Distributions of aluminum, manganese, cobalt, and lead in the western South Pacific: Interplay between the South and North Pacific

Aluminum (Al), manganese (Mn), cobalt (Co), and lead (Pb) are strongly scavenged from seawater. We reported that each element is uniquely related to ocean circulation in the North Pacific (Zheng et al., 2019). Herein, we present the full-depth distributions of these elements in the western South Pacific, which include meridional sections along 170°W (GEOTRACES GP19). We determined dissolved (d) and total dissolvable (td) concentrations using filtered and unfiltered seawater without UV treatment, and we calculated labile particulate (lp) concentrations as the difference between td and d concentrations. This and the previous studies present the basin scale distributions, which enable us to investigate first order processes that drive the biogeochemistry of Al, Mn, Co, and Pb in the Pacific Ocean. The meridional section of dAl along 170°W (GP19)-160°W (GPc06) from 64°S to 54°N indicates that elevated concentrations (maximum 6.1 nmol/kg) occur between 40°S and 10°S from surface to bottom. However, the maxima of lpAl occur at high latitudes. The lpAl/tdAl ratio has a minimum of 0.26 ± 0.12 (ave ± sd, n = 116) in the zone from 30°S to 0°S. Based on these results, we propose a hypothesis that weathering on land has a significant effect on the distribution of Al in the ocean. Intensive weathering on tropical and subtropical islands and Australia forms kaolinite-dominated soils and laterite. This process provides dAl and kaolinite to the ocean. The supply of kaolinite results in kaolinite-dominated sediments that become a major bottom source for dAl. In contrast, strong sources of Mn and Co are continental shelves around the northern boundary. Dissolved Mn and dCo are released from sediments by manganese reduction and carried by intermediate water circulation. In particular, dCo spreads in the North Pacific Intermediate Water (NPIW), Equatorial Pacific Intermediate Water (EqPIW), and Antarctic Intermediate Water (AAIW); 23–59 pmol/kg at a potential density anomaly (σθ) of 27.0. This is partly owing to the uptake of dCo by phytoplankton and remineralization from settling particles. The dPb concentrations are 10 ± 6 pmol/kg (n = 397) in the South Pacific and 30 ± 20 pmol/kg (n = 566) in the North Pacific. The distribution of dPb is characterized by a maximum in the Subtropical Mode Water (SMW) and Central Mode Water (CMW) with σθ∼26 in the North Pacific. These results indicate that Pb is predominantly supplied by anthropogenic aerosols from Asia and Russia to the Pacific Ocean. Because Pb is not actively taken up by phytoplankton, Pb enters mode waters during winter convection and is transported with mode waters

Solid-phase extraction of palladium, platinum, and gold from water samples: comparison between a chelating resin and a chelating fiber with ethylenediamine groups

Dissolved palladium (Pd), platinum (Pt), and gold (Au) form inert chloride complexes at low concentrations of pmol/kg in environmental water, thus rendering difficulty in the development of a precise analytical method for these metals. Herein, we report the preconcentration of Pd, Pt, and Au with a chelating fiber Vonnel-en and a chelating resin TYP-en with ethylenediamine (en) groups. Batch adsorption experiments reveal the adsorption capacity of Vonnel-en for Pd(II), Pt(IV), and Au(III) in 0.10 M HCl as 0.53, 0.22, and 0.27 mmol/g, respectively. The adsorption capacity of TYP-en for Pd(II), Pt(IV), and Au(III) in 0.10 M HCl is 0.31, 0.17, and 0.52 mmol/g, respectively. In column extraction experiments using small-volume samples containing Pd(II), Pt(II), Pt(IV), Au(I), or Au(III) at concentrations of μmol/kg, TYP-en is able to quantitatively recover Pd, Pt, and Au from 0.01 to 0.2 M HCl irrespective of their oxidation states. In contrast, Vonnel-en is unable to quantitatively recover Au(I). In column extraction experiments using large-volume samples containing Pd(II), Pt(IV), and Au(III) at concentrations of pmol/kg, the recovery of Pd(II), Pt(IV), and Au(III) by TYP-en from 0.07 M HCl is 100–105%. However, the recovery of Pd(II), Pt(IV), and Au(III) by Vonnel-en from 0.03 to 0.3 M HCl is 102–110, 7–15, and 20–52%, respectively. Thus, the chelating resin TYP-en has a high potential for the multielemental determination of Pd, Pt, and Au in environmental water

Sectional Distribution Patterns of Cd, Ni, Zn, and Cu in the North Pacific Ocean: Relationships to Nutrients and Importance of Scavenging

The North Pacific Ocean is located at the end of the thermohaline circulation of deep water. This study reports on basin-scale full-depth sectional distributions of total dissolvable (td), dissolved (d), and labile particulate (lp) Cd, Ni, Zn, and Cu along three transects: the GEOTRACES transects GP18 (165°E) and GP02 (47°N), and along 160°W. We find that scavenging is an important factor that significantly affects the distributions of dZn, dNi, and dCu, of which the magnitude of influence increases in the order of Cd 800 m deep, which is in the range of the phytoplankton Cd/P ratio. This is indicative of the dominant effect of water circulation and biological processes on dCd distribution. The dissolved metals (dMs) to PO₄ ratios of other examined metals were either partially or completely outside the range of typical biomass ratios. They generally increased with depth in waters >800 m deep; the magnitude of increase was the highest for Cu and moderate for Ni and Zn. Below 800 m, an increase in the apparent oxygen utilization from 150 to 300 μmol/kg was concurrent with a decrease in the dMs/PO4 ratios: 4 ± 3% for Cd, 21 ± 4% for Zn, 21 ± 3% for Ni, and 69 ± 7% for Cu

Distribution of stable isotopes of Mo and W from a river to the ocean: signatures of anthropogenic pollution

Molybdenum and tungsten are redox-sensitive elements, and their stable isotope ratios have attracted attention as paleoceanographic proxies. However, our knowledge of the distribution of stable Mo and W isotopes in the modern hydrosphere remains limited. In this study, we provided the concentrations and isotope ratios of dissolved Mo and W in the oceans (the North Pacific and Indian Oceans), marginal seas (the East China Sea and Sea of Japan), and a river-estuary system in Japan (from the Uji-Yodo rivers to Osaka Bay). In the North Pacific and Indian Oceans, the W concentration was 48.2 ± 6.2 pmol/kg (ave ± 2sd, n = 109), δ186/184W was 0.52 ± 0.06 ‰, the Mo concentration was 105.1 ± 8.0 nmol/kg, and δ98/95Mo was 2.40 ± 0.06 ‰. The results indicate that W has the constant concentration and isotopic composition in the modern ocean as well as Mo. In the East China Sea and the Sea of Japan, the W concentration and δ186/184W in the upper water (< 1000 m depth) were different from those in the ocean (W = 56 ± 18 pmol/kg, δ186/184W = 0.45 ± 0.06 ‰, n = 24). However, the concentrations in deeper water were congruent with those in the oceans (W = 49.9 ± 7.6 pmol/kg, δ186/184W = 0.50 ± 0.02 ‰, n = 7). The Mo concentration was 105.4 ± 3.1 nmol/kg and δ98/95Mo was 2.36 ± 0.03 ‰ (n = 31) throughout the water column, congruent with those in the ocean. In the Uji River-Yodo River-Osaka Bay system, the W concentration reached 1074 pmol/kg and δ186/184W reached 0.20 ‰. We propose that the enrichment of W with a low δ186/184W in the river-estuary system and marginal seas is caused by anthropogenic pollution. Anthropogenic Mo pollution was not detected in marginal seas. However, the Mo concentration and δ98/95Mo showed high anomalies above the mixing line of river water and seawater in the lower Yodo River and Osaka Bay, implying possible anthropogenic pollution of Mo in the metropolitan area

Isotopic analysis of Ni, Cu, and Zn in freshwater for source identification

Nickel (Ni), copper (Cu), and zinc (Zn) are commonly used in human activities and pollute aquatic environments including rivers and oceans. Recently, Ni, Cu, and Zn isotope ratios have been measured to identify their sources and cycles in environments. We precisely determined the Ni, Cu, and Zn isotope ratios in rain, snow, and rime collected from Uji City and Mt. Kajigamori in Japan, and investigated the potential of isotopic ratios as tracers of anthropogenic materials. The isotope and elemental ratios suggested that road dust is the main source of Cu in most rain, snow, and rime samples and that some of the Cu may originate from fossil fuel combustion. Zinc in the rain, snow, and rime samples may be partially attributed to Zn in road dust. Zinc isotope ratios in the Uji rain samples are lower than those in the road dust, which would be emitted via high temperature processes. Nickel isotope ratios are correlated with V/Ni ratios in the rain, snow, and rime samples, suggesting that their main source is heavy oil combustion. Furthermore, we analyzed water samples from the Uji and Tawara Rivers and the Kakita River spring in Japan. Nickel and Cu isotope ratios in the river water samples were significantly heavier than those in rain, snow, and rime samples, while Zn isotope ratios were similar. This is attributed to isotopic fractionation of Cu and Ni between particulate-dissolved phases in river water or soil

Magnesium and zinc stable isotopes as a new tool to understand Mg and Zn sources in stream food webs

Non‐traditional stable isotopes of metals were recently shown as new dietary tracers in terrestrial and marine mammals. Whether these metal stable isotopes can be used to understand feeding habits in stream food webs is not known yet. In this study, we explored the potential of stable isotopes of essential Mg (δ26Mg) and Zn (δ66Zn) as a new tool in stream ecology. For this purpose, we determined δ26Mg and δ66Zn values of stream organisms and their potential metal sources in upper and lower reaches of two streams in the Lake Biwa catchment, Central Japan. Our goals were (1) to explore variations in δ26Mg and δ66Zn across organisms of different feeding habits and (2) to understand Mg and Zn sources to stream organisms. Overall, δ26Mg and δ66Zn values of organisms were neither related to each other, nor to δ13C and δ15N values, indicating different elemental sources and factors controlling isotopic fractionation depending on element and taxa. Low δ26Mg values in filter‐feeding caddisfly larvae and small gobies indicated aqueous Mg uptake. Higher δ26Mg values in leaf‐shredding crane fly and grazing mayfly larvae suggested Mg isotopic fractionation during Mg uptake from the diet. While the δ26Mg values of stonefly nymphs reflected those of caddisfly larvae as a potential prey, the highest δ26Mg values found in dobsonfly nymphs can be explained by 26Mg enrichment during maturing. δ66Zn values of caddisfly and mayfly larvae indicated Zn was a mixture of aqueous and dietary available Zn, while higher δ66Zn values in crane fly larvae pointed to Zn isotopic fractionation during Zn uptake from plant litter. δ66Zn values in stonefly and dobsonfly nymphs were often in the range of those of caddisfly larvae as their prey, while dragonfly nymphs and small goby were depleted in 66Zn relative to their dietary Zn sources. We conclude that δ26Mg is a promising indicator to assess Mg sources in stream ecology depending on taxa, while the use of δ66Zn is limited due to the complexity in Zn sources

Magnesium and zinc stable isotopes as a new tool to understand Mg and Zn sources in stream food webs

Non-traditional stable isotopes of metals were recently shown as new dietary tracers in terrestrial and marine mammals. Whether these metal stable isotopes can be used to understand feeding habits in stream food webs is not known yet. In this study, we explored the potential of stable isotopes of essential Mg (δ²⁶Mg) and Zn (δ⁶⁶Zn) as a new tool in stream ecology. For this purpose, we determined δ²⁶Mg and δ⁶⁶Zn values of stream organisms and their potential metal sources in upper and lower reaches of two streams in the Lake Biwa catchment, Central Japan. Our goals were (1) to explore variations in δ²⁶Mg and δ⁶⁶Zn across organisms of different feeding habits and (2) to understand Mg and Zn sources to stream organisms. Overall, δ²⁶Mg and δ⁶⁶Zn values of organisms were neither related to each other, nor to δ¹³C and δ¹⁵N values, indicating different elemental sources and factors controlling isotopic fractionation depending on element and taxa. Low δ²⁶Mg values in filter-feeding caddisfly larvae and small gobies indicated aqueous Mg uptake. Higher δ²⁶Mg values in leaf-shredding crane fly and grazing mayfly larvae suggested Mg isotopic fractionation during Mg uptake from the diet. While the δ²⁶Mg values of stonefly nymphs reflected those of caddisfly larvae as a potential prey, the highest δ²⁶Mg values found in dobsonfly nymphs can be explained by ²⁶Mg enrichment during maturing. δ⁶⁶Zn values of caddisfly and mayfly larvae indicated Zn was a mixture of aqueous and dietary available Zn, while higher δ⁶⁶Zn values in crane fly larvae pointed to Zn isotopic fractionation during Zn uptake from plant litter. δ⁶⁶Zn values in stonefly and dobsonfly nymphs were often in the range of those of caddisfly larvae as their prey, while dragonfly nymphs and small goby were depleted in ⁶⁶Zn relative to their dietary Zn sources. We conclude that δ²⁶Mg is a promising indicator to assess Mg sources in stream ecology depending on taxa, while the use of δ⁶⁶Zn is limited due to the complexity in Zn sources

Inter-calibration of a proposed new primary reference standard AA-ETH Zn for zinc isotopic analysis

We have prepared a large volume of pure, concentrated and homogenous zinc standard solution. This new standard solution is intended to be used as a primary reference standard for the zinc isotope community, and to serve as a replacement for the near-exhausted current reference standard, the so-called JMC-Lyon Zn. The isotopic composition of this new zinc standard (AA-ETH Zn) has been determined through an inter-laboratory calibration exercise, calibrated against the existing JMC-Lyon standard, as well as the certified Zn reference standard IRMM-3702. The data show that the new standard is isotopically indistinguishable from the IRMM-3702 zinc standard, with a weighted d66/64Zn value of 0.28±0.02‰ relative to JMC-Lyon. We suggest that this new standard be assigned a value d66/64Zn of +0.28‰ for reporting of future Zn isotope data, with the rationale that all existing published Zn isotope data are presented relative to the JMC-Lyon standard. Therefore our proposed presentation allows a direct comparison with all previously published data, and that is directly traceable to a certified reference standard, IRMM-3702 Zn. This standard will be made freely available to all interested labs through contact with the corresponding author

The whole blood transcriptional regulation landscape in 465 COVID-19 infected samples from Japan COVID-19 Task Force

「コロナ制圧タスクフォース」COVID-19患者由来の血液細胞における遺伝子発現の網羅的解析 --重症度に応じた遺伝子発現の変化には、ヒトゲノム配列の個人差が影響する--. 京都大学プレスリリース. 2022-08-23.Coronavirus disease 2019 (COVID-19) is a recently-emerged infectious disease that has caused millions of deaths, where comprehensive understanding of disease mechanisms is still unestablished. In particular, studies of gene expression dynamics and regulation landscape in COVID-19 infected individuals are limited. Here, we report on a thorough analysis of whole blood RNA-seq data from 465 genotyped samples from the Japan COVID-19 Task Force, including 359 severe and 106 non-severe COVID-19 cases. We discover 1169 putative causal expression quantitative trait loci (eQTLs) including 34 possible colocalizations with biobank fine-mapping results of hematopoietic traits in a Japanese population, 1549 putative causal splice QTLs (sQTLs; e.g. two independent sQTLs at TOR1AIP1), as well as biologically interpretable trans-eQTL examples (e.g., REST and STING1), all fine-mapped at single variant resolution. We perform differential gene expression analysis to elucidate 198 genes with increased expression in severe COVID-19 cases and enriched for innate immune-related functions. Finally, we evaluate the limited but non-zero effect of COVID-19 phenotype on eQTL discovery, and highlight the presence of COVID-19 severity-interaction eQTLs (ieQTLs; e.g., CLEC4C and MYBL2). Our study provides a comprehensive catalog of whole blood regulatory variants in Japanese, as well as a reference for transcriptional landscapes in response to COVID-19 infection

DOCK2 is involved in the host genetics and biology of severe COVID-19

「コロナ制圧タスクフォース」COVID-19疾患感受性遺伝子DOCK2の重症化機序を解明 --アジア最大のバイオレポジトリーでCOVID-19の治療標的を発見--. 京都大学プレスリリース. 2022-08-10.Identifying the host genetic factors underlying severe COVID-19 is an emerging challenge. Here we conducted a genome-wide association study (GWAS) involving 2, 393 cases of COVID-19 in a cohort of Japanese individuals collected during the initial waves of the pandemic, with 3, 289 unaffected controls. We identified a variant on chromosome 5 at 5q35 (rs60200309-A), close to the dedicator of cytokinesis 2 gene (DOCK2), which was associated with severe COVID-19 in patients less than 65 years of age. This risk allele was prevalent in East Asian individuals but rare in Europeans, highlighting the value of genome-wide association studies in non-European populations. RNA-sequencing analysis of 473 bulk peripheral blood samples identified decreased expression of DOCK2 associated with the risk allele in these younger patients. DOCK2 expression was suppressed in patients with severe cases of COVID-19. Single-cell RNA-sequencing analysis (n = 61 individuals) identified cell-type-specific downregulation of DOCK2 and a COVID-19-specific decreasing effect of the risk allele on DOCK2 expression in non-classical monocytes. Immunohistochemistry of lung specimens from patients with severe COVID-19 pneumonia showed suppressed DOCK2 expression. Moreover, inhibition of DOCK2 function with CPYPP increased the severity of pneumonia in a Syrian hamster model of SARS-CoV-2 infection, characterized by weight loss, lung oedema, enhanced viral loads, impaired macrophage recruitment and dysregulated type I interferon responses. We conclude that DOCK2 has an important role in the host immune response to SARS-CoV-2 infection and the development of severe COVID-19, and could be further explored as a potential biomarker and/or therapeutic target