USAF OEHL REPORT 83-213EH0Jf7GFB

BACKGROUND LEVELS OF HYDRAZINE, UDMH, AND NDMA

AT TITAN II COMPLEXES

DAVIS-MONTHAN AFB/ ARIZONA

JULY 1983

USAF Occupational and Environmental Health Laboratory Aerospace Medical Division (AFSC) Brooks Air Force BaseTexas 78235

20091020316

UNCLASSIFIED

SECURITY CLASSIFICATION OF THIS PAGE (When Data^Entered)^

REPORT DOCUMENTATION PAGE READ INSTRUCTIONS BEFORE COMPLETING FORM

t. REPORT NUMBER

83-213EH047GFB

2. GOVT ACCESSION NO 3. RECIPIENT'S CATALOG NUMBER

4. TITLE (and Subtitle)

Background Levels of Hydrazine, UDMH, and NDMA at Titan II Complexes Davis-Monthan AFB, Arizona

5. TYPE OF REPORT a PERIOD COVERED

FINAL 4 Nov 82-8 Apr 83 6. PERFORMING OIG. REPORT NUMBER

7. AUTHORfs,)

Edward C. Bishop, Captain, USAF, BSC

B. CONTRACT OR GRANT NUMBERS

9. PERFORMING ORGANIZATION NAME AND ADDRESS

DSAF Occupational and Environmental Health Laboratory, Brooks AFB TX 78235

10. PROGRAM ELEMENT. PROJECT, TASK AREA a WORK UNIT NUMBERS

II. CONTROLLING OFFICE NAME AND ADDRESS

HQ SAC/SGPB Offutt AFB NE 68113

12. REPORT DATE

July 1983 13. NUMBER OF PAGES

27 14. MONITORING AGENCY NAME & ADDRESSfi/ different from Controlling Oflice) 15. SECURITY CLASS, (ol this report)

UNCLASSIFIED 15s. DECLASSIFICATION DOWNGRADING

SCHEDULE

16. DISTRIBUTION ST AT EM EN T (ol this Report)

8/4/98: Approved for public releasel;! , distribution unlimited.

17. DISTRIBUTION STATEMENT (ol the abstract entered In Block 20, il dillerent from Report)

18. SUPPLEMENTARY NOTES

19. KEY WORDS (Continue on reverse side if necessary and identity by block number)

Hydraz ine UDMH NDMA

background levels Titan II

20. ABSTRACT (Continue on reverse side If necessary and Identify by block number)

This survey evaluated potential exposure levels of hydrazine, UDMH and NDMA during normal Titan II alert operations.

DD I JAN 73 1473 EDITION OF 1 NOV 65 IS OBSOLETE UNCLASSIFIED SECURITY CLASSIFICATION OF THIS PAGE (When Data Knlerail)

Report No. 83-213EH047GFB

DSAF OCCUPATIONAL AND ENVIRONMENTAL

HEALTH LABORATORY

Brooks AFB, Texas 78235

BACKGROUND LEVELS OF HYDRAZINE, UDMH, AND NDMA

AT TITAN II COMPLEXES

DAVIS-MONTHAN AFB, ARIZONA

JULY 1983

Prepared by:

EDWARD C. BISHOP, Captain, TJSAF, BSC Consultant, Industrial Hygiene Engineer

Reviewed by:

(JC^~ +-tL c^*-«.-c -**-

ARTHUR P. CALDWELL, Col, USAF, BSC Chief, Consultant Services Division

Approved by:

JOHAN E. BAYER, Colonel, USAF, BSC Vice Commander

TABLE OF CONTENTS

Page

List of Tables ii

I. INTRODUCTION 1

II. AIR SAMPLING AND ANALYSIS 1

II. EXPOSURE STANDARDS 2

TV. RESULTS AND DISCUSSION 2

V. CONCLUSIONS 3

VI. RECOMMENDATIONS 3

REFERENCES 5

APPENDIX A 7

Distribution 6

LIST OF TABLES

Table Page

I Sample Dates 3

II Sample Result Summary, NPT Cone., ug/ms, Bydrazine/UDMH/NDMA 4

ii

I. INTRODUCTION

A. Background and Purpose:

The USAF Hospital Davis Monthan, Bioenvironmental Engineering Services, Davis-Monthan AFB (USAF Hospital DM/SGPB) performed sampling for hydrazine, unsymmetrical dimethyl hydrazine (UDMH), and nitrosodimethylamine (NDMA) at five active Titan II complexes. These surveys were performed during the period 4 November 1982 through 8 April 1983 at the request of Headquarters Strategic Air Command, Bioenvironmental Engineering Division (HQ SAC/SGPB). The purpose of these surveys was to determine background levels of hydrazine, UDMH and NDMA at typical Titan II complexes in alert status for comparison with results reported during deactivation fuel propellant download operations.

B. USAF Hospital DM/SGPB Survey Personnel:

1. Maj Robert J. Sutay, Certified Industrial Hygienist

2. Capt Arnold R. Ferguson, Bioenvironmental Engineer

3. SSgt James B. Heggie, Bioenvironmental Engineering Technician

II. AIR SAMPLING AND ANALTSIS

A. Sampling and Analysis Techniques

1. Hydrazine/UDMH

Area and personal samples for hydrazine and UDMH were collected using Gas Chrom RR (30/60 mesh) (firebrick) sampling tubes with P200, P200A, P2S00, or P2S00A DuPont pumps with flow rates ranging from .2 to 2.0 Lpm. Analysis of firebrick tubes was performed by the USAF Occupational and Environmental Health Laboratory, Analytical Services Division (USAF OEHL/SA). After desorption with deionized water, the samples were split and analyzed separately by colorimetric determination for UDMH and hydrazine.

2. NDMA

R Area and personal samples were collected using Thermosorb/N

adsorption media purchased from Thermo Electron Corporation, Waltham MA, with P200, P200A, P2500, and P2500A DuPont pumps at flow rates of .2 to 2.0 Lpm. Samples were analyzed by the National Institute for Occupational Safety and Health (NIOSH), Cincinnati OH. The adsorption media was desorbed with metha- nol and dichloromethane (25%/75%) and analyses were accomplished by gas chro- matography with detection of NDMA by a Thermal Energy Analyzer (TEA). Pres- ence of NDMA was confirmed by gas chromatography/mass spectroscopy (GC/MS).

III. EXPOSURE STANDARDS

The following standards apply to this survey.

A. Hydrazine

AFOSH Standard 161-13, Hydrazine1, establishes the permissible expo- sure limit (PEL) of .1 mg/m* (100 ug/m*). Hydrazine is also an industrial substance suspect of carcinogenic potential for man and skin absorption can be a significant route of exposure.1

B. UDMH

The current American Conference of Governmental Industrial Hygienists (ACGIH) Threshold Limit Values (TLVR) are incorporated into AFOSH Standard 161-8, Permissible Exposure Limits for Chemical Substances.4 UDMH has an assigned TLV of 1.0 mg/m» (1000 ug/m») and also has "skin" and A2 notations,1

indicating UDMH is an industrial substance suspect of carcinogenic potential for man and skin absorption can be a significant route of exposure.

C. NDMA

NDMA produces tumors in laboratory animals and is covered by AFOSH Standard 161-3, Carcinogenic Substances* and 29 CFR 1910.1016, N-nitrosodi- methylamine.* These regulations specifically apply to mixtures which contain greater than 1% NDMA by weight in the solid or liquid. USAF UDMH and 50/50 mixture analyzed to date contained significantly less than 1% NDMA. However, NDMA may be formed by oxidation of UDMH in air, and due to its potent animal carcinogenicity, human exposures must be lowered as much as possible. NDMA does not have an assigned TLV but does have "skin" and A2 notations.1

IV. RESULTS AND DISCUSSION

A. General

Sample results are presented in Tables A-I through A-V in Appendix A. The NPT CONC column in the tables is the concentration in micrograms per cubic meter measured during the sample period adjusted to 25°C, 760 mm Hg (normal pressure and temperature). The TWA CONC column is the concentration time- weighted over 8 hours adjusted to 25°C, 760 mm Hg, assuming no exposure for the unsampled period. Comparisons with previous download surveys are based upon the NPT rather than TWA concentrations to eliminate sampling duration differences. The results with < symbols associated with nondetected (ND) samples indicate the minimum concentration which could have been measured under the sampled conditions.

B. Background Levels

The complexes and dates sampling was performed are presented in Table I and the sample results are summarized in Table II.

TABLE I

Sample Dates

Site Date

570-1 570-4 570-6 571-4 571-9

15 Feb 83 8 Apr 83

27 Jan 83 26 Jan 83 4 Nov 82

1. Hydrazine and UDMH

Hydrazine and UDMH levels measured did not exceed 1% and 10% 8-hour PEL levels respectively. However, many of the UDMH values could be false positives associated with the analytical method.

2. NDMA

NDMA was detect an average concentration of measured. It was also dete plexes at average concentra (0.06 ppb) respectively for at complex 570-1 on the P-5 ppb) and in the launch duct complex 571-9 at levels of respectively.

ed at the silo exhaust at four complexes with 0.62 ug/m1 (0.20 ppb) for all five complexes cted at the "W" and the MSA platform at two com- tions of 0.30 ug/m* (0.10 ppb) and 0.18 ug/m» all complexes measured. NDMA was also detected platform at a concentration of 0.24 ug/m* (0.08 on Level 8 and the equipment area on Level 2 of

0.35 ug/m» (0.12 ppb) and 0.12 ug/m» (0.04 ppb)

Y. CONCLUSIONS

A. UDMH and hydrazine are not significant health hazards based upon current exposure standards.

B. NDMA was not detected in the LCC.

C. NDMA, while present at some locations in the silo area at sub parts per billion concentrations, is not a significant health hazard due to the low levels measured and the limited time spent in the silo by crewmembers (less than 2 hr/alert). This was further confirmed by the lack of NDMA detected on personal samplers worn by crewmembers.

VI. RECOMMENDATIONS

A. Inform missile crewmembers of the presence of NDMA and possible health hazards similar to information briefed to Propellant Transfer System (PTS) personnel.

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References

n 1. American Conference of Governmental Industrial Hygienists. (1982) TLVs ,

Threshold Limit Values for Chemical Substances .aid. Physical Agents in Hie. Workplace Environment with Intended Changes for 1982. ACGIH, Cincinnati OH.

2. AFOSH Standard 161-3, Carcinogenic Substances, 20 Jun 1977.

3. AFOSH Standard 161-13, Occupational Health Exposure to Hydazine, 26 Dec 79.

4. AFOSH Standard 161-8, Permissible Exposure Limits for Chemical Substances, 20 Jun 78.

5. Code of Federal Regulations, 29 CFR 1910, Nitrosodimethylamine.

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