Photocatalytic mineralization of glyphosate in a small-scale plug flow simulation reactor by UV/TiO2

The present work involves the photocatalytic mineralization of glyphosate on a plug flow reactor by UV/TiO(2). 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 (K(2)S(2)O(8), H(2)O(2) and KBrO(3)) and photosencitizer (humic acid) can significantly enhance glyphosate mineralization. Photocatalysis oxidation ability of the three studied oxidants decrease in the order of: S(2)O(8)(2-) > BrO(3)(-) > H(2)O(2). Finally, the Langmuir-Hinshelwood (L-H) model was used to rationalize the mechanisms of reactions occurring on TiO(2) surfaces and L-H model constants were also determined.     

The role of halogen species in the troposphere

While the role of reactive halogen species (e.g. Cl, Br) in the destruction of the stratospheric ozone layer is well known, their role in the troposphere was investigated only since their destructive effect on boundary layer ozone after polar sunrise became obvious. During these 'Polar Tropospheric Ozone Hole' events O(3) is completely destroyed in the lowest approximately 1000 m of the atmosphere on areas of several million square kilometres. Up to now it was assumed that these events were confined to the polar regions during springtime. However, during the last few years significant amounts of BrO and Cl-atoms were also found outside the Arctic and Antarctic boundary layer. Recently even higher BrO mixing ratios (up to 176 ppt) were detected by optical absorption spectroscopy (DOAS) in the Dead Sea basin during summer. In addition, evidence is accumulating that BrO (at levels around 1-2 ppt) is also occurring in the free troposphere at all latitudes.In contrast to the stratosphere, where halogens are released from species, which are very long lived in the troposphere, likely sources of boundary layer Br and Cl are autocatalytic oxidation of sea salt halides (the 'Bromine Explosion'), while precursors of free tropospheric BrO and coastal IO probably are short-lived organo-halogen species. At the levels suggested by the available measurements reactive halogen species have a profound effect on tropospheric chemistry: In the polar boundary layer during 'halogen events' ozone is usually completely lost within hours or days. In the free troposphere the effective O(3)-losses due to halogens could be comparable to the known photochemical O(3) destruction. Further interesting consequences include the increase of OH levels and (at low NO(X)) the decrease of the HO(2)/OH ratio in the free troposphere.     

铁氧化物复合氧化铝催化臭氧化过程中溴酸盐的生成控制

以市售活性炭、硅藻土和氧化铝小球为载体,考察了负载铁基活性组分对催化臭氧化过程中溴酸盐的控制情况,其中,铁基复合氧化铝小球体现出更好的溴酸盐还原特性和催化剂稳定性,证实催化剂中铁氧化物是溴酸盐得到有效控制的主要活性组分。进一步考察了铁基复合氧化铝小球催化臭氧化处理实际原水过程中对溴酸盐的生成控制,以及反应过程中溶解性有机碳（DOC）的去除情况。结果表明,与单独臭氧化相比,该催化剂既能有效去除水中的溶解性有机物,又能明显抑制溴酸盐的生成,反应50h,其活性并没有明显下降。催化剂失活主要归因于吸附位点数量的下降,可以通过负载铁氧化物来实现催化剂的再生。     

The use of oxyhalogen in photocatalytic reaction to remove o-chloroaniline in TiO2 dispersion

Photodecay of o-chloroaniline (o-ClA) in various combinations of UV sources, TiO2, and oxyhalogens was investigated. To improve the conventional photocatalytic process by using UV/TiO2, the addition of oxyhalogens (ClO3(-), BrO3(-) and IO3(-)) into UV/TiO2 system was studied and the effect in such addition is very encouraging for all the selected additives. Oxyhalogens are capable of deferring the electron-hole recombination of TiO2 which significantly improved its catalytic performance. The presence of IO3(-) in UV/TiO2 resulted in the fastest o-ClA decay among three oxhalogens at the same dosage. The decay of o-ClA in UV/TiO2/oxyhalogen process is characterized by a two-stage pseudo-kinetics, where a faster initial decay was followed by a retardation state. A mathematics model was successfully established for the prediction of the two-stage decay of o-ClA in UV/TiO2/IO3(-) with any designed [IO3(-)] concentration.     

High bromine oxide concentrations in the semi-polluted boundary layer

Bromine chemistry in the marine boundary layer is recognized to play an important role through catalytic ozone destruction, changes to the atmospheric oxidising capacity (by changing the OH/HO₂ and NO/NO₂ ratio) and oxidation of compounds such as dimethyl sulphide (DMS). However, the chemistry of bromine in polluted environments is not well understood and its effects are thought to be inhibited by reactions involving NO_x (NO₂ & NO). This paper describes long-path Differential Optical Absorption Spectroscopy (DOAS) observations of bromine oxide (BrO) at a semi-polluted coastal site in Roscoff, France. Significant concentrations of BrO (up to 7.5 ± 1.0 pptv) were measured during daytime, indicating the presence of unknown sources or efficient recycling of reactive bromine from bromine nitrate (BrONO₂), which should be the major reservoir for bromine in a high NO_x environment. These measurements indicate that bromine chemistry can play an important role in polluted environments.     

The effect of atmospheric mercury depletion events on the net deposition flux around Hudson Bay,Canada

Atmospheric Mercury Depletion Events (AMDE) occur in Arctic and Antarctic regions during polar sunrise. During AMDE, reactive gaseous Hg is rapidly formed through in-situ oxidation of gaseous Hg⁰ by halogens, notably atomic Br and radical BrO. This leads to high Hg deposition fluxes yet an unknown fraction of deposited Hg is reemitted to the atmosphere through subsequent photo-reduction, so that the net deposition flux related to AMDE is not well constrained. Here, Hg and halogens were measured in lichens hanging in tree branches around Hudson Bay where AMDE were reported. Hg concentrations are strongly correlated to halogen elements Br, Cl and I (r² of 0.91, 0.76, 0.81) and decrease with distance from Hudson Bay. We interpret this trend as the result of AMDE, supported by a 1D numerical Br and BrO oxidation model for Hg⁰. Organic carbon normalized Hg contents of down-core lake sediments reported in the literature also show a decreasing trend away from Hudson Bay. Combined observations suggest that at least 50% of Hg deposited during AMDE is reemitted to the atmosphere. Finally, the latitudinal Hg gradient observed in lake sediments suggests that AMDE were active in the Hudson Bay area during the last 90 to 200 years.     

Hydrogen peroxide-assisted UV photodegradation of Lindane

Aqueous solutions of gamma-hexachlorocyclohexane (Lindane) were photolyzed (lambda=254 nm) under a variety of solution conditions. The initial concentrations of hydrogen peroxide (H(2)O(2)) and Lindane varied from 0 to 20 mM and 0.21 to 0.22 microM, respectively, the pH ranged from 3 to 11, and several concentration ratios of Suwannee River humic acid and fulvic acid were dissolved in the irradiated solutions. Lindane rapidly reacted, and the maximum reaction rate constant (9.7 x 10(-3) s(-1)) was observed at pH 7 and initial [H(2)O(2)]=1 mM. Thus, 90% of the Lindane is destroyed in approximately 4 min under these conditions. In addition, within 15 min, all chlorine atoms were converted to chloride ion, indicating that chlorinated organic by-products do not accumulate. The reactor was characterized by measuring the photon flux (7.04 x 10(-6) E s(-1)) and the cumulative production of *OH during irradiation. The cumulative *OH production during irradiation was fastest at an initial [H(2)O(2)]=5 mM (k=0.77 micro M s(-1)).     

Degradation of bisphenol A using UV and UV/H2O2 processes

Bisphenol A (BPA; 4-[2-(4-hydroxyphenyl)propan-2-yl]phenol) is a substance typically used in the plastic industry. It is used in the production of epoxy resins, polycarbonate, or fire retardants or as a stabilizer and an antioxidant in numerous types of plastics. Bisphenol A is introduced into the environment via municipal and industrial wastewater. Because of its hydrophobic properties, BPA has the potential for sorption on activated sludge during the biological wastewater treatment processes. This study investigated the degradation of BPA by means of UV-radiation and in the UV/H2O2 process with the presence and absence of hydrocarbonate ions (HCO3(-)) as hydroxyl radicals (OH*) scavengers. The calculated value of quantum yield was equal to 0.18, and the value of BPA rate constant with hydroxyl radicals was equal to 3.3 x 10(9) M(-1) s(-1).     

Bromate formation on the non-porous TiO2 photoanode in the photoelectrocatalytic system

The increasing use of ozone in water disinfection processes has been the focus of considerable concern in regards to inorganic disinfection by product formation of bromate in waters containing bromide. Due to the public health risk caused by the presence of bromate as a suspected carcinogen, attention had been addressed to the conditions under which bromate is formed. In this study, photoanodic bromine generation and bromate (BrO(3)(-)) formation were investigated using a TiO(2) electrode in a photoelectrocatalytic (PEC) treatment process. The separation of anodic and cathodic reactions in the PEC system resulted in a pH decrease from 9.3 to 3.0 in the photoanode compartment and an increase to 11.0 in the cathode compartment. Under a photo-illumination intensity of 5.7 m W cm(-2) UV, a biasing potential of +1.0V vs SCE, a pH of 6.0 and at a NaBr concentration of 1.0 x 10(-2) M, active bromine formation increased over time with 2.4 x 10(-6) M min(-6) rate and reached a steady-state concentration of 1.44 x 10(-4) M in 60 min. Bromate formation was detected after a lag-period of 15 min and exhibited a continuous increasing trend with respect to irradiation time. No bromate formation was observed below pH 6.5 whereas an increasing bromate concentrations and pH up to pH=8.5 were noted.     

A new approach to quantify the degradation kinetics of linuron with UV, ozonation and UV/O3 processes

The degradation of linuron, one of phenylurea herbicides, was investigated for its reaction kinetics by different treatment processes including ultraviolet irradiation (UV), ozonation (O₃), and UV/O₃. The decay rate of linuron by UV/O₃ process was found to be around 3.5 times and 2.5 times faster than sole-UV and ozone-alone, respectively. Experimental results also indicate overall rate constants increased exponentially with pH above 9.0 while the increase of rate constants with pH below 9 is insignificant in O₃ system. All dominant parameters involved in the three processes were determined in the assistant of proposed linear models in this study. The approach was found useful in predicting the process performances through the quantification of quantum yield (rate constant for the formation of free radical HOO⁻ from ozone decomposition at high pH), rate constant of linuron with ozone (k_O3,LNR), rate constant of linuron with hydroxyl radical (k_OH,LNR), and α (the ratio of the production rate of OH and the decay rate of ozone in UV/O₃ system).     

UV/ozone degradation of gaseous hexamethyldisilazane (HMDS)

As a carcinogen, hexamethyldisilazane (HMDS) is extensively adopted in life science microscopy, materials science and nanotechnology. However, no appropriate technology has been devised for treating HMDS in gas streams. This investigation evaluated the feasibility and effectiveness of the UV (185+254nm) and UV (254nm)/O(3) processes for degradation of gaseous HMDS. Tests were performed in two batch reactors with initial HMDS concentrations of 32-41mgm(-3) under various initial ozone dosages (O(3) (mg)/HMDS (mg)=1-5), atmospheres (N(2), O(2), and air), temperatures (28, 46, 65 and 80 degrees C), relative humilities (20%, 50%, 65%, 99%) and volumetric UV power inputs (0.87, 1.74, 4.07 and 8.16Wl(-1)) to assess their effects on the HMDS degradation rate. Results indicate that for all conditions, the decomposition rates for the UV (185+254nm) irradiation exceeded those for the UV (254nm)/O(3) process. UV (185+254nm) decompositions of HMDS displayed an apparent first-order kinetics. A process with irradiation of UV (185+254nm) to HMDS in air saturated with water at temperatures of 46-80 degrees C favors the HMDS degradation. With the condition as above and a P/V of around 8Wl(-1), k was approximately 0.20s(-1) and a reaction time of just 12s was required to degrade over 90% of the initial HMDS. The main mechanisms for the HMDS in wet air streams irradiated with UV (185+254nm) were found to be caused by OH free-radical oxidation produced from photolysis of water or O((1)D) produced from photolysis of oxygen. The economic evaluation factors of UV (185+254nm) and UV (254nm)/O(3) processes at different UV power inputs were also estimated.     

TiO2/H2O2/UV和TiO2/O3/UV降解对氯苯甲酸和喹啉的试验研究

主要叙述TiO2/H2O2/UV和TiO2/O3/UV体系降解对氯苯甲酸(4-CBA)和喹啉的试验研究.研究表明,(1)在TiO2/H2O2/UV体系里目标物降解速度先随过氧化氢投加量的增加而提高,但超过一定浓度之后便开始下降;(2)在TiO2/O3/UV体系中,目标降解物的反应速度都非常快,且臭氧浓度高的时候降解速度更快;(3)二氧化钛催化剂在TiO2/O3/UV体系中作为积极因素有助于提高反应速率,而在TiO2/H2O2/UV体系是消极因素,会降低反应速率.     

臭氧与TiO2/UV协同降解对氯苯酚

利用O3／UV、TiO2／UV和O3／TiO2／UV降解对氯苯酚表明，臭氧与TiO2／UV具有明显的协同作用，如在本实验条件下降解5min后，上述3者对对氯苯酚的去除率分别为55％、10％和77%。O3／TiO2／UV协同作用的本质是由于臭氧能带走二氧化钛光致电子空穴对中的电子，从而产生了更多的羟基自由基，加速了有机物的降解。     

Kinetics of quinoline degradation by O3/UV in aqueous phase

The kinetics of quinoline degradation by O3/UV in aqueous phase was studied in this paper. It was found that the stoichiometric factor for the number of ozone molecule consumed by per quinoline molecule was 1. The second-order rate constants at 15 degrees C for the direct reaction of quinoline with ozone and that for the reaction of quinoline with *OH were determined to be 51.0 and 7.24 x 10(9) M(-1)s(-1), respectively. In O3/UV reaction system, *OH was the more important oxidant to degrade quinoline than ozone. For a comparison, in O3 reaction system, the relative importance of the two oxidants depended on the pH value greatly. To make the degradation of quinoline more practical, improvement of the concentration of *OH is more feasible.     

Fouling mechanisms in a laboratory-scale UV disinfection system.

The fouling of quartz sleeves surrounding UV disinfection lamps is a perennial problem affecting both drinking water and wastewater applications. The mechanisms of fouling are not fully understood, but factors promoting fouling are believed to include heat, high hardness and/or high iron concentrations, and hydrodynamic forces. The role of UV radiation itself is unclear. The goal of this paper is to attempt to isolate the fouling mechanisms and to provide key information about those induced by UV radiation, using a unique laboratory-scale continuous-flow UV reactor. Its design allowed for irradiated and nonirradiated zones and control of both temperature and UV intensity at the fouling surface. Synthetic wastewater samples were tested with two levels of calcium, iron, phosphorus, and biochemical oxygen demand (as beef broth), and constant levels of magnesium and nitrogen to assess the effects of the four key variables. Average UV fluence before fouling exceeded 35 mJ/cm2, based on collimated beam tests. Foulant accumulation was monitored by UV intensity measurements and by mass and composition of foulant collected after an average of 56 hours of continuous operation. Tests showed that relative UV intensity dropped by as much as 100% when iron was present. Detailed results were assessed and yielded support for the following three UV-induced fouling mechanisms: (a) precipitation of ferric hydroxide [Fe(OH)3], (b) release of calcium from calcium-organics complexes followed by precipitation of iron-organics complexes, and (c) calcium carbonate precipitation. Other fouling mechanisms, such as sedimentation of preformed particles and sorption of calcium onto preformed colloids of Fe(OH)3, occurred outside the zone of UV radiation. Hence, these could be confused with concurrent UV-induced mechanisms in full-scale reactors. Iron and/or calcium undoubtedly created the most favorable conditions for fouling to occur; in the absence of both, fouling would be unlikely. The rates of fouling were enhanced when organics were also present; however, when phosphorus was present, fouling in the UV section was reduced. Indeed, UV may be viewed as inhibiting the fouling caused by phosphate complexes.     

非均相UV/Fenton氧化法降解水中六氯苯的研究

采用超声辐照促进浸渍法制备了非均相UV/Fenton催化剂Fe/Al2O3,并对其进行了表征.以制备的催化剂对水中六氯苯进行非均相UV/Fenton法氧化降解.考察了铁的负载量、初始pH、H2O2投加量、催化剂投加量和反应时间对六氯苯降解效果的影响,并探讨了六氯苯的降解动力学规律.结果表明,制备的催化剂表面活性组分分散均匀,对六氯苯具有较高的催化活性和重复利用性.非均相UV/Fenton法降解六氯苯的最佳实验条件为:铁的负载量为2%,废水初始pH为3,H2O2和Fe/Al2O3催化剂的投加量分别为34 mg/L和150 mg/L,反应时间为20 min.在此条件下,浓度为500μg/L的六氯苯降解效率达94.5%.HCB的降解反应动力学规律可用Langmuir-Hinshwood方程很好地描述.六氯苯在催化剂表面的吸附常数为1.962 L/mg,表面反应速率常数为0.08 mg/(L·min).     

SMX degradation by ozonation and UV radiation: a kinetic study

The rate constants of sulfamethoxazole (SMX) degradation by ozonation and UV₂₅₄ radiation were investigated under various parameters including influent ozone gas concentration, initial SMX concentration, UV light intensity, ionic strength, water quality in terms of varying anions (bicarbonate, sulfate and nitrate), humic acid (HA) and pH. The results indicated that the removal of SMX by ozonation and UV₂₅₄ radiation fitted well to a pseudo first-order kinetic model and the rate constants were in the range of (0.9-9.8) × 10⁻³ and (1.7-18.9) × 10⁻³ s⁻¹, respectively. The second-order rate constants of SMX with ozone (k_O3), under varying operational parameters, were also determined and varied in the range of (0.60-3.38) ± 0.13 × 10⁵ M⁻¹ s⁻¹. In addition, SMX degradation through UV pretreatment followed by ozonation in the presence of HA was proved to be an effective method which can remove SMX with a low ozone dose. The results suggested that ozonation of SMX was more affected by concentration of influent ozone gas, alkalinity, and HA, while incident UV light intensity, pH, and HA were the dominant factors influencing UV degradation of SMX.     

紫外活化过硫酸盐工艺降解水中磺胺二甲氧嘧啶动力学特征与机理

采用紫外活化过硫酸盐(UV/PS)工艺降解典型磺胺类抗生素磺胺二甲氧嘧啶(SDM),比较单一紫外(UV)、单一过硫酸盐(PS)和UV/PS对SDM的去除效果,考察各因素对降解动力学的影响,并探究其降解机理,对SDM及其中间产物进行毒性测定和风险评价.结果显示,UV/PS可以加速SDM降解,反应速率常数分别是单一UV和单...     

Oxidation of MCPA and 2,4-D by UV radiation, ozone, and the combinations UV/H2O2 and O3/H2O2

The phenoxyalkyl acid derivative herbicides MCPA (4-chloro 2-methylphenoxyacetic acid) and 2,4-D (2,4-dichlorophenoxyacetic acid) were oxidized in ultrapure water by means of a monochromatic UV irradiation and by ozone, as well as by the combinations UV/H2O2 and O3/H2O2. In the direct photolysis of MCPA, the quantum yield at 20 degrees C was directly evaluated and a value of 0.150 mol Eins(-1) was obtained in the pH range 5-9, while a lower value of 0.41 x 10(-2) mol Eins(-1) was determined at pH=3. Similarly, for 2,4-D a value of 0.81 x 10(-2) mol Eins(-1) was deduced, independent of the pH of work. The influence of the additional presence of hydrogen peroxide was established in the combined process UV/H2O2, and the specific contribution of the radical pathway to the global photo-degradation was evaluated. The oxidation by ozone and by the combination O3/H2O2 was also studied, with the determination of the rate constants for the reactions of both herbicides with ozone and hydroxyl radicals at 20 degrees C. These rate constants for the direct reactions with ozone were 47.7 and 21.9 M(-1) s(-1) for MCPA and 2,4-D respectively, while the found values for the rate constants corresponding to the radical reactions were 6.6 x 10(9) and 5.1 x 10(9) M(-1) s(-1).     

Heterogeneous photocatalytic degradation of methyl orange in schwertmannite/oxalate suspension under UV irradiation

Introduction

Schwertmannite was synthesized through an oxidation of FeSO₄ by Acidithiobacillus ferrooxidans LX5 cell suspension at an initial pH?2.5 and 28°C for 3?days and characterized using X-ray diffraction spectroscopy and scanning electron microscope. The schwertmannite photocatalytic degradation of methyl orange (MO) by oxalate was investigated at different initial pH values, concentrations of schwertmannite, oxalate, and MO.

Results

The results demonstrated that photodegradation of MO in the presence of schwertmannite or oxalate alone was very weak. However, the removal of MO was significantly enhanced when schwertmannite and oxalate coexisted in the reaction system. Low pH (4 or less) was beneficial to the degradation of MO. The optimal doses of schwertmannite and oxalate were 0.2?g?L^?1 and 2?mM, respectively. Hydroxyl radicals (·OH) and Fe(II), the intermediate products, were also examined during the reaction to explore their correlation with the degradation of MO.

Conclusion

A possible mechanism for the photocatalytic decomposition of MO in the study was proposed. The formation of Fe(III)-oxalate complexes on the surface of schwertmannite was a precursor of H₂O₂ and Fe(II) production, further leading to the yield of ·OH responsible for the decomposition of MO.