Pierre Le Pape

X-ray absorption fine structure evidence for amorphous zinc sulfide as a major zinc species in suspended matter from the Seine River downstream of Paris, Ile-de-France, France.

Zinc is one of the most widespread trace metals (TMs) in Earth surface environments and is the most concentrated TM in the downstream section of the Seine River (France) due to significant anthropogenic input from the Paris conurbation. In order to better identify the sources and cycling processes of Zn in this River basin, we investigated seasonal and spatial variations of Zn speciation in suspended particulate matter (SPM) in the oxic water column of the Seine River from upstream to downstream of Paris using synchrotron-based extend X-ray absorption fine structure (EXAFS) spectroscopy at the Zn K-edge. First-neighbor contributions to the EXAFS were analyzed in SPM samples, dried and stored under a dry nitrogen atmosphere or under an ambient oxygenated atmosphere. We found a sulfur first coordination environment around Zn (in the form of amorphous zinc sulfide) in the raw SPM samples stored under dry nitrogen vs an oxygen first coordination environment around Zn in the samples stored in an oxygenated atmosphere. These findings are supported by scanning electron microscopy and energy dispersive X-ray spectrometry observations. Linear combination fitting of the EXAFS data for SPM samples, using a large set of EXAFS spectra of Zn model compounds, indicates dramatic changes in the Zn speciation from upstream to downstream of Paris, with amorphous ZnS particles becoming dominant dowstream. In contrast, Zn species associated with calcite (either adsorbed or incorporated in the structure) are dominant upstream. Other Zn species representing about half of the Zn pool in the SPM consist of Zn-sorbed on iron oxyhydroxides (ferrihydrite and goethite) and, to a lesser extent, Zn-Al layered double hydroxides, Zn incorporated in dioctahedral layers of clay minerals and Zn sorbed to amorphous silica. Our results highlight the importance of preserving the oxidation state in TM speciation studies when sampling suspended matter, even in an oxic water column.

Arsenic(V) Incorporation in Vivianite during Microbial Reduction of Arsenic(V)-Bearing Biogenic Fe(III) (Oxyhydr)oxides.

The dissolution of arsenic-bearing iron(III) (oxyhydr)oxides during combined microbial iron(III) and arsenate(V) reduction is thought to be the main mechanism responsible for arsenic mobilization in reducing environments. Besides its mobilization during bioreduction, arsenic is often resequestered by newly forming secondary iron(II)-bearing mineral phases. In phosphate-bearing environments, iron(II) inputs generally lead to vivianite precipitation. In fact, in a previous study we observed that during bioreduction of arsenate(V)-bearing biogenic iron(III) (oxyhydr)oxides in phosphate-containing growth media, arsenate(V) was immobilized by the newly forming secondary iron(II) and iron(II)/iron(III)mineral phases, including vivianite. In the present study, changes in arsenic redox state and binding environment in these experiments were analyzed. We found that arsenate(V) partly replaced phosphate in vivianite, thus forming a vivianite-symplesite solid solution identified as Fe3(PO4)1.7(AsO4)0.3·8H2O. Our data suggests that in order to predict the fate of arsenic during the bioreduction of abiogenic and biogenic iron(III) (oxyhydr)oxides in arsenic-contaminated environments, the formation of symplesite-vivianite minerals needs to be considered. Indeed, such mineral phases could contribute to a delayed and slow release of arsenic in phosphate-bearing surface and groundwater environments.

Complete removal of arsenic and zinc from a heavily contaminated acid mine drainage via an indigenous SRB consortium

Acid mine drainages (AMD) are major sources of pollution to the environment. Passive bio-remediation technologies involving sulfate-reducing bacteria (SRB) are promising for treating arsenic contaminated waters. However, mechanisms of biogenic As-sulfide formation need to be better understood to decontaminate AMDs in acidic conditions. Here, we show that a high-As AMD effluent can be decontaminated by an indigenous SRB consortium. AMD water from the Carnoulès mine (Gard, France) was incubated with the consortium under anoxic conditions and As, Zn and Fe concentrations, pH and microbial activity were monitored during 94days. Precipitated solids were analyzed using electron microscopy (SEM/TEM-EDXS), and Extended X-Ray Absorption Fine Structure (EXAFS) spectroscopy at the As K-edge. Total removal of arsenic and zinc from solution (1.06 and 0.23mmol/L, respectively) was observed in two of the triplicates. While Zn precipitated as ZnS nanoparticles, As precipitated as amorphous orpiment (am-AsIII2S3) (33-73%), and realgar (AsIIS) (0-34%), the latter phase exhibiting a particular nanowire morphology. A minor fraction of As is also found as thiol-bound AsIII (14-23%). We propose that the formation of the AsIIS nanowires results from AsIII2S3 reduction by biogenic H2S, enhancing the efficiency of As removal. The present description of As immobilization may help to set the basis for bioremediation strategies using SRB.

Zinc Speciation in the Suspended Particulate Matter of an Urban River (Orge, France): Influence of Seasonality and Urbanization Gradient

Among trace metal pollutants, zinc is the major one in the rivers from the Paris urban area, such as the Orge River, where Zn concentration in the suspended particulate matter (SPM) can reach 2000 mg/kg in the most urbanized areas. In order to better understand Zn cycling in such urban rivers, we have determined Zn speciation in SPM as a function of both the seasonal water flow variations and the urbanization gradient along the Orge River. Using TEM/SEM-EDX and linear combination fitting (LCF) of EXAFS data at the Zn K-edge, we show that Zn mainly occurs as tetrahedrally coordinated Zn(2+) sorbed to ferrihydrite (37-46%), calcite (0-37%), amorphous SiO2 (0-21%), and organic-P (0-30%) and as octahedrally coordinated Zn(2+) in the octahedral layer of phyllosilicates (18-25%). Moreover, the Zn speciation pattern depends on the river flow rate. At low water flow, Zn speciation changes along the urbanization gradient: geogenic forms of Zn inherited from soil erosion decrease relative to Zn bound to organic-phosphates and amorphous SiO2. At high water flow, Zn speciation is dominated by soil-borne forms of Zn regardless the degree of urbanization, indicating that erosion of Zn-bearing minerals dominates the Zn contribution to SPM under such conditions.

Arsenic Incorporation in Pyrite at Ambient Temperature at Both Tetrahedral S–I and Octahedral FeII Sites: Evidence from EXAFS–DFT Analysis

Pyrite is a ubiquitous mineral in reducing environments and is well-known to incorporate trace elements such as Co, Ni, Se, Au, and commonly As. Indeed, As-bearing pyrite is observed in a wide variety of sedimentary environments, making it a major sink for this toxic metalloid. Based on the observation of natural hydrothermal pyrites, As-I is usually assigned to the occupation of tetrahedral S-I sites, with the same oxidation state as in arsenopyrite (FeAsS), although rare occurrences of AsIII and AsII have been reported. However, the modes of As incorporation into pyrite during its crystallization under low-temperature diagenetic conditions have not yet been elucidated because arsenic acts as an inhibitor for pyrite nucleation at ambient temperature. Here, we provide evidence from X-ray absorption spectroscopy for AsII,III incorporation into pyrite at octahedral FeII sites and for As-I at tetrahedral S-I sites during crystallization at ambient temperature. Extended X-ray absorption fine structure (EXAFS) spectra of these As-bearing pyrites are explained by local structure models obtained using density functional theory (DFT), assuming incorporation of As at the Fe and S sites, as well as local clustering of arsenic. Such observations of As-I incorporation at ambient temperature can aid in the understanding of the early formation of authigenic arsenian pyrite in subsurface sediments. Moreover, evidence for substitution of AsII,III for Fe in our synthetic samples raises questions about both the possible occurrence and the geochemical reactivity of such As-bearing pyrites in low-temperature subsurface environments.

Occurrence, Sources and Pathways of Antimony and Silver in an Urban Catchment

The recently introduced and increasing uses of silver (Ag) and antimony (Sb) have resulted in an increasing concern on their impacts to the environment. Nevertheless, little information can be found about anthropogenic impacts on the geochemical behaviour of such trace metals in urban river. In the course of our studies dedicated to the Seine River basin, France (67,400 km2), a large set of data was collected. Silver and antimony inputs to the Seine River Basin were estimated using three relevant sources: atmospheric deposition, waste water treatment plants effluents and combined sewer overflows. The Ag and Sb dissolved/solid partition in the river was also estimated on an annual basis. Results showed that Ag output river flux cannot be balanced with the input fluxes, unless to consider another source, which could be the erosion of contaminated soils. In opposite, the Sb budget is well balanced, with atmospheric deposition dominating the input fluxes to the river. The Ag and Sb geochemical behaviors (i.e., their dissolved/solid partition) are highly contrasted, especially for Sb, which dissolved/solid partition is even more fluctuant depending on the emission route.

Local environment of arsenic in sulfide minerals: insight from high-resolution X-Ray spectroscopies, and first-principle calculations at the As K-edge

Whereas electronic properties of As-bearing compounds find various industrial applications in smartphone and photovoltaic devices, or in superconductor materials, arsenic is a toxic element present in a variety of contaminated surface environments. In natural media, the knowledge of its chemical speciation and oxidation state is crucial to apprehend its mobility, bioavailability and toxicity towards the ecosystems. To that purpose, chemical selective experimental methods, such as X-ray absorption spectroscopy (XAS) and related techniques are powerful tools. Here, a selection of As species in the As–Fe–S system presenting various oxidation states and local structures are thoroughly discriminated using resonant inelastic X-ray scattering (RIXS), high-energy fluorescence detection (HERFD-XANES), and first-principles X-ray absorption near-edge structure (XANES) calculations, highlighting the interest of going beyond the usual fingerprint analysis of standard experimental XANES spectra. The position of maximum fluorescence on the RIXS plane is proved to be an advanced fingerprint of the As local environment. HERFD-XANES spectra are found to significantly improve the spectral resolution and to reduce the signal background at the As K-edge, but have to be interpreted carefully as they present different shifts in energy compared to their standard XANES counterparts. First-principles As K-edge XANES calculations are performed for reference compounds with arsenic oxidation states ranging from −I to +III (arsenopyrite (FeAsS), lollingite (FeAs2), realgar (AsS) and orpiment (As2S3)). Comparison with experimental spectra shows that the oxidation state of As can be retrieved from the position of the inflection point of the edge. XANES calculations are also carried out for As incorporated as an impurity in pyrite either at the S tetrahedral or Fe octahedral sites, allowing us to draw conclusions on the oxidation state of As in this mineral ubiquitous in the environment.

Arsenic speciation in Mekong Delta sediments depends on their depositional environment

Arsenic contamination in groundwater is pervasive throughout deltaic regions of Southeast Asia and threatens the health of millions. The speciation of As in sediments overlying contaminated aquifers is poorly constrained. Here, we investigate the chemical and mineralogical compositions of sediment cores collected from the Mekong Delta in Vietnam, elucidate the speciation of iron and arsenic, and relate them to the sediment depositional environment. Gradual dissolution of ferric (oxyhydr)oxides with depth is observed down to 7 m, corresponding to the establishment of reducing conditions. Within the reduced sediment, layers originating from marine, coastal or alluvial depositional environments are identified and their age is consistent with a late Holocene transgression in the Mekong Delta. In the organic matter- and sulfur-rich layers, arsenic is present in association with organic matter through thiol-bonding and in the form of arsenian pyrite. The highest arsenic concentration (34-69 ppm) is found in the peat layer at 16 m and suggests the accumulation of arsenic due to the formation of thiol-bound trivalent arsenic (40-55%) and arsenian pyrite (15-30%) in a paleo-mangrove depositional environment (∼8079 yr BP). Where sulfur is limited, siderite is identified, and oxygen- and thiol-bound trivalent arsenic are the predominant forms. It is also worth noting that pentavalent arsenic coordinated to oxygen is ubiquitous in the sediment profile, even in reduced sediment layers. But the identity of the oxygen-bound arsenic species remains unknown. This work shows direct evidence of thiol-bound trivalent arsenic in the Mekong Delta sediments and provides insight to refine the current model of the origin, deposition, and release of arsenic in the alluvial aquifers of the Mekong Delta.