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The unconformity-related uranium (URU) deposits in the Proterozoic Athabasca Basin are one of the most important U resources in the world. This type of U deposit can be divided into monometallic (U) and polymetallic (U-Ni-Co-As) subtypes. While it is generally agreed that the URU deposits formed from reaction between oxidizing, basinal brines carrying U and/or Ni-Co-As with reducing basement fluids or lithologies, it is debatable whether the polymetallic deposits formed from co-enrichment of U-Ni-Co-As or enrichment of U superimposed by a separate Ni-Co-As mineralization event. This study addresses this problem through mineralogical, geochemical and fluid inclusion investigation of the Midwest U-Ni-Co-As deposit. Petrographic studies indicate that the sequence of ore precipitation started with uraninite, followed by Ni-Co arsenides and sulfoarsenides and then Cu-Pb-Fe sulfides, and this sequence was repeated episodically. This observation suggests that the deposit did not form from two separate U and Ni-Co-As mineralization events, but rather multiple episodes of U-Ni-Co-As mineralization. Linear correlations between chemical ages and Si-Ca-Fe contents of the most pristine uraninite U1 suggest a maximum primary mineralization of ca. 1600 Ma, which is consistent with the inferred primary U mineralization age in the Athabasca Basin. Microthermometric and laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) analyses of fluid inclusions in syn-mineralization drusy quartz indicate that the composition of the ore-forming fluids is characterized by the H2O-NaCl-CaCl2-KCl-MgCl2 system and comparable to those from both monometallic and polymetallic URU deposits. The relationship between U and Ni + Co in the fluid inclusions and its comparison with other URU deposits support a model in which U and Ni-Co were co-enriched in a unified mineralization process. The development of breccia structures in the ores and the dramatic fluid pressure fluctuation revealed by fluid inclusions suggest that the deposit formed from multiple episodes of fluid flow related to repeated reactivation of basement-rooted faults. [ABSTRACT FROM AUTHOR]

The tea-dust glaze ancient porcelain is one of the earliest crystalline glazes, which is rarely studied deeply because of its rarity. In this study, the mineral crystals in tea-dust glaze made in the Ding Kiln of the Northern Song Dynasty were analyzed by optical microscope (OM), laser ablation-inductively coupled plasma-mass spectrometry (LA-ICP-MS), scanning electron microscopy coupled with an X-ray energy dispersive spectrometer (SEM-EDS), laser confocal Raman spectrometer (LRS), and high-resolution time of flight-secondary ion mass spectrometry (ToF-SIMS). The results show that the main crystal phase in the glaze is the same as that of the Longquanwu Kiln in the Liao and Jin Dynasty, which is anorthite and augite. The overall performance of the glaze is that the sauce-black glaze matrix is rich in iron (Fe2O3 mean 9.73%) and the mineral crystal is rich in iron (Fe2O3 mean 11.33%). In addition to α-Fe2O3 crystals, Fe3O4 crystals and other recrystallized minerals after melting, the glaze also has pleonaste, residual kaolinite and other unmelted minerals from raw glaze materials. The residual kaolinite shows that the firing temperature of the samples in this study was most likely below 1200℃. [ABSTRACT FROM AUTHOR]

Discovered within the North Himalayan Metallogenic Belt (NHMB), the Zhaxikang Pb–Zn–Ag–Sb deposit stands as the sole super-large scale ore deposit in the region. This deposit holds significant quantities of Pb and Zn (2.066 million tons at 6.38% average grade), Ag (2661 tons at an average of 101.64 g/t), and Sb (0.235 million tons at 1.14% average grade), making it one of China's foremost Sb–polymetallic deposits. Stibnite represents the main carrier of Sb in this deposit and has been of great attention since its initial discovery. However, the trace element composition of stibnite in the Zhaxikang deposit has not yet been determined. This study carried out an analysis of the distribution patterns and substitution processes of trace elements within stibnite gathered from the Zhaxikang deposit, aiming to provide crucial information on ore-forming processes. Utilizing high-precision laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS), we discovered that the studied stibnite is notably enriched in arsenic (~100 ppm) and lead (~10 ppm). Furthermore, the notably consistent time-resolved profiles suggest that elements such as Fe, Cu, As, In, Sn, Hg, and Pb predominantly exist as solid solutions within stibnite. Consequently, it is probable that the enrichment of Cu, Pb, and Sn in stibnite is due to isomorphic substitution reactions, including 3Pb2+↔2Sb3+, Cu+ + Pb2+↔Sb3+, and In3+ + Sn3+↔2Sb3+. Apart from that, Mn, Pb, and Hg with the spiky signals indicate their existence within stibnite as micro-inclusions. Overall, we found that the trace element substitutions in stibnite from the Zhaxikang Pb–Zn–Ag–Sb deposit are complicated. Incorporations of trace elements such as Pb, Cu, and In into stibnite are largely influenced by a variety of factors. The simple lattice structure and constant trace elements in studied stibnite indicate a low-temperature hydrothermal system and a relatively stable process for stibnite formation. [ABSTRACT FROM AUTHOR]

The conducted study shows that apatite is one of the key accessory minerals in the ultramafic-mafic rocks of the Khudolaz differentiated complex in the Southern Urals, including late pegmatoid gabbro. Petrographic and mineralogical investigations determine apatite crystallizing simultaneously with hornblende in pegmatoid gabbro from the residual water-saturated melt after plagioclase crystallization at a temperature of 990–800 °C, a pressure of 1–3 kbar, oxygen fugacity from −13.9 to −10.7, and water content of 3.9–5.5 wt. %. Pegmatoid gabbro apatite (Appg) from the Severnyi Buskun composite massif differs from early ultramafic-mafic apatite having a fairly high potential for sulfide-platinum metal mineralization in low chlorine and high fluorine content. Low sulfur concentrations in Appg testify to the lack of sulfide-platinum metal mineralization potential of pegmatoid gabbro, but a scanty potential for rare-metal mineralization (e.g., REE) is possible. Appg is quite poor in REE despite the enrichment of pegmatoid gabbros in REE relative to early ultramafic-mafics, which indicates REE accumulation in the fluid. The ratios of cerium and europium anomalies characterize the Appg crystallization under conditions transitional from the magmatic to the hydrothermal stage. Generally, apatite is a good indicator of the difference in the conditions of formation of late pegmatoid gabbro and early ultramafic-mafic rocks, which determines the importance of this mineral in mineralogical and petrological studies. [ABSTRACT FROM AUTHOR]

The effects of different regional tectonic events on the Neoproterozoic basement rocks of the Arabian–Nubian Shield in Sinai, as well as the Egyptian unstable and stable shelves, remain uncertain. Coupling fission-track thermochronometry findings with the modeling of the time–temperature history has proved to be an effective method for tackling these issues. The obtained zircon fission-track ages were differentiated into two groups from the Ediacaran–Cambrian and the Ordovician–Carboniferous periods, while the apatite fission-track data revealed two separate groups of cooling ages of the Carboniferous–Triassic and Late Cretaceous ages. The integration of these cooling ages and modeling of the time–temperature history revealed four discrete cooling pulses during the Neoproterozoic, Devonian–Carboniferous, Cretaceous, and Oligocene–Miocene eras. After integrating our findings with the regional tectonic historical and sedimentological records, these could be identified as cooling/exhumation pulses activated in response to the post-accretional event of erosion, Variscan tectonism, the disintegration of Gondwana, and the Gulf of Suez rifting, respectively. Furthermore, the southern border of the Egyptian unstable shelf was found to extend southward to South Sinai and south of the Bahariya depression. [ABSTRACT FROM AUTHOR]

Garnet U‐Pb dating by laser ablation‐inductively coupled plasma‐mass spectrometry requires the development of matrix‐matched reference materials of variable chemistry and U mass fraction for accurate analysis. Additional calibration of existing primary reference materials is also justified based on the relatively poor calibration of some of the widely available primary reference materials that are currently utilised by the geoscience community. We present a micro sampling workflow combined with a refined ID‐TIMS methodology for the generation of high precision (~ 0.1%) U‐Pb dates from domains within garnet single crystals. Using this workflow, we calibrated two new natural andradite reference materials, the Jumbo andradite (And99; 110.34 ± 0.03 (0.04) [0.13] Ma, n = 7, MSWD = 1.21) and the Tiptop andradite (And87; 209.57 ± 0.11 (0.13) [0.26] Ma, n = 6, MSWD = 1.39). We also present additional calibration of the widely utilised Willsboro‐Lewis andradite primary reference material (And90; 1024.7 ± 9.5 (9.6) [9.6] Ma (2s; overdispersed), n = 6). Wafers of the Jumbo and Tiptop andradite reference materials are available from the authors upon request. [ABSTRACT FROM AUTHOR]

The Xiaoqinling gold province, located in the southern margin of the North China Craton (NCC), is the second largest gold-enriched region in China. In this region, the Mesozoic Huashan (HS) and Wenyu (WY) plutons are the major magmatic intrusions coeval with gold mineralization, although they show contrasting characteristics in the distribution of gold. In this study, we use geochemical features of titanite determined by LA-ICP-MS and EPMA analyses and elemental mapping to decipher the mechanisms that led to the difference in gold enrichment related to the two plutons. Titanite from the Wenyu granitic pluton exhibits significantly higher (La/Sm)N, (La/Yb)N, ΣLREE/ΣHREE ratios, and ΣREE concentration and slightly higher (Gd/Yb)N values than those of the Huashan Pluton, suggesting that the Wenyu pluton might have experienced more complex magmatic evolution, widespread hydrothermal alteration, and higher silica activity in the melt than the Huashan pluton. The titanite grains from the Huashan pluton show higher (Nb/Ta)N and (Lu/Hf)N values and significantly lower Zr concentration than those of the Wenyu pluton. The titanite grains from the Wenyu pluton show higher vanadium and gallium concentrations and Fe/Al ratio than those of the Huashan pluton, indicating comparatively higher f o 2 . Furthermore, the titanite grains from Wenyu pluton indicate higher water content in the magma. In addition, magma mingling and magmatic hydrothermal fluids derived from the crust/mantle are critical sources for ore-forming materials. These results suggest that the Wenyu pluton is more conducive to gold migration and enrichment than the Huashan pluton. [ABSTRACT FROM AUTHOR]

Azurite, a historical blue mineral pigment, has previously been described to contain certain elemental impurities. These may originate from host rocks, vein fillings, or the primary copper ore mineralization. In this study, azurites (and also green malachites) from three important Central European deposits with a potential of being exploited for pigment usage already in the Middle Ages have been studied, together with azurite from Chessy, France, with a different geological setting. Using electron probe microanalysis and, more importantly, laser ablation inductively coupled plasma mass spectroscopy for trace elemental analysis, several indicators were pinpointed as important for provenance: characteristic elemental fingerprint of the deposit, e.g., elevated lead (Pb) in combination with rare earth elements, may be combined with zinc (Zn)/arsenic (As) ratio (indicating sources of excess Zn in the primary deposit) and the overall amount of metal impurities (suggesting the source mineral of copper for azurite formation). In addition, malachites from the same deposits were found to preferentially incorporate primary ore metal elements as well as Cd, Mg, Mn, or U. Therefore, if azurite pigment contains an elevated amount of malachite as an impurity, it may significantly influence the overall elemental composition. The results obtained on geological samples were applied to two micro-samples of works of art containing azurite-rich layers originating from the 13th–14th and 16th centuries. It was shown that it is highly beneficial to focus on the overall trace elemental composition of the paint layer and not on the admixed mineral grains, as their presence, especially in minute micro-samples, is largely accidental and thus not representative. Although a higher number of samples need to be studied in the future, the newly described criteria made it possible to exclude some of the localities of the employed azurite pigment. This confirmed the key importance of trace elements analysis of mineral pigments for the provenance studies of fine arts. [ABSTRACT FROM AUTHOR]

Glass beads from two Islamic archaeological sites in the Tagus valley in central Spain were selected and analysed by laser ablation inductively coupled plasma mass spectrometry (LA‐ICP‐MS), and a subset of samples (n = 6) was analysed for Pb isotopes by multicollector thermal ionization mass spectrometry (MC‐TIMS). The analytical and isotopic data of the beads from Ciudad de Vascos (Toledo) and Albalat (Cáceres) demonstrate beyond reasonable doubt that glass beads were produced in the Iberian Peninsula during the Islamic period using local Pb‐silica and soda‐rich plant‐ash glass. The bead workshops in al‐Andalus were evidently part of an efficient system of glass collection and recycling, and used only relatively simple bead‐making techniques such as winding and folding. At present it is unclear to what extent the Islamic bead‐makers in the Iberian Peninsula were involved in the international trade in glass beads or whether their products were mainly destined for a regional market. Despite local production, some samples show compositional and typological features that suggest the import of finished glass beads, perhaps from Central Asia. [ABSTRACT FROM AUTHOR]

The Gulf of Suez is a continental rift basin that has been developed during the Oligocene-Miocene as a northern extension of the Red Sea rift system. The Oligo-Miocene rift-activated flanks are represented by exposures of the Neoproterozoic basement rocks of the Arabian-Nubian Shield. An additional thermal overprint (i.e. mantle plume) and the preceding tectono-thermal events that also affected the rifting dynamics and the uplift of its flanks remain uncertain. We here present thermochronological data for 20 basement samples collected from the Gabal Somr ElQaa area at the northwestern flank of the Gulf of Suez. The resulted zircon fission-track ages could be divided temporospatially into two groups: the Cambrian and the Silurian-Devonian with average ages of 503 ± 14 Ma and 407 ± 11 Ma, respectively. While apatite fission-track data reveal three different age groups of the Devonian-Carboniferous, the Permian-Triassic, and the Late Cretaceous, with average ages of 349 ± 10 Ma, 246 ± 6 Ma, and 81 ± 5 Ma, respectively. The modelled t-T histories indicate four cooling pulses during the Neoproterozoic, the Devonian-Carboniferous, the Cretaceous, and the Oligocene-Miocene. Integrating our findings with the regional tectonism and depositional records indicates that these cooling pulses could be attributed to synchronous activities of the post-accretion erosional event, the Variscan tectonic event, the Mid-Atlantic Ridge spreading, and the Gulf of Suez rifting. The Gulf of Suez is a passive rift, formed by a single and rapid rifting pulse within the framework of the Red Sea rift system. An additional east-southward far-field thermal overprint from the Arabian marginal plume partially affected the Suez rifting process. This thermal print affected only the rift’s southern portion of its eastern flank, causing syn-rift cooling ages, highly elevated rift flanks, and an increased heat flow. The western rift flank and the northern segment of the eastern flank are characterized by pre-rift cooling ages, modest rift flanks, and reduction in heat flow. [ABSTRACT FROM AUTHOR]

Germanium (Ge) is a critical raw material for emerging high-tech and green industries, resulting in considerable recent interest in understanding its distribution and geochemical behavior in ore deposits. In this contribution, the distribution of Ge and related trace elements in the Fule Pb-Zn(-Ge) deposit, South China, is investigated to reveal the distribution of Ge in the hydrothermal ores and during sulfide weathering, using multiple microanalytical techniques, including scanning electron microscopy, electron probe microanalysis and laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS). In the Fule MVT deposit, sphalerite (ZnS) is the most significant Ge-carrier relative to other sulfides, though the five recognized textural types of sphalerite display progressive depletion in Ge from the first sphalerite generation to the late one. In the early stage, sphalerite with fine-grained chalcopyrite inclusions has the highest Ge concentrations, probably accounting for a significant proportion of the total Ge. We interpret that high Ge concentrations in the early sphalerite may be attributable to high Cu activity in the mineralizing fluids. During oxidative weathering, Ge was redistributed from its original host, sphalerite, to the weathering product willemite (Zn2SiO4) rather than smithsonite (ZnCO3), with high levels of Ge (up to 448 μg/g) present in the willemite. The formation of abundant willemite largely prevents the dispersion of Ge during weathering. In principle, willemite-hosted Ge should be fully recoverable, and the Zn-silicate ores may, therefore, be a potential target to meet future demand. This study provides new information on how Ge behaves from sulfide- to weathering-stage in MVT systems, which directly impacts Ge mobility and deportment changes and the development of metallurgical strategies for Ge recovery. [ABSTRACT FROM AUTHOR]

A simple and reliable external calibration strategy of LA-ICP-MS for fresh plant soft tissues was developed. The prepared plant suspension was frozen by the designed cryogenic ablation cell and used as external standard for quantitative elemental imaging analysis of fresh plant tissues. The controllable water content of the prepared external standards provides a similar matrix with fresh soft tissues, and a homogeneous elemental distribution could be ensured due to the fine grinding particle sizes. More interestingly, the presence of water increased the signal intensity produced by the suspension by a factor of 1.6 (Pb) to 66.6 (La) compared to that of the pressed cake. The excellent dispersing property and advantage of long-term use were achieved owing to the employment of 0.1% PAANa as suspending agent. A series of plant reference materials were analyzed, and the relative errors of most elements were less than 10 %, indicating that there is a reliable accuracy of the proposed method. The limits of detection (LODs) ranged from 0.1 ng·g−1 (La) to 1279 ng·g−1 (S). This method was used for elemental imaging analysis in rice leaves under arsenic stress, and the results were consistent with previous studies, which mean that the proposed method could provide technical support for researchers in the fields of agriculture and environment. [ABSTRACT FROM AUTHOR]

U–Pb dating of zircon via laser ablation‐inductively coupled plasma‐mass spectrometry (LA‐ICP‐MS) has become a primary method for determining the age of crystalline rocks and the provenance and maximum depositional age of (meta)sedimentary rocks. Although chemical abrasion has become a standard approach for mitigating Pb loss in zircon dated via high‐resolution thermal ionization mass spectrometry (CA‐TIMS), laser ablation dating is rarely accompanied by chemical abrasion. We evaluate the accuracy of U–Pb dates acquired via LA‐ICP‐MS relative to CA‐TIMS through analysis of a large database of paired analyses from the same zircon crystals. We show that laser ablation 206Pb/238U dates are systematically younger than their CA‐TIMS counterparts, with a greater shift in detrital zircon (−2.0%) versus igneous or metamorphic zircon (−0.9%). Although systematic biases related to “matrix effects” may be a contributing factor, our analysis suggests that unmitigated cryptic Pb loss is likely widespread in laser ablation U–Pb datasets. [ABSTRACT FROM AUTHOR]

Bark paintings represent a unique artform that originated in Australia and continues to this day. This paper presents a scientific investigation into both the pigments and binders used by Aboriginal artists from across the Northern Territory (NT) and the Kimberley region in Western Australia (WA) and represents the first major study dedicated to identifying these materials in samples taken from paintings. Laser ablation-inductively coupled plasma-mass spectrometry (LA-ICP-MS), Fourier transform infrared (FTIR) and Raman spectroscopy were used to identify the pigments in the four colors commonly associated with works by Aboriginal artists: red, yellow, black, and white. Iron oxides are used for red and yellow. Typically, kaolin is used for white and carbon or natural manganese ores are used for black, although the use of other pigments such as huntite (white) and battery black were seen in paintings from specific locations. Evidence of trade could not be established during this study; however, analysis shows that artists may use different pigments based on location and availability. A combination of FTIR and pyrolysis-gas chromatography-mass spectrometry (pyrolysis-GC-MS) was utilized to investigate the presence of a binder in the paint. Plant-based materials were identified as the binder in the majority of the paintings. The use of orchid juice was common, both as a preparatory layer on the bark substrate and as a paint binder. The presence of synthetic resins was more widespread than anticipated, attributed to both conservation efforts and more modern painting practices. [ABSTRACT FROM AUTHOR]

The Perron deposit, located in the northern part of the Archean Abitibi belt, bears some of the highest gold-grade mineralization for orogenic-vein-type deposits worldwide (High-Grade Zone: HGZ). More than 13 gold-bearing zones with different sulfide assemblages, hydrothermal alterations, and gold grades have been recently outlined, and they range from volcanogenic to orogenic in origin. In addition, seven zones are hosted in a restricted volume of ~1 km3, which is called the Eastern Gold Zone. Pyrite, sphalerite, pyrrhotite, and chalcopyrite—each from a different gold-bearing zone—were analyzed with LA-ICP-MS to decipher their genetic links, mineralizing processes, and temperature of formation. The temperatures calculated with the sphalerite GGIMFis thermometer range from 348 to 398 °C. All gold-bearing zones recorded volcanogenic hydrothermal inputs at different intensities, manifested by pyrrhotite. Pyrite was late-metamorphic and related to the orogenic gold system induced by the contact metamorphism of amphibolite facies. The pyrrhotite grains had very homogeneous trace element signatures in all zones, which is a characteristic of metamorphic recrystallization, exhibiting a loss of mobile elements (Au, Te, Bi, Tl, Sn, W, In) but high concentrations of Ni, Co, and As. Conversely, the pyrite was systematically enriched with all elements depleted from pyrrhotite, bearing five specific signatures of element enrichments: W, Tl, Sn, In-Cd-Zn, and Bi-Te-Au. For gold-rich zones (e.g., the HGZ), gold was linked to the Bi-Te-Au signature of pyrite, with Bi enrichment occurring at up to 72,000 times the background level in Archean shale pyrite. It was concluded that gold was transported, at least in part, as Bi-Te melts in the previously documented non-aqueous orogenic fluids, hence accounting for the very-high-grade gold content of the HGZ. Genetically, the metamorphism of primary gold-bearing volcanogenic mineralizations was the main source of gold during the overprinting of amphibolite (600 °C) in a metamorphically induced orogenic mineralizing event. A strong volcanogenic pre-enrichment is considered the main factor accounting for the gold endowment of the Eastern Gold Zone. [ABSTRACT FROM AUTHOR]

The Bou Dahar Pb-Zn district, located in the Moroccan High Atlas, is a typical carbonate-hosted Pb-Zn ore district (>30 Mt at 4 wt.% Pb, 4 wt.% Zn). In situ trace element analysis was performed using laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) on galena and cerussite from different ore types. The galena is generally enriched in Ag and Sb, secondarily enriched in Cu, with a trace amount of Cd and As, but extremely depleted in Bi and Tl. The main substitution mechanism in galena is (Ag, Cu)+ + Sb3+ ↔ 2Pb2+, and at high Sb concentrations, the further substitution of 2Sb3+ + □ ↔ 3Pb2+ (where □ represents a vacancy) took place. Micro-inclusions of Cu-Sb-bearing minerals (such as tetrahedrite) and Ag-bearing minerals (such as acanthite) may exist in some situations. The features of trace elements in galena show the existence of different coupled substitutions in vein-related ore, breccia-related ore, and strata-bound ore. This suggests that the Bou Dahar district experienced multistage mineralization. The MVT model alone cannot fully explain the ore-forming process. The cerussite replacing strata-bound galena is enriched in Sr, Ba, Ag, and Cu, with minor Sb, As, and Tl. Strontium and Ba are directly substituted with Pb in the cerussite lattice. Copper and Ag are likely present in cerussite as nano-inclusions, which differs from the coupled substitution mechanism of the original galena. High concentrations of Ag may occur due to minor electrum inclusions. The enrichment of Ag, Cu, and Au in cerussite during the oxidation process may guide the optimization of ore processing, especially in extracting valuable trace/minor elements. [ABSTRACT FROM AUTHOR]

Raman spectroscopy and laser ablation‐inductively coupled plasma‐mass spectrometry were used to characterize the chemical composition of 34 red garnet beads from Lower Nubian sites, dated between about 3200 BCE and 600 CE. All beads from the A‐Group to the Meroitic period feature a similar calcium‐poor almandine composition (69%–78% almandine, 15%–22% pyrope, 2%–6% grossular, 3%–9% spessartine), which differs from other calcium‐poor almandine garnet types, sourced mostly from Indian deposits in Antiquity. The Nubian beads constitute a new garnet type, named "cluster I", featuring high yttrium (180 to 1205 ppm), moderately low chromium (13–70 ppm), and high scandium (119–213 ppm) concentrations. Their compositions match with previous and two new analyses from two alluvial garnet deposits, Wadi El‐Haraz and Wadi Abu Dom, near the Fourth Cataract of the Nile in Upper Nubia, about 670 km as the crow flies from the Lower Nubian graves. Garnet trade between the Bayuda desert and Lower Nubia sites, and possibly even Egypt, flourished for almost four millennia. Northeastern Africa is the cradle for the oldest use of a gemstone that is harder than quartz—the red almandine garnet. A Post‐Meroitic bead, the youngest in the assembly, displays an unusual faceting, a diamond tipped drill hole, excellent polish, distinct short‐ and long‐prismatic colorless mineral inclusions, and a calcium‐ and manganese‐poor pyrope composition. This suggests that it was not of a local, Nubian, production, but imported, most probably from a South Asian site. [ABSTRACT FROM AUTHOR]

In addition to his astronomical observations the famous Renaissance astronomer Tycho Brahe (1546–1601) was known also for his interest in alchemy. He equipped his castle Uraniborg on the island of Ven with a state-of-the-art alchemical laboratory when it was erected around 1580. After Brahe's death Uraniborg was demolished upon a royal decree from 1601, a process which was completed around 1650. In the present study we have analysed four glass shards and one ceramic shard most likely from the alchemical laboratory and retrieved during an archaeological excavation in 1988–90. Cross sections of the shards have been analysed for 31 trace elements by Laser Ablation Inductively Coupled Plasma with Mass Spectrometry with the aim of detecting any traces of the chemical substances on the inside or outside of the shards used in the laboratory. Four of the elements found in excess on the exterior surfaces of the shards, Cu, Sb, Au, and Hg, are in accordance with the reconstructed recipes of the three Paracelsian medicines for which Brahe was famous—Medicamenta tria. This is the first experimental data casting light on the alchemical experiments that took place at Uraniborg 1580–1599. [ABSTRACT FROM AUTHOR]

Apatite fission track (AFT) dating is now routinely performed using LA‐ICP‐MS, and U‐Pb age data are often acquired at the same time, allowing double dating of individual grains. Furthermore, additional geochemical data, such as REE mass fractions are readily acquired during the analysis. It is therefore of practical interest to identify a single material as a quality control on ages and composition. Here we present AFT and U‐Pb data for the McClure Mountain Syenite (MMS) apatite, already widely used as an age reference material by the U‐Pb community. We performed double dating on 238 grains, in thirteen measurement sessions over two years. The AFT data show remarkable reproducibility with an overall central age of 254.1 ± 5.1 Ma. The U‐Pb results agree with the reference age for individual sessions (and for all data together). The results show that that the McClure Mountain apatite is a valid quality control material for double dating, allowing the use of the same material for both methods. We also propose to extend the quality control using MMS to trace element measurements performed in conjunction AFT and U‐Pb dating. [ABSTRACT FROM AUTHOR]

This study investigates the potential of laser ablation inductively coupled plasma mass spectrometry (LA‐ICP‐MS) U‐Pb dating for carbonate nodules in the Late Triassic Ischigualasto Formation of northwestern Argentina. We establish a fully characterized paragenetic sequence to guide the analysis of three pedogenic carbonates and compare the U‐Pb ages with published geochronology from volcanic ashes within the sedimentary succession. Our findings demonstrate the importance of interpreting U‐Pb data within a well‐defined paragenetic framework for accurate age interpretation of pedogenic carbonates. We observe variations in U‐Pb isotopic signatures across different generations of carbonate precipitates and identify syn‐pedogenic and early burial calcite cements as most suitable for precise dating. Respectively, these two calcite cements are interpreted as microcodium and crack‐lining calcite cements formed early in the paragenetic sequence during pedogenesis to early burial of the paleosols as they transitioned from the unsaturated vadose to saturated phreatic zone below the water table. The U‐Pb ages obtained from the carbonate nodules agree with the radioisotopic ages of volcanic ashes, supporting the validity of our dating strategy. These results contribute to advancing U‐Pb carbonate geochronology and highlight its increased potential for dating sedimentary records in the terrestrial realm. Future research should focus on replicating similar work on different carbonate nodules within the Ischigualasto Fm and expanding the application of LA‐ICP‐MS U‐Pb dating to other carbonate‐bearing formations, especially in successions with limited absolute ages or where volcanic ashes are sparse or absent. Plain Language Summary: Carbonate minerals that formed in fossil soils can provide valuable insights into past physical, biological, and chemical processes on Earth's surface. Despite their significance in reconstructing ancient climates and environments, determining the age of these fossil soils via uranium‐to‐lead dating has proven challenging. This difficulty arises from factors associated with soil carbonate minerals, including low uranium content, high lead content, complex formation chemistry, multiple formation episodes (generations), and potential for post‐formation chemical alteration. To address these issues, we first identified the order in which carbonate minerals formed within three samples from the Late Triassic Ischigualasto Formation of Argentina. Then, we dated each generation within each sample and compared the results to identify and understand the most optimal sample locations for dating. Analysis of our data shows that carbonate minerals formed due to biological processes near the surface as well as during the burial and submersion of the fossil soils below the water table are the most suitable for dating and approximate the timing of soil formation. Importantly, the ages from these soil carbonate samples align with ages from volcanic ashes found within the Ischigualasto Formation, thus validating our results and the potential to apply our strategy in other locations. Key Points: A well‐defined paragenetic framework is necessary to interpret laser ablation inductively coupled plasma mass spectrometry U‐Pb data for accurate age interpretation of pedogenic carbonatesU‐Pb isotopic signatures vary across generations of carbonate precipitates, with syn‐pedogenic and early burial cements being the most suitable for precise datingSyn‐pedogenic and early burial cements approximate the timing of pedogenesis and transition from the unsaturated vadose to the saturated phreatic zone, respectively [ABSTRACT FROM AUTHOR]

The preparation of matrix-matched material for elemental quantitative analysis in rice flour matrix is proposed here for the first time as part of a feasibility study using the SN-ICP-MS and LA-ICP-MS methods. It was prepared via the spiking process in colloidal solution of rice flour with different levels of arsenic (As), cadmium (Cd) and lead (Pb), followed by drying in a climatic chamber. Comparative studies of the results on external calibration and gravimetric standard addition ICP-MS approaches through the use of calibration standard solutions were discussed. Method bias from the external calibration method was investigated, demonstrating the systematic effect arising from the sample matrix. Characterizing the concentration of measurands was then reasonably proposed using the gravimetric standard addition ICP-MS. Using powdered rice matrix reference material for ICP-MS calibration following acid digestion, the study showed a good agreement of recovery studies. A feasibility study of the LA-ICP-MS method as a direct solid analysis performed on the matrix-matched standard was then discussed. In the study, large fluctuation of signals was found for constructing calibration curve, generating poor linearity, especially for As and Pb, although yttrium (Y) as internal standard was applied. This might be ascribed to a limited microscale of homogeneity, and particularly laser-induced preferential evaporation of volatile elements. Using a number of measured data points, the mean and median were statistically recommended to improve precision. An attempt to use of similar matrix in both standard and sample is a critical point to consider to minimize the elemental fractionation effect. The proposed approach to prepare matrix-matched material could be a potential means for achieving elemental quantitation. [ABSTRACT FROM AUTHOR]

Innate immune systems alter the concentrations of trace elements in host niches in response to invading pathogens during infection. This work reports the interplay between d-block metal ions and their associated biomolecules using hyphenated elemental techniques to spatially quantify both elemental distributions and the abundance of specific transport proteins. Here, lung tissues were collected for analyses from naïve and Streptococcus pneumoniae-infected mice fed on a zinc-restricted or zinc-supplemented diet. Spatiotemporal distributions of manganese (55Mn), iron (56Fe), copper (63Cu), and zinc (66Zn) were determined by quantitative laser ablation–inductively coupled plasma–mass spectrometry. The murine transport proteins ZIP8 and ZIP14, which are associated with zinc transport, were also imaged by incorporation of immunohistochemistry techniques into the analytical workflow. Collectively, this work demonstrates the potential of a single instrumental platform suitable for multiplex analyses of tissues and labelled antibodies to investigate complex elemental interactions at the host-pathogen interface. Further, these methods have the potential for broad application to investigations of biological pathways where concomitant measurement of elements and biomolecules is crucial to understand the basis of disease and aid in development of new therapeutic approaches. [ABSTRACT FROM AUTHOR]

The aim of this work is to evaluate two quantitative methods, based on the external calibration applied in laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) analysis, known as (i) analytical curve and (ii) one-point calibration, using the concept of matrix matching to quantify three potentially toxic elements (PTEs) in wood samples. These can biologically register changes in the abiotic environment and be applied to monitoring climate change or environmental toxicity. In this case, standard sample preparation was evaluated to prepare the standard pellets using Pinus taeda species as a matrix-matching concept. Six pellets of P. taeda, with different Pb, Cd, and Ba concentrations, were prepared to build the analytical curve and one-point calibration strategies. The LA-ICP-MS parameters were optimised for 206Pb, 208Pb, 112Cd, 114Cd, 137Ba, and 138Ba isotope analysis in wood samples. The two calibration strategies provided 74–110% analytical recovery from certified reference materials and similar results to those obtained by ICP-MS through the acid digestion of environmental wood samples from São Paulo City (Brazil). This demonstrated the applicability of the one-point calibration strategy in quantifying PTEs in wood samples, which could be used with environmental analyses. Differences observed between the Ba isotope results obtained via LA-ICP-MS and ICP-MS quantification were related to sampling by LA-ICP-MS and the ICP-MS sample introduction, as well as to laser matrix and transport effects because of the difference between the wood species evaluated. [ABSTRACT FROM AUTHOR]

This study presents U-Pb age data obtained using an in situ LA-ICP-MS technique applied to wolframite samples from Polski Gradets (Bulgaria) and Barruecopardo (Spain). Analytical conditions were optimized using YGX2113 (wolframite) and GJ1 (zircon) natural standard reference materials (SRMs). Applying both SRMs, very similar U-Pb age results were obtained. Furthermore, the results were within the reported age error range of the host granites and granodiorites. The tungsten mineralization at Barruecopardo was dated at 315.2±5.3 Ma, while for Polski Gradets wolframite, an age of 79.0±6.8 Ma was obtained. The applied technique is assessed as applicable and suitable for further direct dating of tungsten deposits. [ABSTRACT FROM AUTHOR]

Simultaneous U–Pb and U–Th dating using laser ablation-inductively coupled plasma-mass spectrometry (LA-ICP-MS) was performed on the ca. 0.1 Ma Toya tephra and the ca. 0.08 Ma SS14-28 U–Th zircon reference material. In U–Pb dating, both Th/U and Pa/U partitioning between magma and minerals were considered. In U–Th dating, both abundance sensitivity and molecular interferences on 230Th were reevaluated. As a result, the Toya tephra yielded an accurate weighted mean U–Pb age of 0.103 ± 0.029 Ma (2σ) using zircon and monazite. Conversely, the SS14-28 zircon yielded an inaccurate U–Pb age (0.25 ± 0.10 Ma), which was attributed to low 206Pb signal intensity. Both the Toya tephra zircon and the SS14-28 zircon yielded accurate U–Th model ages of 0.108 ± 0.014 Ma and 0.078 ± 0.007 Ma, respectively. The agreement of U–Pb and U–Th ages for Toya indicates that simultaneous U–Pb and U–Th dating is possible and viable. The inappropriate age of SS14-28 U–Pb age and appropriate U–Th model age also indicates it is preferable to apply both U–Pb and U–Th dating simultaneously for young (<0.4 Ma) zircons to check internal consistency. The proposed double dating approach may be especially useful for small grains when it otherwise would be impossible to obtain multiple ages from a single grain. By adopting simultaneous U–Pb and U–Th dating using LA-ICP-MS, zircon crystallization ages as old as 4.5 Ga to as young as 0.1 Ma (or even younger) can be obtained in a quick and cost-effective manner with a reasonable (~5% at 1σ) uncertainty. [ABSTRACT FROM AUTHOR]

Alzheimer's disease (AD) is a prevalent neurodegenerative disorder characterized by cognitive decline and neuropathological hallmarks, including β-amyloid (Aβ) plaques, Tau tangles, synaptic dysfunction and neurodegeneration. Emerging evidence suggests that abnormal iron (Fe) metabolism plays a role in AD pathogenesis, but the precise spatial distribution of the Fe and its transporters, such as ferroportin (FPN), within affected brain regions remains poorly understood. This study investigates the distribution of Fe and FPN in the CA1 region of the human hippocampus in AD patients with a micrometer lateral resolution using laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS). For this purpose, we visualized and quantified Fe and FPN in three separated CA1 layers: stratum molecular–radial (SMR), stratum pyramidal (SP) and stratum oriens (SO). Additionally, chromogenic immunohistochemistry was used to examine the distribution and colocalization with Tau and Aβ proteins. The results show that Fe accumulation was significantly higher in AD brains, particularly in SMR and SO. However, FPN did not present significantly changes in AD, although it showed a non-uniform distribution across CA1 layers, with elevated levels in SP and SO. Interestingly, minimal overlap was observed between Fe and FPN signals, and none between Fe and areas rich in neurofibrillary tangles (NFTs) or neuritic plaques (NP). In conclusion, the lack of correlation between Fe and FPN signals suggests complex regulatory mechanisms in AD Fe metabolism and deposition. These findings highlight the complexity of Fe dysregulation in AD and its potential role in disease progression. [ABSTRACT FROM AUTHOR]

Rutile stands as a classical mineral within U‐Pb geochronology, offering insights into both magmatic and metamorphic events, and contributing to the understanding of provenance of detrital sedimentary rocks. Addressing the paucity of high‐quality Archaean rutile reference materials suitable for microbeam U‐Pb dating, we present a natural rutile (RKV01) sourced from the Kaap Valley pluton, South Africa, positing it as a potential Archaean reference material. Major element determination was executed via electron probe microanalysis, while trace element determination was conducted using laser ablation‐inductively coupled plasma‐mass spectrometry (LA‐ICP‐MS). The determination of U‐Pb ages involved the application of isotope dilution‐thermal ionisation mass spectrometry (ID‐TIMS), secondary ion mass spectrometry (SIMS) and LA‐ICP‐MS. The ID‐TIMS mean 207Pb/206Pb age is 3225.61 ± 0.64 Ma (2s, MSWD = 0.83), interpreted as the best estimate for the crystallisation age. The relatively high U mass fraction (~ 83 μg g‐1), extremely low Th mass fraction (~ 0.003 μg g‐1), negligible common Pb and isotopically homogeneous compositions collectively facilitated precise 207Pb/206Pb age determination via microbeam methods. Both LA‐ICP‐MS and SIMS 207Pb/206Pb ages are characterised by reproducibility and were consistent with the ID‐TIMS age within 2s analytical uncertainty. The results underscore the potential of RKV01 rutile as an Archaean reference material for microbeam U‐Pb dating. [ABSTRACT FROM AUTHOR]

The determination of elemental impurities in uranium ore concentrates (UOCs) is of great importance in the fields of nuclear forensics and nuclear safeguards and more generally for the nuclear industry. To avoid the use of chemical reagents, prevent waste generation, and reduce the duration of the analysis, a simple method based on sample preparation involving the conversion of UOCs into glass beads by alkaline fusion followed by direct measurement by laser ablation—sector-field ICP-MS (LA-ICP-MS) is proposed. External calibration was performed with a mix of UOCs and geological standard reference materials. Accurate results were obtained for most of the 48 elements of interest in six UOC materials. The lowest detection limits are in the ng g−1 range. With this method, concentrations of a wide range of elements can be determined within 24 h. [ABSTRACT FROM AUTHOR]

Chemical analysis of glass from African archaeological sites has become a standard research tool over the past decades. Despite the multiplication of studies, the continent still exhibits vast unexplored regions. One of these is the surroundings of Lake Chad. This paper discusses the results of LA‐ICP‐MS analysis of recently excavated glass beads from the late medieval Chadian site of Tié. We demonstrate that the composition of those glass beads largely matches assemblages from along the East African coast. This indicates that most of the beads examined entered the region via a hitherto undocumented east–west Sudanic route linking Northeast Africa with Lake Chad. [ABSTRACT FROM AUTHOR]

Toenails are a common monitoring tool for arsenic exposure, but the risk of external contamination of toenails has cast doubt on its usefulness. The main objective of this study is to investigate the micro-distribution of arsenic through the dorsoventral plane of nail clippings to understand endogenous vs exogenous sources. We used laser-ablation inductively coupled plasma mass spectrometry to measure arsenic through a dorsoventral cross-section of the nail plate collected from reference (N = 17) and exposed individuals (N = 35). Our main results showed (1) bulk toenail concentrations measured using ICP-MS in this study ranged from 0.54 to 4.35 µg/g; (2) there was a double-hump pattern in arsenic concentrations, i.e., dorsal and ventral layers had higher arsenic than the inner layer; (3) the double-hump was more pronounced in the exposed group (ventral: 6.25 μg/g; inner: 0.75 μg/g; dorsal: 0.95 μg/g) than the reference group (ventral: 0.58 μg/g; inner: 0.15 μg/g; dorsal: 0.29 μg/g) on average; (4) the distribution was, in part, associated with different binding affinity of nail layers (i.e., ventral > dorsal > inner); (5) most individuals in the higher exposure group showed > 25% contamination in ventral and dorsal nail layers; and (6) there were no statistically significant correlations between LA-ICP-MS arsenic with either bulk toenail arsenic or urine arsenic from the same individuals. Our results on micro-distribution and binding affinity provide insight into the impact of external contamination on arsenic concentrations and show how LA-ICP-MS can access the protected inner nail layer to provide a more accurate result. [ABSTRACT FROM AUTHOR]

A total of 146 glass samples from Daoye, Daoye South, and Wujiancuo in southwestern Taiwan were subjected to elemental analysis using LA-ICP-MS and SEM–EDS. These samples cover a time span from the first to the eighth century CE. The results provide evidence of the existence of multiple long-distance glass exchange networks that directly or indirectly connected Taiwan to Southeast Asia, South Asia, West Asia, and possibly the Mediterranean region. The predominance of the South Asian m-Na-Al glass sub-type 1 suggests that Taiwan mainly participated in the South China Sea maritime glass exchange network, while the identification of a newly recognised sub-type, m-Na-Al low Al low Ca, indicates the possibility of small-scale glass production workshops or a less controlled recipe for m-Na-Al glass production. Furthermore, this research reveals compelling evidence linking early v-Na-Ca glass found in Taiwan to origins in Mesopotamia or Sasanian territories, with the secondary production areas remain unclear. In addition, a potash glass and a Roman HIMT glass were also discovered. The chemical profiles of the potash glass do not align with those of early potash glass, while the HIMT glass can be attributed to the Roman Mediterranean. Taken together, these findings shed light on the intricate maritime exchange networks that operated over vast distances, spanning from the eastern part of the South China Sea to West Asia, covering over eight thousand kilometers. This study thus addresses a significant research gap regarding the maritime exchange of glass during the understudied period of the early to mid-1st millennium CE around the South China Sea and beyond. [ABSTRACT FROM AUTHOR]

Two calcite LA-ICP-MS U-Pb ages of 534 ± 26 Ma (MSWD = 5.9) and 456 ± 43 Ma (MSWD = 3.8) were obtained from the Nanfen Formation, Xihe Group in the southern Liaoning Province, northeastern China, which significantly postdate the theoretical depositional age of sampling horizon. This means they represent timing of post-depositional hydrothermal event possibly induced by synchronous far-field magmatism in the South Qinling. Occurrence of common Pb enriched muddy components coupled with input of "mantle"-like common Pb could account for the relatively low U contents and high common Pb contents in the dated muddy carbonates. We recommend that micro-domains of carbonates are prescreened by rapid in situ carbonate U-Pb geochronology to demonstrate whether they are of primary or secondary origin before utilizing them for chemostratigraphic study. [ABSTRACT FROM AUTHOR]

The cellular accumulation and the underlying mechanisms for the two ruthenium-based anticancer complexes [RuII(cym)(HQ)Cl] 1 (cym = η6-p-cymene, HQ = 8-hydroxyquinoline) and [RuII(cym)(PCA)Cl]Cl 2 (PCA = N-fluorophenyl-2-pyridinecarbothioamide) were investigated in HCT116 human colorectal carcinoma cells. The results showed that the cellular accumulation of both complexes increased over time and with higher concentrations, and that 2 accumulates in greater quantities in cells than 1. Inhibition studies of selected cellular accumulation mechanisms indicated that both 1 and 2 may be transported into the cells by both passive diffusion and active transporters, similar to cisplatin. Efflux experiments indicated that 1 and 2 are subjected to efflux through a mechanism that does not involve p-glycoprotein, as addition of verapamil did not make any difference. Exploring the influence of the Cu transporter by addition of CuCl2 resulted in a higher accumulation of 1 and 2 whilst the amount of Pt detected was slightly reduced when cells were treated with cisplatin. Complexes 1 and 2 were further explored in zebrafish where accumulation and distribution were determined with ICP-MS and LA-ICP-MS. The results correlated with the in vitro observations and zebrafish treated with 2 showed higher Ru contents than those treated with 1. The distribution studies suggested that both complexes mainly accumulated in the intestines of the zebrafish. [ABSTRACT FROM AUTHOR]

In this work, we prepared three CaWO4 single crystals (CaW‐0, CaW‐1 and CaW‐3) doped with rare earth elements (REEs) at nominal mass fractions of 50, 250 and 5000 μg g‐1 using the Czochralski method. Electron probe microanalysis (EPMA) and laser ablation‐inductively coupled plasma‐mass spectrometry (LA‐ICP‐MS) were employed to evaluate the within‐ and between‐unit homogeneity of major elements and REEs, respectively. The within‐unit variation (sr) of 0.40–0.84% and between‐unit sr of 0.14–1.48% for major elements were obtained. Within‐ and between‐unit sr of 0.53–5.56% were also found for REEs by LA‐ICP‐MS spot analyses. A comparison of the sr of repeat analyses was compared with the analytical uncertainty (u), i.e., the mean square weighted deviation (MSWD), which is close to or slightly higher than 1, indicating that no obvious chemical heterogeneity was found in these crystals. Reference values for these elements were obtained through various analytical methods across four different laboratories and applications of the reference materials to calibrating REE mass fractions in a natural scheelite were performed. No significant difference of the results was found as t values are less than 2.75 at the 99% confidence interval. The excellent linearity (R2 > 0.98) between the REE mass fractions and both LA‐ICP‐MS signal intensity and wafer absorbance was found, but the crater height and the absolute mass transported into ICP‐MS decreased when REE mass fractions as well as the colour of crystals increased. These results suggest that the reference materials have the potential to calibrate REE mass fractions in natural scheelite. [ABSTRACT FROM AUTHOR]

We characterise zircon megacrysts from the Kawisigamuwa carbonatite as a new potential reference material for laser ablation‐inductively coupled plasma‐mass spectrometry U‐Pb and Hf isotope measurement. We studied ten 0.5–4 cm long, brown megacrysts that consist of oscillatory zoned (OZ) and nearly featureless cathodoluminescence‐bright recrystallised (RX) zircon domains. The zircons have low to moderate radiation damage (total α‐dose < 0.5 x 1018 events g‐1), tested by the measured FWHM of the ν3 (SiO4) Raman band < 5 cm‐1. An ID‐TIMS weighted mean 206Pb/238U age of 532.39 ± 0.66 Ma (2s uncertainty) was determined for OZ zircon domains of three grains. While hafnium content varies within and between crystals (6630–9960 μg g‐1) the in situ mean 176Hf/177Hf ratios of ten crystals overlap within uncertainty. We recommend a mean 176Hf/177Hf ratio of 0.282003 ± 0.000020 (2s) as preliminary working value for OZ domains. Two OZ megacrysts yield indistinguishable δ18OVSMOW of 12.1 ± 0.4‰ and 12.2 ± 0.4‰ (2s). Elevated Th/U (> 1.5), Zr/Hf (59–75) and low hafnium contents in OZ domains are similar to those of zircons from carbonatites of mantle origin, while high δ18O and low εHfi (‐15.8 to ‐17.1) indicate a crustal contribution. The zircons probably grew from crustal‐derived carbonate melts under high grade metamorphic conditions. [ABSTRACT FROM AUTHOR]

We present the results of a study to generate reference glasses that reflect an environment analogous to historic nuclear fallout samples of interest for post‐detonation nuclear forensics. The glasses were generated by melting and then quenching SiO2, Al2O3 and CaCO3 powders. Two suites of glasses with three distinct U isotopic ratios were successfully made with enrichments in the 235U isotope (~ natural [0.72%], ~ 53% and 94%), but the bulk elemental data showed heterogeneity (~ 10% RSD) with U mass fractions ranging from 331.47 to 373.63 μg g‐1. Spatially resolved U isotopic measurements were performed using three mass spectrometry techniques (secondary ion mass spectrometry‐single stage accelerator mass spectrometry [SIMS‐SSAMS], large geometry [LG] ‐ SIMS, and laser ablation‐inductively coupled plasma‐mass spectrometry [LA‐ICP‐MS]) across five National Laboratories. The results showed good agreement with the bulk U isotopic data for the low, medium, and high U mass fractions. We conclude that despite elemental heterogeneity, these samples can serve as useful working reference materials for spatially resolved nuclear fallout analyses, as well as for other related spatially resolved analyses. [ABSTRACT FROM AUTHOR]

This study examined the impact of two different transport mechanisms and water/cement (w/c) ratios on the ingress depth of damaging ions into hardened cement paste (hcp). In addition, the effect of sample preparation, i.e. drying before and after exposure, is considered within this study. We applied Laser Ablation Inductively Coupled Plasma Mass Spectrometry (LA‐ICP‐MS) as an analytical method to determine the ion ingress depth. The results show that post‐drying of the samples (after exposure) significantly affects the ion ingress depth in hcp as determined by LA‐ICP‐MS. Our results confirmed, as previous studies, that ions ingress the hcp faster due to capillary suction than diffusion. This work shows that although LA‐ICP‐MS is not commonly applied in the analysis of construction material, it has a vast potential to examine the profile ingress of damaging ions. [ABSTRACT FROM AUTHOR]

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 0.17 μg·L−1 (Mn) to 8.67 μg·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 the microwell 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. [ABSTRACT FROM AUTHOR]

The compositional zoning of the major divalent cations in metamorphic garnet is a useful tool in reconstructing the pressure–temperature path. However, trace elements can provide a better-preserved record of petrogenetic evolution due to their strong affinity in garnet and slow diffusion rates. In this study, three high-pressure micaschist samples of varying composition and garnet textures from the Krušné hory Mountains (Saxothuringian zone, Bohemian Massif) were examined. By utilizing electron probe micro-analysis and laser ablation inductively coupled plasma mass spectrometry, three distinct types of compositional zoning in garnet were identified by compositional mapping. The zoning types were classified as continuous core-to-rim change, concentric annular changes, and overprinting of a pre-existing distribution; all three provide information on the original mineral composition and texture before garnet overgrowth. The transition from overprint to annular zoning shows relation to temperature increment. The annular zoning allowed the identification of several coupled substitutions, including alkali (sodium and lithium) + yttrium and the alkali + phosphorus substitution which is typical of high- to ultra-high-pressure conditions. The formation of annuli zoning was interpreted to originate not only from the decomposition of trace element bearing phases, but also to be related to the availability of fluid medium during garnet growth. Two samples contained atoll texture garnets, interpreted to be originated from the dissolution of the garnet central part, chemically distinct from the new garnet growing coevally on the rim or replacing the original central part. This proposed process is evidenced by the mass balance calculation of yttrium and heavy rare earth elements between the dissolved garnet and newly formed parts. [ABSTRACT FROM AUTHOR]

BACKGROUND: Trace element information in carbonates provides key constraints for investigating ancient environments, paleoclimate evolution, shell-mantle interactions, diagenesis and mineralization processes. The accurate determination of trace element content in carbonate minerals have always been a primary focus. Laser ablation-inductively coupled plasma-mass spectrometry (LA-ICP-MS) can provide detailed information on trace element content in carbonate minerals. However, the elemental concentrations in carbonate minerals are usually extremely low (from hundreds of pg/g to tens of ng/g). A large spot size (from 44 to 100μm) is often used for trace element measurements in carbonate minerals. Therefore, the detection capability of low-content elements in carbonate minerals and the spatial resolution of LA determination still need to be improved. OBJECTIVES: To develop a new analytical method for determination of low-content trace elements in carbonate minerals with LA-ICP-MS. METHODS: A new local aerosol extraction ablation cell was proposed in this study. Laser ablation was performed using high-repetition rates with the new designed ablation cell. The elemental contents in carbonate reference materials MACS-3, CGSP-A, CGSP-B, CGSP-C, and CGSP-D were determined with both ns and fs LA-Q-ICP-MS with a spot size of 32μm. Here, NIST 610 glass was used as an external calibration material and Ca was used as an internal standard. RESULTS: The obtained peak height of a single laser shot was enhanced by a factor of 13 with the local aerosol extraction ablation cell because of the rapid washout time. The signal intensities were increased by 1.5 times under high-repetition rate laser ablation mode. Therefore, the detection limits of trace elements in carbonate minerals obtained from nanosecond laser ablation at high repetition rates (20Hz) were reduced by 5-8 times compared to conventional analysis (6Hz). The detection limits of trace elements were reduced by 5-10 times with the frequency of femtosecond laser ablation increased from 10Hz to 100Hz. The elemental contents in carbonate reference materials were measured with both ns and fs LA-Q-ICP-MS with a spot size of 32μm. The obtained results of lithophile elements (e.g., Sc, Sr, Y, Ba, La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, and Th) in carbonate CGSP series and carbonate MACS-3 showed good agreement with their reference values. However, the measured results of siderophile and chalcophile elements (e.g., Ni, Cu, Zn, As, Cd, Sn, Sb, and Pb) showed systematic bias (>20%), which may be related to the “downhole” fractionation effect caused by the high-repetition rate laser ablation used in this study. CONCLUSIONS: The new designed local aerosol extraction ablation cell combined with high-repetition rate laser ablation mode significantly improved the spital resolution and determination ability of low-content elements in carbonate minerals. The obtained results of lithophile elements in carbonate CGSP series and carbonate MACS-3 showed good agreement with their reference values using ns- and fs-LA-Q-ICP-MS with a spot size of 32µm. It is worth noting that the spatial resolution and the detection capability of ultra-low-content elements in carbonate minerals could be further improved with the proposed LA method combined with high-sensitivity magnetic sector mass spectrometry. [ABSTRACT FROM AUTHOR]

In the Chemnitz Basin (Saxony, central Germany), up to 1,500 m thick early Permian sediments with intercalated, predominantly acidic pyroclastics were deposited. Numerous fossil records allow a biostratigraphic correlation of the strata with other early Permian successions of the middle Variscides. Significant floral and faunal elements were found in the Planitz Formation of the Chemnitz Basin, which is bounded at the base by the Grüna Tuff and at the top by the Planitz Ignimbrite. Radioisotopic data are only available for the Planitz Ignimbrite, but they contradict biostratigraphic data. Based on LA-ICP-MS measurements, new U-Pb zircon ages are determined for the Planitz Ignimbrite and, for the first time, also U-Pb zircon ages for the Grüna Tuff. The challenge of deriving an extrusion age for both the Planitz Ignimbrite and Grüna Tuff from these data is discussed. [ABSTRACT FROM AUTHOR]

Sedimentary rocks exposed at Dob's Linn, Scotland, have significantly influenced our understanding of how life evolved over the Ordovician to Early Silurian. The current interpreted chronostratigraphic boundary between the Ordovician and Silurian periods is a Global Boundary Stratotype Section and Point (GSSP), calibrated to 443.8 ± 1.5 Ma (Hirnatian–Rhuddanian age), based on biostratigraphic markers, radioisotopic dates and statistical modelling. However, challenges arise due to tectonic disturbances, complex correlation issues and the lack of systematic dating in Ordovician–Silurian stratigraphic sections. Here, hundreds of zircon grains from three metabentonite ash horizons were dated using Laser Ablation Inductively Coupled Plasma Mass Spectrometry (LA-ICP-MS). A subset of the grains were re-analyzed using Chemical Abrasion Isotope Dilution Thermal Ionization Mass Spectrometry (CA-ID-TIMS). We present a high-precision CA-ID-TIMS 238U-206Pb weighted mean date of 440.44 ± 0.55/0.56/0.72 Ma (±analytical/with tracer/with U-decay constant) for the Coronagraptus cyphus biozone. However, the study reports younger, and in certain cases, older LA-ICP-MS zircon dates within the Coronagraptus cyphus , Akidograptus ascensus and Dicellograptus anceps zones, suspected as being influenced by Pb loss and LA-ICP-MS matrix mismatch. The study reports concerns about the suitability of Dob's Linn as a GSSP section and examines various LA-ICP-MS maximum depositional age (MDA) approaches, suggesting the use of the TuffZirc date and the youngest mode weighted mean (YMWM) as suitable MDA calculations consistent with CA-ID-TIMS results. [ABSTRACT FROM AUTHOR]

In the last century, a blue–green colored gemstone known as Larimar with a special sea-wave pattern was discovered in the Dominican Republic. Larimar is composed of the mineral pectolite, which has a chemical composition of NaCa2Si3O8(OH) and is usually white in color. Cu2+ has always been considered to be the primary genesis of the blue color shown in Larimar, because native copper often grows together with Larimar. To clarify whether copper is the main reason for the origin of blue–green pectolite, we utilized laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) techniques to analyze trace elements in the pectolite samples and compared the relationship between elements and colors. The results show that vanadium and iron are the main origins of the sky-blue and green color of Larimar. We also discovered that it is not only the chemical elements that affect the color shades of the mineral, but the orientation of the radial fiber crystals also plays a critical role. The sea-wave pattern and the changes in the color saturation of radial pectolite are due to the transmittance of visible light through different viewed angles under changing crystal orientations. Our results reveal the chemical and physical factors behind the color and sea-wave pattern of Larimar. In addition, to our knowledge, this is the first time that the formation age of Larimar has been proven to be approximately equal to or younger than 40 ka, using the U-Th dating of calcite growth together with pectolite. [ABSTRACT FROM AUTHOR]

In this work, the iconography and cultural contexts of two duplicate Maya effigy cylinders reportedly found in caves and rock shelters at Lake Pethá, Department of Ocosingo, Chiapas, are studied. Following a comparative analysis, we tentatively identify a new regional Maya style of flanged (aletas) ceramic cylinders focused around the ancient Maya center of Toniná in the Ocosingo Valley. The iconographic attributes chronologically place the cylinders to around the Postclassic to Early Colonial period. Additionally, the application of archaeometry, specifically Laser Ablation Inductively Coupled Mass Spectrometry (la-icp-ms) and Neutron Activation Analysis (naa) indicate that the two cylinders were likely made at the same time with the same clay. The results demonstrate the authenticity of the cylinders and their possible production by the same artist or ceramic workshop at Lake Pethá or nearby in the Ocosingo Valley. [ABSTRACT FROM AUTHOR]

Columbite‐tantalite LA‐ICP‐MS U‐Pb dating is a fast and useful method to determine the age of rare‐metal deposits and fingerprint the provenance of columbite‐tantalite ore concentrates. Accurate LA‐ICP‐MS U‐Pb dating requires matrix‐matched reference materials. We analysed three columbite‐tantalite samples (SN3, HND and RL2) from China using ID‐TIMS and LA‐ICP‐MS to assess their potential as reference materials for in situ U‐Pb dating. Coltan 139 and these three columbite‐tantalite samples with variable compositions yielded internally consistent LA‐ICP‐MS U‐Pb ages when using each other for calibration and the weighted mean 206Pb/238U ages are comparable to respective ID‐TIMS ages. Composition‐dependent U‐Pb fractionation seems to be insignificant under the LA‐ICP‐MS conditions used. Sample SN3 has a low percentage of heterogeneity for 206Pb/238U ages (4%) with low common Pb contributions (f206 < 1%) and shows a good potential in calibrating unknown samples as primary reference material for LA‐ICP‐MS analysis. Samples RL2 and HND have altered sections characterised by high LREE contents, flat LREE patterns and old 206Pb/238U apparent ages, and are not suited as reference materials. The low 207Pb/206Pb intercepts for samples RL2 and HND lack geological meaning but provide strong evidence that the disturbed U‐Pb systematics with anomalous apparent 206Pb/238U ages is a secondary feature. [ABSTRACT FROM AUTHOR]

A new reference material, STDGL3, for the calibration of in situ analyses of sulfide minerals by LA‐ICP‐MS has been developed and characterised. It represents a lithium‐borate‐based glass containing a mixture of Zn‐ and Fe‐sulfide concentrates doped with several chalcophile elements as well as Zr, Gd, Hf and Ta required for assessing common interferences on Ag, Au and Pt. STDGL3 has a wider range of elements and a better homogeneity compared with existing reference materials for LA‐ICP‐MS analysis of sulfides. Compositional variations for most elements are below 3% RSD, below 5% RSD for Ag, Au and Pt, and below 7% RSD for Se, when performing spot analyses with a 50 μm beam size. Its preparation recipe is reproducible allowing for multiple batches to be made. Use of STDGL3 significantly improves accuracy of sulfide mineral analysis by LA‐ICP‐MS when compared with use of other available reference materials. Performance of STDGL3 was evaluated using several different laser systems. No significant change was observed between 193 nm ArF excimer lasers with 5 and 20 ns pulse widths, but use of 213 and 248 nm lasers displays more systematic differences, especially when analysing galena. Correction coefficients are needed for some elements (Zn and Cd in particular) when analysing sulfide minerals using STDGL3 as a calibration reference material. [ABSTRACT FROM AUTHOR]

Four natural chromite samples (LBS13‐04, LBS13‐06 and LBS13‐13) from the Luobusa ophiolite (China) and 16SW2‐6 from the Stillwater Complex (USA) were developed as reference materials for in situ element microanalysis. Approximately 8 g of chromite fragments with grain sizes of 0.5–1.5 mm from each chromite sample were separated under a binocular microscope and analysed by EPMA, XRF, LA‐ICP‐MS and solution nebulisation ICP‐MS techniques for major and trace elements at six laboratories. The results show that the four chromite samples are homogeneous with respect to MgO, Al2O3, Cr2O3, FeO, Sc, Ti, V, Mn, Co, Ni, Zn and Ga. These samples are thus suitable to be used as reference materials for in situ microanalysis. [ABSTRACT FROM AUTHOR]

The concentrations of trace elements in pyrite and enargite-luzonite from target 185 of the copper-gold high sulphidation Chelopech deposit were determined by LA-ICP-MS. Their average contents in ppm based on 12 analyses of pyrite and 10 analyses of enargite-luzonite are respectively: Ti (6548) > Cu (3449) > V (580) > Mn (299) > Pb (173) > As (157) > Se (149) > Te (122) > Zn (80) > Co (79) > Bi (41) > Cr (29) > W (25) > Sn (22) > Ni (17) > Au, Ga (15) > Ag (14) > Mo (9) > Sb (5) > Tl (4) > Hg (1) > In (0.2) for the first one and Fe (26531) > Zn (22140) > Sb (11014) > Bi (7956) > Se (1730) > Sn (1016) > Pb (995) > Te (326) > Mn (205) > Mo (170) > Hg (100) > Ge (88) > Ag (46) > Ti (42) > W (25) > Cd (24) > V (19) > Au (16) > In (4) > Tl (3) > Ga (1) for the second. [ABSTRACT FROM AUTHOR]

In the process of in situ zircon U–Pb dating, it is an effective means to overcome the matrix effect by using a matrix-matched external reference material. However, the limited number of available zircon reference materials still makes it difficult to meet the research needs. In this paper, we performed a preliminary analysis of the gemological characteristics, trace elements and U–Pb ages of natural zircon CAM18 to assess its suitability as a reference material for laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) U–Pb dating. This tawny, gem-quality zircon has no visible inclusions and weighs approximately 0.55 g. Its density, full width at half maximum (FWHM) of the Raman peak and alpha flux (Dα) indicate that the sample has suffered mild-to-moderate radiation damage without any thermal treatment. The LA-ICP-MS U–Pb dating results reveal that the trace elements content and U–Pb ages of the sample are fairly homogeneous at the 50 μm scale, and there is no obvious loss of radiogenic Pb. The 206Pb/238U age (571.0 ± 3.0 Ma, 2s) and 207Pb/235U age (573.4 ± 6.0 Ma, 2s) are consistent within the analytical uncertainty, and the calculated concordia age is 571.4 ± 1.4 Ma (2s, n = 20). The variation in the 206Pb/238U ages is small, with a measurement repeatability of 0.46% (RSD), which is within the uncertainty of the age accuracy obtained by LA-ICP-MS. The oscillatory zoning, Th/U ratio (0.2) and chondrite-normalized rare-earth element (REE) pattern imply a magmatic origin of zircon CAM18. The Ti-in-zircon temperature ranges from 714 to 742 °C, and the oxygen fugacity ranges from ΔFMQ−2.87 to ΔFMQ−3.17, suggesting that it is crystallized in a reducing environment. All the results show that zircon CAM18 may has great potential in LA-ICP-MS U–Pb dating. [ABSTRACT FROM AUTHOR]

Dengjiashan is a large‐scale Pb–Zn deposit discovered in the western part of the Xicheng ore field within the West Qinling metallogenic belt. Information regarding the distribution and occurrence of trace elements in ore minerals and mineralization, as well as the genesis of this deposit, remains scarce. Laser ablation inductively coupled plasma mass spectrometry (LA‐ICP‐MS) analysis and elemental mapping were used to determine the distribution and occurrence of trace elements in the sulfide minerals of the Dengjiashan deposit, as well as delineate the process of its genesis. Our results showed that the trace elements enriched in the different sulfides were significantly different. Sphalerite is the main carrier mineral of the scattered elements Cd, Ge and Ga. Based on the trace element content and ratio, principal component analysis and colour of the sphalerite and pyrite, the deposit likely formed in a medium‐temperature environment. The comparative analysis of trace elements from multiple deposits of different origins, combined with the geological characteristics and distribution of sulfide trace elements, suggests that Dengjiashan is a sedimentary exhalative (SEDEX)‐type deposit. As the metallogenic process had a closer relationship to medium‐low temperature hot brine and later tectonic metamorphic hydrothermal fluid, than with magmatic hydrothermal fluid, the deposit is likely of non‐magmatic SEDEX–hot brine superimposed transition origin. This study provides additional insight on the distribution of trace elements in the sulfide minerals of the Dengjiashan deposit, as well as the processes that led to its formation, and may further facilitate ongoing and future key metal prospecting and exploration efforts. [ABSTRACT FROM AUTHOR]