In this study, we assessed past and present influence of ancient mining activity on metal(loid) enrichment in sediments of a former mining watershed (Gardon River, SE France), that is now industrialized and urbanized. A sedimentary archive and current sediments were characterized combining geochemical analyses, zinc isotopic analyses and sequential extractions. The archive was used to establish local geochemical background and recorded (i) increasing enrichment factors (EFs) for Pb, Zn, Cd, Tl, Hg, As and Sb throughout the industrial era, (ii) a contamination peak in 1976 attributed to a tailings dam failure, and (iii) current levels in 2002 and 2011 similar to those of 1969, except for Sb and Hg, reflecting a persisting contamination pattern. Inter-element relationships and spatial distribution of EF values of current sediments throughout the watershed suggested that both ancient and current contamination had a common origin for Pb, Zn, Cd, Tl and As related to the exploitation of Pb/Zn mineralization while old Sb mines and coal extraction area were the main sources for Sb and Hg respectively. This prevailing mining origin was reflected for Zn by a relatively uniform isotopic composition at δ(66)Zn=0.23 ± 0.03‰, although slight decrease from 0.23‰ to 0.18‰ was recorded from upstream to downstream sites along the river course in relation with the contribution of the lighter δ(66)Zn signature (~0.08‰) of acid mine drainage impacted tributaries. Results from sequential extractions revealed that the potential mobility of the studied metal(loid)s varied in the order Sb

Passive water treatments based on biological attenuation can be effective for arsenic-rich acid mine drainage (AMD). However, the key factors driving the biological processes involved in this attenuation are not well-known. Here, the efficiency of arsenic (As) removal was investigated in a bench-scale continuous flow channel bioreactor treating As-rich AMD (∼30-40 mg L). In this bioreactor, As removal proceeds via the formation of biogenic precipitates consisting of iron- and arsenic-rich mineral phases encrusting a microbial biofilm. Ferrous iron (Fe(II)) oxidation and iron (Fe) and arsenic removal rates were monitored at two different water heights (4 and 25 mm) and with/without forced aeration. A maximum of 80% As removal was achieved within 500 min at the lowest water height. This operating condition promoted intense Fe(II) microbial oxidation and subsequent precipitation of As-bearing schwertmannite and amorphous ferric arsenate. Higher water height slowed down Fe(II) oxidation, Fe precipitation and As removal, in relation with limited oxygen transfer through the water column. The lower oxygen transfer at higher water height could be partly counteracted by aeration. The presence of an iridescent floating film that developed at the water surface was found to limit oxygen transfer to the water column and delayed Fe(II) oxidation, but did not affect As removal. The bacterial community structure in the biogenic precipitates in the bottom of the bioreactor differed from that of the inlet water and was influenced to some extent by water height and aeration. Although potential for microbial mediated As oxidation was revealed by the detection of aioA genes, removal of Fe and As was mainly attributable to microbial Fe oxidation activity. Increasing the proportion of dissolved As(V) in the inlet water improved As removal and favoured the formation of amorphous ferric arsenate over As-sorbed schwertmannite. This study proved the ability of this bioreactor-system to treat extreme As concentrations and may serve in the design of future in-situ bioremediation system able to treat As-rich AMD.

Although leaded gasoline was banned at the end of the last century, lead (Pb) remains significantly enriched in airborne particles in large cities. The remobilization of historical Pb deposited in soils from atmospheric removal has been suggested as an important source providing evidence for the hypothetical long-term persistency of lead, and possibly other pollutants, in the urban environment. Here, we present data on Pb isotopic composition in airborne particles collected in London (2014 to 2018), which provide strong support that lead deposited via gasoline combustion still contributes significantly to the lead burden in present-day London. Lead concentration and isotopic signature of airborne particles collected at a heavily trafficked site did not vary significantly over the last decade, suggesting that sources remained unchanged. Lead isotopic composition of airborne particles matches that of road dust and topsoils and can only be explained with a significant contribution (estimate of 32 ± 10 to 43 ± 9% based on a binary mixing model) of Pb from leaded gasoline. The lead isotopes furthermore suggest significant contributions from nonexhaust traffic emissions, even though isotopic signatures of anthropogenic sources are increasingly overlapping. Lead isotopic composition of airborne particles collected at building height shows a similar signature to that collected at street level, suggesting effective mixing of lead within the urban street canyon. Our results have important implications on the persistence of Pb in urban environments and suggest that atmospheric Pb reached a baseline in London that is difficult to decrease further with present policy measures.

In this study, antimony (Sb) isotopic composition was determined in natural water samples collected along two hydrosystems impacted by historical mining activities: the upper Orb River and the Gardon River watershed (SE, France). Antimony isotope ratio was measured by HG-MC-ICP-MS (Hydride Generation Multi-Collector Inductively Coupled Plasma Mass Spectrometer) after a preconcentration and purification step using a new thiol-cellulose powder (TCP) procedure. The external reproducibility obtained for δ(123)Sb measurements of our in-house Sb isotopic standard solution and a certified reference freshwater was 0.06‰ (2σ). Significant isotopic variations were evident in surface waters from the upper Orb River (-0.06‰≤δ(123)Sb≤+0.11‰) and from the Gardon River watershed (+0.27‰≤δ(123)Sb≤+0.83‰). In particular, streams that drained different former mining sites exploited for Sb or Pb-Zn exhibited contrasted Sb isotopic signature, that may be related to various biogeochemical processes occurring during Sb transfer from rocks, mine wastes and sediments to the water compartment. Nevertheless, Sb isotopic composition appeared to be stable along the Gardon River, which might be attributed to the conservative transport of Sb at distance from mine-impacted streams, due to the relative mobile behavior of Sb(V) in natural oxic waters. This study suggests that Sb isotopic composition could be a useful tool to track pollution sources and/or biogeochemical processes in hydrologic systems.

Microbial oxidation of iron (Fe) and arsenic (As) followed by their co-precipitation leads to the natural attenuation of these elements in As-rich acid mine drainage (AMD). The parameters driving the activity and diversity of bacterial communities responsible for this mitigation remain poorly understood. We conducted batch experiments to investigate the effect of temperature (20 vs 35 °C) and nutrient supply on the rate of Fe and As oxidation and precipitation, the bacterial diversity (high-throughput sequencing of 16S rRNA gene), and the As oxidation potential (quantification of aioA gene) in AMD from the Carnoulès mine (France). In batch incubated at 20 °C, the dominance of iron-oxidizing bacteria related to Gallionella spp. was associated with almost complete iron oxidation (98%). However, negligible As oxidation led to the formation of As(III)-rich precipitates. Incubation at 35 °C and nutrient supply both stimulated As oxidation (71-75%), linked to a higher abundance of aioA gene and the dominance of As-oxidizing bacteria related to Thiomonas spp. As a consequence, As(V)-rich precipitates (70-98% of total As) were produced. Our results highlight strong links between indigenous bacterial community composition and iron and arsenic removal efficiency within AMD and provide new insights for the future development of a biological treatment of As-rich AMD.

The variation of dissolved and particulate metal(loid) concentrations was investigated during a Mediterranean flood in a former mining watershed, the Gardon River (SE France), using high-temporal resolution sampling. Dissolved antimony originating from the Upper Gardon River watershed underwent dilution during flood. Conversely, dissolved As and particulate As, Pb, Zn, Cd and Tl concentrations exhibited increased values during rising flood compared to low and receding flow conditions, with a double-peak shape. As, Pb, Cd and Tl concentration data in suspended particulate matter from this double-peak were distributed along two different correlation lines, showing the successive mobilization of two groups of particles highly enriched with As and Cd or Pb and Tl, both inherited from ancient Pb/Zn mines. Metal(loid) loads during the monitored 24 h-flood event were: 0.5 kg for Cd, 19.4 kg for Sb and 204 kg for As in the dissolved phase and 24 kg for Cd, 38 kg for Tl, 94 kg for Sb, 1915 kg for As, 2860 kg for Pb and 5214 kg for Zn in the particulate phase. Altogether, these results highlighted the importance of floods in the mobilization of metals and metalloids from ancient mining sites in Mediterranean regions, showing the need for high-temporal resolution monitoring of flood events to accurately assess the long-term contribution of mining activity to metal(loid) loads of downstream watershed.Please cite this article as: Resongles, E., et al., Variation of dissolved and particulate metal(loid) (As, Cd, Pb, Sb, Tl, Zn) concentrations under varying discharge during a Medite.

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The speciation and behaviour of antimony were investigated in surface waters downstream from the abandoned Pb-Zn Carnoulès mine (Gard, France). These waters exhibit a permanent gradient of oxygen concentration and pH, ranging from acid suboxic in Reigous Creek at the outlet of sulfide tailings impoundment, to near neutral oxygenated at downstream sites along the rivers Amous and Gardon. The concentration of total dissolved (<0.22 μm) antimony, acquired through a seven-year monitoring, decreased from 7.7-409.9 μg L(-1) at the source of Reigous Creek to 0.22-0.45 μg L(-1) in the Gardon River, showing natural Sb attenuation. Speciation analysis carried out during three surveys indicated that Sb(III) represented up to 70% of the total dissolved Sb concentration at the source of Reigous Creek, while Sb(V) represented less than 50%. Field characterization showed that Sb(III) and Sb(V) species were attenuated through dilution and were also removed from the dissolved phase during downstream transport. Speciation analysis in suspended particulate matter extracts gave a distribution of particulate Sb into 70 to 100% of Sb(III) and less than 30% of Sb(V). The removal of Sb(III) and Sb(V) species from the dissolved phase was concordant with the oversaturation of Reigous Creek water relative to Sb(III)- and Sb(V)-oxides and Sb(III)- and Sb(V)-Fe oxides. Sb(III) was more efficiently removed than Sb(V) or As(III) and it was no more detectable in the dissolved phase at downstream sites in the rivers Amous and Gardon. Conversely, the concentration of Sb(V) in the rivers Amous and Gardon still denoted contamination arising from the Carnoulès mine. The range of log Kd values, from 2.4 L kg(-1) to 4.9 L kg(-1), indicated that Sb was mainly transported in the dissolved phase downstream the Reigous Creek input. Altogether, these results give a better understanding of the fate of Sb downstream from sulfide-rich mining wastes.