Product Stewardship Manual: Version II - U.S.A., 2004

P r o d u c t S t e w a rd s h i p M a n u a l
Version II U.S.A., 2004
BENZENE
PRODUCT STEWARDSHIP
Shell Chemicals* Commitment
to Health, Safety and the Environment
Shell Chemicals are committed to health, safety,
and the environment (HSE). In this way we aim to
have an HSE performance we can be proud of, to
earn the confidence of our customers, shareholders
and society at large, to be a good neighbour and
to contribute to sustainable development. The
full text of Shells Commitment to HSE and Policy
are in Appendix A.
SHELL PRODUCT STEWARDSHIP PROGRAM

Shell Chemicals are committed to developing ways
to assist our customers in reducing the potential
risks of handling and using our products. We
believe our customers value this commitment. It is
consistent with our goal to be a preferred supplier
and a leading contributor to the safe use of products in the petro-chemical industry.
SHELL BENZENE PRODUCT STEWARDSHIP

The Aromatics Business follows the general
principles of Product Stewardship as embodied by
the American Chemistry Council (ACC) Responsible
Care** Product Stewardship Code of Management
Practices and other responsible care programs in
countries around the world.
PURPOSE AND SCOPE

The purpose of Product Stewardship is to make
health, safety, and environmental protection an
integral part of designing, manufacturing, marketing,
distributing, using, recycling, and ultimate disposing
of products. This process covers all stages of a
products life. Successful implementation of Product

Stewardship is a shared responsibility. Everyone
involved with the product has the responsibility to
address societys interest in a healthful environment
and in products that can be used safely.
GOALS
Shell Chemicals wish to develop working relationships with its customers and suppliers to further the
purposes of product stewardship with the following
goals:
To promote understanding of the health,
safety, and the environmental aspects of
distributing, using, and disposing of benzene.
To develop options for effective risk
management practices for benzene.
To responsibly deal with public concerns
related to benzene.
These goals can be achieved most effectively
when suppliers and customers work together.
BASE CHEMICALS PRODUCT STEWARDSHIP

It is vital for the entire industry to cooperate
in this common goal of protecting our employees,
communities, and the environment. For additional
information on material contained in this binder,
and/or the Shell Benzene Product Stewardship
process, please contact your sales executive. We
encourage your response on the value of the
information provided, and hope it will prove to be
a useful resource for you.
*The expression Shell Chemicals refers to the companies of the Royal Dutch/Shell Group engaged in the chemicals business. Each of the companies
that make up the Royal Dutch/Shell Group of companies is an independent entitiy and has its own seperate identity.
**Responsible Care is a registered tradenmark of the American Chemistry Council
9/04
ACC Product Stewardship Code

of Management Practices
Shell Chemicals have always been committed to the
health and safety of our employees, communities,
customers, and the environment. When the
Chemical Manufacturers Association (now ACC)
Responsible Care initiative began in 1989, we not
only adopted it, we contributed significantly to its
development and made it an important part of our
culture. The principles of Responsible Care are at
the very core of our goal of being a preferred
employer, welcomed neighbor, and preferred
supplier. Shell is a partner in the American Chemistry
Councils Responsible Care initiative, and is a full
participant in the ACC Responsible Care program.
The Shell Product Stewardship Program, based
on the ACCs Product Stewardship Management
Practices identified below, is our commitment to
produce and market products responsibly. This
commitment is the responsibility of each and
every individual involved with our products from
initial R&D to manufacturing, distribution, sale, and
ultimate disposal. These management practices are
imbedded in the Responsible Care Management
System.
MANAGEMENT LEADERSHIP AND COMMITMENT

1. Leadership: Demonstrates senior management
leadership through written policy, active
participation, and communication.
2. Accountability and Performance Measurement:
Establishes goals and responsibilities for
implementing product stewardship throughout
the organization. Measures performance against
these goals.
3. Resources: Commits resources necessary to
implement and maintain product stewardship
practices.
INFORMATION AND CHARACTERIZATION

4. Health, Safety, and Environmental Information:
Establishes and maintains information on
health, safety, and environmental hazards and
reasonably foreseeable exposures from new
and existing products.
5. Product Risk Characterization: Characterizes
new and existing products with respect to their
foreseeable risk using information about health,
safety, and environmental hazards, and
reasonably foreseeable exposures. Establishes
a system that initiates re-evaluation.
RISK MANAGEMENT
6. Risk Management System: Establishes a system
to identify, document, and implement health,
safety, and environmental risk management
actions appropriate to foreseeable product risk.
7. Product and Process Design and Improvement:
Establishes and maintains a system that makes
health, safety, and environmental impacts,
including the use of energy and natural
resources, key considerations in designing,
developing, and improving products and
processes.
8. Employee Education and Product Use Feedback:
Educates and trains employees, on the proper
handling, recycling, use, and disposal of products
as well as the known product uses. Implements
a system that encourages employees to provide
information on new uses, identified misuses,
or adverse effects for use in product
characterization.
9. Contract Manufacturers: Selects contract
manufacturers who employ appropriate practices
for health, safety, and environmental protection
for the operations under contract; or, works
with contract manufacturers to help them
implement such practices. Provides information
and guidance appropriate to the product and
process risk to foster proper handling, use,
recycling, and disposal. Periodically reviews
performance of contract manufacturers.
9/04
10. Suppliers: Requires suppliers to provide

appropriate health, safety, and environmental
information and guidance on their products.
Factors adherence to sound health, safety,
and environmental principles, such as those
contained in Responsible Care, into
procurement positions.
11. Distributors: MSDS provides health, safety, and
environmental information to distributors.
Commensurate with product risk, selects, works
with, and periodically reviews distributors to
foster proper use, handling, recycling, disposal,
and transmittal of appropriate information to
downstream users. When a company identifies
improper practices involving a product, it will
work with the distributor to improve those
practices. If, in the companys independent
judgment, improvement is not evident, the
company should take further measures, up to
and including termination of the business
relationship. This management practice should
be implemented in conjunction with the
Distribution Code of Management Practices*.
12. Customers and Other Direct Receivers: MSDS
provides health, safety, and environmental
information to direct product receivers.
Commensurate with product risk, works with
them to foster proper use, handling, recycling,
disposal, and transmittal of information to
downstream users. When a company identifies
improper practices involving a product, it will
work with the product receiver to improve
those practices. If, in the companys
independent judgment, improvement is not
evident, the company should take further
measures up to and including termination of
product sale.
*americanchemistry.org
9/04
Disclaimer
The sole purpose of this package is to provide
information regarding Shell Chemicals Benzene
Product Stewardship efforts to customers. Any
information within this package should not be
considered as a recommendation. Shell Chemicals
has acted in good faith in the preparation of all
information provided as part of this package, but
Shell Chemicals does not guarantee the accuracy or
completeness of such information. Shell Chemicals
makes no representations or warranties, express or
implied, as to the accuracy or completeness of any
of the information contained herein. Parties should
conduct their own studies and rely on their own
analysis. Shell Chemicals expressly disclaims any and
all liability, including loss and damages suffered,
based on or relating to the use or errors of and
omissions from such information. Shell Chemicals
disclaims any obligation or intent to update this web
site or any information contained within to reflect
future events or developments.The information is
based on U.S. regulations and the American
Chemistry Council Responsible Care program.
The expression Shell Chemicals refers to the

companies of the Royal Dutch/Shell Group engaged
in the chemicals business. Each of the companies
that make up the Royal Dutch/Shell Group of
companies is an independent entitiy and has its
own seperate identity.
This web site may include links to external web
sites. These links are provided in order to help you
find relevant web sites, services and/or products
that may be of interest to you quickly and easliy.
It is your responsibility to decide whether any
services and/or products available through any of
these web sites are suitable for your purposes. Shell
Chemicals is not responsible for the owners or
operators of these web sites or for any goods or
services they supply or for the content of their web
sites, and does not give or enter into any conditions,
warranties or other terms or representations in
relation to any of these or accept any liability in
relation to any of these (including any liability
arising out of any claim that the content of any
external web site to which this web site includes a
link infringes the intellectual property rights of any
third party).
http://www.shell.com/chemicals
9/04
BENZENE PRODUCT STEWARDSHIP VERSION II U.S.A., 2004
TABLE OF CONTENTS
Page
1.
CHEMICAL IDENTIFICATION, PRODUCTION, AND USE

1.1
1.2
1.3
1.4
1.5
1.6
2.
2.8
2.9
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1-1
1-1
1-3
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2-1
2-1
2-2
2-2
2-2
2-3
2-3
1-6
1-13
1-14
General Information . . . . . . . . . . . .
Overview of Benzene Health Hazards
Eye Contact . . . . . . . . . . . . . . . . . .
Skin Contact . . . . . . . . . . . . . . . . . .
Acute Inhalation Exposure . . . . . . . .
Ingestion . . . . . . . . . . . . . . . . . . . .
Subchronic/Chronic Toxicity . . . . . . .
Carcinogenicity
Reproductive Toxicity
Developmental Toxicity
Genotoxicity
Epidemiology . . . . . . . . . . . . . . . .
Medical Surveillance . . . . . . . . . . . .
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. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2-5
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2-5
ECOTOXICITY/ECOLOGICAL FATE
3.1
3.2
9/04
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HEALTH HAZARD INFORMATION

2.1
2.2
2.3
2.4
2.5
2.6
2.7
3.
Product Identification . . . . . . . . . . . . . . . . .
Benzene Manufacturing Process Information
Benzene End Uses . . . . . . . . . . . . . . . . . .
General Information . . . . . . . . . . . . .
Uses of Benzene . . . . . . . . . . . . . . .
Chemical and Physical Properties of Benzene
Benzene Product Quality . . . . . . . . . . . . . .
Benzene Reactivities and Incompatibilities . .
Ecotoxicity . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3-1
Aquatic Toxicity
Aquatic Properties
Ecological Fate . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3-1
Fate in Soil
Fate in Water
Fate in Air
Page
4.
REGULATORY OVERVIEW
4.1
4.2
4.3
4.4
4.5
4.6
4.7
4.8
4.9
Benzene Health and Safety Standards . . . . . . . . . . . . . . . . . . . . . . . . . .

Occupational Safety and Health Administration (OSHA)
U.S. Coast Guard
Occupational Exposure Limits for Benzene . . . . . . . . . . . . . . . . . . . . . .
General Information on Occupational Exposure Limits
Occupational Exposure Limits for Benzene
Biological Exposure Indices
Federal Environmental Regulatory Overview . . . . . . . . . . . . . . . . . . . . .
Resource Conservation and Recovery Act (RCRA)
Comprehensive Environmental Response,
Compensation and Liability Act (CERCLA)
Title III of Superfund Amendments and Reauthorization Act
(SARA Title III)
Clean Air Act (CAA)
Clean water Act (CWA)
Toxic Substances Control Act (TSCA)
Federal Regulatory Management for Prevention of Accidental Releases . . .
OSHA - Process Safety Management of Highly Hazardous
Chemicals (29 CFR 1910.119)
EPA - Prevention of Accidental Releases of Hazardous Air Pollutants
State Right-to-Know Laws/Regulations . . . . . . . . . . . . . . . . . . . . . . . . . .
State Right-to-Know Listings
California Safe Drinking Water and Toxics Enforcement
Act of 1986 (Proposition 65)
Food and Drug Administration (FDA) . . . . . . . . . . . . . . . . . . . . . . . . . .
Consumer Product Safety Commission (CPSC) . . . . . . . . . . . . . . . . . . . .
International Regulations . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Canada
Foreign Chemical Inventories
Hazard Ratings for Benzene . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
National Fire Protection Association (NFPA) Hazard Rating
NFPA Hazard Rating for Benzene
National Paints and Coatings Association (NPCA) Hazardous
Materials Identification System (HMIS) Rating
NPCA HMIS Rating for Benzene
. . . . . . . 4-1
. . . . . . . 4-2
. . . . . . . 4-3
. . . . . . . 4-6
. . . . . . . 4-7
. . . . . . . 4-8
. . . . . . . 4-8
. . . . . . . 4-9
. . . . . . . 4-9
9/04
Page
5.
HANDLING AND STORAGE INFORMATION

5.1
5.2
5.3
6.
FIRE SAFETY & SPILLS AND LEAKS

6.1
6.2
6.3
6.4
7.
7.2
7.3
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6-1
6-3
6-3
6-4
General Information on Benzene Transportation . . . . . . . . . . . . . . . . . . . . . . . . . . 7-1

Barge Shipments
Cleaning of Equipment
Emergency Response . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 7-2
Transport Classifications for Benzene . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 7-3
POLLUTION PREVENTION
8.1
8.2
9/04
Fire and Explosion Hazard

Fire Prevention . . . . . . . .
Fire Fighting . . . . . . . . . .
Spills and Leaks . . . . . . .
TRANSPORTATION
7.1
8.
Personal Protective Equipment . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5-1

Respiratory Protection
Chemical Protective Clothing
Eye and Face Protection
Exposure Monitoring . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5-3
General Information on Storage and Handling . . . . . . . . . . . . . . . . . . . . . . . . . . . 5-4
Equipment
Bulk Movement of Benzene by Barge
Bulk Storage of Benzene
Benzene Reactivities and Incompatibilities
SARA Title III Toxics Release Inventory (TRI) Data . . . . . . . . . . . . . . . . . . . . . . . . 8-1

Emission Reduction Measures . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 8-2
Page
APPENDIX A
Shells Commitment to HSE and Policy . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . A-1
APPENDIX B
OSHA Benzene Standard (29 CFR 1910.1028), Including
its Appendices A through D . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . B-1
APPENDIX C
Marine Occupational Safety and Health Standard for Benzene . . . . . . . . . . . . . . . . . . . . . C-1
APPENDIX D
NIOSH Sampling and Analytical Procedure for Benzene
(Method 1501 Hydrocarbons, Aromatic) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . D-1
APPENDIX E
3M TECH DATA Bulletin Number 59 Sampling for Benzene . . . . . . . . . . . . . . . . . . . . . E-1
APPENDIX F
Shell Declaration of Inspection and Benzene Addendum . . . . . . . . . . . . . . . . . . . . . . . . F-1
9/04
1. CHEMICAL IDENTIFICATION,
PRODUCTION, AND USE
1.1 Product Identification
1.2 Benzene Manufacturing

Process Information
Shell Product Name:
Benzene
Chemical Name:
Benzene
Chemical Family:
Aromatic Hydrocarbon
Chemical Abstract Service

Registry Number:
71-43-2
Chemical Formula:
C6 H6
Benzene is produced commercially by five processes:

destructive distillation of coal (by-product of steel
mill coking process); catalytic reforming of petroleum
-based naphtha; recovery from pyrolysis gasoline
(pygas), a co-product stream from the steam cracking
process used to manufacture ethylene (the ethylene
co-product process); hydrodealkylation of toluene
(HDA process); and the toluene disproportionation
process (TDP).
The first three processes involve the production
of benzene from a C6 hydrocarbon stream by
solvent extraction. In the latter two processes, the
benzene product is separated from the reactants
and co-products by distillation.
Shell chemicals companies currently produce
benzene by the catalytic reforming of naphtha, and
the ethylene co-product process. In both processes,
the benzene-rich streams are processed to remove
the light ends (C 5 and lighter) in a stabilizer
column, and heavy ends (C 7 and heavier) in a
debenzenizer column. After processing, the C 6
fraction consists of a small amount of light ends and
a C 6 concentrate stream. The benzene concentration
of this stream varies between the two processes.
Depending on feed quality and severity of the
catalytic reformer, the benzene concentration of the
C6 concentrate from the naphtha process is about
15% to 30% volume. Benzene concentrate from
the ethylene co-product process has a benzene
concentration of 70% to 75% volume. The remainder
of the components in the C 6 concentrate streams
are called raffinates. These raffinates are highly
paraffinic if they are from catalytic reforming or
have some naphthenic components, if from the
Chemical Structure:
9/04
1-1
ethylene co-product process. Some manufacturers,

particularly those using reformate as feedstock,
extract toluene and xylene in addition to benzene
from a C 6 through C8 mixture, and separate the
three aromatics by distillation. Shell Chemicals
companies use sulfolane (Figure 1.2) as the
extraction solvent.
Figure 1.1 provides an illustrative flow scheme
of the Shell Sulfolane Benzene Extraction Process.
The aromatic rich stream (C6 fraction) is fed to a
liquid-liquid contactor in the extraction process. In
the contactor, essentially all the aromatics in the
feed are dissolved in the extraction solvent and
are drawn from the bottom as fat solvent. The non-
aromatics, called raffinates, are taken off the top

of the contactor.
Sulfolane is the primary solvent used in
aromatics extraction. However, other solvents may
be used, including tetraethylene glycol and
N-methylpyrrolidone.
The fat solvent picks up some light paraffins
that must be removed to meet the benzene
specification, which is accomplished by taking
the paraffins over-head in the paraffin stripping
column. The paraffins are returned to the extraction
contactor and eventually leave the process with
the raffinate. The combination of extraction and
stripping provides a very sharp separation between
FIGURE 1.1: SHELL SULFOLANE BENZENE EXTRACTION PROCESS
1-2
9/04
1.3 Benzene End Uses

GENERAL INFORMATION
aromatics and non-aromatics. The paraffin-free
mixture goes to the aromatics stripper column
where stripping steam, heat, and vacuum are used
to separate the feed into aromatics and lean
solvent. The lean solvent is recycled back to the
extraction contactor.
In the units that process C6 concentrate from
reformate, some olefins are extracted with the
benzene. In these units, there are clay treaters
between the aromatics stripper column and the
benzene fractionator that dimerize any olefins that
may be present. The aromatics stripper tops, after
clay treating, enter the benzene fractionator where
benzene is distilled from any toluene, xylene, or
heavier bottoms. The dimerized olefins are rejected
out of the bottoms of the benzene fractionator and
are circulated back to feed preparation columns
upstream of the extraction section where they are
removed.
The raffinate stream exiting the process is
washed with water for recovery of the sulfolane.
The recovered solvent is returned to the extraction
section.
Benzene is a major product of the petrochemical

industry. It is considered to be the most important
and versatile aromatic compound. As illustrated in
Section 1.1 Product Identification, the chemical
structure of benzene consists of six (6) carbon
atoms arranged in a hexagonal ring to each of
which a hydrogen atom is attached (C6 H6 ). There
are three double bonds in the benzene ring, and
this unsaturation greatly contributes to its chemical
reactivity. As a result, it is a very useful building
block in the synthesis of other chemicals.
Base chemicals such as benzene are converted
into intermediate chemical products which are in
turn converted to other chemicals, plastics, resins,
elastomers, fibers, or surfactants. Primary derivatives
of benzene that have large volume commercial use
are ethylbenzene, cumene, cyclohexane, and
nitrobenzene. Hundreds of benzene derivatives are
formed by the replacement of one or more of its
hydrogen atoms with other elements, groups, or
side chains. Only those derivatives having significant
industrial or commercial value are discussed here.
MAJOR END USES OF BENZENE

FIGURE 1.2: MOLECULAR STRUCTURE OF SULFOLANE
9/04
This subsection briefly discusses the manufacturing

processes used to convert benzene into various
down-stream products. At the conclusion of this
subsection, Figure 1.3 provides an overview of the
major benzene derivatives and the final consumer
products that are made from them.
Ethylbenzene/Styrene: Nearly all ethylbenzene
in the United States is formed by the alkylation of
benzene with ethylene. All but minor quantities of
the ethylbenzene produced are dehydrogenated to
make styrene. Styrene is the largest derivative of
benzene. It is used as a chemical intermediate in a
wide range of processes, including:
Polystyrene resins
Styrene-butadiene rubber
Acrylonitrile-butadiene-styrene (ABS) resins
Styrene-acrylonitrile (SAN) resins
Styrene-butadiene latexes
Styrene-butadiene block copolymers
(SBS, SEBS)
1-3
Styrene-butadiene block copolymers

(SBS, SEBS)
Styrene-maleic anhydride copolymer resins
Methyl methacrylate-butadiene-styrene
(MMBS) resins
Cumene/Phenol/Acetone: Benzene is alkylated
with propylene to form cumene (isopropylbenzene).
The cumene is then oxidized to form cumene
hydroperoxide which is split into phenol and
acetone.
Phenol is an intermediate in the manufacture
of phenol-formaldehyde resins, bisphenol A,
cyclohexanone, chlorophenols, caprolactam, and
salicylic acid.
Acetone is an important solvent and chemical
intermediate. A key acetone derivative is methyl
methacrylate, a monomer used in the manufacture
of acrylic resins.
Cyclohexane: Cyclohexane is obtained either by
extraction from hydrocarbon streams or the catalytic
hydrogenation of benzene. Cyclohexane is used as
a solvent and is also a chemical intermediate for
caprolactam and adipic acid, two chemicals used in
the manufacture of nylon fibers.
Caprolactam is produced by the Beckman
rearrangement of cyclohexanone oxime. Adipic
acid is obtained by a process which involves the
oxidation of cyclohexane.
Nitrobenzene/Aniline: Nitrobenzene is produced
by the nitration of benzene. Aniline is formed via
the reduction of nitrobenzene. A second method
used to produce aniline is by the ammonolysis of
phenol. Aniline is used as a chemical intermediate
in the production of polymeric isocyanates and
acetanilide.
Other End Uses: Benzene is also used as a
chemical intermediate in many processes including
detergent alkylates, chlorobenzene, maleic
anhydride, surfactants, and dyes.
In summary, benzene is an extremely versatile
and significant industrial chemical. Figure 1.3
provides an overview of the major uses of benzene.
1-4
9/04
FIGURE 1.3: MAJOR BENZENE END USES1

1. The types of products identified are intended to be illustrative examples rather than an exhaustive listing.
9/04
1-5
I.4 Chemical and Physical Properties

of Benzene
TABLE 1.1: CHEMICAL AND PHYSICAL PROPERTIES

OF BENZENE
Property
Benzene is a clear, colorless liquid with a
characteristic aromatic hydrocarbon odor. This
odor is distinctive and sweet. Benzene is extremely
flammable. Data pertaining to its chemical and
physical properties are presented in Table 1.1.
Additional data concerning the physical properties
of benzene and their temperature dependence can
be found in Figures 1.4-1.15 (Source DIPPR
Database1 and Shaw3 for Figure 1.14).
Value
Physical State
Liquid
Color
Colorless
Odor
Distinct,
sweet odor
Autoignition Temperature
562 C/1044 F
Boiling Point
80.1 C/176.2 F
Critical Compressibility Factor

Critical Pressure
Critical Temperature
552.2 F
Critical Volume
0.053 ft3/lb
Density (liquid)
54.74 lb/ft3 @ 70 F
885 Kg/m3 @ 15 C/59 F
Electrical Conductivity
<50pS/m @20 C/68 F
Explosive Limits in Air, Vol. %

Lower
Upper
-11 C/12 F
Heat of Vaporization, @ 70 F
187.8 BTU/lb
0.248 BTU/lb2 F
Ideal Gas Heat of Formation
456.6 BTU/lb
Liquid Heat Capacity, @ 70 F
0.415 BTU/lb2 F
Melting Point
5.6 C/42.0 F
Molecular Formula
C6H6
Molecular Weight
78.114
2.7 - 12 ppm
Odor Threshold in Air4,5
1-6
1.4
7.1
Flash Point (closed cup)
Ideal Gas Heat Capacity, @ 70 F
1. Daubert, T.E., Danner, R.P., Sibul, H.M., and Stebbins, C.C.,

DIPPR Data Compilation of Pure Compound Properties,
Project 801 Sponsor Release, January 1994, Design Institute
for Physical Property Data, AIChE, New York, NY.
Note: Semiannual updates released in January and July.
2. Verschueren, K., Handbook of Environmental Data of
Organic Chemicals, 2nd ed. New York, NY: Van Nostrand
Reinhold Co., 1983, p. 237.
3. Shaw, D.G., vol. ed., Solubility Data Series Volume 37,
Hydrocarbons with Water and Seawater Part I:
Hydrocarbons C5 to C7 , New York, NY: Pergamon Press.
4. Shell International Research Maatschappij B.V., Safe
Handling of Benzene and Liquids Containing Benzene, The
Hague, The Netherlands, Shell International Research
Maatschappij B.V., 1980, p. 51.
5. American Conference of Governmental Industrial
Hygienists, Inc., Documentation of Threshold Limit Values
and Biological Exposure Indices, 6th edition, Cincinnati,
OH, 1991, p. 108.
0.271
710.4 psia
Partition Coefficient
n-Octanol/Water2
Log Pow = 1.95-2.13
Refractive Index nD, @ 77 F

Relative Vapor Density (Air=1)2
1.4979
Saturated Concentration in Air
99,000 ppm @ 20 C/68 F

150,000 ppm @ 29 C/85 F
2.77
Solubility of Benzene in Water,

@ 25 C/77 F
1.8 Kg/m3
Solubility of Water in Benzene,

@ 68 F
580 ppmw
Vapor Pressure, @ 70 F
1.52 psia @ 15 C/59 F
Viscosity (liquid) @ 70 F
4.24 x 10-4 lb/sq ft
Viscosity (vapor) @ 70 F
5.02 x 10-6 lb/sq ft
(Source: DIPPR Database1 unless otherwise indicated)
9/04
FIGURE 1.4: LIQUID DENSITY
FIGURE 1.5: VAPOR PRESSURE
9/04
1-7
FIGURE 1.6: HEAT OF VAPORIZATION
FIGURE 1.7: LIQUID HEAT CAPACITY
1-8
9/04
FIGURE 1.8: IDEAL GAS HEAT CAPACITY
FIGURE 1.9: LIQUID VISCOSITY
9/04
1-9
FIGURE 1.10: VAPOR VISCOSITY
FIGURE 1.11: LIQUID THERMAL CONDUCTIVITY
1-10
9/04
FIGURE 1.12: VAPOR THERMAL CONDUCTIVITY
FIGURE 1.13: SURFACE TENSION
9/04
1-11
FIGURE 1.14: SOLUBILITY OF WATER IN BENZENE
FIGURE 1.15: SECOND VIRIAL COEFFICIENT
1-12
9/04
1.5 Benzene Product Quality

Shell Chemicals* product quality objective is to
supply customers with benzene that meets their
current and future needs for purity, specific
impurities, and parameter consistency.
Table 1.2 shows a typical industry specification
for benzene. In some cases, individual customer
specification limits may differ from those given in
the table.
TABLE 1.2: TYPICAL INDUSTRY SPECIFICATION

FOR BENZENE
Specification
ASTM Test
Method
Benzene, Min. Wt.%
99.90
D4492
Sulfur, Max., ppmw
D4045
Thiophene,
Max., ppmw
0.6
D4735
Toluene,
Max., ppmw
300
D2360
Nonaromatic
Hydrocarbons,
Max., ppmw
500
D2360
Acid Wash Color,

Max.
D848
Acidity
None detected
D847
Copper Corrosion
Pass (1A or 1B)
D849
Clear, no free
water or
suspended matter
Visual
20
D1209
Rel. Density
15.56/15.56 C
0.8820-0.8860
D4052
Distillation Range,
Incl. 80.1 C @
760 mm Hg, C
1.0
D850
Solidification
Point, C
5.40
D852
Free of H2S and SO2
D853
Property
Appearance
Color, Max.,
Pt-Co Scale
Sulfur Compounds
9/04
1-13
1.6 Benzene Reactivities

and Incompatibilities
A literature search was conducted to capture the
various chemical reactivities and incompatibilities
that have been reported for benzene. Brethericks
Handbook of Reactive Chemical Hazards, Third
Edition, and the National Fire Protection
Associations Fire Protection Guide on Hazardous

Materials, 9th edition, 1986, are the primary sources
for the information listed in Table 1.3. Benzene also
presents a moderate explosion hazard if heated or
exposed to flame.
TABLE 1.3: CHEMICAL REACTIVITIES AND INCOMPATIBILITIES

REPORTED FOR BENZENE
If benzene comes in contact with...
Then it can...
Diborane
Explode on contact.
Bromine Pentafluoride
Explode on contact.
Permanganic Acid
Explode on contact.
Peroxomonosulfuric Acid
Explode on contact.
Peroxodisulfuric Acid
Explode on contact.
Iodine Pentafluoride
React violently.
Silver Perchlorate
Form a sensitive, explosive mixture.
Nitryl Perchlorate
Nitric Acid
Liquid Oxygen
Ozone
Arsenic Pentafluoride + Potassium Methoxide
Explode above 86 F (30 C).
Sodium Peroxide + Water
Ignite on contact.
Dioxygenyl Tetrafluoroborate
Ignite on contact.
Powdered Chromic Anhydride
Ignite on contact.
Iodine Heptafluoride
Ignite on contact.
Dioxygen Difluoride
Ignite on contact.
Hydrogen + Raney Nickel (above 410 F/210 C)
Form a vigorous or incandescent reaction.
Uranium Hexafluoride
Bromine Trifluoride
Oxidizing Materials (such as chlorine,

chlorine trifluoride, potassium peroxide)
React vigorously and/or explosively.
Perchlorates
Sulfuric Acid + Permanganates
Silver Perchlorate + Acetic Acid
1-14
9/04
2. HEALTH HAZARD
INFORMATION
2.1 MSDS Provides Health Information
2.2 Overview of Benzene Health Hazards
Health hazard information is provided to customers

on the Material Safety Data Sheets (MSDS) that are
sent to customers. The MSDS is in the appropriate
language for the country and in compliance with
the countrys regulation requirements.
MSDS may be accessed on the Shell Chemicals*
web site:
http://www.shell.com/chemicals/home/0,1098,1,00.html.
Select HSE at the top of the home page.
Select "Material Safety Data Sheets (MSDS)"
on the left side.
Select "Search Material Safety Data Sheets"
on the right side.
http://www.euapps.shell.com/MSDS/GotoMsds`
On the search screen, put benzene in the
product name field; select the language and
the country that you want. Click Search.
Benzene can affect the body by various routes of

exposure. These routes include direct liquid
contact, inhalation of vapors, absorption through
the skin, and ingestion. There can be immediate
(acute) as well as delayed (chronic) effects associated
with benzene exposure. These effects are described
briefly in this subsection with further detail provided
in subsequent sections. Liquid benzene is irritating
to the eyes and skin. Exposure to high airborne
concentrations of benzene may cause irritation of
the eyes, nose, throat, and respiratory tract. It may
also cause drowsiness, light-headedness, coughing,
and blurred vision. At very high concentrations,
unconsciousness and death may occur. Ingestion
of benzene may result in vomiting; aspiration
(breathing) of vomitus into the lungs can cause
chemical pneumonitis, which can be fatal.
Prolonged and repeated exposure to high
concentrations of benzene may cause serious
injury to blood-forming organs and is associated
with anemia (depletion of blood cells) and is
linked to the later development of acute
myelogenous leukemia (AML).
9/04
2-1
2.3 Eye Contact
2.5 Acute Inhalation Exposure
Eye contact with liquid benzene or its vapors can

result in irritation. Splash contact may cause a
moderate burning sensation, with slight reversible
corneal damage. If present in high concentrations,
vapors may cause temporary irritation of eyes or
respiratory system.
First Aid: If direct liquid contact occurs,
immediately flush eyes with plenty of water for
at least 15 minutes while holding eyelids open.
Get medical attention.
Generally, inhalation is the most significant route of

exposure because of benzenes high volatility. The
major toxic effect from the inhalation of concentrated
benzene vapors is on the central nervous system
(CNS). Early to moderate CNS depression may be
evidenced by giddiness, headache, dizziness, and
nausea; in extreme cases, unconsciousness, respiratory
depression, and death may occur. High vapor
concentrations may also cause irritation to the
mucous membranes of the nose and respiratory tract.
The severity of effects has been noted to escalate
as the vapor concentration increases. Table 2.1
provides an overview of the types of health effects
experienced by humans for various benzene exposures.
While there is no evidence that exposure to
industrially acceptable levels (i.e., the OSHA PEL)
of benzene has produced cardiac effects in humans,
animal studies have shown that inhalation of
high levels of benzene vapors produced cardiac
sensitization. Such sensitization may cause fatal
changes in heart rhythms. This latter effect was
shown to be enhanced by hypoxia (insufficient
oxygen) or the injection of adrenaline-like agents.
First Aid: DO NOT DELAY. Remove victim
to fresh air and provide oxygen if breathing is
difficult. Get medical attention immediately.
Note to Physician: Potential for cardiac
sensitization, particularly in abuse situations.
Hypoxia or negative inotropes may enhance
these effects. Consider oxygen therapy.
2.4 Skin Contact

Skin contact with liquid benzene may result in
irritation and erythema (reddening of the skin).
Prolonged and repeated contact can result in
defatting and drying of the skin, which may lead
to dermatitis and increased chance of secondary
infection.
Benzene can be absorbed through the skin,
though generally at a much lower rate than through
the mucous membranes of the respiratory system.
In the case of abraded skin, absorption may be
more rapid. Also, benzene may be more readily
absorbed if it is present in a mixture or as a
contaminant in solvents that are readily absorbed.
No signs of acute intoxication due to liquid
benzene absorption have been reported.
In animal studies, insufficient quantities of
benzene were absorbed through the skin to
cause toxicity.
First Aid: Remove contaminated clothing and
shoes. Immediately flush skin with water for 15
minutes. Follow by washing with soap and water.
If irritation occurs, get medical attention. Do not
reuse clothing until cleaned.
TABLE 2.1: HUMAN HEALTH EFFECTS

EXPERIENCED AT VARIOUS BENZENE EXPOSURES1
Exposure
Concentration
(ppm)
Time
(min.)
Health Effects Noted
50-150
300
Headache and fatigue
500-3,000
60
Headache and
increased lethargy
3,000-5,000
30
Signs of intoxication
19,000-20,000
5-10
May be fatal
1. Source: George D. and Florence E. Clayton, Pattys

Industrial Hygiene and Toxicology, Vol. 2B, 4th ed., John
Wiley & Sons, Inc., New York, 1994, pp. 1308 - 1309.
2-2
9/04
2.6 Ingestion
2.7 Subchronic/Chronic Toxicity
The main hazard in the unlikely event of benzene

ingestion is aspiration into the lungs. This may
possibly result in chemical pneumonitis, which
can be fatal.
Ingestion of benzene can also affect the central
nervous system (CNS) as benzene is a neuroconvulsant. It may produce stimulation characterized by
tremors, convulsions, and visual disturbances. Early
to moderate CNS depression may be evidenced by
giddiness, headache, dizziness, and nausea; in
extreme cases, unconsciousness, respiratory
depression, and death may occur.
Oral ingestion of 9 to 12 grams (10-14 milliliters)
of benzene by three (3) humans has been reported
to cause signs of staggering gait, vomiting, sleepiness,
shallow rapid pulse, loss of consciousness, and later
delirium, with subsequent chemical pneumonitis,
collapse due to initial stimulation, then abrupt CNS
depression.
First Aid: Do not induce vomiting. If vomiting
occurs spontaneously, keep head below hips to
prevent aspiration of liquid into the lungs. Get
medical attention.
Note to Physician: If benzene has been
swallowed and vomited, there is a potential for
chemical pneumonitis. Consider gastric lavage
with protected airway, administration of activated
charcoal.
CARCINOGENICITY
9/04
Benzene has been classified as a known human

carcinogen. Prolonged and repeated exposure to
high concentrations of benzene may cause serious
injury to blood-forming organs and is associated
with anemia (depletion of blood cells) and is linked
to the later development of acute myelogenous
leukemia (AML). (See Section 2.8 Epidemiology for
additional information on the association between
AML and occupational exposure to benzene.) There
is not conclusive evidence linking benzene exposure
and other forms of human leukemia. Damage to
the blood-forming organs may be evidenced by
easy fatigability and pallor (red blood cell effect),
decreased resistance to infection (white blood cell
effect), and excessive bruising and bleeding
(platelet effect).
Animal studies have also shown benzene to
be a carcinogen, although the types of tumors
commonly observed are not leukemias. In fact,
there is no currently accepted animal model for
benzene leukemogenesis. In rats and mice,
benzene causes solid tumors in epithelial tissues
such as Zymbals gland and the mammary glands.
Studies of exposed humans have not revealed any
consistent increase in tumors of any organ or tissue
other than AML. Table 2.2 lists the carcinogenicity
classifications for benzene by various organizations.
2-3
REPRODUCTIVE TOXICITY
Benzene does not appear to be a potent
reproductive toxin in experimental animals, based
on available toxicity data. There is limited evidence
of ovarian and testicular toxicity in mice, but not
rats, exposed to benzene vapor at 300 ppm for 13
weeks. One study has shown impaired fertility in
female rats exposed to 210 ppm benzene for 10-15
days prior to mating, but a more recent study in
rats exposed at up to 300 ppm pre-mating through
gestation and lactation showed no effects on fertility,
reproduction or lactation. Benzene has not been
shown to have an effect on human reproduction.
DEVELOPMENTAL TOXICITY
Numerous studies on experimental animals have
failed to detect teratogenic effects (birth defects)
even at doses of benzene toxic to the female
animals. There is some evidence of fetotoxicity
but no malformations in mice and rabbits exposed
to 500 ppm and higher concentrations of benzene
vapor during gestation.
Fetotoxic effects occurred only in the presence
of maternal toxicity. There is no evidence of
adverse developmental effects in humans.
GENOTOXICITY
TABLE 2.2: CARCINOGENICITY

CLASSIFICATIONS OF BENZENE
Organization
Carcinogenicity
Classification
National Toxicology
Program (NTP)
Known carcinogen
International Agency
for Research on
Cancer (IARC)
Group 1: Human
carcinogen
U.S. Environmental
Protection Agency
(EPA) - Integrated Risk
Information System (IRIS)
Group A: Human
carcinogen
National Institute for

Occupational Safety &
Health (NIOSH)
Potential occupational
carcinogen
American Conference of
Governmental Industrial
Hygienists (ACGIH)
Group A1: Confirmed

human carcinogen
Occupational Safety &

Health Administration
(OSHA)
Cancar hazard
European Commission
(EC)
Carcinogen category 1
Benzene has been shown to be non-mutagenic or

weakly mutagenic in a variety of in vitro (test tube)
systems. It has, however, been found to cause other
types of chromosome damage (micronuclei,
chromosome breakage, non-dysjunctional events) in
both laboratory animals and workers exposed to
high doses of benzene. These effects appear to
be related to one or more metabolites of benzene,
possibly acting in combination. Benzene
metabolites can also bind to proteins, forming
detectable complexes (adducts). There is limited
evidence of binding to the genetic material (DNA)
itself. The relationship of these genotoxic effects
to the causation of leukemia or tumors in
experimental animals is unknown.
2-4
9/04
2.8 Epidemiology
2.9 Medical Surveillance
Statistically significant associations between acute

myelogenous leukemia and occupational exposure
to benzene have been shown in a number of
epidemiological studies. The study types in which
this relationship has been observed include both
cohort and case-control.
Timing, extent, and intensity of exposure are
important in predicting benzenes hematotoxic and
leukemogenic responses. According to the
American Petroleum Institute, increased risk of
leukemia has not been observed among petroleum
workers whose exposure was below the original
OSHA PEL of 10 ppm. The current level is 1 ppm.
The American Petroleum Institute also reports that
increased risk of leukemia has only been observed
among those who at some time experienced
exposure to benzene concentrations in excess of
20 to 60 ppm (regardless of cumulative exposure).
OSHAs Benzene Standard in 29 CFR Part

1910.1028(i) specifically requires that a Medical
Surveillance Program be made available for
employees who meet one or more of the specified
exposure categories. The medical surveillance
section in the OSHA standard details what must be
included as a minimum in the initial, periodic, and
emergency medical examinations. Additional
medical examinations and referrals may be
necessitated based on the results of these
examinations. The OSHA Benzene Standard is
contained in Appendix B of this document.
9/04
2-5
3. ECOTOXICITY/ECOLOGICAL
FATE
3.1 Ecotoxicity
AQUATIC TOXICITY
AQUATIC PROPERTIES
Benzene rapidly evaporates from open water. The

data presented here are those of flow-through or
closed static tests. The source for this information
is the unpublished PSE Dossier for Benzene
prepared by Shell International Petroleum
Maatschappij, B.V. (1994).
Benzene is not expected to bioconcentrate in

aquatic organisms. It is also considered to be
readily biodegradable, and will exist predominantly
in the vapor phase if released to the atmosphere.
Table 3.1 provides further details on this data.
3.2 Ecological Fate
Fish
(Classified as toxic since 1< LC50 < 10)
Freshwater: 96 hour LC50
Oncorhynchus mykiss
Marine:
96 hour LC50 Morone saxatilis
FATE IN SOIL
5 mg/l
6 mg/l
Invertebrates
(Classified as slightly toxic since 10 < EC50 < 100)
Freshwater: 48 hour EC50 Daphnia pulex
15 mg/l
48 hour EC50 Ischnura elegans 10 mg/l
Marine:
96 hour EC50
Paleomonestes pugio
27 mg/l
Benzene released to soil will be subject to rapid

volatilization near the surface. The portion that
does not evaporate will be highly mobile in soil
and may leach to ground water. Thus, it is not
expected to significantly adsorb to sediment.
Benzene may be subject to biodegradation in
shallow, aerobic ground waters, but probably not
under anaerobic conditions.
Algae
(Classified as slightly toxic since 10 < EC50 < 100)
Freshwater: 72 hour EC50 Selenastrum
capricornutum
29 mg/l
Marine:
72 hour EC50 Skeletonema

costatrum
20 mg/l
Bacteria/Other Organisms
(Classified as practically non-toxic to bacteria and
protozoa)
6 hour NOEC
Pseudomonas putida
92 mg/l
48 hour NOEC Chilomonas
paramecium
400 mg/l
LC50 = Concentration at which lethal effect observed in 50% of test species.
EC50 = Concentration at which biological effect observed in 50% of test species.
NOEC = No observable effect concentration.
9/04
3-1
FATE IN WATER
FATE IN AIR
Benzene will volatilize rapidly when it is released

into water. The estimated half-life for volatilization
of benzene from a model river is 0.15 days. It is not
expected to appreciably adsorb to sediment, nor is
it susceptible to hydrolysis. According to European
criteria, it is classified as "readily biodegradable."
Benzene released to the atmosphere will exist

predominantly in the vapor phase. Gas-phase
benzene is not subject to direct photolysis, though
it will react, i.e., be degraded, with photochemically
produced hydroxyl radicals. In polluted atmospheres
that contain nitrogen oxides or sulfur dioxides,
the reaction time is accelerated. Products of photo
oxidation include phenol, nitrophenols, nitrobenzene,
formic acid, and peroxyacetyl nitrate. Although its
water solubility is limited, benzene is also removed
from the atmosphere via rain.
TABLE 3.1: ENVIRONMENTAL FATE PROPERTIES OF BENZENE

Property
Value
Comments
Bioconcentration
Octanol Water Partition Coefficient
(log Pow)
2.13
Bioconcentration Factor (BCF)
4.4
Bioconcentration is the increase in tissue concentration

when the rate of intake is > rate of excretion and
metabolism. BCF values < 100 and log Pows < 3.5
indicate that benzene is not expected to
bioconcentrate in aquatic organisms
Biodegradation
Calc. Theoretical Oxygen
Demand (ThOD)
3.08 gO2/g
Closed Bottle Biological

Oxygen Demand (BOD) at 20 C 71% ThOD
Biodegradation is a measure of the ability of a

substance to break down or decompose rapidly under
natural conditions and processes. Benzene is readily
biodegradable, meeting the 10 day window criterion.
Distribution (predicted)
In Air
In Water
In Soil
99.3%
0.7%
0%
Benzene will exist predominantly in the vapor phase

if it is released to the atmosphere. It will evaporate
from both soil and water.
Persistence
Evaporation Half-Life from
Model River
Persistence in Total
Environment (half-life)
3-2
0.15 day
Both of these values are calculated/predicted.
One week
9/04
4. REGULATORY OVERVIEW
The intent of this section is to provide an overview
of the U.S. state, federal, and international health,
safety, and environmental regulations which apply
to benzene. A brief summary/explanation of each
regulation is provided prior to addressing the
regulation as it specifically applies to benzene.
Please note that while this is a fairly encompassing overview, it is NOT an exhaustive summary
of all health, safety, and environmental regulations
which are applicable to benzene. Similarly, the
brief overviews of the regulations at the beginning
of each section are not intended to be complete
interpretations or clarifications. For detailed
information, the specific regulation(s) should be
referenced. The Code of Federal Regulations (CFR),
where the federal information can be located, has
been listed where applicable.
Additional regulatory information is contained
elsewhere in this binder. For information pertaining
to Department of Transportation (DOT) benzenerelated regulations, refer to Section 7.
Transportation.
4.1 Benzene Health and Safety Standards

OCCUPATIONAL SAFETY AND HEALTH
ADMINISTRATION (OSHA)
Benzene exposure in the U.S. workplace is regulated
by OSHA in 29 CFR 1910.1028. This specific health
and safety standard for benzene contains the
permissible exposure limits (PELs) for airborne
concentrations of benzene, as well as various
ancillary provisions. Examples of the ancillary
provisions include medical surveillance, employee
training, exposure monitoring, and record keeping
requirements. OSHA requires compliance with the

PELs through engineering and work practice
controls, and permits respirators only to be used as
an interim measure or where engineering controls
and/or work practices are infeasible, or during
emergencies. The PELs are more fully discussed in
Section 4.2 Occupational Exposure Limits for
Benzene. A copy of the OSHA Benzene Standard,
including its appendices A through D, is contained
in Appendix B of this document.
U.S. COAST GUARD

The Marine Occupational Safety and Health
Standard for Benzene contained in 46 CFR 197
applies to all Coast Guard inspected vessels,
including tank ships and barges that carry liquids
containing 0.5% or greater benzene by volume. The
exposure limits are the same as those contained in
the OSHA Benzene Standard.
Unlike OSHA, the Coast Guard does not specify
what method or combination of methods is to be
used in complying with the regulation. It permits
engineering controls, revised work practices, and/or
personal protective devices to be used without
mandating any specific method. A copy of the
Marine Occupational Safety and Health Standard
for Benzene contained in Appendix C of this
document.
9/04
4-1
4.2 Occupational Exposure Limits

for Benzene
GENERAL INFORMATION ON
OCCUPATIONAL EXPOSURE LIMITS
OCCUPATIONAL EXPOSURE LIMITS

FOR BENZENE
OSHA Permissible Exposure Limits-Time-Weighted

Averages (PEL-TWAs) are the maximum exposures
permitted by OSHA to time-weighted average
airborne concentrations of substances for any 8hour workday of a 40-hour workweek. Employers
must comply with these limits by law. Short-term
exposure limits (STELs) are 15-minute time-weighted
average concentrations not to be exceeded during
the workday. An action level is typically an 8-hour
time-weighted average airborne concentration that,
if exceeded, will trigger a number of the ancillary
provisions of an OSHA health standard.
Threshold Limit Values (TLVs) are limits
established by the American Conference of
Governmental Industrial Hygienists (ACGIH).
TLV-TWAs refer to the time-weighted average
airborne concentrations of substances for a normal
8-hour workday and a 40-hour workweek, to which
nearly all workers may be repeatedly exposed, day
after day, without experiencing an adverse health
effect. TLVs are intended to be used in the practice of
industrial hygiene as guidelines or recommendations
in the control of potential health hazards.
The National Institute of Occupational Health
and Safety (NIOSH) also publishes recommended
exposure limits (RELs). The RELs are usually for up
to a 10-hour work shift and a 40-hour workweek.
Table 4.1 provides a summary of the occupational

exposure limits used in the United States for benzene.
4-2
TABLE 4.1: OCCUPATIONAL EXPOSURE LIMITS

FOR BENZENE IN THE U.S.
Organization/Agency Occupational Exposure Limit
OSHA PEL
1 ppm TWA
5 ppm STEL
0.5 ppm ACTION
Coast Guard
1 ppm TWA
5 ppm STEL
0.5 ppm ACTION
ACGIH TLV
0.5 ppm TWA

2.5 ppm STEL Skin Notation*
NIOSH REL
0.1 ppm TWA

1 ppm STEL
500 ppm IDLH**
* Skin notation: air sampling alone is insufficient to accurately

quantify exposure. Measure to prevent significant skin
absorption may be required
** Immediately Dangerous to Life or Health
BIOLOGICAL EXPOSURE INDICES

The American Conference of Governmental Industrial
Hygienists (ACGIH) has established Biological
Exposure Indices (BEIs) for benzene. BEIs are
similar to TLVs in that they are reference values
intended as guidelines for the evaluation of potential
health hazards in the practice of industrial hygiene.
However, BEIs involve biological monitoring rather
than the workplace air monitoring associated
with TLVs.
The ACGIH specifies that "BEIs represent the
levels of determinants which are most likely to be
observed in specimens collected from a healthy
worker who has been exposed to chemicals to the
same extent as a worker with inhalation exposure
to the TLV." The determinant can be the chemical
itself or its metabolite(s), or a characteristic reversible
biochemical change induced by the chemical. The
BEIs for benzene are listed in Table 4.4.
9/04
TABLE 4.2: OTHER EXPOSURE GUIDELINES

Organization/Agency
Exposure Guideline
American Industrial
Hygienists Association
(AIHA) Emergency
Response Planning
Guidelines (ERPGs)
EPRG-1 50 ppm
EPRG-2 150 ppm
EPRG-3 1000 ppm
EPA ACUTE EXPOSURE GUIDELINE LEVEL PROPOSED

AEGLs represent threshold exposure limits for the
general public and are applicable to emergency
exposure periods ranging from 10 min to 8 h.
AEGL-2 and AEGL-3, and AEGL-1 values as appropriate, will be developed for each of five exposure
periods (10 and 30 min, 1 h, 4 h, and 8 h) and will
be distinguished by varying degrees of severity of
toxic effects. It is believed that the recommended
exposure levels are applicable to the general
population including infants and children, and
other individuals who may be susceptible.
For current status, consult the EPA Website:
www.epa.gov/oppt/aegl/results72.htm
TABLE 4.3: ACUTE EXPOSURE GUIDELINE LEVEL

ppm
10 min
30 min
60 min
4 hr
8 hr
AEGL 1
127
73
52
18
9.0
AEGL 2
2,000*
1,100
800
400
200
AEGL 3
**see below
5,600*
4,000*
2,000*
990
Lower Explosive Limit (LEL) = 14,000 ppm

* = >10% LEL; ** = >50% LEL
AEGL 3 - 10 mins = ** 9,700 ppm
For values denoted as * safety considerations against the hazard(s) of explosion(s) must be taken into account.
For values denoted as ** extreme safety considerations against the hazard(s) of explosion(s) must be taken into account.
9/04
4-3
4.3 Federal Environmental

Regulatory Overview
TABLE 4.4: ACGIH BIOLOGICAL EXPOSURE INDICES
(BEIS) FOR BENZENE
Determinant
Sampling Time
BEI
Total Phenol in Urine
End of shift
50 mg/g
creatinine1
Benzene in Exhaled Air: Prior to next shift

Mixed-Exhaled
0.08 ppm2
End-Exhaled
0.12 ppm2
1. This determinant is the most convenient one to use as a
BEI. Unfortunately, there is a variable amount of phenol
present in the urine collected from subjects who have not
been occupationally exposed to benzene. The ACGIH
indicates that this determinant should, therefore, be applied
only as a group test due to large individual variation. This
determinant is also considered to be nonspecific as it is
observed after exposure to some other chemicals. It is
recommended by the ACGIH that determination of benzene
in exhaled air be used as a confirmatory test.
2. This biological contaminant is an indicator of exposure to
the chemical as benzene is not found in the exhaled air of
persons not exposed to benzene. While this test is specific,
it can be impacted by physical activity during and after
benzene exposure. As a result, the ACGIH recommends this
test as a confirmatory test in connection with phenol in urine.
As noted in the ACGIH TLV and BEI Booklet, it

is essential to consult the specific BEI documentation
published in the Documentation of Threshold Limit
Values and Biological Exposure Indices, 6th edition,
1991, before designing biological monitoring and
interpreting BEIs.
RESOURCE CONSERVATION
AND RECOVERY ACT (RCRA)
The EPAs Resource Conservation and Recovery Act
(RCRA) regulates the management of hazardous and
solid wastes. It gives the EPA authority to control
hazardous wastes from generation to disposal. A
solid waste is hazardous if it exhibits one or more
of the designated characteristics (i.e., ignitability,
corrosivity, reactivity, and toxicity), or is specifically
listed as a RCRA hazardous waste.
Under RCRA (40 CFR 261.33), benzene as a
commercial chemical product, intermediate, or offspecification product that becomes a waste material
is a specifically listed hazardous waste. The RCRA
hazardous waste number for such material is U019.
A solid waste that has a benzene concentration of
0.5 mg/l or greater, as determined by the toxicity
characteristic leaching procedure (TCLP), is regulated
as a characteristic hazardous waste. Per 40 CFR
261.24, the RCRA hazardous waste number for this
material is D018.
In addition to the preceding, there are several
other specifically listed benzene-related RCRA
hazardous wastes. For example, benzene used as a
spent solvent has a hazardous waste code of F005.
40 CFR 261.31 and 261.32 should be referred to for
a complete listing of benzene-related wastes from
non-specific and specific sources.
COMPREHENSIVE ENVIRONMENTAL
RESPONSE, COMPENSATION
AND LIABILITY ACT (CERCLA)
The Comprehensive Environmental Response,
Compensation and Liability Act (CERCLA), also
known as Superfund, established broad federal
authority to respond to releases or threats of
releases of hazardous substances from vessels and
facilities. The list of CERCLA hazardous substances
and their reportable quantities (RQs) is contained
in 40 CFR 302.
Lists of regulated hazardous constituents in
other environmental statutes were used by the EPA
4-4
9/04
to compile the CERCLA hazardous substance list.

Benzene was included in the statutory CERCLA RQ
list on the basis of its designation as a hazardous
constituent in the CAA, CWA, and RCRA. According
to the degree of hazard, RQs are set at either 1,000,
100, 10, or one pound. The statutory RQ for
benzene is 10 pounds based on its carcinogenicity
(40 CFR 302.4). The one-pound RQ is generally
reserved for substances that are acutely or extremely
hazardous. It is not anticipated that the RQ for
benzene will be revised based on its properties.
Immediate notification must be made to the
National Response Center, state and local response
authorities, i.e., SARA Title III - Section 304 notification
requirements, if a CERCLA hazardous substance has
been released in a quantity equal to or greater than
its RQ.
SUPERFUND AMENDMENTS AND

REAUTHORIZATION ACT - TITLE III (SARA TITLE III)
SARA Title III is also known as the Emergency
Planning and Community Right-to-Know Act
(EPCRA). It contains four major sections: emergency
planning (Section 301-303); emergency release
notification (Section 304); community right-to-know
reporting requirements (Section 311/312); and, toxic
chemical release reporting-emissions inventory
(Section 313).
Sections 301-303: Emergency response plans
must be prepared by any facility that has present
any of the listed chemicals (Extremely Hazardous
Substances) in Section 302 (40 CFR 355) at a
quantity equal to or greater than its threshold
planning quantity.
Benzene is not listed as an Extremely
Hazardous Substance.
Section 304: Facilities must make immediate
emergency notifications if there is a release of a
listed hazardous substance that exceeds the
reportable quantity (RQ) for that substance.
Substances subject to this requirement are those
identified on the list of Extremely Hazardous
Substances in Section 302, and those on the list of
CERCLA hazardous substances, found in 40 CFR 302.
9/04
Benzene is a CERCLA hazardous substance with

a 10 pound RQ (See Section 4.3 Comprehensive
Environmental Response, Compensation and Liability
Act (CERCLA)). Immediate emergency notifications
are required for releases in excess of this amount.
Sections 311/312: These sections establish
community right-to-know reporting requirements
for "Hazardous Chemicals." Hazardous Chemicals
are those chemicals regulated under the OSHA
Hazard Communication Standard (29 CFR 1920.1200),
and which require the preparation of a Material
Safety Data Sheet (MSDS).
Section 311 requires a one-time submission of
the MSDS, or alternatively, a list of materials (which
exceed specified reporting thresholds) at the facility.
The list of chemicals must be grouped into five
health or physical hazard categories established
by the EPA for purposes of this report.
Section 312 requires annual "Emergency and
Hazardous Chemical Inventories" be submitted in a
reporting format that identifies the hazard categories
(Tier I reports). It also requires the submittal of
a Tier II inventory upon request. The following
Section 311/312 hazard categories apply to benzene:
Immediate (acute) Health Hazard
Delayed (chronic) Health Hazard
Fire Hazard
Section 313: This section requires an annual
estimate and reporting of toxic chemicals released to
the environment during the prior calendar year. A
list of "Toxic Chemicals" is contained in 40 CFR 372.
Benzene is listed as a toxic chemical and is,
therefore, subject to the Toxic Release Inventory
(TRI) reporting requirements of Section 313. Annual
reporting requirements apply to facilities that
manufacture or process benzene in amounts above
the threshold planning quantity of 25,000 pounds.
There is a 10,000 pound threshold planning quantity
which triggers reporting requirements for facilities
that use benzene in ways other than those defined
by manufacturing or processing.
For more information on the Emergency
Planning and Community Right-to-Know Act, call
the EPAs Information Hotline at 1-800-535-0202.
4-5
CLEAN AIR ACT (CAA)

In 1970, Congress passed the Clean Air Act (CAA)
to provide the structure for the EPAs air pollution
control program. The CAA was most recently
amended in 1990, with some major changes being
made to the act. These changes are often referred
to as the Clean Air Act Amendments of 1990 (CAAA
of 1990). A key element of the CAA is to establish
national ambient air quality standards that represent
the level at which specified air pollutants are
determined by the EPA to be safe.
Section 111: The CAAA of 1990 has standards of
performance for new stationary sources (40 CFR
60). Subpart VV addresses standards of performance
for equipment leaks of volatile organic compounds
in the synthetic organic chemicals manufacturing
industry (SOCMI). There is a listing of chemicals
produced as intermediates or final products, by
process units, covered under this part. Benzene is
one of the chemicals listed as a Potential Human
Health Hazard (40 CFR 60.489).
Section 112: The National Emissions Standards
for Hazardous Air Pollutants (NESHAP) were
established under Section 112 of the Clean Air Act.
The NESHAP requires the EPA to develop standards
related to various industrial and manufacturing
categories for specifically listed hazardous air
pollutants (HAPs). The standards are to provide "an
ample margin of safety to protect human health,"
and to consider the maximum achievable
control technology(MACT).
In 40 CFR par 61 there are NESHAP standards
for eight (8) substances, one of which is benzene.
The benzene NESHAP was originally published by
the EPA on June 8, 1977.Three revisions have been
made to the rule: September 14, 1989; September
19, 1989; and March 7, 1990. The benzene-related
NESHAP standards are located in 40 CFR 61.
The NESHAP program is to augmented by the
Air Toxics Program as detailed in the Clean Air Act
Amendments of 1990. It should be noted, though,
that existing NESHAP regulations remain in effect.
The revised Section 112 of the CAA establishes a
new technology and risk-based program. In April,
4-6
1994, the EPA promulgated a new regulation called

the hazardous organic NESHAP, or HON. The HON
requires sources to achieve emission limits reflecting
the application of MACT, consistent with Sections
112(d) of the CAA.
The rule regulates emission of HAPs at both
new and existing SOCMI sources, and from
equipment leaks at sources in specified processes.
The CAAA lists 189 HAPs, including benzene,
which are to be regulated under the Air Toxics
Program (40 CFR part 63 subparts F, G and H).
Benzene is also listed as a Group I SOCMI chemical
under the HON (40 CFR 63) for wastewater purposes.
In the regulations governing compliance for early
reductions of HAPs, benzene was placed on the list
of high-risk hazardous air pollutants (40 CFR 63.74).
On November 10, 2003, EPA also promulgated
a rule called the Miscellaneous Organic NESHAP
(MON) which governs the emissions of HAPs
(including benzene) from SOCMI processes not
already covered by the HON (40 CFR part 63
subpart FFFF). Benzene is also regulated for other
source categories under other subparts of part 63.
CLEAN WATER ACT (CWA)

The Clean Water Act (CWA) is the cornerstone of
surface water quality protection in the United
States. (The Act does not deal directly with ground
water nor with water quantity issues.) The statute
employs a variety of regulatory and nonregulatory
tools to sharply reduce direct pollutant discharges
into waterways, finance municipal wastewater
treatment facilities, and manage polluted runoff.
These tools are employed to achieve the broader
goal of restoring and maintaining the chemical,
physical, and biological integrity of the nation's
waters so that they can support "the protection
and propagation of fish, shellfish, and wildlife
and recreation in and on the water."
For many years following the passage of CWA
in 1972, EPA, states, and Indian tribes focused
mainly on the chemical aspects of the "integrity"
9/04
goal. During the last decade, however, more

attention has been given to physical and biological
integrity. Also, in the early decades of the Act's
implementation, efforts focused on regulating
discharges from traditional "point source" facilities,
such as municipal sewage plants and industrial
facilities, with little attention paid to runoff from
streets, construction sites, farms, and other
"wet-weather" sources.
Starting in the late 1980s, efforts to address
polluted runoff have increased significantly. For
"nonpoint" runoff, voluntary programs, including
cost-sharing with landowners are the key tool. For
"wet weather point sources" like urban storm
sewer systems and construction sites, a regulatory
approach is being employed.

Evolution of CWA programs over the last
decade has also included something of a shift from
a program-by-program, source-by-source, pollutantby-pollutant approach to more holistic
watershed-based strategies. Under the watershed
approach equal emphasis is placed on protecting
healthy waters and restoring impaired ones. A full
array of issues are addressed, not just those subject
to CWA regulatory authority. Involvement of
stakeholder groups in the development and
implementation of strategies for achieving and
maintaining state water quality and other environmental goals is another hallmark of this approach.
BENZENE IS REGULATED UNDER THE FOLLOWING SECTIONS OF THE CLEAN WATER ACT:
Clean Water Act Section 304(a)(1) Ambient Water Quality Criteria
<https://webinsight.arielresearch.com/ArielFT/NAdoc/CWA_304.htm>
Clean Water Act Section 307(a)(1) Toxic Pollutants (40 CFR 401.15)
Clean Water Act Priority Pollutants for Steam Electric Power Generating Point Source Category
(40 CFR 423,Appendix A) <https://webinsight.arielresearch.com/ArielFT/NAdoc/CWA_PRI.htm>
Clean Water Act Section 311 Hazardous Chemicals (40 CFR 116.4)
Clean Water Act Section 311 Hazardous Substances (40 CFR 117.3)
<https://webinsight.arielresearch.com/ArielFT/NAdoc/CWA311X.htm>
The Reportable Quantity Code is A
The Reportable Quantity is 10 lbs
Safe Drinking Water Act MCLs, MRDLs, and Action Levels (40 CFR 141)
<https://webinsight.arielresearch.com/ArielFT/NAdoc/SDWA_MCLS.htm>
SDWA Maximum Contaminant Level: 0.005 mg/l.
Safe Drinking Water Act MCLGs and MRDLGs (40 CFR 141)
<https://webinsight.arielresearch.com/ArielFT/NAdoc/SDWA_MCLG.htm>
SDWA Maximum Contaminant Level Goal: 0 mg/l.
Safe Drinking Water Act 1986 Amendments Statutory Contaminants (53 Fed. Reg. 1892)
<https://webinsight.arielresearch.com/ArielFT/NAdoc/SDWA_86STA.htm>
For additional up-to-date information, go to www.epa.gov <http://www.epa.gov>
and put clean water act in the search field.
9/04
4-7
TOXIC SUBSTANCES CONTROL ACT (TSCA)

The Toxic Substances Control Act (TSCA), passed
by Congress in 1976 (Public Law 94-469), is a
complex and detailed statute which empowers the
U.S. Environmental Protection Agency (EPA) to
evaluate and regulate chemical substances and
mixtures which may have an adverse impact on
human health and the environment. It provides the
EPA with broad authority to regulate the manufacture,
import, processing, distribution, use, and disposal
of chemical substances.
TSCAs coverage is comprehensive. With the
exception of chemicals specifically regulated by
certain other federal laws (i.e. FIFRA for pesticides;
FDA for food, drugs and cosmetics), it potentially
applies to all chemicals manufactured, imported,
processed, distributed, or used in the United States.
TSCA not only affects the chemical industry itself,
but many industries that use its products as well.
The TSCA sections which apply to benzene are
described in the ensuing information.
Section 4 - Chemical Test Rules: Section 4
of TSCA (40 CFR 799) gives the EPA authority
to require testing of chemical substances and
mixtures if the EPA finds that they may present an
unreasonable risk of injury to the environment or
health, or if they will be produced in substantial
quantities resulting in significant human or
environmental exposure.
The EPA is given the authority under Section 4
to require testing of chemical substances and
mixtures. There are presently no testing requirements
for benzene. However, 12 chemical substances,
including benzene, were identified as having
toxicological data needs by the Agency for Toxic
Substances and Disease Registry (ATSDR), National
Toxicological Program (NTP), and the EPA pursuant
to Section 104(i)(5) of the Comprehensive
Environmental Response, Compensation and
Liability Act of 1980 (CERCLA, or Superfund).
4-8
Section 8(b) - Chemical Substances Inventory:

To be used in a commercial application or as a
component in a commercial product, a material has
to be listed on the TSCA Chemical Substances
Inventory (40 CFR 704, 710, 720, and 723).
Benzene, CAS # 71-43-2, is listed on this inventory.
Section 13 - Import Certification: TSCA specifically
requires that any chemical substance mixture, or
article containing a chemical substance or mixture
be refused entry into the customs territory of the
United States if it fails to comply with any rule in
effect under TSCA or is offered for entry in violation
of Section 5, 6, or 7 of TSCA. Regulatory authority
for Section 13 of TSCA lies with the Environmental
Protection Agency (EPA) and U.S. Customs.
Regulations addressing the import requirements of
TSCA may be found at 40 CFR 707.20 and 19 CFR
12.118 -12.128. All imports of benzene must be
positively TSCA certified with US Customs at the
time of importation.
4.4 Federal Regulatory Management

for Prevention of Accidental Releases
OSHA - PROCESS SAFETY MANAGEMENT
OF HIGHLY HAZARDOUS CHEMICALS
(29 CFR 1910.119)
This OSHA section contains requirements for
preventing or minimizing the consequences of
catastrophic releases of toxic, reactive, flammable,
or explosive chemicals. Such releases may result
in toxic, fire, or explosion hazards.
Benzene is not specifically listed as a highly
hazardous chemical in the standard. It does,
though, meet the definition of a flammable liquid
or gas. As a result, a process which involves the
use of benzene on site in one location, in a quantity
of 10,000 pounds or more, is subject to the
requirements of this standard.
9/04
4.5 State Right-to-Know Laws/Regulations

STATE RIGHT-TO-KNOW LISTINGS
In addition to the Federal Right-to-Know requirements
(OSHAs Hazard Communication Standard and
EPAs SARA Title III, which is also known as the
Emergency Planning and Community Right-to-Know
Act of 1986 (EPCRA)), numerous states have
adopted right-to-know laws or regulations.
When the state right-to-know laws are contrasted
with the OSHA rule, significant differences are often
observed regarding the scope, chemicals regulated,
and labeling requirements. Various states have
established specific lists of regulated chemicals
rather than requiring hazard determinations to be
conducted to ascertain whether a chemical should
be considered as "hazardous." Benzene does meet
the definition of a hazardous chemical per OSHAs
Hazard Communication Standard (29 CFR 1910.1200).
Table 4.5 contains a list of the states Shell
Chemical LP monitors that have right-to-know
chemical lists which include benzene. For detailed
information on the requirements of a
particular state right-to-know law, the appropriate
state agency should be contacted.
CALIFORNIA SAFE DRINKING WATER

AND TOXICS ENFORCEMENT ACT OF 1986
(PROPOSITION 65)
The California Safe Drinking Water and Toxics
Enforcement Act of 1986 (better known as
Proposition 65) has two primary objectives:
(1) Prohibition on contaminating drinking water
with chemicals known to cause cancer or
reproductive toxicity, and;
(2) Warning of individuals before exposure to
chemicals known to cause cancer or
reproductive toxicity.
On February 27, 1987, benzene was added to
the list of chemicals known to the state of
California to cause cancer. The No Significant Risk
Level established for benzene by the state is seven
(7) micrograms/day.
For additional information regarding Proposition
65 (California Health and Safety Code Section
25249.5), contact: California Environmental
Protection Agency, Office of Environmental Health
Hazard Assessment, 601 N. 7th Street, P.O. Box
942732, Sacramento, CA 94234-7320.
TABLE 4.5: STATES WITH SPECIFIC RIGHT- TO-KNOW

LISTINGS FOR BENZENE
California
Connecticut
Illinois
Indiana
Kentucky
Louisiana
Massachusetts
Michigan
Minnesota
New Jersey
New York
North Carolina
Pennsylvania
Rhode Island.
9/04
4-9
4.6 Food and Drug Administration (FDA)

The Food and Drug Administration (FDA) has
authority for the regulation of food and pharmaceutical activities in the United States. As detailed in
21 CFR 175.105, benzene can be used only as a
component of adhesives. In this application, it is
considered to be an indirect food additive. The
adhesive in which benzene is used must either be
separated from the food by a functional barrier or
used subject to additional limitations specified in
the regulation.
Any use of benzene in pharmaceutical products
would be subject to approval pursuant to the FDAs
general procedures for testing and certifying
pharmaceutical products.
Shell Chemicals* policy is to not sell benzene
into food, drug or cosmetic applications.
4-10
4.7 Consumer Product Safety

Commission (CPSC)
The Consumer Product Safety Commission (CPSC),
established in 1972 by the Consumer Product Safety
Act (CPSA), has responsibility for protecting the
public from unreasonable risks associated with
consumer products. In 1978, the CPSC proposed a
ban on all consumer products (except gasoline and
solvents or reagents for laboratory use) containing
benzene as an intentional ingredient or as a
contaminant constituting 0.1% or more by volume.
The Commission withdrew its proposed ban in
1981 on the basis of information that benzene, as
currently used in consumer products, did not
present a significant risk to consumers. The data
obtained from contacts in industry and information
provided by manufacturers, importers, and labelers
of such products indicated that benzene was not
currently used intentionally in consumer products.
A labeling regulation established for products
containing more than 5% benzene, and a safety
packaging requirement for paint solvents and
thinners containing 10% or more of petroleum
distillates such as benzene, remains in effect. CPSC
has also recommended in its publication, "School
Science Laboratories A Guide to Some Hazardous
Substances," that benzene not be used or stored in
high school laboratories.
9/04
4.8 International Regulations

CANADA
FOREIGN CHEMICAL INVENTORIES
WHMIS: The Workplace Hazardous Materials

Information System (WHMIS) created, in part,
criteria for the classification of hazardous
substances which are used in the workplace.
(Can. Gaz., Part II, Vol. 122, No. 2, Jan. 20, 1988.)
The WHMIS item number from the English
Ingredient Disclosure List for benzene is 153, and
its concentration threshold is 0.1%.
NPRI: Pursuant to Section 16 of the Canadian
Environmental Protection Act (CEPA), the National
Pollutant Release Inventory (NPRI) established a
list of substances required to be reported for toxic
release purposes. Supplier notification is required
for benzene. (128, Can. Gaz., Part I, 1378, Feb. 26,
1994.)
DSL: The Canadian Chemical Inventory, which
is called the Domestic Substances List (DSL),
contains chemicals which were in commerce in
Canada during the period 1984-86. Chemicals
which are not on the DSL may require testing
prior to being permitted fo use in commerce.
Benzene is listed on the DSL.
In addition to the Canadian Chemical Inventory

(DSL), benzene is also listed on various other
foreign chemical inventories, a number of which
are listed in Table 4.6. Since several countries,
including China and Mexico, are currently in the
process of establishing chemical inventories, this
should not be considered an all-inclusive listing.
TABLE 4.6 LISTING OF FOREIGN CHEMICAL INVENTORIES WHICH INCLUDE BENZENE

Country
Inventory
Australia
Australian Inventory of Chemical Substances (AICS)
Canada
Domestic Substances List (DSL)
China
Inventory of Existing Chemical Substances in China
European Union
European Inventory of Existing Community Commercial Chemical Substances

(EC) (EINECS) 200-753-7
Japan
Existing & New Chemical Substances (ENCS) List of Chemicals (3)-1
Korea
Korean Inventory of Chemicals (KECI) 97-1-99, KE-02150
Philippines
Philippine Inventory (PICCS)
9/04
4-11
4.9 Hazard Ratings for Benzene

NATIONAL FIRE PROTECTION ASSOCIATION
(NFPA) HAZARD RATING
NFPA 704 is the Standard System for the Identification
of Fire Hazards of Materials. It addresses the health,
flammability, reactivity, and related hazards that
could arise during short-term, acute exposure to a
material in a fire, spill, or similar emergency situation.
The intent of the system is to provide basic
information to fire fighting, emergency, and other
personnel to aid them in making decisions related
to an emergency involving a specific material.
The system identifies the hazards of a material
in terms of three principal categories: "health,"
"flammability," and "reactivity." It indicates the
degree of severity by a numerical rating that ranges
from four (4), indicating severe hazard, to zero (0),
indicating no hazard.
NFPA HAZARD RATING FOR BENZENE

Health - 2: Materials that, on intense or short
exposure, could cause temporary incapacitation or
possible residual injury, including those requiring
the use of respiratory protective equipment having
an independent air supply.
Flammability - 3: Liquids and solids that can
be ignited under almost all ambient temperature
conditions. Materials in this degree produce
hazardous atmospheres with air under almost all
ambient temperatures or, though unaffected by
ambient temperatures, are readily ignited under
almost all conditions.
Reactivity - 0: Materials that in themselves are
normally stable, even under fire conditions.
4-12
NATIONAL PAINTS AND COATINGS

ASSOCIATION (NPCA) HAZARDOUS MATERIALS
IDENTIFICATION SYSTEM (HMIS) RATING
The NPCA HMIS ratings use the same principal
categories (Health, Flammability, and Reactivity)
and numerical rating ranges (0-4) as the NFPA
hazard rating system. However, one significant
difference between the two rating systems is that
HMIS ratings are not intended for emergency or
misuse situations. Rather, they are meant to apply
to normal use of the products in the plant.
NPCA HMIS RATING FOR BENZENE

Health - 2*: Materials that may cause temporary
or minor injury. Use of an asterisk (*) indicates
there may be chronic health effects present.
Flammability - 3: Materials capable of ignition
under almost all normal temperature conditions,
including flammable liquids with flash points below
73 F and boiling points above 100 F, as well as
liquids with flash points between 73 F and 100 F
(NFPA Class 1B and 1C).
Reactivity - 0: Materials that are normally stable,
even under fire conditions, and will not react with
water.
9/04
TABLE 4.7 US FEDERAL REGULATORY SUMMARY OF BENZENE

Regulation
CFR Citation
Clean Air Act (CAA)
40 CFR 60-63
Clean Water Act (CWA)
40 CFR 116, 117, 141, 401, 423
Comprehensive Environmental Response,

Compensation and Liability Act (CERCLA)
40 CFR 302
Consumer Product Safety Commission (CPSC)
16 CFR 1500.14(3)
Food and Drug Administration (FDA)
21 CFR 175.105
Marine Occupational Safety and Health Standard

for Benzene
46 CFR 197
OSHA Benzene Standard
29 CFR 1910.1028
OSHA -Process Safety Management

of Highly Hazardous Chemicals
29 CFR 1910.119
Resource Conservation and Recovery Act (RCRA)
40 CFR 261
Superfund Amendment and Reauthorization Act

(SARA Title III), also known as the Emergency
Planning and Community Right-to-Know Act
(EPCRA)
40 CFR
section 301-303: emergency release notification
section 304: community right-to-know reporting
requirements
section 311/312: community right-to-know
reporting requirements for Hazardous
Chemicals grouped in 5 hazard categories
section 313: annual estimate and reporting of
toxic chemicals released to the environment
during the prior calendar year.
TOXIC SUBSTANCES CONTROL ACT (TSCA)
40 CFR 700-799
9/04
4-13
5. HANDLING AND
STORAGE INFORMATION
5.1 Personal Protective Equipment
RESPIRATORY PROTECTION
Per the OSHA Benzene Standard (29 CFR
1910.1028), engineering controls and work practices
should be instituted to reduce and maintain exposure
to airborne concentrations of benzene at or below
the permissible exposure limits (PELs). Where these
controls are not feasible or where the provisions of
the standard allow, respiratory protection is permitted
to be used to control employee exposure to or
below the PELs. Table 5.1 contains the respiratory
requirements listed in the OSHA Benzene Standard.

For additional details on methods of compliance
and respiratory protection requirements, please
refer to Appendix B, where a complete copy of
the OSHA Benzene Standard is located.
Persons should not be assigned to tasks
requiring the use of respirators unless they have
been trained and it has been determined they
are physically able to perform the work and use
the equipment.
TABLE 5.1: RESPIRATORY PROTECTION FOR BENZENE1

Airborne Concentration of Benzene
or Condition of Use
Respirator Type1
(a) Less than or equal to 10 ppm.
(1) Half-mask air-purifying respirator with organic vapor cartridge
(b) Less than or equal to 50 ppm.
(1) Full face piece respirator with organic vapor cartridges

(2) Full face piece gas mask with chin style canister2
(c) Less than or equal to 100 ppm.
(1) Full face piece powered air purifying respirator with organic
vapor canister2
(d) Less than or equal to 1,000 ppm.
(1) Supplied air respirator with full face piece in positivepressure mode
(e) Greater than 1,000 ppm or

unknown concentration.
(1) Self-contained breathing apparatus with full face piece in

positive-pressure mode
(2) Full face piece positive-pressure supplied-air respirator with
auxiliary self-contained air supply
(f) Escape
(1) Any organic vapor gas mask; or

(2) Any self-contained breathing apparatus with full face piece
(g) Fire fighting
(1) Full face piece self-contained breathing apparatus in

positive-pressure mode
1. Requirements as specified in the OSHA Benzene Standard (29 CFR 1910.1028).

2. Canisters must have a minimum service life of four (4) hours when tested at 150 ppm benzene, at a flow rate of 64 LPM, 25 C,
and 85% relative humidity for non-powered air purifying respirators. The flow rate shall be 115 LPM and 170 LPM, respectively,
for tight fitting and loose fitting powered air purifying respirators.
9/04
5-1
CHEMICAL PROTECTIVE CLOTHING (CPC)

The purpose of chemical protective clothing (CPC)
is to prevent and/or limit skin contact with chemicals
that are hazardous. As indicated in Section 2.
Health Hazard Information, skin contact with liquid
benzene may result in irritation and erythema
(reddening of the skin). Prolonged and repeated
skin contact can result in defatting and drying of
the skin, which may lead to dermatitis and increased
chance of secondary infection. In addition, liquid
benzene can be absorbed through the skin.
The specific level of CPC required will depend
on the conditions. The level of protection selected
should be based on the potential benzene concentration and likelihood of contact. It could range
from no CPC being required, such as when
benzene is handled in closed systems and there
is no personnel exposure, to chemical splash-suits
with positive-pressure-supplied air respirators
being required, as would be the case in certain
spill situations.
While one cannot recommend the specific level
of CPC to be used without thoroughly evaluating
the conditions, some general CPC selection
recommendations for benzene are provided in the
Shell MSDS for Benzene. The MSDS notes that test
data from published literature and/or glove and
clothing manufacturers indicate that the best
protection is provided by Viton, polyvinyl alcohol
(PVA), and North Silver Shield (or similar material).
It is important to be aware that materials listed on
the Shell MSDS should in no way be considered a
complete list of all materials that are acceptable
for use with benzene.
References such as those identified below
provide test data and/or recommendations on
various materials which can be used to assist in the
selection of CPC for benzene. Again, this reference
listing should not be considered an all-inclusive set
of sources from which CPC chemical resistance
performance data can be obtained.
Chemical Protective Clothing, Vols. I and II,
Eds. Johnson, J.S. and K.J. Anderson,
American Industrial Hygiene Association,
Fairfax, VA, 1990.
5-2
Quick Selection Guide to Chemical Protective

Clothing, Second Ed., Mansdorf, S.Z. and K.
Forsberg, Van Nostrand Reinhold, New
York, NY.
Instant Gloves + CPC Database, Forsberg, K.
and L.H. Keith, 1995 (CD-ROM Database).
Guidelines for the Selection of Chemical
Protective Clothing, Schwope, A. et al.
American Conference of Governmental
Industrial Hygienists, Cincinnati, OH.
The data contained in the references generally
take into account two important measures of the
chemical resistance of CPC to benzene. These
measures include:
Degradation: The deleterious change in physical
properties of a clothing material upon contact by a
chemical. Examples of properties which can be
evaluated include thickness, weight, elongation, tear
strength, cut resistance, and puncture resistance.
Permeation: The diffusion of a chemical on a
molecular level through CPC. The term breakthrough time is used to define the time it takes the
chemical to pass through the CPC and be detected
by an analytical instrument.
In addition to the chemical breakthrough
performance information, i.e., the resistance of the
CPC to benzene, there are additional factors which
need to be considered in CPC selection. For
example, a third factor that may not be considered
in the references is that of penetration. Penetration
is the flow of material through CPC at a nonmolecular level, i.e., through rips, tears, seams,
closures, and other damage or manufacturing
imperfections. Along with penetration, a number
of these factors have been listed below:
Physical resistance of CPC (resistance to cuts
and tears, i.e., penetration).
Thickness and flexibility of CPC.
Dexterity required to perform task(s).
Ambient temperature at which CPC to be
used. (In general, reduced temperature
will result in reduced permeation rate
and increased break-through time.
Increased temperature will result in
increased permeation rate and reduced
breakthrough time.)
9/04
5.2 Exposure Monitoring

Chemical contact time.
Extent of chemical contact (liquid immersion
vs. liquid splash vs. saturated vapor).
Chemical mixture effects.
When selecting specific products, the material
manufacturer should be contacted for actual product
data. One reason this is important is because the
chemical resistance of a generic material such as
polyvinyl alcohol may vary between manufacturers
of CPC. Selection of hand protection (gloves)
should also be in accordance with 29 CFR 1910.138.
EYE AND FACE PROTECTION

In accordance with the OSHA standard for Eye and
Face Protection (29 CFR 1910.133), protective
eye and face devices should be worn when there is
exposure to eye or face hazards from liquid
chemicals or chemical gases or vapors.
At a minimum, chemical safety goggles should
be worn if there is a potential for liquid benzene to
get in the eyes. Additional splash protection may be
obtained with the use of a face shield.
Protective eye/face devices purchased after July
5, 1994, must comply with ANSI Z87.1-1989. If
purchased on or before July 5, 1994, protective
devices should at least comply with ANSI Z87.1-1968.
Refer to the latest ANSI Z87.1-2003 for information
on protective eye/face devices.
9/04
A number of methods are available for monitoring

employee exposures to benzene; the following
information addresses some of these methods.
Please note that this section is not intended to be a
complete review and evaluation of benzene sampling
and analytical methods. The employer is responsible for a methods accuracy and precision relevant
to the unique conditions of the specific workplace,
no matter what method is chosen. OSHA requires
that the method of monitoring must be accurate, to
a confidence level of 95%, to within plus or minus
25% for airborne concentrations of benzene greater
than or equal to 0.5 ppm..
The names of equipment manufacturers have
been listed to provide a reference to enable additional
information to be obtained if desired. It is not an
endorsement or recommendation of a specific
manufacturer, but rather a listing of those which
we know have sampling equipment of that type.
Sampling Pumps and Charcoal Tubes: The
standard monitoring methods for benzene involve
the use of charcoal tubes and sampling pumps,
followed by analysis of the samples using gas
chromatography (GC). Differences between
methods may include the use of different desorbing
solvents and variations in analytical equipment.
Appendix D contains NIOSH Method 1501,
which applies to the sampling and analysis of
benzene. OSHA Method No. 12 is contained in
Appendix B as it is listed in OSHAs Benzene
Standard. Both methods use charcoal tubes,
sampling pumps, and GC analysis.
Passive Monitors: Passive dosimeter badges are
available for monitoring airborne concentrations of
benzene. One type of badge for benzene is the 3M
Organic Vapor Monitor #3500. The 3M TECH DATA
Bulletin #59 contains information regarding the
usage of this badge with respect to sampling for
benzene; a copy of this document has been
attached in Appendix E. The passive dosimeter
badge is analyzed in the same manner as the
charcoal tube.
5-3
5.3 General Information on

Storage and Handling
Direct Reading, Portable Instruments: There are
portable instruments utilizing flame ionization or
photo ionization detectors that can be used to
measure benzene in low-to-sub-ppm concentrations.
(Examples include the Photovac Micro-Tip and the
Foxboro TVA-1000 Analyzers.) These instruments
respond to a wide range of hydrocarbons. As a
result, they are nonspecific for benzene and can be
affected by the presence of other hydrocarbons.
Detector Tubes: A number of companies
manufacture detector tubes for use with volumetric
pumps to measure benzene concentrations. These
colorimetric indicating tubes provide a direct
reading of the benzene concentration. A specified
amount of air is drawn through the tube, the
benzene present in the air reacts with the solid
sorbent to produce a color change whose length is
directly proportional to the benzene concentration.
National Draeger, Sensidyne, Mine Safety
Appliances, and Kitagawa are among the
manufacturers who offer detector tubes for benzene
sampling. A potential concern with the usage of
these tubes is the lack of specificity when other
hydrocarbons, especially aromatics, are present. As
a result, manufacturers offer several types of detector
tubes for benzene. Consult with the manufacturers
to select the most appropriate tube.
Gas Chromatography (GC): The presence of
other hydrocarbons or certain gases may significantly
interfere with readings obtained by benzene detector
tubes or other direct-reading hydrocarbon analyzers.
When this occurs, a GC method is a recommended
option.
Portable GCs may be taken to the field for
direct on-site measurements or, alternatively, a
syringe may be used to collect the sample which
can then be injected into a GC for analysis.
5-4
The intent of this section is to provide an overview

of various benzene storage and handling issues.
Topics addressed in the following subsections
include materials of construction for use in benzene
service, bulk movement of benzene by barge, and
bulk benzene storage. Benzene handling and
storage practices are often similar to those used
for gasoline because of comparable volatility and
flammability. However, because of benzenes
greater toxicity, some additional measures are
necessary to minimize personnel exposure and
releases of this chemical to the atmosphere. Section
8.2 Emission Reduction Measures details many
practices which Shell Chemicals* have adopted in
order to reduce benzene emissions and may be
referenced for further information.
EQUIPMENT
Lines: Materials of construction found to be
acceptable for use with benzene include mild
or stainless steel lines. In areas of low ambient
temperatures, heat tracing of the lines may be
required. Insulation of the lines is recommended,
particularly in low temperature climates, even
when heat tracing is not required.
Hoses: Hard piping is preferred to the use of
hoses where it is possible and practical. For
example, loading arms connected to a marine vapor
recovery system are preferred to hoses. If hoses are
used, they should be inspected and pressure-tested
at the intervals required by the appropriate
regulations. U.S. Coast Guard regulations 33 CFR
Parts 154.500 and 156.710 apply to hoses used for
bulk transfers to and from tank vessels.
For guidance on bonding and grounding
measures recommended for marine transfers, refer
to Section 6.1 Fire and Explosion Hazard.
9/04
Jointing: Spiral wound gaskets with inner and

outer rings have been successfully utilized in
benzene service. While screwed joints are code
acceptable (ANSI Code B-31.3), their use is
discouraged.
Pumps: Centrifugal pumps are recommended.
Positive displacement pumps may also be used, and
should be fitted with a pressure relief valve which
must not be integral with the pump.
Pump seals must be capable of meeting EPA
emission standards. Typically, this requires tandem
or double seals.
Valves: For pigged pipelines, full-bore ball
valves are preferred. For other than pigged
pipelines, gate valves, butterfly valves, or ball
valves may be used.
Materials of construction recommended for
valves include cast iron or cast steel. For valve
packing, lubricated Teflon (PTFE) or equivalent
may be used.
Incompatible Materials: Polyvinyl chloride and
natural, butyl, neoprene, and nitrile rubbers are all
incompatible materials of construction for use with
benzene.
BULK MOVEMENT OF BENZENE BY BARGE

Vapor Return Line During Loading: The loading
of this product in certain states, e.g., Texas,
Louisiana and Illinois, may require the use of vapor
control. In the absence of a regulatory requirement,
closed loading should be carried out with vapor
return to shore when these facilities are available.
Closed Gauging: Gauging must consist of a
closed device for use during transfer (e.g., sight
glasses), and a restricted device to determine
product quantity during transfer.
Pressure: Atmospheric pressure. Cargo to be
carried at not more than 10 pounds per square
inch, exclusive of static head.
Acceptable Internal Tank Surface: Clean stainless
steel or rust-free mild steel tanks, or mild steel
tanks lined with a phenolic epoxy paint or zinc silicate paint, are recommended. If an amine or
amine-adduct cured epoxy paint lining is used, it
should be of a multi-coat, spray-applied, heat-cured
system. Cold-cured epoxy resin-based paint systems
applied by brush or spray will tend to soften.
9/04
Shipping Temperature:
Ambient (50 F minimum).
Loading & Discharge Temperature:
Maximum Product Temperature:
Minimum Product Temperature:
50 F. The product freezes at 42 F.
Nitrogen Blanketing: Not required.
Personal Protective Equipment: Refer to
Section 5.1 Personal Protective Equipment
for information.
BULK STORAGE OF BENZENE

Tank Type: Internal floating roof tanks are
recommended for the bulk storage of benzene.
Acceptable Internal Tank Surface: Clean stainless
steel or rust-free mild steel tanks, or mild steel tank
lined with a phenolic epoxy paint or zinc
silicate paint, are recommended. If an amine or
amine-adduct cured epoxy paint lining is used, it
should be of a multi-coat, spray-applied, heat-cured
system. Cold-cured epoxy resin-based paint systems
applied by brush or spray will tend to soften.
Nitrogen Blanketing: Not required. However,
Shell Chemicals do use nitrogen blanketing on
some of its shipping tanks, and does have a routine
inspection program for timely repair of tank seals.
Driers: Not required.
Maximum Storage Time: Not critical.
Maximum Storage Temperature: Ambient (50 F
minimum).
Minimum Storage Temperature: 50 F. The
product freezes at 42 F.
Heating: In temperate or cold climates, tanks
should be insulated and fitted with steam heating
coils.
Cooling: Storage tanks should ideally be painted
white externally. For fire-fighting purposes, a water
cooling facility is required.
Insulation: In areas of high ambient temperatures,
insulation will minimize losses. Insulation will
also prevent heat loss in areas of low ambient
temperatures.
5-5
Pumping Rate: Because of the possibility of

generating a high electrostatic charge, restrict line
velocity during pumping to < 1m/sec until fill pipe
submerged to twice its diameter, then < 7m/sec.
Avoid splash filling. Refer to Section 6.1 Fire and
Explosion Hazard for additional information on
static electricity and the pumping rate. Do not use
compressed air for filling, discharging, or handling.
Personal Protective Equipment: Refer to Section
5.1 Personal Protective Equipment for information.
BENZENE REACTIVITIES
AND INCOMPATIBILITIES
If exposed to flame or heated, benzene presents a
moderate explosion hazard. Benzene also has a
number of chemical reactivities and incompatibilities
which can result in explosive and/or vigorous
reactions. Information is detailed in Section 1.6
Benzene Reactivities and Incompatibilities regarding
the specific compounds and potential outcome of
the reactivities and incompatibilities.
5-6
9/04
6. FIRE SAFETY
& SPILLS AND LEAKS
6.1 Fire and Explosion Hazard
Benzene is an extremely flammable liquid, flash
point = -11C/12 F (closed cup). The flash point is
the lowest temperature at which vapor is given off
in sufficient quantity such that the vapor/air mixture
above the surface of the material will propagate a
flame away from the source of ignition, i.e., form
an ignitable mixture. The closed cup indication
denotes the type of method used to determine
the flash point.
Benzene meets the definition of a Class 1B
Flammable Liquid in both the OSHA Standard
for Flammable and Combustible Liquids (29 CFR
1910.106) and the National Fire Protection
Association Flammable and Combustible Liquids
Code (NFPA 30). A Class 1B Liquid is defined as
having a flash point below 23 C/73 F and a
boiling point at or above 38 C/100 F. Transportation
authorities classify benzene as a flammable liquid
(See Section 7.3 Transport Classifications
for Benzene for additional information).
Explosive mixtures can be formed when
benzene concentrations in air are between 1.4%
and 7.1%. If an ignition source is present, a
fire and/or explosion can result. At or above
temperatures of approximately 562 C/ 1,044 F,
this material can autoignite. In other words, it can
spontaneously ignite without the application of a
flame or spark if it is heated above this temperature.
Vapors of benzene are heavier than air. Thus, these
vapors may accumulate and travel along the ground
a significant distance to an ignition source, resulting

in a flash-fire.
Flammable liquids such as benzene expand
when heated. As a result, tanks should not be
completely filled so that the danger of overflow can
be avoided. This is especially true when cool liquid
is placed into a warm environment. Above-ground
tanks are often painted with aluminum or white
paint to reflect heat so the temperature rise of the
liquid contents is decreased.
In a fire situation, hazardous conditions can
develop which could lead to dangerous explosions
and further fire danger. The buildup of pressure in
closed containers of benzene caused by elevated
temperatures can result in container failure. If the
pressure buildup created by exposure to elevated
temperatures (such as may be present with an
exposure fire) is not properly vented, it can result
in a phenomenon called a Boiling Liquid
Expanding Vapor Explosion (BLEVE). The result
of such a scenario can be a "pressure release
explosion," characterized by the extremely quick
mixing of benzene vapor and air, causing a fireball
upon ignition by the fire that initially caused the
BLEVE. This fireball and the resultant liquid ground
fire is not as severe as that of a Liquefied Petroleum
Gas BLEVE, but will still result in the potential for
death to personnel and serious property damage in
the immediate area.
9/04
6-1
There are a number of factors which can

increase the danger of tank failure from internal
pressure when exposed to fire. These include:
The characteristics of the liquid, i.e., whether
it is very volatile (such as benzene) and will
readily give off vapors to increase the
internal pressure.
The size and type of the tank, i.e., the smaller
the tank the less fire heat is needed to build
internal pressure to the failure point.
The type of relief protection on the tank, i.e.,
without relief protection the tank will fail in
a very short time.
Benzene is a static accumulator. Static electricity
can also accumulate and create a fire hazard.
Electrostatic discharge may be generated during
pumping. Ensure electrical continuity by bonding
and grounding (earthing) all equipment. Restrict the
line velocity (flow rate) during pumping in order to
avoid generation of electrostatic discharge - <= 1
meter/second until fill pipe is submerged to twice
its diameter, then <= 7 meters/second. Avoid splash
filling. DO NOT USE compressed air for filling,
discharging, or handling operations. In practical
terms, loading by gravity only at this stage of the
loading operation is most desirable.
Based on the recommendations of the
International Safety Guide for Oil Tankers and
Terminals, Shell Chemicals* have abandoned the
use of ship to shore bonding lines in favor of
insulating flanges. In the past, it was common to
connect vessel and shore systems by using a
bonding wire via a flameproof switch before the
cargo connection was made, and to maintain this
bonding wire in position until after the cargo
connection was broken. The use of this bonding
wire had no relevance to electrostatic charging. It
was an attempt to short-circuit the vessel/shore
electrolytic/cathodic protection systems and to
reduce the vessel/shore voltage to such an extent
that currents in hoses or metal arms would be
6-2
negligible. However, because of the large current

availability and the difficulty of achieving a
sufficiently small electrical resistance in the
vessel/shore bonding wire, this method has
been found to be quite ineffective for its
intended purpose.
The use of vessel/shore bonding wires is
ineffective as a safety device and potentially
dangerous, and therefore, should not be used.
Nevertheless, it has to be accepted that local
regulations in some areas still require that bonding
cables be used and these regulations should be
followed.Where such local regulations exist, the
connection should be accomplished with the use
of a flameproof switch. Insulating flanges in the
pipe risers to the hose connections provide the best
assurance against arcing at the point of connection
and disconnection of the hose.
Insulating flanges at the shore end of the wharf
piping are effective where stray currents arise from
onshore facilities. Insulating flanges at both locations
are employed to prevent arcing at those connections,
and to prevent stray or cathodic protection current
flow between the wharf and shore piping. To
ensure that insulating flanges are working properly,
they must be tested annually to minimum resistance
of 1,000 ohms (more frequent testing may be
required when maintenance work is performed
around the flange area).
Articles 500 through 504 of the National Electric
Code (NEC-NFPA 70) address the requirements for
electrical equipment and wiring in locations where
fire or explosion hazards may exist due to flammable
gases or vapors, flammable liquids, combustible
dust, or ignitable fibers or flyings. Locations are
classified depending on the properties of the
hazardous material. For purposes of the National
Electric Code, benzene is categorized as a Class I,
Group D material. Articles 500 through 504 of
NEC-NFPA 70 should be referenced for additional
information on this subject.
9/04
6.2 Fire Prevention
6.3 Fire Fighting
Benzene is a significant fire and explosion hazard

based on its physical properties, including its flash
point, vapor pressure, and boiling point. It can
quite readily form explosive mixtures in air as
a result of its high vapor pressure. Therefore,
preventive measures must be taken to minimize
the potential for a fire or explosion from occurring.
Four general fire prevention guidelines are
provided in the following:
1. When locating storage and handling areas,
the neighboring properties, as well as nearby plant
operations and activities, should be taken into
consideration. All potential sources of ignition
should be reviewed.
2. Storage and handling equipment should be
designed and maintained in conformance with
applicable regulations and codes (ASME, OSHA,
NFPA, API, DOT, National Electric Code, etc.).
3. Stringent hot work practices and systems
should be in place which fully address benzenes
fire and explosion hazard. (Hot work is defined as
including but not limited to welding, cutting, and
burning.) Personnel should make necessary work
practice changes, i.e., ventilation, cleanup, etc., to
ensure benzene vapor is not present during any
spark-producing activities.
4. Preventive measures against the accumulation
of static electricity should be employed.
Fire brigade members should be provided information on the hazards of benzene, quantities present,
and location(s).
The fire fighting measures for benzene are
similar to those for flammable liquids in general. If
there is a benzene fire or benzene is in a fire area,
the fire area should be cleared of unauthorized
and/or unprotected personnel and isolated. For
incidents involving a tank, rail car, or tank truck,
the U.S. Department of Transportations Emergency
Response Guidebook (Guide Number 27)
recommends isolation of the area for a half-mile
in all directions. This safety zone should be
established to protect personnel from tank car or
tank truck BLEVE fire failures, and to ensure
personnel without proper personal protective
equipment (PPE) are not overexposed to benzene
vapors. Fire fighters should be wearing full bunker
gear at a minimum (helmet with face shield, bunker
coats and pants, gloves, and rubber boots), including
a positive pressure, NIOSH-approved (or other
appropriate regulatory authority), self-contained
breathing apparatus (SCBA).
To extinguish a benzene fire, use dry chemical,
foam, or carbon dioxide. Water can be used to
cool adjacent drums and tanks as long as the dike
containment capacity is not exceeded. Water will
not normally extinguish a flammable liquid such
as benzene when it is on fire.
Disperse vapors with a sustained flow of water
fog or blanket with foam. Keep liquid and vapor
away from heat, sparks, and flames. Surfaces that
are sufficiently hot may ignite liquid benzene, even
in the absence of sparks or flame. Precautions must
be taken to eliminate all potential sources of ignition.
Benzene vapors are heavier than air and may travel
a considerable distance to a source of ignition and
flash back.
Containers of benzene exposed to intense heat
from fires should be cooled with large quantities of
water to prevent vapor pressure buildup, which
could result in container failure and/or weakening
of the container structure. In fighting tank fires, it is
imperative that the shell above the liquid level is
9/04
6-3
6.4 Spills and Leaks

cooled to keep the steel from overheating.
Regardless of the adequacy of the venting system
on the tank, it can bulge and rupture if this is not
done. Water should be applied from a safe distance
and until well after the fire is out. Stay away from
the ends of the containers. If possible, the cooling
of the containers should be done with unmanned
hose holders or monitor nozzles. If water supplies
are limited or not available, fire fighters should be
withdrawn and the fire allowed to burn.
Immediate withdrawal of fire fighting personnel
should take place in case of the rising sound of a
venting safety device or localized heating and discoloration of the tank due to fire. (This would
appear as a reddening, much like a steel plate
when heated with a torch.)
In the event there is residual benzene contamination after a fire has been extinguished, the
cleanup activities must be conducted in accordance
with the local requirements (i.e. in the US, OSHA
Hazardous Waste Operations and Emergency
Response (HAZWOPER) Standard (29 CFR
1910.120). Experience has shown that after such an
incident, benzene will most likely be present in
levels that exceed the permissible exposure level.
Proper PPE, especially respiratory and skin
protection, will be needed.
6-4
Spill and leak activities must be conducted in

accordance with the requirements of the OSHA
Hazardous Waste Operations and Emergency
Response (HAZWOPER) Standard (29 CFR
1910.120). In part, this requires that an emergency
response plan be developed and implemented
to handle anticipated emergencies prior to the
commencement of emergency response operations.
The information contained in the remainder of this
section should be considered in the development
of such a plan.
In the event of a benzene spill or leak, the
hazard area should be isolated and entry denied
to unnecessary personnel. Individuals should stay
upwind and keep out of low areas.
Wearing appropriate respiratory equipment and
chemical protective clothing, response personnel
should eliminate all ignition sources if it is safe to
do so. The spilled benzene should be diked and
contained. It is particularly important to keep
benzene or benzene-contaminated runoff from
entering sewers and water-ways, due to the potential
fire and explosive hazards which will be created. In
addition, there is the aquatic toxicity concern as
detailed in Section 3. Ecotoxicity/Ecological Fate.
If a benzene leak is occurring, it should be
stopped only if it can be done safely. Use water
spray to disperse vapors and to flush spills away
from exposures, with the runoff being contained.
Be aware that water spray may reduce vapors, but
it may not prevent ignition in closed spaces. The
use of foam to blanket vapors will also assist in
leak control.
The material should be removed with vacuum
trucks or pumped to storage/salvage vehicles. An
absorbent such as clay, sand, or other suitable
material can be used to soak up the residue. This
residue should be placed in non-leaking containers
for appropriate disposal. Small spills can be taken
up in a similar manner to the residue of large spills.
To remove trace residues from either large or small
spills, flush the area and collect the flush solution
for disposal.
9/04
Keep liquid and vapor away from heat, sparks,

and flames. Surfaces that are sufficiently hot may
ignite liquid benzene, even in the absence of
sparks or flame. Precautions must be taken to
eliminate all potential sources of ignition. Benzene
vapors are heavier than air and may travel a
considerable distance to a source of ignition and
flash back.
Static electricity can also accumulate and create
a fire hazard. Refer to Section 6.1 Fire and Explosion
Hazard for precautions and recommendations
relative to the use of bonding cables and static
electricity.
If an amount equal to or greater than the
CERCLA reportable quantity (RQ) for benzene is
released, immediate emergency notifications must
be made to the National Response Center, as well
as to appropriate state and local response authorities.
The current CERCLA RQ for benzene is 10 pounds.
Please refer to Section 4.3 Comprehensive
Environmental Response, Compensation and
Liability Act (CERCLA) for more detailed information
on these requirements.
9/04
6-5
7. TRANSPORTATION
7.1 General Information on Benzene
Transportation
BARGE SHIPMENTS
It is Shell Chemicals* objective to ensure that
benzene is safely transported to its customers
facilities. Shell chemicals companies transport
benzene primarily by barge, and this mode of
transportation is discussed in further detail below.
Benzene is conveyed via pipeline from the
manufacturing facility to barge loading facilities.
Shell chemicals companies ship benzene in tank
trucks or tank cars only on an exception basis.
The physical and health hazards of benzene
must be considered when arranging for transport of
this material. In previous sections, many of these
hazards have been discussed in detail. We would
advise shippers to become familiar with all
precautions discussed in the previous sections and
all other applicable safety precautions and/or legal
requirements. Highlights of some of the shipping
considerations are given below.
Shipping Conditions: For information on
shipping conditions, refer to Section 5.3 Bulk
Movement of Benzene by Barge.
Regulatory Controls: Shipments and releases
of benzene are regulated by various agencies. It
may be helpful to review the discussion of the U.S.
Coast Guard requirements below and refer to
Section 4. Regulatory Overview, of this document
for a more detailed discussion.
The shipment of benzene by barge is regulated by

the U.S. Coast Guard. Barges used for the carriage
of benzene (and products containing greater than
0.5% benzene by volume) are regulated by 46 CFR
Part 151, Subchapter O, as dangerous cargo. The
Certificate of Inspection for the barge issued by the
U.S. Coast Guard must be specifically endorsed for
benzene or the benzene mixture being moved.
Whereas the Coast Guard permits the carriage
of benzene in barges with Type III hulls, Shell
Chemicals recommend the use of Type II hulls.
Type II hulls provide a higher standard of
protection and significant measures to halt
uncontrolled releases of cargo, and must retain
stability if holed on the bottom or side shell
plating, except at a transverse bulkhead.
Unloading and loading should be controlled in
such a way to minimize employee exposure and
environmental releases. Both OSHA and the U.S.
Coast Guard have introduced a number of regulations
applicable to personnel involved in handling
benzene. Among others, the benzene regulations
include, but are not limited to, the following
elements:
1. Exposure Limits.
2. Monitoring, Regulated Areas, and
Warning Signs.
3. Employee Training.
4. Personal Protective Equipment.
9/04
7-1
7.2 Emergency Response

To place due emphasis on the transfer of
benzene (or hydrocarbon mixtures containing
in excess of 0.5% benzene by volume) at Shell
marine terminals, an Addendum to the Declaration
of Inspection is used. Appendix F of this
document contains a copy of both the Declaration
of Inspection and the Benzene Addendum used
by Shell chemicals companies. The signers of this
Addendum certify that detailed requirements for
handling benzene are complied with before
transfer occurs.
CLEANING OF EQUIPMENT
Unless the shipper or unloader has its own cleaning
facilities that can clean and dispose of the residue
responsibly, it is advised that a qualified contractor
be used to clean, inspect, and repair barges in
which benzene is shipped.
7-2
In the event a transportation incident involving

benzene does occur, the Chemical Transportation
Emergency Center (CHEMTREC) should be
contacted for immediate assistance. CHEMTREC
is a public service organization established by the
American Chemistry Council (ACC) and its members
to provide assistance in hazardous materials incidents.
CHEMTRECs toll-free Emergency Assistance
Number is 1-800-424-9300. Ships at sea can contact
CHEMTREC through the International and Maritime
Number: 1-703-527-3887. The CHEMTREC center is
staffed 24-hours-a-day, 7-days-a-week, by trained
communicators.
CHEMTREC uses a two-step approach in
responding to emergencies involving hazardous
materials. First, immediate emergency response
information for the product involved in the incident
is provided to the caller. This information is generally
obtained from the manufacturers Material Safety
Data Sheet (MSDS) for the product in question.
The Department of Transportations Emergency
Response Guidebook may also be referenced;
Guide 27 of this document applies to emergency
actions for benzene incidents.
The second step is for CHEMTREC to notify
the 24-hour emergency contact designated by the
shipper or manufacturer of the material involved
in the incident. Shell chemicals companies have
emergency response procedures in place to provide
additional technical advice and assistance.
In addition, benzene is covered through a
mutual aid response agreement, known as the
Chemical Industry Mutual Aid Network (CHEMNET).
This agreement enables a fellow participating
company that is located closer to the incident,
to respond to the incident
This section focuses on benzene transportation
incidents. Please be aware that CHEMTREC can also
be contacted for non-transportation and medical
incidents.
9/04
7.3 Transport Classifications for Benzene

Road/Rail - U.S. Department of Transportation (DOT)
Proper Shipping Name:
Benzene
Hazard Class or Division:
3
Packing Group:
II
Identification Number:
UN1114
Label/Placard Required:
Flammable
Hazardous Substance RQ:
Benzene, 10 pounds
Emergency Response Guide: 130
Air - International Civil Aviation Organization (ICAO)
International Air Transport Association (IATA)
Benzene
Class:
3
Packing Group:
II
UN Number:
UN1114
Symbol:
Flammable Liquid
Sea - International Maritime Organization (IMO)
Benzene
Class:
3.2
Packing Group:
II
UN Number:
UN1114
Symbol:
Flammable Liquid
Pollution Category:
C
European Behavior
Classification:
F, E (Floater, Evaporator)
A variety of restrictions apply to the preceding
classifications. Please refer to the appropriate
regulation for specific details regarding classification
requirements and restrictions. 46 CFR, Parts 150-154,
should also be referenced for information regarding
U.S. Coast Guard regulations concerning the
transportation of benzene.
9/04
7-3
8. POLLUTION PREVENTION
8.1 SARA Title III Toxics
Release Inventory (TRI) Data
The Toxics Release Inventory (TRI) was established
under the Emergency Planning and Community
Right-to-Know Act of 1986 (EPCRA). The TRI is a
publicly available database that contains specific
toxic chemical release and transfer information
from manufacturing facilities throughout the United
States. Toxics Release Inventory (TRI) Program
<http://www.epa.gov/tri/>
Each year, manufacturing facilities meeting
certain activity thresholds must report their
estimated releases and transfers of listed toxic

chemicals to the EPA and to the state in which the
facility is located. Benzene was included among the
listed chemicals.
Industry has been very involved in reducing
the level of benzene emissions. Figure 8.1 shows
the TRI volumes for total benzene releases for the
last 10 reporting years. It should be noted that
approximately 95% of the benzene releases
are to air.
FIGURE 8.1: TOTAL BENZENE TRI RELEASES 1990-2001

30
20
10
0
(Sources: 1992 and 1993 Toxics Release Inventory)
9/04
8-1
8.2 Emission Reduction Measures

Shell Chemical LP has been actively involved in its
own as well as government required programs to
reduce benzene emissions from its manufacturing
and distribution facilities. Government programs
include the National Emissions Standards for
Hazardous Air Pollutants (NESHAP), to reduce
benzene emissions from waste streams, vents, and
fugitive emission sources. In addition to the
benzene NESHAP program, the EPA established a
voluntary pollution prevention initiative called the
33/50 Program. Using 1988 TRI reporting data as a
baseline, the EPA selected 17 priority chemicals for
which an interim goal was to achieve 33% reduction
by 1992, and 50% or more reduction in reported
TRI releases by 1995.
Benzene was one of the 17 priority chemicals.
Through 1992, a 33% reduction in benzene TRI
releases had been achieved by Shell Chemicals*;
the company also met the 50% reduction target
by 1995. Benzene emission reduction activities that
have been planned, completed, or are in progress
at Shell Chemicals include those listed below.
These activities are provided to present information
for consideration on various ways that benzene
releases can be reduced.
Elimination of deep-well waste
disposal at Norco.
Installation of marine vapor recovery facilities
for benzene barge loading at Norco for all
marine gasoline loadings.
9/04
Installation of a pipeline to transport benzene

from Deer Park to a contract terminal with
marine vapor recovery facilities.
Implementation of a more aggressive
fugitive emission monitoring program. Leak
threshold for valves, pumps, and flanges
decreased to 500 ppm.
Replacement of pump seals (design changed
to double seals).
Inspection of benzene tank seals for timely
repair and upgrade of nitrogen blanketing
systems for these tanks.
Routing of water streams with potential
benzene contamination, including some
recovered groundwater, to closed systems to
collect and process.
Installation of "closed loop" sample stations in
the unit and at the process tanks.
Upgrade of the vacuum system on the
extraction plants to remove steam eductor
exhaust from the atmosphere.
8-2
APPENDIX A
The Shell Chemicals Companies
Commitment to Health, Safety and
the Environment
In Shell chemicals companies we strive to:
pursue the goal of no harm to people,
protect the environment,
use material and energy efficiently to provide
our services,
develop services and strategic advice
consistent with these aims,
publicly report on our performance,
play a leading role in promoting best practice
in our industries,
manage HSE matters as a critical
business activity,
promote a culture where all employees
share this commitment.
In this way, we aim to have an HSE performance
we can be proud of, to earn the confidence of our
customers, shareholders and society at large, to be
good neighbors and to contribute to sustainable
development.
SHELL CHEMICALS COMPANIES HSE POLICY:

The Shell chemicals companies:
have a systematic approach to HSE
management designed to ensure compliance
with the law and to achieve continuous
performance improvement,
set targets for improvement and measures,
appraises and reports performance,
require contractors to manage HSE in line
with this policy,
require staff appointed as Shell Chemicals*
nominated directors to joint ventures to help
ensure that those joint ventures comply with
the appropriate HSE policy requirements of
the Shell chemicals companies,
include HSE performance in appraisals
of all staff and reward compliance
accordingly.
4/04
A-1
APPENDIX B
Disclaimer: The following information is an excerpt from the Code of Federal Regulations (CFR) and is provided solely
for information purposes. A complete description of the OSHA Benzene Standard can be found in the CFR. In
furnishing this information, Shell Chemicals*, its affiliates and their representatives undertake no obligation to provide
the recipient with access to any additional information or to update this document.
OSHA Benzene Standard (29 CFR 1910.1028)

(A) SCOPE AND APPLICATION
(1) This section applies to all occupational exposures
to benzene. Chemical Abstracts Service Registry
No. 71-43-2, except as provided in paragraphs
(A)(2) and (A)(3) of this section.
(2) This section does not apply to:
(i) THE STORAGE, TRANSPORTATION,
DISTRIBUTION, DISPENSING, SALE OR USE
of gasoline, motor fuels, or other fuels
containing benzene subsequent to its final
discharge from bulk wholesale storage
facilities, except that operations where
gasoline or motor fuels are dispensed for
more than 4 hours per day in an indoor
location are covered by this section.
(ii)LOADING AND UNLOADING operations at
bulk wholesale storage facilities which use
vapor control systems for all loading and
unloading operations, except for the provisions
of 29 CFR 1910.1200 as incorporated into this
section and the emergency provisions of
paragraphs (G) and (I)(4) of this section.
(iii) THE STORAGE, TRANSPORTATION, DISTRIBUTION OR SALE of benzene or liquid
mixtures containing more than 0.1 percent
benzene in intact containers or in transportation pipelines while sealed in such a manner
as to contain benzene vapors or liquid,
except for the provisions of 29 CFR

1910.1200 as incorporated into this section
and the emergency provisions of paragraphs
(G) and (I)(4) of this section.
(iv) CONTAINERS AND PIPELINES carrying
mixtures with less than 0.1 percent benzene
and natural gas processing plants processing
gas with less than 0.1 percent benzene.
(v) WORK OPERATIONS where the only exposure
to benzene is from liquid mixtures containing
0.5 percent or less of benzene by volume, or
the vapors released from such liquids until
September 12, 1988; work operations where
the only exposure to benzene is from liquid
mixtures containing 0.3 percent or less of
benzene by volume or the vapors released
from such liquids from September 12, 1988,
to September 12, 1989; and work operations
where the only exposure to benzene is from
liquid mixtures containing 0.1 percent or less
of benzene by volume or the vapors released
from such liquids after September 12, 1989;
except that tire building machine operators
using solvents with more than 0.1 percent
benzene are covered by paragraph (I) of this
section.
(vi) OIL AND GAS DRILLING, PRODUCTION
AND SERVICING OPERATIONS.
9/04
B-1
(vii) COKE OVEN BATTERIES.

(3) The cleaning and repair of barges and tankers
which have contained benzene are excluded from
paragraph (F) methods of compliance, paragraph
(E)(1) exposure monitoring-general, and paragraph
(E)(6) accuracy of monitoring. Engineering and
work practice controls shall be used to keep B-1
OSHA Benzene Standard.exposures below 10 ppm
unless it is proven to be not feasible.
(B) DEFINITIONS
Action level means an airborne concentration
of benzene of 0.5 ppm calculated as an 8-hour
time-weighted average.
Assistant Secretary means the Assistant
Secretary of Labor for Occupational Safety and
Health, U.S. Department of Labor, or designee.
Authorized person means any person specifically
authorized by the employer whose duties require
the person to enter a regulated area, or any person
entering such an area as a designated representative
of employees for the purpose of exercising the right
to observe monitoring and measuring procedures
under paragraph (L) of this section, or any other
person authorized by the Act or regulations issued
under the Act.
Benzene (C6 H6 ) (CAS Registry No. 71-43-2)
means liquefied or gaseous benzene. It includes
benzene contained in liquid mixtures and the
benzene vapors released by these liquids. It does
not include trace amounts of unreacted benzene
contained in solid materials.
Bulk wholesale storage facility means a bulk
terminal or bulk plant where fuel is stored prior to
its delivery to wholesale customers.
Container means any barrel, bottle, can,
cylinder, drum, reaction vessel, storage tank, or the
like, but does not include piping systems.
Day means any part of a calendar day.
Director means the Director of the National
Institute for Occupational Safety and Health, U.S.
Department of Health and Human Services, or
designee.
Emergency means any occurrence such as,
but not limited to, equipment failure, rupture of
containers, or failure of control equipment which
B-2
may or does result in an unexpected significant

release of benzene.
Employee exposure means exposure to
airborne benzene which would occur if the
employee were not using respiratory protective
equipment.
Regulated area means any area where airborne
concentrations of benzene exceed or can reasonably
be expected to exceed, the permissible exposure
limits, either the 8-hour time weighted average
exposure of 1 ppm or the short-term exposure limit
of 5 ppm for 15 minutes.
Vapor control system means any equipment
used for containing the total vapors displaced
during the loading of gasoline, motor fuel or other
fuel tank trucks and the displacing of these vapors
through a vapor processing system or balancing the
vapor with the storage tank. This equipment also
includes systems containing the vapors displaced
from the storage tank during the unloading of the
tank truck which balance the vapors back to the
tank truck.
(C) PERMISSIBLE EXPOSURE LIMITS (PELS)

(1) TIME-WEIGHTED AVERAGE LIMIT (TWA)
The employer shall assure that no employee

exposed to an airborne concentration of
benzene in excess of one part of benzene parts
of air (1 ppm) as an 8-hour time-weighted
average.
(2) SHORT-TERM EXPOSURE LIMIT (STEL)
The employer shall assure that no employee

is exposed to an airborne concentration of
benzene in excess of five (5) ppm as averaged
over any 15 minute period.
(D) REGULATED AREAS

(1) The employer shall establish a regulated area
wherever the airborne concentration of benzene
exceeds or can reasonably be expected to exceed
the permissible exposure limits, either the 8-hour
time weighted average exposure of 1 ppm or the
short-term exposure limit of 5 ppm for 15 minutes.
(2) Access to regulated areas shall be limited to
authorized persons.
9/04
(3) Regulated areas shall be determined from the

rest of the workplace in any manner that minimizes
the number of employees exposed to benzene
within the regulated area.
(E) EXPOSURE MONITORING

(1) GENERAL
(i) Determinations of employee exposure shall

be made from breathing zone air samples
that are representative of each employees
average exposure to airborne benzene.
(ii) Representative 8-hour TWA employee
exposures shall be determined on the basis
of one sample or samples representing the
full shift exposure for each job classification
in each work area.
(iii) Determinations of compliance with the STEL
shall be made from 15 minute employee
breathing zone samples measured at
operations where there is reason to believe
exposures are high, such as where tanks are
opened, filled, unloaded or gauged; where
containers or process equipment are opened
and where benzene is used for cleaning or as
a solvent in an uncontrolled situation. The
employer may use objective data, such as
measurements from brief period measuring
devices, to determine where STEL monitoring
is needed.
(iv) Except for initial monitoring as required
under paragraph (E)(2) of this section, where
the employer can document that one shift
will consistently have higher employee
exposures for an operation, the employer
shall only be required to determine
representative employee exposure for that
operation during the shift on which the
highest exposure is expected.
(2) INITIAL MONITORING
section shall monitor each of these work

places and work operations to determine
accurately the airborne concentrations of
benzene to which employees may be exposed.
(ii) The initial monitoring required under
paragraph (E)(2)(i) of this section shall be
completed by 60 days after the effective date
of this standard or within 30 days of the
introduction of benzene into the workplace.
Where the employer has monitored within
one year prior to the effective date of this
standard and the monitoring satisfies all other
requirements of this section, the employer
may rely on such earlier monitoring results to
satisfy the requirements of paragraph (E)(2)(i)
of this section.
(3) PERIODIC MONITORING
AND MONITORING FREQUENCY
(i) If the monitoring required by paragraph

(E)(2)(i) of this section reveals employee
exposure at or above the action level but at
or below the TWA, the employer shall repeat
such monitoring for each such employee at
least every year.
(ii) If the monitoring required by paragraph
exposure above the TWA, the employer shall
repeat such monitoring for each such
employee at least every six (6) months.
(iii) The employer may alter the monitoring
schedule from every six months to annually
for any employee for whom two consecutive
measurements taken at least 7 days apart
indicate that the employee exposure has
decreased to the TWA or below, but is at or
above the action level.
(iv) Monitoring for the STEL shall be repeated as
necessary to evaluate exposures of employees
subject to short term exposures.
(i) Each employer who has a place of employment covered under paragraph (A)(1) of this
9/04
B-3
(4) TERMINATION OF MONITORING
(i) If the initial monitoring required by paragraph

exposure to be below the action level the
employer may discontinue the monitoring for
that employee, except as otherwise required
by paragraph (E)(5) of this section.
(ii) If the periodic monitoring required by
paragraph (E)(3) of this section reveals that
employee exposures, as indicated by at least
two consecutive measurements taken at least
7 days apart, are below the action level the
employer may discontinue the monitoring for
that employee, except as otherwise required
by paragraph (E)(5).
(5) ADDITIONAL MONITORING
(i) The employer shall institute the exposure

monitoring required under paragraphs (E)(2)
and (E)(3) of this section when there has
been a change in the production, process,
control equipment, personnel or work
practices which may result in new or additional
exposures to benzene, or when the employer
has any reason to suspect a change which
may result in new or additional exposures.
(ii) Whenever spills, leaks, ruptures or other
breakdowns occur that may lead to employee
exposure, the employer shall monitor (using
area or personal sampling) 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.
(6) ACCURACY OF MONITORING
Monitoring shall be accurate, to a confidence level

of 95 percent, to within plus or minus 25 percent
for airborne concentrations of benzene.
(7) EMPLOYEE NOTIFICATION OF

MONITORING RESULTS
(i) The employer shall, within 15 working days

after the receipt of the results of any
monitoring performed under this standard,
notify each employee of these results in
writing either individually or by posting of
results in an appropriate location that is
accessible to affected employees.
(ii) Whenever the PELs are exceeded, the written
notification required by paragraph (E)(7)(i) of
this section shall contain the corrective action
being taken by the employer to reduce the
employee exposure to or below the PEL, or
shall refer to a document available to the
employee which states the corrective actions
to be taken.
(F) METHODS OF COMPLIANCE

(1) ENGINEERING CONTROLS AND WORK PRACTICES
(i) The employer shall institute engineering

controls and work practices to reduce and
maintain employee exposure to benzene at
or below the permissible exposure limits,
except to the extent that the employer can
establish that these controls are not feasible
or where the provisions of paragraph
(F)(1)(iii) or (G)(1) of this section apply.
(ii) Wherever the feasible engineering controls
and work practices which can be instituted
are not sufficient to reduce employee exposure
to or below the PELs, 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 which complies with
the requirements of paragraph (G) of this
section.
(iii) Where the employer can document that
benzene is used in a workplace less than a
total of 30 days per year, the employer shall
use engineering controls, work practice
controls or respiratory protection or any
B-4
9/04
combination of these controls to reduce

employee exposure to benzene to or below
the PELs, except that employers shall use
engineering and work practice controls, if
feasible, to reduce exposure to or below 10
ppm as an 8-hour TWA.
(2) COMPLIANCE PROGRAM
(i) When any exposures are over the PEL, the

employer shall establish and implement a
written program to reduce employee exposure
to or below the PEL primarily by means of
engineering and work practice controls, as
required by paragraph (F)(1) of this section.
(ii) The written program shall include a schedule
for development and implementation of the
engineering and work practice controls.
These plans shall be reviewed and revised as
appropriate based on the most recent exposure
monitoring data, to reflect the current status
of the program.
(iii) Written compliance programs shall be
furnished upon request for examination
and copying to the Assistant Secretary, the
Director, affected employees and designated
employee representatives.
(G) RESPIRATORY PROTECTION

(1) GENERAL
The employer shall provide respirators and

assure that they are used, where required by this
section. Respirators shall be used in the following
circumstances:
(i) During the time period necessary to install
or implement feasible engineering and work
practice controls;
(ii) In work operations for which the employer
establishes that compliance with either the
TWA or STEL through the use of engineering
and work practice controls is not feasible,
such as some maintenance and repair activities,
9/04
vessel cleaning, or other operations where

engineering and work practice controls are
infeasible because exposures are intermittent
in nature and limited in duration;
(iii) In work situations where feasible engineering
and work practice controls are not yet sufficient
or are not required under paragraph (F)(1)(iii)
of this section to reduce exposure to or
below the PELs; and (iv) In emergencies.
(2) RESPIRATOR SELECTION
(i) Where respirators are required or allowed

under this section, the employer shall select
and provide, at no cost to the employee, the
appropriate respirator as specified in Table 1,
and shall assure that the employee uses the
respirator provided.
(ii) The employer shall select respirators from
among those jointly approved by the Mine
Safety and Health Administration and the
National Institute for Occupational Safety and
Health under the provisions of 30 CFR Part
11. Negative pressure respirators shall have
filter elements approved by MSHA/NIOSH
for organic vapors or benzene.
(iii) Any employee who cannot wear a negative
pressure respirator shall be given the option
of wearing a respirator with less breathing
resistance such as a powered air-purifying
respirator or supplied air respirator.
(3) RESPIRATOR PROGRAM
The employer shall institute a respiratory protection

program in accordance with 29 CFR 1910.134 (B),
(D), (E) and (F).
(4) RESPIRATOR USE
(i) Where air-purifying respirators are used,

the employer shall replace the air purifying
element at the expiration of service life or at
the beginning of each shift in which they
will be used, whichever comes first.
B-5
TABLE 1: RESPIRATORY PROTECTION FOR BENZENE

Airborne Concentration
of Benzene or
Condition of Use
Respirator Type
(a) Less than or

equal to 10 ppm.
(1) Half-mask air-purifying

respirator with organic
vapor cartridge.
(b) Less than or

equal to 50 ppm.
(1) Full facepiece

vapor cartridges.
(2) Full facepiece gas
mask with chin
style canister.1
(c) Less than or

equal to 100 ppm.
(1) Full facepiece

powered air-purifying
vapor canister.1
(d) Less than or

equal to 1,000 ppm.
(1) Supplied air respirator

with full facepiece in
positive-pressure mode.
(e) Greater than 1,000

ppm or unknown
concentration.
(1) Self-contained breathing

apparatus with full
facepiece in positive
pressure mode.
(2) Full facepiece positive
pressure supplied-air
respirator with
auxiliary self-contained
air supply.
(f) Escape
(1) Any organic vapor gas

mask; or
(2) Any self-contained
breathing apparatus
with full facepiece.
(g) Firefighting
(1) Full facepiece

self-contained breathing
apparatus in positive
pressure mode.
1Canisters must have a minimum service life of four (4) hours

when tested at 150 ppm benzene, at a flow rate of 64 LPM,
and 85% relative humidity for non-powered air-purifying
respirators. The flow rate shall be 115 LPM and 170 LPM
respectively for tight fitting and loose fitting powered
air-purifying respirators.
B-6
(ii) If an air purifying element becomes available

with an end of useful life indicator for
benzene approved by MSHA/NIOSH, the
element may be used until such time as the
indicator shows no further useful life.
(iii) The employer shall permit employees who
wear respirators to leave the regulated area
to wash their faces and respirator facepieces
as necessary in order to prevent skin irritation
associated with respirator use or to change
the filter elements of air-purifying respirators
whenever they detect a change in breathing
resistance or chemical vapor breakthrough.
(5) RESPIRATOR FIT TESTING
(i) The employer shall perform, and certify the

results of, either quantitative or qualitative fit
tests at the time of initial fitting and at least
annually thereafter for each employee
wearing a negative pressure respirator.
The test shall be used to select a respirator
facepiece which exhibits minimum leakage
and provides the required protection as
prescribed in Table 1. The employer shall
provide and assure that the employee wears
a respirator demonstrated by the fit test to
provide the required protection.
(ii) The employer shall follow the test protocols
outlined in Appendix E of this standard for
whichever type of fit testing the employer
chooses.
(H) PROTECTIVE CLOTHING

AND EQUIPMENT
Personal protective clothing and equipment shall be
worn where appropriate to prevent eye contact and
limit dermal exposure to liquid benzene. Protective
clothing and equipment shall be provided by the
employer at no cost to the employee and the
employer shall assure its use where appropriate.
Eye and face protection shall meet the requirements
of 29 CFR 1910.133.
9/04
(I) MEDICAL SURVEILLANCE

(1) GENERAL
(i) The employer shall make available a medical

surveillance program for employees who are
or may be exposed to benzene at or above
the action level 30 or more days per year; for
employees who are or may be exposed to
benzene at or above the PELs 10 or more
days per year; for employees who have been
exposed to more than 10 ppm of benzene for
30 or more days in a year prior to the effective
date of the standard when employed by their
current employer; and for employees
involved in the tire building operations called
tire building machine operators, who use
solvents containing greater than 0.1% benzene.
(ii) The employer shall assure that all medical
examinations and procedures are performed
by or under the supervision of a licensed
physician and that all laboratory tests are
conducted by an accredited laboratory.
(iii) The employer shall assure that persons other
than licensed physicians who administer the
pulmonary function testing required by this
section shall complete a training course in
spirometry sponsored by an appropriate
governmental, academic or professional
institution.
(iv) The employer shall assure that all
examinations and procedures are provided
without cost to the employee and at a
reasonable time and place.
other hematological toxins,

(2) A family history of blood dyscrasias
including hematological neoplasms;
(3) A history of blood dyscrasias including
genetic hemoglobin abnormalities,
bleeding abnormalities, abnormal
function of formed blood elements;
(4) A history of renal or liver dysfunction;
(5) A history of medicinal drugs routinely
taken;
(6) A history of previous exposure to
ionizing radiation and
(7) Exposure to marrow toxins outside of
the current work situation.
(B) A COMPLETE PHYSICAl EXAMINATION.
(C) LABORATORY TESTS-A complete blood
count including a leukocyte count with
differential, a quantitative thrombocyte
count, hematocrit, hemoglobin,
erythrocyte count and erythrocyte indices
(MCV, MCH, MCHC). The results of these
tests shall be reviewed by the examining
physician.
(D) ADDITIONAL TESTS as necessary in the
opinion of the examining physician,
based on alterations to the components
of the blood or other signs which may be
related to benzene exposure; and
(E) For all workers required to wear
respirators for at least 30 days a year, the
physical examination shall pay special
attention to the CARDIOPULMONARY
SYSTEM and shall include a PULMONARY
FUNCTION TEST.
(2) INITIAL EXAMINATION
(i) Within 60 days of the effective date of this

standard, or before the time of initial
assignment, the employer shall provide each
employee covered by paragraph (I)(1)(i) of
this section with a medical examination
including the following elements:
(A) A DETAILED OCCUPATIONAL HISTORY
which includes:
(1) Past work exposure to benzene or any
9/04
(ii) No initial medical examination is required

to satisfy the requirements of paragraph
(I)(2)(i) of this section if adequate records
show that the employee has been examined
in accordance with the procedures of
paragraph (I)(2)(i) of this section within the
twelve months prior to the effective date of
this standard.
B-7
(3) PERIODIC EXAMINATIONS
(i) The employer shall provide each employee

covered under paragraph (I)(1)(i) of this
section with a medical examination annually
following the previous examination. These
periodic examinations shall include at least
the following elements:
(A) A brief history regarding any new
exposure to potential marrow toxins,
changes in medicinal drug use, and the
appearance of physical signs relating to
blood disorders:
(B) A complete blood count including a
leukocyte count with differential,
quantitative thrombocyte count,
hemoglobin, hematocrit, erythrocyte
count, and erythrocyte indices (MCV,
MCH, MCHC); and
(C) Appropriate additional tests as necessary,
in the opinion of the examining physician,
in consequence of alterations in the
components of the blood or other signs
which may be related to benzene
exposure.
(ii) Where the employee develops signs and
symptoms commonly associated with toxic
exposure to benzene, the employer shall
provide the employee with an additional
medical examination which shall include
those elements considered appropriate by
the examining physician.
(iii) For persons required to use respirators for
at least 30 days a year, a pulmonary function
test shall be performed every three (3) years.
A specific evaluation of the cardiopulmonary
system shall be made at the time of the
pulmonary function test.
(4) EMERGENCY EXAMINATIONS
(i) In addition to the surveillance required by

(I)(1)(i), if an employee is exposed to
benzene in an emergency situation, the
employer shall have the employee provide
a urine sample at the end of the employees
shift and have a urinary phenol test
B-8
performed on the sample within 72 hours.

The urine specific gravity shall be corrected
to 1.024.
(ii) If the result of the urinary phenol test is
below 75 mg phenol/L of urine, no further
testing is required.
(iii) If the result of the urinary phenol test is
equal to or greater than 75 mg phenol/L of
urine, the employer shall provide the
employee with a complete blood count
including an erythrocyte count, leukocyte
count with differential and thrombocyte
count at monthly intervals for a duration of
three (3) months following the emergency
exposure.
(iv) If any of the conditions specified in paragraph
(I)(5)(i) of this section exists, then the further
requirements of paragraph (I)(5) of this
section shall be met and the employer shall,
in addition, provide the employees with
periodic examinations if directed by the
physician.
(5) ADDITIONAL EXAMINATIONS AND REFERRALS
(i) Where the results of the complete blood

count required for the initial and periodic
examinations indicate any of the following
abnormal conditions exist, then the blood
count shall be repeated within 2 weeks.
(A) The hemoglobin level or the hematocrit
falls below the normal limit [outside the
95% confidence interval (C.I.)] as
determined by the laboratory for the
particular geographic area and/or these
indices show a persistent downward
trend from the individuals pre-exposure
norms; provided these findings cannot be
explained by other medical reasons.
(B) The thrombocyte (platelet) count varies
more than 20 percent below the
employees most recent values or falls
outside the normal limit (95% C.I.) as
determined by the laboratory.
9/04
(7) PHYSICIANS WRITTEN OPINIONS
(C) The leukocyte count is below 4,000 per

mm 3 or there is an abnormal differential
count.
(ii) If the abnormality persists, the examining
physician shall refer the employee to a
hematologist or an internist for further
evaluation unless the physician has good
reason to believe such referral is unnecessary.
(See Appendix C for examples of conditions
where a referral maybe unnecessary.)
(iii) The employer shall provide the hematologist
or internist with the information required to
be provided to the physician under paragraph (I)(6) of this section and the medical
record required to be maintained by paragraph
(K)(2)(ii) of this section.
(iv) The hematologists or internists evaluation
shall include a determination as to the need
for additional tests, and the employer shall
assure that these tests are provided.
(6) INFORMATION PROVIDED TO THE PHYSICIAN
The employer shall provide the following

information to the physician:
(i) A copy of this regulation and its appendices;
(ii) A description of the affected employees
duties as they relate to the employees
exposure;
(iii) The employees actual or representative
exposure level;
(iv) A description of any personal protective
equipment used or to be used; and
(v) Information from previous employmentrelated medical examinations of the affected
employee which is not otherwise available to
the examining physician.
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(i) For each examination under this section, the

employer shall obtain and provide the
employee with a copy of the examining
physicians written opinion within 15 days of
the examination. The written opinion shall be
limited to the following information:
(A) The occupationally pertinent results of
the medical examination and tests;
(B) The physicians opinion concerning
whether the employee has any detected
medical conditions which would place
the employees health at greater than
normal risk of material impairment from
exposure to benzene;
(C) The physicians recommended limitations
upon the employees exposure to
benzene or upon the employees use of
protective clothing or equipment and
respirators.
(D) A statement that the employee has been
informed by the physician of the results
of the medical examination and any
medical conditions resulting from
benzene exposure which require further
explanation or treatment.
(ii) The written opinion obtained by the employer
shall not reveal specific records, findings and
diagnoses that have no bearing on the
employees ability to work in a benzeneexposed workplace.
(8) MEDICAL REMOVAL PLAN
(i) When a physician makes a referral to a

hematologist/internist as required under
paragraph (I)(5)(ii) of this section, the
employee shall be removed from areas
where exposures may exceed the action
level until such time as the physician makes
a determination under paragraph (I)(8)(ii)
of this section.
(ii) Following the examination and evaluation
by the hematologist/internist, a decision to
remove an employee from areas where
benzene exposure is above the action level
B-9
or to allow the employee to return to areas

where benzene exposure is above the action
level shall be made by the physician in
consultation with the hematologist/internist.
This decision shall be communicated in
writing to the employer and employee. In the
case of removal, the physician shall state the
required probable duration of removal from
occupational exposure to benzene above the
action level and the requirements for future
medical examinations to review the decision.
(iii) For any employee who is removed pursuant
to paragraph (I)(8)(ii) of this section,
the employer shall provide a follow-up
examination. The physician, in consultation
with the hematologist/ internist, shall make a
decision within 6 months of the date the
employee was removed as to whether the
employee shall be returned to the usual job
or whether the employee should be removed
permanently.
(iv) Whenever an employee is temporarily
removed from benzene exposure pursuant to
paragraph (I)(8)(i) or (I)(8)(ii) of this section,
the employer shall transfer the employee to a
comparable job for which the employee is
qualified (or can be trained for in a short
period) and where benzene exposures are as
low as possible, but in no event higher than
the action level. The employer shall maintain
the employees current wage rate, seniority
and other benefits. If there is no such job
available, the employer shall provide medical
removal protection benefits until such a job
becomes available or for 6 months, whichever
comes first.
in a short period) and where benzene

exposures are as low as possible but in no
event higher than the action level. The
employer shall assure that such employee
suffers no reduction in current wage rate,
seniority or other benefits as a result of
the transfer.
(9) MEDICAL REMOVAL PROTECTION BENEFITS
(i) The employer shall provide to an employee 6

months of medical removal protection benefits immediately following each occasion an
employee is removed from exposure to
benzene because of hematological findings
pursuant to paragraphs (I)(8)(i) and (ii) of
this section, unless the employee has been
transferred to a comparable job where
benzene exposures are below the action
level.
(ii) For the purposes of this section, the requirement that an employer provide medical
removal protection benefits means that the
employer shall maintain the current wage
rate, seniority and other benefits of an
employee as though the employee had not
been removed.
(iii) The employers obligation to provide medical
removal protection benefits to a removed
employee shall be reduced to the extent that
the employee receives compensation for
earnings lost during the period of removal
either from a publicly or employer-funded
compensation program, or from employment
with another employer made possible by
virtue of the employees removal.
(v) Whenever an employee is removed

permanently from benzene exposure based
on a physicians recommendation pursuant to
paragraph (I)(8)(iii) of this section, the
employee shall be given the opportunity to
transfer to another position which is available
or later becomes available for which the
employee is qualified (or can be trained for
B-10
9/04
(J) COMMUNICATION OF BENZENE

HAZARDS TO EMPLOYEES
(1) SIGNS AND LABELS
(i) The employer shall post signs at entrances

to regulated areas. The signs shall bear the
following legend:
DANGER
BENZENE
CANCER HAZARD
FLAMMABLE-NO SMOKING
AUTHORIZED PERSONNEL ONLY
RESPIRATOR REQUIRED
(ii) The employer shall ensure that labels or
other appropriate forms of warning are
provided for containers of benzene within
the workplace. There is no requirement to
label pipes. The labels shall comply with the
requirements of 29 CFR 1910.1200(f) and in
addition shall include the following legend:
DANGER
CONTAINS BENZENE
CANCER HAZARD
(2) MATERIAL SAFETY DATA SHEETS
(i) Employers shall obtain or develop, and shall

provide access to their employees, to a
material safety data sheet (MSDS) which
addresses benzene and complies with 29
CFR 1910.1200.
(ii) Employers who are manufacturers or
importers shall:
(A) Comply with paragraph (A) of this
section, and
(B) Comply with the requirement in OSHAs
Hazard Communication Standard,
29 CFR 1910.1200, that they deliver to
downstream employers an MSDS which
addresses benzene.
9/04
(3) INFORMATION AND TRAINING
(i) The employer shall provide employees with

information and training at the time of their
initial assignment to a work area where
benzene is present. If exposures are above
the action level, employees shall be provided
with information and training at least
annually thereafter.
(ii) The training program shall be in accordance
with the requirements of 29 CFR 1910.1200
(H)(1) and (2), and shall include specific
information on benzene for each category of
information included in that section.
(iii) In addition to the information required under
29 CFR 1910.1200, the employer shall:
(A) Provide employees with an explanation
of the contents of this section, including
Appendices A and B, and indicate to
them where the standard is available; and
(B) Describe the medical surveillance
program required under paragraph (I) of
this section, and explain the information
contained in Appendix C.
(K) RECORDKEEPING
(1) EXPOSURE MEASUREMENTS
(i) The employer shall establish and maintain an

accurate record of all measurements required
by paragraph (E) of this section, in accordance
with 29 CFR 1910.20.
(ii) This record shall include:
(A) The dates, number, duration, and results
of each of the samples taken, including a
description of the procedure used to
determine representative employee
exposures;
(B) A description of the sampling and
analytical methods used;
(C) A description of the type of respiratory
protective devices worn, if any; and
B-11
(D) The name, social security number, job

classification and exposure levels of the
employee monitored and all other
employees whose exposure the
measurement is intended to represent.
(iii) The employer shall maintain this record for at
least 30 years, in accordance with 29 CFR
1910.20.
(2) MEDICAL SURVEILLANCE
(i) The employer shall establish and maintain an

accurate record for each employee subject to
medical surveillance required by paragraph
(I) of this section, in accordance with 29 CFR
1910.20.
(ii) This record shall include:
(A) The name and social security number of
the employee;
(B) The employers copy of the physicians
written opinion on the initial, periodic
and special examinations, including
results of medical examinations and all
tests, opinions and recommendations;
(C) Any employee medical complaints related
to exposure to benzene;
(D) A copy of the information provided to
the physician as required by paragraphs
(I)(6)(ii) through (v) of this section; and
(E) A copy of the employees medical and
work history related to exposure to
benzene or any other hematologic toxins.
(iii) The employer shall maintain this record for
at least the duration of employment plus 30
years, in accordance with 29 CFR 1910.20.
(3) AVAILABILITY
(i) The employer shall assure that all records

required to be maintained by this section
shall be made available upon request to the
Assistant Secretary and the Director for examination and copying.
(ii) Employee exposure monitoring records
required by this paragraph shall be provided
B-12
upon request for examination and copying to

employees, employee representatives, and
the Assistant Secretary in accordance with 29
CFR 1910.20 (A) through (E) and (G) through
(I).
(iii) Employee medical records required by this
paragraph shall be provided upon request for
examination and copying, to the subject
employee, to anyone having the specific
written consent of the subject employee, and
to the Assistant Secretary in accordance with
29 CFR 1910.20.
(4) TRANSFER OF RECORDS
(i) The employer shall comply with the requirements involving transfer of records set forth
in 29 CFR 1019.20(H).
(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 notify the Director, at least
three (3) months prior to disposal, and transmit them to the Director if required by the
Director within that period.
(L) OBSERVATION OF MONITORING

(1) EMPLOYEE OBSERVATION
The employer shall provide affected employees, or

their designated representatives, an opportunity to
observe the measuring or monitoring of employee
exposure to benzene conducted pursuant to paragraph (E) of this section.
(2) OBSERVATION PROCEDURES
When observation of the measuring or monitoring

of employee exposure to benzene requires entry
into areas where the use of protective clothing and
equipment or respirators is required, the employer
shall provide the observer with personal protective
clothing and equipment or respirators required to
be worn by employees working in the area, assure
the use of such clothing and equipment or respirators, and require the observer to comply with all
other applicable safety and health procedures.
9/04
(M) DATES
APPENDIX A TO 1910.1028-SUBSTANCE SAFETY DATA

SHEET, BENZENE
(1) EFFECTIVE DATE
(I) SUBSTANCE IDENTIFICATION

(A) SUBSTANCE: Benzene.
(B) PERMISSIBLE EXPOSURE: Except as to the
use of gasoline, motor fuels and other fuels
subsequent to discharge from bulk terminals
and other exemptions specified in
1910.1028(A)(2):
(1) AIRBORNE: The maximum time-weighted
average (TWA) exposure limit is 1 part of
benzene vapor per million parts of air (1
ppm) for an 8-hour workday and the
maximum short-term exposure limit (STEL)
is 5 ppm for any 15-minute period.
(2) DERMAL: Eye contact shall be prevented and
skin contact with liquid benzene shall be
limited.
(C) APPEARANCE AND ODOR: Benzene is a
clear, colorless liquid with a pleasant, sweet
odor. The odor of benzene does not provide
adequate warning of its hazard.
The standard shall become effective December 10,

1987.
(2) START-UP DATES
(i) The requirements of paragraph (A) through

(M) of this section, except the engineering
control requirements of paragraph (F)(1) of
B-12 2/96.this section shall be completed
within sixty (60) days after the effective date
of the standard.
(ii) Engineering and work practice controls
required by paragraph (F)(1) of this section
shall be implemented no later than 2 years
after the effective date of the standard.
(iii) Coke and coal chemical operations may
comply with paragraph (M)(2)(ii) of this
section or alternately include within the
compliance program required by paragraph
(F)(2) of this section, a requirement to phase
in engineering controls as equipment is
repaired and replaced. For coke and coal
chemical operations choosing the latter
alternative, compliance with the engineering
controls requirements of paragraph (F)(1)
of this section shall be achieved no later
than 5 years after the effective date of this
standard and substantial compliance with the
engineering control requirements shall be
achieved within 3 years of the effective date
of this standard.
(N) APPENDICES
The information contained in Appendices A, B, C,
and D is not intended, by itself, to create any
additional obligations not otherwise imposed or to
detract from any existing obligations. The protocols
on respiratory fit testing in Appendix E are mandatory.
(Approved by the Office of Management and
Budget under control number 1218-0129)
9/04
(II) HEALTH HAZARD DATA

(A) WAYS IN WHICH BENZENE AFFECTS YOUR
HEALTH: Benzene can affect your health if
you inhale it, or if it comes in contact with
your skin or eyes. Benzene is also harmful if
you happen to swallow it.
(B) EFFECTS OF OVEREXPOSURE
(1) SHORT-TERM (ACUTE) OVEREXPOSURE: If
you are overexposed to high concentrations
of benzene, well above the levels where its
odor is first recognizable, you may feel
breathless, irritable, euphoric, or giddy; you
may experience irritation in eyes, nose, and
respiratory tract. You may develop a
headache, feel dizzy, nauseated, or intoxicated.
Severe exposures may lead to convulsions
and loss of consciousness.
(2) LONG-TERM (CHRONIC) EXPOSURE:
Repeated or prolonged exposure to benzene,
even at relatively low concentrations, may
result in various blood disorders, ranging
from anemia to leukemia, an irreversible,
B-13
fatal disease. Many blood disorders associated

with benzene exposure may occur without
symptoms.
(III) PROTECTIVE CLOTHING AND EQUIPMENT
(A) RESPIRATORS: Respirators are required for
those operations in which engineering controls
or work practice controls are not feasible to
reduce exposure to the permissible level.
However, where employers can document
that benzene is present in the workplace less
than 30 days a year, respirators may be used
in lieu of engineering controls. If respirators
are worn, they must have joint Mine Safety
and Health Administration and the National
Institute for Occupational Safety and Health
(NIOSH) seal of approval, and cartridge or
canisters must be replaced before the end of
their service life, or the end of the shift,
whichever occurs first. If you experience
difficulty breathing while wearing a respirator,
you may request a positive pressure respirator
from your employer. You must be thoroughly
trained to use the assigned respirator, and the
training will be provided by your employer.
(B) PROTECTIVE CLOTHING: You must wear
appropriate protective clothing (such as
boots, gloves, sleeves, aprons, etc.) over any
parts of your body that could be exposed to
liquid benzene.
(C) EYE AND FACE PROTECTION: You must
wear splash-proof safety goggles if it is
possible that benzene may get into your
eyes. In addition, you must wear a face
shield if your face could be splashed with
benzene liquid.
(IV) EMERGENCY AND FIRST AID PROCEDURES
(A) EYE AND FACE EXPOSURE: If benzene is
splashed in your eyes, wash it out immediately
with large amounts of water. If irritation
persists or vision appears to be affected see
a doctor as soon as possible.
(B) SKIN EXPOSURE: If benzene is spilled
on your clothing or skin, remove the
contaminated clothing and wash the exposed
skin with large amounts of water and soap
B-14
immediately. Wash contaminated clothing

before you wear it again.
(C) BREATHING: If you or any other person
breathes in large amounts of benzene, get the
exposed person to fresh air at once. Apply
artificial respiration if breathing has stopped.
Call for medical assistance or a doctor as
soon as possible. Never enter any vessel
or confined space where the benzene
concentration might be high without proper
safety equipment and at least one other
person present who will stay outside. A
life line should be used.
(D) SWALLOWING: If benzene has been
swallowed and the patient is conscious,
do not induce vomiting. Call for medical
assistance or a doctor immediately.
(V) MEDICAL REQUIREMENTS
If you are exposed to benzene at a concentration at
or above 0.5 ppm as an 8-hour time-weighted
average, or have been exposed at or above 10 ppm
in the past while employed by your current
employer, your employer is required to provide a
medical examination and history and laboratory
tests within 60 days of the effective date of this
standard and annually thereafter. These tests shall
be provided without cost to you. In addition, if you
are accidentally exposed to benzene (either by
ingestion, inhalation, or skin/eye contact) under
emergency conditions known or suspected to
constitute toxic exposure to benzene, your employer
is required to make special laboratory tests
available to you.
(VI) OBSERVATION OF MONITORING
Your employer is required to perform measurements
that are representative of your exposure to benzene
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.
9/04
(VII) ACCESS TO RECORDS

You or your representative are entitled to see the
records of measurements of your exposure to
benzene upon written request to your employer.
Your medical examination records can be furnished
to yourself, your physician or designated representative upon request by you to your employer.
(VIII) PRECAUTIONS FOR SAFE USE, HANDLING
AND STORAGE
Benzene liquid is highly flammable. It should be
stored in tightly closed containers in a cool, well
ventilated area. Benzene vapor may form explosive
mixtures in air. All sources of ignition must be controlled. Use nonsparking tools when opening or
closing benzene containers. Fire extinguishers,
where provided, must be readily available. Know
where they are located and how to operate them.
Smoking is prohibited in areas where benzene is
used or stored. Ask your supervisor where benzene
is used in your area and for additional plant safety
rules.
APPENDIX B TO 1910.1028-SUBSTANCE
TECHNICAL GUIDELINES, BENZENE
(I) PHYSICAL AND CHEMICAL DATA
(A) SUBSTANCE IDENTIFICATION
(1) SYNONYMS: Benzol, benzol, coal
naphtha, cyclohexatriene, phene, phenyl
hydride, and pyrobenzol. (Benzin,
petroleum benzin and Benzine do not
contain benzene.)
(2) FORMULA: C6 H6 (CAS Registry
Number: 71-43-2)
(B) PHYSICAL DATA
(1) BOILING POINT (760 mm Hg); 80.1 C
(176 F)
(2) SPECIFIC GRAVITY (water=1): 0.879
(3) VAPOR DENSITY (air=1): 2.7
(4) MELTING POINT: 5.5 C (42 F)
(5) VAPOR PRESSURE AT 20 C (68 F):
75 mm Hg
(6) SOLUBILITY IN WATER: .06%
(7) EVAPORATION RATE (ether=1): 2.8
(8) APPEARANCE AND ODOR: Clear,
colorless liquid with a distinctive sweet
odor.
9/04
(II) FIRE, EXPLOSION, AND REACTIVITY HAZARD

DATA
(A) FIRE
(1) FLASH POINT (closed cup): -11 C (12 F)
(2) AUTOIGNITION TEMPERATURE: 580 C
(1076 F)
(3) FLAMMABLE LIMITS IN AIR: % by
Volume: Lower: 1.3%, Upper: 7.5%
(4) EXTINGUISHING MEDIA: Carbon dioxide,
dry chemical, or foam.
(5) SPECIAL FIRE-FIGHTING PROCEDURES:
Do not use a solid stream of water, since
a stream will scatter and spread fire. Fine
water spray can be used to keep fireexposed containers cool.
(6) UNUSUAL FIRE AND EXPLOSION
HAZARDS: Benzene is a flammable
liquid. Its vapors can form explosive
mixtures. All ignition sources must be
controlled when benzene is used,
handled, or stored. Where liquid or vapor
may be released, such areas shall be
considered as hazardous locations.
Benzene vapors are heavier than air; thus
the vapors may travel along the ground
and be ignited by open flames or sparks
at locations remote from the site at which
benzene is handled.
(7) Benzene is classified as a 1B flammable
liquid for the purpose of conforming to
the requirements of 29 CFR 1910.106. A
concentration exceeding 3,250 ppm is
considered a potential fire explosion
hazard. Locations where benzene may be
present in quantities sufficient to produce
explosive or ignitable mixtures are
considered Class I Group D for the
purposes of conforming to the
requirements of 29 CFR 1910.309.
(B) REACTIVITY
(1) CONDITIONS CONTRIBUTING TO
INSTABILITY: Heat.
(2) INCOMPATIBILITY: Heat and oxidizing
materials.
(3) HAZARDOUS DECOMPOSITION
PRODUCTS: Toxic gases and vapors
(such as carbon monoxide).
B-15
(III) SPILL AND LEAK PROCEDURES

(A) STEPS TO BE TAKEN IF THE MATERIAL IS
RELEASED OR SPILLED: As much benzene as
possible should be absorbed with suitable
materials such as dry sand or earth. That
remaining must be flushed with large
amounts B-15 2/96.of water. Do not flush
benzene into a confined space, such as a
sewer, because of explosion danger. Remove
all ignition sources. Ventilate enclosed places.
(B) WASTE DISPOSAL METHOD: Disposal
methods must conform to other jurisdictional
regulations. If allowed, benzene may be
disposed of: (a) By absorbing it in dry sand
or earth and disposing in a sanitary landfill;
(b) if small quantities, by removing it to a
safe location from buildings or other
combustible sources, pouring it in dry sand
or earth and cautiously igniting it; and (c) if
large quantities, by atom-izing it in a suitable
combustion chamber.
(IV) MISCELLANEOUS PRECAUTIONS
(A) HIGH EXPOSURE TO BENZENE can occur
when transferring the liquid from one
container to another. Such operations should
be well ventilated and good work practices
must be established to avoid spills.
(B) USE NON-SPARKING TOOLS to open
benzene containers which are effectively
grounded and bonded prior to opening
and pouring.
(C) EMPLOYERS MUST ADVISE EMPLOYEES of
all plant areas and operations where exposure
to benzene could occur. Common operations
in which high exposures to benzene may be
encountered are: the primary production and
utilization of benzene, and transfer of benzene.
APPENDIX C TO 1910.1028-MEDICAL
SURVEILLANCE GUIDELINES FOR BENZENE
(I) ROUTE OF ENTRY
Inhalation; skin absorption.
(II) TOXICOLOGY
Benzene is primarily an inhalation hazard. Systemic
absorption may cause depression of the hematopoietic
B-16
system, pancytopenia, aplastic anemia, and

leukemia. Inhalation of high concentrations can
affect central nervous system function. Aspiration
of small amounts of liquid benzene immediately
causes pulmonary edema and hemorrhage of
pulmonary tissue. There is some absorption through
the skin. Absorption may be more rapid in the case
of abraded skin, and benzene may be more readily
absorbed if it is present in a mixture or as a
contaminant in solvents which are readily absorbed.
The defatting action of benzene may produce
primary irritation due to repeated or prolonged
contact with the skin. High concentrations are
irritating to the eyes and the mucous membranes
of the nose, and respiratory tract.
(III) SIGNS AND SYMPTOMS
Direct skin contact with benzene may cause
erythema. Repeated or prolonged contact may
result in drying, scaling dermatitis, or development
of secondary skin infections. In addition, there is
benzene absorption through the skin. Local effects
of benzene vapor or liquid on the eye are slight.
Only at very high concentrations is there any
smarting sensation in the eye. Inhalation of high
concentrations of benzene may have an initial
stimulatory effect on the central nervous system
characterized by exhilaration, nervous excitation,
and/or giddiness, followed by a period of depression,
drowsiness, or fatigue. A sensation of tightness
in the chest accompanied by breath-lessness
may occur and ultimately the victim may lose
consciousness. Tremors, convulsions and death
may follow from respiratory paralysis or circulatory
collapse in a few minutes to several hours following
severe exposures.
The detrimental effect on the blood-forming
system of prolonged exposure to small quantities
of benzene vapor is of extreme importance. The
hematopoietic system is the chief target for
benzenes toxic effects which are manifested by
alterations in the levels of formed elements in the
peripheral blood. These effects have occurred at
concentrations of benzene which may not cause
irritation of mucous membranes, or any unpleasant
sensory effects. Early signs and symptoms of
benzene morbidity are varied, often not readily
9/04
noticed and non-specific. Subjective complaints of

headache, dizziness, and loss of appetite may
precede or follow clinical signs. Rapid pulse and
low blood pressure, in addition to a physical
appearance of anemia, may accompany a subjective
complaint of shortness of breath and excessive
tiredness. Bleeding from the nose, gums, or mucous
membranes, and the development of purpuric spots
(small bruises) B-16 2/96.may occur as the condition
progresses. Clinical evidence of leukopenia, anemia,
and thrombocy-topenia, singly or in combination,
has been frequently reported among the first signs.
Bone marrow may appear normal, aplastic, or
hyperplastic, and may not, in all situations, correlate
with peripheral blood-forming tissues. Because of
variations in the susceptibility to benzene morbidity,
there is no typical blood picture. The onset of
effects of prolonged benzene exposure may be
delayed for many months or years after the actual
exposure has ceased and identification or correlation
with benzene exposure must be sought out in the
occupational history.
(IV) TREATMENT OF ACUTE TOXIC EFFECTS
REMOVE FROM EXPOSURE IMMEDIATELY.
Make sure you are adequately protected and do not
risk being overcome by fumes. Give oxygen or
artificial resuscitation if indicated. Flush eyes, wash
skin if contaminated and remove all contaminated
clothing. Symptoms of intoxication may persist
following severe exposures. Recovery from mild
exposures is usually rapid and complete.
(V) SURVEILLANCE AND PREVENTIVE
CONSIDERATIONS
(A) GENERAL
The principal effects of benzene exposure
which form the basis for this regulation are
pathological changes in the hematopoietic
system, reflected by changes in the
peripheral blood and manifesting clinically
as pancytopenia, aplastic anemia, and
leukemia. Consequently, the medical
surveillance program is designed to observe,
on a regular basis, blood indices for early
signs of these effects, and although early
signs of leukemia are not usually available,
9/04
emerging diagnostic technology and innovative

regimes make consistent surveillance for
leukemia, as well as other hematopoietic
effects, essential.
Initial examinations are to be provided
within 60 days of the effective date of this
standard, or at the time of initial assignment,
and periodic examinations annually thereafter.
There are special provisions for medical tests
in the event of hematologic abnormalities or
for emergency situations.
The blood values which require referral to
a hematologist or internist are noted in the
standard in paragraph (I)(5). The standard
specifies that blood abnormalities that persist
must be referred unless the physician has
good reason to believe such referral is
unnecessary (paragraph (I)(5)). Examples
of conditions that could make a referral
unnecessary despite abnormal blood limits
are iron or folate deficiency, menorrhagia, or
blood loss due to some unrelated medical
abnormality.
Symptoms and signs of benzene toxicity
can be non-specific. Only a detailed history
and appropriate investigative procedures
will enable a physician to rule out or confirm
conditions that place the employee at
increased risk. To assist the examining
physician with regard to which laboratory
tests are necessary and when to refer an
employee to the specialist, OSHA has
established the following guidelines.
(B) HEMATOLOGY GUIDELINES
A minimum battery of tests is to be performed
by strictly standardized methods.
(1)Red cell, white cell, platelet counts, white
blood cell differential, hematocrit and red
cell indices must be performed by an
accredited laboratory. The normal ranges
for the red cell and white cell counts are
influenced by altitude, race, and sex, and
therefore should be determined by the
accredited laboratory in the specific area
where the tests are performed.
B-17
Either a decline from an absolute

normal or an individuals base line to a
subnormal value or a rise to a supranormal value, are indicative of potential
toxicity, particularly if all blood parameters
decline. The normal total white blood
count is approximately 7,200/mm 3 plus or
minus 3,000. For cigarette smokers, the
white count may be higher and the upper
range may be 2,000 cells higher than
normal for the laboratory. In addition,
infection, allergies B-17 2/96.and some
drugs may raise the white cell count. The
normal platelet count is approximately
250,000 with a range of 140,000 to
400,000. Counts outside this range should
be regarded as possible evidence of
benzene toxicity. Certain abnormalities
found through routine screening are of
greater significance in the benzeneexposed worker and require prompt
consultation with a specialist, namely:
a. THROMBOCYTOPENIA.
b. A TREND OF DECREASING WHITE
CELL, RED CELL, OR PLATELET
INDICES in an individual over time
is more worrisome than an isolated
abnormal finding at one test time. The
importance of trend highlights the need
to compare an individuals test results
to baseline and/or previous periodic
tests.
c. A CONSTELLATION OR PATTERN OF
ABNORMALITIES in the different blood
indices is of more significance than a
single abnormality. A low white count
not associated with any abnormalities in
other cell indices may be a normal
statistical variation, whereas if the low
white count is accompanied by decreases
in the platelet and/or red cell indices,
such a pattern is more likely to be
associated with benzene toxicity and
merits thorough investigation.
Anemia, leukopenia, macrocytosis
or an abnormal differential white blood
cell count should alert the physician to
B-18
further investigate and/or refer the

patient if repeat tests confirm the
abnormalities. If routine screening
detects an abnor-mality, follow-up tests
which may be helpful in establishing
the etiology of the abnormality are
the peripheral blood smear and the
reticulocyte count.
The extreme range of normal for
reticulocytes is 0.4 to 2.5 percent of the
red cells, the usual range being 0.5 to
1.2 percent of the red cells, but the
typical value is in the range of 0.8 to
1.0 percent. A decline in reticulocytes
to levels of less than 0.4 percent is to
be regarded as possible evidence
(unless another specific cause is found)
of benzene toxicity requiring accelerated
surveillance. An increase in reticulocyte
levels to about 2.5 percent may also
be consistent with (but is not as
characteristic of) benzene toxicity.
(2) An important diagnostic test is a careful
examination of the peripheral blood smear.
As with reticulocyte count the smear
should be with fresh uncoagulated blood
obtained from a needle tip following
venipuncture or from a drop of earlobe
blood (capillary blood). If necessary,
the smear may, under certain limited
conditions, be made from a blood sample
anticoagulated with EDTA (but never with
oxalate or heparin). When the smear is to
be prepared from a specimen of venous
blood which has been collected by a
commercial Vacutainer type tube
containing neutral EDTA, the smear should
be made as soon as possible after the
venesection. A delay of up to 12 hours
is permissible between the drawing of
the blood specimen into EDTA and the
prepa-ration of the smear if the blood
is stored at refrigerator (not freezing)
temperature.
(3) The minimum mandatory observations to
be made from the smear are:
a. The differential white blood cell count.
9/04
b. Description of abnormalities in the

appearance of red cells.
c. Description of any abnormalities in the
platelets.
d. A careful search must be made throughout every blood smear for immature
white cells such as band forms (in more
than normal proportion, i.e., over 10
percent of the total differential count),
any number of metamyelocytes, myelocytes or myelo-blasts. Any nucleate or
multinucleated red blood cells should
be reported. Large giant platelets or
fragments of megakaryocytes must be
recognized. B-18 2/96.
An increase in the proportion of
band forms among the neutrophilic
granulocytes is an abnormality deserving special mention, for it may
represent a change which should be
considered as an early warning of
benzene toxicity in the absence of
other causative factors (most commonly
infection). Likewise, the appearance of
metamyelocytes, in the absence of
another probable cause, is to be considered a possible indication of
benzene-induced toxicity.
An upward trend in the number of
basophils, which normally do not
exceed about 2.0 percent of the total
white cells, is to be regarded as possible evidence of benzene toxicity. A rise
in the eosinophil count is less specific
but also may be suspicious of toxicity if
it rises above 6.0 percent of the total
white count.
The normal range of monocytes is
from 2.0 to 8.0 percent of the total
white count with an average of about
5.0 percent. About 20 percent of individuals reported to have mild but
persisting abnormalities caused by
exposure to benzene show a persistent
monocytosis. The findings of a monocyte count which persists at more than
10 to 12 percent of the normal white
9/04
cell count (when the total count is

normal) or persistence of an absolute
monocyte count in excess of 800/mm 3
should be regarded as a possible sign
of benzene-induced toxicity.
A less frequent but more serious
indication of benzene toxicity is the
finding in the peripheral blood of the
so-called pseudo (or acquired) PelgerHuet anomaly. In this anomaly many,
or some-times the majority, of the neutrophilic granulocytes possess two
round nuclear segments-less often one
or three round segments -rather than
three normally elongated segments.
When this anomaly is not hereditary, it
is often but not invariably predictive of
subsequent leukemia. However, only
about 2% of patients who ultimately
develop acute myelogenous leukemia
show the acquired Pelger-Huet
anomaly. Other tests that can be administered to investigate blood
abnormalities are discussed below;
however, such procedures should be
undertaken by the hematologist.
The normal range of monocytes is
from 2.0 to 8.0 percent of the total
white count with an average of about
5.0 percent. About 20 percent of individuals reported to have mild but
persisting abnormalities caused by
exposure to benzene show a persistent
monocytosis. The findings of a monocyte count which persists at more than
10 to 12 percent of the normal white
cell count (when the total count is
normal) or persistence of an absolute
monocyte count in excess of 800/mm 3
should be regarded as a possible sign
of benzene-induced toxicity.
A less frequent but more serious
indication of benzene toxicity is the
finding in the peripheral blood of the
so-called pseudo (or acquired) PelgerHuet anomaly. In this anomaly many,
or some-times the majority, of the
B-19
neutrophilic granulocytes possess two

round nuclear segments-less often one
or three round segments -rather than
three normally elongated segments.
When this anomaly is not hereditary, it
is often but not invariably predictive of
subsequent leukemia. However, only
about 2% of patients who ultimately
develop acute myelogenous leukemia
show the acquired Pelger-Huet
anomaly. Other tests that can be
administered to investigate blood
abnormalities are discussed below;
however, such procedures should be
undertaken by the hematologist.
An uncommon sign, which cannot
be detected from the smear, but can be
elicited by a sucrose water test of
peripheral blood, is transient paroxysmal
nocturnal hemoglobinuria (PNH), which
may first occur insidiously during a
period of established aplastic anemia,
and maybe followed within one to a
few years by the appearance of rapidly
fatal acute myelogenous leukemia.
Clinical detection of PNH, which occurs
in only one or two percent of those
destined to have acute myelogenous
leukemia, may be difficult; if the
sucrose water test is positive, the
somewhat more definitive Ham test,
also known as the acid-serum hemolysis
test, may provide confirmation.
e. Individuals documented to have
developed acute myelogenous leukemia
years after initial exposure to benzene
may have progressed through a
preliminary phase of hematologic
abnormality. In some instances,
pancytopenia (i.e., a lowering in the
counts of all circulating blood cells of
bone marrow origin, but not to the
extent implied by the term aplastic
anemia) preceded leukemia for many
years. Depression of a single blood cell
type or platelets may represent a
harbinger of aplasia or leukemia. The
B-20
finding of two or more cytopenias, or

pancytopenia in a benzene-exposed
individual, must be regarded as highly
suspicious of more advanced although
still reversible, toxicity. Pancytopenia
coupled with the appear-ance of
immature cells (myelocytes, myeloblasts,
erythroblasts, etc.), with B-19
2/96.abnormal cells (pseudo PelgerHuet anomaly, atypical nuclear
heterochromatin, etc.), or unexplained
elevations of white blood cells must be
regarded as evidence of benzene overexposure unless proved otherwise.
Many severely aplastic patients
manifested the ominous finding of 5-10
percent myeloblasts in the marrow,
occasional myeloblasts and myelocytes
in the blood and 20-30% monocytes. It
is evident that isolated cytopenias,
pancytopenias, and even aplastic
anemias induced by benzene may be
reversible and complete recovery has
been reported on cessation of exposure.
However, since any of these
abnormalities is serious, the employee
must immediately be removed from any
possible exposure to benzene vapor.
Certain tests may substantiate the
employees prospects for progression or
regression. One such test would be an
examination of the bone marrow, but
the decision to perform a bone marrow
aspiration or needle biopsy is made by
the hematologist.
The findings of basophilic stippling
in circulating red blood cells (usually
found in 1 to 5% of red cells following
marrow injury), and detection in the
bone marrow of what are termed
ringed sideroblasts must be taken
seriously, as they have been noted in
recent years to be premonitory signs
of subsequent leukemia.
Recently peroxidase-staining of
circulating or marrow neutrophil
granulocytes, employing benzidine
9/04
dihydrochloride, have revealed the

disappearance of, or diminution in,
peroxidase in a sizable proportion of
the granulocytes, and this has been
reported as an early sign of leukemia.
However, relatively few patients have
been studied to date. Granulocyte
granules are normally strongly
peroxidase positive. A steady decline in
leukocyte alkaline phosphatase has also
been reported as suggestive of early
acute leukemia. Exposure to benzene
may cause an early rise in serum iron,
often but not always associated with a
fall in the reticulocyte count. Thus,
serial measurements of serum iron
levels may provide a means of
determining whether or not there is a
trend representing sustained suppression
of erythropoiesis.
Measurement of serum iron,
determination of peroxidase and
of alkaline phosphatase activity in
peripheral granulocytes can be
performed in most pathology
laboratories. Peroxidase and alkaline
phosphatase staining are usually
undertaken when the index of
suspicion for leukemia is high.
APPENDIX D TO 1910.1028-SAMPLING
AND ANALYTICAL METHODS FOR BENZENE
MONITORING AND MEASUREMENT PROCEDURES
Measurements taken for the purpose of determining
employee exposure to benzene are best taken so
that the representative average 8-hour exposure
may be determined from a single 8-hour sample or
two (2) 4-hour samples. Short-time interval samples
(or grab samples) may also be used to determine
average exposure level if a minimum of five
measurements are taken in a random manner over
the 8-hour work shift. Random sampling means that
any portion of the work shift has the same chance
of being sampled as any other. The arithmetic
average of all such random samples taken on one
work shift is an estimate of an employees average
9/04
level of exposure for that work shift. Air samples

should be taken in the employees breathing zone
(air that would most nearly represent that inhaled
by the employee). Sampling and analysis must be
performed with procedures meeting the requirements
of the standard.
There are a number of methods available for
monitoring employee exposures to benzene.
The sampling and analysis may be performed by
collection of the benzene vapor or charcoal
absorption tubes, with subsequent chemical analysis
by gas chromatography. Sampling and analysis may
also be performed by portable direct reading
instruments, real-time B-20 2/96.continuous
monitoring systems, passive dosimeters or other
suitable methods. The employer has the obligation
of selecting a monitoring method which meets the
accuracy and precision requirements of the standard
under his unique field conditions. The standard
requires that the method of monitoring must have
an accuracy, to a 95 percent confidence level,
of not less than plus or minus 25 percent for
concentrations of benzene greater than or
equal to 0.5 ppm.
The OSHA Laboratory modified NIOSH Method
S311 and evaluated it at a benzene air concentration
of 1 ppm. A procedure for determining the benzene
concentration in bulk material samples was also
evaluated. This work, reported in OSHA Laboratory
Method No. 12, includes the following two analytical
procedures:
(I) OSHA METHOD 12 FOR AIR SAMPLES
ANALYTE: Benzene
MATRIX: Air
PROCEDURE: Adsorption on charcoal,
desorption with carbon disulfide, analysis by GC.
DETECTION LIMIT: 0.04 ppm
RECOMMENDED AIR VOLUME AND
SAMPLING RATE: 10L to 0.2 L/min.
1. PRINCIPLE OF THE METHOD
1.1 A known volume of air is drawn through a
charcoal tube to trap the organic vapors present.
B-21
1.2 The charcoal in the tube is transferred to a

small, stoppered vial, and the analyte is desorbed
with carbon disulfide.
3.3 Gas chromatograph equipped with a flame

ionization detector.
1.3 An aliquot of the desorbed sample is injected

into a gas chromatograph.
3.4 Column (10-ft. x 1/8-in stainless steel) packed

with 80/100 Supelcoport coated with 20 percent SP
2100, 0.1 percent CW 1500.
1.4 The area of the resulting peak is determined

and compared with areas obtained from standards.
3.5 An electronic integrator or some other suitable

method for measuring peak area.
2.ADVANTAGES AND DISADVANTAGES

OF THE METHOD
2.1 The sampling device is small, portable, and
involved no liquids. Interferences are minimal, and
most of those which do occur can be eliminated by
altering chromatographic conditions. The samples
are analyzed by means of a quick, instrumental
method.
3.6 Two-milliliter sample vials with Teflon-lined

caps.
2.2 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.
3.9 Volumetric flasks: convenient sizes for making

standard solutions.
3.APPARATUS
3.1 A calibrated personal sampling pump whose
flow can be determined within 5 percent at the
recommended flow rate.
3.2 Charcoal tubes: Glass with both ends flame
sealed, 07 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 back-up section. A
plug of silanized 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.
B-22
3.7 Microliter syringes: 10-microliter (10-mL)

syringe, and other convenient sizes for making
standards, 1-mL syringe for sample injections.
3.8 Pipets: 1.0 mL delivery pipets
4. REAGENTS
4.1 Chromatographic quality carbon disulfide (CS2
): Most commercially available carbon disulfide
contains a trace of benzene which must be
removed. It can be removed with the following
procedure:
Heat under reflux for 2 to 3 hours, 500 mL of
carbon disulfide, 10 mL concentrated sulfuric acid,
and 5 drops of concentrated nitric acid. The
benzene is converted to nitrobenzene. The carbon
disulfide layer is removed, dried with anhydrous
sodium sulfate, and distilled. The recovered carbon
disulfide should be benzene free. (It has recently
been determined that benzene can also be removed
by passing the carbon disulfide through 13x
molecular sieve.)
4.2 Benzene, reagent grade.
4.3 p-Cymene, reagent grade, (internal standard).
4.4 Desorbing reagent: The desorbing reagent is
prepared by adding 0.05 mL of p-cymene per
milliliter of carbon sulfide. (The internal standard
offers a convenient means of correcting analytical
9/04
response for slight inconsistencies in the size of

sample injections. If the external standard technique
is preferred, the internal standard can be eliminated.)
5.3.8 Take necessary shipping and packing

precautions to minimize breakage of samples.
5.4 Analysis of samples.
4.5 Purified GC grade helium, hydrogen and air.

5. PROCEDURE
5.1 Cleaning of equipment: All glassware used for
the laboratory analysis should be properly cleaned
and free of organics which could interfere in the
analysis.
5.2 Calibration of personal pumps: Each pump
must be calibrated with a representative charcoal
tube in the line.
5.3 Collection and shipping of samples.
5.3.1 Immediately before sampling, break the ends
of the tube to provide an opening at least one-half
the internal diameter of the tube (2 mm).
5.3.2 The smaller section of the charcoal is used
as the backup and should be placed nearest the
sampling pump.
5.3.3 The charcoal tube should be placed in a
vertical position during sampling to minimize
channeling through the charcoal.
5.3.4 Air being sampled should not be passed
through any hose or tubing before entering the
charcoal tube.
5.4.1 Preparation of samples: In preparation for

analysis, each charcoal tube is scored with a file in
front of the first section of charcoal and broken
open. The glass wool is removed and discarded.
The charcoal in the first (larger) section is transferred
to a 2-ml vial. The separating section of foam is
removed and discarded; the second section is
transferred to another capped vial. These two
sections are analyzed separately.
5.4.2 Desorption of samples: Prior to analysis, 1.0
mL of desorbing solution is pipetted into each
sample container. The desorbing solution consists
of 0.05 L internal standard per mL of carbon
disulfide. The sample vials are capped as soon as
the solvent is added. Desorption should be done
for 30 minutes with occasional shaking.
5.4.3 GC conditions: Typical operating conditions
for the gas chromatograph are:
1. 30 mL/min (60 psig) helium carrier gas flow.
2. 30 mL/min (40 psig) hydrogen gas
flow to detector.
3. 240 mL/min (40 psig) air flow to detector.
4. 150 C injector temperature.
5. 250 C detector temperature.
6. 100 C column temperature.
5.4.4 Injection size: 1 mL.
5.3.5 A sample size of 10 liters is recommended.

Sample at a flow rate of approximately 0.2 liters per
minute. The flow rate should be known with an
accuracy of at least 5 percent.
5.3.6 The charcoal tubes should be capped with the
supplied plastic caps immediately after sampling.
5.3.7 Submit at least one blank tube (a charcoal
tube subjected to the same handling procedures,
without having any air drawn through it) with each
set of samples.
5.4.5 Measurement of area: The peak areas are

measured by an electronic integrator or some other
suitable form of area measurement.
5.4.6 An internal standard procedure is used: The
integrator is calibrated to report results in ppm for a
10 liter air sample after correction for desorption
efficiency.
5.5 Determination of desorption efficiency.
5.5.1 Importance of determination: The desorption
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B-23
5.5.1 Importance of determination: The desorption

efficiency of a particular compound can vary from
one laboratory to another and from one lot of
chemical to another. Thus, it is necessary to
determine, at least once, the percentage of the
specific compound that is removed in the desorption
process, provided the same batch of charcoal is used.
5.5.2 Procedure for determining desorption efficiency: The reference portion of the charcoal tube is
removed. To the remaining portion, amounts representing 0.5X, 1X, and 2X and (X represents target
concentration) based on a 10 L air sample are
injected into several tubes at each level. Dilutions
of benzene with carbon disulfide 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. Desorption efficiency is determined by dividing the amount of
benzene found by the amount spiked on the tube.
6. CALIBRATION AND STANDARDS
A series of standards varying in concentration over
the range of interest is prepared and analyzed
under the same GC conditions that will be used on
the samples. A calibration curve is prepared by
plotting concentration (_mg/mL) versus peak area.
7. CALCULATIONS
Benzene air concentration can be calculated from
the
following equation:
mg/m3 = (A)(B)/(C)(D)
Where:
A=mg/mL benzene, obtained from the
calibration curve
B = desorption volume (1 mL)
C= Liters of air sampled
D= desorption efficiency
The concentration in mg/m3 can be converted to
ppm (at 25 C and 760 mm) with following equation:
ppm = (mg/m3)(24.46)/(78.11)
Where: 24.46 = molar volume of an ideal gas
25 C and 760 mm
78.11 = molecular weight of benzene
B-24
8. BACKUP DATA
8.1 Detection limit -Air Samples.
The detection limit for the analytical procedure is
1.28 ng with a coefficient of variation of 0.023 at
this level. This would be equivalent to an air
concentration of 0.04 ppm for a 10 L air sample.
This amount provided a chromatographic peak that
could be identifiable in the presence of possible
interferences. The detection limit data were
obtained by making 1 mL injections of a 1.283
mg/mL standard.
Injection
Area
Count
655.4
617.5
662.0
X= 640.2
641.1
SD = 14.9
636.4
CV= 0.023
629.2.
8.2 Pooled coefficient of variation -Air Samples:

The pooled coefficient of variation for the analytical
procedure was determined by 1 mL replicate
injections of analytical standards. The standards
were 16.04, 32.08, and 64.16 mg/mL, which are
equivalent to 0.5, 1.0, and 2.0 ppm for a 10 L air
sample, respectively.
Area Counts
1.0 ppm 2.0 ppm
Injection
0.5 ppm
3996.5
8130.2
16481
4059.4
8235.6
16493
4052.0
8307.9
16535
4027.2
8263.2
16609
4046.8
8291.1
16552
4137.9
8288.8
16618
X=
4053.3
8254.0
16548.3
SD =
47.2
62.5
57.1
CV =
0.0116
0.0076
0.0034
CV =0.008
9/04
8.3 Storage data -Air Samples.

Samples were generated at 1.03 ppm benzene at
80% relative humidity, 22 C, and 643 mm. All
samples were taken for 50 minutes at 0.2 L/min. Six
samples were analyzed immediately and the rest of
the samples were divided into two groups by
fifteen samples each. One group was stored at
refrigerated temperature of -25 C, and the other
group was stored at ambient temperature (approximately 23 C). These samples were analyzed over a
period of fifteen days. The results are tabulated
below.
PERCENT RECOVERY
8.4 Desorption data.

Samples were prepared by injecting liquid benzene
onto the A section of charcoal tubes. Samples were
prepared that would be equivalent to 0.5, 1.0, and
2.0 ppm for a 10 L air sample.
PERCENT RECOVERY
Sample
0.5 ppm
1.0 ppm
2.0 ppm
99.4
98.8
99.5
99.5
98.7
99.7
99.2
98.6
99.8
99.4
99.1
100.0
99.2
99.0
99.7
Day Analyzed
Refrigerated
Ambient
99.8
99.1
99.9
97.4 98.7 98.9
97.4 98.7 98.9
X=
99.4
98.9
99.8
SD =
0.22
0.21
0.18
0.0022
0.0021
0.0018
97.1 100.6 100.9 97.1 100.6 100.9
95.8 96.4 95.4
95.4 96.6 96.9
CV =
93.9 93.7 92.4
92.4 94.3 94.1
X = 99.4
93.6 95.5 94.6
95.2 95.6 96.6
13
94.3 95.3 93.7
91.0 95.0 94.6
15
96.8 95.8 94.2
92.9 96.3 95.9
8.5 Carbon disulfide.

Carbon disulfide from a number of sources was
analyzed for benzene contamination. The results
are given in the following table. The benzene contaminant can be removed with the procedures given
in section 4.1.
mg
Benzene/
mL
ppm
equivalent
(for 10 L
air sample)
Aldrich Lot 83017
4.20
0.13
Baker Lot 720364
1.01
0.03
Baker Lot 822351
1.01
0.03
Malinkrodt Lot WEMP
1.74
0.05
Malinkrodt Lot WDSJ
5.65
0.18
Malinkrodt Lot WHGA
2.90
0.09
Treated CS2
Sample
9/04
B-25
(II) OSHA LABORATORY METHOD NO. 12

FOR BULK SAMPLES
ANALYTE: Benzene.
MATRIX: Bulk Samples.
PROCEDURE: Bulk Samples are analyzed
directly by high performance liquid
chromatography (HPLC).
DETECTION LIMITS: 0.01% by volume.
3.5 An electronic integrator or some other suitable

method of measuring peak areas.
3.6 Microliter syringes -10 mL syringe and other
convenient sizes for making standards. 10 mL
syringe for sample injections.
3.7 Volumetric flasks, 5 mL and other convenient
sizes for preparing standards and making dilutions.
1. PRINCIPLE OF THE METHOD

1.1 An aliquot of the bulk sample to be analyzed is
injected into a liquid chromatograph.
4. REAGENTS
4.1 Benzene, reagent grade.
1.2 The peak area for benzene is determined and

compared to areas obtained from standards.
4.2 HPLC grade water, methyl alcohol, and isopropyl alcohol.
2. ADVANTAGES AND DISADVANTAGES

OF THE METHOD
2.1 The analytical procedure is quick, sensitive, and
reproducible.
5. COLLECTION AND SHIPMENT OF SAMPLES

5.1 Samples should be transported in glass
containers with Teflon-lined caps.
2.2 Reanalysis of samples is possible.

2.3 Interferences can be circumvented by proper
selection of HPLC parameters.
2.4 Samples must be free of any particulates
that may clog the capillary tubing in the liquid
chromatograph. This may require distilling the
sample or clarifying with a clarification kit.
3. APPARATUS
3.1 Liquid chromatograph equipped with a UV
detector.
3.2 HPLC Column that will separate benzene
from other components in the bulk sample being
analyzed. The column used for validation studies
was a Waters uBondapack C18, 30 cm x 3.9 mm.
3.3 A clarification kit to remove any particulates in
the bulk if necessary.
5.2 Samples should not be put in the same

container used for air samples.
6. ANALYSIS OF SAMPLES
6.1 Sample preparation.
If necessary, the samples are distilled or clarified.
Samples are analyzed undiluted. If the benzene
concentration is out of the working range, suitable
dilutions are made with ispropyl alcohol.
6.2 HPLC conditions.
The typical operating conditions for the high
performance liquid chromatograph are:
1. Mobile phase -Methyl alcohol/water, 50/50
2. Analytical wavelength -254 nm
3. Injection size -10 mL
6.3 Measurement of peak area and calibration.
Peak areas are measured by an integrator or other
suitable means. The integrator is calibrated to
report results % in benzene by volume.
3.4 A micro-distillation apparatus to distill any

samples if necessary.
B-26
9/04
7. CALCULATIONS
Since the integrator is programmed to report results
in % benzene by volume in an undiluted sample,
the following equation is used:
% Benzene by Volume = A x B
Where: A = % by volume on report
B = Dilution Factor
(B = 1 for undiluted sample)
8. BACKUP DATA
8.1 Detection limit - Bulk Samples.
The detection limit for the analytical procedure
for bulk samples is 0.88 mg, with a coefficient of
variation of 0.019 at this level. This amount provided
a chromatographic peak that could be identifiable
in the presence of possible interferences. The
detection limit data were obtained by making 10
mL injections of a 0.10% by volume standard.
Injection
Area
Count
45386
44214
43822
X = 44040.1
44062
SD = 852.5
8.2 Pooled coefficient of variation -Bulk Samples.

The pooled coefficient of variation for analytical
procedure was determined by 50 mL replicate
injections of analytical standards. The standards
were 0.01, 0.02, 0.04, 0.10, 1.0, and 2.0% benzene
by volume.
AREA COUNT (PERCENT)

Injection No.
0.01
0.02
0.04
0.10
1.0
2.0
45386
84737
166097
448497
4395380
9339150
44241
84300
170832
441299
4590800
9484900
43822
83835
164160
443719
4593200
9557580
44062
84381
164445
444842
4642350
9677060
44006
83012
168398
442564
4646430
9766240
42724
81957
173002
443975
4646260
X=
44040.1
83703.6
167872
444149
4585767
9564986
SD =
852.5
1042.2
3589.8
2459.1
96839.3
166233
CV =
0.0194
0.0125
0.0213
0.0055
0.0211
0.0174
CV =
0.017
The following information is an excerpt from the Code of Federal Regulations (CFR) and is provided solely for information
purposes. A complete description of the OSHA Benzene Standard can be found in the CFR. In furnishing this information, Shell, its
affiliates and their representatives undertake no obligation to provide the recipient with access to any additional information or to
update this document.
9/04
B-27
APPENDIX C
Coast Guard Benzene Rule
References:
46 CFR Parts 30, 151, 153, and 197.
Federal Register, Vol. 56, No. 201, pages 52122 - 52152.
9/04
C-1
APPENDIX D
NIOSH Sampling and Analytical Procedure
for Benzene (Method 1501-Hydrocarbons, Aromatic)
METHOD:
1501, Issue 2
EVALUATION: Partial
ISSUE 1:
15 February 1984
ISSUE 2:
15 August 1994
SAMPLING
Sampler:
Solid Sorbent Tube

(coconut shell charcoal,
100 mg/50 mg)
Formula:
Table 1
Flow Rate,
Volume:
Table 3
MW:
Table 1
Shipment:
Routine
CAS:
Table 1
Sample
Stability:
Not determined
RTECS:
Table 1
Blanks:
2 to 10 field blanks per set
OSHA:
Table 2
Bulk Sample:
NIOSH:
Table 2
Desirable, 1 to 10 mL; ship

in separate containers from
samples
ACGIH:
Table 2
Properties:
Table 1
Range Studied: Table 3
Compounds:
(Synonyms
in Table 1)
benzene
cumene
a-methylstyrene
styrene
vinyltoluene
p-tert-butyltoluene
ethylbenzene
naphthalene
toluene
xylene
Bias:
Table 3
Overall
Precision
n( SrT):
Table 3
Accuracy:
Table 3
ACCURACY
NIOSH Manual of Analytical Methods (NMAM), Fourth Edition, 8/15/94.

9/04
D-1
MEASUREMENT
INTERFERENCES
Technique:
Gas Chromatography, FID
Analyte:
Hydrocarbons listed above
Desorption:
1 mL CS 2 ; stand 30 min
Injection Volume:
5 L
Temperature
Injection:
Detector:
Column:
225 C
225 C
See step 11
Carrier Gas:
N 2 or He, 25 mL/min
Column:
Glass, 3.0 m __2-mm, 10%

OV-275 on 100/120 mesh
Chromosorb W-AW or
equivalent (Table 4)
Use of the recommended column may help reduce

interference by alkanes. Under conditions of high
humidity, the breakthrough volumes may be
reduced by as much as 50%. Other volatile organic
solvents, e.g., alcohols, ketones, ethers,
and halogenated hydro-carbons, are possible
interferences. If interference is suspected, using a
less polar column or changing column temperature
may help reduce such interference.
OTHER METHODS
This method is based on and supercedes Methods
P&CAM 127, benzene, styrene, toluene and xylene
[2]; S311, benzene [4]; S22, p-tert-butyltoluene [3];
S23, cumene [3]; S29, ethylbenzene [3]; S26, amethylstyrene [3]; S292, naphthalene [4]; S30,
styrene [3]; S343, toluene [4]; S25, vinyltoluene [3];
S318, xylene [4].
REAGENTS
Calibration:
Analytes in CS2
Range and
Precision ( - Sr ):
Table 4
Estimated LOD:
0.001 to 0.01 mg per sample

with capillary column [1]
APPLICABILITY
This method is for peak, ceiling and TWA
determinations of aromatic hydrocarbons. It may
be used for simultaneous measurements, though
there is the possibility that interactions between
analytes may reduce the breakthrough volumes
and change desorption efficiencies.
1. Eluent: Carbon disulfide*, chromatographic

quality containing (optional) suitable internal
standard.
2. Analytes, reagent grade.*
3. Nitrogen or helium, purified.
4. Hydrogen, prepurified.
5. Air, filtered.
6. Naphthalene calibration stock solution,
0.40 g/mL in CS2.
* See SPECIAL PRECAUTIONS.
SPECIAL PRECAUTIONS
Carbon disulfide is toxic and extremely flammable
(flash point = -30 C); benzene is a suspect
carcinogen. Prepare samples and standards in a
well-ventilated hood.

D-2
9/04
EQUIPMENT
CALIBRATION AND QUALITY CONTROL
1. Sampler: glass tube, 7 cm long, 6-mm OD, 4-mm

ID, flame-sealed ends, containing two sections of
activated (600 C) coconut shell charcoal (front =
100 mg, back = 50 mg) separated by a 2-mm
urethane foam plug. A silylated glass wool plug
precedes the front section and a 3-mm urethane
foam plug follows the back section. Pressure
drop across the tube at 1 L /min airflow must
be less than 3.4 kPa. Tubes are commercially
available.
2. Personal sampling pumps, 0.01 to 1 L/min
(Table 3), with flexible connecting tubing.
3. Gas chromatograph, FID, integrator, and column
(page 1501-1).
4. Vials, glass, 1-mL, with PTFE-lined caps.
5. Pipet, 1-mL, and pipet bulb.
6. Syringes, 5-, 10-, 25- and 100-mL.
7. Volumetric flasks, 10-mL.
8. Calibrate daily with at least six working standards

over the appropriate range (ca. 0.01 to 10 mg
analyte per sample; see Table 4).
a. Add known amounts of analyte (calibration stock
solution for naphthalene) to eluent in 10-mL
volumetric flasks and dilute to the mark.
b. Analyze together with samples and blanks
(steps 11 through 13).
c. Prepare calibration graph (peak area of analyte
vs. mg analyte per sample).
9. Determine desorption efficiency (DE) at least
once for each batch of charcoal used for
sampling in the calibration range (step 8).
Prepare three tubes at each of five levels plus
three media blanks.
a. Remove and discard back sorbent section of
a media blank sampler.
b. Inject a known amount of analyte (calibration
stock solution for naphthalene) directly onto
front sorbent section with a microliter
syringe.
c. Cap the tube. Allow to stand overnight.
d. Desorb (steps 5 through 7) and analyze
together with working standards
(steps 11 through 13).
e. Prepare a graph of DE vs. mg analyte
recovered.
10. Analyze three quality control blind spikes and
three analyst spikes to insure that the
calibration graph and DE graph are in control.
SAMPLING
1. Calibrate each personal sampling pump with a
representative sampler in line.
2. Break the ends of the sampler immediately
before sampling. Attach sampler to personal
sampling pump with flexible tubing.
3. Sample at an accurately known flow rate
between 0.01 and 0.2 L/min (to 1 L /min for
naphthalene or styrene) for a total sample size as
shown in Table 3.
4. Cap the samplers with plastic (not rubber) caps
and pack securely for shipment.
SAMPLE PREPARATION
5. Place the front and back sorbent sections of the
sampler tube in separate vials. Discard the glass
wool and foam plugs.
6. Add 1.0 mL eluent to each vial. Attach crimp
cap to each vial immediately.
7. Allow to stand at least 30 min with occasional
agitation.

9/04
D-3
MEASUREMENT
11. Set gas chromatograph according to
manufacturers recommendations and to
conditions given on page 1501-1. Select
appropriate column temperature:
Note: Alternatively, column and
temperature may be taken from Table 4.
Substance
15. Calculate concentration, C, of analyte in the air

volume sampled, V (L):
(Wf +Wb- Bf - Bb) 103 , mg/m3.
C = ____________________________
V
Approximate Retention Time (min), at Indicated Column Temperature

50 C
100 C
150 C
Programmed b
benzene
2.5
2.5
toluene
4.3
1.1
4.2
xylene (para)
7.0
1.4
5.2
ethylbenzene
7.0
1.4
5.5
xylene (meta)
7.2
1.5
5.6
cumene
8.3
1.6
6.0
xylene (ortho)
10
1.9
6.5
styrene
16
2.6
7.6
a-methylstyrene
3.2
1.0
8.1
vinyltoluene (meta)
3.8
1.2
8.5
naphthalene
25
4.3
12
a Data not available for p-tert-butyltoluene and p-vinyltoluene.

b Temperature program: 50 C for 3 min, then 15 C / min to 200 C.
EVALUATION OF METHOD
12. Inject sample aliquot manually using solvent
flush technique or with autosampler.
Note: If peak area is above the linear
range of the working standards, dilute
with eluent, reanalyze and apply the
appropriate dilution factor in calculations.
13. Measure peak area.
CALCULATIONS
14. Determine the mass, mg (corrected for DE) of
analyte found in the sample front (Wf) and back
(Wb) sorbent sections, and in the average media
blank front (Bf) and back (Bb) sorbent sections.
Note: If Wb > Wf /10, report breakthrough and
possible sample loss.
Precisions and biases listed in Table 3 were

determined by analyzing generated atmospheres
containing one-half, one, and two times the
OSHA standard. Generated concentrations were
independently verified. Breakthrough capacities
were determined in dry air. Storage stability was
not assessed. Measurement precisions given in
Table 4 were determined by spiking sampling
media with amounts corresponding to one-half,
one, and two times the OSHA standard for nominal
air volumes. Desorption efficiencies for spiked
samplers containing only one compound exceeded
75%. Reference [9] provides more specific
information.

D-4
9/04
REFERENCES
[1] User check, UBTL, NIOSH Sequence #4121-S
(unpublished, December 7, 1983).
[2] NIOSH Manual of Analytical Methods, 2nd. ed.,
V. 1, P&CAM 127, U.S. Department of Health,
Education, and Welfare, Publ. (NIOSH) 77-157-A
(1977).
[3] Ibid, V. 2, S22, S23, S25, S26, S29, S30, U.S.
Department of Health, Education, and Welfare,
Publ. (NIOSH) 77-157-B (1977).
[4] Ibid, V. 3, S292, S311, S318, S343, U.S.
Department of Health, Education, and Welfare,
Publ. (NIOSH) 77-157-C (1977).
[5] R. D. Dreisbach. Physical Properties of
Chemical Compounds; Advances in Chemistry
Series, No. 15; American Chemical Society,
Washington (1955).
[6] Code of Federal Regulations; Title 29 (Labor),
Parts 1900 to 1910; U.S. Government Printing
Office, Washington (1989); 29 CFR 1910.1000.
[7] NIOSH Recommendations for Occupational
Safety and Health. U.S. Department of Health
and Human Services. DHHS (NIOSH)
Publication No. 92-100 (1992).
[8] 1992-1993 Threshold Limit Values for Chemical
Substances and Physical Agents and Biological
Exposure Indices, ACGIH, Cincinnati, OH (1992).
[9] Documentation of the NIOSH Validation Tests,
S22, S23, S25, S26, S29, S30, S292, S311, S318,
S343, U.S. Department of Health, Education,
and Welfare; Publ. (NIOSH) 77-185 (1977).
METHOD REVISED BY
R. Alan Lunsford, Ph.D., based on results of NIOSH
Contract CDC-99-74- 45.

9/04
D-5
TABLE 1. SYNONYMS, FORMULA, MOLECULAR WEIGHT, PROPERTIES (5).

Empirical
Formula
Molecular
Weight
Boiling
Point
(C)
benzene
CAS #71-43-2
RTECS CY1400000
C6 H6
78.11
80.1
95.2
12.7
0.879
p-tert-butyltoluene
CAS #98-51-1
1-tert-butyl-4-methylbenzene
RTECS XS8400000
C 11 H 16
148.25
192.8
0.7
0.09
0.861
cumene
CAS #98-82-8
isopropylbenzene
RTECS GR8575000
C 9 H 12
120.20
152.4
4.7
0.63
0.862
ethylbenzene
CAS #100-41-4
RTECS DA0700000
C 8 H 10
106.17
136.2
9.6
1.28
0.867
a-methylstyrene
CAS #98-83-9
isopropenylbenzene
(1-methylethenyl)-benzene
RTECS WL5075300
C 9 H 10
118.18
165.4
2.5
0.33
0.911
naphthalene
CAS #91-20-3
RTECS QJ0525000
C 10 H 8
128.18
80.2a
0.2
0.03
1.025
styrene
CAS #100-42-5
vinylbenzene
RTECS WL3675000
C8 H8
104.15
145.2
6.1
0.81
0.906
toluene
CAS #108-88-3
methylbenzene
RTECS XS5250000
C7 H8
92.14
110.6
28.4
3.79
0.867
vinyltoluene b
CAS #25013-15-4
methylstyrene
(p-vinyltoluene)
methylvinylbenzene
RTECS WL5075000
C 9 H 10
118.18
(meta)
(para)
167.7
171.6
172.8
1.6
1.9
1.8
0.22
0.26
0.24
0.898
0.911
0.911
(ortho)
169.8
1.8
0.24
0.904
xylene c
CAS #1330-20-7
dimethylbenzene (p-xylene)
RTECS ZE2100000
C 8 H 10
144.4
139.1
138.4
6.7
8.4
8.8
0.89
1.12
1.18
0.880
0.864
0.861
Name/Synonyms
a
b
c
(ortho)
(meta)
(para)
Vapor Pressure
@ 25 C
(mm Hg)
(kPa)
Density
@ 20 C
(g/mL)
106.17
Melting point.
Commercial mixture of meta and para isomers.
Mixture of isomers.

D-6
9/04
TABLE 2. PERMISSIBLE EXPOSURE LIMITS, PPM [6-8].

OSHA
TWA
TWA
NIOSH
C
benzene
0.1 c
p-tert-butyltoluene
10
10
50
(skin)
50
(skin)
ethylbenzene
100
100
125
100
125
4.34
a-methylstyrene
100
50
100
50
100
4.83
naphthalene
10
10 d
15
10
15
5.24
styrene
100
50
100
50**
100
(skin)
4.26
toluene
200
100
150
50
(skin)
vinyltoluene
100
100
xylene
100
100
Substance
cumene
a
b
c
ACGIH
STEL
TLV
10 f
3.19
6.06
50
(skin)
4.91
20
150
e
d
Maximum duration 10 min in 8 h.

Maximum duration 5 min in any 3 h.
Potential carcinogen.
e
f
STEL
mg/m 3
per ppm
3.77
50
100
4.83
100
150
4.34
Group III Pesticide.

Group I Pesticide.
Suspect carcinogen.
TABLE 3. SAMPLING FLOWRATE a, VOLUME, CAPACITY, RANGE, OVERALL BIAS AND PRECISION [3, 4, 9].
Breakthrough
Sampling
Flowrate Volume b (L)
(L/min) MIN MAX
Substance
Volume @
Range at
Concentration VOL-MIN
(L) ( mg/m 3) (mg/m 3)
Overall
Bias
Precision
(%)
( SrT)
Accuracy
( % )
benzene
<0.20
30
>45
149
42 -165
- 0.4
0.059
11.4
p-tert-butyltoluene
< 0.20
29
44
112
29-119
-10.3
0.071
20.7
cumene
< 0.20
30
>45
480
120 - 480
5.6
0.059
15.2
ethylbenzene
< 0.20
24
35
917
222- 884
-7.6
0.089
17.1
a-methylstyrene
< 0.20
30
>45
940
236 - 943
-7.6
0.061 d
16.9
naphthalene
< 1.0
100
200
>240
81
19 - 83
-2.6
0.055
11.5
styrene
< 1.0
14
21
1710
426 - 1710
-7.9
0.058 d
16.7
toluene
< 0.20
12
2294
548-2190
1.6
0.052
10.9
vinyltoluene
< 0.20
24
36
952
256 - 970
-7.0
0.061 d
16.3
xylene
< 0.20
23
35
870
218- 870
-1.2
0.060
2.2
Minimum recommended flow is 0.01 L/min.

V Min = minimum sample volume @ OSHA TWA;
V Max = maximum sample volume @ OSHA TWA.
c
10-min sample.
d
Corrected value, calculated from data in Reference [9].
f
g
Naphthalene shows poor desorption efficiency at low loading;

100-L minimum volume is recommended.
15-min sample.
5-min sample.

9/04
D-7
TABLE 4. MEASUREMENT RANGE, PRECISION AND CONDITIONS a [3, 4, 9].
Substance
Desorption
Volume
(mL)
Measurement
Range
Precision
(mg)
( Sr)
Carrier
Flow
(mL/min)
Column Parameters b
t
Length
(C)
(m)
Packing c
benzene
1.0
0.09 - 0.35
0.036
50
115
0.9
p-tert-butyltoluene
0.5
0.27- 1.09
0.021 d
50
115
3.0
cumene
0.5
0.86 - 3.46
0.010
50
99
3.0
ethylbenzene
0.5
2.17- 8.67
0.010
50
85
3.0
a-methylstyrene
0.5
0.69 - 3.57
0.011
50
115
3.0
naphthalene
1.0
4.96 -19.7
0.019
30
125
3.0
styrene
0.5
2.17- 8.49
0.013 d
50
109
3.0
toluene
1.0
1.13 - 4.51
0.011
50
155
0.9
vinyltoluene
0.5
2.41- 9.64
0.008
50
120
3.0
xylene
1.0
2.60 - 10.4
0.010
50
180
0.9
Injection volume, 5.0 mL; nitrogen carrier gas.

All columns stainless steel, 3.2-mm outside diameter.
c
A, 50/80 mesh Porapak P; B, 10% FFAP on 80/100 mesh Chromosorb W AW- DMCS;
C, 10% OV-101 on 100/120 mesh Supelcoport; D, 50/80 mesh Porapak Q.
d
Corrected value, calculated from data in [9].
b

D-8
9/04
NUMBER:
PRODUCT:
SUBJECT:
59
3M Organic Vapor Monitor #3500/3510/3520/3530
Sampling For Benzene
1. INTRODUCTION
This technical data bulletin contains information to be used when sampling atmospheres
for benzene using the 3M Organic Vapor Monitors #3500, #3510, #3520, or #3530.
Because benzene vapors are often found in combination with toluene and xylene vapors,
sampling rates for those compounds are also listed in this bulletin.
2. SAMPLING RATE
g/ppm-hr
cc/min
Benzene
6.78
35.5
Toluene
7.08
31.4
Xylene
7.09
27.3
3. CAPACITY (MAXIMUM)
Benzene
13 milligrams
4. MINIMUM QUANTITATION LEVEL

Benzene
2.0 micrograms
5. MINIMUM SENSITIVITY
Benzene
0.3 ppm-hr
3M Occupational Health and Safety Products Division

Building 220-3E-04, 3M Center
St. Paul, Minnesota 55144-1000.D-2
9/04
E-1
6. RECOMMENDED SAMPLING TIMES

The minimum sampling time for benzene is shown in Figure 1.
The minimum sampling time is defined as the time required to collect the minimum quantitation level,
2.0 micrograms.
Since the organic vapor monitors exhibit a large capacity for benzene, no maximum sampling time
is listed. The maximum concentration which could be sampled continuously for 8 hours is:
Benzene
240 ppm
FIGURE 1: MINIMUM SAMPLING TIME FOR BENZENE COLLECTED

ON #3500/3510/3520/3530 ORGANIC VAPOR MONITORS
BEN4.DAT JAK 3/86
E-2
9/04
7. OVERALL SYSTEM ACCURACY

Meets OSHA requirement of 25% at 95% confidence level.
8. ANALYTICAL PARAMETERS
A. Desorbing Solvent:
Carbon Disulfide
B. Recovery Coefficient:
It is recommended that the

analyst run a working curve
for each batch of analysis.
Typical values would be 1.00-1.05.
9. MONITORING FOR BENZENE, TOLUENE, AND XYLENE

Benzene, toluene, and xylene can all be collected on the same monitor simultaneously.
Since benzene has the lowest PEL, and the lowest sensitivity, sampling times should be
based upon benzene.
9/04
E-3
DECLARATION OF INSPECTION
PRIOR TO BULK CARGO TRANSFER
VESSELS:
RADIO NO.
DATE/
TIME ISSUED
TANKERMANS
SIGNATURE
DATE/
TIME RETURNED
DOCKMANS
SIGNATURE
TRANSFER
FACILITY:
LOCATION:
S-11065 (REV. 3-84)
The following list refers to requirements set forth in detail in 33 CFR 156.150 and 46 CFR 35.35-30
The spaces adjacent to items on the list are provided to indicate that the detailed requirement has been met.
INITIAL
FACILITY
VESSEL
1. Communication System/Language Fluency. (156.120 (q) (154.560) (154.785) (156.120V))

2. Warning Signs and red Warning Signal. (35.35-30)
3. Adequate Vessels Moorings. (156.120 (a))
4. Transfer System Alignment. (156.120) (d))
5. Transfer System; unused components (156.120 (e) (f) (154.120) (155.805))
6. Transfer System; fixed piping. (156.120 (g))
7. Overboard. Discharges/Sea Suction Lashed Valves. (156.120 (h))
8. Hoses or Loading Arms condition. (156.120) (i) (j) (154.500) (154.510))
9. Hoses; length and support. (156.120 (b) (c))
10. Connections. (156.120 (k) (p) (156.130))
11. Monitoring Devices. (156.120 (l) (154.525))
12. Discharge Containment System Capacity Maintained. (156.120 (m) (n) (p) (154.530) (155.310) (155.320) (154.545))
13. Scuppers or Drains. (156.120 (o) (155.310))
14. Emergency Shutdown. (156.120 (r) (154.550) (155.780))
15. Repair Work Authorization. (35.35-30)
16. Boiler and Galley Fires Safety. (35.35-30)
17. Fires or Open Flames. (35.35-30)
18. Lighting (sunset to sunrise). (156.120 (y) (z) (154.570) (155.790))
19. Safe Smoking Spaces. (35.35-30)
20. Spill and Emergency shutdown procedures. (156.120W)
21. Sufficient Personnel. (156.120 (s) (156.115 (u))
22. Pre-Transfer Conference - refer to the reverse side for the items to be discussed (156.120 (w))
23. Agreement to begin Transfer. (156.120 (x))
24. Persons-In-Charge in immediate vicinity/positioned to observe and supervise transfer (156.160)
25. Cargo Information Card - Reviewed and Issued (151.45-2 (e) (3)).
26. Inert Gas System - Operating Properly (32.53).
I do certify that I have personally inspected this facility or vessel with reference to the requirements set forth in section 35.35-30 and that opposite each
of them I have indicated by my initials that the regulations have been complied with.
SIGNATURE
SIGNATURE
FACILITY TITLE
VESSEL TITLE
TIME AND DATE
TIME AND DATE
I certify that I have read the above declaration and detailed requirements and all conditions remain satisfactory.
UNIT
SUBSEQUENT PERSON-IN-CHARGE
TITLE
VESSEL
FACILITY
VESSEL
FACILITY
VESSEL
TIME AND DATE COMPLETED
FACILITY
TIME AND DATE
156.120 Requirements for oil transfer.

No person may conduct an oil transfer operation
unless...
(a) the vessel's moorings are strong enough to hold
during all expected conditions of surge, current, and
weather and are long enough to allow adjustment for
changes in draft, drift, and tide during the transfer
operation:
(b) oil transfer hoses and loading arms are long enough
to allow the vessel to move to the limits of its moorings
without placing strain on the hose, loading arm, or oil
transfer piping system;
(c) each hose is supported to prevent kinking or other
damage to the hose and strain on its coupling;
(d) each part of the oil transfer system is aligned to allow
the flow of oil;
(e) each part of the oil transfer system not necessary for
the transfer operation is securely blanked or shut off;
(f) the end of each hose and loading arm that is not
connected for the transfer of oil is blanked off using
the closure devices required by 154.120 and 155.805 of
this chapter;
(g) the transfer system is attached to a fixed connection
on the vessel and the facility except that when a vessel is
receiving fuel, an automatic back pressure shutoff nozzle
may be used;
(h) each overboard discharge or sea suction valve that is
connected to the vessel's oil transfer or cargo tank system
is sealed or lashed in the closed position; except when used
to receive or discharge ballast in compliance with 33 CFR
157;
(i) each oil transfer hose has no unrepaired loose covers,
kinks, bulges, soft spots, or any other defect which would
permit the discharge of oil through the hose material and
no gauges, cuts, or slashes that penetrate the first layer of
hose reinforcement (reinforcement means the strength
members of the hose consisting of fabric, cord, and/or
metal);
(j) each hose or loading arm in use meets 54.500 and
154.510 of this chapter, respectively;
(k) each connection meets 156.130;
(l) any monitoring devices required by 154.525 of this
chapter are installed and operating properly;
(m) the discharge containment equipment required by
154.545 of this chapter is readily accessible or deployed as
applicable;
(n) the discharge containment required by 154.530,
155.310, and 155.320 of this chapter, as applicable, is in
place and periodically drained to provide the required
capacity;
(o) each drain and scupper is closed by the mechanical
means required by 156.310;
(p) all connections in the oil transfer system are leak free
except that a component in an oil transfer system, such as
the packing glands of a pump, may leak at a rate that does
not exceed the capacity of the discharge containment provided during the transfer operation;
(q) the communications required by 154.560 and
156.785 of this chapter are operable for the transfer
operation;
(r) the emergency means of shutdown required by
154.550 and 155.780 of this chapter, as applicable, is in
position and operable;
(s) there is a person in charge on the transferring vessel
or facility and the receiving vessel or facility except as
otherwise authorized under 156.115;
(t) each person in charge required by paragraph(s) of
this section...
(1) is at the site of the oil transfer operation and immediately available to the oil transfer personnel;
(2) has in his or her possession a copy of the facility
operations manual or vessel oil transfer procedures, as
appropriate; and
(3) conducts the transfer operation in accordance with
the facility operations manual or vessel oil transfer procedures, as appropriate;
(u) the personnel required, under the facility operations
manual and the vessel oil transfer procedures, to conduct
the oil transfer operation...
(1) are on duty; and
(2) conduct the transfer operation in accordance with the
facility operations manual or vessel oil transfer procedures,
as appropriate;
(v) at least one person is at the site of the oil transfer
operation who fluently speaks the language or languages
spoken by both persons in charge;
(w) the person in charge of oil transfer operations on the
transferring vessel or facility and the person in charge of all
transfer operations on the receiving vessel or facility have
held a conference, to ensure that each person in charge
understands the following details of the transfer operation...
(1) the identity of the product to be transferred;

(2) the sequence of transfer operations;
(3) the transfer rate;
(4) the name or title and location of each person participating in the transfer operation;
(5) details of the transferring and receiving systems;
(6) critical stages of the transfer operations;
(7) federal, state, and local rules that apply to the transfer
of oil;
(8) emergency procedures;
(9) discharge containment procedures;
(10) discharge reporting procedures;
(11) watch or shift arrangement;
(12) transfer shutdown procedures;
(x) the person in charge of oil transfer operations on the
transferring vessel or facility and the person in charge of oil
transfer operations on the receiving vessel or facility agree
to begin the transfer operation;
(y) between sunset and sunrise the lighting required by
154.570 and 155.790 of this chapter is provided; and
(z) for transfer operations between tank barges from
sunset to sunrise, lighting is provided as described in
155.790 of this chapter.
156.130 Connection
(a) Each person who makes a connection for oil transfer
operations shall...
(1) use suitable material in joints and couplings to ensure
a leak-free seal;
(2) use a bolt in at least every other hole, and in non case
less than four bolts, in each temporary bolted connection
that uses a flange that meets American National Standards
Institute (ANSI) standard flange requirements under
154.500(d)(2) of this chapter;
(3) use a bolt in each hole in each temporary bolted
connection that uses a flange other than one that meets
ANSI standards;
(4) use a bolt in each hole of each permanently connected flange;
(5) use bolts of the correct size in each bolted connection; and
(a) tighten each bolt and nut uniformly to distribute the
load and sufficiently to ensure a leak-free seal;
(b) a person who makes a connection for oil transfer
operations must not use any bolt that shows signs of strain
or is elongated or deteriorated.
(c) Except as provided in paragraph (d) of this section,
no person may use a connection for oil transfer operations
unless it is...
(1) a bolted or full threaded connection; or
(2) a quick-connect coupling acceptable to the
Commandant.
(d) No person may transfer oil to a vessel that has a fill
pipe for which containment cannot practically be provided
unless an automatic back pressure shutoff nozzle is used.
156.150 Declaration of Inspection.
(a) No person may transfer oil to or from a vessel unless
each person in charge, designated under 154.710 and
155.700 of this chapter, has filled out and signed the declaration of inspection form described in paragraph (c) of this
section.
(b) No person in charge may sign the declaration of inspection unless he or she has determined by inspection, and
indicated by initialling in the appropriate space on the declaration of inspection form, that the facility or vessel, as
appropriate, meets 156.120.
(c) The declaration of inspection may be in any form but
must contain at least...
(1) the name or other identification of the transferring
vessel or facility and the receiving vessel or facility;
(2) that address of the facility or location of the transfer
operation if not at a facility;
(3) the date the transfer operation is started;
(4) a list of the requirements in 156.120 with spaces on
the form following each requirement for the person in
charge of the vessel or facility to indicate by initialling that
the requirement is met for the transfer operation; and
(5) a space for the date, time of signing, signature, and
title of each person in charge during oil transfer operations
on the transferring vessel or facility and space for the date,
time of signing, signature, and title of each person in
charge during oil transfer operations on the receiving facility or vessel.
(d) The form for the declaration of inspection may incorporate the declaration-of-inspection requirements under
46 CFR 36.35-30.
(e) The vessel and facility persons in charge shall each
have a signed copy of the declaration of inspection available for inspection by the COTP during the oil transfer
operation.
(f) The operators for each vessel and facility engaged in

an oil transfer operation shall retain a signed copy of the
declaration of inspection on board the vessel or at the
facility for at least 1 month from the date of signature.
156.160 Supervision by person in charge.
(a) No person may connect or disconnect a hose, top off
a tank, or engage in any other critical procedures during an
oil transfer operation unless the person in charge, required
by 156.120(s), supervises that procedure.
(b) No person may start the flow of oil to or from a vessel
unless instructed to do so by either person in charge.
(c) No person may transfer oil to or from a vessel unless
each person in charge is in the immediate vicinity and
immediately available to the oil transfer personnel.
35.35-30 Declaration of Inspection for tankships
T/ALL.
After completing the inspection required by 35.35-20
and prior to giving his approval to start the cargo transfer
operation, the master or senior deck officer on duty shall fill
in the following Declaration of Inspection in duplicate. The
original of the Declaration of Inspection shall be kept
aboard for the information of authorized persons. The duplicate, where required, shall be handed to the terminal
superintendent or his representative, who shall on demand
be given the opportunity to satisfy himself that the condition of the vessel is as stated in the Declaration of
Inspection.
Declaration of Inspection Prior to Bulk Cargo
Transfer
Date____________________
$________________ Port of ________________________
I, ____________________, being the master or senior
deck officer in charge of the transfer of bulk flammable and
combustible cargo about to be undertaken, do certify that I
have personally inspected this vessel with reference to the
following requirements set forth in 35.35-20 and that
opposite each of them I have indicated that the regulations
have been complied with.
(1) Are warnings displayed as required?
(2) Is there any repair work in way of cargo spaces being
carried on for which permission has not been given?
(3) Have cargo connections been properly made and are
cargo valves properly set?
(4) Have all cargo connections for loading Grades A, B,
and C cargoes been made to vessel's pipelines?
(5) Are there any fires or open flames present on the deck
or in any compartment which is located on, facing, open
and adjacent to the main deck of the vessels on which the
cargo connections have been made?
(6) Has the shore terminal or other tank vessel concerned reported itself in readiness for transfer of cargo?
(7) Are sea valves connected to the cargo system closed?
(8) If Grades A, B, and C cargoes are to be loaded and
boiler fires are lighted, has an inspection been made to
determine that they may be operated with reasonable
safety?
(9) If Grades A, B, and C cargoes are to be loaded and
galley fires are lighted, has an inspection been made to
determine that they may be operated with reasonable
safety?
(10) If Grades A, B, and C cargoes are to be loaded, has
an inspection been made to determine whether smoking is
to be permitted?
(11) If smoking is to be permitted, have spaces been
designated for this purpose?
35.35-36 Duties of senior deck officer during transfer
operations TB/ALL
The senior deck officer on duty shall control the operations as follows:
(a) Supervise the operations of cargo system valves.
(b) Start transfer of cargo slowly.
(c) Observe cargo connections for leakage.
(d) Observe operating pressure on cargo system.
(e) Observe rate of loading for the purpose of avoiding
overflow of tanks.
S-12094 (R EV 3- 92)
Declaration Of Inspection - Addendum

Benzene
This addendum is to be read and acknowledged by the signature of all parties handling
benzene, or Hydrocarbon mixtures containing in excess of 0.5% benzene by volume.
BENZENE REGULATION - U.S.C.G. (10/17/91)

U.S. Coast Guard Regulation 46 CFR, Part 197 concerning benzene requires that the
licensed officer, certified tankerman or person in charge of a barge should insure that no
person on the barge is exposed to an airborne concentration of benzene in excess of:
(1) One part per million (1 ppm) as an eight-hour time weighted average.
(2) Five parts per million (5 ppm) as a time-weighted average over any fifteen-minute
period.
The USCG requires that the words: BENZENE. REGULATED AREA,
CANCER CAUSING AGENT, FLAMMABLE - NO SMOKING, AUTHORIZED PERSONNEL
ONLY, RESPIRATOR REQUIRED, be on the warning signs specified in 46 CFR, Part
197.535(c). The warning sign required for Benzene barges must be permanently affixed to
the barge.
IN CASE OF ACCIDENT
Spill or Leak
Shut off all ignition sources. Keep people away. Keep upwind.
Shut off leak if without risk. Wear self-contained breathing
apparatus. Use water spray to knock down vapor. Flush area
with water spray. Run-off to waterway creates fire hazard (floats
on water); notify fire, health and pollution control agencies.
Fire
On small fire use dry chemical or carbon dioxide. On large fire

use water spray or foam. Cool exposed tanks with water.
Exposure
Remove to fresh air. If not breathing apply artificial respiration,

oxygen. If breathing is difficult, administer oxygen. Call a
physician.
INITIAL PERSON-IN-CHARGE
DELI V ERIN G
FUNCTION
UNIT TITLE
UNIT
INITIAL PERSON-IN-CHARGE
TIME AND DATE
SUBSEQUENT PERSON-IN-CHARGE
RECEI VING
UNIT TITLE
TIME AND DATE
TITLE
DELIVERING
RECEIVING
DELIVERING
RECEIVING
DELIVERING
RECEIVING
I CERTIFY THAT I HAVE READ THE ABOVE

ADDENDUM AND DETAILED REQUIREMENTS AND
ALL CONDITIONS REMAIN SATISFACTORY
SIGNATURE
TIME AND DATE COMPLETED

Product Stewardship Manual: Version II - U.S.A., 2004

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P r o d u c t S t e w a rd s h i p M a n u a l

Version II U.S.A., 2004

SHELL PRODUCT STEWARDSHIP PROGRAM

SHELL BENZENE PRODUCT STEWARDSHIP

PURPOSE AND SCOPE

products life. Successful implementation of Product

BASE CHEMICALS PRODUCT STEWARDSHIP

ACC Product Stewardship Code

MANAGEMENT LEADERSHIP AND COMMITMENT

INFORMATION AND CHARACTERIZATION

10. Suppliers: Requires suppliers to provide

The expression Shell Chemicals refers to the

BENZENE PRODUCT STEWARDSHIP VERSION II U.S.A., 2004

CHEMICAL IDENTIFICATION, PRODUCTION, AND USE

HEALTH HAZARD INFORMATION

Benzene Health and Safety Standards . . . . . . . . . . . . . . . . . . . . . . . . . .

HANDLING AND STORAGE INFORMATION

FIRE SAFETY & SPILLS AND LEAKS

General Information on Benzene Transportation . . . . . . . . . . . . . . . . . . . . . . . . . . 7-1

Fire and Explosion Hazard

Personal Protective Equipment . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5-1

SARA Title III Toxics Release Inventory (TRI) Data . . . . . . . . . . . . . . . . . . . . . . . . 8-1

1.2 Benzene Manufacturing

Shell Product Name:

Chemical Abstract Service

Benzene is produced commercially by five processes:

ethylene co-product process. Some manufacturers,

aromatics, called raffinates, are taken off the top

FIGURE 1.1: SHELL SULFOLANE BENZENE EXTRACTION PROCESS

1.3 Benzene End Uses

Benzene is a major product of the petrochemical

MAJOR END USES OF BENZENE

This subsection briefly discusses the manufacturing

Styrene-butadiene block copolymers

FIGURE 1.3: MAJOR BENZENE END USES1

I.4 Chemical and Physical Properties

TABLE 1.1: CHEMICAL AND PHYSICAL PROPERTIES

Critical Compressibility Factor

<50pS/m @20 C/68 F

Explosive Limits in Air, Vol. %

Ideal Gas Heat of Formation

Liquid Heat Capacity, @ 70 F

Odor Threshold in Air4,5

Flash Point (closed cup)

Ideal Gas Heat Capacity, @ 70 F

1. Daubert, T.E., Danner, R.P., Sibul, H.M., and Stebbins, C.C.,

Log Pow = 1.95-2.13

Refractive Index nD, @ 77 F

Saturated Concentration in Air

99,000 ppm @ 20 C/68 F

Solubility of Benzene in Water,

Solubility of Water in Benzene,

1.52 psia @ 15 C/59 F

4.24 x 10-4 lb/sq ft

5.02 x 10-6 lb/sq ft

(Source: DIPPR Database1 unless otherwise indicated)

FIGURE 1.4: LIQUID DENSITY

FIGURE 1.5: VAPOR PRESSURE

FIGURE 1.6: HEAT OF VAPORIZATION

FIGURE 1.7: LIQUID HEAT CAPACITY

FIGURE 1.8: IDEAL GAS HEAT CAPACITY

FIGURE 1.9: LIQUID VISCOSITY

FIGURE 1.10: VAPOR VISCOSITY