(1) Scope and
application.
(a) This section applies to all
occupational exposures to 1,3-Butadiene (BD), Chemical Abstracts Service
Registry No. 106-99-0, except as provided in (b) of this subsection.
(b)
(i)
Except for the recordkeeping provisions in subsection (13)(a) of this section,
this section does not apply to the processing, use, or handling of products
containing BD or to other work operations and streams in which BD is present
where objective data are reasonably relied upon that demonstrate the work
operation or the product or the group of products or operations to which it
belongs may not reasonably be foreseen to release BD in airborne concentrations
at or above the action level or in excess of the STEL under the expected
conditions of processing, use, or handling that will cause the greatest
possible release or in any plausible accident.
(ii) This section also does not apply to
work operations, products or streams where the only exposure to BD is from
liquid mixtures containing 0.1% or less of BD by volume or the vapors released
from such liquids, unless objective data become available that show that
airborne concentrations generated by such mixtures can exceed the action level
or STEL under reasonably predictable conditions of processing, use or handling
that will cause the greatest possible release.
(iii) Except for labeling requirements and
requirements for emergency response, this section does not apply to the
storage, transportation, distribution or sale of BD or liquid mixtures in
intact containers or in transportation pipelines sealed in such a manner as to
fully contain BD vapors or liquids.
(c) Where products or processes containing
BD are exempted under (b) of this subsection, the employer must maintain
records of the objective data supporting that exemption and the basis for the
employer's reliance on the data, as provided in subsection (13)(a) of this
section.
(2)
Definitions: For the purpose of this section, the following definitions shall
apply:
Action level. A concentration of airborne BD of
0.5 ppm calculated as an 8-hour time-weighted average.
Authorized person. Any person specifically
designated by the employer, whose duties require entrance into a regulated
area, or a person entering such an area as a designated representative of
employees to exercise the right to observe monitoring and measuring procedures
under subsection (4)(h) of this section, or a person designated under the WISH
Act or regulations issued under the WISH Act to enter a regulated area.
1,3-Butadiene. An organic compound with
chemical formula CH(2)=CH-CH=CH(2) that has a molecular weight of approximately
54.15 gm/mole.
Business day. Any Monday through Friday, except
those days designated as federal, state, local or company specific
holidays.
Complete blood count (CBC). Laboratory tests
performed on whole blood specimens and includes the following: White blood cell
count (WBC), hematocrit (Hct), red blood cell count (RBC), hemoglobin (Hgb),
differential count of white blood cells, red blood cell morphology, red blood
cell indices, and platelet count.
Day. Any part of a calendar day.
Director. The director of the department of
labor and industries, or authorized representatives.
Emergency situation. Any occurrence such as,
but not limited to, equipment failure, rupture of containers, or failure of
control equipment that may or does result in an uncontrolled significant
release of BD.
Employee exposure. Exposure of a worker to
airborne concentrations of BD which would occur if the employee were not using
respiratory protective equipment.
Objective data. Monitoring data, or
mathematical modelling or calculations based on composition, chemical and
physical properties of a material, stream or product.
Permissible exposure limits (PELs). Either the
8-hour time-weighted average (8-hour TWA) exposure or the short-term exposure
limit (STEL).
Physician or other licensed health care professional.
An individual whose legally permitted scope of practice (i.e., license,
registration, or certification) allows them to independently provide or be
delegated the responsibility to provide one or more of the specific health care
services required by (k) of this subsection.
Regulated area. Any area where airborne
concentrations of BD exceed or can reasonably be expected to exceed the 8-hour
time-weighted average (8-hour TWA) exposure of 1 ppm or the short-term exposure
limit (STEL) of 5 ppm for 15 minutes.
This section. This 1,3-butadi-ene
standard.
(3) Permissible
exposure limits (PELs).
(a) Time-weighted
average (TWA) limit. The employer must ensure that no employee is exposed to an
airborne concentration of BD in excess of one part BD per million parts of air
(ppm) measured as an eight (8)-hour time-weighted average.
(b) Short-term exposure limit (STEL). The
employer must ensure that no employee is exposed to an airborne concentration
of BD in excess of five parts of BD per million parts of air (5 ppm) as
determined over a sampling period of fifteen minutes.
(4) Exposure monitoring.
(a) General.
(i)
Determinations of employee exposure must be made from breathing
zone air samples that are representative of the 8-hour TWA and 15-minute
short-term exposures of each employee.
(ii)
Representative 8-hour TWA employee exposure must be determined on
the basis of one or more samples representing full-shift exposure for each
shift and for each job classification in each work area.
(iii) Representative 15-minute short-term
employee exposures must be determined on the basis of one or more samples
representing 15-minute exposures associated with operations that are most
likely to produce exposures above the STEL for each shift and for each job
classification in each work area.
(iv)
Except for the initial monitoring required under (b) of this
subsection, where the employer can document that exposure levels are equivalent
for similar operations on different work shifts, the employer need only
determine representative employee exposure for that operation from the shift
during which the highest exposure is expected.
(b) Initial monitoring.
(i) Each employer who has a workplace or
work operation covered by this section, must perform initial monitoring to
determine accurately the airborne concentrations of BD to which employees may
be exposed, or must rely on objective data pursuant to subsection (1)(b)(i) of
this section to fulfill this requirement. The initial monitoring required under
this subitem must be completed within sixty days of the introduction of BD into
the workplace.
(ii) Where the
employer has monitored within two years prior to the effective date of this
section and the monitoring satisfies all other requirements of this section,
the employer may rely on such earlier monitoring results to satisfy the
requirements of (b)(i) of this subsection, provided that the conditions under
which the initial monitoring was conducted have not changed in a manner that
may result in new or additional exposures.
(c) Periodic monitoring and its frequency.
(i) If the initial monitoring required by
(b) of this subsection reveals employee exposure to be at or above the action
level but at or below both the 8-hour TWA limit and the STEL, the employer must
repeat the representative monitoring required by (a) of this subsection every
twelve months.
(ii) If the initial
monitoring required by (b) of this subsection reveals employee exposure to be
above the 8-hour TWA limit, the employer must repeat the representative
monitoring required by (a)(ii) of this subsection at least every three months
until the employer has collected two samples per quarter (each at least 7 days
apart) within a two-year period, after which such monitoring must occur at
least every six months.
(iii) If
the initial monitoring required by (b) of this subsection reveals employee
exposure to be above the STEL, the employer must repeat the representative
monitoring required by (a)(iii) of this subsection at least every three months
until the employer has collected two samples per quarter (each at least 7 days
apart) within a two-year period, after which such monitoring must occur at
least every six months.
(iv) The
employer may alter the monitoring schedule from every six months to annually
for any required representative monitoring for which two consecutive
measurements taken at least 7 days apart indicate that employee exposure has
decreased to or below the 8-hour TWA, but is at or above the action
level.
(d) Termination
of monitoring.
(i) If the initial monitoring
required by (b) of this subsection reveals employee exposure to be below the
action level and at or below the STEL, the employer may discontinue the
monitoring for employees whose exposures are represented by the initial
monitoring.
(ii) If the periodic
monitoring required by (c) of this subsection reveals that employee exposures,
as indicated by at least two consecutive measurements taken at least 7 days
apart, are below the action level and at or below the STEL, the employer may
discontinue the monitoring for those employees who are represented by such
monitoring.
(e)
Additional monitoring.
(i) The employer must
institute the exposure monitoring required under subsection (4) 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
BD or when the employer has any reason to suspect that a change may result in
new or additional exposures.
(ii)
Whenever spills, leaks, ruptures or other breakdowns occur that may lead to
employee exposure above the 8-hour TWA limit or above the STEL, the employer
must monitor (using leak source, such as direct reading instruments, area or
personal monitoring), after the cleanup of the spill or repair of the leak,
rupture or other breakdown, to ensure that exposures have returned to the level
that existed prior to the incident.
(f) Accuracy of monitoring.
Monitoring must be accurate, at a confidence level of 95
percent, to within plus or minus 25 percent for airborne concentrations of BD
at or above the 1 ppm TWA limit and to within plus or minus 35 percent for
airborne concentrations of BD at or above the action level of 0.5 ppm and below
the 1 ppm TWA limit.
(g)
Employee notification of monitoring results.
(i)
The employer must, within 5 business days after the receipt of
the results of any monitoring performed under this section, notify the affected
employees of these results in writing either individually or by posting of
results in an appropriate location that is accessible to affected
employees.
(ii) The employer must,
within 15 business days after receipt of any monitoring performed under this
section indicating the 8-hour TWA or STEL has been exceeded, provide the
affected employees, in writing, with information on the corrective action being
taken by the employer to reduce employee exposure to or below the 8-hour TWA or
STEL and the schedule for completion of this action.
(h) Observation of monitoring.
(i) Employee observation. The employer must
provide affected employees or their designated representatives an opportunity
to observe any monitoring of employee exposure to BD conducted in accordance
with this section.
(ii)
Observation procedures. When observation of the monitoring of employee exposure
to BD requires entry into an area where the use of protective clothing or
equipment is required, the employer must provide the observer at no cost with
protective clothing and equipment, and must ensure that the observer uses this
equipment and complies with all other applicable safety and health
procedures.
(5)
Regulated areas.
(a) The
employer must establish a regulated area wherever occupational exposures to
airborne concentrations of BD exceed or can reasonably be expected to exceed
the permissible exposure limits, either the 8-hour TWA or the STEL.
(b) Access to regulated areas must be
limited to authorized persons.
(c)
Regulated areas must be demarcated from the rest of the workplace in any manner
that minimizes the number of employees exposed to BD within the regulated
area.
(d) An employer at a
multiemployer worksite who establishes a regulated area must communicate the
access restrictions and locations of these areas to other employers with work
operations at that worksite whose employees may have access to these
areas.
(6) Methods of
compliance.
(a) Engineering controls and
work practices.
(i) The employer must
institute engineering controls and work practices to reduce and maintain
employee exposure to or below the PELs, except to the extent that the employer
can establish that these controls are not feasible or where subsection
(8)(a)(i) of this section applies.
(ii)
Wherever the feasible engineering controls and work practices
which can be instituted are not sufficient to reduce employee exposure to or
below the 8-hour TWA or STEL, the employer must use them to reduce employee
exposure to the lowest levels achievable by these controls and must supplement
them by the use of respiratory protection that complies with the requirements
of subsection (8) of this section.
(b) Compliance plan.
(i) Where any exposures are over the PELs,
the employer must establish and implement a written plan to reduce employee
exposure to or below the PELs primarily by means of engineering and work
practice controls, as required by (a) of this subsection, and by the use of
respiratory protection where required or permitted under this section. No
compliance plan is required if all exposures are under the PELs.
(ii) The written compliance plan must
include a schedule for the development and implementation of the engineering
controls and work practice controls including periodic leak detection
surveys.
(iii) Copies of the
compliance plan required in (b) of this subsection must be furnished upon
request for examination and copying to the director, affected employees and
designated employee representatives. Such plans must be reviewed at least every
12 months, and must be updated as necessary to reflect significant changes in
the status of the employer's compliance program.
(iv) The employer must not implement a
schedule of employee rotation as a means of compliance with the PELs.
(7) Exposure goal
program.
(a) For those operations and job
classifications where employee exposures are greater than the action level, in
addition to compliance with the PELs, the employer must have an exposure goal
program that is intended to limit employee exposures to below the action level
during normal operations.
(b)
Written plans for the exposure goal program must be furnished upon request for
examination and copying to the director, affected employees and designated
employee representatives.
(c) Such
plans must be updated as necessary to reflect significant changes in the status
of the exposure goal program.
(d)
Respirator use is not required in the exposure goal program.
(e) The exposure goal program must include
the following items unless the employer can demonstrate that the item is not
feasible, will have no significant effect in reducing employee exposures, or is
not necessary to achieve exposures below the
action level:
(i) A leak prevention, detection, and repair
program.
(ii) A program for
maintaining the effectiveness of local exhaust ventilation systems.
(iii) The use of pump exposure control
technology such as, but not limited to, mechanical double-sealed or seal-less
pumps.
(iv) Gauging devices
designed to limit employee exposure, such as magnetic gauges on rail
cars.
(v) Unloading devices
designed to limit employee exposure, such as a vapor return system.
(vi) A program to maintain BD concentration
below the action level in control rooms by use of engineering
controls.
(8)
Respiratory protection.
(a)
General. For employees who use respirators required by this section, the
employer must provide each employee an appropriate respirator that complies
with the requirements of this subsection. Respirators must be used during:
(i) Periods necessary to install or
implement feasible engineering and work-practice controls;
(ii) Nonroutine work operations that are
performed infrequently and for which exposures are limited in
duration;
(iii) Work operations
for which feasible engineering controls and work-practice controls are not yet
sufficient to reduce employee exposures to or below the PELs;
(iv) Emergencies.
(b) Respirator program.
(i) The employer must implement a
respiratory protection program as required by chapter
296-842 WAC, except WAC
296-842-13005
and
296-842-14005,
which covers each employee required by this section to use a
respirator.
(ii) If air-purifying
respirators are used, the employer must replace the air-purifying filter
elements according to the replacement schedule set for the class of respirators
listed in Table 1 of this section, and at the beginning of each work
shift.
(iii) Instead of using the
replacement schedule listed in Table 1 of this section, the employer may
replace cartridges or canisters at 90% of their expiration service life,
provided the employer:
(A) Demonstrates that
employees will be adequately protected by this procedure;
(B) Uses BD breakthrough data for this
purpose that have been derived from tests conducted under worst-case conditions
of humidity, temperature, and air-flow rate through the filter element, and the
employer also describes the data supporting the cartridge- or canister-change
schedule, as well as the basis for using the data in the employer's respirator
program.
(iv) A label
must be attached to each filter element to indicate the date and time it is
first installed on the respirator.
(v)
If NIOSH approves an end-of-service-life indicator (ESLI) for an
air-purifying filter element, the element may be used until the ESLI shows no
further useful service life or until the element is replaced at the beginning
of the next work shift, whichever occurs first.
(vi) Regardless of the air-purifying element
used, if an employee detects the odor of BD, the employer must replace the
air-purifying element immediately.
(c) Respirator selection.
(i) The employer must select appropriate
respirators from Table 1 of this section.
Table 1. - Minimum Requirements for Respiratory
Protection for Airborne BD
Concentration of Airborne BD (ppm) or condition of
use
|
Minimum required respirator
|
Less than or equal to 5 ppm (5 times
PEL)
|
(a) Air-purifying half mask or full facepiece
respirator equipped with approved BD or organic vapor cartridges or canisters.
Cartridges or canisters shall be replaced every 4 hours.
|
Less than or equal to 10 ppm (10 times
PEL)
|
(a) Air-purifying half mask or full facepiece
respirator equipped with approved BD or organic vapor cartridges or canisters.
Cartridges or canisters shall be replaced every 3 hours.
|
Less than or equal to 25 ppm (25 times
PEL)
|
(a) Air-purifying full facepiece respirator equipped
with approved BD or organic vapor cartridges or canisters. Cartridges or
canisters shall be replaced every 2 hours.
|
(b) Any powered air-purifying respirator equipped
with approved BD or organic vapor cartridges. PAPR cartridges shall be replaced
every 2 hours.
|
(c) Continuous flow supplied air respirator equipped
with a hood or helmet.
|
Less than or equal to 50 ppm (50 times
PEL)
|
(a) Air-purifying full facepiece respirator equipped
with approved BD or organic vapor cartridges or canisters. Cartridges or
canisters shall be replaced every 1 hour.
|
(b) Powered air purifying respirator equipped with a
tight-fitting facepiece and an approved BD or organic vapor cartridges. PAPR
cartridges shall be replaced every 1 hour.
|
Less than or equal to 1,000 ppm (1,000 times
PEL)
|
(a) Supplied air respirator equipped with a half
mask or full facepiece and operated in a pressure demand or other positive
pressure mode.
|
Greater than 1,000 ppm
|
(a) Self-contained breathing unknown concentration,
or apparatus equipped with a fire fighting full facepiece and operated in a
pressure demand or other positive pressure mode.
|
(b) Any supplied air respirator equipped with a full
facepiece and operated in a pressure demand or other positive pressure mode in
combination with an auxiliary self-contained breathing apparatus operated in a
pressure demand or other positive pressure mode.
|
Escape from IDLH Conditions
|
(a) Any positive pressure self-contained breathing
apparatus with an appropriate service life.
|
(b) Any air-purifying full facepiece respirator
equipped with a front or back mounted BD or organic vapor canister.
|
Notes:
|
Respirators approved for use in higher concentrations
are permitted to be used in lower concentrations. Full facepiece is required
when eye irritation is anticipated.
|
(ii)
Air-purifying respirators must have filter elements certified by NIOSH for
organic vapor or BD.
(iii) When an
employee whose job requires the use of a respirator cannot use a
negative-pressure respirator, the employer must provide the employee with a
respirator that has less breathing resistance than the negative-pressure
respirator, such as a powered air-purifying respirator or supplied-air
respirator, when the employee is able to use it and if it provides the employee
adequate protection.
(9)
Protective clothing and equipment. Where appropriate to prevent
eye contact and limit dermal exposure to BD, the employer must provide
protective clothing and equipment at no cost to the employee and must ensure
its use. Eye and face protection must meet the requirements of WAC
296-800-160.
(10) Emergency situations. Written plan. A
written plan for
emergency situations must be developed, or an existing plan
must be modified, to contain the applicable elements specified in WAC
296-24-567
Employee
emergency plans and fire prevention plans, and in chapter
296-843 WAC,
Hazardous waste operations , for each workplace where there is a possibility of
an
emergency.
(11) Medical
screening and surveillance.
(a) Employees
covered. The employer must institute a medical screening and surveillance
program as specified in this subsection for:
(i)
Each employee with exposure to BD at concentrations at or above
the action level on 30 or more days or for employees who have or may have
exposure to BD at or above the PELs on 10 or more days a year;
(ii) Employers (including successor owners)
must continue to provide medical screening and surveillance for employees, even
after transfer to a non-BD exposed job and regardless of when the employee is
transferred, whose work histories suggest exposure to BD:
(A) At or above the PELs on 30 or more days
a year for 10 or more years;
(B)
At or above the action level on 60 or more days a year for 10 or more years;
or
(C) Above 10 ppm on 30 or more
days in any past year; and
(iii)
Each employee exposed to BD following an emergency
situation.
(b) Program
administration.
(i) The employer must ensure
that the health questionnaire, physical examination and medical procedures are
provided without cost to the employee, without loss of pay, and at a reasonable
time and place.
(ii) Physical
examinations, health questionnaires, and medical procedures must be performed
or administered by a physician or other licensed health care
professional.
(iii) Laboratory
tests must be conducted by an accredited laboratory.
(c) Frequency of medical screening
activities. The employer must make medical screening available on the following
schedule:
(i) For each employee covered
under (a)(i) and (ii) of this subsection, a health questionnaire and complete
blood count (CBC) with differential and platelet count every year, and a
physical examination as specified below:
(A)
An initial physical examination that meets the requirements of this rule, if
twelve months or more have elapsed since the last physical examination
conducted as part of a medical screening program for BD exposure;
(B) Before assumption of duties by the
employee in a job with BD exposure;
(C)
Every 3 years after the initial physical examination;
(D) At the discretion of the physician or
other licensed health care professional reviewing the annual health
questionnaire and CBC;
(E) At the
time of employee reassignment to an area where exposure to BD is below the
action level, if the employee's past exposure history does not meet the
criteria of (a)(ii) of this subsection for continued coverage in the screening
and surveillance program, and if twelve months or more have elapsed since the
last physical examination; and
(F)
At termination of employment if twelve months or more have elapsed since the
last physical examination.
(ii)
Following an emergency situation, medical screening must be
conducted as quickly as possible, but not later than 48 hours after the
exposure.
(iii) For each employee
who must wear a respirator, physical ability to perform the work and use the
respirator must be determined as required by chapter
296-842 WAC.
(d) Content of medical screening.
(i) Medical screening for employees covered
by (a)(i) and (ii) of this subsection must include:
(A)
A baseline health questionnaire that includes a comprehensive
occupational and health history and is updated annually. Particular emphasis
must be placed on the hematopoietic and reticuloendothelial systems, including
exposure to chemicals, in addition to BD, that may have an adverse effect on
these systems, the presence of signs and symptoms that might be related to
disorders of these systems, and any other information determined by the
examining physician or other licensed health care professional to be necessary
to evaluate whether the employee is at increased risk of material impairment of
health from BD exposure. Health questionnaires must consist of the sample forms
in Appendix C to this section, or be equivalent to those samples;
(B) A complete physical examination, with
special emphasis on the liver, spleen, lymph nodes, and skin;
(C) A CBC; and
(D) Any other test which the examining
physician or other licensed health care professional deems necessary to
evaluate whether the employee may be at increased risk from exposure to
BD.
(ii) Medical
screening for employees exposed to BD in an emergency situation must focus on
the acute effects of BD exposure and at a minimum include: A CBC within 48
hours of the exposure and then monthly for three months; and a physical
examination if the employee reports irritation of the eyes, nose, throat,
lungs, or skin, blurred vision, coughing, drowsiness, nausea, or headache.
Continued employee participation in the medical screening and surveillance
program, beyond these minimum requirements, must be at the discretion of the
physician or other licensed health care professional.
(e) Additional medical evaluations and
referrals.
(i) Where the results of medical
screening indicate abnormalities of the hematopoietic or reticuloendothelial
systems, for which a nonoccupational cause is not readily apparent, the
examining physician or other licensed health care professional must refer the
employee to an appropriate specialist for further evaluation and must make
available to the specialist the results of the medical screening.
(ii) The specialist to whom the employee is
referred under this subsection must determine the appropriate content for the
medical evaluation, e.g., examinations, diagnostic tests and procedures,
etc.
(f) Information
provided to the physician or other licensed health care professional. The
employer must provide the following information to the examining physician or
other licensed health care professional involved in the evaluation:
(i) A copy of this section including its
appendices;
(ii) A description of
the affected employee's duties as they relate to the employee's BD
exposure;
(iii) The employee's
actual or representative BD exposure level during employment tenure, including
exposure incurred in an emergency situation;
(iv) A description of pertinent personal
protective equipment used or to be used; and
(v)
Information, when available, from previous employment-related
medical evaluations of the affected employee which is not otherwise available
to the physician or other licensed health care professional or the
specialist.
(g) The
written medical opinion.
(i) For each
medical evaluation required by this section, the employer must ensure that the
physician or other licensed health care professional produces a written opinion
and provides a copy to the employer and the employee within 15 business days of
the evaluation. The written opinion must be limited to the following
information:
(A) The occupationally
pertinent results of the medical evaluation;
(B)
A medical opinion concerning whether the employee has any
detected medical conditions which would place the employee's health at
increased risk of material impairment from exposure to BD;
(C) Any recommended limitations upon the
employee's exposure to BD; and
(D)
A statement that the employee has been informed of the results of the medical
evaluation and any medical conditions resulting from BD exposure that require
further explanation or treatment.
(ii) The written medical opinion provided to
the employer must not reveal specific records, findings, and diagnoses that
have no bearing on the employee's ability to work with BD.
Note: |
This provision does not negate the ethical obligation of
the physician or other licensed health care professional to transmit any other
adverse findings directly to the employee. |
(h)
Medical surveillance.
(i) The
employer must ensure that information obtained from the medical screening
program activities is aggregated (with all personal identifiers removed) and
periodically reviewed, to ascertain whether the health of the employee
population of that employer is adversely affected by exposure to BD.
(ii) Information learned from medical
surveillance activities must be disseminated to covered employees, as defined
in (a) of this subsection, in a manner that ensures the confidentiality of
individual medical information.
(12) Communication of BD hazards.
(a) Hazard communication - General.
(i) Chemical manufacturers, importers,
distributors and employers must comply with all requirements of the Hazard
Communication Standard (HCS), WAC
296-901-140
for BD.
(ii) In classifying the
hazards of BD at least the following hazards are to be addressed: Cancer; eye
and respiratory tract irritation; central nervous system effects; and
flamma-bility.
(iii) Employers
must include BD in the hazard communication program established to comply with
the HCS, WAC
296-901-140.
Employers must ensure that each employee has access to labels on containers of
BD and to safety data sheets, and is trained in accordance with the
requirements of HCS and (b) of this subsection.
(b) Employee information and training.
(i) The employer must train each employee
who is potentially exposed to BD at or above the
action level or the STEL in
accordance with the requirements of WAC
296-901-140
Hazard communication.
(ii) The
employer must institute a training program for all employees who are
potentially exposed to BD at or above the action level or the STEL, ensure
employee participation in the program and maintain a record of the contents of
such program.
(iii) Training must
be provided prior to or at the time of initial assignment to a job potentially
involving exposure to BD at or above the action level or STEL and at least
annually thereafter.
(iv) The
training program must be conducted in a manner that the employee is able to
understand. The employer must ensure that each employee exposed to BD over the
action level or STEL is informed of the following:
(A)
The health hazards associated with BD exposure, and the purpose
and a description of the medical screening and surveillance program required by
this section;
(B) The quantity,
location, manner of use, release, and storage of BD and the specific operations
that could result in exposure to BD, especially exposures above the PEL or
STEL;
(C) The engineering controls
and work practices associated with the employee's job assignment, and emergency
procedures and personal protective equipment;
(D) The measures employees can take to
protect themselves from exposure to BD;
(E)
The contents of this standard and its appendices; and
(F) The right of each employee exposed to BD
at or above the
action level or STEL to obtain:
(I)
Medical examinations as required by subsection (10) of this
section at no cost to the employee;
(II)
The employee's medical records required to be maintained by
subsection (13)(c) of this section; and
(III)
All air monitoring results representing the employee's exposure
to BD and required to be kept by subsection (13)(b) of this section.
(c) Access
to information and training materials.
(i)
The employer must make a copy of this standard and its appendices readily
available without cost to all affected employees and their designated
representatives and must provide a copy if requested.
(ii) The employer must provide to the
director, or the designated employee representatives, upon request, all
materials relating to the employee information and the training
program.
(13)
Recordkeeping.
(a) Objective
data for exemption from initial monitoring.
(i)
Where the processing, use, or handling of products or streams
made from or containing BD are exempted from other requirements of this section
under subsection (1)(b) of this section, or where objective data have been
relied on in lieu of initial monitoring under subsection (4)(b)(ii) of this
section, the employer must establish and maintain a record of the objective
data reasonably relied upon in support of the exemption.
(ii) This record must include at least the
following information:
(A) The product or
activity qualifying for exemption;
(B)
The source of the objective data;
(C) The testing protocol, results of
testing, and analysis of the material for the release of BD;
(D) A description of the operation exempted
and how the data support the exemption; and
(E)
Other data relevant to the operations, materials, processing, or
employee exposures covered by the exemption.
(iii) The employer must maintain this record
for the duration of the employer's reliance upon such objective data.
(b) Exposure measurements.
(i) The employer must establish and maintain
an accurate record of all measurements taken to monitor employee exposure to BD
as prescribed in subsection (4) of this section.
(ii) The record must include at least the
following information:
(A) The date of
measurement;
(B) The operation
involving exposure to BD which is being monitored;
(C) Sampling and analytical methods used and
evidence of their accuracy;
(D)
Number, duration, and results of samples taken;
(E) Type of protective devices worn, if
any;
(F) Name, Social Security
number and exposure of the employees whose exposures are represented;
and
(G) The written corrective
action and the schedule for completion of this action required by subsection
(4)(g)(ii) of this section.
(iii)
The employer must maintain this record for at least 30 years in
accordance with chapter
296-802 WAC.
(c) Medical screening and surveillance.
(i) The employer must establish and maintain
an accurate record for each employee subject to medical screening and
surveillance under this section.
(ii)
The record must include at least the following information:
(A) The name and Social Security number of
the employee;
(B) Physician's or
other licensed health care professional's written opinions as described in
subsection (11)(e) of this section;
(C)
A copy of the information provided to the physician or other
licensed health care professional as required by subsection (11)(e) of this
section.
(iii) Medical
screening and surveillance records must be maintained for each employee for the
duration of employment plus 30 years, in accordance with chapter
296-802
WAC.
(d) Availability.
(i) The employer, upon written request, must
make all records required to be maintained by this section available for
examination and copying to the director.
(ii)
Access to records required to be maintained by (a) and (b) of
this subsection must be granted in accordance with chapter
296-802
WAC.
(e) Transfer of
records. The employer shall transfer medical and exposure records as set forth
in WAC
296-802-60005.
(14) Start-up dates.
(a) The initial monitoring required under
subsection (4)(b) of this section must be completed immediately or within sixty
days of the introduction of BD into the workplace.
(b) The requirements of subsections (3)
through (13) of this section, including feasible work practice controls but not
including engineering controls specified in subsection (6)(a) of this section,
must be complied with immediately.
(15) Appendices.
Appendices A, B, C, D, and F to this section are
informational and are not intended to create any additional obligations not
otherwise imposed or to detract from any existing obligations.
Appendix A. Substance Safety Data Sheet For 1,3-Buta-diene
(Non-Mandatory)
(1) Substance
Identification.
(a) Substance: 1,3-Butadiene
(CH(2)=CH-CH=CH(2)).
(b) Synonyms:
1,3-Butadiene (BD); butadiene; biethylene; bi-vinyl; divinyl; butadiene-1,3;
buta-1,3-diene; erythrene; NCI-C50602; CAS-106-99-0.
(c) BD can be found as a gas or
liquid.
(d) BD is used in
production of styrenebutadiene rubber and polybutadiene rubber for the tire
industry. Other uses include copolymer latexes for carpet backing and paper
coating, as well as resins and polymers for pipes and automobile and appliance
parts. It is also used as an intermediate in the production of such chemicals
as fungicides.
(e) Appearance and
odor: BD is a colorless, noncorrosive, flammable gas with a mild aromatic odor
at standard ambient temperature and pressure.
(f) Permissible exposure: Exposure may not
exceed 1 part BD per million parts of air averaged over the 8-hour workday, nor
may short-term exposure exceed 5 parts of BD per million parts of air averaged
over any 15-minute period in the 8-hour workday.
(2) Health Hazard Data.
(a) BD can affect the body if the gas is
inhaled or if the liquid form, which is very cold (cryogenic), comes in contact
with the eyes or skin.
(b) Effects
of overexposure: Breathing very high levels of BD for a short time can cause
central nervous system effects, blurred vision, nausea, fatigue, headache,
decreased blood pressure and pulse rate, and unconsciousness. There are no
recorded cases of accidental exposures at high levels that have caused death in
humans, but this could occur. Breathing lower levels of BD may cause irritation
of the eyes, nose, and throat. Skin contact with liquefied BD can cause
irritation and frostbite.
(c)
Long-term (chronic) exposure: BD has been found to be a potent carcinogen in
rodents, inducing neoplastic lesions at multiple target sites in mice and rats.
A recent study of BD-exposed workers showed that exposed workers have an
increased risk of developing leukemia. The risk of leukemia increases with
increased exposure to BD. OSHA has concluded that there is strong evidence that
workplace exposure to BD poses an increased risk of death from cancers of the
lymphohematopoietic system.
(d)
Reporting signs and symptoms: You should inform your supervisor if you develop
any of these signs or symptoms and suspect that they are caused by exposure to
BD.
(3) Emergency
First-Aid Procedures.
In the event of an emergency, follow the emergency plan and
procedures designated for your work area. If you have been trained in first-aid
procedures, provide the necessary first aid measures. If necessary, call for
additional assistance from co-workers and emergency medical personnel.
(a) Eye and Skin Exposures: If there is a
potential that liquefied BD can come in contact with eye or skin, face shields
and skin protective equipment must be provided and used. If liquefied BD comes
in contact with the eye, immediately flush the eyes with large amounts of
water, occasionally lifting the lower and the upper lids. Flush repeatedly. Get
medical attention immediately. Contact lenses should not be worn when working
with this chemical. In the event of skin contact, which can cause frostbite,
remove any contaminated clothing and flush the affected area repeatedly with
large amounts of tepid water.
(b)
Breathing: If a person breathes in large amounts of BD, move the exposed person
to fresh air at once. If breathing has stopped, begin cardiopulmonary
resuscitation (CPR) if you have been trained in this procedure. Keep the
affected person warm and at rest. Get medical attention immediately.
(c) Rescue: Move the affected person from
the hazardous exposure. If the exposed person has been overcome, call for help
and begin emergency rescue procedures. Use extreme caution so that you do not
become a casualty. Understand the plant's emergency rescue procedures and know
the locations of rescue equipment before the need arises.
(4) Respirators and Protective Clothing.
(a) Respirators: Good industrial hygiene
practices recommend that engineering and work practice controls be used to
reduce environmental concentrations to the permissible exposure level. However,
there are some exceptions where respirators may be used to control exposure.
Respirators may be used when engineering and work practice controls are not
technically feasible, when such controls are in the process of being installed,
or when these controls fail and need to be supplemented or during brief,
nonroutine, intermittent exposure. Respirators may also be used in situations
involving nonroutine work operations which are performed infrequently and in
which exposures are limited in duration, and in
emergency situations. In some
instances cartridge respirator use is allowed, but only with strict time
constraints. For example, at exposure below 5 ppm BD, a cartridge (or canister)
respirator, either full or half face, may be used, but the cartridge must be
replaced at least every 4 hours, and it must be replaced every 3 hours when the
exposure is between 5 and 10 ppm.
If the use of respirators is necessary, the only respirators
permitted are those that have been approved by the National Institute for
Occupational Safety and Health (NIOSH). In addition to respirator selection, a
complete respiratory protection program must be instituted which includes
regular training, maintenance, fit testing, inspection, cleaning, and
evaluation of respirators. If you can smell BD while wearing a respirator,
proceed immediately to fresh air, and change cartridge (or canister) before
reentering an area where there is BD exposure. If you experience difficulty in
breathing while wearing a respirator, tell your supervisor.
(b) Protective Clothing: Employees should be
provided with and required to use impervious clothing, gloves, face shields
(eight-inch minimum), and other appropriate protective clothing necessary to
prevent the skin from becoming frozen by contact with liquefied BD (or a vessel
containing liquid BD).
Employees should be provided with and required to use
splash-proof safety goggles where liquefied BD may contact the eyes.
(5) Precautions for
Safe Use, Handling, and Storage.
(a) Fire
and Explosion Hazards: BD is a flammable gas and can easily form explosive
mixtures in air. It has a lower explosive limit of 2%, and an upper explosive
limit of 11.5%. It has an autoignition temperature of 420 deg. C (788 deg. F).
Its vapor is heavier than air (vapor density, 1.9) and may travel a
considerable distance to a source of ignition and flash back. Usually it
contains inhibitors to prevent self-polymerization (which is accompanied by
evolution of heat) and to prevent formation of explosive peroxides. At elevated
temperatures, such as in fire conditions, polymerization may take place. If the
polymerization takes place in a container, there is a possibility of violent
rupture of the container.
(b)
Hazard: Slightly toxic. Slight respiratory irritant. Direct contact of
liquefied BD on skin may cause freeze burns and frostbite.
(c) Storage: Protect against physical damage
to BD containers. Outside or detached storage of BD containers is preferred.
Inside storage should be in a cool, dry, well-ventilated, noncombustible
location, away from all possible sources of ignition. Store cylinders
vertically and do not stack. Do not store with oxidizing material.
(d) Usual Shipping Containers: Liquefied BD
is contained in steel pressure apparatus.
(e)
Electrical Equipment: Electrical installations in Class I
hazardous locations, as defined in Article 500 of the National Electrical Code,
should be in accordance with Article 501 of the Code. If explosion-proof
electrical equipment is necessary, it shall be suitable for use in Group B.
Group D equipment may be used if such equipment is isolated in accordance with
Section 501-5(a) by sealing all conduit 1/2-inch size or larger. See Venting of
Deflagrations (NFPA No. 68, 1994), National Electrical Code (NFPA No. 70,
1996), Static Electricity (NFPA No. 77, 1993), Lightning Protection Systems
(NFPA No. 780, 1995), and Fire Hazard Properties of Flammable Liquids, Gases
and Volatile Solids (NFPA No. 325, 1994).
(f)
Fire Fighting: Stop flow of gas. Use water to keep fire-exposed
containers cool. Fire extinguishers and quick drenching facilities must be
readily available, and you should know where they are and how to operate
them.
(g) Spill and Leak: Persons
not wearing protective equipment and clothing should be restricted from areas
of spills or leaks until clean-up has been completed. If BD is spilled or
leaked, the following steps should be taken:
(i)
Eliminate all ignition sources.
(ii) Ventilate area of spill or
leak.
(iii) If in liquid form, for
small quantities, allow to evaporate in a safe manner.
(iv) Stop or control the leak if this can be
done without risk. If source of leak is a cylinder and the leak cannot be
stopped in place, remove the leaking cylinder to a safe place and repair the
leak or allow the cylinder to empty.
(h) Disposal: This substance, when discarded
or disposed of, is a hazardous waste according to Federal regulations (40
C.F.R. part
261). It is listed as hazardous waste number D001 due to its
ignitability. The transportation, storage, treatment, and disposal of this
waste material must be conducted in compliance with 40 C.F.R. parts
262,
263,
264,
268 and
270. Disposal can occur only in properly permitted facilities.
Check state and local regulation of any additional requirements as these may be
more restrictive than federal laws and regulation.
(i) You should not keep food, beverages, or
smoking materials in areas where there is BD exposure, nor should you eat or
drink in such areas.
(j) Ask your
supervisor where BD is used in your work area and ask for any additional plant
safety and health rules.
(6)
Medical Requirements.
Your employer is required to offer you the opportunity to
participate in a medical screening and surveillance program if you are exposed
to BD at concentrations exceeding the action level (0.5 ppm BD as an 8-hour
TWA) on 30 days or more a year, or at or above the 8-hr TWA (1 ppm) or STEL (5
ppm for 15 minutes) on 10 days or more a year. Exposure for any part of a day
counts. If you have had exposure to BD in the past, but have been transferred
to another job, you may still be eligible to participate in the medical
screening and surveillance program.
The WISHA rule specifies the past exposures that would
qualify you for participation in the program. These past exposure are work
histories that suggest the following:
(a)
That you have been exposed at or above the PELs on 30 days a year
for 10 or more years;
(b) That you
have been exposed at or above the action level on 60 days a year for 10 or more
years; or
(c) That you have been
exposed above 10 ppm on 30 days in any past year.
Additionally, if you are exposed to BD in an emergency
situation, you are eligible for a medical examination within 48 hours. The
basic medical screening program includes a health questionnaire, physical
examination, and blood test. These medical evaluations must be offered to you
at a reasonable time and place, and without cost or loss of pay.
(7) Observation of
Monitoring.
Your employer is required to perform measurements that are
representative of your exposure to BD and you or your designated representative
are entitled to observe the monitoring procedure. You are entitled to observe
the steps taken in the measurement procedure, and to record the results
obtained. When the monitoring procedure is taking place in an area where
respirators or personal protective clothing and equipment are required to be
worn, you or your representative must also be provided with, and must wear, the
protective clothing and equipment.
(8)
Access to Information.
(a)
Each year, your employer is required to inform you of the information contained
in this appendix. In addition, your employer must instruct you in the proper
work practices for using BD, emergency procedures, and the correct use of
protective equipment.
(b) Your
employer is required to determine whether you are being exposed to BD. 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 and of the schedule to implement
these actions.
(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 thirty years.
(d) Your employer is required to release
your exposure and medical records to you or your representative upon your
request.
Appendix B. Substance Technical Guidelines for 1,3-Butadiene
(Non-Mandatory)
(1) Physical and
Chemical Data.
(a) Substance identification:
(i) Synonyms: 1,3-Butadiene (BD); butadiene;
biethylene; bivinyl; divinyl; butadiene-1,3; buta-1,3-diene; erythrene;
NCI-C50620; CAS-106-99-0.
(ii)
Formula: (CH(2)=CH-CH=CH(2)).
(iii)
Molecular weight: 54.1.
(b) Physical data:
(i)
Boiling point (760 mm Hg): -4.7 deg. C (23.5 deg. F).
(ii) Specific gravity (water = 1):0.62 at 20
deg. C (68 deg. F).
(iii) Vapor
density (air = 1 at boiling point of BD): 1.87.
(iv) Vapor pressure at 20 deg. C (68 deg.
F): 910 mm Hg.
(v) Solubility in
water, g/100 g water at 20 deg. C (68 deg. F): 0.05.
(vi) Appearance and odor: Colorless,
flammable gas with a mildly aromatic odor. Liquefied BD is a colorless liquid
with a mildly aromatic odor.
(2) Fire, Explosion, and Reactivity Hazard
Data.
(a) Fire:
(i)
Flash point: -76 deg. C (-105 deg. F) for take out; liquefied BD;
Not applicable to BD gas.
(ii)
Stability: A stabilizer is added to the monomer to inhibit formation of polymer
during storage. Forms explosive peroxides in air in absence of
inhibitor.
(iii) Flammable limits
in air, percent by volume: Lower: 2.0; Upper: 11.5.
(iv) Extinguishing media: Carbon dioxide for
small fires, polymer or alcohol foams for large fires.
(v) Special fire fighting procedures: Fight
fire from protected location or maximum possible distance. Stop flow of gas
before extinguishing fire. Use water spray to keep fire-exposed cylinders
cool.
(vi) Unusual fire and
explosion hazards: BD vapors are heavier than air and may travel to a source of
ignition and flash back. Closed containers may rupture violently when
heated.
(vii) For purposes of
compliance with the requirements of WAC
296-24-330, BD
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, BD is
classified as a Class B fire hazard.
(ix)
For purposes of compliance with WAC
296-24-956 and
296-800-280,
locations classified as hazardous due to the presence of BD shall be Class
I.
(b) Reactivity:
(i) Conditions contributing to instability:
Heat. Peroxides are formed when inhibitor concentration is not maintained at
proper level. At elevated temperatures, such as in fire conditions,
polymerization may take place.
(ii)
Incompatibilities: Contact with strong oxidizing agents may cause
fires and explosions. The contacting of crude BD (not BD monomer) with copper
and copper alloys may cause formations of explosive copper compounds.
(iii) Hazardous decomposition products:
Toxic gases (such as carbon monoxide) may be released in a fire involving
BD.
(iv) Special precautions: BD
will attack some forms of plastics, rubber, and coatings. BD in storage should
be checked for proper inhibitor content, for self-polymerization, and for
formation of peroxides when in contact with air and iron. Piping carrying BD
may become plugged by formation of rubbery polymer.
(c) Warning Properties:
(i) Odor Threshold: An odor threshold of
0.45 ppm has been reported in The American Industrial Hygiene Association
(AIHA) Report, Odor Thresholds for Chemicals with Established Occupational
Health Standards. (Ex. 32-28C).
(ii)
Eye Irritation Level: Workers exposed to vapors of BD
(concentration or purity unspecified) have complained of irritation of eyes,
nasal passages, throat, and lungs. Dogs and rabbits exposed experimentally to
as much as 6700 ppm for 7 1/2 hours a day for 8 months have developed no
histologically demonstrable abnormality of the eyes.
(iii) Evaluation of Warning Properties:
Since the mean odor threshold is about half of the 1 ppm PEL, and more than
10-fold below the 5 ppm STEL, most wearers of air purifying respirators should
still be able to detect breakthrough before a significant overexposure to BD
occurs.
(3)
Spill, Leak, and Disposal Procedures.
(a)
Persons not wearing protective equipment and clothing should be restricted from
areas of spills or leaks until cleanup has been completed. If BD is spilled or
leaked, the following steps should be taken:
(i)
Eliminate all ignition sources.
(ii) Ventilate areas of spill or
leak.
(iii) If in liquid form, for
small quantities, allow to evaporate in a safe manner.
(iv) Stop or control the leak if this can be
done without risk. If source of leak is a cylinder and the leak cannot be
stopped in place, remove the leaking cylinder to a safe place and repair the
leak or allow the cylinder to empty.
(b) Disposal: This substance, when discarded
or disposed of, is a hazardous waste according to Federal regulations (40
C.F.R. part
261). It is listed by the EPA as hazardous waste number D001 due to
its ignitability. The transportation, storage, treatment, and disposal of this
waste material must be conducted in compliance with 40 C.F.R. parts
262,
263,
264,
268 and
270. Disposal can occur only in properly permitted facilities.
Check state and local regulations for any additional requirements because these
may be more restrictive than federal laws and regulations.
(4) Monitoring and Measurement Procedures.
(a) Exposure above the Permissible Exposure
Limit (8hr TWA) or Short-Term Exposure Limit (STEL):
(i)
8-hr TWA exposure evaluation: Measurements taken for the purpose
of determining employee exposure under this standard are best taken with
consecutive samples covering the full shift. Air samples must be taken in the
employee's breathing zone (air that would most nearly represent that inhaled by
the employee).
(ii) STEL exposure
evaluation: Measurements must represent 15 minute exposures associated with
operations most likely to exceed the STEL in each job and on each
shift.
(iii) Monitoring
frequencies: Table 1 gives various exposure scenarios and their required
monitoring frequencies, as required by the final standard for
occupational
exposure to butadiene.
Table 1. - Five Exposure Scenarios and Their Associated
Monitoring Frequencies
Action Level |
8-hr TWA |
STEL |
Required Monitoring Activity |
_* |
__ |
__ |
No 8-hour TWA or
STEL monitoring required. |
+* |
__ |
__ |
No STEL
monitoring required. Monitor 8-hr TWA annually. |
+ |
__ |
__ |
No STEL monitoring
required. Periodic monitoring 8-hour TWA, in accordance with (4)(c)(iii).**
|
+ |
+ |
+ |
Periodic monitoring
8-hour TWA, in accordance with (4)(c)(iii)**. Periodic monitoring STEL in
accordance with (4)(c)(iii). |
+ |
__ |
+ |
Periodic monitoring
STEL, in accordance with (4)(c)(iii). Monitor 8-hour TWA annually. |
Footnote (*)
|
Exposure Scenario, Limit Exceeded: + = Yes, - = No.
|
Footnote (**)
|
The employer may decrease the frequency of exposure
monitoring to annually when at least 2 consecutive measurements taken at least
7 days apart show exposures to be below the 8-hour TWA, but at or above the
action level.
|
(iv)
Monitoring techniques: Appendix D describes the validated method of sampling
and analysis which has been tested by OSHA for use with BD. The employer has
the obligation of selecting a monitoring method which meets the accuracy and
precision requirements of the standard under his or her unique field
conditions. The standard requires that the method of monitoring must be
accurate, to a 95 percent confidence level, to plus or minus 25 percent for
concentrations of BD at or above 1 ppm, and to plus or minus 35 percent for
concentrations below 1 ppm.
(5) Personal Protective Equipment.
(a) Employees should be provided with and
required to use impervious clothing, gloves, face shields (eight-inch minimum),
and other appropriate protective clothing necessary to prevent the skin from
becoming frozen from contact with liquid BD.
(b)
Any clothing which becomes wet with liquid BD should be removed
immediately and not reworn until the butadiene has evaporated.
(c) Employees should be provided with and
required to use splash proof safety goggles where liquid BD may contact the
eyes.
(6) Housekeeping
and Hygiene Facilities.
For purposes of complying with WAC
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.
(b) Adequate washing
facilities with hot and cold water are to be provided and maintained in a
sanitary condition.
(7)
Additional Precautions.
(a) Store BD 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.
(c) Do not incinerate BD
cartridges, tanks or other containers.
(d)
Employers must advise employees of all areas and operations where
exposure to BD might occur.
Appendix C. Medical Screening and Surveillance for
1,3-Butadiene (Nonmandatory)
(1)
Basis for Medical Screening and Surveillance Requirements.
(a) Route of Entry Inhalation.
(b) Toxicology.
Inhalation of BD has been linked to an increased risk of
cancer, damage to the reproductive organs, and fetotoxicity. Butadiene can be
converted via oxidation to epoxybutene and diepoxybutane, two genotoxic
metabolites that may play a role in the expression of BD's toxic effects. BD
has been tested for carcinogenicity in mice and rats. Both species responded to
BD exposure by developing cancer at multiple primary organ sites. Early deaths
in mice were caused by malignant lymphomas, primarily lymphocytic type,
originating in the thymus.
Mice exposed to BD have developed ovarian or testicular
atrophy. Sperm head morphology tests also revealed abnormal sperm in mice
exposed to BD; lethal mutations were found in a dominant lethal test. In light
of these results in animals, the possibility that BD may adversely affect the
reproductive systems of male and female workers must be considered.
Additionally, anemia has been observed in animals exposed to
butadiene. In some cases, this anemia appeared to be a primary response to
exposure; in other cases, it may have been secondary to a neoplastic
response.
(c)
Epidemiology.
Epidemiologic evidence demonstrates that BD exposure poses an
increased risk of leukemia. Mild alterations of hematologic parameters have
also been observed in synthetic rubber workers exposed to BD.
(2) Potential Adverse Health
Effects.
(a) Acute.
Skin contact with liquid BD causes characteristic burns or
frostbite. BD in gaseous form can irritate the eyes, nasal passages, throat,
and lungs. Blurred vision, coughing, and drowsiness may also occur. Effects are
mild at 2,000 ppm and pronounced at 8,000 ppm for exposures occurring over the
full workshift.
At very high concentrations in air, BD is an anesthetic,
causing narcosis, respiratory paralysis, unconsciousness, and death. Such
concentrations are unlikely, however, except in an extreme emergency because BD
poses an explosion hazard at these levels.
(b) Chronic.
The principal adverse health effects of concern are
BD-induced lymphoma, leukemia and potential reproductive toxicity. Anemia and
other changes in the peripheral blood cells may be indicators of excessive
exposure to BD.
(c)
Reproductive.
Workers may be concerned about the possibility that their BD
exposure may be affecting their ability to procreate a healthy child. For
workers with high exposures to BD, especially those who have experienced
difficulties in conceiving, miscarriages, or stillbirths, appropriate medical
and laboratory evaluation of fertility may be necessary to determine if BD is
having any adverse effect on the reproductive system or on the health of the
fetus.
(3)
Medical Screening Components At-A-Glance.
(a)
Health Questionnaire.
The most important goal of the health questionnaire is to
elicit information from the worker regarding potential signs or symptoms
generally related to leukemia or other blood abnormalities. Therefore,
physicians or other licensed health care professionals should be aware of the
presenting symptoms and signs of lymphohematopoietic disorders and cancers, as
well as the procedures necessary to confirm or exclude such diagnoses.
Additionally, the health questionnaire will assist with the identification of
workers at greatest risk of developing leukemia or adverse reproductive effects
from their exposures to BD.
Workers with a history of reproductive difficulties or a
personal or family history of immune deficiency syndromes, blood dyscrasias,
lymphoma, or leukemia, and those who are or have been exposed to medicinal
drugs or chemicals known to affect the hematopoietic or lymphatic systems may
be at higher risk from their exposure to BD. After the initial administration,
the health questionnaire must be updated annually.
(b) Complete Blood Count (CBC).
The medical screening and surveillance program requires an
annual CBC, with differential and platelet count, to be provided for each
employee with BD exposure. This test is to be performed on a blood sample
obtained by phlebotomy of the venous system or, if technically feasible, from a
fingerstick sample of capillary blood. The sample is to be analyzed by an
accredited laboratory.
Abnormalities in a CBC may be due to a number of different
etiologies. The concern for workers exposed to BD includes, but is not limited
to, timely identification of lym-phohematopoietic cancers, such as leukemia and
non-Hod-gkin's lymphoma. Abnormalities of portions of the CBC are identified by
comparing an individual's results to those of an established range of normal
values for males and females. A substantial change in any individual employee's
CBC may also be viewed as "abnormal" for that individual even if all
measurements fall within the population-based range of normal values. It is
suggested that a flowsheet for laboratory values be included in each employee's
medical record so that comparisons and trends in annual CBCs can be easily
made.
A determination of the clinical significance of an abnormal
CBC shall be the responsibility of the examining physician, other licensed
health care professional, or medical specialist to whom the employee is
referred. Ideally, an abnormal CBC should be compared to previous CBC
measurements for the same employee, when available. Clinical common sense may
dictate that a CBC value that is very slightly outside the normal range does
not warrant medical concern. A CBC abnormality may also be the result of a
temporary physical stressor, such as a transient viral illness, blood donation,
or menorrhagia, or laboratory error. In these cases, the CBC should be repeated
in a timely fashion, i.e., within 6 weeks, to verify that return to the normal
range has occurred. A clinically significant abnormal CBC should result in
removal of the employee from further exposure to BD. Transfer of the employee
to other work duties in a BD-free environment would be the preferred
recommendation.
(c)
Physical Examination.
The medical screening and surveillance program requires an
initial physical examination for workers exposed to BD; this examination is
repeated once every three years. The initial physical examination should assess
each worker's baseline general health and rule out clinical signs of medical
conditions that may be caused by or aggravated by occupational BD exposure. The
physical examination should be directed at identification of signs of
lymphohematopoietic disorders, including lymph node enlargement, splenomegaly,
and hepatomegaly.
Repeated physical examinations should update objective
clinical findings that could be indicative of interim development of a
lymphohematopoietic disorder, such as lymphoma, leukemia, or other blood
abnormality. Physical examinations may also be provided on an as needed basis
in order to follow up on a positive answer on the health questionnaire, or in
response to an abnormal CBC. Physical examination of workers who will no longer
be working in jobs with BD exposure are intended to rule out
lymphohematopoietic disorders.
The need for physical examinations for workers concerned
about adverse reproductive effects from their exposure to BD should be
identified by the physician or other licensed health care professional and
provided accordingly. For these workers, such consultations and examinations
may relate to developmental toxicity and reproductive capacity.
Physical examination of workers acutely exposed to
significant levels of BD should be especially directed at the respiratory
system, eyes, sinuses, skin, nervous system, and any region associated with
particular complaints. If the worker has received a severe acute exposure,
hospitalization may be required to assure proper medical management. Since this
type of exposure may place workers at greater risk of blood abnormalities, a
CBC must be obtained within 48 hours and repeated at one, two, and three
months.
Appendix D: Sampling and Analytical Method for 1,3-Butadiene
(Nonmandatory)
OSHA Method No.: 56.
Matrix: Air.
Target concentration: 1 ppm (2.21 mg/m(3)).
Procedure: Air samples are collected by drawing known volumes
of air through sampling tubes containing charcoal adsorbent which has been
coated with 4-tert-butylcatechol. The samples are desorbed with carbon
disulfide and then analyzed by gas chromatography using a flame ionization
detector.
Recommended sampling rate and air volume: 0.05 L/min and 3
L.
Detection limit of the overall procedure: 90 ppb (200
ug/m(3)) (based on 3 L air volume).
Reliable quantitation limit: 155 ppb (343 ug/m(3)) (based on
3 L air volume).
Standard error of estimate at the target concentration:
6.5%.
Special requirements: The sampling tubes must be coated with
4-tert-butylcatechol. Collected samples should be stored in a freezer.
Status of method: A sampling and analytical method has been
subjected to the established evaluation procedures of the Organic Methods
Evaluation Branch, OSHA Analytical Laboratory, Salt Lake City, Utah
84165.
(1) Background.
This work was undertaken to develop a sampling and analytical
procedure for BD at 1 ppm. The current method recommended by OSHA for
collecting BD uses activated coconut shell charcoal as the sampling medium
(Ref. 5.2). This method was found to be inadequate for use at low BD levels
because of sample instability.
The stability of samples has been significantly improved
through the use of a specially cleaned charcoal which is coated with
4-tert-butylcatechol (TBC). TBC is a polymerization inhibitor for BD (Ref.
5.3).
(a) Toxic effects.
Symptoms of human exposure to BD include irritation of the
eyes, nose and throat. It can also cause coughing, drowsiness and fatigue.
Dermatitis and frostbite can result from skin exposure to liquid BD. (Ref.
5.1)
NIOSH recommends that BD be handled in the workplace as a
potential occupational carcinogen. This recommendation is based on two
inhalation studies that resulted in cancers at multiple sites in rats and in
mice. BD has also demonstrated mutagenic activity in the presence of a liver
microsomal activating system. It has also been reported to have adverse
reproductive effects. (Ref. 5.1)
(b)
Potential workplace exposure.
About 90% of the annual production of BD is used to
manufacture styrenebutadiene rubber and Polybutadiene rubber. Other uses
include: Polychloroprene rubber, acrylonitrile butadiene-styrene resins, nylon
intermediates, styrenebutadiene latexes, butadiene polymers, thermoplastic
elastomers, nitrile resins, methyl methacrylatebutadiene styrene resins and
chemical intermediates. (Ref. 5.1)
(c)
Physical properties (Ref. 5.1).
CAS No.: 106-99-0
Molecular weight: 54.1
Appearance: Colorless gas
Boiling point: -4.41 deg. C (760 mm Hg)
Freezing point: -108.9 deg. C
Vapor pressure: 2 atm (a) 15.3 deg. C; 5 atm (a) 47 deg.
C
Explosive limits: 2 to 11.5% (by volume in air)
Odor threshold: 0.45 ppm
Structural formula: H(2)C:CHCH:CH(2)
Synonyms: BD; biethylene; bivinyl; butadiene; divinyl;
buta-1,3-diene; alpha-gamma-butadiene; erythrene; NCI-C50602; pyrrolylene;
vinylethylene.
(d) Limit
defining parameters.
The analyte air concentrations listed throughout this method
are based on an air volume of 3 L and a desorption volume of 1 mL. Air
concentrations listed in ppm are referenced to 25 deg. C and 760 mm Hg.
(e) Detection limit of the
analytical procedure.
The detection limit of the analytical procedure was 304 pg
per injection. This was the amount of BD which gave a response relative to the
interferences present in a standard.
(f)
Detection limit of the overall procedure.
The detection limit of the overall procedure was 0.60 ug per
sample (90 ppb or 200 ug/m(3)). This amount was determined graphically. It was
the amount of analyte which, when spiked on the sampling device, would allow
recovery approximately equal to the detection limit of the analytical
procedure.
(g) Reliable
quantitation limit.
The reliable quantitation limit was 1.03 ug per sample (155
ppb or 343 ug/m(3)). This was the smallest amount of analyte which could be
quantitated within the limits of a recovery of at least 75% and a precision
(+/- 1.96 SD) of +/-25% or better.
(h)
Sensitivity. (1)
Footnote (1) |
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 operation parameters. |
The sensitivity of the analytical procedure over a
concentration range representing 0.6 to 2 times the target concentration, based
on the recommended air volume, was 387 area units per ug/mL. This value was
determined from the slope of the calibration curve. The sensitivity may vary
with the particular instrument used in the analysis.
(i) Recovery.
The recovery of BD from samples used in storage tests
remained above 77% when the samples were stored at ambient temperature and
above 94% when the samples were stored at refrigerated temperature. These
values were determined from regression lines which were calculated from the
storage data. The recovery of the analyte from the collection device must be at
least 75% following storage.
(j)
Precision (analytical method only).
The pooled coefficient of variation obtained from replicate
determinations of analytical standards over the range of 0.6 to 2 times the
target concentration was 0.011.
(k)
Precision (overall procedure).
The precision at the 95% confidence level for the
refrigerated temperature storage test was +/- 12.7%. This value includes an
additional +/- 5% for sampling error. The overall procedure must provide
results at the target concentrations that are +/- 25% at the 95% confidence
level.
(1) Reproducibility.
Samples collected from a controlled test atmosphere and a
draft copy of this procedure were given to a chemist unassociated with this
evaluation. The average recovery was 97.2% and the standard deviation was
6.2%.
(2) Sampling
procedure.
(a) Apparatus. Samples are
collected by use of a personal sampling pump that can be calibrated to within
+/- 5% of the recommended 0.05 L/min sampling rate with the sampling tube in
line.
(b) Samples are collected
with laboratory prepared sampling tubes. The sampling tube is constructed of
silanetreated glass and is about 5-cm long. The ID is 4 mm and the OD is 6 mm.
One end of the tube is tapered so that a glass wool end plug will hold the
contents of the tube in place during sampling. The opening in the tapered end
of the sampling tube is at least one-half the ID of the tube (2 mm). The other
end of the sampling tube is open to its full 4-mm ID to facilitate packing of
the tube. Both ends of the tube are fire-polished for safety. The tube is
packed with 2 sections of pre-treated charcoal which has been coated with TBC.
The tube is packed with a 50-mg backup section, located nearest the tapered
end, and with a 100-mg sampling section of charcoal. The two sections of coated
adsorbent are separated and retained with small plugs of silanized glass wool.
Following packing, the sampling tubes are sealed with two 7/32 inch OD plastic
end caps. Instructions for the pretreatment and coating of the charcoal are
presented in Section 4.1 of this method.
(c)
Reagents. None required.
(d)
Technique.
(i) Properly label
the sampling tube before sampling and then remove the plastic end
caps.
(ii) Attach the sampling
tube to the pump using a section of flexible plastic tubing such that the
larger front section of the sampling tube is exposed directly to the
atmosphere. Do not place any tubing ahead of the sampling tube. The sampling
tube should be attached in the worker's breathing zone in a vertical manner
such that it does not impede work performance.
(iii) After sampling for the appropriate
time, remove the sampling tube from the pump and then seal the tube with
plastic end caps. Wrap the tube lengthwise.
(iv)
Include at least one blank for each sampling set. The blank
should be handled in the same manner as the samples with the exception that air
is not drawn through it.
(v) List
any potential interferences on the sample data sheet.
(vi) The samples require no special shipping
precautions under normal conditions. The samples should be refrigerated if they
are to be exposed to higher than normal ambient temperatures. If the samples
are to be stored before they are shipped to the laboratory, they should be kept
in a freezer. The samples should be placed in a freezer upon receipt at the
laboratory.
(e)
Breakthrough.
(Breakthrough was defined as the relative amount of analyte
found on the backup section of the tube in relation to the total amount of
analyte collected on the sampling tube. Five-percent breakthrough occurred
after sampling a test atmosphere containing 2.0 ppm BD for 90 min. at 0.05
L/min. At the end of this time 4.5 L of air had been sampled and 20.1 ug of the
analyte was collected. The relative humidity of the sampled air was 80% at 23
deg. C.)
Breakthrough studies have shown that the recommended sampling
procedure can be used at air concentrations higher than the target
concentration. The sampling time, however, should be reduced to 45 min. if both
the expected BD level and the relative humidity of the sampled air are
high.
(f) Desorption
efficiency.
The average desorption efficiency for BD from TBC coated
charcoal over the range from 0.6 to 2 times the target concentration was 96.4%.
The efficiency was essentially constant over the range studied.
(g) Recommended air volume and
sampling rate.
(h) The recommended
air volume is 3 L.
(i) The
recommended sampling rate is 0.05 L/min. for 1 hour.
(j) Interferences.
There are no known interferences to the sampling
method.
(k) Safety
precautions.
(i) Attach the sampling
equipment to the worker in such a manner that it will not interfere with work
performance or safety.
(ii) Follow
all safety practices that apply to the work area being sampled.
(3) Analytical
procedure.
(a) Apparatus.
(i) A gas chromatograph (GC), equipped with
a flame ionization detector (FID).(2)
Footnote (2) |
A Hewlett-Packard Model 5840A GC
was used for this evaluation. Injections were performed using a Hewlett-Packard
Model 7671A automatic sampler. |
(ii)
A GC column capable of resolving the analytes from any
interference.(3)
Footnote (3) |
A 20-ft x 1/8-inch OD stainless
steel GC column containing 20% FFAP on 80/100 mesh Chromabsorb W-AW-DMCS was
used for this evaluation. |
(iii)
Vials, glass 2-mL with Teflon-lined caps.
(iv) Disposable Pasteur type pipets,
volumetric flasks, pipets and syringes for preparing samples and standards,
making dilutions and performing injections.
(b) Reagents.
(i)
Carbon disulfide.(4)
Footnote (4) |
Fisher Scientific Company A.C.S.
Reagent Grade solvent was used in this evaluation. |
The benzene contaminant that was present in the carbon
disulfide was used as an internal standard (ISTD) in this evaluation.
(ii) Nitrogen, hydrogen and air,
GC grade.
(iii) BD of known high
purity. (5)
Footnote (5) |
Matheson Gas Products, CP Grade
1,3-butadiene was used in this study. |
(c)
Standard preparation.
(i)
Prepare standards by diluting known volumes of BD gas with carbon disulfide.
This can be accomplished by injecting the appropriate volume of BD into the
headspace above the 1-mL of carbon disulfide contained in sealed 2-mL vial.
Shake the vial after the needle is removed from the septum. (6)
Footnote (6) |
A standard containing 7.71 ug/mL
(at ambient temperature and pressure) was prepared by diluting 4 uL of the gas
with 1-mL of carbon disulfide. |
(ii)
The mass of BD gas used to prepare standards can be determined by
use of the following equations:
MV = (760/BP)(273+t)/(273)(22.41)
Where:
MV = ambient molar volume
BP = ambient barometric pressure
T = ambient temperature
ug/uL = 54.09/MV
ug/standard = (ug/uL)(uL) BD used to prepare the
standard
(d)
Sample preparation.
(i) Transfer the 100-mg
section of the sampling tube to a 2-mL vial. Place the 50-mg section in a
separate vial. If the glass wool plugs contain a significant amount of
charcoal, place them with the appropriate sampling tube section.
(ii) Add 1-mL of carbon disulfide to each
vial.
(iii) Seal the vials with
Teflon-lined caps and then allow them to desorb for one hour. Shake the vials
by hand vigorously several times during the desorption period.
(iv) If it is not possible to analyze the
samples within 4 hours, separate the carbon disulfide from the charcoal, using
a disposable Pasteur-type pipet, following the one hour. This separation will
improve the stability of desorbed samples.
(v)
Save the used sampling tubes to be cleaned and repacked with
fresh adsorbent.
(e)
Analysis.
(i) GC Conditions.
Column temperature: 95 deg. C
Injector temperature: 180 deg. C
Detector temperature: 275 deg. C
Carrier gas flow rate: 30 mL/min.
Injection volume: 0.80 uL
GC column: 20-ft x 1/8-in OD stainless steel GC column
containing 20%
FFAP on 80/100 Chromabsorb W-AW-DMCS.
(ii) Chromatogram. See Section
4.2.
(iii) Use a suitable method,
such as electronic or peak heights, to measure detector response.
(iv) Prepare a calibration curve using
several standard solutions of different concentrations. Prepare the calibration
curve daily. Program the integrator to report the results in ug/mL.
(v) Bracket sample concentrations with
standards.
(f)
Interferences (analytical).
(i) Any compound
with the same general retention time as the analyte and which also gives a
detector response is a potential interference. Possible interferences should be
reported by the industrial hygienist to the laboratory with submitted
samples.
(ii) GC parameters
(temperature, column, etc.) may be changed to circumvent
interferences.
(iii) A useful
means of structure designation is GC/MS. It is recommended that this procedure
be used to confirm samples whenever possible.
(g) Calculations.
(i)
Results are obtained by use of calibration curves. Calibration
curves are prepared by plotting detector response against concentration for
each standard. The best line through the data points is determined by curve
fitting.
(ii) The concentration,
in ug/mL, for a particular sample is determined by comparing its detector
response to the calibration curve. If any analyte is found on the backup
section, this amount is added to the amount found on the front section. Blank
corrections should be performed before adding the results together.
(iii) The BD air concentration can be
expressed using the following equation:
mg/m(3) = (A)(B)/(C)(D)
Where:
A = ug/mL from Section 3.7.2
B = volume
C = L of air sampled
D = efficiency
(iv)
The following equation can be used to convert results in mg/m(3)
to ppm:
ppm = (mg/m(3))(24.46)/54.09 Where:
mg/m(3) = result from Section 3.7.3.
24.46 = molar volume of an ideal gas at 760 mm Hg and 25
deg. C.
(h)
Safety precautions (analytical).
(i) Avoid
skin contact and inhalation of all chemicals.
(ii) Restrict the use of all chemicals to a
fume hood whenever possible.
(iii)
Wear safety glasses and a lab coat in all laboratory areas.
(4) Additional
Information.
(a) A procedure to prepare
specially cleaned charcoal coated with TBC.
(i)
Apparatus.
(A) Magnetic
stirrer and stir bar.
(B) Tube
furnace capable of maintaining a temperature of 700 deg. C and equipped with a
quartz tube that can hold 30 g of charcoal.(8)
Footnote (8) |
A Lindberg Type 55035 Tube
furnace was used in this evaluation. |
(C)
A means to purge nitrogen gas through the charcoal inside the quartz
tube.
(D) Water bath capable of
maintaining a temperature of 60 deg. C.
(E)
Miscellaneous laboratory equipment: One-liter vacuum flask, 1-L
Erlenmeyer flask, 350-M1 Buchner funnel with a coarse fitted disc, 4-oz brown
bottle, rubber stopper, Teflon tape etc.
(ii) Reagents.
(A)
Phosphoric acid, 10% by weight, in water.(9)
Footnote (9) |
Baker Analyzed Reagent grade was
diluted with water for use in this evaluation. |
(B)
4-tert-Butylcatechol (TBC).(10)
Footnote (10) |
The Aldrich Chemical Company 99%
grade was used in this evaluation. |
(C)
Specially cleaned coconut shell charcoal, 20/40 mesh. (11)
Footnote (11) |
Specially cleaned charcoal was
obtained from Supelco, Inc. for use in this evaluation. The cleaning process
used by Supelco is proprietary. |
(D)
Nitrogen gas, GC grade.
(iii)
Procedure.
Weigh 30g of charcoal into a 500-mL Erlenmeyer flask. Add
about 250 mL of 10% phosphoric acid to the flask and then swirl the mixture.
Stir the mixture for 1 hour using a magnetic stirrer. Filter the mixture using
a fitted Buchner funnel. Wash the charcoal several times with 250-mL portions
of deionized water to remove all traces of the acid. Transfer the washed
charcoal to the tube furnace quartz tube. Place the quartz tube in the furnace
and then connect the nitrogen gas purge to the tube. Fire the charcoal to 700
deg. C. Maintain that temperature for at least 1 hour. After the charcoal has
cooled to room temperature, transfer it to a tared beaker. Determine the weight
of the charcoal and then add an amount of TBC which is 10% of the charcoal, by
weight.
CAUTION-TBC is toxic and should only be handled in a fume
hood while wearing gloves.
Carefully mix the contents of the beaker and then transfer
the mixture to a 4-oz bottle. Stopper the bottle with a clean rubber stopper
which has been wrapped with Teflon tape. Clamp the bottle in a water bath so
that the water level is above the charcoal level. Gently heat the bath to 60
deg. C and then maintain that temperature for 1 hour. Cool the charcoal to room
temperature and then transfer the coated charcoal to a suitable
container.
The coated charcoal is now ready to be packed into sampling
tubes. The sampling tubes should be stored in a sealed container to prevent
contamination. Sampling tubes should be stored in the dark at room temperature.
The sampling tubes should be segregated by coated adsorbent lot number.
(b) Chromatograms.
The chromatograms were obtained using the recommended
analytical method. The chart speed was set at 1 cm/min. for the first three
min. and then at 0.2 cm/min. for the time remaining in the analysis.
The peak which elutes just before BD is a reaction product
between an impurity on the charcoal and TBC. This peak is always present, but
it is easily resolved from the analyte. The peak which elutes immediately
before benzene is an oxidation product of TBC.
(5) References.
(a)
"Current Intelligence Bulletin 41, 1,3-Butadiene," U.S. Dept. of
Health and Human Services, Public Health Service, Center for Disease Control,
NIOSH.
(b) "NIOSH Manual of
Analytical Methods," 2nd ed.; U.S. Dept. of Health Education and Welfare,
National Institute for Occupational Safety and Health: Cincinnati, OH. 1977,
Vol. 2, Method No. S91 DHEW (NIOSH) Publ. (U.S.), No. 77-157-B.
(c) Hawley, G.C., Ed. "The Condensed
Chemical Dictionary," 8th ed.; Van Nostrand Rienhold Company: New York, 1971;
139.5.4. Chem. Eng. News (June 10, 1985), (63), 22-66.
Appendix E: Reserved.
APPENDIX F, MEDICAL QUESTIONNAIRES, (Non-mandatory)
1,3-Butadiene (BD) Initial Health Questionnaire
DIRECTIONS:
You have been asked to answer the questions on this form
because you work with BD (butadiene). These questions are about your work,
medical history, and health concerns. Please do your best to answer all of the
questions. If you need help, please tell the doctor or health care professional
who reviews this form.
This form is a confidential medical record. Only information
directly related to your health and safety on the job may be given to your
employer. Personal health information will not be given to anyone without your
consent.
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