Detection of several volatile organic compounds through Ar+ induced chemical ionisation using inductively coupled plasma-tandem mass spectrometry (ICP-MS/MS).

A new analytical technique for detection of organic compounds using inductively coupled plasma-tandem mass spectrometry (ICP-MS/MS) is described. Volatile organic compounds (VOCs) were introduced into the collision/reaction cell (CRC), instead of through the ICP ion source, and the molecules were ionised through an ion reaction, induced by collision with the primary ions (Ar+) produced in the ICP. The ionisation characteristics of this new approach were investigated by mass spectrometric analysis of eight VOCs (i.e., benzene, toluene, ethyl acetate, methyl butyrate, ethyl butyrate, pentyl acetate, pyridine, and 2-methylfuran). These molecules were detected as molecular ions (M+), protonated ions ([M + H]+), or deprotonated ions ([M - H]+), demonstrating that soft ionisation was achieved by the present ionisation protocol using ICP-MS/MS. In addition, a volatile selenium-containing organic compound, dimethyl diselenide (Se2(CH3)2), was also analysed to investigate the feasibility of this ionisation protocol to achieve soft and hard ionisation simultaneously. Several Se-related ions such as Se+, SeH+, Se2+, [SeCH3]+, and [Se2CH3]+, together with [Se2(CH3)2]+, were observed, suggesting that while soft ionisation was possible, ion reaction-induced-fragmentation and hard ionisation also occurred. To demonstrate the analytical capability of the present technique, volatile components released from coffee beans were subjected to the present mass spectrometric analysis. Many ion peaks originating from VOCs were detected from the coffee beans. The data obtained here demonstrated that ICP-MS equipped with a CRC can become an effective tool for analyzing both elements and molecules.

Future redistribution of fishery resources suggests biological and economic trade-offs according to the severity of the emission scenario.

Climate change is anticipated to have long-term and pervasive effects on marine ecosystems, with cascading consequences to many ocean-reliant sectors. For the marine fisheries sector, these impacts can be further influenced by future socio-economic and political factors. This raises the need for robust projections to capture the range of potential biological and economic risks and opportunities posed by climate change to marine fisheries. Here, we project future changes in the abundance of eight commercially important fish and crab species in the eastern Bering Sea and Chukchi Sea under different CMIP6 Shared Socioeconomic Pathways (SSPs) leading to contrasting future (2021-2100) scenarios of warming, sea ice concentration, and net primary production. Our results revealed contrasting patterns of abundance and distribution changes across species, time periods and climate scenarios, highlighting potential winners and losers under future climate change. In particular, the least changes in future species abundance and distribution were observed under SSP126. However, under the extreme scenario (SSP585), projected Pacific cod and snow crab abundances increased and decreased, respectively, with concurrent zonal and meridional future shifts in their centers of gravity. Importantly, projected changes in species abundance suggest that fishing at the same distance from the current major port in the Bering Sea (i.e., Dutch Harbor) could yield declining catches for highly valuable fisheries (e.g., Pacific cod and snow crab) under SSP585. This is driven by strong decreases in future catches of highly valuable species despite minimal declines in maximum catch potential, which are dominated by less valuable taxa. Hence, our findings show that projected changes in abundance and shifting distributions could have important biological and economic impacts on the productivity of commercial and subsistence fisheries in the eastern Bering and Chukchi seas, with potential implications for the effective management of transboundary resources.

Variation in the relationship between odd isotopes of tin in mass-independent fractionation induced by the magnetic isotope effect.

Experimental results are presented showing the variation in the relationship between odd isotopes of tin (Sn) in mass-independent fractionation caused by the magnetic isotope effect (MIE), which has previously only been observed for mercury. These results are consistent with the trend predicted from the difference between the magnitudes of nuclear magnetic moments of odd isotopes with a nuclear spin. However, the correlation between odd isotopes in fractionation induced by the MIE for the reaction system used in this study (solvent extraction using a crown ether) was different from that reported for the photochemical reaction of methyltin. This difference between the two reaction systems is consistent with a theoretical prediction that the correlation between odd isotopes in fractionation induced by the MIE is controlled by the relationship between the spin conversion time and radical lifetime. The characteristic changes in the correlation between odd isotopes in fractionation induced by the MIE observed for Sn in this study provide a guideline for quantitatively determining fractionation patterns caused by the MIE for elements that have multiple isotopes with a nuclear spin. These results improve our understanding of the potential impact of the MIE on mass-independent fractionation observed in natural samples, such as meteorites, and analytical artifacts of high-precision isotope analysis for heavy elements.

Cretaceous to early Paleogene sediment provenance transition from continental to magmatic arc systems in the Northwestern Pacific Region.

Unraveling the Paleo-Kuril Arc's origins is key to understanding northwest Pacific tectonics. The Paleo-Kuril Arc is viewed as an intraoceanic arc from trench subduction between the Izanagi and Pacific Plates. Alternatively, several studies suggest the Paleo-Kuril Arc as a continental magmatic arc, hypothesizing the existence of a mid-oceanic ridge and Paleogene subduction, placing the Paleo-Kuril Arc near the Okhotsk Block's southern edge. This study clarifies these hypotheses, previously clouded by limited geochronological data on deposits in the Paleo-Kuril Arc. We conducted U-Pb dating to examine the origins of detrital zircons from the Cretaceous-Paleogene Tokoro and Nemuro Belts of the Paleo-Kuril Arc. Cluster analysis, merging new and existing data, identified two unique detrital zircon age clusters. The abundance of Precambrian zircons in Cretaceous-Paleocene Paleo-Kuril Arc sandstones (Type 1 Cluster) suggests a continental magmatic origin, supporting the ridge subduction model. However, an early Eocene shift to a consistent local volcanic source (Type 2 Cluster) highlights a significant provenance change. This geochronological evidence, indicating a separation from continental sources, calls for further research to decode the simultaneous development of sediment sources in different geological belts, potentially tied to the ridge subduction event.

U-Pb dating for zircons from granitic rocks in southwestern Cambodia.

U-Pb dating was conducted for zircons from a total of 14 samples from 13 granite bodies in southwestern Cambodia using LA-ICP-MS. The granitic rock samples were collected from southwestern Cambodia, southwest of the Mae Ping Fault extending from northwest Cambodia via Tonle Sap Lake to southern Vietnam. The studied rock bodies belong to the ilmenite-series, except for three granitic rock bodies. They were identified as I-or A-type. The analysis yielded three distinct age ranges: 295-309, 191-232, and 75-98 Ma. The 295-309 Ma ages are associated with the Paleo-Tethys Sea subduction beneath the Indochina Block. The ages of 191-232 Ma may correspond to the amalgamation period of the Sibumasu and Indochina Blocks during the Indosinian Orogeny. Granitic rocks with ages of 75-98 Ma occur near the southeastern Cambodia-southern Vietnam border. Formation of these granitic rocks was associated with the Paleo-Pacific Ocean Plate (the Izanagi Plate) subduction beneath the Indochina Block. The region in which these granitic rocks occur is part of the Dalat-Kratie Zone.

Quantitative imaging of trace elements in solid samples by online isotope dilution laser ablation-inductively coupled plasma-mass spectrometry.

For quantitative visualization of trace elements, an online isotope dilution (ID) laser ablation-inductively coupled plasma-mass spectrometry (LA-ICP-MS) method capable of accurately correcting the detection amount of targets is presented. Two aerosols from an ablated sample and a nebulized isotopically enriched spike solution were mixed online using a dual-port spray chamber. In this paper, transmission efficiency (TE) of each of the two gas streams to the ICP-MS detector is revealed, and the quantification values were corrected by including the ratio of TEs in the calculation of the online ID method. To verify the developed method, Fe and Sr as model elements in five certified reference materials (CRMs, glass: SRM 610, 612, 614, alloy: SS-356, -383) were quantified without the use of matrix-matched CRMs. The resultant values agreed with the certified values of CRMs in the range of 92.7-104.7% and 92.8-109.0% for Fe and Sr, respectively. The LODs (3σ) were 0.54 and 0.17 µg g-1 for Fe and Sr, respectively. In addition, the applicability of this method to quantitative imaging of unknown solid samples was demonstrated for actual biological hard tissues (a mouse incisor, human primary tooth, and fish otolith) using the result of shot-analysis. The results were consistent with the reported concentration range obtained by wet chemical analysis.

Size Uncertainty in Individual Nanoparticles Measured by Single Particle Inductively Coupled Plasma Mass Spectrometry.

Single particle inductively coupled plasma mass spectrometry has been used for size measurements of individual nanoparticles (NPs). Here, uncertainties in size analysis based upon two calibration approaches were evaluated: (i) the use of particle size standard and (ii) the use of ion standard solution. For particle size standard approach, the source of uncertainty to determine the target NP diameter was related to the variation in the signal intensities of both target NPs and particle size standard, and the size distribution of the particle size standard. The relative uncertainties of the 50 nm silver NP as the target were 15.0%, 9.9%, and 10.8% when particle size standards of 30 nm, 60 nm, and 100 nm silver NPs were used, respectively. As for the ion standard solution approach, the sources of uncertainty were the concentration of working standard solution, sample flow rate, transport efficiency, slope of calibration curve, and variation in the signal intensity of the ion standard solution and of the target NPs. The relative uncertainties for the 50 nm silver NP were 18.5% for 1 ng/g, 7.6% for 10 ng/g, and 4.7% for 100 ng/g solutions. The lower uncertainty obtained with a high concentration working standard solution is recommended to improve precision on particle size determinations by spICP-MS.

BioQuant: Data Processing Software for Simultaneous Imaging Analysis for Elements and Molecules Using Two Mass Spectrometers.

Simultaneous imaging analysis for both elements and molecules was conducted by introducing laser-induced sample particles into two separate mass spectrometers (i.e., an inorganic spectrometer and an organic mass spectrometer) through the split-flow protocol. The timing of ion detections for elements and molecules can be different, reflecting the differences in mass scan rates, lengths for transport tubing, and flow rates of carrier gases, and thus, the timing of ion detections must be carefully aligned to discuss abundance correlations between elements and molecules. To achieve this, a new data processing software "BioQuant" was developed to correct the time difference of the signal intensities for components obtained by the two mass spectrometers. With the BioQuant software, signal intensity data obtained from several unit cells were merged into a newly defined unit cell, calculated by the common time intervals from both mass spectrometers. With the newly defined unit cells, correlation analysis between the elements and molecules can be conducted. Combination of the BioQuant software and laser ablation system connected to two separated mass spectrometers can become a benchmark technique for simultaneous imaging analysis for both the elements and molecules from single sample material.

Dispersion Function of a Protein, DP-1, Identified in Collimonas sp. D-25, for the Synthesis of Gold Nanoparticles.

Collimonas sp. (D-25), found in the soil of Akita Prefecture, is a gram-negative bacterium with the ability to synthesize gold nanoparticles (AuNPs). During the synthesis of AuNPs, one specific protein (DP-1) was found to have disappeared in the sonicated solution of the bacterium. Recombinant DP-1 (rDP-1) from Escherichia coli BL21 (DE3) was used to study the effect of DP-1 on the synthesis of AuNPs. AuNPs synthesized with rDP-1 result in small, stabilized nanoparticles. AuNPs synthesized by DP-1 retained the stability of both the dispersion and nano-size particles under high salt concentrations. Isothermal titration calorimetry was employed to investigate the bonding ratio of rDP-1 to AuNPs. Several thousand rDP-1 proteins are attached to the surface of an AuNP to form a protein corona containing multiple layers. These results suggest that DP-1 obtained from D-25 has a size and stability control function during AuNP synthesis.

Direct Analysis of Bio-Molecules in Solid Materials Using Electrospray Ionisation Mass Spectrometry Coupled with Laser Ablation and a Liquid Sampling Technique.

In situ and rapid analysis of organic compounds using a combination of a newly-developed laser ablation in liquid (LAL) sampling technique combined with electrospray ionisation mass spectrometry (ESI-MS) is reported. The LAL is a technique that allows laser ablation to be conducted in a liquid medium containing organic compounds that were effectively extracted from solid materials into the liquid medium. Three organic compounds (valine, caffeine, and benzyl butyl phthalate (BBP)) were subjected to analysis. The LAL sampling was conducted in the fast-laser scanning mode using Galvanometric optics, and the total ablation time required for the sampling from a 1 mm2 area was about 3 s, thus providing rapid sampling. The resulting sample solution was directly introduced into the ESI-MS system, without the need for any chromatographic separation. To evaluate the analytical capability of the LAL technique coupled with ESI-MS, both the overall transmission efficiencies of analytes from solid materials to the ion detector, and the repeatabilities of the measurements were rigorously tested. This involved the use of synthetic, in-house prepared standard materials containing the analytes. The overall ion yields were about 1.1×10-3% for valine, 8.7×10-3% for caffeine, and 6.7×10-4% for BBP. By comparing the ion yields obtained by the injection of an analyte solution and a standard solution through the mass spectrometer, the recoveries through the LAL sampling were approximately 31% for valine, 45% for caffeine, and 37% for BBP. In addition, the analytical repeatabilities for all analytes were better than 6%. The analytical repeatabilities were mainly affected by either the heterogeneity of the in-house standard materials or changes in the plasma temperature by coexisting, laser-induced sample particles. It should be noted that not only water-soluble compounds (caffeine and valine), but also non-soluble compound (BBP) could be measured by the LAL-ESI-MS, which is one of the great advantages over the conventional liquid extraction surface analysis technique. The data obtained here clearly demonstrate that the LAL-ESI-MS has the potential for being a fast and user-friendly analytical technique for the in-situ detection for both the water-soluble and water-insoluble molecules.

Size Analysis of Silver and Gold Nanoparticles Using Laser Ablation Single Particle ICP Mass Spectrometry: Evaluation of the Laser-Induced Disintegration of Nanoparticles.

Single particle inductively coupled plasma mass spectrometry combined with the laser ablation technique (LA-spICP-MS) has been used for the determination of particle size and the spatial distribution of metal nanoparticles (MNPs) in various solid samples such as biological samples and semiconductor materials. In this study, we investigated the effect of the fluence of the laser being used on the disintegration of MNPs. Commercially available MNPs of silver and gold (Ag NPs and Au NPs), the sizes of which were determined by transmission electron microscopy (TEM), were analyzed with LA-spICP-MS. We evaluated the degree of disintegration of the original-sized particles, based on a comparison of the size distributions obtained by LA-spICP-MS and other analytical techniques. The disintegration of both the Ag NPs and Au NPs was induced by a laser ablation process when the laser fluence was higher than 1.0 J cm-2, whereas no disintegration was observed when the fluence was lower than 1.0 J cm-2. Moreover, the mean diameter and standard deviation of the determined diameters obtained by LA-spICP-MS were in good agreement with solution-based spICP-MS and TEM analysis within analytical uncertainty. The data obtained here demonstrates that LA-spICP-MS represents a promising potential analytical technique for accurately determining the size of individual MNPs and their spatial distribution in solid samples.

Pan-Arctic marine biodiversity and species co-occurrence patterns under recent climate.

The Arctic region is experiencing drastic climatic changes bringing about potential ecological shifts. Here, we explored marine biodiversity and potential species associations across eight Arctic marine areas between 2000 and 2019. We compiled species occurrences for a subset of 69 marine taxa (i.e., 26 apex predators and 43 mesopredators) and environmental factors to predict taxon-specific distributions using a multi-model ensemble approach. Arctic-wide temporal trends of species richness increased in the last 20 years and highlighted potential emerging areas of species accrual due to climate-driven species redistribution. Further, regional species associations were dominated by positive co-occurrences among species pairs with high frequencies in the Pacific and Atlantic Arctic areas. Comparative analyses of species richness, community composition, and co-occurrence between high and low summer sea ice concentrations revealed contrasting impacts of and detected areas vulnerable to sea ice changes. In particular, low (high) summer sea ice generally resulted in species gains (loss) in the inflow and loss (gains) in the outflow shelves, accompanied by substantial changes in community composition and therefore potential species associations. Overall, the recent changes in biodiversity and species co-occurrences in the Arctic were driven by pervasive poleward range shifts, especially for wide-ranging apex predators. Our findings highlight the varying regional impacts of warming and sea ice loss on Arctic marine communities and provide important insights into the vulnerability of Arctic marine areas to climate change.

Historical changes of 236U/238U and 235U/238U isotopic ratios in Tokyo Bay from the 1960s to the 2000s.

We examine the historical changes of 236U/238U and 235U/238U in a sediment core collected in Tokyo Bay and elucidate the anthropogenic sources of uranium in the 1960s-2000s. Uranium-236 was detected in samples deposited in the 1960s-2000s, and the 236U/238U ratio of the sediment core shows peak values in the 1970s. The 235U/238U isotopic ratios in samples deposited in the early 1960s are almost identical to that of natural uranium, implying that the 236U might have originated from global fallout. A decrease in 235U/238U was observed in the late 1960s-2000s, suggesting that depleted uranium from nuclear fuel reprocessing increased the 236U/238U ratios in the sediment. The 236U/238U values in sediments from the 1980s-2000s were lower than those in the 1970s but considerably higher than those in the 1960s, suggesting that the main source of depleted uranium still remains around Tokyo Bay. Our results demonstrated that the depleted uranium released in the 1970s should be considered as an important end-member when using uranium isotopic ratios as environmental tracers in closed aquatic environments around industrial cities.

Improvement of spatial resolution of elemental imaging using laser ablation-ICP-mass spectrometry.

Laser ablation-ICP-mass spectrometer (LA-ICPMS) now becomes one of the most principal analytical technique for mapping analysis for major to trace elements in rocks, minerals, functional materials, or biological tissue samples. In this study, imaging analysis was conducted with coupling of small volume cell and off-set laser ablation protocol to improve the spatial resolution. Combination of newly designed small volume cell and in-torch gas mixing protocols provides faster washout time of the signals (about 0.8 s for reducing 238U being one part in a hundred, 1% level). This is very important to improve the spatial resolution in a direction of laser scanning. Moreover, combination of small distances between the laser-line scan (laser pitch distance) and preferential and total ablation of only biological tissue samples placed on glass substrate results in laser ablation of smaller areas than the size of laser ablation pit (shaving ablation). With the shaving ablation, laser-line scanning with narrower-band width (e.g., 2 µm) can be achieved even by the laser beam of 8 µm diameter. To demonstrate the practical usage of the present technique, imaging analysis of Gd-ethylenediamine tetra-methylene phosphonic acid-doped mouse bone was conducted. Preferential distribution of Gd at the edge of the apatite cell was more clearly identified by the present technique. Combination of the shorter washout system setup and the shaving ablation protocol enables us to improve the spatial resolution of the elemental imaging obtained with the LA-ICPMS technique.

Size Analysis of Small Metal Nanoparticles Using Single Particle ICP Mass Spectrometry.

For size analysis of small nanoparticles (i.e., nanoparticles smaller than 10 nm) using spICP-MS, two approaches were employed to improve the signal-to-noise ratio of ion signals emanating from small nanoparticles. The first one was enhancement of the instrumental sensitivity using a desolvating system. The second approach was separation of the ion signals from background signals through a deconvolution method. A combination of these approaches enabled us to measure 5 nm gold nanoparticles, and the calculated size detection limit was 3.8 nm.

Zircon U-Pb chronology on plutonic rocks from northeastern Cambodia.

Zircon U-Pb geochronology was carried out on plutonic rocks from Phnom Daek, Phnom Koy Rmeas, Svay Chras, Kon Mom, Koh Nheak, Andong Meas, Oyadav South, Svay Leu, and Phnom Soporkaley. The zircon U-Pb ages from the plutonic rocks determined in this study can be roughly divided into two groups. One is the Late Permian to Triassic ages of 278-202 Ma for the Phnom Daek, Phnom Koy Rmeas, Oyadav South, Svay Leu, and Phnom Soporkaley, and the other is the early Cretaceous ages of 118-98 Ma for the Svay Chras, Kon Mom, Koh Nheak, and Andong Meas samples. The plutonic rocks from Phnom Daek, Phnom Koy Rmeas, Svay Leu, Oyadav South, and Phnom Soporkaley were likely formed by magmatic activity in the Loei Fold Belt. These plutonic rocks were likely formed in an extensional setting and/or a region where the continental crust was thin. The plutonic rocks of Svay Chras, Kon Mom, Koh Nheak, and Andong Meas were likely formed by magmatic activity in the Dalat-Kratie Fold Belt, related to the NW-directed subduction of the Paleo-Pacific Ocean plate. These plutonic rocks are thought to correspond to the Dinhquan suite in southern Vietnam. The Kon Mom and Koh Nheak plutonic rocks fall within the alkaline series, which suggests that the magma genesis was deep and far from the western Paleo-Pacific Ocean plate. Magmatic activity in the Dalat-Kratie Fold Belt migrated oceanward as a whole during the Cretaceous.

Marine biodiversity refugia in a climate-sensitive subarctic shelf.

The subarctic shelf of the Eastern Bering Sea (EBS) is one of the world's most productive marine environments, exposed to drastic climate changes characterized by extreme fluctuations in temperature, sea ice concentration, timing, and duration. These climatic changes elicit profound responses in species distribution, abundance, and community composition. Here, we examined the patterns of alpha and temporal beta diversity of 159 marine taxa (66 vertebrates and 93 invertebrate species) from 29 years (1990-2018) of species observations from the NOAA bottom trawl surveys in the EBS. Based on these data, we identified geographically distinct refugial zones in the northern and southern regions of the middle shelf, defined by high species richness and similarity in community species composition over time. These refugial zones harbor higher frequencies of occurrence for representative taxa relative to the regions outside of refugia. We also explored the primary environmental factors structuring marine biodiversity distributions, which underpinned the importance of the winter sea ice concentration to alpha and temporal beta diversity. The spatial biodiversity distributions between high and low winter sea ice regimes highlighted contrasting signals. In particular, the latter showed elevated species richness compared to the former. Further, the temporal beta diversity between the high and low winter sea ice periods underpinned an overall increase in the compositional similarity of marine communities in the EBS. Despite these spatiotemporal differences in biodiversity distributions, the identified refugia represent safe havens of marine biodiversity in the EBS. Distinguishing these areas can help facilitate conservation and management efforts under accelerated and ongoing climatic changes.

Radiometric Calibration for a Multispectral Sensor Onboard RISESAT Microsatellite Based on Lunar Observations.

Radiometric calibration utilizing the Moon as a reference source is termed as lunar calibration. It is a useful method for evaluating the performance of optical sensors onboard satellites orbiting the Earth. Lunar calibration provides sufficient radiometric calibration opportunities without requiring any special equipment, and is suitable for nano/microsatellites. This study applies lunar calibration to a multispectral sensor, Ocean Observation Camera (OOC), on board a microsatellite named Rapid International Scientific Experiment Satellite. Simulating the brightness of the Moon based on the RObotic Lunar Observatory and SELENE/Spectrum Profiler models, sensitivity degradation was proven to be negligible in any of the four spectral bands of the OOC with the sensor temperature correction. A bluing trend in the OOC's sensor sensitivity was revealed, indicating a shorter observation wavelength shows larger irradiance. Comparing the top-of-atmosphere reflectance of Railroad Valley Playa with the Radiometric Calibration Network dataset revealed that the derived calibration parameter from the lunar calibration was valid for correcting the bluing trend in the visible range. Although the lunar and vicarious calibration parameters for the infrared band were unexpectedly inconsistent, lunar calibration could potentially contribute toward estimating the contaminated background radiance in the Earth observation images.

Quantitative Visualization of Lanthanum Accumulation in Lanthanum Carbonate-Administered Human Stomach Tissues Using Mass Spectrometry Imaging.

Platinum, a transition metal that is widely used in anti-cancer agents, also results in the development of nephropathy due to severe adverse reactions caused by platinum-induced nephrotoxicity. Reports on imaging with metals other than platinum remain are limited, even in preclinical studies. Furthermore, most of these are case reports, and the relationship between the distribution of the metal and clinical observations in human samples is not well understood. Here we report on visualizing lanthanum (139La), a component of Fosrenol, which is usually used for the treatment of hyperphosphatemia. Gastric inflammation, also known as hemorrhagic gastritis, is the main adverse event caused by Fosrenol. To conduct this study, 139La was visualized in gastric biopsy samples obtained from a patient using quantitative laser ablation-inductively coupled plasma-mass spectrometry (LA-ICP-MS). We also compared the distribution of 139La in tissue and histochemical results. The areas where 139La accumulated corresponded to the macrophage-positive areas observed in immunohistochemistry studies using an anti-CD68 antibody. In contrast, we observed a debris-like crystal morphology in hematoxylin and eosin staining tissues. The debris was also associated with 139La accumulation. The abnormal accumulation of 139La crystals caused the observed inflammation. This phenomenon was previously characterized, but this is the first report in which 139La distribution and histochemical results are compared using LA-ICP-MS.