In situ Sr/Sr investigation of igneous apatites and carbonates using laser-ablation MC-ICP-MS

In situ Sr isotopic compositions of coexisting apatite and carbonate for carbonatites from the Sarfartoq alkaline complex, Greenland, have been determined by laser-ablation multicollector inductively coupled plasma mass spectrometry. This study is the first to examine the extent of Sr isotopic homogeneity among coexisting igneous minerals containing high Sr (>3000 ppm) and low Rb (?1 ppm) contents within a single ∼50-μm-thick thin-section mount. This technique is capable of producing measured ⁸⁷Sr/⁸⁶Sr values with analytical precision (∼0.005%, 2σ) approaching those obtained by thermal ionization mass spectrometry but in a much shorter interval of time (100 s vs. >1 h, respectively). The combined total analyses (n = 107) of apatite and carbonate yield ⁸⁷Sr/⁸⁶Sr compositions ranging from ∼0.7025 to ∼0.7031. This relatively large variation in Sr isotopic compositions (∼0.0006) is ∼1 order of magnitude larger than the estimated external reproducibility (∼0.00005, 2σ) of the method. The large range in ⁸⁷Sr/⁸⁶Sr values suggests that apatite and carbonate precipitated predominantly under nonequilibrium conditions. The isotopic variations observed within individual hand specimens may therefore reflect larger (regional) scale open-system processes, possibly involving mixing of carbonatitic melts derived from distinct mantle sources or from a common isotopically heterogeneous mantle.     

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

     

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.     

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.     

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.     

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.     

Determination of Pb/Pb ages on zircon and monazite by laser-ablation ICPMS and application to a study of sedimentary provenance and metamorphism in southeastern Brazil

The recently developed method of laser ablation-inductively coupled plasma mass spectrometry (LA-ICPMS) allows the determination of ²⁰⁷Pb/²⁰⁶Pb ages of single zircon grains. The main advantages of the method are minimal sample preparation, low cost, and high throughput. In this work we present an analytical routine for geochronological analyses of zircon and monazite by LA-ICPMS and its application to the Ribeira Belt of the Brazilian Orogen in southeastern Brazil. The ²⁰⁷Pb/²⁰⁶Pb ages of one hundred and thirty-seven detrital zircons from amphibolite facies quartzites from three lithotectonic domains in the central Ribeira Belt indicate that they are derived mainly from Paleoproterozoic crust of Transamazonian age (2.0−2.3 Ga). A small number of zircons originated in 2.6−2.9 Ga Archean crust. These results are coherent with 2.1−2.2 Ga and 2.6−3.0 Ga U---Pb ages previously obtained for basement gneisses. The viability of the method to date monazite is also assessed. Monazites from the same quartzite samples yield ages between 2.1 Ga and 0.57 Ga. indicating variable resetting of the U---Pb system during amphibolite facies metamorphism. In contrast, monazite from a basement migmatite and syn-metamorphic granitoids yields ages in the 500–700 Ma range, in general agreement with U-Pb ages of 590-565 Ma for the main metamorphic event.

The LA-ICPMS ²⁰⁷Pb/²⁰⁶Pb ages are coherent and agree with expected results based on previous U---Pb geochronology, and show that the method has immediate applicability. At present, the most significant limitations of the method are the inability to yield reliable U/Pb values, analytical precision in the 1–10% range, and the requirement of grains larger than 80 gmm The method may be advantageous for provenance studies of Precambrian detrital sequences.     

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     

Sr/Sr and Sr/Ca in speleothems for paleoclimate reconstruction in Central China between 70 and 280 kyr ago

Limestone cave deposits (speleothems) provide archives for past changes in regional climates over a range of timescales. While δ¹⁸O and δ¹³C in speleothem calcite have been commonly used for reconstruction of paleoclimates, we report here further efforts in the use of ⁸⁷Sr/⁸⁶Sr and Sr/Ca signals in speleothem calcite to deduce paleomonsoon variability near the Loess Plateau of central China. A two end-member mass-balance model of concentration and isotopic composition of strontium in a cave system is used to estimate variation of the ⁸⁷Sr/⁸⁶Sr ratio in sediments overlying a limestone cave. We show that this ratio reflects climate-driven variations in the provenance and the extent of chemical weathering of the epikarstic sediments. The measurements of ⁸⁷Sr/⁸⁶Sr made on a well-dated stalagmite, SFL, from Buddha Cave (33^o40N′ 109^o05′E) show ratios of 0.71092 to 0.71133 (±0.00001 as 2σ) during relatively cold periods (e.g., Marine Isotope Stage (MIS) 5b, 5d, and 8), lower than ratios of 0.71133 to 0.71194 during relatively warm periods (e.g., MIS 5a, 5c, 5e, and 7). As changes in the Sr/Ca ratio may affect speleothem ⁸⁷Sr/⁸⁶Sr, we show that the direct use of speleothem ⁸⁷Sr/⁸⁶Sr is less ideal than our modeled ⁸⁷Sr/⁸⁶Sr for the exogenic Sr source above the cave as a paleomonsoon proxy. Using the δ¹⁸O, δ¹³C, Sr/Ca, and ⁸⁷Sr/⁸⁶Sr records of the stalagmite, we reconstruct the variability of the East Asian monsoon for the time period between 70 and 280 kyr ago. The results show that summer monsoons were more intense during interglacial periods than during glacial periods.     

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。      

Combined Sr isotope and trace element analysis of melt inclusions at sub-ng levels using micro-milling, TIMS and ICPMS

This paper describes a technique, which allows precise and accurate Sr isotope measurement combined with trace element analysis of individual melt inclusions, of sample sizes  1 ng of Sr. The technique involves sampling by micro-milling, chemical dissolution, micro Sr column chemistry, TIMS, and ICPMS analyses. A 10% aliquot of each sample solution is used for trace element analysis by double focusing magnetic sector field ICPMS, while Sr is chemically separated from the remaining 90% and used for ⁸⁷Sr/⁸⁶Sr determinations by TIMS.During the development of the technique outlined above, we documented in detail the potential sources of blank contributions and their magnitude. The average size and Sr isotope composition of our laboratory total procedural blank during this study was 5.4 pg ± 0.3 pg Sr (n = 21) with an ⁸⁷Sr/⁸⁶Sr of 0.7111 ± 0.0002 (2SE, n = 3). The total procedural Rb blank was 1.9 ± 0.7 pg (n = 21). The total procedural blank was found to have minimal effect (< 150 ppm shift) on the ⁸⁷Sr/⁸⁶Sr of sample material containing down to  250 pg Sr. Applying a blank correction allows ‘in house’ standards of this size to be corrected back to within 175 ppm of their accepted values. By applying blank corrections we can confidently measure the Sr isotope composition on sample sizes down to  25 pg Sr to an accuracy better than 400 ppm.The utility of the technique is illustrated by application to a suite of melt inclusions from NW Iceland and their host olivines. It is shown that the effect of a small amount of entrainment of the host olivine during sampling of 50 μm melt inclusions has a negligible effect on the measured Sr isotope and trace element composition. Furthermore, where melt inclusions are < 50 μm it is possible to obtain Sr isotope and trace element data on multiple melt inclusions hosted in a single olivine. This provides similar information to that of the single melt inclusions.     

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)。     

Ba/Sr,Ca/Sr and 87Sr/86Sr ratios in soil water and groundwater: implications for relative contributions to stream water discharge

Barium/Sr and Ca/Sr ratios have been used to model the relative importance of different sources of stream water. Major and trace element concentrations together with ⁸⁷Sr/⁸⁶Sr ratios were measured in precipitation, soil water, groundwater and stream water in a small (9.4 km²) catchment in northern Sweden. The study catchment is drained by a first order stream and mainly covered with podzolized Quaternary till of granitic composition. It is underlain by a 1.8 Ga granite. A model with mixing equations used in an iterative mode was developed in order to separate the stream water into 3 subsurface components: soil water, shallow groundwater, and deep groundwater. Contributions from precipitation are thus not included in the model. This source may be significant for the stream water generation, but it does not interfere with the calculations of the relative contributions from the subsurface components. The results show that the deep groundwater constitutes between 5 and 20% of the subsurface water discharge into the stream water. The highest values of the deep groundwater fraction occur during base flow. Soil water dominates during snowmelt seasons, whereas during base flow it is the least important fraction. Soil water accounts for 10–100% of the subsurface water discharge into the stream water. Shallow groundwater accounts for up to 80% of the subsurface water discharge with the lowest values at peak discharge during snowmelt seasons and the highest values during base flow. The validity of the model was tested by comparing the measured ⁸⁷Sr/⁸⁶Sr ratios in the stream water with the ⁸⁷Sr/⁸⁶Sr ratios predicted by the model. There was a systematic difference between the measured and modelled ⁸⁷Sr/⁸⁶Sr ratios which suggests that the fraction of soil water is overestimated by the model, especially during spring flood. As a consequence of this overestimation of soil water the amount of shallow groundwater is probably underestimated during this period. However, it is concluded that the differences between measured and predicted values are relatively small, and that element ratios are potentially effective tracers for different subsurface water flowpaths in catchments.     

电感耦合等离子体发射光谱法测定水中硅和锶

本文提出的等离子体发射光谱法测定水中的硅和锶,具有检出限低、线性范围宽,样品无需处理,可直接进样测量等优点。检出限：硅(以二氧化硅计)为0．5mg／L;锶为0．001mg／L。方法简便、准确,结果令人满意。     

Controls on Sr/Ca and Mg/Ca in scleractinian corals: The effects of Ca-ATPase and transcellular Ca channels on skeletal chemistry

The Sr/Ca of aragonitic coral skeletons is a commonly used palaeothermometer. However skeletal Sr/Ca is typically dominated by weekly-monthly oscillations which do not reflect temperature or seawater composition and the origins of which are currently unknown. To test the impact of transcellular Ca²⁺ transport processes on skeletal Sr/Ca, colonies of the branching coral, Pocillopora damicornis, were cultured in the presence of inhibitors of Ca-ATPase (ruthenium red) and Ca channels (verapamil hydrochloride). The photosynthesis, respiration and calcification rates of the colonies were monitored throughout the experiment. The skeleton deposited in the presence of the inhibitors was identified (by ⁴²Ca spike) and analysed for Sr/Ca and Mg/Ca by secondary ion mass spectrometry. The Sr/Ca of the aragonite deposited in the presence of either of the inhibitors was not significantly different from that of the solvent (dimethyl sulfoxide) control, although the coral calcification rate was reduced by up to 66% and 73% in the ruthenium red and verapamil treatments, respectively. The typical precision (95% confidence limits) of mean Sr/Ca determinations within any treatment was <±1% and differences in skeletal Sr/Ca between treatments were correspondingly small. Either Ca-ATPase and Ca channels transport Sr²⁺ and Ca²⁺ in virtually the same ratio in which they are present in seawater or transcellular processes contribute little Ca²⁺ to the skeleton and most Ca is derived from seawater transported directly to the calcification site. Variations in the activities of Ca-ATPase and Ca-channels are not responsible for the weekly-monthly Sr/Ca oscillations observed in skeletal chronologies, assuming that the specificities of Ca transcellular transport processes are similar between coral genera.     

On the interpretation of the oceanic variations in87Sr/86Sr as recorded in marine limestones

The present published inventory of fluvial Sr and⁸⁷Sr/⁸⁶Sr data, combined with new information from the big rivers of Eastern Siberia (a combined total of ∼ 1,000 measurements), is used to investigate the probable origin of the large rise in the marine isotopic ratio, recorded in limestones, over the last ∼ 20 million years. With the exception of the data from the Ganga-Brahmaputra all measurements fall on what is proposed to be called the “Wickman trend”, essentially a mixing line between the limestone sink for Sr, with the integrated marine ratio, and the flux from the weathering of average continental crust. However, time-variations along this trend, i.e. changes in relative weathering intensity, cannot explain the observations from limestones. They can only be caused by very high and radiogenic fluxes of Sr as are occurring from the present Himalayan orogeny, lying far above the Wickman trend and caused by metamorphic remobilization of radiogenic Sr during underthrusting and subsequent unroofing associated with the collision of India with Eurasia. In general the variations in the ratio are therefore caused by specific tectonic events, not by general climatic variations in the intensity of aluminosilicate weathering.     

Possible causes of quasiperiodic variations in geomagnetic reversal frequency and Sr/Sr ratios in marine carbonates through the Phanerozoic

Variations in frequency of geomagnetic reversals through the Phanerozoic have been analyzed jointly with ⁸⁷Sr/ ⁸⁶Sr ratios in marine carbonate sediments. The time series of both parameters contain principal components with periods from 90 to 110 Ma and show a certain correlation. Namely, (i) both time series have five local minimums spaced at similar intervals (period lengths); (ii) the minimums in the Δ⁸⁷Sr/⁸⁶Sr curve follow in time those of the reversal frequency, with a lag from 12 Myr in the Ordovician to 38 Myr in the Cretaceous; (iii) the rate of heat transfer from processes at the core-mantle boundary (in D″ layer) which control the Earth's geological life was from 7 to 25 cm/yr in the Phanerozoic. This rate approaches the observed velocities of horizontal plate motion and the predicted mantle convection rates.     

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.     

Competition between iron- and carbon-based colloidal carriers for trace metals in a freshwater assessed using flow field-flow fractionation coupled to ICPMS

Flow field-flow fractionation (FlFFF) coupled to an inductively coupled plasma mass spectrometer (ICPMS) has been used to determine the chemical composition of colloids from a freshwater sample as a function of size. Organic carbon and iron are the most abundant colloidal components, and are considered as the major carrier phases for other chemical elements present. The size distribution of organic carbon colloids shows a single peak with an estimated hydrodynamic diameter between 1 and 1.5 nm, while the iron colloids show a more complex distribution centred at larger colloid sizes with estimated hydrodynamic diameters up to 5 nm. The association of 32 trace elements with these two carrier colloids has been quantified by deconvolution analysis, and the resulting distributions are shown to be chemically consistent. The observed distributions are also shown to be broadly consistent with predictions from speciation modelling for the subset of 8 elements for which appropriate stability constants are available.