Development and validation of a method for the determination of trace alkylphenols and phthalates in the atmosphere

An analytical method has been developed for the simultaneous extraction and determination of trace tertiary octylphenol (t-OP), technical nonylphenol isomers (NP), nonylphenol monoethoxylate isomers (NP1EO) and seven phthalates in the atmosphere using gas chromatography-mass spectrometry (GC-MS). High volume samples were collected using a high-volume pump equipped with a PUF/XAD-2 column for air and glass fiber filter for particles. The detection limits of the method for alkylphenols (APs) and the phthalates ranged from 0.0006 to 0.034 ng m⁻³ in air. The recoveries of t-OP, NP, NP1EO and the phthalates for the entire procedure were satisfactory (>69%). The method was successfully applied to the determination of the analytes in the atmosphere samples collected over land and the ocean. The concentrations of t-OP, NP, NP1EO showed decline trends from land to the open sea, and the phthalates present over land and the North Sea were comparable. It is suggested that the atmosphere is a significant pathway for the transport of alkylphenols and the phthalates in the environment.     

Electron Spectroscopy - A Potentially Useful Tool for Environmental Studies

The technique of electron spectroscopy (ESCA) is reviewed. Those aspects are discussed which seem to be of greatest potential interest to workers in environmental studies. Basic theory of the photoelectron ejection process is considered along with the Auger effect. Factors affecting the calculation of electron binding energies are discussed. Instrumentation utilizing both magnetic and electrostatic monochromators is discussed in some detail.

The nature of ESCA data is considered, along with an extensive tabulation of chemical shifts observed for 15 elements. Application of ESCA to surface studies is reviewed, using examples like effect of layers of material on electron intensities, investigations of zeolites and some elementary catalysis studies. A review of the quantitative aspects of ESCA considers the determination of arsenic in soils and the measurement of mixed oxide ratios.     

Efficient unbiased variance reduction techniques for Monte Carlo simulations of radiative transfer in cloudy atmospheres: The solution

We present five new variance reduction techniques applicable to Monte Carlo simulations of radiative transfer in the atmosphere: detector directional importance sampling, n-tuple local estimate, prediction-based splitting and Russian roulette, and circum-solar virtual importance sampling. With this set of methods it is possible to simulate remote sensing instruments accurately and quickly. In contrast to all other known techniques used to accelerate Monte Carlo simulations in cloudy atmospheres - except for two methods limited to narrow angle lidars - the presented methods do not make any approximations, and hence do not bias the result. Nevertheless, these methods converge as quickly as any of the biasing acceleration techniques, and the probability distribution of the simulation results is almost perfectly normal. The presented variance reduction techniques have been implemented into the Monte Carlo code MYSTIC (“Monte Carlo code for the physically correct tracing of photons in cloudy atmospheres”) in order to validate the techniques.     

The millimeter-wave spectrum of chlorine nitrate (ClONO2): The ν6 vibrational state

The pure rotational spectrum of chlorine nitrate in its v₆ = 1 excited vibrational state has been studied. A total of 2901 lines, with K_a extending to 33 in the ³⁵Cl isotopologue and 30 in the ³⁷Cl isotopologue, respectively, have been recorded and assigned. This analysis, along with our recently reported study of the ν₅/ν₆ν₉ dyad and the improved energy levels of ν₉ reported in this paper, should make possible accurate simulation of the corresponding ν₆ band and its complex hot band structure near 435 cm⁻¹.     

Nucleation of atmospheric aerosol particles

A significant fraction of the total number of particles present in the atmosphere is formed originally by nucleation from the gas phase. Binary nucleation of sulphuric acid and water, ternary nucleation of sulphuric acid, water and ammonia and ion-induced nucleation are thought to be the most important aerosol nucleation processes in the atmosphere. Within the last two decades, instrumentation to observe and characterize nucleation has improved greatly and numerous observations of nucleation have been made including quantification of the nucleation rate, characterization of the growth process and first chemical characterizations of the freshly formed particles. Nucleation has been observed at many different places in the atmosphere: in the boundary layer, in the free troposphere, in remote locations, in coastal areas, in boreal forests as well as urban areas and pollution plumes. In most cases gaseous sulphuric acid is assumed to be the key precursor gas. After nucleation, other supersaturated substances, especially low vapour pressure organics often take part in the subsequent aerosol growth. Iodine oxides seem to be responsible for nucleation observed in some coastal areas.Recent advances in modelling allow for a kinetic treatment of the nucleation process based on measured thermochemical data for the cluster formation. Considerable improvement over the classical nucleation treatment is expected from this approach.A detailed understanding of atmospheric aerosol nucleation processes is needed as the freshly formed particles directly influence the number concentration and size distribution of the atmospheric aerosol. The formation of clouds and precipitation is affected and influences on climate are anticipated. Anthropogenic emissions influence atmospheric aerosol nucleation processes considerably.Despite the comprehensive research efforts, substantial inconsistencies remain and conflicting results of laboratory studies, model studies as well as atmospheric observations persist. Several key questions about the predictability of atmospheric nucleation in general, about the substances, that take part in nucleation and subsequent growth and about the size and composition of the critical cluster, have not been resolved so far. To cite this article: J. Curtius, C. R. Physique 7 (2006).     

Gamma-ray emission from thunderstorm discharges

Fine features of gamma-ray radiation registered during a thunderstorm at Tien-Shan Mountain Cosmic Ray Station are presented. Long duration (100-600 ms) gamma-ray bursts are found. They are for the first time identified with atmospheric discharges (lighting). Gamma-ray emission lasts all the time of the discharge and is extremely non-uniform consisting of numerous flashes. Its peak intensity in the flashes exceeds the gamma-ray background up to two orders of magnitude. Exclusively strong altitude dependence of gamma radiation is found. The observation of gamma radiation at the height 4-8 km could serve as a new important method of atmospheric discharge processes investigation.     

PLS分析与RBF神经网络耦合环境模型

鉴于城市大气环境质量受到诸多复杂因素影响,且各因素间存在多重相关性,本文将偏最小二乘(PLS)分析与人工神经网络径向基网络(RBF)耦合,建立偏最小二乘径向基神经网络模型(PLSRBF),应用于贵阳大气环境质量的检验和预测。实例表明:PLSRBF模型可对原多自变量模型进行降维简化,并可有效提取解释变量信息,防止信息丢失,且具有较强的拟合能力。     

A sensitivity study on spectroscopic parameter accuracies for a mm/sub-mm limb sounder instrument

The purpose of this paper is to perform a detailed error analysis for a mm/sub-mm limb sounding instrument with respect to spectroscopic parameters. This is done in order to give some insight into the most crucial spectroscopic parameters and to work out a list of recommendations for measurements that would yield the largest possible benefit for an accurate retrieval. The investigations cover a variety of spectroscopic line parameters, such as line intensity, line position, air and self broadening parameters and their temperature exponents, and pressure shift. The retrieval process is performed with the optimal estimation method (OEM). The OEM allows one to perform an assessment of the total statistical error, as well as of the model parameter error, such as the error coming from spectroscopic parameters. The instrument parameters assumed are those of the MASTER instrument studied by the European Space Agency, one of the candidate instruments for a future atmospheric chemistry mission. However, the same principle and method of analysis can be applied to any other millimeter/sub-millimeter limb sounding instrument, for instance the Japanese instrument JEM/SMILES, the Swedish instrument Odin, and the Earth Observing System Microwave Limb Sounder. We find that an uncertainty in the intensity of the strong lines give an error of similar magnitude on the retrieved species to which the lines belong. Uncertainties in the line position have overall a small impact on the retrieval, indicating that the line positions are known with sufficient accuracy. The air broadening parameters and their temperature exponents of a few strong lines dominate the error budget. On the other hand, the self broadening parameters and the pressure shifts are found to have a rather small impact on the retrieval.     

Reinvestigation of pressure broadening parameters at 60-GHz band and single 118.75 GHz oxygen lines at room temperature

Low pressure measurements of broadening parameters of the 118.75 GHz fine structure line of oxygen molecule have been made by a BWO-based spectrometer with acoustic detector (RAD) at room temperature. Pressure broadening parameters were obtained for the buffer gases O₂, N₂, Ne, He, Ar, H₂O, CO₂, and CO and have the following values 2.23 ± 0.01, 2.245 ± 0.02, 1.375 ± 0.02, 1.62 ± 0.03, 2.005 ± 0.02, 2.52 ± 0.04, 2.66 ± 0.08, and 2.31 ± 0.05 MHz/Torr, respectively. Measured central frequency is 118 750.340 ± 0.007 MHz. The central frequencies and broadenings by O₂ and N₂ of fine structure lines 1⁺, 5⁻, 7⁺, 11⁺, and 15⁻ belonging to the 60-GHz band are also measured. Comparison of previous and recent data on electronic, rotational, and fine structure lines broadenings reveals their close values (within 10%) and dependencies on corresponding rotational quantum numbers for these different oxygen spectra stretching from millimeter through submillimeter up to the optical bands. Such similarity could be used for estimation of the broadenings of not measured yet oxygen lines.