温和预氧化提高后续生物修复石油污染土壤

为得到一种能促进后期生物阶段高效降解石油烃(TPH)的温和Fenton预氧化方式,本文考察了不同Fenton预氧化过程中羟基自由基(·OH)特征、后续生物修复过程中营养消耗、土著菌活性(CO_2)以及TPH去除量的差异,结果表明,温和Fenton预氧化组(·OH存在时间:73 h;双氧水浓度:225 mmol·L~(-1))中·OH存在时间短H_2O_2用量少,残余细菌活性高,后续对石油的生物降解率高,不加菌就能够达到与加菌相同的修复效果(TPH去除率38%左右).且在不加菌的条件下,后期生物阶段TPH去除率,温和预氧化组(38%)要高于普通预氧化组(15. 32%～33. 15%).进一步分析各链烃的去除效果,发现在后续生物修复阶段,温和预氧化组能减少对链烃组分(C17～C21)的抑制;而对比各组的土著菌活性,发现温和预氧化可以适当刺激土著微生物生长并提高其活性,这些因素均有利于TPH的去除.温和预氧化在后期生物修复阶段对TPH的去除不加菌就能够达到与加菌相同的处理效果,是一种低成本可行的修复方式.     

Cu2+强化UV活化过氧乙酸降解水中的双氯芬酸

研究了Cu²⁺强化UV活化过氧乙酸（Cu²⁺/UV/PAA）对水中双氯芬酸（DCF）的降解,考察了pH值、PAA投加量、Cu²⁺投加量、无机阴离子（Cl^-、SO₄^2-、NO₃^-和CO₃^2-）和溶解有机物（DOM）对DCF去除的影响;探讨了DCF在该体系中的降解产物和转化机理.结果表明：UV和Cu²⁺都能活化PAA产生活性自由基促进DCF降解.DCF在Cu²⁺/UV/PAA中的降解遵循准一级动力学,其降解可能归因于直接光解、HO^·氧化和CH₃COO^·、CH₃COOO^·等其它自由基氧化.在pH=3~11范围内,DCF降解的最佳pH=8.5.DCF的降解效率随着PAA投加量的增大而逐渐增高,过量的PAA能与DCF竞争HO^·.Cu²⁺用量的提高也能促进DCF的去除,但是过量的Cu²⁺可生成Cu（OH）₂导致其催化能力下降.由于NO₃^-在UV照射下可以产生HO^·,其对DCF降解有促进作用,且NO₃^-浓度越高,促进作用越明显.不同浓度的Cl^-、SO₄^2-、CO₃^2-和DOM对DCF降解影响较小.在Cu²⁺/UV/PAA降解DCF的过程中,共检测出13种降解产物.根据这些降解产物,提出了DCF可能的转化机理,包括8种不同的反应路径.     

光照下铜离子对水中氢氧自由基生成量的影响

研究了水溶液中铜离子与抗坏血酸、柠檬酸盐及藻等配合体系在高压汞灯光照下产生氢氧自由基的情况,其中铜与抗坏血酸系统反应最强,高压汞灯光照增强了铜与抗坏血酸反应产生氢氧自由基的过程,高压汞灯光照时所产生的自由基量为不光照时的6～7倍。同时铜(或抗坏血酸)单一的水溶液在光照条件下也能产生氢氧自由基。铜离子与柠檬酸钠溶液混合在光照下能产生氢氧自由基;铜离子与藻液混合能加倍藻液中氢氧自由基的产生。     

广州大气中羰基化合物特征

在广州选择不同的区研究了广州大气中羰基化合物的浓度水平,分布特征及来源。广州大气中羰基化合物的浓度在城区不同的采样地点,不同的采样时间变化不大;浓度水平与世界上其他污染比较严重的几个城市相当。利用文献中羰基化合物与.OH的反应常数,计算出在广州大气中羰基化合物对.OH消除贡献。     

水体中常见无机阴离子对TiO_2薄膜光催化还原Cr(Ⅵ)的影响

选择了5种水体中常见的阴离子(Cl~-,SO_4~(2-),HCO_3~-,NO_3~-以及HPO_4~(2-)/H_2P_4~-),分别考察了其对TiO_2薄膜光催化还原模拟Cr(Ⅵ)废水的影响.从上述离子的光吸收,对·OH的捕获作用以及与Cr(Ⅵ)的竞争吸附三个方面讨论了上述离子影响TiO_2薄膜光催化还原Cr(Ⅵ)速率的原因.结果表明,体系酸性越强,越有利于Cr(Ⅵ)的还原;在pH值约为6时,HCO_3~-,Cl~-和SO_4~(2-)对TiO_2薄膜光催化还原Cr(Ⅵ)具有促进作用,NO_3~-具有抑制作用,H_2PO_4~-/HPO_4~(2-)在低浓度时具有促进作用,而在高浓度时具有抑制作用.造成上述结果的主要原因是Cl~-,SO_4~(2-)和HCO_3~-具有较强的·OH捕获作用和在TiO_2表面较低的吸附能力;H_2PO_4~-/HPO_4~(2-)在TiO_2表面具有较强的吸附能力;NO_3~-对紫外光吸收作用降低了TiO_2表面的紫外光强度以及自身光化学反应产生了·OH.     

水中羟基氧化铁催化臭氧分解和氧化痕量硝基苯的机理探讨

测定了木质颗粒活性炭(GAC)和负载在GAC上的羟基氧化铁(FeOOH)催化水中臭氧分解的速率常数并探讨了催化臭氧分解的途径.以水中几种氧化物表面羟基密度和表面零电荷pH值(pH_zpc)为表征氧化物表面性质的参数,考察了2个参数对催化臭氧氧化水中硝基苯的影响.GAC和负载在GAC上的FeOOH使水中臭氧一级分解速率常数分别提高了68%和108%,用叔丁醇捕获掉生成的羟基自由基后,前者的分解速率常数降低了9%,后者降低了20%.GAC在催化臭氧分解时主要起到吸附剂和还原剂的作用,FeOOH催化臭氧分解过程中促进了羟基自由基生成.氧化物表面羟基密度和催化臭氧氧化水中硝基苯的效果之间没有直接的关系,由氧化物的pH_zpc决定的表面电荷状态与催化氧化效果有关,表面接近电中性时对催化氧化硝基苯有利.高密度的表面羟基会使表面羟基之间形成较强的氢键,使催化作用减弱.     

天然水体腐殖质对双酚A光降解影响的研究

以中压汞灯模拟太阳光光源,研究了双酚A(BPA)在水体腐殖质中的光降解过程,探讨了不同来源的腐殖质、腐殖质浓度、BPA初始浓度、溶解氧等因素对BPA光解速率的影响,实验结果表明,BPA在纯水体系中直接光解很慢,但在腐殖质溶液中光解迅速,符合拟一级动力学反应,改变BPA初始浓度对BPA光解速率的影响不明显,增大溶解氧浓度会抑制BPA光解,通过活性氧分子探针鉴定了腐殖质吸收光辐射产生的羟基与单线态氧,利用GC-MS鉴定了双酚A在Nordic湖富里酸(NOFA)中的光敏化降解产物,推测出BPA敏化降解的可能历程为能量转移导致的直接光解、羟基加成和羟基氧化。     

Experimental investigation on extinguishing performance of a novel nanocomposite for gaseous fires

A novel nanocomposite was synthesized by incorporating three different types of flame-retardants and its extinguishing performance was tested for gaseous fires. The nanocomposite consists of the inorganic magnesium hydroxide (MH) nanoparticles as the dominant component, the nitrogen-based melamine cyanurate (MCA), and the phosphorus-based ODOPB. The wet mixing, dry mixing, and ultrasonic agitation were employed in the preparation process to enhance the homogeneity of the nanocomposite. The prepared powders were characterized using a series of analytical instruments including X-ray diffraction (XRD), scanning electron microscopy (SEM), thermal gravity analyzer (TGA), and differential scanning calorimeter (DSC). The efficiency of various samples in extinguishing gaseous fires was investigated in a lab-scale extinguishing system. The fire extinguishing tests indicated that the nanocomposite is considerably more effective in fire extinguishing than other powders in terms of extinction time and agent mass consumed. The fire extinction time of nanocomposite was 45.2% shorter than that of commercial ABC-MAP powder. Furthermore, the consumed amount of nanocomposite was 63.2% less than that of commercial powder. In addition, the order of extinguishing mass concentrations was as follows: the novel nanocomposite (103.7 g/m³) < MH/MCA (148.1 g/m³) < MH/ODOPB (155.6 g/m³) < MH (170.4 g/m³) < commercial ABC powder (281.5 g/m³) < MCA/ODOPB (384.1 g/m³). The fire suppression mechanisms of the nanocomposite were also discussed. It was inferred that the extinguishing mechanism of nanocomposite comprised of simultaneous chemical and physical inhibition actions involving chemical inhibition action, cooling action, and asphyxiation action. This study provides a promising attempt to gain benefits from the striking features of nanotechnology and flame-retardants in extinguishing gaseous fires.     

Persistent free radicals in humin under redox conditions and their impact in transforming polycyclic aromatic hydrocarbons

• Regulation of redox conditions promotes the generation of free radicals on HM. • HM-PFRs can be fractionated into active and inactive types depending on stability. • The newly produced PFRs readily release electrons to oxygen and generate ROS. • PFR-induced ROS mediate the transformation of organic contaminants adsorbed on HM. The role of humic substance-associated persistent free radicals (PFRs) in the fate of organic contaminants under various redox conditions remains unknown. This study examined the characterization of original metal-free peat humin (HM), and HM treated with varying concentrations of H₂O₂ and L-ascorbic acid (VC) (assigned as H₂O₂-HM and VC-HM). The concentration of PFRs in HM increased with the addition of VC/H₂O₂ at concentrations less than 0.08 M. The evolution of PFRs in HM under different environmental conditions (e.g., oxic/anoxic and humidity) was investigated. Two types of PFRs were detected in HM: a relatively stable radical existed in the original sample, and the other type, which was generated by redox treatments, was relatively unstable. The spin densities of VC/H₂O₂-HM readily returned to the original value under relatively high humidity and oxic conditions. During this process, the HM-associated “unstable” free radicals released an electron to O₂, inducing the formation of reactive oxygen species (ROS, i.e., ^•OH and ^•O₂⁻). The generated ROS promoted the degradation of polycyclic aromatic hydrocarbons based on the radical quenching measurements. The transformation rates followed the order naphthalene>phenanthrene>anthracene>benzo[a]pyrene. Our results provide valuable insight into the HM-induced transformation of organic contaminants under natural conditions.     

Pathway of the ozonation of 2,4,6-trichlorophenol in aqueous solution

The reaction mechanism and pathway of the ozonation of 2,4,6-trichlorophenol (2,4,6-TCP) in aqueous solution were investigated. The removal efficiency and the variation of H₂O₂, Cl⁻ formic acid, and oxalic acid were studied during the semi-batch ozonation experiments (continuous for ozone gas supply, fixed volume of water sample). The results showed that when there was no scavenger, the removal efficiency of 0.1 mmol/L 2,4,6-TCP could reach 99% within 6 min by adding 24 mg/L ozone. The reaction of molecular ozone with 2,4,6-TCP resulted in the formation of H₂O₂. The maximal concentration of H₂O₂ detected during the ozonation could reach 22.5% of the original concentration of 2,4,6-TCP. The reaction of ozone with H₂O₂ resulted in the generation of a lot of OH• radicals. Therefore, 2,4,6-TCP was degraded to formic acid and oxalic acid by ozone and OH• radicals together. With the inhibition of OH• radicals, ozone molecule firstly degraded 2,4,6-TCP to form chlorinated quinone, which was subsequently oxidized to formic acid and oxalic acid. Two reaction pathways of the degradation of 2,4,6-TCP by ozone and O₃/OH• were proposed in this study. Translated from Acta Scientiae Circumstantiae, 2005, 25(12): 1619–1623 [译自: 环境科学学报]