(a) This section includes requirements for the control of employee
exposure to vinyl chloride (chloroethene), Chemical Abstracts
Service Registry No. 75014.
(b) This section applies to the manufacture, reaction, packaging,
repackaging, storage, handling or use of vinyl chloride or polyvinyl
chloride, but does not apply to the handling or use of fabricated
products made of polyvinyl chloride.
(c) This section applies to the transportation of vinyl chloride
or polyvinyl chloride except to the extent that the department
of transportation may regulate the hazards covered by this section.
(2) Definitions.
(a) “Action level” means a concentration
of vinyl chloride of 0.5 ppm averaged over an 8-hour work day.
(b) “Authorized person” means
any person specifically authorized by the employer whose duties
require him/her to enter a regulated area or any person entering
such an area as a designated representative of employees for
the purpose of exercising an opportunity to observe monitoring
and measuring procedures.
(c) “Director” means the director of department
of labor and industries or his/her designated representative.
(d) “Emergency” means any occurrence such
as, but not limited to, equipment failure, or operation of a
relief device which is likely to, or does, result in massive
release of vinyl chloride.
(e) "Fabricated product" means a product made wholly
or partly from polyvinyl chloride, and which does not require
further processing at temperatures, and for times, sufficient
to cause mass melting of the polyvinyl chloride resulting in
the release of vinyl chloride.
(f) “Hazardous operation” means any operation,
procedure, or activity where a release of either vinyl chloride
liquid or gas might be expected as a consequence of the operation
or because of an accident in the operation, which would result
in an employee exposure in excess of the permissible exposure
limit.
(g) “Polyvinyl chloride” means polyvinyl
chloride homopolymer or copolymer before such is converted to
a fabricated product.
(h) “Vinyl chloride” means vinyl chloride
monomer.
(3) Permissible exposure limit.
(a) No employee may be exposed to vinyl chloride at concentrations
greater than 1 ppm averaged over any 8-hour period, and
(b) No employee may be exposed to vinyl chloride at concentrations
greater than 5 ppm averaged over any period not exceeding 15
minutes.
(c) No employee may be exposed to vinyl chloride by direct
contact with liquid vinyl chloride.
(4) Monitoring.
(a) A program of initial monitoring and measurement shall be
undertaken in each establishment to determine if there is any
employee exposed, without regard to the use of respirators,
in excess of the action level.
(b) Where a determination conducted under subdivision (a) of
this subsection shows any employee exposures without regard
to the use of respirators, in excess of the action level, a
program for determining exposures for each such employee shall
be established. Such a program:
(i) Shall be repeated at least monthly where any employee
is exposed, without regard to the use of respirators, in excess
of the permissible exposure limit.
(ii) Shall be repeated not less than quarterly where any
employee is exposed, without regard to the use of respirators,
in excess of the action level.
(iii) May be discontinued for any employee only when at least
two consecutive monitoring determinations, made not less than
5 working days apart, show exposures for that employee at
or below the action level.
(c) Whenever there has been a production, process or control
change which may result in an increase in the release of vinyl
chloride, or the employer has any other reason to suspect that
any employee may be exposed in excess of the action level, a
determination of employee exposure under subdivision (a) of
this subsection shall be performed.
(d) The method of monitoring and measurement shall have an
accuracy (with a confidence level of 95 percent) of not less
than plus or minus 50 percent from 0.25 through 0.5 ppm, plus
or minus 35 percent from over 0.5 ppm through 1.0 ppm, plus
or minus 25 percent over 1.0 ppm, (methods meeting these accuracy
requirements are available from the director).
(e) Employees or their designated representatives shall be
afforded reasonable opportunity to observe the monitoring and
measuring required by this subsection.
(5) Regulated area.
(a) A regulated area shall be established where:
(i) Vinyl chloride or polyvinyl chloride is manufactured,
reacted, repackaged, stored, handled or used; and
(ii) Vinyl chloride concentrations are in excess of the permissible
exposure limit.
(b) Access to regulated areas shall be limited to authorized
persons.
(6) Methods of compliance. Employee exposures to vinyl chloride
shall be controlled to at or below the permissible exposure limit
provided in subsection (3) of this section by engineering, work-practice,
and personal protective controls as follows:
(a) Feasible engineering and work-practice controls shall immediately
be used to reduce exposures to at or below the permissible exposure
limit.
(b) Wherever feasible engineering and work-practice controls
which can be instituted immediately are not sufficient to reduce
exposures to at or below the permissible exposure limit, they
shall nonetheless be used to reduce exposures to the lowest
practicable level, and shall be supplemented by respiratory
protection in accordance with subsection (7) of this section.
A program shall be established and implemented to reduce exposures
to at or below the permissible exposure limit, or to the greatest
extent feasible, solely by means of engineering and work-practice
controls, as soon as feasible.
(c) Written plans for such a program shall be developed and
furnished upon request for examination and copying to the director.
Such plans shall be updated at least every six months.
(7) Respiratory protection.
(a) General. For employees who use respirators required by
this section, the employer must provide respirators that comply
with the requirements of this section.
(b) Respirator program. The employer must develop, implement,
and maintain a respiratory protection program as required in
chapter 296-842
WAC, Respirators, except for the requirements in WAC 296-842-13005
that address change out of vapor or gas respirator cartridges
or canisters.
(c) Respirator selection. The employer must:
(i) Select and provide to employees appropriate respirators
as specified in this section and WAC 296-842-13005 in the
respirator rule.
(ii) Provide organic vapor cartridges that have a service
life of at least one hour when employees use air-purifying
respirators in vinyl chloride concentrations up to 10 parts
per million (ppm).
(iii) Make sure the following respirators, when selected,
are equipped with a canister with a service life of at least
4 hours when used in vinyl chloride concentrations up to 25
ppm.
(A) Helmet, hood, or full-facepiece PAPRs
OR
(B) Gas masks with a front- or back-mounted canister.
(d) Where air-purifying respirators are used:
(i) Air-purifying canisters or cartridges must be replaced
prior to the expiration of their service life or the end of
the shift in which they are first used, whichever occurs first,
and
(ii) A continuous monitoring and alarm system must be provided
when concentrations of vinyl chloride could reasonably exceed
the allowable concentrations for the devices in use. Such
system shall be used to alert employees when vinyl chloride
concentrations exceed the allowable concentrations for the
devices in use, and
(iii) Respirators specified for higher concentrations may
be used for lower concentration.
(8) Hazardous operations.
(a) Employees engaged in hazardous operations, including entry
of vessels to clean polyvinyl chloride residue from vessel walls,
shall be provided and required to wear and use;
(i) Respiratory protection in accordance with subsections
(3) and (7) of this section; and
(ii) Protective garments to prevent skin contact with liquid
vinyl chloride or with polyvinyl chloride residue from vessel
walls. The protective garments shall be selected for the operation
and its possible exposure conditions.
(b) Protective garments shall be provided clean and dry for
each use.
(c) Emergency situations. A written operational plan for emergency
situations shall be developed for each facility storing, handling,
or otherwise using vinyl chloride as a liquid or compressed
gas. Appropriate portions of the plan shall be implemented in
the event of an emergency. The plan shall specifically provide
that:
(i) Employees engaged in hazardous operations or correcting
situations of existing hazardous releases shall be equipped
as required in subdivisions (a) and (b) of this subsection;
(ii) Other employees not so equipped shall evacuate the area
and not return until conditions are controlled by the methods
required in subsection (6) of this section and the emergency
is abated.
(9) Training.
Each employee engaged in vinyl chloride or polyvinyl chloride
operations shall be provided training in a program relating to
the hazards of vinyl chloride and precautions for its safe use.
(a) The program shall include:
(i) The nature of the health hazard from chronic exposure
to vinyl chloride including specifically the carcinogenic
hazard;
(ii) The specific nature of operations which could result
in exposure to vinyl chloride in excess of the permissible
limit and necessary protective steps;
(iii) The purpose for, proper use, and limitations of respiratory
protective devices;
(iv) The fire hazard and acute toxicity of vinyl chloride,
and the necessary protective steps;
(v) The purpose for and a description of the monitoring program;
(vi) The purpose for and a description of, the medical surveillance
program;
(vii) Emergency procedures:
(A) Specific information to aid the employee in recognition
of conditions which may result in the release of vinyl chloride;
and
(B) A review of this standard at the employee's first training
and indoctrination program, and annually thereafter.
(b) All materials relating to the program shall be provided
upon request to the director.
(10) Medical surveillance. A program of medical surveillance
shall be instituted for each employee exposed, without regard
to the use of respirators, to vinyl chloride in excess of the
action level. The program shall provide each such employee with
an opportunity for examinations and tests in accordance with this
subsection. 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.
(a) At the time of initial assignment, or upon institution
of medical surveillance;
(i) A general physical examination shall be performed with
specific attention to detecting enlargement of liver, spleen
or kidneys, or dysfunction in these organs, and for abnormalities
in skin, connective tissues and the pulmonary system (see
Appendix A).
(ii) A medical history shall be taken, including the following
topics:
(A) Alcohol intake,
(B) Past history of hepatitis,
(C) Work history and past exposure to potential hepatotoxic
agents, including drugs and chemicals,
(D) Past history of blood transfusions, and
(E) Past history of hospitalizations.
(iii) A serum specimen shall be obtained and determinations
made of:
(D) Serum glutamic pyruvic transaminase (SGPT), and
(E) Gamma glustamyl transpeptidase.
(b) Examinations provided in accordance with this subdivision
shall be performed at least:
(i) Every 6 months for each employee who has been employed
in vinyl chloride or polyvinyl chloride manufacturing for
10 years or longer; and
(ii) Annually for all other employees.
(c) Each employee exposed to an emergency shall be afforded
appropriate medical surveillance.
(d) A statement of each employee's suitability for continued
exposure to vinyl chloride including use of protective equipment
and respirators, shall be obtained from the examining physician
promptly after any examination. A copy of the physician's statement
shall be provided each employee.
(e) If any employee's health would be materially impaired by
continued exposure, such employee shall be withdrawn from possible
contact with vinyl chloride.
(f) Laboratory analyses for all biological specimens included
in medical examinations shall be performed in laboratories licensed
under 42 CFR Part 74.
(g) If the examining physician determines that alternative
medical examinations to those required by subdivision (a) of
this subsection will provide at least equal assurance of detecting
medical conditions pertinent to the exposure to vinyl chloride,
the employer may accept such alternative examinations as meeting
the requirements of subdivision (a) of this subsection, if the
employer obtains a statement from the examining physician setting
forth the alternative examinations and the rationale for substitution.
This statement shall be available upon request for examination
and copying to authorized representatives of the director.
(11) Signs and labels.
(a) Entrances to regulated areas shall be posted with legible
signs bearing the legend:
CANCER-SUSPECT AGENT AREA AUTHORIZED PERSONNEL
ONLY
(b) Areas containing hazardous operations or where an emergency
currently exists shall be posted with legible signs bearing
the legend:
CANCER-SUSPECT AGENT IN THIS AREA PROTECTIVE
EQUIPMENT REQUIRED AUTHORIZED PERSONNEL ONLY
(c) Containers of polyvinyl chloride resin waste from reactors
or other waste contaminated with vinyl chloride shall be legibly
labeled:
CONTAMINATED WITH VINYL CHLORIDE CANCER-SUSPECT
AGENT
(d) Containers of polyvinyl chloride shall be legibly labeled:
POLYVINYL CHLORIDE (OR TRADE NAME) CONTAINS
VINYL CHLORIDE VINYL CHLORIDE IS A CANCER-SUSPECT AGENT
(e) Containers of vinyl chloride shall be legibly labeled either:
VINYL CHLORIDE EXTREMELY FLAMMABLE GAS UNDER
PRESSURE CANCER-SUSPECT AGENT (or)
(f) In accordance with 49 CFR Part 173, Subpart H, with the
additional legends:
CANCER-SUSPECT AGENT
Applied near the label or placard.
(g) No statement shall appear on or near any required sign,
label or instruction which contradicts or detracts from the
effect of any required warning, information or instruction.
(12) Records.
(a) All records maintained in accordance with this section
shall include the name and social security number of each employee
where relevant.
(b) Records of required monitoring and measuring and medical
records shall be provided upon request to employees, designated
representatives, and the director in accordance with chapter
296-802 WAC. These records shall be provided upon request
to the director. Authorized personnel rosters shall also be
provided upon request to the director.
(i) Monitoring and measuring records shall:
(A) State the date of such monitoring and measuring and
the concentrations determined and identify the instruments
and methods used;
(B) Include any additional information necessary to determine
individual employee exposures where such exposures are determined
by means other than individual monitoring of employees;
and
(C) Be maintained for not less than 30 years.
(ii) Medical records shall be maintained for the duration
of the employment of each employee plus 20 years, or 30 years,
whichever is longer.
(c) In the event that the employer ceases to do business and
there is no successor to receive and retain his/her records
for the prescribed period, these records shall be transmitted
by registered mail to the director, and each employee individually
notified in writing of this transfer. The employer shall also
comply with any additional requirements set forth in chapter
296-802 WAC.
(d) Employees or their designated representatives shall be
provided access to examine and copy records of required monitoring
and measuring.
(e) Former employees shall be provided access to examine and
copy required monitoring and measuring records reflecting their
own exposures.
(f) Upon written request of any employee, a copy of the medical
record of that employee shall be furnished to any physician
designated by the employee.
(13) Reports.
(a) Not later than 1 month after the establishment of a regulated
area, the following information shall be reported to the director.
Any changes to such information shall be reported within 15
days.
(i) The address and location of each establishment which
has one or more regulated areas; and
(ii) The number of employees in each regulated area during
normal operations, including maintenance.
(b) Emergencies and the facts obtainable at that time, shall
be reported within 24 hours to the director. Upon request of
the director, the employer shall submit additional information
in writing relevant to the nature and extent of employee exposures
and measures taken to prevent future emergencies of similar
nature.
(c) Within 10 working days following any monitoring and measuring
which discloses that any employee has been exposed, without
regard to the use of respirators, in excess of the permissible
exposure limit, each such employee shall be notified in writing
of the results of the exposure measurement and the steps being
taken to reduce the exposure to within the permissible exposure
limit.
(14) Appendix A supplementary medical information.
APPENDIX A SUPPLEMENTARY MEDICAL INFORMATION
When required tests under subsection (10)(a) of this section
show abnormalities, the tests should be repeated as soon as practicable,
preferably within 3 to 4 weeks. If tests remain abnormal, consideration
should be given to withdrawal of the employee from contact with
vinyl chloride, while a more comprehensive examination is made.
Additional tests which may be useful:
(A) For kidney dysfunction: Urine examination for albumin,
red blood cells, and exfoliative abnormal cells.
(B) Pulmonary system: Forced vital capacity, forced expiratory
volume at 1 second, and chest roentgenogram (posterior-anterior,
14 x 17 inches).
(C) Additional serum tests: Lactic acid dehydrogenase,
lactic acid dehydrogenase isoenzyme, protein determination,
and protein electrophoresis.
(D) For a more comprehensive examination on repeated abnormal
serum tests: Hepatitis B antigen, and liver scanning.
(a) This section applies to all occupational exposure to acrylonitrile
(AN), Chemical Abstracts Service Registry No. 000107131, except
as provided in (b) and (c) of this subsection.
(b) 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-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.
(c) An employer relying upon exemption under (1)(b)(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 subsection (17) of this section.
(2) Definitions, as applicable to this section:
(a) “Acrylonitrile” or “AN”
- acrylonitrile monomer, chemical formula CH2 = CHCN.
(b) “Action level” - a concentration of
AN of 1 ppm as an eight-hour time-weighted average.
(c) “Authorized person” - 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 subsection (18) of this section.
(d) “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 ppm as an eight-hour
time-weighted average.
(e) “Director” - the director of labor and
industries, or his authorized representative.
(f) “Emergency” - any occurrence such as,
but not limited to, equipment failure, rupture of containers,
or failure of control equipment, which is likely to, or does,
result in unexpected exposure to AN in excess of the ceiling
limit.
(g) “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.
(h) “Polyacrylonitrile” or “PAN”
- polyacrylonitrile homopolymers or copolymers, except for materials
as exempted under subsection (1)(b) of this section.
(3) Permissible exposure limits.
(a) 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 parts acrylonitrile per
million parts of air (2 ppm), as an eight-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 10 ppm as averaged over any fifteen-minute period
during the working day.
(b) Dermal and eye exposure. The employer shall assure that
no employee is exposed to skin contact or eye contact with liquid
AN or PAN.
(4) Notification of use and emergencies.
(a) Use. Within ten days of the effective date of this standard,
or within fifteen days following the introduction of AN into
the workplace, every employer shall report, unless he has done
so pursuant to the emergency temporary standard, the following
information to the director for each such workplace:
(i) The address and location of each workplace in which AN
is present;
(ii) A brief description of each process of operation which
may result in employee exposure to AN;
(iii) The number of employees engaged in each process or
operation who may be exposed to AN and an estimate of the
frequency and degree of exposure that occurs; and
(iv) A brief description of the employer's safety and health
program as it relates to limitation of employee exposure to
AN. Whenever there has been a significant change in the information
required by this subsection, the employer shall promptly amend
such information previously provided to the director.
(b) Emergencies and remedial action. Emergencies, and the facts
obtainable at that time, shall be reported within 24 hours of
the initial occurrence to the director. Upon request of the
director, the employer shall submit additional information in
writing relevant to the nature and extent of employee exposures
and measures taken to prevent future emergencies of a similar
nature.
(5) Exposure monitoring.
(a) 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-hour period.
(ii) For the purposes of this section, employee exposure
is that which would occur if the employee were not using a
respirator.
(b) 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. Such monitoring may
be done on a representative basis, provided that the employer
can demonstrate that the determinations are representative of
employee exposures.
(c) 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. The employer shall continue
these quarterly measurements until at least two consecutive
measurements taken at least seven days apart, are below the
action level, and thereafter 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 below the
permissible exposure limits, the employer shall repeat such
monitoring for each such employee at least quarterly.
(iii) If the monitoring required by this section reveals
employee exposure to be in excess of the permissible exposure
limits, the employer shall repeat these determinations for
each such employee at least monthly. The employer shall continue
these monthly measurements until at least two consecutive
measurements, taken at least seven days apart, are below the
permissible exposure limits, and thereafter the employer shall
monitor at least quarterly.
(d) Additional monitoring. Whenever there has been a production,
process, control or personnel change which may result in new
or additional exposure 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 subsection shall be conducted.
(e) Employee notification.
(i) Within five working days after the receipt of monitoring
results, the employer shall notify each employee in writing
of the results which represent that employee's exposure.
(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.
(f) 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 25 percent for concentrations of AN
at or above the permissible exposure limits, and plus or minus
35 percent for concentrations of AN between the action level
and the permissible exposure limits.
(g) Weekly survey of operations involving liquid AN. In addition
to monitoring of employee exposures to AN as otherwise required
by this subsection, the employer shall survey areas of operations
involving liquid AN at least weekly to detect points where AN
liquid or vapor are being released into the workplace. The survey
shall employ an infra-red gas analyzer calibrated for AN, a
multipoint gas chromatographic monitor, or comparable system
for detection of AN. A listing of levels detected and areas
of AN release, as determined from the survey, shall be posted
prominently in the workplace, and shall remain posted until
the next survey is completed.
(6) Regulated areas.
(a) The employer shall establish regulated areas where AN concentrations
are in excess of the permissible exposure limits.
(b) 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.
(c) Access to regulated areas shall be limited to authorized
persons or to persons otherwise authorized by the act or regulations
issued pursuant thereto.
(d) The employer shall assure that in the regulated area, food
or beverages are not present or consumed, smoking products are
not present or used, and cosmetics are not applied, (except
that these activities may be conducted in the lunchrooms, change
rooms and showers required under subsections (13)(a)-(13)(c)
of this section.
(7) Methods of compliance.
(a) Engineering and work-practice controls.
(i) The employer shall institute engineering or 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 subsection (8) of this section.
(b)
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 subsection (7)(a) 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) 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 limits;
(D) A detailed schedule for the implementation of engineering
or work-practice controls; 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 for such a program shall be submitted
upon request to the director, and shall be available at the
worksite for examination and copying by the director, or any
affected employee or representative.
(v) The plans required by this subsection shall be revised
and updated at least every six months to reflect the current
status of the program.
(8) Respiratory protection.
(a) General. For employees who use respirators required by
this section, the employer must provide respirators that comply
with the requirements of this subsection. 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.
(b) Respirator program. Employers must develop,implement and
maintain a respiratory protection program in accordance with
chapter 296-842
WAC, Respirators.
(c) Respirator selection. The employer must:
(i) Select and provide to employees appropriate respirators
by following the requirements in this section and WAC 296-842-13005
in the respirator rule.
(ii) Provide to employees, for escape, any organic vapor,
air-purifying respirator or any self-contained breathing apparatus
(SCBA) that meet the selection requirements of WAC 296-842-13005
in the respirator rule.
(9) Emergency situations.
(a) Written plans.
(i) A written plan for emergency situations shall be developed
for each workplace where 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 subsection (8) of this section until the
emergency is abated.
(b) Alerting employees.
(i) Where there is the possibility of employee exposure
to AN in excess of the ceiling limit due to the occurrence
of an emergency, a general alarm shall be installed and
maintained to promptly alert employees of such occurrences.
(ii) 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.
(10) Protective clothing and equipment.
(a) Provision and use. Where eye or skin contact with liquid
AN or PAN may occur, the employer shall provide at no cost
to the employee, and assure that employees wear, appropriate
protective clothing or other equipment in accordance with
WAC
296-800-160 to protect any area of the body which may
come in contact with liquid AN or PAN.
(b) Cleaning and replacement.
(i) The employer shall clean, launder, maintain, or replace
protective clothing and equipment required by this subsection,
as needed to maintain their effectiveness.
In addition, the employer shall provide clean protective
clothing and equipment at least weekly to each affected
employee.
(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- or PAN-contaminated
protective clothing and equipment is placed and stored in
closable containers which prevent dispersion of the AN or
PAN outside the container.
(iv) 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.
(v) The employer shall assure that no employee removes
AN- or PAN-contaminated protective equipment or clothing
from the change room, except for those employees authorized
to do so for the purpose of laundering, maintenance, or
disposal.
(vi) The employer shall inform any person who launders
or cleans AN-or PAN-contaminated protective clothing or
equipment of the potentially harmful effects of exposure
to AN.
(vii) The employer shall assure that containers of contaminated
protective clothing and equipment which are to be removed
from the workplace for any reason are labeled in accordance
with subsection (16)(c)(ii) of this section, and that such
labels remain affixed when such containers leave the employer's
workplace.
(a) All surfaces shall be maintained free of accumulations
of liquid AN and of PAN.
(b) For operations involving liquid AN, the employer shall
institute a program for detecting leaks and spills of liquid
AN, including regular visual inspections.
(c) 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.
(d) Liquids. Where AN is present in a liquid form, or as
a resultant vapor, all containers or vessels containing AN
shall be enclosed to the maximum extent feasible and tightly
covered when not in use, with adequate provision made to avoid
any resulting potential explosion hazard.
(e) Surfaces.
(i) Dry sweeping and the use of compressed air for the
cleaning of floors and other surfaces where AN and PAN are
found is prohibited.
(ii) Where vacuuming methods are selected, 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 AN is not reintroduced into
the workplace air; and
(B) Portable vacuum units used to collect AN may not
be used for other cleaning purposes and shall be labeled
as prescribed by subsection (16)(c)(ii) of this section.
(iii) Cleaning of floors and other contaminated surfaces
may not be performed by washing down with a hose, unless
a fine spray has first been laid down.
(12) Waste disposal. AN and PAN waste, scrap, debris, bags,
containers or equipment, shall be disposed of in sealed bags
or other closed containers which prevent dispersion of AN outside
the container, and labeled as prescribed in subsection (16)(c)(ii)
of this section.
(13) Hygiene facilities and practices. 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 subsection (11) of this section,
or where otherwise found to be appropriate, the facilities required
by WAC
296-800-230 shall be provided by the employer for the use
of those employees, and the employer shall assure that the employees
use the facilities provided. In addition, the following facilities
or requirements are mandated.
(a) Change rooms. The employer shall provide clean change
rooms in accordance with WAC
296-800-230.
(b) Showers.
(i) The employer shall provide shower facilities in accordance
with WAC
296-800-230.
(ii) In addition, the employer shall also assure that employees
exposed to liquid AN and PAN shower at the end of the work
shift.
(iii) 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.
(c) Lunchrooms.
(i) Whenever food or beverages are consumed in the workplace,
the employer shall provide lunchroom facilities which have
a temperature controlled, positive pressure, filtered air
supply, and which are readily accessible to employees exposed
to AN above the permissible exposure limits.
(ii) In addition, the employer shall also assure that employees
exposed to AN above the permissible exposure limits wash
their hands and face prior to eating.
(14) Medical surveillance.
(a) General.
(i) The employer shall institute a program of medical surveillance
for each employee who is or will be exposed to AN above
the action level. The employer shall provide each such employee
with an opportunity for medical examinations and tests in
accordance with this subsection.
(ii) The employer shall assure that all medical examinations
and procedures are performed by or under the supervision
of a licensed physician, and shall be provided without cost
to the employee.
(b) 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 non-specific symptoms, such as headache, nausea, vomiting,
dizziness, weakness, or other central nervous system dysfunctions
that may be associated with acute or chronic exposure to
AN.
(ii) A physical examination giving particular attention
to central nervous system, gastrointestinal system, respiratory
system, skin and thyroid.
(iii) A “14 x 17” posteroanterior chest x-ray.
(iv) Further tests of the intestinal tract, including fecal
occult blood screening, and proctosigmoidoscopy, 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.
(c) Periodic examinations.
(i) The employer shall provide examinations specified in
this subsection at least annually for all employees specified
in subsection (14)(a) of this section.
(ii) If an employee has not had the examinations prescribed
in subsection (14)(b) of this section within six months
of termination of employment, the employer shall make such
examination available to the employee upon such termination.
(d) Additional examinations. If the employee for any reason
develops signs or symptoms commonly associated with exposure
to AN, the employer shall provide appropriate examination
and emergency medical treatment.
(e) Information provided to the physician. The employer shall
provide the following information to the examining physician:
(i) A copy of this standard and its appendices;
(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.
(f) 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 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.
(15)
Employee information and training.
(a) Training program.
(i) The employer shall institute a training program for
all employees where there is occupational exposure to AN
and shall assure their participation in the training program.
(ii) The training program 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 Appendices A, B and
C;
(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 subsection (14) of this section;
(E) The emergency procedures developed, as required by
subsection (9) of this section; and
(F) The engineering and work-practice controls, their
function and the employee's relationship thereto; and
(G) A review of this standard.
(b) 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 director.
(16) Signs and labels.
(a) General.
(i) The employer may use labels or signs required by other
statutes, regulations, or ordinances in addition to, or
in combination with, signs and labels required by this subsection.
(ii) The employer shall assure that no statement appears
on or near any sign or label, required by this subsection,
which contradicts or detracts from such effects of the required
sign or label.
(b) 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:
DANGER
ACRYLONITRILE (AN)
CANCER HAZARD
AUTHORIZED PERSONNEL ONLY
RESPIRATORS REQUIRED
(ii) The employer shall assure that signs required by this
subsection are illuminated and cleaned as necessary so that
the legend is readily visible.
(c) Labels.
(i) The employer shall assure that precautionary labels
are affixed to all containers of AN, and to containers of
PAN and products fabricated from PAN, except for those materials
for which objective data is provided as to the conditions
specified in subsection (1)(b) of this section. The employer
shall assure that the labels remain affixed when the AN
or PAN are sold, distributed or otherwise leave the employer's
workplace.
(ii) The employer shall assure that the precautionary labels
required by this subsection are readily visible and legible.
The labels shall bear the following legend:
(i) Where the processing, use, and handling of products
fabricated from PAN are exempted pursuant to subsection
(1)(b) 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 the following information:
(A) The relevant condition in subsection (1)(b) upon
which exemption is based;
(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.
(b) Exposure monitoring.
(i) The employer shall establish and maintain an accurate
record of all monitoring required by subsection (5) 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 subsection
(5)(f) of this section;
(C) Type of respiratory protective devices worn, if any;
and
(D) Name, social security number 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.
(c) Medical surveillance.
(i) The employer shall establish and maintain an accurate
record for each employee subject to medical surveillance
as required by subsection (14) of this section.
(ii) This record shall include:
(A) A copy of the physicians' 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 subsection (14)(f) 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 years or for the duration of employment
plus twenty years, whichever is longer.
(d) Availability.
(i) The employer shall assure that all records required
to be maintained by this section be made available upon
request to the director for examination and copying.
(ii) Records required by subdivisions (a) through (c) of
this subsection shall be provided upon request to employees,
designated representatives, and the assistant director in
accordance with chapter
296-802 WAC. Records required by subdivision (a) of
this section shall be provided in the same manner as exposure
monitoring records.
(iii) The employer shall assure that employee medical records
required to be maintained by this section, be made available,
upon request, for examination and copying, to the affected
employee or former employee, or to a physician designated
by the affected employee, former employee, or designated
representative.
(e) 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.
(ii) Whenever the employer ceases to do business and there
is no successor employer to receive and retain the records
for the prescribed period, these records shall be transmitted
to the director.
(iii) At the expiration of the retention period for the
records required to be maintained pursuant to this section,
the employer shall transmit these records to the director.
(iv) The employer shall also comply with any additional
requirements involving transfer of records set forth in
chapter
296-802 WAC.
(18) Observation of monitoring.
(a) 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 subsection (5) of this section.
(b) 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
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, 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.
(19) Appendices. The information contained in the appendices
is not intended, by itself, to create any additional obligation
not otherwise imposed, or to detract from any obligation.
(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:
(i) Two parts AN per million parts of air (2 ppm) averaged
over the eight-hour workday; or
(ii) Ten parts AN per million parts of air (10 ppm) averaged
over any fifteen-minute period in the workday.
(iii) In addition, skin and eye contact with liquid AN
is prohibited.
(2) Health hazard data.
(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:
(i) 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.
(ii) 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.
(iii) 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.
(3) Emergency first aid procedures.
(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.
(4) Respirators and protective clothing.
(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 certified for use with organic
vapors. For effective protection, respirators must fit your
face and head snugly. Respirators should not be loosened or
removed in work situations where their use is required.
(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:
(i) 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.
(ii) Replace or repair impervious clothing that has developed
leaks.
(iii) 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.
(5) Precautions for safe use, handling, and storage.
(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 nonsparking 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 nonimpervious 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.
(6) Access to information.
(a) Each year, your employer is required to inform you of
the information contained in this Substance Safety Data Sheet
for acrylonitrile. In addition, your 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 years or for the period
of your employment plus twenty years, whichever is longer.
(d) Your employer is required to release your exposure
and medical records to you or your representative upon your
request.
(ii) Specific gravity (water = 1): 0.81 (at 20°C or 68°F);
(iii) Vapor density (air = 1 at boiling point of acrylonitrile):
1.83;
(iv) Melting point: -83°C (-117°F);
(v) Vapor pressure (@20°F): 83 mm Hg;
(vi) Solubility in water, percent by weight @20°C (68°F):
7.35;
(vii) Evaporation rate (Butyl Acetate = 1): 4.54; and
(viii) 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.
(iv) Extinguishing media: Alcohol foam, carbon dioxide,
and dry chemical.
(v) 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.
(vi) 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.
(vii) For purposes of compliance with the requirements
of WAC
296-800-300, 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.
(viii) For purposes of compliance with WAC
296-24-59207, acrylonitrile is classified as a Class
B fire hazard.
(ix) For purpose of compliance with WAC
296-24-95613, locations classified as hazardous due
to the presence of acrylonitrile shall be Class I, Group
D.
(b) Reactivity:
(i) 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.
(ii) 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.
(iii) Hazardous decomposition 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.
(iv) Special precautions: Liquid acrylonitrile will attack
some forms of plastics, rubbers, and coatings.
(3) Spill, leak, and disposal procedures.
(a) If acrylonitrile is spilled or leaked, the following
steps should be taken:
(i) Remove all ignition sources.
(ii) The area should be evacuated at once and re-entered
only after the area has been thoroughly ventilated and washed
down with water.
(iii) 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 materials 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.
(4) Monitoring and measurement procedures.
(a) Exposure above the permissible exposure limit:
(i) Eight-hour exposure evaluation: Measurements taken
for the purpose of determining employee exposure under this
section are best taken so that the average eight-hour exposure
may be determined from a single eight-hour sample or two
four-hour samples.
Air samples should be taken in the employee's breathing
zone (air that would most nearly represent that inhaled
by the employee).
(ii) 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 measurements should be taken on one work shift.
The average of all measurements taken is an estimate of
the employee's ceiling exposure.
(iii) 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.
(iv) 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/her 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.
(5) Protective clothing.
(a) 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.
(b) Employers should ascertain that the protective garments
are impermeable to acrylonitrile. Nonimpermeable 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.
(c) 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.
(6) Housekeeping and hygiene facilities. For purposes of complying
with WAC 296-24-120, 296-800-220
and 296-800-230,
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.
(7) Miscellaneous precautions.
(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) Nonsparking 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.
(8) Common operations. 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.
WAC
296-62-07339 Appendix C--Medical surveillance guidelines
for acrylonitrile.
(1) Route of entry.
(a) Inhalation;
(b) Skin absorption;
(c) Ingestion.
(2) Toxicology.
(a) Acrylonitrile vapor is an asphyxiant due to inhibitory
action on metabolic enzyme systems. Animals exposed to 75
or 100 ppm for seven 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
poisoning 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.
(b) Results after one year of a planned two-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.
(c) 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.
(3) Signs and symptoms of acute overexposure. 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 dermatitis.
(4) Treatment of acute overexposure. 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 respiration 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.
(5) Surveillance and preventive considerations.
(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.
(b) 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.
(c) 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.
(d) 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.
(i) 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.
(ii) Respiratory disease. The duPont data indicate an increased
risk of lung cancer among employees exposed to acrylonitrile.
(iii) Gastrointestinal disease. The duPont 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.
(iv) 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.
(e) 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.
WAC
296-62-07340 Appendix D--Sampling and analytical methods
for acrylonitrile.
(1) 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.
(2) 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.
(3) 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 NIOSH Method P & CAM
127.
(4) 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.
(5) Whatever method the employer chooses, he must assure himself
of the method's accuracy and precision under the unique conditions
present in his workplace.
(6) NIOSH Method S-156 (unmodified)
Analyte: Acrylonitrile.
Matrix: Air.
Procedure: Absorption on charcoal, desorption with methanol,
GC.
(a) Principle of the method. Reference (k)(i) of this subsection.
(i) A known volume of air is drawn through a charcoal tube
to trap the organic vapors present.
(ii) The charcoal in the tube is transferred to a small,
stoppered sample container, and the analyte is desorbed
with methanol.
(iii) An aliquot of the desorbed sample is injected into
a gas chromatograph.
(iv) The area of the resulting peak is determined and compared
with areas obtained for standards.
(b) Range and sensitivity.
(i) 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 twenty-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.
(ii) 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 (f)(ii) of this subsection.
If a particular atmosphere is suspected of containing a
large amount of contaminant, a smaller sampling volume should
be taken.
(c) Interference.
(i) 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.
(ii) 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.
(iii) 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.
(iv) If the possibility of interference exists, separation
conditions (column packing, temperature, etc.) must be changed
to circumvent the problem.
(d) Precision and accuracy.
(i) The coefficient of variation (CVt) 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 (k)(ii) of
this subsection.
(ii) 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 (j)(v) of this subsection.
(e) Advantages and disadvantages of the method.
(i) 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.
(ii) 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.
(iii) 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.
(iv) 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.
(f) Apparatus.
(i) A calibrated personal sampling pump whose flow can
be determined within ±5 percent at the recommended flow
rate. Reference (k)(iii) of this subsection.
(ii) 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 charcoal is
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.
(iii) Gas chromatograph equipped with a flame ionization
detector.
(iv) Column (4 ft x 1/4 in stainless steel) packed with
50/80 mesh Poropak, type Q.
(v) An electronic integrator or some other suitable method
for measuring peak areas.
(vi) Two-milliliter sample containers with glass stoppers
or Teflonlined caps. If an automatic sample injector is
used, the associated vials may be used.
(vii) Microliter syringes: Ten-microliter and other convenient
sizes for making standards.
(viii) Pipets: 1.0 ml delivery pipets.
(ix) Volumetric flask: 10 ml or convenient sizes for making
standard solutions.
(g) Reagents.
(i) Chromatographic quality methanol.
(ii) Acrylonitrile, reagent grade.
(iii) Hexane, reagent grade.
(iv) Purified nitrogen.
(v) Prepurified hydrogen.
(vi) Filtered compressed air.
(h) Procedure.
(i) Cleaning of equipment. All glassware used for the laboratory
analysis should be detergent washed and thoroughly rinsed
with tap water and distilled water.
(ii) 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.
(iii) Collection and shipping of samples.
(A) Immediately before sampling, break the ends of the
tube to provide an opening at least one-half the internal
diameter of the tube (2mm).
(B) The smaller section of charcoal is used as a backup
and should be positioned nearest the sampling pump.
(C) The charcoal tube should be placed in a vertical
direction during sampling to minimize channeling through
the charcoal.
(D) Air being sampled should not be passed through any
hose or tubing before entering the charcoal tube.
(E) 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.
(F) The temperature and pressure of the atmosphere being
sampled should be recorded. If pressure reading is not
available, record the elevation.
(G) The charcoal tubes should be capped with the supplied
plastic caps immediately after sampling. Under no circumstances
should rubber caps be used.
(H) With each batch of ten 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.
(I) Capped tubes should be packed tightly and padded
before they are shipped to minimize tube breakage during
shipping.
(J) A sample of the bulk material should be submitted
to the laboratory in a glass container with a Teflonlined
cap. This sample should not be transported in the same
container as the charcoal tubes.
(iv) Analysis of samples.
(A) 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.
(B) 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.
(C) GC conditions. The typical operating conditions for
the gas chromatograph are:
(I) 50 ml/min (60 psig) nitrogen carrier gas flow.
(II) 65 ml/min (24 psig) hydrogen gas flow to detector.
(III) 500 ml/min (50 psig) air flow to detector.
(IV) 235°C injector temperature.
(V) 255°C manifold temperature (detector).
(VI) 155°C column temperature.
(D) 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 five 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.
(E) 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.
(v) Determination of desorption efficiency.
(A) 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.
(B) Procedure for determining desorption efficiency.
(I) 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.
(II) The amount injected is equivalent to that present
in a twenty-liter air sample at the selected level.
(III) 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 (h)(iv) of
this subsection.
(IV) 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.
(V) 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
Average weight recovered (mg)
D.E. = ---------------------------------------
weight added (mg)
(VI) 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 (j)(iv) of this subsection to
correct for adsorption losses.
(i) 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.
Note: 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.
(j) Calculations.
(i) 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.
(ii) Corrections for the bank must be made for each sample.
mg = mg sample-mg blank
Where:
mg sample = mg found in front section of sample tube.
mg sample = mg found in front section of blank tube.
Note: A similar procedure is followed for the backup sections.
(iii) Add the weights found in the front and backup sections
to get the total weight in the sample.
(iv) Read the desorption efficiency from the curve (reference
(h)(v)(B) of this subsection) for the amount found in the
front section. Divide the total weight by this desorption
efficiency to obtain the corrected mg/sample.
Total
weight
Corrected mg/sample = --------------
D.E.
(v) The concentration of the analyte in the air sampled
can be expressed in mg/cu m.
1,000 (liter/cu m)
mg/cu m = Corrected mg (see (j)(iv)) x ------------------------------------------
air volume sampled (liter)
(vi) Another method of expressing concentration is ppm.
ppm = mg/cu m x 24.45/M.W. x 760/P x T + 273/298
Where:
P = Pressure (mm Hg) of air sampled.
T = Temperature (°C) of air sampled.
24.45 = Molar volume (liter/mole) at 25°C and 760 mm Hg.
M.W. = Molecular weight (g/mole) of analyte.
760 = Standard pressure (mm Hg).
298 = Standard temperature (°K).
(k) References.
(i) 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).
(ii) Documentation of NIOSH Validation Tests, NIOSH Contract
No. CDC-99-74-45.
(iii) Final Report, NIOSH Contract HSM-99-71-31, “Personal
Sampler Pump for Charcoal Tubes,” September 15, 1972.
(7) NIOSH Modification of NIOSH Method S-156. The NIOSH recommended
method for low levels for acrylonitrile is a modification of
method S-156. It differs in the following respects:
(a) Samples are desorbed using 1 ml of 1 percent acetone
in CS2 rather than methanol.
(b) The analytical column and conditions are:
(i) Column: 20 percent SP-1000 on 80/100 Supelcoport 10
feet x 1/8 inch S.S.
(ii) Conditions:
Injector temperature: 200°C.
Detector temperature: 100°C.
Column temperature: 85°C.
Helium flow: 25 ml/min.
Air flow: 450 ml/min.
Hydrogen flow: 55 ml/min.
(c) A 2 µl injection of the desorbed analyte is used.
(d) A sampling rate of 100 ml/min is recommended.
(8) OSHA Laboratory Modification of NIOSH Method S-156.
(a) Analyte: Acrylonitrile.
(b) Matrix: Air.
(c) Procedure: Adsorption on charcoal, desorption with methanol,
GC.
(d) Principle of the method (subsection (1)(a) of this section).
(i) A known volume of air is drawn through a charcoal tube
to trap the organic vapors present.
(ii) The charcoal in the tube is transferred to a small,
stoppered sample vial, and the analyte is desorbed with
methanol.
(iii) An aliquot of the desorbed sample is injected into
a gas chromatograph.
(iv) The area of the resulting peak is determined and compared
with areas obtained for standards.
(e) Advantages and disadvantages of the method.
(i) 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.
(ii) This method may not be adequate for the simultaneous
analysis of two or more substances.
(iii) 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.
(iv) 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.
(f) Apparatus.
(i) A calibrated personal sampling pump whose flow can
be determined within ±5 percent at the recommended flow
rate.
(ii) 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 absorbing 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 silicated 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.
(iii) Gas chromatograph equipped with a nitrogen phosphorus
detector.
(iv) Column (10 ft x 1/8 in stainless steel) packed with
100/120 Supelcoport coated with 10 percent SP 1000.
(v) An electronic integrator or some other suitable method
for measuring peak area.
(vi) Two-milliliter sample vials with Teflonlined caps.
(vii) Microliter syringes: 10 microliter, and other convenient
sizes for making standards.
(viii) Pipets: 1.0 ml delivery pipets.
(ix) Volumetric flasks: Convenient sizes for making standard
solutions.
(g) Reagents.
(i) Chromatographic quality methanol.
(ii) Acrylonitrile, reagent grade.
(iii) Filtered compressed air.
(iv) Purified hydrogen.
(v) Purified helium.
(h) Procedure.
(i) Cleaning of equipment. All glassware used for the laboratory
analysis should be properly cleaned and free of organics
which could interfere in the analysis.
(ii) Calibration of personal pumps. Each pump must be calibrated
with a representative charcoal tube in the line.
(iii) Collection and shipping of samples.
(A) 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).
(B) The smaller section of the charcoal is used as the
backup and should be placed nearest the sampling pump.
(C) The charcoal should be placed in a vertical position
during sampling to minimize channeling through the charcoal.
(D) Air being sampled should not be passed through any
hose or tubing before entering the charcoal tube.
(E) 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.
(F) The temperature and pressure of the atmosphere being
sampled should be recorded.
(G) The charcoal tubes should be capped with the supplied
plastic caps immediately after sampling. Rubber caps should
not be used.
(H) 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.
(I) Take necessary shipping and packing precautions to
minimize breakage of samples.
(iv) Analysis of samples.
(A) 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.
(B) 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.
(C) GC conditions. The typical operating conditions for
the gas chromatograph are:
(I) 30 ml/min (60 psig) helium carrier gas flow.
(II) 3.0 ml/min (30 psig) hydrogen gas flow to detector.
(III) 50 ml/min (60 psig) air flow to detector.
(IV) 200°C injector temperature.
(V) 200°C dejector temperature.
(VI) 100°C column temperature.
(D) Injection. Solvent flush technique or equivalent.
(E) 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.
(v) Determination of desorption efficiency.
(A) 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.
(B) 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.
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.
Note: 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.
(j) 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.
(a) This section applies to occupational exposure to 1,2-dibromo-3-chloropropane
(DBCP).
(b) 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 liquids, except for
the requirements of subsections (11), (16) and (17) of this
section.
(2) Definitions applicable to this section:
(a) “Authorized person” - any person specifically
authorized by the employer and whose duties require the person
to be present in areas where DBCP is present; and any person
entering this area as a designated representative of employees
exercising an opportunity to observe employee exposure monitoring.
(b) “DBCP” - 1,2-dibromo-3-chloropropane,
Chemical Abstracts Service Registry Number 96-12-8, and includes
all forms of DBCP.
(c) “Director” - the director of labor
and industries, or his authorized representative.
(d) “Emergency” - any occurrence such
as, but not limited to equipment failure, rupture of containers,
or failure of control equipment which may, or does, result
in unexpected release of DBCP.
(3) Permissible exposure limits.
(a) Inhalation.
(i) Time-weighted average limit (TWA). The employer shall
assure that no employee is exposed to an airborne concentration
in excess of 1 part DBCP per billion part of air (ppb) as
an eight-hour time-weighted average.
(ii) Ceiling limit. The employer shall assure that no employee
is exposed to an airborne concentration in excess of 5 parts
DBCP per billion parts of air (ppb) as averaged over any
15 minutes during the working day.
(b) Dermal and eye exposure. The employer shall assure that
no employee is exposed to eye or skin contact with DBCP.
(4) Notification of use. Within ten days of the effective date
of this section or within ten days following the introduction
of DBCP into the workplace, every employer who has a workplace
where DBCP is present shall report the following information
to the director for each such workplace:
(a) The address and location of each workplace in which DBCP
is present;
(b) A brief description of each process or operation which
may result in employee exposure to DBCP;
(c) The number of employees engaged in each process or operation
who may be exposed to DBCP and an estimate of the frequency
and degree of exposure that occurs;
(d) A brief description of the employer's safety and health
program as it relates to limitation of employee exposure to
DBCP.
(5) Regulated areas. The employer shall establish, within each
place of employment, regulated areas wherever DBCP concentrations
are in excess of the permissible exposure limit.
(a) The employer shall limit access to regulated areas to
authorized persons.
(b) All employees entering or working in a regulated area
shall wear respiratory protection in accordance with Table
I.
(6) Exposure monitoring.
(a) General. Determinations of airborne exposure levels shall
be made from air samples that are representative of each employee's
exposure to DBCP over an eight-hour period. (For the purposes
of this section, employee exposure is that exposure which
would occur if the employee were not using a respirator.)
(b) 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.
(c) Frequency.
(i) If the monitoring required by this section reveals
employee exposures to be below the permissible exposure
limits, the employer shall repeat these determinations at
least quarterly.
(ii) If the monitoring required by this section reveals
employee exposure to be in excess of the permissible exposure
limits, the employer shall repeat these determinations for
each such employee at least monthly. The employer shall
continue these monthly determinations until at least two
consecutive measurements, taken at least seven days apart,
are below the permissible exposure limit, thereafter the
employer shall monitor at least quarterly.
(d) 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 other reason to suspect a change which may result in new
or additional exposure to DBCP, additional monitoring which
complies with subsection (6) shall be conducted.
(e) Employee notification.
(i) Within five working days after the receipt of monitoring
results, the employer shall notify each employee in writing
of results which represent the employee's exposure.
(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 limits.
(f) Accuracy of measurement. The method of measurement shall
be accurate, to a confidence level of 95 percent, to within
plus or minus 25 percent for concentrations of DBCP at or
above the permissible exposure limits.
(7) Methods of compliance.
(a) 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.
(b) Compliance program.
(i) The employer shall establish and implement a written
program to reduce employee exposure to DBCP to or below
the permissible exposure limit solely by means of engineering
and work-practice controls as required by this section.
(ii) The written program shall include a detailed schedule
for development and implementation of the engineering and
work-practice controls. These plans shall be revised at
least every six months to reflect the current status of
the program.
(iii) Written plans for these compliance programs shall
be submitted upon request to the director, and shall be
available at the worksite for examination and copying by
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.
(8) Respiratory protection.
(a) General. For employees who are required to use respirators
under this section, the employer must provide respirators
that comply with the requirements of this subsection. 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.
(b) The employer must develop, implement, and maintain a
respiratory protection program as required by chapter 296-842
WAC, Respirators.
(c) Respirator selection. The employer must:
(i) Select and provide to employees appropriate respirators
according to this chapter and WAC 296-842-13005 in the respirator
rule.
(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 full-facepiece
air-line respirator operated in a pressure-demand or other
positive-pressure mode or continuous-flow mode and an
auxiliary self-contained breathing apparatus (SCBA) operated
in a pressure-demand or positive-pressure mode;
OR
(B) A full-facepiece SCBA operated in a pressure-demand
or other positive-pressure mode.
(9) Reserved.
(10) Emergency situations.
(a) 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.
(b) Employees engaged in correcting conditions shall be equipped
as required in subsection (11) of this section until the emergency
is abated.
(c) 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.
(d) 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.
(e) Medical surveillance. For any employee exposed to DBCP
in an emergency situation, the employer shall provide medical
surveillance in accordance with subsection (14) of this section.
(f) Exposure monitoring.
(i) Following an emergency, the employer shall conduct
monitoring which complies with subsection (6) 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.
(11) Protective clothing and equipment.
(a) Provision and use. Where eye or skin contact with liquid
or solid DBCP may occur, employers shall provide at no cost
to the employee, and assure that employees wear impermeable
protective clothing and equipment in accordance with WAC
296-800-160 to protect the area of the body which may
come in contact with DBCP.
(b) Cleaning and replacement.
(i) The employer shall clean, launder, maintain, or replace
protective clothing and equipment required by this subsection
to maintain their effectiveness. In addition, the employer
shall provide clean protective clothing and equipment at
least daily to each affected employee.
(ii) Removal and storage.
(A) The employer shall assure that employees remove DBCP
contaminated work clothing only in change rooms provided
in accordance with subsection (13) of this section.
(B) 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.
(C) 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, or
disposal.
(iii) The employer shall assure that DBCP-contaminated
protective work clothing and equipment is placed and stored
in closed containers which prevent dispersion of DBCP outside
the container.
(iv) The employer shall inform any person who launders
or cleans DBCP-contaminated protective clothing or equipment
of the potentially harmful effects of exposure to DBCP.
(v) The employer shall assure that the containers of contaminated
protective clothing and equipment which are to be removed
from the workplace for any reason are labeled in accordance
with subsection (16)(c) of this section.
(vi) The employer shall prohibit the removal of DBCP from
protective clothing and equipment by blowing or shaking.
(12) Housekeeping.
(a) Surfaces.
(i) All surfaces shall be maintained free of accumulations
of DBCP.
(ii) Dry sweeping and the use of air for the cleaning of
floors and other surfaces where DBCP dust or liquids are
found is prohibited.
(iii) Where vacuuming methods are selected, 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 subsection (16)(c) of this section.
(iv) Cleaning of floors and other contaminated surfaces
may not be performed by washing down with a hose, unless
a fine spray has first been laid down.
(b) 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.
(c) Waste disposal. DBCP waste, scrap, debris, bags, containers
or equipment, shall be disposed in sealed bags or other closed
containers which prevent dispersion of DBCP outside the container.
(13) Hygiene facilities and practices.
(a) 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 subsections (8),
(9) and (11) of this section.
(b) 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 WAC
296-800-230.
(c) 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.
(d) 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 WAC
296-800-230.
(e) 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.
(14) Medical surveillance.
(a) General. The employer shall institute a program of medical
surveillance for each employee who is or will be exposed,
without regard to the use of respirators, to DBCP. The employer
shall provide each such employee with an opportunity for medical
examinations and tests in accordance with this subsection.
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.
(b) Frequency and content. At the time of initial assignment,
annually thereafter, and whenever exposure to DBCP occurs,
the employer shall provide a medical examination for employees
who work in regulated areas, which includes at least the following:
(i) A complete medical and occupational history with emphasis
on reproductive history.
(ii) A complete physical examination with emphasis on the
genito-urinary tract, testicle size, and body habitus including
the following tests:
(A) Sperm count;
(B) Complete urinalysis (U/A);
(C) Complete blood count; and
(D) Thyroid profile.
(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 multiphasic analysis (SMA 12);
(B) Serum follicle stimulating hormone (FSH);
(C) Serum luteinizing hormone (LH); and
(D) Serum estrogen (females).
(iv) Any other tests deemed appropriate by the examining
physician.
(c) 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.
(d) Information provided to the physician. The employer shall
provide the following information to the examining physician:
(i) A copy of this standard 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.
(e) 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;
(C) Any recommended limitations upon the employee's exposure
to DBCP or upon the use of protective clothing and equipment
such as respirators; and
(D) A statement that the employee was 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 DBCP.
(iii) The employer shall provide a copy of the written
opinion to the affected employee.
(f) 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 is unable to produce a semen specimen, the
hormone tests contained in subsection (14)(b) of this section.
The employer shall provide these same tests three months later.
(15)
Employee information and training.
(a) Training program.
(i) Within thirty days of the effective date of this standard,
the employer shall institute a training program for all
employees who may be exposed to DBCP and shall assure their
participation in such training program.
(ii) The employer shall assure that each employee is informed
of the following:
(A) The information contained in Appendices A, B and
C;
(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, limitations, and other training
requirements covering respiratory protection as required
in chapter
296-842 WAC.
(D) The purpose and description of the medical surveillance
program required by subsection (14) of this section; and
(E) A review of this standard.
(b) 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 nformation and training program
to the director.
(16) Signs and labels.
(a) General.
(i) The employer may use labels or signs required by other
statutes, regulations, or ordinances in addition to or in
combination with, signs and labels required by this subsection.
(ii) The employer shall assure that no statement appears
on or near any sign or label required by this subsection
which contradicts or detracts from the required sign or
label.
(b) Signs.
(i) The employer shall post signs to clearly indicate all
work areas where DBCP may be resent. These signs shall bear
the legend:
(ii) Where airborne concentrations of DBCP exceed the permissible
exposure limits, the signs shall bear the additional legend:
RESPIRATOR REQUIRED
(c) Labels.
(i) The employer shall assure that precautionary labels
are affixed to all containers of DBCP and of products containing
DBCP, and that the labels remain affixed when the DBCP or
products containing DBCP are sold, distributed, or otherwise
leave the employer's workplace. 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 subsection need not be affixed.
(ii) The employer shall assure that the precautionary labels
required by this subsection are readily visible and legible.
The labels shall bear the following legend:
DANGER 1,2-Dibromo-3-chloropropane
CANCER HAZARD
(17) Recordkeeping.
(a) Exposure monitoring.
(i) The employer shall establish and maintain an accurate
record of all monitoring required by subsection (6) 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 worn, if any; and
(D) Name, Social Security number, 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 years or the duration of employment plus twenty years,
whichever is longer.
(b) Medical surveillance.
(i) The employer shall establish and maintain an accurate
record for each employee subject to medical surveillance
required by subsection (14) of this section.
(ii) This record shall include:
(A) The name and Social Security number 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 subsection (14)(c) 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
forty years or the duration of employment plus twenty years,
whichever is longer.
(c) Availability.
(i) The employer shall assure that all records required
to be maintained by this section be made available upon
request to the director for examination and copying.
(ii) Employee exposure monitoring records and employee
medical records required by this subsection shall be provided
upon request to employees' designated representatives and
the assistant director in accordance with chapter 296-802
WAC
(d) 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 this section for the prescribed period.
(ii) If the employer ceases to do business and there is
no successor employer to receive and retain the records
for the prescribed period, the employer shall transmit these
records by mail to the director.
(iii) At the expiration of the retention period for the
records required to be maintained under this section, the
employer shall transmit these records by mail to the director.
(iv) The employer shall also comply with any additional
requirements involving transfer of records set forth in
chapter 296-802 WAC.
(18) Observation of monitoring.
(a) Employee observation. The employer shall provide affected
employees, or their designated representatives, an opportunity
to observe any monitoring of employee exposure to DBCP conducted
under subsection (6) of this section.
(b) 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 BCP performed at the place of exposure;
and
(C) Record the results obtained.
(19) 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.
WAC
296-62-07343 Appendix A--Substance safety data sheet for
DBCP.
(1) Substance identification.
(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:
(i) Airborne. 1 part DBCP vapor per billion parts of air
(1 ppb); time-weighted average (TWA) for an eight-hour workday.
(ii) 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.
(2) Health hazard data.
(a) Routes of entry: Employees may be exposed:
(i) Through inhalation (breathing);
(ii) Through ingestion (swallowing);
(iii) Skin contact; and
(iv) Eye contact.
(b) Effects of exposure:
(i) 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.
(ii) 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 people.
(iii) 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.
(3) Emergency first-aid procedures.
(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.
(4) Respirators and protective clothing.
(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 label issued by the National Institute
for Occupational Safety and Health (NIOSH) under the provisions
of 42 CFR part 84 stating that the respirators have been certified
for use with organic vapors. 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. Respirators must not be loosened or removed in
work situations where their use is required.
(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 splashproof safety goggles
where there is any possibility of DBCP liquid or dust contacting
your eyes.
(5) Precautions for safe use, handling, and storage.
(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.
(6) Access to information.
(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, they are 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 forty years or the
duration of your employment plus twenty 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.
WAC
296-62-07344 Appendix B--Substance technical guidelines
for DBCP.
(1) Physical and chemical data.
(a) Substance identification.
(i) 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.
(ii) Formula: C3H5Br2
C1.
(iii) Molecular weight: 236.
(b) Physical data:
(i) Boiling point (760 mm HG): 195C (383F)
(ii) Specific gravity (water = 1): 2.093.
(iii) Vapor density (air = 1 at boiling point of DBCP):
Data not available.
(iv) Melting point: 6C (43F).
(v) Vapor pressure at 20C (68F): 0.8 mm HG
(vi) Solubility in water: 1000 ppm.
(vii) Evaporation rate (Butyl Acetate = 1): Very much less
than 1.
(c) Appearance and odor: Dense yellow or amber liquid with
a pungent odor at high concentrations. Any detectable odor
of DBCP indicates overexposure.
(2) Fire explosion and reactivity hazard data.
(a) Fire.
(i) Flash point: 170F (77C)
(ii) Autoignition temperature: Data not available.
(iii) Flammable limits in air, percent by volume: Data
not available.
(v) 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.
(vi) Unusual fire and explosion hazards: None known.
(vii) For purposes of complying with the requirements of
WAC
296-24-330, liquid DBCP is classified as a Class III
A combustible liquid.
(viii) For the purpose of complying with chapter 296-24
WAC Part L, the classification of hazardous locations
as described in article 500 of the National Electrical Code
for DBCP shall be Class I, Group D.
(ix) For the purpose of compliance with WAC
296-24-592, DBCP is classified as a Class B fire hazard.
(x) For the purpose of compliance with WAC
296-24-230, locations classified as hazardous locations
due to the presence of DBCP shall be Class I, Group D.
(xi) Sources of ignition are prohibited where DBCP presents
a fire or explosion hazard.
(b) Reactivity.
(i) Conditions contributing to instability: None known.
(ii) Incompatibilities: Reacts with chemically active metals,
such as aluminum, magnesium and tin alloys.
(iii) Hazardous decomposition products: Toxic gases and
vapors (such as HBr, HC1 and carbon monoxide) may be released
in a fire involving DBCP.
(iv) Special precautions: DBCP will attack some rubber
materials and coatings.
(3) Spill, leak and disposal procedures.
(a) If DBCP is spilled or leaked, the following steps should
be taken:
(i) The area should be evacuated at once and re-entered
only after thorough ventilation.
(ii) Ventilate area of spill or leak.
(iii) If in liquid form, collect for reclamation or absorb
in paper, vermiculite, dry sand, earth or similar material.
(iv) 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:
(i) 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.
(ii) 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.
(4) Monitoring and measurement procedures.
(a) Exposure above the permissible exposure limit.
(i) Eight hour exposure evaluation: Measurements taken
for the purpose of determining employee exposure under this
section are best taken so that the average eight-hour exposure
may be determined from a single eight-hour sample or two
four-hour samples. Air samples should be taken in the employee's
breathing zone (air that would most nearly represent that
inhaled by the employee).
(ii) 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 twenty-five
percent. If charcoal tubes are used, a total volume of ten
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.
(5) Protective clothing. 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 splashproof safety goggles where there is any possibility
of DBCP contacting the eyes.
(6) Housekeeping and hygiene facilities.
(a) The workplace must be kept clean, orderly and in a sanitary
condition.
(b) 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.
(c) 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.
(d) 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.
(7) Miscellaneous precautions.
(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 knowledgeable
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.
(8) Common operations. Common operations in which exposure
to DBCP is likely to occur are: During its production; and during
its formulation into pesticides and fumigants.
WAC
296-62-07346 Appendix C--Medical surveillance guidelines
for DBCP.
(1) Route of entry.
(a) Inhalation;
(b) Skin absorption.
(2) Toxicology. 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 five 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.
(3) Signs and symptoms.
(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.
(4) Special tests.
(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:
(i) 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.
(ii) 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.
(iii) 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.
(iv) Semen volume should be measured to the nearest 1/10
of a cubic centimeter.
(v) 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.
(vi) 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.
(vii) 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.
(viii) 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 radiommuno-assay techniques using National
Institutes of Health (NIH) specific antigen or antigen preparations
of equivalent sensitivity:
(i) Serum follicle stimulating hormone (FSH),
(ii) Serum luteinizing hormone (LH), and
(iii) Serum total estrogen (females only).
(5) Treatment. 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.
(6) Surveillance and preventive considerations.
(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:
(i) 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.
(ii) 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.
(iii) Skin disease. 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.
(iv) 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.
(v) 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.
(7) References.
(a) 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).
(b) 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).
(c) 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).
(d) 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.
(e) Torkelson, T. R. et al.: Toxicologic Investigations of
1,2-Dibromo-3-chloropropane, Toxicology and Applied Pharmacology,
3, 1961 pp. 545-559.
(1) WAC
296-62-07355 through
296-62-07389 applies to all occupational exposures to ethylene
oxide (EtO), Chemical Abstracts Service Registry No. 75-21-8,
except as provided in subsection (2) of this section.
(2) WAC
296-62-07355 through 296-62-07389
does not apply to the processing, use, or handling of products
containing EtO where objective data are reasonably relied upon
that demonstrate that the product is not capable of releasing
EtO in airborne concentrations at or above the action level,
and may not reasonably be foreseen to release EtO in excess
of the excursion limit, under the expected conditions of processing,
use, or handling that will cause the greatest possible release.
(3) Where products containing EtO are exempted under subsection
(2) of this section, the employer shall maintain records of
the objective data supporting that exemption and the basis for
the employer's reliance on the data, as provided in WAC
296-62-07375(1).
(1) “Action level” means a concentration
of airborne EtO of 0.5 ppm calculated as an eight-hour time-weighted
average.
(2) “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 right to observe monitoring and
measuring procedures under WAC
296-62-07377, or any other person authorized by chapter
49.17 RCW or regulations issued under chapter 49.17 RCW.
(3) “Director” means the director of the
department of labor and industries, or designee.
(4) “Emergency” means any occurrence such as, but
not limited to, equipment failure, rupture of containers, or
failure of control equipment that is likely to or does result
in an unexpected significant release of EtO.
(5) “Employee exposure” means exposure to airborne
EtO which would occur if the employee were not using respiratory
protective equipment.
(6) “Ethylene oxide” or “EtO”
means the three-membered ring organic compound with chemical
formula C2H4O.
(1) Eight-hour time-weighted average (TWA). The employer shall
ensure that no employee is exposed to an airborne concentration
of EtO in excess of one part EtO per million parts of air (1
ppm) as an eight-hour time-weighted average. (Eight-hour TWA.)
(2) Excursion limit. The employer shall ensure that no employee
is exposed to an airborne concentration of EtO in excess of
five parts of EtO per million parts of air (5 ppm) as averaged
over a sampling period of fifteen minutes.
(a) Determinations of employee exposure shall be made from
breathing zone air samples that are representative of the
eight-hour TWA and fifteen-minute short-term exposures of
each employee.
(b) Representative eight-hour TWA employee exposure shall
be determined on the basis of one or more samples representing
full-shift exposure for each shift for each job classification
in each work area. Representative fifteen-minute short-term
employee exposures shall be determined on the basis of one
or more samples representing fifteen-minute exposures associated
with operations that are most likely to produce exposures
above the excursion limit for each shift for each job classification
in each work area.
(c) Where the employer can document that exposure levels
are equivalent for similar operations in different work shifts,
the employer need only determine representative employee exposure
for that operation during one shift.
(2) Initial monitoring.
(a) Each employer who has a workplace or work operation covered
by WAC
296-62-07355 through 296-62-07389,
except as provided in WAC
296-62-07355(2) or (b) of this subsection, shall perform
initial monitoring to determine accurately the airborne concentrations
of EtO to which employees may be exposed.
(b) Where the employer has monitored after June 15, 1983,
and the monitoring satisfies all other requirements of WAC
296-62-07355 through 296-62-07389,
the employer may rely on such earlier monitoring results to
satisfy the requirements of (a) of this subsection.
(c) Where the employer has previously monitored for the excursion
limit and the monitoring satisfies all other requirements
of this section, the employer may rely on such earlier monitoring
results to satisfy the requirements of (a) of this subsection.
(3) Monitoring frequency (periodic monitoring).
(a) If the monitoring required by subsection (2) of this
section reveals employee exposure at or above the action level
but at or below the eight-hour TWA, the employer shall repeat
such monitoring for each such employee at least every six
months.
(b) If the monitoring required by subsection (2)(a) of this
section reveals employee exposure above the eight-hour TWA,
the employer shall repeat such monitoring for each such employee
at least every three months.
(c) The employer may alter the monitoring schedule from quarterly
to semiannually for any employee for whom two consecutive
measurements taken at least seven days apart indicate that
the employee's exposure has decreased to or below the eight-hour
TWA.
(d) If the monitoring required by subsection (2)(a) of this
section reveals employee exposure above the fifteen-minute
excursion limit, the employer shall repeat such monitoring
for each such employee at least every three months, and more
often as necessary to evaluate the employee's short-term exposures.
(4) Termination of monitoring.
(a) If the initial monitoring required by subsection (2)(a)
of this section reveals employee exposure to be below the
action level, the employer may discontinue TWA monitoring
for those employees whose exposures are represented by the
initial monitoring.
(b) If the periodic monitoring required by subsection (3)
of this section reveals that employee exposures, as indicated
by at least two consecutive measurements taken at least seven
days apart, are below the action level, the employer may discontinue
TWA monitoring for those employees whose exposures are represented
by such monitoring.
(c) If the initial monitoring required by subsection (2)(a)
of this section reveals the employee exposure to be at or
below the excursion limit, the employer may discontinue excursion
limit monitoring for those employees whose exposures are represented
by the initial monitoring.
(d) If the periodic monitoring required by subsection (3)
of this section reveals that employee exposures, as indicated
by at least two consecutive measurements taken at least seven
days apart, are at or below the excursion limit, the employer
may discontinue excursion limit monitoring for those employees
whose exposures are represented by such monitoring.
(5) Additional monitoring. Notwithstanding the provisions of
subsection (4) of this section, the employer shall institute
the exposure monitoring required under subsections (2)(a) and
(3) of this section whenever there has been a change in the
production, process, control equipment, personnel or work-practices
that may result in new or additional exposures to EtO or when
the employer has any reason to suspect that a change may result
in new or additional exposures.
(6) Accuracy of monitoring.
(a) Monitoring shall be accurate, to a confidence level of
ninety-five percent, to within plus or minus twenty-five percent
for airborne concentrations of EtO at the 1 ppm TWA and to
within plus or minus thirty-five percent for airborne concentrations
of EtO at the action level of 0.5 ppm.
(b) Monitoring shall be accurate, to a confidence level of
ninety-five percent, to within plus or minus thirty-five percent
for airborne concentrations of EtO at the excursion limit.
(7) Employee notification of monitoring results.
(a) The employer shall, within fifteen working days after
the receipt of the results of any monitoring performed under
WAC
296-62-07355 through 296-62-07389,
notify the affected employee of these results in writing either
individually or by posting of results in an appropriate location
that is accessible to affected employees.
(b) The written notification required by (a) of this subsection
shall contain the corrective action being taken by the employer
to reduce employee exposure to or below the TWA and/or excursion
limit, wherever monitoring results indicated that the TWA
and/or excursion limit has been exceeded.
(1) The employer shall establish a regulated area wherever
occupational exposures to airborne concentrations of EtO may
exceed the TWA or wherever the EtO concentration exceeds or
can reasonably be expected to exceed the excursion limit.
(2) Access to regulated areas shall be limited to authorized
persons.
(3) Regulated areas shall be demarcated in any manner that
minimizes the number of employees within the regulated area.
(a) The employer shall institute engineering controls and
work-practices to reduce and maintain employee exposure to
or below the TWA and to or below the excursion limit, except
to the extent that such controls are not feasible.
(b) Wherever the feasible engineering controls and work-practices
that can be instituted are not sufficient to reduce employee
exposure to or below the TWA and to or below the excursion
limit, the employer shall use them to reduce employee exposure
to the lowest levels achievable by these controls and shall
supplement them by the use of respiratory protection that
complies with the requirements of WAC
296-62-07367.
(c) Engineering controls are generally infeasible for the
following operations: Collection of quality assurance sampling
from sterilized materials removal of biological indicators
from sterilized materials: Loading and unloading of tank cars;
changing of ethylene oxide tanks on sterilizers; and vessel
cleaning. For these operations, engineering controls are required
only where the director demonstrates that such controls are
feasible.
(2) Compliance program.
(a) Where the TWA or excursion limit is exceeded, the employer
shall establish and implement a written program to reduce
employee exposure to or below the TWA and to or below the
excursion limit by means of engineering and work-practice
controls, as required by subsection (1) of this section, and
by the use of respiratory protection where required or permitted
under WAC
296-62-07355 through 296-62-07389.
(b) The compliance program shall include a schedule for periodic
leak detection surveys and a written plan for emergency situations,
as specified in WAC
296-62-07369 (1)(a).
(c) Written plans for a program required in this subsection
shall be developed and furnished upon request for examination
and copying to the director, affected employees and designated
employee representatives. Such plans shall be reviewed at
least every twelve months, and shall be updated as necessary
to reflect significant changes in the status of the employer's
compliance program.
(d) The employer shall not implement a schedule of employee
rotation as a means of compliance with the TWA or excursion
limit.
WAC
296-62-07367 Respiratory protection and personal protective
equipment.
(1) General. For employees who use respirators required by
this section, the employer must provide respirators that comply
with the requirements of WAC
296-62-07355 through 296-62-07389.
Respirators must be used during:
(a) Periods necessary to install or implement feasible engineering
and work-practice controls;
(b) Work operations, such as maintenance and repair activities,
vessel cleaning, or other activities, for which engineering
and work-practice controls are not feasible;
(c) Work operations for which feasible engineering and work-practice
controls are not yet sufficient to reduce employee exposure
to or below the TWA or excursion limit;
(d) Emergencies.
(2) Respirator program. The employer must establish, implement,
and maintain a respiratory protection program as required in
chapter 296-842
WAC, except WAC
296-842-13005 and 296-842-14005.
(3) Respirator selection. The employer must select the appropriate
respirator from Table 1 of this section.
Table 1.-Minimum Requirements for Respiratory
Protection for Airborne EtO
Condition
of use or concentration of airborne EtO (ppm)
Minimum
required respirator
Equal to or less than
50
(a) Full facepiece respirator
with EtO approved canister, front-or back-mounted.
Equal to or less than
2,000
(a) Positive-pressure
supplied-air respirator, equipped with full facepiece,
hood or helmet, or
(b) Continuous-flow supplied-air
respirator (positive pressure) equipped with hood, helmet
or suit.
Concentration above 2,000
or unknown concentration (such as in emergencies)
(a) Positive-pressure
self-contained breathing apparatus (SCBA), equipped
with full facepiece, or
(b) Positive-pressure
full facepiece supplied-air respirator equipped with
an auxiliary positive- pressure self-contained breathing
apparatus.
Firefighting
(a) Positive-pressure
self-contained breathing apparatus equipped with full
facepiece.
Escape
(a) Any respirator described
above.
Note: Respirators approved for use in
higher concentrations are permitted to be used in lower concentrations.
(4) Protective clothing and equipment. Where employees could
have eye or skin contact with EtO or EtO solutions, the employer
must select and provide, at no cost to the employee, appropriate
protective clothing or other equipment in accordance with WAC
296-800-160, and to protect any area of the body that may
come in contact with liquid EtO or EtO in solution, and must
ensure that the employee wears the protective clothing and equipment
provided.
(a) A written plan for emergency situations shall be developed
for each workplace where there is a possibility of an emergency.
Appropriate portions of the plan shall be implemented in the
event of an emergency.
(b) The plan shall specifically provide that employees engaged
in correcting emergency conditions shall be equipped with
respiratory protection as required by WAC
296-62-07367 until the emergency is abated.
(c) The plan shall include the elements prescribed in WAC
296-24-567, “Employee emergency plans and fire prevention
plans.”
(2) Alerting employees. Where there is a possibility of employee
exposure to EtO due to an emergency, means shall be developed
to alert potentially affected employees of such occurrences
promptly. Affected employees shall be immediately evacuated
from the area in the event that an emergency occurs.
(i) The employer shall institute a medical surveillance
program for all employees who are or may be exposed to EtO
at or above the action level, without regard to the use
of respirators, for at least thirty days a year.
(ii) The employer shall make available medical examinations
and consultations to all employees who have been exposed
to EtO in an emergency situation.
(b) Examination by a physician. The employer shall ensure
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, without loss of pay,
and at a reasonable time and place.
(2) Medical examinations and consultations.
(a) Frequency. The employer shall make available medical
examinations and consultations to each employee covered under
subsection (1)(a) of this section on the following schedules:
(i) Prior to assignment of the employee to an area where
exposure may be at or above the action level for at least
thirty days a year.
(ii) At least annually each employee exposed at or above
the action level for at least thirty days in the past year.
(iii) At termination of employment or reassignment to an
area where exposure to EtO is not at or above the action
level for at least thirty days a year.
(iv) As medically appropriate for any employee exposed
during an emergency.
(v) As soon as possible, upon notification by an employee
either (A) that the employee has developed signs or symptoms
indicating possible overexposure to EtO, or (B) that the
employee desires medical advice concerning the effects of
current or past exposure to EtO on the employee's ability
to produce a healthy child.
(vi) If the examining physician determines that any of
the examinations should be provided more frequently than
specified, the employer shall provide such examinations
to affected employees at the frequencies recommended by
the physician.
(b) Content
(i) Medical examinations made available pursuant to (a)(i)
through (iv) of this subsection shall include:
(A) A medical and work history with special emphasis
directed to symptoms related to the pulmonary, hematologic,
neurologic, and reproductive systems and to the eyes and
skin.
(B) A physical examination with particular emphasis given
to the pulmonary, hematologic, neurologic, and reproductive
systems and to the eyes and skin.
(C) A complete blood count to include at least a white
cell count (including differential cell count), red cell
count, hematocrit, and hemoglobin.
(D) Any laboratory or other test which the examining
physician deems necessary by sound medical practice.
(ii) The content of medical examinations or consultation
made available pursuant to (a)(i)(v) of this subsection
shall be determined by the examining physician, and shall
include pregnancy testing or laboratory evaluation of fertility,
if requested by the employee and deemed appropriate by the
physician.
(3) Information provided to the physician. The employer shall
provide the following information to the examining physician:
(b) A description of the affected employee's duties as they
relate to the employee's exposure.
(c) The employee's representative exposure level or anticipated
exposure level.
(d) A description of any personal protective and respiratory
equipment used or to be used.
(e) Information from previous medical examinations of the
affected employee that is not otherwise available to the examining
physician.
(4) Physician's written opinion.
(a) The employer shall obtain a written opinion from the
examining physician. This written opinion shall contain the
results of the medical examination and shall include:
(i) The physician's opinion as to whether the employee
has any detected medical conditions that would place the
employee at an increased risk of material health impairment
from exposure to EtO;
(ii) Any recommended limitations on the employee or upon
the use of personal protective equipment such as clothing
or respirators; and
(iii) A statement that the employee has been informed by
the physician of the results of the medical examination
and of any medical conditions resulting from EtO exposure
that require further explanation or treatment.
(b) The employer shall instruct the physician not to reveal
in the written opinion given to the employer specific findings
or diagnoses unrelated to occupational exposure to EtO.
(c) The employer shall provide a copy of the physician's
written opinion to the affected employee within fifteen days
from its receipt.
(a) The employer shall post and maintain legible signs demarcating
regulated areas and entrances or accessways to regulated areas
that bear the following legend:
DANGER
ETHYLENE OXIDE
CANCER HAZARD AND REPRODUCTIVE HAZARD
AUTHORIZED PERSONNEL ONLY
RESPIRATORS AND PROTECTIVE CLOTHING MAY BE
REQUIRED
TO BE WORN IN THIS AREA
(b) The employer shall ensure that precautionary labels are
affixed to all containers of EtO whose contents are capable
of causing employee exposure at or above the action level
or whose contents may reasonably be foreseen to cause employee
exposure above the excursion limit, and that the labels remain
affixed when the containers of EtO leave the workplace. For
the purpose of this subsection, reaction vessels, storage
tanks, and pipes or piping systems are not considered to be
containers. The labels shall comply with the requirements
of chapter 296-839
WAC, Content and distribution of material safety data
sheets (MSDSs) and label information, and
WAC 296-800-170 of the Safety and health core rules. Labels
shall include the following legend:
(i)
DANGER
CONTAINS ETHYLENE OXIDE
CANCER HAZARD AND REPRODUCTIVE HAZARD, and
(ii) A warning statement against breathing airborne concentrations
of EtO.
(c) The labeling requirements under WAC
296-62-07355 through 296-62-07389
do not apply where EtO is used as a pesticide, as such term
is defined in the Federal Insecticide, Fungicide, and Rodenticide
Act (7 U.S.C. 136 et seq.), when it is labeled pursuant to
that act and regulations issued under that act by the Environmental
Protection Agency.
(2) Material safety data sheets. Employers who are manufacturers
or importers of EtO shall comply with the requirements regarding
development of material safety data sheets as specified in WAC
296-62-05413 of the hazard communication standard.
(3) Information and training.
(a) The employer shall provide employees who are potentially
exposed to EtO at or above the action level or above the excursion
limit with information and training on EtO at the time of
initial assignment and at least annually thereafter.
(b) Employees shall be informed of the following:
(i) The requirements of WAC 296-62-07353 through 296-62-07389
with an explanation of its contents, including Appendices
A and B;
(ii) Any operations in their work area where EtO is present;
(iii) The location and availability of the written EtO
final rule; and
(iv) The medical surveillance program required by WAC
296-62-07371 with an explanation of the information
in Appendix C.
(c) Employee training shall include at least:
(i) Methods and observations that may be used to detect
the presence or release of EtO in the work area (such as
monitoring conducted by the employer, continuous monitoring
devices, etc.);
(ii) The physical and health hazards of EtO;
(iii) The measures employees can take to protect themselves
from hazards associated with EtO exposure, including specific
procedures the employer has implemented to protect employees
from exposure to EtO, such as work-practices, emergency
procedures, and personal protective equipment to be used;
and
(iv) The details of the hazard communication program developed
by the employer, including an explanation of the labeling
system and how employees can obtain and use the appropriate
hazard information.
(a) Where the processing, use, or handling of products made
from or containing EtO are exempted from other requirements
of WAC
296-62-07355 through 296-62-07389
under WAC
296-62-07355, or where objective data have been relied
on in lieu of initial monitoring under WAC
296-62-07361 (2)(b), the employer shall establish and
maintain an accurate record of objective data reasonably relied
upon in support of the exemption.
(b) This record shall include at least the following information:
(i) The product qualifying for exemption;
(ii) The source of the objective data;
(iii) The testing protocol, results of testing, and/or
analysis of the material for the release of EtO;
(iv) A description of the operation exempted and how the
data support the exemption; and
(v) Other data relevant to the operations, materials, processing,
or employee exposures covered by the exemption.
(c) The employer shall maintain this record for the duration
of the employer's reliance upon such objective data.
(2) Exposure measurements.
(a) The employer shall keep an accurate record of all measurements
taken to monitor employee exposure to EtO as prescribed in
WAC
296-62-07361.
(b) This record shall include at least the following information:
(i) The date of measurement;
(ii) The operation involving exposure to EtO which is being
monitored;
(iii) Sampling and analytical methods used and evidence
of their accuracy;
(iv) Number, duration, and results of samples taken;
(v) Type of protective devices worn, if any; and
(vi) Name, Social Security number and exposure of the employees
whose exposures are represented.
(c) The employer shall maintain this record for at least
thirty years, in accordance with chapter
296-802 WAC.
(3) Medical surveillance.
(a) The employer shall establish and maintain an accurate
record for each employee subject to medical surveillance by
WAC
296-62-07371 (1)(a), in accordance with chapter
296-802 WAC.
(b) The record shall include at least the following information:
(i) The name and Social Security number of the employee;
(ii) Physicians' written opinions;
(iii) Any employee medical complaints related to exposure
to EtO; and
(iv) A copy of the information provided to the physician
as required by WAC
296-62-07371(3).
(c) The employer shall ensure that this record is maintained
for the duration of employment plus thirty years, in accordance
with chapter
296-802 WAC.
(4) Availability.
(a) The employer, upon written request, shall make all records
required to be maintained by WAC
296-62-07355 through 296-62-07389
available to the director for examination and copying.
(b) The employer, upon request, shall make any exemption
and exposure records required by WAC
296-62-07377 (1) and (2) available for examination and
copying to affected employees, former employees, designated
representatives and the director, in accordance with chapter
296-802 WAC.
(c) The employer, upon request, shall make employee medical
records required by subsection (3) of this section available
for examination and copying to the subject employee, anyone
having the specific written consent of the subject employee,
and the director, in accordance with chapter
296-802 WAC.
(5) Transfer of records.
(a) The employer shall comply with the requirements concerning
transfer of records set forth in chapter
296-802 WAC.
(b) Whenever the employer ceases to do business and there
is no successor employer to receive and retain the records
for the prescribed period, the employer shall notify the director
at least ninety days prior to disposal and transmit them to
the director.
(1) Employee observation. The employer shall provide affected
employees or their designated representatives an opportunity
to observe any monitoring of employee exposure to EtO conducted
in accordance with WAC
296-62-07361.
(2) Observation procedures. When observation of the monitoring
of employee exposure to EtO requires entry into an area where
the use of protective clothing or equipment is required, the
observer shall be provided with and be required to use such
clothing and equipment and shall comply with all other applicable
safety and health procedures.
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.
(c) Ethylene oxide can be found as a liquid or vapor.
(d) EtO is used in the manufacture of ethylene glycol, surfactants,
ethanolamines, glycol ethers, and other organic chemicals.
EtO is also used as a sterilant and fumigant.
(e) Appearance and odor: Colorless liquid below 10.7°C (51.3°F)
or colorless gas with ether-like odor detected at approximately
700 parts EtO per million parts of air (700 ppm).
(f) Permissible exposure: Exposure may not exceed 1 part
EtO per million parts of air averaged over the 8-hour work
day.
(2) Health hazard data
(a) Ethylene oxide can cause bodily harm if you inhale the
vapor, if it comes into contact with your eyes or skin, or
if you swallow it.
(b) Effects of overexposure:
(i) Ethylene oxide in liquid form can cause eye irritation
and injury to the cornea, frostbite, and severe irritation
and blistering of the skin upon prolonged or confined contact.
Ingestion of EtO can cause gastric irritation and liver
injury. Acute effects from inhalation of EtO vapors include
respiratory irritation and lung injury, headache, nausea,
vomiting, diarrhea, shortness of breath, and cyanosis (blue
or purple coloring of skin). Exposure has also been associated
with the occurrence of cancer, reproductive effects, mutagenic
changes, neurotoxicity, and sensitization.
(ii) EtO has been shown to cause cancer in laboratory animals
and has been associated with higher incidences of cancer
in humans. Adverse reproductive effects and chromosome damage
may also occur from EtO exposure.
(c) Reporting signs and symptoms: You should inform your
employer if you develop any signs or symptoms and suspect
that they are caused by exposure to EtO.
(3) Emergency first aid procedures
(a) Eye exposure: If EtO gets into your eyes, wash your eyes
immediately with large amounts of water, lifting the lower
and upper eyelids. Get medical attention immediately. Contact
lenses should not be worn when working with this chemical.
(b) Skin exposure: If EtO gets on your skin, immediately
wash the contaminated skin with water. If EtO soaks through
your clothing, especially your shoes, remove the clothing
immediately and wash the skin with water using an emergency
deluge shower. Get medical attention immediately. Thoroughly
wash contaminated clothing before reusing. Contaminated leather
shoes or other leather articles should not be reused and should
be discarded.
(c) Inhalation: If large amounts of EtO are inhaled, the
exposed person must be moved to fresh air at once. If breathing
has stopped, perform cardiopulmonary resuscitation. Keep the
affected person warm and at rest. Get medical attention immediately.
(d) Swallowing: When EtO has been swallowed, give the person
large quantities of water immediately. After the water has
been swallowed, try to get the person to vomit by having him
or her touch the back of the throat with his or her finger.
Do not make an unconscious person vomit. Get medical attention
immediately.
(e) Rescue: Move the affected person from the hazardous exposure.
If the exposed person has been overcome, attempt rescue only
after notifying at least one other person of the emergency
and putting into effect established emergency procedures.
Do not become a casualty yourself. Understand your emergency
rescue procedures and know the location of the emergency equipment
before the need arises.
(4) Respirators and protective clothing
(a) Respirators:
(i) You may be required to wear a respirator for nonroutine
activities, in emergencies, while your employer is in the
process of reducing EtO exposure through engineering controls,
and in areas where engineering controls are not feasible.
Only air supplied positive-pressure, full-facepiece respirators
are approved for protection against EtO. If air-purifying
respirators are worn in the future, they must have a label
issued by the National Institute for Occupational Safety
and Health (NIOSH) under the provisions of 42 CFR part 84
stating that the respirators have been certified for use
with ethylene oxide. 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.
(ii) EtO does not have a detectable odor except at levels
well above the permissible exposure limits. If you can smell
EtO while wearing a respirator, proceed immediately to fresh
air. If you experience difficulty breathing while wearing
a respirator, tell your employer.
(b) Protective clothing:
(i) You may be required to wear impermeable clothing, gloves,
a face shield, or other appropriate protective clothing
to prevent skin contact with liquid EtO or EtO-containing
solutions. Where protective clothing is required, your employer
must provide clean garments to you as necessary to assure
that the clothing protects you adequately.
(ii) Replace or repair protective clothing that has become
torn or otherwise damaged.
(iii) EtO must never be allowed to remain on the skin.
Clothing and shoes which are not impermeable to EtO should
not be allowed to become contaminated with EtO, and if they
do, the clothing should be promptly removed and decontaminated.
Contaminated leather shoes should be discarded. Once EtO
penetrates shoes or other leather articles, they should
not be worn again.
(c) Eye protection: You must wear splashproof safety goggles
in areas where liquid EtO or EtO-containing solutions may
contact your eyes. In addition, contact lenses should not
be worn in areas where eye contact with EtO can occur.
(5) Precautions for safe use, handling, and storage
(a) EtO is a flammable liquid, and its vapors can easily
form explosive mixtures in air.
(b) EtO must be stored in tightly closed containers in a
cool, well-ventilated area, away from heat, sparks, flames,
strong oxidizers, alkalines, and acids, strong bases, acetylide
forming metals such as copper, silver, mercury and their alloys.
(c) Sources of ignition such as smoking material, open flames
and some electrical devices are prohibited wherever EtO is
handled, used, or stored in a manner that could create a potential
fire or explosion hazard.
(d) You should use nonsparking tools when opening or closing
metal containers of EtO, and containers must be bonded and
grounded in the rare instances in which liquid EtO is poured
or transferred.
(e) Impermeable clothing wet with liquid EtO or EtO-containing
solutions may be easily ignited. If you are wearing impermeable
clothing and are splashed with liquid EtO or EtO-containing
solution, you should immediately remove the clothing while
under an emergency deluge shower.
(f) If your skin comes into contact with liquid EtO or EtO-containing
solutions, you should immediately remove the EtO using an
emergency deluge shower.
(g) You should not keep food, beverages, or smoking materials
in regulated areas where employee exposures are above the
permissible exposure limits.
(h) Fire extinguishers and emergency deluge showers for quick
drenching should be readily available, and you should know
where they are and how to operate them.
(i) Ask your supervisor where EtO is used in your work area
and for any additional plant safety and health rules.
(6) Access to information.
(a) Each year, your employer is required to inform you of
the information contained in this standard and appendices
for EtO. In addition, your employer must instruct you in the
proper work-practices for using EtO emergency procedures,
and the correct use of protective equipment.
(b) Your employer is required to determine whether you are
being exposed to EtO. You or your representative has the right
to observe employee measurements and to record the results
obtained. Your employer is required to inform you of your
exposure. If your employer determines that you are being overexposed,
he or she is required to inform you of the actions which are
being taken to reduce your exposure to within permissible
exposure limits.
(c) Your employer is required to keep records of your exposures
and medical examinations. These exposure records must be kept
by the employer for at least thirty years. Medical records
must be kept for the period of your employment plus thirty
years.
(d) Your employer is required to release your exposure and
medical records to your physician or designated representative
upon your written request.
(7) Sterilant use of EtO in hospitals and health care facilities.
(a) This section of Appendix A, for informational purposes,
sets forth EPA's recommendations for modifications in workplace
design and practice in hospitals and health care facilities
for which the Environmental Protection Agency has registered
EtO for uses as a sterilant or fumigant under the Federal
Insecticide, Fungicide, and Rodenticide Act, 7 U.S.C. 136
et seq. These new recommendations, published in the Federal
Register by EPA at 49 FR 15268, as modified in today's Register,
are intended to help reduce the exposure of hospital and health
care workers to EtO to 1 ppm. EPA's recommended workplace
design and workplace practice are as follows:
(i) Workplace design
(A) Installation of gas line hand valves. Hand valves
must be installed on the gas supply line at the connection
to the supply cylinders to minimize leakage during cylinder
change.
(B) Installation of capture boxes. Sterilizer operations
result in a gas/water discharge at the completion of the
process. This discharge is routinely piped to a floor
drain which is generally located in an equipment or an
adjacent room. When the floor drain is not in the same
room as the sterilizer and workers are not normally present,
all that is necessary is that the room be well ventilated.
(C) The installation of a “capture box” will
be required for those work place layouts where the floor
drain is located in the same room as the sterilizer or
in a room where workers are normally present. A “capture
box” is a piece of equipment that totally encloses
the floor drain where the discharge from the sterilizer
is pumped. The “capture box” is to be vented
directly to a nonrecirculating or dedicated ventilation
system. Sufficient air intake should be allowed at the
bottom of the box to handle the volume of air that is
ventilated from the top of the box. The “capture
box” can be made of metal, plastic, wood or other
equivalent material. The box is intended to reduce levels
of EtO discharged into the work room atmosphere. The use
of a “capture box” is not required if: (I)
The vacuum pump discharge floor drain is located in a
well ventilated equipment or other room where workers
are not normally present or (II) the water sealed vacuum
pump discharges directly to a closed sealed sewer line
(check local plumbing codes).
(D) If it is impractical to install a vented “capture
box” and a well ventilated equipment or other room
is not feasible, a box that can be sealed over the floor
drain may be used if: (I) The floor drain is located in
a room where workers are not normally present and EtO
cannot leak into an occupied area, and (II) the sterilizer
in use is less than 12 cubic feet in capacity (check local
plumbing codes).
(ii) Ventilation of aeration units.
(A) Existing aeration units. Existing units must be vented
to a nonrecirculating or dedicated system or vented to
an equipment or other room where workers are not normally
present and which is well ventilated. Aerator units must
be positioned as close as possible to the sterilizer to
minimize the exposure from the off-gassing of sterilized
items.
(B) Installation of new aerator units (where none exist).
New aerator units must be vented as described above for
existing aerators. Aerators must be in place by July 1,
1986.
(iii) Ventilation during cylinder change. Workers may be
exposed to short but relatively high levels of EtO during
the change of gas cylinders. To reduce exposure from this
route, users must select one of three alternatives designed
to draw off gas that may be released when the line from
the sterilizer to the cylinder is disconnected:
(A) Location of cylinders in a well ventilated equipment
room or other room where workers are not normally present.
(B) Installation of a flexible hose (at least four inches
in diameter) to a nonrecirculating or dedicated ventilation
system and located in the area of cylinder change in such
a way that the hose can be positioned at the point where
the sterilizer gas line is disconnected from the cylinder.
(C) Installation of a hood that is part of a nonrecirculating
or dedicated system and positioned no more than one foot
above the point where the change of cylinders takes place.
(iv) Ventilation of sterilizer door area. One of the major
sources of exposure to EtO occurs when the sterilizer door
is opened following the completion of the sterilization
process. In order to reduce this avenue of exposure, a hood
or metal canopy closed on each end must be installed over
the sterilizer door. The hood or metal canopy must be connected
to a nonrecirculating or dedicated ventilation system or
one that exhausts gases to a well ventilated equipment or
other room where workers are not normally present. A hood
or canopy over the sterilizer door is required for use even
with those sterilizers that have a purge cycle and must
be in place by July 1, 1986.
(v) Ventilation of sterilizer relief valve. Sterilizers
are typically equipped with a safety relief device to release
gas in case of increased pressure in the sterilizer. Generally,
such relief devices are used on pressure vessels. Although
these pressure relief devices are rarely opened for hospital
and health care sterilizers, it is suggested that they be
designed to exhaust vapor from the sterilizer by one of
the following methods:
(A) Through a pipe connected to the outlet of the relief
valve ventilated directly outdoors at a point high enough
to be away from passers by, and not near any windows that
open, or near any air conditioning or ventilation air
intakes.
(B) Through a connection to an existing or new nonrecirculating
or dedicated ventilation system.
(C) Through a connection to a well ventilated equipment
or other room where workers are not normally present.
(vi) Ventilation systems. Each hospital and health care
facility affected by this notice that uses EtO for the sterilization
of equipment and supplies must have a ventilation system
which enables compliance with the requirements of (a)(i)(B)
through (v) of this subsection in the manner described in
these sections and within the timeframes allowed. Thus,
each affected hospital and health care facility must have
or install a nonrecirculating or dedicated ventilation equipment
or other room where workers are not normally present in
which to vent EtO.
(vii) Installation of alarm systems. An audible and visual
indicator alarm system must be installed to alert personnel
of ventilation system failures, i.e., when the ventilation
fan motor is not working.
(b) Workplace practices
(i) All the workplace practices discussed in this unit
must be permanently posted near the door of each sterilizer
prior to use by any operator.
(ii) Changing of supply line filters.
Filters in the sterilizer liquid line must be changed when
necessary, by the following procedure:
(A) Close the cylinder valve and the hose valve.
(B) Disconnect the cylinder hose (piping) from the cylinder.
(C) Open the hose valve and bleed slowly into a proper
ventilating system at or near the in-use supply cylinders.
(D) Vacate the area until the line is empty.
(E) Change the filter.
(F) Reconnect the lines and reverse the valve position.
(G) Check hoses, filters, and valves for leaks with a
fluorocarbon leak detector (for those sterilizers using
the eighty-eight percent chlorofluorocarbon, twelve percent
ethylene oxide mixture (12/88)).
(iii) Restricted access area.
(A) Areas involving use of EtO must be designated as
restricted access areas. They must be identified with
signs or floor marks near the sterilizer door, aerator,
vacuum pump floor drain discharge, and in-use cylinder
storage.
(B) All personnel must be excluded from the restricted
area when certain operations are in progress, such as
discharging a vacuum pump, emptying a sterilizer liquid
line, or venting a nonpurge sterilizer with the door ajar
or other operations where EtO might be released directly
into the face of workers.
(iv) Door opening procedures.
(A) Sterilizers with purge cycles. A load treated in
a sterilizer equipped with a purge cycle should be removed
immediately upon completion of the cycle (provided no
time is lost opening the door after cycle is completed).
If this is not done, the purge cycle should be repeated
before opening door.
(B) Sterilizers without purge cycles. For a load treated
in a sterilizer not equipped with a purge cycle, the sterilizer
door must be ajar six inches for fifteen minutes, and
then fully opened for at least another fifteen minutes
before removing the treated load. The length of time of
the second period should be established by peak monitoring
for one hour after the two fifteen-minute periods suggested.
If the level is above 10 ppm time-weighted average for
eight hours, more time should be added to the second waiting
period (door wide open). However, in no case may the second
period be shortened to less than fifteen minutes.
(v) Chamber unloading procedures.
(A) Procedures for unloading the chamber must include
the use of baskets or rolling carts, or baskets and rolling
tables to transfer treated loads quickly, thus avoiding
excessive contact with treated articles, and reducing
the duration of exposures.
(B) If rolling carts are used, they should be pulled
not pushed by the sterilizer operators to avoid offgassing
exposure.
(vi) Maintenance. A written log should be instituted and
maintained documenting the date of each leak detection and
any maintenance procedures undertaken. This is a suggested
use practice and is not required.
(vii) Leak detection. Sterilizer door gaskets, cylinder
and vacuum piping, hoses, filters, and valves must be checked
for leaks under full pressure with a Fluorocarbon leak detector
(for 12/88 systems only) every two weeks by maintenance
personnel. Also, the cylinder piping connections must be
checked after changing cylinders. Particular attention in
leak detection should be given to the automatic solenoid
valves that control the flow of EtO to the sterilizer. Specifically,
a check should be made at the EtO gasline entrance port
to the sterilizer, while the sterilizer door is open and
the solenoid valves are in a closed position.
(viii) Maintenance procedures. Sterilizer/aerator door
gaskets, valves, and fittings must be replaced when necessary
as determined by maintenance personnel in their biweekly
checks; in addition, visual inspection of the door gaskets
for cracks, debris, and other foreign substances should
be conducted daily by the operator.
(ii) Specific gravity (water = 1): 0.87 (at 20°C or 68°F);
(iii) Vapor density (air = 1): 1.49;
(iv) Vapor pressure (at 20°C): 1,095 mm Hg;
(v) Solubility in water: Complete;
(vi) Appearance and odor: Colorless liquid; gas at temperature
above 10.7°F or 51.3°C with ether-like odor above 700 ppm.
(2) Fire, explosion, and reactivity hazard data:
(a) Fire:
(i) Flash point; Less than 0°F (open cup);
(ii) Stability: Decomposes violently at temperatures above
800°F;
(iii) Flammable limits in air, percent by volume: Lower:
3, Upper: 100;
(iv) Extinguishing media: Carbon dioxide for small fires,
polymer or alcohol foams for large fires;
(v) Special fire fighting procedures: Dilution of ethylene
oxide with 23 volumes of water renders it nonflammable;
(vi) Unusual fire and explosion hazards: Vapors of EtO
will burn without the presence of air or other oxidizers.
EtO vapors are heavier than air and may travel along the
ground and be ignited by open flames or sparks at locations
remote from the site at which EtO is being used.
(vii) For purposes of compliance with the requirements
of WAC
296-24-330, EtO is classified as a flammable gas. For
example, 7,500 ppm, approximately one-fourth of the lower
flammable limit, would be considered to pose a potential
fire and explosion hazard.
(viii) For purposes of compliance with WAC 296-24-585,
EtO is classified as a Class B fire hazard.
(ix) For purpose of compliance with chapter 296-24
WAC Part L, and WAC
296-800-280, locations classified as hazardous due to
the presence of EtO shall be Class I.
(b) Reactivity:
(i) Conditions contributing to instability: EtO will polymerize
violently if contaminated with aqueous alkalies, amines,
mineral acids, metal chlorides, or metal oxides. Violent
decomposition will also occur at temperatures above 800°F;
(ii) Incompatibilities: Alkalines and acids;
(iii) Hazardous decomposition products: Carbon monoxide
and carbon dioxide.
(3) Spill, leak, and disposal procedures:
(a) If EtO is spilled or leaked, the following steps should
be taken:
(i) Remove all ignition sources.
(ii) The area should be evacuated at once and re-entered
only after the area has been thoroughly ventilated and washed
down with water.
(b) Persons not wearing appropriate protective equipment
should be restricted from areas of spills or leaks until cleanup
has been completed.
(c) Waste disposal method: Waste material should be disposed
of in a manner that is not hazardous to employees or to the
general population. In selecting the method of waste disposal,
applicable local, state, and federal regulations should be
consulted.
(4) Monitoring and measurement procedures:
(a) Exposure above the permissible exposure limit:
(i) Eight-hour exposure evaluation: Measurements taken
for the purpose of determining employee exposure under this
section are best taken with consecutive samples covering
the full shift. Air samples should be taken in the employee's
breathing zone (air that would most nearly represent that
inhaled by the employee.)
(ii) Monitoring techniques: The sampling and analysis under
this section may be performed by collection of the EtO 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 as long as measurements taken using
these methods accurately evaluate the concentration of EtO
in employees' breathing zones.
(iii) Appendix D describes the validated method of sampling
and analysis which has been tested by OSHA for use with
EtO. Other available methods are also described in Appendix
D. The employer has the obligation of selecting a monitoring
method which meets the accuracy and precision requirements
of the standard under his/her unique field conditions. The
standard requires that the method of monitoring should be
accurate, to a 95 percent confidence level, to plus or minus
25 percent for concentrations of EtO at 1 ppm, and to plus
or minus 35 percent for concentrations at 0.5 ppm. In addition
to the method described in Appendix D, there are numerous
other methods available for monitoring for EtO 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 measurement procedures, employers
should assure that the evaluation of employee exposures is
performed by a technically qualified person.
(5) Protective clothing and equipment:
(a) Employees should be provided with and be required to
wear appropriate protective clothing wherever there is significant
potential for skin contact with liquid EtO or EtO-containing
solutions. Protective clothing shall include impermeable coveralls
or similar full-body work clothing, gloves, and head coverings,
as appropriate to protect areas of the body which may come
in contact with liquid EtO or EtO-containing solutions.
(b) Employers should ascertain that the protective garments
are impermeable to EtO. Permeable clothing, including items
made of rubber, and leather shoes should not be allowed
to become contaminated with liquid EtO. If permeable clothing
does become contaminated, it should be immediately removed,
while the employer is under an emergency deluge shower.
If leather footwear or other leather garments become wet
from EtO they should be discarded and not be worn again,
because leather absorbs EtO and holds it against the skin.
(c) Any protective clothing that has been damaged or is
otherwise found to be defective should be repaired or replaced.
Clean protective clothing should be provided to the employee
as necessary to assure employee protection. Whenever impermeable
clothing becomes wet with liquid EtO, it should be washed
down with water before being removed by the employee. Employees
are also required to wear splashproof safety goggles where
there is any possibility of EtO contacting the eyes.
(6) Miscellaneous precautions:
(a) Store EtO in tightly closed containers in a cool, well-ventilated
area and take all necessary precautions to avoid any explosion
hazard.
(b) Nonsparking tools must be used to open and close metal
containers. These containers must be effectively grounded
and bonded.
(c) Do not incinerate EtO cartridges, tanks or other containers.
(d) Employers should advise employees of all areas and operations
where exposure to EtO occurs.
(7) Common operations:
Common operations in which exposure to EtO is likely to occur
include the following: (a) Manufacture of EtO, (b) surfactants,
(c) ethanolamines, (d) glycol ethers, (e) specialty chemicals,
and (f) use as a sterilant in the hospital, health product and
spice industries.
WAC
296-62-07387 Appendix C--Medical surveillance guidelines
for ethylene oxide (nonmandatory).
(1) Route of entry: Inhalation.
(2) Toxicology:
(a) Clinical evidence of adverse effects associated with
the exposure to EtO is present in the form of increased incidence
of cancer in laboratory animals (leukemia, stomach, brain),
mutation in offspring in animals, and resorptions and spontaneous
abortions in animals and human populations respectively. Findings
in humans and experimental animals exposed to airborne concentrations
of EtO also indicate damage to the genetic material (DNA).
These include hemoglobin alkylation, unscheduled DNA synthesis,
sister chromatid exchange chromosomal aberration, and functional
sperm abnormalities.
(b) Ethylene oxide in liquid form can cause eye irritation
and injury to the cornea, frostbite, severe irritation, and
blistering of the skin upon prolonged or confined contact.
Ingestion of EtO can cause gastric irritation and liver injury.
Other effects from inhalation of EtO vapors include respiratory
irritation and lung injury, headache, nausea, vomiting, diarrhea,
dyspnea and cyanosis.
(3) Signs and symptoms of acute overexposure:
(a) The early effects of acute overexposure to EtO are nausea
and vomiting, headache, and irritation of the eyes and respiratory
passages. The patient may notice a “peculiar taste”
in the mouth. Delayed effects can include pulmonary edema,
drowsiness, weakness, and incoordination. Studies suggest
that blood cell changes, an increase in chromosomal aberrations,
and spontaneous abortion may also be casually related to acute
overexposure to EtO.
(b) Skin contact with liquid or gaseous EtO causes characteristic
burns and possible even an allergic-type sensitization. The
edema and erythema occurring from skin contact with EtO progress
to vesiculation with a tendency to coalesce into blebs with
desquamation. Healing occurs within three weeks, but there
may be a residual brown pigmentation. A 40-80% solution is
extremely dangerous, causing extensive blistering after only
brief contact. Pure liquid EtO causes frostbite because of
rapid evaporation. In contrast, the eye is relatively insensitive
to EtO, but there may be some irritation of the cornea.
(c) Most reported acute effects of occupational exposure
to EtO are due to contact with EtO in liquid phase. The liquid
readily penetrates rubber and leather, and will produce blistering
if clothing or footwear contaminated with EtO are not removed.
(4) Surveillance and preventive considerations:
(a) As noted above, exposure to EtO has been linked to an
increased risk of cancer and reproductive effects including
decreased male fertility, fetotoxicity, and spontaneous abortion.
EtO workers are more likely to have chromosomal damage than
similar groups not exposed to EtO. At the present, limited
studies of chronic effects in humans resulting from exposure
to EtO suggest a causal association with leukemia. Animal
studies indicate leukemia and cancers at other sites (brain,
stomach) as well. The physician should be aware of the findings
of these studies in evaluating the health of employees exposed
to EtO.
(b) Adequate screening tests to determine an employee's potential
for developing serious chronic diseases, such as cancer, from
exposure to EtO do not presently exist. Laboratory tests may,
however, give evidence to suggest that an employee is potentially
overexposed to EtO. It is important for the physician to become
familiar with the operating conditions in which exposure to
EtO is likely to occur. The physician also must become familiar
with the signs and symptoms that indicate a worker is receiving
otherwise unrecognized and unacceptable exposure to EtO. These
elements are especially important in evaluating the medical
and work histories and in conducting the physical exam. When
an unacceptable exposure in an active employee is identified
by the physician, measures taken by the employer to lower
exposure should also lower the risk of serious long-term consequences.
(c) The employer is required to institute a medical surveillance
program for all employees who are or will be exposed to EtO
at or above the action level (0.5 ppm) for at least 30 days
per year, without regard to respirator use. All examinations
and procedures must be performed by or under the supervision
of a licensed physician at a reasonable time and place for
the employee and at no cost to the employee.
(d) Although broad latitude in prescribing specific tests
to be included in the medical surveillance program is extended
to the examining physician, WISHA requires inclusion of the
following elements in the routine examination:
(i) Medical and work histories with special emphasis directed
to symptoms related to the pulmonary, hematologic, neurologic,
and reproductive systems and to the eyes and skin.
(ii) Physical examination with particular emphasis given
to the pulmonary, hematologic, neurologic, and reproductive
systems and to the eyes and skin.
(iii) Complete blood count to include at least a white
cell count (including differential cell count), red cell
count, hematocrit, and hemoglobin.
(iv) Any laboratory or other test which the examining physician
deems necessary by sound medical practice.
(e) If requested by the employee, the medical examinations
shall include pregnancy testing or laboratory evaluation of
fertility as deemed appropriate by the physician.
(f) In certain cases, to provide sound medical advice to
the employer and the employee, the physician must evaluate
situations not directly related to EtO. For example, employees
with skin diseases may be unable to tolerate wearing protective
clothing. In addition those with chronic respiratory diseases
may not tolerate the wearing of negative pressure (air purifying)
respirators. Additional tests and procedures that will help
the physician determine which employees are medically unable
to wear such respirators should include: An evaluation of
cardiovascular function, a baseline chest x-ray to be repeated
at five year intervals, and a pulmonary function test to be
repeated every three years. The pulmonary function test should
include measurement of the employee's forced vital capacity
(FVC), forced expiratory volume at one second (FEV1), as well
as calculation of the ratios of FEV1 to FVC, and measured
FVC and measured FEV1 to expected values corrected for variation
due to age, sex, race, and height.
(g) The employer is required to make the prescribed tests
available at least annually to employees who are or will be
exposed at or above the action level, for 30 or more days
per year; more often than specified if recommended by the
examining physician; and upon the employee's termination of
employment or reassignment to another work area. While little
is known about the long-term consequences of high short-term
exposures, it appears prudent to monitor such affected employees
closely in light of existing health data. The employer shall
provide physician recommended examinations to any employee
exposed to EtO in emergency conditions. Likewise, the employer
shall make available medical consultations including physician
recommended exams to employees who believe they are suffering
signs or symptoms of exposure to EtO.
(h) The employer is required to provide the physician with
the following information: A copy of this standard and its
appendices; a description of the affected employee's duties
as they relate to the employee exposure level; and information
from the employee's previous medical examinations which is
not readily available to the examining physician. Making this
information available to the physician will aid in the evaluation
of the employee's health in relation to assigned duties and
fitness to wear personal protective equipment, when required.
(i) The employer is required to obtain a written opinion
from the examining physician containing the results of the
medical examinations; the physician's opinion as to whether
the employee has any detected medical conditions which would
place the employee at increased risk of material impairment
of his or her health from exposure to EtO; any recommended
restrictions upon the employee's exposure to EtO, or upon
the use of protective clothing or equipment such as respirators;
and a statement that the employee has been informed by the
physician of the results of the medical examination and of
any medical conditions which require further explanation or
treatment. This written opinion must not reveal specific findings
or diagnoses unrelated to occupational exposure to EtO, and
a copy of the opinion must be provided to the affected employee.
(j) The purpose in requiring the examining physician to supply
the employer with a written opinion is to provide the employer
with a medical basis to aid in the determination of initial
placement of employees and to assess the employee's ability
to use protective clothing and equipment.
WAC
296-62-07389 Appendix D--Sampling and analytical methods
for ethylene oxide (nonmandatory).
(1) A number of methods are available for monitoring employee
exposures to EtO. Most of these involve the use of charcoal
tubes and sampling pumps, followed by analysis of the samples
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, methods using passive dosimeters, gas sampling
bags, impingers, and detector tubes have been utilized for determination
of EtO exposure. In addition, there are several commercially
available portable gas analyzers and monitoring units. This
appendix contains details for the method which has been tested
at the OSHA Analytical Laboratory in Salt Lake City. Inclusion
of this method in the appendix does not mean that this method
is the only one which will be satisfactory. Copies of descriptions
of other methods available are available in the rulemaking record,
and may be obtained from the OSHA Docket Office. These include
the Union Carbide, Dow Chemical, 3M, and DuPont methods, as
well as NIOSH Method S-286. These methods are briefly described
at the end of this appendix.
(2) Employers who note problems with sample breakthrough using
the OSHA or other charcoal methods should try larger charcoal
tubes. Tubes of larger capacity are available. In addition,
lower flow rates and shorter sampling times should be beneficial
in minimizing breakthrough problems. Whatever method the employer
chooses, he/she must assure himself/herself of the method's
accuracy and precision under the unique conditions present in
his workplace.
(3) Ethylene oxide:
(a) Method No.: 30.
(b) Matrix: Air.
(i) Target concentration: 1.0 ppm (1.8 mg/m3)
(ii) Procedure: Samples are collected on two charcoal tubes
in series and desorbed with 1% CS2 in benzene. The samples
are derivatized with HBr and treated with sodium carbonate.
Analysis is done by gas chromatography with an electron
capture detector.
(iii) Recommended air volume and sampling rate: 1 liter
and 0.05 Lpm.
(iv) Detection limit of the overall procedure: 13.3 ppb
(0.024 mg/m3) (based on 1.0 liter air sample).
(v) Reliable quantitation limit: 52.2 ppb (0.094 mg/m3)
(based on 1.0 liter air sample).
(vi) Standard error of estimate: 6.59% (see backup section
4.6).
(vii) Special requirements: Samples must be analyzed within
15 days of sampling date.
(viii) Status of method: The sampling and analytical method
has been subject to the established evaluation procedures
of the Organic Method Evaluations Branch.
(c) Date: August 1981.
(d) Chemist: Wayne D. Potter
(e) Organic Solvents Branch, OSHA Analytical Laboratory,
Salt Lake City, Utah
(f) General discussion:
(i) Background.
(A) History of procedure.
(I) Ethylene oxide samples analyzed at the OSHA laboratory
have normally been collected on activated charcoal and
desorbed with carbon disulfide. The analysis is performed
with a gas chromatograph equipped with a FID (flame
ionization detector) as described in NIOSH Method S286
(Ref. (3)(j)(i)). This method is based on a PEL of 50
ppm and has a detection limit of about 1 ppm.
(II) Recent studies have prompted the need for a method
to analyze and detect ethylene oxide at very low concentrations.
(III) Several attempts were made to form an ultraviolet
(UV) sensitive derivative with ethylene oxide for analysis
with HPLC. Among those tested that gave no detectable
product were: p-anisidine, methylimidazole, aniline,
and 2,3,6-trichlorobenzoic acid. Each was tested with
catalysts such as triethylamine, aluminum chloride,
methylene chloride and sulfuric acid but no detectable
derivative was produced.
(IV) The next derivatization attempt was to react ethylene
oxide with HBr to form 2-bromoethanol. This reaction
was successful. An ECD (electron capture detector) gave
a very good response for 2-bromoethanol due to the presence
of bromine. The use of carbon disulfide as the desorbing
solvent gave too large a response and masked the 2-bromoethanol.
Several other solvents were tested for both their response
on the ECD and their ability to desorb ethylene oxide
from the charcoal. Among those tested were toluene,
xylene, ethyl benzene, hexane, cyclohexane and benzene.
Benzene was the only solvent tested that gave a suitable
response on the ECD and a high desorption. It was found
that the desorption efficiency was improved by using
1% CS2 with the benzene. The carbon disulfide did not
significantly improve the recovery with the other solvents.
SKC Lot 120 was used in all tests done with activated
charcoal.
(A) Detection limit of the analytical procedure. The
detection limit of the analytical procedure is 12.0 picograms
of ethylene oxide per injection. This is the amount of
analyte which will give a peak whose height is five times
the height of the baseline noise. (See backup data section
(3)(i)(i).)
(B) Detection limit of the overall procedure.
(I) The detection limit of the overall procedure is
24.0 ng of ethylene oxide per sample.
(II) This is the amount of analyte spiked on the sampling
device which allows recovery of an amount of analyte
equivalent to the detection limit of the analytical
procedure. (See backup data section (3)(i)(ii).)
(C) Reliable quantitation limit.
(I) The reliable quantitation limit is 94.0 nanograms
of ethylene oxide per sample. This is the smallest amount
of analyte which can be quantitated within the requirements
of 75% recovery and 95% confidence limits. (See backup
data section (3)(i)(ii).)
(II) It must be recognized that the reliable quantitation
limit and detection limits reported in the method are
based upon optimization of the instrument for the smallest
possible amount of analyte. When the target concentration
of an analyte is exceptionally higher than these limits,
they may not be attainable at the routine operating
parameters. In this case, the limits reported on analysis
reports will be based on the operating parameters used
during the analysis of the samples.
(D) Sensitivity.
(I) The sensitivity of the analytical procedure over
a concentration range representing 0.5 to 2 times the
target concentration based on the recommended air volume
is 34105 area units per ug/mL. The sensitivity is determined
by the slope of the calibration curve (see backup data
section (3)(i)(iii)).
(II) The sensitivity will vary somewhat with the particular
instrument used in the analysis.
(E) Recovery. The recovery of analyte from the collection
medium must be 75% or greater. The average recovery from
spiked samples over the range of 0.5 to 2 times the target
concentration is 88.0% (see backup section (3)(i)(iv)).
At lower concentrations the recovery appears to be nonlinear.
(F) Precision (analytical method only). The pooled coefficient
of variation obtained from replicate determination of
analytical standards at 0.5X, 1X and 2X the target concentration
is 0.036 (see backup data section (3)(i)(v)).
(G) Precision (overall procedure).
(I) The overall procedure must provide results at the
target concentration that are 25% or better at the 95%
confidence level. The precision at the 95% confidence
level for the 15 day storage test is plus or minus 12.9%
(see backup data section(3)(i)(vi)).
(II) This includes an additional plus or minus 5% for
sampling error.
(iii) Advantages.
(A) The sampling procedure is convenient.
(B) The analytical procedure is very sensitive and reproducible.
(C) Reanalysis of samples is possible.
(D) Samples are stable for at least 15 days at room temperature.
(E) Interferences are reduced by the longer GC retention
time of the new derivative.
(iv) Disadvantages.
(A) Two tubes in series must be used because of possible
breakthrough and migration.
(B) The precision of the sampling rate may be limited
by the reproducibility of the pressure drop across the
tubes. The pumps are usually calibrated for one tube only.
(C) The use of benzene as the desorption solvent increases
the hazards of analysis because of the potential carcinogenic
effects of benzene.
(D) After repeated injections there can be a buildup
of residue formed on the electron capture detector which
decreases sensitivity.
(E) Recovery from the charcoal tubes appears to be nonlinear
at low concentrations.
(g) Sampling procedure.
(i) Apparatus.
(A) A calibrated personal sampling pump whose flow can
be determined within plus or minus 5% of the recommended
flow.
(B) SKC Lot 120 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 coconut shell charcoal
separated by a 2-mm portion of urethane foam. The adsorbing
section contains 100 mg of charcoal, the backup section
50 mg.
A 3-mm portion of urethane foam is placed between the
outlet end of the tube and the backup section. A plug
of silylated glass wool is placed in front of the adsorbing
section.
(ii) Reagents. None required.
(iii) Sampling technique.
(A) Immediately before sampling, break the ends of the
charcoal tubes. All tubes must be from the same lot.
(B) Connect two tubes in series to the sampling pump
with a short section of flexible tubing. A minimum amount
of tubing is used to connect the two sampling tubes together.
The tube closer to the pump is used as a backup. This
tube should be identified as the backup tube.
(C) The tubes should be placed in a vertical position
during sampling to minimize channeling.
(D) Air being sampled should not pass through any hose
or tubing before entering the charcoal tubes.
(E) Seal the charcoal tubes with plastic caps immediately
after sampling. Also, seal each sample with OSHA seals
lengthwise.
(F) With each batch of samples, submit at least one blank
tube from the same lot used for samples. This tube should
be subjected to exactly the same handling as the samples
(break, seal, transport) except that no air is drawn through
it.
(G) Transport the samples (and corresponding paperwork)
to the lab for analysis.
(H) If bulk samples are submitted for analysis, they
should be transported in glass containers with Teflonlined
caps. These samples must be mailed separately from the
container used for the charcoal tubes.
(iv) Breakthrough.
The breakthrough (5% breakthrough) volume for a 3.0 mg/m3
ethylene oxide sample stream at approximately 85% relative
humidity, 22°C and 633 mm is 2.6 liters sampled at 0.05
liters per minute. This is equivalent to 7.8 µg of ethylene
oxide. Upon saturation of the tube it appeared that the
water may be displacing ethylene oxide during sampling.
(v) Desorption efficiency.
(A) The desorption efficiency, from liquid injection
onto charcoal tubes, averaged 88.0% from 0.5 to 2.0 x
the target concentration for a 1.0 liter air sample. At
lower ranges it appears that the desorption efficiency
is nonlinear (see backup data section (3)(i)(ii)).
(B) The desorption efficiency may vary from one laboratory
to another and also from one lot of charcoal to another.
Thus, it is necessary to determine the desorption efficiency
for a particular lot of charcoal.
(vi) Recommended air volume and sampling rate.
(A) The recommended air volume is 1.0 liter.
(B) The recommended maximum sampling rate is 0.05 Lpm.
(vii) Interferences.
(A) Ethylene glycol and Freon 12 at target concentration
levels did not interfere with the collection of ethylene
oxide.
(B) Suspected interferences should be listed on the sample
data sheets.
(C) The relative humidity may affect the sampling procedure.
(viii) Safety precautions.
(A) Attach the sampling equipment to the employee so
that it does not interfere with work performance.
(B) Wear safety glasses when breaking the ends of the
sampling tubes.
(C) If possible, place the sampling tubes in a holder
so the sharp end is not exposed while sampling.
(h) Analytical method.
(i) Apparatus.
(A) Gas chromatograph equipped with a linearized electron
capture detector.
(B) GC column capable of separating the derivative of
ethylene oxide (2-bromoethanol) from any interferences
and the 1% CS2 in benzene solvent. The column used for
validation studies was: 10 ft x 1/8 inch stainless steel
20% SP-2100, .1% Carbowax 1500 on 100/120 Supelcoport.
(C) An electronic integrator or some other suitable method
of measuring peak areas.
(D) Two milliliter vials with Teflonlined caps.
(E) Gas tight syringe--500 µL or other convenient sizes
for preparing standards.
(F) Microliter syringes--10 µL or other convenient sizes
for diluting standards and
1 µL for sample injections.
(G) Pipets for dispensing the 1% CS2 in benzene solvent.
The Glenco 1 mL dispenser is adequate and convenient.
(H) Volumetric flasks--5 mL and other convenient sizes
for preparing standards.
(I) Disposable Pasteur pipets.
(ii) Reagents.
(A) Benzene, reagent grade.
(B) Carbon disulfide, reagent grade.
(C) Ethylene oxide, 99.7% pure.
(D) Hydrobromic acid, 48% reagent grade.
(E) Sodium carbonate, anhydrous, reagent grade.
(F) Desorbing reagent, 99% Benzene/1% CS2.
(iii) Sample preparation.
(A) The front and back sections of each sample are transferred
to separate 2-mL vials.
(B) Each sample is desorbed with 1.0 mL of desorbing
reagent.
(C) The vials are sealed immediately and allowed to desorb
for one hour with occasional shaking.
(D) Desorbing reagent is drawn off the charcoal with
a disposable pipet and put into clean 2-mL vials.
(E) One drop of HBr is added to each vial. Vials are
resealed and HBr is mixed well with the desorbing reagent.
(F) About 0.15 gram of sodium carbonate is carefully
added to each vial. Vials are again resealed and mixed
well.
(iv) Standard preparation.
(A) Standards are prepared by injecting the pure ethylene
oxide gas into the desorbing reagent.
(B) A range of standards are prepared to make a calibration
curve. A concentration of 1.0 µL of ethylene oxide gas
per 1 mL desorbing reagent is equivalent to 1.0 ppm air
concentration (all gas volumes at 25°C and 760 mm) for
the recommended 1 liter air sample. This amount is uncorrected
for desorption efficiency (see backup data section (3)(i)(ii),
for desorption efficiency corrections).
(C) One drop of HBr per mL of standard is added and mixed
well.
(D) About 0.15 grams of sodium carbonate is carefully
added for each drop of HBr (a small reaction will occur).
(v) Analysis.
(A) GC conditions.
Nitrogen flow rate--10mL/min.
Injector temperature--250°C
Detector temperature--300°C
Column temperature--100°C
Injection size--0.8 µL
Elution time--3.9 minutes
(B) Peak areas are measured by an integrator or other
suitable means.
(C) The integrator results are in area units and a calibration
curve is set up with concentration vs. area units.
(vi) Interferences.
(A) Any compound having the same retention time of 2-bromoethanol
is a potential interference. Possible interferences should
be listed on the sample data sheets.
(B) GC parameters may be changed to circumvent interferences.
(C) There are usually trace contaminants in benzene.
These contaminants, however, posed no problem of interference.
(D) Retention time date on a single column is not considered
proof of chemical identity. Samples over the 1.0 ppm target
level should be confirmed by GC/Mass Spec or other suitable
means.
(vii) Calculations.
(A) The concentration in µg/mL for a sample is determined
by comparing the area of a particular sample to the calibration
curve, which has been prepared from analytical standards.
(B) The amount of analyte in each sample is corrected
for desorption efficiency by use of a desorption curve.
A x B
EtO, mg/m3 = ----------------
C
(C) Analytical results, A, from the two tubes that compose
a particular air sample are added together.
(D) The concentration for a sample is calculated by the
following equation:
where:
A = µg/mL
B = desorption volume in milliliters
C = air volume in liters.
(E) To convert mg/m3 to parts per million
(ppm) the following relationship is used:
mg/m3 x 24.45
EtO, ppm = ----------------------------------
44.05
where:
mg/m3 = results from 3.7.4
24.45 = molar volume at 25°C and 760mm Hg
44.05 = molecular weight of EtO.
(viii) Safety precaution.
(A) Ethylene oxide and benzene are potential carcinogens
and care must be exercised when working with these compounds.
(B) All work done with the solvents (preparation of standards,
desorption of samples, etc.) should be done in a hood.
(C) Avoid any skin contact with all of the solvents.
(D) Wear safety glasses at all times.
(E) Avoid skin contact with HBr because it is highly
toxic and a strong irritant to eyes and skin.
(i) Backup data.
(i) Detection limit data.
The detection limit was determined by injecting 0.8 µL
of a 0.015 µg/mL standard of ethylene oxide into 1% CS2
in benzene. The detection limit of the analytical procedure
is taken to be 1.20 x 10-5 µg per injection. This is equivalent
to 8.3 ppb (0.015 mg/m3) for the recommended
air volume.
(ii) Desorption efficiency. Ethylene oxide was spiked into
charcoal tubes and the following recovery data was obtained:
Amount
Spiked (µg)
Amount
Recovered (µg)
Percent
Recovery
4.5
3.0
2.25
1.5
1.6
.75
.375
.375
.1875
.094
4.32
2.61
2.025
1.365
1.38
.6525
.315
.312
.151
.070
96.0
87.0
90.0
91.0
92.0
87.0
84.0
83.2
80.5
74.5
Note: At lower amounts the recovery appears
to be nonlinear.
(iii) Sensitivity data. The following data was used to
determine the calibration curve:
Injection
0.5
x .75 µg/mL
1 x
1.5 µg/mL
2 x
3.0 µg/mL
1
2
3
4
X
30904
30987
32555
32242
31672
59567
62914
58578
57173
59558
111778
106016
106122
109716
108408
Slope = 34.105.
(iv) Recovery. The recovery was determined by spiking ethylene
oxide onto lot 120 charcoal tubes and desorbing with 1%
CS2 in Benzene. Recoveries were done at 0.5, 1.0, and 2.0
X the target concentration (1 ppm) for the recommended air
volume.
Percent Recovery
Sample
0.5x
1.0x
2.0x
1
2
3
4
5
X
88.7
83.8
84.2
88.0
88.0
86.5
95.0
95.0
91.0
91.0
86.0
90.5
91.7
87.3
86.0
83.0
85.0
87.0
Weighted average = 88.2
(v) Precision of the analytical procedure. The following
data was used to determine the precision of the analytical
method:
(vi) Storage data. Samples were generated at 1.5 mg/m3
ethylene oxide at 85% relative humidity, 22°C and 633 mm.
All samples were taken for 20 minutes at 0.05 Lpm. Six samples
were analyzed as soon as possible and fifteen samples were
stored at refrigerated temperature (5°C) and fifteen samples
were stored at ambient temperature (23°C). These stored
samples were analyzed over a period of nineteen days.
Percent Recovery
Day
Analyzed
Refrigerated
Ambient
1
87.0
87.0
1
93.0
93.0
1
94.0
94.0
1
92.0
92.0
4
92.0
91.0
4
93.0
88.0
4
91.0
89.0
6
92.0
--
6
92.0
--
8
--
92.0
8
--
86.0
10
91.7
--
10
95.5
--
10
95.7
--
11
--
90.0
11
--
82.0
13
78.0
--
13
81.4
--
13
82.4
--
14
--
78.5
14
--
72.1
18
66.0
--
18
68.0
--
19
--
64.0
19
--
77.0
(vii) Breakthrough data.
(A) Breakthrough studies were done at 2 ppm (3.6 mg/m3)
at approximately 85% relative humidity at 22°C (ambient
temperature). Two charcoal tubes were used in series.
The backup tube was changed every 10 minutes and analyzed
for breakthrough. The flow rate was 0.050 Lpm.
Tube
No.
Time
(minutes)
Percent
Breakthrough
1
2
3
4
5
6
7
8
9
10
11
12
10
20
30
40
50
60
70
80
90
100
110
120
(*)
(*)
(*)
1.23
3.46
18.71
39.2
53.3
72.0
96.0
113.0
133.9
*None.
(B) The 5% breakthrough volume was reached when 2.6 liters
of test atmosphere were drawn through the charcoal tubes.
(j) References.
(i) “NIOSH Manual of Analytical Methods,” 2nd
ed. NIOSH: Cincinnati, 1977; Method S 286.
(ii) “IARC Monographs on the Evaluation of Carcinogenic
Risk of Chemicals to Man.” International Agency for
Research on Cancer: Lyon, 1976; Vol. II, p. 157.
(iii) Sax., N.I. “Dangerous Properties of Industrial
Materials,” 4th ed.; Van Nostrand Reinhold Company,
New York, 1975; p. 741.
(iv) “The Condensed Chemical Dictionary,” 9th
ed.; Hawley, G.G., ed.; Van Nostrand Reinhold Company, New
York, 1977; p. 361.
(4) Summary of other sampling procedures. OSHA believes that
several other types of monitoring equipment and techniques exist
for monitoring time-weighted averages. Considerable research
and method development is currently being performed, which will
lead to improvements and a wider variety of monitoring techniques.
A combination of monitoring procedures can be used. There probably
is no one best method for monitoring personal exposure to ethylene
oxide in all cases. There are advantages, disadvantages, and
limitations to each method. The method of choice will depend
on the need and requirements. Some commonly used methods include
the use of charcoal tubes, passive dosimeters, Tedler gas sampling
bags, detector tubes, photoionization detection units, infrared
detection units and gas chromatographs. A number of these methods
are described below.
(a) Charcoal tube sampling procedures.
(i) Qazi-Ketcham method (Ex-11-133)--This method consists
of collecting EtO on Columbia JXC activated carbon, desorbing
the EtO with carbon disulfide and analyzing by gas chromatography
with flame ionization detection. Union Carbide has recently
updated and revalidated this monitoring procedure. This
method is capable of determining both eight-hour time-weighted
average exposures and short-term exposures. The method was
validated to 0.5 ppm. Like other charcoal collecting procedures,
the method requires considerable analytical expertise.
(ii) ASTM-proposed method--The Ethylene Oxide Industry
Council (EOIC) has contracted with Clayton Environmental
Consultants, Inc. to conduct a collaborative study for the
proposed method. The ASTM-Proposed method is similar to
the method published by Qazi and Ketcham in the November
1977 American Industrial Hygiene Association Journal, and
to the method of Pilney and Coyne, presented at the 1979
American Industrial Hygiene Conference. After the air to
be sampled is drawn through an activated charcoal tube,
the ethylene oxide is desorbed from the tube using carbon
disulfide and is quantitated by gas chromatography utilizing
a flame ionization detector. The ASTM-proposed method specifies
a large two-section charcoal tube, shipment in dry ice,
storage at less than -5°C, and analysis within three weeks
to prevent migration and sample loss. Two types of charcoal
tubes are being tested--Pittsburgh Coconut-Based (PCB) and
columbia JXC charcoal. This collaborative study will give
an indication of the inter- and intralaboratory precision
and accuracy of the ASTM/proposed method. Several laboratories
have considerable expertise using the Qazi-Ketcham and Dow
methods.
(b) Passive monitors--Ethylene oxide diffuses into the monitor
and is collected in the sampling media. The DuPont Pro-Tek
badge collects EtO in an absorbing solution, which is analyzed
colorimetrically to determine the amount of EtO present. The
3M 350 badge collects the EtO on chemically treated charcoal.
Other passive monitors are currently being developed and tested.
Both 3M and DuPont have submitted data indicating their dosimeters
meet the precision and accuracy requirements of the proposed
ethylene oxide standard. Both presented laboratory validation
data to 0.2 ppm (Exs. 11-65, 4-20, 108, 109, 130).
(c) Tedlar gas sampling bags-samples are collected by drawing
a known volume of air into a Tedlar gas sampling bag. The
ethylene oxide concentration is often determined on-site using
a portable gas chromatograph or portable infrared spectometer.
(d) Detector tubes--A known volume of air is drawn through
a detector tube using a small hand pump. The concentration
of EtO is related to the length of stain developed in the
tube. Detector tubes are economical, easy to use, and give
an immediate readout. Unfortunately, partly because they are
nonspecific, their accuracy is often questionable. Since the
sample is taken over a short period of time, they may be useful
for determining the source of leaks.
(e) Direct reading instruments:
(i) There are numerous types of direct reading instruments,
each having its own strengths and weaknesses (Exs. 135B,
135C, 107, 11-78, 11-153). Many are relatively new, offering
greater sensitivity and specificity. Popular ethylene oxide
direct reading instruments include infrared detection units,
photoionization detection units, and gas chromatographs.
(ii) Portable infrared analyzers provide an immediate,
continuous indication of a concentration value; making them
particularly useful for locating high concentration pockets,
in leak detection and in ambient air monitoring. In infrared
detection units, the amount of infrared light absorbed by
the gas being analyzed at selected infrared
wavelengths is related to the concentration of a particular
component. Various models have either fixed or variable
infrared filters, differing cell pathlengths, and microcomputer
controls for greater sensitivity, automation, and interference
elimination.
(iii) A fairly recent detection system is photoionization
detection. The molecules are ionized by high energy ultraviolet
light. The resulting current is measured. Since different
substances have different ionization potentials, other organic
compounds may be ionized. The lower the lamp energy, the
better the selectivity. As a continuous monitor, photoionization
detection can be useful for locating high concentration
pockets, in leak detection, and continuous ambient air monitoring.
Both portable and stationary gas chromatographs are available
with various types of detectors, including photoionization
detectors. A gas chromatograph with a photoionization detector
retains the photoionization sensitivity, but minimizes or
eliminates interferences. For several GC/PID units, the
sensitivity is in the 0.1-0.2 ppm EtO range. The GC/PID
with microprocessors can sample up to 20 sample points sequentially,
calculate and record data, and activate alarms or ventilation
systems. Many are quite flexible and can be configured to
meet the specific analysis needs for the workplace.
(iv) DuPont presented their laboratory validation data
of the accuracy of the Qazi-Ketcham charcoal tube, the PCB
charcoal tube, Miran 103 IR analyzer, 3M #3550 monitor and
the DuPont C-70 badge. Quoting Elbert V. Kring:
(v) We also believe that OSHA's proposed accuracy in this
standard is appropriate. At plus or minus 25 percent at
one part per million, and plus or minus 35 percent below
that. And, our data indicates there's only one monitoring
method, right now, that we've tested thoroughly, that meets
that accuracy requirements. That is the DuPont Pro-Tek badge*
* *. We also believe that this kind of data should be confirmed
by another independent laboratory, using the same type dynamic
chamber testing (Tr. 1470).
Additional data by an independent laboratory following
their exact protocol was not submitted. However, information
was submitted on comparisons and precision and accuracy
of those monitoring procedures which indicate far better
precision and accuracy of those monitoring procedures than
that obtained by DuPont (Ex. 4-20, 130, 11-68, 11-133, 130,
135A).
(vi) The accuracy of any method depends to a large degree
upon the skills and experience of those who not only collect
the samples but also those who analyze the samples. Even
for methods that are collaboratively tested, some laboratories
are closer to the true values than others. Some laboratories
may meet the precision and accuracy requirements of the
method; others may consistently far exceed them for the
same method.
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