Secondary Reference Materials Research Articles

Criminological Study of Traffic Violations on Numbing Island

Traffic violations are no longer commonplace among society. This often happens in the community, sometimes even causing economic and physical losses due to traffic accidents. Positive law in Indonesia has explicitly regulated traffic safety rules which are regulated in Law Number 22 of 2009 concerning Road Traffic and Transportation. To study this, researchers took the research location Numbing Island, which is one of the islands in the Riau Islands Province. And from a criminological perspective, researchers want to examine in more depth what is the basis for the perpetrator to commit this offense. The research method used is empirical juridical research. As support in building the arguments for this research, researchers used primary and secondary reference materials. Data collection techniques used by researchers include observation methods, interviews and literature review. The research data analysis technique was carried out using a qualitative method, then in developing a line of thinking, the researcher used a deductive method. The results of this research show that the level of traffic violations on Numbing Island is sociologically caused by a lack of public awareness on the grounds that the application of traffic laws in the island area is not necessary, in terms of law enforcement factors, supervision by Bhabinkamtibmas is still not strictly implemented so that there is a form of negligence on the part of the authorities. law enforcers to enforce traffic regulations.

Vermilion monazite: A new Archean reference material for U-Pb and Sm-Nd microanalysis

Monazite (Vermilion) from the ∼2.7 Ga Vermilion Granitic Complex (Minnesota, USA) was investigated as a potential reference material for U-Pb geochronology, using electron microprobe, high-precision ID-TIMS and high-spatial resolution techniques (LA-(Q/SF/MC)-ICP-MS and SHRIMP). Vermilion monazite is relatively homogeneous in BSE images. It is characterised as a monazite-(Ce) with uniform, relatively LREE-enriched chondrite-normalised REE patterns (Eu/Eu* = 0.074–0.085). ID-TIMS U-Pb analyses yielded concordant to slightly (−0.6% to 1.8%) discordant isotope data with weighted mean 207Pb*/206Pb* dates of 2668.6 ± 1.8 Ma (2σ, MSWD = 1.3, n = 3) and 2666.8 ± 1.8 Ma (2σ, MSWD = 4.0, n = 4). High-spatial resolution data from SHRIMP and LA-(Q/SF/MC)-ICP-MS agree with the ID-TIMS age. Using Vermilion monazite as primary reference material, LA-SF-ICP-MS analyses reproduced the age of several other reference monazites within −1.13% to +1.64% accuracy. Nd isotopes obtained via ID-TIMS and solution MC-ICP-MS returned consistent 143Nd/144Nd ratios of 0.510694 ± 0.000040 (2σ) and 0.510726 ± 0.000014 (2σ), respectively. The LA-MC-ICP-MS 143Nd/144Nd ratios of 0.51071 ± 0.00001 (2σ) and 0.51065 ± 0.00001 (2σ) are also in agreement within uncertainties. Results of Sm-Nd isotope analyses by LA-MC-ICP-MS from two laboratories yielded mean 147Sm/144Nd ratios of 0.0869 ± 0.0002 (2.5% RSD, 2σ, n = 58) and 0.0835 ± 0.0001 (2.2% RSD, 2σ, n = 50), reflecting small variations in individual fragments. The initial epsilon Nd (εNdi) varies from −0.8 ± 0.5 to 0.6 ± 0.4 (2σ). The reproducibility of our results shows that Vermilion monazite can be used as a primary reference material for U-Pb geochronology and is suitable as a secondary reference material for Sm-Nd isotopic tracing. The Archean age of Vermilion monazite, the oldest available as a reference material, will facilitate the investigation of Archean crustal evolution processes and broaden the prospect of studying ancient metamorphic events by combining matrix-matched U-Pb geochronology and Sm-Nd isotopic tracing.

International standards for monoclonal antibodies for assessing the biological activity of medicines: A status update

Scientific relevance. The clinical effects and the expiration of patents for original (reference) biotechnological medicines based on monoclonal antibodies (mAbs) stimulated the development of biosimilar mAbs. The quality profile of a biosimilar mAb should correspond to the quality of the reference medicinal product. When demonstrating biosimilarity and determining the activity of medicines as part of batch quality control, analysts should study the biological properties of mAbs using suitable reference standards. The lack of international standards (ISs) makes mAb manufacturers use in-house reference standards. There is a risk of obtaining non-uniform quality and efficacy data because of the use of in-house reference standards, the heterogeneity and structural complexity of mAbs, and the relationship between the biological activity and efficacy of mAbs.Aim. This study aimed to analyse the relevance of and need for ISs for the biological activity of biotherapeutic mAbs and to define the role of reference medicinal products and ISs in assessing biosimilarity and testing medicines throughout their lifecycle.Discussion. This review covers the issues arising from the lack of ISs for assessing the biological activity of mAbs and the role and significance of reference products and ISs for biosimilars. The authors describe the specifics of studying the biological properties of mAbs and summarise the data on the need to develop and use ISs for the standardisation of biological tests. This review presents the results of studies on the first ISs established by the World Health Organisation to assess the biological activity of mAbs; these results suggest the need to standardise mAbs using ISs to ensure the quality, safety, and efficacy of mAb therapy.Conclusions. The use of ISs for mAbs plays a key role in harmonising biological activity assessments. Publicly available ISs serve as primary standards for the calibration of secondary reference materials. Moreover, ISs are required for the harmonisation of activity evaluation (in IU) between laboratories and for the consistency of the activity of various medicinal products from different manufacturers that share the same INN. The use of ISs by mAb manufacturers will contribute to ensuring the quality of mAbs and clinical monitoring of the effectiveness of their use.

B-202 Improving Performance of an LC-MS C-peptide Reference Method

Abstract Background C-peptide is a useful biomarker for distinguishing among different types of diabetes and is a proxy measure of endogenous insulin production, useful in diabetes management. Additionally, C-peptide tests can be used to diagnose non-diabetic hypoglycemia and insulinoma. However, differences among clinical assays can limit the application of C-peptide testing. To address this issue, efforts are underway to standardize manufacturer assays with serum-based secondary reference materials where values are assigned by a reference LC-MS method. Clinical evidence suggests that patients with diabetes can benefit from residual beta-cell function, yet many clinical assays have high variability at lower levels of C-peptide. Here we explore different approaches for improving sensitivity and selectivity of C-peptide reference measurements with a focus at the lower end of the measurement range. Methods Two methods were developed to evaluate and determine the most effective approach. The first method involved spiking serum samples with isotope-labeled c-peptide (Sigma) and then enriching and enzymatically digesting them. The enrichment process included removing abundant serum proteins by using methanol, followed by centrifugation and filtration through C18 cartridges. The resulting solution was then passed through a strong anion-exchange column after correcting its pH with ammonium formate buffer. The eluent was evaporated, and the residue was dissolved in ammonium carbonate buffer. Enzymatic digestion was performed by adding dithiothreitol and iodoacetamide followed by addition of Glu-C. The digested peptides were then analyzed by LC-MS/MS (QTRAP 6500+) in MRM mode. The second method followed the same steps as the first method, except that the evaporation and digestion step were skipped, and MRM was performed on the intact C-peptide chain. Two separate calibration curves were constructed for each method using isotope labeled c-peptide (Sigma) and certified reference material (National Metrology Institute of Japan) as native c-peptide. Results The first method, which measures intact C-peptide using MRM, had a slope of 1.14 and an intercept of −0.01 nmol/L (Deming regression, R = 0.917) when compared to the reference method. The method demonstrated CV within 0.4%–11.9%. The second method, which quantifies digested peptides, showed a slope of 1.02 and an intercept of −0.21 nmol/L compared to the reference method (Deming regression, R = 0.995). The method demonstrated CV within 4.4–20.0%. Controlling the three MRM transitions improved the specificity and accuracy of the results. For the first method two MRM transitions were adequate. Both methods showed no significant matrix effects. The first method is simpler to implement due to a smaller number of separation steps. Conclusion We have explored two new alternative workflows for C-peptide quantitation that include first, an enzymatic digestion then MRM quantitation and second, MRM quantitation of intact C-peptide. To improve the analytical performance of the methods, further optimization is still required.

Development of a secondary reference material for application in carbon-14 specific activity determination by thermal oxidation and liquid scintillation counting method

Abstract Carbon-14 (14C) is a pure beta-emitting radionuclide with a half-life of 5730 ± 30 y. Considering the long half-life and its biological importance, significant attention is given to monitoring 14C in the vicinity of nuclear facilities. The 14C measurement technique employed by the majority of environmental monitoring laboratories for impact assessments in the vicinity of nuclear facilities is based on the thermal oxidization of the samples and the determination of activity by liquid scintillation counting. One of the difficulties faced by these laboratories is the nonavailability of a suitable matrix-matching reference material which is truly representative of the type of sample being analyzed. In this study, an effort has been made to develop a reference material that is representative and has a similar thermal oxidation/combustion property as that of a typical terrestrial plant biota observed in the vicinity of the nuclear power plants of India for quality assurance programs. A prebomb era wood (~150 years old) was identified as a potential secondary reference material. The stable carbon ratio (d13C) of the sample was determined by isotopic ratio mass spectrometer (IRMS), and the mean value was −26.33 ± 0.47 ‰. The 14C specific activity of the sample was determined by accelerator mass spectrometry and a mean value of 221.6 ± 0.6 Bq kg−1 C was assigned as the reference value to the prebomb wood. In addition, measurements were performed by thermal oxidation in a tube furnace and by analysis of the 14C activity in a liquid scintillation counter.

Laser ablation (in situ) Lu-Hf dating of magmatic fluorite and hydrothermal fluorite-bearing veins

Fluorite (CaF2) is a common hydrothermal mineral, which precipitates from fluorine-rich fluids with an exceptional capacity to transport metals and Rare Earth Elements (REEs). Hence, the ability to date fluorite has important implications for understanding the timing of metal transport in hydrothermal systems. Here we present, for the first time, fluorite Lu-Hf dates from fluorite-carbonate veins from the Olympic Cu-Au Province in South Australia. The fluorite dates were obtained in situ using the recently developed LA-ICP-MS/MS Lu-Hf dating method. A fluorite-calcite age of 1588 ± 19 Ma was obtained for the Torrens Dam prospect, consistent with the timing of the formation of the nearby Olympic Dam iron-oxide copper gold Breccia Complex. Veins in the overlying Neoproterozoic successions were dated at 502 ± 14 Ma, indicating a temporal link between Cu-sulphide remobilisation and the Delamerian Orogeny. Additionally, we present a multi-session reproducible date for magmatic fluorite from a monzogranite in the Pilbara Craton (Lu-Hf age of 2866 ± 19 Ma). This age is consistent with a garnet Lu-Hf age from the same sample (2850 ± 12 Ma) and holds potential to be developed into a secondary reference material for future fluorite Lu-Hf dating.

U‐Th‐Pb and Trace Element Evaluation of Existing Titanite and Apatite LA‐ICP‐MS Reference Materials and Determination of 208Pb/232Th‐206Pb/238U Date Discordance in Archaean Accessory Phases

The last decade has seen a marked increase in U‐Th‐Pb petrochronological studies focused on titanite and apatite. This has motivated the need for detailed, phase‐specific method development and well‐characterised reference materials with a wide variety of ages and chemical compositions. This study presents new U‐Th‐Pb isotope and major‐, minor‐ and trace‐element mass fraction data for ten titanite and five apatite reference materials based on integrated EPMA, LA‐ICP‐MS and isotope‐dilution (ID) multi‐collector (MC)‐ICP‐MS characterisation. Cross‐comparison of EPMA and LA‐ICP‐MS data for the same titanite reference material suite demonstrates that careful selection of EPMA primary reference materials is necessary to minimise inaccuracies. We further identify a significant X‐ray interference when measuring low Ce abundances in Ti‐bearing phases and outline a method for its correction. New ID‐MC‐ICP‐MS and LA‐ICP‐MS data suggest tri‐concordance (defined as concordant ages for the 238U‐206Pb, 235U‐207Pb and 232Th‐208Pb decay systems) of the MKED‐1 titanite reference material and demonstrate the reproducibility of 208Pb/232Th measurements in some secondary titanite reference materials. Integration of 208Pb/232Th results with U‐Pb geochronology provides a meaningful tool to help interpret complex U‐Th‐Pb isotopic age spectra. We provide example applications of 208Pb/232Th LA‐ICP‐MS measurements toward interpreting Archaean titanite ages from the Acasta Gneiss Complex, Northwest Territories, Canada.

Characterisation of Three Sri Lankan Zircon Megacrysts as Potential Reference Materials for Microbeam U‐Pb Geochronology and Hf‐O‐Zr Isotope Measurements

In situ U‐Pb geochronology and hafnium, oxygen and zirconium isotope measurements in zircons using laser ablation‐inductively coupled plasma‐mass spectrometry (LA‐ICP‐MS) and ion microprobe techniques can provide essential isotopic data to constrain geological evolutionary histories. Developing reliable zircon reference materials is the cornerstone for in situ zircon chronology and isotopic studies. In this study, the homogeneity of U‐Pb ages and Hf‐O‐Zr isotope ratios in three Sri Lankan zircon megacrysts (SLZA, SLZB and SLZC) were investigated using multiple analytical methods. The obtained U, Th, Pb and Hf mass fractions of the SLZA zircon were 839 ± 56 μg g‐1 (1s), 151 ± 15 μg g‐1 (1s), 198 ± 28 μg g‐1 (1s) and 8635 ± 286 μg g‐1 (1s), respectively. The mass fractions of U, Th, Pb and Hf in the SLZB zircon were 1106 ± 106 μg g‐1 (1s), 331 ± 61 μg g‐1 (1s), 376 ± 57 μg g‐1 (1s) and 9673 ± 976 μg g‐1 (1s), respectively. The U, Th, Pb and Hf mass fractions determined in the SLZC zircon were 551 ± 35 μg g‐1 (1s), 111 ± 8 μg g‐1 (1s), 129 ± 18 μg g‐1 (1s) and 7881 ± 393 μg g‐1 (1s), respectively. The chemical abrasion isotope dilution thermal ionisation mass‐spectrometry (CA‐ID‐TIMS) method yielded a Th‐corrected weighted mean 206Pb/238U age of 556.94 ± 1.29 Ma (95% conf., n = 5) for the SLZA zircon, 552.90 ± 1.29 Ma (95% conf., n = 7) for the SLZB zircon and 560.83 ± 1.29 Ma (95% conf., n = 7) for the SLZC zircon. The obtained Hf isotopic compositions of the SLZA, SLZB and SLZC zircons determined with the solution MC‐ICP‐MS method were 0.281651 ± 0.000014 (2s, n = 10), 0.281704 ± 0.000008 (2s, n = 10) and 0.281676 ± 0.000006 (2s, n = 10), respectively. The obtained O isotopes of the SLZA and SLZB zircons measured with the laser fluorination method were 12.14 ± 0.56‰ (2s, n = 4) and 11.91 ± 0.30‰ (2s, n = 4), respectively. The Zr isotopes of the SLZA, SLZB and SLZC zircons determined with double spike TIMS analysis yielded mean δ94/90ZrSRM3169 values of ‐0.03 ± 0.06‰ (2s, n = 10), ‐0.03 ± 0.04‰ (2s, n = 10) and 0.00 ± 0.07‰ (2s, n = 8), respectively. The SLZA zircon can be used as a primary reference or quality control material for microbeam U‐Pb, Hf and Zr isotope measurements because of its slight heterogeneity. The U‐Pb, Hf and Zr isotopic compositions of the SLZB and SLZC megacrysts were homogeneous. The O isotopic compositions in the SLZA and SLZB zircon were slightly dispersed, indicating that these two megacrysts can only serve as secondary reference materials for microbeam O isotope measurements.

A New Natural Secondary Reference Material for Garnet U‐Pb Dating by TIMS and LA‐ICP‐MS

Gem quality andradite‐rich garnet (IUC‐1), obtained from the Miocene trachyte dome near Ankara city (Turkey), has been identified as a potential natural secondary reference material for U‐Pb dating. In this study, U‐Pb dating was performed in five different laboratories using isotope dilution TIMS and laser ablation ICP‐MS to determine the homogeneity of euhedral garnet crystals. The U‐Pb ID‐TIMS data for IUC‐1 yielded 207Pb/235U and 206Pb/238U ages of 20.9 ± 0.4 and 20.6 ± 0.8 Ma respectively, and these values are consistent with U‐Pb LA‐ICP‐MS analyses, in which different garnet crystals yielded ages of 20.8 ± 0.1, 20.7 ± 0.1, 20.7 ± 0.2 and 20.2 ± 0.1 Ma. An andradite (IUC‐2) from the Serçeören wollastonite skarn (Turkey) can be used as a secondary reference material provided detailed imaging of the crystals is undertaken. ID‐TIMS data yielded 207Pb/235U and 206Pb/238U ages of 20.4 ± 0.4 and 20.9 ± 1.0 Ma respectively, and yielded U‐Pb ages on different grains of 20.5 ± 0.1, 20.7 ± 1.0, 20.8 ± 1.7 and 20.9 ± 1.6 Ma. The assigned weighted mean age of IUC‐1 (20.4 ± 0.5 Ma, 2s) is proposed as a 2023 reference value. IUC‐1 garnet is expected to contribute significantly to rapidly developing garnet geochronology in the near future.

Commutability Assessment of Candidate Reference Materials for Lipoprotein(a) by Comparison of a MS-based Candidate Reference Measurement Procedure with Immunoassays.

Elevated concentrations of lipoprotein(a) [Lp(a)] are directly related to an increased risk of cardiovascular diseases, making it a relevant biomarker for clinical risk assessment. However, the lack of global standardization of current Lp(a) measurement procedures (MPs) leads to inconsistent patient care. The International Federation for Clinical Chemistry and Laboratory Medicine working group on quantitating apolipoproteins by mass spectrometry (MS) aims to develop a next-generation SI (International system of units)-traceable reference measurement system consisting of a MS-based, peptide-calibrated reference measurement procedure (RMP) and secondary serum-based reference materials (RMs) certified for their apolipoprotein(a) [apo(a)] content. To reach measurement standardization through this new measurement system, 2 essential requirements need to be fulfilled: a sufficient correlation among the MPs and appropriate commutability of future serum-based RMs. The correlation among the candidate RMP (cRMP) and immunoassay-based MPs was assessed by measuring a panel of 39 clinical samples (CS). In addition, the commutability of 14 different candidate RMs was investigated. Results of the immunoassay-based MPs and the cRMPs demonstrated good linear correlations for the CS but some significant sample-specific differences were also observed. The results of the commutability study show that RMs based on unspiked human serum pools can be commutable with CS, whereas human pools spiked with recombinant apo(a) show different behavior compared to CS. The results of this study show that unspiked human serum pools are the preferred candidate secondary RMs in the future SI-traceable Lp(a) Reference Measurement System.

Testing Nano‐Powder and Fused‐Glass Mineral Reference Materials for In SituRb‐Sr Dating of Glauconite, Phlogopite, Biotite and Feldspar via LA‐ICP‐MS/MS

Reference materials (RMs) with well‐characterised composition are necessary for reliable quantification and quality control of isotopic analyses of geological samples. For in situ Rb‐Sr analysis of silicate minerals via laser ablation inductively coupled plasma tandem mass spectrometry (LA‐ICP‐MS/MS) with a collision/reaction cell, there is a general lack of mineral‐specific and matrix‐matched RMs, which limits wider application of this new laser‐based dating technique to certain minerals. In this work, pressed nano‐powder pellets (NP) of four RMs, GL‐O (glauconite), Mica‐Mg (phlogopite), Mica‐Fe (biotite) and FK‐N (K‐feldspar), were analysed and tested for in situ Rb‐Sr dating, complemented by isotope dilution (ID) MC‐ICP‐MS Rb‐Sr analyses of GL‐O and Mica‐Mg. In addition, we attempted to develop alternative flux‐free and fused ‘mineral glasses’ from the above RMs for in situ Rb‐Sr dating applications. Overall, the results of this study showed that among the above RMs only two NP (Mica‐Mg‐NP and GL‐O‐NP) were suitable and robust for in situ dating applications. These two nano‐powder reference materials, Mica‐Mg‐NP and GL‐O‐NP, were thus used as primary RMs to normalise and determine Rb‐Sr ages for three natural minerals: MDC phlogopite and GL‐O glauconite grains, and also Mica‐Fe‐NP (biotite). Our in situ analyses of the above RMs yielded Rb‐Sr ages that are in good agreement (within 8%) of published ages, which suggests that both Mica‐Mg‐NP and GL‐O‐NP are suitable RMs for in situ Rb‐Sr dating of phlogopite, glauconite and biotite. However, using secondary RMs is recommended to monitor the quality of the obtained ages.

Dating fluid infiltration and deformation in the subducted ultramafic oceanic lithosphere by perovskite geochronology

Carbonated ultramafic rocks (i.e., ophicarbonates) form by peridotite serpentinization and carbonation at the seafloor. Their metamorphic evolution is linked to that of serpentinites, hence dating deformation and metamorphism in ophicarbonates will add constraints to the P-T-t history of the subducted ultramafic lithosphere. A potential, yet underexplored, suitable mineral for geochronology in ophicarbonates is perovskite (CaTiO3). We present trace element and geochronological data (LA-ICPMS and ID-TIMS) from perovskite in ophicarbonate rocks and calcite veins from two metamorphic terranes, Lanzo Massif and Val Malenco (Alps). Metamorphic perovskite in ophicarbonates is characterized by enrichment in heavy REE, and strong negative anomalies in Zr and Hf, as well as Sr and Pb, which are attributed to coexistence of a Zr-rich phase and mobilization of these elements by fluids, respectively. Other trace elements broadly reflect the composition of the protolith and allow the distinction of perovskite from mafic and ultramafic rocks.In the Lanzo Massif, the 49.6 ± 1.0 Ma age of perovskite in shear bands constrains H2-mediated carbonate reduction and abiotic methane and graphite formation at near peak metamorphic conditions during deformation. Perovskite from Val Malenco is found in calcite veins cutting across serpentinite shear foliation and its age of 48.9 ± 0.5 Ma coincides with a major thrusting and extension event that is distinct in age from the initial nappe stacking. The Val Malenco perovskite age can be reproduced by LA-ICPMS and ID-TIMS and is proposed as a suitable secondary reference material for metamorphic, low U perovskite. These results show that metamorphic perovskite geochronology yields geologically meaningful UPb ages and is a viable tool to date deformation and fluid flow in the subducted oceanic lithosphere.

Revisiting the Happy Jack Uraninite Reference Material: A Combined Electron Beam and Laser Ablation In Situ Study.

This new comprehensive in situ mineral-chemical characterisation of the Happy Jack uraninite has discovered additional information regarding matrix effects and trace element homogeneity, relevant to proposals that it could serve as a reference material (RM). On the LA-ICP-MS instrumentation used, there was an absence of discernible matrix effects relative to the silicate glass NIST SRM 610. Lanthanides and Y are found to be very homogeneously distributed in Happy Jack uraninite, Zr, Nb and Ti mass fractions reproducible but only within individual fragments, and other elements still generally heterogeneous. This means that the Happy Jack uraninite can serve as a secondary RM for quality control in studies of natural uraninites. In terms of absolute accuracy and intermediate measurement precision, the Happy Jack uraninite can be used for the homogeneous elements. For elements that are homogeneous within individual fragments only, intermediate measurement precision can still be evaluated, while information values will be obtained for the generally heterogeneous elements. Two distinct groups (high vs. low Zr) were distinguished to exist among different Happy Jack fragments in association with minor variation of REE mass fractions, which possibly explains the observed (heavy) REE discrepancy between in situ laser ablation and bulk solution ICP-MS analyses.

An easy, fast, and efficient assay for the quantification of peptide Hepcidin-25 in serum and plasma with LC-MS/MS.

The peptide hormone hepcidin-25 plays an important role in iron metabolism. Low or high levels of hepcidin-25 are associated with various iron disorders; therefore, hepcidin-25 is an important biomarker. This study describes an easy and fast analytical assay for the quantification of hepcidin-25 with liquid chromatography-tandem mass spectrometry (LC-MS/MS). Sample preparation was performed by protein precipitation with trichloroacetic acid, and injection onto a LC-MS/MS was directly conducted from a LoBind 96-well plate. The concentration range covered by the quality control samples, ranged from 0.25nmol/L (12.3% CV) to 11.9nmol/L (CV < 9%). Matrix effect was limited (mean recovery of 99.9% with a CV of 6.4%). The assay was validated for serum, EDTA and heparin plasma. An international secondary reference material was used for calibration. The reference interval (90% CL) was estimated for hepcidin-25 by analysing serum and plasma samples from 156 healthy subjects with a lower limit: 0.12 (0.07-0.19) and upper limit: 11.2nmol/L (9.5-13.0). We present a fast and easy assay for the quantification of hepcidin-25 in serum and plasma samples. The assay was successfully used for the detection of various forms of hereditary haemolytic anaemias, to characterize the interplay between erythropoiesis and iron levels.

Natural Allanite Reference Materials forIn SituU‐Th‐Pb and Sm‐Nd Isotopic Measurements by LA‐(MC)‐ICP‐MS

Allanite is a common accessory mineral that generally incorporates considerable amounts of Th, U and light rare Earth elements in its structure, making it a useful mineral forin situU‐Th‐Pb geochronology and Sm‐Nd isotope measurements. Here, we presentin situU‐Th‐Pb ages and Sm‐Nd isotopic compositions for nine allanite samples considered as potential reference materials (CAPb, Tara, Daibosatsu, LE40010, LE2808, A007, A011, A012 and SQ‐51), with ages ranging from ~ 2650 Ma to ~ 12 Ma. Our study indicates that Daibosatsu and LE40010 have relatively homogeneous147Sm/144Nd and143Nd/144Nd isotopic compositions (147Sm/144Nd ratio variation is less than 2%) and, thus, can serve as primary reference materials for Sm‐Nd microanalysis. In contrast, CAPb, Tara, LE2808, A007, A011 and A012 all show homogeneous calculated initial143Nd/144Nd isotopic compositions, but with variable147Sm/144Nd compositions, and thus can be used only as secondary reference materials for Sm‐Nd microanalysis. Of these materials, LE40010 allanite can serve as a suitable primary reference material forin situU‐Pb dating, CAPballanite can serve as a suitable primary reference material forin situTh‐Pb dating, and LE2808, LE40010, A007, A011 and A012 can serve as suitable secondary reference materials forin situU‐Pb geochronology. In addition, Daibosatsu is suitable as a secondary reference material for Cenozoic Th‐Pb dating to monitor data reproducibility.

Development of human serum matrix-based unconjugated estriol-certified reference material by recommended ID-LC-MS/MS reference method.

To solve long-term lack of traceability of commercial calibrator kits and standardize clinical routine assays, we developed a human serum matrix-based unconjugated estriol (uE3) reference material (RM) with five concentration gradients. The RMs of uE3 were certified by the National Institute of Metrology (NIM) with the codes of GBW (E) 091048, GBW (E) 091049, GBW (E) 091050, GBW (E) 091051, and GBW (E) 091052. The RMs were determined by isotope dilution liquid chromatography-tandem mass spectrometry (ID-LC-MS/MS) reference method which was developed in our group and recommended by the Joint Committee on Traceability on Laboratory Medicine (JCTLM). GBW09224 is intended for use as a primary reference material to enable the SI-traceable measurement of uE3. This study describes the development process of these certified RMs. The candidate material was prepared by collecting from the remaining serum samples after routine clinical testing. Satisfactory homogeneity and stability were shown in these RMs. They are also commutable between the reference method and the three routine clinical immunoassay systems. To improve the accuracy of value assignment, a collaborative study in nine reference laboratories was conducted which was performed according to ISO/WD 15725-1 and all of the reference laboratories have been confirmed by China National Accreditation Service for Conformity Assessment (CNAS). The raw results were statistically analyzed and processed, coupled with uncertainty evaluation, to obtain the certified value: GBW (E) 091048 is 22.1 ± 1.3 nmol/L, GBW (E) 091049 is 33.6 ± 1.6 nmol/L, GBW (E) 091050 is 10.4 ± 0.8 nmol/L, GBW (E) 091051 is 15.5 ± 1.0 nmol/L, GBW (E) 091052 is 47.0 ± 2.0 nmol/L. The preparation process of human serum matrix-based reference material and the lack of these type of secondary (commutable) reference material of unconjugated estriol lead to the interruption of its traceability chain, which is a problem to be solved in its standardization as mentioned in the metrological traceability in ISO 17511, 2020.

LA‐ICP‐MS/MS Single‐Spot Rb‐Sr Dating

Due to developments in reaction cell technologies, it is now possible to collect large 87Rb/86Sr and 87Sr/86Sr data sets using LA‐ICP‐MS/MS. Until now, LA‐ICP‐MS/MS Rb‐Sr ages were constrained using conventional isochrons on a contiguous set of Rb‐Sr data. In this contribution, we present a straightforward procedure on how to measure, calculate and validate Rb‐Sr ages from individual laser spots even from detrital grains devoid of context. This approach does not only allow provenance studies of detrital micas, but also furthermore opens the opportunity to produce age maps with unprecedented spatial resolution, both for zoned single crystals and targeting different textural domains. The main challenge for calculating single‐spot Rb‐Sr ages is the estimation of the initial 87Sr/86Sr composition, if it cannot be constrained through analysis of a paragenetic phase. In this case, we propose to use a range of geologically relevant initial 87Sr/86Sr compositions rather than one fixed value: (1) 0.703 ± 0.003 (for mantle derived magmatic rocks), (2) 0.715 ± 0.015 (for evolved magmatic rocks) and (3) 0.730 ± 0.030 (for crustal rocks). Modelling shows that the 87Sr/86Sr ratio of the targeted material delineates the accuracy and precision of single‐spot Rb‐Sr ages. If the measured Sr isotopic composition is sufficiently radiogenic [87Sr/86Sr of &gt; 1.0 for scenario (1) to &gt; 4.5 for scenario (3)], the calculated age and its uncertainty are not significantly influenced by the initial 87Sr/86Sr composition. Using Mica‐Mg as the primary reference material, single‐spot Rb‐Sr dating was tested on biotite (Mount Dromedary, La Posta, McClure Mountain), muscovite (Högsbo) and a nano‐powder tablet (Mica‐Fe) that we further propose using as secondary reference materials for Rb‐Sr geochronology.

Analytical feasibility of a new reference material (IRMM-524A Fe metal) for the in situ Fe isotopic analysis of pyrite and ilmenite without matrix effects by femtosecond LA-MC-ICP-MS

Evaluation of the IRMM-524A Fe metal as a primary reference material and natural samples of pyrite and ilmenite as secondary reference materials is presented for the Fe isotopic analysis using femtosecond LA-MC-ICP-MS.

Sr Isotopic Composition of NIES Certified Reference Material No. 28 Urban Aerosols

An interlaboratory study of the National Institute for Environmental Studies (NIES) certified reference material (CRM) No. 28 Urban Aerosols collected from the filters of a central ventilating system in a building in the Beijing city center from 1996 to 2005 was performed to obtain an information value of the Sr isotopic composition. The Sr isotopic composition was measured using multi-collector-inductively coupled plasma-mass spectrometry (MC-ICP-MS) to confirm the CRM’s within- and between-bottle homogeneity, and the results showed a 87Sr/86Sr ratio of 0.710227 ± 0.000019 (2SD, n = 18). The Sr isotopic compositions were intercompared using thermal ionization mass spectrometry (TIMS), which showed good agreement with values obtained at NIES. Subsequently, a consistent 87Sr/86Sr ratio was observed between two dissolution (hotplate vs. high-pressure bomb) and Sr separation (Sr spec resin vs. cation exchange resin) methods. To validate and reproduce the accuracy of our analytical methods, the Sr isotopic compositions of secondary reference materials, JB-1b and JA-2, were also measured. Our results showed that NIES CRM No. 28 is appropriate for the quality control of Sr isotope measurements of particulate matter analyses for environmental and geochemical studies.

Use of Non‐Matrix Matched Reference Materials for the Accurate Analysis of Calcium Carbonate by LA‐ICP‐MS

Advances in laser ablation inductively coupled plasma‐mass spectrometry have improved analytical precision for mineral analysis, expanding geological interpretations from LA‐ICP‐MS results. However, with improvements in analytical precision, systematic errors from calibration can become more obvious and affect data quality. To improve the accuracy of the LA‐ICP‐MS technique, a fully quantified method is presented for the analysis of minerals with a CaCO3 matrix. An in‐house calcite sample (P‐Cal) was developed with an independently constrained composition and compared with measurement results from LA‐ICP‐MS analysis, generated using multiple spot sizes, laser fluences and calibration methods. For many elements, calibration against NIST SRM 612 as a calibration reference material and USGS GSD‐1G and USGS BCR‐2G as secondary reference materials (calibration B) provided the best accuracy for CaCO3 analysis. Ablation rates and element yield (ICP‐MS signal intensity in counts per second for a given isotope relative to the mass fraction of the respective element) in calcium carbonate closely resembles NIST SRM 612; however, the down‐hole fractionation curves of USGS BCR‐2G (basaltic glass matrix) are a better fit for carbonate. Variations in accuracy for measurements at different spot sizes are negligible compared with the other effects discussed. Additionally, ablation characteristics for powdered crystals versus large fragments produce a negligible effect on the accuracy of the results for calcium carbonate.