Effect of substituents in hydroxyl radical-mediated degradation of azo pyridone dyes: Theoretical approaches on the reaction mechanism

Understanding the degradation behavior of azo dyes in photocatalytic wastewater treatment is of fundamental and practical importance for their application in textile-processing and other coloration industries. In this study, quantum chemistry, as density functional theory, was used to elucidate different degradation pathways of azo pyridone dyes in a hydroxyl radical (HO^?)-initiated photocatalytic system. A series of substituted azo pyridone dyes were synthesized by changing the substituent group in the para position of the benzene moiety, ranging from strong electron-donating to strong electron-withdrawing groups. The effect of dye molecular structure on the photocatalytic degradation reaction mechanism was analyzed and quantification of substituent effects on the thermodynamic and kinetics parameters was performed. Potential energy surface analysis revealed the most susceptible reaction site for the HO^? attack. The calculated reaction barriers are found to be strongly affected by the nature of substituent group with a good correlation using Hammett σ_p constants and experimentally determined reaction rates. The stability of pre-reaction complexes and transition state complexes were analyzed applying the distortion-interaction model. The increased stability of the transition state complexes with the distancing from the substituent group has been established.     

Reactive uptake of NO2 on volcanic particles: A possible source of HONO in the atmosphere

The heterogeneous degradation of nitrogen dioxide (NO₂) on five samples of natural Icelandic volcanic particles has been investigated. Laboratory experiments were carried out under simulated atmospheric conditions using a coated wall flow tube (CWFT). The CWFT reactor was coupled to a blue light nitrogen oxides analyzer (NO_x analyzer), and a long path absorption photometer (LOPAP) to monitor in real time the concentrations of NO₂, NO and HONO, respectively. Under dark and ambient relative humidity conditions, the steady state uptake coefficients of NO₂ varied significantly between the volcanic samples probably due to differences in magma composition and morphological variation related with the density of surface OH groups. The irradiation of the surface with simulated sunlight enhanced the uptake coefficients by a factor of three indicating that photo-induced processes on the surface of the dust occur. Furthermore, the product yields of NO and HONO were determined under both dark and simulated sunlight conditions. The relative humidity was found to influence the distribution of gaseous products, promoting the formation of gaseous HONO. A detailed reaction mechanism is proposed that supports our experimental observations. Regarding the atmospheric implications, our results suggest that the NO₂ degradation on volcanic particles and the corresponding formation of HONO is expected to be significant during volcanic dust storms or after a volcanic eruption.     

短期干旱胁迫对马尾松排放挥发性有机物的影响

为探究干旱环境对BVOCs排放的影响,应用动态封闭式采样系统和热脱附-气相色谱-飞行质谱仪,对短期干旱胁迫作用下马尾松的BVOCs排放进行了实验室测量,定量分析BVOCs排放速率和排放组成的变化.结果表明,干旱胁迫时异戊二烯的排放受到抑制,排放速率降低约50%;单萜烯和倍半萜烯的排放水平增强,排放速率分别为137.85和0.98μg/（m²·h）,是未受胁迫时的2.9和2.0倍.除反式-α-香柠檬烯外,干旱胁迫促进各单萜烯和倍半萜烯化合物的排放,是未受胁迫时的1.3~42.4倍,其中3-蒈烯排放的响应最敏感,α-葑烯、α-水芹烯和石竹烯的响应最弱.干旱胁迫时单萜烯和倍半萜烯的排放组成有所变化,但主导的化合物种类不变,单萜烯以α-蒎烯、香桧烯和β-蒎烯为主,占比分别为48%、17%和17%;倍半萜烯以石竹烯和长叶烯为主,占比分别为57%和34%.     

Mercury levels in human population from a mining district in Western Colombia

A biomonitoring study was carried out to examine the adverse impacts of total mercury in the blood(HgB), urine(Hg U) and human scalp hair(HgH) on the residents of a mining district in Colombia. Representative biological samples(scalp hair, urine and blood) were collected from volunteered participants(n = 63) to estimate the exposure levels of THg using a Direct mercury analyzer. The geometric mean of THg concentrations in the hair,urine and blood of males were 15.98 μg/g, 23.89 μg/L and 11.29 μg/L respectively, whereas the females presented values of 8.55 μg/g, 5.37 μg/L and 8.80 μg/L. Chronic urinary Hg(HgU)levels observed in male workers(32.53 μg/L) are attributed to their long termed exposures to inorganic and metallic mercury from gold panning activities. On an average, the levels of THg are increasing from blood(10.05 μg/L) to hair(12.27 μg/g) to urine(14.63 μg/L).Significant positive correlation was found between hair and blood urinary levels in both male and female individuals. Thus the present biomonitoring investigation to evaluate the Hg levels and associated health issues would positively form a framework for further developmental plans and policies in building an ecofriendly ecosystem.     

用广义λ—分布拟合空气污染数据

广义λ-分布是一个四参数可变通的概率模型,包括多种单变量分布,这一模型可用于表示空气污染浓度的频率分布。本文采用土耳其安卡拉每日的烟和SO_2监测数据,来证明广义λ-分布具有良好的拟合性质。这里还讨论了与分位数估计和拟合优度有关的一些结果,并与经典对数正态分布进行了比较。     

地球化学

<正> 无论从空间无线电光谱、遥感来考虑,还是从检测晶体表面少数原子来看,地球化学技术在灵敏度和显示器方面都有很大的改进。随着技术的改进,新的认识层出不穷。地球化学令人向往的领域,仍然包括宇宙空间中元素和天体起源的经典范围,但是,地球化学新技术对于我们了解当前环境的紧迫问题,已是必不可少的了。地球化学家仍然是分析化学的先导。本文只举几个事件。     

煤转化废水可处理性能的评价

引言大多数煤转化工艺都含有或设计有好氧生物处理,以作为从工艺废水中去除酚和其它有机杂质的主要方法。但是,在这些其它的有机物质中,有一些迄今连种类和生物可降解性都不清楚,所以也不能确切地予断它们能被生物处理法去除到何种程度。而实际废水的复杂性所导致的协合作用和对抗作用更是千变万化,不可捉摸。因为生物处理法在最佳运行状态下,具     

关于斜长岩体成因的理论

这里提出各种斜长岩体,均由安山岩岩浆或玄武岩岩浆在粒变岩的变质条件下,经结晶和分离作用所形成。对于任何一个单独的岩体,其母岩浆的类型可以通过检验伴生岩石类型的垂直层序来确定。     

坦桑尼亚霞水母章鱼(Octopus cyanea Gray)的个体渔业

2000年4月期间坦桑尼亚霞水母章鱼(1849)个体渔业的初步结果到2001年6月才被提供.对在坦噶、马菲亚岛和姆特瓦拉三地的2546个单个渔获物和15 473个样品进行了分析.     

厦门港和员当湖表层沉积物中的石油烃和多环芳香烃

2002年4月厦门港沿岸设9个站，员当湖设两个站采集表层沉积物，用有机溶剂萃取，硅胶柱色层分离，气相色谱—质谱联机带SIM数据采集系统对样品的石油烃类(M／Z=55)，多环芳香烃类进行分析，结果显示员当湖石油烃和多环芳香烃质量分数分别高达1397和1376．5ng／g。厦门港船只活动，厦门港四周工业废水、车辆燃油滴漏是石油烃和多环芳香烃污染的主要来源。