Photochemical production of molecular hydrogen in lake water and coastal seawater

Samples of lake water and coastal seawater from Nova Scotia, Canada, were irradiated with natural or artificial sunlight to investigate the potential for photochemical hydrogen production. Hydrogen photo-production was observed in all natural water samples. Rates of hydrogen formation were highest in coloured lake water (range: 98–163 pmol L^− 1h^− 1) and lower in seawater (range: 19–45 pmol L^− 1 h ^− 1). Dilutions of the most highly coloured lake sample (Kejimkujik Lake) showed a positive linear relationship between H₂ production rates and CDOM concentration. Photo-production rates normalised to UV absorption coefficients at 350 nm indicated that the photochemical efficiency of hydrogen formation varied between samples, perhaps due to differences in the CDOM composition. Photochemical hydrogen formation was also seen in solutions of syringic acid and acetaldehyde: two low-molecular-weight carbonyl compounds found in natural waters. Photochemistry may therefore offer least a partial explanation for the persistently high levels of hydrogen observed in the low-latitude surface ocean.     

Combined experimental and theoretical studies on methane photolysis at 121.6 and 248 nm—implications on a program of laboratory simulations of Titan’s atmosphere

Methane is, together with N₂, the main precursor of Titan’s atmospheric chemistry. In our laboratory, we are currently developing a program of laboratory simulations of Titan’s atmosphere, where methane is intended to be dissociated by multiphotonic photolysis at 248 nm. A preliminary study has shown that multiphotonic absorption of methane at 248 nm is efficient and leads to the production of hydrocarbons such as C₂H₂ (Romanzin et al., 2008). Yet, at this wavelength, little is known about the branching ratios of the hydrocarbon radicals (CH₃, CH₂ and CH) and their following photochemistry. This paper thus aims at investigating methane photochemistry at 248 nm by comparing the chemical evolution observed after irradiation of CH₄ at 248 and at 121.6 nm (Ly-α). It is indeed important to see if the chemistry is driven the same way at both wavelengths in particular because, on Titan, methane photolysis mainly involves Ly-α photons. An approach combining experiments and theoretical analysis by means of a specifically adapted 0-D model has thus been developed and is presented in this paper. The results obtained clearly indicate that the chemistry is different depending on the wavelength. They also suggest that at 248 nm, methane dissociation is in competition with ionisation, which could occur through a three-photon absorption process. As a consequence, 248 nm photolysis appears to be unsuitable to study methane neutral photochemistry alone. The implications of this result on our laboratory simulation program and new experimental developments are discussed. Additional information on methane photochemistry at 121.6 nm are also obtained.     

Identification and Apportionment of Sources of Ozone‐forming Potential for Proper Reduction Strategies

In this study, results of source identification and apportionment for ambient volatile organic compounds (VOCs) from a previous work were used to estimate ozone‐forming potentials (OFPs) of effective sources for developing proper strategies for reduction of tropospheric ozone pollution. The source identification and apportionment of ambient VOC pollution within Yildiz Technical University's Davutpasa Campus (Istanbul, Turkey) was done by positive matrix factorization (PMF). The results suggested five effective source groups with the emissions related with paint use and solvent use having the highest contributions (36.8 and 28.2%). The results from PMF were used along with maximum incremental reactivities to estimate potentials of individual sources for ozone formation. It was found that biogenic emissions (3.78) and traffic related emissions (gasoline and diesel vehicle exhaust) (3.83 and 3.15, respectively) have the highest potential for ozone formation in terms of grams O₃/g VOC emitted. The results were used to suggest proper source‐based reduction strategies for OFP.     

光化学烟雾的控制试验

利用MM5与RADM的耦合模式,设计了3个削减源排放的试验,用以探讨控制光化学污染的有效途径。试验结果表明,在NMHC/NOx比值很大的前提条件下,NOx地面源排放的削减对降低大气中O3含量的作用最显著,而削减NMHC对降低大气中PAN含量的作用明显,同时削减NMHC和NOx是降低大气光化学污染强度的最佳途径。     

基于MODIS数据的广州市光化学污染预警等级研究

 分析MODIS数据反演的大气气溶胶光学厚度（AOD）与大气环境污染的关系，结果表明： 当空气没有污染时，AOD＜0.3； 轻度污染时，0.3＜AOD＜1.0； 污染严重时，AOD＞1.0。在分析AOD与地面大气污染关系的基础上，结合空气污染指数，将城市光化学污染预警等级分为无、微弱、较弱、较强和强5级，并结合广州市实例进行了验证分析，为进一步建设城市光化学污染预警系统提供基础。     

Observed and modelled “chemical weather” during ESCOMPTE

The new MOdèle de Chimie Atmosphérique à Grande Echelle (MOCAGE) three-dimensional multiscale chemistry and transport model (CTM) has been applied to study heavy pollution episodes observed during the ESCOMPTE experiment. The model considers the troposphere and lower stratosphere, and allows the possibility of zooming from the planetary scale down to the regional scale over limited area subdomains. Like this, it generates its own time-dependent chemical boundary conditions in the vertical and in the horizontal. This paper focuses on the evaluation and quantification of uncertainties related to chemical and transport modelling during two intensive observing periods, IOP2 and IOP4 (June 20–26 and July 10–14, 2001, respectively). Simulations are compared to the database of four-dimensional observations, which includes ground-based sites and aircraft measurements, radiosoundings, and quasi-continuous measurements of ozone by LIDARs. Thereby, the observed and modelled day-to-day variabilities in air composition both at the surface and in the vertical have been assessed. Then, three sensitivity studies are conducted concerning boundary conditions, accuracy of the emission dataset, and representation of chemistry. Firstly, to go further in the analysis of chemical boundary conditions, results from the standard grid nesting set-up and altered configurations, relying on climatologies, are compared. Along with other recent studies, this work advocates the systematic coupling of limited-area models with global CTMs, even for regional air quality studies or forecasts. Next, we evaluate the benefits of using the detailed high-resolution emissions inventory of ESCOMPTE: improvements are noticeable both on ozone reactivity and on the concentrations of various species of the ozone photochemical cycle especially primary ones. Finally, we provide some insights on the comparison of two simulations differing only by the parameterisation of chemistry and using two state-of-the-art chemical schemes for regional photochemical modelling. Regional air quality modelling is found to be highly sensitive to the emission inventory dataset and also to the vertical and horizontal boundary conditions and detailed representation of chemistry. Interestingly enough, they infer the same range of errors compared to total model errors.     

Diurnal cycling of carbon monoxide (CO) in the upper ocean near Bermuda

A coupled photochemical–physical model for the upper ocean carbon monoxide concentration is presented. The coupled model uses a spectral optical model and a number of different mixing parameterizations. It is run using the meteorological forcing conditions measured during a 9-day investigation near Bermuda in the Sargasso Sea in March 1993 in the declining phase of the spring bloom. The baseline runs of the model are successful in simulating measurements made during the campaign, and form the basis of an optimization routine to find better estimates of the production and destruction constants of the photochemical tracer. The optimized values derived in this inverse procedure depend on the mixing parameterization and the assumed dark production rate of carbon monoxide.     

A 24‐h Forecast of Oxidant Concentration in Tokyo Using Neural Network and Fuzzy Learning Approach

In this study, several types of adaptive network‐based fuzzy inference system (ANFIS) with different membership functions (MFs) and artificial neural network (ANN) were employed to predict hourly photochemical oxidants that were oxidizing substances such as ozone and peroxiacetyl nitrate produced by photochemical reactions. The results indicated that ANFIS statistically outperforms ANN in terms of hourly oxidant prediction. The minimum mean absolute percentage errors (MAPEs) of 4.99% could be achieved using ANFIS with bell shaped MFs. The maximum correlation coefficient, the minimum mean square errors, and the minimum root mean square errors were 0.99, 0.15, and 0.39, respectively. ANFIS's architecture consists of both ANN and fuzzy logic including linguistic expression of MFs and if‐then rules, so it can overcome the limitations of traditional neural network and increase the prediction performance.     

The Australian Air Quality Forecasting System: Exploring First Steps Towards Determining The Limits of Predictability For Short-Term Ozone Forecasting

Physical parameterisations of turbulent transfer processes in the atmospheric boundary layer, such as the stability parameterisations developed by Joost Businger, and recent advances in computing capabilities, have been important factors leading to the emergence of operational, numerical air quality forecasting systems. The present paper investigates the performance of the Australian Air Quality Forecasting System (AAQFS) in forecasting the peak 1 h ozone for the current or next day. These 24/36 h forecasts are generated for the Sydney and Melbourne regions and issued twice daily. Quantitative evidence is presented of the potential for the AAQFS to provide accurate numerical air quality forecasts. A second goal is to provide an initial benchmark for investigating the limits of predictability for air quality in the Sydney and Melbourne regions by looking at the dependence of the forecasts on the domain spatial scale (while maintaining the same model grid resolution), the starting time and length of the forecast (0000 UTC starts are 36-h forecasts and 1200 UTC starts are 24-h forecasts), and the sophistication of the photochemical mechanism (simple chemistry, Generic Reaction Set (GRS) and complex chemistry, Carbon Bond IV (CBIV)). The probability of detection by the forecast model is much better than persistence, showing considerable skill. The normalised bias, in general, decreases going from regional scale to sub-regional scale and becomes negative at the station scale. In Melbourne the gross error increases as the domain spatial scale decreases, but in Sydney there is a dip in the error at the sub-regional scale due to a sampling artifact. Better results are obtained at the smaller domain scales for 1200 UTC forecasts in Sydney. These are attributed to the shorter forecast period and secondarily to greater model spin-up effects at 0000 UTC. In Melbourne the results are ambiguous. Similar conclusions are derived from scatter plots of forecasts versus observations. Dividing the scatter plots into four sections by plotting vertical and horizontal lines (at 60 ppb) forms contingency tables for categorical forecasting. These plots show the increase in missed forecasts due to underprediction and the decrease in the number of extreme events detected as the spatial scale decreases. A comparison of the highly condensed GRS photochemical mechanism with the comprehensive CBIV mechanism indicates that, in general, GRS performs well for predicting ozone in urban situations provided that the background concentrations are appropriately specified. The potential to improve the forecasts at the smaller spatial scales, particularly for extreme events at high ozone concentrations, may require moving to a more complex mechanism as computer resources become available. This paper is dedicated to Joost Businger, who had strong ties with the atmospheric boundary-layer community in Australia over the past 40 years. It was while visiting CSIRO in Aspendale, Victoria, in 1965–1966 that Joost determined the stability dependence of the Monin-Obukhov surface-layer profiles. He immediately walked over to Arch Dyer’s office to show Arch his results. Arch carefully examined them, and then opened his desk drawer and pulled out his own plots of the stability dependence that he and Bruce Hicks had obtained. They showed the same curves, and thus the Businger-Dyer-Hicks stability functions were born. Arch and Bruce at the time were struggling with how to handle the internal politics; they needed Bill Swinbank’s approval, as Assistant Divisional Chief, before they could submit their results for publication. Bill had his own very strong ideas that conflicted with observations. Joost’s independent confirmation of their results provided a way forward (Bruce Hicks, personal communication, 2003). Joost has contributed significantly, either directly or indirectly, to experimental field programs both within Australia and overseas and to the development of parameterisations of turbulent transfer processes in the boundary layer.     

区域对流层光化学过程研究

将 MM5和 RADM耦合 ,建立了一个区域大气光化学模式。用此模式来研究区域大气光化学过程。分析了大气光化学过程中前体物、自由基以及主要产物的时空分布及其随时间的变化情况。得到了大气光化学过程各主要成分的分布及其演变特征。在此基础上 ,分析了水平平流、垂直扩散及沉降以及化学转化等物理、化学过程在大气光化学过程中的相对重要性 ,结果表明 ,水平平流和垂直扩散及沉降等物理过程对大气光化学过程中各种成分的浓度分布及其随时间的变化有重要的作用。