Multi-collector Inductively-coupled Plasma Mass Research Articles

High-precision K isotopic analysis of cerebrospinal fluid and blood serum microsamples via multicollector inductively coupled plasma-mass spectrometry equipped with 1013 Ω faraday cup amplifier resistors

BackgroundPotassium isotopic analysis is increasingly performed in both geological and biological contexts as a result of the introduction of MC-ICP-MS instrumentation either equipped with a collision/reaction cell or having the capability of working at “extra-high” mass resolution in order to deal with spectral interference caused by argon hydride (ArH+) ions. Potassium plays an important role in the central nervous system, and its isotopic analysis could provide an enhanced insight into the corresponding processes, but K isotopic analysis of cerebrospinal fluid is challenging due to the small volume, a few microliter only, typically available. This work aimed at developing a method for determining the K isotopic signature of serum and cerebrospinal fluid at a final K concentration of 25 ng mL−1 using Faraday cup amplifiers equipped with a 1013 Ω resistor. ResultsPotassium isotope ratios obtained for reference materials measured at a final K concentration of 25 ng mL−1 were in excellent agreement with the corresponding reference values and the internal and external precision for the δ41K value was 0.11 ‰ (2SE, N = 50) and 0.10 ‰ (2SD, N = 6), respectively. The robustness against the presence of matrix elements and the concentration mismatch between sample and standard observed at higher K concentrations is preserved at low K concentration. Finally, K isotopic analysis of serum and cerebrospinal fluid (3–12 μL of sample) of healthy mice of both sexes was performed, revealing a trend towards an isotopically lighter signature for serum and cerebrospinal fluid from female individuals, however being significant for serum only. SignificanceThis work provides a robust method for high-precision K isotopic analysis at a concentration of 25 ng mL−1. By monitoring both K isotopes, 39K and 41K, with Faraday cups connected to amplifiers with 1013 Ω resistors, accurate K isotope ratio results are obtained with a two-fold improvement in internal and external precision compared to those obtained with the set-up with traditional 1011 Ω resistors. The difference in the K isotope ratio in CSF and serum between the sexes, is possibly indicating an influence of the sex or hormones on the fractionation effects accompanying cellular uptake/release.

Sensitive 236U/238U Isotopic Analysis of Trace Uranium in Safeguards Environmental Samples Using Multicollector Inductively Coupled Plasma Mass Spectrometry.

A sensitive analytical technique was developed for determining a 10-7 level low 236U/238U ratio using multicollector inductively coupled plasma mass spectrometry. This analytical technique can determine the subnanogram amount of uranium in safeguards environmental samples. To increase the sensitivity of the 236U/238U ratio, (1) the feed solution was concentrated to one-tenth of that in the conventional method and (2) data acquisition was started from the beginning of the solution uptake until all of the solution was exhausted. All signal intensities were recorded. This technique was applied to the IRMM-184 uranium isotopic standard solution with a 1.2410 × 10-7 236U/238U ratio. The IRMM-184 uranium solution (0.2 mL of 1 ng g-1 uranium) was prepared, and the 236U/238U ratios were determined using our new data collection method. The 236U/238U ratios were in agreement with the certified value within the uncertainty (k = 2) evaluated using the Guide to the Expression of Uncertainty in Measurement (GUM) workbench. The uncertainties obtained with this new technique (32% on average) were revised to be 10 times smaller than those obtained with the conventional method using 0.1 ng g-1 IRMM-184. The tailing effect from the 238U intense peak was determined using 10 times higher concentrations of NBL CRM U0002 uranium isotopic standard solution (10 ng g-1 uranium) to improve its uncertainty. Approximately 1-2% of the uncertainties of 236U/238U could be further reduced using this improved correction factor.

The isotopic composition of the new enriched silicon crystal Si28-31Pr11: maintaining the realization and dissemination of the mole and the kilogram via the XRCD method

The molar mass and isotopic composition of a new silicon single crystal material (Si28-31Pr11) highly enriched in 28Si has been determined in the context of the x-ray crystal density method used for the realization and dissemination of the SI base units‒the mole and the kilogram. Isotope ratio measurements have been performed using a high-resolution multicollector-inductively coupled plasma mass spectrometer (MC-ICP-MS) with improved technical performance. By applying the Virtual-Element Isotope Dilution Mass Spectrometry method, different crystal areas enclosing the locations of two silicon spheres have been investigated with respect to the magnitude of tentative variations in the molar mass and isotopic composition of the respective samples as a function of their original location in the crystal ingot. In total, 18 subsamples from four different axial and several related radial positions have been characterized. An average molar mass M(Si28-31Pr11) = 27.976 941 464(41) g mol−1 corresponding to a relative combined uncertainty u c,rel(M(Si28-31Pr11)) = 1.4 × 10−9 was yielded. The average enrichment in 28Si of the crystal is expressed by the mean amount-of-substance fraction x(28Si) = 0.999 985 350(37). Two spheres were cut from the crystal ingot. The average molar masses of the spheres Si28kg_03_a and Si28kg_03_b are: M(Si28kg_03_a) = 27.976 941 467(43) g mol−1 and M(Si28kg_03_b) = 27.976 941 461(44) g mol−1, respectively. The results are discussed using uncertainty budgets according to the Guide to the expression of uncertainty in measurement. A homogeneous distribution of the molar mass throughout the crystal is suggested, qualifying it as a material for a primary standard–a silicon sphere–for the realization and dissemination of the mole and the kilogram. A comparison with enriched silicon crystals that are already available is given.

#3539 CALCIUM ISOTOPE RATIOS IN SERUM ARE THE STRONGEST PREDICTOR OF BONE CALCIUM BALANCE IN PATIENTS ON DIALYSIS

Abstract Background and Aims Dysregulated mineral homeostasis is common in chronic kidney disease (CKD) and associated with bone demineralization and vascular calcification. The balance between bone formation and resorption, which reflect the bone calcium (Ca) balance (BCaB), cannot be determined without bone biopsy which is invasive and not easily repeatable. Recently, we have shown that stable (i.e. non-radioactive) Ca isotopes, 42Ca and 44Ca, can be measured in serum and their ratio (δ44/42Caserum) quantitatively determines net bone gain or loss of Ca. Thus, when bone formation exceeds bone resorption, the net BCaB is positive and δ44/42Caserum is high, and when bone resorption is the predominant process δ44/42Caserum is low compared to age-matched controls. In this study we compared δ44/42Caserum against δ44/42Cabone and arterial biopsy samples (δ44/42Caartery) and the sensitivity of δ44/42Ca in predicting changes in bone histology. Method Adults receiving chronic dialysis who underwent bone and arterial biopsies at the time of kidney transplantation were recruited. Patients who had parathyroidectomy or received cinacalcet or anti-resorptive agents were excluded. All participants had Dual Energy X-ray Absorptiometry (DXA) of the hip and lumbar spine. Ca44 and Ca42 measurements were performed in serum and bone and arterial biopsy samples using a multi-collector inductively-coupled plasma mass spectrometer (Thermo Fisher Scientific, Germany). Results Nineteen patients, median age 59.8 years, 84% male, median time on dialysis 3.3 years were included. δ44/42Ca was significantly higher in serum compared to bone or arterial biopsy samples (p < 0.0001), with the lowest isotope ratios in bone (Fig. 1A). δ44/42Cabone was significantly lighter than δ44/42Caartery (p = 0.0002; Fig. 1B). δ44/42Cabone correlated positively with the osteoblastic markers BAP and P1NP (p = 0.0006, R2 = 0.51 and p = 0.009, R2 = 0.31) and inversely with PTH and the osteoclastic marker RANKL (p = 0.0017, R2 = 52 and p = 0.02, R2 = 0.29 respectively; Fig. 2). Both the DXA hip and lumbar spine T-scores and z-scores correlated positively with δ44/42Cabone. δ44/42Caserum showed an inverse correlation with the osteoid area (p = 0.04, R2 = 0.22) and a positive correlation with the absolute mineralized area and the trabecular thickness (p = 0.0004, R2 = 0.58 and p = 0.013, R2 = 0.34 respectively. The were no significant correlations with δ44/42Caartery. On multivariable linear regression analysis significant predictors of δ44/42Caserum were δ44/42Cabone (p = 0.018, 95%CI −1.35 to −0.16), age (p = 0.02, 95%CI 0.002 to 0.02) and BAP (p = 0.019, 95%CI 0.04 to 0.38), together predicting 71% of the variability in δ44/42Caserum. The only significant predictor of δ44/42Cabone was the δ44/42Caserum: p = 0.004, 95%CI −1.6 to −0.37, model R2 = 69%. Conclusion δ44/42Caserum is a significant and independent maker of BCaB, correlating with bone histology measures, and may provide a more sensitive measure than DXA or bone biomarkers. Further studies are required to determine the clinical utility of using δ44/42Caserum to guide management of mineral bone disease in CKD.

Genesis of the Gaolong gold deposit in Northwest Guangxi Province, South China: Insights from in situ trace elements and sulfur isotopes of pyrite

The Guangxi-Yunnan-Guizhou district, also named Dian-Qian-Gui “Golden Triangle”, in Southwest China has a large amount of Carlin-type Au deposits. Gaolong is one source of Carlin-type Au deposit in the northwestern Guangxi Province. Pyrites are the major Au-bearing sulfides. Majority of Au are structurally bound Au+, with a few nanoparticles (Au0) occurring in the sulfides. In this study, in situ chemical and S isotopes of pyrites in the Gaolong Au deposit were analyzed by laser ablation inductively-coupled plasma mass spectrometry and laser ablation multi-collector inductively-coupled plasma mass spectrometry, respectively. Backscattered electron (BSE) images and chemical composition analysis showed that the pyrites were divided into four main types: (1) As-poor Py1 (pre-ore sedimentary or diagenetic stage, with prominent spotted and aggregate structures. These are fine-grained pyrite aggregates with rough surfaces and low brightness under the BSE, with edges often eroded by hydrothermal fluid); (2) As-weak Py2 (early ore stage, the core of the rim pyrite, with good crystallization and characteristic corrosion spots in the particle, and with the edge dissolved to show irregular structure); (3) As-rich Py3 (main ore stage, the narrow pyrite rims overgrowing Py1 and Py2, irregularly-shaped and less than 50 μm in width); and (4) As-rich Py4 (fine-grained pyrite, with good crystallization, high brightness, and symbiotic with Py3 and Py1, or an isolated distribution). Py1 contains higher concentrations of S, Fe, and W, and lower Co/Ni ratios (average of 0.91), suggesting a pre-ore origin. The ore-stage pyrites Py2, Py3, and Py4, have elevated mineralization elements—Au of 0.25–72 ppm, As of 2214–40613 ppm, Tl of 0.95–109 ppm, Sb of 31.16–1851 ppm, Cu of 49.09–910 ppm, with average Co/Ni ratios of 0.43. Au was positively correlated with As, Tl, Cu, and Ni in these pyrites. Electron micro probe analyzer (EMPA) elemental mappings show that: 1) Py1 has a low Au content, while Py2, Py3, and Py4 have high Au, As, Cu, Ti, and Mg contents; 2) Au occurs in As-rich pyrite in the form of invisible gold; 3) Rim pyrite contains high concentrations of Cu, which has a good positive correlation with As, while As and Au are decoupled on a smaller scale. The Au contents and Au/As ratios show that the Au-carrying fluids are unsaturated with Au. In situ S isotopes show that the δ34S values range from 10.19‰ to 13.79‰ with a mean value of 12.07‰ for Py1, 8.60‰ to 10.78‰ with a mean value of 9.77‰ for Py2, 1.42‰ to 8.29‰ with a mean value of 6.81‰ for Py3, and − 0.49‰ to 4.42‰ with a mean value of 1.67‰ for Py4. The δ34S data decreased from Py1 to Py4, whereas the As content increased significantly. This indicates that Au and As are enriched in ore-forming fluids, and the ore-forming fluids have low S isotope values. Based on a comprehensive study of geological and geochemical data, we believe that the magmatic hydrothermal genetic model can explain the genesis of the Gaolong gold deposit. We conclude that the S isotope of pyrites resulted from the mixing of magmatic S and sedimentary S, and the Au-bearing fluid came from deep-concealed granite, establishing a magma genesis of the Gaolong Au deposit.

A Novel Approach for the Determination of the Ge Isotope Ratio Using Liquid-Liquid Extraction and Hydride Generation by Multicollector Inductively Coupled Plasma Mass Spectrometry.

In this work, a method for the accurate and precise determination of the Ge isotope ratio in synthetic water and natural samples of geological origin using multicollector inductively coupled plasma mass spectrometry (MC-ICPMS) with hydride generation was developed. The method was based on the liquid–liquid extraction of Ge to eliminate all elements affecting the generation of germanium hydrides. The standard-sample bracketing method was used to correct instrumental bias. Registration of analytical signal in time-resolved mode gave way to choose signals with best parameters and improved the precision of the results. Controlling the pH by using acetic buffer boosted the sensitivity by nearly five times in comparison to hydride generation methods suggested by other authors. The newly developed method is much simpler and quicker, does not need laborious Ge separation with ion-exchange resins, and thanks to its superior sensitivity, allows measurements of the Ge isotopic ratio in materials with relatively low Ge content. Delta values of the 74Ge/70Ge isotope ratio were measured in standard reference materials for which reference values were available in the GeoREM database. We demonstrated that the accuracy and precession of this method are equally good or better than methods proposed by other authors.

Determination of Picomolar Titanium in Seawater by Isotope Dilution Multicollector Inductively Coupled Plasma Mass Spectrometry after Mg(OH)2 Coprecipitation.

A new isotope dilution inductively coupled plasma mass spectrometry (ICPMS) method is developed to determine picomolar concentrations of titanium (Ti) in seawater. The method applies Mg(OH)2 coprecipitation to concentrate Ti from seawater, and uses a new 49Ti-47Ti isotope dilution to eliminate the need for separating Ti from seawater Ca, resulting in an isobaric interference-free analysis by high-resolution multicollector ICPMS. The method uses a 1.8 mL seawater sample with a detection limit of 1.6 pmol L-1 that is determined mainly by Ti contamination during sample preparation rather than by ICPMS sensitivity, instrumental Ti background, or isobaric interferences. An oceanographically consistent vertical profile of dissolved Ti in the Sargasso Sea near Bermuda is measured with this method.

Sensitivity and High-Precision Lead Isotopic Analysis by Multicollector Inductively Coupled Plasma Mass Spectrometry Based on Liquid Spray Dielectric Barrier Discharge Plasma-Induced Chemical Vapor Generation

Sensitivity and High-Precision Lead Isotopic Analysis by Multicollector Inductively Coupled Plasma Mass Spectrometry Based on Liquid Spray Dielectric Barrier Discharge Plasma-Induced Chemical Vapor Generation

Urban contamination sources in tunnel dusts from São Paulo city: Elemental and isotopic characterization

Elemental and isotopic composition of tunnel dusts collected from Jânio Quadros (JQ) and Maria Maluf (MM) tunnels in São Paulo city were analyzed aiming to determine the potential sources of trace elements in these environments. Sampling was performed in the summer and winter of 2017. Elemental mass fractions were determined by Instrumental Neutron Activation Analysis (INAA) and Graphite Furnace Electrothermal Atomic Absorption Spectrometry (GF-AAS) for 28 elements. Isotopic signatures of Pb and Zn were determined by Thermal Ionization Mass Spectrometry (TIMS) and Multicollector Inductively Coupled Plasma Mass Spectrometry (MC-ICP-MS), respectively. The mean mass fractions of elements, such as Pb, Cd, Zn, Sb and Cu, were in general similar to the reported in the literature, in studies that demonstrated urban contamination by potentially toxic elements. Statistics demonstrated significant differences in mass fractions between the tunnels for most analyzed elements. Results showed that rare earth elements, U and Th, mostly associated with geogenic sources, presented higher concentrations in MM tunnels, while elements frequently related to vehicular emissions (Sb, Zn, Ba, Cu and Pb) presented mean mass fraction values higher in JQ tunnel, pointing to a more important contamination in JQ tunnel. No significant differences in the mass fractions between campaigns were observed, evidencing that tunnels are not much affected by external weather conditions. Pb isotopic analysis presented 206Pb/207Pb ratios between 1.1715 and 1.1791 and 208Pb/206Pb ratios between 2.0889 and 2.0961, which pointed out to a vehicular signature, related to tailpipe emissions. On the other hand, Zn isotope data also suggested a vehicular signature, but mostly related to the wear of tires and brakes. Grain size distribution analysis showed that the smallest fractions of dust contained, on average, about 10% of particulate matter of aerodynamic diameter smaller than 10 μm, fractions highly inhalable, what may be a concern to human health. Enrichment factors (EFs) showed that Cr, Zn, Cu, Cd, Pb and Sb are the most enriched elements, in both tunnels, but higher EFs were found for JQ tunnel. Principal Component Analysis revealed a profile for a crustal source, marked by U, Th and rare earth elements, whereas vehicular sources were characterized mostly by Pb, Ti and V from gasoline/diesel combustion; Pb and Ti from road paints; Sb, Ba and Zn from brakes, and Zn from wear of steel and tires. These results indicate an important anthropic impact in the tunnels and that vehicular traffic is the main source of potentially toxic elements.

Simultaneous lead isotope ratio and gold-lead-bismuth concentration analysis of silver by laser ablation MC-ICP-MS

A new approach is presented for the simultaneous analysis of lead isotope ratios and gold, lead, and bismuth concentrations in metallic silver using nanosecond laser ablation multi-collector inductively-coupled plasma mass spectrometry (LA-MC-ICP-MS). Corrections for both isotope and concentration analyses are performed using an in-house matrix matched silver reference material RM3834. Accuracy and external reproducibility are demonstrated by repeat analyses of a further seven silver reference materials all characterised by solution (MC)-ICP-MS approaches. Typical internal precisions, expressed as two relative standard errors (S.E.) of the mean of the cycles comprising one analysis, are <0.5% for 206Pb/204Pb, 207Pb/204Pb and 208Pb/204Pb, and <0.03% for 207Pb/206Pb and 208Pb/206Pb. External reproducibilities, based on repeat analyses over a 10 month period and expressed as two relative standard deviations (S.D.) of the mean, are <0.4% for 206Pb/204Pb, 207Pb/204Pb and 208Pb/204Pb and <0.2% for 207Pb/206Pb and 208Pb/206Pb. Internal precisions and external reproducibilities of gold, lead and bismuth concentration analyses are typically <25%. Data are consistent with solution-based approaches. Methods are further demonstrated through analyses of a set of Islamic silver dirhams from the mint of al-Muhammadiyya, highlighting their applicability to geochemical studies of archaeological artefacts.

Forensic isoscapes based on intra-individual temporal variation of δ 18O and 206Pb/207Pb in human teeth

Isotopic signatures used in the georeferencing of human remains are largely fixed by spatially distinct geologic and environmental processes. However, location-dependent temporal changes in these isotope ratios should also be considered when determining an individual’s provenance and/or trajectory. Distributions of the relevant isotopes can be impacted by predictable external factors such as climate change, delocalisation of food and water sources and changes in sources and uses of metals. Using Multi-Collector Inductively-Coupled Plasma Mass Spectrometer (MC-ICP-MS) analyses of 206Pb/207Pb in tooth enamel and dentin from a population of 21 ± 1-year-old individuals born circa 1984 and isotope ratio mass spectrometry (IRMS) of δ 18O in their enamel, we examined the expected influence of some of these factors. The resulting adjustments to the geographic distribution of isotope ratios (isoscapes) found in tooth enamel and dentin may contain additional useful information for forensic identification, but the shifts in values can also impact the uncertainty and usefulness of identifications if they are not taken into account. KEY POINTS Isoscapes of 206Pb/207Pb and δ 18O used for geolocation are not static. Within a few years, the enamel and dentin of a person may exhibit measurable differences in 206Pb/207Pb even without changing locations. Changes in climatic patterns tied to rising temperatures are more significant than the direct effect of increasing temperature on δ 18O fixed in tooth bioapatite. Third molar (M3) enamel mineralisation includes material incorporated from before formal amelogenesis takes place.

Comparison of the Isotopic Composition of Silicon Crystals Highly Enriched in 28Si

The isotopic composition and molar mass M of silicon in a new crystal (code: Si28-33Pr11) measured by isotope ratio mass spectrometry using a high-resolution multicollector-inductively coupled plasma mass spectrometer (MC-ICP-MS) is presented using the virtual-element isotope dilution mass spectrometry (VE-IDMS) method. For this new crystal, M = 27.976 950 48 (16) g/mol was determined with urel(M) = 5.7 × 10−9. The “X-ray-crystal-density (XRCD) method”, one of the primary methods for realizing and disseminating the SI units kilogram and mole in the recently revised SI, is based on “counting” silicon atoms in silicon single crystal spheres. One of the key quantities is the isotopic composition—expressed by the molar mass M—of the three stable isotopes 28Si, 29Si, and 30Si in the material highly enriched in 28Si. M was determined with lowest possible uncertainty using latest improvements of the experimental techniques. All uncertainties were estimated according to the “Guide to the expression of uncertainty in measurement, GUM”. The results of the new crystal are discussed and compared with the four previously available crystals, establishing a worldwide limited pool of primary reference spheres of highest metrological quality.

Shocked titanite records Chicxulub hydrothermal alteration and impact age

Hydrothermal activity is a common phenomenon in the wake of impact events, yet identifying and dating impact hydrothermal systems can be challenging. This study provides the first detailed assessment of the effects of shock microstructures and impact-related alteration on the U-Pb systematics and trace elements of titanite (CaTiSiO5), focusing on shocked granite target rocks from the peak ring of the Chicxulub impact structure, Mexico. A > 1 mm long, shock-twinned titanite grain preserves a dense network of irregular microcracks, some of which exploit shock twin interfaces. Secondary microcrystalline anatase and pyrite are heterogeneously distributed along some microcracks. In situ laser ablation multi-collector inductively-coupled plasma mass spectrometry (LA-MC-ICPMS) analysis reveals a mixture of three end-member Pb components. The Pb components are: 1) common Pb, consistent with the Pb isotopic signature of adjacent alkali feldspar; 2) radiogenic Pb accumulated since magmatic crystallization; and 3) a secondary, younger Pb signature due to impact-related complete radiogenic Pb loss. The youngest derived ages define a regression from common Pb that intersects Concordia at 67 ± 4 Ma, in agreement with the established age of 66.04 ± 0.05 Ma for the Chicxulub impact event. Contour maps of LA-MC-ICPMS data reveal that the young ages are spatially restricted to microstructurally-complex domains that correlate with significant depletion in trace elements (REE-Y-Zr-Nb-Mo-Sn-Th) and reduction in magnitude of the Eu/Eu* anomaly. Mapping by time-of-flight secondary ion mass spectrometry (ToF-SIMS) show that patterns of localised element depletion in titanite are spatially related to microcracks, which are enriched in Al. The spatial correlation of ages and trace element abundance is consistent with localised removal of Pb and other trace elements from a pervasive network of fast fluid pathways in fractured domains via a fluid-mediated element transport process associated with the impact event. Here we interpret the 67 ± 4 Ma U-Pb age to represent hydrothermal Pb-loss in the Chicxulub peak ring in the wake of the impact event. These results highlight the potential of our analytical approach using titanite geochronology and geochemistry for dating post-impact hydrothermal activity in impact structures elsewhere.

Physiologic requirement for iron in pregnant women, assessed using the stable isotope tracer technique

BackgroundKnowledge of the physiologic requirement for iron, the core index for the formulation of a dietary reference intake (DRI), is of great importance for the health of a pregnant woman and her fetus, and can help a mother accurately plan her iron supplementation. However, direct measurements of the physiologic requirement for iron during pregnancy are still lacking.MethodEleven women of reproductive age from Hebei Province, China, who planned to become pregnant in the near future, were enrolled between January and March 2015 and included in the final analysis. Subjects participated in a 2-week metabolic trial in which they consumed 50 mg of the stable isotope 58Fe, and were then followed for ~ 2 years. The abundance of 58Fe and the total iron concentration in the circulation were measured using Multi-collector Inductively-Coupled Plasma Mass Spectrometry and Atomic Absorption Spectroscopy, respectively. The physiologic requirement for iron during pregnancy was then calculated by the formula derived from our previously published work.ResultsThe mean physiologic requirement for iron in the 11 subjects, across their entire pregnancies, was 3.05 mg.d− 1 in total and 44.0 μg.kg− 1.d− 1 after adjustment for body mass. The physiologic requirements for iron in the first, second, and third trimesters were 2.04 mg.d− 1, 3.26 mg.d− 1, and 4.13 mg.d− 1, respectively. When adjusted for body mass, the physiologic requirements for iron in different trimesters were 32.3 μg.kg− 1.d− 1, 46.9 μg.kg− 1.d− 1, and 55.7 μg.kg− 1.d− 1, respectively.ConclusionWe preliminarily explored the physiologic requirement for iron in pregnant women. The data demonstrated that pregnant women needed about twice iron than non-pregnant women. This research may be helpful for the design of future studies and the modification of iron DRIs.Trial registrationChiCTR, ChiCTR-OCH-14004302. Registered 14 February 2014, http://www.chictr.org.cn/showproj.aspx?proj=5267

Nanosecond Laser Ablation-Multicollector Inductively Coupled Plasma-Mass Spectrometry for in Situ Fe Isotopic Analysis of Micrometeorites: Application to Micrometer-Sized Glassy Cosmic Spherules.

This work evaluates the use of nanosecond laser ablation-multicollector inductively coupled plasma-mass spectrometry (ns-LA-MC-ICP-MS) for Fe isotopic analysis of glassy cosmic spherules. Several protocols for data acquisition from the transient signals were compared, with the integration method, i.e., isotope ratios obtained by dividing the corresponding signal intensities integrated over the selected signal segment, providing the best precision. The bias caused by instrumental mass discrimination was corrected for by a combination of internal correction using Ni as an internal standard (coming from a conebulized standard solution) and external correction using a matrix-matched standard. Laser spot size and repetition rate were adapted to match the signal intensities for sample and standard within ±10%. For in situ isotopic analysis, the precision of the δ56Fe values ranged between 0.02 and 0.11‰ (1 SD, based on 4 measurement sessions, each based on ablation along 5 lines for 30 s each) and 0.03-0.17‰ (SD, based on 3 measurement sessions) for glass reference materials and micrometeorites, respectively. Despite this excellent reproducibility, the variation of the isotope ratios along a single ablation line indicated isotopic inhomogeneity exceeding 1‰ in some micrometeorites. Isotopic analysis via pneumatic nebulization MC-ICP-MS, after sample digestion and chromatographic Fe isolation, was performed to validate the results obtained by in situ isotopic analysis, and good agreement was achieved between the δ-values obtained via both approaches and with those reported in literature for MPI-DING and USGS glass reference materials. Also for the glassy cosmic spherules, overall, there was a good match between the ns-LA-MC-ICP-MS and solution MC-ICP-MS results.

Determination of isotope fractionation of Cr(iii) during oxidation by LC/low-resolution MC-ICPMS

A robust and sensitive method for the precise isotopic analysis of 53Cr/50Cr during Cr(iii) oxidation by coupling ion pair reversed-phase chromatography and Multicollector Inductively Coupled Plasma Mass Spectrometry (MC-ICPMS) is presented.

Experimental observations of marine iodide oxidation using a novel sparge-interface MC-ICP-MS technique

Iodine speciation is used as a redox indicator and water mass tracer. However, the kinetics and mechanisms of oxidation of the reduced iodine species, iodide (I−), in seawater remain largely unresolved. Here, we provide constraints on I− oxidation rates from seawater incubation experiments using a sensitive radiotracer–incubation approach with high-precision mass spectrometry. Samples are inoculated with iodine-129 as I−, incubated under controlled conditions, then oxidized and reduced iodine species are isolated using liquid chromatographic separation. Samples are subsequently aspirated using a novel sparging interface, and the 129I/127I ratio of both iodine species is determined via multi-collector inductively-coupled plasma mass spectrometry. This highly-sensitive analytical approach is optimized for estimating the predicted slow rates of iodine redox transformations in small volume seawater samples at marine-relevant total iodine concentrations. Application of this method to coastal samples from Martha's Vineyard Sound, USA, evidences the heretofore-elusive oxidation of I− under marine-analogue conditions. Our results demonstrate an increase in the 129I/127I of aqueous oxidized iodine species in unamended seawater, most likely due to formation of hypoiodous acid and then dissolved organic iodine, at rates of 118–189 nM/ yr. These rates are comparable to those inferred from previous open ocean mass balance approaches but have the benefit of directly linking iodine speciation changes to in situ I− oxidation. Though our treatment experiments do not definitively isolate the oxidation mechanism, they provide preliminary insight into important roles for both abiotic and biotic factors as well as iodine transformations between dissolved, particulate, and gaseous forms. Ultimately, the derived rates and novel experimental technique have potential to improve marine iodine cycling models and provide constraints on the importance of in situ processes in setting patterns of iodine speciation.

Physiological requirements for iron in women of reproductive age assessed by the stable isotope tracer technique

BackgroundIron nutrition is important for the health of women of reproductive age, and defining the physiologic requirement for iron can help them accurately plan the iron intake. However, research on the physiologic requirement for iron in women is insufficient worldwide. This study aimed to further improve the methodology and get more precise data for the physiological requirements for iron in women of reproductive age on the basis of our previous study.MethodSixty-one women of reproductive age who had not been pregnant before and during the whole study were included from Hebei province, China in 2015. Each subject participated in a 2-week metabolic trial with consuming 50 mg of the stable isotope 58Fe, and were then followed for ~ 800 days. The abundance of 58Fe and the total iron concentration in the circulation were measured using multi-collector inductively-coupled plasma mass spectrometry and atomic absorption spectroscopy. The physiologic requirement for iron in women of reproductive age was then calculated.ResultsThe average iron circulation rate was 80.4%, and the steady period started from about 1 year. The average physiological requirement for iron of 21 subjects obtained by formula calculation was 1.55 mg/d and 23.63 μg.kg− 1.d− 1 after adjustment for body mass, and that of 33 subjects obtained by linear regression was 1.29 mg/d, 20.98 μg.kg− 1.d− 1 after adjustment for body mass. The results by two methods showed no significant difference. The EAR and RNI calculated from this results was 11–13 mg/d and 15–18 mg/d, respectively, both of which were slightly lower than the recommended value in Chinese Dietary Reference Intake (2013).ConclusionThe physiological requirements for iron in women of reproductive age were in accordance with other studies, while the EAR and RNI calculated from which were slightly lower than Chinese present recommended value.Trial registrationChiCTR, ChiCTR-OCH-14004302. Registered 14 February 2014, http://www.chictr.org.cn/enindex.aspx

Production and characterization of 60Fe standards for accelerator mass spectrometry.

Accelerator Mass Spectrometry (AMS) is one of the most sensitive analysis techniques to measure long-lived radionuclides, reaching detection limits for isotopic ratios down to 10−15–10−16 in special cases. Its application portfolio covers nearly every field of environmental research, considering processes in the atmosphere, biosphere, hydrosphere, cryosphere, lithosphere and the cosmosphere. Normally, AMS measures the content of isotopes in comparison to a validated standard. However, in some cases like for example 60Fe, well characterized standard materials are difficult to produce due to the extreme rareness of the isotope. We report here on the manufacturing of a set of 60Fe standards, obtained by processing irradiated copper from a beam dump of the high-power proton accelerator (HIPA) at the Paul Scherrer Institute (PSI). The isotopic ratios of the standards have been adjusted via a dilution series of a master solution, isotopic content of which has been characterized by Multi Collector–Inductively Coupled Plasma–Mass Spectrometry (MC-ICP-MS). In total, we produced three samples with isotopic ratios of 1.037(6)·10−8, 1.125(7)·10−10 and 1.234 (7)·10-12, respectively. The latter had already been applied in three pioneering AMS studies investigating the remaining signal of injected matter of nearby super novae explosions in sediment archives.

Extraction and Analysis of Available Boron Isotopes in Soil Using Multicollector Inductively Coupled Plasma Mass Spectrometry.

As a result of the important roles of boron (B) in the growth of plants, the uptake of B by plants is dependent upon the existing form and content of available B in soil, which can bring about the local cycle of B isotope equilibrium. A method using water-heating extraction combined with three-step ion-exchange chromatography was developed for the extraction and isotopic analysis of available B in soil. The extraction efficiency and fractionation of B isotopic composition in the procedure were investigated. The results showed that, in the upper layers of soils, the change of δ11B values was opposite that of the mass concentration and a similar variation between δ11B and content occurred in the lower layers. The isotope of available B in soil can create a featured isotopic signature to further understand the geochemical details related to the soil properties and molecular mechanism of B uptake in plants.