Removal of 2,4-dinitrophenol using hybrid methods based on ultrasound at an operating capacity of 7 L.

Sonochemical removal of 2,4-dinitrophenol (DNP) has been investigated using ultrasonic bath, with an operating capacity of 7 L, fitted with a large transducer with longitudinal vibrations having a 1 kW rated power output and operating frequency of 25 kHz. It has been revealed from calorimetric studies that maximum power is dissipated at a capacity of 7 L. The concentration of DNP has been monitored with an objective of evaluation of the efficacy of ultrasonic reactor in combination with process intensifying approaches for the removal of DNP. The effect of operating pH and additives such as hydrogen peroxide and ferrous iron activated persulfate on the extent of removal of DNP has been investigated. It has been observed that the extent of removal is greater at lower pH (pH 2.5 and 4) than at higher pH (pH 10). The combined treatment strategies such as ultrasound (US)/Fenton, US/advanced Fenton and US/CuO/H2O2 have also been investigated with an objective of obtaining complete removal of DNP using hybrid treatment strategies. The extent of removal has been found to increase significantly in US/Fenton process (98.7%) as compared to that using US alone (5.8%) which demonstrates the efficacy of the combined process. First order kinetics has been fitted for all the approaches investigated in the work. Calculations of cavitational yield indicated the superiority of the reactor design as compared to the conventional ultrasonic horn type reactors. The main intermediates formed during the process of removal of DNP have been identified.

[Preparation, characterization and adsorption performance of high surface area biomass-based activated carbons].

High surface area activated carbons were prepared with Spartina alterniflora and cotton stalk as raw materials and KOH as activating agent. Effects of materials type, impregnation ratio, activation temperature and heat preservation time on the yield, elemental composition and adsorptive capacity of activated carbon were studied. The properties and pore structure of the carbons were characterized with nitrogen adsorption, powder X-ray diffractometry (XRD), infrared spectroscopy (FTIR) and scanning electron microscopy (SEM). Main pore characteristics of activated carbons were analyzed by BET equation, Horvath-Kawazoe BET method and DFT method. The considerable preparation conditions are obtained as follows: impregnation ratio of 3: 1, an activation temperature of 800 degrees C and an activation time of 1.5 h. The BET surface area of activated carbon prepared from Spartina alterniflora reached 2 825 m2 x g(-1) when its total pore volume, yield, iodine number and methylene blue adsorption were 1.374 cm3 x g(-1), 16.36%, 1797 mg x g(-1) and 495 mg x g(-1) respectively under above conditions. The activated carbon from cotton stalk was prepared with BET surface area of 2 135 m2 x g(-1), total pore volume of 1.038 cm3 x g(-1), yield of 11.22%, methylene blue adsorption of 1 251 mg x g(-1), and iodine number of 478 mg x g(-1), respectively. The methylene blue adsorption and iodine number are much higher than the national first level for activated carbon. The Langmuir maximum adsorption capacities of 2,4-dinitrophenol on the two carbons were 932 mg x g(-1) and 747 mg x g(-1), respectively, which are superior to ordinary activated carbon and activated carbon fiber.

[Use of the analytical method LC-MS/MS for finding dinoseb and dinoterb in agricultural products, livestock products and seafood].

A simple determination method of dinoseb and dinoterb in agricultural products, livestock products and seafood by LC-MS/MS was developed. Agricultural samples were extracted with acetone (in the case of rice, soybean and tea leaf, phosphoric acid was added). An aliquot of crude extract was partitioned with hexane and sat. sodium chloride solution. In the case of livestock products and seafood, samples were extracted with a mixture of acetone, hexane, water and sodium chloride, and the organic layer was collected. Clean-up was performed using a PSA mini column. The LC separation was performed on a C18 column with methanol-water (19 : 1) containing 0.005 v/v% acetic acid as a mobile phase, and MS with negative ion electrospray ionization was used for detection. The calibration curve was linear between 0.0005 to 0.04 µg/mL for each compound. Average recoveries (n=5) of dinoseb and dinoterb from 20 kinds of agricultural products, livestock products and seafood fortified at the MRLs were 77-111%, and the relative standard deviations were 2-15%. The limits of quantitation were 0.001 µg/g for both compounds.

Study on the aerobic biodegradability and degradation kinetics of 3-NP; 2,4-DNP and 2,6-DNP.

Four biodegradability tests (BOD(5)/COD ratio, production of carbon dioxide, relative oxygen uptake rate and relative enzymatic activity) were used to determine the aerobic biodegradability of 3-nitrophenol (3-NP), 2,4-dinitrophenol (2,4-DNP) and 2,6-dinitrophenol (2,6-DNP). Furthermore, biodegradation kinetics of the compounds was investigated in sequencing batch reactors both in the presence of glucose (co-substrate) and with nitrophenol as the sole carbon source. Among the three tested compounds, 3-NP showed the best biodegradability while 2,6-DNP was the most difficult to be biodegraded. The Haldane equation was applied to the kinetic test data of the nitrophenols. The kinetic constants are as follows: the maximum specific degradation rate (K(max)), the saturation constants (K(S)) and the inhibition constants (K(I)) were in the range of 0.005-2.98 mg(mgSS d)(-1), 1.5-51.9 mg L(-1) and 1.8-95.8 mg L(-1), respectively. The presence of glucose enhanced the degradation of the nitrophenols at low glucose concentrations. The degradation of 3-NP was found to be accelerated with the increasing of glucose concentrations from 0 to 660 mg L(-1). At high (1320-2000 mg L(-1)) glucose concentrations, the degradation rate of 3-NP was reduced and the K(max) of 3-NP was even lower than the value obtained in the absence of glucose, suggesting that high concentrations of co-substrate could inhibit 3-NP biodegradation. At 2,4-DNP concentration of 30 mg L(-1), the K(max) of 2,4-DNP with glucose as co-substrate was about 30 times the value with 2,4-DNP as sole substrate. 2,6-DNP preformed high toxicity in the case of sole carbon source degradation and the kinetic data was hardly obtained.

Dynamic studies of nitrophenols adsorption on perfil in a fixed-bed column: application of single and two resistance model.

The mechanism of 4-nitrophenol (4-NP) and 2,4-dinitrophenol (2,4-DNP) adsorption on perfil-natural mineral taken from Bulgarian deposits, in a fixed-bed column was investigated. The single component experiments were conducted at constant initial sorbate concentration, volumetric flow rate, temperature and pH. The effect of adsorbent bed depth (Z 1, 2, 3, 6 cm) and sorbate nature on the adsorption capacity, mass transfer parameters and mechanisms was studied. The equilibrium behaviour of the system 4-NP-perfil was described by Langmuir, Freundlich and Redlich-Peterson models. The single resistance Thomas model, including Reynolds-Richards and Walter solutions, and the two-resistance Arnold model were applied for mathematical modeling of the experimental data. The comparative analyses indicated that external mass transfer was the rate limiting mechanism during the initial adsorption stages, while intraparticle diffusion was dominant in the middle and high concentration ranges. The effect of axial dispersion on the dynamics of adsorption was evaluated.

Remediating dinoseb-contaminated soil with zerovalent iron.

Dinoseb, a dinitroherbicide, was once commonly used in aerial crop dusting of agronomic crops in the western United States. Widespread use combined with improper disposal practices at rural air strips has contaminated numerous sites. Our objective was to determine if zerovalent iron (Fe(0)) could remediate dinoseb-contaminated soil. This was accomplished by conducting a series of batch experiments where we first determined if Fe(0) could remove dinoseb in aqueous solutions, then in contaminated soil slurries, and finally, in unsaturated soil microcosms (25 degrees C, theta(g)=0.30 kg H(2)O kg(-1)). Results showed quantitative dinoseb removal in the presence of Fe(0) in all three media (aqueous solutions, soil slurries, moist soils) and that removal increased by including either ferrous or aluminum sulfate with the iron treatment. Incubating contaminated soils with Fe(0) or Fe(0) plus salts (FeSO(4) or Al(2)(SO(4))(3)) resulted in 100% removal of dinoseb within 7 d. Liquid chromatography/mass spectrometry (LC/MS) analysis of degradation products showed the transformations imposed by the iron treatments were reduction of one or both nitro groups to amino groups. These amino degradation products were further transformed to quinonimine and benzoquinone and did not persist. These results support the use of zerovalent iron for on-site treatment of dinoseb-contaminated soil.

Sorption behaviors of aromatic anions on loess soil modified with cationic surfactant.

Modification of soils with hydrophobic cationic surfactants is an effective approach for enhancing the sorptive capabilities of soil in the vadose zone for the purpose of retaining organic contaminants prior to cleanup. The objective of this study was to examine the sorptive behavior of the cationic surfactant-modified loess soil for aromatic anions in the aqueous phase in an attempt to define the sorptive mechanisms. Some dominant factors governing the sorption, such as ionic strength and divalent heavy metal cation, were investigated. The sorption isotherms of 2,4-dinitrophenol (DNP) and benzoic acid (BA) in the modified soil samples were obtained using the batch equilibration method. Under the laboratory conditions, the modified loess soil utilized in this study was prepared by replacing the cations of loess soil with a cationic surfactant-hexadecyltrimethylammonium (HDTMA) bromide. The acidic aromatic compounds, DNP and BA existing as aromatic anions in the natural mixture of loess soil and aqueous phase, were selected as indicator compounds to measured the sorption behaviors of aromatic anions on the HDTMA-modified loess soil. The results confirmed that the sorptive capabilities of aromatic anions in loess soil were greatly enhanced by modification with HDTMA. The increase of ionic strength and the addition of divalent heavy metal cation Zn(2+) significantly increased the sorption of aromatic anions on the HDTMA-modified loess soil. In binary solute systems, the sorbed amounts either of DNP or BA on the HDTMA-modified loess soil were reduced if two compounds existed simultaneously in the soil. This results indicated that competitive adsorption between the two aromatic anions occurred in soil matrix.