Urban ozone measurements using differential optical absorption spectroscopy

In order to improve the air quality in Europe the European Commission has issued a number of directives with regard to acceptable levels of a range of gaseous pollutants, which includes ozone. Therefore, monitoring of this compound is necessary to comply with EU legislation, to provide improved pollution warnings for those who are sensitive to air pollutants as well as providing valuable data for environmental planning. Open-path spectroscopic techniques, such as differential optical absorption spectroscopy (DOAS), are ideal for monitoring pollutants because of the advantages they offer over classical methods and point-source analysers. A DOAS system has been installed in Dublin city centre to monitor a range of criteria pollutants including ozone. Observations of urban background ozone concentrations are presented. The measurements are compared with those obtained using a UV point-source analyser and are presented in the context of the current EU directive. The influence of trans-boundary pollution from mainland Europe leading to ozone episodes is also discussed. Observations of high ozone during this measurement campaign coincided with the influx of photochemically polluted air masses which originated over continental Europe. For the analysed time interval, the data suggest that the ground ozone level in Dublin might be significantly influenced by long-range transport from the United Kingdom and continental Europe.Awarded a Poster Prize on the occasion of the Colloquium Spectroscopicum Internationale XXXIII, Granada, 7–12 September 2003     

Remote sensing measurements for evaluation of air quality in an urban area

The Differential Optical Absorption Spectrometry (DOAS) is a remote-sensing technique finding greater consents in these last years. The analytical principle of the DOAS system is based on the light absorption in the near-UV and Vis regions of those pollutants with fine vibrational structures such as SO2, NO2, O3, nitrous acid, formaldehyde, benzene, toluene, etc.. The relationship among the adsorbed light intensity and the xompound concentrations is ruled by the Lambert-Beer's law. The DOAS analysis allows to study and to interpretate the complex mechanisms of the formation and transformation of the pollutants and particularly of those of secondary origin. In this paper we have reported and discussed the behaviors of NO2, O3, HNO2, formaldehyde, benzene and toluene measured by this system during the 2000--2003 period in the Rome area (an area highly influenced by anthropogenic sources) and in Pietracupa (Molise) area (considered as remote site). The results show how the DOAS system highlight very well the secondary pollution evolution; this, described by the profiles of NO2 and O3 being at the same time products and precursors of the photochemical smog, is not influenced by the emission flow intensity and consequently assumes homogeneous values in the whole urban area.     

Interpretation of atmospheric pollution phenomena in relationship with the vertical atmospheric remixing by means of natural radioactivity measurements (radon) of particulate matter

In this paper the results of seasonal monitoring campaign for primary (benzene and carbon monoxide) and secondary (nitrogen dioxide and ozone) pollutants and for the natural radioactivity of the particulate matter in the urban area of Rome, are reported to investigate acute atmospheric pollution episodes. Comparing the daily concentration trends of primary and secondary pollutants with those of the natural radioactivity, considered as index of the vertical diffusion in the low boundary layer, it has been evidenced that the acute pollution episodes in Rome occur in the winter period for the high atmospheric stability (primary pollution) and in the summer period for the strong diurnal atmospheric remixing (secondary pollution).     

Long pathlength differential optical absorption spectroscopy (D O A S) measurements of gaseous HONO,NO2 and HCNO in the California South Coast Air Basin

A differential optical absorption spectrometer (DOAS) system was operated at Long Beach, CA during the 1987 SCAQS Fall episodes to measure atmospheric concentrations of nitrous acid (HONO), as well as ambient levels of nitrogen dioxide (NO₂) and formaldehyde (HCHO). The rapid scanning (-3000 spectra per min) spectrometer was interfaced to a 25 m basepath open, multiple reflection system operated routinely at a total optical path of 800 m. During several of the Fall episodes at Long Beach, levels of gaseous HONO were the highest (>15 ppb) reported to date by the DOAS technique. Although approximately half, to all, of the measured nighttime HONO concentrations could be accounted for by proposed heterogeneous formation pathways involving NO₂, HONO concentrations correlated well with primary pollutants such as CO and NO, suggesting that elevated nighttime HONO concentrations in the western end of the Los Angeles basin may be influenced by emissions of HONO from combustion sources. This has significant implications for models which assume HONO arises only from secondary formation, rather than a combination of direct emissions and atmospheric reactions. Estimates of hydroxyl (OH) radical production show that photolysis of HONO shortly after sunrise on these episode days produces a large pulse of OH radicals at a time of the day when OH production from photolysis of O₃ and HCHO is low. In terms of integrated OH radical production, HONO is of comparable importance to HCHO and much more important than O₃ during these Fall periods.     

宽带差分吸收光谱与区域毒气探测技术的研究

论述了气体的吸收光谱与区域有害气体光谱探测技术的基本原理,探讨了差分吸收光谱技术,提出了区域远程毒气快速探测的实现方法,介绍了宽光谱光束探测痕量气体入侵、多组光谱仪测试,利用差分吸收光谱法研究出毒气报警系统,并对仪器的发展趋势进行了展望.     

Detection of atmospheric nitrogen dioxide using a miniaturised fibre-optic spectroscopy system and the ambient sunlight

A miniaturised fibre-optic spectrometer based system is presented for direct detection of one of the major atmospheric pollutants, nitrogen dioxide, by absorption spectroscopy using the ambient sunlight as light source. The detection system consists of a 10 cm collimator assembly, a fibre-optic cable and a portable diode-array spectrometer. The absorbance spectrum of the open-path is calculated using a reference spectrum recorded when the nitrogen dioxide (NO2) concentration in the atmosphere is low. The relative concentration of the pollutant is calculated normalising the detected spectra and subtracting the background broadband spectrum from the specific NO2 absorbance features, since the broadband spectrum changes according to atmospheric conditions and solar intensity. Wavelengths between 400 and 500 nm are used in order to maximise sensitivity and to avoid interference from other species. Calibration is carried out using Tedlar sample bags of known concentration of the pollutant. A commercial differential optical absorption spectroscopy (DOAS) system is used as a reference standard detection system to compare the results with the new system. Results show that detection of NO2 at typical urban atmospheric levels has been achieved using an inexpensive field based fibre-optic spectrometer and a readily available, easy to align, light source. In addition the new system can be used to get a semi-quantitative estimation of the nitrogen dioxide concentration within errors of 20%. While keeping the typical benefits of open-path techniques, the new system has important advantages over them such as cost, simplicity and portability.     

Measurements of NO2, SO2, O3, benzene and toluene using differential optical absorption spectroscopy (DOAS) in Shanghai, China

NO2, SO2, O3, benzene, and toluene were measured in Taopu industry park of Shanghai during the period June to August 2003 by differential optical absorption spectroscopy (DOAS) technique. The daily average concentrations of SO2, NO2, and O3 ranged from 5.7 ppb to 40 ppb, 22 ppb to 123 ppb, and 10.6 ppb to 23 ppb respectively. SO2 and NO2 concentrations were found to depend on wind direction. The diurnal variation of NO2 concentrations had two peaks due to traffic emission. Our DOAS measurements of NO2, SO2 and O3 were compared with the conventional measurement instruments (API automatic monitoring instrument). The concept of a percent difference (PD) and linear regression methods were employed to study the difference between DOAS and API instruments. The correlation analysis between PD values and meteorological parameters and analysis of abnormal higher absolute PD values indicated that the lower visibility induced the bad compatibility between the two systems. The results showed that both systems exhibited strong compatibility with good correlation, therefore the DOAS system is able to provide reliable information on distribution patterns of major air pollutants. Average benzene and toluene concentrations were 1.4 and 8.0 ppb respectively.     

Transport of atmospheric pollutants in a semi-rural area of central Italy

An environmental monitoring program aimed to the evaluation of the air quality in the surroundings of Gallese (near Viterbo, in central Italy) was carried out from July 1998 to July 2000. The goal of the program was the comprehension of the transport and transformation mechanisms of nitrogen and sulphur pollutants, and the evaluation of photochemical smog episodes. In this framework, a wide range of atmospheric pollution events was studied, and for many of them it was possible to detect the main source of the pollution. We report in this paper the interpretation of ozone episodes, sulphur dioxide episodes and sea-salts episodes, due to transport from the urban area of Rome, the industrial area of Narni-Tarni and the coastal areas of the Tyrrhenian Sea, respectively.     

大气复合污染及灰霾形成中非均相化学过程的作用

城市和区域大气复合污染的特征为污染源排放的一次污染物通过大气中的化学反应生成高浓度的氧化剂(臭氧等)及细颗粒物等二次污染物,它们在静稳天气下积累,导致低能见度的灰霾现象并严重影响人体健康和气候.大气复合污染中同时存在高浓度的一次排放和二次转化的气态及颗粒污染物,这为细颗粒表面非均相反应提供了充足的反应物;而气态污染物在细颗粒表面的非均相反应可改变大气氧化性及颗粒物的化学组分、物化性质和光学性质,从而可能对大气复合污染和灰霾的形成起到促进的作用.利用漫反射红外傅里叶变换光谱和单颗粒显微拉曼原位在线技术,我们对大气气态污染物NO2、SO2、O3、甲醛在CaCO3、高岭石、蒙脱石、NaCl、海盐、Al2O3和TiO2等大气主要颗粒物表面的反应进行了系统的反应动力学和机制研究,我们发现反应主要产物为硫酸盐、硝酸盐或甲酸盐,它们可极大改变颗粒物吸湿性和消光性质.通过分析这些非均相反应的动力学过程,我们识别出NO2-颗粒物-H2O、SO2-颗粒物-O3、有机物/SO2-颗粒物-光照等三元反应体系的协同作用机制,这些协同机制对于阐明大气复合污染及灰霾形成的反馈机制和非线性过程提供了实验证据和理论依据.     

Atmospheric concentrations of sulfur dioxide, nitrogen oxides, ammonia, hydrogen chloride, nitric acid, formic and acetic acids in the south of Vietnam measured by the passive sampling method.

A passive sampling method was applied to measure the concentrations of air pollutants, such as sulfur dioxide, nitrogen oxides, ammonia, hydrogen chloride, and nitric, formic and acetic acids, in the ambient air at four test sites in the southern region of Vietnam. The monthly averages and the average concentrations of air pollutants during the period from July 2001 to September 2002 are reported here. The concentrations of air pollutants varied widely, depending on the test sites and the sampling periods. The average concentrations of sulfur dioxide in the air during the period from July 2001 to September 2002 at the four test sites were 3.3-16.9 ppb, and those of nitrogen dioxide were 5.4-12.8 ppb. The concentrations of nitrogen monoxide and hydrogen chloride were very low at all of the test sites. The observed concentrations of all of the above-mentioned pollutants were lower than those of the Vietnamese standards of air pollutants.     

The roles of heterogeneous chemical processes in the formation of an air pollution complex and gray haze

Urban and regional air pollutions are characterized by high concentrations of secondary pollutants such as photo-oxidants (mainly ozone) and fine particulate matter,which are formed through chemical reactions of the primary pollutants emitted from various sources.The accumulation of these pollutants under stagnant meteorological conditions results in the formation of gray haze,reducing visibility and causing major impacts on human health and climate.In an air pollution complex,the coexistence of high concen...     

Designing Novel Strategy to Produce Active Nanohybrids in Sunlight for Purification of Water Based on Inorganic Nanolayers,Magnetic Nanocomposites and Organic Species

Energy and water related problems have attracted strong attention from scientists across the world because of deficient energy and water pollution. Following this line, new strategy depended on preparing nanolayers of Al/Zn and magnetic nanoparticles of cobalt iron oxides nanocomposite in addition to long chains of hydrocarbons of stearic acid to be used as roofs, fillers and pillars; respectively, to design optical-active nanohybrids in sunlight for removing the colored pollutants from water in few minutes. By using long chains of hydrocarbons of stearic acid, X-ray diffraction (XRD) results and TEM images showed expansion of the interlayered spacing from 0.76 nm to 2.02 nm and insertion of magnetic nanoparticles among the nanolayers of Al/Zn. The optical properties and activities showed that the nanohybrid structure based on zinc oxide led to clear reduction of the band gap energy from 3.3 eV to 2.75 eV to be effective in sunlight. Photocatalytic degradation of the dye of acid green 1 confirmed the high activity of the prepared zinc oxide nanohybrids because of a complete removal of the dye after ten minutes in sunlight. Finally, this strategy was effective for producing photo-active nanohybrids for using renewable and non-polluting energy for purifying water.     

SiO2负载的TiO2光催化剂可见光催化降解染料污染物

 采用酸催化溶胶-凝胶法制备了SiO2负载的TiO2光催化剂,考察了制备条件对负载型TiO2光催化剂的晶相、结构、比表面积和可见光催化活性的影响. 结果表明,采用SiO2为载体时,TiO2以纳米颗粒的形态分散在载体表面,负载型TiO2/SiO2催化剂的比表面积大、等电点低而且热稳定性能良好. 偶氮染料酸性橙7的可见光催化降解实验结果表明,染料污染物在催化剂表面的吸附是影响催化剂可见光催化活性的重要因素. 与试剂TiO2样品相比,负载型TiO2/SiO2光催化剂具有更好的光催化活性和沉降性能.     

Methods of Determination of Antibiotic Residues in Honey

Monitoring antibiotics residues in honey and honey products helps to assess the potential risk of these products to human health. These data provide an insight in the extent of antibiotic treatment that has been used during the beekeeping and enable the evaluation of potential environment pollution with antibiotic residues. This article offers an overview of methods for identification and determination of different antibiotics potentially present in honey, as well as of maximum residue limits for antibiotics in bee products, in particular honey. It is important to stress the importance of strict monitoring system and validation of analytical methods that will enable an accurate, precise and reliable determination of acceptable minimal concentrations of pollutants in honey.     

The analysis of seasonal air pollution pattern with application of neural networks

Air pollution monitoring includes measuring the concentrations of air contaminants such as nitrogen dioxide, sulfur dioxide, some polycyclic aromatic hydrocarbons(PAHs), suspended particulate matter (PM) and tar substances. The purpose of this study was to determine the possibility of using artificial neural networks for identification of any patterns occurring during heating and nonheating seasons. The samples included in the study were collected over a period of 5 years (1997–2001) in the area of the city of Gdansk and the levels of pollutants measured in the samples collected were used as inputs to two different types of neural networks: multilayer perceptron (MLP) and self-organizing map (SOM). The MLP was used as a tool to predict in what heating season a certain sample was collected, and the SOM was applied for mapping all samples to recognize any similarities between them. This study also presents the comparison between two projection methods—linear (principal component analysis, PCA) and nonlinear (SOM)—in extracting valuable information from multidimensional environmental data. In the research the MLP model with 13-12-1 topology was developed and successfully trained for classification of air samples from different seasons. The sensitivity analysis on the inputs to the MLP indicated benz[α]anthracene, benzo[α]pyrene, PM₁, SO₂, tar substances and PM₁₀ as the most distinctive variables, while PCA pointed to PAHs and PM₁.     

小波降噪技术在差分吸收光谱浓度检测中的应用

为了实现对工业气体SO₂的浓度进行监控,基于紫外差分吸收光谱法开发了SO₂在线检测系统。针对系统噪声和Mie散射使吸收光谱叠加带来的误差,本文提出采用小波变换降噪技术代替传统光谱处理方法中的多项式平滑滤波技术来提高检测精度。通过对应用了Symlets、Daubechies、Coiflet和Biorthogonal这4种不同小波函数的实验数据分析和对传统小波阈值选取方式的改进,最终确定了基于rigisure阈值的小波阈值去噪的信号处理方法,并提出一种新的信噪比量来衡量信号处理的效果。这种方法可以快速可靠地处理光谱信号,处理后所得的监测浓度准确度基本控制在1.5%以内。在实验室环境下和工业现场环境下的大量实验结果表明本方法能有效的减小噪声对SO₂浓度监测带来的影响。     

Fluorescence monitoring of ultrasound degradation processes

Ultrasound-based water treatment is often applied for degradation of stable organic pollutants, such as polycyclic aromatic hydrocarbons and halogenated compounds. Monitoring the degradation process, during the application of ultrasound radiation, is of considerable economical interest. In this work, the possibility of performing on-line spectral analysis during sonication was examined and it was found that direct absorption or fluorescence readings are misleading. Optical monitoring is strongly affected by the absorption and scattering of light by cavitation micro-bubbles and ultrasound induced particulates. A model was developed to account for these effects and to allow for on-line fluorescence analysis. The model takes into account the absorption and scattering coefficients of the micro-bubbles and particulates, as well as their time dependent concentration. The model parameters are found from independent measurements where the pollutants are added to already sonicated pure water. Then, the model is tested for predicting the actual fluorescence behavior during the sonication process. It has been shown that the model allows for recovery of the true degradation data, as obtained by off-line HPLC measurements.     

Working principle and application of photocatalytic optical fibers for the degradation and conversion of gaseous pollutants

Photocatalytic optical fibers are promising for the degradation of gaseous and volatile pollutants in air due to their high specific surface area, high light utilization efficiency, easy regeneration, and sustainability. In particular, photocatalytic optical fibers have proven highly useful for the removal and conversion of different kinds of air pollutants in air. However, these fibers suffer from low photocatalytic degradation efficiencies. In this review, we have focused on introducing photocatalytic quartz optical fibers and photocatalytic plastic optical fibers for the degradation and transformation of gas-phase air pollutants. The principle of photocatalytic optical fibers and main methods for improving their photocatalytic and light utilization efficiencies based on semiconductor photocatalytic coatings are summarized. Moreover, the Langmuir-Hinshelwood kinetic rate equation was summarized to analyze the photocatalytic reduction of gaseous pollutants. Finally, an outlook on the future of photocatalytic optical fibers toward the removal and conversion of gaseous air pollutants is discussed.     

The Detection of Source Levels of Sulfur Dioxide Using a Piezo-Electric Detector and Permeation Membrane

Abstract

The detection of gaseous pollutants using a coated vibrating quartz crystal has been the topic of several studies. Detection of sulfur dioxide with an alkanoamine-coated crystal has already been shown feasible for ambient air pollution levels. Detection of sulfur dioxide at source levels using the piezo-electric method has previously not been proven successful. This work presents the refinements, calibration, and performance of a source monitoring instrument which incorporates a sulfur dioxide permeable membrane as a dilution interface.