A multi-residue method for characterization and determination of atmospheric pesticides measured at two French urban and rural sampling sites

The extensive use of pesticides to protect agricultural crops can result in the transfer of these compounds into the atmosphere and their diffusion towards urban areas. Precise evaluation of the geographic impact of this type of pollution is important environmentally. In this paper, analytical methods for the sampling, characterization, and determination of agricultural pesticides in air were developed; the methods were then applied in the Paris and Champagne regions. Sixteen pesticides belonging to nine chemical families were monitored. Sampling was carried out in urban (Paris) and rural (Aube district) sites, utilizing either a high-volume pump (12.5 m³ h^–1) (urban site) or a low-volume pump (2.3 m³ h^–1) for the rural site. Quartz filters and polyurethane foams (PUF) were used for sampling in all cases. After extracting the samples and concentrating the recovered solutions, high-performance liquid chromatography (HPLC) analysis with UV detection was performed. Identification of the pesticides was confirmed by applying to the HPLC measurements a novel UV-detection procedure based on the normalized absorbance variation with wavelength (Noravawa procedure). The presence of metsulfuron methyl, isoproturon, linuron, deltamethrin (and/or malathion), and chlorophenoxy acids (2,4-D and MCPP) was found at the urban sampling site at levels ranging from about 1 to 1130 ng m^–3 of air, depending on the compound and sampling period. On the rural sampling site residues of isoproturon, deltamethrin (and/or malathion), MCPP, and 2,4-D were generally detected at higher levels (19–5130 ng m^–3) than on the urban site, as expected. The effects of the weather conditions and agricultural activity on the atmospheric concentrations of pesticides are discussed, as are long-range atmospheric transfer processes for these pesticides.     

Partition function data and impact on retrieval quality for an mm/sub-mm limb sounder

The partition function plays a major role as it mainly governs the dependence of the spectral line strength (or line intensity) on the temperature. A wrong partition function will lead to an incorrect line strength, which will lead to a systematic error in the retrieval. Therefore, a careful investigation of the available partition function data and the sensitivity of the retrieval to this is required. Two partition function data sets, the HITRAN and the JPL, are considered in this paper. In a first step, we investigate the spread of the partition function ratios from the simple approximation values given by theory. We find that the HITRAN partition functions are usually higher than the values quoted by the simple approximation. The JPL partition functions are much closer to the values given by the approximation. Comparing directly the two datasets, with some exceptions, a good agreement is found. Only for 16 molecules (from 66 considered molecules), the deviations in the two data sets are larger than 2%. The retrieval error analysis shows that, for the case of the molecular species with strong signatures, an uncertainty in the partition function is directly translated into a retrieval error of the species in question. However, the uncertainty in the partition function of this species can have a high impact on the quality of weak species retrieval.     

基于功率谱的大口径望远镜面型评价

为了更好地评价与研究受视宁影响的观测系统,引入了基于功率谱的分析方法.使用不同截止频率以及衰减系数的卡曼谱来反演系统的中高频误差,同时使用Zernike多项式来表征系统低阶起伏,结合这两种误差,得到了系统误差的数值模型.最后,通过分析实际波前叠加数值模拟大气扰动前后的功率谱,验证了本方法评价受视宁影响的大口径系统的可行性.     

New measurements of the water vapor continuum in the region from 0.3 to 2.7 THz

We present a spectroscopic study of the water vapor continuum absorption in the far-IR region from 10 to 90 cm⁻¹ (0.3-2.7 THz). The experimental technique combines a temperature-stabilized multipass absorption cell, a polarizing (Martin-Puplett) interferometric spectrometer, and a liquid-He-cooled bolometer detector. The contributions to the absorbance resulting from the structureless H₂O-H₂O and H₂O-N₂ continua have been measured in the temperature range from 293 to 333 K with spectral resolution of 0.04-0.12 cm⁻¹. The resonant water vapor spectrum was modeled using the HITRAN04 database and a Van Vleck-Weisskopf lineshape function with a 100 cm⁻¹ far-wing cut-off. Within experimental uncertainty, both the H₂O-H₂O and H₂O-N₂ continua demonstrate nearly quadratic dependencies of absorbance on frequency with, however, some deviation near the 2.5 THz window. The absorption coefficients of 3.83 and 0.185 (dB/km)/(kPa THz)² were measured for self- and foreign-gas continuum, respectively. The corresponding temperature exponents were found to be 8.8 and 5.7. The theoretically predicted foreign continuum is presented and a reasonable agreement with experiment is obtained.     

Time series analysis of long-term data sets of atmospheric mercury concentrations

Different aspects and techniques of time series analysis were used to investigate long-term data sets of atmospheric mercury in the Northern Hemisphere. Two perennial time series from different latitudes with different seasonal behaviour were chosen: first, Mace Head on the west coast of Ireland (53°20N, 9°54W), representing Northern Hemispherical background conditions in Europe with no indications for so-called atmospheric mercury depletion events (AMDEs); and second, Alert, Canada (82°28N, 62°30W), showing strong AMDEs during Arctic springtime. Possible trends were extracted and forecasts were performed by using seasonal decomposition procedures, autoregressive integrated moving average (ARIMA) methods and exponential smoothing (ES) techniques. The application of time series analysis to environmental data is shown in respect of atmospheric long-term data sets, and selected advantages are discussed. Both time series have not shown any statistically significant temporal trend in the gaseous elemental mercury (GEM) concentrations since 1995, representing low Northern Hemispherical background concentrations of 1.72±0.09 ng m^–3 (Mace Head) and 1.55±0.18 ng m^–3 (Alert), respectively. The annual forecasts for the GEM concentrations in 2001 at Alert by two different techniques were in good agreement with the measured concentrations for this year.     

Numerical and laboratory prediction of smoke lofting in the atmosphere over large area fires

We analyze the lofting of aerosol in the atmosphere over a large scale fire. According to the well-known theory of “nuclear winter”, soot, rising in the atmosphere, may spread in the stratosphere and screen sun rays, which may in turn result in long-term catastrophic consequences for the climate. The height reached by the soot is critical for the climate modeling because long-term global consequences can only be caused by a significant quantity of soot injected into the stratosphere. Most of the studies in the present literature are devoted to long-term modeling. The study of the initial (pyrocumulus) stage of the problem has attracted much less attention with the amount of the soot injected into the mid-latitude stratosphere often being postulated. The amount of smoke that enters the stratosphere is crucial for climate consequences. It is therefore important to predict accurately the active stage of a large-scale fire, which is accompanied by the development of convective columns. The paper is devoted to the analysis of different approaches to the prediction of the altitude of smoke lofting over large scale fires. Some numerical, laboratory and analytical methods are considered. The latter two approaches are based on the theory of similarity. The results obtained by different techniques are compared with each other. Special attention is given to high resolution simulations, which accurately enough resolve gravity waves.     

Multiwavelength lidar for measurements of atmospheric aerosol

We represent the results of our investigations on size distribution of atmospheric aerosol particles by means of a multiwavelength lidar based on Nd : YAG and Ti : Sa lasers equipped with frequency multipliers. The measurements were performed in mountainous areas.     

Quantification of VOC emission rates from the biosphere

Determining which volatile organic compounds (VOCs) are synthesized by plants and emitted into the atmosphere and at what rates is a critical component of our understanding of the Earth system, as is understanding how these emissions respond to environmental controls and how they may change in the future. Here, we review the methods used to sample biogenic VOC emissions, from the leaf scale to the regional scale, and focus on the challenges that this task presents.     

均相配位反应中硫氰酸根配体配位模式的影响因素研究

研究了均相硫氰化铜反应中,试剂的初始浓度对硫氰酸根配位模式的影响。结果表明,水溶液中铜离子的德拜厚度直接影响了硫氰酸根的配位模式。     

湖泊沉积物中腐殖酸的紫外—可见分光光度法测定

从湖泊沉积物中提取腐殖酸（主要是胡敏酸）用紫外可见吸收光谱进行了测定，并通过其吸光度对波长求二阶导数对腐殖酸结构进行了分析鉴定。