Global natural concentrations of Rare Earth Elements in aquatic organisms: Progress and lessons from fifty years of studies.

Rare Earth Elements (REEs) consist of a coherent group of elements with similar physicochemical properties and exhibit comparable geochemical behaviors in the environment, making them excellent tracers of environmental processes. For the past 50 years, scientific communities investigated the REE concentrations in biota through various types of research (e.g. exploratory studies, environmental proxies). The extensive development of new technologies over the past two decades has led to the increased exploitation and use of REEs, resulting in their release into aquatic ecosystems. The bioaccumulation of these emerging contaminants has prompted scientific communities to explore the fate of anthropogenic REEs within aquatic ecosystems. To achieve this, it is necessary to determine the natural concentration levels of REEs in aquatic organisms and the factors controlling REE dynamics. However, knowledge gaps still exist, and no comprehensive approach currently exists to assess the REE concentrations at the ecosystem scale or the factors controlling these concentrations in aquatic organisms. Based on a database comprising 102 articles, this study aimed to: i) provide a retrospective analysis of research topics over a 50-year period; ii) establish reference REE concentrations in several representative phyla of aquatic ecosystems; and iii) examine the global-scale influences of habitat and trophic position as controlling factors of REE concentrations in organisms. This study provides reference concentrations for 16 phyla of freshwater or marine organisms. An influence of habitat REE concentrations on organisms has been observed on a global scale. A trophic dilution of REE concentrations was highlighted, indicating the absence of biomagnification. Lastly, the retrospective approach of this study revealed several research gaps and proposed corresponding perspectives to address them. Embracing these perspectives in the coming years will lead to a better understanding of the risks of anthropogenic REE exposure for aquatic organisms.

First assessment of Rare Earth Element organotropism in Solea solea in a coastal area: The West Gironde Mud Patch (France).

Few studies exist on concentration and internal distribution of Rare Earth Elements (REEs) in marine fishes. REEs organotropism was determined in common sole (Solea solea) from the West Gironde Mud Patch (WGMP; N-E Atlantic Coast, France). The highest ∑REEs concentrations occurred in liver (213 ± 49.9 µg kg-1 DW) and gills (119 ± 77.5 µg kg-1 DW) followed by kidneys (57.7 ± 25.5 µg kg-1 DW), whereas the lowest levels were in muscles (4.53 ± 1.36 µg kg-1 DW) of Solea solea. No significant age- or sex-related differences were observed. The organotropism varied among groups of REEs. Light and heavy REEs preferentially accumulated in liver and gills, respectively. All considered organs showed different normalized REEs patterns, suggesting differences in internal distribution processes between organs. Further work should address: (1) baseline levels worldwide, and (2) factors controlling uptake and organ-specific concentration of REEs.

European fluxes of medical gadolinium to the ocean: A model based on healthcare databases.

Marine ecosystems are exposed to a multitude of stresses, including emerging metals as Rare Earth Elements. The management of these emerging contaminants represents a significant environmental issue. For the past three decades, the increasing medical use of gadolinium-based contrast agents (GBCAs) has contributed to their widespread dispersion in hydrosystems, raising concerns for ocean conservation. In order to control GBCA contamination pathways, a better understanding of the cycle of these elements is needed, based on the reliable characterization of fluxes from watersheds. Our study proposes an unprecedented annual flux model for anthropogenic gadolinium (Gdanth) based on GBCA consumption, demographics and medical uses. This model enabled the mapping of Gdanth fluxes for 48 European countries. The results show that 43 % of Gdanth is exported to the Atlantic Ocean, 24 % to the Black Sea, 23 % to the Mediterranean Sea and 9 % to the Baltic Sea. Together, Germany, France and Italy contribute 40 % of Europe's annual flux. Our study was therefore able to identify the current and future major contributors to Gdanth flux in Europe and identify abrupt changes related to the COVID-19 pandemic.

Impacts of Highway Runoff on Metal Contamination Including Rare Earth Elements in a Small Urban Watershed: Case Study of Bordeaux Metropole (SW France).

High temporal resolution sampling of runoff (15 samples/4 h) and river water (24 samples/24 h) was performed during a major rainstorm (41 mm/4 h) in the Bordeaux Metropole, after a dry and high vehicle-density period. Runoff was sampled at the outlet of one collector draining Northern Bordeaux Highway (NBH; 80,000-93,000 vehicles/day) and river water in the downstream Jalle River. The studied metals, including priority and emergent (Rare Earth Elements [REEs]) contaminants, showed major temporal and spatial variations in the dissolved and particulate concentrations. Hierarchical cluster analyses distinguished metal groups, reflecting different: (i) sources (i.e., automotive traffic: Zn-Cu-Ce and wastewater treatment plant: Cd-Ag-Gd) and/or (ii) processes (i.e., groundwater dilution by rainwater and sorption processes). The contribution of the particulate fraction to total metal fluxes was predominant in the NBH collector (except for Sr and Mo) and highly variable in the Jalle River, where the highest particulate metal loads were due to the export of road dusts exported by the NBH collector. Metal fluxes from the NBH collector represented highly variable fractions of daily fluxes into the Gironde Estuary at the outlet of the Jalle River, depending on elements and partitioning. The resulting relative contributions ranged from: 5% (Sr) to 40% (Cu) for dissolved phases and 30% (As) to 88% (Cu) for particulate phases. The first 40 min of the event accounted for 65% of the suspended particulate matter flux (and associated particulate metals) exported by the NBH collector, whereas the respective water flux contribution was 35%. This finding clearly demonstrates the importance of monitoring the first minutes of rainy events when establishing mass balances in urban systems.

Corbicula fluminea: A sentinel species for urban Rare Earth Element origin.

The increase in the global population, coupled with growing consumption of Rare Earth Elements (REEs), has led to increasing transfer of these emerging contaminants into the environment, particularly through the effluents from wastewater treatment plants (WWTP). The objectives of this study were to determine the geochemical quality of a French river subject to strong urban pressure (the Jalle River in the Bordeaux area) and to examine the bioavailability of natural and anthropogenic REEs in a model species of freshwater bivalve, the Asian clam Corbicula fluminea. To this end, two fractions (dissolved and total) of the water from the Jalle River were sampled and the bivalves were exposed by in situ caging during a three-month monitoring period. The REE patterns obtained showed the presence of Gadolinium (Gd) anomalies in the dissolved and total fractions as well as in Corbicula fluminea. The apparent bioavailability of natural REEs was in the following order for the dissolved fraction: Medium REEs (MREEs) > Light REEs (LREEs) > Heavy REEs (HREEs) and for the particulate fraction: MREEs > LREEs = HREEs. These results highlight the importance of the particulate fraction in the study of the bioavailability of REEs in bivalves. An increase of anthropogenic Gd (Gdanth) was observed in the dissolved fraction between the upstream site (3.4 ng.L-1) and the WWTP Downstream site (48.4 ng.L-1). The Gd anomaly observed in the water was also observed in Corbicula fluminea with a significant increase in the bioaccumulation of Gdanth, from 1.5 ± 1 ng.gDW-1 upstream to 4.1 ± 0.7 ng.gDW-1 downstream of the WWTP effluents, thus confirming the enhanced bioavailability of medical-origin Gd to freshwater bivalves. This study strongly suggests that Corbicula fluminea can be used as a sentinel species in the monitoring of Gd contamination of medical origin. It would thus appear important to consider the potential entry of this contaminant into the human food chain via other, commercially exploited bivalve species.

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.

Whole-transcriptome response to wastewater treatment plant and stormwater effluents in the Asian clam, Corbicula fluminea.

The increase in human population and urbanization are resulting in an increase in the volume of wastewater and urban runoff effluents entering natural ecosystems. These effluents may contain multiple pollutants to which the biological response of aquatic organisms is still poorly understood mainly due to mixture toxicity and interactions with other environmental factors. In this context, RNA sequencing was used to assess the impact of a chronic exposure to wastewater treatment plant and stormwater effluents at the whole-transcriptome level and evaluate the potential physiological outcomes in the Asian clam Corbicula fluminea. We de-novo assembled a transcriptome from C. fluminea digestive gland and identified a set of 3,181 transcripts with altered abundance in response to water quality. The largest differences in transcriptomic profiles were observed between C. fluminea from the reference site and those exposed to wastewater treatment plant effluents. On both anthropogenically impacted sites, most differentially expressed transcripts were involved in signaling pathways in relation to energy metabolism such as mTOR and FoxO, suggesting an energy/nutrient deficit and hypoxic conditions. These conditions were likely responsible for damages to proteins and transcripts in response to wastewater treatment effluents whereas exposure to urban runoff might result in immune and endocrine disruptions. In absence of comprehensive chemical characterization, the RNAseq approach could provide information regarding the mode of action of pollutants and then be useful for the identification of which parameters must be studied at higher integration level in order to diagnose sites where the presence of complex and variable mixtures of chemicals is suspected.