Document JrrGjJoq8oK8RdB7jz3LqNzYr

NATIONAL PETROLEUM REFINERS ASSOCIATION Founded 1902 SUITE 802 1725 DESALES STREET NW WASHINGTON D C 20036 TtLEPHONC >302' 6 3 8-37 22 AT R WRI Gi_EY Oii*eCToR. industrial Relations 8 aPstt TO: FROM: Refinery and Petrochemical Plant Safety Directors NPRA's Fire & Accident Prevention Comnittee Pat R. Wrigley We have enclosed for your information a copy of OSHA's Reconmended Guidelines for Control of Occupational Exposure to Benzene. We have also enclosed a copy of the Department of Labor press release dealing with the Guidelines. 1/13/77 # MCD 000013020 Un.iec Stares Department News of Labor Office of Information Washington, D C. 20210 :ional safety & health ST RAT I ON ;;e After nouns: James Foster '202} 523-31 51 (703) 941-6793 USDL-- 77-37 FOR RELEASE: A.m. EjI'IuNS Friday * Jan. 14, '97 OSHA ISSUES GUIDELINES ON BENZENE EXPOSURE Guidelines that would limit worker exposure to benzene have been issued by the Labor Department's Occupational Safety and Health Administration (OSHA). The guidelines recommend that worker exposure to benzene in the air not exceed an eight-hour time-weighted average concentration of one part per million (ppm) in any eight-hour shift of a 40-hour week. The guidelines, which are not legally binding, call for preventive steps in volving monitoring employee exposure levels, medical surveillance, employee train ing, respiratory protection, protective clothing, good personal hygiene, and fire and safety precautions. OSHA has sent copies of the guidelines to the American Petroleum Institute, Organization Resources Counselors, Inc,, various unions, and the Manufacturers' Chemists Association for dissemination to constituent groups and others. In issuing the guidelines. Assistant Secretary Morton Corn said, "The toxic and flatrmable properties of benzene plus its wide use in industry combine to make it a major occupational health hazard. Voluntary compliance with these nonmandatory guidelines will further the overall objective of 0SHA--to assure safe and healthful working conditions." Or. Corn also noted that the issuance of the guidelines "does not alter our intention to continue enforcing current standards." OSHA's guidelines constitute an interim measure until a revised stanaard for benzene can be promulgated. The guidelines do not supersede, however, OSHA's -MORE- a1' requirements concerninq benzene, r-ier the ^resent standard, the permissible exposure limits to benzene are ^i "':->,our time-weiqnted average concentration of 10 ppm and a ceiling con:entrd''on of 25 ppm except for a maximum peak up to 50 ppm, or whatever limits :e ret by a state agency in a state with an approved safety and health plan. I* employee exposure is in excess of permissible limits, the employer must >T'iemer.t feasible engineering or administrative controls. Such controls must be implemented evon i* they do not completely reduce exposure to permissible limits. Only when all feasible controls have been implemented, and the level of benzene still exceeds permissible limits, may an employer rely on a respiratory protection program. re National Institute for Occupational Safety and Health (NIOSH) announced in August 1976 that available evidence that benzene is leukemogenic is conclusive. NIOSH recommended, therefore, that .'or requlatory purposes benzene be considered carcinogenic in man. Based on available evidence, NIOSH has recommended that the permissible ex posure limit for benzene be lowered to a two-hour time-weighted average concentration of 1 ppm in air. OSHA currently is considering this recownendation. For a single, free copy of the guidelines, write to B.K. Kwon, Room N3603, U.S. Department of Labor, 3rd St. and Constitution Ave., N.W., Washington, D.C. 2 0210. m 00001.3022 MCD 1.*W UWW6.C3 wUtt., ,1, ft. Washington, 0. C. 20036 U S. DEPARTMENT OF LABOR Occupational Safety and Health Administration WASHINGTON. D C 10210 Office of the Assistant Secretary January 4, 1977 Dear Sir: The nature of work ac your establishment indicates to the Occupational Safety and Health Administration (OSHA) that benzene may be used in your operations. As you know, the present permissible exposure limits to benzene are an 8 hour time-weighted average concentration of 10 parts per million (ppm) and a ceiling concentration of 25 ppm except for a maximum peak up to 50 ppm for a maximum duration of 10 minutes in an 8 hour shift, or limits set by a state agency whenever a state administered Occupational Safety and Health Plan is in effect. If the employee expo sure is found to be in excess of the permissible limits, you must implement feasible engineering or administrative controls or maintain an effective respiratory protection program should such controls be found infeasible. The National Institute for Occupational Safety and Health has recommended that the permissible exposure limit for benzene be lowered to a 2 hour time-weighted average concentration of 1 ppm in air. This recommendation is currently being considered by OSHA. As an interim measure until such time as a complete standard is promulgated we are forwarding herewith recommended guidelines for protection of your employees against the risk of disease or injury resulting from exposure to benzene. These recommendations involve preventive steps of monitoring employee exposure levels, medical surveillance, employee training, respi ratory protection, protective clothing, good personal hygiene, and fire and safety precautions which should ensure a reduced health risk for those of your employees who engage in operations Involving benzene. The issuance of these guidelines does not alter our intention to continue our compliance activities. The toxic and flammable properties of benzene plus its wide use in our nation's industries combine to make benzene a major occupational health hazard. Therefore, voluntary compliance with the enclosed nonmandatory guidelines would further the overall objective of the Occupational Safety and Health Act - to assure so far as possible, safe and healthful working conditions. Your cooperation in this matter is greatly appreciated. Protection of erexposure to benzene Is, I am confident, our common Os**/'/ ^ oert M. ConcKlin Deputy Assistant Secretary MCD 000013023 Guidelines_foc_Control_of_Occuoational_Exposure 1 7 W *2 to Benzene Washington, D. C* 2GQob In accordance with the Occuoational Safety and Health Administration's (OSHA) standard for air contaminants (29 CFR 1910.1000,Table Z-2) emoloyee exposure to benzene shall not exceed the oermissible exposure limits of an 3 hour time-weighted average concentration of 10 parts oer million (ppm) and a ceilinq concentration of 25 oom, except for a maximum oeak up to 50 oom for a maximum duration of 10 minutes in an 8 hour shift, or a limit set by a state agency whenever a state administered Occuoational Safety and Health Plan is in effect. The first mandatory requirement is that emoloyee exoosure to benzene above the permissible exposure limits be eliminated through the implementation of feasible engineering controls. Such controls must be implemented even if they do not completely reduce exposure to permissible exoosure limits. After all such controls are implemented and if they do not sufficiently reduce levels of benzene to or below those listed in Table Z-2, each emoloyer must rotate his emoloyees to the extent possible in order to reduce exoosure. Only when all feasible engineering or administrative controls have been implemented, and the level of benzene still exceeds oermissible exoosure limits, may an employer rely on a respirator program pursuant to the mandatory requirements of 1910.134. In addition to 1910.1000 and 1910.134 the foliowinq standards must be met where employees are exposed to benzene: If skin or eye contact with benzene may occur, the require ments of 1910.132 and .133 must be met. Where employees wear protective clothinq, clean change rooms shall be provided in accordance with 1910.141 (e). No employee shall be allowed to consume food or beverages in any area where airborne concentrations of benzene are above the oermissible exposure limits in accordance with 1910.141(g)(2). Inasmuch as benzene is a Class 19 flammable liquid, storage and handling practices must meet the require ments of 1910.106. Locations where benzene may be present in quantities sufficient to oroduce explosive or iqnitable mixtures are considered Class I Group 0 and must conform to the requirements of 1910.309. If there is no standard which addresses a recoqnized hazard, which is likely to cause death or serious physical harm to employees, Section 5(a)(1) of the Act, the general duty clause, may aoply. In August 1976, the National Institute for Occuoational Safety and Health (NIOSH) announced that it considers the accumulated evidence from clinical and eoidemiological data to be conclusive at this time that benzene is leukemogenic. On the basis of this evidence, NIOSH recommended that, for requlatory purooses, benzene be considered carcinogenic in man and that exposure to benzene be lowered to a two hour time-weighted averaqe con centration of 1 ppm in air, as determined by an air sample collected at one liter per minute for two hours. Due to the information supplied by NIOSH, OSHA strongly recommends that exoosure to benzene in air not ex ceed an eight hour time-weighted averaqe concentration of 1 ppm in any eight hour shift of a 40 hour week. -1- MCD C0Q13024 following ecoT'T.^ndat ions ate Pad^ tc ensues that employe exnosu:^ en7.ene if: rontro11ed to a time-weighted average concent r a 11 c n of Hf 'C'-'cr, the mandatory 03FA tequ iretents -cmair. in effect and tc- ^ac. r n r.i'i'SSQ qu ide.'. i nes the mandator'' requirements are identi fy me *?r;' liable h.qiA regulation ?>ch emc'oyer who has a olace of employee:-1 in which benzene is on -.uo-tionaliv produced, reacted, released, packaged, repackaged, q:an?to"t-'vf, stored, handled, c: uced should inspect each workn\ac* '-rd work 'Donation to determine if any employee may be exnosed to benzene at or *bove * time-weighted average concentration of ' of' ' r '.o repeated skin contact with .liquid benzen. As soon *s n -.rets of benzene- oxoor.u;^ have been identified, the employe a'-culd l irv t as much as possible the number of people entering `these areas. Indicators that an evaluation of employee exposure shcul'*' be indot* aken would include: ' 'i . .1:' (iv; Ar-v j.r.formation or observations which would indicate empln/0~ cynosure to benzene; Ar.v measurement of airborne concentrations of benzene cbove - . ime-we i ch ced average concentration of 1 ppm. -nv e^tloyoe complaints of symptoms which may be attributable euconu'e to benzene? and Any ^reduction, process, -,r control change which may result in or increare in the airborne concentration of benzene, or '''env'e'- th--' omoloyer has ary other reason tc suspect an in crease in the airborne concentrations of benzene. Air Monitoring {:.) ill, Emtd.o';?^ exposure measurements should represent the actual brnathina 'ore exposure conditions for each employee. Any appropriate combination of iona-teem or short-term samples * ho acceptable, but tctal sampling time should not be less than ? hours ihen det:rrining the time-weighted average of employees '.c-.u;:a-;v of Pc-asut -.merit. ?ht method of non itoring and ans.vris should have no accuracy, tc a confidence level of 95%, o.` not lass than olu o~ minus 15* for concentrations of benzene eoual to c-: rr".;^r than r. time-weighted average concent: - - . ' of 1 opm (One method of analysis meeting this accuracT reou.r mart is available in the VT'~SK Manual of Anal^ticaJL -Sothodf^ :tp* rn*?en t ? ; ir.t' r'"; Office .took v ->, lfq3-w':04t3 . For pc*** ir.ir.ary c*nge finding tests, PIOSH certified detector * o: + * v'itl'i &n accuracy of olus or minus 15% nay be used. -2 HCD 000013025 (iii) Freauencv of Monitoring. where the employer has detert i nee that employees are exoosed to benzene in excess of a timeweighted averaae concen t r a t ion of 1 com, nonitorno should ce reoeated quarterly. If OLoioaical monitoring is done, it should be scheduled to coincide with air monitoring. 2. MEDICAL SURVEILLANCE Each emDlover should institute a medical surveillance oroqram for all em ployees who are or will be exoosed to oenzene above a time-weighted averaae concentration of 1 pom. The employer should orovide each emolovee with an oooortunity for medical examination, oerformed by or under the supervision of a licensed physician, durinq the emolovee's normal workina hours or at soecifically assigned hours designated on the oasis of Physician avail ability, without cost to the employee. a. Medical Examination (i) Each employer should orovide a medical examination which in cludes a complete medical history and Physical examination, a complete blood count, urinary phenol evaluation, and serum bilirubin evaluation to each employee exposed to benzene in excess of a time-weighted average concentration of 1 oom. (a) A complete history should include oast work exposures to benzene or any other hematoloaic toxins, a history of blood dyscrasias including genetically related hemo globin alterations, bleeding abnormalities, abnormal function of formed blood elements, a history of renal or liver disfunction, alcoholic intake and systemic infec tions . (b) A complete blood count should include: hematocrit, hemo globin determination, mean corpuscular volume, white blood cell count includinq a differential count, and a platelet estimation of the differential slide. {ii5 Medical examinations should also be made available: (a) To employees prior to their assignment to areas in which airborne concentrations of benzene are above a time-weiahted average concentration of 1 ppm; (b) At least biannually for each employee exposed to airborne concentrations of benzene above a time-weighted average concentration of 1 ppm at any time durina the Drecedina six months; < c) Immediately, upon notification by the employee that the employee has developed signs or symptoms commonly associ ated with chronic exposure to benzene. (d) At least monthly for each employee who shows alterations in components of the blood. This schedule should continue for at least three months or until there is evidence of a return to normal values. 3- - MCD 000013026 i Where medical examinations are oerformed, the employer should provide the examining physician with the following information: (a) The reason for the medical examination requested; (o) A description of the affected employee's duties as they relate to the employee's exoosure; (c) A description of any personal protective eauipment used or to be used; (d) The results of the employee's exposure measurements, if available; (e) The employee's anticipated or estimated exposure level; (f) Upon request of the physician/ information concerning previous medical examination of the affected employee. Biological Monitorinq. Biological monitoring should be scheduled to coincide with air monitoring. By so doing, the route of entry and/or the source of exposure to benzene may be indicated if not already aoparent. fi) Recommended Method Urinary phenol analysis should be the method of biological monitoring used. According to presently available literature, the urinary ohenol evaluation is a method to determine dose when exoosure to benzene is in the range of a time-weighted average concentration of 10 ppm or greater. Since the liter ature supporting this opinion is limited, OSHA also recommends the use of this method where exposure levels are in excess of a time-weighted average concentration of 1 oom. Data generated by such testinq may clarify the effectiveness of the urinarv ohenol evaluation as an indicator of exposure to benzene. A method of analysis for phenol in urine is described in the Annals of Occupational Hygiene, 1970, Volume 13, po. 125-146. An automated method which determines total phenol in urine and allows for the analysis of a large number of samples per day is described in the American Industrial Hygiene Association Joujrnal, June 1972, pp. J78-38I" For the analysis, 100 milliliters of urine having a specific gravity of at least 1.010 should be collected as close to the end of the working day as possible. For the best assessment of the work related absorption of benzene, the following factors should be considered since they can contribute to a high urine phenol level: (a) The foods or beverages consumed which are likely to increase the total bodily production of phenol, such as but not limited to foods or beverages of the grape family. (b) Any medications or drugs, especially phenobarbital, taken with in the previous 24 hour period. (c) Non-work related exposures to benzene which occurred within the previous 24 hour period. (d) Recent exposure to biphenyls. -4- MCI> 000013027 'u) Frequency of Monitoring (a) If possible, a urine samole should be obtained of all emoiovees prior to assignment to areas where benzene in air concentrations exceed a time-weighted average concentration of 1 opm. io) For employees exoosed to more than a time-weighted average con centration of benzene in air of 1 opm, urine sampling and anal ysis should be done every three months. ,c) Each enolovee whose urinary Phenol level exceeds 75 milligrams oer liter should be provided, within one wee* of the receipt of the results, with two follow-up urinary phenol evaluations per formed on two samples taken on the same day* one as close to the beginning and one as close to the end of the working day as oossiole. If the oriqmal elevated finding is confirmed and aooear to be due to occupational exposure to benzene, the employee's x oosure to benzene should be reduced. (d) Each employee whose urinary Phenol level exceeds 75 milligrams per liter should be examined by a physician as soon as oracticac after such absorption is demonstrated and confirmed, and at leas monthly thereafter or more frequently as deemed necessary by tee physician until the urinary phenol levels have returned to below 75 milligrams per liter. lii) Elevated Group Levels (a) The results of employee urine samolinq should also be consider ed as a grouo exposure by area of assignment and/or by job de scription. Elevated group urinary phenol levels should be a cause for review of ooerational practices, process controls, and a change in either or both to reduce employee exposure. (o) If several employee urine samples from the same area of assign ment indicate excessive urinary phenol levels, corrective ar:zi^r in the area should be started by the employer immediately. Physician's Written Opinion (i) The employer should obtain and furnish the employee with a writt** opinion from the examining physician containing the following: (a) The signs or symptoms of benzene exposure manifested by the employee, if any? (b) The physician's opinion as to whether the employee has any detected medical condition which would place the employee's health at increased risk of impairment from exposure to benzene or other substances or which would directly or in directly aggravate any detected medical condition? (c) Any recommended limitation upon the employee's exposure to benzene or other substances or upon the use of personal protective equipment and respirators? and (d) A statement that any medical condition which has been dis covered as a result of the examination has been called to the employee's attention for further examination or treatme-* (ii) The written opinion obtained by the employer should not reveal specific findings or diagnoses unrelated to occupational exposer# to benzene or other substances. -5- 000013028 MCD ( i) if the emoloyer determines, on the basis of the ohvsician's written opinion, that any emplovee's health would be materi ally impaired bv maintaining the existing exposure to benzene or other substances, the employer should Diace specific limi tations, based on the ohysician's written ooinion, on the emDloyee's continued exposure to benzene or other substances. TRAINING a. Each employer should orovide a training orogram for employees assiqned to workplace areas where benzene is produced, reacted, re leased, packaged, repackaged, transported, stored, handled, or used. d. The training program should be provided at the time of initial as signment and at least annually thereafter, c. The employer should: (i) (ii) (iii) (iv) (v) (vi) (vii) (viii) fix) Inform employees who work or will be working with benzene of potential health hazards? Advise employees of the signs and symtoms of exposure to benzene described in the appendix and instruct employees to advise the employer of the development of such signs or symptoms. Inform employees of the specific nature of operations which could result in exposure to benzene above a time-weighted average concentration of 1 ppm, as well as safe work practices where benzene is produced, reacted, released, packaged, repackaged, transported, stored, handled or used? Instruct employees in proper housekeeping practices? Inform employees of the correct emergency procedures to be fol lowed in case of spills, leaks, or fire, and the personal pro tective eguipment necessary in emergencies? Inform employees of measures necessary to protect them from exposures in excess of the permissible exposure limit. The wearing and turning in of protective clothing should be stressed; Instruct employees as to the purpose of respirators. Provide employees with a description of and explain the puroose for the medical surveillance orogram; Inform employees where written procedures and hazard information are available on the premises. d. Pursuant to 1910.134(b)(3) the users of respirators shall be trained in their proper use and limitations. . RESPIRATORY PROTECTION a. Respiratory Protection Program. Engineering controls shall be used to maintain employee exposure to benzene within the per missible exposure limits in Table Z-2. (1910.1000(e)) while engineering controls are being implemented or when employee exposure to airborne concentrations of benzene cannot be fully reduced by feasible engineering or administrative controls, an employer shall utilize a orogram of respiratory protection to protect every employee exposed. (1910.134(a) and 1910.1000(e)) -6- MCD 00001302S b. Respirator Selection and Usage (i) When respirators are used their use shall comply with the requirements of 1910.134. (1910.1000(e)) Only those re spiratory protective devices which have been approved by the Bureau of Mines, the Mining Enforcement and Safety Administration or the National Institute for Occupational Safety and Health under the provisions of 30 CFR Part 11 snail be used. (1910.134{b)(11) ) (i i > The employer should select and provide an appropriate respirator from the table on the next page. (iii) A respirator specified for use in higher concentrations of airborne benzene may be used in atmospheres of lower concentrations . (iv) Employees experiencing freauent or continuous breathing dif ficulty while using respirators should be evaluated by a phy sician to determine the ability of the worker to wear a re spirator . (v) Employees who wear respirators in a hot environment should be allowed to leave work areas to wash the face and respirator facepiece to prevent potential skin irritation associated with respirator use. (vi) When employees are exposed to other toxic substances in addition to benzene, appropriate combinations of respi ratory protection shall be provided. (1910.134(b)(2)) c. There should be an established in-plant procedure and means and facilities provided to issue respiratory protective equipment, to return used, contaminated equipment, to decontaminate and disin fect the equipment, and to repair or exchange damaqed equipment. PROTECTIVE CLOTHING a. Employers shall provide and require employees to wear protective clothing and gloves, or any other appropriate protective equip ment deemed necessary to prevent skin contact from repeated spills, splashes, or sprays of liquid benzene. (1910.132(a)) It is recommended that such equipment be imoervious to benzene. b. The employer shall provide and require employees to use splash proof safety goggles where eye contact with benzene sprays or splashes may occur. (1910.133(a)(1)) c. The employer should provide and require employees to use full length face shields (eight inch minimum) where the employee's face may be splashed with liquid benzene. d. Employers should ensure that any permeable clothing heavily con taminated with benzene be removed immediately and not reworn until the benzene is removed from the clothing. e. The employer should launder, maintain, and/or dispose of all heavily contaminated protective clothing or heavily contaminated personal clothing discarded by employees. -7- MCD 000013030 'ECT'IMENDATICNS EOR RESPIRATOR USAGE AT BENZENE CONCENTRATIONS GREATER THAN 1 PPM r ;'.'-?`,trat:on of Benzene or Condition of Use Less than or equal to 10 ppm Less than or equal to 50 ppm Less than or equal to 1000 ppm Less than or equal to 2000 opm Less than or equal to 10,000 ppm Entry into unknown concentrations or Fire Fighting Escape Only Respirator Type (1) Chemical cartridge respirator with organic vapor cartridges and half mask. (2) Any supplied air respirator with half mask. (1) Chemical cartridge resoirator with organic vapor cartridges and full facepiece. (2) Any supplied air respirator with full facepiece. {3} Any organic vapor gas mask. (4) Any self-contained breathing apparatus with full facepiece (1) Supplied air respirator with half mask in positive pressure mode. (1) Supplied air respirator with full facepiece helmet or hood in positive pressure mode. (1) Supplied air respirator and auxiliary self-contained breathing apparatus with full facepiece in positive pressure mode. (2) Open circuit self-contained breathing apparatus with full facepiece in positive pressure mode. (1) Open circuit self-contained breathing apparatus with full facepiece in positive pressure mode. (1) Any organic vapor gas mask. (2) Any self-contained breathing apparatus with full facepiece. MCD 000013031 6. PERSONAL HYGIENE FACILITIES AND PRACTICES a. All food, beverages, tobacco products, and unapplied cosmetics should be orohibited in areas where airborne concentrations of benzene are above a time-weighted average concentration of 1 pom. 0. Wnere the eyes of an employee may be exposed to liquid benzene, suitable eauipment for drenching or flushing the eyes with water should be provided in the immediate work area for emergency use. c. The emoloyer should ensure that an employee whose face or extre mities become wet with liquid benzene promptly washes to remove any oenzene from the skin. d. Where the body (other than face or extremities) of an emoloyee may become wet with liquid benzene, the employer should provide showers. e. When feasible, an eyewash fountain and emergency shower should oe available in the same location for emergency use. f. Where employees wear protective clothing, clean change rooms shall be provided in accordance with 1910.141(e). 7. FIRE AND SAFETY a. Liouid benzene is classified as a Class IB flammable liquid and its vapor may form explosive mixtures in air. Sources of ignition such as smoking or ooen flames shall be prohibited where benzene is used or stored. (1910.106(b),(d),{e),(f),(g) and (h)) b. Benzene should be stored in tightly closed containers in a cool area. c. Benzene storage areas shall be well ventilated. (1910.106(b), (d ) ,(e ) , and (f)) d. Benzene containers should be grounded prior to opening. e. Benzene containers shall be electrically interconnected to the receiving container prior to pouring. (1910.106{e),(f), and (h)) f. Non-sparking tools shall be used when opening or closing benzene containers. (1910.106(b),(e), and (h)) g. High exposures to benzene can occur when transferring the liquid from one container to another. Such operations shall be well ventilated (1910.106(f)) and good work practices should be estab lished to avoid soilis. h. Spills of benzene should be cleaned up immediately after eliminating potential sources of ignition and providing available ventilation. 1. Large amounts of water should be used to flush the areas where spills have occurred. j. Liquid benzene shall not be allowed to enter a confined space such as a public sewer, because of the possibility of explosion. (1910.106(b),(e),(f),(g) and (h)) Sewers designed for chemical waste are permitted. k. Large volumes of benzene should be disposed of by atomizing it in a suitable combustion chamber or by absorbing it in dry sand or earth and disposing it in a sanitary land fill. l. Rags contaminated with benzene should be temporarily stored in tightly closed containers. m. The local fire department should be informed of the exact location of the storage areas and the hazards in case of fire. -9- MCD 000013032 - , S-'.-ATIONS j. A written plan for emergency sit; aticns should oe developed :'or eacn operation wnere mere is a possibility of a passive release of oenzene or where extensive skin contact may occur. b. The plan should require: (i) (ii) (iii) (iv) {v) (vi) Employees engaged in correcting emergency conditions to be provided with the aoprooriate protective cloth ing and resoiratory protective devices. Employees not engaged in correcting the emergency to be restricted from the area, and normal operations in the affected area(s) not to be resumed until the emergency is abated. A local alarm system to be installed and maintained to promptly alert employees that an emergency situation exists. Equipment for quick drenchina or flushing be avail able for employees who have splashed benzene in their eyes. Employees who have had a large amount of benzene spilled on their clothing or skin to remove any contaminated clothing and to immediately wash the exposed skin with large amounts of soap and water. Contaminated clothing should be washed before wearing again. Employees who have inhaled benzene at high concentra tions to be removed at once to fresh air. If breathing has stopped, artificial respiration or oxygen should be used, if indicated. -10- MCD 000013033 APPENDIX CHARACTERISTICS Of BENZENE I. PnysiCdl and Chemical Data A. Synonyms: Benzol, benzole, coal naptna, cyclonexdttlene, pnene, pnenyl nyaiide, pyrobenzol. (Benzin, petroleum oenzin, ana benzine do not contain benzene). B . Formula: nr u. Appearance dna oaoi ; Benzene is <a clear, colorless liquid with a pleasant, sweet oaot. The odor of benzene does not proviae adequate warning of its hazard. 0. Boiling Point: (760 mm Hg) : 8Q.1*C t. Melting Point: 5.5~C (42rF) fr. Specific Gravity (water*l): 0.879 u. vapor Density (air*l): 2.7 ti. Vapor Pressure at 2Q*C (68*F): 75 mm Hg 1. Solubility in Water: .06% - .08% J. Evaporation Rate (ethet*l); 2.8 II. Fire ana Explosion Hazard Data A. Flash Point (closed cup): -11C (12F) B. Autoignition Temperature: 580C (1Q76GF) C. Flammable Limits in Air, % by Volume: Lower: 1.3% Upper: 7.1% 0. Benzene is classified as a class IS flammable liquid for the purpose of conforming to the requirements of 29 CFR 1910.106. Class 13 includes liquids having a flashpoint oelow 73"F (22.8~C) and having a boiling point at or above 100`F (37.8"C). E. A benzene concentration exceeding 3250 ppm is considered a potential fire or explosion hazard. Benzene vapors are heavier than air; thus the vapors may travel along the ground and be ignited by open flames or sparks at locations remote from the site at which benzene is handled. Locations where benzene may be present in quantities sufficient to produce explosive or ignitable mixtures are considered Class I Group D for the purposes of conforming to the requirements of 29 CFR 1910.309. MCD 000013034 seoeioooo aow * pu: uiTqoiA qq Axsqpunqxn pup ssussxuqp iq Aq pT updujooop - ' uq ui ssuqq6xq 30 uonpsues p q /.pui 3qx *o6TqiA 10 #'ri3P3 'uoTSSsidap 30 poxid p Aa pMoxxog 'S5utpdt> io/dup 'uoTqpqTDX snoAidu ' uot q p 3 T 7 t qx e Aq pz T 3 q dp 3 p qo uisqsAs "?ai9u 7ps3ud qq uo qosgge Aioqpxnunqs XPiqTUT up apu Apid *insodx qnop) uzuq 30 suoxqpiquaouoo qbxq 30 uoTqpxPUuj A7DT dp i 6ut ia -or'! 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Tp^TboxoTp *p obdto/.p c ssxuquou cxnoqs qopquoo utxs 'uot3ptpuut pta U0T3C3OSOP 03 D 3 P d UI 0 0 7 P UJ T U T U.' ST UTXS U3 PTA UCT3C10SCP urcu3Tv 'uoTqdToscP utxs pup UOT3PJPUUT j/iqu'? 30 qnoy *v pqpn r 3 P 2 P H U 3 T P P TOCO STSUTF3U00 PSSOdx 0TT3 dSSV 03 DOSn O UPC /.PICS 103"'- ` 1 ' 1 T0TCS OUP 1 3 3 P O S t 7 T W IL'P913S OUTS 7S3PW 30 '.rTijs r'j Tns s r 30 v o c t ? 91 r. o?r o i <? 5ut3':6t - i t 3 7 p' 0 c f *r> r. ' - ic 3 r 7 1 - ' DOT y C~ o : " 3 '3 V 6u ' V ' ' ''O jr 7 lose consciousness. Convulsions ana tiemois occui riequenii/, ana ueatn may follow from cespuacoLy paralysis ol circulatory collapse in a few minutes to several r.outs following severe exposuies. Prolonged exposuie to small quantities of oer.zene vapoc (cmonic exposuie) is of extLeme importance cue to the uieveisiDle effects on tne olood-fotmmg system. Tne development of sucn effects is msiaious as tney nave ceen notea to occui at concent! ations of oenzene wmcn may not cause irritation of mucous memoianes or any unpleasant sensory effects. barly signs ana symptoms of oenzene moroidity ace varied, vague, ana not specific fot Denzene exposure. Suojective complaints of neaaache, dizziness, and loss of appetite may pieceae or accompany clinical symptomatology. Bleeaing from tne nose, gums, oc mucous memoianes and tne aevelopment of puipuric spots may occur as the condition progresses. Rapid pulse and low olooa pressure in audition to a pnysical appearance of anemia may accompany a subjective complaint of snottness of oreatn. Clinical evidence of leucopenia ana anemia are the most common abnotmalities reportea, noweverf macrocytosis ana thromoocytopenia are also frequently present. The bone marrow may appear normal, aplastic, or hyperplastic ana may not in all situations correlate with peripheral oloou finaings maicating hypo- oc hyper-activity of blood forming tissues, inete are great variations in the susceptibility to benzene morbidity which prohibit the identification of a typical" olooa picture. The effects of piolongea benzene exposure may appear several weeks or years after tne actual exposure n'as ceased . MCI) 0013036 RECOMMENDED METHOD OF 3IOLOGICAL MONITORING The cecommended method of biological monitoring is a urine analysis to determine the concentration of phenol and its conjugates, sulfate and I ucucon ide , in urine. It also determines orthocresol and meta and pardcresols. Urine is hydrolyzed with perchloric acid at 95^C, and the phenols and cresols are extracted with isopropyl ether and deternned by gas chromatography. I. Collection of urine samples '`Spot" urine specimens of about 100 milliters (ml) are collec ted as close to the end of the workday as possible. After thoroughly washing their hands with soap and water, wor kers should collect urine samples from single voidings in clean, dry specimen containers having tight closures and at least a 120 ml capa city. Collection containers may be glass, wax-coated paper, or other disposable types if desired. Following collection of urine specimens, 1 ml of a 10% copper sulfate solution is added to each sample as a preservative and samples ace immediately stored under refrigeration, preferably at 0-4 *C. Refrigerated specimens will remain stable for approximately 90 days. If shipment of samples is necessary to perform analysis, the most rapid method available shall be employed utilizing acceptable packing procedures as specified by the carrier. Proper identification of each specimen shall include as a minimum, the worker's name, date, and time of collection. II. Analytical A* Principle of the Method Urine samples are treated with perchloric acid at 95C to hy drolyze the phenol conjugates, phenyl sulfate and phenyl glucuronide, formed as detoxification products following ben zene absorption. The total phenol is extracted with diiso propyl ether and the phenol concentration is determined by gas chromatographic analysis of the diisopropyl ether extract B. Apparatus 1. Gas chromatograph with a flame ionization detector and equipped with a 5 foot x 3/16 inch column packed with 2% w/w polyethylene-glycol adipate on Universal "8" support. Operating conditions are as follows: Column temperature 150*C Detector. Flame ionization, 250*C Injection point temperature 200*C Carrier gas Nitrogen Carrier gas flowrate 60 ml/min MOD OOOOJ3Q37 2. Water bath at 9 5aC. 3. Glass-scoppered , 10 ml volumetric flasxs 4. L ml, 2 ml# and 5 ml volumetric pipets 5. 5 microliter (ul) syringe C . Rea 2e n t^s 1 . Pheno1 2. 15% Perchloric acid ( Perchloric acid can probably be replaced with hydrochloric acid. The use of perchloric acid should be avoided if at all possible.) 3. Diisopropyl ether 4. Distilled water D. Procedure 1. Hydrolysis of phenol conjugates Pipet 5 ml of urine into a 10 ml, volumetric flask. Add 2 ml perchloric acid, mix by swirling, and transfer the lightly stoppered flask to a water bath at 95*C. After 2 hours remove the flask and allow to cool at room temperatur e. 2. Diisopropyl ether extraction of phenol and cresols Pipet 1 ml of diisoptopyl ether into the flask and adjust the volume to 10 ml with distilled water. Shake vigorously for one minute to extract the phenol and cresols. Allow the aqueous and ether layers to separate. 3. Gas chromatographic analysis for phenol Inject 5 microliters (ul) of the diisoptopyl ether layer into the gas chromatograph and record the attenuation and area of the phenol peak. Under the conditions described, phenol is eluted in 100 seconds, o-cresol in 130 seconds, and m- and p- cresols in 320 seconds. E. standards Preparation A 50 mg/liter standard aqueous solution of phenol is prepared. A 5 ml aliauot of the standard solution is then subjected to the hydrolysis, extraction, and gas chromatographic analysis descr ibed above. MOD nocG13038 f. Calculations DetenTune tne pnenol concenti ation m tne mine oy compai mg me gas cht omatog i apn ic pea* aiea of tne sample witn tnat of tne 5u mg/licet standaia ana adjust tne value to a specific gtavity of 1.024. u. ogecitic^iayity Collection uue to tne magnitude of collection lequiiea, samples navmg specinc giavities less tnan l.ulO snoulo oe lejectea ana anotnei sample ODtainec. Collected Concenctation OoseL_yeu Concenti at ion x 24 Lait-2-aigIts of sp gc (eg 1.021) Refeience: Snetwooa, k.J. ana r.w.G. Caitei. me i-ieasuiement of Occupational Exposuie to Benzene Vapoui. Ann. occup. hyg. , vol. 13, pp. 125-146 , 1970 5PO 13*033 000013039 MCD