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1.
The degradation of paracetamol in aqueous solutions in the presence of hydrogen peroxide was carried out by photochemistry, electrolysis and photoelectrolysis using modified 100 pores per inch reticulated vitreous carbon electrodes. The electrodes were coated with catalysts such as TiO2 and CuO/TiO2/Al2O3 by electrophoresis followed by heat treatment. The results of the electrolysis with bare reticulated vitreous carbon electrodes show that 90% paracetamol degradation occurs in 4 h at 1.3 V vs. SCE, forming intermediates such as benzoquinone and carboxylic acids followed by their complete mineralisation. When the electrolysis was carried out with the modified electrodes such as TiO2/RVC, 90% degradation was achieved in 2 h while with CuO/TiO2/Al2O3/RVC, 98% degradation took only 1 h. The degradation was also carried out in the presence of UV reaching 95% degradation with TiO2/RVC/UV and 99% with CuO/TiO2/Al2O3/RVC/UV in 1 h. The reactions were followed by spectroscopy UV-Vis, HPLC and total organic carbon analysis. These studies show that the degradation of paracetamol follows a pseudo-first order reaction kinetics.  相似文献   

2.
Hu XY  Fan J  Zhang KL  Wang JJ 《Chemosphere》2012,87(10):1155-1160
In this work, Bi4NbxTa(1−x)O8I photocatalysts have been synthesized by solid state reaction method and characterized by powder X-ray diffraction, scanning electron microscope and UV-Vis near infrared diffuse reflectance spectroscopy. The photocatalytic activity of these photocatalysts was evaluated by the degradation of methyl orange (MO) in aqueous solutions under visible light, UV light and solar irradiation. The effects of catalyst dosage, initial pH and MO concentration on the removal efficiency were studied, and the photocatalytic reaction kinetics of MO degradation as well. The results indicated that Bi4NbxTa(1−x)O8I exhibited high photocatalytic activity for the removal of MO in aqueous solutions. For example, the removal efficiency of MO by Bi4Nb0.1Ta0.9O8I was as high as 92% within 12 h visible light irradiation under the optimal conditions: initial MO concentration of 5-10 mg L−1, catalyst dosage of 6 g L−1 and natural pH (6-8), the MO molecules could be completely degradated by Bi4Nb0.1Ta0.9O8I within 40 min under UV light irradiation, and the photodegradation efficiency reaches to 60% after 7 h solar irradiation. Furthermore, the photocatalytic degradation of Bisphenol A (BPA) was also investigated under visible light irradiation. It is found that 99% BPA could be mineralized by Bi4Nb0.1Ta0.9O8I after 16 h visible light irradiation. Through HPLC/MS, BOD, TOC, UV-Vis measurements, we determined possible degradation products of MO and BPA. The results indicated that MO was degradated into products which are easier to be biodegradable and innocuous treated, and BPA could be mineralized completely. Furthermore, the possibility for the photosensitization effect in the degradation process of MO under visible light irradiation has been excluded.  相似文献   

3.
Dong H  Guan X  Wang D  Li C  Yang X  Dou X 《Chemosphere》2011,85(7):1115-1121
Batch experiments were carried out to investigate the influences of H2O2/Fe(II) molar ratio, pH, sequence of pH adjustment, initial As(V) concentration, and interfering ions on As(V) removal in H2O2-Fe(II) process from synthetic acid mine drainage (AMD). The optimum H2O2/Fe(II) molar ratio was one for arsenate removal over the pH range of 4-7. Arsenate removal at pH 3 was poor even at high Fe(II) dosage due to the high solubility of Fe(III) formed in situ. With the increase of Fe(II) dosage, arsenate removal increased progressively before a plateau was reached at pH 5 as arsenate concentration varied from 0.05 to 2.0 mg L−1. However, arsenate removal was negligible at Fe/As molar ratio <3 and then experienced a striking increase before a plateau was reached at pH 7 and arsenate concentration ≥1.0 mg L−1. The co-occurring ions exerted no significant effect on arsenate removal at pH 5. The experimental results with synthetic AMD revealed that this method is highly selective for arsenate removal and the co-occurring ions either improved arsenate removal or slightly depressed arsenate removal at pH 5-7. The extended X-ray absorption fine structure (EXAFS) derived As-Fe length, 3.27-3.30 Å, indicated that arsenate was removed by forming bidentate-binuclear complexes with FeO(OH) octahydra. The economic analysis revealed that the cost of the H2O2-Fe(II) process was only 17-32% of that of conventional Fe(III) coagulation process to achieve arsenate concentration below 10 μg L−1 in treated solution. The results suggested that the H2O2-Fe(II) process is an efficient, economical, selective and practical method for arsenate removal from AMD.  相似文献   

4.
Hong J  Lu S  Zhang C  Qi S  Wang Y 《Chemosphere》2011,84(11):1542-1547
A new Vis-Fe0-H2O2-citrate-O2 system comprising zero-valent iron, hydrogen peroxide, citrate anion and aeration at circumneutral pH under visible irradiation was studied. 21 μmol L−1 of Rhodamine B (RhB) was chosen as the substrate to be tested. Experiments were conducted under conditions of 2.9 mmol L−1 of H2O2, 12.6 g of Fe0 and 1.0 mmol L−1 of citrate at pH 7.5. Results showed that, in 1 h reaction, 54% of RhB was removed with corresponding 26% of COD reduced. Meanwhile, the amount of released dissolved irons from Fe0 surface was found to be at a very low level as <5.4 μmol L−1. Extinguishing tests with isopropanol suggested that RhB oxidation by hydroxyl radicals was the main process taken place in Vis-Fe0-H2O2-citrate-O2 system, which accounted for 75% of substrate removal in 3 h reaction. Control and factor influencing experiments showed that the prohibitive extents of individual factor importance on RhB removal followed a decreasing order of Fe0 > H2O2 > citrate > Vis > O2. This study showed an excellent system that could remove refractory organic compounds from water in laboratory researches, and also provided a good idea to reduce secondary contamination by dissolved irons in future investigations.  相似文献   

5.
Hou MF  Liao L  Zhang WD  Tang XY  Wan HF  Yin GC 《Chemosphere》2011,83(9):1279-1283
Degradation of rhodamine B by Fe(0)-based Fenton process with H2O2 was investigated. The effects of H2O2 dose, Fe(0) dose, initial concentration of rhodamine B and initial pH value on the degradation of rhodamine B were examined. The results showed that the degradation and mineralization of rhodamine B occurred with low dose of H2O2 and Fe(0). The intermediates of rhodamine B were analyzed with UV-Vis spectrophotometry and ion chromatography and the mechanism of oxidative degradation of rhodamine B was also discussed. The reactive oxygen species (·OH) produced in Fe(0)-based Fenton process with H2O2 is the key to the degradation of rhodamine B by ways of N-de-ethylation, chromophore cleavage, ring-opening and mineralization.  相似文献   

6.
Two types of nano-pore substrates, waste-reclaimed (WR) and soil mineral (SM) with the relatively low density, were modified by the reaction with irons (i.e. Fe(II):Fe(III) = 1:2) and the applicability of the modified substrates (i.e. Fe-WR and Fe-SM) on cyanide removal was investigated. Modification (i.e. Fe immobilization on substrate) decreased the BET surface area and PZC of the original substrates while it increased the pore diameter and the cation exchange capacity (CEC) of them. XRD analysis identified that maghemite (γ-Fe2O3) and iron silicate composite ((Mg, Fe)SiO3) existed on Fe-WR, while clinoferrosilite (FeSiO3) was identified on Fe-SM. Cyanide adsorption showed that WR adsorbed cyanide more favorably than SM. The adsorption ability of both original substrates was enhanced by the modification, which increased the negative charges of the surfaces. Without the pH adjustment, cyanide was removed as much as 97% by the only application of Fe-WR, but the undesirable transfer to hydrogen cyanide was possible because the pH was dropped to around 7.5. With a constant pH of 12, only 54% of cyanide was adsorbed on Fe-WR. On the other hand, the pH was kept as 12 without adjustment in Fe-WR/H2O2 system and cyanide was effectively removed by not only adsorption but also the catalytic oxidation. The observed first-order rate constant (kobs) for cyanide removal were 0.49 (±0.081) h−1. Moreover, the more cyanate production with the modified substrates indicated the iron composites, especially maghemite, on substrates had the catalytic property to increase the reactivity of H2O2.  相似文献   

7.
Reductive transformation of 2,4-dichlorophenoxyacetic acid (2,4-D) by nanoscale and microscale Fe3O4 was investigated and compared. Disappearance of the parent species and formation of reaction intermediates and products were kinetically analyzed. Results suggest that the transformation of 2,4-D followed a primary pathway of its complete reduction to phenol and a secondary pathway of sequential reductive hydrogenolysis to 2,4-dichlorophenol (2,4-DCP), chlorophenol (2-CP, 4-CP) and phenol. About 65% of 2,4-D with initial concentration of 50 μ M was transformed within 48 h in the presence of 300 mg L?1 nanoscale Fe3O4, and the reaction rates increased with increasing dosage of nanoscale Fe3O4. The decomposition of 2,4-D proceeded rapidly at optimum pH 3.0. Chloride was identified as a reduction product for 2,4-D in the magnetite–water system. Reductive transformation of 2,4-D by microscale Fe3O4 was slower than that by nanoscale Fe3O4. The reactions apparently followed pseudo-first-order kinetics with respect to the 2,4-D transformation. The degradation rate of 2,4-D decreased with the increase of initial 2,4-D concentration. In addition, anions had a significant adverse impact on the degradation efficiency of 2,4-D.  相似文献   

8.
Chang YK  Wu CC  Lee LT  Lin RS  Yu YH  Chen YC 《Chemosphere》2012,87(1):26-30
A mass screening of lung function associated with air pollutants for children is limited. This study assessed the association between air pollutants exposure and the lung function of junior high school students in a mass screening program in Taipei city, Taiwan. Among 10,396 students with completed asthma screening questionnaires and anthropometric measures, 2919 students aged 12-16 received the spirometry test. Forced vital capacity (FVC) and forced expiratory flow in 1 s (FEV1) in association with daily ambient concentrations of particulate matter with diameter of 10 μm or less (PM10), sulfur dioxide (SO2), carbon monoxide (CO), nitrogen dioxide (NO2), and ozone (O3) were assessed by regression models controlling for the age, gender, height, weight, student living districts, rainfall and temperature. FVC, had a significant negative association with short-term exposure to O3 and PM10 measured on the day of spirometry testing. FVC values also were reversely associated with means of SO2, O3, NO2, PM10 and CO exposed 1 d earlier. An increase of 1-ppm CO was associated with the reduction in FVC for 69.8 mL (95% CI: −115, −24.4 mL) or in FEV1 for 73.7 mL (95% CI: −118, −29.7 mL). An increase in SO2 for 1 ppb was associated with the reductions in FVC and FEV1 for 12.9 mL (95% CI: −20.7, −5.09 mL) and 11.7 mL (95% CI: −19.3, −4.16 mL), respectively. In conclusion, the short-term exposure to O3 and PM10 was associated with reducing FVC and FEV1. CO and SO2 exposure had a strong 1-d lag effect on FVC and FEV1.  相似文献   

9.
The effect of elevated CO2 and O3 on apparent quantum yield (?), maximum photosynthesis (Pmax), carboxylation efficiency (Vcmax) and electron transport capacity (Jmax) at different canopy locations was studied in two aspen (Populus tremuloides) clones of contrasting O3 tolerance. Local light climate at every leaf was characterized as fraction of above-canopy photosynthetic photon flux density (%PPFD). Elevated CO2 alone did not affect ? or Pmax, and increased Jmax in the O3-sensitive, but not in the O3-tolerant clone. Elevated O3 decreased leaf chlorophyll content and all photosynthetic parameters, particularly in the lower canopy, and the negative impact of O3 increased through time. Significant interaction effect, whereby the negative impact of elevated O3 was exaggerated by elevated CO2 was seen in Chl, N and Jmax, and occurred in both O3-tolerant and O3-sensitive clones. The clonal differences in the level of CO2 × O3 interaction suggest a relationship between photosynthetic acclimation and background O3 concentration.  相似文献   

10.
In the present study we investigate the fate of citalopram (CIT) at neutral pH using advanced water treatment technologies that include O3, ClO2 oxidation, UV irradiation and Fenton oxidation. The ozonation resulted in 80% reduction after 30 min treatment. Oxidation with ClO2 removed >90% CIT at a dosage of 0.1 mg L−1. During UV irradiation 85% reduction was achieved after 5 min, while Fenton with addition of 14 mg L−1 (Fe2+) resulted in 90% reduction of CIT. During these treatment experiments transformation products (TPs) were formed from CIT, where five compounds were identified by using high resolution and tandem mass spectrometry. Among these desmethyl-citalopram and citalopram N-oxide have been previously identified as human metabolites, while three are novel and published here for the first time. The three TPs are a hydroxylated dimethylamino-side chain derivative, a butyrolactone derivative and a defluorinated derivative of CIT.  相似文献   

11.
Particle-bound polychlorinated dibenzo-p-dioxins and polychlorinated dibenzofurans (PCDD/Fs) in ambient air were monitored together with particulate matter less than 10 μm (PM10) at three sampling sites of the Andean city of Manizales, Colombia; during September 2009 and July 2010. PCDD/Fs ambient air emissions ranged from 1 fg WHO-TEQ m−3 to 52 fg WHO-TEQ m−3 in particulate fraction. The PM10 concentrations ranged from 23 μg m−3 to 54 μg m−3. Concentrations of PM10 and PCDD/Fs in ambient air observed for Manizales - a medium sized city with a population of 380 000 - were comparable to concentrations in larger cities. The highest concentrations of PCDD/Fs and PM10 found in this study were determined at the central zone of the city, characterized by public transportation density, where diesel as principal fuel is used. In addition, hypothetical gas fractions of PCDD/Fs were calculated from theoretical Kp data. Congener profiles of PCDD/Fs exhibited ratios associated with different combustion sources at the different sampling locations, ranging from steel recycling to gasoline and diesel engines. Taking into account particle and gas hypothetical fraction of PCDD/Fs, Manizales exhibited values of PCDD/Fs equivalent to rural and urban-industrial sites in the southeast and center of the city respectively. Poor correlation of PCDDs with PM10 (r = −0.55 and r = 0.52) suggests ambient air PCDDs were derived from various combustion sources. Stronger correlation was observed of PCDFs with PM10. Poor correlation between precipitation and reduced PM10 concentration in ambient air (r = −0.45) suggested low PM10 removal by rainfall.  相似文献   

12.
We examined the effect of ozone (O3) on Norway spruce (Picea abies) needle epicuticular wax over three seasons at the Kranzberg Ozone Fumigation Experiment. Exposure to 2× ambient O3 ranged from 64.5 to 74.2 μl O3 l−1 h AOT40, and 117.1 to 123.2 nl O3 l−1 4th highest daily maximum 8-h average O3 concentration. The proportion of current-year needle surface covered by wax tubes, tube aggregates, and plates decreased (P = 0.011) under 2× O3. Epistomatal chambers had increased deposits of amorphous wax. Proportion of secondary alcohols varied due to year (P = 0.004) and O3 treatment (P = 0.029). Secondary alcohols were reduced by 9.1% under 2× O3. Exposure to 2× O3 increased (P = 0.037) proportions of fatty acids by 29%. Opposing trends in secondary alcohols and fatty acids indicate a direct action of O3 on wax biosynthesis. These results demonstrate O3-induced changes in biologically important needle surface characteristics of 50-year-old field-grown trees.  相似文献   

13.
Xu W  Wang H  Liu R  Zhao X  Qu J 《Chemosphere》2011,83(7):1020-1027
Ferric and manganese binary oxide (FMBO) has been successfully used to remediate arsenic-polluted river, but there still lacks sufficient data to evaluate its effects on environments. The release behaviors of iron (Fe), manganese (Mn), and arsenic (As) in different Eh ranges were investigated for As-bearing FMBO sediment after remediating As-polluted DaSha River by FMBO. Under high Eh range (+550 to +400 mV), slight dissolution of Fe and Mn, which corresponded to 12.2% and 25.6%, and less than 5% of As release were observed in 336 h. Under lower Eh range (+50 to −100 mV), elevated extent of the dissolution of Mn and Fe were observed, which corresponded to as high as 61.3% and 70.1%. Under such conditions, the dissolution rate of Mn was higher than that of Fe. Furthermore, from the established relationship of As release and the dissolution of Fe and Mn, the release of As seemed dominated by the dissolution of Fe. X-ray photoelectron spectroscopy (XPS) analysis demonstrated the release of Fe, Mn, As(III), and As(V) after sodium ascorbate-treatment, and the re-adsorption of As(V), as indicated from the increased binding energy of As 3d from 44.78 to 45.83 eV. Surface element composition analysis indicated significant decrease of Mn from 3.22% to 0.54%, slight increase of Fe from 12.45% to 13.67%, and elevated ratio of As from 0.11% to 0.32% accordingly. The main reactions of Fe and Mn dissolution and the pathways of As release under different Eh ranges were also proposed.  相似文献   

14.
15.
Stomatal closure and biosynthesis of antioxidant molecules are two fundamental components of the physiological machinery that lead to stress adaptation during plant's exposure to salinity. Since high stomatal resistance may also contribute in counteracting O3 damages, we hypothesized that soil salinization may increase O3 tolerance of crops. An experiment was performed with alfalfa grown in filtered (AOT40 = 0 in both years) and non-filtered (AOT40 = 9.7 in 2005 and 6.9 ppm h in 2006) open-top chambers. Alfalfa yield was reduced by O3 (−33%) only in plants irrigated with salt-free water, while the increasing levels of soil salinity until 1.06 dS m−1 reduced both stomatal conductance and plant O3 uptake, thus linearly reducing O3 effects on yield. Therefore a reliable flux-based model for assessing the effects of O3 on crop yield should take into account soil salinity.  相似文献   

16.
Peroxyacetyl nitrate (PAN) in air has been well known as the indicator of photochemical smog due to its frequent occurrences in Seoul metropolitan area. This study was implemented to assess the distribution characteristics of atmospheric PAN in association with relevant parameters measured concurrently. During a full year period in 2011, PAN was continuously measured at hourly intervals at two monitoring sites, Gwang Jin (GJ) and Gang Seo (GS) in the megacity of Seoul, South Korea. The annual mean concentrations of PAN during the study period were 0.64 ± 0.49 and 0.57 ± 0.46 ppb, respectively. The seasonal trends of PAN generally exhibited dual peaks in both early spring and fall, regardless of sites. Their diurnal trends were fairly comparable to each other. There was a slight time lag (e.g., 1 h) in the peak occurrence pattern between O3 and PAN, as the latter trended to peak after the maximum UV irradiance period (16:00 (GJ) and 17:00 (GS)). The concentrations of PAN generally exhibited strong correlations with particulates. The results of this study suggest that PAN concentrations were affected sensitively by atmospheric stability, the wet deposition of NO2, wind direction, and other factors.  相似文献   

17.
Gene expression responses of paper birch (Betula papyrifera) leaves to elevated concentrations of CO2 and O3 were studied with microarray analyses from three time points during the summer of 2004 at Aspen FACE. Microarray data were analyzed with clustering techniques, self-organizing maps, K-means clustering and Sammon's mappings, to detect similar gene expression patterns within sampling times and treatments. Most of the alterations in gene expression were caused by O3, alone or in combination with CO2. O3 induced defensive reactions to oxidative stress and earlier leaf senescence, seen as decreased expression of photosynthesis- and carbon fixation-related genes, and increased expression of senescence-associated genes. The effects of elevated CO2 reflected surplus of carbon that was directed to synthesis of secondary compounds. The combined CO2 + O3 treatment resulted in differential gene expression than with individual gas treatments or in changes similar to O3 treatment, indicating that CO2 cannot totally alleviate the harmful effects of O3.  相似文献   

18.
Gotoh Y  Iwata G  Choh K  Kubota M  Matsuda H 《Chemosphere》2011,85(4):637-642
A comparison of CaOs produced by calcining two types of hydrated lime and calcium carbonate was made for decomposition of trichloroethylene and in-situ dry sorption of the decomposed Cl-products using a lab-scale gas flow type tubular packed bed reactor. About 20 mg of CaO sample was mixed with about 2 g of Al2O3 particles and packed in the reactor and allowed to react with a flowing standard gas containing 500 ppm of C2HCl3 (N2 balance) at 673 and 873 K, under the condition that the reaction of CaO with C2HCl3 might be completed within a few hours.It was found that no thermal decomposition of C2HCl3 at or below 673 K was observed in a reactor packed only with Al2O3 particles. However, a considerable amount of decomposition of C2HCl3 was obtained in a reactor packed with CaO and Al2O3, even at 673 K. For 1 mol of CaO prepared by calcining highly reactive Ca(OH)2 at 673 K, decomposition of 0.42 mol of C2HCl3 and in-situ absorption product of 0.53 mol of CaCl2 were obtained. At 873 K, about 46% of C2HCl3 was thermally decomposed. The total amount of C2HCl3 decomposed in CaO-Al2O3 particle bed at 873 K became nearly twice larger than that at 673 K. For 1 mol of CaO prepared by calcining highly reactive Ca(OH)2 at 873 K, decomposition of 0.59 mol of C2HCl3 and in-situ absorption product of 0.67 mol of CaCl2 were obtained. Small amounts of C2Cl2, C2Cl4, CCl4, etc. were detected during decomposition of C2HCl3 at 673 and 873 K.It was recognized that the data on decomposition of C2HCl3 as well as in-situ dry sorption of Cl-products in CaO particle bed were correlated with specific surface area of the CaO employed.  相似文献   

19.
Wang HC  Liang HS  Chang MB 《Chemosphere》2011,82(8):1090-1095
In this study, we examined the experimental catalytic oxidation of gaseous monochlorobenzene (MCBz) with O3 over Fe2O3 in a packed bed reactor to investigate the feasibility of economical low temperature decomposition at a high space velocity (SV). We investigated the effects of several reaction parameters (temperature, O3 concentration, and SV) on the MCBz oxidation. At 150 °C, the conversion of MCBz over Fe2O3 in the absence of O3 was only 3%; it increased to 91% over Fe2O3 in the presence of 1200 ppm of O3 at a high SV of 83 s−1. A long-term operation study revealed that the conversion of MCBz was stable for more than 96 h. In the steady state, the carbon and chlorine balances were 88% and 86%, respectively. Applying a Langmuir-Hinshelwood kinetic model, we estimated an activation energy of 16.7 kJ mol−1 for MCBz oxidation over Fe2O3 in the presence of O3.  相似文献   

20.
The organic matter present in the concentrate streams generated from reverse osmosis (RO) based municipal wastewater reclamation processes poses environmental and health risks on its disposal to the receiving environment (e.g., estuaries, bays). The potential of a biological activated carbon (BAC) process combined with pre-oxidation using a UVC/H2O2 advanced oxidation process for treating a high salinity (TDS ∼ 10 000 mg L−1) municipal wastewater RO concentrate (ROC) was evaluated at lab scale during 90 d of operation. The combined treatment reduced the UVA254 and colour of the ROC to below those for the influent of the RO process (i.e., biologically treated secondary effluent), and the reductions in DOC and COD were approximately 60% and 50%, respectively. UVC/H2O2 was demonstrated to be an effective means of converting the recalcitrant organic compounds in the ROC into biodegradable substances which were readily removed by the BAC process, leading to a synergistic effect of the combined treatment in degrading the organic matter. The tests using various BAC feed concentrations suggested that the biological treatment was robust and consistent for treating the high salinity ROC. Using Microtox analysis no toxicity was detected for the ROC after the combined treatment, and the trihalomethane formation potential was reduced from 3.5 to 2.8 mg L−1.  相似文献   

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