AIR POLLUTION CONTROL
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by Frank Y. Speight, ASTM, Philadelphia, Pa., and F. S. Mallette, Resources Research Inc., New York, Ν. Υ.
Standardization Aspects of Air Pollution Control Ordinances and laws for air pollution control are a form of standard, but there is great need for standardized terminology, sampling and analysis procedures
AsLS early as the 17th century, air pollu tion was recognized as a problem. Coal smoke, then the major contaminant, is now largely under control; however, with increasing industrialization, many new pollutants such as oxides of sulfur and nitrogen, ozone, hydrocarbons, and particulate matter in a variety of forms have appeared. Air pollution is caused not only by industrial activity, but also by such things as trash burning, automotive exhaust, or forest fires. It m a y cause unsavory odors, health injuries, and d a m a g e — estimated at a considerable figure— by deterioration, corrosion, soiling, and crop injury. In order to minimize such losses, standardized techniques and cri teria are increasingly necessary for gaging degree of air pollution, and m a x i m u m concentrations allowable. Nature of Standards T h e need for generally acceptable terminology and standard procedures for sampling and analysis of pollutants is most clearly seen at the local level where the problem of defining allowable limits for various pollutants is encountered. T h e Philadelphia ordinance (72), for ex ample, contains a section in which are defined such terms as dust, fume, gas, mist, odor, smoke, vapor, air pollution, and air pollution nuisance. These terms, also defined in other city and county control measures, show considerable lack of agreement. Also, allowable concentra tions for various pollutants are seldom specified quantitatively. This indicates strongly the need for quantitative and objective standards which can be used or cited both in local ordinances, and for uniform presentation of data in air pollution surveys. Industry is spending large sums of money for control of effluents dispersed into the atmosphere. Its motives in clude growing social responsibility, im provement of public relations, and vol untary or involuntary compliance with 1 Presented at Delaware Valley Regional Meeting, American Chemical Society, February 16, 1956.
local ordinances. Occasionally there is an added incentive—the recovery of salable and sometimes valuable by products. Performance standards for air-cleaning equipment are needed and an effort toward this end is going forward. Industrial Atmospheres While the problems of industrial atmos pheres—work areas where healthy workers are exposed for limited durations —are somewhat akin to those of outdoor air pollution, the differences are impor tant and should be clearly stated. T h e American Conference of Governmental Industrial Hygienists, over a n u m b e r of years, has developed a list of m a x i m u m allowable concentrations for a n u m b e r of workroom pollutants which represents the best current information available. This list has been published (6) and is used as a basis for safe operation in industry. These levels are not directly applicable for air pollution control and a formula by which they might be extrap olated for this purpose has not yet been developed. T h e general population in cludes the very young, the very old, and the infirm, so that from an injury-tohealth standpoint, entirely different criteria from those applied to industrial workers must be considered. This is a n involved a n d complex problem not within the scope of this article. T h e American Standards Association in its long-standing activity of fostering national safety standards has had for a number of years, a project on the establishment of m a x i m u m allowable concentrations for toxic dusts and gases in industrial atmospheres (4). Fifteen standards have been published, each of which establishes the concentration of its subject substance permissible in the atmosphere of working places from the viewpoint of occupational disease pre vention. Each standard sets forth physiical and chemical properties, summarizes test methods, and includes a compre hensive bibliography. As part of the work of the American Society of Mechanical Engineers' Com mittee on Air Pollution Controls, Barkley
(7) assembled information on accepted m a x i m u m permissible concentrations of air pollutants from the standpoints of health, damage to vegetation, and dam age to property. Included in the report of this work is a tabulation of maximum allowable concentrations of (industrial) atmospheric contaminants set forth by the American Conference of Govern mental Industrial Hygienists, and those included in several state regulations re garding industrial atmospheres. T h e Russians have established maxi m u m allowable concentrations for both industrial atmospheres and for air pollu tion control (74) and claim this as an other Russian first. Table I shows m a x i m u m allowable concentrations of various pollutants, some of which have been approved by the Bureau of Sanitary Inspection of the U S S R for atmospheric air (outdoors). As mentioned previously this is a step not yet taken in this country except for industrial atmospheres. Compared with the U . S. values (6), those of the Russians are very low. For example, the U . S. permissible limit for lead (8-hour daily exposure in industrial atmosphere) is 0.15 mg./cubic meter, while the Russian value is 0.0007 m g . / cubic meter (daily average), a figure over 200 times smaller. Partial explana tion of these values m a y be found in the original Russian publication (73).
National Organizations Concerned with Standards American Standards Association. T h e ASA serves as a clearing house for national standards. There are two ASA projects in this area, the objectives of which are indicated by the titles: Z37, Allow able Concentrations of Toxic Dusts and Gases mentioned previously (4) and Z74, Fundamentals of Performance of Effluent Air and Gas Cleaning Equipment. Project Z74, jointly sponsored by the American Society of Mechanical Engi neers and the American Society of Heating and Air-Conditioning Engineers is currently in process of organization and as yet no standards have been issued. American Petroleum Institute. VOL. 48, NO. 9
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SEPTEMBER 1956
69 A
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AIR POLLUTION CONTROL
T h e A P I Committee on Analytical R e search has a subcommittee on analytical methods for the atmosphere which is engaged in the development of new analytical methods for hydrocarbons and related substances. O n e current standardization project is the evaluation of a procedure for determining hydrocarbons in air, as developed by the Standard Oil Development Co. If the method is found reliable, it would presumably be adopted as standard for the petroleum industry work in air pollution. T h e API Committee on Disposal of Refinery Wastes has prepared a manual, volume 5 of which deals with the sampling and analysis of waste gases and particulate matter. This committee is also sponsoring a project on which it is collecting information on the design of dust-collecting devices, primarily cyclones. Air Pollution Control Association. T h e APCA Committee on Air Pollution Measurement is engaged in preparing a m a n u a l , Standard Methods for a Continuing Dustfall Survey (8). Other proposed standards of the APCA will be entitled : Recommended Standard Method for Fine Particulate Survey Recommended Standard Method for Gaseous Contaminants Recommended Standard Method for O d o r Survey Effect of Meteorology on an Air Pollution Survey American Society of Mechanical Engineers. T h e A S M E Committee on Air Pollution Controls, organized in 1949, includes in its scope: " T o collaborate in the formulation and publication of standards of appropriate n a t u r e . " Most of the efforts of this committee toward establishment of standards have been in cooperation with other groups such as the American Society of Heating and Air-Conditioning Engineers in ASA project Z74 mentioned previously, and by participation of various individuals in the work of American Society for Testing Materials Committee D-22 on Methods of Atmospheric Sampling and Analysis. O n the legislative aspect of standards, T h e American Society of Mechanical Engineers has m a d e a major contribution by its development of the "model smoke l a w , " more properly termed "Example Sections for a Smoke Regulation Ordin a n c e " (7). T h e model smoke law includes a section relating to standards of measurement. In 1940, the A S M E Model Smoke Law Committee was organized under the chairmanship of John F. Barkley of the U . S. Bureau of Mines. Its 18th and final meeting was held in 1948. Its " E x a m p l e Sections for a Smoke Regulation O r d i n a n c e " was adopted by A S M E 70 A
A Workbook Feature and has been used as the basis for most of the municipal smoke and fly-ash ordinances in the United States. T h e American Iron and Steel Institute. T h e AISI Air Pollution Committee, W. O . Everling, Chairman, has supported research into the development of inexpensive air-sampling and measuring instruments, in particular, for determining and recording air-borne dust. T h e instrument has also been adapted for detecting hydrogen sulfide. American Meteorological Society. This organization has a committee on air pollution abatement which has published "A Statement on the Present Possibilities of Applying Meteorology in Air-Pollution Abatement." If these activities do not include standardization, at least they will provide worth-while background information for other groups engaged in standardization in this area. American Society for Testing Materials. In 1951, Committee D-22 on Methods of Atmospheric Sampling and Analysis, under the chairmanship of L. C. M c C a b e , was established in A S T M . A long-standing policy of A S T M is to have represented all major interests in a particular field which have the competence to advance the work of a technical committee. T h a t this has been accomplished in the case of Committee D-22 is evident from the membership list (3). This committee serves as a meeting ground for national interests in establishing standards for atmospheric sampling and analysis. Only by having adequate representation can it be assured that the work of this committee will be accepted generally as authoritative and that it will carry the weight necessary for national acceptance and use. T h e first tentative recommended practices and methods of analysis developed by Committee D-22 were approved for publication by the society in 1955. During this time the committee was charting a new area and agreement was necessary on each step before proceeding to the next. A tentative ( A S T M Tentative Method of Test or Recommended Practice) may later become a standard and it must be considered for adoption as standard within two years after it is published as a tentative. T o illustrate the steps in development of a tentative, we will use as an example, T h e Tentative Method for Continuous Analysis and Automatic Recording of the Sulfur Dioxide Content of the Atmosphere ( A S T M Designation D135555T). T h e history of this method goes back to 1922. T h e chairman of the subcommittee which developed it was M . D . T h o m a s who, in 1922, was using the method of Marston and Wells (75) for determining low concentrations of sulfur dioxide in air. Prior to 1922, bubbler trains had been
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used to collect the gas, and the gravimetric method was often applied. Later, a program was initiated at American Smelting and Refining Co. which required m a n y gas analyses, and soon the shortcomings of the Marston-Wells method became painfully evident. O n e test could be m a d e in five minutes if the approximate gas concentration of the samples were known, but when 12 tests an hour were required, which was often the case, the operator was sorely fatigued from the manual labor required in shaking the 5-gallon bottles used in the test. In 1927, T h o m a s and his colleague, R. J. Cross, took steps to improve the method. I n a communication, Thomas wrote : " W e were amazed to find how readily sulfur dioxide was absorbed in an iodine solution using a very simple bubbler. We then built our first sampling unit which required a turntable on which to collect successive samples. We adapted an old circular-tub washing machine for this purpose, using many of the old gears. It had a noisy "wheelb a r r o w " movement but it turned out samples at 2-minute intervals, as rapidly as a chemist could titrate them. We had increased the sensitivity of the method from 0.1 to 0.01 p.p.m. and changed from intermittent to continuous sampling. T o replace the titration we used hydrogen peroxide in distilled water and measured the electrical conductivity of the acid produced. " I n M a y 1929, we had assembled an 'autometer' (so christened by Dr. George R. Hill) complete with a Leeds and X o r t h r u p conductivity recorder and installed it in an agricultural area adjacent to a smelter. This and replacement instruments have operated continuously at the same location to the present. Even the earliest records were quite satisfactory. In 1930, about 20 more analyzers were built, including a considerable number for the American and Canadian investigators who were starting the study of the Trail Smelter question. M a n y of these instruments are still in operation. In subsequent years, mechanical modifications were m a d e in the instrument, but the fundamental principle of its operation remained u n c h a n g e d . " These developments are fully documented (70) and as indicated, the T h o m a s autometer is the instrument around which was written the A S T M Tentative Method for Continuous Analysis and Automatic Recording of the Sulfur Dioxide Content of the Atmosphere. W h e n a method is suggested for consideration by an A S T M subcommittee, it is often necessary to evaluate it in comparison with alternate methods before making a recommenda-
AIR POLLUTION CONTROL
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tion to the committee. I n the case of the sulfur dioxide recorder, this evaluation step was not necessary because of the long history of successful operation of the instrument a n d the adequate litera ture on its principles and performance. T h e first step in development of this method as a n A S T M tentative, was drafting t h e method in suitable form. T h e draft was distributed to the sub committee members with a ballot form on which they could record suggested changes. These were noted a n d dis cussed a t a meeting. W h e n general accord was reached that the draft was satisfactory, a recommendation was made for a similar ballot of the entire Committee D-22. I n the committee ballot, a wider interest group has an opportunity to approve the item as it stands or to suggest changes. Following committee approval, a recommendation was m a d e to the society for approval and publication of the method as a n A S T M tentative. A committee recom mendation such as this m a y be approved by the society a t its annual meeting or between annual meetings by the Admin istrative Committee on Standards. T h e sulfur dioxide method, after approval, was published as a n A S T M tentative and copies m a d e available to the public. T h e A S T M procedures for developing and publishing standards m a y seem rather involved b u t each step h a s a purpose a n d the e n d result is wide acceptance and use of A S T M standards. T h e r e is a great need for a standardized and generally accepted terminology in this field. Committee D-22 has made a good start in this direction with the Tentative Definitions of T e r m s Relating to Atmospheric Sampling a n d Analysis (D1356-55T) which first appeared, as approved, with the 1955 preprint of the annual report of Committee D-22. Definitions of additional terms are to be added to this list in the future.
Sampling There are many pitfalls a n d chances for error in sampling the atmosphere for analysis. T o serve as a basis for proper sampling, the committee has recom mended a n d received approval for p u b lication of a Tentative Recommended Practice for Planning the Sampling of the Atmosphere (D1357-55T). T h e need for the kind of effort represented in development of this recommended prac tice and other work of Committee D-22, particularly the subcommittee on sam pling, was recognized, and a very appro priate statement was made by A. O . Beckman a t the TJ. S. Technical Con ference on Air Pollution (70) : " . . . one of the major areas in which some funda mental investigation can be carried out to good advantage is the investigation of the theory of sampling and the develop-
AIR POLLUTION CONTROL
Table I. Maximum Allowable Concen trations of Atmospheric Pollutants ( 7 3)
Pollutant
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0.03 O.S 6.0 0.5 0.1S
0.01 0.15 2.0 0.15 0.0003 0.05
0.75 0.30 0.05 0.5
0.0007 0.25 0.10 0.015 0.15
0.05
0.003 0.015
0.15
0.05
0.03 0.10
0.01 0.03
" These concentrations have been ap proved by the VGSI (Bureau of Sanitary Inspection, USSR). Remaining concen trations have been accepted by the com mission but not yet approved by the VGSI. 6 The norms for lead are not applicable to its organic compounds. '• The norms for the inorganic compounds of arsenic are not applicable to hydrogen arsenide. ment of sampling methods which could become more or less standard. " W h o will undertake this type of work? Unquestionably, some of the fundamental aspects of sampling could well become the subject of research for a national body, such as an appropriate federal agency or a university or research institution. It would seem unfortunate if each locality and each group working in air pollution should have to do this work in unnecessary duplication." Odor Measurements
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Formula
M a n g a n e s e and its compounds MnOj Nitrogen oxides" N2Os Carbon monoxide" CO Nontoxic dust" Metallic mercury" Hg Soot" Lead and its com pounds" •' Pb Sulfur dioxide" S02 Sulfuric acid H2S04 Hydrogen sulfide" H2S Carbon disulfide" CS 2 Arsenic compounds 0 (inorganic) As Phenol CHsOH Phosphoric anhydride P2Os Fluorine compounds F Chlorine" Cl
Concentration, Mg./Cu. M. Daily Single average
Measurements relating to odor con tinue to offer greater difficulties than many other determinations because of the subjective nature of odor detection. Research aspects of the nature of odor, its detection, and measurement have occupied wide attention and literature on this subject is growing (2, 5). A completed project of Committee D-22 on this subject is the Tentative Method for Determination of Concentration of Odor ous Vapors (D1354-55T) which has been published. In this method, the vapors are adsorbed on activated carbon and then removed for quantitative and qualitative analyses. Another method which actually involves odor measure ment and is referred to as the "dilution m e t h o d " has been developed by the committee and is designated A S T M Method D 1391-56T.
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M a n y other methods are under active consideration in Committee D-22 and its subcommittees. It is expected that new and improved methods and defini tions will be produced by the committee at an increasing rate in the future. Its work has only just begun. Industry and Municipal Standard Methods A vast reservoir of standardized methods for possible consideration by A S T M Committee D-22 and other nationally recognized standards-writing bodies lies in the active files of industry and various municipal control groups. A good example of work in industry which might be construed as coming at least partially under the general heading of standardization is that carried out by the Manufacturing Chemists' Association under the auspices of the Air Pollution Abatement Committee. T h e M C A Air Pollution Abatement M a n u a l includes much worth-while information on such subjects as terminology, sampling pro cedures, and analytical methods. Its bibliography supplement includes a section of references on standards. O t h e r organizations, governmental and industrial, are doing similar work. T h u s standardization of a kind is wide spread, but often it is of a somewhat un official character. References (1) Am. Soc. Mech. Engrs., New York, "Example Sections for a Smoke Regulation Ordinance." Inform. Bull., 1949. (2) Am. Soc. Testing Materials, Sym posium on Odor, STP 164, 57th Annual Meeting, Chicago, 111., June 15, 1954. (3) Ibid., Yearbook, 1955. (4) Am. Standards Assoc, New York, American Standards Z37, "Allowa ble Concentrations of Toxic Dusts and Gases," 1941-9. (5) Ann. New York Acad. Sci. 58, 13-260 (1954). (6) Arch, of Ind. Hyg. and Occupational Med. 9, 530-4 (June 1954). (7) Barkley, J. F., U. S. Bureau of Mines Circ. 7682, May 1954. (8) J. Air Pollution Control Assoc, Manual APM 1-A, November 1955. (9) Mallette, F. S., Proc. Inst. Mech. Engrs. 168, No. 22 (1954). (10) McCabe, L. C , "Air Pollution," pp. 5, 11, 567, McGraw-Hill, New York, 1952. (11) Mech. Eng. 75, 712-14 (September 1953); Am. Soc. Mech. Engrs., "Guide to Research in Air Pollu tion," May 1955. (12) Philadelphia, Pa., Dept. of Public Health, City Bill No. 366, 1953. (13) Riazonov, V. Α., "Sanitary Safe guarding of Atmospheric Air," Official USSR Publishing Bureau, Moscow, 1954. (14) Smog News (Nov. 30, 1955). (15) U. S. Bureau of Mines, Setby Smelter Report, Bull. 98. (16) U. S. 84th Congress, Public Law 159.
