Strong evidence for the continued contribution of lead deposited during the 20th century to the atmospheric environment in London of today.

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.

Contrasting arsenic biogeochemical cycling in two Moroccan alkaline pit lakes.

Pit lakes resulting from the flooding of abandoned mines represent a valuable freshwater reserve. However, water contamination by toxic elements, including arsenic, compromises their use for freshwater supply. For a better management of these reserves, our aim was to gain insight into arsenic cycling in two Moroccan alkaline pit lakes. We first showed that dimethylarsenic dominated in stratified lake ZA whereas in lake ZL1, As(V) was prevailing. Because microbially mediated processes largely contribute to arsenic cycling, the diversity of arsenic-methylating and -oxidizing bacteria was determined through the sequencing of arsM and aioA genes. Diverse arsM-carrying bacteria were thriving in ZA while a low diversity of aioA genes was detected in ZL1. We also determined the structure of the total bacterial communities by fingerprinting (ARISA). Contrasting arsenic speciation and bacterial communities in the two lakes were associated with differences of conductivity, Total Organic Carbon and temperature. In ZA, dissolved oxygen and redox potential were the main factors driving the total bacterial community structure and the ArsM diversity. In ZL1, stable bacterial communities were associated with limited water physico-chemistry variations. Our study provides new insights into the biogeochemical behavior of arsenic and the role of arsenic transforming bacteria in alkaline pit lakes.

Temperature and nutrients as drivers of microbially mediated arsenic oxidation and removal from acid mine drainage.

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 environmental legacy of historic Pb-Zn-Ag-Au mining in river basins of the southern edge of the Massif Central (France).

The main rivers (Aude, Orb, Herault) that discharge into the Gulf of Lions and the west bank tributaries of the Rhone River including the Gardon have former non-ferrous metal mines in their upper drainage basin. Using unpublished data and data from the literature, this study provides an integrated overview of the contamination of water and sediment along the continent-sea continuum and of its impacts on the biota and on human health. In the upper part of these basins, water and stream sediments are enriched in metal(-loids) compared to median European concentrations. Arsenic is the main contaminant in the rivers Aude and Gardon d'Anduze, Sb in the Orb and Gardon d'Alès, and Tl in the Herault river. A rapid reduction in dissolved and particulate concentrations was systematically observed along the river due to dilution and precipitation. The high concentrations of metal(-loid)s observed suggest that the former mining activity still represents a potential threat for the environment, but the lack of high temporal resolution monitoring, especially during Mediterranean floods, prevents accurate assessment of metal fluxes from these rivers to the Mediterranean Sea. Studies dedicated to the impacts on human health are too rare, given that studies have shown a higher rate of arsenic-specific cancer near Salsigne mine in the Aude River basin and cases of saturnism in children in the upper Herault River basin. These studies underline the need to take environmental health issues into consideration not only in these watersheds but around the entire Mediterranean basin, which harbors numerous metalliferous ores that have been mined for millennia.

Antimony isotopic composition in river waters affected by ancient mining activity.

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.

Persisting impact of historical mining activity to metal (Pb, Zn, Cd, Tl, Hg) and metalloid (As, Sb) enrichment in sediments of the Gardon River, Southern France.

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

Fate of Sb(V) and Sb(III) species along a gradient of pH and oxygen concentration in the Carnoulès mine waters (Southern France).

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.