Kinetics and mechanism of nitrite oxidation by hypochlorous acid in the aqueous phase

The rate coefficient for the reaction of nitrite with hypochlorite and hypochlorous acid has been studied using spectrophotometric measurements. The reaction rate has been determined in a wide range of H(+) concentration (5< or =-log[H(+)]< or =11). The kinetics were carried out as a function of NO(2)(-), H(+) and total hypochlorite ([HOCl](total)=[HOCl]+[ClO(-)]+[ClNO(2)]) concentrations. The observed overall rate law is described by: -d[HClO](T)dt=[a[NO(2)(-)](2)+b[NO(2)(-)]][H(+)](2)c+d[H(+)]+e[NO(2)(-)][H(+)](2)[HOCl](total)At T=298 K and in Na(2)SO(4) at an ionic strength (I=1.00 M), we obtained using a nonlinear fitting procedure: a=(1.83+/-0.36)x10(7) s(-1), b=(1.14+/-0.23)x10(5) Ms(-1), c=(1.12+/-0.17)x10(-13) M, d=(1.43+/-0.29)x10(-6) M(2) and e=(1.41+/-0.28)x10(3) M where the errors represent 2sigma. According to the overall rate law, a/b=k(1)/k(3), b/e=k(3), c=K(w), d/c=K(a), d=K(a)K(w) and e=K(1)K(a). In Na(2)SO(4) at an ionic strength (I=1.00 M), the values of K(1) and K(a) are (1.1+/-0.1)x10(-4) and 1.28x10(7) M(-1), respectively. A mechanism is proposed for the NO(2)(-) oxidation which involves the reversible initial step: NO(2)(-)+HOCl left harpoon over right harpoon ClNO(2)+OH(-) (K(1)), while ClNO(2) undergoes the two parallel reactions: attack by NO(2)(-) (k(1)) and hydrolysis (k(3)). ClNO(2) and N(2)O(4) are proposed as important intermediates as they control the mechanism. The rate coefficients k(1) and k(3) have been determined at different ionic strengths in NaCl and Na(2)SO(4). The influence of the ionic strength and ionic environment has been studied in this work.     

Photochemistry in the mixed aqueous solution of nitrobenzene and nitrous acid as initiated by the 355 nm UV light

The 355 nm photon-initiated microscopic reaction mechanisms of the mixed aqueous solution of nitrobenzene and nitrous acid in the presence or absence of O(2) were studied by the laser flash photolysis technique. The main transient absorption peaks in the recorded spectra were assigned and the growth/decay trends of several transient species were investigated. It was found that the OH radical formed from the photolysis of nitrous acid triggered most of the subsequent radical reactions. The rate constant of the reaction between OH radical and nitrobenzene was measured to be (3.4 +/- 0.1) x 10(9) l mol(-1) s(-1). The product from this reaction, namely C(6)H(5)NO(2)-OH adduct, was found to react with O(2) to yield C(6)H(5)NO(2)-OHO(2) adduct with a rate constant of (1.6 +/- 0.2) x 10(9) l mol(-1) s(-1). Final steady-state products were identified by GC/MS analysis and were in accordance with the transient spectroscopic results. The possible reaction pathways were proposed.     

二氧化钛/碳纳米管/壳聚糖薄膜的制备及对苯的降解性能

研究了光催化降解挥发性有机化合物过程中催化剂二氧化钛/碳纳米管/壳聚糖薄膜的制备以及该催化剂对苯的光催化性能。首先采用溶胶-凝胶法制备纳米复合材料二氧化钛/碳纳米管,然后利用壳聚糖作为交联剂,制得二氧化钛/碳纳米管/壳聚糖复合材料催化薄膜。通过傅立叶红外光谱(FT-IR)、X射线衍射(XRD)透射电镜扫描(TEM)和紫外-可见光漫反射(UV-Vis)等技术分析了复合材料薄膜的组成、结构、形貌和对光的吸收性能,然后使用该催化剂对室内常见的污染物苯进行降解,并在同样的实验条件下,使用催化剂二氧化钛(P25)/壳聚糖对苯进行降解,对两者催化性能进行对比,结果表明,二氧化钛/碳纳米管/壳聚糖对苯有更强的吸附能力和更高的催化活性。     

Different reaction mechanisms of diphenylether and 4-bromodiphenylether with nitrous acid in the 355 nm laser flash photolysis of mixed aqueous solution

The microscopic reaction mechanisms of diphenylether (DPE) and 4-bromodiphenylether (4-BrDPE) with nitrous acid (HNO(2)) in the absence of O(2) have been explored by the 355nm laser flash photolysis. It was proposed that OH radical, from the photolysis of HNO(2), added to DPE forms the C(12)H(10)O-OH adduct while added to 4-BrDPE forms the 4-BrDPE-OH and 4-BrOH-DPE adducts. The first-order decay rate constants of the C(12)H(10)O-OH adduct, 4-BrDPE-OH adduct and 4-BrOH-DPE adduct were measured to be (1.86+/-0.14)x10(5)s(-1), (2.19+/-0.04)x10(5)s(-1) and (1.56+/-0.03)x10(5)s(-1), respectively. The final photolysis products of DPE and HNO(2) identified by GC/MS analysis were phenol, o-hydroxydiphenylether, p-hydroxydiphenylether and p-nitrodiphenylether, while the final photolysis product of 4-BrDPE and HNO(2) identified by LC/MS analysis was mainly the dimer.     

Photooxidation of phenol in aqueous solution in the presence of hydrogen peroxide

The combination of ultraviolet light and hydrogen peroxide was demonstrated to be a useful method for removing COD and TOC in aqueous phenol solutions. Both COD and TOC decreased to nearly zero in the presence of hydrogen peroxide.     

Dietary habits associated with the presence of organochlorine pesticides in human milk

Abstract

This study aims to establish the relationship between the consumption of certain foods and the presence of organochlorine pesticides in human milk. A total of 167 samples of breastmilk were collected. Sample analysis was carried out by gas chromatography with electron capture detector. Pesticide concentrations (op’DDT, pp’DDT, pp’DDE, Σ-DDT, HCB, β-HCH) were grouped by consumption level of fish, dairy products, meat, eggs, and seafood and then were compared to each other. The odds ratio (OR) was calculated between the concentration of pesticides (higher and/or lower than median) and the exposure variable (high consumption). The results indicated low median concentrations of HCB, β???HCH, op’DDT and pp’DDT, whose fluctuations and trends between different frequencies of food consumption were not significant. pp’DDE and Σ???DDT values according to the increase in consumption of fish were significantly increased. Women with high fish consumption have a higher risk of high concentrations of pp’DDE and Σ-DDT (OR: high consumption: 5.6 (1.3–23.6). A protective effect was observed in the consumption of dairy products (β-HCH and op’DDT), meat (HCB), and seafood (pp’DDT). These results suggest that it is possible that the consumption of fish, dairy products, meat, and seafood influences the presence of organochlorine pesticides in the studied population.     

Photochemical degradation of 1,3-dinitrobenzene in aqueous solution in the presence of hydrogen peroxide

A study on the destruction of 1,3-dinitrobenzene (1,3-DNB) in aqueous solution was carried out under ultraviolet (UV) irradiation alone and UV irradiation in the presence of hydrogen peroxide (H2O2). The combination of UV and H2O2 is significantly effective in degrading 1,3-DNB in terms of initial reaction rate and the mineralization of organic carbons. The photodegradation process can be influenced in certain extent by increasing the content of H2O2 and the acidity of reaction matrices. It was found that a variety of phenolic intermediates and inorganic acid were formed via hydroxyl radicals attacking the parent compound. The UV/H2O2 oxidation of 1,3-DNB was characterized by pseudo-zero order reaction for the degradation of 1,3-DNB with a 20 times enhanced rate constant of 1.36 x 10(-7) Ms(-1) and the initial rate constant was dependent on the initial concentration of 1,3-DNB.     

Mg/Al/Fe型类水滑石焙烧产物吸附去除水中硫酸根离子

通过共沉淀法制备了Mg/AUFe型类水滑石(MgAlFe-HTLCs)并在500℃下焙烧得焙烧产物(HTLCs-500),利用HTLCs-500吸附去除水中的硫酸根离子,并用X射线衍射对MgAlFe-HTLCs及HTLCs-500吸附硫酸根离子前后的结构进行了表征,研究了环境中其他因素对HTLCs-500吸附硫酸根离子的影响.结果表明,实验数据对准二级动力学模型的拟合结果最好;吸附过程符合Langmuir吸附等温模型,通过实验得到HTLCs-500对硫酸根离子的最大吸附量为157.73 mg/g,和Langmuir等温线得到的理论最大吸附量161.29 mg/g相差不大,对硫酸根离子具有良好的吸附性能;硫酸根溶液的初始pH值对HTLCs-500吸附硫酸根离子的性能影响不大,最佳pH值为3;X射线衍射结果表明,HTLCs-500吸附去除硫酸根离子的机理之一为HTLCs-500通过吸附硫酸根离子来恢复层状结构.     

芬顿氧化法处理水中酸性品红的研究

研究了酸性品红在Fenton体系中的降解过程,反应30 min后,在[Fe2+]0=0.06 mmol/L、[H2O2]0=0.3 mmol/L、pH=3、T=30℃的条件下,初始浓度为20 mg/L的酸性品红的去除率达到97%以上。升高反应温度,有利于Fenton体系中酸性品红的降解,但影响并不显著。根据不同温度下的速率常数,并结合Arrhenius方程求出了Fenton试剂降解酸性品红的反应活化能,仅为11.63 kJ/mol。C1?的存在对酸性品红在Fenton体系中的降解表现出明显的阻碍作用,并且随着C1?浓度的增加,抑制作用越来越大;SO24-和NO3-的存在也降低了Fenton试剂的氧化性能。     

Photophysical and photochemical properties of the pharmaceutical compound salbutamol in aqueous solutions

Salbutamol is a potent β₂-adrenergic receptor agonist widely used in the treatment of bronchial asthma and chronic obstructive pulmonary disease. An increasing number of studies have detected salbutamol in natural water systems worldwide. Studies have shown that sunlight degrades salbutamol resulting in the formation of products; some showing higher toxicity to bacteria Vibrio fischeri than the parent compound. In this contribution, steady-state absorption and emission techniques, high-performance liquid chromatography, and transient absorption spectroscopy are used to investigate the photochemistry of salbutamol in aqueous buffer solutions at controlled pH values. Ground- and excited-state calculations that include solvent effects are performed to guide the interpretation of the experimental results. Salbutamol is sensitive to UVB light absorption in the pH range from 3 to 12, forming products that absorb light at longer wavelengths than the parent compound. Quantum yields of degradation reveal that the deprotonated species is 10-fold more photo-active than the protonated species. In line with this result, the fluorescence quantum yield of the protonated species is more than an order of magnitude higher than that of the deprotonated species. Transient absorption spectroscopy shows that population of the triplet state occurs with a rate constant of 7.1 × 10⁸ s⁻¹ in the protonated species, while a rate constant of 1.7 × 10¹⁰ s⁻¹ is measured for the deprotonated species. While degradation of the deprotonated species is not affected by the presence of molecular oxygen, a twofold increase in the photodegradation yield of the protonated species in air-saturated conditions is observed.     

Effects of fulvic acid concentration and origin on photodegradation of polycyclic aromatic hydrocarbons in aqueous solution: Importance of active oxygen

With an Xe arc lamp house as simulated sunlight, the influences of fulvic acid (FA) concentration and origins on photodegradation of acenaphthene, fluorine, phenanthrene, fluoranthene and pyrene in aqueous solution have been studied. Similar effects of FAs, collected from five places around China, on polycyclic aromatic hydrocarbon (PAH) photodegradation have been observed. Active oxygen was of significance in PAH photodegradation with the presence of FAs. For systems with 1.25 mg L⁻¹ FAs, the contributions of OH to PAH photodegradation rates were from 33% to 69%. FAs had two opposite effects, i.e., stimulating the generation of active oxygen and advancing PAH photodegradation; competing with PAHs for energy and photons and restraining PAH photodegradation. Generally, photodegradation rates of the 5 PAHs decreased with the increase of FAs concentration; except fluoranthene and pyrene were advanced in solutions with low FA concentration. The influences of FA concentration on PAH photodegradation were more significant than FA origin.     

Phototransformation of methabenthiazuron in the presence of nitrate and nitrite ions

The influence of nitrate and nitrite ions on the degradation of methabenzthiazuron upon irradiation using artificial solar light has been investigated. The rate of degradation of methabenzthiazuron (1 microM) was accelerated by NO3- (0.1 mM) by a factor of 10. The irradiation of methabenzthiazuron (0.1 mM) in the presence of NO3- (1 mM) or NO2- (0.1 mM) yielded numerous intermediary photoproducts. Mineralization was achieved after prolonged exposure. Some were identified with the help of LC-ESI-MS and flow injection APCI-MS techniques. Both oxidations of the aromatic ring and of the urea chain were observed. The former started by hydroxylation of the ring. Further oxidation of the ring led to cleavage of the benzenic ring with formation of dialdehydic, diacidic and anhydric compounds. Complete removal of the lateral urea chain took place subsequently to demethylation of the terminal methyl group and loss of the CO-NH2 group. Nitration was a minor process. This work shows that the photodegradation of methabenzthiazuron in the presence of nitrate or nitrite ions is highly non-specific.     

Phenol photonitration upon UV irradiation of nitrite in aqueous solution II: effects of pH and TiO2.

Phenol photonitration and photonitrosation were studied both in homogeneous and in heterogeneous phase in the presence of TiO2 particles. The effect of pH as well as of the semiconductor particles on the kinetics and products of the reaction was observed. Formation of nitrophenols is enhanced at acidic pH, due to thermal processes initiated by nitrous acid, as well as in the presence of TiO2, due to the photocatalytic oxidation of nitrite.     

Phenol photonitration upon UV irradiation of nitrite in aqueous solution I: effects of oxygen and 2-propanol.

Nitrophenols are formed in aqueous solution upon UV irradiation of phenol and nitrite. The formation of nitrophenols is enhanced by dissolved oxygen and inhibited by the addition of 2-propanol. The mechanism of phenol photonitration involves both .NO2 (or N2O4, reacting with phenol, and 4-nitrosophenol, which is oxidised to 4-nitrophenol. A reaction scheme is proposed based on experimental results.     

Degradation and photodegradation of tetraacetylethylenediamine (TAED) in the presence of iron (III) in aqueous solution

The dark degradation of tetraacetylethylenediamine (TAED) was investigated. It is a slow process which is favored in acidic medium. There is a hydrolysis of an imide group with the scission of the C---N bond giving rise to the triacetyl derivative (TAED'). When allowed to stand for longer times a second acetyl group is eliminated with the formation of the symetric diacetyl derivative (DAED). The degradation of TAED photoinduced by iron (III) was also investigated. It appears a faster degradation which does not lead to the same products. The process only involves ^•OH radicals formed upon photolysis of aquocomplex of iron (III). They preferentially abstract a hydrogen from the methylene group. The degradation is then assisted by oxygen and leads to the formation of carbonylated oxidation products.     

Global environmental cycling of γ-HCH and DDT in the 1980s – A study using a coupled atmosphere and ocean general circulation model

A coupled atmosphere–ocean general circulation model, ECHAM5-MPIOM, was used to study the multicompartmental cycling and long-range transport of persistent and semivolatile organics. Multiphase systems in air and ocean are covered by submodels for atmospheric aerosols, HAM, and marine biogeochemistry, HAMOCC5, respectively. The model, furthermore, encompasses 2D surface compartments, i.e. top soil, vegetation surfaces and sea-ice. The total environmental fate of γ-hexachlorocyclohexane (γ-HCH, lindane) and dichlorophenyltrichloroethane (DDT) in agriculture were studied.DDT is mostly present in the soils, the water-soluble γ-HCH in soils and ocean. DDT has the longest residence time in almost all compartments. Quasi-steady state with regard to substance accumulation is reached within a few years in air and vegetation surfaces. In seawater the partitioning to suspended and sinking particles contributes to the vertical transport of substances. On the global scale deep water formation is, however, found to be more efficient. Up to 30% of DDT but only less than 0.2% of γ-HCH in seawater are stored in particulate matter.On the time scale studied (1 decade) and on global scale substance transport in the environment is determined by the fast atmospheric circulation. The meridional transport mechanism, for both compounds, is significantly enhanced by multi-hopping. Net meridional transport in the ocean is effective only regionally, mostly by currents along the western boundaries of Africa and the Americas. The total environmental burdens of the substances experience a net northward migration from their source regions, which is more pronounced for DDT than for γ-HCH. Due to the application distribution, however, after 10 years of simulation 21% of the global environmental burden of γ-HCH and 12% of DDT have accumulated in the Arctic.     

Comparison of the degradation of p-hydroxybenzoic acid in aqueous solution by several oxidation processes

A comparative study is made of 12 methods of chemical oxidation applied to degrading p-hydroxybenzoic acid in aqueous solution. The oxidation processes tested were: UV, O3, UV/TiO2, O3/Fe2+, O3/H2O2, O3/UV, UV/H2O2, H2O2/Fe2+, H2O2/Fe2+/O3, UV/H2O2/O3, H2O2/Fe2+/UV and O3/UV/H2O2/Fe2+. The 12 processes were ranked by reactivity. In a kinetic study, the overall kinetic rate constant was split up into three components: direct oxidation by UV irradiation (photolysis), direct oxidation by ozone (ozonation), and oxidation by free radicals (mainly OH*).     

The enhanced PC and PEC oxidation of formic acid in aqueous solution using a Cu-TiO2/ITO film

The photocatalytic (PC) and photoelectrocatalytic (PEC) activity of Cu-TiO2/ITO films for degrading formic acid in aqueous solution was investigated in this study. Compared with a TiO2/ITO film, the degradation efficiency of formic acid on the Cu-TiO2 films increased markedly in both the PC and PEC oxidation processes. However, it was found that the photodeposited Cu metal on the Cu-TiO2 films could electrochemically dissolute during the PEC reaction, while an electrical bias with the voltage higher than 1.48 V was applied. It is believed this is a common problem occurred for several metals deposition on the TiO2 films, which results in a poor stability of the metal-deposited TiO2 electrode in PEC processes. To improve the stability of the Cu-TiO2 electrode, an alternative process between PC and PEC reactions was investigated. It was found that the dissolute Cu metal during the PEC process was re-deposited on the Cu-TiO2 film again during the PC process. The experiments with repeated runs demonstrated that this alternative process could not only overcome the loss of Cu, but also enhance the PEC oxidation efficiency of the Cu-TiO2 films.     

The effects of LMWOAs on biodegradation of multi-component PAHs in aqueous solution using dual-wavelength fluorimetry

Biodegradation of dissolved fluorene (Flu), phenanthrene (Ph) and pyrene (Py), three polycyclic aromatic hydrocarbons (PAHs), singly or as a mixture of the three, by two bacterial strains, MEBIC 5140 (Mycobacterium flavescens) and MEBIC 5141 (Mycobacterium scrofulaceum), as well as the effects of low molecular weight organic acids (LMWOAs), e.g. malic acid, citric acid and butyric acid on biodegradation of the three PAHs in mineral salts medium aqueous solution were investigated using a newly established dual-wavelength fluorimetric method. The results showed that biodegradation processes can be monitored simultaneously, quickly and simply by dual-wavelength fluorimetry. Both co-metabolism and inhibitory effects were found during the biodegradation of the three PAHs by MEBIC 5140 and MEBIC 5141. Positive effects of butyric acid and negative effects of citric acid on biodegradation of the three PAHs in a mixture were observed.     

Mineralization of Reactive Black 5 in aqueous solution by basic oxygen furnace slag in the presence of hydrogen peroxide

Basic oxygen furnace slag (BOF slag) is a solid waste arisen from the steel making process. FeO is one of the major components of BOF slag. The FeO-containing property of BOF slag makes it possible to catalyze the Fenton reaction. Reactive Black 5 (RB5) dye is chosen as the target compound in this study. This study has investigated the catalytic performance of BOF slag on the Fenton reaction to decompose RB5 in aqueous solution. A first-order kinetic model with respect to TOC was adopted to explain the mineralization of RB5 by the H(2)O(2)/BOF slag process. The experimental results in this study suggested that dosage with 1.49 x 10(-4)M min(-1) H(2)O(2) and 12.5 g l(-1) BOF slag in the solution at pH 2 provided the optimal operation conditions for the mineralization of RB5 yielding a 51.2% treatment efficiency at 100 min reaction time, and complete decoloration can be achieved within 30 min reaction time. The H(2)O(2)/Fe(2+) ratio was then determined to be 6.06:1.