APPLIED April 1959 Part 11
Review of
AIR POLLUTION
APPLIED
Kingsley Kay Department of National Health and Welfare, Ottawa, Canada
T
review covers the two years 1957 and 1958, supplementing previous analytical reviews by the author (209, 210). I n a recent general review (211) the author dealt with a limited number of analytical advances. The period has been marked by greatly increased interest in automobile exhaust analysis, in atmospheric carcinogens, and in measurement of radioactive air pollutants. The Committee on Air Pollution, American Chemical Society, has continued to organize symposia under the auspices of appropriate sections. Nitrogen oxides were featured a t New York in 1957 and sulfur oxides a t Chicago in 1958. A regional conference on the subject was organized by the European Office of the World Health Organization in Milan in 1956 and a committee of experts met later in Genera. There was a national conference in Washington last year. An active campaign has been under way in Russia (387). The important Geneva Conference on Peaceful Uses of Atomic Energy dealt with air pollution by radioactive materials (427). The 1958 conference on detection of nuclear explosions will undoubtedly lead to analytical advances in this area of HIS
measurement. The joint WHO/FAO Expert Committee on Radiochemical Methods of Analysis met in Geneva last September. An international journal of air pollution is now published from London (184). There have been a few general papers on measurement techniques in air pollution (9, 50,179, 186, 342, 344, 411). ASTM Committee D-22 has adopted tentative standards for nitrogen oxides, oxidants, inorganic fluorides, and sampling techniques for gases and vapors (14). Karplus and others (907) have made a n analog computer study on atmospheric diffusion of air pollutants. Application of numerical methods in studies of atmospheric pollution has been outlined by Frenkiel (133, 134). Reference may be made to rei.' Tiew on fundamental developments in analysis appearing biennially in this journal (15), to reviews on Russian analytical chemistry (466), coulometry (588), the EDTA titration @4),ion exchange resins (161, 568), polarography ( l 7 3 ) , paper electrophoresis (993), and flame spectroscopy (960). STUDIES ON AEROSOLS
An outstanding book of the period
contained the collected studies of Dautrebande on aerosols (90). There was an important Russian book on the mechanics of aerosols (138) and this was reviewed in America (200). Particulate clouds, dusts, smokes, and mists formed the subject of a book by Green and Lane in England (155), where air sampling for dust was also considered in a book by Davies (93). I n France, Avy has composed a book on aerosols which features filtration of industrial smokes (21). Scorer has dealt with natural aerodynamics (370). New Importance of Aerosols. The continuing progress in delineation of the fundamental reactions of polluted atmospheres has centered new analytical attention on the aerosols. Doyle and Renzetti (101) produced submicron particulates by irradiation of auto exhaust and showed that these were of sufficient size and concentration to reduce visibility. Tabor and Warren studied the distribution of metals in the atmosphere of some United States cities (409) and the characteristics of organic particulate matter (408). Adley and others (6) examined particulates in rural atmospheres. Cholak and coworkers (73) and Junge (901) have obVOL. 31, NO. 4, APRIL 1959
* 633
served concentration relationships as between the gaseous and particulate fractions of air. Oddie (306) has provided a review covering findings from a European network for the study of airborne inorganic salts and chemical content of rain water. Others have contributed on atmospheric assessment (114, 117, 20s). A second influence on the analytical approach to aerosols has been the accelerating research effort devoted to study of effects on the lungs. While this review does not cover biological advances, reference is warranted to the work of Dautrebande (90, 91), who has shown that dusts exert a constrice ing action and that submicron sizes are deposited to a high degree in the lungs. Work of Levis and others (233, 234) and Morrow and corr-orkers (283, 284) has also contributed to knowledge regarding the deposition of submicron particles in the lungs. The consequent need to assess filters and collection devices with submicron sizes follows (88, 89). Influence of hygroscopic property on retention has been shown by Milburn and coworkers (274). Interest in a possible biological action related to particle shape has been aroused by the n-ork of Lengerova and others on phagocytosis (232). Svirbely and Saltzman (406) have assessed the effect of particle size and wind speed on nasal penetration of windborne particles. The potentiating effect of aerosols on irritant gases first noted by Dautrebande in 1939 has since been observed with both particles (228, 311) and submicron droplets (12). These biological accomplishments must clearly influence the course of analytical developments on aerosols. AEROSOL EVALUATION TECHNIQUES
A critical assessment of aerosol collection techniques originally presented a t the 1956 American Chemical Society symposium has nom been published (363). Whitby and coworkers (449) studied physical properties of dusts in relation to their removal by air cleaners. Isokinetic sampling probes were dealt with (95) and automatic isokinetic sampling has been attempted (351). Other apparatus has included a n air flow interrupter for respiratory 11-ork (287), a multipurpose sampler for use with impinger or filter heads (108),and directional samplers (291, 341). Balloons and helicopters have been used for sampling stack effluents in study of diffusion patterns (143, 247). Two studies of the influence of design on dust fall collectors were conducted (246, 297). Sticky paper has been reexamined (168). The procedure of collecting radioactive fallout in trays of sand has been mentioned (1.99). 634
ANALYTICAL CHEMISTRY
The transmission principle in a smoke inspection guide has been found superior to the Ringelmann chart (347, 548). Incinerator and pulp mill discharge assessment was reviewed (3, 144). Measurement of absorbance of smoke in a chimney was considered (240). Field techniques used for stack height and exit diameter estimation were discussed (32). Hasenclever (166) activated dust by adsorption of radioactive gas as a tracer for testing of filters and the efficiency of the thermal precipitator. Corrosivity tests n ere assessed (129). Filtration. Fundamental research on filtration has made significant progress. Yoder and Empson (462) claim that it is now possible, with material for ivhich the penetration characteristics are known, to design a filter and secure any degree of protection desired for aerosols. The bases for prediction of filter particle size retention have been considered (467). Adhesion mechanisms in filters were delineated by Larsen (230). Gallily (142) has built filter models of grids composed of equally spaced metallic wires. M‘ith these models the calculation of the collection efficiency of single fibers within filters has been assayed and declared to be one of the most important and difficult problems in the theory of aerosol filtration. Fitzgerald and Detwiler (128) used potassium permanganate droplets to establish the optimum particle size for penetration of millipore type filters. Efficiencies of Type AA a t face velocities in range 10 to 40 em. per second \yere over 99% for particles over 0.1 micron and around 40% for particles less than 0.01 micron. These investigators have experimented on other filter media (127) with Duralumin particles in the range 0.005 to 0.1 micron in diameter. Spurny and Vondracek (396) have examined the filtration efficiency of membrane types using radioactive aerosols. Limitations of these filters for air sampling were assessed (312). Stephan and others (398) have developed a b-ray thickness gage for determining mass of filter cakes. A filter velocity probe on the thermal anemometer principle includes an accelerating device in n-hich low velocity air is collected. A constant pressure valve has been used in stabilizing air flow through filters (583). The filtration of radioactive exhaust from flame spectrophotometers vias considered (110). Filter Samplers. The method of estimating mass concentration of particulates from absorbance of filtered deposits in filter samplers has been closely examined. Johnson (196) demonstrated the validity of an equation relating reflectance of a filtered deposit
to the mass per unit area. The effect of aerosol and filter was considered and found to be highly significant. Pertinent to this problem n a s a subsequent paper by Rose ( 3 4 4 , mho developed a relationship between reflectivity and particle size for a number of materials including carbon black. Last year a paper by Katz and coworkers (208) provided a comprehensive analysis of the influence of particle size and composition on the reliability of the procedure. These latter factors are highly dependent on meteorological conditions, so that the validity of the procedure has been examined in this relation. Shephard and others (377) tested this type of instrument in domestic premises and found it unaffected by the changes in median particle size which occurred. An interesting paper last year by Rees (333) in England introduced a unit of air dirtiness, the “murk.” It was defined as when 0.1 cu. meter of air d r a m through 1 sq. mm. of Whatman No. 1 filter paper produced an increase in reflection density (a decrease in log,, reflection factor) of 0.1. The index ranged from 1 in midsummer inside a n air-cleaned space to 13,000 outdoors during severe fog. An automatic programming filter sampler has been conceived (332). A filter-type dust sampler eliminates large size particles by gravity settling (241). A filtering recorder for incinerators was considered (118). An automatic air sampler was designed for use with membrane filters (242). Impaction. A definitive publication on the principles of inertial impaction has been prepared by Ranz, well known for his fundamental contributions to the subject (330). Brink and Contant (45) have recently made a series of tests in the Venturi scrubber collection of phosphoric acid mist. Mist particle size, injection velocity, and number of spray jets were correlated. There Tvere also industrial tests of poir-er input on efficiency of dust scrubbers of various types by Semrau and others (372). Hoy and con-orkers (118) tested the annular impactor of Tait (410) for efficiency in collecting radioactive materials. That collected was found to be 89% > 1 micron in diameter. For a,p, and y-emitting particles, efficiency was similar to that of Khatman No. 41 paper. For radon decay products, efficiency vias only one tenth as high as that of Whatman 41. The cascade impactor has been designed for adiabatic nieasurenients on industrial processes (44). There is a German report of a fractionating konimeter on the cascade impactor principle, having three stages for 0.25-, 0.7-, and 2.3-micron radius particles (145). TKO papers on efficiency of liquid inipingers
have been noted (69, 161). An automatic liquid impinger sampling arrangement has been evolved (461). Thermal Precipitation. Examination of factors influencing precipitation has continued. A further paper on thermal forces has been written by Schadt and Cadle (364). There !vas a n examination of the relationship between particle size of deposition and sampling rate by Watson (439). Counting errors due to overlapping particles Tvere estimated by Roach (339), who compared counts of pairs of samples in which one of the pair m-as five times as dense as the other. It mas considered that the error was very high with the standard precipitator for concentrations of dust typical of those occurring in coal mines. An earlier paper (26) on a statistical examination of precipitator performance is noteworthy. Uniformity of particle deposition \vas secured in a hot tape design by Walkenhorst (434) and the use of this instrument has been spreading. Last year a continuous example embodying a moving tape was conceived by Orr and Martin (308). This approach overcomes the low sampling capacities and flow rates of the noncontinuous instruments. Electrostatic Precipitation. dllander and Matts (11) in Germany have carried out an interesting investigation of the particle size-deposition relationship. They have provided a means to predict the effect of varying the dimensions of the precipitator and the gas velocitl- or, inversely, to measure the spread of particle size in the dust. Evans (119) described a precipitator for liquid droplets based on the Wilkening principle (463) of introducing droplets parallel to the precipitating field so as to offset the resistance to entry of small droplets caused by the wind from the corona discharge. A large volume precipitator has been tested by Stern and coworkers (400) with bacterial spores 0.5 t o 1.5 microns in diameter, in the concentration range 2 X lo5 t o 3 X 105 particles per liter. Air flow of 700 liters per minute yielded 39% efficiency u-hich rose to 91% a t 260 liters per minute. There was reference to a reciprocating attachment for random collection of particles ( 5 ) . Centrifugation. Earlier systems of sample collection by centrifugation have not been suitable for submicron sizes. Now, Walter (435) has produced a small cyclone type capable of collecting particles as small as 0.5 micron. Subsequently Walter extended the principle to a probe type (436, 437). Hawksley and coworkers (168) recently designed a cyclone probe for dust loading estimations on flue gases but the lon-er particle size was 5 microns in diameter. The probability function was em-
ployed in a graphical method for determining the average efficiency of cyclones (10). Sonic Collection. T o date, sonic collection has given promise of cheaper industrial dust collection but has not superseded earlier small-scale collection techniques. There has been a review of sonic and ultrasonic agglutination by Boucher (41) n i t h an extensive bibliography. This author has stressed industrial applications in a subsequent two-part review (39, 40). The research of Brun and Boucher (48) on air jet sonic generators of static type \vith secondary resonance chambers was described. The approach yielded higher agglutination efficiency. Particle Characteristics. Most measurements of size and concentration of aerosols have been carried out by established procedures, notably microscopy, though interest has continued in development of automatic counting and sizing. There has been a useful review of available methods by Phelps (316). Cartwight also outlined methods (6‘3). Sources of error in determination of size distribution 17-ere comprehensively dealt with in a German paper by Bate1 (25). Mathematical laws underlying the subject Lvere discussed in relation to particle size distribution of air-borne mine dust by Sichel (381). Size determination by radioactivation has been an interesting approach by Abraham and coworkers (1). Following neutron irradiation, particle size is deduced from Stoke’s law, because particle size is proportional t o the number of atoms present and so to y activity. Ranz and Hofelt (331) have evolved a standard test method for determining drop size distribution of a nozzle spray. Inertial inpaction in a special flow system yielded a relative numerical measure of size distribution. Tn-o new papers have appeared on the spray droplet method for particle counting of liquid suspensions. Nixon and Fishee (303) reduced droplet size and improved accuracy. Williamson and Taylor (455) have also made a number of improvements in the technique. Thompson (419) size-fractionated aerosol by passing from a sampling probe through a series of jet impactors of characteristic diameters. The fraction air-borne after each jet was measured by light scattering to yield size distribution in terms of scattered light intensity. Rose (346) established a relationship between reflectivity and particle size for carbon black and certain other materials. Reflectivity corresponded to particle, not to aggregate size. There was a report by Dimmick and coworkers (99) on a light-scattering method for use in tank settling of particles. Numbers of fluorescent tracer particles in air from pollution transport
tests (264) have been estimated by measuring the intensity of the fluorescent light emitted (350). A device for simplifying manual assessment of particle sizes from microprojections was detailed (5). An additional example of the use of small-angle scattering for particle size determination covered pigments (266). Approaches to automatic counting and sizing were discussed by Thomas (418). An adaptation of the principle of the Gucker-O’Konski counter (159) n as made by Beirne and Hutcheon (68). Particles in the size range 50 to 700 microns in diameter n-ere moved along a capillary under a microscope objective t o cut off light from a photomultiplier tube. Another device 1151) is claimed to classify particles of 1 to 64 microns in diameter into 12 size groups a t the rate of 100 per second. A recording sedimentation balance has been used to weigh settling particles (329) and from this data good size estimation was obtained in the range 2 to 30 microns in diameter as compared with the Andreasen pipet technique. Christmas and Hosey (74) considered the present status of automatic counting. Propane was used for measuring specific surface area in Russia (212). Very small surface areas, under 1 sq. meter per gram, have been determined by Haul (167)using krypton adsorption. An automatic direct reading apparatus based on powder permeability was developed by Spillane (395). Cartmight (62) has used low temperature nitrogen sorption in conjunction with an electron microscope to demonstrate that quartz particles have an amorphous silica layer in the thickness range 10 to 50 A. The density of polystyrene and polyvinyl toluene latex particles has been reported (367). Production of Aerosols. Available methods of producing droplets 11 ere discussed by Browning and coworkers (47) last year. Hrubecky (179) carried out experiments on liquid atomization by air streams, using various methods of injection among other variables. I t was found that water injection into the region of maximum velocity parallel to air flow, gave highest degree of atomization under similar conditions. An electrically driven disk atomizer for high speeds of rotation \vas designed by Ryley (366). Farlow and French (122) calibrated liquid aerosol collectors n-ith droplets containing uniform size particles. Dautrebande and others (92) used liquid aerosol jet type generators and submicron particles in suspension to produce aerosols of particle size below 0.5 micron on dispersion. Gordieyeff (150) experimented with a compressed gas pistol for dispersion of solids without using liquids. A syringe technique VOL. 31,
NO. 4, APRIL 1959
635
was used for bacterial aerosols (46). Burdekin and coworkers (61) evolved a method of producing a standard dust cloud for test purposes by feeding dust into a small wind tunnel with arrangements for varying wind speed. Whitby and others (448) have reported on apparatus for evaluating air cleaning equipment, the essential feature being to produce a counterpart to natural airborne dust. Cember and coworkers (68) used clay particles as carriers of thallium for point source irradiation in the lungs of animals. Other Fundamental Aerosol Studies. I n a review by the author last year (211) fundamental aerosol studies during 1956-57 were dealt with. Additional work has included two papers by Milburn (272, 273) on theoretical aspects of evaporating water clouds. It was assumed that water droplets were fixed in space and began with equal diameters. Continuous field functions correlated vapor concentration, temperature, and droplet size. A nonlinear differential equation was developed to govern the propagation of such fields in space and time. Jarman (192) found that the evaporation of droplets in sprays of dyed kerosine fitted the theoretical deductions of Probert (326). Orr and coworkers (307) have examined the important relationship of aerosol size and relative humidity already considered biologically by Milburn (274). Gain and loss of water with humidity change were estimated for sodium chloride, ammonium sulfate, calcium chloride hexahydrate, silver iodide, lead iodide, and potassium chloride particles of radius 0.01 and 0.1 micron. Such particles adsorb a few molecular layers of water a t low relative humidities. They dissolved as humidity increased, becoming saturated droplets with an abrupt size increase. With increasing humidity the droplets grew and became more dilute. At a humidity considerably below that a t which particles originally dissolved, they recrystallized, dropping in size sharply. Late in 1958, Benton and others (31) experimented with the coalescence of droplets using ammonium or potassium thiocyanate and ferric ammonium sulfate which reacted to produce red droplets of ferric thiocyanate. These were examined microscopically after settling on vaselinecoated slides. It was found that concentrations of reactants influenced coalescence. Surface active agents were tested and found to have a marked effect. Ion distribution on the surface of droplets was proposed as an explanation of the phenomena. A connection was established between the shape factor distribution relating the projected area diameters and the Stoke’s law diameters of particles in a dust cloud, and the penetration ef-
636
ANALYTICAL CHEMISTRY
ficiency of a standard elutriator. This was based on microscopic examination of thermal precipitator samples taken with and without elutriator. This work, by Dawes and others (94), extended a n earlier theoretical and experimental study by Walton (438). CHEMICAL ANALYSIS
OF
POLLUTANTS
Current trends in air pollution have given new importance to certain areas of chemical analysis. The increasing application of nuclear energy has made necessary the development of radiochemical tests for assessment of pollution levels. Apart from this connection the advances in analytical methods available through radiochemistry have been exploited by air pollution workers. It has been known for some time that polycyclic aromatic hydrocarbons of carcinogenic potency exist in polluted atmospheres. This finding has been associated with epidemiological evidence in various countries of a higher incidence of lung cancer in urban populations than among rural dwellers. More recently Kotin and Falk (226) reported on experimental induction of pulmonary tumors in mice exposed to an atmosphere of ozonized gasoline. Such observations have aroused a search for additional examples of this class of hydrocarbons and research on new techniques has thus been stimulated. The gradual delineation of mechanisms responsible for Los Angeles smog has been a third influence on the trend of air pollution analysis during the review period. It has led to active research on auto exhaust. I n the area of sulfur effluents there have been significant advances. Amdur (1%’) reported in 1957 that submicron sulfuric acid mist potentiated the action of sulfur dioxide on laboratory animals. Two papers in 1958, by Johnstone (197) and Junge @OS), dealt with the role of metallic catalysts in bringing about the oxidation of sulfur dioxide to sulfuric acid in moist atmospheres. Johnstone calculated that rate of conversion in natural fog would be about 500 times the rate of oxidation of sulfur dioxide in air in intense sunlight. Interest continues in the effects of pollution on plant life. Recent developments were summarized by the author last year (211). There has been a subsequent review of the subject (270). Among the most toxic plant and animal poisons is fluorine, which presents analytical problems of sample preparation and removal of interfering substances. Arsenic and beryllium continue to occur widely in effluents and also present similar analytical problems. As a result much research can be reported on methods of analysis for these substances. Arsenic. Errors of loss and gain in current methods of arsenic deter-
mination have been reviewed by Satterlee (360). Volatile derivatives occurring in biological work represent an important potential loss. An extensive list of sources of gain included arsenic from gas burners and from air exhaled by humans. Schrenk and Schreibeis (367) have estimated the urinary arsenic levels occurring in the general population and among exposed workers. A molybdenum blue procedure was used. There have been two radiochemical methods advanced, one covering determination of arsenic in bone (222) and one designed to measure as little as 1 p.p.m. in hydrocarbon reforming catalysts (378). Cember (67) has calculated that as little as 6 X gram of arsenic in a sample may be estimated by neutron activation. Polarography was explored and the existence of two well-defined waves was confirmed for trivalent arsenic in hydrochloric acid solution (422). Magnesium fusion has been used on organic material to produce arsine which was oxidized by bromine and titrated iodometrically (204). Internal electrolysis was used to reduce low concentrations of arsenite to arsine, subsequently determined by the Gutzeit method (463). Arsenic as arsine has been determined in microgram quantity by the production of color in silica gel treated with mercuric chloride (220) or gold trichloride (221). Entrainment of arsenic by nascent sulfur was claimed to increase the sensitivity of spectrographic estimation (49). Berkhout (33) has put forward modifications of the Berkhout-Jongen version (34) of the molybdenum blue technique. New variations in sample preparation for this technique may be recorded (20, 126, 298, 464). Arsenomolybdate on paper has been spectrophotometrically estimated (86). Beryllium. The present state of the analytical chemistry of beryllium has been reviewed in Russia by Goryushina (16%’). Beryllium in the organs of several mammals has been determined (406) using morin according to the method of Klemperer (217). Two radiochemical methods have come out, a rapid one by Gold (149) using filter paper collection and polonium-210 and another by BleshinskiI and coworkers (36) using iron-59. Colorimetric determination of small quantities of beryllium has been considered by use of Eriochrome cyanine R ( 1 7 4 , Chrome blue K (206), resorcinol (429), Beryllon I and I1 (248), 8-hydroxyquinaldine (286, 186),and paper chromatographic separation from zinc and aluminum, then quinalizarin (168). A technique for rapid and sensitive spectrographic estimation involved collecting the beryllium on a small filter which was placed in a cavity in the
electrode (126). A microgravimetric method (320) capable of determining 500 y in 3 ml. of solution involved use of hexaammonium cobalt trichloride. A titrimetric method (468) based on the reaction of beryllium hydroxide and potassium fluoride will detect 0.4 y per milliliter. Fluorine. A definitive review of analytical methods by Ma (263) appeared late in 1958. Other interesting contributions may be mentioned. Thron and Gribhob (420)collaborated with ten chemists in a test of certain methods for water analysis and an assessment of interferences. Shoup (380) described a method of removing a number of the common interferences in the Scott-Sanchis technique. Vrotek and others (430) examined exhaustively the interferences in the decolorization of ferric thiocyanate. Adams and others (4) found improved recovery of fluorine from bovine urine when the Smith-Gardner (384)modification of the salt-acid-thorium titration of Williams (454)was used to eliminate the necessity for the removal of chlorine by silver, The analysis of bones and blood was also studied by Samachson and others (359) using distillation from sulfuric acid and colorimetric estimation with stable modified alizarin reagent a t 525 mp. Celechovsky and Holer (66) claim that excess of chlorine or sulfate does not interfere in the photometric determination by decolorization of the purple-red complex of phenazone with ferric ion in the presence of fluorine. Loss of fluoride ions on glass was studied by Specht (393), while Fremlin and others (132) based a fluorine-18 method on this phenomenon. The limed filter paper technique has been re-examined by Adams (2) and Robinson (340). Amperometric titration of fluoride with thorium (87, 165) and ferric iron (292) has been considered. Two colorimetric methods used in Russia for fluorine in air have been (313). Chromatography described calcium chloride-thorium nitrate-impregnated paper has been used to detect fluorine by Hall (162). Kielczewski (214) founded a method on paper impregnated with uranyl ferricyanide. Other new methods include one to detect as little as 0.005 y of fluorine using Chromazurol S (23), a rapid photometric method (29) directly applicable to water in the range 0 to 1.5 y per liter and finally a volatile metal fluoride detector for production purposes which is sensitive to large amounts of fluoride in air (376). The biennial review of gas analysis appearing in this journal in April 1958 should also be referred to. The present review is supplementary. Lead and Other Inorganic Substances. A study by Jecklin (193) has shown t h a t the lead content of
the people of the Ruhr is increasing year by year. This author has suggested t h a t the origin of t h e lead is combustion of gasoline. The subject has also been considered, in Switzerland by Dettling (97). I n America, Tufts (4.93) has estimated, in Chicago, lead a t .street level using tetrahydroxyquinone. The amount of lead correlated with the number of cars passing a given point and the average speed. It may be expected that this subject will receive further attention in highly polluted centers. Meanwhile improvements in lead determination have been sought. There have been modifications suggested (263) for speed and accuracy in the American Public Health Association version of the dithizone method. These included use of a colorimeter with a green Corning 4010 filter. Other contributions toward improving the dithizone (98, 260) and the chromate diphenylcarbazide procedures (250) were made. A portable microscrubber with aspirator operated by a Freon propellant has been designed (100). Reagents for conducting the leaddithizone test according to the version of Snyder and coworkers (389) are included. Mayer and Schweda (26.2) have discussed sources of error in the dithizone method and the polarographic technique. A spectrographic micromethod for lead in biological materials has been offered by Pfeilsticker (315) with a special sample preparation technique. Good agreement was obtained in tests using dithizone and a polarograph. Campbell and others (59) have prepared an extensive treatise on aluminum in the environment of man, Diaminochrysazin for boron determination has been proposed by Cogbill and Yoe (75) because of its rapid color development which was found superior to other colorimetric reagents. An electrochromatography method (175) for boron will detect 0.01 y. Similar sensitivity has been claimed for a spot test using curcumin (294). Occella and coworkers (304, 306) have reviewed methods for the determination of quartz. An extensive bibliography on the modification of the silicomolybdate method and its application to mineral dust was prepared by King and others (216) in 1955. A new colorimetric version designed for analyzing the total silica content of dust and fumes collected from the atmosphere has been described by Talvitie and Hyslop (412). A correlation was established between uranium in air and in urinary levels (176). A new approach to uranium analysis (148) has been made by spectrophotometry and 1(2-pyridylazo)-2-naphthol. The method will estimate in the range 40 to 400 7. Electrodeposition of uranium a t the microgram level has been carried out
(353). A new indicator, quercetin, was used (267) in titrating thorium with EDTA to a detectable limit of 2 y. Microscopy and Diffraction in Analysis. The electron microscope was used for microchemical analysis in Russia by Zemlyanova and Kushnir (465) who placed nitrocellulose film on the surface of solutions to be analyzed and on the film, a drop of reagent. Washed film was then viewed by electron microscopy. Very low levels of ion concentration can be determined. A comparable procedure for identification of halide and sulfate in submicron particles was described by Tufts and Lodge (424). Particles on grid-supported Formvar membranes were placed sample side down on a drop of mercurous fluorosilicate (5%) and after 2 minutes were put on sb drop of water, sample side up. After washing for 5 minutes the sample was dried in a desiccator to show groups of mercurous chloride crystals. For sulfate, grid is placed on a drop of saturated barium nitrate or lead nitrate. Crystals are then identified by electron microscopy. These authors also dealt with chemical identification of submicron and micron particles and the relationship of the halo size to particle size in earlier communications (2.43, 244). Ionophoretic and chromatographic analysis of single dust particles was reported by Turner (426). Tufts (423) has evolved a method for detecting lead particles using a chemical procedure previously adapted to lead determination ( I S ) . An alcoholic solution of tetrahydroxyquinone is applied to particles collected on filillipore filters. A red precipitate with lead is formed. The original size of the particles can be calculated by optical microscopic examination. TKO interesting papers on analysis techniques in electron microscopy were presented by Reis (334, 336). Pfefferkorn (514) offered a method of avoiding aggregation of collected particles by catching these on fine crystalline needles of suboptical dimensions produced by the oxidation of metal. There were other papers, including new developments in dispersion staining microscopy (54), the problem of overlapping of particles in using the flying spot microscope (65), and the electron microscopy of myelinic bodies and collagenous fibrils from silicotic lung lesions (322, 3%). Differential analysis of lung dust from a ceramic worker has been carried out by electron microscopy and microchemical tests (301). Adley (5) designed a microscope attachment for detecting and isolating radioactive particles. A combination of microscopy and x-ray diffraction has been discussed by Mitchell and Ryland (279) with specific reference to identification of dinitrophenylhydrazones of aldehydes, VOL. 31, NO. 4, APRIL 1959
637
Electron diffraction alone or in conjunction with microscopy offers new possibilities for analysis of submicron material. As early as 1954 Jacobi (188) used the combination to measure size distribution and chemical constitution of unipolarly charged aerosols of high dispersity and diameters of 50 to 1000A. The use of electron diffraction on selected areas of an electron microscope specimen has been simplified by Agar (8). Yamaguchi (461) has discussed electron diffraction for analysis of simple inorganic mixtures. Preparation of x-ray diffraction powder specimens of active or toxic metals by sealing filings in silica quills was outlined (281). Gamma-ray spectrometry has been used lately for investigation of plutonium-contaminated wounds (328). Birks and Brooks (35) have described a 1- to 3-micron electron probe x-ray microanalyser for spectrochemical analysis of lorn concentration material. X-ray shadow microscopy has been advanced by Yamaguchi (460) for preliminary detection in powdered samples of elements such as thorium and uranium. Radiochemical Analysis. Several communications have come out on the methodology of radiochemical analysis (153, ,894,231, 366), and there was a recent symposium on the subject in this journal (16). A comprehensive German monograph reviewing methods of measurement of radioactive constituents (623) was prepared. Neutron activation analysis has been reviewed (66) and a comparison of its sensitivity with other methods has been presented by Meinke (965). Reference has already been made to neutron activation techniques for arsenic (67, 229, 378) and beryllium (36, 149). Cember (67) has presented an interesting paper on the usefulness of the technique in air pollution, describing the success attained in study of stack effluent patterns by means of discharged antimony oxide, neutron-activated after collection. The concentration of stable strontium and barium in human bones has also been estimated by this technique (352). It has been used for particle size determination (1). Kinsman (916) and Solon and others (391) have reported on background radiation exposure of the general population. Rosholt (349) has outlined the results of a major study of quantitative radiochemical methods for determination of the complex of sources of natural radioactivity. Settler and others (374) have outlined simple laboratory methods for the analysis of radioactivity in surface waters and in biological samples. Total LY and p activity is estimated. It is claimed that the health significance can be interpreted from decay measure-
638
ANALYTICAL CHEMISTRY
ments or known radionuclide composition. Bradshaw and Setter (42) examined air particles by autoradiography. Total absolute activity of of small radioactive precipitates on filter paper has been estimated by Wagner and coworkers (432) using a windowless flow cpunter with assessment of both sides of paper. A comprehensive treatment of mathematical relationships governing diffusion and deposition in relation to reactors has been provided by Smith and Singer (385). A more recent paper by Stewart and coworkers (401) deals with a study of atmospheric diffusion of gases from the stack of the Harwell Reactor BEPO. Argon-41 was used as tracer gas, b- and -prays being measured. The composition of fallout contributing gamma radiation from an underwater explosion was given by Heiman (170). The expected composition of underwater and land surface detonations n-as discussed by Miller and others (276, 277). A radiochemical method of analysis for rubidium-106, strontium-90, cesium137, and cerium-144 in environmental materials has been developed lately by Merritt (269). Osmond and coworkers (309)in England have provided methods for determination of strontium-89, strontium-90, cesium-137, and cerium144 in rain water. Special steps were described for separating strontium from any calcium and sulfate in rain water. From the same laboratory a method for radiocalcium and radiostrontium in effluentshas been reported by Loveridge (945). A radiochemical method for strontium and barium in human urine was given by Farabee (121),most of the separations being carried out in a cation exchange resin column. Potassium-40 was separated. Carriers were not needed. Strontium and barium isotopes were coprecipitated with alkaline earth phosphate from an alkaline solution. Calcium and magnesium were preferentially chelated by EDTA over strontium and barium. It mas noted that, owing to its shorter half life, radiobarium will probably not be present in urine samples. Langham (229) provided a mathematical expression for the rate of excretion following intravenous administration of plutonium. Healy (165)has extended this work t o estimation of plutonium lung burden by urinalysis. An electrodeposition-nuclear track film technique was developed by Schwendiman and Healy (369) for this study. A liquid scintillation spectrometer has been used lately by Horrocks and Studier (177) for low level estimation of plutonium-241 a t a detection limit of 10-16 gram. The water vapor system for counting tritium first developed by Drever (104) has lately been improved by Merritt (268).
I n a series of papers on monitoring of effluents for alpha emitters, Jenkins and Sneddon (19.4) have described a radiochemical method for radium involving two stages of coprecipitation, one with lead sulfate, another with barium chloride. Courtier in 1957 published expressions relating the concentration of radon and thoron in the atmosphere with the observed activity from decay products in a filtration type of determination (83). Andreeva and Kovalev (17) determined radium aerosols in the presence of other a-active aerosols by collecting radon emitted over a 3-day storage period. The radon content of ground level air a t Harwell was estimated by Gale and Peaple (141) from p counting with an instrument calibrated against a point source of cobalt-134, chosen because of the similarity of its p energy to radium-& A portable radon detector for continuous air monitoring in the range 25 to 20,000 ppc. per liter is an important advance in instrumentation by Harris, LeVine, and "atnick (164). Air is passed a t 3 liters per minute through a flask coated on the inside with zinc sulfide phosphor. Scintillations are counted by a photomultiplier tube. There was a contribution by Martin (258) dealing with the variability of radon in repeated breath samples. A later paper r\-ith Kovar (959) discussed effects of psychogenic factors in the elimination of radon. An inexpensive scintillation flask for radon assay has been conceived (297). Gas Chromatography. Extensive use of gas chromatography has been made in the air pollution field, b u t in view of the biennial review on chromatography appearing in this journal in April 1958 no attempt will be made to present a composite picture of the subject in the present paper. Rushing (354) described chromatographic apparatus and procedures for air pollution study. ?\lore recently West and coworkers (446) presented details of a new procedure adapted to the very low concentrations of organic materials encountered in this field. Activated charcoal, silica gel, and activated alumina were compared for sampling, the charcoal being found most effective. Effects of temperature of sampling, moisture, and magnesium perchlorate drying were among other aspects considered. Transfer of the sample to columns was accomplished by heating the charcoal in an oil bath a t 200" C., passing the vapor through magnesium perchlorate, and sweeping it with helium. Infrared and M a s s Spectrometry. A description of a long path infrared spectroscope, designed a t the Franklin Institute, for air pollution studies has been given by Stephens (359). A catalog of infrared spectra for 66 gases
and vapors likely to be present as products of the combustion of rocket fuel was a valuable contribution by Pierson and coworkers (318). A substantial treatise on the interpretation of mass spectra of condensates from urban atmospheres has been prepared by Weaver and others (441) on the basis of examination of condensates from seven United States cities. Separate components from urban atmospheric condensates could not be resolved even after distillation into 50 fractions. Some simplification was possible to the extent that the compounds characterizing 12 pollutant sources were delineated. Production of Gas Mixtures. T K O new procedures for producing mixtures of gases may be added t o the many now in the literature (205, 262). A valuable investigation has been carried out by Wilson and Buchberg (458) on the effect of various factors on the types of materials used for construction of air pollution reaction chambers and the effect of such niaterials on chamber air. Among factors considered were transmission of solar radiation, pollution removal by rvvalls, diffusion of gases through walls, and contamination of chamber air by plastic !\-all material. Apart from plastics, tests were conducted with aluminum, stainless steel, painted aluminum, unpainted maple, and other materials. Chemicals used in the tests included nitrogen dioxide, pentane, and cyclohexene. Other G a s Analysis Techniques. The biennial review of gas analysis appearing in this journal in April 1958 gave an account of developments during 1957. An ingenious method for the analysis of very m a l l gas samples has been devised (235). The area of a small-rolume bubble of gas (0.001 to 0.1 ml.) in water between two glass plates is compared with its volume after addition of specific absorbents. The theory and principle of the sonic gas analyzer were the subject of an informative paper by Martin (267). SULFUR AND COMPOUNDS
The demand for the automatic recording of sulfur dioxide and related sulfur compounds has provided further designs. A colorimetric unit was brought out by Helwig and Gordon (171) late in 1958 with the object of attaining specificity for sulfur dioxide. The fuchsin-formaldehyde reagent had been found sensitive to nitrogen dioxide ($82). The color method of K e s t and Gaeke (444) which involved pararosaniline hydrochloride and formaldehyde was modified by the elimination of a mercury fixative and by reduction in pararosaniline of such concentration as to yield greater response. Tests
with nitrogen dioxide showed that less than 1 p.p.m. in air caused no interference when sulfur dioxide was present a t 4 p.p.m. Ozone a t 0.08 and 2.0 p.p.m. caused no interference in sulfur dioxide response a t 0.11 and 2.5 p.p.m., respectively. The p H of the reagent x a s critical for stability, resistance to interference, and optimum response. The instrument was sensitive to 0.002 y of sulfur dioxide per ml. of reagent in the range 0.01 to 5 y. Another apparatus designed in Czechoslovakia by Gottfried (154) provided for polarographic recording of sulfur dioxide in waste gases without interference by sulfur trioxide. A device invented by Densham and others (96) involved continuous estimation of the absorption of infrared or ultraviolet radiation a t relatively specific wave lengths. Provision for the catalytic conversion of hydrogen sulfide to sulfur dioxide mas made. A comparable device was invented by Cherrier (71), who used ultraviolet a t 305 to 320 mp or a t 265 to 285 mp. A manual stack gas method for refinery use and designed to avoid nitrogen oxides and ammonia interference has been evolved by Seidman (37’1) from the procedure of Fritz and Freeland (136). Sulfur trioxide Tvas absorbed in 8070 isopropyl alcohol solution. This inhibited sulfur dioxide oxidation to negligible proportions under test conditions. Titration with barium chloride and Thorin indicator was employed. Initial oxidation with hydrogen peroxide may be carried out if the level of total sulfur oxides is desired. The test was investigated in the range 10 to 200 p.p.m. (by volume) of sulfur trioxide and 200 to 3000 p.p.m. of total oxides. Sulfides in the parts per billion range were estimated by Jacobs and coworkers (189). Collection v a s in a cadmium hydroxide solution nith estimation by methylene blue. A specific spot test sensitive to 2.5 y of sulfide ion with no interference by sulfur oxides has been reported (286). It xas based on reaction with a complex salt of mercuric ion and diphenyl carbazide. There has been a n invention for the determination of atmospheric sulfur dioxide by a color reaction m-ith vanadatesilica gel (310). Analysis for sulfate ion in microgram quantities has been attempted electrometrically (64) by reaction with lead nitrate and titration of the excess lead with chromate. TWO spectrophotometric methods measured excess chromate following reaction with barium chloride (111, 186). Flame photometry of excess barium or strontium after reaction mith sulfate has been attempted (52). A chromatographic spot test depending on darkening of paper by sulfuric acid had a detection limit of 5 y (137).
TKOpolarographic methods (106,106) and an x-ray absorption technique (109) for elemental sulfur in petroleum and fractions have been noted. Analysis for odoriferous sulfur compounds has been approached by gas chromatography (355, $94). Alercaptans have been identified with 2,4-dinitrobenzenesulfenyl chloride (37). Aliphatic mercaptans TTere separated and identified by chromatography of the 2,4-dinitrophenyl sulfides (61). Aliphatic thiols have been separated chromatographically and estimated coulometrically (936). A paper chromatographic method for thiols as colored azo products was reported (324). There were two colorimetric methods for thiols, one based on the reaction with N-ethylmaleimide (30) and another with p-aminodimethylaniline in the presence of ferric chloride (346). Infrared absorption bands for alkylthio groups were determined (266). Three chemical methods and a polarographic technique for disulfides in petroleum were tested on a number of pure compounds (180). Disulfides n ere determined without interference from sulfides by reduction n ith sodium borohydride (397). Odor Measurement. Selective fatigue in the classification of odors was among the aspects discussed by Duncan (107) Nevers (302) in a n early paper described the preparation of controlled odorous atmospheres for olfactory research In a paper on current techniques, Kader (296) described the syringe technique of Byrd (65) and other devices, including his own apparatus (295) 17-hichwas provided with odor-free, odorous, and calibrated odorous air supplies to reduce subjectiveness by establishing standards for comparative evaluation. The effect of humidity in decreasing perception was mentioned by Kerka and Kaiser (213). Prince and Ince (325) have approached measurement of the intensity of odor 11-ith a method providing for the dilution necessary to make odor just detectable in a mixture with odor-free air. Another dilution technique was noted (131). Rounds and Pearsall (352) proposed a procedure of direct assessment of odor FT-hich had been applied to different engines operating under various conditions and compared R ith chemical determination of various constituents. Chemical analysis was not in expected agreement with the odor assessment. Auto Exhaust. The research program of the United States auto industry, directed toward ultimate control of exhaust, has been the notable development in this aspect of air pollution during the period under review. There was a study of driving patterns over a representative Los Angeles route by Teague and others VOL. 31,
NO. 4, APRIL 1959
639
'(414). The percentage of time was determined statistically for such stages of motion as acceleration, deceleration, cruise, and idle. Then, in a related investigation by Way and Fagley (440), exhaust emission rates from a representative group of cars were assessed with analytical techniques worked up by Sturgis and others (402-4). These included engine airflow by the technique of Millar and Stahman (276) and infrared analysis for carbon monoxide, carbon dioxide, and hydrocarbons. The hydrocarbon detector cell of one instrument was sensitized with hexane t o indicate C8hydrocarbons and higher. In another instrument a mixture of benzene, ethylene, and acetylene was used for sensitization. A third assessment involved collection of exhaust samples in bottles, for oxides of nitrogen analysis according to the classical phenoldisulfonic acid technique. The results of the tests by these methods were totalized by the use of a n electronic multiplication and integration setup arranged by van Derveer and coworkers (428). An infrared interference filter photometer was developed under this program by Neerman and Rlillar (999). Investigation of catalysts for the combustion of exhaust gases was also undertaken and a report, on results of single cylinder engine tests of promising materials, has been rendered by Cannon and others (60). In relation to the study of engine exhaust a paper by Mader and coworkers (254) has clearly shown that the amounts and types of olefins in the fuel blend influence the composition of the exhaust and, specifically, the portion which takes part in photochemical processes leading to formation of eye irritants. Hydrocarbons. Chromatographic methods have been preponderant in this field. Hurn and others (183) have reported results of a project to develop a method for analyzing the hydrocarbon content of exhaust gas using gasliquid partition chromatography. Separation and identification of Cz to ( 2 6 hydrocarbons in the chromatograph mas accomplished. This included also Cg paraffins and Cs olefins and aromatics. Identification of C6 and higher nonaroniatics and Cs and heavier aromatics v-ere considered the most serious problem. James and Martin (191) separated and identified some volatile paraffinic, naphthenic, olefinic, and aromatic hydrocarbons. Eggertsen and Nelsen (113) hare dealt with Cz to Ca hydrocarbons in engine exhaust and city atmospheres. Other chromatographic procedures have covered C1 to Cq hydrocarbons (SQO), C5 to C7 saturates (112), Cs t o C? saturates on natural sorbents (18), separation of benzene, toluene, hexane and iso-octane (70), Csand Cg olefins (218), and aromatic hydrocarbons (416).
640
e
ANALYTICAL CHEMISTRY
Classical techniques for analysis of hydrocarbons were considered (146). Aromatic hydrocarbons have been determined by mass spectrometry (19). The differentiation of olefins and certain other classes, notably monocycloparaffins occurring in gasoline, has now been accomplished by Mikkelsen and others (%'I) who made benzenesulfenyl chloride react with the olefins to form a high boiling addition product making negligible contribution to the nonolefinic mass spectrum. A detector tube approach to estimation of benzene vapor was evolved in Japan with a limit of detection of 0.03 y of n-hexane by passage through chromic acid-soaked silica gel (219).
Polycyclic Aromatic Hydrocarbons. These compounds have been found in garages (82), vehicular exhaust, (261, 166), rural and urban air (77), smoke and tar from a curing kiln (481), oysters from polluted water (68), soot from human lungs (120), and other related sources. The range of compounds identified has increased but 3,4-benzpyrene remained the most frequently reported. Lyons and Johnston (261) listed 11 examples isolated from exhaust and atmospheric soot. The advantages of paper chromatography have been sought in separation of polynuclear hydrocarbons by Wieland and Kracht (452). The method was ascending chromatography on partly acetylated filter paper with methanolether-water (4 :4 :I). Ultraviolet fluorescence a t 254 mp was employed or ultraviolet absorption if the compounds were nonfluorescing. Fluorescein or acridine were used, as their fluorescence is quenched by light-absorbing materials. Ten compounds, Clz to C20, were separated. The method was used by Johne and coworkers (195) who, for quantitative work, cut out zones and extracted for subsequent spectrophotometry. Column chromatography has been refined by Cahnmann (67), who found that gradual addition of water to activated silica led to an optimum deactivation a t which better defined chromatographic zones were obtained in fractionation of polycyclic aromatic hydrocarbons. Lindsey and coworkers (138)standardized alumina with water vapor over sulfuric acid, a procedure based on the work of Wedgwood and Cooper (442). The procedure has also been used in the method of Wedgwood and Cooper (443) and by Commins (76, 7 7 ) . The latter has improved spectrophotometric identification of polynuclear aromatics by introducing additional wave lengths. Muel and others (290) separated 3,4,9,10-dibenapyrene from 3,4-benzpyrene and recorded the fluorescence spectrum. BuuHoi and Jacquignon (63) impregnated alumina with halogenated phthalic
anhydride to produce colors with polynuclear aromatics. Certain polynuclear aromatics have been detected a t the microgram level in dimethylformamide when treated with aqueous tetraethylammonium hydroxide according to Sawicki and coworkers (361). Such compounds have also been detected in the form of a diarylmethane dye (362). Thomas and others (416) separated synthetic mixtures by sublimation, but resinous substances interfered when atmospheric samples were used. I n France, the fluorescence of air samples a t 480 mp due to irradiation a t 386.5 mp was assessed as a measure of polycyclic aromatic hydrocarbon content (22). Urban samples were five times as fluorescent as rural. The synthesis of a number of polynuclear aromatics may be noted (102, 317). Infrared spectra have been examined for certain examples (18.9). Nitrogen Oxides. The method of analysis of Saltzman (367)is now n-idely used in America. Some modification of the continuous apparatus of Thomas and coworkers (417) based on the Saltzman reaction has been effected (7, $79). Jacobs and Hochheiser (190) have contributed a method for part per hundred million levels. Automatic collection of nitrogen dioxide in sodium hydroxide and in butyl alcohol was provided. Samples were analyzed by a variation of the Griess-Ilosvay method. Diazotization with sulfanilamide and coupling with N-(1-naphthyl)-ethylenediamine hydrochloride were carried out. The azo dye was determined spectrophotometrically a t 550 mp. Absorbed sulfur dioxide mas oxidized t o sulfate by hydrogen peroxide and did not interfere, Chromatography was tried for the separation of nitric oxide (407) and for the determination of nitrogen dioxide (166) as nitric oxide by conversion on a Molecular Sieve column. Smith and coWorkers (386) have provided for separation and determination of mixtures of nitrogen, nitrous oxide, nitric oxide, and carbon monoxide or nitrogen, nitric oxide, carbon monoxide, and carbon dioxide. TWOsilica gel layers separated by iodine pentoxide were employed. Silica gel impregnated with m-phenylenediamine was the basis of a micromethod for nitric oxide and nitrogen dioxide (321). A continuous method for nitric oxide in coke gas was founded on oxidation of this gas to nitrogen dioxide by ozone and absorption in m-phenylenediamine (38). Automatic photometry of extinction was provided. A Japanese contribution covered the reaction of nitrous acid and ammonium sulfamate in acetic acid solution to produce gaseous nitrogen which was determined in a nitrometer (469).
The occurrence of nitrogen oxides in the upper atmosphere was discussed by Miller (278) and in urban atmospheres by Rogers (343). A paper on the catalytic decomposition of nitric oxide has appeared (338). Ozone and Peroxides. A fundamental study on the kinetics of formation of atmospheric oxidants by Saltzman (358) emphasized the unsatisfactory state of knowledge regarding the stoichiochemistrg of the iodometric method for ozone. Apart from this work, Renzetti and Romanovsky (3%) had pointed out the high results given by the potassium iodide method a t peak smog times and the lorn results a t other times, comparison being made with the ultraviolet technique. Other investigators have reported on work with iodide method (72,419). A comprehensive examination of the problem has been reported by Byers and Saltzman (64). It was found that 1% potassium iodide in neutral buffered or alkaline solutions was more stable and useful than 20yo potassium iodide for collection and analysis. A correction for the difference in stoichiochemistry had to be applied to results by alkaline 1% solutions over the range 0.01 to 30 p.p.m. (v./v.) ozone to provide conformity with the 1% neutral buffered solution. Haagen-Smit and Brunelle (160) have recently re-examined the phenolphthalein reaction which was the basis of a n oxidant method developed by Haagen-Smit. It was emphasized that results conformed to subjective observations of smog irritation, though results were higher than those for neutral buffered potassium iodide and rubber cracking tests. Possible reasons for differences rvere discussed. Another version of the iodometric procedure was given by Wadelin (431). Ozone mas absorbed in a potassium iodide solution having a measured excess of sodium thiosulfate according to the method of Ehmert (115). Instead of back-titration with iodine, M7adelin titrated with potassium iodate to an amperometric end point, using calomel and platinum electrodes, and a sensitive galvanometer. The range of the method was given as 2 to 10,000 p.p.h.m. (v.!~.), but comparative results rvith other methods were not reported. A polarographic method for peroxides and hydroperoxides was developed by Willits and others (456) in 1952, Ricciuti and coworkers (397) carried out a statistical comparison of three methods for organic peroxides and showed that only the polarographic method distinguished between peroxides and hydroperoxides. Skoog and Lauwzecha (38%’) have examined alkyhydroperoxides by polarography and found half-wave potentials too close for
identification purposes. Whisman and Eccleston (447) have recently modified the polarographic procedure to increase the rapidity of measurement of hydroperoxides in gasoline. Analysis of peroxy compounds including peroxy diacid groupings has been dealt with (86) Carbon Monoxide. A review of carbon monoxide methods to 1955 has been prepared by Beatty (27). I n a comparison of colorimetric carbon monoxide detectors underground, Greig (157) found nitrogen oxides to be the only interfering gases. Around 30 pap.m. affected the yellow silico molybdate complex. Iodine pentoxide and palladium sulfate were less sensitive. Fowler (150) described a standardized procedure for tests on carbon monoxide in passenger cars. Infrared spectroscopy has been used for carbon monoxide determination in blood (140, %’89), comparing favorably with conventional methods. Infrared analysis data have been published by Scheddel (365). Preparation of standard carbon monoxide mixtures for infrared standardization was described (288). Hopcalite catalyst was used in a procedure for determining carbon monoxide in volumes of 0.02 t o 500 ml. (237). Carbon dioxide released in reaction between diiodopentoxide and carbon monoxide mas used for conductometric estimation (433). This reaction was the basis for a polarographic procedure in which the iodine released was oxidized by ozone to iodate (2%) and for a procedure in which it is measured spectrophotometrically to = t 2 p.p.m. (v./v.) in a potassium iodide solution (300). Displacement of the absorption bands of oxyhemoglobin has been found proportional to the carbon monoxide in blood and from this observation a direct reading apparatus was designed for a sample of 0.001 ml. (147). A Russian paper described determination of carbon monoxide using indicator tubes containing palladium sulfate, ammonium sulfate, and ammonium molybdate (280). Phenols. Interest in phenols as air pollutants has followed their observation in smoke from wastes. There were a series of papers by Commins and Lindsey (78-81) on determination of phenols in snioke by chromatography and spectrophotometry of the methyl ethers. Braverman and others (43) estimated part per billion levels in air colorimetrically using paminodimethylaniline sulfate. Phenols in tar acid mixtures have been estimated chromatographically (460). Phenol and o-cresol have been determined by paper chromatography (181). The phenolic group was detected with diazotised p-nitroaniline. Phenols R ere estimated using 4-aminophenazone f
(103).
Aldehydes and Ketones. There has been a review by Farr (123) on colorimetric determination of aldehydes and ketones. Formaldehyde in air was estimated colorimetrically using silica gel impregnated with phenylhydrazine hydrochloride and an oxidizing agent (124). Spectrophotometric estimation of traces was handled by interaction of formaldehyde and chromotropic acid in sulfuric acid (446). Sodium bisulfite was used for the fixation of atmospheric carbonyl compounds, notably formaldehyde (467), after 1-1hich iodometric titration Tvas carried out. Other aldehydes and ketones have been similarly estimated (182, 457). Microscopic and diffraction identification of 2,4-dinitrophenylhydrazones has been outlined (279). These derivatives have been titrated n ith tetrabutylammoniuni hydroxide (375),separated by paper chromatography (116, 426) and by column chromatography (249, 319). There was a spectrophotometric study of the derivatives (198). Aliphatic aldehydes were separated by paper chromatography of the hydroxamic acid compounds (187). Mass spectra of a large number of ketones (376) and acetal-type compounds Ivith formaldehyde, acetaldehyde, and propionaldehyde (135) have been published. BIBLIOGRAPHY
(1) Abraham, B. M., Flotlow, H. E.,
Carlson, R. D., ANAL. CHEM.29, 1058 (1957). (2) Adams, D. F., J . Air Pollution Control Assoc. 7, 88 (1957). (3) Adams, D. F., Koppe, R. K., T a p p i 41, 366 (1958). (4) Adams, D. F., Koppe, R. K., Mayhew, D. J., AXAL. CHEM.29, 1108 (1957). (5) Adley, F. E., Am. Znd. Hyg. Assoc. J . 19,75 (1958). (6) Adley, F. E., Gill, W. E., Ibid., 19, 271 (1958). (7) Adley, F. E., Skillern, C. P., Ibid., 19,233 (1958). ( 8 ) Agar, A. W., Brit. J . Appl. Phys. 9, 419 (1958). (9) “Air Pollution,” ed. by M. W. Thring, Butterw-orthP, London, 1957. (10) Allander, C. G., Staub 18, 15 (1958). (11) Allander, C. G., Matts, S., Zbid., 12, 738 (1957). (12) Amdur; M. O.,Am. Znd. Hyg. Assoc. Quart. 18, 149 (1957). (13) Amdur. M. 0.. Silverman. L.. Arch. ‘ Ind. Hyg: Occupatzonal Med. 10, 152 (1954). (14) Am. Soc. Testing Materials, Philadelphia, Pa., Rept. of Committee D-22 on Atmospheric Sampling and Analysis, 6lst Annual Meeting, June 1958. (15) ANAL.CHERT. 29, 30, Part 11, KO.4, (1957, 1958). (16) Ibzd., 30, 1745-62 (1958). (17) Andreeva, 0. S., Kovalev, E. E., Gigiena i Sanit. 5 , 27 (1957). (18) Andronikashvili, T. G., Kuz’mina, L. P., Zavodskaya Lab. 22, 1403 (1956). (19) Araki, S., Nozawa, G., J . Chem. Soc. Japan, I d . Chem. Sect. 59, 675 (1956). VOL. 31, NO. 4, APRIL 1959
641
(20) Aranovich, B. S., Report of Symposium, Iskusstvennoe Volokno 10 M 86 (1955); Zhur. Khim. 65,288 $,l956). (21) Avy, P., “Le9 Aerosols, Dunod, Paris, 1956. (22) Bftlgairies, E., Claeys, C., Rev. mdd. minzere 10,20 (1957). (23) Ballczo, H., Weisz, H., Mikrochim. Acta 5, 751 (1957). (24) Barnard, -4.J., Jr., Broad, W. C., Flaschka, H., Chemist Analyst 45, 86 (1956). (25) Batel, W., Chem.-Ing.-Tech. 28, 81 (1956). (26) Beadle, D. G., Kerrich, J. E., J . Chem. Met. Minina Soc. S. Africa 56. 219 (1955). (27) Beatty, R. L., U . S.Bur. Mines, Bull. 557 (1955). (28) Beirne, T., Hutcheon, J. M., J . Sci Instr. 34,196 (1957). (29) Bellack, E., Schouboe, P. J., ANAL. CHEX30,2032 (1958). (30) Benesch, R., Benesch, R. E., Gutcho, M., Laufer, L., Science 123, 981 (1956). (31) Benton, D. P., Elton, G. A. H.,
Peace, E. h.,Picknett, R. G., Intern. J . Air Pollution 1,44 (1958). (32) Berghout, C. F., Am. Ind. Hyg. Assoc. Quart. 18,242 (1957). (33) Berkhout, H. W,,Chemist Analyst
45,24 (1956). (34) Berkhout, H. W., Jongen, G. H., Ibid., 43,60 (1954). (35) Birks, L. S., Brooks, E. J., Rev. Sci. Instr. 28, 709 (1957). (36) BleshinskiI, S. V., Abramova, V. F., Zzuest. Akad. Nauk, S.S.S.R. 37, (1955); Zhur. Khim. 16,362 (1956). (37) Bohme, H., Stachel, H., 2. anal. Chem. 154,27 (1957). (38) Borok, 31. T., Zavodskaya Lab. 23, 1420 (1957). (39) Biuche;, R. 31. G., Gdnie chim. 77, 163 (1957). (40) Ibid., 78, 14 (1957). (41) Boucher, R. M. G., Mines 6, 497 (1956). (42) Bradshaw, R. L., Setter, L. R., Publ. Health Rents. (U.S.)73, 431 ’
(58) .Cahnman, H. F., Karatsune, ill., (95) Dennis, R., Samples, W. R., Anderson, D. M., Silverman, L., Ind. Eng. Ibzd.. 29. 1312 (1957). Chem. 49, 294 (1957). (59) Campbell, I: R., Cass, J. S., Cholak, (96) Densham, A. B., Marsh, J. D. F., J., Kehoe, R. A., Arch. Ind. Health 15, Newling, W, B. S., Brit. Patent 769,997 359 (1957). (hlay 13, 1954). (60) Cannon, W. A., Hill, E. F., Welling, (97) Dettling, J., 2. Praventivmed. 2, 140 C. E., “Single Cylinder Engine Tests (1957). of Oxidation Catalysts,” Paper 174, (98) Diaper, D. G. M., Kuksis, A., Can. J . ‘‘Motor Vehicle Industry Efforts to Chem. 35, 1278 (1957). Reduce Air Pollution from Exhaust,” (99) Dimmick, R. L., Hatch, M. T., Automobile Mfr. ASSOC., Detroit, Mich., 195’7. Ng, J., Arch. Ind. Health 18, 23 (1958). (100) Dowling, T., Davis, R. B., Charsha, (6i)Carson, J. F., Wong, F. F., J . Org. R. C., Linch, A. L., Am. Ind. Hyg. Chem. 22, 1725 (1957). Assoc. J . 19,330 (1958). (62) Cartmright, J., Brit. J . Appl. Physics (101) Doyle, G. J., Renzetti, N. A., 9,306 (1958). J . Air Pollution Control Assoe. 8, 23 (63) Cartmight, J., “Preparation and (1958). Assessmyt of Size Graded Mineral (102) Doyle, W. C., Jr., Daub, G. H., Samples, Research Rept. 128, Safety J . Am. Chem. SOC.80,5252 (1958). in Mines Research Establ., Sheffield, (103) Drabek, R., Chem. Tech. Berlin England, 1956. 9, 77 (1957). (64) Cassidy, N. G., Analyst 81, 169 (104) Drever, R. W. P., Moljk, 8., (1956). Rev. Sci. Instr. 27, 650 (1956). (65) Causley, D., Young, J. Z., Nature (105) Drushel, H. V., Miller, J. F., Anal. 176, 453 (1955). Chim. Acta 15,389 (1956). (66) Celechovsky, J., Holer, J., Chem. (106) Drushel, H. V., Miller, J. F., listy 51, 2129 (1957). Hubis, W.,Clark, R. O., Ibid., 15, 394 (67) Cember, H., Arch. Ind. Health 17, (1956). 527 (1958). (107) Duncan, D. R., Paint Technol. 20, (68) Cember, H., Watson, J. A., Grucci, 243 (1956). T. B., Ibid., 15, 449 (1957). (108) Earhart, R. E., Am. Ind. Hyg. (69) Chalhub, H. L., Brenner, R. R., Assoc. J . 19, 63 (1958). Industria y qufm. (Buenos Aires) 16, (109) Eccleston, B. H., Whisman, M. L., 462 (1954). ANAL.CHEM.28,545 (1956). (70) Chemodanova, L. S., Turkel’taub, (110) Edgerton J. H., Davis, H. G., N. M., Zavodskaua Lab. 22, 1406 Henley, L. Kelley, M. T., Ibid., (1956). 28,557 (1956). (71) Cherrier, C. M., Brit. Patent 771,531 (111) Egami, F., Takahashi, N., Bull. (March 20, 1952); U. S. Patent 2,736,Chem. Soc. Japan 30,442 (1957). 813 (Feb. 28,1956). (112) Eggertsen, F. T., Groennings, S., (72) Cholak, J., Schafer, L. J., Yeager, ANAL.CHEM.30,20 (1958). D., Younker, W. J., Arch. Ind. Health (113) Eggertsen, F. T., Nelsen, F. M., 15; 198 (1957). Ibid., 30, 1040 (1958). (73) Cholak, J., Schafer, L. J., Younker, (114) Egner, H., Brodin, G., Johansson, R. J., Yeager, D. W., A m. Znd. Hyg. 0.. Kol. Lantbruks-Hoaskol. Ann. 22. Assoc. J . 19, 371 - . - (19.58) 369 (1855). (74) Christmas , R. P., Hosey, A. D., (115) Ehmert, A,, J . Atmospheric Terrest. Ibid., 18, 119 (1957). Phys. 2,189 (1952). ( 7 5 ) Cogbill, E;, C., Yoe, J. H., ANIL. (116) Ellis, R., Gaddis, A. M., Currie, CHEM.29, 1251 (1’957). G. T., ANAL.CHEW30,475J1958). (76) Commins. B. T.. Analust 83. 386 (117) Emanuelsson, A., Eriksson, E., ‘ (1958). ’ Egner, H., Tellus 3,262 (1954). (i?)Cbmmins, B. T., Intern. J . Air (118) Ettinger, I., Braverman, M. M., Pollution 1, 14 (1958). Jacobs, M. B., J . Air Pollution Control (78) Commins, B. T., Lindsey, A. J., Assoc. 8, 120 (1958). Anal. Chim. Acta 15,446 (1956). (119) Evans, E. C., Am. Ind. Hyg. Assoc. (79) Ibid., p. 551. Quart. 18,253 (1957). (80) Ibid.. D. 554. (120) Falk, H. L., Kotin, P., Markul, I., ($1) Ibid.; 557. Cancer 2,482 (1958). (82) Commins, B. T., Waller, R. E., (121) Farabee, L. B., drch. Ind. Health Lawther, P. J., Brit. J . Ind. M e d . 14, 17,200 (1958). 232 (1957). (122) Farlow, N. H., French, F. L4., (83) Courtier, G. B., Nature 180, 382 J . Colloid Sci. 11, 177 (1956). (1957). ’ (123) Farr, J. P. G., I d . Chemist 32, (84) Crossman, G. C., Am. Znd. Hyg. 389 (1956). Assoc. Quart. 18, 341 (1957). (124) Fedotov, V. P., Gigiena i Sanit. 9, (85) Csanyi, L. J., Solymosi, F., Acta 87 (1956). Chim. Acad. Sci. Hung. 13,9 (1957). (125) Finkl’shtein, D. N., Kryuchkova, (86) Damon, J. M. O., Bfellon, M. G., G. N., Zhur. Anal. Khim. 12, 196, ANAL.CHEM.30,1849 (1958). (1957). (87) D’Amore, G‘., Faraone,’ G., Ann. (126) Fitzgerald, J. J., Arch. I d . Health chim. Rome 47,142 (1957). 15, 68 (1957). 188) L.. Rev. .nratiaue , . ~Dautrebande. , - du (127) Fitzgerald, J. J., Detwiller, C. G., jroid 136,45 (1957). ’ Am. Ind. Hyg. Assoc. Quart. 18, 47 (89) Ibid., 137, 36 (1957). (1957). 190), Dautrebande. L.. “Studies on hero(128) Fitzgerald, J. J., Detwiler, C. G., sols,” Off. Tech. Sirvices, Dept. ComArch. Ind. Health 15, 3 (1957). merce, Washington, D. C., 1959. (1291 Foran. >I. R., Gibbons, E. V., (91) Dautrebande. L.. Beckmann. H.. * Wellington, J. R., dhem. in Can. 10, 33 lqalkenhorst, I$., Arch. Znd. Health (1958). 16, 179 (1957). (130) Foder, D. G., “Development of a (921 Dautrebande. L.. Beckmann. H., Test Procedure for Measurement of ‘ l$alkenhorst, W., Arch. intern. phrm: Carbon Monoxide in AEtomobile Pasacodynamie 116, 170 (1958). senger Compartments, Paper 175, (93) Davies, C. N., “Dust is Dangerous,” “Motor Vehicle Industry Efforts t o Faber & Faber, London, 1954. Reduce Air Pollution from Exhaust,” (94) Dawes, J. G., Greenough, G. K., Automobile Mfrs. Assoc., Detroit, Mich., Seager, J. S., Brit. J . Appl. Phys. 8, 236 1957. (1958).
b,,
\----,-
i.
I
\ -
\ -
642
ANALYTICAL CHEMISTRY
(131) Fox, E. X., Gex, 5’. E., J . A i r Pollution Control Assoc. 7, 60 (1957). (132) Fremlin. J. H.. Hardwick, J. L., Suthers, J., h’ature 180, 1179 (1957). (133) Frenkiel, F. X., Sci. Proc. Intern. Assoc. Meteorology, Rome, September 1954, Buttern-orths Publications, London, 1956. (134) Frenkiel, F. N.,Smithsonian Inst. Publs. Repfs., No. 269 (1957). (135) Friedel, R. A , Sharkey, A. G., Jr., ANAL. CHEU. 28, 940 (1956). (136) Fritz, .J. S., Freeland, XI. Q., Zbid., 26, la93 (1954). (137) Frugoni, J. A. C., J . Chronzatography 1, 00 (1958). (138) ?chs, 1.*I., “Rlechanica .herosolei, Xcad. Sei. U.S.S.R., Rloscon-, 1955: 11391 Fuson. X.. Josien. AI. L..’ J . Am. Chem. Soc 78,’3049 (1956). (140) Gaensler, E. A , Cadigan, J. B., Ellicott, M.F., Jones, R. H., Marks, A4., J . Lab. Clin. M e d . 49,945 (1957). (141) Gale, H . J., Peaple, L. H. J., Intern. J . A i r Polliition 1, 103 (1958). (142) Gallily, I., J . Colloid Sci. 12, 161 (1957). (143) Gartrell, F. E., Carpenter, S. B., J . Meteorol. 12, 215 (1955). (144) Geisheker, B. J., Public Works 88, 151 (1957). (145) Georgii, H. W.,Staub 47, 628 (1956 ). (146) Getoff, X., Sattler-Dornbacher, E., Prakt. Chem. 7, 159 (1956). (147) Giacomo, P., Guillot, M., Jacquinot, P., Conipt. rend. 243,985 (1956). (148) Gill, H. H., Rolf, R. F., Brmstrong, G. IT’., ANAL.CHEM.30,1788 (1958). (149) Gold, R., IL’ucleonics 15, 114 (1957). (150) Gordieyeff, V. A., drch. Znd. Health 15. 510 (lS53. (151j Gordon, E. S., illaxwell, D. C., Jr., Alexander, S. E., Electronics 29, 188 flWi6) . (152) Goryushina, V. G., Zanodskaya Lab. 23, 1300 (1957). (153) Gotte., H.., Mikrochim. Acta 1-3. 27 (1956). (154) Gottfried, J., Chem. prQmysl. 6, 143 (1956). (155) Green, H. L., Lane, W. R., “Particulate Clouds, Dusts, Smokes and Mists,” E. and F. X. Spon, London, 1957. (156) Greene, S. A,, Pust, H., ASAL. CHELI.30,1039 (1958). (157) Greig, J. D., J . X i n e Vent. Soc. S . Africa 10, 77 (1957). (158) Gruber, C. W., Jutze, G. A,, J . A i r Pollution Control Assoc. 7, 115 (1957). (159) Gucker, F. T., O’Konski, C. T., J . Colloid Sci. 4. 541 11949’1. (160) Haagen-Sm(t, -4. J., Brunelle, &I.F., Intern. J . A i r Pollution 1, 51 (1958). (161) Hale, D. K., Analyst 8 3 , 3 (1958). (162) Hall, R. J.. Ibid.. 82, 663 (1957). (163) Harasan-a,’ S., Sakamoto, T., J . ~
0
\--I-
Chem. SOC. Japan, Pure Chem. Sect.
77, 168 (1956).
(164) Harris, W, B., LeVine, H. D., Watnick, S. I., ilrch. 2nd. Health 16,
493 (1957’1. (165) Harris, W. E., ANAL. CHEM.30, 1000 (19%). (166) Hasenclever, D., Staub 44, 159 (1956). (167) Haul, R. 4. IT., Angew. Chem. 68, 238 (1986). (168) Hawksley, P. G. FI7.,Badzioch, S., Blackett, J. H., J . Inst. Fuel 31, 147 (1958). (169) Healy, J. W., Am. 2nd. Hyg. Assoc. Quart. 18, 261 (1957). (170) Heiman, W.J., J . Colloid Sei. 13. ‘ 329 (1958). ‘ (171) Helwig, H. L., Gordon, C. L., ASAL.CHEM.30, 1810 (1958).
(172) Hendrickson, E. R., J . S a n k Eng. Diu., Proc. Am. SOC.Civil Engrs. 84, 1776 (1958). (173) Heyrovsky, J., Collection Czechoslov. Chem. Communs. 21, Suppl. 1(1956). (174) Hill, U. T., AXAL. CHEJI. 30, 521 (1958): (175jHi11, 117. H., Xferrill, H. J. M., Palm, B. J., Arch. 2nd. Health 15. 152 (1957). (176) Hoover, R. L., Proc. Health Phys. Soc. 1,49 (1956). (177) Horrocks. D. L.. Studier. bl. H.. ‘ A s A L . CHEM.’30, 174i (1958). ’ (178) Hoy, J. E., Croley, J . J., Jr., Am. 2nd. Hyg. Assoc. Quait. 18, 312 (1957). (179) Hrubecky, H. F., J . A p p l . Phys. 29, 573 (19%). (180) Hubbard, R. L., Haines, IT. E., Bell, J. S., ASAL. CHEU.30, 91 (1958). (181) Hudecek, S Beranova, D., Chem. listy 50, 1456 (1956). (182) Hunter, I. R., Potter, E. F., ANAL. CHEJL30,293 (1958). (183) Hurn, R. W., Hughes, K.J., Chase, J. O., “Application of Gas Chromatography t o Analysis of Exhaust Gas,” Paper 1IC, “Motor Vehicle Industry Efforts to Reduce Air Pollution from Exhaust,” Automobile Mfrs. Assoc., Detroit, Mich., 1958. (184) Intern. J . A i r Pollution, Pergamon Press, London. (185) Iv-anoff, T., Chem. Tech. Berlin 10.35 11958). (186j I&aki,‘I., Utsumi, S., Hagino, IC, Tarutani, T., Ozan-a, T., Bull. Chem. SOC.J a p a n 30,847 (1957). (187) Izumi, G., Yamadda, Y.. J. Chem. ‘ Soc. Japan, 2nd. Chem. ‘Sect. 60, 1525 f 1957). (188) Jacobi, W.,Strahlentherapie 94, 472 (1954). (189) Jacobs, M.B., Braverman, M. AI., Hochheiser, S.,- 4 s . h ~ . CHm. 29, 1349 (1957). (190) Jacobs, AT. B., Hochheiser, S., Ibid., 30,426 (1958). (191) James. A. T.. hlartin. A. J. P.. . J.’Appl. Chern. (Lbndon) 6,’105 (1956’1: (192) Jarman, R. T., Brit. J . -4ppl. Phys. 9, 153 (1958). (193) Jecklin, I,., Arch. Gewerbepathol. Gewerbehyg. 14, 626 (1956). (194) Jenkins, E. N., Sneddon, G. K., “Monitoring of Effluent for Alpha Emitters. 111. Ra,” Atomic Energy Research Establ. (Gr. Brit.), Rept. C/R 2385,1958. (195 ) Johne, K., Kleiss, I., Reuter, X., Angew. Chem. 69, 675 (1957). (196) Johnson, I
