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/ '* r- )t - -* AIR HYGIENE FOUNDATION OF AMERICA, Inc. Preventive Engineering Series, Bulletin No. 2, Part 8 < "X Routine Sampling for Control of Atmospheric Impurities PITTSBURGH, PEXXSYLVAX1A JANUARY, 1030 01026 5 PLAINTIFF'S < 2 5 EXHIBIT ^ i Ea ROUTINE SAMPLING FOR CONTROL OF ATMOSPHERIC IMPURITIES* The control and sampling of atmospheric contaminants in routine pro duction operations are matters with which plant and mine managers today are definitely concerned. A few years ago, such control was more or less limited to firms that were losing a valuable product through faulty operation, or to those that knew that neglect of dust, fly ash, or gas control meant a health, nuisance, or explosion risk, cither to themselves or to their neighbors. Today, however, twenty-eight states (Table 1) have industrial hygiene bureaus whose function it is to advise industry on the control of its indus trial hazards, while many insurance companies are well equipped to investi gate industrial hygiene problems from both the engineering ami medical aspect.f Baltimore, Maryland; Detroit, Michigan; Rockford, Illinois, and St. Ivouis, Missouri, are reported as having industrial hygiene bureaus. The formulation of codes of good practice is a trend of comparatively recent date. Underwriters' codes covering fire and explosion risks have been available for some years. To them is now being added information, such as the National Silicosis Conference's recommendations on dust counts in relation to silicosis prevention1, New York State's codes on silica dust control in rock drilling2, and the American Foundrymen's Association's codes on exhaust systems for general foundry work-'1. The American Standards Association has a committee which, it is understood, will suggest, from time to time, safe concentrations of various contaminants. Some states now furnish, on request, a list of maximum safe concentrations which they recommend for various dusts and gases. (The Massachusetts list is given in Table 2). In some instances, as in Wisconsin and New Y'ork, the codes have been made legally binding. Other states have issued the lists merely for the guidance of persons who ask how clean the air of a workplace should be. It is not our intention to criticize these codes. The concentrations gen erally are not fixed by accepted medical standards, but represent zones or ranges arrived at by practical trial. Obviously, the figures must be revised from time to time as medical knowledge on the subject progresses, and especially as industry improves its housekeeping. The purpose of this bulletin is to give in brief form descriptions of apparatus and methods which arc actually being used by one or more labora tories in appraising the environment in which men work. In making such appraisals, two distinct steps are involved: first, measurement of air cur rents, and second, estimation of impurities. The resulting data can then be applied to the design of control equipment or to the appraisal of the results brought about by such equipment. Air Movement Low Air ['clodlies Air velocities in workplaces generally are below 100 F. P. M. (feet per minute). Exceptions are warm places where fans or air blasts are used for their cooling effect, mine shafts and haulage ways used as ventilation ducts. This is pan S in the series Issued as I'.uUetin No. 2, uml>-r the auspices of the Preventive lhi^itieei itne Committee. t Detailed information on iiiMuome-comi'nny activities can be had from American Mutual Allinm-c, SIS North Mi. hiftun Avenue, Chicago, and the Association of Cas ualty Surely Kxeeuliyes, t.o John Street, New York Cite1. 1 /' : ? , ! i ! i i j | I ; i' j i ! ) ! t j j l i i 1 i ! ! j > and atmospheres within the immediate zone of exhaust hoods. Low veloci ties must be measured by special instruments as they are below the ranee measurable by pitot tube, venturi meter, or vane anemometer. Smoke Bombs: In schoolrooms or auditoriums, air conditioning engineers usually study air distribution by the use of smoke. Smoke from tobacco is of too fine a tex ture to serve as well as the coarser smoke made from hygroscopic substances. Titanium tetrachloride smoke tubes for testing work are safer to use and give satisfactory results. They can be made as follows: glass serum ampoules, costing about S2.40 a gross, are filled with 0.10 cc. of titanium tetrachloride. The ampoule is then sealed and the r.eck pl'-4 out about 0.25 inch, dipped in water-glass as an adhesive, and about an inch of wicking pushed over the neck. The wicking used in a sulfur lamp is satisfactory. Since the compound reacts with air and becomes vitiated, the ampoules should be sealed promptly. When a smoke test is desired, the neck of the ampoule is broken by laying it on a hard surface and pressing down with the thumb; the wicking will protect the thumb against cutting with the glass. The TiCl^ runs out into the wick and smoke immediately results. A smoke gun can be made by soaking pumice with titanium chloride and packing in small glass tubes, such as calcium chloride drying tubes. Air is then blown through the pumice by means of a rubber aspirator bulb, When not in use, the ends of the tube should be closed with stoppers, Titanium tetrachloride is carried by most supply houses and costs about 75 cents per quarter pound, which is enough to fill a large number of ampoules. Smoke tubes and smoke guns in convenient form arc supplied by (g), (j).-' Thermo-anemometer: C. P. Yaglou has recently developed4 a simple thermo-anemometer capable of measuring velocities between 10 and 6,000 F. P. M. The temperature of the wire is only 10 to 40 above air temperature and is indicated on an ordinary thermometer around the bulb of which the wire is wound. Small dry cells furnish the heating current and the voltage is regulated by means of a rheostat. These auxiliaries are assembled in a small box. Readings to be taken are temperature of heated and of unheated thermometer and voltage used. The velocity is read off a table or chart, or computed from an equation. By varying the voltage, any velocity can be measured with an accuracy of 9Sci. A unit which is vest-pocket size and sensitive to very low velocities will be available shortly. This instrument compensates for variations of air density due to temperature changes, and is negligibly affected by humidity, radiant heat, and convectional currents which it causes. It is particularly useful for measureing air movement in rooms and in exploring "point" velocities in front of exhaust hoods, because it offers negligible obstruction to airflow. Its disadvantages are that it is not direct reading, it requires a short time for the heated thermometer to reachequilibrium, and itsreadings must be corrected for partial stemimmersionwhen usedinside small pipes. The instrument is too new to have had any widespread field use. It is supplied by (m). ________ (a), (b). etc., vefer to Arms supplying equipment. For full list and addresses, see Table i. rage IS. of tills bulletin, O e-te-ss 01028 r -V... High Air I'clwitifi In the effective zone of exhaust hoods, the minimum velocity is about 150-200 feet per minute extending on up to 1,000 F. P. M. or more at the face of the hood. It is often desirable to increase the hood's effectiveness by changes in design. Velocity contours can he sketched out as indicated in Figure 1 of Bulletin No. 2 of this series. For measurements in such velocity ranges, Yaglou's thermo-anemometer device is well suited. Vane Anemometer: In the ease of large koous, such as those placed over electroplating >' vats, either a velometer or a small vane anemometer is convenient. For exploring small hoods, however, both instruments take up too much space and interfere seriously with the normal air currents which the hood is in tended to form. Furthermore, the portable vane anemometer is a delicate instrument; it needs frequent calibration, and is easily damaged by corrosive chemicals, by dusts, and even by steam or water vapor. It is advisable to use the vane anemometer only when no corrosive substances are being generated. Velometer: This is a direct-reading device consisting of a double-pivoted vane which is deflected by impact against the air stream. A pointer attached to the vane indicates the velocity on a calibrated scale. All moving parts are housed in a small case. For low-range readings, the air enters the meter directly through a small port and the whole case must be placed into the air stream. For high-velocity readings, various size orifices are placed within the port to reduce vane deflections. For measurements of velocity inside pipes, a double-pitot tube is provided and connected to the meter ports by rubber tubing. Velometer readings are instantaneous, but several must be taken to insure a good average. One can measure velocities of several thousand feet per minute, as in exhaust ducts, or a few hundred feet per minute in the vicinity of large exhaust hoods. Although a dust-filter attachment is now available for keeping the mechanism dean, it is questionable whether it is wise to use the instrument in any but clean air. The device is supplied by (h). A less accurate, but very practical instrument, known as the "Grillometer," has been developed for measuring air velocities through grills. It is a torsion device and is direct reading. It is supplied by (d). Pitot Tube, Venturi Meter and Orifice Meter: While these three instruments measure flow rather than velocity, they are too well known to need any description. The pitot tube has- long been the sole "self-standard" instrument and the most used for determining flow in pipes or ducts, for making traverses, and the like. Recording venturi meters and orifice meters for measuring the flow of fluids (liquids and gases) are sold today by several firms. In the construction of exhaust systems, it is well to consider the permanent installation of a venturi, or an orifice meter, or even a recording meter near the exhaust fan. The A. S. M. E. book7 gives full details of the basic principles, design, and use of these instruments. 01029 * / / Atmospheric Impurities For the purposes of selecting sampling and control methods, in relation to exhaust systems in plants or mines, several distinct types of atmospheric impurities must be considered: A. Relatively insoluble mineral dusts, such as silica, many silicates, and fly ash. B. Relatively soluble mineral dusts, like calcite (limestone). C. Finely-divided fume substances that are difficult to catch in water. Examples are lead, lead oxide, and zinc oxide. D. Dusts that may be affected by water. Examples are flour, leather, and oUap. Many of these dusts are explosive if mixed with air. E. Aqueous mists, such as chromic acid entrained from electroplat ing baths, or condensate from vats of various sorts. F. Water-soluble gases, such as hydrochloric acid. Such soluble gases usually contain mist as well as gas, the proportions depending upon local conditions. G. Gases or organic vapors, like benzene, soluble with difficulty. These react slowly with most liquids but may be adsorbed readily by solids, such as activated carbon. Jmpinger: Instruments for Dust Sampling The impinger is commonly used in sampling dusts, like classes A, B, and occasionally mists, like class E, and some gases, like class F. It is definitely unsuited to class G gases, like chlorine or organic vapors. It is liot efficient against finely-divided fume substances. Class C, such as lead or zinc oxide, and rarely is it suited to sampling organic dusts, like class D. The impinger5 consists in a flask in which a tube with tapered end is held at a fixed distance from an attached glass plate or from the bottom of the flask. Air is drawn through the tube and the impurities are trapped in the liquid in which the tip of the tube is immersed. Suitable fractions of the dusty suspension are then withdrawn and the dust particles counted under the microscope or the total dust concentration is estimated by the usual analytical procedures. The impinger is now made in two sizes, one sampling at one cubic foot per minute, and the other at three to five liters per minute. Used originally with water as the dust-catching medium, it is now common practice to use other liquids, such as isopropyl alcohol, limitation depending upon volatility of the liquid and its readiness to foam. The suction device for the impinger can be run by a compressed-air actuated ejector or by a pump driven by an electric motor. The midgot- impinger equipment is much smaller and can be run by hand. It is lighter than the large unit. Furthermore, it is hand operable, all of which makes it particularly suited to mine-air sampling. Both types of impinger were developed by the U. S. Bureau of Mines, which recommends both for general use in measuring dustiness. Jmpingers, either large or midget size, are supplied by (e), (i), (j), (k), (m). For sampling finely-divided fume substances, like lead, which are well dispersed, a small electric precipitator gives accurate results. While the complete precipitator assembly is not expensive, it requires a transformer 0*030 weighing some 15-25 pounds to raise the voltage to 15,000 to 25,000. Con struction details with a list of equipment needed for making such precipi tators are given in Drinker & Hatch0. This equipment is available from (m). Barnes & Penney, of the Westinghousc Electric & Manufacturing Com pany, have described5 a small precipitator which should be well adapted to field use and is now available from (j). The high-tension side of this newtype precipitator is grounded, making it more practicable for general field use. Sampling Dust for Direct Microscopy and Counting The purpose of taking and counting dust samples is to determine how much the dustiness of the air in question departs from some arbitrary figure or accepted standard. The grab-sample instruments, via., the kor.imel.ei (j), the Bausch & Lomb dust counter (a), (m), and the Owens jet dust counter (e), give useful indications of changes in dustiness. All three instruments are light and are operated entirely by hand. However, they do not imitate the impinger in any way, so that it is impossible to convert impinger to grab-sample counts. The reason why such conversions are faulty is because the grab samplers favor dust sizes below the size-particle range for which the impinger technic is best adapted. A skilled technician can count about twelve impinger samples in a day. It is easy, however, to compare some thirty to forty grab samples in a short time. In practical field work with the grab sampler, the effectiveness of dust-control equipment or methods can thus be demonstrated rapidly. Explosive Dusts Most explosive dusts are affected by water, while some of them, espe cially organic dusts, such as flour, are difficult to wet. Explosive concentra tions of all such dusts are very high (10-15 gms./m3) as compared with dust concentrations of hygienic significance (0.5 gms./m3), so that explosive dusts are determined by weight rather than by count. Air is drawn through a weighed paper extraction thimble and the increase in weight caused by the dust from a known volume of air is noted. An objection to this procedure is the trouble and time required to equilibrate the paper thimble against the moisture in the air. This objection, however, is not serious if the weight of the dust sample, as in the case of explosive dusts, approximates that of the thimble. It should be remembered that in sampling explosive dusts one must use a suction device that avoids the chance of electric sparks. Quantitative' Analysis In the case of all dusts, classes A, B, C, and D, the estimation of the sample taken from the air can be made by counting representative fractions under the microscope, or the sample can be analyzed by appropriate chemi cal methods, or the material can be weighed. The large impinger and the electric precipitator are equally well adapted to either procedure. The mid get impinger collects, in reasonable sampling time, a relatively small amount of dust, but enough for counting. Dusts, like silica, that are troublesome to determine chemically, are generally counted, while those like lead, manganese, and cadmium, are determined chemically. In places where composition of the dust and the particle size remain 5 substantially the same day after day, it is possible to estimate roughly dusti ness in impinger samples from the turbidity of the dusty emulsions. Such estimates can be made in Kessler tubes, by tyndallmcter,;, or by an adapta tion of the turbidity methods commonly used in water analysis. Light-Field vs. Dark-Field Counting For routine control work, the relative advantages of these two methods of counting dust samples (no matter what sampling instrument is used) are unimportant. It is immaterial which method is used. If the person doing the counting feels that the light-field set-up is bard on bis eyes, or the mag nification too low, by -'ll means he should try the darV-fie'd method. On. the other hand, if he is using the impinger and wishes to copy in exact detail the procedure recommended by the U. S. Public Health Service, then lightfield counts must be made. The Bureau of Mines recommends a micro-pro jection method for impinger counts5. The konimetcr, recommended by the Bureau of Mines for control sampling, is used in South Africa, where it originated, with dark-field, while the Bausch & Lomb counter is.available with dark-field only. Owens samples can be counted by either light- or dark-field. Gas Sampling Gas concentrations commonly met in sanitary air analysis are very low. Concentrations that men may breathe usually are given in parts per million by volume (P. P. M.), or in milligrams per liter, or per cubic meter under specified temperatures and pressures. Some gases and vapors, notably carbon monoxide, hydrogen sulfide, and mercury, in minute amounts, give strong chemical reactions which makes possible rapid estimations and still better, continuous records of pollution. However, the great bulk of gases and vapors from organic solvents, such as benzene, carbon tetrachloride, and carbon disulfide, cannot be caught effi ciently unless sampled at slow rates, such as 2 to 1 liter per minute. Some of them, such as benzene, can be absorbed directly in special solvents or adsorbants, like charcoal or silica gel, or can be converted into another compound which can then be estimated by an appropriate method. The greatest difficulty in estimating organic vapors in air occurs when mixtures of vapors are present. Unfortunately, tin's is all too often the case. Then, the devising of short cuts in itself offers a major problem, but local conditions sometimes permit the approximations of the proportions of the several ingredients in the collected sample and calculation of the total by estimating only the most easily-determined single constituent. Condensation The general availability of "dry ice" (temperature -- --79 C.) makes convenient the routine collection and estimation of volatile compounds, like gasoline, for which liquid air (temperature = --192 0.) formerly was used. A convenient cooling mixture is made by pouring ethyl alcohol or gasoline on cracked dry ice. The condensation apparatus is then immersed in the cooling mixture. Liquid air is available in most large cities and offers a convenient cooling medium, but it should be remembered that it forms explosive mixtures with inflammable dusts or gases. 6 ,-m. ....... Vapor-Pressure Measurements If only one substance is present--ami that in a high degree of purity-- measurements of concentration can be made conveniently and quickly by condensing the vapor with the dry-ice mixture and then estimating the con centration by the Burrell-Jones vapor-tension method1'. This procedure is not in common use in industrial hygiene problems and needs further study. Routine Sampling and Recording of Air Impurities If control equipment has been installed, samples should be taken period ically for check-ups. This is the best way to tell whether the equipment is functioning as it should. If concentrations obviously are high, it is usually a waste of time to take the sample and to estimate it. For instance, a leaky elevator in a crushing plant or a defective rattler or an unhooded swing grinder in a foundry may cause such high dust concentrations that an impinger sample will be turbid in a few minutes. Little is gained by going through the sampling routine in such cases, unless one wishes to have records before and after repairs have been made. Today, many plants operate crushing units and other dust producers at night to take advantage of reduced power rates and to stagger employment over twenty-four hours. During the night shift, dust inspections can be made rapidly, using nothing but the beam from an ordinary flash light to detect dust leaks. In the case of some gases and vapors, one's sense of smell often permits detection of gas concentrations which exceed desirable limits. Such a test is quite unreliable unless one returns frequently to clean air or carries with him a respirator with an activated charcoal cartridge through which he takes several breaths before attempting to gauge the strength of the odor. One becomes used to even such dangerous or disagreeable odors as hydrogen sulfide in a few monments and it is, therefore, risky to estimate their strength by smell. Such crude tests do not take the place of regular sampling technic. How often the routine samples should be taken depends entirely upon local conditions. In some places, they are taken daily, while in others, several times a year is enough. It is well to play safe and to take them too often rather than too seldom. The men quickly become used to such sampling and pay no attention to the procedure. Obviously, the sooner" the sampler has the man's interest in his results, the better will be the outcome. It is com mon for the workmen to ask what the results are and to see to it that the samples in their particular departments are satisfactory. We know of one mining company whose concentrating plant is equipped for the taking of monthly dust samples. Various sampling stations have compressed air piped to convenient points and each station has an arrange ment for holding the impinger bottles. In this plant, it is usual for one operator to take, at the same time, samples on four floors of a single building. Samples should be taken wherever men work. It is a mistake to ignore places where one believes that there is no dust or gas. The samples are about the only proof that the employer can bring forth that he has taken proper precautions to prevent a disease, such as silicosis or a chronic poison ing from benzol. The mere statement that he or anyone else thought the atmosphere sufficiently clean is not enough. It is advisable to plot the results of periodic samples with the days or months as abscissae and the concentrations or dust counts as ordinates. Such plots can be made conveniently on a master sheet, comments noted on the plot which is blue printed with c-ach new batch of samples, and the prints given to the appropriate departments. Continuous Records It is obvious that continuous records of either dust or gaseous impuri ties are more informative than occasional or intermittent records. It is possible to take continuous records of relatively heavy pollution, as in the stacks of power plants, and also of ordinary atmospheric pollution which is of relatively low concentration. It is understood that Mine Safety Appli ances Company, Pittsburgh, will offer shortly a dust recorder that may prove useful in common sanitary air analyses. As noted previously, gases that give strong chemical reactions, particu larly those involving pronounced heat or color changes, are suited to estima tion by continuous recorders. A carbon monoxide recorder (j), which meas ures the heat liberated by a catalytic combustion reaction, is in wide use today. A recorder for mercury vapor (f) has also found considerable appli cation. The applicability of recorders in sanitary air analyses has hardly been touched upon and it is reasonably certain that others will be developed as need arises. Photographs It is common practice in power-plant operation automatically to take photographs at regular intervals of the smoke escaping from the stack. Such records provide useful evidence if the plant is accused of faulty operation. Occasional photographs of various plant and mine operations are often of greater practical usefulness than are records of dust counts or of gas or vapor concentrations. AS an exhibit on the company's bulletin boards, photo graphs are effective warnings to the men to clean up. In routine sampling, they should certainly be taken occasionally and incorporated as part of the inspector's report. 8 0id34 TABLES I.Summary of Industrial Hygiene Activities in States and Cities in the United States from June, 1938. List fur nished by the Division of Industrial Hygiene, U. S. Public Health Service, Washington, D. C. II. Concentrations of Inflammable Vapors, Suggested by the U. S. Bureau of Mines, and Limits for Practical Control, Suggested by the Massachusetts Division of Occupational Diseases. III. Analytical Procedures in Current Use in Industrial Hygiene. IV. Firms Supplying Equipment Mentioned in this Bulletin. 9 / / f I I 10 0 * 1 > K) 6 oso to W fr> < H to J! I?:! f 11 ILL ' 'K. s: : Sr ; S? . 2 Si O K WH > rw a b a*- xo w-< H>-< O n a < to TJ H i va .5 H <! K to O U a to *w-( H -< K i> <H HO < oo C/ }Q Sli sijfrS :i Sia rz .S' ;.;> )3 f\ 'rs W a QO Q^ ~ w>-t o >-* !!ilj!il!! 11K V | > v (v i v k5 Ct~i 7. 7 7\7, 7. H to i a Q i !) *-* t*4 XS*V? jr* *r i;,*cC*"nm, \rrr*-` r* r r- iS IO- to ??n c* N X },-r?-T -IXo' ^- o 1{ % i i < S3 S citrt r^'f-'x r- o x * -- S g Sig y 2js c-f!*; --' z\i/ x I' -**'*' 21 x j-^;w a to O .5 2 -iis *roa )*v- v - . o)<j )tli-!KO *.C ir te ,,fcifcfe tCi.ICtO I'f,,ol -X t, 1 r O O ,!&--;{*- C5 l yca}|Cos0 h :h 2 Hto .xs>-- slSfis.......... n 010 37 TABLE II CONCENTRATIONS OF INFLAMMABLE VAPORS, SUGGESTED BY THE U. S. BUREAU OF MINES, AND LIMITS FOR PRACTICAL CONTROL, SUGGESTED BY THE MASSACHUSETTS DIVISION OF OCCUPATIONAL DISEASES GAS OR VAPOR Lower Limit, by Volume % Ammonia ................................................. 36 Acetaldehyde .......................................... 4 Acetone ................................................. 3 Acetone (turbulent mixture)..... 2.5 Acetylene ............................................. 3.0 Acetylene (turbulent mixture).... 2.3 Benzene ............................................... 1.4 Benzine ................................................ 1*1 Blast furnace pas .............................. 35 Butane ................................................... 1.0 Butyl acetate (30 C.) .................... 1.7 Carbon disulfide ................................ 1.0 Carbon monoxide ......... 12.5 Cylclohexane ...................................... 1.3 Dichlorethylene .................................. 10 Ethane .................................................. 3.2 Ethyl acetate .................................... 2.5 Ethyl alcohol ..... .............................. 4 Ethyl bromide .................................. 7 Ethyl chloride .................................... 4 Ethyl ether ........................................ 1.7 Ethyl formate .................................... 3.5 Ethyl nitrite ...................................... 3 Ethylene .............................................. 3.0 Ethylene dichloride ....................... 6 Eihvlene oxide ................................ 3.0 Furfural <325* C.) ............................ 2 Gasoline ....................................... 1.4 Hydrogen ............................................ 4.1 Illuminating Gas Methane .......................................... Methane (turbulent mixture).. Methyl .acetate .............................. Methyl alcohol .............................. Methyl bromide ........................... Methyl chloride ............................ Methyl cyclohexane ................... Methyl ethyl ketone ....... ........... Methyl formate ............................ Natural pas .................................... Pentane ............................................ Propane ............................................ Propvl acetate .............................. Pyridine (70* C.) ......................... Toluene ........................................... . Vinyl chloride ................................ Water pas ....................................... 5.3 5.3 5.0 4.1 7 33.5 5 1.2 2 6 4.$ 1.45 2.4 2.0 1.8 1.4 4 6 to 0 * Milllprams/cu. meter Maximum Concentration Suggested by Massacb" GAS OR VAPOR P. P. M. Ammonia .................................... 100 Amyl acetate ........ 400 Aniline ............................................. Arsine ................................................. 5 1 Benzol ................................................. 75 Cadmium ........................................ Butyl acetate ................................ Carbon bisulfide ............................ Carbon monoxide ........................ Carbon tetrachloride .................. Chlorine ............................................. Chlorodiphenvls ............................ Chloronaphthalenes .................... Chromic acid ................................ Dichlorbenzene .............................. Dichlorethyl ether........................ Ether ....... .................... ...................... 0.1* 400 15 100 100 1 1* 1 to 5* 0.1* 75 35 400 Ethylene dichloride .................... 100 Formaldehyde ........................ 20 Gasoline ....................................... 1000 Hydrochloric acid ........................ 3 0 Hydropen cyanide ........................ 20 Hydrocen fluoride ........................ 3 Hydropen sulfide .......................... 20 Dead ................................................... 0.15* Mercury ............................................. 0.1* Methanol ........................................... 200 Monochlorbenzene 75 Nitrobenzene .................................. Nitropen oxides ............................ Ozone ...... Phosgene ......................................... Phosphine ......................................... Sulfur dioxide ................................ Tetrachlorethane .......................... Tetrachlorethylene ................ Toluol .............................................. Trichlorethylene ............................ Turpentine ...................................... Xylol, coal tar naphtha.............. Zinc oxide fume............................ 5 10 1 1 2 10 10 200 200 200 200 200 15? 12 0iJ38 TABLE III. ANALYTICAL PROCEDURES IN CURRENT USE IN INDUSTRIAL HYGIENE The substances listed in the following: table are more or less commonly found in industrial atmospheres. Methods of deter mination which are suggested have all been used by laboratories in this country and found to be satisfactory. Not all of the methods listed, hDiM'"v are specific. It is assumed that the user of this table is familiar with common analytical procedures and with the general methods of sampling or collecting atmospheric impurities. For example, lead as a dust, such as lead arsenate, would be caught b)r impinger; lead fume from lead burning by electric precipitator; while lead tetraethyl would be collected by means of a bubbler. Differ ent rates of flow would be used in each case. MATERIAL Acetone Ammonia Aniline Arsenic (dust) Arsine (gas) Benzene Bromine Method of Collection Draw air through bubbler containing H-O. Draw air through H-SO* so lution in gas wash bottle. Low Cone. Draw air through bubbler containing acidified (H-SO,) dist. water and methyl red indicator. Continue to end point. Cone. Greater Than 1 % Draw air through bubbler containing 50 cc. of a satur ated solution ot boric acid. Draw air through bubblers! containing 10^ H:SO. Draw air through impinger containing water. Draw air through bubbler containing alcoholic KOH. Draw air through nitrating acid. Draw air through Indicating instrument. Draw air through bubbler containing D solution in KI with starch. Method of Determination Modified iodometric lu. Determine XH, by A. P. H. A. Standard Method . Calculate XH- concentration as in ordinary aeidimetry. Titrate with 0.025 X. H.SO, using methyl red indicator. Depends- upon reaction of aniline with Er- usingsodium indigo disulfonate as an indi cator vs. Iodometric. Modified Gutzeit10. Colorimetric or volumetric determination as dinitroben zene. Ref.: Air Hyg. Bull. No. 2, Part 1 (Jan., 193S). Equipment from (J). Iodometric. 13 0 i d?9 MATERIAL Carbon dioxide Carbon disulfide Carbon disulfide and hydrogen sulfide in presence of each other Carbon monoxide Chlorine Chlorinated hydrocarbons, general Carbon tetrachloride Chromic acid (mist) Method of Collection Draw nr through 'aferantc'* after removing water Yapur on drierite** and weigh. Draw air through bubbler containing a buffered N;i H( H > solution and phenolsulphonophthalein indicator. Gas-collecting bottles. Draw air through alcoholic KOH to form potassium ethyl xanthate. Draw air through 10% CdCU solution, then through 2.5% ILSOi and through 5% acohoiic* KOH. Low concentrations, 10 to 1,500 PPM. by heat liberated from combustion with Hnpcalite as catalyst. Concen tration on dial of a milliammeter. High concentrations, 0.05 to 1.0% (500*10,000 PPM) use detector depending upon liberation of I2 from 1.0- or color reaction with PdClampoules. Details from makers of the above equipment (b) (c) (j). Draw air through O-tolidine reagent in special absorption tube. Draw air through 10% KT solution. Physical method such as ab sorption on activated char coal or by use of interfer ometer. Thermal decomposition meth od. <As above). Method of Determination Compare resulting color against standards. Itef.: Hig gins & Marriott. J. .\m. Chem. Soo., vol. 39, p. 3$ (1917). Volumetric gas anal, method. Ref.: U. S. Bureau of Mines Bulletin No. i ;> and I. C. 7017 (PCS). Determine xnnthate iodometrirally. Ref.: Matuszak, M. P.: Ind. Kng. Chem., Anal. Ed., vol. 4, pp. 9S-100 (1932). Iodometric. Determine CS-,,. as above. Ref.: Bnrthelemy, H. L.: Tubize Chatillon Corp., Rome, Ga., or Div. of Ind. Hyg., N. Y. State Dept, of Labor, SO Centre St., New York. Ref. r U. S. Bureau of Mines. Tech. Paper 5S2. Also: Drinker, C. K.: Carbon Monoxide Asphyxia, Chapt. S by Sendroy. Oxford Univer sity Press, New York, 193S. Transfer sample to Nessler tube and compare with stan dards after standing. Ref.: Porter: J. Ind. Rne\ Chem., vol. IS, p 730 (1920 >'. Iodometric. Ref.: Air Hvg. Bulletin No. 2, Part 3 (March, 193$). Equipment from (l) (m). Imptnger with approximately normal NaOH, or with elec tric precipitator. Iodometric. Ref: Bloomfield and Blum: U. S. Pub. Health Rep., No. 43. p. 2300 (192S). Determine chromate with x- diphenylcarbazide as indi cator. Ref.: Toe, J. H.: Photochem ical analysis. 2 vols. "Wiley & Sons, New York. 192S-1929. / MATERIAL Method of Collection Method of Determination Esters Gas-collecting bottles. Hydrolyze with NnOH, back titrate excess NnOH. Kef.: Pattv, Yant anl Sehrenk: U. S. Pub. Health Hep. No. 5J, p. Sll (l'OC). Ethyl bromide Ethyl chloride See MeBr. Formaldehyde Draw air through bubbh-r containing water. Colorimetric* method using Sehiffs soln. ,-. Also, Dc-nige method. Chapin, R. M.: J. Tud. Eng. Chem., vol. 1Z, p. .>-us tlS*21b Hydrocarbons, general (1) Zeiss portable interfer ometer. (2) Absorption on solid ma terials, such as activated charcoal' or silica pa-1 V Full information from <n>. Gas-collecting bottle. Volumetric gas analysis method 1C. Also, U. S. Bureau Mines I. C. 7017 (193S). Self-contained instruments operate on tlie heat of com bustion principle and give readings of the percentage of the lower explosive limits di rectly on dials. Special cali brations of the dials can be obtained depending on the application. Equipment from (b) (c) fj) cl). Hydrochloric acid Draw .air through glycerulpotassium carbonate-water soln. of the ratio 1:1:1. Determine chloride ion by Volhard method. Ref.: Hel ler: Gesund. Ingenieur. vol. 55. p. 2C1 (lfr32>. Chem. Abst., vol. 27, p. 355 (K*r;3). Hydrofluoric acid Draw air through bubbler containing KOH. Distill fluorides as hydrofiuosilicic acid. Titrate fluorides .in distillate with thorium nitrate s*dn. using sodium alizarine sulfonate as indi cator. I Ref.: Willard- and Winter: Ind. Kng. Chem., Anal. Kd., vol. 5. p. 7 flfCD. Boruff and Abbott. fibhD. vol. 5, p. 23G norm). l Hydrogen Draw air through bubblers Titrate with AgXfV.. cyanide containing 0.5rc KOH. l Colorimetric indicator. Range of 50-1.000 PP.M. Equipment from (j). Hydrogen See also carbon disulfide. Concentration is indicated by II sulfide Draw air through activated alumina coated with AgCN length of color change. Ref.: Littlefield, Yant and IVior: or TbAc. U. S. Bureau Mines, R. I. No. 3276 (June, 3SCSI. Instrument using this method sensitive to 25-100 PPM. In strument for colorimetric method using test paper sen sitive to 0.02*T supplied hv (j). See also: Reed. .T. D.: .T. Foe. Them. Ind., vol. 57. pp. 43-H (1!*3S). Draw air through bubbler containing P soln. in KI with starch. lodomet rk\ 15 OU'41 i / MATERIAL Lead, as dust or tyrne Mercury Methane Methanol Methyl bromide Methyl chloride Ethyl bromide Ethyl chloride Nitric acid Nitrooen tetroxide Oxygen Method of Collection Method of Determination Implnger or electric precipi tator. Draw air against SeS coated paper Lampshade detector (using SeS) available from (O O'). Frceze vapor with dry Ice. Gas-collecting bottle. Combustible gas indicator from (b) (c) U) (1). Flame Safety Lamps from (b) (c) (j). See Air Ilvg. Bulletin Xo. 2, Part 6 (153S). Compare color change against standards. Ref.: Xordlander, B. W.: Ind. Eng. Client., vol. 19, p. 522 (192.7). Rtf.: Fraser: J. Ind. Hyg. & Tox., vol. 1C, p. 67 (1534). Vol. gas anal, method *. Ref.: Hoet--v. syne, Currie. U. S. Bureau Mines Buli. Xo. 331 (1530). See also: U. S. Bureau Mines I. C. Xo. 33 (1537). Draw air through bubbler containing water. Collect sample in partly evacuated bottle. Absorb MeOlI in distilled water by thorough agitation of water in tlic bottle. Discussion. Ref.: Wright, L. O.: Ind. Eng. Chem., vol. 19, p. 750 (1527). Oxidiz.e to formaldehyde and determine color imetrically (Denige method) u. See also: Formaldehyde, Chapin's method. Determine by modified Dcntge method. Ref.: Schrenk and Tant: U. S. Bureau Mines. Personal communication (1533). Collect samples by He dis placement. Analyze volumetrically by slow combustion with a white-hot platinum coil and large excess of 0. Ref.:Payers, Yant, Thomas, and Berger. U. S. Public Health Bull. Xo. 1S5 (1929). For MoBr see also: Busbey and Drake: Ind. Kng. Chem., Anal. Kil., vol. 10, p. 390 (153S). Draw air through an acidi fied 5Co H-O* bubbler followed by 2 or 3 5c.'o KOH HsOj bub blers. Draw air through liquid air trap. Determine XaO- with phenolsulfonic acid by A. P. H. A. Standard method11. Ref.: Drinker and Snell: J. Ind. Hyg. & Tox., vol. 20, p. 321, (193S). Oxidize as above and deter mine by nitron acetate method. Ref.: Coltman: J. Ind. Hyg. & Tox., vol. 20, p. 2S9 (193S). Gas-collecting bottle. 16 Vol. gas anal, method 18. II. S. Bureau Mines I. C., 7017) (193S). 010 4 2 MATERIAL Ozone Phenol Phosgene Phosphorus trichloride Radioactive substances Sulfur chloride Sulfur dioxide Sulfuric acid (mist) Toluol Trichlor- ethylene Method of Collection Method of Determination Partially evae. bottles con taining starch-Ki solution. In presence of by liquid air. collect Draw air through bubbler containing NaOH solution. Draw air through bubbler containing aniline water sat urated with diphenyl-urea. Draw air' through bubbler containing Br water. Physical methods using elec troscope. Draw air slowly through HXOs solution of AgNOa. Draw air through IS-KI starch solution. Partially evacuated bottle containing I-KI starch soln. Draw air automatically through acid Draw air through NaOH in impinger. Draw air through fuming HKOa. Draw air through specially designed absorption tube containing absolute EtOH. Combustion method for chlorinated hydrocarbons. Indomclric Ref.: Collman and McPher son, J. ind. Hyg. &. Tox., Vol. .20, p. 4G5 (193S). Determine colorimetvlcally n. Kilter off precipitate of di phenyl-urea in tared Gooch crucible, dry and weigh, dis solve diphenyl-uvea with alcohol, dry, and . :v'iigh. Ref.: Yant, et al.: Ind. Eng. Chem., Anal. Ed., vol. S, p. 20 (1930. Boll and determine P by colorimetric molybdate meth od w Ref.: Schwartz, et ah: J. Ind. Hyg. & Tox., vol. 15, p. 362, 368, 433 (1933). Dissolve the precipitated AgCl in NH4OH again precipitat ing with HNOa55. Iodometric. Ref.: Griffin and Skinner, Ind. Eng. Chem., vol. 24, p. S62 (1932). Solution from sampling bottle brought to same intensity as a blank by addition of stan dard iodine solution. Ref.: TJ. S. Bureau Mines, R. I. Xo. 3005 0930). Conductivity method with recorder. Ref.: Thomas: Ind. Eng. Chem., Anal. Ed., vol. 4, p. 253 (1932). Acidify with HC1 and deter mine sulfate as BaSO<. Similar to U. S. Bureau Mines method for CH using KOH instead of XaOH. Determine colorimetrically .on reaction with pyridine and 50% sodium hydroxide. Ref.: Barrett: J. Ind. llvg. & Tox., vol. 18, p. 341 (193G). Air Ilyg. Bulletin Xo. 2, Part 3 (March, 1938). t- TABLE IV. FIRMS SUPPLYING EQUIPMENT MENTIONED IN THIS BULLETIN (a) Bausch & Bomb Company Rochester, New York. (b) E. D. Bullard Company 275 Eighth Street, San Francisco. California. (c) Davis Emergency Equipment Co. 55 Van Dam Street, New York. New York. 1 (d) Detroit Air Meter Company Detroit, Michigan. (e) Fisher Scientific Co. 709-717 Forbes Street, Pittsburgh. Pennsylvania. i ! i '- i : <f) General Electric Company 1 River Rd., Schenectady, New Y'ork. te> E. V. Hill Co. 179 West Washington Street, Chicago, Illinois. <h) Illinois Testing Laboratories, Inc. 420 N. LaSalle Street, Chicago. Illinois. (i) Macalaster Bicknell Co. 171 Washington Street, Cambridge, Massachusetts. . i!i { i ! <j) Mine Safety Appliances Company Pittsburgh, Pennsylvania. (k) Pulmosan Safety Equipment Corp. 176 Johnson Street, Brooklyn, New York. 0) Union Carbide Company---Linde Air Products, Inc. SO East 42nd Street, New York, New York. (m) Willson Products, Inc. 1 Reading, Pennsylvania. () Zeiss Company 485 Fifth Avenue, New York, New Y'ork. *- 18 010 4-4 .. * ' * V References 1. Report of National Silicosis Conference. U. S. Dept. Labor, Div. Labor Standards. Washington, D. C. 2. Industrial Code. Bulletin No. 33, New York State Dept. Labor. Rules Relating to the Control of Silica Dust in Rock Drilling (May, 1937). 3. Tentative Recommended Good Practice Code and Handbook on the Fundamentals of Design, Construction. Operation, and Maintenance of Exhaust Systems. American Foundrymen's Association, 222 IV. Adams Street, Chicago, Illinois. Price S-1.00. 4. Yaglou, C. P.: Thu INoN-d Thermometer Anemometer. J. R-.J. Hyg. & Tox., 20: 497, 193S. 5. Brown, C. E.; and Schrenk, H. H.: A Technique for Use of the Impinger Method.. U. S. Bureau Mines, I. C. 7026, June, 1938. 6. Drinker, P.; and Hatch, T.: Industrial Dust. McGraw-Hill Book Com pany, New York, New'York. Price S4.00. 7. American Society of Mechanical Engineers: Fluid Meters. 4th Edition, 1937. 29 West 39th Street, New York, New York. Price S3.00. I 8. Barnes, E. C.; and Penney, G. W.: An Electrostatic Dust Weight Samp ler. J. Ind. Hyg. & Tox., 20: 259-2C5. 1938. 9. The Vapor Pressure Method for Estimating the Concentration of Organic Vapors, such as Gasoline, in Air. U. S. Bureau Mines, Tech. Paper No. 87 (1916). This Bulletin is out of print. 10. Scott, W. IV.: Standard Methods of Chemical Analysis. 4th Edition. Van Nostrand Company, New York, New York. 1927. 11. Standard Methods for the Examination of Water and Sewage. 9th Edition. I93G. American Public Health Association, New York, New York. 12. Zhitkova. A. S.; Kaplan, S. D.; and Ficklen, J. B.: Some Methods for the Detection and Estimation of Poisonous Gases and Vapors in the Air. A Practical Manual for the Industrial Hygienist. Service to Industry, Box 133, West Hartford, Connecticut, pp. 198. 13. Cook, W. A.; and Coleman, A. L.: Determination of Solvent Vapors in Air by Means of Activated Char-coal. J. Ind. Hvg. & Tox., 18: 194-210, 1936. 14. Cook, W. A.: The Industrial Hygiene Laboratory. J. Ind. Hyg. & Tox., 18: G23-636, 1936. 15. Flury, F.; and Zernik, F.: Schadlicbe Gase. Julius Springer, Berlin (1931) 16. Gas Chemist's Handbook. American Gas Association, New York, New York. Revised from time to time. 19