acrylonitrile - cornerstone chemical company

AcrylonitrileProperties, Handling & Storage Manual

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TABLE OF CONTENTS

Page

Introduction ...................................................................................................................................................... 4

Occupational Safety and Health................................................................................................................. 5

Medical Response and Emergency First Aid Procedures ................................................................ 7

Technical Information................................................................................................................................... 9

Fire Safety ........................................................................................................................................................ 12

Storage of Acrylonitrile............................................................................................................................... 12

Shipping and Handling of Acrylonitrile ................................................................................................ 15

Environmental Protection ......................................................................................................................... 16

Appendix I: NIOSH Analytical Method 1604 ..................................................................................... 20

Appendix II: Medical Surveillance Program ...................................................................................... 25

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INTRODUCTION

This manual was prepared for individuals who handle acrylonitrile. It was designed as a guide to the responsible handling of acrylonitrile and to provide practical information to the reader. Before handling, always consult a current Material Safety Data Sheet (MSDS). An MSDS sheet has been placed in the rear jacket of this manual. Future updates can be obtained from Cornerstone Chemical Company. Appropriate safety practices and work procedures must be followed when using acrylonitrile. It is imperative that employees and affected individuals be aware and informed of the primary hazards of the chemical and how to handle it safely. These hazards include flammability, toxicity, reactivity, and polymerization.

Acrylonitrile ... Physical Properties

Acrylonitrile is a colorless to pale yellow liquid with a pungent odor, which can be detected by smell at levels above 13-19 ppm. It is a flammable liquid, and its vapors can easily form an explosive mixture with air. Acrylonitrile vapors are heavier than air and may travel along the ground and be ignited at locations remote from the handling site.

Acrylonitrile...Effects ofOverexposure

Acrylonitrile easily permeates the skin. Direct skin contact, ingestion or inhalation of acrylonitrile can produce serious acute toxicity, including loss of con-sciousness or death. According to Ledou Text of Occupational Medicine, speed and preparedness are the prerequisite of successful treatment of overexpo-sure. All persons working with or around acrylonitrile should be given specific and detailed instructions on the use of antidote kits. Antidote kits for use by medical personnel should contain the following:

2 boxes of amyl nitrite ampules, 0.3 ml/ampule

CYANOKIT®

2 sterile 10-ml syringes with intravenousneedles

1 sterile 50-ml syringe with intravenousneedle

1 tourniquet 1 gastric tube (rubber) 1 non sterile 100-ml syringe

Acrylonitrile contact causes eye and skin irritation. Acrylonitrile liquid can penetrate leather shoes,belts, wallets, or other leather goods and causedelayed burns to the skin. Acrylonitrile has beenshown to cause cancer in laboratory rats and isregulated as a carcinogen by OSHA (29 CFR1910.1045). Acrylonitrile has been shown to causebirth defects and adverse effects on male andfemale reproduction in laboratory animal tests. Riskof chronic hazard depends on duration and level of exposure. Biologic monitoring may be useful in themanagement of occupational exposures.

Acrylonitrile ChemicalProperties

Acrylonitrile is a reactive olefinic nitrile which serves many chemical functions. Care should be taken to avoid contact of acrylonitrile with strong bases and oxidizers, especially bromine or caustic soda solutions,copper, copper alloys, ammonia and amines. Thiscontact can produce serious decomposition reactions,resulting in fire or explosion. Chemical compatibilityshould be checked before acrylonitrile comes incontact with any other chemical.

Acrylonitrile will spontaneously polymerize when overheated. The heat released results in atemperature rise that can lead to additionalpolymerization, resulting in an over-pressurizationhazard. Cornerstone adds inhibitors to thecommercial product to reduce the risk of self-polymerization, but this does not eliminate allpossibility of polymerization.

We urge you to read the rest of this manual indetail for further explanation about procedures toreduce the risks associated with storage andhandling of acrylonitrile.

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OCCUPATIONAL SAFETY ANDHEALTH

Signsand Symptoms ofExposure

Acrylonitrile is a colorless to pale yellow liquidwith a pungent odor. Acrylonitrile may enterthe body by inhalation, absorption through theskin or ingestion. Signs of overexposure includenausea, vomiting, headache, confusion,cyanosis, limb weakness, and light-headedness. Severe overexposure may produce loss of consciousness or death. Acrylonitrile is anirritant causing eye and skin irritation. Thisirritation may appear several hours followingexposure. Based on animal evidence, chronicexposure to acrylonitrile may cause cancer.However, the carcinogenicity of acrylonitrile hasbeen investigated in humans. A Cornerstonesponsored epidemiological study involving2671 workers, 1774 of whom were exposed toacrylonitrile, did not show any significantincrease in cancer mortality due to acrylonitrileexposure.

For more toxicological information, please referto Cornerstone’s Material Safety Data Sheet foracrylonitrile, which is enclosed in the jacketpocket to this manual.

Permissible Exposure Limits

The U.S. Occupational Safety and Health Administration (OSHA) have establishedpermissible exposure limits and work practicesfor occupational exposure to acrylonitrile.Other countries have also establishedoccupational limits for acrylonitrile exposure. Consult your local government regulations for compliance with applicable limits. Pleaseconsult the Cornerstone MSDS enclosed withthis booklet for further details.

OSHA Permissible Exposure Limits

The OSHA acrylonitrile standard states that employers with workers handling acrylonitrile shall assure that:

(a) No employee is exposed to an airborneconcentration of acrylonitrile in excess of two (2) partsof acrylonitrile per million parts of air (2 ppm), as aneight-hour time weighted average (The OSHA PEL). OSHAhas established an action level of 1 ppm acrylonitrile.(b) No employee is exposed to an airborneconcentration of acrylonitrile in excess of ten (10) ppmas averaged over any fifteen (15) minute period duringthe work day (the OSHA Ceiling Limit).(c) No employee is exposed to skin contact or eye contact with liquid acrylonitrile.

The OSHA standard regulates acrylonitrile as a carcinogen. If you have an area of your facility in whichthe air concentration of acrylonitrile exceeds 2 ppm,this is a regulated area. This area must be posted withsigns:

“DANGER ACRYLONITRILE (AN) CANCER HAZARDAUTHORIZED PERSONNEL ONLY RESPIRATORS MAY BE REQUIRED”

Exposure Monitoring

Airborne levels of acrylonitrile can be determined eitherthrough personal monitoring involving sampling pumpsand charcoal tubes, or area monitoring involving directreading instruments. Monitoring to evaluate anemployee’s 8-hour exposure should be conducted usingthe National Institute of Occupational Safety and Health(NIOSH) Analytical Method 1604 (See Appendix I formethod details). This method requires the collection of airborne acrylonitrile vapor on a charcoal tube,followed by desorption and analysis by gaschromatography. Monitoring to evaluate an employee’s15-minute or ceiling exposure must be taken duringperiods of maximum expected airborne concentrations

The frequency of employee monitoring shall be determined using the results of the initial exposure monitoring as follows:

Below action level of 1 ppm: Monitoring may bediscontinued

At or above the action level but below the PEL: Repeatmonitoring at least every 6 months until 2 consecutivemeasurements taken 7 days apart are below the actionlevel. Monitoring may then be discontinued.

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Above the PEL:Repeat monitoring at least quarterly until 2 consecutive measurements taken 7 days apart are below the PEL. Continue monitoring on a 6 month basis. Additional monitoring should be conductedwhenever there has been a production, process, control, or personnel change which may result innew or additional exposures to acrylonitrile.

Personal Protective Equipment

Respiratory Protection

Proper respiratory protection must be usedwhenever engineering and work practice controls arenot sufficient to reduce exposures below thepermissible exposure limits. Where adequateengineering controls are in effect, and measurementsconfirm airborne concentrations are below theexposure limit, no respiratory protection is required. Proper respiratory protection should be used in thefollowing circumstances:

1. During the time period necessary to installengineering controls.

2. During maintenance and repair operations, or reactor cleaning where engineering and work practice controls are not feasible.

3. Where feasible engineering and work practice controls are not sufficient to reduce exposures below the Permissible Exposure Limits.

4. During emergencies.

5. When the air concentrations are not known and may exceed 2 ppm.

All employees who are required to wear respiratory protection must be properly trained on respiratoruse. Respiratory protection training should include:

1. The reasons why respirators must be worn.

2. The limitations of the respirator.

3. Proper maintenance and inspection procedures.

4. Hands-on demonstration on the proper fit and adjustment of the respirator.

5. Conditions to avoid, such as the presence of facialhair, or interference with the respirator’s sealingsurface which can be caused by eye glasses.

Used respirator cartridges should be discarded atthe end of each work shift. These respirators mustbe selected specifically for use with acrylonitrile. Theappropriate respirator must be approved by NIOSH.

Protective Equipment

Leather goods should be forbidden whereacrylonitrile is in use. Contaminated leatherproducts, such as shoes, belts, wallets, andwatchbands, must be disposed of properly. (SeeWaste Issues within the Environmental section). Leather cannot be safely decontaminated aftercontact with acrylonitrile.

For operations where it is possible for acrylonitrile to come into contact with skin, wear full imperviousprotective clothing to prevent such contact. The head, face, hands, and feet must be protected. Suitable impervious protective clothing, including gloves, boots,

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and suits should be selected based on thepotential level of exposure. All employeesworking with acrylonitrile must wear eyeprotection where eye contact with acrylonitrile ispossible. Splash proof safety goggles and faceshields must be worn in all areas where liquidacrylonitrile is handled. Permeation and materialdegradation must be considered whenevaluating protective clothing. Permeation datashould be obtained from equipment manufacturer.Hygiene Facilities

1. Eyewash and safety showers must beprovided and appropriately located in allareas where acrylonitrile is used andhandled.

2. Where employees are exposed to airborneconcentrations of acrylonitrile abovepermissible exposure limits, or whereemployees are required to wear PPE,shower facilities and clean change roomsshould be provided. Employers should assure that employees use these facilities.Those who work with acrylonitrile shouldshower at the end of every work shift.

3. Protective equipment must be washedthoroughly before removing.

4. In the event of skin or eye contact withacrylonitrile, employers should assure thatthe affected employee immediately washesexposed area with plenty of soap and water. Contaminated clothing and shoes should beremoved without delay. Contaminatedleatherwear must be destroyed.

5. Employers should assure that employeesworking with acrylonitrile wash their handsand face with soap and water prior toeating, drinking or smoking. No food,beverage or tobacco products arepermitted where acrylonitrile is in use.

6. Change rooms with individual lockers should be provided to prevent the contamination of street clothes. Used work clothing and contaminated protective gear should be laundered at the completionof each work shift and prior to reuse. Used workclothing and contaminated protective gear must bestored in closed containers for cleaning or properdisposal.

MEDICAL RESPONSE AND EMERGENCYFIRST AID

If accidental exposure to acrylonitrile occurs, call for assistance immediately and begin treatment inaccordance with the Emergency First Aid Procedurespublished at 29 CFR 1910.1045 and reprinted below:

Eye Exposure

If acrylonitrile gets into your eyes, wash your eyes immediately with large amounts of water, lifting thelower and upper lids occasionally. Get medicalattention immediately.

Skin Exposure

If acrylonitrile gets on your skin, immediately wash thecontaminated skin with water. If acrylonitrile soaksthrough your clothing, especially your shoes, remove the clothing immediately and wash the skin withwater. If symptoms occur after washing, get medicalattention immediately. Thoroughly wash the clothingbefore reusing. Contaminated leather shoes or otherleather articles should be discarded. See Waste Issueswithin the Environmental section

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Inhalation

If you or any other person breathes in largeamounts of acrylonitrile, move the exposed personto fresh air at once. If breathing has stopped,perform artificial respiration. Keep the affectedperson warm and at rest. Get medical attention as soon as possible.

Swallowing

When acrylonitrile has been swallowed, give theperson large quantities of water immediately. Afterthe water has been swallowed, try to get the personto vomit by having them touch the back of theirthroat with their finger. Do not make anunconscious person vomit. Get medical attentionimmediately.

Rescue

Move the affected person from the hazardousexposure. If the exposed person has beenovercome, notify someone else and put into effectthe established emergency procedures. Do notbecome a casualty yourself. Understand youremergency rescue procedures and know thelocation of the emergency equipment before theneed arises.

Special First Aid Procedures

First aid kits containing an adequate supply (atleast two dozen) of amyl nitrite pearls, eachcontaining 0.3 ml, should be maintained at eachsite where acrylonitrile is used. When a person issuspected of receiving an overexposure toacrylonitrile, immediately remove that person fromthe contaminated area using established rescue

procedures. Contaminated clothing must beremoved and the acrylonitrile washed from theskin immediately. Artificial respiration should be started at once if breathing has stopped. If theperson is unconscious, amyl nitrite may be usedas an antidote by a properly trained individualin accordance with established emergencyprocedures. Medical aid should be obtainedimmediately.

If the patient shows signs of poisoning, break an amyl nitrite ampule in a handkerchief and holdit about one inch from the patient’s nose for 15seconds, then away for 15 seconds and repeatif the symptoms have not disappeared. Use anew ampule every two minutes until emergencymedical assistance arrives.

If a physician is present, further therapy maybe started. Inject, intravenously, 10cc of 3%aqueous solution of sodium nitrite at a rate of 2-to-5cc per minute; then 50cc of 25%solution of sodium thiosulfate at the samerate.

When signs of poisoning persist or reappear, the injection of sodium nitrite and sodiumthiosulfate may be repeated, using half thequantity originally used. In any case, a secondinjection of the antidotal solutions (using 1⁄2the original quantities) may be given two hourslater for prophylactic purposes.

If it is necessary to take the patient to thehospital, take a copy of these instructions anda cyanide kit along with the patient and askthe staff to follow these instructions explicitly.

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TECHNICAL INFORMATIONPhysical Properties

Appearance and Odor: Colorless to Pale Yellow Liquid with a Pungent OdorMolecular Weight: 53.06Freezing Point: -82˚C to -84˚CBoiling Point: 171˚F, 77.3˚C at 760 mm Hg Pressure

Vapor Pressure: 84 mm Hg @ 20˚C ( S e e f i g u r e 3 )

Flash Point: 30˚F, -1˚C Closed Cup

Auto ignition Temperature: 898˚F, 481˚CFlammable Limits: Lower: 3.0%; Upper: 17%, by volume in air at

25˚C Vapor Density: 1.83 (Air = 1.0)

Density: (See Figure 4)% Volatile by Weight: 100Saturation in Air: 11.1 @ 20˚C, 760mm Hg (% by Volume)Evaporation Rate: 4.54; (Butyl acetate = 1) @ 20˚C Solubility in Water: 7.4% @ 20˚C (See Figures1 & 2)

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SolubilityAcrylonitrile in WaterTemperature, ˚C

100

SolubilityWater in Acrylonitrile

Temperature, ˚C100

80

60

40

20

07 8 9 10 11 12

Solubility – % Acrylonitrile in Water

80

60

40

20

01 2 3 4 5 6 7 8 9 10 11 12

Solubility – % Water in Acrylonitrile

Figure 1 Figure 2

Density ofAcrylonitrile

Temperature, ˚C50

40

30

20

10

0

-106.55 6.60 6.65 6.70 6.75 6.80 6.85 6.90 6.95

Density of Acrylonitrile – Pounds per Gallon

Figure 4

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Product SpecificationSales Specifications

Acrylonitrile, as produced by Cornerstone is a highly pure chemical. An inhibitor and water are addedto reduce the likelihood of polymerization and color formation. The sales specifications are shown below:

Item Minimum/Maximum*

1. Acetone, ppm by weight 75 maximum2. Acetonitrile, ppm by weight 300 maximum3. Appearance Clear liquid, free from suspended matter.4. Color (APHA) 5 maximum5. Acrolein, ppm by weight 1 maximum6. Oxazole, ppm by weight 10 maximum7. Hydrocyanic Acid, ppm by weight 5 maximum8. Inhibitor -- MEHQ, ppm by weight 35 minimum/45 maximum9. Peroxides, as H2O2, ppm by weight 0.2 maximum10. Water, % by weight 0.2 minimum/ 0.5 maximum

Typical Properties

Item Value*

1 Infrared Spectra Conforms to published data2. Non-Volatile Matter, ppm by weight 100 maximum3. Total Iron, ppm by weight 0.1 maximum4. Acidity as Acetic Acid, ppm by weight 10 maximum

*Analytical test methods for determining or monitoring product quality are available from Cornerstone on request.

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FIRE SAFETY

Acrylonitrile is flammable and may easily ignite by heat, sparks or flame. Vapors can form explosive mixtures with air and travel to an ignition source and flash back. Most vapors are heavier than air and will spread along the ground and collect in low or con-fined areas such as sewers or basements. These vapors could present an explosion or toxicity hazard.

For small fires, use dry chemical, carbon dioxide,water spray, or alcohol-resistant foam. For largefires, use alcohol-resistant foam, water spray, or fog.Move containers from fire area if it can be done with-out risk.

Water spray may be ineffective as an extinguishing agent, but can be used to cool containers anddisperse vapors. Do not use a solid stream of water, since the stream will scatter and spread the fire.Dike fire control water for later disposal. (See Waste Issues within the Environmental section).

Approach fire from upwind to avoid hazardous vapors and toxic decomposition products. For fires involving tanks or car/trailer loads, fight fire from maximum distance or use unmanned hose holdersor monitor nozzles. Cool containers with flooding quantities of water until well after fire is out. If tank, rail car, tank truck or other large quantity of material is involved in a fire, Isolate for 800 meters (1⁄2 mile) in all directions and consider initial evacuation for800 meters (1⁄2 mile) in all directions.

Elevated temperatures or contamination can cause material to polymerize causing a pressure buildupthat may violently rupture tanks or containers. In the event material begins to polymerize, isolate the area and use water fog or spray from unmanned hose streams to control vapors. Take defensive actions only. Let the reaction run its course. Once thereaction is complete, follow normal precautions forthis material.

Wear self-contained, positive pressure breathing apparatus and full firefighting protective clothing. Structural firefighter’s protective clothing isrecommended for fire situations only and is noteffective in spill situations.

STORAGE OF ACRYLONITRILE

The following safe handling and storage practices are designed to reduce potential hazards from occurring.

Acrylonitrile may polymerize exothermically when properstorage practices are not followed. Vaporization of theacrylonitrile at the elevated temperature caused byexothermic polymerization can result in explosion.

Acrylonitrile in its uninhibited form should never be stored. Acrylonitrile quality is easy to maintain when it is properly stored and handled. The main problem which may beencountered is formation of polymer and discoloration. Acrylonitrile in static storage must be analyzed regularly for quality, color, appearance, inhibitor content and water content. Testing frequency will vary with customer location conditions such as predominate weather, volume, tank turn-over, etc. Sampling more frequently may be required if abnormal storage conditions develop. Store Acrylonitrile only in clean, dedicated storage tanks.Acrylonitrile vapors are not inhibited and may polymerize,clogging vessel vents. These vents must be checkedregularly to verify that they are open

To reduce the chance of accidental polymerization, acrylonitrile is stabilized with an inhibitor system.

This inhibitor system consists of water @ 0.2-0.5% by weight and 35-45 ppm MEHQ (methyl ether of hydroquinone). Water inhibits ionic polymerization bytrapping basic or acidic intermediates. MEHQ inhibits freeradical polymerization by trapping free radicalintermediates. MEHQ levels should be maintained atlevels of 35 to 45 ppm during long-term storage. MEHQrequires dissolved oxygen in acrylonitrile for properinhibition of polymerization.

Free radical catalysts, such as peroxides and hydroperoxides,can initiate spontaneous exothermic polymerization. Avoidmixing with basic or alkaline materials, such as sodiumhydroxide, potassium hydroxide or ammonia; mixing withLewis acid catalysts, such as boron trifluoride, titaniumtetrachloride and sodium borohydride; contact with strongmineral or organic acids; and exposure to high energyradiation, such as UV light, X-rays and gamma rays.

The vapor space above acrylonitrile in storage should beblanketed with nitrogen to purge oxygen to levels below8% in order to reduce the flammability. The MEHQ andwater inhibitor systems will remain effective below an 8%oxygen level in the vapor space

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Storage Tank Design andConstruction

Storage and handling of acrylonitrile must comply withregional government regulations and controls and goodengineering practices such as API650, NFPA. Theseregulations and standards must there- fore beconsidered in the design of any acrylonitrile storagefacility.

Tank Location

The location of storage tanks should be based on:

• Accessibility for normal operations.

• Routine maintenance activities.

• Access for emergency response personnel and equipment.

Tank farm design should take into account thepossibility of accidental spills and fires. Segregatedstorage of other chemically reactive materials is required to prevent accidental mixing of acrylonitrile with thesematerials.

Storage tanks should be constructed at ground level and in the open air. If a leak develops, ground level construction improves the detection of any vapor emissions and allows natural ventilation to disperse these vapors. Storage tanks must be located away frompotential sources of ignition. Heat radiation from fires inan adjacent area should also be considered in choosing the tank location.

All storage tanks should be surrounded by a concrete dike capable of containing 110% of the largest tank within the dike plus the collected rainfall from a 24- hour,25-year storm. The dike wall and floor should be impervious to liquid acrylonitrile and designed towithstand a full hydrostatic head. The height of the dike walls should not be higher than five feet to ensure adequate ventilation of the storage area, and to allow easy access and escape for emergency personnel. Intermediate dike walls are recommended to divide tanksinto groups to contain any accidental leakage and tominimize the surface area of the spill. The tank should beequipped with a leak detection system.

The floor of the diked area must be sloped to prevent small spills from collecting below any storage tank.

Drainage of collected precipitation within thestorage dike should be accomplished using an air-driven pump or an electric pump with aflameproof motor. If dike drains are used for theremoval of collected precipitation, then the drainvalves should be located outside the dike walls.Written procedures should ensure that the valvesremain closed and locked, except when collectedprecipitation is being removed. Contaminatedprecipitation must be pumped to a suitablecontainer for proper disposal according to localregulations.

Tank Design and Construction

The storage tank design should consider theexpected delivery vehicle and the requiredcapacity. The tanks should be the smallestcompatible with shipping and receivingrequirements. Storage times in excess of sixmonths should be avoided to prevent thedegradation of acrylonitrile quality. Storage tanksmay be constructed from carbon steel, stainlesssteel or aluminum. Copper or copper alloys shouldnever be used as copper may discolor theacrylonitrile and can initiate polymerization.

Carbon steel tanks must be cleaned by chemical or physical means to remove rust prior to initial use. To reduce the potential for chemical reaction,further cleaning with water is required, if chemicalcleaning procedures were used.

The use of a multi-compartmented tank is notrecommended because of the risk of productcontamination or heating from adjacentcompartments.

While acrylonitrile storage tanks generally do not require insulation or refrigeration, the tanksshould be painted white to reduce anytemperature rises, and thus, the amount of acrylonitrile vapor.

Capability for storage tank agitation or circulationis recommended for uniformity of productsampling and for addition and circulation of inhibitors

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A manhole of a minimum of 20 inches should be included on all tanks to allow for internalinspection and cleaningTo prevent possible build-up of static charge in atop- loading system, the inlet pipe must extendnearly to the bottom of the tank to prevent free-falling of a flammable liquid. Storage tanks shouldbe constructed to allow full drainage of the tankcontents sloped to an outlet with no trappedareas.

The tank design must allow for measuring liquidlevel and temperature by a method which doesnot require opening a tank gauge hatch. Openinga gauge hatch increases the potential foremployee exposure to acrylonitrile. Closedgauging systems are commercially available. Tankliquid levels may be measured by any reliablesystem. Level indicators should be intrinsically safefor use with acrylonitrile based on nationallyaccepted standards. High level alarms andinterlocks should be included to prevent overfilling.

Piping

All piping should be constructed of the samematerial as that of the tank and have a minimumpipe diameter of two inches. The tank dischargeline should be installed on the bottom or side of thetank and should be fitted with an isolating valve as close to the tank wall as possible. Discharge fromthe tank must be made by pump. The dischargepump and controls should be outside thecontainment dike.

Tanks must be designed with a capacity fordraining. This drain piping should be fitted fromthe lowest point on the tank and have anisolation valve. The isolation valve should beclosed and locked out when not in use. Whereverpossible, continuously welded pipe work shouldbe used. Flange joints may be used where pipesare periodically disconnected for maintenance or inspection. Flanges should conform to the ANSIStandard and Grafoil®* gaskets or equivalent should be used. Screwed fittings should not beused except for stainless steel instrumentation.

Piping should not be located over doorways or windows or close to possible sources of ignition.

Fixed, dedicated loading/unloading arms arerecommended. All hoses used for loading or unloadingmust be acrylonitrile-resistant lined armored asthenicsteel flex hose. Hoses must be inspected for wear ordamage on a frequent basis and replaced as necessary.

Pumps

Pumps must be located outside of tank dikes on an impervious base in an open space. Pumps should not be located in a walled-off or confined area.

Centrifugal pumps designed to ANSI Standards are normally used for acrylonitrile. Single or double mechanical, self-flushing seals should be used. Seal face materials should be made of carbon againstsilicon carbide or carbon against tungsten carbide.

Pumps should be constructed of either cast steelor stainless steel. Plastic pumps should not beused.

Pumps may be driven pneumatically, hydraulically or electrically. Where electric motors are used to drive the pump, the National Electrical Code (NFPA 70) should be followed. If pumps are remotely con-trolled, then a stop button must be installed at the pump delivery point. Pump output should notexceed the recommended design capacity of thepiping system.

Note that gravitational flow may occur in acentrifugal pump when the pump is stopped. Thisflow should be anticipated, and the design shouldcompensate for it.

Valves

Valves should be installed directly on all bottom out-lets of a tank unless these branches are blanked off. Isolating valves may be ball, gate, Angle or globe withPTFE seats. Note that diaphragm valves must not beused with acrylonitrile.

Valve bonnet gaskets may be soft iron, spiral wound or equivalent. Valve stem packings should be graphite packing or equivalent.

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Vapor Containment and Recovery

The vapor pressure of acrylonitrile is sufficiently high as to result in relatively significant storage tank breathingand fill losses. A closed-loop balance venting systemshould be installed so that vapors from the storage tankare returned to the rail car or tank truck during storagetank filling.

Vapors discharged from the vents during normal breathing, due to temperature-pressure changes and evaporation rate should be controlled according to localgovernment regulations. Depending on specific needsand circumstances, use one or more of the followingcontrol methods:

1) Pressure storage or conservation vents

2) Floating tank roof

3) Refrigerated condenser

4) Wet scrubbing

5) Flaring or incineration

Electrical Concerns

The tank, pumps, valves and piping should be electricallygrounded to prevent the accumulation of static electricalcharges. Tanks should be bonded and fitted withgrounding point and connected to a good ground witha resistance of at most five ohms at any point in thesystem. The same guideline applies to the groundingpoint of all discharge equipment, which should beconnected to the same ground. If discharge equipmentis grounded independently, the ground should haveminimal resistance between the discharge equipmentand the tank pipe work system.

SHIPPING AND HANDLING OF ACRYLONITRILE

Shipping Containers

Acrylonitrile is shipped in tank cars, tank trucks, barges and ships, all of which are unlined. Tank cars and trucks are constructed of either carbon steel (ASTM A-285, Grade C) or stainless steel (316) Containers used to ship, store or handle acrylonitrile in any manner should be thoroughly cleaned, since contaminated containers may catalyze polymerization of acrylonitrile or

cause rapid decomposition.

Specifically, the presence of concentrated causticalkali will initiate violent, exothermic polymerizationof acrylonitrile. Large amounts of acid may promotehydration of the acrylonitrile or may hydrolyze theacrylonitrile to acrylic acid.

Methods of Handling

Unloading Tank Cars and Tank Trucks

Written operating procedures should be available for unloading acrylonitrile from tank cars or tank trucks. Personnel involved in unloading should be fully trained in these procedures. The instructionsshould recognize the specific hazards of acrylonitrile, and ensure the correct operation of unloading equipment in both normal andemergency situations. Before unloadingacrylonitrile from tank cars, several precautionsshould be observed. Make certain that the traincrew accurately spots the car at the unloading lineand that the brakes are set and the wheels arechocked.

Clearly visible caution signs should be placed in accordance with 49 CFR 174.67(a) (4). The derail signs should be placed in accordance with 29 CFR 1910.176(f). Once properly clothed (see Occupational Safety and Health Section IV of this manual) for unloading, inspect the car carefully for leaks. If leaks are discovered, notify the facility’s emergency response team.

Before making any connections, using non-sparking tools, ground the tank car, the unloadingline, and the pumping equipment, in order todissipate static electricity. Make permanentconnections between the rails on which the tankcar stands and the piping to the storage tankusing No. 4 standard copper wire. Put bondedconnections across all gasketed surfaces.

Firefighting equipment should be immediatelyavailable to the unloading crew, and they should bethoroughly familiar with its proper use. Dry chemicalextinguishers are recommended. Shower andeyewash fountains should be available in theimmediate area.

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Tank cars should be unloaded only in the daytime or whenadequate lighting is provided. Do not unload if lightning ispresent. Suitable spill containment should be provided.Top unloading by use of a dedicated self-priming pump isrecommended rather than by inert gas pressureunloading. Acrylonitrile is not shipped in tank cars or tanktrucks with a bottom outlet.

These procedures may also be used to unload tank trucks. To eliminate spills and to reduce acrylonitrile exposure, it is mandatory that the receiving site pro- videthe following dedicated equipment: self-primingunloading pump, hose with a two inch dry disconnectand a two inch vapor return line. Suitable spillcontainment should also be provided

ENVIRONMENTAL PROTECTION

Acrylonitrile is a highly regulated substance. As with allchemicals, releases into the environment that containacrylonitrile should be minimized, and controls to mitigate planned or unplanned releases to theenvironment are necessary. In addition, emissions and effluents containing acrylonitrile should be reviewed with respect to environmental permits and regulationssuch that compliance is ensured and environ- mentalhealth remains protected.

The following sections provide environmental information and data to be used in handling in anenvironmentally protective manner.

Air Issues

Acrylonitrile is defined as an air toxic and a volatile organic compound under U.S. environmental regulations(40 CFR 63). As such, emissions of acrylonitrile in generalshould be mitigated or controlled.Emissions routinely emanate from transfer operations, storage vessels, process vents, wastewater management,and fugitive leaks. Fugitive leaks are releases of acrylonitrile vapor from connections, seals, or packing onflanges, pumps, valves, compressors, etc.

While source elimination should be the method of choice for controlling air emissions, ultimately it is necessary to have an atmospheric vent or fugitive emission source. Control methods are normally

dependent on the type of equipment whichemits the compound. In general, however,transfer operations and storage vessels utilizescrubbers, flares, carbon adsorption, etc. Process vents may utilize these and/orincinerators, boilers, process heaters, absorbers,etc. Fugitive emissions are best controlled bycomponent elimination, but a routine leakdetection and repair (LDAR) program issuggested (and in some cases required byregulation) for controlling these types of emissions. Contact Cornerstone for informationon a suggested LDAR program.

In the U.S., the EPA has established specificationsfor control devices and their operation. Theseshould be reviewed for application to the devicesinstalled for controlling acrylonitrile emissions. Inaddition, the U.S. Coast Guard has requirementson control devices used to minimize emissionsfrom marine loading operations. ContactCornerstone for guidance on the type of controldevice desired for controlling emissions of Cornerstone’s acrylonitrile product.Since acrylonitrile is a suspected carcinogen, asdiscussed elsewhere in this brochure, some stateshave established maximum concentrations ofacrylonitrile in ambient air based on the theoreticalrisk to human populations. As of 1995, a level of1.47 µg/m3 was considered to cause a 1 in 10,000risk of cancer. Estimates of acrylonitrile emissionsfrom handling, use, and disposal operations couldbe compared to any such maximum limits forcompliance purposes. In addition, a permit isrequired for emissions from stationary sources.Various methods are available for calculatingemissions, but most notably, the document AirPollution Control Document Number 42 (AP-42) hasbeen developed by the U.S. EPA for this use. ContactCornerstone if guidance is needed in calculating acrylonitrile emissions from the use of our product.

Waste Issues

Acrylonitrile product is defined under U.S. law as a hazardous waste when discarded (40 CFR 261.33). In the U.S., users of acrylonitrile product may be required to notify the government that they

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generate hazardous waste if there is a potential thatthey may generate acrylonitrile wastes from spills, leaks,tank cleanouts, or similar sources. Acrylonitrile wastesinclude materials contaminated with the product, such as PPE, soil and debris. Notification forms should beobtained from your state or federal government.

Generators of hazardous waste must comply with additional requirements outlined in 40 CFR 262, includingrequirements relating to training employees, effectiveemergency procedures, maintaining records, and filingreports. Generators may accumulate such waste for upto 90 days in tanks or containers without a permitprovided certain standards are met. Generatorsmanaging waste in other ways should obtain a permit.

Acrylonitrile product carries a hazardous waste code of atleast U009. Depending on the amount of product in thewaste, codes of D001 (flammable) and D018 (benzenetraces) may be appropriate for the waste, as well.

Containers which have held acrylonitrile must be managed under hazardous waste regulations unless theyhave been emptied to a level so that they do not qualifyas hazardous waste per 40 CFR 261.7. A list of drumreclaimers used by Cornerstone is available on request.

Cleanouts from stationary tanks which held acrylonitrileproduct must be managed as hazardous waste. Ingeneral, leaks and spills of acrylonitrile must be handledas hazardous waste. Use personal protective equipmentdesignated elsewhere in this brochure when respondingto such acrylonitrile releases.

Once Cornerstone’s acrylonitrile product enters theproduction process as a raw material, wastes emanating from that process, even if they contain acrylonitrile, mayor may not be classified as hazardous. An assessment of such wastes as to the characteristics of ignitability, corrosivity, reactivity, or toxicity (as defined in 40 CFR 261)should be made to determine appropriate handlingrequirements.

Under U.S. hazardous waste regulations, acrylonitrile cannot be managed in land management units, such as surface impoundments, landfills and injection wells,unless an exemption is granted or unless it meetscertain criteria. A “Universal Treatment Standard” (UTS)or 0.24 mg/l in wastewater and 84 mg/kg in non-wastewater (e.g., soil) is required before acrylonitrile

can enter a land management unit. Likewise,certain UTS levels of acrylonitrile impurities arealso mandated. Refer to 40 CFR 268, or contactCornerstone for more guidance on landmanagement of acrylonitrile waste.

If acrylonitrile waste is sent offsite formanagement, additional transportationrequirements exist. Specific Department of Transportation containers must be labeled andused. If hazardous, the waste must be reportedon a “Uniform Hazardous Waste Manifest.” These documents can be obtained from yourstate environment regulatory agency. Transporters who are licensed to transporthazardous waste must be used.

Only certain types of disposal techniques areallowed for hazardous wastes such as acrylonitrile product wastes. In general,incineration is the method used to dispose of acrylonitrile. Guidance on such techniques canbe found under hazardous waste regulations,orby contacting Cornerstone.

Even when acrylonitrile wastes fall into the “non-hazardous” category, they should be handled withcare. State regulations should be reviewed todetermine if local rules governing non-hazardouschemical wastes exist. In the absence of local rules,non-hazardous acrylonitrile contaminated wastesmust be handled in a secure, industrial landfill if notincinerated. Cornerstone will provide a list of sitesused for non-hazardous acrylonitrile contaminatedwater, hazardous waste disposal, or hazardouswaste transporters, upon request

Wastewater Issues

Process wastewater containing acrylonitrile mustbe treated before discharging to water under a “National Pollutant Discharge Elimination System” (NPDES) wastewater permit. Most acrylonitrileusers, as well as producers, are subject to federallimitations on chemicals present in wastewaterdischarges.These limits apply to those facilities that use bio-chemical treatment, non-biochemical treatment,or that indirectly discharges into a publicly owned

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treatment works (POTW). One of the chemicals limited is acrylonitrile; some acrylonitrile impurities are also limited. These limitations can be found in 40 CFR 414.

If the acrylonitrile wastewaters meet the definition of “hazardous,” they must be managed by some means other than surface impoundments. Surface impoundments may be allowable under federal rules ifcertain levels of contamination are met; however, Cornerstone does not recommend their use forhazardous acrylonitrile waste. If used for non-hazardousacrylonitrile waste, leak detection or other monitoring system is recommended to verify that the impoundmentprotects groundwater.

Groundwater Issues

Cornerstone recommends that facilities and equipment which hold acrylonitrile product be constructed above asystem designed to protect groundwater. Suchprotection systems include secondary containment,which also provides spill protection, as well as leakdetection for systems where visual inspection is notpossible. However, studies have shown that if spilled onsoil, acrylonitrile readily biodegrades. Higherconcentrations in soil tend to slow the degradationprocess. A level of 100 mg/kg or below has been shownto readily biodegrade. Spills of acrylonitrile to soil shouldbe cleaned to less than this level in an effort to protectgroundwater. Spill cleanup criteria may vary based onlocal regulations. Check with the locality to obtain therecommended criteria.

Accidentaland Permitted ReleasesAccidental releases of acrylonitrile to the environment include unpermitted leaks, spills, and emissions. In theU.S., such releases of acrylonitrile in excess of 100 pounds(about 13 gallons) are immediately reportable togovernmental authorities. In some localities, any release of acrylonitrile, even if below 100 pounds, is alsoreportable.

Local rules should be reviewed to determine the reportablequantity for that location.

Annual total environmental releases of acrylonitrile, amongother things, may be reportable to local, state, and federalauthorities by July 1 of each year. Total releases include allpermitted and non-permitted discharges to air, water,and land. This reporting is required if a facility meets

certain SIC code, employee number, and acrylonitrileuse criteria.Refer to 40 CFR 372 or contact Cornerstone forguidance or more information. Some acrylonitrile impurities are also reportable under this rule, if theyexceed the exemption level of one percent in theproduct.

Spill or Release ResponseIn the event of a spill or release of acrylonitrile,standard response procedures should beimplemented. Initial control systems should be usedto stop or control the release.

The source of the release should be shut off, and containment of released material should beimplemented. Personal protective equipmentshould be used at all times in responding to anacrylonitrile release.

For spills of acrylonitrile, berms, dikes, trenches, or other containment devices should be employed to reduce the horizontal extent of the spill. Firefighting foam is recommended for placement on the spill tominimize volatilization, reduce personnel exposure, and prevent potential ignition.

Once contained, a spill of acrylonitrile should be picked up without delay to avoid furthercontamination. Non-sparking equipment andmethods that prevent friction or ignition should beemployed. Although it is preferable to

keep the quantity of waste small by avoidingdilution, in the interest of safety is may be necessaryto dilute with water or other material to reduceexposure and ignition potential. Spills andcontaminated media should be assessed forcompliance with solid waste rules regarding storageand disposal.

Residue that remains after cleanup of the spill canbe treated with sodium metabisulfate to morequickly degrade remaining low levels of acrylonitrile. The sodium metabisulfite should beleft on the residue for several days. Sodiummetabisulfite should NEVER be used on pureacrylonitrile as a violent reaction and fire couldresult.Environmental Impacts

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Acrylonitrile is unstable in the environment. In the atmosphere, acrylonitrile may react with oxygen, hydrogenand oxygen, or ozone. Where nitric oxides are present,hydrogen cyanide, formyl cyanide, nitric acid, carbonmonoxide, and ozone may be formed when acrylonitrilereacts. In water, acrylonitrile decomposes or is biodegraded. Some acrylonitrile may volatilize from water. Light candegrade acrylonitrile in the air and water.

Biodegradation of acrylonitrile in the environment generallyoccurs, although very high levels of acrylonitrile can inhibitbioactivity. In soil, levels of acrylonitrile below 100 mg/kghave been shown to readily degrade, and biodegradationcan generally achieve a 99% reduction in this media. Bioaccumulation of acrylonitrile does not occur.

Aquatic life can be adversely affected where acrylonitrilelevels of more than 10 mg/l are present. The following acutetoxicity data has been collected on acrylonitrile:

Acute toxicity - LC50 24 hr mg/l 48 hr mg/l

Water flea 13 7-22Brown shrimp 8-26 NA Carp 37 25Fathead minnow 33 15-21Bluegill sunfish 25 14

Acrylonitrile Product Components

Acrylonitrile as manufactured by Cornerstone is over99% pure. However, as with any chemical product,some impurities may exist within the commodityform of the material. The following is a list of potential trace impurities that may be present inCornerstone’s acrylonitrile. This list should be reviewedrelative to regulatory listings to determine if any suchcomponents are of concern for the purposes of environmental permits and regulatory notifications.Contact Cornerstone if you need assistance inassessing regulatory implications.Where noted with an asterisk (*), these chemicals may be present on various U.S. environmental regulatory lists:

Acetic acid* Acetone* Acetonitrile* Acrolein* Acrylamide* Benzene* Crotonitrile Hydrogen cyanide* Hydroquinone* Methacrylonitrile*Methyl ether hydroquinone OxazolePeroxide

Propionitrile*

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Regulatory Listings

In the United States, acrylonitrile is contained on the following environmental regulatory lists at a minimum and is subject to the standards contained in those regulations.

40 CFR 372 - Toxic Chemicals Release Reporting-Community Right to Know - Requires reporting of annual quantities of acrylonitrile used and released to theenvironment.

40 CFR 302 & 355 - Comprehensive EnvironmentalResponse, Compensation and Liability Act (CERCLA)Designation, Reportable Quantities andNotification; Emergency Planning and Notification -Requires immediate reporting of releases of acrylonitrileto air, water, or land.

40 CFR 261 - Identification and Listing of HazardousWaste - Requires management of discarded acrylonitrileas a hazardous waste.

CAA Section 112 - Clean Air Act (CAA) - Requires management of emissions of acrylonitrile to air.

40 CFR 116, 117, 401 & 414 - Federal Water Pollution Control Act - Requires management of acrylonitrile as a toxic pollutant in wastewater.

55 FR 1470 - Safe Drinking Water Act - Requires priority management of acrylonitrile in drinking water.

40 CFR Parts 152, 180, 185 & 186 - Federal Insecticide, Fungicide and Rodenticide Act (FIFRA) - Requires special handling of acrylonitrilewhen used as an insecticide, fungicide or rodenticide.

Test Methods

References that contain analytical methods fortesting acrylonitrile and its impurities inenvironmental media include “Test Methods forEvaluating Solid Waste” (SW-846) for water andwastes; and 40 CFR 60Appendix A, Method 18 for air emissions. Both of these references can be obtained from the U.S. Government printing office (202-783-3238). Contact your local Cornerstone technical salesrepresentative for more information on theseanalytical procedures.

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APPENDIX I - NIOSH ANALYTICAL METHOD 1604ACRYLONITRILE 1604

CH2=CHCN MW : 53.06 CAS: 107-13-1 RTECS: AT5250000

Method: 1604, Issue 2 Evaluation: Full Issue 1: 15 February 1984Issue 2: 15 August 1994

OSHA: 2 ppm; C 10 ppm (skin) Properties: liquid; d 0.806 g/mL @ 20˚C;NIOSH: carcinogen; 1 ppm; C 10 ppm/15 min; BP 77.2˚C; VP 11 kPa (83 mm Hg 11%

v/v)Group 1 Pesticide (skin) @ 20˚C; explosive range 3 to 17% v/v inairACGIH: carcinogen; 2 ppm (skin)

(1 ppm = 2.17 mg/m3 @ NTP)Synonyms: 2-propenenitrile; vinyl cyanide; AN.

SAMPLING

Sampler: SOLID SORBENT TUBE (coconut shell charcoal,100 mg/50 mg)

Flow Rate: 0.01 to 0.2 L/min

Vol-Min: 3.5 L @ 2 ppm -Max: 20 L

Shipment: Routine

SampleStability: At least 7 days @ 25˚C [1,2]Blanks: 2 to 10 field blanks per set

ACCURACY

Range Studied: 1 to 100 mg/m3

[1,2] (20-L samples)Bias: -4.8%OverallPrecision (srT): 0.06 [1,2]Accuracy: ±14.1%

MEASUREMENT

Technique: GAS CHROMATOGRAPHY, FIDAnalyte: acrylonitrile

Desorption: 1 mL 2% (v/v) acetone in carbon disulfide (CS2); letit stand for 30 min.

Injection Volume: 2 µLTemperature-Injection: 200˚C

-Detector: 200˚C-Column: 85˚C

Carrier Gas: N2 or He, 25 mL/minColumn: 3-m x 3-mm stainless steel,

20% SP-1000 on 80/100Chromosorb WHP

Calibration: Standard solutionsof distilledacrylonitrile in hexane

Range: 15 to 1000 µg per sample [1]Estimated LOD: 1 µg per sample [1]Precision (Sr) 0.06 @ 16 µg per sample [1]

Applicability: The working range is 0.7 to 46 ppm (1.5 to 100 mg/m3) for a 10-L air sample. This methodis applicable to 15-minute ceiling measurements. NIOSH has sampled for acrylonitrile at acrylic andelectric plants.Interferences: None known. An alternate chromatographic column is a fused silica capillary, 30m x 0.32-mm, coated with0.5 µm DB-WAX or 1 µm DB-5.Other Methods: This revises NIOSH Method S156 [1,3] and Method 1604 (dated 2/15/84). P&CAM 202has been dropped because of poor sensitivity (LOD 0.1 mg per sample) [4]. Marano et al. [5] have shownthat the use of a nitrogen selective detector (NPD) increases the sensitivity and specificity of the analysis.

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

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APPENDIX I - NIOSH ANALYTICAL METHOD 1604 ACRYLONITRILE 1604

Reagents:1. Carbon disulfide, chromatographic quality.*2. Acetone, chromatographic quality.3. Hexane, reagent grade.4. Eluent: 2% acetone (v/v) in carbon disulfide.*5. Acrylonitrile, stabilized.* Stable at least one month at 4˚C.6. Acrylonitrile, freshly distilled.*7. Calibration stock solution, 4 µg/µL. Add 50 µL freshly distilled

acrylonitrile to 10 mL hexane. Stable one week at 4˚C.8. Helium, purified.9. Hydrogen, prepurified.10. Air, filtered.*See Special Precautions

Equipment:1. Sampler: glass tube, 7 cm long, 6-mm OD,

4-mm ID, flame-sealed ends with plastic caps, 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 foamplug follows the back section. Pressure dropacross the tube at 1 L/min airflow must beless than3.4 kPa. Tubes are commercially available.

2. Personal sampling pump, 0.01 to 0.2 L/min, with flexible connecting tubing.

3. Gas chromatograph, flame ionization detector, integrator and column (page 1604-1).

4. Micro-distillation apparatus for vacuumdistillation of acrylonitrile.

5. Vials, 2-mL, PTFE-lined crimp caps.6. Syringe, 10-µL and other sizes as needed,

readable to 0.1µL.7. Volumetric flasks, 10-mL.8. Pipets, 1-mL, with pipet bulb.

Special Precautions: Carbon disulfide is toxic and a severe fire and explosion hazard (flash point = -30˚C). Acrylonitrile is explosive, flammable, toxic, and a suspect carcinogen [3]. Work with these compounds only in a hood.

Sampling:1. Calibrate each personal sampling pump with a representative sampler in line.2. Break the ends of the sampler immediately before sampling. Attach sampler to personal sampling pump with flexible

tubing.3. Sample at an accurately known flow rate between 0.01 and 0.2 L/min for a total sample size of 3.5 to 20 L.4. Cap the samplers pack securely for shipment.

Sample Preparation:5. Place the front and back sorbent sections of the sampler tube in separate vials. Discard the glass wool and foam

plugs.6. Add 1.0 mL eluent to each vial. Attach crimp cap to each vial.

NOTE: An internal standard, e.g., 0.1% (v/v) benzene or n-hexane, may be added at this step.7. Allow to stand 30 min with occasional agitation.


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Calibration and QualityControl8. Calibrate daily with at least five working

standards over the range 1 to 1000 µgacrylonitrile per sample.a. Add known amounts of calibration stock

solution, or a serial dilution thereof, toeluent in 10-mL volumetric flasks and diluteto the mark with eluent (2% acetone inCS2).

b. Analyze together with samples and blanks(steps 11 and 12).

c. Prepare calibration graph (peak area vs. µg acrylonitrile).NOTE: Compare the peak areas of the working standards with a 0.1 mg/mLreference standard prepared fromstabilized (undistilled) acrylonitrile inhexane.When the concentration of the working standards starts to decrease, prepare newworking standards.

9. Determine desorption efficiency (DE) at least once for each batch of charcoal used forsampling in the calibration range (step 8).Prepare three tubes at each of five levels plusthree media blanks.a. Remove and discard back sorbent section

of a media blank sampler.b. Inject a known amount of calibration stock

solution directly onto front sorbent section with a micro liter syringe.

c. Cap the tube. Allow to stand overnight.

d. Desorb (steps 5 through 7) and analyze together with working standards (steps11 and 12).

e. Prepare a graph of DE vs. µg acrylonitrile recovered.

10. Analyze three quality control blind spikes and three analyst spikes to insure that thecalibration graph and DE graph are in control.

Measurement:

11. Set gas chromatograph according to manufacturer’srecommendations and to conditions given on page 1604-1. Inject sample aliquot manually using solventflush technique orwith autosampler.

NOTE 1: If peak area is above the linear range of the working standards, dilute with eluent, reanalyze and apply the appropriate dilution factor incalculations.NOTE 2: Under these conditions trfor acrylonitrile is ca. 8.5 min.

12. Measure peak area.

Calculations:13. Determine the mass, µg (corrected for DE) of acrylonitrile found

in the sample front (Wf) and back (Wb) sorbent sections, and inthe average media blank front (Bf) and back (Bb) sorbent sections.

NOTE: If Wb > Wf/10, report breakthrough andpossible sample loss.

14. Calculate concentration, C, of acrylonitrile in the air volumesamples, V (L):

C = [(Wf + Wb) - (Bf + Bb)], mg/m3

V

Evaluation of Method:Method S156 [2] was validated at levels of 0.48,0.95, and 1.91 mg per sample, using samplesof acrylonitrile prepared both by samplingstandard atmospheres generated bycalibrated syringe drive and by spikingstandard solutions in hexane on to thecharcoal [6].

After the OSHA standard for acrylonitrile waslowered to 2 ppm, the method was evaluated byNIOSH at levels of 8.6 and 16.6 µg per sample(desorption solvent 2% acetone in CS2), usingsamples from gas bag atmospheres and by


24


spiking the charcoal with standard solutions of acrylonitrile inhexane [1]. At the higher levels (> 16 µg), the recoveries of acrylonitrile averaged 94% and the Sr was 0.06. At the lower level(8.6 µg), the recovery for the two sets of samples prepared fromstandard atmospheres averaged 79% with a Sr of 0.14. The sampleset prepared by spiking charcoal at the lower level had a recoveryof 94%. The parity between the recoveries of samples obtainedfrom test atmospheres and from liquid spikes at the lower levelsuggested a possible problem with accuracy at this level [1].Samples were found to be stable for at least seven days at room temperature [1,6]. Several breakthrough studies have beenreported. At 80% relative humidity, breakthrough occurred after184 minutes (36.7 L) sampling 8 mg/m3 at 0.2 L/min [7].Breakthrough did not occur after sampling dry air at 92 mg/m3 at0.2 L/min for 4 hours [6].

References:[1] Gagnon, Y.T. and Posner, J.C. Recovery of Acrylonitrile from

Charcoal Tubes at Low Levels ,Am Ind. Hyg. Assoc. J., 40, 923-925 (1979).

[2] NIOSH Manual of Analytical Methods, 2nd ed., V.3, S156, U.S.Department of Health, Education, and Welfare, Publ. (NIOSH)77-157-C (1977).

[3] Criteria for a Recommended Standard...OccupationalExposure to Acrylonitrile, U.S. Department of Health, Education, and Welfare, Publ. (NIOSH) 78-116 (1978); revisedMar., 1978 as part of NIOSH testimony at OSHA hearing.

[4] NIOSH Manual of Analytical Methods, 2nd ed.,V.1, P&CAM 202, U.S. Department of Health, Education and Welfare, Publ. (NIOSH) 77-157-A (1977).

[5] Marano, R.S., Levine, S.P. and T.M. Harvey. Trace Determination of Subnanogram Amounts of Acrylonitrile in Complex Matrices by Gas Chromatography with a Nitrogen Selective Detector. Anal. Chem. 50, 1948 (1978).

[6] Documentation of the NIOSH Validation Tests, S156, U.S. Department of Health, Education,and Welfare, Publ. (NIOSH) 77-185 (1977).

[7] OSHA Report, Acrylonitrile Method 37, Organic Methods Evaluation Branch, OSHA Analytical Laboratory, Salt Lake City, UT (May 1982).

Method Revised by:Y.T. Gagnon, NIOSH/DPSE; S156 originally validated under NIOSH Contract CDC-99-74-45.


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APPENDIX II - MEDICAL SURVEILLANCE PROGRAMAll medical examinations and procedures mustbe performed by or under the supervision of alicensed physician. The physician should beaware of the results of recent investigations of the effects of exposure to acrylonitrile. (See29 CFR 1910.1045) It is important for thephysician to become familiar with theoperating conditions in which exposure of employees to acrylonitrile may occur.Employees having skin diseases may nottolerate the required protective clothing; inaddition, those with chronic respiratoryailments may not tolerate the wearing of negative-pressure respirators.

Medical histories and laboratory examinationsare required for each employee subject tooccupational exposure to acrylonitrile abovethe action level (one (1) part per million, time-weighted average (TWA)) by the U.S.Occupational Health and Safety Administration (OSHA) in the U.S. withoutregard to the use of respirators. Employersmust screen employees for history of certainmedical conditions which might place theemployees at increased risk from exposure;(a) central nervous system (CNS) dysfunction;(b) respiratory disease; (c) gastrointestinal disease; (d) skin disease. The purpose of themedical procedures outlined above is toestablish a baseline for future healthmonitoring. Persons, who are unusuallysusceptible to the effects of anoxia, or thosewith anemia, would be expected to be at increased risk if exposed to acrylonitrile. Inaddition to the emphasis on the CNS,

respiratory and gastrointestinal systems, the cardiovascularsystem, liver, and kidney functions should also be stressed.Consult the OSHA Acrylonitrile standard for specific guidance.

General Principles

A. For Acrylonitrile, the OSHA action level for medicalsurveillance for employees with potential exposure toacrylonitrile monomer is at or above one part permillion (1 PPM) as an eight hour time weighted average.

B. The OSHA permissible exposure limit for acrylonitrilemonomer is 2 ppm as an 8-hour time weighted average. A ceiling of 10 ppm over a 15-minute period is established.

C. Pre placement and periodic examinations of employeesshould be performed by licensed physicians.

D. Pre placement and periodic, and/or respiratoryexaminations should be mandatory for those exposed or potentially exposed to acrylonitrile at the statedconcentrations.

E. Exposures to acrylonitrile may result in diseases of thenervous, respiratory and hematologic systems.

ExaminationsA. Pre placement Examination

1. The pre placement examination for those workerswith potential assignments in areas whereacrylonitrile (AN) exposure is possible should includebut not be limited to:a. A work history and medical history with special

attention to skin, respiratory, and gastrointestinal systems, and those non-specific symptoms, such as headache, nausea,vomiting, dizziness, weakness, or other centralnervous system dysfunctions that may beassociated with acute or with chronic exposureto AN;

b. A complete physical examination giving particular attention to the peripheral and central nervous system, gastrointestinal system,respiratory system, skin, and thyroid;

26

c. A 14- by 17-inch posteroanterior chest X-ray;and

d. Further tests of the intestinal tract, includingfecal occult blood screening, for all workers 40years of age or older and for any other affectedemployees for whom, in the opinion of thephysician, such testing is appropriate.

B. Periodic Examination 1. A periodic examination consisting of the same basic

components as a pre- placement exam should be offered to employees on an annual basis.

2. If an employee is terminated for any reason and a periodic exam has not been performed within a six-month period, the former employer should offer suchan exam at that time.

3. An additional exam should be provided if an employeeexhibits any signs or symptoms associated withexposure to acrylonitrile.

Informationto Physician

A. Examining physicians should be familiar with the effects of acrylonitrile exposure. The physician should have thefollowing information available when performing examsfor acrylonitrile.1. A copy of Standard 29 CFR 1910.1045 and its

appendixes;2. A description of the affected employee’s duties as

they relate to the employee’s exposure;3. The employee’s representative exposure level;4. The employee’s anticipated or estimated exposure

level (for pre placement examinations or in cases of exposure due to an emergency);

5. A description of any personal protective equipmentused or to be used;

6. Information from previous medical examinations of the affected employee which is not otherwiseavailable to the examining physician.

Information fromExamining Physicians

A. Following each examination, the examining physician must provide a written opinionregarding the findings. This opinion shouldinclude:1. The results of the medical examination

and tests performed;2. The physician’s opinion as to whether

the employee has any detected medicalcondition(s) which would place theemployee at an increased risk of material impairment of the employee’shealth from exposure to AN;

3. Any recommended limitations upon the employee’s exposure to AN or upon theuse of protective clothing andequipment such as respirators;

4. A statement that the employee hasbeen informed by the physician of theresults of the medical examination andany medical conditions which requirefurther examination or treatment.

B. Employees should be provided with a copyof the written opinion regarding their exam.

C. The employer shall instruct the physician notto reveal in the written opinion specificfindings or diagnosis unrelated tooccupational exposure to acrylonitrile.

Medical RecordsUnder OSHA (29 CFR 1910.1045) medicalrecords must be maintained during thecourse of employment plus 40 years. Localregulations may vary.

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Customer ServiceFortier Complex - U.S. (Louisiana)Telephone: 504-431-6189 or Toll free: 1-800-236-0977

After Office Hours, please call:

(504) 431-6353 OR (504) 431-9511

PRT 794

acrylonitrile - cornerstone chemical company

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