Light and temperature effects on Sr/Ca and Mg/Ca ratios in the scleractinian coral Acropora sp.

This study was designed to investigate the effect of light and temperature on Sr/Ca and Mg/Ca ratios in the skeleton of the coral Acropora sp. for the purpose of evaluating temperature proxies for paleoceanographic applications. In the first experiment, corals were cultivated under three light levels (100, 200, 400 μmol photons m⁻² s⁻¹) and constant temperature (27 °C). In the second experiment, corals were cultivated at five temperatures (21, 23, 25, 27, 29 °C) and constant light (400 μmol photons m⁻² s⁻¹). Increasing the water temperature from 21 to 29 °C, induced a 5.7-fold increase in the rate of calcification, which induced a 30% increase in the Mg/Ca ratio. In contrast, by increasing the light level by a factor of 4, the rate of calcification was increased only by a factor of 1.7, with a corresponding 9% increase in the Mg/Ca ratio. Thus, the relative change in the calcification rate in the two experiments (5.7 vs. 1.7) scales with the corresponding relative change in Mg/Ca ratio (30% vs. 9%). We conclude that there is a strong biological control on the incorporation of Mg.For Sr/Ca, good correlations were also observed with water temperature and the calcification rate induced by temperature changes. However, in sharp contrast with the Mg/Ca ratio, a temperature-induced 5.7-fold increase in the calcification rate only induced a 4.5% change (decrease) in the Sr/Ca ratio. An important finding for paleoceanographic applications is that the Sr/Ca ratio did not appear to be sensitive to changes in the light level, or to changes in calcification rate induced by changes in the light level. Thus, in this study, water temperature was found to be the dominant parameter controlling the skeletal Sr/Ca ratio.     

Diagenesis and its impact on Sr/Ca ratio in Holocene Acropora corals

The effect of early diagenesis on Sr/Ca ratios encapsulated in coral skeletons was evaluated by comparing mineralogical, structural and geochemical characteristics of modern and Holocene, branching Acropora colonies. The modern specimens (Acropora danai, Acropora formosa) come from Réunion island (Western Indian Ocean) and the Great Barrier Reef of Australia respectively. The Sr/Ca ratios of modern specimens range from 9.08 to 9.37 mmol/mol. The fossil acroporids (Acropora group danai-robusta) were collected from a 50-m core drilled through a barrier reef in Tahiti island; their C-14 ages range from 3,200 to 10,200 calendar years B.P. Fossil skeletons are 100% aragonite. Earlier diagenesis has occurred in the marine environment; it is expressed by growth of secondary inorganic aragonite over primary skeletal aragonite needles, development of syntaxial aragonite cements within intraskeletal cavities and decrease in size of original 1-1,050-µm-wide pores (residual porosity ranges from 25 to 28%), which results in a volume reduction by 34 to 49%. Cementation increases with increasing age of the corals. Later diagenesis has occurred in a mixed marine-freshwater environment. It includes partial dissolution of skeletal and growth of cement aragonite fibres in the form of spherolites, irregular meshes of large squarely terminated laths; this results in an increase in porosity from 30 to 59%. By reference to modern well-preserved acroporids, this diagenetic alteration has led to an increase of Sr/Ca values (from 9.08-9.37 to 8.89-10.55 mmol/mol). This variation in Sr/Ca ratio can be linked to the increase in the amount of Sr-enriched cements relative to the volume of the skeletal aragonite and to a more homogeneous distribution of these cements throughout the skeleton. The uncritical use of Sr/Ca ratios as paleothermometers from diagenetically altered skeletons may cause serious misinterpretations. Accordingly, estimate of the degree of diagenetic alteration in skeletons is a prerequisite to any paleoclimatic reconstruction based on coral records.     

洞穴次生碳酸盐沉积的Mg/Ca与Sr/Ca比值研究进展——兼论洞穴次生沉积物Mg/Ca与Sr/Ca的影响机制

微量元素是岩溶洞穴沉积中非常重要的一类古气候环境替代指标,为近20年来国内外的一个研究热点。总结前人的研究,主要取得了以下一些重要认识:（1）洞穴上覆土壤 和围岩是洞穴次生碳酸盐沉积Mg、Sr的主要来源;（2）Mg/Ca与Sr/Ca能够指示气候环境变化,但需结合其它指标综合考虑。（3）洞穴次生碳酸盐沉积Mg/Ca与Sr/Ca受多种气候环境因素（包括土壤和围岩的组成和性质、水-岩相互作用、先期碳酸盐沉积、分配系数等）影响,其古气候环境指示意义具有多解性;（4）矿物结晶作用对Mg/Ca与Sr/Ca有一定的影响,特别是文石在向方解石转变的过程中容易丢失Mg、Sr,此外,杂质的混入也将抑制Mg、Sr进入方解石,从而引起洞穴次生碳酸盐沉积Mg/Ca与Sr/Ca比值的变化。今后应进一步加强对石笋中这些微量元素的影响机制研究,尤其是对一些影响因素与微量元素含量变化之间的定量关系进行探讨。      

Assessing scleractinian corals as recorders for paleo-pH: Empirical calibration and vital effects

Laboratory experiments on the branching, symbiont-bearing coral genus Porites and Acropora have been carried out to determine the dependence of the skeletal boron isotopic composition (δ¹¹B) on the pH of seawater. The results show a clear relationship similar to previously established empirical calibrations for planktonic foraminifera and inorganic calcite. A −0.6‰ offset exists between P. cylindrica and A. nobilis which is systematic over the pH range of 7.7-8.2. To test whether the δ¹¹B of coral skeletons changes with physiological processes such as photosynthesis and respiration, corals were grown along a depth transect in their natural environment and under controlled conditions in the laboratory at varying light intensities and food supply. Although we also observe an isotopic offset between P. compressa and Montipora verrucosa, neither experimental treatment systematically changed the δ¹¹B of the two species. These findings are encouraging for using the boron isotope paleo-pH proxy in corals, because it appears that seawater pH is the dominant control on the boron isotopic composition in corals.     

延河泉岩溶水系统Sr/Mg、Sr/Ca分布特征及其应用

山西省延河泉岩溶水系统是我国北方岩溶大泉之一。依据碱土金属比值Sr Mg、Sr Ca与矿化度关系,分析了延河泉岩溶水系统Sr Mg、Sr Ca分布规律及形成条件。从补给区到径流区、排泄区,Sr Mg、Sr Ca值逐渐增高;径流条件好,Sr Mg、Sr Ca值低;径流条件差,其值高;径流滞缓区最高。并且Sr Mg、Sr Ca值主要受径流条件控制,不受人为作用的影响。因此,Sr Mg、Sr Ca是比较理想的天然示踪剂。根据Sr Mg、Sr Ca值将延河泉岩溶水系统划分为三个子系统,即下河泉子系统(泉1、2、3、5),延河泉子系统(泉4、6),南部散泉子系统(泉7、8、9)。     

The impact of salinity on the Mg/Ca and Sr/Ca ratio in the benthic foraminifera Ammonia tepida: Results from culture experiments

Over the last decade, sea surface temperature (SST) reconstructed from the Mg/Ca ratio of foraminiferal calcite has increasingly been used, in combination with the δ¹⁸O signal measured on the same material, to calculate the δ¹⁸O_w, a proxy for sea surface salinity (SSS). A number of studies, however, have shown that the Mg/Ca ratio is also sensitive to other parameters, such as pH or , and salinity. To increase the reliability of foraminiferal Mg/Ca ratios as temperature proxies, these effects should be quantified in isolation. Individuals of the benthic foraminifera Ammonia tepida were cultured at three different salinities (20, 33 and 40 psu) and two temperatures (10-15 °C). The Mg/Ca and Sr/Ca ratios of newly formed calcite were analyzed by Laser Ablation ICP-MS and demonstrate that the Mg concentration in A. tepida is overall relatively low (mean value per experimental condition between 0.5 and 1.3 mmol/mol) when compared to other foraminiferal species, Sr being similar to other foraminiferal species. The Mg and Sr incorporation are both enhanced with increasing temperatures. However, the temperature dependency for Sr disappears when the distribution factor D_Sr is plotted as a function of calcite saturation state (Ω). This suggests that a kinetic process related to Ω is responsible for the observed dependency of Sr incorporation on sea water temperature. The inferred relative increase in D_Mg per unit salinity is 2.8% at 10 °C and 3.3% at 15 °C, for the salinity interval 20-40 psu. This implies that a salinity increase of 2 psu results in enhanced Mg incorporation equivalent to 1 °C temperature increase. The D_Sr increase per unit salinity is 0.8% at 10 °C and 1.3% at 15 °C, for the salinity interval 20-40 psu.     

The isotopic composition of respired carbon dioxide in scleractinian corals: Implications for cycling of organic carbon in corals

The origin of δ¹³C variations within the skeletons of zooxanthellate scleractinian corals is still a matter of considerable debate. In particular, the role respired CO₂ plays in controlling the eventual δ¹³C of the skeleton remains unclear. In this study, the temporal variability of the δ¹³C of respired CO₂ produced by Montastraea faveolata has been measured at approximately monthly intervals over a 1-year period. In these experiments, three corals maintained on a platform at 8 m depth near Molasses Reef in the Florida Keys were incubated in closed chambers for 24-h periods and samples of the incubation water analyzed for the δ¹³C of the dissolved inorganic carbon (ΣCO₂) at ∼3-h intervals. Throughout the incubation, the concentration of O₂ was measured continuously within the chamber. Our results show that during daylight, the δ¹³C of the ΣCO₂ in the incubation water becomes enriched in ¹³C as a result of fractionation during the fixation of C by photosynthesis, whereas at night the δ¹³C of the ΣCO₂ becomes more negative. The δ¹³C of the respiratory CO₂ ranges from −9‰ in the late spring to values as low as −17‰ in the autumn. The lighter values are significantly more negative than those reported by previous workers for coral tissue and zooxanthellae. An explanation for this discrepancy may be that the corals respire a significant proportion of isotopically negative substances, such as lipids, which are known to have values up to 10‰ lighter compared to the bulk δ¹³C of the tissue. The clear seasonal cycle in the δ¹³C of the respiratory CO₂ suggests that there is also seasonal variability in either the δ¹³C of the coral tissue or the type and/or amount of organic material being respired. A similar temporal pattern and magnitude of change was observed in the δ¹³C of the coral tissue samples collected from a nearby reef at monthly intervals between 1995 and 1997. These patterns are similar in timing to the δ¹³C measured in the coral skeletons. We have also calculated an annual mean value for the fractionation factor between dissolved CO₂⁻ in the external environment and photosynthate fixed by the zooxanthellae of 1.0121 (±0.003). This value is inversely correlated with the ratio of photosynthesis to respiration (P/R) of the entire organism and shows the highest values during the summer months.     

Carbon and oxygen isotope fractionation in scleractinian corals: a review

The present theories on the fractionation of stable isotopes in scleractinian corals are critically discussed in the light of data available on primary productivity, respiration and stable isotope chemistry. These data support a model of fractionation in which the carbon and oxygen isotopes are decoupled. Calcification occurs from a reservoir of carbon dioxide derived from both organic and inorganic sources. Photosynthesis preferentially fixes¹³C and thereby leaves behind¹³C. Increases in the rate of photosynthesis therefore also enrich the carbon isotope ratio of the skeleton. From theoretical considerations, photosynthesis has little effect on the oxygen isotope ratio of the skeleton, a fact confirmed by available data. The process of respiration adds depleted carbon and oxygen to the calcification reservoirs. The varying correlations between carbon and oxygen isotopes seen in hermatypic corals are caused by changes in the relationship between photosynthesis and respiration at different geographical localities. The isotopic compositions in the skeletons of non-zooxanthellate corals, which show a consistent positive correlation, can also be explained by the above scenario.     

Constraints on paleowater dissolved loads and on catchment weathering over the past 16 ka from Sr/Sr ratios and Ca/Mg/Sr chemistry of freshwater ostracode tests in sediments of Lake Constance, Central Europe

Sr isotope and Ca/Mg/Sr chemical compositions of freshwater ostracode tests separated from a sediment core represent the last 16 ka of sedimentation in Lake Constance, Central Europe. The chemical evolution of the paleowater's dissolved load of Lake Constance was estimated by correcting the ostracode data for Ca/Mg/Sr fractionation due to biogenic calcification. Since the Late Pleistocene deglaciation, the Ca/Sr molar ratios of paleowaters increased systematically from about 100 (a near marine signature) to about 200. Ca/Mg molar ratios varied in the range of 1–25. The ⁸⁷Sr/⁸⁶Sr ratios indicate Late Pleistocene paleowater compositions of 0.7086–0.7091, significantly more radiogenic than present day waters (0.7085). Sr isotopes and Ca/Mg/Sr chemical data together show that weathering of Mesozoic evaporites consistently dominated the dissolved Sr load (80–90%). Carbonate and silicate weathering were less important (1–10%). Trends of Sr dissolved loads were therefore not related to Mg which was mainly mobilized by carbonate weathering. Biotite weathering was an important source of radiogenic Sr in the paleowaters. The short-term release (duration about 600–800 years) of radiogenic Sr during glacier retreat started 15.2 ka ago and was due to enhanced biotite weathering at the glacier base. Long-term release of radiogenic Sr was due to biotite weathering in glacial soils and silicate rocks, and has gradually declined since the Late Pleistocene/Holocene transition.     

Sr/Ca and Ca/Ca fractionation during inorganic calcite formation: I. Sr incorporation

Partitioning of strontium during spontaneous calcite formation was experimentally studied using an advanced CO₂-diffusion technique. Results at different precipitation rates and T = 5, 25, and 40 °C show that at constant temperature Sr incorporation into calcite is controlled by the precipitation rate (R in μmol/m²/h) according to the individual expressions

     

Seasonal dripwater Mg/Ca and Sr/Ca variations driven by cave ventilation: Implications for and modeling of speleothem paleoclimate records

A 4-year study in a central Texas cave quantifies multiple mechanisms that control dripwater composition and how these mechanisms vary at different drip sites. We monitored cave-air compositions, in situ calcite growth, dripwater composition and drip rate every 4-6 weeks. Three groups of drip sites are delineated (Groups 1-3) based on geochemical variations in dripwater composition. Quantitative modeling of mineral-solution reactions within the host carbonate rock and cave environments is used to identify mechanisms that can account for variations in dripwater compositions. The covariation of Mg/Ca (and Sr/Ca) and Sr isotopes is key in delineating whether Mg/Ca and Sr/Ca variations are dictated by water-rock interaction (i.e., calcite or dolomite recrystallization) or prior calcite precipitation (PCP). Group 1 dripwater compositions reflects a narrow range of the extent of water-rock interaction followed by varying amounts of prior calcite precipitation (PCP). Group 2 dripwater compositions are controlled by varying amounts of water-rock interaction with little to no PCP influence. Group 3 dripwater compositions are dictated by variable extents of both water-rock interaction and PCP. Group 1 drip sites show seasonal variations in dripwater Mg/Ca and Sr/Ca, whereas the other drip sites do not. In contrast to the findings of most previous dripwater Mg/Ca-Sr/Ca studies, these seasonal variations (at Group 1 drip sites) are independent of changes in water flux (i.e., rainfall and/or drip rate), and instead significantly correlate with changes in cave-air CO₂ concentrations. These results are consistent with lower cave-air CO₂, related to cool season ventilation of the cave atmosphere, enhancing calcite precipitation and leading to dripwater geochemical evolution via PCP. Group 1 dripwater Mg/Ca and Sr/Ca seasonality and evidence for PCP as a mechanism that can account for that seasonality, have two implications for many other regions where seasonal ventilation of caves is likely: (1) speleothem trace-element records may provide seasonal signals, and (2) such records may be biased toward recording climate conditions during the season when calcite is depositing. Additionally, we use our results to construct a forward model that illustrates the types of speleothem Mg/Ca and Sr/Ca variations that would result from varying controls on dripwater compositions. The model provides a basis for interpreting paleo-dripwater controls from high frequency Mg/Ca and Sr/Ca variations for speleothems from caves at which long term monitoring studies are not feasible.     

南海北部珊瑚Sr/Ca和Mg/Ca温度计及高分辨率SST记录重建尝试

利用全谱直读等离子体光谱(ICPAES)的分析方法精确分析了南海珊瑚的SrCa和MgCa比值,结合实测表层海水温度(SST),标定了海南岛南部三亚海域和西沙海域两个滨珊瑚的SrCa和MgCa温度计。在此基础上,尝试对两个南海北部全新世时期的珊瑚进行SST记录重建。结果显示约540aB.P.(小冰期)西沙海域夏季月均SST较现代低约1℃,而约6500aB.P.(大暖期)海南岛三亚海域夏季月均SST则高出现代1.0～1.5℃。     

Improving SST reconstructions from coral Sr/Ca records: multiple corals from Tahiti (French Polynesia)

We reconstruct SST from coral Sr/Ca ratios measured at three coral cores taken from the lagoon of Tahiti (French Polynesia). Two coral cores were drilled from the same coral colony (one horizontally and one vertically), and a third core was drilled vertically from another coral growing at a different site. We evaluate several Sr/Ca records as proxies for regional SST variations: (1) the three single-core records from Tahiti, (2) an average Sr/Ca record computed from the two cores drilled from the same coral colony, (3) an average Sr/Ca record computed from all three Tahiti cores, and (4) an average Sr/Ca record computed from the three Tahiti cores and a fourth core taken from a different island (Rarotonga). On a monthly scale, the average Sr/Ca record including the four coral cores from Tahiti and Rarotonga shows the best correlation with regional SST. The variance of the SST reconstruction is very realistic and the residual SST is low. This suggests that reconstructing SST from average proxy records gives a better representation of regional SST variations. Of the three Tahiti cores, the one that was drilled horizontally shows the best correlation with grid-SST on an annual mean scale. All three Tahiti corals show much larger interannual SST variations than that indicated by grid-SST.     

Environmental and biological controls on elemental (Mg/Ca, Sr/Ca and Mn/Ca) ratios in shells of the king scallop Pecten maximus

The relationship between potential elemental proxies (Mg/Ca, Sr/Ca and Mn/Ca ratios) and environmental factors was investigated for the bivalve Pecten maximus in a detailed field study undertaken in the Menai Strait, Wales, U.K. An age model constructed for each shell by comparison of measured and predicted oxygen-isotope ratios allowed comparison on a calendar time scale of shell elemental data with environmental variables, as well as estimation of shell growth rates. The seasonal variation of shell Mn/Ca ratios followed a similar pattern to one previously described for dissolved Mn²⁺ in the Menai Strait, although further calibration work is needed to validate such a relationship. Shell Sr/Ca ratios unexpectedly were found to co-vary most significantly with calcification temperature, whilst shell Mg/Ca ratios were the next most significant control. The temporal variation in the factors that control shell Sr/Ca ratios strongly suggest the former observation most likely to be the result of a secondary influence on shell Sr/Ca ratios by kinetic effects, the latter driven by seasonal variation in shell growth rate that is in turn influenced in part by seawater temperature. P. maximus shell Mg/Ca ratio to calcification temperature relationships exhibit an inverse correlation during autumn to early spring (October to March-April) and a positive correlation from late spring through summer (May-June to September). No clear explanation is evident for the former trend, but the similarity of the records from the three shells analysed indicate that it is a real signal and not a spurious observation. These observations confirm that application of the Mg/Ca proxy in P. maximus shells remains problematic, even for seasonal or absolute temperature reconstructions. For the range of calcification temperatures of 5-19 °C, our shell Mg/Ca ratios in P. maximus are approximately one-fourth those in inorganic calcite, half those in the bivalve Pinna nobilis, twice those in the bivalve Mytilus trossulus, and four to five times higher than Mg/Ca ratios in planktonic and benthonic foraminifera. Our findings further support observations that Mg/Ca ratios in bivalve shell calcite are an unreliable temperature proxy, as well as substantial taxon- and species-specific variation in Mg incorporation into bivalves and other calcifying organisms, with profound implications for the application of this geochemical proxy to the bivalve fossil record.     

Ostracod Mg/Sr/Ca and 87Sr/86Sr geochemistry from Tibetan lake sediments: Implications for early to mid‐Pleistocene Indian monsoon and catchment weathering

Jin, Z. D., Bickle, M. J., Chapman, H. J., Yu, J., An, Z., Wang, S. & Greaves, M. J. 2010: Ostracod Mg/Sr/Ca and ⁸⁷Sr/⁸⁶Sr geochemistry from Tibetan lake sediments: Implications for early to mid‐Pleistocene Indian monsoon and catchment weathering. Boreas, 10.1111/j.1502‐3885.2010.00184.x. ISSN 0300‐9483 Lacustrine sediment serves as a valuable archive for tracing catchment weathering processes associated with past climatic and/or tectonic changes. High‐resolution records of fossil ostracod Mg/Ca, Sr/Ca and ⁸⁷Sr/⁸⁶Sr ratios from a lake sediment core from the central Tibetan Plateau reveal a temporal link between lake‐water chemistry and catchment weathering and distinct monsoonal oscillations over the early to mid‐Pleistocene. Between 2.01 and 0.95 Ma, lake‐water chemistry was dominated by a high proportion of carbonate weathering related to variations in the Indian monsoon, resulting in relatively low and constant ostracod ⁸⁷Sr/⁸⁶Sr but obvious fluctuations in Mg/Ca, Sr/Ca and δ¹⁸O. Across the mid‐Pleistocene transition (MPT), a significant increase in ⁸⁷Sr/⁸⁶Sr and frequently fluctuating ratios of ostracod Mg/Ca, Sr/Ca and δ¹⁸O are coincident with increases in both Chinese loess grain size and Arabian Sea lithogenic flux. This correlation indicates an increased glaciation and a strong monsoon seasonal contrast over the plateau. The increase in lake‐water ⁸⁷Sr/⁸⁶Sr across the MPT highlights a change in catchment weathering patterns, rather than one in climate‐enhanced weathering intensity, with an increased weathering of ⁸⁷Sr‐rich minerals potentially induced by marked extensive glaciation and strong seasonality in the central plateau.     

习水县岩溶水系统ρ(Sr2+)、ρ(Sr)/ρ(Ca)、ρ(Sr)/ρ(Mg)分布特征及其应用

通过对流域内不同类型水取样分析,发现流经不同岩层的地下水具有不同的ρ(Sr2+)、ρ(Sr)/ρ(Ca)、ρ(Sr)/ρ(Mg)值.一般来说,流经砂岩层的基岩裂隙水ρ(Sr2+)低,而ρ(Sr)/ρ(Ca)、ρ(Sr)/ρ(Mg)值较高,当砂岩中的基岩裂隙水受到灰岩岩溶水或煤系地层水补给时,其ρ(Sr2+)、ρ( Sr...     

High precision measurements of Mg/Ca and Sr/Ca ratios in carbonates by cold plasma inductively coupled plasma quadrupole mass spectrometry

We present a new high precision analytical method for the determination of Mg/Ca and Sr/Ca ratios in carbonates using an inductively coupled plasma quadrupole mass spectrometer (ICP-QMS) with a 650-W cold plasma technique and a desolvation introduction system. Signal intensities are detected in pulse-counting mode and Mg/Ca and Sr/Ca ratios are calculated directly from intensity ratios of ²⁴Mg/⁴³Ca and ⁸⁶Sr/⁴³Ca using external matrix-matched standards for every 4–5 samples to correct for instrumental mass discrimination and low-frequency ratio drift. Significant matrix effect of Ca content on Mg/Ca determination (− 0.018 Mg/Ca (mmol/mol)/[Ca] (ppm)), can be overcome by diluting [Ca] to 6–8 ppm in the sample solution or using an empirical correction. The Sr/Ca ratio affects the Mg/Ca determination, with a factor of − 0.32% Mg/Ca per mmol/mol. This is mainly caused by the influence of doubly charged ⁸⁶Sr, which biases the intensity measurement of the ⁴³Ca⁺ ion beam. This effect results in a trivial offset of less than 0.1% on Mg/Ca measurements for Quaternary foraminiferal and coral samples. The internal precision of our method ranges from 0.1 to 0.2%. Replicate measurements made on standards and samples show long-term external uncertainties (2σ) of Mg/Ca = 0.84% and Sr/Ca = 0.49%. The minimum sample size requirement is only 3.5 μg of carbonate. The application of this newly developed technique on the planktonic foraminifera Globigerinoides ruber from a core recovered in the southern South China Sea yields a glacial–interglacial difference in sea surface temperature (SST) of 3 °C. Three-year coral Sr/Ca data suggest that the seasonal SST ranged from 22.6–23.8 °C in winter to 26.9–27.9 °C in summer in Nanwan, south Taiwan, during 2000–2002. The coral-Sr/Ca inferred SSTs in 2002 match well with instrumental records, which demonstrates the validity of this ICP-QMS method.     

An Isotope Dilution ICP‐MS Method for the Determination of Mg/Ca and Sr/Ca Ratios in Calcium Carbonate

Mg/Ca and Sr/Ca ratios in calcium carbonate are important components of many palaeoclimate studies. We present an isotope dilution method relying on a single mixed spike containing ²⁵Mg, ⁴³Ca and ⁸⁷Sr. Dozens of samples per day, as small as 10 μg of carbonate, could be dissolved, spiked and run in an ICP‐MS with a precision of 0.8% (2 RSD). Two instruments types, a sector field and a quadrupole ICP‐MS, were compared. The best long term precision found was 0.4% (2 RSD), although this increased by up to a factor of two when samples of very different Mg or Sr content were run together in the same sequence. Long term averages for the two instruments concurred. No matrix effects were detected for a range of Ca concentrations between 0.2 and 2 mmol l^‐1. Accuracy, tested by measuring synthetic standard solutions, was 0.8% with some systematic trends. We demonstrate the strength of this isotope dilution method for (a) obtaining accurate results for sample sets that present a broad Mg and Sr range and (b) testing solid carbonates as candidate reference materials for interlaboratory consistency. Mg/Ca and Sr/Ca results for reference materials were in good agreement with values from the literature.     

Sr/Ca and Ca/Ca fractionation during inorganic calcite formation: II. Ca isotopes

Ca isotope fractionation during inorganic calcite formation was experimentally studied by spontaneous precipitation at various precipitation rates (1.8 < log R < 4.4 μmol/m²/h) and temperatures (5, 25, and 40 °C) with traces of Sr using the CO₂ diffusion technique.Results show that in analogy to Sr/Ca [see Tang J., Köhler S. J. and Dietzel M. (2008) Sr²⁺/Ca²⁺ and ⁴⁴Ca/⁴⁰Ca fractionation during inorganic calcite formation: I. Sr incorporation. Geochim. Cosmochim. Acta] the ⁴⁴Ca/⁴⁰Ca fractionation during calcite formation can be followed by the Surface Entrapment Model (SEMO). According to the SEMO calculations at isotopic equilibrium no fractionation occurs (i.e., the fractionation coefficient α_calcite-aq = (⁴⁴Ca/⁴⁰Ca)_s/(⁴⁴Ca/⁴⁰Ca)_aq = 1 and Δ^44/40Ca_calcite-aq = 0‰), whereas at disequilibrium ⁴⁴Ca is fractionated in a primary surface layer (i.e., the surface entrapment factor of ⁴⁴Ca, F_44Ca < 1). As a crystal grows at disequilibrium, the surface-depleted ⁴⁴Ca is entrapped into the newly formed crystal lattice. ⁴⁴Ca depletion in calcite can be counteracted by ion diffusion within the surface region. Our experimental results show elevated ⁴⁴Ca fractionation in calcite grown at high precipitation rates due to limited time for Ca isotope re-equilibration by ion diffusion. Elevated temperature results in an increase of ⁴⁴Ca ion diffusion and less ⁴⁴Ca fractionation in the surface region. Thus, it is predicted from the SEMO that an increase in temperature results in less ⁴⁴Ca fractionation and the impact of precipitation rate on ⁴⁴Ca fractionation is reduced.A highly significant positive linear relationship between absolute ⁴⁴Ca/⁴⁰Ca fractionation and the apparent Sr distribution coefficient during calcite formation according to the equation

Δ^44/40Ca_calcite-aq=(−1.90±0.26)·logD_Sr−2.83±0.28     

Evidence of rainfall variations in Southern Brazil from trace element ratios (Mg/Ca and Sr/Ca) in a Late Pleistocene stalagmite

Trace element ratios in the Bt2 stalagmite from Botuverá cave, Southern Brazil, are explored as a proxy for changes in the local rainfall recharge during the last 116 ky. BP Mg/Ca and Sr/Ca ratios, measured with an electron microprobe, are significantly positively correlated with one another throughout the entire record, and vary in a way that is very consistent with variations of δ¹⁸O in the same speleothem during the last glacial period. We suggest that prior calcite precipitation in the vadose zone of the cave system is the main factor affecting the incorporation of Mg and Sr into calcite of the stalagmite. This interpretation is supported by trace element correlation patterns and by results from a hydrochemistry study performed in a cave located in the same region and in a similar environmental setting. Therefore, we conclude that higher (lower) Mg/Ca and Sr/Ca values are associated with lower (higher) levels of recharge into the karstic aquifer, as such conditions lead to an increase (decrease) in the volume of calcite precipitated in the unsaturated zone above the cave during dry (wet) climate periods.Trace element variations point to generally dryer (wetter) conditions during lower (high) phases of summer insolation in the southern hemisphere. These periods coincide with decreased (increased) activity of the South American summer monsoon, as revealed by δ¹⁸O stalagmite records. In addition trace element variations show that rather wet conditions persisted throughout most of the last glacial period from approximately 70 to 17 ky BP. We suggest that during this period the glacial boundary conditions, especially ice volume buildup in the northern hemisphere, played an important role for monsoon rainfall intensification in the region.