A chemical status predictor. A methodology based on World-Wide sediment samples.

As a consequence of the limited resources of underdeveloped countries and the limited interest of the developed ones, the assessment of the chemical quality of entire water bodies around the world is a utopia in the near future. The methodology described here may serve as a first approach for the fast identification of water bodies that do not meet the good chemical status demanded by the European Water Framework Directive (WFD). It also allows estimating the natural background (or reference values of concentration) of the areas under study using a simple criterion. The starting point is the calculation the World-Wide Natural Background Levels (WWNBLs) and World-Wide Threshold Values (WWTVs), two indexes that depend on the concentration of seven elements present in sediments. These elements, As, Cd, Cr, Cu, Ni, Pb and Zn, have been selected taking into account the recommendations of the UNEP (United Nations Environment Programme) and USEPA (United States Environmental Protection Agency), that describe them as elements of concern with respect to environmental toxicity. The methodology has been exemplified in a case study that includes 134 sediment samples collected in 11 transitional water bodies from 7 different countries and 4 different continents. Six of the water bodies considered met the good chemical status demanded by the WFD. The rest of them exceeded the reference WWTVs, at least for one of the elements. The estuaries of the Nerbioi-Ibaizabal (Basque Country) and Cavado (Portugal), the sea inlet of Río San Pedro (Spain), the Sepetiba Bay (Brazil) and the Yucateco lagoon (Mexico) belong to that group.

Geographical distribution of metals and metalloids along the estuary of the Oka River in the biosphere reserve of Urdaibai, Spain.

Sediments sampled at the estuary of the Oka River in the biosphere reserve of Urdaibai, Spain were analyzed for trace elements. Sediments were collected at 45 points of the estuary and the concentration of 14 elements was measured. The geoaccumulation indexes (Igeo), Normalized Average Weighted Concentrations (NAWC) and mean Effect Range-Median quotients (mERMq) were calculated. The results obtained were complementary and allowed intra- and inter-estuary comparison. According to the present findings, the estuary was classified as healthy, since the anthropogenic contribution of metals and metalloids was generally small. However, shipping and fishing activities at the ports of Bermeo and Mundaka and urban and industrial wastes from Gernika were regarded as the major pollution sources. Nevertheless, only slightly contaminated and toxic sediments, especially related to Ni and Cu, were found in the towns of Gernika and Mundaka.

Homogeneity assessment of the SuperCam calibration targets onboard rover perseverance.

The SuperCam instrument, onboard the Perseverance rover (Mars 2020 mission) is designed to perform remote analysis on the Martian surface employing several spectroscopic techniques such as Laser Induced Breakdown Spectroscopy (LIBS), Time-Resolved Raman (TRR), Time-Resolved Fluorescence (TRF) and Visible and Infrared (VISIR) reflectance. In addition, SuperCam also acquires high-resolution images using a color remote micro-imager (RMI) as well as sounds with its microphone. SuperCam has three main subsystems, the Mast Unit (MU) where the laser for chemical analysis and collection optics are housed, the Body Unit (BU) where the different spectrometers are located inside the rover, and the SuperCam Calibration Target (SCCT) located on the rover's deck to facilitate calibration tests at similar ambient conditions as the analyzed samples. To perform adequate calibrations on Mars, the 22 mineral samples included in the complex SCCT assembly must have a very homogeneous distribution of major and minor elements. The analysis and verification of such homogeneity for the 5-6 replicates of the samples included in the SCCT has been the aim of this work. To verify the physic-chemical homogeneity of the calibration targets, micro Energy Dispersive X-ray Fluorescence (EDXRF) imaging was first used on the whole surface of the targets, then the relative abundances of the detected elements were computed on 20 randomly distributed areas of 100 × 100 µm. For those targets showing a positive Raman response, micro-Raman spectroscopy imaging was performed on the whole surface of the targets at a resolution of 100 × 100 µm. The %RSD values (percent of relative standard deviation of mean values) for the major elements measured with EDXRF were compared with similar values obtained by two independent LIBS set-ups at spot sizes of 300 µm in diameter. The statistical analysis showed which elements were homogeneously distributed in the 22 mineral targets of the SCCT, providing their uncertainty values for further calibration. Moreover, nine of the 22 targets showed a good Raman response and their mineral distributions were also studied. Those targets can be also used for calibration purposes of the Raman part of SuperCam using the wavenumbers of their main Raman bands proposed in this work.

In-situ multianalytical approach to analyze and compare the degradation pathways jeopardizing two murals exposed to different environments (Ariadne House, Pompeii, Italy).

This study aimed at using portable analytical techniques to characterize original and decayed materials from two murals paintings of Ariadne House (archaeological site of Pompeii, Italy) and define the degradation pathways threatening their conservation. The first wall, located in an outdoor environment, has been directly exposed to degradation processes triggered by weathering and atmospheric pollution. The second wall, placed in a basement under the ground floor, has been constantly sheltered from sunlight exposure and drastic temperature fluctuations. The analytical data obtained in-situ by using Raman spectroscopy and Laser Induced Breakdown Spectroscopy (LIBS) correlates the degradation patterns affecting the two surfaces to their environmental context. The deterioration processes detected on the outdoor wall, which entailed the complete loss of the paint layer, were mostly related to leaching and thermal fluctuation phenomena. The mural painting from the basement instead, showed deep degradation issues due to soluble salt infiltration and biological colonization. The results obtained from this unique case of study highlight the indispensable role of in-situ spectroscopic analysis to understand and predict the degradation pathways jeopardizing the cultural heritage and provide to the Archaeological Park of Pompeii important inference to consider in future conservation projects.

Brazilian coal mining residues and sulphide oxidation by Fenton's reaction: an accelerated weathering procedure to evaluate possible environmental impact.

Fenton's reaction is proposed as an accelerated weathering test for sulphides associated with Brazilian Coal Mining Residues (CMR), that are exposed to oxygen and water during the mining of coal. TEM and SEM/EDX were used to evaluate the nature, occurrence and distribution of minerals in remaining coals and other lithological units, before and after applying the test. Oxidation of CMRs was examined by analyzing soluble sulphur (sulphate) and dissolved metals by ICP-MS or ICP OES. As dissolved sulphate increases, dissolved Zn, Cd, Cu and Co concentrations increase, leading to undetectable amounts in the remaining solid phases; dissolved Ni and Mn also increase with the mobilized sulphur, but the remainder in the solids is the most important fraction; Fe and Pb are not mobilized due to precipitation as jarosite or hematite in the case of Fe or as sulphate in the case of Pb. Agreement between the observed results and the predictions by geochemical modelling is discussed.