Header:
TITLE 8. INDUSTRIAL RELATIONS
DIVISION 1. DEPARTMENT OF INDUSTRIAL RELATIONS
CHAPTER 4. DIVISION OF INDUSTRIAL SAFETY
SUBCHAPTER 7. GENERAL INDUSTRY SAFETY ORDERS
GROUP 16. CONTROL OF HAZARDOUS SUBSTANCES
ARTICLE 110. REGULATED CARCINOGENS
Date:
11/25/2013
Document:
ยง 5220. Ethylene Oxide
(a) Scope and Application.
(1) This section applies to all occupational exposures to ethylene oxide (EtO) except as provided in subsection (a)(2).
(2) This section does not apply to the processing, use, or handling of products made from or containing EtO where objective data demonstrate that the product is not capable of releasing airborne EtO in concentrations at or above the action level under conditions of processing, use, or handling that would reasonably be expected to cause the greatest possible release.
(3) Where a product is exempted pursuant to subsection (a)(2), the employer shall maintain a record of the objec-tive data supporting that exemption and the basis for the employer's reliance on the data, as provided in subsection (k)(1).
(4) Sections 5221 and 5222 also apply where EtO is used in walk-in chambers for fumigation or sterilization pur-poses.
(5) Every employer using EtO shall report such use(s) to the Chief in accordance with subsection (m) except to the extent that the use of EtO is exempt under the provisions of subsection (a)(2).
(b) Definitions: For the purpose of this section, the following definitions shall apply:
"Action Level." Employee exposure to airborne EtO at an 8-hour time-weighted average concentration of 0.5 part EtO per million parts of air (0.5 ppm).
"Authorized Person." Any person specifically authorized by the employer whose duties require the person to en-ter a regulated area, or any person entering such an area as a designated representative of employees for the purpose of exercising the right to observe monitoring and measuring procedures under subsection (3).
"Chief." The chief administrative officer of the Division of Occupational Safety and Health, P.O. Box 420603, San Francisco, CA 94142.
"Director." The Director of the National Institute for Occupational Safety and Health, U.S. Department of Health and Human Services, or designee.
"Emergency." Any occurrence such as, but not limited to, equipment failure, rupture of containers, or failure of control equipment that is likely to or does result in an unexpected significant release of EtO.
"Employee Exposure." Exposure to airborne EtO without regard to the employee's use of respiratory protective equipment.
"Ethylene Oxide" or "EtO." The three-membered ring compound with the empirical chemical formula, C2H4O, and Chemical Abstracts Service Register No. 75-21-8.
(c) Permissible Exposure Limit (PEL).
(1) Permissible Exposure Limit (PEL). The employer shall ensure that no employee is exposed to an 8-hour time-weighted average concentration of airborne EtO in excess of one (1) part EtO per million parts of air (1 ppm).
(2) Short Term Exposure Limit (STEL). The employer shall ensure that no employee is exposed to a concentration of airborne EtO in excess of 5 parts of EtO per million parts of air (5 ppm) as averaged over a sampling period of fifteen (15) minutes.
(d) Exposure Monitoring.
(1) General.
(A) Determinations of employee exposure shall be made from breathing zone air samples that are representative of the 8-hour time-weighted average exposure of each employee.
(B) Determinations of representative employee exposure shall be based on one or more samples representing full-shift exposure for each shift for each job classification in each work area.
(C) Where the employer can document that exposure levels are equivalent for similar operations on different work shifts, the employer need only determine representative employee exposure for such operations during one shift.
(2) Initial Monitoring.
(A) Each employer who has a workplace or work operation covered by this regulation, except as provided for in subsections (a)(2) or (d)(2)(B), shall perform initial monitoring to determine accurately the concentrations of airborne EtO to which employees may be exposed.
(B) Where the employer has monitored after June 15, 1983 and the monitoring satisfies all other requirements of this section, the employer may rely on such earlier monitoring results to satisfy the requirements of subsection (d)(2)(A).
(3) Monitoring Frequency (Periodic Monitoring).
(A) If the monitoring required by subsection (d)(2) reveals employee exposure at or above the action level but not above the permissible exposure limit, the employer shall repeat such monitoring for each such employee at least every 6 months.
(B) If the monitoring required by subsection (d)(2)(A) reveals employee exposure above the permissible exposure limit, the employer shall repeat such monitoring for each such employee at least every 3 months.
(C) The employer may alter the monitoring schedule from quarterly to semiannually for any employee for whom two consecutive measurements taken at listed 7 days apart indicate that the employee's exposure has decreased to or below the permissible exposure limit.
(D) If the monitoring required by subsection (d) (2) (A) reveals employee exposure above the STEL, the employer shall repeat such monitoring for each such employee at least every 3 months, and more often as necessary to evaluate the employee's short term exposures.
(4) Termination of Monitoring.
(A) If the initial monitoring required by subsection (d)(2)(A) reveals employee exposure to be below the action level, the employer may discontinue the monitoring for those employees whose exposures are represented by the initial monitoring.
(B) If the periodic monitoring required by subsection (d)(3) reveals that employee exposures, as indicated by at least two consecutive measurements taken at least 7 days apart, are below the action level, the employer may discon-tinue the monitoring for those employees whose exposures are represented by such monitoring.
(C) If the initial monitoring required by subsection (d) (2) reveals employee exposure to be at or below the STEL, the employer may discontinue short term exposure monitoring for those employees whose exposures are represented by the initial monitoring.
(D) If the periodic monitoring required by subsection (d) (3) (D) reveals that employee exposures, as indicated by at least two consecutive measurements taken at least 7 days apart, are at or below the STEL, the employer may dis-continue short term exposure monitoring for those employees whose exposures are represented by such monitoring.
(5) Additional Monitoring. Notwithstanding the provisions of subsection (d)(4), the employer shall institute the exposure monitoring required under subsections (d)(2)(A) and (d)(3) whenever there has been a change in the pro-duction, process, control equipment, personnel or work practices that may result in new or additional employee ex-posures or when the employer has any reason to suspect that a change may result in new or additional exposures.
(6) Accuracy of Monitoring.
(A) Monitoring shall be accurate, to a confidence level of 95 percent, to within plus or minus 25 percent for con-centrations of airborne EtO at the permissible exposure limit and to within plus or minus 35 percent for concentrations of airborne EtO at the action level.
(B) Monitoring shall be accurate, to a confidence level of 95 percent, to within plus or minus 35 percent for con-centrations of airborne EtO at the STEL.
(7) Employee Notification of Monitoring Results.
(A) The employer shall, within 15 working days after the receipt of the results of any monitoring performed under this regulation, notify the affected employee of these results in writing either individually or by posting the results in an appropriate location that is accessible to affected employees.
(B) The written notification required by subsection (d)(7)(A) shall describe the corrective action being taken by the employer to reduce employee exposure to or below the PEL or STEL wherever monitoring results indicated that the PEL and/or STEL has been exceeded.
(e) Regulated Areas.
(1) The employer shall establish a regulated area wherever employee exposures may exceed the PEL or can rea-sonably be expected to exceed the STEL.
(2) Access to regulated areas shall be limited to authorized persons.
(3) Regulated areas shall be demarcated in any manner that minimizes the number of employees within the regu-lated area.
(4) Regulated areas shall be posted in accordance with subsection (j)(1).
(f) Methods of Compliance.
(1) Engineering Controls and Work Practices.
(A) The employer shall institute engineering controls and work practices to reduce and maintain employee expo-sure to or below the PEL except to the extent that such controls are not feasible.
(B) Wherever the feasible engineering controls and work practices that can be instituted are not sufficient to re-duce employee exposure to or below the PEL, the employer shall use them to reduce employee exposure to the low-est levels achievable by these controls and shall supplement them by the use of respiratory protection that complies with the requirements of subsection (g).
Note: Engineering controls are generally infeasible for the following operations: collection of quality assurance sampling from sterilized materials; removal of biological indicators from sterilized materials; loading and unloading of tank cars; changing of ethylene oxide tanks on sterilizers; and vessel cleaning. For these operations, engineering con-trols are required only where the Assistant Secretary of Labor for Occupational Safety and Health, U.S. Department of Labor or the Chief demonstrate that such controls are feasible.
(2) Compliance Program.
(A) Where the PEL is exceeded, the employer shall establish and implement a written program to reduce employ-ee exposure to or below the PEL by means of engineering and work practice controls, as required by subsection (f)(1), and by the use of respiratory protection where required or permitted under this section.
(B) The compliance program shall include a schedule for periodic leak detection surveys and, as specified in sub-section (h)(1), a written plan for emergency situations.
(C) Written plans for a program required in subsection (f)(2) shall be developed and furnished upon request for examination and copying to authorized representatives of the Chief, the Director, affected employees and designated employee representatives. Such plans shall be reviewed at least every 12 months, and shall be updated as necessary to reflect significant changes in the status of the employer's compliance program.
(D) The employer shall not implement a schedule of employee rotation as a means of compliance with the PEL or the STEL.
(g) Respiratory Protection and Personal Protective Equipment.
(1) General. For employees who are required to use respirators by this section, the employer must provide respi-rators that comply with the requirements of this subsection. Respirators must be used during:
(A) Periods necessary to install or implement feasible engineering and work practice controls;
(B) Work operations such as maintenance and repair activities, vessel cleaning, or other activities for which engi-neering and work practice controls are not feasible;
(C) Work operations for which feasible engineering and work practice controls are not yet sufficient to reduce exposure to or below the PEL; and
(D) Emergencies.
(2) Respirator program. The employer must implement a respiratory protection program in accordance with sec-tion 5144(b) (except (d)(1)(C)) through (m).
(3) Respirator Selection.
(A) The employer shall select, and provide to employees, the appropriate respirators specified in Section 5144(d)(3)(A)1; however, employers shall not select or use half masks of any type because EtO may cause eye irritation or injury.
(B) Each air-purifying, full facepiece respirator shall be equipped with a front- or back-mounted canister approved for protection against ethylene oxide.
(C) For escape, the employer shall provide employees with any respirator permitted for use under subsections (g)(3)(A) and (B).
(4) Protective Clothing and Equipment. Where eye or skin contact with liquid EtO or EtO solutions may occur, the employer shall select and provide, at no cost to the employee, appropriate protective clothing or other equipment in accordance with Sections 3380, 3382, 3383, and 3384 to protect any area of the body that may come in contact with liquid EtO or EtO in solution and shall ensure that the employee wears the protective clothing and equipment provided.
(h) Emergency Situations.
(1) Written Plan.
(A) A written plan for emergency situations shall be developed for each workplace where there is a possibility of an emergency. Appropriate portions of the plan shall be implemented in the event of an emergency.
(B) The plan shall specifically provide that employees engaged in correcting emergency conditions shall be equipped with respiratory protection as required by subsection (g) until the emergency is abated.
(C) The plan shall include the elements prescribed by Section 3220, Emergency Action Plan, and Section 3221, Fire Prevention Plan.
(2) Alerting Employees. Where there is the possibility of employee exposure to EtO due to an emergency, means shall be developed and provided to promptly alert potentially affected employees upon such occurrences. Affected employees not engaged in correcting the emergency conditions shall be immediately evacuated from the area and shall not be permitted to return until the emergency is abated.
(3) Reporting of Emergencies. Emergencies shall be reported to the Chief in accordance with subsection (m).
(i) Medical Surveillance.
(1) General.
(A) The employer shall institute a medical surveillance program for all employees who are or may be exposed to EtO at or above the action level, without regard to the use of respirators, for at least 30 days a year.
(B) The employer shall make available medical examinations and consultations to all employees who have been exposed to EtO in an emergency situation.
(C) The employer shall ensure that all medical examinations and procedures are performed by or under the su-pervision of a licensed physician and are provided without cost to the employee, without employee loss of pay, and at a reasonable time and place.
(2) Frequency of Medical Examinations and Consultations. The employer shall make medical examinations and consultations available to each employee covered under subsections (i)(1)(A) and (B) on the following schedules:
(A) Prior to assignment of the employee to an area where exposure may be at or above the action level for at least 30 days a year.
(B) At least annually for each employee exposed at or above the action level for at least 30 days in the preceding year.
(C) At termination of employment or upon reassignment to an area where employee exposure is not at or above the action level for at least 30 days a year.
(D) As medically appropriate for any employee exposed during an emergency.
(E) As soon as possible following notification of the employer by an employee either (1) that the employee has developed signs or symptoms indicating possible overexposure to EtO, or (2) that the employee desires medical advice concerning the effects of current or past exposure to EtO on the employee's ability to produce a healthy child.
(F) If the examining physician determines that any of the examinations should be provided more frequently than specified, the employer shall provide such examination to affected employees at the frequencies recommended by the physician.
(3) Content of Medical Examinations and Consultations.
(A) Medical examinations made available pursuant to subsection (i)(2)(A)-(D) shall include:
1. A medical and work history with special emphasis directed to symptoms related to the pulmonary, hematologic, neurologic, and reproductive systems and to the eyes and skin;
2. A physical examination with particular emphasis given to the pulmonary, hematologic, neurologic, and repro-ductive systems and to the eyes and skin;
3. A complete blood count to include at least a white cell count (including differential cell count) and red cell count and hematocrit and hemoglobin determinations; and
4. Any laboratory or other test which the examining physician deems necessary by sound medical practice.
(B) The content of medical examinations or consultations made available pursuant to subsection (i)(2)(E) shall be determined by the examining physician and shall include pregnancy testing or laboratory evaluation of fertility if re-quested by the employee and deemed appropriate by the physician.
(4) Information Provided to the Physician. The employer shall provide the following information to the examining physician:
(A) A copy of this standard and Appendices A, B and C;
(B) A description of the affected employee's duties as they relate to the employee's exposure;
(C) The employee's representative exposure level or anticipated exposure level;
(D) A description of any personal protective and respiratory equipment used or to be used; and
(E) Information from previous medical examinations of the affected employee that is not otherwise available to the examining physician.
(5) Physician's Written Opinion.
(A) The employer shall obtain a written opinion from the examining physician. This written opinion shall contain the results of the medical examination and shall include:
1. The physician's opinion as to whether the employee has any detected medical conditions that would place the employee at an increased risk of material health impairment from exposure to EtO;
2. Any recommended limitations on the employee or upon the use of personal protective equipment such as clothing or respirators; and
3. A statement that the employee has been informed by the physician of the results of the medical examination and of any medical conditions resulting from EtO exposure that require further explanation or treatment.
(B) The employer shall instruct the physician not to reveal in the written opinion given to the employer specific findings or diagnoses unrelated to occupational exposure to EtO.
(C) The employer shall provide a copy of the physician's written opinion to the affected employee within 15 days from its receipt.
(j) Communication of Hazards.
(1) Hazard communication--general.
(A) Chemical manufacturers, importers, distributors and employers shall comply with all requirements of the Haz-ard Communication Standard (HCS) (Section 5194) for EtO.
(B) In classifying the hazards of EtO at least the following hazards are to be addressed: Cancer; reproductive ef-fects; mutagenicity; central nervous system; skin sensitization; skin, eye and respiratory tract irritation; acute toxicity effects; and flammability.
(C) Employers shall include EtO in the hazard communication program established to comply with the HCS (Section 5194). Employers shall ensure that each employee has access to labels on containers of EtO and to safety data sheets, and is trained in accordance with the requirements of HCS and subsection (j)(3) of this section.
(2) Signs and Labels.
(A) Signs.
1. The employer shall post and maintain legible signs demarcating regulated areas and entrances or access ways to regulated areas that bear the following legend:
DANGER
ETHYLENE OXIDE
MAY CAUSE CANCER
MAY DAMAGE FERTILITY OR THE UNBORN CHILD
RESPIRATORY PROTECTION AND PROTECTIVE CLOTHING
MAY BE REQUIRED IN THIS AREA
AUTHORIZED PERSONNEL ONLY
2. Prior to June 1, 2016, employers may use the following legend in lieu of that specified in subsection (j)(2)(A)1. of this section:
DANGER
ETHYLENE OXIDE
CANCER HAZARD AND REPRODUCTIVE HAZARD
AUTHORIZED PERSONNEL ONLY
RESPIRATORS AND PROTECTIVE CLOTHING MAY BE
REQUIRED TO BE WORN IN THIS AREA
(B) Labels.
1. The employer shall ensure that precautionary labels are affixed to all containers the contents of which are ca-pable of causing employee exposure at or above the action level, or the contents of which may reasonably be foreseen to cause employee exposure above the excursion limit and that the labels remain affixed when the containers leave the workplace. For the purposes of this subsection (j)(2)(B), reaction vessels, storage tanks and pipes or piping systems are not considered to be containers.
2. Prior to June 1, 2015, employers may include the following information on containers of EtO in lieu of the la-beling requirements in subsection (j)(1)(A) of this section:
a. DANGER
CONTAINS ETHYLENE OXIDE
CANCER HAZARD AND REPRODUCTIVE HAZARD;
b. A warning statement against breathing airborne concentrations of EtO.
(C) The labeling requirements under this section do not apply where EtO is used as a pesticide, as such term is de-fined in the Federal Insecticide, Fungicide and Rodenticide Act (7 U.S.C.136 et seq.), when it is labeled pursuant to that Act and regulations issued under that Act by the Environmental Protection Agency.
(3) Information and Training.
(A) The employer shall provide employees who are potentially exposed to EtO at or above the action level with information and training on EtO at the time of initial assignment and at least annually thereafter.
(B) Employees shall be informed of the following:
1. The requirements of this regulation with an explanation of its contents, including Appendices A and B;
2. All operations in their work area where EtO is present;
3. The location and availability of this regulation within the workplace; and
4. The medical surveillance program required by subsection (i) with an explanation of the information in Appendix C.
(C) Employee training shall include at least:
1. Methods and observations that may be used to detect the presence or release of EtO in the work area (such as monitoring conducted by the employer, continuous monitoring devices, etc.);
2. The physical and health hazards of EtO;
3. The measures employees can take to protect themselves from hazards associated with EtO exposure, including specific procedures the employer has implemented to protect employees from exposure to EtO, such as work practic-es, emergency procedures, and personal protective equipment to be used; and
4. The details of the hazard communication program developed by the employer in accordance with Section 5194, including an explanation of the labeling system and how employees can obtain and use the appropriate hazard infor-mation.
(k) Recordkeeping.
(1) Objective Data For Exempted Operations.
(A) Where the processing, use, or handling of products made from or containing EtO are exempted from other requirements of this regulation under subsection (a)(2), or where objective data such as earlier monitoring have been relied on in lieu of initial monitoring under subsection (d)(2)(B), the employer shall establish and maintain an accurate record of objective data reasonably relied upon in support of the exemption.
(B) This record shall include at least the following information:
1. The product qualifying for exemption;
2. The source of the objective data;
3. The testing protocol, results of testing, and/or analysis of the material for the release of EtO;
4. A description of the operation exempted and how the data support the exemption; and
5. Other data relevant to the operations, materials, processing, or employee exposures covered by the exemption.
(C) The employer shall maintain this record for the duration of the employer's reliance upon such objective data.
(2) Exposure Measurements.
(A) The employer shall keep an accurate record of all measurements taken to monitor employee exposure to EtO as prescribed in subsection (d).
(B) This record shall include at least the following information:
1. The date of measurement;
2. The operation involving exposure to EtO which is being monitored;
3. Sampling and analytical methods used and evidence of their accuracy;
4. Number, duration, and results of samples taken;
5. Type of protective devices worn, if any; and
6. Name, social security number and exposure of the employees whose exposures are represented.
(C) The employer shall maintain this record for at least thirty (30) years.
(3) Medical Surveillance.
(A) The employer shall establish and maintain an accurate record for each employee subject to medical surveil-lance as prescribed by subsection (i)(1).
(B) The record shall include at least the following information:
1. The name and social security number of the employee;
2. Physicians' written opinions;
3. Any employee medical complaints related to exposure to EtO; and
4. A copy of the information provided to the physician as required by subsection (i)(4).
(C) The employer shall ensure that this record is maintained for the duration of employment plus thirty (30) years.
(4) Availability.
(A) The employer, upon written request, shall make all records required to be maintained by this section available to authorized representatives of the Chief and the Director for examination and copying.
(B) The employer, upon request, shall make any exemption and exposure records required by subsections (k)(1) and (k)(2) of this section available for examination and copying to affected employees, former employees, designated representatives, and authorized representatives of the Chief, in accordance with Section 3204(a)-(e) and (g)-(i).
(C) The employer, upon request, shall make employee medical records required by subsection (k)(3) available for examination and copying to the subject employee, anyone having the specific written consent of the subject employee, and authorized representatives of the Chief, in accordance with Section 3204.
(5) Transfer of Records.
(A) The employer shall comply with the requirements concerning transfer of records set forth in Section 3204(h).
(B) Whenever the employer ceases to do business and there is no successor employer to receive and retain the records for the prescribed period, the employer shall notify the Director in writing at least 90 days prior to their dis-posal and shall transmit them to the Director if requested to do so within the 90-day period.
(l) Observation of Monitoring.
(1) Employee Observation. The employer shall provide affected employees or their designated representatives an opportunity to observe any monitoring of employee exposure to EtO conducted in accordance with subsection (d).
(2) Observation Procedures. When observation of the monitoring of employee exposure to EtO requires entry into an area where the use of protective clothing or equipment is required, the observer shall be provided with and be required to use such clothing and equipment and shall be required to comply with all of the applicable safety and health procedures.
(m) Notification of Use and Emergencies. See section 5203.
(n) Appendices. The information contained in the appendices is not intended by itself to create any additional ob-ligations nor otherwise imposed by this section or to detract from any existing obligation.
Appendix A
Substance Safety Data Sheet
for Ethylene Oxide
I. SUBSTANCE IDENTIFICATION
(A) Substance: Ethylene oxide.
(B) Synonyms: dihydrooxirene, dimethylene oxide, EO, 1, 2-epoxyethane, EtO, ETO, oxacyclopropane, oxane, ox-idoethane, alpha/beta-oxidoethane, oxiran, oxirane.
(C) Ethylene oxide can be found as a liquid or vapor.
(D) EtO is used in the manufacture of ethylene glycol, surfactants, ethanolamines, glycol ethers, and other organic chemicals. EtO is also used as a sterilant and fumigant.
(E) Appearance and color: Colorless liquid below 10.7oC (51.3oF) or colorless gas with an ether-like odor detecta-ble at approximately 700 parts EtO per million parts of air (700 ppm).
(F) Permissible exposure limit: Exposure may not exceed 1 part EtO per million parts of air averaged over the 8-hour work day.
(G) Short term exposure limit: Exposure may not exceed 5 parts EtO per million parts of air averaged over a sam-pling period of 15 minutes.
II. HEALTH HAZARD DATA
(A) Routes of exposure. Ethylene oxide can cause bodily harm if you inhale the vapor, if it comes into contact with your eyes or skin, or if you swallow it.
(B) Effects of overexposure.
(1) Ethylene oxide in liquid form can cause eye irritation and injury to the cornea, frostbite, and severe irritation and blistering of the skin upon prolonged or confined contact. Ingestion of EtO can cause gastric irritation and liver injury. Acute effects from inhalation of EtO vapors include respiratory irritation and lung injury, headache, nausea, vomiting, diarrhea, shortness of breath, and cyanosis (blue or purple coloring of skin). Exposure has also been associ-ated with the occurrence of cancer, reproductive effects, mutagenic changes, neurotoxicity, and sensitization.
(2) EtO has been shown to cause cancer in laboratory animals and has been associated with higher incidences of cancer in humans. Adverse reproductive effects and chromosome damage may also occur from EtO exposure.
(C) Reporting signs and symptoms: You should inform your employer if you develop any signs or symptoms that you suspect are caused by exposure to EtO.
III. EMERGENCY FIRST AID PROCEDURES
(A) Eye exposure: If EtO gets into your eyes, wash your eyes immediately with large amounts of water, lifting the lower and upper eyelids. Get medical attention immediately. Contact lenses should not be worn when working with this chemical.
Section 3400(d) of the General Industry Safety Orders requires that where the eyes or body of any person may be exposed to injurious corrosive materials (such as liquid EtO or EtO-containing solutions), suitable facilities for quick drenching or flushing of the eyes and body shall be provided within the work area for immediate emergency use.
(B) Skin exposure: If EtO gets on your skin, immediately wash the contaminated skin with water. If EtO wets your clothing, including your shoes, remove the clothing immediately and wash the skin with water using an emergency deluge shower. Get medical attention immediately. Thoroughly wash contaminated clothing before reusing. Contam-inated leather shoes or other leather articles should not be reused and should be discarded.
(C) Inhalation: If large amounts of EtO are inhaled, the exposed person must be moved to fresh air at once. If breathing has stopped, perform cardiopulmonary resuscitation. Keep the affected person warm and at rest. Get med-ical attention immediately.
(D) Swallowing: When EtO has been swallowed, give the person large quantities of water immediately. After the water has been swallowed, try to get the person to vomit by having him or her touch the back of the throat with his or her finger. Do not make an unconscious person vomit. Get medical attention immediately.
(E) Rescue: Move the affected person from the hazardous exposure. If the exposed person has been overcome, attempt rescue only after notifying at least one other person of the emergency and putting into effect established emergency procedures. Do not become a casualty yourself. Understand your emergency rescue procedures and know the location of the emergency equipment before the need arises.
IV. RESPIRATORS AND PROTECTIVE CLOTHING
(A) Respirators: You may be required to wear a respirator in emergencies, during nonroutine activities, while your employer is installing engineering controls for the reduction of EtO exposures, or when engineering controls are not feasible. As of the effective date of the EtO regulation, only air supplied positive-pressure, full-facepiece respirators are approved for protection against EtO. If air-purifying respirators are worn in the future, they must have a label is-sued by the National Institute for Occupational Safety and Health (NIOSH) under the provisions of 42 CFR part 84 stating that the respirators have been approved for use with ethylene oxide. For effective protection, respirators must fit your face and head snugly. Respirators should not be loosened or removed in work situations where their use is required.
EtO does not have a detectable odor except at levels well above the permissible exposure limit. If you can smell EtO while wearing a respirator, proceed immediately to fresh air. If you experience difficulty breathing while wearing a respirator, tell your employer.
(B) Protective clothing: You may be required to wear impermeable clothing, gloves, a face shield, or other appro-priate protective clothing to prevent skin contact with liquid EtO or EtO-containing solutions. Where protective clothing is required, your employer must provide clean garments to you as necessary to assure that the clothing protects you adequately.
Replace or repair protective clothing that has become torn or otherwise damaged.
EtO must never be allowed to remain on the skin. Clothing and shoes which are not impermeable to EtO should not be allowed to become contaminated with EtO, and if they do, the clothing should be promptly removed and de-contaminated. Once EtO penetrates shoes or other leather articles, they should not be worn again.
(C) Eye protection: You must wear splashproof safety goggles in areas where liquid EtO or EtO-containing solutions may contact your eyes. In addition, contact lenses should not be worn in areas where eye contact with EtO can occur.
V. PRECAUTIONS FOR SAFE USE, HANDLING, AND STORAGE
(A) EtO is a flammable liquid, and its vapors can easily form explosive mixtures in air.
(B) EtO must be stored in tightly closed containers in a cool, well-ventilated area, away from heat, sparks, flames, strong oxidizers, alkalies and strong bases, acids, and acetylide-forming metals such as copper, silver, mercury and their alloys.
(C) Sources of ignition such as smoking materials, open flames and some electrical devices are prohibited wher-ever EtO is handled, used, or stored in a manner that could create a potential fire or explosion hazard.
(D) You should use non-sparking tools when opening or closing metal containers of EtO, and containers must be bonded and grounded in the rare instances in which liquid EtO is poured or transferred.
(E) Impermeable clothing wet with liquid EtO or EtO-containing solutions may be easily ignited and should be washed down with water before removal. If you are wearing clothing which is not impermeable to EtO and are splashed with liquid EtO or EtO-containing solution, you should immediately remove the clothing while under an emergency deluge shower.
(F) If your skin comes into contact with liquid EtO or EtO-containing solutions, you should immediately use an emergency deluge shower to remove the EtO.
(G) You should not keep food, beverages, or smoking materials in regulated areas where employee exposures are above the permissible exposure limit.
(H) Fire extinguishers and emergency deluge showers for quick drenching should be readily available, and you should know where they are and how to operate them.
(I) Ask your supervisor where EtO is used in your work area and for any additional plant safety and health rules.
VI. ACCESS TO INFORMATION
(A) Each year, your employer is required to inform you of the information contained in this standard and appen-dices for EtO. In addition, your employer must instruct you in the proper work practices for using EtO, in emergency procedures, and in the correct use of protective equipment.
(B) Your employer is required to determine whether you are being exposed to EtO. You or your representative has the right to observe employee measurements and to record the results obtained. Your employer is required to inform you of your exposure. If your employer determines that you are being overexposed, he or she is required to inform you of the actions which are being taken to reduce your exposure to within permissible exposure limits.
(C) Your employer is required to keep records of your exposures and medical examinations. The exposure records must be kept by the employer for at least thirty (30) years. Medical records must be kept for the period of your em-ployment plus thirty (30) years.
(D) Your employer is required to release your exposure records to you and your designated representative and to release your medical records to your physician or designated representative upon your written request in accordance with the provisions of Section 3204, Access to Employee Exposure and Medical Records.
VII. STERILANT USE OF EtO IN HOSPITALS AND HEALTH CARE FACILITIES.
This section of Appendix A, for informational purposes, sets forth EPA's recommendations for modifications in workplace design and practice in hospitals and health care facilities for which the Environmental Protection Agency has registered EtO for uses as a sterilant or fumigant under the Federal Insecticide, Fungicide, and Rodenticide Act, 7 U.S.C. 136 et seq. Published in the Federal Register as mandatory provisions by the EPA at 49 FR 15268 on April 18, 1984 and relegated to advisory status at 49 FR 25675 on June 22, 1984 (concurrent with OSHA's publication of the Federal standard for occupational exposure to EtO), these recommended workplace design and workplace practices are intended to help reduce the exposure of hospital and health care workers to EtO to 1 ppm. For the purposes of this appendix, EPA language which could be misinterpreted to impose mandatory provisions for workplace design and work practices has been amended, primarily by the replacement of "must" by "should," in the recommendations which follow:
1. WORKPLACE DESIGN
(a) Installation of gas line hand valves. Hand valves should be installed on the gas supply line at the connection to the supply cylinders to minimize leakage during cylinder change.
(b) Installation of capture boxes. Sterilizer operations result in a gas/water discharge at the completion of the process. This discharge is routinely piped to a floor drain which is generally located in an equipment or an adjacent room. When the floor drain is not in the same room as the sterilizer and workers are not normally present, all that is necessary is that the room be well ventilated.
A "capture box" should be installed in those workplace layouts where the floor drain is located in the same room as the sterilizer or in a room where workers are normally present. A "capture box" is a piece of equipment that totally encloses the floor drain into which the discharge from the sterilizer is pumped. The "capture box" should be vented directly to a non-recirculating or dedicated ventilation system. Sufficient air intake should be allowed at the bottom of the box to handle the volume of air that is ventilated from the top of the box. The "capture box" can be made of metal, plastic, wood or other equivalent material. The box is intended to reduce levels of EtO discharged into the work room atmosphere. The use of a "capture box" is not needed if: (1) the vacuum pump discharge floor drain is located in a well ventilated equipment or other room where workers are not normally present; or (2) the water sealed vacuum pump discharges directly to a closed sealed sewer line (check local plumbing codes).
If it is impractical to install a vented "capture box" and a well ventilated equipment or other room is not feasible, a box that can be sealed over the floor drain may be used if: (1) The floor drain is located in a room where workers are not normally present and EtO cannot leak into an occupied area; and (2) the sterilizer in use is less than 12 cubic feet in capacity (check local plumbing codes).
(c) Ventilation of aeration units.
[i] Existing aeration units. Existing units should be vented to a non-recirculating or dedicated ventilation system or vented to an equipment or other room where workers are not normally present and which is well ventilated. Aerator units should be positioned as close as possible to the sterilizer to minimize the exposure from the off-gassing of steri-lized items.
[ii] Installation of new aerator units (where none exist). New aerator units should be vented as described above for existing aerators.
(d) Ventilation during cylinder change. Workers may be exposed to short but relatively high levels of EtO during the change of gas cylinders. To reduce exposure from this route, users should select one of three alternatives designed to draw off gas that may be released when the line from the sterilizer to the cylinder is disconnected:
[i] Location of cylinders in a well ventilated equipment room or other room where workers are not normally pre-sent.
[ii] Installation of a flexible hose (at least 4 " in diameter) to a non-recirculating or dedicated ventilation system and located in the area of cylinder change in such a way that the hose can be positioned at the point where the sterilizer gas line is disconnected from the cylinder.
[iii] Installation of a hood that is part of a non-recirculating or dedicated ventilation system and is positioned no more than one foot above or behind the point where the change of cylinders takes place.
(e) Ventilation of sterilizer door area. One of the major sources of exposure to EtO occurs when the sterilizer door is opened following the completion of the sterilization process. In order to reduce this avenue of exposure, a hood or metal canopy closed on each end should be installed over the sterilizer door. The hood or metal canopy should be connected to a non-recirculating or dedicated ventilation system or one that exhausts gases to a well ventilated equipment or other room where workers are not normally present. A hood or canopy over the sterilizer door should be installed for use even with those sterilizers that have a purge cycle.
(f) Ventilation of sterilizer relief valve. Sterilizers are typically equipped with a safety relief device to release gas in case of increased pressure in the sterilizer. Generally, such relief devices are used on pressure vessels. Although these pressure relief devices are rarely opened for hospital and health care sterilizers, it is suggested that they be designed to exhaust vapor from the sterilizer by one of the following methods:
[i] Through a pipe connected to the outlet of the relief valve ventilated directly outdoors at a point high enough to be away from passers-by, and not near any windows that open, nor near any air conditioning or ventilation air intakes.
[ii] Through a connection to an existing or new non-recirculating or dedicated ventilation system.
[iii] Through a connection to a well ventilated equipment or other room where workers are not normally present.
(g) Ventilation systems: Each hospital and health care facility that uses EtO for the sterilization of equipment and supplies should have a ventilation system which enables compliance with the recommendations of section (b) through (f) in the manner described in these sections. Thus, each affected hospital and health care facility should have or install a non-recirculating or dedicated ventilation system or have available a well ventilated equipment or other room where workers are not normally present in which to vent EtO.
(h) Installation of alarm systems. An audible and visual indicator alarm system should be installed to alert personnel of ventilation system failures, i.e., when the ventilation fan motor is not working.
2. WORKPLACE PRACTICES
All the workplace practices discussed in this unit should be permanently posted near the door of each sterilizer prior to use by any operator.
(a) Changing of supply line filters. Filters in the sterilizer liquid line should be changed when necessary by the fol-lowing procedure:
[i] Close the cylinder valve and the hose valve.
[ii] Disconnect the cylinder hose (piping) from the cylinder.
[iii] Open the hose valve and bleed slowly into a proper ventilating system at or near the in-use supply cylinders.
[iv] Vacate the area until the line is empty.
[v] Change the filter.
[vi] Reconnect the lines and reverse the valve position.
[vii] Check hoses, filters, and valves for leaks with a fluorocarbon leak detector (for those sterilizers using the 88 percent chlorofluorocarbon and 12 percent ethylene oxide mixture).
(b) Restricted access area.
[i] Areas involving use of EtO should be designated as restricted access areas. They should be identified with signs or floor marks near the sterilizer door, aerator, vacuum pump floor drain discharge, and in-use cylinder storage.
[ii] All personnel should be excluded from the restricted area when certain operations are in progress, such as discharging a vacuum pump, emptying a sterilizer liquid line, or venting a non-purge sterilizer with the door ajar or other operations where EtO might be released directly into the face of workers.
(c) Door opening procedures.
[i] Sterilizers with purge cycles. A load treated in a sterilizer equipped with a purge cycle should be removed im-mediately upon completion of the cycle (provided no time is lost opening the door after cycle is completed). If this is not done, the purge cycle should be repeated before opening door.
[ii] Sterilizers without purge cycles. For a load treated in a sterilizer not equipped with a purge cycle, the sterilizer door should be ajar 6 " for 15 minutes, and then fully opened for at least another 15 minutes before removing the treated load. The length of time of the second period should be established by peak monitoring for one hour after the two 15-minute periods suggested. If the level is above 10 ppm time-weighted average for 8 hours, more time should be added to the second waiting period (door wide open). However, in no case should the second period be shortened to less than 15 minutes.
(d) Chamber unloading procedures.
[i] Procedures for unloading the chamber should include the use of baskets or rolling carts, or baskets and rolling tables to transfer treated loads quickly, thus avoiding excessive contact with treated articles and reducing the duration of exposures.
[ii] If rolling carts are used, they should be pulled not pushed by the sterilizer operators to avoid off-gassing ex-posure.
(e) Maintenance. A written log should be instituted and maintained documenting the date of each leak detection and any maintenance procedures undertaken.
[i] Leak detection. Sterilizer door gaskets, cylinder and vacuum piping, hoses, filters, and valves should be checked for leaks under full pressure with a fluorocarbon leak detector (for 12/88 systems only) every two weeks by mainte-nance personnel. Also, the cylinder piping connections must be checked after changing cylinders. Particular attention in leak detection should be given to the automatic solenoid valves that control the flow of EtO to the sterilizer. Specif-ically, a check should be made at the EtO gasoline entrance port to the sterilizer, while the sterilizer door is open and the solenoid valves are in a closed position.
[ii] Maintenance procedures. Sterilizer/aerator door gaskets, valves, and fittings should be replaced when neces-sary as determined by maintenance personnel in their bi-weekly checks; in addition, visual inspection of the door gas-kets for cracks, debris, and other foreign substances should be conducted daily by the operator.
Appendix B
Substance Technical Guidelines
for Ethylene Oxide
I. PHYSICAL AND CHEMICAL DATA
(A) Substance identification
(1) Synonyms: dihydrooxirene, dimethylene oxide, EO, 1, 2-epoxyethane, EtO, ETO, oxacyclopropane, oxane, ox-idoethane, alpha/beta-oxidoethane, oxiran, oxirane
(2) Formula: [SEE FORMULA IN ORIGINAL]
(3) Molecular weight: 44.06
(B) Physical data:
(1) Boiling point (760 mm Hg): 10.7oC (51.3oF)
(2) Specific gravity (water = 1): 0.87 (at 20oC or 68oF)
(3) Vapor density (air = 1): 1.49
(4) Vapor pressure (at 20oC): 1,095 mm Hg
(5) Solubility in water: complete
(6) Appearance and odor: colorless liquid; gas at temperatures above 10.7oF (51.3oC) with an ether-like odor de-tectable above 700 ppm
II. FIRE, EXPLOSION, AND REACTIVITY HAZARD DATA
(A) Fire:
(1) Flash point: less than 0oF (open cup);
(2) Stability: decomposes violently at temperatures above 800oF;
(3) Flammable limits in air, percent by volume: Lower: 3, Upper: 100;
(4) Extinguishing media: Carbon dioxide for small fires, polymer or alcohol foams for large fires;
(5) Special fire fighting procedures: Dilution of ethylene oxide with 23 volumes of water renders it non-flammable;
(6) Unusual fire and explosion hazards: Vapors of EtO will burn without the presence of air or other oxidizers. EtO vapors are heavier than air and may travel along the ground and be ignited by open flames or sparks at locations re-mote from the site at which EtO is being used.
(7) For purposes of compliance with the requirements of Articles 141 through 148 of the General Industry Safety Orders, EtO is classified as a flammable gas. For example, 7,500 ppm, approximately one-fourth of the lower flammable limit, would be considered to pose a potential fire and explosion hazard.
(8) For purposes of compliance with regulations for fire protection, EtO is classified as a Class B fire hazard.
(9) For purposes of compliance with the Electrical Safety Orders (California Administrative Code, Title 8, Subchap-ters 5 and 6), locations classified as hazardous due to the presence of EtO shall be Class I.
(B) Reactivity:
(1) Conditions contributing to instability: EtO will polymerize violently if contaminated with aqueous alkalies, amines, mineral acids, metal chlorides, or metal oxides. Violent decomposition will also occur at temperatures above 800oF;
(2) Incompatibilities: Alkalies and acids;
(3) Hazardous decomposition products: Carbon monoxide and carbon dioxide.
III. SPILL, LEAK, AND DISPOSAL PROCEDURES
(A) If EtO is spilled or leaked, the following steps should be taken:
(1) Remove all ignition sources.
(2) The area should be evacuated at once and re-entered only after the area has been thoroughly ventilated and washed down with water.
(B) Persons not wearing appropriate protective equipment must be restricted from areas of spills or leaks until cleanup has been completed.
(C) Waste disposal methods: Waste material shall be disposed of in a manner that is not hazardous to employees or to the general population. In selecting the method of waste disposal, applicable local, State, and Federal regulations should be consulted.
IV. MONITORING AND MEASUREMENT PROCEDURES
(A) Exposure above the Permissible Exposure Limit:
(1) Measurements taken for the purpose of determining employee exposure under this section are best taken with consecutive samples covering the full shift. Air samples must be taken in the employee's breathing zone (air that would most nearly represent that inhaled by the employee).
(2) The sampling and analysis under this section may be performed by collection of the EtO vapor on charcoal ad-sorption tubes or other composition adsorption tubes, with subsequent chemical analysis. Sampling and analysis may also be performed by instruments such as a real-time continuous monitoring systems, portable direct reading instru-ments, or passive dosimeters provided measurements taken using these methods accurately evaluate the concentra-tion of EtO in employees' breathing zones.
Appendix D describes the validated method of sampling and analysis which has been tested by Federal OSHA for use with EtO. The employer has the obligation of selecting a monitoring method which meets the accuracy and preci-sion requirements of the standard under his or her unique field conditions. The standard requires that the method of monitoring must be accurate, to a 95 percent confidence level, to plus or minus 25 percent for concentrations of EtO at 1 ppm and to plus or minus 35 percent for concentrations at 0.5 ppm.
(B) Since many of the employer's duties under the regulation depend upon the results of employee exposure measurements, employers must assure that the evaluation of employee exposures is performed by a technically quali-fied person.
V. PROTECTIVE CLOTHING AND EQUIPMENT
Employees shall be provided with and be required to wear appropriate protective clothing wherever there is sig-nificant potential for skin contact with liquid EtO or EtO-containing solutions. Protective clothing shall include imper-meable coveralls or similar full-body work clothing, gloves, and head coverings, as appropriate to protect areas of the body which may come in contact with liquid EtO or EtO-containing solutions.
Employers must ascertain that the protective garments are impermeable to EtO. Permeable clothing, including items made of rubber, and leather shoes should not be allowed to become contaminated with liquid EtO or EtO-containing solutions. If permeable clothing does become contaminated, it should be immediately removed while the employee is under an emergency deluge shower. If leather footwear or other leather garments become wet from EtO they should be discarded and not be worn again because leather absorbs EtO and holds it against the skin.
Any protective clothing that has been damaged or is otherwise found to be defective should be repaired or re-placed. Clean protective clothing should be provided to the employee as necessary to assure employee protection. Whenever impermeable clothing becomes wet with liquid EtO or EtO-containing solutions, it should be washed down with water before being removed by the employee. Employees are also required to wear splash-proof safety goggles where there is any possibility of EtO contacting the eyes.
VI. MISCELLANEOUS PRECAUTIONS
(A) Store EtO in tightly closed containers in a cool, well-ventilated area and take all necessary precautions to avoid any explosion hazard.
(B) Non-sparking tools must be used to open and close metal containers. These containers must be effectively grounded and bonded.
(C) Do not incinerate EtO cartridges, tanks or other containers.
(D) Employers shall advise employees of all areas and operations where exposure to EtO could occur.
VII. COMMON OPERATIONS
Common operations in which exposure to EtO is likely to occur include the following: Manufacture of EtO, surfac-tants, ethanolamines, glycol ethers, and specialty chemicals, and use as a sterilant and fumigant in the hospital, health product and spice industries.
Appendix C
Medical Surveillance Guidelines
for Ethylene Oxide
I. ROUTE OF ENTRY
Inhalation.
II. TOXICOLOGY
Clinical evidence of adverse effects associated with exposure to EtO is present in the form of increased incidence of cancer in laboratory animals (leukemia, stomach, brain), mutation in offspring in animals, and resorptions and spontaneous abortions in animals and human populations, respectively. Findings in humans and experimental animals exposed to airborne EtO also indicate damage to the genetic material (DNA). These include hemoglobin alkylation, unscheduled DNA synthesis, sister chromatid exchange, chromosomal aberration, and functional sperm abnormalities.
Ethylene oxide in liquid form can cause eye irritation and injury to the cornea, frostbite, severe irritation, and blistering of the skin upon prolonged or confined contact. Ingestion of EtO can cause gastric irritation and liver injury. Other effects from inhalation of EtO vapors include respiratory irritation and lung injury, headache, nausea, vomiting, diarrhea, dyspnea and cyanosis.
III. SIGNS AND SYMPTOMS OF ACUTE OVEREXPOSURE
The early effects of acute overexposure to EtO are nausea and vomiting, headache, and irritation of the eyes and respiratory passages. The patient may notice a "peculiar taste" in the mouth. Delayed effects can include pulmonary edema, drowsiness, weakness, and incoordination. Studies suggest that blood cell changes, an increase in chromosomal aberrations, and spontaneous abortion may also be causally related to acute overexposure to EtO.
Skin contact with liquid or gaseous EtO causes characteristic burns and possibly even an allergic-type sensitization. The edema and erythema occurring from skin contact with EtO progress to vesiculation with a tendency to coalesce into blebs with desquamation. Healing occurs within three weeks, but there may be a residual brown pigmentation. A 40-80% solution is extremely dangerous, causing extensive blistering after only brief contact. Pure liquid EtO causes frostbite because of rapid evaporation.
Most reported acute effects of occupational exposure to EtO are due to contact with EtO in liquid phase. The liquid readily penetrates rubber and leather, and will produce blistering if clothing or footwear contaminated with EtO are not removed.
IV. SURVEILLANCE AND PREVENTIVE CONSIDERATIONS
As noted above, exposure to EtO has been linked to an increased risk of cancer and reproductive effects including decreased male fertility, fetotoxicity, and spontaneous abortion. EtO workers are more likely to have chromosomal damage than similar groups not exposed to EtO. At the present, limited studies of chronic effects in humans resulting from exposure to EtO suggest a causal association with leukemia. Animal studies indicate leukemia and cancers at other sites (brain, stomach) as well. The physician should be aware of the findings of these studies in evaluating the health of employees exposed to EtO.
Adequate screening tests to determine an employee's potential for developing serious chronic diseases, such as cancer, from exposure to EtO do not presently exist. Laboratory tests may, however, give evidence to suggest that an employee is potentially overexposed to EtO. It is important for the physician to become familiar with the operating conditions in which exposure to EtO is likely to occur. The physician also must become familiar with the signs and symptoms that indicate a worker is receiving otherwise unrecognized and unacceptable exposure to EtO. These ele-ments are especially important in evaluating the medical and work histories and in conducting the physical examination. When an unacceptable exposure in an active employee is identified by the physician, measures taken by the employer to lower exposure should also lower the risk of serious long-term consequences.
The employer is required to institute a medical surveillance program for all employees who are or will be exposed to EtO at or above the action level (0.5 ppm) for at least 30 days per year, without regard to respirator use. All exami-nations and procedures must be performed by or under the supervision of a licensed physician at a reasonable time and place for the employee and at no cost to the employee.
Although broad latitude in prescribing specific tests to be included in the medical surveillance program is extend-ed to the examining physician, OSHA requires inclusion of the following elements in the routine examination:
[i] Medical and work histories with special emphasis directed to symptoms related to the pulmonary, hematologic, neurologic, and reproductive systems and to the eyes and skin.
[ii] Physical examination with particular emphasis given to the pulmonary, hematologic, neurologic, and reproduc-tive systems and to the eyes and skin.
[iii] Compete blood count to include at least a white cell count (including differential cell count), red cell count, hematocrit, and hemoglobin.
[iv] Any laboratory or other test which the examining physician deems necessary by sound medical practice.
If requested by the employee, the medical examinations shall include pregnancy testing or laboratory evaluation of fertility as deemed appropriate by the physician.
In certain cases, to provide sound medical advice to the employer and the employee, the physician must evaluate situations not directly related to EtO. For example, employees with skin diseases may be unable to tolerate wearing protective clothing. In addition, those with chronic respiratory diseases may not tolerate the wearing of negative pressure (air purifying) respirators. Additional tests and procedures that will help the physician determine which em-ployees are medically unable to wear such respirators should include: an evaluation of cardiovascular function, a base-line chest X-ray to be repeated at five-year intervals, and a pulmonary function test to be repeated every three years. The pulmonary function test should include measurement of the employee's forced vital capacity (FVC) and forced expiratory volume at one second (FEV1), the calculation of the ratio of FEV1 to FVC, and the calculation of the ratio of measured FVC and measured FEV1 values to predicted FVC and FEV 1 values based on age, sex, race, and height.
The employer is required to make the prescribed tests available at least annually to employees who are or will be exposed at or above the action level for 30 or more days per year; more often than specified if recommended by the examining physician; and upon the employee's termination of employment or reassignment to another work area. While little is known about the long term consequences of high short-term exposures, it appears prudent to monitor such affected employees closely in light of existing health data. The employer shall provide physician-recommended examinations to any employee exposed to EtO in emergency conditions. Likewise, the employer shall make available medical consultations including physician-recommended examinations to employees who believe they are suffering signs or symptoms of exposure to EtO.
The employer is required to provide the physician with the following information: a copy of this standard and its appendices; a description of the affected employee's duties as they relate to the employee exposure level; and infor-mation from the employee's previous medical examinations which is not readily available to the examining physician. Making this information available to the physician will aid in the evaluation of the employee's health in relation to assigned duties and the employee's fitness to wear personal protective equipment, if required.
The employer is required to obtain a written opinion from the examining physician containing the results of the medical examinations; the physician's opinion as to whether the employee has any detected medical conditions which would place the employee at increased risk of material impairment of his or her health from exposure to EtO; any recommended restrictions upon the employee's exposure to EtO, or upon the use of protective clothing or equipment such as respirators; and a statement that the employee has been informed by the physician of the results of the med-ical examination and of any medical conditions which require further explanation or treatment. This written opinion must not reveal specific findings or diagnoses unrelated to occupational exposure to EtO, and a copy of the opinion must be provided to the affected employee.
The purpose in requiring the examining physician to supply the employer with a written opinion is to provide the employer with a medical basis to aid in the determination of initial placement of employees and to assess the em-ployee's ability to use protective clothing and equipment.
Appendix D
Sampling and Analytical Method
Ethylene Oxide
This appendix contains details for the method which has been tested at the OSHA Analytical Laboratory in Salt Lake City. Inclusion of this method in the appendix does not mean that this method is the only one which will be satisfactory.
Employers who note problems with sample breakthrough using the OSHA or other charcoal methods should try larger charcoal tubes. Tubes of larger capacity are available. In addition, lower flow rates and shorter sampling times should be beneficial in minimizing breakthrough problems.
ETHYLENE OXIDE METHOD NO. : 30
Matrix: Air.
Target Concentration: 1.0 ppm (1.8 mg/m3).
Procedure: Samples are collected on two charcoal tubes in series and desorbed with 1% CS 2 in benzene. The samples are derivatized with HBr and treated with sodium carbonate. Analysis is done by gas chromatography with an electron capture detector.
Recommended Air Volume and Sampling Rate: 1 liter and 0.05 Lpm.
Detection Limit of the Overall Procedure: 13.3 ppb (0.024 mg/m 3) (Based on 1.0 liter air sample).
Reliable Quantitation Limit: 52.2 ppb (0.094 mg/m3) (Based on 1.0 liter air sample).
Standard Error of Estimate: 6.59%.
Special Requirements: Samples must be analyzed within 15 days of sampling date.
Status of Method: The sampling and analytical method has been subjected to the established evaluation proce-dures of the Organic Method Evaluations Branch.
1. General Discussion.
1.1 Background.
1.1.1 History of Procedure.
In studies to develop a method for the analysis of EtO at very low concentrations, it was found that the reaction of EtO with HBr (hydrobromic acid) gave a derivative, 2-bromoethanol, readily detectable by an ECD (electron capture detector) due to the presence of the bromine. Of solvents tested for their response on the ECD and their ability to desorb EtO from the charcoal, benzene was the only solvent tested that gave a suitable response on the ECD and a high desorption. The desorption efficiency was improved by using 1% CS 2 (carbon disulfide) with the benzene.
1.1.2 Physical Properties.
See Section 5220, Appendix B.
1.2 Limit Defining Parameters.
1.2.1 Detection Limit of the Analytical Procedure.
The detection limit of the analytical procedure is 12.0 picograms of ethylene oxide per injection. This is the amount of analyte which will give a peak whose height is five times the height of the baseline noise.
1.2.2 Detection Limit of the Overall Procedure.
The detection limit of the overall procedure is 24.0 nanograms of ethylene oxide per sample. This is the amount of analyte spiked on the sampling device which allows recovery of an amount of analyte equivalent to the detection limit of the analytical procedure.
1.2.3 Reliable Quantitation Limit.
The reliable quantitation limit is 94.0 nanograms of ethylene oxide per sample. This is the smallest amount of an-alyte which can be quantiated within the requirements of 75% recovery and 95% confidence limits.
It must be recognized that the reliable quantitation limit and detection limit are based upon optimization of the instrument for the smallest possible amount of analyte. When the target concentration of an analyte is exceptionally higher than these limits, they may not be attainable at the routine operating parameters. The limits reported on analysis reports must be based on the operating parameters used during the analysis of the samples.
1.2.4 Sensitivity.
The sensitivity of the analytical procedure over a concentration range representing 0.5 to 2 times the target con-centration based on the recommended air volume is 34105 area units per m g/mL. The sensitivity is determined by the slope of the calibration curve.
The sensitivity will vary somewhat with the particular instrument used in the analysis.
1.2.5 Recovery.
The recovery of analyte from the collection medium must be 75% or greater. The average recovery from spiked samples over the range of 0.5 to 2 times the target concentration is 88.0%. At lower concentrations the recovery ap-pears to be non-linear.
1.2.6 Precision (Analytical Method Only).
The pooled coefficient of variation obtained from replicate determinations of analytical standards at 0.5X, 1X and 2X the target concentration is 0.036.
1.2.7 Precision (Overall Procedure).
The overall procedure must provide results at the target concentration that are 25% or better at the 95% confi-dence level. The precision at the 95% confidence level for the 15-day storage test is plus or minus 12.9%.
This includes an additional plus or minus 5% for sampling error.
1.3 Advantages.
1.3.1 The sampling procedure is convenient.
1.3.2 The analytical procedure is very sensitive and reproducible.
1.3.3 Reanalysis of samples is possible.
1.3.4 Samples are stable for at least 15 days at room temperature.
1.3.5 Interferences are reduced by the long GC retention time of the derivative.
1.4 Disadvantages.
1.4.1 Two tubes in series must be used because of possible breakthrough and migration.
1.4.2 The precision of the sampling rate may be limited by the reproducibility of the pressure drop across the tubes. The pumps are usually calibrated for one tube only.
1.4.3 The use of benzene as the desorption solvent increases the hazards of analysis because of the potential car-cinogenic effects of benzene.
1.4.4 After repeated injections there can be a buildup of residue formed on the electron capture detector which decreases sensitivity.
1.4.5 Recovery from the charcoal tubes appears to be nonlinear at low concentrations.
2. Sampling Procedure.
2.1 Apparatus.
2.1.1 A calibrated personal sampling pump whose flow can be determined within plus or minus 5% of the recom-mended flow.
2.1.2 Charcoal tubes: glass tube with both ends flame sealed, 7 cm long with a 6-mm O.D. and a 4-mm I.D., con-taining 2 sections of coconut shell charcoal separated by a 3-mm portion of urethane foam. The adsorbing section contains 100 mg of charcoal, the backup section 50 mg. A 3-mm portion of urethane foam is placed between the outlet end of the tube and the backup section. A plug of silylated glass wool is placed in front of the adsorbing section.
2.2 Reagents.
2.2.1 None required.
2.3 Sampling Technique.
2.3.1 Immediately before sampling, break the ends of the charcoal tubes. All tubes must be from the same lot.
2.3.2 Connect two tubes in series to the sampling pump with a short section of flexible tubing. A minimum amount of tubing is used to connect the two sampling tubes together. The tube closer to the pump is used as a backup. This tube should be identified as the backup tube.
2.3.3 The tubes should be placed in a vertical position during sampling to minimize channeling.
2.3.4 Air being sampled should not pass through any hose or tubing before entering the charcoal tubes.
2.3.5 Seal the charcoal tubes with plastic caps immediately after sampling. Also, seal each sample with OSHA seals lengthwise.
2.3.6 With each batch of samples, submit at least one blank tube from the same lot used for samples. This tube should be subjected to exactly the same handling as the samples (break, seal, transport) except that no air is drawn through it.
2.3.7 Transport the samples (and corresponding paperwork) to the lab for analysis.
2.3.8 If bulk samples are submitted for analysis, they should be transported in glass containers with Teflon-lined caps. These samples must be mailed separately from the container used for the charcoal tubes.
2.4 Breakthrough.
2.4.1 The breakthrough (5% breakthrough) volume for a 3.0 mg/m 3 ethylene oxide sample stream at approxi-mately 85% relative humidity, 22oC and 633 mm is 2.6 liters sampled at 0.05 liters per minute. This is equivalent to 7.8 m g of ethylene oxide. Upon saturation of the tube it appeared that the water may be displacing ethylene oxide during sampling.
2.5 Desorption Efficiency.
2.5.1 The desorption efficiency, from liquid injection onto charcoal tubes, averaged 88.0% from 0.5 to 2.0 x the target concentration for a 1.0-liter air sample. At lower ranges it appears that the desorption efficiency is non-linear.
2.5.2 The desorption efficiency may vary from one laboratory to another and also from one lot of charcoal to an-other. Thus, it is necessary to determine the desorption efficiency for a particular lot of charcoal.
2.6 Recommended Air Volume and Sampling Rate.
2.6.1 The recommended air volume is 1.0 liter.
2.6.2 The recommended maximum sampling rate is 0.05 Lpm.
2.7 Interferences.
2.7.1 Ethylene glycol and Freon 12 at target concentration levels did not interfere with the collection of ethylene oxide.
2.7.2 Suspected interferences should be listed on the sample data sheets.
2.7.3 The relative humidity may affect the sampling procedure.
2.8 Safety Precautions.
2.8.1 Attach the sampling equipment to the employee so that it does not interfere with work performance.
2.8.2 Wear safety glasses when breaking the ends of the sampling tubes.
2.8.3 If possible, place the sampling tubes in a holder so the sharp end is not exposed while sampling.
3. Analytical Method.
3.1 Apparatus.
3.1.1 Gas chromatograph equipped with a linearized electron capture detector.
3.1.2 GC column capable of separating the derivative of ethylene oxide (2-bromoethanol) from any interferences and the 1% CS 2 in benzene solvent. The column used for validation studies was: 10 ft x 1/8-inch stainless steel 20% SP-2100, 0.1% Carbowax 1500 on 100/120 Supelcoport.
3.1.3 An electronic integrator or some other suitable method of measuring peak areas.
3.1.4 Two milliliter vials with Teflon-lined caps.
3.1.5 Gas tight syringe -500 L or other convenient sizes for preparing standards.
3.1.6 Microliter syringes -10 L or other convenient size for diluting standards and 1 L for sample injections.
3.1.7 Pipets for dispensing the 1% CS 2 in benzene solvent. The Glenco 1 mL dispenser is adequate and conven-ient.
3.1.8 Volumetric flasks -5 mL and other convenient sizes for preparing standards.
3.1.9 Disposable Pasteur Pipets.
3.2 Reagents.
3.2.1 Benzene, reagent grade.
3.2.2 Carbon disulfide, reagent grade.
3.2.3 Ethylene oxide, 99.7% pure.
3.2.4 Hydrobromic acid, 48% reagent grade.
3.2.5 Sodium carbonate, anhydrous, reagent grade.
3.2.6 Desorbing reagent, 99% benzene/1% CS2.
3.3 Sample Preparation.
3.3.1 The front and back sections of each sample are transferred to separate 2-mL vials.
3.3.2 Each sample is desorbed with 1.0 mL of desorbing reagent.
3.3.3 The vials are sealed immediately and allowed to desorb for one hour with occasional shaking.
3.3.4 Desorbing reagent is drawn off the charcoal with a disposable pipet and put into clean 2-mL vials.
3.3.5 One drop of HBr is added to each vial. Vials are resealed and HBr is mixed well with the desorbing reagent.
3.3.6 About 0.15 gram of sodium carbonate is carefully added to each vial. Vials are again resealed and mixed well.
3.4 Standard Preparation.
3.4.1 Standards are prepared by injecting the pure ethylene oxide gas into the desorbing reagent.
3.4.2 A range of standards are prepared to make a calibration curve. A concentration of 1.0 m L of ethylene oxide gas per 1 mL desorbing reagent is equivalent to 1.0 ppm air concentration (all gas volumes at 25oC and 760 mm) for the recommended 1-liter air sample. This amount is uncorrected for desorption efficiency.
3.4.3 One drop of HBr per mL of standard is added and mixed well. 3.4.4 About 0.15 grams of sodium carbonate is carefully added for each drop of HBr (a small reaction will occur).
3.5 Analysis.
3.5.1 GC Conditions. Nitrogen flow rate -10mL/min. Injector Temperature -250oC Detector Temperature -300oC Column Temperature -100oC Injection size -0.8 m L Elution time -3.9 minutes
3.5.2 Peak areas are measured by an integrator or other suitable means.
3.5.3 The integrator results are in area units and a calibration curve is set up with concentration vs. area units.
3.6 Interferences.
3.6.1 Any compound having the same retention time of 2-bromoethanol is a potential interference. Possible in-terferences should be listed on the sample data sheets.
3.6.2 GC parameters may be changed to circumvent interferences.
3.6.3 There are usually trace contaminants in benzene. These contaminants, however, posed no problem of in-terference.
3.6.4 Retention time data on a single column is not considered proof of chemical identity. Samples over the 1.0 ppm target level should be confirmed by GC/Mass Spec or other suitable means.
3.7 Calculations.
3.7.1 The concentration in g/mL for a sample is determined by comparing the area of a particular sample to the calibration curve, which has been prepared from analytical standards.
3.7.2 The amount of analyte in each sample is corrected for desorption efficiency by use of a desorption curve.
3.7.3 Analytical results (A) from the two tubes that compose a particular air sample are added together.
3.7.4 The concentration for a sample s calculated by the following equation:
EtO, mg/m3 = (A x B) / C
where:
A = mg/mL
B = desorption volume in milliliters
C = air volume in liters.
3.7.5 To convert mg/m3 to parts per million (ppm) the following relationship is used:
EtO, ppm = (mg/m3 x 24.45) / 44.05
where:
mg/m3 = results from 3.7.4
24.45 = molar volume at 25oC and 760 mm Hg
44.05 = molecular weight of EtO.
3.8 Safety Precautions
3.8.1 Ethylene oxide and benzene are potential carcinogens and care must be exercised when working with these compounds.
3.8.2 All work done with the solvents (preparation of standards, desorption of samples, etc.) should be done in a hood.
3.8.3 Avoid any skin contact with all of the solvents.
3.8.4 Wear safety glasses at all times.
3.8.5 Avoid skin contact with HBr because it is highly toxic and a strong irritant to eyes and skin.
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