Enhanced photocatalytic reduction reaction over Bi(3+)-TiO(2) nanoparticles in presence of formic acid as a hole scavenger

A series of Bi(3+)-doped TiO(2) (Bi(3+)-TiO(2)) catalysts with a doping concentration up to 2wt% were prepared by a sol-gel method. The prepared photocatalysts were characterized by different means to determine their chemical composition, surface structure and light absorption properties. The photocatalytic activity of different Bi(3+)-TiO(2) catalysts was evaluated in the photocatalytic reduction of nitrate in aqueous solution under UV illumination. In the experiments, formic acid was used as a hole scavenger to enhance the photocatalytic reduction reaction. The experiments demonstrated that nitrate was effectively degraded in aqueous Bi(3+)-TiO(2) suspension by more than 83% within 150min, while the pH of the solution increased from 3.19 to 5.83 due to the consumption of formic acid. The experimental results indicate that the presence of Bi(3+) in TiO(2) catalysts substantially enhances the photocatalytic reaction of nitrate reduction. It was found that the optimal dosage of 1.5wt% Bi(3+) in TiO(2) achieved the fastest reaction of nitrate reduction under the experimental condition. Bismuth ions deposit on the TiO(2) surface behaves as sites where electrons accumulate. Better separation of electrons and holes on the modified TiO(2) surface allows more efficient channeling of the charge carriers into useful reduction and oxidation reactions rather than recombination reactions. Two intermediate products of nitrite and ammonia during the reaction were also monitored to explore the possible mechanisms of photoluminescence quenching and photocatalytic reduction in the context of donor-acceptor interaction with electron trapping centers.     

Polychlorinated naphthalenes and coplanar polychlorinated biphenyls in tissues of harbor seals (Phoca vitulina) from the northern Gulf of Alaska

Blubber, liver and kidney samples of harbor seals (Phoca vitulina) from the northern Gulf of Alaska were collected during 2000-2001 for the analysis of polychlorinated naphthalenes (PCNs) and coplanar polychlorinated biphenyls (CoplPCBs). On the lipid weight (lw) base, the total concentrations of PCNs (Sigma PCNs) ranged from 0.3 to 27 ng/g lw, and the total concentrations of CoplPCBs (Sigma CoplPCBs) were 3.6-546 ng/g lw in all the tissue samples. Di-ortho PCBs and mono-ortho PCBs were dominant followed by non-ortho PCBs and PCNs. Sigma Mono-ortho PCBs and Sigma di-ortho PCBs in nursing seals were apparently lower than those in male adult seals, but Sigma PCNs and Sigma non-ortho PCBs in female adults were not significantly different from those in male adults. Differences in PCNs and CoplPCBs congener profiles in female and male adult seals are apparently related to their chemical structure and properties, animal's developmental stages and physiological conditions. A large quantity of mono-ortho and di-ortho PCBs might be transferred to newborns from the nursing seals during lactation, while non-ortho PCBs and PCNs were relatively accumulative in the mother seals. Sigma PCNs and Sigma CoplPCBs in the harbor seals correlated with ages, gender, body weight and blubber thickness, but the blubber Sigma PCNs and Sigma CoplPCBs in Kodiak Island and Southern Alaska Peninsula (KIAP) did not significantly differ from those in Prince William Sound (PWS). In addition to the new PCB data, this first report on PCN contamination in Alaskan harbor seal tissues is useful for the wildlife and ecosystem management and human health protection.     

Study of urban atmospheric pollution in Navarre (Northern Spain)

An ambient air quality study was undertaken in two cities (Pamplona and Alsasua) of the Province of Navarre in northern Spain from July 2001 to June 2004. The data were obtained from two urban monitoring sites. At both monitoring sites, ambient levels of ozone, NO_x, and SO₂ were measured. Simultaneously with levels of PM₁₀ measured at Alsasua (using a laser particle counter), PM₁₀ levels were also determined at Pamplona (using a beta attenuation monitor). Mean annual PM₁₀ concentrations in Pamplona and Alsasua reached 30 and 28 μg m⁻³, respectively. These concentrations are typical for urban background sites in Northern Spain. By using meteorological information and back trajectories, it was found that the number of exceedances of the daily PM₁₀ limit as well as the PM₁₀ temporal variation was highly influenced by air masses from North Africa. Although North African transport was observed on only 9% of the days, it contributed the highest observed PM₁₀ levels. Transport from the Atlantic Ocean was observed on 68% of the days; transport from Europe on 13%; low transport and local influences on 7%; and transport from the Mediterranean region on 3% of the days. The mean O₃ concentrations were 45 and 55 μg m⁻³ in Pamplona and Alsasua, respectively, which were above the values reported for the main Spanish cities. The mean NO and NO₂ levels were very similar in both sites (12 and 26 μg m⁻³, respectively). Mean SO₂ levels were 8 μg m⁻³ in Pamplona and 5 μg m⁻³ in Alsasua. Hourly levels of PM₁₀, NO and NO₂ showed similar variations with the typically two coincident maximums during traffic rush hours demonstrating a major anthropogenic origin of PM₁₀, in spite of the sporadic dust outbreaks.     

Enhanced photoelectrocatalytic performance of Zn-doped WO(3) photocatalysts for nitrite ions degradation under visible light

WO(3) and Zn-doped WO(3) thin films were prepared on indium-tin oxide glass by a dip-coating. The composite films were characterized by UV-Vis absorption spectra, X-ray diffraction and scanning electron microscope. The effect of preparation conditions (concentration of Zn, annealing temperature, number of layers) on the photocurrent was studied. It was found that the photocurrent under visible light displayed the highest value for 2% Zn-WO(3) films annealed at 400 degrees C. The photocatalytic activity of the Zn-doped WO(3) was evaluated in terms of decay rate of nitrite ions under visible light. The influence of applied potential, initial pH and nitrite concentration on the reaction rate was studied. The experiments demonstrated that NO(2)(-) could be efficiently degraded on the doped photoanode that showed a higher activity than the undoped WO(3) especially under high anodic potential (>0.7 V). The rate of degradation was enhanced in aqueous NaCl solutions. Furthermore, it was demonstrated that the photodegradation mechanism of NO(2)(-) proceeded mainly indirectly via OH radicals. The possible reason of enhancement of reaction rate was also discussed.     

Henry's law constants of phenol and mononitrophenols in water and aqueous sulfuric acid

Phenols are widely present in the atmosphere and nitration probably in the aerosol phase leads to nitrophenols. Nitration by nitric acid in sulfuric acid can be rapid, but little is known of the process under atmospheric conditions. The Henry's law constants K(H)(dagger) of phenol and 2-, 3- and 4-nitrophenol were all measured by a bubble stripping method as: 2820mol kg(-1) atm(-1) (at 298K), 147mol kg(-1) atm(-1) (at 298K), 1.6x10(4)mol kg(-1)atm(-1) (at 308K) and 2.1x10(4)mol kg(-1) atm(-1) (at 308K), respectively. The Henry's law constant of phenol in sulfuric acid systems is lower by more than a factor of two at 1020mol kg(-1) atm(-1) (at 298K) in 40wt% sulfuric acid, which is in line with salting-out of oxygen-containing aromatic compounds in water-sulfuric acid systems. The Henry's law constants of 2- and 4-nitrophenol behave differently and are almost independent of sulfuric acid concentration. The variation of K(H)(dagger) with temperature (T) described in terms of -dln(K(H)(dagger))/d(1/T) does not to vary with sulfuric acid concentration, suggesting enthalpy of dissolution for phenol is independent of sulfuric acid. The series of Henry's law constants measured here can describe the equilibrium situation for phenols in careful determinations of phase partitioning in the atmosphere.     

Effects of 2,4-dichlorophenol, pentachlorophenol and vegetation on microbial characteristics in a heavy metal polluted soil

The aim of this study was to evaluate the soil microbial characteristics in historically heavy-metal polluted soil, which was also affected by organic co-contaminants, 2,4-dichlorophenol or pentachlorophenol, which often occur due to the conventional use of pesticides. It was observed that the normalized microbial biomass (microbial biomass per unit soil organic C) of the contaminated soil was very low, less than 1% in both non-planted and ryegrass planted soil, and showed a decreasing trend with the treatment of organic co-contaminants. The microbial biomass and substrate-induced respiration (SIR) in the ryegrass planted soil were much larger, as compared with the non-planted soil with or without organic pollutants. The different resistant bacterial community and its physiological diversity in the rhizosphere further suggested that the effect of vegetation on microbial activity was not just a general increase in the mass or activity of pre-existing microorganisms, but rather acted selectively on microbial growth so that the relative abundance of different microbial groups in soil was changed. In sum, high concentrations of organic co-contaminants, especially pentachlorophenol (PCP), could strengthen the deterioration of microbial ecology. The adverse effect of heavy metal-organic pollutants on the soil microbial biomass and activity might be the reason for the slow degradation of PCP that has high chlorinated and high toxicity. Vegetation might be the efficient way to assist in improving and restoring the utilization of agricultural ecosystems. The beneficial microbial effect of vegetation could cause the rapid dissipation of 2,4-dichlorophenol (2,4-DCP) that has less chlorinated and less toxicity in the planted soils.     

Application of an enzyme-linked immunosorbent assay for the detection of clenbuterol residues in swine urine and feeds

The present study outlines applications of an enzyme-linked immunosorbent assay (ELISA) for the analysis of clenbuterol residues. Antisera were raised from rabbits immunized with diazotized clenbuterol-bovine serum albumin (BSA) conjugate. The assay was specific to clenbuterol with a half-maximum inhibition concentration (IC(50)) of 1.8 ng/mL and 2.5 ng/mL in blank swine urine and phosphate buffer solution, respectively. The assay had high cross-reactivity (86%) with mabuterol, but low with other adrenergic agonists and antagonists. The average recovery of clenbuterol, as measured with the ELISA, ranged from 90% to 112% in swine urine samples and from 86% to 95% in feeds, respectively. This new assay was compared with commercial ELISA test kits. An excellent correlation (r(2) = 0.98) between the two methods and satisfactory recoveries suggest that the new assay can be suitable for the determination of clenbuterol residues in real samples. The assay was used to analyze clenbuterol residues in 103 swine urine samples and 68 feed samples collected from northern China. Approximately 50% of the urine samples and 25% of the feed samples analyzed were found positive (concentration of clenbuterol > or = 1 ppb). The results indicate that clenbuterol was misused in some of the areas surveyed.     

Effects of the arbuscular mycorrhizal fungus Glomus mosseae on growth and metal uptake by four plant species in copper mine tailings

A greenhouse experiment was conducted to evaluate the potential role of arbuscular mycorrhizal fungi (AMF) in encouraging revegetation of copper (Cu) mine tailings. Two native plant species, Coreopsis drummondii and Pteris vittata, together with a turf grass, Lolium perenne and a leguminous plant Trifolium repens associated with and without AMF Glomus mosseae were grown in Cu mine tailings to assess mycorrhizal effects on plant growth, mineral nutrition and metal uptake. Results indicated that symbiotic associations were successfully established between G. mosseae and all plants tested, and mycorrhizal colonization markedly increased plant dry matter yield except for L. perenne. The beneficial impacts of mycorrhizal colonization on plant growth could be largely explained by both improved P nutrition and decreased shoot Cu, As and Cd concentrations. The experiment provided evidence for the potential use of local plant species in combination with AMF for ecological restoration of metalliferous mine tailings.     

Fate of PCBs, PAHs and their source characteristic ratios during composting and digestion of source-separated organic waste in full-scale plants

Composting and digestion are important waste management strategies. However, the resulting products can contain significant amounts of organic pollutants such as polychlorinated biphenyls (PCBs) and polycyclic aromatic hydrocarbons (PAHs). In this study we followed the concentration changes of PCBs and PAHs during composting and digestion on field-scale for the first time. Concentrations of low-chlorinated PCBs increased during composting (about 30%), whereas a slight decrease was observed for the higher chlorinated congeners (about 10%). Enantiomeric fractions of atropisomeric PCBs were essentially racemic and stable over time. Levels of low-molecular-weight PAHs declined during composting (50-90% reduction), whereas high-molecular-weight compounds were stable. The PCBs and PAHs concentrations did not seem to vary during digestion. Source apportionment by applying characteristic PAH ratios and molecular markers in input material did not give any clear results. Some of these parameters changed considerably during composting. Hence, their diagnostic potential for finished compost must be questioned.     

Modeling transport and fate of nitrogen from urea applied to a near-trench paddy field

A simple but comprehensive model is developed to quantify N losses from urea applied to a near-trench paddy field, considering all the N-transformations such as urea hydrolysis, volatilization, nitrification, denitrification, and all the important transportations like runoff, lateral seepage, vertical leaching and crop uptake. Seasonal average data of field observations for three crop seasons were used for model calibration and validation, which showed that ammonia volatilization accounted for 26.5-29.4% of the applied N and N uptake by crop occupied 38.2-44.8%, while N losses via surface runoff, vertical leaching and lateral seepage varied from 5.6-7.7%, 4.0-4.9% to 5.0-5.3% of the applied N, respectively. These observed results were well predicted by our model, indicating that the model performed effectively at quantifying N losses via individual processes in a wide range of urea application rates and benefit for developing water and fertilizer management strategies for near-trench paddy fields.