Compositions and mobility of major, δD, δ18O, trace, and REEs patterns in water sources at Benue River Basin-Cameroon: implications for recharge mechanisms, geo-environmental controls, and public health.

Hydro-geochemical data are required for understanding of water quality, provenance, and chemical composition for the 2,117,700 km2 Niger River Basin. This study presents hydro-geochemical analysis of the Benue River Basin, a major tributary of the Niger River. The distribution of major ions, Si, δD, and δ18O, trace and rare-earth elements (TE and REEs, respectively) composition in 86 random water samples, revealed mixing of groundwater with surface water to recharge shallow aquifers by July and September rains. Equilibration of groundwater with kaolinite and montmorillonites, by incongruent dissolution, imprints hydro-chemical signatures that vary from Ca + Mg - NO3 in shallow wells to Na + K - HCO3 in boreholes and surface waters, with undesirable concentrations of fluoride identified as major source of fluorosis in the local population. Our results further indicate non-isochemical dissolution of local rocks by water, with springs, wells and borehole waters exhibiting surface water-gaining, weakest water-rock interaction, and strongest water-rock interaction processes, respectively. Poorly mobile elements (Al, Th and Fe) are preferentially retained in the solid residue of incongruent dissolution, while alkalis, alkaline earth and oxo-anion-forming elements (U, Mo, Na, K, Rb, Ca, Li, Sr, Ba, Zn, Pb) are more mobile and enriched in the aqueous phase, whereas transition metals display an intermediate behavior. Trace elements vary in the order of Ba > Sr > Zn > Li > V > Cu > Ni > Co > As > Cr > Sc > Ti > Be > Pb > Cd, with potentially harmful elements such as Cd, As, and Pb mobilized in acidic media attaining near-undesirable levels in populated localities. With the exception of Y, REEs distribution in groundwater in the order of Eu > Sm > Ce > Nd > La > Gd > Pr > Dy > Er > Yb > Ho > Tb > Tm differs slightly with surface water composition. Post-Archean Average Australian Shale-normalized REEs patterns ranging from 1.08 to 199 point to the dissolution of silicates as key sources of trace elements to groundwater, coupled to deposition by eolian dust.

Reuse of solid petroleum waste in the manufacture of porcelain stoneware tile.

This study investigates the incorporation of solid petroleum waste as raw material into a porcelain stoneware tile body, in replacement to natural kaolin material by up to 5 wt.%. Tile formulations containing solid petroleum waste were pressed and fired at 1240 °C by using a fast-firing cycle. The tile pieces were tested to determine their properties (linear shrinkage, water absorption, apparent density, and flexural strength), sintered microstructure, and leaching toxicity. The results therefore indicated that the growing addition of solid petroleum waste into tile formulations leads to a decrease of linear shrinkage, apparent density, and flexural strength, and to an increase of water absorption of the produced tile materials. It was also found that the replacement of kaolin with solid petroleum waste, in the range up to 2.5 wt.%, allows the production of porcelain stoneware tile (group BIa, ISO 13006 standard). All concentrations of Ag, As, Ba, Cd, Cr (total), Hg, and Pb of the fired porcelain stoneware tile pieces in the leachate comply with the current regulatory limits. These results indicate that the solid petroleum waste could be used for high-quality porcelain stoneware tile production, thus giving rise to a new possibility for an environmentally friendly management of this abundant waste.

Controlled release formulations of acephate: water and soil release kinetics.

Controlled release formulations of insecticide acephate (O,S-dimethyl acetylphosphoramidothioate) have been prepared using commercially available polyvinyl chloride, carboxy methyl cellulose and carboxy methyl cellulose with kaolinite. Kinetics of acephate release in soil and water from the different formulations was studied in comparison with the commercially available formulation 75 DF. Release from the commercial formulation was faster than the new controlled pesticide release (CR) formulations. Addition of clay in the carboxy methyl cellulose matrix reduced the rate of release. The diffusion exponent (n value) of acephate in water and soil ranged from 0.462 to 0.875 and 0.420 to 0.547 respectively in the tested formulations. The release was diffusion controlled with a half release time (T(1/2)) of 2.97 to 52.41 days in water and 2.98 to 76.38 days in soil from different matrices. The maximum release of acephate in water and soil from controlled released formulations occurred between 6.33 to 36.34 and 12.49 to 29.09 days respectively. The results suggest that depending upon the polymer matrix used, the application rate of acephate can be optimized to achieve insect control at the desired level and period.

Structural characteristics of humic-like acid from microbial utilization of lignin involving different mineral types.

This paper determines the impact of two clay minerals (kaolinite and montmorillonite) and three oxides (goethite, δ-MnO2, and bayerite) on the elemental composition and FTIR spectra of humic-like acid (HLA) extracted from microbial-mineral residue formed from the microbial utilization of lignin in liquid shake flask cultivation. Goethite, bayerite, and δ-MnO2 showed higher enrichment capabilities of C and O + S in the HLA than kaolinite and montmorillonite. Goethite showed the highest retention of organic C, followed by bayerite, but kaolinite exhibited the least exchangeability. Kaolinite and montmorillonite enhanced microbial consumption of N, resulting in the absence of N in HLA. A few aliphatic fractions were preferentially gathered on the surfaces of kaolinite and montmorillonite, making the H/C ratios of HLA from the clay mineral treatments higher than those of HLA from the oxide treatments. δ-MnO2 was considered the most effective catalyst for abiotic humification, and goethite and bayerite ranked second and third in this regard. This trend was proportional to their specific surface areas (SSAs). However, comparing the effects of different treatments on the promotion of HLA condensation by relying solely on the SSA of minerals was not sufficient, and other influencing mechanisms had to be considered as well. Additionally, Si-O-Al and Si-O of kaolinite participated in HLA formation, and Si-OH, Si-O, and Si-O-Al of montmorillonite also contributed to this biological process. Fe-O and phenolic -OH of goethite, Mn-O of δ-MnO2, and Al-O of bayerite were all involved in HLA formation through ligand exchange and cation bridges. Lignin was better protected from microbial decomposition by the kaolinite, bayerite, and δ-MnO2 treatments, which caused lignin-like humus (HS) formation. Under the treatments of δ-MnO2, goethite, and bayerite, HLA showed a greater degree of condensation compared to HLA precipitated by kaolinite and montmorillonite. Contributions from Si-O, and Si-O-Al of clay minerals, and Fe-O, Mn-O, and Al-O of oxides were the mechanisms by which minerals catalyzed the formation of HS from lignin.

Experimental study on flue gas purifying of MSW incineration using in-pipe jet adsorption techniques.

This paper presents the experimental research process and results about flue gas purifying of municipal solid wastes (MSW) incineration using in-pipe jet adsorption techniques. MSW incineration was carried out in a fluidized bed test rig, and the flue gas purifying was carried out in an in-pipe jet adsorption test rig. The experimental results are as follows: when the feedstock of activated carbon is 1.6g/Nm(3), the desulfurization efficiency is 83%, the denitrification efficiency is 41%, and the dechlorination efficiency is 27%. The order of purifying effect of the three kinds of adsorbents on acidic gases from MSW incineration is activated carbon>activated bauxite>kaolin. Comparison of adsorption capabilities of the three kinds of adsorbents to heavy metals shows that activated carbon is the best additive to remove Cd, Pb and Cu, kaolin is inferior, and activated bauxite is the worst one. However, activated bauxite is the best additive to remove Hg, and it can remove Cd effectively. PAHs in fly ash are dominated by three-, four-, and five-ringed PAHs, and PAHs in the flue gas mainly include three- and four-ringed PAHs. When the injected quantity of additive is constant, the order of cleaning effect on PAHs is kaolin>activated carbon>activated bauxite. These three kinds of adsorbents have different purifying effects on acidic gases, heavy metals and PAHs in the flue gas from MSW incineration. In general, activated carbon has a better adsorption capability.

Modification of clay barriers with a cationic surfactant to improve the retention of pesticides in soils.

In this work, the efficiency of reactive clay barriers in the immobilisation of organic pesticides in a sandy soil was studied. Reactive barriers were prepared by modification of montmorillonite, kaolinite and palygorskite clay minerals, and of a clayey soil with the cationic surfactant octadecyltrimethylammonium bromide (ODTMA). Percolation curves of the pesticides linuron, atrazine and metalaxyl of different hydrophobic character, were obtained in columns packed with a natural sandy soil with these barriers intercalated under saturated flow conditions. The cumulative curves in the unmodified soil indicated a leaching of pesticides greater than 85% of the total amount of compound added. After barrier intercalation, the breakthrough curves (BTC) indicated a dramatic decrease in the amounts of linuron leached in all columns and a significant modification of the leaching kinetics of atrazine and metalaxyl. Retardation factors, R, of the pesticides in the columns were significantly correlated with the organic matter content (OM) derived from the ODTMA of the organo clay/soil barriers (r2>or=0.78). Significant correlations were also found between these R factors and the pore volume values corresponding to the maximum peaks of the BTCs (r2=0.83; p<0.01) or the total volumes leached (r2=0.44; p<0.05) for the pesticides atrazine and metalaxyl. The results obtained point to the interest in the use of reactive clay barriers for almost complete immobilisation of hydrophobic pesticides or for decreasing the leaching of moderately hydrophobic pesticides coming from point-like sources of pollution. These barriers would avoid the generation of elevated concentrations of these compounds in the soils due to their rapid washing.

Uptake properties of Ni2+ by nCaO.Al2O3.2SiO2 (n=1-4) prepared from solid-state reaction of kaolinite and calcite.

A series of nCaO.Al2O3.2SiO2 samples (n=1-4) were prepared by solid-state reaction of mechanochemically treated mixtures of kaolinite and calcite fired at 600-1000 degrees C for 24 h. All the samples were X-ray amorphous after firing at 600-800 degrees C but had crystallized by 900 degrees C. The main crystalline phases were anorthite (n=1), gehlenite (n=2 and 3) and larnite (n=4). The uptake of Ni2+ by nCaO.Al2O3.2SiO2 samples fired at 800 and 900 degrees C was investigated at room temperature using solutions with initial Ni2+ concentrations of 0.1-50 mmol/l. Amorphous samples (fired at 800 degrees C) showed a higher Ni2+ uptake capacity than crystalline samples (fired at 900 degrees C). Ni2+ uptake was found to increase with increasing of CaO content. Amorphous 4CaO.Al2O3.2SiO2 showed the highest Ni2+ uptake capacity (about 9 mmol/g). The Ni2+ uptake abilities of the present samples are higher than those of other materials reported in the literature. Since the sorbed Ni2+/released Ca2+ ratios of these samples are close to unity, ion replacement of Ni2+ for Ca2+ is thought to be the principal mechanism of Ni2+ uptake by the present samples.

Electrokinetic removal of caesium from kaolin.

Soil, in the form of kaolin and a sample of natural soil from an industrial site, was artificially contaminated with caesium and subjected to electrokinetic treatment. The effect of catholyte pH control on the process was investigated using different acids to control the catholyte pH. During treatment the in situ pH distribution, the current flow, and the potential distribution were monitored. At the end of the treatment the pore fluid conductivity and the caesium concentration distribution was measured. The results of these experiments showed that for caesium contamination, catholyte pH control is essential in order to create a suitable environment throughout the soil to enable contaminant removal. It was found that the type of acid used to control the catholyte pH affected the rate of caesium removal (nitric, sulphuric, acetic and citric acids were tested). All of the acids tested were effective, but the highest caesium extraction was achieved when nitric acid was used to control the catholyte pH. The relatively high adsorption capacity of the soil for caesium was found to significantly reduce the rate of removal. After 240 h of treatment at 1 Vcm(-1) (using sulphuric acid to control the catholyte pH), less than 80% of the caesium was removed from a 30 cm long sample of kaolin. Electrokinetic treatment of the industrial soil sample was slower than for the kaolin, but a significant extraction rate for caesium was achieved.

Enhancement of copper and cadmium adsorption on kaolin by the presence of humic acids.

The competitive adsorption equilibrium isotherms of Cu2+ and Cd2+ on kaolin have been measured at 298 K, in the presence and the absence of humic acids (HAs). HAs were found to enhance the metal adsorption capacity of mineral surfaces, in particular kaolin. This enhancement was also observed in the competitive adsorption of copper and cadmium on kaolin and kaolin-HA complex. This competitive adsorption shows that the presence of Cd2+ has not an important effect on Cu2+ adsorption, whereas a dramatic decrease is observed on the adsorption of Cd2+ in the presence of Cu2+. The Freundlich isotherm equation was found to provide an excellent fit to the experimental data. These results were compared with the independent adsorption of both heavy metals.

Emission and control characteristics for incineration of Sedum plumbizincicola biomass in a laboratory-scale entrained flow tube furnace.

Experiments were conducted to investigate and control pollutant emission from incineration of Sedum plumbizincicola plants on a laboratory scale using an entrained flow tube furnace. Without control technologies, the flue gas contained 0.101 mg Nm(-3) of Cd, 46.4 mg Nm(-3) of Zn, 553 mg Nm(-3) of NOx, 131 pg Nm(-3) of polychlorinated dibenzo-p-dioxin and polychlorinated dibenzofuran (PCDD/Fs) and 35.4 mg Nm(-3) of polycyclic aromatic hydrocarbons (PAHs). In pollutants control experiments. Al2O3, CaO, and kaolin were compared as adsorbents and activated carbon was used as an end-of-pipe method for the capture of pollutants. Kaolin, the most effective of the three adsorbents, removed 91.2% of the Cd in flue gas. While 97.6% of the Cd and 99.6% of the PAHs were removed by activated carbon. Incineration may therefore be regarded as a viable option for the safe disposal of the biomass of the zinc and cadmium hyperaccumulator species S. plumbizincicola.

Preparation and characterization of photoactive composite kaolinite/TiO(2).

Preparation of nanocomposite kaolinite/TiO(2), using hydrolysis of titanyl sulfate in the presence of kaolin was addressed. A variable (kaolin)/(titanyl sulfate) ratio has been used in order to achieve the desired TiO(2) content in prepared nanocomposites. Calcination of the composites at 600 °C led to the transformation of the kaolinite to metakaolinite and to origination of metakaolinite/TiO(2) composites. The prepared samples were investigated using X-ray fluorescence spectroscopy, X-ray powder diffraction, Fourier transform infrared spectroscopy, scanning electron microscopy, thermogravimetry and diffuse reflectance spectroscopy in the UV-VIS region. Structural ordering of TiO(2) on the kaolinite particle surface was modeled using empirical force field atomistic simulations in the Material Studio modeling environment. Photodegradation activity of the composites prepared was evaluated by the discoloration of Acid Orange 7 aqueous solution.

High-temperature sorption of cesium and strontium on dispersed kaolinite powders.

Sorption of cesium and strontium on kaolinite powders was investigated as a means to minimize the emissions of these metals during certain high-temperature processes currently being developed to isolate and dispose of radiological and mixed wastes. In this work, nonradioactive aqueous cesium acetate or strontium acetate was atomized down the center of a natural gas flame supported on a variable-swirl burner in a refractory-lined laboratory-scale combustion facility. Kaolinite powder was injected at a postflame location in the combustor. Cesium readily vaporized in the high-temperature regions of the combustor, but was reactively scavenged onto dispersed kaolinite. Global sorption mechanisms of cesium vapor on kaolinite were quantified, and are related to those available in the literature for sodium and lead. Both metal adsorption and substrate deactivation steps are important, so there is an optimum temperature, between 1400 and 1500 K, at which maximum sorption occurs. The presence of chlorine inhibits cesium sorption. In contrast to cesium, and in the absence of chlorine, strontium was only partially vaporized and was, therefore, only partially scavengeable. The strontium data did not allow quantification of global kinetic mechanisms of interaction, although equilibrium arguments provided insight into the effects of chlorine on strontium sorption. These results have implications for the use of sorbents to control cesium and strontium emissions during high-temperature waste processing including incineration and vitrification.

Mineralogical and hydrochemical effects on adsorption removal of cesium-137 and strontium-90 by kaolinite.

Adsorption characteristics of the nuclides onto kaolinite were investigated by batch experiment under various pH conditions and concentrations of groundwater cations (Ca2+, Mg2+, K+ and Na+) and anions (HCO3-, CO3(2-) and SO4(2-). Adsorption removal of 137Cs and 90Sr by kaolinite greatly increased as the concentration of groundwater cations increased from 10(-5) to 10(-1) M. In contrast, the pH exerted a small effect on the adsorption of 137Cs and 90Sr onto kaolinite. The zeta potential of kaolinite particles showed a negative increase of amphoteric surface charge with increasing pH. The adsorption behavior of 90Sr was also highly dependent on the concentration of bicarbonate. The thermodynamic saturation index indicated that bicarbonate exerts great effect on strontium adsorption by the precipitation of a strontianite (SrCO3) and a change in pH.