生物滤床对净化槽处理生活污水水质的影响

构建了适合于家庭分散式小型多功能一体化生活污水净化槽,通过逐步在净化槽内添加好氧、厌氧生物滤床,测定了各区COD和氨氮的变化,研究了生物滤床对净化槽污水净化效果的影响。实验结果表明:随着净化槽各区生物滤床的加入,抗冲击性能逐步增强,处理效果明显提高,当各区都加入填料且运行稳定时,出水ρ(COD)和ρ(氨氮)的平均值分别为37.8 mg/L和9.64 mg/L,优于国家一级排放标准。     

真菌漆酶介导自由基偶联和接枝反应在绿色化学中的应用

漆酶(p-苯二醇:分子氧氧化还原酶;EC 1.10.3.2)是自然界中普遍存在的一类胞外含铜多酚氧化还原酶.漆酶能够以环境中氧分子作为电子接受体,催化4个底物分子的单电子氧化形成4个相应的反应活性自由基或醌类中间体,随后这些活性中间体在酶促位点外发生步进式偶联反应,生成多种具有复杂结构的大分子C—C、C—O—C或C—N—C共价聚合产物.该反应过程中仅生成唯一副产物水,具有反应温和、底物广谱、催化效率高、操作可控和经济环保等优点.目前,真菌漆酶介导低分子有机物和高分子化合物的自由基偶联和接枝反应已经被应用于生物技术领域,该技术克服了传统物理化学方法存在的弊端,在保护人群健康和生态安全等方面具有广泛地应用前景和商业价值.本文详细地概述了真菌漆酶催化不同底物分子的自由基偶联和接枝反应在环境修复、生物监测、食品加工、纤维改性、纺织染色、制药行业和有机合成等绿色化学中的最新研究进展,旨在为开发和拓展真菌漆酶在绿色化学技术领域中的多功能应用提供科学的理论依据和技术指导.     

A comparative study of abiological granular sludge (ABGS) formation in different processes for zinc removal from wastewater

Abiological granular sludge (ABGS) formation is a potential and facile strategy for improving sludge settling performance during zinc removal from wastewater using chemical precipitation. In this study, the effect of pH, seed dosage, and flocculant dosage on ABGS formation and treated water quality was investigated. Results show that settling velocity of ABGS can reach up to 4.00 cm/s under optimal conditions, e.g., pH of 9.0, zinc oxide (ZnO) seeds dosage of 1.5 g/l, and polyacrylamide (PAM) dosage of 10 mg/l. More importantly, ABGS formation mechanism was investigated in NaOH precipitation process and compared with that in bio-polymer ferric sulfate (BPFS)–NaOH precipitation process regarding their sludge structure and composition. In the NaOH precipitation process, ABGS formation depends on some attractions between particles, such as van der Waals attraction and bridging attraction. However, during the BPFS–NaOH sludge formation process, steric repulsion becomes dominant due to the adsorption of BPFS on ZnO seeds. This repulsion further causes extremely loose structure and poor settling performance of BPFS–NaOH sludge.     

大气细粒子阳离子表面有机活性物质分析方法的优化

分别从样品前处理和分析测定两方面对大气细粒子中阳离子表面有机活性物质的二硫蓝分光光度分析法进行优化,并采用优化方案对北京市大气细粒子进行了分析.结果表明:① 优化的最佳样品前处理条件中超声提取频率为40 Hz、初始水浴温度为30℃、超声提取时间为30 min;② 优化的最佳分析测定条件中二硫蓝使用量为1.29 mg（0.5 mL的2.58 g/L二硫蓝溶液）、最佳静置时间为30 min、醋酸盐缓冲液（pH为5）最佳使用量为3 mL.二硫蓝分光光度法优化方案标准曲线的R2为0.9986,线性较好.采用该优化方案测得的北京市大气细粒子中阳离子表面有机活性物质浓度的平均值为12.87 pmol/m3,其浓度水平数量级是阴离子表面有机活性物质的1/10,其浓度水平高于英国诺威奇与爱丁堡,但低于马来西亚吉隆坡.      

Mechanism of OH-initiated atmospheric photooxidation of the organophosphorus insecticide (C2H5O)3PS

O,O,O-triethyl phosphorothioate ((C₂H₅O)₃PS, TEPT) is a widely used organophosphorus insecticide. TEPT may be released into the atmosphere where it can undergo transport and chemical transformations, which include reactions with OH radicals, NO₃ radicals and O₃. The mechanism of the atmospheric reactions of TEPT has not been fully understood due to the short-lifetime of its oxidized radical intermediates, and the extreme difficulty in detection of these species experimentally. In this work, we carried out molecular orbital theory calculations for the OH radical-initiated atmospheric photooxidation of TEPT. The profile of the potential energy surface was constructed, and the possible channels involved in the reaction are discussed. The theoretical study shows that OH addition to the PS bond and H abstractions from the CH₃CH₂O moiety are energetically favorable reaction pathways. The dominant products TEP and SO₂ arise from the secondary reactions, the reactions of OH-TEPT adducts with O₂. The experimentally uncertain dominant product with molecular weight 170 is mostly due to (C₂H₅O)₂P(S)OH and not (C₂H₅O)₂P(O)SH.     

Interactions of sulfuric acid with common atmospheric bases and organic acids: Thermodynamics and implications to new particle formation

Interactions of the three common atmospheric bases, dimethylamine ((CH₃)₂NH), methylamine (CH₃NH₂), ammonia (NH₃), all considered to be efficient stabilizers of binary clusters in the Earth's atmosphere, with H₂SO₄, the key atmospheric precursor, and 14 common atmospheric organic acids (COAs) (formic, acetic, oxalic, malonic, succinic, glutaric acid, adipic, benzoic, phenylacetic, pyruvic, maleic acid, malic, tartaric and pinonic acids) have been studied using the density functional theory (DFT) and composite high-accuracy G3MP2 method. The thermodynamic stability of mixed (COA)(H₂SO₄), (COA)(B1), (COA)(B2) and (COA)(B3) dimers and (COA)(H₂SO₄)(B1), (COA)(H₂SO₄)(B2) and (COA)(H₂SO₄)(B3) trimers, where B1, B2 and B3 refer to (CH₃)₂NH, CH₃NH₂ and NH₃, respectively, have been investigated and their impacts on the thermodynamic stability of clusters containing H₂SO₄ have been studied. Our investigation shows that interactions of H₂SO₄ with COA, (CH₃)₂NH, CH₃NH₂ and NH₃ lead to the formation of more stable mixed dimers and trimers than (H₂SO₄)₂ and (H₂SO₄)₂(base), respectively, and emphasize the importance of common organic species for early stages of atmospheric nucleation. We also show that although amines are generally confirmed to be more active than NH₃ as stabilizers of binary clusters, in some cases mixed trimers containing NH₃ are more stable thermodynamically than those containing CH₃NH₂. This study indicates an important role of COA, which coexist and interact with that H₂SO₄ and common atmospheric bases in the Earth atmosphere, in formation of stable pre-nucleation clusters and suggests that the impacts of COA on new particle formation (NPF) should be studied in further details.     

Mechanism and rate constants for complete series reactions of 19 fluorophenols with atomic H

Fluorine-containing halogenated fluorophenol may have efect as intermediate species involved in the formation of polyfluorinated dibenzo-p-dioxin/dibenzofurans(PFDDs/Fs). The mechanism for the atomic H initiated reactions with complete series of nineteen fluorophenol congeners was studies using the density functional theory. At the MPWB1K/6-31+G(d,p) level, the geometries and frequencies of reactants, transition states, and products were obtained, and the accurate energetic values were acquired at the MPWB1K/6-311+G(3df,2p) level. The rate constants were evaluated by the canonical variational transition-state theory with the small curvature tunneling contribution over a wide temperature range of 600–1000 K. The study shows that the intramolecular hydrogen-bond in the ortho-substituted FPs as well as the inductive efect of the electron-withdrawing fluorine and steric repulsion of multiple substitutions may ultimately be responsible for the relative strength of the O–H bonds in FPs. The results can be used for further studies on PFDD/Fs formation mechanism.