Ba Concentrations Research Articles

Evaluation of human and ecological health risks associated with the potentially toxic heavy metals in groundwater of Vellore city, Tamil Nadu, India

Groundwater pollution by heavy metals is a significant and alarming threat globally, through its chronic effect on human health and ecosystem. The current study evaluated the identification and risk assessment of heavy metals in groundwater of the Vellore city, Tamilnadu, India. Groundwater samples were collected from 32 locations over a continuous period of 2022–2023 for every three months on seasonal basis. The samples were analysed for pH, Total Dissolved Solids (TDS), Hardness and heavy metals (Al, As, Ba, Cd, Cu, Pb, Al and Zn). The analysed mean concentrations of these heavy metals were found in the order: As > Cd > Pb > Ba >Zn >Al> Cu. Elevated concentrations of heavy metals were observed in 2022, likely influenced by rainfall and land use patterns. Heavy metals such as Al, As, Pb, and Cd exceeded the BIS limits and whereas Ba, Cu, and Zn concentrations remain within desirable limits. Groundwater Quality Index (GWQI) classified 41% as 'unfit for drinking'. Ecological risk indices (ERI) indicate significant contamination in 34% of samples, with Al and Pb being primary contributors. Non-carcinogenic health risk assessments reveal, chronic hazards, where children facing higher risks followed by men and women groups. Carcinogenic risk assessments indices such as Heavy metal pollution Index (HPI) shown 25% of samples in critical quality, Heavy metal Evaluation Index (HEI) evaluated all samples were in low contamination and Contamination Index (CI) shown 72% samples under high contamination posing high risk to humans. Probable Cancer Risk (PCR) values for As, Pb, and Cd exceed acceptable ranges across all demographic groups posing cancer risk to humans particularly children. The present study highlights the need for groundwater treatment and regulatory interventions to mitigate health and ecological risks due to the contamination of heavy metals in Vellore city.

The roles of celestine and barite in modulating strontium and barium water column concentrations in the northeast Pacific Ocean

The water column distributions of the alkaline earth metals strontium (Sr) and barium (Ba) were studied along a transect from Hawaii to Alaska. Despite similarity in the chemical properties of Sr and Ba, we find that changes in their concentrations along the transect are governed by different chemical and biological processes, meaning that these elements can be treated as independent variables in modern and ancient environments. Alaskan margin sediments are a particularly important source of dissolved Ba to the North Pacific, likely through a combination of saline submarine groundwater discharge and reductive dissolution of manganese (Mn) oxides. Abyssal North Pacific sediments are also a source of Ba to the bottom waters but a sink for Sr. We find that over 90 % of the water column variability in Sr concentrations is driven by precipitation and dissolution of the celestine (SrSO4) skeletons of Acantharia. However, the high Ba content of Acantharia celestine accounts for only 5–8 % of the global ocean variability in Ba concentrations in the water column. Similarly, the effects of barite (BaSO4) precipitation and/or dissolution on the marine Sr cycle is negligible, accounting for <1 % of the water column concentration structure for Sr and ∼3 % of the sedimentary Sr burial. The Sr-Ba-PO4 concentration distributions in the North Pacific are inconsistent with significant export of barite to the deep ocean and sediment. This suggests most of the barite formed at intermediate depths dissolves at similar horizons to its formation. The Ba content of phytoplankton organic matter is too low to constitute a major source for particulate Ba in the mesopelagic North Pacific, which suggests Ba is concentrated in marine aggregates by heterotrophic micro-organisms.

Effect Of Cytokinin BA And Different Concentrations Of Chemical Stress Treatments On The Multiplication Of Vegetative Shoots Of The Plant Antirrhinum Magus L. Grown In Vitro

The study was conducted on the multiplication of Antirrhinum magus L. plant using the micropropagation technique, represented by culture vegetative shoots on MS nutrient medium prepared with different concentrations of cytokinin BA and different levels of chemical stress treatments. The treatment of 4.44 μmol.L–1 BA with a NAA concentration of 0.54 μmol.L–1 gave the highest significant increase in the average number of vegetative shoots per plantlet, shoot length, number of leaves per plantlet, and leaf width, which amounted to 6.40 shoot explant-1, 4.00 cm, 20.60 shoot leaves -1, 0.68 cm, respectively, while a significant decrease in the average vegetative traits was observed when the concentration of BA in the medium was increased in the two treatments (8.88, 11.10) μmol.L–1 BA, which did not differ significantly between them. The results of chemical stress showed that reducing the level Mannitol to 15gm L-1 in multiplication medium led to a significant and inverse increase in the average number of vegetative shoots per plantlet, shoot length, number of leaves per shoot, and leaf width reached 4.80 shoot explant-1, 3.50 cm, 11.40 shoot explant1-, 0.44 cm in succession, and their averages decreased. By increasing the concentration in the middle. It was also observed that there was an inverse relationship between the average vegetative traits and the levels of PEG8000, where the control treatment achieved the highest significant increase in the average of all vegetative traits, amounting to 6.60 shoot explant-1, 4.06 cm, and 7.60 shoot explant-1, 0.92 cm, respectively, compared to the other averages of water stress whenever the level of PEG8000 increased. In the nutrient medium down to the level of 45g. L-1.

Modulating the structural and electrical properties of SrFeO3–δ by a-site alkali metal ion doping

The electrical properties of perovskite structured SrFeO3–δ can be modulated by A site doping. The present work focuses on the influence of concentration and ionic radii of alkali metal cation on the structural and electrical properties of Sr1–xAxFeO3–δ (A = Ca, Ba and x = 0, 0.25, 0.50, 0.75). The x-ray diffraction studies confirm the phase change from cubic to orthorhombic with Ca content while orthorhombic to cubic structural translation was observed with Ba concentration. A lattice contraction and expansion were observed for doping depending on the ionic radii of dopant cation. The x-ray photoelectron spectroscopy results indicate the presence of Fe in mixed valence state of +2, +3, +4 state and adsorbed oxygen content was found to be higher upon Ba doping than that of Ca. A maximum conductivity of 1.82 × 10−3 S cm−1 (x = 0.25) and 5.31 × 10−3 S cm−1 (x = 0.5) was observed at 800 °C for Ca and Ba doped samples, respectively, one order higher than the base SrFeO3–δ .Thus, our results emphasise the importance of dopant addition on tailoring the electrode properties for SOFC application.

Sulfated Bile Acids in Serum as Potential Biomarkers of Disease Severity and Mortality in COVID-19.

The fight against coronavirus disease 2019 (COVID-19) continues. Since the pandemic's onset, several biomarkers have been proposed to assess the diagnosis and prognosis of this disease. This research aimed to identify potential disease severity biomarkers in serum samples of patients with COVID-19 during the disease course. Data were collected using untargeted and targeted mass spectrometry methods. The results were interpreted by performing univariate and multivariate analyses. Important metabolite classes were identified by qualitative untargeted metabolomics in 15 serum samples from survivors of COVID-19. Quantitative targeted metabolomics on a larger patient cohort including 15 non-survivors confirmed serum 3-sulfate bile acids (i.e. GLCA-3S) were significantly increased in non-survivors compared to survivors during the early disease stage (p-value < 0.0001). Notably, it was associated with a higher risk of mortality (odds ratio of 26). A principal component analysis showed the ability to discriminate between survivors and non-survivors using the BA concentrations. Furthermore, increased BA-S is highly correlated with known parameters altered in severe clinical conditions.

Geochemistry and conditions of formation of Mesoarchean banded iron formations (BIF-1) from the Kostomuksha Greenstone belt, Karelian Craton

Three variably old groups of banded iron formation (BIF) are known in the Kostomuksha Greenstone belt (KGB) of the Karelian Craton. This paper deals with the earliest of them, Mesoarchean (2.87–2.81 Ga) – BIF-1. BIF-1 occurs among the komatiite-basalt unit of the KGB. BIF-1 consists mainly of quartz and magnetite, with varying amounts of amphibole, biotite, and garnet; they contain 48.3-58.6 SiO2 and 21.34–33.82 wt. %, Fe2O3T, suggesting that the rocks are BIF. BIF-1 of the KGB, as well as most Archean BIFs, contain high Fe2O3T, concentration, display a contrasting positive Eu anomaly, lost of Ce anomaly, the depletion of LREE relative to HREE. However, they stand out among other BIFs with high Al2O3, TiO2, MgO, K2O, Cr, Ni, Zr, Ba, Cu and Zn concentrations. BIF-1 was formed in a marine basin in an anoxic atmosphere due to hydrothermal fluids, the proportion of which varies from 20 to 80 %, and a terrigenous component derived mainly from basalts, komatiites, and dacites in host rocks. Mesoarchean BIF-1 of the KGB s was formed in a small rift within an oceanic volcanic plateau, the formation of which is associated with the influence of a mantle plume on the oceanic lithosphere.

Onset and tempo of ignimbrite flare-up volcanism in the eastern and central Mogollon-Datil volcanic field, southern New Mexico, USA

The Cenozoic ignimbrite flare-up (40–18 Ma) generated multiple volcanic fields in the southwestern United States and northern Mexico resulting from asthenospheric mantle upwelling after removal of the Farallon slab. The correlation of tuffs to one another and to source calderas within these volcanic fields is essential for determining spatiotemporal patterns in volcanism and magma geochemistry, which have been used to deduce migration of the Farallon slab at depth and associated mantle melting. However, the correlation of Eocene–Oligocene tuffs in the southwestern U.S. is difficult because of post-emplacement erosion and faulting. This study focuses on spatiotemporal patterns of the initial episode of ignimbrite flare-up activity (ca. 36.5–33.8 Ma) in the Mogollon-Datil volcanic field in south-central New Mexico, USA. We show that alkali feldspar major and trace element geochemistry is an effective tool for correlating tuffs when combined with high-precision, single-crystal 40Ar/39Ar geochronology and bulk-rock geochemistry. Using these data, we correlate several tuff units and differentiate other tuffs that have the same eruption age but very different geochemistry, and we conclude that there was a broadly northwestward migration in volcanism over time. The new tuff correlations are used to investigate spatiotemporal variations in magma geochemistry, erupted volumes, and recurrence intervals during the initial episode of Mogollon-Datil volcanic field volcanism. Early-erupted tuffs restricted to the eastern Mogollon-Datil volcanic field share similarities with western U.S. topaz rhyolites, which suggests that the silicic magmas were generated by partial melting of mafic lower crustal rocks. We also find differences in the compositions, crystallinities, and mineral assemblages between the early- and late-erupted tuffs. The early-erupted tuffs tend to have single-feldspar mineralogies, lower feldspar Or contents, large negative Eu anomalies, and low-whole–rock Ba concentrations. Conversely, late-erupted tuffs have two feldspar plus quartz assemblages, lesser Eu anomalies, higher whole-rock Ba concentrations, and feldspars have higher Or contents. Thus, we suggest that for some of the early eruptions, after magmas underwent crystal fractionation in the crust, the silicic melt largely separated from the crystalline mush prior to eruption, whereas late-erupted tuff magmas underwent crystal fractionation at near the eutectic minimum and were remobilized and erupted with a larger proportion of their crystalline mush. Using our new ages, correlations, and previously published data, we find that the initial phase of Mogollon-Datil volcanic field volcanism produced at least 15 eruptions between 36.5 Ma and 33.8 Ma, with a minimum total erupted volume of ~1350 km3 and an average recurrence interval of 170 k.y. However, eruptions were generally smaller in volume (most &amp;lt;15 km3) than in other coeval fields, and most eruptions (n = 11) occurred in the first 1.2 m.y. (ca. 36.5–35.3 Ma) of activity. Altogether, our work sheds new light on variations in the composition, timing, and migration of volcanism during the initial phase of Mogollon-Datil volcanic field activity and highlights the utility of feldspar geochemistry in both “fingerprinting” tuffs and elucidating magma evolution.

Multivariate statistical “unmixing” of Indian and Pacific Ocean sediment provenance

AbstractThe geochemistry of marine sediment is a massive archive of (paleo)oceanographic information. Accessing that information requires “unmixing” the various influences on marine sediment geochemistry to understand individual sources and marine geochemical processes. Q‐mode factor analysis (QFA) and independent component analysis (ICA) are multivariate statistical techniques that have successfully been applied to large datasets of marine sediment element concentrations to identify the number and composition of marine sediment sources or end‐members. In this study, we apply both techniques to two datasets of marine sediment geochemistry, compare the output, and discuss the advantages of each approach. In both datasets, ICA identified a mixing trend between carbonates and dust, whereas QFA represented the end‐members as two separate factors. In the Pacific and Indian Oceans dataset, both techniques produced three factors or independent components involving rare earth elements, but two of the QFA factors explained a small, almost negligible, amount of the variability of the dataset. Also, QFA identified more aluminosilicate end‐members (dust or volcanic ash) than ICA. In the Indian Ocean Sites 738 and 752 dataset, ICA identified two processes affecting Sr and Ba concentrations as separate independent components, while QFA created a factor representing the covariation of Sr and Ba over intervals of the site's paleoceanographic history. The results of this study exemplify that QFA identifies covariances and finds discrete end‐members contributing to the bulk mass of sediment. ICA works best with non‐Gaussian element distributions and finds geochemical signals and mixing trends that constitute the characteristic structure of the multielemental data.

Constraint on boric acid resistance and tolerance evolvability in Candida albicans.

Boric acid is a broad-spectrum antimicrobial used to treat vulvovaginal candidiasis when patients relapse on the primary azole drug fluconazole. Candida albicans is the most common cause of vulvovaginal candidiasis, colloquially referred to as a "vaginal yeast infection". Little is known about the propensity of C. albicans to develop BA resistance or tolerance (the ability of a subpopulation to grow slowly in high levels of drug). We evolved 96 replicates from eight diverse C. albicans strains to increasing BA concentrations to test the evolvability of BA resistance and tolerance. Replicate growth was individually assessed daily, with replicates passaged when they had reached an optical density consistent with exponential growth. Many replicates went extinct quickly. Although some replicates could grow in much higher levels of BA than the ancestral strains, evolved populations isolated from the highest terminal BA levels (after 11 weeks of passages) surprisingly showed only modest growth improvements and only at low levels of BA. No large increases in resistance or tolerance were observed in the evolved replicates. Overall, our findings illustrate that there may be evolutionary constraints limiting the emergence of BA resistance and tolerance, which could explain why it remains an effective treatment for recurrent yeast infections.

Dissolved Barium Causes Toxicity to Groundwater Cyclopoida.

Barium (Ba) dissolution and mobilization in groundwater are predominantly controlled by sulfate because of the low solubility of barium sulfate (BaSO4) minerals. Naturally present at low concentrations in groundwater, elevated concentrations of Ba can occur as a result of anthropogenic activities, including use of barite in drill operations, and geogenic sources such as leaching from geological formations. No toxicity data exist for Ba with groundwater organisms (stygofauna) to assess the risk of elevated Ba concentrations. The present study measured Ba toxicity to two stygobiont Cyclopoida species: one collected from Wellington and the other from Somersby, New South Wales, Australia. Toxicity was measured as cyclopoid survival over 2, 4, 7, 14, 21, and 28 days in waters of varying sulfate concentration (<1-100 mg SO4/L). When sulfate was present, dissolved Ba concentrations decreased rapidly in toxicity test solutions forming a BaSO4 precipitate until dissolved sulfate was depleted. Barium in excess of sulfate remained in the dissolved form. The toxicity of Ba to cyclopoids was clearly attributed to dissolved Ba. Precipitated Ba was not toxic to the Wellington cyclopoid species. Toxicity values for dissolved Ba for the Wellington and Somersby cyclopoid species included a (21-day) no-effect concentration of 3.3 mg/L and an effective concentration to cause 5% mortality of 4.8 mg/L (at 21 days). Elevated dissolved Ba concentrations due to anthropogenic and/or biogeochemical processes may pose a risk to groundwater organisms. Further toxicity testing with other stygobiont species is recommended to increase the data available to derive a guideline value for Ba that can be used in contaminant risk assessments for groundwaters. Environ Toxicol Chem 2024;00:1-14. © 2024 The Author(s). Environmental Toxicology and Chemistry published by Wiley Periodicals LLC on behalf of SETAC.

New insights into the petrogenesis of granitic rocks in southern Thailand, SE Asia tin belt: evidence from petrochemistry and geochronology

ABSTRACT The granitic rocks in the Prachuap Khiri Khan Province, southern Thailand, SE Asia Tin Belt, comprise gneissic biotite monzogranite, porphyritic muscovite–biotite monzogranite, and porphyritic biotite monzogranite. Comprehensive field observations, petrography, mineral chemistry, and geochemistry establish gneissic biotite monzogranites as part of the Central Belt Granites (CBGs), while porphyritic muscovite–biotite monzogranite and porphyritic biotite monzogranite as part of the Western Belt Granites (WBGs). CBG and WBG granitic units exhibit peraluminous, alkali-calcic, and magnesian magmatic series traits, reflecting an S-type granite character resulting from crustal partial melting. Significantly, scatter correlations in variation diagrams, combined with the enrichment of Cs, Rb, Th, U, Pb, Nd, and P, and the depletion of Ba, Nb, and Ti contents, point towards an S-type granite signature formed during collisional events. Crystallization conditions reveal CBG gneissic biotite monzogranite encountered P–T conditions of 2.97–3.85 kbar/680°C–733°C/11.1–14.4 km, while WBG’s porphyritic muscovite–biotite monzogranite and porphyritic biotite monzogranite experienced 2.73–4.15 kbar/628°C–732°C/10.2–15.5 km and 2.47–3.80 kbar/651°C–728°C/9.2–14.2 km, respectively. Geochronological data indicate that CBG’s gneissic biotite monzogranite was emplaced from Early Cretaceous collision (128–119 Ma) of Indochina and Sibumasu terranes, while WBG’s porphyritic muscovite–biotite monzogranite and porphyritic biotite monzogranite were formed during the syn-collision of Sibumasu and West Burma terranes during Early Cretaceous (121–111 Ma) to Paleocene. Mineralogical and geochemical attributes of these granitic rocks exhibit strong relevance to Sn-W mineralization processes, indicative of a profound association.

Active methane release from the early Cambrian seafloor? Clues from Ba isotopes

The Cambrian Explosion coincided with a global greenhouse climate, but the mechanism behind this warming event remains unclear, impeding our understanding of their essential link. To address this, an integrated study of δ138Ba, δ34S, Scanning Electron Microscopy, and Energy Dispersive Spectroscopy was carried out on the lower Cambrian shales from a range of water depths in the Nanhua Basin of South China. These shales are characterized by variably elevated Ba concentrations (>10,000 ppm), primarily hosted by barite and Ba-feldspar, with the latter found only in a deep-water setting. The Ba-isotopic compositions of the study shales (δ138Ba, −0.15‰ to +0.60‰), along with the large size and euhedral shape of barite crystals and associated soft-sediment deformation, indicate that barite and Ba-feldspar were formed in porewaters close to the sulfate-methane-transition zone during early diagenesis under sulfate-rich and sulfate-poor conditions, respectively. We propose that low sulfate in the early Cambrian ocean, coupled with the high organic matter content of the sediment, may have resulted in large methane emissions from the sediment to the atmosphere, generating an early Cambrian greenhouse climate at the time of the Cambrian Explosion.

Evaluating the portable X-ray fluorescence reliability for metal(loid)s detection and soil contamination status.

Marginalized communities experience barriers that can prevent soil monitoring efforts and knowledge transfer. To address this challenge, this study compared two analytical methods: portable X-ray fluorescence spectroscopy (pXRF, less time, cost) and inductively coupled plasma mass spectrometry (ICP-MS, "gold standard"). Surface soil samples were collected from residential sites in Arizona, USA (N = 124) and public areas in Troy, New York, USA (N = 33). Soil preparation differed between groups to account for community practice. Statistical calculations were conducted, paired t test, Bland-Altman plot, and a two-way ANOVA indicated no significant difference for As, Ba, Ca, Cu, Mn, Pb, and Zn concentrations except for Ba in the t test. Iron, Ni, Cr, and K were statistically different for Arizona soils and V, Ni, Fe, and Al concentrations were statistically different for New York soils. Zinc was the only element with high R2 and low p value. Pollution load index (PLI), enrichment factors (EF), and geo-accumulation index (Igeo) were calculated for both methods using U.S. Geological Survey data. The PLI were > 1, indicating soil pollution in the two states. Between pXRF and ICP-MS, the Igeo and EF in Arizona had similar degree of contamination for most elements except Zn in garden and Pb in yard, respectively. For New York, the Igeo of As, Cu, and Zn differed by only one classification index between the two methods. The pXRF was reliable in determining As, Ba, Ca, Cu, Mn, Pb, and Zn in impacted communities. Therefore, the pXRF can be a cost-effective alternative to using ICP-MS techniques to screen soil samples for several environmentally relevant contaminants to protect environmental public health.

Determination of macro‐ and microelements concentrations by wavelength‐dispersive X‐ray fluorescence spectrometry in the objects of the technogenic ecosystem

AbstractThe wavelength‐dispersive X‐ray fluorescence (WDXRF) spectrometry was applied to determine Na, Mg, Al, P, S, K, Ca, Cr, Mn, Fe, Ni, Cu, Zn, Sr, Ba, and Pb concentrations in the needles of dwarfish spruce Picea canadensis conica and the blue prickly spruce Picea pungens glauca, as well in technogenic soil of Irkutsk city, in which these spruce species grow. All measurements were performed in vacuum using WDXRF spectrometer S8 TIGER produced by Bruker AXS, Germany. The calculated values of instrumental limit of detection (ILD) ranged from 0.5 for Ni to 67 mg/kg for Al for soil certified reference materials (CRMs) such as OOKO151 (light chestnut soil) and from 0.2 for Cu and Ni to 18–24 mg/kg for Na for the plant CRMs such as LB‐1 (birch leaf) and EC‐1 (Canadian waterweed). The repeatability is satisfactory. The values of relative standard deviations (RSDs) do not exceed 15% for soils and available plant material. With calculated T‐statistics, it was found that the WDXRF data do not contain systematic errors. The values of relative discrepancy for WDXRF, total reflection X‐ray fluorescence (TXRF) spectrometry, and atomic emission spectrometry with arc discharge (d.c. arc‐AES) results do not exceed 30% for studied elements.

PROPAGATION AND CALLUS REGENERATION OF POTATO (SOLANUM TUBEROSUM L.) CULTIVAR ‘DESIREE’ UNDER SALT STRESS CONDITIONS

Under laboratory conditions, segments of potato with single nodes were exposed to varying doses of Sodium Chloride (NaCl) (0 mM, 20 mM, 40 mM, 60 mM, 80 mM and 100 mM), using the Murashige and Skoog growth medium to assess how NaCl salt stress affects micropropagation, callus formation, and regeneration in the ‘Desiree’ potato plant cultivar, and also seeks to determine the ability of this cultivar to thrive in salt stress conditions. The data were collected after a six-week period for each salt treatment. Remarkably, a significant increase in the mass of green and dry stems and roots was observed specifically under the 40 mM NaCl treatment. Conversely, the length of shoots and branches experienced a reduction as the NaCl concentration increased. The overall impact of the NaCl treatments strongly influenced root weight. Concerning the formation (development) and revitalization of callus, segments of potato microtubers were exposed to the above-mentioned NaCl concentrations, resulting in an intermediate level of salt stress that significantly reduced callus weights as NaCl concentration increased. Furthermore, a gradual decrease in the regeneration rate was noted with increasing concentrations of the plant growth regulator BA (1 to 4 mg/l). The most profound relative regeneration rate occurred at 1 mg/l BA. Notably, the counteractive effect of salt was more apparent with higher NaCl concentrations, with exceptions at 20 mM and 40 mM. These findings propose that the ‘Desiree’ potato cultivar exhibits moderate tolerance to salt stress and indicates a capacity to endure salinity. Moreover, this valuable variety could potentially be harnessed through genetic manipulation to enhance its salt resilience.

Seawater barium and sulfide removal improved marine habitability for the Cambrian Explosion of early animals.

An increase in atmospheric pO2 has been proposed as a trigger for the Cambrian Explosion at ∼539-514Ma but the mechanistic linkage remains unclear. To gain insights into marine habitability for the Cambrian Explosion, we analysed excess Ba contents (Baexcess) and isotope compositions (δ138Baexcess) of ∼521-Myr-old metalliferous black shales in South China. The δ138Baexcess values vary within a large range and show a negative logarithmic correlation with Baexcess, suggesting a major (>99%) drawdown of oceanic Ba inventory via barite precipitation. Spatial variations in Baexcess and δ138Baexcess indicate that Ba removal was driven by sulfate availability that was ultimately derived from the upwelling of deep seawaters. Global oceanic oxygenation across the Ediacaran-Cambrian transition may have increased the sulfate reservoir via oxidation of sulfide and concurrently decreased the Ba reservoir by barite precipitation. The removal of both H2S and Ba that are deleterious to animals could have improved marine habitability for early animals.

Li-mineralized pegmatite of anatectic origin: Constraints from Li[sbnd]Hf isotopes and geochemical modeling

Pegmatites are important reservoirs of lithium resources. There is an ongoing debate as to whether Li-mineralized pegmatites were generated from evolved granitic systems via extreme differentiation or by direct melting of metasedimentary rocks. The Chinese Altay is one of the largest pegmatite provinces in the world, and includes many rare-metal pegmatites (e.g., Koktokay, Kelumute, Kaluan and Azubai). However, they display significant differences in formation ages and isotopic compositions compared with the neighbouring or potential parental granites. In this contribution, we present a case study of the Kaluan Li ore deposit in the Chinese Altay, elucidating the origins of pegmatites and related Li mineralization. The Kaluan Li-mineralized pegmatites are characterized by high SiO2, K2O, Na2O, Li, Cs, Ta, and Rb contents; low Fe2O3T, MgO, Ba, and Sr contents; and peraluminous signatures. They have homogeneous HfLi isotopic compositions (εHf (t) = −0.6 to +2.5; δ7Li = +1.6 to +5.8‰) that are within the range of HfLi isotopic compositions of the Kulumuti Group schists (εHf (t) = −2.8 to +7.5; δ7Li = −8.6 to +10.8‰). In addition, the chemical compositions of the melt derived from the partial melting of the Kulumuti Group by phase equilibrium modeling are compatible with our analyses of the Kaluan Li-mineralized pegmatites. These similarities suggest that the Kaluan Li-mineralized pegmatites were derived from the partial melting of the Kulumuti Group schists at depths during the Triassic, in a post-orogenic and extensional setting. The generation of these pegmatites was mostly controlled by biotite dehydration melting at relatively high temperatures, rather than by the low-temperature melting of muscovite. Trace elements modeling results show that approximately 33–36% partial melting of the average Kulumuti Group schist may produce melts with maximum Li concentrations ranging from 664 to 751 ppm. Subsequently, a high degree of fractionation exceeding 85%, was required for the Li concentration of the residual melt to reach concentrations suitable for crystallization into albite-spodumene pegmatites. Based on our research, an anatectic origin model may have general applicability in explaining the genesis and mineralization of rare-metal pegmatites in the Chinese Altay.

Anatomy and genesis of the world’s largest carbonate-hosted Zn-Pb deposit: New insights from ore characteristics, Zn-Pb-C-O isotopes, and trace element constraints of the Huoshaoyun deposit, Karakorum Range, Xinjiang

The Huoshaoyun deposit in the Karakorum area of NW China is the world’s largest zinc-lead carbonate ore deposit. Here we investigate the genesis of the mineralization based on multiproxy investigations. The deposit contains zinc-lead carbonate and sulfide minerals, with smithsonite (Smt), cerussite (Cer), and sulfides accounting for 85%, 10%, and 5% of the total lead and zinc resources, respectively. Three ore-forming stages, involving Smt, Cer, and sulfides ores were summarized. The Smt mineralization is characterized by veined, massive, and stratified Smt forming horizontal sedimentary layered ore and vertical feeder veins similar to the SEDEX-type deposits. The sulfide and Cer veins display typical hydrothermal characteristics and are superimposed on the massive Smt ores. The Smt ores show high Li, Be, Cr, Y, Ba, Nd, Yb, and Zr contents, whereas the Cer veins have extremely high Sr contents (up to 3814–9174 ppm) and low Zr contents (less than 0.01 ppm). Galena and sphalerite show higher Cd concentrations compared to Smt and Cer ores.The Smt ores differ with different spatial locations, with Smt ores formed at the vent have δ66Zn values of +0.15‰ to +0.21‰, the massive Smt formed close to the vent show a value of +0.13‰, and those formed away from the vent show a value of 0.05‰, all values being close to 0. The sulfides have δ66Zn values of −0.09‰ to +0.04‰. The C-O isotopes of Smt ores are similar to both altered and unaltered host limestone, suggesting that the limestone was a potential source for carbon and oxygen. Quartz with veined Smt shows magmatic signatures with δ18OVSMOW of +1.14‰ to +2.23‰, high Pb (115–401 ppm) and Zn concentrations (390–997 ppm), whereas quartz associated with sulfide has meteoric fluid signature with the lowest δ18OVSMOW (−14‰ to −10.7‰), low Pb (11.6–49.0 ppm) and Zn (18.1–72.8 ppm) concentrations. The temperature of equilibration computed based on oxygen isotope fractionation between Smt and coeval quartz indicate a dual source with that of quartz derived from an aqueous fluid, whereas the source for Smt might involve CO2 or HCO3−.We trace multiple metallogenic stages for this deposit including exhalation, hydrothermal deposition, and fault-controlled sulfide vein formation. The largest orebody (III-1) preserves a 16 Mt reserve of Zn and was formed by crust-mantle interaction at ca. 195 Ma in the early development of the Linjitang post-arc rift system. Fluid convection, zinc enrichment driven by granitic magma, volcanic activity, and karst alteration induced by acid rain in a lagoonal environment promoted ore enrichment.

Analysis of the Concentration of Selected Elements in Teeth Hard Tissues and Their Role in Biomineralization Processes

The role of trace elements, heavy metals, and their effect on the development of hard tissue mineralization balance is poorly documented and the available results are often contradictory. The aim of the present study was the assessment of the concentration of the selected elements in the teeth of deer (Capreolus capreolus) and red deer (Cervus elaphus) with respect to their potential role in maintaining biomineralization balance in teeth hard tissues. Moreover, the aim was to determine whether trace elements accumulate in teeth with age. This study was conducted on 22 molar teeth of red deer (Cervus elaphus) and 54 molar teeth of roe deer (Capreolus capreolus) from Poland. Samples were analyzed with the use of inductively coupled plasma optical emission spectrometry equipped with a concentric nebulizer and cyclonic spray chamber in order to determine their Al, Ba, Cd, Fe, K, Li, Mg, Na, Ni, Pb, Sr, and Zn contents. There were strong positive correlations between strontium and zinc with heavy metals, particularly in dentine, which may affect the neutralization of the negative effects of heavy metals on tooth tissue and, consequently, maintaining ionic balance. The accumulation of trace elements with age in serenades has not been confirmed.

An alternative to the igneous crust fluid + sediment melt paradigm for arc lava geochemistry.

A long-standing paradigm of arc geochemistry is that the trace element compositions of arc lavas arise from two compositionally distinct slab components: an aqueous dehydration fluid from the subducting igneous ocean crust that transports "fluid-mobile" elements, such as barium (Ba), and a sediment melt that supplies thorium (Th) and the light rare earth elements. This two-component framework has been widely called upon to explain global geochemical trends as well as geochemical variations within individual arcs, such as the Marianas. Here, we show that this paradigm is inconsistent with mass balance, due to the low Ba contents of igneous ocean crust, and with experimental data, which show that aqueous fluids from the igneous oceanic crust would be too dilute to substantially affect arc compositions. Observations previously attributed to the sediment melt/igneous-crust-fluid hypothesis are better explained by diverse subducting sediment compositions coupled with ambient mantle wedge heterogeneity, both globally and for the Marianas.