Interaction of pyrene fluoroprobe with natural and synthetic humic substances: Examining the local molecular organization from photophysical and interfacial processes.

The direct and indirect interaction mechanisms of pyrene with: (i) various molecular weight fractions of a synthetic humic-like substance (SyHA) and (ii) extracts of natural humic acids (NHA) from Moselle River suspended matter were investigated using quenching fluorescence and surface tension measurements. Humic materials were characterized in a previous study. The Stern-Volmer associative constants were determined from the quenching technique. Surface tension measurements revealed an increase in surface activity as a function of concentration for each humic fraction independently of the pyrene presence in solution, even during the formation of humic micelles. The results obtained suggest the possibility of specific intermolecular interactions occurring during pyrene entrapment within humic acids. In addition, we show that molecular weight, aliphatic chains (especially those containing nitrogen groups) and number of acidic groups are determinant characteristics for pollutant entrapment capacity at concentrations below the critical micellar concentration (CMC) of humic substances.

Chemical coagulation of combined sewer overflow: heavy metal removal and treatment optimization.

The coagulation of combined sewer overflow (CSO) was investigated by jar-testing with two commercial coagulants, a ferric chloride solution (CLARFER) and a polyaluminium chloride (WAC HB). CSO samples were collected as a function of time during various wet-weather events from the inlet of Boudonville retention basin, Nancy, France. Jar-tests showed that an efficient turbidity removal can be achieved with both coagulants, though lower optimum dosages and higher re-stabilization concentrations were obtained with the aluminum-based coagulant. Optimum turbidity removal also yielded effective heavy metal elimination. However, the evolution with coagulant dosage of Cu, Zn, Pb, Cr, soluble and suspended solids contents followed various patterns. The removal behaviors can be explained by a selective aggregation of heavy metal carriers present in CSO and a specific interaction between hydrolyzed coagulant species and soluble metals. Stoichiometric relationships were established between optimal coagulant concentration, range of optimal dosing, and CSO conductivity, thus providing useful guidelines to adjust the coagulant demand during the course of CSO events.

Synthesis of a red iron oxide/montmorillonite pigment in a CO2-rich brine solution.

The homoionic calcium-montmorillonite was used to synthesize a red iron oxide/clay pigment in a CO2-rich brine solution (0.5 M of NaCl) by using an agitated batch-reactor (engineer autoclave). The operating conditions were 15 days of reaction, 200 bars of pressure and 150 degrees C of temperature. SEM/EDS, STEM/EDS, XRD and Infrared Spectrometry were performed to characterize before and after reaction the solid phase. The results showed the precipitation of spherical nanoparticles (50-500 nm) of iron oxide (Fe2O3) dispersed and/or coagulated in the clay-matrix. Evidently, this oxide produced red coloration in the final product. For this case, the Fe3+ cation was provided to the aqueous solution by the dissolution of Ca-montmorillonite, particularly, the dissolution of most fine particles contained in the starting clay material. The cation exchange process and precipitation of polymorph silica were also observed.

Low-pressure argon adsorption assessment of micropore connectivities in activated carbons.

Low-pressure argon adsorption has been used to study the energetic distribution of microporous activated carbons differing by their burn-off. The collected isotherms were analyzed using the derivative isotherm summation method. Some oscillations on the experimental curves for very low partial pressures were detected. The results are analyzed and discussed according to the literature and could be attributed to local overheating caused by spontaneous mass transfer of argon through constrictions between former pores and the new opening pore or deadend pores. We used the dynamic character of the experimental method and mainly the discrepancy of the quasi-equilibrium state to deduce key parameters related to the porosity topology.

Role of exchangeable cations on geometrical and energetic surface heterogeneity of kaolinites.

Textural and energetic proprieties of kaolinite were studied by low-pressure argon adsorption at 77 K. The heterogeneity of four kaolinites (two low-defect and two high-defect samples) modified on their surface by cation exchange with Li+, Na+, or K+ was studied by DIS analysis of the derivative argon adsorption isotherms. The comparison between the derivative adsorption isotherms shows that the nature of the surface cation influences the adsorption phenomena on edge and basal faces. In the case of basal faces, two adsorption domains are observed: for the first one, argon adsorption is slightly sensitive to the nature of the surface cation; for the second one, argon adsorption energy depends on the nature of surface cation suggesting their presence on theoretically uncharged basal faces. This study also shows that the shape of elementary particles, as derived from basal and edge surface areas, changes with the nature of cation. This anomalous result is due to the decrease of edge surface area with increasing the size of the cation. This surface cation dependence can be accounted for the area occupied by the edge surface cations in the first argon monolayer.

Assessment of the surface areas of silica and clay in acid-leached clay materials using concepts of adsorption on heterogeneous surfaces.

Two clays of the areas of Kaélé and Kousseri (extreme North Cameroon) containing mainly smectites and minor amounts of kaolinite were activated with sulfuric acid (1 to 8 N). Crystal-chemical properties were studied using X-ray diffraction, Fourier transform infrared spectroscopy, and chemical analysis, while textural properties were analyzed by step-by-step nitrogen adsorption at 77 K and low-pressure quasi-equilibrium argon adsorption at 77 K. As is generally observed, smectite is more sensitive to acid leaching than kaolinite. As a result of smectite decomposition, amorphous Al-containing silica forms, leading to an increase in the specific surface area of the leached materials. The content of the clay minerals and amorphous silica can be estimated on the basis of changes in the chemical composition of the samples upon acid leaching. As far as adsorption energy distributions derived from low-pressure argon derivative adsorption isotherms are concerned, the main modifications occur when 1 N sulfuric acid is used, due to the replacement of calcium and sodium compensating cations by protons. When higher acid concentrations are used, variations in adsorption energy distribution can be assigned to the presence of amorphous silica. It was possible to model experimental adsorption energy distributions as weighted sums of argon adsorption energy distributions obtained on (i) 1 N samples representing protonated clays and (ii) a silica gel used as a reference aluminous silica. Using such an approach, increasing acid concentration results in an increase in the surface area of silica, whereas the surface area of the remaining clay minerals remains roughly constant.

Separation of hydrocarbons and lipid from water using treated bark.

This paper explores the possibility of using treated bark to remove oily compounds from water. Bark was first biologically or chemically treated and saturated with transition metal ions (TMI) to avoid the release of soluble organic compounds from the bark in the treated effluents. Several experimental parameters affecting the oil removal efficiency (RE) were studied (initial oil concentration, temperature, time, etc.). Saturated bark was characterized using Fourier transform infrared (FTIR) spectroscopy and bark wetting index was determined. Results of the retention of lipids suggested that their removal could exceed 95% of initial oil concentration. The uptake of lipid by treated bark varied from 0.2 to 2.0 g of organic oil/g of dry sorbent. No significant chemical modifications of saturated bark were observed in infrared spectroscopy after the sorption of oleic acid on bark treated with transition metal ions. The structure of adsorbed tridimensional layer of oleic acid molecules seemed to take place through the double bond. The hydrocarbon RE exceeded 95% using oil-water mixture with a hydrocarbon/bark ratio of one. The sorption reaction of hydrocarbons and lipids was quasi-instantaneous and seemed to be influenced by the temperature. This indicated that the retention mechanism was related to the capillary action. Results of FTIR spectroscopy suggested that no chemical bonds between barks and oily compounds were established.

Structural and Energetic Nonuniformities of Pyrocarbon-Mineral Adsorbents.

Several series of pyrocarbon-mineral adsorbents (carbosils) were studied using the nitrogen adsorption method to compute structural and energetic parameters within the scope of overall adsorption isotherm approximation applying a regularization procedure with consideration for surface heterogeneity. A portion of pyrocarbon deposits (graphene clusters) fills mesopores of the oxide supports, but another portion represents relatively large nonporous pyrocarbon globules formed on the outer surfaces of the oxide matrices. Contributions of these two types of pyrocarbon deposits depend on the nature of oxide matrices and carbonized precursors. The characteristics of pyrocarbon formed on the silica (silica gel, fumed silica) surfaces differ from those for deposits prepared on the surfaces of titania/silica and alumina/silica or by the pyrolysis of metal acetylacetonates (Zr(AcAc)(4), TiO(AcAc)(2), Ni(AcAc)(2), Zn(AcAc)(2), Cr(AcAc)(3), Co(AcAc)(2)) on mesoporous silica gel. The structural and energetic characteristics estimated using the adsorption method with consideration for the adsorbent heterogeneity are fruitful for comparative analysis of the (1)H NMR spectra of water adsorbed on carbosils from the gas phase or unfrozen in the aqueous suspensions at T < 273 K. Copyright 2001 Academic Press.

Characterization of Titania/Silica Gel by Means of Low-Pressure Nitrogen Adsorption.

Adsorbents synthesized by grafting of titania onto mesoporous silica gel surfaces at different temperatures were studied by means of nitrogen adsorption-desorption and water desorption. The pore size distribution f(R(p)) of titania/silica gel depends on the titania concentration (C(TiO(2))) and the temperature of titania synthesis. Nonuniformity of TiO(2) phase is maximal at a low C(TiO(2)) value (3.2 wt.% anatase deposited at 473 K), and two peaks of the fractal dimension distribution f(D) are observed at such a concentration of titania, but at larger C(TiO(2)) values, only one f(D) peak is seen. More ordered filling of pores and adsorption sites by nitrogen, reflecting in the shape of adsorption energy distributions f(E) at different pressures of adsorbate, is observed for adsorbent with titania (rutile+anatase) grafted on silica gel at a higher temperature (673 K). Copyright 2000 Academic Press.