Laser Ablation Inductively Coupled Plasma Mass Spectrometry Research Articles

LA–ICP–MS analysis of sulfides from the Jianzhupo deposit, Guangxi Province, China: Insights into element incorporation mechanisms and ore genesis

The Jianzhupo deposit, the largest Zn-Sb deposit in the Wuxu orefield in China, contains abundant sphalerite and jamesonite, contrasting with typical Sb deposits elsewhere. Whether the Sb and Zn in the deposit derived from similar parental sources is not clearly resolved. Here, trace-element compositions of sulfides from the deposit were determined by laser ablation–inductively coupled plasma–mass spectrometry (LA-ICP-MS). Results indicate that jamesonite is an important Cd-bearing sulfide with Cd contents of 523–764 ppm and minor or no significant Cd variations were observed within jamesonite crystals. Trace-element compositions of jamesonite indicates that Cd enters the lattice by coupled substitution as 2Fe2+ ↔ Zn2+ + Cd2+. Due to similar geochemical behaviors between Zn and Cd in hydrothermal systems, Zn/Cd ratio of sphalerite was suggested as a robust geochemical tracer to distinguish metal sources in such systems. Here, we summarized the Zn/Cd ratios of sphalerite from various hydrothermal systems and the results show that values between 169 and 233, and lower than 44 are from high- and low-temperature temperature fluid conditions, respectively. Due to different Zn/Cd ratios between sediments and igneous rocks, we conclude that metals in sphalerite from the Jianzhupo deposit were likely derived from granite; in contrast, metals in jamesonite were related to sedimentary rocks. These conclusions are consistent with previous studies on the deposit. Overall, our results indicate that ore-forming fluids of the Jianzhupo deposit were derived from magmatic–hydrothermal and basin water. This study extends the application of trace-element compositions in resolving the sources of sulfides in hydrothermal systems.

Sex influences elemental variation in the mineralized vertebrae cartilage of round stingray (Urobatis halleri)

The elemental composition of mineralized vertebral cartilage has proven useful for reconstructing the movement and environmental history of elasmobranchs. However, the effects of intrinsic and extrinsic factors on vertebral chemistry have not been well explored, making meaningful interpretations of results difficult. This study quantified trace element incorporation along the corpus calcareum of 116 Round Stingray (Urobatis halleri) vertebrae and explored the influence of intrinsic (i.e., sex) and extrinsic (i.e., location and year) factors on vertebral edge chemical variations. We quantified eight element/Ca ratios (Li/Ca, Mg/Ca, Mn/Ca, Co/Ca, Cu/Ca, Zn/Ca, Sr/Ca, Ba/Ca) by laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS). Behavioral sexual segregation by Round Stingrays explained differences found in Mn/Ca, Zn/Ca, Sr/Ca, and Ba/Ca ratios. Higher vertebral Mn/Ca and Zn/Ca in females likely originate from the use of salt marsh habitats as a refuge as well as higher reproductive hormone concentrations during gestation, respectively. Female and male Round Stingrays were also found to have an inverse relationship between Sr/Ca and Ba/Ca, likely due to environmental differences (e.g., temperature) between their sexually segregated habitats. This study demonstrates how multielement signatures in vertebral cartilage may improve understanding of habitat use and migration throughout life and advances the development of biomineral usage as an environmental proxy in elasmobranchs.

Application of two-dimension, high-resolution evidences to reveal the biogeochemical process patterns of trace metals in reservoir sediments

Pollutions of trace metals (TMs) in reservoirs are blooming due to TMs were trapped efficiently in reservoir sediments by dams. Despite the mobilization of TMs in sediments have been well-documented, the patterns of biogeochemical processes occurred in sediments remain poorly understanding. Herein, a deep reservoir was selected to investigate the patterns of TMs biogeochemical processes in sediments by using high-resolution ZrO-Chelex-AgI diffusive gradient in thin films technique (HR-ZCA DGT) and the laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS). 2-dimension high-resolution (2D-HR) images showed significant differential spatial enrichment of TMs (V, Mn, Fe, Co, Zn and Sb) in sediments, indicating strong heterogeneity in sediments. Correlations of TMs within microniches (diameter < 1 mm) in horizontal were usually different even contrast with that in vertical profile, suggesting distinct biogeochemical process patterns occurred in vertical vs. in horizontal. Further analyses from 2D-HR images showed the distributions of TMs in microniches reflected their mobilization that was driven by microenvironmental conditions. In contrast, distributions in sediment vertical profile recorded the diagenesis in different deposition depth. The diagenesis in sediment vertical is continuously accumulated by the discrete, microniches mobilization of TMs in horizontal. Collectively, our findings evidenced that 2D-HR data is an update complement to 1-dimension data for better interpret the biogeochemical process patterns of TMs in sediments, that have implication for water management to metals pollution in reservoir ecosystems.

Relationship between cathodoluminescence response and trace element characterization of cassiterite from the Yunling tin deposit in western Yunnan, China: Implications for substitution mechanism and ore genesis

Cathodoluminescent (CL) imaging, combined quantitative geochemical analyses using laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS), was employed to study the cassiterite crystals from the Yunling tin deposit in western Yunnan Province, China. This investigation aimed to establish a connection between CL response with trace element compositions. The CL imaging of a well-formed centimeter-scale euhedral single crystal of cassiterite revealed two types of primary growth domains, namely oscillatory and sector zoning. High spatial resolution LA-ICP-MS spot analysis along three centimeter-scale profiles revealed that the oscillatory zoning patterns were primarily defined by the concentrations of Nb and Ta. The CL response associated with the oscillatory zoning was attributed to the interplay between activators such as Ti, Nb, Ta, and V, and quenchers like Fe. On the other hand, sector zoning exhibited significantly high W content, reaching three orders of magnitude greater than that in the oscillatory zoning. Consequently, the sectors displayed a dark CL response. Furthermore, U showed a sectoral preference, with contents within the sector zoning examined in this study reaching up to 10 ppm. The systematic variations in geochemical compositions suggest that the incorporation of trace elements in Yunling cassiterite involves a coupled substitutional mechanism of pentavalent and trivalent elements (e.g., Sc3+ + V5+ ↔ 2Sn4+) with H+ potentially serving as a compensating ion for the Fe3+ excess.It is worth noting that the trace element enrichment and potential substitution in the sector and non-sector regions of the single crystal may differ significantly. Therefore, the use of cassiterite trace elements as indicators of the mineralization environment requires careful consideration, particularly when analyzing randomly selected particles obtained from crushing. In such instances, it is recommended to utilize cassiterite samples that exhibit a preserved crystal texture extending from the core to the rim, such as cassiterite in thin sections or morphology-integral cassiterite separates. Moreover, the contrasting W contents observed between the sector and non-sector zones may provide an explanation for two trends in the Fe–W diagram of cassiterite associated with granite that were previously-unspecified.

Pre-cleaning of hair is not beneficial in LA-ICP-MS studies of chronic metal exposure.

Chronic exposure to toxic metals is a serious global health concern. However, population-wide biomonitoring is costly and carries several sampling constraints. Though hair sampling can be a useful way to assess environmental exposure, external contamination is a long-standing concern, and a pre-cleaning step prior to metal quantification has long been recommended despite a lack of evidence for its efficacy. In this study, we quantified the spatial distribution of 16 elements in unwashed human hair samples using Laser Ablation Inductively Coupled Plasma Mass Spectrometry (LA-ICP-MS), then tested how two common pre-cleaning treatments (Triton-ethanol, Triton-nitric acid) affected metal content in external and interior layers of hair using LA-ICP-MS. We show that elements differ in their spatial distribution across hair and that pre-cleaning is not consistent in its effect on element concentrations and decreases interior concentrations of some elements. We demonstrate that differences among individuals can be quantified reliably with LA-ICP-MS analysis of interior concentrations of unwashed hair. Our study tests the widespread notion that pre-cleaning is essential in analyses of hair for environmental exposure to metals, and examines the benefits of a unified approach to analysis of metals in hair using LA-ICP-MS.

Direct multi-elemental analysis of cerebrospinal fluid samples by LA-ICP-MS employing an aerosol local extraction cryogenic ablation cell.

A novel method for direct high-throughput analysis of multi-elements in cerebrospinal fluid (CSF) samples by laser ablation inductively coupled plasma mass spectrometry with an aerosol local extraction cryogenic ablation cell (ALEC-LA-ICP-MS) was developed. Microliter-level CSF samples were frozen by a designed cryogenic ablation cell and directly analyzed by laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) without time-consuming pretreatment. Compared with the precision obtained at room temperature (20℃), that obtained at low temperature (- 25℃) was significantly improved; the RSDs were reduced from 8.3% (Zn) to 32.6% (Mn) to 2.2% (Pb) to 6.5% (Mn) with six times parallel determination. To meet the analytical requirement of the micro-volume CSF samples, the laminar flow aerosol local extraction strategy was adopted to improve the transmission efficiency of aerosols, and the signal intensity was increased by four times compared with the standard commercial ablation cell. The standard solution with 0.4% bovine serum albumin (BSA) matrix was used as matrix-match external standard, and Rh was added into the samples as internal standard. The limits of detection (LODs) ranged from 0.17μg·L-1 (Mn) to 8.67μg·L-1 (Mg). Standard addition recovery experiments and the determination of CRM serum L-1 and L-2 were carried out to validate the accuracy of the method; all results indicated there were excellent accuracy and precision in the proposed method. The matrix-scanning function in the GeoLas software combined with themicrowell plate realizes the high-throughput automatic analysis. Twenty-four CSF samples from different patients were determined; the results showed that there might be a correlation between the metal elements in CSF and the diseases, which means that the proposed method has potential in the diagnosis of neurological diseases.

The blue road: Provenance study of azurite samples from historical locations through the analysis of minor and trace elements

The pigments used by artists since ancient times play an important role in historical, artistic, and cultural investigations. They allow the acquisition of useful information for the study of human and technological development. This research aims at differentiating the various sources of azurite exploited in antiquity, based on the study of minor and trace elements. Azurite is one of the most important blue pigments in art history, widely used during the Middle Age and Renaissance. However, very few studies investigated the provenance of the pigment, so today it is still not possible to clearly identify the sources of azurite exploited in the past. This study is based on the analysis of several samples of azurite belonging to the MUST collection (Museum of Earth Sciences, Sapienza University of Rome, Italy) and coming from different historical localities: UK, Italy, Germany, France, Romania and Slovakia (both representative of the resources within the ancient Kingdom of Hungary), Greece and Russia. The samples were analysed by electron microscopy (EMPA and SEM-EDX) and laser ablation-inductively coupled plasma-mass spectrometry (LA-ICP-MS), with the aim of detecting chemical features that are specific to the different azurite ore deposits.Among the trace elements analysed, Zn, As, Sn, Ca and Sr prove the most suitable for discriminating the origin of the samples, as well as rare earth elements. In particular, Ce and Eu anomalies are suggested as markers for the German and Hungarian localities.

Trace Element Analysis of Pyrite and Arsenopyrite Using the LA-ICPMS Technique in Pulai, Central Belt of Peninsular Malaysia

The Pulai gold deposit is one of the most promising gold prospects in the Central Belt of Peninsular Malaysia. It is found within the Permian-Triassic Gua Musang sequence of metasediments and metavolcanics and in a structurally controlled NE-SW major fault. Various ore minerals, including pyrite, arsenopyrite, chalcopyrite, sphalerite, pyrrhotite, and galena are typically associated with this deposit. Four types of pyrite (Pyrite 1, Pyrite 2, Pyrite 3, and Pyrite 4) and two types of arsenopyrite (Arsenopyrite 1 and Arsenopyrite 2) were characterised based on their morphological and textural differences. In this region, gold occurs as refractory gold in the nanoparticle form and in the state of Au+ within the structure of sulphides of variable concentrations. Through the detailed laser ablation inductively coupled plasma mass spectrometry (LA-ICPMS) trace element mapping analysis of pyrite and arsenopyrite, the main Au-bearing sulphides were found within vein-hosted Pyrite 4 and Arsenopyrite 2 during late phase mineralisation, while Pyrite 3 had the lowest Au concentration. Two phases of Au enrichment were recorded in Pyrite 4, mainly in the core (2 to 11.7 ppm; average 1.4 ppm) and margin of the grain (0.3 to 8.8 ppm; average 1.2 ppm), whereas the highest Au content was detected in the core of Arsenopyrite 2 (0.3 to 137.1 ppm; mean 31.9 ppm). The enrichment of Au is associated with As, forming a zoning elemental pattern distribution. Other trace elements, including Co, Ni, Sb, Pb, Bi, Cu, and Zn, show systematic variation in their composition between the various types of pyrite and arsenopyrite. For early-phase sulphides, the Au enrichment localised at the margin of Pyrite 2 and Arsenopyrite 1, together with Co–Ni, Pb–Bi–Sb, and Ag in the same oriented pattern, suggesting the remobilisation and redistribution of Au in sulfides. Meanwhile, the late crystallisation phase of vein-hosted sulphides formed a rich Au–As ore zoning pattern in the core of Arsenopyrite 2 and Pyrite 4. The second phase of Au enrichment continued at the margin of Pyrite 4 through the remobilisation and precipitation of Au together with Ni, Co, Sb, Pb, Bi, Ag, and Cu. Subsequent deformation then reactivated the late fluid system with the enrichment of Sr, Ba, Rb, Ag, and Zn along the fractures and outermost rim of Pyrite 4 and Rb–Sr–Ba–Pb–Bi along the rim of Arsenopyrite 2. The Pulai gold prospect is interpreted as an orogenic-style gold mineralisation where arsenic can be used as an indicator for proximity to ore mineralisation in exploration.

The effect of platinum-group minerals on differentiation of platinum-group elements in magmatic sulfide deposits: Evidence from the Cu-Ni-PGE deposits in the Yangliuping area of the Emeishan large igneous province, SW China

Platinum-group minerals (PGM) are important host phases for platinum-group elements (PGE) in magmatic sulfide deposits. Recent studies have demonstrated that some PGM, such as sperrylite, can crystallize early from sulfide liquids. It is important to determine whether and how these PGM particles affect the enrichment and differentiation of PGE in Cu-Ni-PGE deposits. The magmatic sulfide deposits in the Yangliuping area (mainly consisting of the Yangliuping deposit and Zhengziyanwo deposit) are the largest Cu-Ni-PGE deposits in the Emeishan large igneous province, SW China. Primitive-mantle normalized PGE patterns and fractional crystallization modelling show that massive ores in the Yangliuping deposit are enriched in Pd and Pt. In contrast, massive ores, breccia ores and Cu-rich ores in the Zhengziyanwo deposit are depleted in Pt. Scanning electron microscopy (SEM), laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS), focused ion beam (FIB) and transmission electron microscopy (TEM) were used to constrain the occurrence of PGE in the massive ores from the two deposits. Mass balance calculation shows that <7% of Ir, Rh and Pt occur in base metal sulfides (BMS, mainly pyrrhotite, pentlandite and chalcopyrite) as solid solution in both the Yangliuping and Zhengziyanwo massive ores. 17% and 91% Pd are present in solid solution within BMS in the Yangliuping and Zhengziyanwo massive ores, respectively. In the Yangliuping massive ores, PtAs2 and Pd-PGM particles were commonly found within BMS crystals, and Ir-Rh-(Pt) sulfarsenides enclosed in cobaltite-gersdorffite solid solution (CGSS) are enriched in Pt. In contrast, in the Zhengziyanwo massive ores, no PtAs2 particles and fewer Pd-PGM particles were found, and Ir-Rh-(Pt)AsS particles enclosed in CGSS are poor in Pt. The distribution, mineralogy and microstructures of Ir-Rh-(Pt)AsS, PtAs2 and Pd-PGM particles in both the Yangliuping and Zhengziyanwo deposits suggest that they mainly crystallized from sulfide liquids or formed from Pd-Pt-semimetal-rich droplets. We suggest that the incorporation of Pd-PGM and PtAs2 particles into MSS cumulates led to the enrichment of Pd and Pt in the Yangliuping massive ores. In the Zhengziyanwo deposit, early fractional crystallization of PtAs2 reduced the Pt content in sulfide liquids and resulted in the formation of Pt-depleted sulfide ores and low-Pt Ir-Rh-(Pt)AsS particles, but no Pt-rich sulfide ores have been found to date. As a result, the role of PGM particles should be considered when using PGE to trace the formation process of Cu-Ni-PGE deposits. This study also provides additional evidence that the behavior of Pt in sulfide liquids is influenced by thermodynamic conditions and As, and suggests a potential for Pt-rich sulfide ores exploration in the Zhengziyanwo deposit.

U-Pb-Hf isotope compositions of detrital zircons from Tongtian River sediments of northern-central Tibetan Plateau: Implications for the closure of the Jinshajiang Ocean

The closure time of the Jinshajiang Ocean (a branch ocean of the Paleo-Tethys) has been widely debated due to the complex structure and strong deformation of the northern-central Tibetan Plateau. In this paper, the U-Pb-Hf isotope compositions of detrital zircons from Tongtian River sand sediments from the northern-central Tibetan Plateau were analyzed via laser ablation-inductively coupled plasma-mass spectrometry (LA-ICP-MS). The UPb ages of the detrital zircons from Tongtian River sand sediments were distributed in six major groups: 2685–2346 Ma, 2035–1676 Ma, 1220–580 Ma, 544–407 Ma, 297–157 Ma, and 46–20 Ma. The εHf(t) values (range from −30 to +19) of the detrital zircons varied within a wide range from negative to positive, indicating that the zircons were sourced from diverse host magmas. The 46–20 Ma zircons and their Hf isotope compositions reveal that the far-field effect of the Cenozoic India-Eurasia plate collision triggered reworking of the Neoproterozoic basement of the North Qiangtang terrane. The U-Pb-Hf isotope compositions of these detrital zircons indicate that the Tongtian River sand sediments are composed of a mixture of materials from the Bayan Har-Songpan Ganzi terrane and the North Qiangtang terrane, with a contribution ratio of 3:7. The UPb ages and Hf isotope compositions of the zircons from the Tongtian River sediments and regional igneous rocks suggest that the εHf(t) values of the Permian zircons are predominantly positive while those of the Triassic, especially the Late Triassic, are negative. This marked shift most likely indicates that the closure of the Jinshajiang Ocean occurred by at least the Late Triassic.

High-carbon wood ash biochar for mine tailings restoration: A field assessment of planted tree performance and metals uptake

Unique properties of biochar render it appealing for revegetating and decontaminating historic, barren, and chemically complex mine tailings. Bottom ash from bioenergy facilities can contain high levels of charcoal residue, and thus qualify as a type of biochar; the wide availability of this material at low cost makes it of particular interest in the context of tailings remediation. Nevertheless, bottom ash is variable and often contains residual toxic metal/loids that could be phytoabsorbed into plant tissues. We implemented a replicated field trial on historic contaminated metal mine tailings in Northern Ontario (Canada) over a range of high‑carbon wood ash biochar (HCWAB) dosages (0–30 t/ha) to evaluate tree and substrate responses. Sapling survivorship and aboveground biomass growth were quantified over a 4-year period; substrate chemical parameters were measured using acid-digestion and ICP-MS, as well as ion exchange resin probes. To assess elemental composition of sapling tissues, we used electron probe microanalysis combined with laser-ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) on intact samples across the range of dosages applied. Survival and growth of saplings peaked at mid-range ash dosages of 3–6 t/ha. Similarly, substrate ion availability of P, K, and Zn were stable at lower dosages, but increased above 6 t/ha. The trace amounts of toxic metal/loids of concern measured in wood ash (As, Cd, Cu, and Pb) did not result in significantly increased sapling tissue concentrations at low to moderate dosages, but in some cases tissue contaminant levels were elevated at the highest dosage examined (30 t/ha). Our findings highlight the potential for high‑carbon wood ash biochar to be used for metal mine restoration at low to moderate dosages.

Pyritization and Preservation Model of Chrysophyte Cyst Fossils in Shales during the Triassic Carnian Pluvial Episode, Ordos Basin, China: Evidence from Cyclostratigraphy, Radiometric Dating and Geochemical Analyses

Chrysophyte cyst fossils were widely pyritized and preserved in black shales from the seventh member (Ch7 Mbr) of the Yanchang Formation in the Ordos Basin. The age, pyritization, and preservation model of these fossils have not been studied previously. In this study, the astronomical orbital cycles of the Ch7 Mbr were determined based on the gamma ray series of the Yan56 and Zhen 421 wells. An astronomical time scale (ATS) analysis revealed that the depositional duration of Ch7 Mbr was approximately 5 Ma. According to the 206Pb/238U radiometric dating of zircons using laser ablation inductively coupled plasma mass spectrometry (La-ICP-MS), the tuffs at the bottom of Ch7 Mbr were crystallized at 234 Ma, which served as a geological anchor. The ages of three submembers in Ch7 Mbr were estimated at 234.0–232.4 Ma, 232.4–230.8 Ma, and 230.8–229.1 Ma based on ATS analysis. In addition, chrysophyte cyst fossils were well preserved by pyritization in the Ch7 Mbr black shales. There were six types of microscopic morphologies with different pores, collars, and surface ornamentation under scanning electron microscopy (SEM). The age of the chrysophyte cyst fossils was at least 233.6 Ma in the Triassic Carnian Pluvial Episode (CPE) based on the 405 kyr tuned ATS. Moreover, the paleoredox conditions in Ch7 Mbr were reconstructed, and a preservation model of chrysophyte cyst fossils was established based on geochemical analyses. Fossil pyritization was caused by bacterial sulfate reduction near the water-sediment interface under suboxic to anoxic environmental conditions. Pyritization was initiated on the walls of the chrysophyte cysts by the formation of microcrystalline pyrite. Because of the gradual pyritization of the chrysophyte cyst wall, the organic matter in the interior of the fossil was well preserved.

Behavior of palladium during fractionation of sulfide liquid: New constraints from the Kalatongke Cu-Ni sulfide-bearing intrusion in the central Asian orogenic belt, NW China

The distribution of platinum-group elements (PGE; Os, Ir, Ru, Rh, Pt, and Pd) in base metal sulfides (BMS) of magmatic Ni-Cu-(PGE) sulfide deposits has been extensively studied. However, the origin of Pd in pentlandite and the role of Te, As, Bi, Sb, and Se (TABS) in collecting PGE during fractionation of sulfide liquid have not yet been well constrained. Representative massive sulfide ores of the Kalatongke Cu-Ni sulfide-bearing mafic intrusion in the central Asian orogenic belt (CAOB) were selected to identify platinum-group minerals (PGM) using a scanning electron microscope (SEM) and to investigate the distribution of PGE and TABS in the BMS using in situ laser-ablation inductively coupled-plasma mass spectrometry (LA-ICP-MS). The results show that concentrations of Os, Ir, Ru, Rh, and Pt in the BMS are all below or close to the detection limits and only pentlandite contains 0.1 to 3.6 ppm Pd. Three generations of pentlandite are recognized in the massive sulfide ores; i.e., coarse-grained, granular pentlandite that crystallized earlier from monosulfide solid solution (MSS) prior to crystallization of pyrrhotite, loop-textured pentlandite around pyrrhotite that crystallized after pyrrhotite, and pentlandite that crystallized from evolved Fe-rich MSS and is associated with fine-grained myrmekitic magnetite. Granular pentlandite contains higher Pd (1.4 to 3.6 ppm) than that of loop-textured pentlandite (0.8 to 1.7 ppm Pd) and pentlandite associated with myrmekitic magnetite (0.1 to 0.5 ppm Pd). Given that Pd is incompatible to MSS during fractionation of sulfide liquid and is preferentially concentrated to residual sulfide liquid, we propose that the distribution of Pd in pentlandite may be attributed to rapid diffusion of Pd from the residual sulfide liquid into MSS/pentlandite on cooling and that Pd concentrations in the three generations were likely controlled by their crystallization sequence from MSS. In addition, LA-ICP-MS elemental mapping for BMS shows that TABS are not preferentially concentrated in chalcopyrite and euhedral Ni-merenskyite [(Pd,Pt)(Te,Bi)2] grains are mainly enclosed within pyrrhotite (n = 187) rather than chalcopyrite (n = 19). The random distribution of Ni-merenskyite in the BMS is supportive of an idea that Pt and a portion of Pd were likely stabilized by the presence of Te and Bi ligands in sulfide liquid and Te-Bi-Pd-Pt associations were then randomly distributed in MSS and intermediate solid solution (ISS) during fractionation of sulfide liquid. This study shows that the formation of TABS-bearing PGM in the massive sulfide ores of the Kalatongke intrusion was not controlled by fractionation of sulfide liquid, providing a new case that the behavior of PGE is mainly controlled by TABS rather than their partitioning coefficients in sulfide liquid.

Technical note: In situ U–Th–He dating by 4He ∕ 3He laser microprobe analysis

Abstract. In situ U–Th–He geochronology is a potentially disruptive technique that combines laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) with laser microprobe noble gas mass spectrometry. Despite its potential to revolutionize (detrital) thermochronology, in situ U–Th–He dating is not widely used due to persistent analytical challenges. A major issue is that current in situ U–Th–He dating approaches require that the U, Th, and He measurements are expressed in units of molar concentration, in contrast with conventional methods, which use units of molar abundance. Whereas molar abundances can be reliably determined by isotope dilution, accurate concentration measurements are not so easy to obtain. In the absence of matrix-matched U–Th concentration standards and accurate He ablation pit measurements, the required molar concentration calculations introduce an uncertainty that is higher than the conventional method, an uncertainty that is itself difficult to accurately quantify. We present a solution to this problem by using proton-induced 3He as a proxy for ablation pit volume and by pairing samples with a standard of known U–Th–He age. Thus, the U–Th–He age equation can be solved using relative rather than absolute concentration measurements. Pilot experiments show that the new method produces accurate results. However, it is prone to overdispersion, which is attributed to gradients in the proton fluence. These gradients can be measured, and their effect can be removed by fixing the geometry of the sample and the standard during the proton irradiation.

Analysis of the elemental species-dependent uptake of lanthanide complexes in Arabidopsis thaliana plants by LA-ICP-MS

Gadolinium-based contrast agents (GBCAs) are found increasingly in different water bodies, making the investigation of their uptake and distribution behavior in plants a matter of high interest to assess their potential effects on the environment. Depending on the used complexing agent, they are classified into linear or macrocyclic GBCAs, with macrocyclic complexes being more stable. In this study, by using TbCl3, Gd-DTPA-BMA, and Eu-DOTA as model compounds for ionic, linear, and macrocyclic lanthanide species, the elemental species-dependent uptake into leaves of Arabidopsis thaliana under identical biological conditions was studied. After growing for 14 days on medium containing the lanthanide species, the uptake of all studied compounds was confirmed by means of laser ablation-inductively coupled plasma-mass spectrometry (LA-ICP-MS). Furthermore, the uptake rate of TbCl3 and the linear Gd-DTPA-BMA was similar, with Tb and Gd hotspots colocated in the areas of hydathodes and the trichomes of the leaves. In contrast, in the case of the macrocyclic Eu-DOTA, Eu was mainly located in the leaf veins. Additionally, Eu was colocated with Tb and Gd in the hydathode at the tip of the leave. Removal of the lanthanide species from the medium led to a decrease in signal intensities, indicating their subsequent release to some extent. However, seven days after the removal, depositions of Eu, Gd, and Tb were still present in the same areas of the leaves as before, showing that complete elimination was not achieved after this period of time. Overall, more Eu was present in the leaves compared to Gd and Tb, which can be explained by the high stability of the Eu-DOTA complex, potentially leading to a higher transport rate into the leaves, whereas TbCl3 and Gd-DTPA-BMA could interact with the roots, reducing their mobility.

The transition from hydrothermal oxic conditions to restricted euxinia in the lower cambrian yurtus formation black shale, Tarim Basin

The Yurtus Formation is generally believed as one of the most potential hydrocarbon source rocks under the Cambrian gypsum-salt bed in the Tarim Basin of China. This formation exhibits unique geochemical characteristics during the Ediacaran-Cambrian transition period. In this study, we investigated the lower and upper black shales from the Yurtus Formation for the high-resolution geochemical analysis in order to further characterize the prevailing redox conditions and sedimentary mechanisms involved in the organic matter accumulation process. During the deposition of the lower black shale with high TOC in Unit2, the high concentrations of phosphorite and barite, and the REE geochemistry manifested a mixture of hydrothermal fluid and seawater. Through in-situ laser ablation–inductively coupled plasma–mass spectrometry (LA-ICP-MS), we explored the element distribution of the drill-core-preserved phosphate nodule, indicating that the phosphogenesis may be related to the involvement of bacteria activities under intermittently oxic bottom waters or consistently free oxygen conditions. Biomarker evidence by the identification of green sulfur bacteria demonstrated the occurrence of photic zone euxinia (PZE), and the trace metal patterns revealed intermittently bottom water oxygenation and stratified ocean which was consistent with the scenario of phosphate nodule formation. In contrast, the upper black shale with relatively low TOC was characterized by a detrital input, with significantly decreasing redox-sensitive trace mental enrichment (UEF, MoEF, VEF) and positive excursion of carbon isotopes, as well as a positive relationship between ∑REE and Al. The present study provides more explicit insights into not only the sedimentary mechanism of the black shale, but also the evolution of the Earth system at the key interval of the early Cambrian.

Inferring the territoriality of Upper Palaeolithic hunter-gatherer’s groups settled at Cueva del Gato 2 (Épila, Zaragoza)

In recent decades, the development of different analytical procedures applied to the study of archaeological lithic remains has allowed us to approach the territoriality of past societies. The application of geochemical tools has improved the study of lithic raw materials, allowing direct connections between archaeological samples and specific geological formations. In a similar way, the incorporation of GIS tools to the study of past mobility and territoriality has allowed to define which could have been the most probable routes used by past groups to stock up on rocks. In this paper, we present the results obtained after the geochemical study by Laser Ablation Inductively Coupled Plasma Mass Spectrometry (LA-ICP-MS) of lithic cherts found at Upper Palaeolithic human occupations at Cueva del Gato 2 (Épila, Zaragoza, Spain) as well as the least cost path routes obtained after GIS analyses. The Cueva del Gato 2 archaeological site is a large cave placed in the first foothills of the Iberian System, close to the Middle Ebro Basin, in Eastern Iberia. The archaeological work has revealed a long sequence of occupation with archaeological levels from the Bronze Age, the Ancient Neolithic and the Upper Palaeolithic. In this paper, we have focused on the study of level II, which has been dated in the range 21,000–23,000 cal BP. Results have demonstrated that past human groups from the Last Glacial Maximum knew and frequented the Sierra de Lanaja – Montes de Castejón lacustrine chert sources, outcropping in the Middle Ebro Basin.

Short note. A new U-PB age for the Talampaya Formation: Stratigraphic and paleoclimatic implications

This paper presents a new U–Pb zircon age of 253.40 ± 1.06 Ma for the middle part of the Talampaya Formation, which is consistent with the previously reported dating of 252.38 ± 0.22 Ma at the top of the unit. The age herein presented was obtained from a tuff level intercalated into a fluvial sequence formed by finning-up cycles of massive conglomerates, cross-bedded sandstones, and laminated sandy mudstones interpreted as deposited by sandy meandering rivers with dominant sandy floodplains. In this context, a vitric tuff from a floodplain located 140 m from the base of the unit provided the zircons dated by the combination of LA-ICP-MS (Laser Ablation – Inductively Coupled Plasma – Mass Spectrometry).The radiometric age of 253.40 ± 1.06 Ma confirms the relocation of the Talampaya Formation in the Late Permian and demonstrates that at least the upper half and probably the whole of this unit was deposited during the Lopingian, a time interval scarcely represented in South America. This assumption is consistent with the age of 249.66 ± 0.11 Ma (early Triassic) reported in the overlying La Veteada Formation.The new age presented has paleoclimatic implications regarding the worldwide climatic aridification event that occurred at the end of the Late Paleozoic since it gives a relatively precise approximation to the onset of the aridization in this part of Gondwana during the Lopingian (circa 252.38 Ma).

Geochemical Characteristics of Garnet from Zinc–Copper Ore Bodies in the Changpo–Tongkeng Deposit and Its Geological Significance

The Changpo–Tongkeng tin polymetallic deposit in Dachang, Guangxi, is a world-class, superlarge, polymetallic tin deposit consisting of lower skarn zinc–copper ore bodies and upper tin polymetallic ore bodies. Garnet is the main gangue mineral in the skarn zinc–copper ore bodies and has a granular texture. Based on hand specimens and microscopic observations, the existing garnet can be divided into two generations: an early generation (Grt I) and a late generation (Grt II). The results of electron probe microanalysis (EPMA) and laser ablation-inductively coupled plasma-mass spectrometry (LA-ICP-MS) in situ microanalysis show that the contents of SiO2 and CaO in the garnets from the two generations present limited variations, while the FeOT and Al2O3 contents vary significantly, indicating the grossular–andradite solid solution series (Gro29–82And12–69). Compared with Grt I (Gro72And25), Grt II (Gro39And59) is Fe-enriched and oscillatory zoning is developed. The total rare earth element (REE) contents in the two generations of garnet are relatively low, showing light rare earth element (LREE) depletion and heavy rare earth element (HREE) enrichment patterns. Grt II has higher REE content than Grt I and exhibits significant negative Eu anomalies (δEu = 0.18–0.44). The contents and variation characteristics of the major and trace elements in the two generations of garnet suggest that there were variable redox conditions and water/rock ratios in the hydrothermal system during the crystallization process of garnet. In the early stage, skarnization was in a relatively closed and low-oxygen fugacity system, with hydrothermal diffusion metasomatism being dominant, forming homogeneous Grt I lacking well-developed zoning. In the late stage of skarnization, the oxygen fugacity of the ore-forming fluids increased, with infiltration metasomatism being dominant, forming Grt II with well-developed oscillatory zoning. The contents of Sn, As, W, In, and Ge in the garnets are relatively high and increase with the proportion of andradite. Sn in zinc–copper ore bodies mainly exists in the form of isomorphic substitution in garnet, which may be the main reason for the lack of tin ore bodies during the skarn stage. This paper compares the trace element contents in garnets from domestic skarn deposits. The results indicate that the Sn content and δEu in garnet can be used to evaluate the tin-forming potential of skarn deposits.

Age and origin of Early Cretaceous magmatism in the southernmost Omineca Belt, northern U.S. Cordillera

We present results of a geochronological and geochemical study of the Kaniksu batholith, located in northern Idaho and Washington near the Canadian border. This batholith occurs at the southern end of the Omineca Belt and forms an integral part of the Priest River metamorphic complex. The Kaniksu batholith is compositionally diverse, but granitoids can be grouped into a volumetrically major peraluminous and metaluminous suite and a volumetrically minor alkalic suite based on lithology and major-element composition; additional compositionally similar alkalic plutons extend far to the south of the main footprint of the batholith. Laser ablation−inductively coupled plasma−mass spectrometry (LA-ICP-MS) U-Pb zircon dating revealed that most granitoids of the batholith formed in the Early Cretaceous between 120 Ma and 100 Ma, although magmatism continued until ca. 73 Ma. The dominance of Early Cretaceous ages closely matches magmatic age distributions elsewhere in the Omineca Belt. There is no clear relationship between age and suite assignment or other geochemical characteristics. Whole-rock Sr, Nd, and Pb isotope data along with zircon Hf isotope data suggest that the alkalic and metaluminous suites can largely be explained as mixtures of partial melts from the Mesoproterozoic Moyie sills and metasedimentary rocks of the Belt Supergroup, whereas a third component, perhaps Paleoproterozoic or Neoarchean meta-igneous basement, is required to explain the origin of the peraluminous suite. All of these granitoids formed well behind the Cordilleran arc front in an area characterized by multiple episodes of crustal thickening. As there is little evidence of contemporaneous mantle-derived magmatism, crustal thickening was probably the main driver of batholith formation.