Title 29—Labor--Volume 1
PART 1910—OCCUPATIONAL SAFETY AND HEALTH STANDARDS
§ 1910.1043   Cotton dust.
(a) Scope and application. (1) This section, in its entirety, applies to the control of employee exposure to cotton dust in all workplaces where employees engage in yarn manufacturing, engage in slashing and weaving operations, or work in waste houses for textile operations.
(2) This section does not apply to the handling or processing of woven or knitted materials; to maritime operations covered by 29 CFR Parts 1915 and 1918; to harvesting or ginning of cotton; or to the construction industry.
(3) Only paragraphs (h) Medical surveillance, (k)(2) through (4) Recordkeeping—Medical Records, and appendices B, C and D of this section apply in all work places where employees exposed to cotton dust engage in cottonseed processing or waste processing operations.
(4) This section applies to yarn manufacturing and slashing and weaving operations exclusively using washed cotton (as defined by paragraph (n) of this section) only to the extent specified by paragraph (n) of this section.
(5) This section, in its entirety, applies to the control of all employees exposure to the cotton dust generated in the preparation of washed cotton from opening until the cotton is thoroughly wetted.
(6) This section does not apply to knitting, classing or warehousing operations except that employers with these operations, if requested by NIOSH, shall grant NIOSH access to their employees and workplaces for exposure monitoring and medical examinations for purposes of a health study to be performed by NIOSH on a sampling basis.
(b) Definitions. For the purpose of this section:
Assistant Secretary means the Assistant Secretary of Labor for Occupational Safety and Health, U.S. Department of Labor, or designee;
Blow down means the general cleaning of a room or a part of a room by the use of compressed air.
Blow off means the use of compressed air for cleaning of short duration and usually for a specific machine or any portion of a machine.
Cotton dust means dust present in the air during the handling or processing of cotton, which may contain a mixture of many substances including ground up plant matter, fiber, bacteria, fungi, soil, pesticides, non-cotton plant matter and other contaminants which may have accumulated with the cotton during the growing, harvesting and subsequent processing or storage periods. Any dust present during the handling and processing of cotton through the weaving or knitting of fabrics, and dust present in other operations or manufacturing processes using raw or waste cotton fibers or cotton fiber byproducts from textile mills are considered cotton dust within this definition. Lubricating oil mist associated with weaving operations is not considered cotton dust.
Director means the Director of the National Institute for Occupational Safety and Health (NIOSH), U.S. Department of Health and Human Services, or designee.
Equivalent Instrument means a cotton dust sampling device that meets the vertical elutriator equivalency requirements as described in paragraph (d)(1)(iii) of this section.
Lint-free respirable cotton dust means particles of cotton dust of approximately 15 micrometers or less aerodynamic equivalent diameter;
Vertical elutriator cotton dust sampler or vertical elutriator means a dust sampler which has a particle size cut-off at approximately 15 micrometers aerodynamic equivalent diameter when operating at the flow rate of 7.4 ±0.2 liters of air per minute;
Waste processing means waste recycling (sorting, blending, cleaning and willowing) and garnetting.
Yarn manufacturing means all textile mill operations from opening to, but not including, slashing and weaving.
(c) Permissible exposure limits and action levels —(1) Permissible exposure limits (PEL). (i) The employer shall assure that no employee who is exposed to cotton dust in yarn manufacturing and cotton washing operations is exposed to airborne concentrations of lint-free respirable cotton dust greater than 200 µg/m 3 mean concentration, averaged over an eight-hour period, as measured be a vertical elutriator or an equivalent instrument.
(ii) The employer shall assure that no employee who is exposed to cotton dust in textile mill waste house operations or is exposed in yarn manufacturing to dust from “lower grade washed cotton” as defined in paragraph (n)(5) of this section is exposed to airborne concentrations of lint-free respirable cotton dust greater than 500 µg/m 3 mean concentration, averaged over an eight-hour period, as measured by a vertical elutriator or an equivalent instrument.
(iii) The employer shall assure that no employee who is exposed to cotton dust in the textile processes known as slashing and weaving is exposed to airborne concentrations of lint-free respirable cotton dust greater than 750 µg/m 3 mean concentration, averaged over an eight hour period, as measured by a vertical elutriator or an equivalent instrument.
(2) Action levels. (i) The action level for yarn manufacturing and cotton washing operations is an airborne concentration of lint-free respirable cotton dust of 100 µg/m 3 mean concentration, averaged over an eight-hour period, as measured by a vertical elutriator or an equivalent instrument.
(ii) The action level for waste houses for textile operations is an airborne concentration of lint-free respirable cotton dust of 250 µg/m 3 mean concentration, averaged over an eight-hour period, as measured by a vertical elutriator or an equivalent instrument.
(iii) The action level for the textile processes known as slashing and weaving is an airborne concentration of lint-free respirable cotton dust of 375 µg/m 3 mean concentration, averaged over an eight-hour period, as measured by a vertical elutriator or an equivalent instrument.
(d) Exposure monitoring and measurement —(1) General. (i) For the purposes of this section, employee exposure is that exposure which would occur if the employee were not using a respirator.
(ii) The sampling device to be used shall be either the vertical elutriator cotton dust sampler or an equivalent instrument.
(iii) If an alternative to the vertical elutriator cotton dust sampler is used, the employer shall establish equivalency by reference to an OSHA opinion or by documenting, based on data developed by the employer or supplied by the manufacturer, that the alternative sampling devices meets the following criteria:
(A) It collects respirable particulates in the same range as the vertical elutriator (approximately 15 microns);
(B) Replicate exposure data used to establish equivalency are collected in side-by-side field and laboratory comparisons; and
(C) A minimum of 100 samples over the range of 0.5 to 2 times the permissible exposure limit are collected, and 90% of these samples have an accuracy range of plus or minus 25 per cent of the vertical elutriator reading with a 95% confidence level as demonstrated by a statistically valid protocol. (An acceptable protocol for demonstrating equivalency is described in appendix E of this section.)
(iv) OSHA will issue a written opinion stating that an instrument is equivalent to a vertical elutriator cotton dust sampler if
(A) A manufacturer or employer requests an opinion in writing and supplies the following information:
( 1 ) Sufficient test data to demonstrate that the instrument meets the requirements specified in this paragraph and the protocol specified in appendix E of this section;
( 2 ) Any other relevant information about the instrument and its testing requested by OSHA; and
( 3 ) A certification by the manufacturer or employer that the information supplied is accurate, and
(B) if OSHA finds, based on information submitted about the instrument, that the instrument meets the requirements for equivalency specified by paragraph (d) of this section.
(2) Initial monitoring. Each employer who has a place of employment within the scope of paragraph (a)(1), (a)(4), or (a)(5) of this section shall conduct monitoring by obtaining measurements which are representative of the exposure of all employees to airborne concentrations of lint-free respirable cotton dust over an eight-hour period. The sampling program shall include at least one determination during each shift for each work area.
(3) Periodic monitoring. (i) If the initial monitoring required by paragraph (d)(2) of this section or any subsequent monitoring reveals employee exposure to be at or below the permissible exposure limit, the employer shall repeat the monitoring for those employees at least annually.
(ii) If the initial monitoring required by paragraph (d)(2) of this section or any subsequent monitoring reveals employee exposure to be above the PEL, the employer shall repeat the monitoring for those employees at least every six months.
(iii) Whenever there has been a production, process, or control change which may result in new or additional exposure to cotton dust, or whenever the employer has any other reason to suspect an increase in employee exposure, the employer shall repeat the monitoring and measurements for those employees affected by the change or increase.
(4) Employee notification. (i) The employer must, within 15 working days after the receipt of the results of any monitoring performed under this section, notify each affected employee of these results either individually in writing or by posting the results in an appropriate location that is accessible to employees.
(ii) Whenever the results indicate that the employee's exposure exceeds the applicable permissible exposure limit specified in paragraph (c) of this section, the employer shall include in the written notice a statement that the permissible exposure limit was exceeded and a description of the corrective action taken to reduce exposure below the permissible exposure limit.
(e) Methods of compliance —(1) Engineering and work practice controls. The employer shall institute engineering and work practice controls to reduce and maintain employee exposure to cotton dust at or below the permissible exposure limit specified in paragraph (c) of this section, except to the extent that the employer can establish that such controls are not feasible.
(2) Whenever feasible engineering and work practice controls are not sufficient to reduce employee exposure to or below the permissible exposure limit, the employer shall nonetheless institute these controls to reduce exposure to the lowest feasible level, and shall supplement these controls with the use of respirators which shall comply with the provisions of paragraph (f) of this section.
(3) Compliance program. (i) Where the most recent exposure monitoring data indicates that any employee is exposed to cotton dust levels greater than the permissible exposure limit, the employer shall establish and implement a written program sufficient to reduce exposures to or below the permissible exposure limit solely by means of engineering controls and work practices as required by paragraph (e)(1) of this section.
(ii) The written program shall include at least the following:
(A) A description of each operation or process resulting in employee exposure to cotton dust at levels greater than the PEL;
(B) Engineering plans and other studies used to determine the controls for each process;
(C) A report of the technology considered in meeting the permissible exposure limit;
(D) Monitoring data obtained in accordance with paragraph (d) of this section;
(E) A detailed schedule for development and implementation of engineering and work practice controls, including exposure levels projected to be achieved by such controls;
(F) Work practice program; and
(G) Other relevant information.
(iii) The employer's schedule as set forth in the compliance program, shall project completion of the implementation of the compliance program no later than March 27, 1984 or as soon as possible if monitoring after March 27, 1984 reveals exposures over the PEL, except as provided in paragraph (m)(2)(ii)(B) of this section.
(iv) The employer shall complete the steps set forth in his program by the dates in the schedule.
(v) Written programs shall be submitted, upon request, to the Assistant Secretary and the Director, and shall be available at the worksite for examination and copying by the Assistant Secretary, the Director, and any affected employee or their designated representatives.
(vi) The written program required under paragraph (e)(3) of this section shall be revised and updated when necessary to reflect the current status of the program and current exposure levels.
(4) Mechanical ventilation. When mechanical ventilation is used to control exposure, measurements which demonstrate the effectiveness of the system to control exposure, such as capture velocity, duct velocity, or static pressure shall be made at reasonable intervals.
(f) Respiratory protection —(1) General. For employees who are required to use respirators by this section, the employer must provide each employee an appropriate respirator that complies with the requirements of this paragraph. Respirators must be used during:
(i) Periods necessary to install or implement feasible engineering and work-practice controls.
(ii) Maintenance and repair activities for which engineering and work-practice controls are not feasible.
(iii) Work operations for which feasible engineering and work-practice controls are not yet sufficient to reduce employee exposure to or below the permissible exposure limits.
(iv) Work operations specified under paragraph (g)(1) of this section.
(v) Periods for which an employee requests a respirator.
(2) Respirator program. (i) The employer must implement a respiratory protection program in accordance with § 1910.134(b) through (d) (except (d)(1)(iii)), and (f) through (m), which covers each employee required by this section to use a respirator.
(ii) Whenever a physician determines that an employee who works in an area in which the cotton-dust concentration exceeds the PEL is unable to use a respirator, including a powered air-purifying respirator, the employee must be given the opportunity to transfer to an available position, or to a position that becomes available later, that has a cotton-dust concentration at or below the PEL. The employer must ensure that such employees retain their current wage rate or other benefits as a result of the transfer.
(3) Respirator selection. (i) Employers must:
(A) Select, and provide to employees, the appropriate respirators specified in paragraph (d)(3)(i)(A) of 29 CFR 1910.134; however, employers must not select or use filtering facepieces for protection against cotton dust concentrations greater than five times (5 × ) the PEL.
(B) Provide HEPA filters for powered and non-powered air-purifying respirators used at cotton dust concentrations greater than ten times (10 × ) the PEL.
(ii) Employers must provide an employee with a powered air-purifying respirator (PAPR) instead of a non-powered air-purifying respirator selected according to paragraph (f)(3)(i) of this standard when the employee chooses to use a PAPR and it provides adequate protection to the employee as specified by paragraph (f)(3)(i) of this standard.
(g) Work practices. Each employer shall, regardless of the level of employee exposure, immediately establish and implement a written program of work practices which shall minimize cotton dust exposure. The following shall be included were applicable:
(1) Compressed air “blow down” cleaning shall be prohibited where alternative means are feasible. Where compressed air is used for cleaning, the employees performing the “blow down” or “blow off” shall wear suitable respirators. Employees whose presence is not required to perform “blow down” or “blow of” shall be required to leave the area affected by the “blow down” or “blow off” during this cleaning operation.
(2) Cleaning of clothing or floors with compressed air shall be prohibited.
(3) Floor sweeping shall be performed with a vacuum or with methods designed to minimize dispersal of dust.
(4) In areas where employees are exposed to concentrations of cotton dust greater than the permissible exposure limit, cotton and cotton waste shall be stacked, sorted, baled, dumped, removed or otherwise handled by mechanical means, except where the employer can show that it is infeasible to do so. Where infeasible, the method used for handling cotton and cotton waste shall be the method which reduces exposure to the lowest level feasible.
(h) Medical surveillance —(1) General. (i) Each employer covered by the standard shall institute a program of medical surveillance for all employees exposed to cotton dust.
(ii) The employer shall assure that all medical examinations and procedures are performed by or under the supervision of a licensed physician and are provided without cost to the employee.
(iii) Persons other than licensed physicians, who administer the pulmonary function testing required by this section shall have completed a NIOSH-approved training course in spirometry.
(2) Initial examinations. The employer shall provide medical surveillance to each employee who is or may be exposed to cotton dust. For new employees, this examination shall be provided prior to initial assignment. The medical surveillance shall include at least the following:
(i) A medical history;
(ii) The standardized questionnaire contained in appendix B; and
(iii) A pulmonary function measurement, including forced vital capacity (FVC) and forced expiratory volume in one second (FEV 1 ), and determination of the FEV 1 /FVC ratio shall be made. FVC, FEV 1 , and FEV 1 /FVC ratio values shall be compared to appropriate race/ethnicity-specific Lower Limit of Normal (LLN) values and predicted values published in Spirometric Reference Values from a Sample of the General U.S. Population, American Journal of Respiratory and Critical Care Medicine, 159(1): 179-187, January 1999 (commonly known as the NHANES III reference data set) (incorporated by reference, see § 1910.6). To obtain reference values for Asian-Americans, Spirometric Reference Values FEV 1 and FVC predicted and LLN values for Caucasians shall be multiplied by 0.88 to adjust for ethnic differences. These determinations shall be made for each employee before the employee enters the workplace on the first day of the work week, preceded by at least 35 hours of no exposure to cotton dust. The tests shall be repeated during the shift, no less than 4 and no more than 10 hours after the beginning of the work shift; and, in any event, no more than one hour after cessation of exposure. Such exposure shall be typical of the employee's usual workplace exposure.
(iv) Based upon the questionnaire results, each employee shall be graded according to Schilling's byssinosis classification system.
(3) Periodic examinations. (i) The employer shall provide at least annual medical surveillance for all employees exposed to cotton dust above the action level in yarn manufacturing, slashing and weaving, cotton washing and waste house operations. The employer shall provide medical surveillance at least every two years for all employees exposed to cotton dust at or below the action level, for all employees exposed to cotton dust from washed cotton (except from washed cotton defined in paragraph (n)(3) of this section), and for all employees exposed to cotton dust in cottonseed processing and waste processing operations. Periodic medical surveillance shall include at least an update of the medical history, standardized questionnaire (App. B-111), Schilling byssinosis grade, and the pulmonary function measurements in paragraph (h)(2)(iii) of this section.
(ii) Medical surveillance as required in paragraph (h)(3)(i) of this section shall be provided every six months for all employees in the following categories:
(A) An FEV 1 greater than the LLN, but with an FEV 1 decrement of 5 percent or 200 ml. on a first working day;
(B) An FEV 1 of less than the LLN; or
(C) Where, in the opinion of the physician, any significant change in questionnaire findings, pulmonary function results, or other diagnostic tests have occurred.
(iii) An employee whose FEV 1 is less than 60 percent of the predicted value shall be referred to a physician for a detailed pulmonary examination.
(iv) A comparison shall be made between the current examination results and those of previous examinations and a determination made by the physician as to whether there has been a significant change.
(4) Information provided to the physician. The employer shall provide the following information to the examination physician:
(i) A copy of this regulation and its Appendices:
(ii) A description of the affected employee's duties as they relate to the employee's exposure;
(iii) The employee's exposure level or anticipated exposure level;
(iv) A description of any personal protective equipment used or to be used; and
(v) Information from previous medical examinations of the affected employee which is not readily available to the examining physician.
(5) Physician's written opinion. (i) The employer shall obtain and furnish the employee with a copy of a written opinion from the examining physician containing the following:
(A) The results of the medical examination and tests including the FEV 1 , FVC, AND FEV 1 /FVC ratio;
(B) 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 the employee's health from exposure to cotton dust;
(C) The physician's recommended limitations upon the employee's exposure to cotton dust or upon the employee's use of respirators including a determination of whether an employee can wear a negative pressure respirator, and where the employee cannot, a determination of the employee's ability to wear a powered air purifying respirator; and,
(D) A statement that the employee has been informed by the physician of the results of the medical examination and any medical conditions which require further examination or treatment.
(ii) The written opinion obtained by the employer shall not reveal specific findings or diagnoses unrelated to occupational exposure.
(i) Employee education and training —(1) Training program. (i) The employer shall train each employee exposed to cotton dust in accordance with the requirements of this section. The employer shall institute a training program and ensure employee participation in the program.
(ii) The training program shall be provided prior to initial assignment and shall be repeated annually for each employee exposed to cotton dust, when job assignments or work processes change and when employee performance indicates a need for retraining.
(2) Access to training materials. (i) Each employer shall post a copy of this section with its appendices in a public location at the workplace, and shall, upon request, make copies available to employees.
(ii) The employer shall provide all materials relating to the employee training and information program to the Assistant Secretary and the Director upon request.
(j) Signs. (1) The employer shall post the following warning sign in each work area where the permissible exposure limit for cotton dust is exceeded:
(2) Prior to June 1, 2016, employers may use the following legend in lieu of that specified in paragraph (j)(1) of this section:
(k) Recordkeeping —(1) Exposure measurements. (i) The employer shall establish and maintain an accurate record of all measurements required by paragraph (d) of this section.
(ii) The record shall include:
(A) A log containing the items listed in paragraph IV (a) of appendix A, and the dates, number, duration, and results of each of the samples taken, including a description of the procedure used to determine representative employee exposure;
(B) The type of protective devices worn, if any, and length of time worn; and
(C) The names, job classifications, and exposure levels of employees whose exposure the measurement is intended to represent.
(iii) The employer shall maintain this record for at least 20 years.
(2) Medical surveillance. (i) The employer shall establish and maintain an accurate medical record for each employee subject to medical surveillance required by paragraph (h) of this section.
(ii) The record shall include:
(A) The name and description of the duties of the employee;
(B) A copy of the medical examination results including the medical history, questionnaire response, results of all tests, and the physician's recommendation;
(C) A copy of the physician's written opinion;
(D) Any employee medical complaints related to exposure to cotton dust;
(E) A copy of this standard and its appendices, except that the employer may keep one copy of the standard and the appendices for all employees, provided that he references the standard and appendices in the medical surveillance record of each employee; and
(F) A copy of the information provided to the physician as required by paragraph (h)(4) of this section.
(iii) The employer shall maintain this record for at least 20 years.
(3) Availability. (i) The employer shall make all records required to be maintained by paragraph (k) of this section available to the Assistant Secretary and the Director for examination and copying.
(ii) Employee exposure measurement records and employee medical records required by this paragraph shall be provided upon request to employees, designated representatives, and the Assistant Secretary in accordance with 29 CFR 1910.1020 (a) through (e) and (g) through (i).
(4) Transfer of records. (i) Whenever the employer ceases to do business, the successor employer shall receive and retain all records required to be maintained by paragraph (k) of this section.
(ii) The employer shall also comply with any additional requirements involving transfer of records set forth in 29 CFR 1910.1020(h).
(l) Observation of monitoring. (1) The employer shall provide affected employees or their designated representatives an opportunity to observe any measuring or monitoring of employee exposure to cotton dust conducted pursuant to paragraph (d) of this section.
(2) Whenever observation of the measuring or monitoring of employee exposure to cotton dust requires entry into an area where the use of personal protective equipment is required, the employer shall provide the observer with and assure the use of such equipment and shall require the observer to comply with all other applicable safety and health procedures.
(3) Without interfering with the measurement, observers shall be entitled to:
(i) An explanation of the measurement procedures:
(ii) An opportunity to observe all steps related to the measurement of airborne concentrations of cotton dust performed at the place of exposure; and
(iii) An opportunity to record the results obtained.
(m) Washed Cotton —(1) Exemptions. Cotton, after it has been washed by the processes described in this paragraph, is exempt from all or parts of this section as specified if the requirements of this paragraph are met.
(2) Initial requirements. (i) In order for an employer to qualify as exempt or partially exempt from this standard for operations using washed cotton, the employer must demonstrate that the cotton was washed in a facility which is open to inspection by the Assistant Secretary and the employer must provide sufficient accurate documentary evidence to demonstrate that the washing methods utilized meet the requirements of this paragraph.
(ii) An employer who handles or processes cotton which has been washed in a facility not under the employer's control and claims an exemption or partial exemption under this paragraph, must obtain from the cotton washer and make available at the worksite, to the Assistant Secretary, to any affected employee, or to their designated representative the following:
(A) A certification by the washer of the cotton of the grade of cotton, the type of washing process, and that the batch meets the requirements of this paragraph;
(B) Sufficient accurate documentation by the washer of the cotton grades and washing process; and
(C) An authorization by the washer that the Assistant Secretary or the Director may inspect the washer's washing facilities and documentation of the process.
(3) Medical and dyed cotton. Medical grade (USP) cotton, cotton that has been scoured, bleached and dyed, and mercerized yarn shall be exempt from all provisions of this standard.
(4) Higher grade washed cotton. The handling or processing of cotton classed as “low middling light spotted or better” (color grade 52 or better and leaf grade code 5 or better according to the 1993 USDA classification system) shall be exempt from all provisions of the standard except the requirements of paragraphs (h) medical surveillance, (k)(2) through (4) recordkeeping—medical records, and Appendices B, C, and D of this section, if they have been washed on one of the following systems:
(i) On a continuous batt system or a rayon rinse system including the following conditions:
(A) With water;
(B) At a temperature of no less than 60 °C;
(C) With a water-to-fiber ratio of no less than 40:1; and
(D) With the bacterial levels in the wash water controlled to limit bacterial contamination of the cotton.
(ii) On a batch kier washing system including the following conditions:
(A) With water;
(B) With cotton fiber mechanically opened and thoroughly prewetted before forming the cake;
(C) For low-temperature processing, at a temperature of no less than 60 °C with a water-to-fiber ratio of no less than 40:1; or, for high-temperature processing, at a temperature of no less than 93 °C with a water-to-fiber ratio of no less than 15:1;
(D) With a minimum of one wash cycle followed by two rinse cycles for each batch, using fresh water in each cycle, and
(E) With bacterial levels in the wash water controlled to limit bacterial contamination of the cotton.
(5) Lower grade washed cotton. The handling and processing of cotton of grades lower than “low middling light spotted,” that has been washed as specified in paragraph (n)(4) of this section and has also been bleached, shall be exempt from all provisions of the standard except the requirements of paragraphs (c)(1)(ii) Permissible Exposure Limit, (d) Exposure Monitoring, (h) Medical Surveillance, (k) Recordkeeping, and Appendices B, C and D of this section.
(6) Mixed grades of washed cotton. If more than one grade of washed cotton is being handled or processed together, the requirements of the grade with the most stringent exposure limit, medical and monitoring requirements shall be followed.
(n) Appendices. (1) Appendices B and D of this section are incorporated as part of this section and the contents of these appendices are mandatory.
(2) Appendix A of this section contains information which is not intended to create any additional obligations not otherwise imposed or to detract from any existing obligations.
(3) Appendix E of this section is a protocol which may be followed in the validation of alternative measuring devices as equivalent to the vertical elutriator cotton dust sampler. Other protocols may be used if it is demonstrated that they are statistically valid, meet the requirements in paragraph (d)(l)(iii) of this section, and are appropriate for demonstrating equivalency.
The sampling procedures must be designed so that samples of the actual dust concentrations are collected accurately and consistently and reflect the concentrations of dust at the place and time of sampling. Sufficient number of 6-hour area samples in each distinct work area of the plant should be collected at locations which provide representative samples of air to which the worker is exposed. In order to avoid filter overloading, sampling time may be shortened when sampling in dusty areas. Samples in each work area should be gathered simultaneously or sequentially during a normal operating period. The daily time-weighted average (TWA) exposure of each worker can then be determined by using the following formula:
(a) Sampler. The instrument selected for monitoring is the Lumsden-Lynch vertical elutriator. It should operate at a flow rate of 7.4±0.2 liters/minute.
(b) Filter Holder. A three-piece cassette constructed of polystyrene designed to hold a 37-mm diameter filter should be used. Care must be exercised to insure that an adequate seal exists between elements of the cassette.
(c) Filers and Support Pads. The membrane filters used should be polyvinyl chloride with a 5-um pore size and 37-mm diameter. A support pad, commonly called a backup pad, should be used under the filter membrane in the field monitor cassette.
(d) Balance. A balance sensitive to 10 micrograms should be used.
(e) Monitoring equipment for use in Class III hazardous locations must be approved for use in such locations, in accordance with the requirements of the OSHA electrical standards in subpart S of part 1910.
Samplers shall be calibrated when first received from the factory, after repair, and after receiving any abuse. The samplers should be calibrated in the laboratory both before they are used in the field and after they have been used to collect a large number of field samples. The primary standard, such as a spirometer or other standard calibrating instruments such as a wet test meter or a large bubble meter or dry gas meter, should be used. Instructions for calibration with the wet test meter follow. If another calibration device is selected, equivalent procedures should be used:
(a) Level wet test meter. Check the water level which should just touch the calibration point at the left side of the meter. If water level is low, add water 1-2 °F. warmer than room temperature of till point. Run the meter for 30 minutes before calibration;
(b) Place the polyvinyl chloride membrane filter in the filter cassette;
(c) Assemble the calibration sampling train;
(d) Connect the wet test meter to the train.
(e) Operate the system for ten minutes before starting the calibration;
(f) Check the vacuum gauge on the pump to insure that the pressure drop across the orifice exceeds 17 inches of mercury;
(g) Record the following on calibration data sheets:
(1) Wet test meter reading, start and finish;
(2) Elapsed time, start and finish (at least two minutes);
(3) Pressure drop at manometer;
(4) Air temperature;
(5) Barometric pressure; and
(6) Limiting orifice number;
(h) Calculate the flow rate and compare against the flow of 7.4±0.2 liters/minute. If flow is between these limits, perform calibration again, average results, and record orifice number and flow rate. If flow is not within these limits, discard or modify orifice and repeat procedure;
(i) Record the name of the person performing the calibration, the date, serial number of the wet test meter, and the number of the critical orifices being calibrated.
(a) Sampling data sheets should include a log of:
(1) The date of the sample collection;
(2) The time of sampling;
(3) The location of the sampler;
(4) The sampler serial number;
(5) The cassette number;
(6) The time of starting and stopping the sampling and the duration of sampling;
(7) The weight of the filter before and after sampling;
(8) The weight of dust collected (corrected for controls);
(9) The dust concentration measured;
(10) Other pertinent information; and
(11) Name of person taking sample
(b) Assembly of filter cassette should be as follows:
(1) Loosely assemble 3-piece cassette;
(2) Number cassette;
(3) Place absorbant pad in cassette;
(4) Weigh filter to an accuracy of 10 µg;
(5) Place filter in cassette;
(6) Record weight of filter in log, using cassette number for identification;
(7) Fully assemble cassette, using pressure to force parts tightly together;
(8) Install plugs top and bottom;
(9) Put shrink band on cassette, covering joint between center and bottom parts of cassette; and
(10) Set cassette aside until shrink band dries thoroughly.
(c) Sampling collection should be performed as follows:
(1) Clean lint out of the motor and elutriator;
(2) Install vertical elutriator in sampling locations specified above with inlet 4 1/2 to 5 1/2 feet from floor (breathing zone height);
(3) Remove top section of cassette;
(4) Install cassette in ferrule of elutriator;
(5) Tape cassette to ferrule with masking tape or similar material for air-tight seal;
(6) Remove bottom plug of cassette and attach hose containing critical orifice;
(7) Start elutriator pump and check to see if gauge reads above 17 in. of Hg vacuum;
(8) Record starting time, cassette number, and sampler number;
(9) At end of sampling period stop pump and record time; and
(10) Controls with each batch of samples collected, two additional filter cassettes should be subjected to exactly the same handling as the samples, except that they are not opened. These control filters should be weighed in the same manner as the sample filters.
(d) Shipping. The cassette with samples should be collected, along with the appropriate number of blanks, and shipped to the analytical laboratory in a suitable container to prevent damage in transit.
(e) Weighing of the sample should be achieved as follows:
(1) Remove shrink band;
(2) Remove top and middle sections of cassette and botton plug;
(3) Remove filter from cassette and weigh to an accuracy of 10 µg; and
(4) Record weight in log against original weight
(f) Calculation of volume of air sampled should be determined as follows:
(1) From starting and stopping times of sampling period, determine length of time in minutes of sampling period; and
(2) Multiply sampling time in minutes by flow rate of critical orifice in liters per minute and divide by 1000 to find air quantity in cubic meters.
(g) Calculation of Dust Concentrations should be made as follows:
(1) Substract weight of clean filter from dirty filter and apply control correction to find actual weight of sample. Record this weight (in µg) in log; and
(2) Divide mass of sample in µg by air volume in cubic meters to find dust concentration in µg/m. Record in log.
The spirometric measurements of pulmonary function shall conform to the following minimum standards, and these standards are not intended to preclude additional testing or alternate methods which can be determined to be superior.
a. The instrument shall be accurate to within ±50 milliliters or within ±3 percent of reading, whichever is greater.
b. 1. Instruments purchased on or before May 14, 2020 should be capable of measuring vital capacity from 0 to 7 liters BTPS
2. Instruments purchased after May 14, 2020 should be capable of measuring vital capacity from 0 to 8 liters BTPS.
c. The instrument shall have a low inertia and offer low resistance to airflow such that the resistance to airflow at 12 liters per second must be less than 1.5 cm H 2 O/(liter/sec).
d. The zero time point for the purpose of timing the FEV 1 shall be determined by extrapolating the steepest portion of the volume time curve back to the maximal inspiration volume (1, 2, 3, 4) or by an equivalent method.
e. 1. Instruments purchased on or before May 14, 2020 that incorporate measurements of airflow to determine volume shall conform to the same volume accuracy stated in paragraph (a) of this section I when presented with flow rates from at least 0 to 12 liters per second.
2. Instruments purchased after May 14, 2020 that incorporate measurements of airflow to determine volume shall conform to the same volume accuracy stated in paragraph (a) of this section I when presented with flow rates from at least 0 to 14 liters per second.
f. The instrument or user of the instrument must have a means of correcting volumes to body temperature saturated with water vapor (BTPS) under conditions of varying ambient spirometer temperatures and barometric pressures.
g. 1. Instruments purchased on or before May 14, 2020 shall provide a tracing or display of either flow versus volume or volume versus time during the entire forced expiration. A tracing or display is necessary to determine whether the patient has performed the test properly. The tracing must be stored and available for recall and must be of sufficient size that hand measurements may be made within the volume accuracy requirements of paragraph (a) of this section I. If a paper record is made it must have a paper speed of at least 2 cm/sec and a volume sensitivity of at least 10.0 mm of chart per liter of volume.
2. Instruments purchased after May 14, 2020 shall provide during testing a paper tracing or real-time display of flow versus volume and volume versus time for the entire forced expiration. Such a tracing or display is necessary to determine whether the worker has performed the test properly. Flow-volume and volume-time curves must be stored and available for recall. Real-time displays shall have a volume scale of at least 5 mm/L, a time scale of at least 10 mm/s, and a flow scale of at least 2.5 mm/L/s, when both flow-volume and volume-time displays are visible. If hand measurements will be made, paper tracings must be of sufficient size to allow those measurements to be made within the volume accuracy requirements of paragraph (a) of this section I. If a paper record is made it must have a paper speed of at least 2 cm/sec and a volume sensitivity of at least 10.0 mm of chart per liter of volume.
h. 1. Instruments purchased on or before May 14, 2020 shall be capable of accumulating volume for a minimum of 10 seconds and shall not stop accumulating volume before (i) the volume change for a 0.5-second interval is less than 25 milliliters, or (ii) the flow is less than 50 milliliters per second for a 0.5 second interval.
2. Instruments purchased after May 14, 2020 shall be capable of accumulating volume for a minimum of 15 seconds and shall not stop accumulating volume before the volume change for a 1-second interval is less than 25 milliliters.
i. The forced vital capacity (FVC) and forced expiratory volume in 1 second (FEV 1 ) measurements shall comply with the accuracy requirements stated in paragraph (a) of this section. That is, they should be accurately measured to within ±50 ml or within ±3 percent of reading, whichever is greater.
j. 1. Instruments purchased on or before May 14, 2020 must be capable of being calibrated in the field with respect to the FEV 1 and FVC. This calibration of the FEV 1 and FVC may be either directly or indirectly through volume and time base measurements. The volume calibration source should provide a volume displacement of at least 2 liters and should be accurate to within + or−30 milliliters.
2. Instruments purchased after May 14, 2020 must be capable of having its calibration checked in the field and be recalibrated, if necessary, if the spirometer requires the technician to do so. The volume-calibration syringe shall provide a volume displacement of at least 3 liters and shall be accurate to within ± 0.5 percent of 3 liters (15 milliliters).
a. Use of a nose clip is recommended but not required. The procedures shall be explained in simple terms to the worker who shall be instructed to loosen any tight clothing and stand in front of the apparatus. The worker may sit, but care should be taken on repeat testing that the same position be used and, if possible, the same spirometer. Particular attention shall be given to ensure that the chin is slightly elevated with the neck slightly extended. The worker shall be instructed to make a full inspiration from a normal breathing pattern and then blow into the apparatus, without interruption, as hard, fast, and completely as possible. At least three and no more than eight forced expirations shall be carried out. During the maneuvers, the worker shall be observed for compliance with instruction. The expirations shall be checked visually for technical acceptability and repeatability from flow-volume or volume-time tracings or displays. The following efforts shall be judged technically unacceptable when the worker:
1. Has not reached full inspiration preceding the forced expiration,
2. Has not used maximal effort during the entire forced expiration,
3. Has not tried to exhale continuously for at least 6 seconds and the volume-time curve shows no change in volume (<0.025 L) for at least one second,
4. Has coughed in the first second or closed the glottis,
5. Has an obstructed mouthpiece or a leak around the mouthpiece (obstruction due to tongue being placed in front of mouthpiece, false teeth falling in front of mouthpiece, etc.),
6. Has an unsatisfactory start of expiration, one characterized by excessive hesitation (or false starts), and, therefore, not allowing back extrapolation of time 0 (extrapolated volume on the volume-time tracing must be less than 150 milliliters or 5 percent of the FVC, whichever is greater.), and
7. Has an excessive variability between the acceptable curves. The difference between the two largest FVCs from the satisfactory tracings shall not exceed 150 milliliters and the difference between the two largest FEV 1 s of the satisfactory tracings shall not exceed 150 milliliters.
b. Calibration checks of the volume accuracy of the instrument for recording FVC and FEV 1 shall be performed daily or more frequently if specified by the spirometer manufacturer, using a 3-liter syringe. Calibration checks to ensure that the spirometer is recording 3 liters of injected air to within ±3.5 percent, or 2.90 to 3.10 liters, shall be conducted. Calibration checks of flow-type spirometers shall include injection of 3 liters air over a range of speeds, with injection times of 0.5 second, 3 seconds, and 6 or more seconds. Checks of volume-type spirometers shall include a single calibration check and a check to verify that the spirometer is not leaking more than 30 milliliters/minute air.
a. The first step in evaluating a spirogram should be to determine whether or not the worker has performed the test properly or as described in section II of this appendix. From the three satisfactory tracings, the forced vital capacity (FVC) and forced expiratory volume in 1 second (FEV 1 ) shall be measured and recorded. The largest observed FVC and largest observed FEV 1 shall be used in the analysis regardless of the curve(s) on which they occur.
b. [Reserved]
Technicians who perform pulmonary function testing should have the basic knowledge required to produce meaningful results. Training consisting of approximately 16 hours of formal instruction should cover the following areas.
a. Basic physiology of the forced vital-capacity maneuver and the determinants of airflow limitation, with emphasis on the relation to repeatability of results.
b. Instrumentation requirements, including calibration check procedures, sources of error, and their correction.
c. Performance of the testing including worker coaching, recognition of improperly performed maneuvers and corrective actions.
d. Data quality with emphasis on repeatability.
e. Actual use of the equipment under supervised conditions.
f. Measurement of tracings and calculations of results.
§ 1910.1044   1,2-dibromo-3-chloropropane.
(a) Scope and application. (1) This section applies to occupational exposure to 1,2-dibromo-3-chloropropane (DBCP).
(2) This section does not apply to:
(i) Exposure to DBCP which results solely from the application and use of DBCP as a pesticide; or
(ii) The storage, transportation, distribution or sale of DBCP in intact containers sealed in such a manner as to prevent exposure to DBCP vapors or liquid, except for the requirements of paragraphs (i), (n) and (o) of this section.
(b) Definitions. Authorized person means any person required by his duties to be present in regulated areas and authorized to do so by his employer, by this section, or by the Act. Authorized person also includes any person entering such areas as a designated representative of employees exercising an opportunity to observe employee exposure monitoring.
DBCP means 1,2-dibromo-3-chloropropane, Chemical Abstracts Service Registry Number 96-12-8, and includes all forms of DBCP.
Director means the Director, National Institute for Occupational Safety and Health, U.S. Department of Health and Human Services, or designee.
Emergency means any occurrence such as, but not limited to equipment failure, rupture of containers, or failure of control equipment which may, or does, result in an unexpected release of DBCP.
OSHA Area Office means the Area Office of the Occupational Safety and Health Administration having jurisdiction over the geographic area where the affected workplace is located.
Assistant Secretary means the Assistant Secretary of Labor for Occupational Safety and Health, U.S. Department of Labor, or designee.
(c) Permissible exposure limit —(1) Inhalation. The employer shall assure that no employee is exposed to an airborne concentration of DBCP in excess of 1 part DBCP per billion parts of air (ppb) as an 8-hour time-weighted average.
(2) Dermal and eye exposure. The employer shall assure that no employee is exposed to eye or skin contact with DBCP.
(d) [Reserved]
(e) Regulated areas. (1) The employer shall establish, within each place of employment, regulated areas wherever DBCP concentrations are in excess of the permissible exposure limit.
(2) The employer shall limit access to regulated areas to authorized persons.
(f) Exposure monitoring —(1) General. (i) Determinations of airborne exposure levels shall be made from air samples that are representative of each employee's exposure to DBCP over an 8-hour period.
(ii) For the purposes of this paragraph, employee exposure is that exposure which would occur if the employee were not using a respirator.
(2) Initial. Each employer who has a place of employment in which DBCP is present, shall monitor each workplace and work operation to accurately determine the airborne concentrations of DBCP to which employees may be exposed.
(3) Frequency. (i) If the monitoring required by this section reveals employee exposures to be at or below the permissible exposure limit, the employer must repeat these measurements at least every 6 months.
(ii) If the monitoring required by this section reveals employee exposures to be in excess of the permissible exposure limit, the employer must repeat these measurements for each such employee at least quarterly. The employer must continue quarterly monitoring until at least two consecutive measurements, taken at least seven (7) days apart, are at or below the permissible exposure limit. Thereafter the employer must monitor at least every 6 months.
(4) Additional. Whenever there has been a production, process, control, or personnel change which may result in any new or additional exposure to DBCP, or whenever the employer has any reason to suspect new or additional exposures to DBCP, the employer shall monitor the employees potentially affected by such change for the purpose of redetermining their exposure.
(5) Employee notification. (i) The employer must, within 15 working days after the receipt of the results of any monitoring performed under this section, notify each employee of these results either individually in writing or by posting the results in an appropriate location that is accessible to employees.
(ii) Whenever the results indicate that employee exposure exceeds the permissible exposure limit, the employer shall include in the written notice a statement that the permissible exposure limit was exceeded and a description of the corrective action being taken to reduce exposure to or below the permissible exposure limit.
(6) Accuracy of measurement. The employer shall use a method of measurement which has an accuracy, to a confidence level of 95 percent, of not less than plus or minus 25 percent for concentrations of DBCP at or above the permissible exposure limit.
(g) Methods of compliance —(1) Priority of compliance methods. The employer shall institute engineering and work practice controls to reduce and maintain employee exposures to DBCP at or below the permissible exposure limit, except to the extent that the employer establishes that such controls are not feasible. Where feasible engineering and work practice controls are not sufficient to reduce employee exposures to within the permissible exposure limit, the employer shall nonetheless use them to reduce exposures to the lowest level achievable by these controls, and shall supplement them by use of respiratory protection.
(2) Compliance program. (i) The employer shall establish and implement a written program to reduce employee exposures to DBCP to or below the permissible exposure limit solely by means of engineering and work practice controls as required by paragraph (g)(1) of this section.
(ii) The written program shall include a detailed schedule for development and implementation of the engineering and work practice controls. These plans must be revised at least annually to reflect the current status of the program.
(iii) Written plans for these compliance programs shall be submitted upon request to the Assistant Secretary and the Director, and shall be available at the worksite for examination and copying by the Assistant Secretary, the Director, and any affected employee or designated representative of employees.
(iv) The employer shall institute and maintain at least the controls described in his most recent written compliance program.
(h) Respiratory protection —(1) General. For employees who are required to use respirators by this section, the employer must provide each employee an appropriate respirator that complies with the requirements of this paragraph. Respirators must be used during:
(i) Periods necessary to install or implement feasible engineering and work-practice controls.
(ii) Maintenance and repair activities for which engineering and work-practice controls are not feasible.
(iii) Work operations for which feasible engineering and work-practice controls are not yet sufficient to reduce employee exposure to or below the permissible exposure limit.
(iv) Emergencies.
(2) Respirator program. The employer must implement a respiratory protection program in accordance with § 1910.134(b) through (d) (except (d)(1)(iii)), and (f) through (m), which covers each employee required by this section to use a respirator.
(3) Respirator selection. Employers must:
(i) Select, and provide to employees, the appropriate atmosphere-supplying respirator specified in paragraph (d)(3)(i)(A) of 29 CFR 1910.134.
(ii) Provide employees with one of the following respirator options to use for entry into, or escape from, unknown DBCP concentrations:
(A) A combination respirator that includes a supplied-air respirator with a full facepiece operated in a pressure-demand or other positive-pressure or continuous-flow mode, as well as an auxiliary self-contained breathing apparatus (SCBA) operated in a pressure-demand or positive-pressure mode.
(B) An SCBA with a full facepiece operated in a pressure-demand or other positive-pressure mode.
(i) Emergency situations —(1) Written plans. (i) A written plan for emergency situations shall be developed for each workplace in which DBCP is present.
(ii) Appropriate portions of the plan shall be implemented in the event of an emergency.
(2) Employees engaged in correcting emergency conditions shall be equipped as required in paragraphs (h) and (j) of this section until the emergency is abated.
(3) Evacuation. Employees not engaged in correcting the emergency shall be removed and restricted from the area and normal operations in the affected area shall not be resumed until the emergency is abated.
(4) Alerting employees. Where there is a possibility of employee exposure to DBCP due to the occurrence of an emergency, a general alarm shall be installed and maintained to promptly alert employees of such occurrences.
(5) Medical surveillance. For any employee exposed to DBCP in an emergency situation, the employer shall provide medical surveillance in accordance with paragraph (m)(6) of this section.
(6) Exposure monitoring. (i) Following an emergency, the employer shall conduct monitoring which complies with paragraph (f) of this section.
(ii) In workplaces not normally subject to periodic monitoring, the employer may terminate monitoring when two consecutive measurements indicate exposures below the permissible exposure limit.
(j) Protective clothing and equipments —(1) Provision and use. Where there is any possibility of eye or dermal contact with liquid or solid DBCP, the employer shall provide, at no cost to the employee, and assure that the employee wears impermeable protective clothing and equipment to protect the area of the body which may come in contact with DBCP. Eye and face protection shall meet the requirements of § 1910.133 of this part.
(2) Removal and storage. (i) The employer shall assure that employees remove DBCP contaminated work clothing only in change rooms provided in accordance with paragraph (l) (1) of this section.
(ii) The employer shall assure that employees promptly remove any protective clothing and equipment which becomes contaminated with DBCP-containing liquids and solids. This clothing shall not be reworn until the DBCP has been removed from the clothing or equipment.
(iii) The employer shall assure that no employee takes DBCP contaminated protective devices and work clothing out of the change room, except those employees authorized to do so for the purpose of laundering, maintenance, of disposal.
(iv) DBCP-contaminated protective devices and work clothing shall be placed and stored in closed containers which prevent dispersion of the DBCP outside the container.
(v) Containers of DBCP-contaminated protective devices or work clothing which are to be taken out of change rooms or the workplace for cleaning, maintenance or disposal shall bear labels with the following information: CONTAMINATED WITH 1,2-Dibromo-3-chloropropane (DBCP), MAY CAUSE CANCER.
(3) Cleaning and replacement. (i) The employer shall clean, launder, repair, or replace protective clothing and equipment required by this paragraph to maintain their effectiveness. The employer shall provide clean protective clothing and equipment at least daily to each affected employee.
(ii) The employer shall inform any person who launders or clean DBCP-contaminated protective clothing or equipment of the potentially harmful effects of exposure to DBCP.
(iii) The employer shall prohibit the removal of DBCP from protective clothing and equipment by blowing or shaking.
(k) Housekeeping —(1) Surfaces. (i) All workplace surfaces shall be maintained free of visible accumulations of DBCP.
(ii) Dry sweeping and the use of compressed air for the cleaning of floors and other surfaces is prohibited where DBCP dusts or liquids are present.
(iii) Where vacuuming methods are selected to clean floors and other surfaces, either portable units or a permanent system may be used.
( a ) If a portable unit is selected, the exhaust shall be attached to the general workplace exhaust ventilation system or collected within the vacuum unit, equipped with high efficiency filters or other appropriate means of contaminant removal, so that DBCP is not reintroduced into the workplace air; and
( b ) Portable vacuum units used to collect DBCP may not be used for other cleaning purposes and shall be labeled as prescribed by paragraph (j)(2)(v) of this section.
(iv) Cleaning of floors and other surfaces contaminated with DBCP-containing dusts shall not be performed by washing down with a hose, unless a fine spray has first been laid down.
(2) Liquids. Where DBCP is present in a liquid form, or as a resultant vapor, all containers or vessels containing DBCP shall be enclosed to the maximum extent feasible and tightly covered when not in use.
(3) Waste disposal. DBCP waste scrap, debris, containers or equipment, shall be disposed of in sealed bags or other closed containers which prevent dispersion of DBCP outside the container.
(l) Hygiene facilities and practices —(1) Change rooms. The employer shall provide clean change rooms equipped with storage facilities for street clothes and separate storage facilities for protective clothing and equipment whenever employees are required to wear protective clothing and equipment in accordance with paragraphs (h) and (j) of this section.
(2) Showers. (i) The employer shall assure that employees working in the regulated area shower at the end of the work shift.
(ii) The employer shall assure that employees whose skin becomes contaminated with DBCP-containing liquids or solids immediately wash or shower to remove any DBCP from the skin.
(iii) The employer shall provide shower facilities in accordance with 29 CFR 1910.141(d)(3).
(3) Lunchrooms. The employer shall provide lunchroom facilities which have a temperature controlled, positive pressure, filtered air supply, and which are readily accessible to employees working in regulated areas.
(4) Lavatories. (i) The employer shall assure that employees working in the regulated area remove protective clothing and wash their hands and face prior to eating.
(ii) The employer shall provide a sufficient number of lavatory facilities which comply with 29 CFR 1910.141(d) (1) and (2).
(5) Prohibition of activities in regulated areas. The employer shall assure that, in regulated areas, food or beverages are not present or consumed, smoking products and implements are not present or used, and cosmetics are not present or applied.
(m) Medical surveillance —(1) General. (i) The employer shall make available a medical surveillance program for employees who work in regulated areas and employees who are subjected to DBCP exposures in an emergency situation.
(ii) All medical examinations and procedures shall be performed by or under the supervision of a licensed physician, and shall be provided without cost to the employee.
(2) Frequency and content. At the time of initial assignment, and annually thereafter, the employer shall provide a medical examination for employees who work in regulated areas, which includes at least the following:
(i) A medical and occupational history including reproductive history.
(ii) A physical examination, including examination of the genito-urinary tract, testicle size and body habitus, including a determination of sperm count.
(iii) A serum specimen shall be obtained and the following determinations made by radioimmunoassay techniques utilizing National Institutes of Health (NIH) specific antigen or one of equivalent sensitivity:
( a ) Serum follicle stimulating hormone (FSH);
( b ) Serum luteinizing hormone (LH); and
( c ) Serum total estrogen (females).
(iv) Any other tests deemed appropriate by the examining physician.
(3) Additional examinations. If the employee for any reason develops signs or symptoms commonly associated with exposure to DBCP, the employer shall provide the employee with a medical examination which shall include those elements considered appropriate by the examining physician.
(4) Information provided to the physician. The employer shall provide the following information to the examining physician:
(i) A copy of this regulation and its appendices;
(ii) A description of the affected employee's duties as they relate to the employee's exposure;
(iii) The level of DBCP to which the employee is exposed; and
(iv) A description of any personal protective equipment used or to be used.
(5) Physician's written opinion. (i) For each examination under this section, the employer shall obtain and provide the employee with a written opinion from the examining physician which shall include:
( a ) The results of the medical tests performed;
( b ) The physician's opinion as to whether the employee has any detected medical condition which would place the employee at an increased risk of material impairment of health from exposure to DBCP; and
( c ) Any recommended limitations upon the employee's exposure to DBCP or upon the use of protective clothing and equipment such as respirators.
(ii) The employer shall instruct the physician not to reveal in the written opinion specific findings or diagnoses unrelated to occupational exposure.
(6) Emergency situations. If the employee is exposed to DBCP in an emergency situation, the employer shall provide the employee with a sperm count test as soon as practicable, or, if the employee has been vasectionized or is unable to produce a semen specimen, the hormone tests contained in paragraph (m)(2)(iii) of this section. The employer shall provide these same tests three months later.
(n) Employee information and training —(1) Training program. (i) The employer shall train each employee who may be exposed to DBCP in accordance with the requirements of this section. The employer shall institute a training program and ensure employee participation in the program.
(ii) The employer shall assure that each employee is informed of the following:
( a ) The information contained in appendix A;
( b ) The quantity, location, manner of use, release or storage of DBCP and the specific nature of operations which could result in exposure to DBCP as well as any necessary protective steps;
( c ) The purpose, proper use, and limitations of respirators;
( d ) The purpose and description of the medical surveillance program required by paragraph (m) of this section; and
( e ) A review of this standard, including appendices.
(2) Access to training materials. (i) The employer shall make a copy of this standard and its appendices readily available to all affected employees.
(ii) The employer shall provide, upon request, all materials relating to the employee information and training program to the Assistant Secretary and the Director.
(o) Communication of hazards —(1) Hazard communication—general. (i) Chemical manufacturers, importers, distributors and employers shall comply with all requirements of the Hazard Communication Standard (HCS) (§ 1910.1200) for DBCP.
(ii) In classifying the hazards of DBCP at least the following hazards are to be addressed: Cancer; reproductive effects; liver effects; kidney effects; central nervous system effects; skin, eye and respiratory tract irritation; and acute toxicity effects.
(iii) Employers shall include DBCP in the hazard communication program established to comply with the HCS (§ 1910.1200). Employers shall ensure that each employee has access to labels on containers of DBCP and to safety data sheets, and is trained in accordance with the requirements of HCS and paragraph (n) of this section.
(iv) The employer shall ensure that no statement appears on or near any sign or label required by this paragraph (o) which contradicts or detracts from the meaning of the required sign or label.
(2) Signs. (i) The employer shall post signs to clearly indicate all regulated areas. These signs shall bear the legend:
(ii) Prior to June 1, 2016, employers may use the following legend in lieu of that specified in paragraph (o)(2) of this section:
(3) Labels. (i) Where DBCP or products containing DBCP are sold, distributed or otherwise leave the employer's workplace bearing appropriate labels required by EPA under the regulations in 40 CFR Part 162, the labels required by this paragraph (o)(3) need not be affixed.
(ii) The employer shall ensure that the precautionary labels required by this paragraph (o)(3) are readily visible and legible.
(iii) Prior to June 1, 2015, employers may include the following information on containers of DBCP or products containing DBCP, DBCP-contaminated protective devices or work clothing or DBCP-contaminated portable vacuums in lieu of the labeling requirements in paragraphs (j)(2)(v), (k)(l)(iii)(b) and (o)(1)(i) of this section:
(p) Recordkeeping —(1) Exposure monitoring. (i) The employer shall establish and maintain an accurate record of all monitoring required by paragraph (f) of this section.
(ii) This record shall include:
( a ) The dates, number, duration and results of each of the samples taken, including a description of the sampling procedure used to determine representative employee exposure;
( b ) A description of the sampling and analytical methods used;
( c ) Type of respiratory protective devices worn, if any; and
( d ) Name and job classification of the employee monitored and of all other employees whose exposure the measurement is intended to represent.
(iii) The employer shall maintain this record for at least 40 years or the duration of employment plus 20 years, whichever is longer.
(2) Medical surveillance. (i) The employer shall establish and maintain an accurate record for each employee subject to medical surveillance required by paragraph (m) of this section.
(ii) This record shall include:
( a ) The name of the employee;
( b ) A copy of the physician's written opinion;
( c ) Any employee medical complaints related to exposure to DBCP;
( d ) A copy of the information provided the physician as required by paragraphs (m)(4)(ii) through (m)(4)(iv) of this section; and
( e ) A copy of the employee's medical and work history.
(iii) The employer shall maintain this record for at least 40 years or the duration of employment plus 20 years, whichever is longer.
(3) Availability. (i) The employer shall assure that all records required to be maintained by this section be made available upon request to the Assistant Secretary and the Director for examination and copying.
(ii) Employee exposure monitoring records and employee medical records required by this paragraph shall be provided upon request to employees, designated representatives, and the Assistant Secretary in accordance with 29 CFR 1910.1020 (a) through (e) and (g) through (i).
(4) Transfer of records. (i) If the employer ceases to do business, the successor employer shall receive and retain all records required to be maintained by paragraph (p) of this section for the prescribed period.
(ii) The employer shall also comply with any additional requirements involving transfer of records set forth in 29 CFR 1910.1020(h).
(q) Observation of monitoring —(1) Employee observation. The employer shall provide affected employees, or their designated representatives, with an opportunity to observe any monitoring of employee exposure to DBCP required by this section.
(2) Observation procedures. (i) Whenever observation of the measuring or monitoring of employee exposure to DBCP requires entry into an area where the use of protective clothing or equipment is required, the employer shall provide the observer with personal protective clothing or equipment required to be worn by employees working in the area, assure the use of such clothing and equipment, and require the observer to comply with all other applicable safety and health procedures.
(ii) Without interfering with the monitoring or measurement, observers shall be entitled to:
( a ) Receive an explanation of the measurement procedures;
( b ) Observe all steps related to the measurement of airborne concentrations of DBCP performed at the place of exposure; and
( c ) Record the results obtained.
(r) Appendices. The information contained in the appendices is not intended, by itself, to create any additional obligations not otherwise imposed or to detract from any existing obligation.
A. Synonyms and trades names: DBCP; Dibromochloropropane; Fumazone (Dow Chemical Company TM); Nemafume; Nemagon (Shell Chemical Co. TM); Nemaset; BBC 12; and OS 1879.
B. Permissible exposure:
1. Airborne. 1 part DBCP vapor per billion parts of air (1 ppb); time-weighted average (TWA) for an 8-hour workday.
2. Dermal. Eye contact and skin contact with DBCP are prohibited.
C. Appearance and odor: Technical grade DBCP is a dense yellow or amber liquid with a pungent odor. It may also appear in granular form, or blended in varying concentrations with other liquids.
D. Uses: DBCP is used to control nematodes, very small worm-like plant parasites, on crops including cotton, soybeans, fruits, nuts, vegetables and ornamentals.
A. Routes of entry: Employees may be exposed:
1. Through inhalation (breathing);
2. Through ingestion (swallowing);
3. Skin contact; and
4. Eye contact.
B. Effects of exposure:
1. Acute exposure. DBCP may cause drowsiness, irritation of the eyes, nose, throat and skin, nausea and vomiting. In addition, overexposure may cause damage to the lungs, liver or kidneys.
2. Chronic exposure. Prolonged or repeated exposure to DBCP has been shown to cause sterility in humans. It also has been shown to produce cancer and sterility in laboratory animals and has been determined to constitute an increased risk of cancer in man.
3. Reporting Signs and Symptoms. If you develop any of the above signs or symptoms that you think are caused by exposure to DBCP, you should inform your employer.
A. Eye exposure. If DBCP liquid or dust containing DBCP gets into your eyes, wash your eyes immediately with large amounts of water, lifting the lower and upper lids occasionally. Get medical attention immediately. Contact lenses should not be worn when working with DBCP.
B. Skin exposure. If DBCP liquids or dusts containing DBCP get on your skin, immediately wash using soap or mild detergent and water. If DBCP liquids or dusts containing DBCP penetrate through your clothing, remove the clothing immediately and wash. If irritation is present after washing get medical attention.
C. Breathing. If you or any person breathe in large amounts of DBCP, move the exposed person to fresh air at once. If breathing has stopped, perform artificial respiration. Do not use mouth-to-mouth. Keep the affected person warm and at rest. Get medical attention as soon as possible.
D. Swallowing. When DBCP has been swallowed and the person is conscious, give the person large amounts of water immediately. After the water has been swallowed, try to get the person to vomit by having him touch the back of his throat with his finger. Do not make an unconscious person vomit. Get medical attention immediately.
E. Rescue. Notify someone. Put into effect the established emergency rescue procedures. Know the locations of the emergency rescue equipment before the need arises.
A. Respirators. You may be required to wear a respirator in emergencies and while your employer is in the process of reducing DBCP exposures through engineering controls. If respirators are worn, they must have a National Institute for Occupational Safety and Health (NIOSH) approval label (Older respirators may have a Bureau of Mines Approval label). For effective protection, a respirator must fit your face and head snugly. The respirator should not be loosened or removed in work situations where its use is required. DBCP does not have a detectable odor except at 1,000 times or more above the permissible exposure limit. If you can smell DBCP while wearing a respirator, the respirator is not working correctly; go immediately to fresh air. If you experience difficulty breathing while wearing a respirator, tell your employer.
B. Protective clothing. When working with DBCP you must wear for your protection impermeable work clothing provided by your employer. (Standard rubber and neoprene protective clothing do not offer adequate protection).
DBCP must never be allowed to remain on the skin. Clothing and shoes must not be allowed to become contaminated with DBCP, and if they do, they must be promptly removed and not worn again until completely free of DBCP. Turn in impermeable clothing that has developed leaks for repair or replacement.
C. Eye protection. You must wear splash-proof safety goggles where there is any possibility of DBCP liquid or dust contacting your eyes.
A. DBCP must be stored in tightly closed containers in a cool, well-ventilated area.
B. If your work clothing may have become contaminated with DBCP, or liquids or dusts containing DBCP, you must change into uncontaminated clothing before leaving the work premises.
C. You must promptly remove any protective clothing that becomes contaminated with DBCP. This clothing must not be reworn until the DBCP is removed from the clothing.
D. If your skin becomes contaminated with DBCP, you must immediately and thoroughly wash or shower with soap or mild detergent and water to remove any DBCP from your skin.
E. You must not keep food, beverages, cosmetics, or smoking materials, nor eat or smoke, in regulated areas.
F. If you work in a regulated area, you must wash your hands thoroughly with soap or mild detergent and water, before eating, smoking or using toilet facilities.
G. If you work in a regulated area, you must remove any protective equipment or clothing before leaving the regulated area.
H. Ask your supervisor where DBCP is used in your work area and for any additional safety and health rules.
A. Each year, your employer is required to inform you of the information contained in this Substance Safety Data Sheet for DBCP. In addition, your employer must instruct you in the safe use of DBCP, emergency procedures, and the correct use of protective equipment.
B. Your employer is required to determine whether you are being exposed to DBCP. You or your representative have the right to observe employee exposure measurements and to record the result obtained. Your employer is required to inform you of your exposure. If your employer determines that you are being overexposed, he is required to inform you of the actions which are being taken to reduce your exposure.
C. Your employer is required to keep records of your exposure and medical examinations. Your employer is required to keep exposure and medical data for at least 40 years or the duration of your employment plus 20 years, whichever is longer.
D. Your employer is required to release exposure and medical records to you, your physician, or other individual designated by you upon your written request.
A. Substance Identification
1. Synonyms: 1,2-dibromo-3-chloropropane; DBCP, Fumazone; Nemafume; Nemagon; Nemaset; BBC 12; OS 1879. DBCP is also included in agricultural pesticides and fumigants which include the phrase “Nema—” in their name.
2. Formula: C3H5Br2 C1.
3. Molecular Weight: 236.
B. Physical Data:
1. Boiling point (760 mm HG): 195C (383F)
2. Specific gravity (water = 1): 2.093.
3. Vapor density (air = 1 at boiling point of DBCP): Data not available.
4. Melting point: 6C (43F).
5. Vapor pressure at 20C (68F): 0.8 mm Hg
6. Solubility in water: 1000 ppm.
7. Evaporation rate (Butyl Acetate = 1): very much less than 1.
8. Appearance and odor: Dense yellow or amber liquid with a pungent odor at high concentrations. Any detectable odor of DBCP indicates overexposure.
A. Fire
1. Flash point: 170F (77C)
2. Autoignition temperature: Data not available.
3. Flammable limits in air, percent by volume: Data not available.
4. Extinguishing media: Carbon dioxide, dry chemical.
5. Special fire-fighting procedures: Do not use a solid stream of water since a stream will scatter and spread the fire. Use water spray to cool containers exposed to a fire.
6. Unusual fire and explosion hazards: None known.
7. For purposes of complying with the requirements of § 1910.106, liquid DBCP is classified as a Category 4 flammable liquid.
8. For the purpose of complying with § 1910.309, the classification of hazardous locations as described in article 500 of the National Electrical Code for DBCP shall be Class I, Group D.
9. For the purpose of compliance with § 1910.157, DBCP is classified as a Class B fire hazard.
10. For the purpose of compliance with § 1910.178, locations classified as hazardous locations due to the presence of DBCP shall be Class I, Group D.
11. Sources of ignition are prohibited where DBCP presents a fire or explosion hazard.
B. Reactivity
1. Conditions contributing to instability: None known.
2. Incompatibilities: Reacts with chemically active metals, such as aluminum, magnesium and tin alloys.
3. Hazardous decomposition products: Toxic gases and vapors (such as HBr, HCl and carbon monoxide) may be released in a fire involving DBCP.
4. Special precautions: DBCP will attack some rubber materials and coatings.
A. If DBCP is spilled or leaked, the following steps should be taken:
1. The area should be evacuated at once and re-entered only after thorough ventilation.
2. Ventilate area of spill or leak.
3. If in liquid form, collect for reclamation or absorb in paper, vermiculite, dry sand, earth or similar material.
4. If in solid form, collect spilled material in the most convenient and safe manner for reclamation or for disposal.
B. Persons not wearing protective equipment must be restricted from areas of spills or leaks until cleanup has been completed.
C. Waste Disposal Methods:
1. For small quantities of liquid DBCP, absorb on paper towels, remove to a safe place (such as a fume hood) and burn the paper. Large quantities can be reclaimed or collected and atomized in a suitable combustion chamber equipped with an appropriate effluent gas cleaning device. If liquid DBCP is absorbed in vermiculite, dry sand, earth or similar material and placed in sealed containers it may be disposed of in a State-approved sanitary landfill.
2. If in solid form, for small quantities, place on paper towels, remove to a safe place (such as a fume hood) and burn. Large quantities may be reclaimed. However, if this is not practical, dissolve in a flammable solvent (such as alcohol) and atomize in a suitable combustion chamber equipped with an appropriate effluent gas cleaning device. DBCP in solid form may also be disposed in a state-approved sanitary landfill.
A. Exposure above the permissible exposure limit.
1. Eight Hour Exposure Evaluation: Measurements taken for the purpose of determining employee exposure under this section are best taken so that the average 8-hour exposure may be determined from a single 8-hour sample or two (2) 4-hour samples. Air samples should be taken in the employee's breathing zone (air that would most nearly represent that inhaled by the employee).
2. Monitoring Techniques: The sampling and analysis under this section may be performed by collecting the DBCP vapor on petroleum based charcoal absorption tubes with subsequent chemical analyses. The method of measurement chosen should determine the concentration of airborne DBCP at the permissible exposure limit to an accuracy of plus or minus 25 percent. If charcoal tubes are used, a total volume of 10 liters should be collected at a flow rate of 50 cc. per minute for each tube. Analyze the resultant samples as you would samples of halogenated solvent.
B. Since many of the duties relating to employee protection are dependent on the results of monitoring and measuring procedures, employers should assure that the evaluation of employee exposures is performed by a competent industrial hygienist or other technically qualified person.
Employees should be required to wear appropriate protective clothing to prevent any possibility of skin contact with DBCP. Because DBCP is absorbed through the skin, it is important to prevent skin contact with both liquid and solid forms of DBCP. Protective clothing should include impermeable coveralls or similar fullbody work clothing, gloves, headcoverings, and workshoes or shoe coverings. Standard rubber and neoprene gloves do not offer adequate protection and should not be relied upon to keep DBCP off the skin. DBCP should never be allowed to remain on the skin. Clothing and shoes should not be allowed to become contaminated with the material, and if they do, they should be promptly removed and not worn again until completely free of the material. Any protective clothing which has developed leaks or is otherwise found to be defective should be repaired or replaced. Employees should also be required to wear splash-proof safety goggles where there is any possibility of DBCP contacting the eyes.
1. The workplace must be kept clean, orderly and in a sanitary condition;
2. Dry sweeping and the use of compressed air is unsafe for the cleaning of floors and other surfaces where DBCP dust or liquids are found. To minimize the contamination of air with dust, vacuuming with either portable or permanent systems must be used. If a portable unit is selected, the exhaust must be attached to the general workplace exhaust ventilation system, or collected within the vacuum unit equipped with high efficiency filters or other appropriate means of contamination removal and not used for other purposes. Units used to collect DBCP must be labeled.
3. Adequate washing facilities with hot and cold water must be provided, and maintained in a sanitary condition. Suitable cleansing agents should also be provided to assure the effective removal of DBCP from the skin.
4. Change or dressing rooms with individual clothes storage facilities must be provided to prevent the contamination of street clothes with DBCP. Because of the hazardous nature of DBCP, contaminated protective clothing must be stored in closed containers for cleaning or disposal.
A. Store DBCP in tightly closed containers in a cool, well ventilated area.
B. Use of supplied-air suits or other impervious clothing (such as acid suits) may be necessary to prevent skin contact with DBCP. Supplied-air suits should be selected, used, and maintained under the supervision of persons knowlegeable in the limitations and potential life-endangering characteristics of supplied-air suits.
C. The use of air-conditioned suits may be necessary in warmer climates.
D. Advise employees of all areas and operations where exposure to DBCP could occur.
Common operations in which exposure to DBCP is likely to occur are: during its production; and during its formulation into pesticides and fumigants.
Inhalation; skin absorption
Recent data collected on workers involved in the manufacture and formulation of DBCP has shown that DBCP can cause sterility at very low levels of exposure. This finding is supported by studies showing that DBCP causes sterility in animals. Chronic exposure to DBCP resulted in pronounced necrotic action on the parenchymatous organs ( i.e. , liver, kidney, spleen) and on the testicles of rats at concentrations as low as 5 ppm. Rats that were chronically exposed to DBCP also showed changes in the composition of the blood, showing low RBC, hemoglobin, and WBC, and high reticulocyte levels as well as functional hepatic disturbance, manifesting itself in a long prothrombin time. Reznik et al. noted a single dose of 100 mg produced profound depression of the nervous system of rats. Their condition gradually improved. Acute exposure also resulted in the destruction of the sex gland activity of male rats as well as causing changes in the estrous cycle in female rats. Animal studies have also associated DBCP with an increased incidence of carcinoma. Olson, et al. orally administered DBCP to rats and mice 5 times per week at experimentally predetermined maximally tolerated doses and at half those doses. As early as ten weeks after initiation of treatment, DBCP induced a high incidence of squamous cell carcinomas of the stomach with metastases in both species. DBCP also induced mammary adenocarcinomas in the female rats at both dose levels.
A. Inhalation: Nausea, eye irritation, conjunctivitis, respiratory irritation, pulmonary congestion or edema, CNS depression with apathy, sluggishness, and ataxia.
B. Dermal: Erythema or inflammation and dermatitis on repeated exposure.
A. Semen analysis: The following information excerpted from the document “Evaluation of Testicular Function”, submitted by the Corporate Medical Department of the Shell Oil Company (exhibit 39-3), may be useful to physicians conducting the medical surveillance program;
In performing semen analyses certain minimal but specific criteria should be met:
1. It is recommended that a minimum of three valid semen analyses be obtained in order to make a determination of an individual's average sperm count.
2. A period of sexual abstinence is necessary prior to the collection of each masturbatory sample. It is recommended that intercourse or masturbation be performed 48 hours before the actual specimen collection. A period of 48 hours of abstinence would follow; then the masturbatory sample would be collected.
3. Each semen specimen should be collected in a clean, widemouthed, glass jar (not necessarily pre-sterilized) in a manner designated by the examining physician. Any part of the seminal fluid exam should be initialed only after liquifaction is complete, i.e., 30 to 45 minutes after collection.
4. Semen volume should be measured to the nearest 1/10 of a cubic centimeter.
5. Sperm density should be determined using routine techniques involving the use of a white cell pipette and a hemocytometer chamber. The immobilizing fluid most effective and most easily obtained for this process is distilled water.
6. Thin, dry smears of the semen should be made for a morphologic classification of the sperm forms and should be stained with either hematoxalin or the more difficult, yet more precise, Papanicolaou technique. Also of importance to record is obvious sperm agglutination, pyospermia, delayed liquifaction (greater than 30 minutes), and hyperviscosity. In addition, pH, using nitrazine paper, should be determined.
7. A total morphology evaluation should include percentages of the following:
a. Normal (oval) forms,
b. Tapered forms,
c. Amorphous forms (include large and small sperm shapes),
d. Duplicated (either heads or tails) forms, and
e. Immature forms.
8. Each sample should be evaluated for sperm viability (percent viable sperm moving at the time of examination) as well as sperm motility (subjective characterization of “purposeful forward sperm progression” of the majority of those viable sperm analyzed) within two hours after collection, ideally by the same or equally qualified examiner.
B. Serum determinations: The following serum determinations should be performed by radioimmuno-assay techniques using National Institutes of Health (NIH) specific antigen or antigen preparations of equivalent sensitivity:
1. Serum follicle stimulating hormone (FSH);
2. Serum luteinizing hormone (LH); and
3. Serum total estrogen (females only).
Remove from exposure immediately, give oxygen or artificial resuscitation if indicated. Contaminated clothing and shoes should be removed immediately. Flush eyes and wash contaminated skin. If swallowed and the person is conscious, induce vomiting. Recovery from mild exposures is usually rapid and complete.
A. Other considerations. DBCP can cause both acute and chronic effects. It is important that the physician become familiar with the operating conditions in which exposure to DBCP occurs. Those with respiratory disorders may not tolerate the wearing of negative pressure respirators.
B. Surveillance and screening. Medical histories and laboratory examinations are required for each employee subject to exposure to DBCP. The employer should screen employees for history of certain medical conditions (listed below) which might place the employee at increased risk from exposure.
1. Liver disease. The primary site of biotransformation and detoxification of DBCP is the liver. Liver dysfunctions likely to inhibit the conjugation reactions will tend to promote the toxic actions of DBCP. These precautions should be considered before exposing persons with impaired liver function to DBCP.
2. Renal disease. Because DBCP has been associated with injury to the kidney it is important that special consideration be given to those with possible impairment of renal function.
3. Skin desease. DBCP can penetrate the skin and can cause erythema on prolonged exposure. Persons with pre-existing skin disorders may be more susceptible to the effects of DBCP.
4. Blood dyscrasias. DBCP has been shown to decrease the content of erythrocytes, hemoglobin, and leukocytes in the blood, as well as increase the prothrombin time. Persons with existing blood disorders may be more susceptible to the effects of DBCP.
5. Reproductive disorders. Animal studies have associated DBCP with various effects on the reproductive organs. Among these effects are atrophy of the testicles and changes in the estrous cycle. Persons with pre-existing reproductive disorders may be at increased risk to these effects of DBCP.
1. Reznik, Ya. B. and Sprinchan, G. K.: Experimental Data on the Gonadotoxic effect of Nemagon, Gig. Sanit., (6), 1975, pp. 101-102, (translated from Russian).
2. Faydysh, E. V., Rakhmatullaev, N. N. and Varshavskii, V. A.: The Cytotoxic Action of Nemagon in a Subacute Experiment, Med. Zh. Uzbekistana, (No. 1), 1970, pp. 64-65, (translated from Russian).
3. Rakhmatullaev, N. N.: Hygienic Characteristics of the Nematocide Nemagon in Relation to Water Pollution Control, Hyg. Sanit., 36(3), 1971, pp. 344-348, (translated from Russian).
4. Olson, W. A. et al.: Induction of Stomach Cancer in Rats and Mice by Halogenated Aliphatic Fumigants, Journal of the National Cancer Institute, (51), 1973, pp. 1993-1995.
5. Torkelson, T. R. et al.: Toxicologic Investigations of 1,2-Dibromo-3-chloropropane, Toxicology and Applied Pharmacology, 3, 1961 pp. 545-559.
§ 1910.1045   Acrylonitrile.
(a) Scope and application. (1) This section applies to all occupational exposures to acrylonitrile (AN), Chemical Abstracts Service Registry No. 000107131, except as provided in paragraphs (a)(2) and (a)(3) of this section.
(2) This section does not apply to exposures which result solely from the processing, use, and handling of the following materials:
(i) ABS resins, SAN resins, nitrile barrier resins, solid nitrile elastomers, and acrylic and modacrylic fibers, when these listed materials are in the form of finished polymers, and products fabricated from such finished polymers;
(ii) Materials made from and/or containing AN for which objective data is reasonably relied upon to demonstrate that the material is not capable of releasing AN in airborne concentrations in excess of 1 ppm as an eight (8)-hour time-weighted average, under the expected conditions of processing, use, and handling which will cause the greatest possible release; and
(iii) Solid materials made from and/or containing AN which will not be heated above 170 °F during handling, use, or processing.
(3) An employer relying upon exemption under paragraph (a)(2)(ii) shall maintain records of the objective data supporting that exemption, and of the basis of the employer's reliance on the data, as provided in paragraph (q) of this section.
(b) Definitions. Acrylonitrile or AN means acrylonitrile monomer, chemical formula CH 2 = CHCN.
Action level means a concentration of AN of 1 ppm as an eight (8)-hour time-weighted average.
Assistant Secretary means the Assistant Secretary of Labor for Occupational Safety and Health, U.S. Department of Labor, or designee.
Authorized person means any person specifically authorized by the employer whose duties require the person to enter a regulated area, or any person entering such an area as a designated representative of employees for the purpose of exercising the opportunity to observe monitoring procedures under paragraph (r) of this section.
Decontamination means treatment of materials and surfaces by water washdown, ventilation, or other means, to assure that the materials will not expose employees to airborne concentrations of AN above 1 means the Director, National Institute for Occupational Safety and Health, U.S. Department of Health and Human Services, or designee.
Emergency means any occurrence such as, but not limited to, equipment failure, rupture of containers, or failure of control equipment, which results in an unexpected massive release of AN.
Liquid AN means AN monomer in liquid form, and liquid or semiliquid polymer intermediates, including slurries, suspensions, emulsions, and solutions, produced during the polymerization of AN.
OSHA Area Office means the Area Office of the Occupational Safety and Health Administration having jurisdiction over the geographic area where the affected workplace is located.
(c) Permissible exposure limits —(1) Inhalation. (i) Time weighted average limit (TWA). The employer shall assure that no employee is exposed to an airborne concentration of acrylonitrile in excess of two (2) parts acrylonitrile per million parts of air (2 ppm) as an eight (8)-hour time-weighted average.
(ii) Ceiling limit. The employer shall assure that no employee is exposed to an airborne concentration of acrylonitrile in excess of ten (10) ppm as averaged over any fifteen (15)-minute period during the work day.
(2) Dermal and eye exposure. The employer shall assure that no employee is exposed to skin contact or eye contact with liquid AN.
(d) [Reserved]
(e) Exposure monitoring —(1) General. (i) Determinations of airborne exposure levels shall be made from air samples that are representative of each employee's exposure to AN over an eight (8)-hour period.
(ii) For the purposes of this section, employee exposure is that exposure which would occur if the employee were not using a respirator.
(2) Initial monitoring. Each employer who has a place of employment in which AN is present shall monitor each such workplace and work operation to accurately determine the airborne concentrations of AN to which employees may be exposed.
(3) Frequency. (i) If the monitoring required by this section reveals employee exposure to be below the action level, the employer may discontinue monitoring for that employee.
(ii) If the monitoring required by this section reveals employee exposure to be at or above the action level but at or below the permissible exposure limits, the employer must repeat such monitoring for each such employee at least every 6 months. The employer must continue these measurements every 6 months until at least two consecutive measurements taken at least seven (7) days a part, are below the action level, and thereafter the employer may discontinue monitoring for that employee.
(iii) If the monitoring required by this section reveals employee exposure to be in excess of the permissible exposure limits, the employer must repeat these determinations for each such employee at least quarterly. The employer must continue these quarterly measurements until at least two consecutive measurements, taken at least seven (7) days apart, are at or below the permissible exposure limits, and thereafter the employer must monitor at least every 6 months.
(4) Additional monitoring. Whenever there has been a production, process, control, or personnel change which may result in new or additional exposures to AN, or whenever the employer has any other reason to suspect a change which may result in new or additional exposures to AN, additional monitoring which complies with this paragraph shall be conducted.
(5) Employee notification. (i) The employer must, within 15 working days after the receipt of the results of any monitoring performed under this section, notify each affected employee of these results either individually in writing or by posting the results in an appropriate location that is accessible to employees.
(ii) Whenever the results indicate that the representative employee exposure exceeds the permissible exposure limits, the employer shall include in the written notice a statement that the permissible exposure limits were exceeded and a description of the corrective action being taken to reduce exposure to or below the permissible exposure limits.
(6) Accuracy of measurement. The method of measurement of employee exposures shall be accurate to a confidence level of 95 percent, to within plus or minus 35 percent for concentrations of AN at or above the permissible exposure limits, and plus or minus 50 percent for concentrations of AN below the permissible exposure limits.
(f) Regulated areas. (1) The employer shall establish regulated areas where AN concentrations are in excess of the permissible exposure limits.
(2) Regulated areas shall be demarcated and segregated from the rest of the workplace, in any manner that minimizes the number of persons who will be exposed to AN.
(3) Access to regulated areas shall be limited to authorized persons or to persons otherwise authorized by the act or regulations issued pursuant thereto.
(4) The employer shall assure that food or beverages are not present or consumed, tobacco products are not present or used, and cosmetics are not applied in the regulated area.
(g) Methods of compliance —(1) Engineering and work practice controls. (i) By November 2, 1980, the employer shall institute engineering and work practice controls to reduce and maintain employee exposures to AN, to or below the permissible exposure limits, except to the extent that the employer establishes that such controls are not feasible.
(ii) Wherever the engineering and work practice controls which can be instituted are not sufficient to reduce employee exposures to or below the permissible exposure limits, the employer shall nonetheless use them to reduce exposures to the lowest levels achievable by these controls, and shall supplement them by the use of respiratory protection which complies with the requirements of paragraph (h) of this section.
(2) Compliance program. (i) The employer shall establish and implement a written program to reduce employee exposures to or below the permissible exposure limits solely by means of engineering and work practice controls, as required by paragraph (g)(1) of this section.
(ii) Written plans for these compliance programs shall include at least the following:
(A) A description of each operation or process resulting in employee exposure to AN above the permissible exposure limits;
(B) An outline of the nature of the engineering controls and work practices to be applied to the operation or process in question;
(C) A report of the technology considered in meeting the permissible exposure limits;
(D) A schedule for implementation of engineering and work practice controls for the operation or process, which shall project completion no later than November 2, 1980; and
(E) Other relevant information.
(iii) The employer shall complete the steps set forth in the compliance program by the dates in the schedule.
(iv) Written plans shall be submitted upon request to the Assistant Secretary and the Director, and shall be available at the worksite for examination and copying by the Assistant Secretary, the Director, or any affected employee or representative.
(v) The plans required by this paragraph must be revised and updated at least annually to reflect the current status of the program.
(h) Respiratory protection —(1) General. For employees who use respirators required by this section, the employer must provide each employee an appropriate respirator that complies with the requirements of this paragraph. Respirators must be used during:
(i) Periods necessary to install or implement feasible engineering and work-practice controls.
(ii) Work operations, such as maintenance and repair activities or reactor cleaning, for which the employer establishes that engineering and work-practice controls are not feasible.
(iii) Work operations for which feasible engineering and work-practice controls are not yet sufficient to reduce employee exposure to or below the permissible exposure limits.
(iv) Emergencies.
(2) Respirator program. (i) The employer must implement a respiratory protection program in accordance with § 1910.134(b) through (d) (except (d)(1)(iii), (d)(3)(iii)(b)(1), and (2)), and (f) through (m), which covers each employee required by this section to use a respirator.
(ii) If air-purifying respirators (chemical-cartridge or chemical-canister types) are used:
(A) The air-purifying canister or cartridge must be replaced prior to the expiration of its service life or at the completion of each shift, whichever occurs first.
(B) A label must be attached to the cartridge or canister to indicate the date and time at which it is first installed on the respirator.
(3) Respirator selection. Employers must:
(i) Select, and provide to employees, the appropriate respirators specified in paragraph (d)(3)(i)(A) of 29 CFR 1910.134.
(ii) For escape, provide employees with any organic vapor respirator or any self-contained breathing apparatus permitted for use under paragraph (h)(3)(i) of this standard.
(i) Emergency situations —(1) Written plans. (i) A written plan for emergency situations shall be developed for each workplace where liquid AN is present. Appropriate portions of the plan shall be implemented in the event of an emergency.
(ii) The plan shall specifically provide that employees engaged in correcting emergency conditions shall be equipped as required in paragraph (h) of this section until the emergency is abated.
(iii) Employees not engaged in correcting the emergency shall be evacuated from the area and shall not be permitted to return until the emergency is abated.
(2) Alerting employees. Where there is the possibility of employee exposure to AN in excess of the ceiling limit, a general alarm shall be installed and used to promptly alert employees of such occurrences.
(j) Protective clothing and equipment —(1) Provision and use. Where eye or skin contact with liquid AN may occur, the employer shall provide at no cost to the employee, and assure that employees wear, impermeable protective clothing or other equipment to protect any area of the body which may come in contact with liquid AN. The provision of §§ 1910.132 and 1910.133 shall be complied with.
(2) Cleaning and replacement. (i) The employer shall clean, launder, maintain, or replace protective clothing and equipment required by this section as needed to maintain their effectiveness.
(ii) The employer shall assure that impermeable protective clothing which contacts or is likely to have contacted liquid AN shall be decontaminated before being removed by the employee.
(iii) The employer shall assure that an employee whose nonimpermeable clothing becomes wetted with liquid AN shall immediately remove that clothing and proceed to shower. The clothing shall be decontaminated before it is removed from the regulated area.
(iv) The employer shall assure that no employee removes protective clothing or equipment from the change room, except for those employees authorized to do so for the purpose of laundering, maintenance, or disposal.
(v) The employer shall inform any person who launders or cleans protective clothing or equipment of the potentially harmful effects of exposure to AN.
(k) Housekeeping. (1) All surfaces shall be maintained free of visible accumulations of liquid AN.
(2) For operations involving liquid AN, the employer shall institute a program for detecting leaks and spills of liquid AN, including regular visual inspections.
(3) Where spills of liquid AN are detected, the employer shall assure that surfaces contacted by the liquid AN are decontaminated. Employees not engaged in decontamination activities shall leave the area of the spill, and shall not be permitted in the area until decontamination is completed.
(l) Waste disposal. AN waste, scrap, debris, bags, containers, or equipment shall be decontaminated before being incorporated in the general waste disposal system.
(m) Hygiene facilities and practices. (1) Where employees are exposed to airborne concentrations of AN above the permissible exposure limits, or where employees are required to wear protective clothing or equipment pursuant to paragraph (j) of this section, the facilities required by 29 CFR 1910.141, including clean change rooms and shower facilities, shall be provided by the employer for the use of those employees, and the employer shall assure that the employees use the facilities provided.
(2) The employer shall assure that employees wearing protective clothing or equipment for protection from skin contact with liquid AN shall shower at the end of the work shift.
(3) The employer shall assure that, in the event of skin or eye exposure to liquid AN, the affected employee shall shower immediately to minimize the danger of skin absorption.
(4) The employer shall assure that employees working in the regulated area wash their hands and faces prior to eating.
(n) Medical surveillance —(1) General. (i) The employer shall institute a program of medical surveillance for each employee who is or will be exposed to AN at or above the action level, without regard to the use of respirators. The employer shall provide each such employee with an opportunity for medical examinations and tests in accordance with this paragraph.
(ii) The employer shall assure that all medical examinations and procedures are performed by or under the supervision of a licensed physician, and that they shall be provided without cost to the employee.
(2) Initial examinations. At the time of initial assignment, or upon institution of the medical surveillance program, the employer shall provide each affected employee an opportunity for a medical examination, including at least the following elements:
(i) A work history and medical history with special attention to skin, respiratory, and gastrointestinal systems, and those nonspecific symptoms, such as headache, nausea, vomiting, dizziness, weakness, or other central nervous system dysfunctions that may be associated with acute or with chronic exposure to AN;
(ii) A complete physical examination giving particular attention to the peripheral and central nervous system, gastrointestinal system, respiratory system, skin, and thyroid;
(iii) A 14- by 17-inch or other reasonably-sized standard film or digital posterior-anterior chest X-ray; and
(iv) Further tests of the intestinal tract, including fecal occult blood screening, for all workers 40 years of age or older, and for any other affected employees for whom, in the opinion of the physician, such testing is appropriate.
(3) Periodic examinations. (i) The employer shall provide the examinations specified in paragraphs (n)(2)(i), (ii), and (iv) of this section at least annually for all employees specified in paragraph (n)(1) of this section.
(ii) If an employee has not had the examination specified in paragraphs (n)(2)(i), (ii), and (iv) of this section within 6 months preceding termination of employment, the employer shall make such examination available to the employee prior to such termination.
(4) Additional examinations. If the employee for any reason develops signs or symptoms which may be associated with exposure to AN, the employer shall provide an appropriate examination and emergency medical treatment.
(5) Information provided to the physician. The employer shall provide the following information to the examining physician:
(i) A copy of this standard and its appendixes;
(ii) A description of the affected employee's duties as they relate to the employee's exposure;
(iii) The employee's representative exposure level;
(iv) The employee's anticipated or estimated exposure level (for preplacement examinations or in cases of exposure due to an emergency);
(v) A description of any personal protective equipment used or to be used; and
(vi) Information from previous medical examinations of the affected employee, which is not otherwise available to the examining physician.
(6) Physician's written opinion. (i) The employer shall obtain a written opinion from the examining physician which shall include:
(A) The results of the medical examination and test performed;
(B) The physician's opinion as to whether the employee has any detected medical condition(s) which would place the employee at an increased risk of material impairment of the employee's health from exposure to AN;
(C) Any recommended limitations upon the employee's exposure to AN or upon the use of protective clothing and equipment such as respirators; and
(D) A statement that the employee has been informed by the physician of the results of the medical examination and any medical conditions which require further examination or treatment.
(ii) The employer shall instruct the physician not to reveal in the written opinion specific findings or diagnoses unrelated to occupational exposure to AN.
(iii) The employer shall provide a copy of the written opinion to the affected employee.
(o) Employee information and training —(1) Training program. (i) The employer shall train each employee exposed to AN above the action level, each employee whose exposures are maintained below the action level by engineering and work practice controls, and each employee subject to potential skin or eye contact with liquid AN in accordance with the requirements of this section. The employer shall institute a training program and ensure employee participation in the program.
(ii) Training shall be provided at the time of initial assignment, or upon institution of the training program, and at least annually thereafter, and the employer shall assure that each employee is informed of the following:
(A) The information contained in appendixes A and B;
(B) The quantity, location, manner of use, release, or storage of AN, and the specific nature of operations which could result in exposure to AN, as well as any necessary protective steps;
(C) The purpose, proper use, and limitations of respirators and protective clothing;
(D) The purpose and a description of the medical surveillance program required by paragraph (n) of this section;
(E) The emergency procedures developed, as required by paragraph (i) of this section;
(F) Engineering and work practice controls, their function, and the employee's relationship to these controls; and
(G) A review of this standard.
(2) Access to training materials. (i) The employer shall make a copy of this standard and its appendixes readily available to all affected employees.
(ii) The employer shall provide, upon request, all materials relating to the employee information and training program to the Assistant Secretary and the Director.
(p) Communication of hazards —(1) Hazard communication—general. (i) Chemical manufacturers, importers, distributors and employers shall comply with all requirements of the Hazard Communication Standard (HCS) (§ 1910.1200) for AN and AN-based materials not exempted under paragraph (a)(2) of this section.
(ii) In classifying the hazards of AN and AN-based materials at least the following hazards are to be addressed: Cancer; central nervous system effects; liver effects; skin sensitization; skin, respiratory, and eye irritation; acute toxicity effects; and flammability.
(iii) Employers shall include AN and AN-based materials in the hazard communication program established to comply with the HCS (§ 1910.1200). Employers shall ensure that each employee has access to labels on containers of AN and AN-based materials and to safety data sheets, and is trained in accordance with the requirements of HCS and paragraph (o) of this section.
(iv) The employer shall ensure that no statement appears on or near any sign or label required by this paragraph (p) that contradicts or detracts from the required sign or label.
(2) Signs. (i) The employer shall post signs to clearly indicate all workplaces where AN concentrations exceed the permissible exposure limits. The signs shall bear the following legend:
(ii) The employer shall ensure that signs required by this paragraph (p)(2) are illuminated and cleaned as necessary so that the legend is readily visible.
(iii) Prior to June 1, 2016, employers may use the following legend in lieu of that specified in paragraph (p)(2)(i) of this section:
(3) Labels. (i) The employer shall ensure that precautionary labels are in compliance with paragraph (p)(1)(i) of this section and are affixed to all containers of liquid AN and AN-based materials not exempted under paragraph (a)(2) of this section. The employer shall ensure that the labels remain affixed when the materials are sold, distributed, or otherwise leave the employer's workplace.
(ii) Prior to June 1, 2015, employers may include the following information on precautionary labels required by this paragraph (p)(3) in lieu of the labeling requirements in paragraph (p)(1) of this section:
(iii) The employer shall ensure that the precautionary labels required by this paragraph (p)(3) are readily visible and legible.
(q) Recordkeeping —(1) Objective data for exempted operations. (i) Where the processing, use, and handling of materials made from or containing AN are exempted pursuant to paragraph (a)(2)(ii) of this section, the employer shall establish and maintain an accurate record of objective data reasonably relied upon in support of the exemption.
(ii) This record shall include at least the following information:
(A) The material qualifying for exemption;
(B) The source of the objective data;
(C) The testing protocol, results of testing, and/or analysis of the material for the release of AN;
(D) A description of the operation exempted and how the data supports the exemption; and
(E) Other data relevant to the operations, materials, and processing covered by the exemption.
(iii) The employer shall maintain this record for the duration of the employer's reliance upon such objective data.
(2) Exposure monitoring. (i) The employer shall establish and maintain an accurate record of all monitoring required by paragraph (e) of this section.
(ii) This record shall include:
(A) The dates, number, duration, and results of each of the samples taken, including a description of the sampling procedure used to determine representative employee exposure;
(B) A description of the sampling and analytical methods used and the data relied upon to establish that the methods used meet the accuracy and precision requirements of paragraph (e)(6) of this section;
(C) Type of respiratory protective devices worn, if any; and
(D) Name and job classification of the employee monitored and of all other employees whose exposure the measurement is intended to represent.
(iii) The employer shall maintain this record for at least forty (40) years, or for the duration of employment plus twenty (20) years, whichever is longer.
(3) Medical surveillance. (i) The employer shall establish and maintain an accurate record for each employee subject to medical surveillance as required by paragraph (n) of this section.
(ii) This record shall include:
(A) A copy of the physician's written opinions;
(B) Any employee medical complaints related to exposure to AN;
(C) A copy of the information provided to the physician as required by paragraph (n)(5) of this section; and
(D) A copy of the employee's medical and work history.
(iii) The employer shall assure that this record be maintained for at least forty (40) years, or for the duration of employment plus twenty (20) years, whichever is longer.
(4) Availability. (i) The employer shall make all records required to be maintained by this section available, upon request, to the Assistant Secretary and the Director for examination and copying.
(ii) Records required by paragraphs (q)(1) through (q)(3) of this section shall be provided upon request to employees, designated representatives, and the Assistant Secretary in accordance with 29 CFR 1910.1020 (a) through (e) and (q) through (i). Records required by paragraph (q)(1) shall be provided in the same manner as exposure monitoring records.
(5) Transfer of records. (i) Whenever the employer ceases to do business, the successor employer shall receive and retain all records required to be maintained by this section for the prescribed period.
(ii) The employer shall also comply with any additional requirements involving transfer of records set forth in 29 CFR 1910.1020(h).
(r) 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 AN conducted pursuant to paragraph (e) of this section.
(2) Observation procedures. (i) Whenever observation of the monitoring of employee exposure to AN requires entry into an area where the use of protective clothing or equipment is required, the employer shall provide the observer with personal protective clothing and equipment required to be worn by employees working in the area, assure the use of such clothing and equipment, and require the observer to comply with all other applicable safety and health procedures.
(ii) Without interfering with the monitoring, observers shall be entitled:
(A) To receive an explanation of the measurement procedures;
(B) To observe all steps related to the measurement of airborne concentrations of AN performed at the place of exposure; and
(C) To record the results obtained.
(s) [Reserved]
(t) Appendixes. The information contained in the appendixes is not intended, by itself, to create any additional obligation not otherwise imposed, or to detract from any obligation.
A. Substance: Acrylonitrile (CH 2 CHCN).
B. Synonyms: Propenenitrile; vinyl cyanide; cyanoethylene; AN; VCN; acylon; carbacryl; fumigrian; ventox.
C. Acrylonitrile can be found as a liquid or vapor, and can also be found in polymer resins, rubbers, plastics, polyols, and other polymers having acrylonitrile as a raw or intermediate material.
D. AN is used in the manufacture of acrylic and modiacrylic fibers, acrylic plastics and resins, speciality polymers, nitrile rubbers, and other organic chemicals. It has also been used as a fumigant.
E. Appearance and odor: Colorless to pale yellow liquid with a pungent odor which can only be detected at concentrations above the permissible exposure level, in a range of 13-19 parts AN per million parts of air (13-19 ppm).
F. Permissible exposure: Exposure may not exceed either:
1. Two parts AN per million parts of air (2 ppm) averaged over the 8-hour workday; or
2. Ten parts AN per million parts of air (10 ppm) averaged over any 15-minute period in the workday.
3. In addition, skin and eye contact with liquid AN is prohibited.
A. Acrylonitrile can affect your body if you inhale the vapor (breathing), if it comes in contact with your eyes or skin, or if you swallow it. It may enter your body through your skin.
B. Effects of overexposure: 1. Short-term exposure: Acrylonitrile can cause eye irritation, nausea, vomiting, headache, sneezing, weakness, and light-headedness. At high concentrations, the effects of exposure may go on to loss of consciousness and death. When acrylonitrile is held in contact with the skin after being absorbed into shoe leather or clothing, it may produce blisters following several hours of no apparent effect. Unless the shoes or clothing are removed immediately and the area washed, blistering will occur. Usually there is no pain or inflammation associated with blister formation.
2. Long-term exposure: Acrylonitrile has been shown to cause cancer in laboratory animals and has been associated with higher incidences of cancer in humans. Repeated or prolonged exposure of the skin to acrylonitrile may produce irritation and dermatitis.
3. Reporting signs and symptoms: You should inform your employer if you develop any signs or symptoms and suspect they are caused by exposure to acrylonitrile.
A. Eye exposure: If acrylonitrile gets into your eyes, wash your eyes immediately with large amounts of water, lifting the lower and upper lids occasionally. Get medical attention immediately. Contact lenses should not be worn when working with this chemical.
B. Skin exposure: If acrylonitrile gets on your skin, immediately wash the contaminated skin with water. If acrylonitrile soaks through your clothing, especially your shoes, remove the clothing immediately and wash the skin with water. If symptoms occur after washing, get medical attention immediately. Thoroughly wash the clothing before reusing. Contaminated leather shoes or other leather articles should be discarded.
C. Inhalation: If you or any other person breathes in large amounts of acrylonitrile, move the exposed person to fresh air at once. If breathing has stopped, perform artificial respiration. Keep the affected person warm and at rest. Get medical attention as soon as possible.
D. Swallowing: When acrylonitrile 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 touch the back of his throat with his 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, notify someone else and put into effect the 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.
F. Special first aid procedures: First aid kits containing an adequate supply (at least two dozen) of amyl nitrite pearls, each containing 0.3 ml, should be maintained at each site where acrylonitrile is used. When a person is suspected of receiving an overexposure to acrylonitrile, immediately remove that person from the contaminated area using established rescue procedures. Contaminated clothing must be removed and the acrylonitrile washed from the skin immediately. Artificial respiration should be started at once if breathing has stopped. If the person is unconscious, amyl nitrite may be used as an antidote by a properly trained individual in accordance with established emergency procedures. Medical aid should be obtained immediately.
A. Respirators. You may be required to wear a respirator for nonroutine activities, in emergencies, while your employer is in the process of reducing acrylonitrile exposures through engineering controls, and in areas where engineering controls are not feasible. If respirators are worn, they must have a label issued by the National Institute for Occupational Safety and Health under the provisions of 42 CFR part 84 stating that the respirators have been approved for use with organic vapors. For effective protection, respirators must fit your face and head snugly. Respirators must not be loosened or removed in work situations where their use is required.
Acrylonitrile does not have a detectable odor except at levels above the permissible exposure limits. Do not depend on odor to warn you when a respirator cartridge or canister is exhausted. Cartridges or canisters must be changed daily or before the end-of-service-life, whichever comes first. Reuse of these may allow acrylonitrille to gradually filter through the cartridge and cause exposures which you cannot detect by odor. If you can smell acrylonitrile while wearing a respirator, proceed immediately to fresh air. If you experience difficulty breathing while wearing a respirator, tell your employer.
B. Supplied-air suits: In some work situations, the wearing of supplied-air suits may be necessary. Your employer must instruct you in their proper use and operation.
C. Protective clothing: You must wear impervious clothing, gloves, face shield, or other appropriate protective clothing to prevent skin contact with liquid acrylonitrile. Where protective clothing is required, your employer is required to provide clean garments to you as necessary to assume that the clothing protects you adequately.
Replace or repair impervious clothing that has developed leaks.
Acrylonitrile should never be allowed to remain on the skin. Clothing and shoes which are not impervious to acrylonitrile should not be allowed to become contaminated with acrylonitrile, and if they do the clothing and shoes should be promptly removed and decontaminated. The clothing should be laundered or discarded after the AN is removed. Once acrylonitrile penetrates shoes or other leather articles, they should not be worn again.
D. Eye protection: You must wear splashproof safety goggles in areas where liquid acrylonitrile may contact your eyes. In addition, contact lenses should not be worn in areas where eye contact with acrylonitrile can occur.
A. Acrylonitrile is a flammable liquid, and its vapors can easily form explosive mixtures in air.
B. Acrylonitrile must be stored in tightly closed containers in a cool, well-ventilated area, away from heat, sparks, flames, strong oxidizers (especially bromine), strong bases, copper, copper alloys, ammonia, and amines.
C. Sources of ignition such as smoking and open flames are prohibited wherever acrylonitrile 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 acrylonitrile, and containers must be bonded and grounded when pouring or transferring liquid acrylonitrile.
E. You must immediately remove any non-impervious clothing that becomes wetted with acrylonitrile, and this clothing must not be reworn until the acrylonitrile is removed from the clothing.
F. Impervious clothing wet with liquid acrylonitrile can be easily ignited. This clothing must be washed down with water before you remove it.
G. If your skin becomes wet with liquid acrylonitrile, you must promptly and thoroughly wash or shower with soap or mild detergent to remove any acrylonitrile from your skin.
H. You must not keep food, beverages, or smoking materials, nor are you permitted to eat or smoke in regulated areas where acrylonitrile concentrations are above the permissible exposure limits.
I. If you contact liquid acrylonitrile, you must wash your hands thoroughly with soap or mild detergent and water before eating, smoking, or using toilet facilities.
J. Fire extinguishers and quick drenching facilities must be readily available, and you should know where they are and how to operate them.
K. Ask your supervisor where acrylonitrile is used in your work area and for any additional plant safety and health rules.
A. Each year, your employer is required to inform you of the information contained in this Substance Safety Data Sheet for acrylonitrile. In addition, you employer must instruct you in the proper work practices for using acrylonitrile, emergency procedures, and the correct use of protective equipment.
B. Your employer is required to determine whether you are being exposed to acrylonitrile. 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. These records must be kept by the employer for at least forty (40) years or for the period of your employment plus twenty (20) years, whichever is longer.
D. Your employer is required to release your exposure and medical records to you or your representative upon your request.
A. Substance identification: 1. Synonyms: AN; VCN; vinyl cyanide; propenenitrile; cyanoethylene; Acrylon; Carbacryl; Fumigrain; Ventox.
2. Formula: CH2 = CHCN.
3. Molecular weight: 53.1.
B. Physical data: 1. Boiling point (760 mm Hg): 77.3 °C (171 °F);
2. Specific gravity (water = 1): 0.81 (at 20 °C or 68 °F);
3. Vapor density (air = 1 at boiling point of acrylonitrile): 1.83;
4. Melting point: −83 °C (−117 °F);
5. Vapor pressure (@20 °F): 83 mm Hg;
6. Solubility in water, percent by weight @20 °C (68 °F): 7.35;
7. Evaporation rate (Butyl Acetate = 1): 4.54; and
8. Appearance and odor: Colorless to pale yellow liquid with a pungent odor at concentrations above the permissible exposure level. Any detectable odor of acrylonitrile may indicate overexposure.
A. Fire: 1. Flash point: −1 °C (30 °F) (closed cup).
2. Autoignition temperature: 481 °C (898 °F).
3. Flammable limits air, percent by volume: Lower: 3, Upper: 17.
4. Extinguishing media: Alcohol foam, carbon dioxide, and dry chemical.
5. Special fire-fighting procedures: Do not use a solid stream of water, since the stream will scatter and spread the fire. Use water to cool containers exposed to a fire.
6. Unusual fire and explosion hazards: Acrylonitrile is a flammable liquid. Its vapors can easily form explosive mixtures with air. All ignition sources must be controlled where acrylonitrile is handled, used, or stored in a manner that could create a potential fire or explosion hazard. Acrylonitrile vapors are heavier than air and may travel along the ground and be ignited by open flames or sparks at locations remote from the site at which acrylonitrile is being handled.
7. For purposes of compliance with the requirements of 29 CFR 1910.106, acrylonitrile is classified as a class IB flammable liquid. 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 29 CFR 1910.157, acrylonitrile is classified as a Class B fire hazard.
9. For purpose of compliance with 29 CFR 1919.309, locations classified as hazardous due to the presence of acrylonitrile shall be Class I, Group D.
B. Reactivity:
1. Conditions contributing to instability: Acrylonitrile will polymerize when hot, and the additional heat liberated by the polymerization may cause containers to explode. Pure AN may self-polymerize, with a rapid build-up of pressure, resulting in an explosion hazard. Inhibitors are added to the commercial product to prevent self-polymerization.
2. Incompatibilities: Contact with strong oxidizers (especially bromine) and strong bases may cause fires and explosions. Contact with copper, copper alloys, ammonia, and amines may start serious decomposition.
3. Hazardous decompostion products: Toxic gases and vapors (such as hydrogen cyanide, oxides of nitrogen, and carbon monoxide) may be released in a fire involving acrylonitrile and certain polymers made from acrylonitrile.
4. Special precautions: Liquid acrylonitrile will attack some forms of plastics, rubbers, and coatings.
A. If acrylonitrile 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.
3. If liquid acrylonitrile or polymer intermediate, collect for reclamation or absorb in paper, vermiculite, dry sand, earth, or similar material, or wash down with water into process sewer system.
B. Persons not wearing protective equipment should be restricted from areas of spills or leaks until clean-up 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. Spills of acrylonitrile and flushing of such spills shall be channeled for appropriate treatment or collection for disposal. They shall not be channeled directly into the sanitary sewer system. In selecting the method of waste disposal, applicable local, State, and Federal regulations should be consulted.
A. Exposure above the Permissible Exposure Limit:
1. Eight-hour exposure evaluation: Measurements taken for the purpose of determining employee exposure under this section are best taken so that the average 8-hour exposure may be determined from a single 8-hour sample or two (2) 4-hour samples. Air samples should be taken in the employee's breathing zone (air that would most nearly represent that inhaled by the employee.)
2. Ceiling evaluation: Measurements taken for the purpose of determining employee exposure under this section must be taken during periods of maximum expected airborne concentrations of acrylonitrile in the employee's breathing zone. A minimum of three (3) measurements should be taken on one work shift. The average of all measurements taken is an estimate of the employee's ceiling exposure.
3. Monitoring techniques: The sampling and analysis under this section may be performed by collecting the acrylonitrile vapor on charcoal adsorption tubes or other composition adsorption tubes, with subsequent chemical analysis. Sampling and analysis may also be performed by instruments such as real-time continuous monitoring systems, portable direct-reading instruments, or passive dosimeters. Analysis of resultant samples should be by gas chromatograph.
Appendix D lists methods of sampling and analysis which have been tested by NIOSH and OSHA for use with acrylonitrile. NIOSH and OSHA have validated modifications of NIOSH Method S-156 (See appendix D) under laboratory conditions for concentrations below 1 ppm. The employer has the obligation of selecting a monitoring method which meets the accuracy and precision requirements of the standard under his unique field conditions. The standard requires that methods of monitoring must be accurate, to a 95-percent confidence level, to ±35-percent for concentrations of AN at or above 2 ppm, and to ±50-percent for concentrations below 2 ppm. In addition to the methods described in appendix D, there are numerous other methods available for monitoring for AN in the workplace. Details on these other methods have been submitted by various companies to the rulemaking record, and are available at the OSHA Docket Office.
B. Since many of the duties relating to employee exposure are dependent on the results of monitoring and measuring procedures, employers shall assure that the evaluation of employee exposures is performed by a competent industrial hygienist or other technically qualified person.
Employees shall be provided with and required to wear appropriate protective clothing to prevent any possibility of skin contact with liquid AN. Because acrylonitrile is absorbed through the skin, it is important to prevent skin contact with liquid AN. Protective clothing shall include impermeable coveralls or similar full-body work clothing, gloves, head-coverings, as appropriate to protect areas of the body which may come in contact with liquid AN.
Employers should ascertain that the protective garmets are impermeable to acrylonitrile. Non-impermeable clothing and shoes should not be allowed to become contaminated with liquid AN. If permeable clothing does become contaminated, it should be promptly removed, placed in a regulated area for removal of the AN, and not worn again until the AN is removed. If leather footwear or other leather garments become wet from acrylonitrile, they should be replaced and not worn again, due to the ability of leather to absorb acrylonitrile and hold it against the skin. Since there is no pain associated with the blistering which may result from skin contact with liquid AN, it is essential that the employee be informed of this hazard so that he or she can be protected.
Any protective clothing which has developed leaks or is otherwise found to be defective shall be repaired or replaced. Clean protective clothing shall be provided to the employee as necessary to assure its protectiveness. Whenever impervious clothing becomes wet with liquid AN, it shall 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 acrylonitrile contacting the eyes.
For purposes of complying with 29 CFR 1910.141, the following items should be emphasized:
A. The workplace should be kept clean, orderly, and in a sanitary condition. The employer is required to institute a leak and spill detection program for operations involving liquid AN in order to detect sources of fugitive AN emissions.
B. Dry sweeping and the use of compressed air is unsafe for the cleaning of floors and other surfaces where liquid AN may be found.
C. Adequate washing facilities with hot and cold water are to be provided, and maintained in a sanitary condition. Suitable cleansing agents are also to be provided to assure the effective removal of acrylonitrile from the skin.
D. Change or dressing rooms with individual clothes storage facilities must be provided to prevent the contamination of street clothes with acrylonitrile. Because of the hazardous nature of acrylonitrile, contaminated protective clothing should be placed in a regulated area designated by the employer for removal of the AN before the clothing is laundered or disposed of.
A. Store acrylonitrile in tightly-closed containers in a cool, well-ventilated area and take necessary precautions to avoid any explosion hazard.
B. High exposures to acrylonitrile can occur when transferring the liquid from one container to another.
C. Non-sparking tools must be used to open and close metal acrylonitrile containers. These containers must be effectively grounded and bonded prior to pouring.
D. Never store uninhibited acrylonitrile.
E. Acrylonitrile vapors are not inhibited. They may form polymers and clog vents of storage tanks.
F. Use of supplied-air suits or other impervious coverings may be necessary to prevent skin contact with and provide respiratory protection from acrylonitrile where the concentration of acrylonitrile is unknown or is above the ceiling limit. Supplied-air suits should be selected, used, and maintained under the immediate supervision of persons knowledgeable in the limitations and potential life-endangering characteristics of supplied-air suits.
G. Employers shall advise employees of all areas and operations where exposure to acrylonitrile could occur.
Common operations in which exposure to acrylonitrile is likely to occur include the following: Manufacture of the acrylonitrile monomer; synthesis of acrylic fibers, ABS, SAN, and nitrile barrier plastics and resins, nitrile rubber, surface coatings, specialty chemicals, use as a chemical intermediate, use as a fumigant and in the cyanoethylation of cotton.
Inhalation; skin absorption; ingestion.
Acrylonitrile vapor is an asphyxiant due to inhibitory action on metabolic enzyme systems. Animals exposed to 75 or 100 ppm for 7 hours have shown signs of anoxia; in some animals which died at the higher level, cyanomethemoglobin was found in the blood. Two human fatalities from accidental poisioning have been reported; one was caused by inhalation of an unknown concentration of the vapor, and the other was thought to be caused by skin absorption or inhalation. Most cases of intoxication from industrial exposure have been mild, with rapid onset of eye irritation, headache, sneezing, and nausea. Weakness, lightheadedness, and vomiting may also occur. Exposure to high concentrations may produce profound weakness, asphyxia, and death. The vapor is a severe eye irritant. Prolonged skin contract with the liquid may result in absorption with systemic effects, and in the formation of large blisters after a latent period of several hours. Although there is usually little or no pain or inflammation, the affected skin resembles a second-degree thermal burn. Solutions spilled on exposed skin, or on areas covered only by a light layer of clothing, evaporate rapidly, leaving no irritation, or, at the most, mild transient redness. Repeated spills on exposed skin may result in dermatitis due to solvent effects.
Results after 1 year of a planned 2-year animal study on the effects of exposure to acrylonitrile have indicated that rats ingesting as little as 35 ppm in their drinking water develop tumors of the central nervous system. The interim results of this study have been supported by a similar study being conducted by the same laboratory, involving exposure of rats by inhalation of acrylonitrile vapor, which has shown similar types of tumors in animals exposed to 80 ppm.
In addition, the preliminary results of an epidemiological study being performed by duPont on a cohort of workers in their Camden, S.C. acrylic fiber plant indicate a statistically significant increase in the incidence of colon and lung cancers among employees exposed to acrylonitrile.
Asphyxia and death can occur from exposure to high concentrations of acrylonitrile. Symptoms of overexposure include eye irritation, headache, sneezing, nausea and vomiting, weakness, and light-headedness. Prolonged skin contact can cause blisters on the skin with appearance of a second-degree burn, but with little or no pain. Repeated skin contact may produce scaling dermatits.
Remove employee from exposure. Immediately flush eyes with water and wash skin with soap or mild detergent and water. If AN has been swallowed, and person is conscious, induce vomiting. Give artificial resuscitation if indicated. More severe cases, such as those associated with loss of consciousness, may be treated by the intravenous administration of sodium nitrite, followed by sodium thiosulfate, although this is not as effective for acrylonitrile poisoning as for inorganic cyanide poisoning.
A. As noted above, exposure to acrylonitrile has been linked to increased incidence of cancers of the colon and lung in employees of the duPont acrylic fiber plant in Camden, S.C. In addition, the animal testing of acrylonitrile has resulted in the development of cancers of the central nervous system in rats exposed by either inhalation or ingestion. The physician should be aware of the findings of these studies in evaluating the health of employees exposed to acrylonitrile.
Most reported acute effects of occupational exposure to acrylonitrile are due to its ability to cause tissue anoxia and asphyxia. The effects are similar to those caused by hydrogen cyanide. Liquid acrylonitrile can be absorbed through the skin upon prolonged contact. The liquid readily penetrates leather, and will produce burns of the feet if footwear contaminated with acrylonitrile is not removed.
It is important for the physician to become familiar with the operating conditions in which exposure to acrylonitrile may occur. Those employees with skin diseases may not tolerate the wearing of whatever protective clothing may be necessary to protect them from exposure. In addition, those with chronic respiratory disease may not tolerate the wearing of negative-pressure respirators.
B. Surveillance and screening. Medical histories and laboratory examinations are required for each employee subject to exposure to acrylonitrile above the action level. The employer must screen employees for history of certain medical conditions which might place the employee at increased risk from exposure.
1. Central nervous system dysfunction. Acute effects of exposure to acrylonitrile generally involve the central nervous system. Symptoms of acrylonitrile exposure include headache, nausea, dizziness, and general weakness. The animal studies cited above suggest possible carcinogenic effects of acrylonitrile on the central nervous system, since rats exposed by either inhalation or ingestion have developed similar CNS tumors.
2. Respiratory disease. The du Pont data indicate an increased risk of lung cancer among employees exposed to acrylonitrile.
3. Gastrointestinal disease. The du Pont data indicate an increased risk of cancer of the colon among employees exposed to acrylonitrile. In addition, the animal studies show possible tumor production in the stomachs of the rats in the ingestion study.
4. Skin disease. Acrylonitrile can cause skin burns when prolonged skin contact with the liquid occurs. In addition, repeated skin contact with the liquid can cause dermatitis.
5. General. The purpose of the medical procedures outlined in the standard is to establish a baseline for future health monitoring. Persons unusually susceptible to the effects of anoxia or those with anemia would be expected to be at increased risk. In addition to emphasis on the CNS, respiratory and gastro-intestinal systems, the cardiovascular system, liver, and kidney function should also be stressed.
There are many methods available for monitoring employee exposures to acrylonitrile. Most of these involve the use of charcoal tubes and sampling pumps, with analysis by gas chromatograph. The essential differences between the charcoal tube methods include, among others, the use of different desorbing solvents, the use of different lots of charcoal, and the use of different equipment for analysis of the samples.
Besides charcoal, considerable work has been performed on methods using porous polymer sampling tubes and passive dosimeters. In addition, there are several portable gas analyzers and monitoring units available on the open market.
This appendix contains details for the methods which have been tested at OSHA Analytical Laboratory in Salt Lake City, and NIOSH in Cincinnati. Each is a variation on NIOSH Method S-156, which is also included for reference. This does not indicate that these methods are the only ones which will be satisfactory. There also may be workplace situations in which these methods are not adequate, due to such factors as high humidity. Copies of the other methods available to OSHA are available in the rulemaking record, and may be obtained from the OSHA Docket Office. These include, the Union Carbide, Monsanto, Dow Chemical and Dow Badische methods, as well as NISOH Method P & CAM 127.
Employers who note problems with sample breakthrough should try larger charcoal tubes. Tubes of larger capacity are available, and are often used for sampling vinyl chloride. In addition, lower flow rates and shorter sampling times should be beneficial in minimizing breakthrough problems.
Whatever method the employer chooses, he must assure himself of the method's accuracy and precision under the unique conditions present in his workplace.
1. Principle of the method (Reference 11.1).
1.1 A known volume of air is drawn through a charcoal tube to trap the organic vapors present.
1.2 The charcoal in the tube is transferred to a small, stoppered sample container, and the analyte is desorbed with methanol.
1.3 An aliquot of the desorbed sample is injected into a gas chromatograph.
1.4 The area of the resulting peak is determined and compared with areas obtained for standards.
2. Range and sensitivity.
2.1 This method was validated over the range of 17.5-70.0 mg/cu m at an atmospheric temperature and pressure of 22 °C and 760 MM Hg, using a 20-liter sample. Under the conditions of sample size (20-liters) the probable useful range of this method is 4.5-135 mg-cu m. The method is capable of measuring much smaller amounts if the desorption efficiency is adequate. Desorption efficiency must be determined over the range used.
2.2 The upper limit of the range of the method is dependent on the adsorptive capacity of the charcoal tube. This capacity varies with the concentrations of acrylonitrile and other substances in the air. The first section of the charcoal tube was found to hold at least 3.97 mg of acrylonitrile when a test atmosphere containing 92.0 mg/cu m of acrylonitrile in air was sampled 0.18 liter per minute for 240 minutes; at that time the concentration of acrylonitrile in the effluent was less than 5 percent of that in the influent. (The charcoal tube consists of two sections of activated charcoal separated by a section of urethane foam. See section 6.2.) If a particular atmosphere is suspected of containing a large amount of contaminant, a smaller sampling volume should be taken.
3. Interference.
3.1 When the amount of water in the air is so great that condensation actually occurs in the tube, organic vapors will not be trapped efficiently. Preliminary experiments using toluene indicate that high humidity severely decreases the breakthrough volume.
3.2 When interfering compounds are known or suspected to be present in the air, such information, including their suspected identities, should be transmitted with the sample.
3.3 It must be emphasized that any compound which has the same retention time as the analyte at the operating conditions described in this method is an interference. Retention time data on a single column cannot be considered proof of chemical identity.
3.4 If the possibility of interference exists, separation conditions (column packing, temperature, etc.) must be changed to circumvent the problem.
4. Precision and accuracy.
4.1 The Coefficient of Variation (CV T ) for the total analytical and sampling method in the range of 17.5-70.0 mg/cu m was 0.073. This value corresponds to a 3.3 mg/cu m standard deviation at the (previous) OSHA standard level (20 ppm). Statistical information and details of the validation and experimental test procedures can be found in Reference 11.2.
4.2 On the average the concentrations obtained at the 20 ppm level using the overall sampling and analytical method were 6.0 percent lower than the “true” concentrations for a limited number of laboratory experiments. Any difference between the “found” and “true” concentrations may not represent a bias in the sampling and analytical method, but rather a random variation from the experimentally determined “true” concentration. Therefore, no recovery correction should be applied to the final result in section 10.5.
5. Advantages and disadvantages of the method.
5.1 The sampling device is small, portable, and involves no liquids. Interferences are minimal, and most of those which do occur can be eliminated by altering chromatographic conditions. The tubes are analyzed by means of a quick, instrumental method.
The method can also be used for the simultaneous analysis of two or more substances suspected to be present in the same sample by simply changing gas chromatographic conditions.
5.2 One disadvantage of the method is that the amount of sample which can be taken is limited by the number of milligrams that the tube will hold before overloading. When the sample value obtained for the backup section of the charcoal tube exceeds 25 percent of that found on the front section, the possibility of sample loss exists.
5.3 Furthermore, the precision of the method is limited by the reproducibility of the pressure drop across the tubes. This drop will affect the flow rate and cause the volume to be imprecise, because the pump is usually calibrated for one tube only.
6. Apparatus.
6.1 A calibrated personal sampling pump whose flow can be determined within ±5 percent at the recommended flow rate. (Reference 11.3).
6.2 Charcoal tubes: Glass tubes with both ends flame sealed, 7 cm long with a 6-mm O.D. and a 4-mm I.D., containing 2 sections of 20/40 mesh activated charcoal separated by a 2-mm portion of urethane foam. The activated charcoals prepared from coconut shells and is fired at 600 °C prior to packing. 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 silicated glass wool is placed in front of the adsorbing section. The pressure drop across the tube must be less than 1 inch of mercury at a flow rate of 1 liter per minute.
6.3 Gas chromatograph equipped with a flame ionization detector.
6.4 Column (4-ft × 1/4 -in stainless steel) packed with 50/80 mesh Poropak, type Q.
6.5 An electronic integrator or some other suitable method for measuring peak areas.
6.6 Two-milliliter sample containers with glass stoppers or Teflon-lined caps. If an automatic sample injector is used, the associated vials may be used.
6.7 Microliter syringes: 10-microliter and other convenient sizes for making standards.
6.8 Pipets: 1.0-ml delivery pipets.
6.9 Volumetric flask: 10-ml or convenient sizes for making standard solutions.
7. Reagents.
7.1 Chromatographic quality methanol.
7.2 Acrylonitrile, reagent grade.
7.3 Hexane, reagent grade.
7.4 Purified nitrogen.
7.5 Prepurified hydrogen.
7.6 Filtered compressed air.
8. Procedure.
8.1 Cleaning of equipment. All glassware used for the laboratory analysis should be detergent washed and thoroughly rinsed with tap water and distilled water.
8.2 Calibration of personal pumps. Each personal pump must be calibrated with a representative charcoal tube in the line. This will minimize errors associated with uncertainties in the sample volume collected.
8.3 Collection and shipping of samples.
8.3.1 Immediately before sampling, break the ends of the tube to provide an opening at least one-half the internal diameter of the tube (2 mm).
8.3.2 The smaller section of charcoal is used as a backup and should be positioned nearest the sampling pump.
8.3.3 The charcoal tube should be placed in a vertical direction during sampling to minimize channeling through the charcoal.
8.3.4 Air being sampled should not be passed through any hose or tubing before entering the charcoal tube.
8.3.5 A maximum sample size of 20 liters is recommended. Sample at a flow of 0.20 liter per minute or less. The flow rate should be known with an accuracy of at least ±5 percent.
8.3.6 The temperature and pressure of the atmosphere being sampled should be recorded. If pressure reading is not available, record the elevation.
8.3.7 The charcoal tubes should be capped with the supplied plastic caps immediately after sampling. Under no circumstances should rubber caps be used.
8.3.8 With each batch of 10 samples submit one tube from the same lot of tubes which was used for sample collection and which is subjected to exactly the same handling as the samples except that no air is drawn through it. Label this as a blank.
8.3.9 Capped tubes should be packed tightly and padded before they are shipped to minimize tube breakage during shipping.
8.3.10 A sample of the bulk material should be submitted to the laboratory in a glass container with a Teflon-lined cap. This sample should not be transported in the same container as the charcoal tubes.
8.4 Analysis of samples.
8.4.1 Preparation of samples. In preparation for analysis, each charcoal tube is scored with a file in front of the first section of charcoal and broken open. The glass wool is removed and discarded. The charcoal in the first (larger) section is transferred to a 2-ml stoppered sample container. The separating section of foam is removed and discarded; the second section is transferred to another stoppered container. These two sections are analyzed separately.
8.4.2 Desorption of samples. Prior to analysis, 1.0 ml of methanol is pipetted into each sample container. Desorption should be done for 30 minutes. Tests indicate that this is adequate if the sample is agitated occasionally during this period. If an automatic sample injector is used, the sample vials should be capped as soon as the solvent is added to minimize volatilization.
8.4.3 GC conditions. The typical operating conditions for the gas chromatograph are:
1. 50 ml/min (60 psig) nitrogen carrier gas flow.
2. 65 ml/min (24 psig) hydrogen gas flow to detector.
3. 500 ml/min (50 psig) air flow to detector.
4. 235 °C injector temperature.
5. 255 °C manifold temperature (detector).
6. 155 °C column temperature.
8.4.4 Injection. The first step in the analysis is the injection of the sample into the gas chromatograph. To eliminate difficulties arising from blowback or distillation within the syringe needle, one should employ the solvent flush injection technique. The 10-microliter syringe is first flushed with solvent several times to wet the barrel and plunger. Three microliters of solvent are drawn into the syringe to increase the accuracy and reproducibility of the injected sample volume. The needle is removed from the solvent, and the plunger is pulled back about 0.2 microliter to separate the solvent flush from the sample with a pocket of air to be used as a marker. The needle is then immersed in the sample, and a 5-microliter aliquot is withdrawn, taking into consideration the volume of the needle, since the sample in the needle will be completely injected. After the needle is removed from the sample and prior to injection, the plunger is pulled back 1.2 microliters to minimize evaporation of the sample from the tip of the needle. Observe that the sample occupies 4.9-5.0 microliters in the barrel of the syringe. Duplicate injections of each sample and standard should be made. No more than a 3 percent difference in area is to be expected. An automatic sample injector can be used if it is shown to give reproducibility at least as good as the solvent flush method.
8.4.5 Measurement of area. The area of the sample peak is measured by an electronic integrator or some other suitable form of area measurement, and preliminary results are read from a standard curve prepared as discussed below.
8.5 Determination of desorption efficiency.
8.5.1 Importance of determination. The desorption efficiency of a particular compound can vary from one laboratory to another and also from one batch of charcoal to another. Thus, it is necessary to determine at least once the percentage of the specific compound that is removed in the desorption process, provided the same batch of charcoal is used.
8.5.2 Procedure for determining desorption efficiency. Activated charcoal equivalent to the amount in the first section of the sampling tube (100 mg) is measured into a 2.5 in, 4-mm I.D. glass tube, flame sealed at one end. This charcoal must be from the same batch as that used in obtaining the samples and can be obtained from unused charcoal tubes. The open end is capped with Parafilm. A known amount of hexane solution of acrylonitrile containing 0.239 g/ml is injected directly into the activated charcoal with a microliter syringe, and tube is capped with more Parafilm. When using an automatic sample injector, the sample injector vials, capped with Teflon-faced septa, may be used in place of the glass tube.
The amount injected is equivalent to that present in a 20-liter air sample at the selected level.
Six tubes at each of three levels (0.5X, 1X, and 2X of the standard) are prepared in this manner and allowed to stand for at least overnight to assure complete adsorption of the analyte onto the charcoal. These tubes are referred to as the sample. A parallel blank tube should be treated in the same manner except that no sample is added to it. The sample and blank tubes are desorbed and analyzed in exactly the same manner as the sampling tube described in section 8.4.
Two or three standards are prepared by injecting the same volume of compound into 1.0 ml of methanol with the same syringe used in the preparation of the samples. These are analyzed with the samples.
The desorption efficiency (D.E.) equals the average weight in mg recovered from the tube divided by the weight in mg added to the tube, or
The desorption efficiency is dependent on the amount of analyte collected on the charcoal. Plot the desorption efficiency versus weight of analyte found. This curve is used in section 10.4 to correct for adsorption losses.
9. Calibration and standards.
It is convenient to express concentration of standards in terms of mg/1.0 ml methanol, because samples are desorbed in this amount of methanol. The density of the analyte is used to convert mg into microliters for easy measurement with a microliter syringe. A series of standards, varying in concentration over the range of interest, is prepared and analyzed under the same GC conditions and during the same time period as the unknown samples. Curves are established by plotting concentration in mg/1.0 ml versus peak area.
Since no internal standard is used in the method, standard solutions must be analyzed at the same time that the sample analysis is done. This will minimize the effect of known day-to-day variations and variations during the same day of the FID response.
10. Calculations.
10.1 Read the weight, in mg, corresponding to each peak area from the standard curve. No volume corrections are needed, because the standard curve is based on mg/1.0 ml methanol and the volume of sample injected is identical to the volume of the standards injected.
10.2 Corrections for the bank must be made for each sample.
A similar procedure is followed for the backup sections.
10.3 Add the weights found in the front and backup sections to get the total weight in the sample.
10.4 Read the desorption efficiency from the curve (see sec. 8.5.2) for the amount found in the front section. Divide the total weight by this desorption efficiency to obtain the corrected mg/sample.
10.5 The concentration of the analyte in the air sampled can be expressed in mg/cu m.
10.6 Another method of expressing concentration is ppm.
11. References.
11.1 White, L. D. et al., “A Convenient Optimized Method for the Analysis of Selected Solvent Vapors in the Industrial Atmosphere,” Amer. Ind. Hyg. Assoc. J., 31: 225 (1970).
11.2 Documentation of NIOSH Validation Tests, NIOSH Contract No. CDC-99-74-45.
11.3 Final Report, NIOSH Contract HSM-99-71-31, “Personal Sampler Pump for Charcoal Tubes,” September 15, 1972.
The NIOSH recommended method for low levels for acrylonitrile is a modification of method S-156. It differs in the following respects:
(1) Samples are desorbed using 1 ml of 1 percent acetone in CS 2 rather than methanol.
(2) The analytical column and conditions are:
Column: 20 percent SP-1000 on 80/100 Supelcoport 10 feet × 1/8 inch S.S.
(3) A 2 µl injection of the desorbed analyte is used.
(4) A sampling rate of 100 ml/min is recommended.
1. Principle of the Method (Reference 1).
1.1 A known volume of air is drawn through a charcoal tube to trap the organic vapors present.
1.2 The charcoal in the tube is transferred to a small, stoppered sample vial, and the analyte is desorbed with methanol.
1.3 An aliquot of the desorbed sample is injected into a gas chromatograph.
1.4 The area of the resulting peak is determined and compared with areas obtained for standards.
2. Advantages and disadvantages of the method.
2.1 The sampling device is small, portable, and involves no liquids. Interferences are minimal, and most of those which do occur can be eliminated by altering chromatographic conditions. The tubes are analyzed by means of a quick, instrumental method.
2.2 This method may not be adequate for the simultaneous analysis of two or more substances.
2.3 The amount of sample which can be taken is limited by the number of milligrams that the tube will hold before overloading. When the sample value obtained for the backup section of the charcoal tube exceeds 25 percent of that found on the front section, the possibility of sample loss exists.
2.4 The precision of the method is limited by the reproducibility of the pressure drop across the tubes. This drop will affect the flow rate and cause the volume to be imprecise, because the pump is usually calibrated for one tube only.
3. Apparatus.
3.1 A calibrated personal sampling pump whose flow can be determined within ±5 percent at the recommended flow rate.
3.2 Charcoal tubes: Glass tube with both ends flame sealed, 7 cm long with a 6-mm O.D. and a 4-mm I.D., containing 2 sections of 20/40 mesh activated charcoal separated by a 2-mm portion of urethane foam. The activated charcoal is prepared from coconut shells and is fired at 600 °C prior to packing. The adsorbing section contains 100 mg of charcoal, the back-up section 50 mg. A 3-mm portion of urethane foam is placed between the outlet end of the tube and the back-up section. A plug of sililated glass wool is placed in front of the adsorbing section. The pressure drop across the tube must be less than one inch of mercury at a flow rate of 1 liter per minute.
3.3 Gas chromatograph equipped with a nitrogen phosphorus detector.
3.4 Column (10-ft × 1/8″-in stainless steel) packed with 100/120 Supelcoport coated with 10 percent SP 1000.
3.5 An electronic integrator or some other suitable method for measuring peak area.
3.6 Two-milliliter sample vials with Teflon-lined caps
3.7 Microliter syringes: 10-microliter, and other convenient sizes for making standards.
3.8 Pipets: 1.0-ml delivery pipets.
3.9 Volumetric flasks: convenient sizes for making standard solutions.
4. Reagents.
4.1 Chromatographic quality methanol.
4.2 Acrylonitrile, reagent grade.
4.3 Filtered compressed air.
4.4 Purified hydrogen.
4.5 Purified helium.
5. Procedure.
5.1 Cleaning of equipment. All glassware used for the laboratory analysis should be properly cleaned and free of organics which could interfere in the analysis.
5.2 Calibration of personal pumps. Each pump must be calibrated with a representative charcoal tube in the line.
5.3 Collection and shipping of samples.
5.3.1 Immediately before sampling, break the ends of the tube to provide an opening at least one-half the internal diameter of the tube (2 mm).
5.3.2 The smaller section of the charcoal is used as the backup and should be placed nearest the sampling pump.
5.3.3 The charcoal should be placed in a vertical position during sampling to minimize channeling through the charcoal.
5.3.4 Air being sampled should not be passed through any hose or tubing before entering the charcoal tube.
5.3.5 A sample size of 20 liters is recommended. Sample at a flow rate of approximately 0.2 liters per minute. The flow rate should be known with an accuracy of at least ±5 percent.
5.3.6 The temperature and pressure of the atmosphere being sampled should be recorded.
5.3.7 The charcoal tubes should be capped with the supplied plastic caps immediately after sampling. Rubber caps should not be used.
5.3.8 Submit at least one blank tube (a charcoal tube subjected to the same handling procedures, without having any air drawn through it) with each set of samples.
5.3.9. Take necessary shipping and packing precautions to minimize breakage of samples.
5.4 Analysis of samples.
5.4.1 Preparation of samples. In preparation for analysis, each charcoal tube is scored with a file in front of the first section of charcoal and broken open. The glass wool is removed and discarded. The charcoal in the first (larger) section is transferred to a 2-ml vial. The separating section of foam is removed and discarded; the section is transferred to another capped vial. These two sections are analyzed separately.
5.4.2 Desorption of samples. Prior to analysis, 1.0 ml of methanol is pipetted into each sample container. Desorption should be done for 30 minutes in an ultrasonic bath. The sample vials are recapped as soon as the solvent is added.
5.4.3 GC conditions. The typical operating conditions for the gas chromatograph are:
1. 30 ml/min (60 psig) helium carrier gas flow.
2. 3.0 ml/min (30 psig) hydrogen gas flow to detector.
3. 50 ml/min (60 psig) air flow to detector.
4. 200 °C injector temperature.
5. 200 °C dejector temperature.
6. 100 °C column temperature.
5.4.4 Injection. Solvent flush technique or equivalent.
5.4.5 Measurement of area. The area of the sample peak is measured by an electronic integator or some other suitable form of area measurement, and preliminary results are read from a standard curve prepared as discussed below.
5.5 Determination of desorption efficiency.
5.5.1 Importance of determination. The desorption efficiency of a particular compound can vary from one laboratory to another and also from one batch of charcoal to another. Thus, it is necessary to determine, at least once, the percentage of the specific compound that is removed in the desorption process, provided the same batch of charcoal is used.
5.5.2 Procedure for determining desorption efficiency. The reference portion of the charcoal tube is removed. To the remaining portion, amounts representing 0.5X, 1X, and 2X (X represents TLV) based on a 20 l air sample are injected onto several tubes at each level. Dilutions of acrylonitrile with methanol are made to allow injection of measurable quantities. These tubes are then allowed to equilibrate at least overnight. Following equilibration they are analyzed following the same procedure as the samples A curve of the desorption efficiency amt recovered/amt added is plotted versus amount of analyte found. This curve is used to correct for adsorption losses.
6. Calibration and standards.
A series of standards, varying in concentration over the range of interest, is prepared and analyzed under the same GC conditions and during the same time period as the unknown samples. Curves are prepared by plotting concentration versus peak area.
Since no internal standard is used in the method, standard solutions must be analyzed at the same time that the sample analysis is done. This will minimize the effect of known day-to-day variations and variations during the same day of the NPD response. Multiple injections are necessary.
7. Calculations.
Read the weight, corresponding to each peak area from the standard curve, correct for the blank, correct for the desorption efficiency, and make necessary air volume corrections.
8. Reference. NIOSH Method S-156.