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.

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.

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.

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.

Simultaneous Determination of Size and Position of Silver and Gold Nanoparticles in Onion Cells using Laser Ablation-ICP-MS.

Size distribution and mapping analyses of Ag and Au nanoparticles (NPs) have been made using an ICP-MS combined with laser ablation sampling technique (LA-ICP-MS). With the femtosecond laser (Ti:S laser) ablation system, the measured size distribution was modified to be smaller, whereas this disintegration could be reduced when the nanosecond laser (ArF Excimer laser) ablation was employed. This suggests that both the size and position of the NPs can be defined by the nanosecond LA-ICP-MS technique. More importantly, based on the peak-height analyses (PHA) of the measured signal intensity profiles, the present form of the analytes, whether particulate or ionic form, could be defined. This is very important to investigate the transport of the NPs within biological samples. To demonstrate the unique feature of the technique, imaging analyses of Ag and Au NPs, together with distribution analysis of the ionic form, were conducted on onion cells, prepared through dosing experiments of the Ag and Au NPs. There were clear differences in both the increasing rates of the numbers of NPs and the concentration range of the ionic form between the Ag and Au. The data obtained here demonstrate clearly that the LA-ICP-MS technique can become a major analytical tool to obtain both the size distribution and position of NPs from tissue samples.

Quantitative Imaging of Silver Nanoparticles and Essential Elements in Thin Sections of Fibroblast Multicellular Spheroids by High Resolution Laser Ablation Inductively Coupled Plasma Time-of-Flight Mass Spectrometry.

We applied high resolution laser ablation inductively coupled plasma time-of-flight mass spectrometry (LA-ICP-TOF-MS) with cellular spatial resolution for bioimaging of nanoparticles uptaken by fibroblast multicellular spheroids (MCS). This was used to quantitatively investigate interactions of silver nanoparticles (Ag NPs) and the distributions of intrinsic minerals and biologically relevant elements within thin sections of a fibroblast MCS as a three-dimensional in vitro tissue model. We designed matrix-matched calibration standards for this purpose and printed them using a noncontact piezo-driven array spotter with a Ag NP suspension and multielement standards. The limits of detection for Ag, Mg, P, K, Mn, Fe, Co, Cu, and Zn were at the femtogram (10-15 g) level, which is sufficient to investigate intrinsic minerals in thin MCS sections (20 µm thick). After incubation for 48 h, Ag NPs were enriched in the outer rim of the MCS but not detected in the core. The localization of Ag NPs was inhomogeneous in the outer rim, and they were colocalized with a single-cell-like structure visualized by Fe distribution (pixel size of elemental images: 5 × 0.5 µm). The quantitative value for the total mass of Ag NPs in a thin section by the present method agreed with that obtained by ICP-sector field (SF)-MS with a liquid mode after acid digestion.

Imaging of Ag NP transport through collagen-rich microstructures in fibroblast multicellular spheroids by high-resolution laser ablation inductively coupled plasma time-of-flight mass spectrometry.

We investigated the penetration of silver nanoparticles (Ag NPs) into a three-dimensional in vitro tissue analog using NPs with various sizes and surface coatings, and with different incubation times. A high-resolution laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) time-of-flight (TOF) instrument was applied for imaging the distributions of elements in thin sample sections (20 µm thick). A fibroblast multicellular spheroid (MCS) was selected as the model system and cultured for more than 8 days to produce a natural barrier formed by the extracellular matrix containing collagen. The MCS was then exposed for up to 48 h to one of four types of Ag NPs (∅ 5 nm citrate coated, ∅ 20 nm citrate coated, ∅ 20 nm polyvinylpyrrolidone coated, and ∅ 50 nm citrate coated). Imaging showed that the penetration pathway was strongly related to steric networks formed by collagen fibrils, and Ag NPs with a hydrodynamic diameter of more than 41 nm were completely trapped in an outer rim of the MCSs even after incubation for 48 h. In addition, we examined the impact of these NPs on essential elements (P, Fe, Cu, and Zn) in areas of Ag NP accumulation. We observed a linear increase at the sub-femtogram level in the total concentration of Cu (fg per pixel) in samples treated with small or large Ag NPs (∅ 5 nm or ∅ 50 nm) for 48 h.

High-resolution laser ablation inductively coupled plasma mass spectrometry used to study transport of metallic nanoparticles through collagen-rich microstructures in fibroblast multicellular spheroids.

We have efficiently produced collagen-rich microstructures in fibroblast multicellular spheroids (MCSs) as a three-dimensional in vitro tissue analog to investigate silver (Ag) nanoparticle (NP) penetration. The MCS production was examined by changing the seeding cell number (500 to 40,000 cells) and the growth period (1 to 10 days). MCSs were incubated with Ag NP suspensions with a concentration of 5 µg mL-1 for 24 h. For this study, laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) was used to visualize Ag NP localization quantitatively. Thin sections of MCSs were analyzed by LA-ICP-MS with a laser spot size of 8 µm to image distributions of 109Ag, 31P, 63Cu, 66Zn, and 79Br. A calibration using a NP suspension was applied to convert the measured Ag intensity into the number of NPs present. The determined numbers of NPs ranged from 30 to 7200 particles in an outer rim of MCS. The particle distribution was clearly correlated with the presence of 31P and 66Zn and was localized in the outer rim of proliferating cells with a width that was equal to about twice the diameter of single cells. Moreover, abundant collagens were found in the outer rim of MCSs. For only the highest seeding cell number, NPs were completely captured at the outer rim, in a natural barrier reducing particle transport, whereas Eosin (79Br) used as a probe of small molecules penetrated into the core of MCSs already after 1 min of exposure. Graphical abstract Fibroblast MCS could build up the barrier only for nanoparticles.

The effect of Mg and Sr on the crystallinity of bones evaluated through Raman spectroscopy and laser ablation-ICPMS analysis.

We investigated the possible linkage between the crystallinity and elemental ratios (Mg/Ca and Sr/Ca) of the femoral cortical bones of rats with chronic kidney disease (CKD) or diabetes mellitus (DM). The Mg/Ca and Sr/Ca ratios were measured by using the laser ablation-inductively coupled plasma mass spectrometry (LA-ICPMS) technique and the crystallinity was evaluated by Raman spectroscopy on the same sample slice. The measured crystallinity varied significantly along the radial direction, reflecting the heterogeneities in the Mg/Ca ratio for the bone samples. For the endosteal cortical bone of CKD rats, the Mg/Ca ratio became higher. This is explained by the increase of the abundance of Mg in the bone, possibly due to the higher absorption efficiency of Mg in the intestine or due to the lower excretion efficiency of Mg from the kidney. For areas with a higher Mg/Ca ratio, the crystallinity of the bone was significantly more degraded than that for areas with a lower Mg/Ca ratio, suggesting that the substitution of Ca by Mg induced the deterioration of the crystallinity of hydroxyapatite (HAp). In addition, the measured Mg/Ca and Sr/Ca ratios of the bone were positively correlated with those found in serum samples. The data obtained here demonstrated that the metabolic alterations for inorganic elements caused the ionic substitutions of Ca by foreign cationic ions, and that the contents of foreign ions in the bone greatly affected the crystallinity of HAp.

Kantis: A new Australopithecus site on the shoulders of the Rift Valley near Nairobi, Kenya.

Most Plio-Pleistocene sites in the Gregory Rift Valley that have yielded abundant fossil hominins lie on the Rift Valley floor. Here we report a new Pliocene site, Kantis, on the shoulder of the Gregory Rift Valley, which extends the geographical range of Australopithecus afarensis to the highlands of Kenya. This species, known from sites in Ethiopia, Tanzania, and possibly Kenya, is believed to be adapted to a wide spectrum of habitats, from open grassland to woodland. The Kantis fauna is generally similar to that reported from other contemporaneous A. afarensis sites on the Rift Valley floor. However, its faunal composition and stable carbon isotopic data from dental enamel suggest a stronger C4 environment than that present at those sites. Although the Gregory Rift Valley has been the focus of paleontologists' attention for many years, surveys of the Rift shoulder may provide new perspective on African Pliocene mammal and hominin evolution.

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.

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.

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.

Generalized ocean color inversion model for retrieving marine inherent optical properties.

Ocean color measured from satellites provides daily, global estimates of marine inherent optical properties (IOPs). Semi-analytical algorithms (SAAs) provide one mechanism for inverting the color of the water observed by the satellite into IOPs. While numerous SAAs exist, most are similarly constructed and few are appropriately parameterized for all water masses for all seasons. To initiate community-wide discussion of these limitations, NASA organized two workshops that deconstructed SAAs to identify similarities and uniqueness and to progress toward consensus on a unified SAA. This effort resulted in the development of the generalized IOP (GIOP) model software that allows for the construction of different SAAs at runtime by selection from an assortment of model parameterizations. As such, GIOP permits isolation and evaluation of specific modeling assumptions, construction of SAAs, development of regionally tuned SAAs, and execution of ensemble inversion modeling. Working groups associated with the workshops proposed a preliminary default configuration for GIOP (GIOP-DC), with alternative model parameterizations and features defined for subsequent evaluation. In this paper, we: (1) describe the theoretical basis of GIOP; (2) present GIOP-DC and verify its comparable performance to other popular SAAs using both in situ and synthetic data sets; and, (3) quantify the sensitivities of their output to their parameterization. We use the latter to develop a hierarchical sensitivity of SAAs to various model parameterizations, to identify components of SAAs that merit focus in future research, and to provide material for discussion on algorithm uncertainties and future emsemble applications.

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.

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.

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.

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.

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.