Multi-collector Inductively Coupled Plasma Mass Spectrometry Research Articles

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.

Source attributions of Cadmium contamination in rice grains by Cadmium isotope composition analysis: A field study

Cd contamination in rice grains has become a topic of great concern because of the high health risks associated with the long-term consumption of Cd-contaminated rice. Identification of Cd sources in rice grains by scientific methods is important for controlling heavy metal pollution and protecting human health. Here, the Cd concentrations and Cd isotopic compositions of rice plants (root, stem, leaf, and grain) and topsoil, and possible pollution sources (agricultural fertilizers, industrial dust, and automobile exhaust) were analyzed using an instrument of inductively coupled plasma mass spectrometry (ICP-MS) and multi-collector inductively coupled plasma mass spectrometry (MC-ICP-MS). The results showed variations in the Cd isotopes of different components of rice plants and the fractionation coefficient of rice grains relative to topsoil (Δ114/110Cdrice grains−topsoil = 0.25‰). The contributions of pollution sources to rice grains were realized by combining the Cd isotopic composition with an isotopic mixing model (Isosource). The analysis showed that all three possible pollution sources contributed to the Cd in the rice grains in the field, the average Cd contribution of industrial dust, agricultural fertilizers and automobile exhaust was 87%, 9%, and 4%, respectively. Our study provides a feasible method for the identification of pollution sources of Cd in rice grains at the field scale and demonstrates that Cd isotopic composition is one of the powerful tools to trace the pollution sources of Cd in crops.

Recent advances in method development and application of multi-collector inductively coupled plasma mass spectrometry

稳定同位素分析是分析化学一项颇具前景的分支,通过精确测定物质的稳定同位素比值,可以追溯物质来源并探究其转化过程。高精度稳定同位素分析技术的进步依赖于新一代质谱仪的不断发展。其中,多接收器电感耦合等离子体质谱(MC-ICP-MS)是近年发展迅速的一种同位素组成测定工具。稳定同位素分析对样品基质十分敏感,复杂基质能严重干扰同位素测定的精密度和准确度。这对MC-ICP-MS的样品净化提出了极高要求,目前也是同位素分析领域的热点问题。该文聚焦于近年来MC-ICP-MS在样品净化及仪器联用方法方面的相关研究进展,并展望了MC-ICP-MS稳定同位素分析的应用前景。

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.

A Rapid and Simple Method for Lithium Purification and Isotopic Analysis of Geological Reference Materials by MC-ICP-MS.

A simple method has been developed to purify lithium (Li) from matrix elements in geological reference materials, using a single-column packed with AGMP-50 cation exchange resin, followed by high-precision Li isotope measurements by multi-collector inductively coupled plasma mass spectrometry (MC-ICP-MS). A series of tests, such as different types of resin, loading amount of Li, loading volumes, and various eluents, were conducted to ascertain the optimal conditions for Li purification and the effects of intensity, acidity, and presence of potential matrix elements on Li isotope measurements were also evaluated. In our experiment, Al and high-field-strength elements (HFSEs), such as Ti, Zr, and Hf, were eluted by 0.2 M HCl + 0.3 M HF, and 0.73 M HCl was used to separate Li from other matrix elements, such as Na. This method is suitable for processing large amount of Li (60–270 ng) and enabling a Li recovery of close to 100%, with effective removal of matrix elements such as Na and Ca. Besides, our method achieves low matrix interferences (e.g., Na/Li << 1 and Ca/Li << 1 for rock and seawater via a single-column procedure; Ca/Li < 2 for carbonate via a two-column procedure) and also uses small volume of eluents and is rapid (~5 h), enabling a total separation to be completed in ~0.5 d. Using this method, we report Li isotopic compositions of various geological reference materials, including igneous rocks, seawater, and carbonate. The Li isotopic compositions are consistent with the data published previously for the analyzed reference materials. As such, the reported method is ideally suited for Li separation from multiple types of geological samples prior to isotopic analysis.

Multicollector Inductively Coupled Plasma-Mass Spectrometry with 1013 Ω Faraday Cup Amplifiers for Ultrasensitive Mg Isotopic Analysis of Cerebrospinal Fluid Microsamples.

Magnesium isotopic analysis of cerebrospinal fluid (CSF) is a potentially interesting approach for studies on neurodegeneration. However, this type of analysis is challenging because of the invasiveness of the sampling and small sample volume. In this work, a novel analytical method was developed for ultrasensitive Mg isotopic analysis of CSF microsamples via multicollector inductively coupled plasma-mass spectrometry (MC-ICP-MS) using high-gain 1013 Ω Faraday cup amplifiers. The intermediate and internal errors on the δ26Mg value were improved up to fourfold using 1013 Ω resistors for the monitoring of both the 24Mg and 26Mg isotopes and up to twofold using a 1011 Ω resistor for the most abundant 24Mg isotope and a 1013 Ω resistor for the 26Mg isotope. Magnesium isotope ratios measured at a concentration level of 7-10 μg L-1 were in good agreement with those obtained using the conventional method at a concentration level of 150 μg L-1. The expanded uncertainty for the quality control CSF material obtained at the ultratrace level was ±0.16‰. Ultrasensitive Mg isotopic analysis was carried out for CSF from hydrocephalus patients using only 5 μL of sample. δMg values thus obtained were not significantly different from those obtained using the conventional method using a sample volume of 400 μL instead (p ≤ 0.05). The Mg isotopic composition of the CSF from hydrocephalus patients ranged between -0.65 and 0.30‰, with a mean δ26Mg value of -0.14 ± 0.27‰.

Novel Approach for the Accurate Determination of Se Isotope Ratio by Multicollector ICP-MS.

In this work, a method for the accurate and precise determination of 82Se/78Se isotope ratio in natural samples of environmental and biological origin, using multicollector inductively coupled plasma mass spectrometry in a wet plasma mode without using neither hydride generation nor separation of Se, was developed. It was based on the optimized regression model with standard–sample bracketing (ORM–SSB) to efficiently correct instrumental isotopic fractionation/mass bias and matrix effects. In addition, three mass bias correction models of SSB alone, SSB combined with internal standard (IS–SSB), and ORM–SSB were compared for the Se isotope ratio measurements. NIST SRM 987 Sr was used as an internal standard, and the reproducibility of the results obtained with the proposed method was verified by measuring NIST SRM 3149 standard over different days (nine independent measurement sessions). Delta values of the 82Se/78Se isotope ratio were measured in selenium-enriched yeast-certified reference material SELM-1, natural selenomethionine samples, and model solutions of artificial seawater. Solutions obtained after thiol resin treatment were measured to demonstrate the applicability of the proposed method in eliminating matrix effects due to residual of thiol resin in the sample solutions. Among three mass bias correction models, ORM–SSB correction model proved to be the best to eliminate the matrix effects and instrumental drift. IS–SSB model offered also a good precision but was slightly less accurate. Both models showed good robustness against effects of different sample matrices. Finally, the SSB alone could not be recommended for Se isotope analysis as it produces inaccurate and imprecise results.

Isotopic analysis of potassium by total evaporation and incipient emission thermal ionisation mass spectrometry

The isotopic compositions of the natural potassium chloride sample NIST SRM 999b, and the isotopically enriched material GSC K-40 that is used in an ongoing study of the half-life of 40K by decay counting, were determined using total evaporation thermal ionisation mass spectrometry (TE-TIMS) and incipient emission thermal ionisation mass spectrometry (IE-TIMS). Both methods were comprehensively calibrated for precision and accuracy by multiple analyses against gravimetrically prepared synthetic mixtures of enriched 39K and 41K. These mixtures of enriched isotopic materials characterised for purity and stoichiometry, have 41K/39K with uncertainty of ca. 0.02%, and can be used for calibration of either TIMS or MC-ICPMS (multi-collector inductively coupled plasma mass spectrometry) measurements of K isotopic composition independently of the currently accepted IUPAC value. The TE-TIMS and IE-TIMS analyses of potassium using some, but not all, combinations of loading medium, filament configuration, and data processing methods can yield accurate “absolute” isotopic compositions without standardisation. The 41K/39K ratio in NIST SRM 999b determined in this study with TE-TIMS and IE-TIMS has the value of 41K/39K = 0.072247 ± 0.000086, 95% confidence level), which is consistent within 95% confidence limits with the isotopic composition of this material derived from the calibration of Garner et al. (1975), which serves as the basis of the current IUPAC recommendation and is used as a reference in the rapidly growing field of potassium stable isotope geochemistry. The isotopic abundance of 40K in the enriched GSC K-40 is determined with the total uncertainty of 0.075% (95% confidence level), and is suitable for precise calculation of the half-life of 40K in our ongoing decay counting study.

High‐precision isotopic analysis of essential mineral elements: capabilities as a diagnostic/prognostic tool

AbstractAll elements with two or more isotopes show natural variation in their isotopic composition as a result of the isotope fractionation that accompanies (bio)chemical reactions and (bio)physical processes. Multicollector inductively coupled plasma‐mass spectrometry (MC‐ICP‐MS) offers the precision required to reveal and quantify the differences in isotope ratios thus caused, although they are often of sub‐permil magnitude only. Using MC‐ICP‐MS, it has been shown that (a) in different body compartments, essential mineral elements may display different isotopic compositions, and (b) disease conditions may alter the isotopic composition of an essential mineral element in a biofluid and/or tissue. As a result, high‐precision isotopic analysis of these elements is a powerful way to unravel the actual role these essential mineral elements play in specific biochemical processes. Moreover, isotope ratio shifts also show promise as a diagnostic or prognostic tool. Despite the intensive sample pretreatment preceding MC‐ICP‐MS isotopic analysis and the high purchase and running costs of the instrumentation, this approach may be valuable, especially for diseases that can otherwise only be established at a later stage and/or via a more invasive approach. This review paper describes the basics of “biomedical isotopic analysis” and uses selected cases from the literature to sketch the state‐of‐art and illustrate in which context isotope ratio markers could be exploited in a clinical context.

Source apportionment of cadmium pollution in agricultural soil based on cadmium isotope ratio analysis

Anthropogenic activities, especially industrial production and agricultural practices have led to Cd accumulation in the agricultural soil locating near to the industrial areas of China threatening soil environmental quality and food security. In this study, the sources of Cd pollution were accurately analyzed, which may lead to efficiently control the Cd content in the soil. The samples of agricultural topsoil, four possible pollution sources such as smelter dust, automobile exhaust, cement factory dust and agricultural fertilizer were collected, and the Cd concentrations and Cd isotope ratios were analyzed using the instrument of Inductively Coupled Plasma Mass Spectrometry (ICP-MS) and Multi-collector Inductively Coupled Plasma Mass Spectrometry (MC-ICP-MS). The results indicated that the Cd concentration of agricultural topsoil (11.72 ± 0.30 mg kg−1) was much higher than the recommended value (0.6 mg kg−1). The highest δ114/110CdNIST3108 value (−0.15 ± 0.14‰) was observed for smelter dust and the lowest δ114/110CdNIST3108 value (−0.64‰) was found in cement factory dust. Similarly, the highest Cd concentration was found in smelter dust and it was clearly distinguishable from the other samples based on δ114/110CdNIST108 values. Cd isotope analysis suggested that smelter along with agricultural fertilizer were the major sources of Cd accumulation in agricultural topsoil. In addition, based on the IsoSource software, the relative Cd contribution rates due to automobile exhaust, cement factory, agricultural fertilizer, and smelter dust were 14%, 7%, 20%, and 59%, respectively, demonstrating that smelter dust is the main pollution source of Cd in the study area. Cd isotope analysis is a promising tool to accurately identify the heavy metal pollution sources.

A comparison of sulfur isotope measurements of geologic materials by inductively coupled plasma and gas source mass spectrometry

Sulfur isotope measurements by multi collector-inductively coupled plasma-mass spectrometry (MC-ICP-MS) require up to one hundred times less sulfur than traditional measurements via elemental analyzer isotope ratio mass spectrometry (EA-IRMS). Here, we report an improved MC-ICP-MS protocol for measuring δ34S values in different natural samples, specifically, calcium-sulfate minerals, carbonate associated sulfate, and dissolved sulfate in water. Sample preparation and subsequent anion exchange chromatography quantitatively recovers sulfur as sulfate. However, for samples with high and complex anion budgets, such as meteoric water, a stronger retention of sulfate on the anion exchange resin is observed relative to samples that contain sulfur as pure sulfate such as calcium-sulfate minerals and carbonate associated sulfate. An extended elution scheme with HNO3 is therefore required to achieve full recovery of sulfur, and thus accurate and reproducible δ34S values for the different materials investigated. Sulfur isotope measurements were performed on a Neptune Plus MC-ICP-MS coupled to an Apex-Ω desolvator, resulting in a “dry” plasma, negligible level of isobaric interferences, a sensitivity of >40 V ppm−1 sulfur, and a precision of 0.2‰ (2 S.D.) for δ34S for as little as 70 ng sulfur of a pure sulfate solution. The accuracy of the procedure was tested against duplicate δ34S EA-IRMS measurements for eleven different geologic samples. The EA-IRMS and MC-ICPMS values generally agree well within analytical uncertainty. However, procedural blank levels are on the order of a few tens of nanogram sulfur, and are thus the main limiting factor for accurate low-level sulfur isotope measurements with MC-ICP-MS.

Copper Isotope Ratio Measurements of Cu-Dominated Minerals Without Column Chromatography Using MC-ICP-MS.

This study performed a series of comparable experiments (with or without column chromatography) to evaluate whether non-deviated Cu isotope ratios can be obtained directly by Nu Plasma II multi-collector inductively coupled plasma-mass spectrometry (MC-ICP-MS) using standard-sample bracketing with Ga as internal mass bias correction model (C-SSBIN) without column chromatography. Twelve Cu-dominated minerals (copper plate, native copper, chalcopyrite, bornite, chalcocite, digenite, covellite, tetrahedrite, azurite, malachite, atacamite, and cyanotrichite) displayed little drift in δ65Cu values compared with those of minerals with column chromatography, with Δδ65Cuwithout−with ranging from −0.04 to +0.02‰. This means that Cu isotope ratios in Cu-dominated minerals can be achieved without column chromatography, due to the simple matrix and the stability of the machine by using C-SSBIN mode. The acidity and internal standard concentration mismatch effects, as well as the matrix effect, were strictly assessed by Nu Plasma II MC-ICP-MS in a wet-plasma mode in the State Key Laboratory of Continental Dynamics (SKLCD). Finally, a long-term reproducibility of better than ±0.03‰ [n = 38, 2 standard deviations (2s)] were achieved by repeatedly measuring chalcopyrite without column chromatography over 4 months.

Hyphenation of capillary electrophoresis with MC-ICP-MS – A novel tool for uranium age dating

Capillary electrophoresis (CE) was hyphenated to multi-collector inductively coupled plasma mass spectrometry (MC-ICP-MS) to determine the model age of a highly enriched uranium (HEU) sample using the 234U/230Th radiochronometer. The use of hydroxymethylbutyric acid (HMBA) as the CE electrolyte was investigated, and a complexation stacking method was developed to increase the thorium signal obtained. The age of the material was determined by measuring the 230Th content of the HEU sample using isotope dilution in conjunction with the CE-MC-ICP-MS protocol. The CE-MC-ICP-MS protocol and a standard offline protocol using gravitational chromatography both gave results in accordance within uncertainties with the production date of the HEU sample (March 1965). Liquid waste production was only of a few microliters with the use of CE. The hyphenation of CE with MC-ICP-MS render the measurement of the age of the HEU material in less than one day possible. Obtaining results in a timely fashion is of particular importance for nuclear forensics studies.

Method development for on-line species-specific sulfur isotopic analysis by means of capillary electrophoresis/multicollector ICP-mass spectrometry

In this work, a method for species-specific isotopic analysis of sulfur via capillary electrophoresis hyphenated on-line with multicollector ICP-MS (CE/MC-ICP-MS) was developed. Correction for the mass bias caused by instrumental mass discrimination was realized via external correction with multiple-injection sample-standard bracketing. By comparing the isotope ratio measurement results obtained using the newly developed on-line CE/MC-ICP-MS method with those obtained via traditional MC-ICP-MS measurement after analyte/matrix separation by anion exchange chromatography for isotopic reference materials and an in-house bracketing standard, the most suitable data evaluation method could be identified. The repeatability for the sulfate-δ34S value (calculated from 18 measurements of a standard conducted over seven measurement sessions) was 0.57‰ (2SD) and thereby only twice that obtained with off-line measurements (0.30‰, n = 68). As a proof of concept for analysis of samples with a real matrix, the determination of the sulfur isotopic composition of naturally present sulfate was performed for different river systems. The CE/MC-ICP-MS results thus obtained agreed with the corresponding off-line MC-ICP-MS results within the 2SD ranges, and the repeatability of consecutive δ34S measurements (n = 3) was between 0.3‰ and 1.3‰ (2SD). Finally, the isotopic analysis of two different S-species in a river water sample spiked with 2-pyridinesulfonic acid (PSA) was also accomplished.Graphical abstractThe CE/MC-ICP-MS method developed allows for species-specific S isotopic analysis in samples containing multiple species. Mass bias is corrected for by multiple-injection sample-standard bracketing, while the repeatability (2SD) of the resulting 34δ-values is <1‰.

The impact of MC-ICP-MS plasma conditions on the accuracy and precision of stable isotope measurements evaluated for barium isotopes

Stable barium isotope measurements with multi-collector inductively coupled plasma mass spectrometry (MC-ICP-MS) remain an analytical challenge and can be considerably affected by the presence of matrix elements, even when applying double spiking. Therefore significant efforts were invested in previous studies to develop efficient barium purification methods. However, due to the high variability in matrix/barium ratios for diverse sample matrices, potential matrix effects can still not be excluded. While a lot of effort has been invested into improving the chemical separation protocols, the impact of plasma conditions on the accuracy and precision of stable isotope measurements has rarely been considered. Here we present a systematic investigation of the relationship between plasma conditions, instrumental mass fractionation (IMF) and impurity (i.e. matrix) concentrations. The Normalised Ar Index (NAI) and Matrix-Ar Index (MA) are used to quantify MC-ICP-MS plasma conditions and plasma mass loading, respectively. Our results show that the effect of matrix elements on IMF is largely linked to plasma conditions (i.e. NAI) and behaves as a linear function of mass loading (i.e. MA). Accordingly, the matrix effects can be significantly attenuated by increasing the NAI thereby minimising the risk of plasma “over-loading”. The improved understanding of the behaviour of the matrix-induced IMF allows us to define a matrix tolerance plasma state for barium isotope analysis. The accuracy of this recommended method is further assessed by analyses of two well-studied reference materials, the GEOTRACES seawater reference sample SAFe D2 and the carbonate reference material JCp-1. We expect that the analytical protocol described in this study is applicable not only to barium isotope analysis, but also to a wide range of other stable isotope measurements with MC-ICP-MS.

Lead and strontium isotopes as palaeodietary indicators in the Western Cape of South Africa

We analysed the isotopic compositions of bioavailable strontium (Sr) and lead (Pb) in 47 samples of animals and plants derived from the various geological substrates of southwestern South Africa, to explore the utility of these isotope systems as dietary tracers. Measurements were made using high-resolution multi-collector inductively-coupled-plasma mass spectrometry (MC-ICP-MS). 87Sr/86Sr could efficiently discriminate between geologically recent sediments of marine origin in near-coastal environments and older geologies further inland. However, 87Sr/86Sr was not able to distinguish between the Cape Granite Suite and the Cape System (Table Mountain sandstones), whereas Pb isotopes could, demonstrating the utility of this hitherto underused isotope system. Bioavailable 87Sr/86Sr in near-coastal terrestrial environments is influenced by marine input, whereas Pb isotopic ratios are not, because of low concentrations of Pb in seawater. There is considerable potential to use Pb isotopes as a dietary and palaeodietary tracer in near-coastal systems in fields as diverse as archaeology, palaeontology, wildlife ecology and forensics.&#x0D; Significance:&#x0D; &#x0D; This study is the first investigation of the potential of Pb isotopes as a dietary tracer in southwestern South Africa.&#x0D; Pb isotopes are a valuable dietary tracer; used in combination with 87Sr/86Sr, they can extend our knowledge of landscape usage in coastal-marine environments.&#x0D; Pb isotopes have also shown to be useful in samples from the 1980s, collected during the time when leaded petrol was in use in South Africa; however, these samples were from remote areas with low motor vehicle emissions.&#x0D;

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.

Automation of boron chromatographic purification for δ11 B analysis of coral aragonite.

To detect the small changes in past pH, the boron isotope ratio of coral carbonates, expressed as the δ11 B value, needs to be both precise and accurate (2sd <<1‰). Boron measurements by Multi-Collector Inductively Coupled Plasma Mass Spectrometry (MC-ICPMS) require the boron to be carefully purified before analysis, which is time consuming, and requires specialist training. Here, we use the prepFAST-MC method that enables the automatic extraction of B (up to 25 ng load) from a CaCO3 matrix. Samples were purified using the prepFAST-MC automated system with a ~25-μL column of Amberlite IRA743 resin. Boron isotope measurements were performed by MC-ICPMS. The effects of matrix load, speed of sample loading onto the column, and blank contamination were tested to evaluate the effects on the purification process. The optimised protocol was tested on various standards and samples of aragonite corals. The blank contribution for the approach is ~60 pg and is negligible given our sample size (<0.2% sample size). Efficiency of matrix removal is demonstrated with the addition of up to 1.6 mg of dissolved low-B calcium carbonate to NIST SRM 951 with no impact on the accuracy of δ11 B values. The Japanese Geological Survey Porites reference material JCp-1, boric acid standard NIST SRM 951, and seawater, all processed on the prepFAST-MC system, give δ11 B values within error of literature values (δ11 BJCp-1 = 24.31 ± 0.20‰ (2sd, n = 20); δ11 BNIST 951 = -0.02 ± 0.15‰ (2sd, n = 13) and δ11 BSeawater = 39.50 ± 0.06‰ (2sd, n = 2)). Results obtained from the coral Siderastrea siderea purified with the prepFAST-MC system show an average offset from the manual ion-exchange protocols of Δδ11 B = 0.01 ± 0.28‰ (2sd, n = 12). Our study demonstrates the capacity of the prepFAST-MC method to generate accurate and reproducible δ11 B values for a range of materials, without fractionation, with efficient matrix removal and with negligible blank contribution.

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

Fighting and burial: the production of bronze weapons in the Shu state based on a case study of Xinghelu cemetery, Chengdu, China

This article discusses the bronze weapons discovered in the Xinghelu cemetery of Chengdu, China in order to study the production of bronze weapons in the Shu state. Metallographic microscopy, inductively coupled plasma atomic emission spectroscopy (ICP-AES) and multi-collector inductively coupled plasma mass spectrometry (MC-ICP-MS) were used to analyze 56 bronze samples. The results show that normal size weapons contain more lead or tin than the equivalent small weapons. Some normal size weapons were made from the same lead sources as the small ones; others, such as the dagger-axe and scabbards, might be imported products. To match the imported scabbards, swords of comparable size were cast or chosen. Most of the small weapons may have been produced by type, while the variable alloying composition and size for each weapon suggests multiple casting processes.