Coupled Plasma Sector-field Mass Spectrometry Research Articles

New insights on Late Pliensbachian-Early Toarcian seawater chemistry based on belemnite rostra element content

Belemnites were a type of cephalopod abundant in the Jurassic and Cretaceous, whose fossils have been extensively used for paleo-oceanographic studies. For this study, we analyzed 69 elements by Inductively Coupled Plasma-Sector Field Mass Spectrometry (ICP-SFMS) in 15 belemnite rostra from the West Rodiles section in the Asturian Basin, Northern Spain. We aim to determine if belemnite rostra carbonate chemistry reflects changes in seawater chemistry during the Late Pliensbachian–Early Toarcian time interval and examine how belemnites can be used to trace known drivers of the Early Toarcian Oceanic Anoxic Event (T-OAE) and associated oceanographic processes.Discarding drastic intra-species effects and assuming a similar influence of growth rates, diet, and other physiological processes for all analyzed belemnite specimens and taking into consideration the sizeable analytical uncertainty, we assess if determined belemnite rostra element chemistry reflects broad and relative changes in paleo-seawater chemistry. Many determined elements are present in only ppb amounts, and their interpretation is uncertain. We found that Mg, Mn, and P increase in the interval chronocorrelative to the T-OAE. This is interpreted to have resulted from an increase in these elements' inventory in seawater due to an increase in continental weathering and fluvial runoff associated with this global event. Iron, K, and Na contents decrease upwards in the section, potentially indicating that these elements became limited and likely hampered oceanic productivity. Our study also found a correspondence between a change in the behaviour of several elements, warming, the T-OAE negative CIE, and a reduction in the diversity and size of both calcareous nannofossils and belemnites in the study area.

Changes in Cerebrospinal Fluid Concentrations of Selenium Species Induced by Tofersen Administration in Subjects with Amyotrophic Lateral Sclerosis Carrying SOD1 Gene Mutations.

Amyotrophic lateral sclerosis (ALS) is a fatal neurodegenerative disease affecting the brain and spinal cord motor neurons. On 25 April 2023, the drug tofersen, an antisense oligonucleotide, received the US Food and Drug Administration approval for treating ALS in adults carrying mutations of the SOD1 gene. We aimed at assessing whether cerebrospinal fluid concentrations of selenium, an element of both toxicological and nutritional interest possibly involved in disease etiology and progression, are modified by tofersen administration. We determined concentrations of selenium species by anion exchange chromatography hyphenated to inductively coupled plasma-dynamic reaction cell-mass spectrometry and overall selenium by using inductively coupled plasma sector-field mass spectrometry, at baseline and 6months after active tofersen treatment in ten Italian ALS patients carrying the SOD1 gene mutation. Concentrations of total selenium and many selenium species substantially increased after the intervention, particularly of inorganic (tetravalent and hexavalent) selenium and of the organic species selenomethionine and a compound co-eluting with the selenocystine standard. Overall, these findings suggest that tofersen treatment markedly alters selenium status and probably the redox status within the central nervous system, possibly due to a direct effect on neurons and/or the blood-brain barrier. Further studies are required to investigate the biological and clinical relevance of these findings and how they might relate to the pharmacological effects of the drug and to disease progression.

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.

Exploring Pt-Pd Alloy Nanoparticle Cluster Formation through Conventional Sizing Techniques and Single-Particle Inductively Coupled Plasma-Sector Field Mass Spectrometry.

Accurate characterization of Pt-Pd alloy nanoparticle clusters (NCs) is crucial for understanding their synthesis using Gas-Diffusion Electrocrystallization (GDEx). In this study, we propose a comprehensive approach that integrates conventional sizing techniques-scanning electron microscopy (SEM) and dynamic light scattering (DLS)-with innovative single-particle inductively coupled plasma-sector field mass spectrometry (spICP-SFMS) to investigate Pt-Pd alloy NC formation. SEM and DLS provide insights into morphology and hydrodynamic sizes, while spICP-SFMS elucidates the particle size and distribution of Pt-Pd alloy NCs, offering rapid and orthogonal characterization. The spICP-SFMS approach presented enables detailed characterization of Pt-Pd alloy NCs, which was previously challenging due to the absence of multi-element capabilities in conventional spICP-MS systems. This innovative approach not only enhances our understanding of bimetallic nanoparticle synthesis, but also paves the way for tailoring these materials for specific applications, marking a significant advancement in the field of nanomaterial science.

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).

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.

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.

Material Characterization and Influence of Sliding Speed and Pressure on Friction and Wear Behavior of Self-Lubricating Bearing Materials for Hydropower Applications

Nowadays, hydropower plants are forced to have more frequent power control and the self-lubricated bearings used in the applications are one of the most critical components affected by the continuously changing operating conditions. In this study, microstructure and composition of two commercially available bearing materials (Orkot TXM Marine and Thordon ThorPlas) used in hydropower turbines were studied. In addition, the influence of sliding speed and applied pressure on the friction and wear behavior of the materials was investigated systematically for dry sliding conditions. The bearing materials were characterized using X-ray microtomography, Nuclear Magnetic Resonance (NMR) spectroscopy and Inductively Coupled Plasma–Sector Field Mass Spectrometry (ICP-SFMS) techniques. Friction and wear tests were carried out with a polymer pin sliding against a stainless steel (SS2333) plate with a linear reciprocating motion. Test conditions were: room temperature, 9–28 MPa pressure and 10–40 mm/s sliding speed ranges. Surface analysis of the polymer pins and the wear tracks were performed by optical profilometry, Scanning Electron Microscope (SEM) and Energy Dispersive Spectroscopy (EDS) techniques. Test results show that, for both materials, the coefficient of friction (COF) is decreasing at higher pressures. Surface analysis reveals higher concentrations of solid lubricants in the transfer layers formed at higher pressures, explaining the decrease in COF. Furthermore, the specific wear rate coefficients are increasing at higher sliding speeds, especially at lower pressures. Results of this study demonstrate that, under dry sliding conditions, changes in sliding speed and pressure have a significant influence on the tribological behavior of these bearing materials.

Selenium and sulphur in Athabasca bituminous sands mineral and bitumen fractions

There is increasing environmental concern regarding the emission of selenium (Se) from mining and upgrading of bitumen extracted from the Athabasca bituminous sands (ABS) in northern Alberta, Canada. However, there remains a lack of high quality analytical data for Se in this massive hydrocarbon reserve. Accurate analytical determinations of Se in bitumen from ABS are an important first step toward understanding its potential to be emitted to the environment. This has been a challenge due to the low abundance of Se combined with the preponderance of entrained mineral material (sand, clay) and the generally inadequate sensitivity of analytical methods used in the past. To overcome these issues, samples of ABS ores (McMurray Formation) underwent a toluene extraction procedure under ultra-clean lab conditions to separate bitumen from mineral particles. Separated bitumen, residual mineral material, and bulk ores were then subjected to acid-digestion and analysis using inductively coupled plasma sector-field mass spectrometry (ICP-SFMS) as well as hydride generation atomic fluorescence spectroscopy (HG-AFS). Unlike many other potentially toxic trace elements (Ag, As, Be, Cd, Cu, Pb, Sb, Tl and Zn) which exist almost exclusively in the mineral fraction, Se was found primarily (ca. 80%) in the organic (bitumen) fraction. Sulphur was determined in the same acid digests using both ICP-SFMS and inductively coupled plasma-optical emission spectroscopy (ICP-OES) and it too, was found almost exclusively in the bitumen fraction. Despite the limited number of samples available to our study, the positive, linear correlation between Se and S concentrations in bitumen suggests that S concentrations can be used as a guide to estimate their Se content. Given that Se is found mainly in the organic fraction of the ABS, there is considerable potential for mobilization of this element during upgrading and refining. The analytical methods successfully employed here have sufficient sensitivity to support studies of Se contamination of environmental media in the ABS region.

Trace Element Analysis of Borrelia burgdorferi by Inductively Coupled Plasma-Sector Field Mass Spectrometry.

Transition metal ions play important structural, regulatory, and catalytic roles in all biological systems by serving as cofactors for proteins. Due to their relatively low levels in the cell compared to abundant metal ions such as potassium and magnesium, transition metals are often considered micronutrients and referred to as trace elements. Manganese (Mn), iron (Fe), copper (Cu), and zinc (Zn) are the most prevalent transition metals in the Lyme disease spirochete Borrelia burgdorferi. Here, we describe a method for the accurate measurement of these trace elements in B. burgdorferi utilizing inductively coupled plasma-sector field mass spectrometry (ICP-SFMS).

Study of the Accumulation of Toxic and Essential Ultra-Trace Elements in Fruits of Sorbus domestica L.

In the present work, the accumulation of selected toxic and essential ultra-trace elements in fruits of service tree (Sorbus domestica L.) were determined depending on harvest time. Samples were collected from the same sampling area in two different years and within one year in September and October (maturity state). Harvesting the fruits in the same area excludes the influence of metals taken up via roots, thus the impact of airborne contamination by heavy metal translocation can be studied. All samples were dried and digested using an acidic microwave assisted digestion system prior to quantification by inductively coupled plasma—sector field mass spectrometry (ICP–SFMS). The elements chosen were Arsenic and Cadmium as well as Lithium, Molybdenum, and Selenium. The Arsenic content rose with maturity in mesocarp. Cadmium found in the mesocarp was unaffected by ripeness. For Selenium and Molybdenum, no statistically significant effect of ripeness could be found on their content in mesocarp. Lithium could not be detected in the majority of fruit samples. Differences between the metal concentrations based on the year of harvest were found for Arsenic, Molybdenum, and Selenium, depending on precipitation. The drier the season, the more Arsenic was accumulated. For Molybdenum and Selenium, the opposite effect was observed.

Radionuclide Determination In Surface Water Samples By Inductively Coupled Plasma With Sector Field Mass Spectrometry (ICP-SFMS)

The determination of naturally occurring radionuclides in the environment by inductively coupled plasma mass spectrometry of high resolution (ICP-SFMS) has gained recognition over the last fifteen years, relative to the radiometric techniques, as the result of improvement in instrumental performance, sample introduction equipment and sample preparation. With the increase in instrumental sensitivity, it is now possible to measure ultratrace levels of many radioisotopes.The aim of this work was to determined the natural radionuclides (232Th, 234U, 235U and 238U) in surface water using Inductively Coupled Plasma-Sector Field Mass Spectrometry (ICP-SFMS). The samples were sampling from Lerma river, State of Mexico at february to april 2015. The process of treatment of sample consisted in perform an acid digestion according to the 3015A USEPA method followed of the direct measurement in ICP-SFMS. Results obtained were: a) identify the presence of 232Th, 234U, 235U and 238U isotopes in water, b) isotopic ratios were for 234U/238U=1.133 ± 0.016. ICP-SFMS has gained popularity in the field of radiochemistry, particularly as a method of detection for long lived-actinides.

One-million year Rare Earth Element stratigraphies along an Antarctic marine sediment core

An integrated system, based on Inductively Coupled Plasma-Sector Field Mass Spectrometry (ICP-SFMS) and Inductively Coupled Plasma-Atomic Emission Spectrophotometry (ICP-AES) techniques, was optimised for the geochemical characterisation of soils and marine sediments. Sample mineralization was carried out with HF, HNO3 and HClO4. Operative blanks were at least two orders of magnitude lower than the lowest concentration measured in real samples. For ICP-SFMS, the detection power of the method in high resolution mode was sufficient for an accurate quantification of metals, yet avoiding REEs' (Rare Earth Elements) isobaric interferences. Once tested the accuracy on six certified materials, the methods were applied to the analysis of 39 major and trace metals on the top 90m of sediments from the ANDRILL AND-1B core, covering the last million years.Stratigraphies of REEs and of normalised markers from this core clearly highlight a discontinuity at about 660,000years before present. This pattern is well shown by the results of a PMF (Positive Matrix Factorization) statistical analysis, revealing two different sources for the sedimentary material, whose relative contribution changed around that time. Such a result is consistent with previous studies and confirms the net change in the provenance of glacial fluxes in the McMurdo region (Ross Ice Shelf, Antarctica) in the last million years.

Improved performance of a shielded torch using ethanol in inductively coupled plasma–sector field mass spectrometry

To improve the accuracy and precision of trace element analysis, higher analytical sensitivity and lower interference are required. In this study, we investigated the effects of the addition of ethanol in combination with a shielded torch on the signal intensities of elements from 7Li to 238U, oxide yields, doubly charged ion yields, isobaric interferences and ion distributions in inductively coupled plasma–sector field mass spectrometry (ICP–SFMS). For the 39 investigated elements in this study, using the shielded torch increases the sensitivity by a factor of 17–58. The well-known drawback of using a shielded torch is that it will increase the oxide yield. In this study, the CeO+/Ce+ ratio is increased by a factor of 3.3 in the GE-on mode compared to that in the GE-off mode at normal conditions (without ethanol). In the GE-on mode, the addition of 4% ethanol in ICP–SFMS is found not only to decrease the CeO+/Ce+ ratio by a factor of 4 but also to suppress the Ce2+/Ce+ ratio by a factor of 4.2. In large contrast, the effect of 2–6% ethanol on the oxide yield and doubly charged ratio is minimal in the GE-off mode. Except for As, Se, Sb, Te and Au, for which the signal intensities are increased by a factor of 1.4–3.7 in the presence of 2–6% ethanol, an increased concentration of ethanol suppresses intensities of other elements. In the GE-off mode, the suppression of the analyte signal due to increased ethanol concentration is more significant than that in the GE-on mode. Compared to the spatial profiles of the ion distributions in the normal mode (without ethanol), the addition of 2–4% ethanol leads to significantly wider axial and radial profiles. The significantly wider axial and radial ion distribution had a dilution effect on the ion densities, which subsequently reduced the ion signal intensities. The addition of 4% ethanol was also found to suppress the interferences of Xe by a factor of 2.8 and increase the sensitivity of Te determination in ICP–SFMS by a factor of 2.1 relative to the values obtained in conventional 2% (v/v) HNO3 solution at the corresponding optimum operating conditions in the GE-on mode. The addition of 4% ethanol in combination with the GE-on mode was successfully applied to the direct determination of nanogram levels of Te in a series of geological reference materials.

Determination of relative rare earth element distributions in very small quantities of uranium ore concentrates using femtosecond UV laser ablation – SF-ICP-MS coupling

An alternative analytical method has been developed to determine lanthanide distribution using hundreds of nanograms of uranium ore concentrates by femtosecond ultra-violet laser ablation coupled to inductively coupled plasma sector-field mass spectrometry.

Different uranium distribution patterns in cytosolic protein pool of zebrafish gills after chronic and acute waterborne exposures

The toxicity of uranium (U) to aquatic organisms depends notably on its compartmentalization in organs, tissues, cells as well as on its distribution among biomolecules. In order to contribute to the understanding of U accumulation and associated toxicity mechanisms in case of waterborne exposure, this study focused on U fate in the gills epithelia, uptake pathway, of the fish model Danio rerio (zebrafish). U distribution among cytosolic biomolecules was investigated after no addition (0μgL−1 (c0) for 3 and 30d), chronic (20μgL−1 (c20) for 30d) and acute (20μgL−1 (c20) and 250μgL−1 (c250) for 3d) exposures to depleted U. Cytosolic U accounted for an average of 24–32% of gills burden for c20 and c250, respectively. Size Exclusion Chromatography (SEC) coupled with Inductively Coupled Plasma-Sector Field Mass Spectrometry (ICP-SFMS) allowed identification of ecotoxicologically relevant U-containing fractions among cytosolic biomolecules as a function of exposure conditions. In c0 and c20 samples, most U (ca.80%) was found in the Low Molecular Weight fraction (LMW, <18kDa), often considered as a detoxifying fraction. In c250 exposed fish, U was equally distributed between LMW (40%) and High Molecular Weight (HMW, 150–670kDa; 40%) fractions, the latter including sensitive metalloproteins. Uranium-biomolecules were co-eluted with endogenous essential metal (Fe, Cu and Zn) species, however, no major influence on their cytosolic concentration and distribution pattern among cytosolic proteins was found.

Characterization of brines and evaporites of Lake Katwe, Uganda

Lake Katwe brines and evaporites were investigated to determine their chemical, mineralogical and morphological composition. 30 brine samples and 3 solid salt samples (evaporites) were collected from different locations of the lake deposit. Several analytical techniques were used to determine the chemical composition of the samples including Inductively Coupled Plasma–Atomic Emission Spectrometry (ICP–AES), Inductively Coupled Plasma–Sector Field Mass Spectrometry (ICP–SFMS), ion chromatography, and potentiometric titration. The mineralogical composition and morphology of the evaporites was determined using X-ray diffraction (XRD) and scanning electron microscopy (SEM), respectively. Physical parameters of the lake brines such as density, electrical conductivity, pH, and salinity were also studied. The results show that the lake brines are highly alkaline and rich in Na+, Cl−, CO32-, SO42-, and HCO3- with lesser amounts of K+, Mg2+, Ca2+, Br−, and F− ions. The brines show an intermediate transition between Na–Cl and Na–HCO3 water types. Among the trace metals, the lake brines were found to be enriched in B, I, Sr, Fe, Mo, Ba, and Mn. The solid salts are composed of halite mixed with other salts such as hanksite, burkeite and trona. It was also observed that the composition of the salts varies considerably even within the same grades.

Determination of bismuth in open ocean waters by inductively coupled plasma sector-field mass spectrometry after chelating resin column preconcentration

A novel low-blank method is described for the analysis of bismuth in seawater based on preconcentration using an ethylenediaminetriacetic acid chelating resin column followed by determination with inductively coupled plasma sector-field mass spectrometry (ICPSFMS). A sample is siphoned into and drains through the column with the flow rate being kept constant by using a flotation device. Bi in 250mL of acidified seawater is extracted onto the column in this process and eluted with 2mL of 3M HNO3 followed by 3mL of ultra-high purity water. The concentration of Bi in the eluate is measured by ICPMS. The benefits of the method compared to others are its simplicity, a smaller amount of seawater, and lower procedural blanks and detection limits at pgkg−1 levels. Data on dissolved Bi in open ocean reference samples of SAFe and GEOTRACES programs are presented for the first time.

Distribution of dissolved and particulate metals in Antarctic sea ice

Samples were collected in East Antarctic sea ice in late winter/early austral spring 2007 to assess the distributions of Al, Cr, Mn, Cu, Zn, Mo, Cd and Ba. Total dissolved (< 0.2 μm) and particulate (> 0.2 μm) concentrations were measured by Inductively Coupled Plasma-Sector Field Mass Spectrometry (ICP-SFMS) in snow, pack ice and fast ice. Particulate concentrations were also determined in underlying seawater for these elements. The concentrations of particulate metals were one to two orders of magnitude higher in sea ice than in snow and seawater, except for Mo and Cr. Barite maxima in sea ice vertical profiles at all sites may indicate heterotrophic activity. Particulate Al and Mn distributions suggest a signal from Antarctica's shelf sediments. Dissolved metals were one order of magnitude higher in sea ice as compared to snow, although they were not enriched in sea ice as compared to data reported in the literature for Antarctic surface waters. An analysis of dissolved-to-total metal ratios showed that all studied metals were found almost exclusively in the dissolved phase in Antarctic pack ice. Dissolved metals distributions indicate that spatial variability does not seem to be strong. Our results also demonstrate that dissolved Al, Cr, Mo and Ba behaved conservatively with bulk ice salinity gradients. This would confirm the main source of trace metals to Antarctic sea ice comes from seawater and not from direct atmospheric deposition. Dissolved bioactive metals Mn, Cu, Zn and Cd concentrations were scattered when plotted against bulk ice salinity, but did not show a seasonal decrease nor reach limitation status. Finally, seasonal ice melt does not seem to contribute significantly to the supply of dissolved bioactive metals, other than Fe, to Antarctic surface waters.

A new method integrating high-precision U–Pb geochronology with zircon trace element analysis (U–Pb TIMS-TEA)

Increased precision in isotope-dilution thermal ionization mass spectrometry (ID-TIMS) U–Pb geochronology has revealed age complexities in zircon populations that require new tools for understanding how the growth of zircon is related to geologic processes. U and Pb are routinely separated from other elements in dated minerals by ion exchange separation prior to TIMS isotope measurement. We develop a method in which trace elements in the exact same volume of zircon are redissolved and analyzed using solution nebulization inductively coupled plasma sector-field mass spectrometry with matrix-matched external liquid calibration. Using <0.5 ml solution, resulting concentrations are between <1 ppt for elements such as Ti, Nb and Ta and tens of ppb for Zr. By analyzing a series of standard solutions, zircons and procedural blanks, we show that accurate measurements are performed on Zr, Hf, Y, Sc, and the HREE while low-concentration elements can be measured accurately to <5 ppt. We performed combined U–Pb ID-TIMS geochronology with trace element analysis (here called U–Pb TIMS-TEA) on zircons from eight volcanic rocks comprising several volcanic systems and one metamorphic sample. Similar to previous in situ trace element analyses, zircon geochemistry is distinct between different samples and records petrogenetic processes such as fractional crystallization, assimilation and/or magma mixing. Unique from in situ analysis, U–Pb TIMS-TEA can trace geochemical evolution in accessory minerals with adequate age precision to resolve magmatic processes in rocks at least 200 million years old. This provides a means to identify auto-, ante- and xenocrystic zircon and lead to more robust age interpretations in ID-TIMS U–Pb geochronology. One suite of Cretaceous andesitic zircons shows correlations in geochemistry and absolute time that record evolution of a magmatic system over ∼250 ka prior to eruption. Future work will combine U–Pb TIMS-TEA with solution isotopic analysis of Nd, Sr and Hf and will be applied to a host of datable minerals such as monazite, sphene, apatite, rutile, xenotime, and baddeleyite. These combined tools will provide access to an improved understanding of a wide range of igneous and metamorphic processes as a function of time.