Potential CFC replacements: Tropospheric lifetimes of C3 hydrofluorocarbons and hydrofluoroethers

Attack by tropospheric hydroxyl radicals results in much shorter residence times for hydrofluorocarbons (HFCs) than for the fully halogenated chlorofluorocarbons (CFCs). Empirical structure-activity relations, previously calibrated for HFCs containing two carbon atoms, are used with semi-empirical and ab initio calculations to provide realistic first estimates of tropospheric lifetimes of various chlorine-free HFCs and hydrofluoroethers (HFEs) containing three carbon atoms. The heavily fluorinated HFEs are of particular interest in that they are likely to possess thermophysical properties which are suited to a range of applications for which CFCs are currently employed. Many of the HFEs are predicted to have shorter lifetimes than HFC-134a (CF₃CH₂F), which is already in large-scale commercial production as an alternative refrigerant. Factors are identified which appear to favour short lifetimes for HFEs.     

Evaluation of ozone-alkylpyridine reaction kinetics using spectroscopic measurements

Rate constants for bimolecular reactions between ozone and a group of alkylpyridines were estimated by application of a pseudo-first-order technique involving time-course monitoring of reactor contents. The method used was a modification of an existing protocol for evaluation of gas-phase reaction kinetics. Reaction progress was followed spectroscopically. The method was found to be inadequate for accurate determination of kinetic parameters due to absorptive interferences; however, it was sufficient for defining lower limits of reaction rate constants. Tropospheric reactions of alkylpyridines with ozone were found to be extremely slow, with atmospheric lifetimes of the order of years.     

溴代烷烃的臭氧消耗潜势值的计算

溴代烷烃是破坏臭氧层很重要的一类物质,为了估计臭氧消耗潜势（ＯＤＰ）值,利用流动放电共振荧光技术测定ＣＨ３Ｂｒ和ＣＨ２Ｂｒ２与ＯＨ自由基反应速率常数,计算出它们在大气中的寿命;用半经验的方法,采用最新文献报道的有关数据,计算出ＣＨ３Ｂｒ和ＣＨ２Ｂｒ２的ＯＤＰ值分别为０．３３和０．０７６．并与文献结果进行了比较．     

典型生物质燃烧排放酚类有机物的大气液相氧化动力学

生物质燃烧排放有机物是大气二次有机气溶胶(SOA)的重要前体物,但相关反应参数仍较为匮乏。选择其中4种代表性物质,间苯二酚(RES)、4-乙基苯酚(4-EP)、丁香酚(Eug)和2,4,6-三甲基苯酚(Trmp),利用相对速率法测定了其与·OH在液相(云雾条件)中的二级反应动力学参数,并估算了其在实际大气条件下的液相反应寿命。在pH=5.4,T=298 K条件下,测定以上4种前体物液相氧化的二级动力学常数(K)分别为(7.68±0.04)×109,(18.12±0.56)×109,(23.11±0.60)×109,(16.90±0.58)×109 L/(mol·s),所得到的K值不确定性为3.5%~12%。此外,还测定了体系在T=293,288 K时的K值,发现288 K时的K值比298 K时的低了22%~38%,说明温度对于酚类液相反应的双分子速率常数有一定影响。研究还发现,反应过程中前体物浓度为初始值1/2时,pH降低,说明反应过程中可能生成一定量的有机酸;这些化合物在不同情境下使用CAPRAM 3.0多相机制计算得到的大气寿命在数十秒到数十小时之间,进一步说明生物质燃烧排放酚类化合物对SOA的生成贡献值得重视。     

相对速率法测量氯原子与几种酮类物质的反应速率常数

在(298±2) K和一个大气压条件下,采用相对速率法研究了一系列酮类物质与氯原子的反应动力学.使用丙醛和乙苯作为参比物,光解三氯乙酰氯作为氯原子产生源,测得2-己酮与氯原子的反应速率常数为(1.80±0.42)×10~(-10) cm~3·molecule~(-1)·s~(-1),与已有文献报道值非常符合,验证了实验方法和所选参比物的可靠性.首次测得了(298±2) K和一个大气压条件下2-庚酮和2-辛酮与氯原子反应的速率常数,分别为(2.54±0.62)×10~(-10)和(2.12±0.63)×10~(-10) cm~3·molecule~(-1)·s~(-1).与其母体烷烃的反应速率对比发现,酮类物质中羰基的存在使得其反应速率都比其母体烷烃变慢.利用所测的速率常数和氯原子的浓度信息估算这些酮类物质在大气中的平均寿命,结果显示,在海洋边界层或沿海地区等氯原子浓度较高的地区,这些物质与氯原子反应的大气化学寿命都在小时量级,完全可以与OH自由基的反应相竞争,是这些物质在大气中的重要降解途径.另外,在内陆污染地区或工业聚集区,氯原子的反应及其对二次污染物生成的贡献同样不能忽视.     

A detailed mechanism for the gas-phase atmospheric reactions of organic compounds

A gas-phase reaction mechanism for the atmospheric photooxidations of over 100 alkanes, alkenes, aromatic hydrocarbons, alcohols, ethers and other compounds representative of the range of reactive organics emitted into polluted atmospheres is described. Most of these organic species are represented using generalized reactions with variable rate constants and product yield coefficients for which individual assignments were made or estimated. This mechanism employs 19 species to repsent the reactive oxygenated and organic nitrate products, and includes the gas-phase reactions of SO₂, but does not include heterogeneous or liquid-phase reactions. The evaluation of this mechanisms, by comparison of its predictions against the results over 500 environmental chamber experiments, described in a separate paper. This detailed mechanism can be used in assessments of relative atmospheric reactivities of organic compounds, and can provide the basis for the derivation of more condensed mechanisms for use in air quality simulation models.     

江河中有机污染物在鲤鱼体内富集与释放的模拟研究

以第二松花江重点有机污染物硝基芳烃为研究对象,用改进的双膜理论预测了７种硝基芳烃的挥发速率常数,快速测定了它们在鱼体内的富集与释放速率常数,用获得的参数及二室模型预测这７种化合物的鱼体内的迁移过程,并与模拟实验测定的结果进行比较,得到了比较满意的结果。     

NO3自由基与3种环醚的大气化学反应动力学研究

在自制的大气反应烟雾箱模拟实验装置中,利用相对速率法研究了3种工业常用溶剂四氢呋喃、1,3-二氧五环、1,4-二氧六环与NO3自由基在298 K±1 K和1.01×105 Pa条件下的反应,目的是通过了解这些挥发性有机化合物（volatile organiccompounds,VOCs）在大气中的降解反应动力学来评估这些化合物对环境可能造成的影响.利用配有氢火焰离子化检测器（FID）的气相色谱（GC）检测反应物浓度变化,测得NO3自由基与四氢呋喃的反应速率常数为（5.36±1.93）×10-15cm3·（molecule·s）-1,与文献报道值在误差范围内非常吻合,验证了实验装置和实验方法的可靠性.实验首次测定了298 K±1K和1.01×105 Pa条件下1,3-二氧五环以及1,4-二氧六环与NO3自由基反应的速率常数,分别为（1.84±0.70）×10-15cm3·（molecule·s）-1和（3.20±0.67）×10-16 cm3.（molecule·s）-1.利用所测反应速率常数估算这些化合物在大气中的平均寿命都在1 d甚至十几d,因此,其排放可能会对区域大气环境产生一定的影响.     

rGO@nZVI-BC修饰的PRB增强糖皮质激素还原转化性能研究

为制备环境功能材料rGO@nZVI-BC,以此材料构建可渗透反应墙(PRB)实现对地下水中含氟糖皮质激素(FGCs)的有效阻控.结果表明,阻控过程可用改进Yoon-Nelson模型描述,在rGO@nZVI-BC和土壤系统中吸附速率和生物降解速率常数分别为0.485和0.035d^-1、0.233和0.029d^-1.提升阻控效能的主要机理是强化吸附和生物降解功能.其中运行初期以吸附作用占主导,贡献比为76.12%左右.生物强化机制主要为nZVI为GCs还原提供了电子供体,从而增强了还原脱氟功能,该部分贡献比约为87.06%,并伴随着脱羟基、氧化侧链降解和开环等降解.此外具有还原性脱卤属的功能性微生物(Xanthomonadaceae,Desulfuromonas和Sphingomonadaceae)物种丰度的增加进一步索证了功能材料rGO@nZVI-BC的效能.本研究为地下水中GCs的污染阻控提供了一种有效的方法.     

Polynuclear aromatic hydrocarbon degradation by heterogeneous reactions with N2O5 on atmospheric particles

The degradation of particulate polynuclear aromatic hydrocarbons (PAH) on atmospheric soot particles in the presence of gas phase dinitrogen pentoxide (N₂O₅) was explored. Dilute diesel and wood soot particles containing PAH were reacted with∼10ppm of N₂O₅ in a 200 ℓ continuous stirred tank reactor (CSTR). To provide a stable source of particles for reaction in the CSTR, diesel or wood soot particles were injected at night into a 25 m³ Teflon outdoor chamber. The large chamber served as a reservoir for the feed aerosol, and the aerosol could then be introduced at a constant flow rate into the CSTR. PAH-N₂O₅ heterogeneous rate constants for wood soot at 15°C ranged from2 × 10⁻¹⁸to5 × 10⁻¹⁸ cm³ molecules⁻¹ s⁻¹. For diesel soot the rate constants at 16°C were higher and ranged from5 × 10⁻¹⁸to30 × 10⁻¹⁸ cm³ molecules⁻¹ s⁻¹. Comparisons with other studies suggest that sunlight is the most important factor which influences PAH decay. This is followed by ozone, NO₂, N₂O₅ and nitric acid. The rate constants of nitro-PAH formation from a parent PAH and N₂O₅ were of the order of1 × 10⁻¹⁹−1 × 10⁻¹⁸ molecules⁻¹s⁻¹. The uncertainty associated with all of these rate constants is± a factor of 3. Given, however, the small magnitude of the rate constants and the low levels of N₂O₅ present in the atmosphere, we concluded that PAH heterogeneous reactions with gas phase N₂O₅ degrade particle-bound PAH or to form nitro-PAH from PAH arenot very important. (Direct application of the specific rate constants derived in this study to ambient atmospheres should not be undertaken unless the ambient particle size distributions and chemical composition of the particles are similar to the ones reported in this study.)     

全氟和多氟烷基类化合物(PFASs)的环境转化与分类管控

全氟和多氟烷基类化合物(per- and polyfluoroalkyl substances, PFASs)具有环境持久性、生物累积性和生物毒性(PBT),其暴露所引发的环境与健康风险已在世界范围内引起关注. 近期,有学者提议将PFASs作为一类高持久性物质进行全面管控,并淘汰PFASs的所有非必要用途. 鉴于PFASs在工业领域的不可或缺性,加快PFASs的淘汰进程势必会对社会和经济产生较大影响. 因此,淘汰PFASs需要一个漫长的过渡期. 在这期间,亟需开展积极有效的应对措施,最大程度地将PFASs暴露对生态环境乃至人体健康产生的潜在危害降到最低. 笔者认为加强PFASs的降解转化研究是目前较为有效且可行的策略之一,这将有助于理解PFASs的PBT特性,进而推动PFASs的分类管理. 笔者提出可在“疑似靶向/非靶向高分辨率质谱技术开发”“PFASs的传递、积累、代谢和消除行为”和“PFASs转化产物与不良健康影响之间关系的系统毒理学网络”等方面开展PFASs的降解转化研究. 通过高效筛查识别PFASs的分子转化机制,解析转化产物的PBT性质,进而对PFASs进行合理归类划分,并为制定PFASs及替代品的分类管控决策提供依据.      

氟代有机物的环境影响及其降解

氟代有机物应用日益广泛。其环境影响也逐渐引起人们的关注。本文综述了几类氟代有机物的环境影响和降解途径。氯氟烃破坏臭氧层，其替代物氢氯氟烃和氢氟烃却被认为可加重温室效应。两类物质分别在同温层和对流层氧化降解。不挥发性氟代有机物中全氟有机物难脱氟降解，但并非生物惰性。     

分子连接性指数法预测多氯联苯醚(PCDEs)的理化性质

通过计算多氯联苯醚(PCDEs)所有209种可能分子结构的分子连接性指数,以106种PCDEs理化性质的实验值为建模样本,建立并优选了PCDEs的饱和蒸气压(PO_L)、水溶解度(S_w)和正辛醇/水分配系数(K_ow)的定量结构--性质相关(QSPR)方程,检验结果表明方程相关性显著.在此基础上对其余103种文献中尚未报道实验值的PCDEs的上述参数进行了预测.利用得到的预测值,进一步给出了另外3种理化性质--亨利常数(H)、空气/水分配系数(K_gw)、空气/正辛醇分配系数(K_go)的计算结果.      

Mechanism and kinetics study on the ozonolysis reaction of 2,3,7,8-TCDD in the atmosphere

The ozonolysis of 2,3,7,8-tetra-chlorodibenzo-p-dioxin(2,3,7,8-TCDD) is an efcient degradation way in the atmosphere. The ozonolysis process and possible reactions path of Criegee Intermediates with NO and H2 O are introduced in detail at the method of MPWB1K/6-31+G(d,p)//MPWB1K/6-311+G(3df,2p) level. In ozonolysis, H2O is an important source of OH radical formation and initiated the subsequent degradation reaction. The Rice-Ramsperger-Kassel-Marcus(RRKM) theory was applied to calculate rate constants with the temperature ranging from 200 to 600 K. The rate constant of reaction between 2,3,7,8-TCDD and O3 is 4.80 × 10 20cm3/(mole·sec) at 298 K and 760 Torr. The atmospheric lifetime of the reaction species was estimated according to rate constants, which is helpful for the atmospheric model study on the degradation and risk assessment of dioxin.     

十溴联苯醚的环境降解行为研究进展

Deca-BDEs(十溴联苯醚)可在光照、微生物作用、高温下通过降解脱溴转变为毒性更强的低溴系联苯醚. BDE209是Deca-BDEs的主要成分,研究BDE209的环境降解行为对确定环境中低溴系联苯醚的来源进而消除其对环境的污染具有重要意义. 已有研究从BDE209降解机理向分析不同光源、不同降解阶段的降解产物推进,并以探求快速、有效的处置技术为出发点,对影响BDE209降解行为的辐照光强、有机溶剂的种类、固相介质等相关因素进行实验室模拟和对比分析,研究结果表明,太阳光照下BDE209的降解速率小于紫外光源,降解程度也低于紫外光源,二者的降解产物也有所不同. 光降解是Deca-BDEs在环境中转化的最主要途径,现有研究揭示了BDE209的光降解反应遵循准一级反应,表明其主要是一个逐级脱溴的过程,最终降解产物中含有大量的低溴系同系物,但鲜见对光解反应过程中潜在的一系列降解步骤及全面的光降解机理的研究,未来对相关机理、影响因素及降解途径的阐述仍需完善. 对微生物降解的研究主要集中在细菌、淀粉酶等特定微生物种类的降解特性(包括降解速率、降解效果)方面,对Deca-BDEs降解途径、转化及降解产物的鉴定尚不完全清楚. 此外,对高温下Deca-BDEs转化为溴代二英的机理研究比较缺乏. 由于BDE209具有极高的疏水性,并且其在大气中主要以固相形式存在于颗粒物中,因此今后的研究应更注重BDE209的气相和固相的光降解行为,注重微生物降解法在Deca-BDEs污染土壤修复技术的应用以及电子废物拆解过程中Deca-BDEs的降解途径和影响因素等方面.      

羟基化多溴联苯醚(OH-PBDEs)在小鼠肝脏S9中的体外代谢研究

羟基化多溴联苯醚(OH-PBDEs)是一类具有内分泌干扰性质的酚类化合物,且内分泌干扰效应大于其母体多溴联苯醚(PBDEs),研究OH-PBDEs的体外代谢行为对于理解其在生物体内的富集转化具有重要意义.以小鼠肝脏S9部分作为研究对象,考察了3-OH-BDE-47、5-OHBDE-47、6-OH-BDE-47和2'-OH-BDE-68在小鼠肝脏中的体外代谢.结果表明小鼠肝脏S9中的I相酶和II相酶均能代谢4种OH-PBDEs;醚键与OH官能团及Br原子互为邻位时,I相酶对OH-PBDEs的代谢率最高,即6-OH-BDE-47表现出较高的代谢率,此外,4种OH-PBDEs经I相酶代谢后均能生成2,4-二溴苯酚,表明醚键断裂是其主要的I相酶代谢途径;OH-PBDEs的OH官能团与醚键互为间位时,II相酶对其葡萄糖醛酸结合反应最高,也就是5-OH-BDE-47表现出较高的去除率.     

On discrepancies between different laboratory measurements of kinetic parameters for the reaction of the hydroxyl radical with halocarbons

This paper discusses laboratory-measured rate coefficients for the reaction of hydroxyl radicals with halogenated organic compounds. A knowledge of such rate coefficients is vital in assessing the tropospheric lifetimes of the compounds. There appear to be significant differences between measurements from different laboratories. Possible sources of the discrepancies are discussed critically, and the possible influence of the technique employed (flash-photolysis or discharge-flow) is considered. Reactive impurities, secondary losses of OH and unanticipated heterogeneous processes might each invalidate the experimental measurements. The effects of these influences are analysed in turn. The conclusion is drawn that the most probable source of error derives from surface phenomena, and some experimental evidence is given that supports this idea. In these circumstances, it may turn out that the most reliable data are those obtained at high temperatures and that, contrary to received wisdom, it may be advantageous to extrapolate high-temperature data to calculate rate coefficients at tropospheric temperatures.     

基于烟雾箱模拟的己烯醇与O3气相反应的动力学研究

为了研究O₃与挥发性不饱和醇的动力学常数以及反应活性差异的原因,使用绝对速率法在烟雾箱中对5种己烯醇和O₃的反应动力学进行研究.结果表明:Z-2-己烯-1-醇、E-2-己烯-1-醇、Z-4-己烯-1-醇、E-4-己烯-1-醇、5-己烯-1-醇与O₃在298 K、101 325 Pa下的反应动力学常数分别为（8.94×10-17±0.80×10-17）、（13.95×10-17±0.48×10-17）、（8.82×10-17±0.31×10-17）（10.01×10-17±1.03×10-17）和（0.82×10-17±0.04×10-17）cm3/（molecule·s）,并通过理论计算结果来解释和讨论动力学常数的变化趋势,发现不同烯醇与O₃反应的活性会受到—OH和双键相对位置的影响.通过试验所得动力学数据与大气氧化剂平均浓度计算得到各种己烯醇的大气寿命,发现O₃、OH自由基和NO₃自由基在消除Z-2-己烯-1-醇、E-2-己烯-1-醇、Z-4-己烯-1-醇和E-4-己烯-1-醇的过程中均属于竞争反应,但在高O₃污染地区,这4种己烯醇的消除是由O₃所主导的,5-己烯-1-醇因结构的原因,其大气寿命较长,超过7 h.研究显示:O₃对这5种己烯醇的清除作用明显;研究数据为环境空气质量预测模式提供了相关的动力学参数;己烯醇中各官能团的不同位置对其与O₃反应活性的影响结果,可为类似烯醇与O₃的反应速率常数的测定和预测提供理论支持.      

鲤鱼对硝基苯的生物积累、消除与代谢研究

应用流动式摄取及释放装置，对鲤鱼进行了硝基苯的生物积累，代谢研究，结果表明，鲤鱼对硝基苯浓缩很快，全鱼，肌肉，其它组织中的生物积累曲线地均呈现快速增长至峰，后又快速下降至低浓度水平稳态的峰形曲线，释放呈双曲线形，对数作图可得到两条不同斜度的直线。     

Enhanced photoelectrocatalytic degradation of ammonia by in situ photoelectrogenerated active chlorine on TiO2 nanotube electrodes

TiO_2 nanotube(Ti NT) electrodes anodized in fluorinated organic solutions were successfully prepared on Ti sheets. Field-emission scanning electron microscopy(FE-SEM) and X-ray diffraction(XRD) were performed to characterize the TiNT electrodes. The linear voltammetry results under irradiation showed that the TiNT electrode annealed at 450°C presented the highest photoelectrochemical activity. By combining photocatalytic with electrochemical process, a significantly synergetic effect on ammonia degradation was observed with Na_2SO_4 as supporting electrolyte at pH 10.7. Furthermore, the photoelectrocatalytic efficiency on the ammonia degradation was greatly enhanced in presence of chloride ions without the limitation of pH. The degradation rate was improved by 14.8 times reaching 4.98 × 10~(-2) min~(-1) at pH 10.7 and a faster degradation rate of 6.34 × 10~(-2) min~(-1)was obtained at pH 3.01. The in situ photoelectrocatalytic generated active chlorine was proposed to be responsible for the improved efficiency. On the other hand, an enhanced degradation of ammonia using TiNT electrode fabricated in fluorinated organic solution was also confirmed compared to TiNT electrode anodized in fluorinated water solution and TiO_2 film electrode fabricated by sol–gel method. Finally, the effect of chloride concentration was also discussed.