Photocatalytic oxidation of gas-phase elemental mercury by nanotitanosilicate fibers

Photocatalytic fibers were generated from the continuous evaporation of titanium tetraisopropoxide with tetraethyl orthosilicate through a flame burner. The morphology, the crystal form, and the components of the nanotitanosilicate fibers were analyzed by Raman spectroscopy, Field emission-scanning electron microscope, X-ray diffraction, and Brunauer-Emmett-Teller surface area analysis. The nanotitanosilicates prepared by three different carrier gases (air, N(2), and Ar) were tested for their photocatalytic ability to remove/oxidize gas-phase elemental mercury. Under UV black light, the Hg(0) capture efficiencies were 78%, 86%, and 85% for air, N(2), and Ar, respectively. For air, the value was close to 90%, even under household fluorescent light. The Hg(0) capture efficiency by nanotitanosilcate was measured under fluorescent light, UV black light, and sunlight.     

Degradation rates of CFC-11, CFC-12 and CFC-113 in anoxic shallow aquifers of Araihazar, Bangladesh

Chlorofluorocarbons CFC-11 (CCl(3)F), CFC-12 (CCl(2)F(2)), and CFC-113 (CCl(2)F-CClF(2)) are used in hydrology as transient tracers under the assumption of conservative behavior in the unsaturated and saturated soil zones. However, laboratory and field studies have shown that these compounds are not stable under anaerobic conditions. To determine the degradation rates of CFCs in a tropical environment, atmospheric air, unsaturated zone soil gas, and anoxic groundwater samples were collected in Araihazar upazila, Bangladesh. Observed CFC concentrations in both soil gas and groundwater were significantly below those expected from atmospheric levels. The CFC deficits in the unsaturated zone can be explained by gas exchange with groundwater undersaturated in CFCs. The CFC deficits observed in (3)H/(3)He dated groundwater were used to estimate degradation rates in the saturated zone. The results show that CFCs are degraded to the point where practically no (<5%) CFC-11, CFC-12, or CFC-113 remains in groundwater with (3)H/(3)He ages above 10 yr. In groundwater sampled at our site CFC-11 and CFC-12 appear to degrade at similar rates with estimated degradation rates ranging from approximately 0.25 yr(-1) to approximately 6 yr(-1). Degradation rates increased as a function of reducing conditions. This indicates that CFC dating of groundwater in regions of humid tropical climate has to be carried out with great caution.     

Performance of an electrochemical COD (chemical oxygen demand) sensor with an electrode-surface grinding unit

An electrochemical COD (chemical oxygen demand) sensor using an electrode-surface grinding unit was investigated. The electrolyzing (oxidizing) action of copper on an organic species was used as the basis of the COD measuring sensor. Using a simple three-electrode cell and a surface grinding unit, the organic species is activated by the catalytic action of copper and oxidized at a working electrode, poised at a positive potential. When synthetic wastewater was fed into the system, the measured Coulombic yields were found to be dependent on the COD of the synthetic wastewater. A linear correlation between the Coulombic yields and the COD of the synthetic wastewater was established (10-1000 mg L(-1)) when the electrode-surface grinding procedure was activated briefly at 8 h intervals. When various kinds of wastewater samples obtained from various sewage treatment plants were measured, linear correlations (r(2)> or = 0.92) between the measured EOD (electrochemical oxygen demand) value and COD of the samples were observed. At a practical wastewater treatment plant, the measurement system was successfully operated with high accuracy and good stability over 3 months. These experimental results show that the application of the measurement system would be a rapid and practical method for the determination of COD in water industries.     

Perfluorinated compounds in the Pearl River and Yangtze River of China

A total of 14 perfluorinated compounds (PFCs) were quantified in river water samples collected from tributaries of the Pearl River (Guangzhou Province, south China) and the Yangtze River (central China). Among the PFCs analyzed, perfluorooctane sulfonate (PFOS) and perfluorooctanoic acid (PFOA) were the two compounds with the highest concentrations. PFOS concentrations ranged from 0.90 to 99 ng/l and <0.01–14 ng/l in samples from the Pearl River and Yangtze River, respectively; whereas those for PFOA ranged from 0.85 to 13 ng/l and 2.0–260 ng/l. Lower concentrations were measured for perfluorobutane sulfonate (PFBS), perfluorohexane sulfonate (PFHxS), perfluorooctanesulfoamide (PFOSA), perfluorohexanoic acid (PFHxA), perfluoroheptanoic acid (PFHpA), perfluorononaoic acid (PFNA), perfluorodecanoic acid (PFDA), and perfluoroundecanoic acid (PFUnDA). Concentrations of several perfluorocarboxylic acids, including perfluorododecanoic acid (PFDoDA), perfluorotetradecanoic acid (PFTeDA), perfluorohexadecanoic acid (PFHxDA) and perfluorooctadecanoic acid (PFOcDA) were lower than the limits of quantification in all the samples analyzed. The highest concentrations of most PFCs were observed in water samples from the Yangtze River near Shanghai, the major industrial and financial centre in China. In addition, sampling locations in the lower reaches of the Yangtze River with a reduced flow rate might serve as a final sink for contaminants from the upstream river runoffs. Generally, PFOS was the dominant PFC found in samples from the Pearl River, while PFOA was the predominant PFC in water from the Yangtze River. Specifically, a considerable amount of PFBS (22.9–26.1% of total PFC analyzed) was measured in water collected near Nanjing, which indicates the presence of potential sources of PFBS in this part of China. Completely different PFC composition profiles were observed for samples from the Pearl River and the Yangtze River. This indicates the presence of dissimilar sources in these two regions.     

Analysis of Pesticides Using a Polyppyrole Modified Electrode

Electrochemical methods can provide fast, sensitive and sometimes real time detection of pesticides. In the course of this work, a dispersed mercury electrode has been used to detect pesticides electrochemically. The electrode was prepared by depositing a thin mercury film on a glassy carbon disc and then coating a layer of polypyrrole on the disc. The effect of coating thickness on detection sensitivity was studied. A thin mercury film of 0.34 µm dispersed by one cycle polymerization of pyrrole was preferred. The influence of electrolyte, pH and organic solvent content on pesticide response was also investigated. The polypyrrole dispersed mercury electrode (Hg-PPy/GC) was not suitable for a pH above 6 but it can tolerate acetonitrile up to 10% at which concentration the mercury film coated glassy carbon electrode (Hg/GC) failed to response. Methyl parathion, methyl azinphos, parathion and fenitrothion were detected. The sensitivity of the dispersed mercury electrode was similar to a normal thin mercury film electrode in this case. A good response can be obtained for 1 ppm pesticides using fast linear sweeping voltammetry.     

First-trimester screening for Down syndrome; the role of nasal bone assessment in the Korean population

Objectives The aim of this study was to evaluate the role of nasal bone assessment in first-trimester screening for Down syndrome (DS) in the Korean population. Methods From July 2004 to March 2006, we prospectively evaluated the fetal nasal bones at 11–14 weeks' gestation in the Korean population. Results A successful evaluation was possible in 6490 of 6787 fetuses (95.6%). Absent, hypoechoic, and short nasal bones were seen in 4 (26.7%), 4 (26.7%), and 1 (6.7%) of 15 fetuses with DS, respectively, whereas in 5 (0.1%), 11 (0.2%), and 246 (3.8%) of 6456 normal fetuses. The incidence of absent and hypoechoic nasal bone showed significant differences between normal fetuses and fetuses with DS (P < 0.0005, both). Screening for DS using an absent or hypoechoic nasal bone resulted in a sensitivity of 53.3%, a specificity of 99.8%, a positive likelihood ratio of 215.2, and a negative likelihood ratio of 0.5. Conclusion Our study showed that nasal bone abnormality at 11–14 weeks of gestation had a high association with DS in the Korean population. This suggests that nasal bone assessment can be used to supplement the current first-trimester screening for DS in the Korean population. Copyright © 2007 John Wiley & Sons, Ltd.     

Trends in concentration of ground-level ozone and meteorological conditions during high ozone episodes in the Kao-Ping Airshed, Taiwan

This work analyzes the variations in daily maximum 1-hr ozone (O3) concentrations and the long-term trends in annual means of hourly ambient concentrations of O3, nitrogen oxides (nitrous oxide + nitrogen dioxide), and nonmethane hydrocarbons in the three administrative regions of Kao-Ping airshed in southern Taiwan over a recent 8-yr period. The annual or monthly means of all maxima, most 95th percentiles, and some 90th percentiles of the daily maximum 1-hr O3 concentrations exceed the daily limit of 120 parts per billion by volume in all three regions, namely, Kao-hsiung City, Kso-hsiung County, and P'ing-tung County. The monthly means of daily maximum 1-hr O3 concentrations exhibit distinct seasonal variations, with a bimodal form with the maxima in autumn and late winter to the middle of spring and a minimum in summer. The long-term variations in the annual means of hourly O3 concentrations in the three regions exhibit increasing trends. These increases in O3 are associated with the decline in ambient concentrations of nitrogen oxides and nonmethane hydrocarbons. High O3 episodes occur most often in autumn and most rarely in summer. The seasonal mean mixing heights in descending order follow the order of spring, summer, autumn, and winter. Meteorological parameters in autumn and winter indicate that the ground-level O3 tends to accumulate and trigger a high O3 episode on a warm day with sufficient sunlight and low wind in a high-pressure system, consistent with the low mixing heights in these two seasons.     

Photochemical and photocatalytic degradation of gaseous toluene using short-wavelength UV irradiation with TiO2 catalyst: comparison of three UV sources

The feasibility of the use of short-wavelength UV (254+185 nm) irradiation and TiO2 catalyst for photodegradation of gaseous toluene was evaluated. It was clear that the use of TiO2 under 254+185 nm light irradiation significantly enhanced the photodegradation of toluene relative to UV alone, owed to the combined effect of photochemical oxidation in the gas phase and photocatalytic oxidation on TiO2. The photodegradation with 254+185 nm light irradiation was compared with other UV wavelengths (365 nm (black light blue lamp) and 254 nm (germicidal UV lamp)). The highest conversion and mineralization were obtained with the 254+185 nm light. Moreover, high conversions were achieved even at high initial concentrations of toluene. Catalyst deactivation was also prevented with the 254+185 nm light. Regeneration experiments with the deactivated catalyst under different conditions revealed that reactive oxygen species played an important role in preventing catalyst deactivation by decomposing effectively the less reactive carbon deposits on the TiO2 catalyst. Simultaneous elimination of photogenerated excess ozone and residual organic compounds was accomplished by using a MnO2 ozone-decomposition catalyst to form reactive species for destruction of the organic compounds.     

Selective removal of organic contaminants from sediments: a methodology for toxicity identification evaluations (TIEs)

Aqueous slurries of a test sediment spiked with dibenz[a,h]anthracene, 2,4,5,2',4',5'-hexachlorobiphenyl, p,p'-DDE, or phenanthrene were subjected to decontamination experimentation. The spiked sediments were agitated at elevated temperatures for at least 96 h in the presence of either of the two contaminant-absorbing media: clusters of polyethylene membrane or lipid-containing semipermeable membrane devices (SPMDs). The effects of treatment temperature and surface area of media on the removal of contaminants were explored. This work is part of a larger methodology for whole-sediment toxicity identification evaluation (TIE). A method is being sought that is capable of detoxifying sediments with respect to organic contaminants while leaving toxicity attributable to inorganic contaminants unaffected.