, a ⁶Li spike was employed. The experiments demonstrate that quartz and muscovite are susceptible to pronounced, rapid shifts in Li isotopic composition by diffusion through interaction with a Li-bearing fluid, particularly at 500°C. At 500°C, fractionation factors were determined to be Δ_{quartz-aqueous} ≅ +8 to + 12‰ and Δ_{muscovite-aqueous} ≅ +18 to + 20‰. An intermineral fractionation factor is given by Δ_{muscovite-quartz} ≈ +9‰. At 400°C, the results suggest Δ_{quartz-aqueous} ≈ +4 to + 6‰. The study provides evidence of systematic fractionation in lithium isotopes at the temperatures of some magmatic processes, such as those associated with porphyry-type ore systems and pegmatites.     

Stable isotopes in deep-sea corals and a new mechanism for “vital effects”

Offsets from isotopic equilibrium in biogenic carbonates have complicated paleoclimate reconstructions for decades. A new archive of climate, deep-sea corals, is used to evaluate the calcification processes, independent of photosynthesis, that contribute to these offsets. Carbon and oxygen stable isotope data from six modern deep-sea corals show strong linear trends between δ¹³C and δ¹⁸O. Slopes of these trends between samples are similar and range between 1.9 to 2.6 for Δδ¹³C/Δδ¹⁸O. Linear trends intersect isotopic equilibrium for δ¹⁸O and are slightly depleted for δ¹³C. Variations in the isotopic ratios are strongly correlated with the density banding structure. Isotopically depleted aragonite is associated with light, quickly precipitating bands, whereas isotopically enriched points correspond to slowly accumulating, less dense aragonite. The densest white band at the trabecular center is furthest from isotopic equilibrium for both carbon and oxygen. Data from this region fall off the linear trend between δ¹⁸O and δ¹³C. This deviation, where δ¹³C remains constant while the δ¹⁸O continues to decrease, does not support “vital effect” mechanisms that call upon kinetic fractionation to explain offsets from isotopic equilibrium. We propose a new mechanism for vital effects in these deep-sea corals that is based on a thermodynamic response to a biologically induced pH gradient in the calcifying region.     

Stable lead isotopes reveal a natural source of high lead concentrations to gasoline-contaminated groundwater

Concentrations of total lead as high as 1,600 g/L were detected in gasoline-contaminated and uncontaminated groundwater at three gasoline-release sites in South Carolina. Total lead concentrations were highest in turbid groundwater samples from gasoline-contaminated and uncontaminated wells, whereas lower turbidity groundwater samples (collected using low-flow methods) had lower total lead concentrations. Dissolved lead concentrations in all wells sampled, however, were less than 15 g total lead/L, the current United States Environmental Protection Agency (US EPA) maximum contaminant level (MCL). Because many total lead concentrations exceeded the MCL, the source of lead to the groundwater system at two of the three sites was investigated using a stable lead isotope ratio approach. Plots of the stable isotope ratios of lead (Pb) in groundwater as ²⁰⁷Pb/²⁰⁶Pb versus ²⁰⁸Pb/²⁰⁶Pb, and ²⁰⁸Pb/²⁰⁴Pb versus ²⁰⁶Pb/²⁰⁴Pb were similar to ratios characteristic of lead-based minerals in local rocks of the southeastern US, and were not similar to the stable lead isotopes ratios characteristic of distant lead ore deposits such as Broken Hill, Australia, used to produce tetraethyl lead in gasoline products prior to its phase-out and ban in the United States. Moreover, the isotopic composition of dissolved lead was equivalent to the isotopic composition of total lead in turbid samples collected from the same well, suggesting that the majority of the lead detected in the groundwater samples was associated with sediment particulates of indigenous aquifer material, rather than lead associated with spilled leaded gasoline. The results of this investigation indicate that (1) lead detected at some gasoline-release sites may be derived from the local aquifer material, rather than the gasoline release, and consequently may affect site-specific remediation goals; (2) non-low flow groundwater sampling methods, such as a disposable bailer, may result in turbid groundwater samples and high total lead concentrations, and; (3) stable lead isotopes can be used to clarify the source of lead detected above permissible levels in gasoline-contaminated groundwater systems.     

Stable water isotopes of precipitation in China simulated by SWING2 models

The stable water isotope ratio in precipitation is a useful tracer of atmospheric circulation. Such observations, however, are very limited in space and time. To solve this problem, many isotope-enabled general circulation models (GCMs) are used to help the interpretation of isotope proxies. In this paper, several isotope-enabled GCMs released by the second Stable Water Isotope Intercomparison Group (SWING2) were selected to assess the spatial pattern of deuterium (δD) and the deuterium excess (d) of precipitation in China. The isotopic data of the Global Network of Isotopes in Precipitation (GNIP) and the Chinese Network of Isotopes in Precipitation (CHNIP) were also applied to verify the simulations. The results indicate that these models accurately simulate the spatial characteristics of δD and d of precipitation in China. The correlation between the observations and simulations for LMDZ is the highest among these models, while the root-mean-square (RMS) and standard deviation are not perfect. In addition, LMDZ is worse than other models in capturing the low signal in certain regions, such as CAM, GISS_E, and MIROC. For the monthly variation, most SWING2 models underestimate δD of the precipitation but overestimate the value of d, except for isoGSM. The simulated monthly variation of the water isotopes from SWING2 models is in general similar to the observations, and the trend corresponds to the monthly variation in the Northern Hemisphere. Moreover, all models are good at illustrating the temperature and precipitation amount effects, while they exhibit varying skills in interpreting the altitude and continental effects.     

Stable carbon isotopes in freshwater mussel shells: Environmental record or marker for metabolic activity?

Mussel shells have been used in a number of paleoecological and environmental studies. The interpretation of stable carbon isotopic composition of shell material is still controversial. The carbon for shell carbonate precipitation can either be derived from ambient dissolved inorganic carbon (DIC), with shells recording environmental signals, or from metabolic CO₂, with the potential to disguise environmental signals. To gain insight into this question, we investigated four nearly 100-yr long-term records of aragonite shells from an extant freshwater bivalve species, the endangered freshwater pearl mussel (Margaritifera margaritifera L.). Single growth increments of the outer prismatic and the inner nacreous zones were successfully and easily separated with a simple heat treatment for chronological analyses of δ¹³C in single layers of each zone. Autocorrelation and semivariance statistical methods reveal that mussels show distinct individual signal patterns, which extend up to 25 yr. Signal patterns are reliably reproduced with replicate samples from defined layers within one shell and show similar patterns with a slight offset for inner nacreous and outer prismatic layers for individual animals. Mussels exposed to the same environmental conditions exhibit distinct and contradictory signature patterns, which do not match between individuals. This observation can only be explained by strong metabolic influences on shell precipitation. Environmental changes in pH, temperature, electric conductivity and atmospheric carbon signature had no or little (<5%) influence, whereas body tissue protein and body tissue δ¹³C signatures negatively correlated with the youngest produced shell δ¹³C signatures, indicating that respiration causes a preferential loss of light isotopes from body mass and an inverse enrichment in shell aragonite. Hence, the shells of the freshwater pearl mussel yield a long-term record of metabolic activity, whereas the use of δ¹³C in these shells as recorder for environmental signals is questionable. This may also be true for shells from other species, for which metabolic carbon incorporation has been acknowledged.     

Mg同位素应用研究进展

Mg是地球常量元素,几乎参与了地球上的所有地球化学过程;Mg也是陨石的重要元素,是构成陨石26Al-26Mg年代学的一部分.多接收器等离子体质谱(MC-ICP-MS)高精度测定Mg同位素技术的发展,使Mg同位素成为地球化学、宇宙化学和医学等方面研究的新工具.已取得的成果显示,Mg同位素在陨石难熔包体的形成年龄、古环境重建和人体的食物Mg吸收率等方面很有应用前途.     

Stable carbon and oxygen isotopes distribution in carbonates from the Central Barents Sea shelf sediments

Carbonate macrofaunal remains and diagenetic tubes collected from a number of structures in the Central Barents Sea area during the 18th TTR (Training Through Research) cruise were subdivided into three groups according to the results of stable carbon and oxygen isotopes analysis. The first group includes carbonates that were formed from bicarbonate only from surrounding sea waters. The carbonates of the second group were formed during diagenesis with use of mixed sources of bicarbonate. The fourth group includes methane-derived carbonates that were formed as a result of anaerobic oxidation of methane (AOM).     

Ordovician sediments in the southeastern Siberian Platform: lithostratigraphy and ostracod zoning

The results of studying Ordovician ostracods from the southeastern Siberian Platform are presented. Ordovician sections are described in brief from outcrop and core studies. Four of the ostracod zones distinguished in the Ordovician strata of the Siberian Platform have been found in the Volgian, Kirenskian–Kudrinoan, Chertovskayan, and Baksanian Horizons. Stratigraphic correlation takes into account the available data on the distribution of other groups (e.g., conodonts and cephalopods)..