Special provisions for air contional Safety and Health, U.S. Depart-

(iii) A brief description of each proctaminants. ment of Labor, or designee. ess or operation which results in em- "Authorized person" means any ployee exposure to AN in regulated person specifically authorized by the areas; and employer whose duties require the (iv) The number of employees en- (c) Acrylonitrile. Section 1910.1045 person to enter a regulated area, or gaged in each process or operation shall apply to the exposure of every employee to acrylonitrile in every emany person entering such an area as a within each regulated area which reployment and place of employment designated representative of employsults in exposure to AN, and an estiees for the purpose of exercising the mate of the frequency and degree of covered by §§ 1910.12, 1910.13, 1910.14, opportunity to observe monitoring exposure that occurs. 1910.15, or 1910.16, in lieu of any difprocedures under paragraph (r) of this Whenever there has been a signififerent standard on exposure to acrysection. cant change in the information relonitrile which would otherwise be ap- "Decontamination" means treatquired to be reported by this paraplicable by virtue of any of those secment of materials and surfaces by graph, the employer shall promptly tions. water washdown, ventilation, or other provide the new information to the 1910.1000 [Amended] means, to assure that the materials OSHA Area Office. will not expose employees to airborne (2) Emergencies. Emergencies, and concentrations of AN above 1 means the facts obtainable at that time, shall the Director, National Institute for be reported within seventy-two (72) 2. Section 1910.1000 is amended by Occupational Safety and Health, U.S. hours of the initial occurrence to the deleting the line "Acrylonitrile Department of Health, Education, and OSHA Area Office. Upon request of 20 from table Z-1 of that sec- Welfare, or designee. the OSHA Area Office, the employer tion. "Emergency" means any occurrence shall submit additional information in 3. Section 1910.1045 is revised to such as, but not limited to, equipment writing relevant to the nature and read as follows: failure, rupture of containers, or failextent of employee exposures and ure of control equipment, which remeasures taken to prevent future 1910.1045 Acrylonitrile. sults in an unexpected massive release emergencies of a similar nature. (a) Scope and application. (1) This of AN. (e) Exposure monitoring.-(1) Genersection applies to all occupational ex- "Liquid AN" means AN monomer in al. (i) Determinations of airborne exposures to acrylonitrile (AN), Chemiliquid form, and liquid or semiliquid posure levels shall be made from air cal Abstracts Service Registry No. polymer intermediates, including slursamples that are representative of 000107131, except as provided in pararies, suspensions, emulsions, and solueach employee's exposure to AN over graphs (a)(2) and (a)(3) of this section. tions, produced during the polymerizaan eight (8)-hour period. (2) This section does not apply to extion of AN. (ii) For the purposes of this section, posures which result solely from the "OSHA Area Office" means the employee exposure is that exposure processing, use, and handling of the Area Office of the Occupational which would occur if the employee following materials: Safety and Health Administration were not using a respirator. FEDERAL REGISTER, VOL 43, NO. 192-TUESDAY, OCTOBER 3, 1978 45810 RULES AND REGULATIONS (2) Initial monitoring. Each employ- AN below the permissible exposure sure to AN above the permissible expoer who has a place of employment in limits. sure limits; which AN is present shall monitor (f) Regulated areas. (1) The employ- (B) An outline of the nature of the each such workplace and work operer shall establish regulated areas engineering controls and work pracation to accurately determine the airwhere AN concentrations are in excess tices to be applied to the operation or borne concentrations of AN to which of the permissible exposure limits. process in question; employees may be exposed. (2) Regulated areas shall be demar- (C) A report of the technology con- (3) Frequency. (1) If the monitoring cated and segregated from the rest of sidered in meeting the permissible exrequired by this section reveals emthe workplace, in any manner that posure limits; ployee exposure to be below the action minimizes the number of persons who (D) A schedule for implementation level, the employer may discontinue will be exposed to AN. of engineering and work practice conmonitoring for that employee. (3) Access to regulated areas shall be trols for the operation or process, (ii) If the monitoring required by limited to authorized persons or to which shall project completion no this section reveals employee exposure persons otherwise authorized by the later than November 2, 1980; and to be at or above the action level but act or regulations issued pursuant (E) Other relevant information. below the permissible exposure limits, thereto. (iii) The employer shall complete the employer shall repeat such moni- (4) The employer shall assure that the steps set forth in the compliance toring for each such employee at least food or beverages are not present or program by the dates in the schedule. quarterly. The employer shall continconsumed, tobacco products are not (iv) Written plans shall be submitted ue these quarterly measurements until present or used, and cosmetics are not upon request to the Assistant Secreat least two consecutive measurements applied in the regulated area. tary and the Director, and shall be taken at least seven (7) days apart, are (g) Methods of compliance.-(1) Enavailable at the worksite for examinabelow the action level, and thereafter gineering and work practice controls. tion and copying by the Assistant Secthe employer may discontinue moni- (i) By November 2, 1980, the employer retary, the Director, or any affected toring for that employee. (iii) If the monitoring required by shall Institute engineering and work employee or representative. (v) The plans required by this parathis section reveals employee exposure practice controls to reduce and maingraph shall be revised and updated at to be in excess of the permissible expotain employee exposures to AN, to or least every six (6) months to reflect sure limits, the employer shall repeat below the permissible exposure limits, the current status of the program. these determinations for each such except w the extent that the employ- (h) Respiratory protection.-(1) Genemployee at least monthly. The emer establishes that such controls are eral. The employer shall assure that ployer shall continue these monthly not feasible. respirators are used where required by measurements until at least two con- (ii) Wherever the engineering and this section to reduce employee expowork practice controls which can be sure to within the permissible exposecutive measurements, taken at least instituted are not sufficient to reduce sure limits. Respirators shall be used seven (7) days apart, are below the permissible exposure limits, and thereemployee exposures to or below the in the following circumstances: (i) During the time period necessary after the employer shall monitor at permissible exposure limits, the emto install or implement feasible engileast quarterly. ployer shall nonetheless use them to neering and work practice controls; (4) Additional monitoring. Whenreduce exposures to the lowest levels (ii) In work operations, such as ever there has been a production, achievable by these controls, and shall maintenance and repair activities or process, control, or personnel change supplement them by the use of respireactor cleaning, in which the employwhich may result in new or additional ratory protection which complies with er establishes that engineering and exposures to AN, or whenever the emthe requirements of paragraph (h) of work practice controls are not feasible; ployer has any other reason to suspect this section. a change which may result in new or (iii) In work situations where feasi- (2) Compliance program. (i) The emadditional exposures to AN, additional ble engineering and work practice conployer shall establish and implement a trols are not yet sufficient to reduce monitoring which complies with this written program to reduce employee exposure to or below the permissible paragraph shall be conducted. exposures to or below the permissible exposure limits; and (5) Employee notification. (i) Within exposure limits solely by means of en- (iv) In emergencies. five (5) working days after the receipt gineering and work practice controls, of the results of monitoring required (2) Respirator selection. (1) Where as required by paragraph (g)(1) of this respiratory protection is required by. this paragraph, the employer shall section. under this section, the employer shall notify each employee in writing of the (ii) Written plans for these compliselect and provide, at no cost to the results which represent that employance programs shall include at least employee. the appropriate type of resee's exposure. (ii) Whenever the results indicate the following: pirator from table I below, and shall (A) A description of each operation assure that the employee wears the that the representative employee exor process resulting in employee exporespirator provided. posure exceeds the permissible exposure limits, the employer shall. include TABLE I.-Respiratory Protection for Acrylonitrile (AN) in the written notice a statement that the permissible exposure limits were exceeded and a description of the cor- Consestitution of AN or condition of use Respirator type rective action being taken to reduce (a) Less than or equal to 20 ppm (1) Chemical cartridge respirator with organic vapor exposure to or below the permissible cartridge(s) and half-mask facepiece: or exposure limits. (2) Supplied air respirator with half-mask facepiece. (6) Accuracy of measurement. The (b) Loss than or equal to 100 ppm or (1) Full facepiece respirator with (A) organic vapor cartridges, method of measurement of employee maximum use concentration (MUC) of (B) organic vapor gas mask chin-style, or (C) organic vapor cartridges or canisters, whichever is gas mask canister, front- or back-mounted; exposures shall be accurate, to a confilower. dence level of 95 percent, to within (2) Supplied air respirator with full facepiece: or (3) Self-contained breathing apparatus with full faceplece. plus or minus 35 percent for concen- (c) Less than or equal to 4,000 ppm (1) Supplied air respirator operated in the positive pressure trations of AN at or above the permismode with full facepiece, helmet, suit, or hood. sible exposure limits. and plus or (d) Grester than 4,000 ppm or unknown (1) Supplied air and auxillary self-contained breathing apparaminus 50 percent for concentrations of tue with full (aception in positive pressure mode; or FEDERAL 43, NO. 192-TUESDAY, OCTOBER 3, 1978 RULES AND REGULATIONS 45811 TABLE I.-Respiratory Protection for Acrylonitrile (AN) (k) Waste disposal. AN waste, scrap, debris, bags, containers, or equipment shall be decontaminated before being Concentration of AN or condition of use Respirator type incorporated in the general waste disposal system. (2) Self-contained breathing apparatus with full facepiece in (m) Hygiene facilities and practices. positive pressure mode. (e) Firefighting Self-contained breathing apparatus with full facepiece in posi- (1) Where employees are exposed to tive pressure mode. airborne concentrations of AN above (f) Escape (1) Any organic vapor respirator, or the permissible exposure limits, or (2) Any self-contained breathing apparatus. where employees are required to wear (ii) The employer shall select respito AN in excess of the ceiling limit, a protective clothing or equipment purrators from among those approved for general alarm shall be installed and suant to paragraph (j) of this section, use with organic vapors by the Nationthe facilities required by 29 CFR used to promptly alert employees of al Institute for Occupational Safety such occurrences. 1910.141, including clean change and Health under the provisions of 30 rooms and shower facilities, shall be (j) Protective clothing and equip- CFR part 11. provided by the employer for the use ment.-(1) Provision and use. Where (3) Respirator program. (i) The emof those employees, and the employer eye or skin contact with liquid AN ployer shall institute a respiratory shall assure that the employees use may occur, the employer shall provide protection program in accordance with the facilities provided. at no cost to the employee, and assure 29 CFR 1910.134 (b), (d), (e), and (f). (2) The employer shall assure that that employees wear, impermeable (ii) Where air/purifying respirators employees wearing protective clothing protective clothing or other equipment (chemical cartridge- or canister-type) or equipment for protection from skin to protect any area of the body which are used, the air-purifying canister or contact with liquid AN shall shower at may come in contact with liquid AN. cartridge(s) shall be replaced prior to the end of the work shift. The provision of 1910.132 and the expiration of their service life or (3) The employer shall assure that, 1910.133 shall be complied with. at the completion of each shift, whichin the event of skin or eye exposure to (2) Cleaning and replacement. (i) ever occurs first. A label shall be atliquid AN, the affected employee shall tached to the cartridge or canister to The employer shall clean, launder, shower immediately to minimize the indicate the date and time at which it maintain, or replace protective clothdanger of skin absorption. is first installed on the respirator. ing and equipment required by this (4) The employer shall assure that section as needed to maintain their ef- (iii) Testing. Fit testing of respiraemployees working in the regulated fectiveness. tors shall be performed to assure that area wash thefr hands and faces prior the respirator selected provides the (ii) The employer shall assure that to eating. protection required by table I. impermeable protective clothing (n) Medical surveillance.-(1) Gener- (A) Qualitative fit. The employer which contacts or is likely to have conal. (i) The employer shall institute a shall perform qualitative fit tests at tacted liquid AN shall be decontamiprogram of medical surveillance for the time of initial fitting and at least nated before being removed by the each employee who is or will be exsemiannually thereafter for each ememployee. posed to AN at or above the action ployee wearing respirators. (iii) The employer shall assure that level, without regard to the use of res- (B) Quantitative fit. Each employer an employee whose nonimpermeable pirators. The employer shall provide with more than 10 employees wearing clothing becomes wetted with liquid each such employee with an opportunegative pressure respirators shall per- AN shall immediately remove that nity for medical examinations and form quantitative fit testing at the clothing and proceed to shower. The tests in accordance with this paratime of initial fitting and at least semiclothing shall be decontaminated graph. annually thereafter for each such embefore it is removed from the regulat- (ii) The employer shall assure that ployee. ed area. all medical examinations and proce- (iv) Employees who wear respirators (iv) The employer shall assure that dures are performed by or under the shall be allowed to wash their faces no employee removes protective clothsupervision of a licensed physician, and to wipe clean the face-to-facepiece ing or equipment from the change and that they shall be provided withseals on their respirators to minimize room, except for those employees auout cost to the employee. potential skin irritation associated thorized to do so for the purpose of (2) Initial examinations. At the time with-respirator use. laundering, maintenance, or disposal. of initial assignment, or upon institu- (i) Emergency situations.-(1) Writ- (v) The employer shall inform any tion of the medical surveillance proten plans. (i) A written plan for emerperson who launders or cleans protecgram, the employer shall provide each gency situations shall be developed for tive clothing or equipment of the poaffected employee an opportunity for each workplace where liquid AN is tentially harmful effects of exposure a medical examination, including at present. Appropriate portions of the to AN. least the following elements: plan shall be implemented in the (k) Housekeeping. (1) All surfaces (i) A work history and medical histoevent of an emergency. shall be maintained free of visible acry with special attention to skin, respi- (ii) The plan shall specifically procumulations of liquid AN. ratory, and gastrointestinal systems, vide that employees engaged in cor- (2) For operations involving liquid and those nonspecific symptoms, such recting emergency conditions shall be AN, the employer shall institute a proas headache, nausea, vomiting, dizziequipped as required in paragraph (h) gram for detecting leaks and spills of ness, weakness, or other central nerof this section until the emergency is liquid AN, including regular visual invous system dysfunctions that may be abated. spections. associated with acute or with chronic (3) Where spills of liquid AN are deexposure to AN; (iii) Employees not engaged in correcting the emergency shall be evacutected, the employer shall assure that (ii) A complete physical examination ated from the area and shall not be surfaces contacted by the liquid AN giving particular attention to the pepermitted to return until the emergenare decontaminated. Employees not ripheral and central nervous system, cy is abated. engaged in decontamination activities gastrointestinal system, respiratory shall leave the area of the spill, and system, skin, and thyroid; (2) Alerting employees. Where there shall not be permitted in the area (iii) A 14- by 17-inch posteroanterior is the possibility of employee exposure until decontamination is completed. chest X-ray; and FEDERAL REGISTER, VOL. 43, NO. 192-TUESDAY, OCTOBER 3, 1978 45812 RULES AND REGULATIONS (iv) Further tests of the intestinal opinion specific findings or diagnoses DANGER tract, including fecal occult blood unrelated to occupational exposure to ACRYLONITRILE (AN) screening, for all workers 40 years of AN. age or older, and for any other affect- (iii) The employer shall provide a CANCER HAZARD ed employees for whom, in the opinion copy of the written opinion to the af- AUTHORIZED PERSONNEL ONLY of the physician, such testing is approfected employee. priate. (o) Employee information and train- RESPIRATORS MAY BE (3) Periodic examinations. (i) The ing. (1) Training program. (i) By Jan- REQUIRED employer shall provide the examinauary 2, 1979, the employer shall institions specified in paragraph (n)(2) of (ii) The employer shall assure that tute a training program for and assure this section at least annually for all signs required by this paragraph are ilthe participaton of all employees exluminated and cleaned as necessary so employees specified in paragraph posed to AN above the action level, all (n)(1) of this section. that the legend is readily visible. employees whose exposures are main- (ii) If an employee has not had the (3) Labels. (i) The employer shall tained below the action level by engiexamination specified in paragraph assure that precautionary labels are neering and work practice controls, (n)(2) of this section within 6 months affixed to all containers of liquid AN and all employees subject to potential preceding termination of employment, and AN-based materials not exempted skin or eye contact with liquid AN. the employer shall make such examiunder paragraph (a)(2) of this stand- (ii) Training shall be provided at the nation available to the employee prior ard. The employer shall assure that time of initial assignment, or upon into such termination. the labels remain affixed when the (4) Additional examinations. If the stitution of the training program, and materials are sold, distributed, or othemployee for any reason develops at least annually thereafter, and the erwise leave the employer's workplace. signs or symptoms which may be assoemployer shall assure that each em- (ii) The employer shall assure that cated with exposure to AN, the employee is informed of the following: the precautionary labels required by ployer shall provide an appropriate ex- (A) The information contained in this paragraph are readily visible and amination and emergency medical appendixes A and B; legible. The labels shall bear the foltreatment. (B) The quantity, location, manner lowing legend: (5) Information provided to the phyof use, release, or storage of AN, and DANGER sician. The employer shall provide the the specific nature of operations following information to the examinwhich could result in exposure to AN, CONTAINS ACRYLONITRILE (AN) ing physician: as well as any necessary protective CANCER HAZARD (i) A copy of this standard and its steps; appendixes; (C) The purpose, proper use, and (q) Recordkeeping. (1) Objective data (ii) A description of the affected emlimitations of respirators and protecfor exempted operations. (i) Where the ployee's duties as they relate to the tive clothing; processing, use, and handling of mateemployee's exposure; (D) The purpose and a description of rials made from or containing AN are (iii) The employee's representative the medical surveillance program reexempted pursuant to paragraph exposure level; quired by paragraph (n) of this sec- (a)(2) (ii) of this section, the employer (iv) The employee's anticipated or tion; shall establish and maintain an accuestimated exposure level (for preplace- (E) The emergency procedures derate record of objective data reasonment examinations or in cases of expoveloped, as required by paragraph (i) ably relied upon in support of the exsure due to an emergency); of this section; emption. (v) A description of any personal (F) Engineering and work practice (ii) This record shall include at least protective equipment used or to be controls, their function, and the emthe following information: used; and ployee's relationship to these controls; (A) The material qualifying for ex- (vi) Information from previous mediand emption; cal examinations of the affected em- (B) The source of the objective data; (G) A review of this standard. ployee, which is not otherwise availa- (2) Access to training materials. (i) (C) The testing protocol, results of ble to the examining physician. The employer shall make a copy of testing, and/or analysis of the materi- (6) Physician's written opinion. (i) al for the release of AN; this standard and its appendixes readi- The employer shall obtain a written (D) A description of the operation ly available to all affected employees. opinion from the examining physician exempted and how the data supports which shall include: (ii) The employer shall provide, the exemption; and (A) The results of the medical examupon request, all materials relating to (E) Other data relevant to the operination and tests performed; the employee information and trainations, materials, and processing cov- (B) The physician's opinion as to ing program to the Assistant Secretary ered by the exemption. whether the employee has any detectand the Director. (iii) The employer shall maintain ed medical condition(s) which would (p) Signs and labels. (1) General. (i) this record for the duration of the emplace the employee at an increased The employer may use labels or signs ployer's reliance upon such objective risk of material impairment of the emrequired by other statutes, reguladata. ployee's health from exposure to AN; tions, or ordinances in addition to, or (2) Exposure monitoring. (i) The em- (C) Any recommended limitations in combination with, signs and labels ployer shall establish and maintain an upon the employee's exposure to AN required by this paragraph accurate record of all monitoring reor upon the use of protective clothing (ii) The employer shall assure that quired by paragraph (e) of this secand equipment such as respirators; no statement appears on or near any tion. and (D) A statement that the employsign or label required by this para- (ii) This record shall include: ee has been informed by the physician graph which contradicts or detracts (A) The dates, number, duration, of the results of the medical examinafrom the required sign or label. and results of each of the samples tion and any medical conditions which (2) Signs. (i) The employer shall post taken, including a description of the require further examination or treatsigns to clearly indicate all workplaces sampling procedure used to determine ment. where AN concentrations exceed the representative employee exposure; (ii) The employer shall instruct the permissible exposure limits. The signs (B) A description of the sampling physician not to reveal in the written shall bear the following legend: and analytical methods used and the FEDERAL REGISTER, VOL. 43, NO. 192-TUESDAY, OCTOBER 3, 1978 RULES AND REGULATIONS 45813 data relied upon to establish that the rector at least 3 months prior to the bers, and other organic chemicals. It has methods used meet the accuracy and disposal of the records, and shall also been used as a fumigant. precision requirements of paragraph transmit them to the Director upon E. Appearance and odor: Colorless to pale (e)(6) of this section; request. yellow liquid with a pungent odor which can (C) Type of respiratory protective (r) Observation of monitoring. (1) only be detected at concentrations above devices worn, if any; and Employee observation. The employer the permissible exposure level, in a range of 13-19 parts AN per million parts of air (13- (D) Name, social security number, shall provide affected employees, or 19 ppm). and job classification of the employee their designated representatives, an F. Permissible exposure: Exposure may monitored and of all other employees opportunity to observe any monitoring not exceed either: whose exposure the measurement is of employee exposure to AN conduct- 1. Two parts AN per million parts of air (2 intended to represent. ed pursuant to paragraph (e) of this ppm) averaged over the 8-hour workday; or (iii) The employer shall maintain section. 2. Ten parts AN per million parts of air this record for at least forty (40) (2) Observation procedures. (i) (10 ppm) averaged over any 15-minute years, or for the duration of employperiod in the workday. Whenever observation of the monitor- 3. In addition, skin and eye contact with ment plus twenty (20) years, whiching of employee exposure to AN reliquid AN is prohibited. ever is longer. quires entry into an area where the (3) Medical surveillance. (i) The emuse of protective clothing or equip- II. HEALTH HAZARD DATA ployer shall establish and maintain an ment is required, the employer shall A. Acrylonitrile can affect your body if accurate record for each employee provide the observer with personal you inhale the vapor (breathing), if it comes subject to medical surveillance as reprotective clothing and equipment rein contact with your eyes or skin, or if you quired by paragraph (n) of this secquired to be worn by employees workswallow it. It may enter your body through tion. ing in the area, assure the use of such your skin. (ii) This record shall include: clothing and equipment, and require B. Effects of overexposure: 1. Short-term exposure: Acrylonitrile can cause eye irrita- (A) A copy of the physician's written the observer to comply with all other tion, nausea, vomiting, headache, sneezing, opinions; applicable safety and health proceweakness, and light-headedness. At high (B) Any employee medical comdures. concentrations, the effects of exposure may plaints related to exposure to AN; (ii) Without interfering with the go on to loss of consciousness and death. (C) A copy of the information promonitoring, observers shall be enti- When acrylonitrile is held in contact with vided to the physician as required by tled: the skin after being absorbed into shoe paragraph (n)(5) of this section; and (A) To receive an explanation of the leather or clothing, it may produce blisters (D) A copy of the employee's medimeasurement procedures; following several hours of no apparent effect. Unless the shoes or clothing are recal and work history. (B) To observe all steps related to moved immediately and the area washed, (iii) The employer shall assure that the measurement of airborne concenblistering will occur. Usually there is no this record be maintained for at least trations of AN performed at the place pain or inflammation associated with blister forty (40) years, or for the duration of of exposure; and formation. employment plus twenty (20) years, (C) To record the results obtained. 2. Long-term exposure: Acrylonitrile has whichever is longer. (s) Effective date. been shown to cause cancer in laboratory animals and has been associated with (4) Availability. (i) The employer (1) This section shall become effechigher incidences of cancer in humans. Reshall make all records required to be tive November 2, 1978. peated or prolonged exposure of the skin to maintained by this section available, (2) Monitoring and medical surveilacrylonitrile may produce irritation and derupon request, to the Assistant Secrelance conducted since January 17, matitis. tary and the Director for examination 1978, under the provisions of the 3. Reporting signs and symptoms: You and copying. emergency temporary standard may should inform your employer if you develop (ii) The employer shall make records be relied upon by the employer to any signs or symptoms and suspect they are required by paragraph (q)(1) and meet the initial monitoring and initial caused by exposure to acrylonitrile. (q)(2) of this section available upon remedical surveillance requirements of III. EMERGENCY FIRST AID PROCEDURES quest, for examination and copying, to this section. A. Eye exposure: If acrylonitrile gets into affected employees, former employees, (3) Training programs must be imyour eyes, wash your eyes immediately with or their designated representatives. plemented by January 2, 1979. large amounts of water, lifting the lower (iii) The employer shall make an em- (4) Engineering and work practice and upper lids occasionally. Get medical atployee's medical records required to be controls required by paragraph (g) of tention immediately. Contact lenses should maintained by this section available this section shall be implemented no not be worn when working with this chemiupon request, for examination and later than November 2, 1980. cal. copying, to the affected employee or (t) Appendixes. The information con- B. Skin exposure: If acrylonitrile gets on your skin, immediately wash the contamiformer employee, or to a physician tained in the appendixes is not intendnated skin with water. If acrylonitrile soaks designated by the affected employee ed, by itself, to create any additional through your clothing. especially your or former employee. obligations not otherwise imposed, or shoes, remove the clothing immediately and (5) Transfer of records. (i) Whenever to detract from any obligation. wash the skin with water. If symptoms the employer ceases to do business, occur after washing, get medical attention the successor employer shall receive APPENDIX A-SUBSTANCE SAFETY DATA SHEET immediately. Thoroughly wash the clothing FOR ACRYLONITRILE and retain all records required to be before reusing. Contaminated leather shoes or other leather articles should be discardmaintained by this section for the pre- I. SUBSTANCE IDENTIFICATION ed. scribed period. A. Substance: Acrylonitrile (CH,=CHCN). C. Inhalation: If you or any other person (ii) Whenever the employer ceases to B. Synonyms: Propenenitrile; vinyl cyabreathes in large amounts of acrylonitrile, do business and there is no successor nide; cyanoethylene; AN; VCN; acrylon; carmove the exposed person to fresh air at employer to receive and retain the recbacryl; fumigrain; ventox. once. If breathing has stopped, perform arords for the prescribed period, these C. Acrylonitrile can be found as a liquid or tificial respiration. Keep the affected records shall be transmitted to the Divapor, and can also be found in polymer person warm and at rest. Get medical attenrector. resins, rubbers, plastics, polyols, and other tion as soon as possible. polymers having acrylonitrile as a raw or in- D. Swallowing: When acrylonitrile has (iii) At the expiration of the retentermediate material. been swallowed, give the person large quantion period for the records required to D. AN is used in the manufacture of acryltities of water immediately. After the water be maintained pursuant to this secic and modiacrylic fibers, acrylic plastics has been swallowed, try to get the person to tion, the employer shall notify the Diand resins, speciality polymers, nitrile rubvomit by having him touch the back of his FEDERAL REGISTER, VOL. 43, NO. 192-TUESDAY, OCTOBER 3, 1978 45814 RULES AND REGULATIONS throat with his finger. Do not make an unnated with acrylonitrile, and if they do the quired to inform you of the actions which conscious person vomit. Get medical attenclothing and shoes should be promptly reare being taken to reduce your exposure to tion immediately. moved and decontaminated. The clothing within permissible exposure limits. E. Rescue: Move the affected person from should be laundered or discarded after the C. Your employer is required to keep recthe hazardous exposure. If the exposed AN is removed. Once acrylonitrile peneords of your exposures and medical examiperson has been overcome, notify someone trates shoes or other leather articles, they nations. These records must be kept by the else and put into effect the established should not be worn again. employer for at least forty (40) years or for emergency procedures. Do not become a cas- D. Eye protection: You must wear splashthe period of your employment plus twenty ualty yourself. Understand your emergency proof safety goggles in areas where liquid (20) years, whichever is longer. rescue procedures and know the location of acrylonitrile may contact your eyes. In addi- D. Your employer is required to release the emergency equipment before the need tion, contact lenses should not be worn in your exposure and medical records to your arises. areas where eye contact with acrylonitrile physician upon your written request. F. Special first aid procedures: First aid can occur. kits containing an adequate supply (at least APPENDIX B-SUBSTANCE TECHNICAL two dozen) of amyl nitrite pearls, each con- V. PRECAUTIONS FOR SAFE USE, HANDLING, AND GUIDELINES FOR ACRYLONITRILE taining 0.3 ml, should be maintained at each STORAGE site where acrylonitrile is used. When a I. PHYSICAL AND CHEMICAL DATA A. Acrylonitrile is a flammable liquid, and person is suspected of receiving an overexits vapors can easily form explosive mix- A. Substance identification: 1. Synonyms: posure to acrylonitrile, immediately remove tures in air. AN; VCN; vinyl cyanide; propenenitrile; that person from the contaminated area B. Acrylonitrile must be stored in tightly cyanoethylene; Acrylon; Carbacryl; Fumiusing established rescue procedures. Conclosed containers in a cool, well-ventilated grain; Ventox. taminated clothing must be removed and area, away from heat, sparks, flames, strong 2. Formula: CH2=CHCN. the acrylonitrile washed from the skin imoxidizers (especially bromine), strong bases, 3. Molecular weight: 53.1. mediately. Artificial respiration should be copper, copper alloys, ammonia, and amines. B. Physical data: 1. Boiling point (760 mm started at once if breathing has stopped. If C. Sources of ignition such as smoking and Hg): 77.3°C (171° F); the person is unconscious, amyl nitrite may open flames are prohibited wherever acry- 2. Specific gravity (water=1): 0.81 (at 20° be used as an antidote by a properly trained lonitrile is handled, used, or stored in a C or 68° F); individual in accordance with established manner that could create a potential fire or 3. Vapor density (air=1 at boiling point of emergency procedures. Medical aid should explosion hazard. acrylonitrile): 1.83; be obtained immediately. D. You should use non-sparking tools 4. Melting point: -83° C F); when opening or closing metal containers of 5. Vapor pressure (@20° F): 83 mm Hg; IV. RESPIRATORS AND PROTECTIVE CLOTHING acrylonitrile, and containers must be 6. Solubility in water, percent by weight A. Respirators: You may be required to bonded and grounded when pouring or @20° C (68' F): 7.35; wear a respirator for nonroutine activites, in transferring liquid acrylonitrile. 7. Evaporation rate (Butyl Acetate=1): emergencies, while your employer is in the E. You must immediately remove any non- 4.54; and process of reducing acrylonitrile exposures impervious clothing that becomes wetted 8. Appearance and odor: Colorless to pale through engineering controls, and in areas with acrylonitrile, and this clothing must yellow liquid with a pungent odor at concenwhere engineering controls are not feasible. not be reworn until the acrylonitrile is retrations above the permissible exposure If respirators are worn, they must have a moved from the clothing. level. Any detectable odor of acrylonitrile Mine Safety and Health Administration F. Impervious clothing wet with liquid may indicate overexposure. (MSHA or MESA) or National Institute for acrylonitrile can be easily ignited. This Occupational Safety and Health (NIOSH) clothing must be washed down with water II. FIRE, EXPLOSION, AND REACTIVITY HAZARD label of approval for use with organic before you remove it. DATA vapors. (Older respirators may have a G. If your skin becomes wet with liquid A. Fire: 1. Flash point: -1° C (30° F) Bureau of Mines approval label.) For effecacrylonitrile, you must promptly and thor- (closed cup). tive protection, respirators must fit your oughly wash or shower with soap or mild 2. Autoignition temperature: 481° C (898° face and head snugly. Respirators should detergent to remove any acrylonitrile from F). not be loosened or removed in work situayour skin. 3. Flammable limits air, percent by tions where their use is required. H. You must not keep food, beverages, or volume: Lower: 3, Upper: 17. Acrylonitrile does not have a detectable smoking materials, nor are you permitted to 4. Extinguishing media: Alcohol foam, odor except at levels above the permissible eat or smoke in regulated areas where acrycarbon dioxide, and dry chemical. exposure limits. Do not depend on odor to lonitrile concentrations are above the per- 5. Special fire-fighting procedures: Do not warn you when a respirator cartridge or missible exposure limits. use a solid stream of water, since the stream canister is exhausted. Cartridges or canis- I. If you contact liquid acrylonitrile, you will scatter and spread the fire. Use water to ters must be changed daily or before the must wash your hands thoroughly with cool containers exposed to a fire. end-of-service-life, whichever comes first. soap or mild detergent and water before 6. Unusual fire and explosion hazards: Reuse of these may allow acrylonitrile to eating, smoking, or using toilet facilities. Acrylonitrile is a flammable liquid. Its gradually filter through the cartridge and J. Fire extinguishers and quick drenching vapors can easily form explosive mixtures cause exposures which you cannot detect by facilities must be readily available, and you with air. All ignition sources must be conodor. If you can smell acrylonitrile while should know where they are and how to optrolled where acrylonitrile is handled, used, wearing a respirator, proceed immediately erate them. or stored in a manner that could create a to fresh air. If you experience difficulty K. Ask your supervisor where acrylonitrile potential fire or explosion hazard. Acrylonibreathing while wearing a respirator, tell is used in your work area and for any additrile vapors are heavier than air and may your employer. tional plant safety and health rules. travel along the ground and be ignited by B. Supplied-air suits: In some work situaopen flames or sparks at locations remote tions, the wearing of supplied-air suits may VI. ACCESS TO INFORMATION from the site at which acrylonitrile is being be necessary. Your employer must instruct A. Each year, your employer is required to handled. you in their proper use and operation. inform you of the information contained in 7. For purposes of compliance with the re- C. Protective clothing: You must wear imthis Substance Safety Data Sheet for acryquirements of 29 CFR 1910.106, acrylonipervious clothing, gloves, face shield, or lonitrile. In addition, your employer must trile is classified as a class IB flammable other appropriate protective clothing to preinstruct you in the proper work practices liquid. For example, 7,500 ppm, approxivent skin contact with liquid acrylonitrile. for using acrylonitrile, emergency procemately one-fourth of the lower flammable Where protective clothing is required, your dures, and the correct use of protective limit, would be considered to pose a potenemployer is required to provide clean garequipment. tial fire and explosion hazard. ments to you as necessary to assume that B. Your employer is required to determine 8. For purposes of compliance with 29 the clothing protects you adequately. whether you are being exposed to acryloni- CFR 1910.157, acrylonitrile is classified as a Replace or repair impervious clothing trile. You or your representative has the Class B fire hazard. that has developed leaks. right to observe employee measurements 9. For purpose of compliance with 29 CFR Acrylonitrile should never be allowed to and to record the results obtained. Your em- 1919.309, locations classified as hazardous remain on the skin. Clothing and shoes ployer is required to inform you of your exdue to the presence of acrylonitrile shall be which are not impervious to acrylonitrile posure. If your employer determines that Class I, Group D. should not be allowed to become contamiyou are being overexposed, he or she is re- B. Reactivity: FEDERAL REGISTER, VOL. 43, NO. 192-TUESDAY, OCTOBER 3, 1978 RULES AND REGULATIONS 45815 1. Conditions contributing to instability: position adsorption tubes, with subsequent VI. HOUSEKEEPING AND HYGIENE FACILITIES Acrylonitrile will polymerise when hot, and chemical analysis. Sampling and analysis the additional heat liberated by the poly- For purposes of complying with 29 CFR may also be performed by instruments such merimation may cause centainers to explode. 1910.141. the following Items should be emas real-time continuous monetoring systems, Pure AN may self-polymerime, with a rapid phasized: portable direct-reading instruments, or pasbuild-up of pressure, resulting in an explo- A. The workplace should be kept clean, orsive dosimeters. Analysis of resultant samsion hazard. Inhibitors are added to the derly. and in a sanitary condition. The emples should be by gas chromatograph. commercial product to prevent self-polymerployer is required to institute a leak and Appendix D lists methods of sampling and ization. spill detection program for operations inanalysis which have been tested by NIOSH 2. Incompatibilities: Contact with strong volving liquid AN in order to detect sources and OSHA for use with acrylonitrile. oxidizers (especially bromine) and strong of fugitive AN emissions. NIOSH and OSHA have validated modificabases may cause fires and explosions. Con- B. Dry sweeping and the use of comtions of NIOSH Method 8-156 (See Appentact with copper, copper alloys, ammonia, pressed air is unsafe for the cleaning of dix D) under laboratory conditions for conand amines may start serious decomposifloors and other surfaces where liquid AN centrations below 1 ppm. The employer has tion. may be found. the obligation of selecting a monitoring 3. Hazardous decomposition products: C. Adequate washing facilities with hot method which meets the accuracy and pre- Toxic gases and vapors (such as hydrogen and cold water are to be provided, and maincision requirements of the standard under cyanide, oxides of nitrogen, and carbon tained in a sanitary condition. Suitable his unique field conditions. The standard remonoxide) may be released in a fire involvcleansing agents are also to be provided to quires that methods of menitoring must be ing aerylonitrile and certain polymers made assure the effective removal of acrylonitrile from acrylonitrile. accurate, to a 96-percent confidence level, to from the skin. +35-percent for concentrations of AN at or 4. Special precautions: Liquid acrylonitrile D. Change or dressing rooms with individabove 2 ppm, and to +50-percent for conwill attack some forms of plastics, rubbers, usl clothes storage facilities must be procentrations below 2 ppm. In addition to the and coatings. vided to prevent the contamination of street methods described in Appendix D. there are clothes with acrylonitrile. Because of the III. SPILL, LEAK, AND DISPOSAL PROCEDURES numerous other methods available for monihazardous nature of acrylonitrile, contamitoring for AN in the workplace. Details on nated protective clothing should be placed A. If acrylonitrile is spilled or leaked, the these other methods have been submitted in a regulated area designated by the emfollowing steps should be taken: by various companies to the rulemaking ployer for removal of the AN before the 1. Remove all ignition sources. record, and are available at the OSHA clothing is laundered or disposed of. 2. The area should be evacuated at once Docket Office. and re-entered only after the area has been B. Since many of the duties relating to VII. MISCELIANEOUS PRECAUTIONS thoroughly ventilated and washed down employee exposure are dependent on the rewith water. A. Store acrylonitrile in tightly-closed consults of monitoring and measuring proce- 3. If liquid acrylonitrile or polymer intertainers in a cool, well-ventilated area and dures, employers shall assure that the evalmediate, collect for reclamation or absorb in take necessary precautions to avoid any exuntion of employee exposures is performed paper, vermiculite, dry sand, earth, or simiplesion hazard. by a competent industrial hygienist or other lar material, or wash down with water into B. High exposures to acrylonitrile can technically qualified person. process sewer system. occur when transferring the liquid from one B. Persons not wearing protective equipcontainer to another. V. PROTECTIVE CLOTHING ment should be restricted from areas of C. Non-sparking tools must be used to spills or leaks until clean-up has been com- Employees shall be provided with and reopen and close metal acrylonitrile containpleted. quired to wear appropriate protective clothers. These containers must be effectively C. Waste disposal methods: Waste materiing to prevent any possibility of skin contact grounded and bonded prior to pouring. al shall be disposed of in a manner that is with liquid AN. Because acrylonitrile is ab- D. Never store uninhibited acrylonitrile. not hazardous to employees or to the genersorbed through the skin, It is important to E. Acrylonitrile vapors are not inhibited. al population. Spills of acrylonitrile and prevent skin contact with liquid AN. Protec- They may form polymers and clog vents of flushing of such spills shall be channeled tive clothing shall include impermeable COVstorage tanks. for appropriate treatment or collection for eralls or similar full-body work clothing. F. Use of supplied-air suits or other Imperdisposal. They shall not be channeled digloves, head-coverings, as appropriate to vious coverings may be necessary to prevent rectly into the sanitary sewer system. In seprotect areas of the body which may come skin contact with and provide respiratory lecting the method of waste disposal, appliin contact with liquid AN. protection from acrylonitrile where the concable local, State, and Federal regulations Employers should ascertain that the procentration of acrylonitrile is unknown or is should be consulted. tective garments are impermeable to acryabove the celling limit. Supplied-air suits lonitrile. Non-impermeable clothing and should be selected, used, and maintained IV. MONOTORING AND MEASUREMENT shoes should not be allowed to become conunder the immediate supervision of persons PROCEDURES taminated with liquid AN. If permeable knowledgeable in the limitations and poten- A. Exposure above the Perminaible Expoclothing does become containinated, it tial life-endangering characteristics of supsure Limit: should be promptly removed, placed in a plied-air suits. 1. Eight-hour exposure evaluation: Mearegulated area for removal of the AN, and G. Employers shall advise employees of all surements taken for the purpose of deternot worn again until the AN is removed. If areas and operations where exposure to mining employee expesure under this seeleather footwear or other leather garments acrylonitrile could occur. tion are best taken so that the average 8- become was from acrylenitrile, they should VIII. COMMON OPERATIONS hour expesure may be determined from a be replaced and not worn again, due to the single 8-hour sample or two (2) 4-hour - ability of leather to absorb aerylonitrile and Common operations in which exposure to ples. Air samples should be taken in the - hold it against the skin. Since there is no acrylonitrile is likely to occur include the ployee's breathing some (air that would pain associated with the blistering which following: Manufacture of the acrylonitrile most nearly represent that inhaled by the may result from skin contact with Mquid monomer; aynthesis of acrylic fibers, ABS, employee.) AM, it is consential that the employee be in- SAN, and nitrile barrier plastics and reains, 2. Celling evaluation: Measurements taken formed lef this hanard so that he or she can nitrile rubber, surface coatings, specialty for the purpose of determining employee be protected. chemicals, use as a chemical intermediate, exposure under this section must be taken Any protective clothing which has develuse as a fumigant and in the cyanoethyladuring periods of maximum expected airoped leaks or is otherwise found to be defeetion of cotton. borne concentrations of acrylenitrile in the tive shall be repaired or replaced. Clean proemployee's breathing sone. A of tective clothing shall be provided to the ema- APPENDIX C-MEDICAL SURVEILLANCE three (3) measurements should be taken on playee as necessary to assure its protéctive- GUIMELINES FOR ACRYLONITRILE one work shift. The average of all measurenees. Whenever impervious clothing be L ROUTE OF ENTRY ments taken is an estimate of the employcomes wet with liquid AN, it shall be washed 00's ceiling exposure. down with water before being removed by Inhalation: skin absorption: ingestion. 3. Menitoring techniques: The sampling the employee. Employees are also required and analysis under this section may be perto wear splash-proof safety goggles where II. TOXICOLOGY formed by collecting the acrylemitrile vaper there is any pensibility of acrylemitrile - Aerylonitrile vapor is an asphyxiant due on charcoal adsorption tubes or other somtasting the eyes. to inhibitory action on metabolic enzyme REGISTER, VOL. 4a, NO. 198-TUMERAY, OCTOBER & 1078 45816 RULES AND REGULATIONS systems. Animals exposed to 75 or 100 ppm Camden, S.C. In addition, the animal testof charcoal, and the use of different equipfor 7 hours have shown signs of anoxia; in ing of acrylonitrile has resulted in the develment for analysis of the samples. some animals which died at the higher level, opment of cancers of the central nervous Besides charcoal, considerable work has cyanomethemoglobin was found in the system in rats exposed by either inhalation been performed on methods using porous blood. Two human fatalities from accidental or ingestion. The physician should be aware polymer sampling tubes and passive dostpoisoning have been reported; one was of the findings of these studies in evaluating meters. In addition, there are several portacaused by inhalation of an unknown concenthe health of employees exposed to acrylonble gas analyzers and monitoring units availtration of the vapor, and the other was itrile. able on the open market. thought to be caused by skin absorption or Most reported acute effects of occupation- This appendix contains details for the inhalation. Most cases of intoxication from al exposure to acrylonitrile are due to its methods which have been tested at OSHA industrial exposure have been mild, with ability to cause tissue anoxia and asphyxia. Analytical Laboratory in Salt Lake City, rapid onset of eye irritation, headache, The effects are similar to those caused by and NIOSH in Cincinnati. Each is a varisneezing, and nausea. Weakness, lightheahydrogen cyanide. Liquid acrylonitrile can ation on NIOSH Method S-156, which is dedness, and vomiting may also occur. Expobe absorbed through the skin upon proalso included for reference. This does not insure to high concentrations may produce longed contact. The liquid readily penedicate that these methods are the only ones profound weakness, asphyxia, and death. trates leather, and will produce burns of the which will be satisfactory. There also may The vapor is a severe eye irritant. Prolonged feet if footwear contaminated with acrylonibe workplace situations in which these skin contract with the liquid may result in trile is not removed. methods are not adequate, due to such facabsorption with systemic effects, and in the It is important for the physician to tors as high humidity. Copies of the other formation of large blisters after a latent become familiar with the operating condimethods available to OSHA are available in period of several hours. Although there is tions in which exposure to acrylonitrile may the rulemaking record, and may be obtained usually little or no pain or inflammation, occur. Those employees with skin diseases from the OSHA Docket Office. These inthe affected skin resembles a second-degree may not tolerate the wearing of whatever clude the Union Carbide, Monsanto, Dow thermal burn. Solutions spilled on exposed protective clothing may be necessary to pro- Chemical and Dow Badische methods, as skin, or on areas covered only by a light tect them from exposure. In addition, those well as NIOSH Method P & CAM 127. layer of clothing, evaporate rapidly, leaving with chronic respiratory disease may not Employers who note problems with no irritation, or, at the most, mild transient tolerate the wearing of negative-pressure sample breakthrough should try larger redness. Repeated spills on exposed skin respirators. charcoal tubes. Tubes of larger capacity are may result in dermatitis due to solvent ef- B. Surveillance and screening. Medical available, and are often used for sampling fects. histories and laboratory examinations are vinyl chloride. In addition, lower flow rates Results after 1 year of a planned 2-year required for each employee subject to expoand shorter sampling times should be beneanimal study on the effects of exposure to sure to acrylonitrile above the action level. ficial in minimizing breakthrough problems. acrylonitrile have indicated that rats ingest- The employer must screen employees for Whatever method the employer chooses, ing as little as 35 ppm in their drinking history of certain medical conditions which he must assure himself of the method's acwater develop tumors of the central nervous might place the employee at increased risk curacy and precision under the unique consystem. The interim results of this study from exposure. ditions present in his workplace. have been supported by a similar study 1. Central nervous system dysfunction. NIOSH METHOD S-156 (UNMODIFIED) being conducted by the same laboratory, in- Acute effects of exposure to acrylonitrile volving exposure of rats by inhalation of generally involve the central nervous Analyte: Acrylonitrile. acrylonitrile vapor, which has shown similar system. Symptoms of acrylonitrile exposure Matrix: Air. types of tumors in animals exposed to 80 include headache. nausea, dizziness, and Procedure: Absorption on charcoal, desorpppm. general weakness. The animal studies cited tion with methanol, GC. In addition, the preliminary results of an above suggest possible carcinogenic effects epidemiological study being performed by 1. Principle of the method (Reference of acrylonitrile on the central nervous duPont on a cohort of workers in their 11.1). system, since rats exposed by either inhala- 1.1 A known volume of air is drawn Camden, S.C. acrylic fiber plant indicate a tion or ingestion have developed similar statistically significant increase in the incithrough a charcoal tube to trap the organic CNS tumors. dence of colon and lung cancers among-emvapors present. 2. Respiratory disease. The du Pont data 1.2 The charcoal in the tube is transployees exposed to acrylonitrile. indicate an increased risk of lung cancer ferred to a small, stoppered sample contain- III. SIGNS AND SYMPTOMS OF ACUTE among employees exposed to acrylonitrile. er, and the analyte is desorbed with metha- OVEREKPOSURE 3. Gastrointestinal disease. The du Pont nol. data indicate an increased risk of cancer of 1.3 An aliquot of the desorbed sample is Asphyxia and death can occur from expothe colon among employees exposed to acryinjected into a gas chromatograph. sure to high concentrations of acrylonitrile. lonitrile. In addition, the animal studies 1.4 The area of the resulting peak is de- Symptoms of overexposure include eye irrishow possible tumor production in the stomtermined and compared with areas obtained tation, headache, sneezing, nausea and vomachs of the rats in the ingestion study. for standards. iting, weakness, and light-headedness. Pro- 4. Skin disease. Acrylonitrile can cause 2. Rangeand sensitivity. longed skin contact can cause blisters on the skin burns when prolonged skin contact 2.1 This method was validated over the skin with appearance of a second-degree with the liquid occurs. In addition, repeated range of 17.5-70.0 mg/cu m at an atmosburn, but with little or no pain. Repeated skin contact with the liquid can cause derpheric temperature and pressure of 22' C skin contact may produce scaling dermatitis. matitis. and 760 mm Hg. using a 20-liter sample. 5. General. The purpose of the medical Under the conditions of sample size (20 IV. TREATMENT OF ACUTE OVEREXPOSURE procedures outlined in the standard is to - liters) the probable useful range of this Remove employee from exposure. Immetablish a baseline for future health monitormethod is 4.5-135 mg-cu m. The method is diately flush eyes with water and wash skin ing. Persons unusually susceptible to the efcapable of measuring much smaller with soap or mild detergent and water. If fects of anoxia or those with anemia would amounts if the desorption efficiency is ade- AN has been swallowed, and person is conbe expected to be at increased risk. In addiquate. Descrption efficiency must be deterscious, induce vomiting. Give artificial retion to emphasis on the CNS, respiratory mined over the range used. suscitation if indicated. More severe cases, and gastro-intestinal systems, the cardiovas- 2.2 The upper limit of the range of the such as those associated with loss of concular system, liver, and kidney function method is dependent on the adsorptive casciousness, may be treated by the intraveshould also be stressed. pacity of the charcoal tube. This capacity nous administration of sodium nitrite, folvaries with the concentrations of acrylonilowed by sodium thiosulfate, although this APPENDIX D.-SAMPLING AND ANALYTICAL trile and other substances in the air. The is not as effective for acrylonitrile poisoning METHODS FOR ACRYLONITRILE first section of the charcoal tube was found as for inorganic cyanide poisoning. There are many methods available for to hold at least 3.97 mg of acrylonitrile monitoring employee exposures to acryloniwhen a test atmosphere containing 92.0 mg/ V. SURVEILLANCE AND PREVENTIVE trile. Most of these involve the use of charou m of acrylonitrile in air was sampled 0.18 CONSIDERATIONS coal tubes and sampling pumps, with analyliter per minute for 240 minutes: at that A. As noted above, exposure to acrylonisis by - chromatograph. The easential diftime the concentration of acrylonitrile in trile has been linked to increased incidence ferences between the charecal tube methods the effluent was less than 5 percent of that of cancers of the colon and lung in employinclude, among others, the use of different in the influent. (The charcoal tube consists ees of the duPont acrylic fiber plant in desorbing solvents, the use of different lots of two sections of activated char FEDERAL REGISTER, VOL. 43, NO. 192-TUESDAY, OCTOBER 3, 1978 RULES AND REGULATIONS 45817 rated by a section of urethane foam. See 6.1 A calibrated personal sampling pump 8.3.8 With each batch of 10 samples section 6.2.) If a particular atmosphere is whose flow can be determined within +5 submit one tube from the same lot of tubes suspected of containing a large amount of percent at the recommended flow rate. which was used for sample collection and contaminant, a smaller sampling volume (Reference 11.3). which is subjected to exactly the same hanshould be taken. 6.2 Charcoal tubes: Glass tubes with dling as the samples except that no air is 3. Interference. both ends flame sealed, 7 cm long with a 6- drawn through it. Label this as a blank. 3.1 When the amount of water in the air mm O.D. and a 4-mm I.D., containing 2 sec- 8.3.9 Capped tubes should be packed is so great that condensation actually occurs tions of 20/40 mesh activated charcoal sepatightly and padded before they are shipped in the tube, organic vapors will not be rated by a 2-mm portion of urethane foam. to minimize tube breakage during shipping trapped efficiently. Preliminary experi- The activated charcoals prepared from coco- 8.3.10 A sample of the bulk material ments using toluene indicate that high hunut shells and is fired at 600° C prior to should be submitted to the laboratory in a midity severely decreases the breakthrough packing. The adsorbing section contains 100 glass container with a Teflon-lined cap. This volume. mg of charcoal, the backup section 50 mg. A sample should not be transported in the 3.2 When interfering compounds are 3-mm portion of urethane foam is placed besame container as the charcoal tubes. known or suspected to be present in the air, tween the outlet end of the tube and the 8.4 Analysis of samples. such information, including their suspected backup section. A plug of silicated glass 8.4.1 Preparation of samples. In preparaidentities, should be transmitted with the wool is placed in front of the adsorbing section for analysis, each charcoal tube is sample. tion. The pressure drop across the tube scored with a file in front of the first sec- 3.3 It must be emphasized that any commust be less than 1 inch of mercury at a tion of charcoal and broken open. The glass pound which has the same retention time as flow rate of 1 liter per minute. wool is removed and discarded. The charthe analyte at the operating conditions de- 6.3 Gas chromatograph equipped with a coal in the first (larger) section is transscribed in this method is an interference. flame ionization detector. ferred to a 2-ml stoppered sample container. Retention time data on a single column 6.4 Column (4-ft 1/4-in stainless steel) The separating section of foam is removed cannot be considered proof of chemical packed with 50/80 mesh Poropak, type Q. and discarded; the second section is transidentity. 6.5 An electronic integrator or some ferred to another stoppered container. 3.4 If the possibility of interference other suitable method for measuring peak These two sections are analyzed separately. exists, separation conditions (column packareas. 8.4.2 Desorption of samples. Prior to ing, temperature, etc.) must be changed to 6.6 Two-milliliter sample containers with analysis, 1.0 ml of methanol is pipetted into circumvent the problem. glass stopers or Teflon-lined caps. If an each sample container. Desorption should 4. Precision and accuracy. automatic sample injector is used, the assobe done for 30 minutes. Tests indicate that 4.1 The Coefficient of Variation (CVT) ciated vials may be used. this is adequate if the sample is agitated OC for the total analytical and sampling 6.7 Microliter syringes: 10-microliter, and casionally during this period. If an automat method in the range of 17.5-70.0 mg/cu m other convenient sizes for making standic sample injector is used, the sample vials was 0.073. This value corresponds to a 3.3 ards. should be capped as soon as the solvent is mg/cu m standard deviation at the (previ- 6.8 Pipets: 1.0-ml delivery pipets. added to minimize volatilization. ous) OSHA standard level (20 ppm). Statisti- 6.9 Volumetric flask: 10-ml or convenient 8.4.3 GC conditions. The typical operatcal information and details of the validation sizes for making standard solutions. ing conditions for the gas chromatograph and experimental test procedures can be 7. Reagents. are: found in Reference 11.2. 7.1 Chromatographic quality methanol. 1. 50 ml/min (60 psig) nitrogen carrier gas 4.2 On the average the concentrations 7.2 Acrylonitrile, reagent grade. flow. obtained at the 20 ppm level using the over- 7.3 Hexane, reagent grade. 2. 65 ml/min (24 psig) hydrogen gas flow all sampling and analytical method were 6.0 7.4 Purified nitrogen. to detector. percent lower than the "true" concentra- 7.5 Prepurified hydrogen. 3. 500 ml/min (50 psig) air flow to detec tions for a limited number of laboratory ex- 7.6 Filtered compressed air. tor. periments. Any difference between the 8. Procedure. 4. 235° C injector temperature. "found" and "true" concentrations may not 8.1 Cleaning of equipment. All glassware 5. 255° C manifold temperature (detector). represent a bias in the sampling and analytused for the laboratory analysis should be 6. 155° C column temperature. ical method, but rather a random variation detergent washed and thoroughly rinsed 8.4.4 Injection. The first step in the analfrom the experimentally determined "true" with tap water and distilled water. ysis is the injection of the sample into the concentration. Therefore, no recovery cor- 8.2 Calibration of personal pumps. Each gas chromatograph. To eliminate difficulrection should be applied to the final result personal pump must be calibrated with a ties arising from blowback or distillation in section 10.5. representative charcoal tube in the line. within the syringe needle, one should 5. Advantages and disadvantages of the This will minimize errors associated with employ the solvent flush injection techmethod. uncertainties in the sample volume collectnique. The 10-microliter syringe is first 5.1 The sampling device is small, portaed. flushed with solvent several times to wet ble, and involves no liquids. Interferences 8.3 Collection and shipping of samples. the barrel and plunger. Three microliters of are minimal, and most of those which do 8.3.1 Immediately before sampling, break solvent are drawn into the syringe to inoccur can be eliminated by altering chromathe ends of the tube to provide an opening crease the accuracy and reproducibility of tographic conditions. The tubes are anaat least one-half the internal diameter of the injected sample volume. The needle is lyzed by means of a quick, instrumental the tube (2 mm). removed from the solvent, and the plunger method. 8.3.2 The smaller section of charcoal is is pulled back about 0.2 microliter to sepa- The method can also be used for the siused as a backup and should be positioned rate the solvent flush from the sample with multaneous analysis of two or more subnearest the sampling pump. a pocket of air to be used as a marker. The stances suspected to be present in the same 8.3.3 The charcoal tube should be placed needle is then immersed in the sample, and sample by simply changing gas chromatoin a vertical direction during sampling to a 5-microliter aliquot is withdrawn, taking graphic conditions. minimize channeling through the charcoal. into consideration the volume of the needle, 5.2 One disadvantage of the method is 8.3.4 Air being sampled should not be since the sample in the needle will be comthat the amount of sample which can be passed through any hose or tubing before pletely injected. After the needle is removed taken is limited by the number of millientering the charcoal tube. from the sample and prior to injection, the grams that the tube will hold before over- 8.3.5 A maximum sample size of 20 liters plunger is pulled back 1.2 microliters to loading. When the sample value obtained is recommended. Sample at a flow of 0.20 minimize evaporation of the sample from for the backup section of the charcoal tube liter per minute or less. The flow rate the tip of the needle. Observe that the exceeds 25 percent of that found on the should be known with an accuracy of at sample occupies 4.9-5.0 microliters in the front section, the possibility of sample loss least +5 percent. barrel of the syringe. Duplicate injections of exists. 8.3.6 The temperature and pressure of each sample and standard should be made. 5.3 Furthermore, the precision of the the atmosphere being sampled should be re- No more than a 3 percent difference in area method is limited by the reproducibility of corded. If pressure reading is not available, is to be expected. An automatic sample inthe pressure drop across the tubes. This record the elevation. jector can be used if it is shown to give redrop will affect the flow rate and cause the 83.7 The charcoal tubes should be producibility at least as good as the solvent volume to be imprecise, because the pump is capped with the supplied plastic caps immeflush method. usually calibrated for one tube only. diately after sampling. Under no circum- 8.4.5 Measurement of area. The area of 6. Apparatus. stances should rubber caps be used. the sample peak is measured by an electron- FEDERAL REGISTER, VOL. 43, NO. 192-TUESDAY, OCTOBER 3, 1978 45818 RULES AND REGULATIONS ic integrator or some other suitable form of effect of known day-to-day variations and Detector temperature: 100° C. area measurement, and preliminary results variations during the same day of the FID Column temperature: 85° C. are read from a standard curve prepared as response. Helium flow: 25 ml/min. discussed below. Air flow: 450 ml/min. 10. Calculations. 8.5. Determination of desorption efficien- 10.1 Read the weight, in mg, correspond- Hydrogen flow: 55 ml/min. cy. ing to each peak area from the standard (3) A 2 µl injection of the desorbed ana- 8.5.1 Importance of determination. The curve. No volume corrections are needed, belyte is used. desorption efficiency of a particular comcause the standard curve is based on mg/1.0 (4) A sampling rate of 100 ml/min is recpound can vary from one laboratory to anml methanol and the volume of sample inommended. other and also from one batch of charcoal jected is identical to the volume of the to another. Thus, it is necessary to deterstandards injected. OSHA LABORATORY MODIFICATION OF NIOSH mine at least once the percentage of the 10.2 Corrections for the blank must be METHOD S-156 specific compound that is removed in the made for each sample. desorption process, provided the same batch Analyte: Acrylonitrile. of charcoal is used. mg = mg sample - mg blank Matrix: Air. 8.5.2 Procedure for determining desorp- Procedure: Adsorption on charcoal, desorp- Where: tion efficiency. Activated charcoal equivation with methanol, GC. mg sample = mg found in front section of lent to the amount in the first section of the sample tube. 1. Principle of the Method (Reference 1). sampling tube (100 mg) is measured into a mg sample = mg found in front section of 1.1 A known volume of air is drawn 2.5 in, 4-mm I.D. glass tube, flame sealed at blank tube. through a charcoal tube to trap the organic one end. This charcoal must be from the same batch as that used in obtaining the A similar procedure is followed for the vapors present. 1.2 The charcoal in the tube is transsamples and can be obtained from unused backup sections. charcoal tubes. The open end is capped with 10.3 Add the weights found in the front ferred to a small, stoppered sample vial, and and backup sections to get the total weight the analyte is desorbed with methanol. Parafilm. A known amount of hexane soluin the sample. 1.3 An aliquot of the desorbed sample is tion of acrylonitrile containing 0.239 g/ml is injected directly into the activated charcoal 10.4 Read the desorption efficiency from injected into a gas chromatograph. with a microliter syringe, and tube is capped the curve (see sec. 8.5.2) for the amount 1.4 The area of the resulting peak is dewith more Parafilm. When using an autofound in the front section. Divide the total termined and compared with areas obtained matic sample injector, the sample injector weight by this desorption efficiency to for standards. vials, capped with Teflon-faced septa, may obtain the corrected mg/sample. 2. Advantages and disadvantages of the be used in place of the glass tubes. method. Corrected mg/sample = Total weight/D.E. The amount injected is equivalent to that 2.1 The sampling device is small, portapresent in a 20-liter air sample at the select- 10.5 The concentration of the analyte in ble, and involves no liquids. Interferences ed level. the air sampled can be expressed in mg/cu are minimal, and most of those which do Six tubes at each of three levels (0.5X, 1X, m. occur can be eliminated by altering chromaand 2X of the standard) are prepared in this tographic conditions. The tubes are anamanner and allowed to stand for at least mg/cu m = Corrected mg (section 10.4) 1,000 (liter/cu m)/air volume sampled (liter) lyzed by means of a quick, instrumental overnight to assure complete adsorption of method. the analyte onto the charcoal. These tubes 10.6 Another method of expressing con- 2.2 This method may not be adequate for are referred to as the sample. A parallel centration is ppm. the simultaneous analysis of two or more blank tube should be treated in the same substances. manner except that no sample is added to it. ppm = mg/cu X 24.45/M.W. X 760/P T + 273/298 2.3 The amount of sample which can be The sample and blank tubes are desorbed taken is limited by the number of milliand analyzed in exactly the same manner as Where: grams that the tube will hold before overthe sampling tube described in section 8.4. P = Pressure (mm Hg) of air sampled. loading. When the sample value obtained Two or three standards are prepared by T = Temperature (°C) of air sampled. for the backup section of the charcoal tube injecting the same volume of compound into 24.45 = Molar volume (liter/mole) at 25° C exceeds 25 percent of that found on the 1.0 ml of methanol with the same syringe and 760 mm Hg. front section, the possibility of sample loss used in the preparation of the samples. M. Molecular weight (g/mole) of anaexists. These are analyzed with the samples. lyte. 2.4 The precision of the method is limit- The desorption efficiency (D.E.) equals 760 = Standard pressure (mm Hg). ed by the reproducibility of the pressure the average weight in mg recovered from 298 = Standard temperature (°K). drop across the tubes. This drop will affect the tube divided by the weight in mg added to the tube, or 11. References. the flow rate and cause the volume to be im- 11.1 White, L. D. et al., "A Convenient precise, because the pump is usually cali- D.E. = Average weight recovered (mg)/ Optimized Method for the Analysis of Sebrated for one tube only. weight added (mg) lected Solvent Vapors in the Industrial At- 3. Apparatus. The desorption efficiency is dependent on mosphere," Amer. Ind. Hyg. Assoc. J., 31:225 3.1 A calibrated personal sampling pump the amount of analyte collected on the (1970). whose flow can be determined within +6 charcoal. Plot the desorption efficiency 11.2 Documentation of NIOSH Validapercent at the recommended flow rate. versus weight of analyte found. This curve tion Tests, NIOSH Contract No. CDC-99- 3.2 Charcoal tubes: Glass tube with both is used in section 10.4 to correct for adsorp- 74-45. ends flame sealed, 7 cm long with a 6-mm tion losses. 11.3 Final Report, NIOSH Contract O.D. and a 4-mm I.D., containing 2 sections 9. Calibration and standards. HSM-99-71-31, "Personal Sampler Pump of 20/40 mesh activated charcoal separated It is convenient to express concentration for Charcoal Tubes," September 15, 1972. by a 2-mm portion of urethane foam. The of standards in terms of mg/1.0 ml methaactivated charcoal is prepared from coconut NIOSH MODIFICATION OF NIOSH METHOD S- nol, because samples are desorbed in this shells and is fired at 600* c prior to packing. 156 amount of methanol. The density of the an- The absorbing section contains 100 mg of alyte is used to convert mg into microliters The NIOSH recommended method for low charcoal, the back-up section 50 mg. A 3-mm for easy measurement with a microliter sylevels for acrylonitrile is a modification of portion of urethane foam is placed between ringe. A series of standards, varying in conmethod S-156. It differs in the following rethe outlet end of the tube and the back-up centration over the range of interest, is prespects: section. A plug of sililated glass wool is pared and analyzed under the same GC con- (1) Samples are desorbed using 1 ml of 1 placed in front of the adsorbing section. ditions and during the same time period as percent acetone in CS, rather than metha- The pressure drop across the tube must be the unknown samples. Curves are estabnol. less than one inch of mercury at a flow rate lished by plotting concentration in mg/1.0 (2) The analytical column and conditions of 1 liter per minute. ml versus peak area. are: 3.3 Gas chromatograph equipped with a Column: 20 percent SP-1000 on 80/100 Su- NOTE.-Since no internal standard is used nitrogen phosphorus detector. pelcoport 10 feet X 1/2 inch S.S. in the method, standard solutions must be 3.4 Column (10-ft X 1/8"-in stainless analyzed at the same time that the sample Conditions: steel) packed with 100/120 Supelcoport analysis is done. This will minimise the Injector temperature: 200' C. coated with 10 percent SP 1000. FEDERAL REGISTER, VOL. 43, NO. 192-TUESDAY, OCTOBER 3, 1978 RULES AND REGULATIONS 45819 3.5 An electronic integrator or some 5.3.8 Submit at least one blank tube (a specific compound that is removed in the other suitable method for measuring peak charcoal tube subjected to the same handesorption process, provided the same batch areas. dling procedures, without having any air of charcoal is used. 3.6 Two-milliliter sample vials with drawn through it) with each set of samples. 5.5.2 Procedure for determining desorp- Teflon-lined caps. 5.3.9 Take necessary shipping and packtion efficiency. The reference portion of the 3.7 Microliter syringes: 10-microliter, and ing precautions to minimize breakage of charcoal tube is removed. To the remaining other convenient sizes for making standsamples. portion, amounts representing 0.5X, 1X, and ards. 5.4 Analysis of samples. 2X (X represents TLV) based on a 20 1 air 3.8 Pipets: 1.0-ml delivery pipets. 5.4.1 Preparation of samples. In preparasample are injected onto several tubes at 3.9 Volumetric flasks: convenient sizes tion for analysis, each charcoal tube is each level. Dilutions of acrylonitrile with for making standard solutions. scored with a file in front of the first secmethanol are made to allow injection of 4. Reagents. tion of charcoal and broken open. The glass measurable quantities. These tubes are then 4.1 Chromatographic quality methanol. wool is removed and discarded. The charallowed to equilibrate at least overnight. 4.2 Acrylonitrile, reagent grade. coal in the first (larger) section is trans- Following equilibration they are analyzed 4.3 Filtered compressed air. ferred to a 2-ml vial. The separating section following the same procedure as the sam- 4.4 Purified hydrogen. of foam is removed and discarded; the secples. A curve of the desorption efficiency 4.5 Purified helium. tion is transferred to another capped vial. amt recovered/amt added 5. Procedure. These two sections are analyzed separately. 5.1 Cleaning of equipment. All glassware 5.4.2 Desorption of samples. Prior to is plotted versus amount of analyte found. used for the laboratory analysis should be analysis, 1.0 ml of methanol is pipetted into This curve is used to correct for adsorption properly cleaned and free of organics which each sample container. Desorption should losses. could interfere in the analysis. be done for 30 minutes in an ultrasonic 6. Calibration and standards. 5.2 Calibration of personal pumps. Each bath. The sample vials are recapped as soon A series of standards, varying in concenpump must be calibrated with a representaas the solvent is added. tration over the range of interest, is pretive charcoal tube in the line. 5.4.3 GC conditions. The typical operatpared and analyzed under the same GC con- 5.3 Collection and shipping of samples. ing conditions for the gas chromatograph ditions and during the same time period as 5.3.1 Immediately before sampling, break are: the unknown samples. Curves are prepared the ends of the tube to provide an opening 1. 30 ml/min (60 psig) helium carrier gas by plotting concentration versus peak area. at least one-half the internal diameter of flow. the tube (2 mm). 2. 3.0 ml/min (30 psig) hydrogen gas flow NOTE-Since no internal standard is used 5.3.2 The smaller section of the charcoal to detector. in the method, standard solutions must be is used as the backup and should be placed 3. 50 ml/min (60 psig) air flow to detector. analyzed at the same time that the sample nearest the sampling pump. 4. 200° C injector temperature. analysis is done. This will minimize the 5.3.3 The charcoal should be placed in a 5. 200° C dejector temperature. effect of known day-to-day variations and vertical position during sampling to mini- 6. 100° C column temperature. variations during the same day of the NPD mize channeling through the charcoal. 5.4.4 Injection. Solvent flush technique response. Multiple injections are necessary. 5.3.4 Air being sampled should not be or equivalent. passed through any hose or tubing before 7. Calculations. 5.4.5 Measurement of area. The area of entering the charcoal tube. the sample peak is measured by an electron- Read the weight, corresponding to each 5.3.5 A sample size of 20 liters is recomic integator or some other suitable form of peak area from the standard curve, correct mended. Sample at a flow rate of approxiarea measurement, and preliminary results for the blank, correct for the desorption efmately 0.2 liters per minute. The flow rate are read from a standard curve prepared as ficiency, and make necessary air volume corshould be known with an accuracy of at rections. discussd below. least ±5 percent. 5.5 Determination of desorption efficien- 8. Reference. NIOSH Method S-156. 5.3.6 The temperature and pressure of cy. (Secs. 4, 6, 8, 84 Stat. 1592, 1593, 1596, 1599 the atmosphere being sampled should be re- 5.5.1 Importance of determination. The (29 U.S.C. 653, 655, 657); Secretary of corded. desorption efficiency of a particular com- Labor's Order No. 8-76 (41 FR 25059); 29 5.3.7 The charcoal tubes should be pound can vary from one laboratory to an- CFR Part 1911.) capped with the supplied plastic caps immeother and also from one batch of charcoal diately after sampling. Rubber caps should to another. Thus, it is necesary to deternot be used. mine, at least once, the percentage of the [FR Doc. 78-27880 Filed 9-29-78; 8:45 am] FEDERAL REGISTER, VOL. 43, NO. 192-TUESDAY, OCTOBER 3, 1978