Air Pollution A. P. Altshuller, U.S. Department of Health, Education, and Welfare, Public Health Service, Consumer Protection and Environmental Health Service, National Air Pollufion Control Administration, Division of Chemistry and Physics, Cincinnati, Ohio. 45226
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includes papers published during 1967 and 1968, and also some published earlier in less accessible journals. The previous review ( 9 ) encompassed mainly papers published or presented between November 1964 and November 1966. I n the past, oral presentations not published as journal articles or in symposium volumes were cited (8, 9 ) . Although this approach gives the reader the most current materials, it has objectionable features: The presentation may never be published, in which case the reader may have no access to details. Also, even if the paper is published later, the reader has a reference to the oral presentation only. Consequently, this reviewer has decided to discontinue references to work t h a t has received only oral presentation. Oral presentations previously cited are not repeated in this review, even if they have been published. Total activity in terms of published work has increased significantly since the last review. I n particular, the current review covers many more publications on analysis of particulates and analysis of emissions than did the April 1967 review. Work on analysis of organic gases and vapors and on the analytical aspects of field studies also is a t higher levels t h a n in the past. As usual, many papers of analytical interest in air pollution were presented a t national and regional meetings of the American Chemical Society in 1967 and 1968; many of these papers have not yet been published. A number of sessions a t meetings of the Air Pollution Control Association in 1967 and 1968 were concerned with analytical applications. The California State Department of Public Health also has continued its sponsorship of conferences on analytical methods in air pollution and industrial hygiene studies. d second edition of “Air Pollution,” now a three-volume monograph, has appeared. Volume I1 is concerned with analysis, monitoring, and surveying. T h e following topics discussed in seven of the chapters should be of particular interest to analytical chemists: air sampling and quantity measurement (127); analysis of inorganic gaseous pollutants (154); analysis of organic gaseous pollutants (10); chemical analysis of inorganic particulate pollutants ($11) ; chemical analysis and carcinogenic bioassays of organic particulate pollutants (134); analysis of number and size of particulate pollutants (115) ; morphoHIS REVIEW
logical analysis of particulate pollutants (195).
An interesting review concerned with global abundance and removal mechanisms for various atmospheric pollutants has been prepared for the American Petroleum Institute (243). Methods of atmospheric analysis by gas chromatography have been reviewed recently (11). Analyses of rainwater and air over the British Isles and Eire have been discussed (288). Ionization methods for trace gases have been reviewed and compared with colorimetric, polarographic, and spectrographic methods (77). Interest in standardization of analytical methods for air pollutants has increased in the past few years. Several papers have discussed the need for standardization (157. 249, 250) and t h e initiation of work on standardization of methods for air pollutants within what is now the National Air Pollution Control Administration (249). BIOLOGICAL INDICATORS
The present status of research on airborne carcinogens has been reviewed (252).Work on the photodynamic assay procedure for potential carcinogens continues, with application to the neutral subfractions of organic extracts of airborne particulates (97). Concurrent work by the same group of investigators involved assay by use of neonatal mice (96). The toxicity of air pollutants related to photochemical atmospheric reactions has been evaluated by use of luminescent bacteria (2‘71). Electron spin resonance spectrometry has made possible the detection of free radicals in the reaction of ozone with linoleic acid ( 1 1 7 ) . This work suggests t h a t biological damage caused by ozone may be associated with reaction of ozone with unsaturated fatty acids located in cell membranes. SAMPLING AND CALIBRATION
The efficiency of extraction of several types of polynuclear aromatic compounds from airborne particulates by various organic solvents has been evaluated (284). Untreated glass fiber filters have been reported to be unsuitable for sampling sulfates from airborne particulates because of high sulfate blanks (83). Silica gel has been utilized in sampling procedures in source testing (103). Aromatic and halogenated hydrocarbons can be concentrated from air in charcoal
tubespriortogaschromatography (240). A sampler consisting of a fluidized bed of Teflon powder coated with Apiezon L was developed for concentration of organic vapors in an olfactory study (79). T h e adsorption and desorption characteristics of sulfur dioxide and carbon monoxide on glass and on various metal and plastic tubings have been evaluated (323, 324). Several analytical procedures have shown t h a t Teflon permeation tubes are satisfactory for generation of low partper-million levels of sulfur dioxide (266). A pressure calibration procedure has been developed for use in the determination of carbon dioxide by infrared gas analyzers (169). This procedure is more accurate than the usual calibration with standard gases, b u t it still requires correction for pressure-broadening. I n the same study, correction factors were given in the use of interference filters and drying of gases to eliminatr the water vapor interference in the measurement. Effects of temperature, humidity, wind speed, and dosage were investigated in the calibration of limed filter paper for measuring hydrogen fluoride (313). A precise dynamic method has been developed for producing knoa n concentrations of gases and vapors in air (211). Diffusion tube procedures were reported in the past for generation of known levels of vapors in air; the molecular diffusion coefficients needed to apply these procedures now have been obtained for many vapors in air (183).Various techniques and associated apparatus for production of radioactivity-labeled aerosols have been discussed (283). PARTICULATES AND AEROSOLS
Current research on particle-size distribution studies, interaction of sulfur dioxide with particulates, metal film techniques for acid aerosols, and particulates in plumes has been reviewed (306). A review is available on the application of membrane filters to analysis of collected particulates by a wide variety of analytical procedures (282). An electrical charging system has been developed for particle counting and measuring size distribution of aerosols in the 0.015- to 1-p size range (314). Continuous monitoring of aerosols over the 0.001- to 10-p range was accomplished by use of three instruments utilizing condensation, light scattering, and electric counting and sizing (226). Particle VOL. 41, NO. 5, APRIL 1969
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number and size mere compared for urban and nonurban sites by use of the Goetz aerosol spectrometer (139). Surface properties of airborne particulates and the nature of volatile and nonvolatile pollutants present on the surfaces were studied (172). Measurements of specific surface area and density of suspended particulates collected in Pittsburgh have been obtained (69). -4 continuous-wave helium-neon laser has been used to measure surface area of dust particles below 5 p (234). Lidar techniques have been applied t o in situ measurements of atmospheric particulates with estimates of particle concentrations (20). The integrating nephelometer of Beuttel and Brewer has been modified for application to direct measurements of atmospheric light-scattering coefficients in studies of visibility and pollution (53). Measurements by this light-scattering technique have been correlated with data on mass concentration of atmospheric aerosols (52). Other investigators also have been concerned with the ability to relate visibility reduction to aerosol concentrations in urban air (215). Atmospheric turbidity, which is a function of atmospheric aerosol loading, has been suggested as responsible for the decrease in worldrride air temperatures in the past 20 to 30 years (19.4). The correlation of light scattering with nitrogen oxide concentrations has been claimed to indicate an important contribution of particulates from automobile exhaust to visibility reduction in cities (35). -4 reference volume is available for positive identification of fine particles and dusts by microscopic techniques (196) Microscopic analysis has been applied to the identification of particulates in emissions from power plants, feed mills, and other combustion sources (105). The combined electron microscope-electron microanalyzer has considerable potential for various analytical applications, including analysis of individual particles (199). A microspectrophotometric technique has been described for obtaining the infrared spectrum of microgram quantities of atmospheric dust (25). The generation of ice nuclei occurs when emissions of lead aerosols or tetraethyl lead in gasoline vapors are mixed with iodine vapor (137). Inorganic Particulates.A new atomic absorption/flame emission instrument is available to provide quantitative analysis of 12 metallic elements after collection of air particulates on filters (206). A flame emission aerosol particle analyzer has been designed and used to determine aerosol particles containing lithium, sodium, potassium, calcium, magnesium, iron, and manganese (70). A direct-reading single-beam atomic absorption spectrometer for rapid measurement of beryllium has been develI
2 R * ANALYTICAL CHEMISTRY
oped (28). Research has been done on a mass spectrometric technique for determination of beryllium a t subnanogram concentrations (197). A colorimetric method for beryllium utilizing aluminon reagent has been developed (192) and applied to airborne dust samples (193). A photometric method has been used to determine concentrations of soluble and insoluble calcium compounds from impactor samples (198). Results were discussed in terms of the origin of atmospheric calcium compounds. The use of X-ray fluorescence spectrometry for determination of airborne metallic dusts has been discussed, and analyses for iron collected on glass fiber papers by X-ray fluorescence have been compared with those obtained by atomic absorption spectrometry (49). The characteristics of the signal obtained in electron spin resonance measurements of airborne particulates collected a t a site in the Netherlands indicate the ferromagnetic nature of the absorption, which is probably associated with iron in the form of a ferric oxide hydrate complex (289). The characteristics of an electron spin resonance signal in airborne particulates collected in New York City were associated in another study with the presence of manganous iron (316). The determination of copper, cadmium, and zinc by atomic absorption spectrometry has been investigated (236). .4n alternative technique for copper involves use of dithio-oxamide crayons and the ring oven technique (312). Zinc and cadmium have been determined by the ring oven technique with reagent crayons (313). Zinc in airborne particulates has been analyzed by both atomic absorption spectrometry and polarography (6). The atomic absorption procedure was considered less time-consuming than the polarographic method. Other investigators have used polarography to determine vanadium in air particulates (150). An inverse polarographic technique for lead in hydrocarbons has been reported capable of determining lead in the 1 to 100 ppb range (247). A novel technique involves the reaction of lead with iodine as the basis of an analytical procedure (202). The lead iodide formed initiates formation of ice nucleation, which can be detected with an acoustical detector. This approach is not necessarily specific for lead, because silver and terpenes also can initiate the formation of ice nuclei. Particle size distribution of a number of metal components in particulates from urbanair was determined by atomic absorption spectrometry (168). The mass median diameters of iron, cadmium, magnesium, chromium, and copper were all above 1 w, whereas the mass median diameter of lead was only 0.2 I).
Methods are available for microchemical analysis of ammonium and nitrate ions in particles collected on membrane filters (185). Techniques have been recommended for analysis of sulfate on gelatin and other types of substrates (15). Particle size distribution measurements for sulfate have been made on particulate samples collected with the Goetz aerosol spectrometer in the Los Angeles and San Francisco Bay areas (182). The mass median diameters, which are in the 0.1- to 1-p range with an average of about 0.35 p, were discussed as functions of relative humidity, diurnal variations, and sampling sites. Two reviews partially concerned with sampling and analysis of particulate fluorides were published during 1967 (31, 100). A ring oven technique has been developed for determination of orthophosphate in airborne particulates (248). X-Ray diffraction has been used to analyze quartz particles in the 0.5- to 2-fi range in dusts (216). Organic Particulates. Several groups of investigators have concerned themselves with modes of formation or destruction of polynuclear aromatic hydrocarbons. The formation of polycyclic aromatic hydrocarbons in premixed acetylene-oxygen flames was followed by use of gas chromatography and ultraviolet spectrometry (177) The effects of temperature and ultraviolet radiation on the oxidation of pyrene to diones, diols, and other products on garden soil, silica gel, and alumina were investigated; products were identified by thin layer and column chromatography (101). The structural characteristics of soots and the presence of polynuclear aromatic hydrocarbons on surfaces of particulates have been considered (296). The finding that photooxidation causes rapid reaction of benzo(a)pyrene on small particles was based on measurements of color changes, disappearance of fluorescence, and variations in characteristics of the carbonhydrogen bending frequencies in the infrared. Many other similar hydrocarbons including anthracene, pyrene, b e n z (a) a n t h r a c en e, b en z o( e) p y r ene, perylene, dibenz(a,h)anthracene, dibenzo(a,h)pyrene, and dibenzo(a,c)pyrene did not show corresponding changes in their infrared spectra (296). Many strains of a spore-forming bacteria including the Bacillus megateriurn species have been shown capable of destroying benzo(a)pyrene in nutrient media in soils (229). An interesting and useful paper conipares 11 procedures for analysis of benzo(a)pyrene (265). I n this work and other studies by the same investigators (265, 286), thin layer chromatography has been emphasized as a key to rapid and specific analysis for benzo(a)pyrene. -4procedure involving column chromaI
tography followed b y paper chromatography with fluorimetric analysis in sulfuric acid has been suggested for routine use (175);however, the author in a n addendum notes t h a t the thin layer approach is preferable. Other European investigators also obtained separations b y two-dimensional thin layer chromatography, followed by spectrophotofluorimetric analysis (159).The same type of procedure has been used for identification and estimation of dibenz(a,e)pyrene ( 2 2 ) . Direct evaluation of fluorescence on chromatographic strips has been studied ( 2 3 ) . Other workers continue t o favor the use of modified column chromatography procedures alone or combined with extraction procedures prior to spectrophotofluorometry (84, 201, 827). M a n y of the d a t a on benzo(a)pyrene in air in the literature may be seriously in error because the interference of benzo(k)fluoranthene was not eliminated (3%'). T h e presence of 4-methyl pyrene in airborne particulates was discerned b y use of alumina column chromatography and ultraviolet spectra (297). T h e application of quasilinear fluorescence spectra in polynuclear aromatic hydrocarbon analysis has been discussed (3, 146). The advantages of t h e sharp structured spectra and sensitivity of this technique involving measurements of polynuclear aromatic hydrocarbons in n-heptane frozen a t liquid nitrogen temperature appear t o offer a n improvement on current procedures (146). Interest in applying gas-liquid partition chromatography to separation of polynuclear aromatic hydrocarbons continues (16, 32, 50, 51). However, key separations of such components as benzo(a)pyrene from benzo(e)pyrene and perylene remain difficult. I n a study using glass capillary columns coated with S E 52, with linear programming from 100" to 300", t h e components in a 44-component polynuclear aromatic hydrocarbon mixture were separated and detected with flame ionization and electron capture techniques (50). When fractions of cigarette smoke condensates were analyzed, however, the same conditions did not provide significant separation of benzo(a)pyrene from benzo(e)pyrene (50). I n analyses of polynuclear aromatic hydrocarbons produced from ethylene or ethane diffusion flames with separation on columns packed with SE 52 o n Chromosorb If-, benzo(a)pyrene, benzo(e)pyrene, and perylene were not resolved from each other (51). Identifications required collection of peak effluents in cyclohexane and measurement of ultraviolet absorption spectra. In t h e previously cited comparison of methods for analysis of benzo(a)pyrene, gas chromatography was used subsequent to thin layer chromatography (265). Incomplete resolution of benzo(a) pyrene and benzo(e) pyrene still
was a problem. I n addition, because of poorer sensitivity with a flame ionization detector, longer analysis time, and greater number of man hours per analysis, the method was not competitive with the fluorimetric methods tested (265). An apparatus combining gas chromatographic separation with spectrophotofluorometry for analysis of polynuclear aromatic hydrocarbons involves use of a flowing liquid interface ( 3 2 ) . This approach offers considerable potential in terms of both specificity and sensitivity of analysis. Published investigations on classes of large organic molecules in airborne particulates other than polynuclear aromatic hydrocarbons are largely associated with the studies of Sawicki and coworkers. Several methods for estimation of benz(c)acridineand benzo(h)quinoline in urban particulates involving use of thin layer chromatography with analysis b y fluorimetry have been evaluated and compared with the use of column chromatography with analysis b y spectrophotometry (263). Paper electrophoretic separations for polynuclear aza heterocyclics in air particulates have been developed (260). This technique is more rapid than paper chromatography, and resolution is as good. An improved thin layer chromatographic procedure for separation of polynuclear aromatic acridines and quinolines on silica gel has been developed and evaluated (93). A new colorimetric reagent, 7,7,8,8-tetracyanoquinodimethan (TCNQ), has been introduced for determination of mercaptans, prolines, and free radical precursors (258). A number of procedures for determination of 7-H-benz(de)anthracen-7-one and phenalen-1-one in airborne particles b y thin layer chromatography with analysis by filter fluorimetry, quenchofluorimetry, or spectrophotofluorimetry have been compared (261). -1rapid procedure for analysis of 7-H-benz(de)anthracen-7-one and phenalen-1-one involving separation on glass fiber paper impregnated with silica gel (ITLC) with spectrophotofluorimetry or even visual estimation has been developed and evaluated Lvith urban airborne particulates (94). T h e polynuclear ring carbonyl, 9-acridanone, has been identified and assayed in urban airborne particulates b y the development of several procedures involving two-dimensional thin layer chromatography and fluorimetry (264) Ribose and some other sugars form furfural derivatives in acid solution t h a t react with azulene; colorimetric methods based on this reaction have been developed t o initiate compositional studies of polyhydroxy organic compounds in polluted atmospheres (257). This azulene method has been compared with use of other reactions for location of spots of thin layer chromatograms
(95). This new method was used to identify 5-hydroxymethylfurfural in t h e effluent from a coffee-roasting plant. il number of colorimetric procedures, including use of 3-methyl-2-benzothiazoline hydrazone, have been compared in their application for t h e determination of sugars and other a-glycolic derivatives (262). When the procedure was evaluated with airborne particulates, i t was shown t h a t the samples used contained substantial amounts of water-soluble a-glycolic substances. Three reagents and a variety of fluorimetric procedures have been developed for analysis of a-glycolic compounds (225). These procedures also indicated t h e presence of large a m o u n t s of a-glycolic compounds in aqueous extracts of airborne particulates. fluorimetric method for determination of glycine and other amino acids has been developed for use in analysis of urban particulates (253). An oxidative method for conversion of olefins to aldehydes has been used with 3-methyl3-benzo-thiazoline hydrazone in developing a procedure for higher molecular weight olefinic substances in urban airborne particulates (259). Another precursor method involves spectrophotofluorimetric determination of aldehydic fragments of polyhydroxy organics in airborne particulates (266). INORGANIC GASES
Carbon Monoxide and Carbon Dioxide. T h e gas chromatographic procedure for carbon monoxide involving separation on molecular sieve column, hydrogenation to methane, and analysis with a flame ionization detector is capable of analyzing carbon monoxide in the range of 0.05 t o 2 ppm with good precision (12). This technique was shown earlier to be useful at higher carbon monoxide concentrations ( 9 ) . A mercury vapor-type analyzer has been modified t o determine low concentrations of carbon monoxide at nonurban sites (241). Hydrogen, olefins, and organic oxygenates could possibly interfere in sampling a t urban sites. Studies using colorimetric analysis for carbon monoxide in air have been reported (57, 58). However, t h e procedures are useable only down to 20 ppm and require contact times as long as 20 hours (58). T h e classical potassium pallado sulfite detection technique was used in a study comparing carbon monoxide in exhaled air with carboxyhemoglobin levels in blood (237). A high inlet pressure, mass spectrometric technique has been used t o determine carbon dioxide in nitrogen and air with a n accuracy of better than 1% (1.41, 162). X carbon dioxide laser has been used to analyze carbon dioxide in exhaled human breath (143). Sulfur Dioxide and Hydrogen Sulfide. A new rotary scrubber has been developed to eliminate the use of soVOL. 41,
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dium tetrachloromercurate in sampling sulfur dioxide from air in a continuous monitoring instrument based on the West and Gaeke colorimetric method (184). A study was made of a number of pollutant gases t h a t might interfere in analysis of sulfur dioxide with t h e Thomas Autometer (164). Hydrogen chloride, ammonia, a n d chlorine, if present, would cause significant errors in the sulfur dioxide measurement. An open-path instrument based on correlation spectrometry using the finestructured bands in the 3000-A region has been developed for sulfur dioxide. This instrument can determine low concentrations of the pollutant over long path lengths (155). More work has been reported on the stability of the collecting solution, on development and fading of color, and on precision in the West and Gaeke method for sulfur dioxide (299). Purification of parafuchsine dyes has been carried out by paper chromatography andextraction (214).Modificationshave been discussed in the preparation and analysis of sulfation candles (140). Polarographic analysis of sulfur dioxide in acidic solution has been used in the range of 10 to 1000 pg of sulfur dioxide per ml of solution after reduction of tetrachlorate mercurate t o mercury to prevent obscuration of the sulfur dioxide polarographic wave (56). Nitrogen oxides and nitrite ion were eliminated as possible interferences by reduction with hydrazine. Total sulfur collected from air has been converted t o barium sulfate and the barium determined b y measuring the intensity of the L-alpha emission produced by Xray excitation (47). Higher oxide of s u l f u r levels mere o b t a i n e d by t h i s method than by the West and Gaeke method in analysis of samples from a gas-burning incinerator containing from 1 to 10 ppm of oxides of sulfur. Triton X-305 on Chromosorb G (DMCS-treated) and Porapak Q columns were evaluated for use in gas chromatographic analysis of sulfur dioxide and hydrogen sulfide (161). Concentrations below 25 ppm of sulfur dioxide and 0.2 ppm of hydrogen sulfide could n o t b e detected. B e t t e r substrates still are desirable for analysis of sulfur compounds. A S 3 5 0 2 scintillation technique has been applied t o the investigation of reactions involving sulfur dioxide (302). Hydrogen sulfide and sulfur dioxide have been measured after concurrent absorption on collective tubes using the molybdenum blue method for the hydrogen sulfide and sulfur dioxide (after reduction) or the West-Gaeke method for sulfur dioxide (36). =1 modification of the methylene blue method for hydrogen sulfide resulted in elimination of precipitates (124). Levels of hydrogen sulfide down to 0.005 mg per 4 R * ANALYTICAL CHEMISTRY
m3 can be determined with 200 1 of air sample. A procedure for estimating hydrogen sulfide dosage has been developed, based on the loss of reflectance of the silver surface of silver metal membrane filters when exposed to hydrogen sulfide (99). Kitrogen oxides and ozone do not interfere. I n o r g a n i c Nitrogen C o m p o u n d s . Buck and Stratman have reported a change in the stoichiometric factor in the Saltzman procedure for nitrogen dioxide from 0.62 to 1 with increasing nitrogen dioxide concentration (37). I n another investigation, the stoichiometric factor of 0.72 obtained by most investigators was confirmed (272). The suggestion was made t h a t the values obtained b y Buck and Stratman may result from modifications of the reagent solution. Work has been done to increase the response time of reagent, gas-liquid contactor, and optical systems for monitoring nitrogen dioxide (162). Subminute response was obtained from a reagent containing.Y,iY( 1naphthylacety1)ethyl diamine, 2-aminop-benzene disulfonic acid, and sulfuric acid. I n collection of nitrogen dioxide from air, the nitrogen dioxide should be collected in hydrogen peroxide solution rather than potassium hydroxidehydrogen peroxide solution, and the solution should be made alkaline only after absorption (163); this procedure was accurate for nitrogen dioxide only in the absence of nitric oxide. -1visual comparator method for nitrogen dioxide has been evaluated (133). The calibration, response to nitric oxide and nitrogen dioxide, and speed of response of a commercial flow colorimeter for nitrogen oxides have been discussed (76). The conversion efficiencies of “dichromate” paper for nitric oxide in the 1 to 5 ppm range have been evaluated (318). The substrate was highly effective u p to 1 ppm a t 50% relative humidity. At concentrations above 1 ppm, efficiency decreased, b u t calibrations can be made. Aromatic hydrocarbons such as m-xylene and 1,3,5-trimethylbenzene can reduce the efficiency of the “dichromate” paper when present concurrently with nitric oxide (318). Operating conditions have been evalu a t e d i n use of pulsed voltage for electron-capture gas chromatographic determination of parts per million quantities of nitrogen dioxide (203). =1 temperature-programmed 11olecular Sieve 5A column has been used to obtain separations of a number of inorganic gases, including nitric oxide and nitrous oxide (75). Sitrogen dioxide was not eluted as a peak b u t did not interfere. Limits of detection with the thermal conductivity detector used for nitric oxide and nitrous oxide were 12 and 25 ppm, respectively. Atmospheric nitrous oxide has been concentrated with Molecular
Sieve 5A at ambient temperature and desorbed at 250” t o 300” followed b y gas chromatographic analysis (27). Atmospheric concentrations obtained were in the 0.19 t o 0.29 ppm range. Analysis of ammonia by the indophenol reaction was reported t o be equal in detectability and presicion to the Nessler reaction (170). The potential for interference b y hydrogen sulfide, nitrite, sulfite, and formaldehyde was evaluated. Formaldehyde does interfere significantly and must be eliminated (170). d colorimetric personal dosimeter for hydrazine has been developed (228). Ozone and Oxidants. B simple titration system for ozone with trans-2butene has been devised to make oxidant analyzers specific for ozone (88). Nitrogen dioxide, peroxyacetyl nitrate, hydrogen peroxide, n-butyl hydroperoxide, and peracetic acid did not interfere with the ozone titration by olefin. The effects of various interfering substances and prolonged sampling have been evaluated for the 1,2-di-(4-pyridy1)ethylene method for ozone in air. (125). A method for analysis of ozone by oxidizing dihydroacridine to acridine and then determining the absorptivity of acridine at 249.5 mp has been discussed, along with a n appropriate sampling procedure (188). A colorimetric method for ozone involves reaction with a mixture of S-phenyl-2naphthlamine and o-dichlorobenzene (113); no inhibition of color by nitrogen oxides was observed. Increases in molar absorptivity of ferrous ammonium sulfate reagent for ozone a t concentrations below 2 ppm have been reported ( 6 2 ) . An acid modification of the colorimetric potassium iodide method for oxidant has been evaluated ( 7 3 ) . T h e procedure provides good color stability, and sulfur dioxide does not interfere. h differential technique involving decomposition of ozone on a cotton wool plug has been used for determining ozone in the presence of nitrogen diovide (61). A sensitive colorimetric procedure for hydrogen peroxide in air is based on the colored product formed when hydrogen peroxide reacts with titanium(1V) and 8-quinolinol (63). Hydrogen Fluoride and Fluorine. Two reviews of methods of sampling and analyzing hydrogen fluoride and also particulate fluoride were published in 1967 (31, 100). An analyzer for atmospheric hydrogen fluoride has been redesigned to simplify operation and reduce bulk and weight (298). Analyses for hydrogen fluoride and watersoluble particulate fluorides in air have been performed b y use of a fluoridesensitive specific ion electrode (91). The method for determination of hydrogen fluoride colorimetrically with titanium sulfate-chromotropic acid re-
agent has been improved (622). A portable instrument capable of detecting fluorine in the parts per billion range has been developed, based on capture of 1 2 1 3 1 in sodium thiosulfate solution after oxidation of iodide (89). T h e procedure is not specific and could be used as an oxidant method. ORGANIC GASES AND VAPORS
Use of a cryogenic sampling technique with infrared spectrophotometry has been discussed as a n analytical approach of considerable generality (246). Computer analysis and data transmission were considered as aspects of t h e potential application of the approach t o air pollution. A comprehensive study of the photoionization detector indicated considerably higher responses to organic vapors than have been obtained with the flame ionization detector (253). The photoionization detector also responds to some molecules, such as formaldehyde, hydrogen sulfide, ammonia, and nitric oxide, to n hich the flame ionization detector does not respond. T h e chromatographic equilibration technique previously described ( 3 ) has been applied as a conv e n i e n t field m e t h o d f o r s a m p l i n g benzene, chlorobenzene, and nitrobenzene in air (269). Hydrocarbons. The cryogenic sampling technique discussed above has been specifically applied t o multicomponent misturcs of c', to Ca hydrocarbons (245). T h e narrow vibrational bands obtained a t 20 "C appreciably improve the specificity of infrared analysis. However, the sensitivities presently available appear inadequate for atmospheric analysis. especially as compared t o alternative methods such as gas chromatography. Another interesting nen technique involves detection of aliphatic hydrocarbons by their infrared emission as stimulated by a carbon dioxide laser a t 10.6 p (244). Detection limits are determined b? the sample volume, which is defined by t h e diameter of the laser beam and the entrance slit of the spectrometer. T h e highest sensitivity reported in this initial study, 1 fig for ethylene in 1 ml of effective sample volume, is clearly inadequate for air pollution application, and much-improved sensitivity will be needed. ai temperature-programmed 200-ft squalane capillary column has been used to obtain 240 chromatographic peaks in analysis of full-range motor gasolines (251); 180 of these were identified in the C, to C i 2hydrocarbon range. The technique has evident potential for analyses of automobile exhaust and evaporative losses. -1 gas chromatographic technique has been reported for quantitative measurement of photochemically reactive aromatic hydrocarbons in enamels and thinners,
which contribute t o organic solvent losses (98). Organic Oxygenates. Application of the chromotropic acid method to analysis of formaldehyde in the presence of appreciable concentrations of nitrogen oxides has been investigated (48). Absorption in bisulfite solution followed b y boiling of the solution is recommended t o eliminate interference of nitrates and nitrites. T h e separation and identification of aromatic carbonyl compounds as azines or 4-nitrophenylhydrazones b y paper and thin layer chromatography have been reported (18, 19). These techniques have been used to identify and analyze benzaldehyde, salicylaldehyde, acetophenone, and ortho and meta hydroxybenzophenone in automobile exhaust (18, 19). Two new reagents, dimedone a n d 1,3-cyclohexmedione, have been introduced for fluorimetric determination of aldehydes ( 2 ~ 4 ) .Four procedures involving these reagents were compared with fluorimetric procedures using Jacid and 2,4-pentanedione as reagents, and recommendations were made for use of these various procedures in analysis of aliphatic or aromatic aldehydes. Losses of esters and alcohols were reported to occur in attempts to chromatograph such substances as air contaminants on silanized Chromosorb W coated with a nonpolar liquid phase (149). T h e difference in behavior of such polar substances on substrates coated with nonpolar and with polar liquid phases was suggested as a means of discriminating such substances from other materials present. Organic Nitrates. dnalyses for P A S by nuclear magnetic resonance, electron spin resonance, infrared spectrometry, chemical tests, a n a l y t i c a l t i t r a t i o n , direct oxygen analysis, and freezingpoint depression were made to obtain s t r u c t u r a l information (212). M o s t of the results were consistent with the peroxyacetyl nitrate structure. The products of alkaline hydrolysis, however, were indicative of a mixed anhydride of nitrous acid and acetic acid, but because other work has shown t h a t molecular oxygen was produced by t h e alkaline hydrolysis of P=IN (287),these products also are consistent with t h e peroxyacetyl nitrate structure. T h e calibration conditions and anal y t i c a l c o l u m n s used for peroxyacyl nitrates and alkyl nitrate analyses in irradiation chamber experiments have been described. I n a different gas chromatographic analysis, lower molecular weight compounds were separated from higher molecular weight compounds b y use of different column lengths and flow rate conditions but the same substrate, consisting of 5% G E Versilute F-50 on 90- t o 100-mesh Anakrom F-50 packed in a Teflon tube thermostated a t 0" (76). I n a n investigation of t h e
photooxidation of propylene in the presence of nitrogen oxides, analyses for peroxyacetyl nitrate in t h e concentration range between about 0.006 and 0.6 ppm and methyl nitrate in the concentration range u p to 0.02 ppm were performed on 8 feet of 1/8-in. 0.d. borosilicate glass column packed with 10% polyethylene glycol 400 on 60- to 80mesh Gas Chrom Z at 28" (12). I n other work on irradiated mixtures of hydrocarbons and nitrogen oxides, peroxyacetyl nitrate was separated at room temperature on 4 feet of 1/8-in. diameter glass column packed with 3.8% SE 30 on 80- to 100-mesh Diatoport S (1.29). I n this same study, peroxybenzoyl nitrate was identified for the first time as a reaction product. The peroxybenzoyl nitrate could be separated a t 50" on a 10-in. length of I/*-in. 0.d. glass column packed with 3.8% SE 30 on 80- to 100-mesh Diatoport S. The minimum detectable concentration of peroxybenzoyl nitrate in this system was 0.002 ppm. Organic Peroxides. Avariety of colorimetric, coulometric, and ultraviolet procedures for oxidants have been evaluated with respect to response to both inorganic and organic oxidants, including peracetic acid, a c e t y l peroxide, several alkyl hydroperoxides, peroxyacetyl nitrate, and perosypropionyl nitrate (64). These organic peroxides shorn significant differences in reactivity with most of the colorimetric reagents investigated. Kinetic colorimetry was applied with use of potassium iodide and ferrous thiocyanate reagents t o the same group of oxidants (255). Peracetic acid reaction was essentially instantaneous; many of the other organic peroxides can be distinguished on t h e basis of their kinetic half times. T h e applications of these techniques to photochemical air pollution studies are discussed (64, 255). Tetraalkyl Lead Compounds. Calibration and analytical procedures for organic lead involving collection on activated charcoal, decomposition, and extraction from charcoal followed b y a single extraction dithizone analysis have been given (279). Evaluation of these procedures with synthetic tetramethyl lead in air mixtures and air samples collected in Los Angeles indicated t h a t precision was sufficient readily to measure organic lead at levels below 0.1 pg/ per m3 in air samples of 100 t o 200 m3. ,4 direct method of analysis for tetraalkyl lead compounds with a n atomic absorption spectrophotometer has been discussed (294). T h e method, with a limit of detection of 1 pg per m3, is useful in the vicinity of production facilities. A polarographic procedure for tetraethyl lead has been evaluated a n d c o m p a r e d with t h e dithizone method (275). Several investigations discussed apVOL. 41, NO. 5, APRIL 1969
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plication of gas chromatography t o analysis of tetraalkyl lead compounds (46,224,280). Methyl ethyl lead alkyls and halide scavengers have been determined following chromatographic separation and catalytic hydrogenation as methane and ethane with flame ionization detection (280). T h e equilibration method (9) followed b y gas chromatographic analysis b y electron capture has been used to determine tetraethyl lead down to 0.1 ppm in the vicinity of production facilities (46). I n other work on the gas chromatographic analysis of tetraethyl lead, known samples of tetraethyl lead in the 3 t o 400 pg per m3 range were recovered with 95 t o 99% efficiency (224). Pesticides and Related Compounds. Methyl and ethyl mercury compounds used as fungicides and seed disinfectants mere collected in air in impingers containing iodine monochloride in hydrochloric acid solution (174). Calibration mas b y permeation tubes, and analysis by the dithiozone method. Continuous monitoring of organophosphorous compounds down to 0.1 pg per 1 of air was accomplished with a n alkali metal-dual flame ionization detector (232). .1 colorimetric procedure for mobile sampling of mevinphos (2methoxycarbonyl-1-methylvinyldimethyl phosphase) has been described (176). Colorimetric methods also have been evaluated for determination of methoxone (sodium salt of 2-methy1-4chlorophenoxy acetic acid) and for 2,4-D (2,4-dichlorophenoxy acetic acid derivatives) in air (112, 500). Organic Sulfur Compounds. Sampling and direct gas chromatographic analysis of kraft mill effluents for methyl mercaptan, dimethyl sulfide, and dimethyl disulfide have been studied (317 ) . Various organic solvents and mercuric cyanide solutions have been evaluated for collection of methyl mercaptan (218). Methyl mercaptan, along with ethyl mercaptan and dimethyl sulfide, v a s separated on a 4-m tricresyl phosphate column prior to gas chromatographic analysis (218). Losses of methyl mercaptan on various tubings have been determined, as well as t h e detectable concentrations with direct injection and through TritonChromosorb G and Poropak Q columns (161). ANALYSES OF SOURCES OF POLLUTION
Vehicular Emissions. Cold trapping at -70' follomed by temperature programming of a 150-foot long, 0.02-in. i.d. capillary column coated with DomCorning DC-200 silicone oil has separated over 200 peaks in chromatograms of automobile exhaust in 25 to 30 min (223). The minimum detectable concentration of each hydrocarbon was 1 ppb. I n Japanese work, t h e 6 R
ANALYTICAL CHEMISTRY
C, to C, hydrocarbons, carbon monoxide, and carbon dioxide were analyzed b y gas chromatography in the exhaust from a n idling small automobile engine (273). The cooperative C R C program on measurement of evaporative losses has been discussed, with emphasis on sampling techniques for carburetor and fuel t a n k hydrocarbon losses (308). A plastic-bag sampling technique for collection of carburetor evaporative losses has bcen developed, and the relationship of fuel composition to reactivity was discussed (205). A comparison has been made of infrared, heat of combustion, and heat conductivity techniques for measuring carbon monoxide emissions from internal combustion engines (268). Only the infrared technique was considered fully satisfactory. The relationship of nitrogen oxide and organic oxygenate formation to combustion processes in engines has been investigated ( 7 ) . X t r i c oxide in engine exhaust has been determined in the 100 to 5000 ppm range by ozonization of nitric oxide to nitrogen dioxide with ultraviolet analysis (274). Unburned hydrocarbons in the exhaust had a n undesirable effect on response characteristics. Ammonia has been measured by the Kjeldahl method in engine exhaust (122). Ammonia is a minor constituent; concentrations ranged from 1 to 6 ppm, with a n average value of 2 ppm over a trffic cycle. A number of aliphatic carbonyl compounds and benzaldehyde have been analyzed in exhaust gases by gas chromatographic separation of their 2,4-dinitrophenylhydrazones and flame ionization analysis (107). Formaldehyde made u p about 70 mole per cent of the carbonyls determined. I n animal exposure studies in which sulfur dioxide was added t o diluted automobile exhaust, a commercial colorimetric analyzer was modified for use with the iron-phenanthroline method for sulfur dioxide (187). The lead content of automobile exhaust was determined b y X-ray fluorescence (204). Particle sizing indicated t h a t about 40% of the lead aerosol was smaller than 0.3-p diameter. Several papers have been published on polynuclear aromatic hydrocarbons in automobile exhaust. T o determine the contribution of polynuclear aromatic hydrocarbons in the fuel to exhaust composition, benzo(a)pyrene with carbon-14 tracer was added to the gasoline (21). The benzo(a)pyrene in the fuel contributed 3601, of the benzo(a)pyrene in the exhaust. Benzo(a)pyrene accumulated in the crankcase oil also (21). When a 50% benzene-50% xylene mixture was used as a fuel, exhaust emissions contained phenol, pyrene, and dibenz(a,j)acridine (44). -1small European automobile, operated on idle with
a commercial gasoline, produced in its exhaust emissions anthracene, fluoranthene, pyrene, coronene, 1,2-benzanthracene, benzo(a) pyrene, and benzo(e)pyrene (45). Analysis involved acetone extraction and column chromatography on alumina followed b y spectrophotometric analysis. I n another study with a European automobile, with LPG as fuel, several p ol y n u c 1e a r aromatic h y d r o c a r b o ns were separated b y thin layer chrom a t o g r a p h y a n d analyzed spectrophotometrically (166). Fluorescence analysis a t -197' was used to identify benzo(a)pyrene, anthanthrene, and 1, 12-benzperyleneinexhaust gases of fourcycle gasoline engines (147). I n a summary report on polynuclear aromatic hydrocarbons from various sources, results on motor vehicle emissions are included (120). The composition of diesel exhaust has been investigated for a variety of substances (135). Carbon monoxide was reported a t not over 0.1 to 0.15% and often below 0.05%. Sitrogen oxide concentrations mere higher in the directfuel-injection engines. Benzo(a) pyrene was considered of concern only if the engine operated under high mean pressure. A study of particulates from diesel exhaust included particle size distribution, specific surface area, free acidity of total particulate, hydrocarbon content of total particulate, and spectrographic analysis for a number of metals (108). Composition of exhaust emissions from several types of turbine engines has been investigated. Hydrocarbon and particulate contents of a regenerative turbine engine were measured (173). Oxides of nitrogen levels varied from less than 50 ppm in a n industrial gas turbine to 100 to 350 ppm in aircraft turbojet engines, with concentration levels adjusted to stoichiometric conditions (277). I n a more comprehensive composition s t u d y , various types of hydrocarbons, nitrogen oxides, carbon monoxide, aldehydes, and particulates were measured in emissions from three types of jet engines (180). Other Emission Sources. A summary report presented analyses of polynuclear aromatic hydrocarbon emissions from various heat generation, incineration, and industrial processes (120). Emissions from six coal-burning power plants were analyzed for sulfur dioxide, nitric oxide, carbon monoxide, total hydrocarbons, formaldehyde, polynuclear aromatic hydrocarbons, and total particulates (71).Relationships between operating conditions and emissions of sulfur dioxide, nitric oxide, and particulate were considered. Levels of polynuclear aromatic hydrocarbons in emissions from various types of coal-fired installations have been discussed (74). Qualitative measurements of sulfur di-
oxide in stack gases were made with a remote sensing infrared multiple-scan interferometry system (179). Methods, procedures, and problems have been evaluated for automated equipment used in on-stream measurement of sulfur oxides in flue gases during combustion of a No. 6 residue oil averaging 2.35y0 sulfur and 300 ppm vanadium (210). An infrared instrument for sulfur dioxide in flue gases was desensitized to carbon monoxide and carbon dioxide response, while water vapor interference was reduced by removal of the vapor in a sulfuric acid drip column (328). T h e instrumentation was used with flue gases during testing of desulfurization b y dolomite-calcium hydroxide and limestone. -4 radioactive method for measurement of sulfur dioxide in flue gases employed a 40-pc Fe66 source to provide soft gamma radiation (80, 81). The equipment was tested in a power plant burning soft coal, and particulates u p to 1 g per 1113 caused negligible interference. T h e arsenazo I11 procedure involving acid-base titration was used t o determine sulfur oxides in stack gases (110). Possibilities for interferences by various ions were tested. An instrument utilizing a condensation technique was rcported for use in determining sulfuric acid aerosol in flue gases (310). An analytical procedure that compensates for reaction of sulfuric acid with dust in combustion gases has been discussed (315).Sampling and analysis techniques for oxides of sulfur and nitrogen oxides in emissions from large coal-fired steam generators have been discussed (278). Use of a nondispersive infrared analyzer for nitrogen dioxide in stack gases has been considered, including compensation for interference of water vapor (227). -1gas chromatograph has been used t o analyze hydrogen, nitrogen, carbon monoxide, and carbon dioxide in blastfurnace gases; results were compared with those obtained by infrared and o t h e r spectrometric methods ( 1 4 8 ) . Measurements of sulfur dioxide and particulate emissions from small- and medium-sized incinerators in Dusscldorf and Cologne have been reported (267). The sulfur dioxide levels in copper converter gases were measured with a commercial infrared system (87) ; t h e method appeared practical, but modifications were needed to make t h e system riccurate. Gaseous and particulate emissions from oil-fired stoves have been measured (102). Emissions from combustion of municipal refuse, landscape refuse, and automobile components have been analyzed for carbon monoxide, carbon dioxide, total hydrocarbon, formaldehyde, organic acids, nitrogen oxides, and polynuclear aromatic hydrocarbons (114). Open burning resulted in most of these pollutants being produced in
concentrations appreciably higher than t h o s e from municipal incineration. Sulfur dioxide, carbon monoxide, and benzo(a)pyrcne have been measured as products of spontaneous combustion in slag heaps (41) ; carbon monoxide and sulfur dioxide were produced in appreciable quantities. Analyses for polynuclear aromatic hydrocarbons were obtained at three coke plants in Czechoslovakia (191). i l n extraction procedure, thin layer chromatography, a n d spectrophotometric analysis have been used to separate and analyze several polynuclear aromatic hydrocarbons in rubber dusts and carbon blacks (276). Continuous monitoring for nitrogen oxides in chemical plant effluents was conducted by photometric analysis, n ith prior osidation of nitric oxide to nitrogen dioside (136). Methods of analysis of gases from the Kraft pulp process have been reviewed ( I ) . A commercial process gas chromatograph has been uscd to analyze thousands of samples from a recovery furnace for hydrogen sulfide, sulfur dioside, and methyl mercaptan (309). Efficiency of furnace operations was indicated better b y changes in hydrogen sulfide concentrations in the 100 t o 400 ppm range than b y analyses of oxygen or combustibles. Use of a bromine microcoulometric d e t e c t o r with Triton X-305 on Chromosorb G (DJICS-treated) as substrate was proposed for direct analysis of hydrogen sulfide, sulfur dioxide, and various organic sulfur compounds from recovery furnaces, digestor blow gas, evaporators, and other emission source of Kraft mill gases ( 2 ) . Different types of effluents from several Swedish pulp mills were determined by adsorption of 200- to 300-cc samples of silica gel a t room temperature, and desorption a t 120" t o 150" followed by gas chromatographic analysis ( 1 4 ) . Application of gas chromatography with flame ionizatiion and microcoulometric detectors also has made i t possible to detect more than 60 substances in Kraft black liquor, many of which appear in the pyrolysis gases (84). Compounds detected include inorganic gases including hydrogen sulfide, several hydrocarbons, and more than 20 sulfur-containing organic compounds. I n other work, the low boiling constituents of relief and blow gases were determined by gas chromatography and mass spectrometry (24). ilmong the 25 compounds identified were hydrogen sulfide, thiophene, and three sulfides. A recording electrolytic titrator has been used for total sulfur determination on samples from Kraft recovery furnace ducts, oxidation tower vents, and lime kiln stacks (295). Samples ranging in concentration from 100 ppb t o 800 ppm were analyzed in 7 t o 10 min per sample.
A polarographic method has been described for determining hydrogen sulfide and carbonyl sulfide in waste gases containing sulfur dioxide (325). Measurements of hydrogen sulfide emissions from recovery furnaces have been reported (209). A source sampling technique for particulate and gaseous fluorides involves use of a heated glass probe to convert hydrogen fluoride to silicon tetrafluoride (78). Measurements b y this technique showed t h a t ratios of gaseous to particulate fluorides vary over a wide range, from less than 0.01 to 1 to 25 t o 1, for different industrial processes. A similar sampling procedure has been used with a fluoride-specific ion electrode to analyze water-soluble fluorides in stack gases ( 9 1 ) . FIELD STUDIES
-llthough many investigators continue to report results of field studies, critical discussions of the utilization of such results are not frequent. TKOpublications during 196i emphasized the treatment of data and the use of dosage or dosage times area in interpretation of results (86, 167). I n one study, CAMP d a t a for 1962, 1963, and 1964 were used to obtain dosages (concentration times duration) and to develop equations for computation of the frequencies of occurrence, n hich were used for prediction of acute plant damage (167'). I n the other investigation, the product of dosage times area was introduced as a n operationally useful concept (86). T h e patterns of dosage times area for oxidant were computed and used with meteorological conditions in assessment of a smog episode. Research continues on the use of gaseous tracer techniques. Earlier analytical studies have been extended, with particular emphasis on sulfur hesafluoride as a tracer substance (60, 301). Concentration techniques were combined with ultrasensitive gas chroniatographic detection to obtain sensitivities don n t o 1 part of sulfur hesafluoride in 1014 parts of air (60). Such sensitivity levels are at or below atmospheric background. Application of the technique t o a n atmospheric diffusion experiment to distances of 7 5 miles was discussed (60). Further details also were reported (213) on field experiments using the sulfur hexafluoride, octofluorocyclobutane, and bromotrifluoromethane multipletracer technique previously developed (9), together with fluorescent particles for short-range work, and sulfur hexafluoride and fluorescent particles for longer-range measurements. A report of other work on gaseous tracers also discussed c o n c e n t r a t i o n procedures (301).I n this work measurements of sulfur hexafluoride background levels in Manhattan ranged from below 0.01 VOL. 41, NO. 5, APRIL 1969
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ppb near a power plant using SF6as a n insulator; a n interesting test of t h e use of sulfur hexafluoride as a tracer of stack effluents also was described. I n similar work in Japan, dichlorodifluoromethane and cobalt sulfate particles mere injected into stacks and the maximum ground level concentrations determined (131). The effects of pollutants on corrosion, fading of fabrics, discoloration of paints, and other adverse responses of materials have received further consideration. The horizontal and vertical distribution of corrosion rates of mild carbon steel plates in Jacksonville, Fla., in the center of the urban area correlated with sulfur dioxide and not with sea salt levels (121). The effects of sulfur dioxide, chlorides, and moisture on corrosion rates for various types of steel, copper, zinc, nickel, and aluminum have been discussed ( I S ) . The effects of oxidants on rubber products, textiles, dyed fabrics, and asphaltic materials have been reviewed (145). Fading of dyed fabrics occurs more rapidly than normal in urban sites during seasons of higher pollution ( 4 ) . Controlled environment studies of irradiated automobile exhaust with and without added sulfur dioxide showed fading caused by photochemically produced products; added sulfur dioxide produced more than an additive effect on fading of fabrics ( 4 ) . Identification of lead sulfide and mercuric sulfide on the surface of paints containing lead pigments or fungicides containing mercury as a result of hydrogen sulfide fumigation can be accomplished by use of a n electron diffraction technique (239). Several technical reports have described detailed air quality studies of both particulate and gaseous pollutants. A technical study in t h e Xew York-New Jersey area related to abatement activities included measurements for sulfur dioxide, particulate sulfate, sulfuric acid aerosol, hydrogen sulfide, carbon monoxide, and total suspended particulates (303). A similar technical study in the Washington, D . C., area included measurements of particulates, sulfur dioxide, carbon monoxide, hydrocarbons, nitrogen oxides, and oxidants (304). A special report was prepared on the meteorology and air quality of t h e Eastern United States during the Thanksgiving air pollution episode in 1966. This publication presented measurements made in a number of Eastern cities for particulates, sulfur dioxide, nitric oxide, nitrogen dioxide, hydrocarbons including methane, and carbon monoxide (104). Trends in Xew York City between 1954 and 1965 for concentrations of particulates measured by several different methods and for carbon monoxide, sulfur dioxide, nitrogen dioxide, 8 R
ANALYTICAL CHEMISTRY
and oxidant have been presented and discussed (33). Levels of particulates, sulfur oxides, polynuclear aromatic hydrocarbons, and a number of other gaseous and particulate pollutants have been obtained at two sites in London between 1954 and 1964 (67). Trends, cumulative frequency distributions, and levels during episodes are presented and discussed. Measurements were made in Basel, Switzerland, from 1961 t o 1964 in areas of dense traffic for carbon monoxide, lead, nitrogen dioxide, aldehyde, sulfur dioxide, and ammonia (207). Because of concern about pollution in historic toil ns, measurements were made in the main street of Warwick, England, for particulates, lead, and sulfur oxides (39). Measurements have been made in the Sumner Tunnel, used as a oneand two-way tube, for benzene-soluble particulates, polynuclear aromatic hydrocarbons, lead, carbon monoxide, oxides of nitrogen, and aliphatic aldehydes (68). Automobile exhaust was the predominant contributor of most of these pollutants. Analyses have been obtained at sites in three cities near Osaka, Japan, for beryllium, cadmium, chromium, copper, iron, nickel, titanium, and vanadium (290). The levels of chromium, copper, iron, nickel, titanium, and vanadium reported for one of these cities were considerably higher than the levels reported for U.S.or British cities. Measurements around the Yokahama area of Japan mere made of particle size and composition of particulate (130). Silica, ferric oxide, and sulfate were the chief constituents; the sulfate content of suspended particulate correlated well with sulfur dioxide concentrations. Analyses have been obtained for iron, aluminum, silica, and calcium in samples collected near a variety of industrial sites (251). Analysis of precipitation samples from a number of U.S.S.R. cities has shown t h a t the samples always contain silica, copper, and manganese; often contain iron; and sometimes contain beryllium, lead, aluminum, barium, and titanium (82). Analyses of samples collected a t sites in England by neutron activation for chlorine, bromide, manganese, sodium, aluminum, and vanadium have been reported (156). These authors do not mention the earlier work on use of neutron activation for determination of halogens in air (9). Additional work on halogens b y use of this earlier technique is cited later in this section. Samgiing for lead was conducted from moving vehicles in Cincinnati, Los Angeles, and San Francisco and on rural routes (160). Mean lead levels ranged from 3 t o 6pg per m3 on rural routes, t o 9 t o 38 pg per m3 for weekday downtown and freeway routes, to more than 40 pg per m3 on the Los Angeles freeway
system. Measurements of lead particulate in Cagliari, Italy, at locations where traffic was interrupted by traffic lights gave levels of 16 to 24 pg per m3 (189). Atmospheric lead concentrations obtained near the Philadelphia Airport have been related t o meteorological parameters (26). Particle size distributions of urban lead aerosols were obtained a t sites in downtown, industrial, and residential areas in Los Angeles, San Francisco, Chicago, Cincinnati, and Philadelphia and at remote sites in Oklahoma and Arizona (242). A t the urban locations, the average lead concentrations ranged from 3 to 9 pg per m3. T h e average mass median diameter was 0.25 p, with the lower and upper quartile points 0.16 and 0.43 M. Despite differences in industrial activities a t the various sites, the particle size distributions were similar (242). Talc has been used extensively in pesticide formations. Talc and other minerals have been characterized by X-ray diffraction techniques in samples collected in San Diego and remote sites and in a glacial sample (326). Talc is suggested as a promising tracer for the study of the dispersion of solids and t h e translocation of pesticides. A large number of analyses for fluorine compounds were carried out over a &year period in the neighborhood of a n aluminum plant (132). The concentrations of total and gaseous fluorides exceeded 0.03 pg per m3 in 65 and 41y0 of the samples, respectively. Interest continues in field studies involving measurement of benzo(a)pyrene or a group of polynuclear aromatic hydrocarbons in airborne particulates. The benzo(a)pyrene content of dust samples in Vienna was determined following benzene extraction and thin layer chromatography by ultraviolet and fluorescent analyses (221). The average daily intake of 2 pg was reported to be equivalent to the amount inhaled from 50 t o 60 cigarettes. Benzo(a)pyrene and carbon monoxide were analyzed in samples collected at sites near and remote from vehicular traffic (326).
Samples collected over 10- t o 12meek periods on cotton fibers were used in separating pyrene, 3-methyl pyrene, benzo(a) pyrene, benzo(e)pyrene, triphenylene, chrysene, 1,12-benzperylene, and picene as 1,3,5-trinitrobenzene complexes with identification by infrared, ultraviolet, mass spectrometry, and melting points (59). A variety of polynuclear aromatic hydrocarbons were determined in 1965 and 1966 in airborne particulate samples collected in Siena, Italy (30). I n 1965 and 1966, airborne particulate samples mere collected in Rome, Italy, and later were analyzed for eleven polynuclear aromatic hydrocarbons (305). Identification of 1,2,4,5- and 3,4,9,10-
dibenspyrenes in airborne particulates from Leningrad was accomplished b y column and thin layer chromatography with identification b y quasilinear fluorescent spectrometry (88). Beneo(a)pyrene was determined in particulates collected near a coal briquet factory (158) and a n iron and steel works (291). A rapid thin layer chromatographic procedure has been used to determine benzo(a)pyrene, benx(c)acridine, and 7H-bena(de) anthracen-7-onein airborne particulates from over 50 U.S. cities (285). Concentrations, in micrograms per 1000 cubic meters, ranged from 0.2 t o 18, 0 to 1.5, and 1 to 13 for benao(a)pyrene, benz(c)acridine, and 7H-bena(de) a n t h r a c en-7-on e. T o t a1 organic carbon, amino acids, sugars, proteins, carbohydrates, organic acids, esters, and amines h a r e been determined in atmospheric precipitationsamples (270). Organic acids and esters constituted the major part of the organic matter identified. Carbon monoxide levels were determined a t five sites on Manhattan in New York City (151). Local traffic determined the diurnal carbon monoxide patterns at sites in Manhattan, and levels can be predicted approximately from early-morning readings. Concentrations of carbon monoxide were measured a t 12 street-level sites in Detroit, Kew York, and Los Angeles (65). K e e k d a y average values ranged from 2 t o 10.5 ppm, with a minimum value of 1 ppin and a maximum value of 38 ppm for 1 h. Carbon monoxide levels were related t o sampling site, season, traffic density, wind speed, and air stability. Carbon monoxide samples have been taken a t 317 locations, including tunnels, from 1959 to 1966 in Paris ( 5 5 ) . Carbon monoxide levels and traffic dcnsity correlated well, as did carbon monoxide and lead content. T h e correlations werr poor betlveen carbon monoxide and benzo(a)pyrene, with only 10 t o 2094 of the benao(ajpyrene attributed to automotive emissions. Measurements of carbon monoxide and nitrogen dioxide nere obtained at intersections and in a tunnel in Zurich from 1961 to 1965 (128). The carboxyhemoglobin levels of traffic police were related to time, wind velocity, and traffic density. Carbon monoxide lrvels from 1.7 to 17 ppm were obtained, along with ammonia levels of 0.05 to 0.30 ppm, at 18 locations in Cagliari, Italy (281). I n seven parking garages, carbon monoxide levels ranged from 10 t o 95 ppm, with the mean for all samples at 58 ppm (238). Measurements of carbon monoside, carbon dioxide, and nitrogen dioxide have been made in a 10,000foot-long ventilated tunnel and related to diesel train operation in the tunnel (136). Isotopic carbon in carbon dioxide was determined in samples collected
in Manhattan; results indicated about a 20% increase in atmospheric carbon dioxide from automobile exhaust emissions (109). Two papers compared t h e measurement of sulfur dioxide b y the WestGaeke and conductivity methods. I n work done in Japan, higher levels were consistently obtained b y the conductivity instrument; ratios were 1.68 t o 1 in cold weather and 1.42 to 1 in warm weather (292). I n measurements at eight sites in Chicago, the conductivity measurements averaged higher, with a ratio of 1.2 t o 1 ( 2 9 ) ; the relationship was variable, however, n i t h the WestGaeke method sometimes giving higher values than t h e conductivity method. Both studies mention interference problems, including interference by nitrogen dioxide and heavy metals in the West-Gaeke method. However, in both studies, the original Kest-Gaeke method appears t o have been follon ed, and the series of papers between 1962 and 1966 on procedures for eliminating interferences in the \Test-Gaeke method apparently is not utilized (8, 9 ) . Considerations involved in establishing a telemetered air quality network in Chicago h a r e been discussed (126). A network of ground-level and aircraft measurements for sulfur dioxide and meteorological parameters has been developed for a research program on urban air pollution dynamics in Xew York. T h e report of this work (72) gives examples of three-dimensional distributions of temperature and sulfur dioxide within t h e urban area. Gravimetric and conductiometric measurements for sulfur dioxide and measurements for carbon monoxide in Lausanne in 1965-66 have been reported (54). Results were related to seasonal and diurnal variations and compared n i t h those reported for other cities. Sulfur dioxide levels in Reading, England, have been measured a t 40 sites: the chief contributors to pollution appeared t o be emission from domestic and loir level industrial chimneys (190). * i n escess of sulfur dioxide from the east was attributed t o a contribution from London’s pollution. Considerable effort has been made on measurement of levels of sulfur dioside in the vicinity of power plants. Continuous sulfur dioxide measurements have been made for a 2-year period around a modern 1000 RIW power plant located in a rural area (116). A discussion was given of instrumentation and sampling sites for sulfur dioxide measurement in the vicinity of a 360MK power plant with 100-m stacks in Great Britain (181). T h e ground-level sulfur dioxide measurements obtained in this study have been discussed as they vary with averaging time, wind speed, stability classifications, and heat emission effects (200). I n a n investiga-
tion in the U.S.S.R., ground-level concentrations of sulfur dioxide Ivere obtained out to 14 km. from a large power plant with 100-m stacks (119). Sulfur dioxide measurements also have been made with 30-min averaging tinies a t ground level downwind of two power plants and t h e results compared n i t h those obtained by various diffusion equations (92). A number of papers presented a t t h e Symposium on the Physicochemical Transformation of Sulfur Compounds in the Atmosphere and the Formation of . k i d Smogs were concerned with field studies of sulfur oxides. I n a study in Gothenburg, Sweden. measurements of sulfur dioxide, total sulfate, sulfuric acid aerosol, and total particulate were reported (225). Most of the sulfate and sulfuric acid aerosol n-ere associated with emissions from oil heating rather than atmospheric reactions. Measurements in Germany included free hydrogen ion concentration, and the sulfate, ammonia, chloride, and nitrate contents of various size particulates (152). I n atmospheric measurements made in England, acid concentration correlated well with the product of sulfur dioxide and particulate matter when particulate acid exceeded 50 p g per 1113 (66). lleasurements were made of sulfur dioxide, total sulfate, and sulfuric acid in urban and nonurban locations in Japan and of hydrogen sulfide a t Yellowstone Sational Park in the LIS. (260). The roles of manganese, iron, carbon, and calcium carbonate in the formation of sulfate and sulfuric acid aerosol were discussed. T h e same investigator has reported elsewherr on the formation of acid particles in the atmosphere (217‘) and on the presence of sulfate and other substances in fogs and clouds (219). Variations in sulfate concentration and particle size distribution in samples from four 1’3. cities have been discussed 11 ith regard to location. humidity, sulfur dioxidr level, and time of day (SOT). Measurements of sulfate and nitrate concentrations in particulate samples collectrd at different locations and seasons in the Los *ingrles Basin area have heen reported (186). Hydrogen sulfide concentrations measured in Karsaw in 1965 averaged near 0.6 fig per 1113, with little variation in concentration (40). d number of publications were concerned with field studies of reactants and products associated with photochemical air pollution. Measurements of C z to C5 aliphatic hydrocarbons in samples from the Los Angeles 13asin during 1967 were reported and the results related to emissions and t o oxidants levels (118). & i nexcess of light paraffins, especially propane, \vas confirmed. Ratios of exhaust hydrocarbons t o nitrogen oxides in the atmosVOL. 41, NO. 5, APRIL 1969
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phere did not agree well with exhaust composition measurements made with the California test cycle. C6 to clo aromatic hydrocarbons in samples collected in Los Angeles have been measured; the distribution of concentrations and concentration ratios of pairs of hydrocarbons was discussed in regard to emission sources (178). Analyses of C z to C6 aliphatic hydrocarbons in urban air samples in Japan also have been reported (153). T h e continuous air monitoring measurements for oxidants have been reviewed and the frequency of days on which oxidant exceeded various levels has been tabulated (144). A 2-year study relating oxidant levels to wind speed and direction was made in two small communities in New Jersey (171). Higher oxidant levels were associated with air trajectories from heavily populated and industrialized areas in Xew Jersey. Analyses for oxidant in samples taken in Moscow and elsewhere in the U.S.S.R. give indications of oxidant in the air and of photochemical smog as a potential problem (230). The fuchsin procedure for formaldehyde (inversion of West-Gaeke method) was used in Berlin (165). I n summer, the levels averaged 13.4 pg per m3, whereas in winter the levels averaged only 2.7 pg per ma. A number of studies during the past 2 years have been concerned primarily with ground level concentrations of pollutants and other substances of geophysical interest. Lead and Pb-210 were sampled near drgonne National Laboratory and a t a nonurban site 125 miles northeast (295). Results suggest t h a t atmospheric mixing a t loiv altitudes does not eliminate local variations in the rate of injection of lead into the atmosphere. Analyses of rainwater samples give a mean residence time for lead of about 1 month. Selenium in snow and rain samples collected in Xew England was determined by neutron activation along with sulfate by gravimetric or turbidimetric analysis (123). The weight ratio of Se/S was 1 X Comparison of this ratio with geochemical sources and seawater suggests a terrestrial, including pollution, source for selenium as well as for sulfur. Lead was determined b y inverse polarography and halogens by neutron activation on samples collected during the winter of 1965 a t sites in Alaska, Hawaii, and Massachusetts (85, 320, 322). Lead levels varied from G Mg per m3 in the center of Fairbanks, Alaska, t o 0.2 pg per m 3 outside the city (321). T h e I/Br ratios obtained were 0.1 to 0.2 to 1 (320). Iodine and bromine were associated with aerosols of smaller size and longer residence times than chlorine-rich aerosols (380). The bromine and iodine were considered t o be in part distilled from sea salt particles, photooxidized, and condensed as aero10 R
ANALYTICAL CHEMISTRY
sols. T h e bromine to chlorine ratio was low compared with the levels expected from gasoline additives. This result was interpreted as indicating loss of bromine from lead particulates by oxidation and volatilization (321). Analyses of particles collected from the ilntarctic atmosphere in the winter of 1966 showed hydrogen and ammonium as cations along with SO,- and Sa04- anions (4.2). T h e S/C1 ratio was high. T h e particles in volcanic fume appear to be XH4S04,on the basis of microchemical tests and electron diffraction (43). Traces of nitrogen dioxide, sulfur dioxide, and aldehydes in the parts per billion range were found a t times in samples collected in Antarctica (106). Possible sources of these gases were discussed. Ozone measurements were made in Antarctica using Regner and hIast type instruments from 1962 to 1965 ( 5 ) . Monthly means ranged between 2 and 4 pphm, with Mast values 10 t o 40% lower t h a n t h e Regner values. Ozone measurements were obtained in rural areas over bare soil and short dry grass (111). T h e ozone fluxes from 200 meters t o surface mere coinputed. The ozonic levels ranged from 10 to 50 pg per m3. Measurements of methane between ground level and 23 k m in a Southwestern U.S. location showed nearly constant mixing ratios to the tropopause, with mixing ratio decreasing rapidly in the lower atmosphere ( 1 7 ) . T h e results suggest t h a t the troposphere is the major region for destruction of methane. I n another study of methane, vertical profiles were obtained over Scotts Bluff, Neb. (90). Absolute concentrations varied considerably on different flight days. Results of this study indicate t h a t the production and destruction of methane are fast compared with the times required for atmospheric mixing. Use of a high resolution infrared spectrometer on a balloon flight in the lower stratosphere indicated the presence of nitric acid and nitrogen dioxide (608). LITERATURE CITED
(1) hdams, D. F., Proc. Intern. Conf. AtmosDheric Emissions from Sulfate Piilping, Sanibel Island, Fla., pp 96-110, Anril 1966. _... ~~
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