Document jgXJxwDmBqELzQJG9XQdJgQo5

ALLIED CHEMICAL CORPORATION MEMORANDUM received BY APR 9 1974 j. M. QU1NI1 April 5, 1974 To : Mr--J. -M. Quinn Dr. A. R. Paterson Mr. R. J. O'Leary Subject: Vinyl Chloride Sampling and Analyses Attached herewith are photocopies of two items con cerned with the sampling and analyses of Vinyl Chloride: one from the Shell Oil Company, and the other from the MCA office. If there are any questions regarding Shell procedure, it is suggested you proceed as directed by Mr. Kusnetz. 77~ W. A. Knapp WAK:mn Attach. AS! 00023577 Analytical Method IIC-604-74 2 (i) Nylon Web Straps, 13-foot length, Thcae straps are used to construct a harness to fit the worker and are used to support the air-sampling bag. See appendix for description. (j) Glass Syringe, 100-cc. (k) Hypodermic Needles, 1-1/2" length, 18-gauge, PROCEDURE FOR 7- TO 8-HOUR AVERAGE SAMPLES 4. (a) Fasten the belt supporting the SKC Model 222-2 modified pump around the waist of the worker. The pump is worn on the worker's left side. (b) Fit a nylon webbing strap "jacket" equipped with a cloth sack to the operator. The cloth sack with inserted plastic bag is worn on the upper part of the worker's shoulders above chairback level. See Figures 1 and 2, Choose the proper 9" x 9" or 6" x 12" bag material according to the material expected to be sampled. See Tables I and II, In choosing the bag, consider bag loss and memory. (c) Attach the Teflon air intake line of the pump to the worker's collar by means of a spring-loaded clip, so that the open end of the line is 3 to 4 inches below the chin. (d) Route the Teflon tubing from the pump discharge over the worker's left shirt pocket, over the left shoulder, and across the back to the rubber serum stopper valve of the air bag. Secure the line in place by attaching it to the strap jacket supporting the cloth sack and bag by means of safety pins through tabs of glass tape wrapped around the line. Also pin the line to the cloth sack at the top edge of the sack between the shoulders. Inspect the line for best positioning so as not to interfere with worker's movement. Attach a 1-1/2-inch 18-gauge hypodermic needle, bent at a 90 angle, to the end of the pump discharge line and puncture the rubber serum stopper closure on the bag valve, (e) Turn the pump switch to the "ON" position. Note the time of day, (f) At the end of the 7- to 8-hour sample period, turn the pump switch to the "OFF" position, remove the sampling equipment from the worker. Note the time of day. (g) Before analysis, mix the contents of the plastic sampling bag by kneading. Withdraw g.ir from the bag into a 100-cc glass syringe 7y.u return to the bag several times to make sure the air contained ny the valve stem is the same as in the bag. Withdraw a measured volume of air for analysis by gas chromatography, ASj 00023584 (h) Recharge the pump battery for a 16-hour period before reuse. Analytical Method IIC--604--74 3 NOTE: This pump has been found to have a constant pump rate over the 7- to 8-hour period- The pump rate should be verified once a week at the beginning and end of the shift. This can be done by attaching the pump discharge line to a soap film meter and timing the pump delivery with a stopwatch over a 5-minute period. The pump should be checked for proper working order each day before use by observing the volume of a single pulse (can 0.7-0,8 cc), PROCEDURE FOR TAKING EXCURSION SAMPLES NOTE: This procedure is used for taking samples for short periods of time from 10 minutes to 1 hour duration in areas of suspected higher-than-8-houraverage concentrations. 5, (a) Attach the Calibrated Instruments pump to a strap or web belt which can be worn loosely around the worker's neck with the pump resting against the worker's chest below the chin, See Figure 3, If the worker's duties involve bending over, attach a nylon strap around his body (under the arms) and through the strap supporting the pump. This prevents the pump from swinging away from the body when bending over. (b) Attach a cloth sack containing a plastic air bag to the strap or belt supporting the pump so the sack is positioned between the worker's shoulder blades. See Figure 4. (c) Route the 1/8" OD Teflon tube from the pump exhaust to the plastic air bag by going under the worker's left arm. Attach an 18-gauge needle, bent at right angles, to the end of the delivery tube and puncture the rubber serum stopper. Secure the delivery tube to the worker's clothing by means of safety pins pinned through tabs of glass tape wrapped around the delivery tube, (d) Turn the pump switch to the "ON" position and record the time of day. (e) When the sample has been collected, turn the pump switch to the "OFF" position and record the time of day. (f) Remove the sampling equipment from the worker. (g) BAG CLEANUP Be turf' analysis, mix the contents of the plastic bag by kneading the bag. Withdraw air from the bag with a 100-cc glass syringe and return the air to the bag several times to make sure the air contained in the valve stem is representative of the air in the bag. Withdraw a measured volume of air for analysis by gas chromatography. ASI 00023585 6. Bags may be reused if they are cleaned after each use. The cleanup procedure is as follows: Analytical Method HC-604-74 4 (a) Puncture the serum stopper with an 13-gauge needle and evacuate the bag. (b) Fill the bag with clean water-pumped compressed air. (c) Evacuate the bag and fill with air. (d) Let the bag stand for 24 hours. (e) Repeat steps (a)-(d) as many times as necessary to reduce the bag memory to acceptable limits. Refer to Table II for bag memory data. Clean-up time is one day less than the cumulative time given in the table. DOCUMENTATION 7. Record the following information in a bound permanent record book: (a) Name of the worker. (b) Job assignment or description. (c) Date of sample. (d) Time of day at start and end of sample period. (e) Bag material used to collect the sample. (f) Wind direction and speed. (g) Pertinent facts regarding conditions during period of taking the sample such as known high exposures and duration of high exposure, leaks, spills, etc. Ch) Pump rate at beginning and end of sample period each time it is checked. (i) The analytical data for the sample. (j) The analyst should sign and date each page of the record book. Houston Plant March 5, 1974 WMA:oc AS] 00023586 Analytical Method 110-604-/4 APPENDIX PUMP MODIFICATIONS The SKC Model 222-2 pump can not be used as received to pump air into plastic bags. It was designed for drawing air through a trap. The major modi fications consist of removing the supplied diaphragm pump and check valve and replacing them with a shortened 5-cc glass syringe to act as a pump and a differ ent check valve. Figures 5 and 6 show the modifications from a side view and a top view. The detailed procedure for modification of the pump is as follows: 1. Remove the three Phillips screws in the pump top. Lift the top and cut the rubber tubing inside. Raise the metal can surrounding the pump and drop the top cover through the can. .2 Loosen the three slotted screws in the bottom plaice of the pump. This permits lifting the plate resting on top of the battery. Remove the screws holding the check valve and diaphragm pump. Discard the valve and diaphragm pump. 3. Enlarge one of the screw holes in the plate and insert an 8-32 x 2" flathead screw to serve as a pivot post for the syringe. Secure with a nut. See Figure 6 for proper location of pivot post. 4. Install a 6-32 x 2" flathead screw In one of the existing check valve screw holes. Secure with a nut. This screw will be used to secure the new check valve. See Figures 6 and 7. Replace the slotted screws removed in Step 2 and position battery and clear plastic spacer in place between the bottom of the pump and the plate on top of the plastic spacer. 6, Cut a hole in the rubber sheet on the underside of the top cover plate of the pump. Refer to Figure 9 for the location. Use a 3/8" OD cork borer. Drill a 21/64" diameter hole in the metal cover. Install a 1/8" stainless steel 316 Swagelok Bulkhead Union (200-61-316) in the hole. Blow all metal fragments from pump. 1\ Remove the screw holding the ball bearing race. Save parts. 8. Loosen the Allen head screws in side of the top 1-5/32" diameter aluminum drive disc. Lift off the disc. 9. Drill a ho1c through the disc. 6 rm off center, and tap with 5-40 threads. .10 Replace the drive disc and tighten the Allen head screws. ASI 00023587 11. Cut: a 9/16" length of 1/4" OD stainless steel tubing. Remove burrs from inside tubing. Secure a 20-gauge needle hub to the tubing by either cementing with epoxy cement or by silver soldering. The position of the needle relative to the tubing is 90. When the epoxy cement has cured, make a bend in the 20-gauge needle close to the hub. The bend should be a 90 bend and downward. Refer to Figure 5 for correct position. Analytical Method HC--604--74 - Appendix 2 12. Using a glass saw, cut a 5-cc glass syringe with metal Luer-Lok tip at the 2-4-cc mark. Cut the plunger 1/16" longer than the syringe barrel, 13. Machine a brass plug to fit snugly inside the sawed-off glass plunger. Dimensions are 3/8" length, 0-33" diameter. Drill a hole (0.1015" diameter, if38 tap drill size) longitudinally in the center of the plug, 14. Cut a 7/8" length of 1/4" stainless steel tubing (remove burrs) and slip over the pivot post for the syringe. 15. Cut the connecting pin, which formerly connected the ball bearing race to the pump diaphragm, in half, 16. Screw one-half length of the connecting pin into the ball bearing, 17. Fasten the ball bearing to the aluminum drive disc with a 5-40 x 1/2" roundhead screw. Place enough flat washers under the bearing to raise it enough so the glass plunger will clear the top surface of the drive disc when the syringe is at the end of the intake stroke 18. Carefully measure the distance from the base plate to the center of the piston rod. Add sufficient flat washer spacers to the pivot post to obtain the same measured distance between the base plate and the center of the syringe needle, 19. Apply epoxy cement to the inside of the glass plunger (the first 1/2" of the open end), the outside walls of the brass plug, and the hole in the plug, Remove the ball bearing from the disc. Assemble as a unit the ball bearing, piston rod, brass plug, glass plunger, syringe barrel, and needle hub. Lower the unit into place, slipping the needle hub over the pivot post and secure the bearing in place over the proper number of flat washers. Tighten the screw holding the bearing. 20. Start the motor and rotate the drive disc until the bearing is at the posi tion of full compression. Stop the motor. Position the plunger in the syringe barrel to read zero volume. Position the brass plug in the open end of the syringe plunger. Let the epoxy cement cure with the parts remaining in this position. 21. Apply a "dot" of epoxy cement to the piston rod where it screws into the ball bearing race to prevent its unscrewing during later use. Also, apply epoxy cement to the juncture of the Luer-Lok tip portion of the syringe barrel and the needle hub to prevent loosening of the syringe barrel during later us-'ge, 22. When the epoxy cement has cured, start the syringe motor and let it operate and inspect to see if properly aligned. A slight up-and-down motion of the needle hub on the pivot post is permissible. Slip one flat washer over the pivot post and then two nuts, Position the bottom nut so there is space the thickness of a washer remaining between the washer and the nut at all times during operation of the syringe. Do not tighten to bind the syringe. Tighten the second nut against the first nut to lock both nuts in place. AS I 00023588 Analytical Method 1IC--604--74 - appendix 3 23. Fasten the new check valve [No. 3094 (470V) valve from a Becton-Dickinson No 3560 filling outfit, Curtin No, 221-523] to a 6-32 x 2" flathead screw installed in Step 4 Secure by wire or any other convenient means. 24. Attach an adapter (female Luer slip to 1/8" ID tubing, Becton-Dickinson Part No. L/606) to the discharge end of the check valve. Attach another adapter (Becton-Dickinson No0 H/468L, male Lucr-Lok slip to 1/8" ID tubing) to the syringe end of the check valve. Sec Figure 7. NOTE: The adapters In Steps 24 and 25 are not shown in the photograph of an early model check valve, A later model uses the adapters. 25. Slip a 3" length of 1/16" OD Teflon tubing over die syringe needle and insert the other end inside the adapter on the syringe end of the check valve, Epoxy cement in place on the check valve adapter, 26. Cut a 5-1/2" length of 1/8" OD Teflon tubing. Attach one end to the adapter on the check valve discharge. Use a short sleeve of Tygon tubing to slip over the adapter and the Teflon tubing. Butt fit the Teflon tubing against the adapter so there will be minimum contact of sample with Tygon. The other end of the Teflon tube will be attached later to a 1/8" stainless steel 316 Swagelok bulkhead union, installed in the top cover of the pump. 27. Cut a 2-1/2-foot length of 1/16" OD Teflon tubing and attach to the check valve intake. Insert one end inside a one-inch length of 15-gauge SW Teflon spaghetti. This is a tight fit. Insert the end of the 15-gauge spaghetti into a 1/2" length of 1/8" OD Teflon tubing with an ID of 0.09". Butt fit the assembled pieces of Teflon tubing to the check valve intake with a short sleeve of Tygon tubing. If any part of the smallest Teflon tubing protrudes inside the check valve entrance, make sure it does not touch the small rubber poppet valve inside the check valve. Apply epoxy cement at the junctures of the various pieces of tubing. Let cure, 28. Remove the stainless belt loop on the side of the pump can and replace it with a loop that will accommodate a large belt See Figure 8 for dimensions of the new loop. 29. Reassemble the pump inside its container, Pull the top cover through the can as tne can is lowered over the pump Slip the 2-1/2" x 1/16" Teflon air intake tube through the air intake hole in the top of the can. Attach the 5-1/2" length of 1/8" OD Teflon tubing from the discharge of the check valve to the bottom end of the bulkhead union When everything is in place, fasten the top cover in place with the three Phillips screws. iu ,, Attach a spring-loaded clip to the end of the air intake tube as the tube may be attached to the worker's collar, A glass tape tab may be formed around the Teflon tubing and the clip can be fastened to the tab. Cut a 2-1/2-foot length of 1/8" OD Teflon tubing- Attach one end to the Swagelok bulkhead union on top of the pump cover. This tube is the pump discharge line. To the other end attach an adapter (Becton-Dickinson male Luer-Lok slip to 1/8" ID tubing, Part No H/468L). Using a sleeve of Tygon tubing, butt fit the Teflon against the adapter. AS I 00023589 Analytical Method HC-604-74 - Appendix 4 32. Attach fiberglas tape tabs at various locations along the length of the pump discharge line so the line can he pinned to the strap harness used to support the plastic bag. Loops in the line that interfere with the worker's movements must be avoided. 33r bend a 1-1/2-inch length 18-gauge needle at right angles midway on the length of the needle- This needle will be attached to the Luer-Lok adapter on the end of the pump discharge line and penetrate the rubber serum stopper closure of the plastic bag. GAS SAMPLE BAGS Before using the plastic sample bags, open the Nalkey-Roberts valve wide open. Seal around the base of the valve stem with epoxy cement to prevent the valve from leaking in the open position. The valve openings are closed with rubber serum stoppers. Stick two 2-inch lengths of plastic electrical tape, criss-cross fashion, to the bag on the side opposite the valve. This protects the bag from punctures caused by pressing the metal valve against a hard surface during cleaning the bag or changing septums. New aluminum foil-polyester bags should be leak tested before use. This can be done by inflating with clean air and immersing under water. Leaks are sometimes found at the sealed edges of new bags. STRAP HARNESS FOR 7- TO 8-HOUR SAMPLES A nylon strap harness was constructed to support a cloth sack contain ing the plastic air bag. It is not desirable to pin the cloth sack directly to the worker's clothing. In cold weather, the worker often needs to wear a coat. It is undesirable to wear the coat over the bag. If all of the air lines and air bag are attached to the strap harness, he may remove the harness with sampling equipment intact while putting his coat on or taking it off and then return the strap harness to its normal wearing position- The harness may be constructed from nylon strap tie-downs for automobile car top carriers These are available at auto accessory stores. Approximately 13 feet of material is needed. The harness consists of a waistband with a buckle on one end, a shoulder strap over each shoulder, a horizontal strap across the shoulders, and buckle straps in an area below the chin. The waistband is cut to 50 inches length. The two shoulder straps (42" each) are sewed to the waist band at a point 20 inches from the buckle- The other end of one of the shoulder straps is sewed to the waistband at a point 5 inches from the buckle.. A loop is sewn in the other end of the second shoulder strap so the waist hand can slip through the loop.. A strap 11 inches long is attached to each shoulder strap 20 inches from where the shoulder straps attach to the waistband in the back, This forms a horizontal strap across the shoulders for attaching a cloth sack Short 6-inch straps, one with a buckle, are sewn to each shoulder strap at a point 15 inches above where the shoulder straps attach to the waistband in front of the worker. 00023590 Analytical Method HC-604-74 - Appendix 5 BAG LOSS Bag loss data for Teflon bags and the aluinlnized-polyoster bags were determined by preparing a mixture of the organic chlorides at the 5- and 40-ppm level in 1000 cc of air in each bag. Each mixture was analyzed in duplicate immediately after make-up and again after standing 8 hours and 24 hours. The loss of peak area (FID detector) for each component was calculated as the percent loss of component, The experimental data are summarized in Table I, BAG MEMORY Teflon and aluminized-polyester bags were filled with 1000 cc of an air mixture of the organic chlorides at the few multiples of 10 ppm level and stored for 24 hours. The bags were then evacuated and filled with air several times to get rid of the concentrated air mixture,, One thousand cc of clean air was measured into each bag, and the bag was allowed to stand for 24 hours at room temperature before analysis. After analysis, the bags were emptied and flushed as above and again filled with 1000 cc of air and allowed to stand for 24 hours before analysis,. This process was repeated after each 24-hour period, The bag memory samples were analyzed by gas chromatography with an FID detector, Freconcentration of the sample was achieved by trapping sample sizes ranging from 100 cc to 600 cc in a liquid-nitrogen-cooled trap before charging to the gas chromatograph. The experimental data are given in Table II. In determining the time of cleanup required for reuse of the bag, it must be remembered that the cleanup time is one day less than the cumulative number of days in the table. For example, If the bag was cleaned for one day followed by air removal and the bag was used on the second day, the value in the table for the second day is the contribution from the bag to 1000 cc of sample for a 24-hour period. If an eight-hour sample were taken and analyzed immediately, the bag memory effect would be less than shown in the table. AS I 0023591 TABLE T BAG LOSS DATA Vinyl Chloride Ethyl Chloride Isopropyl Chloride Allyl Chloride Ethylene Dichloride 1,2-Dichloropropane cis 1,3Dlchloropropene Epichlorohydrin trans 1,3Dlchloropropene 1,2,3-Trichloropropane Teflon (6" x 12 ") Storage Time Initial ppm (v) 3~Hr, % Loss 24-Hr, % Loss 5 -1 _-67 43 -2 5 0 -5 46 --4 -7 6 0 -4 49 -2 -5 8 -2 -9 54 -4 -9 4 -8 -19 41 -7 -19 5 _4 -15 33 -7 -17 _ --35 -12 -29 5 0 -26 27 -2 -28 5 -18 -42 33 -11 -35 2 -13 -45 11 -22 -47 Aluminum-Polyester (9" x 9") Storage Time Initial pptn (v) 8-Hr, % Loss 24-Hr, % Loss 4 -1 -2 44 0 -2 4 0 -1 44 0 -1 5 0 -1 47 0 -1 5 -1 -4 52 -1 -3 4 -7 -18 33 -1 -6 3 -4 -10 25 -3 -4 3 -8 -24 24 -9 -13 2 -7 -40 20 -6 -19 2 -11 -35 19 -8 -17 1 -12 -25 4 -21 -20 As* 00023592 TEFLON (6" x 12") Vinyl Chloride Ethyl Chloride Isopropyl Chloride Allyl Chloride Ethylene Dichloride 1,2-Dichloropropane cis 1,3-Dichloropropene Epichlorohydrin trans 1,3-Dichloropropene 1,2,3-Trichloropropane TABLE II BAG MEMORY DATA Initial Exposure ppm (v) 40 42 57 67 35 41 31 44 45 16 Day 1 0.5 0.5 0.7 1.9 2.1 2.2 27 3.4 4.2 1.3 ppm (v) Day 2 Day 3 Day 4 0.09 0.01 0.06 0.08 0.13 0.22 0.29 0.27 0.41 0.22 0.05 0.01 0.03 0.02 0.04 0.09 0,06 0.07 0.10 0.22 0.02 N,D. 0.03 0,02 0.02 0,06 0,03 0.05 0.06 0.10 Day 5 0.06 0.01 0.02 0,02 0.02 0,06 0.01 0.01 0.03 0.09 ALUMINIZED-POLYESTER (9" x 9") Vinyl Chloride Ethyl Chloride Isopropyl Chloride Allyl Chloride Ethylene Dichloride 1,2-Dichloropropane cis 1,3-Dichloropropene Epichlcro*irin trans 1,3-Dichloropropene 1,2,3-Trichloropropane Initial Exposure ppm (v) 40 42 57 67 35 41 31 44 45 16 gy_A 0.4 0.4 0.9 1.6 2.1 3.5 2,5 4.5 4.0 1.7 ppm (v) Day 2 Day 3 Day 4 Day 5 0.09 0.04 0.03 0,16 0-. 29 0.51 0,43 0.87 0.86 0.72 0,08 0.03 0.01 0.09 0.13 0.13 0,18 0.49 0.46 0.65 0.06 0.02 <0.01 0.07 0.10 0,06 0.11 0,31 0.32 0,33 0.05 0.01 <0.01 0.05 0.08 0.05 0.09 0.25 0.24 0.24 00023593 AS I i fcnrc ^ front vlf.w of woukkr_and .]C,HT HOUR SAMPLING EQUIPMENT AS I 00023594 1 i,'l . l' ' >\< ,TU ^ ?! 1 ;!(; ({'74 .....1 - ife * 7,4*^ v;^ kmssb^.JYj - .* -*i? fc *%&%* i ;; .f* -----t#^V.,v jtvvfx" /, !' r\Vr<$J\0$k ' -v. X^"''P 7 f>i '<^. '/.' ivvi.vv^fsj^ "ft * l " . e '. ,p.' .7,1 '>*' '`I L-*n" * !L: lu .* , ''.- VVv'^'i` > l * V" 'jvfeVJi f)V s . .. h. -;!Vl,-it* p.S*fe^p./<*. 1 ,v W'VTl J>* r;?' wh'.^yi ~ 'i;W lT i'V ^Vte;;#1 iRure 2. REAR VIEW OF WORKER AND EIGHT HOUR SAMPLING EQUIPMENT AS I 00023595' Figure 3. FRONT VIEW OF WORKER AND EXCURSION SAMPLING EQUIPMENT AS I 023596 Figure 4. REAR VIEW OF WORKER AND EXCURSION SAMPLING EQUIPMENT AS1 0002359? ASI 00023598 i f j f !Ii i f Figure 6. TOP VIEW OF PUMP MODIFICATIONS ASI 00023599 ! Figure 7. SIDE VIEW OF CHECK VALVE INSTALLATION AS I 00023600 Dia. FIGURE 9. TOP VIEW OF TOP PUMP COVER AS I 00023GO 1