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.
Platinum (Pt) is considered a Technology Critical Element (TCE) and an emerging metallic contaminant with increasing release into the environment. Gaps in knowledge and understanding of environmental ...levels, fate and effects of Pt still exist, especially in the marine environment. This work presents Pt concentrations in the northwestern Mediterranean coast including: (i) temporal variability from sediment cores and farmed mussels in the Toulon Bay (historically affected by intense human activities) and (ii) spatial distribution from recent wild mussels collected along ∼ 700 km coastline with contrasting ecosystems (including natural reserves), quantified using voltammetry and inductively coupled plasma-mass spectrometry. The historical (>100 years) record of Pt in sediments from the Toulon Bay suggests the existence of non-negligible Pt sources older than those related to vehicle emission devices, such as petrol industry and coal-fired activities. A strong Pt increase in more recent sediments (from ∼12 to 16 ng g−1) and mussels (8-fold increase from ∼0.12 to 0.80 ng g−1) covering the past 25 years reflect the overall evolution of Pt demand in Europe (∼20-fold increase for vehicle catalysts in 20 years). Spatial biomonitoring of Pt in mussels along the northwestern Mediterranean coast is assumed to reflect inter-site differences of Pt exposure (0.09–0.66 ng g−1) despite seasonal effect on tissue development. This study highlights the need for thorough and regular monitoring of Pt levels in sediments and biota from urbanized coastal areas in order to better assess the environmental impact of this TCE, including potential risks for marine organisms.
•Platinum levels were monitored in contrasting sites of the NW Mediterranean coast.•Historical sediments reflect non-vehicle related, old Pt anthropogenic sources.•Past 25-years sediments and mussels show recent vehicle related Pt contamination.•Biomonitoring mussels reflect the degree of Pt contamination in coastal environment.
Platinum (Pt) is a Technology Critical Element (TCE) which, since the 1990s, has been mainly used in the industry in catalytic converters for automobile emission control. Previous studies have shown ...Pt contamination of road-side sediments and surface sediments in urban rivers and lakes but few of them have addressed temporal variations. The present work presents historical Pt concentration trends in 137Cs-dated sediment cores from floodplains or secondary channels at the outlets of three major French watersheds (Loire, Rhone, and Seine Rivers) covering the past ∼110 years, i.e., from the 1910s to 2021. Platinum baseline levels in the sediment were estimated for the Loire River (0.76 ± 0.22 μg kg−1 for the period ∼1910-∼1955) and the Rhone River (1.64 ± 0.41 μg kg−1), and historical Pt variations seem to reflect variations in hydrodynamics and grain size composition. Since the early 2000s, Pt concentrations in the Loire and the Rhone River sediments tend to increase (>2.5 μg kg−1) and were attributed to the use of car catalytic converters, an emerging technology since the 1990s using >50 % of European Pt demand. High and variable historical Pt concentrations (up to 14.6 μg kg−1) in the Seine River sediments may reflect legacy Pt sources due to former anthropogenic activities in this watershed, such as the use of Pt-based catalysts for petroleum refinery since the end of the 1940s, coal handling and precious metals refining, probably concealing the likely presence of an emerging traffic-related Pt signal. This first comparison of historical Pt concentration trends in sediments from contrasting watersheds allows to distinguish signals originating from different natural and anthropogenic sources (background level, historical sources, road traffic).
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•Few studies on Pt level in sediment for reconstructing the past geochemical quality•Ad-CSV analysis on selected sediments collected in dated cores in 3 French rivers•Temporal evolution of Pt concentrations (trajectory) between 1910 and 2021•Signals originating from different natural (baseline) and anthropogenic sources•Highest Pt concentrations in the Seine R. to past/historical and emerging sources
Using Wi-Fi IEEE 802.11 standard, radio frequency waves are mainly used for communication on various devices such as mobile phones, laptops, and smart televisions. Apart from communication ...applications, the recent research in wireless technology has turned Wi-Fi into other exploration possibilities such as human activity recognition (HAR). HAR is a field of study that aims to predict motion and movement made by a person or even several people. There are numerous possibilities to use the Wi-Fi-based HAR solution for human-centric applications in intelligent surveillance, such as human fall detection in the health care sector or for elderly people nursing homes, smart homes for temperature control, a light control application, and motion detection applications. This paper’s focal point is to classify human activities such as EMPTY, LYING, SIT, SIT-DOWN, STAND, STAND-UP, WALK, and FALL with deep neural networks, such as long-term short memory (LSTM) and support vector machines (SVM). Special care was taken to address practical issues such as using available commodity hardware. Therefore, the open-source tool Nexmon was used for the channel state information (CSI) extraction on inexpensive hardware (Raspberry Pi 3B+, Pi 4B, and Asus RT-AC86U routers). We conducted three different types of experiments using different algorithms, which all demonstrated a similar accuracy in prediction for HAR with an accuracy between 97% and 99.7% (Raspberry Pi) and 96.2% and 100% (Asus RT-AC86U), for the best models, which is superior to previously published results. We also provide the acquired datasets and disclose details about the experimental setups.
We report here on the development and application of a submersible, compact, low power consumption, integrated multichannel trace metal sensing probe (TracMetal). This probe is unique in that it ...allows high-resolution, simultaneous in-situ measurements of the potentially bioavailable (so-called dynamic) fraction of Hg(II), As(III), Cd(II), Pb(II), Cu(II), Zn(II). The TracMetal incorporates nanostructured Au-plated and Hg-plated gel-integrated microelectrode arrays. In addition to be selective to the fraction of metal potentially bioavailable, they offer protection against fouling and ill-controlled convective interferences. Sensitivities in the low pM for Hg(II) and sub-nM for the other target trace metals is achieved with precision ≤ 12%. The TracMetal is capable of autonomous operation during deployment, with routines for repetitive measurements (1-2 h−1), data storage and management, data computer visualization, and wireless data transfer. The system was successfully applied in the Arcachon Bay, to study the temporal variation of the dynamic fraction of the trace metals targeted. The in situ autonomous TracMetal measurements were combined with in situ measurements of the master bio-physicochemical parameters and sample collection for complementary measurements of the dissolved metal concentrations, organic matter concentrations and proxy for biological activities. The integration of all data revealed that various biotic and abiotic processes control the temporal variation of the dynamic fractions of the target metals (Medyn). The difference in the percentage of the dynamic forms of the metals studied and the short-term processes influencing their variation highlight the TracMetal potentiality as metal bioavailability-assessment sentinel to achieve comprehensive environmental monitoring of dynamic aquatic systems.
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•Unique submersible autonomous multichannel tool for in situ metal quantification.•Simultaneous detection of the bioavailable fraction of six hazardous metals.•Autonomous monitoring of short-term temporal variation of bioaccessible metal species.•Biotic and abiotic processes influencing the speciation of the trace metals targeted.
Platinum (Pt) is a technology critical element (TCE) for which biogeochemical cycles are still poorly understood. This lack of knowledge includes Pt effects on marine organisms, which proved to be ...able to bioconcentrate this trace element. Oysters
Crassostrea gigas
were exposed to stable Pt isotope spiked daily in seawater for 35 days. Seawater was renewed daily and spiked (with Pt(IV)) to three nominal Pt concentrations (50, 100, and 10,000 ng L
−1
) for two replicate series. Organotropism study revealed that gills, and to a lesser extent mantle, are the key organs regarding Pt accumulation, although a time- and concentration-dependent linear increase in Pt levels occurred in all the organs investigated (i.e., digestive gland, gonads, gills, mantle, and muscle). In oysters exposed to Pt concentrations of 10,000 ng L
−1
, significant biomarker impairments occurred, especially at cellular levels. They reflect altered lipofuscin and neutral lipid contents, as well as intralysosomal metal accumulation. These observations were attributed to activation of excretion/detoxification mechanisms, including Pt elimination through feces and clearly support the importance of the digestive gland in the response to direct Pt exposure. Despite relatively constant condition index, the integrative biological response (IBR) index suggests a generally decreasing health status of oysters.
Two-dimensional electron systems, as exploited for device applications, can lose their conducting properties because of local Coulomb repulsion, leading to a Mott-insulating state. In triangular ...geometries, any concomitant antiferromagnetic spin ordering can be prevented by geometric frustration, spurring speculations about 'melted' phases, known as spin liquid. Here we show that for a realization of a triangular electron system by epitaxial atom adsorption on a semiconductor, such spin disorder, however, does not appear. Our study compares the electron excitation spectra obtained from theoretical simulations of the correlated electron lattice with data from high-resolution photoemission. We find that an unusual row-wise antiferromagnetic spin alignment occurs that is reflected in the photoemission spectra as characteristic 'shadow bands' induced by the spin pattern. The magnetic order in a frustrated lattice of otherwise non-magnetic components emerges from longer-range electron hopping between the atoms. This finding can offer new ways of controlling magnetism on surfaces.
The Lot–Garonne fluvial system is known for its historic heavy metal pollution resulting from mining and smelting activities since the late 19th century. Here, we report
137Cs activities and heavy ...metal (Cd, Zn, Cu, Pb and V) concentration–depth profiles from sediment cores retrieved in 2001 from three reservoirs in the Lot River. High mean sedimentation rates of 2.4–2.8
cm
a
−1 are indicated by
137Cs dating. The reservoir sediments have recorded the heavy metal deposition and thus allow establishing a connection between the temporal evolution of the heavy metal pollution and historical changes in smelting and waste-treatment proceedings. Based on heavy metal concentrations in sediments upstream of the anthropogenic inputs and bottom-sediments of the furthest downstream core (interpreted as old soil or riverbed), concentrations of ∼17, ∼82, ∼0.33 and ∼28
mg
kg
−1 for Cu, Zn, Cd and Pb, respectively, are proposed as natural background values for the Lot fluvial system. The geoaccumulation index (
I
geo Müller, G., 1979. Schwermetalle in den Sedimenten des Rheins-Veränderungen seit. Umschav 79, 133–149.) revealed that the Lot River sediments must be considered as “severely polluted” in Cd and Zn. Moreover, despite remediation efforts undertaken in the former smelting site, the Lot River is still “severely” (
I
geo
∼
4) and “moderately to severely” (
I
geo
>
2) impacted by Cd and Zn inputs, respectively.
Reservoir sediments provide fine-scale information on the historical record of metal pollution in a watershed.
Heavily contaminated sediments are a serious concern for ecosystem quality, especially in coastal areas, where vulnerability is high due to intense anthropogenic pressure. Surface sediments (54 ...stations), 50 cm interface cores (five specific stations), river particles, coal and bulk Pb plate from past French Navy activities, seawater and mussels were collected in Toulon Bay (NW Mediterranean Sea). Lead content and Pb stable isotope composition have evidenced the direct impact of sediment pollution stock on both the water column quality and the living organisms, through the specific Pb isotopic signature in these considered compartments. The history of pollution events including past and present contaminant dispersion in Toulon Bay were also demonstrated by historical records of Pb content and Pb isotope ratios in sediment profiles. The sediment resuspension events, as simulated by batch experiments, could be a major factor contributing to the high Pb mobility in the considered ecosystem. A survey of Pb concentrations in surface seawater at 40 stations has revealed poor seawater quality, affecting both the dissolved fraction and suspended particles and points to marina/harbors as additional diffuse sources of dissolved Pb.
Inorganic arsenic (As) speciation and behaviour were studied in the Gironde Estuary, a major European estuary in the south west of France. For the first time ever, the dynamic (potentially ...bioavailable) fraction of inorganic arsenite, As(III), and arsenate, As(V), were quantified in this estuary, using an antifouling gel-integrated gold microelectrode interrogated by square wave anodic stripping voltammetry (GIME-SWASV). The concentrations of dissolved As(III) and As(V) were determined by hydrid generation-flow injection-atomic absorption spectrometry (HG-FI-AAS) and inductively coupled plasma-mass spectrometry (ICP-MS) in collected samples following filtration through 0.2 μm, as well as 0.02 μm pore size filters. The concentrations of arsenite in the dynamic fraction, As(III)dyn, ranged from 1.3 to 3.3 nM, contributing almost completely to the dissolved arsenite, As(III)diss, which ranged between 0.9 and 3.1 nM in the 0.2 μm fraction, and between 1.2 and 3.7 nM in the 0.02 μm fraction. Concentrations of arsenate in the dynamic fraction, As(V)dyn, ranged from 0.9 to 22.9 nM, and contributed to the dissolved arsenate, As(V)diss, by 4–73% in the 0.2 μM fraction, and by 5–90% in the 0.02 μm fraction. The concentrations of As(V)diss in the 0.2 μm fraction were between 14.5 and 36.2 nM, and between 15.2 and 34.9 nM in the 0.02 μm fraction.
The impact of this work is two-fold. Measurements of As species with different techniques allowed one to validate the on-board GIME voltammetric measurements. In addition, determination of As species in different fractions, as well as combining the obtained results with the conducted measurements of dissolved Mn and Fe, particulate suspended matters, and master physicochemical parameters (T, pH, O2, redox E), helped to broaden the understanding of biotic and abiotic processes governing the distribution of arsenic, especially its potentially bioavailable forms, in the Gironde Estuary.
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•Speciation of inorganic arsenic was conducted in the Gironde Estuary.•For the first time, the dynamic (potentially bioavailable) fractions of As(III) and As(V) were determined together.•As(III) was mostly present in the fraction available for bio-uptake.•Marine biota and small (<20 nm) colloidal manganese influence As speciation.•Dissolved arsenic concentrations are similar to those reported 20 years ago.