Trace elements in the water column of high-altitude Pyrenean lakes: Impact of local weathering and long-range atmospheric input.

High altitude (alpine) lakes are efficient sentinels of environmental processes, including local pollution and long-range atmospheric transfer, because these lakes are highly vulnerable to ongoing climate changes and increasing anthropogenic pressure. Towards improving the knowledge of trace element geochemistry in the water column of alpine lakes, we assessed 64 physico-chemical parameters, including macro- and micronutrients, major and trace element concentrations in the water column of 18 lakes in the Pyrenees, located along the border between France and Spain. Lake depth, morphology, retention time and watershed rock lithology did not exhibit sizable impact on major and trace element concentrations in the water column. However, acidic (pH = 4.7 ± 0.2) lakes were distinctly different from circumneutral lakes (pH = 6.8 ± 0.5) as they exhibited >10 times higher concentrations of SO42- and trace metals (Fe, Mn, Zn, Cd, Pb, Co, Ni, Be, Al, Ga and REEs). While some of these elements clearly mark the presence of sulphide-rich minerals within the watershed (Fe, Zn, Cd and Pb), the increased mobility of lithogenic elements (Be, Al, Ga and REEs) in acidic lakes may reflect the leaching of these elements from silicate dust derived from atmospheric deposits or surrounding granites. At the same time, compared to circumneutral lakes, acidic lake water displayed lower concentrations of dissolved oxyanions (As, Mo, V, B and W) and elevated SO42- concentrations. The latter could lead to efficient Ba removal from the water column. The exploitation of metal ores within the watershed of three lakes clearly impacted high Zn and Cd concentrations observed in their water column, despite two of these lakes not being acidic. We conclude that local impacts have a greater effect on the water column than long-range atmospheric inputs and that dissolved trace element concentration measurements can be used for revealing sulphide-rich minerals or acid mine drainage within the lakes' watershed.

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.

Combined use of 87Sr/86Sr and carbon isotopes with multielemental analysis for the geographical authentication of Tunisian and European olive oils.

The geographical authentication in the agrifood industry has become a major issue to guarantee the quality of food products. Olive oil (OO) is particularly a complex matrix and establishing a reliable approach for linking OO samples to their origin is an analytical challenge. In this study, the isotopic composition of carbon, strontium and the concentrations of seventeen elements were determined in OOs from Tunisia, Southern France and the South Basque country. The preliminary results overlapped and showed that, taken individually, the isotopic and elemental approaches were not discriminant. A linear discriminant analysis applied to δ13C, 87Sr/86Sr and to the concentrations of 4 selected trace elements (Fe, Mn, V and Cr) allowed to classify, with high resolution, olive oils into 3 groups according to their provenance. The combination of the plant growing environment, the geological background, the mineral composition of the soil and the production process lead to a novel approach to deal with fraudulent practices in OO sector.

Dynamics, distribution, and transformations of mercury species from pyrenean high-altitude lakes.

While mercury (Hg) is a major concern in all aquatic environments because of its methylation and biomagnification pathways, very few studies consider Hg cycling in remote alpine lakes which are sensitive ecosystems. Nineteen high-altitude pristine lakes from Western/Central Pyrenees were investigated on both northern (France) and southern (Spain) slopes (1620-2600 m asl.). Subsurface water samples were collected in June 2017/2018/2019 and October 2017/2018 for Hg speciation analysis of inorganic mercury (iHg(II)), monomethylmercury (MMHg), and dissolved gaseous mercury (DGM) to investigate spatial and seasonal variations. In June 2018/2019 and October 2018, more comprehensive studies were performed in four lakes by taking water column depth profiles. Besides, in-situ incubation experiments using isotopically enriched Hg species (199iHg(II), 201MMHg) were conducted to investigate Hg transformation mechanisms in the water column. While iHg(II) (0.08-1.10 ng L-1 in filtered samples; 0.11-1.19 ng L-1 in unfiltered samples) did not show significant seasonal variations in the subsurface water samples, MMHg (<0.03-0.035 ng L-1 in filtered samples; <0.03-0.062 ng L-1 in unfiltered samples) was significantly higher in October 2018, mainly because of in-situ methylation. DGM (0.02-0.68 ng L-1) varies strongly and can exhibit higher levels in comparison with other pristine areas. Depth profiles and incubation experiments highlighted the importance of in-situ biotic methylation triggered by anoxic conditions in bottom waters. In-situ incubations confirm that significant methylation, demethylation and photoreduction extents are taking place in the water columns. Overall, drastic environmental changes occurring daily and seasonally in alpine lakes are providing conditions that can both promote Hg methylation (stratified anoxic waters) and MMHg photodemethylation (intense UV light). In addition, light induced photoreduction is a major pathway controlling significant gaseous Hg evasion. Global warming and potential eutrophication may thus have direct implications on Hg turnover and MMHg burden in those remote ecosystems.

Selenium distribution and speciation in waters of pristine alpine lakes from central-western Pyrenees (France-Spain).

The speciation of both redox reactive and volatile selenium (Se) compounds, barely reported in pristine aquatic environments, has never been investigated in remote alpine lakes, considered as sensitive ecosystems to detect the effect of global change. This work presents an integrated investigation on Se distribution and speciation conducted in 20 high altitude pristine lakes from the central-western Pyrenees. Five seasonal sampling campaigns were carried out after snowmelt (June/July) and in early fall (October) for the period 2017-2019. Concentrations of total dissolved Se (TDSe) ranged from 7 to 78 ng L-1, with selenate being ubiquitously observed in most cases (median of 61% of TDSe). Selenite was only occasionally detected up to 4 ng L-1, therefore a fraction of TDSe was presumably in the forms of elemental Se(0) and/or selenides. Depth profiles obtained in different lakes showed the occurrence of such Se(-II, 0) pools in bottom hypoxic to anoxic waters. The production of volatile Se compounds presented a low median total concentration (TVSe) of 33 pg L-1 (range 3-120 pg L-1), mainly in the form of dimethylselenide in subsurface samples (median of 82% of TVSe). The Se concentration in lake waters was significantly correlated with the sulphate concentration (ρ = 0.93, p < 0.0001), demonstrating that it is influenced by erosion and dissolution of Se and S-enriched parent bedrocks. In addition, for Se depleted alpine lake-bedrock systems, long-range transport and wet atmospheric depositions represent a major source of Se for lake waters.

Characterization of atmospheric aerosols in the Antarctic region using Raman Spectroscopy and Scanning Electron Microscopy.

The non-destructive spectroscopic characterization of airborne particulate matter (PM) was performed to gain better knowledge of the internal structures of atmospheric aerosols at the particle level in the Antarctic region, along with their potential sources. PM and soil samples were collected during the 2016-2017 austral summer season at the surroundings of the Spanish Antarctic Research Station "Gabriel de Castilla" (Deception Island, South Shetland Islands). PM was deposited in a low-volume sampler air filter. Raman spectroscopy (RS) and Scanning Electron Microscopy with Energy-Dispersive X-ray Spectroscopy (SEM-EDS) were used to determine the elemental and molecular composition of the individual aerosol and soil particles. Filter spectra measured by these techniques revealed long-range atmospheric transport of organic compounds (polystyrene and bacteria), local single and cluster particles made of different kinds of black carbon (BC), exotic minerals (polyhalite, arcanite, niter, ammonium nitrate, syngenite and nitrogen, phosphorus, and potassium (NPK) fertilizer), and natural PM (sea salts, silicates, iron oxides, etc.). In addition to the filter samples, forsterite and plagioclase were discovered in the soil samples together with magnetite. This is the first report of the presence of a microplastic fiber in the Antarctic air. This fact, together with the presence of other pollutants, reflects that even pristine and remote regions are influenced by anthropogenic activities.

Trace Elements Analysis of Tunisian and European Extra Virgin Olive Oils by ICP-MS and Chemometrics for Geographical Discrimination.

The aim of this study was to investigate the levels of trace elements in olive oils from different locations and their use for geographical authentication. Concentrations of seventeen elements were determined in a total of 42 olive oils from Tunisia, Spain (Basque country), and southern France, and in nine soil samples from Tunisia by quadrupole inductively plasma mass spectrometry. The compilation of appropriate techniques integrated into the analytical procedure achieved a precision (RSD) between 2% and 15% and low limits of detection (between 0.0002 and 0.313 µg kg-1). The accuracy of the analytical method applied for olive oil analysis was evaluated using SRM NIST 2387 Peanut butter. The recoveries obtained after microwave-assisted digestion for the certified elements ranged between 86% and 102%. Concentrations of non-certified elements (V, Cr, Co, Ni, Ba, Rb, Sr, Cd, Pb, and As) were presented. The use of Pearson correlation applied on paired Tunisian oil/soil samples has shown that several elements (Mg, Mn, Ni, and Sr) were significantly correlated. The multivariate statistics using principal component analysis have successfully discriminated against three studied origins. The most significant variables were the elemental concentrations of Cu, Cr, Fe, Mn, Sr, V, and Zn. This study shows the potential of applying trace elements profiles for olive oil geographical discrimination.

Multiple regression analysis to assess the contamination with metals and metalloids in surface sediments (Aveiro Lagoon, Portugal).

An innovative multiple regression analysis was used to evaluate metal/metalloid contamination in the surface sediments of a coastal lagoon. The concentrations of metals/metalloids were represented as a function of geochemical characteristics of the sediments (fine fraction, concentrations of organic carbon, Ca, Al, Mn) and distances between sampling points. The effect of distances on the concentrations were negligible for Li, Co, Ni, Ba, V, Cr, and only geochemical variables specific for each element explained its spatial variation. The concentrations of As, Cu, Zn and Pb were influenced by both geochemical and geographical distance variables, the latter representing the anthropogenic influence and the extent of transport of contaminants away from the upstream source. Enrichment of the sediment with Ba, As, Co, Cr and V was determined mainly by enrichment with Mn. The proposed approach is supplementary to the traditional utilization of enrichment factors, and is better suited for systems with anthropogenic influence.

Modeling phaeopigment concentrations in water from a shallow mesotrophic lagoon.

Concentrations of phaeopigments (Pha) and chlorophyll a (Chl) were determined in surface waters from a temperate lagoon during six sampling campaigns at high and at low tide. In order to develop models for phaeopigment concentration in water, it was necessary to replace Chl with photosynthetic pigment concentration (Pt  = Pha+Chl) as one of the explanatory variables. Under first approximation, food availability and water temperature (T) could be considered as independent variables. The concentrations of Pha were then determined following seasonal change of response curves of the consumer community on T. However, multiple regression models with Pt , T and, eventually, salinity as explanatory variables were better able to depict Pha. All equations, developed with Pt , were also solved using Chl as an input variable. Although part of the performance was lost, such back-transformed models can be used at low/medium T and moderate to high concentrations of Chl. The developed equations about middle to long-term variations of Pha could be applied to study the biogeochemistry of contaminants related to Pha and to evaluate the dependence on temperature of phytoplankton utilization by consumers. PRACTITIONER POINTS: Phaeopigment concentration depicted by chlorophyll (Chl), temperature (T), and salinity. Better results obtained at low to medium T and moderate to high Chl concentration. Multiple regression (MR) better for extrapolation than model (S) with variable separation. Thermal response of consumer community in mesotrophic lagoon studied using model S.

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.

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.

Portable Raman spectroscopy for an in-situ monitoring the ripening of tomato (Solanum lycopersicum) fruits.

Ripening is one of the most important transformations that fruits and vegetables suffer, from an unripe to a ripe stage. In this study, it was followed up and analyzed the variations in the composition of tomato fruits at different ripening stages (green or unripe, orange or middle ripe, red or ripe and brown or overripe). The results obtained from the Raman measurements carried out showed a change in the composition of tomato fruits in the transit from green to brown. The analysis confirmed an increase of carotenoids from an unripe to a ripe stage of these fruits, being lycopene the characteristic carotenoid of the optimum ripe stage. The presence of chlorophyll and cuticular waxes decrease from the unripe to the ripe stage. Moreover, the relative intensity of phytofluene, a transition compound in the carotenoid biosynthetic pathway, is higher in the orange or middle ripening stage. The results obtained in-situ, without cutting and handling the tomato fruits, by means of a portable Raman spectrometer offered the same information that can be achieved using a more expensive and sophisticated confocal Raman microscope.

Characterization of ferruginous cements related with weathering of slag in a temperate anthropogenic beachrock.

This work outlines a temperate latitude beachrock occurrence, which represents the legacy of heavy anthropogenic environmental disturbance. The units contain high amounts of slag and iron-rich wastes derived from metallurgical activities that attest the impact of the past industrial development on such coastal systems. The exposition of the anthropogenic wastes to weathering processes, such as the influence of marine aerosols and the chemical attack of acid gases like the SOx coming from the nearby urban-industrial atmosphere, gave rise to the formation of early diagenetic ferruginous cements. A new analytical methodology based on the combination of micro-Raman spectroscopy (MRS), Raman chemical imaging, SEM-EDS and the Structural and Chemical Analyzer (SCA, an emerging system that hyphenates micro-Raman and SEM-EDS), was applied for the first time to characterize the ferruginous cements. The MRS analyses revealed Fe2+/Fe3+ oxides and oxyhydroxides, CaCO3 polymorphs and less frequently silicates. The Fe mineral species detected were hydrated goethite, hematite, magnetite, magnesioferrite, lepidocrocite and goethite. Complementary Raman imaging, SEM-EDS and SCA analyses unraveled the preferential distribution of hydrated goethite. The identified iron mineral phases are weathering sub-products of hematite commonly derived from atmospheric/aqueous leaching processes triggered by the chemical attack of the acid gases. EDS showed the existence of other elements such as Si, Mg, Cl, Na, Al, K and sporadically S that indicated the importance of permeability, atmospheric deposition and the acid attack. Additionally, calcite and gypsum minerals also evidenced the action of meteoric waters, dry deposition processes or the attack of SOx acid gases. The presence of such compounds is modifying the cement stratigraphy and suggests that the dissolution of carbonates is currently taking place. Those facts influence the erosive susceptibility and the release of the anthropogenic materials trapped originally in the beachrocks, which could act as potential secondary sources of contaminants to the coastal environment.

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 mobilization of hazardous elements after a tropical storm event in a polluted estuary.

The Tubarão River (Santa Catarina, Brazil) is affected by hazardous elements (HEs) pollution from abandoned coal mines, agricultural activities, urban discharges, industrial and leisure zones, etc. In order to study the distribution and sources of HEs contamination in a polluted estuary after a tropical storm, waters and surface sediments were collected from 15 sampling sites along the Tubarão River. The concentration of 24 elements (Ag, Al, As, Ba, Cd, Co, Cr, Cu, Fe, Hg, Mg, Mn, Mo, Ni, Pb, Sb, Se, Sn, Sr, Ti, Tl, V, W, and Zn) were measured by Inductively Coupled Plasma Mass Spectrometry (ICP-MS) and the mineralogical composition of the sediments by Raman spectroscopy and X-ray diffraction (XRD). The metal concentrations in water and sediment showed wide spatial variation due to the variability in water discharges and anthropogenic inputs after a storm. In general, higher metal concentration in water and lower in sediments were found upstream (closer to coal mining). Downstream sampling sites and the Oratorio River sampling site (one of the eight tributaries of the estuary) showed the highest values in sediment samples. Normalized and Weighed Average Concentrations (NWAC) were calculated, which allow us to identify, in a very simple way, the sampling sites of higher concern (hotspots of contamination) in the studied area. NWAC suggested that the strong rainfall events could affect to the metal distribution in sediments. The results of this study were compared with a previous study in the same area during dry season by Principal Component Analysis (PCA), showing changes in environmental pollution of the sediment after a strong storm event.

Accumulation and Translocation of Essential and Nonessential Elements by Tomato Plants (Solanum lycopersicum) Cultivated in Open-Air Plots under Organic or Conventional Farming Techniques.

A 5-month experiment was performed to study the accumulation of several inorganic elements in tomato plants cultivated using organic or synthetic fertilizer. Plants were harvested in triplicate at six sampling dates during their life cycle. Statistical and chemometric analysis of data indicated the sequestration of toxic elements and of Na, Zn, Fe, and Co in roots, while the rest of the elements, including Cd, were mainly translocated to aboveground organs. A general decreasing trend in element concentrations with time was observed for most of them. A negative correlation between some element concentrations and ripening stage of fruits was identified. Conventionally grown plants seemed to accumulate more Cd and Tl in their tissues, while organic ones were richer in some nutrients. However, there was no clear effect of the fertilizer used (organic vs synthetic) on the elemental composition of fruits.

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.

Metals and metalloids in fruits of tomatoes (Solanum lycopersicum) and their cultivation soils in the Basque Country: concentrations and accumulation trends.

The concentrations of several elements (Al, Fe, As, Cu, Cd, Co, Cr, Mn, Ni, Pb, Sn, V, and Zn) were measured in soils and the edible part of different vegetables (tomatoes (Solanum lycopersicum "Raf") peppers (Capsicum annuum), chards (Betavulgaris var. cicla), artichokes (Cynarascholymus)) and fruits (Raspberries (Rubusidaeus)) from 13 orchards in the Basque Country affected by different pollution sources. Multivariate analysis of data was used to look for possible correlations between metals in soil and metals in the edible part of the plant. Only manganese showed a correlation significantly different from zero. The metal concentrations found in the edible part were always below the upper limits recommended by the European legislation in force. The Bioaccumulation Index was used to investigate how efficient the plant is to uptake an element from the cultivation soil and to preserve its edible part from the element.