Christophe Brach-Papa

Impact of galvanic anode dissolution on metallic trace element concentrations in marine waters

Submerged harbor steel structures often employ cathodic protection using galvanic anodes to guard against corrosion. A laboratory experiment, with three different cathodic protection configurations by galvanic aluminum-based anodes, was performed to evaluate the potential metal transfer from the anodic alloy dissolution into the surrounding marine water. The anode dissolution rate is proportional to the imposed current demands and induced a significant Al, In, and Zn transfer in the dissolved and particulate fractions of the corrosion product layers covering the anode surface. These layers were poorly adherent, even under low hydrodynamic conditions. Consequently, at the anode vicinity, the suspended particle matter and dissolved fraction of surrounding marine waters showed strong enrichments in Al and Zn, respectively, the values of which could potentially affect the adjacent biota. After the anode activation period, however, the metal inputs from galvanic anode dissolution are rapidly diluted by seawater renewal. At regional scale, these metal fluxes should be negligible compared to river and wastewater fluxes. These results also showed that it is difficult to assess the impact of the anode dissolution on the concentrations of metals in the natural environment, especially for metals included in trace amounts in the anode alloy (i.e., Cu, Fe, In, Mn, and Si) in the aquatic compartment.

Evidencing the Impact of Coastal Contaminated Sediments on Mussels Through Pb Stable Isotopes Composition

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.

3D-printed flow system for determination of lead in natural waters

The development of 3D printing in recent years opens up a vast array of possibilities in the field of flow analysis. In the present study, a new 3D-printed flow system has been developed for the selective spectrophotometric determination of lead in natural waters. This system was composed of three 3D-printed units (sample treatment, mixing coil and detection) that might have been assembled without any tubing to form a complete flow system. Lead was determined in a two-step procedure. A preconcentration of lead was first carried out on TrisKem Pb Resin located in a 3D-printed column reservoir closed by a tapped screw. This resin showed a high extraction selectivity for lead over many tested potential interfering metals. In a second step, lead was eluted by ammonium oxalate in presence of 4-(2-pyridylazo)-resorcinol (PAR), and spectrophotometrically detected at 520nm. The optimized flow system has exhibited a linear response from 3 to 120µgL-1. Detection limit, coefficient of variation and sampling rate were evaluated at 2.7µgL-1, 5.4% (n=6) and 4 sampleh-1, respectively. This flow system stands out by its fully 3D design, portability and simplicity for low cost analysis of lead in natural waters.

Integrated monitoring of chemicals and their effects on four sentinel species, Limanda limanda, Platichthys flesus, Nucella lapillus and Mytilus sp., in Seine Bay: A key step towards applying biological effects to monitoring

The International workshop on Integrated Assessment of CONtaminants impacts on the North sea (ICON) provided a framework to validate the application of chemical and biological assessment thresholds (BACs and EACs) in the Seine Bay in France. Bioassays (oyster larval anomalies, Corophium arenarium toxicity assay and DR Calux) for sediment and biomarkers: ethoxyresorufin-O-deethylase (EROD) activity, acetylcholinesterase (AChE) activity, lysosomal membrane stability (LMS), DNA strand breaks using the Comet assay, DNA adducts, micronucleus (MN), PAH metabolites, imposex, intersex and fish external pathologies were analysed in four marine sentinel species (Platichthys flesus, Limanda limanda, Mytilus sp. and Nucella lapilus). Polycyclic aromatic hydrocarbons (PAHs), polychlorinated biphenyls (PCBs) and heavy metals were analysed in biota and sediment. Results for sediment and four species in 2008-2009 made it possible to quantify the impact of contaminants using thresholds (Environmental Assessment Criteria/EAC2008: 70% and EAC2009: 60%) and effects (EAC2008: 50% and EAC2009: 40%) in the Seine estuary. The Seine estuary is ranked among Europes most highly polluted sites.

3D-printed lab-on-valve for fluorescent determination of cadmium and lead in water

In recent years, the development of 3D printing in flow analysis has allowed the creation of new systems with various applications. Up to now, 3D printing was mainly used for the manufacture of small units such as flow detection cells, preconcentration units or mixing systems. In the present study, a new 3D printed lab-on-valve system was developed to selectively quantify lead and cadmium in water. Different technologies were compared for lab-on-valve 3D printing. Printed test units have shown that stereolithography or digital light processing are satisfactory techniques for creating complex lab-on-valve units. The lab-on-valve system was composed of two columns, eight peripheral ports and a central port, and a coil integrating baffles to increase mixing possibilities. A selective extraction of lead was first carried out by TrisKem Pb™ Resin column. Then, cadmium not retained on the first column was extracted on a second column of Amberlite® IR 120 resin. In a following step, lead and cadmium were eluted with ammonium oxalate and potassium iodide, respectively. Finally, the two metals were sequentially detected by the same Rhod-5N™ fluorescent reagent. This 3D printed lab-on-valve flow system allowed us to quantify lead and cadmium with a linear response from 0.2 to 15 µg L-1 and detection limits of 0.17 and 0.20 µg L-1 for lead and cadmium, respectively, which seems adapted for natural water analysis.

Growth, condition and metal concentration in juveniles of two Diplodus species in ports

High abundances of juvenile fish in certain ports suggest they might provide alternative nursery habitats for several species. To further investigate this possibility, post-settlement growth, metal uptake and body condition were estimated in 127 juveniles of two seabream species, collected in 2014-15, inside and outside the highly polluted ports of the Bay of Toulon. This showed that differences in local pollution levels (here in Hg, Cu, Pb and Zn) are not consistently mirrored within fish flesh. Muscle metal concentrations, below sanitary thresholds for both species, were higher in ports for Cu, Pb and V only. Otherwise, fish muscle composition principally differed by species or by year. Juvenile growth and condition were equivalent at all sites. Higher prey abundance in certain ports might therefore compensate the deleterious effects of pollution, resulting in similar sizes and body conditions for departing juvenile fish than in nearby natural habitats.

Spatial and temporal distribution of mercury and methylmercury in bivalves from the French coastline

Marine mercury (Hg) concentrations have been monitored in the French coastline for the last half a century using bivalves. The analyses presented in this study concerned 192 samples of bivalves (mussels: Mytilus edulis and Mytilus galloprovincialis and oysters: Crassostrea gigas and Isognomon alatus) from 77 sampling stations along the French coast and in the French Antilles sea. The goals of this study were to assess MeHg levels in various common bivalves from French coastline, and to identify possible geographic, taxonomic or temporal variations of concentrations. We show that the evolution of methylmercury (MeHg) concentrations covary with total mercury (HgT) concentrations. Moreover, in most of the study sites, HgT concentrations have not decreased since 1987, despite regulations to decrease or ban mercury used for anthropic activities.

Carbon and nitrogen elemental and isotopic ratios of filter-feeding bivalves along the French coasts: An assessment of specific, geographic, seasonal and multi-decadal variations

Primary consumers play a key role in coastal ecosystems by transferring organic matter from primary producers to predators. Among them, suspension-feeders, like bivalve molluscs are widely used in trophic web studies. The main goal of this study was to investigate variations of C and N elemental and isotopic ratios in common bivalves (M. edulis, M. galloprovincialis, and C. gigas) at large spatial (i.e. among three coastal regions) and different temporal (i.e. from seasonal to multi-decadal) scales in France, in order to identify potential general or specific patterns and speculate on their drivers. The observed spatial variability was related to the trophic status of the coastal regions (oligotrophic Mediterranean Sea versus meso- to eutrophic English Channel and Atlantic ocean), but not to ecosystem typology (estuaries, versus lagoons versus bays versus littoral systems). Furthermore, it highlighted local specificities in terms of the origin of the POM assimilated by bivalves (e.g., mainly continental POM vs. marine phytoplankton vs. microphytobenthic algae). Likewise, seasonal variability was related both to the reproduction cycle for C/N ratios of Mytilus spp. and to changes in trophic resources for δ13C of species located close to river mouth. Multi-decadal evolution exhibited shifts and trends for part of the 30-year series with decreases in δ13C and δ15N. Specifically, shifts appeared in the early 2000s, likely linking bivalve isotopic ratios to a cascade of processes affected by local drivers.

Oligotrophy as a major driver of mercury bioaccumulation in medium-to high-trophic level consumers: A marine ecosystem-comparative study

Mercury (Hg) is a global contaminant of environmental concern. Numerous factors influencing its bioaccumulation in marine organisms have already been described at both individual and species levels (e.g., size or age, habitat, trophic level). However, few studies have compared the trophic characteristics of ecosystems to explain underlying mechanisms of differences in Hg bioaccumulation and biomagnification among food webs and systems. The present study aimed at investigating the potential primary role of the trophic status of systems on Hg bioaccumulation and biomagnification in temperate marine food webs, as shown by their medium-to high-trophic level consumers. It used data from samples collected at the shelf-edge (i.e. offshore organisms) in two contrasted ecosystems: the Bay of Biscay in the North-East Atlantic Ocean and the Gulf of Lion in the North-West Mediterranean Sea. Seven species including crustaceans, sharks and teleost fish, previously analysed for their total mercury (T-Hg) concentrations and their stable carbon and nitrogen isotope compositions, were considered for a meta-analysis. In addition, methylated mercury forms (or methyl-mercury, Me-Hg) were analysed. Mediterranean organisms presented systematically lower sizes than Atlantic ones, and lower δ13C and δ15N values, the latter values especially highlighting the more oligotrophic character of Mediterranean waters. Mediterranean individuals also showed significantly higher T-Hg and Me-Hg concentrations. Conversely, Me-Hg/T-Hg ratios were higher than 85% for all species, and quite similar between systems. Finally, the biomagnification power of Hg was different between systems when considering T-Hg, but not when considering Me-Hg, and was not different between the Hg forms within a given system. Overall, the different parameters showed the crucial role of the low primary productivity and its effects rippling through the compared ecosystems in the higher Hg bioaccumulation seen in organisms from oligotrophic Mediterranean waters.

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.