Rapid determination of chromium species in environmental waters using a diol-bonded polymer-stationary column under water-rich conditions coupled with ICPMS.

Chromium speciation analysis in environmental water is of great significance for the monitoring of water pollution and assessing its influences on human health. This study proposes a rapid analytical approach for the simultaneous determination of Cr(VI) and Cr(III) in environmental waters by hydrophilic interaction chromatography (HILIC) coupled with ICPMS under a water-rich condition. 2,6-Pyridinedicarboxylic acid (PDCA) was used to unify Cr(III) species in various chemical forms into a stable Cr(III)-PDCA anion complex and then separated from Cr(VI) oxyanion on a diol-bonded polymer-based HILIC column. An aqueous mobile phase containing 50 mmol L-1 ammonium acetate (pH 7.0), 2 mmol L-1 PDCA, and 4% acetonitrile successfully separates chromium species as well as chloride ions. In addition, our method elutes Cr(VI) preferentially over Cr(III)-PDCA, enabling rapid determination of Cr(VI), and both chromium species were analyzed within 6.2 min. The detection limits of 0.19 µg L-1 for Cr(VI) and 0.35 µg L-1 for Cr(III) at m/z 52 under He collision mode are comparable to or better than the conventional ion exchange chromatography-ICPMS methods, and quantitative recovery was obtained from spike-recovery tests on river water samples containing various levels of matrix. Optimization experiments of the HPLC conditions indicate that the retentions of Cr(VI) and Cr(III)-PDCA are characterized by electrostatic and nonpolar interactions, respectively. The retention behavior of inorganic anions and cations in water-rich conditions observed in this study will provide new insights into the separation mechanism in polymer-based HILIC columns, which has been poorly understood.

Simultaneous and sensitive analysis of glyphosate, glufosinate, and their metabolites in surface water by HPLC-ICP-MS/MS.

Organophosphorus pesticides such as glyphosate and glufosinate are used worldwide, and environmental regulatory values are being adopted in many countries due to their potential toxicity. In the present work, a pretreatment-free analytical method is established in which these two compounds with their metabolites are isolated from each other by anion-exchange HPLC using ammonium acetate (70 mM, pH 3.7) as eluent, and they are detected by triple quadrupole ICP-MS. Very low detection limits of 0.03-0.17 µg L-1 are acquired through the detection of P+ as PO+ via oxygen reaction mode, and quantitative recovery was obtained from the spike-recovery test on river water samples containing phosphate ion as an isobaric interferent. In addition, a constant sensitivity per molar concentration was achieved regardless of the compounds due to the powerful ion source of ICP-MS. This property suggests that semi-quantitative analysis of unknown P-bearing compounds is possible from one calibration curve.

Failure-Experiment-Supported Optimization of Poorly Reproducible Synthetic Conditions for Novel Lanthanide Metal-Organic Frameworks with Two-Dimensional Secondary Building Units.

Invited for the cover of this issue are Daisuke Tanaka at Kwansei Gakuin University and co-workers at Kwansei Gakuin University, Hokkaido University, Kyoto University, Japan and KU Leuven, Belgium. The image is a depiction of exploring the desired crystal by decision tree analysis. Read the full text of the article at 10.1002/chem.202102404.

Failure-Experiment-Supported Optimization of Poorly Reproducible Synthetic Conditions for Novel Lanthanide Metal-Organic Frameworks with Two-Dimensional Secondary Building Units*.

Novel metal-organic frameworks containing lanthanide double-layer-based secondary building units (KGF-3) were synthesized by using machine learning (ML). Isolating pure KGF-3 was challenging, and the synthesis was not reproducible because impurity phases were frequently obtained under the same synthetic conditions. Thus, dominant factors for the synthesis of KGF-3 were identified, and its synthetic conditions were optimized by using two ML techniques. Cluster analysis was used to classify the obtained powder X-ray diffractometry patterns of the products and thus automatically determine whether the experiments were successful. Decision-tree analysis was used to visualize the experimental results, after extracting factors that mainly affected the synthetic reproducibility. Water-adsorption isotherms revealed that KGF-3 possesses unique hydrophilic pores. Impedance measurements demonstrated good proton conductivities (σ=5.2×10-4  S cm-1 for KGF-3(Y)) at a high temperature (363 K) and relative humidity of 95 % RH.

Stable isotopes show that earthquakes enhance permeability and release water from mountains.

Hydrogeological properties can change in response to large crustal earthquakes. In particular, permeability can increase leading to coseismic changes in groundwater level and flow. These processes, however, have not been well-characterized at regional scales because of the lack of datasets to describe water provenances before and after earthquakes. Here we use a large data set of water stable isotope ratios (n = 1150) to show that newly formed rupture systems crosscut surrounding mountain aquifers, leading to water release that causes groundwater levels to rise (~11 m) in down-gradient aquifers after the 2016 Mw 7.0 Kumamoto earthquake. Neither vertical infiltration of soil water nor the upwelling of deep fluids was the major cause of the observed water level rise. As the Kumamoto setting is representative of volcanic aquifer systems at convergent margins where seismotectonic activity is common, our observations and proposed model should apply more broadly.

A Rapid and Precise Determination of Boron Isotope Ratio in Water and Carbonate Samples by Multiple Collector ICP-MS.

We developed a method for rapid and precise determination of B isotope ratios by MC-ICP-MS through an optimization of washout method, mass-discrimination correction and chemical separation. Resultant reproducibility of δ11B values was ±0.4‰ (2 × SD) when a simple standard-sample bracketing technique was used, and it was improved to be better than ±0.2‰ by a mass discrimination correction with a 7Li/6Li isotopic reference. A mixed solution, which consists of HNO3-HF-mannitol, allowed a rapid washout of B memory in the sample introduction line. The validation of this technique to a wide range of δ11B value and various B signal intensities was confirmed from a series of B reference solutions with δ11B values of -20 to +40‰ and 25 to 125 ng/g B. Analyses of seawater standard (BCR-403) and carbonate standard (JCp-1) with sample sizes of less than 50 ng B gave δ11B values consistent with those determined by TIMS as Cs2BO2+. The simple and high-precision technique developed here is applicable to various types of commercially supplied multiple collector ICP mass spectrometers without any modification of the sample introduction system from their original instrumental setting.

A simple and rapid method for isotopic analysis of nickel, copper, and zinc in seawater using chelating extraction and anion exchange.

Stable isotope ratios of nickel, copper, and zinc are powerful tools for elucidating the biogeochemical cycling of trace metals in the ocean. However, analytical difficulties have impeded isotopic studies of these metals. We present a simple and rapid method for simultaneous analysis of Ni, Cu, and Zn isotope ratios in seawater using NOBIAS Chelate-PA1 resin and anion exchange resin. A NOBIAS Chelate-PA1 resin column was used to quantitatively collect Ni, Cu, and Zn from seawater and thoroughly remove the seawater matrix. Subsequent anion exchange purified and separated the Ni, Cu, and Zn from each other. The blanks used in this method (0.22 ng for Ni, 0.29 ng for Cu, and 0.53 ng for Zn) were sufficiently low to determine the isotope ratios of Ni, Cu, and Zn in surface seawater. Using this method, we analyzed GEOTRACES reference seawater samples (i.e., SAFe D1 and SAFe D2), National Research Council Canada certified materials (i.e., CASS-5 and NASS-6), and seawater samples collected from different depths in the subarctic South Pacific. The results were consistent with previously reported values. This method is expected to accelerate isotopic research and contribute to our understanding of biogeochemical cycling in the ocean.

Isotopic constraints on biogeochemical cycling of copper in the ocean.

Trace elements and their isotopes are being actively studied as powerful tracers in the modern ocean and as proxies for the palaeocean. Although distributions and fractionations have been reported for stable isotopes of dissolved Fe, Cu, Zn and Cd in the ocean, the data remain limited and only preliminary explanations have been given. Copper is of great interest because it is either essential or toxic to organisms and because its distribution reflects both biological recycling and scavenging. Here we present new isotopic composition data for dissolved Cu (δ(65)Cu) in seawater and rainwater. The Cu isotopic composition in surface seawater can be explained by the mixing of rain, river and deep seawater. In deep seawater, δ(65)Cu becomes heavier with oceanic circulation because of preferential scavenging of the lighter isotope ((63)Cu). In addition, we constrain the marine biogeochemical cycling of Cu using a new box model based on Cu concentrations and δ(65)Cu.

Identification of sources of lead in the atmosphere by chemical speciation using X-ray absorption near-edge structure (XANES) spectroscopy.

Sources of Pb pollution in the local atmosphere together with Pb species, major ions, and heavy metal concentrations in a size-fractionated aerosol sample from Higashi-Hiroshima (Japan) have been determined by X-ray absorption near-edge structure (XANES) spectroscopy, ion chromatography, and ICP-MS/AES, respectively. About 80% of total Pb was concentrated in fine aerosol particles. Lead species in the coarse aerosol particles were PbC2O4, 2PbCO3 Pb(OH)2, and Pb(NO3)2, whereas Pb species in the fine aerosol particles were PbC2O4, PbSO4, and Pb(NO3)2. Chemical speciation and abundance data suggested that the source of Pb in the fine aerosol particles was different from that of the coarse ones. The dominant sources of Pb in the fine aerosol particles were judged to be fly ash from a municipal solid waste incinerator and heavy oil combustion. For the coarse aerosol particles, road dust was considered to be the main Pb source. In addition to Pb species, elemental concentrations in the aerosols were also determined. The results suggested that Pb species in size-fractionated aerosols can be used to identify the origin of aerosol particles in the atmosphere as an alternative to Pb isotope ratio measurement.

Determination of isotopic composition of dissolved copper in seawater by multi-collector inductively coupled plasma mass spectrometry after pre-concentration using an ethylenediaminetriacetic acid chelating resin.

Copper is an essential trace metal that shows a vertical recycled-scavenged profile in the ocean. To help elucidate the biogeochemical cycling of Cu in the present and past oceans, it is important to determine the distribution of Cu isotopes in seawater. However, precise isotopic analysis of Cu has been impaired by the low concentrations of Cu as well as co-existing elements that interfere with measurements by multi-collector inductively coupled plasma mass spectrometry (MC-ICP-MS). The objective of this study is to develop a simple Cu pre-concentration method using Nobias-chelate PA1 resin (Hitachi High Technologies). This extraction followed by anion exchange, allows precise analysis of the Cu isotopic composition in seawater. Using this method, Cu was quantitatively concentrated from seawater and >99.9999% of the alkali and alkaline earth metals were removed. The technique has a low procedural blank of 0.70 ng for Cu for a 2L sample and the precision of the Cu isotopic analysis was ±0.07‰ (±2SD, n=6). We applied this method to seawater reference materials (i.e., CASS-5 and NASS-6) and seawater samples obtained from the northwestern Pacific Ocean. The range of dissolved δ(65)Cu was 0.40-0.68‰.

Heavy element stable isotope ratios: analytical approaches and applications.

Continuous developments in inorganic mass spectrometry techniques, including a combination of an inductively coupled plasma ion source and a magnetic sector-based mass spectrometer equipped with a multiple-collector array, have revolutionized the precision of isotope ratio measurements, and applications of inorganic mass spectrometry for biochemistry, geochemistry, and marine chemistry are beginning to appear on the horizon. Series of pioneering studies have revealed that natural stable isotope fractionations of many elements heavier than S (e.g., Fe, Cu, Zn, Sr, Ce, Nd, Mo, Cd, W, Tl, and U) are common on Earth, and it had been widely recognized that most physicochemical reactions or biochemical processes induce mass-dependent isotope fractionation. The variations in isotope ratios of the heavy elements can provide new insights into past and present biochemical and geochemical processes. To achieve this, the analytical community is actively solving problems such as spectral interference, mass discrimination drift, chemical separation and purification, and reduction of the contamination of analytes. This article describes data calibration and standardization protocols to allow interlaboratory comparisons or to maintain traceability of data, and basic principles of isotope fractionation in nature, together with high-selectivity and high-yield chemical separation and purification techniques for stable isotope studies.

Mg isotope fractionation in biogenic carbonates of deep-sea coral, benthic foraminifera, and hermatypic coral.

High-precision Mg isotope measurements by multiple collector inductively coupled plasma mass spectrometry were applied for determinations of magnesium isotopic fractionation of biogenic calcium carbonates from seawater with a rapid Mg purification technique. The mean δ(26)Mg values of scleractinian corals, giant clam, benthic foraminifera, and calcite deep-sea corals were -0.87‰, -2.57‰, -2.34‰, and -2.43‰, suggesting preferential precipitation of light Mg isotopes to produce carbonate skeleton in biomineralization. Mg isotope fractionation in deep-sea coral, which has high Mg calcite skeleton, showed a clear temperature (T) dependence from 2.5 °C to 19.5 °C: 1,000 × ln(α) = -2.63 (±0.076) + 0.0138 (±0.0051) × T(R(2) = 0.82, p < 0.01). The δ(26)Mg values of large benthic foraminifera, which are also composed of a high-Mg calcite skeleton, can be plotted on the same regression line as that for deep-sea coral. Since the precipitation rates of deep-sea coral and benthic foraminifera are several orders of magnitude different, the results suggest that kinetic isotope fractionation may not be a major controlling factor for high-Mg calcite. The Mg isotope fractionation factors and the slope of temperature dependence from deep-sea corals and benthic foraminifera are similar to that for an inorganically precipitated calcite speleothem. Taking into account element partitioning and the calcification rate of biogenic CaCO(3), the similarity among inorganic minerals, deep-sea corals, and benthic foraminiferas may indicate a strong mineralogical control on Mg isotope fractionation for high-Mg calcite. On the other hand, δ(26)Mg in hermatypic corals composed of aragonite has been comparable with previous data on biogenic aragonite of coral, sclerosponges, and scaphopad, regardless of species differences of samples.

Preconcentration method of antimony using modified thiol cotton fiber for isotopic analyses of antimony in natural samples.

It is very important to investigate antimony geochemical behavior in order to identify its source, or reveal contamination processes, since antimony and its compounds are considered to be pollutants of high priority by the Environmental Protection Agency of the United States (USEPA). However, the concentration of antimony in most geological samples is very low, and its stable isotope mass difference is only 1.6%. An antimony preconcentration method for isotope analysis using modified Thiol Cotton Fiber has been developed. Using this new method, the recovery of antimony was 99.5 ± 3.6% (n = 3) and blank values were <0.1 ng. The standard error of the ε(123)Sb isotope ratios in the proposed method is only 0.4ε, much smaller than those of the previous method. The proposed method is therefore effective in the preconcentration and separation of antimony for antimony isotope analysis.

Anthropogenic lead inputs to the western Pacific during the 20th century.

Unlike in the North Atlantic, no continuous record of anthropogenic lead (Pb) has been available in the western Pacific. We reconstructed historical changes in anthropogenic Pb on the basis of Pb isotope ratios recorded in annually-banded coral retrieved from Ogasawara Island, Japan. Whereas the predominant natural source of Pb to the surface of the western Pacific apparently is Chinese loess, anthropogenic Pb has affected the western Pacific at least since the late 19th century. From the late 19th to the early 20th century, Australian Pb used in Japan was an important source of anthropogenic Pb. During 1920-1940, Pb emitted from parts of the world other than Japan contributed somewhat to the western Pacific, and the amount of Pb imported from Australia declined. Alkyl Pb used in Japan became the main source from 1950 until the mid-1970s, when leaded gasoline began to be regulated in Japan. Since the mid-1980s, aerosols from China have been the predominant source of Pb in the western Pacific. During the 1990s, around 60% of Pb in the surface of the western Pacific was from Chinese aerosols. We also investigated the present spatial distribution and likely sources of Pb in the western Pacific by using coral samples. Enrichment in 208Pb, which is a characteristic of Pb from China, was found in all coral samples except that from Pohnpei, Micronesia, suggesting that at present anthropogenic Pb is transported to the western Pacific mainly from China via westerly winds.

Absolute isotopic composition and atomic weight of commercial zinc using inductively coupled plasma mass spectrometry.

Inductively coupled plasma mass spectrometry is introduced as a method for determining the absolute isotopic composition of zinc. The high ionization efficiency and time-independent characteristics of the mass spectrometry permit the absolute isotopic composition of high ionization potential elements. The mass discrimination of the instrument is calibrated by synthetic isotope mixtures prepared from highly enriched isotopes of zinc. The resulting isotope ratios yield atomic percents of 64Zn, 49.188 +/- 0.030; 66Zn, 27.792 +/- 0.041; 67Zn, 4.041 +/- 0.009; 68Zn, 18.378 +/- 0.050; and 70Zn, 0.600 +/- 0.003. This isotopic composition is different from those of conventional mass spectrometric measurements. Their differences depend on the mass differences about 0.8-1.2%/amu with enhancement of heavier isotopes. The atomic weight calculated from our isotopic composition is 65.3756 +/- 0.0040. The obtained atomic weight is fully consistent with that of a precise coulometric measurement in contrast to the previous mass spectrometric measurements. An isotopic variation of commercial zinc reagents has been investigated. A mass-dependent fractionation of 0.12%/amu is observed in a high-purity metal zinc, NIST-SRM 682, among five reagents. This mass dependence is probably inherited through their purification process.