5-year leaching experiments to evaluate a modified bauxite residue: remediation of sulfidic mine tailings.

The ALTEO company produces approximately 300,000 tons per year of bauxite residue after alumina extraction, which is washed and dried in a press filter to produce Bauxaline®. In this study, different ways for recovering and reusing this residue were explored, namely transformation into a vegetated soil, use in acid mine drainage depollution, and application in sulfide-mine tailings remediation. The Bauxaline® was therefore transformed into modified bauxite residue (MBR), resulting in reduced alkalinity, salinity, and sodicity. To counterbalance the net acid generation potential of two sulfidic mine tailings with 1 mol H+ kg-1 (1.5% sulfide) and 3.3 mol H+ kg-1 (5.3% sulfide), respectively, various treatments were applied. These treatments included the addition of 10% MBR or 10% MBR plus limestone, or by limestone only, within 40-l lysimeters. Six lysimeters were monitored over a 5-year period to assess the long-term emissions from treated materials. Vegetation was tested under various conditions, and its impact on emission was evaluated. The emissions of mine tailings treated with MBR and limestone were very low. The mine tailings with limestone showed intermittent peaks of emission, probably due to the coating of calcite grain by ferric oxide, hindering contact with percolating water. Vegetation successfully grew in the treated tailings. This study demonstrated that the alkalinity of limestone can temporarily immobilize elements in sulfidic mine tailings, with a reduction factor of emissions of 300 and 40 for the two mine tailings, respectively. For long-term immobilization, the alkalinity provided by both limestone and MBR and the Al and Fe oxides of MBR are more effective and necessary for long-term immobilization, with a reduction factor of 300 and 900, respectively.

Nanoplastic production procedure for scientific purposes: PP, PVC, PE-LD, PE-HD, and PS.

Studies on the environmental impact of nanoplastics face challenges in plastic analysis and a scarcity of nanoplastic materials necessary for the development of analytical techniques and experiments on biota impact. Here we provide detailed procedures for obtaining nanoparticles suspended in water for the most commonly used polymers: Polypropylene (PP), Polyvinylchloride (PVC), Low- and High-Density Polyethylene (PE-LD, PE-HD), and Polystyrene (PS). We dissolved larger size material to reprecipitate nanoparticles. For all plastic types, we obtained nanoparticles with a size between 50 and 300 nm, and a mainly spherical morphology. We verified that no irreversible agglomeration or coalescence of the particles occurred after 5 days of storage. The concentrations obtained in the final carrier solution were of the order of 109 particles mL-1. To prevent the persistence of reagents in the final carrier solution, a filtration step was implemented at the end of the process. The method proved unsuitable for Polyethylene Terephthalate (PET).

Metal speciation in sludges: a tool to evaluate risks of land application and to track heavy metal contamination in sewage network.

The agricultural spreading of dehydrated sewage sludge from urban sewage treatment plants is economically profitable provided that the soil agronomic quality and the absence of contamination, in particular of heavy metals, are maintained. We evaluated the variability of sludge between five treatment plants in northern Algeria. We determined parameters that account for their agronomic quality and total content of Ag, Cd, Co, Cr, Cu, Ni, Pb, Ti and Zn. The speciation of metals, which determines their bioavailability, was characterized by sequential extraction into five fractions: easily exchangeable, acid-soluble, bound to carbonates and Fe-sulphides, bound to Fe-Mn oxides, bound to organic matter or sulphides, residual. All the sludges analysed showed satisfactory properties for plant growth. High total Ni contents for three of the sludges indicated that they were not landfillable under French or Chinese regulations. Ni, however, was contained in poorly bioavailable fractions and therefore presented a low risk to soils. In contrast, the total Cu was lower than the regulatory limit values, but mainly contained in very bioavailable fractions whose accumulation over time could reach toxic levels for plants over a period of 3 to 11 years depending on the sludges. These results showed that regulations are not adapted and must take into account the bioavailability with regard to the characteristics of the soils on which to spread. The speciation of metals in the sludge has also, on the one hand, made it possible to identify the zone of the sewerage network in which the sources of contamination must be sought and, on the other hand, has given indications on the possible nature of these sources.

Considering the ionic strength for proper use of 1 or 2-ligands model for static fluorescence quenching or enhancement.

We formally describe a 1- or 2-ligands fluorescence quenching or exhaustion model that takes ionic strength into account. We give ready-to-use formulas, which are easy to implement on a common spreadsheet, to determine complexing capacities and apparent stability constants of fluorescence ligands by adjusting quenching or enhancing experimental curves. The strength of our model is to consider parameters that have rarely taken in account in the literature, resulting in a significant improvement in the quality of the modeling: the charge associated with one or two ligands, and ionic strength. The model predicted fluorescence at various ionic strengths from parameters determined at a given ionic strength. This model is suitable for many applications, such as complexation of dissolved natural organic matter with metal ions, even in sea water, or biologic media.

Evidence of humic acid-aluminium­silicon complexes under controlled conditions.

The chemistry of silicon (Si), the second most abundant element in soil after oxygen, is not yet fully understood in the soil-water-plant continuum. Although Si is widely accepted as an element that has little or no interaction with natural organic matter, some data seems to show the opposite. To identify a potential interaction between natural organic matter and Si, batch experiments were achieved at various pH and Si concentrations, involving also Al3+ as a common ion in soil and using humic acid (HA) as a typical model for natural organic matter. Several complementary techniques were used to characterize the possible complexes formed in the dissolved or solid phases: molecular fluorescence spectroscopy, 29Si solid-state NMR, Fourier transform infrared spectroscopy, quantification of Si, Al and organic carbon, and nanoparticle size distribution. These tools revealed that humic acid indeed interacts, but weakly, with Si alone. In the presence of Al, however, a ternary complex HA-Al-Si forms, likely with Al as the bridging atom. The presence of Si promotes the maintenance of both Al and dissolved organic matter (DOM) in solution, which is likely to modify the result or the kinetics of pedogenesis. Such complexes can also play a role in the control of Al toxicity towards plants and probably also exists with other metals, such as Fe or Mn, and other metalloids such as As.

PDMPO: a specific silicon or silica, pH sensitive fluorescent probe?

In order to understand Si behavior and biodisponibility in soils and plants, we evaluated the use of PDMPO (2-(4-pyridyl)-5-((4-(2-dimethylaminoethylaminocarbamoyl)methoxy)phenyl)oxazole) that was supposed to be a Si-specific fluorescence marker and to have a pH-dependent fluorescence. We studied the interactions between PDMPO and water-dissolved Si, Al and natural organic matter (humic acids, HA). Six systems with different HA, Si and Al concentrations were studied by fluorescence spectroscopy at pH 4, 7 and 9. The Al-PDMPO complex was characterized by infrared spectroscopy and the particle size distribution in solution was characterized by nano tracking analysis. We found that when usual pH buffers are not present, the PDMPO fluorescence was not pH dependent and was not Si-specific. In the PDMPO-Si-HA system, the PDMPO fluorescence signals were greatly enhanced, suggesting the formation of highly fluorescent ternary HA-PDMPO-Si groups. When Al was added to the system, the fluorescence was strongly quenched, suggesting the formation of low-fluorescence quaternary HA-PDMPO-Si-Al groups. The PDMPO fluorescence is therefore greatly sensitive to complexable metals and to natural organic matter and is therefore difficult to be applied for the quantification of Si or pH in a complex medium.

Soil sample conservation from field to lab for heterotrophic respiration assessment.

We evaluated (1) whether the sample transport time could lead to a significant loss of carbon through microbial respiration and to a change of measured respiration rates, which can be a problem in areas difficult to access, with a long travel time from field to laboratory; (2) whether the method used to quantify heterotrophic respiration for agricultural soils is adequate for horizons that remain always water-saturated or close to saturation. Surface horizons and deep Bh of Amazonian podzols were sampled and kept under refrigeration to maintain moisture of sampling time. Incubations of aliquot of the same sample were initiated on the sampling day and 3, 6, 9 and 12 days after sampling. Other aliquots were conducted on a tension table to given water potential (60 cm H2O) prior to incubation.•Soil samples, whether disturbed or not, should not be dried but kept at sampling moisture in semi-open plastic bags under refrigeration at 4 °C, respiration monitoring must be conducted without prior water potential adjustment.•In such conditions,12 days between sampling and beginning of measurement did not affected respiration results.•The method used for agricultural soils gave different results and does not make sense for soils under perudic moisture regime.

Long-term, low technicality sewage sludge amendment and irrigation with treated wastewater under Mediterranean climate: impact on agronomical soil quality.

We evaluated the agronomic quality of loam to clay-loam soils from a Mediterranean area, which have been submitted for more than 10 years to irregular and poorly controlled treated wastewater (TWW) irrigation and sewage sludge (SS) amendment, both TWW and SS issuing from a domestic effluent treatment plant. A soil was submitted to SS amendment only, another to TWW irrigation only, another to both treatments, and another was not submitted to any of these treatments. We found that the agronomic quality of the treated soils has not decreased. In treated soils, it was observed a slight increase of pH, an increase of the cation exchange capacity, and no change of either salinity or electrical conductivity. Sodium adsorption ratio and exchangeable sodium percentage remained satisfactory, below 13 and 15, respectively, and no infiltration problems were observed, indicating that rainwater percolation was sufficient to leach the salt brought by SS or TWW. The soil organic matter (SOM) increased in all SS-amended and/or TWW-irrigated soils, the increase being higher in SS-amended soils. The SOM kept a satisfactory C/N ratio, lower than 15; the SUVA (Specific UV Absorbance) and E2/E3 index showed normal characteristics of the water-extracted organic matter (WEOC). Both SS amendment and TWW irrigation brought high amounts of nutrients in the considered soils and increased the nutrients disponibility, especially regarding K and P, as shown by the nutrient concentrations in the soil water extracts. The pH increase does not seem to be a problem for the bioavailability of trace elements, at least regarding Cu, Zn, Co, and Fe. Complementary studies should be undertaken for Ni. These observations highlight the potential agronomical benefits of application of wastewater and sewage sludge, even without great technicality, the better results being obtained using both SS amendment and TWW irrigation.

Fluorescence spectroscopy to study dissolved organic matter interactions with agrochemicals applied in Swiss vineyards.

UV/Vis fluorescence spectroscopy was used to study the possible interactions of dissolved organic matter (DOM) with the herbicide glyphosate and copper-based fungicide used in vineyards. The study focused on the role of DOM in the transport of these micropollutants from parcels to surface waters (river, lake). Soil solution and river water samples were collected in the Lavaux vineyard area, western Switzerland. Their fluorescence excitation emission matrices (EEM) were decomposed using parallel factor (PARAFAC) analysis, and compared to their content in glyphosate and copper. PARAFAC analysis of EEM of both types of samples showed the contribution of protein-like and humic-like fluorophores. In soil water samples, complexes between fulvic-like and humic-like fluorophores of DOM, copper, and glyphosate were likely formed. In surface water, DOM-copper and glyphosate-copper interactions were observed, but not between glyphosate and DOM.

Copper sorption on a straw lignin: experiments and EPR characterization.

Spectroscopic and physicochemical data, X-ray photoelectron spectroscopy (XPS), solid-state (13)C cross-polarization magic-angle-spinning NMR, GC/MS, specific surface area, site density, and surface acidity constants have been recorded or determined for a ligno-cellulosic substrate (LS) extracted from straw. Its copper(II)-bound ability has also been studied. The LS solid that exhibits two types of binding sites, carboxylic and phenolic groups, has a great affinity for copper(II), with a maximum of adsorption at around 4 mg g(-1) as early as the pH reaches 6. The structural characterization of the Cu(II) surface complexes has been investigated using EPR spectroscopy. The CuO(4) chromophore of the inner-sphere surface complexes is a slightly distorted square. A surface oxidation occurred simultaneously, which leads to semiquinonic radicals. Furthermore, our empirical approach, which used a correlation between thermodynamics data and EPR parameters, has led to a surface complexation constant log beta equal to 12.6. This indicates that copper(II) surface complexes are relatively stable.

Selective extraction of PAHs from a sediment with structural preservation of Natural Organic Matter.

Selective extraction of Polycyclic Aromatic Hydrocarbons (PAH) without structural modification of the Natural Organic Matter (NOM) from a heavily contaminated sediment was investigated using various solvents mixtures. Structural modification of the NOM was monitored after extraction using 3D-fluorescence spectroscopy. Better results were obtained with a 15-h PAH extraction under reflux with a dichloromethane/cyclohexane 20/80 mixture. The experimental procedure was validated with NOM standard materials before to be applied on natural sediments. It could be applied to any environmental solid sample such as sediments and soils.

Molecular scale speciation of first-row transition elements bound to ligneous material by using X-ray absorption spectroscopy.

To develop a solid scientific basis for maintaining soil quality and formulating effective remediation strategies, it is critical to determine how environmentally-important trace metals are sequestered in soils at the molecular scale. The speciation of Mn, Fe and Cu in soil organic matter has been determined by synchrotron-based techniques: extended X-ray absorption fine structure (EXAFS) and X-ray absorption near edge structure (XANES). We show the structural similarity between the surface complexes of Mn(II), Fe(III) and Cu(II). These cations are bound to the surface through oxygen atoms. Each one presents a more or less tetragonal-distorted octahedral geometry. The use of X-ray absorption spectroscopy provides a relevant method for determining trace-metal speciation in both natural and contaminated environmental materials.

Spectroscopic study of copper(II)--wheat straw cell wall residue surface complexes.

The sorption of copper(II) by wheat straw cell wall residue (CWR) was studied and revealed a relatively stable surface complexation on the acid sites of the substrate (carboxylic and phenolic moieties). The copper binding capacity at pH = 5.75 and ionic strength of 0.1 M was evaluated at 63 micromol x g(-1) CWR. The Langmuir and Freundlich isotherm equations were then used to describe the partitioning behavior for the system at different pH values. Batch experiments have been achieved in the presence of calcium in order to mimic the calcareous soil of the Champagne region. A competitive effect on copper complexation has been shown, which is presumably due to the calcium ability to form outer-sphere complexes far less stable than copper(II) ones. Electron spin resonance and X-ray absorption spectroscopy were combined to obtain information on the geometry and structure of Cu bound to CWR. At least two different binding sites for Cu2+ were found to take place in CWR. From ESR parameters, we deduced that copper(II) ions, when complexed with CWR, are coordinated in a square-planar arrangement with four oxygen-containing groups. EXAFS and XANES experiments revealed that Cu(II) is surrounded by four oxygen atoms, with an average Cu-O equatorial distance equal to 1.94 A.

Preparation of Re(I)- and (99m)Tc(I)-metallocarboranes in water under weakly basic reaction conditions.

A new method for the preparation of Re- and (99m)Tc-metallocarboranes in water under mild reaction conditions was developed. Three nido-carborane ligands were reacted with [Re(CO)(3)Br(3)](2)(-) in the presence of aqueous potassium fluoride to give the corresponding eta(5)-Re(CO)(3)-carborane complexes. The use of KF as a base afforded the desired Re-metallocarboranes in good yields while avoiding the formation of Re clusters, which are byproducts commonly observed when reactions are carried out in the presence of strong aqueous bases. The reaction was also performed at the tracer level producing the first (99m)Tc-carborane complex, which was isolated in 80% radiochemical yield following a simple Sep-Pak purification process. The resulting organometallic complex was stable to cysteine and histidine challenges for more than 24 h.

Structural Characterization and Iron(III) Binding Ability of Dimeric and Polymeric Lignin Models.

To understand the complexation in solution and the sorption of iron(III) on soluble and solid fractions of lignin, a dimeric model (guaiacyl-beta-guaiacylglycerol ether, called beta-O-4) and a polymeric model (dehydrogenation polymer resulting from polymerization of coniferyl alcohol) of lignin have been synthesized and characterized with chromatographic, solution, and solid state (13)C CP-MAS NMR and XPS spectroscopies. The beta-O-4 dimer is a monoacid (HL). Potentiometric studies in aqueous solution at 25 degrees C and 1 mol L(-1) ionic strength (KNO(3)) indicated formation of two stable complexes, FeL(2+) and probably FeL(OH)(+), which shows that the soluble fraction of lignin binds metals, indicating that they are transported by water through the soils. The binding of iron(III) on the DHP polymer was then investigated. The sorption experiments have shown a great affinity of iron for the solid with a maximum of adsorption since pH 5. A pulsed-ESR study has revealed surface oxidation by the iron(III) cation, which leads to iron(II) and semiquinonic radicals on the polymer surface, with a radical concentration of about 5x10(17) spin/g. Copyright 2001 Academic Press.