Theoretical Analysis on the Removal of Cyclic Volatile Organic Compounds by Non-thermal Plasma

Volatile organic compounds (VOCs) from anthropogenic sources, especially cyclic organics with stable structure and strong toxicity (e.g., cyclohexane and benzene), exert hazards to atmospheric environment and human health, and need to be controlled urgently. As an emerging technology for VOC removal, non-thermal plasma (NTP) with low-energy consumption and high removal efficiency is widely studied. However, in contrary to the abundant experiments, theoretical studies are only few, and the degradation mechanisms and pathways of VOCs are still open questions, which hinders the effective VOC removal. Herein, the density function theory (DFT) calculations of NTP degradations for two typical cyclic organics, cyclohexane and benzene, are performed. The degradations of cyclic organics are mainly resulted by the dehydrogenation, decarburation, elimination, and ring-opening reactions and can be markedly promoted with radical ·OH, H·, and O· produced by background gas (H2O and O2). For cyclohexane degradations, the presence of O· decreases the energy barrier from 81.9 to 8.7 kcal/mol in the initial step, leading to an optimal degradation pathway with minimum plasma energy at around 0.5 eV. For benzene degradations, the presence of ·OH decreases the energy barrier from 118.4 to 5.5 kcal/mol in the initial step, triggering an optimal degradation pathway with minimum plasma energy at around 6 eV. The higher plasma energy required in degradation of benzene is due to its more stable structure than alkanes ring. Moreover, the O₂ concentration and plasma energy are suggested to increase for efficient degradation of cyclohexane and benzene, respectively.     

Photodegradation of 3,5,6-trichloro-2-pyridinol in aqueous solution

A medium-pressure mercury lamp, emitting strongly in the 200–400 nm range was applied for the degradation of 3,5,6-trichloro-2-pyridinol (TCP), a hydrolysis product of chlorpyrifos. Photodegradation of TCP in aqueous solution exhibited pseudo-first order kinetics with a rate constant that was wavelength dependent and increased below 300 nm. The TCP degradation rate and quantum yield increased with solution pH up to a constant maximum value of (6.40 ± 0.046) × 10^?3 cm² mJ^{? 1} and 0.178 ± 0.002 mol E^?1 respectively, at pH 5 and above. Addition of 5 mg L^{? 1} H₂O₂ to generate OH radicals led to an increase in removal rates by a factor of 1.5. Addition of phosphate buffer resulted in decreased photolysis at 3 < pH < 6.     

Assessment on the Removal of Methylene Blue Dye using Tamarind Fruit Shell as Biosorbent

Tamarind fruit shell was used as a low-cost biosorbent for the removal of methylene blue from aqueous solution. The various factors affecting adsorption, such as agitation, pH, initial dye concentration, contact time, and temperature, were investigated. The dye adsorption capacity was strongly dependent on solution pH as well as temperature. The Langmuir isotherm model showed good fit to the equilibrium adsorption data, and the maximum adsorption capacity obtained was 1.72 mg g^?1 at 303 K. The kinetics of adsorption followed the pseudo-second-order model and the rate constant increased with increase in temperature, indicating endothermic nature of adsorption. The Arrhenius equation was used to obtain the activation energy (E _a) for the adsorption system. The activation energy was estimated to be 19.65 kJ mol^?1. Thermodynamic parameters such as Gibbs free energy (ΔG ⁰), enthalpy (ΔH ⁰), and entropy (ΔS ⁰) were also investigated. Results suggested that adsorption of methylene blue onto tamarind fruit shell was a spontaneous and endothermic process. The present investigation suggests that tamarind fruit shell may be utilized as a low-cost adsorbent for methylene blue removal from aqueous solution.     

Photocatalytic Degradation of Herbicide Quinmerac in Various Types of Natural Water

The efficiency of the photocatalytic degradation of the herbicide quinmerac in aqueous TiO₂ suspensions was examined as a function of the type of light source, TiO₂ loading, pH, temperature, electron acceptors, and hydroxyl radical (^?OH) scavenger. The optimum loading of catalyst was found to be 0.25?mg?mL^?1 under UV light at pH?7.2, with the apparent activation energy of the reaction being 13.7?kJ?mol^?1. In the first stage of the reaction, the photocatalytic degradation of quinmerac (50???M) followed approximately a pseudo-first order kinetics. The most efficient electron acceptor appeared to be H₂O₂ along with molecular oxygen. By studying the effect of ethanol as an ^?OH scavenger, it was shown that the heterogeneous catalysis takes place mainly via ^?OH. The results also showed that the disappearance of quinmerac led to the formation of a number of organic intermediates and ionic byproducts, whereas its complete mineralization occurred in about 120?min. The reaction intermediates (7-chloro-3-methylquinoline-5,8-dione, three isomeric phenols hydroxy-7-chloro-3-methylquinoline-8-carboxylic acids, and 7-chloro-3-(hydroxymethyl)quinoline-8-carboxylic acid) were identified and the kinetics of their appearance/disappearance was followed by LC?CESI?CMS/MS. Tentative photodegradation pathways were proposed and discussed. The study also encompassed the effect of quality of natural water on the rate of removal of quinmerac.     

Organics Wastewater Degradation by a Mesoporous Chromium-Functionalized γ-Al<Subscript>2</Subscript>O<Subscript>3</Subscript> with H<Subscript>2</Subscript>O<Subscript>2</Subscript> Assistance

In this study, a mesoporous chromium-functionalized γ-Al₂O₃ (Cr/γ-Al₂O₃) catalyst was prepared by an impregnation method, and the catalytic activity was evaluated by the degradation of organics wastewater. The prepared catalyst was characterized by X-ray photoelectron spectroscopy, X-ray diffraction, nitrogen adsorption-desorption experiments, and scanning electron microscopy. The characterization results confirmed that the pores in the Cr/γ-Al₂O₃ catalyst distributed broadly in the mesoporous region, and the active chromium species were highly dispersed on the catalyst surface. The catalytic activity tests showed that the Cr/γ-Al₂O₃ catalyst exhibited a superior performance for the degradation of organics wastewater with H₂O₂ assistance. And the methylene blue (MB) disappeared within 20 min and the COD removal reached 76.5% within 40 min for the MB-simulated wastewater; for the phenol-simulated wastewater, the phenol removal was above 95% and the corresponding COD removal reached 71% within 40 min. Such an excellent catalytic performance demonstrates that the Cr/γ-Al₂O₃ catalyst has a potential application in the degradation of complex organics wastewater simultaneously.     

Degradation of Monoethanolamine in Aqueous Solution by Fenton’s Reagent with Biological Post-treatment

Alkanolamines in the wastewater from gas treating plants are not readily biodegradable. In this work, we have investigated the effectiveness of the Fenton’s reagent (H₂O₂-Fe²⁺) to treat monoethanolamine (MEA) as a model compound in simulated wastewater. Degradation studies were carried out in a jacketed glass reactor. The effects of concentrations of ferrous sulfate, hydrogen peroxide, and the pH of a solution on the rate of reaction were determined. A pH of 3 was found to be the optimum. The degradation reaction proceeds very fast at the beginning but slows down significantly at a longer time. A larger fractional degradation of the organics in solution was observed if the initial chemical oxygen demand (COD) of the feed solution was high. Gradual addition of H₂O₂ to the reaction mixture increased the COD removal by about 60% compared to one-time addition of the reagent at the beginning of the process. A rate equation for mineralization of the amine was developed on the basis of a simplified mechanistic model, and the lumped value of the rate constant for COD removal was determined. A partially degraded MEA solution as well as “pure” MEA was subjected to biological oxidation by activated sludge. The former substrate degraded much faster. The degradation rate and biomass generation data could be fitted by the Monod kinetic equations.     

The Oxidation of Di-(2-Ethylhexyl) Phthalate (DEHP) in Aqueous Solution by UV/H2O2 Photolysis

The oxidation of di-(2-ethylhexyl) phthalate (DEHP) in solution using UV/H₂O₂ and direct UV photolysis are analyzed in this study. It was found that DEHP was 100% removal in the solution by 180-min UV/H₂O₂ treatment and 73.5% removal by 180-min direct UV photolysis. The effect of different factors, such as DEHP concentration, H₂O₂ concentration, and UV light intensity, on photochemical degradation was investigated. The degradation mechanism of DEHP and the acute toxicity of intermediates were also studied. The photochemical degradation process was found to follow pseudo-first-order kinetics. The results of our study suggested that the concentration with 40 mg/L H₂O₂ and 5 μg/mL DEHP in the solution at pH 7 with 10.0?×?10^?6 Einstein l^?1?s^?1 UV was the optimal condition for the photochemical degradation of DEHP. The photochemical degradation with UV/H₂O₂ can be an efficient method to remove DEHP in wastewater.     

Solar Decolorization of Methylene Blue by Magnetic MgFe<Subscript>2</Subscript>O<Subscript>4</Subscript>-MWCNT/Ag<Subscript>3</Subscript>VO<Subscript>4</Subscript> Visible Active Photocatalyst

MgFe₂O₄-MWCNT/Ag₃VO₄ photocatalyst was prepared for benefiting the visible region of solar spectrum. Prepared catalyst was characterized by using scanning electron microscope (SEM), X-ray diffraction (XRD), and energy-dispersive X-ray spectroscopy (EDX). Photocatalytic activity was measured by methylene blue (MB) decolorization under visible light obtained from a 105-W tungsten light bulb. Dye decolorization and its kinetics were followed up by means of a UV-vis spectrophotometer. Kinetic model of decolorization was found to be compatible with first-order kinetics. The effects of pH and concentration of MB solution on the decolorization efficiency were determined. Low and high pH conditions were found to be more effective in increasing the MB decolorization yield and rate. On the other hand, due to the low transparency of concentrated MB solutions, an increase on decolorization time and a lowering in decolorization yield were encountered. Thanks to the magnetic MgFe₂O₃ nanoparticles, 96% of the catalyst could be recovered by a simple magnetic bar. It was observed that simulated wastewater containing MB was also successfully decolorized showing that visible region-sensitive MgFe₂O₄-MWCNT/Ag₃VO₄ photocatalyst can be benefited as a potential, efficient, and reusable material for the removal organic pollutants in aquatic environment.     

Biosorption of Methylene Blue from Aqueous Solutions by Hazelnut Shells: Equilibrium, Parameters and Isotherms

This paper presents a study on the batch adsorption of a basic dye, methylene blue (MB), from aqueous solution onto ground hazelnut shell in order to explore its potential use as a low-cost adsorbent for wastewater dye removal. A contact time of 24 h was required to reach equilibrium. Batch adsorption studies were carried out by varying initial dye concentration, initial pH value (3–9), ionic strength (0.0–0.1 mol L^?1), particle size (0–200 μm) and temperature (25–55°C). The extent of the MB removal increased with increasing in the solution pH, ionic strength and temperature but decreased with increase in the particle size. The equilibrium data were analysed using the Langmuir and Freundlich isotherms. The characteristic parameters for each isotherm were determined. By considering the experimental results and adsorption models applied in this study, it can be concluded that equilibrium data were represented well by Langmuir isotherm equation. The maximum adsorption capacities for MB were 2.14?×?10^?4, 2.17?×?10^?4, 2.20?×?10^?4 and 2.31?×?10^?4 mol g^?1 at temperature of 25, 35, 45 and 55°C, respectively. Adsorption heat revealed that the adsorption of MB is endothermic in nature. The results indicated that the MB strongly interacts with the hazelnut shell powder.     

MINERALOGY AND GENESIS OF CLAYS IN RED-BLACK SOIL TOPOSEQUENCES ON BASIC IGNEOUS ROCKS IN KENYA

The clay mineralogy of two red-black soil toposequences on basic igneous rocks in Kenya has been investigated. Besides some illite and amorphous material kaolinites predominate in the slope soils (ultisols) whereas smectites are the main clay minerals in the soils of the depressions (vertisols). The kaolinites are poorly crystalline and have high surface area. According to chemical analysis, IR spectroscopy, and D.T.A. the smectites appear to be a ferriferous member of the montmorillonite-beidellite series having approximately 0·5 Fe³⁺ in octahedral and 0·2 Al per O₁₀(OH)₂ in the tetrahedral position. The profile and slope distribution of kaolinites and smectites led to the conclusion that the smectites are the first weathering product and, depending on hydrological conditions governing the soil solution composition (Si, Mg, pH), either persist (depression) or are decomposed (slope) and followed by kaolinites.     

A Stable Fe<Subscript>2</Subscript>O<Subscript>3</Subscript>/Expanded Perlite Composite Catalyst for Degradation of Rhodamine B in Heterogeneous Photo-Fenton System

A stable and efficient Fe₂O₃/expanded perlite (Fe₂O₃-Ep) composite catalyst was synthesized by a simple hydrothermal method for degradation of refractory contaminants in heterogeneous photo-Fenton system. X-ray diffraction and FT-IR analyses confirmed the presence of the Fe₂O₃ in the synthesized catalyst. The catalytic activity of the Fe₂O₃-Ep catalyst was evaluated by the degradation of rhodamine B (RhB, 5 mg/L) and metronidazole (MET, 5 mg/L) in the presence of H₂O₂ under visible light irradiation. The Fe₂O₃-Ep catalyst exhibited high efficiency for degradation of RhB at a wide pH range from 2 to 10 and showed excellent catalytic property for decomposition of MET as well. The degradation ratio of RhB was achieved 99%, and the removal ratio of COD was 62% within 90 min at the best experimental conditions (0.5 g/L of Fe₂O₃-Ep catalyst, 2 mL/L of H₂O₂). Furthermore, iron leaching of the Fe₂O₃-Ep catalyst during the catalytic degradation reaction was negligible and the catalyst still exhibited high catalytic activity and stability after five cycles. These results show that the catalyst can be used as a highly efficient heterogeneous photo-Fenton catalyst for the degradation of non-biodegradable refractory pollutants in water.     

Removal of As(III) from Aqueous Solution Using Fe<Subscript>3</Subscript>O<Subscript>4</Subscript> Nanoparticles: Process Modeling and Optimization Using Statistical Design

In this study, Extran (biodegradable surfactant) was used for the preparation of Fe₃O₄ nanoparticles by microemulsion process to improve removal efficiency of As(III) from aqueous solution. Fe₃O₄ nanoparticles were characterized by XRD, FTIR, FESEM, TEM, HRTEM, and VSM instrumental techniques. The effect of different parameters such as adsorbent dose, initial As(III) concentration, and solution pH were studied by response surface methodology (RSM) based on Box-Behnken design (BBD). The optimized condition for adsorption of As(III) from aqueous solution was obtained as adsorbent dose of 0.70 mg/g, solution pH of 7.7, and initial As(III) concentration of 33.32 mg/L. In this optimum condition, about 90.5% of As(III) was removed from the aqueous solution. Isotherm studies have been done at optimal condition, and it was observed that the Langmuir isotherm models were fitted well with experimental data having a high correlation coefficient of 0.993. From the Langmuir isotherm data, the maximum adsorption capacity of Fe₃O₄ nanoparticles was found to be 7.18 mg/g at pH 7.7 in room temperature. This study revealed that Fe₃O₄ nanoparticles can be used as an efficient, eco-friendly, and effective material for the adsorptive removal of As(III) from aqueous system.     

Equilibrium, Kinetics and Mechanism of Removal of Methylene Blue from Aqueous Solution by Adsorption onto Pine Cone Biomass of Pinus radiata

The kinetics and mechanism of methylene blue adsorption onto raw pine cone biomass (Pinus radiata) was investigated under various physicochemical parameters. The extent of the methylene blue dye adsorption increased with increases in initial dye concentration, contact time and solution pH but decreases with the amount of adsorbent, salt concentration and temperature of the system. Overall the kinetic studies showed that the methylene blue adsorption process followed pseudo-second-order kinetics among various kinetic models tested. The different kinetic parameters including rate constant, half-adsorption time and diffusion coefficient are determined at different physicochemical conditions. Equilibrium data were best represented by Langmuir isotherm among Langmuir and Freundlich adsorption isotherm. The maximum monolayer adsorption capacity of pine cone biomass was 109.89 mg/g at 30°C. The value of separation factor, R _L, from Langmuir equation and Freundlich constant, n, both give an indication of favourable adsorption. Thermodynamic parameters such as standard Gibbs free energy (?G ⁰), standard enthalpy (?H ⁰), standard entropy (?S ⁰) and the activation energy (A) were calculated. A single-stage batch absorber design for the methylene blue adsorption onto pine cone biomass has been presented based on the Langmuir isotherm model equation.     

Adsorption of Methylene Blue from Aqueous Solution onto Perlite

Adsorption of methylene blue from aqueous solutionsonto unexpanded and expanded perlite samples activatedby H₂SO₄ and NaCl solutions has beeninvestigated, to assess the possibility of usingperlite for removing cationic dyes from aqueoussolutions. The effects of pH and temperature of dyesolution on the adsorption capacities have beenevaluated. The experimental data were correlatedreasonably well by the Langmuir adsorption isothermand the isotherm parameters (Q _m and K) have beencalculated. The removal efficiency (P) anddimensionless separation factor (R) have shown thatperlite can be used for removal of methylene blue fromaqueous solutions, but unexpanded perlite is more effective.     

Evaluation of methods for determining sulphur‐35 and sulphur‐32 in the same trapping solution of Johnson and Nishita method

Abstract

A laboratory study was conducted to investigate whether the Zn‐Na acetate solution, used for trapping H₂S in the Johnson‐Nishita method (1952), could be used to quantitatively determine ³⁵S and ³²S in the same trapping solution, as the Zn‐Na acetate solution allows more sensitive S determination using methylene blue than does the bismuth sulphide colour development of H₂S trapped in NaOH solution. Results obtained using the Zn‐Na acetate solution were variable compared with those obtained from the normal procedure of using NaOH as the H₂S trapping solution, indicating that the Zn‐Na acetate solution was unsuitable, probably because of the rapid transformation of H₂S to water‐insoluble ZnS.

The applicability of methylene blue development for H₂S trapped in NaOH solution was also investigated. Results showed that ³²S could be determined quantitatively provided methylene blue colour development was conducted less than 30 minutes after the removal of H₂S‐trapping NaOH solution from the Johnson‐Nishita digestion‐distillation unit. A delay of more than 30 minutes caused a significant linear reduction (R² = 0.86 ‐ 0.92***) in methylene blue colour, indicating that H₂S in NaOH solution was readity: oxidized to other S forms which did not undergo methylene blue development.

Toluene and dioxane were compared as liquid scintillants for assaying ³⁵S activity trapped as H₂S in either NaOH or Zn‐Na acetate solution before and after methylene blue development. Before colour development, toluene improved the counting efficiency of ³⁵S in NaOH solution by 23 to 27%. After colour development, toluene improved the counting efficiency of both NaOH and Zn‐Na acetate solutions.     

Photodegradation of Sulfamethoxazole Applying UV- and VUV-Based Processes

The efficiency of UV- and VUV-based processes (UV, VUV, UV/H₂O₂, and VUV/H₂O₂) for removal of sulfamethoxazole (SMX) in Milli-Q water and sewage treatment plant (STP) effluent was investigated at 20??C. The investigated factors included initial pH, variety of inorganic anions (NO ₃ ^? and HCO ₃ ^? ), and humic acid (HA). The results showed that the degradation of SMX in Milli-Q water at both two pH (5.5 and 7.0) followed the order of VUV/H₂O₂ > VUV > UV/H₂O₂ > UV. All the experimental data well fitted the pseudo-first order kinetic model and the rate constant (k) and half-life time (t _1/2) were determined accordingly. Indirect oxidation of SMX by generated ^?OH was the main degradation mechanism in UV/H₂O₂ and VUV/H₂O₂, while direct photolysis predominated in UV processes. The quenching tests showed that some other reactive species along with ^?OH radicals were responsible to the SMX degradation under VUV process. The addition of 20?mg?L^?1 HA significantly inhibited SMX degradation, whereas, the inhibitive effects of NO ₃ ^? and HCO ₃ ^? (0.1?mol?L^?1) were observed as well in all processes except in UV irradiation for NO ₃ ^? . The removal rate decreased 1.7?C3.6 times when applying these processes to STP effluent due to the complex constituents, suggesting that from the application point of view the constituents of these complexes in real STP effluent should be considered carefully prior to the use of UV-based processes for SMX degradation.     

Sorption Behavior of Ofloxacin to Kaolinite: Effects of pH,Ionic Strength,and Cu(II)

Sorption of antibiotics to clay minerals is a key process controlling their transport and fate in environment. In this study, the effects of pH, ionic strength, and Cu(II) on ofloxacin (OFL) sorption to kaolinite were investigated by batch sorption experiments. The results of sorption edge experiments suggested that OFL sorption to kaolinite was pH and ionic strength dependent. Cation exchange was a major contributor to the sorption of OFL⁺ to kaolinite. The decreased OFL sorption with increasing ionic strength indicated the formation of outer-sphere complexation. When solution pH was lower than 7.0, Cu-OFL complexes facilitated OFL sorption through electrostatic attraction or formation of kaolinite-Cu-OFL and kaolinite-OFL-Cu ternary surface complexes. However, existence of free Cu(II) cation in solution competed for sorption sites, and thus suppressed OFL sorption. When solution pH was higher than 7.0, Cu(II) existed as Cu(OH)₂, and the Cu-OFL complexes in aqueous phase and solid phase (precipitation) enhanced OFL removal efficiency from solution. The results imply that Cu(II) effects should be taken into account in the evaluation of OFL mobility in environment.     

Removal of Natural Organic Matter from River Water Using Potassium Ferrate(VI)

In this research, we have investigated the removal efficiency of natural organic matter (NOM) from river and stream water using potassium ferrate(VI). For the study, ferrate was added in 100-ml water sample mixed either with humic acid or with fulvic acid. The removal efficiency at the ferrate dose of 2–46 mg/l (as Fe) was 21–74% for 10 mg/l humic acid and 48–78% for 10 mg/l fulvic acid. NOM was more effectively removed either at lower pH or at higher temperature. The removal performance by ferrate was comparable to that by traditional coagulants (i.e., alum, FeSO₄·7H₂O, and FeO(OH)). In addition, the removal rate of humic acid using traditional coagulants was improved by pretreatment with a very small dose of ferrate. The reaction between ferrate and humic acid was completed within 60 s, while showing first-order kinetic, and then reached a steady state.     

Effects of changes in pH, ionic strength, and sulphate concentration on the CEC of temperate acid forest soils

As the acidity of rain diminishes, changes in the pH, ionic strength, and ion activities of the soil solution will influence the charge characteristics of soil. We have investigated the response of cation exchange capacity (CEC) of three acid forest soils of variable charge to small changes in pH, ionic strength, and SO^2?₄ concentration. The variable charge for these temperate soils has the same significance as for tropical soils and those from volcanic ash. Maximum absolute increase in CEC on increasing pH by 0·2–0·5 units reached 5 cmol_c kg^-1 in O horizons. The increase in CEC on doubling ionic strength in EA and Bsh horizons of a Cambic Podzol was about half that amount, but relative gains compared to effective CEC were 65 and 46%, respectively. For other soil horizons, absolute changes were smaller, and relative changes were between 10 and 30%. Halving the SO^2?₄ concentration significantly influenced CEC only in some samples. Both pH and ionic strength must be adjusted with care when determining CEC_c of acid forest soils. Decreasing acid deposition will not inevitably increase CEC_c because in some soils pH effects may be balanced by simultaneous decrease in ionic strength.     

Equilibrium, Kinetics, and Thermodynamics of Methylene Blue Adsorption by Pine Tree Leaves

The adsorption capacity of pine tree leaves for removal of methylene blue (MB) from aqueous solution was investigated in a batch system. The effects of the process variables, such as solution pH, contact time, initial dye concentration, amount of adsorbent, agitation speed, salt concentration, and system temperature on the adsorption process were studied. The extent of methylene blue dye adsorption increased with increase in initial dye concentration, contact time, agitation speed, temperature, and solution pH but decreased with increased in amount of adsorbent and salt concentration. Equilibrium data were best described by both Langmuir isotherm and Freundlich adsorption isotherm. The maximum monolayer adsorption capacity of pine tree leaves biomass was 126.58?mg/g at 30?°C. The value of separation factor, R _L , from Langmuir equation and Freundlich constant, n, both give an indication of favorable adsorption. The intrapartical diffusion model, liquid film diffusion model, double exponential model, pseudo-first and second order model were used to describe the kinetic and mechanism of adsorption process. A single stage bath adsorber design for the MB adsorption onto pine tree leaves has been presented based on the Langmuir isotherm model equation. Thermodynamic parameters such as standard Gibbs free energy (??G ⁰), standard enthalpy (??H ⁰), and standard entropy (??S ⁰) were calculated.