Application of Pattern Mining Methods to Assess Exposures to Multiple Airborne Chemical Agents in Two Large Occupational Exposure Databases from France.

Surveys of the French working population estimate that approximately 15% of all workers may be exposed to at least three different chemical agents, but the most prevalent coexposure situations and their associated health risks remain relatively understudied. To characterize occupational coexposure situations in France, we extracted personal measurement data from COLCHIC and SCOLA, two large administrative occupation exposure databases. We selected 118 chemical agents that had ≥100 measurements with detected concentrations over the period 2010-2019, including 31 carcinogens (IARC groups 1, 2A, and 2B). We grouped measurements by work situations (WS, combination of sector, occupation, task, and year). We characterized the mixtures across WS using frequent itemset mining and association rules mining. The 275,213 measurements extracted came from 32,670 WS and encompassing 4692 unique mixtures. Workers in 32% of all WS were exposed to ≥2 agents (median 3 agents/WS) and 13% of all WS contained ≥2 carcinogens (median 2 carcinogens/WS). The most frequent coexposures were ethylbenzene-xylene (1550 WS), quartz-cristobalite (1417 WS), and toluene-xylene (1305 WS). Prevalent combinations of carcinogens also included hexavalent chromium-lead (368 WS) and benzene-ethylbenzene (314 WS). Wood dust (6% of WS exposed to at least one other agent) and asbestos (8%) had the least amount of WS coexposed with other agents. Tasks with the highest proportions of coexposure to carcinogens include electric arc welding (37% of WS with coexposure), polymerization and distillation (34%), and construction drilling and excavating (34%). Overall, the coexposure to multiple chemical agents, including carcinogens, was highly prevalent in the databases, and should be taken into account when assessing exposure risks in the workplace.

AltrexChimie, a Web Application for the Management and the Interpretation of Occupational Exposure Measurements to Chemical Substances.

In most occupational settings, several chemical agents are commonly found, and the associated exposure risk for workers must be assessed. For this purpose, air samples can be collected and analyzed. AltrexChimie is a web application that helps industrial hygienists in the organization of the air sampling strategy and in the subsequent phases of data management, analysis, and communication. AltrexChimie contains a database of more than 550 chemical substances and their respective French Occupational Exposure Limit Values (OELV): Custom OELVs can also be defined by the user. AltrexChimie helps with the definition of key features of the sampling strategy, in particular by promoting a methodology for the design of Similar Exposure Groups (SEGs). Once measurement data are entered, they can be analyzed to obtain exposure diagnostics. Data management features allow for the easy storage and retrieval of measurements, and comprehensive dashboards help industrial hygienists (IHs) in the communication of results. Finally, with AltrexChimie it is also possible to assess exposure to multiple chemical substances and their additive effects. While most free software applications for the assessment of chemical exposure focus on the statistical computation of specific indicators, AltrexChimie offers several tools to assist IHs in the exposure assessment workflow. AltrexChimie is available without registration from INRS at https://altrex.inrs.fr.

Bioaccumulation of thallium and other trace metals in Biscutella laevigata nearby a decommissioned zinc-lead mine (Northeastern Italian Alps).

The mineral body exploited in Salafossa (Eastern Dolomites) was one of the largest lead/zinc-containing mineral deposits in Europe. Both metals were mainly present as sulphides (sphalerite, ZnS and galena, PbS). Mining activity started around 1550, but it was only around 1960 that the richest veins of the minerals were discovered. The mine closed in 1985, and concentrations of several trace metals, such as thallium (Tl), iron (Fe), manganese (Mn), lead (Pb) and zinc (Zn), were detected in the soils and plant samples (Biscutella laevigata L.) that were collected from eighteen sites selected outside the mine. B. laevigata is a pseudometallophyta species, and it often grows near mining areas where the soil's metal concentrations are significantly higher than those of soil with a natural geochemical background. The total metal concentrations in the plant tissue (roots and leaves of Biscutella laevigata) and in the soil samples - both bulk-soil and the B. laevigata root system (rhizo-soil) - were determined through Inductively Coupled Plasma Optical Emission Spectrometry (ICP-OES). The metal extractability and leachability of the soil samples were estimated using soil extractions with DTPA (Diethylenetriaminepentaacetic acid). In addition, metal mobility caused by rainwater runoff was estimated by using a leaching test with a dilute solution of H2SO4 and HNO3. The results showed that metals were present in a chemical form available for uptake by the plants' roots. In fact, high concentrations of the metals were also found in the plant tissue (roots and leaves) of B. laevigata, and these concentrations were higher than those whose soils present natural geochemical background levels in the corresponding rhizo-soil. Thus, B. laevigata has shown a marked ability to bioaccumulate trace metals, especially Tl and, to a lesser extent, Zn, Pb, Fe and Mn, and it can influence metal mobility in the rhizo-soil. To assess the uptake and translocation processes of the trace metals, resulting in their bioaccumulation, two different indices were calculated: the enrichment factor in roots (EFr), as the ratio between the metal concentration in belowground biomass and in the respective rhizo-soil, and the translocation factor (TF), as the ratio between the metal concentration in the leaves and the corresponding roots. For both indices, values > 1 denoted enrichment of the metal in the roots or its translocation to the upper tissues. The results showed that EFr and TF were considerably high only for Tl, reaching a maximum value of 60 for EFr and 11.6 for TF. Conversely, the other investigated metals did not show significant bioaccumulation (EFr < 1), and they showed TF > 1 only at a few sites.

DoE optimization of a mercury isotope ratio determination method for environmental studies.

By using the experimental design (DoE) technique, we optimized an analytical method for the determination of mercury isotope ratios by means of cold-vapor multicollector ICP-MS (CV-MC-ICP-MS) to provide absolute Hg isotopic ratio measurements with a suitable internal precision. By running 32 experiments, the influence of mercury and thallium internal standard concentrations, total measuring time and sample flow rate was evaluated. Method was optimized varying Hg concentration between 2 and 20 ng g(-1). The model finds out some correlations within the parameters affect the measurements precision and predicts suitable sample measurement precisions for Hg concentrations from 5 ng g(-1) Hg upwards. The method was successfully applied to samples of Manila clams (Ruditapes philippinarum) coming from the Marano and Grado lagoon (NE Italy), a coastal environment affected by long term mercury contamination mainly due to mining activity. Results show different extents of both mass dependent fractionation (MDF) and mass independent fractionation (MIF) phenomena in clams according to their size and sampling sites in the lagoon. The method is fit for determinations on real samples, allowing for the use of Hg isotopic ratios to study mercury biogeochemical cycles in complex ecosystems.

Mobility of heavy metals from polluted sediments of a semi-enclosed basin: in situ benthic chamber experiments in Taranto's Mar Piccolo (Ionian Sea, Southern Italy).

In situ benthic flux experiments were conducted at two stations in the Mar Piccolo of Taranto (Italy), one of the most industrialised and contaminated coastal areas of the Mediterranean. Sediments of the two stations are notably different in their trace metal content, with a station closer to a Navy harbour showing higher mean concentrations of almost all investigated metals (Al, As, Cd, Cr, Cu, Fe, Hg, Mn, Ni, Pb, V and Zn). Conversely, both stations are characterised by significant Hg contamination, compared to the local baseline. Results of a sequential extraction scheme on surface sediments suggest a relatively scarce mobility of the examined metals (Zn > Ni > Cr > As > Cu > Pb). A Hg-specific extraction procedure showed that most of the element (93.1 %) occurs in a fraction comprising Hg bound to Fe/Mn oxi-hydroxides. Reduction of these oxides may affect Hg remobilisation and redistribution. Porewater profiles of dissolved trace metals were quite similar in the two sites, although significant differences could be observed for Al, Cu, Fe and Hg. The highest diffusive fluxes were observed for As, Fe and Mn. Mobility rates of several trace elements (Al, As, Cd, Cr, Cu, Fe, Hg, Mn, Ni, Pb, V and Zn) were directly measured at the sediment-water interface. Results from benthic in situ incubation experiments showed increasing dissolved metal concentrations with time, resulting in higher fluxes for Cu, Fe, Hg, V and Zn in the most contaminated site. Conversely, fluxes of Mn, Ni and Pb were comparable between the two stations. The estimated flux of Hg (97 µg m(-2) day(-1)) was the highest observed among similar experiments conducted in other highly contaminated Mediterranean coastal environments. Benthic fluxes could be partially explained by considering rates of organic matter remineralisation, dissolution of Fe/Mn oxy-hydroxides and metal speciation in sediments. Seasonal and spatial variation of biogeochemical parameters can influence metal remobilisation in the Mar Piccolo area. In particular, metals could be promptly remobilised as a consequence of oxygen depletion, posing a serious concern for the widespread fishing and mussel farming activities in the area.

Oxygen, carbon, and nutrient exchanges at the sediment-water interface in the Mar Piccolo of Taranto (Ionian Sea, southern Italy).

In the shallow environment, the nutrient and carbon exchanges at the sediment-water interface contribute significantly to determine the trophic status of the whole water column. The intensity of the allochthonous input in a coastal environment subjected to strong anthropogenic pressures determines an increase in the benthic oxygen demand leading to depressed oxygen levels in the bottom waters. Anoxic conditions resulting from organic enrichment can enhance the exchange of nutrients between sediments and the overlying water. In the present study, carbon and nutrient fluxes at the sediment-water interface were measured at two experimental sites, one highly and one moderately contaminated, as reference point. In situ benthic flux measurements of dissolved species (O2, DIC, DOC, N-NO3 (-), N-NO2 (-), N-NH4 (+), P-PO4 (3-), Si-Si(OH)4, H2S) were conducted using benthic chambers. Furthermore, undisturbed sediment cores were collected for analyses of total and organic C, total N, and biopolymeric carbon (carbohydrates, proteins, and lipids) as well as of dissolved species in porewaters and supernatant in order to calculate the diffusive fluxes. The sediments were characterized by suboxic to anoxic conditions with redox values more negative in the highly contaminated site, which was also characterized by higher biopolymeric carbon content (most of all lipids), lower C/N ratios and generally higher diffusive fluxes, which could result in a higher release of contaminants. A great difference was observed between diffusive and in situ benthic fluxes suggesting the enhancing of fluxes by bioturbation and the occurrence of biogeochemically important processes at the sediment-water interface. The multi-contamination of both inorganic and organic pollutants, in the sediments of the Mar Piccolo of Taranto (declared SIN in 1998), potentially transferable to the water column and to the aquatic trophic chain, is of serious concern for its ecological relevance, also considering the widespread fishing and mussel farming activities in the area.