Low Concentrations Of Trace Elements Research Articles

Extraction of Pb and Zn from crude oil for high-precision isotopic analysis by MC-ICP-MS

Radiogenic and stable isotopic tracing of crude oils has not so far been undertaken, largely because of the difficulties of dealing with the low trace element contents of oil samples for high-precision isotopic measurements. Here, we present a novel analytical protocol that allows for precise and accurate determination of radiogenic Pb and stable Zn isotopic compositions on as little as 5 ml of crude oil from a variety of geographically, geologically, and environmentally diverse settings. The 41 Pb and Zn samples measured to validate the new protocol were separated from their respective crude oils by liquid-liquid extraction into an aqueous phase readily handled in a clean laboratory for subsequent purification of Pb and Zn by standard anion-exchange column chromatography. Lead and Zn isotopic compositions on the same 5 ml sample of crude oil were obtained by MC-ICP-MS on 95% of the total extracted Pb and Zn, while elemental concentrations were measured by Q-ICP-MS on 5% aliquots. To the best of our knowledge, the present technique is the first efficient procedure for Pb and Zn isotopic analysis of crude oil, which, owing to the elimination of the organic fraction at the liquid-liquid extraction stage, does not require any specialized equipment, neither for the wet chemistry nor for the mass spectrometry. The high extraction yields of the method and the low detection limits and high sensitivity of, respectively, Q-ICP-MS and MC-ICP-MS permit analysis of very small sample quantities (down to 2 ng and 100 ng, respectively, of Pb and Zn for isotopic analysis, and a few hundred pg for abundance measurements). Reproducibility is on a par with routine state-of-the-art Pb and Zn isotopic measurements of other types of geological materials, while total procedural blanks for both elements are negligible relative to the amounts of Pb and Zn typically separated from crude oil.

Revisiting the Lushan-Taihua Complex: New perspectives on the Late Mesoarchean-Early Neoarchean crustal evolution of the southern North China Craton

The Taihua Complex in the Lushan area was divided into gneisses series and supracrustal rocks. The former is mainly composed of TTG gneisses and amphibolites, and records the Late Mesoarchean-Early Neoarchean crustal evolution of the southern North China Craton (NCC). Late Mesoarchean amphibolites (>2.84 Ga) are enriched in light rare-earth elements (LREEs) and large-ion-lithophile elements (LILEs) with negative Nb-Ta and Ti anomalies, derived from partial melting of a metasomatic mantle source. Late Mesoarchean TTG gneisses (>2.81 Ga) have high La/Yb and Sr/Y ratios and low MgO, Cr and Ni contents, and are interpreted as resulting from partial melting of a thickened lower crust with residual garnet and amphibole in the source. Early Neoarchean amphibolites (2.80–2.73 Ga) show flat REE patterns but slightly negative Nb-Ta and Ti anomalies due to the fractionation of Ti-rich minerals and have depleted Hf-Nd isotopes, and were derived from large degree partial melting of a depleted mantle source. Most of the Early Neoarchean TTG gneisses show pronounced positive Eu anomalies and have relatively lower trace element concentrations and more depleted Nd-Hf isotopes than the Late Mesoarchean TTG gneisses, resulted from the partial melting of thickened juvenile lower crust with residual garnet and amphibole in the source and subsequent plagioclase accumulation. In addition, some of the Early Neoarchean TTG gneisses have high MgO, Cr and Ni contents, which were likely derived from partial melting of delaminated lower crust or a thickened lower crust interacting with mafic melt.Late Mesoarchean amphibolites and TTG gneisses are restricted in the center of Lushan area, denoting an ancient continental nucleus. In contrast, Early Neoarchean amphibolites and TTG gneisses outcrop in peripheral of the ancient nucleus, exhibiting as an elongated belt along the Dangzehe River, which is evidence for the subduction. Overall, the Lushan amphibolites and TTG gneisses show slightly negative to positive whole-rock εNd(t) and εHf(t) values and zircon εHf(t) values, indicating a dominant crustal accretion with subordinate crustal reworking. Therefore, the continental growth recorded in the Lushan-Taihua Complex was caused by the subduction-accretion process, suggesting a convergent margin in the southern NCC during the Late Mesoarchean and Early Neoarchean.

Trace element contents in foods from the first French total diet study on infants and toddlers

Occurrence data for aluminium, antimony, arsenic, barium, cadmium, chrome, cobalt, gallium, germanium, nickel, strontium, silver, tellurium, tin and vanadium were compiled during the first French Total Diet Study on infants and toddlers. For infant foods, meat-/fish-based and vegetable-based ready-to-eat meals were among the most contaminated food categories for most trace elements, except for gallium, antimony and vanadium, for which the concentrations were relatively similar in all food categories. Soups/purees and cereal-based foods had the highest levels of aluminium (653 and 630 μg kg−1, respectively), whereas fruit purees had the highest level of tin (424 μg kg−1). Infant and follow-on formulae and growing-up milks had relatively low mean contents of trace elements compared with the other infant food categories: e.g. aluminium (220 μg kg−1), arsenic (1.80 μg kg−1), cadmium (0.51 μg kg−1). Chocolate-based foods contributed substantially to the higher levels of aluminium, cadmium, cobalt, chromium and nickel in sweet and savoury biscuits and bars, dairy-based desserts and croissant-like pastries. Only the contribution of chromium and barium levels were statistically different between infant and common foods, with median concentrations being slightly higher in infant foods. The results were largely comparable to those from other surveys on baby food.

Oxidative Stress Parameters, Selenium Levels, DNA Damage, and Phthalate Levels in Plastic Workers.

Di(2-ethylhexyl)phthalate (DEHP) is the most widely used phthalate. DEHP is highly used in PVC floorings and PVC windows and carpeting. The objective of this study was to determine sex hormone levels, oxidative stress parameters, selenium levels, DNA damage, and phthalate levels in plastics workers (n = 24, age = 20-58 years) working in the production of rubber mechanical goods and exposed to DEHP in workplace. The control group (n = 29, age = 25-54, all male) was selected from age-matched healthy adults. Antioxidant parameters and DNA damage were determined by spectrophotometry. Selenium levels were determined by atomic absorption spectroscopy. Plasma hormone levels were measured by chemiluminescence microparticle immunoassay. Plasma phthalate levels were determined by high-pressure liquid chromatography. Plastic workers had lower serum testosterone and free T4 levels and higher follicle-stimulating hormone levels vs. controls. Liver enzyme activities were markedly higher in workers vs. controls. There were also increases in plasma glutathione peroxidase levels and marked decreases in plasma selenium and erythrocyte total glutathione levels in plastics workers (P < 0.05 vs. control). Plasma 8-hydroxy-2'-deoxyguanosine levels were 14-fold higher in plastics workers than in controls. Plasma DEHP and mono(2-ethylhexyl)phthalate were also markedly higher in workers vs. controls. The results of this study show that occupational exposure to DEHP may lead to disturbances in sex hormones, increased liver problems, higher oxidative stress and DNA damage levels, and lower trace element concentrations in workers. More comprehensive and mechanistic studies with higher numbers of subjects are needed to show the unwanted effects of occupational exposure to DEHP.

The Influence of Karst Aquifer Mineralogy and Geochemistry on Groundwater Characteristics: West Bank, Palestine

This work reports, for the first time, the mineralogical and geochemical characteristics of karst aquifers in the Central West Bank (CWB) catchment in Palestine. It provides an integrated study approach by correlating the geochemistry of the lithology and hydrochemical data of groundwater samples. Mineralogical analysis showed that all of the samples were dominantly composed of either calcite CaCO3 (5–100 wt. %) or dolomite CaMg(CO3)2 (4–100 wt. %), with minor amounts of quartz and feldspar, which is supported by the inorganic carbon content (9–13 wt. %) and hydrochemical composition of the spring water samples. The whole-rock geochemical data indicated that the samples have low contents of trace elements and transition metals. In contrast, the concentrations of alkaline earth elements (Mg, Ca, Sr, Ba) and Mn were high in the rock and groundwater samples. Generally, the trace elements of rock samples with concentrations &gt;10 ppm included Sr (17–330 ppm), Mn (17–367 ppm), Ba (2–32 ppm), W (5–37 ppm), Cr (3–23 ppm), Zn (1.7–28 ppm), V (4–23 ppm), and Zr (1–22 ppm), while the concentrations of all the other trace elements was below 10 ppm. Ionic ratios and hierarchical cluster analysis (HCA) suggested that the chemical evolution of groundwater was mainly related to the geogenic (rock–water) interaction in the study area. This is clear in the alkaline earth elements (Mg, Ca, Sr, Ba) ratios, especially regarding the Sr values. The calcite rock samples had higher Sr (mean 160 ppm, n = 11) than those of the dolomite rocks (mean 76 ppm, n = 9).

Bioindication of Heavy-Metal Pollution in the Coastal Marine Waters of Russky Island (Peter the Great Bay, Sea of Japan)

The first assessment of the condition of coastal waters around Russky Island, Peter the Great Bay, in the vicinity of Vladivostok, has been made based on the data on concentrations of Fe, Zn, Cu, Cd, Pb, and Ni in the brown algae Sargassum miyabei and S. pallidum collected along the coast of the island in July and August 2016. It has been found that the concentrations of heavy metals in algae from waters off Russky Island mostly exceed their background levels in Sargassum algae from the northwestern Sea of Japan. On the southeastern side of the island, facing Ussuri Bay, which is distinguished by a rocky/bouldery coast and beds of S. pallidum, algae are characterized by lower concentrations of trace elements than those on the other sides.

Heterogeneity of melts in impact deposits and implications for their origin (Ries suevite, Germany)

AbstractImpact melt‐bearing clastic deposits (suevites) are one of the most important records of the impact cratering process. A deeper understanding of their composition and formation is therefore essential. This study focuses on impact melt particles in suevite at Ries, Germany. Textures and chemical evidence indicate that the suevite contains three melt types that originate from different shock levels in the target. The most abundant melt type (“melt type 1”) represents well‐mixed whole‐rock melting of crystalline basement and includes incompletely mixed mafic melt schlieren (“melt type 1 mafic”). Polymineralic melt type 2 comprises mixes between monomineralic melt types 3 and melt type 1. Melt types 2 and 3 are located within melt type 1 as small patches or schlieren but also isolated within the suevite matrix. The main melt type 1 is heterogeneous with respect to trace elements, varying geographically around the crater: in the western sector, it has lower values in trace elements, e.g., Ba, Zr, Th, and Ce, than in the eastern sector. The west–east zoning likely reflects the heterogeneous nature of crystalline basement target rocks with lower trace element contents, e.g., Ba, Zr, Th, and Ce, in the west compared to the east. The chemical zoning pattern of suevite melt type 1 indicates that mixing during ejection and emplacement occurred only on a local (hundreds of meters) scale. The incomplete larger scale mixing indicated by the preservation of these local chemical signatures, and schlieren corroborate the assumption that mixing, ejection, and quenching were very rapid, short‐lived processes.

Trace Metal Distribution in Sulfide Minerals from Ultramafic-Hosted Hydrothermal Systems: Examples from the Kairei Vent Field, Central Indian Ridge

The ultramafic-hosted Kairei vent field is located at 25°19′ S, 70°02′ E, towards the Northern end of segment 1 of the Central Indian Ridge (CIR-S1) at a water depth of ~2450 m. This study aims to investigate the distribution of trace elements among sulfide minerals of differing textures and to examine the possible factors controlling the trace element distribution in those minerals using LA-ICP-MS spot and line scan analyses. Our results show that there are distinct systematic differences in trace element distributions throughout the different minerals, as follows: (1) pyrite is divided into three types at Kairei, including early-stage euhedral pyrite (py-I), sub-euhedral pyrite (py-II), and colloform pyrite (py-III). Pyrite is generally enriched with Mo, Au, As, Tl, Mn, and U. Pyrite-I has high contents of Se, Te, Bi, and Ni when compared to the other types; py-II is enriched in Au relative to py-I and py-III, but poor in Ni; py-III is enriched in Mo, Pb, and U but is poor in Se, Te, Bi, and Au relative to py-I and py-II. Variations in the concentrations of Se, Te, and Bi in pyrite are most likely governed by the strong temperature gradient. There is generally a lower concentration of nickel than Co in pyrite, indicating that our samples precipitated at high temperatures, whereas the extreme Co enrichment is likely from a magmatic heat source combined with an influence of serpentinization reactions. (2) Chalcopyrite is characterized by high concentrations of Co, Se, and Te. The abundance of Se and Te in chalcopyrite over the other minerals is interpreted to have been caused by the high solubilities of Se and Te in the chalcopyrite lattice at high temperatures. The concentrations of Sb, As, and Au are relatively low in chalcopyrite from the Kairei vent field. (3) Sphalerite from Zn-rich chimneys is characterized by high concentrations of Sn, Co, Ga, Ge, Ag, Pb, Sb, As, and Cd, but is depleted in Se, Te, Bi, Mo, Au, Ni, Tl, Mn, Ba, V, and U in comparison with the other minerals. The high concentrations of Cd and Co are likely caused by the substitution of Cd2+ and Co2+ for Zn2+ in sphalerite. A high concentration of Pb accompanied by a high Ag concentration in sphalerite indicates that Ag occurs as Pb–Ag sulfosalts. Gold is generally low in sphalerite and strongly correlates with Pb, suggesting its presence in microinclusions of galena. The strong correlation of As with Ge in sphalerite from Kairei suggests that they might precipitate at medium temperatures and under moderately reduced conditions. (4) Bornite–digenite has very low concentrations of most trace elements, except for Co, Se, and Bi. Serpentinization in ultramafic-hosted hydrothermal systems might play an important role in Au enrichment in pyrite with low As contents. Compared to felsic-hosted seafloor massive sulfide deposits, sulfide minerals from ultramafic-hosted deposits show higher concentrations of Se and Te, but lower As, Sb, and Au concentrations, the latter often attributed to the contribution of magmatic volatiles. As with typical ultramafic-hosted seafloor massive sulfide deposits, Se enrichment in chalcopyrite from Kairei indicates that the primary factor that controls the Se enrichment is temperature-controlled mobility in vent fluids.

Metal remobilization and ore-fluid perturbation during episodic replacement of auriferous pyrite from an epizonal orogenic gold deposit

Mineral-scale episodic replacement of auriferous pyrite by texturally-complex pyrite, marcasite and minor arsenopyrite occurred in breccia ores from the Daqiao epizonal orogenic gold deposit, West Qinling Orogen, China. This study uses a novel combination of laser ablation-inductively coupled plasma-mass spectrometry (LA-ICP-MS), Nanoscale secondary ion mass spectrometry (NanoSIMS), and secondary ion mass spectrometry (SIMS) to investigate the remobilization and re-concentration of gold and other trace elements during this complex replacement process and the probable mechanism. Several lines of evidence including some degree of preservation of external morphology, sharp contacts and compositional differences between the parent pyrite and product pyrite and marcasite, and reaction-induced porosity suggest that the replacement of parent pyrite proceeds via a two-step replacement via a dissolution and reprecipitation mechanism, plus an additional marcasite overgrowth. During the replacement of euhedral pyrite, depletion of gold and other trace elements (Te, Se, Zn, Co, Tl, Ni, W, and As) in porous product pyrite relative to its precursor indicate exsolution and remobilization of these metals from crystal lattice of the original pyrite. In the subsequent replacement of porous pyrite by two types of marcasite and minor arsenopyrite, euhedral product marcasite contains low contents of trace elements, possibly due to high metal solubility in the acidic fluids favorable for marcasite precipitation. The complex-zoned marcasite significantly enriched in gold and other metals relative to porous pyrite (W, Tl, As, Sb, Ag, Se, and Zn) is thought to have formed via precipitation triggered by further oxidation and/or immediate reduction in threshold supersaturation. Dissolution of the impurity-rich pyrite and precipitation of new pyrite and marcasite generations could have occurred at low pH plus high concentrations of dissolved Fe2+ condition caused by partial oxidation of aqueous H2S and/or S2− in ore fluids. The fluid oxidation is evidenced by a general decreasing trend of δ34S values from the parent euhedral pyrite, to product porous pyrite, euhedral marcasite, and complex-zoned marcasite. The isotopic results are consistent with ore fluid oxidation controlled by pressure fluctuations during multistage hydraulic fracturing in a fault-valve regime at Daqiao deposit. This quantitative study emphasizes that the pressure-driven hydrothermal process plays a key role in the micron- to nano-scale redistribution and re-enrichment of gold and other trace metals during episodic replacement of auriferous pyrite in brittle rheological zones from epizonal orogenic gold systems.

Enzyme activity indicates soil functionality affectation with low levels of trace elements

The use of the soil can alter its functionality and influence the (bio)availability of any contaminants present. Our study considers two types of agricultural soils, rainfed and olive soils, managed according to conventional practices that apply contaminants directly to the soil (fertilizers, pesticides, fungicides, etc.) and receive contaminants from the atmosphere (traffic, industry, etc.); and a forest soil that is not subject to these agricultural practices. In this scenario, we consider a mixture of 16 trace elements (As, Ba, Be, Cd, Co, Cr, Cu, Hg, Mo, Ni, Pb, Se, Sb, Sn, V and Zn), since their interactions with the soil can produce synergistic and/or antagonistic effects that are not considered in most studies. We studied whether the content and (bio)availability of low concentrations of a mixture of trace elements affect the soil functionality in terms of the activity of some key enzymes We analysed the total, potentially and immediately available fractions, the soil parameters and soil enzyme activity. The results show that the functionality of the soils studied was affected despite the low concentrations of trace elements. The highest concentrations of total trace elements and available fractions were found in forest soils compared to the other two uses. Soil enzyme activity is best explained by the potentially available fraction of a mixture of trace elements and physico-chemical soil variables. In our study, pH, total nitrogen, organic carbon and fine mineral particles (silt and clay) had an influence on soil enzyme activity and the (bio)available fractions of trace elements.

Mineralogical and geochemical criteria to identify the origin and the depositional environment of the upper Numidian babouchite siliceous rocks, northwestern Tunisia

The lower Miocene babouchite siliceous rocks from the Numidian Formation were widely deposited in the Northwestern of Tunisia, with a total thickness ranging from 20 to 50 m. The samples are principally composed of quartz and clay minerals (smectite, illite and kaolinite), with total lack of amorphous silica. The bulk chemical composition of the babouchite siliceous rocks is represented by high SiO2 (73.60–91.45%) and Al2O3 (5.78–10.55%) with negligible amounts of CaO, MgO, K2O and TiO2. The enrichment of these cherts by Mn and Cu, and the low content of the other trace elements are indicators of oxic condition in the water column. The ratio of Al/(Al + Fe + Mn) (0.65–0.87) is > 0.6 which is typical of a biogenic origin. Furthermore, the high ratios of Si/(Si + Al + Fe) justify the biogenic origin. All the analyzed samples from Babouch member fall into the non-hydrothermal sediment field of the Al-Fe-Mn diagram. Moreover, according to the environment discriminating diagrams, such as Al2O3/(100-SiO2) vs. Fe2O3/(100-SiO2), Al2O3/SiO2 vs. Fe2O3/SiO2 and Al2O3/(Al2O3+Fe2O3) vs. Fe2O3/TiO2, the babouchite siliceous rocks were deposited on a passive continental margin. The δ18O value of the chert, range from 24.9‰ to 27.9‰. The forming temperature determined by oxygen isotopic composition indicates formation at a slightly high temperature, about 65 °C.

Ancient volcanism on the Moon: Insights from Pb isotopes in the MIL 13317 and Kalahari 009 lunar meteorites

Lunar meteorites provide a potential opportunity to expand the study of ancient (>4000 Ma) basaltic volcanism on the Moon, of which there are only a few examples in the Apollo sample collection. Secondary Ion Mass Spectrometry (SIMS) was used to determine the Pb isotopic compositions of multiple mineral phases (Ca-phosphates, baddeleyite K-feldspar, K-rich glass and plagioclase) in two lunar meteorites, Miller Range (MIL) 13317 and Kalahari (Kal) 009. These data were used to calculate crystallisation ages of 4332±2 Ma (95% confidence level) for basaltic clasts in MIL 13317, and 4369±7 Ma (95% confidence level) for the monomict basaltic breccia Kal 009. From the analyses of the MIL 13317 basaltic clasts, it was possible to determine an initial Pb isotopic composition of the protolith from which the clasts originated, and infer a 238U/204Pb ratio (μ-value) of 850±130 (2σ uncertainty) for the magmatic source of this basalt. This is lower than μ-values determined previously for KREEP-rich (an acronym for K, Rare Earth Elements and P) basalts, although analyses of other lithological components in the meteorite suggest the presence of a KREEP component in the regolith from which the breccia was formed and, therefore, a more probable origin for the meteorite on the lunar nearside. It was not possible to determine a similar initial Pb isotopic composition from the Kal 009 data, but previous studies of the meteorite have highlighted the very low concentrations of incompatible trace elements and proposed an origin on the farside of the Moon. Taken together, the data from these two meteorites provide more compelling evidence for widespread ancient volcanism on the Moon. Furthermore, the compositional differences between the basaltic materials in the meteorites provide evidence that this volcanism was not an isolated or localised occurrence, but happened in multiple locations on the Moon and at distinct times. In light of previous studies into early lunar magmatic evolution, these data also imply that basaltic volcanism commenced almost immediately after Lunar Magma Ocean (LMO) crystallisation, as defined by Nd, Hf and Pb model ages at about 4370 Ma.

Iron ore deposits associated with Hormuz evaporitic series in Hormuz and Pohl salt diapirs, Hormuzgan province, southern Iran

Three types of iron ore, including banded ore, hydrothermal-metasomatic ore and earthy hematite ochre occur in Hormuz and Pohl salt diapirs. Primary banded ores of upper Neoproterozoic age contain alternating iron-rich and silica-rich bands, which characterized by the presence of folded hematite-rich bands and glacial diamictite fragments of quartz, dropstone and other clastics. Hematite as specularite and oligist is the major mineral in the iron-rich bands with minor goethite, pyrite, magnetite and rare siderite. Textural relationships between the ore and gangue minerals indicate that these ores are Rapitan-type sedimentary banded iron deposits. This is supported by the geochemical data of iron ores, such as low concentration of Al2O3, TiO2, Ba, V, Cr, Co, Ni, Cu and other trace elements, plus high value of MnO, Fe/V and Fe/Ti ratios, and REE patterns. Subsequent to the formation of iron ore deposits, an immense thickness of evaporitic rocks was formed in the oceanic marginal basins. Negative δ13C and δ18O values of the cap carbonates and strong positive δ34S values of the underlying sulfates are similar to the isotopic patterns of Ediacaran Rapitan-type iron deposits. Due to salt diapirism in the upper Mesozoic and Cenozoic eras, secondary iron deposits were formed by the activation of hot hydrothermal fluids during salt rising. High contents of some indicative elements such as Sr, Zr, U, Th, Pb, Zn, Sn, W and Mo in the metasomatic iron ores showed that they are the products of iron ore remobilization–redeposition in a hydrothermal system. The nearness of these ores to the fault zones is consistent with the scheme of migration and redeposition of iron compounds as metasomatic deposits under oxidizing conditions. Finally, earthy ochre was formed following the weathering and erosion of pre-existent iron ores.

In seam variation of element-oxides and trace elements in coal from the eastern Ordos Basin, China

This paper investigated the mineralogical and geochemical compositions of the upper Pennsylvanian coal from Hedong Coalfield, in the eastern Ordos basin, China, using SEM, XRD, ICP-MS, ICP-CCT-MS, DMA-80 and ISE methods. The bituminous coal samples were collected form Nos. 3 and 4 Coal, which had low ash yield and were medium volatile, and had low sulfur content and low hazardous trace elements concentrations (Be, F, As, Hg, U and Pb). Maceral compositions were dominated by vitrinite (up to 90.2%), and to a lesser extent by inertinite and liptinite, all subgroups were detected in the coal samples. Minerals included quartz, clay minerals, sulfide and other oxide minerals. SiO2 and Al2O3 were the dominant major elements-oxides in both coal seams with much higher concentrations than in Chinese coal, while other major elements-oxides (Na2O, K2O, Fe2O3, MgO) had average values compared to Chinese coal. No. 3 Coal was enriched in Li and Zr, and No. 4 Coal was enriched in Li, Be, Cu, Se, and In. Elemental occurrence was studied using statistical methods, and Li, Rb, Zr, Cs, Ba, Hf, Tl, Pb, and Th were inorganic affinities, while F, V, Cr, Ga, Ni, As, In, Ta occurred as inorganic–organic affinities and Fe and S may have occurred in pyrite. Coal facies indicators (GI, TPI, GWI, and VI) plots suggested that the two coal seams were deposited in different environments: No. 3 Coal was deposited in a wet forest swamp, while No. 4 Coal was formed in a mesotrophic to ombrotrophic environment. The geochemistry of these coal samples (Al2O3/TiO2, TiO2/Zr, Zr/Sc and Th/Sc ratios) indicated that the coal samples sediment was sourced from intermediate and felsic igneous rocks.

Geochemistry of Paleo to Mesoproterozoic Metasedimentary Units of Chandil Formation, North Singhbhum Crustal Province: Implications for Provenance and Source Area Weathering

ABSTRACT The Mesoproterozoic metasedimentary units of Chandil Formation belong to the northern part of Singhbhum crustal province, eastern India. The Formation lies north of Dalma volcano-sedimentary belt and is separated from the Meso-Neoproterozoic Chhotanagpur granite gneissic complex (CGGC) by Tamar-Porapahar shear zone (TPSZ), i.e. South Purulia shear zone, (SPSZ) at its northern boundary. The metasedimentary unit comprises of quartz-mica-sericite-schist, quartzite, amphibolites and carbonaceous phyllites, which have not been studied well, so far in terms of their geochemistry, source rock and provenance characterization. In this work, the existing gaps in all those aspects are studied to infer the provenance of these meta-sedimentary sequences. The high silica contents of the Chandil Formation (∼95% for the quartzites and ∼70% for the metapelites) and low trace element concentrations indicate silica-rich source. The REE patterns of the quartzites and the metapelites exhibit LREE enrichment and HREE depletion with moderate negative Eu-anomalies which strongly favor felsic nature of the provenance. The significant enrichment of LREE, flat HREE patterns and negative Eu-anomalies of the metapelites suggest their derivation from an old upper continental crust, which is composed of felsic components and the negative Eu-anomalies indicate intra-crustal differentiation. The higher concentrations of the HFSE i.e. Zr, Hf and Ta, within the Chandil metasediments relative to those of EPC (Early Proterozoic Continental Crust), also suggests a felsic provenance. The geochemical signatures of the Chandil metasediments indicate that the sediments were derived during a prolonged period of weathering due to the slow upliftment and unroofing of the southern evolving Singhbhum granitic complex (SGC).

The contrasting geochemical message from the New Caledonia gabbronorites: insights on depletion and contamination processes of the sub-arc mantle in a nascent arc setting

The New Caledonia ophiolite hosts one of the rare examples of crust-mantle sections built in a nascent arc environment, providing the unique opportunity to investigate the first stages of arc magmatism in a subduction setting. The sequence consists of refractory harzburgites, overlain by ultramafic (dunites and wehrlites) and mafic lithologies (gabbronorites). The gabbronorites occur in the upper part of the sequence as decimetre to metre-size sills. They are mainly formed (≃ 55 to 70 vol%) of Ca-rich plagioclase (An up to 96 mol%) and high Mg# (88–92), Al2O3-poor (1.5–2.4 wt%) clinopyroxene (8–20 vol%), often rimmed by interstitial or poikilitic orthopyroxene (6–27 vol%). Mg-rich olivine (3–15 vol%, Fo = 87–89 mol%) occurs as anhedral, resorbed crystals. Whole rock (WR) compositions exhibit high Mg# (86–92) and strikingly low trace element contents. They own LREE-depleted patterns, with nearly flat (0.82 ≤ DyN/YbN ≤ 1.00) and low HREE (YbN = 0.2–0.9) and positive Eu anomalies. Clinopyroxene trace element chemistry mirrors the extreme depletion of the WR. By contrast, FME enrichments are observed for WR and clinopyroxene. Geochemical models show that the gabbronorites crystallized from primitive, ultra-depleted melts bearing evidence of fluid contamination processes, but with significantly different geochemical signatures compared to boninitic rocks worldwide, i.e. lower LREE-MREE, and absence of Nb depletion and Zr–Hf enrichments. Nd isotopes (+ 8.2 ≤ eNdi ≤ + 13.1), together with radiogenic Pb isotopic ratios, support an origin from a DMM source variably modified by slab fluids. We propose that the geochemical signature of the New Caledonia gabbronorites reflect emplacement of primitive, non-aggregated, magma batches in the lower fore-arc crust, during the first phases of arc formation.

Nanosilver crystals capped with Bauhinia acuminata phytochemicals as new antimicrobials and mosquito larvicides

To develop novel nanoformulated insecticides and antimicrobials, herein we produced Ag nanoparticles (AgNPs) using the Bauhinia acuminata leaf extract. This unexpensive aqueous extract acted as a capping and reducing agent for the formation of AgNPs. We characterized B. acuminata-synthesized AgNPs by UV–vis and FTIR spectroscopy, XRD and TEM analyses. UV–vis spectroscopy analysis of B. acuminata-synthesized AgNPs showed a peak at 441.5 nm. FTIR shed light on functional groups from the phytoconstituents involved in nanosynthesis. XRD of B. acuminata-synthesized AgNPs suggested a face-centered cubic structure, with a highly crystalline nature. TEM of B. acuminata-synthesized AgNPs revealed mean size of 25 nm, with round shape. AgNPs tested at 60 μg/mL inhibited the growth of 5 bacteria and 3 fungal pathogens. In the insecticidal assays on important mosquito species, LC50 of the aqueous extract of B. acuminata leaves on the larvae of Anopheles stephensi, Aedes aegypti, and Culex quinquefasciatus were 204.07, 226.02, and 249.24 μg/mL, respectively. The B. acuminata-synthesized AgNPs exhibited higher larvicidal efficacy, with LC50 values of 24.59, 27.19, and 30.19 μg/mL, respectively. Therefore, herein we developed a single-step, reliable, inexpensive, and environmentally non-toxic synthesis process to obtain AgNPs with high bioactivity against pathogens and vectors. Given the effective antimicrobial and larvicidal activity, nanoparticles fabricated using plant extracts and extremely low concentrations of trace elements, such as silver, can be exploited for multipurpose activities. Our results pointed out that B. acuminata-synthesized AgNPs have a promising potential in antimicrobial food packaging, as well as a foliar spray to control plant pathogens in the field, and to synergize the efficacy of fungicidal and larvicidal formulations.

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.

Tectonothermal events in the Olympic IOCG Province constrained by apatite and REE-phosphate geochronology

ABSTRACTThe Olympic iron oxide–copper–gold province in South Australia contains numerous deposits and prospects, including the Olympic Dam Cu–U–Au–Ag deposit and the Acropolis prospect. The Acropolis prospect comprises massive, coarse-grained magnetite–apatite veins partly replaced by a hematite-stable assemblage. The apatite grains in the veins contain zones with abundant inclusions of other minerals (including monazite and xenotime) and low trace-element concentrations relative to the inclusion-free zones. The inclusion-rich apatite zones are interpreted to be formed from the recrystallisation of the inclusion-free apatite and remobilisation of U, Th and rare earth element (REE) from apatite into monazite and xenotime. Apatite, monazite and xenotime are all established U–Th–Pb geochronometers and offer the potential to constrain the alteration history of the Acropolis prospect. The LA-ICPMS U–Pb age of inclusion-free apatite is within error of the age of the host volcanic units (ca 1.59 Ga). Inclusion-rich apatite yields both near-concordant analyses that are within error of the inclusion-free apatite as well as highly disturbed (discordant) analyses. The most concordant analyses of monazite (Th–Pb) inclusions and xenotime (U–Pb) inclusions and rim grains indicate an alteration event occurred at ca 1.37 Ga and possibly also at ca 500 Ma. The disparity in age of the inclusion-rich apatite and the REE-phosphate inclusions (and rim grains) is suggested to be owing to the apatite being initially recrystallised at ca 1.59 Ga and modified again by a later event that also formed (or coarsened) most of the inclusions. Partial resetting of the majority of the monazite inclusions as well as the presence of significant amounts of common Pb has complicated the interpretation of the monazite results. In contrast, xenotime is a more robust geochronometer in this setting. The ages of the two post-1.59 Ga events that appear to have affected the Acropolis prospect do not correspond to any events known to have occurred in the Gawler Craton. The earlier (ca 1.37 Ga) age instead corresponds best with metamorphic–magmatic–hydrothermal activity in Laurentia, consistent with the proximity of Laurentia and the Gawler Craton inferred from palaeogeographic reconstructions. The later (ca 500 Ma) event corresponds to the Delamerian Orogeny and has been shown by prior studies to have also affected the Olympic Dam deposit.

Arsenic and Other Elemental Concentrations in Mushrooms from Bangladesh: Health Risks.

Mushroom cultivation has been increasing rapidly in Bangladesh. Arsenic (As) toxicity is widespread in the world and Bangladesh faces the greatest havoc due to this calamity. Rice is the staple food in Bangladesh and among all the crops grown, it is considered to be the main cause of As poisoning to its population after drinking water. Consequently, rice straw, an important growing medium of mushrooms in Bangladesh, is known to have high As content. The objective of this study was, therefore, to determine the concentrations of As in mushrooms cultivated in Bangladesh and to assess the health risk as well. It also considered other elements, including Cd, Cr, Co, Cu, Pb, Mn, Hg, Ni, and Zn concentrations in mushrooms from Bangladesh. The mean concentrations (mg/kg) of As, Cd, Cr, Co, Cu, Pb, Mn, Hg, Ni, and Zn in mushrooms were 0.51, 0.38, 0.28, 0.01, 13.7, 0.31, 11.7, 0.12, 0.28, and 53.5, respectively. Based on the dietary intake of mushrooms, the weekly intakes of As, Cd, Cr, Co, Cu, Pb, Mn, Hg, Ni, and Zn from mushrooms for adults were 0.0042, 0.0030, 0.0024, 0.0001, 0.1125, 0.0019, 0.1116, 0.0011, 0.0023, and 0.4734 mg, respectively. Due to the low concentrations of As and other trace elements observed in mushrooms from Bangladesh, as well as relatively lower consumption of this food in people’s diet, it can be inferred that consumption of the species of mushrooms analysed will cause no toxicological risk.