Document 0q6V7qnR6wkGLM2qDomLbnXgm

R&S 004081 4 &c~~ -- /Umt (Z&NJ- J THE DOW CHEMICAL COMPANY 5^ TEXAS DIVISION FREEPORT, TEXAS 77541 L. Adcock, OCD c.v R- L. Daniel, A-1201 D. E. Hamilton, Sarnia W. Rittershausen, Stade F. Vreugdenhil, Terneuzen B. J. Williams, Ulsan C. L. Melancon, Plaquemine R. R. Oubre, A- 2410 cc: t^Ghet Otis, Midland Irving Snyder, Midland R. C. Walker, B-1903 CONTINUOUS AIR MONITORING FOR CHLORINATED HYDROCARBONS Attached is a copy of equipment requirements for continuous air monitoring, source directory for equipment, and backup data. It is the recommendation of the Chlorinated Hydro carbons Technology Center that each plant install one of these units so that we can have a permanent record of our chlorinated hydrocarbons levels throughout the plant. If you need further details please contact A. A. Allemang, 238-4640. We have enclosed background data so you can have some knowledge of the problems you will encounter. pm end C-.i C. A. Christian Technical Manager Chlorinated Hydrocarbons Technology Center A-1201 December 1, 1972 R&S 004082 EQUIPMENT REQUIREMENTS FOR CONTINUOUS AIR MONITORING FOR CHLORINATED HYDROCARBONS CHROMATOGRAPH A single column, isothermal unit equipped with a flame ionization detector. Suitable chromatographs can be purchased from Varian Aerograph, Beckman Instruments, Hewlett-Packard, Perkin-Elmer, Amsco, and a number of other manufacturers. RECORDER One millivolt, with one second, full scale response time. Recommended are Bristol Dynamaster, Leeds and Northrup Speedomax XL-610, and Sargent SR-20. PROGRAMMER A process analyzer Sample Selecting System for use with a multi-stream analyzer (12 sample streams minimum). The programmer must be capable of operating solenoid and air operated valves. Suitable units are available from'Beckman Instruments and Process Analyzers, Inc. A Dow designed unit is manufactured by Amsco. AUTOMATIC ATTENUATOR A solid state automatic attenuator is recommended. Acceptable units are manufactured by Esterlingangus, Areas, and Process Analyzers, Inc. Non-solid state automatic attenuators are available from Hewlett-Packard and Perkin-Elmer. SAMPLE VALVE A t'dtary gas sample valve manufactured by Valeo (available ffff Antek Instruments) is recommended. Slide valves, manu factured by Areas or Beckman may also be useci. hit perated toggle valves (from In-Val-Co) should be used fi the hydrogen supply to the detector as a safety feature. COMPANY DIRECTORY Amsco P. 0. Drawer HH Angleton, Texas 77515 Antek Instruments, Inc, 6005 N. Freeway Houston, Texas 77022 In-Val-Co P. 0. Box 556 Tulsa, Qkla. Leeds and Northrup Summeytown Pike North Wales, Pa. 19454 Areas 2040 Kipling Houston, Texas 77006 Beckman Instruments, Inc. 2500 Harbor Blvd. Fullerton, Calif. 92634 Perkin-Elmer Corp. 702-G Main Avenue Norwalk, Conn. 06852 Precision Scientific Co. 3737 W. Cortland St. Chicago, 111. 60647 R&S 004083 Curtin Scientific Co. P. 0. Box 1546 Houston, Texas 77001 Esterlingangus Div. of Esterling Corp. Box 2400 Indianapolis, Indiana 46224 Fisher Scientific Co. 711 Forbes Ave. Pittsburgh, Pa. 15219 Process Analyzers, Inc. 6400 S.W. Freeway Suite 400 Houston, Texas 77036 Sargent-Welch Scientific Co. 7300 N. Linder Ave. Skokie, '111. 60076 Varian Aerograph 2700 Mitchell Dr. Walnut Creek, Calif. 94598 Hewlett-Packard 1430 East Orangethrope Ave. Fullerton, Calif. 92631 - '`jit R&S 004084 00 EXPOSURE TO CHLORINATED HYDROCARBONS ' COMPOUND OSHA STD. Vinyl Chloride Ethyl Chloride Vinylidene Chloride Methylene Chloride 1,1-dichloroethane Chloroform 1,1,1-trichloroethane Carbon Tetrachloride Ethylene Dichloride Trichloroethylene Propylene Dichloride 1,1,2-trichloroethane Perchloroethylene 1', 1,1, 2-tetra- chloroethane 1,1,2,2-tetra- chloroethane 500 ppmm 1000 25 500 100 50 350 10 50 100 75 10 100 100 5 A O H O ViV2 EXPOSURE * 7.0 ppmm 1.2 0.34 0.29 0.32 <0.10 0.86 <0.10 0.64 <0.10 <0.10 0.18 <0.10 <0.10 OCD expos u: 0.35 ---- -- -- -- -- -- -- -- ---- 0.10 -- -- MM NOTE 1. OSHA STD - Occupational Safety and.Health Act maximum exposure level, 8-hour time weighted average 2. .Dow standard for vinyl chloride is 50 ppm^ 3. OCD found an area during their survey where personnel could be exposed to concentration of vinyl chloride as high as 1000 ppmm. AAA:pm 12-4-72 R&S 004085 AIR MONITORING FOR CHLORINATED HYDROCARBONS SCOPE This method is applicable to the determination of chlorinated hydrocarbons in ambient air.at concentrations from 0.1 ppm. EQUIPMENT Chromatograph Conditions: - Dow designed, Amsco built flame ionization detector Column - 12' x 1/4" 14% Polyethylene grease SD446 on Chromosorb W-NAW, 60/80 mesh Temperature 85C Carrier - Nitrogen, .50 mls/min. Air - 250 mls/min. Hydrogen - 25 mls/min. Sample size - 2 ml. Recorder - Bristol Dynamaster Programmer - Dow designed, Amsco built Automatic attenuator - Dow designed, Amsco built Sa'mple valve - air operated MOBIL SAMPLING STATION The base of the mobil sampling station is a trailer 36" x 72". A wooden cabinet (3/4" plywood) 60" x 30" x 30" is mounted on the trailer to house the chromatograph and associated equipment. Four gas cylinders, air, hydrogen and nitorgen are placed on the rear of the trailer and chained to the wooden cabinet. Racks are pro vided on the rear of the cabinet for the power cord, sampling lines, and air line. To make the sampling station intrinsically safe all corners of the cabinet are sealed. All service lines enter through holes drilled in the' rear of the cabinet and these are sealed with Silastic2'. The doors of the cabinet are stripped with polyurethane. The cabinet is under a slight air pressure supplied by an air line connected to the plant air system. Automatic shut down switches are installed as follows: 1) loss of carrier gas pressure shuts down electrical power and hydrogen flow; 2) loss of cylinder air pressure shuts down hydrogen flow; and 3) loss of air purge to the cabinet shuts down electrical power and hydrogen flow. If a shut down occurs, manual reset is required before start up of the unit. STANDARDIZATION A standard mixture of the chlorinated hydrocarbons of interest is made. Ten microliters or a multiple thereof is placed in a calibrated one gallon bottle. The bottle is capped and stirred using a magnetic stirrer until all the liquid has evaporated. The cap is them rauoved and a line from the chromatograph sample valve is dropped to the bottom of t.ne bottle. Sample from the bottle is purged through the sample loop for one minute then the sample valve is manually operated. Mole parts per million of each chlorinated hydrocarbon is calculated from the number of moles added to the bottle in the 10 ul of standard mixture divided by the total moles of air in the bottle at ambient conditions. From the valves, peak height factors are developed for calculation of concentrations of chlorinated hydrocarbons in air. Samples are brought to the station through 1/4" Saran-1' tubing from remote locations S', 15' and 30' above ground level. An air as pirator moves t.os air through the Saran'' tubing into the chromato graph sample valve. A solenoid valve, downstream of the sample loop closes to allow the sample loop to come to atmospheric pressure. The programmer then activates the air operated sample valve. Sampling is at thirty minute intervals alternating between the t^ree .---- v^. . A. A. .-.Hemsno A-2422 fn R&S 004086 MONITORING PERSONNEL EXPOSURE TO CHLORINATED HYDROCARBONS SCOPE This procedure is a fast, effective and accurate method for determiningpersonnel equivalent exposures to chlorinated hydrocarbons in an in dustrial work environment. STANDARDIZATION To prepare standard concentrations in air permeation tubes are used. Intramedic1' polyethylene tubing, from Curtin Scientific with an I.D. of 0.962", O.D. of 0.032", and 12 cm length was used to make the permeation tubes. The polyethylene was heated slightly in an open flame until soft and was then sealed by crimping with pliers. The tube was then filled to one-half volume with the chlorinated hydrocarbon to be tested, and the open end sealed, being careful to pinch the tubing to avoid contacting the liquid with the flame. For lighter materials, i.e. vinyl chloride, one end of a piece of nylon tubing (Samuel Moore Co., 1/4" x 0.062" wall, 12 cm long) was capped with a brass Swagelok tubing fitting and the other end was fitted with a Microsep^ (teflon backed chromatographic septum) in a Swagelok nut. Vinyl chloride was cooled in a dry ice-vinyl chloride bath and injected into the tube using a Hamilton syringe. After preparation, the permeation tube was weighed and placed in an adsorption apparatus consisting of (Figure 1) two 1/2" x 2" steel swages coupled together anc connected to a Moore air filter. (Fig. 2). Thirty (30) mis of activated carbon were charged to the air filter and supported by a double layer of screen. Glass wool was placed above the carbon. The screen is held in place by a plastic cap. Air is purged through the apparatus at 2.8 1/min. After' 2-6 hours, the air flow is stopped and the permeation tube removed and reweighec. The carbon was extracted with one mole of carbon disulfide which is analyzed by gas chromatography. The grams of chlorinated hydrocarbon recovered are used with the weight loss of the permeation tube to calculate the efficiency of the adsorption-extraction procedure. R* S 004087 R&s 004088 CHROMATOGRAPHIC Instrument - Varian Aerograph Series 1400 temperature pro grammed, flame ionization detector. Column - 12' x 1/4" 16% polyethylene grease SD 446 on 60/80 mesh Chromosorb W-NAW Conditions - Temperature Inlet - Detector Column - 110C 200C programmed from 60C for 340 secs to 120C at 20C/min. -- Ga s e s Carrier Air H2 N2/ 30 ml/min. 250 mls/min 25 mls/min Sample Size - 10 ul Elution Times - see attached PERSONNEL MONITOR: Unico C110 Air Sampler - See attached bulletin To the side of this unit, a plexiglass holder, 1-3/8" square by 6 V long was attached. This held a glass adsorption column, 1" glass tubing, 5-3/4" long, closed at one end. A 1/4" glass tube extends down the center of this tube to within 1/2" of the bottom and pro trudes 1/2" above the top of the 1" tube. Thirty grams of carbon is charged to the adsorption column. (Figure 3). This unit is then strapped to the individual to be monitored. At the end of the sampling period (8 hours) the carbon is removed and extracted with CS2 and analyzed by gas chromatography. CALCULATIONS Efficiency of the adsorption - Extraction Efficiency - grams recovered in CS? x 100 weight loss of tube in grams Exposure Concentration Sample concentration in air = (A)(B) ppm mole (C)(D) Where: A = sample concentration in CS2 from chromatogram,ppm. B = moles CS2 C = Adsorption-Extraction efficiency D = Total moles of air sampled .............. ' " Equivalent Exposure for a mixture of air contaminants Em = C; Li + C2 L2 + . ........... Cn Ln Where: Em = equivalent exposure for .the mixture C = concentration of a specific contaminant L = exposure limit for that contaminant (OSHA Standard) (attached) A- A. Allemang A-2422 11/22/72 fn 33 flo CO OO <cooo JO 8 w o otoou 2I^`r, vrC GLASS WOOL 30 MLS ACTIVATED CARBON PLASTIC CAP SCREEN R&S 004091 R&S 004092 FIGURE 3 3rictiYsid' C?' Ri.inE 18 ELUTION' TIMES (minutes from injection! R&s 004093 COMPOUND TIME/ MINUTE?. VINYL CHLORIDE 2.1 ETHYL CHLORIDE 2.6 METHYLENE .CHLORIDE 4.0 V1NYLIDENE CHLORIDE . 4.3 1,1-DICHLOROETHANE 5.5 CARBON DISULFIDE 6.5 CHLOROFORM 7.4 ETHYLENE BICHLORIDE S.2 1,1,1-TRICHLOROETHANE 8.7 CARBON TETRACHLORIDE 9.6 PROPYLENE DICHLORIDE 10.1 TRICHLOROETHYLENE 10.9 1,1,2-TRICHLOROETHANE 12.7 PERCHLOROETHYLENE . 16.8 1.1.1.2-TETRACHL0R0ETHANE 17.5 1.1.2.2-TETRACHLOROETHANE 22.1 BULLETIN 8065 APPROVED DY U.S. BUREAU OF MINES FOR INTRINSICALLY SAFE OPERATION IN EXPLOSIVE ATMOSPHERES .. R&S 004094 The only lightweight, compact personnel monitor powered by a rechargeable Nickel Cadmium battery designed to these exacting Bureau of Mines Specifications. Eight hours continuous Midget Impinger sampling at a calibrated flow of 2.8 liters per minute. Eight hours continuous sampling with a Two-Stage Respirable Mass Sampler. The Unico Model CllO is the only personnel air sampler capabte of providing full-shift sampling at a calibrated air flow of 2.3 liters per minute. Eight hours continuous sampling through any filter media. UNICO UNICO ENVIRONMENTAL INSTRUMENTS, INC FALL RIVER. MASSACHUSETTS OS72Q