Relation between solid phase speciation and oral/lung bioaccessibility of metal(loid)s polluted soils in inhabited area: Contribution of synchrotron-based experiment.

The presence of contaminated sites/soils in or near cities can pose significant risks to public health. The city of Viviez (France) was taken in reference site bears significant industrial responsibility, particularly in zinc metallurgy, with the presence of a now rehabilitated smelter. This has led to soil contamination by zinc (Zn), lead (Pb), arsenic (As), and cadmium (Cd), with concentrations reaching up to 4856 mg kg-1, 1739 mg kg-1, 195 mg kg-1, and 110 mg kg-1, respectively. The aim of this study is to comprehend the contamination patterns of the site post-rehabilitation, the geochemical behavior of each element, and their speciation (analyzed through BCR, XRD, and XANES) in relation to associated health risks due to metals accessibility for oral ingestion and inhalation by the local population. The findings revealed that elements inducing health risks were not necessarily those with the highest metal contents. All results are discussed in terms of the relationship between element speciation, stability of bearing phases, and their behavior in different media. XANES is an important tool to determine and estimate the Pb-bearing phases in garden soils, as well as the As speciation, which consist of Pb-goethite, anglesite, and Pb-humate, with variations in proportions (the main phases being 66 %, 12 % and 22 % for Pb-goethite, anglesite, and Pb-humate, respectively) whereas As-bearing phase are As(V)-rich ferrihydrite-like. A new aspect lies in the detailed characterization of solid phases before and after bioaccessibility tests, to qualify and quantify the bearing phases involved in the mobility of metallic elements to understand the bioaccessibility behavior. Ultimately, the health risk associated with exposure to inhabitants, in terms of particle ingestion and inhalation, was assessed. Only ingestion-related risk was deemed unacceptable due to the levels of As and Pb.

Investigating the relationship between speciation and oral/lung bioaccessibility of a highly contaminated tailing: contribution in health risk assessment.

Anthropogenic activities such as industrial, mining, or agricultural are the main sources of environmental contamination. One of the most problematic contaminations concerns metals and metalloids from mining activities. This contamination raises the question of the environmental risk induced and the spread of this pollution (geographical and trophic) and the associated health risk. The integrated, multi-analytical approach of this study conducted on the mining district of Cartagena-La Union (Murcia, Spain) as part of the Interreg SUDOE European project "Soil Take Care" aims to (i) precisely define the speciation of contaminants of interest (Zn, Pb, Cd, As), (ii) predict the environmental risk related to storage stability, and (iii) establish the link between the speciation of the bearing phases and the associated health risk. To do this, a representative zone in the Cartagena-La Union mining district close to the populations was chosen. A physic-chemical characterization of the samples was performed (pH, electrical conductivity, CEC, and total metal(loid) concentrations), and the mineralogy was determined using XRD and SEM-EDS. The environmental risk was highlighted from sequential BCR-type extractions and EN-12457 leaching tests. Finally, the health risk was defined using the PSF inhalation bioaccessibility test and UBM bioaccessibility protocol (based on an operational chemical methodology mimicking soil ingestion and its residence in the gastrointestinal tract of the human body). These analyses revealed 2 groups of samples with distinct behavior. The first group of samples presents relatively stable bearing phases, mainly found in the residual fraction (As and Pb), presenting only a low health risk (very low bioaccessible). The second group consists of Cd and/or Zn-bearing phases, mainly labile (resulting from dissolution/precipitation phenomena), while gastric bioaccessibility reaches more than 85%. Note that Pb, Cd, and Zn have the potential to cause non-carcinogenic risks to children and As and Pb present a carcinogenic risk for children and adults even if only the bioaccessible fraction is considered. It has therefore been shown that the meteoric alteration of the tailing induces a change in speciation leads to an increase in environmental and health risks. These results are essential because they highlight the need for an integrated approach in order to clearly highlight the presence of risks but also that this approach will allow a better understanding of the potential rehabilitation path of this site.

Atmospheric dust characterisation in the mining district of Cartagena-La Unión, Spain: Air quality and health risks assessment.

Nowadays, air pollution has a major impact on the environment and human health. Owen gauges allow the sampling of atmospheric depositions in polluted sites for further characterisation. This paper shows the study of the air particles of an old mining zone in Cartagena-La Unión (South-east of Spain) in order to quantify their potential risk on human health. There were 4 strategic sites monitored: the main mining tailing (Avenque), the urban area (La Unión), an agricultural zone (formerly mining) and a site in the Mediterranean coast. Physico-chemical and mineralogical characterisation was applied to atmospheric fallouts. The granulometry revealed a dust particle size around 15 µm, with the coarsest particles in the urban area and the thinnest at the tailing site. XRD analyses showed the presence of quartz, carbonates, sulphides and sulphates. Observations with SEM-EDX confirmed chemical spectra and allowed us to classify the particles into well-crystallised minerals and heterogeneous dusts. Total metal content determination was carried out by ICP-MS analyses and results showed Zn, Pb, As and Cd fluxes (respectively 2549, 1275, 68 and 7 µg·m-2·d-1) exceeding the limit values set by European legislations in the mining area. The fluxes of Zn, Pb and As also exceed these standards in the urban area whereas the coastal zone only exceeds the thresholds in the case of As. Inhalation health risk (defined by US EPA, 2009) was quantified in the sites using total and bioaccessible metal contents of the dusts. Risk calculations using total metal content considering a residential scenario showed acceptable risk for all sites except for the mining tailing which presented non-acceptable cancer and hazard risk mainly due to the total As and Pb contents. When considering the bioaccessible fraction of As and Pb, the risk diminished to acceptable values, demonstrating the overestimation produced when using total metal contents.

Identification of disinfection by-products of selected triazines in drinking water by LC-Q-ToF-MS/MS and evaluation of their toxicity.

During the development of an on-line solid phase extraction-liquid chromatography-ultraviolet detection (SPE-LC-UV) analytical method for determination of eight selected triazines; ametryn, atrazine, cyanazine, metrybuzine, prometryn, propazin, simazine, and terbutryn, in drinking water, it was observed that the retention times of three of them (ametryn, prometryn, and terbutryn) in Milli-Q water were different from those in chlorinated Milli-Q water, indicating the formation of new products. The cause of this change was found in the oxidation of the molecules as a result of chlorination with sodium hypochlorite. Experiments performed at varying concentrations of triazines and hypochlorite showed that the extent of the reaction depended on their relative concentrations. At the maximum admissible level of 100 ng/l for individual pesticides in drinking water, no apparent transformation was observed in the absence or at low concentrations (0.05 mg/l) of hypochlorite; however, on increasing the concentration of hypochlorite to the level typically present in drinking water (0.9 mg/l) the transformation was complete. The reaction is quite fast; within 1 h the parent compound is completely degraded and after 22 h the concentrations of the by-products are constant. Investigation of the by-products by ultra performance liquid chromatography-quadrupole-time of flight- tandem mass spectrometry (UPLC-Q-ToF-MS/MS) has shown that all three triazines follow a similar transformation pathway, forming four new molecules whose structure have been elucidated. The acute toxicity of the new products was investigated using a standard method based on the bioluminescence inhibition of Vibrio fischeri, and the by-products showed a higher toxicity than that of the parent compounds.