甲硫醚废气制取二甲基亚砜技术研究

选择双氧水作氧化剂，将具有恶臭气味的涕灭威生产的副产物甲硫醚氧化成无臭的二甲基亚砜。通过实验，优化了工艺条件，减少了安全隐患，提高了二甲基亚砜的产率，消除了恶臭污染。     

Effect of selected organic and inorganic snow and cloud components on the photochemical generation of nitrite by nitrate irradiation

The effect of selected organic and inorganic compounds, present in snow and cloudwater was studied. Photolysis of solutions of nitrate to nitrite was carried out in the laboratory using a UVB light source. The photolysis and other reactions were then modelled. It is shown that formate, formaldehyde, methanesulphonate, and chloride to a lesser extent, can increase the initial formation rate of nitrite. The effect, particularly significant for formate and formaldehyde, is unlikely to be caused by scavenging of hydroxyl radicals. The experimental data obtained in this work suggest that possible causes are the reduction of nitrogen dioxide and nitrate by radical species formed on photooxidation of the organic compounds. Hydroxyl scavenging by organic and inorganic compounds would not affect the initial formation rate of nitrite, but would protect it from oxidation, therefore, increasing the concentration values reached at long irradiation times. The described processes can be relevant to cloudwater and the quasi-liquid layer on the surface of ice and snow, considering that in the polar regions irradiated snow layers are important sources of nitrous acid to the atmosphere. Formate and (at a lesser extent) formaldehyde are the compounds that play the major role in the described processes of nitrite/nitrous acid photoformation by initial rate enhancement and hydroxyl scavenging.     

Photolysis of the herbicide bispyribac sodium in aqueous medium under the influence of UV and sunlight in presence or absence of sensitizers

The photolysis of a rice herbicide Bispyribac sodium (Sodium 2, 6-bis [(4, 6-dimethoxypyrimidin-2-yl) oxy] benzoate) has been studied in different aqueous medium (distilled water, pond water and Irrigation water) under the influence of UV (λ max ≥ 250 nm) and sunlight in presence or absence of sensitizers (TiO₂ and KNO₃). The study was conducted under laboratory simulated condition which made it possible to evaluate the contribution of different factors viz. source of irradiation, solvent and sensitizers towards the photolysis of bispyribac sodium. The photodegradation proceeds via first order reaction Kinetics in all the cases. Five photo metabolites (M₁-M₅) were isolated in pure form by column chromatographic method from the irradiation system under UV influenced and TiO₂ as sensitizer. From the different spectral data (IR, NMR, UV-VIS, Mass) the structure of these five metabolites were assigned as M₁ (Phenol), M₂ [2, 6-Dihydroxy benzoic acid], M₃ [2, 6-bis [(4, 6 dimethoxypyrimidin-2yl) oxy] benzoic acid], M₄ [2-(3-Hydroxy-phenoxy)-pyrimidine-4, 6-diol] and M₅ as [2,4-Dihydroxy-3, 5-dimethoxy-6-(4-methoxy pyrimidine-2-yloxy)-benzoic acid]. Moreover, another six photometabolites (M₆-M₁₁) were identified from the different irradiation system on the basis of Micromass analysis. On the basis of MS/MS data analysis, the structure of these six photometabolites were assigned as M₆ [2-(4, 6-Dimethoxy-pyrimidin-2-yloxy)-6-hydroxy-benzoic acid], M₇ [2-Hydroxy-6-(4-hydroxy-6-methoxy-pyrimidin-2-yloxy)-benzoic acid], M₈ [4, 6-Dimethoxy-pyrimidin-2-ol], M₉ [6-Methoxy-pyrimidine-2, 4-diol], M₁₀ [2-Hydroxy-6-(pyrimidin-2-yloxy)-benzoic acid] and M₁₁ [2, 4, 6-Trimethoxy-pyrimidine]. The plausible Photodegradation pathways of bispyribac sodium in the present investigation were portrayed which proceeds via hydrolysis, hydrolytic cleavage, O-dealkylation, decarboxylation, dehydroxylation, O-alkylation and hydroxylation.     

The structure of the fire fighting foam surfactant Forafac®1157 and its biological and photolytic transformation products

For several decades, perfluorooctane sulfonate (PFOS) has widely been used as a fluorinated surfactant in aqueous film forming foams used as hydrocarbon fuel fire extinguishers. Due to concerns regarding its environmental persistence and toxicological effects, PFOS has recently been replaced by novel fluorinated surfactants such as Forafac®1157, developed by the DuPont company. The major component of Forafac®1157 is a 6:2 fluorotelomer sulfonamide alkylbetaine (6:2 FTAB), and a link between the trade name and the exact chemical structure is presented here to the scientific community for the first time. In the present work, the structure of the 6:2 FTAB was elucidated by ¹H, ¹³C and ¹⁹F nuclear magnetic resonance spectroscopy and high-resolution mass spectrometry. Moreover, its major metabolites from blue mussel (Mytilus edulis) and turbot (Scophthalmus maximus) and its photolytic transformation products were identified. Contrary to what has earlier been observed for PFOS, the 6:2 FTAB was extensively metabolized by blue mussel and turbot exposed to Forafac®1157. The major metabolite was a deacetylated betaine species, from which mono- and di-demethylated metabolites also were formed. Another abundant metabolite was the 6:2 fluorotelomer sulfonamide. In another experiment, Forafac®1157 was subjected to UV-light induced photolysis. The experimental conditions aimed to simulate Arctic conditions and the deacetylated species was again the primary transformation product of 6:2 FTAB. A 6:2 fluorotelomer sulfonamide was also formed along with a non-identified transformation product. The environmental presence of most of the metabolites and transformation products was qualitatively demonstrated by analysis of soil samples taken in close proximity to an airport fire training facility.     

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.     

Leaching,mobility and persistence of tebufenozide in columns packed with forest litter and soil

Abstract

Leaching, downward mobility and persistence of tebufenozide was investigated under laboratory conditions in columns packed with forest litter and soil, after fortification with the analytical grade material (purity > 99.6%) and with two commercial formulations, RH‐5992 2F (aqueous flowable) and RH‐5992 ES (emulsion suspension). Two types of litter and soil were used: one type with relatively high amounts of sand and the other with high amounts of clay.

The concentrations eluted in the leachates were lower when the analytical material (dissolved in acetone) was used for fortification, than when the two formulations (diluted with water) were used. The amount leached was higher for RH‐5992 2F than for RH‐5992 ES. The type of substrate, i.e., sandy or clay type, had only marginal influence on the amounts eluted in the leachates. Downward movement of tebufenozide from the top 2‐cm layer to the untreated middle and bottom layers (3‐cm segments) was consistently lower when the analytical material was used for fortification, than when the two formulations were used. Downward movement was higher for RH‐5992 2F than for RH‐5992 ES. Persistence of tebufenozide in substrates, maintained under submerged conditions for 70 days after leaching, indicated an initial 2‐week lag period prior to the onset of degradation. Formulation‐related differences were observed in the half‐life (DT₅₀) values. When the analytical material was used for fortification, the DT₅₀ ranged from ca 54 to 59 d. However, when the formulations were used for fortification, the DT₅₀ showed a higher range, i.e., from ca 62 to 67 d for RH‐5992 2F and ca 70 to 80 d for RH‐5992 ES. Formulation ingredients appear to have caused enhanced adsorption of tebufenozide onto the substrates, thus delaying degradation.     

聚合氯化铝铁絮凝剂的性能研究

煤矸石是采煤过程之废料。本文利用煤矸石制备出了聚合氯化铝铁（ＰＡＦＣ）：一种新型无机高分子絮凝剂，探讨了Ｆｅ＾３＋的稳定性与溶液离子强度之间的关系，发现溶液的离子强度越大，则产生Ｆｅ（ＯＨ）３沉淀时的ＰＨ越高。研究了ＰＡＦＣ水解产物的ζ电位及絮凝效果随ＰＨ的变化情况，比较了ＰＡＦＣ、ＰＡＣ和ＰＦＳ的除浊性能，ＰＡＦＣ在ＰＨ为７．０－８．２范围内除浊效果最佳，ＰＡＦＣ的除浊效果优于ＰＡＣ。     

三十烷醇在水体中的光解与水解特性

按化学农药环境安全评价试验准则的要求进行了三十烷醇在水体中光解与水解的试验研究。结果表明，三十烷醇在该试验条件下光降解缓慢，半衰期为５６４ｄ；在５０ｄ的试验期内，三十烷醇在不同酸度的水体中几乎不发生水解。     

分子连接性指数对部分有机污染物溶解度及疏水参数的预测

以化学键为基础定义了键连接性指数和分子键连接性指数，分子键连接性指数与卤代烷、环烷烃、烷基苯和含氧原子醇、酮、醚及卤代苯等有机污染物的溶解度和辛醇／水分配系数都具有良好的线性关系，使用该模型对化合物的溶解度及疏水参数的估算结果接近实验值，能很好地反映有机化合物的结构特性，可应用于不饱和碳氢体系和各类杂原子体系，且具有良好的预测能力。