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Eingeladener Vortrag
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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.
In the past, δ26/24Mg measurements were referenced to NIST SRM 980, the initial zero of the δ26/24Mg scale. With the development of MC-ICPMS, the detection of small but measurable isotopic differences in different chips of SRM 980 became apparent. To solve this problem a suite of magnesium isotope reference materials, ERM-AE143, -AE144 and -AE145, has been certified in a first study by applying an ab initio calibration for absolute Mg isotope ratios without any a priori assumptions, a procedure which fulfils all requirements of a primary method of measurement. We could achieve for the first time measurement uncertainties for isotope amount ratios close to the typical precision of magnesium delta values, δ26/24Mg, which are at the 0.1 ‰ level (2SD). In addition, it was demonstrated that commonly used fractionation laws are invalid for correcting Mg isotope ratios in multi-collector ICPMS as they result in a bias which is not covered by its associated uncertainty. Depending on their type, fractionation laws create a bias up to several per mil, with the exponential law showing the smallest bias between 0.1 ‰ to 0.7 ‰.
With these isotope reference materials, it is possible to establish SI-traceability for magnesium delta measurements. To realize this, we organized a second study within which five expert laboratories participated to cross-calibrate all available magnesium isotope standards, which are NIST SRM 980, IRMM-009, ERM-AE143, ERM-AE144, ERM-AE145 and the standards DSM3 and Cambridge-1. The mean δ26/24Mg values for the individual iRMs, calculated from the laboratory means show 2 SD reproducibilities varying between 0.025 and 0.093 ‰. Propagated measurement uncertainties suggest a standard uncertainty of about 0.1‰ for δ26/24Mg determinations (2SD). Thus, SI traceability for magnesium isotope amount ratios and delta values is demonstrated to be established.
ICP-MS has played a key role in inorganic chemical metrology for 25 years, from the 1993 CIPM feasibility study which led to establishment of the CCQM. Since that time, the Inorganic Analysis Working Group of the CCQM has organised 56 international comparisons involving measurements by ICP-MS and, in a recent comparison, 16 different national institutes submitted their results using the technique. Metrological applications of ICP-MS currently address an enormous range of measurements using a wide variety of instrumentation, calibration strategies and methodologies. This review provides an overview of the ICP-MS field with an emphasis on developments which are of particular relevance to chemical metrology.
Examples from CCQM comparisons and the services available from the participants are used to illustrate how the capability and scope of ICP-MS methods have expanded far beyond the expectations of 1993. This is due in part to the research and development Programmes of the national institutes which participate in the CCQM. They have played a key role in advancing new instrumentation and applications for elemental analysis, isotope dilution mass spectrometry, determination of isotopic ratio or composition, and speciation of organometallic compounds. These developments are continuing today, as demonstrated by work in new fields such as heteroatom quantitation of proteins, characterisation and counting of nanoparticles using spICP-MS, and LA-ICP-MS analysis of solid materials.
In isotope ratio applications metrological principles such as measurement uncertainty and SI traceability often are not considered or realized. This is also well-documented by the traceability exception related to delta scale isotope ratio measurements CCQM requested from the CIPM. Generally, delta scale isotope ratio measurements can be performed on a precision level that is significantly lower than the uncertainty level of isotope amount ratio measurements. In the case of magnesium, we demonstrated for the first time that isotope amount ratios can be measured with uncertainties close to the typical precision of magnesium delta values, δ26/24Mg, which are at the 0.1 ‰ level.
In the past, δ26/24Mg measurements were referenced to NIST SRM 980, the initial zero of the δ26/24Mg scale. With the development of MC-ICPMS, the detection of small but measurable isotopic differences in different chips of NIST SRM 980 became apparent and NIST SRM 980 was replaced by an intermediate artefact, DSM3. To solve this problem a suite of magnesium isotope reference materials, ERM-AE143, -AE144, and -AE145, has been certified in a first study by applying an ab initio calibration for absolute Mg isotope ratios without any a priori assumptions, a procedure which fulfils all requirements of a primary method of measurement. Thus, these materials qualified to establish SI-traceability for magnesium delta measurements. In a second study five expert laboratories participated to cross-calibrate all available magnesium isotope standards, which are NIST SRM 980, IRMM-009, ERM-AE143, ERM-AE144, ERM-AE145 and the standards DSM3 and Cambridge-1. The mean δ26/24Mg values for the individual iRMs, calculated from the laboratory means show 2 SD reproducibilities varying between 0.025 and 0.093 ‰. Propagated measurement uncertainties suggest a standard uncertainty of about 0.1 ‰ for δ26/24Mg determinations. Thus, SI traceability for magnesium isotope amount ratios and delta values is demonstrated to be established.
Lead isotopes are a well-established tool to trace the geographic origin of samples and artefacts in archaeology and geochemistry. In archaeology, lead isotopes are often applied to gain information on the provenance of the used ores especially in lead and silver artefacts. The assignment of a specific and unambiguous provenance in most cases is not possible or at least hindered due to several limitations such as ore deposits overlapping in their lead isotopic composition, a large spread within one ore deposit or a missing overlap with known mining sites. Such difficult cases can only be solved by using information from sources being independent of the isotope data. This information can be of chemical nature such as concentrations of key elements or they can be of archaeological nature such as cultural or trade route information.Within this study, we combined lead isotope data of ores and artefacts with silver mass fractions in the ore deposits, Au/Ag-ratios in ores and artefacts and finally archaeological Information on the cultural context in the Mediterranean and Anatolian Region. This approach enabled us to significantly reduce the potential number of mining regions. Finally, the potential sources could be narrowed down to the three remaining locations the Central Taurus, Arap Dağ and the Eastern Troad. Beneath these three locations, the Central Taurus shows the highest probability for the geographic origin of the galena which has been used to create the Trojan silver artefacts.
What isotopes can do...
(2019)
Rationale: 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.
Methods: 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.
Results: The B isotope compositions of Irrigation water and bell pepper samples suggest passive diffusion of the heavy 11B isotope into the roots during low to high B concentrations while uptake of the light 10B isotope was promoted during B depletion, probably by active processes. A systematic enrichment of the heavy 11B isotope in higher located plant parts was observed (average Δ11Bleaf‐roots = 20.3 ± 2.8‰ (1 SD)), possibly by a facilitated transport of the heavy 11B isotope to growing Meristems by B transporters.
Conclusions: 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.
In most chemical reactions, stable isotopes are fractionated in a mass-dependent manner, yielding correlated isotope ratios in elements with three or more stable isotopes. The proportionality between isotope ratios is set by the triple isotope fractionation exponent θ that can be determined precisely for, e.g., sulfur and oxygen by IRMS, but not for metal(loid) elements due to the lower precision of MC-ICP-MS analysis and smaller isotopic variations. Here, using Mg as a test case, we compute a complete metrologically robust uncertainty budget for apparent θ values and, with reference to this, present a new measurement Approach that reduces uncertainty on θ values by 30%. This approach, namely, direct educt-product bracketing (sample−sample bracketing), allows apparent θ values of metal(loid) isotopes to be determined precisely enough to distinguish slopes in three-isotope space. For the example of Mg, we assess appropriate quality Control standards for interference-to-signal ratios and Report apparent θ values of carbonate−seawater pairs. We determined apparent θ values for marine biogenic carbonates, where the foraminifera Globorotalia menardii yields 0.514 ± 0.005 (2 SD), the coral Porites, 0.515 ± 0.006 (2 SD), and two specimens of the giant clam Tridacna gigas, 0.508 ± 0.007 (2 SD) and 0.509 ± 0.006 (2 SD), documenting differences in the uptake pathway of Mg among marine calcifiers. The capability to measure apparent θ values more precisely adds a new dimension to metal(loid) δ values, with the potential to allow us to resolve different modes of fractionation in industrial and natural processes.
During R/V Meteor cruise 141/1, pore fluids of near surface sediments were investigated to find indications for hydrothermal activity in the Terceira Rift (TR), a hyperslow spreading center in the Central North Atlantic Ocean. To date, submarine hydrothermal fluid venting in the TR has only been reported for the D. João de Castro seamount, which presently seems to be inactive. Pore fluids sampled close to a volcanic cone at 2,800‐m water depth show an anomalous composition with Mg, SO4, and total alkalinity concentrations significantly higher than seawater and a nearby reference core. The most straightforward way of interpreting these deviations is the dissolution of the hydrothermally formed mineral caminite (MgSO4 0.25 Mg (OH)2 0.2H2O). This interpretation is corroborated by a thorough investigation of fluid isotope systems (δ26Mg, δ30Si, δ34S, δ44/42Ca, and 87Sr/86Sr). Caminite is known from mineral assemblages with anhydrite and forms in hydrothermal recharge zones only under specific conditions such as high fluid temperatures and in altered oceanic crust, which are conditions generally met at the TR. We hypothesize that caminite was formed during hydrothermal activity and is now dissolving during the waning state of the hydrothermal system, so that caminite mineralization is shifted out of its stability zone. Ongoing fluid circulation through the basement is transporting the geochemical signal via slow advection toward the seafloor.