Air Pollution A. P. Altshuller, Bureau o f Disease Prevention and Environmental Control, National Center for Air Pollution Control, U. S. Department o f Health, Education, and Welfare, Public Health Service, 4676 Columbia Parkway, Cincinnati, Ohio 45226
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discussed in this review was published or presented between November 1964 and November 1966. Some references are included even though they were published before November 1964 because the work appeared in journals that are not available on a current basis. Conversely, references from readily available journals are included through December 1966. The previous review (6) included papers published or presented between October 1962 and October 1964, with a few more recent references. Presentations cited in the previous review ordinarily are not cited again as publications in the present review. Comparison with the previous review s h o w that a small decrease in analytical chemical research activity has occurred. This decrease amounts to about 15% if the field studies references are not included in the comparison. Even a small decrease in effort is unexpected, since an overall increase in technical activity and public concern about air pollution has occurred in the U.S. in the last few years. Methods for analysis of inorganic pollutants greatly outnumber those for organic pollutants in the present review. A large number of publications were concerned with analysis of polynuclear aromatic compounds, of sulfur dioxide and hydrogen sulfide, and of auto exhaust emissions. As usual, many of the papers a t the symposia and general sessions on air pollution held a t the spring and fall meetings of the American Chemical Society in 1965 and 1966 were in the field of analytical chemistry. Papers reporting analytical chemical applications were presented a t the 1965 and 1966 meetings of the Air Pollution Control Association and the American Industrial Hygiene Conference. The California State Department of Public Health sponsored a conference including analytical aspects of air pollution in January 1965. Several review articles were published on special topics in the analysis of air pollutants (118, 138,264). A collection of selected methods for the measurement of air pollutants was made available (212). The formation of an Analytical Methods Evaluation Service for air pollutants within the Public Health Service was announced (226). A 12th volume literature of translations of the U.S.S.R. consists of the 1963 volume of Gigiena i 10 R
OST OF THE WORK
ANALYTICAL CHEMISTRY
Sanitariya (148). Air quality measure-
ments on suspended particulates, 17 metals, three nonmetals, and six gases during 1964-65 in U.S. cities have been summarized (209). Continuous air monitoring data for gases in Cincinnati and Washington, D. C., in 1962-63 have been tabulated and discussed (210,211).
BIOLOGICAL INDICATORS
Various biological substrates have been used as indicators in laboratory studies. Additional studies have been reported of the ability of various components of the organic fraction of air particulate matter to immobilize Paramecium caudatum. The use of eye irritation panels as subjective indicators in laboratory investigations of photooxidation reactions is continuing. The use of plants as indicators of air pollution has been reviewed (98). The relationships between tobacco fleck injury and ozone levels in the field and greenhouse have been reviewed (100). A synergistic effect of sulfur dioxide on ozone damage to tobacco plants has been reported (172). Ozone-type injury was not observed with fumigation by 3 pphm of ozone, but injury was observed when 3 pphm of ozone was present concurrently with about 25 pphm of sulfur dioxide. The responses of tobacco wrapper Bel-W3 and pinto bean to various ozone concentrations ranging from 10 to 55 pphm for 0.5 to 4 hours of fumigation have been reported (99). Both ozone and peroxyacetyl nitrate can oxidize the reduced forms of nicotinamide adenine dinucleotides (180). Peroxyacetyl nitrate can inactivate enzymes by oxidation of enzyme sulfhydryl groups and also can inhibit incorporation of acetate into fatty acids (180). Preliminary results have been reported on the relation of ozone and peroxyacetyl nitrate concentrations to the corresponding types of plant damage as a result of funiigations with photooxidized propylenenitrogen oxide mixtures ( 7 ) . The bioassay of 15 benzene extracts of atmospheric particulates collected in various U. S. cities for carcinogenic activity was reported in terms of the immobilization of Paramecium caudatum exposgd to ultraviolet radiation in the 3600 A region (74). High activity was shown by an aromatic fraction, high to moderate activity by oxygenated fractions (not containing benzo [alpy-
rene), and intermediate activity by the crude benzene extracts. Promising results were obtained in the comparison of this same bioassay technique with an assay techniqiLe for carcinogenic activity in neonatal mice (73). Possible methods for the determination of lacrimatory potential have been considered (1.40). A polarographic determination involving catalytic reaction of sulfhydryl groups a t a dropping mercury electrode in a cobalt-containing buffer solution was applied to a variety of lacrimators. Eye irritation intensity responses were discussed as a function of hydrocarbon and nitrogen oxide concentrations in the photooxidation of the propylenenitric oxide system (234). Only part of the intensity of response could be accounted for by the formaldehyde produced, and the remainder of the response was not attributable to peroxyacyl nitrate a t the concentrations present in the reaction mixtures. Data on eye irritation responses as a function of time were obtained in other work on the photooxidation of propylene-nitrogen oxide mixtures and of diluted auto exhaust mixtures (221). The effects of reducing hydrocarbon, nitrogen oxide, or both reactants were discussed for the reactant concentration ranges investigated. Results of previous irradiation chamber experiments have been examined by statistical procedures to determine the effects of hydrocarbon and nitrogen oxide concentrations on eye irritation responses (188).
SAMPLING AND CALIBRATION METHODS
The high sulfate concentrations obtained in shorter-time sampling of air on glass-fiber filters result from oxidation of sulfur dioxide to sulfate on the filters (144). The discrepancy is reduced with longer-time sampling because the sulfate from sulfur dioxide reaches a saturation level. The efficiencies of the midget impinger and a new 2-ml micro-impinger were compared under various sampling conditions (160); the microimpinger is equivalent or superior to the midget impinger in sampling for sulfur dioxide, aniline, and dust. Improved collection efficiency in atmospheric sampling by the stacking of three fritted filters was reported (256). A sixfold sampler with sintered. glass filters has been discussed (15). Collection efficiencies in the sixfold absorber were consistently higher
than those in the normrtl fritted bubbler for hydrogen sulfide, nitrogen dioxide, carbon dioxide, benzene., and butanone. The use of hypodermic. needles as critical orifices in air samples has been evaluated (166). I n an investigation with 35S02as a tracer, significant loss of sampling efficiency below 10 pphm in both the conductometric and colorimetric pararosaniline methods was reported (281). I n another study with the same tracer technique, contradictory results were obtained. A 999; collection efficiency was found for wlfur dioxide in tetrachloromercurate solution a t 1.2 liters per minute in the range from 1 to 10 pphm (23). I n this same study 98% and higher collection efficiencies were found for sulfur dioxide in hydrogen peroxide solution a t rates as high as 6 liters per minute in tho range from 0.3 to 17 pphm sulfur dioxide. Another group of investigators rtlso has reported efficiencies near 99% in the 1- to 25pphm range for sulfur dioxide into hydrogen peroxide soluticn a t a flow rate of 1.4 liters per minute ( 2 7 ) . The absorption efficiencies of 6- to 60turn spiral contact columns were evaluated a t several air and liquid flow rates with two formulations of the Saltzmantype nitrogen dioxide reagent (903). I n another investigaticln the Saltzman and Jacobs-Hochheiser colorimetric procedures for nitrogen dinxide were compared for collection efficiencies under various conditions (232). Further evaluation of glass-fiber filters has been reported in the sampling of hydrogen fluoride (197). Calibration of limed filter papers has been discussed for measuring short-term hydrogen fluoride dosages (206). Interest in charcoal sampling tubes for sampling gases and vapors continues. The effects of sampling rate and volume collected on efficiency of collection on charcoal sampling tubes prior to gas chromatographic anal;rsis was determined for methyl ethyl ketone, toluene, trichloroethylene, butyl acetate, 2methylcyclohexanol, arid styrene (80). The absorption and recovery efficiencies of acrolein, methyl sulfille, and n-propyl mercaptan were evaluated on two different activated carbons (31). Sampling of the tracer substance, sulfur hexafluoride, onto carbon lollowed by desorption by heating permitted subsequent electron-capture gas chromatographic analysis to the 10-9-ppm level (46) The use of activated silica gel as an adsorbent for atmospheric contaminants has been reviewed wi1,h specific consideration of studies of adsorption of aromatic hydrocarbons, halogenated hydrocarbons, and acetone (34). Measurements of collection efficiencies on silica gel as a function of flow rate and sample volume were reported for ben-
zene, toluene, trichloroethylene, perchloroethylene, carbon tetrachloride, butyl acetate, ethyl acetate, formaldehyde, nitrogen dioxide, and other vapors (179). Silica gel tubes have been used for the collection of solvents such as perchloroethylene, mineral spirits, aromatic solvents, and ethyl acrylate from stacks (204). Dimethyl sulfoxide was satisfactory for recovery of a number of solvents, with subsequent gas chromatographic analysis (77). For Stoddard solvent, naphtha, and higher-boiling solvents, carbon disulfide and carbon disulfide-water were used for desorption, with subsequent infrared analysis (77). A chromatographic method for the concentration of trace impurities in the atmosphere has been developed, based on the theory of phase equilibrium (189). Short tubes containing the gas chromatographic substrates silicone elastomer E-301 and polyethylene glycol 400 on Celite 545 were used to evaluate the method. The precision available in the use of plastic bags mas determined to average *3y0 with 50 to 150 ppm of trichloroethylene (11). Pressure-volume characteristics of plastic bags have been reported (25). Use of the permeation rates of gases from sections of plastic tubing permits the dispersing of nanogram quantities with precision a t constant temperature (193). Permeation rates as functions of temperature vere obtained for sulfur dioxide, nitrogen dioxide, propane, and butane. Methods for the fabrication, calibration, and use of permeation tubes were described (193). I n a later report, modifications ivere suggested for extending the range of use of permeation tubes (192). Permeation tubes containing sulfur dioxide were studied in more detail; in this study the gravimetric method of calibration compared favorably with colorimetric and coulometric methods (247). Permeation tubes made of Teflon should be useful for preparing accurate concentrations of atmospheric pollutants, for calibrating instruments, and for developing or comparing analytical methods. A portable gas dilution apparatus has been developed and applied t o generation of sulfur dioxide, hydrogen sulfide, nitric oxide, and nitrogen dioxide (276). I n this same work, the satisfactory generation of sulfur dioxide a t concentrations from 0.01 to 32 ppm by thepermeation tube technique was confirmed. A simple compact dilution device can be used to dilute gaseous samples 3000 to 1 with accuracy within +1% (227). An automated variable-level dispersing system for hydrogen fluoride has been developed (114). An ultraviolet-type ozone generator has been used for producing ozone over a wide concentration range (257). Calibration of several coulometric
oxidant analyzers for ozone response by infrared techniques has been discussed (259). Methods for the synthesis and purification of peroxyacyl nitrates by preparative-scale gas chromatography have been described, along with the storage and handling characteristics of the products diluted in nitrogen (261). A dynamic calibration procedure for an acid aerosol analyzer has been reported (246)* PARTICULATES A N D AEROSOLS
Inorganic Particulates. An automatic air sampling system has been combined with a direct-reading spectrograph to analyze beryllium in particulates every 7 5 seconds with a sensitivity of 0.5 pg per cubic meter (224). After lead is collected on an iodine column or millipore filter and extracted, lead can be determined by atomic absorption spectroscopy with a sensitivity of 0.013 ppm a6 2170 A by use of an oxyhydrogen flame and T-piece adapter (39). Anionic interferences were eliminated by use of EDTA. A rapid analysis for lead on filter paper has been obtained by use of diphenylcarbazide in ethanol (94). Analyses of lead in particulates by the spectrographic, polarographic, spectrophotometric (tetrahydroxyquinone), and turbidimetric procedures (sodium rhodizonate or potassium dichromate) have been compared (218). Application of the Goetz aerosol spectrometer to particle-size distribution of lead in particulates has been discussed (157). Zinc can be determined by paper chromatography and complexonietric analysis in the range of 5 to 150 pg (222). Application of the ring-oven technique to the identification and determination of airborne particulates has been reviewed (288).
Fluorides have been measured in the range of 2 to 10 &g per cubic meter of air by the alizarin-complexion method after collection in a series of three silver tubes filled with silver balls (35). The determination of fluoride in air and plant tissues by the Willard-Winter and semiautomated methods was discussed (120). Analyses of the subcellular distribution of fluoride in orange leaves have been reported (40). An improved diffusion chamber, elimination of transfer steps, and application of sodium 2 - ( p sulfophenylazo) -1,8 - dihydroxynaphthalene-3,6-disulfonate zirconium lake have been developed for spectrophotometric determination of microgram amounts of fluoride in samples of biological material (41). A method has been made available for the analysis of chloride, bromide, and iodide in atmospheric samples; the method involves neutron activation followed by chemical separations (69). An improved method has been reported for determination of
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VOL. 39, NO. 5, APRIL 1967
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micro-sized sulfate particles (164). Sulfates have been determined by use of x-ray emission spectrometry (286). Macro- and microscopic applications of dispersion staining in air pollution have been described (66). Aerosols. A review of current problems in atmospheric aerosol research considered such topics as sampling procedures, distribution of chemical components with particle size, size analysis of acid aerosols, and gas-particle interactions (284). A number of aerosol generators have been developed. Three generators, an atomizer-impactor combination and two spinning disk systems, have been used for preparing homogeneous, monodisperse, spherical, and electrically neutral sclid particles of a fluorescent dye (291). Homogeneous aerosol production of solid particles by electrical atomization also has been reported (2Q6). Monodisperse aerosols have been generated with various shape factors (163). A new impaction device was developed for determination of aerosol concentration and composition (83). Size analysis of acid aerosols by a metal film technique has been discussed (110). Microscopic and electron-microscopic techniques can be used to identify sulfuric acid aerosol in presence of other substances in particulates (131). Hydrogen-flame emission spectrophotometry has been used in the monitoring of sulfuric acid aerosol (54). Hydrogenflame ionization analyzers were shown theoretically and experimentally to have potential for detecting and sizing organic aerosols (81, 191). A radiotracer study of lower-molecular-weight olefins irradiated with and without sulfur dioxide proved that no organic aerosols are formed in these systems (96). Organic Particulates. The nature of the benzene-soluble fraction of air particulates has been discussed (272). The n-alkanes in air particulates can be separated and analyzed by removing unsaturates by bromination and by separating n-alkanes and isoalkanes by molecular sieves, combined with gasliquid partition chromatography (171). Benzo [alpyrene is extractable from bituminous coal (279). The adsorption and extraction of benzo [alpyrene from soots has been investigated (137). The degree of volatilization of polycyclic hydrocarbons has been related to particle size and temperature (223). Ultraviolet irradiation of benzo [a]pyrene and perylene in diluted particulate matter caused 35 to 650/, of these hydrocarbons to disappear (274). Similar losses did not occur in the dark. Further work has been reported on possible modes of disappearance of benzo [alpyrene (276). Photochemical oxidation of benzo [alpyrene in benzene solution with oxygen present produced a t least three polynuclear aromatic
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0
ANALYTICAL CHEMISTRY
quinones, which were identified by melting point, by elemental analysis, and by infrared or ultraviolet spectra (164)*
Studies continue on various modifications of chromatographic, spectrophotometric, and fluorescent procedures for separation and analysis of benzo [a]pyrene and other polynuclear aromatic hydrocarbons. -4combination column and paper chromatographic system has been used for the separation of benzo[alpyrene (290). Liquid-liquid partition chromatography on silica gel for concentration followed by column chromatography on alumina and spectrophotometric analysis has been used to determine 13 polycyclic hydrocarbons (87). The spectrophotometric determination of benzo [alpyrene in the presence of pyrene has been discussed (186). Thin layer chromatography on alumina followed by low-temperature fluorescence spectrometry has been used to analyze for benzo[a]pyrene (121). The determination of 1,2,4,5-dibenzopyrene and of 3,4,9,10-dibenzopyrene in atmospheric samples can be accomplished by column or thin layer chromatography combined with fluorescent spectroscopy (62). Fluorescent spectrometry also has been applied in the measurement of benzo [alpyrene and benzo [klfluoranthrene by use of appropriate excitation wavelengths (66). Recoveries and background problems in analysis of polycyclic hydrocarbons by fluorescent spectroscopy have been studied (297). Programmed-temperature operation of glass capillary columns coated with SE-52, in combination Kith flame ionization or electron-capture detectors, provided separation and analysis of many polycyclic hydrocarbons, including partial separation of benzo [alpyrene and benzo[e]pyrene (38). A dual-column, dual-flame ionization detector apparatus has been used in the separation and analysis of six polycyclic hydrocarbons in air particulate samples (68). Partial separation of benzo [alpyrene from benSeveral zo[e]pyrene was reported. alkylated derivatives of polycyclic hydrocarbons have been identified in air particulate samples (246). Identifications were made by gas-liquid partition chromatography followed by fluorometric measurement of the bands, and by mixed-adsorbent two-dimensional thin layer chromatography followed by fluorometric measurement of the spots. Direct fluorometric scanning of thin layer chromatograms has been applied to mixtures of polycyclic hydrocarbons, mixtures of polynuclear aza heterocyclics, and coal-tar pitch fumes (242). Eight polycyclic hydrocarbons and 25 aza heterocyclic hydrocarbons were identified by their fluorescent spectra and by quenchofluorometric techniques after column and thin layer chromatography of coal-tar pitch, petroleum re-
finery incinerator effluents, and coal combustion stack effluents (241). A column chromatographic procedure has been developed for separating basic polynuclear aromatic compounds in complex mixtures (240). Several procedures for fluorometric analysis of benz [clacridine and other aza heterocyclic compounds after thin layer separation have been evaluated for use with air particulate and coal-tar samples (243). The chromatographic separation and spectral analysis of polynuclear aromatic amines and heterocyclic imines have been investigated (235). Spectral characterization of nitroarenes and amines and of polycyclic aldehydes, ketones, and quinones has been reported (122). Eight fluorescent quenching techniques have been applied in the direct analysis of thin layer chromatographic spots of various acridines, quinolines, and large-ring carbonyls (234). Column and thin layer chromatographic procedures were investigated for the separation of polynuclear ring carbonyl compounds (244). Phenalen-lone and 7-H-benz [d,e]anthracen-7-one in air particulate and source effluent samples have been identified and analyzed through use of one- and two-dimensional thin layer chromatography and direct spectrophotofluorometric examination of the thin layer plates (236). Various modifications of these thin layer chromatographic-fluorometric procedures for 7-H-benz [d,e]anthracen-7-one and phenalen-1-one were compared (236). Appropriate reagents have been discussed for making fluorescent formaldehyde and especially nonfluorescent aromatic substances that are precursors to formaldehyde on paper and thin layer chromatography (268). Based on indications of monocyclic carbonyl compounds in auto exhaust, an investigation has shown that 1,4-cyclohexanedione can be condensed with o-phthalaldehyde to form pentacenquinone, which can be determined spectrophotometrically as the neutral compound or dicationic salt in sulfuric acid solution and also spectrophotofluorometrically in acid solution (232). The purification of allergenic macromolecular compounds isolated from air particulates was accomplished by thin layer and preparative chromatography (84). A highly sensitive and selective colorimetric method has been developed for amino acids or primary amine precursors following thin layer chromatography (233). INORGANIC GASES
The sensitivity limitations involved in the direction of atmospheric vapors by surface-related effects have been considered (66). The condensation nuclei counter and its application to gas
analysis was discussed, with detailed consideration of sulfur dioxide, nitrogen dioxide, and phosgene analysis (282). Improved sampling and analysis procedures have been reported for measurement of sulfur dioxide, nitrogen dioxide, ammonia, and hydrogen sulfide in the National Air Sampling h'etwork of the Public Health Service (178). Interferences with various methods for analysis of inorganic gases in ajr have been reviewed (183). A simple modificat,ion of a comniercial sulfur dioxide analyzer allows its use for a variety of other atmospheric pollutants (187). A new colorimet,ric monitoring instrument for the sequent,ial determination of sulfur dioxide, nitric oxide, r.itrogen dioxide, hydrogen sulfide, chlor,ine, ozone, and fluoride has been described (82). Carbon Monoxide a.nd Carbon Dioxide. An extensive bibliography on carbon monoxide presents abstracts of analytical niet,hods (50). Carbon monoxide analyses by a Hersch-type galvanic cell and by gas chromatography have been evaluated (68). Carbon monoxide also wits analyzed gas chromatographically in a laboratory phot'ooxidat'ion reaction study (6). A gas chromat'ographic procedure for carbon dioxide in air has been described (184). Sulfur Dioxide. -in extensive bibliography on sulfur oxides presents abst.ract,s of analytical methods (51). Several groups of investigators have compared two or more methods for the analysis of sulfur dioxide. Closely comparable results were obtained in the comparison of the silica gel procedure of Stratmann with the colorimetric pararosaniline method with collection in tetrachloromercurat'e ijolution (265). Comparison of this spect'rophot.ometric method, the hydrogen peroxide method, and an electroconductometric instrument in analyses of amtiient air samples showed significant variations from city to city that suggested varying interference patterns (109). A laboratory comparison of t,he conductometric, t'itrimet.ric, and spect'rophotometric procedures for sulfur dioxide in air showed no significant. difference in responses among the several niethl3ds (276). Several investigations assessed the use of the lead dioxide cylinders for measurement' of sulfur compounds. The critical parameters considered in design of lead dioxide CJ linders included optimum loadings, lead dioxide particle size, use of various binders, and presence of reducing-type sulfur compounds (105). A statist.ica1 analysis has been reported after 4 years of measurement a t 20 sit,es. Result,s from adjacent lead dioxide cylinders and hydrogen peroxide-type instruments were compared (70); no generally applicable direct calibration between these two methods could be obtained. A titrimetric
method for sulfate in lead dioxide candles involved conversion of lead sulfate to ammonium sulfate followed by titration with barium perchlorate with Thoron as an indicator (217). Several suggested modifications in the colorimetric pararosaniline method for sulfur dioxide include a procedure for purification and standardization of the pararosaniline dye, use of phosphoric acid to control acidity, and use of sulfamic acid to eliminate nitrogen dioxide interference (249). The same authors previously reported a study of reagent purification, p H effects, stability of complex, and stability of colored product (248). With the sulfamic acid modification, application of the pararosaniline method to a large group of samples from U. S. cities resulted in sulfur dioxide concentrations averaging 30% higher than the concentrations obtained in the absence of sulfamic acid (178). I n another study with synthetic gas mixtures, very little decrease in absorbance was reported for the pararosaniline method with nitrogen dioxide added as compared to absorbances measured with no nitrogen dioxide added (276). The use of the reagent p-aminoazabenBene has been investigated for the determination of sulfur dioxide (133). Sulfur dioxide has been analyzed by x-ray emission spectrometry (285). Hydrogen flame emission spectrophotometry also has been applied to the analysis of sulfur dioxide in atmospheric samples (54)*
A number of new or modified monitoring instruments for sulfur dioxide have been evaluated. X modified AutoAnalyzer was used to determine sulfur dioxide as sulfate a t concentrations from 0 to 10 pg per ml by spectrophotometric titration with barium perchlorate and Thoron in dioxane-water solvent (202). Collection was in hydrogen peroxide rather than tetrachloromercurate solution because of somewhat better storage properties. A portable apparatus based on the pararosaniline reagent was developed for determining sulfur dioxide. Sampling time was 8 minutes, with a 15minute period for color formation; accuracy was +15y0 (102). Modifications of the Cummings-Redfern sulfur dioxide instrument (based on the reaction with the starch-iodine complex) allow recording of results, shorten the response time, and provide multiple full-scale ranges (12). Another instrument, also based on the starch-iodine complex reaction, prints out 0.5-hour mean values (19). Since the starchiodine reaction has poor specificity, a platinum catalyst with added hydrogen was built into the apparatus to eliminate interference by ozone and nitrogen dioxide. A galvanic-coulometric monitoring instrument based on the iodineiodide reaction has been developed for sulfur dioxide in air (103). The method
has high sensitivity, and a response time of several minutes, but shows poor specificity without a scrubber. Ozone interference is eliminated by a silver screen-granular silver column; interference by nitrogen dioxide is claimed to be only 2y0,with hydrogen sulfide, mercaptans, organic sulfides, and aldehydes interfering to varying extents (103, 167). A combination sulfur dioxide and ozone analyzer has been constructed; the system is based on oxidation of iodide to iodine by ozone in one channel and consumption of iodine by sulfur dioxide in the other channel, with amperometric measurements of the iodine concentration (250). Ozone is removed from the air going to the sulfur dioxide channel by a bed of ferrous sulfate crystals, and sulfur dioxide is removed from the ozone channel by a bed of quartz chips soaked in a solution of chromium trioxide in aqueous phosphoric acid. Sensitivity of this instrument is reported to be high, but its response time is no better than that of several other sulfur dioxide instruments. Potential interferences are discussed but not investigated (250). A sulfur-specific microcoulometric cell for use in gas chromatography was modified to provide improved response characteristics, longer electrolyte life, and higher sensitivity ( 2 ) . The detection limits of the detector are 5 pphm for sulfur dioxide and 1 pphm for hydrogen sulfide; the detector also responds to mercaptans and organic sulfides. This same cell has been used for direct analysis of sulfur dioxide, hydrogen sulfide, and organic sulfur compounds by use of selective prefilters to remove all but one of the sulfur compounds before the sample stream reaches the detector (4). Hydrogen Sulfide. The absorption efficiency of the cadmium hydroxide suspension t h a t has been used prior to the spectrophotometric methods for hydrogen sulfide has been determined by the H23% isotopic tracer technique (24). When three types of collectors were evaluated, the impinger with sintered glass disk gave the best efficiencies, averaging 9770Ja t flow rates up to 6 liters per minute a t hydrogen sulfide concentrations between 1 and 30 pphm. Various methods for analyzing hydrogen sulfide have been reviewed, and the methylene blue procedure recommended for atmospheric analysis (119). The flow rates suggested in this latter discussion, especially a t lower hydrogen sulfide concentrations, are higher than those recommended as a result of the H23% isotopic tracer study (24). A study of the light sensitivity of the cadmium sulfide suspension formed after collection of hydrogen sulfide in cadmium hydroxide indicates the need to protect the cadmium sulfide suspension from exposure to light ( I 39). VOL. 39, NO. 5, APRIL 1967
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Another investigation showed that in collecting hydrogen sulfide in cadmium hydroxide the midget impinger could be used at 3 liters per minute, and that a multijet bubbler could be used at 15 liters per minute (276). I n this same work, sulfur dioxide at 33 pphm increased the absorbance by 15%, ozone at 24 pphm decreased the absorbance slightly, and nitrogen dioxide had little or no effect. A portable hydrogen sulfide analyzer has been developed which achieves good sensitivity by use of tetraacetoxymercurifluorescein as a fluorescent indicator for hydrogen sulfide (9). A potentiometric method for low concentrations of hydrogen sulfide that uses sulfide-sensitive electrodes was reported (190). Membrane filters impregnated with lead acetate have been used in another method for hydrogen sulfide (196). Sulfur dioxide interference was eliminated by use of a potassium bicarbonate-impregnated filter; however, nitrogen dioxide also can interfere above 20 pphm. Fading of the lead sulfide spots in the lead acetate-impregnated paper-tape samplers can be caused by oxidation by air or ozone or by the action of sulfur dioxide and light (830). o-Phenyl phenol was an effective antioxidant, but use of this compound is not recommended for quantitative determination of hydrogen sulfide (230). I n another investigation parallel fading characteristics of the lead sulfide spots also were observed, and a lack of reliability of lead acetate paper tapes in automatic samplers was suggested (200). A mercuric chloride reagent for paper-tape sampling was developed which does not fade in light or under prolonged exposure to 10 ppm of ozone, nitrogen oxides, and sulfur dloxide (200). Nitrogen Oxides. Glass-fiber disks impregnated with acid dichromate were evaluated for use in oxidizing nitric oxide to nitrogen dioxide (124). Although this process is more efficient than the standard permanganate bubbler a t relative humidities between 19 and 46%, the efficiency of the acid dichromate decreased rapidly as the relative humidity was increased above 46% (12s). A modification of the permanganate oxidation involving permanganate reagent on glass beads was useful at concentrations up to 4 ppm of nitric oxide at relative humidities between 10 and 70% (S6). A study of the stoichiometry and of potential interferences with the reagent formulated by Saltzman has been reported. The investigators disagree with the 0.72 stoichiometry factor reported earlier (229), and find instead 1 mole of nitrogen dioxide equivalent to 1 mole of nitrite (266). These workers found no interference from fluoride, formaldehyde, or nitric oxide but claimed some interference from sulfur di14 R
*
ANALYTICAL CHEMISTRY
oxide, which could be eliminated by addition of sodium tetrachloromercurat,e. KOsignificant sulfur dioxide interference with this type of coupling react,ion with nitrogen dioxide has been found in other recent investigations (185, 276). The method based on the Saltzmantype reagent, and the Jacobs-Hochheiser method were compared by analysis of atmospheric samples for nit'ric oxide and nitrogen dioxide (107). A colorimetric reagent wit8h rapid color development and with improved intensity and stability has been formulated for nitrogen dioxide analysis; sodium 2-naphthol 3,6-disulfonate (R-salt) is used as a promoter and tartaric acid is substituted for acetic acid (162). Because it requires only a few minutes for full color development t'his reagent is of special interest. for use in monitoring inst,rumentat,ion. I n other work, acetic acid was omit.ted from t'he Saltzman reagent formulation for use in a continuous analyzer; results were satisfactory, and t,he reagent is less toxic, less corrosive, and less expensive (711. A more detailed study of various azodye reagent formulations resulted in the use of a reagent cont'aining citric acid, and sulfanilamide with '2:-(1-naphthyl)ethylenediamine in water (182). I n analysis of nitrogen dioxide by an AutoAnalyzer unit t'he reagent. cont.ained phosphoric acid, sulfanilamide, and Y(1-napht'hy1)ethylenediamine in water (178).
X met'hod was developed for the analysis of both nitric oxide and nitrogen dioxide in the 100- to 5000-ppm range by formation of the FeSO?.XO complex and spectrophotometric measurement a t 445 or 580 mp (1%). Another procedure for nitric oxide and nitrogen dioxide involved collect'ing in alkaline solution, acidifying, adding hydrogen peroxide, making basic and evaporat'ing, reacidifying, adding hydrogen peroxide, making basic and evaporat,ing,reacidifying, adding o-hydroxybenzoic acid, diluting with alkali, and reading color intensity (135). Ozone a n d Oxidants. A group of laboratory analytical methods including t h e colorimetric potassium iodide, phenolphthalein, sodium diphenylamine sulfonate, fluorescein, a n d 4,4'-dimethoxystilbene reagents a n d the nitrogen dioxide equivalent a n d rubber-cracking methods were evaluated for collection and analysis of low concentrations of ozone (101). The nitrogen dioxide equivalent method was preferred for ozone, but rubber cracking proved convenient for field survey work. Anot'her comparison st,udy evaluated t,he utility of t,he colorimet,ric potassium iodide, coulometric, and galvanictype analyzers, an ultraviolet photometer, and rubber cracking in application to atmospheric analysis (42). Differences in response t'o atmospheric
samples were attributed to differences in response to interferences. I n a third study of various ozone and oxidant met.hods, a wide variety of existing and new methods were considered with respect t'o sensitivity and specificity for ozone, nitrogen dioxide, hydrogen peroxide, alkyl hydroperoxides, peroxyacyl nit,rates, acyl peroxides, and peracids (215). These methods were evaluated for their effectiveness in different,iating the various tj,pes of oxidant material. A newly developed spect,rophotometric method for ozone involves react'ion of ozone with 1,2-di-(4-pyridyl)ethylene in glacial acetic acid and formation of pyridine-4-aldehyde, which is reacted wit,h 3-met8hyl-2-benzothiazolinone hydrazone hydrochloride (3RII3TH) to form an azine that can be determined at 442 mp (97'). Calibration, precision, and sensit'ivity, air sampling, and interferences have been considered. Sulfur dioxide, nitrogen dioxide, peroxyacyl nitrat,e, and other oxidants do not, interfere appreciably (97). However, hydrogen peroxide will interfere ~ignificant~ly if present in concent'rations comparable to those of ozone (215). A new method for atmospheric oxidant is based on the oxidation in ethanol of 9,lOdihydroacridine to t,he fluorescent acridine, acidification wit'h acetic acid, and measurement a t 482 mw (288). The sensitivity of the method is high, and the product is stable wit'hin 1 hour after sampling. Sulfur dioxide and hydrogen peroxide do not interfere, but nitrogen dioxide interferes significantly. A chemiluminescence method for ozone involving use of gallic acid with rhodamine B has been investignt,ed (16). A recording potentiometric analyzer for oxidants using iYH4Fe(C20Jzas a reducing agent has been reported (268). Other Inorganic Gaseous Pollutants. Phosgene has been determined in the part-per-billion range a n d higher by elect'ron-capture gas chromatography (208). Various colorimetric reagent,s for phosgene were evaluat,ed in liquid solution, impregnated on paper, and on granular solids (151). Hydrogen cyanide has been determined electrometrically by bromine tit,rat'ion with biamperometric indication a t concentrations from 0 to 1 kg per lit'er (263).
ORGANIC GASES A N D VAPORS
-4pplications of gas chromatography and infrared spectroscopy to the determination of organic pollutants have been reviewed (88). Portable instruments have been fabricated and evaluated for total organics and gas chromatographic analysis of trace constituents (89). Preliminary results in evaluating substrates for subtractive analysis or reactive organics in air have been reported (194). Combinations of various sub-
t,ractive techniques, column substrates, and gas chromatographic detectors were used to ident,ify various hydrocarbons, chlorinated hydrocarbons, organic sulfur compounds, and organic nitrates in atmospheric samples (292). A wide variety of silica gels were evaluated wit,h respect to rl..-eragepore diameter, water content., and added organic liquid phases in the sepiration of CI t'o CS paraffins, C2 to C4 olefins, and acetylene in at,mospheric sample:; ( I S ) . Aromatic hydrocarbons in the Cs to Clorange have been concentrated and analyzed by flame ionization after separation on an open-tubular-column subst,rate (185). Several groups of investigators have discussed concent'ration and separat'ion techniques for hydrocarbons (78, 127, 128, 260) similar to th'ise previously reported ( 5 ) . -4 seniiautomatic gas chromat,ographic system was developed for deterniining n-paraffir s and hydrocarbon t'\-pes (86). Collection efficiencies and molar absorptivities have been measured for acetaldehyde and propionaldehyde in the 3-methyl-2-benzothiazolone hydrazone method for aldehydes in air ( 4 7 ) . A procedure was reported for reducing the int,erference from oxides of nitrogen in the chroniotropic acid method for fornialdehyde (2%). =in evaluation of colorinietric methods for trace analysis of' acrolein indicat'ed i.hat t,he 4-hexylresorcinol method r i a ; superior to the tryptophan method in sensitivit,y, precision, and selectivity (1,?6). d procedure has been developed for neutron activation analysis of chlorinated hydrocarbons collected from the atmosphere on charcoal (177). The Fujiwarz reaction for the colorimetric analysis of chlorinatctd hydrocarbons was evaluated for dekrmination of carbon tetrachloroethane in air (160). An electron-capture gas chromatographic method has been developed for the ultramicroanalysis of bromotrifluoromethane and octofluorocyclobutane as well as sulfur hexafluoride as meteorological tracer substances in t'he at'nioijphere (228). --lliphatic alcohols in the C1 to Clo range in air can be septrated and determined by paper chromatography (205). A colorimetric determination of phenols in air utilizes a stabilized diazonium salt (53). An evaluation of substrates and detect'or characteristit's has been reported for the electron-capture gas chromatographic analysis of peroxyacyl nitrates in air (14). An electron-capture gas chromatographic method was developed for nitroethjlene and l-nitro1-propane in air with a detection limit of 0.001 ppm (262). The microcoulometric detect'or either with gas chromatographic or subtractive separation of sulfur compounds has been evaluated for the organic sulfur coinpounds methyl mercalhm, methyl sulfide, and dimet,hyl sulfide (2, 4).
ANALYSES
OF
SOURCES OF POLLUTION
Vehicular Emissions. Various problems associated with t h e sampling and holding of automobile exhaust gases have been discussed (79, 253). Losses in containers, lines, and traps and by chemical reactions can occur. The responses of the nondispersive infrared analyzer and the flame ionization analyzer for various hydrocarbons were measured and compared (115). It was concluded that the flame ionization analyzer, when operated at conditions giving approximately equal responses to hydrocarbons and low oxygen interference, gave a better approximation to total hydrocarbon concentration in automobile exhaust samples than did the nondispersive infrared analyzer. A rapid-response flame ionization detector has been constructed, with a response time of less than 1 second (85). An apparatus has been developed for analyzing hydrocarbon classes in less than 5 minutes by use of subtractive column substrates with flame ionization detection (132). This technique was evaluated in analyses of samples from large groups of automobiles on the road and on dynamometers (22,255). Analyses of a variety of aliphatic and aromatic hydrocarbons have been accomplished by temperature programming of open tubular colums from subambient temperatures (117, 166). One of these gas chromatographic systems also required the analysis of each sample for all components and then use of mercuric perchlorate to remove all but the paraffinic hydrocarbons before a second analysis for paraffinic components only (166). This system has been used in an evaluation of engine modifications on exhaust composition and in a comparison of several automobiles with engine modification and air injection control systems (116). The other system (117)has been used to evaluate the effect of gasoline composition on exhaust emissions of a vehicle with an air injection device (198).
I n another gas chromatographic system several larger-diameter open tubular column substrates were used under isothermal conditions along with a silica gel substrate for light hydrocarbons (13, 255). This system has been employed in a series of studies of automobiles whose exhausts were sampled on the road under normal driving conditions (254, of automobiles' exhaust emissions after both hot and cold starts in winter and summer, with sampling on the road (169), and of exhaust emissions from groups of automobiles equipped with air injection or engine modification devices or unequipped, again with sampling on the road (255). A gas chromatographic system involving temperature programming of packed columns previously discussed (5) has
been used in an evaluation of exhausts from various models of device-equipped and unequipped automobiles operated on dynamometers (22). Unsaturate compositions of exhaust emissions with gasolines of different compositions were determined in another investigation by gas chromatography with a subtractive technique (112). I n this study the exhaust compositions have been related to several reaction parameters in photochemical irradiation chamber measurements on the diluted exhaust emissions. Several methods for analyzing nitric oxide in aut,omobile exhaust emissions have been evaluated; these methods involved conductivity, spectral measurement of nitrogen dioxide after oxidation of nitric oxide, and direct mass spectrometric analysis (37). The mass spectrometric method \vas evaluated for interferences under different engine conditions. Difficulties in obtaining high precision in nitrogen oxide analyses even under steady-state operation were shown to result from engine variations. This mass spectrometric method compared favorably with the usual colorimetric analysis for nitrogen oxides. Another preliminary evaluation of mass spectrometric analysis of nitric oxide has been reported (60). Colorimetric analyses of nitrogen oxides in automobile exhaust by several different procedures n-ere compared (63). Water vapor, surface effects, and reactions between nitrogen dioxide and certain unsaturated hydrocarbons influenced losses of nitrogen oxides in these procedures. Carbonyl compounds in automobile exhaust emissions have been collected in bubblers containing aqueous 2,4-dinitrophenylhydrazone reagent. The hydrazones were filtered, extracted, and dissolved in carbon disulfide and then analyzed by gas chromatography with a flame ionization detector (181). Sampling efficiencies, analytical errors, and potential interferences were evaluated. I n another investigation of the determination of formaldehyde in liquid mixtures, the 2,4-dinitrophenylhy(irazone was used similarly and the possible application to air pollutants suggested (146). Carbonyls in auto exhaust emissions can be identified by collection in bisulfite reagent' folloived by combined gas-liquid chromatography and infrared techniques (72). Emissions from a group of automobiles and tracks have been analyzed for carbon monoxide, carbon dioxide, nitrogen oxides, total hydrocarbons, benzenesoluble particulates, and 10 of the polynuclear aromatic hydrocarbons (93). The presence of aza heterocyclic hydrocarbons such as benzo [h]quinoline, benzo [clacridine, and indenoquinolines in automobile exhaust has been demonstrated (238). The ratio of aza heterocyclics to polynuclear aromatic hydrocarbons in automobile exhaust is much VOL. 39, NO. 5, APRIL 1967
15 R
smaller than in other emission sources, a n indication that automobile exhaust is only a very minor contributor to atmospheric levels of aza heterocyclic compounds. Diesel exhaust emissions from twoand four-cycle engines have been analyzed for light hydrocarbons, nitrogen oxides, formaldehyde, acrolein, total aliphatic aldehydes, total particulates, and polynuclear aromatic hydrocarbons (219). Emissions from truck-type diesel engines were analyzed for nitrogen oxides, for formaldehyde, and for hydrocarbons including those from the unburned fuel (113). The gas chromatographic method used for higher-molecular-weight hydrocarbons in this latter study has been reported (251). An investigation was made into the effect of barium additives used to suppress smoke from diesels on the concentrations of hydrocarbons, oxides of nitrogen, and aldehydes in diesel exhaust from a two-cycle and a four-cycle engine (252). Other Sources of Emissions. A portable combustion analyzer for hydrocarbons, carbon monoxide, and carbon dioxide has been developed for use in air pollution source testing (20). Solvent vapors have been analyzed directly on polyethylene glycol 400 or squalane substrates with an argon ionization detector ( 7 5 ) . Solvent analysis has been done in another investigation by use of both gas chromatographic and infrared analysis ( 7 7 ) . The formation of nitrogen oxides in combustion of pulverized coal has been studied to determine effects of excess air and of recirculation of combustion gas (17 ) . Four methods for analyzing sulfur dioxide in flue gases were compared and found to give comparable results (125). Sulfur dioxide can be determined in flue gases by a colorimetric method employing alizarin and thorium salts (111). Polynuclear aromatic hydrocarbons have been analyzed in emissions from several industrial processes including asphalt air blowing, asphalt hot-road mix, and manufacture of carbon black, steel, coke, and chemicals (283). Effluents from the stack of a coal-burning residence, from two industrial sources, and from air contaminated with coal-tar pitch fumes have been analyzed for 12 polynuclear aromatic hydrocarbons and 11aza heterocyclics including the animal carcinogens benzo [alpyrene, benz [a]anthracene, dibenz [a,h]acridine, and dibenz [a,j]acridine (239). The concentrations of benzo [alpyrene measured in gas-works retort houses were 100 to 10,000 times the levels present in the ambient atmosphere of London (141). The amounts of total hydrocarbon, various aliphatic hydrocarbons, carbon monoxide, carbon dioxide, and nitrogen oxides were determined when a special tower built to simulate agricultural burning was used with various agricul16 R
ANALYTICAL CHEMISTRY
tural materials (57). The results indicated that the contribution of those pollutants associated with photochemical air pollution from agricultural burning was much less than from automobile exhaust emissions. Methods for sulfur compounds and odorants from kraft pulp mill manufacturing processes were reviewed (95). Gas chromatographic analyses of sulfurcontaining gases associated with kraft mills included analyses for oxygen, nitrogen, carbon monoxide, water vapor, hydrogen sulfide, sulfur dioxide, and methyl mercaptan using flame ionization, electron-capture, coulometric, thermionic emission and thermal conductivity detectors ( 3 ) . Analytical methods have been presented for a wide variety of gases from kraft pulp mill operations including hydrogen sulfide, sulfur dioxide, methyl mercaptan, ethyl mercaptan, dimethylsulfide, and other sulfides and disulfides (269). A PHS report has been published on atmospheric emissions from sulfuric acid manufacturing processes (214). Several methods of analysis for nitrogen oxides in gases from a pressure nitric oxide plant were evaluated (76). FIELD STUDIES
Work continues on the development of methods for atmospheric tracer substances to be used in meteorological investigations. The use of fluorescent particles as atmospheric tracers has been reviewed (145). Problems of calibration, separation, field operations, and background levels in the use of the gaseous tracers sulfur hexafluoride and dichlorodifluoromethane have been discussed (278).The atmospheric stabilities of sulfur hexafluoride, bromotrifluoromethane, and octafluorocyclobutane have been evaluated with respect to reactions with various atmospheric pollutants, effects of ultraviolet radiation, and washout (228). These three substances have high stability in such processes. The effects of air pollutants on exposed cotton fabrics have been measured (32). Atmospheric corrosion studies have been made in two metropolitan areas (280). The horizontal and vertical distribution of corrosion rates were determined in an industrialized city on the seacoast (129). Trends in suspended particulates in the air of U. S. cities for 1957 to 1964 have been reviewed (170). Total solids, iron, manganese, copper, tin, lead, and zinc were determined in the Paris area and the values compared to those in U. S. cities ( 5 3 ) . Sodium, potassium, calcium, and magnesium were determined along with sulfate, ammonium, nitrate, and nitrite and related to meteorological variations in areas of Asahikowa, Japan (195).
Much activity has occurred in discussions and measurements of lead as an atmospheric pollutant. Sources of atmospheric lead and of atmospheric lead levels were reviewed in a PHS publication (166). Concern has been expressed about possible biological effects of the lead levels presently existing in urban atmospheres (201). I n another review of biological aspects no hazard was considered to exist (92). X survey of the lead content of the atmospheres of three U.S. cities has been made (159) and the results presented in a PHS publication (213). Several thousand analyses for lead by a polarographic method were obtained on samples from 18 cities in Ontario, Canada (67). Lead analyses were made as part of more comprehensive analytical studies of the atmospheric coniposition in London (256), Paris region (63, 277), Japan (213),and Cambridge, Mass. (158). Lead isotopic composition of aerosols was determined in Los Angeles and found similar to that in rural snow (43). The high lead content in rainwater and on the surface of the sea were attributed to lead from automobile exhaust emissions. The chloride, bromide, and iodide content of cascade impactor samples were determined by neutron activation analysis a t t n o sites in Cambridge, Mass. (152). The results for chlorides and iodides related well to measurements made in unpolluted areas, while the bromide content was similar to that in polluted environments. Strong correlation of lead and bromide contents during low visibility situations and in curbside samples suggested a common source in the particulate from automobile exhausts. Several studies involving samples from Los Angeles Basin, San Francisco Bay area, Chicago, and Cincinnati all gave mass median diameters of 0.3 to 0.4 micron for sulfate-containing particulate (143, 158, 220). These investigations, as did one conducted in Pittsburgh (52), indicated that 80 to 90% of the sulfate-containing particulate was in the respirable size range. Some increase in mass median diameter occurred with increasing relative humidity (143). Seasonal variations were reported for sulfate concentrations in samples collected in Budapest (173). Fluoride concentrations were measured in an industrial region and surrounding rural area in France (26). The carcinogen benzo [alpyrene continued to be one of the most lvidely measured atmospheric pollutants. Analyses for benzo [alpyrene by fluorescent or spectrophotometric techniques frequently \vith thin layer chromatographic separation were reported for samples from London (286), Paris (142,277), Vienna (199),several cities in Germany (104), Leningrad (6'3, several cities in South Africa (156),Tokyo (225), Sidney, Australia (45), a number of cities
in Ontario, Canada (276), and Pittsburgh (59). I n the study of German cities, a number of other polynuclear aromatic hydrocarbons xere analyzed including anthracene, phenanthrene, pyrene, fluoranthene, 1,3-benzanthracene, chrysene, benzo [elpyrlme, 1,2,5,6-dibenzanthracene, and coronene (104). I n Sidney, after extrrxtion with acetone or cyclohexane and separation on long alumina columns, samples were analyzed by ultraviolet spectroscopy for pyrene, fluoranthene, 1,2 benzanthracene, chrysene, benzo [a Ipyrene, benzo[elpyrene, 1,12-benzope*ylene,and coronene (45). Possible interferences and unresolved fractions ako are discussed. I n the Pittsburgh study, gas-liquid partition chromatography was used to separate and measure pyrme, 1,a-benzanthracene, chrysene, benzo [k 1fluoranthene, benzo [elpyrene, and benzo [a]pyrene (59). I n a sample of Nashbille air, 19 polynuclear quinolines, iscquinolines, and acridines were identified (237). I n this same study, 11 polynuclear aromatic hydrocarbons, three benzacridines, and three quinolines were measured in samples from Atlanta, Cincinnati, Los Angeles, Nashville, New Orleans, and Philadelphia. A composite from 100 U. S. cities was analyzed for nine polynuclear aromatic hydrocarbons, 12 nalkanes, three benzacridines, and three quinolines. The weight ratio of aliphatic hydrocarbons to aromatic hydrocarbons to aza heterocydics measured in this composite sample was 300:24:1 (237). In a sample of particulates scraped off walls in a Naples tunnel, extraction, column chromitographic separation, followed by t h i i layer chromatography on several substrates, resulted in the identification of 74 compounds (64). Chlorinated hydrocarbon and thiophosphate type pesticides have been analyzed in particula ;e samples obtained from agricultur a1 communities during spraying operations and from communities with pest control programs (270). Use of the electron-capture and the sodium thermionic cetectors made i t possible to measure a variety of chlorinated hydrocarbons i,icluding D D T , chlordane, aldrin, toxaphrene, malathion, and traces of sweral thiophosphates. Dust transported over long distances u as analyzed by electron-caplure and microcoulometric chromatographic methods; analyses indicated the presence of D D T , chlordane, D D E , and ronnel and smaller ccmcentrations of heptachlor epoxide, 2,4,S-T, and dieldrin (48). Total organic chlorine was 1.3 ppm and total organic sulfur, 0.5 ppm. A rotating-disk impactor and a midget impinger have been used to collect both aerosol and gaseous fractions of airborne di- and trichlorophenox.yacetic acid and derivatives (2,4-D) (1). Following
analyses by the electron-capture chromatographic method over a 100-day period, the 24-hour average concentrations of aerosol and gaseous 2,4-D compounds were reported. Airborne particulates in Pittsburgh have been analyzed for D D T by gas chromatography (10). A brief review has been presented on automatic and manual data logging systems for air quality measurements of gases (149). The results from the Continuous Air Monitoring Program (CAMP) of the Public Health Service in six U. S. cities have been summarized for 1962-64 (161). One- and two-year means; maximum monthly, daily, hourly, and 5-minute values; and seasonal and diurnal variations were reported for sulfur dioxide, nitric oxide, nitrogen dioxide, oxidant, carbon monoxide, and total hydrocarbons. The results of 5 years operation of another Public Health Service network in 50 U. S. cities in which sulfur dioxide and nitrogen dioxide have been collected in impinges on a 24-hour basis also have been reported (271). Where possible these 24-hour results were compared with results from the continuous air monitoring program. Details on Sampling and analyzing the sulfur dioxide and nitrogen dioxide are given (271). I n a more recent presentation on this gas network, the details of dutohnalyzer analysis have been given for sulfur dioxide, nitrogen dioxide, hydrogen sulfide, and aldehydes (178). A monitoring system for sulfur dioxide, nitrogen oxides, oxidants, and aldehydes has been developed in New Jersey Ivith direct analysis by Autohalyzer units (293, 294). Reagent consumption rates, operating costs, on-stream factors, and a lostrtime analysis have been discussed (294). A variety of gaseous pollutants including carbon monoxide, carbon dioxide, sulfur dioxide, nitrogen dioxide, oxidants, and formaldehyde have been determined on a toll road and in a parking area in Japan (273). Considerable work has been done on the analysis of carbon monoxide both in the ambient atmosphere and in possible high-risk situations inside automobiles, a t traffic intersections, and in tunnels. Analyses were made inside the passenger compartment over a 30-mile commuter route in Los hngeles a t various times of the day (90). Average carbon monoxide concentrations above 50 ppm for 40to 80-minute driving periods were reported, with peaks up to 120 ppm. During the winter on this route, carbon monoxide concentrations exceeded 30 pprn for 50% of the time and exceeded 45 ppm for 10% of the time. Similar but more extensive measurements of carbon monoxide have been made in a number of U. S. cities both inside motor vehicles and alongside traffic routes (30).
For the various routes used in these cities, 50% of the 20 to 30 minute integrated carbon monoxide values exceeded 20 to 40 ppm; 10% of these values exceeded 30 to 60 ppm. Comparison with carbon monoxide values from CAMP stations in the same cities showed the ratio of in-traffic to station values varied from 1.3 to 6.8 ( S O ) . Mean values for carbon monoxide during peak traffic hours a t the largest traffic section in Dayton, Ohio, were near 40 ppm whereas a t all other times the mean values for carbon monoxide were 26 ppm (216). Carbon monoxide values exceeded 100 ppm about 10% of the time a t this intersection during peak traffic hours. Comparisons also were made with relation to traffic volume, meteorological variations, and concentrations a t other urban sites (216). Measurements of carbon monoxide in the central districts of Paris showed that the highest average values were in the range of 26 to 47 ppm during 1960 to 1964 (277). Concentrations of carbon monoxide have been reported in several tunnels (28, 91). Carbon monoxide measurements have been made in several cities by use of nondispersive infrared analyzers; results have been integrated a t 30-minute intervals for comparison with two modified detector tube methods. (108). I n general, higher carbon monoxide levels were obtained by the nondispersive infrared measurements than by the detector tube procedures. Carbon dioxide measurements with a nondispersive infrared analyzer have been obtained in several U.S. cities (44). It was demonstrated that the variations in urban carbon dioxide concentrations above the background level result from both combustion and natural sources. Since it is not yet possible to predict the contribution from natural sources to urban carbon dioxide levels measurements of urban carbon dioxide were considered to have only limited utility as an index of air pollution (44). A statistical approach to determining the frequency distribution of sulfur dioxide concentrations has been shown to fit the experimental values obtained a t 20 measuring places (267). The empirical function obtained can be used in assessment of emission limits for sulfur dioxide. The role of wind parameters has been considered in determining sulfur dioxide concentrations in New Jersey (147). Investigators in England and in the U.S.S.R. have been concerned with the determination of sulfur dioxide distributions about power plants (21. 163). A detailed study has been reported on sulfur dioxide levels in an industrial region and adjacent rural area during 1961-63 (26). I n measurements during the winter in the center of Gothenburg, Sweden, good agreement was obtained for the pararosaniline method, a conVOL. 39, NO. 5, APRIL 1967
0
17 R
ductometric method, and a new modification of the hydrogen peroxide method (202).
hleasurements for hydrogen sulfide by the method involving lead acetatetreated filter paper in a community containing a Kraft pulp mill gave values from 0 to 10 pphm (106). Analyses also were made with the methylene blue method. These analytical results were compared with results from exposure of silver specimens (106). I n another study testing for hydrogen sulfide with lead acetate paper, unglazed tiles and visual examination were used to evaluate paint darkening and to develop a dosage relation for nonhealth air pollution effects of hydrogen sulfide (292). Analyses for nitric oxide and nitrogen dioxide were made by both the Saltzman and the Jacobs-Hochheiser methods in several cities (107). Field experience with the mast oxidant analyzer has been discussed in terms of calibration, sampling, maintenance, collection of data, and costs of operation (207). Continuous monitoring for methane, total hydrocarbon, and nonmethane hydrocarbon has been carried out in Los Angeles and Cincinnati by use of modified flame ionization analyzers (8). Although methane values are similar in the two cities, nonmethane levels were 4 times as high in Los Angeles as in Cincinnati. The distribution patterns indicated a different and more constant source for methane than for the other pollutants. Hydrocarbons have been measured on 20- to 30-minute integrated samples from insides of vehicles in several U.S. cities and compared with the levels recorded at CAJIP stations (SO). The hydrocarbon values were 1.4 to 2.7 times higher inside vehicles than a t the monitoring site. I n several cities, the upper 10% of hydrocarbon values exceeded 10 carbon ppm (30). The concentrations of a number of sixto 10-carbon aromatic hydrocarbons have been measured in samples collected at various locations in the Los Xngeles Basin (185). The concentrations of a number of aliphatic hydrocarbons were determined for samples collected in the Los Angeles Basin (260). These samples were subjected to photochemical irradiation in the laboratory to obtain the rates of consumption of the individual hydrocarbons in atmospheric samples. Aliphatic hydrocarbons have been analyzed in 200 samples collected at 21 locations in Tokyo during 1964 and 1965 both a t ground level and from aircraft (127). It was concluded that the main source of pollution in Tokyo is automobile exhaust gases. Measurements for aliphatic hydrocarbons have been reported in an industrial area in England ( l a d ) . Although nitroolefins can be analyzed a t concentrations as low as 0.001 ppm in the atmosphere, the first two members of the nitroolefin series 18 R
ANALYTICAL CHEMISTRY
could not be detected in samples collected in the Los Angeles Basin (262). An air pollution evaluation of Titan I1 testing firings has been made (61). The air pollution control program a t Cape Kennedy has been reviewed (168). Work continued on attempts to associate asthma episodes with specific atmospheric pollutants. Measurements have been made of aerosols, air ions, and gaseous pollutants in order to isolate causes of asthma episodes in S e w Orleans (130). I n Minnesota, measurements were obtained on particulates, sulfur dioxide, and nitrogen dioxide to relate these pollutants to occurrences of bronchial asthma (17 4 ) . Pollutant concentrations inside homes or apartments have been compared to ambient levels. I n S e w York City, the concentrations of hydrocarbons and nitrogen oxides inside an apartment house adjacent to a n expressway were significantly higher than at the air pollution laboratory sampling site, especially on days of high pollution (29). I n measurements made in Tokyo, particulates and sulfur dioxide levels outside were higher than inside, but nitrogen dioxide and formaldehyde levels were nearly the same inside and outside (175). Samples collected in living rooms of homes in Rotterdam showed on the average 80% of the particulate and 20% of the sulfur dioxide levels measured in the outside air (18). Fleck damage on tobacco in Southern Ontario was shown to relate to ozone levels of equal or greater than 20 pphmhour although measurements were made for a number of other pollutants (49).
LITERATURE CITED
(1) Adams, D. F., Barnesberger, W.,
150th Xational Meeting, ACS, Atlantic City, N. J., Sept. 12-17, 1965. (2) Adams, D. F., Jensen, G. A,, Steadman, J. P., Koppe, R. K., Ilobertson, T. J., ANAL.CHEY.38, 1094 (1966). (3) Adams, D. F., Koppe, R. K., Tuttle,
W. N., J . Air Pollution Control Assoc.
15, 31 (1965). (4) Adams, D. F., Rohertson, T. J., 152nd National Meeting, ACS, Sew York, N. Y., Sept. 11-16, 1966. ( 5 ) Altshuller, il. P., ANAL. CHEhl. 37, 11 (1965). (6) Altshuller, A. P., Cohen, I. R., Pnrcell, T. C., Can. J . Chem. 44,2973 (1966). ( 7 ) Altihuller, A. P., KopcLgnski, S. L., Lonneman, W.,Becker, T. L., Slater, R., Bellar, T. A,, Hindawi, I. J., 149th Xational Meeting, ACS, Detroit, hIich., April 5-9, 1965. (8) Altshuller, A. P., Ortman, G. C., Saltzman, B. E., Seligan, R. E., J . Air Pollution Control Assoc. 16, 57 (1966). (9) Andrew, T. R., Kichols, P. N . R., Analyst 90, 367 (1965). (10) Antommaria, P., Corn, X., DehIaio, L., Science 150, 1476 (1965). (11) Apol, .4.G., Cook, W.A,, Lawenee, E. F., Am. Ind. Hyg. Assoc. J . 27, 149 (1966). (12) Bassett, P. &I.,Davies, I., Intern. J . Air Water Pollution 10, 663 (1966).
(13) Bellar, T. A., Sigsby, J. E., 151st National Meeting, ACS, Pittsburgh, Pa., March 22-31, 1966. (14) Bellar, T. A., Slater, R. W., 150th National hleeting, ACS, Atlantic City, N. J., Sept. 12-17, 1965. (15) Bergshoeff, G., Intern. J . Air Water Pollution 10, 629 (1966). (16) Bersis, D., Vassilion, E., Analyst 91, 499 (1966). (17) Bienstock, D., Amsler, R. L., Bauer, E. R., J . Air Pollution Control Assoc. 16, 442 11966’). (18) ‘Biersteker,’K., de Graaf, H., Nass, Ch. A. G., Intern. J . Air Water Pollution 9, 343 (1965). (19) Bokhoven, C., Niessen, H. L. J., Ibid., 10, 233 (1966). (20) Bolduc, RI. J., Severs, R. K., Air Ena. 7. 26 (1965’3. (21) Boldyvev, E.’ N., Gigiena i Sanit, 29, 128 (1964). (22) Bonamassa, F., Wong-Woo, H., l52nd National Meeting, ACS, Sew York, K, Y., Sept. 11-16, 1966 (23) Bostrom, C. E., Intern. J . Air Water Pollution 9. 333 11965’3. (24) Ibid., 10, 435 11966). (25) Boubel, R. (V., Am. Ind. Hyg. Assoc. J . 26, si8 (1965). (26) Bourbon, P., Atmospherique Pollutton 27, 362 (1965). (27) Bracewel I,, J. hI., Hodgson, A. E. M.,Intern. J . il i r Water Pollution 9, 431 (1965’3. (28) Braja, hI., Trompeo, G., Rass. M e d . Znd. (Rome)33, 411 (1964). (29) Braverman, 11. >I., Smith, C., Am. Ind. H y g . Assoc. J . 26, 84 (1965). (30) Brice, R. >I., Roesler, J. F.. J . Air Pollution Control Assoc. 16, 597 (1966). (31) Brooman, D. L., Edgerley, E., Ibid., 16,25 (1966). (32) Brysson, R. J., Upham, J. .B., Trask, B. J., 59th Annual Meeting, Air Pollution Control Assoc., San Francisco, Calif., June 20-24, 1966. (33) Buchwald, H., Ann. Occupational H y g . (London) 9, 7 (1966). (34) Buchwald, H., Occupational Health Rev. (Ottawa) 17, 14 (1965). (35) Buck, &I.,Stratmann, H., BrennstofChem. 46, 231 (1965). (36) Calhoun, J. C., Brooks, C. R., Seventh Conf. Methods Air Pollution Studies, Los Angeles, Calif., Jan. 25-26, 1965. (37) Campau, R. hI., Neerman, J. C., Automotive Engineering Congr., Detroit, llich., Jan. 10-14, 1966. (38) Cantuti, V., Cartoni, G. P., Liberti, A., Torri, A. G., J . Chromatog. 17, 60 (1965). (39) Chakrabarti, C. L., Robinson, J. W., West. P. W.. Anal. Chim. Acta 34. 269 (1966). (40) Chang, C. W.,Thompson, C. R., Intern. J . Air Water Pollution 9, 685 (1965). (41) Chang, C. W., Thompson, C. R., Seventh Conf. hlethods Air Pollution Calif., Jan. 25-26, Studies, Los Angeles, 1965. (42) Cherniak, I., Bryan, R. J., J . Air Pollution Control Assoc. 15, 351 (1965). (43) Chow, T. J., Johnstone, AI. S., Science 147, 502 (1965). (44) Clarke, J. F., Faoro, R. B., J . Air Pollution Control Assoc. 16, 212 (1966). (45) Cleary, G. J., Sullivan, J. L., AIed. J . Australia 52, 758 (1965). (46) Clemons, C. A., Coleman, A. I., Saltaman, B. E., 152nd National hIeeting, ACS, New York, N. Y., Sept. 11-16, 1966. (47) Cohen, I. R., Altshuller, A. P., AXAL.CHEX 38, 1418 (1966). (48) Cohen, J. M., Pinkerton, C., 150th National hleeting, ACS, Atlantic City, N. J., Sept. 12-17, 1965.
(49) Cole, A. W., Ksrtz, SI., J . Air Pollution Control Assoc. 16, 201 (1966). (50)Cooper, A. G., “Carbon Monoxide. A Bibliography with Abstracts,” HEW, PHS, K’ashington, D. C., 1966. (51) Cooper, A. G., “Sulfur Oxides and Other Sulfur Compounds. A Bibliography with Abstracts,” HEW, PHS, Wastington, D. C., 1Cl65. (52) Corn, AI., Demaio, L., J . Air Pollution Control Aa,oc. 15, 26 (1965). (53) Courtecuisse, S., Atmospherique Pollution 27, 326 (1965). (54) Crider, W. L., ANAL. CHEM. 37, 1770 (1965). (55) Crossmon, G., Alicrochem. J . 10, 273 (1966). (56) Danetskaia, 0 . L., DiKun, P. P., Gigiena i Sunit. 29, 121 (1964). (57) Uarley, E. F., Burleson, F. R., AIateer, E. H., Middleton, J. T., Osterli. V. P.. J . Air Pollution Control Asaoc. ’11. 685 119661. (5s) DeSIaio, L., Ccrn, AI., ANAL. CHFM . 38. 131 I1966’1
(59) De>Ido;-L:,
Coin, AI., J . Air Pollution Control rlssoc. 16, 67 (1966).
(60) Denver, D. F., 1491h National Meeting. .4CS, Detroit, Llich., April 5-9, 1935. (61) Diamond, P., Johnson, H. K., Am. Znd. Hug. ilssoc. J . 20, 419 (1965). . 12, 90 (62) DiKun, P. P., V o ~ r Onkol. (1966). (63) Dimitriades, B., l52nd Kational AIeeting, ACS, New York, N. Y., Sept. 11-16, 1966. (64) Dovinola, V., Imperato, F., Rend. Accad. Fis. Mat. 31, 338 (1964). (65) Dravnieks, A., Weber, H. S.,Conf. Surface Efects Detection, Washington, D. C., l’J64, p. 277 (Pub. 1965). (66) Dubois, L., hlonkrian, J. L., Intern. J . Air Water Pollutioii 9, 131 (1965). (67) Dubois, L., Teichman, T., Airth, J. XI., Monkman, J. L., J . Air Pollution Control Assoc. 16, 77 (1966). (68) Dubois, L., Zdrojewski, X., Monkman, J. L., Zbad., p. 125. (69) Duce, R. A., Winchester, J. W., Radzochim. Acta 4, 100 (1965). (70) Eaves, A., RIacaul2y, R. C., Intern. J . i l z r Water Pollution 8, 645 (1964). (71) Elias, T. C., Calhoun, J. C., Kayne, K.,Seventh Conf. Methods Air Pollution Studies, Los An Seles, Calif., Jan. 25-26, 1965. (72) Ellis, G. F., Kendall, R. F., Eccleston, B. H., ANAL.CHEW37, 511 (1965). (73) Epstein, S.S., J . i i i r Pollution Control Assoc. 16, 545 (1966). (741 Epitein, S. S., Srr all, X., Sawicki, h., Falk, H. L., Zbid., 15, 174 (1965). (75) Fallentin, B., Sccialmed. Tidskr. (Stockholm)41, 30 (1964). (761 Faucett, H. L., ;\IcRight, T. C., Graham, H. G., AVAL. CHEX. 38, 1090 (1966). (77) Feldstein, RI., Ba eatrieri, S., 59th Annual Meeting, Air Pollution Control Assoc., San Francisco Calif., June 2024, 1966. (78) Feldstein, XI., Balestrieri, S., J . Air Pollutzon Control Assol.. 15, 177 (1965). (79) Fleming, 11. D., Dimitriades, B., Ham, Ii. W., Zbid., p. 371. (SO) Frauat, C. L., IIerrnann, E. R., Am. Znd. Hug: ilssoc. J . 27, 68 (1966). (81) Frostling, H., Lindgren, P. H., J. Gas Chromatog. 4, 24:: (1966). (82) Fuhrmsnn, H., S t a , ~ b25, 266 (1965). (83) Goetz, A., 152nd r\ ational Meeting, ACS, New York, N. Y., Sept. 11-16, 1966. (84) Goppers, V., Paulu., H. J., Am. Znd. Hug. AssoC. J . 27, 144 (1966). (8$) Graiff, L. B., 149th Xational bleetc ing, ACS, Detroit, hlich,, Apr. 5-9, 1965. (86) Green, L. E., Albert, D. K., Barber,
H. H., J . Gas Chromatog.4, 319 (1966). (87) Grimmer, G., Hildebrandt, A., J . Chromatog. 20, S9 (1965). (88) Grupinski, L., Staub 25, 484 (1965). (89) Guerrant, G. O., ANAL. CHEM.37, 516 (1965). (90) Haagen-Smit, A. J., Arch. Environ. Health 12, 548 (1966). (91) Hajek, F., Silnicni Doprara 12, 4 (1964). --, \ - -
(92) Haley, T. J., Arch. Environ. Health 12, 781 (1966). (93) Hangebrauck, R. P., Lauch, R. P., Xeeker, J. E., S m . Znd. Hug. ASSOC. J. ”” 27, 47 (1966). (94) Hara, S . , Ind. Health (Kawasaki, Japan) 3, 101 (1965). (95) Harding, C. I., Landry, J. E., Tappi 49, 61A (1966). (96) Harkins, J., Xicksic, S. W.,J . Air Pollutzon Control Assoc. 15, 218 (1965). (97) Hauaer, T. Ii., Bradley, D. W., A Y I L . CHEM. 38, 1 5 B (1966). (9s) Heck, IF‘. W.,Intern. J . dir Water Pollutzon 10, 99 (1966). (99) Heck, W. IT., Dunning, J. A., Hindawi, I. J., Science 151, 577 (1966). (100) Heggestad, H. E., J . Air Pollution Control Assoc. 11, 691 (1966). (101) Hendrick, Ii. II., Larson, L. B., Am. Znd. H y y . .lssoc. J . 27, 80 (1966). (102) Herrmann, G., Staub 25, 271 (1965). (103) Herach, P., Deuringer, R., 149th Kational lleeting, ACS, Detroit, Xich., April 1965, (104) Hettche, H. O., Staub 25, 365 (1965). (105) Hickey, H. R., Hendrickson, E. R., J . dar Pollution Control Assoc. 15,
409 (1965). (106) High, 11. D., Horstman, S. W., Am. Znd. Hug. rlssoc. J . 26, 366 (1965). (107) Ilochheiser, S., 150th Sational Aleeting, A4CS, Atlantic City, N. J., Sept. 12-17, 1965. (108) Ilochheiser, S.,Santner, J., 152nd Xational Meeting, ACS, New York, K.Y., Sept. 11-16, 1966. (109) Hochheiser, S., Santner, J., Ludmann, W. F., J . Air Pollution Control dssoc. 16, 266 (1966). (110) Ilorstman, S. W., Tagman, J., Annual Conf. Am. Ind. Hyg. Assoc., Pittsburgh, Pa., X a y 16-20, 1966. (111) Hraseva, J’., Vocel, J., Energetica 16, 344 (1966). (112) Hurn, R. W., Dimitriades, B., Fleming, R. D., 1965 Midyear hleeting SAE, Chicago, Ill., AIay 17-21, 1965. (113) Hurn, W.,Seitzinger, D. E., Am. Petrol. Inst. Proc. 45, 127 (1965). (114) Ivie, J. O., Thompson, C. R., Seventh Conf. Methods Air Pollution Studies, Los Angeles, Calif., Jan. 25-26, 1965. (115) Jackson, 31. W.,J . Air Pollution Control dssoc. 11, 697 (1966). (116) Jackson, 11. W.,1966 Midyear Meeting, SAE, Detroit, RIich., June 6-10, 1966. (117) Jacobs, E. S., ANAL. CHEM.38, 43 (1966). (118) Jacobs, AI. B., Encycl. Znd. Chem. Anal. 1. 99 119661. (119) Jacbbs, ‘31. B., J . Air Pollution Control Assoc. 15, 314 (1965). (120) Jacobson, J. S., blcCune, D. C., Weinstein, L. H., Hitchcock. A. E.. J . Air Pollution Control Assoc. 16, 367 (1966). (121) Jaeger, J., Lugrova, O., Chern. Zvesti 19, 774 (1965). (122) Johnson, H., Sawicki, E., Talanta 13. 1361 11966’1. (i23j ~oIlesjE. E., Pierce, L. B., hlueller, P. K., Seventh Conf. Methods Air Pollution Studies, Los Angeles, Calif., Jan. 25-26. 1965. (124) Jones, ’K., Green, R., A‘ature 205, 67 (1965).
(125) Kanno, S., Fukui, S., Kaito, S., Kaneko, AI., AIiyazaki, H., Ui, K., Ando, H., Kovayashii, C., Abe, T., Yasue, G., Toi, K., Japan Analyst 14, 1013 (1965). (126) Kaszper, IT., M e d . Pracy 16, 453 (1965). (127) Kato, T., Mem. Fac. Tech. Tokyo Metropol. Cniv. 15, 1267 (1965). (128) Kato, T., Bunscki, K., Bunseki Kagaku 15, 14 (1966). (129) Kelly, T.. R., ITarding, ,C. I., 59th Annual Neeting, Air Pollution Control Assoc., San Francisco, Calif., June 20-24, 1966. (130) Kenline, P. .4.,Arch. Environ. Health 12, 295 (1966). (131) Kimura, K., Tada, O., Kimotmki, K., Kakaaki, K., J . Sci. Labour 41, ,501 (1965). (132) Klosterman, D. L., Sigsby, J. E., 150th Kational Meeting, ACS, Atlantic Citv. N. J.. SeDt. 12-17. 1965.
1966. (135) Kosheler, K. F., Ulitin, Yu. G., Gigiena i Sunit 31, 48 (1966). (136) Kothny, E. L., Mueller, P. K., Seventh Conf. hlethods Air Pollution Studies, Los Angeles, Calif., Jan. 25-26, 1965. (137) Kutscher, W., Tomingas, R., Petkauskas, B., Staub 26, 92 (1966). (138) Lahmann, E., Zbid., 25, 346 (1965). (139) Lahmann, E., Prescher, K. E., Stauh 25, 527 (1965). (140) Lampe, K. F., Znd. ,$led. Surg. 34, 797 (1965). (141) Lawther, P. J., Commins, B. T., Waller, R. E., Brit. J . Znd. X e d . (London)22, 13 (1965). (142) Lebbe, AI. J., Atmospherique Pollution 27, 316 (1965). (143) Lee, R. E., Axt,. C. J.? Wagman, J., 59th Annual Meeting, Air Pollution Control Xssoc., San Francisco, Calif., June 20-24, 1966. (144) Lee, R. E., Wagman, J., Am. Ind. Hyg. Assoc. J . 27, 266 (1966). (145) Leighton, P. A., Perkins, W. A., Grinnell, S. W., Webster, F. X., J . Appl. Aleterol. 4, 334 (1965). (146) Leonard, R. E., Kiefer, 3. E., J . Gas Chromatog. 4, 142 (1966). (147) Leone, I. A., Brennan, E., Daines, R. H., Intern. J . Air Water Pollution 10, 113 (1966). (148) Levine, B. S., “1T.S.S.R. Literature on Air Pollution,,ancl Related Occupational Diseases, Vole 12, Clearing House for Federal Scientific and Technical Information, IT. S. Dept. Commerce, Springfield, T-a., 1966, (149) Lewis, R. J., Smith, R., Znfern. J . Air Waler Pollution 10, 161 (1966). (150) Linch, A. L., Corn, M.,Am. l n d . Hyg. Assoc. J . 26, 601 (1965). (151) Linch, A. L., Lord, S. S., Kubitz, K. A., DeBrunner, 11. R., Am. Znd. Hyg. Assoc. J . 26, 465 (1965). (152) Lininger, R. L., Duce, R. A., Wincheqter, J. W.,Matson, IT. R., J . Geophys. Res. 71, 2457 (1966). (153) Lippman, AI., Spiegelman, J., Albert, R. E., Annual Conf., ,4m. Ind. Hyg. Assoc., Houston, Texas, RIay 1965. (154) Lodge, L. P., Frank, E. R., Anal. Chim. Acta 35, 271 (1966). (155) Lodge, J. P., Pate, J. B., Ammons, B. E., Swanson, G. A, J . Azr Pollution Control dssoc. 16, 197 (1966). (156) Louw, C. W., Am. Znd. Hyg. Assoc. J . 26, 520 (1965). (157) Ludwig, F. L., Robinson, E., J . Air Pollution Control Assoc. 15, 102 (1965). VOL. 39, NO. 5, APRIL 1967
e
19 R
(158) Ludwig, F. L., Robinson, E., J . Colloid Sci. 20, 571 (1965). (159) Ludwig, J. H., Diggs, D. R., Hesselberg, H. E., >raga, J. A,, Amer. Znd. Hyg. Assoc. J . 26, 270 (1965). (160) Luap. G. A,, , 4 ~ . 4 CHEM. ~. 38, 1532 ‘ (1966).-(161) Lynn, D. A., bIchIullen, T. B., J . Air Pollution Control Assoc. 16, 186 (1966). (162) Lyshkow, S . A., Zbid., 15, 481 (i965j. (163) Martin, A., Barber, F. R., J. Znst. Fuel (London) 39, 294 (1966). (164) Masuda, L., Kuratsune, RI., Intern. J . Air Water Pollution 10, 805 (1966). (165) AIcCaldin, R. O., USPHS Publ. Y o . 14440, 7 (1965). (166) McEwen, D. J., ANAL.CHEM.38, 1047 (1966). (167) NcGee, J. J., 59th Annual Air Pollution Control Assoc. hleetine. San Fmnriwo. Calif.. June 20-24. 19g6. -.. .. (168) IIcLduth, il. E., Terry, J. P., Am. Ind. H y g . Bssoc. J . 26, 172 (1965). (169) hlchlichael, W. F., Sigsby, J. E.,
J . Air Pollution Control Assoc. 16,
474 (1966). (170) MclIullen, T. B., Smith, R., “The Trend of Suspended Particulates in Urban Air 1957-1964,” Public Health Service, Division of Air Pollution, Cincinnati, Ohio, September 1965. (171) RIcPherson, S. P., Sawicki, E., Fox, F. T., J . Gas Chromatog. 4, 156 (1966). (172) Menser, H. A., Haggstad, H. E., Science 153, 424 (1966). (173) Jlebzaros, E., Zdojaras (Budapest) 68, 43 (1964). (174) LIill, R. A., Hollenbeck, A. H., Paulus, H. J., Am. Znd. Hyg. Assoc. J . 26, 510 (1965): (175) RIiura, T., Kimura, K., Kimotsuki, K., Okusa,,H., Tada, O., and Sawano, T.. J . Scz. Labour (Tokuo) 41, 493 (1065). (176) Moore, G. E., Katz, RI., Dronley, W.B., J . Air Pollution Control Assoc. 16, 402 (1966). (177) Morgan, D. J., Duxbury, G., Ann. Occupatzonal Hyg. (London) 8, 253 (1965). (178) Morgan, G. B., Golden, C., 59th Annual Meeting, Air Pollution Control ASSOC.,San Francisco, Calif., June 20-24, 1966. (179) Mourik, Van, J. H. C., Am. Znd. Hyg. Assoc. J . 26, 498 (1965). (180) Mudd. J . B., Arch. Environ. Health ‘ lo: 10; 201 (1965). ‘ (181) Alueller, (isij A I U ~ . , P. K., Fracchia, 31. F , Schette, F. J., 152nd National ’Meeting; Meeting, ACS, Sew York, N. Y., Sept. 11-16, 1966. (182) RIueller, P. K., Kothny, E. L., Fansah, N. O., Tokiwa, Y., 59th Annual Meeting, Air Pollution Control ASSOC., San Francisco, Calif., June 20-24, 1966. (183) Mueller, P. K., Terraglio, F. P., Tokiwa, Y., Seventh Conf. Methods Air Pollution Studies, Los Angeles, Calif., Jan. 25-26, 1965. (184) Murray, J. N., Doe, J. B., ANAL. CHEM.37, 942 (1965). (185) Seligan, R. E., Leonard, 11. J., Bryan, R. J., 150th National Meeting, ACS, Atlantic City, N. J., Sept. 12-17, 1965. (186) Xenasheva, S. K., Giqiena i Sanit. 31, 50 (1966). (187) Kichols, P. N. R., Chem. Znd. (London) 39, 1654 (1964). (188) Kicksic. S.W., Harkins, J., Painter, ‘ L. J., Intern. J . Air Water Pollution 10, 15 (1966). (189’1 Novak. J.. Vasak, V.,Janak, J., ANAL.CHEX 37, 660 (1966). %
~
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ANALYTICAL CHEMISTRY
(190) Oehme, F., Wyden, H., Glas-Znstr. Tech. 9, 107 (1965). (191) Ohline, R. W., ANAL. CHEM.37, 93 (1965). (192) O’Keeffe, A. E., 152nd National LIeetine, rlCS, New York, N. Y.. Sept. li-16, 1966. (193) O’Keeffe, A . E., Ortman, G. C., AXIL. CHEM.38, 760 (1966). (194) O’Keeffe, A. E., Ortman, G. C., Saltzman, B. E., l52nd National Meeting, ACS, Kew York, K.Y., Sept. 11-16, 1966. (195) Okita, T., Intern. J . Air Water Pollution 9, 323 (1965). (196) Okita, T., Lodge, J. P., Seventh Conf. Methods Air Pollution Studies, Los Angele-, Calif., Jan. 25-26, 1965. (197) Pack, RI. R., Hill, A. C., J . Air Pollution Control Assoc. 15, 166 (1965). (198) Pahnke, A. J., Conte, J. F., Harris, W.C., hlorris, W.E., l52nd Xational Meeting, ACS, New York, K. Y., Sept. 11-16, 1966. (199) Pailer, RI., Begutter, H., Baumann, Schedling, J. A., Oesterr. ChemakerZtg. 67, 222 (1966). (200) PavC, J. P., J . Air Pollution Control Assoc. 16, 325 (1966). (201) Patterson, C. C., Arch. Environ. Health 11, 344 (1965). (202) Person, G. A., Intern. J . Air Water Pollution 10, 845 (1966). (203) Pierce, L., Tokiwa, Y., Kishikawa, K., J . Air Pollution Control Assoc. 15, 204 (1965). (204) Ping, A. Y., Clayton, L. R., McEwen, T., 59th Annual RIeeting, Air Pollution Control ASSOC., San Francisco, Calif., June 20-24, 1966. (205) Pinipina, I. A,, Giaiena i Sanit. 30, 65 (196fl. (206) Poppe, W. H., Wilson, W. L., Campbell, A I . W., Eddy, L. D., Annual Conf. Am. Ind. Hyg. Assoc., Pittsburgh, Pa., May 16-20, 1966. (207) Potter, L., Duckworth, S., J . Air Pollution Control Assoc. 15, 207 (1965). (208) Priestley, L. J., Critchfield, F. E., Ketcham, N. H., Cavender, J. D., A s i ~ CHEM. . 37, 70 (1965);< (209) Public Health Service, Air Quality Data for the National Air Sampling Setworks and Contributing State and Local Ketworks 1964-1965,” Cincinnati, Ohio, 1966. (210) Public Health Service, “Continuous Air Monitoring Program in Cincinnati 1962-1963,” Division of Air Pollution, Cincinnati, Ohio, January 1965. (211) Public Health Service, Continuous Air Monitoring Program in Washington, D. C., 1962-1963,” Division of Air Pollution, Cincinnati, Ohio, September 1966. (212) Public Health Service Publication No. 999-AP-11, “Selected Methods for the Measurement of Air Pollutants,” Interbranch Chemical Advisory Committee. Division of Air Pollution. Cincinnati, Ohio, May 1965. (213) Zbid., 999-AP-12,“Survey of Lead in the Atmosphere of Three TTrban Communities,” Division of Air Pollution, Cincinnati, Ohio, January 1965. (214) Ibid., 999-AP-13, “Atmospheric Emission from Sulfuric Acid Manufacturing Processes,” Division of Air Pollution, Cincinnati, Ohio, 1965. (215) Purcell, T. C., Cohen, I. R., 152nd Sational hIeeting, ACS, New York, N. Y., Sept. 11-16, 1966. (216) Ramsey, J. >I., Arch. Entiiron. Health 13, 44 (1966). (217) Raytier, A. C., J . Air Pollution Control Assoc. 16, 418 11966). (218) Razumov, V.. A., Aidavov, T. K., Gigiena i Sanit. 30, 42 (1965). (219) Recker, L. R., Scott, W. E., Biller
W. F., Am. Petrol. Inst. Proc. 45, 133 (1965). (220) Roesler, J. F., Stevenson, H. J. R., Nader, J. S., J . Air Pollution Control Assoc. 15, 576 (1965). (221) Romanovsky, J. C., Ingels, Gordon, R. J., 59th A4nnualMeeting, Air Pollution Control Assoc., San Francisco, Calif., June 20-24, 1966. (222) Romanowski, H., Med. Pracy. 16, 461 (1965). (223) Rondia, D., Intern. J . Air Water Pollution 9, 113 (1965). (224) Rozsa, J. T., Stone, J., Uguccini, 0 . W., A p p l . Spectry. 19, 7 (1965). (225) Sakabe, H., RIatsushita, H., Hayashi, H., Nozaki, K., Suzuki, Y., Ind. Health (Kawasaki) 3, 126 (1965). (226) Saltzman, B. E., J . Air Pollution Control Assoc. 16, 498 (1966). (227) Saltzman, B. E., Clemons, C. A., ANAL.CHEM.38. 800 (1966). (228) Saltzman, B. E., Coleman, A. I., Clemons, C. A,, Ibid., p. 753. (229) Saltzman, B. E., Wartburg, A. F., Zbid., 37, 1261 (1965). (230) Sanderson, H. P., Thomas, R., Katz. bI.. J . Air Pollution Control Asso;. 16,’328 (1966). (231) Sanano, T., Nakaaki, K., J . Sci. Labour 40, 511 (1964). (232) Sawicki, E., Johnson, H., A n d . Chim. Acta. 34, 381 (1966). (233) Sawicki, E., Johnson, H., Chemist Analyst 55, 101 (1966). (234) Sawicki, E., Johnson, H., J . Chromatog. 23, 142 (1966). (235) Sawicki, E., Johnson, H., Kosinski, K., Microchem. J . 10, 72 (1966). (236) Sawicki, E., Johnson, H., Morgan, M., 152nd National Meeting, ACS, New York, N. Y., Sept. 11-16, 1966. (237) Sanicki, E., McPherson, S. P., Stanley, T. W., Meeker, J., Elbert, W. C Intern. J . Air Water Pollution 9 , 5ik (1965). (238) Sawicki, E., Meeker, J. E., Morgan, M. J.. Arch. Environ. Health 11, 773 (1965). (239) Sawicki, E., Meeker, J. E., Morgan, h l . J., Intern. J. Air Water Pollution 9, 291 (1965). (240) Sawicki, E., Meeker, J. E., Morgan, M. J., J . Chromatog. 17, 252 (1965). (241) Sawicki, E., Stanley, T. W., Elbert, W. C., J . Chromatog. 18, 512 (1965). (242) Ibid., 20, 348 (1965). (243) Sawicki, E., Stanley, T. W., Elbert, W. C., l52nd National Meeting, ACS, Kew York, N. Y., Sept. 11-16, 1966. (244) Sawicki, E., Stanley, T. W., Elbert, W. C., Morgan, M., Talanta 12, 605 (1965). (245) Sawicki, E., Stanley, T. W., MCPherson, S., Morgan, AI., Zbid., 13, 619 (1966). (246) Scaringelli, F. P., Boone, R. E., Jutze, G. A., J . Air Pollution C‘ontrol Assoc. 16, 310 (1966). (247) Scaringelli, F. P., Frey, S. A., Saltzman, B. E., Annual Conf. Am. Ind. Hyg. ASSOC.,Pittsburgh, Pa.‘ May 16-20, 1966. (248) Scaringelli, F. P., Saltzman, B. E., Frey, S. A,, 150th National Meeting, ACS, Atlantic City, N. J., Sept. 12-17, 1965. (249) Scaringelli, F. P., Saltzman, B. E., Frey, S. A,, 151st National Meeting, ACS, Pittsburgh, Pa., hlarch 22-31, 1966. (250’1 Schulze. F.. ANAL. CHEM. 38. ‘ 748 (1966).’ ’ (251) Seizinger, D. E., 150th Xational Meeting, ACS, Atlantic City, N. J., Sept. 12-17, 1965. (252) Seizinger, D. E., Hurn, R. W., Fleming. R. D.. 152nd National Meeb ing, A(%, New’York, N. Y., Sept. 1116, 1966.
(253) Sigsby, J. E., Bellar, T. A., Bellar, M. L., Klosterman, D. L., 150t,h National Meeting, ACS, Atlantic City, N. J., Sept. 12-17, 1965. (254) Sigsby, J. E., Bellar, M. L., Klosterman, D. L., 149th National Meeting, ACS, Detroit, Mich., April 5-9, 1965. (255) Sigsby, J. E., Rose, A. H., 152nd National Meeting, A.CS, New York, ?;. Y., Sept. 11-16, 1S66. (256) Skare, I., Intern. J . Air Water Pollution 9, 129 (1965). (257) Ibid., p. 601. (258) Stanley, T. W., Sawicki, E., ANAL. CHEM.37, 938 (1965). (259) Stephens, E. R., Seventh Conf. Methods Air Pollution Studies, Los Angeles, Calif., Jan. 25-26, 1965. (260) Stephens, E. R., Burleson, F. R., 59th Annual Meeting, Air Pollution Control Assoc., San Francisco, Calif., June 20-24, 1966. (261) Stephens, E. R., Burleson, F. R., Cardiff, E. A,, J . Air Pollution Control Assoc. 15, 87 (1965). (262) Stephens, E. R., Price, hI. A., Ibid., p. 295. (263) Strafelda, F., Dolt?zal, J., Pokorny, P Collection Czech. Chem. Commun. 31, 2251 (1966). (264) Stratmann, H., Stcub 25,341 (1965). (265) Stratmann, H., Buck, bl., Intern. J . Air Water Pollutiori 9, 199 (1965). (266) Ibid., 10, 313 (1966). (267) Stratmann, H., Rosin, D., Staub 24, 520 (1964). (268) Suzuki, S.,Miura, S., Kogyo Kagaku Zasshi 68, 470 (1965). (269) Suzuki, Y., Nishigama, K., Oe, M., Kametani, F., Tokushima J . Exptl. Med. 11, 120 (1964).
(270) Tabor, E. C., J . Air Pollution Control Assoc. 15, 415 (1965). (271)- Tabor, E. C., Golden, C. C., Ibid., p. 7. (272) Tabor, E. C., Smith, G. V., 59th Annual Meeting, Air Pollution Control ASSOC.,San Francisco, Calif., June 20-24, 1966. (273) Tada, O., Sawano, T., Sakaaki, K., J . Sci. Labour 42, 463 (1966). (274) Tebbens, B. D., Thomas, J. F., Mukai, M., Am. Ind. Hyg. Assoc. J . 27, 415 (1966). (275) Thomas, J. F., Mukai, G., Tebbens, B. D., 152nd National Meeting, ACS, Kew York, N. Y., Sept. 11-16, 1966. (276) Thomas, &I. D., Amtowr, R. E., J . Air Pollution Control Assoc. 16, 618 (1966). (277) Tuffert, L., Lebbe, J., Chovin, P., Z. Praeventivmed. 11. 134 (1966). (278) Turk, A., Edmond, S. PI.;Mark, H., Collins, G. F., Bartlett, F., 149th National Meeting, - ACS, Detroit, Mich., April 5-9, 1965. (279) Tye, R., Horton, A. W., Rapien, I., Am. Ind. Hyg. Assoc. J . 27,25 (1966). (280) Upham, J. B., 59th Annual Meeting, Air Pollution Control Assoc., San Francisco, Calif., June 20-24, 1966. (281) Urone, P., Evans, J. B., Koyes, C. hl., ANAL.CHEM.37, 1104 (1965). (282) Van Luik, F. W., Skala, G. F., Murphy, C. B., Annual Conf. Am. Ind. Hyg. Assoc. Houston, Texas, hIav 1965. (283) “Von Lehmden, D. J., Hangebrauck, R. P., Meeker, J. E., J . Air Pollution Control Assoc. 15, 295 (1965). (284) Wagman, J., Intern. J . Air Water Pollution 10, 777 (1966).
(285) Walkley, J. E., “The Determination of Sulfur Dioxide and Sulfates by X-ray Emission Spectrometry,” Annual Conf. Am. Ind. Hyg. ASSOC.,Pittsburgh, Pa., May 16-20, 1966. (286) Walkley, J. E., “Reduction of Interference from Oxides of Nitrogen in the Chromotr;pic Acid Method for Formaldehyde, Annual Conf. Am. Ind. Hyg. Assoc., Pittsburgh, Pa., May 16-20,1966, (287) Waller, R. E., Commins, B. T., Lawther, P. J., Brit. J . Ind. Med. (London)22, 128 (1965). (288) Watanabe, H., Nakodoi, T., J . Air Pollution Control Assoc. 16, 614 (1966). (289) West, P. W., Ibid., 16, 601 (1966). (290) Wettig, K. Hygiene Sanit. 29, 66 (1964). (291) Whitby, K. T., Lundgren, D. A,, Peterson, C. M., Intern. J . Air Water Pollution 9, 263 (1965). (292) Williams, I. H., AXAL. CHEM.37, 1723 (1965). (293) Wohlers, H. C., Feldstein, M., J . Air Pollution Control Assoc. 16, 19 (1966). (294) Yunghans, R. S., Munroe, W. A,, Technicon Symposium, Automation in Analytical Chemistry, New York, N. Y., Sept. 8, 1965. (295) Yunghans, R. S.,Munroe, W. A., Lewis, N. J., Technicon Symposium, Automation in Analytical Chemistry, New York, K. Y., Oct. 19, 1966. (296) Yurkstas, E. P., Meisenzehl, AEC Res. Develop. Rept. UR-652, Oct. 30, 1964. (297) Zdrojewski, A., Dubois, L., Moore, G. E., Thomas, R., Rlonkman, J. L., 151st National Meeting, ACS, Pittsburgh, Pa., March 22-31, 1966.
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