Detangling past and modern zinc anthropogenic source contributions in an urbanized coastal river by combining elemental, isotope and speciation approaches.

The accumulation of trace metals in the environmental compartments of coastal rivers is a global and complex environmental issue, requiring multiple tools to constrain the various anthropogenic sources and biogeochemical processes affecting the water quality of these environments. The Valao fluvio-estuarine system (Rio de Janeiro, Brazil) presents a challenging case of a coastal river contaminated by both modern and historical anthropogenic metal sources, located in the land and in the intra-estuary, continuously mixed by tidal cycles. This study employed a combination of spatial distribution analysis of trace metals including gadolinium (Gd), zinc (Zn) isotopic analyses, and X-ray absorption spectroscopy (XAS) to distinguish between these sources. The concentrations of metals in both dissolved (water samples) and surficial sediment compartments (Suspended Particulate Matter and sediment samples) display an overall enrichment trend from upstream to downstream. Multivariate statistical analysis allows to discriminate geogenic elements derived from watershed geology (Ti, K, and Mg) vs anthropogenic contaminants from urban runoff and domestic sewage discharges (Cu, Cr, Pb, Zn, and Gd); and legacy metal contaminants (Zn and Cd) remobilized from ancient metallurgical wastes and transported upstream in the estuary during tidal cycles. The anthropogenic Gd concentration in the dissolved compartment increases along the watercourse, highlighting continuous ongoing sewage discharge. Zinc solid speciation also indicates that Zn contribution from legacy metallurgy waste is primarily associated with sulfide-Zn and Zn-phyllosilicate in the outlet estuary, while in upstream sediments of fluvio-estuarine system, Zn is found bound to organic matter. Zinc isotope systematically reveals a progressive downstream shift to heavier isotope compositions. Upstream, the relatively pristine site and the urbanized section of the river exhibit a relatively uniform δ66/64Zn value (+0.20 ± 0.07 ‰) in suspended particulate matter (SPM) and surficial sediments. These results indicate that domestic sewage discharges contribute to Zn enrichment in sediments of the Valao fluvio-estuarine system but without modifying its isotope signature in sediments. The sediment of the downstream estuarine section shows a heavier δ66/64Zn value (+0.48 ± 0.08 ‰), indicating the strong influence of the intra-estuarine source identified as the historical metallurgic contamination. An integrated view of the geochemical tracers allows thus inferring that the untreated sewage and legacy metallurgical contamination are the primary sources of anthropogenic Zn contamination. It highlights the progressive mixing along the estuarine gradient under tidal dynamics. The influence of the former source continuously expands from the headland towards the estuary.

Fate of antimony contamination generated by road traffic - A focus on Sb geochemistry and speciation in stormwater ponds.

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 ±â€¯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 ±â€¯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.

Precipitation of greigite and pyrite induced by Thermococcales: an advantage to live in Fe- and S-rich environments?

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 Fe3 S4 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.

Quick extended x-ray absorption fine structure instrument with millisecond time scale, optimized for in situ applications.

In order to learn about in situ structural changes in materials at subseconds time scale, we have further refined the techniques of quick extended x-ray absorption fine structure (QEXAFS) and quick x-ray absorption near edge structure (XANES) spectroscopies at beamline X18B at the National Synchrotron Light Source. The channel cut Si (111) monochromator oscillation is driven through a tangential arm at 5 Hz, using a cam, dc motor, pulley, and belt system. The rubber belt between the motor and the cam damps the mechanical noise. EXAFS scan taken in 100 ms is comparable to standard data. The angle and the angular range of the monochromator can be changed to collect a full EXAFS or XANES spectrum in the energy range 4.7-40.0 KeV. The data are recorded in ascending and descending order of energy, on the fly, without any loss of beam time. The QEXAFS mechanical system is outside the vacuum system, and therefore changing the mode of operation from conventional to QEXAFS takes only a few minutes. This instrument allows the acquisition of time resolved data in a variety of systems relevant to electrochemical, photochemical, catalytic, materials, and environmental sciences.