Hydroxyl radical and ozone initiated photochemical reactions of 1,3-butadiene

1,3-Butadiene, classified as hazardous in the 1990 Clean Air Act Amendments, is an important ambient air pollutant. Understanding its atmospheric transformation is useful for its own sake, and is also helpful for eliciting isoprene's fate in the atmosphere (isoprene dominates the biogenic emissions in US). In this paper, samples from both hydroxyl- and ozone-initiated photooxidation of 1,3-butadiene were analyzed by derivatization with O- (2,3,4,5,6-pentafluorobenzyl)-hydroxylamine followed by separation and detection by gas chromatography/ion trap mass spectrometry to detect and identify carbonyl compounds. The following carbonyls were observed: formaldehyde, acrolein, glycolaldehyde, glycidaldehyde, 3-hydroxy-propanaldehyde, hydroxy acetone, and malonaldehyde, which can be classified into three categories: epoxy carbonyls, hydroxyl carbonyls, and di-carbonyls. Three non-carbonyls, furan, 1,3-buatdiene monoxide, and 1,3-butadiene diepoxide, were also found. To confirm their identities, both commercially available and synthesized standards were used. To investigate the mechanism of 1,3-butadiene, separate batch reactor experiments for acrolein and 1,3-butadiene monoxide were carried out. Time series samples for several products were also taken. When necessary, computational chemistry methods were also employed. Based on these results, various schemes for the reaction mechanism are proposed.     

Degradation of gas-phase propylene glycol monomethyl ether acetate by ultraviolet/ozone process: A kinetic study

A pilot-scale plug-flow reactor was built to investigate its performance in treating airborne propylene glycol monomethyl ether acetate (PGMEA) via ozonation, ultraviolet (UV) photolysis and UV/O3 technologies. Governing factors, such as the initial molar ratio of ozone (O3) to PG-MEA, UV volumetric electric power input, and moisture content in the influent airstream, were investigated. A 1-L batch reactor was used to investigate some photodegradation characteristics of PGMEA in advance. Experiments were conducted at a fixed influent PGMEA concentration of approximately 50 ppm and an ambient temperature of 26 degrees C. A gas space time of 85 sec in the plug-flow reactor was kept for either ozonation or photolysis reaction, whereas a gas space time of 170 sec was used for the UV/O3 degradation. Results show that an initial molar ratio of O3 to PGMEA of >2.91 and an UV volumetric electric input power of 0.294 W/L(-1) sufficed to obtain PGMEA decompositions of >90% by UV/O3. Kinetic analyses indicate that all types of PGMEA decomposition are pseudo-first order with respect to its concentration. Moisture content (relative humidity = 15-99%) and UV volumetric electric input power (0.147 and 0.294 W/L(-1)) were major factors that strongly affect the PGMEA degradation rate.     

Decomposition of gas-phase trichloroethene by the UV/TiO2 process in the presence of ozone.

The decomposition of gas-phase trichloroethene (TCE) in air streams by direct photolysis, the UV/TiO2 and UV/O3 processes was studied. The experiments were carried out under various UV light intensities and wavelengths, ozone dosages, and initial concentrations of TCE to investigate and compare the removal efficiency of the pollutant. For UV/TiO2 process, the individual contribution to the decomposition of TCE by direct photolysis and hydroxyl radicals destruction was differentiated to discuss the quantum efficiency with 254 and 365 nm UV lamps. The removal of gaseous TCE was found to reduce by UV/TiO2 process in the presence of ozone possibly because of the ozone molecules could scavenge hydroxyl radicals produced from the excitation of TiO2 by UV radiation to inhibit the decomposition of TCE. A photoreactor design equation for the decomposition of gaseous TCE by the UV/TiO2 process in air streams was developed by combining the continuity equation of the pollutant and the surface catalysis reaction rate expression. By the proposed design scheme, the temporal distribution of TCE at various operation conditions by the UV/TiO2 process can be well modeled.     

Decomposition of 2-nitrophenol in aqueous solution by ozone and UV/ozone processes.

The decomposition of 2-nitrophenol in aqueous solutions by ozone and UV/ozone processes was found to be technically feasible under adequate experimental conditions. Formation of nitrate ions was observed following the decomposition of 2-nitrophenol by ozone and UV/ ozone processes. Increasing ozone dosage and UV light intensity accelerated the decomposition rate of 2-nitrophenol in an aqueous solution. The species distribution of 2-nitrophenol under various solution conditions plays a significant role in determining decomposition behavior. In most experiments conducted in this study, the decomposition of 2-nitrophenol by ozone and UV/ozone processes was favored to occur in alkaline conditions. The addition of 2-butanol accelerated the rate of gaseous ozone transfer to an aqueous phase by reducing the surface tension of aqueous solution and therefore enhancing the decomposition rate of 2-nitrophenol by ozone and UV/ozone processes.     

Decomposition of Gas Phase 1,3-Butadiene by Ultraviolet/Ozone Process

Abstract

A pilot-scale plug-flow reactor was built to investigate its performance in treating airborne 1,3-butadiene (BD) via ozonation (O₃) and ultraviolet (UV)/O₃ technologies. Governing factors, such as the initial molar ratio of ozone to BD, UV volumetric electric input power, and moisture content in the influent airstream, were investigated. Experiments were conducted at an influent BD concentration of ～50 ppm, an ambient temperature of 26 °C, and a gas retention time of 85 sec. Results show that an initial molar ratio of ozone to BD of 3.5 and 2 sufficed to obtain BD decompositions of >90% for ozonation and UV/O₃, respectively. The UV irradiance did not directly promote the decomposition of BD, rather, it played a role in promoting the production of secondary oxidants, such as hydroxyl radicals. Kinetic analyses indicate that both types of BD decomposition are peudo–first-order with respect to BD concentrations. Moisture content (relative humidity = 40–99%) and UV volumetric electric input power (0.147 and 0.294 W/L) are both factors that weakly affect the rate of BD decomposition. Economic evaluation factors, including both energy of ozone production and UV electric input power, were also estimated.     

气相中嗅味物质—壬醛的真空紫外光降解研究

在建立热脱附-气相色谱法分析气相中低浓度壬醛的基础上,研究了不同条件下真空紫外光对气相中低浓度壬醛的光化学降解。结果表明,壬醛的真空紫外光降解率基本不受初始浓度的影响,在所研究的浓度范围(0.13～1.74mg/m3)内符合一级动力学,其表观反应速率常数为2.3 min-1。相对湿度一开始增加时均使得不同浓度的壬醛的去除率降低,但低浓度壬醛的降解随后几乎不再受相对湿度变化的影响,而较高浓度壬醛的去除率则先随相对湿度增加而下降,随后则又上升。壬醛能在极干燥的氮气气氛中被真空紫外光降解,同时它在氮气气氛中的降解率随相对湿度的增加而增加,壬醛在极干燥的氮气、空气和氧气气氛中的降解率依次上升,说明真空紫外光直接光解、光解产生的羟基自由基、光解产生的氧原子或臭氧均能导致壬醛的有效降解,且这3种机制相互影响。     

臭氧-过硫酸钠高级氧化降解土霉素废气

为去除禽畜养殖粪便高温堆肥过程产生的土霉素(OTC)废气,采用臭氧-过硫酸钠(O₃/PS)高级氧化方法,在喷淋装置中降解土霉素(OTC)废气。通过对比不同条件下装置对OTC废气的去除率,考察了O₃及PS对OTC废气去除率及耦合作用。结果表明：O₃/PS喷淋塔对OTC去除率可达94.7%,O₃直接氧化作用的加入使OTC的去除率提高了6.2%~15.9%;加入PS后,OTC的去除率增加了13.9%~23.2%,这是由8.6%~13.7%的·OH氧化作用和4.5%~7.5%的${\rm{SO}}_4^{ \cdot - }$氧化作用引起的。结合高分辨液质联用仪(LC-TOF-MS/MS)分析OTC的降解产物,可以看出,OTC在O₃/PS喷淋塔中经过O₃、·OH和${\rm{SO}}_4^{ \cdot - }$的氧化后,生成了4种主要中间产物,即C₂₀H₁₈N₂O₈、C₂₂H₂₀N₂O₈、C₁₂H₁₆O₂和C₁₃H₂₁O₃。由此可知,OTC废气能被喷淋装置有效去除,并被O₃/PS氧化降解。以上研究结果为含OTC废气的产生、检测和处理提供了参考。     

真空紫外/紫外/过硫酸盐工艺降解水中全氟辛酸

全氟辛酸(PFOA)是一种水中检出频率较高的全氟和多氟烷基物质,常规水处理工艺难以有效去除。紫外(UV)/过硫酸盐(PDS)工艺对PFOA具有较好的处理效果。相对于传统低压汞灯,新型光源真空UV/UV(VUV/UV)汞灯,可在不增加电能输入下,额外输出185 nm VUV光子有效光解PFOA。因此,采用VUV/UV汞灯驱动UV/PDS工艺具有高效降解PFOA的潜力。选用前期研发的配装VUV/UV汞灯的细管流光反应系统开展研究,通过微量过氧化氢生成法和化学感光剂(尿苷)测定VUV和UV辐照强度分别为1.16×10⁻⁴ einstein·(m²·s)⁻¹和1.39×10⁻³ einstein·(m²·s)⁻¹。结果表明,相对于单独UV和VUV/UV辐照,PDS的投加会生成SO₄⁻·,进而强化PFOA的降解。由于额外的185 nm VUV光子辐照,VUV/UV/PDS工艺相对于UV/PDS工艺具有明显强化降解作用。当PDS浓度在0~0.9 mmol·L⁻¹时,协同因子(R)均低于1,表明尽管VUV/UV汞灯可强化UV/PDS工艺对PFOA的去除,但PDS和VUV/UV的联用并没有明显的协同作用。PDS浓度的提升会增加SO₄⁻·的生成,强化自由基降解的贡献(18%上升为35%),但同时竞争吸收VUV光子导致PFOA的直接VUV降解作用减弱(82%下降为65%),总体PFOA降解的协同效果有所减弱。以上研究结果表明VUV的加入可强化UV/PDS工艺去除PFOA的效率,为VUV/UV/PDS工艺应用于水中PFOA高效去除提供参考。     

Degradation of tert-butyl formate and its intermediates by an ozone/UV process

In this paper, the oxidation of tert-butyl formate (TBF) in aqueous solution by an ozone/UV process was described. The oxidation process was investigated experimentally in a semibatch reactor. The results of the study indicated that the ozone/UV process was very effective in oxidizing TBF. tert-Butyl alcohol (TBA), hydroxy-iso-butyraldehyde (HiBA), acetone, formaldehyde, and formic acid were identified as major primary intermediates during the oxidation of TBF. About 90% organic carbon balance was obtained indicating that most reaction intermediates have been identified and quantified. Some of the primary intermediates were also oxidized in the ozone/UV system. Accordingly, HiBA, acetone, formaldehyde, and formic acid were the primary intermediates of TBA oxidation. The oxidation of acetone in the ozone/UV system generated formaldehyde, pyruvaldehyde, acetic acid, formic acid as primary intermediates. It was also observed that the reaction intermediates formed during the oxidation of TBF react well in the ozone/UV system and complete mineralization could be achieved by the process.     

Degradation of tert-butyl formate and its intermediates by an ozone/UV process

In this paper, the oxidation of tert-butyl formate (TBF) in aqueous solution by an ozone/UV process was described. The oxidation process was investigated experimentally in a semibatch reactor. The results of the study indicated that the ozone/UV process was very effective in oxidizing TBF. tert-Butyl alcohol (TBA), hydroxy-iso-butyraldehyde (HiBA), acetone, formaldehyde, and formic acid were identified as major primary intermediates during the oxidation of TBF. About 90% organic carbon balance was obtained indicating that most reaction intermediates have been identified and quantified. Some of the primary intermediates were also oxidized in the ozone/UV system. Accordingly, HiBA, acetone, formaldehyde, and formic acid were the primary intermediates of TBA oxidation. The oxidation of acetone in the ozone/UV system generated formaldehyde, pyruvaldehyde, acetic acid, formic acid as primary intermediates. It was also observed that the reaction intermediates formed during the oxidation of TBF react well in the ozone/UV system and complete mineralization could be achieved by the process.     

Treatment of groundwater contaminated with gasoline components by an ozone/UV process

In this paper, the treatment of real groundwater samples contaminated with gasoline components, such as benzene, toluene, ethylbenzene, and xylene (BTEX), methyl tert-butyl ether (MTBE), tert-butyl alcohol (TBA), and other gasoline constituents in terms of total petroleum hydrocarbons as gasoline (TPHg) by an ozone/UV process was investigated. The treatment was conducted in a semi-batch reactor under different experimental conditions by varying ozone gas dosage and incident UV light intensity. The groundwater samples contained BTEX compounds, MTBE, TBA, and TPHg in the ranges of 5-10000, 3000-5500, 80-1400, and 2400-20000mugl(-1), respectively. The ozone/UV process was very effective compared to ozonation in the removal of the gasoline components from the groundwater samples. For the various gasoline constituents, more than 99% removal efficiency was achieved for the ozone/UV process and the removal efficiency for ozonation was as low as 27%. The net ozone consumed per mol of organic carbon (from BTEX, MTBE, and TBA) oxidized varied in the range of 5-60 for different types of groundwater samples treated by the ozone/UV process. In ozonation experiments, it was observed that the presence of sufficient amount of iron in groundwater samples improved the removal of BTEX, MTBE, TBA, and TPHg.     

Transport characteristics of gas phase ozone in unsaturated porous media for in-situ chemical oxidation

Encapsulation technology is being investigated as a method for controlling pH in situ at contaminated groundwater sites where pH may limit remediation of organic contaminants. This study examined the effectiveness of using KH2PO4 buffer encapsulated in a pH-sensitive coating to neutralize pH in laboratory sand columns (1.5-1) under a simulated groundwater flow rate and characterized the pattern of capsule release in the flow-through system. Denitrification was used in the columns to increase the pH of the pore water. Each of three columns was equipped with three miniature mesh wells to allow contact of the buffer with column pore water, but capsules (15 g) were inserted into only one column (amended). The two other columns served as amendment (no buffer) and abiotic (no denitrification) controls. Oxidation-reduction potential, dissolved organic and inorganic carbon, NH4+, NO3- +NO2-, PO(4)3-, and pH were measured in the influent, two side ports, and effluent of the columns over time. Near complete conversion of 80 mg N/1 of nitrate and 152 mg/l of ethanol per day resulted in a mean pH increase from 6.2 to 8.2 in the amendment control column. The amended column maintained the target pH of 7.0 +/- 0.2 for 4 weeks until the capsules began to be depleted, after which time the pH slowly started to increase. The capsules exhibited pulses of buffer release, and were effectively dissolved after 7.5 weeks of operation. Base-neutralizing capacity contributed by the encapsulated buffer over the entire study period, calculated as cation equivalents, was 120 mM compared to 8 mM without buffer. This study demonstrates the potential for this technology to mediate pH changes and provides the framework for future studies in the laboratory and in the field, in which pH is controlled in order to enhance organic contaminant remediation by pH-sensitive systems.     

超声/臭氧组合工艺降解乐果农药废水的实验研究

采用超声波(US)/臭氧(O3)组合工艺降解乐果农药废水,考察了pH值、O3流量、反应时间、COD浓度对处理效果的影响。结果表明,采用变频、低功率(40 W)的US设备与O3组合使用,其处理效果比单独US和O3的处理效果好,二者具有明显的协同作用;通过模拟乐果农药废水确定实验参数,考察组合工艺对实际废水的处理效果,优化工艺参数并得出最佳的实验条件:处理水量为5 L、pH3、O3流量5.20 mg/L、反应时间150 min、废水初始COD浓度4 000 mg/L,COD去除率为29.06%,B/C比由0.20提高至0.35。这表明:在较低能耗和较短时间内,该组合工艺对农药废水具有良好的预处理效果,利于后续好氧生化处理。     

Ce-ZnO/AC在真空紫外下催化降解对二甲苯废气

将Ce掺杂ZnO光催化剂通过负载活性炭 (AC)的方式制备Ce-ZnO/AC吸附-催化复合材料,并以对二甲苯为典型挥发性有机污染物(VOC),研究其在真空紫外体系中光催化转化性能。结果表明：活性炭的负载能有效提高臭氧的利用效率,强化对二甲苯的去除率和矿化率;当Ce-ZnO与活性炭的负载比例为1∶2时,复合材料的光催化性能达到最优,此时对二甲苯的转化率达到95%以上;活性炭的负载不仅可使污染物与催化剂充分接触,还可有效利用臭氧从而产生·OH等自由基,协同促进对二甲苯的降解,同时更多的中间产物被降解。复合催化材料显示了良好的稳定性,在利用5次后,仍可再生恢复其光催化性能至初始状态。相对于单独的真空紫外光解,Ce-ZnO/AC吸附-催化复合材料与真空紫外体系耦合降解二甲苯的能量利用率提高了2倍,经济性好。     

光催化氧化处理有机废水

介绍了光催化氧化法的原理,对光催化氧化法处理有机废水的可行性进行了试验,探讨了ＣＯＤ随反应时间的变化规律及催化剂用量,温度、浓度的影响。试验表明,光催化氧化可降解象洗涤剂这样难降解的有机物,反应１２０ｍｉｎＣＯＤ去除率可达５０％以上。     

Atmospheric oxidation of elemental mercury by ozone in the aqueous phase

The aqueous phase oxidation of elemental mercury by ozone has been investigated in the laboratory using a quartz glass reactor with gas phase concentrations of 400–1800ng m⁻³ and 70–200 ppb for Hg(0) and O₃, respectively. The absorption of Hg in the water phase was increased by three orders of magnitude with O₃ present. If the oxidation were to proceed with the same speed in liquid water in contact with the atmosphere,conversion rales of 1–4% h⁻¹ would be implied. Experiments using ambient urban air with 2–6 ng Hg m⁻³ confirm the process at elevated O₃ concentrations. At ambient O₃ concentrations competitive reactions become important, e.g. O₃ consumption by SO₂, hydrocarbons etc., and even some reduction of Hg²⁺ could occur. The atmospheric oxidation of Hg(0) by O₃ in water is thus considered important at high O₃ levels in regionally polluted or remote areas.     

臭氧气浮工艺处理城市合流制溢流污染

合流制溢流(CSO)污水具有水质水量波动大、非连续产生的特点,采用臭氧气浮技术对CSO污水进行处理,研究该技术对化学需氧量(COD)、总磷(TP)、悬浮固体(SS)等污染指标的控制效果。实验室小试结果表明,在最适工艺条件下,混凝-臭氧同步处理对CSO实际污水SS、TP、COD去除率分别为77.8%、73.6%和57.9%,显著削弱了腐殖质类有机物荧光强度,混凝与臭氧氧化之间表现出良好的协同作用,能够实现CSO污染的有效控制。进一步设计了臭氧气浮撬装式设备,并在武汉市开展了CSO处理现场实验研究,运行结果表明,臭氧气浮工艺系统对SS、TP、COD的平均去除率分别为81.8%、75.4%和61.7%,净化效果良好,实现了对CSO典型污染物的协同治理。通过实验室研究和工程实验结果,证实了臭氧气浮工艺用于CSO污水治理的工程可行性,上述研究结果可为CSO污水的多水质目标协同控制提供理论指导和技术参考。     

Decomposition of nitrotoluenes from trinitrotoluene manufacturing process by Electro-Fenton oxidation

Oxidative degradation of dinitrotoluene (DNT) isomers and 2,4,6-trinitrotoluene (TNT) in spent acid was conducted by Electro-Fenton's reagents. The electrolytic experiments were carried out to elucidate the influence of various operating parameters on the performance of mineralization of total organic compounds (TOC) in spent acid, including reaction temperature, dosage of oxygen, sulfuric acid concentration and dosage of ferrous ions. It deserves to note that organic compounds could be completely destructed by Electro-Fenton's reagent with in situ electrogenerated hydrogen peroxide obtained from cathodic reduction of oxygen, which was mainly supplied by anodic oxidation of water. Based on the spectra analyzed by gas chromatograph/mass spectrometer, it is proposed that initial denitration of 2,4,6-TNT gives rise to formation of 2,4-DNT and/or 2,6-DNT, which undergo the cleavage of nitro group into o-mononitrotoluene, followed by denitration to toluene and subsequent oxidation of the methyl group. Owing to the removal of both TOC and partial amounts of water simultaneously, the electrolytic method established is potentially applied to regenerate spent acid from toluene nitration processes in practice.     

Behavior of benzene and 1,3-butadiene concentrations in the urban atmosphere of Tokyo,Japan

Benzene and 1,3-butadiene concentration profiles in the urban ambient air were generated to investigate their levels at two specified sampling locations, roadside and residential, in Tokyo, Japan. Air monitoring data for benzene and 1,3-butadiene were obtained from the Air Quality Monitoring Information of the Tokyo Metropolitan Government. Air samples were continuously obtained and analyzed every hour for volatile organic compounds (VOCs) using an automated GC–MS system. The diurnal variations in benzene and 1,3-butadiene concentrations showed bi-modal patterns, which were considered to be related to the increasing and decreasing trends of vehicle emissions and vertical mixing depths in a day. The frequencies of occurrence of various benzene and 1,3-butadiene concentrations were examined. The results of each concentration showed log-normal forms with almost straight lines. The frequency distributions of both pollutants were confirmed to have a log-normal, rather than a simple normal, form. The relationship between benzene and 1,3-butadiene concentrations at both the roadside and residential site were examined. Separate observations of day and night trends revealed that photochemical decomposition showed a greater influence on the data in the residential site than that in the roadside site. These results were considered as direct evidences of photochemical decomposition of 1,3-butadiene in the atmosphere.     

中压紫外/氯水处理工艺过程中氯的分解规律

在中压紫外/氯高级氧化技术应用于去除水中微量污染物的过程中,氯的浓度会由于光解作用而降低,直接影响该技术的处理效率.为解决上述问题,通过测定不同中压紫外剂量下氯浓度的变化,研究了氯的分解规律,以及氯投加量、pH、温度、腐殖酸和常见阴离子等条件对氯分解速率的影响.结果表明,氯的分解遵循一级动力学,其分解速率常数kobs随...