Metals and metalloids in high-altitude Pyrenean lakes: sources and distribution in pre-industrial and modern sediments.

High-altitude Pyrenean lakes are ecosystems far from local pollution sources, and thus they are particularly sensitive to the atmospheric deposition of metals and metalloids. This study aims to quantify the effect of human activity in 18 lakes located in both side of the France-Spain frontier. Sediment cores were collected in summer 2013, sampled at a 1cm resolution and the concentration of 24 elements was measured by ICP-MS. Statistic and chemometric analysis of the results highlights the influence of the geographical position and lithogenic features of each lake basin on trapping pollutants. More than the 80% of the lakes showed values of enrichment factor (EF) above 2 for at least one of the elements investigated in at least one core interval, which corroborates the existence of historical anthropogenic inputs of elements in the studied area. The results demonstrate the natural origin of As and Ti in Pyrenees, together with the significant anthropogenic inputs of Cd, Pb, Sb and Sn from ancient times. The data set points mining activities as the main historical source of pollution and illustrate the large impact of the industrial revolution. The regional variability could reflect also differential long-range transport, followed by dry or wet deposition.

PM10 spatial distribution and metals speciation study in the Bilbao metropolitan area during the 2017-2018 period.

Speciation of respirable particles is becoming increasingly important from an epidemiological and analytical point of view to determine the potential effects of air pollution on human health. For this reason, current laws and analytical sampling methods focus on particle size, as it turns out to be the main factor for the greater or lesser penetration into the airways. In this sense, particles of less than 10 µm in diameter (<10 µm), referred to as PM10, are the particles that have a higher capacity for access to the respiratory tract and, therefore, more significant effect on them. In this sense, one of the most important factors that have a key role in the PM10 atmospheric pollution effect is the dispersion effect with the direct influence of natural effects such as wind, rain, topography apart from others. In this work, PM10 data extracted from the Basque Government environmental stations (19 sampling points) in the Biscay province (Basque Country, north of Spain) were combined with the results obtained from the use of self-made passive samplers (SMPS) in the same sampling points areas and subsequently, the sample analysis with a non-invasive elemental technique (Scanning Electron Microscope coupled to Energy Dispersive X-ray Spectrometry) was carried out. Thanks to this methodology, it was possible to determine a wide variety of metals in PM10 such as Al, Fe, Cr, Ni, Pb, Zn, Ti, etc. Most of them present as oxides and others as part of natural aggregations such as quartz, aluminosilicates, phosphates etc.

Impact assessment of metals on soils from Machu Picchu archaeological site.

Machu Picchu is an archaeological Inca sanctuary from the 15th century, located 2430 m above the sea level in the Cusco Region, Peru. In 1983, it was declared World Heritage Site by UNESCO. The surroundings and soils from the entire archaeological site are carefully preserved together with its grass parks. Due to the importance of the archaeological city and its surroundings, the Decentralized Culture Directorate of Cusco-PAN Machu Picchu decided to carry out a careful monitoring study in order to determine the ecological status of the soils. In this work, elemental and molecular characterization of 17 soils collected along the entire park was performed by means of X-ray Diffraction (XRD) and Inductively Coupled Plasma Mass Spectrometry (ICP-MS) after acidic digestion assisted by microwave energy. Thanks to the combination of these analytical techniques, it was possible to obtain the mineral composition and metal concentrations of all soils from these 17 sampling points. Finally, different statistical treatments were carried out in order to confirm the ecological status of the different sampling points from Machu Picchu archaeological site concluding that soils are not impacted.

Long term monitoring of metal pollution in sediments as a tool to investigate the effects of engineering works in estuaries. A case study, the Nerbioi-Ibaizabal estuary (Bilbao, Basque Country).

The Nerbioi-Ibaizabal estuary (Bilbao, Basque Country) suffered an important input of contaminants, including metals and metalloids, between 1875 and 1975. We collected sediments in the tidal part of the river in January 2018 and measured the concentrations of 27 elements in them. At that time, two important construction works were taking place in the area: the extension of the commercial port and the opening of long semi-closed channel. Comparing the current metallic hotspots with the geographical distribution of elements in previous years (2009, 2010 and 2014) showed us that these works seem to have significantly influenced the distribution of toxic elements in the estuary, even if the critical point of the second one is still to arrive with the inundation of the connection to the mainland. Long term pollution monitoring reveals as a powerful tool to check the effects of ongoing engineering works in estuarine environments.

Evidence of mercury sequestration by carbon nanotubes and nanominerals present in agricultural soils from a coal fired power plant exhaust.

Mercury (Hg) in agricultural soils could have negative effects on the environment and the human health. The exposure to high level of Hg through different absorption pathways, such as ingestion and diet through soil-plant system could permanently damage developing foetus of animals and humans. With the aim to assess the potential environmental and health risk and to study the behaviour and fate of Hg from agricultural soils to the environment, 47 soil samples were collected around a thermoelectric power plant in the Santa Catarina (Brazil). The Hg concentration measured by inductively coupled plasma mass spectrometry (ICP-MS) ranged from 0.16 to 0.56 mg kg-1. The distribution obtained by kriging interpolation allowed the identification of the main pollution sources. To see the morphology and composition of soil samples, field emission scanning electron microscopy (FE-SEM) and high resolution transmission electron microscopy (HR-TEM) were used combined with energy dispersive X-ray spectroscopy (EDS), showing that the carbon nanotubes and magnetite as nanomineral contributed to Hg retention. The mentioned molecular characterization, and the low Contamination Factors (CF) values obtained, suggested that there is low risk to the food security of the agro-ecosystems area near to the CFPP in the terms of Hg inputs and contamination.

Evaluating the role of particle size on urban environmental geochemistry of metals in surface sediments.

In this study, non-destructive techniques (X-ray Diffraction, Infrared and Scanning Electron Microscopy with Energy Dispersive spectroscopies) and invasive procedures (pseudo-total and sequential metal extraction methodologies) were used to highlight the significance of evaluating different particle sizes of sediments for assessing the potential environmental and health implications of metal geochemistry in an urban ecosystem. The variability in composition and properties between bulk (<2 mm) and fine (<63 µm) fractions influenced the availability, and by extension, the toxicity of metals. Indeed, the fine fraction presented not only higher metal pseudo-contents, but also greater available metal percentages. Besides the larger surface area per unit of mass and the high content of clay minerals, it was observed that it was principally Fe/Mn oxyhydroxides that favour adsorption of metals on the fine surface sediments. However, although we demonstrated that the origin of metals in the bulk surface sediments was predominantly lithogenic, use of the <2 mm fraction proved to be a useful tool for identifying different sources of available metals throughout the Deba River catchment. Specifically, discharges of untreated industrial and urban wastewaters, and even effluents from wastewater treatment plants were considered to greatly increase the health risk associated with metal availability. Finally, an evaluation of sediment dynamics in different hydrological conditions has highlighted the role played by each particle size as a vector of metal transport towards the coastal area. While resuspension of fine surface sediments notably induced significantly higher particulate metal concentrations in water during the dry season, resuspension of bulk surface sediments and, fundamentally, downstream transport of suspended particulate matter became more relevant and lowered the ecological risk during the wet season. Greater attention therefore needs to be paid to the new hydrological scenarios forecast to result from climate change, in which longer seasons with low river discharges are forecast.

Metal contaminations impact archaeal community composition, abundance and function in remote alpine lakes.

Using the 16S rRNA and mcrA genes, we investigated the composition, abundance and activity of sediment archaeal communities within 18 high-mountain lakes under contrasted metal levels from different origins (bedrock erosion, past-mining activities and atmospheric depositions). Bathyarchaeota, Euryarchaeota and Woesearchaeota were the major phyla found at the meta-community scale, representing 48%, 18.3% and 15.2% of the archaeal community respectively. Metals were equally important as physicochemical variables in explaining the assemblage of archaeal communities and their abundance. Methanogenesis appeared as a process of central importance in the carbon cycle within sediments of alpine lakes as indicated by the absolute abundance of methanogen 16S rRNA and mcrA gene transcripts (105 to 109 copies g-1 ). We showed that methanogen abundance and activity were significantly reduced with increasing concentrations of Pb and Cd, two indicators of airborne metal contaminations. Considering the ecological importance of methanogenesis in sediment habitats, these metal contaminations may have system wide implications even in remote area such as alpine lakes. Overall, this work was pioneer in integrating the effect of long-range atmospheric depositions on archaeal communities and indicated that metal contamination might significantly compromise the contribution of Archaea to the carbon cycling of the mountain lake sediments.

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.

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.

Uptake and Distribution of Trace Elements in Dominant Mangrove Plants of the Indian Sundarban Wetland.

Absorption, accumulation and translocation of 12 trace elements in nine dominant mangrove plants in the Indian Sundarban Wetland revealed both organ-specific and site-specific characteristics. An overall enrichment of elements was recorded in rhizosediment, exceeding the prescribed effects range-low (ER-L) of consensus based sediment quality guidelines (SQGs) for Cu and Pb. Avicennia officinalis, A. alba, Ceriops decandra and Excoecaria agallocha exhibited unique potential for accumulating Al, Cd, Co, Cr, Cu, Ni, Mn and Zn and could be considered efficient accumulators. Maximum element accumulation in trunk bark (As 6.16, Cr 49.9, Co 2.67, Cu 91.00 and Zn 85.5 mg kg-1) and root/pneumatophore (Al 1000 and Fe 2430 mg kg-1) was recorded. Maximum bioconcentration factor (6.23) in A. officinalis and translocation factor (17.5 for Mn) in C. decandra distinguished their phytoremediation capacity. These halophytes could be used for trace element phytoremediation in stressed sites of Sundarban.

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.

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.

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.

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.

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.