Overview of Radioactive Materials and the OSHA Hazard

Communication Standard

DOE and DOE Contractors Industrial Hygiene Meeting 5/20/19

By

Elliot Stein, MPH, CIH, CSPU.S. Department of Energy

Office of ScienceIntegrated Support Center – Chicago Office (ISC-CH)

Safety and Technical Services

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Why is Chemical Safety/Haz Com Important Regarding Radioactive Materials ? *

• Many chemicals that have ionizing radiation hazards have chemical hazards. Employees who are unaware of these hazards may be at increased risk of accidents, injuries and illnesses.

• It is sometimes mistakenly believed that if radioactive chemicals are regulated as ionizing radiation their chemical hazards are unregulated.

• ESH professionals need to know which radioactive chemicals meet OSHA Hazard Communication Standard criteria in order for these chemicals to be part of the organization’s hazard communication program.

* Stein, E., Radioactive materials and the OSHA Hazard Communication Standard, Journal of Chemical Health and Safety, July/August, 2018.

Note: This presentation discusses general provisions of the Hazard Communication Standard and radioactive materials applicable to non-DOE facilities as well as selected DOE facilities. DOE entities may need to review with their site office and headquarters elements whether or not particular provisions of the Hazard Communication Standard are applicable to their organization.

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Are Radioactive Substances Included in Haz Com Standard ?

2012 Hazard Communication Standard (29 CFR 1910.1200)

Does not apply to:1910.1200(b)(6)(xi) Ionizing and non-ionizing radiation

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DOE/EH-0003 Sept.1985 ESH Bulletin Radioisotopes Exempt from Haz Com

The production, use, sale or transfer of radioisotopes within or between DOE facilities and the sale or transfer of radioisotopes to a Nuclear Regulatory Commission ore agreement state licensee are exemptfrom this standard. Requirements for labeling, employee education and radiation production are covered in separate Orders, standards and regulations.

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DOE Safety and Health Regulatory and Policy Response LineHazard Communication for Radiological Hazards

(File D93-08-026) 8/17/1993

Question: “Does the Hazard Communication Standard exempt radiological hazards? The caller thought that a DOE bulletin had come out on this question, but has been unable to locate it. The caller's specific query relates to thoriated tungsten electrodes which are alpha emitters.”

Answer: “DOE /1940 states that the ionizing hazard from radioactive materials are not covered by the Hazard Communication standard. If a radioactive material, however, presents other types of chemical hazards, then the chemical would be covered for those hazards. Tungsten is listed as a hazardous chemical by virtue of its inclusion in 1910 Subpart Z. ccordingly,1910.1200(d)(3)(i) requires that a thoriated tungsten electrode be treated as a hazardous chemical. For radioactive chemicals which are not included in the Hazard Communication Standard, the advice of your local health physicist should be sought.”

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OSHA Interpretation Letter from 4/15/13 –New Brunswick Laboratory *

“When the laboratory ships nuclear standards that have only ionizing radiation hazards, it is not required to comply with the HCS requirements. Nevertheless, it has been OSHA 's longstanding position that if the radioactive material contains another type of chemical hazard that is not the result of the radioactivity of the chemical, the HCS requirements apply… Therefore, when the nuclear standards that are shipped have a chemical hazard that is not the result of the radioactivity of the chemical, the standards must be labeled for those chemical hazards and have a Material Safety Data Sheet (MSDS) or SDS.”

* Letter of Interpretation from Thomas Galassi, Director US DOL OSHA Directorate of Enforcement Programs dated April 15, 2013

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DOE Safety and Health Regulatory and Policy Response LineLabeling Radioisotopes Under the OSHA Hazard

Communication Standard (File D18-04-001) - 4/16/2018

Question: “DOE ESH Bulletin 0003-Sept 1985 exempts DOE from labeling radioisotopes under the OSHA Hazard Communication Standard1... An example would be Strontium-82 with a half life of 25.34 days transitioning to rubidium-82 which could be shipped to DOE funded facilities or private commercial facilities as Strontium chloride in 0.05-0.5 N hydrochloric acid…The bulletin refers to DOE O 5480.4 Environmental Protection, Safety and Health Protection Standards, which has been superseded by 10 CFR 851. Does the above bulletin still apply…?”Answer: “Title 10 CFR 851.23(A)(3) incorporates by reference 29 CFR 1910 which includes 1910.1200 Hazard Communication Standard…Accordingly, the requirements under the HSC do not apply if your facility produces and ships standards that have ionizing radiation hazards only. However…hydrochloric acid is considered a hazardous chemical under the HCS. The container would be subject to the requirement of the HCS for the chemical hazard that is presented along with the radioactive material…”1 ”The production, use, sale, or transfer of radioisotopes within or between DOE facilities and the sale or transfer of radioisotopes to a Nuclear Regulatory Commission or agreement state licensee are exempt from this standard. Requirements for labeling, employee education, and radiation protection are covered in separate Orders, standards and regulations.”

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Common Chemical (Physical or Health) Hazards of Radioactive Materials

Unrelated to Radioactivity

• Is material acidic or basic (i.e. uranyl nitrate, plutonium nitrate, etc.)?• Is material reactive (i.e. uranium or plutonium shavings/powder are

pyrophoric, etc.)?• Can material form hazardous byproducts (i.e. uranium hexafluoride

exposed to moisture in air generates hydrogen fluoride (acutely toxic) and uranyl oxyfluoride, etc.).

• Does material have toxicity unrelated to radioactivity (i.e. depleted uranium is toxic as heavy metal, depleted or normal enrichment UF4 is acutely toxic, etc.).

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When are radioactive substances exempt from Haz Com Requirements ?

• There is no known chemical health hazard evidence (e.g. is not carcinogenic, mutagenic, reproductive hazard – e.g. californium-252)

• There is no known physical hazard (e.g. is not pyrophoric, flammable, oxidizer, etc.)

• The quantity is so small so as to not pose a health or physical hazard• The radioisotope is in a form where exposure is highly unlikely (e.g.

sealed source/embedded in a metal or ceramic, isotope has very short half life, etc.)

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Are DOT and OSHA Haz Com Requirements the same ?

1. DOT requirements apply mostly to the outside labels/ placards/markings and packaging.

2. DOT hazard symbols may be different than OSHA GHS pictographs. OSHA pictograms have a red border.

3. DOT 9 classes for hazardous chemicals in transportation. OSHA hazardous chemicals in the workplace.

4. Some OSHA pictograms for health have no corresponding DOT labels/placards/markings equivalent.

5. Different criteria for hazard classifications.

DOT Labels/Placards OSHA Pictogramfor

Uranium Hexafluoride (UF6)

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Radioactive Material Requirements relative to OSHA Laboratory and Haz Com Standards

• Laboratories storing or using radioactive materials with chemical hazards must comply with OSHA “Lab Standard” (Occupational Exposure to Hazardous Chemicals in the Laboratory, 29 CFR 1910.1450) requiring labeling, SDSs, training, chemical hygiene plan, etc.

• Non-laboratory areas of facility must comply with HCS requirements requiring labeling, SDSs, training, etc.

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Haz Com Requirements for Radioactive Materials*

• Chemical Inventory (usually not radiologic)• Safety Data Sheets (hybrid or only chemical)• Chemical Labeling (hybrid or only chemical)• Training (incorporated with radiologic or separate)• Written Compliance Plan (manufacturer / User)

*Note: Some radioisotope distributers believe Haz Com does not apply to radionuclides. (e.g. Eckhert and Ziegler in 2015 incorrectly stated that Haz Com did not apply to radioisotopes citing 1910.1200(b)(6)(xi).

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OSHA Occupational Exposure to Hazardous Chemicals in the Laboratory (29 CFR 1910.1450)

Hazard Communication Standard covers areas outside the laboratory.OSHA Occupational Exposure to Hazardous Chemicals in the Laboratory covers work performed with “handling or use of chemicals on a laboratory scale which are not part of a production process”.

Employers must:• Ensure labels on incoming containers are not removed or defaced.• Maintain Safety Data Sheets. Includes Radionuclides ? • Write Safety Data Sheets for substances produced in the laboratory with

appropriate labels. • Prepare a written chemical hygiene plan. Includes Radionuclides ?• Train employees regarding detection or release of hazardous substances, medical

consultation and examinations and use of containment devices such as fume hoods.

Note: Filtered fume hoods may be required; Remember – you may have both radiation and chemical exposure at the same time.

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Function of the New Brunswick Laboratory (NBL)

• NBL prepared nuclear Certified Reference Materials (i.e. uranium, plutonium, thorium, etc.) from 1949 to 2016 as a GOGO – Government Owned and Government Operated federal facility. It was for most of its existence as a Hazard Category 2 or Hazard Category 3 Nuclear Facility.

• NBL closed as an active lab in 2016 and became a program office (NBL Program Office), contracting out the production of nuclear reference materials to various DOE National Laboratories.

• NBL was a de facto small chemical manufacturer/distributor and is currently a program office with a primary distribution center for nuclear reference materials at the CNS Y-12 National Security Complex in Oak Ridge, TN.

Note: This presentation will discuss the former NBL not NBL Program Office activities.

http://www.nbl.doe.gov

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U.S. Department of EnergyNew Brunswick Laboratory9800 S. Cass Ave., Building 350

Argonne, IL 604391-630-252-CRMS

Off Hours Emergency Numbers: 1-630-252-6131 or 1-630-252-5731

URANIUM HEXAFLUORIDE (CRM 113-A, CRM 113-B )

Danger!Fatal if Inhaled

Causes Severe Skin Burns and Eye DamageToxic to aquatic life with long lasting effects

Radioactive

Do not breathe gasDo not get on skin or in eyes.

Wear respiratory protection, gloves and goggles.

First Aid: Inhalation: Immediately call 911 . Remove to fresh air at once. External/Eyes : Immediately call 911 Wash continuously with fresh water for 15 minutes. Apply calcium gluconate gel to skin surfaces.

In Case of Fire: Negligible fire hazard. Use triclass, dry chemical or carbon dioxide fire extinguisher. For larger fires use water spray, fog or foam.

Example of NBL Haz Com Label, Uranium Hexafluoride

UF6 HazardsUpon exposure to moisture in air can generate:

UF6 + 2 H2O → UO2F2 + 4 HFHF - 3 ppm ceiling valueHF - 50-250 ppm 5 minutes lethal dose (LC50) or

1,000–3,000 ppm 5-10 seconds3 deaths at DOE facilities – tank farms

Original Unlabeled UF6 Cylinder

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Example of NBL Haz Com Label Plutonium Nitrate – Abbreviated Label for Small

Ampoules/Bottles

OSHA permits abbreviated label on primary container for small ampules and vials. The full label can be on secondary/outer package. (June 4, 2013 OSHA Letter of Interpretation to NIST regarding small ampules/bottles. “As a practical accommodation, where the manufacturer can show that it is not feasible to use pull-out labels, fold back labels, or tags, containing the full HCS 2012 required information, the shipped small container (i.e., the actual container holding the hazardous chemical), at a minimum, must contain the following: Product identifier; Appropriate pictograms; Manufacturer's name and phone number; Signal word; A statement indicating the full label information for the chemical is provided on the outside package.”)

Original Non Haz Com Labels

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Example of NBL and NIST SDS, Uranyl Nitrate

Both SDS discuss radiological and chemical hazards (hybrid) although Haz Com only requires chemical hazard information.

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Chemical Inventory at NBLInventory includes rad (by category) and non-rad chemicals.

Chemical Inventory Datasheet Location: C138

HSC: Date of Most Recent Inspection: January 25, 2014

ACIDS/OXIDIZERS CHEMICAL FORMULA QUANTITY( rounded)

HIGHEST CONC. STORED

Hydrofluoric acid HF 500 mL conc (48%)Nitric acid HNO3 15 L conc (16 M)Phosphoric Acid H3PO4 10 L conc (85%)Sulfamic Acid, solution H2NSO3H 8.0 L 1.5 MSulfuric acid H2SO4 9.5 L conc (18 M)Fuming acid solution (sulfuric, nitric and perchloric) H2SO4, HNO3, HCLO4 800 ml

90%Ammonium molybdate/nitric acid/Sulfamic Acid oxidizing reagent (NH4)6M07O24.4H20, + HNO3 + NH4SO3H 8L

0.4% Moly, 50% HN03, 1.46% Sulfamic

CARCINOGEN ( as listed in NBL Chemical Hygiene Plan, June 2013) CHEMICAL FORMULA QUANTITY( rounded)

HIGHEST CONC. STORED

Potassium Dichromate, solid K2CrO7 3 kg N/APotassium Dichromate, solution K2CrO7 8.0 L 2%

COMPRESSED GASES (*including liquid N2) CHEMICAL FORMULA QUANTITY( rounded)

HIGHEST CONC. STORED

FLAMMABLES CHEMICAL FORMULA QUANTITY( rounded)

Acetone CH3COCH3 600 mL N/A

NUCLEAR MATERIAL TYPES CHEMICAL FORMULA QUANTITY( rounded)

Uranium hexafluoride UF6 6 P-10 tubes max 13g eachUranium metal, uranium in nitric acid, uranium tetrafluoride, uranium oxide, uranium in phosphoric acid

U, U in HN03, UF4, U03, U308, U02

OTHER CHEMICAL FORMULA QUANTITY( rounded)

HIGHEST CONC. STORED

Bon Ami, cleanser N/A 400 g N/ADrierite (Calcium Sulfate) CaSO4 1800 g N/A

Ferrous Sulfate Heptahydrate, solid FeSO4.7H2O 1000 g N/A

Ferrous Sulfate, solution FeSO4 150 mL 1.0 MJoy dishwashing liquid N/A 1000 mL N/AMicro-90 cleaning solution N/A 2.0 L N/A

Potassium Chloride, solid KCl 750 g N/A

Potassium Chloride, solution KCl 150 mL saturated

Potassium Pyrosulfate K2S2O7 1700 g N/A

Radiac solution N/A 2.0 L N/A

Vanadyl Sulfate, solid VOSO4XH2O 300 g N/A

bar soap - pumice 4 bars

Sulfamic Acid, solid NH2SO3H 500 g N/A

Ammonium Molybdate, solid (NH4)6MO7O24.4H2O 500g N/A

Windex 1000 mL N/A

Sea Sand 1000 g N/A

Silicon Lubricant N/A 6 oz N/A

Ink stamp-pad NA 2 oz NA

Bio-Rad ( AG 1X-8) pre-filled 2-mL resin column NA 300 columns NA

Bio-Rad ( AG 1X-8) resin NA 500 g

eichrom UTEVA pre-filled 1-mL resin column NA 100 columns

SHELF-LIFE RESTRICTED CHEMICAL FORMULA QUANTITY( rounded)

Expiration Date

Calcium Gluconate, 2% CH2OH (CHOH)4COO)2Ca 30g 60g July-14

Americium Am U U Uno MSDS available

Carnotite OresK2(UO2)2(VO4)

2·3H2O 3 0 0 XCesium Cs 3 4 3 X

Cobalt 60 Co-60 U U Uno MSDS available

Europium Eu 2 0 0 X

Monozite Sand Ore Materials

Ce(Ce, La, Pr, Nd, Th, Y)PO4 3 2 1 X

Neptunium Np U U Uno MSDS available

Pitchblende Ore Uraninite 3 0 0 XPlutonium in Nitric Acid Pu + HN03 3 0 0 XPlutonium Metal Pu U 3 2 XPlutonium Nitrate Pu-HN03 U 0 0 XPu Oxide Pellets Pu Oxide Pu02 U U U XPlutonium sulfate tetrahydarade

Pu(SO4)2 4H2O U U U X

Polonium 210 Po U U Uno MSDS available

Protactinium Pa U U Uno MSDS available

Radium Ra 3 0 0 XRubidium Ru 3 3 2 XThorium Metal Th 3 2 2 XThorium Oxide ThO2 2 0 0 XUranium-Alumina Powder U-Al2O3 U U U

no MSDS available

Uranium Depleted DU, U 1 1 0 XUranium Hexafluoride UF6 4 0 1 X

HEU + isopropyl alcohol(CH3)2 CHOH + U3O8 2 3 0 X

Uranium in Phosphoric Acid U + H3P04 2 0 0 XUranium Metal U U 3 3 XUranium oxide pellets or powder Uranium Oxide U3O8 U 0 0 XUranium Oxide Uranium Oxide U02 3 0 0 XUranium Tetrafluoride UF4 4 0 1 XUranium Trioxide UO3 3 0 1 XUranyl Nitrate all enrichments Uranyl nitrate UO2(NO3)2 3 0 0 XUranyl Nitrate Hexahydrate N2O8U·6H2O 3 0 3 X

U hazard rating = Unknown

RADIOIACTIVE CHEMICALS COMMON NAME CHEMICAL NAME CHEMICAL FORMULA NFPARATING Health Fire Hazard Reactivity Specific Hazard MSDS Available NFPA info missing

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Door Signs

Temp Lab Container Labels

Questions

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