Tailings containing mining and ore treatment waste, accumulated over long time periods are major contaminant sources at the watershed scale and may seriously impair environmental quality of river-sea ...continuums. A critical review of existing work in different disciplines addressing the multi-metal contamination of the Gironde Watershed, a major fluvial-estuarine model system representative of many other systems worldwide, has provided a condensed, yet pertinent overview on various aspects of this environmental problem. Combining long-term observation and contamination records from different environmental archives, there is a clear trend towards resilience for the main historical contaminants (Cd, Zn, Pb and Cu), yet suggesting that resilience needs appropriate management of both, tailings as the initial source and contaminated sediments acting as temporary metal traps which may transform into delayed sources. Contaminated sediment management is an increasingly important challenge due to (i) successful remediation at the contamination source itself (ii) global-change induced factors and strategies and (iii) lacking coordination of actions between upstream and downstream parts of the fluvial-estuarine continuum. Less studied and emerging metallic contaminants show recent trends in sediments and biota that are decoupled from the legacy contaminant trajectories due to recent sources and applications, suggesting that further work is needed to assess their potential impact on the environmental quality of the Gironde fluvial-estuarine system and that of other systems, especially in a context of worldwide rapidly growing mining activity and metal use.
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•Long-term observation, and environmental archives provide contamination trajectories.•Tailing and sediment management remain challenging for future resilience.•Less-studied and emerging metallic contaminants need strengthened research.•Forecast of worldwide mining activity warrants real-time surveillance of impacts.
A new submersible probe for the in situ detection of nitrate, nitrite, and chloride in seawater is presented. Inline coupling of a desalination unit, an acidification unit, and a sensing flow cell ...containing all-solid-state membrane electrodes allows for the potentiometric detection of nitrate and nitrite after removal of the key interfering ions in seawater, chloride and hydroxide. Thus, the electrodes exhibited attractive analytical performances for the potentiometric detection of nitrate and nitrite in desalinated and acidified seawater: fast response time (t 95 < 12 s), excellent stability (long-term drifts of <0.5 mV h–1), good reproducibility (calibration parameter deviation of <3%), and satisfactory accuracy (uncertainties <8%Diff compared to reference technique). The desalination cell, which can be repetitively used for about 30 times, may additionally be used as an exhaustive, and therefore calibration-free, electrochemical sensor for chloride and indirect salinity detection. The detection of these two parameters together with nitrate and nitrite may be useful for the correlation of relative changes in macronutrient levels with salinity cycles, which is of special interest in recessed coastal water bodies. The system is capable of autonomous operation during deployment, with routines for repetitive measurements (every 2 h), data storage and management, and computer visualization of the data in real time. In situ temporal profiles observed in the Arcachon Bay (France) showed valuable environmental information concerning tide-dependent cycles of nitrate and chloride levels in the lagoon, which are here observed for the first time using direct in situ measurements. The submersible probe based on membrane electrodes presented herein may facilitate the study of biogeochemical processes occurring in marine ecosystems by the direct monitoring of nitrate and nitrite levels, which are key chemical targets in coastal waters.
The determination of palladium (Pd) in environmental samples by ICP-MS is challenging as all its isotopes are extensively interfered due to isobaric (e.g. 110Cd on 110Pd, 106Cd on 106Pd), polyatomic ...(e.g. 92Mo16O on 108Pd, 89Y16O on 105Pd) and doubly-charged (e.g. 208Pb2+ on 104Pd) species formed in the plasma from elements usually present at concentrations several orders of magnitude higher. As a result, the determination of Pd in natural waters is extremely scarce despite is has been proven that this metal is subject to a significant anthropogenic impact mainly linked to its use in catalytic converters in motor vehicles. In order to overcome this situation, we have developed an ultra-trace interference-free methodology for the determination of Pd in natural waters by ICP-MS after on-line matrix separation and preconcentration. The method is based on the strong affinity of Pd towards a commercially-available carboxymethylated polyethylenimine resin, which also has the ability to retain most of the transition metals. However, Pd is not eluted from the resin at typical elution conditions (e.g. 2 M HNO3, which removes all the interference-forming metals), but this can be attained by passing a diluted thiourea solution (10−3 M). Therefore, the interference-free on-line determination of Pd in natural waters was successfully achieved using a two-step elution procedure. Procedural blank values were 0.012 ± 0.003 ng kg−1 (n = 6), which results in a detection limit of 0.010 ng kg−1, allowing the determination of dissolved Pd in natural samples at low, ambient concentrations. The optimized methodology was applied to determine the concentrations of Pd in the Gironde estuary, which represents the first dissolved Pd profile along an estuarine salinity gradient and one of the first dataset of Pd concentrations in natural waters at ambient levels in almost 4 decades. The simplicity of the preconcentration setup and the possibility for its automation offers new analytical opportunities, which will be useful for future studies aiming to improve our understanding of the behavior of Pd in natural waters.
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•Ultra-trace on-line separation and preconcentration ICP-MS determination of Pd in waters.•Interference-free determination of Pd in natural samples at ambient concentrations.•First dissolved Pd profile along an estuarine salinity gradient reported.
Large-gap quantum spin Hall insulators are promising materials for room-temperature applications based on Dirac fermions. Key to engineer the topologically non-trivial band ordering and sizable band ...gaps is strong spin-orbit interaction. Following Kane and Mele's original suggestion, one approach is to synthesize monolayers of heavy atoms with honeycomb coordination accommodated on templates with hexagonal symmetry. Yet, in the majority of cases, this recipe leads to triangular lattices, typically hosting metals or trivial insulators. Here, we conceive and realize "indenene", a triangular monolayer of indium on SiC exhibiting non-trivial valley physics driven by local spin-orbit coupling, which prevails over inversion-symmetry breaking terms. By means of tunneling microscopy of the 2D bulk we identify the quantum spin Hall phase of this triangular lattice and unveil how a hidden honeycomb connectivity emerges from interference patterns in Bloch p
± ip
-derived wave functions.
High temporal resolution sampling of runoff (15 samples/4 h) and river water (24 samples/24 h) was performed during a major rainstorm (41 mm/4 h) in the Bordeaux Metropole, after a dry and high ...vehicle-density period. Runoff was sampled at the outlet of one collector draining Northern Bordeaux Highway (NBH; 80,000–93,000 vehicles/day) and river water in the downstream Jalle River. The studied metals, including priority and emergent (Rare Earth Elements REEs) contaminants, showed major temporal and spatial variations in the dissolved and particulate concentrations. Hierarchical cluster analyses distinguished metal groups, reflecting different: (i) sources (i.e., automotive traffic: Zn–Cu–Ce and wastewater treatment plant: Cd–Ag–Gd) and/or (ii) processes (i.e., groundwater dilution by rainwater and sorption processes). The contribution of the particulate fraction to total metal fluxes was predominant in the NBH collector (except for Sr and Mo) and highly variable in the Jalle River, where the highest particulate metal loads were due to the export of road dusts exported by the NBH collector. Metal fluxes from the NBH collector represented highly variable fractions of daily fluxes into the Gironde Estuary at the outlet of the Jalle River, depending on elements and partitioning. The resulting relative contributions ranged from: 5% (Sr) to 40% (Cu) for dissolved phases and 30% (As) to 88% (Cu) for particulate phases. The first 40 min of the event accounted for 65% of the suspended particulate matter flux (and associated particulate metals) exported by the NBH collector, whereas the respective water flux contribution was 35%. This finding clearly demonstrates the importance of monitoring the first minutes of rainy events when establishing mass balances in urban systems.
We relate the definition of an ultrametric space to the topological distance algorithm—an algorithm defined in the context of peer-to-peer network applications. Although (greedy) algorithms for ...constructing minimum spanning trees such as Prim’s or Kruskal’s algorithm have been known for a long time, they require the complete graph to be specified and the weights of all edges to be known upfront in order to construct a minimum spanning tree. However, if the weights of the underlying graph stem from an ultrametric, the minimum spanning tree can be constructed incrementally and it is not necessary to know the full graph in advance. This is possible, because the join algorithm responsible for joining new nodes on behalf of the topological distance algorithm is independent of the order in which the nodes are added due to the property of an ultrametric. Apart from the mathematical elegance which some readers might find interesting in itself, this provides not only proofs (and clearer ones in the opinion of the author) for optimality theorems (i.e., proof of the minimum spanning tree construction) but a simple proof for the optimality of the reconstruction algorithm omitted in previous publications too. Furthermore, we define a new algorithm by extending the join algorithm to minimize the topological distance and (network) latency together and provide a correctness proof.
The increase in the global population, coupled with growing consumption of Rare Earth Elements (REEs), has led to increasing transfer of these emerging contaminants into the environment, particularly ...through the effluents from wastewater treatment plants (WWTP). The objectives of this study were to determine the geochemical quality of a French river subject to strong urban pressure (the Jalle River in the Bordeaux area) and to examine the bioavailability of natural and anthropogenic REEs in a model species of freshwater bivalve, the Asian clam Corbicula fluminea. To this end, two fractions (dissolved and total) of the water from the Jalle River were sampled and the bivalves were exposed by in situ caging during a three-month monitoring period. The REE patterns obtained showed the presence of Gadolinium (Gd) anomalies in the dissolved and total fractions as well as in Corbicula fluminea. The apparent bioavailability of natural REEs was in the following order for the dissolved fraction: Medium REEs (MREEs) > Light REEs (LREEs) > Heavy REEs (HREEs) and for the particulate fraction: MREEs > LREEs = HREEs. These results highlight the importance of the particulate fraction in the study of the bioavailability of REEs in bivalves. An increase of anthropogenic Gd (Gdanth) was observed in the dissolved fraction between the upstream site (3.4 ng.L−1) and the WWTP Downstream site (48.4 ng.L−1). The Gd anomaly observed in the water was also observed in Corbicula fluminea with a significant increase in the bioaccumulation of Gdanth, from 1.5 ± 1 ng.gDW−1 upstream to 4.1 ± 0.7 ng.gDW−1 downstream of the WWTP effluents, thus confirming the enhanced bioavailability of medical-origin Gd to freshwater bivalves. This study strongly suggests that Corbicula fluminea can be used as a sentinel species in the monitoring of Gd contamination of medical origin. It would thus appear important to consider the potential entry of this contaminant into the human food chain via other, commercially exploited bivalve species.
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•REE concentrations measured in urban river and caged freshwater bivalves•Anthropogenic Gd anomaly observed in geochemical and biological samples•Bioavailability of natural and anthropogenic REEs in freshwater bivalves•Particulate phase appears to be important for REEs uptake by benthic bivalves.•Corbicula fluminea is a sentinel species for anthropogenic Gd from WWTP effluents.
New and rapidly developing technologies imply the emission of emerging potentially toxic contaminants such as Rare Earth Elements (REEs). Yet, the lithology-derived quantities and anthropogenic ...contributions, especially from urban areas, to annual REE fluxes into fluvial-estuarine systems remain widely unknown. The Garonne River drains water from ~20% of the French land surface hosting about 5,200,000 inhabitants and two large cities. Based on long-term monitoring (2003–2017) of water discharges and dissolved REEs concentrations at the outlet of the Garonne Watershed upstream from Bordeaux, this study aims at assessing REE anomalies and evaluating temporal evolution of annual dissolved REE fluxes into the Gironde Estuary. Additionally, potential urban sources (e.g. domestic, medical) in the urban area of Bordeaux (1,190,000 inhab.) were analyzed to evaluate respective signatures and contributions. Gadolinium (Gd) showed clear anomalies in all samples, with annual average anthropogenic concentrations ranging from 1.8 to 7.2 ng·L−1 (0.011 to 0.046 nmol·L−1) in the Garonne River. If variations in annual Gd fluxes depend on hydrology, anthropogenic Gd fluxes have shown an overall increasing trend from 32 kg·year−1 (204 mol·year−1) in 2003 to 75 kg·year−1 (475 mol·year−1) in 2017. Sewer waters from the third largest hospital complex of France, the hospital group Pellegrin, contributed 25% to the incoming daily Gd flux into Bordeaux major Waste Water Treatment Plant (WWTP), owed to Gd use as contrast agent for Magnetic Resonance Imaging (MRI). Due to weak removal efficiency in the WWTP, the Bordeaux Metropole significantly contributes (>27 kg·year−1; 172 mol·year−1) to Gd fluxes in the Gironde Estuary. The temporal evolution of anthropogenic Gd fluxes in the Garonne River may be related with the growing regional population and the increasing number of MRI instruments, highlighting the importance of new high-tech applications in urban areas on contaminant fluxes and their potential harmful effects in fluvial-estuarine systems in the future.
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•Dissolved REE assessment in a major French river (Garonne).•Temporal evolution of annual REE fluxes between 2013 and 2017.•A two-fold increase of annual anthropogenic gadolinium (Gdanthr) in 15 years.•Annual Gdanthr fluxes are related to increasing number of MRI scans.•Effluent from one hospital accounted for 25% of the Gdanthr transport.
Zusammenfassung
Der vorliegende Aufsatz gibt persönliche Erfahrungen des Autors als Leiter der Abteilung Sicherungsverwahrung der Justizvollzugsanstalt Werl wieder. Bei dieser Abteilung handelt es ...sich um die bundesweit größte Einrichtung für diese Form des Maßregelvollzugs mit 140 Plätzen bei einer Zuständigkeit für das gesamte Land Nordrhein-Westfalen. Der Beitrag stellt – aus Sicht des Autors – wesentliche Aspekte der Praxis der Sicherungsverwahrung dar und erhebt weder Anspruch auf Vollständigkeit noch hinsichtlich der Übertragbarkeit auf andere Einrichtungen anderer Länder; allerdings lassen die Rückmeldungen, die den Autor auf der 23. Berliner Junitagung für Forensische Psychiatrie und Psychologie erreichten, auf eine hohe Übereinstimmung der Verhältnisse im Bundesgebiet schließen.
Preparation of SiC(0001) substrates is of high relevance to graphene growth. Yet, if only a smooth surface could be achieved, heteroepitaxy of many other two-dimensional materials comes into reach. ...Here we report a novel approach to hydrogen etching of SiC, based on stepwise ultrapure H exposure with slow substrate cooling rates. For the first time, the atomic evolution of the surface structure is witnessed by scanning tunneling microscopy. A detailed picture of the gas phase chemistry emerges, such as a zipper-like material desorption at step edges. The Si–C sheets are removed in layer-by-layer fashion, leading to large terraces with straight rims. The process ultimately results in an atomically smooth surface with complete H-passivation, with no detectable defect states in photoemission. The degree of perfection achieved suggests the use of this substrate as a versatile nanostructure template.
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