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.     

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.     

Theoretical study of the dimerization of calcium carbonate in aqueous solution under natural water conditions

First principles calculations have been used to investigate the condensation reactions of hydrated calcium bicarbonate monomers in a simulated aqueous environment. The reaction pathway for the calcium bicarbonate dimerization process has been computed at the density functional theory-PBE level with the COSMO dielectric continuum model to simulate the hydrated environment. The results indicate that calcium bicarbonate dimers form via an associative mechanism: the first step involves a sevenfold calcium bicarbonate intermediate followed by the loss of one water molecule from the first coordination shell of calcium. Both steps are characterised by a low energy barrier of approximately 2 kcal mol⁻¹, suggesting that the dimerization process is not kinetically hindered in aqueous solution. However, the Gibbs free energies for the condensation reactions to form the calcium bicarbonate dimers and the species Ca(HCO₃)₂(H₂O)₄, Ca(HCO₃)₃(H₂O)₃⁻ and Ca₂(HCO₃)(H₂O)₁₀³⁺, computed using the PBE and mPW1B95 density functional theory levels for the gas-phase component and the UAHF-CPCM solvation model for the hydration contribution, are all positive, which indicates that the formation of these early calcium bicarbonate clusters is thermodynamically unfavourable in aqueous solutions. Our calculations therefore suggest that the oligomerization of calcium carbonate is not spontaneous in water, at the conditions considered in our simulations, i.e. T = 298 K and neutral pH, which indicates that the nucleation of calcium carbonate cannot occur through a homogeneous process when calcium-bicarbonate ion pairs are the major source of CaCO₃ in the aqueous environment.     

Hydrogeochemical characterization and quality assessment of groundwater around Umrer coal mine area Nagpur District,Maharashtra, India

Quality assessment as well as hydrogeochemical characterization of 45 representative groundwater samples around Umrer coal mine area was undertaken. The pH of the water lies in the normal range i.e. from 7.5 to 8.5, the electrical conductivity varies from 826 to 1,741, the total hardness varies from 289 to 1,302 and the TDS values range from 528.6 to 1,114.2 mg/l which reflects variation in lithology and thus, the distinction in hydrogeological regime. The cation chemistry is dominated by Ca²⁺ and Mg²⁺ while anion chemistry is dominated by Cl^? and HCO₃ ^?. Out of total ten hydrochemical facies, the two dominant facies are Mg–Ca–HCO₃ (37.7 %) and Ca–Mg–SO₄–HCO₃ (17.7 %). The groundwater in the study area, in general, is useful for drinking and domestic use; however, it has marginal utility for irrigation purpose. Standard US Salinity Laboratory classification shows that water of the study area belongs to C2–S1 and C3–S1 classes. The concentration of 9 trace elements analysed from 18 samples did not exceed the desirable limit.     

Determination of element/Ca ratios in foraminifera and corals using cold- and hot-plasma techniques in inductively coupled plasma sector field mass spectrometry

We have developed a rapid and precise procedure for measuring multiple elements in foraminifera and corals by inductively coupled plasma sector field mass spectrometry (ICP-SF-MS) with both cold- [800 W radio frequency (RF) power] and hot- (1200 W RF power) plasma techniques. Our quality control program includes careful subsampling protocols, contamination-free workbench spaces, and refined plastic-ware cleaning process. Element/Ca ratios are calculated directly from ion beam intensities of ²⁴Mg, ²⁷Al, ⁴³Ca, ⁵⁵Mn, ⁵⁷Fe, ⁸⁶Sr, and ¹³⁸Ba, using a standard bracketing method. A routine measurement time is 3–5 min per dissolved sample. The matrix effects of nitric acid, and Ca and Sr levels, are carefully quantified and overcome. There is no significant difference between data determined by cold- and hot-plasma methods, but the techniques have different advantages. The cold-plasma technique offers a more stable plasma condition and better reproducibility for ppm-level elements. Long-term 2-sigma relative standard deviations (2-RSD) for repeat measurements of an in-house coral standard are 0.32% for Mg/Ca and 0.43% for Sr/Ca by cold-plasma ICP-SF-MS, and 0.69% for Mg/Ca and 0.51% for Sr/Ca by hot-plasma ICP-SF-MS. The higher sensitivity and enhanced measurement precision of the hot-plasma procedure yields 2-RSD precision for μmol/mol trace elements of 0.60% (Mg/Ca), 9.9% (Al/Ca), 0.68% (Mn/Ca), 2.7% (Fe/Ca), 0.50% (Sr/Ca), and 0.84% (Ba/Ca) for an in-house foraminiferal standard. Our refined ICP-SF-MS technique, which has the advantages of small sample size (2–4 μg carbonate consumed) and fast sample throughput (5–8 samples/hour), should open the way to the production of high precision and high resolution geochemical records for natural carbonate materials.     

Hydrochemical characteristics of surface and groundwater and suitability for drinking and agricultural use in the Upper Tigris River Basin,Diyarbakır–Batman,Turkey

Investigations were undertaken into the quality of surface water and groundwater bodies within the Upper Tigris Basin in Turkey to determine their suitability for potable and agricultural use. In the study area, the majority of the groundwater and surface water samples belong to the calcium–magnesium–bicarbonate type (Ca–Mg–HCO₃) or magnesium–calcium–bicarbonate type (Mg–Ca–HCO₃). Chemical analysis of all water samples shows that the mean cation concentrations (in mg/L) were in the order Ca²⁺ > Mg²⁺ > Na⁺ > K⁺ and that of anions are in the order \( \text{HCO}_{3}^{ - } \) > \( \text{SO}_{4}^{2 - } \) > Cl^? > \( \text{CO}_{3}^{ - } \) for all groundwater and surface water samples. The Mg²⁺/Ca²⁺ ratio ranges from 0.21 to 1.30 with most of the values greater than 0.5, indicating that weathering of dolomites is dominant in groundwater. The analysis reveals that all of the samples are neutral to slightly alkaline (pH 7.0–8.7). Groundwater and surface water suitability for drinking usage was evaluated according to the World Health Organization and Turkish Standards (TSE-266) and suggests that most of the samples are suitable for drinking. Various determinants such as sodium absorption ratio, percent sodium (Na %), residual sodium carbonate and soluble sodium percentage revealed that most of the samples are suitable for irrigation. According to MH values, all of the well water samples were suitable for irrigation purposes, but 80 and 81.82% of Zillek springs and surface water samples were unsuitable. As per the PI values, the water samples from the study area are classified as Class I and Class II and are considered to be suitable for irrigation.     

Calcium isotope (δCa) fractionation along hydrothermal pathways, Logatchev field (Mid-Atlantic Ridge, 14°45′N)

We investigate the Logatchev Hydrothermal Field at the Mid-Atlantic Ridge, 14°45′N to constrain the calcium isotope hydrothermal flux into the ocean. During the transformation of seawater to a hydrothermal solution, the Ca concentration of pristine seawater ([Ca]_SW) increases from about 10 mM to about 32 mM in the hydrothermal fluid endmember ([Ca]_HydEnd) and thereby adopts a δ^44/40Ca_HydEnd of −0.95 ± 0.07‰ relative to seawater (SW) and a ⁸⁷Sr/⁸⁶Sr isotope ratio of 0.7034(4). We demonstrate that δ^44/40Ca_HydEnd is higher than that of the bedrock at the Logatchev field. From mass balance calculations, we deduce a δ^44/40Ca of −1.17 ± 0.04‰ (SW) for the host-rocks in the reaction zone and −1.45 ± 0.05‰ (SW) for the isotopic composition of the entire hydrothermal cell of the Logatchev field. The values are isotopically lighter than the currently assumed δ^44/40Ca for Bulk Earth of −0.92 ± 0.18‰ (SW) [Skulan J., DePaolo D. J. and Owens T. L. (1997) Biological control of calcium isotopic abundances in the global calcium cycle. Geochim. Cosmochim. Acta61,(12) 2505-2510] and challenge previous assumptions of no Ca isotope fractionation between hydrothermal fluid and the oceanic crust [Zhu P. and Macdougall J. D. (1998) Calcium isotopes in the marine environment and the oceanic calcium cycle. Geochim. Cosmochim. Acta62,(10) 1691-1698; Schmitt A. -D., Chabeaux F. and Stille P. (2003) The calcium riverine and hydrothermal isotopic fluxes and the oceanic calcium mass balance. Earth Planet. Sci. Lett. 6731, 1-16]. Here we propose that Ca isotope fractionation along the fluid flow pathway of the Logatchev field occurs during the precipitation of anhydrite. Two anhydrite samples from the Logatchev Hydrothermal Field show an average fractionation of about Δ^44/40Ca = −0.5‰ relative to their assumed parental solutions. Ca isotope ratios in aragonites from carbonate veins from ODP drill cores indicate aragonite precipitation directly from seawater at low temperatures with an average δ^44/40Ca of −1.54 ± 0.08‰ (SW). The relatively large fractionation between the aragonite precipitates and seawater in combination with their frequent abundance in weathered mafic and ultramafic rocks suggest a reconsideration of the marine Ca isotope budget, in particular with regard to ocean crust alteration.     

Mg and Ca isotopic study of individual microscopic crystals from the Allende meteorite by the direct loading technique

We have developed a direct loading technique for determining the isotopic composition of Mg in chemically unseparated samples. This technique has a sensitivity and precision comparable with those of the conventional technique of analyzing pure Mg salt and eliminates contamination introduced during the chemical separation of Mg. This results in a significant reduction in sample size required for an analysis. This technique was combined with other characterization techniques of microscopic samples (e.g. optical microscopy, SEM, EPMA), and was applied to four single crystals of pure phases from an Allende inclusion ranging in size from 25 to 150 μm. Using a total sample of 4 μ, we found an anorthite crystal showing an enrichment in ²⁶Mg of 10% and were able to construct an ²⁶Al-²⁶Mg isochron which confirms our previous results obtained on macroscopic samples of the same inclusion. The isotopic composition of Ca was also measured along with Mg, on a directly loaded anorthite crystal from this inclusion, during the same mass spectrometer run and was shown to be essentially normal. Thus, the direct loading technique is applicable to Ca and will be useful in a correlative study of isotopic effects of different elements on individual microscopic samples. The extension of this technique to other elements appears feasible but will require extensive testing to control possible interferences.     

Calcium isotope ratios in animal and human bone

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

Synergistic effect of calcium and bicarbonate in enhancing arsenate release from ferrihydrite

Many groundwater systems contain anomalously high arsenic concentrations, associated with less than expected retention of As by adsorption to iron (hydr)oxides. Although carbonates are ubiquitous in aquifers, their relationship to arsenate mobilization is not well characterized. This research examines arsenate release from poorly crystalline iron hydroxides in abiotic systems containing calcium and magnesium with bicarbonate under conditions of static and dynamic flow (pH 7.5-8). Aqueous arsenic levels remained low when arsenate-bearing ferrihydrite was equilibrated with artificial groundwater solution containing Ca, Mg, and HCO₃⁻. In batch titrations in which a solution of Ca and HCO₃⁻ was added repeatedly, the ferrihydrite surface became saturated with adsorbed Ca and HCO₃⁻, and aqueous As levels increased by 1-2 orders of magnitude. In columns containing Ca or Mg and HCO₃⁻, As solubility initially mimicked titrations, but then rapidly increased by an additional order of magnitude (reaching 12 μM As). Separately, calcium chloride and other simple salts did not induce As release, although sodium bicarbonate and lactate facilitated minor As release under flow. Results indicate that adsorption of calcium or magnesium with bicarbonate leads to As desorption from ferrihydrite, to a degree greater than expected from competitive effects alone, especially under dynamic flow. This desorption may be an important mechanism of As mobilization in As-impacted, circumneutral aquifers, especially those undergoing rapid mineralization of organic matter, which induces calcite dissolution and the production of dissolved calcium and bicarbonate.     

Ca isotope fingerprints of early crust-mantle evolution

The utility of ⁴⁰Ca/⁴⁴Ca as a tracer of pre-existing crustal contributions in early Archaean cratons has been explored to identify traces of Hadean crust and to assess the style of continental growth. The relatively short half-life of ⁴⁰K (∼1.3 Gy) means that its decay to ⁴⁰Ca occurs dominantly during early Earth History. If Archaean crust had a significant component derived from a more ancient protolith, as anticipated by “steady state” crustal evolution models, this should be clearly reflected in radiogenic ⁴⁰Ca/⁴⁴Ca ratios (or positive initial ε_Ca) in different Archaean cratons. A high precision thermal ionisation technique has been used to analyse the ⁴⁰Ca/⁴⁴Ca ratios of plagioclase separates and associated whole rocks in ∼3.6 Ga (early Archaean) samples from Zimbabwe and West Greenland. Three out of four tonalite, trondhjemite, granodiorite (TTG) suite samples from Zimbabwe display initial ⁴⁰Ca/⁴⁴Ca ratios indistinguishable from our measured modern MORB value (i.e., ε_Ca(3.6) ∼ 0). Greenland samples, however, are very diverse ranging from ε_Ca(3.7) = 0.1 in mafic pillow lavas and felsic sheets from the Isua supracrustal belt, up to very radiogenic signatures (ε_Ca(3.7) = 2.9) in both mafic rocks of the Akilia association and felsic TTG from the coastal Amîtsoq gneisses.At face value, these results imply the Zimbabwe crust is juvenile whereas most Greenland samples include an earlier crustal component. Yet the west Greenland craton, as with many Archaean localities, has experienced a complex geological history and the interpretation of age-corrected initial isotope values requires great care. Both felsic and mafic samples from Greenland display ε_Ca(3.7) so radiogenic that they are not readily explained by crustal growth scenarios. The presence of such radiogenic ⁴⁰Ca/⁴⁴Ca found in low K/Ca plagioclases requires Ca isotope exchange between plagioclase and whole rock during later metamorphic event(s). In addition the unexpectedly radiogenic Ca isotope ratios in some mafic samples reflect anomalous K/Ca ratios as a result of intense K-metasomatism ∼3.6 Ga. Thus Ca isotope measurements are not a robust tracer of crustal growth in the presence of intense tectono-metamorphic processes. Coupled with other isotope data, however, the degree of overprint can be estimated and the ⁴⁰Ca/⁴⁴Ca ratio of a little disturbed sample hints at a small contribution of Hadean protocrust in the coastal part of the Godthåbsfjord area (Southwest Greenland). In the majority of Zimbabwe TTG samples, unradiogenic initial Ca isotope ratios point to very little prior crustal history and minor subsequent disturbance. We thus infer that the modest initial ε_Nd ∼0.8 of the Zimbabwean samples is representative of the depleted mantle at ∼3.6 Ga. Furthermore, Ca isotope systematics provide little support for a “steady state” model of crustal growth.     

The effect of calcium on aqueous uranium(VI) speciation and adsorption to ferrihydrite and quartz

Recent studies of uranium(VI) geochemistry have focused on the potentially important role of the aqueous species, CaUO₂(CO₃)₃²⁻ and Ca₂UO₂(CO₃)₃⁰(aq), on inhibition of microbial reduction and uranium(VI) aqueous speciation in contaminated groundwater. However, to our knowledge, there have been no direct studies of the effects of these species on U(VI) adsorption by mineral phases. The sorption of U(VI) on quartz and ferrihydrite was investigated in NaNO₃ solutions equilibrated with either ambient air (430 ppm CO₂) or 2% CO₂ in the presence of 0, 1.8, or 8.9 mM Ca²⁺. Under conditions where the Ca₂UO₂(CO₃)₃⁰(aq) species predominates U(VI) aqueous speciation, the presence of Ca in solution lowered U(VI) adsorption on quartz from 77% in the absence of Ca to 42% and 10% at Ca concentrations of 1.8 and 8.9 mM, respectively. U(VI) adsorption to ferrihydrite decreased from 83% in the absence of Ca to 57% in the presence of 1.8 mM Ca. Surface complexation model predictions that included the formation constant for aqueous Ca₂UO₂(CO₃)₃⁰(aq) accurately simulated the effect of Ca²⁺ on U(VI) sorption onto quartz and ferrihydrite within the thermodynamic uncertainty of the stability constant value. This study confirms that Ca²⁺ can have a significant impact on the aqueous speciation of U(VI), and consequently, on the sorption and mobility of U(VI) in aquifers.     

Calcite and barite precipitation in CaCO<Subscript>3</Subscript>-BaSO<Subscript>4</Subscript>-NaCl and BaSO<Subscript>4</Subscript>-NaCl-CaCl<Subscript>2</Subscript> aqueous systems: kinetic and microstructural study

During the production of hydrocarbons from subterranean reservoirs, scaling with calcium carbonate and barium sulfate causes flux decline and dangerous problems in production facilities. This work is intended to study the effect of calcium ions on the precipitation of barium sulfate (barite); then, the effect of the formed barite on calcium carbonate crystallization. The conductometric and pH methods were used to follow the progress of the precipitation reaction in aqueous medium. The obtained precipitates were characterized by FTIR, RAMAN, SEM, and XRD. It was shown that Ca²⁺ in the reaction media does not affect the microstructure of barite even for higher calcium–barium molar ratio. It influences the precipitation kinetics and the solubility of barite by the formation of CaSO₄° ion pairing as a predominant role of complex formation (CaSO4) and the increase of the ionic strength. In Ca(HCO₃)₂-BaSO₄-NaCl aqueous system, experiments have showed that added or formed barite in the reaction media accelerates calcite precipitation. No effect on the microstructure of heterogeneous formed calcite which remain calcite shape. However the presence of carbonate ions affects slightly the microstructure of barite.     

Calcium isotope fractionation in modern scleractinian corals

The ⁴⁴Ca/⁴⁰Ca ratios of cultured (Acropora sp.) and open ocean (Pavona clavus, Porites sp.) tropical reef corals are positively correlated with growth temperature. The slope of the temperature-fractionation relation is similar to inorganic aragonite precipitates. However, δ^44/40Ca of the coral aragonite is offset from inorganic and sclerosponge aragonite by about +0.5‰. This offset can neither be explained by the very fast, biologically controlled calcification of scleractinian corals, nor as a consequence of calcification from a partly closed volume of fluid. As corals actively transport calcium through several cell layers to the site of calcification, the most likely explanation for the offset is a biologically induced fractionation. Our results indicate a limited use of Ca isotopes in scleractinian corals as temperature proxy.     

Ca isotopes in carbonate sediment and pore fluid from ODP Site 807A: The Ca(aq)-calcite equilibrium fractionation factor and calcite recrystallization rates in Pleistocene sediments

The calcium isotopic compositions (δ⁴⁴Ca) of 30 high-purity nannofossil ooze and chalk and 7 pore fluid samples from ODP Site 807A (Ontong Java Plateau) are used in conjunction with numerical models to determine the equilibrium calcium isotope fractionation factor (α_s−f) between calcite and dissolved Ca²⁺ and the rates of post-depositional recrystallization in deep sea carbonate ooze. The value of α_s−f at equilibrium in the marine sedimentary section is 1.0000 ± 0.0001, which is significantly different from the value (0.9987 ± 0.0002) found in laboratory experiments of calcite precipitation and in the formation of biogenic calcite in the surface ocean. We hypothesize that this fractionation factor is relevant to calcite precipitation in any system at equilibrium and that this equilibrium fractionation factor has implications for the mechanisms responsible for Ca isotope fractionation during calcite precipitation. We describe a steady state model that offers a unified framework for explaining Ca isotope fractionation across the observed precipitation rate range of ∼14 orders of magnitude. The model attributes Ca isotope fractionation to the relative balance between the attachment and detachment fluxes at the calcite crystal surface. This model represents our hypothesis for the mechanism responsible for isotope fractionation during calcite precipitation. The Ca isotope data provide evidence that the bulk rate of calcite recrystallization in freshly-deposited carbonate ooze is 30-40%/Myr, and decreases with age to about 2%/Myr in 2-3 million year old sediment. The recrystallization rates determined from Ca isotopes for Pleistocene sediments are higher than those previously inferred from pore fluid Sr concentration and are consistent with rates derived for Late Pleistocene siliciclastic sediments using uranium isotopes. Combining our results for the equilibrium fractionation factor and recrystallization rates, we evaluate the effect of diagenesis on the Ca isotopic composition of marine carbonates at Site 807A. Since calcite precipitation rates in the sedimentary column are many orders of magnitude slower than laboratory experiments and the pore fluids are only slightly oversaturated with respect to calcite, the isotopic composition of diagenetic calcite is likely to reflect equilibrium precipitation. Accordingly, diagenesis produces a maximum shift in δ⁴⁴Ca of +0.15‰ for Site 807A sediments but will have a larger impact where sedimentation rates are low, seawater circulates through the sediment pile, or there are prolonged depositional hiatuses.     

Calcium Isotopic Fractionation during Ion‐Exchange Column Chemistry and Thermal Ionisation Mass Spectrometry (TIMS) Determination

Significant isotopic fractionation can occur during column chemistry and determination by mass spectrometry. Improper correction may produce uncertainties in the isotopic composition of geological samples. We investigated calcium isotopic fractionation during these two processes and set up a model to check data quality. The δ^44/40Ca_915a value of IAPSO seawater in different Ca cuts (e.g., 0–20, 20–40, 40–60, 60–80 and 80–100%) on column chemistry ranged from ~ 4‰ to 0‰. The more Ca was eluted, the lower the δ^44/40Ca_915a value of the elution was found. The isotopic fractionation of calcium on the column appeared to follow the exponential law. However, TIMS instrumental fractionation during Ca runs did not always follow the exponential law due to mixing effects from sample reservoirs on the filament. Our results show that errors could be caused if the instrumental fractionation deviates from the exponential law, especially when the fractionation degree is large. To improve the measurement uncertainty, a model is proposed to check the behaviour and degree of instrumental fractionation, which will provide a quick and reasonable verdict on the data quality of TIMS runs.     

Modelling weathering processes at the catchment scale: The WITCH numerical model

A numerical model of chemical weathering in soil horizons and underlying bedrock (WITCH) has been coupled to a numerical model of water and carbon cycles in forest ecosystems (ASPECTS) to simulate the concentration of major species within the soil horizons and the stream of the Strengbach granitic watershed, located in the Vosges Mountains (France). For the first time, simulations of solute concentrations in soil layers and in the catchment river have been performed on a seasonal basis. The model is able to reproduce the concentrations of most major species within the soil horizons, as well as catching the first-order seasonal fluctuations of aqueous calcium, magnesium and silica concentrations. However, the WITCH model underestimates concentrations of Mg²⁺ and silica at the spring of the catchment stream, and significantly underestimates Ca²⁺ concentration. The deficit in calculated calcium can be compensated for by dissolution of trace apatite disseminated in the bedrock. However, the resulting increased Ca²⁺ release yields important smectite precipitation in the deepest model layer (in contact with the bedrock) and subsequent removal of large amount of silica and magnesium from solution. In contrast, the model accurately accounts for the concentrations of major species (Ca, Mg and silica) measured in the catchment stream when precipitation of clay minerals is not allowed. The model underestimation of Mg²⁺ and H₄SiO₄ concentrations when precipitation of well crystallized smectites is allowed strongly suggests that precipitation of well crystallized clay minerals is overestimated and that more soluble poorly crystallized and amorphous materials may be forming. In agreement with observations on other watersheds draining granitic rocks, this study indicates that highly soluble trace calcic phases control the aqueous calcium budget in the Strengbach watershed.     

Determination of Sr isotopes in calcium phosphates using laser ablation inductively coupled plasma mass spectrometry and their application to archaeological tooth enamel

The determination of accurate Sr isotope ratios in calcium phosphate matrices by laser ablation multi-collector ICP-MS is demonstrated as possible even with low Sr concentration archaeological material. Multiple on-line interference correction routines for doubly-charged REE, Ca dimers and Rb with additional calibration against TIMS-characterised materials are required to achieve this. The calibration strategy proposed uses both inorganic and biogenic apatite matrices to monitor and correct for a ⁴⁰Ca-³¹P-¹⁶O polyatomic present at levels of 0.3-1% of the non-oxide peak, which interferes on ⁸⁷Sr causing inaccuracies of 0.03-0.4% in the ⁸⁷Sr/⁸⁶Sr isotope ratio. The possibility also exists for synthetic materials to be used in this calibration. After correction for interferences total combined uncertainties of 0.04-0.15% (2SD) are achieved for analyses of 13-24 μg of archaeological tooth enamel with Sr concentrations of ca. 100-500 ppm using MC-ICP-MS. In particular, for samples containing >300 ppm Sr, total uncertainties of ∼0.05% are possible utilising 7-12 ng Sr. Data quality is monitored by determination of ⁸⁴Sr/⁸⁶Sr ratios.When applied to an archaeological cattle tooth this approach shows Sr-isotope variations along the length of the tooth in agreement with independent TIMS data. The ⁴⁰Ca-³¹P-¹⁶O polyatomic interference is the root cause of the bias at mass 87 during laser ablation ICP-MS analysis of inorganic and biogenic calcium phosphate (apatite) matrices. This results in inaccurate ⁸⁷Sr/⁸⁶Sr ratios even after correction of Ca dimers and doubly charged rare earth elements. This interference is essentially constant at specific ablation conditions and therefore the effect on ⁸⁷Sr/⁸⁶Sr data varies in proportion to changes in the Sr concentration of the ablated material. Complete elimination of this interference is unlikely through normal analytical mechanisms and therefore represents a limitation on the achievable accuracy of LA-(MC-)ICP-MS ⁸⁷Sr/⁸⁶Sr data without rigorous calibration to known reference materials.     

The anomalous Ca cycle in the Ediacaran ocean: Evidence from Ca isotopes preserved in carbonates in the Three Gorges area,South China

The Ediacaran–Cambrian was one of the most important periods for the evolution of life. Recent studies have provided detailed chemostratigraphies that decipher the linkages between ambient surface environmental changes and biological evolution. The occurrence of skeletal fossils in Ediacaran rocks suggests that the possible onset of Ca-biomineralization started in the latest Neoproterozoic. Molecular clocks also predict the emergence of animals containing Ca-carbonate spicules in the Neoproterozoic. Therefore, it is important to estimate the transition of the Ca cycle in seawater. Ancient Ca cycles in the oceans are estimated from the calcium isotopic compositions of carbonate rocks. However, the lack of continuous Ca isotopic data in the Ediacaran leaves the Ca cycle unresolved.The almost continuously exposed, Ediacaran and Cambrian strata in South China mainly comprise carbonate rocks with subordinate black shales and sandstones, which contain many fossils, suitable for the study of environmental and biological changes. We conducted drilling from the Liantuo, via the Nantuo, Doushantuo, Dengying and Yanjiahe to the Shuijingtuo formation at four sites in the Three Gorges area in order to obtain continuous, fresh samples without surface alteration and oxidation. We analyzed ⁴⁴Ca/⁴²Ca ratios in carbonate rocks with a multiple collector-inductively coupled plasma-mass spectrometer (MC-ICP-MS) screened for diagenetic alteration.The resultant δ^44/42Ca ratios exhibit a smooth curve. The values of δ^44/42Ca are anomalously high relative to those in the Phanerozoic, and they gradually decrease towards the end of the Ediacaran. Our new Ca isotope chemostratigraphy suggests that a different Ca cycle had existed during the Ediacaran. The long-term, high δ^44/42Ca is not simply explicable by changes in temperature, differences in carbonate mineralogy, or changes in the input/output fluxes of Ca to the ocean. We propose three possible explanations for the observed high δ^44/42Ca ratios in the Ediacaran: high δ^44/42Ca ratios of Ca inputs, potential undiscovered sinks of Ca with low δ^44/42Ca values, and negligible isotope fractionation between carbonate and seawater; we consider that one or all of these contributed to the high δ^44/42Ca ratios. Of these, we prefer the small isotope fractionation, which implies that the Ca concentration in seawater was initially low in the early Ediacaran and increased throughout that period.     

Immiscibility of Fluoride–Calcium and Silicate Melts in Trachyrhyolitic Magma: Data on Acidic Volcanic Rocks from the Nyalga Basin,Central Mongolia

An Early Cretaceous (120 ± 5 Ma) trachyrhyolite lava sheet in the Nyalga basin, Central Mongolia, includes a domain (～0.5 km²) of unusual fluorite-enriched rocks with anomalously high concentrations of CaO (1.2–25.7 wt %) and F (0.6–15 wt %). The textures and structures of the rocks suggest that they were produced by two immiscible melts: fluoride–calcium (F–Ca) and trachyrhyolitic. Data on mineral-hosted inclusions and SEM EDS studies of the matrixes of the rocks indicate that a F–Ca melt occurred in the trachyrhyolitic magmas during its various evolutionary episodes, starting from the growth of minerals in a magmatic chamber and ending with eruptions on the surface. Elevated fluorine concentrations (up to 1.5–2 wt %) in local domains of the trachyrhyolitic melt may have resulted in the onset of its liquid immiscibility and the exsolution of a F–Ca liquid phase. This was associated with the redistribution of trace elements: REE, Y, Sr, and P were preferably concentrated in the F–Ca melt, while Zr, Hf, Ta, and Nb were mostly redistributed into the immiscible silicate liquid. The F–Ca melt contained oxygen and aqueous fluid and remained mobile until vitrification of the trachyrhyolitic magma. The oxygen-enriched F–Ca phase was transformed into fluorite at 570–780°? and a high oxygen fugacity Δlog fO₂ (0.9–1.7) relative to the NNO buffer. Ferrian ilmenite, monazite-group As-bearing minerals, and cerianite crystallized under oxidizing conditions, and the titanomagnetite was replaced by hematite. The Ca- and F-enriched rocks were affected by low-density (0.05–0.1 g/cm³) aqueous fluid, which was released from the crystallizing trachyrhyolitic melt, and this led to the partial removal of REE from the F–Ca phase. The chondrite-normalized REE and Y patterns of the fluidmodified rocks show positive Y anomalies and W-shaped minima from Gd to Ho. A composition of the F–Ca phase close to the original one is conserved in mineral-hosted inclusions and in relict isolations in the rocks matrix. It is so far unclear why fluorite did not crystallize from the F–Ca melt contained in the trachyrhyolitic magma. Conceivably, this was favored by high-temperature oxidizing conditions under which the melt accommodated oxygen and aqueous fluid. The possible origin of mobile oxygen-bearing fluorite–calcic melt at subsolidus temperature should be taken into account when magmatic rocks and ores are studied. Fluorite and accompanying ore mineralization might have been formed in certain instances not by hydrothermal–metasomatic processes but during the fluid–magmatic stage as a result of the transformation of F–Ca melt enriched in REE, Y, and other trace elements.