Air quality, metal(loid) sources identification and environmental assessment using (bio)monitoring in the former mining district of Salsigne (Orbiel valley, France).

The former mining district of Salsigne is situated in the Orbiel valley. Until the 20th century, it was the first gold mine in Europe and the first arsenic mine in the world. Rehabilitation has been performed during the 20 years that followed closure of the mines and factories, which led to the accumulation of storage of several million tons of waste in this valley. Nevertheless, a detailed description of the air quality of this area is still missing. The goal of the present study is to evaluate atmospheric contamination in the valley and identify the potential sources of this contamination. Active monitors (particulate matter samplers) and passive bioindicators (Tillandsia usneoides) were placed in strategic sites including remote areas. Over the year 2022, we assessed the air quality using microscopic and spectroscopic techniques, as well as environmental risk indicators to report the level of contamination. Results indicate that the overall air quality in the valley is good with PM10 levels in accordance with EU standards. Elemental concentrations in the exposed plants were lower than reported in the literature. Among the different sites studied, Nartau and La Combe du Saut, corresponding to waste storage and former mining industry sites, were the most affected. Chronic exposure over 1 year was highlighted for Fe, Ni, Cu, Pb, Sb and As. Pollution Load Index and Enrichment Factors, which provided valuable information to assess the environmental condition of the valley's air, suggested that dust and resuspension of anthropogenic materials were the principle sources for most of the elements. Finally, this study also highlights that using T. usneoides could be a convenient approach for biomonitoring of metal (loid)-rich particles in the atmosphere within a former mining area, for at least one year. These results in turn allow to better understand the effects of chronic exposure on the ecosystem.

The importance of simulated lung fluid (SLF) extractions for a more relevant evaluation of the oxidative potential of particulate matter.

Particulate matter (PM) induces oxidative stress in vivo, leading to adverse health effects. Oxidative potential (OP) of PM is increasingly studied as a relevant metric for health impact (instead of PM mass concentration) as much of the ambient particle mass do not contribute to PM toxicity. Several assays have been developed to quantify PM oxidative potential and a widely used one is the acellular dithiothreitol (DTT) assay. However in such assays, particles are usually extracted with methanol or Milli-Q water which is unrepresentative of physiological conditions. For this purpose, OPDTT measurements after simulated lung fluids (SLF) extraction, in order to look at the impact of simulated lung fluid constituents, were compared to Milli-Q water extraction measurements. Our major finding is a significant decrease of the OPDTT when the artificial lysosomal fluid (ALF) solution was used. Indeed, ligand compounds are present in the SLF solutions and some induce a decrease of the OP when compared to water extraction. Our results suggest that the effect of ligands and complexation in lining fluids towards PM contaminants probably has been underestimated and should be investigated further.

Toxicity of TiO2 nanoparticles on soil nitrification at environmentally relevant concentrations: Lack of classical dose-response relationships.

Titanium-dioxide nanoparticles (TiO2-NPs) are increasingly released in agricultural soils through, e.g. biosolids, irrigation or nanoagrochemicals. Soils are submitted to a wide range of concentrations of TiO2-NPs depending on the type of exposure. However, most studies have assessed the effects of unrealistically high concentrations, and the dose-response relationships are not well characterized for soil microbial communities. Here, using soil microcosms, we assessed the impact of TiO2-NPs at concentrations ranging from 0.05 to 500 mg kg-1 dry-soil, on the activity and abundance of ammonia-oxidizing archaea (AOA) and bacteria (AOB), and nitrite-oxidizing bacteria (Nitrobacter and Nitrospira). In addition, aggregation and oxidative potential of TiO2-NPs were measured in the spiking suspensions, as they can be important drivers of TiO2-NPs toxicity. After 90 days of exposure, non-classical dose-response relationships were observed for nitrifier abundance or activity, making threshold concentrations impossible to compute. Indeed, AOA abundance was reduced by 40% by TiO2-NPs whatever the concentration, while Nitrospira was never affected. Moreover, AOB and Nitrobacter abundances were decreased mainly at intermediate concentrations nitrification was reduced by 25% at the lowest (0.05 mg kg-1) and the highest (100 and 500 mg kg-1) TiO2-NPs concentrations. Path analyses indicated that TiO2-NPs affected nitrification through an effect on the specific activity of nitrifiers, in addition to indirect effects on nitrifier abundances. Altogether these results point out the need to include very low concentrations of NPs in soil toxicological studies, and the lack of relevance of classical dose-response tests and ecotoxicological dose metrics (EC50, IC50…) for TiO2-NPs impact on soil microorganisms.

Metal concentration and bioaccessibility in different particle sizes of dust and aerosols to refine metal exposure assessment.

Refined exposure assessments were realized for children, 7-9yrs, in the mining/smelting city of Oruro, Bolivia. Aerosols (PM>2.5, PM1-2.5, PM0.4-1 and PM0.5) and dust (separated in different particle size fractions: 2000-200µm, 200-50µm, 50-20µm, 20-2µm and <2µm) were sampled on football fields highly frequented by children in both the mining and smelting areas. Trace element concentrations (Ag, As, Cd, Cu, Pb, Sb, Sn and Zn) in each size fraction of dust and aerosols, lung bioaccessibility of metals in aerosols, and gastric bioaccessibility of metals in dust were measured. Exposure was assessed considering actual external exposure (i.e. exposure pathways: metals inhaled and ingested) and simulated internal exposure (i.e., complex estimation using gastric and lung bioaccessibility, deposition and clearance of particles in lungs). Significant differences between external and simulated internal exposure were attributed to dissemblances in gastric and lung bioaccessibilities, as well as metal distribution within particle size range, revealing the importance of both parameters in exposure assessment.