Reactivity and bioconcentration of stable cesium in a hyperturbid fluvial-estuarine continuum: A combination of field observations and geochemical modeling.

Effective, post-accidental management needs an accurate understanding of the biogeochemical behavior of radionuclides in surface environments at a regional scale. Studies on stable isotopes (element homologs) can improve this knowledge. This work focuses on the biogeochemical behavior of stable cesium (Cs) along a major European fluvial-estuarine system, the Gironde Estuary (SW France). We present results obtained from (i) a long-term monitoring (2014-2017) of dissolved (Csd) and particulate (Csp) Cs concentrations at five sites along the freshwater continuum of the Garonne watershed, (ii) Csd and Csp concentrations during four oceanographic campaigns at contrasting hydrological conditions along longitudinal profiles of the estuarine system, (iii) a 24 h cycle of Csp at the estuary mouth, and (iv) a historical trend of Cs bioconcentration in wild oysters at the estuary mouth (RNO/ROCCH, 1984-2017). In addition, we model the partitioning of Cs within the estuarine environment for clay mineral interactions via PhreeqC. At fluvial sites, we observe a geogenic dependence of the Csp and a seasonal variability of Csd, with a downstream increase of the solid-liquid partitioning (log10 Kd values from 3.64 to 6.75 L kg-1) for suspended particulate matter (SPM) < 200 mg L-1. Along the estuarine salinity gradients, Cs shows a non-conservative behavior where fresh SPM (defined as Cs-depleted particles recently put in contact with Csd) act as a Cs sink during both flood and low discharge (drought) conditions. This sorption behavior was explained by the geochemical model, highlighting the relevance of ionic strength, water and SPM residence times. However, at high salinities, the overall log10 Kd value decreases from 6.02 to 5.20 for SPM ∼300-350 mg L-1 due to the Csd oceanic endmember. Despite wild oysters showing low bioconcentration factors (∼1220 L kg-1) at the estuary mouth, they are sensitive organisms to Cs fluxes.

Combined X-ray absorption and SEM-EDX spectroscopic analysis for the speciation of thorium in soil.

Mobility and bioavailability of radionuclides in the environment strongly depend on their aqueous speciation, adsorption behavior and the solubility of relevant solid phases. In the present context, we focus on naturally occurring Th-232 at a location in central Sri Lanka presenting high background radiation levels. Four different soil samples were characterized using X-ray Absorption Spectroscopy (XAS) at the Th L3-edge (16.3 keV), Scanning Electron Microscopy (SEM) and Energy Dispersive X-ray (EDX) spectroscopy. X-ray Absorption Near Edge Structure (XANES) spectra are applied as a fingerprint indication for Th existing in different chemical environments. Linear combination fitting (LCF) of the Extended X-ray Absorption Fine Structure (EXAFS) data involving reference Th-monazite (phosphate) and thorianite (oxide) compounds suggested that Th is mostly present as Th-phosphate (76 ± 2%) and Th-oxide (24 ± 2%), even though minor amounts of thorite (silicate) were also detected by SEM-EDX. Further studies on selected individual particles using micro-focus X-ray Fluorescence (µ-XRF) and micro-X-ray Absorption Spectroscopy (µ-XAS) along with SEM-EDX elemental mapping provided information about the nature of Th-bearing mineral particles regarding mixed phases. This is the first study providing quantitative and XAS based speciation information on Th-mineral phases in soil samples from Sri Lanka.

Surface characterisation reveals substrate suitability for cyanobacterial phototaxis.

Cyanobacteria respond to light stimulation, activating localised assembly of type IV pili for motility. The resulting phototactic response is highly dependent on the nature of the incoming light stimulus, and the final motility parameters depend on the surface properties. Conventionally, phototaxis studies are carried out on hydrogel surfaces, such as agarose, with surface properties that vary in time due to experimental conditions. This study considers five substrates, widely utilized in microfluidic technology, to identify the most suitable alternative for performing reliable and repeatable phototaxis assays. The surfaces are characterised via a contact angle goniometer to determine the surface energy, white light interferometry for roughness, zeta-potentials and AFM force distance curves for charge patterns, and XPS for surface composition. Cell motility assays showed 1.25 times increment on surfaces with a water contact angle of 80° compared to a reference glass surface. To prove that motility can be enhanced, polydimethylsiloxane (PDMS) surfaces were plasma treated to alter their surface wettability. The motility on the plasma-treated PDMS showed similar performance as for glass surfaces. In contrast, untreated PDMS surfaces displayed close to zero motility. We also describe the force interactions of cells with the test surfaces using DLVO (Derjaguin-Landau-Verwey-Overbeek) and XDLVO (extended DLVO) theories. The computed DLVO/XDLVO force-distance curves are compared with those obtained using atomic force microscopy. Our findings show that twitching motility on tested surfaces can be described mainly from adhesive forces and hydrophobicity/hydrophilicity surface properties. STATEMENT OF SIGNIFICANCE: The current article focuses on unravelling the potential Micro-Electro-Mechanical System (MEMS) compatible surfaces for studying phototactic twitching motility of cyanobacteria. This is the first exhaustive surface characterization study coupled with phototaxis experiments, to understand the forces contributing to twitching motility. The methods shown in this paper can be further extended to study other surfaces and also to other bacteria exhibiting twitching motility.

Historical mass balance of cadmium decontamination trends in a major European continent-ocean transition system: Case study of the Gironde Estuary.

Despite the effective remediation efforts following the end of the metallurgic activity thirty years ago upstream the Lot River watershed, the levels of cadmium (Cd) accumulated in wild oysters from the downstream Gironde Estuary still exceed nowadays the admissible human consumption limit (5 mg/kg, d.w.). The main goal of this work is to quantify the role of sediments as long-term intra-estuarine sources or sinks of Cd and the transport of this contaminant towards the estuary mouth taking as case study the example of the highly turbid Gironde Estuary. The original estimation for the annual net fluxes of the suspended particulate matter ( [Formula: see text] and particulate Cd ( [Formula: see text] ) presented in this work between 1990 and 2020 indicates that 80% of the Cd discharged into the ocean is in dissolved form (Cdd). The values of [Formula: see text] vary proportionally to those of [Formula: see text] and ranged between 0.1 and 1.4 t/y, with a ten-year average decreasing from 0.8 to 0.6 t/y for the past 30 years. The differences between ten-year total (Cdp + Cdd) gross and net fluxes show that Cd has effectively been stored in estuarine sediments. This Cd storage was of about 43, 22 and 13 t for the 1990s, 2000s and 2010s, respectively. However, during years of low gross fluxes, estuarine sediments act as additional, secondary sources of bio-available/dissolved Cd into the water column, potentially relating to the continued observations of high Cd concentrations in wild oysters at the estuary mouth. In addition to the natural solubility of Cdp along the salinity and turbidity gradients of the estuary, natural and anthropogenic remobilization of bottom sediment particles further contribute to its mobilization from the particle phase, along with other numerous inorganic/organic pollutants. The mass balances presented in this work could support a new sediment management policy potentially more beneficial to the estuarine ecosystem.

Structure and Surface Complexation at the Calcite(104)-Water Interface.

Calcite is the most stable polymorph of calcium carbonate (CaCO3) under ambient conditions and is ubiquitous in natural systems. It plays a major role in controlling pH in environmental settings. Electrostatic phenomena at the calcite-water interface and the surface reactivity of calcite in general have important environmental implications. They may strongly impact nutrient and contaminant mobility in soils and other subsurface environments, they control oil recovery from limestone reservoirs, and they may impact the safety of nuclear waste disposal sites. Besides the environmental relevance, the topic is significant for industrial applications and cultural heritage preservation. In this study, the structure of the calcite(104)-water interface is investigated on the basis of a new extensive set of crystal truncation rod data. The results agree with recently reported structures and resolve previous ambiguities with respect to the coordination sphere of surface Ca ions. These structural features are introduced into an electrostatic three-plane surface complexation model, describing ion adsorption and charging at the calcite-water interface. Inner surface potential data for calcite, as measured with a calcite single-crystal electrode, are used as constraints for the model in addition to zeta potential data. Ion adsorption parameters are compared with molecular dynamics simulations. All model parameters, including protonation constants, ion-binding parameters, and Helmholtz capacitances, are within physically and chemically plausible ranges. A PhreeqC version of the model is presented, which we hope will foster application of the model in environmental studies.

The Influences of Cement Hydration and Temperature on the Thixotropy of Cement Paste.

The rheological properties of fresh cement paste are highly influenced by a large number of parameters, among which the most important factors are the applied shear stress, and the shear history, the age of the sample and the temperature. The effects of these parameters on the yield stress (designated as structural limit stress in this work), the viscosity and the structural recovery rate (i.e., the change in dynamic viscosity with time at rest) were studied. In parallel, the changes in ion composition of the carrier liquid, mineral phase content and granulometry were investigated. The results reveal that all investigated rheological parameters exhibit an approximated bi-linear trend with respect to the degree of hydration, with a period of quasi-constant properties until a degree of hydration of approximately 0.07, followed by a non-linear increase. This increase could be attributed to the formation of calcium hydroxide (CH) and calcium-silicate-hydrate (C-S-H) via calorimetry results. With regard to the effect of the shear history of the sample on the rheological properties, the structural limit stress showed a minor dependency on the shear history immediately after the end of shearing, which, however, vanished within the first minute at rest. The same is true for the structural recovery rate. The presented results give detailed insights into the influences of hydration and shear on the rheological properties-especially the thixotropy-of fresh cement pastes.

Tin-113 and Selenium-75 radiotracer adsorption and desorption kinetics in contrasting estuarine salinity and turbidity conditions.

Batch experiments were performed to study adsorption and desorption of 75Se and 113Sn radiotracers at environmentally representative concentrations of ~0.3 ng L-1 and ~3 ng L-1, respectively. The radiotracers were incubated with wet bulk sediments from the Gironde Estuary and the Rhône River, combining freshwater and coastal seawater salinity (S = 0, S = 32) and three different Suspended Particulate Matter (SPM) concentrations (10 mg L-1, 100 mg L-1, 1000 mg L-1) to simulate six hydrologically contrasting situations for each particle type. Results showed no measurable adsorption for 75Se under the experimental conditions, whereas >90% of 113Sn rapidly adsorbed onto the particles during the first hours of exposure. Adsorption efficiency increased with increasing SPM concentration and seemed to be slightly greater for the Rhône River sediments, potentially related to the intrinsic mineral composition. Desorption of spiked sediments exposed to filtered, unspiked freshwater and seawater only occurred for 113Sn (<15% of the previously adsorbed 113Sn) in the Garonne River sediments. This study provides insights to the potential environmental behaviour of hypothetical radionuclide releases of Se and Sn into highly dynamic and contrasting aquatic systems. Multiple accidental scenarios for the case of the Gironde Estuary and the Rhône River are discussed. These scenarios suggest that the environmental fate of soluble radionuclides like Se will be associated to water hydrodynamics and potentially more bioavailable whereas highly particle-active radionuclides like Sn will follow natural river/estuarine sedimentary regimes. Information on reactivity of radionuclides is important for improving the precision of current approaches aiming at modelling environmental radionuclide dispersion in continent-ocean transition systems.

Platinum in sediments and mussels from the northwestern Mediterranean coast: Temporal and spatial aspects.

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.

Rare Earth Element fluxes over 15 years into a major European Estuary (Garonne-Gironde, SW France): Hospital effluents as a source of increasing gadolinium anomalies.

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.

Tracing platinum accumulation kinetics in oyster Crassostrea gigas, a sentinel species in coastal marine environments.

Platinum Group Elements (PGEs) are extremely scarce in the Earth's Crust and of strong interest for high-end technologies due to their specific properties. They belong to the Technology Critical Elements (TCEs) for which use is forecast to increase, implying growing emissions into the environment in the following years. In particular, with the intensive use of platinum (Pt) in car catalytic converters, the anthropogenic geochemical cycle of this element has surpassed the natural cycle. Yet, environmental Pt levels are still in the sub picomolar range, making its analytical detection a challenge. Few studies cover the behavior of Pt in marine waters in terms of speciation, reactivity and possible transfer to the biota. In this study, oysters (Crassostrea gigas) from an unpolluted estuary were exposed to the stable isotope 194Pt in seawater at a range of concentrations during 35days. Seawater was renewed daily and spiked to three nominal Pt concentrations (50, 100, and 10,000ng·L-1) for two replicate series. In addition, control conditions were monitored. Five oysters from each tank were dissected after 3, 7, 14, 21, 28, 35days of Pt exposure, and analyzed by ICP-MS. Accuracy of this analytical method applied to biological matrix was checked by an inter-method comparison with a voltammetrical technique. A concentration-dependent accumulation of Pt in oysters increasing with exposure time occurred. After 28days, oyster Pt accumulation from low and intermediate exposure conditions reached a plateau. This was not the case of the highest exposure condition for which oyster tissues showed increasing concentrations until the last day of the experiment. A linear correlation exists between seawater concentrations and Pt content in oysters for low and intermediate exposure concentrations i.e. closer to environmental concentrations. By showing high Pt accumulation potential, oysters may serve as sentinels, ensuring biomonitoring of Pt concentrations in marine coastal waters.

SCHeMA EU Project Summer School Report (Bilbao June 16 - 17, 2016).

This conference report describes the training activities that took place in the frame of the Integrated in Situ Chemical MApping probe (SCHeMA) summer school organized from the 14th to the 16th of June 2016 in Bilbao (Spain).

Effects of ocean acidification on the brown alga Padina pavonica: decalcification due to acute and chronic events.

Since the industrial revolution, anthropogenic CO2 emissions have caused ocean acidification, which particularly affects calcified organisms. Given the fan-like calcified fronds of the brown alga Padina pavonica, we evaluated the acute (short-term) effects of a sudden pH drop due to a submarine volcanic eruption (October 2011-early March 2012) affecting offshore waters around El Hierro Island (Canary Islands, Spain). We further studied the chronic (long-term) effects of the continuous decrease in pH in the last decades around the Canarian waters. In both the observational and retrospective studies (using herbarium collections of P. pavonica thalli from the overall Canarian Archipelago), the percent of surface calcium carbonate coverage of P. pavonica thalli were contrasted with oceanographic data collected either in situ (volcanic eruption event) or from the ESTOC marine observatory data series (herbarium study). Results showed that this calcified alga is sensitive to acute and chronic environmental pH changes. In both cases, pH changes predicted surface thallus calcification, including a progressive decalcification over the last three decades. This result concurs with previous studies where calcareous organisms decalcify under more acidic conditions. Hence, Padina pavonica can be implemented as a bio-indicator of ocean acidification (at short and long time scales) for monitoring purposes over wide geographic ranges, as this macroalga is affected and thrives (unlike strict calcifiers) under more acidic conditions.