Standard Operating Procedure

1,4-Dioxane

Print a copy and insert into your
Laboratory Safety Manual and Chemical Hygiene Plan.

Department: / Chemistry
Date SOP was written: / 11/29/2012
Date SOP was approved by PI/lab supervisor: / 11/29/2012
Principal Investigator: / Richmond Sarpong
Internal Lab Safety Coordinator/Lab Manager: / Rebecca Murphy
Lab Phone: / 510-643-2485
Office Phone: / 510-643-6312
Emergency Contact: / Richmond Sarpong (626)-644-2407
(Name and Phone Number)
Location(s) covered by this SOP: / Latimer 834,836,837,838,839,842,844,847,907
(Building/Room Number)

Type of SOP: Process Hazardous Chemical Hazardous Class

Purpose

1,4-Dioxane is a select carcinogen and a peroxide former. Like some other ethers, dioxane combines with atmospheric oxygen on standing to form explosive peroxides. Distillation of dioxane concentrates these peroxides, thus increasing the danger. If not stored and handled properly, this can pose a serious threat to the health and safety of laboratory personnel, emergency responders and chemical waste handlers. Hence, it is important to follow safety protocols to handle this chemical.

1,4-Dioxane (dioxane), a cyclic ether, is used as a degreasing agent, as a component of paint and varnish removers, and as a wetting and dispersion agent in the textile industry. Dioxane is used as a solvent in chemical synthesis, as a fluid for scintillation counting, and as a dehydrating agent in the preparation of tissue sections for histology.

Physical & Chemical Properties/Definition of Chemical Group

CAS#: 123-91-1

Class: Peroxide forming chemical and carcinogen,

Molecular Formula: C4H8O2

Form (physical state): liquid

Color: colorless

Boiling point: 100-102 ºC

Potential Hazards/Toxicity

This product is or contains a component that has been reported to be possibly carcinogenic.

Target Organs

Liver, Kidney, Central nervous system

Other hazards

May form explosive peroxides.

Potential Health Effects

Inhalation: May be harmful if inhaled. Causes respiratory tract irritation

Skin: May be harmful if absorbed through skin. Causes skin irritation.

Eyes: Causes eye irritation.

Ingestion: May be harmful if swallowed.

CalOSHA Permissible Exposure Limit (PEL): 0.28 ppm

Engineering Controls

All operations involving 1,4-dioxane must be carried out in a certified chemical fume hood (certified once every year by EH&S).

Personal Protective Equipment (PPE)

Respiratory Protection

NOTE: Lab personnel intending to use/wear a respirator mask must be trained and fit-tested by EH&S. This is a regulatory requirement.

Refer to 8 CCR 5144 for selection of respirators. A respiratory protection program that meets 8 CCR 5144 must be followed whenever workplace conditions warrant use of a respirator.

Respirators should be used only under any of the following circumstances:

·  As a last line of defense (i.e., after engineering and administrative controls have been exhausted).

·  When Permissible Exposure Limit (PEL) has exceeded or when there is a possibility that PEL will be exceeded.

·  Regulations require the use of a respirator.

·  An employer requires the use of a respirator.

·  There is potential for harmful exposure due to an atmospheric contaminant (in the absence of PEL)

·  As PPE in the event of a chemical spill clean-up process

Hand Protection

Handle with butyl gloves.

NOTE: Consult with your preferred glove manufacturer to ensure that the gloves you plan on using are compatible with 1,4-dioxane.

Refer to glove selection chart from the links below:

http://www.ansellpro.com/download/Ansell_8thEditionChemicalResistanceGuide.pdf

OR

http://www.allsafetyproducts.biz/page/74172

OR

http://www.showabestglove.com/site/default.aspx

OR

http://www.mapaglove.com/

Eye Protection

Safety goggles or glasses.

Skin and Body Protection

Fire/flame resistant lab coat (100% cotton based), cotton based clothing/attire, full length pants or equivalent, closed toe shoes.

Hygiene Measures

Avoid contact with skin, eyes and clothing. Wash hands before breaks and immediately after handling 1,4-dioxane.

First Aid Procedures

If inhaled

If breathed in, move person into fresh air. If not breathing, give artificial respiration. Consult a physician.

In case of skin contact

Wash off with soap and plenty of water. Consult a physician.

In case of eye contact

Rinse thoroughly with plenty of water for at least 15 minutes and consult a physician.

If swallowed

Do NOT induce vomiting. Never give anything by mouth to an unconscious person. Rinse mouth with water. Consult a physician.

General advice:

Consult a physician. Show this safety data sheet to the doctor in attendance. Move out of dangerous area.

Special Handling and Storage Requirements

Precautions for safe handling

Avoid contact with skin and eyes. Avoid inhalation of vapor or mist. Keep away from sources of ignition (such as Bunsen burners). Take measures to prevent the build-up of electrostatic charge.

Conditions for safe storage

Keep container tightly closed in a dry and well-ventilated place. Containers which are opened must be carefully resealed and kept upright to prevent leakage.

Possibility of hazardous reactions

Vapors may form explosive mixture with air.

Conditions to avoid

Heat, flames and sparks. Extremes of temperature and direct sunlight.

Materials to avoid

Oxygen, Oxidizing agents, Halogens, Reducing agents, Perchlorates, Trimethylaluminum

Hazardous decomposition products

Hazardous decomposition products formed under fire conditions. - Carbon oxides

Spill and Accident Procedure

Chemical Spill Dial 911

Spill – Assess the extent of danger. Help contaminated or injured persons. Evacuate the spill area. Avoid breathing vapors. If possible, confine the spill to a small area using a spill kit or absorbent material. Keep others from entering contaminated area (e.g., use caution tape, barriers, etc.).

Small (<1 L) – If you have training, you may assist in the clean-up effort. Use appropriate personal protective equipment and clean-up material for chemical spilled. Double bag spill waste in clear plastic bags, label and take to the next chemical waste pick-up.

Large (>1 L) – Dial 911 and 510-642-9090 for assistance.

Chemical Spill on Body or Clothes – Remove clothing and rinse body thoroughly in emergency shower for at least 15 minutes. Seek medical attention. Notify supervisor and EH&S immediately. Follow up with a call to 510-642-9090 to report the incident.

Chemical Splash Into Eyes – Immediately rinse eyeball and inner surface of eyelid with water from the emergency eyewash station for 15 minutes by forcibly holding the eye open. Seek medical attention. Notify supervisor and EH&S immediately. Follow up with a call to 510-642-9090 to report the incident.

Medical Emergency Dial 911

Life Threatening Emergency, After Hours, Weekends And Holidays – Dial 911 or go to the nearest emergency room. Note: All serious injuries must be reported to EH&S within 8 hours. Follow up with a call to 510-642-9090 to report the incident.

Non-Life Threatening Emergency – Go to the Occupational Health Facility (Tang Health Center). After hours go to the nearest emergency room. Note: All serious injuries must be reported to EH&S within 8 hours. Follow up with a call to 510-642-9090 to report the incident.

Needle stick/puncture exposure (as applicable to chemical handling procedure) – Wash the affected area with antiseptic soap and warm water for 15 minutes. For mucous membrane exposure, flush the affected area for 15 minutes using an eyewash station. Go to the Occupational Health Facility (Tang Health Center). After hours go to the nearest emergency room. Note: All needle stick/puncture exposures must be reported to EH&S within 8 hours. Follow up with a call to 510-642-9090 to report the incident.

Decontamination/Waste Disposal Procedure

Dispose of 1,4-dioxane container before the expiration date as marked by the manufacturer on the container, or, within 1 year from the date of opening, whichever is sooner.

General hazardous waste disposal guidelines:

Label Waste

·  Label all containers with the label provided at http://ehs.berkeley.edu/hm/279-new-hazardous-waste-program-hwp.html. See the EH&S Fact Sheet, “Hazardous Waste Management” for general instructions on procedures for disposing of hazardous waste.

Dispose of Waste

·  Dispose of regularly generated chemical waste within 6 months

·  Call EH&S for questions

Safety Data Sheet (SDS) Location

SDS can be accessed online at http://ucmsds.com

Protocol/Procedure

When used as a solvent for chemical reactions, 1,4-Dioxane should be handled by lab members wearing a flame-resistant lab coat, gloves, and chemical safety goggles and used only inside a functioning fume hood. Dioxane is used in quantities ranging from <1mL up to 2L, and at temperatures up to 120 ºC. If being used at a temperature higher than its boiling point (101 ºC), the reaction vessel must be capable of handling the pressure buildup and the use of a blast shield is recommended for all volumes, and required if >50mL dioxane is used. After completion of the reaction, any remaining dioxane should be disposed as hazardous waste. If Dioxane is to be evaporated using a rotavap, then a dry ice condenser must be employed to trap any volatiles and these disposed of as hazardous waste.

Dioxane is also purified by distillation and is kept on a still in the lab. Efforts should be made to prevent the dioxane from coming into contact with air to limit the danger of developing peroxides. Additionally, the distilled dioxane should be refreshed every couple of days to prevent any buildup of peroxides. Distilled dioxane can also stored in an airtight schlenk tube. All dioxane, whether distilled or not should be peroxide tested every 6 months and disposed of through EH&S if peroxides are detected. As a peroxide forming chemical, all containers should be dated with the date they are received and opened. If any old containers of dioxane test positive for the presence of peroxides or are suspected of containing peroxides (due to the presence of white crystals, etc.) they should be tagged as hazardous waste and disposed of properly. Containers should never be shaken if peroxides are suspected, and care should be taken in trying to open old containers of dioxane.

Protocol/Procedure for– 1,4 Dioxane

CAS # 123-91-1

Preparation / Never open a dented or otherwise compromised container of 1,4 Dioxane. Alert lab safety manager immediately.
Never open/use/move a 1,4 Dioxane container that is suspected to contain peroxides or is in contact with crystals indicative of peroxide formation. Do not touch the crystals. Alert lab safety manager immediately.
Know the location of the nearest fire extinguisher, eyewash, and safety shower before beginning work.
Never work alone. Make sure there is another worker present who is also trained in the 1,4 Dioxane SOP.
Know the location of the nearest fire extinguisher, eyewash, and safety shower before beginning work.
Lab-specific Information / If not in use 1,4 Dioxane containers have to be safely stored in the ventilated flammable storage cabinets.
Store and transport 1,4 Dioxane containers in secondary containment (for example polyethylene bottle carrier).
Keep storage container closed (air tight) when not in use.
Maintain the smallest amount necessary for ongoing work. Use in the smallest practical quantities for the experiment being performed.
Purchase 1,4 Dioxane with inhibitors added (for peroxide-forming) when possible.
Due to its peroxide-forming hazard, 1,4 Dioxane containers must be dated upon receipt and at the time they are opened (mark the date on the bottle). If tested, note the date it was tested on the bottle.
Test open 1,4 Dioxane containers with peroxide test strips every 3 months.
An opened container can be stored for a maximum of 6 months. Dispose of unused amounts after that period of time has passed (or if peroxides are found to be present by testing).
Degassed 1,4 Dioxane may be stored in resealable Schlenk flasks under an atmosphere of argon or nitrogen, or stored in closed containers in a glove box with a nitrogen or argon atmosphere.
Procedure/Use / Scale / Engineering Controls/Equipment / PPE (eye, face, gloves, clothing) / Procedure Steps and Special Precautions for this Procedure
1. 1,4 Dioxane is used in the lab as a solvent. / Up to 2L 1,4 Dioxane per reaction or extraction / All work using 1,4 Dioxane must be performed in a ventilated fume hood. 1,4 Dioxane is a known carcinogen.
Eliminate ignition sources such as open flames, hot surfaces, steam baths, static electricity, and operation of mechanical and electrical equipment that is not intrinsically safe.
Ensure proper grounding and avoid creating static electricity. Be sure to ground metal containers when transferring flammable liquids.
Use a blast shield if 1,4 Dioxane may be distilled to dryness or evaporated to dryness. / Eye protection: Wear tight-fitting safety goggles or safety glasses with side shields.
Face protection: Wear a face shield when handling containers of 1,4 Dioxane that are not behind a lab hood sash or blast shield.
Gloves: 1,4 Dioxane penetrates most common lab gloves rapidly. Extended contact with 1,4 Dioxane is not allowed. To protect against incidental contact, wear Laminate Film gloves (e.g. Ansell Barrier) or double nitrile or butyl gloves (8 mil). Change outer glove as soon as contaminated. Note: 1,4 Dioxane penetrates 4 mil gloves nearly instantaneously.
Clothing: Wear fire/flame resistant lab coat (100% cotton based); cotton based clothing/attire; full length pants or equivalent; and close-toed, close-heeled shoes. / 1. Use in a fume hood and cap container when not in use.
2. Draw out necessary amount with as little exposure to ambient moisture as possible.
3. Dispose of 1,4 Dioxane-contaminated gloves and glassware in sealed containers.
Do not allow to evaporate to near dryness unless absence of peroxides has been shown.
If 1,4 Dioxane is concentrated on the rotary evaporator use two dry ice traps to collect the solvent vapors.
Distillation/evaporation of 1,4 Dioxane efficiently removes all stabilizers. Collected fractions (rotavap) must be treated as unstabilized 1,4 Dioxane and must be disposed of soon after generation.
Pressure can be built up if 1,4 Dioxane is used in reactions. Adequate ventilation (pressure bubbler on Schlenk manifold, or an equilibrating balloon) has to be used to prevent dangerous over pressurization.
Pressure is built up if 1,4 Dioxane is used in extractions. Adequate ventilation (open the valve frequently during the extraction) has to be used to prevent dangerous over pressurization.
If heated, the reaction apparatus has to be fitted with an adequately sized condenser and an adequate flow of cooling water has to be provided to prevent evaporation. Cooling hoses have to be secured with metal hose clamps to the condenser and the outlet.
Notes / Any deviation from this SOP requires approval from PI.
Initials of individuals using this procedure

1,4-Dioxane 11 Date: 12/19/2012

UCLA- EH&S GKM/PY

Documentation of Training (signature and initials of all users is required)

·  Prior to conducting any work with peroxide forming chemicals, designated personnel must provide training to his/her laboratory personnel specific to the hazards involved in working with the specific chemical(s) used, work area decontamination, and emergency procedures.