Free Radicals and Fast Photochemistry during BERLIOZ

The free radicals OH, HO₂, RO₂, and NO₃ are known to be the driving force for most chemical processes in the atmosphere. Since the low concentration of the above radicals makes measurements particularly difficult, only relatively few direct measurements of free radical concentrations have been reported to date.We present a comprehensive set of simultaneous radical measurements performed by Laser Induced Fluorescence (LIF), Matrix Isolation –Electron spin Resonance (MI-ESR), Peroxy Radical Chemical Amplification (PERCA), and Differential Optical Absorption Spectroscopy (DOAS) during the BERLIner OZonexperiment (BERLIOZ) during July and August of 1998 near Berlin, Germany. Most of the above radical species were measured by more than one technique and an intercomparison gave good agreement. This data set offered the possibility to study and quantify the role of each radical at a rural, semi-polluted site in the continental boundary layer and to investigate interconnections and dependencies among these free radicals.In general (box) modelled diurnal profiles of the different radicals reproduced the measurements quite well, however measured absolute levels are frequently lower than model predictions. These discrepancies point to disturbing deficiencies in our understanding of the chemical system in urban air masses.In addition considerable night-time peroxy radical production related to VOC reactions with NO₃ and O₃ could be quantified.     

Simultaneous measurements of peroxy and nitrate radicals at Schauinsland

We present simultaneous field measurements of NO₃ and peroxy radicals made at night in a forested area (Schauinsland, Black Forest, 48° N, 8° N, 1150 ASL), together with measurements of CO, O₃, NO _x , NO _y , and hydrocarbons, as well as meteorological parameters. NO₂, NO₃, HO₂, and (RO₂) radicals are detected with matrix isolation/electron spin resonance (MIESR). NO₃ and HO₂ were found to be present in the range of 0–10 ppt, whilst organic peroxy radicals reached concentrations of 40 ppt. NO₃, RO₂, and HO₂ exhibited strong variations, in contrast to the almost constant values of the longer lived trace gases. The data suggest anticorrelation between NO₃ and RO₂ radical concentrations at night.The measured trace gas set allows the calculation of NO₃ and peroxy radical concentrations, using a chemical box model. From these simulations, it is concluded that the observed anthropogenic hydrocarbons are not sufficient to explain the observed RO₂ concentrations. The chemical budget of both NO₃ and RO₂ radicals can be understood if emissions of monoterpenes are included. The measured HO₂ can only be explained by the model, when NO concentrations at night of around 5 ppt are assumed to be present. The presence of HO₂ radicals implies the presence of hydroxyl radicals at night in concentrations of up to 10⁵ cm^–3.     

Modelled and measured concentrations of peroxy radicals and nitrate radical in the U.S. Gulf Coast region during TexAQS 2006

Measurements of total peroxy radicals (HO₂?+?RO₂) and nitrate radical (NO₃) were made on the NOAA research vessel R/V?Brown along the U.S. Gulf Coast during the TexAQS 2006 field campaign. The measurements were modelled using a constrained box-model based upon the Master Chemical Mechanism (MCM). The agreement between modelled and measured HO₂?+?RO₂ was typically within ??40% and, in the unpolluted regions, within 30%. The analysis of the model results suggests that the MCM might underestimate the concentrations of some acyl peroxy radicals and other small peroxy radicals. The model underestimated the measurements of NO₃ by 60?C70%, possibly because of rapid heterogeneous uptake of N₂O₅. The MCM model results were used to estimate the composition of the peroxy radical pool and to quantify the role of DMS, isoprene and alkenes in the formation of RO₂ in the different regions. The measurements of HO₂?+?RO₂ and NO₃ were also used to calculate the gas-phase budget of NO₃ and quantify the importance of organic peroxy radicals as NO₃ sinks. RO₂ accounted, on average, for 12?C28% of the total gas-phase NO₃ losses in the unpolluted regions and for 1?C2% of the total gas-phase NO₃ losses in the polluted regions.     

Chemical ionisation mass spectrometer for measurements of OH and Peroxy radical concentrations in moderately polluted atmospheres

A new version of an atmospheric pressure chemical ionisation mass spectrometer has been developed for ground based in situ atmospheric measurements of OH and total peroxy (HO₂ + organic peroxy) radicals. Based on the previously developed principle of chemical conversion of OH radicals to H₂SO₄ in reaction with SO₂ and detection of H₂SO₄ using an ion molecule reaction with NO₃^─, the new instrument is equipped with a turbulent chemical conversion reactor allowing for measurements in moderately polluted atmosphere at NO concentrations up to several ppb. Unlike other similar devices, where the primary NO₃^─ ions are produced using radioactive ion sources, the new instrument is equipped with a specially developed corona discharge ion source. According to laboratory measurements, the overall accuracy and detection limits are estimated to be, respectively, 25% and 2 × 10⁵ molecule cm^-3 for OH and 30% and 1 × 10⁵ molecule cm^-3 for HO₂ at 10 min integration times. The detection limit for measurements of OH radicals under polluted conditions is 5 × 10⁵ molecules cm^-3 at 10 min integration times. Examples of ambient air measurements during a field campaign near Paris in July 2007 are presented demonstrating the capability of the new instrument, although with reduced performance due to the employment of non isotopic SO₂.     

On the Budget of OH Radicals and Ozone in an Urban Plume from the Decay of C5–C8 Hydrocarbons and NOx

Simultaneous measurements of ozone and ozoneprecursors were made during a field campaign atSchauinsland in the Black Forest and in the valleynorth of Schauinsland that channels the flow ofpolluted air from the city of Freiburg to the site.From the decay of hydrocarbons and NO_x between the twomeasuring sites and the known rate coefficients, theconcentration of OH radicals was calculated. From abudget analysis of OH and HO_x it is concluded that therelatively high OH concentrations (5–8 ×10⁶cm^-3) in the presence of high NO₂concentrations cannot be explained by the knownprimary sources. The budget can be closed if efficientrecycling of OH via HO₂ is assumed to occur andthat, based on the measured hydrocarbons, 2 HO₂molecules are formed for each OH radical that reactswith a hydrocarbon molecule. This assumption is inaccordance with the budget of O_x obtained from ourmeasurements and with results from earliermeasurements of alkylnitrates and peroxy radicals atSchauinsland. A possible conclusion is that the decayof precursors and production of photooxidants in urbanplumes proceeds at a faster rate than is currentlyassumed. The potential role of biogenichydrocarbons for the radical budget is alsodiscussed.     

Atmospheric chemistry of alkanes

The reactions of the alkanes under atmospheric conditions and in the presence of oxides of nitrogen are reviewed and evaluated. Particular emphasis is placed upon their subsequent reactions after the initial OH radical reaction under conditions where the alkyl peroxy radicals produced react predominantly with NO, rather than with HO₂ and/or RO₂ radicals. Methods are discussed for estimating the overall OH radical rate constants, the number of molecules of NO consumed per alkane molecule reacted, and the products formed and their yields.     

Hydroxyl and Peroxy Radical Chemistry in a Rural Area of Central Pennsylvania: Observations and Model Comparisons

Atmospheric hydroxyl (OH), hydroperoxy (HO₂), total peroxy (HO₂ and organic peroxy radicals, RO₂) mixing ratios and OH reactivity (first order OH loss rate) were measured at a rural site in central Pennsylvania during May and June 2002. OH and HO₂ mixing ratios were measured with laser induced fluorescence (LIF); HO₂ + RO₂ mixing ratios were measured with chemical ionization mass spectrometry (CIMS). The daytime maximum mixing ratios were up to 0.6 parts per trillion by volume (pptv) for OH, 30 pptv for HO₂, and 45 pptv for HO₂ + RO₂. A parameterized RACM (Regional Atmospheric Chemistry Mechanism) box model was used to predict steady state OH, HO₂ and HO₂ + RO₂ concentrations by constraining the model to the measured OH reactivity and previously measured volatile organic compound (VOC) distributions. The averaged model calculations are generally in good agreement with the observations. For OH, the model matched the observations for day and night, with an average observed-to-modeled ratio of 0.80. In previous studies such as PROPHET98, nighttime NO was near 0 pptv and observed nighttime OH was significantly larger than modeled OH. In this study, nighttime observed and modeled OH agree to within measurement and model uncertainties because the main source of the nighttime OH was the reaction HO₂ + NO → OH + NO₂, with the NO being continually emitted from the surrounding fertilized corn field. The observed-to-modeled ratio for HO₂ is 1.0 on average, although daytime HO₂ is underpredicted by a factor of 1.2 and nighttime HO₂ is over-predicted by a factor of ∼2. The average measured and modeled HO₂ + RO₂ agree well during daytime, but the modeled value is about twice the measured value during nighttime. While measured HO₂ + RO₂ values agree with modeled values for NO mixing ratios less than a few parts per billion by volume (ppbv), it increases substantially above the expected value for NO greater than a few ppbv. This observation of the higher-than-expected HO₂ + RO₂ with the CIMS technique confirms the observed increase of HO₂ above expected values at higher NO mixing ratios in HO₂ measurements with the LIF technique. The maximum instantaneous O₃ production rate calculated from HO₂ and RO₂ reactions with NO was as high as 10–15 ppb h⁻¹ at midday; the total daily O₃ production varied from 13 to 113 ppbv d⁻¹ and was 48 ppbv d⁻¹ on average during this campaign.     

The Measurement of Active Chlorine in the Atmosphere by Chemical Amplification

Chemical amplification, CA, a method commonly used for the detection of peroxy radicals, HO₂ and RO₂, was found to be sensitive towards ClOx (Cl+ClO+OClO) as well. ClOx is reduced by NO to Cl atoms which react with carbon monoxide in the presence of O₂. The reaction sequence thus initiated oxidizes CO to CO₂ and NO to NO₂, with a chain length of 300 ± 60. This allows the atmospheric ClOx content to be measured under ambient conditions with a detection limit of better than 1 ppt. In parallel peroxy radicals are indicated with a chain length of 160 ± 15. Chemical amplification is not specific and does not indicate which radical chain it is seeing. Identification relies solely on plausibility. During the ARCtic Tropospheric Ozone Chemistry (ARCTOC) campaign in spring 1995 and 1996 the CA technique was used at Ny-Ålesund. ClOx at mixing ratios of up to 2 ppt were found in the boundary layer under certain conditions. The low concentrations of ClOx indicate that the arctic boundary ozone depletion is mainly driven by bromine.     

Dynamics of photosynthetic photon flux density (PPFD) and estimates in coastal northern California

Plants require solar radiation for photosynthesis and their growth is directly related to the amount received, assuming that other environmental parameters are not limiting. Therefore, precise estimation of photosynthetically active radiation (PAR) is necessary to enhance overall accuracies of plant growth models. This study aimed to explore the PAR radiant flux in the San Francisco Bay Area of northern California. During the growing season (March through August) for 2?years 2007?C2008, the on-site magnitudes of photosynthetic photon flux densities (PPFD) were investigated and then processed at both the hourly and daily time scales. Combined with global solar radiation (R _S) and simulated extraterrestrial solar radiation, five PAR-related values were developed, i.e., flux density-based PAR (PPFD), energy-based PAR (PARE), from-flux-to-energy conversion efficiency (fFEC), and the fraction of PAR energy in the global solar radiation (fE), and a new developed indicator??lost PARE percentages (LPR)??when solar radiation penetrates from the extraterrestrial system to the ground. These PAR-related values indicated significant diurnal variation, high values occurring at midday, with the low values occurring in the morning and afternoon hours. During the entire experimental season, the overall mean hourly value of fFEC was found to be 2.17???mol?J^?1, while the respective fE value was 0.49. The monthly averages of hourly fFEC and fE at the solar noon time ranged from 2.15 in March to 2.39???mol?J^?1 in August and from 0.47 in March to 0.52 in July, respectively. However, the monthly average daily values were relatively constant, and they exhibited a weak seasonal variation, ranging from 2.02?mol?MJ^?1 and 0.45 (March) to 2.19?mol?MJ^?1 and 0.48 (June). The mean daily values of fFEC and fE at the solar noon were 2.16?mol?MJ^?1 and 0.47 across the entire growing season, respectively. Both PPFD and the ever first reported LPR showed strong diurnal patterns. However, they had opposite trends. PPFD was high around noon, resulting in low values of LPR during the same time period. Both were found to be highly correlated with global solar radiation R _S, solar elevation angle h, and the clearness index K _t. Using the best subset selection of variables, two parametric models were developed for estimating PPFD and LPR, which can easily be applied in radiometric sites, by recording only global solar radiation measurements. These two models were found to be involved with the most commonly measured global solar radiation (R _S) and two large-scale geometric parameters, i.e., extraterrestrial solar radiation and solar elevation. The models were therefore insensitive to local weather conditions such as temperature. In particular, with two test data sets collected in USA and Greece, it was verified that the models could be extended across different geographical areas, where they performed well. Therefore, these two hourly based models can be used to provide precise PAR-related values, such as those required for developing precise vegetation growth models.     

The Role of In Situ Photochemistry in the Control of Ozone during Spring at the Jungfraujoch (3,580 m asl) – Comparison of Model Results with Measurements

A photochemical box model has been used to model themeasured diurnal ozone cycle in spring at Jungfraujochin the Swiss Alps. The comparison of the modelleddiurnal ozone cycle with the mean measured diurnalozone cycle in spring, over the period 1988–1996,shows a good agreement both with regard to the shapeand amplitude. Ozone concentrations increase duringthe daytime and reach a maximum at about 16:00–17:00(GMT) in both the modelled and the mean observed ozonecycle, indicative of net ozone production during thedaytime at Jungfraujoch in spring. The agreement isbetter when the modelled ozone cycle is compared withthe mean measured diurnal cycle (1988–1996) filteredfor north-westerly winds >5 m/s (representative ofregional background conditions at Jungfraujoch). Inaddition to ozone, the modelled diurnal cycle of[HO₂] + [CH₃O₂] also shows rather goodagreement with the mean diurnal cycle of the peroxyradicals measured during FREETEX '96, a FREETropopsheric Experiment at Jungfraujoch in April/May1996. Furthermore, this mean diurnal cycle of the sumof the peroxy radicals measured during FREETEX '96 isused to calculate, using steady-state expressions, therespective diurnal cycle of the OH radical. Thecomparison of the OH diurnal cycle, calculated fromthe peroxy radical measurements during FREETEX '96,with the modelled one, reveals also good agreement.The net ozone production rate during the day-time is0.27 ppbv h^-1 from the model, and 0.13 ppbvh^-1 from the observations during FREETEX '96. Theobservations and model results both suggest that thediurnal ozone variation in spring at Jungfraujoch isprimarily of photochemical origin. Furthermore, theobserved and modelled positive net ozone productionrates imply that tropospheric in situphotochemistry contributes significantly to theobserved high spring ozone values in the observedbroad spring-summer ozone maximum at Jungfraujoch.     

The annual cycle of peroxides and ozone in marine air at Cape Grim, Tasmania

The concentration of gas-phase peroxides has been measured almost continuously at the Cape Grim baseline station (41° S) over a period of 393 days (7702 h of on-line measurements) between February 1991 and March 1992. In unpolluted marine air a distinct seasonal cycle in concentration was evident, from a monthly mean value of>1.4 ppbv in summer (December) to <0.2 ppbv in winter (July). In the summer months a distinct diurnal cycle in peroxides was also observed in clean marine air, with a daytime build-up in concentration and decay overnight. Both the seasonal and diurnal cycles of peroxides concentration were anticorrelated with ozone concentration, and were largely explicable using a simple photochemical box model of the marine boundary layer in which the central processes were daytime photolytic destruction of ozone, transfer of reactive oxygen into the peroxides under the low-NO_x ambient conditions that favour self-reaction between peroxy radicals, and continuous heterogeneous removal of peroxides at the ocean surface. Additional factors affecting peroxides concentrations at intermediate timescales (days to a week) were a dependence on air mass origin, with air masses arriving at Cape Grim from higher latitudes having lower peroxides concentrations, a dependence on local wind speed, with higher peroxides concentrations at lower wind speeds, and a systematic decrease in peroxides concentration during periods of rainfall. Possible physical mechanisms for these synoptic scale dependencies are discussed.     

A Seasonal Comparison of the Ozone Photochemistry in Clean and Polluted Air Masses at Mace Head, Ireland

Measurements of the sum of peroxy radicals [HO₂ + RO₂],NO_x (NO + NO₂) and NO_y (the sum of oxidisednitrogen species) made at Mace Head, on the Atlantic coast of Ireland in summer 1996 and spring 1997 are presented. Together with a suite of ancillary measurements, including the photolysis frequencies of O₃ O(¹D)(j(O¹D)) and NO₂ (j(NO₂)), the measured peroxy radicals are used to calculate meandailyozone tendency (defined as the difference of the in-situphotochemical ozone production and loss rates); these values are compared with values derived from the photochemical stationary state (PSS) expression. Although the correlation between the two sets of values is good, the PSS values are found to be significantly larger than those derived from the peroxy radical measurements, on average, in line with previous published work. Possible sources of error in these calculations are discussed in detail. The data are further divided up into five wind sectors, according to the instantaneous wind direction measured at the research station. Calculation of mean ozone tendencies by wind sector shows that ozone productivity was higher during spring (April–May) 1997 than during summer (July–August) 1996across all airmasses, suggesting that tropospheric photochemistry plays an important role in the widely-reported spring ozone maximum in the Northern Hemisphere. Ozone tendencies were close to zero for the relatively unpolluted south-west, west and north-west wind sectors in the summer campaign, whereas ozone productivity was greatest in the polluted south-east sector for both campaigns. Daytime weighted average ozone tendencies were +(0.3± 0.1) ppbv h^–1 for summer 1996 and +(1.0± 0.5) ppbvh^–1 for spring 1997. These figures reflect the higher mixing ratios of ozone precursors in spring overall, as well as the higher proportion of polluted air masses from the south-east arriving at the site during the spring campaign. The ozone compensation point, where photochemical ozone destruction and production processes are in balance, is calculated to be ca. 14 pptv NO for both campaigns.     

Hydroxyl Radical Concentrations Estimated from Measurements of Trichloroethylene during the EASE/ACSOE Campaign at Mace Head, Ireland during July 1996

During the EASE/OXICOA campaign of the NERC ACSOE programme, trichloroethylene and a wide range of man-made halocarbons and radiatively-active trace gases were monitored with high precision and high frequency throughout July 1996 at Mace Head on the Atlantic Ocean coast of Ireland. Trichloroethylene concentrations in concert with many other trace gases became elevated as regionally-polluted and photochemically-aged air masses reached Mace Head. However, as the anticyclonic air masses retreated during 19 and 20 July, trace gas concentrations remained elevated for a significant period. During this 2–4 day period, trichloroethylene concentrations decayed significantly, though the concentrations of the other more chemically-inert trace gases did not. A detailed interpretation of this behaviour using a Lagrangian dispersion model has allowed the estimation of average and peak OH radical concentrations of 3 and 9×10⁶ molecule cm^-3, respectively, during the travel from the source areas in the U.K. and the low countries out to Mace Head. Using a simple box model, the available Mace Head measurements, when combined into a detailed chemical mechanism, generated OH radical concentrations which peaked at 7×10⁶ molecule cm^-3, in close agreement with the estimates based on trichloroethylene decay.     

Estimation of hydroxyl radical concentrations in the marine atmospheric boundary layer using a reactive atmospheric tracer

Hydroxyl radical (OH) concentrations in the atmospheric boundary layer over a number of remote ocean locations are calculated from the measured diurnal variation in atmospheric dimethylsulfide (DMS). By using averaged DMS data sets from extended periods, the calculation yields OH concentrations averaged over periods from several days to weeks. These average OH concentrations range from 7×10⁵ to 2.9×10⁶ molecules cm^-3, corresponding to midday maxima of 3 to 12×10⁶ molecules cm^-3. The lowest values correspond to studies with the lowest light intensity (Antarctic summer and South Atlantic winter), and the highest values to regions with probable anthropogenic influence. In addition to the long term averages, daily average OH levels can be calculated for most days in a two week period from a cruise in the tropical eastern Pacific. These calculations are in good argeement with global average OH levels derived from other tracers, and are consistent with model OH calculations when allowance is made for variation in ambient ozone levels between the studies. Estimates of gas exchange made from the diurnal variation of DMS suggest that either the gas exchange coefficient of DMS or the boundary layer mixing depth may have been overestimated in past analyses.     

拉萨紫外辐射特征分析及估算公式的建立

本文利用2005~2010年的辐射观测资料对拉萨地区紫外辐射的时间变化特征及紫外辐射与总辐射比值的变化特征进行了分析,结果表明,紫外辐射与太阳总辐射的变化规律基本一致,日变化表现为正午大、早晚小;季变化特征是夏季6月最大,冬季1月最小.紫外辐射日累积值6年平均为0.87 MJ·m-2·d-1;紫外辐射有逐年递减的趋势.紫外辐射与总辐射比值也存在着明显日变化,表现为正午大、早晚小的规律;其季节变化也是夏季最大,冬季最小.紫外辐射与总辐射比值6年平均为0.0418;紫外辐射与总辐射比值也呈现逐年递减的趋势.利用2010年大气质量数和晴空指数,建立了适合于拉萨紫外辐射估量的公式,估算值的瞬时值与观测值的平均相对误差最大为8.66%,紫外辐射日累积重构值与观测值平均相对误差仅为5.5%.     

Peroxy Radical Kinetics Resulting from the OH-Initiated Oxidation of 1,3-Butadiene, 2,3-Dimethyl-1,3-Butadiene and Isoprene

The laser flash photolysis/UV absorption spectrometry technique has been used to investigate the kinetics of the peroxy radical permutation reactions (i.e. self and cross reactions) arising from the OH-initiated oxidation of isoprene (2-methyl-1,3-butadiene), and of the simpler, but related conjugated dienes, 1,3-butadiene and 2,3-dimethyl-1,3-butadiene. The results of the two simpler systems are analysed to provide values of the rate coefficients for the 6 peroxy radical permutation reactions of the three types of isomeric peroxy radical produced in each system (T = 298 K, P = 760 Torr). The rate coefficients are all significantly larger than values estimated previously by extrapolation of structure-reactivity relationships based on the kinetics of a limited dataset of simpler radicals containing similar structural features. The results are discussed in terms of trends in self and cross reaction reactivity of primary, secondary and tertiary peroxy radicals containing combinations of allyl, -hydroxy and -hydroxy functionalities. Since the peroxy radicals formed in these systems are structurally very similar to those formed in the isoprene system, the kinetic parameters derived from the results of the simpler systems are used to assist the assignment of kinetic parameters to the 21 permutation reactions of the six types of isomeric peroxy radical generated in the isoprene system. Kinetic models describing the OH-initiated degradation of all three conjugated dienes to first generation products in the absence of NO_x are recommended, which are also consistent with available end product studies. The model for isoprene is considered to be a further improvement on that suggested previously for its OH-initiated oxidation in the absence of NO_x. The mechanism is further extended to include chemistry applicable to NO_x-present conditions, and calculated product yields are compared with those reported in the literature.     

Air pollutant emission rates and concentrations in medieval churches

A series of indoor air quality parameters were determined in two medieval churches, in Cyprus (temperature, relative humidity, total and UV solar radiation, CO₂ indoors and O₃, NO, NO₂ ^*, HNO₃ ^*, HCl, HCOOH, CH₃COOH indoors and outdoors). These data were used as input in a validated indoor air quality model to predict indoor air pollutant source strengths and species concentrations that resulted from dark or photochemical reactions. The NO and NO₂ emission rates due to the burning of incense or candles were estimated. Model results revealed that heterogeneous NO formation takes place simultaneously with the heterogeneous HONO formation. Also, model application has shown that indoor NO_x emissions resulted in decreased free radical concentrations, in contrast to the organic compound emissions, which increased free radical concentrations. This effect of indoor emissions on indoor radicals can partly explain the indoor enhancement/depression of indoor gaseous acid formation.     

Kinetics of the Gas-Phase Reactions of OH and NO3 Radicals and O3 with the Monoterpene Reaction Products Pinonaldehyde, Caronaldehyde, and Sabinaketone

Using a relative rate method, rate constants have been measured for the gas-phase reactions of OH and NO3 radicals with pinonaldehyde, caronaldehyde and sabinaketone at 296 ± 2 K. The OH radical reaction rate constants obtained are (in units of 10–12 cm3 molecule–1 s–1): pinonaldehyde, 48 ± 8; caronaldehyde, 48 ± 8; and sabinaketone, 5.1 ± 1.4, and the NO3 radical reaction rate constants are (in units of 10–14 cm3 molecule–1 s–1): pinonaldehyde, 2.0 ± 0.9; caronaldehyde, 2.5 ± 1.1; and sabinaketone, 0.036 ± 0.023, where the error limits include the estimated overall uncertainties in the rate constants for the reference compounds. Upper limits to the O3 reaction rate constants were also obtained, of <2 × 10–20 cm3 molecule–1 s–1 for pinonaldehyde and caronaldehyde, and <5 × 10–20 cm3 molecule–1 s–1 for sabinaketone. These reaction rate constants are combined with estimated ambient tropospheric concentrations of OH radicals, NO3 radicals and O3 to calculate tropospheric lifetimes and dominant transformation process(es) of these and other monoterpene reaction products.     

Analysis of 40 year records of solar radiation data in Shanghai,Nanjing and Hangzhou in Eastern China

Summary In this paper, we analyze global, direct and diffuse solar radiation data on a horizontal surface observed at stations in Shanghai, Nanjing and Hangzhou for the period of 1961 to 2000. The data include monthly averages of the daily clearness index (G/G₀: the ratio of global to extraterrestrial solar radiation) and the diffuse fraction (D/G: the ratio of diffuse to global solar radiation. The present study has processed and analyzed the data, including variables or statistics of mean, and annual monthly and daily total, the diurnal variation and the frequency of daily totals of global solar radiation. A correlation between daily values of clearness index and diffuse fraction is obtained and recommended correlation equations were calculated. The annual variations and trend of yearly series are analyzed for daily global, direct and diffuse radiation on a horizontal surface, as well as for daily clearness index and diffuse fraction in Shanghai, Nanjing and Hangzhou. The results show: 1) the east China is characterized by a decrease in global and direct radiation and a little increase in diffuse radiation and a negative linear relationship was obtained between clearness index and diffuse fraction. 2) The annual variations of global, direct and diffuse radiation for Shanghai, Nanjing and Hangzhou are similar with relative low values of global and direct radiation in June due to the Meiyu period. 3) The acceleration of air pollution and decrease of relative sunshine are the possible causes for the decrease of global and direct radiation.     

Uptake of the NO <Subscript>3</Subscript> Radical on Aqueous Surfaces

Using a single drop experiment, the uptake of NO₃ radicals on aqueous solutions of the dye Alizarin Red S and NaCl was measured at 293 K. Uptake coefficients in the range (1.7–3.1) ⋅ 10^{− 3} were measured on Alizarin Red S solutions. The uptake coefficients measured on NaCl solutions were in the range of (1.1–2.0) ⋅ 10⁻³ depending on the salt concentration. Both experiments lead to a consistent result for the mass accommodation coefficient of α_NO3 = (4.2_{− 1.7}^+2.2)⋅ 10⁻³. The product H(D_l k_Cl−^II)^0.5 for the NO₃ radical was determined to be (1.9 ± 0.2) M atm^{− 1} cm s^−0.5 M^−0.5 s^−0.5 by fitting the uptake data for the NaCl solutions to the so-called resistance model. The yield of the chemical NO₃ radical source was characterized using UV-VIS and FT-IR spectroscopy. The amount of gas-phase NO₃ radicals measured at elevated humidities was less than expected. Instead, a rise of the gas-phase HNO₃ concentration was found indicating a conversion of gas-phase NO₃ radicals to gas-phase HNO₃ on the moist reactor walls.