benzene ps manual

Produc t S tew ardship Manua l

Version II–U.S.A., 2004

BENZENEPRODUCT 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 tohave an HSE performance we can be proud of, toearn 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 Shell’s Commitment to HSE and Policyare in Appendix A.

SHELL PRODUCT STEWARDSHIP PROGRAMShell Chemicals are committed to developing waysto assist our customers in reducing the potentialrisks of handling and using our products. Webelieve our customers value this commitment. It isconsistent with our goal to be a preferred supplierand a leading contributor to the safe use of prod-ucts in the petro-chemical industry.

SHELL BENZENE PRODUCT STEWARDSHIPThe Aromatics Business follows the general principles of Product Stewardship as embodied bythe American Chemistry Council (ACC) “ResponsibleCare®**” Product Stewardship Code of ManagementPractices and other responsible care programs incountries around the world.

PURPOSE AND SCOPEThe purpose of Product Stewardship is to makehealth, safety, and environmental protection anintegral part of designing, manufacturing, marketing,distributing, using, recycling, and ultimate disposingof products. This process covers all stages of a

product’s life. Successful implementation of ProductStewardship is a shared responsibility. Everyone involved with the product has the responsibility toaddress society’s interest in a healthful environmentand in products that can be used safely.

GOALSShell Chemicals wish to develop working relation-ships with its customers and suppliers to further thepurposes of product stewardship with the followinggoals:

• 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 effectivelywhen suppliers and customers work together.

BASE CHEMICALS PRODUCT STEWARDSHIPIt is vital for the entire industry to cooperate in this common goal of protecting our employees,communities, and the environment. For additionalinformation on material contained in this binder,and/or the Shell Benzene Product Stewardshipprocess, please contact your sales executive. Weencourage your response on the value of the information provided, and hope it will prove to be a useful resource for you.

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*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

ACC Product Stewardship Code of Management Practices

Shell Chemicals have always been committed to thehealth and safety of our employees, communities,customers, and the environment. When theChemical Manufacturers Association (now ACC)Responsible Care® initiative began in 1989, we notonly adopted it, we contributed significantly to itsdevelopment and made it an important part of ourculture. The principles of Responsible Care are atthe very core of our goal of being a preferredemployer, welcomed neighbor, and preferred supplier. Shell is a partner in the American ChemistryCouncil’s Responsible Care initiative, and is a fullparticipant in the ACC Responsible Care program.

The Shell Product Stewardship Program, basedon the ACC’s Product Stewardship ManagementPractices identified below, is our commitment toproduce and market products responsibly. Thiscommitment is the responsibility of each and every individual involved with our products – frominitial R&D to manufacturing, distribution, sale, andultimate disposal. These management practices areimbedded in the Responsible Care ManagementSystem.

MANAGEMENT LEADERSHIP AND COMMITMENT1. 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 toimplement and maintain product stewardship practices.

INFORMATION AND CHARACTERIZATION4. 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 MANAGEMENT6. 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 productsas 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 practicesfor 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.

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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 company’s 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 company’s independent judgment, improvement is not evident, the company should take further measures up to and including termination of product sale.

*americanchemistry.org

DisclaimerThe 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 thecompanies of the Royal Dutch/Shell Group engaged in the chemicals business. Each of the companiesthat make up the Royal Dutch/Shell Group of companies is an independent entitiy and has itsown seperate identity.

This web site may include links to external websites. These links are provided in order to help youfind relevant web sites, services and/or productsthat may be of interest to you quickly and easliy. It is your responsibility to decide whether any services and/or products available through any ofthese web sites are suitable for your purposes. ShellChemicals is not responsible for the owners oroperators of these web sites or for any goods orservices they supply or for the content of their websites, 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 inrelation to any of these (including any liabilityarising out of any claim that the content of anyexternal web site to which this web site includes alink infringes the intellectual property rights of anythird party).

http://www.shell.com/chemicals 9/04

CHEMICAL IDENTIFICATION, PRODUCTION, AND USE1.1 Product Identification . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1-1

1.2 Benzene Manufacturing Process Information . . . . . . . . . . . . . . . . . . . . . . . . . 1-1

1.3 Benzene End Uses . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1-3

General Information . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

Uses of Benzene . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

1.4 Chemical and Physical Properties of Benzene . . . . . . . . . . . . . . . . . . . . . . . . . 1-6

1.5 Benzene Product Quality . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1-13

1.6 Benzene Reactivities and Incompatibilities . . . . . . . . . . . . . . . . . . . . . . . . . . . 1-14

2. HEALTH HAZARD INFORMATION2.1 General Information . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2-1

2.2 Overview of Benzene Health Hazards . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2-1

2.3 Eye Contact . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2-2

2.4 Skin Contact . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2-2

2.5 Acute Inhalation Exposure . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2-2

2.6 Ingestion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2-3

2.7 Subchronic/Chronic Toxicity . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2-3

Carcinogenicity

Reproductive Toxicity

Developmental Toxicity

Genotoxicity

2.8 Epidemiology . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2-5

2.9 Medical Surveillance . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2-5

3. ECOTOXICITY/ECOLOGICAL FATE3.1 Ecotoxicity . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3-1

Aquatic Toxicity

Aquatic Properties

3.2 Ecological Fate . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3-1

Fate in Soil

Fate in Water

Fate in Air

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

TABLE OF CONTENTS

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Page

4. REGULATORY OVERVIEW4.1 Benzene Health and Safety Standards . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4-1

Occupational Safety and Health Administration (OSHA)

U.S. Coast Guard

4.2 Occupational Exposure Limits for Benzene . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4-2

General Information on Occupational Exposure Limits

Occupational Exposure Limits for Benzene

Biological Exposure Indices

4.3 Federal Environmental Regulatory Overview . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4-3

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)

4.4 Federal Regulatory Management for Prevention of Accidental Releases . . . . . . . . . . 4-6

OSHA - Process Safety Management of Highly Hazardous

Chemicals (29 CFR 1910.119)

EPA - Prevention of Accidental Releases of Hazardous Air Pollutants

4.5 State Right-to-Know Laws/Regulations . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4-7

State Right-to-Know Listings

California Safe Drinking Water and Toxics Enforcement

Act of 1986 (Proposition 65)

4.6 Food and Drug Administration (FDA) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4-8

4.7 Consumer Product Safety Commission (CPSC) . . . . . . . . . . . . . . . . . . . . . . . . . . . 4-8

4.8 International Regulations . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4-9

Canada

Foreign Chemical Inventories

4.9 Hazard Ratings for Benzene . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4-9

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

HANDLING AND STORAGE INFORMATION5.1 Personal Protective Equipment . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5-1

Respiratory Protection

Chemical Protective Clothing

Eye and Face Protection

5.2 Exposure Monitoring . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5-3

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

6. FIRE SAFETY & SPILLS AND LEAKS6.1 Fire and Explosion Hazard . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 6-1

6.2 Fire Prevention . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 6-3

6.3 Fire Fighting . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 6-3

6.4 Spills and Leaks . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 6-4

7. TRANSPORTATION7.1 General Information on Benzene Transportation . . . . . . . . . . . . . . . . . . . . . . . . . . 7-1

Barge Shipments

Cleaning of Equipment

7.2 Emergency Response . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 7-2

7.3 Transport Classifications for Benzene . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 7-3

8. POLLUTION PREVENTION8.1 SARA Title III Toxics Release Inventory (TRI) Data . . . . . . . . . . . . . . . . . . . . . . . . 8-1

8.2 Emission Reduction Measures . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 8-2

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APPENDIX AShell’s Commitment to HSE and Policy . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . A-1

APPENDIX BOSHA Benzene Standard (29 CFR 1910.1028), Including

its Appendices A through D . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . B-1

APPENDIX CMarine Occupational Safety and Health Standard for Benzene . . . . . . . . . . . . . . . . . . . . . C-1

APPENDIX DNIOSH Sampling and Analytical Procedure for Benzene

(Method 1501–Hydrocarbons, Aromatic) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . D-1

APPENDIX E3M TECH DATA Bulletin Number 59 – Sampling for Benzene . . . . . . . . . . . . . . . . . . . . . E-1

APPENDIX FShell Declaration of Inspection and Benzene Addendum . . . . . . . . . . . . . . . . . . . . . . . . F-1

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1. CHEMICAL IDENTIFICATION,PRODUCTION, AND USE

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1.1 Product Identification

Shell Product Name: Benzene

Chemical Name: Benzene

Chemical Family: Aromatic Hydrocarbon

Chemical Abstract ServiceRegistry Number: 71-43-2

Chemical Formula: C6 H6

Chemical Structure:

1.2 Benzene ManufacturingProcess Information

Benzene is produced commercially by five processes:destructive distillation of coal (by-product of steelmill coking process); catalytic reforming of petroleum-based naphtha; recovery from pyrolysis gasoline(pygas), a co-product stream from the steam crackingprocess used to manufacture ethylene (the ethyleneco-product process); hydrodealkylation of toluene(HDA process); and the toluene disproportionationprocess (TDP).

The first three processes involve the productionof benzene from a C6 hydrocarbon stream bysolvent extraction. In the latter two processes, thebenzene product is separated from the reactantsand co-products by distillation.

Shell chemicals companies currently producebenzene by the catalytic reforming of naphtha, andthe ethylene co-product process. In both processes,the benzene-rich streams are processed to removethe light ends (C5 and lighter) in a stabilizercolumn, and heavy ends (C7 and heavier) in adebenzenizer column. After processing, the C6

fraction consists of a small amount of light ends anda C6 concentrate stream. The benzene concentrationof this stream varies between the two processes.Depending on feed quality and severity of the catalytic reformer, the benzene concentration of theC6 concentrate from the naphtha process is about15% to 30% volume. Benzene concentrate from the ethylene co-product process has a benzeneconcentration of 70% to 75% volume. The remainderof the components in the C6 concentrate streamsare called raffinates. These raffinates are highlyparaffinic if they are from catalytic reforming orhave some naphthenic components, if from the



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FIGURE 1.1: SHELL SULFOLANE BENZENE EXTRACTION PROCESS

ethylene co-product process. Some manufacturers,particularly those using reformate as feedstock,extract toluene and xylene in addition to benzenefrom a C6 through C8 mixture, and separate thethree aromatics by distillation. Shell Chemicals companies use sulfolane (Figure 1.2) as the extraction solvent.

Figure 1.1 provides an illustrative flow schemeof the Shell Sulfolane Benzene Extraction Process.The aromatic rich stream (C6 fraction) is fed to aliquid-liquid contactor in the extraction process. Inthe contactor, essentially all the aromatics in thefeed 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 maybe used, including tetraethylene glycol and N-methylpyrrolidone.

The fat solvent picks up some light paraffinsthat must be removed to meet the benzene specification, which is accomplished by taking the paraffins over-head in the paraffin strippingcolumn. The paraffins are returned to the extractioncontactor and eventually leave the process with the raffinate. The combination of extraction andstripping provides a very sharp separation between

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aromatics and non-aromatics. The paraffin-freemixture goes to the aromatics stripper columnwhere stripping steam, heat, and vacuum are usedto separate the feed into aromatics and leansolvent. The lean solvent is recycled back to theextraction contactor.

In the units that process C6 concentrate fromreformate, some olefins are extracted with thebenzene. In these units, there are clay treatersbetween the aromatics stripper column and thebenzene fractionator that dimerize any olefins thatmay be present. The aromatics stripper tops, afterclay treating, enter the benzene fractionator wherebenzene is distilled from any toluene, xylene, orheavier bottoms. The dimerized olefins are rejectedout of the bottoms of the benzene fractionator andare circulated back to feed preparation columnsupstream of the extraction section where they areremoved.

The raffinate stream exiting the process iswashed with water for recovery of the sulfolane.The recovered solvent is returned to the extractionsection.

1.3 Benzene End Uses

GENERAL INFORMATIONBenzene is a major product of the petrochemicalindustry. It is considered to be the most importantand versatile aromatic compound. As illustrated inSection 1.1 Product Identification, the chemicalstructure of benzene consists of six (6) carbonatoms arranged in a hexagonal ring to each ofwhich a hydrogen atom is attached (C6 H6 ). Thereare three double bonds in the benzene ring, andthis unsaturation greatly contributes to its chemicalreactivity. As a result, it is a very useful buildingblock in the synthesis of other chemicals.

Base chemicals such as benzene are convertedinto intermediate chemical products which are inturn converted to other chemicals, plastics, resins,elastomers, fibers, or surfactants. Primary derivativesof benzene that have large volume commercial useare ethylbenzene, cumene, cyclohexane, andnitrobenzene. Hundreds of benzene derivatives areformed by the replacement of one or more of itshydrogen atoms with other elements, groups, orside chains. Only those derivatives having significantindustrial or commercial value are discussed here.

MAJOR END USES OF BENZENEThis subsection briefly discusses the manufacturingprocesses used to convert benzene into variousdown-stream products. At the conclusion of thissubsection, Figure 1.3 provides an overview of themajor benzene derivatives and the final consumerproducts that are made from them.

Ethylbenzene/Styrene: Nearly all ethylbenzenein the United States is formed by the alkylation ofbenzene with ethylene. All but minor quantities ofthe ethylbenzene produced are dehydrogenated tomake styrene. Styrene is the largest derivative ofbenzene. It is used as a chemical intermediate in awide 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)

FIGURE 1.2: MOLECULAR STRUCTURE OF SULFOLANE

• Styrene-butadiene block copolymers (SBS, SEBS)

• Styrene-maleic anhydride copolymer resins• Methyl methacrylate-butadiene-styrene

(MMBS) resinsCumene/Phenol/Acetone: Benzene is alkylated

with propylene to form cumene (isopropylbenzene).The cumene is then oxidized to form cumenehydroperoxide which is split into phenol andacetone.

Phenol is an intermediate in the manufacture of phenol-formaldehyde resins, bisphenol A, cyclohexanone, chlorophenols, caprolactam, andsalicylic acid.

Acetone is an important solvent and chemicalintermediate. A key acetone derivative is methylmethacrylate, a monomer used in the manufactureof acrylic resins.

Cyclohexane: Cyclohexane is obtained either byextraction from hydrocarbon streams or the catalytichydrogenation of benzene. Cyclohexane is used asa solvent and is also a chemical intermediate forcaprolactam and adipic acid, two chemicals used inthe manufacture of nylon fibers.

Caprolactam is produced by the Beckmanrearrangement of cyclohexanone oxime. Adipic acid is obtained by a process which involves theoxidation of cyclohexane.

Nitrobenzene/Aniline: Nitrobenzene is producedby the nitration of benzene. Aniline is formed viathe reduction of nitrobenzene. A second methodused to produce aniline is by the ammonolysis ofphenol. Aniline is used as a chemical intermediatein the production of polymeric isocyanates andacetanilide.

Other End Uses: Benzene is also used as achemical intermediate in many processes includingdetergent alkylates, chlorobenzene, maleic anhydride, surfactants, and dyes.

In summary, benzene is an extremely versatileand significant industrial chemical. Figure 1.3 provides an overview of the major uses of benzene.

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FIGURE 1.3: MAJOR BENZENE END USES1

1. The types of products identified are intended to be illustrative examples rather than an exhaustive listing.

I.4 Chemical and Physical Properties of Benzene

Benzene is a clear, colorless liquid with a characteristic aromatic hydrocarbon odor. This odor is distinctive and sweet. Benzene is extremelyflammable. Data pertaining to its chemical andphysical properties are presented in Table 1.1.Additional data concerning the physical propertiesof benzene and their temperature dependence canbe found in Figures 1.4-1.15 (Source DIPPR ®

Database1 and Shaw3 for Figure 1.14).

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TABLE 1.1: CHEMICAL AND PHYSICAL PROPERTIESOF BENZENE

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. (Source: DIPPR® Database1 unless otherwise indicated)

Property 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 0.271

Critical Pressure 710.4 psia

Critical Temperature 552.2 °F

Critical Volume 0.053 ft3/lb

Density (liquid) 54.74 lb/ft3 @ 70 °F885 Kg/m3 @ 15 °C/59 °F

Electrical Conductivity <50pS/m @20 °C/68 °F

Explosive Limits in Air, Vol. %Lower 1.4Upper 7.1

Flash Point (closed cup) -11 °C/12 °F

Heat of Vaporization, @ 70 °F 187.8 BTU/lb

Ideal Gas Heat Capacity, @ 70 °F 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

Odor Threshold in Air4,5 2.7 - 12 ppm

Partition Coefficient n-Octanol/Water2 Log Pow = 1.95-2.13

Refractive Index nD, @ 77 °F 1.4979

Relative Vapor Density (Air=1)2 2.77

Saturated Concentration in Air2 99,000 ppm @ 20 °C/68 °F150,000 ppm @ 29 °C/85 °F

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

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FIGURE 1.4: LIQUID DENSITY

FIGURE 1.5: VAPOR PRESSURE

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FIGURE 1.6: HEAT OF VAPORIZATION

FIGURE 1.7: LIQUID HEAT CAPACITY

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FIGURE 1.8: IDEAL GAS HEAT CAPACITY

FIGURE 1.9: LIQUID VISCOSITY

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FIGURE 1.10: VAPOR VISCOSITY

FIGURE 1.11: LIQUID THERMAL CONDUCTIVITY

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FIGURE 1.12: VAPOR THERMAL CONDUCTIVITY

FIGURE 1.13: SURFACE TENSION

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FIGURE 1.14: SOLUBILITY OF WATER IN BENZENE

FIGURE 1.15: SECOND VIRIAL COEFFICIENT

1.5 Benzene Product Quality

Shell Chemicals* product quality objective is tosupply customers with benzene that meets theircurrent and future needs for purity, specific impurities, and parameter consistency.

Table 1.2 shows a typical industry specificationfor benzene. In some cases, individual customerspecification limits may differ from those given inthe table.

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TABLE 1.2: TYPICAL INDUSTRY SPECIFICATIONFOR BENZENE

ASTM Test Property Specification Method

Benzene, Min. Wt.% 99.90 D4492

Sulfur, Max., ppmw 1 D4045

Thiophene, Max., ppmw 0.6 D4735

Toluene,Max., ppmw 300 D2360

Nonaromatic Hydrocarbons,Max., ppmw 500 D2360

Acid Wash Color, Max. 1 D848

Acidity None detected D847

Copper Corrosion Pass (1A or 1B) D849

Appearance Clear, no free water or

suspended matter Visual

Color, Max., Pt-Co Scale 20 D1209

Rel. Density15.56/15.56 °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

Sulfur Compounds Free of H2S and SO2 D853

1.6Benzene Reactivities and Incompatibilities

A literature search was conducted to capture thevarious chemical reactivities and incompatibilitiesthat have been reported for benzene. Bretherick’sHandbook of Reactive Chemical Hazards, ThirdEdition, and the National Fire Protection

Association’s Fire Protection Guide on HazardousMaterials, 9th edition, 1986, are the primary sourcesfor the information listed in Table 1.3. Benzene alsopresents a moderate explosion hazard if heated orexposed to flame.

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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 Form a sensitive, explosive mixture.

Nitric Acid Form a sensitive, explosive mixture.

Liquid Oxygen Form a sensitive, explosive mixture.

Ozone Form a sensitive, explosive mixture.

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 Form a vigorous or incandescent reaction.

Bromine Trifluoride Form a vigorous or incandescent reaction.

Oxidizing Materials (such as chlorine,chlorine trifluoride, potassium peroxide) React vigorously and/or explosively.

Perchlorates React vigorously and/or explosively.

Sulfuric Acid + Permanganates React vigorously and/or explosively.

Silver Perchlorate + Acetic Acid React vigorously and/or explosively.

TABLE 1.3: CHEMICAL REACTIVITIES AND INCOMPATIBILITIESREPORTED FOR BENZENE

2.1 MSDS Provides Health Information

Health hazard information is provided to customerson the Material Safety Data Sheets (MSDS) that aresent to customers. The MSDS is in the appropriatelanguage for the country and in compliance withthe country’s 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.

2.2 Overview of Benzene Health Hazards

Benzene can affect the body by various routes ofexposure. These routes include direct liquidcontact, inhalation of vapors, absorption throughthe skin, and ingestion. There can be immediate(acute) as well as delayed (chronic) effects associatedwith benzene exposure. These effects are describedbriefly in this subsection with further detail providedin subsequent sections. Liquid benzene is irritatingto the eyes and skin. Exposure to high airborneconcentrations of benzene may cause irritation ofthe eyes, nose, throat, and respiratory tract. It mayalso 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 causechemical pneumonitis, which can be fatal.Prolonged and repeated exposure to high concentrations of benzene may cause serious injury to blood-forming organs and is associatedwith anemia (depletion of blood cells) and is linked to the later development of acute myelogenous leukemia (AML).

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2. HEALTH HAZARDINFORMATION



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TABLE 2.1: HUMAN HEALTH EFFECTSEXPERIENCED AT VARIOUS BENZENE EXPOSURES1

ExposureConcentration Time Health Effects Noted

(ppm) (min.)

50-150 300 Headache and fatigue

500-3,000 60 Headache andincreased 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, Patty’sIndustrial Hygiene and Toxicology, Vol. 2B, 4th ed., JohnWiley & Sons, Inc., New York, 1994, pp. 1308 - 1309.

2.3 Eye Contact

Eye contact with liquid benzene or its vapors canresult in irritation. Splash contact may cause a moderate burning sensation, with slight reversiblecorneal damage. If present in high concentrations,vapors may cause temporary irritation of eyes orrespiratory 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.

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 secondaryinfection.

Benzene can be absorbed through the skin,though generally at a much lower rate than throughthe mucous membranes of the respiratory system.In the case of abraded skin, absorption may bemore rapid. Also, benzene may be more readilyabsorbed if it is present in a mixture or as a contaminant in solvents that are readily absorbed.No signs of acute intoxication due to liquidbenzene absorption have been reported. In animal studies, insufficient quantities of benzene were absorbed through the skin to cause toxicity.

First Aid: Remove contaminated clothing andshoes. Immediately flush skin with water for 15minutes. Follow by washing with soap and water. If irritation occurs, get medical attention. Do notreuse clothing until cleaned.

2.5 Acute Inhalation Exposure

Generally, inhalation is the most significant route ofexposure because of benzene’s high volatility. Themajor toxic effect from the inhalation of concentratedbenzene vapors is on the central nervous system(CNS). Early to moderate CNS depression may beevidenced by giddiness, headache, dizziness, andnausea; in extreme cases, unconsciousness, respiratorydepression, and death may occur. High vapor concentrations may also cause irritation to themucous membranes of the nose and respiratory tract.

The severity of effects has been noted to escalateas the vapor concentration increases. Table 2.1 provides an overview of the types of health effectsexperienced by humans for various benzene exposures.

While there is no evidence that exposure toindustrially 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 cardiacsensitization. Such sensitization may cause fatalchanges in heart rhythms. This latter effect wasshown to be enhanced by hypoxia (insufficientoxygen) 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.

2.6 Ingestion

The main hazard in the unlikely event of benzeneingestion is aspiration into the lungs. This may possibly result in chemical pneumonitis, which can be fatal.

Ingestion of benzene can also affect the centralnervous system (CNS) as benzene is a neuroconvul-sant. It may produce stimulation characterized bytremors, convulsions, and visual disturbances. Earlyto moderate CNS depression may be evidenced bygiddiness, headache, dizziness, and nausea; inextreme 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 reportedto cause signs of staggering gait, vomiting, sleepiness,shallow rapid pulse, loss of consciousness, and laterdelirium, with subsequent chemical pneumonitis,collapse due to initial stimulation, then abrupt CNSdepression.

First Aid: Do not induce vomiting. If vomitingoccurs spontaneously, keep head below hips toprevent aspiration of liquid into the lungs. Getmedical attention.

Note to Physician: If benzene has been swallowed and vomited, there is a potential forchemical pneumonitis. Consider gastric lavage with protected airway, administration of activatedcharcoal.

2.7 Subchronic/Chronic Toxicity

CARCINOGENICITYBenzene has been classified as a known humancarcinogen. Prolonged and repeated exposure tohigh concentrations of benzene may cause seriousinjury to blood-forming organs and is associatedwith anemia (depletion of blood cells) and is linkedto the later development of acute myelogenousleukemia (AML). (See Section 2.8 Epidemiology foradditional information on the association betweenAML and occupational exposure to benzene.) Thereis not conclusive evidence linking benzene exposureand other forms of human leukemia. Damage tothe blood-forming organs may be evidenced byeasy fatigability and pallor (red blood cell effect),decreased resistance to infection (white blood celleffect), 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 forbenzene leukemogenesis. In rats and mice, benzene causes solid tumors in epithelial tissuessuch as Zymbal’s gland and the mammary glands.Studies of exposed humans have not revealed anyconsistent increase in tumors of any organ or tissueother than AML. Table 2.2 lists the carcinogenicityclassifications for benzene by various organizations.

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REPRODUCTIVE TOXICITY Benzene does not appear to be a potent reproductive toxin in experimental animals, basedon available toxicity data. There is limited evidenceof ovarian and testicular toxicity in mice, but notrats, exposed to benzene vapor at 300 ppm for 13weeks. One study has shown impaired fertility infemale rats exposed to 210 ppm benzene for 10-15days prior to mating, but a more recent study inrats exposed at up to 300 ppm pre-mating throughgestation and lactation showed no effects on fertility,reproduction or lactation. Benzene has not beenshown to have an effect on human reproduction.

DEVELOPMENTAL TOXICITY Numerous studies on experimental animals havefailed to detect teratogenic effects (birth defects)even at doses of benzene toxic to the femaleanimals. There is some evidence of fetotoxicity but no malformations in mice and rabbits exposedto 500 ppm and higher concentrations of benzenevapor during gestation.

Fetotoxic effects occurred only in the presenceof maternal toxicity. There is no evidence ofadverse developmental effects in humans.

GENOTOXICITYBenzene has been shown to be non-mutagenic orweakly mutagenic in a variety of in vitro (test tube)systems. It has, however, been found to cause othertypes of chromosome damage (micronuclei, chromosome breakage, non-dysjunctional events) inboth laboratory animals and workers exposed tohigh 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, formingdetectable complexes (adducts). There is limitedevidence 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.

TABLE 2.2: CARCINOGENICITYCLASSIFICATIONS OF BENZENE

Organization Carcinogenicity Classification

National ToxicologyProgram (NTP) Known carcinogen

International Agencyfor Research on Group 1: HumanCancer (IARC) carcinogen

U.S. Environmental Protection Agency (EPA) - Integrated Risk Group A: HumanInformation System (IRIS) carcinogen

National Institute forOccupational Safety & Potential occupationalHealth (NIOSH) carcinogen

American Conference of Governmental Industrial Group A1: Confirmed Hygienists (ACGIH) human carcinogen

Occupational Safety & Health Administration(OSHA) Cancar hazard

European Commission(EC) Carcinogen category 1

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2.8 Epidemiology

Statistically significant associations between acutemyelogenous leukemia and occupational exposureto benzene have been shown in a number of epidemiological studies. The study types in whichthis relationship has been observed include bothcohort and case-control.

Timing, extent, and intensity of exposure areimportant in predicting benzene’s hematotoxic andleukemogenic responses. According to theAmerican Petroleum Institute, increased risk ofleukemia has not been observed among petroleumworkers whose exposure was below the originalOSHA PEL of 10 ppm. The current level is 1 ppm.The American Petroleum Institute also reports thatincreased risk of leukemia has only been observedamong those who at some time experienced exposure to benzene concentrations in excess of 20 to 60 ppm (regardless of cumulative exposure).

2.9 Medical Surveillance

OSHA’s Benzene Standard in 29 CFR Part1910.1028(i) specifically requires that a MedicalSurveillance Program be made available foremployees who meet one or more of the specifiedexposure categories. The medical surveillancesection in the OSHA standard details what must beincluded as a minimum in the initial, periodic, andemergency medical examinations. Additionalmedical 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.

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3.1 Ecotoxicity

AQUATIC TOXICITYBenzene rapidly evaporates from open water. Thedata presented here are those of flow-through orclosed static tests. The source for this information is the unpublished PSE Dossier for Benzene prepared by Shell International PetroleumMaatschappij, B.V. (1994).

AQUATIC PROPERTIESBenzene is not expected to bioconcentrate inaquatic organisms. It is also considered to bereadily biodegradable, and will exist predominantlyin the vapor phase if released to the atmosphere.Table 3.1 provides further details on this data.

3.2 Ecological Fate

FATE IN SOILBenzene released to soil will be subject to rapidvolatilization near the surface. The portion thatdoes not evaporate will be highly mobile in soiland may leach to ground water. Thus, it is notexpected to significantly adsorb to sediment.Benzene may be subject to biodegradation inshallow, aerobic ground waters, but probably notunder anaerobic conditions.

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3. ECOTOXICITY/ECOLOGICALFATE

Fish(Classified as toxic since 1< LC50 < 10)

Freshwater: 96 hour LC50

Oncorhynchus mykiss 5 mg/l

Marine: 96 hour LC50 Morone saxatilis 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

Algae(Classified as slightly toxic since 10 < EC50 < 100)

Freshwater: 72 hour EC50 Selenastrum

capricornutum 29 mg/l

Marine: 72 hour EC50 Skeletonemacostatrum 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.




TABLE 3.1: ENVIRONMENTAL FATE PROPERTIES OF BENZENE

Property Value Comments

Bioconcentration

Octanol Water Partition Coefficient 2.13 Bioconcentration is the increase in tissue concentration(log Pow) when the rate of intake is > rate of excretion and

metabolism. BCF values < 100 and log Pows < 3.5 Bioconcentration Factor (BCF) 4.4 indicate that benzene is not expected to

bioconcentrate in aquatic organisms

Biodegradation

Calc. Theoretical Oxygen 3.08 gO2/g Biodegradation is a measure of the ability of a Demand (ThOD) substance to break down or decompose rapidly under

natural conditions and processes. Benzene is readily Closed Bottle Biological biodegradable, meeting the 10 day window criterion.

Oxygen Demand (BOD) at 20 °C 71% ThOD

Distribution (predicted)

In Air 99.3% Benzene will exist predominantly in the vapor phase In Water 0.7% if it is released to the atmosphere. It will evaporate In Soil 0% from both soil and water.

Persistence

Evaporation Half-Life from 0.15 day Both of these values are calculated/predicted.Model River

Persistence in Total Environment (half-life) One week

FATE IN WATERBenzene will volatilize rapidly when it is releasedinto water. The estimated half-life for volatilizationof benzene from a model river is 0.15 days. It is notexpected to appreciably adsorb to sediment, nor isit susceptible to hydrolysis. According to Europeancriteria, it is classified as "readily biodegradable."

FATE IN AIRBenzene released to the atmosphere will exist predominantly in the vapor phase. Gas-phasebenzene is not subject to direct photolysis, thoughit will react, i.e., be degraded, with photochemicallyproduced hydroxyl radicals. In polluted atmospheresthat contain nitrogen oxides or sulfur dioxides, the reaction time is accelerated. Products of photooxidation include phenol, nitrophenols, nitrobenzene,formic acid, and peroxyacetyl nitrate. Although itswater solubility is limited, benzene is also removedfrom the atmosphere via rain.

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4. REGULATORY OVERVIEW

The intent of this section is to provide an overviewof the U.S. state, federal, and international health,safety, and environmental regulations which applyto benzene. A brief summary/explanation of eachregulation is provided prior to addressing the regulation as it specifically applies to benzene.

Please note that while this is a fairly encom-passing overview, it is NOT an exhaustive summaryof all health, safety, and environmental regulationswhich are applicable to benzene. Similarly, the brief overviews of the regulations at the beginningof each section are not intended to be completeinterpretations 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, hasbeen listed where applicable.

Additional regulatory information is containedelsewhere in this binder. For information pertainingto Department of Transportation (DOT) benzene-related 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 regulatedby OSHA in 29 CFR 1910.1028. This specific healthand 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, employeetraining, exposure monitoring, and record keeping

requirements. OSHA requires compliance with thePELs through engineering and work practice controls, and permits respirators only to be used asan interim measure or where engineering controlsand/or work practices are infeasible, or duringemergencies. The PELs are more fully discussed inSection 4.2 Occupational Exposure Limits forBenzene. A copy of the OSHA Benzene Standard,including its appendices A through D, is containedin Appendix B of this document.

U.S. COAST GUARDThe Marine Occupational Safety and HealthStandard for Benzene contained in 46 CFR 197applies to all Coast Guard inspected vessels, including tank ships and barges that carry liquidscontaining 0.5% or greater benzene by volume. Theexposure limits are the same as those contained inthe OSHA Benzene Standard.

Unlike OSHA, the Coast Guard does not specifywhat method or combination of methods is to beused in complying with the regulation. It permitsengineering controls, revised work practices, and/orpersonal protective devices to be used withoutmandating any specific method. A copy of theMarine Occupational Safety and Health Standard for Benzene contained in Appendix C of this document.



TABLE 4.1: OCCUPATIONAL EXPOSURE LIMITSFOR BENZENE IN THE U.S.

Organization/Agency Occupational Exposure Limit

OSHA PEL 1 ppm TWA5 ppm STEL0.5 ppm ACTION

Coast Guard 1 ppm TWA5 ppm STEL0.5 ppm ACTION

ACGIH TLV 0.5 ppm TWA2.5 ppm STEL Skin Notation*

NIOSH REL 0.1 ppm TWA1 ppm STEL500 ppm IDLH**

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4.2 Occupational Exposure Limits for Benzene

GENERAL INFORMATION ON OCCUPATIONAL EXPOSURE LIMITSOSHA Permissible Exposure Limits-Time-WeightedAverages (PEL-TWAs) are the maximum exposurespermitted by OSHA to time-weighted average airborne concentrations of substances for any 8-hour workday of a 40-hour workweek. Employersmust comply with these limits by law. Short-termexposure limits (STELs) are 15-minute time-weightedaverage concentrations not to be exceeded duringthe workday. An action level is typically an 8-hourtime-weighted average airborne concentration that,if exceeded, will trigger a number of the ancillaryprovisions of an OSHA health standard.

Threshold Limit Values (TLVs) are limits established by the American Conference ofGovernmental Industrial Hygienists (ACGIH). TLV-TWAs refer to the time-weighted average airborne concentrations of substances for a normal8-hour workday and a 40-hour workweek, to whichnearly all workers may be repeatedly exposed, dayafter day, without experiencing an adverse healtheffect. TLVs are intended to be used in the practice ofindustrial hygiene as guidelines or recommendationsin the control of potential health hazards.

The National Institute of Occupational Healthand Safety (NIOSH) also publishes recommendedexposure limits (RELs). The RELs are usually for upto a 10-hour work shift and a 40-hour workweek.

OCCUPATIONAL EXPOSURE LIMITSFOR BENZENETable 4.1 provides a summary of the occupationalexposure limits used in the United States for benzene.

* Skin notation: air sampling alone is insufficient to accuratelyquantify exposure. Measure to prevent significant skin absorption may be required

** Immediately Dangerous to Life or Health

BIOLOGICAL EXPOSURE INDICESThe American Conference of Governmental IndustrialHygienists (ACGIH) has established BiologicalExposure Indices (BEIs) for benzene. BEIs aresimilar to TLVs in that they are reference valuesintended as guidelines for the evaluation of potentialhealth hazards in the practice of industrial hygiene.However, BEIs involve biological monitoring ratherthan the workplace air monitoring associated with TLVs.

The ACGIH specifies that "BEIs represent thelevels of determinants which are most likely to beobserved in specimens collected from a healthyworker who has been exposed to chemicals to thesame extent as a worker with inhalation exposureto the TLV." The determinant can be the chemicalitself or its metabolite(s), or a characteristic reversiblebiochemical change induced by the chemical. TheBEIs for benzene are listed in Table 4.4.

EPA ACUTE EXPOSURE GUIDELINE LEVEL – PROPOSEDAEGLs represent threshold exposure limits for thegeneral public and are applicable to emergencyexposure periods ranging from 10 min to 8 h.AEGL-2 and AEGL-3, and AEGL-1 values as appro-priate, will be developed for each of five exposureperiods (10 and 30 min, 1 h, 4 h, and 8 h) and willbe distinguished by varying degrees of severity oftoxic effects. It is believed that the recommendedexposure levels are applicable to the general population including infants and children, andother individuals who may be susceptible.

For current status, consult the EPA Website:www.epa.gov/oppt/aegl/results72.htm

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TABLE 4.2: OTHER EXPOSURE GUIDELINES

Organization/Agency Exposure Guideline

American Industrial EPRG-1 – 50 ppmHygienists Association EPRG-2 – 150 ppm(AIHA) Emergency EPRG-3 – 1000 ppmResponse PlanningGuidelines (ERPGs)

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% LELAEGL 3 - 10 mins = ** 9,700 ppmFor 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.

1. This determinant is the most convenient one to use as aBEI. 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, itis essential to consult the specific BEI documentationpublished in the Documentation of Threshold Limit

Values and Biological Exposure Indices, 6th edition,1991, before designing biological monitoring andinterpreting BEIs.

4.3 Federal Environmental Regulatory Overview

RESOURCE CONSERVATION AND RECOVERY ACT (RCRA)The EPA’s Resource Conservation and Recovery Act(RCRA) regulates the management of hazardous andsolid wastes. It gives the EPA authority to controlhazardous wastes from generation to disposal. Asolid waste is hazardous if it exhibits one or moreof the designated characteristics (i.e., ignitability,corrosivity, reactivity, and toxicity), or is specificallylisted as a RCRA hazardous waste.

Under RCRA (40 CFR 261.33), benzene as acommercial chemical product, intermediate, or off-specification product that becomes a waste materialis a specifically listed hazardous waste. The RCRAhazardous waste number for such material is U019.A solid waste that has a benzene concentration of0.5 mg/l or greater, as determined by the toxicitycharacteristic leaching procedure (TCLP), is regulatedas a characteristic hazardous waste. Per 40 CFR261.24, the RCRA hazardous waste number for thismaterial is D018.

In addition to the preceding, there are severalother specifically listed benzene-related RCRA hazardous wastes. For example, benzene used as aspent solvent has a hazardous waste code of F005.40 CFR 261.31 and 261.32 should be referred to fora complete listing of benzene-related wastes fromnon-specific and specific sources.

COMPREHENSIVE ENVIRONMENTALRESPONSE, COMPENSATION AND LIABILITY ACT (CERCLA)The Comprehensive Environmental Response,Compensation and Liability Act (CERCLA), alsoknown as Superfund, established broad federalauthority to respond to releases or threats of releases of hazardous substances from vessels andfacilities. The list of CERCLA hazardous substancesand their reportable quantities (RQs) is contained in 40 CFR 302.

Lists of regulated hazardous constituents inother environmental statutes were used by the EPA

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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 shiftMixed-Exhaled 0.08 ppm2

End-Exhaled 0.12 ppm2

to compile the CERCLA hazardous substance list.Benzene was included in the statutory CERCLA RQlist on the basis of its designation as a hazardousconstituent in the CAA, CWA, and RCRA. Accordingto the degree of hazard, RQs are set at either 1,000,100, 10, or one pound. The statutory RQ forbenzene is 10 pounds based on its carcinogenicity(40 CFR 302.4). The one-pound RQ is generallyreserved for substances that are acutely or extremelyhazardous. It is not anticipated that the RQ forbenzene will be revised based on its properties.

Immediate notification must be made to theNational Response Center, state and local responseauthorities, i.e., SARA Title III - Section 304 notificationrequirements, if a CERCLA hazardous substance hasbeen released in a quantity equal to or greater thanits RQ.

SUPERFUND AMENDMENTS AND REAUTHORIZATION ACT - TITLE III (SARA TITLE III)SARA Title III is also known as the EmergencyPlanning and Community Right-to-Know Act(EPCRA). It contains four major sections: emergencyplanning (Section 301-303); emergency release notification (Section 304); community right-to-knowreporting requirements (Section 311/312); and, toxicchemical release reporting-emissions inventory(Section 313).

Sections 301-303: Emergency response plansmust be prepared by any facility that has presentany of the listed chemicals (Extremely HazardousSubstances) in Section 302 (40 CFR 355) at a quantity equal to or greater than its threshold planning quantity.

Benzene is not listed as an ExtremelyHazardous Substance.

Section 304: Facilities must make immediateemergency notifications if there is a release of alisted hazardous substance that exceeds thereportable quantity (RQ) for that substance.Substances subject to this requirement are thoseidentified on the list of Extremely HazardousSubstances in Section 302, and those on the list ofCERCLA hazardous substances, found in 40 CFR 302.

Benzene is a CERCLA hazardous substance witha 10 pound RQ (See Section 4.3 ComprehensiveEnvironmental Response, Compensation and LiabilityAct (CERCLA)). Immediate emergency notificationsare required for releases in excess of this amount.

Sections 311/312: These sections establish community right-to-know reporting requirementsfor "Hazardous Chemicals." Hazardous Chemicalsare those chemicals regulated under the OSHAHazard Communication Standard (29 CFR 1920.1200),and which require the preparation of a MaterialSafety Data Sheet (MSDS).

Section 311 requires a one-time submission ofthe MSDS, or alternatively, a list of materials (whichexceed specified reporting thresholds) at the facility.The list of chemicals must be grouped into fivehealth or physical hazard categories established by the EPA for purposes of this report.

Section 312 requires annual "Emergency andHazardous Chemical Inventories" be submitted in areporting format that identifies the hazard categories(Tier I reports). It also requires the submittal of a Tier II inventory upon request. The followingSection 311/312 hazard categories apply to benzene:

• Immediate (acute) Health Hazard• Delayed (chronic) Health Hazard• Fire HazardSection 313: This section requires an annual

estimate and reporting of toxic chemicals released tothe environment during the prior calendar year. Alist 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. Annualreporting requirements apply to facilities that manufacture or process benzene in amounts abovethe threshold planning quantity of 25,000 pounds.There is a 10,000 pound threshold planning quantitywhich triggers reporting requirements for facilitiesthat use benzene in ways other than those definedby manufacturing or processing.

For more information on the EmergencyPlanning and Community Right-to-Know Act, callthe EPA’s Information Hotline at 1-800-535-0202.

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CLEAN AIR ACT (CAA)In 1970, Congress passed the Clean Air Act (CAA)to provide the structure for the EPA’s air pollutioncontrol program. The CAA was most recentlyamended in 1990, with some major changes beingmade to the act. These changes are often referredto as the Clean Air Act Amendments of 1990 (CAAAof 1990). A key element of the CAA is to establishnational ambient air quality standards that representthe level at which specified air pollutants are determined by the EPA to be safe.

Section 111: The CAAA of 1990 has standards ofperformance for new stationary sources (40 CFR60). Subpart VV addresses standards of performancefor equipment leaks of volatile organic compoundsin the synthetic organic chemicals manufacturingindustry (SOCMI). There is a listing of chemicalsproduced as intermediates or final products, byprocess units, covered under this part. Benzene isone of the chemicals listed as a Potential HumanHealth Hazard (40 CFR 60.489).

Section 112: The National Emissions Standardsfor Hazardous Air Pollutants (NESHAP) were established under Section 112 of the Clean Air Act.The NESHAP requires the EPA to develop standardsrelated to various industrial and manufacturing categories for specifically listed hazardous air pollutants (HAPs). The standards are to provide "anample margin of safety to protect human health,"and to consider the maximum achievable control technology(MACT).

In 40 CFR par 61 there are NESHAP standardsfor eight (8) substances, one of which is benzene.The benzene NESHAP was originally published bythe EPA on June 8, 1977.Three revisions have beenmade to the rule: September 14, 1989; September19, 1989; and March 7, 1990. The benzene-relatedNESHAP standards are located in 40 CFR 61.

The NESHAP program is to augmented by theAir Toxics Program as detailed in the Clean Air ActAmendments of 1990. It should be noted, though,that existing NESHAP regulations remain in effect.The revised Section 112 of the CAA establishes anew technology and risk-based program. In April,

1994, the EPA promulgated a new regulation calledthe hazardous organic NESHAP, or HON. The HONrequires sources to achieve emission limits reflectingthe application of MACT, consistent with Sections112(d) of the CAA.

The rule regulates emission of HAPs at bothnew 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 ToxicsProgram (40 CFR part 63 subparts F, G and H).Benzene is also listed as a “Group I” SOCMI chemicalunder the HON (40 CFR 63) for wastewater purposes.In the regulations governing compliance for earlyreductions of HAPs, benzene was placed on the listof 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 notalready covered by the HON (40 CFR part 63subpart FFFF). Benzene is also regulated for othersource categories under other subparts of part 63.

CLEAN WATER ACT (CWA)The Clean Water Act (CWA) is the cornerstone ofsurface water quality protection in the UnitedStates. (The Act does not deal directly with groundwater nor with water quantity issues.) The statuteemploys a variety of regulatory and nonregulatorytools to sharply reduce direct pollutant dischargesinto waterways, finance municipal wastewater treatment facilities, and manage polluted runoff.These tools are employed to achieve the broadergoal of restoring and maintaining the chemical,physical, and biological integrity of the nation'swaters 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 CWAin 1972, EPA, states, and Indian tribes focusedmainly on the chemical aspects of the "integrity"

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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.

goal. During the last decade, however, more attention has been given to physical and biologicalintegrity. Also, in the early decades of the Act'simplementation, efforts focused on regulating discharges from traditional "point source" facilities,such as municipal sewage plants and industrialfacilities, with little attention paid to runoff fromstreets, 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, includingcost-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 froma program-by-program, source-by-source, pollutant-by-pollutant approach to more holisticwatershed-based strategies. Under the watershedapproach equal emphasis is placed on protectinghealthy waters and restoring impaired ones. A fullarray of issues are addressed, not just those subjectto CWA regulatory authority. Involvement of stakeholder groups in the development and implementation of strategies for achieving andmaintaining state water quality and other environ-mental goals is another hallmark of this approach.

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TOXIC SUBSTANCES CONTROL ACT (TSCA)The Toxic Substances Control Act (TSCA), passedby Congress in 1976 (Public Law 94-469), is acomplex and detailed statute which empowers theU.S. Environmental Protection Agency (EPA) toevaluate and regulate chemical substances and mixtures which may have an adverse impact onhuman health and the environment. It provides theEPA with broad authority to regulate the manufacture,import, processing, distribution, use, and disposalof chemical substances.

TSCA’s coverage is comprehensive. With theexception of chemicals specifically regulated bycertain other federal laws (i.e. FIFRA for pesticides;FDA for food, drugs and cosmetics), it potentiallyapplies 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 aredescribed 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 anunreasonable risk of injury to the environment orhealth, or if they will be produced in substantialquantities resulting in significant human or environmental exposure.

The EPA is given the authority under Section 4to require testing of chemical substances and mixtures. There are presently no testing requirementsfor benzene. However, 12 chemical substances,including benzene, were identified as having toxicological data needs by the Agency for ToxicSubstances and Disease Registry (ATSDR), NationalToxicological Program (NTP), and the EPA pursuantto Section 104(i)(5) of the ComprehensiveEnvironmental Response, Compensation andLiability Act of 1980 (CERCLA, or Superfund).

Section 8(b) - Chemical Substances Inventory:

To be used in a commercial application or as acomponent in a commercial product, a material hasto be listed on the TSCA Chemical SubstancesInventory (40 CFR 704, 710, 720, and 723).Benzene, CAS # 71-43-2, is listed on this inventory.

Section 13 - Import Certification: TSCA specificallyrequires that any chemical substance mixture, orarticle containing a chemical substance or mixturebe refused entry into the customs territory of theUnited States if it fails to comply with any rule ineffect under TSCA or is offered for entry in violationof Section 5, 6, or 7 of TSCA. Regulatory authorityfor Section 13 of TSCA lies with the EnvironmentalProtection Agency (EPA) and U.S. Customs.Regulations addressing the import requirements ofTSCA may be found at 40 CFR 707.20 and 19 CFR12.118 -12.128. All imports of benzene must be positively TSCA certified with US Customs at thetime 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 highlyhazardous chemical in the standard. It does,though, meet the definition of a flammable liquidor gas. As a result, a process which involves theuse of benzene on site in one location, in a quantityof 10,000 pounds or more, is subject to the requirements of this standard.

4.5 State Right-to-Know Laws/Regulations

STATE RIGHT-TO-KNOW LISTINGSIn addition to the Federal Right-to-Know requirements(OSHA’s Hazard Communication Standard andEPA’s SARA Title III, which is also known as theEmergency Planning and Community Right-to-KnowAct of 1986 (EPCRA)), numerous states haveadopted right-to-know laws or regulations.

When the state right-to-know laws are contrastedwith the OSHA rule, significant differences are oftenobserved regarding the scope, chemicals regulated,and labeling requirements. Various states haveestablished specific lists of regulated chemicalsrather than requiring hazard determinations to beconducted to ascertain whether a chemical shouldbe considered as "hazardous." Benzene does meetthe definition of a hazardous chemical per OSHA’sHazard Communication Standard (29 CFR 1910.1200).

Table 4.5 contains a list of the states ShellChemical LP monitors that have right-to-knowchemical lists which include benzene. For detailedinformation on the requirements of a particular state right-to-know law, the appropriatestate agency should be contacted.

CALIFORNIA SAFE DRINKING WATER AND TOXICS ENFORCEMENT ACT OF 1986(PROPOSITION 65)The California Safe Drinking Water and ToxicsEnforcement Act of 1986 (better known asProposition 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 ofCalifornia to cause cancer. The No Significant RiskLevel established for benzene by the state is seven(7) micrograms/day.

For additional information regarding Proposition65 (California Health and Safety Code Section25249.5), contact: California EnvironmentalProtection Agency, Office of Environmental HealthHazard Assessment, 601 N. 7th Street, P.O. Box942732, Sacramento, CA 94234-7320.

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TABLE 4.5: STATES WITH SPECIFIC RIGHT- TO-KNOWLISTINGS FOR BENZENE

California

Connecticut

Illinois

Indiana

Kentucky

Louisiana

Massachusetts

Michigan

Minnesota

New Jersey

New York

North Carolina

Pennsylvania

Rhode Island.

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4.6 Food and Drug Administration (FDA)

The Food and Drug Administration (FDA) hasauthority for the regulation of food and pharmaceu-tical activities in the United States. As detailed in 21 CFR 175.105, benzene can be used only as acomponent of adhesives. In this application, it isconsidered to be an indirect food additive. Theadhesive in which benzene is used must either beseparated from the food by a functional barrier orused subject to additional limitations specified inthe regulation.

Any use of benzene in pharmaceutical productswould be subject to approval pursuant to the FDA’sgeneral procedures for testing and certifying pharmaceutical products.

Shell Chemicals* policy is to not sell benzeneinto food, drug or cosmetic applications.

4.7 Consumer Product Safety Commission (CPSC)

The Consumer Product Safety Commission (CPSC),established in 1972 by the Consumer Product SafetyAct (CPSA), has responsibility for protecting thepublic from unreasonable risks associated with consumer products. In 1978, the CPSC proposed aban on all consumer products (except gasoline andsolvents or reagents for laboratory use) containingbenzene as an intentional ingredient or as a contaminant constituting 0.1% or more by volume.

The Commission withdrew its proposed ban in1981 on the basis of information that benzene, ascurrently used in consumer products, did notpresent a significant risk to consumers. The dataobtained from contacts in industry and informationprovided by manufacturers, importers, and labelersof such products indicated that benzene was notcurrently used intentionally in consumer products.

A labeling regulation established for productscontaining more than 5% benzene, and a safetypackaging requirement for paint solvents and thinners containing 10% or more of petroleum distillates such as benzene, remains in effect. CPSChas also recommended in its publication, "SchoolScience Laboratories – A Guide to Some HazardousSubstances," that benzene not be used or stored inhigh school laboratories.

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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)

4.8 International Regulations

CANADA 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 EnglishIngredient Disclosure List for benzene is 153, andits concentration threshold is 0.1%.

NPRI: Pursuant to Section 16 of the CanadianEnvironmental Protection Act (CEPA), the NationalPollutant Release Inventory (NPRI) established a list of substances required to be reported for toxicrelease purposes. Supplier notification is requiredfor benzene. (128, Can. Gaz., Part I, 1378, Feb. 26,1994.)

DSL: The Canadian Chemical Inventory, whichis called the Domestic Substances List (DSL), contains chemicals which were in commerce inCanada 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.

FOREIGN CHEMICAL INVENTORIES In addition to the Canadian Chemical Inventory(DSL), benzene is also listed on various otherforeign chemical inventories, a number of whichare listed in Table 4.6. Since several countries,including China and Mexico, are currently in theprocess of establishing chemical inventories, thisshould not be considered an all-inclusive listing.

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4.9 Hazard Ratings for Benzene

NATIONAL FIRE PROTECTION ASSOCIATION(NFPA) HAZARD RATINGNFPA 704 is the Standard System for the Identificationof Fire Hazards of Materials. It addresses the health,flammability, reactivity, and related hazards thatcould arise during short-term, acute exposure to amaterial in a fire, spill, or similar emergency situation.

The intent of the system is to provide basicinformation to fire fighting, emergency, and otherpersonnel to aid them in making decisions relatedto an emergency involving a specific material.

The system identifies the hazards of a materialin terms of three principal categories: "health,""flammability," and "reactivity." It indicates thedegree of severity by a numerical rating that rangesfrom four (4), indicating severe hazard, to zero (0),indicating no hazard.

NFPA HAZARD RATING FOR BENZENEHealth - 2: Materials that, on intense or short

exposure, could cause temporary incapacitation orpossible residual injury, including those requiringthe use of respiratory protective equipment havingan independent air supply.

Flammability - 3: Liquids and solids that can be ignited under almost all ambient temperatureconditions. Materials in this degree produce hazardous atmospheres with air under almost allambient temperatures or, though unaffected byambient temperatures, are readily ignited underalmost all conditions.

Reactivity - 0: Materials that in themselves arenormally stable, even under fire conditions.

NATIONAL PAINTS AND COATINGS ASSOCIATION (NPCA) HAZARDOUS MATERIALSIDENTIFICATION SYSTEM (HMIS) RATINGThe NPCA HMIS ratings use the same principal categories (Health, Flammability, and Reactivity)and numerical rating ranges (0-4) as the NFPAhazard rating system. However, one significant difference between the two rating systems is thatHMIS ratings are not intended for emergency ormisuse situations. Rather, they are meant to applyto normal use of the products in the plant.

NPCA HMIS RATING FOR BENZENEHealth - 2*: Materials that may cause temporary

or minor injury. Use of an asterisk (*) indicatesthere may be chronic health effects present.

Flammability - 3: Materials capable of ignitionunder almost all normal temperature conditions,including flammable liquids with flash points below73 °F and boiling points above 100 °F, as well asliquids 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 withwater.


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 40 CFR (SARA Title III), also known as the Emergency • section 301-303: emergency release notification Planning and Community Right-to-Know Act • section 304: community right-to-know reporting (EPCRA) 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

5.1 Personal Protective Equipment

RESPIRATORY PROTECTIONPer the OSHA Benzene Standard (29 CFR1910.1028), engineering controls and work practicesshould be instituted to reduce and maintain exposureto airborne concentrations of benzene at or belowthe permissible exposure limits (PELs). Where thesecontrols are not feasible or where the provisions ofthe standard allow, respiratory protection is permittedto be used to control employee exposure to orbelow the PELs. Table 5.1 contains the respiratory

requirements listed in the OSHA Benzene Standard.For additional details on methods of complianceand respiratory protection requirements, pleaserefer 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 havebeen trained and it has been determined they are physically able to perform the work and use the equipment.

5. HANDLING ANDSTORAGE INFORMATION

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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 organicvapor canister2

(d) Less than or equal to 1,000 ppm. (1) Supplied air respirator with full face piece in positive-pressure mode

(e) Greater than 1,000 ppm or (1) Self-contained breathing apparatus with full face piece in unknown concentration. positive-pressure mode

(2) Full face piece positive-pressure supplied-air respirator withauxiliary 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 inpositive-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.

TABLE 5.1: RESPIRATORY PROTECTION FOR BENZENE1



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CHEMICAL PROTECTIVE CLOTHING (CPC)The purpose of chemical protective clothing (CPC)is to prevent and/or limit skin contact with chemicalsthat are hazardous. As indicated in Section 2.Health Hazard Information, skin contact with liquidbenzene may result in irritation and erythema (reddening of the skin). Prolonged and repeatedskin contact can result in defatting and drying ofthe skin, which may lead to dermatitis and increasedchance of secondary infection. In addition, liquidbenzene can be absorbed through the skin.

The specific level of CPC required will dependon the conditions. The level of protection selectedshould be based on the potential benzene concen-tration and likelihood of contact. It could rangefrom no CPC being required, such as whenbenzene is handled in closed systems and there is no personnel exposure, to chemical splash-suitswith positive-pressure-supplied air respirators being required, as would be the case in certain spill situations.

While one cannot recommend the specific levelof CPC to be used without thoroughly evaluatingthe conditions, some general CPC selection recommendations for benzene are provided in theShell MSDS for Benzene. The MSDS notes that testdata from published literature and/or glove andclothing 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 onthe Shell MSDS should in no way be considered acomplete list of all materials that are acceptable for use with benzene.

References such as those identified belowprovide test data and/or recommendations onvarious materials which can be used to assist in theselection of CPC for benzene. Again, this referencelisting should not be considered an all-inclusive setof 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.

• Quick Selection Guide to Chemical Protective

Clothing, Second Ed., Mansdorf, S.Z. and K.Forsberg, Van Nostrand Reinhold, NewYork, 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 GovernmentalIndustrial Hygienists, Cincinnati, OH.

The data contained in the references generallytake into account two important measures of thechemical resistance of CPC to benzene. These measures include:

Degradation: The deleterious change in physicalproperties of a clothing material upon contact by achemical. Examples of properties which can beevaluated include thickness, weight, elongation, tearstrength, cut resistance, and puncture resistance.

Permeation: The diffusion of a chemical on amolecular level through CPC. The term break-

through time is used to define the time it takes thechemical to pass through the CPC and be detectedby an analytical instrument.

In addition to the chemical breakthrough performance information, i.e., the resistance of theCPC to benzene, there are additional factors whichneed to be considered in CPC selection. Forexample, a third factor that may not be consideredin the references is that of penetration. Penetrationis the flow of material through CPC at a non-molecular level, i.e., through rips, tears, seams, closures, and other damage or manufacturingimperfections. Along with penetration, a number of these factors have been listed below:

• Physical resistance of CPC (resistance to cutsand 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 reducedbreakthrough time.)

• 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 productdata. One reason this is important is because thechemical resistance of a generic material such aspolyvinyl alcohol may vary between manufacturersof CPC. Selection of hand protection (gloves)should also be in accordance with 29 CFR 1910.138.

EYE AND FACE PROTECTIONIn accordance with the OSHA standard for Eye andFace Protection (29 CFR 1910.133), protective eye and face devices should be worn when there isexposure to eye or face hazards from liquid chemicals or chemical gases or vapors.

At a minimum, chemical safety goggles shouldbe worn if there is a potential for liquid benzene toget in the eyes. Additional splash protection may beobtained with the use of a face shield.

Protective eye/face devices purchased after July5, 1994, must comply with ANSI Z87.1-1989. If purchased on or before July 5, 1994, protectivedevices should at least comply with ANSI Z87.1-1968.Refer to the latest ANSI Z87.1-2003 for informationon protective eye/face devices.

5.2 Exposure Monitoring

A number of methods are available for monitoringemployee exposures to benzene; the followinginformation addresses some of these methods.Please note that this section is not intended to be acomplete review and evaluation of benzene samplingand analytical methods. The employer is responsi-ble for a method’s accuracy and precision relevantto the unique conditions of the specific workplace,no matter what method is chosen. OSHA requiresthat the method of monitoring must be accurate, toa confidence level of 95%, to within plus or minus25% for airborne concentrations of benzene greaterthan or equal to 0.5 ppm..

The names of equipment manufacturers havebeen listed to provide a reference to enable additionalinformation to be obtained if desired. It is not anendorsement 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 involvethe use of charcoal tubes and sampling pumps, followed by analysis of the samples using gas chromatography (GC). Differences betweenmethods may include the use of different desorbingsolvents and variations in analytical equipment.

Appendix D contains NIOSH Method 1501,which applies to the sampling and analysis ofbenzene. OSHA Method No. 12 is contained inAppendix B as it is listed in OSHA’s BenzeneStandard. Both methods use charcoal tubes, sampling pumps, and GC analysis.

Passive Monitors: Passive dosimeter badges areavailable for monitoring airborne concentrations ofbenzene. One type of badge for benzene is the 3MOrganic Vapor Monitor #3500. The 3M TECH DATABulletin #59 contains information regarding theusage of this badge with respect to sampling forbenzene; a copy of this document has beenattached in Appendix E. The passive dosimeterbadge is analyzed in the same manner as the charcoal tube.

5-39/04

Direct Reading, Portable Instruments: There areportable instruments utilizing flame ionization orphoto ionization detectors that can be used tomeasure benzene in low-to-sub-ppm concentrations.(Examples include the Photovac Micro-Tip and theFoxboro TVA-1000 Analyzers.) These instrumentsrespond to a wide range of hydrocarbons. As aresult, they are nonspecific for benzene and can beaffected by the presence of other hydrocarbons.

Detector Tubes: A number of companies manufacture detector tubes for use with volumetricpumps to measure benzene concentrations. Thesecolorimetric indicating tubes provide a directreading of the benzene concentration. A specifiedamount of air is drawn through the tube, thebenzene present in the air reacts with the solidsorbent to produce a color change whose length isdirectly proportional to the benzene concentration.

National Draeger, Sensidyne, Mine SafetyAppliances, and Kitagawa are among the manufacturers who offer detector tubes for benzenesampling. A potential concern with the usage ofthese tubes is the lack of specificity when otherhydrocarbons, especially aromatics, are present. Asa result, manufacturers offer several types of detectortubes for benzene. Consult with the manufacturersto select the most appropriate tube.

Gas Chromatography (GC): The presence ofother hydrocarbons or certain gases may significantlyinterfere with readings obtained by benzene detectortubes or other direct-reading hydrocarbon analyzers.When this occurs, a GC method is a recommendedoption.

Portable GCs may be taken to the field fordirect on-site measurements or, alternatively, asyringe may be used to collect the sample whichcan then be injected into a GC for analysis.

5.3 General Information on Storage and Handling

The intent of this section is to provide an overviewof various benzene storage and handling issues.Topics addressed in the following subsectionsinclude materials of construction for use in benzeneservice, bulk movement of benzene by barge, andbulk benzene storage. Benzene handling andstorage practices are often similar to those used for gasoline because of comparable volatility andflammability. However, because of benzene’sgreater toxicity, some additional measures are necessary to minimize personnel exposure andreleases of this chemical to the atmosphere. Section8.2 Emission Reduction Measures details many practices which Shell Chemicals* have adopted inorder to reduce benzene emissions and may be referenced for further information.

EQUIPMENTLines: 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 berequired. 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 ofhoses where it is possible and practical. Forexample, loading arms connected to a marine vaporrecovery system are preferred to hoses. If hoses areused, they should be inspected and pressure-testedat the intervals required by the appropriate regulations. U.S. Coast Guard regulations 33 CFRParts 154.500 and 156.710 apply to hoses used forbulk transfers to and from tank vessels.

For guidance on bonding and grounding measures recommended for marine transfers, referto Section 6.1 Fire and Explosion Hazard.

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5-59/04

Jointing: Spiral wound gaskets with inner andouter rings have been successfully utilized inbenzene service. While screwed joints are codeacceptable (ANSI Code B-31.3), their use is discouraged.

Pumps: Centrifugal pumps are recommended.Positive displacement pumps may also be used, andshould be fitted with a pressure relief valve whichmust not be integral with the pump.

Pump seals must be capable of meeting EPAemission standards. Typically, this requires tandemor double seals.

Valves: For pigged pipelines, full-bore ballvalves are preferred. For other than piggedpipelines, gate valves, butterfly valves, or ballvalves may be used.

Materials of construction recommended forvalves include cast iron or cast steel. For valvepacking, lubricated Teflon (PTFE) or equivalentmay be used.

Incompatible Materials: Polyvinyl chloride andnatural, butyl, neoprene, and nitrile rubbers are allincompatible materials of construction for use withbenzene.

BULK MOVEMENT OF BENZENE BY BARGEVapor Return Line During Loading: The loading

of this product in certain states, e.g., Texas,Louisiana and Illinois, may require the use of vaporcontrol. In the absence of a regulatory requirement,closed loading should be carried out with vaporreturn to shore when these facilities are available.

Closed Gauging: Gauging must consist of aclosed device for use during transfer (e.g., sightglasses), and a restricted device to determineproduct quantity during transfer.

Pressure: Atmospheric pressure. Cargo to becarried at not more than 10 pounds per squareinch, exclusive of static head.

Acceptable Internal Tank Surface: Clean stainlesssteel or rust-free mild steel tanks, or mild steeltanks lined with a phenolic epoxy paint or zinc sili-cate paint, are recommended. If an amine oramine-adduct cured epoxy paint lining is used, itshould be of a multi-coat, spray-applied, heat-curedsystem. Cold-cured epoxy resin-based paint systemsapplied by brush or spray will tend to soften.

Shipping Temperature:

Ambient (50 °F minimum).Loading & Discharge Temperature:

Ambient (50 °F minimum).Maximum Product Temperature:

Ambient (50 °F minimum).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 BENZENETank 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 tanklined with a phenolic epoxy paint or zinc silicate paint, are recommended. If an amine oramine-adduct cured epoxy paint lining is used, itshould be of a multi-coat, spray-applied, heat-curedsystem. Cold-cured epoxy resin-based paint systemsapplied by brush or spray will tend to soften.

Nitrogen Blanketing: Not required. However,Shell Chemicals do use nitrogen blanketing onsome of its shipping tanks, and does have a routineinspection 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 heatingcoils.

Cooling: Storage tanks should ideally be paintedwhite externally. For fire-fighting purposes, a watercooling 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.

Pumping Rate: Because of the possibility of generating a high electrostatic charge, restrict linevelocity during pumping to < 1m/sec until fill pipesubmerged to twice its diameter, then < 7m/sec.Avoid splash filling. Refer to Section 6.1 Fire andExplosion Hazard for additional information onstatic electricity and the pumping rate. Do not usecompressed air for filling, discharging, or handling.

Personal Protective Equipment: Refer to Section5.1 Personal Protective Equipment for information.

BENZENE REACTIVITIES AND INCOMPATIBILITIESIf exposed to flame or heated, benzene presents amoderate explosion hazard. Benzene also has anumber of chemical reactivities and incompatibilitieswhich can result in explosive and/or vigorous reactions. Information is detailed in Section 1.6Benzene Reactivities and Incompatibilities regardingthe specific compounds and potential outcome ofthe reactivities and incompatibilities.


6. FIRE SAFETY& SPILLS AND LEAKS

6.1 Fire and Explosion Hazard

Benzene is an extremely flammable liquid, flashpoint = -11°C/12 °F (closed cup). The flash point isthe lowest temperature at which vapor is given offin sufficient quantity such that the vapor/air mixtureabove the surface of the material will propagate aflame away from the source of ignition, i.e., forman ignitable mixture. The closed cup indicationdenotes the type of method used to determine the flash point.

Benzene meets the definition of a Class 1BFlammable Liquid in both the OSHA Standard for Flammable and Combustible Liquids (29 CFR1910.106) and the National Fire ProtectionAssociation Flammable and Combustible LiquidsCode (NFPA 30). A Class 1B Liquid is defined ashaving a flash point below 23 °C/73 °F and aboiling point at or above 38 °C/100 °F. Transportationauthorities classify benzene as a flammable liquid(See Section 7.3 Transport Classifications for Benzene for additional information).

Explosive mixtures can be formed whenbenzene 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 canspontaneously ignite without the application of aflame or spark if it is heated above this temperature.Vapors of benzene are heavier than air. Thus, thesevapors may accumulate and travel along the ground

a significant distance to an ignition source, resultingin a flash-fire.

Flammable liquids such as benzene expandwhen heated. As a result, tanks should not be completely filled so that the danger of overflow canbe avoided. This is especially true when cool liquidis placed into a warm environment. Above-groundtanks are often painted with aluminum or white paint to reflect heat so the temperature rise of theliquid contents is decreased.

In a fire situation, hazardous conditions candevelop which could lead to dangerous explosionsand further fire danger. The buildup of pressure inclosed containers of benzene caused by elevatedtemperatures can result in container failure. If thepressure buildup created by exposure to elevatedtemperatures (such as may be present with anexposure fire) is not properly vented, it can resultin a phenomenon called a Boiling LiquidExpanding Vapor Explosion (BLEVE). The result of such a scenario can be a "pressure release explosion," characterized by the extremely quickmixing of benzene vapor and air, causing a fireballupon ignition by the fire that initially caused theBLEVE. This fireball and the resultant liquid groundfire is not as severe as that of a Liquefied PetroleumGas BLEVE, but will still result in the potential fordeath to personnel and serious property damage inthe immediate area.

6-19/04



9/046-2

There are a number of factors which canincrease the danger of tank failure from internalpressure 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 electricitycan also accumulate and create a fire hazard.Electrostatic discharge may be generated duringpumping. Ensure electrical continuity by bondingand grounding (earthing) all equipment. Restrict theline velocity (flow rate) during pumping in order toavoid generation of electrostatic discharge - <= 1meter/second until fill pipe is submerged to twiceits diameter, then <= 7 meters/second. Avoid splashfilling. DO NOT USE compressed air for filling, discharging, or handling operations. In practicalterms, loading by gravity only at this stage of theloading operation is most desirable.

Based on the recommendations of theInternational Safety Guide for Oil Tankers andTerminals, Shell Chemicals* have abandoned theuse of ship to shore bonding lines in favor of insulating flanges. In the past, it was common toconnect vessel and shore systems by using abonding wire via a flameproof switch before thecargo connection was made, and to maintain thisbonding wire in position until after the cargo connection was broken. The use of this bondingwire had no relevance to electrostatic charging. Itwas an attempt to short-circuit the vessel/shore electrolytic/cathodic protection systems and toreduce the vessel/shore voltage to such an extentthat currents in hoses or metal arms would be

negligible. However, because of the large currentavailability and the difficulty of achieving a sufficiently small electrical resistance in thevessel/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 wharfpiping are effective where stray currents arise fromonshore facilities. Insulating flanges at both locationsare employed to prevent arcing at those connections,and to prevent stray or cathodic protection currentflow between the wharf and shore piping. Toensure that insulating flanges are working properly,they must be tested annually to minimum resistanceof 1,000 ohms (more frequent testing may berequired when maintenance work is performedaround the flange area).

Articles 500 through 504 of the National ElectricCode (NEC-NFPA 70) address the requirements forelectrical equipment and wiring in locations wherefire or explosion hazards may exist due to flammablegases or vapors, flammable liquids, combustibledust, or ignitable fibers or flyings. Locations areclassified depending on the properties of the hazardous material. For purposes of the NationalElectric Code, benzene is categorized as a Class I,Group D material. Articles 500 through 504 of NEC-NFPA 70 should be referenced for additionalinformation on this subject.

6-39/04

6.2 Fire Prevention

Benzene is a significant fire and explosion hazardbased on its physical properties, including its flashpoint, vapor pressure, and boiling point. It canquite 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 plantoperations and activities, should be taken into consideration. All potential sources of ignitionshould be reviewed.

2. Storage and handling equipment should bedesigned and maintained in conformance withapplicable regulations and codes (ASME, OSHA,NFPA, API, DOT, National Electric Code, etc.).

3. Stringent hot work practices and systemsshould be in place which fully address benzene’sfire and explosion hazard. (Hot work is defined asincluding but not limited to welding, cutting, andburning.) Personnel should make necessary workpractice changes, i.e., ventilation, cleanup, etc., toensure benzene vapor is not present during anyspark-producing activities.

4. Preventive measures against the accumulationof static electricity should be employed.

6.3 Fire Fighting

Fire brigade members should be provided informa-tion on the hazards of benzene, quantities present,and location(s).

The fire fighting measures for benzene aresimilar to those for flammable liquids in general. Ifthere is a benzene fire or benzene is in a fire area,the fire area should be cleared of unauthorizedand/or unprotected personnel and isolated. Forincidents involving a tank, rail car, or tank truck,the U.S. Department of Transportation’s EmergencyResponse 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 ortank truck BLEVE fire failures, and to ensure personnel without proper personal protectiveequipment (PPE) are not overexposed to benzenevapors. Fire fighters should be wearing full bunkergear at a minimum (helmet with face shield, bunkercoats and pants, gloves, and rubber boots), includinga positive pressure, NIOSH-approved (or otherappropriate regulatory authority), self-containedbreathing 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 dikecontainment capacity is not exceeded. Water willnot normally extinguish a flammable liquid such as benzene when it is on fire.

Disperse vapors with a sustained flow of waterfog or blanket with foam. Keep liquid and vaporaway from heat, sparks, and flames. Surfaces thatare sufficiently hot may ignite liquid benzene, evenin the absence of sparks or flame. Precautions mustbe taken to eliminate all potential sources of ignition.Benzene vapors are heavier than air and may travela considerable distance to a source of ignition andflash back.

Containers of benzene exposed to intense heatfrom fires should be cooled with large quantities ofwater to prevent vapor pressure buildup, whichcould result in container failure and/or weakeningof the container structure. In fighting tank fires, it isimperative that the shell above the liquid level is

9/046-4

cooled to keep the steel from overheating.Regardless of the adequacy of the venting systemon the tank, it can bulge and rupture if this is notdone. Water should be applied from a safe distanceand until well after the fire is out. Stay away fromthe ends of the containers. If possible, the coolingof the containers should be done with unmannedhose holders or monitor nozzles. If water suppliesare limited or not available, fire fighters should bewithdrawn and the fire allowed to burn.

Immediate withdrawal of fire fighting personnelshould take place in case of the rising sound of aventing safety device or localized heating and dis-coloration of the tank due to fire. (This wouldappear as a reddening, much like a steel platewhen heated with a torch.)

In the event there is residual benzene contami-nation after a fire has been extinguished, thecleanup activities must be conducted in accordancewith the local requirements (i.e. in the US, OSHAHazardous Waste Operations and EmergencyResponse (HAZWOPER) Standard (29 CFR1910.120). Experience has shown that after such anincident, benzene will most likely be present inlevels that exceed the permissible exposure level.Proper PPE, especially respiratory and skin protection, will be needed.

6.4 Spills and Leaks

Spill and leak activities must be conducted in accordance with the requirements of the OSHAHazardous Waste Operations and EmergencyResponse (HAZWOPER) Standard (29 CFR1910.120). In part, this requires that an emergencyresponse plan be developed and implemented to handle anticipated emergencies prior to the commencement of emergency response operations.The information contained in the remainder of thissection should be considered in the development of such a plan.

In the event of a benzene spill or leak, thehazard area should be isolated and entry denied to unnecessary personnel. Individuals should stayupwind and keep out of low areas.

Wearing appropriate respiratory equipment andchemical protective clothing, response personnelshould eliminate all ignition sources if it is safe todo so. The spilled benzene should be diked andcontained. It is particularly important to keepbenzene or benzene-contaminated runoff fromentering sewers and water-ways, due to the potentialfire and explosive hazards which will be created. Inaddition, there is the aquatic toxicity concern asdetailed in Section 3. Ecotoxicity/Ecological Fate.

If a benzene leak is occurring, it should bestopped only if it can be done safely. Use waterspray to disperse vapors and to flush spills awayfrom exposures, with the runoff being contained.Be aware that water spray may reduce vapors, butit may not prevent ignition in closed spaces. Theuse of foam to blanket vapors will also assist inleak control.

The material should be removed with vacuumtrucks or pumped to storage/salvage vehicles. Anabsorbent such as clay, sand, or other suitablematerial can be used to soak up the residue. Thisresidue should be placed in non-leaking containersfor appropriate disposal. Small spills can be takenup in a similar manner to the residue of large spills.To remove trace residues from either large or smallspills, flush the area and collect the flush solutionfor disposal.


Keep liquid and vapor away from heat, sparks,and flames. Surfaces that are sufficiently hot mayignite liquid benzene, even in the absence ofsparks or flame. Precautions must be taken to eliminate all potential sources of ignition. Benzenevapors are heavier than air and may travel a considerable distance to a source of ignition andflash back.

Static electricity can also accumulate and createa fire hazard. Refer to Section 6.1 Fire and ExplosionHazard for precautions and recommendations relative to the use of bonding cables and staticelectricity.

If an amount equal to or greater than theCERCLA reportable quantity (RQ) for benzene isreleased, immediate emergency notifications mustbe made to the National Response Center, as wellas to appropriate state and local response authorities.The current CERCLA RQ for benzene is 10 pounds.Please refer to Section 4.3 ComprehensiveEnvironmental Response, Compensation andLiability Act (CERCLA) for more detailed informationon these requirements.

7. TRANSPORTATION

7-19/04

7.1 General Information on BenzeneTransportation

It is Shell Chemicals’* objective to ensure thatbenzene is safely transported to its customers’ facilities. Shell chemicals companies transportbenzene 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 tanktrucks or tank cars only on an exception basis.

The physical and health hazards of benzenemust be considered when arranging for transport ofthis material. In previous sections, many of thesehazards have been discussed in detail. We wouldadvise shippers to become familiar with all precautions discussed in the previous sections andall other applicable safety precautions and/or legalrequirements. Highlights of some of the shippingconsiderations are given below.

Shipping Conditions: For information on shipping conditions, refer to Section 5.3 BulkMovement of Benzene by Barge.

Regulatory Controls: Shipments and releasesof benzene are regulated by various agencies. Itmay be helpful to review the discussion of the U.S.Coast Guard requirements below and refer toSection 4. Regulatory Overview, of this documentfor a more detailed discussion.

BARGE SHIPMENTSThe shipment of benzene by barge is regulated bythe U.S. Coast Guard. Barges used for the carriageof benzene (and products containing greater than0.5% benzene by volume) are regulated by 46 CFRPart 151, Subchapter O, as dangerous cargo. The Certificate of Inspection for the barge issued by theU.S. Coast Guard must be specifically endorsed forbenzene or the benzene mixture being moved.Whereas the Coast Guard permits the carriage of benzene in barges with Type III hulls, ShellChemicals 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 insuch a way to minimize employee exposure and environmental releases. Both OSHA and the U.S.Coast Guard have introduced a number of regulationsapplicable to personnel involved in handlingbenzene. Among others, the benzene regulationsinclude, 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.



9/047-2

To place due emphasis on the transfer ofbenzene (or hydrocarbon mixtures containing in excess of 0.5% benzene by volume) at Shellmarine terminals, an Addendum to the Declarationof Inspection is used. Appendix F of this document contains a copy of both the Declarationof Inspection and the Benzene Addendum used by Shell chemicals companies. The signers of thisAddendum certify that detailed requirements forhandling benzene are complied with before transfer occurs.

CLEANING OF EQUIPMENT Unless the shipper or unloader has its own cleaningfacilities that can clean and dispose of the residueresponsibly, it is advised that a qualified contractorbe used to clean, inspect, and repair barges inwhich benzene is shipped.

7.2 Emergency Response

In the event a transportation incident involvingbenzene does occur, the Chemical TransportationEmergency Center (CHEMTREC®) should be contacted for immediate assistance. CHEMTREC is a public service organization established by theAmerican Chemistry Council (ACC) and its membersto provide assistance in hazardous materials incidents.

CHEMTREC’s toll-free Emergency AssistanceNumber is 1-800-424-9300. Ships at sea can contactCHEMTREC through the International and MaritimeNumber: 1-703-527-3887. The CHEMTREC center isstaffed 24-hours-a-day, 7-days-a-week, by trainedcommunicators.

CHEMTREC uses a two-step approach inresponding to emergencies involving hazardousmaterials. First, immediate emergency responseinformation for the product involved in the incidentis provided to the caller. This information is generallyobtained from the manufacturer’s Material SafetyData Sheet (MSDS) for the product in question. The Department of Transportation’s EmergencyResponse Guidebook may also be referenced;Guide 27 of this document applies to emergencyactions for benzene incidents.

The second step is for CHEMTREC to notify the 24-hour emergency contact designated by theshipper or manufacturer of the material involved in the incident. Shell chemicals’ companies haveemergency response procedures in place to provideadditional technical advice and assistance.

In addition, benzene is covered through amutual aid response agreement, known as theChemical Industry Mutual Aid Network (CHEMNET).This agreement enables a fellow participatingcompany that is located closer to the incident, to respond to the incident

This section focuses on benzene transportationincidents. Please be aware that CHEMTREC can alsobe contacted for non-transportation and medicalincidents.


7.3 Transport Classifications for Benzene

Road/Rail - U.S. Department of Transportation (DOT)Proper Shipping Name: BenzeneHazard Class or Division: 3Packing Group: IIIdentification Number: UN1114Label/Placard Required: FlammableHazardous Substance RQ: Benzene, 10 poundsEmergency Response Guide: 130

Air - International Civil Aviation Organization (ICAO)International Air Transport Association (IATA)Proper Shipping Name: BenzeneClass: 3Packing Group: IIUN Number: UN1114Symbol: Flammable Liquid

Sea - International Maritime Organization (IMO)Proper Shipping Name: BenzeneClass: 3.2Packing Group: IIUN Number: UN1114Symbol: Flammable LiquidPollution Category: CEuropean BehaviorClassification: 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.

8. POLLUTION PREVENTION

8-19/04

0

10

20

30

FIGURE 8.1: TOTAL BENZENE TRI RELEASES 1990-2001

(Sources: 1992 and 1993 Toxics Release Inventory)

8.1 SARA Title III Toxics Release Inventory (TRI) Data

The Toxics Release Inventory (TRI) was establishedunder the Emergency Planning and CommunityRight-to-Know Act of 1986 (EPCRA). The TRI is apublicly available database that contains specifictoxic chemical release and transfer information from manufacturing facilities throughout the UnitedStates. Toxics Release Inventory (TRI) Program

<http://www.epa.gov/tri/>

Each year, manufacturing facilities meetingcertain activity thresholds must report their

estimated releases and transfers of listed toxicchemicals to the EPA and to the state in which thefacility is located. Benzene was included among thelisted chemicals.

Industry has been very involved in reducing the level of benzene emissions. Figure 8.1 showsthe TRI volumes for total benzene releases for thelast 10 reporting years. It should be noted thatapproximately 95% of the benzene releases are to air.




8.2 Emission Reduction Measures

Shell Chemical LP has been actively involved in itsown as well as government required programs toreduce benzene emissions from its manufacturingand distribution facilities. Government programsinclude the National Emissions Standards forHazardous Air Pollutants (NESHAP), to reducebenzene emissions from waste streams, vents, andfugitive emission sources. In addition to thebenzene NESHAP program, the EPA established avoluntary pollution prevention initiative called the33/50 Program. Using 1988 TRI reporting data as abaseline, the EPA selected 17 priority chemicals forwhich an interim goal was to achieve 33% reductionby 1992, and 50% or more reduction in reportedTRI releases by 1995.

Benzene was one of the 17 priority chemicals.Through 1992, a 33% reduction in benzene TRIreleases had been achieved by Shell Chemicals*; the company also met the 50% reduction target by 1995. Benzene emission reduction activities thathave been planned, completed, or are in progress at Shell Chemicals include those listed below. These activities are provided to present informationfor consideration on various ways that benzenereleases 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.

• 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 blanketingsystems for these tanks.

• Routing of water streams with potentialbenzene contamination, including somerecovered groundwater, to closed systems tocollect and process.

• Installation of "closed loop" sample stations inthe unit and at the process tanks.

• Upgrade of the vacuum system on the extraction plants to remove steam eductorexhaust from the atmosphere.

A-14/04

The Shell Chemicals CompaniesCommitment 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 ourcustomers, shareholders and society at large, to begood neighbors and to contribute to sustainabledevelopment.

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.

APPENDIX A



B-19/04

(A) SCOPE AND APPLICATION(1) This section applies to all occupational exposuresto benzene. Chemical Abstracts Service RegistryNo. 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 finaldischarge from bulk wholesale storage facilities, except that operations where gasoline or motor fuels are dispensed formore than 4 hours per day in an indoor location are covered by this section.

(ii)LOADING AND UNLOADING operations atbulk wholesale storage facilities which usevapor control systems for all loading andunloading operations, except for the provisionsof 29 CFR 1910.1200 as incorporated into thissection and the emergency provisions ofparagraphs (G) and (I)(4) of this section.

(iii) THE STORAGE, TRANSPORTATION, DISTRI-BUTION OR SALE of benzene or liquidmixtures containing more than 0.1 percentbenzene in intact containers or in transporta-tion pipelines while sealed in such a manneras to contain benzene vapors or liquid,

except for the provisions of 29 CFR 1910.1200 as incorporated into this sectionand the emergency provisions of paragraphs(G) and (I)(4) of this section.

(iv) CONTAINERS AND PIPELINES carrying mixtures with less than 0.1 percent benzeneand natural gas processing plants processinggas with less than 0.1 percent benzene.

(v)WORK OPERATIONS where the only exposureto benzene is from liquid mixtures containing0.5 percent or less of benzene by volume, orthe vapors released from such liquids untilSeptember 12, 1988; work operations wherethe only exposure to benzene is from liquidmixtures containing 0.3 percent or less ofbenzene by volume or the vapors releasedfrom such liquids from September 12, 1988,to September 12, 1989; and work operationswhere the only exposure to benzene is fromliquid mixtures containing 0.1 percent or lessof benzene by volume or the vapors releasedfrom such liquids after September 12, 1989;except that tire building machine operatorsusing solvents with more than 0.1 percentbenzene are covered by paragraph (I) of thissection.

(vi)OIL AND GAS DRILLING, PRODUCTIONAND SERVICING OPERATIONS.

APPENDIX B

OSHA Benzene Standard (29 CFR 1910.1028)

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.



B-2 9/04

(vii) COKE OVEN BATTERIES.

(3) The cleaning and repair of barges and tankerswhich have contained benzene are excluded fromparagraph (F) methods of compliance, paragraph(E)(1) exposure monitoring-general, and paragraph(E)(6) accuracy of monitoring. Engineering andwork practice controls shall be used to keep B-1OSHA Benzene Standard.exposures below 10 ppmunless 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-hourtime-weighted average.

“Assistant Secretary” means the AssistantSecretary of Labor for Occupational Safety andHealth, U.S. Department of Labor, or designee.“Authorized person” means any person specificallyauthorized by the employer whose duties requirethe person to enter a regulated area, or any personentering such an area as a designated representativeof employees for the purpose of exercising the rightto observe monitoring and measuring proceduresunder paragraph (L) of this section, or any otherperson authorized by the Act or regulations issuedunder the Act.

“Benzene” (C6 H6 ) (CAS Registry No. 71-43-2)means liquefied or gaseous benzene. It includesbenzene contained in liquid mixtures and thebenzene vapors released by these liquids. It doesnot include trace amounts of unreacted benzenecontained in solid materials.

“Bulk wholesale storage facility” means a bulkterminal or bulk plant where fuel is stored prior toits delivery to wholesale customers.

“Container” means any barrel, bottle, can, cylinder, drum, reaction vessel, storage tank, or thelike, 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, ordesignee.

“Emergency” means any occurrence such as,but not limited to, equipment failure, rupture ofcontainers, or failure of control equipment which

may or does result in an unexpected significantrelease of benzene.

“Employee exposure” means exposure to airborne benzene which would occur if theemployee were not using respiratory protectiveequipment.

“Regulated area” means any area where airborneconcentrations of benzene exceed or can reasonablybe expected to exceed, the permissible exposurelimits, either the 8-hour time weighted average exposure of 1 ppm or the short-term exposure limitof 5 ppm for 15 minutes.

“Vapor control system” means any equipmentused for containing the total vapors displacedduring the loading of gasoline, motor fuel or otherfuel tank trucks and the displacing of these vaporsthrough a vapor processing system or balancing thevapor with the storage tank. This equipment alsoincludes systems containing the vapors displacedfrom the storage tank during the unloading of thetank truck which balance the vapors back to thetank 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 averagedover any 15 minute period.

(D) REGULATED AREAS(1) The employer shall establish a regulated areawherever the airborne concentration of benzeneexceeds or can reasonably be expected to exceedthe permissible exposure limits, either the 8-hourtime weighted average exposure of 1 ppm or theshort-term exposure limit of 5 ppm for 15 minutes.

(2) Access to regulated areas shall be limited toauthorized persons.

B-39/04

(3) Regulated areas shall be determined from therest of the workplace in any manner that minimizesthe number of employees exposed to benzenewithin the regulated area.

(E) EXPOSURE MONITORING

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

be made from breathing zone air samplesthat are representative of each employee’saverage exposure to airborne benzene.

(ii) Representative 8-hour TWA employee exposures shall be determined on the basisof one sample or samples representing thefull shift exposure for each job classificationin each work area.

(iii)Determinations of compliance with the STELshall be made from 15 minute employeebreathing zone samples measured at operations where there is reason to believeexposures are high, such as where tanks areopened, filled, unloaded or gauged; wherecontainers or process equipment are openedand where benzene is used for cleaning or asa solvent in an uncontrolled situation. Theemployer may use objective data, such asmeasurements from brief period measuringdevices, to determine where STEL monitoringis needed.

(iv) Except for initial monitoring as requiredunder paragraph (E)(2) of this section, wherethe employer can document that one shiftwill consistently have higher employee exposures for an operation, the employershall only be required to determine representative employee exposure for thatoperation during the shift on which thehighest exposure is expected.

(2) INITIAL MONITORING(i) Each employer who has a place of employ-

ment covered under paragraph (A)(1) of this

section shall monitor each of these workplaces and work operations to determineaccurately the airborne concentrations ofbenzene to which employees may be exposed.

(ii) The initial monitoring required under paragraph (E)(2)(i) of this section shall becompleted by 60 days after the effective dateof this standard or within 30 days of theintroduction of benzene into the workplace.Where the employer has monitored withinone year prior to the effective date of thisstandard and the monitoring satisfies all otherrequirements of this section, the employermay rely on such earlier monitoring results tosatisfy 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 employeeexposure at or above the action level but ator below the TWA, the employer shall repeatsuch monitoring for each such employee atleast every year.

(ii) If the monitoring required by paragraph(E)(2)(i) of this section reveals employeeexposure above the TWA, the employer shallrepeat such monitoring for each suchemployee at least every six (6) months.

(iii) The employer may alter the monitoringschedule from every six months to annuallyfor any employee for whom two consecutivemeasurements taken at least 7 days apartindicate that the employee exposure hasdecreased to the TWA or below, but is at orabove the action level.

(iv)Monitoring for the STEL shall be repeated asnecessary to evaluate exposures of employeessubject to short term exposures.

9/04B-4

(4) TERMINATION OF MONITORING(i) If the initial monitoring required by paragraph

(E)(2)(i) of this section reveals employeeexposure to be below the action level theemployer may discontinue the monitoring forthat employee, except as otherwise requiredby paragraph (E)(5) of this section.

(ii) If the periodic monitoring required by paragraph (E)(3) of this section reveals thatemployee exposures, as indicated by at leasttwo consecutive measurements taken at least7 days apart, are below the action level theemployer may discontinue the monitoring forthat employee, except as otherwise requiredby 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 hasbeen a change in the production, process,control equipment, personnel or work practices which may result in new or additionalexposures to benzene, or when the employerhas any reason to suspect a change whichmay result in new or additional exposures.

(ii) Whenever spills, leaks, ruptures or otherbreakdowns occur that may lead to employeeexposure, the employer shall monitor (usingarea or personal sampling) after the cleanupof the spill or repair of the leak, rupture orother breakdown to ensure that exposureshave returned to the level that existed priorto the incident.

(6) ACCURACY OF MONITORINGMonitoring shall be accurate, to a confidence levelof 95 percent, to within plus or minus 25 percentfor airborne concentrations of benzene.

(7) EMPLOYEE NOTIFICATION OFMONITORING RESULTS

(i) The employer shall, within 15 working daysafter the receipt of the results of any monitoring performed under this standard,notify each employee of these results inwriting either individually or by posting ofresults in an appropriate location that isaccessible to affected employees.

(ii) Whenever the PELs are exceeded, the writtennotification required by paragraph (E)(7)(i) ofthis section shall contain the corrective actionbeing taken by the employer to reduce theemployee exposure to or below the PEL, orshall refer to a document available to theemployee which states the corrective actionsto be taken.

(F) METHODS OF COMPLIANCE

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

controls and work practices to reduce andmaintain employee exposure to benzene ator below the permissible exposure limits,except to the extent that the employer canestablish that these controls are not feasibleor where the provisions of paragraph(F)(1)(iii) or (G)(1) of this section apply.

(ii) Wherever the feasible engineering controlsand work practices which can be institutedare not sufficient to reduce employee exposureto or below the PELs, the employer shall usethem to reduce employee exposure to thelowest levels achievable by these controlsand shall supplement them by the use of respiratory protection which complies withthe requirements of paragraph (G) of thissection.

(iii)Where the employer can document thatbenzene is used in a workplace less than atotal of 30 days per year, the employer shalluse engineering controls, work practice controls or respiratory protection or any

B-59/04

combination of these controls to reduceemployee exposure to benzene to or belowthe PELs, except that employers shall useengineering and work practice controls, iffeasible, to reduce exposure to or below 10ppm as an 8-hour TWA.

(2) COMPLIANCE PROGRAM(i) When any exposures are over the PEL, the

employer shall establish and implement awritten program to reduce employee exposureto or below the PEL primarily by means ofengineering and work practice controls, asrequired by paragraph (F)(1) of this section.

(ii) The written program shall include a schedulefor development and implementation of theengineering and work practice controls.These plans shall be reviewed and revised asappropriate based on the most recent exposuremonitoring data, to reflect the current statusof the program.

(iii)Written compliance programs shall be furnished upon request for examination and copying to the Assistant Secretary, theDirector, affected employees and designatedemployee representatives.

(G) RESPIRATORY PROTECTION

(1) GENERALThe employer shall provide respirators and assure that they are used, where required by thissection. Respirators shall be used in the followingcircumstances:

(i) During the time period necessary to install or implement feasible engineering and workpractice controls;

(ii) In work operations for which the employerestablishes that compliance with either theTWA or STEL through the use of engineeringand work practice controls is not feasible,such as some maintenance and repair activities,

vessel cleaning, or other operations whereengineering and work practice controls areinfeasible because exposures are intermittentin nature and limited in duration;

(iii) In work situations where feasible engineeringand work practice controls are not yet sufficientor are not required under paragraph (F)(1)(iii)of this section to reduce exposure to orbelow the PELs; and (iv) In emergencies.

(2) RESPIRATOR SELECTION(i) Where respirators are required or allowed

under this section, the employer shall selectand provide, at no cost to the employee, theappropriate respirator as specified in Table 1,and shall assure that the employee uses therespirator provided.

(ii) The employer shall select respirators fromamong those jointly approved by the MineSafety and Health Administration and theNational Institute for Occupational Safety andHealth under the provisions of 30 CFR Part11. Negative pressure respirators shall havefilter elements approved by MSHA/NIOSH for organic vapors or benzene.

(iii)Any employee who cannot wear a negativepressure respirator shall be given the optionof wearing a respirator with less breathingresistance such as a powered air-purifyingrespirator or supplied air respirator.

(3) RESPIRATOR PROGRAMThe employer shall institute a respiratory protectionprogram 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 purifyingelement at the expiration of service life or atthe beginning of each shift in which they will be used, whichever comes first.

9/04B-6

(ii) If an air purifying element becomes availablewith an end of useful life indicator forbenzene approved by MSHA/NIOSH, theelement may be used until such time as theindicator shows no further useful life.

(iii) The employer shall permit employees whowear respirators to leave the regulated areato wash their faces and respirator facepiecesas necessary in order to prevent skin irritationassociated with respirator use or to changethe filter elements of air-purifying respiratorswhenever they detect a change in breathingresistance or chemical vapor breakthrough.

(5) RESPIRATOR FIT TESTING(i) The employer shall perform, and certify the

results of, either quantitative or qualitative fittests at the time of initial fitting and at leastannually thereafter for each employeewearing a negative pressure respirator. The test shall be used to select a respiratorfacepiece which exhibits minimum leakageand provides the required protection as prescribed in Table 1. The employer shallprovide and assure that the employee wearsa respirator demonstrated by the fit test toprovide the required protection.

(ii) The employer shall follow the test protocolsoutlined in Appendix E of this standard forwhichever type of fit testing the employerchooses.

(H) PROTECTIVE CLOTHINGAND EQUIPMENT

Personal protective clothing and equipment shall beworn where appropriate to prevent eye contact andlimit dermal exposure to liquid benzene. Protectiveclothing and equipment shall be provided by theemployer at no cost to the employee and theemployer shall assure its use where appropriate.Eye and face protection shall meet the requirementsof 29 CFR 1910.133.

TABLE 1: RESPIRATORY PROTECTION FOR BENZENE

Airborne Concentration

of Benzene or Respirator Type

Condition of Use

(a) Less than or (1)Half-mask air-purifying

equal to 10 ppm. respirator with organic

vapor cartridge.

(b) Less than or (1)Full facepiece

equal to 50 ppm. respirator with organic

vapor cartridges.

(2)Full facepiece gas

mask with chin

style canister.1

(c) Less than or (1)Full facepiece

equal to 100 ppm. powered air-purifying

respirator with organic

vapor canister.1

(d) Less than or (1) Supplied air respirator

equal to 1,000 ppm. with full facepiece in

positive-pressure mode.

(e) Greater than 1,000 (1) Self-contained breathing

ppm or unknown apparatus with full

concentration. 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-79/04

(I) MEDICAL SURVEILLANCE

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

surveillance program for employees who areor may be exposed to benzene at or abovethe action level 30 or more days per year; foremployees who are or may be exposed tobenzene at or above the PELs 10 or moredays per year; for employees who have beenexposed to more than 10 ppm of benzene for30 or more days in a year prior to the effectivedate of the standard when employed by theircurrent employer; and for employeesinvolved in the tire building operations calledtire building machine operators, who use solvents containing greater than 0.1% benzene.

(ii) The employer shall assure that all medicalexaminations and procedures are performedby or under the supervision of a licensedphysician and that all laboratory tests areconducted by an accredited laboratory.

(iii) The employer shall assure that persons otherthan licensed physicians who administer thepulmonary function testing required by thissection shall complete a training course inspirometry sponsored by an appropriate governmental, academic or professional institution.

(iv) The employer shall assure that all examinations and procedures are providedwithout cost to the employee and at a reasonable time and place.

(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 eachemployee covered by paragraph (I)(1)(i) ofthis section with a medical examinationincluding the following elements:(A) A DETAILED OCCUPATIONAL HISTORY

which includes:

(1) Past work exposure to benzene or any

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 PULMONARYFUNCTION TEST.

(ii) No initial medical examination is required to satisfy the requirements of paragraph(I)(2)(i) of this section if adequate recordsshow that the employee has been examinedin accordance with the procedures of paragraph (I)(2)(i) of this section within thetwelve months prior to the effective date ofthis standard.

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(3) PERIODIC EXAMINATIONS(i) The employer shall provide each employee

covered under paragraph (I)(1)(i) of thissection with a medical examination annuallyfollowing the previous examination. Theseperiodic examinations shall include at leastthe 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 andsymptoms commonly associated with toxicexposure to benzene, the employer shallprovide the employee with an additionalmedical examination which shall includethose elements considered appropriate by the examining physician.

(iii) For persons required to use respirators for at least 30 days a year, a pulmonary functiontest shall be performed every three (3) years.A specific evaluation of the cardiopulmonarysystem 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 tobenzene in an emergency situation, theemployer shall have the employee provide a urine sample at the end of the employee’sshift and have a urinary phenol test

performed on the sample within 72 hours.The urine specific gravity shall be correctedto 1.024.

(ii) If the result of the urinary phenol test isbelow 75 mg phenol/L of urine, no furthertesting is required.

(iii) If the result of the urinary phenol test isequal to or greater than 75 mg phenol/L ofurine, the employer shall provide theemployee with a complete blood countincluding an erythrocyte count, leukocytecount with differential and thrombocytecount at monthly intervals for a duration ofthree (3) months following the emergencyexposure.

(iv) If any of the conditions specified in paragraph(I)(5)(i) of this section exists, then the furtherrequirements of paragraph (I)(5) of thissection shall be met and the employer shall,in addition, provide the employees with periodic examinations if directed by thephysician.

(5) ADDITIONAL EXAMINATIONS AND REFERRALS(i) Where the results of the complete blood

count required for the initial and periodicexaminations indicate any of the followingabnormal conditions exist, then the bloodcount 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 individual’s 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 employee’s most recent values or falls outside the normal limit (95% C.I.) as determined by the laboratory.

B-99/04

(C) The leukocyte count is below 4,000 per mm 3 or there is an abnormal differential count.

(ii) If the abnormality persists, the examiningphysician shall refer the employee to a hematologist or an internist for further evaluation unless the physician has goodreason to believe such referral is unnecessary.(See Appendix C for examples of conditionswhere a referral maybe unnecessary.)

(iii) The employer shall provide the hematologistor internist with the information required tobe provided to the physician under para-graph (I)(6) of this section and the medicalrecord required to be maintained by paragraph(K)(2)(ii) of this section.

(iv) The hematologist’s or internist’s evaluationshall include a determination as to the needfor additional tests, and the employer shallassure that these tests are provided.

(6) INFORMATION PROVIDED TO THE PHYSICIANThe employer shall provide the following

information to the physician:

(i) A copy of this regulation and its appendices;

(ii) A description of the affected employee’sduties as they relate to the employee’s exposure;

(iii) The employee’s actual or representativeexposure level;

(iv) A description of any personal protectiveequipment used or to be used; and

(v) Information from previous employment-related medical examinations of the affectedemployee which is not otherwise available tothe examining physician.

(7) PHYSICIAN’S WRITTEN OPINIONS(i) For each examination under this section, the

employer shall obtain and provide theemployee with a copy of the examiningphysician’s written opinion within 15 days ofthe examination. The written opinion shall belimited to the following information:(A) The occupationally pertinent results ofthe medical examination and tests;(B) The physician’s opinion concerning

whether the employee has any detected medical conditions which would place the employee’s health at greater than normal risk of material impairment from exposure to benzene;

(C) The physician’s recommended limitations upon the employee’s exposure to benzene or upon the employee’s 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 employershall not reveal specific records, findings anddiagnoses that have no bearing on theemployee’s ability to work in a benzene-exposed 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, theemployee shall be removed from areas where exposures may exceed the action level until such time as the physician makesa determination under paragraph (I)(8)(ii) of this section.

(ii) Following the examination and evaluation by the hematologist/internist, a decision toremove an employee from areas wherebenzene exposure is above the action level

9/04B-10

or to allow the employee to return to areaswhere benzene exposure is above the actionlevel shall be made by the physician in consultation with the hematologist/internist.This decision shall be communicated inwriting to the employer and employee. In thecase of removal, the physician shall state therequired probable duration of removal fromoccupational exposure to benzene above theaction level and the requirements for futuremedical examinations to review the decision.

(iii) For any employee who is removed pursuantto paragraph (I)(8)(ii) of this section, the employer shall provide a follow-upexamination. The physician, in consultationwith the hematologist/ internist, shall make adecision within 6 months of the date theemployee was removed as to whether theemployee shall be returned to the usual jobor whether the employee should be removedpermanently.

(iv) Whenever an employee is temporarilyremoved from benzene exposure pursuant toparagraph (I)(8)(i) or (I)(8)(ii) of this section,the employer shall transfer the employee to acomparable job for which the employee isqualified (or can be trained for in a shortperiod) and where benzene exposures are aslow as possible, but in no event higher thanthe action level. The employer shall maintainthe employee’s current wage rate, seniorityand other benefits. If there is no such jobavailable, the employer shall provide medicalremoval protection benefits until such a jobbecomes available or for 6 months, whichevercomes first.

(v) Whenever an employee is removed permanently from benzene exposure basedon a physician’s recommendation pursuant toparagraph (I)(8)(iii) of this section, theemployee shall be given the opportunity totransfer to another position which is availableor later becomes available for which theemployee is qualified (or can be trained for

in a short period) and where benzene exposures are as low as possible but in noevent higher than the action level. Theemployer shall assure that such employeesuffers 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 bene-fits immediately following each occasion anemployee is removed from exposure tobenzene because of hematological findingspursuant to paragraphs (I)(8)(i) and (ii) ofthis section, unless the employee has beentransferred to a comparable job wherebenzene exposures are below the actionlevel.

(ii) For the purposes of this section, the require-ment that an employer provide medicalremoval protection benefits means that theemployer shall maintain the current wagerate, seniority and other benefits of anemployee as though the employee had notbeen removed.

(iii) The employer’s obligation to provide medicalremoval protection benefits to a removedemployee shall be reduced to the extent thatthe employee receives compensation forearnings lost during the period of removaleither from a publicly or employer-fundedcompensation program, or from employmentwith another employer made possible byvirtue of the employee’s removal.

B-119/04

(J) COMMUNICATION OF BENZENEHAZARDS TO EMPLOYEES

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

to regulated areas. The signs shall bear thefollowing legend:

DANGERBENZENE

CANCER HAZARDFLAMMABLE-NO SMOKING

AUTHORIZED PERSONNEL ONLYRESPIRATOR REQUIRED

(ii) The employer shall ensure that labels orother appropriate forms of warning are provided for containers of benzene withinthe workplace. There is no requirement tolabel pipes. The labels shall comply with therequirements of 29 CFR 1910.1200(f) and inaddition shall include the following legend:

DANGERCONTAINS 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) whichaddresses benzene and complies with 29 CFR 1910.1200.

(ii) Employers who are manufacturers orimporters shall:(A) Comply with paragraph (A) of this

section, and(B) Comply with the requirement in OSHA’s

Hazard Communication Standard, 29 CFR 1910.1200, that they deliver to downstream employers an MSDS which addresses benzene.

(3) INFORMATION AND TRAINING(i) The employer shall provide employees withinformation and training at the time of theirinitial assignment to a work area wherebenzene is present. If exposures are abovethe action level, employees shall be providedwith information and training at leastannually thereafter.

(ii) The training program shall be in accordancewith the requirements of 29 CFR 1910.1200(H)(1) and (2), and shall include specificinformation on benzene for each category ofinformation included in that section.

(iii) In addition to the information required under29 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 requiredby paragraph (E) of this section, in accordancewith 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

9/04B-12

(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 atleast 30 years, in accordance with 29 CFR1910.20.

(2) MEDICAL SURVEILLANCE(i) The employer shall establish and maintain an

accurate record for each employee subject tomedical surveillance required by paragraph(I) of this section, in accordance with 29 CFR1910.20.

(ii) This record shall include:(A) The name and social security number of

the employee;(B) The employer’s copy of the physician’s

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 employee’s medical and work history related to exposure to benzene or any other hematologic toxins.

(iii) The employer shall maintain this record forat least the duration of employment plus 30years, in accordance with 29 CFR 1910.20.

(3) AVAILABILITY(i) The employer shall assure that all records

required to be maintained by this sectionshall be made available upon request to theAssistant Secretary and the Director for exam-ination and copying.

(ii) Employee exposure monitoring recordsrequired by this paragraph shall be provided

upon request for examination and copying toemployees, employee representatives, andthe Assistant Secretary in accordance with 29CFR 1910.20 (A) through (E) and (G) through(I).

(iii) Employee medical records required by thisparagraph shall be provided upon request forexamination and copying, to the subjectemployee, to anyone having the specificwritten consent of the subject employee, andto the Assistant Secretary in accordance with29 CFR 1910.20.

(4) TRANSFER OF RECORDS(i) The employer shall comply with the require-

ments involving transfer of records set forthin 29 CFR 1019.20(H).

(ii) If the employer ceases to do business andthere is no successor employer to receive andretain the records for the prescribed period,the employer shall notify the Director, at leastthree (3) months prior to disposal, and trans-mit them to the Director if required by theDirector within that period.

(L) OBSERVATION OF MONITORING

(1) EMPLOYEE OBSERVATIONThe employer shall provide affected employees, ortheir designated representatives, an opportunity toobserve the measuring or monitoring of employeeexposure to benzene conducted pursuant to para-graph (E) of this section.

(2) OBSERVATION PROCEDURESWhen observation of the measuring or monitoringof employee exposure to benzene requires entryinto areas where the use of protective clothing andequipment or respirators is required, the employershall provide the observer with personal protectiveclothing and equipment or respirators required tobe worn by employees working in the area, assurethe use of such clothing and equipment or respira-tors, and require the observer to comply with allother applicable safety and health procedures.

B-139/04

(M) DATES

(1) EFFECTIVE DATEThe standard shall become effective December 10,1987.

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

(M) of this section, except the engineeringcontrol requirements of paragraph (F)(1) ofB-12 2/96.this section shall be completedwithin sixty (60) days after the effective dateof the standard.

(ii) Engineering and work practice controlsrequired by paragraph (F)(1) of this sectionshall be implemented no later than 2 yearsafter the effective date of the standard.

(iii) Coke and coal chemical operations maycomply with paragraph (M)(2)(ii) of thissection or alternately include within the compliance program required by paragraph(F)(2) of this section, a requirement to phasein engineering controls as equipment isrepaired and replaced. For coke and coalchemical operations choosing the latter alternative, compliance with the engineeringcontrols requirements of paragraph (F)(1) of this section shall be achieved no later than 5 years after the effective date of thisstandard and substantial compliance with the engineering control requirements shall beachieved within 3 years of the effective dateof 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 todetract from any existing obligations. The protocolson respiratory fit testing in Appendix E are mandatory.(Approved by the Office of Management andBudget under control number 1218-0129)

APPENDIX A TO §1910.1028-SUBSTANCE SAFETY DATASHEET, BENZENE(I) SUBSTANCE IDENTIFICATION

(A) SUBSTANCE: Benzene.(B) PERMISSIBLE EXPOSURE: Except as to the

use of gasoline, motor fuels and other fuelssubsequent to discharge from bulk terminalsand other exemptions specified in § 1910.1028(A)(2):

(1) AIRBORNE: The maximum time-weightedaverage (TWA) exposure limit is 1 part ofbenzene vapor per million parts of air (1ppm) for an 8-hour workday and themaximum short-term exposure limit (STEL) is 5 ppm for any 15-minute period.

(2) DERMAL: Eye contact shall be prevented andskin contact with liquid benzene shall belimited.

(C) APPEARANCE AND ODOR: Benzene is aclear, colorless liquid with a pleasant, sweetodor. The odor of benzene does not provideadequate warning of its hazard.

(II) HEALTH HAZARD DATA(A) WAYS IN WHICH BENZENE AFFECTS YOUR

HEALTH: Benzene can affect your health ifyou inhale it, or if it comes in contact withyour skin or eyes. Benzene is also harmful ifyou happen to swallow it.

(B) EFFECTS OF OVEREXPOSURE(1) SHORT-TERM (ACUTE) OVEREXPOSURE: If

you are overexposed to high concentrationsof benzene, well above the levels where itsodor is first recognizable, you may feelbreathless, irritable, euphoric, or giddy; youmay experience irritation in eyes, nose, andrespiratory tract. You may develop aheadache, feel dizzy, nauseated, or intoxicated.Severe exposures may lead to convulsionsand loss of consciousness.

(2) LONG-TERM (CHRONIC) EXPOSURE:Repeated or prolonged exposure to benzene,even at relatively low concentrations, mayresult in various blood disorders, rangingfrom anemia to leukemia, an irreversible,

9/04B-14

fatal disease. Many blood disorders associatedwith benzene exposure may occur withoutsymptoms.

(III) PROTECTIVE CLOTHING AND EQUIPMENT(A) RESPIRATORS: Respirators are required for

those operations in which engineering controlsor work practice controls are not feasible toreduce exposure to the permissible level.However, where employers can documentthat benzene is present in the workplace lessthan 30 days a year, respirators may be usedin lieu of engineering controls. If respiratorsare worn, they must have joint Mine Safetyand Health Administration and the NationalInstitute for Occupational Safety and Health(NIOSH) seal of approval, and cartridge orcanisters must be replaced before the end oftheir 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 respiratorfrom your employer. You must be thoroughlytrained to use the assigned respirator, and thetraining will be provided by your employer.

(B) PROTECTIVE CLOTHING: You must wearappropriate protective clothing (such asboots, gloves, sleeves, aprons, etc.) over anyparts of your body that could be exposed toliquid benzene.

(C) EYE AND FACE PROTECTION: You mustwear splash-proof safety goggles if it is possible that benzene may get into youreyes. In addition, you must wear a faceshield if your face could be splashed withbenzene liquid.

(IV) EMERGENCY AND FIRST AID PROCEDURES(A) EYE AND FACE EXPOSURE: If benzene is

splashed in your eyes, wash it out immediatelywith 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 exposedskin with large amounts of water and soap

immediately. Wash contaminated clothingbefore you wear it again.

(C) BREATHING: If you or any other personbreathes in large amounts of benzene, get theexposed person to fresh air at once. Applyartificial respiration if breathing has stopped.Call for medical assistance or a doctor assoon as possible. Never enter any vessel or confined space where the benzene concentration might be high without propersafety equipment and at least one otherperson 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 medicalassistance or a doctor immediately.

(V) MEDICAL REQUIREMENTSIf you are exposed to benzene at a concentration ator above 0.5 ppm as an 8-hour time-weightedaverage, or have been exposed at or above 10 ppmin the past while employed by your currentemployer, your employer is required to provide amedical examination and history and laboratorytests within 60 days of the effective date of thisstandard and annually thereafter. These tests shallbe provided without cost to you. In addition, if youare accidentally exposed to benzene (either byingestion, inhalation, or skin/eye contact) underemergency conditions known or suspected to constitute toxic exposure to benzene, your employeris required to make special laboratory tests available to you.

(VI) OBSERVATION OF MONITORINGYour employer is required to perform measurementsthat are representative of your exposure to benzeneand you or your designated representative are entitled to observe the monitoring procedure. You are entitled to observe the steps taken in themeasurement procedure, and to record the resultsobtained. When the monitoring procedure is takingplace in an area where respirators or personal protective clothing and equipment are required tobe worn, you or your representative must also beprovided with, and must wear the protective clothing and equipment.

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(VII) ACCESS TO RECORDSYou or your representative are entitled to see therecords of measurements of your exposure tobenzene upon written request to your employer.Your medical examination records can be furnishedto yourself, your physician or designated represen-tative upon request by you to your employer.

(VIII) PRECAUTIONS FOR SAFE USE, HANDLINGAND STORAGEBenzene liquid is highly flammable. It should bestored in tightly closed containers in a cool, wellventilated area. Benzene vapor may form explosivemixtures in air. All sources of ignition must be con-trolled. Use nonsparking tools when opening orclosing benzene containers. Fire extinguishers,where provided, must be readily available. Knowwhere they are located and how to operate them.Smoking is prohibited in areas where benzene isused or stored. Ask your supervisor where benzeneis used in your area and for additional plant safetyrules.

APPENDIX B TO §1910.1028-SUBSTANCETECHNICAL 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.

(II) FIRE, EXPLOSION, AND REACTIVITY HAZARDDATA

(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 fire-exposed 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).

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(III) SPILL AND LEAK PROCEDURES(A) STEPS TO BE TAKEN IF THE MATERIAL IS

RELEASED OR SPILLED: As much benzene aspossible should be absorbed with suitablematerials such as dry sand or earth. Thatremaining must be flushed with largeamounts B-15 2/96.of water. Do not flushbenzene into a confined space, such as asewer, because of explosion danger. Removeall ignition sources. Ventilate enclosed places.

(B) WASTE DISPOSAL METHOD: Disposalmethods must conform to other jurisdictionalregulations. If allowed, benzene may be disposed of: (a) By absorbing it in dry sandor earth and disposing in a sanitary landfill;(b) if small quantities, by removing it to asafe location from buildings or other combustible sources, pouring it in dry sandor earth and cautiously igniting it; and (c) iflarge quantities, by atom-izing it in a suitablecombustion chamber.

(IV) MISCELLANEOUS PRECAUTIONS(A) HIGH EXPOSURE TO BENZENE can occur

when transferring the liquid from one container to another. Such operations shouldbe well ventilated and good work practicesmust be established to avoid spills.

(B) USE NON-SPARKING TOOLS to openbenzene containers which are effectivelygrounded and bonded prior to opening and pouring.

(C) EMPLOYERS MUST ADVISE EMPLOYEES ofall plant areas and operations where exposureto benzene could occur. Common operationsin which high exposures to benzene may beencountered are: the primary production andutilization of benzene, and transfer of benzene.

APPENDIX C TO §1910.1028-MEDICALSURVEILLANCE GUIDELINES FOR BENZENE(I) ROUTE OF ENTRYInhalation; skin absorption.

(II) TOXICOLOGYBenzene is primarily an inhalation hazard. Systemicabsorption may cause depression of the hematopoietic

system, pancytopenia, aplastic anemia, andleukemia. Inhalation of high concentrations canaffect central nervous system function. Aspiration of small amounts of liquid benzene immediatelycauses pulmonary edema and hemorrhage of pulmonary tissue. There is some absorption throughthe skin. Absorption may be more rapid in the caseof abraded skin, and benzene may be more readilyabsorbed if it is present in a mixture or as a contaminant in solvents which are readily absorbed.The defatting action of benzene may produceprimary irritation due to repeated or prolongedcontact with the skin. High concentrations are irritating to the eyes and the mucous membranes of the nose, and respiratory tract.

(III) SIGNS AND SYMPTOMSDirect skin contact with benzene may cause erythema. Repeated or prolonged contact mayresult in drying, scaling dermatitis, or developmentof secondary skin infections. In addition, there isbenzene absorption through the skin. Local effectsof benzene vapor or liquid on the eye are slight.Only at very high concentrations is there any smarting sensation in the eye. Inhalation of highconcentrations of benzene may have an initial stimulatory effect on the central nervous systemcharacterized 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 circulatorycollapse in a few minutes to several hours followingsevere exposures.

The detrimental effect on the blood-formingsystem of prolonged exposure to small quantities of benzene vapor is of extreme importance. Thehematopoietic system is the chief target forbenzene’s toxic effects which are manifested byalterations in the levels of formed elements in theperipheral blood. These effects have occurred atconcentrations of benzene which may not causeirritation of mucous membranes, or any unpleasantsensory effects. Early signs and symptoms ofbenzene morbidity are varied, often not readily

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noticed and non-specific. Subjective complaints ofheadache, dizziness, and loss of appetite mayprecede or follow clinical signs. Rapid pulse andlow blood pressure, in addition to a physicalappearance of anemia, may accompany a subjectivecomplaint of shortness of breath and excessivetiredness. Bleeding from the nose, gums, or mucousmembranes, and the development of purpuric spots(small bruises) B-16 2/96.may occur as the conditionprogresses. 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, orhyperplastic, and may not, in all situations, correlatewith peripheral blood-forming tissues. Because ofvariations in the susceptibility to benzene morbidity,there is no “typical” blood picture. The onset ofeffects of prolonged benzene exposure may bedelayed for many months or years after the actualexposure has ceased and identification or correlationwith benzene exposure must be sought out in theoccupational history.

(IV) TREATMENT OF ACUTE TOXIC EFFECTSREMOVE FROM EXPOSURE IMMEDIATELY.Make sure you are adequately protected and do notrisk being overcome by fumes. Give oxygen or artificial resuscitation if indicated. Flush eyes, washskin if contaminated and remove all contaminatedclothing. Symptoms of intoxication may persist following severe exposures. Recovery from mildexposures is usually rapid and complete.

(V) SURVEILLANCE AND PREVENTIVECONSIDERATIONS

(A) GENERALThe principal effects of benzene exposurewhich form the basis for this regulation arepathological changes in the hematopoieticsystem, reflected by changes in the peripheral blood and manifesting clinically as pancytopenia, aplastic anemia, andleukemia. Consequently, the medical surveillance program is designed to observe,on a regular basis, blood indices for earlysigns of these effects, and although earlysigns of leukemia are not usually available,

emerging diagnostic technology and innovativeregimes make consistent surveillance forleukemia, as well as other hematopoieticeffects, essential.

Initial examinations are to be providedwithin 60 days of the effective date of thisstandard, or at the time of initial assignment,and periodic examinations annually thereafter.There are special provisions for medical testsin the event of hematologic abnormalities orfor emergency situations.

The blood values which require referral toa hematologist or internist are noted in thestandard in paragraph (I)(5). The standardspecifies that blood abnormalities that persistmust be referred “unless the physician hasgood reason to believe such referral is unnecessary” (paragraph (I)(5)). Examples of conditions that could make a referralunnecessary despite abnormal blood limitsare iron or folate deficiency, menorrhagia, orblood loss due to some unrelated medicalabnormality.

Symptoms and signs of benzene toxicitycan be non-specific. Only a detailed historyand appropriate investigative procedures will enable a physician to rule out or confirmconditions that place the employee atincreased risk. To assist the examining physician with regard to which laboratorytests are necessary and when to refer anemployee to the specialist, OSHA has established the following guidelines.

(B) HEMATOLOGY GUIDELINESA minimum battery of tests is to be performedby strictly standardized methods.(1)Red cell, white cell, platelet counts, white

blood cell differential, hematocrit and redcell indices must be performed by anaccredited laboratory. The normal rangesfor the red cell and white cell counts areinfluenced by altitude, race, and sex, andtherefore should be determined by theaccredited laboratory in the specific areawhere the tests are performed.

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Either a decline from an absolutenormal or an individual’s base line to asubnormal value or a rise to a supra-normal value, are indicative of potentialtoxicity, particularly if all blood parametersdecline. The normal total white bloodcount is approximately 7,200/mm 3 plus orminus 3,000. For cigarette smokers, thewhite count may be higher and the upperrange may be 2,000 cells higher thannormal for the laboratory. In addition,infection, allergies B-17 2/96.and somedrugs may raise the white cell count. Thenormal platelet count is approximately250,000 with a range of 140,000 to400,000. Counts outside this range shouldbe regarded as possible evidence ofbenzene toxicity. Certain abnormalitiesfound through routine screening are ofgreater significance in the benzene-exposed worker and require promptconsultation with a specialist, namely:a. THROMBOCYTOPENIA.b. A TREND OF DECREASING WHITE

CELL, RED CELL, OR PLATELETINDICES in an individual over time is more worrisome than an isolated abnormal finding at one test time. Theimportance of trend highlights the needto compare an individual’s test resultsto baseline and/or previous periodictests.

c. A CONSTELLATION OR PATTERN OFABNORMALITIES in the different bloodindices is of more significance than asingle abnormality. A low white countnot associated with any abnormalities inother cell indices may be a normal statistical variation, whereas if the lowwhite count is accompanied by decreasesin the platelet and/or red cell indices,such a pattern is more likely to be associated with benzene toxicity andmerits thorough investigation.

Anemia, leukopenia, macrocytosisor an abnormal differential white bloodcell count should alert the physician to

further investigate and/or refer thepatient if repeat tests confirm theabnormalities. If routine screeningdetects an abnor-mality, follow-up testswhich may be helpful in establishingthe etiology of the abnormality are the peripheral blood smear and thereticulocyte count.

The extreme range of normal forreticulocytes is 0.4 to 2.5 percent of thered cells, the usual range being 0.5 to1.2 percent of the red cells, but thetypical value is in the range of 0.8 to1.0 percent. A decline in reticulocytesto levels of less than 0.4 percent is tobe regarded as possible evidence(unless another specific cause is found)of benzene toxicity requiring acceleratedsurveillance. An increase in reticulocytelevels 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 carefulexamination of the peripheral blood smear.As with reticulocyte count the smearshould be with fresh uncoagulated bloodobtained from a needle tip followingvenipuncture or from a drop of earlobeblood (capillary blood). If necessary, the smear may, under certain limited conditions, be made from a blood sampleanticoagulated with EDTA (but never withoxalate or heparin). When the smear is tobe prepared from a specimen of venousblood which has been collected by a commercial Vacutainer® type tube containing neutral EDTA, the smear shouldbe made as soon as possible after thevenesection. A delay of up to 12 hours is permissible between the drawing of the blood specimen into EDTA and theprepa-ration of the smear if the blood is stored at refrigerator (not freezing) temperature.

(3) The minimum mandatory observations tobe made from the smear are:a. The differential white blood cell count.

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b. Description of abnormalities in theappearance of red cells.

c. Description of any abnormalities in theplatelets.

d. A careful search must be made through-out every blood smear for immaturewhite cells such as band forms (in morethan normal proportion, i.e., over 10percent of the total differential count),any number of metamyelocytes, myelo-cytes or myelo-blasts. Any nucleate ormultinucleated red blood cells shouldbe reported. Large “giant” platelets orfragments of megakaryocytes must berecognized. B-18 2/96.

An increase in the proportion ofband forms among the neutrophilicgranulocytes is an abnormality deserv-ing special mention, for it mayrepresent a change which should beconsidered as an early warning ofbenzene toxicity in the absence ofother causative factors (most commonlyinfection). Likewise, the appearance ofmetamyelocytes, in the absence ofanother probable cause, is to be consid-ered a possible indication ofbenzene-induced toxicity.

An upward trend in the number ofbasophils, which normally do notexceed about 2.0 percent of the totalwhite cells, is to be regarded as possi-ble evidence of benzene toxicity. A risein the eosinophil count is less specificbut also may be suspicious of toxicity ifit rises above 6.0 percent of the totalwhite count.

The normal range of monocytes isfrom 2.0 to 8.0 percent of the totalwhite count with an average of about5.0 percent. About 20 percent of indi-viduals reported to have mild butpersisting abnormalities caused byexposure to benzene show a persistentmonocytosis. The findings of a mono-cyte count which persists at more than10 to 12 percent of the normal white

cell count (when the total count isnormal) or persistence of an absolutemonocyte count in excess of 800/mm 3should be regarded as a possible signof benzene-induced toxicity.

A less frequent but more seriousindication of benzene toxicity is thefinding in the peripheral blood of theso-called “pseudo” (or acquired) Pelger-Huet anomaly. In this anomaly many,or some-times the majority, of the neu-trophilic granulocytes possess tworound nuclear segments-less often oneor three round segments -rather thanthree normally elongated segments.When this anomaly is not hereditary, itis often but not invariably predictive ofsubsequent leukemia. However, onlyabout 2% of patients who ultimatelydevelop acute myelogenous leukemiashow the acquired Pelger-Huetanomaly. Other tests that can be admin-istered to investigate bloodabnormalities are discussed below;however, such procedures should beundertaken by the hematologist.

The normal range of monocytes isfrom 2.0 to 8.0 percent of the totalwhite count with an average of about5.0 percent. About 20 percent of indi-viduals reported to have mild butpersisting abnormalities caused byexposure to benzene show a persistentmonocytosis. The findings of a mono-cyte count which persists at more than10 to 12 percent of the normal whitecell count (when the total count isnormal) or persistence of an absolutemonocyte count in excess of 800/mm 3should be regarded as a possible signof benzene-induced toxicity.

A less frequent but more seriousindication of benzene toxicity is thefinding in the peripheral blood of theso-called “pseudo” (or acquired) Pelger-Huet anomaly. In this anomaly many,or some-times the majority, of the

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neutrophilic granulocytes possess tworound nuclear segments-less often oneor three round segments -rather thanthree normally elongated segments.When this anomaly is not hereditary, itis often but not invariably predictive ofsubsequent leukemia. However, onlyabout 2% of patients who ultimatelydevelop acute myelogenous leukemiashow the acquired Pelger-Huetanomaly. Other tests that can be administered to investigate bloodabnormalities are discussed below;however, such procedures should beundertaken by the hematologist.An uncommon sign, which cannot be detected from the smear, but can beelicited by a “sucrose water test” ofperipheral blood, is transient paroxysmalnocturnal hemoglobinuria (PNH), whichmay first occur insidiously during aperiod of established aplastic anemia,and maybe followed within one to afew years by the appearance of rapidlyfatal acute myelogenous leukemia.Clinical detection of PNH, which occursin only one or two percent of thosedestined to have acute myelogenousleukemia, may be difficult; if the“sucrose water test” is positive, thesomewhat more definitive Ham test,also known as the acid-serum hemolysistest, may provide confirmation.

e. Individuals documented to have developed acute myelogenous leukemiayears after initial exposure to benzenemay have progressed through a preliminary phase of hematologicabnormality. In some instances, pancytopenia (i.e., a lowering in thecounts of all circulating blood cells ofbone marrow origin, but not to theextent implied by the term “aplasticanemia”) preceded leukemia for manyyears. Depression of a single blood celltype or platelets may represent a harbinger of aplasia or leukemia. The

finding of two or more cytopenias, orpancytopenia in a benzene-exposedindividual, must be regarded as highlysuspicious of more advanced althoughstill reversible, toxicity. “Pancytopenia”coupled with the appear-ance of immature cells (myelocytes, myeloblasts,erythroblasts, etc.), with B-192/96.abnormal cells (pseudo Pelger-Huet anomaly, atypical nuclearheterochromatin, etc.), or unexplainedelevations of white blood cells must beregarded as evidence of benzene over-exposure unless proved otherwise.Many severely aplastic patients manifested the ominous finding of 5-10percent myeloblasts in the marrow,occasional myeloblasts and myelocytesin the blood and 20-30% monocytes. Itis evident that isolated cytopenias, pancytopenias, and even aplasticanemias induced by benzene may bereversible and complete recovery hasbeen reported on cessation of exposure.However, since any of these abnormalities is serious, the employeemust immediately be removed from anypossible exposure to benzene vapor.Certain tests may substantiate theemployee’s prospects for progression orregression. One such test would be anexamination of the bone marrow, butthe decision to perform a bone marrowaspiration or needle biopsy is made bythe hematologist.

The findings of basophilic stipplingin circulating red blood cells (usuallyfound in 1 to 5% of red cells followingmarrow injury), and detection in thebone marrow of what are termed“ringed sideroblasts” must be taken seriously, as they have been noted inrecent years to be premonitory signs of subsequent leukemia.

Recently peroxidase-staining of circulating or marrow neutrophil granulocytes, employing benzidine

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dihydrochloride, have revealed the disappearance of, or diminution in, peroxidase in a sizable proportion ofthe granulocytes, and this has beenreported as an early sign of leukemia.However, relatively few patients havebeen studied to date. Granulocyte granules are normally strongly peroxidase positive. A steady decline inleukocyte alkaline phosphatase has alsobeen reported as suggestive of earlyacute leukemia. Exposure to benzenemay cause an early rise in serum iron,often but not always associated with afall in the reticulocyte count. Thus,serial measurements of serum ironlevels may provide a means of determining whether or not there is atrend representing sustained suppressionof 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 alkalinephosphatase staining are usually undertaken when the index of suspicion for leukemia is high.

APPENDIX D TO §1910.1028-SAMPLINGAND ANALYTICAL METHODS FOR BENZENEMONITORING AND MEASUREMENT PROCE-DURESMeasurements taken for the purpose of determiningemployee exposure to benzene are best taken sothat the representative average 8-hour exposuremay be determined from a single 8-hour sample ortwo (2) 4-hour samples. Short-time interval samples(or grab samples) may also be used to determineaverage exposure level if a minimum of five measurements are taken in a random manner overthe 8-hour work shift. Random sampling means thatany portion of the work shift has the same chanceof being sampled as any other. The arithmeticaverage of all such random samples taken on onework shift is an estimate of an employee’s average

level of exposure for that work shift. Air samplesshould be taken in the employee’s breathing zone(air that would most nearly represent that inhaledby the employee). Sampling and analysis must beperformed with procedures meeting the requirementsof the standard.

There are a number of methods available formonitoring employee exposures to benzene. The sampling and analysis may be performed bycollection of the benzene vapor or charcoal absorption tubes, with subsequent chemical analysisby gas chromatography. Sampling and analysis mayalso be performed by portable direct reading instruments, real-time B-20 2/96.continuous monitoring systems, passive dosimeters or othersuitable methods. The employer has the obligationof selecting a monitoring method which meets theaccuracy and precision requirements of the standardunder his unique field conditions. The standardrequires that the method of monitoring must havean 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 MethodS311 and evaluated it at a benzene air concentrationof 1 ppm. A procedure for determining the benzeneconcentration in bulk material samples was alsoevaluated. This work, reported in OSHA LaboratoryMethod No. 12, includes the following two analyticalprocedures:

(I) OSHA METHOD 12 FOR AIR SAMPLESANALYTE: BenzeneMATRIX: AirPROCEDURE: Adsorption on charcoal, desorption with carbon disulfide, analysis by GC.DETECTION LIMIT: 0.04 ppmRECOMMENDED AIR VOLUME ANDSAMPLING RATE: 10L to 0.2 L/min.

1. PRINCIPLE OF THE METHOD

1.1 A known volume of air is drawn through acharcoal tube to trap the organic vapors present.

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1.2 The charcoal in the tube is transferred to asmall, stoppered vial, and the analyte is desorbedwith carbon disulfide.

1.3 An aliquot of the desorbed sample is injectedinto a gas chromatograph.

1.4 The area of the resulting peak is determinedand compared with areas obtained from standards.

2.ADVANTAGES AND DISADVANTAGES

OF THE METHOD

2.1 The sampling device is small, portable, andinvolved no liquids. Interferences are minimal, andmost of those which do occur can be eliminated byaltering chromatographic conditions. The samplesare analyzed by means of a quick, instrumentalmethod.

2.2 The amount of sample which can be taken islimited by the number of milligrams that the tubewill hold before overloading. When the samplevalue obtained for the backup section of the charcoaltube exceeds 25 percent of that found on the frontsection, the possibility of sample loss exists.

3.APPARATUS

3.1 A calibrated personal sampling pump whoseflow can be determined within ±5 percent at therecommended flow rate.

3.2 Charcoal tubes: Glass with both ends flamesealed, 07 cm long with a 6-mm O.D. and a 4-mmI.D., containing 2 sections of 20/40 mesh activatedcharcoal separated by a 2-mm portion of urethanefoam. The activated charcoal is prepared fromcoconut shells and is fired at 600 °C prior topacking. The adsorbing section contains 100 mg of charcoal, the backup section 50 mg. A 3-mmportion of urethane foam is placed between theoutlet end of the tube and the back-up section. Aplug 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.

3.3 Gas chromatograph equipped with a flame ionization detector.

3.4 Column (10-ft. x 1/8-in stainless steel) packedwith 80/100 Supelcoport coated with 20 percent SP2100, 0.1 percent CW 1500.

3.5 An electronic integrator or some other suitablemethod for measuring peak area.

3.6 Two-milliliter sample vials with Teflon-linedcaps.

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

3.9 Volumetric flasks: convenient sizes for makingstandard solutions.

4. REAGENTS

4.1 Chromatographic quality carbon disulfide (CS2): Most commercially available carbon disulfide contains a trace of benzene which must beremoved. It can be removed with the followingprocedure:

Heat under reflux for 2 to 3 hours, 500 mL ofcarbon disulfide, 10 mL concentrated sulfuric acid,and 5 drops of concentrated nitric acid. Thebenzene is converted to nitrobenzene. The carbondisulfide layer is removed, dried with anhydroussodium sulfate, and distilled. The recovered carbondisulfide should be benzene free. (It has recentlybeen determined that benzene can also be removedby 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 isprepared by adding 0.05 mL of p-cymene per milliliter of carbon sulfide. (The internal standardoffers a convenient means of correcting analytical

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response for slight inconsistencies in the size ofsample injections. If the external standard techniqueis preferred, the internal standard can be eliminated.)

4.5 Purified GC grade helium, hydrogen and air.

5. PROCEDURE5.1 Cleaning of equipment: All glassware used forthe laboratory analysis should be properly cleanedand free of organics which could interfere in theanalysis.

5.2 Calibration of personal pumps: Each pumpmust be calibrated with a representative charcoaltube in the line.

5.3 Collection and shipping of samples.

5.3.1 Immediately before sampling, break the endsof the tube to provide an opening at least one-halfthe 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 thesampling 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 passedthrough any hose or tubing before entering thecharcoal tube.

5.3.5 A sample size of 10 liters is recommended.Sample at a flow rate of approximately 0.2 liters perminute. The flow rate should be known with anaccuracy of at least ±5 percent.

5.3.6 The charcoal tubes should be capped with thesupplied plastic caps immediately after sampling.

5.3.7 Submit at least one blank tube (a charcoaltube subjected to the same handling procedures,without having any air drawn through it) with eachset of samples.

5.3.8 Take necessary shipping and packing precautions to minimize breakage of samples.

5.4 Analysis of samples.

5.4.1 Preparation of samples: In preparation foranalysis, each charcoal tube is scored with a file infront of the first section of charcoal and brokenopen. The glass wool is removed and discarded.The charcoal in the first (larger) section is transferredto a 2-ml vial. The separating section of foam isremoved 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, 1.0mL of desorbing solution is pipetted into eachsample container. The desorbing solution consistsof 0.05 µL internal standard per mL of carbon disulfide. The sample vials are capped as soon asthe solvent is added. Desorption should be donefor 30 minutes with occasional shaking.

5.4.3 GC conditions: Typical operating conditionsfor 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.

5.4.5 Measurement of area: The peak areas aremeasured by an electronic integrator or some othersuitable form of area measurement.

5.4.6 An internal standard procedure is used: Theintegrator is calibrated to report results in ppm for a10 liter air sample after correction for desorptionefficiency.

5.5 Determination of desorption efficiency.

5.5.1 Importance of determination: The desorption

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5.5.1 Importance of determination: The desorptionefficiency of a particular compound can vary fromone laboratory to another and from one lot ofchemical to another. Thus, it is necessary to determine, at least once, the percentage of the specific compound that is removed in the desorptionprocess, provided the same batch of charcoal is used.

5.5.2 Procedure for determining desorption efficien-cy: The reference portion of the charcoal tube isremoved. To the remaining portion, amounts repre-senting 0.5X, 1X, and 2X and (X represents targetconcentration) based on a 10 L air sample areinjected into several tubes at each level. Dilutionsof benzene with carbon disulfide are made to allowinjection of measurable quantities. These tubes arethen allowed to equilibrate at least overnight.Following equilibration they are analyzed followingthe same procedure as the samples. Desorption effi-ciency is determined by dividing the amount ofbenzene found by the amount spiked on the tube.

6. CALIBRATION AND STANDARDSA series of standards varying in concentration overthe range of interest is prepared and analyzedunder the same GC conditions that will be used onthe samples. A calibration curve is prepared byplotting concentration (_mg/mL) versus peak area.

7. CALCULATIONSBenzene air concentration can be calculated fromthefollowing equation:

mg/m3 = (A)(B)/(C)(D)Where:A=mg/mL benzene, obtained from the calibration curveB = desorption volume (1 mL)C= Liters of air sampledD= desorption efficiency

The concentration in mg/m3 can be converted toppm (at 25 °C and 760 mm) with following equation:

ppm = (mg/m3)(24.46)/(78.11)Where: 24.46 = molar volume of an ideal gas25 °C and 760 mm78.11 = molecular weight of benzene

8. BACKUP DATA8.1 Detection limit -Air Samples.The detection limit for the analytical procedure is1.28 ng with a coefficient of variation of 0.023 atthis 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 thatcould be identifiable in the presence of possibleinterferences. The detection limit data wereobtained by making 1 mL injections of a 1.283mg/mL standard.

8.2 Pooled coefficient of variation -Air Samples: The pooled coefficient of variation for the analyticalprocedure was determined by 1 mL replicate injections of analytical standards. The standardswere 16.04, 32.08, and 64.16 mg/mL, which areequivalent to 0.5, 1.0, and 2.0 ppm for a 10 L airsample, respectively.

Injection Area

Count

1 655.4

2 617.5

3 662.0 X= 640.2

4 641.1 SD = 14.9

5 636.4 CV= 0.023

6 629.2.

Area Counts

Injection 0.5 ppm 1.0 ppm 2.0 ppm

1 3996.5 8130.2 16481

2 4059.4 8235.6 16493

3 4052.0 8307.9 16535

4 4027.2 8263.2 16609

5 4046.8 8291.1 16552

6 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 —— —— ——

Day Analyzed Refrigerated Ambient

0 97.4 98.7 98.9 97.4 98.7 98.9

0 97.1 100.6 100.9 97.1 100.6 100.9

2 95.8 96.4 95.4 95.4 96.6 96.9

5 93.9 93.7 92.4 92.4 94.3 94.1

9 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

B-259/04

8.3 Storage data -Air Samples.Samples were generated at 1.03 ppm benzene at80% relative humidity, 22 °C, and 643 mm. Allsamples were taken for 50 minutes at 0.2 L/min. Sixsamples were analyzed immediately and the rest ofthe samples were divided into two groups byfifteen samples each. One group was stored atrefrigerated temperature of -25 °C, and the othergroup was stored at ambient temperature (approxi-mately 23 °C). These samples were analyzed over aperiod of fifteen days. The results are tabulatedbelow.

8.4 Desorption data.Samples were prepared by injecting liquid benzeneonto the A section of charcoal tubes. Samples wereprepared that would be equivalent to 0.5, 1.0, and2.0 ppm for a 10 L air sample.

8.5 Carbon disulfide.Carbon disulfide from a number of sources wasanalyzed for benzene contamination. The resultsare given in the following table. The benzene cont-aminant can be removed with the procedures givenin section 4.1.

PERCENT RECOVERY

Sample 0.5 ppm 1.0 ppm 2.0 ppm

1 99.4 98.8 99.5

2 99.5 98.7 99.7

3 99.2 98.6 99.8

4 99.4 99.1 100.0

5 99.2 99.0 99.7

6 99.8 99.1 99.9

X = 99.4 98.9 99.8

SD = 0.22 0.21 0.18

CV = 0.0022 0.0021 0.0018

X = 99.4

PERCENT RECOVERY

ppm

Sample mg equivalent

Benzene/ (for 10 L

mL 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 —— ——

9/04B-26

(II) OSHA LABORATORY METHOD NO. 12FOR BULK SAMPLESANALYTE: Benzene.MATRIX: Bulk Samples.PROCEDURE: Bulk Samples are analyzed directly by high performance liquid chromatography (HPLC).DETECTION LIMITS: 0.01% by volume.

1. PRINCIPLE OF THE METHOD1.1 An aliquot of the bulk sample to be analyzed isinjected into a liquid chromatograph.

1.2 The peak area for benzene is determined andcompared to areas obtained from standards.

2. ADVANTAGES AND DISADVANTAGES OF THE METHOD2.1 The analytical procedure is quick, sensitive, andreproducible.

2.2 Reanalysis of samples is possible.

2.3 Interferences can be circumvented by properselection of HPLC parameters.

2.4 Samples must be free of any particulates that may clog the capillary tubing in the liquidchromatograph. This may require distilling thesample or clarifying with a clarification kit.

3. APPARATUS3.1 Liquid chromatograph equipped with a UVdetector.

3.2 HPLC Column that will separate benzene from other components in the bulk sample beinganalyzed. The column used for validation studieswas a Waters uBondapack C18, 30 cm x 3.9 mm.

3.3 A clarification kit to remove any particulates inthe bulk if necessary.

3.4 A micro-distillation apparatus to distill anysamples if necessary.

3.5 An electronic integrator or some other suitablemethod of measuring peak areas.

3.6 Microliter syringes -10 mL syringe and otherconvenient sizes for making standards. 10 mLsyringe for sample injections.

3.7 Volumetric flasks, 5 mL and other convenientsizes for preparing standards and making dilutions.

4. REAGENTS4.1 Benzene, reagent grade.

4.2 HPLC grade water, methyl alcohol, and iso-propyl alcohol.

5. COLLECTION AND SHIPMENT OF SAMPLES5.1 Samples should be transported in glass containers with Teflon-lined caps.

5.2 Samples should not be put in the same container used for air samples.

6. ANALYSIS OF SAMPLES6.1 Sample preparation.If necessary, the samples are distilled or clarified.Samples are analyzed undiluted. If the benzeneconcentration is out of the working range, suitabledilutions 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, 50/502. Analytical wavelength -254 nm3. Injection size -10 mL

6.3 Measurement of peak area and calibration. Peak areas are measured by an integrator or othersuitable means. The integrator is calibrated toreport results % in benzene by volume.

B-279/04

7. CALCULATIONSSince the integrator is programmed to report resultsin % benzene by volume in an undiluted sample,the following equation is used:

% Benzene by Volume = A x BWhere: A = % by volume on reportB = Dilution Factor(B = 1 for undiluted sample)

8. BACKUP DATA8.1 Detection limit - Bulk Samples.The detection limit for the analytical procedure for bulk samples is 0.88 mg, with a coefficient ofvariation of 0.019 at this level. This amount provideda chromatographic peak that could be identifiablein the presence of possible interferences. Thedetection limit data were obtained by making 10mL injections of a 0.10% by volume standard.

8.2 Pooled coefficient of variation -Bulk Samples.The pooled coefficient of variation for analyticalprocedure was determined by 50 mL replicate injections of analytical standards. The standardswere 0.01, 0.02, 0.04, 0.10, 1.0, and 2.0% benzeneby volume.

AREA COUNT (PERCENT)

Injection No. 0.01 0.02 0.04 0.10 1.0 2.0

1 45386 84737 166097 448497 4395380 9339150

2 44241 84300 170832 441299 4590800 9484900

3 43822 83835 164160 443719 4593200 9557580

4 44062 84381 164445 444842 4642350 9677060

5 44006 83012 168398 442564 4646430 9766240

6 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

Injection Area

Count

1 45386

2 44214

3 43822 X = 44040.1

4 44062 SD = 852.5

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.

C-19/04

Coast Guard Benzene Rule

References:

46 CFR Parts 30, 151, 153, and 197.

Federal Register, Vol. 56, No. 201, pages 52122 - 52152.

APPENDIX C



D-19/04

METHOD: 1501, Issue 2

EVALUATION: Partial

ISSUE 1: 15 February 1984

ISSUE 2: 15 August 1994

Formula: Table 1

MW: Table 1

CAS: Table 1

RTECS: Table 1

OSHA: Table 2

NIOSH: Table 2

ACGIH: Table 2

Properties: Table 1

Compounds: benzene(Synonyms cumenein Table 1) a-methylstyrene

styrenevinyltoluenep-tert-butyltolueneethylbenzenenaphthalenetoluenexylene

SAMPLINGSampler: Solid Sorbent Tube

(coconut shell charcoal,100 mg/50 mg)

Flow Rate,

Volume: Table 3

Shipment: Routine

Sample

Stability: Not determined

Blanks: 2 to 10 field blanks per set

Bulk Sample: Desirable, 1 to 10 mL; shipin separate containers fromsamples

ACCURACYRange Studied: Table 3

Bias: Table 3

Overall

Precision

n(SrT): Table 3

Accuracy: Table 3

APPENDIX D

NIOSH Sampling and Analytical Procedure for Benzene (Method 1501-Hydrocarbons, Aromatic)

NIOSH Manual of Analytical Methods (NMAM), Fourth Edition, 8/15/94.



9/04D-2

MEASUREMENTTechnique: Gas Chromatography, FID

Analyte: Hydrocarbons listed above

Desorption: 1 mL CS 2 ; stand 30 min

Injection Volume: 5 µL

Temperature

Injection: 225 °CDetector: 225 °CColumn: 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 meshChromosorb W-AW orequivalent (Table 4)

Calibration: Analytes in CS2

Range and

Precision ( - Sr ): Table 4

Estimated LOD: 0.001 to 0.01 mg per samplewith capillary column [1]

APPLICABILITYThis method is for peak, ceiling and TWA determinations of aromatic hydrocarbons. It may be used for simultaneous measurements, thoughthere is the possibility that interactions betweenanalytes may reduce the breakthrough volumes and change desorption efficiencies.

INTERFERENCESUse of the recommended column may help reduce interference by alkanes. Under conditions of highhumidity, the breakthrough volumes may bereduced by as much as 50%. Other volatile organicsolvents, e.g., alcohols, ketones, ethers, and halogenated hydro-carbons, are possible interferences. If interference is suspected, using aless polar column or changing column temperaturemay help reduce such interference.

OTHER METHODSThis method is based on and supercedes MethodsP&CAM 127, benzene, styrene, toluene and xylene[2]; S311, benzene [4]; S22, p-tert-butyltoluene [3];S23, cumene [3]; S29, ethylbenzene [3]; S26, a-methylstyrene [3]; S292, naphthalene [4]; S30,styrene [3]; S343, toluene [4]; S25, vinyltoluene [3];S318, xylene [4].

REAGENTS1. 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 PRECAUTIONSCarbon disulfide is toxic and extremely flammable(flash point = -30 °C); benzene is a suspect carcinogen. Prepare samples and standards in awell-ventilated hood.


D-39/04

EQUIPMENT1. 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.

SAMPLING1. 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 PREPARATION5. 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.

CALIBRATION AND QUALITY CONTROL8. 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.


MEASUREMENT11. Set gas chromatograph according to

manufacturer’s recommendations and to conditions given on page 1501-1. Select appropriate column temperature:

Note: Alternatively, column and temperature may be taken from Table 4.

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.

CALCULATIONS14. Determine the mass, mg (corrected for DE) ofanalyte found in the sample front (Wf) and back(Wb) sorbent sections, and in the average mediablank front (Bf) and back (Bb) sorbent sections.Note: If Wb > Wf /10, report breakthrough andpossible sample loss.

15. Calculate concentration, C, of analyte in the airvolume sampled, V (L):

(Wf +Wb- Bf - Bb) • 103C = ____________________________ , mg/m3.

V

EVALUATION OF METHODPrecisions and biases listed in Table 3 were determined by analyzing generated atmospherescontaining one-half, one, and two times the OSHA standard. Generated concentrations wereindependently verified. Breakthrough capacitieswere determined in dry air. Storage stability wasnot assessed. Measurement precisions given inTable 4 were determined by spiking samplingmedia with amounts corresponding to one-half,one, and two times the OSHA standard for nominalair volumes. Desorption efficiencies for spiked samplers containing only one compound exceeded75%. Reference [9] provides more specific information.


Approximate Retention Time (min), at Indicated Column Temperature

Substance a 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.

9/04D-4

D-59/04

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 PrintingOffice, 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 ChemicalSubstances and Physical Agents and BiologicalExposure 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 BYR. Alan Lunsford, Ph.D., based on results of NIOSHContract CDC-99-74- 45.


TABLE 1. SYNONYMS, FORMULA, MOLECULAR WEIGHT, PROPERTIES (5).

Boiling Vapor Pressure DensityName/Synonyms Empirical Molecular Point @ 25 °C @ 20 °C

Formula Weight (°C) (mm Hg) (kPa) (g/mL)

benzene C 6 H 6 78.11 80.1 95.2 12.7 0.879CAS #71-43-2RTECS CY1400000

p-tert-butyltoluene C11 H16 148.25 192.8 0.7 0.09 0.861CAS #98-51-11-tert-butyl-4-methylbenzeneRTECS XS8400000

cumene C9 H12 120.20 152.4 4.7 0.63 0.862CAS #98-82-8isopropylbenzeneRTECS GR8575000

ethylbenzene C8 H10 106.17 136.2 9.6 1.28 0.867CAS #100-41-4RTECS DA0700000

a-methylstyrene C9 H10 118.18 165.4 2.5 0.33 0.911CAS #98-83-9isopropenylbenzene(1-methylethenyl)-benzeneRTECS WL5075300

naphthalene C10 H8 128.18 80.2a 0.2 0.03 1.025CAS #91-20-3RTECS QJ0525000

styrene C8 H8 104.15 145.2 6.1 0.81 0.906CAS #100-42-5vinylbenzeneRTECS WL3675000

toluene C7 H8 92.14 110.6 28.4 3.79 0.867CAS #108-88-3methylbenzeneRTECS XS5250000

vinyltolueneb C9 H10 118.18 167.7 1.6 0.22 0.898CAS #25013-15-4 (meta) 171.6 1.9 0.26 0.911methylstyrene (para) 172.8 1.8 0.24 0.911

(p-vinyltoluene)methylvinylbenzene (ortho) 169.8 1.8 0.24 0.904RTECS WL5075000

xylenec C8 H10 106.17CAS #1330-20-7 (ortho) 144.4 6.7 0.89 0.880dimethylbenzene (p-xylene) (meta) 139.1 8.4 1.12 0.864RTECS ZE2100000 (para) 138.4 8.8 1.18 0.861

a Melting point.b Commercial mixture of meta and para isomers.c Mixture of isomers.

9/04D-6


TABLE 2. PERMISSIBLE EXPOSURE LIMITS, PPM [6-8].

OSHA NIOSH ACGIH mg/m 3

Substance TWA TWA C STEL TLV STEL per ppm

benzene 1 0.1c 1 10 f 3.19

p-tert-butyltoluene 10 10 20 1 6.06

cumene 50 50 50 4.91(skin) (skin) (skin)

ethylbenzene 100 100 125 100 125 4.34

a-methylstyrene 100 50 100 50 100 4.83

naphthalene 10 10d 15 10 15 5.24

styrene 100 50 100 50** 100 4.26(skin)

toluene 200 100 150 50 3.77(skin)

vinyltoluene 100 100 50 100 4.83

xylene 100 100e 150 100 150 4.34a Maximum duration 10 min in 8 h. d Group III Pesticide.b Maximum duration 5 min in any 3 h. e Group I Pesticide.c Potential carcinogen. f Suspect carcinogen.

D-79/04


TABLE 3. SAMPLING FLOWRATE a, VOLUME, CAPACITY, RANGE, OVERALL BIAS AND PRECISION [3, 4, 9].

Breakthrough

Sampling Volume @ Range at Overall

Flowrate Volume b (L) Concentration VOL-MIN Bias Precision Accuracy

Substance (L/min) MIN MAX (L) (mg/m 3) (mg/m 3) (%) ( SrT) (± % )

benzene <0.20 5 30 >45 149 42 -165 - 0.4 0.059 11.4

p-tert-butyltoluene < 0.20 1 29 44 112 29-119 -10.3 0.071d 20.7

cumene < 0.20 1 30 >45 480 120 - 480 5.6 0.059 15.2

ethylbenzene < 0.20 1 24 35 917 222- 884 -7.6 0.089d 17.1

a-methylstyrene < 0.20 1 30 >45 940 236 - 943 -7.6 0.061d 16.9

naphthalene e < 1.0 100 200 >240 81 19 - 83 -2.6 0.055 11.5

styrene < 1.0 1 14 21 1710 426 - 1710 -7.9 0.058 d 16.7

toluene < 0.20 1 8 12 2294 548-2190 1.6 0.052 10.9

vinyltoluene < 0.20 1 24 36 952 256 - 970 -7.0 0.061d 16.3

xylene < 0.20 2 23 35 870 218- 870 -1.2 0.060 2.2a Minimum recommended flow is 0.01 L/min. e Naphthalene shows poor desorption efficiency at low loading;b V Min = minimum sample volume @ OSHA TWA; 100-L minimum volume is recommended.

V Max = maximum sample volume @ OSHA TWA. f 15-min sample.c 10-min sample. g 5-min sample. d Corrected value, calculated from data in Reference [9].

TABLE 4. MEASUREMENT RANGE, PRECISION AND CONDITIONS a [3, 4, 9].

Desorption Measurement Carrier Column Parameters b

Volume Range Precision Flow t Length

Substance (mL) (mg) ( -Sr) (mL/min) (°C) (m) Packing c

benzene 1.0 0.09 - 0.35 0.036 50 115 0.9 A

p-tert-butyltoluene 0.5 0.27- 1.09 0.021d 50 115 3.0 B

cumene 0.5 0.86 - 3.46 0.010 50 99 3.0 B

ethylbenzene 0.5 2.17- 8.67 0.010 50 85 3.0 B

a-methylstyrene 0.5 0.69 - 3.57 0.011 50 115 3.0 B

naphthalene 1.0 4.96 -19.7 0.019 30 125 3.0 C

styrene 0.5 2.17- 8.49 0.013d 50 109 3.0 B

toluene 1.0 1.13 - 4.51 0.011 50 155 0.9 D

vinyltoluene 0.5 2.41- 9.64 0.008 50 120 3.0 B

xylene 1.0 2.60 - 10.4 0.010 50 180 0.9 Da Injection volume, 5.0 mL; nitrogen carrier gas.b 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].

9/04D-8


NUMBER: 59

PRODUCT: 3M Organic Vapor Monitor #3500/3510/3520/3530

SUBJECT: Sampling For Benzene

1. INTRODUCTION

This technical data bulletin contains information to be used when sampling atmospheresfor 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

Benzene Toluene Xyleneµg/ppm-hr 6.78 7.08 7.09cc/min 35.5 31.4 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 CenterSt. Paul, Minnesota 55144-1000.D-2

E-19/04

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 timeis listed. The maximum concentration which could be sampled continuously for 8 hours is:

Benzene 240 ppm

9/04E-2

FIGURE 1: MINIMUM SAMPLING TIME FOR BENZENE COLLECTEDON #3500/3510/3520/3530 ORGANIC VAPOR MONITORS

BEN4.DAT JAK 3/86

E-39/04

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 theanalyst 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 bebased upon benzene.

S-11065 (REV. 3-84)

DECLARATION OF INSPECTION PRIOR TO BULK CARGO TRANSFERRADIO NO.

DATE/TIME ISSUED

TANKERMAN’SSIGNATURE

DATE/TIME RETURNED

DOCKMAN’SSIGNATURE

VESSELS:

TRANSFERFACILITY:

LOCATION:

INITIALFACILITY 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).

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.

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 eachof them I have indicated by my initials that the regulations have been complied with.

FACILITY VESSELSIGNATURETITLETIME AND DATE

SIGNATURETITLETIME 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 TIME AND DATE

VESSEL

FACILITY

VESSEL

FACILITY

VESSEL

FACILITY

TIME AND DATE COMPLETED

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§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 forchanges 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 ofthis chapter;(g) the transfer system is attached to a fixed connection

on the vessel and the facility except that when a vessel isreceiving fuel, an automatic back pressure shutoff nozzlemay 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 usedto receive or discharge ballast in compliance with 33 CFR157;(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 ofhose reinforcement (“reinforcement” means the strengthmembers 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 asapplicable;(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 doesnot exceed the capacity of the discharge containment pro-vided 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 imme-

diately 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, asappropriate; and(3) conducts the transfer operation in accordance with

the facility operations manual or vessel oil transfer proce-dures, 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 languagesspoken by both persons in charge;(w) the person in charge of oil transfer operations on thetransferring vessel or facility and the person in charge of alltransfer operations on the receiving vessel or facility haveheld a conference, to ensure that each person in chargeunderstands the following details of the transfer opera-tion...

(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 partici-

pating 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 oiltransfer 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 transferoperations 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 StandardsInstitute (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 meetsANSI standards;(4) use a bolt in each hole of each permanently connect-

ed flange;(5) use bolts of the correct size in each bolted connec-

tion; 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 operationsunless it is...(1) a bolted or full threaded connection; or

(2) a quick-connect coupling acceptable to theCommandant.(d) No person may transfer oil to a vessel that has a fill

pipe for which containment cannot practically be providedunless an automatic back pressure shutoff nozzle is used.

§ 156.150 Declaration of Inspection.

(a) No person may transfer oil to or from a vessel unlesseach person in charge, designated under §§ 154.710 and155.700 of this chapter, has filled out and signed the decla-ration of inspection form described in paragraph (c) of thissection.(b) No person in charge may sign the declaration of inspec-tion unless he or she has determined by inspection, andindicated by initialling in the appropriate space on the dec-laration of inspection form, that the facility or vessel, asappropriate, 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 facili-ty or vessel.(d) The form for the declaration of inspection may incor-

porate 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 availa-ble 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 anoil 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 transferoperation, the master or senior deck officer on duty shall fill in the following Declaration of Inspection in duplicate. Theoriginal of the Declaration of Inspection shall be kept aboard for the information of authorized persons. The du-plicate, where required, shall be handed to the terminalsuperintendent or his representative, who shall on demand be given the opportunity to satisfy himself that the condi-tion 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 seniordeck officer in charge of the transfer of bulk flammable andcombustible cargo about to be undertaken, do certify that Ihave personally inspected this vessel with reference to thefollowing requirements set forth in § 35.35-20 and that opposite each of them I have indicated that the regulationshave 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 thecargo connections have been made?

(6) Has the shore terminal or other tank vessel con-cerned 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 todetermine 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 opera-tions 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.

FUNCTION UNIT SUBSEQUENT PERSON-IN-CHARGE TITLE

DELIVERING

RECEIVING

DELIVERING

RECEIVING

DELIVERING

RECEIVING

INITIAL PERSON-IN-CHARGE INITIAL PERSON-IN-CHARGE

UNIT TITLE TIME AND DATE UNIT TITLE TIME AND DATE

S-12094 (REV 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 PERSONNELONLY, 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

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.

On small fire use dry chemical or carbon dioxide. On large fire use water spray or foam. Cool exposed tanks with water.

Remove to fresh air. If not breathing apply artificial respiration, oxygen. If breathing is difficult, administer oxygen. Call a physician.

Spill or Leak

Fire

Exposure

DELIVERING RECEIVING

I CERTIFY THAT I HAVE READ THE ABOVE SIGNATURE TIME AND DATE COMPLETEDADDENDUM AND DETAILED REQUIREMENTS ANDALL CONDITIONS REMAIN SATISFACTORY

benzene ps manual

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