Characterization of Fe(III) (hydr)oxides in arsenic contaminated soil under various redox conditions by XAFS and Mössbauer spectroscopies

Characterization of Fe(III) (hydr)oxides in soils near the Ichinokawa mine was conducted using X-ray absorption fine structure (XAFS) and Mössbauer spectroscopies, and the structural changes were correlated with the release of As into pore-water. The Eh values decreased monotonically with depth. Iron is mainly present as poorly-ordered Fe(III) (hydr)oxides, such as ferrihydrite, over a wide redox range (from Eh = 360 to −140 mV). Structural details of the short-range order of these Fe(III) (hydr)oxides were examined using Mössbauer spectroscopy by comparing the soil phases with synthesized ferrihydrite samples having varying crystallinities. The crystallinity of the soil Fe (hydr)oxides decreased slightly with depth and Eh. Thus, within the redox range of this soil profile, ferrihydrite dominated, even under very reducing conditions, but the crystalline domain size, and, potentially, particle size, changed with the variation in Eh. In the soil–water system examined here, where As concentration and the As(III)/As(V) ratio in soil water increased with depth, ferrihydrite persisted and maintained or even enhanced its capacity for As retention with increased reducing conditions. Therefore, it is concluded that As release from these soils largely depends on the transformation of As(V) to As(III) rather than reductive dissolution of Fe(III) (hydr)oxide.     

Phytoplankton assemblage in the Plio-Pleistocene record of Lake Baikal as indicated by sedimentary steryl chlorin esters

Past changes in phytoplankton assemblages in Lake Baikal over the last 4.5 Ma, both in population and composition, are inferred from the downcore profiles of the relatively stable chlorophyll derivatives steryl esters of pyropheophorbides a and b (steryl chlorine esters; SCEs) in the 0–200 m section of the BDP-98 drill core, supplemented by the data on biogenic silica (BSi) and total organic carbon (TOC) contents. SCEs-a and -b dominate among sedimentary chlorophyll derivatives in the BDP-98 sediments except for the upper few meters, indicating their high stability during diagenetic alteration of sediments. The depth (age) profiles of SCEs-a are consistent with BSi and TOC profiles and are interpreted as reflecting primary productivity of the lake in the past. Baikal proxies reveal close correlation with marine oxygen isotope records (MIS stratigraphy). These observations confirm that climate change in the northern hemisphere has been a primary factor controlling the total phytoplankton productivity in Lake Baikal during the last several million years.Among SCEs-a, C₃₀ (dinostanol)-SCE-a, a marker of dinoflagellates was identified by GC–MS analysis. SCE-b, a marker of green algae, was identified by its UV–vis spectrum. The ratio of C₃₀-SCE-a to total SCEs-a (TSCEs-a) was higher during 4.5–4.2 and 1.7–1.3 Ma, suggesting that dinoflagellates proliferated preferentially in those periods. The early Pleistocene maximum of this ratio corresponds to the broad minimum of diatom abundance previously suggested to have recorded a prolonged regional cooling. An abrupt increase in the SCE-b/TSCEs-a ratio was observed at 2.5–2.6 Ma, indicating that green algae containing chlorophyll b have proliferated in Lake Baikal during this period. This interval has also been suggested to contain evidence for a significant regional cooling based on minima of diatom abundance and BSi in sediments. The depth profile of C₂₇Δ⁵ (cholesterol)-SCE-a relative to TSCEs-a showed a trend similar to that of BSi, suggesting that C₂₇Δ⁵-SCE-a/TSCEs-a ratio is a potential marker of diatoms in Lake Baikal.Certain mismatches between the Lake Baikal profiles of biological indicators and the marine oxygen isotope records, as well as the slight temporal offsets between different Lake Baikal biological marker signals suggest that the regional component of climatic and/or lacustrine environmental changes also have played a role in determining the composition of the Lake Baikal Plio-Pleistocene phytoplankton assemblage.     

Holocene climate changes in the mid-high-latitude-monsoon margin reflected by the pollen record from Hulun Lake, northeastern Inner Mongolia

Pollen-assemblage data from a sediment core from Hulun Lake in northeastern Inner Mongolia describe the changes in the vegetation and climate of the East Asian monsoon margin during the Holocene. Dry steppe dominated the lake basin from ca. 11,000 to 8000 cal yr BP, suggesting a warm and dry climate. Grasses and birch forests expanded 8000 to 6400 cal yr BP, implying a remarkable increase in the monsoon precipitation. From 6400 to 4400 cal yr BP, the climate became cooler and drier. Chenopodiaceae dominated the interval from 4400 to 3350 cal yr BP, marking extremely dry condition. Artemisia recovered 3350-2050 cal yr BP, denoting an amelioration of climatic conditions. Both temperature and precipitation decreased 2050 to 1000 cal yr BP as indicated by decreased Artemisia and the development of pine forests. During the last 1000 yr, human activities might have had a significant influence on the environment of the lake region. We suggest that the East Asian summer monsoon did not become intensified until 8000 cal yr BP due to the existence of remnant ice sheets in the Northern Hemisphere. Changes in the monsoon precipitation on millennial to centennial scales would be related to ocean-atmosphere interactions in the tropical Pacific.     

Climate teleconnections influence on West Africa's terrestrial water storage

There is some evidence of rapid changes in the global atmosphere and hydrological cycle caused by the influence of climate variability. In West Africa, such changes impact directly on water resources leading to incessant extreme hydro‐meteorological conditions. This study examines the association of three global climate teleconnections—El‐Niño Southern Oscillation (ENSO), Indian Ocean Dipole (IOD), and Atlantic Multi‐decadal Oscillation (AMO) with changes in terrestrial water storage (TWS) derived from both Modern‐Era Retrospective Analysis for Research and Applications (MERRA, 1980–2015) and Gravity Recovery and Climate Experiment (GRACE, 2002–2014). In the Sahel region, positive phase of AMO coincided with above‐normal rainfall (wet conditions) and the negative phase with drought conditions and confirms the observed statistically significant association (r = 0.62) between AMO and the temporal evolutions of standardised precipitation index. This relationship corroborates the observed presence of AMO‐driven TWS in much of the Sahel region (though considerably weak in some areas). Although ENSO appears to be more associated with GRACE‐derived TWS over the Volta basin (r =?0.40), this study also shows a strong presence of AMO‐ and ENSO‐induced TWS derived from MERRA reanalysis data in the coastal West African countries and most of the regions below latitude 10°N. The observed presence of ENSO‐ and AMO‐driven TWS is noticeable in tropical areas with relatively high annual/bimodal rainfall and strong inter‐annual variations in surface water. The AMO has a wider footprint and sphere of influence on the region's TWS and suggests the important role of North Atlantic Ocean. IOD‐related TWS also exists in West Africa and its influence on the region's hydrology maybe secondary and somewhat complementary. Nonetheless, presumptive evidence from the study indicates that ENSO and AMO are the two major climatic indices more likely to impact on West Africa's TWS.     

Carbon isotope anatomy of a single graphite crystal in a metapelitic migmatite revealed by high-spatial resolution SIMS analysis

High-spatial resolution carbon isotope analyses of natural graphite using secondary ion mass spectrometry (SIMS), together with conventional mass spectrometry techniques, demonstrate isotopic heterogeneity within single graphite crystals precipitated from a partially melted metamorphic rock. SIMS ¹³C/¹²C measurements were calibrated using an internal graphite standard previously analyzed by conventional isotope ratio mass spectrometry, which gave a reproducibility of 0.3‰ (1σ) at a spatial resolution of 2–3 μm. This resolution helped to identify an unusual carbon isotope distribution in a single graphite crystal from a metapelitic leucosome, showing remarkable core to rim variations with sharp δ¹³C steps up to 10‰. The results suggest that the graphite crystal grew from one edge to other forming layers perpendicular to the c-axis. The sharp isotopic steps indicate the presence of disequilibrium carbon isotope zoning in graphite and points to the possible existence of carbon isotope sector zoning. Intra-crystalline carbon isotope disequilibrium in graphite is believed to have resulted from the difference in diffusivity between ¹²C and ¹³C in the growth medium to the interface of graphite precipitation in different growth sectors.     

Evolution and decay of a warm-core ring within the western subarctic gyre of the North Pacific,as observed by profiling floats

This study investigated temporal variations in the vertical structure and water properties of a warm-core ring that migrated into the western subarctic gyre of the North Pacific, based on analyses of temperature and salinity data derived from two profiling floats, together with shipboard and satellite observation data. The floats were initially deployed into cold and fresh Oyashio water in September 2003, and were entrained into a warm-core ring in October 2003, remaining within the ring until detrainment in December 2004. Drastic cooling and freshening of the upper core water of the ring were observed during the above entrainment of the floats with cold and fresh water into the ring, whereas moderate variations in structure and water properties were observed during a quasi-isolated phase from November 2003 to November 2004 when the ring did not experience major interactions with ambient hydrographic features. The upper part of the core water (upper core), with relatively warm/saline water above 26.6 σ _θ , was under the influence of the atmosphere in winter via the formation of a deep mixed layer exceeding 300 dB, and had a prominent pycnostad below the seasonal pycnocline from spring to autumn. In contrast, the lower core, with relatively cold and fresh water below 26.6 σ _θ , was not ventilated throughout the observation period. Isopycnal surfaces showed a shoaling trend of about 50 dB/year during the quasi-isolated phase, suggesting viscous decay over a timescale of several years. Markedly cold and thick water was also frequently observed within the ring, indicating the intrusion of water from the Sea of Okhotsk.     

Dating of the Dome Fuji shallow ice core based on a record of volcanic eruptions from AD 1260 to AD 2001

We measured the concentration of non-sea-salt sulfate () in the Dome Fuji shallow ice core (Antarctica) from the surface to 40 m depth with the aim of dating the core with reference to the record of volcanic eruptions. Three huge spikes related to large-scale volcanic eruptions were detected at depths of 12.5, 29.9, and 38.8 m, correlated to the eruptions of Tambora (AD 1815), Kuwae (AD 1452) and an unknown event (AD 1259), respectively. We identified another nine spikes related to accurately dated eruption events. The shallow ice core was dated from AD 1260 to AD 2001 based on these 12 eruption events and the assumption of constant annual snow accumulation in the periods between eruption events. The results yield a maximum correction of ∼20 years compared with the dating proposed in a previous study. The annual accumulation varied within ±∼15% of the average water equivalent value over the study period (25.5 mm).     

Non－LTE Analysis of the Sodium Abundance of Metal－Poor Stars in the Galactic Disk and Halo

We performed an extensive non-LTE analysis of the neutral sodiumlines of Na I 5683/5688, 5890/5896, 6154/6161, and 8183/8195 in disk/halo starsof types F-K covering a wide metallicity range (-4 [Fe/H] +0.4), using ourown data as well as data collected from the literature. For comparatively metal-rich disk stars (-1 [Fe/H] +0.4) where the weaker 6154/6161 lines are thebest abundance indicators, we confirmed [Na/Fe] ～ 0 with an "upturn" (i.e., ashallow/broad dip around -0.5 [Fe/H] 0) as already reported in previousstudies. For the metal-deficient halo stars, where the much stronger 5890/5896 or8183/8195 lines subject to considerable (negative) non-LTE corrections amountingto 0.5 dex have to be used, our analysis suggests mildly "subsolar" [Na/Fe] valuesdown to ～ -0.4 (with a somewhat large scatter of ～±0.2 dex) on the average at thetypical halo metallicity of [Fe/H] ～ -2, followed by a rise again to a near-solar ratioof [Na/Fe] ～ 0 at the very metal-poor regime [Fe/H] ～ -3 to -4. These resultsare discussed in comparison with the previous observational studies along with thetheoretical predictions from the available chemical evolution models.     

Sodium‐metasomatism in chondrules in CO3 chondrites: Relationship to parent body thermal metamorphism

Abstract— We have studied the mineralogy and petrology of mesostases of 783 type I chondrules in seven CO3 chondrites that range in petrologic subtype from 3.0 to 3.7. Chondrule mesostases in the CO chondrite of subtype 3.0 consist mainly of primary glass and plagioclase, while chondrule mesostases in the CO chondrites of higher subtypes (3.2–3.7) contain various amounts of nepheline in addition to glass and plagioclase. Nepheline has replaced glass and plagioclase, forming finegrained aggregates and thin parallel lamellar intergrowths with plagioclase. The nephelinization has proceeded preferentially from the outer margins of chondrules toward the inside. Although the degree of nephelinization differs widely among chondrules in each of the metamorphosed chondrites, our modal analyses and bulk chemical analyses of individual mesostases indicate that the amounts of nepheline in chondrules systematically increase with the increasing petrologic subtype of the host chondrites. Nepheline also has a tendency to increase in grain size with increasing petrologic subtype. We conclude that nepheline in chondrules in the CO3 chondrites has formed largely as a result of effects related to heating on the meteorite parent body. We suggest that nepheline initially formed as hydrous nepheline under the presence of aqueous fluids and subsequently was dehydrated after exhaustion of aqueous fluids. The degree of hydrothermal activity must have increased with increasing degree of heating, and thus, chondrules in more thermally metamorphosed chondrites produced larger amounts of nepheline. The results imply that CO3 chondrites have gone through low‐grade aqueous alteration and subsequent dehydration at the early stage of heating on the meteorite parent body.