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1.
Fenoll J  Ruiz E  Hellín P  Flores P  Navarro S 《Chemosphere》2011,85(8):1262-1268
The efficiency of ZnO and TiO2 suspensions in the photocatalytic degradation of two fungicides (cyprodinil and fludioxonil) in leaching water was investigated. The experiments were carried out at pilot plant scale using compound parabolic collectors under natural sunlight. The blank experiments for both irradiated compounds solutions showed that both oxides strongly enhanced the removal of the fungicides. The addition of an oxidant (Na2S2O8) to the ZnO or TiO2 increased the rate of photooxidation. The degradation of cyprodinil and fludioxonil followed first order kinetics according to the Langmuir-Hinshelwood model. Complete degradation of both fungicides was achieved within 4 h (t30W = 18 min) when treated with illuminated ZnO. The disappearance time (DT75), when referred to the normalized illumination time (t30W), was lower than 40 and 550 min (t30W = 2 and 40 min) for both fungicides using ZnO or TiO2, respectively. ZnO appeared to be more effective in cyprodinil and fludioxonil oxidation than TiO2 probably due to its nonstoichiometry.  相似文献   

2.
In the present study, the photocatalytic degradation of five sulfonylurea herbicides (chlorsulfuron, flazasulfuron, nicosulfuron, sulfosulfuron and triasulfuron) has been investigated in aqueous suspensions of zinc oxide (ZnO), tungsten (VI) oxide (WO3), tin (IV) oxide (SnO2) and zinc sulfide (ZnS) at pilot plant scale under natural sunlight. Photocatalytic experiments, especially those involving ZnO photocatalysis, showed that the addition of semiconductors in tandem with the oxidant (Na2S2O8) strongly enhances the degradation rate of the herbicides in comparisons carried out with photolytic tests. The degradation of the herbicides follows a first order kinetics according to the Langmuir-Hinshelwood model. In our conditions, the amount of time required for 50% of the initial pesticide concentration to dissipate (t½) ranged from 8 to 27 min (t30W = 0.3-1.2 min) for sulfosulfuron and chlorsulfuron, respectively in the ZnO/Na2S2O8 system. None of the studied herbicides was found after 120 min of illumination (except chlorsulfuron, 0.2 μg L−1).  相似文献   

3.
This is the first study describing the chemical oxidation of hexachlorocyclohexanes (HCHs) in contaminated soil under water saturated and unsaturated flow through conditions. Soil contaminated with β-HCH (45 mg kg?1) and γ-HCH (lindane, 25 mg kg?1) was sampled from former lindane waste storage site. Efficiency of following treatments was tested at circumneutral pH: H2O2 alone, H2O2/FeII, Na2S2O8 alone, Na2S2O8/FeII, and KMnO4. Experimental conditions (oxidant dose, liquid/solid ratio, and soil granulometry) were first optimized in batch experiments. Obtained results revealed that increasing dose of H2O2 improved the oxidation efficiency while in Na2S2O8 system, maximum HCHs were removed at 300 mM. However, oxidation efficiency was slightly improved by FeII-activation. Increasing the solid/liquid ratio decreased HCH removal in soil samples crushed to 500 μm while an opposite trend was observed for 2-mm samples. Dynamic column experiments showed that oxidation efficiency followed the order KMnO4 > Na2S2O8/FeII > Na2S2O8 whatever the flow condition, whereas the removal extent declined at higher flow rate (e.g., ~50% by KMnO4 at 0.5 mL/min as compared to ~30% at 2 mL/min). Both HCH removal and oxidant decomposition extents were found higher in saturated columns than the unsaturated ones. While no significant change in relative abundance of soil mineral constituents was observed before and after chemical oxidation, more than 60% of extractable organic matter was lost after chemical oxidation, thereby underscoring the non-selective behavior of chemical oxidation in soil. Due to the complexity of soil system, chemical oxidation has rarely been reported under flow through conditions, and therefore our findings will have promising implications in developing remediation techniques under dynamic conditions closer to field applications.  相似文献   

4.
Limited information is available on the environmental behavior and associated potential risk of manufactured oxide nanoparticles (NPs). In this research, toxicity of nanoparticulate and bulk ZnO, Al2O3 and TiO2 were examined to the nematode Caenorhabditis elegans with Escherichia coli as a food source. Parallel experiments with dissolved metal ions from NPs were also conducted. The 24-h median lethal concentration (LC50) and sublethal endpoints were assessed. Both NPs and their bulk counterparts were toxic, inhibiting growth and especially the reproductive capability of the nematode. The 24-h LC50 for ZnO NPs (2.3 mg L−1) and bulk ZnO was not significantly different, but significantly different between Al2O3 NPs (82 mg L−1) and bulk Al2O3 (153 mg L−1), and between TiO2 NPs (80 mg L−1) and bulk TiO2 (136 mg L−1). Oxide solubility influenced the toxicity of ZnO and Al2O3 NPs, but nanoparticle-dependent toxicity was indeed observed for the investigated NPs.  相似文献   

5.
The present work involves the photocatalytic mineralization of glyphosate on a plug flow reactor by UV/TiO2. The effect of catalyst loading shows an optimal value (0.4 g L?1) which is necessary to mineralize glyphosate. The kinetic rate of glyphosate mineralization decreases with the increasing initial concentration of glyphosate, and the data can be described using the first-order model. An alkaline environment is conducive to glyphosate mineralization. The mineralization efficiency increases with elevated flow rate to 114 mL min?1, which is followed by a decrease with a further increase in flow rate due to the reduction of the residence time. The presence of external oxidants (K2S2O8, H2O2 and KBrO3) and photosencitizer (humic acid) can significantly enhance glyphosate mineralization. Photocatalysis oxidation ability of the three studied oxidants decrease in the order of: S2O8 2? > BrO3 ? > H2O2. Finally, the Langmuir–Hinshelwood (L-H) model was used to rationalize the mechanisms of reactions occurring on TiO2 surfaces and L-H model constants were also determined.  相似文献   

6.
采用双氰胺甲醛缩聚物混凝去除水中酸性红B染料的研究   总被引:1,自引:0,他引:1  
以双氰胺和甲醛为原料制备了聚合双氰胺甲醛,并对其进行红外光谱表征.采用聚合双氰胺甲醛与硫代硫酸钠共同作用对酸性红B染料溶液进行混凝脱色实验.对比了单独使用聚合双氰胺甲醛,以及聚合双氰胺甲醛与硫代硫酸钠共同作用的脱色效果.探讨了硫代硫酸钠和聚合双氰胺甲醛的用量以及pH值对脱色率的影响.结果表明,投加硫代硫酸钠可以明显地提高聚合双氰胺甲醛的脱色率,增大絮凝范围,使絮凝剂对pH值的变化有很强的适应性,pH值为7~12的范围内,脱色率均能维持在96%以上.此外,还对混凝脱色的机理进行了研究.  相似文献   

7.
ABSTRACT

The primary production of Pb via the sinter plant-blast furnace method resulted in a large number of Pb and other phases, reflecting the complex reactions occurring within each of the processes. Optical microscopy and X-ray diffraction (XRD) techniques have been used to characterize fugitive emissions and dusts generated during sintering, smelting, Cu drossing, refining, and slag fuming at a primary Pb-Zn smelter. The results displayed a complex array of phases, with the mineralogy of the dusts and fume reflecting conditions of the particular metallurgical operation. The principal Pb species followed a transformation from PbS through PbSO4 and PbO to Pb° (metal) from raw materials to the refinery. The fugitive emissions generated by the blast furnace were of a finer size with more complex chemistry than fugitive material from other source areas. XRD identified a mixture of PbS, ZnO, and ZnS, associated with one or more of the Cl-bearing phases Pb(OH)Cl, PbCl2, Pb4O3Cl2, Na3Pb2(SO4)3Cl, Pb10(SO4)Cl2O8, Pb4SCl6, and Pb7S2Cl10. The presence of Cl-bearing phases in the fume has possible health implications.  相似文献   

8.
Kumar A  Pandey AK  Singh SS  Shanker R  Dhawan A 《Chemosphere》2011,83(8):1124-1132
Extensive production and consumption of nanomaterials such as ZnO and TiO2 has increased their release and disposal into the environment. The accumulation of nanoparticles (NPs) in ecosystem is likely to pose threat to non-specific targets such as bacteria. The present study explored the effect of ZnO and TiO2 NPs in a model bacterium, Salmonella typhimurium. The uptake of ZnO and TiO2 bare NPs in nano range without agglomeration was observed in S. typhimurium. TEM analysis demonstrated the internalization and uniform distribution of NPs inside the cells. Flow cytometry data also demonstrates that both ZnO and TiO2 NPs were significantly internalized in the S. typhimurium cells in a concentration dependent manner. A significant increase in uptake was observed in the S. typhimurium treated even with 8 and 80 ng mL−1 of ZnO and TiO2 NPs with S9 after 60 min, possibly the formation of micelles or protein coat facilitated entry of NPs. These NPs exhibited weak mutagenic potential in S. typhimurium strains TA98, TA1537 and Escherichia coli (WP2uvrA) of Ames test underscoring the possible carcinogenic potential similar to certain mutagenic chemicals. Our study reiterates the need for re-evaluating environmental toxicity of ZnO and TiO2 NPs presumably considered safe in environment.  相似文献   

9.
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   

10.
Indoxacarb was applied at 75 and 150 g a.i. ha? 1 for two years to an eggplant (Solanum melongena L.) crop grown in the field plots in order to evaluate its efficacy for management of the lepidopteron pest, shoot and fruit borer. The residues of the insecticide were quantified by high-pressure liquid chromatography (HPLC). The mean initial deposits of indoxacarb on eggplant fruits were found to be 2.60–2.634 mg kg? 1 and 3.64–3.68 mg kg? 1 from the two rates of applications, respectively. They declined with time and reached to non-detectable (< 0.02 mg kg? 1) after 15–20 d. Residues dissipated with a half-life of 3.0–3.8 d from both first and second-year application. A 3 d waiting period for harvest of fruits after insecticide application and processing resulted in the residue levels that were below the Codex maximum residue limit (MRL) of 0.5 mg kg? 1 thereby achieving a maximum safety and minimum risk to consumers. The best combination of chemicals for decontamination of indoxacarb was found to be by washing with a mixture of alkali and potassium permanganate (KMnO4) thereby resulting in the removal of 67.5% and 59.2 % residues for 5 and 10 μ g g? 1 spiking doses, respectively. Major products formed on reaction of indoxacarb with alkali were identified by electron spray ionization chromatography/mass spectrometry (ESI/MS). The per cent reduction on the weight and number basis of treated eggplant plots were compared to those observed in control plots to demonstrate the effectiveness of indoxacarb treatment on shoot and fruit borer population.  相似文献   

11.
Electrokinetic (EK) remediation has potential to simultaneously remove heavy metals and organic compounds from soil, but the removal percent of these pollutants is very low in general if no enhancing treatment is applied. This study developed a new enhanced-EK remediation technology to decontaminate a heavy metal–organic compound co-contaminated soil by applying different oxidants and pH control. A red soil was used as a model clayed soil, and was spiked with pyrene and Cu at about 500 mg kg?1 for both to simulate real situation. Bench-scale EK experiments were performed using four oxidants (H2O2, NaClO, KMnO4, and Na2S2O8) and controlling electrolyte pH at 3.5 or 10. After the treatments with 1.0 V cm?1 of voltage gradient for 335 h, soil pH, electrical conductivity, and the concentrations and chemical fractionations of soil pyrene and Cu were analyzed. The results showed that there was significant migration of pyrene and Cu from the soil, and the removal percent of soil pyrene and Cu varied in the range of 30–52% and 8–94%, respectively. Low pH favoured the migration of soil Cu, while KMnO4 was the best one for the degradation of pyrene among the tested oxidants, although it unfortunately prevented the migration of soil Cu by forming Cu oxide. Application of Na2S2O8 and to control the catholyte pH at 3.5 were found to be the best operation conditions for decontaminating the Cu-pyrene co-contaminated soil.  相似文献   

12.
TiO2-supported activated carbon felts (TiO2–ACFTs) were prepared by dip coating of felts composed of activated carbon fibers (ACFs) with either polyester fibers (PS-A20) and/or a polyethylene pulp (PE-W15) in a TiO2 aqueous suspension followed by calcination at 250 °C for 1 h. The as-prepared TiO2–ACFTs with 29–35 wt.% TiO2 were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), and N2 adsorption. The TiO2–ACFT(PS-A20) samples with 0 and 29 wt.% TiO2 were microporous with specific surface areas (S BET) of 996 and 738 m2/g, respectively, whereas the TiO2–ACFT(PE-W15) samples with 0 and 35 wt.% TiO2 were mesoporous with S BET of 826 and 586 m2/g, respectively. Adsorption and photocatalytic activity of the as-prepared samples were evaluated by measuring adsorption in the dark and photodegradation of gaseous acetaldehyde (AcH) and methylene blue (MB) in aqueous solution under UV light. The TiO2 loading caused a considerable decrease in the S BET and MB adsorption capacity along with an increase in MB photodegradation and AcH mineralization. Lemna minor was chosen as a representative aquatic plant for ecotoxicity tests measuring detoxification of water obtained from the MB photodegradation reaction with the TiO2–ACFT samples under UV light.  相似文献   

13.
Degradation of bisphenol A (BPA) in aqueous solution was studied with high-efficiency sulfate radical (SO4 ), which was generated by the activation of persulfate (S2O8 2?) with ferrous ion (Fe2+). S2O8 2? was activated by Fe2+ to produce SO4 , and iron powder (Fe0) was used as a slow-releasing source of dissolved Fe2+. The major oxidation products of BPA were determined by liquid chromatography-mass spectrometer. The mineralization efficiency of BPA was monitored by total organic carbon (TOC) analyzer. BPA removal efficiency was improved by the increase of initial S2O8 2? or Fe2+ concentrations and then decreased with excess Fe2+ concentration. The adding mode of Fe2+ had significant impact on BPA degradation and mineralization. BPA removal rates increased from 49 to 97 % with sequential addition of Fe2+, while complete degradation was observed with continuous diffusion of Fe2+, and the latter achieved higher TOC removal rate. When Fe0 was employed as a slow-releasing source of dissolved Fe2+, 100 % of BPA degradation efficiency was achieved, and the highest removal rate of TOC (85 %) was obtained within 2 h. In the Fe0–S2O8 2? system, Fe0 as the activator of S2O8 2? could offer sustainable oxidation for BPA, and higher TOC removal rate was achieved. It was proved that Fe0–S2O8 2? system has perspective for future works.  相似文献   

14.
Abstract

Spinosad is a natural product with biological activity against a range of insects including lepidoptera. It is comprised of two major components namely spinosyns A and D. The degradation of spinosad in soil under aerobic conditions was investigated using two U.S. soils (a silt loam and a sandy loam) which were treated with either 14C‐spinosyn A or ‐spinosyn D at a 2X use rate of 0.4mg/kg soil for spinosyn A and 0.1mg/kg for spinosyn D. Further samples of soil were pre‐sterilised prior to treatment in order to establish whether spinosyns A and D degrade abiotically. Flasks of treated soil were incubated in the dark at 25°C for up to one year after treatment.

HPLC and LC‐MS of soil extracts confirmed that the major degradation product of spinosyn A was spinosyn B, resulting from demethylation on the forosamine sugar. Other dégradâtes were hydroxylation products of spinosyns A and B, with hydroxylation probably taking place on the aglycone portion of the molecule. Half lives were similar for both spinosyns and were in the range 9–17 days, with longer half lives in the pre‐sterilised soils (128–240 days) suggesting that degradation was largely microbial.  相似文献   

15.
A hybrid selective noncatalytic reduction/selective catalytic reduction (SNCR/SCR) system that uses two types of technology, low-temperature SCR process and SNCR process, was designed to develop nitrogen oxide (NOx) reduction technology. SCR was conducted with space velocity (SV) = 2400 hr?1 and hybrid SNCR/SCR with SV = 6000 hr?1, since the study focused on reducing the amount of catalyst and both achieved 98% NOx reduction efficiency. Characteristics of NOx reduction by NH3 were studied for low-temperature SCR system at 150 °C using Mn-V2O5/TiO2 catalyst. Mn-added V2O5/TiO2 catalyst was produced, and selective catalyst reduction of NOx by NH3 was experimented. NOx reduction rate according to added Mn content in Mn-V2O5/TiO2 catalyst was studied with varying conditions of reaction temperature, normalized stoichiometric ratio (NSR), SV, and O2 concentration. In the catalyst experiment according to V2O5 concentration, 1 wt.% V2O5 catalyst showed the highest NOx reduction rate: 98% reduction at temperature window of 200~250 °C. As a promoter of the V2O5 catalyst, 5 wt.% Mn was added, and the catalyst showed 47~90% higher efficiency even with low temperatures, 100~200 °C. Mn-V2O5/TiO2 catalyst, prepared by adding 5 wt.% Mn in V2O5/TiO2 catalyst, showed increments of catalyst activation at 150 °C as well as NOx reduction. Mn-V2O5/TiO2 catalyst showed 8% higher rate for NOx reduction compared with V2O5/TiO2 catalyst in 150 °C SCR. Thus, (5 wt.%)Mn-(1 wt.%)V2O5/TiO2 catalyst was applied in SCR of hybrid SNCR/SCR system of low temperature at 150 °C. Low-temperature SCR hybrid SNCR/SCR (150 °C) system and hybrid SNCR/SCR (350 °C) showed 91~95% total reduction rate with conditions of SV = 2400~6000 hr?1 SCR and 850~1050 °C SNCR, NSR = 1.5~2.0, and 5% O2. Hybrid SNCR/SCR (150 °C) system proved to be more effective than the hybrid SNCR/SCR (350 °C) system at low temperature.

Implications:?NOx control is very important, since they are the part of greenhouse gases as well as the cause of acid rain and ozone hole. A technology, so-called hybrid SNCR/SCR process, was tested using Mn-V2O5/TiO2 monolithic catalyst for NOx reduction, and the method is promising. The results of this study would provide some ideas to parties such as policy makers, environmental engineers, and so on.  相似文献   

16.
研究了1%和10%(V/V)模拟正丙醇废水在UV/TiO2体系、UV/H2O2体系、Fe2+/H2O2体系和UV/TiO2/Fe2+/H2O2体系等4种工艺条件下的降解动力学过程,对比了降解动力学特点及工艺参数对动力学常数的影响,优化工艺参数。结果表明,UV/TiO2体系和Fe2+/H2O2体系的降解过程可分为零级反应阶段和一级反应阶段,转折点分别在反应开始后2 h和氧化剂浓度为6.7 g/L,UV/H2O2体系和UV/TiO2/Fe2+/H2O2体系分别符合零级反应和一级反应规律;相同工艺参数条件下,6 h反应后,组合工艺UV/TiO2/Fe2+/H2O2体系在处理效率达85%,比前3个体系分别高52.0%、8.3%和32.0%,与UV/TiO2体系和Fe2+/H2O2体系的处理效率之和持平,其协同效应提高了速率常数,在目标物浓度降低时依然可维持较高降解速率。而目标物浓度提高10倍后,UV能量利用率提高35.5倍,氧化剂用量是Fe2+/H2O2体系的1/7.1。  相似文献   

17.
Metal oxide nanomaterials have exhibited toxicity to a variety of aquatic organisms, especially microbes and invertebrates. To date, few studies have evaluated the toxicity of metal oxide nanomaterials on aquatic vertebrates. Therefore, this study examined effects of ZnO, TiO2, Fe2O3, and CuO nanomaterials (20-100 nm) on amphibians utilizing the Frog Embryo Teratogenesis Assay Xenopus (FETAX) protocol, a 96 h exposure with daily solution exchanges. Nanomaterials were dispersed in reconstituted moderately hard test medium. These exposures did not increase mortality in static renewal exposures containing up to 1000 mg L−1 for TiO2, Fe2O3, CuO, and ZnO, but did induce developmental abnormalities. Gastrointestinal, spinal, and other abnormalities were observed in CuO and ZnO nanomaterial exposures at concentrations as low as 3.16 mg L−1 (ZnO). An EC50 of 10.3 mg L−1 ZnO was observed for total malformations. The minimum concentration to inhibit growth of tadpoles exposed to CuO or ZnO nanomaterials was 10 mg L−1. The results indicate that select nanomaterials can negatively affect amphibians during development. Evaluation of nanomaterial exposure on vertebrate organisms are imperative to responsible production and introduction of nanomaterials in everyday products to ensure human and environmental safety.  相似文献   

18.
19.
采用H2O2、Fe2(SO43和Fenton溶液对失活的TiO2纳米管进行再生处理,重点考察了3种溶液的浓度和处理时间等对再生效果的影响,初步分析了经处理后TiO2纳米管催化活性得到再生或增强的机理。结果表明,经H2O2溶液处理后TiO2催化活性能得到有效再生,经Fe2(SO43和Fenton溶液处理后其催化活性不仅得到再生,还能显著增强,这与H2O2和Fenton的强氧化作用,及进入TiO2纳米管的Fe3+的阻止电子-空穴对再复合作用有关。  相似文献   

20.
Zhang K  Liu J  Liu W  Yang J 《Chemosphere》2011,85(4):689-692
A novel approach to prepare glass-ceramics from molten steel slag (MSS) was proposed. In laboratory, the water-quenched steel slag was melted at 1350 °C to simulate the MSS. A mixture of additive powders in wt.% (55 quartz powder, 5 Na2O, 16 emery powder, 15 CaO, 8 MgO, 1 TiO2) were melted into liquid at 1350 °C separately. Then the MSS and the molten additives were mixed homogeneously in order to obtain parent glass melt. The proportion of MSS in the melt was 50 wt.%. The melt was subsequently cast, annealed, heat-treated and transformed into glass-ceramics. Their microstructure and crystallization behavior were analyzed. The samples exhibited excellent properties and displayed bulk crystallization. The major crystallized phase was diopside ((Fe0.35Al0.20Mg0.44)Ca0.96(Fe0.08Si0.70Al0.20)2O6.12), which was uniformly distributed in the microstructure. The novel approach may help iron and steel industry achieve zero disposal of steel slag with utilization of the heat energy of the MSS.  相似文献   

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