Nitrate-induced photodegradation of atenolol in aqueous solution: kinetics, toxicity and degradation pathways

The extensive utilization of β-blockers worldwide led to frequent detection in natural water. In this study the photolysis behavior of atenolol (ATL) and toxicity of its photodegradation products were investigated in the presence of nitrate ions. The results showed that ATL photodegradation followed pseudo-first-order kinetics upon simulated solar irradiation. The photodegradation was found to be dependent on nitrate concentration and increasing the nitrate from 0.5 mM L⁻¹ to 10 mM L⁻¹ led to the enhancement of rate constant from 0.00101 min⁻¹ to 0.00716 min⁻¹. Hydroxyl radical was determined to play a key role in the photolysis process by using isopropanol as molecular probe. Increasing the solution pH from 4.8 to 10.4, the photodegradation rate slightly decreased from 0.00246 min⁻¹ to 0.00195 min⁻¹, probably due to pH-dependent effect of nitrate-induced OH formation. Bicarbonate decreased the photodegradation of ATL in the presence of nitrate ions mainly through pH effect, while humic substance inhibited the photodegradation via both attenuating light and competing radicals. Upon irradiation for 240 min, only 10% reduction of total organic carbon (TOC) can be achieved in spite of 72% transformation rate of ATL, implying a majority of ATL transformed into intermediate products rather than complete mineralization. The main photoproducts of ATL were identified by using solid phase extraction-liquid chromatography-mass spectrometry (SPE-LC-MS) techniques and possible nitrate-induced photodegradation pathways were proposed. The toxicity of the phototransformation products was evaluated using aquatic species Daphnia magna, and the results revealed that photodegradation was an effective mechanism for ATL toxicity reduction in natural waters.     

水蒸气抑制甲烷燃烧和爆炸实验研究与数值计算

在爆炸激波管中对水蒸气抑制甲烷燃烧和爆炸进行较系统的实验研究,并对其抑燃、抑爆化学动力学作用机理进行数值计算分析。结果表明:加入一定量的水蒸气后,可以有效降低CH4-O2混合气体的燃烧速度和爆炸强度;当水蒸气量达到某临界值时,CH4-O2混合气体将不能被点燃。化学动力学数值计算结果表明:在混合气体中加入水蒸气后,增大了甲烷的点火延迟时间,降低了燃烧温度和H,O和OH等高活性自由基的浓度。水蒸气能有效抑制甲烷燃烧和爆炸,其作用效果源于其物理抑制和化学阻化的综合效应。     

镉对河南华溪蟹肝胰腺线粒体自由基代谢的影响

为了探明镉对线粒体自由基代谢的毒性机理,采用急性毒性实验方法,研究了不同浓度镉(Cd2+)对河南华溪蟹(Sinopotamon henanen肝胰腺组织线粒体抗超氧阴离子(O2.-)能力、抑制羟自由基(.OH)产生能力、过氧化氢(H2O2)和一氧化氮(NO)含量及一氧化氮合成(NOS)活力的影响.具体实验设置5个Cd2+浓度组(7.25、14.50、29.00、58.00和116.00mg.L-1),分别在24、48、72和96h时对自由基代的相关指标进行测定.结果显示,Cd2+对线粒体自由基代谢的影响表现出时间和浓度效应关系.随着Cd2+浓度的增加和处理时间的延长O2.-能力、抑制.OH产生能力逐渐降低,但H2O2含量逐渐增高,NO含量和NOS活力的变化基本趋于一致,即随着Cd2+浓度的增加和处理间的延长先上升后下降.因此,线粒体中抗O2.-和抑制.OH产生能力、H2O2和NO含量及NOS活力可以作为重金属污染水生生物毒性效应指示物.     

用自旋捕集技术研究氟化物刺激人多形核白细胞呼吸爆发产生的活性氧自由基

用ESR波谱研究证明,F^-刺激人多形核白细胞（PMN）呼吸爆发产生活性氧自由基（O₂^-和·OH）,同时消耗O₂.用DMPO自旋捕集技术表明,在高浓度F^-刺激下PMN产生DMPO-OOH加合物;在低浓度F^-刺激下则产生DMPO-OH;在适中浓度F^-刺激下PMN先产生DMPO-OOH,随浓度降低变为DMPO-OH.用超氧化物歧化酶和过氧化氢酶的实验确定氧自由基主要来自O₂^-.用CTPO和CrOX的自旋探针测氧法证明,PMN受F^-刺激产生氧自由基时消耗的O₂是细胞外介质中的O₂.     

硝酸根对水体中甲基汞光化学降解的影响

为研究硝酸根(NO3-)对水体中甲基汞(MMHg)光化学降解的影响,采用室内模拟试验,验证了不同波长光照条件下,NO3-在MMHg光化学反应中的作用,探讨了NO3-浓度对MMHg光解速率及产物的影响,并根据溶液中Hg2+的浓度分析了MMHg光解反应的进行程度.结果表明,在自然光(NL)和紫外光(UV)条件下,只加入了NO3-的处理MMHg光降解速率分别为0.10、0.046 L.(ng·h)-1,Hg0的释放通量分别为1.05、1.27 ng,Hg2+的最终浓度分别为16.97、28.92 ng·L-1;在未加入NO3-和加入了C6H5COOH的条件下,MMHg的剩余浓度相差不大,其光降解速率也分别在0.052、0.015 L.(ng·h)-1左右,Hg0的释放通量分别为23.81、15.38 ng,Hg2+的浓度均小于10 ng·L-1,且呈现先增加后减小趋势.在可见光(VL)照射下,各处理下MMHg的光降解速率无显著性差异(P=0.56),为0.003 L.(ng·h)-1左右,Hg0的释放通量均为5 ng左右,Hg2+的浓度未超过3 ng·L-1,也呈现出先增加后减小的趋势.在NL条件下,随浓度NO3-的增加,MMHg的光降解速率也增加,且各处理间存在显著性差异(P<0.05),Hg0的生成量随NO3-浓度的增加而减少,而Hg2+的浓度也随NO3-浓度的增加而增加.可见在有紫外光的条件下,NO3-对MMHg光降解反应历程、反应速率以及产物有重要影响.     

Effects of iron (hydr)oxides on the degradation of diethyl phthalate ester in heterogeneous (photo)-Fenton reactions

This work studied the structural effects of hematite(α-Fe2 O3), 2-line ferrihydrite(HFO) and goethite(α-FeOOH) on diethyl phthalate ester(DEP) degradation. The results showed that the degradation of DEP was faster under 365 nm light irradiation than in the dark in the presence of iron(hydr)oxides. The apparent kinetic rates of DEP degradation followed the order HFO goethite ≈ hematite in the dark and HFO hematite goethite under 365 nm light irradiation. Two pathways governed H2 O2 decomposition efficiency on iron(hydr)oxide surfaces:(1) forming UOH on inherent surface hydroxyl groups(Fe-OH) and(2) producing O2 and H2 O on the surface oxygen vacancies. X-ray photoelectron spectroscopy(XPS) analyses indicated that HFO not only has high Fe-OH content but also has high Vo content, resulting in its low H2 O2 utilization efficiency(η). DEP was degraded through hydrogen abstraction and deesterification, and the major products were(OH)2-DEP, mono-ethyl phthalate(MEP), OH-MEP,and phthalate acid(PA). The study is important in understanding the transformation of phthalate esters in top surface soils and surface waters under ultraviolet light.     

Seasonal variation characteristics of hydroxyl radical pollution and its potential formation mechanism during the daytime in Lanzhou

Hydroxyl free radicals (OH radicals) play the main role in atmospheric chemistry and their involving reactions are the dominant rate determining step in the formation of secondary fine particulate matter and in the removal of air pollutants from the atmosphere. In this paper, we studied the seasonal variation characteristics of OH radicals during the daytime in Lanzhou and explored the potential formation mechanism of high concentration OH radicals. We found that the OH radicals in four seasons was 2.7 × 10⁶, 2.6 × 10⁶, 3.1 × 10⁶, and 2.2 × 10⁶ cm^?3, respectively. Since the rainfall was concentrated in summer, the wet deposition had a significant effect on removing OH radicals. Among the four pollutants (including ozone (O₃), volatile organic compounds (VOCs), nitrogen dioxide (NO₂) and fine particulate matter (PM_2.5)), the variation of OH radicals were closely related to ozone concentration especially in spring and summer. In autumn, the correlation between PM_2.5 and OH radicals were the closest among the observing pollutants and its formation mechanism was different conventional regeneration pathway. In Event 1, high concentration of ozone was the main source of OH radicals; under the high humidity condition, except for ozone, the multiple factors including VOCs, NO₂ and PM_2.5 interplayed and leaded to the Event 2.     

2,4-二氯苯酚诱导鲫鱼肝脏自由基的产生和脂质过氧化

以α-苯基-N-叔丁基甲亚胺-N-氧化物(α-phenyl-N-tert-butylnitrone,PBN)为自旋捕获剂,利用电子顺磁共振(electronparamagnetic resonance,EPR)研究了2,4-二氯苯酚(2,4-dichlorophenol,2,4-DCP)腹腔注射24h后,引起鲫鱼(Carassius auratus)幼体肝脏内自由基含量变化.结果表明,不同剂量2,4-DCP(0.025,0.05,0.5,5,25 mg/kg)腹腔注射24h后可引起鲫鱼肝脏内自由基信号明显增强,与对照组相比具有显著性差异(p＜0.05).自由基的产生与2,4-DCP注射剂量呈较好的剂量-效应关系,回归方程为:y=1189ln(x)+9220,r²=0.9856.EPR波谱的3组双重峰分裂谱线为典型的PBN捕获羟自由基形成PBN/'OH的EPR波谱,经谱图解析表明,PBN捕获自由基形成加合物的超精细分裂常数aN=13.7 Gauss,aH=1.8Gauss,g因子为2.0058.与文献报道的PBN捕获羟自由基的特征参数一致.研究发现,2,4-DCP腹腔注射引起鲫鱼肝脏丙二醛(malondialdehyde,MDA)含量明显增加,与对照组相比有显著性差异(p＜0.05),并对2,4-DCP诱导鲫鱼肝脏自由基的产生与脂质过氧化的机理进行了探讨.     

降解偶氮染料AO7的研究：动力学及反应途径

紫外光分解过硫酸盐(S2O2-8)是一种新型的高级氧化技术,可以产生强氧化性的硫酸根自由基(SO-4).以偶氮染料AO7为目标污染物,重点研究了反应体系氧化剂K2S2O8浓度、溶液初始pH值和无机阴离子(H2PO-4、HCO-3、NO-3和Cl-)对反应体系的影响.结果表明,AO7的降解遵循准一级动力学,当AO7初始浓度为0.14 mmol/L时,最佳的氧化剂K2S2O8与污染物AO7的摩尔比为20.pH值对UV/K2S2O8体系降解AO7的反应速率影响较大,增大pH有利于SO-4转化为·OH.溶液中的无机离子对反应体系有一定的抑制作用.采用GC/MS分析了UV/K2S2O8体系降解AO7的主要中间产物(萘酚、1,2-苯并吡喃酮、邻苯二甲酸),并根据中间产物的分析推测了降解途径.     

高级氧化法氧化含邻硝基甲苯废水过程的动力学

研究了水溶液中邻硝基甲苯在有O3或O3／H2O2情况下的氧化反应过程，并建立了动力学模型。在293K、pH值3－10条件下对反应进行测定。实验结果表明，臭氧衰减速率对于O3来说反应级数为1，而对于邻硝基甲苯来说则随pH值变化和H2O3的有无而变化，实验结果与理论预测相吻合。