(C, b us. C, c), while that of the formaldehyde concentration is negligible (C, a us. C, c), indicating that the associative capacity of latex for formaldehyde is larger than that of a potassium chloride solution.
nique has been developed for the analysis of mixtures of aldehydes to ascertain what aldehydes are present in natural polluted atmospheres, and under what conditions, with respect to combustion, aldehydes are produced.
Conclusion
The test at its present stage of development indicates qualitatively and to some extent quantitatively the irritation intensity of certain aerosols. I t has been used in synthetic aerosols as indicator for the degree of association of the irritant gas (HCHO) with airborne particulate matter, by comparative tests, prior to and after passage through the aerosol spectrometer. The findings support the assumption that a fraction of the irritant gas molecules associates with the particle surface, and that this association produces an intensifying (synergistic) effect, which increases with aerosol concentration. The synergistic effect parallels the pattern of Amdur’s tests with guinea pigs, and apparently also those of LaBelle with regard to paraffin oil aerosols in analogy with latex dispersions ( 6 ) . literature Cited (1) Amdur, M. O., IXD. ENG.CHEM.51, 775 (1959). (2) Goetz, A,, J , Air Pollution Control Assoc. 6,72-76 (1956). ( 3 ) Goetz, A., Stevenson, H. J. R., APCA Proc. Semi-Annual Tech. Conf., San Francisco, pp. 268-72, 1957. (4) Goetz, A,, Tsuneishi, N., Clean Air Quart. 2,7-IO (June 1958). (5) J . A m . Water Works Assoc. 45, 1196-210 (1953). (6) LaBelle, Ch. W., Long, J. E., Cristofano, E. E., A M A Arch. I d . Health 11, 297-304 (1955). ( 7 ) Orr, C., Hurd, K. F., Hendrix, W. P., Junge, Chr., J . Meteorol. 15, 240-2 (1958).
RECEIVED for review September 18, 1958 ACCEPTED April 21, 1959 Part of a research program, supported by
~
The complete manuscript (condensed here) has been accepted for publication in A.M.A. Archives of Industrial Health.
Minute quantities of aldehyde react rapidly with methone (5,5-dimethyl-l,3cyclohexanedione) to form crystalline bismethone derivatives (7, 2, 6, 7), which can in turn be dehydrated to crystalline xanthene derivatives. A suitable method for separating a mixture of derivatives to individual components involves the use of a fractional sublimation technique ( 4 ) , as both the bismethone and xanthene derivatives have a wide range of sublimation temperatures, different from each other. The various derivatives can be identified by melting points, infrared spectroscopy, as well as by visually observing the various crystalline forms directly in the sublimation tube using a dissecting microscope (x45). Ultraviolet spectroscopy may be used to differentiate the bismethone derivatives from the xanthene derivatives; the
Table 11.
Combustion
Run 1 2 3 4 5 6
774
19 1-92 172 -73 141-42 176.5-77 157-58 142 -43 134-35 135 -35.5 153-55 155 -56 107-09 154-55 101-03 194-95 204 -06
...
... ...
c
190-92 70-801 185-90 147-49
... 164-65
... ... ... ... ...
... ...
5 Readily converted t o xanthene derivatives. b Limited solubility in m-ater limits yield of bismethone derivative. Apparent decomposition of derivative above 130’ C. d Does not form bismethone derivative
v01. of Air, Cu. Feet Primary Secondary 7.8 7.8 7.8 7.8
Total Aldehyde Production hlg. P.P.hI.n
7.8
Incomplete
Complete
15.6 19.5
13.2
15.6 11.7 7.8 4.7
9.7 4.7 16.4 24.5
15.7 10.0 51.0 120.0
1 2 3 4 5 6
Prouane 110 rrramsib 7.8 7.8 7.8 11.7 7.8 19.5 14.4 9.6 5.8
1 2 3 4
I-Butene (1 1 7.8 7.8 7.8 7.8
5
~-
0.20 0.56 3.07 1.47 2.12 15.3
...
...
grams) 7.8 11.7 15.6 17.6 9.6 5.8
a VoIume of formaldehyde per total stack effiuent volume. burned per 0.5-hour run.
INDUSTRIAL AND ENGINEERING CHEMISTRY
7.8
... ...
...
1.7 4.1 8.5 12.4
8
~
Complete
1.03 3.14
11.7
... ... ... ...
6
in polluted atmospheres are conventionally determined on a composite basis. An applicable tech-
Aldehyde Formaldehyde Acetaldehydea PropionaldehydeQ Butyraldehydea Isobutyraldehydea Valeraldehyde Isovaleraldehyde Hexanaldehydeb Benzaldehyden Crotonaldehyde Acrolein Aldol Glyoxal Furfural Pyruvic aldehyded Phenylacetaldehyde
Methane (14 grams)* Complete
Incomplete ALDEHYDES
Melting Point, C. Bismethone deriva- Xanthene tive derivative
Effect of Secondary Air on Aldehyde Production
7
Sanitary Engineering Research Laboratory, University of California, Berkeley, Calif.
Melting Points of Aldehyde Derivatives
Production increases during complete combustion and decreases during incomplete combustion
Incomplete
Jerome F. T h o m a s , Eldon N. Sanborn, Mitsugi Mukai, a n d Bernard D. Tebbens
Table I.
The aldehydes are all relatively simple
the U. S. Public Health Service, concerning the basic role of aerosols in air pollution.
Aldehyde Production Related to Combustion and Pol I uted Atmospheres
formaldehyde xanthene spectrum is uniquely characteristic. The proposed standardized method for forming the bismethone derivatives from an aqueous phase was applied to 16 simple aldehydes. As indicated in Table I, only six xanthene derivatives could be prepared and, of these, the formaldehyde xanthene derivative only with difficulty. The analytical technique was applied
0.19 1.25 4.45 7.22 8.75 19.2
*
0.3 0.8 3.0 2.6 5.8 67.5
0.3
1.7 5.0 7.5 23.7 85.3
Approximate weight of fuel
A I R POLLUTION to representative atmospheric samples. The presence of a single crystalline form in the sublimation tube, together with melting point and infrared spectroscopy, indicated the presence of only a single aldehyde-formaldehyde. The results were consistent with both bismethone and xanthene derivatives. Formaldehyde cannot be considered the exclusive aldehyde present: The preponderance of formaldehyde may interfere with the detection of other aldehydes; other aldehydes may be present in quantities too small to be detected by this method (sensitivity, 1 5 y of xanthene derivative per 3 ml. of solvent, with ultraviolet spectra) ; or aldehydes are present that cannot be detected by the proposed method. T o determine under what conditions aldehydes are produced, the analytical technique was applied to the combustion effluent of fuels burned under conditions of complete and incomplete combustion. Samples were obtained by specifications slightly modified from those of previous work (3, 5). All atmospheric and combustion samples were in an aqueous phase, obtained by condensation of the gaseous combustion effluent or steam stripping of the particulate component. Formaldehyde was again the only detectable aldehyde and was produced under all but stoichiometric conditions. Even under conditions of apparently complete combustion large quantities of formaldehyde may be produced, proportional within limits to the flow of secondary air. This increase in production is probably due to a cooling action. During incomplete combustion, formaldehyde is always produced in relatively large quantities, but as the flow of secondary air increases, the flame and effluent characteristics begin to approach that of complete combustion, with the aldehyde production being inversely proportional to the flow of secondary air. Beyond a certain point with respect to secondary air flow the cooling effect again becomes dominant, causing an increase in aldehyde production. Because of inherent limitations during combustion, this latter point can be only quantitatively exemplified by using methane as the fuel. Quantitative measurements of the effect of secondary air on aldehyde production during combustion are given in Table 11. The inference from this study on possible atmospheric contamination by controlled combustion processes is selfevident. I n general practice large quantities of secondary air may be introduced to eliminate the smoke plume. A visible atmospheric contaminant may be replaced by an invisible contaminant unless close control over secondary air is maintained.
CONDENSERS
CHAMBER
Samples were handled in an aqueous phase in this burner and combustion system
(REAGENT GRADE) TANK SOURCE
I1 I~T~AIR
SUCTION PUMP
I*AIR TANK SOURCE
FREEZE-OUT TRAPS
EXHAUST
literature Cited (1) Horning, E. C., Horning, M. G., J . Org. Chem. 11, 95 (1946). (2) Klein, G., Linser, H., Mikrochem. PregE Festschr. 204 (1929). (3) Tebbens, B. D., Thomas, J. F., Sanborn, E. N., Mukai, M., Am. Znd. Hyg. Assoc. Quart. 18, 165 (1957). (4) , , Thomas. J. F.. Sanborn. E. N.. Mukai. M., Tebbkns, B,’ D., Anal.‘Chem. 30, 1954 (1958’1. (Sf Thomas, J. F., Tebbens, B. D., Mukai, M., Sanborn, E. N., Zbid., 29, 1835 (1 957). (6) Vorlander, D., Z. anal. Chem. 77, 32 (1929). (7) Yoe, J. E., Reid, L. C., IND. ENG. CHEM.,ANAL.ED. 13, 238 (1941). RECEIVED for review September 18, 1958 ACCEPTEDFebruary 17, 1959 Work supported by research grant RG.4281, National Institutes of Health, U. S.
Public Health Service. A cooperative effort within the University of California of the School of Public Health and the College of Engineering.
The Physiological Response of Guinea Pigs to Atmospheric Pollutants Mary 0. Amdur D e p a r t m e n t of Physiology, H a r v a r d School of Public Health, Boston, Mass.
The complete manuscript, condensed here, was published in the lnfernafional Journal of Air Pollution 1,
170-83 ( 1 959).
IF
THE RESULTS of toxicological studies are to be applied to air pollution, the gradient between the low concentrations occurring even during periods of prolonged meteorological inversion over heavily polluted urban areas and the
high concentrations necessary to produce lung damage and death in experimental animals must be overcome. Methods used in this investigation permit quantitative evaluation of the response of guinea pigs to irritant air pollutants at concentrations of the order of magnitude of those occurring during episodes of acute pollution and below those encountered routinely within industrial plants. T h e primary response to the irritants tested was bronchial constriction, which produced an increase in the resistance offered to flow of air in and out of the lungs. As evaluated by the increase in pulmonary flow resistance and in the work of breathing, the most potent irritant gas tested was formic acid, followed by formaldehyde, acetic acid, and sulfur dioxide in that order. A considerable amount of soluble gas is removed during passage through the upper respiratory tract. I n the case of sulfur dioxide, acetic acid, and formaldehyde the response was greater when the gas was breathed through a tracheal cannula, thus bypassing the protective scrubbing effect of the upper airway. T h e experimental study of mixtures of gases and aerosols has been the subject of much speculation in connection with the acute air pollution disasters. A synergistic toxic action with sulfur dioxide was observed with sulfuric acid mist of 0.8 but not 2.5 microns. The response to sulfur dioxide was increased by a sodium chloride aerosol of 0.04 but 2.5 microns; hence particle size is an important factor in the potentiation of the response to an irritant gas by an aerosol. When the four irritant gases were studied in combination with 10 mg. of sodium chloride per cu. meter, 0.04 micron in diameter, which was itself without effect, the response to sulfur dioxide and to formaldehyde increased but the response to acetic and formic acids remained unchanged. The aeroVOL. 51, NO. 6
*
JUNE 1959
775
