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1.
Gaseous nitrogen dioxide (NO2) represents an oxidant that is present in relatively high concentrations in various indoor settings. Remarkably increased NO2 levels up to 1.5 ppm are associated with homes using gas stoves. The heterogeneous reactions of NO2 with adsorbed water on surfaces lead to the generation of nitrous acid (HONO). Here, we present a HONO source induced by heterogeneous reactions of NO2 with selected indoor paint surfaces in the presence of light (300 nm?<?λ?<?400 nm). We demonstrate that the formation of HONO is much more pronounced at elevated relative humidity. In the presence of light (5.5 W m?2), an increase of HONO production rate of up to 8.6?·?109 molecules cm?2 s?1 was observed at [NO2]?=?60 ppb and 50 % relative humidity (RH). At higher light intensity of 10.6 (W m?2), the HONO production rate increased to 2.1?·?1010 molecules cm?2 s?1. A high NO2 to HONO conversion yield of up to 84 % was observed. This result strongly suggests that a light-driven process of indoor HONO production is operational. This work highlights the potential of paint surfaces to generate HONO within indoor environments by light-induced NO2 heterogeneous reactions.  相似文献   

2.
We evaluated the catalytic activity of a water-soluble iron-porphyrin in an oxidative coupling reaction to form covalent bonds between 2,4-dichlorophenol (2,4-DCP) and humic molecules. The biomimetic catalysis in the presence of H2O2 was tested in the dark and in daylight, and changes in reaction products were revealed by high-performance liquid chromatography (HPLC) and nuclear magnetic resonance (NMR) spectroscopy. In all conditions, iron-porphyrin was effective in promoting complete disappearance of 2,4-DCP, although catalyst activity was enhanced in daylight (with a maximum turnover number of 85.13). Further evidence of the occurred covalent coupling between 2,4-DCP and humic molecules was revealed by diffusion-ordered nuclear magnetic resonance (DOSY-NMR) spectroscopy that showed a reduced diffusivity of 2,4-DCP after the catalytic reaction. These findings indicate that iron-porphyrin is an efficient catalyst for the covalent binding of polyhalogenated phenols to humic molecules, thereby suggesting that the copolymerization reactions may become a useful technology to remediate soils and waters contaminated by halogenated phenols and their analogues.  相似文献   

3.
Oxidative transformation of organic contaminants by manganese oxides was commonly investigated with pure MnO2 suspension, which deviates from the fact that natural manganese oxides are seldom present as a pure form in the natural environment. In this study, we prepared manganese oxide-coated sand (MOCS) and evaluated its oxidative capacity using bisphenol A (BPA) as the model compound. BPA was transformed by MOCS and the reaction followed an exponential decay model. The reaction was pH dependent and followed the order of pH 4.5?>?pH 5.5?>?pH 6.5?>?pH 7.5?>?pH 8.6?>?pH 9.6, indicating that acidic conditions facilitated BPA transformation while basic conditions disfavored the reaction. Coexisting metal ions exhibited inhibitory effects and followed the order of Fe3+ > Zn2+ > Cu2+ > Ca2+ > Mg2+ > Na+. Transformation of BPA by MOCS was much slower than that by pure MnO2 suspension. However, similar transformation products were identified in both studies, suggesting the same reaction pathways. This work suggests that the reactivity of MnO2 in the environment might be overestimated if extrapolating the result from the pure MnO2 suspension because natural MnO2 is mainly present as coating on the surface of soils and sediments.  相似文献   

4.
The ubiquitous dissolved organic matter (DOM) has an important influence on transformation of organic contaminants through the production of reactive substances, such as ?OH, 1O2, and 3DOM*. The photolysis of a higher chlorinated polychlorinated biphenyl (PCB) congener (2,2′,4,4′,5,5′-hexachlorobiphenyl, PCB 153) under simulated sunlight in presence of humic acid (HA) was investigated. Degradation of PCB 153 was accelerated significantly by the addition of HA, with a rate constant of 0.0214, 0.0413, and 0.0358 h?1 in the initial 18 h of irradiation in presence of 1, 5, and 20 mg/L HA, respectively. The main photodegradation products analyzed by gas chromatography mass spectrometry were 4-hydroxy-2,2′,4′,5,5′-pentaCB and 2,4,5-trichlorobenzoic acid. Main reactive species involved were determined by the electron spin-resonance spectroscopy, including 1O2 and ?OH. Special scavengers were added to elucidate the photolysis mechanisms. By using the specific scavengers, it turned out that ?OH accounted for 29.3 % of the degradation, and the intra-DOM reactive species (1O2, ?OH, and 3DOM*) accounted for 59.6 % of the degradation. Photo-transformation sensitized by DOM, which involves both aqueous and intra-DOM reactions of PCBs with reactive species, may be one of the most important mechanisms for natural attenuation of PCBs.  相似文献   

5.
The increasing use of nanoparticles (NPs) worldwide has raised some concerns about their impact on the environment. The aim of the study was to assess the toxicity of metal oxide nanoparticles, singly or combined, in a freshwater fish (Carassius auratus). The fish were exposed for 7, 14, and 21 days to different concentrations of NPs (10 μg Al2O3.L?1, 10 μg ZnO.L?1, 10 μg Al2O3.L?1 plus 10 μg ZnO.L?1, 100 μg Al2O3.L?1, 100 μg ZnO.L?1, and 100 μg Al2O3.L?1 plus 100 μg ZnO.L?1). At the end of each exposure period, antioxidant enzyme activity (catalase, glutathione-S-transferase, and superoxide dismutase), lipid peroxidation, and histopathology were assessed in the gills and livers of C. auratus. The results show an increase in catalase (CAT) and superoxide dismutase (SOD) activity in the gills and livers of fish, especially after 14 days of exposure to single and combined NPs, followed by a reduction at 21 days. An increase in glutathione S-transferase (GST) was observed in gills after 7 days for all tested NP concentrations (single and combined); while in livers, a significant increase was determined after 14 days of exposure to 100 μg.L?1 of both single ZnO and Al2O3 NPs. Lipid peroxidation (LPO) significantly increased in gills after 7 days of exposure to 100 μg.L?1 Al2O3 NPs (single or combined). In livers, LPO increased significantly after 7 days of exposure to all tested concentrations of both single ZnO and Al2O3 (except for 10 μg Al2O3.L?1), and after 14 days of exposure to ZnO (10 and 100 μg.L?1) and Al2O3 (100 μg.L?1). The results from histological observations suggest that exposure to metal oxide NPs affected both livers and gills, presenting alterations such as gill hyperplasia and liver degeneration. However, the most pronounced effects were found in gills. In general, this study shows that the tested NPs, single or combined, are capable of causing sub-lethal effects on C. auratus, but when combined, NPs seem to be slightly more toxic than when added alone.  相似文献   

6.
Fe2O3 and CeO2 modified activated coke (AC) synthesized by the equivalent-volume impregnation were employed to remove elemental mercury (Hg0) from simulated flue gas at a low temperature. Effects of the mass ratio of Fe2O3 and CeO2, reaction temperature, and individual flue gas components including O2, NO, SO2, and H2O (g) on Hg0 removal efficiency of impregnated AC were investigated. The samples were characterized by Brunauer–Emmett–Teller (BET), X-ray diffraction (XRD), scanning electron microscopy (SEM), and X-ray photoelectron spectroscopy (XPS). Results showed that with optimal mass percentage of 3 % Fe2O3 and 3 % CeO2 on Fe3Ce3/AC, the Hg0 removal efficiency could reach an average of 88.29 % at 110 °C. Besides, it was observed that O2 and NO exhibited a promotional effect on Hg0 removal, H2O (g) exerted a suppressive effect, and SO2 showed an insignificant inhibition without O2 to some extent. The analysis of XPS indicated that the main species of mercury on used Fe3Ce3/AC was HgO, which implied that adsorption and catalytic oxidation were both included in Hg0 removal. Furthermore, the lattice oxygen, chemisorbed oxygen, and/or weakly bonded oxygen species made a contribution to Hg0 oxidation.  相似文献   

7.
The influences of HCO3 ?, Cl?, and other components on the UV/TiO2 degradation of the antineoplastic agents ifosfamide (IFO) and cyclophosphamide (CP) were studied in this work. The results indicated that the presence of HCO3 ?, Cl?, NO3 ?, and SO4 2? in water bodies resulted in lower degradation efficiencies. The half-lives of IFO and CP were 1.2 and 1.1 min and increased 2.3–7.3 and 3.2–6.3 times, respectively, in the presence of the four anions (initial compound concentration = 100 μg/L, TiO2 loading =100 mg/L, anion concentration = 1000 mg/L, and pH = 8). Although the presence of HCO3 ? in the UV/TiO2/HCO3 ? system resulted in a lower degradation rate and less byproduct formation for IFO and CP, two newly identified byproducts, P11 (M.W. = 197) and P12 (M.W. = 101), were formed and detected, suggesting that additional pathways occurred during the reaction of ?CO3 ? in the system. The results also showed that ?CO3 ? likely induces a preferred ketonization pathway. Besides the inorganic anions HCO3 ?, Cl?, NO3 ?, and SO4 2?, the existence of dissolved organic matter in the water has a significant effect and inhibits CP degradation. Toxicity tests showed that higher toxicity occurred in the presence of HCO3 ? or Cl? during UV/TiO2 treatment and within 6 h of reaction time, implying that the effects of these two anions should not be ignored when photocatalytic treatment is applied to treat real wastewater.  相似文献   

8.
以三氯生为目标污染物,研究了黄铁矿催化H2O2非均相类Fenton体系对污染物的去除效果,并利用SEM、EDS等手段对天然黄铁矿进行了表征。考察了催化剂、H2O2投加量、溶液初始pH、反应时间等重要因素对催化氧化反应的影响。在H2O2投加量5 mg/L,黄铁矿用量0.1 g/L,溶液初始pH为8,反应10 min后,三氯生的去除率达90%以上。相对于传统Fenton反应,pH对本非均相催化反应的影响较小,在2~10的pH范围内,仍有较高的催化活性。利用GC-MS分析显示,三氯生降解过程能够产生包括2,4-二氯苯酚在内的多种中间产物。  相似文献   

9.

Introduction

A synthetic water-soluble meso-tetra(2,6-dichloro-3-sulfonatophenyl)porphyrinate of iron(III) chloride, Fe-(TDCPPS)Cl, was employed to catalyze the oxidative co-polymerization of penta-halogenated phenols in two humic materials of different origin.

Materials and methods

Co-polymerization of pentachlorophenol (PCP) was followed by high-performance size-exclusion chromatography (HPSEC), the unbound PCP recovered from reacting humic solutions was evaluated by gas-chromatography/electron capture detector, and the oxidative catalyzed coupling of pentafluorophenol (PFP) into humic matter was assessed by liquid-state 19F-NMR spectroscopy. HPSEC showed that the catalyzed oxidative coupling between PCP and humic molecules increased the apparent weight-average molecular weight (M w) values in both humic substances.

Results and discussion

HPSEC further indicated that the co-polymerization reaction turned the loosely bound humic supramolecular structures into more stable conformations, which could no longer be disrupted by the disaggregating effect of acetic acid. The occurrence of covalent linkages established between PCP and humic molecules was also suggested by the very little amount of PCP found free in solution after the catalyzed co-polymerization. 19F-NMR spectroscopy suggested that also PFP could be oxidatively coupled to humic materials. PFP-humic co-polymerization reaction produced 19F-spectra with many more 19F signals and wider chemical shifts spread than for PFP alone or PFP subjected to catalyzed coupling without humic matter.

Conclusions

These findings show that biomimetic iron-porphyrin is an efficient catalyst for the covalent binding of polyhalogenated phenols to humic molecules, thereby suggesting that the co-polymerization reaction may become a useful technology to remediate soils and waters contaminated by polyhalogenated phenols and their analogues.  相似文献   

10.
Considering the increasing incorporation of manufactured nano-material into consumer products, there is a concern about its potential impacts in biological wastewater treatment. In this study, the response of anaerobic sludge to the presence of Bi2WO6 nano-particles (NPs) was investigated in the anaerobic membrane bioreactor (AnMBR). As the concentration of Bi2WO6 in the reactor was controlled around 1 mg/L, there was no significant difference in effluent water quality or bacterial activities before and after NP exposure, partially due to the microbial-induced NP aggregation and stable complex formation. However, with the increasing dosage of Bi2WO6 from 5 to 40 mg/L, great influences on the AnMBR performance were observed, including the reduction of COD removal efficiency, inhibition of the mechanization step, increased production of soluble microbial products, and enhanced secretion of extracellular polymer substrates. Additional investigation with high-throughput sequencing was conducted, clearly demonstrating that Bi2WO6 NPs induced changes in the bacterial community.  相似文献   

11.
The incorporation of xenobiotics into soil, especially via covalent bonds or sequestration has a major influence on the environmental behavior including toxicity, mobility, and bioavailability. The incorporation mode of 4-chloro-2-methylphenoxyacetic acid (MCPA) into organo-clay complexes has been investigated under a low (8.5 mg MCPA/kg soil) and high (1000 mg MCPA/kg soil) applied concentration, during an incubation period of up to 120 days. Emphasis was laid on the elucidation of distinct covalent linkages between non-extractable MCPA residues and humic sub-fractions (humic acids, fulvic acids, and humin). The cleavage of compounds by a sequential chemical degradation procedure (OH?, BBr3, RuO4, TMAH thermochemolysis) revealed for both concentration levels ester/amide bonds as the predominate incorporation modes followed by ether linkages. A possible influence of the soil microbial activity on the mode of incorporation could be observed in case of the high level samples. Structure elucidation identified MCPA as the only nonextractable substance, whereas the metabolite 4-chloro-2-methylphenol was additionally found as bioavailable and bioaccessible compound.  相似文献   

12.
The aqueous photodegradation of fluopyram was investigated under UV light (λ?≥?200 nm) and simulated sunlight irradiation (λ?≥?290 nm). The effect of solution pH, fulvic acids (FA), nitrate (NO3 ?), Fe (III) ions, and titanium dioxide (TiO2) on direct photolysis of fluopyram was explored. The results showed that fluopyram photodegradation was faster in neutral solution than that in acidic and alkaline solutions. The presence of FA, NO3 ?, Fe (III), and TiO2 slightly affected the photodegradation of fluopyram under UV irradiation, whereas the photodegradation rates of fluopyram with 5 mg L?1 Fe (III) and 500 mg L?1 TiO2 were about 7-fold and 13-fold faster than that without Fe (III) and TiO2 under simulated sunlight irradiation, respectively. Three typical products for direct photolysis of fluopyram have been isolated and characterized by liquid chromatography tandem mass spectrometry. These products resulted from the intramolecular elimination of HCl, hydroxyl-substitution, and hydrogen extraction. Based on the identified transformation products and evolution profile, a plausible degradation pathway for the direct photolysis of fluopyram in aqueous solution was proposed. In addition, acute toxicity assays using the Vibrio fischeri bacteria test indicated that the transformation products were more toxic than the parent compound.  相似文献   

13.
The possibilities of application of a three-step system combining hybrid biological treatment followed by advanced UV/O3 oxidation with in situ generated O3 and membrane separation (ultrafiltration (UF) and nanofiltration (NF)) to treat and reuse the wastewater from an industrial laundry are presented. By the application of a hybrid moving bed biofilm reactor (HMBBR), the total organic carbon concentration was reduced for about 90 %. However, since the HMBBR effluent still contained organic contaminants as well as high concentrations of inorganic ions and exhibited significant turbidity (8.2 NTU), its further treatment before a possible reuse in the laundry was necessary. The UV/O3 pretreatment prior to UF was found to be an efficient method of the membrane fouling alleviation. During UF, the turbidity of wastewater was reduced below 0.3 NTU. To remove the inorganic salts, the UF permeate was further treated during NF. The NF permeate exhibited very low conductivity (27–75 μS/cm) and contained only small amounts of Ca2+ and Mg2+; thus ,it could be reused at any stage of the laundry process.  相似文献   

14.
More attention has been paid to the deterioration of water bodies polluted by drinking water treatment sludge (DWTS) in recent years. It is important to develop methods to effectively treat DWTS by avoiding secondary pollution. We report herein a novel investigation for recovery of Si and Fe from DWTS, which are used for the synthesis of two iron oxide@SiO2 composites for adsorption of reactive red X-3B (RRX-3B) and NaNO2. The results show that Fe3+ (acid-leaching) and Si4+ (basic-leaching) can be successfully recovered from roasted DWTS. Whether to dissolve Fe(OH)3 precipitation is the key point for obtaining Fe3O4 or γ-Fe2O3 particles using the solvothermal method. The magnetic characteristics of Fe3O4@SiO2 (390.0 m2 g?1) or Fe2O3@SiO2 (220.9 m2 g?1) are slightly influenced by the coated porous SiO2 layer. Peaks of Fe–O stretching vibration (580 cm?1) and asymmetric Si–O–Si stretching vibrations (1080 cm?1) of Fe3O4@SiO2 indicate the successful coating of a thin silica layer (20–150 nm). The adsorption capacity of RRX-3B and NaNO2 by Fe3O4@SiO2 is better than that of Fe2O3@SiO2, and both composites can be recycled through an external magnetic field. This method is an efficient and environmentally friendly method for recycling DWTS.  相似文献   

15.
The fate of 14C-labeled herbicide prosulfocarb was studied in an agricultural soil and in a sediment-water system, the sediment part of which was derived from Yangtze Three Gorges Reservoir, China. Time-course studies were performed for 28 d and 49 d, respectively. Main transformation routes of 14C-prosulfocarb were mineralization to 14CO2 and formation of nonextractable residues amounting to 12.13% and 10.43%, respectively, after 28 days (soil), and 9.40% and 11.98%, respectively, after 49 d (sediment-water system). Traces of prosulfocarbsulfoxide were detected by means of TLC, HPLC, and LC-MS; other transformation products were not found. Initial extraction of soil assays using 0.01 M CaCl2 solution showed that the bioavailability of the herbicide was considerably low; immediately after application (0.1 d of incubation), only 4.78% of applied radioactivity were detected in this aqueous fraction. DT50 values of 14C-prosulfocarb estimated from radio-TLC and -HPLC analyses were above 28 d in soil and ranged between 29 d and 49 d in the sediment-water system. Partitioning of 14C from water to sediment phase occurred with DT50 slightly above 2 d. With regard to the sediment-water system, adsorption occurred with log Koc = 1.38 (calculated from 2 day assays) and 2.35 (49 d assays). As similarly estimated from portions of 14C found in CaCl2 extracts of the 0.1 d assays, 14C-prosulfocarb's log Koc in soil was 2.96. With both experiments, similar portions of nonextractable radioactivity were associated with all soil organic matter fractions, i.e. nonhumics, fulvic acids, humic acids, and humin/minerals. Throughout all sample preparation, the experiments were severely impaired by losses of radioactivity especially with concentration of samples containing water in vacuo. All findings pointed to volatility of parent prosulfocarb in presence of water rather than volatility of transformation products. According to literature data, this behavior of prosulfocarb was not expected, though volatility was demonstrated under field conditions.  相似文献   

16.

Introduction  

In the present work, we explored the kinetics of dichlorvos (2,2-dichlorvinyl dimethyl phosphate, DDVP) decay through UV-A light-induced TiO2 photocatalysis at pH 4 and 9, and the formation of degradation intermediates and final products under specific experimental conditions. Experimental observations and theoretical considerations allowed us to suggest the degradation mechanism of DDVP by the UV/TiO2 process in aqueous solution.  相似文献   

17.
Yu DJ  Lai BS  Li J  Ma YF  Yang F  Li Z  Luo XQ  Chen X  Huang YF 《Chemosphere》2012,86(1):70-75
Triclosan is used as an antibacterial agent in household items and personal care products. Since this compound is found in maternal milk of humans and bodies of wild animals, there is growing concern among some consumer groups and scientific community that triclosan is adverse for humans and wild animals. In order to estimate adverse actions of triclosan, the effects of triclosan on intracellular Zn2+ concentration and cellular thiol content were studied in rat thymocytes by the use of flow cytometer with appropriate fluorescent probes. Triclosan at 1-3 μM (sublethal concentrations) increased the intensity of FluoZin-3 fluorescence (intracellular Zn2+ concentration) and decreased the intensity of 5-chloromethylfluorescein (5-CMF) fluorescence (cellular thiol content). Negative correlation (r = −0.985) between triclosan-induced changes in FluoZin-3 and 5-CMF fluorescences was found. Removal of external Zn2+ did not significantly affect the triclosan-induced augmentation of FluoZin-3 fluorescence, suggesting an intracellular Zn2+ release by triclosan. These actions of triclosan were similar to those of H2O2 and triclosan significantly potentiated the cytotoxicity of H2O2. Therefore, the results may suggest that triclosan at sublethal concentrations induces oxidative stress that decreases cellular thiol content, resulting in an increase in intracellular Zn2+ concentration by Zn2+ release from intracellular store(s). Since recent studies show many physiological roles of intracellular Zn2+ in cellular functions, the triclosan-induced disturbance of cellular Zn2+ homeostasis may induce adverse actions on the cells.  相似文献   

18.

Background, aim and scope  

Photocatalytic oxidation using UV irradiation of TiO2 has been studied extensively and has many potential industrial applications, including the degradation of recalcitrant contaminants in water and wastewater treatment. A limiting factor in the oxidation process is the recombination of conduction band electrons (e cb) with electron holes (hvb+) on the irradiated TiO2 surface; thus, in aqueous conditions, the presence of an effective electron scavenger will be beneficial to the efficiency of the oxidation process. Ferrate (FeO42−) has received much recent attention as a water treatment chemical since it behaves simultaneously as an oxidant and coagulant. The combination of ferrate [Fe(VI)] with UV/TiO2 photocatalysis offers an oxidation synergism arising from the Fe(VI) scavenging of e cb and the corresponding beneficial formation of Fe(V) from the Fe(VI) reduction. This paper reviews recent studies concerning the photocatalytic oxidation of problematic pollutants with and without ferrate.  相似文献   

19.
The impact of nanoparticles on fish health is still a matter of debate, since nanotechnology is quite recent. In this study, freshwater benthonic juvenile fish Prochilodus lineatus were exposed through water to three concentrations of TiO2 (0.1, 1, and 10 μg l?1) and ZnO (7, 70, and 700 μg l?1) nanoparticles, as well as to a mixture of both (TiO2 1 μg l?1?+?ZnO 70 μg l?1) for 5 and 30 days. Nanoparticle characterization revealed an increase of aggregate size in the function of concentration, but suspensions were generally stable. Fish mortality was high at subchronic exposure to 70 and 700 μg l?1 of ZnO. Nanoparticle exposure led to decreased acetylcholinesterase activity either in the muscle or in the brain, depending on particle composition (muscle—TiO2 10 μg l?1; brain—ZnO 7 and 700 μg l?1), and protein oxidative damage increased in the brain (ZnO 70 μg l?1) and gills (ZnO 70 μg l?1 and mixture) but not in the liver. Exposed fish had more frequent alterations in the liver (necrosis, vascular congestion, leukocyte infiltration, and basophilic foci) and gills (hyperplasia and epithelial damages, e.g., epithelial disorganization and epithelial loss) than the control fish. Thus, predicted concentrations of TiO2 and ZnO nanoparticles caused detectable effects on P. lineatus that may have important consequences to fish health. But, these effects are much more subtle than those usually reported in the scientific literature for high concentrations or doses of metal nanoparticles.  相似文献   

20.
Rare earth (Dy3+ and Sm3+)-doped sodium magnesium borate (NaMgBO3) is synthesized by solution combustion synthesis method keeping their thermoluminescence properties in mind. The reaction produced very stable crystalline NaMgBO3:RE (RE?=?Dy3+, Sm3+) phosphors. The phosphors are exposed to 60Co gamma-ray radiations dose of varying rate from 5 to 25 Gy, and their TL characteristics with kinetic parameters are studied. NaMgBO3:Dy3+ phosphor shows two peaks for lower doping concentration of Dy3+ while it reduced to single peak for the higher concentrations of activator Dy3+. NaMgBO3:Dy3+ shows the major glow peak around 200 °C while NaMgBO3:Sm3+ phosphors show two well-separated glow peaks at 200 and 332 °C respectively. The thermoluminescence intensity of these phosphors was compare with the commercially available TLD-100 (Harshaw) phosphor. The TL responses for gamma-ray radiations dose were found to be linear from 5 to 25 Gy for both phosphors while the fading in each case is calculated for the tenure of 45 days.  相似文献   

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