Xanthan Exopolysaccharide: Cu(2+) Complexes Affected from the pH-Dependent Conformational State; Implications for Environmentally Relevant Biopolymers.

The conformational impact of environmental biopolymers on metal sorption was studied through Cu sorption on xanthan. The apparent Cu(2+) complexation constant (logK; Cu(2+) + L(-) ↔ CuL(+)) decreased from 2.9 ± 0.1 at pH 3.5 to 2.5 ± 0.1 at pH 5.5 (ionic strength I = 0.1). This behavior is in apparent contradiction with basic thermodynamics, as usually the higher the pH the more cations bind. Our combined titration, circular dichroism and dynamic light scattering study indicated that the change observed in Cu bond strength relates to a conformational change of the structure of xanthan, which generates more chelating sites at pH 3.5 than at pH 5.5. This hypothesis was validated by the fact that the Cu sorption constants on xanthan were always higher than those measured on a mixture of pyruvic and glucuronic acids (logK = 2.2), which are the two constitutive ligands present in the xanthan monomer. This study shows the role of the structural conformation of natural biopolymers in metal bond strength. This finding may help to better predict the fate of Cu and other metals in acidic environmental settings such as aquatic media affected by acid mine drainage, as well as peats and acidic soils, and to better define optimal conditions for bioremediation processes.

Ecological Engineering Approaches to Improve Hydraulic Properties of Infiltration Basins Designed for Groundwater Recharge.

Infiltration systems are increasingly used in urban areas for groundwater recharge. The reduction of sediment permeability by physical and/or biological processes is a major problem in management of infiltration systems often requiring expensive engineering operations for hydraulic performance maintenance. To reduce these costs and for the sake of sustainable development, we proposed to evaluate the ability of ecological engineering approaches to reduce the biological clogging of infiltration basins. A 36-day field-scale experiment using enclosures was performed to test the influences of abiotic (light reduction by shading) and biotic (introduction of the macrophyte Vallisneria spiralis (L.) or the gastropod Viviparus viviparus (Linnaeus, 1758)) treatments to limit benthic biofilm biomass and to maintain or even increase hydraulic performances. We coupled biological characterization of sediment (algal biomass, bacterial abundance, total organic carbon, total nitrogen, microbial enzymatic activity, photosynthetic activity, and photosystem II efficiency) with hydraulic conductivity measurements to assess the effects of treatments on sediment permeability. The grazer Viviparus viviparus significantly reduced benthic biofilm biomass and enhanced hydraulic conductivity. The other treatments did not produce significant changes in hydraulic conductivity although Vallisneria spiralis affected photosynthetic activity of biofilm. Finally, our results obtained with Viviparus viviparus are promising for the development of ecological engineering solutions to prevent biological fouling in infiltration systems.

Scale-dependent effects of vegetation on flow velocity and biogeochemical conditions in aquatic systems.

In rivers, scale-dependent feedbacks resulting from physical habitat modifications control the lateral expansion of submerged plant patches, while the mechanisms that limit patch expansion on a longitudinal dimension remain unknown. Our objective was to investigate the effects of patch length on physical habitat modification (i.e., flow velocity, sediment grain size distribution), the consequences for biogeochemical conditions (i.e., accumulation/depletion of nutrients, microbial respiration), and for individual plants (i.e., shoot length). We measured all of these parameters along natural patches of increasing length. These measurements were performed at two sites that differed in mean flow velocity, sediment grain size, and trophic level. The results showed a significant effect of patch length on organic matter content and nutrient concentrations in interstitial water. For the shortest patches sampled, all of these parameters had similar values to those measured at the upstream control position. For longer patches, organic matter content and orthophosphate and ammonium concentrations increased within the patch compared to the upstream bare sediment, whereas nitrate concentrations decreased, suggesting changes in vertical water exchanges and an increase in anaerobic microbial activities. Furthermore, plant height was related to patch length by a quadratic pattern, probably due reduced hydrodynamic stress occurring for increasing patch length, combined with conditions that are less favourable for plants over a threshold length, possibly due to the light limitation or to the high concentration of ammonium that in the concentration range we measured may be toxic for plants. The threshold lengths over which patches influence the nutrient concentrations were reduced for the site with higher nutrient levels. We demonstrated that the plant-induced modifications of the physical habitat exert important effects on biogeochemical conditions, with possible consequences for patch dynamics and ecosystem functioning.

Structural stability, microbial biomass and community composition of sediments affected by the hydric dynamics of an urban stormwater infiltration basin. Dynamics of physical and microbial characteristics of stormwater sediment.

The sedimentary layer deposited at the surface of stormwater infiltration basins is highly organic and multicontaminated. It undergoes considerable moisture content fluctuations due to the drying and inundation cycles (called hydric dynamics) of these basins. Little is known about the microflora of the sediments and its dynamics; hence, the purpose of this study is to describe the physicochemical and biological characteristics of the sediments at different hydric statuses of the infiltration basin. Sediments were sampled at five time points following rain events and dry periods. They were characterized by physical (aggregation), chemical (nutrients and heavy metals), and biological (total, bacterial and fungal biomasses, and genotypic fingerprints of total bacterial and fungal communities) parameters. Data were processed using statistical analyses which indicated that heavy metal (1,841 µg/g dry weight (DW)) and organic matter (11%) remained stable through time. By contrast, aggregation, nutrient content (NH4⁺, 53-717 µg/g DW), pH (6.9-7.4), and biological parameters were shown to vary with sediment water content and sediment biomass, and were higher consecutive to stormwater flows into the basin (up to 7 mg C/g DW) than during dry periods (0.6 mg C/g DW). Coinertia analysis revealed that the structure of the bacterial communities is driven by the hydric dynamics of the infiltration basin, although no such trend was found for fungal communities. Hydric dynamics more than rain events appear to be more relevant for explaining variations of aggregation, microbial biomass, and shift in the microbial community composition. We concluded that the hydric dynamics of stormwater infiltration basins greatly affects the structural stability of the sedimentary layer, the biomass of the microbial community living in it and its dynamics. The decrease in aggregation consecutive to rewetting probably enhances access to organic matter (OM), explaining the consecutive release of NH4⁺, the bloom of the microbial biomass, and the change in structure of the bacterial community. These results open new perspectives for basin management since the risk of OM and pollutant transfer to the aquifer is greatly affected by alternating dry and flood periods.

Combination of Lagrangian Discrete Phase Model and sediment physico-chemical characteristics for the prediction of the distribution of trace metal contamination in a stormwater detention basin.

Elevated trace metal concentrations in sediments pose a major problem for the management of stormwater detention basins. These basins provide a nature-based solution to remove particulate pollutants through settling, but the resuspension of these contaminated deposits may impact the quality of both surface and groundwater. A better understanding of trace metal distribution will help to improve basin design and sediment management. This study aims to predict the distribution of trace metal contamination in a stormwater detention basin through (i) investigation of the correlation between metal content in sediments and their settling velocity, and (ii) the coupling of such correlation with a Lagrangian Discrete Phase Model (LDPM). The correlation between Fe, Cr, Cu, Ni, Pb contents and the settling velocity is firstly investigated, based on the sediments collected from 6 sites (inlet and 5 traps at the bottom of a detention basin situated in Chassieu, France) during 5 campaigns in 2017. Results show that Fe is strongly correlated to settling velocity and can be considered as a good indicator of trace metal contents. The derived correlation is then combined with a LDPM for the prediction of trace metal distribution, producing results consistent with in situ measurements. The proposed methodology can be applied for other stormwater basins (dry or wet). As described in this article, the interactions between hydrodynamics and sediment physico-chemical characteristics is crucial for the design and management of stormwater detention basins, allowing managers to target the highest contaminated sediments.

Distribution of organic pollutants and natural organic matter in urban storm water sediments as a function of grain size.

The sealing of surfaces in urban areas makes storm water management compulsory. Contaminated particles carried from urban surfaces are deposited in infiltration ponds. This gives rise to a highly organic (11% DW) contaminated sedimentary layer (Zn:1.2 mg/g, Cd:15 mg/kg) that could threaten groundwater quality. During infiltration, particle arrangement impacts infiltrating water and sediment exchanges. In this context, understanding particle arrangement and leachable components is essential. This study investigates Organic Matter (OM) not only as a pollutant but also as a substrate and a structuring element. The leachable fraction was collected and grain size fractionation was performed. OM of sediments and isolated fractions were characterized by measuring organic carbon content, isolating aromatic hydrocarbons, saturated hydrocarbons and polar compounds after dichloromethane extraction, and by gas chromatography-mass spectrometry (GC-MS) molecular analyses. The organic compounds observed were petroleum byproducts (steranes and terpanes, unresolved complex mixture (UCM) and polycyclic aromatic hydrocarbons (PAH)), but plant and bacteria biomarkers were also found (phytol and derivatives, sterols). Leachable OM consisted of 6% of sediment OM (associated with particles >0.45 microm). This leachable OM is easily extractable by dichloromethane (96%) and contains fewer macromolecules than other fractions. Isolated grain size fractions showed dissimilarities (total organic carbon from 3.5 mg/g to 88.6 mg/g, extraction rate from 24 to 96%, aromatic hydrocarbon distribution) and similarities (proportions of aromatic and saturated hydrocarbons and polar compounds, molecular distribution of saturated hydrocarbons and polar compounds). The results suggest that organic macromolecules take part in the aggregation of sediments and prevent fine particles (<10 microm) from being leached. On the other hand, leachable particles (20 microm grain size mode) could carry low molecular weight organic molecules. The physical structure of the sediments and the leaching of particles containing contaminants are considerably affected by the presence of OM.

Concomitant Zn-Cd and Pb retention in a carbonated fluvio-glacial deposit under both static and dynamic conditions.

The chemical and physical processes involved in the retention of 10(-2)M Zn, Pb and Cd in a calcareous medium were studied under saturated dynamic (column) and static (batch) conditions. Retention in columns decreased in order: Pb>>Cd approximately Zn. In the batch experiments, the same order was observed for a contact time of less than 40h and over, Pb>>Cd>Zn. Stronger Pb retention is in accordance with the lower solubility of Pb carbonates. However, the equality of retained Zn and Cd does not fit the solubility constants of carbonated solids. SEM analysis revealed that heavy metals and calcareous particles are associated. Pb precipitated as individualized Zn-Cd-Ca- free carbonated crystallites. All the heavy metals were also found to be associated with calcareous particles, without any change in their porosity, pointing to a surface/lattice diffusion-controlled substitution process. Zn and Cd were always found in concomitancy, though Pb fixed separately at the particle circumferences. The Phreeqc 2.12 interactive code was used to model experimental data on the following basis: flow fractionation in the columns, precipitation of Pb as cerrusite linked to kinetically controlled calcite dissolution, and heavy metal sorption onto proton exchanging sites (presumably surface complexation onto a calcite surface). This model simulates exchanges of metals with surface protons, pH buffering and the prevention of early Zn and Cd precipitation. Both modeling and SEM analysis show a probable significant decrease of calcite dissolution along with its contamination with metals.

Assessment of ecotoxicological risks related to depositing dredged materials from canals in northern France on soil.

The implementation of an ecological risk assessment framework is presented for dredged material deposits on soil close to a canal and groundwater, and tested with sediment samples from canals in northern France. This framework includes two steps: a simplified risk assessment based on contaminant concentrations and a detailed risk assessment based on toxicity bioassays and column leaching tests. The tested framework includes three related assumptions: (a) effects on plants (Lolium perenne L.), (b) effects on aquatic organisms (Escherichia coli, Pseudokirchneriella subcapitata, Ceriodaphnia dubia, and Xenopus laevis) and (c) effects on groundwater contamination. Several exposure conditions were tested using standardised bioassays. According to the specific dredged material tested, the three assumptions were more or less discriminatory, soil and groundwater pollution being the most sensitive. Several aspects of the assessment procedure must now be improved, in particular assessment endpoint design for risks to ecosystems (e.g., integration of pollutant bioaccumulation), bioassay protocols and column leaching test design.

Evaluation of the phytotoxicity of contaminated sediments deposited "on soil": II. Impact of water draining from deposits on the development and physiological status of neighbouring plants at growth stage.

As part of a study of the phytotoxic risk of spreading contaminated sediments "on soil", a laboratory experiment was carried out to assess the impact of water draining from sediments on peripheral vegetation. Drainage water was obtained in the laboratory by settling three sediments with different pollutants levels, and the supernatant solutions (respectively A1, B1, C1 drainage waters) were used as soaking water for maize (Zea maïs L.) and ryegrass (Lolium perenne L.). The physicochemical characteristics of the supernatant water, particularly metal contents, showed a pattern of contamination, with C1>A1>B1. The plants tested were grown on soil for 21 days, before being soaked for another 21-day period with drainage water (treatments) and distilled water (control). Biomass parameters (fresh weight, length, etc.), enzymatic activity [glutamine synthetase (GS), phosphoenolpyruvate carboxylase (PEPc)] and Zn, Cu, Cd and Cr contents were measured on both the shoots and roots of each plant. Biomass parameters were stimulated by C1, not affected by A1 and decreased with B1 for maize, whereas they increased for ryegrass in all the treatments. Compared to the control, GS activity was stimulated by C1 in the shoots of both plants and inhibited by treatments B1 and C1 in maize roots. PEPc activity in ryegrass was 1.5-5 times higher with contaminated water treatment, while contrasting effects were observed in maize plants. Both plants showed greater accumulation of chromium and zinc than cadmium and copper. Treatment A1 was found to be less active on plant growth and have a lower impact on the physiological status (enzymatic activities) of both plants. Treatment C1 stimulated the growth and physiological status of the plants, especially in shoots, with higher metal accumulation values in both plants. Treatment B1 was found to show more variable effects on growth indices, enzymatic activity and metal accumulation according to plant species.

Dynamics of dissolved organic carbon (DOC) through stormwater basins designed for groundwater recharge in urban area: Assessment of retention efficiency.

Managed aquifer recharge (MAR) has been developed in many countries to limit the risk of urban flooding and compensate for reduced groundwater recharge in urban areas. The environmental performances of MAR systems like infiltration basins depend on the efficiency of soil and vadose zone to retain stormwater-derived contaminants. However, these performances need to be finely evaluated for stormwater-derived dissolved organic matter (DOM) that can affect groundwater quality. Therefore, this study examined the performance of MAR systems to process DOM during its transfer from infiltration basins to an urban aquifer. DOM characteristics (fluorescent spectroscopic properties, biodegradable and refractory fractions of dissolved organic carbon -DOC-, consumption by micro-organisms during incubation in slow filtration sediment columns) were measured in stormwater during its transfer through three infiltration basins during a stormwater event. DOC concentrations sharply decreased from surface to the aquifer for the three MAR sites. This pattern was largely due to the retention of biodegradable DOC which was more than 75% for the three MAR sites, whereas the retention of refractory DOC was more variable and globally less important (from 18% to 61% depending on MAR site). Slow filtration column experiments also showed that DOC retention during stormwater infiltration through soil and vadose zone was mainly due to aerobic microbial consumption of the biodegradable fraction of DOC. In parallel, measurements of DOM characteristics from groundwaters influenced or not by MAR demonstrated that stormwater infiltration increased DOC quantity without affecting its quality (% of biodegradable DOC and relative aromatic carbon content -estimated by SUVA254-). The present study demonstrated that processes occurring in soil and vadose zone of MAR sites were enough efficient to limit DOC fluxes to the aquifer. Nevertheless, the enrichments of DOC concentrations measured in groundwater below infiltration basins need to be considered in future studies to especially assess their impact on groundwater quality.

Evaluation of the phytotoxicity of contaminated sediments deposited "on soil". I. Impact of water draining from the deposit on the germination of neighbouring plants.

As part of a study of the phytotoxic risk of spreading of contaminated sediments "on soil", we carried out a laboratory experiment assessing the impact of water draining from sediments in a deposit scenario on the peripheral vegetation. The plant tested were the Chinese cabbage (Brassica campestris L. var. chinensis), maize (Zea mays L.) and ryegrass (Lolium perenne L.). The draining water samples (A1, B1 and C1) were obtained after decantation in laboratory of the sediments. The classification of the water sampled in decreasing order of cumulative contamination was C1 > A1 > B1. The B1 and C1 water samples inhibited the germination of seeds tested to various extents. The percentage of seeds that did not germinate was 1.3-fold times higher for Chinese cabbage with B1 than for the control and 2.3-fold times higher for ryegrass with C1 than for the control. Seeds watered with B1 had lower moisture contents than the control: 10% lower for ryegrass and maize and 50% lower for Chinese cabbage. An increase (about 1.5 microg/ml) in total soluble protein (versus the control) was observed for all three plant species tested in the presence of C1. Glutamine synthetase activity was significantly (1.35 times) higher in ryegrass seeds in the presence of C1 than in the control. We also observed changes in the specific activity of phosphoenolpyruvate carboxylase, which increased for ryegrass and decreased for maize as the concentration of contaminants in the water increased. The results show (i) the necessity to use different plant species to evaluate the toxic effect of sediment deposited on soil on the vegetation, and (ii) that soon as on germination an evaluation of an impact is possible.

Experimental study and modeling of the transfer of zinc in a low reactive sand column in the presence of acetate.

Nowadays, it is necessary to understand and identify the reactions governing the fate of heavy metals introduced into the environment with low complexing organic compounds, particularly when they are transferred through soils in urban areas. In this work the concomitant influence of pH and acetate on the fate of zinc on siliceous sand was studied in batch and non-saturated column experiments. Total zinc concentrations varied between 2 and 20 mg/l, and total acetate concentrations were fixed at 22, 72, 132, and 223 mM to obtain solution pHs of 4, 5, 6 and 7, respectively. Natural sand (diameter, 0.3-2 mm), mainly constituted of silica, was used. In batch adsorption experiments, zinc adsorption is insignificant at pH 4, low and linear at pH 5, and increasingly nonlinear, of the Langmuir type, at pH 6 and 7 indicating near-saturation conditions of surface sites at these high pH values. In column experiments, Zn retardation increases and the maximum outlet concentration of Zn decreases with rising pH and acetate concentrations. Previous column tracer experiments revealed the occurrence of regionalized water transport in the column. Modeling these data was based on a non-electrostatic approach. Batch and column data modeling was based on the PHREEQC code that allows concomitant resolution of chemical speciation and regionalized water transport. The speciation calculation indicates that the ZnAcetate+ species is the dominant Zn species in the solutions used. Batch experimental curves are correctly modeled assuming the formation of the three surface species triple bond SiOZn+, triple bond SiOH-Zn Acetate+ and triple bond SiO-Zn(Acetate)2-. The column data could be adequately modeled assuming a two-region water transport and the formation of the same three species with the same thermodynamic constants determined in the batch experiments. The hypothesis of the modeling leads to a slight overestimation of the quantities of zinc eluted (10%) at pH 6 and 7, mostly in the desorption phase. These results show that the methodology used facilitates the correct modeling of both batch and transport experiments and formulation of the hypothesis on the interactions between the low reactive sand and a complex solution.

Review on physical and chemical characterizations of contaminated sediments from urban stormwater infiltration basins within the framework of the French observatory for urban hydrology (SOERE URBIS).

Urban stormwater infiltration basins are designed to hold runoff from impervious surfaces and allow the settling of sediments and associated pollutants. However concerns have been expressed about the environmental impacts that may be exerted by the trapped pollutants on groundwater, soils and ecosystems. In this context, sediment characterization represents a key issue for local authorities in terms of management strategies. During the last two decades, several studies were launched including either physical or chemical characterization of stormwater sediments but without real synthesis of data and methods used. Consequently, there is an important need for reviewing the current experimental techniques devoted to the physico-chemical characterization of sediment. The review is based on the outcomes of two experimental sites for which long term monitoring and data collection have been done: the Cheviré basin (near Nantes) and the Django Reinhardt basin (near Lyon). The authors summarize the studies dealing with bulk properties, pollutant contents, their potential mobility and speciation. This paper aims at promoting the significant progresses that were made through a multidisciplinary approach involving multi-scaled and combined experimental techniques.

Determining the experimental leachability of copper, lead, and zinc in a harbor sediment and modeling.

The potential leaching of pollutants present in harbor sediments has to be evaluated in order to choose the best practices for managing them. Little is known about the speciation and mobility of heavy metals in these specific solid materials. The objective of this paper is to determine and model the leachability of copper, lead, and zinc present in harbor sediments in order to obtain essential new data. The mobility of inorganic contaminants in a polluted harbor sediment collected in France was investigated as a function of physicochemical conditions. The investigation relied mainly on the use of leaching tests performed in combination with mineralogical analysis and thermodynamic modeling using PHREEQC. The modeling phase was dedicated to both confirm the hypothesis formulated to explain the experimental results and improve the determination of the main physico-chemical parameters governing mobility. The experimental results and modeling showed that the release of copper, lead, and zinc is very low with deionized water which is due to the stability of the associated solid phases (organic matter, carbonate minerals, and/or iron sulfides) at natural slightly basic conditions. However, increased mobilization is observed under pH values below 6.0 and above 10.0. This methodology helped to consistently obtain the geochemical parameters governing the mobility of the contaminants studied.

Mineralogical study and leaching behavior of a stabilized harbor sediment with hydraulic binder.

The environmental assessment of potential effects of contaminated harbor sediments stabilized with hydraulic binders and the determination of remediation endpoints require the determination of pollutants leaching potentials. Moreover, little information about the speciation and mobility of inorganic contaminants in these specific solid matrices is available in the literature. The objective of this paper is to investigate the relationship between mineralogy and leachability of contaminants (copper, lead, and zinc) present in a French harbor sediment stabilized with quicklime and Portland cement. Batch equilibrium leaching tests at various pH, chemical analysis of leachates, and mineralogical studies (X-ray diffraction, scanning electron microscopy-energy dispersive spectroscopy, and diffuse reflectance infrared Fourier transform) have been combined in the present investigation. The acid neutralization capacity of the stabilized matrix studied is first controlled by the dissolution of portlandite (pH ~12), followed by the dissolution of C-S-H (pH ~11) and the dissolution of ettringite (pH ~10). Finally, a very high buffering capacity of this stabilized sediment is observed for pH values around 6. This equilibrium is mainly controlled by the dissolution of iron sulfides and carbonate minerals. Consequently, the mobilization of inorganic contaminants as a function of pH remains very low (<0.1 wt%) for pH values above 6 and significantly increases for pH below these values. This research confirms the importance of a combined methodology for the intrinsic characterization of potential mobilization of contaminants in a stabilized sediment and for a better understanding of geochemical processes that affect contaminant fate, transformation, and transport in the subsurface environment.

Microbial communities of urban stormwater sediments: the phylogenetic structure of bacterial communities varies with porosity.

This study focuses on the distribution of bacterial and fungal communities within the microstructure of a multi-contaminated sedimentary layer resulting from urban stormwater infiltration. Fractionation was performed on the basis of differential porosity and aggregate grain size, resulting in five fractions: leachable fitting macroporosity, < 10, 10-160, 160-1000 µm fitting aggregates, > 1000 µm. Amounts of both bacterial and fungal biomasses are greater in the < 10 µm and leachable fractions. The aggregates contain numerous bacteria but very low amounts of fungal biomass. Single-strand conformational polymorphism molecular profiles highlighted the differences between bacterial and fungal communities of the leachable fraction and those of the aggregates. Random Sanger sequencing of ssu clones revealed that these differences were mainly because of the presence of Epsilonproteobacteria and Firmicutes in the leachable fractions, while the aggregates contained more Cyanobacteria. The Cyanobacteria phylotypes in the aggregates were dominated by the sequences related to Microcoleus vaginatus while the leachable fractions presented the sequences of chloroplastic origin. Therefore, more than 50% of the phylotypes observed were related to Proteobacteria while 40% were related to Cyanobacteria and Bacteroidetes. Preferential distribution of clades in almost all the phyla or classes detected was observed. This study provides insight into the identities of dominant members of the bacterial communities of urban sediments. Microcoleus vaginatus appeared to predominate in pioneer soils.