Laser Ablation Inductively Coupled Plasma Mass Spectrometry Research Articles

A novel standard for forensic elemental profiling of polymers by LA-ICP-TOF-MS

Plastic materials are often found on crime scenes in improvised explosive devices. Determining the trace-elemental composition of polymer parts may yield discrimination between samples from different sources. Although quantitative laser ablation-inductively coupled plasma-mass spectrometry (LA-ICP-MS) is well established for forensic glass analysis, the lack of sufficiently reproducible and homogeneous reference standards hampers accurate quantification of trace elements in polymers. Therefore, the present study introduces a new standard for quantitative elemental profiling of polymers. A novel approach was developed for producing polyethylene (PE), polystyrene (PS), and polyvinyl chloride (PVC) standards containing 23 elements at three concentrations. The LA-ICP-TOF-MS measurements showed excellent linear response with R2 > 0.99 for almost all elements and polymer matrices. Additionally, homogeneity was significantly improved to an average of 10% within-, and 17% between-sample variation. PVC and PE matrices presented the best homogeneity which was confirmed by line ablations. The added value of the standards was demonstrated by evaluating a set of realistic forensic polymer evidence items. The between-run variation was substantially reduced from 42% in absence of calibration to 30% when correcting with an elemental internal standard and even to 24% when applying the novel standards. In addition, its discriminating power between different classes was increased, as demonstrated by ANOVA and principal component analysis. In conclusion, this study shows the feasibility of using a novel standard for quantitative analysis of chemical attribution signatures of trace elements in polymers by LA-ICP-TOF-MS. The use of the polymer standards significantly improves classification and forensic comparison of polymer-based evidence.

The Recycling of End-of-Life Lithium-Ion Batteries and the Phase Characterisation of Black Mass

Black mass is the industry term applied to end-of-life (EoL) lithium-ion batteries that have been mechanically processed for potential use as a recycled material to recover the valuable metals present, including cobalt, lithium, manganese, nickel and copper. A significant challenge to the effective processing of black mass is the complexity of the feed material. Two samples of black mass from a European source were analysed using a combination of methods including automated SEM-EDS (AMICS) to characterise and quantify the phases present and particle chemistry. Micro X-CT imaging, overlain onto automated mineralogy images, enabled the 3D morphology of the particles to be determined. Micro-XRF was used to map the copper, nickel, manganese and cobalt-bearing phases. Since Li cannot be detected using SEM-EDS, its abundance was semi-quantified using laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS). The integration of these complimentary analytical methods allowed for detailed phase characterisation, which may guide the potential hydrometallurgical or pyrometallurgical recycling routes and chemical assaying.

A grain-by-grain comparison of apatite fission-track analysis by LA-ICP-MS and the External Detector Method

Laser-ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) is increasingly used in fission-track analysis to determine the uranium content of host mineral specimens, particularly apatite. Fission-track dating by LA-ICP-MS (LAFT) has several advantages over the conventional External Detector Method (EDM), particularly in terms of sample turn-around times and the fact that neutron irradiations and the handling of radioactive materials are no longer necessary, while providing a similar level of in-situ information about parent nuclide (238U) concentrations. In addition, it facilitates the simultaneous measurement of multiple isotopes for double or triple-dating approaches or compositional characterisation. While it is often implicitly assumed that the EDM and LAFT fission-track dating approaches produce equivalent results, this assertion has yet to be adequately tested. We present an extensive dataset of apatite fission track results from 17 samples representing a large range of fission-track ages (∼0–2 Ga), 238U concentrations (0.14–410 ppm) and thermal histories that were analysed grain-by-grain using both techniques in order to investigate whether they yield concordant results during routine fission-track analysis.Apart from a few outliers, our data show that 238U concentrations measured by the EDM and LAFT techniques yield indistinguishable results across at least three orders of magnitude when a similar calibration system against rapidly cooled standards (e.g., Durango) is used. Comparison of single grain pooled and central ages reveals that LAFT ages are within error of EDM ages for apatite fission track standards such as Fish Canyon Tuff or Durango, as well as for a range of other samples whose shorter mean confined track lengths (<13 μm) and broader track distributions indicate they experienced more complex cooling histories. The most important conclusion here is that both the conventional EDM and LAFT methods can be expected to yield identical results for the breadth of ages, 238U concentrations, and underlying thermal histories commonly found in real world apatites.Importantly, the aggregate empirical calibrations for EDM and LAFT mask an underlying assumption that the mean etchable range of fission fragments is a constant having the mean value observed for spontaneous tracks in age standards such as the Durango apatite. Given that this assumption is known to be false in the great majority of samples, it is our view that empirically derived EDM and LAFT fission-track ages are best considered as model ages and that there should be greater clarity about the assumptions involved in their calculation.

In situ Strontium isotope stratigraphy of fish teeth in deep-sea sediments from the western Clarion-Clipperton Fracture Zone, eastern Pacific Ocean

The geochronology of deep-sea sediments beneath the carbonate compensation depth (CCD) presents a challenge due to the calcareous microfossils dissolution, low sedimentation rates, sedimentary hiatus, and redeposition. Fish teeth, commonly found in deep-sea sediments, have been utilized for Sr isotope stratigraphic dating. However, continuous Sr isotope exchange with pore water limits the utility of fish teeth in this context.In this study, we employed laser ablation multi-collector inductively coupled plasma mass spectrometry (LA-MC-ICPMS), scanning electron microscopy (SEM), and laser ablation inductively coupled plasma mass spectrometry (LA-ICPMS) to obtain accurate stratigraphic chronology results from rare earth element and yttrium (REY)-rich sediments in the Clarion-Clipperton Fracture Zone (CCFZ) of the Pacific Ocean.Our analysis indicated that a fish tooth characterized by a dense structure and low La content exhibited a relatively initial 87Sr/86Sr ratio. Additionally, La contents at the same depth displayed a strong positive correlation with 87Sr/86Sr ratios, suggesting that Sr isotopes exchange with pore water during early diagenesis when La and other elements entered the fish teeth. However, certain fish teeth were able to resist early diagenesis alteration due to their dense structure.Based on in situ Sr-isotope stratigraphy results, we estimated the REY-rich layer age in core GC1901 to be 24–32 Ma, consistent with the REY-rich layers of DSDP/ODP in the CCFZ. Our study thus provides a new method for in situ Sr isotope analysis of fish teeth, which improves the accuracy of Sr isotope stratigraphy of pelagic sediments and could be widely used in deep-sea exploration.

Multistage mineralization of the Liling goldfield (NE Hunan) in the Jiangnan Orogen: Constraints from hydrothermal rutile U–Pb dating and sericite Rb–Sr dating

The Liling goldfield located in northeastern (NE) Hunan contains >200 tons of proven gold reserves. The gold mineralization age in Liling has long been controversial due to the lack of datable minerals. In this study, petrographic observations indicate that hydrothermal rutile and sericite were precipitated with auriferous pyrite/arsenopyrite in the ore veins. The electron probe microanalysis (EPMA) results show that the sericite from ores and the sericite from Neoproterozoic slate display distinct compositions (Especially Al, K, and Ti). The high W (1,081–36,456 ppm) and low Zr (21.35–288.7 ppm) contents of the rutile suggests a hydrothermal origin. We reported new laser ablation-inductively coupled plasma-mass spectrometry (LA-ICP-MS) U-Pb ages of ore-stage hydrothermal rutile (415.2 ± 8.3 Ma) for the Tuanshanbei gold deposit, and sericite Rb-Sr ages (417.6 ± 12.9 Ma and 216.9 ± 7.8 Ma) for the Tuanshanbei and Yanlinsi gold deposits in the goldfield. The new data confirm that multistage gold mineralization has occurred in the Liling goldfield, and falls within the generally accepted timing (ca. 430–400 Ma and 250–200 Ma) of gold mineralization in the Jiangnan Orogen. Integration of geological characteristics, tectonic setting, and geochronology of the Liling goldfield suggest two Au mineralization episodes, which occurred in the Late Silurian-Early Devonian intracontinental orogeny and Triassic intracontinental orogeny, respectively.

In-situ elemental quantitative imaging in plant leaves by LA-ICP-MS with matrix-matching external calibration

Due to the enormous interest in plants related to bioscience, environmental and toxicological research, analytical methods are expected with the ability of getting information on elemental transfer, distribution and contents in plants. In this work, a mixture of gelatin (GA) and hydroxypropyl methyl cellulose (HPMC) was prepared to simulate plant matrix, a method based on laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) with matrix-matching external calibration was proposed for direct quantification of multiple elements in plants. The composition of GA&HPMC substrate was optimized, such as the concentration of spiked nitric acid, the mass fraction of both GA and HPMC in the substrate and the mass ratio of GA: HPMC. After spiking elemental solution, coating the mixture onto a glass slide and drying overnight at room temperature, GA&HPMC substrate was obtained. The substrate obtained with GA: HPMC of 8: 2 was used to fabricate the standard series, which exhibited good elemental homogeneity and similar elemental signal intensities in LA-ICP-MS detection to that obtained for plant Certified Reference Material (CRM). CRMs of different plants including Citrus leaf (GBW10019), Tea (GBW07605), Beans (GBW10021) and Scallions (GBW10049) were further pressed into pellets and subjected to the proposed method, and the quantification accuracy was demonstrated. The limits of detections of this method were found to be 0.003 (Ce)-104 (Ca) μg g−1, with a wide linear range (0.01–10000 μg g−1) for 17 target elements. The application potential of the method was further demonstrated by performing elemental imaging in Trigonotis peduncularis leaves. Rapid in-situ quantitative imaging of Zn, Cu, Sr and Mn was achieved, and the elemental quantitative distributions were discussed. The constructed substrate helped direct elemental quantification in plants. It provided a powerful and efficient tool for the investigation of the distribution and transfer of elements in plants, favoring further exploration of elemental bioavailability, transport and toxicity mechanisms.

Metal distributions in human hair strand cross-section: Advanced analysis using LA-ICP-MS in dentistry

Human hair is a biomarker that is crucial in investigating toxic metal exposures. Thirteen elements (Li, Mg, Cr, Mn, Fe, Co, Ni, Cu, Zn, Sr, Ag, Ba, and Hg) commonly found in hair strands from dentistry environments were investigated using laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS). Previous studies have employed partial ablation along hair strands to avoid contamination from mounting materials. The partial ablation can be problematic if element chemistry within the hair is not homogeneous. In this study, element variations along cross-sections of human hair strands were investigated. A number of elements showed internal variations with most elements enriched at the cuticle, emphasizing the importance of complete ablation for the characterization of human hair element chemistry. Complete and partial ablation LA-ICP-MS results were verified against solution nebulization SN-ICP-MS. Complete LA-ICP-MS showed a better agreement with SN-ICP-MS. Therefore, the developed LA-ICP-MS method can be applied to monitor the health of dental workers and students exposed to dental environments.

Quantitative bioimaging of copper in frozen liver specimens from cats using laser ablation-inductively coupled plasma-mass spectrometry.

The aim of this study was to assess laser ablation-inductively coupled plasma-mass spectrometry (LA-ICP-MS) as a tool for measuring concentrations and determining accumulation of copper in frozen liver specimens from cats. Six frozen liver specimens were evaluated by qualitative copper staining and quantitative flame atomic absorption spectroscopy. Tissue specimens were cryo-sectioned and quantitative bioimaging of copper was performed using LA-ICP-MS. Results were compared with those obtained using conventional methods. Of the six specimens, only one showed positive staining for copper with rhodanine. Using flame atomic absorption spectroscopy (FAAS), one specimen showed a deficient copper level (<100 µg/g dry weight), two specimens had copper within the reference interval (RI; 150-180 µg/g) and three specimens had copper concentrations above the RI. Bioimaging from LA-ICP-MS showed inhomogeneous distribution of hepatic copper. The areas with dense copper accumulation were represented as hotspots in the liver specimens. Hepatic copper quantification by LA-ICP-MS correlated well with copper quantified by FAAS (r = 0.96, P = 0.002). Our findings suggest that quantitative bioimaging by LA-ICP-MS could be used to demonstrate the distribution and concentration of copper in frozen liver specimens from cats. The distribution of copper in these specimens was inhomogeneous with dense accumulation represented as hotspots on tissue sections. A positive correlation of hepatic copper concentrations determined by LA-ICP-MS and FAAS was found. Further studies to establish an RI for hepatic copper using this technique and to further determine its clinical utility are warranted.

The new frontier of microstructural impurity research in polar ice

AbstractDeciphering the localisation of solid and dissolved impurities on the micron-scale in glacial ice remains a challenge, but is critical to understand the integrity of ice core records and internal deformation. Here we report on the state-of-the-art in microstructural impurity research by highlighting recent progress in bringing together cryo-Raman spectroscopy and laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS). We show the potential of both methods and discuss possibilities to improve inter-method approaches aiming for a more holistic understanding of the evolution of impurity localisation throughout the ice column, including post-depositional processes. In this framework, we elaborate on future research priorities such as LA-ICP-MS imaging on firn samples and integrating a large cryo-cell with imaging capabilities.

Multimodal Imaging of Metals in a Retinal Degeneration Model to Inform on Ocular Disease

The metallome has been involved in the pathological investigation into ocular tissue for decades; however, as technologies advance, more information can be ascertained from individual tissue sections that were not previously possible. Herein, a demonstration of complementary techniques has been utilized to describe the distribution and concentrations of essential metals in both wildtype (WT) and rhodopsin (Rho−/−) ocular tissues. The multimodal approach described is an example of complementary datasets that can be produced when employing a multifaceted analytical approach. Heterogenous distributions of copper and zinc were observable within both WT and Rho−/− tissue by laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS), and the distributions of further trace elements notoriously problematic for ICP-MS analysis (phosphorous, Sulfur, chlorine, potassium, calcium, iron, and aluminum) were analysed by particle-induced X-ray emission (PIXE).

Coral Sr‐U Thermometry Tracks Ocean Temperature and Reconciles Sr/Ca Discrepancies Caused by Rayleigh Fractionation

AbstractUnderstanding climate change at the spatiotemporal scales necessary to improve climate projections requires proxy records that complement sparse and often contradictory observational temperature data sets. Massive long‐lived corals have tremendous potential in this regard, continuously recording information about ocean conditions as they grow. Nevertheless, extracting accurate ocean temperatures from corals is challenging because factors other than temperature influence skeletal chemistry. Here, we tested the ability of the coral Sr‐U thermometer to accurately capture annual sea surface temperatures (SSTs) in the subtropical Atlantic, where year‐to‐year temperatures vary by ∼1°C. Using laser ablation inductively coupled plasma mass spectrometry (LA‐ICP‐MS), we generated sufficient U/Ca – Sr/Ca pairs from a slow‐growing (1−2 mm/yr) Siderastrea siderea coral to calculate annual Sr‐U values. With the fine‐scale spatial resolution attained using the laser, skeleton accreted during both fast and slow growing times of the year was represented in our sampling. The resulting 30‐year‐long Sr‐U record tracked the amplitude and timing of annual SST to within ±0.2°C of observations (r = −0.71), whereas the Sr/Ca record did not (r = 0.23). Furthermore, Sr‐U corrected for Sr/Ca offsets among adjacent skeletal elements approximately 1 mm apart. These offsets are equivalent to differences of 2–3°C if typical Sr/Ca–SST calibrations are applied. Our observations indicate that Sr‐U can accurately constrain decadal‐to‐multidecadal variability and secular SST trends in regions where this information is urgently needed.

Первые радиометрические датировки тонштейнов из угленосных отложений Кузнецкого бассейна: U-Pb-геохронология тайлуганской свиты

Tonsteins, predominantly solid kaolinite clay interbeds, are widespread in the coals of the Kuznetsk Basin and usually contain idiomorphic zircon grains of magmatic origin in quantities suitable for uranium-lead (U-Pb) radiometric dating. For the first time, tonstein zircons from coal seam 78 of the Tailugan Formation (Fm) are dated by two methods: Laser Ablation Inductively Coupled Plasma Mass Spectrometry (LA-ICP-MS) and Chemical Abrasion Isotope-Dilution Thermal Ionization Mass Spectrometry (CA-ID-TIMS). The CA-ID-TIMS datings of 257.0 ± 1.3 Ma and 256.6 ± 0.4 Ma determine the age of the lower boundary of the Tailugan Fm and the Tailuganian Regional Stage at 257.0 Ma. We estimate the duration of the Tailuganian to be around 4.22 million years. The dating results make it possible to directly correlate the Tailuganian of the Kuzbass with the upper half of the Wuchiapingian and with most of the Changhsingian of the International Chronostratigraphic Scale. The accumulation rate of total sediments of the Tailugan Fm, calculated without considering the compaction index, is approximately 0.13–0.18 mm/year, and the rate of coal accumulation is 0.024 mm/year. Such values are comparable to the accumulation rates of the Late Paleozoic coal-bearing strata of the Donetsk Basin and Western Australia. The rate of peat accumulation during the Tailuganian, calculated at a compaction index of 10:1, has been estimated at 0.24 mm/year. This value is comparable to the rates of peat accumulation in the Holocene bogs of the Kuznetsk Alatau in Siberia and the European part of Russia. The presence of tonsteins in the coal seams of the Tailugan Fm suggests that the upper surface of the peat at the time of its accumulation was below the water level, serving as a protective screen for the thin volcanic deposits and preventing its erosion. The assemblages of macroflora, ostracods, conchostracans and bivalves considerably vary through the section of the Tailugan Fm. This variation makes it possible to identify in Kuzbass the stratigraphic level that corresponds to the boundary between the Wuchiapingian and Changhsingian stages in the future.

The impact of corrosion on the adsorption of gaseous Hg0 onto the surface of steels: Implications for decommissioning in the oil and gas industry

The rate of decommissioning of global oil and gas production facilities will accelerate over coming decades, as mature developments reach the end of use, and consumers transition towards renewable energy. Decommissioning strategies should include thorough environmental risk assessments which consider contaminants which are known to be present in oil and gas systems. Mercury (Hg) is a global pollutant that occurs naturally in oil and gas reservoirs. However, knowledge of Hg contamination in transmission pipelines and process equipment is limited. We investigated the potential for accumulation of Hg0 within production facilities, particularly those transporting gases, by considering the deposition of Hg onto steel surfaces from the gas phase. Following incubation experiments in a Hg saturated atmosphere; fresh API 5L‐X65 and L80–13Cr steels were found to adsorb 1.4 × 10−5 ± 0.04 × 10−5 and 1.1 × 10−5 ± 0.04 × 10−5 g m−2, respectively, while corroded samples of the same steels adsorbed 0.12 ± 0.01 and 0.83 ± 0.02 g m−2; an increase in adsorbed mercury by four orders of magnitude. The association between surface corrosion and Hg was demonstrated by laser ablation ICPMS. The levels of Hg measured on the corroded steel surfaces indicates a potential environmental risk; therefore, mercury speciation (including the presence of ß-HgS, not considered in this study), concentrations and cleaning methods should be considered when developing oil and gas decommissioning strategies.

Microspatial distribution of trace elements in feline dental hard tissues: early life exposure to essential and toxic elements.

Trace elements play a key role in dental tissue development, as dental hard tissues accumulate both essential and toxic trace elements during mineralization. Characterization of the spatial accumulation pattern of trace elements may provide insight into exposure to toxic elements over time and to the nature of disease processes affecting the hard dental tissues. Here, we present the first report of the use of laser ablation-inductively coupled plasma-mass spectrometry (LA-ICP-MS) to map the microspatial distribution of multiple trace elements, essential and toxic, across feline dental hard tissues. Eleven teeth were extracted from 8 cats. Nine teeth were from 7 cats diagnosed with idiopathic tooth resorption on intraoral radiographs prior to extraction. Two teeth were included from a cadaver that had no signs of tooth resorption on intraoral radiographs. The normal dental tissue was analyzed from each sample using LA-ICP-MS to map the microspatial distribution of essential and toxic trace elements across feline enamel, dentin, and cementum. Results showed a higher accumulation of barium and strontium in coronal dentin as compared to root dentin. The timing of the accumulation mirrors nursing timelines seen in teeth from human and non-human primates, consistent with barium and strontium being sourced from maternal milk. Results also showed a higher uptake of lead in the coronal dentin, suggesting this lead exposure was likely passed from mother to offspring. This work characterizes a baseline for elemental distribution in feline teeth linked to early life exposure to toxic elements such as lead and provides a framework for future studies investigating long-term environmental exposures to trace elements, essential and toxic, and their involvement in feline systemic and dental diseases.

Monazite and xenotime petrochronologic constraints on four Proterozoic tectonic episodes and ca. 1705 Ma age of the Uncompahgre Formation, southwestern Colorado, USA

Abstract The Proterozoic tectonic evolution of the southwestern USA remains incompletely understood due to limited constraints on the timing and conditions of the tectono-metamorphic phases and depositional age of metasedimentary successions. We integrated multi-scale compositional mapping, petrologic modeling, and in situ geochronology to constrain pressure-temperature-time paths from samples of Paleoproterozoic basement gneisses and overlying quartzites in southwestern Colorado, USA. Basement gneiss from the western Needle Mountains records metamorphic conditions of 600 °C at 0.75 GPa at 1764 ± 9 Ma and ~575 °C at 1741 ± 10 Ma. Gneiss sampled from drill core near Pagosa Springs, Colorado, records conditions of 700 °C at 1748 ± 9 Ma, 800 °C at 1.1 GPa at 1650 ± 40 Ma, 540 °C at 1570 ± 36 Ma, and 440 °C at 1424 ± 12 Ma. The Uncompahgre Formation was deposited at ca. 1705 Ma, as constrained by detrital monazite (1707 ± 8 Ma) and xenotime (1692 ± 40, 1725 ± 50 Ma), metamorphic xenotime (1650 ± 10 Ma), and published 40Ar/39Ar and detrital zircon data. Compositions of ca. 1705 Ma detrital monazite and xenotime are consistent with derivation from a garnet-bearing source in the Yavapai orogenic hinterland. The Vallecito Conglomerate and Uncompahgre Formation record macroscopic folding and greenschist-facies metamorphism at 1650 ± 10 Ma and temperatures of 270 °C to &amp;gt;570 °C at 1470–1400 Ma. Laser ablation–inductively coupled plasma–mass spectrometry (LA-ICP-MS) zircon geochronology yielded dates of 1775 ± 18 Ma from the Twilight Gneiss and 1696 ± 7 Ma from the Bakers Bridge Granite, supporting previous isotope dilution–thermal ionization mass spectrometry (ID-TIMS) dates. The Eolus Granite yielded a date of 1463 ± 6 Ma, which is older than previous 1.44–1.43 Ga ID-TIMS dates. The newly dated granite of Cataract Gulch is 1421 ± 12 Ma. In situ analysis of detrital and meta-morphic monazite and xenotime, igneous zircon, and quantitative thermobarometry, integrated with previously published constraints, indicate multiple tectonic episodes after the emplacement of 1800–1760 Ma arc-related rocks. The region experienced greenschist- to amphibolite-facies metamorphism (M1) from 1760 Ma to 1740 Ma, which was followed by the intrusion of granites at 1730–1695 Ma and deposition of the Uncompahgre Formation at ca. 1705 Ma, contemporaneous with the Yavapai orogeny. Metamorphism at 1680–1600 Ma was characterized by greenschist-facies conditions near Ouray, Colorado, and granulite-facies conditions near Pagosa Springs (M2) during the Mazatzal orogeny. From 1470 Ma to 1400 Ma, greenschist- to amphibolite-facies metamorphism (M3) and largely granitic plutonism occurred during the protracted Picuris orogeny. These results demonstrate the power of monazite and xenotime analyses to constrain depositional ages, provenance, and pressure-temperature-time (P-T-t) paths to resolve the compound orogenic history that is characteristic of most mountain belts.

Insights into the secondary glass production in Roman Aquileia: A preliminary study

A set of 29 glass shards, selected from numerous ones recovered in 2017 in Aquileia (NE Italy), was studied to provide evidence of local glass production for that specific area in antiquity. These shards can be dated between the 1st and the 4th century AD. The chemical composition of glass samples was obtained using laser ablation-inductively coupled plasma-mass spectrometry (LA-ICP-MS) that enables to quantify the concentration of major, minor, and trace elements needed to investigate provenance and compositional groups and sometimes to suggest a chronological frame of the samples. To ensure that the samples are homogeneous enough to perform accurate quantification, some of them were also analysed by instrumental neutron activation analysis (INAA). Most of the chunks, working wastes, and artefact shards considered in this work exhibited similarities among them in terms of composition, which likely indicates that glass working activities were practised at the site of recovery. The analyses demonstrated the presence of both recycled glass and primary glass. Interestingly, the compositional data of raw primary glass point to both Syro-Palestinian and Egyptian regions as sourcing areas, confirming the role of the Roman city of Aquileia as a network node for the trade of goods. In addition, some particularly coloured glass fragments showed a composition typical of glass produced starting from the 1st or 2nd century AD, requiring specific types of furnaces and procedures for its manufacture, and suggesting the possibility of local highly-specialised production. The preliminary results of this work strengthen the hypothesis that Aquileia was a thriving centre, either for working primary glass or for glass recycling and production of objects with particular colours.

The genetic association between vein and skarn type tungsten mineralization in the Yaogangxian tungsten deposit, South China: Constraints from LA-ICP-MS analysis of individual fluid inclusion

The large-scale Yaogangxian W deposit, located in central of the Nanling metallogenic belt, South China, comprises independent quartz vein-type and skarn-type W mineralization. Wolframite-bearing quartz veins occur invariably in metasandstone and slate to the northwest of the Yaogangxian granitic intrusion, whereas scheelite-skarn are mainly hosted by the limestone to the east. The vertical extension of single wolframite-bearing quartz vein can reach up to 1000 m and we focused on the vein samples collected from the deepest level (26 level) which likely recorded early magmatic fluids. For skarn mineralization, two scheelite precipitation stages were recognized, namely scheelite-1 in retrograde stage and scheelite-2 from sulfide-stage. To reveal the fluid sources and characteristics of two mineralizing systems, detailed petrography and microthermometry analyses were carried out on fluid inclusion assemblages (FIA) in scheelite, wolframite and their coexisting quartz. Fluid compositions were obtained from individual fluid inclusion (FI) in ore and gangue minerals via laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) analysis. These data aid elucidation on the source and nature of fluids in the two distinct W mineralization styles. The chemical compositions of FIs hosted in wolframite and scheelite points to a common magmatic source. The fluid in the scheelite ore section exhibits lower As and B than the wolframite ore section, indicating that boiling may have occurred at early skarn stage. Fluid evolution in the two mineralizing systems suggest that formation of diverse W mineralization styles is mainly controlled by different host lithology and fluid processes. In the wolframite ore section, ore-forming fluid recorded in the deepest level of vein show elevated As, B, K and Rb contents than previously reported ore-forming fluid obtained from the tip of the vein. This likely indicate absence of intensive fluid immiscibility in the deep during wolframite formation, which may rather be accompanied by fluid-rock interaction. In the scheelite ore section, constant injection of meteoric water is revealed. FI hosted in scheelite-1 and 2 exhibit similar compositions, and the lower K content in scheelite-2 fluid is thought to be caused by sericitization in the retrograde stage skarn. The Mo content of scheelite decreased from the retrograde stage to sulfide-stage, indicating a decrease in oxygen fugacity. Based on these conclusion and previous geological and geochronological studies, we propose a metallogenic model of the coupled wolframite-quartz vein and scheelite-skarn mineralization.

Impact of an SLC30A8 loss-of-function variant on the pancreatic distribution of zinc and manganese: laser ablation-ICP-MS and positron emission tomography studies in mice.

Common variants in the SLC30A8 gene, encoding the secretory granule zinc transporter ZnT8 (expressed largely in pancreatic islet alpha and beta cells), are associated with altered risk of type 2 diabetes. Unexpectedly, rare loss-of-function (LoF) variants in the gene, described in heterozygous individuals only, are protective against the disease, even though knockout of the homologous SLC30A8 gene in mice leads to unchanged or impaired glucose tolerance. Here, we aimed to determine how one or two copies of the mutant R138X allele in the mouse SLC30A8 gene impacts the homeostasis of zinc at a whole-body (using non-invasive 62Zn PET imaging to assess the acute dynamics of zinc handling) and tissue/cell level [using laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) to map the long-term distribution of zinc and manganese in the pancreas]. Following intravenous administration of [62Zn]Zn-citrate (~7 MBq, 150 μl) in wild-type (WT), heterozygous (R138X+/-), and homozygous (R138X+/+) mutant mice (14-15 weeks old, n = 4 per genotype), zinc dynamics were measured over 60min using PET. Histological, islet hormone immunohistochemistry, and elemental analysis with LA-ICP-MS (Zn, Mn, P) were performed on sequential pancreas sections. Bulk Zn and Mn concentration in the pancreas was determined by solution ICP-MS. Our findings reveal that whereas uptake into organs, assessed using PET imaging of 62Zn, is largely unaffected by the R138X variant, mice homozygous of the mutant allele show a substantial lowering (to 40% of WT) of total islet zinc, as anticipated. In contrast, mice heterozygous for this allele, thus mimicking human carriers of LoF alleles, show markedly increased endocrine and exocrine zinc content (1.6-fold increase for both compared to WT), as measured by LA-ICP-MS. Both endocrine and exocrine manganese contents were also sharply increased in R138X+/- mice, with smaller increases observed in R138X+/+ mice. These data challenge the view that zinc depletion from the beta cell is the likely underlying driver for protection from type 2 diabetes development in carriers of LoF alleles. Instead, they suggest that heterozygous LoF may paradoxically increase pancreatic β-cell zinc and manganese content and impact the levels of these metals in the exocrine pancreas to improve insulin secretion.

Mineralogy and elemental geochemistry of pyrite coal-balls, Datong Coalfield, Shanxi Province, China: Implications for differentiation mechanism

The pyrite coal-balls found in No.9 coal of Taiyuan Formation in Dongzhouyao Mine of Datong Coalfield were selected to investigate its mineralogy and elemental geochemistry using optical microscope observation, scanning electron microscopy combined with an energy-dispersive X-ray spectrometer (SEM-EDX), inductively coupled plasma mass spectrometry analysis (ICP-MS), laser ablation inductively-coupled plasma mass spectrometry (LA-ICP-MS), and electron probe micro-analysis (EPMA). Due to the high content of pyrite, the major-element oxides in the coal-ball samples were mainly Fe2O3, with an average of 62.68 %. LA-ICP-MS results showed that coal-balls were enriched in Tl (CC = 32.79), Pb (CC = 9.22), and Mo (CC = 2.07), while the coals in the same layer were enriched in Ga (CC = 5.31), Tl (CC = 3.66), and Li (CC = 2.27). Affinities to S or Fe and the variation of elemental concentration in the environment during the formation of coal-balls were the primary factor of the elemental differentiation between coals and coal-balls, as well as within coal-balls. The coal-balls formed in four stages in a marine-continental transition environment, with Fe from terrestrial sources and S from marine phases, and its physical origin is basically consistent with that of some Carboniferous-Permian coals in the Datong Coalfield. According to the formation sequence and geochemical characteristics, four periods of pyrite coal-balls evolution have been proposed.

Early Mesozoic orogenic gold mineralization in the North Qinling Terrane: Insights from rutile U-Pb, mica and K-feldspar 40Ar/39Ar, and H-O-S-Pb isotopes of the Yangxie gold deposit

The North Qinling Terrane is located between China’s second largest, Early Cretaceous gold province (southern North China Craton) to the northeast and the third largest, Triassic gold province (western South Qinling Terrane) to the southwest. However, only several small- to medium-sized Au deposits and occurrences have been found so far in the North Qinling Terrane, and their genesis and possible links with the gold mineralization in the above two large gold provinces remain unclear. In this study, we present a comprehensive geochronology, stable and radiogenic isotope geochemistry study of the Yangxie gold deposit in the North Qinling Terrane to provide new insights into gold genesis in the North Qinling Terrane and its genetic relations to the neighboring gold provinces. The Yangxie gold deposit consists of quartz-sulfides veins that are hosted by NW- and NE-striking brittle faults cutting amphibolite- to granulite-facies metamorphic rocks of the Paleoproterozoic to Neoproterozoic Qinling Group. Gold mineralization is represented by four paragenetic stages consisting of milky quartz-K-feldspar (I), light grey quartz-pyrite (II), light grey quartz-polymetallic sulfides (III), and quartz-calcite (IV). Gold was deposited mainly in stages II and III, forming abundant native gold grains that occur as inclusions in pyrite, microfracture infillings in sulfide minerals, or interstitial growths to other ore and gangue minerals. Ore-related alteration assemblages comprise mainly quartz, sericite, muscovite, K-feldspar, and calcite. Hydrothermal rutile is widely recognized in gold ores and texturally intergrown with gold-bearing pyrite and other alteration minerals, indicating synchronous precipitation of rutile and gold. Laser ablation ICP-MS U-Pb dating on two rutile samples yield reproducible dates of 214.6 ± 5.5 Ma (MSWD = 0.82, 2σ) and 210.1 ± 6.9 Ma (MSWD = 1.3, 2σ), which are interpreted as the time of gold deposition. 40Ar/39Ar dating of sericite, muscovite, and K-feldspar from the alteration assemblages yield more scattered and younger dates ranging from 199.8 ± 1.1 to 119.3 ± 0.6 Ma, which are considered as the cooling ages of the deposit related to later tectonothermal events. Oxygen and hydrogen isotopes of ore-related quartz and extracted fluid inclusion waters are 10.4 ∼ 15.0 and −87.7 ∼ -67.2 per mil, respectively. Pyrite and galena have variable δ34S values ranging from −9.4 to 0.5 per mil. These sulfides have lead isotopic compositions of 17.956–18.067 for 206Pb/204Pb, 15.565–15.621 for 207Pb/204Pb, and 38.045–38.301 for 208Pb/204Pb. The isotope data collectively suggest that the ore-forming fluids and metals were derived from the devolatilization of the early Paleozoic sedimentary rocks distributed in the North Qinling Terrane. The results presented here, combined with independent studies, show that the Yangxie deposit was a product of the Late Triassic orogenic gold mineralization event that formed the western South Qinling gold province. Recognition of the Late Triassic Yangxie gold deposit suggests that faults within and around the metamorphosed Paleozoic sedimentary rocks and subsidiary faults affiliated to the Shangdan Suture in the North Qinling Terrane could be favorable targets for further Triassic orogenic gold exploration.