Successful removal of fluoride from aqueous environment using Al(OH)3@AC: column studies and breakthrough curve modeling.

In this study, we discuss the removal of fluoride from water through column adsorption methods using Al(OH)3@AC as a functional granular activated carbon. The height of the bed, fluoride concentration, and flow rate are the experimental factors used to obtain the breakthrough curves. As the flow rate increased, the breakthrough and saturation times decreased. The analysis of simplified column models, such as the Adams-Bohart, Thomas, and Yoon-Nelson models, revealed that the Clark model best described the adsorption process when fitting the experimental data. The obtained breakthrough curves agreed with the corresponding experimental data. The highest capacity for adsorption obtained during the column procedure was found to be 41.84 mg g-1 with a bed height of 3 cm, an initial fluoride concentration of 10 mg L-1 and a flow rate of 7.5 mL min-1.

Surface modification of biomaterials based on cocoa shell with improved nitrate and Cr(vi) removal.

The present work addresses the development of simple, low-cost and eco-friendly cocoa-shell-based materials for efficient removal of heavy metal hexavalent chromium (Cr(vi)), and toxic nitrate (NO3 -) from aqueous solution. A conventional treatment process was used to purify cocoa shell (CS) into an adsorbent, followed by chemical grafting of dendrimers to promote its surface properties for nitrate and Cr(vi) removal. The morphology, surface charge, structure and stability of the new adsorbent were investigated by scanning electron microscopy, Fourier transform infrared and UV-visible spectroscopies, zeta potential, X-ray photoelectron spectrometry, and differential scanning calorimetry. The successful chemical grafting of the dendrimer (polyethyleneimine, PEI) onto purified CS was confirmed. CS-T-PEI-P proved to be a very efficient candidate for the removal of nitrate and chromium(vi). Removal of the two pollutants at different initial concentrations and pH values was studied and discussed. Sorption of chromium and nitrate was found to obey 2nd-order kinetics and a Freundlich-type isotherm, affording an uptake adsorption of 16.92 mg g-1 for NO3 - and 24.78 mg g-1 for Cr(vi). These results open promising prospects for its potential applications as a low cost catalyst in wastewater treatment.

Silver nanoparticle embedded copper oxide as an efficient core-shell for the catalytic reduction of 4-nitrophenol and antibacterial activity improvement.

A facile and eco-friendly method was developed to prepare a microporous CuO@Ag0 core-shell with high catalytic and antibacterial activities. Scanning and transmission electron microscopy revealed a preponderance of nearly spherical 50 nm particles with slight structure compaction. Comparison of the hysteresis loops confirmed the structure compaction after AgNP incorporation, and a significant decrease of the specific surface area from 55.31 m2 g-1 for CuO to 8.03 m2 g-1 for CuO@Ag0 was noticed. A kinetic study of 4-nitrophenol (4-NP) reduction into 4-aminophenol (4-AP) with sodium borohydride revealed a first order reaction that produces total conversion in less than 18 minutes. CuO@Ag0 also exhibited appreciable antibacterial activity against Staphylococcus aureus. The antibacterial effects were found to strongly depend on the size, contact surface, morphology and chemical composition of the catalyst particles. The addition of Ag0-NPs produced more reactive oxygen species in the bacteria medium. These results open promising prospects for its potential applications as a low cost catalyst in wastewater treatment and antibacterial agent in cosmetics.

Low effect of phenanthrene bioaccessibility on its biodegradation in diffusely contaminated soil.

This study focused on the role of bioaccessibility in the phenanthrene (PHE) biodegradation in diffusely contaminated soil, by combining chemical and microbiological approaches. First, we determined PHE dissipation rates and PHE sorption/desorption isotherms for two soils (PPY and Pv) presenting similar chronic PAH contamination, but different physico-chemical properties. Our results revealed that the PHE dissipation rate was significantly higher in the Pv soil compared to the PPY soil, while PHE sorption/desorption isotherms were similar. Interestingly, increases of PHE desorption and potentially of PHE bioaccessibility were observed for both soils when adding rhamnolipids (biosurfactants produced by Pseudomonas aeruginosa). Second, using 13C-PHE incubated in the same soils, we analyzed the PHE degrading bacterial communities. The combination of stable isotope probing (DNA-SIP) and 16S rRNA gene pyrosequencing revealed that Betaproteobacteria were the main PHE degraders in the Pv soil, while a higher bacterial diversity (Alpha-, Beta-, Gammaproteobacteria and Actinobacteria) was involved in PHE degradation in the PPY soil. The amendment of biosurfactants commonly used in biostimulation methods (i.e. rhamnolipids) to the two soils clearly modified the PHE sorption/desorption isotherms, but had no significant impact on PHE degradation rates and PHE-degraders identity. These results demonstrated that increasing the bioaccessibility of PHE has a low impact on its degradation and on the functional populations involved in this degradation.

Synthesis and properties of ZnO-HMD@ZnO-Fe/Cu core-shell as advanced material for hydrogen storage.

In this paper, a new synthetic strategy towards functionalized ZnO-HMD@ZnO-Fe/Cu core-shell using sol-gel process modified by chemical grafting of hexamethylenediamine (HMD) on the core and in-situ dispersion of Cu0/Fe0 as metallic nanoparticles (M-NPs) on the shell. The as-prepared core-shell materials were fully characterized by transmission electron microscopy, X-ray powder diffractometry, diffuse reflectance and FT-IR spectrophotometery, photoluminescence, and complexes impedance spectroscopy measurements. The XRD patterns agreed with that of the ZnO typical wurtzite structure, indicating good crystallinity of ZnO-HMD@ZnO-Fe/Cu, with the presence of Fe0 and Cu0 phases. Hexamethylenediamine grafting and M-NPs insertion were highly activated and enhanced the core and shell interface by the physiochemical interaction. After functionalization, luminescence intensities and electrical properties of both core and core-shell nanoparticles are improved, indicating the effects of the surface groups on the charge transfer of ZnO-HMD@ZnO-Fe/Cu. The hydrogen capacity retention was depended strongly on the composition and structure of the obtained core-shell. Iron/Copper-loaded ZnO-HMD@ZnO materials exhibited the highest capacity for hydrogen storage. The excellent stability and performance of the ZnO-HMD@ZnO-Fe/Cu core-shell make it an efficient candidate for hydrogen storage.

Influence of the vegetative cover on the fate of trace metals in retention systems simulating roadside infiltration swales.

Large-scale outdoor mesocosms were designed and co-contaminated with metals (Cd, Pb, Zn) and organic compounds to better understand the complex functioning of urban roadside swale environments. Infiltration systems were planted with macrophytes (P. arundinaceae, J. effusus and I. pseudacorus) or grassed, and natural or spiked target metals were monitored over two years. In the non-spiked mesocosms, atmospheric metal inputs were slightly higher than outputs, leading to low metal accumulation in topsoils and to very low outflow water contamination (<0.7% of the initial metal stock). In the spiked infiltration systems that simulated point pollution through water inflow, transfer of the initial stock of metals to the deeper soil layers was quite low and outflow water contamination was very low (<0.6% of the initial stock). The main metal output from these systems occurred in the first days of their installation because of the high metal solubility in water and insufficient plant cover at that time. The infiltration systems stabilized after a few weeks, probably because of stronger sorption to soil aggregates, and because of plant root development. Mephytoextraction in plant roots was more efficient in mesocosms planted with P. arundinacea and grass. Metal phytoextraction in plant aerial parts was also better for grass and P. arundinacea, when considering metal standing stocks instead of their concentration in plants. J. effusus was a good metal accumulator, but its low aboveground biomass development was less favorable to metal removal through harvesting.

Alternative techniques to HPCD to evaluate the bioaccessible fraction of soil-associated PAHs and correlation to biodegradation efficiency.

The total amount of polycyclic aromatic hydrocarbons (PAHs) in soils, given by exhaustive chemical extractions, does not relate directly to environmental risk, since only a fraction may be accessible to soil organisms. The rapid PAH desorbing fraction (Frap), which is weakly and reversibly sorbed to soils, is called the bioaccessible fraction, and can be estimated by non-exhaustive aqueous extractions. In order to better estimate Frap, different mild-extractants were tested, such as various cyclodextrins, surfactants and butanol. Their extractability performances were correlated to the Kd partition coefficients of seven PAHs obtained through sorption isotherms from five soils, but also to the PAHs molecular size and to the amounts of organic matter and of some clays (smectites and kaolinites). If hydroxypropyl-ß-cyclodextrin was actually a good extractant to assess PAH accessibility, the polymer of carboxymethyl-ß-cyclodextrin (pCMCD) was better (with a lower cost) to estimate the rapid mass transfer between soil particles and the soil solution, depending also on soil ageing. But Frap, estimated through pCMCD extractions, did not reflect the biodegradation of the PAHs after three months in soil microcosms. The chemical method underestimated the dissipation of 3-4 ring PAHs and overestimated that of 5-6 ring PAHs. So biodegradation was not only limited by PAHs mass-transfer, but also by biological factors, favoring the access of microorganisms to residual strongly sorbed fractions of 3-4 ring PAHs, and inhibiting the degradation of accessible but highly toxic 5-6 ring PAHs.

Assessment of PAH dissipation processes in large-scale outdoor mesocosms simulating vegetated road-side swales.

Biofilters have been implemented in urban areas due to their ability to improve road runoff quality. However, little is known about the role of soil microorganisms and plants on pollutant remediation in planted swales. Therefore, four large-scale outdoor mesocosms were built and co-contaminated with metals and model polycyclic aromatic hydrocarbons (PAHs) (phenanthrene (Phen), pyrene (Pyr) and benzo[a]pyrene (BaP)), to better understand the complex functioning of swale-like environments. Three macrophyte plant species were tested for enhanced remediation of PAHs: Juncus effusus, Iris pseudacorus, Phalaris arundinacea and a grass mix. Long-term dynamics of PAHs in water outflow and soil was studied. Results showed that only 0.07 to 0.22% of total PAHs were released in water outflow after one year. Two years after contamination, soil sample analyses showed a dissipation of 99.6% for Phen and 99.4% for Pyr whatever the mesocosm considered and ranging from 75.5 to 91% for BaP, depending on plant species. Furthermore, dissipation time-courses may be described by a biphasic process. Experiments showed that the grass mix facilitated BaP long-term biodegradation. Grass appeared also to be the best filter for suspended solids because of its dense rhizosphere, which prevents the transfer of BaP to groundwater.

Application of biosurfactants and periodic voltage gradient for enhanced electrokinetic remediation of metals and PAHs in dredged marine sediments.

Dredged harbor sediment co-contaminated by heavy metals and polycyclic aromatic hydrocarbons (PAHs) was subjected to enhanced electrokinetic treatments, using a mixture of a chelating agent (citric acid CA) and a surfactant as additives in the processing fluids. We tested various operating conditions (at 1 V cm(-1)): different CA concentrations, applying a periodic voltage gradient, pre-conditioning the sediment with the additives, and replacing the synthetic surfactant Tween 20 (TW20) by biosurfactants. Increasing the CA concentration was favorable for both metal and PAH removal. Applying a periodic voltage gradient associated to a low concentration of CA and TW20 provided the best results for Zn, Cd and Pb removal and also for removal of the 16 priority PAHs. Promising results were obtained with solutions containing rhamnolipids (0.028%) and a viscosin-like biosurfactant produced by Pseudomonas fluorescens Pfa7B (0.025%), associated to a periodic voltage gradient. Although the rhamnolipid and the viscosin-like compounds involved a higher electrical current than TW20, metals were less removed from the sediment. The electroosmotic flow was lower when we used biosurfactants, hence a less effective effect on PAH removal.

Correlations between PAH bioavailability, degrading bacteria, and soil characteristics during PAH biodegradation in five diffusely contaminated dissimilar soils.

The natural biodegradation of seven polycyclic aromatic hydrocarbons (PAHs) by native microorganisms was studied in five soils from Normandy (France) from diffusely polluted areas, which can also pose a problem in terms of surfaces and amounts of contaminated soils. Bioavailability tests using cyclodextrin-based extractions were performed. The natural degradation of low molecular weight (LMW) PAHs was not strongly correlated to their bioavailability due to their sorption to geosorbents. Conversely, the very low degradation of high molecular weight (HMW) PAHs was partly correlated to their poor availability, due to their sorption on complexes of organic matter and kaolinites or smectites. A principal component analysis allowed us to distinguish between the respective degradation behaviors of LMW and HMW PAHs. LMW PAHs were degraded in less than 2-3 months and were strongly influenced by the relative percentage of phenanthrene-degrading bacteria over total bacteria in soils. HMW PAHs were not significantly degraded, not only because they were less bioavailable but also because of a lack of degrading microorganisms. Benzo[a]pyrene stood apart since it was partly degraded in acidic soils, probably because of a catabolic cooperation between bacteria and fungi.

Investigation of the release of PAHs from artificially contaminated sediments using cyclolipopeptidic biosurfactants.

Polycyclic aromatic hydrocarbons (PAHs) can be preponderant in contaminated sediments and understanding how they are sorbed in the different mineral and organic fractions of the sediment is critical for effective removal strategies. For this purpose, a mixture of seven PAHs was studied at the sediment/water interface and sorption isotherms were obtained. The influence of various factors on the sorption behavior of PAHs was evaluated, such as the nature of minerals, pH, ionic strength and amount of organic matter. Afterwards, the release of PAHs from the sediment by surfactants was investigated. The effectiveness of sodium dodecyl sulfate (SDS) was compared to natural biosurfactants, of cyclolipopeptidic type (amphisin and viscosin-like mixture), produced by two Pseudomonas fluorescens strains. The desorption of PAHs (from naphthalene to pyrene), from the highly retentive kaolinite fraction, could be favored by adding SDS or amphisin, but viscosin-like biosurfactants were only effective for 2-3 ring PAHs desorption (naphthalene to phenanthrene). Moreover, while SDS favors the release of all the target PAHs from a model sediment containing organic matter, the two biosurfactants tested were only effective to desorb the lowest molecular weight PAHs (naphthalene to fluorene).

A study by spectroelectrochemical FTIR and density functional theory calculations of the reversible complexing ability of an electroactive tetrathiafulvalene crown.

We report on the study of the electrochemically targeted complexation/expulsion of a metal cation (Ba2+) by a crown ether tetra(thiomethyl)tetrathiafulvalene derivative (crown-TTM-TTF). Real time, in situ FTIR spectroelectrochemistry was used to obtain spectroscopic evidence of this electrochemically triggered phenomenon. Density functional theory calculations allowed the spectral information collected to be assigned. Both experimental and theoretical results clearly show that neutral crown-TTM-TTF complexes well Ba2+. Complexation is evidenced by a significant downshift of the frequency corresponding to the asymmetric stretching of the C-O-C ether groups. Concerning the cation crown-TTM-TTF, the spectroscopic signal of the complex form was difficult to identify, first because of the rather low value of the complexation constant and second because the vibration modes involving the oxygen atoms (which are the most affected by the complexation) were found by calculation to occur in the lower spectral region (<1000 cm(-1)), which is not accessible in our experimental conditions. In the case of the dication crown-TTM-TTF, it is now clear that the complex form does not exist, which means that the electrochemical formation of the dication necessarily involves the expulsion of the barium ion.

Tetrathiafulvalene crowns: redox-switchable ligands.

A series of redox-responsive ligands that associate the electroactive tetrathiafulvalene core with polyether subunits of various lengths has been synthesized. X-ray structures are provided for each of the free ligands. The requisite structural criteria for reaching switchable ligands are satisfied for the largest macrocycles, that is, planarity of the 1,1',3,3'-tetrathiafulvalene (TTF) pi system and correctly oriented coordinating atoms. The ability of these ligands to recognize various metal cations as a function of the cavity size has been investigated by various techniques (LSIMS, 1H NMR, and UV/Vis spectroscopy, cyclic voltammetry). These systems exhibit an unprecedented high coordination ability among TTF crown ethers. Their switchable ligating properties have been confirmed by cyclic voltammetry, and metal-cation complexation has been illustrated by X-ray structures of three of the corresponding metal complexes (Pb2+, Sr2+, and Ba2+). Solid-state structures of these complexes display original packing modes with channel-like arrangements.