The sampling of sulfur dioxide in air with impregnated filter paper

A method is suggested for the sampling of sulfur dioxide in air with impregnated filter paper instead of bubblers. The best aqueous impregnating solution contained potassium hydroxide with glycerol or triethanolamine. The possibilities and limitations of the method are discussed. High collection efficiencies (over 95%) were obtained at relative humidities above 25%. Collected sulfur dioxide was stable for at least several weeks when the filters were kept dry after the sampling. The method is especially suited for short-time measurements and for automatic sampling with smoke samplers.     

Radiometric efficiency of analytical filters at different physical conditions

The radiometric efficiency of three analytical filters AFA-RSP-20, AFA-RMP-20 and AFA-RMV-20 was examined at different air velocities and aerosol number concentrations. An experimental setup had been constructed with 2 m³ radon chamber. Alpha radiometry was used to measure the deposited activities in the filters. Aerosols parameters like number concentration and size distribution are measured continuously with an aerosol diffusion spectrometer (ADS). RMV filter has a stable efficiency ~ 99.8%. The RSP and RMP filters efficiency is depending on the aerosol concentration and air sampling velocity. The effect of an aerosol concentration on the filter efficiency is more obvious than the effect of air velocity.

     

催化发光法同时测定空气中的甲醛、苯和二氧化硫

基于甲醛、苯和二氧化硫在纳米Ti3CeY2O11上的催化发光有交叉敏感现象,在3个波长处分别确定甲醛、苯和二氧化硫浓度与催化发光信号强度的响应关系,再依据发光信号强度的叠加性特征即可获取甲醛、苯和二氧化硫的准确浓度,据此建立了同时测定空气中甲醛、苯和二氧化硫的新方法.3个分析波长分别为420、535和680 nm,敏感材料表面温度为280℃,载气流速为130 mL/min.本方法对甲醛、苯和二氧化硫的检出限(3σ)分别为0.04、0.05和0.10 mg/m3,线性范围分别为0.08~75.60 mg/m3、0.10~101.40 mg/m3和0.30~115.00 mg/m3, 回收率分别为96.4%~103.7%、97.8%~102.5%和97.2%~103.3%.常见共存物,如乙醛、甲苯、硫化氢、氨、甲醇、乙醇和二氧化碳等不干扰测定.连续200 h通浓度均为50 mg/m3的甲醛、苯和二氧化硫混合气体,发光强度的相对偏差≤2%,表明此纳米级复合氧化物对甲醛、苯和二氧化硫的敏感性的寿命长.本方法充分利用了交叉敏感现象,可以实现空气中甲醛、苯和二氧化硫的在线分析.     

The adsorption properties of organic sulfur compounds on zeolite-based sorbents impregnated with rare-earth metals

Dimethyl disulfide (DMDS) and dimethyl sulfide (DMS) are non-polar, stable, organic sulfur compounds found in liquefied petroleum gas, and their oxidation in the atmosphere results in the formation of tropospheric sulfur dioxide, which is subsequently converted into sulfuric acid, as the main factor of acid rain. In the present study, adsorption processes were devised based on the use of modified zeolite impregnated with rare-earth metals (Ce, La or Pr) for the adsorption of DMDS and DMS, and their sorption capacities were compared with that of commercial zeolite [Zeolite-Y, Ultra Stable Y(USY)]. The adsorption capacities of adsorbents were tested using a micro liquid flow reactor at room temperature. USY impregnated with cerium oxide (UC-10) had excellent DMDS and DMS adsorption capacities as compared with the other adsorbents tested. It was found that impregnation of USY with rare-earth metal such as Ce improved the sulfur adsorption capacity of zeolite. The form of the Ce promoter impregnated into USY was determined by FT-Raman spectroscopy. Adsorbents were characterized by X-ray fluorescence spectrometer, X-ray diffraction, and BET and the results obtained are discussed.     

Analytical methods for airborne arsine,silane and dichlorosilane by adsorption sampling and AA spectrophotometry

Analytical methods for arsine, silane and dichlorosilane by adsorption sampling and elemental analysis with graphite furnace AA were studied to establish convenient methods for atmospheric contamination surveys. This study included the following five items: (1) primary selection of adsorbents applicable to adsorption sampling; (2) examination of the adsorption capacities of the adsorbents for the gases; (3) improvement of the adsorbents by chemical modification; (4) desorption of the gases adsorbed on the adsorbents with solvents; and (5) quantitative analysis of arsenic and silicon in the solutions. Experimental results showed that active carbon made from synthetic thermosetting resin beads contained no aresenic and little silicon as impurities. This active carbon by itself was proved to adsorb arsine and dichlorosilane, but not silane. Impregnation with sodium hydroxide of the active carbon improved the adsorption capacity for all three gases. Refined silica gel, free from arsenic contamination, did not adsorb arsine by itself but potassium permanganate impregnation produced an adsorption capacity for arsine. The adsorbed arsine on the active carbon was desorbed into a hot dilute nitric acid solution with high efficiency (over 90%), but arsine adsorbed on sodium hydroxide impregnated active carbon or on potassium permanganate impregnated silica gel was dissolved into various solutions only at lower efficiencies. Silane adsorbed on sodium hydroxide-impregnated active carbon was desorbed with hot water with an efficiency higher than 90%. Dichlorosilane adsorbed on the active carbon with or without sodium hydroxide impregnation was desorbed with a nitric acid solution with efficiency of 85%. The lower determination limit for arsine able to discriminate from background interference of arsenie was 0.005 ppm, and those for silane and dichlorosilane were each 0.05 ppm for 3-dm³ air samples.     

Pneumatoamperometric determination of sulfur dioxide in air on ppb level

A simple device for the determination of sulfur dioxide at ppb concentrations in air is described. The device is composed of an enrichment unit operating continuously on the basis of gas extraction into polydisperse aerosol of a liquid transferring sulfur dioxide from liter amount of air into microliter amount of liquid. The analyte is determined pneumatoamperically from the concentrate on a gold-plated porous Teflon electrode. The detection limit is 0.3 ppb (v), i.e. 0.87 microgram/m3 of sulfur dioxide, the linear range covers several orders of magnitude. The analytical response is obtained few tenths of seconds after the gas contaminated with sulfur dioxide has entered the enrichment unit.     

Specific method for the determination of ozone in the atmosphere

A simple, sensitive and specific method for the determination of ozone in the atmosphere is described. Reactions of ozone with several 1-alkenes were studied at room temperature (25°). Eugenol(4-allyl-2-methoxyphenol), when reacted with ozone, was found to produce relatively large amounts of formaldehyde compared to other 1-alkenes tested. The method described was compared with alkaline iodide method for the determination of various concentrations of ozone in the range 0.05–2.0 p.p.m. Hydrogen peroxide, peracetic acid, sulfur dioxide and various reducing agents commonly present in the air, do not interfere. Formaldehyde when present in the air, must be determined simultaneously and the concentration of formaldehyde subtracted from that of the ozone. Any formaldehyde monitoring equipment can be easily adapted for the determination of ozone.     

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.     

A simple diffuse reflectance Fourier transform infrared spectroscopic determination of sulfur dioxide in ambient air using potassium tetrachloromercurate as the absorbing reagent

This paper presents development of a simple, rapid, and precise analytical method for determination of sulfur dioxide in ambient air by a gas to solid-phase conversion method. Sulfur dioxide is determined in the form of sulfite (SO3(2-)) because the absorbing reagent, potassium tetrachloromercurate (TCM), used in this method absorbs sulfur dioxide from the atmosphere in the form of sulfite. Determination of submicrogram levels of sulfur dioxide was based on the selection of a quantitative analytical peak at 495 cm(-1) among the 3 observed vibrational peaks for the dichlorosulfitomercurate complex formed after reaction of sulfur dioxide with TCM and measurement of absorbance using diffuse reflectance Fourier transform infrared spectroscopy. The limits of detection and quantification of the method were found to be 0.09 and 0.4 microg/g SO3(2-), respectively. The precision in terms of standard deviation and relative standard deviation (RSD) at a level of 2 microg SO3(2-)/10.1 g KBr for n = 10 was found to be 0.036 microg SO3(2-) and 1.8%, respectively. The RSD (n = 10) for determination of sulfur dioxide in ambient air was observed to be in the range of 2.7-4.2%. The method proposed is time saving and eliminates the slow and cumbersome steps of pH maintenance of the reaction mixture and color formation of the U.S. Environmental Protection Agency recommended West and Gaeke spectrophotometric method and other methods for quantitative determination of sulfur dioxide.     

Measurement of sulfur dioxide in automobile exhausts and industrial stack gases with a coated piezoelectric crystal detector.

A portable instrument operating on a car battery and based on a quadrol-coated piezoelectric crystal detector has been successfully used for monitoring sulfur dioxide in auto exhausts and refinery stack gases. The concentrations of sulfur dioxide in the auto exhausts lie in the range 20–50 p.p.m. Up to 300 p.p.m. of sulfur dioxide occurs in the refinery stack gases.     

A specific spectrophotometric determination of ozone in air in the presence of sulfur dioxide and nitrogen oxides

A sensitive, specific spectrophotometric method for the determination of ozone in air by the ozonolysis of 1,1-di-phenylethylene (DPE) is described. The yield of formaldehyde from the ozonolysis of several terminal olefins was determined, and DPE was found to give the highest yield, 90%. The method was checked against the EPA iodimetric method, and gives a consistent yield of formaldehyde over the ozone range 0.05–5.00 μg g^-1 of air. As sulfur dioxide is used as a reagent, its presence in air does not interfere. Interference by nitrogen oxides and other free radical oxidants is prevented by the addition of mesitol (2,4,6-trimethylphenol). Formaldehyde in air interferes, but can be determined by using the method with DPE omitted from the sampling train, and so accounted for. In the procedure, formaldehyde is determined by the reverse of the West—Gaeke method for sulfur dioxide.     

Development of a monitoring tape for phosgene in air

A porous cellulose tape impregnated with a processing solution that includes 4-p-nitroben-zylpyridine, N-benzylaniline and methanol is a highly sensitive means of detecting phosgene and maintains stable sensitivity for at least three months in air in a desiccator. When the sample including phosgene was passed through the tape, the color of tape changed to red. The degree of color change was proportional to the concentration of phosgene at a constant sampling time and flow rate. The degree of color change could be recorded by measuring the intensity of reflecting light (555 nm). The detection limit was 6 ppb for phosgene with a sampling time of 60 sec and a flow rate of 400 ml/min. Reproducibility tests showed that the relative standard deviation of response (n = 10) was 2.6% for 0.2 ppm phosgene. No interference was observed from ethanol (1 vol.%), trichloroethylene (1 vol.%), acetone (1 vol.%), carbon dioxide (4.9 vol.%), carbon monoxide (100 ppm), nitrogen dioxide (100 ppm), sulfur dioxide (50 ppm), hydrogen chloride gas (5 ppm), chlorine (3 ppm), acetic acid gas (24 ppm), ammonia (40 ppm), or benzyl chloride (20 ppm).     

The sampling of hydrogen sulfide in air with impregnated filter paper

A method is proposed for the quantitative collection of hydrogen sulfide in air on impregnated filter paper. An aqueous solution of potassium hydroxide, potassium zincate and glycerol is used as impregnating fluid. The stability of the collected sulfide and the efficiency of collection at different humidities, temperatures, hydrogen sulfide concentrations and air velocities were determined.     

Determination of atmospheric lead-210 by alpha-scintillation counting of air filters

Alpha-counting of filters used to sample large volumes of air provides a convenient way of determining atmospheric concentrations of²¹⁰Pb. Following decay of short-lived²²²Rn and²²⁰Rn progeny, alpha activity of the filters increases as²¹⁰Pb decays to²¹⁰Po. After transient equilibrium is reached at about 3 y, alpha activity diminishes with the 22.3 y halflife of²¹⁰Pb. The degree of equilibrium between²¹⁰Pb and²¹⁰Po can be calculated subsequent to sampling, and the average concentration of²¹⁰Pb in the air during the sampling period can be computed. Contributions to the total²¹⁰Pb from ambient short-lived radon progeny are small, typically 2–4%. Using high volume air samplers with collection rates of 1.1–1.7 m³/min for 24 h periods, and using counting times of 2 h for 20 cm² filter sections, we measured alpha counts ranging from 0.0100±0.0050 to 0.200±0.0200 dps. Periodic measurements on 100 of these filters over a 4 y period yielded mean²¹⁰Pb levels with standard deviations less than ±15%. The method requires minimal sample preparation and can be used to determine past atmospheric²¹⁰Pb concentrations on filters stored for up to 20 y and more.     

Application of the denuder technique in filter sampling of airborne chromates at ground level concentrations

The use of the denuder technique for the preserving sampling of chromium(VI) in airborne dust at ground level (immission) concentrations was investigated. A simple denuder with activated charcoal retained by a steelwire-net cylinder was constructed. The sorption abilities of the denuder towards sulfur dioxide, which is responsible for the reduction of sampled Cr(VI) on the filter surface, were examined under various conditions. The measurements provide evidence for a laminar flow inside the denuder. At a flow rate of 100 L/h and a temperature of 27 °C the theoretical sorption value of 99.6% is reached within an experimental error of ±0.1%. A relative humidity of 19–91.5% has no influence on the sorption. In order to check if an experimental sorption value of 99.5% is sufficient to stabilize Cr(VI) on the filter surface, sampling was simulated by sucking SO₂-loaded air through Teflon filters loaded with Cr(VI) containing aerosol particles with diameters of about 0.3 m. Aerosols of two different compositions were generated by a sprayer in combination with a diffusion dryer. The particle size distributions were determined from scanning electron microscopic pictures. Chromium(VI) was eluted from the filters with an alkaline buffer and extracted from the filter eluates with a solution of a liquid anion exchanger. Chromium was determined with graphite furnace atomic absorption spectrometry. The Cr(VI) losses are between 57 and 16% depending on the composition of the aerosol particles and the sampling time. Realistic conditions were chosen regarding the initial Cr(VI) on the filters and the amount of sulfur dioxide which passed through the denuder.Dedicated to Professor Dr. Dieter Klockow on the occasion of his 60th birthday     

Improvement of a monitoring tape for nitrogen dioxide in air

A porous cellulose tape containing a silica gel that was previously impregnated with a processing solution containing p-toluenesulfonic acid, sulfanilic acid, N-1-naphthyl ethylene diamine dihydrochloride, ethylene glycol and methanol has been developed to provide a highly sensitive detection of nitrogen dioxide in air. When the sample including nitrogen dioxide was passed through the tape, the color of tape changed to red, and the degree of color change could be recorded by measuring the intensity of reflecting light (555 nm). The calibration graph was linear up to approximately 0.10 ppm. The detection limit was 0.5 ppb for nitrogen dioxide with a sampling time of 8 min and a flow rate of 60 ml min(-1). No interferences were observed from ammonia (40 ppm), sulfur dioxide (51 ppm), carbon dioxide (21%), ozone (0.75 ppm), hydrogen sulfide (27 ppm) or nitrogen monoxide (99 ppm).     

Effect of Sulfate Anion Additions on the Phase Composition and Structure of Titanium Dioxide

Methods of X-ray diffraction analysis, electron microscopy, and microanalysis were used to examine the phase composition and structure of sulfate-anion-containing titanium dioxide samples into which a modifier was introduced by impregnation and by the sol-gel technique. It was demonstrated that the modification of titanium dioxide by the impregnation method results in that an ordered surface structure is formed, which is constituted by accreted crystallites 8–10 μm in size. In this structure, sulfate anions are stabilized at interblock boundaries. Titanium dioxide modified by the sol-gel method has the form of loosely packed coarse aggregates with sizes of about 30–32 μm. The appearance of the titanium tetrasulfide phase mostly situated on the surface was observed in its composition. The microstructural features and, in particular, enrichment of the surface of a sol-gel sample with sulfur and a decrease in dispersity are determined by the catalyst preparation conditions.     

Measurements of H2S in the Atmosphere

Swamps and tidal flats are believed to he important natural sources of atmospheric H₂S, though it is very difficult to detect the low concentrations of this trace gas above the surface of these regions. In view of this problem an air sampling device has been developed for the sampling of atmospheric H₂S with chemically impregnated filters. The sulfide generated on the filter is analyzed in a washing solution employing a very sensitive fluorescence method. The quality of the method is demonstrated by comparative calibrations. The fluorescence method is calibrated in the liquid phase with standard solutions of sulfide. Furthermore the sampling and analyzing method is calibrated together by using H₂S calibration gases. The detection limit of the method is shown to he 10ng/m³ STP. Data of test-measurements in ambient air and some results of field-measurements in the lower troposphere are presented.     

Determination of low sulfur concentrations in oils and organic solids

A rapid and reasonably precise method was needed for determining low sulfur concentrations (<2oo p pm ) in organic solids, gas oils, and heavier liquids This level of sullfur is below the useful range of conventional procedures, therefore, the development of a new method became necessary and a satisfactory combustion-colorimentic method was developed The method is haded on the oxidation of sulfur to sulfur dioxide by combustion and the subsequent formation of stable. non-volatile dissulfitomercurete(II) ion. A red-violet color develops when disulfitomercurate, p-rosaniline, hydrochloric acid, and formaldeliydc are mixed The absorption of the solution is measured at 560 mμ and is directly proportional to sulfur concentrationThe method is rapid, accurate and piecise The short-term 2-sigma precision limits arc 5 9 p p m sulfur at the' 90 p p m level and 36 p p m At the 10 p p in level Two samples can be analyzcd per hour The succes of the method is due in part to the use of two furnaces at different temperatures during the combustion step This airrangment affords good control of the combustion and is particularly useful where various types of samples are to be analysed     

A new fluorescence method for determination of ozone in ambient air

A new simple method for determination of ozone in ambient air is presented. The reaction employed is based on the known ozonolysis of indigo dye. The indigotrisulfonate molecule contains one carbon–carbon double bond (C═C), which reacts with ozone and generates isatinsulfonates and sulfoanthranilate. The quantitatively formed sulfoanthranilate presents fluorescence (λ_ex 245 nm, λ_em 400 nm). Ozone was collected using two cellulose filters coated with 40 μL of 1.0 × 10^{− 3} mol L^{− 1} of indigotrisulfonate. The analytical response was linear in the range 0–150 ppbv ozone, and a detection limit of 7 ppbv was achieved using a sampling time of 15 min and an optimum sampling air flow rate of 0.4 L min^{− 1}. There was no interference from sulfur dioxide, formaldehyde or nitrogen dioxide. The ozonolysis mechanism and the reaction products are discussed.