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.     

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.     

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.     

Precision of the radiochemical OH measurement method

Twenty-eight radiochemical ¹⁴C tracer measurement of tropospheric hydroxyl radical (OH) concentrations were obtained at a rural site near Washington State University, Pullman, WA (117°W, 47°N). Diurnal OH concentration variations were observed for the five days between 9 August and 14 August 1990. These data made it possible to estimate the midday precision and detection limit of the radiochemical OH measurement method. Experiments performed at a peak O₃ photolysis rate J (O(¹D)) of (3.0±0.2) × 10⁻⁵ s⁻¹ yielded a mean midday OH concentration of (5.6±0.1 (1σ)) × 10⁶ cm⁻³. Other data put an upper bound of 16% on fluctuations of instrument sensitivity. Low-light or nighttime background OH concentrations were less than (2.6±2) × 10⁵ cm⁻³. A lower detection limit of 10⁵ cm⁻³ was obtained when extra care was taken with the low-level ¹⁴C counting procedure.     

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.     

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.     

Wind tunnel experiments on the resuspension of particulate material

A programme of wind tunnel experiments has been carried out in which the resuspension of particulate material of four sizes (4, 10, 18 and 22 μm diameter) from concrete and grass surfaces has been studied. The importance of wind speed has been investigated and the time dependence of the resuspension rate has been evaluated for periods shortly after the onset of resuspension. The results indicate rapidly falling values of the resuspension rate which are approximately related to 1/time. The increase in the resuspension rate with increasing wind speed was most pronounced for large particles, leading to the conclusion that resuspension can be dominated by short-duration episodes which coincide with conditions that favour resuspension. Resuspension rates, averaged over approximately 1 h after the onset of conditions leading to resuspension, were in the range 1 × 10⁻⁶ to 5 × 10⁻⁶ s⁻¹, at moderate wind speeds (less than 5 m s⁻¹), with little difference between the grass and concrete surfaces. For high wind speeds (greater than 6.5 m s⁻¹), several per cent of the total surface deposit of 22 μ diameter particles was removed from both the concrete and grass surfaces within 10 s of the onset of wind.     

The role of copper and oxalate in the redox cycling of iron in atmospheric waters

During daytime, the redox cycling of dissolved iron compounds in atmospheric waters, and the related in-cloud transformations of photooxidants, are affected by reactions of Fe and Cu with hydroperoxy (HO₂) and superoxide (O₂⁻) radicals and the photoreduction of Fe(III)-oxalato complexes. We have investigated several of the important chemical reactions in this redox cycle, through laboratory simulation of the system, using γ-radiation to produce HO₂/O₂⁻. At concentrations comparable to those measured in atmospheric waters, the redox cycling of Fe was dramatically affected by the presence of oxalate and trace concentrations of Cu. At concentrations more than a hundred times lower than Fe, Cu consumed most of the HO₂/O₂⁻, and cycled between the Cu(II) and Cu(I) forms. Cu⁺ reacted with FeOH²⁺ to produce Fe(II) and Cu(II), with a second order rate constant of approximately 3 × 10⁷ M⁻¹s⁻¹. The presence of oxalate resulted in the formation of Fe(III)-oxalato complexes that were essentially unreactive with HO₂/O₂⁻. Only at high oxalate concentrations was the Fe(II)C₂O₄ complex also formed, and it reacted relatively rapidly with hydrogen peroxide (k = (3.1 ± 0.6) × 10⁴ M⁻¹s⁻¹). Simulations incorporating measurements for other redox mechanisms, including oxidation by ozone, indicate that, during daytime, Fe should be found mostly in the ferrous oxidation state, and that reactions of FeOH²⁺ with Cu(I) and HO₂/O₂⁻, and to a lesser degree, the photolysis of Fe(III)-oxalato complexes, are important mechanisms of Fe reduction in atmospheric waters. The catalytic effect of Cu(II)/Cu(I) and Fe(III)/Fe(II) should also significantly increase the sink function of the atmospheric liquid phase for HO₂ present in a cloud. A simple kinetic model for the reactions of Fe, Cu and HO₂/O₂⁻, accurately predicted the changes in Fe oxidation states that occurred when authentic fogwater samples were exposed to HO₂/O₂⁻.     

水力空化强化H2O2氧化降解水中苯酚的研究

采用水力空化强化H₂O₂降解水中苯酚,考察入口压力,ρ(H₂O₂)和溶解气体等因素对苯酚降解的影响;比较了水力空化方法和超声空化方法降解水中苯酚的能耗效率.研究表明:苯酚降解率随着入口压力的增大而增大,入口压力从1.0×105 Pa增大到3.5×105 Pa时,相应地苯酚降解率从17.6%增加到47.6%;在一定条件下,ρ(H₂O₂)有一个最佳值;不同的溶解气体对苯酚降解效果的影响不同,O₂的效果比N₂好.分析ρ(H₂O₂)和溶解气体对苯酚降解效果的影响及苯酚降解中间产物的分布表明,羟基自由基的产生是苯酚降解的主要原因,水力空化的能量利用率是超声空化的5.4倍.      

FTIR spectroscopic measurements of surface bond products of nitrogen oxides on aerosol surfaces—implications for heterogeneous HNO2 production

FTIR spectroscopy measurements have been made to investigate the products of heterogeneous reactions of nitrogen oxides like NO₂, N₂O₅ and HNO₂ in the presence of water vapour on artificial and natural aerosol surfaces. Surface species on NaCl particles differ significantly from those on urban aerosols or fly ash. Evidence for a nighttime production of NO₂⁻ on sea-salt surfaces from reactions of N₂O₅ and water vapour is given.     

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.     

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).     

Theoretical study on the reaction mechanism of ozone addition to the double bonds of keto-limonene

The reaction mechanism of ozone (O₃) addition to the double bonds of gas phase keto-limonene was investigated using ab initio methods. Two different possibilities for O₃ addition to the double bond were considered and two corresponding van derWaals complexes (Complex 1 and Complex 2) were found for 1-endo and 2-endo. The rate constants were calculated using the transition state theory at the CCSD(T)/6-31G(d) + CF//B3LYP/6-31G(d,p) level. The high-pressure limit of the total rate constant at 298 K was 3.51 × 10^-16 cm³/(molecule sec), which was in a good agreement with the experimental data.     

溶解性有机质对罗红霉素光降解的影响研究

近年来,罗红霉素(ROX)因其用量大、检出频率高和生态风险大引起了广泛关注.本文主要研究了环境pH条件下不同的溶解性有机质(DOM),包括富里酸(PLFA)、腐殖酸(SRHA)和天然有机质(SRNOM)对罗红霉素光降解的影响及主要活性物种对其光降解的贡献.结果表明:纯水中罗红霉素可发生自敏化光降解,在pH 6～8条件下,罗红霉素光降解的一级反应速率常数为0.0033～0.0049 h~(-1).DOM促进了罗红霉素光降解,其促进效果从大到小为PLFASRNOMSRHA.DOM共存时罗红霉素光降解的反应速率常数随pH增加而增加,在pH 6时为0.0145～0.0266 h~(-1),在pH 8时为0.0273～0.0577 h~(-1).通过异丙醇淬灭实验发现,羟基自由基(·OH)对罗红霉素光降解起主要贡献,其贡献率在pH 6时为83.45%～98.70%,在pH 8时降低至76.76%～78.02%;3种DOM体系中产生的单态氧(~1O_2)的稳态浓度在(5.15～7.86)×10~(-14) mol·L~(-1)范围内;在pH 6、7和8的条件下,~1O_2与罗红霉素的二级反应速率常数分别为2.27×10~5、1.96×10~6和1.51×10~7 L·mol~(-1)·s~(-1).~1O_2对罗红霉素的光降解的贡献随pH升高而升高,在pH 6时为0.21%～0.43%,在pH 8时为4.85%～11.33%.     

海水养殖场底泥中转化硫和磷化合物的微生物及其多样性

对福建某近海养虾场底泥环境中硫和磷2种元素的微生物代谢进行了研究.结果表明,细菌代谢有机硫和无机硫产H₂S是养殖过程中造成H₂S污染的主要因素,利用半胱氨酸和硫代硫酸钠产生硫化氢的细菌数量分别为 1.6×10⁶和4.35×10³ 个·g^-1底泥;进一步研究发现,芽孢杆菌属、盐芽孢杆菌属和微杆菌属等细菌是产H₂S的优势菌群,而硫酸盐还原菌的数量较少,仅为25个·g^-1,其产H2S的作用不明显.研究还发现,转化有机磷和无机磷酸盐的优势菌群属于好氧细菌,其中分解卵磷脂的细菌和产磷酸酯酶细菌的数量分别为2.17×10⁵和 1.21×10⁶个·g^-1,转化磷酸钙的细菌数量为6.96×10³个·g^-1.本文从微生物学的角度探讨了养殖环境中硫、磷化合物的转化,提出细菌好氧代谢产H₂S是养殖环境潜在的污染因素,给出了一些改善和修复养殖环境生态的建议.     

Observations of N2O5 and NO3 at a suburban environment in Yangtze river delta in China: Estimating heterogeneous N2O5 uptake coefficients

The nitrate radical (NO₃) and dinitrogen pentoxide (N₂O₅) play an important role in the nocturnal atmosphere chemistry. Observations of NO₃ radicals and N₂O₅ were performed in a semirural ground site at Tai'Zhou in polluted southern China using cavity ring down spectroscopy (CRDS) from 23 May to 15 June 2018. The observed NO₃ and N₂O₅ concentrations were relatively low, with 1 min average value of 4.4 ± 2.2 and 26.0 ± 35.7 pptV, respectively. The N₂O₅ uptake coefficient was determined to be from 0.027 to 0.107 based on steady state lifetime method. Fast N₂O₅ hydrolysis was the largest contributor to the loss of NO₃ and contributed to substantial nitrate formation, with an average value of 14.83 ± 6.01 µg/m³. Further analysis shows that the N₂O₅ heterogeneous reactions dominated the nocturnal NO_x loss and the nocturnal NO_x loss rate is 0.14 ± 0.02 over this region.     

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.     

Nitrous oxide emissions from a dung heap measured by chambers and plume methods

Dung heaps provide a large, spatial and temporal variable, source of the greenhouse gas N₂O. In this paper emission rates measured by static and flow through chamber methods, which enclose only a small area of the heap, were compared with Gaussian plume and tracer ratio methods, which measure the emissions from the entire dung heap. The dung heap was a 300 m³ heap, composed of material from nearby cattle sheds. From the flow through and static chambers it was estimated that the dung heap emitted 315 and 51 g N₂ON m⁻³ day⁻¹, respectively. The spatial variability between the chambers and chamber methods was large. Standard deviations of the mean fluxes were >75% of the average flux. The smaller emissions were measured on the slopes of the heap and the larger emissions on the ridge. The plume of N₂O was measured downwind of the dung heap by (1) tunable diode laser spectroscopy and calculation of the N₂O source strength of the heap using Gaussian plume theory and (2) tracer ratio method releasing SF₆ from the heap summit and capture in Tedlar bags downwind with subsequent analysis by gas chromatography. The Gaussian plume theory calculated an average N₂O source strength of 5.3 g N₂ON m⁻³ day⁻¹ (1.4–6.7 g N₂ON m⁻³ day⁻¹). The tracer ratio method calculated a slightly larger average emission rate of 14.4 g N₂ON m⁻³ day⁻¹ (7.4–38.6 g N₂ON m⁻³ day⁻¹). Both methods were successfully validated by point release of SF₆ and N₂O, which suggests that the micrometeorological methods provided a good estimate of the source strength of the heap, whereas the few chamber measurements overestimated its source strength.     

北京城区夏季O3化学生成过程

选取2007年7月1日—8月31日中的21个晴空日,利用观测资料和光化学箱模式计算了北京城区测点的O₃生成速率G(O₃)和O₃生成效率OPE.结果表明,21个晴空日中G(O₃)日最高小时值分布在(18~82)×10^-9h^-1之间;在O₃污染和非污染日G(O₃)最高值的平均水平无显著差异,且与O_x浓度之间不存在一致的对应关系,表明O₃化学生成过程不能全面解释地面O₃浓度的累积,物理传输过程对测点O₃实测浓度有显著作用;各个化学过程对G(O₃)的贡献率对比结果显示,HO₂ 在 NO向NO₂的转化中贡献最大;OPE值分布在2.8~5.8之间,总体水平为4.1±0.1;OPE值与NO_x浓度之间为非线性关系,OPE值随NO_x浓度的增加而减少,表明消减测点附近VOCs排放能有效降低O₃浓度.     

青藏高原植被固定CO2释放O2的经济价值评估

基于研究区植被生产有机质的物质量,结合遥感和野外观测数据,利用生态经济学方法,测算了青藏高原近20年植被固碳释氧(固定CO₂释放O₂)的经济价值. 结果表明:青藏高原植被每年固定CO₂总量为28.1×108 t,释放O₂总量为20.8×108 t;青藏高原植被固碳释氧的总价值为15.6×1011 元/a,利用造林成本法估算植被固定CO₂的价值为7.3×1011 元/a,利用工业制氧法估算植被释放O₂的价值为8.3×1011 元/a;从不同植被类型来看,灌丛的服务价值贡献率最大,亚热带常绿针叶林的单位面积价值最高;在水平方向上,植被固碳释氧价值受降水和植被分布影响,自东南向西北逐渐降低;在垂直方向上,生态系统服务价值受地形影响较大.