Although antimony (Sb) contamination has been documented in urban areas, knowledge gaps remain concerning the contributions of the different sources to the Sb urban biogeochemical cycle, including ...non-exhaust road traffic emissions, urban materials leaching/erosion and waste incineration. Additionally, details are lacking about Sb chemical forms involved in urban soils, sediments and water bodies. Here, with the aim to document the fate of metallic contaminants emitted through non-exhaust traffic emissions in urban aquatic systems, we studied trace element contamination, with a particular focus on Sb geochemistry, in three highway stormwater pond systems, standing as models of surface environments receiving road-water runoff. In all systems, differentiated on the basis of lead isotopic signatures, Sb shows the higher enrichment factor with respect to the geochemical background, up to 130, compared to other traffic-related inorganic contaminants (Co, Cr, Ni, Cu, Zn, Cd, Pb). Measurements of Sb isotopic composition (δ123Sb) performed on solid samples, including air-exposed dusts and underwater sediments, show an average signature of 0.07 ± 0.05‰ (n = 25, all sites), close to the δ123Sb value measured previously in certified reference material of road dust (BCR 723, δ123Sb = 0.03 ± 0.05‰). Moreover, a fractionation of Sb isotopes is observed between solid and dissolved phases in one sample, which might result from Sb (bio)reduction and/or adsorption processes. SEM-EDXS investigations show the presence of discrete submicrometric particles concentrating Sb in all the systems, interpreted as friction residues of Sb-containing brake pads. Sb solid speciation determined by linear combination fitting of X-Ray Absorption Near Edge Structure (XANES) spectra at the Sb K-edge shows an important spatial variability in the ponds, with Sb chemical forms likely driven by local redox conditions: “dry” samples exposed to air exhibited contributions from Sb(V)–O (52% to 100%) and Sb(III)–O (<10% to 48%) species whereas only underwater samples, representative of suboxic/anoxic conditions, showed an additional contribution from Sb(III)–S (41% to 80%) species. Altogether, these results confirm the traffic emission as a specific source of Sb emission in surface environments. The spatial variations of Sb speciation observed along the road-to-pond continuum likely reflect a high geochemical reactivity, which could have important implications on Sb transfer properties in (sub)surface hydrosystems.
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•Highway stormwater ponds concentrate Sb contamination from road runoff.•Sb isotopic composition of stormwater pond sediments is close to that of road dusts.•Sb(V)–O, Sb(III)–O, and Sb(III)–S species occur in the road-to-pond continuum.•Sb(III)–S species are observed as a specific signature of underwater reduced samples.•Sb speciation changes along the waterway show the high geochemical reactivity of Sb.
Abstract
One of the main challenges in Environmental sciences is the identification and chemical evolution of polluting traces (e.g, cadmium or antimony) in soil, which requires long acquistion times ...for accurate measurements at synchrotron facilities. In this context, the potential of a new generation multi-element germanium detectors to identify traces at 0.1-1 ppm in a reasonable time has been studied using Allpix Squared framework 1. This code has been customized to include the three dimensional electric and weighting field maps generated by COMSOL Multiphysics software, and several features to model the sample environment at SOLEIL synchrotron and the signal response of a germanium detector equipped with a Digital Pulse Processor (DPP). The full simulation chain has been validated by experimental data from SAMBA beamline of SOLEIL synchrotron. This work presents a first estimation of the detection limit to cadmium traces in a soil sample for a future multi-element germanium detector, using this simulation chain.
Aims. Rinorea
cf.
bengalensis
is a Ni hyperaccumulator which occurs in Sabah (Malaysia), on Borneo Island, that is able to accumulate considerable amounts of Ni and influences the Ni cycle in surface ...soil layers, both in terms of Ni concentration and Ni isotopic composition. In this study, the biogeochemical processes underpinning Ni isotopic fractionation in the soil-plant system and the mechanisms regulating Ni homeostasis in
R.
cf.
bengalensis
plants were elucidated.
Methods
Two specimens of
R.
cf.
bengalensis
of different ages and associated surface soils were collected from ultramafic soils in Sabah. Soil mineralogy, Ni concentrations, speciation and isotopic signatures were subsequently determined in plant and soil samples.
Results
Nickel in
R.
cf.
bengalensis
leaves is mainly complexed with citrate. Soil Ni available fractions have different δ
60
Ni values depending on the Ni bearing phases.
Rinorea
cf.
bengalensis
specimens take up lighter Ni isotopes and a pronounced isotopic fractionation within the plant is observed, especially in the young specimen.
Conclusions
The results suggest that the observed fractionation in the young plant can be attributable to kinetic effects (lighter isotopes move faster), which become less evident in the older specimen, as Ni is redistributed and homogenized through phloem loading and unloading processes.
Summary
Thermococcales, a major order of archaea inhabiting the iron‐ and sulfur‐rich anaerobic parts of hydrothermal deep‐sea vents, have been shown to rapidly produce abundant quantities of pyrite ...FeS2 in iron–sulfur‐rich fluids at 85°C, suggesting that they may contribute to the formation of ‘low temperature’ FeS2 in their ecosystem. We show that this process operates in Thermococcus kodakarensis only when zero‐valent sulfur is directly available as intracellular sulfur vesicles. Whether in the presence or absence of zero‐valent sulfur, significant amounts of Fe3S4 greigite nanocrystals are formed extracellularly. We also show that mineralization of iron sulfides induces massive cell mortality but that concomitantly with the formation of greigite and/or pyrite, a new generation of cells can grow. This phenomenon is observed for Fe concentrations of 5 mM but not higher suggesting that above a threshold in the iron pulse all cells are lysed. We hypothesize that iron sulfides precipitation on former cell materials might induce the release of nutrients in the mineralization medium further used by a fraction of surviving non‐mineralized cells allowing production of new alive cells. This suggests that biologically induced mineralization of iron‐sulfides could be part of a survival strategy employed by Thermococcales to cope with mineralizing high‐temperature hydrothermal environments.
The vigor of the glacial Antarctic Circumpolar Current (ACC) and the locations of frontal boundaries are important parameters for understanding the role of the Southern Ocean in global climate ...change. Toward the goal of understanding the locations of currents we present a survey of Sr isotope ratios in terrigenous sediments around the perimeter of Antarctica. The pattern of the variations within the modern ACC is used to suggest that terrigenous sediment from Antarctica is injected into the ACC via the Ross and Weddell gyres in the south. North of the main ACC the Sr isotopes reflect continental contributions from Africa, Australia‐New Zealand, and South America. Along a transect northward from the Ross Sea, Sr isotope ratios show a decrease from higher values in the south (Antarctic provenance) to lower values in the north (provenance from New Zealand). This otherwise monotonic decrease is interrupted within the ACC by a “zigzag” to lower and then higher values, which accompanies minimum terrigenous flux. This zigzag requires contributions from two additional sediment sources beyond the main Antarctic and New Zealand end‐members. The lower Sr isotope ratios are attributable to greater contributions from basaltic sources within the current, a consistent pattern around the ACC. The samples with higher Sr isotope ratios point to an additional contributor, possibly a wind‐transported component from Australia. During the LGM there is a systematic geographical variation in the Sr isotope ratios, similar to that of the Holocene. A small offset of the zigzag to the north (approximately 1°–2°) may indicate a small northward shift of the southern boundary of the ACC. More highly resolved data are required to test whether this northward shift is really significant and whether it applies to other ACC fronts during the LGM.
This study determined Cd speciation and release kinetics in a Cd–Zn cocontaminated alkaline paddy soil, under various flooding periods and draining conditions, by employing synchrotron-based ...techniques, and a stirred-flow kinetic method. Results revealed that varying flooding periods and draining conditions affected Cd speciation and its release kinetics. Linear least-squares fitting (LLSF) of bulk X-ray absorption fine structure (XAFS) spectra of the air-dried, and the 1 day-flooded soil samples, showed that at least 50% of Cd was bound to humic acid. Cadmium carbonates were found as the major species at most flooding periods, while a small amount of cadmium sulfide was found after the soils were flooded for longer periods. Under all flooding and draining conditions, at least 14 mg/kg Cd was desorbed from the soil after a 2-hour desorption experiment. The results obtained by micro X-ray fluorescence (μ-XRF) spectroscopy showed that Cd was less associated with Zn than Ca, in most soil samples. Therefore, it is more likely that Cd and Ca will be present in the same mineral phases rather than Cd and Zn, although the source of these two latter elements may originate from the same surrounding Zn mines in the Mae Sot district.
Pyrite formation at low temperature during early diagenesis in (sub-)surface sediments is an essential step of Fe and S biogeochemical cycles and the presence of this ubiquitous mineral of surface ...environments is often used as an indicator of paleo-redox conditions. Pathways of pyrite formation are usually discussed in environmental settings by involving a variety of nanosized Fe-S mineralogical precursors as a function of the local geochemical conditions. However, the influence of trace element impurities such as Ni and As in the solution at the time of pyrite formation has been poorly studied, whereas specific chemical signatures of trace elements are commonly observed in sedimentary pyrites. A better understanding of the impact of Ni and As incorporation at trace levels on pyrite formation is essential to help refining the use of these elements as paleo-redox indicators and to evaluate the role of pyrite as a sink regulating the biogeochemical cycle of potentially toxic trace elements. In this study, we have performed syntheses of pyrite at low temperature via the polysulfide pathway using aqueous Fe(III) and H2S in the presence of trace amounts of Ni(II) (0.001 mol%Fe) and As(III) (0.001 mol%Fe). Analysis of the solids collected at different time steps over the course of the experiments using X-Ray absorption spectroscopy at both the Fe and S K-edges shows that pyrite starts to precipitate within 5 days in presence of Ni(II) and within 32 days in presence of As(III), while the control experiment showed an intermediate precipitation rate of 14 days. Shell-by-shell analysis of Fe K-edge EXAFS data shows that the initial mineralogical precursors are the same in all the experiments and correspond to poorly-crystalline FeS (3.0 ± 0.1 Fe-S@2.25 Å; 1.7 ± 0.2 Fe-Fe@2.67 Å). In addition, XANES qualitative analysis suggests the incorporation of small amounts of Fe(III) within these FeS precursors. Synchrotron-based XRD and WAXS-PDF analysis of the starting solids show that in addition to S(0), the FeS precursors correspond to a continuum of FeS particles that ranges from tetragonal nanocrystalline FeS (a = 3.70(2) Å, c = 5.24(7) Å, MCDab = 41 ± 4 Å MCDc = 21 ± 2 Å) to cluster-type FeS (MCDabc < 8.4 ± 4.3 Å). We propose that Ni(II) and As(III) have a different type of interaction with these FeS precursors, resulting respectively in an increase and a decrease in the rate of pyrite nucleation. While Ni(II) would incorporate within the structure of the FeS precursors, As would interact with (poly)sulfides in solution to form thio-As, possibly binding or precipitating onto FeS surfaces and thus slowing FeS transformation to FeS2. Given that both Ni and As were introduced at trace levels in our experiments, these results suggest that the occurrence of trace amounts of impurities could have a strong influence on pyrite precipitation kinetics in natural settings such as pore-scale microenvironments. In addition to emphasizing the importance of trace elements such as Ni or As on the persistence of mobile colloidal FeS species in anoxic conditions, the results of the present study also point to the importance of considering the actual nature of the impurities when using pyrite composition for ancient environments and past climates reconstruction.
This paper presents new laboratory measurements of the mass absorption efficiency (MAE) between 375 and 850 nm for 12 individual samples of mineral dust from different source areas worldwide and in ...two size classes: PM10. 6 (mass fraction of particles of aerodynamic diameter lower than 10.6 µm) and PM2. 5 (mass fraction of particles of aerodynamic diameter lower than 2.5 µm). The experiments were performed in the CESAM simulation chamber using mineral dust generated from natural parent soils and included optical and gravimetric analyses. The results show that the MAE values are lower for the PM10. 6 mass fraction (range 37–135 × 10−3 m2 g−1 at 375 nm) than for the PM2. 5 (range 95–711 × 10−3 m2 g−1 at 375 nm) and decrease with increasing wavelength as λ−AAE, where the Ångström absorption exponent (AAE) averages between 3.3 and 3.5, regardless of size. The size independence of AAE suggests that, for a given size distribution, the dust composition did not vary with size for this set of samples. Because of its high atmospheric concentration, light absorption by mineral dust can be competitive with black and brown carbon even during atmospheric transport over heavy polluted regions, when dust concentrations are significantly lower than at emission. The AAE values of mineral dust are higher than for black carbon (∼ 1) but in the same range as light-absorbing organic (brown) carbon. As a result, depending on the environment, there can be some ambiguity in apportioning the aerosol absorption optical depth (AAOD) based on spectral dependence, which is relevant to the development of remote sensing of light-absorbing aerosols and their assimilation in climate models. We suggest that the sample-to-sample variability in our dataset of MAE values is related to regional differences in the mineralogical composition of the parent soils. Particularly in the PM2. 5 fraction, we found a strong linear correlation between the dust light-absorption properties and elemental iron rather than the iron oxide fraction, which could ease the application and the validation of climate models that now start to include the representation of the dust composition, as well as for remote sensing of dust absorption in the UV–vis spectral region.
The mineralogy of niobium (Nb) is characterized by multicomponent oxides such as AB2O6, A2B2O7, ABO4, and ABO3 in which Nb is incorporated in the B site. Such complex crystal-chemistry prevents their ...unambiguous identification in ore deposits such as hydrothermal rocks and laterites which exhibit complex and fine-grained textures. The understanding of the processes controlling Nb ore deposit formation in various geological settings is therefore limited, although Nb is a critical element. In this study, we use X-ray absorption spectroscopy (XAS) at the Nb K-edge to investigate the local atomic-scale structure around Nb in a large set of natural and synthetic minerals of geological and technological importance. Our X-ray absorption near-edge structure (XANES) data at the Nb K-edge show three major features of variable position and intensity and then can be related to the local distortion and coordination number of the Nb site. Shell-by-shell fits of the extended X-ray absorption fine structure (EXAFS) data reveal that the NbO6 octahedra are distorted in a variety of pyrochlore species. At least two distinct first shells of O atoms are present while reported crystallographic data yield regular octahedra in the same minerals. Next-nearest Nb–Nb distances in pyrochlore and Nb-bearing perovskite mirror a corner-sharing NbO6 network, whereas the two Nb–Nb distances in columbite are typical of edge- and corner-sharing NbO6 octahedra. Such a resolution on the Nb site geometry and the intersite relationships between the next-nearest NbO6 octahedra is made possible by collecting EXAFS data under optimal conditions at 20 K and up to 16 Å−1. The local structure around substituted Nb5+ in Fe3+, Ti4+, and Ce4+ oxides suffers major changes relative to the unsubstituted structures. The substitution of Nb5+ for Ti4+ in anatase leads to the increase in the interatomic distances between Nb and its first and second Ti4+ neighbors. The substitution of Nb5+ for Ce4+ in cerianite reduces the coordination number of the cation from eight to four, and the Nb–O bonds are shortened compared to Ce–O ones. In hematite, Nb5+ occupies a regular site, whereas the Fe3+ site is strongly distorted suggesting major site relaxation due to charge mismatch. The sensitivity of XANES and EXAFS spectroscopies at the Nb K-edge to the local site geometry and next-nearest neighbors demonstrated in this study would help decipher Nb speciation and investigate mineralogical reactions of Nb minerals in deposit-related contexts such as hydrothermal and lateritic deposits.
Zinc is an important nutrient for plants, but it can be toxic at high concentrations. The solubility and speciation of Zn is controlled by many factors, especially soil pH and Eh, which can vary in ...lowland rice culture. This study determined Zn speciation and release kinetics in Cd–Zn cocontaminated alkaline and acidified paddy soils, under various flooding periods and draining conditions, by employing synchrotron-based techniques and a stirred-flow kinetic method. Results showed almost no change in Zn speciation and release kinetics in the two soils, although the soils were subjected to different flooding periods and draining conditions. The mineral phases in which Zn is immobilized in the soil samples were constrained by linear least squares fitting (LLSF) analyses of bulk X-ray absorption fine structure (XAFS) spectra. Only two main phases were identified by LLSF, i.e., Zn-layered double hydroxides (Zn/Mg-hydrotalcite-like, and ZnAl-LDH) and Zn-phyllosilicates (Zn-kerolite). Under all soil pHs, flooding, and draining conditions, less than 22% of Zn was desorbed from the soil after a two-hour desorption experiment. The information on Zn chemistry obtained in this study will be useful in finding the best strategy to control Cd and Zn bioavailability in the Cd–Zn cocontaminated paddy soils.
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