Sector Field Mass Spectrometry Research Articles

Determination of ultra-trace Te species in open ocean waters based on Mg(OH)2 coprecipitation, anion exchange resin column separation and inductively coupled plasma sector-field mass spectrometry using a 125Te-enriched isotope spike

We present a method for the determination of ultra-trace Te species (Te(IV) and Te(VI)) in open ocean waters. The proposed method is based on Mg(OH)2 coprecipitation, anion exchange resin column separation and inductively coupled plasma sector-field mass spectrometry (ICPSFMS) using a 125Te-enriched isotope spike. The largest advantage of the method is that the use of the spike allows accurate and precise determination when it combines with either isotope dilution or recovery correction. Tellurium-IV and VI are preconcentrated in a Mg(OH)2 precipitate and separated mutually by an anion exchange resin column. Te(IV) is retained to the column, while Te(VI) passing through the column is recovered by a subsequent column procedure after reduction of Te(VI) to Te(IV). Te(IV) is successfully eluted with a small amount of 0.01 M HCl. The additional merit of using this eluent is elimination of components that result in a memory effect during the measurement of Te(IV). Possible mass spectral interference on Te(IV) can be excluded by adjusting the mass window, and the Te(IV) concentrations determined by this approach agree well with those independently obtained by an oxidation procedure which removes the interference. The accuracy of the proposed method is verified with homemade standard seawater for which the measured concentrations agree well with results calculated from the value of the standard solution. Procedural blanks for Te(IV) and Te(VI) are 1.5 ± 0.9 pg kg−1 (n = 11) and 1.3 ± 0.9 pg kg−1 (n = 11) with corresponding overall detection limits of 3.0 pg kg−1 and 2.8 pg kg−1, respectively. Using the method, we have clarified vertical profiles of Te(IV) and Te(VI) in the subarctic western North Pacific for the first time.

Toxic elements in arctic and sub-arctic brown bears: Blood concentrations of As, Cd, Hg and Pb in relation to diet, age, and human footprint

Contamination with arsenic (As), cadmium (Cd), mercury (Hg) and lead (Pb) is a global concern impairing resilience of organisms and ecosystems. Proximity to emission sources increases exposure risk but remoteness does not alleviate it. These toxic elements are transported in atmospheric and oceanic pathways and accumulate in organisms. Mercury accumulates in higher trophic levels. Brown bears (Ursus arctos), which often live in remote areas, are long-lived omnivores, feeding on salmon (Oncorhynchus spp.) and berries (Vaccinium spp.), resources also consumed by humans.We measured blood concentrations of As, Cd, Hg and Pb in bears (n = 72) four years and older in Scandinavia and three national parks in Alaska, USA (Lake Clark, Katmai and Gates of the Arctic) using high-resolution, inductively-coupled plasma sector field mass spectrometry. Age and sex of the bears, as well as the typical population level diet was associated with blood element concentrations using generalized linear regression models.Alaskan bears consuming salmon had higher Hg blood concentrations compared to Scandinavian bears feeding on berries, ants (Formica spp.) and moose (Alces). Cadmium and Pb blood concentrations were higher in Scandinavian bears than in Alaskan bears. Bears using marine food sources, in addition to salmon in Katmai, had higher As blood concentrations than bears in Scandinavia. Blood concentrations of Cd and Pb, as well as for As in female bears increased with age. Arsenic in males and Hg concentrations decreased with age.We detected elevated levels of toxic elements in bears from landscapes that are among the most pristine on the planet. Sources are unknown but anthropogenic emissions are most likely involved. All study areas face upcoming change: Increasing tourism and mining in Alaska and more intensive forestry in Scandinavia, combined with global climate change in both regions. Baseline contaminant concentrations as presented here are important knowledge in our changing world.

Plasma Rhenium and Selenium Concentrations After Repeated Daily Oral Administration of Rhenium(I)-diselenoether in 4T1 Breast Tumor-bearing Mice.

Rhenium(I)-diselenoether (Re-diSe) is a compound combining a rhenium tricarbonyl(I) core with a diselenide ligand. A high dose of 60 mg/kg had a pro-tumor effect in a previous study, in non-immune deficient 4T1 tumor-bearing mice, while doses of 1 and 10 mg/kg did not affect tumor growth, after repeated oral administrations. This study aimed to examine the tumor effects of a lower dose of 0.1 mg/kg with the same experimental design and to assay plasma Re and Se concentrations. Syngenic BALB/cByJ (JAX) mice were orthotopically inoculated with 4T1 mammary breast cancer cells. Re-diSe was daily administered orally for 23 days at doses of 0.1, 1, and 10 mg/kg, whereas controls received no treatment. Tumor and mice weights were measured at the end of the experiment. Plasma Re and Se concentrations were assayed by an inductively coupled plasma sector field mass spectrometry instrument (ICP-sf-MS). The weight of the tumors did not vary in treated versus non-treated mice. The limit of detection (LOD) of Re was 0.34 nmol/l. Plasma Re concentrations were 14±20 nmol/l at doses of 0.1 mg/kg, and increased at higher doses, up to 792±167 nmol/l at doses of 10 mg/kg. Plasma Se concentrations were significantly increased in mice treated with the dose of 0.1 mg/kg (4,262±1,511 nmol/l) versus controls (1,262±888 nmol/l), but not from 0.1 to 1 mg/kg, nor from 1 to 10 mg/kg. The 0.1 mg/kg dose of Re-diSe resulted in detectable plasma Re concentrations and significantly increased plasma Se concentrations. In the future, doses as low as 0.1 mg/kg of Re-diSe will be tested, exploring its potential immune interest as a metronomic schedule of treatment, but in mouse models that readily develop extensive metastatic disease.

Mercury, silver and selenium in serum before and after removal of amalgam restorations: results from a prospective cohort study in Norway

Objective A prospective cohort study on changes of health complaints after removal of amalgam restorations was carried out at the request of the Norwegian Directorate of Health. The aim was to provide and evaluate experimental treatment to patients with health complaints attributed to dental amalgam fillings. Methods Patients (n = 32) with medically unexplained physical symptoms (MUPS), which were attributed to dental amalgam restorations had all their amalgam restorations removed and replaced with other dental restorative materials. Samples of blood were collected before and 1 year after removal of the fillings, and concentration of inorganic mercury (I-Hg), methylmercury (MeHg), silver (Ag) and selenium (Se) in serum was determined by inductively coupled plasma–sector field mass spectrometry. The comparison groups (one with MUPS but without attribution to amalgam [n = 28] and one group of healthy individuals [n = 19]) received no treatment. The participants responded to questionnaires at baseline and at follow-up after 1 and 5 years. Results Concentration of I-Hg and Ag in serum decreased significantly after removal of all amalgam restorations. Concentration of MeHg and Se in serum were not changed. Intensity of health complaints was significantly reduced after amalgam removal, but there were no statistically significant correlations between exposure indicators and health complaints. Conclusions Removal of all amalgam restorations is followed by a decrease of concentration of I-Hg and Ag in serum. The results support the hypothesis that exposure to amalgam fillings causes an increase of the daily dose of both I-Hg and Ag. Even though intensity of health complaints decreased after removal of all amalgam restorations there was no clear evidence of a direct relationship between exposure and health complaints. Trial registration: The project is registered at Clinicaltrials.gov (NCT01682278).

Effect of water filtration infrared-A (wIRA) sauna on inorganic ions excreted through sweat from the human body.

Sweat discharged as a result of exposure to sauna plays an important role in removing inorganic ions accumulated in the body, including heavy metals. In this study, inorganic ions (toxic and nutrient elements) excreted in the form of sweat from the body using a water-filtered infrared-A (wIRA) sauna were determined using inductively coupled plasma sector field mass spectrometry. The analyzed elements included eight toxic elements (Al, As, Be, Cd, Ni, Pb, Ti, and Hg) and 10 nutrient elements (Ca, Co, Cr, Cu, Fe, Mg, Mn, Se, V, and Zn), and their correlations were determined. Analysis of the sweat obtained from 22 people using the wIRA sauna showed a higher inorganic ion concentration than that obtained from conventional activities, such as exercise or the use of wet sauna, and the concentration of toxic elements in sweat was higher in females than in males. Correlation analysis of the ions revealed a correlation between the discharge of toxic elements, such as As, Be, Cd, and Ni, and discharge of Se and V, and Ni was only correlated with Mn. This study provides fundamental information on nutritional element supplementation when using wIRA sauna for detoxification.

Adult Exposures to Toxic Trace Elements as Measured in Nails along the Interoceanic Highway in the Peruvian Amazon.

Deforestation, artisanal and small-scale gold mining (ASGM), and the rapid development related to highway expansion cause opportunities for toxic trace element exposure in the Amazon region of Madre de Dios (MDD), Peru, one of the most biologically diverse places in the world. The objective of this study was to assess the exposure to arsenic, cadmium, lead, and mercury among adults in Madre de Dios. In total, 418 adult (18+ years) participants in the Investigacion de Migracion, Ambiente, y Salud (IMAS) (Migration, Environment, and Health Study) participated in this study. Consent, survey data, and biospecimens were collected between August and November 2014. Nail elements were measured by inductively coupled plasma sector field mass spectrometry. Differences by selected individual and household characteristics and local land uses were tested using one-way ANOVAs and linear mixed models. Adults in ASGM-affected areas had higher nail arsenic and nail cadmium than their non-ASGM counterparts. Higher household fish consumption was positively associated with nail mercury and nail lead. The results indicate that adult exposure to arsenic, cadmium, lead, and mercury is heterogeneous across Madre de Dios, and the exposures related to ASGM communities and fish consumption suggest that exposures from artisanal and small-scale mining are environmentally widespread. Further investigation is warranted to ascertain potential health impacts.

Fire Retardancy and Leaching Resistance of Furfurylated Pine Wood (Pinus sylvestris L.) Treated with Guanyl-Urea Phosphate

Guanyl-urea phosphate (GUP) was introduced into furfurylated wood in order to improve fire retardancy. Modified wood was produced via vacuum-pressure impregnation of the GUP–furfuryl alcohol (FA) aqueous solution, which was then polymerized at elevated temperature. The water leaching resistance of the treated wood was tested according to European standard EN 84, while the leached water was analyzed using ultra-performance liquid chromatography (UPLC) and inductively coupled plasma–sector field mass spectrometry (ICP-SFMS). This new type of furfurylated wood was further characterized in the laboratory by evaluating its morphology and elemental composition using optical microscopy and electron microscopy coupled with energy-dispersive X-ray spectrometry (SEM-EDX). The chemical functionality was detected using infrared spectroscopy (FTIR), and the fire resistance was tested using cone calorimetry. The dimensional stability was evaluated in wet–dry soaking cycle tests, along with the mechanical properties, such as the Brinell hardness and bending strength. The fire retardancy of the modified furfurylated wood indicated that the flammability of wood can be depressed to some extent by introducing GUP. This was reflected in an observed reduction in heat release rate (HRR2) from 454.8 to 264.9 kW/m2, without a reduction in the material properties. In addition, this leaching-resistant furfurylated wood exhibited higher fire retardancy compared to conventional furfurylated wood. A potential method for producing fire-retardant treated furfurylated wood stable to water exposure has been suggested.

Isotopic Imaging Using fsLA Single-Collector ICP-SFMS for Direct U/Th Dating of Small Archaeological Carbonates.

We present a new methodology for the U/Th dating of carbonate materials using femtosecond laser ablation single-collector inductively coupled plasma sector field mass spectrometry (fsLA single-collector ICP-SFMS), isotopic mappings, and image processing. This approach allows working on samples at very low U levels (ng·g-1). One of the major advantages of this imaging method is that it allows us to exploit deteriorated samples that could not be analyzed by conventional bulk U/Th dating methods, thanks to the identification of contaminated or leached areas at the scale of a few tens of microns and the subsequent correction for detrital 230Th incorporation. Only a few milligrams of material are required for measurement, which allows us to work on small samples such as shell fragments. The parameters of the fsLA single-collector ICP-SFMS coupling have been carefully optimized to ensure very high sensitivity detection and ultralow background while preserving good plasma robustness and a spatial resolution of 30 × 50 μm2. The accuracy was evaluated from low-level U speleothems previously dated by a conventional U/Th dating technique involving digestion, resin purification, double spike, and detection by multicollector inductively coupled plasma mass spectrometry (MC-ICPMS). U/Th ages of two archaeological samples with U at low ng·g-1 levels, a giant terrestrial snail shell and a burned ostrich eggshell, were determined. The measured U/Th ages are consistent with the expected ages determined by luminescence dating methods.

The Penetration of Chromium: An Up-To-Date 0.5% Potassium Dichromate Vehicle Comparison.

Chromium (Cr) contact allergy is frequent in many industrialized countries. The knowledge of the factors that can influence percutaneous penetration is very important assessing the risk of human exposure. The aim of the study was to compare the concentration of Cr in various skin layers using 2 different vehicles. Full-thickness (approximately 1 mm) porcine ear skin was mounted in Franz-type diffusion cells. Duplicate potassium dichromate preparations in 0.5% petrolatum (pet) and 0.5% in aqua (aq) were applied to the donor compartment facing the epidermis for 24 hours. After the experiment, the porcine skin samples were cut with a microtome. All samples were analyzed for total Cr concentration by inductively coupled plasma sector field mass spectrometry. The limit of detection was 0.001 μg/cm3. Chromium was detected in both recipient phases. The distribution of Cr in the skin is similar for pet and aq preparations, but the concentration of Cr detected in the skin was almost 2 times lower for pet comparing aq preparations. Both vehicles were suitable for penetrating the skin. Less Cr is found in the skin when pet is used as a vehicle. Acid wipe sampling and finger immersion test results might be false-negative for Cr in occupations involving contact with Cr salts in aq solutions.

Determination of phosphate in seawater by ion chromatography inductively coupled plasma sector field mass spectrometry

AbstractPhosphate in three seawater certified reference materials developed in previous work (NMIJ CRM 7601‐a, 7602‐a, and 7603‐a) was not certified because it was only determined by continuous flow analysis (CFA). To obtain certified values for phosphate, we developed a novel method for the analysis of phosphate in seawater via inductively coupled plasma sector field mass spectrometry (ICP‐SFMS) combined with anion exchange ion chromatography (IC). With use of a Jet‐sampler cone and an X‐skimmer cone on the ICP‐SFMS instrument, the 31P sensitivity derived from phosphate was enhanced by a factor of 18 compared to that of standard cones. To reduce the severe saline‐generated matrix effect, an IC with a switching‐valve system that separates phosphate from saline was employed. By adding an internal standard element (As) to the seawater samples, time‐dependent fluctuation of the 31P sensitivity was corrected and a better calibration curve was obtained. The developed method was applied to the analysis of three types of seawater. Although NMIJ CRM 7601‐a could not be determined because its concentration after dilution for the IC separation is lower than the detection limit (0.005 μmol kg−1), the analytical results for NMIJ CRM 7602‐a and 7603‐a are in good agreement with the values obtained via CFA, considering their expanded uncertainties with the coverage factor of 2. The developed method was validated by analyzing an existing certified reference material (MOOS‐3). This method enabled the measurement of sub‐μmol kg−1 levels of phosphate with high accuracy and sensitivity.

High concentrations of lead (Pb) in blood and milk of free-ranging brown bears (Ursus arctos) in Scandinavia

Exposure to lead (Pb) is a global health problem for both humans and wildlife. Despite a dramatic decline in human Pb exposure following restrictions of leaded gasoline and industry and thereby an overall reduction of Pb entering the environment, Pb exposure continues to be a problem for wildlife species. Literature on scavenging terrestrial mammals, including interactions between Pb exposure and life history, is however limited.We quantified Pb concentration in 153 blood samples from 110 free-ranging Scandinavian brown bears (Ursus arctos), 1–25 years old, using inductively coupled plasma sector field mass spectrometry. We used generalized linear models to test effects of age, body mass, reproduction status and spatial distribution on the blood Pb concentrations of 56 female bears. We sampled 28 females together with 56 dependent cubs and paired their blood Pb concentrations. From 20 lactating females, we measured the Pb concentration in milk.The mean blood Pb concentration was 96.6 μg/L (range: 38.7–220.5 μg/L). Both the mean and range are well above established threshold concentrations for developmental neurotoxicity (12 μg/L), increased systolic blood pressure (36 μg/L) and prevalence of kidney disease in humans (15 μg/L). Lactating females had higher Pb blood concentrations compared to younger, non-lactating females. Blood Pb concentrations of dependent cubs were correlated with their mother's blood Pb concentration, which in turn was correlated with the Pb concentration in the milk.Life-long Pb exposure in Scandinavian brown bears may have adverse effects both on individual and population levels. The high blood Pb concentrations found in brown bears contrast the general reduction in environmental Pb contamination over the past decades in Scandinavia and more research is needed to identify the sources and pathways of Pb exposure in the brown bears.

Low hepatic manganese concentrations in patients with hepatic steatosis – A cohort study of copper, iron and manganese in liver biopsies

Background and aimsHepatic steatosis is the most common histopathological finding on liver biopsy, with the most prevalent etiology being NAFLD. The pathogenesis of hepatic steatosis and NAFLD is multifactorial, however, studies on the importance of manganese in NAFLD are limited. We aimed to study hepatic manganese content, and other trace elements, in relation to hepatic steatosis in patients with chronic liver diseases of different etiology, mainly NAFLD. MethodsPatients with chronically elevated liver function tests underwent a diagnostic work-up, including routine blood tests and two liver biopsies. One of the biopsies was sent for histopathological evaluation, and the other for ultra-trace elemental determinations. Steatosis was graded using conventional histopathological methodology, and fat content was also quantitated in biopsy samples by measuring the steatotic area of the section using stereological point counting (SPC). Ultra-trace elemental analysis was utilized for determining manganese, iron, and copper using inductively coupled plasma sector field mass spectrometry (ICP-SFMS). Results76 patients were included in the study. Hepatic manganese concentrations in patients with steatosis were lower than in patients without hepatic steatosis (3.8 ± 1.1 vs. 6.4 ± 1.8, P < 0.001). Similar results were seen for blood manganese levels and hepatic steatosis. We found a strong inverse correlation between steatosis grade and hepatic manganese content (ρ=-0.743, P < 0.001). Also, low levels of manganese independently predicted the presence of steatosis (aOR 0.07 [95%CI: 0.01−0.63]). ConclusionPatients with NAFLD, or other CLD and concomitant hepatic steatosis, showed lower levels of hepatic manganese content with increasing grade of steatosis.

A survey of arsenic, mercury, cadmium, and lead residues in seafood (fish, crustaceans, and cephalopods) from the south-eastern Mediterranean Sea.

Seafood is capable of bioaccumulating heavy metals (HM), making it a potentially major dietary source of HM for humans. Presently, little data exists on seafood from the eastern-most boundary of the Mediterranean Sea. This study aims to provide exposure insight of the Israeli population to HM through the consumption of locally caught seafood by assessing the levels of arsenic, mercury, cadmium, and lead in raw tissues of seafood. A wide survey of local fisheries was conducted providing 296 samples from 11 different species, including seven fish, two crustacean, and two cephalopod species. Total arsenic, cadmium, and lead were analyzed by graphite-furnace atomic absorption. Total mercury was measured by cold-vapor mercury analyzer. Arsenic speciation was performed by anion chromatography-inductively coupled plasma sector field mass spectrometry. Results suggested that the total arsenic concentrations were significantly higher in crustaceans and cephalopods than fish. Arsenic speciation revealed two samples that exceed 1 mg/kg of inorganic arsenic, whereas methylated arsenic was below the detection limit. Elevated mercury levels were detected in the commercial benthic species Mullus barbatus (red mullet), cadmium was detected in one-third of the samples, and lead detected in eight samples. Comparing the results to health guidelines, 99.4% of seafood tested in this study abide with acceptable levels of heavy metals in seafood, as defined by both Israeli and European Union guidelines.

Normal variability of 22 elements in 24-hour urine samples - Results from a biobank from healthy non-smoking adults.

Urine is often used for biomonitoring the exposure to elements. However, most studies report concentrations in spot urine samples, which may not accurately mirror the "gold standard" of complete 24-h (24h) urine samples. There are relatively few data published for 24h samples, and little information on the within- and between person variability. The present study aimed at assessing variability within and between individuals in 24h excretion for a number of elements in adults from the general population and the typical 24h excretion of these elements. In addition, we assessed concentrations adjusted for creatinine and specific gravity (SG), and associations between elements. 60 healthy non-smokers (31 women and 29 men) from Sweden, aged 21-64 years, collected all urine during 24h (split into six separate samples) on two occasions, about one week apart. Concentrations of As, Br, Cd, Co, Cr, Cu, Fe, Hg, Li, Mn, Mo, Ni, P, Pb, S, Sb, Se, Sn, U, V, W, and Zn in urine were analyzed by inductively coupled plasma sector-field mass spectrometry (ICP-SF-MS) and 24h excretion rates were calculated for each day. The ratio of between-individual variance and the total variance, the intra-class correlation (ICC) was calculated based on natural log-transformed 24h excretion. Correlation coefficients were calculated between excretion rates (mass/24h), and concentrations adjusted for creatinine and SG. Geometric means (GM), and 90-percentiles are presented for each element. The 24h excretion was higher in men than in women for most elements, and the difference was statistically significant for Cr, Cu, Fe, Li, P, Pb, S, Se, U, V, and Zn. However, for Cd and Co, the excretion was higher in women. Variability between days was low for Cd, Co, Hg, Pb, Sn, Se, V, and Zn (ICC 0.75-0.90), highest for Cr (ICC=0.3) and Sb (ICC=0.18), and moderate for the other elements. Spearman's rank correlation coefficients were about 0.8-0.9 for 17 elements, and 0.3-0.7 for Br, Cu, P, S, Se. Excretion of P and S were highly correlated, and also associated with excretion of most of the other elements, especially Cu, Se, V, and Zn. A high correlation was also found between As and Hg, between Mo and W, as well as between Cr, Fe and Mn. These data present normal variability of 24h excretion of a number of elements, and can also be used as updated reference levels for elements with no or limited previous literature available. Information on variability within- and between individuals is important to know when designing studies with urine levels of elements used as exposure biomarker in studies of associations with health outcomes.

Quantification of aluminium release from Finn chambers under different in vitro test conditions of relevance for patch testing.

Contact allergy to aluminium (Al) might pose a risk of false-positive readings of patch-test results when testing with Finn chambers. To quantify the release of Al from empty Al Finn chambers, covered Finn Aqua chambers, and Al Finn chambers containing different baseline patch-test substances. Al Finn chambers of different conditions and with different patch-test substances were tested in artificial sweat and their Al release was analyzed by atomic absorption spectroscopy and inductively coupled plasma sector field mass spectrometry. The amount of Al released from empty Finn chambers corresponded to a skin dose of 0.03%-0.5% Al chloride hexahydrate applied in plastic chambers. Although most patch-test substances reduced the release of Al from the Finn chambers due to covering the surface, some substances significantly increased the release of Al from the Finn chambers, most notable for Caine mix II 10% pet., Myroxylon pereirae 25% pet., and sodium tetrachloropalladate hydrate 3.0% pet. The release of Al from Finn chambers corresponds in some cases to clinically relevant concentrations of Al for Al-sensitized individuals.

U–Pb Dating of Zircon and Zirconolite Inclusions in Marble-Hosted Gem-Quality Ruby and Spinel from Mogok, Myanmar

The Mogok area in Myanmar (Burma) is known since historic times as a source for some of the finest rubies and spinels in the world. In this study, we focus on in-situ U–Pb geochronological analyses of zircon and zirconolite, either present as inclusions in gem-quality ruby and spinel or as accessory minerals in ruby- and spinel-bearing marble and adjacent granulite facies gneisses. The age determination was carried out using both laser ablation inductively coupled plasma time-of-flight mass spectrometry (LA-ICP-TOF-MS) and sector-field mass spectrometry (LA-ICP-SF-MS). In addition, we present multi-element data (REE) of zircon and zirconolite collected with LA-ICP-TOF-MS to further characterize these inclusions. Most of the studied zircon grains display growth zoning (core/rim) regardless if as inclusion in gemstones, or as accessory mineral in host rock samples. U–Pb dating was conducted on both core and rim of zircon grains and revealed most ages ranging from ~200 Ma in the core to ~17 Ma in the rim. The youngest U–Pb ages determined from the rim of zircon inclusions in gem-quality ruby and spinel are 22.26 ± 0.36 Ma and 22.88 ± 0.72 Ma, respectively. This agreement in U–Pb ages is interpreted to indicate a simultaneous formation of ruby and spinel in the Mogok area. In ruby- and spinel-bearing marble from Bawlongyi, the youngest zircon age was determined as 17.11 ± 0.22 Ma. Furthermore, U–Pb age measured on the rim of zircon grains in a biotite-garnet gneiss reveals a Late Oligocene age (26.13 ± 1.24 Ma), however older ages up to Precambrian age were also recorded in the cores of zircon as accessory minerals from this gneiss. These old ages point to a detrital origin of the analysed zircon cores. Although non-matrix matched standard was applied, zirconolite U–Pb age results are narrower in distribution from ~35 Ma to ~17 Ma, falling within the range of zircon ages. Based on results which are well in accordance with previous geochronological data from the Mogok Metamorphic Belt (MMB), we deduce that gem-quality ruby and spinel from Mogok probably formed during a granulite-facies regional metamorphic event in Oligocene to Early Miocene, related to post collision tectonics of the Eurasian and Indian plates. Our data not only provide key information to understand the formation of gem-quality ruby and spinel in the so-called Mogok Stone Tract, but also provide assisting evidence when determining the country of origin of gemstones in gemmological laboratories.

Zeolite Beta Doped with La, Fe, and Pd as a Hydrocarbon Trap

Hydrocarbon trapping is a technique of great relevance, since a substantial part of hydrocarbon emissions from engines are released from engines before the catalyst has reached the temperature for efficient conversion of the hydrocarbons. In this work, the influence of doping zeolite beta (BEA) with Fe, Pd, and La on the storage and release of propene and toluene is studied. Five monolith samples were prepared; Fe/BEA, La/BEA, Pd/BEA, Pd/Fe/BEA, and Pd/La/BEA using incipient wetness impregnation, and the corresponding powder samples were used for catalyst characterization by Inductively coupled plasma sector field mass spectrometry (ICP-SFMS), Temperature-programmed oxidation (TPO), X-ray photoelectron spectroscopy (XPS) and Scanning transmission electron microscopy with Energy dispersive X-ray analysis (STEM-EDX). The hydrocarbon trapping ability of the samples was quantified using Temperature-programmed desorption (TPD) of propene and toluene, and in situ Diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS). The results from the TPD experiments show that the addition of Pd and La to the zeolite affected the release patterns of the stored hydrocarbons on the trapping material in a positive way. The in situ DRIFTS results indicate that these elements provide H-BEA with additional sites for the storage of hydrocarbons. Furthermore, EDX-mapping showed that the La and Pd are located in close connection.

Fe variation characteristics and sources in snow samples along a traverse from Zhongshan Station to Dome A, East Antarctica

Iron concentrations in the Southern Ocean are thought to act as a driver of the regular glacial–interglacial cycles in atmospheric carbon dioxide (CO2). This study presents the concentrations of bioavailable Fe (dissolved Fe (DFe) and total dissolved Fe (TDFe)), major ions (Na+, K+, Mg2+, Ca2+, Cl−,NO3‐,SO42‐ and methanesulfonic acid (MSA)), heavy metal elements (Sr, Pb, V, Ti and Cd), and rare earth elements (REEs; specifically, La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb and Lu) and the oxygen and hydrogen isotopic compositions (δ18O and δD) from a series of surface snow samples collected during from January 22 to February 5, 2017 along a traverse from Zhongshan Station to Dome A in East Antarctica. The results reflect the Antarctic surface snow Fe and the other trace element concentrations on the East Antarctica ice sheet. In particular, the DFe and TDFe concentrations were measured using inductively coupled plasma sector field mass spectrometry (SF-ICP-MS). The concentration patterns of DFe and TDFe show three different stages along this transect. First, there is an abrupt decrease with distance inland from the coast and then a slight decreasing trend with increasing elevation. The maximum concentrations were observed at distances of 450–600 km from the coast, indicating that there are different potential sources and/or transporting air masses. The variations show that the sources and processes that deliver bioavailable Fe differ along this transect. These data are useful for assessing bioavailable Fe release from the Antarctic ice sheet.

Plutonium fallout reconstructed from an Antarctic Plateau snowpack using inductively coupled plasma sector field mass spectrometry

Anthropogenic plutonium (Pu) in the environment is a result of atmospheric nuclear testing during the second half of the 20th century. In this work, we analyzed a 4-meter deep Antarctic Plateau snowpack characterized by a low snow accumulation rate and negligible snow impurities. These sample conditions enabled us to measure the snowpack Pu fallout by applying inductively coupled plasma sector field mass spectrometry to a few mL of snow melt without purification or preconcentration. Pu concentrations in the reconstructed Pu fallout record for the period after 1956 CE increased and decreased in agreement with past atmospheric nuclear testing. Two peaks and two dips associable with historical events were observed, and the highest peak in 1964(±1) CE approximately coincided with the maximum concentration of non-sea-salt sulfate caused by the Mt. Agung eruption in 1963 CE. Enhanced Pu fallout in the 1970s was attributed the geographical proximity of the Southern Hemispheric nuclear test sites. Our results suggest that by improving the instrumental sensitivity and precision, the potential of the Antarctic ice sheet as an archive of Pu fallout can be further explored and utilized for understanding atmospheric dispersion and for dating ice cores.

In situ determination of trace elements in melt inclusions using laser ablation inductively coupled plasma sector field mass spectrometry

In situ trace element analysis of melt inclusions by laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) provides important geochemistry information. However, the precision and accuracy of this technique are affected by many factors, such as matrix effect, laser conditions, and calibration method. In addition, many previous LA-ICP-MS studies ablated entire melt inclusions along with their host minerals and obtained trace element composition by deconvoluting the mixed ablation signal, which may induce much uncertainty. A 193 nm ArF laser ablation system combined with inductively coupled plasma sector field mass spectrometry (ICP-SF-MS) was used to investigate matrix effect, laser conditions, choice of external calibration standards, and data reduction strategy for in situ analysis of 36 major and trace elements in six common silicate reference glasses. The validity of the protocol presented here was demonstrated by measuring trace elements in olivine-hosted melt inclusions. Instead of ablating entire melt inclusions along with their host minerals, melt inclusions were polished to the surface to avoid laser ablating the mineral host. The calibration lines calculated from the calibration standards should cross the coordinate origin, especially for low-concentration elements (<10 ppm). As the laser crater size increased from 17 to 33 μm, the precision was improved from <20% to <8% (2RSD), and accuracy was improved from ±20% to better than ±10%. Most measured trace elements in Dali melt inclusions are consistent with those in their host rocks. For mobile elements (Ba, Sr, Pb), melt inclusions display much smaller variations than their host rocks. A simple but accurate approach for in situ analysis of trace elements in melt inclusions by LA-ICP-SF-MS has been established, which should greatly facilitate the wider application of in situ trace element geochemistry to melt inclusion studies.