Incorporation Of Trace Elements Research Articles

Mg and Sr uptake in benthic foraminifera Ammonia aomoriensis based on culture and field studies

Trace elements incorporated in foraminiferal test are commonly used as paleoproxies, however, the incorporation of trace elements is controlled by more than one environmental parameter. We conducted one year sampling from June 2014 to May 2015 in the Qingdao intertidal flat, the Yellow Sea, and retrieved surface samples in the Jiaozhou Bay (3.9–6.8 m water depth), the Yellow Sea in February 2015, as well as performed a laboratory culture experiment under temperature 6–24 °C and salinity 24–33 psu, by combining δ18Oc values of field A. aomoriensis, parameters controlling Mg/Ca and Sr/Ca ratios of Ammonia aomoriensis were investigated. Under constant seawater chemistry, temperature dominates the magnesium incorporation into A. aomoriensis test by an exponential increase of 5.1% per °C (Mg/Ca = 1.0980 (±0.2073) e0.0510 (±0.0097) T; Mg/Ca = 0.5565 (±0.3897) + 0.1279 (±0.0242) T, 2.4–24 °C including field samples). Whereas, temperature has no significant effect on Strontium uptake. Calcite Sr/Ca of A. aomoriensis is primarily explained by Mg/Ca value (~3% per mmol/mol). Salinity variations are of subordinate importance for both Mg and Sr content in the test of A. aomoriensis, Mg/Ca raises linearly with approximately 2% per salinity unit, and Sr/Ca increases ~1% per salinity unit. Importantly, biological mechanism might be an inestimable factor perturbing Mg and Sr response to environmental parameters in natural waters, complicating the paleoclimate reconstruction.

Trace element systematics and ore-forming processes in mafic VMS deposits: Evidence from the Troodos ophiolite, Cyprus

The volcanogenic massive sulfide (VMS) deposits in the Troodos ophiolite (Cyprus) are ancient analogues for modern day seafloor massive sulfide mineralisation formed in a supra-subduction zone environment. In this study we present the first detailed in situ study of trace elements in sulfides from twenty VMS deposits hosted in the Troodos ophiolite to better understand factors that influence the distribution, enrichment and incorporation of trace elements in different sulfide minerals.On a mineral scale, trace elements exhibit systematic variations between pyrite, chalcopyrite and sphalerite. Pyrite preferentially incorporates As, Sb, Au and Te, whilst chalcopyrite is enriched in Co and Se. Sphalerite is trace element poor with the exception of Ag and Cd. Selenium averages 278 ppm (n = 150) in chalcopyrite but only 42 ppm (n = 1322) in pyrite. Bismuth and Te in pyrite show a weak positive correlation (R2 = 0.35) in some VMS deposits possibly linked with the occurrence of Bi-telluride inclusions. Trace element concentrations also vary between colloform and euhedral pyrite, with an enrichment of Au, As, Sb, Cu and Zn in colloform compared to euhedral pyrite.Time resolved laser ablation profiles reveal that the trace element distribution on a mineral scale is not uniform and varies with crystallographic effects, fluctuating physicochemical fluid conditions such as temperature, pH, fS2, fO2 and ligand availability during sulfide precipitation. Incorporation mechanisms in sulfides differ between elements in pyrite, Ag, As, Se and Pb are hosted in solid solution or as nanoscale inclusions, whilst Au, Sb and Te may form micro-scale inclusions.On a regional scale (20 km) the distribution of trace elements exhibits systematic variations between three major structural domains; namely the Solea, Mitsero and Larnaca grabens. The VMS deposits of the magmatic-tectonic Solea graben are enriched in Se, Co, Te, Au and Cu relative to Mitsero, which is a purely extensional feature. Therefore, we hypothesise that a variable magmatic volatile influx related to a) ‘magma’ volume, b) migration of the magmatic-hydrothermal crack front and associated brine liberation or c) a variation in protolith metal concentration are responsible for regional scale variations in VMS geochemistry. This is suggested to be intrinsically linked to the spreading architecture of Troodos.

From the crust to the cortical: The geochemistry of trace elements in human bone

Abstract Trace element incorporation into human bone depends upon dietary, geological, and environmental inputs as well as biological processes that biopurify essential elements, while depleting nonessential or toxic elements. Thus, the trace element composition of human bones provides a geochemical archive of biological, environmental, anthropological, and/or geographic conditions that have occurred throughout an individual’s life. While the majority of research has focused on the incorporation of a select subset of elements (i.e., Ca, F, Sr, Pb, K, Mg, Zn, Na), less information exists on the abundances of many other geologically informative trace elements and the processes that control their incorporation into human bone. In this study, we use ICP-MS to characterize the distribution of 36 trace elements in cortical bone tissues from femoral heads to investigate their incorporation into modern human bones. We propose a standard system for the evaluation of trace elements in human bone by normalizing trace element contents to bone mineral content (i.e., normalized concentrations of element X = (XN)bone= [X]/[Ca], where X is the measured abundance for a trace element of interest and Ca is the measured calcium content). Because Zn is known to be highly regulated by an individual’s homeostatic processes, we compare trace element abundances to Zn concentrations to determine which elements are modified by homeostatic processes. Using this framework, we identify one subset of trace elements that correlates strongly to Zn consistent with homeostatic regulation and a second subset of elements that exhibits statistically insignificant correlations to Zn, which we infer as a lack of homeostatic regulation. While the first subset of elements experiences homeostatic regulation and therefore do not reflect dietary or environmental inputs, the second subset of trace elements can be linked to geographic location or dietary inputs. Ratios of incorporation (Ri = ((XN)bone)/([X]/[Ca]UCC)) of trace elements into bone quantify the relative deviation for each trace element from the theoretical geological standard for average soil composition, which is assumed here to be equivalent to Upper Continental Crust (UCC). Rare earth elements (REEs) and oxyanions may provide the best proxy for geographical provenance studies.

Chemical activity relation of phosphorus and nitrogen presence in trace elements incorporation into underground water.

Anthropogenic activities can deteriorate the quality of groundwater destined for human use and consumption due to the fact that human activities cause changes in groundwater chemistry. The changes are induced by chemical species coming from industrial waste, which interacts with rocks and minerals. These trigger agents (phosphorus and nitrogen nutrients) which can incorporate trace elements (As, Fe, Mn, Pb, Cd, Ni, Zn). The main objective of the present work was to study the phosphate ions' and nitrogenous species' effects on the incorporation of trace elements into groundwater used for human consumption and to determine the physicochemical processes that participate in the incorporation of trace elements. The physicochemical analysis and elemental analysis by ICP of the groundwater that supplies the study area showed that the phosphorus (P) activity contributes in the incorporation of trace elements into the water. Significant correlations between the activities of P and Fe (0.516), Mn (0.553), Pb (0.756), and As (- 0.747) as well as the correlation of NH4+ with As indicate that the presence of chemical species such as PO43- (2.50-32.20mgL-1), NO3- (0.89-30.80mgL-1), and NH4+ (0.2-12.70mgL-1) are triggering agents that favor the dissolution and mobility of As (0.014-0.020mgL-1), Fe (0.020-1.14mgL-1), Mn (0.007-0.254mgL-1), Ni (0.002-0.0141mgL-1), Zn (0.009-0.459mgL-1), and Pb (0.009-0.0170mgL-1), species with adverse health effects because they are considered carcinogenic. Adequate control of the nitrogenous and phosphated material prevents the dissolution and mobility of trace elements into the water.

Evaluation of the 137Ba mass-marking technique and potential effects in the early life history stages of Sepioteuthis lessoniana

The use of mass-marking techniques of enriched stable isotopes has increased in studies of ecology, movement patterns and the dispersal of marine organisms. However, the efficacy of this technique and its potential effects on hatchling size and statolith chemistry of cephalopods are yet to be investigated. Sepioteuthis lessoniana egg capsules were collected from northern Taiwan and assigned randomly to 137Ba-spiking experimental groups at 0.2, 0.5 and 1ppm and three immersion durations (1, 3 and 7 days). Immersion duration >3 days produced significantly lower 138Ba:137Ba ratios, with 100% marking success, indicating that it is a reliable marking technique. The 137Ba mass marking had a positive effect on size at hatch and was likely to affect statolith trace element incorporation, including Cu, Zn and Pb. These findings highlight that it is necessary to consider the species-specific effects on hatchling size and physiological responses in when using stable isotopes mass-marking techniques.

In-situ elemental and boron isotopic variations of tourmaline from the Sanfang granite, South China: Insights into magmatic-hydrothermal evolution

Tourmaline often occurs in boron-rich granites and its genesis is still in dispute either formed from residual boron-rich silicate melt or from magmatic hydrothermal fluids with or without external fluid involvement. Here, we present a systematic investigation of in-situ major, trace elemental and boron isotopic variations of tourmaline from the Sanfang granite in Guangxi Province of South China, which demonstrate both the magmatic and hydrothermal origin for the formation of the tourmalines. The tourmaline occurs mainly in quartz-tourmaline nodules and tourmaline pegmatitic segregations within the Sanfang granite. Four types of tourmaline are identified: (1) isolated and disseminated tourmaline (Tur-D type) distributed in granite; (2) euhedral and subhedral tourmaline in quartz-tourmaline nodules (Tur-N type); (3) the earlier stage tourmaline (Tur-PE type) in pegmatitic segregations and (4) the later stage tourmaline (Tur-PL type) which replaced the Tur-PE type tourmaline in pegmatitic segregations. All the tourmalines belong to the alkali group representing dravite-schorl solid solution series with the former three types being schorl and the Tur-PL type being dravite. Petrography, chemical discrimination diagrams and Al occupations in the Y-site suggest that the Tur-D, Tur-N and Tur-PE type tourmalines are of magmatic origin and the Tur-PL type tourmalines are of hydrothermal fluid origin. Elemental and boron isotopic composition variations of tourmalines reflect the compositional and environmental evolution from late boron-rich magma to exsolved hydrothermal fluids. Chemical variations from the Tur-D to the Tur-N tourmalines are controlled by magma differentiation. The increase of Mg/(Mg + Fe) and Ca/(Ca + Na) ratios from the Tur-N to the Tur-PE tourmalines suggests the contamination of surrounding strata (e.g. the Sibao Group). Hydrothermal tourmalines have higher Mg/(Mg + Fe) and lower Na/(Na + Ca) ratios than the magmatic tourmalines. There is clear correlation at least in some trace elements (e.g. Sr, Pb) with major elements for all tourmalines, indicating the potential crystal chemical effects on their incorporation. Other trace element incorporation in tourmaline is largely controlled by melt and fluid composition. Hydrothermal tourmalines have high and stable V, Co and Ni contents, indicating relatively constant partition coefficient between hydrothermal tourmalines and the fluid. Hydrothermal tourmalines exhibit lower total REE contents but more pronounced positive Eu anomalies than the magmatic tourmalines. The δ11B values of all tourmalines from the Sanfang granite vary from −14.4‰ to −9.3‰, which indicate the boron in the Sanfang granite was mainly derived from partial melting of the metasedimentary source rocks. Boron isotopic variations of tourmaline are controlled by fractionation between melt-fluid and Rayleigh fractionation.

Ocean acidification can interact with ontogeny to determine the trace element composition of bivalve shell

AbstractWe sought to determine how pCO2 will affect the incorporation of trace elements into bivalve shell. This was to validate that under high pCO2 conditions reconstruction of animal movements is still viable; and to investigate potential trace element proxies for ocean carbonate chemistry. Here, we examined shell of the bivalve Perna canaliculus formed under current CO2 (pCO2 = 400 μatm) conditions and those predicted to exist in 2100 (pCO2 = 1050 μatm). Seventeen trace element:calcium ratios were examined at two locations within shells. Elements that are typically most useful in determining connectivity patterns (e.g., Sr, Mn, Ba, Mg, B) were not affected by pCO2 in shell produced early in individual's lives. This suggests that the effects of ocean acidification on dispersal signatures may be dampened. However, cobalt, nickel, and titanium levels were influenced by pCO2 consistently across shells suggesting their role as potential indicators of CO2 level.

Nanospectroscopy Captures Nanoscale Compositional Zonation in Barite Solid Solutions

Scientists have long suspected that compositionally zoned particles can form under far-from equilibrium precipitation conditions, but their inferences have been based on bulk solid and solution measurements. We are the first to directly observe nanoscale trace element compositional zonation in <10 µm-sized particles using X-ray fluorescence nanospectroscopy at the Hard X-ray Nanoprobe (HXN) Beamline at National Synchrotron Light Source II (NSLS-II). Through high-resolution images, compositional zonation was observed in barite (BaSO4) particles precipitated from aqueous solution, in which Sr2+ cations as well as HAsO42− anions were co-precipitated into (Ba,Sr)SO4 or Ba(SO4,HAsO4) solid solutions. Under high salinity conditions (NaCl ≥ 1.0 M), bands contained ~3.5 to ~5 times more trace element compared to the center of the particle formed in early stages of particle growth. Quantitative analysis of Sr and As fractional substitution allowed us to determine that different crystallographic growth directions incorporated trace elements to different extents. These findings provide supporting evidence that barite solid solutions have great potential for trace element incorporation; this has significant implications for environmental and engineered systems that remove hazardous substances from water.

A New Look on Biomineralization With X-ray Crystalline 3D Microscopy

Biomineralization, the capability exhibited by many living organisms to produce hard tissues (e.g., bones, teeth, shells) involves extraordinarily complex and regular biochemical processes whereby the organo-mineral components are controlled and organized with specific crystalline forms and textures [1,2]. Considering only calcium carbonate polymorphs in molluscs, corals or sponges, a variety of hierarchical sub-millimetric structures and shapes are observed [3]. Consequently, biominerals often present outstanding material properties, like increased damage resistance [4] or bone regeneration induction [5], motivating strong efforts for developing biomimetic materials. Furthermore, the incorporations of trace elements (e.g., Mg, Sr, Cd, Ba) during the shell formation of CaCO 3 marine species directly register the environmental parameters. Thus, these shells are used in paleoclimatology as proxies for ocean paleo-temperature, productivity and circulation [6]. To circumvent the lack of a general model for the trace element incorporation, extensive empirical laws are derived, for each species and environmental conditions [see e.g., 6]. The variations of trace element concentration, observed within the shells [7], further strengthen the need for a deep understanding of the processes underlying the formation of the biominerals. Finally, as CaCO 3 is one of the most prominent minerals in the Earth's crust, it plays a major role in the global Carbon cycle [8]. Understanding the physico-chemical pathways underlying the synthesis of biomineral CaCO 3 in marine species would pave the way for refined models of climate evolution

Barium partitioning in calcite and aragonite as a function of growth rate

Calcite and aragonite growth rate experiments have been performed in the presence of aqueous Ba at 25 °C using the constant addition technique as a function of CaCO3 mineral growth rate (mol/m2/s). The partitioning of Ba in calcite at −8.4 ≤ Logrcalcite ≤ −7.3 exhibits a weak dependence on growth rate that can be expressed as:LogDBa,calcite=0.2477±0.0543×Logrcalcite-0.2949±0.4222;R2=0.81In the case of aragonite, Ba partitioning at −9.0 ≤ Lograragonite ≤ −7.8, exhibits a much stronger dependence on growth rate that can be described as:LogDBa,aragonite=0.4458±0.0563×Lograragonite+3.3407±0.4668;R2=0.84The determined DBa,aragonite values are systematically lower than unity and come in contrast to previous experimental works where Ba partitioning studied during aragonite nucleation. They are, however, in excellent agreement with the theoretical free energy correlation model by Wang and Xu (2001) that considers the effect of ionic radii size on DBa,aragonite. The defined growth rate dependence of Ba incorporation in aragonite provides new insights on the role of ionic radii size during the incorporation of trace elements and the formation of solid-solutions from aqueous solutions at low oversaturation degrees. The data presented here shed light on the process controlling the elevated DBa,aragonite values occurring at high saturation degrees of natural fluids with respect to aragonite that have been recorded in natural samples. Furthermore, the trend experimentally obtained herein has the potential to record variations in growth rate regimes in natural occurring aragonites and to provide information on the environmental conditions of natural waters in the past.

Mn2+ concentrations in coastal fish otoliths: understanding environmental and biological influences from EPR.

The Mn2+ concentrations in the sagittae otoliths of 12 fish families (and 19 species) that co-occur in a coastal area of southeastern Brazil (~21°S) were quantified using electron paramagnetic resonance (EPR). Inferences were made about the relationship between fish habitat and trace element incorporation. Inferences were made on the relationship between trace element concentration and otolith shape. The differences in Mn2+ concentrations among the species suggest that habitat (and feeding habits) might drive the incorporation of this trace element into fish otoliths, with higher values in bottom-associated fish species than in surface-associated species. In surface-associated fish species, the correlation between trace element concentrations and otolith shape was stronger than in bottom-associated species. Thus, while the Mn bioavailability in a fish's habitat, especially from feeding resources, is a local driving influence of trace element incorporation in sagittae otoliths, species-specific requirements also have an influence. Quantitative EPR is a non-destructive technique that is very useful when the available samples cannot be damaged, like with otolith collections.

Sulfur isotope and metal variations in sulfides in the BIF-hosted orogenic Cuiabá gold deposit, Brazil: Implications for the hydrothermal fluid evolution

Textural, chemical and multiple sulfur isotope analyses of sulfides from the Archean world-class Cuiabá orogenic Au deposit, Quadrilátero Ferrífero district, Brazil, were conducted to track distinct trace element signatures from syngenetic to epigenetic-hydrothermal pyrite types in different host units, and to deduce the nature and source of the mineralizing fluids. Gold mineralization in Cuiabá is hosted in greenschist facies volcanic and sedimentary host rocks belonging to the Archean Rio das Velhas Supergroup, especially in association with quartz veins and sulfide minerals. The BIF-hosted Fonte Grande Sul orebody is controlled by quartz veins and disseminated gold-bearing pyrite, pyrrhotite and arsenopyrite in the wall rocks. Five pyrite types are classified based on textural relations as spongy, syngenetic (Py1), porous early-(Py2), smooth main-(Py3) and smooth isolated and overgrown late-stage (Py4 and Py5) types variably present in metamorphosed carbonaceous pelites, BIF and andesite. Besides pyrite, pyrrhotite and arsenopyrite are also defined according to textural and paragenetic differences, and they display significant trace element contents. Trace element abundance maps and LA-ICP-MS analyses display trace element incorporations in Py1 (present only in carbonaceous pelite), Py2 and Py3 (in all host rocks), and Py4 and Py5 (only in BIF). Py1 yields high As, Co, Ni, Pb and Ag concentrations, whereas Py2 (formed by agglomeration of Py1) maintains high trace element concentrations with slightly less of those elements. Trace element incorporation in Py3 is similar to Py1 in carbonaceous pelite. Early-stage Py2 and main-stage Py3 in BIF and andesite have increased Co and Ni, but have less Au and As. Late-stage Py4 is characterized by lower trace element concentrations, whereas Py5 is further enriched in As, Bi, Co, Ni and Pb. The hydrothermal alteration is divided into early-, main- and late-stage, which correlate to the sulfide hydrothermal evolution. The study shows that carbonaceous pelite is pre-enriched in Co, Ni and Pb, whereas certain elements like Ag, Au, Bi and As are only hydrothermally concentrated either during the early, main or late stage in BIF and andesite. This geochemical pattern supports a syngenetic versus hydrothermal origin of distinct elements, including some trace elements now in the ore zones. Multiple sulfur isotope data suggest that mineralizing fluids at the Cuiabá gold deposit reflect a complex mixing of sulfur evolved from three possible sources: seawater, mantle, and reduced elemental sulfur. Spongy, syngenetic Py1 yields Δ33S values ranging from −2.28 to −0.25‰, separated into two ranges, the first from −2.28 to −1.97‰, and the second from −0.96 to −0.25‰. The first range suggests Py1 in the carbonaceous pelite was deposited in a seawater environment. These pyrites probably mixed with later mantle sulfur carrying a near-zero Δ33S signature, which is indicated by the second Δ33S range, or could have mixed with fluids sourced from sedimentary rocks at depth carrying a positive Δ33S signature. The second scenario is more common in sedimentary and diagenetic pyrites. An unequivocal contrast is shown by early-, main- and late-stage pyrite types (Py2, Py3, Py4 and Py5) in carbonaceous pelite, BIF and andesite, which present a continuous process of crustal assimilation values towards increasingly positive δ34S and Δ33S values. This confirms evidence for a sedimentary-derived sulfur source as also indicated by fluid inclusion data of the andesite-hosted orebody at the Cuiabá deposit.

Nanogeochemistry of hydrothermal magnetite

Magnetite from hydrothermal ore deposits can contain up to tens of thousands of parts per million (ppm) of elements such as Ti, Si, V, Al, Ca, Mg, Na, which tend to either structurally incorporate into growth and sector zones or form mineral micro- to nano-sized particles. Here, we report micro- to nano-structural and chemical data of hydrothermal magnetite from the Los Colorados iron oxide–apatite deposit in Chile, where magnetite displays both types of trace element incorporation. Three generations of magnetites (X–Z) were identified with concentrations of minor and trace elements that vary significantly: SiO2, from below detection limit (bdl) to 3.1 wt%; Al2O3, 0.3–2.3 wt%; CaO, bdl–0.9 wt%; MgO, 0.02–2.5 wt%; TiO2, 0.1–0.4 wt%; MnO, 0.04–0.2 wt%; Na2O, bdl–0.4 wt%; and K2O, bdl–0.4 wt%. An exception is V2O3, which is remarkably constant, ranging from 0.3 to 0.4 wt%. Six types of crystalline nanoparticles (NPs) were identified by means of transmission electron microscopy in the trace element-rich zones, which are each a few micrometres wide: (1) diopside, (2) clinoenstatite; (3) amphibole, (4) mica, (5) ulvospinel, and (6) Ti-rich magnetite. In addition, Al-rich nanodomains, which contain 2–3 wt% of Al, occur within a single crystal of magnetite. The accumulation of NPs in the trace element-rich zones suggest that they form owing to supersaturation from a hydrothermal fluid, followed by entrapment during continuous growth of the magnetite surface. It is also concluded that mineral NPs promote exsolution of new phases from the mineral host, otherwise preserved as structurally bound trace elements. The presence of abundant mineral NPs in magnetite points to a complex incorporation of trace elements during growth, and provides a cautionary note on the interpretation of micron-scale chemical data of magnetite.

Impact of salinity on element incorporation in two benthic foraminiferal species with contrasting magnesium contents

Abstract. Accurate reconstructions of seawater salinity could provide valuable constraints for studying past ocean circulation, the hydrological cycle and sea level change. Controlled growth experiments and field studies have shown the potential of foraminiferal Na ∕ Ca as a direct salinity proxy. Incorporation of minor and trace elements in foraminiferal shell carbonate varies, however, greatly between species and hence extrapolating calibrations to other species needs validation by additional (culturing) studies. Salinity is also known to impact other foraminiferal carbonate-based proxies, such as Mg ∕ Ca for temperature and Sr ∕ Ca for sea water carbonate chemistry. Better constraints on the role of salinity on these proxies will therefore improve their reliability. Using a controlled growth experiment spanning a salinity range of 20 units and analysis of element composition on single chambers using laser ablation-Q-ICP-MS, we show here that Na ∕ Ca correlates positively with salinity in two benthic foraminiferal species (Ammonia tepida and Amphistegina lessonii). The Na ∕ Ca values differ between the two species, with an approximately 2-fold higher Na ∕ Ca in A. lessonii than in A. tepida, coinciding with an offset in their Mg content (∼ 35 mmol mol−2 versus ∼ 2.5 mmol mol−1 for A. lessonii and A. tepida, respectively). Despite the offset in average Na ∕ Ca values, the slopes of the Na ∕ Ca–salinity regressions are similar between these two species (0.077 versus 0.064 mmol mol−1 change per salinity unit). In addition, Mg ∕ Ca and Sr ∕ Ca are positively correlated with salinity in cultured A. tepida but show no correlation with salinity for A. lessonii. Electron microprobe mapping of incorporated Na and Mg of the cultured specimens shows that within chamber walls of A. lessonii, Na ∕ Ca and Mg ∕ Ca occur in elevated bands in close proximity to the primary organic lining. Between species, Mg banding is relatively similar, even though Mg content is 10 times lower and that variation within the chamber wall is much less pronounced in A. tepida. In addition, Na banding is much less prominent in this species than it is in A. lessonii. Inter-species differences in element banding reported here are hypothesized to be caused by differences in biomineralization controls responsible for element uptake.

Assessing foraminifera biomineralisation models through trace element data of cultures under variable seawater chemistry

The process by which foraminifera precipitate calcite from seawater has received much attention, in part because a mechanistic basis for empirical calibrations between shell chemistry and environmental parameters is desirable given their widespread application in palaeoceanography. The incorporation of fluorescent membrane-impermeable molecules into the shell demonstrates that seawater, transported by vacuolisation, is present at the site of calcification. However, recent discussion has focused on whether the calcium required for chamber formation is sourced predominantly by transmembrane Ca transport (TMT), with seawater vacuolisation playing a passive role, or vice versa. This debate has arisen in part because of the need to explain the low Mg/Ca ratio of most foraminifera compared to inorganic calcite. Here, we present trace element data of Operculina ammonoides and Globigerinoides ruber, a high-Mg shallow benthic, and low-Mg planktonic species respectively, cultured under variable seawater carbonate and elemental chemistries. We find that Mg incorporation in high and low-Mg species is characterised by an opposite response to the carbonate system, demonstrating that the negative relationship between Mg/Ca and pH or CO32- in several low-Mg foraminifera is not an intrinsic feature of calcite precipitation. Therefore, any biomineralisation model must be able to explain why the mechanism by which seawater Mg/Ca is reduced is impacted by the carbonate system. Moreover, we show that trace element incorporation in G. ruber is consistent with Rayleigh fractionation from unmodified seawater except for Mg-removal, but in very poor agreement with a biomineralisation site [Ca] substantially elevated above that of seawater as required by the TMT hypothesis. In addition, any biomineralisation model must explain the nonlinear relationship between seawater and shell Mg/Ca, and the large number of seawater vacuoles observed in some species. Although there are important inter-species differences in biomineralisation, evident from the observed range of shell Mg/Ca ratios, we argue that these differences are mechanistically related to the degree of Mg exclusion prior to chamber formation. Indeed, whilst our data for both low-Mg and high-Mg species are consistent with biomineralisation via ions sourced through seawater vacuolisation, it is difficult to reconcile many of these observations with a model based on significant transmembrane Ca transport.

The formation and trace elements of garnet in the skarn zone from the Xinqiao Cu-S-Fe-Au deposit, Tongling ore district, Anhui Province, Eastern China

Xinqiao is a large copper-gold deposit and consists of two major mineralization types: stratabound and skarn. The skarn occurs along the contact between a quartz diorite intrusion and Carboniferous-Triassic limestone. Xinqiao has a strongly developed skarn zone, including endoskarn and exoskarn; the exoskarn is divided into proximal and distal exoskarn. We present systematic major, trace and rare earth element (REE) concentrations for garnets from the skarn zone, discuss the factors controlling the incorporation of trace elements into the garnets, and constrain the formation and evolution of the garnet from skarn zone in Xinqiao deposit. Grossular (Adr20–44Grs56–80) mostly occurs in endoskarn and has typical HREE-enriched and LREE-depleted patterns, with small Eu anomalies and low ∑REE. Garnets from the exoskarn show complex textures and chemical compositions. The composition of garnets range from Al-rich andradite (Adr63–81Grs19–47) to andradite (Adr67–98Grs2–33). Garnet in endoskarn has typical HREE-enriched and LREE-depleted patterns. Al-rich andradite in proximal skarn has small Eu anomalies and moderate ∑REE. Andradite from distal exoskarn shows strong positive Eu anomalies and has variable ∑REE. The U, Y, Fe and Al relationship with ∑REE shows that two mechanisms controlled incorporation of REE into the garnets: crystal chemistry (substitution and interstitial solid solution) mainly controlled in the endoskarn garnet (grossular) and the proximal exoskarn (Al-rich andradite), and fluid and rock chemistry (surface adsorption and occlusion) controlled REEs in the distal exoskarn. Furthermore, Al has a negative relationship with ∑REE indicating that REE3+ did not follow a coupled, YAG-type substitution into the garnets. Variations in textures and trace and rare earth elements of garnets suggest that the garnets in the endoskarn formed by slow crystal growth at low W/R ratios and near-neutral pH in a closed system during periods of diffusive metasomatism. The garnets in the exoskarn formed rapidly from externally derived fluids during advective metasomatism, and adsorption had a major control on the REE patterns in distal exoskarn. With the end of water-rock reaction, the contents of REE decreased in the hydrothermal fluid, and the system became nearly closed.

Controls on Trace Element Distribution in Oxides and Silicates

Understanding and quantifying the partitioning of elements at low concentrations is important for petrology, as minor and trace elements are used as tracers of many geological processes. The lattice strain model has consequently been found to be very useful, as it links mineral/melt partition coefficients to the elastic properties of the mineral and to the difference in ionic radius between the trace element and the cation it replaces. However, this model has limitations, particularly in terms of describing crystal strain, due to the form of the equation and from the choice of a hard-sphere model. After a review of the thermodynamics of trace element incorporation into crystal sites and equilibrium between mineral phases, we present classical atomistic modelling using transferable empirical potentials. Following incorporation of one (or more) mismatching element(s), crystal strain appears strongly related to the environment of the site of exchange, with anisotropic, vacancy-rich minerals deforming more than densely-packed minerals, due to anisotropic deformation, rotation and tilting of the surrounding polyhedra. As shown by the computed cation–oxygen length in strained crystal sites, bond strain is smaller than the difference in cation radii, and varies between structures, with densely-packed minerals being less strained. Consequently, computed relaxation energies are smaller in less compressible minerals. This has implications for modelling the partitioning of trace elements, and highlights the limits of using continuum mechanics below crystal cell scale. Neither oxides nor silicates have isotropic elastic properties, and at nanoscale they do not deform like continuous material. Predictions of partitioning between mineral and melt (or fluid) remain hampered by several factors, amongst which are (i) knowledge of the thermodynamics properties of the dissolved species (in melts and fluids); (ii) the precision of estimated defect and strain energies; and (iii) the presence of solid solution in natural systems, even when limited to a few percent. The latter may have orders-of-magnitude effects on the calculated partition coefficients due to interactions between strain fields around minor cations, leading to a chemical mixing regime at low concentration different from solid solutions where phase components are found in high proportions. Partitioning between mineral phases in an assemblage is described with similar equations as for mineral/liquid equilibria. In cases where terms linked to fluid species disappear, such as incorporation with similar substitutions in two minerals, the assumption that crystal strain energy is the preponderant term during cation exchange becomes unnecessary and it is preferable to use defect energies rather than strain energies. Application and discussion of these concepts are presented for mineral/melt partitioning and for partitioning between minerals, using garnet/clinopyroxene equilibria. The advantage of atomistic modelling is that it does not rely on fitting. Agreement with experimental data shows predictive accuracy within an order of magnitude, which is poorer than what may be achieved by fitting the lattice strain model to experimental data, but validating the theoretical approach and sufficient for application to some petrology problems. Improvements of the modelling for better application to minerals like augite involve systematic work on the effect of solid solutions on the strain field around defects and imply solving ordering problems.

Environmental and physiological controls on daily trace element incorporation in Tridacna crocea from combined laboratory culturing and ultra-high resolution LA-ICP-MS analysis

Recent advances in spatially-resolved in-situ geochemical analysis enabled recognizing daily variability in B, Mg, Sr and Ba within bivalve shells of the genus Tridacna (e.g. Sano et al., 2012; Warter and Müller, 2017). However, the causes for such daily chemical variations are not fully understood. We carried out laboratory culture experiments to investigate the effect of varying temperatures and light levels on organism physiology and shell geochemistry of the giant clam Tridacna crocea at daily time-resolution. We find that both temperature and light strongly influence shell growth rates. Besides demonstrating light enhanced calcification, we also observe growth inhibition during culture in continuous darkness. ‘Ultra-high resolution’ LA-ICP-MS analysis (Warter and Müller, 2017) in tandem with 135Ba-labelling allows both to identify newly secreted, cultured aragonite and investigate its trace elemental composition at (sub)daily resolution (B/Ca, Mg/Ca, Sr/Ca, Ba/Ca). Overall, average Element/Calcium (El/Ca) ratios reveal an inverse relation with temperature and light. Strikingly, an increasing trend in all El/Ca ratios is observed in the direction of shell growth, which is interpreted to be metabolically-controlled, possibly related to organism ‘stress’. Daily, cyclic trace element variability can be clearly resolved at ~5–15μm in relatively fast growing shells, which experienced a diurnal light cycle but constant temperatures. We conclude that light (but not temperature) is the primary controlling factor responsible for daily trace element variability. We further demonstrate that high El/Ca ratios correspond to growth during night time, i.e. low light intensities, corroborating field observations by Sano et al. (2012). Yet, because light levels were kept constant during night and day, respectively, light intensity cannot account for the entire range of the El/Ca variability. We hypothesize that Tridacna physiology and biochemistry is controlled by a circadian rhythm, initiated by the external factor light, but endogenously mediated by the giant clam and/or its photosynthetic symbionts.

Incorporation of Mg, Sr, Ba, U, and B in High‐Mg Calcite Benthic Foraminifers Cultured Under Controlled pCO2

AbstractMeasurement of elemental ratios (E/Ca) has been performed in two symbiont‐bearing species of high‐Mg calcite benthic foraminifers (hyaline, Baculogypsina sphaerulata and porcelaneous, Amphisorus hemprichii), cultured under five pCO2 levels, representing preindustrial, modern, and three predicted future values. E/Ca ratios were analyzed by Laser Ablation coupled with Inductively Coupled Plasma Mass Spectrometer (LA‐ICP‐MS). We measured several E/Ca, such as Mg/Ca, Sr/Ca, Ba/Ca, U/Ca, and B/Ca simultaneously. We observed that high‐Mg calcite benthic foraminifers possess higher E/Ca than low‐Mg calcite foraminifers, irrespective of their calcification mode (hyaline or porcelaneous). In both modes of calcification, Mg, Sr, Ba, U, and B incorporation could be controlled by Rayleigh fractionation. However, more data are needed to validate and quantify the relative importance of this process and closely investigate the presence/absence of other mechanism. Therefore, it highlights the need for a multielemental approach when looking at trace element incorporation. Finally, no significant relationship was observed between the different ratios and the pCO2 of the water, suggesting that none of the Mg/Ca, Sr/Ca, Ba/Ca, U/Ca, and B/Ca is sensitive to bottom water pCO2 or pH for these species.

The distribution and coordination of trace elements in Krithe ostracods and their implications for paleothermometry

The Mg and Sr content of ostracod valves have been used to reconstruct past temperature and salinity, and their stable isotopes have been used to reveal aspects of marine, lake and estuary hydrology. However, significant uncertainties surround ostracod calcification processes, the incorporation mechanisms of trace elements, and the sensitivity of proxy tracers to complex confounding factors. The valves of most ostracods are composed of micron-scale crystalline grains embedded in an organic matrix. The fine-scale geochemistry of these structures, and the nature of the influence of biological mineralisation processes on valve chemistry, remain poorly constrained. We have performed sub-micron resolution X-ray microscopy of a marine Krithe ostracod valve, and determined the chemical coordination of Mg, and the distribution of Mg, Na and S throughout the crystal-organic valve structure. These trace elements display systematic sub-micron-scale compositional variations within the mineral grains and inter-granular matrix of the valve ultrastructure. These patterns imply that Krithe biomineralisation processes significantly modulate trace element incorporation at the sub-micron scale. Thus Krithe chemical composition is likely to be decoupled to some extent from the water in which they calcified. Most importantly, Mg K-edge Near-Edge X-Ray Absorption Fine Structure (NEXAFS) spectra, and the coincidence of high-Mg regions with S-rich organic layers reveal that Mg is not primarily hosted in the calcite structure in the valve. Our results highlight the need to understand the processes that drive this fine-scale chemical heterogeneity and their influence on connections between the external environment and valve geochemistry, if ostracods are to be used as sources of paleoenvironmental proxies.