Partitioning Of Trace Metals Research Articles

Trace metal distribution in seagrass-vegetated sediments of an urbanized estuary in Queensland, Australia

Seagrasses increase sediment complexity by trapping particulates and influencing biogeochemical cycles via root oxygen loss and organic matter exudation. However, their impact on trace metal sequestration is poorly studied. We found significantly higher trace metal concentrations in seagrass sediments compared to adjacent bare sediments, correlating with total organic carbon, iron, and fine sediments. Sequential extractions showed that most trace metals were dominated by recalcitrant fractions (oxidizable and residual fractions), representing phases such as organic matter, iron sulfides, and crystalline iron oxides. Depth-dependent trends in trace metal partitioning were evident. For example, arsenic in the oxidizable fraction only weakly correlated with Fe in surface sediments (rsp = 0.55) but correlated strongly in deeper sediments (rsp = 0.87), consistent with iron sulfides being a dominant host-phase. Overall, these results suggest that the unique geochemical conditions facilitated by seagrasses play an important role in sequestering trace metals in urban estuarine sediments.

Trace and Rare Earth Element Fingerprints of Aerobic Oxidation of Methane in Seep‐Dwelling Bivalves

AbstractAerobic methanotrophic bacteria are pivotal in the global carbon cycle by converting methane into biomass and inorganic carbon species. Light rare earth elements (light‐REE; La, Ce) are part of the metalloenzymes mediating the biochemical processes in methanotrophs. However, the partitioning of trace metals and REE in chemosymbiotic megafauna with methanotrophic endosymbionts remains largely unknown. Here we determine stable isotope compositions (δ13C, δ15N) of soft tissues (gill, mantle, foot) as well as trace metal and REE contents of soft tissues and shells of chemosymbiotic bivalves dwelling at methane seeps (Site F and Haima seeps) of the South China Sea. Isotopic compositions of soft tissues are found to reflect the mode of chemosymbiosis (i.e., methanotrophy vs. thiotrophy). Particularly gill tissues of bivalves with methanotrophic endosymbionts display marked light‐REE and trace metal enrichments, which is interpreted to reflect the enzymatic activity of endosymbionts. Additionally, correlations between light‐REE and copper (Cu), zinc (Zn), and molybdenum (Mo) contents in soft tissues of chemosymbiotic mussels are ascribed to the uptake of these elements by the methanotrophic symbionts. An observed higher trace metal content in the tissue of the semi‐infaunal and infaunal bivalves with thiotrophic endosymbionts is believed to reflect the uptake of metals associated with sulfide particles. This study documents diagnostic enrichment of trace metals and light‐REE in the soft tissues of bivalves with chemotrophic endosymbionts and provides new constraints for future identification of chemosymbiosis at ancient seeps.

Trace metal partitioning in the parnaíba delta in dry season, equatorial coast of Brazil

Trace metal concentrations in the particulate fractions (MP), dissolved fractions (MD) and sediments (MS), such as Ba, Cu, Co, Cr, Pb, Ni and Zn, were determined during the dry season of the largest open sea delta of Americas, the Parnaíba River Delta (Brazil). This study aimed to comprehend the distribution, dynamic changes of metal speciation and environmental quality index of trace metals in the particulate fractions and subsurface sediments in scenario of major marine influence over the delta. The trace metals bound to suspended particulate material (SPM) from weathering the drainage basin exhibited a removal trend under increases in salinity and pH. Desorption influenced the partitioning of BaMP, ZnMP, NiMP, CoMP, CuMP, and the adsorption and precipitation of PbMP and CrMP to the surface sediments. The organic matter contents in the sediments acts as an important geochemical carrier of these contaminants, and the dissolved organic carbon influences the binding of PbMD in the subsurface waters. The geoaccumulation index (Igeo) plays a crucial role in revealing potential contamination with ZnMP contents and weak association to this fraction. These results make possible the assessment of ecological risk by metal contamination and global pollution mitigation in coastal tidal estuaries under intensive physical mixing along the equatorial coast.

Characterizing Trace Metal Contamination and Partitioning in the Rivers and Sediments of Western Europe Watersheds

Adsorption and desorption processes occurring on suspended and bed sediments were studied in two datasets from western Europe watersheds (Meuse and Mosel). Copper and zinc dissolved and total concentrations, total suspended sediment concentrations, mass concentrations, and grain sizes were analyzed. Four classes of mineral particle size were determined. Grain size distribution had to be considered in order to assess the trace metal particulate phase in the water column. The partitioning coefficients of trace metals between the dissolved and particulate phases were calculated. The objective of this study was to improve the description of the processes involved in the transportation and fate of trace metals in river aquatic ecosystems. Useful data for future modelling, management and contamination assessment of river sediments were provided. As it is confirmed by a literature review, the copper and zinc partitioning coefficients calculated in this study are reliable. The knowledge related to copper and zinc (e.g., partitioning coefficients) will allow us to begin investigations into environmental modelling. This modelling will allow us to consider new sorption processes and better describe trace metal and sediment fates as well as pressure–impact relationships.

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.

Trace Metal Partitioning in the Salinity Gradient of the Highly Stratified Estuary: A Case Study in the Krka River Estuary (Croatia)

A size partitioning of several trace metals (Zn, Cd, Pb, Cu, Ni, Co, Mn, Fe and Al) between five size fractions (&lt;3 kDa, 3 kDa–0.1 µm, 0.1 µm–1.2 µm, 1.2 µm–5 µm and &gt;5 µm) was studied in the vertical salinity gradient of the highly stratified Krka River estuary. The results indicated a dominant river source for Zn, Co, Mn, Fe and Al and a diluting effect on Cd, Pb and Ni. The truly dissolved fraction (&lt;3 kDa) dominated the Zn, Cd, Cu, Ni and Co pool, and a large part of Pb, Mn, Fe and Al was present in &gt;5 µm particles. Pb, Mn, Fe and Al were closely related, showing a precipitation and colloidal aggregation in the surface layers and dissolution in the seawater layer. The highest percentage (30–37%) of colloids (3 kDa–0.1 µm) in the dissolved pool was found for Pb, Cu, Fe and Al. Differences in size distribution between low and high river flow periods revealed that Zn, Pb, Co, Mn, Fe and Al are introduced by the river mostly in the 3 kDa–5 µm size range. Therefore, a low percentage of colloidally bound metals compared to other coastal areas can be explained by a limited riverine input of terrigenous material, characteristic for this estuary. Correlation with PARAFAC components revealed associations of Cu with protein-like substances and Co with humic-like substances. The accumulation of Cu at the freshwater-seawater interface coupled with an increase of its colloidal fraction was observed, apparently governed by biologically produced organic ligands.

Estuarine dissolved speciation and partitioning of trace metals: a novel approach to study biogeochemical processes

Estuaries are complex systems involving numerous biogeochemical gradients and processes that influence the behavior of trace metals. Lead (Pb), cadmium (Cd), and copper (Cu) speciation and partitioning were studied in the Gironde Estuary (SW France), using a multi-method approach in which data from innovative sensors and laboratory-based techniques were combined. For the first time in this system, the so-called dynamic fractions of the target metals (dissolved forms that are potentially bioavailable) were recorded on-board through voltammetry using unique antifouling gel-integrated microelectrode arrays (GIME) incorporated in a submersible sensing probe (TracMetal). Trace metals in the operationally defined dissolved <0.2 μm and <0.02 μm fractions, as well as complexed with suspended particles (collected after centrifugation) were quantified through sampling/laboratory-based techniques. High spatial resolution trace metal concentrations were monitored along the salinity gradient (S = 0.10 to S = 34.0) together with master bio-physicochemical parameters providing robust cruise-specific information on how well-known abiotic and biotic processes control the Gironde estuarine trace element partitioning, (i.e. conservative behavior, addition/removal). Combining conventional methods with GIME measurements showed: (i) the dominance of Cd dynamic species in the intra-estuarine total dissolved fraction (up to 90%), (ii) the importance of small colloids as trace metal carrier phases, desorbing and complexing dynamic fractions of Pb and Cu, and (iii) the potential influence of photo-redox processes remobilizing Pb under their dynamic forms (up to 80%). Data also suggest trace metal release/sorption by phytoplankton with an increase of dissolved Cu concentrations in the riverine branch, as well as Cu and Cd particulate concentrations showing higher levels towards productive coastal waters. This complete approach allowed to monitor key estuarine biogeochemical processes and highlighted the valuable use of the TracMetal to record subtle variations of potentially bioavailable dissolved metal fractions.

Coprecipitation of metal ions into calcite: an estimation of partition coefficients based on field investigation

Trace elements (and their isotopes) in carbonates are commonly used to reconstruct paleoenvironment and paleoclimate. Understanding the processes and mechanisms of element incorporation into carbonates is thus crucial for using such geochemical parameters as paleoclimate proxies. In contrast to laboratory-based experimental results, the partitioning of trace metals between solid and solution phases in natural carbonate precipitation systems has rarely been reported. In this study, we investigated the partition coefficients of metal ions between solid and solution in the channel of the natural Baishuitai travertine system, Yunnan, China. Our results show that the partition coefficients of Li+, Na+, Mg2+, Sr2+ and Ba2+ are 1, consistent with the results found in previous experimental studies. Although the substitution for Ca2+ is likely the main uptake process of these metals into calcite, depending on their ionic radius and charge, trace elements may also be incorporated by adsorption or physical entrapment. Our study shows that unlike laboratory experiments performed under specific conditions, the partitioning of metals between two phases in the natural travertine system could be controlled by several, even multiple, environmental factors (e.g., carbonate deposition rate, temperature, and pH), which should be taken into account when using trace metals (and their isotopes) in carbonate archives as a paleoclimate proxy.

Investigation on trace metal speciation and distribution in the Scheldt estuary

The biogeochemical behavior of Cd, Co, Cr, Cu, Ni and Pb along the historically polluted Scheldt estuary (Belgium - The Netherlands) was investigated in this study. As never studied before in this area, labile trace metals were measured using the passive sampling technique of Diffusive Gradients in Thin-films (DGT), while total dissolved and particulate trace metal concentrations were assessed using classic active sampling techniques. This dual approach allowed us to highlight the variations of trace metal speciation and distribution in the estuarine surface waters, considering environmental and physicochemical gradients along the transect. The large data set obtained was then compared with literature data of historical measurements along the Scheldt (from 1980 until now), but also from other estuaries. As emphasized by our results, trace metal mobility and partitioning along the Scheldt estuary was mainly driven by biogeochemical reactions which were strongly influenced by gradients of specific estuarine physico-chemical parameters, such as salinity, turbidity, temperature and so on. Hence, all species of trace metals displayed a non-conservative behavior. More precisely, dissolved labile fractions of trace metals showed higher levels in the middle estuary, where many solubilization and remobilization processes occurred due to turbulent mixing mechanisms and an increasing salinity. Our study confirmed the decreasing trend historically observed for particulate metals along the Scheldt, as well as the rising concentrations recorded for dissolved trace metals which might also lead to an increase of their labile fraction measured by the DGT. Finally, these preliminary results suggested that a more regular monitoring of labile metal along the Scheldt estuary is essential to have an in-depth understanding of trace metal speciation and to review bioavailability of trace metals within estuarine ecosystems.

Distribution and availability of rare earth elements and trace elements in the estuarine waters of the Ría of Huelva (SW Spain)

Metal pollution in estuaries represents a serious environmental challenge, especially in areas affected by industrial and mining activities. This study investigates the metal partitioning and availability of rare earth elements (REE), Y and other trace metals (Ag, Tl, U and Cs) in the Ria of Huelva estuary (SW Spain), strongly affected by mining and industrial activities. A 30 h monitoring campaign was performed collecting periodic water samples and deploying diffusive gradient in thin films (DGTs) devices to determine the main factors controlling metal availability. The dissolved concentrations of U (3118–3952 ng/L) and Cs (284–392 ng/L) were in the same order of magnitude than those reported in other estuaries and coastal waters worldwide, however, REE (26–380 ng/L), Y (15–109 ng/L), Ag (14–307 ng/L) and Tl (29–631 ng/L) concentrations exceeded these values for the same salinities. Unlike most metals (i.e. Ag, Tl, U, Cs), which were mainly found in the dissolved form (87–100% of total), REE and Y were found in the particulate phase (22–36% of total). Metal lability was mainly related to the concentration in the water column following this order: U>REE>Y>Ag>Tl. A similar binding mechanism was observed for Tl and Cd, due to its chemical affinity. This relationship between chemical properties and absorption by DGT-resin was also observed for REE (and Y), Rb and Sr, which may cause bioaccumulation upon persistent exposure, considering the ability of these metals to cross the biological membranes. The lability of metals predicted by geochemical codes did not coincide with absorption of labile metals by DGTs due probably to the instability of complexes in contact with the DGT membranes, the inability of metals to form thermodynamically stable complexes or the absorption of colloids. From this work it can be concluded that DGT passive sampling should complement traditional sampling to monitor metal availability in aquatic environments.

Trace metal partitioning in a shallow estuary, Muthupet, India

Dissolved trace metal concentrations of Fe, Cd, Cu and Zn were analysed in the Muthupet estuary, a well-mixed micro-tidal estuary in India during the post-monsoon and pre-monsoon in 2014. There was a significant variation in the salinity and suspended sediment concentration over the seasonal scale with peak salinity occurring at the downstream mouth during the post-monsoon and at intermediate locations during the pre-monsoon. Strong seasonal variations were observed in the concentration of trace metals. The concentration of Fe, Cd and Zn exceeded the USEPA standards, while that of Cu was within the permissible limits. Fe, Cu and Zn showed non-conservative behavior with peak concentrations at mid-estuarine reaches, irrespective of the location of salinity maxima, while the peak concentration of Cd occurred at high salinity reaches. The complexation of Cd as chlorocomplexes enhanced the mobilization of Cd, resulting in a peak value at high salinity reaches. The study indicated that the estuary is influenced by oceanic water and the anthropogenic input is secondary. Resuspension of bed sediments is identified as the major process controlling the trace metal concentration. Partition coefficient (Kd) of Fe, Cu and Zn was observed to be an increasing function of salinity, of which, the effect on Fe was much significant. The coagulation of suspended sediments at high salinity reaches enhanced the removal of Fe as Fe oxyhydroxides.

Effect of deep Southwestern Subtropical Atlantic Ocean circulation on the biogeochemistry of mercury during the last two glacial/interglacial cycles

During glacial/interglacial cycles, changes in the strength of the Atlantic Meridional Overturning Circulation (AMOC) modified the intermediate and deep-water mass proportions and high latitude productivity in the Atlantic Ocean. These factors influence the distribution and geochemical partitioning of trace metals in the ocean. Mercury is a redox and productivity-sensitive trace metal, making it a potential proxy of paleoenvironmental changes. Therefore, this work examines the effect of Atlantic Ocean circulation changes during the last two glacial/interglacial cycles on the biogeochemistry of Hg. For this, a high-resolution record of the total Hg concentration was determined in core GL-1090 collected from the Southwestern Subtropical Atlantic that represents the last 185 thousand years. During the reported glacial/interglacial cycles, Hg showed a distinct trend throughout Marine Isotope Stages with higher concentrations during periods of enhanced penetration of northern component water into the southwestern Atlantic. This is supported by the similarity of mercury variability with benthic foraminifera δ13C, suggesting a strong influence of deep ocean circulation on the availability and accumulation of this metal in deep-sea sediments. Mercury geochemistry and particle scavenging were correlated with organic matter (OM) input at the core site. We also noted that mercury responded to redox variation in sediment after Termination II, which can be explained by the increase in deep ocean ventilation due to AMOC strengthening. This hypothesis was confirmed by the antiphase behavior of Hg and Total Organic Carbon when compared with Mn/Al ratios and CaCO3. Our work, therefore, allows for a better understanding of the processes leading to long-term mercury removal to sediments.

Modeling trace metal partitioning and speciation at the sediment-water interface using a chemical equilibrium model

Isotherm adsorption experiments for Pb, Cd and Zn were carried out with coastal sediments from China under oxic sediment-water conditions. The conditional equilibrium constants (Kads) determined from the adsorption isotherms were found to be most strongly correlated with Mn oxides (MnOx) for Pb and Cd, and with particulate organic carbon (POC) for Zn. MnOx and POC were then used as the surrogate metal-binding phases in a sediment-water chemical equilibrium model (SCEM). The apparent equilibrium constants (βsed, Me⁎) of the SCEM were determined to be 109.56±0.41 for Pb (n = 9), 105.25±0.34 for Zn (n = 7), and 106.51±0.29 for Cd (n = 7). The SCEM was then used to predict the free metal ion activities ({Me2+}) in seawaters of Jinzhou Bay, China. The SCEM-predicted {Me2+} compared well with the measured ones for Pb and Zn in seawater. However, the predicted {Cd2+} was higher than measured, which may reflect a detoxification mechanism of marine organisms in Jinzhou Bay seawater. Overall, a model of this kind can be highly useful for predicting {Men+} in the overlying waters based on the surface sediment chemistry, and can contribute to the development of sediment quality guidelines by linking them with the corresponding water quality criteria.

Trace metal partitioning and potential mobility in the naturally acidic sediment of Lake Caviahue, Neuquén, Argentina

Lake Caviahue, in Patagonia (Argentina), is a very acid water body (Patagonia, Argentina) due to the influx of volcanic fluids. Over the past 18 years, the lake has been progressively alkalinizing and pH is close to the ferric iron precipitation threshold (pH&gt;3,0). Should iron precipitate, wáter and sediment composition will be altered. To set a baseline, trace metal partitioning (Cu, Cd, Cr, Pb, Zn and Mn) was studied for three sediment cores (0 to 16 cm depth) at three sampling stations using a sequential extraction procedure (SEP) and the acid volatile sulfide/simultaneously extracted metals (AVS/SEM) protocol. The total metals content of the sediments ranged between 0 to 408 μg g-1 of dry sediment, with Pb&gt;Cr&gt;Mn&gt;Cu&gt;Zn&gt;Cd. No Cd was measured above the limit of detection. The sediment was richest in Mn and Cr, two non-toxic metals at the pH / Eh combination of the lake basin. Total Pb was at a moderate contamination level although it is associated with the most recalcitrant fraction and therefore has low mobility. The sediment fractions with higher metal content were the oxidizable and residual, the former commonly associated with labile organic matter and pyrite while the latter are related to recalcitrant organic matter and rock forming minerals. In addition, a high correlation was found between Cr, Pb and Mn,thus these metals may be subject to analogous precipitation processes and possibly to co-variation in the volcano effluents. Furthermore, no metals were detected in the exchangeable/carbonates fraction, which is the most labile of all the sediment fractions. The metal content in (SEM) was likewise below the toxicity thresholds of two international sediment quality guidelines and the ratio AVS/SEM was over one, indicative of non-toxicity. Both results indicate that metal mobility in the acidic sediments of lake Caviahue is very low.

Potential availability of trace metals in sediments in southeastern and southern Brazilian shipyard areas using the DGT technique and chemical extraction methods

Speciation and partitioning of trace metals, from solid to solution phases of sediments, control their bioavailability and thus their potential ecological risk to organisms. Therefore, in order to obtain a broad evaluation of their risk, it is necessary to couple methodologies that are able to assess metal mobility in sediment. In this study, the Diffusive Gradients in Thin Films (DGT) technique and the application of 0.1 M HCl acid extraction methods, together with solid-state voltammetric sensors, were used with the objective of assessing mobility and potential availability of Cr, Cu, Ni, Pb, V and Zn in sediment porewaters and solid sediments in southeastern and southern Brazilian shipyard areas. The highest labile metal concentrations were found in shipyards with the longest histories of operations. Trace metal distributions in porewater and in the solid phase of sediments (labile metals) and significant correlations among metals enabled to distinguish the contribution of anti-fouling paint components. The diffusive flux of every metal measured at the surface of the sediment indicated that CuDGT had the highest flux (3.66E−03 mmol·m−2 d−1) in the shipyard with the longest operating time. Therefore, enrichment was observed for Cu, Pb and Zn in sediments, indicating a possible ecological risk level of ‘Effects Range Median’ to ‘Apparent Effects Threshold’ for oyster larvae (Mollusca) (Cu), bivalves (Pb) and the infaunal community (Zn). Probable Effect Concentrations (PEC) to sediment-dwelling biota can be expected as well, related to high concentrations of Cu and Zn in sediment. This study allowed a comprehensive evaluation of potential bioavailability and ecological risk of trace metals in aquatic systems where there is continuous and specific input of these elements. The use of the DGT technique with solid-state voltammetry in the sediment of distinct Brazilian estuarine systems demonstrated its potential to be applied in future environmental network programs.

Comparison of Two Sequential Extraction Procedures for Trace Metal Partitioning in Ore Samples From the Keban Region in Elazig, Turkey

Comparison of Two Sequential Extraction Procedures for Trace Metal Partitioning in Ore Samples From the Keban Region in Elazig, Turkey

The distribution and partitioning of trace metals (Pb, Cd, Cu, and Zn) and metalloid (As) in the Beijiang River.

The concentrations of Cu, Zn, Pb, Cd, and As varied quite differently in the water, suspended particulate matter (SPM), and sediment along the middle reach of the Beijiang River in southern China. The total concentrations of trace metals and As in the water column were significantly affected by the concentration of SPM, while the metals and As in the sediment were mainly influenced by fine particle component, OM and Fe/Mn/Al. The partitioning coefficient of trace metals and As in the water column generally appeared in the following order: Pb > Cd > Cu > Zn > As. Accordingly, approximately 67.9% of Pb migrated with SPM in the river because of its higher particle reactivity, while the SPM-bound Cu, Zn, and As were approximately 43.4, 37.3, and 26.7%, respectively. The fractions of Cd in the dissolved and particulate phases were almost the same. Sediment resuspension and deposition in the Beijiang River were considered as important factors controlling the concentrations of dissolved Cu, Zn, Pb, Cd, and As in the bottom of the water column.

Trace metals partitioning between particulate and dissolved phases along a tropical mangrove estuary (Can Gio, Vietnam)

Mangroves can be considered as biogeochemical reactors along (sub)tropical coastlines, acting both as sinks or sources for trace metals depending on environmental factors. In this study, we characterized the role of a mangrove estuary, developing downstream a densely populated megacity (Ho Chi Minh City, Vietnam), on the fate and partitioning of trace metals. Surface water and suspended particulate matter were collected at four sites along the estuarine salinity gradient during 24 h cycling in dry and rainy seasons. Salinity, pH, DO, TSS, POC, DOC, dissolved and particulate Fe, Mn, Cr, As, Cu, Ni, Co and Pb were measured. TSS was the main trace metals carrier during their transit in the estuary. However, TSS variations did not explain the whole variability of metals distribution. Mn, Cr and As were highly reactive metals while the other metals (Fe, Ni, Cu, Co and Pb) presented stable log KD values along the estuary. Organic matter dynamic appeared to play a key role in metals fractioning. Its decomposition during water transit in the estuary induced metal desorption, especially for Cr and As. Conversely, dissolved Mn concentrations decreased along the estuary, which was suggested to result from Mn oxidative precipitation onto solid phase due to oxidation and pH changes. Extra sources as pore-water release, runoff from adjacent soils, or aquaculture effluents were suggested to be involved in trace metal dynamic in this estuary. In addition, the monsoon increased metal loads, notably dissolved and particulate Fe, Cr, Ni and Pb.

Size partitioning and mixing behavior of trace metals and dissolved organic matter in a South China estuary

The Jiulong River estuary, located in the southeastern China, suffered from metal pollution due to industrial effluent releases. Mixing of effluent and estuarine water may have significantly affected the size distribution of trace metals and their environmental fate. In the present study, colloidal size distribution of organic matter and selected metals were quantified using asymmetric flow field-flow fractionation (AF4) and ICP-MS. We demonstrated a dominance of dissolved metals in the 1–10kDa fraction, and metals such as Cu, Zn, Ni, Co, Pb, Cd and Mn were mostly regulated by terrestrial fulvic acid. The larger inorganic colloids played a limited role, although Fe reduction was likely to affect the size partitioning of colloidal Mn. The holding pond represented a source of trace metals and chromophoric and humic-like dissolved organic matter to the estuary. Scavenging or removal behavior became evident following the intermittent mixing, and the small sized colloidal organic complexes were responsible for binding and stabilizing trace metals. Variations in particle size distributions indicated different sources, fates and geochemical controls of the metals. Our results highlighted the impacts of both natural and anthropogenic processes on the transformation of trace metals among phases in this dynamic estuary system.

Lateral and longitudinal patterns of water physico-chemistry and trace metal distribution and partitioning in a large river floodplain

Floodplain water bodies provide habitat to diversified ecological communities. Floodplains are also among the most impacted aquatic ecosystems. While the link between the lateral connectivity of floodplain sites to the main channel and their plant, fish and invertebrate communities has been well established, detailed information on chemical characteristics and particularly on trace metal spatial distribution and partitioning is scarce. The aim of this study was to examine the link between the lateral connectivity and physico-chemical variables, their trace metal concentrations and partitioning as well as the upstream-downstream gradient of these parameters. In connected and disconnected water bodies of the Rhône River upstream and downstream of the city of Lyon, we measured major ions, dissolved organic carbon, trace metal concentrations (Al, Cr, Ni, Cu, Zn, Cd, Pb and U) in water, suspended particulate matter (SPM) and sediment. The results revealed a clear difference between connected and disconnected water bodies. pH, SPM, Na+, and NO3− concentrations were lower in disconnected sites while conductivity, DOC, Ca2+ and Mg2+ were higher. Conductivity and a part of the major ion concentrations increased in the downstream sections. Trace metal concentrations and partitioning varied between connected and disconnected sites. In the dissolved fraction, trace metal concentrations were higher in connected sites. In the surface sediment, concentrations were higher in disconnected sites for the majority of metals. The upstream-downstream gradient was less important than the connected-disconnected gradient. Only three metals in the dissolved fraction (Cu, Cd and Pb) showed a clear increase in downstream sections. Overall, the study shows that the functioning of floodplains produces strong spatial patterns concerning the concentrations and partitioning of trace metals. These findings improve our understanding of trace metal biogeochemistry in floodplains and have important applications for floodplain restoration projects.