Contamination, speciation, and health risk assessment of arsenic in leafy vegetables in Ambagarh Chowki (India).

Green leafy vegetables are essential for a balanced diet, providing vital nutrients for overall well-being. However, concerns arise due to contamination with toxic substances, such as arsenic, posing risks to food safety and human health. This study analyzes inorganic (iAs), monomethyl (MMA), and dimethyl arsenic (DMA) in specific leafy vegetables (Amaranthus tricolor L., Corchorus olitorius L., Cordia myxa L., Hibiscus sabdariffa L., Ipomoea batatas (L.) Lam., Moringa oleifera Lam., and Spinacia oleracea L.) grown in the heavily polluted Ambagarh Chouki region, Chhattisgarh, India. Concentrations of DMA, MMA, and iAs ranged from 0 to 155, 0 to 7, and 131 to 3579 mg·kg-1, respectively. The health quotient (HQ) for iAs ranged between 0.37 and 3.78, with an average value of 2.58 ± 1.08.

On-line generated ozone as a reactive cell gas for tandem quadrupole inductively coupled plasma mass spectrometry.

On-line generated ozone was introduced as the cell gas of tandem quadrupole inductively coupled plasma mass spectrometry. Product ions of the ozone reaction showed that the formation of singly charged monoxide ions and dioxide ions was apparently improved for most elements, resulting in maximum improvement of the signal intensity by over 1000 times.

A review on arsenic in the environment: bio-accumulation, remediation, and disposal.

Arsenic is a widespread serious environmental pollutant as a food chain contaminant and non-threshold carcinogen. Arsenic transfer through the crops-soil-water system and animals is one of the most important pathways of human exposure and a measure of phytoremediation. Exposure occurs primarily from the consumption of contaminated water and foods. Various chemical technologies are utilized for As removal from contaminated water and soil, but they are very costly and difficult for large-scale cleaning of water and soil. In contrast, phytoremediation utilizes green plants to remove As from a contaminated environment. A large number of terrestrial and aquatic weed flora have been identified so far for their hyper metal removal capacity. In the panorama presented herein, the latest state of the art on methods of bioaccumulation, transfer mechanism of As through plants and animals, and remediation that encompass the use of physicochemical and biological processes, i.e., microbes, mosses, lichens, ferns, algae, and macrophytes have been assessed. Since these bioremediation approaches for the clean-up of this contaminant are still at the initial experimental stages, some have not been recognized at full scale. Nonetheless, extensive research on these primitive plants as bio-accumulators can be instrumental in controlling arsenic exposure and rehabilitation and may result in major progress to solve the problem on a worldwide scale.

A review on arsenic in the environment: contamination, mobility, sources, and exposure.

Arsenic is one of the regulated hazard materials in the environment and a persistent pollutant creating environmental, agricultural and health issues and posing a serious risk to humans. In the present review, sources and mobility of As in various compartments of the environment (air, water, soil and sediment) around the World are comprehensively investigated, along with measures of health hazards. Multiple atomic spectrometric approaches have been applied for total and speciation analysis of As chemical species. The LoD values are basically under 1 µg L-1, which is sufficient for the analysis of As or its chemical species in environmental samples. Both natural and anthropogenic sources contributed to As in air, while fine particulate matter tends to have higher concentrations of arsenic and results in high concentrations of As up to a maximum of 1660 ng m-3 in urban areas. Sources for As in natural waters (as dissolved or in particulate form) can be attributed to natural deposits, agricultural and industrial effluents, for which the maximum concentration of 2000 µg L-1 was found in groundwater. Sources for As in soil can be the initial contents, fossil fuel burning products, industrial effluents, pesticides, and so on, with a maximum reported concentration up to 4600 mg kg-1. Sources for As in sediments can be attributed to their reservoirs, with a maximum reported concentration up to 2500 mg kg-1. It is notable that some reported concentrations of As in the environment are several times higher than permissible limits. However, many aspects of arsenic environmental chemistry including contamination of the environment, quantification, mobility, removal and health hazards are still unclear.

Determination of Rare Earth Elements by Inductively Coupled Plasma-Tandem Quadrupole Mass Spectrometry With Nitrous Oxide as the Reaction Gas.

Nitrous oxide (N2O) was investigated as the reaction gas for the determination of rare earth elements (REEs) by inductively coupled plasma-tandem quadrupole mass spectrometry (ICP-QMS/QMS). The use of N2O as the reaction gas apparently improved the yields of m M16O+ for Eu and Yb in the reaction cell. As a result, the sensitivities for measurement of Eu and Yb were apparently improved in comparison to those obtained with O2 as the reaction gas. A high sensitivity measurement of the whole set of REEs was achieved, providing a typical sensitivity of 300,000 CPS mL/ng for REEs measured with an isotope having isotopic abundance close to 100%. The use of N2O as the reaction gas helped suppress Ba-related spectral interferences with the measurement of Eu, permitting the measurement of Eu in a natural sample without mathematic correction of spectral interferences. The detection limits (unit, pg/mL) for 14 REEs (except for Pm) from La to Lu were 0.028, 0.018, 0.006, 0.026, 0.006, 0.010, 0.017, 0.006, 0.016, 0.010, 0.016, 0.004, 0.023, and 0.012, respectively. The validity of the present method was confirmed by determining REEs in river water-certified reference materials, namely, SLRS-3 and SLRS-4.

Pseudo isotope dilution (PID) as an approach for correcting barium-related spectral interferences on the measurement of europium by inductively coupled plasma mass spectrometry (ICP-MS).

Pseudo isotope dilution (PID) was suggested as a simple and practical approach for the correction of barium-related spectral interferences on the measurement of europium by inductively coupled plasma mass spectrometry (ICP-MS). The interferents, i.e. oxides and hydroxides of barium, were regarded as pseudo europium isotopes. An equation for calculating the concentration of europium was deduced and the net contribution of europium isotopes can be obtained by measuring the signal intensity ratios of 151I/153I in a sample, a europium standard, and a barium standard, respectively. The validity of the approach was confirmed by the determination of europium in standard solutions with different concentrations of barium. Determination of europium in river water and seawater certified reference materials was carried out, whose results were in coincidence with reference values.

Potential Anthropogenic Pollution of High-technology Metals with a Focus on Rare Earth Elements in Environmental Water.

In recent years, the utilization of high-technology metals such as rare earth elements (REEs), which exist in extremely low quantities in the Earth, has rapidly increased with the development of new types of industrial materials and pharmaceutical products. This review provides an overview of a new type of potential anthropogenic pollution caused by high-technology metals, with a focus on REEs released into environmental waters from waste treatment plants. In this paper, potential anthropogenic pollution was defined as pollution caused by metals gradually enriched in the environment by human activity, although standard and guideline concentrations of these elements are not regulated by environmental quality standards for water pollution. We review the analytical methods of REEs and the potential anthropogenic pollution of REEs with a focus on Gd, from the viewpoints of a comparison of the degree of Gd anomaly, chemical speciation, ecotoxicology, and bioaccessibility. Moreover, we also highlight the comprehensive analysis based on multielement analysis of high-technology metals as well as REEs for the further screening for potential anthropogenic pollution.

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.

Development of an Automatic pH Adjustment Instrument for the Preparation of Analytical Samples Prior to Solid Phase Extraction.

An automatic pH adjustment instrument was developed for the preparation of analytical samples prior to solid phase extraction, which is widely used as a pretreatment technique for the separation of sample matrixes and preconcentration of elements for analysis. Real-time monitoring of the sample pH condition was performed by observing the light signal intensity of the pH-sensitive wavelength of the pH indicating reagent. A light of pH-insensitive wavelength was selected as the reference light to cancel the signal intensity variation of the pH-sensitive light due to the difference of pH indicating reagent concentration, possible difference in transparency of sample vessels, and minute fluctuation of the light source. The pH condition was elevated by automatic addition of ammonia solution using a nebulizer in the flow line of which an electromagnetic valve was equipped. Open and close operation of the electromagnetic valve was controlled based on the difference between the real-time pH condition and the target pH condition. The effectiveness of the instrument was confirmed by using various pH indicating reagents and by analyzing trace elements in a seawater certified reference material.

Determination of rare earth elements in seawater samples by inductively coupled plasma tandem quadrupole mass spectrometry after coprecipitation with magnesium hydroxide.

Coprecipitation with magnesium hydroxide was investigated as a pretreatment method for the determination of rare earth elements (REEs) in seawater samples, both for separation of the salt contents and for the enrichment of REEs. The precipitate of magnesium hydroxide was collected on a syringe filter and then subjected to the on-line measurement of REEs by an inductively coupled plasma tandem quadrupole mass spectrometer (ICP-MS/MS). Coprecipitation resulted in a separating rate of over 99% for salt contents, while the on-line measurement of REEs in the magnesium hydroxide provided an enhancement factor of 130-fold for the transient peak height of signal intensities. Mass-shift mode was applied to the measurement of REEs by ICP-MS/MS, where each isotope of the REEs was permitted to pass the first QMS and to react with oxygen gas in the reaction cell so as to form a monoxide ion, which was permitted to pass the second QMS and then measured by the detector. Mass-shift to monoxide ion effectively removed the spectral interferences in the measurement of REEs and permitted the correct determination of REEs in seawater samples. Detection limits were calculated based on the results of 10-set of the replicated blank test, which were low enough for the determination of REEs in natural seawater samples. The effectiveness of the present method was confirmed by the analysis of three certified reference materials of seawater, i.e. CASS-4, CASS-5, and NASS-6.

Automatic Preparation of Calibrating Solutions for Quantitative Analysis by ICP-MS.

An automatic system was developed to prepare calibrating solutions for elemental measurements by inductively coupled plasma mass spectrometry (ICP-MS). The flow-rates of diluting solution, internal standard solution, and initial elementals solution were monitored with a single ultrasonic flow sensor. Multiple calibrating solutions prepared by the present automatic system were analyzed by ICP-MS, whose results provided a correlation coefficient better than 0.999 for calibration curves. The results for multi-elements in a river-water certified reference material (NMIJ CRM 7202-b) agreed with the certified values.

Determination of Rubidium by ID-ICP-QMS/QMS with Fluoromethane as the Reaction Cell Gas to Separate Spectral Interference from Strontium.

A determination of rubidium (Rb) was carried out by isotope dilution (ID) using an inductively coupled plasma tandem quadrupole mass spectrometer (ICP-QMS/QMS) with an octupole reaction-cell (ORC). Spectral interference of 87Sr with the measurement of 87Rb was effectively removed by using fluoromethane (CH3F) as the reaction cell gas at the optimum flow rate. In comparison to the measurement obtained with a mathematical correction, good precision for the analysis of the Rb isotope could be obtained independent of the concentration of Sr without any chemical separation in advance. The usefulness of the present approach was confirmed by an analysis of Rb in multiple certified reference materials (CRMs) for food and environmental analysis, for which the results agreed with their certified values in the range of expanded uncertainty.

Quantitative Analysis of Major and Minor Elements in Lead-free Solder Chip by LA-ICP-MS.

A method was established for the quantitative analysis of the elements (Cu, Ag, Pb, and Sn) in solder samples by laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS), with Sn-based matrix matched standard solutions for defining the calibration curves. It was found that chloride-ion presented in commercially available Sn standard solution resulted in a precipitation of AgCl and caused the deterioration of the linearity of the calibration curve for Ag. Therefore, a laboratory-made chloride-free Sn solution was used to prepare Sn matrix matched standard solutions so as to ensure the stability of the elements including Ag. For the quantitative analysis of solder samples by LA-ICP-MS, the operating conditions of the LA instruments were set to obtain a fluence of over 12 J cm-2. This is mainly because of larger LA-induced elemental fractionations using a fluence of <10 J cm-2. The results for Ag, Cu, Pb, and Sn in a certified reference material (NMIJ CRM 8203-a) were close to, or in agreement with, the certified values, indicating that the present method was valid for the quantitative analysis of the elements in solder samples. In comparison to the certified values, relatively larger uncertainties were obtained for the analytical results by LA-ICP-MS, which could be attributed to the dependence on the homogeneity of the sample because the sample aliquots used for analysis were much smaller than those required for the traditional analytical procedures (i.e., sample quantity ratio of ca. 1:13000). Further improvement of the uncertainty might be obtained by using a larger sample quantity for the analysis by LA-ICP-MS so as to improve the representativeness of the sample.

Applications and Uncertainty Estimation of Single Level Standard Addition Method ICP-MS for Elemental Analysis in Various Matrix.

The standard addition method (SAM) based on gravimetric sample preparation was investigated as an approach for the removal or cancelling of matrix effects in measurements by inductively coupled plasma mass spectrometry (ICP-MS). Deduction of the equations and experimental confirmation of the method are both given in the present work. After measuring both spiked and non-spiked samples by ICP-MS, the concentration of an element could be calculated based on the signal intensity ratio to an internal standard. A practical example was provided for the measurement of Fe in a certified reference material (CRM), i.e. NMIJ CRM 7512-a (milk powder). The validity of the method had been confirmed by the results of international comparisons with various kinds of matrix, including bioethanol, human serum, biodiesel fuel, drinking water, infant formula milk power, and seafood. The suggested method had been applied to measurements of multiple elements in three CRMs, including tap water, milk powder, and tea leave powder, respectively.

Quantification of elemental area densities in multiple metal layers (Au/Ni/Cu) on a Cr-coated quartz glass substrate for certification of NMIJ CRM 5208-a.

Area densities of Au/Ni/Cu layers on a Cr-coated quartz substrate were characterized to certify a multiple-metal-layer certified reference material (NMIJ CRM5208-a) that is intended for use in the analysis of the layer area density and the thickness by an X-ray fluorescence spectrometer. The area densities of Au/Ni/Cu layers were calculated from layer mass amounts and area. The layer mass amounts were determined by using wet chemical analyses, namely inductively coupled plasma mass spectrometry (ICP-MS), isotope-dilution (ID-) ICP-MS, and inductively coupled plasma optical emission spectrometry (ICP-OES) after dissolving the layers with diluted mixture of HCl and HNO3 (1:1, v/v). Analytical results of the layer mass amounts obtained by the methods agreed well with each another within their uncertainty ranges. The area of the layer was determined by using a high-resolution optical scanner calibrated by Japan Calibration Service System (JCSS) standard scales. The property values of area density were 1.84 ± 0.05 µg/mm2 for Au, 8.69 ± 0.17 µg/mm2 for Ni, and 8.80 ± 0.14 µg/mm2 for Cu (mean ± expanded uncertainty, coverage factor k = 2). In order to assess the reliability of these values, the density of each metal layer calculated from the property values of the area density and layer thickness measured by using a scanning electron microscope were compared with available literature values and good agreement between the observed values and values obtained in previous studies.

Cation-mixing stabilized layered oxide cathodes for sodium-ion batteries.

Sodium-ion batteries are promising for large-scale energy storage due to sodium's low cost and infinite abundance. The most popular cathodes for sodium-ion batteries, i.e., the layered sodium-containing oxides, usually exhibit reversible host rearrangement between P-type and O-type stacking upon charge/discharge. Herein we demonstrate that such host rearrangement is unfavorable and can be suppressed by introducing transition-metal ions into sodium layers. The electrode with stabilized P3-type stacking delivers superior rate capability, high energy efficiency, and excellent cycling performance. Owing to the cation-mixing nature, it performs the lowest lattice strain among all reported cathodes for sodium-ion batteries. Our findings highlight the significance of a stable host for sodium-ion storage and moreover underline the fundamental distinction in material design strategy between lithium- and sodium-ion batteries.

Analysis of Fluorine in Drinking Water by ICP-QMS/QMS with an Octupole Reaction Cell.

The analysis of fluorine was carried out by measuring BaF+ ions with an inductively coupled plasma tandem quadrupole mass spectrometer (ICP-QMS/QMS). After optimization, a radio frequency power of 1300 W was found to benefit for the production of BaF+ ions while suppressing the production of BaOH3+ ions. After optimization of the reaction cell gas, it was found that the best performance for measuring BaF+ could be achieved at a flow rate of O2 in the range from 0.65 to 0.75 mL min-1. The signal intensity of BaF+ depended linearly on the concentration of Ba when it was not higher than 100 mg kg-1. The co-existence of metallic cations, such as Na in the sample, might suppress the generation of BaF+ ions in the plasma, while anions might not cause such a kind of interferences. The background equivalent concentration (BEC) and the lower detection limit (LDL) of fluorine were 0.4 and 0.06 mg kg-1, respectively, by adjusting the samples to a 10 mg kg-1 Ba matrix. The concentration of fluorine in a certified reference material (ERM-CA015a) was determined with the present method, for which the observed value was (1.36 ± 0.05)mg kg-1, which agreed with the certified value (1.3 ± 0.1)mg kg-1, where both values were shown as (mean value ± expanded uncertainty) with a coverage factor of (k = 2) for calculating the expanded uncertainty giving a level of confidence of approximately 95%. The present method was applied to the analysis of a tap water sample collected in the laboratory, for which the results of recovery tests gave a recovery around 100% with good reproducibility.

Experimental Confirmation of SrF(CH3F)0-4+ and SrF(H2O)(CH3F)0-3+ Cluster Ions Generated in the Reaction-cell of ICP-QMS/QMS.

Multiple unknown high-order cluster ions were observed as the results of ion-molecule reactions between strontium ions and fluoromethane molecules in the reaction-cell of an inductively coupled plasma tandem quadrupole mass spectrometer (ICP-QMS/QMS). In order to elucidate the structures of these unknown cluster ions, isotope-enriched fluoromethane (CD3F) was used as the reaction-cell gas compared to natural fluoromethane (CH3F). As results, SrF(CH3F)0-4+ and SrF(H2O)(CH3F)0-3+ cluster ions were experimentally confirmed in the present work, while SrF(H2O)(CH3F)0-3+ cluster ions in the reaction-cell of ICP-QMS/QMS were observed and confirmed for the first time in the world.