Biodegradation of crystal violet by Agrobacterium radiobacter.

Agrobacterium radiobacter MTCC 8161 completely decolorized the Crystal Violet with 8 hr (10 mg/L) at static anoxic conditions. The decreased decolorization capability by A. radiobacter was observed, when the Crystal Violet concentration was increased from 10 to 100 mg/L. Semi-synthetic medium containing 1% yeast extract and 0.1% NH4C1 has shown 100% decolorization of Crystal Violet within 5 hr. A complete degradation of Crystal Violet by A. radiobacter was observed up to 7 cycles of repeated addition (10 mg/L). When the effect of increasing inoculum concentration on decolorization of Crystal Violet (100 mg/L) was studied, maximum decolorization was observed with 15% inoculum concentration. A significant increase in the activities of laccase (184%) and aminopyrine N-demethylase (300%) in cells obtained after decolorization indicated the involvement of these enzymes in decolorization process. The intermediates formed during the degradation of Crystal Violet were analyzed by gas chromatography and mass spectroscopy (GC/MS). It was detected the presence of N,N,N',N"-tetramethylpararosaniline, [N, N-dimethylaminophenyl] [N-methylaminophenyl] benzophenone, N, N-dimethylaminobenzaldehyde, 4-methyl amino phenol and phenol. We proposed the hypothetical metabolic pathway of Crystal Violet biodegradation by A. radiobacter. Phytotoxicity and microbial toxicity study showed that Crystal Violet biodegradation metabolites were less toxic to bacteria (A. radiobacter, P. aurugenosa and A. vinelandii) contributing to soil fertility and for four kinds of plants (Sorghum bicolor Vigna radiata, Lens culinaris and Triticum aestivum) which are most sensitive, fast growing and commonly used in Indian agriculture.

Immobilization of bimetallic nanoparticles on microfiltration membranes for trichloroethylene dechlorination.

Highly reactive nanoscale Ni/Fe nanoparticles were synthesized on microfiltration membranes for dechlorination of 20 mg/L trichloroethylene (TCE). Complete degradation of TCE was achieved within 25 min by Nylon 66 membrane with the production of ethane as a major degradation product, depicting that hydrodechlorination is the major reaction mechanism for TCE dechlorination. In addition, the carbon mass balance can be reached to 93%. The surface-area-normalized rate constant (kSA) for TCE degradation by Ni/Fe immobilized on Nylon 66 was 0.172 L h(-1) m(-2), which is higher than that by Ni/Fe in solution. Further TEM and SEM-EDS analyses show that Nylon 66 can retain higher amounts of Ni on the surface of membrane. In addition, the efficiency and rate for TCE dechlorination increased upon increasing mass loading of Ni from 2.5 to 20 wt%. Results obtained in this study clearly demonstrate that the use of Nylon 66 as the support for immobilization of bimetallic Ni/Fe nanoparticles has a good catalytic activity for dechlorination of TCE.

Coupled reduction of chlorinated hydrocarbons and heavy metals by zerovalent silicon.

The feasibility of using zerovalent silicon (Si0) as a novel reductant to remove chlorinated compounds and heavy metals in contaminated sites was investigated. The kinetics and degradation mechanism of carbon tetrachloride (CT) by Si0 were also examined. Results showed that zerovalent silicon could effectively dechlorinate the chlorinated compounds. A nearly complete dechlorination of CT by Si0 was obtained within 14 h. The produced concentrations of chloroform (CF) accounted for 71-88% loss of CT, showing that reductive dechlorination is the major degradation pathway for the degradation of chlorinated hydrocarbons by Si0. The degradation followed pseudo first-order kinetics and the normalized surface reaction rate constant (k(sa)) for CT dechlorination ranged between 0.0342 and 0.0454 L m(-2) h(-1) when CT concentrations were in the range of 3-20 microM. A linear relationship between the k(sa) and pH value was also established. In addition, zerovalent silicon has a high capability in the removal of heavy metals. 83% of Cr(VI) was removed by 0.5g Si0 within 5 h, which is higher than that by Fe0. The removal efficiency of divalent metal ions by Si0 followed the order of Cu(II) > Pb(II) > Ni(II). This indicates that zerovalent silicon is an alternative reductant and can undergo coupled reduction of heavy metals and chlorinated hydrocarbons in contaminated groundwater.

Enhanced remediation of carbon tetrachloride by Fe(II)-Fe(III) systems in the presence of copper ions.

The effect of Cu(II) ion on the dechlorination of carbon tetrachloride (CT) by Fe(II) associated with various iron oxides was investigated. Iron oxides including goethite, hematite, ferrihydrite and magnetite were selected as the model compounds. CT was dechlorinated to chloroform (CF) by 3 mM Fe(II) in iron oxide suspensions at pH 7.2. The dechlorination followed pseudo first-order kinetics and the pseudo first-order rate constants (k(obs)) were 0.048 h(-1), 0.0836 h(-1), 0.0609 h(-1) and 0.0144 h(-1) in goethite-, hematite-, ferrihydrite- and magnetite-amended systems, respectively. Addition of Cu(II) into systems increased the k(obs) for CT dechlorination significantly. A 3- to 120-fold increase in k(obs) relative to the systems without Cu(II) was observed when 0.5 mM Cu(II) was added to the Fe(II)-Fe(III) suspensions. The pH of the system is an important factor controlling the dechlorination rate of CT. The increase in concentrations of Fe(II) and iron oxides also enhanced the dechlorination efficiency and rate of CT. Moreover, a linear relationship between the k(obs) and Cu(II) concentration ranging between 0 and 0.4 mM was observed. Results obtained demonstrate the feasibility of using surface-bound iron species with Cu(III) for the detoxification of chlorinated solvents in the contaminated aquifers.

The influence of pH and cadmium sulfide on the photocatalytic degradation of 2-chlorophenol in titanium dioxide suspensions.

The influence of pH and cadmium sulfide on the photocatalytic degradation of 2-chlorophenol (2-CP) in titanium dioxide suspensions was investigated to evaluate the feasibility of mixed semiconductors on the photodegradation of chlorinated organics in aqueous solution. Apparent first-order rate constants (k(obs)) and initial rate constants were used to evaluate the degradation efficiency of 2-CP. Higher degradation efficiency of 2-CP was observed at higher pH values. The apparent pseudo-first-order rate constant was 0.036 min(-1) at pH 12.5 in TiO2/UV system, while a 2- to 9-fold decrease in k(obs) was observed over the pH range of 2.5-9.5. The addition of phosphate buffer solutions at different pH values have different effects on the degradation of 2-CP. H2PO4- has little effect on the photodegradation of 2-CP, while HPO4(2-) could inhibit the photodegradation efficiency of 2-CP. Chlorocatechol, hydroquinone, benzoquinone and phenol were identified as the predominant aromatic intermediates for the photocatalytic degradation of 2-CP. Moreover, less aromatic intermediates at higher pH were observed. Direct oxidation contributed significantly to the photodegradation of 2-CP. An addition of a semiconductor decreased the initial and apparent first-order rate constants of 2-CP. The cutoff of wavelength of 320nm could diminish the contribution of direct photolysis of 2-CP. The combination of cadmium sulfide and titanium dioxide can lead to an enhanced rate of disappearance of 2-CP compared to those in single semiconductor system. A 1.2 to 2.5-fold increase in rate constant in coupled semiconductor system relative to the single semiconductor system was obtained.

Determination of organochlorine pesticides and their metabolites in soil samples using headspace solid-phase microextraction.

An analytical procedure was developed using headspace solid-phase microextraction (HS-SPME) for the determination of organochlorine pesticides (OCPs) and their metabolites in sandy soil samples. The developed procedures involving fiber selection, temperature effect, absorption time, soil matrix and the addition of solvents of different polarity were optimized. Also, the results were compared to those achieved using Soxhlet extraction standard method. The 100-microm polydimethylsiloxane (PDMS) and 65-microm PDMS-divinylbenzene showed good extraction efficiency for 18 organochlorine pesticides. An increase in the extraction efficiency of organochlorine pesticides and the metabolites was observed when the temperature increased, and an optimum temperature of 70 degrees C for extracting OCPs was obtained. The application of other hydrophilic solvents had different effects on the extraction of organochlorine pesticides and the metabolites. Higher responses of OCPs were obtained when 5 ml of water was added to the soil. Good linearity of OCPs between 0.2 and 4 ng/g soil was observed. The relative standard deviation was found to be lower than 25%. Also the limits of detection were between 0.06 and 0.65 ng/g, which were lower than those obtained using Soxhlet extraction. Moreover, the optimized HS-SPME procedure was applied to the analysis of OCPs in certified reference material (CRM) 804-050 soil and compared with Soxhlet extraction procedure. Results obtained in this study were in good agreement with those obtained using Soxhlet extraction. The mean values obtained using HS-SPME technique were in the range of 16.5 to 1459.6 mg/kg, which corresponds to the recoveries of 68% to 127% of the certified values of CRM soil.

Solid-phase microextraction for determining the distribution of sixteen US Environmental Protection Agency polycyclic aromatic hydrocarbons in water samples.

A solid-phase microextraction (SPME) procedure has been developed for the determination of 16 US Environmental Protection Agency promulgated polycyclic aromatic hydrocarbons (PAHs). Five kinds of SPME fibers were used and compared in this study. The extracted sample was analyzed by gas chromatography with flame ionization detection or mass spectrometry. Parameters affecting the sorption of analyte into the fibers, including sampling time, thickness of the fiber coating, and the effect of temperature, have been examined. Moreover, the feasibility of headspace SPME with different working temperatures was evaluated. The method was also applied to real samples. The 85-microm polyacrylate (PA) and 100-microm poly(dimethylsiloxane) (PDMS) fibers were shown to have the highest affinities for the selected PAHs. The PA fiber was more suitable than the PDMS fiber for the determination of low-ring PAHs while high sensitivity of high-ring PAHs was observed when a 100-microm PDMS fiber was used. The method showed good linearity between 0.1 and 100 ng/ml with regression coefficients ranging from 0.94 to 0.999. The reproducibility of the measurements between fibers was found to be very good. The precisions of PA and PDMS fibers were from 3 to 24% and from 3 to 14%, respectively. Headspace SPME is a valid alternative for the determination of two- to five-ring PAHs. A working temperature of 60 degrees C provides significant enhancement in sensitivity of two- to five-ring PAHs having low vapor pressures (>10(-6) mmHg at 25 degrees C) (1 mmHg = 133.3 Pa) and low Henry's constants (>10 atm ml/mol) (1 atm = 1.01 x 10(5) Pa).

Relationship between electron donor and microorganism on the dechlorination of carbon tetrachloride by an anaerobic enrichment culture.

An investigation involving the supplement of different concentrations of substrates and microorganisms was carried out under anaerobic condition to assess the feasibility of bioremediation of carbon tetrachloride (CCl4) with the amendment of low concentrations of auxiliary substrate and microorganisms. The concentrations of substrate and microorganisms ranged from 10 to 100 mg/l and from 3.7 x 10(4) to 3.7 x 10(6) cell/ml, respectively. The biotransformation rate of CCl4 increased progressively with the increase in the concentrations of the substrate and microorganisms. In the low biomass-amended system (3.7 x 10(4) cells/ml), 28-71% and 57-96% of CCl4 removals were exhibited when 10-100 mg/l of acetate or glucose was supplemented, respectively, whereas nearly complete degradation of CCl4 was observed in the heavily inoculated systems (3.7 x 10(6) cells/ml). An addition of electron donor in the low microbial activity batches enhanced greater efficiency in dechlorination than in the high microbial activity batches. The second-order rate constants ranged from 0.0059 to 0.0092 l/mg/day in high biomass input system, while a two- to four-fold increase in rate constant was obtained in the low microbial activity system. This study indicates that biomass was the more important environmental parameter than substrate affecting the fate of CCl4. The addition of auxiliary substrates was effective only in low biomass-amended batches (0.56 mg-VSS/l) and diminished inversely with the increase of microbial concentration.

Dietary intake and residues of organochlorine pesticides in foods from Hsinchu, Taiwan.

The levels of contamination with various organochlorine pesticides (such as total HCH, heptachlor, heptachlor epoxide, aldrin, dieldrin, endrin, endosulfan, and total DDT) of different foods from 3 traditional markets were determined to estimate Taiwanese daily intake of organochlorine pesticides. Of the 18 organochlorine pesticides investigated, alpha-HCH, beta-HCH, lindane, delta-HCH, heptachlor, heptachlor epoxide, dieldrin, endrin, alpha-endosulfan, p,p'-DDE, and p,p'-DDT were detected at concentrations ranging from 0.26 to 10.2 ng/g wet weight. Contamination with organochlorine pesticides followed the order heptachlor > dieldrin > alpha-endosulfan > HCH isomers > heptachlor epoxide > DDT. Frequencies of detection of organochlorine pesticide residues ranged from 2.0 to 52.3%. alpha-Endosulfan was the most frequently detected organochlorine pesticide in the foods analyzed, followed by heptachlor epoxide (47.6%) and alpha-HCH (38.9%). Estimated daily intakes (EDIs) of organochlorine pesticides from foods were 1.137 micrograms for total HCH, 2.147 micrograms for heptachlor, 0.702 microgram for heptachlor epoxide, 0.624 microgram for endosulfan, 0.098 microgram for cyclodiene, and 0.541 microgram for total DDT. These EDIs were only 0.075% of the acceptable daily intake (ADI) for lindane, 47.5% of ADI for heptachlor and heptachlor epoxide, 0.045% of ADI for total DDT, and 1.01% of ADI for aldrin and dieldrin. Therefore, consumption of the foods analyzed does not pose a risk to consumer health.

Determination of organochlorine pesticide residues in foods using solid-phase extraction clean-up cartridges.

Fourteen organochlorine pesticide residues in fatty foods were determined using a simple and rapid procedure based on solid-phase extraction (SPE) clean-up cartridges with octadecyl (C18)-bonded porous silica, a tandem C18 and Florisil column, Alumina-N and Florisil. A Florisil cartridge eluted with 12 ml petroleum ether-ethyl ether (95 + 5) was the most efficient clean-up procedure capable of eliminating the matrix interference and satisfying the agreed acceptable recovery for the large numbers of organochlorine pesticides in nine kinds of foods having different fat contents. Average recoveries of organochlorine pesticides in shellfish, fish and meats ranged from 77 to 105%, 84 to 98% and 85 to 107%, respectively. In addition, analysis of a certified Standard Reference Material (SRM 1945) verified the satisfactory performance of Florisil clean-up cartridge. This SPE method not only yielded comparable results for nonfatty foods, but also provided a reliable separation and quantification of organochlorine pesticides for analyzing a large number of foods with a wide range of fat content.