A Portable Fiber-Optic Chemical Device for the Quantitative Determination of Carbon Monoxide from Automobile Exhaust Emissions

ABSTRACT

A colorimetxic method for the quantitative determination of CO by diffuse reflectance is described. This method is based on the reduction by CO of Mo (VI) from the indicator reagent molybdosilicic acid (H₈Si[Mo₂O₇]₆). The reduction yielded a change of color from clear yellow to dark green on white disk filter chart paper wetted with reagent indicator solution. The gaseous mixture containing CO was forced to pass through this chart paper, initiating the reaction. The intensity of the color produced, measured by diffuse reflectance, was proportional to the CO concentration present in exhaust gases in the range from 0.02 to 12% volume/volume (v/v). A 650-nm light-emitting diode was used as a light source. A two-fiber-optic system carried the light from the source to the detection system, which was composed of a photodiode, an amplification circuit, and a digital display. The method was applied with success in field measurements for automobiles in the Otto cycle. In a previous paper, this method was used for the quantitative determination of exhaust emissions from diesel-fueled vehicles.¹     

快速测定饮用水中的石油类

使用F2000型红外光度测油仪，测定水质中的石油类，方法是采用一次定量萃取代替两次萃取定容，用直接流出比色代替无水硫酸钠过滤吸水后的比色，而不采用盐析的方法来快速测定饮用水中的石油类。方法的精密度和准确度均达到国家标准要求，减轻了工作强度，节省了时间和药品，适应快速测定的要求。     

Use of diffuse reflectance spectrometry in spot test reactions for quantitative determination of cations in water

Diffuse reflectance spectroscopy can be successfully used for the quantitative determination of small amounts of pollutants like metals. The remission function was found to be linearly proportional to the concentration, when we applied the Kubelka–Munk equation. The color reactions of Cu(II), Co(II), and Ni(II) with dithiooxamide, were realised on filter paper. Reaction between Fe(III) and ammonium thiocyanate was realized on filter paper and gelatine matrix. All measurements were accomplished with a laboratory-constructed reflectometer. We have obtained a calibration curve by plotting the optical density of reflectance A_R vs log of the mol l⁻¹ concentration. Limits of detection at the 10⁻⁴ M level were estimated for all the compounds. Linear dynamic range extend over one order of magnitude and shows the potential of device for the quantitative analysis of environmental pollutants.     

Determination of chlorine in air with the pyridine-pyrazolone reagent

An improved method for the determination of chlorine in air is described. The principle of this method is based on the absorption of chlorine in p-toluenesulfonamide aqueous solution, followed by color development with a pyridine-pyrazolone reagent. Both the chlorine absorbed in the solution and the color developed with the reagent were stable. Positive interference by nitrogen dioxide was not observed.     

A method for removal of CO from exhaust gas using pulsed corona discharge

An experimental study of the oxidation of CO in exhaust gas from a motorcycle has been carried out using plasma chemical reactions in a pulsed corona discharge. In the process, some main parameters, such as the initial CO concentration, amplitude and frequency of pulses, residence time, reactor volume, and relative humidity (RH), as well as their effects on CO removal characteristics, were investigated. O3, which is beneficial to reducing CO, was produced during CO removal. When the exhaust gas was at ambient temperature, more than 80% CO removal efficiency was realized at an initial concentration of 288 ppm in a suitable range of the parameters.     

A Method for Removal of CO from Exhaust Gas Using Pulsed Corona Discharge

ABSTRACT

An experimental study of the oxidation of CO in exhaust gas from a motorcycle has been carried out using plasma chemical reactions in a pulsed corona discharge. In the process, some main parameters, such as the initial CO concentration, amplitude and frequency of pulses, residence time, reactor volume, and relative humidity (RH), as well as their effects on CO removal characteristics, were investigated. O₃, which is beneficial to reducing CO, was produced during CO removal . When the exhaust gas was at ambient temperature, more than 80% CO removal efficiency was realized at an initial concentration of 288 ppm in a suitable range of the parameters.     

Control of diesel gaseous and particulate emissions with a tube-type wet electrostatic precipitator

In this study, experiments were performed with a bench-scale tube-type wet electrostatic precipitator (wESPs) to investigate its effectiveness for the removal of mass- and number-based diesel particulate matter (DPM), hydrocarbons (HCs), carbon monoxide (CO), and oxides of nitrogen (NOx) from diesel exhaust emissions. The concentration of ozone (O3) present in the exhaust that underwent a nonthermal plasma treatment process inside the wESP was also measured. A nonroad diesel generator operating at varying load conditions was used as a stationary diesel emission source. The DPM mass analysis was conducted by means of isokinetic sampling and the DPM mass concentration was determined by a gravimetric method. An electrical low-pressure impactor (ELPI) was used to quantify the DPM number concentration. The HC compounds, n-alkanes, and polycyclic aromatic hydrocarbons (PAHs) were collected on a moisture-free quartz filter together with a PUF/XAD/PUF cartridge and extracted in dichloromethane with sonication. Gas chromatography (GC)/mass spectroscopy (MS) was used to determine HC concentrations in the extracted solution. A calibrated gas combustion analyzer (Testo 350) and an O3 analyzer were used for quantifying the inlet and outlet concentrations of CO and NOx (nitric oxide [NO] + nitrogen dioxide [NO2]), and O3 in the diesel exhaust stream. The wESP was capable of removing approximately 67-86% of mass- and number-based DPM at a 100% exhaust volumetric flow rate generated from 0- to 75-kW engine loads. At 75-kW engine load, increasing gas residence time from approximately 0.1 to 0.4 sec led to a significant increase of DPM removal efficiency from approximately 67 to more than 90%. The removal of n-alkanes, 16 PAHs, and CO in the wESP ranged from 31 to 57% and 5 to 38%, respectively. The use of the wESP did not significantly affect NOx concentration in diesel exhaust. The O3 concentration in diesel exhaust was measured to be less than 1 ppm. The main mechanisms responsible for the removal of these pollutants from diesel exhaust are discussed.     

氮掺杂氧化钛的简易制备及可见光催化活性的研究

为开发对可见光响应的催化剂,以尿素为氮掺杂剂,采用简易溶胶-凝胶法制备氮掺杂氧化钛,并以2,4-DCP的降解检验其光催化活性。XRD、BET、XPS和UV-Vis漫反射光谱分析表明,随着氮/钛原子比（N/Ti)的增大,各催化剂晶粒尺寸减小,比表面积增大,锐钛矿相向金红石相的转变得到抑制,除0#样品出现金红石相外,其他催化剂均只出现锐钛矿相;掺入催化剂的N位于晶格O位点和晶格间隙,替代N和间隙N掺杂使催化剂的光吸收发生明显的红移。荧光光谱分析表明,当N/Ti在0～6范围内增加时,反应体系中·OH自由基的产生速率增加,当N/Ti增大至8时,速率则下降。相似的规律也表现在氮掺杂量对光催化活性的影响。适量氮掺杂能增强氧化钛的可见光催化活性,该改性催化剂可用于有机污染物的太阳光激催化降解。     

The effect of commuting microenvironment on commuter exposures to vehicular emission in Hong Kong

Vehicular exhaust emission has gradually become the major air pollution source in modern cities and traffic related exposure is found to contribute significantly to total human exposure level. A comprehensive survey was conducted from November 1995 to July 1996 in Hong Kong to assess the effect of traffic-induced air pollution inside different commuting microenvironments on commuter exposure. Microenvironmental monitoring is performed for six major public commuting modes (bus, light bus, MTR, railway, tram, ferry), plus private car and roadside pavement. Traffic-related pollutants, CO, NO_x, THC and O₃ were selected as the target pollutants. The results indicate that commuter exposure is highly influenced by the choice of commuting microenvironment. In general, the exposure level in decreasing order of measured pollutant level for respective commuting microenvironments are: private car, the group consisting light bus, bus, tram and pavement, MTR and train, and finally ferry. In private car, the CO level is several times higher than that in the other microenvironments with a trip averaged of 10.1 ppm and a maximum of 24.9 ppm. Factors such as the body position of the vehicle, intake point of the ventilation system, fuel used, ventilation, transport mode, road and driving conditions were used in the analysis. Inter-microenvironment, intra-microenvironment and temporal variation of CO concentrations were used as the major indicator. The low body position and low intake point of the ventilation system of the private car are believed to be the cause of higher intake of exhaust of other vehicles and thus result in high pollution level in this microenvironment. Compared with other metropolis around the world and the Hong Kong Air Quality Objectives (HKAQO), exposure levels of commuter to traffic-related air pollution in Hong Kong are relatively low for most pollutants measured. Only several cases of exceedence of HKAQO by NO₂ were recorded. The strong prevailing wind plus the channeling effect created by the harbor, the fuel used, the relative abundance of new cars and the successful implementation of the vehicle emission control program are factors that compensate the effect of the emission source strength and thus lead to low exposure levels.     

Methodological trends in the design of recent microenvironmental studies of personal CO exposure

This paper describes the designs of three recent microenvironmental studies of personal exposure to carbon monoxide (CO) from motor vehicle exhaust. These studies were conducted sequentially, first in four California cities (Los Angeles, Mountain View, Palo Alto, and San Francisco), then in Honolulu, and, most recently, in metropolitan Washington, D.C. Though study purposes differed, each study faced common methodological issues related to personal exposure monitors (PEMs), quality assurance and data collection procedures, and the selection of microenvironments for study.Two major objectives of the California cities study were to determine the CO concentrations typically found in commercial settings and to define and classify microenvironments applicable to such settings: The Honolulu study measured merchant exposure to CO in shopping centers attached to semienclosed parking garages during business hours and commuter exposure to CO in vehicles (passenger cars and buses) on congested roadways during peak periods. The intent of the Washington study was to develop a model of commuter exposure to motor vehicle exhaust using CO as an indicator pollutant.Certain trends are discernible from reviewing the three studies. There are clearly trends in PEM development that have expanded instrument capabilities and automated data collection and storage. There are also trends towards more rigorous quality assurance procedures and more standardized protocols for collecting exposure data. Further, one can see a trend towards more elaborate indicators for identifying microenvironments for study. Finally, there is a trend towards using personal monitors in public policy review and evaluation.     

纳米TiO2-xNx催化剂的制备及其活性研究

以钛酸丁酯为前驱物、无水乙醇作溶剂、二乙醇胺作为抑制剂,采用溶胶-凝胶法制备TiO2溶胶,在NN3气流中直接进行热处理,制备一系列不同焙烧温度的淡黄色的掺氮纳米TiO2粉体。经XRD、UV-Vis和FTIR分析表明,实验制得的TiO2-xNx在350、400、450、500和550℃热处理3 h后仍为锐钛型;450℃保温3 h掺氮样品具有最佳的紫外-可见光响应,其吸收边红移至720 nm左右。罗丹明B的可见光降解实验及产物分析表明,掺氮样品具有良好的可见光催化活性。     

Quantitative Determination of Formaldehyde in the Parts Per Hundred Million Concentration Level

A new method has been developed for the determination of trace quantities of formaldehyde and appears to be superior to existing methods. The procedure is based on a modification of Schiff’s test for aldehydes. A mixture of dichlorosulfitomercurate II complex and acid bleached pararosaniline hydrochloride is used as the reagent. In the presence of formaldehyde, a purple color is produced. The method is highly sensitive to formaldehyde and acetaldehyde, simple and does not require concentrated acids. When applied to air pollution studies, the method is virtually free of interferences from higher aldehydes. The paper describes the application of this method to spot sampling of the atmosphere and to continuous atmospheric analysis.     

Bench-scale biofilter for removing ammonia from poultry house exhaust

A bench-scale biofilter was evaluated for removing ammonia (NH3) from poultry house exhaust. The biofilter system was equipped with a compost filter to remove NH3 and calcium oxide (CaO) filter to remove carbon dioxide (CO2). Removal of NH3 and CO2 from poultry house exhaust could allow treated air with residual heat to be recirculated back into the poultry house to conserve energy during winter months. Apart from its use as a plant nutrient, NH3 removal from poultry house exhaust could lessen the adverse environmental impacts of NH3 emissions. Ammonia and CO2 were measured daily with gas detector tubes while temperatures in the poultry pen and compost filter were monitored to evaluate the thermal impact of the biofilter on treated air. During the first 37 days of the 54-day study, exhaust air from 33 birds housed in a pen was treated in the biofilter; for the final 17 days, NH3-laden exhaust, obtained by applying urea to the empty pen was treated in the biofilter. The biofilter system provided near-complete attenuation of a maximum short-term NH3 concentration of 73 ppm. During the last 17 days, with a mean influent NH3 concentration of 26 ppm, the biofilter provided 97% attenuation. The CaO filter was effective in attenuating CO2. Compared with a biofilter sized only for NH3 removal, an oversized biofilter would be required to provide supplemental heat to the treated air through exothermic biochemical reactions in the compost. The biofilter could conserve energy in poultry production and capture NH3 for use as plant nutrient. Based on this study, a house for 27,000 broilers would require a compost filter with a volume of approximately 34 m3.     

Reducing the Risk of Accidental Death Due to Vehicle-Related Carbon Monoxide Poisoning

ABSTRACT

Emissions of carbon monoxide (CO) from motor vehicles cause several hundred accidental fatal poisonings annually in the United States. The circumstances that could lead to fatal poisonings in residential settings with motor vehicles as the source of CO were explored. The risk of death in a garage (volume = 90 m³) and a single-family dwelling (400 m³) was evaluated using a Monte Carlo simulation with varying CO emission rates and ventilation rates. Information on emission rates was obtained from a survey of motor vehicle exhaust gas composition under warm idle conditions in California, and information on ventilation rates was obtained from a summary of published measurements in the U.S. housing stock. The risk of death ranged from 16 to 21% for a 3-hr exposure in a garage to 0% for a 1-hr exposure in a house. Older vehicles were associated with a disproportionately high risk of death. Removing all pre-1975 vehicles from the fleet would reduce the risk of death by one-fourth to two-thirds, depending on the exposure scenario. Significant efforts have been made to control CO emissions from motor vehicles with the goal of reducing CO concentrations in outdoor air. Substantial public health benefit could also be obtained if vehicle control measures were designed to take account of acute CO poisonings explicitly.     

Mo-N-TiO_2光催化剂的制备、表征及其活性提高机制

以钼酸铵和氨水分别为钼源和氮源,采用溶胶-凝胶法制备了Mo-N-TiO2光催化剂,并对其进行了XRD、XPS和UV-visDRS表征。XRD结果表明,Mo、N共掺杂有效抑制了TiO2晶粒的生长,提高了TiO2由锐钛矿向金红石相的转变温度。UV-vis表明,Mo-N-TiO2光催化剂可见光吸收能力增强,吸收带边明显＂红移＂,且钼酸铵添加量（相对TiO2）为0.5%的样品＂红移＂程度最大,最大吸收带边为550 nm。XPS分析结果表明,Mo取代了TiO2晶格中的部分Ti4＋,以Mo6＋形式存在的,而N以Ti—N及N—Ti—O形式存在。以罗丹明B为模型污染物,重点考察了钼酸铵添加量与焙烧温度对Mo-N-TiO2光催剂性能的影响。结果表明,400℃焙烧下、钼酸铵添加量为0.5%的样品催化活性最好。模拟太阳光下光照120min对罗丹明B的降解率达到96.8%,是纯TiO2的2.42倍。     

Control of Diesel Gaseous and Particulate Emissions with a Tube-Type Wet Electrostatic Precipitator

Abstract

In this study, experiments were performed with a bench-scale tube-type wet electrostatic precipitator (wESPs) to investigate its effectiveness for the removal of mass- and number-based diesel particulate matter (DPM), hydrocarbons (HCs), carbon monoxide (CO), and oxides of nitrogen (NO_x) from diesel exhaust emissions. The concentration of ozone (O₃) present in the exhaust that underwent a nonthermal plasma treatment process inside the wESP was also measured. A nonroad diesel generator operating at varying load conditions was used as a stationary diesel emission source. The DPM mass analysis was conducted by means of isokinetic sampling and the DPM mass concentration was determined by a gravimetric method. An electrical low-pressure impactor (ELPI) was used to quantify the DPM number concentration. The HC compounds, n-alkanes, and polycyclic aromatic hydrocarbons (PAHs) were collected on a moisture-free quartz filter together with a PUF/XAD/PUF cartridge and extracted in dichloromethane with sonication. Gas chromatography (GC)/mass spectroscopy (MS) was used to determine HC concentrations in the extracted solution. A calibrated gas combustion analyzer (Testo 350) and an O₃ analyzer were used for quantifying the inlet and outlet concentrations of CO and NO_x (nitric oxide [NO] + nitrogen dioxide [NO₂]), and O₃ in the diesel exhaust stream. The wESP was capable of removing approximately 67–86% of mass- and number-based DPM at a 100% exhaust volumetric flow rate generated from 0- to 75-kW engine loads. At 75-kW engine load, increasing gas residence time from approximately 0.1 to 0.4 sec led to a significant increase of DPM removal efficiency from approximately 67 to more than 90%. The removal of n-alkanes, 16 PAHs, and CO in the wESP ranged from 31 to 57% and 5 to 38%, respectively. The use of the wESP did not significantly affect NO_x concentration in diesel exhaust. The O₃ concentration in diesel exhaust was measured to be less than 1 ppm. The main mechanisms responsible for the removal of these pollutants from diesel exhaust are discussed.     

Mo-N-TiO2光催化剂的制备、表征及其活性提高机制

以钼酸铵和氨水分别为钼源和氮源,采用溶胶-凝胶法制备了Mo-N-TiO2光催化剂,并对其进行了XRD、XPS和UV-visDRS表征。XRD结果表明,Mo、N共掺杂有效抑制了TiO2晶粒的生长,提高了TiO2由锐钛矿向金红石相的转变温度。UV-vis表明,Mo-N-TiO2光催化剂可见光吸收能力增强,吸收带边明显"红移",且钼酸铵添加量(相对TiO2)为0.5%的样品"红移"程度最大,最大吸收带边为550 nm。XPS分析结果表明,Mo取代了TiO2晶格中的部分Ti4+,以Mo6+形式存在的,而N以Ti—N及N—Ti—O形式存在。以罗丹明B为模型污染物,重点考察了钼酸铵添加量与焙烧温度对Mo-N-TiO2光催剂性能的影响。结果表明,400℃焙烧下、钼酸铵添加量为0.5%的样品催化活性最好。模拟太阳光下光照120min对罗丹明B的降解率达到96.8%,是纯TiO2的2.42倍。     

Noncatalytic Auto Exhaust Combustor

Present methods for the determination of carbon monoxide are discussed including indicator tubes, the iodine pentoxide reaction and measurement by gas chromatography. In the gas chromatographic method an air sample is separated on a gas-solid chromatogra-phic column and the separated CO is converted to methane by hydrogenation at elevated temperature. The separated CO, in the form of methane, is passed into a hydrogen flame detector and measured. The conversion from CO to methane allows the use of a sensitive ionization detector in place of the thermal conductivity cell which is insufficiently sensitive for the measurement of trace amounts of CO. The optimum operating conditions are discussed. It is possible to determine one ppm CO in air. The iodine pentoxide reaction with CO has been combined with electrometric measurement. The iodine liberated is passed into a Ditte cell and the current generated is measured by an electrometerrecorder combination. This method is continuously direct reading with a permanent record. It is suitable for the continuous routine analysis of one ppm CO.     

Studies on nitric oxide (NO) formation by the green alga Scenedesmus obliquus and the diazotrophic cyanobacterium Anabaena doliolum.

This study provides preliminary evidence that NO production could be a general attribute of algae. Anabaena doliolum was found to be a better NO producer than Scenedesmus and Synechoccocus. Experiments conducted with inhibitors of photosynthesis (DCMU), ATP synthesis (DCCD), and the uncoupler (2,4-DNP) and its analog arsenate clearly revealed that inhibition of nitrite assimilation through the blockage of nitrite reductase (NiR) is primarily responsible for NO emission. A linear relationship between nitrite concentration in the culture medium and NO in the exhaust gas supports the view that accumulation of nitrite is responsible for NO formation. A failure of Scenedesmus, grown in the medium substituted with W for Mo, to produce either NO/NO-2 in light or a 'light-off' peak, and a resumption of these activities upon the addition of Mo proved beyond doubt that a functional nitrate reductase (NR) is necessary for the production of nitrite and NO by algae grown on nitrate as the nitrogen source. Moreover, the appearance of a NO peak immediately after nitrite supplementation under dark conditions in W-substituted cultures with or without glucose ruled out an enzymatic role of NR in NO emission.