Kinetics and equilibrium adsorption study of selenium oxyanions onto Al/Si and Fe/Si coprecipitates.

Inappropriate treatments for the effluents from semiconductor plants might cause the releases and wide distributions of selenium (Se) into the ecosystems. In this study, Al/Si and Fe/Si coprecipitates were selected as model adsorbents as they often formed during the wastewater coagulation process, and the removal efficiency of selenite (SeO3) and selenate (SeO4) onto the coprecipitates were systematically examined. The removal efficiency of SeO3 and SeO4 was highly related to surface properties of Al/Si and Fe/Si coprecipitates. The surface-attached Al shell of Al/Si coprecipitates shielded a portion of negative charges from the core SiO2, resulting in a higher point of zero charge than that of Fe/Si coprecipitates. Thus, adsorption of SeO3/SeO4 was favorable on the Al/Si coprecipitates. Adsorptions of both SeO3 and SeO4 on Al/Si coprecipitates were exothermic reactions. On Fe/Si coprecipitates, while SeO3 adsorption also showed the exothermic behavior, SeO4 adsorption occurred as an endothermic reaction. The kinetic adsorption data of SeO3/SeO4 on Al/Si and Fe/Si coprecipitates were described well by the pseudo-second-order kinetic model. SeO4 and SeO3 adsorption on Fe/Si or Al/Si were greatly inhibited by the strong PO4 ligand, whereas the weak ligand such as SO4 only significantly affected SeO4 adsorption. The weakest complex between SeO4 and Al was implied by the essentially SeO4 desorption as SeO4/PO4 molar ratios decreased from 0.5 to 0.2. These results were further confirmed by the less SeO4 desorption (41%) from Fe/Si coprecipitates than that from Al/Si coprecipitates (78%) while PO4 was added sequentially.

Oxidative removal of arsenite by Fe(II)- and polyoxometalate (POM)-amended zero-valent aluminum (ZVAl) under oxic conditions.

Abiotic transformation of As(III) to As(V) is possible which would decrease As toxicity. This study investigated the potential applications of zero-valent Al (ZVAl) or Al wastes, such as Al beverage cans, for converting As(III) to As(V) in an acidic solution under aerobic conditions. Results showed that As(III) could not be oxidized by ZVAl within 150 min reaction at pH 1 because of the presence of an oxide layer on ZVAl. However, 85 µM As(III) could be completely oxidized with the addition of Fe(II) or POM due to the generation of a Fenton reaction or the enhancement of H2O2 production, respectively, on the ZVAl surfaces. Because Fe(II) or polyoxometalate (POM) exhibited more stable at low pH and scavenged rapidly the H2O2 produced on the aerated ZVAl surfaces, OH radical productions were more efficient and As(III) was rapidly oxidized in the ZVAl/O2 system with theses two catalysts. The catalytic oxidation kinetics of As(III) in the presence of Fe(II) or POM were best described by zero-order reaction, and the rate constants increased with a decrease of pH from 2 to 1. Following the oxidative conversion of As(III) to As(V) in the ZVAl/Fe/O2 system, As(V) was removed by the newly formed hydrous Al/Fe precipitates by increasing the solution pH to 6. Nonetheless, the As(V) removal was incomplete in the ZVAl/POM/O2 system because the hydrolyzed products of POM, e.g., PO4(3-), inhibited As(V) removal due to the competitive adsorption of the oxyanion on Al precipitates. Discarded Al-based beverage cans exhibit a higher efficiency for As(III) oxidation and final As removal compared with that of ZVAl, and thus, the potential application of Al beverage cans to scavenge As in solutions is feasible.

Microwave torrefaction of rice straw and Pennisetum.

Microwave torrefaction of rice straw and pennisetum was researched in this article. Higher microwave power levels contributed to higher heating rate and reaction temperature, and thus produced the torrefied biomass with higher heating value and lower H/C and O/C ratios. Kinetic parameters were determined with good coefficients of determination, so the microwave torrefaction of biomass might be very close to first-order reaction. Only 150W microwave power levels and 10min processing time were needed to meet about 70% mass yield and 80% energy yield for torrefied biomass. The energy density of torrefied biomass was about 14% higher than that of raw biomass. The byproducts (liquid and gas) possessed about 30% mass and 20% energy of raw biomass, and they can be seen as energy sources for heat or electricity. Microwave torrefaction of biomass could be a competitive technology to employ the least energy and to retain the most bioenergy.

Chromate reduction on humic acid derived from a peat soil--exploration of the activated sites on HAs for chromate removal.

Humic substances are a major component of soil organic matter that influence the behavior and fate of heavy metals such as Cr(VI), a toxic and carcinogenic element. In the study, a repetitive extraction technique was used to fractionate humic acids (HAs) from a peat soil into three fractions (denoted as F1, F2, and F3), and the relative importance of O-containing aromatic and aliphatic domains in humic substances for scavenging Cr(VI) was addressed at pH 1. Spectroscopic analyses indicated that the concentrations of aromatic C and O-containing functional groups decreased with a progressive extraction as follows: F1>F2>F3. Cr(VI) removal by HA proceeded slowly, but it was enhanced when light was applied due to the production of efficient reductants, such as superoxide radical and H(2)O(2), for Cr(VI). Higher aromatic- and O-containing F1 fraction exhibited a greater efficiency for Cr(VI) reduction (with a removal rate of ca. 2.89 mmol g(-1) HA under illumination for 3 h). (13)C NMR and FTIR spectra further demonstrated that the carboxyl groups were primarily responsible for Cr(VI) reduction. This study implied the mobility and fate of Cr(VI) would be greatly inhibited in the environments containing such organic groups.

Chromate removal as influenced by the structural changes of soil components upon carbonization at different temperatures.

Surface fire could induce heat transferring into the soil, creating a carbonized environment, which may alter the chemical compositions of soil organic matters (SOM). In the study, a surface soil was carbonized at up to 600 °C with limited air to simulate soils experiencing a surface fire, and Cr(VI) removal on the carbonized soils was investigated. NMR and FTIR analyses demonstrated a remarkable change of SOM structures at 300-400 °C. TGA-MS spectra indicated that (e.g. C(2)H(4), CH(3)OH and C(3)H(8)) were the major components in the evolved gases from the pyrolyzed soil. A maximum amount of Cr(VI) removal (ca. 4 mg g(-1) soil) occurred for the 200 °C-carbonized soils, attributed mainly to a significant increase of Cr(VI) reduction by 0.1 M KCl extractable organic carbon (EOC) with abundant carboxylic groups. Nonetheless, the formation of aromatic C upon carbonization of the soil at >400 °C may be responsible for Cr(VI) reduction.

Removal of methylene blue from water by gamma-MnO2.

Methylene blue (MB) is a cationic dyestuff, which is particularly resistant to biodegradation. The molecular sieved gamma-MnO2 was used as an adsorbent/oxidant to remove the MB at room temperature and in visible light. The removal efficiency was mainly evaluated by X-ray diffractometer (XRD), UV-Vis spectrometer (UV-Vis), total organic carbon (TOC). The results revealed that the mechanisms of MB removal by gamma-MnO2 are significantly influenced by the pH. In acidic conditions, hypsochromic effects (i.e. blue shifts of UV-Vis spectra) resulting from N-demethylation of the dimethylamino group in MB may occur concomitantly with oxidative degradation by gamma-MnO2. However, the TOC in solution after gamma-MnO2 treatment in acidic conditions did not show a dramatic decrease. At near neutral pH conditions, there was almost no UV-Vis absorption for the MB solution, however, only 50% TOC removal was observed. It indicated that MB was not only adsorbed onto gamma-MnO2 but also partially oxidatively degraded to other organic compounds which were colourless for UV-Vis.

Influence of chemical compositions and molecular weights of humic acids on Cr(VI) photo-reduction.

Humic acids (HA) strongly affect the fate of trace metals in soils and aquatic environments. One of the remarkable properties of HA is its ability to reduce Cr(VI), an extremely toxic anion. However, it is unclear which HA components are involved in Cr(VI) reduction and possess the photo-induced properties. In this study, an ultrafiltration technique was used to fractionate HAs into four fractions of different nominal molecular weights (M(w)): >100, 50-100, 10-50 and <10 kDa. Each HA fraction was characterized by spectroscopic analyses followed by examining Cr(VI) removal on each fraction of HA at pH 1-5. Spectroscopic results indicated that low-M(w) HA was enriched with polar and aromatic domains. These polar, including polar C in aliphatic region, and aromatic groups were the major sites for Cr(VI) reduction because they disappeared rapidly upon interaction with Cr(VI). As a result, low M(w) of HA exhibited greater efficiency of Cr(VI) reduction. Light induced the rapid transfer of electrons between chromate-phenol/carboxyl ester, or the formation of peroxide radicals or H(2)O(2) through the ready decay of peroxy radicals associated with polar substituents, explained the rapid scavenging of Cr(VI) on polar and aromatic groups of HAs under illumination.

A sequential method to analyze the kinetics of biomass pyrolysis.

The kinetics of biomass pyrolysis was studied via a sequential method including two stages. Stage one is to analyze the kinetics of biomass pyrolysis and starts with the determination of unreacted fraction of sample at the maximum reaction rate, (1-α)(m). Stage two provides a way to simulate the reaction rate profile and to verify the appropriateness of kinetic parameters calculated in the previous stage. Filter paper, xylan, and alkali lignin were used as representatives of cellulose, hemicellulose, and lignin whose pyrolysis was analyzed with the assumption of the orders of reaction being 1, 2, and 3, respectively. For most of the biomass pyrolysis, kinetic parameters were properly determined and reaction rate profiles were adequately simulated by regarding the order of reaction as 1. This new method should be applicable to most of the biomass pyrolysis and similar reactions whose (1-α)(m) is acquirable, representative, and reliable.

Pyrolysis of biomass by thermal analysis-mass spectrometry (TA-MS).

The kinetic parameters such as pre-exponential factor and activation energy of hemicellulose, cellulose, and lignin were well determined by the linear regressions of selected, sufficient thermogravimetric data, and close to literature values. The pyrolysis of biomass can be divided into four stages. There was only drying in the zeroth stage (<150°C). In the first stage (150-250°C), some light hydrocarbons were produced with the early pyrolysis of biomass. The biomass was mainly pyrolyzed in the second stage (250-500°C) with higher reaction rates than those of other stages. The productions of H(2) and CO(2) in the third stage (>500°C) may be able to be the evidence of self-gasification of char existing at higher temperatures.

Cr(VI) removal on fungal biomass of Neurospora crassa: the importance of dissolved organic carbons derived from the biomass to Cr(VI) reduction.

Interactions of toxic Cr(VI) with renewable biomaterials are considered an important pathway for Cr(VI) removal in ecosystems. Biomaterials are susceptible to dissolution, and their dissolved derivatives may provide an alternative to surface-involved pathway for scavenging of Cr(VI). In this study, dissolved organic carbon (DOC) derived from Neurospora crassa biomass was investigated. The proportion of Cr(VI) reduction by DOC to that on biomass was determined to evaluate the importance of DOC to Cr(VI) reduction. A rapid increase in DOC concentration from 145.6 to 193.7 mg L(-1) was observed when N. crassa-biomass was immersed in 0.01 M KCl solution at pH of 1-5, and polysaccharides, peptides, and glycoproteins with carboxyl, amide, and -NH functional groups, are the major compositions of DOC. On reaction of 96.2 microM Cr(VI) with N. crassa-biomass or DOC, it was estimated that DOC contributed approximately 53.8-59.5% of the total Cr(VI) reduction on biomass in the dark. Illumination enhanced Cr(VI) reduction via photo-oxidation of biomass/DOC under aeration conditions, which formed superoxide for Cr(VI) reduction. At pH 1, photoinduced Cr(VI) reduction by DOC proceeded more rapidly than reduction on the biomass surface. However, at pH >3, with a decrease in Cr(VI) reduction by DOC, photon-excited biomass may become an important electron source for Cr(VI) photoreduction.

Hydrogen-rich fuel gas from rice straw via microwave-induced pyrolysis.

This study aimed to research the productivity of H(2)-rich fuel gas from rice straw using the microwave-induced pyrolysis. The formation constituents of gas product and the mechanism of its production were also discussed. The primary components of gas product were H(2), CO(2), CO, and CH(4), with average percentages of 50.67, 22.56, 16.09, and 7.42vol.%, respectively. According to the TA-MS analysis, it was suggested that focused heating by microwaves made the microwave-induced pyrolysis different from the traditional pyrolysis. A chemical equation could be nearly balanced to illustrate the gas composition generated from rice straw. From the viewpoint of energy consumption, close to 60% of the input energy could be derived and utilized as bioenergy.

Treatment of As(V) and As(III) by electrocoagulation using Al and Fe electrode.

A batch electrocoagulation (EC) process with bipolar electrode and potentiodynamic polarization tests with monopolar systems were investigated as methods to explore the effects of electrode materials and initial solution pH on the As(V) and As(III) removal. The results displayed that the system with Al electrode has higher reaction rate during the initial period from 0 to 25 minutes than that of Fe electrode for alkaline condition. The pH increased with the EC time because the As(V) and As(III) removal by either co-precipitation or adsorption resulted in that the OH positions in Al-hydroxide or Fe-hydroxide were substituted by As(V) and As(III). The pH in Fe electrode system elevate higher than that in Al electrode because the As(V) removal substitutes more OH position in Fe-hydroxide than that in Al-hydroxide. EC system with Fe electrode can successfully remove the As(III) but system with Al electrode cannot because As(III) can strongly bind to the surface of Fe-hydroxide with forming inner-sphere species but weakly adsorb to the Al-hydroxide surface with forming outer-sphere species. The acidic solution can destroy the deposited hydroxide passive film then allow the metallic ions liberate into the solution, therefore, the acidic initial solution can enhance the As(V) and As(III) removal. The over potential calculation and potentiodynamic polarization tests reveal that the Fe electrode systems possess higher over potential and pitting potential than that of Al electrode system due to the fast hydrolysis of and the occurrence of Fe-hydroxide passive film.

Total recovery of resources and energy from rice straw using microwave-induced pyrolysis.

This article presents the application of microwave-induced pyrolysis to total recovery of resources and energy from rice straw. The microwave power and particle size of feedstock were both key parameters affecting the performance of microwave-induced pyrolysis. Under 400-500W microwave power, the reduction of fixed carbon in the biomass was significant. From the experimental results of specific surface area, zeta potential, and Cu2+ adsorption, the applications of solid residues in the water and wastewater treatment could be expected. The major compositions in gaseous product were H2, CO2, CO, CH4 of 55, 17, 13, 10vol.%, respectively. The high H2 content might imply that microwave-induced pyrolysis of biomass waste has the potential to produce the H2-rich fuel gas. Alkanes, polars, and low-ringed polycyclic aromatic hydrocarbons were three primary kinds of compounds in the liquid product.

Relationship between landscape characteristics and surface water quality.

The effects of landscape characteristics on surface water quality were evaluated in terms of land-use condition, soil type and slope. The case area, the Chichiawan stream in the Wulin catchment in Taiwan, is Formosan landlocked salmon's natural habitat. Due to the agriculture behavior and mankind's activities, the water and environmental quality has gradually worsened. This study applied WinVAST model to predict hydrological responses and non-point source pollution (NPSP) exports in the Wulin catchment. The land-use condition and the slope of land surface in a catchment are major effect factors for watershed responses, including flows and pollutant exports. This work discussed the possible variation of watershed responses induced by the change of land-use condition, soil type and slope, etc. The results show that hydrological responses are highly relative to the value of Curve Number (CN); Pollutant exports have large relation to the average slope of the land surface in the Wulin catchment.

Treating chemical mechanical polishing (CMP) wastewater by electro-coagulation-flotation process with surfactant.

The effect of surfactants on the treatment of chemical mechanical polishing (CMP) wastewater by electro-coagulation-flotation (ECF) process was studied. Two surfactants, cetyltrimethylammonium bromide (CTAB) and sodium dodecylsulfate (SDS) were employed in this study to compare the effect of cationic (CTAB) and anodic (SDS) surfactants on ECF. The cationic surfactant can enhance the removal of the turbidity, but anodic surfactant cannot. It can be explained by the hetero-coagulation theory. Moreover, the addition of CTAB in CMP wastewater can reduce the sludge volume and the flotation/sedimentation time in ECF process. The residual turbidity and dissolved silicon dropped with the increase of charge loading. No CTAB pollution problem exists after the ECF process.

Removal of fluoride from semiconductor wastewater by electrocoagulation-flotation.

This work employs an anodic surfactant, sodium dodecyl sulfate (SDS), to improve the flotation performance of the electrocoagulation-flotation (ECF) process to treated fluoride containing semiconductor wastewater following calcium precipitation. The dissolved fluoride ions and CaF(2) particles in the wastewater after calcium precipitation were effectively removed in the ECF process simultaneously. The dosage of SDS required for ECF was much less than those for dispersed air flotation (DiAF) or dissolved air flotation (DAF) processes because the CaF(2) particles can be collected by hydro-fluoro-aluminum flocs in ECF. Thus, SDS only served as a frother to make the bubbles tiny and stable in the ECF defluoridation process. The interference of co-existing anions can be overcome by increasing the dosage of calcium ions and SDS. The optimum initial acidity for ECF is close to the initial fluoride concentration after calcium precipitation; the amount of SS removed dropped rapidly if the initial acidity exceeded the optimal value because the surface charge of the hydro-fluoro-aluminum particles increased. The initial acidity of the wastewater after calcium precipitation can be modified by changing the [Ca(OH)(2)]/[Ca(2+)](T) ratio and the appropriate ratio is approximately given by the acid dissociation constant of hydrofluoric acid and the initial pH of the wastewater before calcium precipitation.

Effects of the molar ratio of hydroxide and fluoride to Al(III) on fluoride removal by coagulation and electrocoagulation.

The effect of the molar ratio of hydroxide and fluoride ions to Al(III) ions (gamma(OH) and gamma(F)) on coagulation and electrocoagulation (EC) was studied to solve the problem of the over addition of acid or base. The efficiency of defluoridation was approximately 100% when the sum of gamma(OH) and gamma(F) (gamma(OH+F)) was close to 3. This finding reveals that the fluoride ions and the hydroxide ions can co-precipitate with Al(III) ions and the formula of the precipitate is Al(n)F(m)(OH)(3n-m). However, when gamma(OH) was less than 2.4, the defluoridation efficiency, given that gamma(OH+F)=3, dropped as gamma(OH) fell, because the amount of aluminum polymer formed dropped. The efficiency of defluoridation of EC exceeded that of coagulation for equal gamma(OH) and gamma(OH+F), when gamma(OH+F)>3, proving the existence of an electrocondensation effect.

Methods for accelerating nitrate reduction using zerovalent iron at near-neutral pH: effects of H2-reducing pretreatment and copper deposition.

Both surface treatments, H2-reducing pretreatment at 400 degrees C and the deposition of copper as a catalyst, were attempted to enhance the removal of nitrate (40 (mg N) L(-1)) using zerovalent iron in a HEPES buffered solution at a pH of between 6.5 and 7.5. After the iron surface was pretreated with hydrogen gas, the removal of the passive oxide layers that covered the iron was indicated by the decline in the oxygen fraction (energy dispersive X-ray analysis) and the overlap of the cyclic polarization curves. The reaction rate was doubled, and the lag of the early period disappeared. Then, the deposition of copper onto freshly pretreated iron promoted nitrate degradation more effectively than that onto a nonpretreated iron surface, because of the high dispersion and small size of the copper particles. An optimum of 0.25-0.5% (w/w) Cu/Fe accelerated the rate by more than six times that of the nonpretreated iron. The aged 0.5% (w/w) Cu/Fe with continual dipping in nitrate solution for 20 days completely restored its reactivity by a regeneration process with H2 reduction. Hence, these two iron surface treatments considerably promoted the removal of nitrate from near-neutral water; the reactivity of Cu/Fe was effectively recovered.

Effects of co-existing anions on fluoride removal in electrocoagulation (EC) process using aluminum electrodes.

Batch experiments with bipolar aluminum electrodes and potentiodynamic polarization tests with monopolar systems were conducted to investigate the effects of the type and concentration of co-existing anions on defluoridation in electrocoagulation (EC) process. The results demonstrate that the type of the dominant anion directs the EC defluoridation reaction. The defluoridation efficiency was almost 100% and most of the fluoride removal reaction occurred on the surface of the anode in the solution without the co-existing anions, due to the electro-condensation effect. In the solutions with co-existing anions, most of the defluoridation took place in bulk solution. The residual fluoride concentration is a function of the total mass of Al(III) liberation from anodes and the types of the functions in the solutions with and without co-existing anions are different. The existence of sulfate ions inhibits the localized corrosion of aluminum electrodes, leading to lower defluoridation efficiency because of lower current efficiency. The presence of chloride or nitrate ions prevented the inhibition of sulfate ions, and the chloride ions were more efficient. Different corrosion types occurred in different anion-containing solutions and the form of corrosion affected the kinetic over-potential. The bypass flow causes the decrease of current efficiency and the proportion of the bypass flow of current increased due to a rise of the kinetic over potential and the conductivity of the solution.

A geometric approach to determine adsorption and desorption kinetic constants.

A geometric method based on Langmuir kinetics has been derived to determine adsorption and desorption kinetic constants. In the conventional procedure, either the adsorption kinetic constant (k(a)c) or desorption kinetic constant (k(d)c) is found from kinetic experiments and the other is calculated by their correlation with the equilibrium constant, i.e, k(d)c = Kcon/k(a)c, where Kcon has been known from equilibrium studies. The determined constants (Kcon, k(a)c, k(d)c), if based only on the conventional procedure, may not be accurate due to their mathematical dependence. Therefore, the objectives of this study are applying a geometric approach to directly determine Langmuir kinetic constants and describe adsorption behavior. In this approach, both adsorption kinetic constant (k(a)g) and desorption kinetic constant (k(d)g) are obtained only from data of kinetic experiments, and a geometric equilibrium constant (Kgeo) is calculated by Kgeo = k(a)g/k(d)g. The deviation between Kgeo and Kcon can prove the accuracy of k(a)g and k(d)g which were determined by this method. This approach was applicable to selenate, selenite and Mg2+ adsorption onto SiO2 regardless of whether the adsorbate formed inner- or outer-sphere complexes. However, this method showed some deviation between Kcon and Kgeo for Mn2+ adsorption because of the formation of surface Mn(II)-hydroxide clusters, which was inconsistent with the basic assumption of this method of monolayer adsorption.