Incorporation Of Trace Elements Research Articles

Trace Element Distribution (Cu, Ga, Ge, Cd, and Fe) IN Sphalerite From the Tennessee MVT Deposits, USA, By Combined EMPA, LA-ICP-MS, Raman Spectroscopy, and Crystallography

Abstract The zinc mines of Tennessee are known to contain high concentrations of certain trace elements (Cu, Ga, Ge, Fe, and Cd). Here, we investigate and compare sphalerites from two mining districts in the center (Central Tennessee Mines: CT) and east (East Tennessee Mines: ET) of Tennessee in order to (1) understand the substitution mechanisms that control the incorporation of trace elements in sphalerite, and (2) relate these mechanisms to the conditions of metal deposition. Electron microprobe and LA-ICP-MS analyses reveal complex chemical zoning in the sphalerites together with coupling of two main groups of trace elements: copper, germanium, and gallium; and iron and cadmium. The zoning is interpreted in terms of substitution mechanisms using different equations, including those previously described, such as 2Cu + + Ge 4+ ↔ 3Zn 2+ , Cu + + Ga 3+ ↔ 2Zn 2+ , Fe 2+ + Cd 2+ ↔ 2Zn 2+ , as well as new equations involving Ge 2+ and vacancies: Ge 2+ ↔ Zn 2+ , □ + Ge 4+ ↔ 2Zn 2+ , and □ + 2Ga 3+ ↔ 3Zn 2+ . Electron microprobe analyses of euhedral crystals of sphalerite highlight a correlation between the presence of trace elements and preferential crystallographic growth directions: copper and germanium are preferentially incorporated along the [010] growth direction, while cadmium is preferentially incorporated along the [110] growth direction. Raman spectroscopy highlights for the first time the possible coexistence of two different crystallographic forms of ZnS in some samples: cubic sphalerite and a non-cubic form, possibly a wurtzite-type structure. This is supported by the LA-ICP-MS data, which demonstrates a relationship between the trace element content and crystallographic structure: the non-cubic form of ZnS is enriched in copper, germanium, and gallium, while iron and cadmium are the most abundant trace elements in the cubic sphalerite. Although most of the main substitution mechanisms are observed in sphalerites from the two mining districts, the sphalerites differ in terms of their germanium grade and valency. These differences can be interpreted both in terms of fluid composition and redox conditions, suggesting that two different episodes of mineralization occurred in Tennessee.

Nanoscale gold clusters in arsenopyrite controlled by growth rate not concentration: Evidence from atom probe microscopy

Auriferous sulfides, most notably pyrite (FeS 2 ) and arsenopyrite (FeAsS), are among the most important economic minerals on Earth because they can host large quantities of gold in many of the world’s major gold deposits. Here we present the first atom probe study of gold distribution in arsenopyrite to characterize the three-dimensional (3D) distribution of gold at the nanoscale and provide data to discriminate among competing models for gold incorporation in refractory ores. In contrast to models that link gold distribution to gold concentration, gold incorporation in arsenopyrite is shown to be controlled by the rate of crystal growth, with slow growth rate promoting the formation of gold clusters and rapid growth rate leading to homogeneous gold distribution. This study yields new information on the controls of gold distribution and incorporation in sulfides that has important implications for ore deposit formation. More broadly this study reveals new information about crystal-fluid interface dynamics that determine trace element incorporation into growing mineral phases.

Anisotropic Morphological Changes in Goethite during Fe(2+)-Catalyzed Recrystallization.

When goethite is exposed to aqueous Fe(2+), rapid and extensive Fe atom exchange can occur between solid-phase Fe(3+) and aqueous Fe(2+) in a process referred to as Fe(2+)-catalyzed recrystallization. This process can lead to the structural incorporation or release of trace elements, which has important implications for contaminant remediation and nutrient biogeochemical cycling. Prior work found that the process did not cause major changes to the goethite structure or morphology. Here, we further investigated if and how goethite morphology and aggregation behavior changed temporally during Fe(2+)-catalyzed recrystallization. On the basis of existing literature, we hypothesized that Fe(2+)-catalyzed recrystallization of goethite would not result in changes to individual particle morphology or interparticle interactions. To test this, we reacted nanoparticulate goethite with aqueous Fe(2+) at pH 7.5 over 30 days and used transmission electron microscopy (TEM), cryogenic TEM, and (55)Fe as an isotope tracer to observe changes in particle dimensions, aggregation, and isotopic composition over time. Over the course of 30 days, the goethite particles substantially recrystallized, and the particle dimensions changed anisotropically, resulting in a preferential increase in the mean particle width. The temporal changes in goethite morphology could not be completely explained by a single mineral-transformation mechanism but rather indicated that multiple transformation mechanisms occurred concurrently. Collectively, these results demonstrate that the morphology of goethite nanoparticles does change during recrystallization, which is an important step toward identifying the driving force(s) of recrystallization.

Determination of aragonite trace element distribution coefficients from speleothem calcite–aragonite transitions

The processes that govern the incorporation of (trace) elements into speleothems can often be linked to environmental changes. Although element incorporation into speleothem calcite is now reasonably well understood, current knowledge regarding trace element variability in speleothem aragonite is very limited. Of particular interest is whether trace element distribution coefficients are above or below one in order to assess the extent to which prior aragonite precipitation has affected speleothem aragonite trace element records.This study uses nine calcite-to-aragonite transitions in seven speleothems from diverse environmental settings to derive the first quantitative estimates of the distribution coefficients for several elements in speleothem aragonite: DMg(Ar)=9.7E−5±9.01E−5, DBa(Ar)=0.91±0.88, DSr(Ar)=1.38±0.53, and DU(Ar)=6.26±4.54 (1σ SD). For one speleothem from western Germany, the distribution coefficients are generally higher, which is potentially related to the very low growth rates (<11μm/year) of this sample. In particular, DSr(Ar) appears to show a negative correlation with growth rate when growth rate is below 20μm/year.In summary, our results demonstrate that speleothem aragonite DMg(Ar) is below one, DU(Ar) is considerably above one, and DSr(Ar) is above one or close to unity. For DBa(Ar), reaching a similar conclusion is difficult due to the relatively high uncertainty. Enhanced prior aragonite precipitation will thus result in lower U and higher Mg concentrations in speleothem aragonite, although in many cases Mg in speleothem aragonite is most likely dominated by other processes. This result suggests that U concentrations in aragonitic stalagmites could serve as a very effective proxy for palaeo-rainfall.

Detailed spectroscopic study of the role of Br and Sr in coloured parts of the Callinectes sapidus crab claw.

The exoskeleton of crustaceans consists mainly of calcium carbonate (CaCO3) minerals and in many cases exhibits vivid colouration due to the presence of proteins rich in carotenoid chromophores. The exposure of aquatic animals in sea water results often in the incorporation of trace elements in their exoskeleton. The bonding configuration of Br and Sr trace elements in regions with different staining (white, orange and blue) of the exoskeleton of the Callinectes sapidus in crab claw are systematically investigated by a number of complementary spectroscopic techniques, including X-ray absorption fine structure spectroscopy (EXAFS), X-ray fluorescence, Raman and visible light reflectivity spectroscopies. It is found that Sr substitutes for Ca and the Sr/Ca ratio is constant along the claw. In the orange region that includes the claw fingers, CaCO3 adopts a calcite-like structure, whereas in the blue and white regions, located in the palm of the claw, an aragonite-like structure dominates. On the other hand, Br, present only in the blue and orange stained parts of the claw, is bound to phenyl and/or phenol rings of amino acid residues, most probably to phenylalanine and/or tyrosine, of the chromophore protein.

Chemical Environment of Unusually Ge- and Pb-Rich Willemite, Tres Marias Mine, Mexico

The Tres Marias carbonate-hosted Zn-Ge deposit in Chihuahua, Mexico contains willemite [Zn2SiO4] with unusually high concentrations of minor and trace elements (e.g., Pb, Ge, As, P, V); Pb concentrations are as high as 2 wt %, and Ge may reach 4000 ppm (average 900 ppm). Electron microprobe analyses and synchrotron X-ray fluorescence maps show that Zn and Ge, as well as Zn and Pb are negatively correlated, whereas Ge and Pb are positively correlated across zoned willemite crystals. In cathodoluminescence (CL) images, those areas of willemite having high trace element concentrations have no, or low CL intensities, whereas zones low in trace elements (except for P) display bright blue CL colors. X-ray absorption fine structure (XAFS) spectroscopy was used to characterize the chemical nature of Ge and Pb in willemite. Comparisons to reference spectra of natural and artificial substances points to the presence of Ge4+ and Pb2+ in Tres Marias willemite. No evidence for Pb4+ was detected. Oscillatory zonation reflects trace element incorporation into willemite from the oxidation of primary Ge-bearing sphalerite and galena (PbS) by siliceous aqueous fluids.

Late Jurassic biogeochemical microenvironments associated with microbialite-coated unionids (Bivalvia), Asturias (N Spain)

The Vega Formation (Upper Jurassic, Asturias, Spain) contains two Kimmeridgian outcrops – the Abeu and Huerres sections – with bivalves coated with carbonate microbialites (oncoids). The bivalve shells in the Abeu section were replaced early by calcite, while those of the Huerres section were dissolved and the moulds filled by late diagenetic cements. For the Abeu shells, there was a loss of Sr and a gain of Mg, Fe and Mn during the replacement process, but much of the original organic matter was retained. Part of the S present can be linked to this organic matter, and part to the sulphate that replaced the carbonate groups in the calcite. The thin microbialites inside the shells of some of the Huerres bivalves have allowed us to estimate the influence of the growth rate on the incorporation of trace elements in calcite. With an approximately six times lower growth rate, the internal microbialite incorporates less Mg and S and more Fe and Mn than the external one, while maintaining the Sr content. The trace element content (Mg, S, Sr, Fe and Mn) of the Huerres and Abeu microbialites are similar; these coatings may therefore have been formed in the same type of freshwater but in different microenvironments. Given the substantial sulphate content of the microbialites from both sections, this freshwater probably came from hot springs. However, the high Fe/Mn ratio of the Abeu microbialites suggests a reducing environment during their formation. Indeed, δ18O and δ13C data confirm that the Abeu and Huerres microbialites were formed in different microenvironments: the positive covariance for δ18O and δ13C of the Abeu microbialites and replaced shells (r2=0.83) and the wide range of variation for δ18O (2.80‰) together suggest that the microbialite crusts grew in isolated ponds where evaporation was dominant. In the Huerres microbialites the positive covariance for δ18O and δ13C (r2=0.59) and the narrow range of variation for δ18O (0.74‰) indicate that the Huerres section was formed in a more open environmental system where degassing predominated over evaporation.

Effects of sample storage and shell orientation on LA-ICPMS trace element measurements on deep-sea mussels

Geochemical markers are being increasingly applied to fundamental questions in population and community ecology in marine habitats because they allow inferences on individuals dispersal, but vital effects, small sample size and instrumental limitation are still challenging particularly in deep-sea studies. Here we use shells of the deep-sea bivalve Idas modiolaeformis to assess potential effects of sample storage, mineralogy, and valve orientation on LA-ICPMS measurements. Trace element concentrations of 24Mg, 43Ca, 88Sr, 137Ba, 208Pb, and 238U are not affected by the two most commonly used storage methods of biologic deep-sea samples (frozen at –20°C and fixed in 95% ethanol); thus combined analysis of differently preserved specimens is possible when the number of individuals is insufficient and distinct sample fixation is needed for multiple purposes. Valve orientation had a strong impact on quantification of trace elements in the calcitic but not in the aragonitic layer of adult shells. Hence, to enable comparisons between adult shells and entirely aragonitic embryonic shells, a reference map of site-specific signatures can potentially be generated using the aragonitic layer of the adult shells. Understanding ontogenetic changes and environmental effects in trace element incorporation is critical before geochemical fingerprinting can be used as a tool for larval dispersal studies in the deep-sea.

A comparison of benthic foraminiferal Mn / Ca and sedimentary Mn / Al as proxies of relative bottom-water oxygenation in the low-latitude NE Atlantic upwelling system

Abstract. Trace element incorporation into foraminiferal shells (tests) is governed by physical and chemical conditions of the surrounding marine environment, and therefore foraminiferal geochemistry provides a means of palaeo-oceanographic reconstructions. With the availability of high-spatial-resolution instrumentation with high precision, foraminiferal geochemistry has become a major research topic over recent years. However, reconstructions of past bottom-water oxygenation using foraminiferal tests remain in their infancy. In this study we explore the potential of using Mn / Ca determined by secondary ion mass spectrometry (SIMS) as well as by flow-through inductively coupled plasma optical emission spectroscopy (FT-ICP-OES) in the benthic foraminiferal species Eubuliminella exilis as a proxy for recording changes in bottom-water oxygen conditions in the low-latitude NE Atlantic upwelling system. Furthermore, we compare the SIMS and FT-ICP-OES results with published Mn sediment bulk measurements from the same sediment core. This is the first time that benthic foraminiferal Mn / Ca is directly compared with Mn bulk measurements, which largely agree on the former oxygen conditions. Samples were selected to include different productivity regimes related to Marine Isotope Stage 3 (35–28 ka), the Last Glacial Maximum (28–19 ka), Heinrich Event 1 (18–15.5 ka), Bølling Allerød (15.5–13.5 ka) and the Younger Dryas (13.5–11.5 ka). Foraminiferal Mn / Ca determined by SIMS and FT-ICP-OES is comparable. Mn / Ca was higher during periods with high primary productivity, such as during the Younger Dryas, which indicates low-oxygen conditions. This is further supported by the benthic foraminiferal faunal composition. Our results highlight the proxy potential of Mn / Ca in benthic foraminifera from upwelling systems for reconstructing past variations in oxygen conditions of the sea floor environment as well as the need to use it in combination with other proxy records such as faunal assemblage data.

Response of Acropora digitifera to ocean acidification: constraints from δ11B, Sr, Mg, and Ba compositions of aragonitic skeletons cultured under variable seawater pH

The response of Acropora digitifera to ocean acidification is determined using geochemical proxy measurements of the skeletal composition of A. digitifera cultured under a range of pH levels. We show that the chemical composition (δ11B, Sr/Ca, Mg/Ca, and Ba/Ca) of the coral skeletons can provide quantitative constraints on the effects of seawater pH on the pH in the calcification fluid (pHCF) and the mechanisms controlling the incorporation of trace elements into coral aragonite. With the decline of seawater pH, the skeletal δ11B value decreased, while the Sr/Ca ratio showed an increasing trend. The relationship between Mg/Ca and Ba/Ca versus seawater pH was not significant. Inter-colony variation of δ11B was insignificant, although inter-colony variation was observed for Ba/Ca. The decreasing trend of pHCF calculated from δ11B was from ~8.5, 8.4, and 8.3 for seawater pH of ~8.1, 7.8, and 7.4, respectively. Model calculations based on Sr/Ca and pHCF suggest that upregulation of pHCF occurs via exchange of H+ with Ca2+ with kinetic effects (Rayleigh fractionation), reducing Sr/Ca relative to inorganic deposition of aragonite from seawater. We show that it is possible to constrain the overall carbonate chemistry of the calcifying fluid with estimates of the carbonate saturation of the calcifying fluid (Ω CF) being derived from skeletal Sr/Ca and pHCF (from δ11B). These estimates suggest that the aragonite saturation state of the calcifying fluid Ω CF is elevated by a factor of 5–10 relative to ambient seawater under all treatment conditions.

Drip water electrical conductivity as an indicator of cave ventilation at the event scale

The use of speleothems to reconstruct past climatic and environmental change through chemical proxies is becoming increasingly common. Speleothem chemistry is controlled by hydrological and atmospheric processes which vary over seasonal time scales. However, as many reconstructions using speleothem carbonate are now endeavouring to acquire information about precipitation and temperature dynamics at a scale that can capture short term hydrological events, our understanding of within cave processes must match this resolution. Monitoring within Cueva de Asiul (N. Spain) has identified rapid (hourly resolution) changes in drip water electrical conductivity (EC), which is regulated by the pCO2 in the cave air. Drip water EC is therefore controlled by different modes of cave ventilation. In Cueva de Asiul a combination of density differences, and external pressure changes control ventilation patterns. Density driven changes in cave ventilation occur on a diurnal scale at this site irrespective of season, driven by fluctuations in external temperature across the cave internal temperature threshold. As external temperatures drop below those within the cave low pCO2 external air enters the void, facilitating the deposition of speleothem carbonate and causing a reduction in measured drip water EC. Additionally, decreases in external pressure related to storm activity act as a secondary ventilation mechanism. Reductions in external air pressure cause a drop in cave air pressure, enhancing karst air draw down, increasing the pCO2 of the cave and therefore the EC measured within drip waters. EC thereby serves as a first order indicator of cave ventilation, regardless of changes in speleothem drip rates and karst hydrological conditions. High resolution monitoring of cave drip water electrical conductivity reveals the highly sensitive nature of ventilation dynamics within cave environments, and highlights the importance of this for understanding trace element incorporation into speleothem carbonate at the event scale.

Interaction of rhyolite melts with monazite, xenotime, and zircon surfaces

The interfacial contact region between a rhyolite melt and the accessory minerals monazite, xenotime, and zircon is investigated using molecular dynamics simulations. On all surfaces, major structural rearrangement extends about 1 nm into the melt from the interface. As evidenced by the structural perturbations in the ion distribution profiles, the affinity of the melt for the surface increases in going from monazite to xenotime to zircon. Alkali ions are enriched in the melt in contact with an inert wall, as well as at the mineral surfaces. Melt in contact with zircon has a particularly strong level of aluminum enrichment. In xenotime, the enrichment of aluminum is less than that in zircon, but still notable. In monazite, the aluminum enrichment in the contact layer is much less. It is expected that the relative surface energies of these accessory minerals will be a strong function of the aluminum content of the melt and that nucleation of zircon, in particular, would be easier for melts with higher aluminum concentration. The crystal growth rate for zircon is expected to be slower at a higher aluminum concentration because of the effectiveness of aluminum in solvating the zircon surface. The variable interfacial concentration profiles across the series of accessory minerals will likely affect the kinetics of trace element incorporation, as the trace elements must compete with the major elements for surface sites on the growing accessory minerals.

Optimizing LA-ICP-MS analytical procedures for elemental depth profiling of foraminifera shells

Laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) is becoming a widespread technique for analyzing elemental ratios in foraminiferal calcite. Here we focus on optimizing LA-ICP-MS for high-resolution depth profiling of elemental ratios through shell walls. This application reveals intrashell variability and provides a unique opportunity to quantify trace element incorporation over short time scales of calcification by an individual foraminifer. High-resolution depth profiling requires careful consideration of both ablation and analytical conditions required to resolve differences in shell chemistry across sub-micron shell thickness. We present laser ablation profiles of NIST SRM 610 standard glass data (in cps) and elemental/Ca ratios (in mmol/mol) from foraminiferal calcite obtained over a range of operating conditions using a Photon Machines 193nm UV excimer laser-ablation system, equipped with a dual-volume ANU HelEx chamber, coupled to an Agilent 7700x quadrupole ICP-MS. Different combinations of energy density, repetition rate, and mass spectrometer cycle time can yield varying elemental profiles. This variability can mimic and/or mask real intrashell trace element heterogeneity in foraminifer shells. At low (<3Hz) laser repetition rates, real intrashell element variation can be obscured depending on the laser energy, whereas using moderate (≥3Hz) laser repetition rates and/or a signal-smoothing device improves the accuracy and precision of intrashell trace element profiles. Shell material is ablated rapidly when using a 5Hz or greater repetition rate and an energy density of 3J/cm2 or greater, resulting in reduced spatial resolution.

Fossil corals as an archive of secular variations in seawater chemistry since the Mesozoic

Numerous archives suggest that the major ion and isotopic composition of seawater have changed in parallel with large variations in geologic processes and Earth’s climate. However, our understanding of the mechanisms driving secular changes in seawater chemistry on geologic timescales is limited by the resolution of data in time, large uncertainties in seawater chemistry reconstructions, and ambiguities introduced by sample diagenesis. We validated the preservation of a suite of ∼60 unrecrystallized aragonitic fossil scleractinian corals, ranging in age from Triassic through Recent, for use as new archives of past seawater chemistry. Optical and secondary electron microscopy (SEM) studies reveal that fossil coral crystal fabrics are similar to those of modern coralline aragonite. X-ray diffractometry (XRD), cathodoluminescence microscopy (CL), and Raman studies confirm that these specimens contain little to no secondary calcite. In order to screen for geochemical changes indicative of alteration, we measured 87Sr/86Sr ratios, clumped isotopes, and trace element ratios sensitive to diagenesis (e.g., Mn/Ca). We retain samples when these tests either fail to identify any diagenetic modifications, or identify specific domains free of detectable alteration.Using the validated fossil coral archive we reconstruct seawater Mg/Ca and Sr/Ca ratios, measured by Secondary Ion Mass Spectrometry (SIMS), back to ∼230Ma. The effects of temperature on coral trace element incorporation cannot explain the trends observed in our fossil coral Mg/Ca and Sr/Ca data. In agreement with independent records, seawater Mg/Ca molar ratios inferred from corals are low (Mg/Ca ∼1) during the Cretaceous and Jurassic, and increase between the Early Cenozoic and present (Mg/Ca=5.2). Seawater Sr/Ca ratios from corals vary systematically between ∼8 and 13mmol/mol since 230Ma, with maximum values in the Cretaceous and Paleogene. The coral Sr/Ca record disagrees with records from hydrothermal CaCO3 veins, but is similar to those reconstructed from other biogenic carbonates, especially benthic foraminifera. The agreement between corals and other archives, for both Sr/Ca and Mg/Ca ratios, further validates our records. In return, fossil coral records improve our understanding of past variations in seawater Mg/Ca and Sr/Ca.

Efficacy of hair analysis for monitoring exposure to uranium: A mini-review

In spite of the ease with which samples may be collected and the stability of the samples after collection, the use of hair mineral analysis for monitoring environmental exposures and evaluating heavy metal poisonings has remained controversial since its initial applications for these purposes in the early 1950s. Among the major arguments against using hair mineral analysis in general were the absence of biokinetic models and/or metabolic data that adequately described the incorporation of trace elements into the hair, the absence of correlations between the concentrations of trace elements in the hair and their concentrations in other tissues, the inability to distinguish between trace elements that were deposited in the hair endogenously and those that were deposited on the hair exogenously, the absence of reliable reference ranges for interpreting the results of hair mineral analysis and a lack of standard procedures for the collecting, preparing and analyzing the hair samples. The developments of the past two decades addressing these objections are reviewed here, and arguments supporting the use of hair analysis for monitoring environmental and/or occupational exposures to uranium are made on the basis of the information presented in this review.

Trace elements and their isotopes in bones and teeth: Diet, environments, diagenesis, and dating of archeological and paleontological samples

Fossil biogenic apatites display trace element (TE) compositions that can record environmental and biological signals, give insights into past water compositions, or be used for dating paleontological and archeological bones and teeth. Processes of TE incorporation into apatites of skeletal phosphatic tissues are described, ranging from those active in living organisms to those active during diagenesis. Abiotic incorporation mechanisms have been modeled theoretically and experimentally and include crystallographic controls on TE partitioning coefficients, inorganic surface adsorption and adsorption mediated through chelation and diffusion–adsorption processes, each leading to specific fractionation patterns. Predictions from models and experiments have been tested against TE concentration and isotopic composition data on remains of contemporary wild or raised animals and on fossils of various ages and environments. In living organisms, TEs incorporated in apatite are separated in two categories, non-essential elements whose concentration is compared to that of an essential element with similar behavior (e.g. Sr/Ca) to reconstruct trophic chains, and essential elements whose isotopic ratios are used to trace metabolic activity, diet, etc. In fossils, elements are incorporated during diagenesis, such as rare earth elements (REEs), and trace diagenetic processes ranging from very early quantitative adsorption likely mediated by chelators, protracted diagenesis through inorganic adsorption and fractionation through diffusion–adsorption, to low-grade metamorphism associated with intense redistribution under crystal-chemical control. These different steps are also identified as steps of radionuclide incorporation. Only samples where the earliest steps can be deciphered are useful for determining stratigraphic and archeological ages. Other samples will date late diagenetic events that have obliterated the paleoenvironmental signals, but may be of geological significance, e.g. tectonic events.

Boron isotopic fractionation and trace element incorporation in various species of modern corals in Sanya Bay, South China Sea

The boron isotope paleo-pH proxy has been extensively studied due to its potential for understanding past climate change, and further calibrations were considered for accurate applications of the proxy because of significant variability related to biocarbonate microstructure. In this work, we studied the boron isotopic fractionation between modern marine corals and their coexisting seawater collected along shallow area in Sanya Bay, South China Sea. The apparent partition coefficient of boron (KD) ranged from 0.83×10−3 to 1.69×10−3, which are in good agreement with previous studies. As the analyzed coral skeleton (∼5 g) spanned the growth time period of 1–2 years, we discussed the boron isotopic fractionation between pristine corals and modern seawater using the annual mean seawater pH of 8.12 in this sea area. Without taking the vital effect into account, (11B/10B)coral values of all living corals spread over the curves of (11B/10B)borate vs. (11B/10B)sw with the α4−3 values ranging from 0.974 to 0.982. After calibrating the biological effect on the calcifying fluid pH, the field-based calcification on calcifying fluid pH (i.e., Δ(pHbiol-pHsw)) for coral species of Acropora, Pavona, Pocillopora, Faviidae, and others including Proites are 0.42, 0.33, 0.36, 0.19, respectively, and it is necessary to be validated by coral culturing experiment in the future. Correlations in B/Ca vs. Sr/Ca and B/Ca vs. pHbiol approve temperature and calcifying fluid pH influence on skeletal B/Ca. Fundamental understanding of the thermodynamic basis of the boron isotopes in marine carbonates and seawater will strengthen the confidence in the use of paleo-pH proxy as a powerful tool to monitor atmospheric CO2 variations in the past.

Crystallinity and microchemistry of Nassarius reticulatus (Caenogastropoda) statoliths: Towards their structure stability and homogeneity

Gastropod statoliths are spherical biocarbonates formed during their lifespan. The stability and homogeneity of these structures' mineral matrix was characterised along their radiuses, using Nassarius reticulatus as a model. Generally, they were proved to be bimineralic. Two of the three CaCO3 crystalline polymorphs occurring in biocarbonates - aragonite and calcite - coexist along statolith radiuses, aragonite being unequivocally the most abundant phase. The presence of a diffuse organic matrix was also perceived by the detection of a weak Raman band between 2800 and 3000 cm(-1) consistently observed along radiuses. Beyond the apparent stability and homogeneity, different crystalline orientations were disclosed by Raman spectroscopy. A change in the intensity pattern of the features related to the lattice and bending modes of aragonite between different radiuses give new insights for a possible spherulitic-like growth of these structures. As expected from the relative homogeneity of both mineral and organic signals, there was no pattern on the distribution of Ca, O, Na and S along radiuses. However, a higher concentration of Sr occurs in growth rings (known as winter tags), corroborating the already described negative correlation between the concentration of this element in statoliths and temperature. Despite the apparent stability and homogeneity of the matrix during its lifespan, the periodic distribution of Sr potentially influences a dissimilar incorporation of trace elements in increments and growth rings. Since gastropod statolith elemental fingerprinting was recently suggested as a new tool to monitor marine environmental changes, the pressing need for further studies on the incorporation of traces in these structures is highlighted.

Controls on trace-element partitioning in cave-analogue calcite

We report trace-element data from a series of carbonate growth experiments in cave-analogue conditions in the laboratory with the goal of better understanding environmental controls on trace-element incorporation in stalagmites. The experimental setup closely mimics natural processes (e.g. precipitation driven by CO2-degassing, low ionic strength solution, thin solution-film) but with a tight control on growth conditions (temperature, pCO2, drip rate, calcite saturation index and the composition of the initial solution). Calcite is dissolved in deionized water in a 20,000ppmV pCO2 environment, with trace-elements (Li, Na, Mg, Co, Sr, Cd, Ba, U) at appropriate concentrations to mimic natural cave drip-waters. This solution is dripped onto glass plates (coated with seed-calcite) in a lower pCO2 environment at 7, 15, 25 and 35°C and drip rates of 2, 6 and 10 drips per minute. D(Sr) was shown to be statistically invariant over the full range of temperature and growth rate studied. No relationship between Sr/Ca and growth rate is therefore expected in stalagmite samples over comparable growth rates. D(Mg) has a relationship with temperature defined by D(Mg)=0.01e0.02[±0.006]T, but temperature is not expected to be the dominant control on Mg/Ca in cave calcite due to the larger impact of calcite precipitation on Mg/Ca. Over short timescales, in conditions where temperature is well buffered, the fraction of calcium remaining in solution (f) is likely to be the dominant control on Mg/Ca and other trace-element ratios. But differences in the response of trace-elements to f and T may allow their combined use to assess past cave conditions. High Cd/Castalagmite is particularly indicative of low amounts of prior calcite precipitation and Cd/Ca would be a useful addition to trace-element studies of natural stalagmites. Significant scatter is observed in trace-element ratios during the laboratory experiments, which cannot be explained by simple Rayleigh distillation. This scatter is well explained by solution mixing and by the mixing of calcite with different fractions of calcite growth. Accounting for the effects of mixing on trace-element concentrations or ratios may help to achieve more robust interpretations of stalagmite chemistry as part of a multi-proxy approach to assessment of past environments.

Optical microscope-cathodoluminescence (OM–CL) imaging as a powerful tool to reveal internal textures of minerals

Optical microscope-cathodoluminescence (OM-CL) microscopy is a modern luminescence technique with widespread applications in geosciences. Many rock-forming and accessory minerals show specific CL properties that can be successfully used in geoscience and materials science research. One of the most spectacular applications is the visualization of growth textures, alteration, and other internal textures in minerals that are not discernible with other analytical techniques. These results provide information about the real structure of minerals and materials and can be used for the reconstruction of geological processes of mineral formation and subsequent alteration. The information obtained from CL imaging in combination with spectral measurements of the CL emission allows for a more thorough understanding of structural states of solids and/or trace-element incorporation. Additional information can be obtained when luminescence studies are combined with other analytical techniques with high sensitivity and high spatial resolution.