Isotope Amount Ratios Research Articles

An improved calibrated mass spectrometry for absolute copper isotope-ratio measurement using two strategies for mass bias correction factor

Modern advances in multi-collector inductively coupled plasma mass spectrometry (MC-ICPMS) have greatly promoted the investigation of copper isotopes in various research fields. To meet the demand, an improved calibrated mass spectrometry for the absolute determination of copper isotopic composition was developed in this study. The method has made progress in the investigation of instrumental mass bias correction factor for copper isotopic analysis using MC-ICPMS through employing two independent strategies. One is the conventional mathematical iterative method based on the MC-ICPMS measurement data; the other one is direct calculation using the absolute copper isotopic compositions in isotopically enriched 63Cu and 65Cu materials by developing a TE-TIMS method. The results of Kiter = 0.95563(16)k = 1 and KTE = 0.95551(17)k = 1 were consistent in their standard uncertainties, demonstrated the first cross-validation of these two strategies. Thereafter, the proposed calibrated mass spectrometry were applied to re-measure the copper isotope amount ratios in three isotopic reference materials, resulted in RNIST SRM 97665/63 = 0.44547(16)k = 2, RERM®−AE63365/63 = 0.44549(16)k = 2, and RERM®−AE64765/63 = 0.44557(16)k = 2, respectively. These expended uncertainties were only one third or one fifth of the stated uncertainties in their certificates. Furthermore, the absolute copper isotopic compositions in four natural-abundance samples and a new copper isotopic reference material GBW04624 were determined, given an average atomic weight of copper as Ar(Cu) = 63.5456(4)k = 2. The δ65Cu values of GBW04624 relative to NIST SRM 976, ERM®-AE633 and ERM®-AE647 were also applied by implementing the C-SSBIN calibration model. This provides an additional independently certified and SI-traceable copper isotopic reference material, in support of various scientific researches.

Certification of Uranium Isotope Amount Ratios in a Suite of Uranium Ore Concentrate Certified Reference Materials

In this study, data from thirteen laboratories from around the world are presented for a successful certification of uranium isotope ratios in uranium ore concentrate (UOC) certified reference materials from the National Research Council Canada. Different mass spectrometric measurement principles (including SF‐ICP‐MS, quadruple ICP‐MS, TIMS, MC‐ICP‐MS, SIMS and AMS) and measurement procedures were employed. In general, data from all sources exhibit good consistency with TIMS and MC‐ICP‐MS showing superior performance. The three candidate UOC CRMs (UCLO‐1, UCHI‐1 and UPER‐1) have natural uranium isotope ratios with certified values of 0.5304(7) × 10−4, 0.5475(2) × 10−4 and 0.5361(4) × 10−4 for n(234U)/n(238U) and 0.007 2563(13), 0.007 2563(10) and 0.007 2542(11) for n(235U)/n(238U), respectively, with expanded uncertainty (k = 2) applicable to the last digit of the value given in the parentheses. Information values for n(236U)/n(238U) in these three CRMs, measured by AMS, are also provided: 10 × 10−12, 200 × 10−12 and 22 × 10−12. The uncertainties of the proposed certified values of uranium isotope ratios in UOC CRMs are superior to available reference materials, and the values of n(234U)/n(238U) and n(236U)/n(238U) show significant variation among the three CRMs.

New reference materials for trace-levels of actinide elements in plutonium

Abstract Two plutonium oxides were prepared as unique reference materials for measurement of actinide elements present as trace constituents. Each reference material unit is approximately 200 mg of PuO2 powder in a quartz glass bottle. Characterized attributes of the oxides included mass fractions of plutonium, americium, neptunium, and uranium. Isotope-amount ratios were also determined for plutonium and uranium, but neptunium and americium were observed to be monoisotopic 237Np and 241Am. Measurements for characterization and verification of the attributes show that plutonium and trace actinides are homogeneous with the exception of limited heterogeneity for uranium, primarily observed for the 238U isotope. Model purification ages calculated from measured americium and uranium attribute values are consistent with material histories and indicate that these impurities are predominantly due to the decay of plutonium isotopes.

Measurement and Traceability Issues in Isotope Amount Ratio Determination of Stable Isotopes

Measurement and Traceability Issues in Isotope Amount Ratio Determination of Stable Isotopes

A double-spike MC TIMS measurement procedure for low-amount Ca isotopic analysis of limited biological tissue samples.

The application of Ca isotopic analysis in biomedical studies has great potential to identify changes in Ca metabolism and bone metabolism. Reliable measurement of Ca isotope-amount ratios is challenging considering limited Ca amounts and significant procedural blank levels. In this study, Ca purification was performed using the DGA Resin, optimized for low procedural blanks and separation of Ca from matrix elements and isobaric interferences (Na, Mg, K, Ti, Fe, Ba), while maintaining quasi-quantitative recoveries which are sufficient since a 42Ca-48Ca double-spike (DS) was applied. Ca isotopic analysis was performed using multicollector thermal ionization mass spectrometry (MC TIMS). The obtained procedural Ca blank of ≤10ng enables processing of limited Ca amounts down to 670ng. Data reduction of the measured Ca isotope-amount ratios was performed using an in-house developed software solving the DS algorithm. Data quality was improved by extension of equilibration time of the sample-DS mixture and implementation of a normalization strategy for raw isotopic data. The reported δ(44Ca/40Ca)NIST SRM 915a of NIST SRM 915a processed as a sample was found to be 0.01‰ ± 0.08‰ (2 SD, n = 15). Ca isotope-amount ratios of the reference material NIST SRM 1400 (bone ash), NIST SRM 1486 (bone meal), GBW07601 (human hair), and IAPSO (seawater) were in good agreement within uncertainty with literature data. Novel data on additional reference materials for biological tissues (hair) is presented, which might indicate a potential fractionation of Ca incorporated into hair tissue when compared to the blood pool.

Certification of a Natural Silicon Reference Material with SI‐Traceable Isotopic Composition

Silicon (Si) is the second most abundant element in the continental crust. Studies have illustrated that silicon isotopes have a potential to be tracers in the biogeochemical silica cycle. This paper details a developed method for the production and certification of a new Si reference material with natural‐like isotopic composition using a fully calibrated multi‐collector inductively coupled plasma‐mass spectrometer (MC‐ICP‐MS). To correct for the mass bias effect, three blend solutions were gravimetrically prepared with isotopically enriched 28Si, 29Si and 30Si materials. Homogeneity and stability tests were performed, and no significant influences were found. Uncertainties of property values were evaluated, and the traceability to the International System of Units (SI) was established. The developed certified reference material (GBW04503) is a silicon powder (≈ 300 mesh) with high purity (≈ 0.999 99 kg kg−1), which can be used in silicon isotopic measurement to support validation of analytical procedures and/or quality control of gas source mass spectrometry (GS‐MS) or MC‐ICP‐MS. The certified isotope amount ratios of n(29Si)/n(28Si) and n(30Si)/n(28Si) are 0.050291(12) mol mol−1 and 0.033397(16) mol mol−1, respectively, (k = 2), and the certified isotope amount fractions of silicon are 92.2776(20)% (28Si), 4.6407(10) % (29Si) and 3.0818(14)% (30Si) (k = 2). Meanwhile, the delta value of δ30/28SiNBS 28 = 1.679(17)‰ was obtained (k = 2).

High-Resolution Atomic Absorption Spectrometry Combined With Machine Learning Data Processing for Isotope Amount Ratio Analysis of Lithium.

An alternative method for lithium isotope amount ratio analysis based on a combination of high-resolution atomic absorption spectrometry and spectral data analysis by machine learning (ML) is proposed herein. It is based on the well-known isotope shift of approximately 15 pm for the electronic transition 22P←22S at around the wavelength of 670.8 nm, which can be measured by the state-of-the-art high-resolution continuum source graphite furnace atomic absorption spectrometry. For isotope amount ratio analysis, a scalable tree boosting ML algorithm (XGBoost) was employed and calibrated using a set of samples with 6Li isotope amount fractions, ranging from 0.06 to 0.99 mol mol-1, previously determined by a multicollector inductively coupled plasma mass spectrometer (MC-ICP-MS). The calibration ML model was validated with two certified reference materials (LSVEC and IRMM-016). The procedure was applied toward the isotope amount ratio determination of a set of stock chemicals (Li2CO3, LiNO3, LiCl, and LiOH) and a BAM candidate reference material NMC111 (LiNi1/3Mn1/3Co1/3O2), a Li-battery cathode material. The results of these determinations were compared with those obtained by MC-ICP-MS and found to be metrologically comparable and compatible. The residual bias was -1.8‰, and the precision obtained ranged from 1.9 to 6.2‰. This precision was sufficient to resolve naturally occurring variations, as demonstrated for samples ranging from approximately -3 to +15‰. To assess its suitability to technical applications, the NMC111 cathode candidate reference material was analyzed using high-resolution continuum source atomic absorption spectrometry with and without matrix purification. The results obtained were metrologically compatible with each other.

Author Correction: Absolute 13C/12C isotope amount ratio for Vienna PeeDee Belemnite from infrared absorption spectroscopy

Author Correction: Absolute 13C/12C isotope amount ratio for Vienna PeeDee Belemnite from infrared absorption spectroscopy

Using Sr-Nd-Pb isotope systems to trace sources of sediment and trace metals to the Weser River system (Germany) and assessment of input to the North Sea

In order to trace the sources of sediment materials and trace metals in the Weser River system (Germany), and the riverine input to the North Sea, Sr, Nd and Pb isotopes, together with multi-elemental compositions, were measured for sediments collected over the entire Weser River Basin, from headwaters to the estuary. Mass fractions of metals, including Ag, Cd, and Pb, and of one metalloid, Sb, higher than their crustal abundance, were observed within the entire Weser Basin. Isotope-amount ratio n(87Sr)/n(86Sr) and εNd ranged from 0.71182 ± 0.00005 to 0.72880 ± 0.00009 and −11.3 ± 0.3 to −21.0 ± 0.3, respectively. n(206Pb)/n(204Pb), n(207Pb)/n(204Pb), and n(208Pb)/n(204Pb) ranged from 18.226 ± 0.008 to 18.703 ± 0.012, 15.613 ± 0.007 to 15.653 ± 0.012 and 38.14 ± 0.02 to 38.84 ± 0.02, respectively. Sr and Nd isotope compositions reflected primarily a mixture of natural materials derived from the Weser Basin. Pb isotope signatures indicated strong anthropogenic influences in the middle-lower Weser region. Pb isotopic compositions in the sediments from the Aller (tributary of the Weser) and its tributary suggested influence from historical Pb-Zn ore mining in the Harz Mountains that might contribute to the observed elevated mass fractions of Ag, Cd, Sb and Pb in that region. K-means cluster and principal component analysis of the Sr, Nd, and Pb isotope data yielded results consistent with their isotope systematics, supporting statistical analysis as an unsupervised tool in isotope fingerprinting studies. Sr, Nd, and Pb isotopic signatures in the sediments of the Weser were distinctively different from those of another major river discharging into the North Sea, the Elbe. This suggested that this Sr, Nd, and Pb isotope dataset can be used to distinguish riverine input of sediment materials and metals between the two rivers, thereby assessing their individual contribution to materials transported into the North Sea.

Absolute 13C/12C Isotope Amount Ratio for Vienna Pee Dee Belemnite from Infrared Absorption Spectroscopy.

Measurements of isotope ratios are predominantly made with reference to standard specimens that have been characterized in the past. In the 1950s, the carbon isotope ratio was referenced to a belemnite sample collected by Heinz Lowenstam and Harold Urey1 in South Carolina's Pee Dee region. Due to the exhaustion of the sample since then, reference materials that are traceable to the original artefact are used to define the Vienna Pee Dee Belemnite (VPDB) scale for stable carbon isotope analysis2. However, these reference materials have also become exhausted or proven to exhibit unstable composition over time3, mirroring issues with the international prototype of the kilogram that led to a revised International System of Units4. A campaign to elucidate the stable carbon isotope ratio of VPDB is underway5, but independent measurement techniques are required to support it. Here we report an accurate value for the stable carbon isotope ratio inferred from infrared absorption spectroscopy, fulfilling the promise of this fundamentally accurate approach6. Our results agree with a value recently derived from mass spectrometry5, and therefore advance the prospects of SI-traceable isotope analysis. Further, our calibration-free method could improve mass balance calculations and enhance isotopic tracer studies in CO2 source apportionment.

Development of Molybdenum Isotopic Certified Reference Materials with SI‐traceable Property Values

Molybdenum isotopes have been widely studied and applied to various fields of Earth and planetary sciences in recent years. Inspired by the increasing demand for reliable and comparable measurement data, three molybdenum isotopic reference materials have been developed by the National Institute of Metrology (China), including one natural‐abundance iCRM (GBW 04504) and two isotopically enriched iCRMs of 97Mo (GBW 04505) and 100Mo (GBW 04506), respectively. The property values of isotope amount ratios and isotopic abundances of these iCRMs have been certified by fully calibrated mass spectrometry using a multi‐collector inductively coupled plasma‐mass spectrometer. The instrumental mass bias correction was performed using five synthetic isotope mixtures, which were gravimetrically prepared by all seven high‐purity molybdenum isotope materials. The determined absolute molybdenum isotopic compositions of GBW 04504, 04505 and 04506 are thus traceable to the SI units kilogram and mole. On the basis of the assessment in ISO Guide 35: 2017, these iCRMs exhibited sufficient homogeneity and stability for the application of molybdenum isotope‐ratio determinations. The δ98/95MoNIST SRM 3134 value of GBW 04504 was measured as −0.31 ± 0.07‰ (1sm) relative to the delta zero reference material NIST SRM 3134 (Lot No. 130418).

Absolute and relative measurement of the 243Am half-life

The half-life of 243Am has been measured by an absolute and a relative method, i.e. by determining the specific activity of 243Am and the specific activity ratio with 241Am. A mixed 241,243Am reference material was produced and certified for its americium mass content and its isotope amount ratios. The characterisation of the mass content of 243Am was established by isotope dilution mass spectrometry using an 241Am spike, produced from highly enriched 241Pu material. The isotope amount ratios n(241Am)/n(243Am) and n(242mAm)/n(243Am) were measured by thermal ionisation mass spectrometry. Activity measurements were performed by alpha-particle counting at a defined solid angle, as well as high-resolution alpha-particle spectrometry. From the 243Am/241Am activity and isotopic amount ratios, a value of 16.988 (24) was derived for the 243Am/241Am half-life ratio. Using a value of 432.6 (6) a for the 241Am half-life, the corresponding 243Am half-life value, 7349 (15) a, is in good agreement with the result obtained from the absolute method, 7342 (14) a. The mean value, 7345 (14) a, agrees well with data from literature and lowers the relative standard uncertainty to 0.2%.

A new highly enriched 233U reference material for improved simultaneous determination of uranium amount and isotope amount ratios in trace level samples

A highly-enriched 233U reference material (>0.99987 n(233U)/n(U)) has been prepared and characterized for use as an isotope dilution mass spectrometry spike. An ion exchange separation was performed on 1 g of high purity 233U to further reduce trace amounts of contaminant Pu in the material. The purified 233U was then prepared as a master solution which was analyzed for molality of uranium by modified Davies and Gray titration. A portion of the master solution was quantitatively diluted and dispensed for reference material units. Selected units were analyzed for verification of uranium amount and to characterize uranium isotope amount ratios by multi-collector inductively couple plasma mass spectrometry. Modelling of spike-corrected isotopic data show that the new spike will enable simultaneous measurements of uranium amount and isotope amount ratios with resulting uncertainties that are substantially less sensitive to over spiking than widely used 233U certified reference materials.

Multivariate modelling techniques applied to metabolomic, elemental and isotopic fingerprints for the verification of regional geographical origin of Austrian carrots

An exploratory study for verifying regional geographical origin of carrots from specific production regions in Austria (“Genussregionen”) was performed by combining chemical fingerprinting methods, namely n(86Sr)/n(87Sr) isotope amount ratios, multi-elemental and metabolomic pattern. Chemometric classification models were built on individual and combined datasets using (data-driven) soft independent modelling of class analogies and (orthogonal) projections to latent structures-discriminant analysis to characterise and differentiate carrots grown in five regions in Austria. A predictive ability of 97% or better (depending on the classification technique) was obtained using combined Sr isotope amount ratios and multi-elemental data. The use of data fusion strategies, in particular the mid-level option (fusion of selected variables from the different analytical platforms), allowed highly efficient (99–100%, except soft independent modelling of class analogy with 97%) and correct classification of carrot samples.

Determination of the Isotopic Composition of Gadolinium Using Multicollector Inductively Coupled Plasma Mass Spectrometry

In this study, we report independent measurements of all stable isotope ratios of gadolinium. Our study employs multicollector inductively coupled plasma mass spectrometry (MC-ICPMS) with National Research Council Canada (NRC) HALF-1 isotopic hafnium standard as a primary calibrator and surveys four commercial gadolinium materials, including a NRC candidate isotopic reference material, GADS-1. The isotopic composition of gadolinium is determined using the regression model without reliance on conventional normalizing isotope ratios or mass-dependent isotope ratio correction models. In this work, all gadolinium isotope ratios were obtained from 160Gd/158Gd which, in turn, was measured from hafnium 178Hf/177Hf either directly or indirectly through 167Er/166Er. The latter approach was used for the final determination of gadolinium isotopic composition, as it provides smaller combined uncertainty. We report high-precision measurements of the isotopic composition of gadolinium, which support a revised standard atomic weight. Isotope amount ratios of R152/158 = 0.008 20(2)k=1, R154/158 = 0.087 98(12)k=1, R155/158 = 0.596 81(63)k=1, R156/158 = 0.825 08(57)k=1, R157/158 = 0.630 60(22)k=1, and R160/158 = 0.879 10(60)k=1, and the atomic weight of Ar(Gd) = 157.2502(6)k=1 were obtained for gadolinium in GADS-1.

Copper Isotopic Analysis in Geological and Biological Reference Materials by MC‐ICP‐MS

The characterisation of relative copper isotope amount ratios (δ65Cu) helps constrain a variety of geochemical processes occurring in the geosphere, biosphere and hydrosphere. The accurate and precise determination of δ65Cu in matrix reference materials is crucial in the effort to validate measurement methods. With the goal of expanding the number and variety of available geological and biological materials, we have characterised the δ65Cu values of ten reference materials by MC‐ICP‐MS using C‐SSBIN model for mass bias correction. SGR‐1b (Green River shale), DOLT‐5 (dogfish liver), DORM‐4 (fish protein), TORT‐3 (lobster hepatopancreas), MESS‐4 (marine sediment) and PACS‐3 (marine sediment) have for the first time been characterised for δ65Cu. Additionally, four reference materials (with published δ65Cu values) have been characterised: BHVO‐1 (Hawaiian basalt), BIR‐1 (Icelandic basalt), W‐2a (diabase) and Seronorm™ Trace Elements Serum L‐1 (human serum). The reference materials measured in this study possess complex and varied matrices with copper mass fractions ranging from 1.2 µg g−1 to 497 µg g−1 and δ65Cu values ranging from −0.20‰ to 0.52‰ with a mean expanded uncertainty of ± 0.07‰ (U, k = 2), covering much of the natural copper isotope variability observed in the environment.

Boron isotope variability related to boron speciation (change during uptake and transport) in bell pepper plants and SI traceable n(11 B)/n(10 B) ratios for plant reference materials.

Boron (B) is an essential micronutrient in plants and its isotope variations are used to gain insights into plant metabolism, which is important for crop plant cultivation. B isotope variations were used to trace intra-plant fractionation mechanisms in response to the B concentration in the irrigation water spanning the range from B depletion to toxic levels. A fully validated analytical procedure based on multi-collector inductively coupled plasma mass spectrometry (MC-ICP-MS), sample decomposition and B matrix separation was applied to study B isotope fractionation. The validation was accomplished by establishing a complete uncertainty budget and by applying reference materials, yielding expanded measurement uncertainties of 0.8‰ for pure boric acid solutions and ≤1.5‰ for processed samples. With this validated procedure SI traceable B isotope amount ratios were determined in plant reference materials for the first time. The B isotope compositions of irrigation water and bell pepper samples suggest passive diffusion of the heavy 11 B isotope into the roots during low to high B concentrations while uptake of the light 10 B isotope was promoted during B depletion, probably by active processes. A systematic enrichment of the heavy 11 B isotope in higher located plant parts was observed (average Δ11 Bleaf-roots = 20.3 ± 2.8‰ (1 SD)), possibly by a facilitated transport of the heavy 11 B isotope to growing meristems by B transporters. The B isotopes can be used to identify plant metabolism in response to the B concentration in the irrigation water and during intra-plant B transfer. The large B isotope fractionation within the plants demonstrates the importance of biological B cycling for the global B cycle.

Certification of ERM‐EB400, the First Matrix Reference Material for Lead Isotope Amount Ratios, and ERM‐AE142, a Lead Solution Providing a Lead Isotopic Composition at the Edge of Natural Variation

Lead isotope amount ratios are commonly used in diverse fields such as archaeometry, geochemistry and forensic science. Currently, five reference materials with certified lead isotope amount ratios are available, namely NIST SRM 981, 982 and 983, GBW‐04442 and NMIJ 3681‐a. Only NIST SRM 981 and NMIJ 3681‐a have approximately natural isotopic compositions, and NIST SRM 981 is predominantly used for correcting mass discrimination/mass fractionation in the applied mass spectrometric procedures. Consequently, there is no other certified reference material available to be used for validation and/or quality control of the analytical procedures applied to lead isotope amount ratio measurements. To fill this gap, two new reference materials have been produced and certified for their lead isotope amount ratios. For both certified reference materials, complete uncertainty budgets have been calculated and SI traceability has been established. This provides the users with independent means for validating and verifying their analytical procedures and for conducting quality control measures. ERM‐EB400 is a bronze material with a nominal lead mass fraction of 45 mg kg−1 and certified lead isotope amount ratios of n(206Pb)/n(204Pb) = 18.072(17) mol mol−1, n(207Pb)/n(204Pb) = 15.578(18) mol mol−1 and n(208Pb)/n(204Pb) = 38.075(46) mol mol−1 with the associated expanded uncertainties (k = 2) given in brackets. ERM‐AE142 is a high‐purity solution of lead in 2% nitric acid with a nominal mass fraction of 100 mg kg−1 and certified Pb isotope amount ratios of n(206Pb)/n(204Pb) = 21.114(17) mol mol−1, n(207Pb)/n(204Pb) = 15.944(17) mol mol−1 and n(208Pb)/n(204Pb) = 39.850(44) mol mol−1 with the associated expanded uncertainties (k = 2) given in brackets. Both materials are specifically designed to fall within the natural lead isotopic variation and to assist users with the validation and verification of their analytical procedures. Note that while one of these reference materials requires the chemical separation of Pb from its matrix (ERM‐EB400), the other does not (ERM‐AE142). As additional information, δ208/206PbNIST SRM981 values are provided for both materials. For ERM‐AE142, a delta value of δ208/206PbNIST SRM981 = −28.21(30)‰ was obtained, and for ERM‐EB400, a delta value of δ208/206PbNIST SRM981= −129.47(38)‰ was obtained, with the associated expanded uncertainties (k = 2) given in brackets.

Contribution of an interlaboratory comparison to the certification of the STAM/IRMM-0243 243Am reference material

Following the expression of the need for an americium (Am) standard and particularly for one with a certified americium-243 (243Am) content, the Commissariat a l’Energie Atomique et aux Energies Alternatives (CEA)/Direction de l’Energie Nucleaire of Marcoule and the European Commission Joint Research Center in Geel carried out a collaborative project for the production of a certified reference material enriched in 243Am. CEA’s Commission d’ETAblissement des Methodes d’Analyse organized an interlaboratory comparison on this material prior to the issuing of its certificate. The usefulness of an interlaboratory comparison to assess the measurement capabilities in the field and to confirm the provisional certified values for the amount contents of 243Am, 241Am, total Am, the isotopic composition and the molar mass of Am has been demonstrated. Furthermore this interlaboratory comparison enabled to derive an indicative value for the n(242mAm)/n(243Am) isotope amount ratio.

Development and characterisation of new glycine certified reference materials for SI-traceable13C/12C isotope amount ratio measurements

Variations in the stable isotopic composition of carbon are used in diverse fields, including biology, environmental sciences, food and drug authentication and forensic applications.