Document 3NExNnZ7z55jN0dnK8R5ZOQdx

7^7/ & I MIC Applied Sciences (CO./OlV./DEPT./LOCATION) REPORT NO.: 3979 JOB/PROJECT NO.: 43-000-760.21 -8502009 DATE: April, 1976 Final________________REPORT (TYPE OF REPORT) RECEIVED MAY 14 1976 Me clmiral ..Mr*ANY .an ST. LOUIS TITLE: FINAL REPORT ON SPECTROSCOPY METHODS AND SPECIAL STUDIES - 1975 AUTHORS: M. W. Dietrich, et al TITLE: FINAL REPORT ON SPECTROSCOPY METHODS AND SPECIAL STUDIES - 1975 AUTHORS: H. W. DU . i c h , e t a l ABSTRACT: This report describes special spectroscopy studies, new techniques investigated and methods developed by the Applied Sciences Spectroscopy Group at St. Louis during 1975- The individual report sections were issued on a continuing basis during the year. These investigations were undertaken utilizing spectroscopy techniques to solve technical problems encountered by business units of Monsanto Industrial Chemicals Company. Fifty-five special spectroscopy studies were completed and three methods developed during 1975- REPT.NO.: 3979 A- L COPY NO.: nrn i Li t COMPANY CONFIDENTIAL Thi* document is the property of Monsanto Company and the recipient is responsibly for its safekeeping and disposition. It contains CONFIDENTIAL INFORMATION which must not ba reproduced, revealed to unauthorized persons or sent outside the Company.without proper authorization. RSV 0010524 DISTRIBUTION COPY NUMBER ABSTRACT ONLY 2. Technical Reports Library (Loan Copy) 3. Technical Reports Library (Loan Copy) 4. Manager, Applied Sciences - R. E. Keller 5. Group Leader, Applied Sciences - M. W. Dietrich 6. Patent Department * J. E. Maurer 7. Circulated Copies (one each to the groups below): a. Director, Technology Planning & Evaluation Manager, Technology Planning Manager, Technology Evaluation Manager, Process Technology b. Director/Managers, R6D Plasticizers Division Process Chemicals Division Rubber Chemicals Division Specialty Chemicals Division c. Product Acceptability Managers Each circulated copy to return to author. Abbreviated Copies* To: I. Manager, Applied Sciences Europe - R. A. Lidgett * Louvain-La-Neuve 2. Manager, Physical Sciences Center * W. E. Koerner * St. Louis j. Manager, Analytical Section, Process Technology, MP&P - R. L. Haute - Texas City 4. Chief Chemists, et al - MIC - U.S. F. Wright * Augusta G. L. Austin - Avon G. Doremus - Camden E. C. Moredock - Carondelet B. Mays - Columbia J. G. DePagter * Columbia J. B. Willmore - Delaware River R. W. Bucknell - B3NA C. F. Ca1 1 i s - B2SL J. R. Darby 0. DeGarmo M. W. Farrar - 1730 - A2SA - R2E H. C. Godt - TIB P. R. Graham - B2SL E. J. Griffith - NlA W. C. Hammann - T3A W. K. Johnson R. E. Keller - B3NA - TIB W. S. Knowles W. R. Knox - T3A R4C R. J. Kozacka R. L. Liss - F4EA - NIA E. A. Matzner - NIA J. E. Maurer - E2NB D. W. McDonald E3SH G. J. MeEwan J. S. Metcalf - NIA - B2NK R. H. Munch - TIB H. K. Nason W. B. Papageorge T. M. Patrick J. H. Payne - G4ND - B3NB - T3B - NIA J. F. Quinn - T3B G. A. Rauh - B3SB W. R. Richard - R2E F. S. Riordan - G5WG W. 0. Robinson - R2E L. G. Scharpf - NIA R. J. Schatz - E3SA R. Schuler/F. C. Meyer - R4B M. J. Scott - NIA C. Y. Shen - NIA C. C. Sisler - R2E A. J. Speziale - C3NA W. F. Symes - NIA Q. E. Thompson - T3E M. C. Throdahl - DID ^Abbreviated reports contain only the index, section titles, introduction and summary. This report contains confidential information which is the property of the Monsanto Company and which shall be disclosed only Co duly authorized persons. The recipient is held accountable for the filing and safe custody of this report vhlch must be returned on demand. COMPANY CONFIDENTIAL Whan no longer needed, or upon request, return this report to Central Reports, R2C. RSV 0010525 DISTRIBUTION Abbreviated Copies* (Cont'd) k. Chief Chemists, et al - MIC ~ U.S. W. M. Mees - Everett D. M. Wlddows - Kearny H, J. Horner - Krummrich L. A. Herman - Long Beach 0. E. Dolin - Nitro R. A. Geisman - Queeny B. S. K. Fung - Seattle E. E. Thomsen - Soda Springs P. Warner - Soda Springs J. V. RobiMard - Trenton A. R. Schroeder - Trenton E. N. Danes, Jr. - Patchogue 5. Chief Chemists, et a) - MIC Europe and Brazil E. G. Bricked - Ruabon (Via 0. Danna) P. Meganck - Antwerp (Via 0. Danna) A. F. Regan " Newport (Via D. Danna) E. Wahnon - Sau Paulo (Via D. Danna) 6. Chief Chemists - Other Monsanto Companies W. W. Klemme - Chocolate Bayou R. K. Hartman - Luting T. G. Lyons * Texas City J. Brown - Anniston 7. Research Group Leaders E. F. Kaelble - St. Louis R. H. Campbell - Akron Abstract Only (Cont'd) R. L. Wasson - T3A J. C. Weber - B2SK J. L. Wikoff B3NH B. L. Williams - R1C J. J. Zeman - B2SK F. B. Zienty - T3A A. Y. Coran - Akron - 1010 W. A. Vaughn - Akron - 1010 R. W. Wise - Akron - 1010 E. E. Hardy - Dayton - 1250 Via D. Danna * E2NB: Melbourne, Australia Montreal, Canada Louvain-La-Neuve Central Reports Library: M. . Madden - R2B RSV 0010526 MONSANTO INDUSTRIAL CHEMICALS COMPANY ST. LOUIS TECHNOLOGY DEPARTMENT St. Louis Research Report No. 3979 FINAL REPORT ON SPECTROSCOPY METHODS AND SPECIAL STUOIES - 1975 Job No. 43-000-760.21-8502009 Date: April, 1976 Work Done and Reported By: M. W. Dietrich L. M. Chapman D. Guerry D. B. Hines B. Katlafsky 0. E. Klnast G. W. Nappes E. S. Tucker H. Yepez -COMPANY C0NF1DENTIALR$V 0010527 TABLE OF CONTENTS Page No. I. INTRODUCTION.................................................. I I I. GENERAL SUMMARY........................................ 1 III. NEW COMPOUNDS FOR SRC........................ I IV. SPECTROSCOPY METHODS............................. 1 V. SPECTROSCOPY SPECIALSTUDIES. . . 2 RSV 00X0528 -1- INTRODUCTION This report describes special spectroscopy studies, new techniques investigated and methods developed by the Applied Sciences Spectroscopy Group at St. Louis during 1375* The individual report sections were Issued on a continuing basis during the year. These investigations were undertaken utilizing spectroscopy techniques to solve technical problems encountered by business units of Monsanto Industrial Chemicals Company. GENERAL SUMMARY Fifty-five special spectroscopy studies were completed and three methods developed during 1375. The studies provided data for MIC projects from the Oetergent and Fine Chemicals, Food and Fine Chemicals, Plasticizer, Process Chemicals, Flavor/Essence and Specialty Products business units. Pollution control projects for the Krumnrich, Nltro, Queeny and Seattle Plants and special studies involving worker safety for the Corporate Medical Department at twelve Monsanto plants or research facilities were also undertaken. NEW COMPOUNDS FOR SRC No new compounds were prepared in the course of these investigations. SPECTROSCOPY METHODS This work is further summarized under each of the appended specific reports (Methods 75-1 to 75"**). A. Component Index (1975) Method No, Component 75-1 Potassium, AA Determination in Aircraft Hydraul1c Fluids 75-2 Potassium, AA Determination in Aircraft Hydraulic Fluids (Revised) 75-3 75-** Not issued Lead, AA Determination in U.S.P. Vanillin -COMPANY CONFIDENTIAL- i RSV 0010529 IV. SPECTROSCOPY METHODS (Cont'd) B. Product Index (1975) Method No. i Product 75-1 75-2 Aircraft Hydraulic Fluids, Potassium Content Aircraft Hydraulic Fluids, Potassium Content (Revised) 75-3 Not issued 75-* Vanillin (U.S.P.). Lead Content V. SPECTROSCOPY SPECIAL STUDIES This work is further sunmarl2ed In each of the appended specific reports (Special Studies 75*1 to 75*57). Report No. Title 75-1 Determination of Volatiles in Decatur, Alabama Plant Air (It) 75-2 Identification of Different Cresylic Phosphate Esters in Stauffer Fluids 75-3 Air Monitoring for Phenol at Port Plastics Plant, Addyston, Ohio 75-4 Analyses for Organics in the Air at Pensacola 75-5 Identification of Minor Components in Ethyl Benzene and Tetrachlorophthalic Anhydride 75-6 J.F. Queeny Plant Standard Oil and Grease Residues 75-7 Radioactivity In Diphenyl Oxide Intermediates, Finished Goods and Environmental Effluent 75-8 75-9 75-10 Tracer Lithium Analyses - Nitro Plant Effluent Maleic Anhydride Refining Process Impurity Analysis of Benzene in Air at Anniston, Alabama Plant 75-11 Analysis of Volatiles in Decatur, Alabama Plant Air (III) -COMPANY CONFIDENTIAL- RSV 0010530 V. SPECTROSCOPY SPECIAL STUDIES (Cont'd) Report Mo, TTtle 75-12 Organic Chemicals in Chocolate Bayou Plant Waters 75-13 Determination of Benzyl Chloride in Oelaware River Plant Air 75-14 Determination of Toluene D2isocyanate in Air in the Super Dome (ll) 75-15 Modification of a Gas Chromatograph for External Use of the Carrier Gas 75-16 NC-220 Quality 75-17 Chlorodibenzo-p-Dtoxins in Pentachlorophenol Treated with Morpholine 75-18 June 1975 Mercury Inventory, W. G. Krummrich Plant, Chloro-Alkali Department 75-19 Determination of Maleic Anhydride and Vinyl Acetate in Air: Port Plastics 75-20 Determination of Chioroprene in Air at Port Plastics Plant, Addyston, Ohio 75-21 Determination of Volatiles in Decatur, Alabama Plant Air (IV) 75-22 Determination of Contaminants in Dimethyl Sulfide 75-23 Volatile Organics Evolved during Thermogravimetric Analysis of Flame and Smoke Retarding PVC Formulations 75-24 Volatiles from ABS and Styrene Polymers at Processing Temperatures 75-25 Determination of 81s(2-chloroethy1) Ether in Phosgards 75-26 Hydrolytic Stability of Pydrauls and Competitive Products 75-27 Determination of Vinyl Chloride, Trichloroethylene and Epichlorohydrin in Air at Baxley, Georgia Plant -COMPANY CONFIDENTIAL- RSV 0010531 -*- V. SPECTROSCOPY SPECIAL STUDIES (Cont'd) Report No. Title 75-28 75-29 75-30 Personnel Honitorlng of PCP Unit at Nitro Plant BIschloromethyl Ether Content of Oequest Products and Everett Plant Air Trace Lithium Analyses - Nitro Plant Effluent (II) 75-31 75-32 Analyses of Nitro Plant Waste Waters for Trace Organic Pollutants Determination of Volatiles in Decatur, Alabama Plant Air (V) 75-33 75-3* Tracer Lithium Analyses - Nitro Plant Effluent (III) Determination of Trichloroethylene (TCE) in Air at Delaware River 75-35 75-36 75-37 75-38 Determination of Benzene in Air at Anniston, Alabama Plant (II) Pydraul 29 ELT/Pydraul 50 E Gel Complaint from Republic Steel Chemical Ionization of Esters and Alcohols Determination of Trichloroethylene (TCE) in Air at St. Peters 75-39 75-*0 Determination of Contaminant in Oxo Alcohol Synthetic Fatty Acid Continuous Pilot Plant Radiotracer Catalyst Study with Iridium-192 -- Feaslbi11ty Investigations 75--41 Synthesis, Analytical Characterization and Preparation of FDA Test Coatings of Modaflow l"C 75-*2 Determination of Aroclor 1016 in Air at Electric Utilities Company, LaSalle, Illinois 75-*3 Determination of Levels of Trlethylamine and Butanol in Air at the Delaware River Plant 75-** 75-*5 Not Issued Determination of Maleic Anhydride and Styrene in Air at Everett, Massachusetts -COMPANY CONFIDENTIAL- RSV 0010532 -5- V. SPECTROSCOPY SPECIAL STUDIES (Cont'd) Report No. Title 75-46 Not Issued 75-47 Synthesis. Characterization and Purification of S-334FMUC 75-48 75-49 75-50 75-51 75-52 75-53 75-54 75-55 Synthesis of Five Radiolabeled (P-32) Food Phosphate Salts Determination of Benzene in Air in the St. Louis Research Center Preparation and Conditioning of Collection Columns for Organic Chemicals in Air GC Modification for Measurement of Organic Chemicals in Air by Thermal Desorption December 1975 Mercury Inventory, V. G. Krummrich Plant, Chior-Alkali Department Determination of Benzyl Chloride and Toluene in Air at the Delaware River Plant Determination of Acetamide (AC), N-Methyl Acetamide (NMAC) and Dimethyl Acetamide (DMAC) in Urine Chlorinated Oibenzofurans in Crude Honochlorobenzene from the Oxychlorination Process 75-56 The Preparation and Characterization of Carbon-14 Labeled Tetradecanol Ethoxylates 75-57 Organic Contaminants In Trenton Phosphate Products COMPANY CONFIDENTIAL LY 0010533 S-75-H-1 DIRECT DETERMINATION OF POTASSIUM IN AIRCRAFT _____ HYORAULIC FLUIDS BY ATOMIC ABSORPTION SCOPE This method Is Intended for the direct determination of potassium In air craft hydraulic fluids at e level of about 18-20 ppm with an estimated precision of 6.71 of the amount present for single analyses. PRINCIPLE A weighed sample of fluid for analysis Is dissolved In a 1:1 (v/v) mixture of glacial acetic acid and methyl Isobutyl ketone and diluted to volume with this mixed solvent. The potassium is determined by the method of standard additions In the presence of a high concentration of'lithium to suppress potassium ionization In the flame. REAGENTS 1. Standard reference solution of 1000 ug/ml potassium (Note 1). 2. Methyl Isobutyl ketone (Note 2). 3. Glacial acetic acid (Note 3). 4. Solution of 1000 ug/ml lithium in 1:1 (v/v) glacial acetic acid/ methyl isobutyl ketone solvent (Note 4). APPARATUS 1. Volumetric ptpets as appropriate. 2. Volumetric flasks as appropriate. 3. Perkln-Elmer Model 403 Atomic Absorption Spectrophotometer equipped with a hollow cathode potassium source and an air/acetylene burner with a 4-inch single slot.4 4. Specific Instrumental conditions for the Perkln-Elmer Model 403 Atomic Absorption Spectrophotometer: a. Hollow cathode lamp: Potassium (Note 5) b. Wavelength: 7665A. c. Slit: 4 (7A.). d. Readout: Digital, concentration mode. e. Burner: Titanium, 4-Inch single slot (Note 6). f. Flame: A1r/acetylene; lean, blue oxidizing. RSV 0010534 Page Two PROCEDURE 1. Weigh accurately about 5 9 of sample Into a 50 ml volumetric flask (Mote 7). 2. Add about 25 ml of mixed solvent, dissolve the fluid sample with agitation and dilute to volume. 3. Prepare a 2 ppm potassium standard in mixed solvent. A. Set up the atomic absorption instrument as follows: a. "Concentration" and "Repeat" mode. b. "Onset" at 0. c. "Magnitude" at 0. d. 10 Average mode. 5* Aspirate mixed solvent Into the flame and set the base line to zero with the "Auto Zero" button. 6. Prepare four standard addition (Note 8) solutions from the sample solution as follows: a. Aliquot 1 ml of the sample solution into four 10-ml volumetric flasks. b. Add 0 ml of 2 ppm potassium standard to the first flask, 1 ml of standard to the second flask, 2 ml of standard to the third flask and 3 ml of standard to the fourth flask. c. Add 5 ml of 1000 ppm lithium solution to each 10--ml flask. d. Dilute each flask to volume with mixed solvent and mix thoroughly. e. The standard addition concentrations are thus 0, 0.2, 0.4 and 0.6 ppm potassium. 7. Briefly aspirate the standard addition solution containing the largest amount of added potassium (0.6 ppm) and set the readout to about 0.250 (Note 3). 8. Depress the "Hanual" and "100 Average" buttons. 9. Check the base line and add or subtract a small correction to each solution reading as required. 10. Measure the observed absorbance of each of the four standard addition solutions. 11. Plot the observed absorbance vs. concentration of added potassium In each solution and determine the concentration of potassium In the usual way from the Intersection of the straight line with the concentration axis (Note 10). RSV 0010535 S-75-M-1 Pag* Three CALCULATIONS where ppm K 1 X 500 W t ppm K determined from the standard addition plot. Step 11. W Sample weight (g) NOTES Cjj ppm K correction due to potassium presence In the lithium solution added to suppress potassium ionization (Note 11). 1. Catalog No. S0-P-351, Fisher Scientific Co., Fair Lawn, N.J. 07410 2. AR grade, Catalog No. 6247* Hallinckrodt, Inc., St. Louis, Ho. 63147 3. AR grade. Catalog No. 2504, Hal IInckrodt, Inc., St. Louts, Ho. 6314? 4. This solution may be prepared from "potassium-free" Li2C0$. Spectro scopic grade L12CO3 from Spex Industries, inc., 3880 Park Ave., Metuchen, N.J., Cat. No. 1234, purity 5-9s (K content 2-3 ppm) is satisfactory. Weigh 5*3249 g of Li2C0) Into a 400-ml beaker. Add slowly with gentle agitation enough glacial acetic acid to neutralize the carbonate with a small excess of acetic acid. Using 1:1 mixture of glacial acetic acid/methyl Isobutyl ketone, quantitatively transfer the solution to a 100-ml volumetric flask and dilute to volume with the mixed solvent and thoroughly mix. Aliquot 10 ml of this solution to a 100-ml volu metric flask and dilute to volume with mixed solvent to obtain the 1000 ug/ml lithium solution for use in the analysis. 5. Catalog No. JA45-36052, Fisher Scientific Co., Fair Lawn, N.J. 07410. Adjust the lamp current to 5-6 HA to avoid severe self-absorption. The current of 12 HA stated on the lamp is much too high. 6. Part No. 303-0418, Perkin-EImer Corp., Norwalk, Conn. 7. This may be easily done with a 5-ml plpet or syringe which delivers about 4.9 g of fluid. 8. Analytical Hethods for Atomic Absorption Spectrophotometry, The PerklnElmer Corp., Norwalk, Conn, (revised 1968).9 9. The results may be conveniently plotted on graph paper having 10 X 10 divisions to the 1/2 Inch, 7 1/2 X 10 Inches (Keuffel and Esser No. 46-1470) with spectrometer readout values on the ordinate with 5 divi sions 0.010. Do not turn the Concentration" dial more than about halfway (500-600)' use a lower readout if necessary. RSV 00L0536 Page Four 10. To avoid bias, tha Intercept of the straight line on the concentration axis Is bast calculated by regression analysis (least squares fit). A Texas Instruments, Model SR-51, Calculator Is used for this purpose In this laboratory. 11. The LIsCOa used In the development of this method of analysis was found to contain 2.6 ppm potassium by our analysis. The correction to be subtracted (<) from each analytical result may be calculated as ~fol lows: 1 (ppm K In LiaCOa) cl i (Fluid Sample" Wt., W) X 1.33 ppm For 2.6 ppm K In LlaCOa and a fluid sample weight of 5 9 the correction to be subtracted would be: (2.6)(1.33) CL| (5) 0.7 ppm APPENDIX A. Precision and Accuracy of Method A standard was prepared in the laboratory containing 18.5 ppm potassium. Five analyses of this standard by the above procedure were done with the following results: Trial PPM K Found Statistical Data: 1 2 3 4 5 18.3 18.0 18.9 18.3 19.1 a. Standard Deviation * 0.46 b. Average 18.52 ppm K c. Standard Deviation of Average 0.206 d. Confidence Limits for single analysis + 1.28 ppm K e. Confidence Limits for five analyses +, 0.57 ppm K f. Precision of single analysis + 6.72 of amount present g. Precision of five analyses - + 3.0t of amount present ss Monsanto Industrial Chemicals Co. Applied Sciences St. Louis, Mo. 8/75 * 0. Guerry, M. W. Dietrich RSV 0010537 Spectroscopy S-75-H-2 (R) REVISED METHOD FOR THE DIRECT DETERMIHATION OF POTASSIUM IN AIRCRAFT HYDRAULIC FLUIDS BY ATOMIC ABSORPTION SCOPE This method Is intended for the direct determination of potassium in air* craft hydraulic fluids at a level of about 18*20 ppm with an estimated precision of 9.5$ of the amount present for single analyses, it should be used in place of S-75-M-1. PRINCIPLE A weighed sample of fluid for analysis Is dissolved in a 1:1 (v/v) mixture of glacial acetic acid and methyl isobutyl ketone and diluted to volume with this mixed solvent. The potassium is determined by the method of standard additions in the presence of a high concentration of lithium to suppress potassium ionization in the flame. REAGENTS1 2 3 1. Standard reference solution of 1000 ug/ml potassium (Note 1). 2. Methyl isobutyl ketone (Note 2). 3. Glacial acetic acid (Note 3) A. Solution of 2000 ug/ml lithium In 1:1 (v/v) glacial acetic acid/ methyl isobutyl ketone solvent (Note A). APPARATUS 1. Volumetric pipets as appropriate. 2. Volumetric flasks as appropriate. 3. Perkin*Elmer Model A03 Atomic Absorption Spectrophotometer equipped with a hollow cathode potassium source and an air/acetylene burner with a 2-inch single slot or a nitrous oxide burner. A. Specific Instrumental conditions for the Perkin-Elmer Model A03 Atomic Absorption Spectrophotometer: a. Hollow cathode lamp: Potassium (Note 5) b. Wavelength: 7&&5A. c. Slit: A (7A.). d. Readout: Digital, concentration mode. e. Burner: 2-inch single slot (Note 6), rotated 90 to direction of the lamp beam. The burner Is rotated perpendicular to the lamp beam to reduce the effects of potassium contamination from the added lithium and from the solvent system. f. Flame: Air/acetylene; lean, blue oxidizing. RSV 0010538 $-75-M-2(R) Page Two PROCEDURE 1. Weigh accurately about 5 g of sample into a 25 ml volumetric flask (Note 7). 2. Add. about 15 ml of mixed solvent, dissolve the fluid sample with agitation and dilute to volume. Mix thoroughly. 3* Prepare a 10 ppm potassium standard in mixed solvent. k. Set up the atomic absoprtlon instrument as follows: a. "Concentration" and "Repeat" mode. b. "Onset" at 0. c. "Magnitude" at 0. d. 10 Average mode. 5. Aspirate mixed solvent into the flame and set the base line to zero with the "Auto Zero" button. 6. Prepare four standard addition (Note 8) solutions from the sample solution as follows: a. Aliquot 2 ml of the sample solution into four 10-mi volumetric flasks. b. Add 0 ml of 10 ppm potassium standard to the first flask, 1 ml of standard to the second flask, 2 ml of standard to the third flask and 3 ml of standard to the fourth flask. c. Add 5 ml of 2000 ppm lithium solution to each 10-mi flask. d. Dilute each flask to volume as required with mixed solvent and mix thoroughly. e. The standard addition concentrations are thus 0, I, 2 and 3 ppm potassium. 7. Briefly aspirate the standard addition solution containing the largest amount of added potassium (3 ppm) and set the readout to about 0.250 (Note 9). 8. Depress the "Manual" and "100 Average" buttons. 9. Check the base line and add or subtract a small correction to each solution reading as required. 10. Measure the observed absorbance of each of the four standard addition solutions. 11. Plot the observed absorbance vs. concentration of added potassium in each solution and determine the concentration of potassium in the usual way from the intersection of the straight line with the concentration axis (Note 10). RS V 0010539 CALCULATIONS S-75-M-2(R) Page Three whgre: ppm K I X 125 W NOTES I " ppm K determined from the standard addition plot* Stp M. W Sample weight (g). 1. Catalog No. S0-P-351, Fisher Scientific Co., Fair Lawn, N.J. 07410. 2. AR grade. Catalog No. 6247, Hallinckrodt, Inc., St. Louis, Mo. 63147. 3. AR grade. Catalog No. 2504, Hallinckrodt, Inc., St. Louis, Mo. 63147. 4. This solution may be prepared from "potassium-free11 LI2CO3. Spectro scopic grade L^COs from Spex Industries, Inc., 3880 Park Ave., Metuchen, N.J., Cat. No. 1234, purity 5*9* (K content * 2-3 ppm) is satisfactory. Weigh 5.3249 g of L^CO} into a 400-ml beaker. Add slowly,with gentleagitation, enough glacial acetic acid to neutralize the carbonate with a small excess of acetic acid. Using glacial acetic acid, quantitatively transfer the solution to a 100-ml volimetrlc flask, dilute to volume with glacial acetic acid and thoroughly mix. Aliquot 20 ml of this solution to a 100-ml volumetric flask and dilute to volume with mixed solvent to obtain the 2000 ug/ml lithium solution for use in the analysis. 5. Catalog No. JA45-36052, Fisher Scientific Co., Fair Lawn, N.J. 07410. Adjust the lamp current to 5*6 MA to avoid severe self-absorption. The current of 12 MA stated on the lamp is much too high. 6. Part No. 303*0420 (2-inch single slot) or 303*0419 (nitrous oxide burner), Perkin-Elmer Corp., Norwalk, Conn. 7. This may be easily done with a 5*ml pi pet or syringe which delivers about 4.9 g of fluid. 8. Analytical Methods for Atomic Absorption Spectrophotometry, The PerkinElmer Corp., Norwalk, Conn, (revised 1966). 9. The results may be conveniently plotted on graph paper having 10 X 10 divisions to the 1/2 inch, 7 1/2 X 10 inches (Keuffei and Esser No. 46-1470) with spectrometer readout values on the ordinate with 5 divi sions 0.010. Do not turn the "Concentration" dial more than about halfway (500-600); use a lower readout If necessary. 10. To avoid bias, the intercept of the straight line on the concentration axis ts best calculated by regression analysis (least squares fit). A Texas Instruments, Model SR--SI Calculator is used for this purpose (n this laboratory. RSV 0010540 S-75-*-2(R) Page Four APPENDIX Precision and Accuracy of Method A standard was prepared In the laboratory calculated to contain 21.5 ppm potassium. Five analyses of this standard by the above procedure were done with the following results: Trial PPM K Found 1 22.3 2 22.2 3 22.5 It 23.0 5 24.1 Statistical Data: 1. Standard Deviation * 0.78 2. Average * 22.82 ppm K 3. Standard Deviation of Average * 0-348 4. 95% Confidence Limits for single analysis + 2.16 ppm K 5. 95% Confidence Limits for five analyses - +0.97 ppm K 6. Precision of single analysis + 9-5% of amount present 7. Precision of five analyses + 4.3% of anount present ss Monsanto Industrial Chemicals Co. Applled Sciences St. Louis, Ho. 11/75 - D. Guerry, M. W. Dietrich R$ V 0010541 Spectroscopy Method S-75-M-4 DETERMINATION OF TRACE LEAD IN U.S.P. VANILLIN BY FLAMELESS ATOMIC ABSORPTION SCOPE This method Is intended for the determination of lead in U.S.P. vanillin at a level of about 0.1 ppm with an estimated precision of 22$ (95$ confidence limits) of the amount present for single analyses. PRINCIPLE A weighed sample for analysis is digested with concentrated nitric acid and 30$ hydrogen peroxide, and made up to volume with water. The lead is determined by the method of standard additions using a flameless atomic absorption technique with a graphite furnace atomizer. REAGENTS 1. Standard reference solution of 1000 yg/yl lead (Note 1). 2. Concentrated nitric acid (Note 2). 3. Hydrogen peroxide, 30$ (Note 3)- APPARATUS 1. Hot plate. 2. Volumetric pipets as appropriate. 3. Volumetric flasks as appropriate. 4. Beakers as appropriate. 5. Eppendorf pipette, 25 microliter volume (Note k). 6. Perkin Elmer Model 303 Atomic Absorption Spectrophotometer equipped with a hollow cathode lead source, a deuterium background corrector and a graphite furnace atomizer for flameless atomic absorption analysis. 7. Specific instrumental conditions for the Perkin Elmer Model 303 Atomic Absorption Spectrophotometer: a. Hollow cathode lamp: Lead (Note 5) b. Wavelength: 2833 A. c. Slit: k (7A). d. Readout: Recorder (Note 6): Chart speed 0.75 In/min, noise suppression 1, scale expansion XI. e. Graphite furnace atomizer: Graphite tube type (Note 7): Drying, 150C for 30see.; Ashing, 700C for 30 sec.; Atomization, 2500C for 8 sec. Nitrogen gas purge rate at 30. PROCEDURE 1. Weigh accurately about 2 g of sample Into a 400-ml beaker. 2. Add slowly and continuously 25 ml of concentrated HN0. and allow to stand until the Initial reaction has moderated. RSV 0010542 S-75-M-4 Page Two PROCEDURE (Cont'd) 3. Place on a hot plate, set at "Medium" and boil off HNO- down to about 5 ml. 3 4. Add 5 ml of 302 hydrogen peroxide. 5. Boll off excess liquids down to about 2-3 ml, remove from the hot plate and cool. 6. Quantitatively transfer to a 10-ml volumetric flask and dilute to volume with water. 7. Prepare a 0.4 ug/ml lead standard. 6. Prepare three standard addition (Note 8) solutions from the sample solution as follows. a. Aliquot 3 ml of the sample solution into three 10-ml volumetric flasks. b. Add 0 ml of 0.4 ug/ml lead standard into the first flask, I ml of standard into the second flask and 2 ml of standard into the third flask. c. Dilute each flask to volume and mix thoroughly. d. The standard addition concentrations are thus 0, 0.04 and 0.08 ug/ml of lead, and 25 microliters (0.025 milliliter) of each of these solutions give 0, I and 2 nanograms of lead respectively. 9. Turn on the recorder and press the "High Temperature" button for 2-3 seconds to clean the graphite furnace before introducing samples for analysis. Note any response (peaks) on the recorder, and continue the cleaning intervals until any peak disappears. 10. Using an Eppendorf pipette, introduce a 25 micro!!ter aliquot of each sample solution in turn into the graphite furnace and atomize each according to the temperature program previously set. 11. Run each solution at least twice and average the peak absorbance values. 12. Plot the observed absorbance vs. concentration of added lead In each solution (absorbance vs. nanograms tead/25 microliters solution) and determine the concentration of lead in the usual way from the Intersection of the straight line with the concentration axis (Note 9). CALCULATIONSI ppm Pb I X 1.333 W where Intersection of the standard addition plot with the concentration axis. Step 12 (nanograms Pb/25 microliters) W Sample weight (g) RSV 00X0543 PRECISION AMD ACCURACY OF METHOD2 3 4 S-75-M-4 Page Three Five standards were prepared in the laboratory by adding 0.5 ppm lead to 2-g samples of U.S.P. vanillin. These five lead*splked standards along with five 2-g blanks of U.S.P. vanillin treated to remove lead (Note 10) were analyzed according to the above procedure. The following results were 1 obtained: 1 t i I Trial Blank (ppm Pb) 0.095 Spiked (ppm Pb) 0.622 1 l 2 0.012 0.712 t 3 0.063 0.646 i i 4 0.115 0.751! i 5 0.198 0.655 1 Average: 0.1006 0.6778 Stand, deviation: 0.0669 0.0539 Stand, deviation average: 0.0299 0.0241 1 Difference: Spiked-Blank t (a) Average, difference - 0.5772 (b) Stand, deviation, difference - 0.0859 i (c) Stand, deviation, average difference 0.0859//To' - 0.0272 For 5 duplicate analyses, average difference: 0.577 ppm Pb relative found. 10.9% For a single analysis of a spiked standard: 0.678 ppm Pb + 22% relative found. i NOTES I 1. Catalog No. SO-L-21, Fisher Scientific Co., Fair Lawn, N.J. 07410 2. BSA Electronics Grade, Code 108-2677, Allied Chemical Co., Specialty Chemicals Division, P.0. Box 1087 R, Norristown, N.J. 07960. 3. Catalog No. 5240, Hal 1 tnckrodt, Inc., St. Louis, Ho. 63147. 4. Catalog No. 21-3700, Flshef Scientific Co., Fair Lawn, N.J. 07410. 5- Catalog No. JA45-36039, Fisher Scientific Co., Fair Lawn, N.J. 07410. RSV 0010544 S-75-M-4 Page Four NOTES (Cont'd) 6. $ervo-rfter It, Texas Instruments, Inc., Dallas, Texas 7S222. 7. Model HGA-2100 Graphite Furnace, The Perkin Elmer Corp, Norwalk, Conn. 8. Analytical Methods for Atomic Absorption Spectrophotometry, The Perkin Elmer Corp., Norwalk, Conn, (revised 1968). 9. 1 t 10. To avoid bias, the intercept of the straight line on the concentration axis is best calculated by regression analysis (least squares fit). A Texas Instruments, Model SR-51, calculator is used for this purpose in this laboratory. U.S.P. vanillin was dissolved in 1:1 (v/v) isopropyl alcohol/water solvent and 152 of its weight of Imac TMR thiol resin (Akzo Chemie, Netherlands) was added. The mixture was stirred overnight, the resin filtered off and the vanillin was recrystal 1ized from the solution. Thiol ion-exchange resins are reported to be efficient in removing heavy metals such as lead. No effort was made to determine whether the apparent 0.1 ppm Pb in the treated vanillin was actually Pb or a background effect. Analyses of 10 random lots of U.S.P. vanillin (untreated) showed an average level of 0.12 ppm and a range of 0.05 to 0.24 ppm Pb. I ) ss Monsanto Industrial Chemicals po. Applied Sciences St. Louis, Mo. 12/75 - 0. Guerry, M. W. Dietrich RSV 0010545 Special Study S-75-SS-I ANALYSIS OF VOLATILES IN DECATUR, ALABAMA PLANT AIR (II) INTRODUCTION This is an investigation to determine concentration levels of vinyl bromide (VBrJ, vinyl acetate (VA), and acrylonitrile (AN) in air at the North polymer area of the Decatur, Alabama plant. The data obtained will be used to determine exposure levels to the worker in this area. SUMMARY Results of the study are found in the attached table. GC reten tion times for VA and AN were so similar under these conditions that they could not be used to distinguish between them. Only one sample contained either, and this was at a level too low for identification with our existing mass spectrometer. VBr was observed and identified by GC/MS at levels from <0.03 ppm to 8.13 ppm. Only one sample contained an unknown, at a concentra tion of <v0.06 ppm as shown in the table. None of the samples contained detectable levels of vinyl chloride or vinylldene chloride. EXPERIMENTAL Refer to Spectroscopy Special Study 74-32 for procedure. A sample calculation Is listed below. Values were based on a vinyl bromide standard. Calculation Volume sampled * flow rate (ml/min.) x minutes x 10"3 ex: L3 Volume sampled * 44 ml/min. x 60 min. x 10~3 - 2.64 L Weight Sample sample area (counts) x xstd. cone*std. area (counts) ex: L3, VBr 122340 x 2.6 1 - 96 Mg wt. sample Concentration sample Mg/l* * wt. sample/volume sampled cone. jig/L - 96 ug/2.64 L - 36*3 ug/L Concentration (ppm) Mg/L x .024/MW x 1000 - 36.3 x .024/107 x 1000 - 8.1 ppm VBr std. 2.6 /ig/)uL x 1 fdL RSV 0010546 Reference: 6C/MS File #75-4. de Monsanto Industrial Chemicals Co. Applied Sciences St. Louis, Missouri 1/75 - L- M. Chapman, M. W. Dietrich S-75-SS-1 Pege 2 RSV 0010547 S-75-SS-I Pge 3 Sample L-3 L-4 L-7 L-ll L-12 L-5 Concentration (ppm) VBr 8.1 0-7 *AN X <0.07 **0.07 aVA X <0.05 *<0.05 <0.03 **0.07 *<0.05 <0.03 <0.03 0.1 *<0.07 0.07 *<0.05 blank Unknown ' -06 ppm x None detected x L-5 and L-4 used the mllllpore M-2 pump for sampling with a :flow rate of 44 ml/mln. L-7, L-ll and L-12 used the air check SKC 222-451 pump for sampling with a flow rate of 17 ral/min. Note AN and VA have the same retention time and values are based on Individual molecular weight* Since the concentration Is so low, mass spectrometrlc confirmation was not attainable* RSV 0010543 Special Study S-75-SS*2 IDENTIFICATION OF DIFFERENT CRESYLIC PHOSPHATE ESTERS IN STAUFFER FLUIDS SUMMARY Three samples of fluids from Stauffer Chemical Company showed significant differences In the type of phosphate ester used. The esters were found to range from a cresyl diphenyl phosphate type to a very highly substituted phosphate ester. DISCUSSION NMR shows that the phosphate esters in three Stauffer fluids, 149 EIT, FQ ISO, and FQ SCF, are cresyl type esters. That is, any substitution on the basic triphenyl phosphate molecule is mainly methyl substitution on the aromatic portion of the molecule. Some ethyl substitution Is also present in these fluids and this is probably the result of ethyl phenols being present in cresols. The GC traces of these fluids, however, are quite different as shown in the figure. The ester in 149 ELT is basically a cresyl diphenyl phosphate with a significant amount of triphenyl phosphate and dicresy! phenyl phosphate. ' The phenol analysis on the bomb hydrollzed esters is shown in the table. The high percentage of phenol for 149 ELT is consistent with the large amount of triphenyl phosphate and cresyl diphenyl phosphate in this ester. The ester in FQ 1$0 is a dicresy! phenyl type with a small amount of triphenyl phosphate. The ester in SCF is even higher boiling and is on the average tricresyl phosphate or xylyl dIcresyl phosphate. The low level of phenol in the table and the large amount of xylenols agree with the high boiling characteristics of the ester. GC/MS analyses of the phenols from bomb hydrolysis is in basic agreement with the identifications done at J. F. Queeny Plant by retention time. Some changes In the Identifications were made because of the GC/MS data and these a clearly Indicated. db Monsanto Industrial Chemicals Co. Applied Sciences St. Louis, Mo. 1/75 ~ G. W. Nappes, M. W. Oietrich RSV 0010549 RSV 0010550 TABLE PHENOL ANALYSIS OF BOMB HYDROLIZED FLUIDS J. F. QUEENY PLANT 19-EEC-74 TIME* 16t13 COMPETITIVE FKCrFHATE ESTER KYCF.0LZATES FL-149ELT LET #4022-4-2 MIC-2S5215 N0FKALIZA7I0N C0M FL'TATI 0N S TIME AT.EA FACT0F. FCT 47 64 68 75 9l 1 00 1 07 1 20 1 32 1 46 l 76 2 OC 553392 8654 329 738 19 119 25565 44686 43437 16718 1789 6 765 829 1.0000 1.0000 1.1000 1.0000 1.0000 1.0000 1.0000 1.0000 1.0000 l.cooc 1.ccoo 50.49 0.61 33.09 I. 74 2. 33 4. 06 3.96 1.71 1.63 0. 0 7 C . Co PHENOL 0-CRES0L MAP-CP.ES0L 2, 6-XYLEN0L 0- ETHYLFH EN0L 2.4A2.5-XYLEN0LS MAP-ETHYLFHBJ0L> 3> 5-XYLE 2/ 3-XYLEN 0L 3. 4-XYLEN0L TM ALKYL FH ENEL AN L HI GH B0 ILEFS 19-CEC-74 TIME* 16:12 C0MFFTI TIVE PKSSPHATE ESTER JiYERCLZATES FC-150 #3503-3-1 N0FMALIZAT10N C0MPLTATI0NS TIME AREA FACTOR PCT 45 66 73 91 1 00 1 06 1 19 1 32 145 1 62 1 75 199 5486 5 37282 100038 2671 2678 33622 3693 1 6923 7153 1355 1876 2728 1.0000 1 .0000 1. 1000 UOOGO 1.0000 l.OOOC 1.coco 1.OCGC 1.0000 l.GQCO l.OOOC 1.0000 18.27 12. 41 36*64 0.89 G.96 11.19 12.96 2*31 2.38 0*45 C* 62 0.91 PHENOL O-CRES0L MAP-CRE50L 2, 6-XYLEN0L 0-ETHYLPHEN0L 2,4*2. 5-XYLEN0LS M4P-ETHYLPHEN0L. 2* 3-XYLEN 0L 3# 4-XYLEN 0L 3j s-xyle TP.I ALKYLFKEN0LS HI E01L RSV 0010551 TABLE Page 2 19-DEC-74 TIM 165 15 COMPETITIVE FH05FHATE E5TEF. HYDFOLEATES MIC-255258 FYFCUEL SCF #4181-1-1 N0Fi4ALIZATI0N C0MFCTATI 0N$ TIME AREA FACTOR FCT 46 61 67 74 91 IOC 1 08 1 24 1 33 1 45 1 61 1 73 194 2 09 2 21 245 9E26C 176668 69 15 153721 6751 7827 261382 39 09 71 9 1 734 898 1 1 28454 44711 488 02 27787 7015 116376 l.GOOC l.OCOO 1.0000 I.1000 WGOOG l.CCGO l.OGCO l.OOCO uccoc l.COOO l.OOCC 1.occo uccco l.COOO i.oooo l.OOCO 5.89 11.28 C*44 10*79 0*43 0* 50 16.68 24*96 5*86 5* 73 1*82 2*85 3* 12 1*77 0* 45 7*43 FHENOL LttKNOW-- O-CRESOL e-er.E30L unknown M*F-CRES0L 2# 6-XYLENOL 0-ETHYLFKEN0L 2,412* 5-XYLEN0L M4F-ETHYLFKEN0L.. 2* 5-XYLE 2* 3-XYLENCL 3, 4-XYLEN0L TRI ALKYL PH EN0LS AND 0THEF. HIGH BOILERS TRIALKYLPHENOLS RSV 0010552 Special Study S-75-SS-3 AIK MONITORING FOR PHENOL AT PORT PLASTICS PLANT, ADDYSTON, OHIO INTRODUCTION This study was made to determine levels of phenol and alkylbenzenes being evolved In the cooling process of phenol formaldehyde resin at the Port Plastics Plant, Addyston, Ohio. SUMMARY The level of phenol In air while the alkylated product was being dropped for cooling was about 23 ppm. A sampling from the second floor gave a level of about I.A ppm and a sampling when no product was on the cooling floor gave none detected (<0.8 PPM). EXPERIMENTAL A Tenax GC glass Insert was used for collection of phenol in air and a Tenax GC served as the analytical column. The Bendix pump Model Cl 15 with a flow rate of 120 ml/min provided the means of sampling the air. See attached table for results. Sampling was made for two minutes. SAMPLE CALCULATIONS Concentration of Std Area of Standard X Area of Sample Concentration Examp1e IX X 108241 - 21.7 ug 10 ^ X Flow Rate X Time of Sample * Volume Example IX 10~3 X 120 ml/raln X 2 min - 240 ml X 10"3 -24 I Cone volume yg/l Example IX 21.7 yg/.2A0 1 90 yg/1 yg/l X 1000 X - ppm Example IX 90 X 1000 X - 23.1 ppm REFERENCE: MS File #75-23. Monsanto Industrial Chemicals Co. Applied Sciences St. Louis, Mo. 2/75 - L. M. Chapman, H. W. Dietrich db RSV 00X0553 1 11 IX XI XIV XVI TABLE PhenoI NO (<0.8 ppm) NO (<0.8 ppm) 23 Ppm 1.4 ppm NO (<0.8 ppm) NO (<0.8 ppm) Alkylbenzenes NO (<0.8 ppm) NO (<0.8 ppm) 1-5 ppm NO (<0.8 ppm) NO (<0.8 ppm) NO (<0.8 ppm) Conments Blank 2 Min. Samp!Ing 2 Min. Sampling 2 Min. Samp!ing Not used Not used RSV 0010554 Special Study S-75-SS-4 ANALYSES FOR ORGANICS IN AIR AT PENSACOLA INTRODUCTION Analyses were performed to Identify and determine levels of organics In the air from the nylon molding resin process at Pensacola. Main compounds of Interest are caprolactam and Dechiorane 25. SUWARY Caprolactam In levels from 0.08-8.6 ppm and 0.03 ppm of tolualdehyde (1 sample only) was found. Dechlorane 25 could not be detected under the GC conditions used. It Is questionable whether the method can be modified to measure Dechlorane 25. No other organics were found with a detection limit of 0.02 ppm. EXPERIMENTAL A 0.15 Tenax GC glass Insert was used for collection with a SKC model 222-451 pump. Thirty minute samples were taken with a flow rate of 60 ml/mln. See attached table for results. CALCULATIONS A) Concentration (ug) * ^ ^ X Area of Samp1e B) Volume (Liters) * Flow Rate (mt/min) X Time of Sample (min) X 10~3 c ,,/, `misri;;lw> 0) PPTM - V9/S- X Molecular- Weight Example (Die Face) Caprolactum A) C * 6.15 ug/ 6.10 X .80 - 1 ug B) V - 10"3 X 60 ml/mln X 30 1.81 C) ug/t - .81/1.8 - .45 D) ppm - .45 X 24.5/113 - 0.10 ppm Reference: MS File #75-30 db Monsanto Industrial Chemicals Co. Applied Sciences St. Louis, Mo. 3/75 - L. M. Chapman, M. W. Dietrich RSV 0010555 sV TABLE I Extruder Nozzle(V) Extruder Hopper(III) Die Face(VII) Change Desk(VIII) Opera tor(X) Extruder Nozzle (XII) Caprolactam Tolualdehyde 8.6 ppm 0.03 ppm N.D. (<.02 ppmT 0.10 ppm 0.16 ppm N.D. (<.02 ppmT 0.08 ppm No other organics were detected. Detection limit 0.02 ppm. RSV 0010556 Special Study S-75-SS-5 IDENTIFICATION OF MINOR COMPONENTS IN ETHYL BENZENE AND TETRACHLOROPHTHALIC ANHYDRIDE INTRODUCTION This analysis was performed to Identify unknown components In ethylbenzene and tetrachlorophthallc anhydride (TCPA) which might Inhibit catalyst perform ance at the Oelaware River Plant. SUMARY The results of the analysis are shown In Table 1 and In attached GC/KS chromatograms. EXPERIMENTAL GC conditions are given In Table II. The ethylbenzene was also run on a flame photometric GC In the sulfur detection mode. The latter confirmed that no volatile sulfur compounds were present. Reference: MS File #75-40. db Monsanto Industrial Chemicals Co. Applied Sciences St. Louis, Mo. 3/75 - L. M. Chapman, M. W. Dietrich RS V 0010557 Peak* 1 2 3 4 5 6 TABLE I ETHYLBENZENE Identlflcation Benzene m 98: possibly dimethyl or methyl pentanone MW 100: possibly methyl Isobutyl ketone or hexanone or methyl pentanone Toluene MW 112: possibly dimethyl cyclo hexane or trlmethyl pentene MW 112: possibly acrolein dimer or dimethyl hexene *$ee attached chromatogram for peak number reference Peak* TCPA Identification 1 Tetrach1oroben zene 2 Pentachlorobenzene 3 Hexachlorobenzene RSV 0010558 TABLE II A HP 5700 GC and HP 5980 mass spectrometer were used for Identification analysis using one microliter Injection of the neat solution. Conditions for Ethylbenzene Column: 3* OV 101 1m with a 1/8" I.D. Program: 0 - 70C 9 4/M1n Hass Gain: 5 Mass Scan: 10-400 amu Conditions for TCPA Column: 3% OV 101 1m with 1/8" I.D. Program: 100-160 9 8/M1n Hass Gain: 4 Mass Scan: 10-400 amu RSV 0010569 U SPECTRUM DXSPUttVESXT ** GALAXY SB DEL RJUgR, GAM 5 REPEAT nm 0978 PAGE 1 16#K b ***" RSV 0010560 TV1P* H SFECTRUH OZSPLRV^GDXT SS TCPA tCLUARE RXUER l&l 191-168 MBCGsrtXN 8-84-71 UK 17 48 93 Pm 8873 pmc i tan 0* RSV 0010561 Special Study S-75-SS-6 J. F. OUEENV PLANT STANDARD OIL AND GREASE RESIDUES SUMMARY Residues from the standard "Oil and Grease" test were found by GC/MS to contain 35 to 45% Monsanto products or Intermediates. The remaining residue could be "Oil and Grease". DISCUSSION Five samples of residue obtained by Standard Method No. 137. American Public Health Association, as applied to the Clean Acid Stream were analyzed by GC/MS. The results are given In the following table. TABLE COMPONENTS OF RESIDUESTKOM THE STANDARD OIL AND GREASE ON CLEAN ACID STREAM Sample Identification Percent Butyl Percent Accounted Percent Phthalyl Butyl Percent Other Lasso Glycolate Materials Hexane 8/26-8/30 Freon 8/26-8/30 35-45 30-40 35-45 N3-4 5-7 /^2h'09 (^-n-c-ch2 cy Freon and Hexane Combined 9/20-9/27 Freon 10/4-10/11 Freon 10/12-10/16 35-45 35-45 60-70 21-27 9-11 24-28 14-18 16-21 24-28 10-13 Not Identified 12-14 Not Identified The material "not Identified" represents 8 to 10 GC peaks of about 1% concen tration. The diethyl aniline derivative HS N-C-CHg Cl is related to Lasso production. db Monsanto Industrial Chemicals Co. Applied Sciences St. Louis, Mo. 3/75 - G. W. Mappes, M. W. Dietrich RSV 0010562 Special Study S-75-SS-7 RADIOACTIVITY' IN DIPHENYL OXIDE INTERMEDIATES, FINISHED GOODS AND ENVIRONMENTAL EFFLUENT INTRODUCTION Manufacturing and Research representatives held a meeting on 2-5-75 in St. Louis to review status of data required for a radioactive materials license application to the state of Texas for the new thoria catalyst diphenyl oxide plant to be built at Chocolate Bayou. The status of this application and additional information required is summarized in D. R. Miller's meeting report of 2-26-75 (Reference 1). This report sum marizes results and conclusions of the additional research support requested at that meeting. SUMMARY 1. Gamma spectrometry was investigated as an alternative/ supplementary radiochemical analytical tool to liquid scintillation spectrometry for measuring radioactivity. In crude DPO, distillation fractions, refined DPO and miscellaneous samples such as vent traps, filters etc. Sensitivity comparisons between gamma and liquid scintillation spectrometry were made on selected crude DPO distillation fractions including refined DPO. 2. Radioactivity material balance measurements were pro vided for a pilot plant scale crude DPO distillation. This experiment was carried out under "worst case" plant simulated time table to learn (a) if measurable radioactivity was present in refined DPO, (b) the fate of short half-lived Radon 220 and daughter products in crude DPO distillation, and (c) if significant longlived radioactivity (Thorium) was present in still bottoms 5* Before-and-after radioactivity measurements were pro vided for evaluation of the effectiveness of a 10 micron opening Teflon disk filter for removing radioactivity from crude DPO. 4. Radioactivity measurements were provided to estimate the amount of radioactivity vented to atmosphere from the crude DPO storage tank under plant simulated "worst case" conditions. 5. Analysis for long half-life radioactivity was made on selected distillation residues and crude DPO samples. A similar investigation was also made on Teflon filter disks from crude DPO flltratlons. RSV 0010563 Special Study S-75-SS-7 Page 2 CONCLUSIONS 1. _ Gamma spectrometry has been demonstrated to have sensi tivity greater than 2 x 10" uci/ml for thorium in DPO process materials. Data appear in Table 1A and footnotes. Comparison with liquid scintillation spectrometry indi cates the gamma method better for dark crude DPO, distillation residues, carbon filters etc. However, liquid scintillation on refined DPO and light colored scintillator-soluble samples is 5-100 times more sensitive than gamma spectrometry (Table IB). 2. The determination of the fate of radioactivity from crude DPO in a plant simulated distillation showed It to be completely held up in the still pot. No detectable amounts were present in the refined DPO. The pilot plant distillation did not employ filtration or vacuum transfer of crude DPO, but did attempt to simulate plant "worst case11 conditions by distillation of the final eight hours of crude DPO production to maximize total radioactivity present. Results appear in Table 2. 3. Filtration of crude DPO through a single 10 micron opening Teflon disk gave no detectable reduction of short-lived radioactivity. 4. Radioactivity vented from the pilot plant storage under plant simulated "worst case" conditions was completely held up in the first of a train-of-three granular active carbon filled absorbers (Nuchar WV-W, 80 x 30 mesh) and was calculated to be equivalent to 9 x 10~7 uci/ml (air) of thorium. The "worst case" conditions were the total filling of the DPO storage container over an eight-hour period totally displacing gas space into the train of absorbers. 5. A very small (unquantlfled) amount of long-lived radio activity (natural thorium plus daughters) has been found to come forward with crude DPO from the reactor and has been found on filter disks and in distillation residues. Additional work Is needed to quantify results since the total amounts of crude DPO used and the quantitativeness of retention/transfer of radioactivity was not suffi ciently documented. All samples associated with eight hours or less of crude DPO production show no detectable levels of long half-life radioactivity (less than 2 x 10- uci/ml thorium) after 120-140 hours monitoring. Data on the individual samples is given in Table 3* RSV 0010564 DETAILS Special Study S-75-S3-7 Page 3 Determination of Radioactivity Vented to Atmosphere from Continuous Pilot Plant Crude DPO Storage Absorption Apparatus Radioactivity absorbers were prepared by filling three pyrex glass tubes 23 mm diameter x 60 mm long open at both ends with Nuchar WV-W, 80 x 30 mesh carbon. The carbon was held In the absorber with a small wad of glass wool on each end and a one-hole rubber stopper. The absorbers were close coupled In series with short lengths of glass tubing. The absort>er tubes were designed to permit insertion into the count well of the 2x2 Nal detector of the RIDL gamma counter after replacement of the end connectors with thin flushmounted rubber stoppers. Absorption Experiment The pilot plant crude DPO effluent tube was connected to an empty 2-liter Erlenmeyer flask through a two-hole stopper. The series train of 3 carbon absorbers was attached to the discharge opening of the collection flask. An electronic timer switch was set to divert the last eight hours of crude DPO production (prior to catalyst bed regeneration) to the special receiver. Sufficient crude DPO was collected to totally fill the receiver and exit line to the absorbers forcing the original 2 liter air volume through the absorber train. Care was then taken that no crude DPO reached the first absorber by holding the absorber train vertically as the line was filled with liquid and diverting flow Just before liquid reached the absorber inlet. Quantification of Radioactivity Found In Carbon Absorbers Immediate check for radioactivity in all three absorbers showed detectable levels only in absorber No. 1. Further counting of absorber No. 1 with inlet and exit ends of the absorber inserted into the detector well respectively indicated higher activity at the inlet side. A radio activity standard was prepared by addition to a section of stoppered glass tubing Identical to the absorbers, 9 ml deionized water, 0.5 ml concentrated nitric acid and 0.0169 gram Thorium (250 >ul of a standard prepared by dissolution of Thorium oxide pellets from the reactor catalyst stock). After mixing the liquid contents the carbon charge (8.4 g.j was added to the tube. An addi tional 1.5 ml deionized water was added to bring water level to top of carbon. The tube was stoppered* mixed and counted. The radioactivity in absorber No. 1 was measured in the same way. The absorber was opened and and the carbon removed and mixed to better distribute the RSV 0010565 Special Study S-75-5S-7 Page 4 radioactivity. Die deionized water and nitric were to the aipty arimrber tube and the mixed carbon charge was back. _ Additional water was added to cover the carbon and the tube was then stoppered, mixed and counted 20 minutes. The same quantity or unexposed carbon, water, and nitric acid was prepared and counted as a background sample. The following count data was obtained. (See Page 4A) REFERENCES 1. mDP0 Radiological Licensing/Safety Research Center Meeting", D. R. Miller, 2-26-75- .2 Notebook Pages MIC 254342-254400, 269401-296406 (D. Hines). Notebook Pages MIC 296001-296063+ (D. Hines). 4. Notebook Pages MIC 0R214268 (J. E. Silver). Monsanto Industrial Chemicals Co. Applied Sciences St. Louis, Missouri 4/75 - D. B. Hines, M. W. Dietrich RSV 0010566 stuuy --o `t*. O O <N RSV 0 0 1 0 5 6 7 .Sample Absorber f-*l Carbon Background Standard Tlme Clock Elupsed (Hrs.) 3:08 PM 12.7 2:43PM Min. Counted 10.0 10.0 Total Counts 7927 2348 Total cpm 792-9 -- Background (235) 234.8 Net cpm 558 -- Remarks Thorium Standard 2:27PM 10.0 9317 931.7 (217) 715 O.OI69 g* Thorium DPO Crude 10:28AM 8.0 5.0 23211 4642 (217) 4425; Elapsed time - 0 3:16 PM 12.8 hr. 5.0 Deionized Water, Background Sample 8:48AM '1:20PM 20.0 18672 3734 4293 4378 -- (217) 214.7) 218.9) 3517! 217 Decay correction standard and backgound The net cpm radioactivity found In the carbon absorber wa3 corrected to zero elapsed time using the crude DPO decay standard. Itils result was computed as equivalent Thorium using the thorium standard and expressed as equivalent uci thorlum/ml using the "empty" volume of the crude storage tank as representing the volume of radioactivity discharged to environ mental air. Calculation: 1. Absorber count data corrected to time zero 558 x 4425 5517 702 net cpm .2 Thorium equivalence of absorber corrected count data 702 x O.OI69 5. Radioactivity expressed as thorium equivalent per ml of crude DPO storage tank displaced air * 1.84 x 10"3 uci Th 2 VTOT ml 9 x IQ"* uci Th/ml 0.0166 g Th 1.84 x 10"3 uci Hi Sample ..(SinzUe 5 20 20 400 400 TABLE 1 'pedal Study S-75 -oS-7 Page i) ANALYTICAL SENSITIVITY OF GAMMA AND LIQUID SCINTILLATION SPECTROMETRY FOR THORIUM A. GAMMA SPECTROMETRY - AQUEOUS THORIUM STANDARDS Sample Radioactivity Count Period (min) Thorium Present (grama) . net cpm (20) uoi (!) Thorium per ml. 1 Sensitivity^ grams/mi. Uftl/tal.------- O 1* 1 0.3397 20.800 (+288) 2.5 x 10"3 2.24 x 2.49 X 10"* 1-5 0.3397 14,509 1.9 x 10"3 1.38 X 10- + 0.8 x X0- (+248) 20 6.76 x 10~4 28.7 3.75 X 10-" 1.17 X 10-* 1.30 x 10- (+9.9) 10 1.69 X 10"3 2i.6 4.69 X 10"T 2.86 x 10" 3*2 x 10"7 10 5.38 X 10 (+14.5) 50.7 (+10.8) 9.38 x 10~T 1.80 X 10"a 2,0 x 10"7 ASV 0 0 1 0 5 6 8 Sample Crude DPO Phenol-Water Cut 1 (Top phase) B. LIQUID SCINTILLATION - CRUDE DPO AND DISTILLATION CUTS Sample Size (ml) Scintillator and Volume Thorium Added As Int.Sfcd. (grams) Sample Radioactivity -------------- u7i~Ti) net cpm (26) Thorium per ml. (2) Sensitivity grams/ml. uci/ml. 2.0 Packard Instagel/ 0.006758 577+15 18.0 ml. 0.86 x 10"4 1.36 x 10"7 1.51 x 10_a Packard Instagel/ 2.0 20.0 ml. 11 03 -- 2.22 x 10~a 2.47 x 10_T Phenol-Water Cut 1 (Bottom Phase) 3*0 11 19*0 ml. it 0+3 Refined DPO 10.0 m 10.0 ml. n 0+3 4. S* it ; n J* / ^ V r -- 1.23 x KTa 1.37 x XO_B - - 6.36 x 10"7 7.07 X 10"fl Table 1 Footnotes Special Study S-75-SS-7 Page 6 (l) DPO process gamma radioactivity may arise from both short- and long-lived nuclides. It Is not practical to duplicate the many gamma energies in the short lived radioactivity of DPO samples with calibrated long-lived standards in order to determine precise counting efficiencies and permit expressing the radio activity levels in the regulatory units of ucl/ml for each nuclide. Instead, the catalyst thorium oxide catalyst pellets which contain these short-lived along with longer lived daughters are dissolved and used as the radioactivity standard. The "catalyst thorium" with its mixture of daughter products is taken to be the "natural thorium" given in the AEC regulations (Part 20, Appendix B). The use of this material as a radioactivity standard has the advantage of a regulations defined weight/radioactivity relationship: 9000 Kg thorium natural equals 1 curie. Therefore, all radioactivity in DPO process samples is expressed as that of an equivalent amount of catalyst thorium radioactivity measured under the same conditions. (2) Method sensitivity is taken as that quantity of thorium catalyst standard giving the net counts per minute equal to twice (2a) the theoretical or experi mental standard deviation of the background determined for the same period of time. Example: The background of 20 ml of distilled water counted in a gamma count vial for 20 minutes is 4^52 counts. The theoretical standard deviation is a = + ^ cpm - + = 3*3 cpra where N is the total number of counts taken and 20 is the minutes counted. The thorium standard used in this study counts 42748 net cpm/gram thorium per 20 ml sample. The sensitivity is then determined as . - 2(fN) _ 2(5.3) = *(grams thorium) 42748 T2746-- Since 9000 Kg natural thorium 1 curie 9 grams thorium * 1 uci and x 10-* Suol thorium * 1-^4- - 1-72 x 10-* Since 20 ml samples are used 1.72 x 10'S - 8.58 x 10-T ucl thorium/ml. S " ---------- 25-------- - 0.86 x 10-6 " RSV 0010569 Special Study S-75-SS-7 Page 7 TABLE 2 CRUDE DPO DISTILLATION EXPERIMENT (DISTRIBUTION OF RADIOACTIVITY.DETERMINED BY GAMMA COUNTING Co)) Component Weight (grams) Crude DPO Charge 2006 Thorium __________ net cpm per 20 g. (20) uci/ml. 3487 + 29^ (32898T + 2748) (Total charge) 4.5 x 10~4 Method Sensitivity' ! 2a \ (uci/ml.) ' (0.86-1.3) x 10'" Phenol-Water Cut 1 Top phase Bottom phase 90 Phenol Cut 1261 0-9-6 + 9*5 0 + 9-3 0-8.6 + 9-3 ND 1.3 x 10"8 ND A 1.3 x 10"a it 11 11 Phenol - DPO Slop Cut Refined DPO Cut Column Holdup Residue Still Pot Rinses Cold Traps Unaccounted for 138 399 84 15 -- 3 16 0-10.9 + 9-5 11.0 + 9*5 27-0 + 9*5 38,448c4) (5) 290,997 -- -- ND * _ 1.3 x 10 ND* 1.3 x 10*8 3.5 x 10"8 5000 x 10~8 37,818 x IQ"6 -- -- it n 11 11 11 --- Table 2 Footnotes: (1) See Footnote 1, Table 1. (2) See Footnote 2, Table 1. (3) The radioactivity of ;fresh crude DPO may hold fairly constant or increase slightly for the first few minutes of elapsed time due to the rapid decay of Rn-220 and Po-2l6 and the buildup of longer lived Pb-212. On older samples the radioactivity holds fairly constant for about the first hour, Ihis value Is the average of the first five 5-minute counts of the crude DPO distillation charge. (4) Hiis level of radioactivity is obtained by applying a linear extrapola tlve based on the ratio of radioactivity in crude DPO at time 0 and at an elapsed time equal to that of the sample(s). TOiIs is not strictly a linear relationship (Fig. l). RSV 0010570 Special Study S-75-SS-7 Page 8 Table 2 Footnotes (continued) (4) (continued) The actual radioactivity balance in charged DPO crude and still bottom residue at the end of distillation was made at the more linear region of the decay curve at the 500-600 elapsed minutes region. (5) The major portion of the radioactivity balance was recovered as a series of eight rinses of the still pot in this order: 1 - acetone, 2-acetone, 3-aqueous radlac concentrate, 4-aqueous radlac concentrate, 5-acetone, 6-chloroform, 7-chioroform, 8-10# HP. (6) The gamma counting was performed on a Radioactive Industry Develop ment Laboratory (RIDL) modular single channel analyzer utilizing a RIDL 2" x 2" Nal (T l) well crystal detector. Well dimensions are 1 inch diameter x 1-1/2 wide deep. Instrument count parameters were optimized using the thorium catalyst standard. Twenty milli liter samples were counted for periods of 1-30 minutes in the evaluation. rs v 00X0571 Page 9 0. U * RSV 0010572 Special Study S-75-SS-7 Page 10 TABLE 3 EXAMINATION OP THORIUM CATALYST DPO PILOT PLANT PROCESS SAMPLES FOR LONG-LIVED RADIOACTIVITY________ A. SAMPLES FROM CRUDE DPO DISTILLATION (8 HRS. OF PILOT PLANT PRODUCTION, RUN E-327)___________________ ____________Sample________ Elapsed Time . fhrs.) N^t^cym Count Method 1- Still Pot Residue 2. Still Pot Rinse 3 (Radlac Concentrate) 3. Still Pot Rinse 6 (Chloroform) 4. Still Pot Rinse J (Chloroform) 0 40 73 139 161 0 73 140 0 120 137 189 0 120 138 22,049 1,866 211 + 11.5 0 + 9.2 0.9 + 6.2 60,043 520 1-9 7-3 39,912 ^ 25.9+ 7.6 29-3+ 6.6 24.5+13-2 27,190 33.2+ 7.7 28.1+ 6.5 Gamma it tt ti I! Spectrometry II ft tl II II tt II II It It II tt ft II It 11 M If tt II M If II 1, B. CRUDE DPO, RUN E-331 FRACTIONS 0-23 AND 24-57 MINUTES FOLLOWING CATALYST REGENERATION Elapsed Fraction Time (Hrs.) Net Com 26 0-23 Min. 23-57 Min. Count Method 0 12,652 6,067 Gamma Spectrometry 4-5 12,485 7,U7 70 187.6 + 9.6 115-7 + 11.4 100 31.6 + 6.6 19*5 + 6.7 11 M 125 10.6 + 5.9 5.2 + 8.5 145 4.0 + 13.1 0 + 8.5 RSV 0010573 Special Study S-75-SS-7 Page 10A TABLE 3 (Continued) C. TEFLON FILTER DISK FROM CRUDE DPO FILTRATION Sample DPO Crude Batch Elapsed Time (Hrs.) Net cpm (2tr) 10 micron opening Teflon Filter Disk, Acetone Rinsed a) 0 4 19 27 48 67 140 164 212 237 310 331 364 57,896 53,737 20,333 14,665 3,321 923 30.4 24.8 + 3-6 24.6 + 7o 27.4 + 3.9 20.8 + 4.9 25.2 + 4,1 21.8 + 4.6 10 micron opening Teflon Filter Disk, Acetone Rinsed E-3 28 (Last 8 hours Collection) 0 26 94 120 150 172 19,912 5241 + 65 65*6 + 7-3 10.5 + 2.8 2.1 + 1.2 0.0 + 1.6 Count Method Flow Proportional Counting ti (l) Sample came from a filtration technique evaluation and represent an estimated 4-000 ml crude DPO. The container, however, had been used to collect numerous batches. RSV 0010574 TABLE 4 jpeclal Study S-75"o.'j-7 Page 11 Sample Crude DPO Charged to distillation Phenol - Water Cut 1 Top Phase Bottom Phase Phenol Cut Refined DPO Cut Phenol - DPO Slop Cut Column Holdup CRUDE DPO DISTILLATION FRACTIONS COUNT DATA UNCORRECTED TO TIME ZERO Clock Time a) Total Counts 8:05AM 8:15AM 8:19AM 8:25AM 8:32AM 8:55AM 9:00AM 11:12AM 12:30PM 2:56 PM 4:50PM 7:05PM 18,560 18,389 18,587 18,485 18,499 18,184 18,048 16,572 3,087 13,484 12,050 10,701 Min. Counted. 5.0 5.0 5-0 5.0 5.0 5.0 5-0 5.0 1.0 5-0 5-0 5-0 Total cpm _Remarks i 3712) 3678) 3717) 3697) 3697) 3637 3610 3314 3087 2697 2410 2140 Average of first 5 counts * 3701 + 27.6 (2o ) 9:42AM 9:47AM 11:34AM 12:25PM 10:01AM 10:11AM 10:43AM 197 2,215 4,517 4,334 218 2,225 4,289 1.0 10.0 20.0 20.0 1.0 10.0 20.0 197 222 226 217 218 223 214 2 :08PM 4,477 20.0 224 1:27PM 4,519 20.0 226 2:29PM 4,507 20.0 225 2:50PM 4,727 20.0 236 RSV 0 0 1 0 5 7 5 Footnotes -- see following page Special Study S-75-SS-7 Page 11A Sample Residue as received (15 grams) Clock Time (1) TABLE 4 (continued) Total Counts Min. Counted Total c pm 12:26PM 44,604 1.0 44,604 Remarks 1 Residue diluted to 20 ml. with acetone Still Pot Rinse 1 (Acetone, 20 ml.) Still Pot Rinse 2 (Acetone, 20 ml.) Still Pot Rinse 3 (Radlac, 20 ml.) Still Pot Rinse 4 (Radlac, 20 ml.) 6:05PM 111,419 1:03 PM 6:55PM 4,885 12,973 1:05PM 6:35PM 1,618 5,227 3:53PM 71,680 6:50PM 301,392 4:43PM 12,306 6:57PM 54,436 5.0 1.0 5-0 1.0 5.0 1.0 5.0 1.0 5.0 22,284 4,885 2,595 1,618 1,045 71,680 60,278 12,306 10,887 RSV 0 0 1 0 5 7 6 Still Pot Rinse 5 (Acetone, 20 ml.) Still Pot Rinse 6 Chloroform, 20 ml. Still Pot Rinse 7 Chloroform, 20 ml. Still Pot Rinse 8 9, 10 (10# HF, 20 ml.) Charcoal Absorber 1 Charcoal Absorber 2 6:20PM 28,234 5-0 5,646 40 ml. rinse, 20 ml. counted 5:03PM 41,670 6:45PM 200,736 6:12PM 137,126 1.0 5.0 5.0 41,670 39,912 27,190 5:51 5:57 2:50PM 3:04 PM 3:06 PM 3:UpM 5,969 29,972 228 979 235 1,162 1.0 5,969 60 ml. rinses combined, 20 5-0 5,994 ml. aliquot counted 1.0 5.0 i\ 1.0 5.0 228) 196) 235 ) 232) Absorbers used between still overhead rec and vacuum pump Special Study 3-75-S3-7 Page 11B TABLE 4 (Continued) Sample Clock Time u> Total Counts Min. Counted Total cpm Remarks Steel wool from DPO Product line of Distillation Equip- ment 3:20PM 221 1.0 221 Deionized Water. 20 ml. 9:50AM 11:06AM 4:14PM 5:44PM 7:20PM 2,140 *1,352 4,664 4,747 2,372 10.0 20.0 20.0 20.0 10.0 214) 218 233, 257 237) Sample was used as background sample. Footnotes: (1) All measurements for radioactivity material balance made on 3-11-75* Time "0" taken as 8:19AM since the 2o confidence limits of the average of the firet 5 five minute counts of crude DPO was indistinguishable from the difference of 1st and 5th count. RSV 0010577 Special Study S-75-SS-8 TRACER LITHIUM ANALYSES - NITRO PLANT EFFLUENT SUMMARY Lithium is used as a tracer to observe the dilution of the Nltro plant liquid effluent. Thirty-one effluent samples ranging from 0.05 to 0.13 ppm LI were analyzed by atomic absorption. DETAILS The samples appeared uniform but cloudy, almost neutral. Cursory analyses showed much sodium, calcium, but less than 1 ppm Li. Both air-acetylene and nitrous oxide-acetylene flames were tried, and the Boling burner. The latter produced acute curvature. The best ratio of response over noise was found with the nitrous oxide burner using air-acetylene as a strongly oxidizing flame. The effects of sodium ion and acid addition were checked. These did not affect the base line run in water. Hydrochloric acid addition had no effect on the sample response. All samples contain sodium which produces enhancement. There is a matrix effect, cause unknown, therefore the method of standard additions for calibration was chosen. Because this method is very time-consuming and because the most dilute sample would have a response of only ten times the noise level, the method was applied to a random selection of five of the samples. All of the samples, including the selected five were run directly, without dilution and without additions. Each sample was agitated, then allowed to stand for one minute before analysis. Each sample was run at least twice, using deionized water as reference. The standard addition zero level was run before and after its set. The five standard addition ppm values were graphically plotted against their direct run absorbance values. The "best line" through this plot was used as the calibration curve from which each sample's absorbance value was read to pro vide the corresponding ppm as listed in the table. db Monsanto Industrial Chemicals Co. Applied Sciences St. Louis, Mo. 4/75 - 0. E. KInast, M. W. Dietrich RSV 0010578 Sample Number I2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 ppm Lt 0.046 .136 (0.134)* .129 .124 .124 .122 .121 .119 (0.122) .115 .113 .111 .108 .104 .100 (0.096) .098 -093 Sample Number 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 ppm LI 0.087 .085 -079 .076 (0.074) .071 .070 .068 .066 .061 .059 (0.061) .057 .055 .052 .051 .049 Values In parentheses were obtained by method of standard additions RSV 0010579 Special Study S-75-SS-9 MALEIC ANHYDRIDE REFINING PROCESS IMPURITY SUMMARY An Impurity with a boiling point between maleic anhydride and dibutyl maleate was observed In the refining step for new process maleic anhydride. The possibility that this Impurity could cause quality problems required that It be Identified. NMR, IR, and two types of mass spectroscopy were required to Identify the Impurity. It was Identified as H lH ! CH3-CH2-CH2-CH2-0-C^ t * 0 DISCUSSION GC analysis of a residue from the maleic refining process showed two unknown impurities which eluted between maleic anhydride and phthallc anhydride. These are designated peaks A and B In the figure. Elec tron Impact GC/MS did not give molecular weight Information on either Impurity and showed unusual fragment Ions for peak A. The IR spectrum of B trapped from the GC separation showed that It was dibutyl maleate. Although succinic anhydride has the same retention time as dibutyl maleate on the GC column used for this analysis, no succinic anhydride was observed In the IR spectrum with a detection limit of 5 to 10% of the dibutyl maleate concentration. The IR spectrum of peak A trapped from the GC separation suggested that this material was not one of the expected process Impurities and that It had some unique structural features. GC/MS analysis of peak A using chemical Ionization mass spectrometry Indicated a molecular weight of 156. Hexane extraction of the residue produced a large enough sample of Impurity A for NMR analyses. This analytical data indicated Impurity A has the structure shown above. Since this Impurity was obtained by extraction as well as GC separation, It could not be the result of some sample decomposition during the GC analysis. db Monsanto Industrial Chemicals Co. Applied Sciences St. Louis, Mo. 5/75 - G. U. Mappes, B. Katlafsky, 0. E. Klnast, M. W. Dietrich RSV 0010580 P h th a llc A nhydride .3A Veo U 40 40 O- 3a no i j ASV 0010581 At j6u t ^ * yI*+* C>-$ A Special Study S-75-SS-10 ANALYSIS OF BENZENE IN AIR AT ANNISTON. ALABAMA PLANT INTRODUCTION ` The purpose of this investigation was to determine worker exposure to benzene, SUMMARY The first three sets of samples collected over an 8-hour day were all below 5 ppm. One high non-representative sample was found due to direct exposure of the collection tube to a benzene bath. During this study*we found that benzene vapors slowly permeate the teflon tape used for sealing the ends of the collection columns. This gave detectable levels of benzene in tubes used as blanks at Anniston. Tubes kept in St. Louis did not have detectable levels of benzene. The levels given in the tables should be considered maximum exposure values since as much as 3 ppm may be due to this benzene blank. The fourth set of samples were taken for fifteen minutes in high exposure regions of the benzene process. The results are given in Table IV. As much as 39 ppm benzene was observed. EXPERIMENTAL GC/MS was used in the verification of benzene and calculations are based on a benzene standard. An example of the calculations is given below. Results shown for the blanks were calculated on the basis of the same volume of air used for the samples. Calculations Volume of Air . pump flow rate x sampling time x io*3 Sampled (liters) (ml/min.) (min.) Wt. of sample (pg) area sample peak x cone, std. (jug/4ul)Vol. ln,1. (ul) (counts) Area of sta. ;counts) Concentration of sample (Mg/1) Concentration of sample (ppm) Weight of sample (jug) ______ Volume of air sampled (liters) 24.5 Mg/1 (sample) x fOT (sample) RSV 0010S82 \ Special Study S-75-SS-10 Page 2 For Sampling #2 of Set 4 ' Volume of air sampled (liters) 817 ml/rain, x 15 min. x 10~3 Wt. of sample (ms) h695 X 1 x 1.0 15^2 Cone. Benzene (fig/1) 1542 . 126 12726 Cone. Benzene (ppm) 39 12.26 Reference: GC/MS File #75-24 Monsanto Industrial Chemicals Company Applied Sciences Section St. Louis, Missouri 4/9/75 - L. M. Chapman, M. W. Dietrich RSV 0010583 Special Study S-75-SS-10 Attachment - 1 TABLE 1 Set I Pump flow, 20 ral/mln. (Model 222-451 SKC pump) Sample Time, 8 hr. Tube #3 #4 #5 # 1 (blank) ppm of Benzene 0.2 0.7 0.7 lost In analysis TABLE II Set II Pump flow, 20 ml/min. (Model 222-451 SKC pump) Sample Time, 8 hr. __________ Tube #16 (blank) # 6 (St. Louis blk.) #17 #18 #19 #25 ppm of Benzene 0.4 0.02 x not a representative 120.0 sample because of direct exposure to benzene. 4.2 1.5 0.2 RSV 0010584 Special Study S-75-SS-10 Attachment - 2 Set III TABLE III Pump flow, 20 ml/min. (Model 222-451, SKC pump) Sample Time, #1 and #2 - 8 hr, and 15 min. Remaining samples - 8 hr. Tube #1 #2 #3 #4 # 5 (blank) # 6 (St. Louis blk.) 1.0 1.0 1.4 2.3 1.5 0.02 TABLE IV Set IV Pump flow, 817 ml/min. (Model C-115# Bendlx pump) Sample Time, 15 min. ________Tube #2 #3 # 4 (blank) #5 #16 #17 (sealed blk.) #25 (St. Louis blk.) ppm of Benzene 39. 33. 3.0 x High level 21. 0.7 0.3 x shut down Instrument RSV 0010585 Special Study S-75-SS-11 ANALYSIS OF VOLATILES IN DECATUR. ALABAMA PLANT AIR (III) INTRODUCTION This Is a continuation of an Investigation to determine concentration levels of vinyl acetate (VA) and acrylonitrile (AN) In air at the north continuous polymer area of the Decatur, Alabama plant. The data obtained will be used to Identify areas where worker safety problems may exist. SUMMARY Results of the study are found In Table I. 6C/MS provided the means of Identification of the volatiles. Acrylonitrile had values of from 0.4 to.2.4 ppm while vinyl acetate values ranged from 0.2 to 1.0 ppm. EXPERIMENTAL Refer to Spectroscopy Method 74-7 for the analyses procedure used. Ten minutes was allowed for the heating of the external collection column to collect the acrylonltrl1e before proceeding as In Method 74-7. Adaptions of hardware have been made for our new HP 6C/MS. An example of the procedure used to calculate concentration Is given In the S-75-SS-1 report. Sample collection was made using a Model 222-451 SKC pump. Calculations were based on known VA and AN standards. Reference: GC/MS File #75-57. db Monsanto Industrial Chemicals Co. Applied Sciences St. Louis, Mo. 4/75 - L. M. Chapman, H. W. Dietrich RSV 0010586 TABLE I *M-3 #7 Reactor cleaning-chipping scale and removal by operator m TR VA <2.4 <1.0 M-4 Reactor overflow sampling and cleaning 0.4 0.9 M-5 Changing filter cloth on B line secondary filter 0.5 0.2 ^Values for M-3 are maxlmums because of possible Interference of other components when calculating concentrations. RS V 0010587 Special Study S-75-SS-12 ORGANIC CHEMICALS IN CHOCOLATE BAYOU PLANT HATERS SUMMARY Haters from various places In the steam and water systems at the Chocolate Bayou plant were analyzed for organics to determine Its suitability for the sorbic acid process. No organics were found in the finished water samples with a de tection limit of 0.5 ppm total. Low levels of aliphatic compounds were found In steam condensate samples. DISCUSSION Hater for plant usage Is taken from the Brazos River, filtered, passed through water softening resins, flash evaporated and pimped to various plant uses. Two sauries of water from each of four points in the purification were taken for analysis. One sample of each pair was acidified to pH*2 with sulfuric acid. Two additional samples of condensate returned from steam usage were also analyzed. One was from the phenol process, the other was from the ethylene process. The results for these samples are given In the table. The filtered water Is river water which has been filtered only. The polished water has been filtered and softened. The evaporator water has been filtered, softened and flash evaporated to remove dissolved solids. The nedlun pressure water Is polished water and condensate returned from steam usage. All were analyzed by methylene chloride extraction as outlined in Spectroscopy New Technique 70-3. Identification was done by GC/MS and IR. Extractable organics were found In only the steam condensate. GC/MS analysis of these organics showed that they were a series of aliphatic compounds. IR showed definite nitrogen content. This suggests that these compounds are related to the Inhibi tor used In the steam lines and probably are decomposition products of the inhibitor. The total organic Carbon TOC values for the steam condensates were done using the Envlrotech DC-50 Organic Analyzer. db Monsanto Industrial Chemicals Co. Applied Sciences St. Louis, Mo. 5/75 - G. H. Mappes, 0. E. Klnast, M. H. Dietrich RSV 0010588 ORGANICS IN CHOCOLATE BAYOU WATER Filtered Water pH 6 pH 2 Extractable Organics Total iE51 <0.5 <0.5 Polished Water pH TO pH 2 <0.5 <0.5 Evaporator Water pH 8 pH 2 <0.5 <0.5 Med. Press. Water pH 10 pH 2 <0.5 <0.5 Steam Condensate Phenol Process 0.5 to 1.0 Steam Condensate Ethylene/Hydrocarbon Process 1.0 to 1.5 Phenol <0.2 <0.2 <0.2 <0.2 <0.2 <0.2 <0.2 <0.2 <0.2 <0.2 TOC (ppw) <5* <5* <5* <5* <5* <5* <5* <5* 6+2 7+2 Determined at Chocolate Bayou ft$V 0010569 Special Study S-75-SS-I3 DETERMINATION OF BENZYL CHLORIDE IN DELAWARE RIVER PLANT AIR INTRODUCTION Personnel monitor for benzyl chloride tn elr to determine worker exposure levels at the Delaware River plant was carried out In the $-160 department. SUMMARY See the attached table for results. Levels of benzyl chloride found were <0.1 Ug/A. Other components Identified were toluene, xylene, chlorotoluene, chloro benzene, dichlorobenzene, dichlorotoluene, and naphthalene. Levels of these components can also be found tn the table. EXPERIMENTAL Tenax GC was used for collection and analysis. GC/MS was used for Identification. Calculations are based on a benzyl chloride standard. Air sample sizes were between 7 and 16 liters with flow rates between 35*65 ml/mln. Calculations Volume of A!r Samples (Liters) Pump Flow Rate (rnA/mln) SanpHng Time v tA_* (min) X 10 Weight Sample (vg) Concentration Sample (lig/L) For Sampling OP-1 Area Sample Peak * Cone. Std. (liq/ut) xVol. Injected (uL) (Counts) * Area of Standard (Counts) Weight Sample (yg)/Volune of Air Sampled (Liters) Volume of Air Sampled (L) 60.6 X 293*6 X 10* - 11.92A Weight Sample (ug) '589*7* X I5l5y.-1.oug Concentration (ug/L) 1.0 TT792 0.08 - 0.1 Reference: GC/MS File #75*89. Benzyl Chloride Method Validation A series of experiments were performed to verify this procedure Is quantitative for benzyl chloride. The set of GC conditions are given at the end of this report; other experimental conditions are described separately. Test I The analytical column was connnected to the GC and an empty glass insert used. Then 1.5 1*A of the standard was injected and the program Initialized. Peak area of benzyl chloride was observed and recorded. RSV 0010590 Teat II Special Study S-75-SS-I3 Page 2 This timer when the analytical column was connected, a packed Insert was placed In the Injection port. Note this was a freshly conditioned Insert and no air had been passed through It* Again 1.5 ut of the standard was Injected, the program Initialized, and peak area of benzyl chloride recorded. Test IM Next, 1.5 of the standard was Injected Into a 50 at gas sampling bulb. A diagram of the apparatus Is given at the end of the report. A SKC-222-k51 pump was used in collecting the sample. A collection with flow 76 ml/m in for one hour was made and the insert placed In the GC as In Test II and run. Test IV The last experiment was the same as Test III except a flow of 25 ml/m In for 5 hours was made. [A sens'!ing for k hours at 4 ml/mln was also conducted with a C-105 Insert and showed 952 recovery.] RESULTS from Test I and II, the results showed that the material absorbed on the Tenax Insert was desorbed fn the analysis. Similarly results from Test III and IV verified that the sample Is quantitatively collected from the air by the Insert whether It be a fast or slow flow rate. Accurate analyses should be obtained as long as the breakthrough volune for benzyl chloride Is not exceeded. See table for percent recovery In the experiments described. GC Conditions GC-7620 H.P. Flame Analytical Column: 2H glass Tenax GC Collection Column: Glass Tenax Insert Program: 50 (k min) - 250 9 15*/Hln. Attenuation: k X 10s X 1 Reference: GC File #75-95- db Monsanto Industrial Chemicals Applied Sciences St. Louis, Mo. Co. 5/75 - L. H. Chapman, M. V. Dietrich RSV 0010591 OP-1 Benzyl Chloride <0.1 COP-1 <0.1 LT-I <0.1 OP-2 <0.1 COP-2 <0.1 OP-3 <0.1 D-l <0.1 LD-I 0.1 OP-4 <0.05 COP-3 <0.05 Unknown <0.1 <0.05 <0.05 <0.05 <0.05 <0.1 <0.05 NO <0.05 <0.05 Toluene* 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.1 <0.1 TABLE Concentration (lig/M Chloro Chloro- benzene Xylene* to1uene NO** <0.1 0.1 NO <0.05 <0.1 <0.05 <0.1 ND <0.05 <0.05 ND <0.05 <0.05 <0.1 <0.1 <0.1 0.1 NO <0.05 <0.1 ND NO ND ND <0.05 ND ND <0.05 <0.05 Dichloro benzene 0.1 <0.1 <0.05 <0.1 <0.1 0.1 ND ND <0.05 <0.05 Dlchlorotoluene <0.1 <0.05 <0.05 <0.05 <0.05 <0.05 <0,05 ND <0.05 <0.05 Naphtha lene <0.05 Comments <0.05 <0.05 ND <0.05 ND Sample partially lost due to leak In system <0.05 ND ND ND *Toluene and xylene results are probably low because the breakthrough volume of these components was exceeded. **ND Detection limit <0.0$ RSV 0 0 1 0 5 9 2 TABLE Test I: Direct Injection on Analytical Column Test II: Injection on Collection Colum and Analytical Column Test III: Collection g 76 ml/ min for 1 Hour on Tenax Test IV: Collection 25 ml/ min for 5 Hours on Tenax Collection g 4 ml/ min for 4 min on C-105 Amount Injected of 1.56 ug/ui Std. I -5 ul Amount Recovered 1001 1.5 Ul 951 1.5 ul 1.5 ul 1.5 u* 831 981 941 RSV 0010593 &I 3 i RSV 0010594 Special Study S-75-SS-H DETERMINATION OF TOLUENE DlISOCYANATE IN AIR (II) _____ IN THE SUPER DOME________________ INTRODUCTION This analyses was undertaken to determine concentrations of toluene dlIsocyanate (TDI) In air during Astroturf installation In the Super Dome at New Orleans. SUMMARY Samples from the Installation showed no TDI detected with a detection limit of 4 ppb. Methyl Ethyl Ketene (MEK) was observed at a level of >0*06 ppm. Con centration of other unidentified organics totaled around 0.02 ppm. A description of the samples Is given In the attached memo. Two samples of the adhesive used In planting the Astroturf were also examined. The first, Vorite 677* an adhesive previously used In this application, showed only MEK and TDI In the headspace. The adhesive now used In Astroturf installa tion, Spencer Kellogg, contained besides MEK and TDI, a considerable amount of toluene and some xylene. Several other trace components not specifically identified appeared to be alkylated benzenes and aliphatic amines. A chromato gram is aetached. In comparing the adhesives with the air samples, toluene does seem to be present In the air samples. The amount would be invalid because breakthrough would have occurred. Reference: GC/MS File #75-93. db Monsanto Industrial Chemicals Co. Applled Sciences St. Louis, Missouri 5/75 - L. M. Chapman, M. W. Dietrich RSV COLO*95 f*jh P f f r"^ n -A-..-! 6 / 6 #U*-"'k-~~ j-crv------ J, 4X/e* AjyC*J> 30 a *-%. o o.4 I \ n_^ RSV 00L0596 Monsanto ri .um iteTiMi Carl D. Bohl - Medical Dept. - A2SA ` April 7, 1975 ec` J. T. Garrett TO : Linda Chapnan - T2B All samples were obtained with a flow rate of 2 1pm Indicated on the rotameter. Two pumps were used, and two orifices only. The sample orifice was always used with the same pump. You have one set for calibration. The other set Is presently at the Luling, Louisiana Plant and will be given to you for cali bration when it is returned. The samples that were obtained were as follows: Tube 98 was sampled using Pump #6 with orifice #56 from 8:30 a.m. to 9:12 a.m. during which time glue was being applied to the back of Astroturf with a 2" paint brush. This was being performed by Mr. Sandy Clark. Tube #64 was obtained using Pump #6 and orifice #56 from the operator of the grass tractor starting at 10:57 a.m. and end ing at 11:19 a.m. Tube #109 was obtained using Pump #2 and orifice #60. The sample was started at 10:32 and ended at 11:52. It is the exposure of the glue tractor driver. At 11:15 a.m. trouble developed with the glue pump, and for the last seven minutes the exposure was during repair of the pump. Tube #57 was obtained using pump #6 with orifice #56. The sample was started at 3:13 and ended at 3:25> and represented the entire time that seam spraying was performed. Tube 97 was obtained with the use of Pump #2 and #60 orifice. It was started at 8:13 a.m. and ended at 10:13 a.m. during the performance of hand seaming. Tube 33 was used with Pump #6 and orifice #56 by the shield man during the spraying of glue. The sample was started at 12:25 p.m. and ended at 1:27 p<~ mlw RSV 0010597 Spectroscopy Special Study 75*15 MODIFICATION OF A GAS CHROMATOGRAPH FOR EXTERNAL USE OF THE CARRIER GAS SUMMARY - This report describes the modification of a gas chromatograph which, makes the carrier gas conveniently available for use external to the chromatograph. For example, the helium carrier gas may be used to purge the organics from an externally mounted air sampling tube onto the head of an analytical column mounted in the CC oven. DISCUSSION Most gas chromatographs have a carrier gas ftttlng which Is connected to the Injection port through a flow controller valve and a molecular sieve trap. A three port valve can be placed In the carrier gas line between the molecular sieve trap and the Injection port and mounted on the top or the side of the chromatograph (see diagram attached). With a valve of this type Installed, the carrier gas can easily be switched to the external line. Since the valve Is after the flow controller, one can use the external helium line for chromatographic purposes. We typically connect this externa) carrier gas line to one end of an air sampling tube. The other end of the tube Is connected to the Injection port of the chromatograph at the septum nut. Using the three port valve the carrier gas can be switched to the external line and used to flush organics from the heated sampling tube onto the head of the analytical GC column, in this position the three port valve closes the normal carrier gas line to the Injection port. This keeps sample and carrier gass from leaving the Injection port through the normal carrier gas line. We have found that a Whltey valve SS-A2XF2 works well for this modification. This valve has an intermediate position at which the input port is connected to neither exit port. This position can be used as a convenient shut-off for the carrier gas. 5S Monsanto Industrial Chemicals Co. Applied Sciences St. Louis, Mo. 7/75 - G. W. Nappes, L. M. Chapman, M. W. Dietrich RSV 0010598 t X T t - ^ 'A u C AKXiER . 6 /iS, DIAGRAM FOR S-75-SS-I5 RSV 0010599 Special Study S-75-SS-16 INTRODUCTION NC-220 QUALITY In a previous study of deposit formation In Pydraul fluids (MICC Applied Sciences Spectroscopy Special Study 74-14), amides were detected In many of the samples analyzed. These amide components could be caused by: 1. Reaction products of the l-methyl-2-pyrrolldone catalyst used in the manufacture of the Pydraul base stock phosphate ester. 2. Contamination by the customer. 3. Nitrogen fixation of the air trapped In the hydraulic system. An In-depth study was made of a reserve production sample of NC-220, the Pydraul base stock, by earth filtration, IR (Infrared) analysis, NMR (nuclear magnetic resonance) analysis, XRF (X-ray fluorescence), and GPC (gel permeation chromatography) to determine If any of the amide components are inherent In the manufacturing process. SUMMARY IR, MIR and XRF analyses of materials isolated from new NC-220 showed: 1. Presence of a reaction product of an amide with the phosphate ester. 2. Pyrophosphate or polyphosphate esters. 3. An amide compound free of phosphorus which is not 1-methyl-2pyrrolldone or 2-pyrrolldone. 4. No epoxy stabilizer-phosphate ester reaction product (NC-220 should contain no epoxide stabilizer). 5. Presence of metallic entitles with calcium as the major and Iron, nickel and zinc as the minor elements detected. Materials isolated from a filter deposit from a Pydraul 50E system at Chevrolet's Messina plant (TSR 74-123) contained mixtures of the epoxy phosphate ester and amide-phosphate ester reaction products. The probable structure of the epoxide reaction product Is Indicated In the discussion. The presence of the epoxide reaction product prevented establishing whether the amide reaction product was the same as that found In new NC-220. Total nitrogen levels In five random reserve samples of NC-220 varied from 0.03 to 0.06S. Filtration through attapulgus earth reduced the nitrogen level in one sample by a factor of three. RESULTS AND DISCUSSION A plant batch of NC-220 flIC 225748-C) was percolated through an "earth" column without dilution. After elution of the fluid, the absorbed materials were recovered by washing the column with acetone and methanol. RSV 0010600 S-75-SS-16 Page No. 2 A filter deposit front a Pydraul 50E Installation at Chevrolet's Messina plant was fractionated by solvent extraction with hexane, chloroform, acetone, oethanol and water. IR analysis of the acetone and methanol fractions from the "earth" filtra tion after hexane washing to remove residual NC-200 Indicated high nitrogen contents, apparently a reaction product of an amide with a partially hydrolyzed phosphate ester. The reaction product contains both 0 N -C-N- , P-0 and P*0 bonding. IR analysis of the fractionated filter deposits showed the same types of products found previously In Pydraul SOE deposits namely the reaction product of the epoxy stabilizer with the partially hydrolyzed phosphate ester base stock, and metal salts of these Interaction products. The fraction Isolated by acetone extraction of the hexane and chloroform Insoluble portion of the deposit showed the presence of an Interaction product of an amide and the phosphate ester. The acetone and the methanol eluted fractions from the earth filtration of the new NC-220 (MIC 225748-C) and the Isolated hexane and chloroform Insoluble/ acetone soluble fraction from TSR 74-123 were further separated by molecular size using GPC. The Isolated fractions were analyzed by IR and NMR. The results tabulated In Tables I and II for the acetone and methanol eluted fractions from the earth filtration showed as expected no Indications for the presence of the sticky epoxy-phosphate ester reaction product associated with valve, filter or pump problems encountered using Pydraul E series fluids (see HICC Applied Sciences Spectroscopy Special Study 74-14). Two types of amide containing reaction products were observed In the acetone eluted fraction: about a 1:1 and about a 2:1 amide-phosphate ester reaction product. Since the catalyst 1-methyl-2-pyrrol 1 done is the only nitrogen containing entity used in the phosphate ester process, it must be assumed that the catalyst is the amide portion of the observed reaction products. The methanol eluted fraction from the earth filtration showed the presence of polyphosphates or pyrophosphates. NMR and IR again indicated the presence of an amide reaction product. The f#4R spectra were very similar to that of N-methyl pyrrol1done Including the presence of a signal attributed to N-methyl. A low molecular weight amide was also found that may be the active component In the reaction product with the phosphate ester. The quan tities Isolated were too small for further characterization by other instrumental methods. The GPC fractionation of the acetone soluble portion of the Chevrolet Messina plant filter deposit (TSR 74-123) showed the presence of mixtures of the epoxy stabilizer-phosphate ester reaction product seen In all the previous problems with Pydraul E series fluids. The NMR spectrum of this adduct looks very much like that of Admex 710 which is further reacted with a molecule containing no ArH and no other RH. A possible mechanism of formation could be reaction of an acid phosphate with Admex 710 followed by hydrolyses of the reaction product. RSV 0010601 A jP 9" J , R C-C + HOP (0Ar)2 -- R C-C-OP (0Ar)2 (Atex 710) e F J) 9" J> R C-C-OP (OAr)2 -- R-C-C-OP <0H)2 S-75-SS-16 Page No. 3 In addition, an amide-phosphate ester was present. Because of Interferences by the epoxy reaction product. It could not be established If the amide reaction product was the same as that found In the new fluid. Total nitrogen analysis of the new NC-220 used In this study before and after earth filtration and of four reserve samples of NC-220 from June 1974 and October 1974 production were obtained by KJeldahl digestion and measurements with an anrnonlum Ion specific electrode. The results tabulated In Table IV show an almost constant level of nitrogen containing contaminants. About a 3-fold decrease in nitrogen level 1$ obtained by earth filtration. XRF (X-ray fluorescence) analysis of SPC F #1 and F #2 of the methanol recovered fraction from the earth filtration Indicated partial metal salts were present in addition to esters of the pyro- and/or polyphosphates. The major metallic element present was calcium and the minor elements detected were Iron, nickel and zinc. References: MR 16-1046, 16-455, 16-1047. IR 74-396, 74-511, 74-512. db Monsanto Industrial Chemicals Co. Applied Sciences St. Louis, No. 6/75 - B. Katlafsky, W. J. Lltschgl, M. W. Dietrich RSV 0010602 S-75-SS-16 Page No. 4 TABLE I GPC SEPARATION OF EARTH COLUMN ACETONE FRACTION FRACTION NO. - GPC VOLUME CUT APPARENT MOL. WT. WEIGHT PERCENT COWENTS 1 33.0-40.0 1170-730 17.8 1:1 reaction produce of amide with phosphate ester - ester portion high In cumylphenyl groups 2 40.0-44.3 730-420 16.1 Similar to F #1, amide content higher, contains cumyl and some nonyl contains N-CH3 3 44.3-47.8 420-255 22.4 Residual NC-220 containing about 10X amide reaction product 4 47.8-51.7 255-150 40.8 Similar to F #3, ^20% amide reaction product 5 51.7-53.6 150-118 1.6 ^*2:1 amide to ester reaction product 6 53.6-60.0 118-70 1.3 Similar to F #5, may Involve preferen tially the cumylphenyl component RSV 0010603 TABLE II GPC SEPARATION OF EARTH COLUMN METHANOL FRACTION S-75-SS-16 Page No. 5 FRACTION NO. 1 GPC VOLUME CUT APPARENT MOL. WT. 31.0-35.1 >3000 2 35.1-37.7 >3000990 3 37.7-43.9 990-420 4 43.9-47.3 420-270 5 47.3-53.1 270-130 6 53.1-58.1 130-66 7 58.1-60.0 <66 8 60.0-65.0 <66 WEIGHT PERCENT 41.6 22.4 10.6 5.5 9.0 5.1 3.1 2.7 COMMENTS Pyro or polyphosphate ester containing a low level of amides - contains ArH and RH, may contain Iron Same as F #1 - XRF analysis of combined F #1 and F #2 indicated the presence of calcium. Iron, nickel and zinc Similar to F #1, amide content much higher 1 amide to orthophosphate ester reaction product Same as F #4, contains cumyl unit, NMR similar to N-methyl pyrrolldone, contains N-methyl Same as F #4 No phosphorus present. A primary and/or secondary amide which Is not 1-methyl 2-pyrrolldone or 2-pyrrolldone, 110 ArH, NMR similar to N-methyl pyrrolldone, contains N-methyl Same as F #7 RSV 0010604 S-75-SS-16 Page No. 6 TABLE III SPC SEPARATION OF ACETONE FRACTION FROM PYORAUL 5QE DEPOSIT (TSR 74-123) FRACTION NO. 1 GPC VOLUME CUT 27.0-30.0 APPARENT MOL. NT. >3000 2 30.0-35.0 >3000-1500 3 35.0-40.0 1500-730 4 40.0-43.9 730-430 5 43.9-45.3 430-360 6 45.3-47.5 360-270 7 47.5-55.0 270-70 WEIGHT PERCENT COWENTS 7.7 Epoxy reaction product with phosphate ester - polymer Is low In aromatic components. Presence of nitrogen de tected qualitatively 46.8 Same as F #1, no aromatic H, contains fatty acid and ester, NMR looks very much like Admex 710 which has reacted with a molecule which contains no ArH and possibly no RH 16.8 %2:1 mixture of epoxy-phosphate and amidephosphate reaction products 12.9 *1:1 mixture of epoxy-phosphate and amidephosphate reaction products 5.2 Phosphate ester salts containing low level of amide 5.8 Similar to F #5 4.8 Similar to F #5 RSV 0010605 1 S-75-SS-16 Page No. 7 TABLE IV TOTAL NITROGEN CONTENT OF PRODUCTION NC-220 -SAMPLE NC-220 MIC 225748-C Neat % NITROGEN 0.04 0.06 NC-220 MIC 225748-C After Earth Filtration 0.01 0.02 NC-220 Lot QD-33 5/29/74 0.03 NC-220 Lot QD-39 6/10/74 0.04 0.04 NC-220 MIC 255274 10/19/74 0.03 0.04 NC-220 MIC 255274 10/21/74 0.04 0.03 RSV 0010606 Special Study S-75-SS-17 CHLOROOIBENZO-p-DIOXINS IN PENTACHLOROPHENOL TREATED WITH MORPHOLINE_____________________ SUWARY The Hewlett-Packard GC/MS system was used to Identify and measure non- phenollcs In five different lots of pentachlorophenol. These samples of penta had been subjected to a morpholine treatment at the W. G. Krumnrlch plant. They were found to contain levels of pentachloro, hexachloro and heptachlorodlbenzodloxlns at least ten times higher than found In pentachlorophenol which has not been treated. This suggests that the morpholine treatment may convert dioxin precursors to dioxins. DISCUSSION Solutions of the non-phenolIcs In benzene were received from Steve Vogel, W. G. Krunmrlch plant containing the non-phenollcs from 0.1 gram of each lot of pentachlorophenol. Phenollcs had been removed by NaOH extraction. The measure ment procedure Is the same as that described In Special Study AC-75-SS-3. The- amounts of various dioxins are reported as ppm based on 0.1 gram sample weight and are given below: Concentration (ppm) Sample Unknown Chloro Identification Aromatlc Penta CDD Hexa CDD Hepta CDD 212180-1 212180-7 211535 KM-261 256338 0.2 0.3 4 0.3 2 <0.1 120 2100 <0.1 110 1800 0.4 73 1400 0.4 50 1500 1.5 180 1600 No dlchloro or trlchlorodlbenzodloxlns were observed with a detection limit of 0.1 ppm. The unknown chloro aromatic has a significantly different GC retention time and mass spectrum from 2,3,7,8-tetrachlorodlbenzodloxln. However, Its spectrum does contain 322 and 259 Ions which would be expected of any tetrachlorodlbenzodloxln. The full mass spectrum, however, contains Ions which should not come from a dioxin. Because this spectrum Is very weak, the possibility that this component Is a tetrachlorodlbenzodloxln (but not the 2,3,7,8 Isomer) cannot be ruled out. db Monsanto Industrial Chemicals Co. Applied Sciences St. Louis, Mo. 6/75 - G. U. Mappes, M. W. Dietrich RSV 0010607 Special Study S-75-SS-18 JUNE 1975 MERCURY INVENTORY, V. O. KRUHMRICH PLANT, CHLOR-ALKALI DEPARTMENT INTRODUCTION AND SUMMARY The mercury Inventory made at V. 6. Krumnrich plant has been completed. The sum of the average weights for the 22 cells was 251,135 pounds 5697 (2 sigma limits). This Is 5166 pounds less then the Inventory of October 1976. Cell house mixing was followed on cells 1, 7, 16, 15 and 22; all cells were completely mixed after 26 hours. Inventory by Individual cells Is tabulated In Table I attached. The 2 sigma confidence estimate of 5697 pounds of mercury (2.273 of total inventory) was double that of most previous Inventories primarily due to abnormally low sample radioactivity. An Investigation showed that the Initial radioactivity In the Mercury-203 shipment was about 1/3 that of previous shipments. Also plant delays of about 20 days of targeted spike date further diminished the 66.7 day halfllfe radioactivity by an additional 253. Subsequent discussions with plant personnel indicated that they did not feel that to recount the samples at longer count Intervals (50 min. per sample vs the normal 20 min.) was justified. REFERENCES Research Notebook MIC 264367A-2643832B. db Monsanto Industrial Chemicals Co. Applied Sciences St. Louis, No. 6/75 - H. Yepez, D. B. Hines, M. V. Dietrich RSV 0010608 A MERCURY INVENTORY TABLE I MERCURY INVENTORY W.G.K. PLANT JUNE 1975 CELL NO* average mercury INVENTORY (LBS) STANDARD DEVIATION (LBS) TWO SIGMA - PERCENT OF TOTAL (LBS) 1 2 3 4 3 6 7 6 9 10 11 12* 13 14* 15 16 17 ia 19 20* 21 22 10266.35 11009.21 11699.56 11306.52 10899.75 11259.05 12076.07 10275.38 11578.00 11272.66 12087.04 9218.55 12524.33 11C09.25 13486.73 11309.94 11216.91 10359.34 119RA.21 10623.32 14134.02 11353.4b 146.90 146.41 97.44 126.39 117.58 67.12 104.51 99.49 118.01 90.51 161.C6 108.00 215.46 96.35 218.29 126.39 .106.45 56.20 97.76 145.47 251.97 158.93 293.81 292.92 174.88 252.76 235.15 134.25 209.02 196.98 236.02 161.02 322.13 216.01 430.91 192.71 436.58 252.78 212.91 116.41 195.52 290.95 503.94 317.66 2.862 2.660 1.471 2.296 2.159 1.192 1.731 1.937 2.039 1.606 2.665 2.343 3.441 1.750 3.237 2.235 1*896 1*124 1.631 2.739 3.565 2.800 . JO to < THE SUM OF THE AVERAGE WEIGHTS IS 251135.86 LBS. o o ..- THE SUM OF ALL TWO-SIGMA IS 5697*41 LBS o O' o fi THE PERCENT THE SUM OF ALL TWO-SIGMAS IS OF THE TOTAL INVENTORY WEIGHT = 2.269 PERCENT CELLS 12, and 20 HAD 836 I VIRGIN MERCURY ADDED AFTER CELLS WERE SPIKED. THE INVENTORIES GIVEN ABOVE WERE BASED ON SAMPLES FROM THE 3 CELLS TAKEN BEFORE THE MERCURY WAS ADDED, Spectroscopy I Specie) Study 75"19 DETERMINATION OF MALEIC ANHYDRIDE AND VINYL ACETATE IN AIR; PORT PLASTICS INTRODUCTION Analyses were performed to determine levels of Maleic Anhydride (HA) and Vinyl Acetate (VA) in air during a maleic anhydride resin process at Port Plastics, Addyston, Ohio. Workers In this area wear inhalation aspirators. The results given are not exposure levels but are the levels workers would be exposed to if they did not have protective equipment. SUMMARY Levels of MA and VA found are given In the attached table. EXPERIMENTAL A glass Tenas GC insert was used for collection and analyses. Calculations and identifications based on known standards, GC retention time and GC/MS verification. Volume of Air Sampled (Liters) Calculations Supplied by Steve Roberts Weight Sample (Mg) Concentration Sample (pg/L) m Area Sample Peak Cone. Std. (pg/uL) Vol. Injected (uL) (counts) x Area of Standard (counts! ~ Weight Sample (ug)/VoIume of Air Sampled (Liters) Concentration Sample (ppm) - W9/L (sample) x -- * For SampIIng 001 ii Volume of Air Sampled - 2.3 liters Weight Sample (ug) - 16069 x HiTTF1'7`2 * Concentration (ug/L) VA - 3.1 pg/L "ssrConcentration (ppm) VA - 3.1 x . 0.9 ppm Reference GC/MS File #75-112 ss Monsanto Industrial Chemicals Co. Applied Sciences i St. Louis, Mo. 6/75 - L. M. Chapman, M. W. Dietrich RSV 00106X0 Sample OOI 002 003 CONCENTRATION (PPH) HA NO (_ .2 ppm) VA 0.9 ppm ND (<6.6 ppm) 1.8 ppm <0.3 ppm 1.1 ppm Comments 2.3 1 sampled 0.75 1 sampled MA wasn't positively identified because of inter* ferences: 2.4 1 sampled RSV 001061L Spectroscopy Special Study 75*20 DETERMINATION OF CHLOROPRENE IN AIK AT POUT PLASTICS PLANT, ADDYSTOM. OHIO INTRODUCTION The purpose of this Investigation was to determine worker exposure in the handling of chloroprene. SUMMARY Two samples were analyzed for chloroprene. One sample taken during a leak In the operation gave a concentration of 1.2 ppm In the air while the other sample had a concentration of 0.8 ppm. Both are well below the TLV. EXPERIMENTAL A C-105 insert was used for collection and a 38 OVI glass analytical column was used for the analysis. A description of the calculations Is given below. Identification was by GC retention time of known standards. Calculations Volume of Air Sampled (Liters) Supplied by Steve Roberts Weight Sample (ug) Concentration Sample (ug/L) Area Sample Peak (counts) Cone. Skd. (wg/uL) Vol. Injected (uL) Area of Standard (counts) Weight Sample (yg)/Volume of Air Sampled (Liters) Concentration Sample (ppm) For Sampling 75*19 Volume of Air Sampled - 9.3 liters Weight Sample (ug) ' 5292 X 25j,fl74:- - **0*7 Ug Reference: GC/MS File #75*111 ss Monsanto Industrial Chemicals Co. Applied Sciences St. Louis, Mo. 6/75 * L. M. Chapman, M. W. Dietrich RSV 0010612 Spectroscopy Special Study 75-21 DETERMINATION OF VOLATILES IN DECATUR, ALABAMA PLANT AIR (IV) INTRODUCTION This Is a continuation of an Investigation to determine levels of vinyl acetate (VA), acrylonitrile (AN), vinyl bromide (Vfir). vlnlyidene chloride (VnClj)# DMAC and OMF In air at the north continuous polymer area of the Decatur, Alabama plant. The data obtained will be used to identify areas where worker safety problems may exist. SUMMARY Results of two sample sets are found In Table I and Table II. GC retention time provided the means of Identification of the volatiles. Acrylonitrile had values of from 0.2 to 2.0 ppm, vinyl acetate values ranged from 0.1 to 11.4 ppm, VBr ranged from 0.1 to 1.6 ppm and vinllldene chloride ranged from 1.2 to 4.0 ppm. Values for DHAC and DMF are uncertain because the columns used for collection have not been fully investigated for these components. EXPERIMENTAL Refer to Spectroscopy Method 74-7 for the analyses procedure used. Twelve minutes were allowed for the heating of the external collection column to collect the acrylonitrile before proceeding as in Method 74-7- An example of the procedure used to calculate concentration is given In the S-75-SS-! report. Sample collection was made using a Model 222-451 SKC pump. Calcu lations were based on known standards. Reference: GC/MS File #75-114 ss Monsanto Industrial Chemicals Co. Applied Sciences St. Louis, Ho. 6/75 - L. M. CCapman, M. V. Dietrich RSV 0010613 TABLE I CONCENTRATION (PPM) VBr AN VA M-3 1.0 PPM 2.0 PPM 0.4 PPM M-4 1.6 2.0 0.3 H-5 0. 1 1.2 0.2 L-4 0.8 0. 1 ND Samples from 5*19-75 Volume sampled ft# 2 liters Flow rate ^ 17 m/min Sampling time 4*2 hours RSV 0010614 TABLE II CONCENTRATIONS (PPM) L-12 L-7 L-ll L-10 L-1 L-3 VBr VnC12 VA AN 0.4 1.6 < 0.1* NO NO 1.2 < 0.1* 0.2* NO NO 1.0 NO 0.4* 4.0 <11.4* NO ------- Lost In analysis ------- Lost in analysis OMF** 2.7 NO 2.0 NO DKAC** NO <. 1.1* NO < 1.7* * Due to interference from other components these are maximum values ** Values for OMF and DMAC are questionable because the columns used for the collection have not been fully investigated for these compounds. Samples from 6-9-75 Volumes sampled^ 2 liters Flow rate m* 16 m/mtn Sampling time a# 2 hours RS V 0010615 Spectroscopy Special Study 75-22 DETERMINATION OF CONTAMINANTS IN DIMETHYL SULFIDE INTRODUCTION Dimethyl sulfide Is a component In an artificial tomato flavor to be sold to General Foods. The purpose of this study was to identify Impurities In certain lots of dimethyl sulfide which cause the product to be nonacceptable to General Foods. SUMMARY Impurities Identified are given In the attached table. The major difference between the acceptable and non-acceptable products was the presence of CjHgS and C^HjqS components In the non-acceptable product. These components may explain the differences observed by General Foods. EXPERIMENTAL A Chromosorb 105 analytical column was used for the analyses. Calculations are based on a dimethyl sulfide standard. GC/MS provided the identification of components. Reference: GC/MS file #75-116 ss Monsanto Industrial Chemicals Co. Applied Sciences St. Louts, Mo. 7/75 L. M. Chapman, M. W. Dietrich RSV 0010616 Table for S-75-SS-22 CONCENTRATION (9/1) DHS Propane* W CjH8* c3h8s C4HI0S Hisc** Phillips (better than acceptable) 997 1.0 2.3 NO ND HD < 0.1 Aldrich 12 (acceptable) 996 1.4 2.8 ND ND ND < 0.1 Penwa1t (not acceptable) 975 1.2 2.4 3.1 1.0 16.7 < 0.2 PenwaIt Ex Drum (not acceptable) 989 1.8 2.5 0.7 0.3 4.8 0.2 * Tentative Identification only ** The sum of other small contaminants not specifically Identified RSV 0 0 1 0 6 1 7 S-75-SS-22 UttVAi dL^Ltft^. -* *200 c 3 00t |OA^4^-vv cro-src^S'*/ djuU^tcrv *<L oJU jkzLx e-/r * I RSV 0010618 RSV 0010620 r S-75-S5-22 ii P tj. I P 1 Spectroscopy Special Study 75*23 VOLATILE ORGANICS EVOLVED DURING THERMOGRAV(METRIC ANALYSIS OF FLAME AND SMOKE RETARDING PVC FORMULATIONS _____ SUMMARY Volatile organics from PVC decomposition between 250 and 350*C were identi fied and quantified. Fifteen components were identified. The total organics observed accounted for from 0.5 to 3 percent of the sample weight. Under these conditions, the TGA indicated from 5 to 60 percent weight loss. The material not measured is presumed to be principally HCI and high boiling organics. OISCUSSIOM The twelve PVC sheets submitted for thermogravimetric analysis. Physical Chemistry Special Study 74*48, were decomposed in the TGS-1 thermobalance using sample weights of 10 to 1$ milligrams. The temperature program rate was lOVmin. with an air purge gas flawing at 10 mi/min. The air and organics exiting from the TGS-1 were sampled by a loop of 1/8. inch 0.0 stainless tubing having a volume of 10 mi. After sampling, the loop was transferred to a gas chromatograph where the gas sample was trapped on the head of a Tenax GC column at ~40*C. The Tenax GC column was temperature programmed from -40 to 250*C. The organics which eluted were identified by a combination of GC/MS and GC retention time. The data from these analyses are presented In two forms. One Is a graph showing both the TGA weight loss and the total organics for each gas sampling as a percent of sample weight. The other is e table for each sample showing component identification and concentration of that component as a percentage of all the organics measured from that sample. The tempera tures are not the same for each table because the gas samples were taken at corresponding points of weight loss on the TGA curve rather than at corresponding temperatures. The sample loops were attached to the TGA apparatus when the apparatus reached the temperature indicated in the table and were left connected during the next 10 degree temperature increase, i.e. for one minute. This means that the concentratIons given in the table reflect an average compo sition over the period of this 10 degree increase. GC/MS identifications were done on the basis of three sample loops. The peaks In the remaining 69 GC separations were identified by retention time relative to the GC/MS data. This is a good method of identification for all of the components except Cg olefin, alkyl chloride and Cjo olefin which are Incompletely resolved. If the Identity of one of these components becomes critical for a given point on the TGA curve of a particular sample, we will have to check that sample by GC/MS. RSV 0010622 c S-75-SS-23 Page Ho. 2 Sow of the very smell peeks ere not Included In the table so that addition of all the entries In each table will not quite equal 1002. ss Monsanto Industrial Chemicals Co. Applied Sciences St. Louis, Mo. 7/75 * 6. V. Mappes, C. Calvert, M. W. Dietrich RSV 0010623 W U fiG t W 9-JL t'b ik s fiM P it: w - SMV9*9 JNJOXJd V s n m 'rt: w - f ?.< 3 S fiv n e : 979- rye ( l'J t .1 / S m M t 999-6 S /M M 3H -S -n % i i 3 U -4 S *W IB : 266- r SS01 S A H P iZi. 3 U -2 , s n n rte 366- Sample 366*1 Percent of Volatile Organics Oetected Temperature Propene Methyl chloride Propane Butene Pentene Pentane Benzene 270 .06 -- .09 -- .11 .20 -- oo 285 .08 . -- .12 -- .04 .63 300 .44 . 16 .44 .23 -- .61 6.88 315 .89 .47 .20 .74 -- .32 21.69 330 31*5 .67 2.25 .29 .25 .73 .56 .12 .17 1.75 -- .69 47.10 Nl .06 Temperature 270 285 300 315 330 3*5 Cj olefin .53 .42 1.71 -- 1.42 __ Toluene __ .006 .097 .26 1.04 __ Cg olefin .06 .16 .50 .81 1 .72 .17 An alkyl chloride ---- -1.19 -- C^q olefin .26 --- -- .24 -- Total organics measure.:: at each temperatui 1.31 1.465 11.067 25-38 55.77 4.65 RSV 0010636 S-75-SS-23 Sample 366-2 Percent of Volatile Organics Detected Temperature Propene Methyl chloride pw oase Butene Pentene Pentane Benzene 250 -- .32 -- -- -- .13 1.18 265 -- .15 .13 .09 -- .31 A.71 260 .03 .09 .06 -- -- .44 6.13 295 .14 .18 .02 .09 -- .07 5.29 310 .06 .07 .09 .08 -- .17 15.71 322 .08 .06 .05 .06 -- .05 16.13 Temperature C7 olefin Toluene C9 olefin An alkyl chloride C10 olefin Total organics measured at each temperatun 250 -17 -83 .19 -- -- 2.82 265 -- 6.33 -- -- -- 11.72 280 -- 9.53 12.92 295 -- 1.49 1.94 310 35 1.7 6.12 322 -- 1.55 3.11 -- -- '-- -- -- 29.20 -- 9.22 -- 24.35 -- 21.09 !I i RSV 0010637 S-75-SS-23 i Sample 366-3 Percent of Volatile Organics Detected Temperature Propene Methyl chloride Propane Butene Pentene Pentane Benzene 260 -- .21 -- -- .08 .06 .20 275 .18 .21 -- ' -- .90 .65 6-74 288 .78 -29 .61 .83 .75 1.52 23.26 300 .15 .05 .08 .08 -- .16 7-32 312 .33 .10 .19 .14 .06 .29 12.28 325 1.47 -38 .82 .70 -- .09 .60 Temperature C7 olefin Toluene Cg olefin An alkyl chloride C IQ olefin Total organics measured at each temperatur 260 275 288 300 312 325 -- -- .07 .94 .05 1.84 12.19 .81 1-91 5.17 .02 .02 9-52 .17 3.01 -- __ __ -- -- .62 .28 -- 11.79 -- -- ^*2.95 -- .-- 13-05 .44 -- 26.53 0 -- 4.06 RSV 0010638 S-75-SS-23 Sample 366 -4 Percent of Volatile Organics Detected Temperature Propene Methyl chloride Propane Butene Pentene Pentane Benzene 252 -- .46 .10 -- .02 .05 .58 265 -- .15 .15 -- .08 -07 1.16 280 -- -47 .28 -- -45 .45 6.60 293 . 11 .03 -- -- -- -- -- 305 .14 316 .06 .08 .02 .18 .22 .15 38 10.33 -- .22 -- -- -- Temperature Cj olefin Toluene Cg olefin An alkyl chloride Cjq olefin Total organics measured at each temperatu; 252 N1 265 .48 280 2.12 293 -- 305 3.91 316 .76 1.73 8.93 -- 6.14 __ 1.22 3.41 14.94 Nl 11.36 __ .28 2.26 6.51 -- 8.47 -- -- .26 1.45 -- 1.40 3-47 9.75 42.20 .14 42.76 -30 RSV 0010639 S-75-SS-23 Sample 366*5 Percent of Volatile Org an \ cs Detected Temperature Propane Methyl chloride Propene Butene Pentene Pentane Benzene 250 -- 31 -- -- -- . 12 .57 262 -- .03 -- .04 ~ .08 2.20 275 .02 .04 -- .11 .10 .36 4.08 290 .02 .02 .001 .02 -- .14 2.00 302 .04 .05 .06 .06 .04 .07 9.22 306 .06 .09 .05 .06 .09 14.00 Temperature C-j olefin Toluene Cg olefin An alkyl chloride Cjq olefin Total organic measured at each temperat 250 .24 262 -35 275 -- 290 .55 302 1.23 306 -- .91 2.04 4.40 1.86 .67 .12 1-95 8.81 11.52 2.30 4.38 .10 1.17 -- -- 3.71 -- -- 1.35 ^-99 1 .02 3.02 2.21 6.15 6.62 18.54 21.65 13.641 18.03 20.72 RSV 0010640 Sample 366*6 Percent of Volatile Organics Detected Temperature Propane Methyl chloride Propene Butene Pentene Pentane Benzene 250 .14 -- -- 8.18 2.05 262 03 .13 -- -- 12.60 5.20 275 .02 .08 -- -- 11.77 5.39 287 .05 .08 -- -- 7-82 8.27 300 09 .06 -- -- 3.84 13. n Temperature Cy olefin Toluene Cg olefin An alkyl chloride C|Q olefin Total organics measured at each temperatL 250 07 .004 .05 262 .37 .04 -- 275 -59 .21 -- 287 .71 .17 .10 300 83 .21 15 .04 .65 11.184 .005 .21 18.585 .16 .87 19.09 .19 .04 17.43 -- -- 18.29 RSV 0010641 S-75-SS-23 Sample 989*1 Percent of Volatile Organics Detected Temoerature Propene Methyl chloride Propane Butene Pentene Pentane Benzene 270 .05 .27 -13 .17 -- .80 .66 283 .29 .60 .55 .82 .16 1.62 8.12 295 .21 -- .10 -19 -- .86 13-30 308 .22 .07 .67 .20 -- -97 21.62 320 .37 .37 .20 .16 .16 .86 25.95 Temperature C7 olefin Toluene Cg olefin An alkyl chloride Cjo olefin Total organi measured at each tempera 270 .86 .06 .76 .56 .62 6.76 283 2.75 -- 2.88 295 -- .17 1.20 308 -- .19 1.75 320 .67 -36 1.02 1.66 .06 1.36 -91 -- 19.03 -- 16.09 .98 27.63 .16 31.13 RSV 0010662 Sample 989-2 Percent of Volatile Organics Detected Temperature Propene Methyl chloride Propane Butene Pentene Pentane Benzene 260 -- 274 -- 1.22 -- .17 -- -- -- .29 -- .18 .52 7.69 287 -- -- .57 -- .56 16.22 300 .42 .12 -50 .12 .82 18.84 313 45 .07 .10 .29 .31 18.76 325 .95 .09 .25 54 .09 .79 17-98 Temperature C7 olefin Toluene C9 olefin An alkyl chlor ide Cjo olefin Total organics measured at each temperatu 260 .70 -- Nl 274 1.89 -- 1.21 287 .20 -- -- 300 -- 1.10 313 -- .13 -69 325 -- .16 -51 .13 1.04 -.15 .17 .03 .15 2.37 -- 12.82 -- 17.55 -- 22.07 -- 20.97 -- 21.39 RSV 0010643 I S-75-S5-23 Sample 989-3 Percent of Volatile Organics Detected Temperature 270 Propene -- Methyl chloride 2.34 Propane 1.05 Butene -- Pentene Nf Pentane 1.27 Benzene 4.02 284 .21 .72 1.40 .08 .20 1.75 8.31 297 .24 .34 1.12 .48 .16 1-71 10.61 309 .50 .14 .93 51 .18 .66 15.49 322 71 .14 1.16 .52 .13 .95 8.58 334 1.29 .11 .62 .68 -- .92 11.10 Temperature 270 284 297 309 322 334 olefin Toluene Cg olefin An alkyl chloride C 10 olefin Total organics measured at each temperatu 2.48 11.16 -- HI 1.56 .10 -- 14.33 1.63 -- .27 -- .73 -- .11 -- -- 17.40 -- 18.41 2.11 .29 2.56 -- -- 17.15 2.16 __ .009 -- 16.889 RSV 0010644 Sample 989*4 Percent of Volatile Organics Detected Temperature Propene Hethvl chloride Propane Butene Pentene Pentane Benzene 250 -- 2.13 .52 -- -- .69 3.45 264 -- .38 .53 -- .18 -- 13-91 281 -- -- .50 -- .21 50 18.58 295 -- .04 .10 -- .07 .13 10.45 308 -- -- .08 -- -- -- 23-13 323 .04 -- -- -- -- -- 21.88 Temperature Cy olefin Toluene Cg olefin An alkyl chloride C jq olefin Total organics measured at each temperatu 250 264 281 295 308 323 -- -- -- -- --- -- -- -- -- -- -- -- -- -- .54 -- -- -- 6.79 -- -- 15-00 -- -- 19-79 -- -- 10.79 -- -- 23-21 -- 1.45 22.46 RSV 0010645 Sample 989*5 Percent of Volatile Organics Detected Temperature Propane Kathy1 chloride Propane Butene Pentene Pentane Benzene 280 -- 294 -- .37 39 .11 .48 .40 9.62 .18 .20 .32 .28 .18 tit.95 306 .10 .16 .14 .31 .12 .21 13.52 318 .19 .14 .10 .49 .12 .11 14.71 330 .25 .16 .23 .38 .06 13 15-40 344 .29 .12 -- .20 .04 15-69 Temperature C7 olefin Toluene 280 -- 1-87 294 -- 1.09 306 -- 1.91 318 -- .93 330 -- .74 344 olefin An alkyl chi oride C ^0 olefin Total organ measured at each temper^ -- -- .15 13.39 -- -- -- 17.20 -- -- -- 16.47 -- -- -- 16.79 -- -- -- 17.35 -- -- -- 16.34 RSV 0010646 Sample 986*6 Percent of Volatile Organics Oetected Temperature Propene Methyl chloride Propane Butene Pentene Pentane Benzene 253 -- -07 .52 -- 8.99 2.19 267 .02 -07 .03 1-37 -- 15.12 3.74 280 -07 -09 .05 3.49 -- 13.22 4.59 293 .07 .10 .03 1.96 -- 10.02 5.53" 306 .21 .10 4.16 -- .55 6.92 Temperature C7 olefin ToIuene Cq olefin An alkyl chloride C10 olefin Total organic: measured at each temperati 253 .06 -- -- 267 90 .03 .04 280 1.00 .01 -- 293 1.21 .12 .58 306 1.03 -- -- -- -55 -- 3-22 .10 -- n .83 -05 21.92 -- 22.52 -- 22.84 -- 13.07 RSV 001064? Spectroscopy Special Study 75-24 VOLATILES FROM ABS AND STYREHC POLYMERS AT PROCESS I MG TEMPERATURES SUMMARY- Two samples of aerylontrlle/butadlene/styrene polymer (ABS) and one sample of high impact polystyrene were heated fn air at 2Q0C and 260*C to simulate processing conditions. Volatiles given off by these polymers ranged in concentration from ten to several hundred ppm of the sample weight and were identified by GC/MS. DISCUSSION A ten to twenty milligram piece of each polymer was placed in a smalt porce lain boat and heated to the desired temperature. This was done in a quartz tube connected to the injection port of the Hewlett Packard GC/HS system. Air flowing at 15 m/mln. passed over the boat and carried volatile materials onto the head of the GC/column (2-51 OV 17) which was held at -40C. After heating for the desired time* the sample was removed from the quartz tube* and helium carrier gas was used to sweep any volatiles remaining In the tube onto the head of the GC column. The GC column was then temperature programmed from -40C to 250C and the eluting components analyzed by mass spectrometry. Each sample was heated for one minute and for 15 minutes at each temperature, 200C and 260C. In order to keep the sampling times the same for all samples, the 15 minute heating was done in a forced air oven. The sample was then transferred rapidly to the quartz tube where It was heated for one minute at the same temperature and sampled for volatiles. The one minute samples were heated for one minute at the desired temperature and sampled for volatiles during the heating period. The attached table shows the volatiles found from each sample at each of the four experimental conditions. Component G may be a substituted indene; component A probabty has a molecular weight of 73 but could not be identified by its mess spectrum. The components In the table account for 902 or more of the components observed by GC/MS (except for the samples heated to 260C for one minute and the LNIFC 500 15 min. f 260 sample). These samples have components with molecular weights higher than 200 that amount to 10-302 of the components measured by GC/MS for each of these samples. They could not be Identified by their mass spectra. However, the data indicate that some are probably styrene dimers. RSV 0010648 / * S-75-SS-2* Page No. 2 The mount of volatiles Measured tn this type of experiment may depend on the surface area exposed to the heated air. AH of the samples analyzed had approximately the same surface area since they were the same size and shape. -A very finely divided sample may give higher values than those reported here. Acidic components such es HCN, HC1 end HSr would not have been measured by this method. ss Monsanto Industrial Chemicals Co. Applied Sciences St. Louis, Mo. 7/75 G. W. Mappes, M. V. Dietrich RSV 0010649 TABLE FOR S-75-SS-24 VOLATILES FROM A8S AND HIPS POLYMERS PPH BASCO ON WEIGHT Of SAMPLE ANALYZED SAMPLE LNIFC 500 AeryIon1trlIn Ethylbenzene Styrene C^alkylbenzene Terplnolene Dibutyl cresol 1 nln g 200C 7k 80 210 43 97 50 15 nln 0 200*C B 11 72 5 25 40 1 nln R 260C 160 160 230 52 120 120 15 nln 0 260C 12 19 8k 10 50 130 LNI 440 Acrylonitrile Ethylbenzene Styrene C^alkylbenzene Terplnolene Dibutyl cresol 1 nln % 200C 230 130 230 38 100 110 15 nln g 200C 20 13 63 6 23 22 I nln 0 260C 260 170 140 41 89 130 15 nln % 260C 11 23 76 10 50 86 G 15 3 92 26 LUSTREX 6400 1 min 8 200C 15 nln 200C 1 nln 260C 15 min 260C A 16 5 3* 18 Ethylbenzene Styrene C^alkylbenzene Terplnolene Dibutyl cresol Styrene diners Tlnuvln-P 210 150 35 <10 55 54 46 15 49 4 <10 15 95 320 400 57 100 100 120 76 10 33 2 11 18 79 RSV 0 0 1 0 6 5 0 Spectroscopy Special Study 75*25 DETERHIMATI ON OF BIS (2-CHLOROETHVL) ETHER IN PHOSCARDS INTRODUCTION The presence of bis (2-chloroethy1) ether (8CEE) may pose a threat to the product acceptability of our Phosgards. Both EPA and NIOSH (administrators of OSHA) have expressed concern over the toxicity and possibly carcino genicity of BCEE. This study was undertaken to determine if any of our Phosgard products contain BCEE and if so to determine the levels. SUMMARY A headspace GC method has been developed for determining BCEE in Phosgards and In ethylene dichiorlde. Data from several product and process samples are given in the attached Table I. As is indicated, BCEE was found in several samples. Values of <.005% are questionable because of possible equipment contamination. The significance of these levels of BCEE in our products is unknown. DETAILS A. Identification of BCEE The presence of BCEE was confirmed by GC/MS techniques using headspace samplings from several products. These Identifications were carried out under modified GC conditions to minimize chances of thermal decom position of other components in the products. The headspace sample was collected from Phosgards at room temperature (this will leave behind high boiling materials). The collected sample was placed in a warm only (100*C) Injection port. GC analyses conditions were chosen so that BCEE eluted below 110 C(see Figure 1). Under these conditions, it is very unlikely that interfering components which liberate BCEE could be present. The mass spectra* from GC/MS, and the GC retention time obtained in this way were identical to known BCEE. B. Alternative Analyses Procedure Liquid Chromatography (LC) and direct GC analyses were also studied. LC appeared promising but did not have sufficient sensitivity. Detec tion limits using the refractive index dectector were only ca 0.1%. BCEE does not have sufficient UV response to allow the use of this detector. Direct GC analyses was found to give erroneously high results on some samples. This Is presumed to be due to a Phosgard component decomposing on the hot injection port of the GC and forming BCEE. Table II compares data obtained by Headspace GC to that obtained by LC and GC. C. Sample Collection * The sample collection apparatus consists of a 125 ml suction flask fitted with a dip tube, stopper, and a two-inch Teflon covered magnetic stir bar. The stopper Is a #12 cork bored to snugly fit a 5 nrt o.d. tube and with the surfaces exposed to the sample covered with Teflon RSV 0010651 Spectroscopy Special Study 75-25 Page Two C. Sangle Collection (cont'd) tape. A 130 mm length of 5 m* o.d. glass tube was Inserted through the Teflon tape until It would clear the flask bottom by ca 20 ran, thus exposing ca 20 mm above the cork. The flask side arm carried a short tube charged with activated charcoal granules. A 15 psi house N2 line was led to the charcoal trap, passed over the stirred sample, through the dip tube and via a short Teflon connection Into a collection tube. An Ideal refrigeration valve after the regulator throttled the N2 flow. N2 flow was measured by a Buble-O-HIter as It left the collector and was adjusted for 100 mi/25 seconds. The collection tube Is a six-inch length of l/k-inch standard stainless steel tubing fitted with two Swazelok nuts back-to-back on one end, the long part measured to fit as an Insert Into the injection port. It is charged with 150 mg Tenax 60/80 retained centrally by plugs of sllanized glass tagol. The inserts are conditional at 200*C and cooled before use. 0. Calibration A standard was prepared that contained 80.5 micrograms of bis-chloroethyl ether per microliter of methylene chloride. A one microllter injection of this standard, with needle correction provided 90.1 micrograms of BCEE. To calibrate the vapor collection, an equilibrium process, a degassed Phosgard 1227 was used. Oegassing was done by passing air at room temperature over a shallow stirred pool of Phosgard for three weeks. Ten mi of this BCEE-free Phosgard 1227 was charged into the flask and a collection made to establish the "zero" level. Then ten mtcroliters of the standard and later an additional 90 ralcrollters to give collections representing 10 and 100 micro!!ters or 80 and 800 ppm in the liquid. The GC results, versus the injected standard. Indicated 0.98 and 6.9 micrograms in air respectively. A calibration curve of micrograms in air versus ppm in liquid from these data was used to determine the ppm of BCEE in the Phosgards analyzed. As a first approximation, BCEE-free Phosgard 1227 was used to calibrate for all the Phosgards analyzed. An all-glass 10 mt syringe equipped with a 3 ran i*d. by 5-inch length of Teflon tube Is used to transfer 10 mJt of the Phosgard sample to the flask. Without the collection tube the dip tube/cork assembly is set in place and with moderate stirring the sample is equilibrated with N2 flow for ten minutes. Then the collection tube is attached for about eight minutes to collect the components swept out of the flask by two liters of N2 flow. *GC analyses Indicated this Phosgard was essentially free of BCEE and other low-boiling Impurities. RSV 0010652 Spectroscopy Specie! Study 75*2$ Page Three Analyses A Hewlett Packard 7620A gas chromatograph capable of sub-ambient opera* tion via liquid nitrogen cooling was used. The analytical column used Is a 1/8-inch by 2 meter 102 S-409 on 60/100 Chrom WHP. With the helium flow off and the injection port at 200*C, the collection tube Is first attached to the head of the analytical column. The collection tube is then inserted into Injection port, secured, and the liquid nitrogen cooling turned on the achieve -30*C. The Autolab Is set at peak width five, slope sensitivity 30 and attenuation one. When ready the helium flow, Autolab and program are Initiated. The temperature program used wes -30*C to !50*C at 20*C per minute, followed by a purge at 180*C for five to ten minutes. GC attenuation is typically 1 X 1000. Quantita tive data were obtained using an Autolab System IV and standatd GC techniques. A typical chromatogram Is attached as Figure 2. ss Honsanto Industrial Chemicals Co. Applied Sciences St. Louis, Ho. 7/75 - 0. E. Klnast, H. W. Dietrich RSV 0010653 n * RSV 0010654 RSV 0010655 V i i< RSV 0010656 A Lt B fiA rto * S-75-SS-25 RSV 0 0 1 0 6 5 7 SAMPLE P 1227 Lot 1053 P 1227 Lot 1050 P 1227 Lot 1054 P C22R, Q0 7250 DOW E0C EDC: Neutralized Ba 7323, P C22R Byproduct EDC: Un-neutral Ized, Ba 7446 P 1227 Run 3, Cut 1 P 1227 Run 6, Cut 1 TABLE I Identification confirmed by GC/HS. Very high level residual chlorobenzenes. X BCEE (HEAOSPACE GCl 0.2 ND <0.3*** 0.2* <,005* <.001 0.03* 0.3* .0005 .001 S-75-SS-25 RSV 0 0 1 0 6 5 8 SAMPLE P 1227 Lot 1053 P 1227 Lot 1050 P 1227 Lot 105^ P C22R, QD 7256 DOW EDC EDC: Neutralized Ba 7323, P C22R Byproduct EDC: Un-neutral lied, BA 7446 P 1227 Run 3, Cut 1 P 1227 Run 6, Cut 1 TABLE 1 HEADSPACE GC 0.2 ND <0.3*,** 0.2* <005* 1-001 0.03* 0.3* .0005 .001 t BCEE LC 0.1 <0.1 0.15 ND ND <0.1 0.15 - GC 1.1 .00! 0.43 - - *1dentlfI cat Ion confirmed by GC/M5. **Very high level residual chlorobenzenes. Special Study S-75-SS-26 HYDROLYTIC STABILITY OF PYDRAULS AMD COMPETITIVE PRODUCTS SUHHARY- UV fluorescence analysis for phenolics In Monsanto and competitive hydraulic fluids using a General Motors stability test and analytical method showed: 1. Pydraul 50 E (QC-12820) with Admix 710 Indicates less stability compared to HS-1120 after seven days in a series run for a General Motors project. The Inhibitlve effect of the HS-1120 decays rapidly and after fourteen days the phenolic levels In both fluids are comparable. 2. Similar stability was observed with 1974 production Pydraul 50 E, Pydraul 30 E and laboratory preparations containing production NC-220 ester (12/2/74) stabilized with Unox 289 (7-day stabilities) as compared to Pydraul 50 (QC-12820) used in G. M. Study (1.). 3* Seven-day and fourteen-day stabilities of production NC-220 ester containing MCS 1562 epoxide were better than the HS-1120 used in the G.M. test. 4. Cartridge clay treatment of the production NC-220 ester with either Unox 289 or MCS 1562 showed significant improvement over untreated ester. The MCS 1562 stabilized system was far superior to HS-1120 used in the G.M. series in both seven-day and fourteen-day phenolic levels. 5. Pydraul 179 B from Europe has a seven-day stability equal to HS-1120 used in the G.M. series and contains 50t less phenolics after fourteen days. 6. The competitive product FQ 220 CF shows a seven-day stability equal to that of the clay-treated production NC-220 ester with MCS 1562. The fourteen-day phenolic level Is the best of all samples analyzed, about 2/3 that of the clay-treated NC 220/MCS 1562 sample or the Pydraul 179 B from Europe. 7. Wide variations were observed In competitive samples having the same designation suggesting changes In formulation. HS-1120 #C228l shows poor stability compared to HS 1120 used In the G.M. series. FQ 220 #3733-5-7 shows poor stability compared to FQ 220 CF. Phenolic levels after seven and fourteen days are equal to those of the production Pydraul 50 E and Pydraul 30 E samples.8 8. At the completion of the tests, fourteen days, all of the Pydraul fluids except Pydraul 179 B, all of the untreated production NC-220 samples containing either Unox 289 or MCS 1562 and all of the laboratory samples of NP cresylfc and NP phenol showed black pre cipitates. No precipitates were observed in the clay-treated NC"220 ester samples or in the competitive products. RSV 0010659 4u S-75-SS-26 Page Two INTRODUCTION A large sales potential for Pydraul fluids exists with General Motors if the hydrolytic stability of Monsanto's products can be shown to be equal to or better than competitive products. A joint project was initiated with Chevrolet's Central Laboratory to measure phenolics generated using their stability test and their UV fluor escence analytical method. General Motors had reported high values, for example 1,200 ppm at 0 hrs. for a Pydraul 50 E sample (lot unknown) which appeared questionable. The program was extended to obtain internal data on the stability of new phosphate esters, production samples of Monsanto Pydraul series fluids, competitive products and the effects of new epoxide acid scavengers to improve the stability of Monsanto products. EXPERIMENTAL lOOg test fluid and 1g water were vigorously shaken for one minute and transferred to a mini o/c tube (1" diameter X 10") equipped with a con- . denser. The test mixture was held in a mini o/c bath at 250*F for seven days. One m2 aliquots were removed periodically for analysis of generated phenolics. The test was extended to fourteen days to overcome an Initial induction period or Inhibitlve action observed with some samples. Analytical data for phenolics were obtained in duplicate. 0.200 to 0.250g of the aliquot was weighed to the nearest mg and sufficient water adjusted to pH 4 with HfPO* added (200 to 250 mi) to give a 1,000:1 mixture of water to sample. The 1,000:1 mixture was vigorously stirred for 30 minutes at room temperature with a magnetic bar, allowed to settle for 15 minutes and filtered through 12.5 cm Whatman #42 paper. The first 25 to 30 mi of fil trate were discarded and the next 100 mi collected for analysis. Samples of new fluids were equilibrated In a similar manner to obtain 0 hour data on phenoHe 1 eve Is. Ultraviolet fluorescence analysis was carried out using an Aminco-Bowman SPF using 1 cm2 cells and a 1.0 iig/mi quinine sulfate solution in 0.1 N H2S0i, as reference. The quinine sulfate was excited at 350 mm and the emission detected at 450 nvn. The UV fluorescence method was calibrated using J. T. Baker's phenol (cat. no. 2858) as the standard. The substitution of phenol for p-cresol, the standard specified by the G.M. method, was mutually agreed on by G.H. and Monsanto because of the long-term storage Instability of the dilute p-cresol solution used to check the spectrofluorometer. A series of standard solu tions containing 0.15 to 3.0 yg phenol/mi water were prepared and fluores cence measurements made using 273 mm excitation and 302 mm emission. A RSV 0010660 S-75-SS-26 Page Three few drops of 0.1 N NaOH were added and the fluorescence measured again. The difference between the acid end base values was the fluorescence due to phenol. A plot of relative fluorescence calculated by: rel. floor. - (IT X sensitlvity)#c|(J - (tT X sensitivity)^^ * sensitivity)^ versus phenol concentration showed a linear relationship in the range of 0.15 to 2.50 ug/mi. Linear regression analysis gave the straight line equation relating phenol concentration to relative fluorescence as: ug phenol rel. floor. + 0.0012 0.1320 and ppm phenol Ics measured as phenol as: ppm 1000 x ug (rel. fluor. * 0.0012) (Vol.) (0.1320) (wt7 of spl.) SYSTEMS STUDIED A. General Motors Series 1. Pydraul 50 E Lot 0C 12820 MIC 255266 2. HS-1120 obtained from Chevrolet Central Laboratory 0$ ring isoprophyl B. NC-220 Ester (12/2/74) - New Epoxides 1. 0.5* Unox 289 MIC 285108 2. I.Ot Unox 289 MIC 285108 3. 1.02 MCS 1562 MIC 285108 4. 1.5% MCS 1562 MIC 285108 C. Cartridge Clay-Treated NC-220 Ester 1. MCS 1742 - 1.0% Unox 289 MIC 285101 2. MCS 1743 - 1.5t MCS 1562 MIC 285101 D. HP Esters with 1.5t Admix 710 epoxide + 30 ppm DCF 1. MCS 1769 NP cresylic 220 MIC 265112 2. MCS 1770 NP cresylic 150 MIC 285115 3- MCS 1776 NP phenol 220 MIC 285128 4. MCS 1779 NP phenol 150 MIC 285129 E. Monsanto Products 1. Pydraul 179 B Europe 9/12/72 MIC 285135 2. Pydraul 30 E Lot Q0 33701 MCS 1772 3. Pydraul 50 E Lot 00 34520 MCS 1771 RSV 0010661 S-75-SS-26 Page Four SYSTEMS STUDIED (CONT'D) F. Competitive Products .1 FQ 220 CF 6/22/73 .2 FQ 220 3733-5-7 3- HS-M20 C-2281 MIC 265135 OS ring isopropyl MiC 285135 2k% ring isopropyl MIC 285135 96* ring isopropyl DISCUSSION The experimental data are tabulated in Tables I to VI and shown graphically in Figures 1 to 7* A. Genera) Motors Series At the end of seven days (the conditions of the Chevrolet Central Lab. test) HS-1120 was considerably better than Pydrau) 50 E (6,300ppm phenol les vs. 31,000). The shape of the HS-1120 curve (cf. Figure 1) shows that up to five days there was an inhibitlve effect on phenolic genera tion. After this induction period, phenolic generation was rapid. On extension of the test to fourteen days, this validity of this premise was demonstrated. Phenolic levels in the HS-1120 system comparable to those In the Pydraul 50 E system were obtained. 8. NC-220 Ester - New Epoxides 1. Unox 289 At the 0.5* level, this epoxide shows some Inhibition to phenolic formation, but between four and seven days this effect is removed and phenolic levels equal to that of the Admix 710 system are obtained. At the 1.02 level of Unox 289, the system shows a pattern similar to HS-1120 with early inhibition. 2. MCS 1562 At both the 1.0 and 1.52 levels, better inhibition to formation of phenolics Is found than in the G.M. HS-1120 series after seven days. After fourteen days, this inhibitlve effect is still operating with phenolic levels 1/2 to 2/3 those observed in the HS-1120 system. C. Cartridge Clay-Treated NC-220 Ester Vast improvements in phenolic levels were observed using either 1.02 Unox 269 or 1.52 MCS 1562 in clay-treated NC-220 Ester. Both systems are better than HS-1120 after both seven days (5300and 1,000 ppm vs. 6,300ppm) and fourteen days (21,000and 15,000ppm vs. 28,000ppm). 0. NP Series Esters with Admix 710 The NP Cresylic 220, the NP Phenol 220 and NP Phenol 150 esters con taining 1.52 Admix 710 show less inhibition to phenolic generation. NP Cresylic 150 containing 1.52 Admix 710 is somewhat better but much higher after seven days than the HS-1120 in the General Motors Series (20,000 ppm phenolics vs. 6,300). RSV 0010662 S-75-SS-26 Page Five E. Monsanto Production Samples Pydraul 179 B (Europe 9/12/72) gives phenolic levels after fourteen days comparable to clay-treated NC-220 ester containing 1.5% HCS 1562. Inhibition time is shorter for Pydraul 179 B. Phenolic levels after fourteen days are lower than HS-1120 and equal to those obtained with clay-treated NC-220 stabilized with HCS 1562. Pydraul 30 E (QD 33701) and Pydraul 50 E (QP 3*520) gave almost identical results to those obtained for Pydraul 50 E (QC 12820) used in the General Motors series. There is minimal inhibition to phenoIic generation. F. Competitive Products FQ 220 CF outperforms all the fluids tested at fourteen days. Sevenday phenolic levels are comparable to HS-1120 (*,200 ppm vs. 6,300 ppm), but higher than clay-treated NC-220 with MCS 1562 (1,000 ppm). FQ 220 #3733-5-7 and HS-1120 IC-22&1 tend to be unstable under these conditions. Both systems show some inhibition to phenolic genera tion for two to three days. Phenolic levels increase rapidly to those found In Pydraul 50 E and Pydraul 30 E after seven and fourteen days. G. Fluid Appearance After Fourteen Days 1. Precipitates Black precipitates were observed in all the production Pydraul samples except Pydraul 179 8, all samples prepared with NC-220 (12/2/7*) and the laboratory batches of NP cresyllc and NP phenol. Pydraul 50 E (QC 12820) G.M. Test Pydraul 50 E (QO 3*520) MCS 1771 Pydraul 30 E (QD 33701) MCS 1772 NC-220 ester - 0.5% Unox 289 NC-220 ester - 1.0% Unox 289 NC-220 ester - 1.0% MCS 1562 NC-220 ester - 1.5% MCS 1562 NP cresylic 220 MCS 1769 NP cresylic 150 MCS 1770 NP phenol 220 MCS 1776 NP phenol 150 MCS 1779 medium to heavy medium to heavy medium to heavy medium light to medium heavy heavy heavy heavy medium to heavy medium to heavy No precipitates were observed In the laboratory clay-treated NC-220 samples, the Pydraul 179 B sample from Europe or In any of the competitive samples. RSV 0010663 S-75-SS-26 Page Six 6. Fluid Appearance After Fourteen Days (Cont'd) 2. Color Orange Pydraul 179 B Europe 9/12/72 FQ 220 CF Slight Darkening HS-1120 G.H.series Clay-treated NC-220 - 1.02 Unox 289 HCS 17^2 Clay-treated NC-220 - 1.52 MC5 1562 HCS 173 Dark NP phenol 220 HCS 1776 FQ 220 #3733-5-7 HS-1120 G.H. test HS-1120 CF 6/22/73 Very Dark Pydraul 50 E (QC 12820) G.H. test Pydraul 50 E (QD 36520) HCS 1771 Pydraul 30 E (QD 33701) HCS 1772 NC-220 0.52 Unox 2$$ NC-220 1.02 Unox 289 NC-220 1.02 HCS 1562 NC-220 1.52 HCS 1562 NP cresylic 220 HCS 1769 NP cresylic 150 HCS 1770 NP phenol 150 HCS 1779 H. Haximum Phenolic Values A theoretical calculation was made to determine the maximum level of phenolics that could be generated under the General Hotors test conditlons. Water 18 g/mole 1 g * 0.0556 moles cumylphenol 212 g/mole monylphenol 220 g/mole 0.0556 moles X 212 g/mole 0.0556 moles X 220 g/mole 11.8g cumylphenol 118.000 ppm cumylphenol 12.2g monylphenol 122.000 ppm monylphenol RSV 0010664 S-75-SS-26 Page Seven If no water is lost during the test, the phenolic levels of 35,000 to 40,000 ppm observed probably represent an equilibrium condition of: " (ArO)3 P(-0) + HjO --Ar0H (Ar0)a P<-0) OH ArOH (ArO) 2 P(-0) OH ------- (ArO)s P(HJ) + H20 References: MIC 255266 MIC 255267 MIC 285101 MIC 285106 MIC 285112 MIC 265115 MIC 285128 MIC 285129 MIC 285135 MIC 285149 ss Monsanto Industrial Chemicals Co. Applied Sciences St. Louts, Mo. 7/75 ~ B. Katlafsky, P. F. Heimsch, M. V. Dietrich RSV 0010665 S-75-SS-26 Hours 0 48 96 120 144 168 240 336 TABLE I HYDROLYTIC STABILITY OF GENERAL MOTORS SERIES ppm PHENOLICS CALUCLATEO AS PHENOL Pydraul 50 E QC 12820 MIC 255266 HS 1120 Chevrolet Centra) L* MIC 255266 450 600 *50 600 3.800 3,750 840 820 26,900 27,000 27.300 25,800 1,100 1,050 30,400 31,500 30,300 32,800 6,250 6,300 35,900 36,800 38.500 38,000 28,000 27,800 Appearance after 336 hours Fluid Tube Very dark Med-heavy black ppt. dark streaks on upper Mai Is Dark-clear Clean i RSV 0010666 S-75-SS-26 Hours 0 48 72 96 144 168 240 336 TABLE II HYDROLYTIC STABILITY OF MO220 ESTER SERIES ppm PHENOL ICS CALCUALTEP AS PHEHOL 0.5% Unox 289 HIC 285108 1.0% UNOX 289 MIC 285108 1.0% MCS 1562 HIC 285108 285 295 278 282 295 278 1,340 . 1,330 1.130 1,220 1,290 1,270 5,200 5,270 2,160 2,730 1,560 l.S'lO 4,180 4,260 34,000 33,700 9,600 9,700 4,140 3,950 33.1*00 33,200 38,500 38,200 15,700 15,900 1.5% MCS 1562 MIC 285108 274 274 1,830 1,760 2,030 2,100 3,280 3.300 18,100 17,900 Appearance after 336 hours Fluid Very dark Very dark Very dark Very dark Tube Heavy black ppt. black spots on upper walls Light to medium black ppt.-black streaks on upper wl Is Heavy black ppt. black spots on upper walls Heavy black black spots upper walls RSV 0010667 S-75-SS-26 TABLE III HYDROLYTIC STABILITY OF CARTRIDGE CLAY-TREATED NC-220 ppm PHENOLICS CALCULATED AS PHENOL Hours HCS 1742 1.0* Unox 269 HIC 285101 HCS 1743 1.5* HCS 1562 HIC 285101 0 445 449 267 267 72 543 600 456 426 96 895 925 168 5,440 5,160 524 566 1,040 980 336 20,900 20.700 14,800 14,900 Appearance after 336 hours Fluid Tube Some darkening Clean Some darkening Clean i t RSV 0010668 S-75-SS-26 Hours 0 68 72 96 168 TABLE IV HYDROLYTIC STABILITY OF HP ESTERS WITH 1.5* ADHIX 710 ppm PHENOLICS CALCULATED AS PHENOL HCS 1769 NP Cresyllc 220 MIC 285112 HCS 1770 NP Cresylic ISO MIC 285115 HCS 1776 NP Phenol 220 MIC 285128 MCS 1779 NP Phenol 150 MIC 285129 532 622 683 652 536 630 695 633 1,720 1,750 2,280 2,270 6,070 6,260 16,100 15,900 2,050 2,030 5,800 5,730 18,600 19,100 18,300 ` 18,100 3*1,300 36,300 20,500 20,300 62,500 61,900 36,000 3*1,900 Appearance after 366 hours Fluid Very dark Tube Heavy black ppt. a few black spots on upper walls Very dark Dark Heavy black ppt. Medium to a few black spots heavy black on upper walls ppt. Very dark Medium to heavy black ppt. RSV 0010669 S-75-SS-26 Hours 0 48 96 144 168 240 336 TABLE V HYDROLYTIC STABILITY OF MONSANTO PRODUCTS ppm PHENOL ICS CALCULATED AS PHEHOL Pydraul 179 8 Europe 9/12/72 MIC 285135 Pydraul 30 E QD-33701 HCS 1772 153 289 149 282 543 532 1,810 1,850 18,100 18,000 30,800 28,900 7,590 7,670 14,600 14,300 39,500 38,300 41,700 41,600 Pydraul 50 E 00-34520 HCS 1771 361 373 25,400 26,600 27,800 27,600 31,800 32,700 35,300 34,400 Appearance after 336 hours Fluid Tube Orange Clean Very dark Medium to heavy black ppt. dark granular spots on upper wal Is Very dark Medium to heavy black ppt. dark granular spots on upper walls RSV 0010670 S-75-SS-26 Hours 0 48 96 168 336 TABLE VI HYDROLYTIC STABILITY OF COMPETITIVE PRODUCTS ppw PHENOL ICS CALCULATED AS PHENOL FQ 220 CF 6/22/73 MIC 285135 551 558 FQ 220 3733-5-7 MIC 265135 1,370 1,400 HS 1120 C-2281 MIC 285135 358 350 710 1,980 1,360 668 1,9*10 1,350 1,000 960 6,370 6,480 8,360 8,360 4,250 4,120 26,400 27.000 22,300 22,800 10,400 10,900 30,700 31,300 28,800 28,700 Appearance after 336 hours Fluid Orange Tube Clean Dark Clean Dark orange Clean R$ V 0010671 `Jl. Jv.lU RSV 0010672 ni" f r i uu r\ t i RSV 0010673 RSV 0010674 Phenolic* HYDROLYTfC STABILITY OF NP CRESYLlC ESTERS Jw -1 <J RSV 0010675 Ppm PhenoJics t-munt 3 HYOROLYTfC STABJ LITY OF HP PHENYL ESTERS .- Lr EOttTAItHUG -i-r5* 'ACM I X~7i0 -EPOX+Dt -- O O' RSV 0010676 0 2 . k 6 8 10 12 l* DAYS RSV 0010678 Spectroscopy S-75-SS-27 DETERMINATION OF VINYL CHLORIDE, TRICHLOROETHYLENE AND EPICHLOROHYDRIN IN AIR AT BAXLEY, GEORGIA PLANT INTRODUCTION This study determined levels of vinyl chloride (VC1), trlchlorethylene (TCE), and epichloropydrln (ECH) In the air at this location. SUMMARY Results are given In the attached table. The values reported in this table may be high due to the presence of Interfering components. They should be considered as upper limits. Concentration for TCE ranged from 2.8 to 0.3 ppm while ECH was detected in amounts of 8.3 to 0.3 ppm. Vinyl chloride was not detected with a detection limit of 0.3 ppm. EXPERIMENTAL Samples were collected on a C-I05 1 meter column and analyzed on a tenax column. Two-hour samples were taken with a flow of about 10 ml/mtn. Spec troscopy Method 74-7 and Special Study 74-34 give details of the method and procedure of analysis and calculations. GC retention times were used for identification. Reference: GC/MS file #75-124 ss Monsanto Industrial Chemicals Co. Applied Sciences St. Louis, Mo. 7/75 * L. M. Chapman, C. Hoffmann, M. W. Dietrich RSV 0010679 S-75-SS-27 SET I* ECH (ppm) *TCE (ppm) i H-4 8:00-10:00 a.m. N.D. <.3 0.4 i M-2 ij 10:00-12:00 p.m. N.D. <.3 1.3 i H-3 i 2:00-4:00 p.m. lost In analysis 4:00-6:00 p.m. 0.4 0.3 , L-4 12:00-2:00 p.m. L-6 2:00-4:00 p.m. M-1 4:00-6:00 p.m. SET II* ECH (ppm) 8.3 0.3 3-0 TCE (ppm) 2.8 N.0. <..3 0.6 *The values reported in this table may be high due to the presence of Interfering components. They should be considered upper limits. RSV 0010680 Spectroscopy S-75-SS-28 PERSONNEL MOWITORIMG OF PCP UNIT AT NITRO PLAHT INTRODUCTION This study was conducted to determine personnel exposure to polychlorinated propenes end propenes. SUMMARY Results are given In the attached table. In sample # P-4003 taken during the process, several chlorinated propanes and propenes were detected. The attached spectrum Illustrates how selected Ion detection (at mass 75) In conjunction with a total Ion scan (Tl) on our new HP MS obtained a good Identification and separation of the following components: dlchloropropene, trans-trIchloropropene, cis-trlchloropropene, tetrachloropropane, and tetrachloropropene. Levels of these materials ranged from 0.4 to about 3.0 ppm. Background samples showed more than thirty organics ranging from 10 to 43 ppm present. This high background may be due to a rubber cap used in shipping the sampling tubes to St. Louis. EXPERIMENTAL For basic procedure, refer to Spectroscopy Method 74-7* An 0V-1 one-meter glass column was used for the analyses and a tenax GC for collection. From 3 to 8 liters of air were taken with an $KC personnel pump. Calculations are based on known standards and identification was made by GC/MS in the selected ion mode. CALCULATIONS Liters of air * supplied by Bruce Eley 0) ............ Weight ^ of . sample area , of , sample X -c-o---n--e--.---s--t--d--.----(-u*q/'1)zvX~evt,oA l. Ini. (ui) -*------------- (ug) Con(cuengt/rl)at I on - nter* of *ir Examp1e #P-4003 trans-trichloropropene Liters of air 6.3 Weight of sample - 992758 X ['^g,' - 5.4 Concentration - 5.476.3 0.9 ug/i Referenca: GC/MS file #75-62 ss Monsanto Industrial Chemicals Co. Applied Sciences St. Louis, Mo. 8/75 " L. M. Chapman, M. W. Dietrich RSV 0010681 S-75-SS-28 RSV 0 0 1 0 6 8 2 St. Louis Blk P6-100I* PB-2001* Dlchloro propane HD NO NO TABLE (ug/1) Trans-trIchloro propane ND Cls-trlchloro propene ND NO NO ND ND Tetrachloro propane ND ND NO Tetrachloro propene ND ND ND Total Other Organics 3 42 18 PB-3001* NO NO ND ND NO 32 P-4Q0I 2.9 ND HD 0.6 ND 25 P-4002 2.3 ND NO 0.4 ND 16 P-4003 1.0** 0.9 0.6 0.5 0.5 10 * Theie samples were taken of the plant air before the process began. ** This value Is the combined concentration of Isomers of dlchloropropenes In Hlx I and Mix II (see attached chromatogram). Nix I also has an unresolved component other than dlchloropropene which appears to be trlchloroethene. Similarly* Nix II also has another component with HW 108. Therefore, the result Is a maximum value. NITRO PLANT PENTACHUmOFROPANE PROCESS RSV 0010663 1 Spectroscopy S-75-SS-29 BISCHLOROMETHYL ETHER CONTENT OF DEQUEST PRODUCTS AND EVERETT PLANT AIR INTRODUCTION This study was undertaken because of concern that some Dequest products may contain harmful levels of blschioromethyl ether (BCME). BCME is listed by OSHA as a human carcinogen. Both final product and air in various produc tion locations were analyzed to insure no safety problems exist for our workers or customers. SUMMARY A method was developed for determining the BCME content in Dequest products via a headspace analyses, l.e. the BCME content of the air above the pro duct was determined rather than the product analyzed directly (see discussion) Results by this method were shown to be consistent with those obtained by a more direct analyses procedure. Our standard methodology for air monitor ing was used for determining the BCME content of air in the Everett Plant Dequest department. Low levels of BCME were found in certain Dequest products and in air taken from a synthesis carried out In a lab reactor. Values found are given in the attached tables. No BCME was found in air taken from a filled Dequest 2041 fiber pack or in air taken in the Dequest department of the Everett Plant. The Monsanto Medical Department has taken the position that they see no reason that the levels of BCME found would constitute a problem. DISCUSSION A headspace GC procedure was chosen for this analysis for two principal reasons. First, it provides a highly sensitive approach free of the matrix effects which might be expected If Dequest products are injected directly into a GC. Interferences have been observed when a similar analysis for BCEE in Phosgards was attempted by direct GC analyses. Extraction of the product followed by GC analyses appears a satisfactory alternative but has poor sensitivity as indicated in Table I. The second reason is more funda mental. Since BCME fs formed if both HC1 and formaldehyde are present, it Is possible that BCME could form in the headspace above Oequest even though there Is no BCME In the product. A headspace procedure covers both possi bilities since, if BCME were in the product, a significant percentage would also be in the headspace. I. BCME in Products A. Sample Collection Headspace over liquid Dequest samples was taken by charging 5 ml of sample via syringe into a 125 ml suction flask containing a Teflon stir bar and fitted with a 5 X 130 mm glass dip tube set In a Teflon covered cork. The dip tube came within 20 n*n of the bottom. The side arm carried a short tube charged with activated charcoal and a T through which excess N2 flowed. Aspiration was applied through the dip tube for 2.5 min. while stirring for equilibration, flow RSV 0010684 S-75-SS-29 Page Two BCHE In Products (Cont'd) A. Sample Collection (Cont'd) rate adjusted to AO ml/mfn. Then a sampling tube was mounted on the dip tube using a short length of Teflon tubing and aspiration continued for usually 7.5 min. Sampling tubes were 1/A" X 6" glass charged with 1$0 mg Tenax GC and conditioned at 250*C. Ether extraction of liquid samples was carried out on SO ml portions transferred via syringe to a stemless short form 60 ml separatory funnel. A small amount of dlethylether was added and after agita tion separation was hastened by centrifuging at low speed in a bucket type centrifuge. An estimated 1.5 ml of the ether dissolves and at least 0.5 ml remains in emulsion. The clear ether extract was used for direct GC injection. B. Analyses With the helium flow off and the vacuum pump to the mass spectro meter off, a 1/A" X 6" Tenax sampling tube Is placed in the heater and externally connected to the Injection port of the GC. At this time, the analytical column is cooled to -50*C with liquid nitrogen. Now, the helium flow is diverted to flow through the precolumn. Quickly, check for leaks In the system, turn on vacuum pump to mass spectrometer, turn on heater and start GC program and clock to mass spectrometer. Heat is supplied by a heater consisting of 86 turns of 2A gauge asbestos covered Chrome! "A" wire ( 75 ft.) coiled to fit Into a 120 mm X 10.1 tm i.d. Pyrex tube. The coil is lined with two turns of 2.5 mil aluminum foil allowing a slide fit for the sampling tubes. Twenty volts brings the sampling tube to 200C in about 2.5 minutes. After four minutes, turn off heater and after 7 1/2 minutes open the valve to the mass spectrometer and start scan at 7 minutes 50 seconds. The following lists the GC/MS parameters: GC - helium flow about 30 ml/min auxiliary temp - 250*C injection port temp - 250*C analytical column - 10X S-A09, 2 meter X 1/8" on 80/100 Chrom V H.P. program - -50*C for A min then up to 1d0*C at 32*/m!n MS - Internal source heater 166*C column A, B. valves 290*C dodecapole 100*0 program SIM masses scanned-79 81, A9, 51 dwell time - 250 each offset - 0 run time - 15 minutes gain - 7 RSV 0010685 S-75-SS-29 Page Three I. BCHE In Products (Cont'd) B. Analyses (Cont'd) After the samples were analyzed, a standard of 0.006 ug/ul of BCHE was Injected into the GC and run under similar conditions. Compari son with the standard by intensity of the characteristic ions and GC retention time provided the means of identlfIcation. Attached is the selected ion chromatogram for BCHE. Selected ion detection provides very high sensitivity by collecting data only from selected fragment ions of the component of interest rather than the total spectrum. In this case, fragment Ions 79 81, 49 and 51 are charac teristic ions of BCHE. Calculations were based on the mass 49 ion, since some interferences were observed at the other ions. The bfschloromethyl ether (BCHE) used for the standard was provided by Hyron J. Holm (lab prep. N6P 222 474 6/73) as a solution ca. 5% in hexane. The standardization was done indirectly on the assump tion that the flame ionization detector should have a reasonably equivalent response for BCHE and 1, 2-dIchloroethane. A standard was prepared of close to 1 g. of 1, 2-dichloroethane in 10 ml of ' hexane solution and was twice diluted 1 to 10 to provide a 1000 ug/ul standard. By trial a comparable dilution for the BCHE was found. Two micro!iters of these were run alternately on the GC under the analytical conditions to give three sets of area print outs on the Autolab. These were averaged and compared to give the value 0.61 U9/UI for the BCHE standard. A thousand-fold dilution provided the working standard labeled #14-0, 0.00061 ug/ul II. Deguest 2041 Fiber Pack A. Sample Collection Headspace over finished goods was sampled using the same type sampling tube. No vacuum line was available at the sIte, therefore a one liter suction flask was equipped with a vacuum gauge and an Ideal refriger ator valve. With the flask evacuated, a program of valve setting ver sus gauge reading was determined to maintain approximately 40 ml/min. flow. A one-half and a one liter sample were collected. B. Analyses The procedure described in Section I was used. III. Laboratory Reactor A. Sample Collection Reactor headspace "grab" samples were obtained by means of 40 mm diameter cylindrical bulbs, approximately 230 ml volume with Teflon corks at each end. The bulbs were first evacuated via the far end. Then the cork was closed and the near end opened to take up headspace through a short connection. The resultant sample contained approximately 2 ml aqueous HC1 condensate. RSV 0010666 S-75-SS-29 Page Four The sample bulb was supported vertical1y, a glass/Tenax sample tube attached at the upper end using a short piece of Teflon tubing. The upper 2/3 of the Tenax packing was equipped with a room temperature ~ water jacket. The upper cork was opened, then gentle aspiration was applied to the sample tube while the lower cork was "cracked*1 to allow a slow bubbling. Nitrogen overflow was supplied to the Inlet. A heat gun was employed during the 15 min. transfer period keeping the lower portions of the bulb hottest, the upper portion definitely warm and the upper cork and tubing up to the Tenax packing just warm enough to avoid condensation. Collections from the reactor at 60 min. and 120 min. were taken. 6. Analyses The procedure described In Section I was used. IV. Everett Plant Air A. Sample Collection Air samples were obtained by drawing air through a Tenax GC pre-column attached to a personnel monitoring pump with rubber tubing. Sample sizes ranged from 4 to 9 liters at the various locations In the plant. See Table 11C for results. 8. Analyses The procedure described in Section I was used. ss Monsanto Industrial Chemicals Co. Applied Sciences St. Louis, Mo. 7/75 " L. M. Chapman, 0. E. Klnast, H. W. Dietrich RSV 0010667 S-75-SS-29 RSV 0010688 S-75-SS-29 TABLE I BCHE IN DEQUESTS A. HEADSPACE Sample Dequest 2060, Final Hexagon, Unstripped Above After Sitting 24 Hours Dequest 2060, Hexagon, Stripped Dequest 2000, Unstripped, 255663 #3 Dequest 2000, EBU18, Stripped Dequest 2054, Lot EC 339-2 Oequest 2006, Unstripped, #255663 #4 (2 Phase) Unfiitered Lonza By-product (Dequest 2000 Type) Filtered Lonza By-product (Dequest 2000 Type) Concentration BCHE 1. PPB In Air ca .5 PPB in Air N.D. .5 PPB in Air N.D. .5 PPB in Air N.D. <^5 PPB in Air N.D. <.5 PPB in Air N.D. <5. PPB 7 in Ai 0.4 PPB in Headspace 1.4 PPB in Headspace B. EXTRACTION (DIETHYL ETHER) Dequest 2060, Hexagon, Unstripped Dequest 2006, Unstripped N.D.* <20 PPB in Liquid N.D.* <100 PPB In Liquid *Assumlng 10% efficiency of solvent extraction RSV 0010689 S-75-SS-29 TABU II OTHER BCHE ANALYSES A. DEQUEST 2041 FIBER PACK Sample Dequest 2041 Lot 176-18-8B B. LABORATORY REACTOR Sample 60 minutes after start of reaction 120 minutes after start of reaction C. EVERETT PLANT AIR Sample #77. 6/4/75 Dequest 2000 drum filling #18, 6/18/75 Airspace above scrub water #68. 6/24/75 Airspace Dequest 2000 drum storage #50. 6/27/75 Airspace above scrub water tank #34, 6/30/75 Airspace near HC1 and formaldehyde storage tanks Concentration BCHE N.D. <.5 PPB In Air Concentrat Ton BCHE 4. PPB In Air 12. PPB In Air Concentration BCHE N.D. <0.5 PPB N.0. <0.5 PPB N.D. <0.5 PPB N.0. <0.5 PPB N.0. <0.5 PPB RSV 0010690 Spectroscopy S-7S-SS-30 TRACER LITHIUM ANALYSES - NITRO PLANT EFFLUENT-11 SUMMARY Lithium Is used as a tracer to observe the dilution of the Nitro plant liquid effluent. Fifty-four effluent samples ranging from 0.05 to 0.2 ppm Li were analyzed by atomic absorption. DETAILS All samples are cloudy and contain some solids. Preliminary survey anal yses show they contain considerable sodium and calcium and roughly 0.02 to 0.4 ppm Li. Instrument changes since the previous set were analyzed required a revision of the method used. Sodium Ion enhances the lithium response, but enough is present so that all samples are equally enhanced. Addition of sodium Ion or hydrochloric acid, agitation or filtration was found to have negligable effect. The lower lithium values are within ten times the system's noise level. Most burner and flame combinations pro duce an upward curvature in the absorbance versus ppm plot. The nitrous oxide burner using a small and very oxidizing flame was found to provide ,, the flattest response when used at 6 ran below the grazing position. There is a matrix effect, l.e. a given amount of LI In the sample does not pro duce the same response as a pure water solution. Therefore the samples were taken In two groups and four from each group were analyzed by the method of standard additions. The values obtained for the selected four were used to peg the response for the group. This enabled the quick method of direct analysis to be used for the bulk of each group, without addition or separations, as in the previous work. The ppm LI are listed in the table. ss Monsanto Industrial Chemicals Co. Applied Sciences St. Louis, Mo. 7/75 - 0. E. KInast, M. W. Dietrich RSV 0010691 SAMPLE NUMBER - Ppm Li tot 0.048 102 .048 103 .047 (0.047)* 104 .045 105 .045 106 .049 107 .062 108 .077 109 .090 no .101 111 .106 112 .104 (0.103) 113 .095 114 .090 115 .088 116 .086 117 .085 SAMPLE NUMBER 118 119 120 121 122 123 124 125 126 127 128 129 130 131 132 133 ppm LI 0.081 .081 .080 .080 (0.080) .077 -075 .074 .074 .071 .067 .066 .059 .060 (0.060) .057 .056 .055 SAMPLE NUMBER 200 201 202 203 204 205 206 207 208 209 210 211 212 213 214 215 216 217 218 219 220 ppm LI 0.050 .054 .054 .049 (0.050) .095 .204 .166 (0.165) .147 .110 .110 .093 (0.095) .082 .074 .072 .067 .059 057 .055 (0.053) .052 .053 .050 * Values In parenthesis were those obtained by standard addition. RSV 0010692 Spectroscopy Special Study S-75-SS-31 ANALYSIS Of MlIRQ PLANT WASTE WATERS FOR TRACE ORGANIC POLLUTANTS INTRODUCTION Plant waste water samples equivalent to those collected by EPA representa tives were analyzed for trace organic pollutants. The Information obtained from these samples will be used to plan possible reaction to EPA results. Analyses of all samples were carried out in accordance with Spectroscopy New Technique 70*3* The analytical techniques used were the same as those it was anticipated the EPA might use. SUMMARY Samples obtained from the river water Intake# tall oil pond# and treatment plant were analyzed. A total of 16 components were observed in the treat ment plant samples and 32 In the tall oil samples. No organic components, <100 ppb, were observed In the river water Intake samples. In general the components identified were associated with plant processes and ranged in concentration from 100 ppb to 9 ppm. RESULTS The components Identified and their approximate levels are shown in Table I. Five of the twelve components observed In the treatment plant samples were identified while only two of the thirty-two components detected In the tall oil samples were Identified. The components not Identified In the tall oil samples appear to be a complex mixture of phenolic and hydrocarbon type constituents. In Table II the GC retention time and concentration of the individual components formed in a set of tall oil pond samples are shown. Only ten of the thirty peaks detected but not identified were at levels greater than 1 ppm. Two differences were noted upon comparison of the peaks found in the extracts of the acidified and non-acid!fled samples. First, the acidified samples contained a larger number of components and secondly# compounds found in both were generally at higher levels In the acidified samples. These dif ferences could be attributed to either microbial degradation or the fact that all samples were extracted as received without any pH adjustment. If the non-acldifled sanples had been acidified higher recoveries of the acidic components might have occurred. In order to Insure that any basic organics were being extracted# the acidi fied saddles were made basic and re-extracted. No addition compounds were detected in the basic extracts. No detectable (<.1 ppm) organics were found In the T-56 (River) 69 and 6/11 samples, both as is and acidified. ss Monsanto Industrial Chemicals Co. Applied Sciences St. Louis# Mo. 6/75 - E. S. Tucker, 0. E. Klnast# M. W. Dietrich RSV 0010693 S-75-SS-31 TABLE 1 - Components f5T75 6-9 a 10 Acid Benzothlazole 0.2 2-Hethylbenzothlazole 0.5 2, 2, 4 - Trlmethyl-6-ethoxy- 1.7 quinoline 2-Hydroxybenzoth1azole 6.7 2-Mercaptobenzoth1azole 1-3 ppm Not Identified 5.9 (6)** ppm Total Organics 16.3 PPM* Found MH #3 mT73 6-9 ft 10 6-11 N.A. Acid NO 0.6 0.8 0.7 2.1 1.3 0.2 5.8 NO 0.7 A.3 (7)** 8.4 (5)** 7.4 17.5 MHl3 6-11 N.A. NO ND NO ND ND ND NO Components Guaiacol (o-methoxyphenol) 1, 2 - dI-methoxybenzene ppm Not Identified ppm Total Organics Tall Oil 6-9 Acid Tall Oil 6-9 N.A. Tall Oil 6-11 Acid Tall Oil 6-11 N.A. 5.2 0.2 NO NO 0.8 NO 0.4 NO 31 .A (30)** 32-9 (29)** 21.4 (29)** 26.4 (26)** 37.4 33-1 21.8 26.4 * Calculated using benzothlazole as an Internal standard ** Number of components NO-None detected, <0.1 ppm RSV 0010694 TABLE II Retention Tlme(See) 37 62 70 76 100 117 131 136 U9 161 173 183 192 200 209 222 236 266 263 286 299 313 326 368 357 376 393 605 621 637 666 665 672 662 692 *99 519 550 583 603 Tell Oil 6-9 Acid PPM Tall Oil 6-9 N.A. NO <0.1 0.1 0.1 0.2 2.1 NO 5.2 1.8 5.3 0.8 0.8 0.8 0.6 0.6 1.9 2.1 1.0 1.0 2.7 0.2 0.7 0.9 ND NO 0.3 0.1 <0.1 2.6 0.3 ND 0.5 1.3 ND 2.1 1.5 0.2 ND <0.1 <0.1 0.2 NO 0.3 ND 0.2 1.3 0.5 0.2 ND 5.9 <0.1 NO 0.3 0.2 ND ND 0.8 0.5 <0.1 0.3 ND ND ND <0.1 <0.1 0.2 ND <0.1 3.6 0.5 <0.1 0.8 1.8 0.9 2.8 2.2 2.1 0.5 0.6 0.6 NO * None detected* <0*1 ppm RSV 0010695 Speetroscopy 5-75-SS-32 DETERMINATION OF VOLATILES IN DECATUR. ALABAMA PLANT AIR (V) INTRODUCTION This is a continuation of an investigation to determine levels of vinyl acetate (VA) acrylonitrile (AN)t vinyl bromide (VBr), vinylldene chloride (VnCIi)* in air at the south continuous polymer area of the Decatur, Alabama plant. The data obtained will be used to identify areas where worker safety problems may exist. SUMMARY Results are found in Table I. GC retention time provided the means of Identjflcation of the volatiles. Acrylonitrile had values from 0.4 to 1.6 ppm, vinyl acetate values ranged from 0.2 to 0.9 ppm, VBr ranged from 0.1 to 1.3 ppm and vinylidene chloride ranged from 0.4 to 3.0 ppm. EXPERIMENTAL Refer to Spectroscopy Method 74*7 for the analyses procedure used. Fifteen^ minutes were allowed for the heating of the external collection column to collect the acrylonitrile before proceeding as in Method 74*7. An example of the procedure used to calculate concentration Is given in the S-75-SS-1 report. Sample collection was made using a Model 222-451 SKC pump. Calcu lations were based on known standards. Reference: GC/MS File #75-150 ss Monsanto Industrial Chemicals Co. Applied Sciences St. Louis, Mo. 8/75 - L. M. Chapman, M. W. Dietrich RSV 0010696 i i. V' $-75-$$-32 H-4 L-12 M-2 H-3 L-9 L-2 L-1 L-5 TABLE I CONCENTRATION PPM VBr VnCI 2 Blank Blank None Detected 0.8 NO 1.3 3.0 0.8 2.1 0.3 0.4 0.1 0.8 AN* 1.1 1.1 1.6 0.6 0.4 VA* 0.2 0.4 0.9 0.6 0.3 j * AN and VA are maximum values because of Interference of other components when calculating concentrations. Volume samp lev 1 "2 liters Flow rate vig ml/min Sampling tlme**1~2 hours RSV 0010697 Spectroscopy S-75-SS-33 TRACER LITHIUM ANALYSES - NITRO PLANT EFFLUENT*II SUMMARY Lithium Is used as a tracer to observe the dilution of the Nltro plant liquid effluent. Fifty-one effluent samples ranging from 0.05 to 0.25 ppm LI were analyzed by atomic absorption. DETAILS This set of fifty-one samples was analyzed In the same manner as the previous (7/75) set. Forty-seven were found to be within a narrow range, the other four are considerably outside this range. The four and a selected spread of seven out of the group were analyzed by the method of standard additions. The values obtained for the selected seven were used to establish the ppm level for the group, all of which were analyzed by direct aspiration. The ppm values In the table are reported as three significant figures because this reflects a real trend In relative values between adjacent samples. However, only two-figure accuracy should be taken for the actual level. ss Monsanto Industrial Chemicals Co. Applied Sciences St. Louts, Mo. 8/75 - 0. E. Klnast, M. V. Dietrich RSV 0010698 Spectroscopy S-75-SS-33 RSV 0010699 of 7/23 ppm Olrect Std Add1tlon ppm 1 ._ 2 -- 3 .187 4-- 5 .206 6 .177 7 .191 8 .183 9 .187 10 .179 11 .173 12 .176 13 .164 14 .165 15 .167 16 .164 17 .166 18 .166 19 .168 20 .162 21 .165 22 .165 23 .161 24 .160 .052 .256 .228 .191 .170 .162 LITHIUH TRACER IN NITWO EFFLUENT AA 813 of 7/24 ppm Direct Std Addition ddhi 1 .161 2 .161 3 .158 4 .157 5 .159 6 .155 7 .152 8 .153 9 .152 10 .149 11 .149 12 .149 13 .149 14 .144 15 .145 16 .143 17 .143 18 .143 19 .139 20 . 140 21 .138 22 . 141 23 .143 24 .140 .158 .149 .136 Sa of: 7/25 ppm Direct .133 Std Addition ddm 1 132 7/26 .120 7/27 -- .107 Spectroscopy S-75-SS-3* DETERMINATION OF TRICHLOROETHYLENE (TCE) IN AIR AT DELAWARE RIVER INTRODUCTION Air in the Phosphate Ester Department of the Delaware River Plant was sampled while Santicizer 148 was being made. The results obtained Indicate worker exposure levels. SUMMARY TCE was detected In the samples from levels of 0.3 to 3*0 ppm, well below the TLV. EXPERIMENTAL A Chromosorb 105 pre-column was used for sample collection. A Tenax GC analytical solumn was used for analysis. Refer to Spectroscopy Method 7*>-7 and Spectroscopy Special Study 73*11 for analysis procedures used. Calculations were based on a known standard. Identification was made by GC retention. Calculations Volume of Air m Pump Flow Rate ,, Sampling Time ,, )f..j Sampled (Liters) (mi/min.) (min.) Weight Sample (pg) Concentration Sample (pg/L) Area Sample Peak (counts) Cone. Std. (pq/pL) Vol. injected (uL) Area of Standard (counts) * Weight Sample (pg)/Vo1ume of Air Sampled (Liters) Concentration Sample (ppm) For Sampling 75*33 Volume of Air Sampled - 32.5 X 120 X 10"3 - 3.896L Weight Sample (pg) 38.k pg Concentration TCE 37855'" 986 "9/L (ug/l) Concentration TCE * 9*86 X (ppm) - 1.85 ppm Reference: GC file #75-151 ss Monsanto Industrial Chemicals Company Applted Sciences St. Louis, Missouri 8/75 - L. M. Chapman, M. W. Dietrich S-75-SS-3* Page Two RSV 00 LO 70 L TABLE Sample Tube 75-33 75-48 75-28 75-45 TCE (ppm)* 1.9 0.4 3.1 0.3 * Pump flow & 32 ml/min Sample volume as 3*9 liters Sample time ft? 2 hours RSV 0010702 Spectroscopy S-75-SS-35 DETERMINATION Of BENZENE IH AIR AT ANNISTON, ALABAMA PLANT 11 INTRODUCTION The purpose of this Investigation was to determine worker exposure to benzene. SUMMARY Benzene ranging from 0.1 to 1.0 ppm was detected. Two samples were obtained for an 8-hour day and two were short-term samplings where high levels of benzene were expected. The results are given in the table. EXPERIMENTAL GC/MS was used In the verification of benzene and calculations are based on a benzene standard. An example of the calculations is given below. Results shown for the blanks were calculated on the basis of the same volume of air used for the settles. Calculations Volume of Air m pump flow rate y sampling time x 10~s Sampled (liters) (ml/min.) (min.) Vt. of sample m area sample peak ,, cone, std, (jig/yl) Vol. Inj. (yl) (ug) " (counts) Area of std. (counts) Concentration of sample Weight of sample (ug) (ug/1) " Volume of air sampled (liters) Concentration of sample yg/l (sample) X 24j--5 (sample) (ppm) " M*W* For Sample 75-34 Benzene unloading dock Volume of air , j,0o M|/m,n> x 15 min. X 10`* - 6 liters sampled (liters) Wt. of sample (ug) Cone. Benzene (ug/1) 25*9 X X 2.0 - 18.4 ug 3.1 ug/l Cone. Benzene (ppm) 3.1 X -j$- 0.96 ft* 1.0 ppm Reference: GC/MS File #75*144 ss Monsanto industrial Chemicals Conpany Applied Sciences St. Louis, Mo. 8/75 * L. M. Chapman, M. W. Dietrich, C. Hoffman RSV 0010703 TABLE ^Draining Benzene Feed Tank *Benzene Unloading Dock **Btph Dept 7-8-75 **Biph Dept 7-9-75 Blank >0.6 ppm*** 1.0 ppm 0.2 ppm 0.1 ppm 0.1 ppm * flow 400 ml/mln sampling time 15 min volume m 6 1 Iters pump - BendIx ** flow - 25 ml/mln sampling time - 8 hours volume - 12 11ters pump - SKC *** Incorrect instrument attenuation used. RSV 0010704 Spectroscopy S-75-SS-36 PYORAUL 29ELT / PYDRAUL 5QE GEL COMPLAINT FROM REPUBLIC STEEL SUMMARY IR (infrared) analysis of fractions isolated by both solvent extraction and GPC (gel permeation chromatography) of the gel formed In a storage tank of a mixture of Pydraul 29ELT and Pydrau) 50E at R public Steel showed the gel was composed of: 1. Residual phosphate ester. 2. Styrenated rubber. 3. Polyglycol. k. Reation procuct of the epoxy stabilizer with the phosphate ester half acid. 5. Metal organopyrophosphate. 6. Inorganic phosphates containing high levels of iron. The IR spectrum, the GPC retention time and the molecular weight by GPC of the polyglycol indicates this is Ucon's polyoxyalkylene glycol 75-H-350,000. This material Is foreign to either Pydraul 29ELT or Pydraul 50E formulations which use Jeffox 0L-2700. The IR and GPC also ruled out Ucon concentrate 700 used in other Pydraul formulations as the glycol source. SEPARATION The mixture of phosphate ester fluid and gel were poured into a 25 X 80 hid cellulose extraction thimble and the bulk of the fluid separated by gravity filtration. The concentrated gel was fractionated by the sequentional solvent extraction scheme shown in Figure 1. The hexane insoluble acetone and chloroform soluble fraction, FII, was further fractionated by GPC column with a linear HW range of 80 to 3000. Because of the unknown quantity or residual fluid held up in the gel, no attempt was made to quantitate the solvent extraction. FII was the largest non-fluid fraction isolated. DISCUSSION Infrared analysis of the solvent extracted and GPC fractions showed the gel contained the following: FI (hexane solubles): residual phosphate ester FII (hexane Insoluble-acetone soluble-chloroform soluble) GPC #1: MW > 3000 - mixture of a polyglycol and a styrenated rubber. GPC #2: MV 3000 - 1550 - reaction product of the epoxy component (Admix 710) with the phosphate ester half acid. GPC 13: HW 1550 - 730 - similar to GPC #2. The -OH stretch absorbance about 1/3 of GPC #2. GPC #*: MW 730 - *70 - similar to GPC #3 V c KSV 0010705 a-<D-aj-ju Page Two DISCUSSION FII (Cont'd) GPC #S: MW 470 - 350 - similar to CPC #3 CPC #6: MW 350 - 270 - phosphate ester containing alcohol and possibly ether components. The very low carboxylate ester content indicates low concentration of the epoxy-phosphate ester reaction product. This fraction is either a physical mixture of the base phosphate esters with a low molecular weight polyglycot, or an interaction product of the phosphate ester half acid with the glycol. GPC #7: MW 270 - 145 - similar to GPC #6. The organo portion in this fraction is associated with phenyl or cresyl groups, whereas GPC #6 was associated with nonylphenyl or cumylphenyl groups. GPC #8: MW 145 * <50 - a metal organopyrophate containing either phenyl or cresyl groups. Fill (hexane insoluble, acetone soluble - chloroform Insoluble): A metal organopyrophosphate similar to GPC #8, differing in that the organo groups are nonylphenyl or cumylphenyl. FIV (hexane, acetone, chloroform and methanol insolubles): Inorganics that are high in phosphorus and iron. Probably a mixture of an iron phosphate and iron oxides. Extraction of the recovered GPC #1 fraction with acetone separated the styrenated rubber from the glycol. The IR spectrum of the glycol showed that it was Ucon's polyoxyalkylene glycol 75-H-350.000, a material foreign to Pydraul formulations. The IR spectrum of the isolated polyglycol ruled out the presence as the main component being Jeffox 0L-2700, the glycol used in Pydraul 29ELT, or Ucon Concentrate 700, a glycol used in other Pydraul formulations. GPC analysis using a column for high molecular weight separations showed the Republic Steel gel contained components with apparent molecular weights of 20,000 and 7900 (relative to polypropylene glycol calibration standards). New Pydraul 29&LT contains apparent MW components of 21,000 and 4300. New Pydraul 50E contains no high molecular entities. GPC analysis of knc*rn components confirmed the 20,000 MW peak Is a styrene-polyisobutylene copolymer and the 7900 MW peak is (icon's 75~H-350,000. Table I lists the observed high molecular weight components In the Republic Steel gel and in all the known materials. References: IR spectra 75-202 A to E, 75-213 to 219, 75-229 to 235, 75-249 to 258. ss Monsanto Industrial Chemicals Co, Applied Sciences St. Louts, Mo. 12/75 - B. Katlafsky, V. J. Lltschgl, M. W. Dietrich RSV 0010706 figure 1 CONCENTRATED GEL HEXANE S-75-SS-36 SOL. FI INSOL. ACETONE SOL INSOL. SOL. FI CHLOROFORM INSOL. Fill SOL. NONE METHANOL INSOL. FIV GPC FRACTIONATED RSV 0010707 S-75-SS-36 TABLE > CPC OF HIGH MOLECULAR WEIGKT COMPONENTS Sample Republic Steel Gel Apparent Molecular Weight 20.000 - 7900 New Pydraul 29ELT 21.000 - - 4300 New Pydraul 50E Jeffox 0L-2700 4000 Ucon 75-H-350.000 7900 Ucon Concentrate 700 11,600 Styrene-Polyisobutylene copolymer 19,500 RSV 0010706 J Spectroscopy S-75-SS-37 CHEMICAL I OK IZAT1OH OF ESTERS AND ALCOHOLS INTRODUCTION The reason for this study was to Identify a competitor's compressor fluid. SUMMARY Sample 1000632-1 seems to be 0 0 0CiaH27 OC1SH27 and sample 1000632*2 from our analysis is 0^ J) ,,C-C7Hi*- OCj 3H27 OC11H27. DISCUSSION The original analysis by NMR revealed the two products to be esters very closely related to ditsodecyl adipate. Due to the high boiling point of these products, GC/MS analysis was impractical. Therefore, the lower boiling methyl esters were formed by hydrolizing the fluids. With the aid of chemical ionization (Cl) mass spectrometry, we were able to obtain the identification of the fluids given In the summary. Cl mass spectrometry of the esters and alcohols worked well. Some of the Cl spectra of these fluids and C7, C alcohol standards are attached. Reference: GC/MS File #75-158 NMR File #16-1059 Analytical Chemistry, Vol. 47, No. 9, Aug. 1975, pg. 1708 Accounts of Chemical Research, Vol. 1, Aug 1967, pg. 48 ss Attachments(5) Monsanto Industrial Chemicals Co. Applied Sciences St. Louis, Mo. 10/75 - L. M. Chapman, G. V. Mappes, M. W. Dietrich RSV 0010709 S-75-SS-37 OWETHYL AZELATE OCHm FPU 21821 SPECTRUM MASS hBUND S3 2 cc 2 6 ST 5.1 ss 6 S9 2.2 60 3.8 61 . 6 toT .3 6 . 1 69 2.1 71 4.8 74 11.6 75 1 1 73 .2 81 6 83 2.3 84 . 6 85 4 4 87 1 6 88 . 2 89 2 93 3 9S .? 97 2 5 ieo 3 :e; 6 192 3 10.* 1 214 RET. TIME It 4 107 3 109 8 111 2 9 113 18 115 1 4 117 1 121 2 123 .7 124 3 125 3 4 127 14 135 137 139 140 141 143 149 151 152 155 156 157 158 163 165 167 169 171 6 6 S .1 .7 62 .2 39 18 .9 2 18 2 .1 .2 2 1 1.3 -- 183 185 186 187 199 203 215 217 212 231 245 246 257 27 100 0 11 2 12 2 11 3 ii 4 mvJ 54 .7 .2 3 5* +** .3 5- +#* >PAU$E ----------- - -- RSV 0010710 S-75-SS-37 DIMETHYL ADIPATE Ot#s o f o<LH3 PRN 21824 SPECTRUM 49 RET TIME 4 3 MASS abund 55 4 Sb 1 57 .6 59 4 60 5 173 175 J74- 4 /nw 65 69 . 2 71 2 "4 7 1 75 . 2 S3 .2 S5 4 S? 1 203 204 215 >PAUSE 4.3.4 2.5- 4* / 97 101 102 .5 -- .. 7 1 . 111 112 113 115 116 7.2 4 .4 23 1 129 6 143 144 145 i9e e 70 8 RSV 00107X1 S-75-SS-37 Cl 3 ALCOHOL CaH,,OM FPN 21822 SPECTRUM mass ss V7 58 59 66 61 69 71 72 T4 75 A8UND 16 9 84 3 54 94 22 9 16 17 6 106 e 73 69 3 25 81 2 1 S3 27 5 S5 94 1 86 6 4 87 2.7 83 .4 95 97 lee 181 18 34.5 53 32 169 111 113 114 115 24 28 9 38 2 66 54 Si RET TIME 5 6 123 125 127 129 10 16 3 13 5 67 139 140 143 144 2.3 14 58 6 11 153 157 14 26 7 165 167 169 170 171 133 185 16 22 65 8 3.5 7 87 189 199 00 >PAUSE 15 1 .6 RSV 0010712 I S-75-SS-37 C7 ALCOHOL z,h9oh FRN 21811 5PECTPUT1 259 RET TIHE 16 4 nss 4? *10 *BUN& SI 70 14 1 71 13 3 73 2 9 S3 23 2 85 5 2 37 39 101 115 10O 6 94 2 27 8.8 (m-t) >PftUSE RSV 001.071.3 C, ALCOHOL c,h,,oh \ rRN 21811 SPECTRUT1 309 RET TIME 18.7 MASS xio A8UND 49 3 98 8 7 57 56 5 59 3 0 67 .9 71 100 0 73 8 31 8 25 71 1 26 4 8 57 5 7 99 7 111 125 143 14 73 3.9 6n-i) >PAUSE RSV 0010714 Spectroscopy S-75-SS-38 DETERMINATION OF TRICHLOROETHYLENE (TCE) IN AIR AT ST. PETERS INTRODUCTION Air at St. Peters In the De-Composer Units was sampled for TCE. The results obtained indicate worker exposure levels. SUMMARY , TCE was detected in levels of 0.04 to 3.1 ppm. Inadvertently, the first five samples in the table sat for two months before sampling, which may have affected the accuracy of the analytical data. EXPERIMENTAL A Chromosorb 105 column was used for collection. A 2 m Tenax column programmed from 0-200C at l6/mln was used for analyses. Multiple Ion detection at masses 95, 130, 132 and 134 was employed for samples I, 2,and 7. Total ion detection with two selected Ions (95 and 130) for san*>1es 3, 4, and 5 provided the means of identification and quantitation as compared to a known standard. Calculations Volume of Air Pump Flow Rate ,, Sampling Time Y lf-s Sampled (Liters) (ml/min.) (min.) Weight Sample (ug) Concentration Sample (ug/L) Area Sample Peak ,, Cone. Std. (yiq/uL) X Vol. Injected (uL) (counts) "Area of Standard (counts) Weight Sample (ug)/Vo1ume of Air Sampled (Liters) Concentration Sample (ppm) pg/L (sample) x MW. (samplej For Sampling #1 Spin Mount Polishing Volume of Air Sampled - 53 X 1 X 60 X 10~3 - 3-18 L Weight Sample (wg) 9177x1 x 1107 X 2.2 217761 X 209657 9C , Concentration TCE 25.3 fi A (ug/L) jrre- - 8- M/L (pp) . B.O X -J35-- 1.5 ppm References: GC/MS File /75~172 ss Monsanto Industrial Chemicals Co. Applied Sciences St. Louis, Ho. 10/75 - L. M. Chapman, M. W. Dietrich RSV 0010715 S-75-SS-38 TABLE SAMPLE #1 Polishing-Spin Mount 8-28-75 tl Polishing-Spin Mount 9-4-75 #3 Poly De-Composer 9-4-75 #4 Poly De-Composer (east) 9-11-75 #5 West Poly De-Composer- clean up 9-15-75 #7 Worn by John Wagner 9-18-75 TCE (ppm) 1*5 2.1 1.2 0.2 0.04 31 Pump flow - 53 mls/min Sample volume % 3.18 liters Sample time * 1 hour RSV 0010716 Spectroscopy Special Study S-75-SS-39 DETERM 1 HAT I ON OF CONTAMINANT IN 0X0 ALCOHOL INTRODUCTION The reason for this analysis was to check possible contamination In oxo alcohol sent to a customer in Taiwan. SUMMARY We found 0.031 dioctylphthalate (DOP) and 0.7% Ci0 hydrocarbon which were not present in a control lot of oxo alcohol. EXPERIMENTAL Several different GC columns were investigated in order to separate the 0.7 unknown component from the major alcohols present. A 3 m 0V 17 glass GC column gave the best separation. From the mass spectra, the molecular weight of this component was 142. MS fragmentation indicated it was either a Cjo hydrocarbon, a C, ketone or a C aldehyde. A reaction with nitrophenylhydrazine was carried out to determine If this component was a ketone or aldehyde. No derivative formed under conditions in which a C$ ketone gave a derivative indicating this impurity Is a Cj0 hydrocarbon. Programming used In the analyses was 50*200 8/min. References: GC/HS File #75"168 NMR File #16-1078 "The Systematic Identification of Organic Compounds" by Shiner, Fusan, Curtin, 4th Ed., pg. 219. ss Monsanto industrial Chemicals Co. Applied Sciences St. Louis, Mo. 10/75 - L. M. Chapman, M. W. Dietrich RSV 00107X7 Spectroscopy Special Study S-75-SS-40 SYNTHETIC FATTY ACID CONTINUOUS PILOT PLANT RADIOTRACER CATALYST STUDY WITH IRIDIUM-192 -- FEASIBILITY INVESTIGATIONS INTRODUCTION Ouring 197^-75, the Detergent and Phosphate Division expended considerable research effort toward the development of a continuous synthetic fatty acid plant process. A key factor to the success of the project was satisfactory demonstrat ion of good performance and manageability of the iridium catalyst system in a continuous plant. The catalyst chemistry is complex and its behavior in the process has been, on occasion, baffling. Iridium analytical chemistry has also proved quite difficult contributing to the overall problem of quantifying catalyst characteristics. The possibility of making a better evaluation of the catalyst performance using the gaovna emitting radiolabeled iridium-192 was recognized and discussed in early 1979- The main advantages foreseen were the possibilities of: 1. A simpler more reliable analytical method for determination of catalyst concentration by continuous, insitu external gamma radioactivity monitoring; 2. Much greater convenience in determining whether observed loss of catalyst activity was due to loss of catalyst per se or to other phenomena (poisoning, etc.); 3. The elucidation (when, where, how much, etc.) of the apparent catalyst losses in the process. SUMMARY Experimental design estimates were made that indicated useful catalyst analytical sensitivities could be probably obtained in the pilot plant using regulatory exempt (10 microcuries) level of radiolabeled iridium-192 (Table IV). Five millicuries of iridium-192 were obtained from New England Nuclear in April and a series of exploratory evaluations were undertaken to assess technical and safety problems involved In the proposed tracer study. Highlights of the feasibility study include: Gamma spectral properties of iridium-192 were checked (photopeak energies and Intensities). Analytical sensitivities were established for continuous gamma monitoring at two pilot plant stages at several iridium concentra tions and In different flow cell designs. (Tables I, V) Analytical sensitivities were determined for intermittent catalyst monitoring of grab samples for radioaetivlty using either the gamma or beta radioactivity of Iridium-192 (Tables li, Vl). A suitable explosion proofing cover for the electrical leads of the continuous ganma detector was developed (Figures 2, 3). Shielding requirement for minimizing radiation background for continuous gamma detectors was explored and two prototype shield designs were fabricated (Figures 2,3)* , c- / ftsv 001071a S-75-SS-^O Page Two SUMMARY (Cont'd) Measures were explored for protecting the ganvna detector from heatup from hot flow lines during continuous monitoring (Figures 2. 3). A'technique was devised for volume calibration of short straight tubular flow cells. A spiral flow cell for enhanced sensitivity at exempt Iridium-192 concentrations was designed, fabricated and evaluated for sensitivity enhancement at simulated reactor concentration of catalyst (Figure 3* Table V). Assessment of gamma radiation dosages to personnel from pilot-plant iridium-192 concentrations ranging from 10*100 microcuries were made (Table Ml). Other radiochemical safety measures for contamination protection of personnel and facility were devised. During the sunvner and fall of 1975, formidible process problems continued to plague pilot plant studies to the extent that no radiotracer experimentation was undertaken. At the end of the year a decision was made to switch from continuous to batch operations. It has not yet been determined whether radioisotope applications will be of continued interest under this modified concept. This report of the experimental design application problems and results obtained in the feasibility study under simulated conditions is believed to have considerable value of a general nature in the application of radioisotopes to pilot plant scale process studies especially in the high pressure laboratory. CONCLUSIONS* V) 1. Two stages of the pilot plant appeared to be adaptable to continuous gamma monitoring - the reactor and the catalyst return line (Figure 1). 2. The reactor stage requires either greater than exempt quantities of iridium192 and/or use of a larger volume flow cell for insitu continuous monitoring. Limitation of tracer to an exempt quantity (10 microcuries) and use of a short section of 1/A" reactor outlet tubing as flow cell does not permit adequate sensitivity (Table V). 3. The reactor stage can be intermittently monitored insitu at exempt iridium-192 concentrations with sensitivities of \% iridium by use of a larger volume flow cell and scaler counting for at least 10 minutes (Table V) or by taking grab samples of 1-2 ml and counting for 90-100 minutes in a 3" X 3" Nal gairma well detector (Table VI). k. The catalyst return line with MO,000 ppm catalyst appears feasible for insitu continuous monitoring but requires either higher Iridium tracer concentration or a larger volume flow cell (Tables l V). The monitor region proposed is very crowded and adequate detector shielding against background wfM be a problem requiring possible redesign. 5. The catalyst return line, as with the reactor stage, can be intermittently monitored insitu by scaler counting or by grab samp I ing/gamma well counting (Tables V, VI). RSV 00107X9 CONCLUSIONS (Cont *d) S-75-SS-40 Page Three 6. A larger volume flow cell that appears practical in concept for the reactor stage and possibly for the catalyst return line was obtained by construction of a stainless steel tubing spiral that encircles the gamma detector (Figure 3, Table V). 7. Iridium-192 counting efficiency is significantly improved in grab sampling over insitu continuous monitoring (Tables 1, II, V, VI). Gamma counting in the larger NaI well detector is believed more useful than liquid scintillation because of the nearly constant count efficiency as a function of sample volume and its greater freedom from Interferences by sample composition, color, etc. (Tables II, VI). 8. Garrma radiation hazard to pilot plant research workers was estimated to be well below safe recommended levels up to 100 microcuries of iridium-192 (Table III). DETAILS The considerable quantity of details is reported only in outline form with page references to the project research notebook. Topic Synthetic Fatty Acid Continuous Pilot Plant Schematics and Spedfications Project Justification/Radiochemical Safety Evaluation/Experimental Oesign Iridium-192 Radioisotope Shipment Data Preparation of Experimental Solutions of Iridium 192 Notebook Page HIC 309101A - 3091026 309156 309I02B - 309107B 309181-86 309108 309112, 309131, 309145, 309152 309120 309135 309147 Determination of lridigm-192 gamma spectrum 309115 - 309H9B 309131, 309165 3091618, 309166B-67 Feasibility studies on insitu continuous gamma monitoring at exempt Iridium-192 levels -simulated catalyst return line of SFA Feasibility studies on alternative counting equipment for analysis of 11-- 192 radioactivity at exempt level in simulated SFA pilot plant grab samples 309121-2, 309125 309126, 309128 309131-2, 309134 309187B-94A 309123-5. 309127 309129-34 309161-63 309194B-96B RSV 0010720 DETAILS (Cont'd) S-75-SS-40 Page Four Topi c feasibility studies on insitu continuous gamma monicoring of Iridium-192 at higher than exempt quant i t ics Notebook Paqe MIC 309135-6, 309141 309I96C-97A Calibration of Victorine 440 and Eberline PRH 4-3 portable radiation detectors for Iridium-192 dosimetry measurement 309137-40 Investigation of gamma radiation hazard to personnel from Iridium-192 at levels up to 10 times exempt 309137-40 309197A-98A Design of shield setup for SFA pilot plant catalyst return line 309144 Determination of lead half thickness values for iridium-192 309149-51B Determination of "actual" monitor volume of short 3/8" stainless steel tubular flow cells 309147-8 Safety assessment of proposed tracer study by Corporate Safety Department 309169-75 Feasibility studies on simulated continuous monitoring of SFA pilot plant reactor stage using exempt Iridium-192 levels as maximum 309154-5 309157-59 309164-68 3091968-2000 Design and evaluation of spiral flow cell and lead shielding for continuous monitoring of SFA pilot plant reactor stage 309152-3 309166 Project Report - Comprehensive Experimental DetaiIs 30918IA-200D ACKNOWLEDGMENTS Assistance of Applied Sciences Instrumentation Group and Research Center Shop for fabrication of lead shielding, flax cells, gamma detector explosion proof adaptor and other miscellaneous hardware is pridefuily acknowledged. References: Research Notebook Pages 309101A-309200D 5S Attachments(9) Monsanto Industrial Chemicals Co. Applied Sciences St. Louis, Mo. 12/75 - Charles Eggert, 0. B. Hines, M. V. Dietrich RSV 0010721 TABLE I. SIMULATED GAMMA MONITORING OF SFA CONTINUOUS PILOT PLANT CATALYST RETURN LINE 2.5" X 3/8" 00 TUBULAR FLOW CELL AND SOLID 2" X 2" NAI DETECTOR Flow Cel 1-Detector SeparatIon Distance (CM) Flow Cel 1 Signal- (Net CPM) BackGround (CPM) lr-192 Count. Eff. (CPM/DPM) Satnpl e-toBackground Ratio Sens 111vl ty (As t of Iridium Concentration) Rate - Scalar Counting Meter (Minutes) Recording 1 10 60 (10 sec Infea) A - 9-24 pc! 1r-192/4 liters (exempt concentration) 0 1.4 2.9 0<2> 1873 1276 846 1331 394 428 428 428 428 19 0.132 0.090 0.060 0.094 0.028 4.38 2.98 1.98 3.1 21.1 13.7 17.8 23.7 17.0 26.5 5-6 1.8 0.7 7.3 2.3 0.9 9.7 3.1 1.3 7.0 2.2 0.9 10.7 3.4 1.4 B - 48 pci 1r-192/4 liters 0 9602 437 0.132 21.9 1.4 6127 437 0.084 14.0 2.9 4319 437 0.059 9-9 5.2 2.1 0.7 0.3 6.7 2.6 0.9 0.4 8.1 3.3 l.l 0.4 O'T -S S -S X -S ftSV 00X 0722 C - 101 pci lr-192/4 1 iters 0 19055 547 0.125 34.8 1.4 11537 547 0.076 21.1 2.9 88o4 547 0.058 16.1 3.6 4.8 5.5 1.5 1.9 2.3 0.5 0.6 0.7 -- -- -- ^^Flow cell was wrapped In asbestos Insulation at thickness slikllar to that used In SFA Pilot Plant. (2) 'A narrow window count of the major lr-192 photopeak was "wde for comparison. TABLE II. ANALYTICAL SENSITIVITY PR0VI0ED BY VARIOUS COUNT OPTIONS ON GRAB SAMPLES AT THE EXEMPT LEVEL OF IRIOIUM-192 Count Technique Sample Size (ml) RIDL Single Channel Analyzer, Manuel Semple Changer, 2" X 2" Well NAI Detector In 2" Lead Shield 0.5 1.0 2.0 5.0 10.0 Sample Net CPM Background CPM 636 1366 2855 7318 IW? 137 137 137 137 137 Count Efficiency (CPM/0PM) 0.269 0.266 0.277 0.286 0.286 Sample-toBackground Ratio 6.6 10. 21 . 53. 106. Sensitivity (As t of Iridium concentration) Count Time. Min 1 10 9.5 3-0 1.2*'* 6.0 1.9 0.8*1* 3.9 1.2 0.5*'* 2.6 0.8 0.3(,J 1.7 0.5 0.2 ^3 Packard Liquid Sclnt11 let Ion Spectrometer Model 336$, Automatic Sample Changer, Low Potassium Glass Count Vial, Packard Instagel Count Cocktail 0.5 1.0 5.0 10.0 1165 2381 11536 21303 21 0.667 56. 21 0.666 112. 21 0.651 563. 21 0.615 1003. 6.0 1.9 0.6(2* 6.1 1.3 oV2* 1.9 0.6 0.2(3J 1.6 0.6 0.2^ 06-SS-SZ-S RSV 0 0 1 0 7 2 3 ^60 minute counting ^100 minute counting ^Counting ^78 min (900,000 count limit) ^Counting ^62 min (900,000 count limit) S-75-SS-40 TABLE III. GAMMA RADIATION DOSAGES FROM A SIMULATED SFA PILOT PLANT STAGE CONTAINING HIGHER THAN EXEMPT LEVELS OF IRIDIUM*192 lr-192 Dosage, 4 Liter Surface Container (mr/hr) Cont ined lr-!9< 10 uci 48 uci 101 uci Allowed Garnna Dosage, NRC Regulations Title 10, Part 20, Par 20.101 (calculated mr/hr) Whole Body Head and Trunk Active Blood Forming Organs Lens of Eye Gonads Hands and Forearms Skin of Whole Body Less than 0. 1 0.25 MJ.45 2.4 36.1 14.4 RSV 0010724 S-75-SS-40 TABLE IV. SYNTHETIC TATTY AC 10 PILOT PLANT SPECIFICATIONS PERTINENT TO CATALYST TRACER STUDY Process Stage Stage Fluid Capacity Ml Grams Iridium Catalyst Distribution Grams Ppm 1ridium-192 Distribution (10 pci total) pci dpm/ml Est. Transit Time (Hours) Reactor 4285 3000 6.00 ^2000 1.42 736 *1 .25 Distil 1 at ton/ Catalyst Recov. 2344 1875 3.75 ^2000 0.89 843 *0.75 Catalyst Return System Tota1s 3785 3243 32.43 *10000 7.69 4510 *7.33 10414 42.18 -- 10.00 -- 9-33 RSV 0010725 TABLE V . SIMULATED GAMMA MONITORING(WITH VARIOUS FLOW CELL OPTIONS)OF SFA CONTINUOUS PILOT PLANT REACTOR AND CATALYST RETURN LIN E AT EQUILIBRATION OF 10 MICROCURIES OF IR -1 9 2 P ilo t P la n t Stage Reactor Type Flow DPM lr - 1 9 2 F low C e ll lr-1 9 2 C ell In Flow S ig nal 0 ) Back- C ount. S e n s itiv ity S am ple-to- (As % o f Irid ib m C o n c e n tra tio n ) F lo w C ell V o lu m e (m l) C ell (O P H /m l) (N e t CPM) Ground (CPU) E ff. (CPM/DPM) Background Rat lo R ateM eter S calar Count v0O --xC 0e *" X Record 1 10 Sec In te g H ln CsSoOO O IA " 00/ss N Ok f*-k -- O CD CD fb ^ . - ia ~ IV --Uk -- nk kA O -- rm- -- i*k y-- -- f*k NN fI*A*> 0N0 OOOO ^ rk .. N-- Ok o\ e.--ao- ceegoo a-ao- ---i*rk CM -- C--O n A VO CfcAokQ--rO- Ok. IA. tb C4 3 /8 " OD/SS mn <T k/> kA IA Uk 0j^--n O kA N 00 -- C a ta lyst R e tu rn L in e 1/4" S p ira l SS 3 /8 " OD/SS PNA o> NOkNfA * -- b eV 2Q aM (A t-- IA *0 t> bU0 --e "Mvo 41 b in 4-< O -O 4) a -- avu S-75-SS-40 4C) o> c by <e wi *3 z +* 19 c if n i" 4> **- x b3 o 1 V) 31 n vig --c *D E --y -- k_ 19 O O *> (A V* c > 10 .0 u jz 4) -- "O ** -- 4) O 4U) f3t 3b S M <A i55 **- y kb J IA -3 S S *i -o c-- <B b 4) b C -- -<On 3nZ* 3 y m gtS ~ge SlJ *-- a. c 4> C (A< < oke3n- RSV 0010726 TABLE VI. ANALYTICAL CRAB SAMPLE SENSITIVITY PROVIDED BY PACKARD AUTO GAMMA (TANDEM MODEL 3365)^ Pilot Plant Staqe Reactor Catalyst Return Line Sample Size (ml) 1 2 3 5 1 2 3 5 Samp1e Net CPM 372 752 1083 1826 2364 4677 6889 11107 BackGround CPM 100 180 180 180 180 180 180 180 Count Efficiency (cpm/dpm) 0.518 0.528 0.503 0.509 0.517 0.511 0.502 0.486 Samp 1 e-toBackground Ratio 2.1 4.2 6.0 10.1 13.1 26.0 38.3 61.7 Sensitivity (A$ t of Iridium Concentration) Count Time. Min. 1 0 $6 100 14.6 4.6 2.1 1.5 8.9 2.8 1.3 0.9 7.0 2.2 0.9 0.7 5.2 1.6 0-7 0.5 4.4 1.4 0.6 3.0 1.0 -- 2.5 0.8 -- --- 1-9 0.6 -- --- 0Y SS-5^-S" RSV 0 0 1 0 7 2 7 0) Catalyst In simulated reactor and catalyst return samples at equilibrium distribution of 10 pCI lr-192. I S-75-SS-JiO u "33 --T3 oI- <o I f I RSV 0010726 I .FIGURE SYNTHETIC FATTY ACID CONTINUOUS PILOT PLANT SCHEMATIC (PR 702*4-K2) 0 OaU 1 cc . o <O_> 4- O lef. o < S-75-SS-^O FIGURE 2. LEAD SHIELDED GAMHA DETECTOR PROPOSED FOR CONTINUOUS MONITORING OF RADIOACTIVE IRIDIUM CATALYST RETURN LINE RSV 0010729 FIGURE 3. SHIELD SCHEMATIC FOR SPIRAL FLOW CELL CONTINUOUS MONITORING OF SFA CONTINUOUS PILOT PLANT REACTOR (Scale, I dlv - I11) ini v((AAin o Inner shield machined to hold the Detector at reproducible geometry RSV 0010730 SFA Reactor Effluent'y- Colls of Spiral 1A 00 SS Flow Cell 3" ID coll 3 1/2" 0D coll wrapped with Insulation tape to reduce transfer to Detector Set collar to effect reproducible geometry H.V. Lead ^-Pre Amp Output C. Schematic of Shield with Detector In monitoring position of Spiral Flow Cel I Can assembly for N? Purge for Explosion Profrlng Detector High Voltage Connections Note 2 essentially Identical shield assemblles required: (1) Houses Spiral Flow Cel 1 from SFA Reactor (2) Side-by-side of first shield to measure an lr-192 std. In an Identical spiral cell, measure BKE and checking of electronics lab of detector Spectroscopy Special Study S-75-SS-4I SYNTHESIS, ANALYTICAL CHARACTERIZATION AND PREPARATION OF FPA TEST COATINGS OF MODAFLOW1*^ INTRODUCTION Monsanto Modaflow is an ethyl acrylate-2 ethylhexyl acrylate copolymer of MO,000 Mol. Wt. that is added to various resin systems such as acrylic and epoxy to produce better quality coatings. One potential application is the inside coating of metal containers targeted for the soft drink and alcoholic beverage industry. Acceptability for this application normally requires either demonstration of low extractabiUty of product into the appropriate solvent system(s) using standard FDA extraction procedure or a feeding study in case of excessive extractabi1ity. Previous extractabi1ity testing of coatings containing Modaflow gave questionable results because of inter ference in the infrared spectroscopic measurement of Modaflow. This work was carried out using resins containing Carbon-|l labeled Modaflow to provide the necessary improvement in sensitivity and specificity. SUMMARY Approximately 190 grams of low specific activity Modaflowl4C was prepared from ethyl acrylate11^ raw material. This material was analyzed by a series of tests (Table I) and shown to have physical properties typical of plant material and to have adequate radioactivity concentration to provide the needed analytical sensitivity. The labeled Modaflow was incorporated into acrylic and epoxy resin formulations and used to prepare radioactive coatings onto special release paper. Solution/slurry coating techniques were used for radiochemical safety reasons instead of the normal dry powder electro static spray method. FDA extractions on the coated sheets were subsequently carried out as described in Special Study AC-75-SS-13 (Reference 1). EXPERIMENTAL Design of Experiment Calculations showed that a labeled product with a relatively low specific activity (3~4 microcuries/gram) provided Modaflow detectability below 1 ppm with normal sample sizes, counting efficiencies and sample analysis times. This specific activity level appeared readily obtainable with M millicurie of radioactive raw material. Raw Material/Solvents Modaflow is prepared by reacting ethyl acrylate and ethylhexyl acrylate (30/70 weight ratio) in a kerosene solvent. The extent of polymerization is controlled by sequential addition of benzoyl peroxide catalyst. Progress is followed by refractive index measurement. Modaflow Is isolated after stripping off kerosene solvent by vacuum distillation. Ethyl acrylate^C was purchased from American Radiochemical Corporation, Sanford, Florida. Due to its extreme susceptabi1ity to polymerization the ethyl acrylate1%C was synthesized {(mediately before our use. The supplier prepared the material, stabilized it with 1000 ppm hydroquinone (the standard agent and level used in plant raw material) and shipped it to Monsanto frozen In dry Ice for next-day use. RSV 0010731 S-75-SS-41 Page Two EXPERIMENTAL Raw Haterial/Solvents (Cont'd) All the non-labeled raw materials and Penneco kerosene solvent were current Nitro, W. Va. plant stocks. Synthesis After the demonstration practice run the solvent stripping procedure following the reaction was modified by (1) the addition of a short, heated column replacing the gooseneck take-over joint and (2) use of a dry Ice bath on the receiver. The labeled synthesis produced 187 g product corresponding to a yield of $&% relative to ethyl acrylate. Of this 187 grams, 83fc was recovered as neat ModaflowlJ*C and 13* recovered as a solution In kerosene. Analytical Characterization The labeled Modaflow was characterized by refractive index, viscosity, molecular weight by GPC and specific activity determination. Refractive Index Two refractive index criteria were met: 1. Modaflow polymerization range was controlled by refractive Index (Rl) measurements on the crude reaction mass. The synthesis procedure allowed a Rl range of 1.A460-1.AA80 at 25C. These values were reported to be the uncorrected range normally found relative to the Nitro Plant Bausch and Lomb refractometer. We obtained a comparable Instrument and constant temperature bath on site and calibrated It over the desired Rl range relative to Cargille Rl standards. The corrected refractive index of the labeled crude obtained at reaction endpoint was 1.AA8 +0.0002 at 25C. 2. The second refractive index specification was I.L130-1.k190 at 25C for a kOfc solution of Hodaflowl4*C in 2,2,4-trimethy1 pentane (isoctane). The corrected value obtained on labeled Modafiow was 1.416 +0.0002. Viscosity The Modaflow viscosity range in Saybolt Furol Seconds (SFS) is specified to be 650-1650 at 210F. The vtscosity of labeled Modaflow and a Nitro plant produetlorv lot were determined by Ostwald Kinematic Method at 100 and I25*C and calculated as SFS at n2IOF according to ASTM Method D-2161-63T. The SFS values found were 965 and 885 respectively for the two products, placing them well within specifications. Molecular Weight Measurement by CPC Gel permeation chromatography was used to determine the peak molecular weight of Modaflow. The instrument used was a Waters Associates ALC-100 equipped with pStyragel columns (Waters Associates) and an R-li00 differential refractometer (Waters Associates). The battery of columns used consisted of 102A, 5 X I02A, I03A* , 10"A, 10SA and 10*A. UV grade tetrahydrofuran (THF) was RSV 0010732 S-75-SS-41 Page Three EXPERIMENTAL Molecular Weight Measurement by GPC (Cont'd) chosen as the eluting solvent at a flow rate of 1 ml per minute. The sample concentratIon was approximately 2 parts THF and I part Modaflow. A 20 ul portion of this sample was then chromatographed. The peak molecular weight versus polypropylene glycol standards was 9600. Specific Activity Determination The experimental design provided for a minimum specific activity of 3*6 microcuries per gram based on the use of one mllllcurte raw material to produce a 278 gram batch. Actual synthesis scale proved to be 195 9 (theory) and American's radioisotope shipment specified 1.25 mtllicuries. A specific activity, therefore, of ^.7 microcuries per gram was expected. Specific activity determination was carried out on a xylene stock solution of labeled Modaflow diluted 100 to 1 with cold Modaflow to reduce glass surface adsorptive effects. Radioactivity was measured by liquid scintil lation counting using internal standardization. An experimental value of 4.53 microcuries per gram was obtained. The discrepancy between theory and experimental specific activities has been attributed to the delivery of less than the specified amount of labeled raw material. Preparation of Hodaf iow^C/Rcs in Coatings for FDA Extraction Studies The conventional electrostatic spraying method used to produce coatings containing Modaflow presented a substantial problem for radiochemical safety. This conventional method consists of several steps likely to produce airborne radioactive powders. An alternative procedure to produce coatings using safer solution/slurry techniques was developed by the Plasticizer application group (Reference 3). Twenty-four sheets of acrylic and epoxy type coatings were prepared on release paper. In spite of considerable care, occasional small "holes" in the coatings were observed where film had not covered the paper. These holes were patched by addition of a drop of slurry to the area before curing. References: 1. Analytical Chemistry Group Special Study AC-75"SS-13, "FDA Extractions of Resin Coatings Containing C-14 Radiolabeled Modaflow."2 3 4 2. R. G. Raley's memo of 7-22-75 to D. Hines and R. Radue, "Status of C^-labelad Modaflow for FDA Extractions." 3. S. F. Joyce's memo of 9-2-75 to P. R. Graham, "ModafIcw-FDA Panels." 4. Research Notebook pages MIC 1,001,101-1,001,173. ss Attachment Monsanto Industrial Chemicals Co. Applled Sciences St. Louis, Mo. 12/75 -0. 8. Hines, A. R. Atkinson, J. W. Htrzy, W. J. Lltschgl, H. W. Luebke, H. Yepez, $. Joyce, M. Y. Dietrich RSV 0010733 S-75-SS-41 TABLE I SPECIFICATION VERSUS MEASURED PROPERTIES OF PLANT AND RADIOACTIVE MODAFLOW Test Specification Lot 817-78, QC-3*3 NB-08-007 Hodaf low1 **C Refractive Index @25C of Reaction Hass Crude 1.4460 - 1.4880 1.486 + 0.0002 Refractive Index g25C of 40% Hodaflow in 2,2,4-trimethyl pentane 1.4130 - 1.4190 1.4170 (Plant Analysis) 1.416 + 0.0002 Viscosity, SFS at 210F 650 - 1650 885 964 Peak Holecular Weight by GPC ----- 9600 9600 Specific Activity mic rocu ries/gram 4.53 RSV 0010734 Spectroscopy S-75-SS-42 DETERMINATION OF AROCLOR 1016 IN AIR AT ELECTRIC UTILITIES COMPANY, LASALLE, ILLINOIS INTRODUCTION The objective of this analysis was to determine levels of polychloro biphenyls (PCBs) in the plant air of Electric Utilities Company. SUMMARY The results are attached. The values detected ranged from 0.2 to 2.3 yg/1. EXPERIMENTAL Tenax was used for collection of the PCBs and a glass 0V 17 was used for the analyses. Identification and quantitation was made with known standards. The calculations are shown below. Calculations Volume of Air _ Pump Plow Rate Y Sampling Time y .--3 Sampled (Liters) (ml/min.) (min.) Weight Sample (pg) Concentration Sample (ug/L) _ Area Sample Peak ,, Cone. Std. (ug/ L) X Vol Injected (pL) (counts) Area of Standard (counts) Weight Sample (ug/L)/Volume of Air Sampled (Liters) For Sampling #1 Plugging Area Volume of Air - 88 X 115 min. X 10"3 - 10.12 liters Sampled (Liters) Weight Sample (ug) - 3058*f X 2.*7 X 3.7 - 17.02 ug TPTT3 Concentration (ug/L) - T37TT " K68 pg/1 % 1,7 119/1 References GC/MS File #75-202 ss Monsanto Industrial Chemicals Co. Applied Sciences St. Louis, Missouri 11/75 - L. M. Chapman, M. W. Dietrich RSV 0010735 S-75-SS-42 Location Plugging Area 0\ TABLE Plugging Area 02 Press Department #3 Assembly Department 0k Impregnation Department #5 Winding Room #6 Plant Manager's Office 01 Standard 18 Aroclor 1016 1.7 Mg/1 2.3 ug/1 0.4 Mg/1 0.5 Mg/1 0.7 Mg/1 0.2 pg/1 ND < 0.1 NO < 0.1 Pump flow 86 ml/min. Samp!ing time 1-5 hrs. Sample volume 5-30 liters RSV 00L0736 Spectroscopy S-75-SS-43 DETERMINATION OF THE LEVELS OF TRIETHYLAMINE AND BUTANOL IN AIR AT THE DELAWARE RIVER PLANT INTRODUCTION This Investigation was undertaken to determine worker exposure levels to triethyI amine (TEA) and butanol. Samples were taken in and around the Santlclzer 160 manufacturing structure. SUMMARY Results are attached. Triethylamine was detected in levels ranging from 0.4 to 44.8 ppm. The levels of butanol detected were 0.1 to 2.8 ppm. Some values of the triethylamine analyses may be high due to interference by other components. EXPERIMENTAL The analytical column used was a 2 meter glass Tenax and collection columns were packed with Chromosorb 103. In identifying and quantitating the samples* knowns were used. Ions 74, 59* 86 and 101 were scanned with the total ion scan in order to get better resolution and identification of butanol and TEA. Calculations Volume of Air m Pump Flow Rate v Sampling Time - .Q-j Sampled (Liters) (ml/min.) (min.) Weight Sample (ug) Area Sample Peak Cone. Std. (pg/uL) X Vol. Injected (uL) (counts) Area of Standard (counts) Concentration Sample (pg/L) Weight Sample (pg/L)/Volume of Air Sampled (Liters) For Sampling 75*1 Triethylamino Volume of Air . 36.8 X 11 X 10~s - 0.4048 liters Sampled (Liters) Weight Sample (Ug) 4226202 X 6.76 X 3.2 -l 1220429 'W9 Concentration (yg/L) 74.9 _ -0l5r ,8S-",S/I Concentration (ppm) . ]g , _ w.g 101 References: &C/MS File #75~200 ss Monsanto Industrial Chemicals Co. Applied Sciences St. Louis, Missouri 11/75 - L. M. Chapman, M. W. Dietrich > tN c RSV 0010737 S-75-SS-43 SAMPLE 75-11 75-10 75-4 75-5 75-1 75-12 75-3 75-8 75-7 75-6 TABLE BUTANOL (ppm) 2.8 TRIETHYLAMINE (pi 0.4 0.3 none detected 0.5 0.5 0.9 0.7 2.5 44.8 1.2 4.0 0.8 2.6 1.8 1.2 0.1 1-5 lost in analysis These values may be high due to other component interference. Pump used -- SKC 222-451 Volume sampled --> 0.5*2 liters Flow rate --> 28-37 ml/mtn Sampling time ---> 10-80 minutes RSV 0010738 Spectroscopy S-75-SS-45 DETERMINATION OF MALEIC ANHYDRIDE AND STYRENE IN AIR AT EVERETT, MASSACHUSETTS INTRODUCTION This study was undertaken to measure worker exposure tevels to maleic anhydride and styrene in air. SUMMARY Two samples contained 0.2 ppm maleic anhydride and 0.1 ppm styrene. One sample overloaded the system and is probably well over the TLV for both materials. Further details are given In the table. EXPERIMENTAL GC separation was made on a S-409 analytical column with identification by GC/MS. Besides scanning the total tons, ions 26, 54, 104 and 103 were also monitored selectively to verify the presence of these components. Calculations Volume of Air m Pump Flow Rate ^ Sampling Time m"* Sampled (Liters) (ml/mln.) (min,) 0 Weight Sample (yg) * Area Sample Peak ,, Cone. Std. (yg/uL) X Vol. Injected (uL) (counts) Area of Standard (counts) Concentration Sample (yg/L) * Weight Sample (yg/l)/Vo1ume of Air Sampled (Liters) Concentration Sample yg/L (sample) X (ppm) 24.45 --(sample) For Sampling Maleic Anhydride 75*60 Volume of Air Sampled Weight Sample (vg) Concentration (yg/L) * 46 ml/mln. X 110 mln.X 10~* * 5.06 - 1.327.660 X 3 - 3.95 Concentration - 0.78 X (ppm) - 0.195 % 0.2 ppm ss References: GC/MS file #75*221 Monsanto Industrial Chemicals Co. Applied Sciences St. Louis, Mo. 12/75 : L. M. Chapman, M. W. Dietrich RSV 0010739 Sample 75-60 North side of #5 Press 75-31 Bag filling Operation * 75-35 Between #5 and #6 Press 75-25 South side #6 Press S-75-SS-45 TABLE Maleic Anhydride (ppm) 0.2 Styrene (ppm) 0.1 0.2 0.1 >10 >20 lost in analyses * These values are estimates because this sample overloaded the system. / / RSV 0010740 Spectroscopy Special Study S-75-S5-47 SYNTHESIS, CHARACTER 12AT I ON AND PURIFICATION OF S-334FHl<tC INTRODUCTION Interest has continued within Monsanto for the development of a polymeric polyester plasticizer to replace DOP in the blood storage bag industry. Continued use of OOP has been questioned by certain medical research workers for several years because of its known extractabi1ity into blood during storage and Its suspected adverse effects upon transfusion recipients. Monsanto's initial efforts produced Santicizer 334F, a polymer of about 2000 molecular weight, the reaction product of adipic acid and 1,3-butylene glycol. Human blood extractab11 Ity of the S-334F was determined in 1972-3 by Monsanto research workers using a carbon-14 labeled form of the product synthesized within Monsanto for this work (References 1,2). The Monsanto study showed that the extractabi1ity reduction differential of S-334F over DOP was not as great as had been anticipated. Research continued toward S-334F modificaton to further reduce extractabi11ty. By late 1973, S-334FM had been produced by acetylation of the S-334F hydroxyl end groups. The modified product exhibited significantly reduced water extractabi1ity compared to S-33^F, One of Monsanto's customers, Baxter Travenol Laboratories, requested a radiotsotopical1y labeled form of the modified product for research purposes. This request initiated this project for synthesis and analytical characterization of S-33AFM1`*C (Reference 3). SUMMARY Monsanto agreed to provide Baxter Travenol Laboratories (BTL) with S-SS^FM^C in which the adipic acid part of the molecule was labeled. S-33^FMl,*C was prepared by acetylating the residual stock of S-334F 1 **C. S-334FM1"C was analytically characterized by radiochemical assay, radiochemical purity, molecular weight distribution by gel permeation chromatography and product Identity confirmation by IR. Part of the S-334FM14C was purified by preparative scale gel permeation chromatography to remove a low molecular weight radioactive impurity discovered in the GPC radiochemical purity analysis. Baxter Travenol Laboratories were supplied with 0.75 miliicuries of GPC purified S-33*)FM1<*C as requested. DETAILS 1. Acetylation of the entire existing stock of S-334F i4C produced an estimated 2.3 gram of S-BS^FK^C having a specific activity of 4.97 miliicuries per gram. 2. The analytical properties of the S-33^FM1%C were considered acceptable with the exception of low molecular weight radiochemical impurity as determined by gel permeation chromatography (GPC). This impurity, estimated at M).4i, if totally extracted Into blood from 5-33*FM plasticized polyvinyl chloride film, represents 1/3 of the total radioactivity previously extracted from the original plasticized PVC film in 30 days at 5C. RSV 0010741 DETAILS (Cont`d) S-75"$S"47 Page Two 3. Waters GPC unit, model 301 equipped with y styragel column proved adaptable without modification for making preparative scale purification of up to D.3 gram samples of the S-334FH,4C. 4. The"low molecular weight radiocative impurity was shown to be absent in CPC purified S-334FM1"C. EXPERIMENTAL DETAILS The details of the synthesis, characterization and purification of S-334Fm14C are found in MIC Research Notebook pages 296101-296161 (Reference 4). An outline of this work with notebook page references follows: Topic Miscellaneous Backgroundoutlining the origin and early planning of project Synthesis Practice Runs Labeled Synthesis, Decolonization, Sol vent Dilution MIC Notebook Page No. 296101-5 296I06A-7B 296108A-9 Analytical Characterization Radiochemical Assay Hoi Wt by GPC (Kenyon) Mol Wt by GPC (Litschgi) Radiochemical Purity (by GPC) IR - samp1e iso1 ation Sumnary Table Inventory Information GPC Purification of S-334FMl**C destined for Baxter Travenol Laboratories 296109A-31A 2961 IIA-12A 296113A-148 296115A-24 296I25A-29B 296132A-B 296130A 29613iA 296133 296134-41B Quotation on 1,3 butylene glycol ll*C raw material for alternative labeled S-334FH synthesis 296142A-3 Technical Information on S-334F/S-334FH for trip to Baxter Travenol Laboratories 296144A-49B GPC Preparative Scale Purification of additional stock of S-334FMl4C 296I50A-60 References I Spectroscopy Special Study 74-36 "Synthesis and Characterization of Santlcizar 334Fl*C". .2 Spectroscopy Special Study 74-37 "Human Blood Extraction Studies of PVC Films Containing Labeled Santicizer 334F". RSV 00107^2 References (Cont'd) S-75-SS-47 Rage Three 3 P. R. Graham's Commercial Development Call Report No. 74*7. Baxter Travenol Laboratories, 2*14*74. 4. MIC Research Notebook pages 296101*60. is Attachment Monsanto Industrial Chemicals Co. Applied Sciences St. Louis, Mo. 12/75 " D. B. Hines, J. W. Hirzy, W. J. Utschgi, H. Yepez, M. V. Dietrich RSV 0010743 S-75-SS-47 TABLE 1 ANALYTICAL CHARACTER!ZATION OF S-33AFH1"C Property Specific Activity Peak Hoi Ut (GPC) Radioactive Impurities (Hoi Wt less than 300) IR S-33AFH1 **C A.97 mci/gm 2700 ^ O.At Yes1 Plant S-33AFM dtd 1-9-7A -- 3000 -- Yes 1 IR trace agreed acceptably with plant sample except labeled material still contained a small amount of solvent benzene. RSV 00X0744 Spectroscopy Special Study S-75-SS-A8 SYNTHESIS OF FIVE RADIOLABELED (P-32) FOOD PHOSPHATE SALTS INTRODUCTION Synthetic linear and cyclic polymeric phosphate salts are commonly employed as food additives because of the desirable qualities they can impart to foods. These food additives, as we 11 as many others, are currently on the Food and Drug Administration's (FDA) "generally regarded as safe" list. The FDA is now soliciting and reviewing all old and new scientific data that will help reestablish the safety of these food additives. In order to provide up-to-date definitive data on the metabolic fate and behavior of this class of compounds, when orally ingested, a rat metabolism study is being conducted on contract at the University of Tennessee. Radiolabeled P-32 food phosphate salts were prepared, by Honsanto Applied Sciences, so that the rat study could be performed. SUHMARY Radiolabeled monosodium (P-32) phosphate (ortho) was purchased and used to successfully prepare five representative food phosphate salts. The salts prepared were the tripoly, trimeta, tetrameta, hexameta and insoluble meta. After preparation each salt was radiochemically characterized, properly packaged and shipped to the University of Tennessee for use in the contracted rat metabolism study. DETAILS A preliminary rat metabolism study was carried out with the ortho, tripoly and trimeta phosphate salts. This study involved dosing (stomach tube) two rats per salt, which had been fed diets containing the respective cold phosphate salts at the Q.\% level for 1A days, with 1.0 milliliter of the P-32 labeled salts containing 25 mg of phosphorus per milliliter with a specific activity in the range of 100-200 yCi/ml. The rats were placed in metabolism cages and fed the same diets and water ad libitum. Periodic fecal and urine collections were made and at the end of 72 hours the rats were sacrificed and liver, kidney, fat (mesenteric) and bone (tibia) samples taken. All samples were analyzed for total activity and the fecal and urine samples characterized chromatographically. A second in depth study was then performed with all six food phosphate salts using ten animals per salt. The ortho, tripoly end trimeta salts were therefore prepared twice and the tetrameta, hexameta and insoluble meat salts once. The details and results of these rat metabolism studies will be published elsewhere Ortho: Carrier free monosodium phosphate: NaH2 ,2P0 in water, 10 mCi/ml, spec]fic activity 500 mCi/mm, redionuclIdle purity >99t, was purchased in 5 mCi packages from New England Nuclear (Catalog No. NEX-063). The ortho salt solution was prepared by syringe addition of an appropriate volume of the P-32 salt to a cold monosodium phosphate solution. After mixing 1.25 ml aliquots were transferred to septum vials and the vials sealed. Trimeta: The appropriate volumes of the P-32 salt and cold monosodium salt solutions were combined in e platinum crucible. After careful mixing the solution was taken to dryness by placing the crucible In a 110C oven overnight RSV 0010745 ,1 c c t DETAILS 5-75-S5-W Page Two Trimeta: (Cont'd) The monosodium salt was then converted to trimeta by calcining it for two hours irr a Ruffle furnace at 550C. The trimeta salt was then removed from the furnace, allowed to cool to room temperature and redissolved in a measured volume of distilled water. Aliquots of this solution (1.25 ml) were then transferred to septum vials and the vials sealed. Tripoly: The tripoly salt is made from a 2:1 aqueous solution of di* and monosodium phosphate, which must be flask dried to prevent selective crystal growth, prior to calcining. In order to do this safely and quantitatively the apparatus shown in Figure 1 was used. The appropriate volumes of the radioactive and cold salt solutions were combined In the feed reservoir and mixed by swirling. The apparatus was then attached to the scrubber train and the nitrogen purge started. The stopcock was then opened to allow the feed solution to slowly drip into the drying vessel. After washing the feed reservoir twice with distilled water, the apparatus was removed from the oil bath, wiped ciean and placed in a k50C muffle furnace for two hours. Once it had cooled to room temperature, the tripoly salt was dissolved in a measured volume of distilled water and transferred to a beaker. Solids which were present were removed by placing a Mi 111 pore Hillex filter unit between the syringe and needle used to transfer the 1.25 ml aliquots to the septum vials. Tetrameta: The tetrameta salt was prepared by combining appropriate volumes of the P-32 salt solution and a solution containing equal molar amounts of cold monosodium phosphate and phosphoric acid in a pyrex beaker followed by evaporation to dryness overnight in a 110C oven. The dried salt was then calcined in a muffle furnace at 325C for 2k hours, removed from the oven and a few seed crystals of cold tetrameta stirred in with a glass rod. The salt was then replaced in the furnace at 325C for another 2k hours. Vhen cool, the tetrameta salt was redissolved in a measured volume of distilled water and 1.25 ml aliquots transferred into septum vials using a Millipore Hillex fitter and syringe to remove solids. Hexame ta: The appropriate amounts of the P-32 salt solution and a 9/1 cold monosodium dlsodlum phosphate salt solution were combined and mixed in a platinum crucible and the water evaporated by placing it in a 110C oven overnight. The salt was then calcined In a muffle furnace at 750C for 20 minutes, removed from the muffle and quickly cooled to room temperature by placing the crucible on a cold ceramic plate. The hexameta salt was then dissolved In a measured volume of distilled water and 1.25 ml aliquots transferred to septum vials using a disposable syringe and Millipore Hillex filter to remove solids. Insoluble Meta: The appropriate amounts of the cold and radiolabeled monosodium phosphate solutions were combined, mixed in a porcelain mortar and the water evaporated by placing it In a 1I0C oven overnight. The salt was then calcined in a muffle furnace at 350C for 2 hours, removed from the RSV 0010746 DETAILS S-7S-S$-<B Page Three Insoluble Meta: (Cont'd) furnace and allowed to coo) to room temperature. The mortar was placed in a plastic glove bag, the salt ground with a pestle and 0.08 gram portions of the powdered salt loaded into #5 gelatin capsules. Each capsule was then placed in a 2 dram screw cap vial prior to removal from the glove bag. RADIOCHEMICAL ASSAY AND PURITY The specific activity and purity of each salt was determined via liquid scintillation spectrometry. Assay Each salt solution was diluted gravimetrically with distilled water such that a five ml aliquot of the final dilution had a count rate in the range of 15*000*25,000 CPH. Four 5 ml aliquots of each diluted salt solution were transferred to tarred glass liquid scintillation counting vials. The vials were then reweighed and the sample weights recorded. Two of each set of four vials contained a weighed amount of a certified aqueous P-32 standard (New England Nuclear, NEX0175). Fifteen ml of Insta-Gel LSC coctail (Packard Instrument Co.* cat. #8002177) were added to each vial and the vials were equilibrated in the counter at 10C prior to counting. The samples were counted with a Mark III Liquid Scintillation Spectrometer (Searle Analytic* Inc. Model 6880) using the preset Isotope quench corrected program k (P-32) mode. Counting efficiencies were In all cases found to be in the range of 97"99fc as determined via the internal standardization method. The insoluble meta phosphate salt had to be initially solubilized by heating with phosphoric acid. Once solubilized it was assayed In the same manner as the soluble salts. Radiochemical Purity License free amounts of each salt were submitted to Industrial Testing Laboratories for separation by paper chromatography. Each sample was spotted in duplicate developed and one-half visualized to aid location of the unvisuaiized components. The radioactive spots on unvisualized paper chromatograms were then cut out and extracted with 10 ml of distilled water. Five ml aliquots of these extracts were then analyzed In the same manner as the soluble salts. The radiochemical purity of the insoluble meta salt was not determined. DATA The analytical data for the phosphate salts are shown In Tables l-lll. RADIATION SAFETY SUMMARY All labeled syntheses were proceeded by successful completion of an equivalent synthesis with unlabeled starting materials and a complete review by the Radiation Safety Committee. The syntheses were performed In the hood In the hot laboratory and were continuously monitored with a VIctorean Model AA0 RSV 0010747 RADIATION SAFETY SUMMARY (Cont'd) S-75-SS-48 Page Four Survey Heter and an Eberline Mode I DRM-k Rate Pulse Meter. All personnel were equipped with film badges and protective clothing. Laboratory air and hood air were also sampled and checked for radiation. In no case were any personnel exposed to radiation levels that exceeded NRC regulations. ss Attachments(4) Monsanto Industrial Chemicals Co. Applied Sciences St. Louis, Mo. 12/75 - E. S. Tucker, H. W. Dietrich RSV 0010748 S-75-SS-48 TABLE I SPECIFIC ACTIVITY AMU PUKtTV OF P-32 PHOSPHATE SALTS 1st Preparation Salt Analyzed Specific Activity1 UCI/ml Sa 11 Species Activity Distribution2 Distribut Ortho (MSP) 152 ortho >98.6* Tripoly (STP) 150 ortho 2.1* pyro tripoly 12.7 82.6 trimeta 1.7 long chain 0.9 0.2* 12.3 B5.7 1.1 0.7 Trimeta (STMP) 169 ortho 1-5* pyro 0.5 tripoly 2.5 trimeta 95.0 1ong cha1n 0.4 0.1* 0.4 2.0 97.5 0.1 1 As of 11-3-75, 10:30 AM CST. 2 Paper chromatography * * Paper chromatography - Liquid Scintillation Counting. > RSV 0010749 S-75-SS-1i8 TABLE II SPECIFIC ACTIVITY AND PURITY OF P-32 PHOSPHATE SALTS 2nd Preparation Salt Analyzed Specific Activity1 uC S/ml Salt Species Activity Distribution12 Distribut ion3 Ortho Tripoly Trimeta 152 ortho >99-5* 150 ortho 0.3 pyro 12.0 tripoly 86.5 trimeta 0.2 long chain 1.0 169 ortho 0.1 pyro 0.1 tripoly 0.8 trimeta long chain 99.0 ___ 99.9* 0.2 9.9 88.6 0.3 0.9 -- 0.1 0.6 99-2 0.1 1 As of 12-3-75. 8:30 AM CST. 2 Paper chromatography - colorimetrically. 2 Paper chromatography - Liquid Scintillation Counting. RSV 0010750 S-75-SS-48 TABLE I I I SPECIFIC ACTIVITY AND PURITY OF P-32 PHOSPHATE SALTS 1st Preparation1 * 3 * 5 Salt Analyzed Specific Activity1 Salt Species Distribution7 Acti vi t' Distribut Tetrameta Hexameta 193 pCi/ml ortho pyro tripoly tetrapoly trimeta tetrameta long chain 65 pCi/ml Hexameta ortho pyro tripoly tetrapoly trimeta tetrameta high meta high poly long chain 16.5 14.4 18.4 9.4 10.9 30.1 0.3 ___ 5 -- -- -- -- -- -- -- 16.7 15.0 18.0 9.1 9.9 31.3 0.2 0.2 0.1 0.3 0.4 2.9 1.8 1.8 90.9 1.7 Insoluble Meta" 2456 yCI/g <197 pCI/capsule) 1 As of 12-23-75, 10:00 AH CST. 3 Paper chromatography - colorimetrlcaMy. 3 Paper chromatography - Liquid Scintillation Counting. * Not analyzed for Impurities. 5 Not analyzed colorlmetrically. RSV 0010751 rigure 1. Drying Vmi1 for Drying 8TP Fed a. Feed reservoir, cloitd with adjustable stopcock. b. Nitrogen sweep, enters above and below stopcock to equalise pressure. c. Drying vessel, pyrex for calcining. d. Oil bath* 10O*C. controlled* with agitation. e. Condensation trap* glass wool. f/g. Scrubbers with fritted glass diffusers and 100 ml.water, h. Vacuum air filter to sample scrubber effluent. \M .\ 8*rSS-SZ-$ RSV 0 0 1 0 7 5 2 DETERMINATION OF BENZENE IN AIR IN THE ST. LOUIS RESEARCH CENTER Spectroscopy Special Study S-75-S$-l*$ INTRODUCTION The purpose of this investigation is to determine worker exposure to benzene in Q building labs 0309 and 0311. SUMMARY Benzene levels ranging from 0.3 to 2.5 ppm were detected. The results are given in the table. EXPERIMENTAL GC retention time was used In the verification of benzene and calculations are based on a benzene standard. An example of the calculations is given below. Calcula tions Volume of Air k Pimp Flow Rate x Sampling Time t 10 5 Sampled (Liters) (ml/min) (min) Weight Sample (pg) m Area Sample Peak Cone. Std. (pg/uL) X Vol. Injected (uL) (counts) Area of Standard (counts) Concentration Sample (u9/L) Weight Sample (pg/L)/Volume of Air Sampled (Liters) Concentration Sample (ppm) P9/L X H.W. (sample) For Sampling 75-frl Volume of Air Sampled - 23-6 ml/min X 2kQ min X 10** - 5-7 L Weight Sample (pg) Concentration (pg/L) - 3776*1 X 5 >V79F " <l5-27 ' ~tlT " 8-00 Concentration (ppm) - 8.00 X - 2.5 ppm Reference: GC/MS File #75-220 ss Attachment Monsanto Industrial Chemicals Co. Applied Sciences St. Louis, Mo. 12/75 - L. H. Chapmen, C. E. Hoffmann, M. W. Dietrich RSV 0010753 S-75-SS-49 TABLE Insert if Flow Rate Samp!ing Time Benzene Concentration in Air 75-41 23.6 ml/min 4 hrs. 2.5 ppm 75-54 24 ml/min 6 hr 20 min 0.7 Ppm 75-35 23.5 ml/min 7 hr 52 min 0.3 ppm 75-45 24 ml/min 3 hr 4t min 2.2 ppm RSV 0010754 Spectroscopy Special Study S-75-SS-50 PREPARATION AND CONDITIONING OF COLLECTION COLUMNS INTRODUCTION This report will explain the procedure for preparing and conditioning collection columns used for analyses of organic chemicals in air. Two types of columns are used most frequently: Tenax GC, used mainly for higher boiling materials and Porapak N, used mainly for low boiling compounds. The preparation of columns with these packings is the same but conditioning processes, described below, are quite different. PREPARING COLLECTION COLUMNS Materials needed:* 1 1/A" O.D. X 1/8" I.D. X 6" Pyrex glass tubing with dimple 1 1/2" from one end Silanated glass wool Tenax-GC 60/80 mesh column packing or Porapak Type N 50/80 mesh Supeltex H-2 I/A" vesbel ferro #02 - 23 20 Glass marking pen Conditioning oven (a GC oven or a column conditioning oven may be used) Procedure: 1. Being sure the glass tubing is clean, take a pinch of glass wool, push it to the dimple, and snuggly pack it down. 2. Fill the tube with 0.18 grams of packing. If Tenax-GC Is used, or 0.31 grams of packing. If Porapak N is used. If the packing for one column is weighed, the rest may be measured by the first. 3. Tap one end of the column on the table so that the packing is firmly packed. This will reduce the chance of having gaps after conditioning. A. Place another piece of glass wool on top of the packing and mark the tube with an identifying number. It is now ready for conditioning. Attached is a diagram of a collection column. TENAX-GC COLUMN CONDITIONING PROCEDURE 1. Purge each tube with nitrogen for five minutes and put in a covered container also purged with nitrogen. Place the container in a 275C oven for 2A hours. 2. After the columns have been removed and cooled, condition them overnight in a 250C GC oven with helium or nitrogen carrier flow of about 30 mls/min, when connecting the column, gas flow should be through the column toward the end with the dimple. Several columns can be attached in series depending on the capacity of the GC. We recommend vesbel ferros for metal to glass connections because they withstand decomposition at high temperatures and are reusable. RSV 0010755 K TENAX GC COLUMN CONDITIONING PROCEDURE (Cont'd) S-75-SS-50 Page Two 3. Remove and cool. The columns are now ready for use. Before a sampling, the columns should be reconditioned at 27SC for IS to 20 minutes with carrier flow of about 30 ml/min. PORAPAK N COLUMN CONDITIONING PROCEDURE 1. Attach the column to the GC oven and set a carrier flow of about 30 ml/min. When connecting the column, gas flow should be through the column toward the end with the dimple. Several columns can be attached in series depending on the capacity of the GC available. 2. Slowly program the oven temperature to 160C and hold overnight or to I90C and hold for 2 hours. 3. Remove and cool. The columns are now prepared and conditioned for use. Before a sampling, the columns should be reconditioned at I90C for 15 to 20 minutes with carrier flow of about 30 ml/min. ss Attachment Monsanto industrial Chemicals Co. Applied Sciences St. louis, ho. 2/76 - L. M. Chapmanv M. W. Dietrich RSV 0010756 S-75-SS-50 Ocl <jrr\AJ r' "in p^*' * 4 ?! : ,*i W Lc**aJLl &<uu * * 1*1 CD. I* i RSV 0010757 Spectroscopy Special Study S-75-SS-5I GC MODIFICATION FOR MEASUREMENTS OF ORGANIC CHEMICALS _______________IN AIR BY THERMAL DESORPTION INTRODUCTION Determination of organic chemicals in air, using the procedure described in Spectroscopy Method 76-1, requires some modifications of a laboratory gas chromatograph. A means must be provided to heat the collection column external to the GC. The heater we use is described In this report. It is also necessary to divert the carrier gas flow to an external line. Finally, the injection port septum nut must be modified so that the collection column can be attached to the GC. These modifications are described in this report for a HP-5710 gas chromatograph. Most other laboratory gas chromatographs can be modified in the same manner. details A. Construction of External Heater* I Below is a description of how to prepare a heater for desorbtion of collection columns. Heater for )/*" Glass 6" Vapor Sampling Tubes Materials: Approximately 8 ft. 2A-gauge BSS Chrome) "A" yellow asbestos covered Fisher Catalog #I5-539C for 100 foot spool 6" length 1/4" S.S. tube 5" X 13/16" paper .003 to .00*" Pyrex tube 10.) mm i.d. X * 3/A", notched both ends for wire 5" of narrow (2 mm) glass braid 2 ft. #30 BS Chrome! "A" base Hoskins Resistance wire I 5/8" X * 11/16" of .0025" anneal led A1 foil 8" X 8" - 1/A" polyurethane pad Straighten yellow heater wire to remove kinks - large bends are O.K. Place I/A" S.S. tube lengthwise along edge of Al foil on foam pad; press down hard and roll. Al will roll up on tube to form a loose-fitting tube. Dampen paper; make one wrap around S.S. tube lengthwise as with foil; dry. Slip S.S. tube and paper shim into the Al tube. Place on smooth, hard surface; press hard and roll in direction of original roll-up. This will make foil into a snug fit of two turns. Tape one end of heater wire onto the assembly and tightly wind on, keeping it close spaced. Slip assembly into glass tube. Cut braid in half and thread onto end of heater wire to form one final turn in end of glass jacket; bend through notch and enough to wrap on with the #30 wire. Take a few turns of wire around braid; wind remainder around jacket snugly and secure. Check resistance (aim for 12.8 to 12.9) before securing second end. Estimate 86 turns with ^7*5 ft. wire overall for A 3/A". Finally, flare ends of Al sleeve to keep it from sliding out. With He flow at ^30 ml/min., empty sampling tube and thermocouple in place situated at median area for the Tenax, a temperature of ^200C is achieved in 2 1/2 min. and held with Variac set at ^20 V. This calibration should be checked with each Variac used RSV 0010758 S-75-SS-51 Page Two 8. GC Modification for External Carrier Gas Flow Host gas chromatographs have a carrier gas fitting which is connected to the injection port through a flow controller valve and a molecular sieve trap. A three port valve can be placed in the carrier gas line between the molecular sieve trap and the injection port and mounted on the top or the side of the chromatograph (see diagram attached). With a valve of this type installed, the carrier gas can easily be switched to the external helium line for chromatographic purposes. We typically connect this external carrier gas line to one end of an air sampling tube. The other end of the tube is connected to the injection port of the chromato graph at the septum nut. Using the three port valve the carrier gas can be switched to the external line and used to flush organics from the heated sampling tube onto the head of the analytical GC coiumn. In this position the three port valve closes the normal carrier gas line to the injection port. This keeps sample and carrier gas from leaving the injection port through the normal carrier gas line. We have found that a Whitey valve SS-42XF2 works well for this modifica tion. This valve has an intermediate position at which the input port is connected to neither exit port. This position can be used as a convenient shut-off for the carrier gas. The diagram is a schematic of how the collection column is attached to the GC. What is not shown is the heater, but the collection column actually fits down into the heater and is attached to the injection port and the external helium flow with 1/4" Swage Iok fittings. C. Modification of Septum Hut A Swagelok SS-400-R-2 fitting is silver soldered to the septum nut as shown in the second figure. The hole in the septum nut must be enlarged to receive the fitting. A septum is still required to prevent leakage. *ss Attachments(2) Monsanto Industrial Chemicals Co. Applied Sciences St. Louis, Ho. 3/76 - L. H. Chapman, H. W. Dietrich RSV 0010759 WS-SS-Si i i i RSV 0010760 S-75-SS-51 RSV 0010761 Spectroscopy S-75-SS-52 DECEMBER 1975 MERCURY INVENTORY, V. G. KRUMMRICH PLANT, ___CHLOR-ALKALI DEPARTMENT INTROPUCTION S SUMMARY The mercury inventory made at the V. G. Krurnmrlch plant on December 2, 1975 has been completed. The sum of the average weights for the 22 cells is 255*294 pounds, +2919.9 (2 sigma limits). This inventory is comparable to that taken in June 1975. Inventory by individual cells Is tabulated in Table i attached. A specific activity of 1-96 X 10 k microcuries per gram was produced on the spiking date December 2, 1975- The cell house was mixed for 60 hours except for cells 2, 10 and 19 which were mixed 36, 10 and 20 hours,respect!vely. Mixing was followed on 7 cells namely 1, 2, 5, 7, 10 and 21. This mixing study indicated complete mixing after 12 hours. On this basis, it was concluded that the three cells mixed less than 60 hours represent an accurate inventory. ss Attachments(10) Reference: Research Notebook MIC 264383*264398 Monsanto Industrial Chemicals Co. Applied Sciences St. Louis, Ho. 12/75 - H. Yepez, 0. 8. Hines, M. V. Dietrich RSV 0010762 vc WtnCUi<Y IMVOTnitr pef cui r nvrfjtary rEcC'pE* 197c CF.LL NO AVERAGE NLPCURY INVENTORY f LRS) STftHiJARn ncviATIPli I LT^ I T*0 Si or.A - PERCENT LF TOTAL <L6SI 1 U91f .60 2 10026*72 3 1U958.50 4 12201*2* 5 lC9r.j6 6 UICO.59 7 1 1620.21 0 107?6,66 9 11365.70 10 11656.35 11 11464.16 12 11290.62 13 12695.30 14 12146.14 15 13204.14 16 16671,91 17 12695,nc le 1041p,0 9 19 11367.36 20 10691.55 21 13340.72 22 11963.93 42.13 71.97 72.03 53.*5 40. ie 50. 3 56.r4 77.95 67.12 62.9? AH.? 2 45.25 64.00 43.72 64.06 54.76 P0.95 37.0 7 65*06 82.26 I 42.63 60.72 84.26 143.94 144.06 107.09 96.35 1*>0.3b 112.00 155.69 134,2* 125.85 176,44 90.51 128.00 87.44 123.00 169.53 If 1.91 74.13 130.12 164.52 285.26 121.43 0.7f 7 1.32 1.315 0.373 0.87S G.991 0. 964 1.457 1.132 1.0*0 1.5*9 0 * c* 1` l 1. i! r r 0,720 0.96 1.55 1.275 0.712 1.143 1.512 2.15*. 1.415 THE SUP OF THE AVERAGE WEIGHTS IS 255294.RP |_3S. THE SUM OF ALL TWO-SIGMA IS 2921.91 LPS. VxtIj IAIA VN/>1 THE PERCENT THE SUM OF ALL TV.O-SlGWftS IS OF THE TOTAL INVENTORY k'EICHT = 1.145 PERCENT RSV 0010763 Spectroscopy S-75-SS-53 DETERMINATION OF BENZYL CHLORIDE AND TOLUENE IN AIR AT THE DELAWARE RIVER PLANT INTRODUCTION The purpose of this study was to determine worker exposure to benzyl chloride and toluene. SUMMARY The results are attached. Levels of benzyl chloride ranged from 0.3 to A.7 ppm. Toluene was detected in levels from 1.4 to 16.1 ppm. EXPERIMENTAL An 0V 17 column was used for the analysis and Tenax tubes for sample col lection. Calculations are based on benzyl chloride standard. Identification is based on GC retention times. Ortho, meta and para chloro toluene are resolved from benzyl chloride on this column. Calculations Volume of Air m Pump Flow Rate Y Sampling Time y ,n-j Sampled (Liters) (ml/min.) Weight Sample (pg) Area Sample Peak Cone. Std. (pg/pL) X Vol, Injected (pL) (counts) Area of Standard (counts) Concentration Sample (pg/L) Weight Sample (pg/L)/Volume of Air Sampled (Liters) Concentration Sample (ppm) pg/L (sample) x _2f M.W. (sample/ For Sampling 75-41 Benzyl Chloride Volume of Air Sampled (Liters) Weight Sample rs) 36.2 X 7 X I0`3 .253 1304 X 0.147 X 1.9 1033 0.35 Concentration (pg/i) 0.35 0.253 1.39 Concentration (ppm) 1.39 X 24.45 0.3 ppm ss Attachment Reference: GC File #75-213 Monsanto Industrial Chemicals Co. Applied Sciences St. Louis, Ho. 12/75 ~ L. M. Chapman, M. V. Dfetrich RSV 0010764 #75-46 Sampling BzCl Refining Columns Toluene Dryer table Toluene (ppm) Benzyl Chloride (ppm) 7-0 0.8 #75-57 Changing Filter Screen on Refining Column Feed 3.7 4.7 #75-41 Benzyl Chloride to Storage 16.) 0.3 #75-37 Benzyl Chloride Operator Rocky 1.4 0.3 #75-61 Operator while Taking Benzyl Chloride Samples 2.0 1.2 * Sampling time % 7-12 min Flow rate 216 ml/min + Sampling time 4-8 min Flow rate 36.2 ml/min RSV 0010765 Spectroscopy Special Study S-75-SS-51 DETERMINATION OF ACETAMIDE (AC), N-METHYL ACETAMIDE (MMAC) AND DIMETHYLACETAMIDE (DMAC) IN URINE INTRODUCTION Samples were analyzed to determine levels of acetamide in the urine of workers at the Decatur, Alabama Plant. Control samples of non*exposed subjects were also analyzed for AC, MMAC and DMAC. SUMMARY The results are attached. Acetamide in the first set was detected at about 10 ppm (see Table I). A portion of the material detected was found to come from the resin used in the extraction before analysis. A blank should be run with each batch of samples to correct for this interference. Identification of acetamide was by GC/MS. The second table shows GC analyses results for acetamide, MMAC and DMAC. EXPERIMENTAL Refer to Standard Test Method STM-00498, Textiles Division for procedure. Identification by GC/MS was made by scanning the selected ions of acetamide 41, 59, and 40. Comparison of GC retention time was also used in identification. References: GC/MS File #75"193 Standard Test Method STM-00498, Textiles Division, January 21, 197$ ss Attachments(2) Monsanto Industrial Chemicals Co. Applied Sciences St. Louis, Mo. 12/75 - L. H. Chapman, C. E. Hoffmann, M. W. Dietrich RSV 0010766 \>*- V TABLE (Set I) S-75-SS-S* Sample James Aldrich Kenneth R. Lanfcert #25 (control) #26 (control) blank Acetamide (ppm) 8.9 11.2 11.3 2.7 \ .2 RSV 0010767 S-75-SS-54 TABLE (Set 2) Sample Number 1 2 3 4 5 6 7 B 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 DMAC CONCENTRATION IN PPM HMAC AC NO ND 7 ND ND ND ND ND ND ND ND ND ND ND ? ND ND ND >5007 ND ND ND ND ND ND ND ND M ND 15 74 ND 3 ND 13 ND 20 ND 15 ND 15 ND 11 5? 25 ND 13 5? 3 ND 7 ND 15 5? 15 ND ND ND 13 ND 7 ND ND ND 7 20? 13 ND 5 ND ND ND 11 5? ND ND ND Other Compounds ca 5 15 0HAC HD < 5 HMAC HD 3 AC HD < 3 Accuracy 0-20 ppm + 2 ppm 500 ppm +100 ppm RSV 0010768 Spectroscopy Special Study S-75-SS-55 CHLORINATED DIBEN20FURANS IN CRUDE HONOCHLOROBENZENE ____________ FROH THE OXYCHLORINATION PROCESS SUMMARY After Process Chemicals research (Dennis Kalota) confirmed the presence of octachiorodibenzofuran on the oxychlorination catalyst, other chlorinated isomers of dibenzofuran were suspected of being produced In the process. GC/MS analysis of crude monochlorobenzene (MCB) and pot residues showed the presence of chlorinated dtbenzofurans (dichlorodfbenzofuran through octachlorodlbenzofuran) at levels In the range of one ppm for the crude MCB and several hundred ppm for the pot residue. DISCUSSION The selected ion monitoring (SIM) mode of operation provided the data used to measure the various chlorinated dibenzofurans. The SIM technique and possible interferences are described in detail at the end of this report. Table I shows the results for a pot residue and a crude MCB from laboratory oxychlorination. All isomers with the same number of chlorines are sunned to give one value in the table. Diphenyl ethers with two more chlorines than the corresponding dibenzofuran are also included in these values since they have fragment ions which interfere with the dibenzofuran measurements. A sample of Hooker Crude MCB was analyzed for tetrachloro through octachlorodibenzofuran; the results are shown In Table li. The initial analyses (Table I) had to be performed on a crude MCB and a pot residue from different laboratory oxychlorinations. Another oxychlori nation provided material from each step which was analyzed for two chlorinated dibenzofurans. The refined MCB (1008348) and the recovered benzene (1008348) contained no tetrachlorodlbenzofuran with a detection limit of 0.2 ppm and no octachlorodibenzofuran with a detection limit of 0.6 ppm. The base scrubbed crude and the unscrubbed crude contained the same level of octachloroand tetrachlorodlbenzofuran. These data along with the corresponding pot residue are shown in Table III. Crude MCB from oxychlorination was also analyzed for chlorodioxins using the SIM technique. No dioxins were found and the detection limits are given In Table IV. EXPERIMENTAL In the selected ion monitoring (SIM) mode of operation, the mass spectrometer is set to continuously monitor one or several Ions characteristic of the compound being measured. SIH is one hundred to one thousand times more sensitive than the standard scanning mode of GC/MS analysis. For this study, electron impact ionization was used to form ions in the mass spectrometer since dibenzofurans and dibenzodioxins give good parent ions and their electron impact fragmentation is documented. The GC conditions used for the analysis are given below. Column: IM, 3* 0V 1, 3 fm I.D. Carrier Gas: He, 30 ml/min Temperature: 110 to 270C ei6/min * RSV 0010769 EXPERIMENTAL (Cont'd) S-75-SS-55 Page Two The SIM measurements for chlorinated dibenzofurans and chlorinated dioxins were made by monitoring the parent ion for each compound and matching retention times with known standards. Confirming ions, parent ion less 63 amu, 'were monitored for tri-, tetra- and octachlorodibenzofuran. The full spectrum of octachlorodibenzofuran was obtained by a solids probe analysis of the material isolated from the oxychlorination catalyst using the Hewlett-Packard 5982 GC/MS system. Quantitation for both dibenzofurans and dibenzodioxlns was done by comparing the response of standards with the response of the corresponding compound in the MCB sample. Because of the low levels being measured the values in the table could vary by 20% of the value. The detection limits for the chlorinated dibenzodiox ins vary because the sensitivity of the mass spectrometer changes as the number of chlorine atoms on the molecule changes. The detection limits for tetra-, hexa-, heptaand octachlorodibenzodioxins were determined by running standards. The detection limit for pentachlorodlbenzodioxin was taken as the average of the detection limits of tetra- and hexachtorodibenzodioxin. The detection limits for mono-, di- and trichlorodibenzodioxin were assumed to be the same as that for tetrachlorodibenzodioxln. This Is a good assumption for calculating limits of detection since the mass spectrometer sensitivity for the dibenzofurans and dibenzodioxins actually increases with a decrease in the number of chlorine atoms. The SIM technique is subject to interferences from compounds having ions at the same mass value as those used to detect the target compounds, e.g. dibenzofurans. Normally, these interfering compounds do not have the same GC retention time as the target compounds and can be distinguished on this basis. The loss of specificity is the price paid for the large increase in sensitivity which makes the SIM technique so useful. The chlorinated dibenzofurans are subject to an unusually severe Interference from chlorinated diphenyl ethers. The mass spectrum of chlorinated diphenyl ethers all have a very strong fragment ion corresponding to the loss of Cl from the original molecule. This means that the mass spectrum of decachlorodiphenyl ether has a strong ion at 510 (molecular wt.) less 70, or kkO. This Is exactly the molecular weight of octachlorodibenzofuran and the LAO ion from the ether also has the same chlorine Isotope pattern as octachlorodibenzofuran. Other fragment Ions from decachlorodiphenyl ether Interfere with possible confirming Ions for octachlorodibenzofuran. This type of interference by diphenyl ethers with two more chlorines than the corresponding dtbenzofuran holds true for ell of the various chlorinated dibenzofurans. The GC retention times of the chlorinated dibenzofurans and the corresponding Interfering ethers are close. The analysis of the ethers and dibenzofurans as separate entities at low levels would be very difficult. The business group has agreed that the measurement of the sum of these two types of compounds wi11 be e useful tool for current process studies. There are definitely chlorinated dibenzofurans in crude MCB which are not obscured by corresponding ethers. Table V gives an estimate of diphenyl ether interference for one sample of pot residue assuming the same sensitivity for both types of compound. RSV 0010770 EXPERIMENTAL (Cont'd) S-75-SS-55 Page Three Table VI Is a survey of likely Interferences for tetrachlorodibenzofuran. Only the major probable interfering ions are listed for each compound. Some of the compounds do not interfere, some interfere with a few ions of tetrachlorodibenzofuran, and hexachlorodiphenyl ether interferes severely* This table illustrates the type of background information which is needed to do careful SIH analysis. ss Attachments(6) Monsanto Industrial Chemicals Co. Applied Sciences St. Louis, Mo. 12/75 * G. W. Happes, M. W. Dietrich RSV 0010771 S-75-SS-55 TABLE I OI8ENZOFURANS AND 01 PHENYL ETHERS IN PPH* Oetach1orodibenzofuran (and decachlorodiphenyl ether) Heptachlorodibenzofuran (and nonachlorodiphenyl ether) Hexach1orodIbenzofuran (and octachlorodTphenyl ether) Pentach1orod1benzofuran (and heptachlorodiphenyl ether) Te trach1orod1benzofuran (and hexachlorodlphenyl ether) Trichlorodlbenzofuran (and pentachlorodiphenyl ether) Dech1orod1benzofuran (and tetrachlorodiphenyl ether) Monochlorod1benzofuran (and trfchlorodiphenyl ether) Pot Residue 1008339-1* 230 590 6.5 460 200 31 < 10 Crude 1008339*8 1.2 0.9 l.l 0.5 0.4 0.2 0.05 < .2 * SIM GC/MS analyses cannot accurately distinguish between these classes of compounds. Both are probably present In most samples (see Table V). RSV 00X0772 S-75-SS-55 TABLE II DIBENZOFURANS AND DIPHENYL ETHERS IN PPH HOOKER CRUDE MCB MIC 1006339*9 Octachlorodibenzofuran (and decachlorodiphenyl ether) Heptachlorod1benzofuran (end nonachlorodiphenyl ether) Hexachlorod1benzofuran (and octachlorodiphenyl ether) PentachlorodIbenzofuran (and heptachlorodiphenyl ether) Tetrachlorod(benzofuran (and hexachlorodlphenyl ether) 13 6.k k. 2 1.6 RSV 0010773 S-75-SS-S5 TABLE 111 DI8EHZ0FURANS AND DIPHENYL ETHERS IN PPH Crude HCB 1008348-1,2,3 Pot Residue 1008348 Octachlorodibenzofuran (and decaehlorodiphenyl ehter) 1.7 110 Tetrachlorodibenzofuran (and hexachlorodipheny1 ether) .20 RSV 0010774 TABLE IV DETECTION LIMITS IN PPM CRUOE MCB 1008339-8 S-75-SS-55 MonochlorodIbenzodI ox In DichlorodibenzodI ox In TrichlorodIbenzodioxIn Tetrachlorod!benzodIoxin Pentachlorodibenzodioxin Hexachlorod t benzodioxin HeptachIorodibenzodioxIn Octachlorodibenzodioxin ND < 0.I ND < 0.1 ND < 0.1 ND < 0.1 ND < 0.2 ND < 0-3 ND < 0.4 ND < 0.4 RSV 0010775 S-75-SS-55 TABLE V ESTIMATED DIPHENYL ETHER INTERFERENCE FOR POT RESIDUE 29*W1 Dibenzofuran ______________ Concentration ________________ Percent contribution from diphenyl ether Octachlorodibenzofuran Heptachlorodibenzofuran 25 ppm 23 ppm 5"10% 10*30% Pentachlorodfbenzofuran 11 ppm 50-80% Tetrachlorodlbenzofuran 39 ppm 50-80% Dichlorodibenzofuran 0.6 ppm 5*10% RSV 0010776 RSV 0010777 Spectroscopy Special Study S-75-SS-56 THE PREPARATION AND CHARACTERIZATION OF CARBON-14 LABELED TETRADECANOL ETHOXYLATES BACKGROUND/SCOPE In recent years* the increased emphasis placed on determining the environmental impact of our products has led to sophisticated investigations of their biological fate. The use of radio-tagged materials has gained wide acceptance as a means of following their biodegradation and biomagnification in organic systems. Carbon-14 labeled sodiun alkyl benzene sulfonates (LAS) have been prepared and their biomagnification studied in aquatic organisms. To place the results of the above study in the proper perspective, the decision was made to prepare carbon-14 labeled nonionic surfactants and to evaluate their, as well as other tagged surfactants', biological fates. This report covers the preparation and characterization of carbon-14 labeled non ionics (tetradecanol ethoxylates) incorporating the following objectives: 1. Adapt existing standard bench ethoxylation procedures and equipment to guarantee personnel safety and commercial quality. 2. Prepare 25 gram quantities of the following ethoxylates: a. 1-tetradecanol-1%C + 7E0; 400 uci/gm. b. 1-tetradecanol + 7E0 - lvC; 340 uci/gm. c. 1-tetradecanol + 14E0 - lfcC; 60 uci/gm. 3. Prepare 400 grams and 100 grams of cold 7 mole and 14 mole ethoxylated 1-tetradecanol to serve as diluent for labeled products. SUMMARY AND CONCLUSIONS A. Existing small-scale Itboxylation procedures and equipment were modified and refined until a high degree of confidence was achieved in providing for personnel safety and high product quality. A final practice ethoxylation was successfully performed in T-305 under actual conditions planned for the tagged syntheses. B. The labeled syntheses carried out to prepare I-tetradecanol-^C + 7E0 and 1-tetradecanol + 14E0 - |4C achieved targeted quality and specific activity. However, a significant labeled ethylene oxide loss (3 grams, 201) which occured during'-the^preparation of the 1-tetradecanol + 7E0 - ,VC ethoxylate resulted In a product containing less than desired ethylene oxide content (actual 5.6 E0) and specific activity (290 uci/gm. vs 3*0 uci/gm). This material has been judged acceptable and a second synthesis was not necessary. Diluent ethoxylates were preparecT'as targeted. C. Radiochemical safety objectives were satisfactorily met. The labeled ethylene oxide leakage did not contaminate either attendant, personnel or facilities, but escaped to the atmosphere via the synthesis hood. V \L RSV 0010778 S-75-SS-56 Page Two SUMMARY AMD CONCLUSIONS (Cont'd) 0. A new technique for determining the ethylene oxide adduct distribution of single homolog alcohol based ethoxylates by high pressure liquid chromatography was developed jointly by the MIC Physical Sciences Group and the authors. This method was useful in confirming product quality of both labeled and diluent ethoxylates and is currently being refined for use in tracing intact or partially degraded ethoxylates in biological systems. E. Aliquots of the labeled and cold ethoxylates were delivered to R. 0. Swisher. Unused portions of the labeled ethoxylates are stored in T-305 for future applications. Reference (Complete Report): 1. Special Report ,rThe Preparation and Characterization of Carbon-14 Labeled Tetradecanol Ethoxylates" by J. B. Hillard and D. B. Hines, Job. No. 74041-10, Report No. 8347- ss Monsanto Industrial Chemicals Co. Applied Sciences St. Louis, Ho. 12/75 - J. B. Hillard, 0. B. Hines, V. J. Lftschgl, M. U. Dietrich RS V 001.0779 Spectroscopy Special Study S-75-SS-57 ORGANIC CONTAMINANTS IN TRENTON PHOSPHATE PRODUCTS INTRODUCTION The Trenton phosphate plant experienced a problem of contaminants in food grade pohsphates that appeared to be related to the soda ash obtained from Wyandotte BASF. The problem Mas felt to be due to organic contamination since no quality problems were encountered with the high temperature polyphosphate and IMP products. A study was initiated to identify the organic contaminants so that either new test procedures or new specifications could be formulated to prevent future quality problems. SUMMARY The contamination problem was Identified In the failure of some phosphate products to pass the food grade patch test. For this test the product is dissolved in water and the solution Is filtered. When this test was carried out on "Bad" sodium acid pyrophosphate (SAPP) a dark oily stain was left on the filter pad. During the period of contamination a balck scale was found in the east MSP hold tank. This contained significant amounts of organic material (^30$) composed mainly of long chain hydrocarbon oil with small amounts of carboxylic acids. This scale is probably not directly responsible for the failure of SAPP to pass the test; however, the scale does represent a likely collection point for any organics getting into the process. Wyandotte essentially agreeswith the analyses of the black scale. Analyses of organics removed from good andbad soda ash and from good and bad SAPP did not give a conclusive reason for the failure of SAPP to pass the test. Small amounts of hydrocarbon oil were found In the bad soda ash but not in the bad SAPP. Hydrocarbon oil was not found In good soda ash or good SAPP. Hydrocarbon oil entering the plant throughthe soda ash raw material and collecting In various parts of the process Is the most likely cause of the patch test failure. RESULTS Infrared, proton nuclear magnetic resonance and gel permeation chromatography of the organic components isolated by either Soxhlet extractions or surface washings of "good" and "bad" SAPP (sodium acid pyrophosphate), "good" and "bad" soda ash from Wyandotte BASF and a black oily scale from the Trenton plant east MSP hold tank showed: A. The black scale Is a matrix of an acid phosphate coated with a mixture of a long chain hydrocarbon oil and polymeric carboxylic acids. B. The chloroform surface washings of "good" and "bad" soda ash showed the "bad" ash contained a low level of a hydrocarbon oil. The "good" soda ash wash was a phthalate ester. C. IR analysis of the chloroform surface washes of "good" and "bad" SAPP Indicated both were phthalate esters. v V' RSV 0010780 RESULTS (Cont'd) S-75-SS-57 Page Two D. IR comparison of the IR spectra of "good" and "bad" soda ash showed a two-fold increase in the level of THF extractables for the "bad" ash. The THF extractables from the "bad" ash are .approximately a 50/50 mixture of a hydroxy carboxylate ester and a phosphate ester. The phosphate ester was not detected in the "good" ash. a E. The THF extractables from "good" and "bad" SAPP showed a seven-fold increase in level of extractables and a difference in chemical identity. The "good" SAPP sample was Identified by IR as a carboxylic acid. The "bad" SAPP extract contained the same type of impurities found In the "bad" ash. F. NMR analysis of the THF extractables from "good" and "bad" soda ash and "good" and "bad" SAPP indicated that the organics isolated from the "good" and "bad" soda ash and the "Bad" SAPP may be principally THF decomposition products. There may be a synergistic effect of a metal Impurity triggering the decomposition of the THF. Several possible mechanisms can be proposed for the decomposition of a THF peroxide or hydroperoxide to yield alcohols and carbonyl compounds. G. IR analysis of the acetone washing of chloroform washed "bad" soda_ ash and "bad" SAPP showed that the "bad" ash contained a primary amide as its principal component. This amide is absent in the "bad" SAPP and In the acetone blank. Optical microscopy of the filter patches obtained from "good" and "bad" soda ash and "good" and "bad" SAPP showed all the samples contained particulates. The "bad" ash and "bad" SAPP patches contained In addition an oil coating on the fiI ter fibers. These results are summarized in Tables I and II. EXPERIMENTAL A. Black Scale from East MSP Hold Tank An 8.000-g sample of the oily black scale from the east MSP hold tank at the Trenton, Michigan phosphate plant was weighed into a cellulose thimble and successively extracted with 50 ml of increasing polarity solvents using a Soxhlet extraction apparatus. The extraction was continued with each solvent (hexane, chloroform, methanol and tetrahydrofuran) until no color was observed in the liquid in the extractor tube. The Isolated fraction was quantitatively transferred to a 100-ml beaker and evaporated to about 5 ml on a hot plate under a stream of nitrogen. The reduced volume sample was filtered through a 0.2-u cellulose filter and the filtrate and filter washings collected in a 3-dram tared vial. The remaining solvent was stripped under a stream of nitrogen on a hot plate. The isolated fractions were placed in a bell jar and pumped to 0.5 to 1 torr to remove any remaining solvent and then weighed. RSV 0010781 S-75-SS-57 Page Three EXPERIMENTAL (Cont'd) 6. Soda Ash and SAPP (Sodium Acid Pyrophate) 1. Forty to fifty g of "good" and "bad" samples were weighed into a . 25 up X 250 mm chromatography column piggges with glass wool and equipped with a Teflon stopcock. The samples were tightly packed using a mechanical vibrator. Fifty ml of chloroform on the column, the stopcock opened and the solvent allowed to percolate by gravity through the packed sample until the solvent just covered the top of the solids. The eluent from the column was collected in a 25-ml graduated cylinder. The column hold-up. about 30 ml. was determined by subtracting the volume of eluent collected from the 50 ml charged. The collected column eluent was quantitatively transferred from the graduated cylinder to a 250-ml beaker. One hundred mi of fresh chloroform added to the column and the eluent combined with the Initial volume collected. When the level of solvent reached the top of the solids, e volume of inhibitor* free tetrahydrofuran (Burdick and Jackson Laboratories, fnc.) equal to the column hold-up was added to the column. This volume of solvent was allowed to flow through the packed solids until the liquid level reached the top of the solids. The eluent was combined with the other chloroform washes. By this means the chloroform was completed, eluted from the column and the packed sample had been washed with about five column volumes of chloroform. One hundred fifty ml of fresh tetrahydrofuran was allowed to percolate through the sample and collected In a clean 250-ml beaker. Both the chloroform and tetrahydrofuran eluents were filtered through a 0.2-y filter to remove any sample fines that might have washed through the glass wool plug. The solvents were stripped to about a 5~m1 volume under a stream of nitrogen on e hot plate. The concentrated solution was incrementally transferred to a tared 1-dram vial and evaporated to near dryness under a stream of nitrogen on a hot plate. The beakers were washed with several small volumes of presh solvent, the washings transferred to the tared vials and the solvent completely stripped under a nitrogen stream on a hot plate. The vials containing the solvent extracted fractions were placed in a drying oven at 110C for about 10 minutes, placed in a bell jar and pumped at 0.5 to 1 torr, cooled in a deslcator and weighed. 2. The same procedure was used on l*bad" soda ash and "bad" SAPP substituting acetone for tetrahydrofuran. 3. Equipment and solvent blanks were carried using the same glassware used for the samples. REFERENCES Ift spectra 75-368 to 75-385; NNR 16-1101 ss Attachments(2) Monsanto Industrial Chemicals Co. Applied Sciences St. Louts, No. 1/76 - 8. Katlafsky, M. V. Dietrich, D. B. Hines, 0. E. Ktnast, V. J. Lftschgi, 6. W. Nappes, C. Deatherage RSV 0010782 S-75-SS-57 TABLE I BUCK SCALE FROM EAST MSP HOLD TANK EXTRACTION SOLVENT PERCENT EXTRACTED IDENTIFICATION Hexane 19.B Long chain hydrocarbon oil Molecular weight 650 [iR, NHR, GPC (gel permeation chromatography)] Chloroform (5.9) Methanol (2.4) THF (0.2) 8.5 Carboxylic acid plus alcohol or ether Molecular weight 400 to 2000 [|R, NMR, GPC] Left after extraction (Includes H2O) 71*7 (By difference) I RSV 0010783 S-75-SS-57 TABLE II ANALYSES OF SAPP AND WYANDOTTE SODA ASH GOOD SODA ASH 7-14 to 9-1 GOOD SAPP Lot **56 _______ BLANK Hicroscopy of plant fI Iter pads Particulates Particulates CHCU Extract Phthalate Ester 15 ppm Phthalate Ester 2 ppm Phthalate Ester 2 ppm THF Extract -'ter CHCI3) Hydroxy ester* 48 ppm Carboxylic Acid 34 Ppm Ester 2 ppm BAD SODA ASH BAD SAPP 1740 W * -.roxcopy of p lant fiIter P^s CHf U Extract Particulates + oi1 coating on fibers Hydrocarbon ol1 < 2 ppm Particulates + ol 1 coatings on fibers Phthalate Ester 41 ppm Phthalate Ester 2 ppm Extract ,.fter CHCI3) Hydroxy Ester + Polyphosphate Ester*.** 78 ppm Ester + Polyphosphate Ester* 229 ppm Ester 2 ppm A.a tone Extract (after CHCI3) 4 ppm 4 ppm 5 ppm All extracts are Highly colored. * Materiel found may be principally THF decomposition products. ** We cannot completely rule out Inorganic phosphate and organic ester as separate components RSV 0010764 1*% . c* APPENDIX I NIOSH PRIORITY LIST FOR CRITERIA FOR TOXIC SUBSTANCES AND HARMFUL PHYSICAL AGENTS, 1972 Criteria Developed: Carbon Monoxide Noise Heat Stress Beryllium Asbestos Coal Dust1 In Progress: Arsenic Benzene Cadmium and Compounds Chromic Acid Mist Cotton Dust Fibrous Glass Lead Mercury Parathion Silica Trichloroethylene Ultraviolet \ -------------------------------------- . Priorities: Bis (Chloromethyl)Ether Coal Tar Pitch Volatiles 1. 2-Naphthylamine Toluene Diisocyanate Radioactive Products of Uranium Mining (Gaseous and Particulate) Benzidine and Its Salts Carbon Tetrachloride 'According to NIOSH, this criterion was developed in conjunc tion with the Bureau of Mines, Department of the Interior, in implementing the Federal Coal Mine Health and Safety Act of 1969. 65 RSV 0010785 APPENDIX I - 2. Ozone Sulfur Dioxide Tin and Compounds 1- Chromium Compounds Diehlorobenzidine 3. Oxides of Nitrogen Sodium Hydroxide Sulfuric Acid Carbaryl Chloroform 4. 4-Dimethylaminoazobenzene Nitric Acid Toluene Ammonia beta*Propiolactone 5. Epoxy Resins Methylene Chloride 4-Nitrodiphenyl Asphalt Fumes Ethylene Dichloride 6. Fluoride and Hydrogen Fluoride Ploychlorinated Biphenyls Tetrachloreethylene 2-Acetylaminofluorene Chlorobenzene 7. Methylene Bisphenyl Isocyanate (MDI) Phosgene Trichioroethane Acetone 4-Aminodiphenyl 8. Dieldrin Malathion N-Nitrosodimethylamine Aniline Copper and Compounds 9. Cyanides Styrene Zinc and Compounds 66 RSV 0010786 c Chlorine Formaldehyde 10. Manganese and Compounds Phenol Platinum and Compounds Acrolein Aluminum and Compounds 11. Carbon Disulfide Methyl Ethyl Ketone Vinyl Chloride Creosote Methyl Chloride 12. Nickel and Compounds Phosphorus and Compounds Tetrachloroethane Acrylonitrile 2, 4-Dinitrophenol 13* Magnesium and Compounds Methyl Alcohol Paraffin v Ammonium Nitrate Cold Stress 14. Dioxane Fluorine Microwaves Hydrogen Chloride Ethyl Benzene 15. Nitroglycerin Vibration Xylene Methyl Butyl Ketone Mineral Spirits 16. Oil Mists Selenium and Compounds Turpentine r APPENDIX I 4 0 \ A f \ j \ ! , j ! *1 i RSV 0010787 APPENDIX I c Arsine Gasoline 17* Kerosene Iron and Compounds Petroleum Naptha Barotrauma Cresol 18. Paraquat Portland Cement Talc Carbon Black Coherent Energy (Laser Radiation) 19. Ethylene Oxide Impact Noise Proteolytic Enzymes Source: NIOSH. r < \ 68 RSV 0010788