Phytohormones enhance heavy metal responses in Euglena gracilis: Evidence from uptake of Ni, Pb and Cd and linkages to hormonomic and metabolomic dynamics.

Over the last decade, significant effort has been made to understand phytohormonal functions (e.g., cytokinins (CKs) and abscisic acid (ABA)) in metal stress responses of higher plants and algae. Despite the potential for these phytohormones to improve industrial remediation by Euglena gracilis (Euglenophyceae), no such roles have been elucidated for this highly adaptive species and its response to heavy metals. This study demonstrates that toxic metals (nickel, lead, cadmium) modify hormonal activity profiles (i.e., CK forms and their concentrations) in E. gracilis. Furthermore, exogenous ABA or CK (tZ) enabled higher metal uptake efficiency (i.e., 9.35% in lead and 9.2% in cadmium uptake with CK) and alleviated metal toxicity through the regulation of endogenous CKs (i.e., total CK, isoprenoid CK) and gibberellin (GAs, GA1 and GA3) levels. These responses suggest that E. gracilis regulates multiple phytohormone signals during metal stress acclimation. A deeper approach, using untargeted metabolomic analyses, gave more detailed insight into phytohormone-controlled pathways and associated modified metabolites, which were frequently related to metal accumulation and the physiological acclimation to metal presence. Significant changes in the levels of cellular metabolites, especially those involved in acclimation to metal stress, were under the influence of phytohormones in algal cells. When grown under metal stress conditions, the presence of exogenous ABA or CKs, caused changes in cellular metabolites which included those from: lipid pathways, riboflavin metabolism, the biosynthesis of cofactors/vitamins, and carbohydrate metabolism. Also, bioactive secondary metabolites (e.g., terpenoids, alkaloids, flavonoids, carotenoids) were modified in algal cells treated with phytohormones. Thus, the study gives a detailed view on the regulatory functions of ABA and CKs in algal metal bioremediation strategies, which are attributed to enhanced metal uptake and in the fine-tuning of plant hormone levels during metal stress response. The results can guide efforts to develop efficient, low-cost and environmentally friendly methods for bioremediation.

Rare earth element uptake mechanisms in plankton in the Estuary and Gulf of St. Lawrence.

The global shift toward green energy alternatives escalates demands for new resources, including rare earth elements (REEs), as per their implications in various green innovations. However, our understanding of their environmental cycle, especially the interactions with aquatic organisms, remains deficient, ultimately hindering environmental protection efforts. Here, we investigate the accumulation of REEs and 18 other elements in bulk and sorted plankton collected with different net mesh sizes (30, 63, 200, 333, 500 µm) in the Estuary and Gulf of St. Lawrence in the summer and winter of 2020. We observed significant correlations between the concentrations of REEs and elements of different charge numbers and ionic radii (Ba, Co, Cs, Fe, Mn, Pb, Rb and V), indicating non-selective uptake of REEs into plankton. All these elements have their highest concentrations in the fluvial corridor and upper estuary, with more significant enrichment in phytoplankton ([La] = 26.4 ± 4.8 mg kg-1) than zooplankton ([La] = 11.6 ± 8.3 mg kg-1). Their concentrations decrease to the minimum in the Gulf of St. Lawrence, especially in zooplankton ([La] = 4.8 × 10-2 ± 3.2 × 10-2 mg kg-1). We also assessed REE patterns to identify differential REE fractionation processes and anomalies. The freshwater plankton exhibits enrichment of middle REEs (MREEs) relative to the light and heavy REEs (LREEs and HREEs), potentially because of the higher binding affinity of MREEs on cellular surface transporters and metal loading effects. In estuarine and marine settings, the REE patterns in biological samples align with suspended particles, exhibiting a linear trend with LREE enrichment. This process is more noticeable in sorted macrozooplankton, which have significant Eu anomalies (Eu/Eu* up to 2), indicating differential incorporation of REEs into the chitin shells. This study highlights the significant enrichment of REEs into freshwater primary producers and the accumulation pathway similar to other inorganic elements.

A multi-tracer approach to disentangle anthropogenic emissions from natural processes in the St. Lawrence River and Estuary.

The ability to differentiate anthropogenic signatures from natural processes in complex hydrological systems is critical for environmental regulation perspectives, especially to curb pollution and implement effective water management strategies. Here, we report variations in the concentrations of 57 chemical variables, including nutrients, major, trace and ultra-trace elements, as well as the concentrations of Escherichia coli in different water masses along the St. Lawrence River-Estuary continuum. The constant ratios among major elements indicate consistent carbonate and silicate weathering processes in the drainage basins. We also suggest applying Ce anomalies to trace waters of low alkalinity and low complexing capacity as the dominance of Ce3+ free ion could promote Ce oxidation, and thus negative Ce anomalies. Furthermore, the positive Eu anomalies and elevated Tl concentrations could highlight the cation exchange processes on clay particles. In the fluvial and estuarine sections of the St. Lawrence System, we demonstrate significant contributions of wastewater discharge and discuss the suitability of several wastewater tracers, e.g., excess of B, Na, K, as well as Rb/Sr and Gd anomalies. We also highlight the inputs of several minor and trace elements (e.g., Mn, Fe, Cu, Co, Ni) from south-shore tributaries to the St. Lawrence System. However, the complex anthropogenic activities in the watersheds did not allow clear source partitioning. Finally, increased mixing of different river water masses upstream of Quebec City, together with the estuarine salt front and suspended sediments, are also responsible for releasing these minor and trace elements into the aquatic media. The results presented here help support further environmental actions to curb the emission of contaminants in the St. Lawrence System and provide more robust tracers of natural and anthropogenic processes in aquatic environments.

Groundwater in Southern Vietnam: Understanding geochemical processes to better preserve the critical water resource.

A thorough understanding of groundwater geochemical characteristics and dominant hydro(bio)geochemical processes in the aquifers is valuable for sustainable groundwater protection. With this respect, this study provides a comprehensive assessment of hydrogeochemical characteristics of groundwater in sedimentary aquifers of the Southern region of Vietnam. The dataset comprised 291 water samples collected in rainy and dry seasons from 155 wells, and their chemical compositions of dissolved ions (Ca2+, Mg2+, Na+, K+, HCO3-, Cl-, SO42-, NO3-, NH4+, Fe, total dissolved solids) and pH. We calculated the groundwater quality index to determine the suitability of groundwater for drinking purposes. Accordingly, about 47% of groundwater samples range from poor to unsuitable quality for drinking purposes, in which total dissolved solid (TDS) and high iron concentrations are primary factors. We also examined hydrogeochemical characteristics by multivariate statistical analyses (Hierarchical Cluster Analysis and Principal Component Analysis). The results demonstrated four groups of water: fresh groundwater (TDS < 1 g/L) in the highland (Group 1), lowland fresh-to-saline groundwater (2a), lowland saline groundwater (2b), and lowland saline/acidic groundwater (2c). Although the highland area is currently not impacted by salinization, the contamination by nitrate and chloride associated with a dense urban population and agricultural practices is deteriorating its fresh groundwater resources. On the other hand, the lowland area of Southern Vietnam is highly vulnerable to seawater intrusion (groups 2b and 2c). Only 34% out of 191 samples collected in the lowland area of southern Vietnam remained fresh. In this light, this study depicted the specific geographical location for various groundwater groups in Southern Vietnam. This finding is significant to assist water scientists and decision-makers in implementing targetted groundwater management measures as prevention and protection strategies should be tailored to groundwater geochemical characteristics and the dominant hydro(bio)geochemical processes.

Rare Earth Element Accumulation and Fractionation in a Lake Ecosystem Impacted by Past Uranium Mining.

Rare earth elements (REEs) are a natural resource of vital economic interest. While REE mining and processing are known for severe environmental issues, REEs are also by-products of other mining processes (e.g. uranium). Here, we provide an in-depth assessment of REE distribution across a lake system impacted by adjacent uranium mining over a long period (Bow Lake, Ontario, Canada). We observed a robust REE-U correlation with a consistent La/U ratio of 2.0 ± 0.2 and La concentrations up to 2200 µg g-1. Selective extraction results demonstrated that 80-94% of REEs were acid extractible, while 3-8% of REEs were extracted by an alkaline solution (i.e. bound to natural organic matter). Analysis of specific REE patterns, together with a strong REE-P correlation, suggest that (co)precipitation with P mineral would be an important mechanism sequestrating REEs into Bow Lake sediments. Moreover, we identified three sources of particles delivering REEs into the lake with unique REE patterns: mine tailings, U ores and Precambrian bedrock. Negative Sm anomalies were detected in three soil samples and associated with the Precambrian bedrock. We also detected positive Gd and La anomalies in the sediments. Lanthanum anomalies were strongly correlated with U authigenic accumulation and thus associated with microbial processes requiring La, such as methanotrophy. This research demonstrates that lake sediments adjacent to U mining could represent ecological risks given that La and other REE concentrations largely exceed the maximum permissible concentrations. Water and sediment quality criteria are therefore required as both primary REE mining and extraction of REEs as by-products from legacy metallurgical tailings are increasing.

Toward the Circular Economy of Rare Earth Elements: A Review of Abundance, Extraction, Applications, and Environmental Impacts.

Rare earth elements (REEs) are increasingly critical to the high-technology and low-carbon economy. With a shift to sustainable socioeconomic development that aims to be less fossil fuel dependent, global demand for REEs continues to rise, despite their uncertain supply chain and high environmental impact of production. Here, we review recent research on REEs, including global reserve assessment, REE-based applications, major REE production pathways, environmental impacts, and the potential to leverage circular economies within the REE industry. The main objective of this review is to provide an overall socioeconomic and environmental perspective of the REE industry with a central focus on environmental impacts of various REE-related activities. The literature reveals significant interest in extracting REEs from secondary materials (e.g., tailings, bauxite residues, coal combustion ash) and electronic wastes. However, some of these REE recovery processes are not yet economically profitable and environmental-friendly. Continued technological advancements and increasing demands for REEs may entice countries with recently discovered REE reserves to break the current monopolistic REE supply chain. Furthermore, the sustainability of REE usage may also depend on consumer awareness of environmental and human health impacts associated with end-of-life electronics that contain REEs. On the other hand, REEs may show promise in sustainable agriculture and environmental applications. Nevertheless, further research on REE ecotoxicological impacts is required to establish environmental regulations that protect the environment and human health.

Hazardous motherboards: Changes in metal contamination related to the evolution of electronictechnologies.

Proper management of electronic waste (e-waste) represents significant economic and environmental challenges because of the tremendous quantity of e-waste, the potential of extracting precious metals from recyclable electronics, and the risks of environmental contamination with a variety of toxic compounds. This study focused on the leaching potential of 57 elements from central processing unit mainboards manufactured over time (1980s-2010s) using river water at different pHs as an environmentally-relevant extractant. The exposure time was set to one week. The calculated contamination factors allowed classification of the elements released from mainboards into five groups with increasing leachability and thus environmental concerns. Also, the results demonstrated a changing nature of e-waste related to the technologies employed and the transition of metal contamination signatures from these electronics; newer computer mainboards have a lower risk of Pb and Sn leaching but a greater release of Li, Sb, and a few rare earth elements (Sm, Eu, Dy). These specific patterns of elemental release could become powerful geochemical forensic tracers of improper recycling activities of e-waste in the environment. Most studies until now have investigated just a few key contaminants, despite the cocktail of pollutants contained in electronics. Therefore, a full assessment of the leaching potential of pollutants from non-properly recycled e-waste and further ecotoxicological studies are timely needed.

Long-term monitoring emphasizes impacts of the dredging on dissolved Cu and Pb contamination along with ultraplankton distribution and structure in Toulon Bay (NW Mediterranean Sea, France).

A long-term monitoring during dredging and non-dredging periods was performed. Total and dissolved Cu and Pb concentrations, DGT-labile Pb, ultraphytoplankton abundance and structure were monitored at four sites: dredging site, dumping site (inside/outside of a geotextile bag) and reference site. During the reference period (non-dredging), an increasing contamination in Pb, Cu and a progressive shift from Synechococcus to photosynthetic picoeukaryotes dominance was observed from reference to dumping site. Pb concentrations were significantly higher during dredging period, pointing out sediment resuspension as Pb major source of contamination. Unlike Pb, Cu concentrations were not statistically different during the two periods. Dredging period did not impact on ultraphytoplankton abundance and structure but influence heterotrophic prokaryotes abundance. Sediment resuspension is therefore a major driver of chemical and biological qualities in Toulon Bay. Furthermore, although the geotextile bag reduces particulate transport of the dredged sediment, the transport in the dissolved phase remains a major problem.

Distribution and diagenesis of trace metals in marine sediments of a coastal Mediterranean area: St Georges Bay (Lebanon).

St Georges Bay of Lebanon's coast is an open bay to the Mediterranean Sea. It is exposed to numerous anthropogenic activities such as industrial effluent, untreated wastewater discharge and maritime activities resulting in increasing chemical contamination, especially with trace metals. Contamination with trace metals (Cu, Cd, Co, Pb, As, Ag and Hg) and the influence of early diagenesis on their distribution were studied on both sediments and waters. For this purpose, sediment cores were collected, then treated under inert atmosphere to retrieve pore waters and solid fraction. The area appears to be seriously impacted by the materials transported by the Beirut River and/or by direct inputs, and recent land reclamation using dumpsite material. The sediments showed a significant level of contamination. Element mobility was studied by selective extraction on sediments. The mobility of trace elements from solid fraction to pore waters is controlled by the Fe/Mn cycle and organic matter.

High-resolution mass spectrometry for molybdenum speciation in sulfidic waters.

High resolution electrospray ionization mass spectrometry (ESI-HRMS) was used to study the speciation of molybdenum in interaction with sulfide and chloride. While reactions between molybdate and sulfide lead to creation of four conventional thiomolybdate species (MoO3S2-, MoO2S22-, MoOS32-, MoS42-), chemical formula assignment of recorded mass spectra confirmed the presence of intermediate thiomolybdate compounds (MoO3S22-, MoO2S32-, MoOS42-, MoS52-, MoS62-) and thio-chloro-molybdate compounds (MoO3Cl-, MoO2SCl-, MoOS2Cl-, MoOS3Cl-). Two of the intermediate thiomolybdate compounds were previously suggested theoretically, and this study provides analytical support for the existence of these compounds. Fast ESI-HRMS analysis has allowed us to conduct a highly-resolved short-term kinetic study of these reactions, and we suggest that the reactivity between molybdate and sulfide is more complex than previously thought, particularly during the first 24 h of interaction. Also, the solution composition will impact reaction pathways, and different outcomes found in the literature may arise from choices of ionic strength and pH adjusting agents in previous studies . The occurrence of the thio-chloro-molybdate species detected in this study should be implemented in future Mo speciation models to better assess Mo reactivity in sulfidic waters and reducing environments.

Kinetic processes of copper and lead remobilization during sediment resuspension of marine polluted sediments.

Contaminated sediments could act as a source of contamination to the surrounding environments by several processes (e.g., diffusive flux, sediment resuspension). This study aimed at highlighting the mechanisms of copper and lead mobilization from resuspended particles to the aqueous phase using laboratory experiments and a kinetic model. Three sediments, differed by their compositions and metal partition from Toulon Bay (SE France) were used. In addition, three solid/liquid ratios (0.1, 1 and 10 g L-1) allowed simulating at best natural and anthropogenic scenarios (e.g., storm, nautical traffic, dredging). We monitored metal concentrations, physicochemical parameters (pH, Eh, [O2]) and organic matter concentration along with their optical properties. Experimental results showed successive reactions over short and long terms (hour and day scale, respectively) that controlled Cu and Pb exchanges between particles and the aqueous phase over 4 weeks. The quick Cu removal was attributed to the implications of newly formed oxides while the long-term Cu release in the dissolved fraction from the more refractory solid pool is more likely related to organic complexation. In fact, we observed a transformation of the dissolved organic matter: an increase in molecular weight and in humic fluorescence properties. However, the Pb removal toward the end of the experiment could be explained by a migration toward the exchangeable sites of higher energy, which could correspond to the particulate organic matter or a combination with organic-coating carrier phases. Both kinetic rate and system response times (τi) were coherent despite the variability of parameters intrinsic to sediments (e.g., sediment composition and initial metal repartition) but also extrinsic parameters (solid/liquid ratios). Such a coherence would imply the universality of the obtained constants to be used in a more predictive approach to assess the potential of metal mobility using metal repartition in contaminated sediments when combined with hydrological and sedimentological models.

Anthropogenic mercury contamination in sediments of Krka River estuary (Croatia).

Coastal and estuarine sediments play an important role in the biogeochemical cycle of mercury (Hg) in the aquatic environment. When contaminated, sediments can act as a potential source of Hg and may pose a long-term risk to aquatic biota. The aim of this research was to assess spatial and historical distribution of Hg in the sediments of the Krka River estuary, an environment that so far has been regarded as relatively unpolluted. To achieve this goal, 40 surface sediment samples and 7 sediment cores were collected along the entire estuary. Hg concentrations in the surface and deep sediments of the Krka River estuary were found in a broad range 0.042-57.8 mg kg-1, demonstrating significant spatial and temporal differences in Hg input to the estuarine sediments. Two distinct areas were distinguished; upper estuary where the Hg content was comparable to other unpolluted Adriatic sediments, and the lower estuary where sediment profiles reflected the history of anthropogenic Hg input associated with the city of Sibenik. The vertical Hg profile from the most affected area of the estuary, combined with 210Pb and 137Cs dating, demonstrated that a significant increase of Hg input started in late 1940s/early 1950s, mainly related to shipyard activities. This study provided more insight on the Hg concentration in the Krka River estuary, demonstrating that the high values obtained, although localized, were comparable to the ones found in some of the most contaminated sites in the Mediterranean.

Rare earth elements in the Pearl River Delta of China: Potential impacts of the REE industry on water, suspended particles and oysters.

Rare earth element (REE) concentrations and patterns were measured in surface water, suspended particles (SP) and oysters from the Pearl River Estuary, China. During the rainy season of 2017, higher REE concentrations were found at the stations in the estuary (ΣREE = 0.06-0.42 µg L-1) than those at the river mouths (referred to as 'outlet' stations, ΣREE = 0.001-0.14 µg L-1). However, the reverse occurred in the dry season of 2016 (ΣREE = 0.07-0.16 µg L-1 in the mid-estuary vs. 0.001-0.02 µg L-1in the outlet stations). Elevated concentrations of Pr, Nd, Dy and Ho, relative to the other REEs were found in water in both seasons at most sampling locations. However, in some estuary stations, no anomalies were detected in the SP or in the oysters while some anomalies were seen in SP from the outlet stations. Significant correlations between REE concentrations in SP and oysters as well as between both total REE concentrations and the La/Yb ratio (reflecting enhanced accumulation of light REEs (LREEs)) in oysters indicate that, in the Pearl River Estuary, the dominant REE uptake pathway in oysters is from particles. The elevated concentrations of Pr, Nd, Dy and Ho, which are reported here for the first time suggest that elevated levels of these elements may result from REE recycling and other industrialized activities in this area of southern China. Specific REEs could be used to indicate emerging contamination by the modern REE industry; furthermore, REE anomalies and patterns may be suitable tools to track REE sources.

Application of ESI-HRMS for molybdenum speciation in natural waters: An investigation of molybdate-halide reactions.

High resolution electrospray ionization mass spectrometry (ESI-HRMS) was used to study the speciation of molybdate in interaction with halides (Cl, F, Br). Desolvation during electrospray ionization induced alteration of aqueous species but method optimization successfully suppressed artefact compounds. At low Mo concentrations, chloro(oxo)molybdate and fluoro(oxo)molybdate species were found and in natural samples, MoO3Cl was detected for the first time, to the best of our knowledge. Apparent equilibrium constants for Cl substitution on molybdate were calculated for a range of pH values from 4.5 to 8.5. A minor alteration in speciation during the gas phase (conversion of doubly charged MoO42- to HMoO4-) did not allow investigation of the molybdate acid-base properties; however this could be determined by speciation modeling. This study provides further evidence that ESI-HRMS is a fast and suitable tool to Deceasedassess the speciation of inorganic compounds such as Mo.

Uranium dispersion from U tailings and mechanisms leading to U accumulation in sediments: Insights from biogeochemical and isotopic approaches.

Uranium contamination is a worldwide problem that grows proportionally to human demands for energy and armory. Understanding U cycling in the environment is of eminent interest, mostly concerning ecosystems directly impacted by point sources. In Bow Lake (Ontario, Canada), which is located adjacent to a former U mine, exceptionally high concentrations of U are related to U dispersion from tailings and biogeochemical processes such as biotic reduction and adsorption. This has been shown by a U-Pb isotope composition model. In this study, we use U isotope fractionation (δ238U) to highlight U cycling and the role of bacteria (Geobacteraceae and sulfate-reducing bacteria) in affecting U cycling. Bacteria affected U cycling directly via biotic U reduction and indirectly via reductive dissolution of carrier phases. All the processes are interconnected through diagenetic reactions with the supply of bioavailable organic matter being the primary driving force of the diagenesis. This study is the first to use multiple biogeochemical and isotopic approaches to track U cycling from a contamination point source to U storage in lake sediments.

Quantitative model of carbon and nitrogen isotope composition to highlight phosphorus cycling and sources in coastal sediments (Toulon Bay, France).

Nutrient loadings from either point or non-point sources to the environment are related to the growing global population. Subsequent negative impacts of nutrient loading to aquatic environments requires a better understanding of the biogeochemical cycling and better tools to track their sources. This study examines the carbon (C), nitrogen (N) and phosphorus (P) discharge and cycling in a Mediterranean coastal area from rivers to marine sediments and assesses the anthropogenic contributions. Carbon and N concentrations and isotope compositions in rivers particles, surface sediments, and sediment cores were investigated to build up a quantitative multiple-end-member mixing model for C and N isotopes. This model predicts the contribution of four natural and one anthropogenic sources to the sediments and highlighted the anthropogenic fraction of P based on the relationship with anthropogenic δ15N. Although P is a monoisotopic element and total P concentration has been the sole index to study P loading, this study suggests an alternative approach to differentiate anthropogenic and non-anthropogenic (diagenetic) P, revealed point and non-point sources of P, and the corresponding P loading. Also, the diagenetic P background has been calculated for the 50-cm sediment layer of the whole Bay.

Remobilization of polycyclic aromatic hydrocarbons and organic matter in seawater during sediment resuspension experiments from a polluted coastal environment: Insights from Toulon Bay (France).

Polycyclic aromatic hydrocarbons (PAHs) and organic matter contents were measured in seawater during resuspension experiments using sediments collected from Toulon Bay (Northwestern Mediterranean Sea, France). The studied sediments were very highly contaminated in PAHs, especially in 4-ring compounds emitted from combustion processes. The sediments used for resuspension experiments were collected at 0-2 cm (diagenetically new organic matter, OM) and 30-32 cm depths (diagenetically transformed OM). They were both mostly composed of fine particles (<63 µm), enriched in organic carbon (8.2 and 6.3%, respectively) and in PAHs (concentration of Σ34 PAHs: 38.2 and 35.7 × 103 ng g-1, respectively). The resuspension of these sediments led to an increase in concentrations of dissolved Σ34 PAHs, dissolved organic carbon (DOC) and dissolved humic- and tryptophan-like fluorophores in seawater up to 10-, 1.3-, 4.4- and 5.7-fold, respectively. The remobilization in seawater was higher for 4-6 ring PAHs, especially benzo(g,h,i)perylene, whose concentration exceeded the threshold values of the European Water Framework Directive. This noted the potential harmful effects of sediment resuspension on marine biota. From these sediment resuspension experiments, we determined OC-normalized partition coefficients of PAHs between sediment and water (Koc) and found that during such events, the transfer of PAHs from sediment particles to seawater was lower than that predicted from octanol-water partition coefficients (Kow) (i.e., measured Koc > Koc predicted from Kow). The results confirmed the sequestration role of sedimentary OC quality and grain size on PAHs; the OM diagenetic state seemed to impact the partition process but in a relatively minor way. Furthermore, differences were observed between 2-4 ring and 5-6 ring PAHs, with the latter displaying a relatively higher mobility towards seawater. These differences may be explained by the distribution of these two PAH pools within different OM moieties, such as humic substances and black carbon.

Uranium Isotope Fractionation during Adsorption, (Co)precipitation, and Biotic Reduction.

Uranium contamination of surface environments is a problem associated with both U-ore extraction/processing and situations in which groundwater comes into contact with geological formations high in uranium. Apart from the environmental concerns about U contamination, its accumulation and isotope composition have been used in marine sediments as a paleoproxy of the Earth's oxygenation history. Understanding U isotope geochemistry is then essential either to develop sustainable remediation procedures as well as for use in paleotracer applications. We report on parameters controlling U immobilization and U isotope fractionation by adsorption onto Mn/Fe oxides, precipitation with phosphate, and biotic reduction. The light U isotope (235U) is preferentially adsorbed on Mn/Fe oxides in an oxic system. When adsorbed onto Mn/Fe oxides, dissolved organic carbon and carbonate are the most efficient ligands limiting U binding resulting in slight differences in U isotope composition (δ238U = 0.22 ± 0.06‰) compared to the DOC/DIC-free configuration (δ238U = 0.39 ± 0.04‰). Uranium precipitation with phosphate does not induce isotope fractionation. In contrast, during U biotic reduction, the heavy U isotope (238U) is accumulated in reduced species (δ238U up to -1‰). The different trends of U isotope fractionation in oxic and anoxic environments makes its isotope composition a useful tracer for both environmental and paleogeochemical applications.