Laser Ablation Inductively Coupled Plasma Mass Spectrometer Research Articles

The influence of oxygen fugacity and chlorine on amphibole–liquid trace element partitioning at upper-mantle conditions

Abstract. The recycling of volatile and incompatible elements through the entire Earth's history is one of the most important processes for the chemical evolution of the lithosphere. In this context, amphiboles are important hydrous minerals playing a key role in the chemical differentiation of the crust–mantle system. We carried out amphibole–liquid partitioning (Amph/LD) experiments starting from a hydrous alkali basalt with variable chlorine content and doped in 37 trace elements of geochemical interest. Experiments were conducted with an end-loaded piston cylinder apparatus at a fixed pressure of 1.4 GPa, temperature from 1015 to 1050 ∘C, and at two different oxygen fugacity conditions (fO2; ΔFMQ ≈-2.6 (log fO2 [experiment] − log fO2 [FMQ buffer]) and ΔFMQ ≈+ 1.7). These conditions approach those of the Earth's upper mantle chemically metasomatised by subduction-derived agents that may occur in several geological settings. All runs show Ti-pargasites and kaersutites, either as individual crystals or replacing former clinopyroxenes, in equilibrium with alkali-rich (4 wt %–6 wt %) and silica-intermediate (52 wt %–59 wt %) melts. A comprehensive trace element dataset (LLEs – light lithophile elements, LILEs – light ion lithophile elements, REEs – rare Earth elements, HFSEs – high field strength elements, actinides, transition metals, chalcophiles) has been determined in glass and amphibole with a laser ablation inductively coupled plasma mass spectrometer (LA-ICP-MS). Although the melt polymerization has a major influence on Amph/LDs, we provide evidence that changes in the fO2 of both the system and Cl content in amphibole (up to 0.88 wt %) also affect the Amph/LDs of several trace elements and their ratios. In particular, at higher fO2 conditions lower Amph/LD values for U and Mo are observed likely in relation to the low capability of amphibole to incorporate the more oxidized forms of these cations. The Amph/LDTh/Amph/LDU ratio is positively correlated with the Cl content in amphibole, while the opposite behavior is shown by Amph/LD ratios of other elements with the same charge and different ionic radius (e.g., Gd / Yb, Nb / Ta, and Pb / Ba). Dimensional modification of the amphibole structure in relation to the incorporation of Cl in the O(3) site are at the origin of the observed variations. General implications of our results are discussed.

Ni–Fe–Co alloy – magnesia-iron-silicate slag equilibria and the behavior of minor elements Cu and P in nickel slag cleaning

The increasing demand for metals and the tightening environmental restrictions on industries have led to a situation where improvements of new and existing process technologies for higher metal recoveries from primary and secondary resources are needed. This, in turn, requires a better understanding of process chemistry. The present study provides important fundamental information on the equilibrium reduction path and the formation of metal alloy in an electric furnace under nickel slag cleaning conditions, as well as the chemical properties of Ni, Co, Cu and P at these conditions. High-temperature equilibration experiments were conducted on magnesia-iron-silicate slags at silica saturation at 1400 ˚C (1637.15 K) and in the oxygen partial pressure range of 10 −11 –10 −7 atm (1.01325 × 10 −6 –10 −2 Pa). The samples were analyzed by electron microprobe (EPMA) for major and minor elements and laser ablation inductively coupled plasma mass spectrometer (LA-ICP-MS) for trace element compositions. Initially the slag contained 2 wt% Ni and 1 wt% Cu, Co and P each, added as oxides, and at P O2 = 10 −7 atm, these metals were only present in the slag with no metal alloy formed. At lower partial pressures, the alloy formed and its composition changed from 90wt-% Ni-rich to 50 wt-% Ni – 40 wt% Fe alloy as the P O2 decreased. Copper vaporized to a great extent at all conditions. The minor metals were shown to be present as NiO, PO 2.5 , CoO and CuO 0.5 species in slag over the P O2 = 10 −8 –10 −10 atm range.

Application of Raman spectroscopy for the identification of phosphate minerals from REE supergene deposit

AbstractAmong critical metals, rare‐earth elements (REEs) are irreplaceable for their role in the high‐tech industry. The REE deposits commonly host REEs in fine‐grained mixtures of phosphate minerals characterized by the variable content of volatile components. However, identification of the volatile components may present challenges for laser‐ablation inductively coupled plasma mass spectrometer (LA‐ICP‐MS) and electron microprobe (EPMA) techniques. Therefore, Raman spectroscopy was applied to laterite and carbonatite samples from the Mount Weld deposit, one of the major REE deposits in Western Australia. The hydrous REE phosphate, rhabdophane, can be confidently distinguished from monazite by the presence of peaks in the region 2800–3600 cm−1. The presence of peaks at 428, 448, 579, 589, and 605 cm−1 in the Raman spectra of apatite from carbonatite allows its identification as hydroxyfluorapatite with high concentrations of F and water, and negligible Cl, SO42−, and SiO42−. The Raman spectra and composition of silcrete and carbonatite apatite are similar; thus, silcrete apatite was identified as hydroxyfluorapatite as well. The content of CO32− in both types of apatite was negligible despite the crystallization from carbonatitic magma. The aluminophosphate florencite is characterized by the presence of PO43−‐related peaks at 639, 1113, and 1609 cm−1 and H2O/OH‐related bands in the 2750–3075 cm−1 and together with rhabdophane has been identified in fine‐grained mineral mixtures. Our study demonstrates that combining Raman spectroscopy with compositional data is a powerful method for the characterization of phosphate minerals in REE deposits.

Imaging of Metal Ions and Nanoparticles on Structured Silicon Surface Using Laser Ablation-Inductively Coupled Plasma-Mass Spectrometer for Contamination Control in Semiconductor Manufacturing Process

In this study, the imaging of metal ions and nanoparticles deposited on a structured silicon surface was investigated using a laser ablation-inductively coupled plasma-mass spectrometry (LA-ICP-MS). For application, 8 $\times $ 8 Petri-dish pillars, each with a diameter of 250 $\mu \text{m}$ and height of 300 $\mu \text{m}$ , were constructed on a silicon wafer. The etched pillar surface took a droplet of approximately 4.3 nL aqueous solution from a capillary tip through the surface-liquid attraction. The dissolved materials were found at the intersecting edge of pillar bottom after evaporation, and their positions were matched with the peaks of elements in the mass spectrum for imaging. Results suggest that the trace contaminants in the cleaning solution are gathered at the intersecting edges of the patterned wafer, and the multi-elemental images of the contaminants can be successfully obtained using LA-ICP-MS.

Petrogenesis of oligocene plutonic rocks in western Anatolia (NW Turkey): Insights from mineral and rock chemistry, Sr-Nd isotopes, and U-Pb, Ar-Ar and (U-Th)/He geochronology

Northwestern Anatolia is characterized by voluminous Paleozoic to Cenozoic granitoid bodies with varying compositions. Most of them are composite plutons emplaced into western Anatolia orogenic crust during the Eocene, Oligocene and Miocene along the İzmir-Ankara-Erzincan suture zone. This paper reports systematic good quality mineral and bulk-rock chemistry, Sr-Nd isotope data, honblend Ar-Ar, zircon U-Pb and first apatite (U-Th)/He (AHe) ages to reveal possible source compositions of the Evciler and Eybek granitoids and petrogenetic/geodynamic processes involved during their genesis, and thermochronology of Oligocene magmatism in the NW Anatolia. The Evciler and Eybek granitoids are mainly granodiorite and composed of K-feldspar (usually orthoclase and rarely microcline), plagioclase (albite, oligoclase), hornblende, biotite, quartz and accessory minerals (e.g., titanite, zircon, apatite, opaque), and secondary minerals such as chlorite, sericite and clay minerals. Estimated temperature-pressure conditions are 690–770 ° C at 1.6–2.7 kbar for the Evciler granitoid and 690–760 ° C at 3.2–4.01 kbar for the Eybek granitoid. These two granitoids enriched in LILEs (e.g., U, Th, Rb, and K), LREEs and Pb, and depleted in HREEs (e.g., Nb, Ti) and Sr, Ba and P relative to LILEs, and display small negative Eu anomalies. They belong to calc-alkaline, high-K calc-alkaline and minor shoshonite series, and display metaluminous and I-type character. Their REE patterns show a large fractionation between LREE and HREE ((La/Yb)N = 4.6–21.4) and a small negative Eu anomaly (Eu* = 0.2–0.3). The Evciler granitoid has homogeneous 87Sr/86Sr = 0.7060−0.7063 and 143Nd/144Nd = 0.51259−0.51262, and the Eybek granitoid has 87Sr/86Sr = 0.7060−0.7080 and 143Nd/144Nd = 0.51243−0.51263. New precise 40Ar/39Ar age data of hornblende and 206Pb–238U ages of zircons and (U-Th)/He ages of apatites from the plutons allow a more accurate temporal reconstruction of the Cenozoic magmatism of the western Anatolia. 40Ar/39Ar dating of hornblendes from the Evciler and Eybek granitoids gave plateau ages of between ca. 28 Ma and 25 Ma. Laser ablation inductively coupled plasma mass spectrometer (LA-ICP-MS) 206Pb-238Pb ages of euhdral magmatic zircons from the samples of these granitoids yield between ca. 28 and 26 Ma. The new high-temperature age constraints indicate Oligocene emplacement ages for the two intrusive bodies. The closeness of the zircon U-Pb and the hornblende Ar-Ar ages show that they experienced quick post-crystallization cooling. However, the significant difference between the apatite (U-Th)/He ages of 19.8 Ma and 7.6 Ma obtained on the Evciler and Eybek granitoids warns that in the post-Oligocene times the two structural blocks had different exhumation histories.

The use of ASH-15 flowstone as a matrix-matched reference material for laser-ablation U − Pb geochronology of calcite

Abstract. Latest advances in laser ablation inductively coupled plasma mass spectrometer (LA-ICPMS) allow for accurate in situ U−Pb dating of carbonate material, with final age uncertainties usually >3 % 2σ. Cross-laboratory reference materials (RMs) used for sample-bracketing are currently limited to WC1 calcite with an age of 254.4±6.5 (2σ). The minimum uncertainty on any age determination with the LA-ICPMS method is therefore ≥2.5 %, and validation by secondary RMs is usually performed on in-house standards. This contribution presents a new reference material, ASH-15, a flowstone that is dated here by isotope dilution (ID) thermal ionization mass spectrometry (TIMS) analysis using 37 sub-samples, 1–7 mg each. Age results presented here are slightly younger compared to previous ID isotope ratio mass spectrometry (IRMS) U−Pb dates of ASH-15 but within uncertainties and in agreement with in situ analyses using WC1 as the primary RM. We provide new correction parameters to be used as primary or secondary standardization. The suggested 238U∕206Pb apparent age, not corrected for disequilibrium and without common-lead anchoring, is 2.965±0.011 Ma (uncertainties are 95 % confidence intervals). The new results could improve the propagated uncertainties on the final age with a minimal value of 0.4 %, which is approaching the uncertainty of typical ID analysis on higher-U materials such as zircon. We show that although LA-ICPMS spot analyses of ASH-15 exhibit significant scatter in their isotopic ratios, the down-hole fractionation of ASH-15 is similar to that of other reference materials. This high-U (≈1 ppm) and low-Pb (<0.01 ppm) calcite is most appropriate as a reference material for other speleothem-type carbonates but requires more-sensitive ICP-MS instruments such as the new generation of single-collector and multi-collector ICP-MS. Reference materials with high-Pb and low-U or both low-U and low-Pb compositions are still needed to fully cover the compositional range of carbonate material but may introduce analytical challenges.

Exploration of Matrix Effects in Laser Ablation Inductively Coupled Plasma Mass Spectrometry Imaging of Cisplatin-Treated Tumors.

The use of a low aerosol dispersion ablation chamber within a laser ablation inductively coupled plasma mass spectrometer (LA-ICP-MS) setup allows for high-resolution, high-speed imaging of the distribution of elements within a sample. Here we show how this enhanced capability creates new analytical problems and solutions. We report the distribution of platinum at the cellular level in non-small cell lung cancer (NSCLC) explant models after treatment with clinically relevant doses of cisplatin. This revealed for the first time a correlation between the platinum signal and the presence of carbon deposits within lung tissue. We show how complementary ion beam analysis techniques, particle-induced X-ray emission (PIXE) and elastic backscattering spectrometry (EBS), can be used to explore potential matrix effects in LA-ICP-MS data. For these samples, it was confirmed that the enhancement was unlikely to have resulted from a matrix effect alone. Thus, the presence of carbon deposits within tissue has potential implications for the effective distribution of the cisplatin drug.

Trace element signatures in hematite and goethite associated with the Kiggavik–Andrew Lake structural trend U deposits (Nunavut, Canada)

Hematite and goethite from 100 samples collected from various uranium deposits and prospects, associated alteration zones, and overlying Thelon sandstones in the Kiggavik–Andrew Lake structural trend (KALST; Nunavut, Canada) were investigated by EPMA (electron probe micro-analyzer) and LA-ICP-MS (laser ablation-inductively coupled plasma-mass spectrometer) to establish discriminant geochemical features in order to constrain indicator mineral exploration for uranium. Three groups of Fe oxides and hydroxides were identified: (1) pre-mineralization—formed during lateritic weathering mainly by replacement of previous metamorphic minerals. This group is variably enriched in P, Pb, Mo, Nb, Cu, Cr, Ni, and Co. (2) Syn-mineralization hydrothermal hematite and goethite intergrown with illite, quartz, chlorite, and calcite ± siderite constituting the typical alteration assemblage associated with the KALST U mineralization. This group can be discriminated because of its enrichment in U, Ca, Mg, Al, Si, Mn, Y, ∑REE, Zr, K, S, and Sr and depletion in P, Fe, Cr, W, Sn and Ta. The flat and un-fractionated REE patterns in this group are comparable with those reported from Kiggavik U mineralized host rocks and are most likely reflecting the signature of parental uraniferous fluids. (3) Post-mineralization hydrothermal specularite and goethite, infilling the KALST host rocks fractures and dissolution pits, are mostly depleted in Mn, Co, Y, Sr, U, and ∑REE but relatively enriched in Cr, Sn, Ta, Ge, and W. Partial least squares-discriminant analysis (PLS-DA) of the geochemical data not only differentiates among different groups of Fe oxides and hydroxides in the KALST samples but also demonstrates the evolution of trace element composition of Fe oxides and hydroxides from the basement host rocks to the mineralization. The results suggest a basement source for the U mineralization in the KALST area.

High-resolution LA-ICP-MS trace-element mapping of magmatic biotite: A new approach for studying syn- to post-magmatic evolution

ABSTRACT Biotite grains from 22 felsic intrusions in New Brunswick were mapped in situ using a laser ablation-inductively coupled plasma-mass spectrometer (LA-ICP-MS). We investigated the extent to which biotite can retain its magmatic zoning patterns and, where zoning does exist, how it can be used to elucidate early to late stage, syn-magmatic to post-crystallization processes. Although the major element and halogen contents of the examined biotite phenocrysts are homogeneous, two-thirds of the grains display trace-element zoning for Ba, Rb, and Cs. The results also indicated that zoning is better retained in larger grains (i.e., > 500 × 500 μm) with minimal alteration and mineral inclusions. An exceptionally well-zoned Li-rich siderophyllite from the Pleasant Ridge topaz granite in southwestern New Brunswick shows Ti, Ta, Sn, W, Cs, Rb, and V (without Li or Ba) zoning. Cesium values increase from 200 to 1400 ppm from core to rim. Conversely, Sn and W values decrease toward the rim (50 to 10 and 100 to 10 ppm, respectively). Tantalum and Ti values show fewer variations but drop abruptly close to the rim of the grain (100 to 20 and 2000 to 500 ppm, respectively). These observations may indicate crystallization of mineral phases with high partition coefficients for these highly incompatible elements (except Ti) (e.g., cassiterite and rutile) followed by fractionation of a fluid phase at a later stage of magma crystallization. The preservation of zoning may indicate rapid cooling post-crystallization of the parent magma.

Constraints on the Genesis of the Qixiashan Pb-Zn Deposit, Nanjing: Evidence from Sulfide Trace Element Geochemistry

The large-scale Qixiashan Pb-Zn Deposit in the eastern Middle-Lower Yangtze metallogenic belt is hosted in carbonate rocks. Based on a detailed mineral paragenesis study, in-situ LA-ICP-MS (laser ablation inductively coupled plasma mass spectrometer) trace element geochemistry data for pyrite and sphalerite from different stages in the Qixiashan Deposit are reported, the Pb-Zn mineralization processes are reconstructed, and a genetic model is constructed. Four paragenetic stages of Pb-Zn ore deposition are identified: the biogenic pyrite mineralization stage (Stage 1), the early stage of hydrothermal Pb-Zn mineralization (Stage 2), the late stage of hydrothermal Pb-Zn mineralization (Stage 3), and the carbonate stage (Stage 4). Stages 2 and 3 are the main ore stages. The trace element characteristics of the sulfide in stages 2 and 3, such as the higher Co/Ni and lower trace element contents of the pyrite and the Fe, Mn, and Ge contents of the sphalerite, indicate that they were generated by magmatic-hydrothermal processes. Furthermore, the lower Cu, Ag, Sb, and Pb contents of the pyrite and sphalerite of Stage 3 compared to Stage 2 suggest an increase in magmatic-hydrothermal activity from Stage 2 to Stage 3. The hydrothermal fluids leached trace elements (e.g., Cu, Ag, Sb, and Pb) from the previously deposited primary pyrite and sphalerite, which were precipitated in the later hydrothermal stage Cu, Au, Ag, Sb, and Pb bearing minerals and secondary pyrite and sphalerite with lower trace element contents (e.g., Cu, Au, Ag, Sb, and Pb). Compared with the pyrite from stages 2 and 3, the Stage 1 pyrite has relatively higher trace elements contents (Sb, Cu, Zn, Au, Ag, Pb, As, and Ni). However, their lower Co/Ni ratio suggests a syngenetic sedimentary origin. Based on the petrographic features and trace element data, a multi-stage mineralization model is proposed. The Stage 1 biogenic pyrite formed stratiform pyrite layers, which provided reducing conditions and a base for the subsequent Pb-Zn mineralization. During Stage 2, subsequent hydrothermal fluid interacted with the stratiform pyrite layers, which resulted in sulfide precipitation and the formation of stratiform Pb-Zn orebodies. In Stage 3, the hydrothermal fluid replaced the limestone along the fractures, which triggered the formation of Pb-Zn vein orebodies.

LA-ICP-MS dating of high‑uranium columbite from no. 1 pegmatite at Dakalasu, the Chinese Altay orogen: Assessing effect of metamictization on age concordance

High‑uranium (~4200 to 8500 ppm U) columbite-group minerals (CGMs) from No. 1 pegmatite at Dakalasu, the Chinese Altay orogen were used to assess the effect of metamictization on the UPb isotopic systematics. Backscattered electron (BSE) imaging shows that the high U concentrations are due to the U in the crystal structure itself. In the rims, the part of CGM next to cracks or pores filled by titan-uranoan fluorcalciomicrolite is altered. The microlite was likely formed via a dissolution-reprecipitation process that resulted in fractionation between U and Pb and potential discordance of the UPb isotopic systematics in the altered CGM.Raman spectroscopy indicates that the columbite samples are metamictized to various extents. However, the CGM samples dated by laser ablation – inductively coupled plasma – mass spectrometer (LA-ICP-MS) show excellent UPb age concordance, with thirty eight out of forty analyses displaying concordant UPb ages (229.0 ± 1.0 Ma to 228.1 ± 0.6 Ma) overlapping within analytical uncertainty (2σ). The alpha-decay doses are estimated to be 1.53 to 2.31 × 1015 α-decay events/mg, indicating that the CGMs are at a transition stage from being crystalline to completely metamict states. Although spatial separation between U and radiogenic Pb isotopes caused by α-recoil is inevitable, the displacement is on sub-micron scale, much smaller than the scale of laser ablation pits (43 μm) for LA-ICP-MS dating. Therefore, the UPb isotopic systematics of partially metamict, U-rich CGM may still remain concordant for CGMs that have not suffered hydrothermal alteration or metasomatism and do not contain U- or Pb-rich inclusions within the laser ablation pits. Additionally, the chemical compositions of the CGM have no control over the UPb isotopic systematics.

Trace element contents and in situ sulfur isotope analyses of pyrite in the Baiyun gold deposit, NE China: Implication for the genesis of intrusion-related gold deposits

Trace elements distribution in minerals and formation mechanism of visible gold are poorly understood in intrusion-related gold systems. Here, we choose the Baiyun gold deposit, which is hosted within the Paleoproterozoic metamorphic rocks in the Liaodong Peninsula, NE North China Craton (NCC), as a case study, to address these issues. The ore deposit geology characteristics and paragenesis are described in details; In situ geochemical and sulfur isotopic compositions of pyrite and bulk Pb isotopic ratios of pyrite were presented to define the genesis of pyrite that is closely associated with gold mineralization. Three generations of pyrite were recognized based on petrographic studies: metamorphic pyrite (Py0), hydrothermal pyrite (Py1) coexisting with milky quartz, and hydrothermal pyrite (Py2) coexisting with smoky quartz. In situ laser ablation-inductively coupled plasma-mass spectrometer (LA-ICP-MS) spot analysis suggests that both Py0 and Py1 contain low contents of invisible gold (mean 0.19 ppm and 0.17 ppm, respectively). However, Py1 is low in most other trace element contents and contains Au-Ag-Cu-Pb-Bi micro-inclusions. In contrast, Py2 contains both invisible gold (mean 0.50 ppm) and Au-Ag-Cu-Pb-Bi micro-inclusions. Furthermore, LA-ICP-MS mapping reveals the distributions of Ag, Cu, Pb, Bi and Te closely mimic that of Au, indicating an episode of ore-forming fluid rich in Au, Ag, Cu, Pb, Bi and Te. In situ sulfur isotope analysis of pyrite shows that Py0 has significantly positive δ34S values (+11.74–17.33‰), suggesting that sulfur was derived from sedimentary sources. Py1 and Py2 have negative δ34S values (–8.53––6.19‰, –10.44––6.86‰, respectively), indicating that sulfur was derived from oxidized magmatic fluids. The magmatic fluids are concluded to be released from the early Cretaceous microdiorite magmas, providing most of the sulfur and ore-forming metals. Proofs include the close spatial association of the ore bodies and the dykes, as well the uniform Pb isotopic ratios of Py1 and the early Cretaceous microdiorite. Lines of geological, mineralogical, geochemical and isotopic evidence consistently suggest that the gold mineralization in the Baiyun deposit is intrusion-related, and was resulted from the ~126 Ma magmatic-hydrothermal activities in the region. Visible gold precipitating in pyrite and fractures was from metal-rich magmatic fluids rather than being remobilized from the metamorphic pyrite.

Geochemistry and δ11 B evolution of tourmaline from tourmalinite as a record of oceanic crust in the Tonian Ibaré ophiolite, southern Brasiliano Orogen.

The isotopic and geochemical evolution of tourmaline constrain the processes of paleo-oceanic lithosphere in ophiolites. The Brasiliano Orogen is a major structure of South America and requires characterization for the understanding of Gondwana supercontinent evolution. We made a pioneering investigation of tourmaline from a tourmalinite in the Ibaré ophiolite by integrating field work with chemical analyses of tourmaline by electron microprobe (EPMA) and δ11B determinations via laser ablation inductively coupled plasma mass spectrometer (LA-ICP-MS). Remarkably massive tourmalinite (>90 vol.% tourmaline, some chlorite) enclosed in serpentinite has homogeneous dravite in chemical and isotopic composition (δ11B = +3.5 to +5.2‰). These results indicate a geotectonic environment in the altered oceanic crust for the origin of the tourmalinite. This first δ11B characterization of tourmaline from tourmalinite sets limits to the evolution of the Neoproterozoic to Cambrian Brasiliano Orogen and Gondwana evolution.

Advances in ICP-MS technology and the application of multi-element geochemistry to exploration

There have been several advances in inductively coupled plasma-mass spectrometer (ICP-MS) analytical technologies in the last decade. Collision/reaction cell ICP-MS and triple quadrupole ICP-MS techniques can produce lower detection limits for select elements that experience interferences with a standard quadrupole (e.g. Se and As). Triple quadrupole ICP-MS, in particular, can eliminate virtually all polyatomic or isobaric interferences for highly accurate measurements of some element isotopes systematics that are of great interest in mineral exploration, namely Pb/Pb. Laser ablation ICP-MS has become more popular as an effective analytical tool to measure mineral grain trace elements, which could assist in vectoring to mineralization or exploration drill targets. The ablation of a spot on a Li-borate fused glass disk paired with XRF analysis has also gained popularity as an alternative to total whole rock characterization packages that employ several separate digestions and analytical methods. While there have been several advancements in ICP-MS technologies in exploration geochemistry, they have not been widely accepted or implemented. This slow adaptation could be due to the extended recession in the mining industry between 2012 and 2017. It is also possible that standard ICP-MS data (i.e. no collision/reaction cell) is still fit for purpose. This stands in stark contrast to implementation of ICP-MS in the previous decade (1997–2007), which was transformational for the industry. Consideration of all elements from large multi-element ICP-MS analytical suites for mineral exploration can be an extremely powerful tool in the exploration toolkit. The discovery of the White Gold District, Yukon, is a prime example of how the utilization of soil geochemical data, when plotted spatially, can vector to gold mineralization. The presence of Au + As + Sb soil anomalies were key to delineating mineralization, especially when accompanied by publicly available geological, geographical and geophysical data. Additionally, elements and element ratios not typically considered in Au exploration, including Ni and U, were utilized to determine the lithological and structural controls on mineralization. The availability of multi-element ICP-MS data was also useful in the discovery of the Cascadero Copper Taron Caesium deposit. Ore-grade Cs was discovered only because Cs was included in the multi-element ICP-MS exploration geochemistry suite. Before the availability of ICP-MS, it is unlikely that this deposit would have been discovered. Thematic collection: This article is part of the Exploration 17 collection available at: https://www.lyellcollection.org/cc/exploration-17

Trace element composition of scheelite in orogenic gold deposits

Scheelite from 25 representative orogenic gold deposits from various geological settings was investigated by EPMA (electron probe micro-analyzer) and LA-ICP-MS (laser ablation-inductively coupled plasma-mass spectrometer) to establish discriminant geochemical features to constrain indicator mineral surveys for gold exploration. Scheelite from orogenic gold deposits displays five REE patterns including a bell-shaped pattern with a (i) positive or (ii) negative Eu anomaly; (iii) a flat pattern with a positive Eu anomaly and, less commonly, (iv) a LREE-enriched pattern, and (v) a HREE-enriched pattern. The REE patterns are interpreted to reflect the source of the auriferous hydrothermal fluids and, perhaps, co-precipitating mineral phases. Scheelite from deposits formed in rocks metamorphosed at upper greenschist to lower amphibolite facies have low contents in REE, Y, and Sr, and high contents in Mn, Nb, Ta, and V, compared to scheelite formed in rocks metamorphosed below the middle greenschist facies. Scheelite from deposits hosted in sedimentary rocks has high Sr, Pb, U, and Th, and low Na, REE, and Y, compared to that hosted in felsic to intermediate rocks. Statistical analysis including elemental plots and multivariate statistics with PLS-DA (partial least square-discriminant analysis) reveal that the metamorphic facies of the host rocks as well as the regional host rock composition exert a strong control on scheelite composition. This is a result of fluid-rock exchange during fluid flow to gold deposition site. PLS-DA and elemental ratio plots show that scheelite from orogenic gold deposits have distinct Sr, Mo, Eu, As, and Sr/Mo, but indistinguishable REE signatures, compared to scheelite from other deposit types.

Columbite U-Pb Geochronology of Kalu’an Lithium Pegmatites in Northern Xinjiang, China: Implications for Genesis and Emplacement History of Rare-Element Pegmatites

The Kalu’an-Azubai pegmatite field, one of the most important rare-metal metallogenic regions in China, contains a large number of pegmatite dikes belonging to spodumene and lepidolite subtypes. Columbite-group minerals (CGMs) collected from three spodumene subtype pegmatites (No. 802, No. 803, and No. 805 pegmatites) were analyzed for major element contents using EPMA (electron probe micro-analyzer) and dated using LA-ICP-MS (laser ablation-inductively coupled plasma mass spectrometer). The crystallization ages of the CGMs from No. 802, No. 803, and No. 805 pegmatites are 209.5 ± 1.4 Ma (2σ), 198.3 ± 2.0 Ma (2σ), and 224.3 ± 2.9 Ma (2σ), respectively. Oscillatory zoning and/or sector zoning along with the associated mineral assemblages suggest that the dated columbite is of magmatic origin. The crystallization ages of the columbite grains thus represent the emplacement ages of the Li pegmatites. Therefore, our dating results indicate that there were three emplacement events of the Li-rich pegmatite-forming melts in a timeframe of ~30 Ma. In combination with previous studies, we conclude that the Li pegmatites were formed before the Be-Ta-Nb pegmatites (~194–192 Ma), which precludes the genesis of rare-metal pegmatites via fractional crystallization of a granitic magma in the Kalu’an-Azubai region.

Source of the Chaoyangzhai Gold Deposit, Southeast Guizhou: Constraints from LA-ICP-MS Zircon U–Pb Dating, Whole-rock Geochemistry and In Situ Sulfur Isotopes

The Chaoyangzhai gold deposit is one of the newly discovered medium to large scale turbidite-hosted gold deposits in Southeast Guizhou, South China. In this study, laser ablation-inductively coupled plasma-mass spectrometer (LA-ICP-MS) zircon U–Pb dating on the tuffaceous- and sandy-slates of Qingshuijiang Formation, Xiajiang Group, and gold-bearing quartz vein yielded similar age distributions, indicating that zircon grains in gold-bearing quartz vein originated from the surrounding tuffaceous- and sandy-slates. In addition, the youngest weighted mean ages of the zircon grains from the tuffaceous- and sandy-slates were 775 ± 13 Ma and 777 ± 16 Ma, respectively, displaying that the tuffaceous- and sandy-slates of the Qingshuijiang Formation were likely deposited in Neoproterozoic. Based on their major and trace element compositions, the tuffaceous- and sandy-slates were sourced from a felsic igneous provenance. The sandy slates have higher contents of Au (mostly ranging from 0.019 to 0.252 ppm), than those of the tuffaceous slates (mostly lower than 0.005 ppm). The δ34SV-CDT values of pyrite and arsenopyrite of the gold-bearing samples range from +8.12‰ to +9.99‰ and from +9.78 to +10.78‰, respectively, indicating that the sulfur source was from the metamorphic rocks. Together with the evidence of similar geochemical patterns between the tuffaceous- and sandy-slates and gold-bearing quartz, it is proposed that the gold might be mainly sourced from sandy slates. The metamorphic devolatilization, which was caused by the Caledonian orogeny (Xuefeng Orogenic Event), resulted in the formation of the ore-forming fluid. Gold was likely deposited in the fractures due to changes of the physico-chemical conditions, leading to the formation of the Chaoyangzhai gold deposit, and the large-scale gold mineralization in Southeast Guizhou.

Effect of EDTA and NTA on cadmium distribution and translocation in Pennisetum purpureum Schum cv. Mott.

The primary objective of this research was to investigate the cadmium (Cd) distribution in Pennisetum purpurem (Napier grass) in the presence of 30mg/L of Cd and different types and concentrations of chelating agents (ethylenediaminetetraacetic acid disodium dihydrate (EDTA), nitrilotriacetic acid (NTA), and EDTA-NTA mixtures). Plant samples were collected every 15d during a 105-d experimental period. Accumulation of Cd in each part of the plant was determined using atomic absorption spectrometer (AAS), and the distribution of Cd was determined by laser ablation inductively coupled plasma mass spectrometer (LA-ICP-MS) and synchrotron radiation micro X-ray fluorescence (SR-micro-XRF). The highest concentrations of Cd accumulation of 889 ± 53mgkg-1 in the underground part (roots) and 265 ± 26mgkg-1 in the aboveground part (stems and leaves) in the presence of 1:1M ratio of Cd:EDTA after 30d of exposure were observed. Plants grown in the presence of either NTA or EDTA-NTA mixtures showed significant lower Cd accumulation levels. The LA-ICP-MS analysis showed that Cd was primarily accumulated in the aboveground part (stems and leaves), especially in the xylem and intercalary meristem. In addition, translocation factor was very low. Thus, P. purpurem could be considered as a candidate plant for cadmium phytostabilization.

Petrogenesis and evolution of the Nuweibi rare-metal granite, Central Eastern Desert, Egypt

The Nuweibi rare-metal granite in the Central Eastern Desert of Egypt is highly evolved fine- to medium-grained leucogranite affected by pervasive albitization and greisenization. The intrusion holds an important tin–tantalum resource in the Egyptian Eastern Desert. Columbite–tantalite and cassiterite disseminations occur within the granite body, while the quartz ± feldspar veins cutting across the Nuweibi granite host only cassiterite disseminations. Microscopically, quartz and alkali-feldspar are the essential mineral constituents of Nuweibi granite, with minor mica (muscovite + rare biotite), while cassiterite, columbite–tantalite, zircon, allanite, beryl, tourmaline, titanite, and fluorite are accessories. Whole-rock geochemistry and micoanalytical data together with laser ablation inductively coupled plasma mass spectrometer (LA-ICP-MS) dating of zircon and columbite have been used to constrain the evolution of the granite intrusion and associated mineralization. The Nuweibi granite is weakly peraluminous with extremely low MgO, CaO, TiO2, P2O5, Ba, and Sr contents and elevated Sn, Ta, Nb, and Rb contents. The REE patterns exhibit distinct tetrad effects, as well as negative Eu and Y anomalies. Also, the bulk rock Zr/Hf ratios are consistently < 10. The Nd isotopic system is disturbed and eNd values suggest a juvenile mantle and/or Neoproterozoic crustal source. The U–Pb system in zircon is disturbed and leaked continuously, while the U–Pb age of columbite is ~ 620 Ma. The geochemical and isotopic systematics of the Nuweibi intrusion reflect very advanced degree of fractionation combined with late magmatic fluid overprint which redistributed Sn and other mobile elements, while Ta still characterizes the igneous system.

Chalcophile-siderophile element systematics of hydrothermal pyrite from martian regolith breccia NWA 7533

Unlike other martian meteorites studied so far, Martian regolith breccia NWA 7533 and paired meteorites that have sampled 4.4 Ga-old impact lithologies show only sulfides of hydrothermal origin (mostly pyrite (<1 vol.%) and scarce pyrrhotite). NWA 7533 pyrite has been analyzed for 25 chalcophile-siderophile trace elements with laser ablation-inductively coupled plasma mass spectrometer (LA-ICPMS). Micronuggets of highly siderophile elements-HSE (Os, Ir, Pt, Ru, Rh) along with occasional detection of Mo and Re were observed in half of the 52 analyzed crystals as random concentration spikes in time-resolved LA-ICPMS data. These nuggets are interpreted as variably altered remnants from repeated meteorite bombardment of the early martian crust, as are chondritic Ni/Co ratios of pyrite (10–20). Pyrite displays superchondritic S/Se (54,000–3300) and Te/Se (0.3 to >1). The reasonably good positive correlation (R2 = 0.72) between Se and Ni reflects a temperature control on the solubility of both elements. Apart from the chalcogens S, Se and Te, pyrite appears to be a minor contributor (<20%) to the whole-rock budget for both HSE (including Ni and Co) and chalcophile metals Ag, As, Au, Cu, Hg, Pb, Sb, Tl and Zn. This deficit can result from (i) high (>400 °C) temperature crystallization for NWA 7533 pyrite, as deduced from its Se and Ni contents, (ii) magmatic sulfide-depletion of brecciated early martian crust, (iii) precipitation from near neutral H2S-HS-H2O-rich hydrothermal fluids that did not provide halogen ligands for extensive transport of chalcophile-siderophile metals. It is suggested that the 1.4 Ga lithification event that precipitated hydrothermal pyrite left the chalcophile-siderophile element budget of the early martian crust nearly unmodified, except for S, Se and Te.