Mercury stable isotopes constrain atmospheric sources to the ocean.

Human exposure to toxic mercury (Hg) is dominated by the consumption of seafood1,2. Earth system models suggest that Hg in marine ecosystems is supplied by atmospheric wet and dry Hg(II) deposition, with a three times smaller contribution from gaseous Hg(0) uptake3,4. Observations of marine Hg(II) deposition and Hg(0) gas exchange are sparse, however5, leaving the suggested importance of Hg(II) deposition6 ill-constrained. Here we present the first Hg stable isotope measurements of total Hg (tHg) in surface and deep Atlantic and Mediterranean seawater and use them to quantify atmospheric Hg deposition pathways. We observe overall similar tHg isotope compositions, with median Δ200Hg signatures of 0.02‰, lying in between atmospheric Hg(0) and Hg(II) deposition end-members. We use a Δ200Hg isotope mass balance to estimate that seawater tHg can be explained by the mixing of 42% (median; interquartile range, 24-50%) atmospheric Hg(II) gross deposition and 58% (50-76%) Hg(0) gross uptake. We measure and compile additional, global marine Hg isotope data including particulate Hg, sediments and biota and observe a latitudinal Δ200Hg gradient that indicates larger ocean Hg(0) uptake at high latitudes. Our findings suggest that global atmospheric Hg(0) uptake by the oceans is equal to Hg(II) deposition, which has implications for our understanding of atmospheric Hg dispersal and marine ecosystem recovery.

Methylmercury exposure of the sponge O. lobularis induces strong tissue and cell defects.

Mediterranean marine biota suffers from various anthropogenic threats. Among them, pollutants such as mercury (Hg) represent important environmental issues that are exacerbated by bioaccumulation and bioamplification along food webs via its organic form, monomethylmercury (MMHg). To date, very little is known regarding the impact of mercury on Porifera and the few available studies have been exclusively focused on Demospongiae. This work studies the effect of MMHgCl at different biological levels of Oscarella lobularis (Porifera, Homoscleromorpha). Bioaccumulation assays show that MMHgCl significantly accumulated in sponge tissues after a 96-h exposure to 0.1 µg L-1. Toxicity assays (LC5096h) show a sensibility that depends on life-stage (adult vs bud). Additionally, we show that the exposure to 1 µg L-1 MMHgCl negatively impacts the epithelial integrity and the regeneration process in buds, as shown by the loss of cell-cell contacts and the alteration of osculum morphogenesis. For the first time in a sponge, a whole set of genes classically involved in metal detoxification and in antioxidant response were identified. Significant changes in catalase, superoxide dismutase and nuclear factor (erythroid-derived 2)-like 2 expressions in exposed juveniles were measured. Such an integrative approach from the physiological to the molecular scales on a non-model organism expands our knowledge concerning sensitivity and toxicity mechanisms induced by MMHg in Porifera, raising new questions regarding the possible defences used by marine sponges.

Statistical distributions of trace metal concentrations in the northwestern Mediterranean atmospheric aerosol.

The concentrations of 11 crustal and anthropogenic trace metals (Li, Al, V, Mn, Fe, Co, Ni, Cu, Zn, Cd, Pb) were measured from 2006 to 2008 in the atmospheric aerosol at a northwestern Mediterranean coast (station of Cap Ferrat, situated on the southeastern coast of France). Statistical models (lognormal, Weibull, and gamma) that best represented the trace metal distribution for this environment are described. The lognormal model was selected for the distributions of (in decreasing strength of the fit) Al, Co, Li, Zn, Mn, Cu, Pb, and Cd, i.e., metals that are introduced into the atmospheric aerosol by pulses inducing temporal variability in their concentrations. The gamma model was associated with Fe, i.e., metals that exhibit less inter-annual variability than the former trace metals. The third mode (Weibull) represented the distribution of the concentrations of V and Ni. The statistical approach presented in this study contributed to better define and constrain the distribution of the 11 trace metals of the atmospheric aerosol from the northwestern Mediterranean coast. In a close future, knowledge of these statistical distributions will allow using convolution models to separate their natural and anthropogenic contributions, therefore increasing our ability to study anthropogenic emissions of trace metals and their impact on the environment.

The sponge Oscarella lobularis (Porifera, Homoscleromorpha) as a suitable biomonitor of metallic contamination in Mediterranean coastal ecosystems.

The biomonitoring of metallic contamination in marine ecosystems is often focused on animal species of commercial interest and in lesser extent on non-model marine invertebrates. The aim of this study was to compare the metal concentrations (Li, Al, Ti, Cr, Fe, Ni, Cu, Zn, As, Ag, Cd, Hg, Pb) in seven marine sponges with a particular interest in the homoscleromorph sponge Oscarella lobularis at different sites of the Bay of Marseille, France. Inter-species variabilities suggest that the seven sponge species studied accumulate metals differently. In O. lobularis, a multi-site analysis shows different bioaccumulation between the eight sampled populations. These inter-site differences may reflect differences in the hydrodynamic features and in past and present industrial activities. Because Oscarella lobularis shows a homogeneous metal accumulation pattern in comparison with the other tested species, it appears to be suitable for metal contamination biomonitoring in Mediterranean coastal waters, in particular of the coralligenous communities.

Bioconcentration, bioaccumulation and biomagnification of mercury in plankton of the Mediterranean Sea.

Plankton plays a prominent role in the bioaccumulation of mercury (Hg). The MERITE-HIPPOCAMPE campaign was carried out in spring 2019 along a north-south transect including coastal and offshore areas of the Mediterranean Sea. Sampling of sea water and plankton by pumping and nets was carried out in the chlorophyll maximum layer. Two size-fractions of phytoplankton (0.7-2.7 and 2.7-20 µm) and five of zooplankton (between 60 and >2000 µm) were separated, and their total mercury (THg) and monomethylmercury (MMHg) contents were measured. Bioconcentration of THg was significantly higher in the smallest phytoplankton size-fraction dominated by Synechococcus spp. The bioaccumulation and biomagnification of MMHg in zooplankton was influenced by size, food sources, biochemical composition and trophic level. MMHg was biomagnified in the plankton food web, while THg decreased toward higher trophic levels. Higher MMHg concentrations were measured in oligotrophic areas. Plankton communities in the Southern Mediterranean Sea had lower MMHg concentrations than those in the Northern Mediterranean Sea. These results highlighted the influence of environmental conditions and trophodynamics on the transfer of Hg in Mediterranean plankton food webs, with implications for higher trophic level consumers.

Contamination of planktonic food webs in the Mediterranean Sea: Setting the frame for the MERITE-HIPPOCAMPE oceanographic cruise (spring 2019).

This paper looks at experiential feedback and the technical and scientific challenges tied to the MERITE-HIPPOCAMPE cruise that took place in the Mediterranean Sea in spring 2019. This cruise proposes an innovative approach to investigate the accumulation and transfer of inorganic and organic contaminants within the planktonic food webs. We present detailed information on how the cruise worked, including 1) the cruise track and sampling stations, 2) the overall strategy, based mainly on the collection of plankton, suspended particles and water at the deep chlorophyll maximum, and the separation of these particles and planktonic organisms into various size fractions, as well as the collection of atmospheric deposition, 3) the operations performed and material used at each station, and 4) the sequence of operations and main parameters analysed. The paper also provides the main environmental conditions that were prevailing during the campaign. Lastly, we present the types of articles produced based on work completed by the cruise that are part of this special issue.

A preliminary study on metal and nutrient concentrations in running water systems in southern New Caledonia.

Metal and nutrient concentrations were measured in five running water sampling sites of New Caledonia. Metal concentrations were homogeneous (Ni; 22.7-50.6 µg L(-1)) or not (Fe; 37-749 µg L(-1)). Concentrations of Ni, Cr, Fe were high, including high dissolved fractions (up to 47.8, 70.8 and 417 µg L(-1), respectively). Concentrations of anthropogenic metals (Ag, As, Cd, Cu, Pb, Sb, V, Zn) were low (maximum: total Cu, 0.6 µg L(-1)). The contamination of waters is presumably due to soil weathering and mining activities. Metal concentrations and phosphate depletion (<0.04 µmol L(-1)) suggest constrained conditions for the development of aquatic life.

Characterization of the submarine disposal of a Bayer effluent (Gardanne alumina plant, southern France): I. Size distribution, chemical composition and settling rate of particles forming at the outfall.

The submarine discharge of the high pH clarified Bayer effluent of the Gardanne alumina plant (Marseille region, France) leads to the formation of concretions at the outfall 324 m underwater and to a plume of white particles. The bulk chemical composition of the concretions has been determined by SF-ICP-MS. Mg and Al are the major elements measured with concentrations of a few hundred mg g-1. Ca and S are also found at concentrations in the range of mg g-1. Among the measured trace elements there is a specific interest in As and V because of environmental concerns pointed out by regulation authorities. Their concentrations are of tens to thousands µg g-1, respectively. Concentrations of the other elements are in the range of a few ng g-1 to few hundreds µg g-1. In order to constrain the dispersion of particles in the environment and to understand how chemical elements can be scavenged from or released to seawater, the size distribution of particles composing the concretions has been measured by settling rate experiments and, for each size class of particles, their chemical composition has been determined. For example, As and V are mainly associated to particles with mean diameters between 15.6 and 63 µm and settling rates around 96 m d-1. Overall, all the main elements (Mg, Al, Ca, S) composing concretions are associated to this size class of particles which represents 53-60% of the total concretion mass.

Human mercury exposure levels and fish consumption at the French Riviera.

Humans are exposed to methylmercury (MeHg), a bioaccumulative neurotoxin, mainly through the consumption of marine fish. Several studies showed that high MeHg exposure can lead to neurological damage. This is particularly relevant for pregnant women, because MeHg exposure negatively impacts foetal development. Populations living near the sea are generally at increased exposure risk due to higher consumption of fish and seafood. Here, we present the first study of MeHg exposure levels of the population living at the French Riviera, using mercury (Hg) concentrations in hair as a proxy for MeHg exposure. We found that older people that consume more fish presented the highest hair Hg concentrations. Compared to other Mediterranean bordering countries and other European countries, the southern France population is among those with high MeHg exposure (median for women of childbearing age is 0.56 µg g-1). A global implementation of the Minamata Convention is necessary to lower MeHg exposure of the population.

Chemical composition and in vitro aryl hydrocarbon receptor-mediated activity of atmospheric particulate matter at an urban, agricultural and industrial site in North Africa (Bizerte, Tunisia).

As recognized risk factor to pose a health threat to humans and wildlife globally, atmospheric particulate matter (PM) were collected from a North African coastal city (Bizerte, Tunisia) for one year, and were characterized for their chemical compositions, including mercury (HgPM), as well as organic contaminants (polycyclic aromatic hydrocarbons (PAHs), polychlorinated biphenyls (PCBs), organochlorine pesticides (OCPs)), organic carbon (OC) and organic nitrogen (ON), determined in a previous study. Then, we applied an in vitro reporter gene assay (DR-CALUX) to detect and quantify the dioxin-like activity of PM-associated organic contaminants. Results showed that average HgPM concentration over the entire sampling period was found to be 13.4 ± 12 pg m-3. Seasonal variation in the HgPM concentration was observed with lower values in spring and summer and higher values in winter and autumn due to the variation of meteorological conditions together with the emission sources. Principal component analysis suggested that fossil fuel combustion and a nearby cement factory were the dominant anthropogenic HgPM sources. Aryl hydrocarbon receptor (AhR)-mediated activities were observed in all organic extracts of atmospheric PM from Bizerte city (388.3-1543.6 fg m-3), and shows significant positive correlations with all PM-associated organic contaminants. A significant proportion of dioxin-like activity of PM was related to PAHs. The dioxin-like activity followed the same trend as PM-associated organic contaminants, with higher dioxin-like activity in the cold season than in the warm season, indicating the advantage and utility of the use of bioassays in risk assessment of complex environmental samples.

Origins and discrimination between local and regional atmospheric pollution in Haiphong (Vietnam), based on metal(loid) concentrations and lead isotopic ratios in PM10.

Southeast Asia is a hotspot of anthropogenic emissions where episodes of recurrent and prolonged atmospheric pollution can lead to the formation of large haze events, giving rise to wide plumes which spread over adjacent oceans and neighbouring countries. Trace metal concentrations and Pb isotopic ratios in atmospheric particulate matter < 10 µm (PM10) were used to track the origins and the transport pathways of atmospheric pollutants. This approach was used for fortnightly PM10 collections over a complete annual cycle in Haiphong, northern Vietnam. Distinct seasonal patterns were observed for the trace metal concentration in PM10, with a maximum during the Northeast (NE) monsoon and a minimum during the Southeast (SE) monsoon. Some elements (As, Cd, Mn) were found in excess according to the World Health Organization guidelines. Coal combustion was highlighted with enrichment factors of As, Cd, Se, and Sb, but these inputs were outdistanced by other anthropogenic activities. V/Ni and Cu/Sb ratios were found to be markers of oil combustion, while Pb/Cd and Zn/Pb ratios were found to be markers of industrial activities. Pb isotopic composition in PM10 revealed an important contribution of soil dusts (45-60%). In PM10, the Pb fraction due to oil combustion was correlated with dominant airflow pathways (31% during the north-easterlies and 20% during the south-easterlies), and the Pb fraction resulting from industrial emissions was stable (around 28%) throughout the year. During the SE monsoon, Pb inputs were mainly attributed to resuspension of local soil dusts (about 90%), and during the NE monsoon, the increase of Pb inPM10 was due to the mixing of local and regional inputs.

Mineralisation of atmospheric aerosol particles and further analysis of trace elements by inductively coupled plasma-optical emission spectrometry.

Several protocols using different treatments (various mixtures of acids at different temperatures for mineralisation) or using several analysis instrumentations were tested with the aim to define the method allowing the analysis of some groups of elements. This study proposes a protocol of sample treatment and analysis permitting in a single batch the determination of 16 elements (Al, As, Ba, Cd, Co, Cu, Fe, K, Mg, Mn, Na, Ni, Pb, Ti, V and Zn) with different chemical features such as volatile or refractory trace elements. This method is specifically adapted to chemical matrices found in unpolluted to moderately polluted atmospheric aerosol samples. Aerosol samples were digested using a mixture aqua regia/hydrofluoric acid at 130 °C during 2 h, and were then analysed with specifically tuned inductively coupled plasma-optical emission spectrometry. •Reduction of costs: use of hot block, use of inductively coupled plasma-optical emission spectrometry (ICP-OES), easiness, reliability and adaptability to routine analysis•Digestion of up to 54 samples at the same time in 2 h and low amount of material required, only 10 mg is necessary.•Better accordance with Occupational Health and Safety requirements (reduced use of acids, in particular HF, no use of high-pressure Teflon bombs).

Abrupt response of chemical weathering to Late Quaternary hydroclimate changes in northeast Africa.

Chemical weathering of silicate rocks on continents acts as a major sink for atmospheric carbon dioxide and has played an important role in the evolution of the Earth's climate. However, the magnitude and the nature of the links between weathering and climate are still under debate. In particular, the timescale over which chemical weathering may respond to climate change is yet to be constrained at the continental scale. Here we reconstruct the relationships between rainfall and chemical weathering in northeast Africa for the last 32,000 years. Using lithium isotopes and other geochemical proxies in the clay-size fraction of a marine sediment core from the Eastern Mediterranean Sea, we show that chemical weathering in the Nile Basin fluctuated in parallel with the monsoon-related climatic evolution of northeast Africa. We also evidence strongly reduced mineral alteration during centennial-scale regional drought episodes. Our findings indicate that silicate weathering may respond as quickly as physical erosion to abrupt hydroclimate reorganization on continents. Consequently, we anticipate that the forthcoming hydrological disturbances predicted for northeast Africa may have a major impact on chemical weathering patterns and soil resources in this region.

Trace metal concentrations in the North-western Mediterranean atmospheric aerosol between 1986 and 2008: seasonal patterns and decadal trends.

Climatic and anthropogenic changes are able to engender modifications in the aerosol composition at different geographical and temporal scales. The present study addresses this question for the trace metal concentrations (TM=Al, Fe, Mn, Co, Ni, Cu, Pb, Cd and Zn) of aerosol from the North-western Mediterranean coast of France (Cap Ferrat, nearby Nice) between 1986 and 2008. From seasonal variations (2006-08) and decadal trends (1986-2008) of TM concentrations, three groups of elements can be distinguished. They consist of different aerosol sources: crustal-derived elements (Al, Fe, Mn and Co), trace metals of anthropogenic origin (Pb, Cd and Zn) and a third, intermediate, group of trace metals that presented both anthropogenic and natural/crustal influences (Ni and Cu). Reproducible seasonal patterns were observed for crustal and intermediate elements with highest concentrations between May and November, while anthropogenic trace metals did not show a pronounced seasonal cycle. Nevertheless, highest concentrations of anthropogenic trace metals occurred mostly in autumn/winter. Aerosol concentrations of anthropogenic TMs decreased remarkably over the last two decades, while crustal trace metals did not show any evolution. Nickel and copper aerosol concentrations remained constant, as well. Lead concentrations decreased from 1986 (29.34 ng m(-3)) to 2008 (3.33 ng m(-3)), overall by 90%. Cadmium and zinc aerosol concentrations decreased by 66 and 54%, respectively, between 1998 and 2006-08, from 0.27 to 0.09 ng m(-3) and from 23.9 to 10.9 ng m(-3), respectively. These findings demonstrate the response of the atmospheric environment to the implementation of antipollution policies. Possible changes of trace metal emissions sources and local influences are discussed.