Contrasting platinum trajectories in three major French rivers using dated sediment cores (1910-2021): From geochemical baseline to emerging source signals.

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).

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.

Platinum Group Element distribution in water and marine biota from two impacted estuarine environments (Douro and Ave estuaries, Portugal).

Platinum Group Elements (PGEs) are contaminants of emerging environmental concern considering their continuous increasing use and subsequent release in the environment. While recent field studies provided PGE levels in seawater, scarce knowledge still exists regarding PGE contamination in marine organisms, especially for rhodium (Rh). Water, macroalgae and mussels were sampled along two representative urbanized estuarine systems and adjacent coastal areas (Douro and Ave estuaries, Portugal). Rhodium and platinum (Pt) concentrations were quantified through both stripping voltammetry and mass spectrometry in collected samples. Spatial mapping of PGE contamination was, to a certain extent, correlated with proxies of urban effluents. The use of Pt/Rh ratios reflected the dominant influence of PGE traffic emissions along the Douro and inputs from various sources (including industries) on the Ave Estuary. Macroalgae and mussels PGE concentrations reflected urban pressure, amplifying environmental signals, and supporting their relevant use as bioindicators of PGE contamination in estuarine/coastal systems.

New insights into trace metal speciation and interaction with phytoplankton in estuarine coastal waters.

In coastal productive zones, phytoplankton activity may influence trace metal speciation and partitioning at short temporal scale. We coupled hourly in situ voltammetry quantification of the lead (Pb), cadmium (Cd), and copper (Cu) potentially bioavailable fractions, using an innovative submersible sensing probe (the TracMetal), to surface water sampling for the quantification of the targeted trace metals in the dissolved <0.2 µm and <0.02 µm fractions, suspended particles, and phytoplankton nets in the Gironde Estuary mouth. The in situ TracMetal monitoring reflected real-time dynamic Cd and Cu regeneration related to algal cells under post-bloom conditions as well as Pb remobilization due to photoreduction of colloids. The potentially bioavailable fraction consisted in 30, 30-50 and <10 % of the total dissolved fraction for Pb, Cd, and Cu, respectively, representing crucial ecotoxicological information. Metal bioconcentration factors using the dynamic fraction concentrations showed levels up to 107 for Cu in phytoplankton.

Speciation of Cu, Cd, Pb and Zn in a contaminated harbor and comparison to environmental quality standards.

The water column of harbors contains significant amounts of (priority) hazardous trace metals that may be released into coastal areas of high societal and economic interests where they may disturb their fragile equilibria. To deepen our understanding of the processes that influence the transport of the various metal fractions and allow for a more rigorous environmental risk assessment, it is important to spatially monitor the relevant chemical speciation of these metals. It is of particular interest to assess their so-called dynamic fraction, which comprises the dissolved chemical forms that are potentially bioavailable to living organisms. In this study this was achieved in the Genoa Harbor (NW Italy) for copper (Cu), lead (Pb), cadmium (Cd) and zinc (Zn) by applying a multi-method approach. For the first time in this system the dynamic fractions of the target metals (CuDyn, CdDyn, PbDyn, ZnDyn) were observed in real-time on-board by voltammetry using innovative electrochemical sensing devices. Trace metals in the operationally defined dissolved <0.2 µm and <0.02 µm fractions were equally quantified through sampling/laboratory-based techniques. The obtained results showed a clear spatial trend for all studied metals from the enclosed contaminated part of the harbor towards the open part. The highest CuDyn and CdDyn fractions were found in the inner part of the harbor while the highest PbDyn fraction was found in the open part. The proportion of ZnDyn was negligible in the sampled area. Small and coarse colloids were involved in Cu, Cd and Zn partitioning while only coarse colloids played an important role in Pb partitioning. The determined concentrations were compared to the Environmental Quality Standards (EQS) established by the EU and those determined by the Australia and New Zealand to trigger for 99 and 95% species protection values. The results of this work allow us to highlight gaps in the EQS for which metal concentration thresholds are excessively high or non-existent and should urgently be revised. They also reflect the need to quantify the potentially bioavailable fraction of hazardous trace metals instead of just their total dissolved concentrations. The data support the establishment of environmental quality standards and guidelines based on realistic risk assessment to protect aquatic life and resources and ultimately human health.

Global Analysis of the Zinc Homeostasis Network in Pseudomonas aeruginosa and Its Gene Expression Dynamics.

Zinc is one of the most important trace elements for life and its deficiency, like its excess, can be fatal. In the bacterial opportunistic pathogen Pseudomonas aeruginosa, Zn homeostasis is not only required for survival, but also for virulence and antibiotic resistance. Thus, the bacterium possesses multiple Zn import/export/storage systems. In this work, we determine the expression dynamics of the entire P. aeruginosa Zn homeostasis network at both transcript and protein levels. Precisely, we followed the switch from a Zn-deficient environment, mimicking the initial immune strategy to counteract bacterial infections, to a Zn-rich environment, representing the phagocyte metal boost used to eliminate an engulfed pathogen. Thanks to the use of the NanoString technology, we timed the global silencing of Zn import systems and the orchestrated induction of Zn export systems. We show that the induction of Zn export systems is hierarchically organized as a function of their impact on Zn homeostasis. Moreover, we identify PA2807 as a novel Zn resistance component in P. aeruginosa and highlight new regulatory links among Zn-homeostasis systems. Altogether, this work unveils a sophisticated and adaptive homeostasis network, which complexity is key in determining a pathogen spread in the environment and during host-colonization.

Implications of kinetically-hindered metals in ecotoxicological studies: Effect of platinum spike aging on its toxicity to Dunaliella salina.

Platinum (Pt) is considered an emerging environmental micro-contaminant due to its increasing use in anthropogenic activities during the past decades. However, there are still important gaps in the understanding of its biogeochemical behavior in the aquatic environment - e.g. its speciation, reactivity and fate - mainly as a result of the analytical challenge of the determination of its typical ultra-trace environmental concentrations. Also, Pt is a kinetically-hindered metal displaying slow reaction kinetics, which has important implications regarding eco-toxicological studies. That is, investigation of its toxicity under laboratory-controlled conditions may therefore require ensuring that equilibrium speciation conditions are reached before starting the experiments. In order to shed further light on this issue, in this study we have monitored the speciation changes during aging of the Pt(IV) spikes in controlled media (seawater) using an UV-Vis spectrophotometry. Platinum toxicity to the green microalgae Dunaliella salina was then compared, using standardized tests, with fresh and aged Pt(IV) spikes at the mg L-1 concentration range. Following 96-hour exposure, ecotoxicological assays consisting in spectrometric measurements of chlorophyll-a concentrations and Effective Concentrations (EC) of Pt resulting in the inhibition of 10% and 50% of algae growth rate were calculated (EC10 and EC50, respectively). Daily monitoring of Pt speciation reflected the transition from PtCl62- (spike) to hydrolyzed species, probably in the form [PtCl3-n(OH)3+n]2-, n = 0-3. Exposure experiments showed that after a short period of aging (10 days), Pt(IV) toxicity increased one order of magnitude compared to freshly spiked media. These results confirm the relevance of considering spike aging to ensure that speciation equilibrium conditions are attained in order to produce environmental realistic eco-toxicological data.

Advanced multichannel submersible probe for autonomous high-resolution in situ monitoring of the cycling of the potentially bioavailable fraction of a range of trace metals.

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.

In Situ Voltammetric Sensor of Potentially Bioavailable Inorganic Mercury in Marine Aquatic Systems Based on Gel-Integrated Nanostructured Gold-Based Microelectrode Arrays.

The development and field validation of newly designed nanostructured gold-plated gel-integrated microelectrode (Au-GIME) arrays applied to the direct in situ square wave anodic stripping voltammetry (SWASV) quantification of the potentially bioavailable inorganic mercury (Hg(II)) species in the coastal area are presented. The Au-GIME consists of arrays of 100-500 interconnected iridium (Ir)-based microdisks that are electroplated with renewable Au nanoparticles (AuNPs) or Au nanofilaments (AuNFs) and covered with an agarose gel. The gel protects the sensor surface from fouling and ensures that mass transport of analytes toward the sensor surface is by pure diffusion only and therefore independent of the ill-controlled convective conditions of the media. The responses of these sensors to direct SWASV measurements of inorganic Hg(II) at near-neutral pH were investigated first in synthetic media and then in UV-irradiated marine samples. The analytical responses were found to be correlated to the number of interconnected microelectrodes and the morphology of the nanostructured Au deposits and independent of the media composition for chloride concentration ≥0.2 M (salinity S ≥ 13) and pH ranging from 7 to 8.5. The AuNF-GIMEs have detection and quantification limits at a low pM level, fulfilling the requirement of sentinel tools for real-time monitoring of the dynamic fraction of Hg(II) in coastal area. The AuNF-GIMEs were incorporated in an in-house advanced multichannel sensing probe for remote in situ high-resolution trace metal monitoring. Field evaluation and validation were successfully performed as a part of a field study in Arcachon Bay (France), from which environmental data are presented. This work marks the first time that an autonomous electrochemical sensing probe successfully measures Hg(II) and its hourly temporal variation in situ without chemical modification of the sample.

Organotropism and biomarker response in oyster Crassostrea gigas exposed to platinum in seawater.

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.

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.

In Situ Detection of Macronutrients and Chloride in Seawater by Submersible Electrochemical Sensors.

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 ( t95 < 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.

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).