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by Frank Y. Speight, ASTM, Philadelphia, Pa., Resources Research lnc., New York, N. Y.
S.Mallette,
Standardization Aspects of Air Pollution Controll Ordinances and laws for air pollution control are a form of standard, but there is great need for standardized terminology, sampling and analysis procedures
AS early as the 17th century, air pollution 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. I t may cause unsavory odors. health injuries, and damageestimated a t a considerable figureby deterioration, corrosion, soiling, and crop injury. Tn order to minimize such losses, standardized techniques and criteria are increasingly necessary for gaging degree of air pollution, and maximum concentrations allowable. Nature of Standards
The need for generally acceptable terminology and standard procedures for sampling and analysis of pollutants is most clearly seen a t the local level where the problem of defining allowable limits for various pollutants is encountered. The Philadelphia ordinance (72). for esample, 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 concentrations 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 include growing social responsibility, improvement of public relations: and voluntary or involuntary compliance \vith Presented at Delaware Valley Regional Meeting, American Chemical Society, February 16, 1956.
local ordinances. Occasionally there is a n added incentive-the recovery of salable and sometimes valuable byproducts. Performance standards for air-cleaning equipment are needed and a n effort toward this end is going forward. Industrial Atmospheres
While the problems ofindustrial atmospheres-work areas where healthy workers are exposed for limited durations -are somewhat akin to those of outdoor air pollution, the differences are important and should be clearly stated. The .American Conference of Governmental Industrial Hygienists, over a number of years, has developed a list of maximum allowable concentrations for a number 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 extrapolated for this purpose has not yet been developed. The general population includes the very young, the very old, and the infirm, so that from a n injury-tohealth standpoint, entirely different criteria from those applied to industrial workers must be considered. This is a n involved and complex problem not within the scope of this article. The 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 maximum 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 prevention. Each standard sets forth physiical and chemical properties, summarizes test methods, and includes a comprehensive bibliography. As part of the work of the American Society of Mechanical Engineers’ Committee on Air Pollution Controls, Barkley
(7) assembled information on accepted maximum permissible concentrations of air pollutants from the standpoints of health, damage to vegetation, and damage 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 Governmental Industrial Hygienists, and those included in several state regulations regarding industrial atmospheres. The Russians have established maximum allowable concentrations for both industrial atmospheres and for air pollution control (74) and claim this as another Russian first. Table I shows maximum allowable concentrations of various pollutants, some of which have been approved by the Bureau of Sanitary Inspection of the USSR for atmospheric air (outdoors). 4 s 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 mg./ cubic meter (daily average), a figure over 200 times smaller. Partial explanation of these values may be found in the original Russian publication (7.3). National Organizations Concerned with Standards
American Standards Association. The ASA serves as a clearing house for national standards. There are two ASA projects in thisarea, theobjectivesofwhich are indicated by the titles: 237, Allowable Concentrations of Toxic Dusts and Gases mentioned previously (4) and 274, Fundamentals of Performance of Effluent Air and Gas Cleaning Equipment. Project 274, jointly sponsored by the American Society of Mechanical Engineers 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
SEPTEMBER 1956
69A
1.
AIR POLLUTION CONTROL The API Committee on Analytical Research has a subcommittee on analytical methods for the atmosphere which is engaged in the development of new analytical methods for hydrocarbons and related substances. One 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. The 4 P I 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. The APCA Committee on Air Pollution Measurement is engaged in preparing a manual, 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 hlethod for Gaseous Contaminants Recommended Standard Method for Odor Survey Effect of Meteorology on a n Air Pollution Survey American Society of Mechanical Engineers. The ASME Committee on .4ir Pollution Controls, organized in 1949, includes in its scope: ”To collaborate in the formulation and publication of standards of appropriate nature.” 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 274 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 .4nalysis. On the legislative aspect of standards, The American Society of Mechanical Engineers has made a major contribution by its development of the “model smoke law,” more properly termed “Example Sections for a Smoke Regulation Ordinance” (7). The model smoke law includes a section relating to standards of measurement. In 1940, the ASME 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 “Example Sections for a Smoke Regulation Ordinance” was adopted by ASME
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 a n d Steel Institute. The AIS1 Air Pollution Committee, W. 0. Everling. Chairman, has supported research into the development of inexpensive air-sampling and measuring instruments, in particular, for determining and recording air-borne dust. The instrument has also been adapted for detecting hydrogen sulfide. American Meteorological Society. This organization has a committee on air pollution abatement \vhich has published “.4 Statement on the Present Possibilities of Applying hleteorology in Air-Pollution Abatement.“ If these activities do not include standardization, a t 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. McCabe, was established in .4SThf. .4 long-standing policy of ASTM is to have represented all major interests in a particular field which have the competence to advance the Lvork of a technical committee. That 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 generallj- as authoritative and that it will carry the weight necessary for national acceptance and use. The 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 (ASTM 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, The Tentative Method for Continuous Analysis and Automatic Recording of the Sulfur Dioxide Content of the Atmosphere (ASTM Designation D135555T). The history of this method goes back to 1922. The chairman of the subcommittee which developed it was M . D. Thomas who, in 1922, was using the method of hfarston and Wells (75)for determining lo\v concentrations of sulfur dioxide in air. Prior to 1922, bubbler trains had been
INDUSTRIAL AND ENGINEERING CHEMISTRY
used to collect the gas. and the gravimetric method was often applied. Later? a program \vas initiated at American Smelting and Refining Co. which required many gas analyses, and soon the shortcomings of the hfarston-Wells method became painfully evident. One test could be made in five minutes if the approximate gas concentration of the samples were known, but when 1 2 tests a n hour lvere required: \vhich \vas 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, Thomas and his colleague, R. J. Cross, took steps to improve the method. I n a communication, Thomas wrote: ”We 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 ivhich required a turntable on which to collect successive samples. LVe adapted a n old circular-tub washing machine for this purpose, using many of the old gears. It had a noisy “whee!barrow” movement but it turned out samples a t 2-minute intervals, as rapidly as a chemist could titrate them. LYe 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 May 1929, \ve had assembled an ’autometer’ (so christened by Dr. George R. Hill) complete with a Leeds and Northrup conductivity recorder and installed it in an agricultural area adjacent to a smelter. This and replacement instruments have operated continuously a t the same location to the present. Even the earliest records were quite satisfactory. I n 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. Many of these instruments are still in operation. I n subsequent years, mechanical modifications were made in the instrument, but the fundamental principle of its operation remained unchanged.“ These developments are fully documented (10) and as indicated, the Thomas autometer is the instrument around which \vas bvritten the ASTM Tentative Method for Continuous Analysis and Automatic Recording of the Sulfur Dioxide Content of the Atmosphere. When a method is suggested for consideration by a n ASTM subcommittee? it is often necessary to evaluate it in comparison v i t h alternate methods before making a recommenda-
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G56.6
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CHEMICAL MATERIALS FOR INDUSTRY
For further information, circle numbers 71 A-1, 71 A-2, 71 A-3 on Readers' Service Card, page 139 A VOL. 48, NO. 9
SEPTEMBER 1956
71 A
n H E R E ' S YOUR
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AIR POLLUTION CONTROL .-_----__________-__~----------------.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 and the adequate literature on its principles and performance. The first step in development of this method as a n ASTM tentative, was drafting the method in suitable form. The draft was distributed to the subcommittee members with a ballot form on which they could record suggested changes. These were noted and discussed a t a meeting. When general accord was reached that the draft was satisfactory, a recommendation was made for a similar ballot of the entire Committee D-22. In the committee ballot, a wider interest group has a n opportunity to approve the item as it stands or to suggest changes. Following committee approval, a recommendation was made to the society for approval and publication of the method as an ASTM tentative. A committee recommendation such as this may be approved by the society a t its annual meeting or between annual meetings by the Administrative Committee on Standards. The sulfur dioxide method, after approval, was published as a n ASTM tentative and copies made available to the public. The ASTM procedures for developing and publishing standards may seem rather involved but each step has a purpose and the end result is wide acceptance and use of ASTM standards. There 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 Terms Relating to Atmospheric Sampling and 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 and chances for error in sampling the atmosphere for analysis. T o serve as a basis for proper sampling, the committee has recommended and received approval for publication of a Tentative Recommended Practice for Planning the Sampling of the Atmosphere (D1357-55T). The need for the kind of effort represented in development of this recommended practice and other work of Committee D-22, particularly the subcommittee on sampling, was recognized, and a very appropriate statement was made by A. 0. Beckman a t the U. S. Technical Conference on Air Pollution (70) : ''. , one of the major areas in which some fundamental investigation can be carried out to good advantage is the investigation of the theory of sampling and the develop-
.
For further information, circle number 72 A on Readers' Service Card, page 139 A
72 A
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t h e c o m p l e t e l y n e w F i l t e r a i d f o r u s e in s t r o n g l y a l k a l i n e I i q u o r s The idea of using carbonaceous filteraids in processes involving caustics os fluorides is not new. But NEROFIL - a processed carbon-based filteraid - is completely n e w . . . and valuable because it overcomes the difficulties often encountered with earlier carbon materials. ( A ) is a photomicrograph of a crushed carbonaceous material (quite similar to previous carbon filteraids) . This, however, is merely the reactor feed from which NEROFIL (B) is made. Both photomicrographs a r e t h e same magnification. T h e marked differences are evident.
NEROFIL's success as a filteraid stems from t v o important features. First, of course, its physical and chemical stability,. , even boiling caustic has negligible effect. Second, the high filter cake porosi t y a n d low cake density of N E R O F I L yield f a s t throughput of liquid and superior clarity of filtrate. This stability and filtration efficiency have led several different industries to adopt NEROFJL in their processing, with excellent results. Complete information on NEROFIL is available to you in a new bulletin, j u s t issued.. .write f o r it.
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VOL. 48, NO. 9
SEPTEMBER 1956
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Table I. Maximum Allowable Concentrations of Atmospheric Pollutants ( I 3) Concentration, .IIg.,'Cu. Daily Formula Single average
x.
Pollutant
Manganese and its compounds MnOz N20j Nitrogen oxides" Carbon monoxide" CO Nontoxic dust" Metallic mercurya Hg sootn Lead and its compounds" Pb Sulfur dioxide" so2 Sulfuric acid H2S04 Hydrogen sulfide" HzS Carbon disulfide" CSn Arsenic compounds (inorganic)c As Phenol CsHsOH Phosphoric anhydride Pzo5 Fluorine F compounds Chlorine" c1
.. ..
ph
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0.01 0.15 2.0 0.15
0.15
0.05
..
..
0.75 0.30 0.05 0.5
..
0.0003 0.0007 0.25
0.10 0.015 0.15
0.003
0.05
0.015
0.15
0.05
0.03 0.10
0.01 0.03
5 These concentrations have been approved by the VGSI (Bureau of Sanitary Inspection, USSR). Remaining concentrations have been accepted by the commission but not yet approved by the VGSI. b The norms for lead are not applicable to its organic compounds. c The norms for the inorganic compounds of arsenic are not applicable to hydrogen arsenide.
ment of sampling methods which couid become more or less standard. "LYho 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. I t would seem unfortunate if each locality and each group \vorking in air pollution should have to d o this Jvork in unnecessary duplication.'' Odor Measurements
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0.03 0.5 6.0 0.5
I I I I I I
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Measurements relating to odor continue to offer greater difficulties than man) 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 (1.5). A completed project of Committee D-22 on this subject is the Tentative Method for Determination of Concentration of Odorous Vapors (D1354-55T) which has been published. I n this method, the vapors are adsorbed on activated carbon and then removed for quantitative and qualitative analyses. Another method which actually involves odor measurement and is referred to as the "dilution method" has been developed by the committee and is designated ASTM Method D 1391-56T
INDUSTRIAL AND ENGINEERING CHEMISTRY
Many other methods are under active consideration in Committee D-22 and its subcommittees. I t is expected that new and improved methods and definitions will be produced by the committee a t a n 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 ASTiM 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 a t 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 MCA Air Pollution Abatement Manual includes much worth-while information on such subjects as terminology, sampiing procedures, and analytical methods. Its bibliography supplement includes a s x t i o n of references on standards. Other organizations, governmental and industrial, are doing similar work. Thus standardization of a kind is widespread, but often it is of a somewhat unofficial character. References
(1 ) Am. SOC.Mech. Engrs.. Kew York, "Example Sections for a Smoke Regulation Ordinance:'' Inform. Bull., 1949. ( 2 ) Am. SOC. Testing Materials, Symposium on Odor, STP 164, 57th Annual Meeting, Chicago, Ill., June 15, 1954. (3) Zbid., Yearbook, 1955. (4) Am. Standards Xssoc., New York, .4merican Standards 237, "Allowable Concentrations of Tosic Dusts and Gases," 1941-9. ( 5 ) ,47272. A'ew York Acad. Sci. 58, 13-260 (1954). (6) Arch. of Ind. Hyg. and Occupationul 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) hlallette, F. S., Proc. Znst. Mech. Engrs. 168. No. 22 (1954). (10) hfcCabe, L. C., ".Air Pollution," pp. 5, 11, 567, McGraw-Hill, New York, 1952. ( 1 1 ) .Mech. Eng. 75, 712-14 (September 1953); Am. SOC. Mech. Engrs., "Guide to Research in Air Pollution." May 1955. (12) Philadelphia, Pa., Dept. of Public Health, City Bill KO. 366, 1953. (13) Riazonov, V. A , "Sanitary Safeguarding of Atmospheric Air," Official USSR Publishing Bureau, Moscow, 1954. (14) Smog h ' e w (Nov. 30, 1955). ( 1 5 ) U. S. Bureau of Mines, Selby Smelter Report, Bull. 98. (16) U. S . 84th Congress, Public Law 159.
