First-order Degradation Rate Constants Research Articles

Effect of Polymer Degradation on Polymer Flooding in Heterogeneous Reservoirs.

Polymer degradation is critical for polymer flooding because it can significantly influence the viscosity of a polymer solution, which is a dominant property for polymer enhanced oil recovery (EOR). In this work, physical experiments and numerical simulations were both used to study partially hydrolyzed polyacrylamide (HPAM) degradation and its effect on polymer flooding in heterogeneous reservoirs. First, physical experiments were conducted to determine basic physicochemical properties of the polymer, including viscosity and degradation. Notably, a novel polymer dynamic degradation experiment was recommended in the evaluation process. Then, a new mathematical model was proposed and an in-house three-dimensional (3D) two-phase polymer flooding simulator was designed to examine both polymer static and dynamic degradation. The designed simulator was validated by comparison with the simulation results obtained from commercial software and the results from the polymer flooding experiments. This simulator further investigated and validated polymer degradation and its effect. The results of the physical experiments showed that the viscosity of a polymer solution increases with an increase in polymer concentration, demonstrating their underlying power law relationship. Moreover, the viscosity of a polymer solution with the same polymer concentration decreases with an increase in the shear rate, demonstrating shear thinning. Furthermore, the viscosity of a polymer solution decreased with an increase in time due to polymer degradation, exhibiting an exponential relationship. The first-order dynamic degradation rate constant of 0.0022 day−1 was greater than the first-order static degradation rate constant of 0.0017 day−1. According to the simulation results for the designed simulator, a 7.7% decrease in oil recovery, after a cumulative injection volume of 1.67 pore volume (PV) was observed between the first-order dynamic degradation rate constants of 0 and 0.1 day−1, which indicates that polymer degradation has a detrimental effect on polymer flooding efficiency.

Titanium dioxide surface modified with both palladium and fluoride as an efficient photocatalyst for the degradation of urea

TiO2 surface modified with both Pd nanoparticles and fluorides (F-TiO2/Pd) was prepared and applied as a photocatalyst in the degradation of urea. Various surface analysis techniques, including X-ray photoelectron spectroscopy, high-resolution transmission electron microscopy, and energy-dispersive X-ray spectroscopy, were used to verify the coexistence of Pd nanoparticles and fluorides on the surface of TiO2 in F-TiO2/Pd. F-TiO2/Pd showed a higher photocatalytic activity than those of bare TiO2 and single-component-modified TiO2 photocatalysts such as fluorinated TiO2 (F-TiO2) and Pd-loaded TiO2 (Pd/TiO2). The higher urea degradation efficiency of F-TiO2/Pd is ascribed to the enhanced production of hydroxyl radicals (OH) by the synergistic action of the surface Pd and fluoride. Pd nanoparticles and fluorides facilitate the transfer of valence band holes (hvb+) and their reaction with water molecules, respectively, synergistically enhancing the production of OH. The photocatalytic activity of F-TiO2/Pd for the degradation of urea increased upon increasing the fraction of the fluorinated TiO2 surface, which is higher at higher fluoride concentrations and lower pH. Although Pt/TiO2 showed higher photocatalytic activity for the degradation of urea than those of Pd/TiO2 and Au/TiO2, the strong positive effect of fluoride complexation was only exhibited by Pd/TiO2 (a slight positive effect and a negative effect were observed for Au/TiO2 and Pt/TiO2, respectively). As a result, the degradation of urea proceeded more rapidly in a UV-irradiated suspension of F-TiO2/Pd than when any of other photocatalysts (i.e., bare TiO2, Pd/TiO2, F-TiO2, Au/TiO2, F-TiO2/Au, Pt/TiO2, and F-TiO2/Pt) were used under the same conditions. The first-order degradation rate constants (k) of urea depending on the type of TiO2 were as follows: 0.097 h−1 for bare TiO2, 0.158 h−1 for Pd/TiO2, 0.151 h−1 for F-TiO2, 0.351 h−1 for F-TiO2/Pd, 0.173 h−1 for Au/TiO2, 0.223 h−1 for F-TiO2/Au, 0.240 h−1 for Pt/TiO2, and 0.165 h−1 for F-TiO2/Pt, respectively. In addition, F-TiO2/Pd proved to be stable in repeated urea degradation cycles.

Enhanced heterogeneous Fenton-like activity by Cu-doped BiFeO3 perovskite for degradation of organic pollutants

Heterogeneous Fenton-like reaction has been extensively investigated to eliminate refractory organic contaminants in wastewater, but it usually shows low catalytic performance due to difficulty in reduction from Fe(III) to Fe(II). In this study, enhanced catalytic efficiency was obtained by employing Cu-doped BiFeO3 as heterogeneous Fenton-like catalysts, which exhibited higher catalytic performance toward the activation of H2O2 for phenol degradation than un-doped BiFeO3. BiFe0.8Cu0.2O3 displayed the best performance, which yielded 91% removal of phenol (10 mg L–1) in 120 min. The pseudo first-order kinetic rate constant of phenol degradation in BiFe0.8Cu0.2O3 catalyzed heterogeneous Fenton-like reaction was 5 times higher than those of traditional heterogeneous Fenton-like catalysts, such as Fe3O4 and goethite. The phenol degradation efficiency could still reach 83% after 4 cycles, which implied the good stability of BiFe0.8Cu0.2O3. The high catalytic activity of BiFe0.8Cu0.2O3 was attributed to the fact that the doping Cu into BiFeO3 could promote the generation of Fe(II) in the catalyst and then facilitate the activation of H2O2 to degrade the organic pollutants.

Immobilization of ZnO/polyaniline heterojunction on electrospun polyacrylonitrile nanofibers and enhanced photocatalytic activity

Polyaniline (PANI) particles were immobilized on electrospun polyacrylonitrile (PAN) nanofibers (NFs) to form PAN@PANI NFs via in situ polymerization at room temperature. Then, ZnO was deposited on the surface of PAN@PANI NFs by atomic layer deposition (ALD) to form PAN@PANI@ZnO NFs. The PANI and ZnO contents were well controlled by adjusting the polymerization time and the number of ALD cycles, respectively. The obtained PAN@PANI@ZnO NFs exhibited higher photocatalytic activity for the degradation of methylene blue under ultraviolet light irradiation than PAN@PANI and PAN@ZnO NFs, and the first-order degradation rate constant (kapp) of PAN@PANI@ZnO NFs formed with 400 ALD cycles was greater than that of PAN@ZnO NFs formed with 400 ALD cycles by a factor of 2.1. The enhanced photocatalytic activity is shown to originate from the improved charge separation of photogenerated electrons and holes due to the formation of ZnO/PANI heterojunctions in PAN@PANI@ZnO NFs. The obtained PAN@PANI@ZnO photocatalysts are easily recycled with little decrease in photocatalytic activity because of their macroscopic mat structure and flexibility.

Derivation of CYP3A4 and CYP2B6 degradation rate constants in primary human hepatocytes: A siRNA-silencing-based approach

The first-order degradation rate constant (kdeg) of cytochrome P450 (CYP) enzymes is a known source of uncertainty in the prediction of time-dependent drug–drug interactions (DDIs) in physiologically-based pharmacokinetic (PBPK) modelling. This study aimed to measure CYP kdeg using siRNA to suppress CYP expression in primary human hepatocytes followed by incubation over a time-course and tracking of protein expression and activity to observe degradation. The magnitude of gene knockdown was determined by qPCR and activity was measured by probe substrate metabolite formation and CYP2B6-Glo™ assay. Protein disappearance was determined by Western blotting. During a time-course of 96 and 60 h of incubation, over 60% and 76% mRNA knockdown was observed for CYP3A4 and CYP2B6, respectively. The kdeg of CYP3A4 and CYP2B6 protein was 0.0138 h−1 (±0.0023) and 0.0375 h−1 (±0.025), respectively. The kdeg derived from probe substrate metabolism activity was 0.0171 h−1 (±0.0025) for CYP3A4 and 0.0258 h−1 (±0.0093) for CYP2B6. The CYP3A4 kdeg values derived from protein disappearance and metabolic activity were in relatively good agreement with each other and similar to published values. This novel approach can now be used for other less well-characterised CYPs.

Remedial function of submersed macrophyte <i>Vallisneria natans</i> to PAHs-contaminated sediments

沉水植物是浅水湖泊生态系统的关键种群，对水环境质量及水生生态系统结构有重要影响.以东太湖大水港和湖湾区2个典型的具有不同污染程度的沉水植物苦草（Vallisneria natans）生长区域为研究对象，考察苦草对多环芳烃（PAHs）的修复效果.结果表明，经过34 d植物修复试验，重度污染的东太湖大水港沉积物中PAHs的去除率为62%，沉积物中PAHs降解速率为0.024 d^-1；而中度污染的东太湖湖湾区沉积物的PAHs去除率为42%，其降解速率为0.015 d^-1.种植苦草的沉积物中PAHs的降解速率是未种植苦草的降解速率的2~3倍.苦草对沉积物中高分子量PAHs的修复效果尤为显著.因此，苦草可以有效地用于PAHs污染沉积物的修复，尤其是在重污染和高分子量PAHs污染沉积物中，苦草的修复作用更加明显.;Submersed macrophytes are an important functional and structural element of shallow aquatic ecosystems. Remedial function of submersed macrophyte (Vallisneria natans) to PAHs in freshwater sediments was investigated in different pollution levels in east Lake Taihu. Over a 34-day plant remediation experiment, the removal rate and the first-order rate constants of PAHs degradation in the heavily contaminated sediments of Dashui harbour from east Lake Taihu was 62% and 0.024 d^-1, respectively. However, 42% PAHs removal and 0.015 d^-1 of PAHs degradation rate was also observed in the moderately contaminated sediments of east Lake Taihu bay. The degradation rate of PAHs in the planted sediments was 2-3 times higher than those in the unplanted sediments. The removal of high molecular weight (HMW) PAHs in sediments with planting V. natans was significantly observed. Thus, V. natans can be effectively used for the remediation of PAHs contaminated sediments, especially in heavily polluted and HMW-PAHs contaminated sediments.

Effect of field site hydrogeochemical conditions on the corrosion of milled zerovalent iron particles and their dechlorination efficiency

Milled zerovalent iron (milled ZVI) particles have been recognized as a promising agent for groundwater remediation because of (1) their high reactivity with chlorinated aliphatic hydrocarbons, organochlorine pesticides, organic dyes, and a number of inorganic contaminants, and (2) a possible greater persistance than the more extensively investigated nanoscale zerovalent iron. We have used laboratory-scale batch degradation experiments to investigate the effect that hydrogeochemical conditions have on the corrosion of milled ZVI and on its ability to degrade trichloroethene (TCE). The observed pseudo first-order degradation rate constants indicated that the degradation of TCE by milled ZVI is affected by groundwater chemistry. The apparent corrosion rates of milled ZVI particles were of the same order of magnitude for hydrogeochemical conditions representative for two contaminated field sites (133–140mmolkg−1day−1, indicating a milled ZVI life-time of 128–135days). Sulfate enhances milled ZVI reactivity by removing passivating iron oxides and hydroxides from the Fe0 surface, thus increasing the number of reactive sites available. The organic matter content of 1.69% in the aquifer material tends to suppress the formation of iron corrosion precipitates. Results from scanning electron microscopy, X-ray diffraction, and iron K-edge X-ray adsorption spectroscopy suggest that the corrosion mechanisms involve the partial dissolution of particles followed by the formation and surface precipitation of magnetite and/or maghemite. Numerical corrosion modeling revealed that fitting iron corrosion rates and hydrogen inhibitory terms to hydrogen and pH measurements in batch reactors can reduce the life-time of milled ZVI particles by a factor of 1.2 to 1.7.

Enhanced bioremediation of nutrient-amended, petroleum hydrocarbon-contaminated soils over a cold-climate winter: The rate and extent of hydrocarbon biodegradation and microbial response in a pilot-scale biopile subjected to natural seasonal freeze-thaw temperatures

A pilot-scale biopile field experiment for nutrient-amended petroleum-contaminated fine-grained soils was performed over the winter at a cold-climate site. The rate and extent of hydrocarbon biodegradation and microbial responses were determined and corresponded to the on-site soil phase changes (from unfrozen to partially frozen, deeply frozen, and thawed) associated with natural seasonal freeze-thaw conditions. Treated and untreated biopiles were constructed (~3500kg each) on an open outdoor surface at a remediation facility in Saskatoon, Canada. The treated biopile received N-P-K-based nutrient and humate amendments before seasonal freezing. Real-time field monitoring indicated significant unfrozen water content in the treated and untreated biopiles throughout the freezing period, from the middle of November to early March. Unfrozen water was slightly more available in the treated biopile due to the aqueous nutrient supply. Soil CO2 production and O2 consumption in the treated biopile were generally greater than in the untreated biopile. Total removal percentages for F2 (>C10–C16), F3 (>C16–C34), and total petroleum hydrocarbons (TPH) in the treated biopile were 57, 58, and 58%, respectively, of which 26, 39, and 33% were removed during seasonal freezing and early thawing between November to early March. F3 degradation largely occurred during freezing while F2 hydrocarbons were primarily removed during thawing. Biomarker-based hydrocarbon analyses confirmed enhanced biodegradation in the treated biopile during freezing. The soil treatment increased the first-order rate constants for F2, F3, and TPH degradation by a factor of 2 to 7 compared to the untreated biopile. Shifts in bacterial community appeared in both biopiles as the biopile soils seasonally froze and thawed. Increased alkB1 gene copy numbers in the treated biopile, especially in the partially thawed phase during early thawing, suggest extended hydrocarbon biodegradation to the seasonal freeze-thaw season, due to the nutrients supplied prior to seasonal freezing.

Calculating in situ degradation rates of hydrocarbon compounds in deep waters of the Gulf of Mexico

Biodegradation is an important process for hydrocarbon weathering that influences its fate and transport, yet little is known about in situ biodegradation rates of specific hydrocarbon compounds in the deep ocean. Using data collected in the Gulf of Mexico below 700m during and after the Deepwater Horizon oil spill, we calculated first-order degradation rate constants for 49 hydrocarbons and inferred degradation rate constants for an additional 5 data-deficient hydrocarbons. Resulting calculated (not inferred) half-lives of the hydrocarbons ranged from 0.4 to 36.5days. The fastest degrading hydrocarbons were toluene (k=−1.716), methylcyclohexane (k=−1.538), benzene (k=−1.333), and C1-naphthalene (k=−1.305). The slowest degrading hydrocarbons were the large straight-chain alkanes, C-26 through C-33 (k=−0.0494 through k=−0.007). Ratios of C-18 to phytane supported the hypothesis that the primary means of degradation in the subsurface was microbial biodegradation. These degradation rate constants can be used to improve models describing the fate and transport of hydrocarbons in the event of an accidental deep ocean oil spill.

Effect of boron on reactivity and apparent corrosion rate of microscale zerovalent irons

The reactivity and apparent corrosion rate of newly produced boron-alloyed microscale zerovalent iron (mZVI) particles toward a variety of chlorinated aliphatic hydrocarbons (CAHs) were assessed in laboratory-scale batch reactors. For comparison, commercially available nanoscale zerovalent irons (nZVIs) were also included in the study. Based on mass normalized (kM) pseudo first-order degradation rate constants, the reactivity of boron-alloyed mZVIs appeared to be one order of magnitude lower than most reactive nZVI. However, specific surface area normalized reaction rate constants (kSA) were 1–2 orders of magnitude higher than for nZVIs showing that boron-alloyed mZVIs can compete with nZVIs. The high reactivity of boron-alloyed mZVIs was attributed to (1) the prevented iron surface passivation during anaerobic corrosion due to the simultaneous iron and boron dissolution kinetics preventing the formation of insoluble oxidized iron species, (2) the involvement of boron in facilitating electron transfer by inducing β-elimination followed by hydrogenation to ethane and/or (3) involvement of boron in improved particle size reduction during milling process leading to increased active surface areas of the particles. Results of this study suggest that boron-alloyed mZVIs could be an efficient alternative to nZVIs for in situ groundwater remediation of different CAHs in terms of their reactivity and apparent corrosion rate.

Enhanced photocatalytic activity of Te-doped Bi2MoO6 under visible light irradiation: Effective separation of photogenerated carriers resulted from inhomogeneous lattice distortion and improved electron capturing ability

Te-doped Bi2MoO6 photocatalyst was hydrothermally synthesized, and nonmetal atoms Te were homogeneously incorporated into Bi2MoO6 lattice with the substitution of Te4+ to Mo6+. With increasing Te-doping concentration in Bi2MoO6, no detectable band-gap narrowing but more and more severe inhomogeneous lattice distortions were determined. The activity of Bi2MoO6 photocatalyst was evaluated through methylene blue degradation under visible light irradiation (λ>410nm) and was greatly enhanced by Te-doping. When Te-doped Bi2MoO6 was synthesized at Te/Mo molar ratio of 7.5%, a maximum first-order rate constant of methylene blue degradation was obtained. The inhomogeneous lattice distortion generated an internal dipole moment, and the holes generated with the substitution of Te4+ to Mo6+ acted as the capturing centers of photogenerated electrons, thus the effective separation of photogenerated carriers was facilitated to result in a relatively high concentration of holes on the surface of Te-doped Bi2MoO6 to be favorable for the efficient methylene blue degradation.

Photolysis of 2,4,6-trinitrotoluene in seawater and estuary water: Impact of pH, temperature, salinity, and dissolved organic matter

The influence of salinity, pH, temperature, and dissolved organic matter on the photolysis rate of 2,4,6-trinitrotoluene (TNT) in marine, estuary, and laboratory-prepared waters was studied using a Suntest CPS+® solar simulator equipped with optical filters. TNT degradation rates were determined using HPLC analysis, and products were identified using LC/MS. Minimal or no TNT photolysis occurred under a 395-nm long pass filter, but under a 295-nm filter, first-order TNT degradation rate constants and apparent quantum yields increased with increasing salinity in both natural and artificial seawater. TNT rate constants increased slightly with increasing temperature (10 to 32°C) but did not change significantly with pH (6.4 to 8.1). The addition of dissolved organic matter (up to 5mg/L) to ultrapure water, artificial seawater, and natural seawater increased the TNT photolysis rate constant. Products formed by TNT photolysis in natural seawater were determined to be 2,4,6-trinitrobenzaldehyde, 1,3,5-trinitrobenzene, 2,4,6-trinitrobenzoic acid, and 2-amino-4,6-dinitrobenzoic acid.

Effect of phenolic compounds on photodegradation of anthracene and benzo[a]anthracene in media of different polarity

Abstract The photodegradation of anthracene (Ant) and benz[a]anthracene (BaA) were studied in air-equilibrated hexane, methanol and pure water solutions in the absence and presence of phenolic compounds (4-methylcatechol, guaiacol and syringol). In the absence of phenolic compound, the pseudo first-order degradation rate constants of Ant and BaA increased with the polarity of solvent, demonstrating the influence of solvent effects on the photoreactivity. The differences can be attributed to factors such as the proton donating potential of the solvent, and the formation potentials of PAH radical cation and hydroxyl radical in solvent. In the presence of phenolic compound, Ant and BaA photodegradation rates were accelerated in hexane and methanol while inhibited in water solutions. Photodegradation kinetics of the phenolic compounds were also measured; and visible colored products were observed in all three solvents. The observed accelerations of Ant and BaA photodecay in the presence of the phenolic compounds can be explained by energy transfer from the phenolic compound to PAH, phenolic hydrogen abstraction by excited PAH and more reactive radical formation from the phenolic compound. However, the inhibition effects of Ant and BaA photodecay in water were more influenced by the quenching of photo-produced reactive oxygen species (ROS) by the phenolic compound and/or its photoproducts. The results indicate that the photodegradation of PAHs will be highly dependent on the aerosol water content. i.e., the chemical composition of the environmental aerosols.

Enhanced reductive dechlorination of trichloroethylene by sulfidated nanoscale zerovalent iron

Direct injection of reactive nanoscale zerovalent iron particles (NZVI) is considered to be a promising approach for remediation of aquifers contaminated by chlorinated organic pollutants. In this study we show that the extent of sulfidation of NZVI enhances the rate of dechlorination of trichloroethylene (TCE) compared to that by unamended NZVI, and the enhancement depends on the Fe/S molar ratio. Experiments where TCE was reacted with NZVI sulfidated to different extents (Fe/S molar ratios 0.62–66) showed that the surface-area normalized first-order TCE degradation rate constant increased up to 40 folds compared to non-sulfidated NZVI. Fe/S ratios in the range of 12–25 provided the highest TCE dechlorination rates, and rates decreased at both higher and lower Fe/S. In contrast, sulfidated NZVI exposed to water in the absence of TCE showed significantly lower hydrogen evolution rate (2.75 μmol L−1 h−1) compared to that by an unamended NZVI (6.92 μmol L−1 h−1), indicating that sulfidation of NZVI suppressed corrosion reactions with water. Sulfide (HS−) ions reacted rapidly with NZVI and X-ray photoelectron spectroscopy analyses showed formation of a surface layer of FeS and FeS2. We propose that more electrons are preferentially conducted from sulfidated NZVI than from unamended NZVI to TCE, likely because of greater binding of TCE on the reactive sites of the iron sulfide outer layer. Resuspending sulfidated NZVI in sulfide-free or sulfide containing solutions altered the TCE degradation rate constants because of changes in the FeS layer thickness. Sulfidated NZVI maintained its high reactivity in the presence of multiple mono and divalent ions and with polyelectrolyte coatings. Thus, sulfide ions in groundwater can significantly alter NZVI reactivity.

Photocatalysis by morphologically tailored mesoporous silica (SBA-15) embedded with SnO2 nanoparticles: Experiments and model

Commonly obtained SBA-15 particles (fiber-like morphology), if used as a catalyst-host, has limitations in diffusion of reactant molecules (e.g. of a dye) inside the pores of the SBA-15 particle. The systematic synthetic approach developed here provides an easy control of SBA-15 particle morphology over a wide range (fiber, rod, and sphere), by only varying the HCl concentration. To assess its effect on molecular diffusion and reaction inside pores, SnO2 nanoparticles of 3.5nm diameter were synthesized in situ, inside the 6.3nm diameter pores of SBA-15. These hybrids were tested for photocatalytic degradation of rhodamine B dye. Sphere-like morphology of SBA-15 with SnO2 nanoparticle loading of 17.7wt% showed the highest first-order degradation rate constant of 0.54h−1, compared to other morphologies (rod—0.51h−1, fiber—0.33h−1). On incorporating rates of diffusion, adsorption, and degradation-reaction of the dye in a single pore-level mathematical model of the SBA-15 particle, we have predicted the experimentally measured temporal variation of dye concentration for different SBA-15 morphologies and SnO2-catalyst loadings. Therefore, the present work identifies the best SBA-15 particle morphology (sphere-like) for such reactions and provides a validated model to optimize such coupled problems of chemical transport and reaction.

Abiotic dechlorination in rock matrices impacted by long-term exposure to TCE

Field and laboratory tests were performed to evaluate the abiotic reaction of trichloroethene (TCE) in sedimentary rock matrices. Hydraulically conductive fractures, and the rock directly adjacent to the hydraulically conductive fractures, within a historically contaminated TCE bedrock aquifer were used as the basis for this study. These results were compared to previous work using rock that had not been exposed to TCE (Schaefer et al., 2013) to assess the impact of long-term TCE exposure on the abiotic dechlorination reaction, as the longevity of these reactions after long-term exposure to TCE was hitherto unknown. Results showed that potential abiotic TCE degradation products, including ethane, ethene, and acetylene, were present in the conductive fractures. Using minimally disturbed slices of rock core at and near the fracture faces, laboratory testing on the rocks confirmed that abiotic dechlorination reactions between the rock matrix and TCE were occurring. Abiotic daughter products measured in the laboratory under controlled conditions were consistent with those measured in the conductive fractures, except that propane also was observed as a daughter product. TCE degradation measured in the laboratory was well described by a first order rate constant through the 118-d study. Observed bulk first-order TCE degradation rate constants within the rock matrix were 1.3×10−8s−1. These results clearly show that abiotic dechlorination of TCE is occurring within the rock matrix, despite decades of exposure to TCE. Furthermore, these observed rates of TCE dechlorination are expected to have a substantial impact on TCE migration and uptake/release from rock matrices.

Evaluation of agomelatine stability under different stress conditions using an HPLC method with fluorescence detection: application to the analysis of tablets and human plasma

A simple and highly sensitive stability-indicating HPLC method was developed and validated for the determination of the new antidepressant agent, agomelatine (AGM). Separation of AGM from its stress-induced degradation products was achieved on a BDS Hypersil phenyl column (250 mm × 4.6 mm i.d., 5 µm particle size) using methanol-0.05 M phosphate buffer of pH 2.5 (35: 65, v/v) as a mobile phase with fluorescence detection at 230/370 nm. Naproxen was used as an internal standard. The method satisfied all the validation requirements, as evidenced by good linearity (correlation coefficient of 0.9999, over the concentration range 0.4-40.0 ng/mL), accuracy (recovery average 99.55 ± 0.90%), precision (intra-day RSD 0.54-1.35% and inter-day RSD 0.93-1.26%), robustness and specificity. The stability of AGM was investigated under different ICH recommended stress conditions including acidic, alkaline, neutral, oxidative and photolytic. AGM was found to be labile to acidic and alkaline degradation and a kinetic study was conducted to explore its degradation behavior. First-order degradation rate constants and half-life times were calculated in each case. The proposed method was applied for the determination of AGM in tablets and spiked human plasma with mean percentage recoveries of 99.87 ± 0.31 (n = 3) and 102.09 ± 5.01 (n = 5), respectively. Hence, the proposed method was successfully applied for the determination of AGM in human volunteer plasma. The results were compared statistically with those obtained by a comparison HPLC method revealing no significant differences between the two methods regarding accuracy and precision.

Accelerated removal of pyrene and benzo[a]pyrene in freshwater sediments with amendment of cyanobacteria-derived organic matter

The removal of pyrene and benzo[a]pyrene (BaP) were investigated in freshwater sediments with amendment of seven different organic matters including cyanobacteria-derived organic matter (COM), plant-derived organic matter (POM), and humic substances (HS). During the 210 days of experiments, the amendment of COM or HS enhanced significantly the removal of pyrene and BaP in sediments, especially with fresh COM (FCOM) treatment much superior to HS. On the contrary, degradation of these polycyclic aromatic hydrocarbons (PAHs) was not significantly improved and even inhibited in POM-amended sediments. The first-order rate constants of pyrene and BaP degradation in the FCOM-amended sediments reached 0.00540±0.00017d−1 and 0.00517±0.00057d−1, respectively, and were about three and five folds of those in the control treatment. The enhanced PAHs degradation in FCOM-amended sediments was related to higher PAH-degrading bacteria number and bioavailability with a result of biostimulation and priming effect by labile carbon and high-value nutrition in FCOM. Thus, this study improved our understanding about effects of settled biomass from cyanobacterial blooms, which occurred frequently in eutrophic aquatic ecosystems, on the natural attenuation of PAHs in sediments. Furthermore, this study would also help develop a new promising approach to remediate PAH-contaminated sediments through utilization of cyanobacterial bloom biomass.

High Photocatalytic Activity of Transparent Films Composed of ZnO Nanosheets

Nanometric thin films were prepared by dip-coating and inkjet printing ZnO nanosheets on glass plates. The side-by-side alignment of the ZnO nanosheets on the substrate resulted in thin, transparent, oriented ZnO surfaces with the high-energy {001} facets exposed. The method of nanosheet deposition affected the film morphology; the dip-coated films were very smooth and nonporous, while the inkjet-printed films were rough and porous with the estimated void volume approximately 60-70% of the total film volume. The first-order rate constants for the photocatalytic degradation of 4-chlorophenol on the nanosheet-based films were approximately 2 times larger than those on nanocolumnar ZnO films or ZnO films prepared by the sol-gel technique. We attribute the high photocatalytic activity of the ZnO nanosheets to the fact that their {001} facets were predominantly exposed to the oxidized substrate. This surface arrangement and the simplicity of fabricating the ZnO nanosheet-based films make them promising for the construction of optical devices and dye-sensitized solar cells.

Biodegradation of methyl parathion in the presence of goethite: The effect of Pseudomonas sp. Z1 adhesion

In this research, the influence of goethite on biodegradation kinetic of methyl parathion was investigated in the presence of Pseudomonas sp. Z1. Semipermeable membrane experiments were performed to demonstrate the role of adhesion of degrading bacteria to surface of goethite in biodegradation of methyl parathion. Sorption of methyl parathion and bacteria onto goethite particles were also measured to assess the distribution of methyl parathion and bacteria between water and goethite surface. The first-order degradation rate constant of methyl parathion in different concentrations of goethite was in the order of 0.1 g L−1 > 0.01 g L−1 > 0 g L−1 > 1 g L−1 > 20 g L−1, suggesting the presence of low concentrations of goethite accelerated the biodegradation of methyl parathion and high concentrations of goethite inhibited this biodegradation process. According to the result of semipermeable membrane experiment, when no bacterial attachment occurred in the system, the promotive effect of 0.1 g L−1 goethite for microbial degradation was disappeared and the inhibition effect of 20 g L−1 goethite increased. The results clearly demonstrated that the adhesion of bacteria to goethite was beneficial to the biodegradation of methyl parathion. The information obtained is of fundamental significance for the understanding of microbial degradation of organic pollution in soil.