Research Journal of Chemistry and Environment

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Vol. 17(11) November 2013

Emission factors of biogenic volatile organic compounds in various stages of growth present in the urban forest of the Metropolitan Region, Chile

Préndez Margarita*, Corada Karina and Morales Johanna

Chile’s capital in the Metropolitan Region has an atmosphere polluted especially by particulate matter in winter and by ozone in summer. Trees are used as a natural strategy for decontamination; however, they emit biogenic volatile organic compounds (BVOCs) whose atmospheric reactions generate secondary chemical species, including ozone. This study presents the experimental emission factors (EF) of BVOCs in young and adult individuals of three native trees (Cryptocarya alba, Quillaja saponaria and Schinus molle) and one non-native (Quercus suber). To distinguish the environmental impact of the young and adult individuals studied, the EF and the Photochemical Ozone Creation Index (POCI) were calculated. Results show that the concentrations of isoprene emitted by the trees studied (young or adult) correlated with neither PAR nor temperature in autumn, monoterpenes correlated with PAR and/or temperature (young or adult), but the specific monoterpene depended on the tree species. The open question is how much would be necessary to normalize the EF in order to obtain better values for introducing an emission inventory which elaborated more reliable decontamination strategies.

Chemotaxis of Cupriavidus necator JMP134 towards aromatic compounds

Ying X. U.

Cupriavidus necator JMP134 grows on a broad range of aromatic compounds as a sole source of carbon and energy. However, not much is known about its chemotactic ability to these aromatics except for 2,4-dichlorophenoxyacetate. In the current study, the chemotactic ability of C. necator JMP134 to thirty aromatic compounds was investigated. Compounds were the metabolizable, nonmetabolizable and nonresearched aromatic compounds for strain JMP134. Among the investigated substrates, strain JMP134 cells were found to be chemotactically attracted to as many as eleven metabolizable aromatic compounds including meta-nitrophenol, 4-methyl-phenol, 2,4-dichlorophenoxyacetate, benzoate, three isomers of mono-hydroxybenzoate and so on; and three nonmetabolizable isomers of chlorophenol. The chemotactic responses of strain JMP134 to these compounds were constitutively expressed except for 2,4-dichlorophenoxyacetate. The “substrate range” for chemotaxis system in strain JMP134 is probably non-specific and substrate-broader than their respective catabolic enzymes for degardation. Furthermore, the chemotaxis response was evidently enhanced after being induced by metabolizable compounds such as meta-nitrophenol.

Chemical profiling of fifty constituents in Qi-gui-yin granule (QGY) by on-line high-performance liquid chromatography coupled with ESI-LTQ-Orbitrap mass spectrometer

Xiaojie Yu, Jiayu Zhang, Qingquan Liu, Zhisheng Wu, Shanshan Liu, Hang Shi1 and Qun Ma*

A systematic and rapid method was established using on-line high performance liquid chromatography- electrospray ionization-linear ion trap-Orbitrap hybrid mass spectrometry (HPLC-ESI-LTQ-Orbitrap) to analyze the bioactive constituents in the extract of Qi-gui-yin granule (QGY), a five-herb traditional Chinese patent medicine which is used for the treatment of multiple drug-resistant Pseudomonas aeruginosa infections. Identification of the constituents was carried out by interpretation of their retention time, ESI-MS and MS/MS data and comparing with reference compounds under the same LC-MS conditions, as well as the data provided by the literature. The analysis was performed in both positive and negative mode to acquire accurate mass data in the full scan MS experiment. In the result, a total of 50 compounds attributed to six categories were identified including 14 flavonoids, 19 phenylpropanoids, 4 anthraquinones, 3 isoflavans, 2 isoflavones and 8 other compounds. Among them, 37 compounds were first characterized in QGY by the developed LC-ESI-MSn method. The results indicated that the developed analytical method could be employed as a rapid, effective technique for structural characterization of the multiple constituents in QGY. Meanwhile, the identification and structural analysis of the chemical constituents have provided essential data for the further studies on material foundation of QGY.

Chemical composition of Toona sinensis essential oil and DPPH scavenging activity of different fractions in ethanol extract of Toona sinensis from China

Chen Congjin,* Li Yue, Liao Dankui, Tong Zhangfa1, and Yang Guoen

Chemical components of essential oil of Toona sinensis (A.Juss.) Roem from China, separated by simultaneous distillation solvent extraction (SDE), were analyzed by GC-FIRD and GC-MS. The DPPH scavenging activity of the essential oil and different fractions of the associated ethanol extract was also evaluated. Seventy-seven compounds were identified in the essential oil of the leaves and eighty-one compounds were identified in the essential oil of the common petioles, the sum of relative mass fraction accounting for 98.86% and 98.64% respectively. The main components in the essential oil from leaves were β-caryophyllene (19.51%), humulen-(v1) (16.04%), himachala-2, 4-diene (5.71%), seychellene (4.82%), longifolene-(V4) - (4.42%), caryophyllene oxide (4.03%), aristolene (3.18%). The main components in the essential oil from common petioles were longifolene- (V4) - (16.4%), himachala - 2, 4-diene ( 14.64% ), β - caryophyllene (6.6%), δ-cadinene (4.41%), humulen-(v1) (4.38%), α-guaiene (3.89%), tau - cadinol (3.85%), α-copaene (3.18%). The essential oil of Toona sinensis can be used as food additives with a special flavor. The weak DPPH scavenging activity of Toona sinensis essential oil indicated weak antioxidant capacity. The ethyl acetate fraction and ethanol extracts from Toona sinensis leaves and common petioles exhibited high DPPH scavenging activity, with that of the common petiole material exceeding that of the leave materials. The results indicated that Toona sinensis may be a useful new source of natural antioxidants.

Mechanism of Mn(II) Absorption and Desorption with 4A Zeolite

Peng Xi, Wu Dandan, Zheng Lei, Li Dongwei* and Xu Zhonghui

Three different Zeolites(3A, 4A and 5A) were used to investigatetheir adsorptivities to Mn(II) in aqueous solution through a preliminary experiment. The one with the best capability would be used in an orthogonal experiment to find out the most appropriate parameters. The Mn(II) loaded zeolite from best condition was put into soduim chloride water solution to get desorbed . X ray diffraction (XRD) was used to characterize the initial and loaded zeolites in order to research its absorption mechanism. The experiment results showed that the three zeolites have various adsorptivities, with 4A ranking top, which exhibits most excellent performance for Mn(Ⅱ) removal with reaction condition as follows:4A zeolite 0.6g, water temperature 35oC，oscillation frequency 115 rpm , contact time 30 min,when it has an adsorption rate of 97.89%. The desorption rate of loaded zeolite in 0.1M soduim chloride water solution for 24 hours is as high as 94.2%.XRD analysis shows ion exchange between Mn2+ in aqueous solution and Zeolite 4A.

Study of Two-Stage Thermal Destruction System for the Treatment of Spent Cation Exchange Resins without releasing Semi-Volatile Caesium

Yang H. C.*, Lee M. W., Whang H. S., Chung D. Y. and Moon J. K.

A two-stage thermal treatment system for spent cation exchange resins that guarantees retention of semi-volatile caesium was proposed and tested. Cation exchange resins doped with radioactive metal surrogates (Co, Sr and Cs) were used as model spent cation exchange waste. Sr and Co did not escape from the pyrolysis residue at the tested temperature range (500-600C). The retention of caesium was greatly influenced by the pyrolysis temperature. Nearly 2% of caesium escaped at 600C. The highest pyrolysis temperature with caesium retention of >99.9% was 560C which was established as the optimum pyrolysis temperature. Numerical modelling and experimental validations were performed to establish optimum conditions of a plug-flow reactor (PFR) type thermal oxidizer. Optimum conditions of a thermal oxidizer with 5-cm ID and 30-cm length for the destruction of hydrocarbons generated from the pyrolysis furnace were determined as an air equivalence ratio () of  0.3 (equals 230 % excess air) and temperature of  750C.

Sulfate removal and sulfur recovery by combined anaerobic reduction and mixotrophic desulfurization-denitrification biofilm process

Wei Li1,*, Xiao Liang, Jianguo Lin and Lei Liu1

Two anaerobic attached-growth bioreactors were set up to treat sulfate-laden organic wastewater by anae-robic reduction and mixotrophic desulfurization-denitrification biofilm process for 370 days. In anae-robic sulfate reduction reactor (AR), the influent sul-fate was increased from 900 mg SO42-/l to 2100 mg SO42-/l, then changed to 1800 mg SO42-/l at HRT of 6 h. The removals of sulfate could reach 93.3%. The sulfide generating rate was high at 97.5%. In mixo-trophic desulfurization-denitrification biofilm reactor (MR), HRT was decreased from 6.63 h to 3.31 h. The sulfide was removed up to 100% and predominantly oxidized to sulfur. The final average removal of sul-fate was 93.8% at volumetric loadings of 7200 mg SO42-/(L•d). The sulfate was finally converted into sul-fur which could be reused and would not cause sec-ondary pollution.

Removal of Cu2+ from aqueous environments using zero-valent iron: Effects of pH, dissolved oxygen and humic acid

Rao Pinhua1, Liu Tongzhou*, Zhang Wenqi, Yao Wei1 and Du Yongtao

To provide extended information for assessing the application of zero-valent iron (Fe0) based technolo-gy in the environment with aquatic characteristics variation, a detailed investigation of Cu2+ removal by Fe0 as influenced by pH, dissolved oxygen and humic acid was conducted in batch settings. Changes of solution pH and dissolved iron concentration in the process of experiments were particularly monitored to reveal removal mechanisms of Cu2+. Results showed that the efficiency of Cu2+ removal decreased with the enhancement of acidity. Compared with deoxygenating condition, oxygenating condition showed unfavorable effects on the removal of Cu2+. The results of MgCl2 solution extraction and HNO3 digestion of the suspended solids formed in oxygenated solutions indicated considerable contribution of adsorption to Cu2+ removal, revealing a risk that surface bound Cu might be eluted from Fe0 medium having high DO condition. In the presence of humic acid, Cu2+ removal kinetics by Fe0 was accelerated or retarded dependently on humic acid concentration. Low concentration of humic acid accelerated Cu2+ removal while high concentration of humic acid decelerated Cu2+ removal. In humic acid-rich environments, the retardation on Cu2+ removal should be considered in the design of Fe0 treatment system to achieve satisfied removal efficiency.

Dissolution and solubility of hydroxylapatite and fluorapatite at 25oC at different pH

Caichun Wei, Yinian Zhu*, Feng Yang, Jiao Li, Zongqiang Zhu and Hongxiang Zhu

Dissolution of the synthetic hydroxylapatite (HAP) and fluorapatite (FAP) was studied at 25oC at differ-ent pH in a series of batch experiments. The XRD, FT-IR and FE-SEM analyses indicated that the HAP and FAP were found to have no obvious variation after dissolution except that the existence of OH groups in FT-IR spectra for FAP after 7200h dissolution at constant pH 2 was observed. During the HAP and FAP dissolution at constant pH 2 and initial pH 2, the release of calcium and phosphate increased and reached a steady state after 1000h. For the dissolution at initial pH 5.6 and 9, the aqueous pH, calcium and phosphate concentrations increased rapidly and reached the peak values after 12-24h and then decreased gradually with time until a steady state was attained. The aqueous calcium and phosphate concentrations during the FAP dissolution were significantly lower than those during the HAP dissolution. The mean logKsp values were calculated by using PHREEQC for HAP of -57.72 (-57.39 ~ -58.05) and for FAP of -59.08 (-58.65 ~ -59.75) at 25oC at initial pH 2, the free energies of formation ΔGfo[HAP] and ΔGfo[FAP] were calculated to be -6310.98 and -6440.64 kJ/mol respectively.

Release characteristics and structure of Gleditsia sinensis polysaccharide-g-N-isopropyl acrylamide hydrogels

Jian Honglei, Gao Zhiyuan and Jiang Jianxin*

Sinomenine hydrochloride (SM) was selected as a model drug to investigate the release characteristics of Gleditsia sinensis polysaccharide- g-N-Isopropyl Acrylamide (GSPNA), the graft copolymer of Gleditsia sinensis polysaccharide (GSP) and N-isopropyl acrylamide (NIPAM). The effects of temperature, ionic strength, release medium pH, the amount of glutaraldehyde and the concentration of Gleditsia sinensis polysaccharide-g-NIPAM on the drug release characteristics were explored. The drug was released at a faster rate in pH 1.0 than in 6.8. No prominent differences in the diffusion coefficient were observed at temperatures below the lower critical solution temperature (LCST). At the LCST of the polymer, the amount of SM released from the thermo-sensitive GSPNA hydrogel was significantly higher than that released from the GSP hydrogel due to conformational transition of the graft-polymer. Furthermore, the ionic strength, the amount of glutaraldehyde and the concentration of Gleditsia sinensis polysaccharide-g-NIPAM also significantly influenced the release of SM. Analysis of the structure and characteristics of the hydrogel by Differential thermal gravimetry, X-ray diffraction and Scanning electron microscopy showed marked differences between the characteristics of the Gleditsia sinensis polysaccharide-g-NIPAM hydrogel and the GSP hydrogel. The Gleditsia sinensis polysaccharide-g- NIPAM hydrogel is temperature and pH sensitive and has potential for use in intelligent drug delivery.

Design and Fabrication of Theophylline loaded Magnetic Nanostructure for Targeted Drug Delivery Application

Sharafi Afsaneh, Sajjadi Perissa Seyed, Farhadyar Nazanin and Seyedsadjadi Mirabdullah,*

In this work we report design and fabrication of theophylline loaded magnetic iron oxide nanostructure by adding appropriate amount of aqueous solution of theophylline in a dispersed solution of Fe3O4@SiO2@APTS conjugate. Dispersed solution of Fe3O4@SiO2@APTS conjugate was prepared by microemulsion technique using water in n-hexane as water in oil phase. Hexadecyltri- methylammonium bromide (CTAB) and n-butanol were used as surfactant and cosurfactant. Surface modification was carried out in pot, using tetraethoxysilane (TESO) and N-aminopropyltri- methoxysilane (APTS). Characterization of the samples was carried out using X-ray powder diffraction (XRD), Scanning electron microscopy, X-ray energy dispersive techniques (SEM-EDX) and Vibrating sample magnetometer (VSM) at room temperature. The loading of theophylline on nanostructured Fe3O4@SiO2@APTS conjugated with fast response to applied magnetic fields, zero remanence and coercivity properties, was confirmed by Fourier transform infrared spectroscopy (FT-IR) and measured by UV spectroscopy.

Aldol Condensation of Acetone over Amberlyst - 15: Batch Kinetics and Process Intensification

Deorukhkar Onkar A. and Mahajan Yogesh S.*

Aldol condensation of acetone (Ac) to yield diacetone-alcohol (DAA) and mesityl-oxide (MO) using Amberlyst -15 as the ion-exchange-resin (IER) catalyst has been explored in this work. IER has proven to be beneficial as catalyst due to several reasons like better conversion and environmental friendliness etc. Green chemistry which employees the concept of carbon economy and better processes/catalysts finds applications in almost every field of reaction engineering, including this reaction which is reported to be catalyzed by acid and base catalysts alike, with obvious advantages and disadvantages. Present work has made an attempt to study the reaction in batch mode with reactive separation (distillation and adsorption). Thus, reactions in batch mode have been compared with those in the semi batch Reactive Distillation (RD) mode and in the Reactive Chromatographic (RC) column. The batch kinetic data was used to regress the kinetic parameters for use in reactive separation modeling. The same was found in-line with the values in the literature. Kinetics revealed that the catalyst is suitable but the rates are low. Hence in order to improve the process and for the purpose of Process Intensification (PI), RD and RC were employed.

Biosorption of Chromium from Synthetic Aqueous Solution using Codium Tomentosum

Suresh Babu P., Dinesh Kumar B. and Anandaraj B.*

Codium tomentosum, a marine macroalgae was investigated for its competence in the effective removal of hexavalent chromium ions from the aqueous solution. It was screened as natural, plentiful, potential and low cost biosorbent to provide an active solution using non-conventional methods by sequential optimization for various influencing parameters like pH, initial Cr6+ ion concentration, adsorbent dosage and equilibrium contact time. Native biomass was milled and sieved to 600 microns size was used throughout the batch experiments. All the experiments were conducted at room temperature. Biosorption strongly depends upon the acidic pH of the solution. The maximum absorption of Cr6+ ion was found to increase with steady increase in the biomass quantity at pH 2. The adsorption equilibrium data was well fitted with Langmuir and Freundlich isotherm models and the results found that adsorption process is irrevocable in nature. Based on the results it is indicating that Codium biomass can be used for chromium removal.

Synthesis and characterization of some ethoxyphthalimide substituted triazole derivatives assembled with benzimidazole and thiazolidinone heterocycles

Kumawat M., Kherodiya B. and Talesara G. L.*

Some alkoxyphthalimide derivatized2-(2-(5-((2-methyl -1H-benzimidazol-1-yl)methyl)-4-(4-oxo-2- substituted phenylthiazolidin-3-yl)-4H-1,2,4-triazol-3-ylthio) eth- oxy)isoindoline-1,3-diones (8a-d) have been synthesized by multistep reaction sequence. Ethyl-2-(2-methyl-1H-benzimidazol-1-yl)-acetate (1) prepared by condensation of 2-methyl benzimidazole with ethylchloroacetate was treated with hydrazine hydrate to obtain 2-(1H-benzoimidazol-1-yl)acetohydrazide (2). Alkali induced cyclisation of (2) with CS2 gave 1,3,4- oxadiazolethione derivative (3). Replacement of ring oxygen with nitrogen to convert (3) into a triazole derivative was carried out by condensing with hydrazine hydrate. Schiff’s base derivatives (6a-d) were obtained by nuleophilic addition cum elimination reaction of amino group of (4) with various araldehydes (5a-d). Condensative cyclisation of benzimidazolylthioxotri- zoles with thiolacetic acid in ZnCl2/DMF gave corresponding phenyl thiazolidinone derivatives (7a-d). Thiol form of triazolethiones was finally condensed with phthalimidoxyethyl bromide to synthesize targeted products (8a-d). Structures of synthesized compounds were confirmed by spectral studies (IR, 1H NMR, Mass), elemental analysis and chemical tests.

Bioremediation of Endosulfan contaminated Soil

Mohanasrinivasan V.*, Suganthi V., Selvarajan E., Subathra Devi C., Ajith E., Muhammed Farhan N. P. and Sreeram Gopalakrishnan

Endosulfan is Cyclodiene organo chlorine currently used as an insecticide all over the world and its residues are posing a serious environmental threat causing long-term harm to human and wildlife. In the present study endosulfan degrading 4 bacterial strains (B1: Staphylococcus B2: Micrococcus B3: Bacillus B4: Pseudomonas) and 5 fungal strains (F1: Mucor F2: Pencillium F3: Aspergillus fumigates F4: Candida F5: Yeast) were isolated from cashew growing soil of Kasargode district at Kerala. The isolated strains were determined for endosulfan degradation potential in lab scale and in pilot plant study. In the lab scale, all the 9 strains differed substantially in their potential to degrade endosulfan ranging from 88 to 93% of the spiked amount (100 mg l–1). The degradation efficiency of the microbes was confirmed in the pilot plant studies with bacterial and fungal consortium. The initial concentration of endosulfan in pilot plant studies was 1000 mg/kg. Bacterial consortium showed 82.5% of degradation after 30 days and fungal consortium showed 80.3% of degradation. B2, F2, bacterial consortium and fungal consortium were analyzed using GC-MS and the degraded product was found to be endosulfan lactone or endolactone. Thus the result of the present study implies that microbial degradation of endosulfan by soil microbes may provide a basis for the development of bioremediation strategies to remediate the pollutants in the environment.

Short Communication:

Feasibility of acetone-butanol-ethanol (ABE) production from the fermentation of oil palm trunk juice

Norhazimah A. H.*, Asmadiyana M. and Faizal C. K. M.

Oil palm trunk (OPT) juice has the potential to be used for acetone-butanol-ethanol (ABE) production. In this study, fermentation of OPT juice was carried out to produce ABE without the addition of nutrient. In general, C. acetobutylicum showed better ABE yield compared to C. beijerinckii even though both strains were capable to convert sugar in OPT juice to ABE. The result showed a maximum acetone, butanol, and ethanol concentration of 12.25, 4.56, and 4.28 g/l respectively using C. acetobutylicum. These results showed that OPT juice has a great potential for ABE production. The procedure used did not require the addition of costly pretreatment and nutrient supplementation.

Review Paper:

Biosorption of heavy metals using low cost agricultural by products

Rangabhashiyam S., Anu N. and Selvaraju N.*

Heavy metal pollution has risen from various sectors of industries like electroplating, fertilizer, leather. paint, pesticide, pharmaceuticals, pulp and paper, mining, oil refinery etc. The removal of heavy metals is of special concern due to their recalcitrance and persistence of existence in the environment. Utilizing agricultural by products as low-cost biosorbents is more attractive because of their biodegradablility in nature, highly economical, reduction of cost in agricultural waste management and having major contribution in the protection of the environment. In general the chemical modifications of agricultural by products bring out enhanced adsorption capacities than in the unmodified forms.