Efficiency of rice bran for removal of organochlorine compounds and benzene from industrial wastewater

Rice bran was found to effectively adsorb several organic compounds, such as dichloromethane, chloroform, carbon tetrachloride, trichloroethylene, tetrachloroethylene, and benzene. Equilibrium adsorption isotherms conformed to the Freundlich type (log-log linear). The adsorption of dichloromethane and chloroform by rice bran was observed over the range of pH 1-11. Therefore, rice bran is applicable for treatment of wastewater over a wide pH range. Dichloromethane was successfully removed from water samples with an average removal efficiency of 70% after 60 min when rice bran was added to water samples containing from 0.006 to 100 mg/L dichloromethane. The removal of these organochlorine compounds and benzene by rice bran was attributed to the uptake by intracellular particles called spherosomes. Here, we report the results of a fundamental study of the efficiency of rice bran for removal of organochlorine compounds and benzene using a batch system on the laboratory scale, and describe elucidation of the mechanism of removal of these compounds by rice bran.     

Determination of spherosomes from lees materials

To evaluate the effectiveness in adsorbing organochlorine compounds such as chloroform, dichloromethane, or benzene by lees materials, the determination of spherosomes from different lees materials was established by using a hemacytometer under an optical microscope. Rice bran, wheat bran, rapeseed, linseed, okara, and sakekasu were used for this investigation, and activated carbon was also used as a standard adsorbent material. The number of spherosomes varied from 1.82 x 10(10) particles/g for sakekasu to 4.95 x 10(10) particles/g for wheat bran. There was a high correlation between the removal efficiency in adsorbing organochlorine compounds such as chloroform, dichloromethane, or benzene by lees materials and the number of spherosomes from different lees materials.     

Efficiency of spherosome for removal of chloroform from water

Spherosomes were elucidated to be a key for removal of chloroform by rice bran (Adachi, A.; Okano, T. Chemosphere 2002, 46, 87-92). On the basis of the above findings, a large amount of spherosomes was separated from rice bran using an industrial scale machine in order to investigate direct removal of chloroform by spherosome from tap water. The efficiency of removal of chloroform from water by rice bran spherosome was evaluated. Equilibrium adsorption isotherms conformed to the Freundlich isotherm (log-log linear). Adsorption of this compound by spherosome was observed in the pH range of 1-12. At equilibrium, the adsorption efficiency of spherosome for chloroform was higher than that of rice bran or activated carbon in the high chloroform concentration range (concentration>0.1 g/L). In the low chloroform concentration range (concentration<0.08 g/L), activated carbon adsorbs more chloroform than spherosome, but the adsorbed amount by spherosome is of the same order as that by activated carbon, which is several orders higher than that by rice bran. Chloroform was removed from tap water with an average removal efficiency of 90% after 90 min when spherosome (2 g/L) was added to tap water containing 0.105 mg/L of chloroform.     

Studies on defatted seed removal efficiency for organochlorine compounds

Defatted seeds were evaluated for effective adsorption of organochlorine compounds such as chloroform, dichloromethane, and trichloroethylene. The amounts of these compounds adsorbed were plotted against the equilibrium concentration of substances in solution on a logarithmic scale. A linear relationship was obtained, indicating that the adsorption reactions were of the Freundlich type. The removal of these organochlorine compounds by defatted seed was attributed to the uptake by intracellular particles called spherosomes.     

Volatile Organic Compounds in the Ambient Air of Rousse,Bulgaria

Volatile organic compounds in the ambient air were measured at four locations in Rousse, Bulgaria for a one year period. A gas chromatograph/mass spectrometer equipped with a cryogenic concentrator was used to analyse the air samples. Forty one compounds (aromatic hydrocarbons and halogen-derivatives of aliphatic and aromatic hydrocarbons) were analysed by EPA method TO-14. Aromatic hydrocarbons, benzene, toluene, styrene, isomers of xylene and isomers of trimethyl benzene were the most frequently occurring pollutants. Styrene, isomers of xylene and isomers of trimethyl benzene frequently exceeded the concentration limits. Among the halogen derivatives, the concentration of chloroform was always very high. A concept called ‘degree of pollution’ was proposed to clarify the contribution of each pollutant to the total air-pollution. Suggestions were made on the need to introduce an integral tolerance parameter to describe the total impact on air-pollution.     

Comparison of methods for extraction of organic N monomers from soil microbial biomass

One way of investigating the function of soil is via the pool of low molecular weight organic compounds in the soil microbial biomass. This is because low molecular weight organic compounds have key roles in metabolism of soil microbes, can function in osmotic adjustment and other stress responses, and are intermediates in the breakdown of polymers to inorganic nutrients. Methods for measuring low molecular weight microbial metabolites in soil rely upon extracting total metabolites and then subtracting the contribution from metabolites in the soil extracellular matrix (i.e. microbial = total − extracellular). Recent studies have tested methods for extracting organic N monomers from the extracellular matrix of soil, but there has not been similar testing of methods for extracting total organic N monomers. The aims of this study were to examine methods for extracting total organic N monomers by a) contrasting chloroform gas fumigation with chloroform direct extraction, and b) examining whether it is possible to extract soil with two methods that combine quenching of metabolic activity with extraction, namely cold methanol/chloroform/water and hot aqueous ethanol. To evaluate methods, organic N compounds were extracted from soil and then capillary electrophoresis–mass spectrometry identified and quantified 42 organic N monomers including amino acids, quaternary ammonium compounds, nucleobases and nucleosides, amines and polyamines. Absolute concentrations of 32 out of the 42 quantified organic N monomers were significantly different between soil extracted by chloroform gas fumigation and chloroform direct extraction. These differences were probably a function of gains and losses of compounds due to oxidation, hydrolysis and deamidation during the two-day chloroform gas fumigation. Cold methanol/chloroform/water yielded large amounts of the extremely labile compound ergothioneine, probably because the extraction method rapidly quenched metabolic activity. The primary limitation of extraction with methanol/chloroform/water is that it was ineffective at extracting strongly cationic compounds (e.g. polyamines). Extraction with hot aqueous ethanol was unsuccessful with soil presumably because soil microbes are difficult to lyse. It is recommended that future studies examining organic N monomers in soil microbial biomass use chloroform direct extraction or cold methanol/chloroform/water rather than chloroform gas fumigation.     

Inhibitory effects of beer and other alcoholic beverages on mutagenesis and DNA adduct formation induced by several carcinogens

The possibility that beer and other alcoholic beverages could be antimutagenic against the heterocyclic amines (HAs), a group of carcinogens produced on cooking proteinaceous foods, has been explored. In the Salmonella mutation assays, beer showed inhibitory effects against several HAs [preactivated Trp-P-1, Trp-P-2(NHOH), and Glu-P-1(NHOH)] that are directly mutagenic in bacteria. Japanese sake, red and white wines, and brandy were also effective. However, ethyl alcohol alone did not show these effects. The formation of O(6)-methylguanine by N-methyl-N'-nitro-N-nitrosoguanidine in the DNA of Salmonella YG7108 was also inhibited by beer. Nonvolatile beer components were administered orally to CDF(1) mice together with Trp-P-2. Adducts in the liver DNA were significantly decreased by the beer, as compared to those in controls fed Trp-P-2 only. Although several phenolic compounds known to be present in beer were antimutagenic toward these mutagens, their effects were very small. It was concluded that some yet to be identified component(s) of beer is (are) responsible for this antimutagenicity.     

Comparison of Halogenation Potential Among Various Fractions of TOC in Water from Jingmi Canal,Beijing

Naturally occurring organic compounds in water from Jingmi Canal were sequentially fractionated into five fractions using filtration and adsorption columns of XAD-8 and XAD-4 resins in tandem: the fractions being particulates, hydrophobic compounds, humic substances, XAD-4 acids and other hydrophilic neutral solutes. Then each fractions was chlorinated simultaneously with sodium hypochlorite, and the dominant halogenated product determined in this experiment was chloroform. Brominated THMs were detected as well. Both TOC abundance and ratio of CHCl₃ product to corresponding fraction of TOC showed that dissolved humic substances and particulate-adsorbed organics were the major precursors of chloroform. Low-molecular-weight hydrophilic XAD-4 acids also possessed noticeable halogenation activity. Other aquatic organic solutes, however, were relatively inert with respect to the three fractions mentioned above. These results suggested that in addition to humic substances, other potential precursors which have not been studied thoroughly before, such as XAD-4 acids, should be considered during water chloronation.     

Evaluation of Activated Carbon-Coated Electrode in Electrostatic Precipitator and Its Regeneration for Volatile Organic Compounds Removal

Activated carbon-coated electrode was developed and applied in electrostatic precipitator to remove volatile organic compound gases simultaneously with dust particles from a contaminated air. The activated carbon coating mixture was made up of powdered activated carbon (AC), carbon black (CB), and polyvinyl acetate (PVA), and methanol was added as a solvent to control the thickness of the mixture for best coating performance. During the coating process, the Brunauer-Emmett-Teller (BET) surface decreased to 86% of the original AC while pore volume percentages of macro pore increased, compared to micro- and meso-sized pores. The adsorption isotherm of benzene, toluene, ethyl benzene, and xylene (BTEX) gases onto the original AC and AC coating mixture (AC thoroughly mixed with PVA and methanol for coating and powdered again after dry) were tested and compared to each other, and it was found that both isotherm were best fitted to Freundlich and Langmuir isotherm with the order of adsorption capacities; ethyl benzene?>?m-xylene?>?toluene?>?benzene. The difference between adsorption capacities was clearer with the absorbent AC but became little with the AC coating mixture. In removing BTEX at increasing linear velocities up to 6.7 cm/s, it appeared that the surface area of AC electrode was directly proportional to its removal rate of BTEX. The thermal desorption was applied to regenerate the AC electrode, and 200 °C was found to be most efficient for benzene desorption, but higher temperature would be required for entire BTEX gases desorption.     

Analysis of aldehydes in beer using solid-phase microextraction with on-fiber derivatization and gas chromatography/mass spectrometry

A new, fast, sensitive, and solventless extraction technique was developed in order to analyze beer carbonyl compounds. The method was based on solid-phase microextraction with on-fiber derivatization. A derivatization agent, O-(2,3,4,5,6-pentafluorobenzyl)hydroxylamine (PFBOA), was absorbed onto a divinyl benzene/poly(dimethylsiloxane) 65-microm fiber and exposed to the headspace of a vial with a beer sample. Carbonyl compounds selectively reacted with PFBOA, and the oximes formed were desorbed into a gas chromatograph injection port and quantified by mass spectrometry. This method provided very high reproducibility and linearity. When it was used for the analysis of aged beers, nine aldehydes were detected: 2-methylpropanal, 2-methylbutanal, 3-methylbutanal, pentanal, hexanal, furfural, methional, phenylacetaldehyde, and (E)-2-nonenal.     

Adsorption of Petroleum Monoaromatics from Aqueous Solutions Using Granulated Surface Modified Natural Nanozeolites: Systematic Study of Equilibrium Isotherms

Petroleum monoaromatics including benzene, toluene, ethylbenzene, and xylenes (BTEX) are among the notorious volatile organic compounds that contaminate water and soil. In this study, a surfactant- modified natural zeolite and its relevant granulated nanozeolites were evaluated as potential adsorbents for removal of petroleum monoaromatics from aqueous solutions. All experiments performed in batch mode at constant temperature of 20°C and pH of 6.8 for 48 h. The results revealed that the amount of BTEX uptake on granulated zeolites nanoparticles were remarkably higher than the parent micron size natural zeolite (in the order of four times). The isotherms data were analyzed using five models namely, Langmuir, Fruendlich, Elovich, Temkin, and Dubinin?CRadushkevich models. It was concluded that the Langmuir model fits the experimental data. The measured adsorption capacities were 3.89 and 4.08 mg of monoaromatics per gram of hexadecyltrimethylammonium-chloride and n-cetylpyridinium bromide (CPB)-modified granulated nanozeolite, respectively. Considering the type of surfactant, adsorbents modified with CPB showed greater tendency for the adsorption of the adsorbates.     

Organo-clays as adsorbents for azinphosmethyl and dichlorvos in aqueous medium

Using adsorption isotherms, a study was performed of the adsorption of two organophosphorus pesticides, azinphosmethyl (sparingly soluble in water) and dichlorvos (moderately soluble in water), by montmorillonites saturated with the cations hexadecyltrimethylammonium (HDTMA⁺), dodecyltrimethylammonium (DDTMA⁺) and tetramethylammonium (TMA⁺) in aqueous media. The results were compared with those obtained for the adsorption of these pesticides by natural montmorillonite, humic acid and by the soil organic matter and with the octanol-water partition coefficient (Kow) of the compounds. Results indicated that regarding the capacity to remove azinphosmethyl from water the organic matter derived from the organic cations HDTMA⁺ and DDTMA⁺ is 5–10 times more effective than humic acid; 10–20 times more effective than the organic matter from the soil and 20–50 times more efficient than octanol. However, both organic phases, that derived from the organic matter of the soil and that of the organic cations, have similar effectiveness for removing dichlorvos from water, in turn, their efficiency is 50 times higher than that of octanol. These findings may find application in the removal of azinphosmethyl or other sparingly water soluble organophosphorus pesticides from aquifers.     

黄棕壤中活性有机碳对Cu吸附的影响

通过盐酸酸化法来去除4种不同利用方式黄棕壤的活性有机碳（AOC）,得到相对稳定的有机碳土壤,用于研究去除活性有机碳前后对Cu2＋吸附行为的影响。结果表明,黄棕壤去除有机碳前后,对Cu2＋吸附量与平衡液浓度的关系符合Langmuir方程和Freundlich方程,其拟合都呈现极显著相关（P〈0.01）,去除AOC后,黄棕壤各层次对Cu2＋的最大吸附量明显降低,是原土Cu2＋最大吸附量的10%～30%。盐酸酸化法对4种不同利用方式的黄棕壤有机碳的去除率为30%～75%,对Cu2＋吸附的减少率为54%～86%。去除活性有机碳前后,有机碳含量与对Cu2＋的吸附量都呈显著线性相关。土壤有机碳的去除率与对Cu2＋吸附的减少率间相关性达到极显著水平。     

有机质对广西酸性富硒土中Se(Ⅳ)吸附解吸特性的影响

为探究有机质在酸性富硒土吸附Se(Ⅳ)过程中的作用，以广西典型富硒区的赤红壤为材料，研究了酸性富硒土去除有机质后，土壤硒的赋存形态、土壤对Se(Ⅳ)的吸附解吸特征及吸附前后土壤基团的变化。结果表明：(1)去除有机质后，土壤中有机结合态硒大幅度减少，铁锰结合态硒成为土壤硒的主要赋存形态。(2)吸附试验表明，土壤对Se(Ⅳ)吸附过程以多分子层的不均质表面吸附为主，吸附过程受控于化学反应与化学吸附；去除有机质后，土壤对Se(Ⅳ)吸附量和吸附强度均显著下降。(3)解吸试验表明，吸附以难解吸的专性吸附为主；去除有机质后，解吸量与解吸率下降，固液分配系数K_d值下降。(4)傅里叶变换红外光谱表明，土壤吸附Se(Ⅳ)与静电引力、络合反应和配位体交换有关；去除有机质减少了有机官能团的数量，导致吸附量减少。综上，有机质的存在，提升了酸性富硒土对Se(Ⅳ)的吸附容量和吸附强度，是造成酸性富硒土硒有效性较低的重要因素。     

Efficiency of rice bran for the removal of selected organics from water: kinetic and thermodynamic investigations

The sorption efficiency of indigenous rice (Oryza sativa) bran for the removal of organics, that is, benzene, toluene, ethylbenzene, and cumene (BTEC), from aqueous solutions has been studied. The sorption of BTEC by rice bran is observed over a wide pH range of 1-10, indicating its high applicability to remove these organics from various industrial effluents. Rice bran effectively adsorbs BTEC of 10 microg mL(-1) sorbate concentration from water at temperatures of 283-323 +/- 2 K. The effect of pH, agitation time between solid and liquid phases, sorbent dose, its particle size, and temperature on the sorption of BTEC onto rice bran has been studied. The pore area and average pore diameter of rice bran by BET method are found to be 19 +/- 0.7 m(2) g(-1) and 52.8 +/- 1.3 nm. The rice bran exhibits appreciable sorption of the order of 85 +/- 3.5, 91 +/- 1.8, 94 +/- 1.4, and 96 +/- 1.2% for 10 microg mL(-1) concentration of benzene, toluene, ethylbenzene, and cumene, respectively, in 60 min of agitation time using 0.1 g of rice bran at pH 6 and 303 K. The sorption data follow Freundlich, Langmuir, and Dubinin-Radushkevich (D-R) models. Sorption capacities have been computed for BTEC by Freundlich (32 +/- 3, 61 +/- 14, 123 +/- 28, and 142 +/- 37 m mol g(-1)), Langmuir (6.6 +/- 0.1, 7.5 +/- 0.13, 9.5 +/- 0.22, and 9.4 +/- 0.18 m mol g(-1)), and D-R isotherms (11 +/- 0.5, 16 +/- 1.3, 30 +/- 2.2, and 33 +/- 2.5 m mol g(-1)), respectively. The Lagergren equation is employed for the kinetics of the sorption of BTEC onto rice bran and first-order rate constants (0.03 +/- 0.002, 0.04 +/- 0.003, 0.04 +/- 0.003, and 0.05 +/- 0.004 min(-1)) have been computed for BTEC at their concentration of 100 mug mL(-1) at 303 K. Studies on the variation of sorption with temperatures (283-323 K) at 100 mug mL(-1) sorbate concentration gave thermodynamic constants DeltaH (kJ mol(-1)), DeltaG (kJ mol(-1)), and DeltaS (J mol(-1) K(-1)). The results indicate that the sorption of organics onto rice bran is exothermic and spontaneous in nature under the optimized experimental conditions selected. This sorbent has been used successfully to accumulate and then to determine benzene, toluene, and ethylbenzene in wastewater sample.     

Removal of Benzene Using the Characteristics of Block Copolymers for Encapsulation

This study assessed the aqueous benzene removal capacity of a polymeric adsorbent, based on an amphiphilic material, in a batch experiment. Two types of polystyrene-block-poly(N-isopropylacrylamide) have structures containing a hydrophobic core and hydrophilic shell. The encapsulation mechanism of benzene by a polymeric adsorbent was investigated, and found to be attributable to the Van der Waals interactions between the benzene aromatic ring and the hydrophobic core of the adsorbent. The equilibrium data were analyzed using the Langmuir and Freundlich adsorption isotherms, and found to be a good fit to both. The maximum adsorption capacity for benzene by the polymeric adsorbent was found to be 194.53 mg/g. The kinetic data followed a pseudo-first-order kinetic model. Polystyrene-block-poly(N-isopropylacrylamide) showed the potential to be an effective adsorbent for application to wastewater treatment.     

Biodegradation of Trichloroethylene in Finished Compost Materials

Growing interest in the use of biofiltration technology to remove toxic organic compounds from gaseous waste streams has led to the investigation of various solid packing materials to support microbial populations capable of contaminant biodegradation. Finished compost material has been used as a biofiltration packing matrix for the treatment of noxious odors and the removal of several gaseous organic contaminants. Trichloroethylene (TCE), a widespread groundwater contaminant, has been shown to undergo aerobic biodegradation under a variety of environmental conditions. The current investigation focused on the capacities of five different finished compost materials to remove TCE from head space vapors in small reaction flasks. Due to the cometabolic nature of aerobic TCE biodegradation, enrichment of compost materials with propane or methane as primary substrates was tested as a means to stimulate biological TCE removal. Results indicate that all of the materials tested removed at least 85 percent of the added TCE (initial head space concentration = 5.0 ppmv) without enrichment and over 99 percent total removal was observed in samples enriched with propane gas. Rapid adsorption of TCE accounted for up to 77 percent of the removal observed in the reactors. This study suggests that finished compost material from a variety of sources has considerable potential for use as a biofiltration packing material for the treatment of chlorinated solvent vapors in waste gas streams.     

Study of nickel sorption onto biological sludges. possibilities for heavy metals removal treatments

Nickel adsorption onto a sludge wasting from a biological aeration tank is described in this work. This procedure is planned as an alternative method for metal removal from industrial effluents containing heavy metals in low concentrations. Experimental results of equilibrium adsorption and laboratory equipment operation are reported. Equilibrium data of nickel adsorption were fitted to the Freundlich equation. On the basis of this equation, the effect of several parameters such us metal concentration, sludge concentration and metal dosing rate were tested. Nickel removal efficiency is about 80% in the most favourable cases. Aeration during metal-sludge contact was also tested but little enhancing in metal uptake was observed. This analysis can be used to define the best operation conditions in practical cases either for metal or organic matter removal.     

Effect of maize root mucilage on phosphate adsorption and exchangeability on a synthetic ferrihydrite

 This study was conducted to determine the influence of root mucilage (RM) from Zea mays, polygalacturonic acid (PGA), and galacturonic acid (GA), on the adsorption, desorption, and exchangeability of orthophosphate (P) on a synthetic ferrihydrite in deionized water. The adsorption rate and affinity on the oxide decreased in the order P>GA>PGA≥RM. The results suggest that P and GA were adsorbed by ligand exchange on Fe-OH surface sites, while RM and PGA might in addition also be adsorbed by hydrogen and van der Waals bonds to the oxide surface. Whereas P and GA could be adsorbed at sites located inside the micropores of ferrihydrite aggregates, PGA and RM probably remained on the external surfaces because of their large molecular weight. The preliminary adsorption of organic compounds decreased the subsequent P adsorption. The larger decrease of P adsorption occurred when dry ferrihydrite powder was directly added to the RM/water suspension. This effect was due to the flocculation of ferrihydrite aggregates, which limited the transport of P to the adsorption sites. Preliminary adsorption of GA also decreased P adsorption, because both compounds competed for the same Fe-OH sites. The ability of the organic compounds to desorb P from the ferrihydrite was not very pronounced and decreased in the order GA>PGA≥RM. The preliminary adsorption of organic compounds on the oxide resulted in an increase in isotopically exchangeable P in 300 min compared to the treatment without organic compounds. However, because of its higher affinity for the oxide surface, P exchangeability was not modified when P was added before the organic compounds. Received: 23 July 1999     

A Novel Pretreatment Method of Lignocellulosic Material as Adsorbent and Kinetic Study of Dye Waste Adsorption

Sulphuric acid-modified bagasse has been used as low-cost adsorbent for the removal of methylene blue (MB) dye from aqueous solution. In order to remove organic compounds that contribute to chemical oxygen demand (COD), pretreatment with thorough washing of adsorbent using boiling distilled water was performed instead of conventional washing using distilled water at room temperature only. This has resulted in the highest efficiency of color removal of 99.45% and COD reduction of 99.36% for MB dye solution at pH 9. Effects of initial pH, dye concentration, adsorbent dosage, temperature, and contact time have been studied. The adsorption of MB dye was pH dependent. Langmuir and Freundlich isotherm models were tested on the adsorption data. The kinetic experimental data were analyzed using pseudo-first order, pseudo-second order, and the intraparticle diffusion model in order to examine the adsorption mechanisms. The adsorption process followed the Langmuir isotherm as well as the Freundlich isotherm and pseudo-second-order kinetic model. The process was found to be endothermic in nature.