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Urban air pollution in West Africa has yet to be well characterized. In the frame of DACCIWA (Dynamics-Aerosol-Chemistry-Cloud Interactions in West Africa) program, intensive measurement campaigns were performed in Abidjan (Côte d'Ivoire) and Cotonou (Benin), in dry (January 2016 and 2017) and wet (July 2015 and 2016) seasons, at different sites chosen to be representative of African urban combustion sources, i.e., domestic fires (ADF), traffic (AT) and waste burning (AWB) sources in Abidjan and traffic source in Cotonou (CT). Both the size distribution of particulate matter (PM) and their chemical composition including elemental carbon (EC), organic carbon (OC), water-soluble organic carbon (WSOC), water-soluble inorganic ions (WSI) and trace metals were examined. Results show very high PM concentrations at all sites and a well-marked seasonality as well as a strong spatial variation. The average PM2.5 mass concentrations during the wet season are 517.3, 104.1, 90.3, and 69.1 µg m−3 at the ADF, CT, AT, and AWB sites, respectively. In the dry season, PM2.5 concentrations decrease to 375.7 µg m−3 at the ADF site, while they increase to 269.7, 141.3, and 175.3 µg m−3 at the CT, AT, and AWB sites, respectively. The annual PM2.5 levels at almost all sites are significantly higher than the WHO guideline level of 10 µg m−3. As for PM mass, (EC) and (OC) concentrations are also maximal at the ADF site, accounting for up to 69 % of the total PM mass. Such a high content is mainly linked to wood burning for domestic cooking and commercial food smoking activities. Dust contributions are dominant at CT (57 %–80 %), AT (20 %–70 %), and AWB (30 %–69 %) sites and especially in the coarse and fine-particle modes at the CT site and in the coarse fraction at the AT site, which may be explained by the impact of long-range desert-dust transport and resuspended particles from the roads, in addition to anthropogenic sources. The contributions of WSI to the total PM mass, mainly driven by chloride, nitrate, and calcium in the fine and/or large particles, are highly variable according to the sites but remain less than 30 %. Values are generally 1–3 times higher in the wet season than in the dry season. This is due not only to anthropogenic emissions but also to nitrate formation by reaction processes and natural emissions. The concentrations of trace elements reflect well the trends in dust at the traffic and AWB sites, with a predominance of Al, Na, Ca, Fe, and K, keys markers of crustal dust. This study constitutes an original database that characterizes specific African combustion sources.

Freshwater reservoirs are a significant source of CO2 to the atmosphere. CO2 is known to be emitted at the reservoir surface by diffusion at the air–water interface and downstream of dams or powerhouses by degassing and along the river course. In this study, we quantified total CO2 emissions from the Nam Theun 2 Reservoir (Lao PDR) in the Mekong River watershed. The study started in May 2009, less than a year after flooding and just a few months after the maximum level was first reached and lasted until the end of 2013. We tested the hypothesis that soils from the drawdown area would be a significant contributor to the total CO2 emissions.Total inorganic carbon, dissolved and particulate organic carbon and CO2 concentrations were measured in 4 pristine rivers of the Nam Theun watershed, at 9 stations in the reservoir (vertical profiles) and at 16 stations downstream of the monomictic reservoir on a weekly to monthly basis. CO2 bubbling was estimated during five field campaigns between 2009 and 2011 and on a weekly monitoring, covering water depths ranging from 0.4 to 16 m and various types of flooded ecosystems in 2012 and 2013. Three field campaigns in 2010, 2011 and 2013 were dedicated to the soils description in 21 plots and the quantification of soil CO2 emissions from the drawdown area. On this basis, we calculated total CO2 emissions from the reservoir and carbon inputs from the tributaries. We confirm the importance of the flooded stock of organic matter as a source of carbon (C) fuelling emissions. We show that the drawdown area contributes, depending on the year, from 40 to 75 % of total annual gross emissions in this flat and shallow reservoir. Since the CO2 emissions from the drawdown zone are almost constant throughout the years, the large interannual variations result from the significant decrease in diffusive fluxes and downstream emissions between 2010 and 2013. This overlooked pathway in terms of gross emissions would require an in-depth evaluation for the soil organic matter and vegetation dynamics to evaluate the actual contribution of this area in terms of net modification of gas exchange in the footprint of the reservoir, and how it could evolve in the future.

The estuarine behavior of organic carbon (OC) and trace elements (TE) was studied for the largest European sub-Arctic river, which is the Severnaya Dvina; this river has a deltaic estuary covered in ice during several hydrological seasons: summer (July 2010, 2012) and winter (March 2009) baseflow, and the November–December 2011 ice-free period. Colloidal forms of OC and TE were assessed for three pore size cutoffs (1, 10, and 50 kDa) using an in situ dialysis procedure. Conventionally dissolved (< 0.22 μm) fractions demonstrated clear conservative behavior for Li, B, Na, Mg, K, Ca, Sr, Mo, Rb, Cs, and U during the mixing of freshwater with the White Sea; a significant (up to a factor of 10) concentration increase occurs with increases in salinity. Si and OC also displayed conservative behavior but with a pronounced decrease in concentration seawards. Rather conservative behavior, but with much smaller changes in concentration (variation within ±30%) over a full range of salinities, was observed for Ti, Ni, Cr, As, Co, Cu, Ga, Y, and heavy REE. Strong non-conservative behavior with coagulation/removal at low salinities (< 5‰) was exhibited by Fe, Al, Zr, Hf, and light REE. Finally, certain divalent metals exhibited non-conservative behavior with a concentration gain at low (~ 2–5‰, Ba, Mn) or intermediate (~ 10–15‰, Ba, Zn, Pb, Cd) salinities, which is most likely linked to TE desorption from suspended matter or sediment outflux. The most important result of this study is the elucidation of the behavior of the "truly" dissolved low molecular weight LMW< 1 kDa fraction containing Fe, OC, and a number of insoluble elements. The concentration of the LMW fraction either remains constant or increases its relative contribution to the overall dissolved (< 0.22 μm) pool as the salinity increases. Similarly, the relative proportion of colloidal (1 kDa–0.22 μm) pool for the OC and insoluble TE bound to ferric colloids systematically decreased seaward, with the largest decrease occurring at low (< 5‰) salinities. Overall, the observed decrease in the colloidal fraction may be related to the coagulation of organo-ferric colloids at the beginning of the mixing zone and therefore the replacement of the HMW1 kDa–0.22 μm portion by the LMW< 1 kDa fraction. These patterns are highly reproducible across different sampling seasons, suggesting significant enrichment of the mixing zone by the most labile (and potentially bioavailable) fraction of the OC, Fe and insoluble TE. The size fractionation of the colloidal material during estuarine mixing reflects a number of inorganic and biological processes, the relative contribution of which to element speciation varies depending on the hydrological stage and time of year. In particular, LMW< 1 kDa ligand production in the surface horizons of the mixing zone may be linked to heterotrophic mineralization of allochthonous DOM and/or photodestruction. Given the relatively low concentration of particulate versus dissolved load of most trace elements, desorption from the river suspended material was less pronounced than in other rivers in the world. As a result, the majority of dissolved components exhibited either conservative (OC and related elements such as divalent metals) or non-conservative, coagulation-controlled (Fe, Al, and insoluble TE associated with organo-ferric colloids) behavior. The climate warming at high latitudes is likely to intensify the production of LMW< 1 kDa organic ligands and the associated TE; therefore, the delivery of potentially bioavailable trace metal micronutrients from the land to the ocean may increase.

Mining areas and in particular those containing massive sulfides have left a heavy environmental legacy with soils and hydrographic networks highly contaminated with metals and metalloids as for example in the Iberian Pyrite Belt (Huelva, Spain). Here, we present new data on copper (Cu) isotopic composition of waters and solids collected along a continuum Mine (Tharsis)-River (Meca)-Lake (Sancho) in the Iberian Pyrite Belt. Our results show that the isotopic signature of pit lakes is spatially variable, but remains stable over the seasons; this signature seems to be controlled by water-rock interaction processes. The data obtained on the Meca River imply a number of attenuation processes such as decrease in the metal concentration by precipitation of secondary minerals. This is accompanied by preferential retention of the heavy isotope ( 65 Cu) with a possibility of living organisms (e.g., algae) participation. The terminal Sancho lake demonstrated constant isotopic signature over the entire depth of the water column despite sizable variations in Cu concentrations, which can be tentatively explained by a superposition of counter-interacting biotic and abiotic processes of Cu fractionation. Overall, the understanding of the isotopic variations along the hydrological continuum is useful for a better understanding of metal element transfer within mining environments and surrounding surface waters., (© 2023. The Author(s), under exclusive licence to Springer-Verlag GmbH Germany, part of Springer Nature.)

Since cacao beans accumulate Cd in high levels and restrictions have been imposed on safe levels of chocolate consumption, concern about whether or not cacao trees store other toxic elements seems to be inevitable. Following a previous study in Ecuador examining Cd content in five cacao varieties collected in pristine areas and in places impacted by oil activities, we present here the concentrations of 11 trace elements (TEs) (As, Ba, Co, Cu, Cr, Mo, Mn, Ni, Pb, V and Zn) in soils, cacao tissues (leaves, pod husks, beans) and cocoa liquor (CL). Several TEs showed concentrations in topsoils above the Ecuadorian limits, and may have a mixed natural and anthropogenic origin. Ba and Mo concentrations in cacao tissues are slightly higher than those reported in other surveys, but this was not the case for toxic elements (As and Pb). TE contents are lower in CL, than in beans, except for Pb and Co, but no risk was identified for human health. Compared with control areas, Enrichment Factors were below 2 in impacted areas, except for Ba. Transfer factors (from soils to cacao) indicated that cacao does not accumulate TEs. A positive correlation was found between Cd and Zn in topsoils and cacao tissues for the CCN-51 variety, and between Cd and Ni for the Nacional variety. Identifying patterns of TE distribution and potential interactions in order to explain plant internal mechanisms, which is also dependent on the cacao variety, is a difficult task and needs further research., (Copyright © 2020 Elsevier Inc. All rights reserved.)

Copper export and mobility in acid mine drainage are difficult to understand with conventional approaches. Within this context, Cu isotopes could be a powerful tool and here we have examined the relative abundance of dissolved (<0.22 μm) Cu isotopes (δ 65 Cu) in the Meca River which is an outlet of the Tharsis mine, one of the largest abandoned mines of the Iberian Pyrite Belt, Spain. We followed the chemical and isotopic composition of the upstream and downstream points of the catchment during a 24-h diel cycle. Additional δ 65 Cu values were obtained from the tributary stream, suspended matter (>0.22 μm) and bed sediments samples. Our goals were to 1) assess Cu sources variability at the upstream point under contrasted hydrological conditions and 2) investigate the conservative vs. non conservative Cu behavior along a stream. Average δ 65 Cu values varied from -0.47 to -0.08‰ (n = 9) upstream and from -0.63 to -0.31‰ downstream (n = 7) demonstrating that Cu isotopes are heterogeneous over the diel cycle and along the Meca River. During dry conditions, at the upstream point of the Meca River the Cu isotopic composition was heavier which is in agreement with the preferential release of heavy isotopes during the oxidative dissolution of primary sulfides. The more negative values obtained during high water flow are explained by the contribution of soil and waste deposit weathering. Finally, a comparison of upstream vs. downstream Cu isotope composition is consistent with a conservative behavior of Cu, and isotope mass balance calculations estimate that 87% of dissolved Cu detected downstream originate from the Tharsis mine outlet. These interpretations were supported by thermodynamic modelling and sediment characterization data (X-ray diffraction, Raman Spectroscopy). Overall, based on contrasted hydrological conditions (dry vs flooded), and taking the advantage of isotope insensitivity to dilution, the present work demonstrates the efficiency of using the Cu isotopes approach for tracing sources and processes in the AMD regions., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2020 Elsevier Ltd. All rights reserved.)

In Southern Europe, soil contamination by heavy metals (HM) due to mining and industrial activities is a long-known problem. Yet, despite soils being widely contaminated through decades, some plants are still able to grow. Some of these plants, like giant reed (Arundo donax) or common reed (Phragmites australis) are capable of accumulating substantial amount of HM. These reeds also contain small silica structures in their shoots, called phytoliths. However, the role of phytoliths in reducing stress caused by these HM remains unknown. The aim of this work is then to determine if phytoliths represent a preferential structure for the bioacccumulation of HM in plants. Therefore, plants from mining-contaminated sites in Spain and France were sampled and HM concentrations in total plant shoots were compared to those in phytoliths for eight metal(oid)s: As, Cd, Cu, Mn, Pb, Sb, Sn and Zn. Results show that Arundo donax and Phragmites australis tend to accumulate Cd, Sb and Sn but limit the uptake of As, Cu, Mn, Pb and Zn in plant shoots despite that the concentration of these HM in soil is quite high. Therefore, reeds appear as tolerant to high metal concentrations in soils, and phytoliths are identified as preferential structures for encapsulation of As, Cu, Mn, Pb and Zn, while Cd, Sb and Sn were mainly found to be accumulated in organic tissues rather than in phytoliths., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2019 Elsevier B.V. All rights reserved.)

Nowadays, atmospheric pollution has a major impact on the human health and the environment, encouraging the development of biomonitors of the air quality over a wide zone. In this study, the relevance of the epiphyte plants Tillandsia usneoides is studied to estimate the transfer of metal(loid)s from a former Zn and Pb mining zone in the Southeast of Spain (Cartagena-La Unión) to the local atmosphere. Biomonitoring was performed by installing plants in 5 sites along a transect from the main mining area to the urban and the coastal zones. An aliquot of plants was collected in every site every 2 months over 1 year. The Tillandsia usneoides have been observed with SEM-EDX, and analysed by ICP-MS to determine trace element concentrations, magnetic susceptibility signals and Zn and Pb isotopes ratios. Results show that atmospheric particles are distributed homogeneously at the plant surface. By comparing elemental contents in Tillandsia usneoides with regard to the values of the geochemical background of the region of Murcia, significant enrichments are observed in the epiphyte plants for Sb, As, Cd, Zn and Pb. The statistical analyses (decentred PCA and PLS) also suggest that the kinetics of dust deposition is slower for the urban and coastal sites compared to the mining sites and highlight an influence of agricultural activities in Cu deposition. The similarity of isotopic compositions (Zn and Pb) between Tillandsia usneoides, soils and atmospheric particles also put in evidence that these plants could be a powerful tool to trace the source of matter in the atmosphere. Finally, this experiment provides new insight to better understand the foliar absorption mechanisms., (Copyright © 2019 Elsevier Ltd. All rights reserved.)

Nowadays, air pollution has a major impact on the environment and human health. Owen gauges allow the sampling of atmospheric depositions in polluted sites for further characterisation. This paper shows the study of the air particles of an old mining zone in Cartagena-La Unión (South-east of Spain) in order to quantify their potential risk on human health. There were 4 strategic sites monitored: the main mining tailing (Avenque), the urban area (La Unión), an agricultural zone (formerly mining) and a site in the Mediterranean coast. Physico-chemical and mineralogical characterisation was applied to atmospheric fallouts. The granulometry revealed a dust particle size around 15 μm, with the coarsest particles in the urban area and the thinnest at the tailing site. XRD analyses showed the presence of quartz, carbonates, sulphides and sulphates. Observations with SEM-EDX confirmed chemical spectra and allowed us to classify the particles into well-crystallised minerals and heterogeneous dusts. Total metal content determination was carried out by ICP-MS analyses and results showed Zn, Pb, As and Cd fluxes (respectively 2549, 1275, 68 and 7 μg·m -2 ·d -1 ) exceeding the limit values set by European legislations in the mining area. The fluxes of Zn, Pb and As also exceed these standards in the urban area whereas the coastal zone only exceeds the thresholds in the case of As. Inhalation health risk (defined by US EPA, 2009) was quantified in the sites using total and bioaccessible metal contents of the dusts. Risk calculations using total metal content considering a residential scenario showed acceptable risk for all sites except for the mining tailing which presented non-acceptable cancer and hazard risk mainly due to the total As and Pb contents. When considering the bioaccessible fraction of As and Pb, the risk diminished to acceptable values, demonstrating the overestimation produced when using total metal contents., (Copyright © 2019 Elsevier B.V. All rights reserved.)

Tropical forests shelter an unparalleled biological diversity. The relative influence of environmental selection (i.e., abiotic conditions, biotic interactions) and stochastic-distance-dependent neutral processes (i.e., demography, dispersal) in shaping communities has been extensively studied for various organisms, but has rarely been explored across a large range of body sizes, in particular in soil environments. We built a detailed census of the whole soil biota in a 12-ha tropical forest plot using soil DNA metabarcoding. We show that the distribution of 19 taxonomic groups (ranging from microbes to mesofauna) is primarily stochastic, suggesting that neutral processes are prominent drivers of the assembly of these communities at this scale. We also identify aluminium, topography and plant species identity as weak, yet significant drivers of soil richness and community composition of bacteria, protists and to a lesser extent fungi. Finally, we show that body size, which determines the scale at which an organism perceives its environment, predicted the community assembly across taxonomic groups, with soil mesofauna assemblages being more stochastic than microbial ones. These results suggest that the relative contribution of neutral processes and environmental selection to community assembly directly depends on body size. Body size is hence an important determinant of community assembly rules at the scale of the ecological community in tropical soils and should be accounted for in spatial models of tropical soil food webs., (© 2018 John Wiley & Sons Ltd.)

In the South-West Europe (Iberian Pyrite Belt), acid mine drainage (AMD) processes are especially problematic because they affect the environmental quality of watersheds, restricting the use of surface water. Recent studies have shown that Cu isotopes are fractionated during the oxidative dissolution of primary sulfide minerals and could be used to trace metal cycling. However the chemistry of Cu in such environment is complex because Cu is redistributed within numerous secondary minerals and strongly dependent on the hydroclimatic conditions that control key parameters (pH, redox conditions). Finally, it remains difficult to compare the various field studies and deliver some strong general tendencies because of these changing conditions. For these reasons, concerted studies on Cu isotopes fractionation in waters impacted by AMD may help to reveal the sources and transport pathways of this important pollutant. To address this issue, we used a representative scenario of strong contamination by AMD in the Iberian Pyrite Belt (SW Spain), the Cobica River. The aim of our study is to measure the Cu isotopes signature in the waters (river, mine lake, water draining waste) of the small Cobica River system (Huelva, Spain), sampled during a short period (8 h) to avoid any change in the hydro-climatic conditions. This provided an instantaneous image of the isotopic Cu signature in a small mining systems and helped us to constrain both the processes affecting Cu isotopes and their use a potential tracer of metals in contaminated environments., (Copyright © 2017 Elsevier Ltd. All rights reserved.)

Stable Zn isotopes fractionation was studied in main biogeochemical compartments of a pristine larch forest of Central Siberia developed over continuous permafrost basalt rocks. Two north- and south-oriented watershed slopes having distinctly different vegetation biomass and active layer depth were used as natural proxy for predicting possible future climate changes occurring in this region. In addition, peat bog zone exhibiting totally different vegetation, hydrology and soil temperature regime has been studied. The isotopic composition of soil profile from Central Siberia is rather constant with a δ(66)Zn value around 0.2‰ close to the value of various basalts. Zn isotopic composition in mosses (Sphagnum fuscum and Pleurozium schreberi) exhibits differences between surface layers presenting values from 0.14 to 0.2‰ and bottom layers presenting significantly higher values (0.5 - 0.7‰) than the underlain mineral surface. The humification of both dead moss and larch needles leads to retain the fraction where Zn bound most strongly thus releasing the lighter isotopes in solution and preserving the heavy isotopes in the humification products, in general accord with previous experimental and modeling works [GCA 75:7632-7643, 2011]. The larch (Larix gmelinii) from North and South-facing slopes is enriched in heavy isotopes compared to soil reservoir while larch from Sphagnum peatbog is enriched in light isotopes. This difference may result from stronger complexation of Zn by organic ligands and humification products in the peat bog compared to mineral surfaces in North- and South-facing slope. During the course of the growing period, Zn followed the behavior of macronutrients with a decrease of concentration from June to September. During this period, an enrichment of larch needles by heavier Zn isotopes is observed in the various habitats. We suggest that the increase of the depth of rooting zone, and the decrease of DOC and Zn concentration in soil solution from the root uptake zone with progressively thawing soil could provoke heavy isotopes to become more available for the larch roots at the end of the vegetative season compared to the beginning of the season, because the decrease of DOC will facilitate the uptake of heavy isotope as it will be less retained in strong organic complexes.

This study presents the determination and comparison of isotopic compositions of Hg in sediments, plankton, roach, and perch of two freshwater systems in the Lake Baikal-Angara River aquatic ecosystem: the man-made Bratsk Water Reservoir contaminated by Hg from a chlor-alkali factory and the noncontaminated Lake Baikal. Isotopic ratios of biota exhibit both significant mass-independent fractionation (MIF) (Δ(199)Hg from 0.20 to 1.87‰) and mass-dependent fractionation (MDF) (δ(202)Hg from -0.97 to -0.16‰), whereas sediments exhibit high MDF (δ(202)Hg from -1.99 to -0.83‰) but no MIF. δ(15)N and δ(13)C are correlated with methylmercury in organisms from both sites, indicating bioaccumulation and biomagnification through food webs of both regions. Combining this with isotopic composition of samples shows that δ(202)Hg increases with the trophic level of organisms and also with methylmercury in fish from Lake Baikal. This study demonstrates that MIF in fish samples from Bratsk Water Reservoir allow to trace anthropogenic Hg, since fish with the highest levels of Hg in muscle have the same isotopic composition as the sediment in which anthropogenic Hg was deposited. Less contaminated fish do not exhibit this anthropogenic signature accumulating relatively lower Hg amount from the contaminated sediments. This work reveals that Hg isotopic composition can be used to track the contribution of anthropogenic sources in fish from a contaminated lake.