Rate constants for the gas-phase reactions of OH and NO3 radicals and O3 with sabinene and camphene at 296±2 K

The rate constants for the gas-phase reactions of sabinene and camphene, two monoterpenes emitted from vegetation, with OH and NO₃ radicals and O₃ have been determined at 296±2 K and one atmosphere total pressure of air. The OH and NO₃ radical reaction rate constants were determined using relative rate techniques. Using rate constants of k(OH + isoprene) = 1.01 × 10⁻¹⁰ cm³ molecule⁻¹ s⁻¹, k(NO₃ + trans-2-butene) = 3.87 × 10⁻¹³ cm³ molecule⁻¹ s⁻¹ and k(NO₃ + 2-methyl-2-butene) = 9.33 × 10⁻¹² cm³ molecule⁻¹ s⁻¹, the following OH and NO₃ radical reaction rate constants (in cm³ molecule⁻¹ s⁻¹ were obtained: OH radical reaction; sabinene, 1.17 × 10⁻¹⁰ and camphene, 5.33 × 10⁻¹¹; NO₃ radical reaction; sabinene, 1.01 × 10⁻¹¹, and camphene, 6.54 × 10⁻¹³. The absolute O₃ reaction rate constants determined were (in cm³ molecule⁻¹ s⁻¹ units): sabinene, 8.07 × 10⁻¹⁷, and camphene, 9.0 × 10⁻¹⁹. These rate constants are compared to literature data for other structural-related alkenes and monoterpenes.     

Photolysis of Fe (III)-hydroxy complexes as sources of OH radicals in clouds,fog and rain

Photolysis of the monohydroxy complex of Fe(III), Fe(OH)²⁺, has been proposed as a major source of OH radicals in rain. It is also a significant source of OH radicals in clouds and fog, and probably in some acidic surface waters. Fe(OH)²⁺ is the dominant monomeric Fe(III)-hydroxy complex between pH 2.5 and 5, based on currently available equilibrium constants for Fe(III)-hydroxy complexes. Quantum efficiencies for the photolysis of Fe(OH)²⁺ are 0.04±0.04 at 313 nm and 0.017±0.003 at 360 nm (293 K, ionic strength = 0.03 M). The measured rate constant for midday June sunlight photolysis of Fe(OH)²⁺ is 6.3 × 10⁻⁴s⁻¹ (half life = 18 min). Model calculations based on measured quantum yields and absorption spectra are in satisfactory agreement with measured sunlight photolysis rates of monomeric Fe(III).     

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.)     

Laboratory studies of some halogenated ethanes and ethers: Measurements of rates of reaction with OH and of infrared absorption cross-sections

We have measured, using a conventional discharge-flow resonance-fluorescence technique, the rates of reaction between the hydroxyl radical and a series of halogenated ethanes and ethers for the temperature range 230–423 K. Our measurements gave the following Arrhenius expressions (units are cm³ molecule⁻¹ s⁻¹): CF₂HCH₃ (HFC-152), 14.2 × 10⁻¹³ exp-(1050/T); CF₂ClCH₃ (HCFC-142b), 2.6 × 10⁻¹³ exp-(1230/T); CFCl₂CH₃ (HCFC-141b), 5.8 × 10⁻¹³ exp-(1100/T); CF₃CFH₂ (HFC-134a), 5.8 × 10⁻¹³ exp-(1350/T); CF₃CF₂H (HFC-125), 2.8 × 10⁻¹³ exp-(1350/T); CF₃CCl₂H (HCFC-123), 11.8 × 10⁻¹³ exp-(900/T); CF₂HOCF₂CFClH, (enflurane), 6.1 × 10⁻¹³ exp-(1080/T); CFH₂OCH(CF₃)₂, (sevoflurane), 15.3 × 10⁻¹³ exp-(900/T). In two cases, we measured rate constants only at room temperature: CF₃CClBrH (halothane), 6 × 10⁻¹⁴ and CF₂HOCClHCF₃ (isoflurane), 2.1 × 10⁻¹⁴.We also report the following values for the integrated absorption cross-sections of the compounds in the spectral region 800–1200 cm⁻¹ in units of cm⁻² atm⁻¹: CF₂HCH₃, 1155; CF₂ClCH₃, 1422; CFCl₂CH₃, 1995; CF₃CFH₂, 2686; CF₃CF₂H, 1970, CF₃CCl₂H, 1411; CF₃CClBrH, 1400; CF₂HOCF₂CFClH, 4800; CF₂HOCClHCF₃, 3900; CFH₂OCH(CF₃)₂, 2550. We use our measurements to calculate ozone depletion potentials and greenhouse warming potentials relative to CFCl₃ for each compound.     

Diurnal variation of OH radical and hydrocarbons in a polluted air mass during long-range transport in central Japan

Long-range transport (LRT) of photochemical air pollution from the coastal area, with large emission sources to the inland mountainous region, occurs frequently in central Japan on clear summer days. Hydrocarbons and other pollutants were measured together with meteorological parameters along this route, and the diurnal variations of OH radical and hydrocarbons in the polluted air mass were investigated in relation with these photochemical reactions.At inland sampling sites, hydrocarbon concentrations in a polluted air mass decreased during LRT in the daytime. In particular, olefins were destroyed significantly because of more active photochemical reactions. From these destruction rates and/or O₃ formation rates the OH radical concentration was estimated and found to increase from 0.5 × 10⁻⁷ in the morning to a maximum of 8.0 × 10⁻⁷ ppm at midday. These values, as well as the diurnal variation, compared well with the numerical result of the comprehensive transport/reaction/removal model (Chang et al., 1989, Atmospheric Environment23, 363–393, 1749–1773). The contribution of each hydrocarbon component to the total hydrocarbon destruction was also discussed.     

Field studies of the SO2/aqueous S(IV) equilibrium in clouds

Concentrations of S(IV) were measured in cloudwater at Great Dun Fell and compared with theoretical HSO₃⁻ assuming equilibrium between aqueous and gaseous phases in cloud. Detectable concentrations of S(IV) in the range of 1 × 10⁻⁶ to 17.2 × 10⁻⁶ mol dm⁻³ were observed only in samples which contained low H₂O₂ concentrations, generally <1 × 10⁻⁶ mol dm⁻³. Concentrations of S(IV) were below the detection limit of 1 × 10⁻⁶ mol dm⁻³ in samples which contained hign H₂O₂ levels (1 × 10⁻⁶−80 × 10⁻⁶ mol dm⁻³) confirming that either SO₂ or H₂O₂ acts as the limiting reagent in the oxidation of SO₂ in cloudwater.Equilibrium HSO₃⁻ concentrations were estimated from the measured cloudwater pH, the gas phase SO₂ concentration and the ambient temperature and found to be on average about 5 times lower than the measured S(IV) concentrations. The possible role of formaldehyde in stabilizing S(IV) in cloudwater is discussed. The kinetic data available in the literature suggest that the complexation reaction between S(IV) and HCHO is too slow to account for the observed difference between measured and calculated S(IV) concentrations over the typical lifetime of clouds in our study.S(IV) accounted for up to 10% of the SO₄²⁻ measured in stored cloudwater samples.     

A hydroxyl radical detection system using gas expansion and fast gating laser-induced fluorescence techniques

An OH radical measurement instrument based on Fluorescence Assay by Gas Expansion(FAGE)has been developed in our laboratory.Ambient air is introduced into a low-pressure fluorescence cell through a pinhole aperture and irradiated by a dye laser at a high repetition rate of 8.5 k Hz.The OH radical is both excited and detected at 308 nm using A-X(0,0)band.To satisfy the high efficiency needs of fluorescence collection and detection,a 4-lens optical system and a self-designed gated photomultiplier(PMT)is used,and gating is actualized by switching the voltage applied on the PMT dynodes.A micro channel photomultiplier(MCP)is also prepared for fluorescence detection.Then the weak signal is accumulated by a photon counter in a specific timing.The OH radical excitation spectrum range in the wavelength of 307.82–308.2 nm is detected and the excited line for OH detection is determined to be Q_1(2)line.The calibration of the FAGE system is researched by using simultaneous photolysis of H_2O and O_2.The minimum detection limit of the instrument using gated PMT is determined to be 9.4×10~5molecules/cm~3,and the sensitivity is 9.5×10~(-7)cps/(OH·cm~(-3)),with a signal-to-noise ratio of 2 and an integration time of 60 sec,while OH detection limit and the detection sensitivity using MCP is calculated to be 1.6×10~5molecules/cm~3and 2.3×10~(-6)cps/(OH·cm~(-3)).The laboratory OH radical measurement is carried out and results show that the proposed system can be used for atmospheric OH radical measurement.     

Studies on the formation of H2O2 in the ozonolysis of alkenes

The formation of H₂O₂ in the reactions of ozone with alkenes, isoprene and some terpenes has been studied with tunable diode laser absorption spectroscopy. The measured yields of H₂O₂ were found to be considerably enhanced in the presence of water vapour. H₂O₂ is thought to be formed in the ozonolysis of the alkene with O₃ by direct reaction of an intermediate with water vapour. The yield of H₂O₂ relative to the reacted alkene in the ozonolysis of trans-2-butene in the presence of water vapour was also studied with long path FTIR spectroscopy. Irrespective of the analytical methods and reaction conditions applied, the H₂O₂ yields in the reaction of O₃ with the different alkenes in the presence of water vapour were found to be in the range of a few per cent or less. Under the assumption that the reactive species forming H₂O₂ in the ozonolysis is the Criegee biradical, the overall rate constants for the reactions of some biradicals with water vapour were measured relative to the rate constant of the biradical with SO₂. For the H₂COO biradical a rate constant of (5.8 ± 2.5) × 10⁻¹⁷ cm³ s⁻¹ was determined and for the (CH₃)₂COO biradical (2.9 ± 1.5) × 10⁻¹⁷ cm³ s⁻¹; in the latter case with the assumption that (CH₃)₂COO reacts with SO₂ as fast as CH₂COO.     

Real-time,in situ measurements of atmospheric optical absorption in the visible via photoacoustic spectroscopy—IV. Visibility degradation and aerosol optical properties in Los Angeles

Aerosol light absorption (b_abs) has been measured in real-time in Los Angeles with a validated photoacoustic technique, and its impact on visibility degradation has been examined. These measurements were collected during ten days in the summer of 1987 for the Southern California Air Quality Study (SCAQS). Aerosol b_abs (λ = 514.5 nm) varied from an hourly average value of 7 × 10⁻⁶ m⁻¹ in the 3–4 and 4–5 a.m. periods of 13 July to 9 × 10⁻⁵ m⁻¹ in the 7–8 a.m. period of both 28 August and 3 September. This b_abs, which is due solely to elemental carbon (EC) showed a distinct diurnal pattern with low values at night, increasing around sunrise to higher values through mid-afternoon. Comparison of these data with aerosol light scattering data clearly illustrates that the contribution of aerosol light absorption to visibility degradation increases in importance under less polluted conditions. Other urban and rural studies show similar results.     

Heterogeneous transformation of peroxyacetylnitrate

The heterogeneous decomposition of peroxyacetylnitrate (PAN) has been investigated using a flow reactor and infrared spectroscopic analysis. The decomposition rate in air due to glass surfaces follows the relation d[PAN]/dt = −S/V([PAN] × 7 × 10⁷ + [CH₃C(O)OO] × 5 × 90¹²)exp(−9382/T) molecules cm⁻³ s⁻¹ (S/V=surface to volume ratio). The rate observed for NH₄HSO₄-covered surfaces is lower than in the glass case. The rate is high enough to affect many laboratory experiments but too slow to have any influence on PAN decomposition under ambient conditions.     

OH自由基绝对标定系统的建立和研究

利用H2 O在 1 85nm紫外光照射下产生定量OH自由基 ,用低压扩散激光诱导荧光技术建立了OH自由基标定系统 .在实验条件下 ,体系产生OH自由基的浓度范围为 3× 1 0 7— 2× 1 0 9个·cm- 3,得到归一化荧光信号 (S)与OH自由基浓度的定量关系为S =6 0 4× 1 0 - 9[OH]- 0 0 4 0 7(R2 =0 987) ,并研究和讨论了饱和效应以及体系中可能存在的干扰 .     

不同交通状况下道路边大气颗粒物数浓度粒径分布特征

研究了不同交通状况下北京交通环境大气颗粒物数浓度的污染特征.应用扫描电迁移率颗粒粒径谱仪(SMPS)测定了2009年8月常规交通状况和2008年8月奥运交通状况下北四环道路边大气颗粒物的数浓度,分析了数浓度的粒径分布特征及其逐时变化规律,目的为辨析交通流改变对交通环境中颗粒物数浓度的影响.常规交通状况下道路边超细颗粒物(10～100nm)和10～478 nm颗粒物总粒数浓度分别为(1.15±0.49)×104个.cm-3、(1.61±0.57)×104个.cm-3,奥运交通状况下分别下降到(0.55±0.14)×104个.cm-3、(1.21±0.24)×104个.cm-3,不同粒径段中超细颗粒物数浓度降幅最高,为52.2%.常规交通状况下道路边大气中颗粒物粒数浓度呈双峰分布,峰值粒径依次为22.5 nm和113.0 nm.奥运期间由于机动车单双号限行和黄标车禁行等措施的实施,22.5 nm处颗粒物数浓度峰值消失.粒径分布逐时变化显示,常规交通状况下00:00～04:00柴油车流量高峰、11:00～13:00高温强光照和17:00～20:00交通晚高峰这3个时段内超细颗粒物数浓度较高;而奥运期间受到交通流量下降、平均车速提高等因素影响,道路边颗粒物数浓度粒径分布逐时变化趋于平缓.     

Three-wavelength nephelometer suitable for aircraft measurement of background aerosol scattering coefficient

A new nephelometer suitable for aircraft measurements of aerosol scattering extinction coefficient (σ_sp) has been constructed and operated under field conditions. This instrument is vacuum tight for operation in a pressurized aircraft cabin and is capable of measuring background tropospheric σ_sp at an averaging time of 1 min. For example, in a typical atmospheric profile the instrument can measure values of about 10⁻⁴ m⁻¹ with a time resolution of 2 s in a polluted region, and about 10⁻⁷ m⁻¹ with a time resolution of 1 min in a clean region. This sensitivity is made possible by: (1) subtracting in real time the air Rayleigh scattering from the total scattering signal by continuously measuring pressure and temperature in the sampling volume of the instrument; (2) correcting for the dark count and sensitivity of the photomultipliers using a rotating shutter; and (3) using a beam splitter arrangement to allow simultaneous detection by three photomultipliers. A laboratory measurement of instrument noise suggests a 550-nm noise level of about 5 × 10⁻⁸ m⁻¹ at an averaging time of 1 min.     

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.     

广州城市大气HOx化学过程初步研究

根据广州城市大气中OH自由基和其它污染物同步测量结果,计算了城市大气HO_x(OH+HO₂)化学过程中主要反应的转化速率,分析了城市大气化学过程的主要特征,并与清洁大气中的化学过程进行了对比.研究结果表明:广州城市大气中OH和HO₂总的生成速率分别约为4.5×10⁸分子/(cm³·s)和3.8×10⁸分子/(cm³·s),比清洁大气中要快得多;城市大气中的OH净生成主要来自气相HNO₂的光解,而OH的去除主要与VOCs、HCHO、NO₂和CO反应,有别于清洁大气.     

臭氧与二甲硫醚和乙烯的反应速率常数测定

在室温和1.01×105 Pa条件下,利用烟雾箱以及气相色谱和臭氧分析仪研究手段,采用绝对方法(准一级反应)获得了臭氧与二甲硫醚(DMS)和乙烯(C2H4)的反应速率常数,分别为:kDMS=(1.48±0.12)×10-20 cm3·molecule-1·s-1;kC2H4=(1.35±0.10)×10-18cm3·molecule-1·s-1.其中,臭氧与乙烯的反应速率常数与文献报道吻合较好,臭氧与DMS的反应速率常数比文献报道的上限值低约两个数量级.     

辽河口湿地沉积物硝化细菌及硝化作用研究

2009年6月和8月,采用现场培养和实验室模拟培养相结合的方法对辽河口湿地表层沉积物硝化细菌数量、硝化速率及影响因素进行了研究.结果表明,辽河口湿地表层沉积物氨氧化细菌(ammonia-oxidizing bacteria,AOB)数量6月在0.54×104～5.69×104个.g-1之间,平均值为(2.21±2.32)×104个.g-1,8月在1.90×104～7.90×104个.g-1之间,平均值为(3.61±2.87)×104个.g-1;沉积物潜在硝化速率6月在9.72～16.45 mmol.(m2.h)-1之间,平均值为(12.54±3.14)mmol.(m2.h)-1,8月在14.66～24.62 mmol.(m2.h)-1之间,平均值为(18.71±4.21)mmol.(m2.h)-1;净硝化作用速率6月(S1站)为0.41 mmol.(m2.h)-1,8月在0.20～0.53 mmol.(m2.h)-1之间,平均值为(0.35±0.16)mmol.(m2.h)-1.潜在硝化速率显著高于净硝化速率,AOB数量、净硝化作用速率和潜在硝化作用速率均表现为8月高于6月,芦苇根际效应对硝化作用有促进作用.通过SPSS 13.0软件统计分析,表明影响辽河口湿地表层沉积物硝化作用的主要环境因子有上覆水NH 4+-N浓度和沉积物pH、有机质、总氮(TN)、总磷(TP)、NH 4+-N含量以及AOB数量(p0.05),其中上覆水NH 4+-N浓度和沉积物总磷(TP)、NH 4+-N含量对硝化作用影响较大,是辽河口湿地硝化作用影响的关键因素.根据研究结果估算辽河口湿地沉积物硝化作用每天可以将1.14×105kg的NH 4+-N转化为NO 3--N,对河口湿地氮的循环具有重要意义.     

Factors affecting airborne monocyclic aromatic hydrocarbon uptake by plants

Three factors influencing foliar uptake of monocyclic aromatic hydrocarbons (MAHs; benzene, toluene, ethylbenzene, xylenes) in situ were investigated. The first factor, the plant species, was found to determine absorption pattern and concentrations. Secondly, time variation studies showed that response of leaf concentrations to small changes in air concentrations only occurs after several days or weeks, whereas adaptation to a much higher level of air pollution takes several months. Thirdly, MAH leaf concentrations were observed to be dependent on mean air pollution at the sampling site. Bioconcentration factors BCF_vs (g m⁻³ of wet leaf/g m⁻³ of air) for MAHs in Pseudotsuga menziesii (Mirb.) Franco leaves were determined to range from 2.7 × 10⁴ to 4.7 × 10⁵.     

中国西部本底大气中CO的连续测量

在中国西北部的瓦里关全球基准站(36°17'N,100°54'E,3810m asl)建立了气相色谱-汞置换法大气CO连续测量系统.组装调试和运行标定表明,色谱方法的基线稳定,分离度高,检测方法可靠,系统具有高自动化的操作性能和严格的质量控制,其设计完全符合世界气象组织(WMO)全球大气本底测量的要求.根据采样现场大气CO浓度的变化,采用经国际比对的CO标准气系列,用峰高外标法设定可调整的标准工作曲线计算环境CO浓度,系统对CO的检测限低至1×10^-9(V/V),检测精度小于0.1%,准确度在±0.05%以内,可提供我国本底地区近地层大气CO连续而精确的现场测量结果.