NIST SRM Research Articles

Effect of the Dry Ashing Method on Cadmium Isotope Measurements in Soil and Plant Samples

A dry ashing method is commonly used to remove organic material from samples prior to geochemical analysis. In the course of this study, the Cd isotope ratios of a series of soil and plant reference materials and samples were studied to evaluate the effect of the dry ashing method on measurement results of Cd isotope ratios. The samples were pre‐treated using the dry ashing method and high‐pressure bomb for comparison. The results show that the digestion using high‐pressure bombs did not lead to Cd loss, but using the dry ashing method would cause different proportions of Cd loss. The whole range of Cd isotope difference between two methods was from −0.07‰ to 3.01‰. There was also an obvious difference in measured Cd isotope ratios from the same leaf sample pre‐treated independently by the dry ashing method, indicating that the amount of Cd loss and the effect on Cd isotope measurement during dry ashing is related to the properties of the samples. Therefore, dry ashing may not be appropriate for the removal of organic material in Cd isotope ratio measurement, especially for samples with high organic contents. The δ114/110Cd values of reference materials NIST SRM 1573a and GSD‐30 are reported for the first time in this study.

A Python-Based Pipeline for Preprocessing LC-MS Data for Untargeted Metabolomics Workflows.

Preprocessing data in a reproducible and robust way is one of the current challenges in untargeted metabolomics workflows. Data curation in liquid chromatography–mass spectrometry (LC–MS) involves the removal of biologically non-relevant features (retention time, m/z pairs) to retain only high-quality data for subsequent analysis and interpretation. The present work introduces TidyMS, a package for the Python programming language for preprocessing LC–MS data for quality control (QC) procedures in untargeted metabolomics workflows. It is a versatile strategy that can be customized or fit for purpose according to the specific metabolomics application. It allows performing quality control procedures to ensure accuracy and reliability in LC–MS measurements, and it allows preprocessing metabolomics data to obtain cleaned matrices for subsequent statistical analysis. The capabilities of the package are shown with pipelines for an LC–MS system suitability check, system conditioning, signal drift evaluation, and data curation. These applications were implemented to preprocess data corresponding to a new suite of candidate plasma reference materials developed by the National Institute of Standards and Technology (NIST; hypertriglyceridemic, diabetic, and African-American plasma pools) to be used in untargeted metabolomics studies in addition to NIST SRM 1950 Metabolites in Frozen Human Plasma. The package offers a rapid and reproducible workflow that can be used in an automated or semi-automated fashion, and it is an open and free tool available to all users.

Measurement harmonization and traceability for trace element analyses across the Children's Health Exposure Analysis Resource laboratory network

Harmonization and traceability are related metrological principles that are indispensable to assuring measurement comparability across different biomonitoring studies. The Children's Health Exposure Analysis Resource (CHEAR) was established in 2015 with six laboratories providing environmental exposure measurements on biospecimens. To ensure harmonization across studies for trace elements, CHEAR used a multi-faceted approach that included: 1) an initial interlaboratory validation exercise based on the analysis of certified blood and urine reference materials; 2) frequent participation in an established interlaboratory proficiency program for trace elements; and 3) analysis of a common pool of well-characterized biological reference materials with each analytical batch. Method accuracy and precision were established for each laboratory via analysis of NIST SRM 955c Toxic Elements in Caprine Blood, SRM 2668 Toxic Elements in Frozen Human Urine and SRM 3668 Mercury, Perchlorate, and Iodide in Frozen Human Urine. The differences among the six laboratories for As, Cd, Hg, and Mn in urine and Cd, Hg, and Pb in whole blood were judged to be fit-for-purpose. Interlaboratory performance over a 5-year period demonstrated an improvement in performance, such that for 2018–2019, >99% of challenges for urine As, Cd, Hg, and Mn, and 95% for whole blood Cd, Hg, Pb, and Mn, were found to be satisfactory. The CHEAR common reference materials were analyzed by at least 5 laboratories for 22 elements in urine and 13–14 elements in whole blood, thus providing a rich source of data to assess intra- and inter-run performance. The suite of trace elements with assigned values in both blood and urine matrices are more comprehensive than similar reference materials from other sources, and is reflective of the concentrations necessary to support biomonitoring studies. While some areas for future improvement were identified, significant progress was made to improve harmonization of trace element measurements in biological matrices among the CHEAR network labs.

Isotope abundance ratio measurements using femtosecond laser ablation ionization mass spectrometry.

Accurate isotope ratio measurements are of high importance in various scientific fields, ranging from radio isotope geochronology of solids to studies of element isotopes fractionated by living organisms. Instrument limitations, such as unresolved isobaric inferences in the mass spectra, or cosampling of the material of interest together with the matrix material may reduce the quality of isotope measurements. Here, we describe a method for accurate isotope ratio measurements using our laser ablation ionization time-of-flight mass spectrometer (LIMS) that is designed for in situ planetary research. The method is based on chemical depth profiling that allows for identifying micrometer scale inclusions embedded in surrounding rocks with different composition inside the bulk of the sample. The data used for precise isotope measurements are improved using a spectrum cleaning procedure that ensures removal of low quality spectra. Furthermore, correlation of isotopes of an element is used to identify and reject the data points that, for example, do not belong to the species of interest. The measurements were conducted using IR femtosecond laser irradiation focused on the sample surface to a spot size of ~12 μm. Material removal was conducted for a predefined number of laser shots, and time-of-flight mass spectra were recorded for each of the ablated layers. Measurements were conducted on NIST SRM 986 Ni isotope standard, trevorite mineral, and micrometer-sized inclusions embedded in aragonite. Our measurements demonstrate that element isotope ratios can be measured with accuracies and precision at the permille level, exemplified by the analysis of B, Mg, and Ni element isotopes. The method applied will be used for in situ investigation of samples on planetary surfaces, for accurate quantification of element fractionation induced by, for example, past or present life or by geochemical processes.

Development of Fast Sampling and High Recovery Extraction Method for Stable Isotope Measurement of Gaseous Mercury

A method involving fast large-volume sampling and bag extraction of total gaseous mercury (TGM) using a 5 mL acid solution was developed for stable mercury isotope ratio measurements. A big gold-coated sand trap (BAuT)—a 45 (i.d.) × 300 mm (length) quartz tube with 131 times more trapping material than a conventional gold trap—was used for the collection of a large amount of TGM. The collected TGM was extracted using 5 mL inversed aqua regia in a 2 L Tedlar bag followed by isotope measurements using a cold vapor generator coupled with a multicollector inductively coupled plasma mass spectrometer. Sampling tests demonstrated that the collection efficiency of the BAuT was 99.9% or higher during the 1–24 h sampling period under the flow rate of 20–100 L min−1. Recovery tests of 24 h bag extraction using 100 ng NIST SRM 8610 exhibited nearly 100% recovery yields. The five measured stable mercury isotope ratios agreed with reference values within 2σ intervals. The overall methodology tested during the pilot field and laboratory studies demonstrated its successful application in analysis, promising highly precise stable mercury isotopic data with a time resolution of less than 24 h.

Non‐Matrix‐Matched Determination of Th‐Pb Ages in Zircon, Monazite and Xenotime by Laser Ablation‐Inductively Coupled Plasma‐Mass Spectrometry

Similar to the U‐Pb system, the 232Th‐208Pb decay scheme is also widely utilised in geochronology of Th‐rich accessory minerals. The matrix‐dependent systemic deviations observed between different accessory minerals and the paucity of well‐characterised reference materials for some minerals of interest (e.g., xenotime and allanite) are the major obstacles to yield accurate and precise Th‐Pb ages with laser ablation‐inductively coupled plasma‐mass spectrometry (LA‐ICP‐MS). In this study, we investigated the effects of the addition of nitrogen, oxygen and water vapour before the ablation cell on the accuracy of Th‐Pb dating of accessory minerals (i.e., zircon, monazite and xenotime) using NIST SRM 610 glass as the calibrating reference material. Our results demonstrate that the measured 208Pb/232Th ages in zircon, monazite and xenotime were approximately 9–24% lower than their isotope dilution thermal ionisation mass spectrometry (ID‐TIMS) ages in normal ablation (without addition of additional gases). The measured 208Pb/232Th ages of zircon (Plešovice, M257 and Qinghu), monazite (44069 and Trebilcock) and xenotime (BS‐1 and MG‐1) showed excellent agreement with their respective reference values with the addition of small amounts of water vapour before the ablation cell. This may be due to the dramatically reduced biases for the down‐hole fractionation of Pb/Th intensity ratios in NIST SRM 610 and accessory minerals in the presence of water vapour. The Th‐Pb ages of zircon, monazite and xenotime were successfully analysed using NIST SRM 610 glass as the calibrating reference material with both 193 nm ArF excimer laser ablation‐quadrupole‐inductively coupled plasma‐mass spectrometry (LA‐Q‐ICP‐MS) and 213 nm Nd:YAG laser ablation‐sector field‐inductively coupled plasma‐mass spectrometry (LA‐SF‐ICP‐MS) in combination with the developed water vapour‐assisted method. This method is an effective and notably simple approach for non‐matrix‐matched analysis of Th‐Pb ages in zircon, monazite and xenotime by LA‐ICP‐MS.

Determination of one year stability of lipid plasma profile and comparison of blood collection tubes using UHPSFC/MS and HILIC-UHPLC/MS

Effects of blood collection tubes, the time period, the sample origin, and the method used on the lipidomic profile are investigated by ultrahigh-performance supercritical fluid chromatography - mass spectrometry (UHPSFC/MS) and hydrophilic interaction liquid chromatography ultrahigh-performance liquid chromatography - mass spectrometry (HILIC-UHPLC/MS). Heparin plasma samples have been obtained from 99 healthy volunteers at three time points separated by six-month intervals together with one collection for EDTA plasma and serum. Furthermore, lipid concentrations in heparin plasma collected at two different sites are compared. 171 lipid species from eight lipid classes are quantified with UHPSFC/MS, and 122 lipid species from four lipid classes with HILIC-UHPLC/MS. The accuracy of both methods is monitored by the quantitation error using two internal standards (IS) per individual lipid classes. No significant differences in lipid profiles are observed for different time points and types of collection tubes (heparin plasma, EDTA plasma, and serum). Most pronounced lipid concentration differences are observed for the comparison of NIST SRM 1950 human plasma and mean lipid concentrations of the investigated cohort. Furthermore, differences in lipid concentrations are observed between employed methods (UHPSFC/MS vs. HILIC-UHPLC/MS), which can be compensated by the normalization using NIST SRM 1950 human plasma used as the quality control sample.

Determination of Total Proteinogenic Amino Acids and Taurine by Pre-column Derivatization and UHPLC: Single Laboratory Validation, First Action Official MethodSM 2019.09.

A method has been developed and validated for selective, accurate, and precise determination of total proteinogenic amino acids and taurine from infant formula and adult/pediatric nutritional formulas (powders, ready-to-feed liquids, and liquid concentrates). The method was reviewed by the AOAC INTERNATIONAL SPIFAN Expert Review Panel (ERP) during the 133rd AOAC Annual Meeting and Expo on September 7, 2019 in Denver, CO, USA, and was recommended to First Action Official MethodsSM status. The method involves protein hydrolysis to amino acids, a simple pre-column derivatization of amino acids and separation of derivatized amino acids by UHPLC. The quantification of amino acids is performed by multi-point calibration using norvaline as the internal standard. The analytical method is capable of quantitative determination for 22 proteinogenic amino acids, but cannot be used to quantitate tryptophan, which is destroyed during the acid hydrolysis step. Asparagine is determined as aspartic acid and glutamine as glutamic acid. Cystine and cysteine are converted to S-2-carboxyethylthiocysteine (CYSx) and the derivative is separated from the other amino acids. Citrulline, which is present in some matrixes, is separated from other amino acids and is not included in the method performance evaluation in the single-laboratory validation (SLV). The proposed method met all the performance requirement limits set in Standard Method Performance Requirement (SMPR®) 2014.013 for total proteinogenic amino acids and taurine. The correlation coefficient of multi-point calibration was not less than 0.999 for any amino acids at any point in the SLV study, confirming the validity of linear dynamic range (LDR) and linearity of the method. The individual amino acids in the chromatogram were identified by absolute retention time and relative retention time (RRT) with respect to the internal standard norvaline. There were no significant (S/N <10) interferences from the reagents or byproducts of derivatization and targeted matrixes. The method demonstrated high selectivity. Accuracy of the method was validated using standard reference materials (SRMs; NIST SRM 1869 and 1849a) and spike recovery studies. The amino acid results in the SRMs were within the ranges of Reference Mass Fraction Values. The accuracy of the method was corroboratively validated by spike recovery studies. The average spike recovery ranged between 93 and 107% ensuring the accuracy of the method for amino acids and compliance with AOAC SMPR 2014.013. Precision data of the method demonstrate that it meets the stakeholder requirements as per the SMPR. The mean RSDr for all the amino acids for 17 matrixes selected for the SLV were not more than 4%. The method is very sensitive and the LOQ can go down to approximately ten times lower than the SMPR requirements. The sensitivity of method is a direct reflection of its signal-to-noise ratio which ensures guaranteed method performance at the lower levels of amino acids in these matrixes. Taurine (aminoethane sulfonic acid), unlike the other amino acids, is a beta-sulfonic amino acid that is not used in protein synthesis but is found as a free amino acid in tissues. The acidic functional group (-COOH) in common amino acids is replaced with a sulfonic acid (-SO3H) group in taurine. The method offers baseline separation of citrulline which is an alpha amino acid generally present in infant formula and adult/pediatric nutritional products. The separation of citrulline eliminates the risk of interference of this compound with other amino acids. The method can also separate and quantitate hydroxyproline, an important component of collagen that is often used to quantitate collagen. The method is simple and does not include any proprietary chemicals or instruments, and it can be performed on any basic reverse phase UHPLC system with UV detection (1-6).

Development of a combined strategy for accurate lipid structural identification and quantification in ion-mobility mass spectrometry based untargeted lipidomics

Lipids are an important class of biomolecules, and play many essential functions in biology. Ion mobility-mass spectrometry (IM-MS) has emerged as a promising technology for lipidomics by providing a holistic and multi-dimensional characterization of lipid structures. However, the lipid identification using the multi-dimensional match (i.e., MS1, retention time, collision cross section, and MS/MS spectra) gives multiple lipid candidates, and often over-reports the structural information. Here, we developed a lipid identification strategy that integrated library-based match and rule-based refinement for accurate lipid structural elucidation in IM-MS based lipidomics. The new strategy took the advantage of multi-dimensional information for high-coverage identification, while it also utilized the fragmentation rules to determine the accurate structural information. We demonstrated that the combined strategy accurately determined the lipid structures as lipid species level, fatty acyl level, or fatty acyl position level for different lipid classes in the lipid standard mixture and various biological samples. The combined strategy efficiently reduced the redundancy and improved the accuracy for different lipid classes, and identified a total of 440–960 lipid species in various biological samples. Finally, we performed quantitative lipidomics analysis of NIST SRM 1950 human plasma using IM-MS technology. The measured concentrations of most quantified lipids (>80%) were highly consistent with values reported from other independent laboratories. In summary, the developed lipid identification strategy allowed for the accurate identification of lipid structures, and facilitated accurate lipid quantification in IM-MS based untargeted lipidomics.

Nontargeted lipidomics of novel human plasma reference materials: hypertriglyceridemic, diabetic, and African-American.

The unavailability of appropriate quality assurance/quality control materials in many lipidomics applications poses a significant challenge for lipidomics research. It is recommended that samples with certified values and/or consensus estimates, such as NIST SRM 1950-Metabolites in Frozen Human Plasma, be implemented in routine analyses to enable community-wide comparisons of lipidomics results and analytical workflows. Herein, we applied a nontargeted lipidomics method for the analysis of a new human plasma reference material suite developed by NIST (hypertriglyceridemic, diabetic, and African-American plasma pools), in addition to SRM 1950. We identified specific lipidomics fingerprints associated with each sample type, including lauric acid-containing lipids and elevated triacylglycerol levels in hypertriglyceridemic plasma, palmitoleic acid-containing lipids in diabetic plasma, and oxidized fatty acid-containing phospholipids in African-American plasma. This work highlights the importance of developing and profiling application-specific reference materials, while establishing reference data that may be used for system suitability and/or quality control metrics.Graphical abstract.

Determination of the tungsten isotope composition in seawater: The first vertical profile from the western North Pacific Ocean

The stable isotope ratio of W is a new tracer in oceanographic studies and a new proxy in paleoceanographic studies; however, precise data for modern seawater have not been reported to date. Because the concentration of W in seawater is as low as 49 pmol kg−1, an ~3000-fold preconcentration is necessary prior to measurement by multicollector inductivity coupled plasma mass spectrometry (MC-ICP-MS). For the preconcentration, we investigated solid-phase extraction using chelating resins, namely, NOBIAS Chelate-PA1 with ethylenediaminetriacetic acid groups and TSK-8HQ with 8-hydroxyquinolie groups. We report that TSK-8HQ is useful because the effects of the seawater matrix are minor thermodynamically and kinetically. We present a novel method for analysis of the concentrations and isotope ratios of W and Mo in seawater, consisting of solid phase extraction, chromatographic separation using anion exchange resin AG1 X8, and measurement by MC-ICP-MS. Both W and Mo are quantitatively recovered by this method, which was applied to seawater samples collected from the North Pacific Ocean. The measured concentration of W and the concentration and isotope ratio of Mo are consistent with those in the literature. The isotope ratio of W is found to be uniform throughout the water column in the western North Pacific Ocean; δ186/184W is 0.55 ± 0.12‰ (ave ± 2sd, n = 7) using NIST SRM 3163 as a reference for W. On the basis of this data, we determined that the isotopic difference in δ186/184W is ~0.49‰ between seawater and oxic sediments in the modern ocean. This value accords with the reported experimental data for the isotope fractionation of W during adsorption on manganese and iron (oxyhydr)oxides, suggesting the validity of our data.

Sr isotopes in arcs revisited: tracking slab dehydration using δ88/86Sr and 87Sr/86Sr systematics of arc lavas

Dehydration of the subducting slab is a crucial process in the generation of hydrous convergent margin magmas, yet the exact processes of how and where the slab dehydrates and how these fluids are transported to the mantle wedge remain obscure. Strontium is a “fluid-mobile” element and as such well suited to investigate the source of slab-derived fluids. We employ mass-dependent Sr isotope systematics (δ88/86Sr; the deviation in 88Sr/86Sr of a sample relative to NIST SRM 987) of primitive arc lavas, in tandem with conventional radiogenic 87Sr/86Sr measurements, as a novel tracer of slab dehydration.To characterise the δ88/86Sr composition of subduction zone inputs, we present new δ88/86Sr data for subducting sediments, altered oceanic crust and MORB. Calcareous sediments are isotopically lighter and carbonate-free sediments are isotopically heavier than mid-ocean ridge basalts (MORB). Samples of the altered oceanic crust display elevated 87Sr/86Sr but only the most intensely altered sample has significantly higher δ88/86Sr than pristine MORB. Mafic arc lavas from the Aegean and Mariana arc invariably have a mass-dependent Sr isotope composition that is indistinguishable from MORB and lower 87Sr/86Sr than upper altered oceanic crust. This δ88/86Sr-87Sr/86Sr signature of the arc lavas, in combination with their high but variable Sr/Nd, can only be explained if it is provided by a fluid that acquired its Sr isotope signature in the deeper, less altered part of the subducted oceanic crust. We propose a model where the breakdown of serpentinite in the slab mantle releases a pulse of fluid at sub-arc depths. These fluids travel through and equilibrate with the overlying oceanic crust and induce wet partial melting of the upper altered crust and sediments. This hydrous melt is then delivered to the mantle source of arc magmas as a single metasomatic component.From mass balance it follows that the slab-derived fluid contributes >70% of the Sr budget of both Mariana and Aegean arc lavas. Whereas this fluid-dominated character is unsurprising for the sediment-poor Mariana arc, the Aegean arc sees the subduction of 3–6 km of calcareous sediments that were found to exert very little control on the Sr budget of the arc magmas and are overwhelmed by the fluid contribution.

Influence of sample surface topography on laser ablation process

In this work we discuss how sample surface topography can significantly influence the laser ablation (LA) process and, in turn, the analytical response of the LA Inductively Coupled Plasma Mass Spectrometry (LA-ICP-MS) method. Six different surface topographies were prepared on a certified aluminium alloy sample BAM 311 and SRM NIST 610 to investigate the phenomenon. All the samples were repetitively measured by LA-ICP-MS using a spot by spot analysis. The effect of laser fluence in the range of 1–13 J/cm2 was studied. For majority of measured isotopes, the ICP-MS signal was amplified with roughening of the sample surface. A stronger effect was observed on the Al alloy sample, where the more than sixty-time enhancement was achieved in comparison to the polished surface of the sample. Since the effect of surface topography is different for each analyte, it can be stated that surface properties affect not only the ICP-MS response, but also elemental fractionation in LA. The presented results show that different surface topographies may lead to misleading data interpretation because even when applying ablation preshots, the signal of individual elements changes. The utmost care must be taken when preparing the surface for single shot analysis or chemical mapping. On the other hand, by roughening the sample surface, it is possible to significantly increase the sensitivity of the method for individual analytes and supress a matrix effect.

Utilizing a Nanocomposite Based on Ion-Imprinted Polydopamine-Coated Magnetic Graphene Oxide for Extraction of Cd(II) and Ni(II) from Water Samples

In this study, a new magnetic ion-imprinted polymer was prepared as a nanosorbent for selective extraction and pre-concentration of low levels of Cd(II) and Ni(II) prior to determination by flame atomic absorption spectrometry. The sorbent material consists of graphene oxide as a carrier, Fe3O4 nanoparticles as magnetic components immobilized on the surface of the carrier and polydopamine as a metal ion-imprinted polymer which is uniformly coated on the surface of the magnetic graphene oxide sheet layer. Several factors affecting the extraction of the analytes were studied and optimized. In the optimum conditions, the calibration graphs were linear in the ranges of 0.1–18 and 0.1–20 ng/mL for Cd(II) and Ni(II), respectively. The limits of detection (3sb/m) for Cd(II) and Ni(II) were 25 and 60 pg/mL, respectively. The accuracy of the method was confirmed by successful analyzing the certified reference material NIST SRM 1643e. The method can be used for the pre-concentration and determination of Ni(II) and Cd(II) in water samples.

Determination of the Isotopic Composition of an Enriched Hafnium Spike by MC‐ICP‐MS Using a Regression Model

The isotope dilution (ID) method, owing to its high precision, is extensively used for the determination of element mass fractions in a wide range of natural samples. One of the prerequisites of the ID method is knowledge of the isotopic composition of an enriched spike, which is often challenging to accurately determine. In this study, we employ a regression mass bias correction model to accurately and precisely measure the isotopic composition of an enriched Hf spike (Lot No. 159293, Oak Ridge National Laboratory). A NIST SRM 3134 Re solution, whose isotopic composition was calibrated by an NRC IRIS‐1 Ir isotope standard, was used to calibrate the isotopic composition of the Hf spike. The obtained ratios of 176Hf/177Hf, 179Hf/177Hf and 180Hf/177Hf were 0.2406 ± 0.0005 (u, k = 1), 2.8620 ± 0.0005 (u, k = 1) and 384.65 ± 0.05 (u, k = 1), respectively, which meet the required precision levels for Hf isotopes in the application of the ID method. The combined uncertainties of the calibrated Re and Hf isotope ratios were evaluated using a Monte Carlo method, in which the uncertainty of the primary calibrator (IRIS‐1, 193Ir/191Ir = 1.6866 ± 0.0005, u, k = 1) was also taken into consideration. The precision of Hf spike was improved significantly compared with the SSB and C‐SSBIN methods. To the best of our knowledge, this is the first report of isotope ratio calibration in an enriched spike using the regression model. The precisely calibrated spike can lower the uncertainty of the Hf mass fraction significantly, thereby increasing the accuracy of the Lu‐Hf chronometer.

Effect of Fe–Ti oxides on Mo isotopic variations in lateritic weathering profiles of basalt

This study aimed to improve our understanding of processes fractionating Mo isotopic compositions during extreme weathering of basalt and to identify a long-term surface reservoir for light δ98Mo signatures, which are key to constraining the isotopic composition of riverine inputs to the oceans. A lateritic weathering profile of basalt from Hainan Island, South China, was studied by determining bulk δ98Mo values as well as δ98Mo values of extracted Fe–Mn (hydro) oxides and residual phases, and parent-rock minerals. δ98Mo values relative to NIST SRM 3134 = +0.25‰ in the lateritic weathering profile were in the ranges of −0.28‰ to +0.48‰, with the δ98Mo values of the upper and middle sections being heavier, and those of the lower section lighter than that of the parent basalt. Rainwater input and changing redox conditions are likely to be the essential factors controlling variations in bulk δ98Mo values in the upper and middle sections, respectively, resulting in their heavier δ98Mo values. In contrast, the lighter values in lower section are likely due to the leaching of primary minerals (e.g., pyroxene and plagioclase) with some heavier δ98Mo being released to aqueous media. The Fe–Mn (hydro) oxides phase in the sequential extraction procedure is thus characterized by heavy δ98Mo values in the lateritic weathering profile, which may be responsible for heavy Mo isotopic composition in bulk samples. Light δ98Mo signatures are preserved in the residual phase, where Mo hosted in Fe–Ti oxides is inherited mainly from parent basalt rock, possibly accounting for light Mo isotopic composition in bulk samples. Owing to their high resistance to weathering and chemical erosion, Fe–Ti oxides might be a potential long-term surface reservoir for light δ98Mo signatures. The difference in degrees of Mo isotopic fractionation between basalt and granite lateritic weathering profiles may reflect variations in Mo behavior in parent-rock host minerals during weathering. The results elucidate mechanisms of Mo isotopic fractionation during chemical weathering and improve understanding of the riverine input of Mo isotopes to oceans.

ELEMENTAL CHARACTERIZATION OF COAL FLY ASH BY NEUTRON ACTIVATION ANALYSIS TOWARDS REFERENCE MATERIAL CERTIFICATION

&lt;p&gt;Coal combustion by-products, such as coal fly ash, has known as a significant source of potentially toxic elements that may affect the environment since the increase of coal utilization as power fuel in Indonesia. Issuing the policies to protect the environment and public health is often based on analytical results. The quality of data analysis is very important since many crucial policies related to public health and environmental protections are based on the analytical results. Considering the need for reference material in ensuring the validity and reliability of the analytical results, reference material candidate of coal fly ash is being developed. Elemental characterization as one of the important parts in certifying the reference material is carried out using Neutron Activation Analysis (NAA) since it considered as high accuracy analytical method and commonly used to certified many reference materials throughout the world. Our NAA facility performance was assessed through optimizing analytical conditions by varying samples weight, method validation, and comparison test with other techniques as well. As much as 25, 100, and 250 mg of sample weight were assessed for its homogeneity effect. Method validation using SRM NIST 1633b had shown good results with bias not more than 10% compared to its certificate values. A comparison test with other results also showed a great agreement.&lt;/p&gt;&lt;p&gt; &lt;/p&gt;

Cadmium isotopic composition of biogenic certified reference materials determined by thermal ionization mass spectrometry with double spike correction

A116Cd–106Cd double‐spike method in combination with thermal ionization mass spectrometry (TIMS) was applied to obtain cadmium (Cd) mass fractions and stable isotope compositions in seven biogenic certified reference materials (pine needles, tomato leaves, spinach leaves, lichen, mussel tissue, oyster tissue, and pig kidney). This sample set was supplemented by the analysis of two manganese nodules and one soil reference material for which the Cd isotopic data has already been reported. The intermediate measurement precision of the whole protocol as determined for the NIST SRM 3108 Cd standard solution yields an excellent value of δ114/110Cd of −0.005 ± 0.029‰ (2SD, n = 47). The Cd isotopic compositions of the biogenic materials, reported as δ114/110Cd relative to NIST SRM 3108, range from −0.52 to +0.50‰. Plants show δ114/110Cd mean values ranging from −0.09 to +0.45‰ whereas the δ114/110Cd value of −0.17‰ was detected in the lichen and the values of −0.51, −0.52, and +0.47‰ were gathered for the oyster, mussel, and pig kidney tissues, respectively. The observed large variation of the δ114/110Cd values in the biogenic reference materials indicates a potential to use the natural mass-dependent Cd isotope fractionation in environmental, biogeochemical, and physiological studies.

Calcium fluoride as a dominating matrix for quantitative analysis by laser ablation-inductively coupled plasma-mass spectrometry (LA-ICP-MS): A feasibility study

Calcium fluoride formed by the reaction between ammonium bifluoride and calcium chloride was investigated as a dominating matrix for quantitative analysis by laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS). Transformation from a solid sample to the calcium fluoride-based matrix permitted quantitative analysis based on calibration standards made from elemental standards. A low abundance stable calcium isotope, i.e. 44Ca+, was monitored as the internal standard for quantitative analysis by LA-ICP-MS. Correlation coefficient factors for multiple elements were obtained with values over 0.999. The results for multiple elements in a certified reference material of soil (NIST SRM 2710a) agreed with the certified values in the range of expanded uncertainty, indicating the present method was valid for quantitation of elements in solid samples.

Chemical footprints of harmattan dust and traffic corridor particulates monitored at two environmentally distinct geopolitical zones in Nigeria.

Harmattan dust and traffic-related pollution have been a serious environmental concern in the West African sub-region. In order to further contribute to the understanding of ambient levels of atmospheric pollution and chemical composition in the region, this study monitored harmattan dust and traffic-related particulate matter at four locations across southwestern (Ile-Ife) and north-western (Zaria) geo-political zones of Nigeria. The collected samples were characterized for their chemical composition using Energy-Dispersive X-Ray Fluorescence spectrometer equipped with an optimized secondary target x-ray excitation conditions (Al, CaF2, Fe, Ge, Zr, Mo, Ag, Al2O3). The objectives are to assess spatio-temporal mass concentrations, chemical footprints, enrichment factors, elemental correlations, and ratios at all locations. The X-ray analytical method was validated with a NIST SRM 2783 air particulate standard, and detection limits for each chemical specie were determined. Validation results showed good reproducibility of the certified reference material with relative standard deviations of the elements much lower by about 1-13% than the corresponding reference values. Mass concentrations reached up to 2200μgm-3 in the north and 1500μgm-3 in the south. The range of mean concentration of crustal marker elements were Al (5-27μgm-3), Si (5-856μgm-3), Ca (0.78-13μgm-3), and Fe (2-13μgm-3), and were most abundant during the harmattan particularly in the southwestern region. Highest mean concentration values of 380, 810, and 420ngm-3 were recorded for Cr, Cu, and Pb respectively at the traffic corridor which also recorded the highest enrichment factors. Black carbon and elemental concentrations contributed between 1 to 54% and 9 to 94% across the locations respectively. Backward trajectories of atmospheric flow over the locations showed two dominant sources; dust laden source from the Sahara desert and maritime flow over the Gulf of Guinea. This study found that chemical footprints (Al, Si, K, Ca, Ti, and Fe) of harmattan-related dust were more correlated (r2 between 0.88 and 0.99) than those attributed to dust re-suspension at the traffic location.