Quantitation of hydroxyl radical during fenton oxidation following a single addition of iron and peroxide

Chemical probes were used to study the formation of hydroxyl radical in aqueous iron-hydrogen peroxide reaction. Hydroxyl radical formation rate and time dependent concentration were determined in pure water, in aqueous fulvic acid (FA) and humic acid (HA) solutions, and in natural surface waters. Indirect determinations of hydroxyl radical were made by quantitating hydroxyl radical reactions with probe compounds under controlled conditions. High probe concentrations were used to determine radical formation rates and low probe concentrations were used to determine time dependent radical concentration. Two independent probes were used for intercomparison: benzoic acid and 1-propanol. Good agreement between the two probes was observed. Natural water matrices resulted in lower radical formation rates and lower hydroxyl radical concentrations, with observed formation rate and yield in natural waters up to four times lower than in pure water. HA and FA also reduced hydroxyl radical formation under most conditions, although increased radical formation was observed with FA at certain pH values. Hydroxyl radical formation increased linearly with hydrogen peroxide concentration.     

Relevance of PCDD/PCDF formation for the evaluation of POPs destruction technologies--review on current status and assessment gaps

One important criterion for assessment of a POPs destruction technology is the potential formation of new POPs and other toxic by-products, in particular whether the highly toxic PCDDs/PCDFs are formed and under which operation conditions their formation is relevant. For incineration processes the formation mechanisms of PCDDs/PCDFs have been investigated thoroughly and strategies and technologies were developed to minimize their formation and emission. A detailed assessment of non-combustion technologies with respect to PCDD/PCDF formation is, however, lacking to date. A comparison of reaction conditions for PCDD/PCDF formation from precursor formation studies and actual applied conditions of a broad range of POPs destruction technologies in the present paper indicates that the operation conditions for a number of destruction technologies have the potential to generate high concentrations of PCDDs/PCDFs if dioxin precursors are present and that also PCDD/PCDF de novo formation can take place. Therefore a strategy and regulations for a more profound assessment and monitoring of the fate of PCDD/PCDF formation and emission is essential for the evaluation of POP destruction technologies and for a sound risk management of POPs. The present paper aims to provide a critical impulse in this respect, discusses the relevant formation pathways with respect to POPs destruction technologies and proposes a basic framework on how evaluations may be performed.     

陶瓷烧成中气氛及温度对NOX生成的影响

通过对不同烧成气氛NOX的生成进行测试分析,得出还原气氛可抑制NOX的生成.但在没有催化剂存在的情况下,CO对NO的还原效果不显著;其次,在烧成温度较低(1 200 ℃以下)、高温阶段温度场均匀性较好且使用洁净燃料(即含氮量较小的燃料)的情况下,快速升温将导致NOX生成的增加,此时快速型NOX起主要作用;第三,烧嘴的合理布置、改善窑体结构和加强高温阶段窑内温度场的均匀性可以减少NOX的生成.     

陶瓷烧成中NOx生成及控制对策

通过对2种不同结构、不同烧成气氛的梭式窑的整个烧成过程中NOx生成进行测试分析，得出快速升温将增加整个陶瓷烧成过程中NOx的生成；其次，烧嘴的合理布置，改善窑体结构，加强高温阶段窑内温度场的均匀性。可以减少NOx的生成；第三，还原气氛可抑制NOx的生成；最后，提出降低陶瓷烧成中NOx生成的几点建议。     

陶瓷烧成中NOx生成及控制对策

通过对2种不同结构、不同烧成气氛的梭式窑的整个烧成过程中NOx生成进行测试分析,得出快速升温将增加整个陶瓷烧成过程中NOx的生成;其次,烧嘴的合理布置,改善窑体结构,加强高温阶段窑内温度场的均匀性,可以减少NOx的生成;第三,还原气氛可抑制NOx的生成;最后,提出降低陶瓷烧成中NOx生成的几点建议.     

The occurrence of cyanide formation in six full-scale publicly owned treatment works.

This paper presents results from an intensive monitoring program implemented at six full-scale publicly owned treatment works (POTWs) to investigate the fate and formation of cyanide in wastewater treatment processes, with a focus on chlorination and dechlorination processes. A review of historical monitoring data for cyanide species in these POTWs was also conducted. This POTW monitoring program provided a database for the investigation of cyanide formation in wastewater secondary treatment. Data from participating POTWs showed evidence of cyanide formation in this 1-year monitoring effort, although the cyanide formation pattern varied significantly from one plant to another and among seasons. Generally, the chlorination of thiocyanate (SCN-) seems to be the most important mechanism for the formation of cyanide in wastewater treatment processes, especially in chlorination and dechlorination. This hypothesis is supported by the findings of a related laboratory study of mechanisms of cyanide formation in POTWs. It is recommended that POTWs monitor SCN in influent and secondary effluent to identify its presence and adjust chlorine dose appropriately.     

好氧颗粒污泥的形成过程、形成机理及相关研究

利用SBR和优势混合菌对造纸废水进行处理,在此过程中驯化出好氧颗粒污泥,对好氧颗粒污泥的形成过程、形成机制等进行研究发现,好氧颗粒污泥的形成经历了细菌增殖、絮状体形成、絮状体聚合、凝絮体形成和好氧颗粒污泥形成五个阶段;其形成至少有菌丝缠绕、小块污泥互相联合、吸附和连接四种机制。优势混合菌的加入,是好氧颗粒污泥之所以能够形成的关键因素。     

NH_4＋和H_2O_2抑制臭氧氧化过程中溴酸盐形成的效能研究

通过纯水条件下的模拟研究,考察NH4＋和H2O2在单独和联用时对臭氧氧化过程中溴酸盐形成的抑制效能。结果表明,单独投加NH4＋能显著降低溴酸盐的生成量,并对水中臭氧浓度衰减无明显影响;投加H2O2大于0.20 mmol/L时,能在一定程度上抑制溴酸盐的形成,但加快了水中臭氧浓度的衰减;同时投加过量H2O2和NH4＋时,相对单独投加过量H2O2条件进一步抑制了溴酸盐的形成,但相对单独投加NH4＋条件却促进了溴酸盐的形成。     

Kinetics of carbon degradation and PCDD/PCDF formation on MSWI fly ash

The native carbon oxidation and PolyChloroDibenzo-p-Dioxins and PolyChloroDibenzoFurans, PCDD/F, formation were simultaneously studied at different temperatures (230-350 degrees C) and times (0-1440 min) in order to establish a direct correlation between the disappearance of the reagent and the formation of the products. The kinetic runs were conducted in an experimental set up where conditions were chosen to gain information on the role of fly ash deposits in cold zones of municipal solid waste incinerators in PCDD/F formation reaction. The carbon oxidation measured as the decrease of total organic carbon of fly ash was in agreement with the carbon evolved as sum of CO and CO(2). The carbon mass balance indicated an increase in the efficiency of carbon conversion in CO and CO(2) with temperature. The CO and CO(2) formation was the result of two parallel pseudo first order reactions thus giving significant information about the reaction mechanism. PCDD/F formation as a function of temperature showed that the maximum formation was achieved in a narrow range around 280 degrees C; the time effect at 280 degrees C was a progressive formation increase at least up to 900 min. The PCDF:PCDD molar ratio increased with temperature and time, and the most abundant homologues were HxCDD, HpCDD, OCDD for PCDD, and HxCDF, HpCDF within PCDF. These experimental results supported the hypothesis that the formation mechanism was the de novo synthesis.     

An expanded reaction kinetic model of the CuO surface-mediated formation of PCDD/F from pyrolysis of 2-chlorophenol

An expanded reaction kinetic model, including 17 surface reactions, is proposed to explain the yields of PCDD/F obtained in an experimental study of the reaction of 2-chlorophenol over a CuO/silica surface. The mechanism is loosely based on the gas-phase mechanism for PCDD/F formation widely discussed in the literature. The principal differences are the impact of chemisorption of 2-chlorophenols to metal oxides on radical formation and the steric hindrance of oxygen-centered radicals on the surface inhibiting radical-radical reaction pathways that lead to formation of dibenzo-p-dioxin (DD). Gas-phase molecule-surface-bound adsorbate reactions are the preferred route of DD formation, while radical-radical surface reactions are the main channel for dichloro-dibenzofuran (DCDF) formation. These results suggest that the Langmuir-Hinshelwood (LH) mechanism, involving radical-radical surface reactions, and the Eley-Rideal mechanism, involving a gas-phase molecule and surface-bound adsorbate, are responsible for PCDF and PCDD formation on surfaces, respectively. The calculated yields of DCDF and DD are in reasonable agreement with experimental results.     

The effect of copper speciation on the formation of chlorinated aromatics on real municipal solid waste incinerator fly ash

A limited amount of information exists regarding the relationship between the chemical form of copper and the formation of chlorinated aromatics in fly ash. To understand the effects of the various forms of copper on the formation of chlorinated aromatics in real fly ash, we determined the chemical forms of copper present in various types of real fly ash using X-ray absorption near edge structure (XANES) and evaluated the relationship between the chemical forms of copper and the formation of chlorinated aromatics. Copper chloride hydroxide (CuCl2 x 3Cu(OH)2) and cuprous chloride (CuCl) were the predominant copper species found in real fly ash. Although pure cupric chloride (CuCl2) is known to be the most active catalyst for the formation of chlorinated aromatics under experimental conditions with synthetic fly ash, CuCl2 was not found in every real fly ash sample. The amount of copper chloride hydroxide was positively correlated with the formation of chlorinated aromatics in real fly ash and is, consequently, considered to be one of the key species involved in the formation of chlorinated aromatics.     

Effects of bromide on the formation of THMs and HAAs

The role of bromide in the formation and speciation of disinfection by-products (DBPs) during chlorination was investigated. The molar ratio of applied chlorine to bromide is an important factor in the formation and speciation of trihalomethanes (THMs) and halogenacetic acids (HAAs). A good relationship exists between the molar fractions of THMs and the bromide incorporation factor. The halogen substitution ability of HOBr and HOCl during the formation of THMs and HAAs can be determined based on probability theory. The formation of HAAs, and their respective concentrations, can also be estimated through use of the developed model.     

The effects of temperature and oxygen content on the PCDD/PCDFs formation in MSW fly ash

In this study, the effects of the temperature, oxygen content in the gas stream and carbon content in ash particles on PCDD/Fs formation on the fly ash surface were investigated. The optimum temperatures for dioxin formation were found at 350 degrees C for boiler ash, 300 degrees C for cyclone ash and 250 degrees C for ESP ash, respectively. Preliminary results indicate that the optimum temperature will decrease as the particle size decreases. When the O2 concentration is varied between 0% and 100%, the optimum oxygen content for PCDD/Fs formation is found to be at 7.5% for cyclone ash, and the PCDD/PCDF ratio increases with the increase of oxygen content. Dioxin formation is observed even for the gas containing no oxygen passed through the fly ash. Hence, other reacted routes that do not need O2 for dioxin formation take place on fly ash. The carbon content in fly ash is varied between 0% and 20% in this study, and the results have indicated that the maximum dioxin formation is to be found at 5%. The precursors are not injected into the fly ash or gas stream in all formation experiments, however, dioxin is still formed in fly ash. Consequently, other chlorinated routes besides Deacon reactions may take place on the fly ash surface.     

Are fuel additives a viable contrail mitigation option?

Fuel additives have been proposed as a potential mitigation option for contrails. They could change the thermodynamic conditions necessary for contrail formation in a way that makes contrail formation more difficult than with standard kerosene fuel. Here I show how additives could affect contrail formation, and I conclude that fuel additives are not a useful way to avoid contrails.     

Formation of chloroform and carbon tetrachloride in foods treated with sodium hypochlorite

The formation of chloroform and carbon tetrachloride during the treatment of fresh vegetable homogenate with sodium hypochlorite was studied.When a n-hexane extract of the reaction mixture of fresh vegetables and sodium hypochlorite was analysed by gas chromatography, chloroform and carbon tetrachloride were detected, and many unidentified peaks were also observed. The formation conditions of chloroform and carbon tetrachloride were studied. The mechanism of chloroform formation may be different from that of carbon tetrachloride according to the study of pH on the formation of both compounds. The formation of chloroform is much greater than that of carbon tetrachoride.     

Formation of PFOA from 8:2 FTOH in closed-bottle experiments with brackish water

The formation of perfluorooctanoate (PFOA) from 1H,1H,2H,2H-perfluorodecanol (8:2 FTOH) was studied for the first time in laboratory experiments with brackish water. The water samples were collected from the Baltic Sea, which is one of the largest brackish water areas in the world and is polluted with PFOA and other perfluorinated compounds. The formation of PFOA was studied in closed-bottle experiments at different water temperatures. As a reference experiment, a modified OECD 310 test was conducted with sludge from a wastewater treatment plant and with brackish water. The PFOA and 8:2 FTOH were concentrated from water samples by solid-phase extraction (SPE) and were analysed using liquid chromatography–mass spectrometry. The effect of oxygen concentration on the formation of PFOA was studied using surface water samples with high and low oxygen contents. Other experiments were performed with oxygen-rich surface water and oxygen-deficient bottom water. The formation of PFOA was observed in all experiments; it was higher in the trial performed with brackish water than in the reference test carried out with sludge. Clear temperature dependence was observed in the formation of PFOA in brackish water tests; after a 30-day test period, a sixfold increase was observed in the amount of PFOA in surface water between the temperatures of 15 and 20 °C. Microbes were suggested as the major cause of the formation of PFOA, but other environmental characteristics, such as oxygen, could also affect the formation potential of PFOA.     

Competition of coagulation sink and source rate: New particle formation in the Pearl River Delta of China

The coagulation sink and its role in new particle formation are investigated based on data obtained during the PRIDE-PRD2004 campaign at Xinken of Pearl River Delta, China. Analysis of size distributions and mode contributions of the coagulation sink show that the observed higher load of accumulation mode particles impose a significant effect on the coagulation sink and result in higher coagulation sinks at Xinken despite of the lower total particle number compared with other areas. Hence it is concluded that the higher coagulation sink may depress the occurrence frequency of new particle formation events. The strategies targeting at controlling accumulation mode particles may have influences on the frequency of new particle formation events at this area. The factors affecting the coagulation sink are evaluated. The relatively lower ambient relative humidities may weaken the coagulation sink and facilitate the occurrence of new particle formation events during noontime, while the surmise of nucleation and growth involving organic matter may imply an actually higher coagulation sink than expected. These factors have a significant influence on the ultimate fate of the newly formed nuclei and new particle formation. A comparison of event and non-event days indicates that the coagulation sink is not the only decisive factor affecting new particle formation, other factors including the precursor vapors and photochemical activity are none the less important either. Competition of coagulation sink and high source rate leads to the occurrence of new particle formation events at Xinken.     

Thermodynamic analysis and kinetic modelling of dioxin formation and emissions from power boilers firing salt-laden hog fuel

Both organic chlorine (e.g. PVC) and inorganic chlorides (e.g. NaCl) can be significant chlorine sources for dioxin and furan (PCDD/F) formation in combustion processes. This paper presents a thermodynamic analysis of high temperature salt chemistry. Its influence on PCDD/F formation in power boilers burning salt-laden wood waste is examined through the relationships between Cl2, HCl, NaCl(g) and NaCl(c). These analyses show that while HCl is a product of combustion of PVC-laden municipal solid waste, NaCl can be converted to HCl in hog fuel boilers by reactions with SO2 or alumino-silicate materials. Cl2 is a strong chlorinating agent for PCDD/F formation. HCl can be oxidized to Cl2 by O2, and Cl2 can be reduced back to HCl by SO2. The presence of sulphur at low concentrations thus enhances PCDD/F formation by increasing HCl concentrations. At high concentrations, sulphur inhibits de novo formation of PCDD/Fs through Cl2 reduction by excess SO2. The effect of NH3, CO and NOx on PCDD/F formation is also discussed. A semi-empirical kinetic model is proposed. This model considers both precursor and de novo formation mechanisms. A simplified version is used as a stack emission model. The kinetic model indicates that stack dioxin emissions will increase linearly with decreasing electrostatic precipitator (ESP) efficiency and exponentially with increasing ESP temperature.     

稳定表流湿地中污泥的形成及除污效果

探讨了温度、植物及不同湿地流态对稳定表流人工湿地中污泥的形成和组成的影响,并考察了湿地在污泥形成过程中的除污效果。结果表明,温度对VSS的影响较大,植物在污泥形成过程中对污泥量没有明显影响,但可以改变污泥组成,湿地流态对污泥形成和组成均有影响,湿地中污泥的含量为0.4～0.6 g/L;种植有风车草的推流挡板湿地(池5)总体效果相对较好;各稳定表流湿地出水水质基本达到《城镇污水处理厂污染物排放标准》(GB18918-2002)二级标准,污泥形成后TN和NH3-N的去除率均有提高。     

氧化镁脱硫结垢研究

对氧化镁脱硫法中的结垢问题进行了系统的研究 ,通过对比实验 ,分析了结垢的机理、氧化镁法在防止结垢方面所具有的优势及其原因 ,提出了实际中判断结垢倾向的方法和避免结垢的合理建议。