Chemical oxidation of sulfadiazine by the Fenton process: Kinetics,pathways, toxicity evaluation

This paper investigated sulfadiazine oxidation by the Fenton process under various reaction conditions. The reaction conditions tested in the experiments included the initial pH value of reaction solutions, and the dosages of ferrous ions and hydrogen peroxide. Under the reaction conditions with pH 3, 0.25 mM of ferrous ion and 2 mM of hydrogen peroxide, a removal efficiency of nearly 100% was achieved for sulfadiazine. A series of intermediate products including 4-OH-sulfadiazine/or 5-OH-sulfadiazine, 2-aminopyrimidine, sulfanilamide, formic acid, and oxalic acid were identified. Based on these products, the possible oxidation pathway of sulfadiazine by Fenton's reagent was proposed. The toxicity evaluation of reaction solutions showed increased antimicrobial effects following the Fenton oxidation process. The results from this study suggest that the Fenton oxidation process could remove sulfadiazine, but also increase solution toxicity due to the presence of more toxic products.     

中国工业园区低碳发展路径研究

中国政府承诺CO₂排放力争于2030年前达到峰值,努力争取2060年前实现碳中和。在工业部门深化应对气候变化和全面推进绿色转型的背景下,数量庞大的工业园区已然成为"十四五"乃至今后一个时期工业领域实现科学、精准碳减排的关键靶点。本研究首先剖析了中国工业园区低碳发展面临的挑战与机遇;进而以2015年为基准年,面向2035和2050年美丽中国建设两阶段战略目标,研究提出了工业园区碳减排的目标、路径和潜力,以期为园区深化低碳发展提供决策参考。研究显示,2015年中国工业园区CO₂排放总量约为28亿吨,占全国总排放量的31%。通过产业结构调整、能效提升、能源结构优化、碳捕集等低碳路径,2015-2050年全国园区预期可减排CO₂ 18亿吨,在2015年基础上减排60%以上;其中,2015-2035年减排8亿吨,2035-2050年减排10亿吨。     

低NOx环境异戊二烯促进甲苯生成甲基丁烯二醛的模拟实验

在低NO_x浓度条件下开展甲苯和异戊二烯复合体系的烟雾箱模拟实验,使用高时间分辨率的在线质子转移反应飞行时间质谱(PTR-TOF-MS)实时监测混合体系中反应物与产物的浓度变化情况,探究人为源与天然源交汇过程中, 自然源挥发性有机物 (BVOCs)对人为挥发性有机物(AVOCs)化学降解的影响.结果表明,异戊二烯与甲苯竞争OH自由基,从而抑制了甲苯的化学降解,该竞争反应开始得越早,抑制效果越显著.研究还发现异戊二烯会增强甲苯RO₂降解途径产物的产量,生成更多1,4不饱和-二羰基化合物(如丁烯二醛和甲基丁烯二醛)与二羰基化合物(如乙二醛和甲基乙二醛),其中甲基丁烯二醛增量最高可达38.6%.此外,异戊二烯快速氧化生成的RO₂自由基碳数更少,可能与甲苯氧化生成的RO₂自由基发生了快速的交叉反应,有利于甲苯RO自由基的生成及裂解,最终导致甲苯RO₂途径裂解产物的增加.     

Phenol degradation in waters with high iodide level by layered double hydroxide-peroxodisulfate: Pathways and products

Recently, layered double hydroxide-peroxodisulfate (LDH-PDS) as an advanced oxidation system can effectively remove organics by the pathway of free radical. However, little has been known if there is a potential risk regarding the formation of high toxic iodine byproducts through another pathway when LDH-PDS is used in high iodide waters at coastal areas. Therefore, this study investigated phenol degradation pathways and transformation products to evaluate both removal mechanism and potential risk by LDH-PDS in high iodide waters. The results showed that in LDH-PDS system, with the degradation of PDS, phenol degraded till below detection limit in 1 hr in the presence of iodide, while PDS and phenol were hardly degraded in the absence of iodide, indicating iodide accelerated the transformation of PDS and the degradation of phenol. What is more, it reached the highest phenol removal efficiency under the condition of 100 mg/L LDH, 0.1 mmol/L PDS and 1.0 mmol/L iodide. In LDH-PDS system, iodide was rapidly oxidized by the highly active interlayer PDS, resulting in the formation of reactive iodine including hypoiodic acid, iodine and triiodide instead of free radicals, which contributed rapid degradation of phenol. However, unfortunately toxic iodophenols were detected. Specifically, 2-iodophenol and 4-iodophenol were formed firstly, afterwards 2,4-diiodophenol and 2,6-diiodophenol were produced, and finally iodophenols and diiodophenols gradually decreased and 2,4,6-Triiodophenol were produced. These results indicated that LDH-PDS should avoid to use in high iodide waters to prevent toxic iodine byproduct formation although iodide can accelerate phenol degradation.     

电子束辐照降解水中氯霉素的研究

本研究对氯霉素(CAP)在不同条件下的电子束辐照降解进行了研究.结果表明,电子束辐照可有效去除水中CAP,低浓度CAP在酸性条件下的辐照降解更为显著,且降解过程符合准一级动力学模型.通过添加不同的自由基清除剂,发现HO·在CAP降解中起关键作用,此外,CAP分子也会吸收辐照而发生分解.水中共存的阴离子和腐殖酸(HA)对CAP辐照降解均有抑制作用,这跟其与HO·的反应速率常数大小有关,并且反应速率越大,其抑制能力越强.CAP在去离子水中的去除率高于其他实际水体,但辐照剂量为4 k Gy时,污水厂污水过滤水和胶体浓缩液中的CAP也可分别去除89.1%和81.7%.利用GC-MS检测到辐照后溶液中有6种中间产物,主要是通过脱水、不对称中心断键和脱酰胺作用形成.此外,IC检测有Cl-、NO-3和NO-2的产生,并且TOC在一定程度上降低,说明部分CAP被矿化.     

吸附模式对有机物光催化降解的影响2.H-酸在TiO2表面的光催化降解途径

水溶液中H-酸通过磺酸基团吸附在TiO2表面,UV照射TiO2所产生的自由基首先进攻吸附在TiO2表面的磺酸基团,从而进一步导致萘环开环.pH 2.5条件下,虽然饱和吸附量较大,但由于H-酸仅通过一个磺酸基团吸附在TiO2表面,过程中产生的硫酸根速率较慢,最终的光降解速率也较慢.pH 5.0条件下,虽然饱和吸附量较小,但由于吸附在TiO2表面的两个磺酸基团同时受到来自TiO2表面自由基的进攻,过程中产生的硫酸根速率较快,最终的光降解速率也较快.吸附模式的差异是导致H-酸在不同pH值条件下光催化降解途径和速率差异的关键因素.     

Heterogeneous photocatalytic degradation of diuron on zinc oxide: Influence of surface-dependent adsorption on kinetics, degradation pathway, and toxicity of intermediates

Heterogeneous photocatalytic reaction has been generally applied for degradation of toxic contaminants. Degradations of a compound using the same kind of catalyst that was synthesized differently are commonly found in literature. However, the reported degradation intermediates are normally inconsistent. This issue is especially important for the degradation of toxic compounds because intermediates may be more toxic than their parent compounds and understanding the reason is necessary if appropriate catalysts are to be designed. This work systematically compares the photocatalytic degradation of diuron, a toxic recalcitrant herbicide, on two forms of zinc oxide (ZnO), i.e., conventional particles with zinc- and oxygen-terminated polar surfaces as the dominating planes, and nanorods with mixed-terminated nonpolar surfaces. Experimental and theoretical results indicate that both the rate of reaction and the degradation pathway depend on the adsorption configuration of diuron onto the surface. Diuron molecules adsorb in different alignments on the two surfaces, contributing to the formation of different degradation intermediates. Both the aliphatic and aromatic sides of diuron adsorb on the polar surfaces simultaneously, leading to an attack by hydroxyl radicals from both ends. On the other hand, on the mixed-terminated surface, only the aliphatic part adsorbs and is degraded. The exposed surface is therefore the key factor controlling the degradation pathway. For diuron degradation on ZnO, a catalyst confined to mixed-terminated surfaces, i.e., ZnO nanorods, is more desirable, as it avoids the formation of intermediates with potent phytotoxicity and cytogenotoxicity.     

生物洗涤塔内产漆酶苯降解菌的分离鉴定及菌剂制备应用

从生物洗涤塔内循环洗涤液中分离鉴定得到3株苯降解菌Kocuria rosea sp. R(玫瑰色考克氏菌属)、Bacillus sp. W(芽孢杆菌属),以及Arthrobacter sp. Y(节杆菌属),通过研究其苯降解动力学,确定苯降解优势菌为Bacillus sp. W,优化其降解条件并探究其代谢途径。结果表明,添加皂角苷可促进苯的生物降解,但根据不同细菌的代谢特点,其影响存在显著差异。在产漆酶菌Bacillus sp. W的降解下,苯的半衰期为8.08 h,而皂角苷与苯共代谢时,苯的半衰期缩短为4.90 h。在最优条件下,即pH为7、起始苯浓度为50 mg·L⁻¹、皂角苷添加量为75 mg·L⁻¹,Bacillus sp. W的漆酶酶活最高为490.21 U·L⁻¹。在漆酶等参与下苯存在独特苯降解通路,苯在加氧酶作用下转化为邻苯二酚,漆酶可催化酚羟基邻位发生甲氧基取代,进而分子内加成为呋喃衍生物,再经一系列下游酶的作用降解成小分子。在生物反应器中添加由分离得到3株菌株复合而成的菌剂,苯去除效率在第5 d达最高81.21%,比常规驯化活性污泥提前了17 d,还增强了反应器的抗冲击能力。将菌剂接种到实验室的泡沫生物洗涤反应器中,实现了反应器快速启动,启动期仅为5 d。本研究可为生物技术治理疏水性和难降解性VOCs提供参考。     

过氧化氢/磷钼酸体系的催化机制及对苯胺的降解效果

以苯胺为目标污染物,通过苯胺的降解实验从3类6种过氧化氢催化剂中筛选出催化效果较好的杂多酸催化剂磷钼酸(PMA)。利用氧化还原电位测定法、电子顺磁共振波谱法、化学发光法以及拉曼光谱法分析了H₂O₂/PMA催化体系的催化机制,初步推测PMA催化H₂O₂生成高活性的[Mo(OO)₂]*和[Mo(OOH)₂]*中间体。同时,考察了PMA用量、pH以及苯胺与活性氧的摩尔比对苯胺降解效果的影响,获得了H₂O₂/PMA体系最佳反应条件。当H₂O₂和PMA质量分数分别为1%和0.365‰、溶液pH为4,在1 min内对4 mg·mL⁻¹苯胺的降解率可达98%以上。通过气相色谱质谱联用仪(GC/MS)、液相色谱质谱联用仪(LC/MS)和离子色谱(IC)等仪器分析方法检测确定苯胺的降解产物,推测其在H₂O₂/PMA催化体系的降解途径主要以N、C原子的氧化和聚合反应为主。     

Photodegradation of Hexafluoropropylene Oxide Trimer Acid under UV Irradiation

As a novel alternative to traditional perfluoroalkyl substances(PFASs), including perfluorooctanoic acid(PFOA) and perfluorooctane sulfonate(PFOS), hexafluoroproplyene oxide trimer acid(HFPO-TA) has been detected worldwide in surface water. Moreover, recent researches have demonstrated that HFPO-TA has stronger bioaccumulation potential and higher hepatotoxicity than PFOA. To treat these contaminants e.g. PFOA and PFOS, some photochemical techniques by adding exogenous substances had been report...