Ainara Gredilla

Use of Reflectance Infrared Spectroscopy for Monitoring the Metal Content of the Estuarine Sediments of the Nerbioi-Ibaizabal River (Metropolitan Bilbao, Bay of Biscay, Basque Country)

Multivariate partial least-squares (PLS) calibration models have been developed for the spatial and seasonal simultaneous monitoring of 14 trace elements (Al, As, Cd, Co, Cr, Cu, Fe, Mg, Mn, Ni, Pb, Sn, V, and Zn) in sediments from 117 samples taken in the estuary of the Nerbioi-Ibaizabal River. Models were based on the chemometric treatment of diffuse reflectance near-infrared (NIR) and attenuated total reflectance (ATR) mid infrared (MIR) spectra, obtained from samples previously lyophilized and sieved with a particle size lower than 63 microm. Vibrational spectra were scanned in both, NIR and MIR regions. Developed PLS models, based on the interaction between trace elements and organic mater provide good screening tools for the prediction of trace elements concentration in sediments.

Fate of hazardous elements in agricultural soils surrounding a coal power plant complex from Santa Catarina (Brazil)

Hazard element contamination coming from coal power plants is something obvious, but when this contamination is accompanied by other contamination sources, such as, urban, coal mining and farming activities the study gets complicated. This is the case of an area comprised in the southern part of Santa Catarina state (Brazil) with the largest private power plant generator. After the elemental analysis of 41 agricultural soils collected in an extensive area around the thermoelectric (from 0 to 47 km), the high presence of As, Co, Cr, Cu, Fe, Mn, Mo, Pb, Sb, Sn, Tl, V and Zn was found in some specific areas around the power plant. Nevertheless, as the NWAC (Normalized-and-Weighted Average Concentration) confirmed, only soils from one site were classified as of very high concern due to the presence of potential toxic elements. This site was located within the sedimentation basin of the power plant. The spatial distribution obtained by kriging in combination with the analysis of the data by Principal Component Analysis (PCA) revealed three important hotspots in the area according to soil uses and geographic localization: the thermoelectric, its area of influence due to volatile compound deposition, and the area comprised between two urban areas. Farming practice turn out to be an important factor too for the quantity of hazard element stored in soils.

Nanominerals and potentially hazardous elements from coal cleaning rejects of abandoned mines: Environmental impact and risk assessment.

Soils around coal mining are important reservoir of hazardous elements (HEs), nanominerals, and ultrafine compounds. This research reports and discusses the soil concentrations of HEs (As, Cd, Cr, Cu, Ni, Pb, and Zn) in coal residues of abandoned mines. To assess differences regarding environmental impact and risk assessment between coal abandoned mines from the Santa Catarina state, eighteen coal cleaning rejects with different mineralogical and chemical composition, from eight abandoned mines were collected. Nanominerals and ultra-fine minerals from mining-contaminated areas were analyzed by X-ray diffraction (XRD), field emission scanning electron microscopy (FE-SEM), and high-resolution transmission electron microscope (HR-TEM), providing new information on the mineralogy and nano-mineralogy of these coal residues. The total contents of 57 elements (HEs, alkali metals, and rare earth elements) were analyzed by Inductively Coupled Plasma Mass Spectrometry (ICP-MS). The calculation of NWACs (Normalized Average Weighted Concentration), together with the chemometric analysis by Principal component analysis (PCA) confirmed the variability of the samples regarding their city and their mine of origin. Moreover, the results confirmed the existence of hotspots in mines near urban areas.

Methodology to assess the mobility of trace elements between water and contaminated estuarine sediments as a function of the site physico-chemical characteristics

This work presents an innovative methodology to have a rapid diagnosis about the mobility of selected trace elements of known toxicity and biological risk (Al, As, Cd, Co, Cr, Cu, Fe, Mn, Ni, Pb, Sn and Zn) present in contaminated sediments. The novel strategy presented in this work uses, therefore, the own estuarine water in contact with sediments as the extracting agent to perform the mobility tests, simulating the real situation of the estuary. This water suffers from different physico-chemical conditions (low and high tides) and gives consequently, rather better information than the one obtained by the routine sequential extraction procedures. The final step of this methodology was the use of spatial modelling by kriging method and multivariate chemometric analysis, both for a better interpretation of the results. To achieve this goal, sediment and water samples were strategically collected at eight different points (four in tributary rivers, one in a closed dock, two in the main channel and another one in the mouth) along the Nerbioi-Ibaizabal River estuary (Metropolitan Bilbao, Basque Country) approximately every three months (summer, autumn, winter and spring) during a whole year. Physico-chemical changes, such as pH, carbonate content and organic matter of the sediments, together with variations in water salinity appear to be responsible for metal mobility from the sediment to the water layer. The influence of these variables was higher in the sites located close to the sea. Moreover, the mobility of trace elements was even higher at high tide in sediments with lower metal content.

Partial least squares X-ray fluorescence determination of trace elements in sediments from the estuary of Nerbioi-Ibaizabal River.

The feasibility of partial least squares (PLS) regression modeling of X-ray fluorescence (XRF) spectra of estuarine sediments has been evaluated as a tool for rapid trace element content monitoring. Multivariate PLS calibration models were developed to predict the concentration of Al, As, Cd, Co, Cr, Cu, Fe, Mg, Mn, Ni, Pb, Sn, V and Zn in sediments collected from different locations across the estuary of the Nerbioi-Ibaizabal River (Metropolitan Bilbao, Bay of Biscay, Basque Country). The study was carried out on a set of 116 sediment samples, previously lyophilized and sieved with a particle size lower than 63 microm. Sample reference data were obtained by inductively coupled plasma mass spectrometry. 34 samples were selected for building PLS models through a hierarchical cluster analysis. The remaining 82 samples were used as a test set to validate the models. Results obtained in the present study involved relative root mean square errors of prediction varying from 21%, for the determination of Pb at hundreds microg g(-1) level, up to 87%, for Ni determination at little tens microg g(-1) level. An average prediction error of +/-37% for the 14 elements under study was obtained, being in all cases mean differences between predicted and reference results of the same order than the standard deviation of three replicates from a same sample. Residual predictive deviation values obtained ranged from 1.1 to 3.9.

Practical comparison of multivariate chemometric techniques for pattern recognition used in environmental monitoring

Environmental datasets usually contain multiple and highly correlated variables. The use of multivariate techniques in this case has experienced a significant development. This paper provides a feasible comparison among several methods for pattern recognition: Principal Component Analysis (PCA), Multivariate Curve Resolution (MCR), Parallel Factor Analysis (PARAFAC) and Tucker3. They have been systematically applied on the same dataset, consisting of the concentration of trace elements measured in sediments of the estuary of the Nerbioi-Ibaizabal river (Basque Country). The results obtained have been critically discussed in terms of ease of use, interpretation of the results, and amount of information provided. The most popular PCA is probably enough for a correct and overall interpretation of the results. MCR, however, may lead to slightly different results due to the non-perceptive orthogonality of the principal components. Both PARAFAC and Tucker3 provide simplified graphical outputs that make easier interpretation of the results.

The properties of the nano-minerals and hazardous elements: Potential environmental impacts of Brazilian coal waste fire

Brazilian coal area (South Brazil) impacted the environment by means of a large number of coal waste piles emplaced over the old mine sites and the adjacent areas of the Criciúma, Urussanga, and Siderópolis cities. The area studied here was abandoned and after almost 30 years (smokeless visual) some companies use the actual minerals derived from burning coal cleaning rejects (BCCRs) complied in the mentioned area for industry tiles or refractory bricks. Mineralogical and geochemical similarities between the BCCRs and non-anthropogenic geological environments are outlined here. Although no visible flames were observed, this study revealed that auto-combustion existed in the studied area for many years. The presence of amorphous phases, mullite, hematite and other Fe-minerals formed by high temperature was found. There is also pyrite, Fe-sulphates (eg. jarosite) and unburnt coal present, which are useful for comparison purposes. Bad disposal of coal-dump wastes represents significant environmental concerns due to their potential influence on atmosphere, river sediments, soils and as well as on the surface and groundwater in the surroundings of these areas. The present study using advanced analytical techniques were performed to provide an improved understanding of the complex processes related with sulphide-rich coal waste oxidation, spontaneous combustion and mineral formation. It is reporting huge numbers of rare minerals with alunite, montmorillonite, szomolnokite, halotrichite, coquimbite and copiapite at the BCCRs. The data showed the presence of abundant amorphous Si-Al-Fe-Ti as (oxy-)hydroxides and Fe-hydro/oxides with goethite and hematite with various degrees of crystallinity, containing hazardous elements, such as Cu, Cr, Hf, Hg, Mo, Ni, Se, Pb, Th, U, Zr, and others. By Principal Component Analysis (PCA), the mineralogical composition was related with the range of elemental concentration of each sample. Most of the nano-minerals and ultra-fine particles found in the burned coal-dump wastes are the same as those commonly associated with coal cleaning rejects, in which oxidation of sulphides plays an important role to environment and human health.

Are children playgrounds safe play areas? Inorganic analysis and lead isotope ratios for contamination assessment in recreational (Brazilian) parks

In city playgrounds, there is a potential risk of harming children’s health by contamination coming from anthropogenic activities. With the aim to determinate the sources and the risk of hazardous elements, soil samples were collected in 19 selected playgrounds of different urban and rural areas from the Rio Grande do Sul state (Brazil). The concentration of 23 metals and metalloids and lead isotopic ratios were determined by ICP-MS. The methodology proposed here, firstly, classified the parks according to the average metal content by means of the NWACs (Normalized-and-Weighted Average Concentrations) and assess the contamination risk determining the Contamination Factors (CFs). Finally, statistical tools (correlation analysis and principal component analysis) were used to identify the most important contamination sources. The statistical tools used, together with lead isotopic composition analysis of the samples, revealed that coal combustion is the main source of contamination in the area. Vegetation was identified as a barrier for the contamination coming from the city. Nonetheless, some of the soils present a possible toxicological risk for humans. In fact, Cr, Sb, and Pb concentrations were higher than the Residential Intervention Values (VIRs) defined by the Environmental Protection Agency of the State of São Paulo, also in Brazil.

Spatial distribution of some trace and major elements in sediments of the Cávado estuary (Esposende, Portugal).

For the first time, the occurrence and spatial distribution of several elements, including some toxic metals, have been investigated in sediments of the estuary of the Cávado River (Esposende, Portugal). The pseudo total concentrations of Al, As, Cd, Co, Cr, Cu, Fe, Mg, Mn, Ni, Pb, Sn, V and Zn in sediments collected at 24 sites covering the tidal part of the estuary were determined. According to the concentrations measured, the Cávado estuary can be considered as non-contaminated. For most of the elements, the concentrations tended to be higher upstream. Only a moderate enrichment in Cr and Ni was detected in a few sites. An important decrease in concentration was observed for the most toxic metals compared to historical data reported in the literature. Several hotspots were identified, but even in those cases the amount of metals stored in the sediments does not represent a toxicological threat to living organisms.

Is there a direct relationship between stress biomarkers in oysters and the amount of metals in the sediments where they inhabit

The effects exerted by metals in oysters are still a matter of debate and require more detailed studies. In this work we have investigated whether the health status of oysters are affected by the amount of metals present in the sediments of their habitat. Sediments and oysters were collected in the tidal part of the estuary of the Oka River (Basque Country), representative of other mesotidal, well mixed and short estuaries of the European Atlantic coast. The concentrations of 14 elements were determined in all the samples. Several biomarkers were also measured in the soft tissues of oysters. According to the concentrations found, the sediments were classified as non-toxic or slightly toxic. In good agreement, the histological alterations observed in oysters were not severe. Interestingly, in those sampling sites where the sediments showed relatively high metal concentrations, the metallic content in oysters was lower, and vice versa.