Safer Use and Storage

Understanding Chemical Hazards

OSHA

Laboratory Regulations

Lab Standard & HAZCOM

Written Plan

Training

Prevent Exposure

Laboratory

Standard

HAZCOM

SDS

Communicate Hazards

Cannot use lab standard

Is chemical handlingdesigned to be

easily and safelymanipulated by 1 person?

Does labsupport or simulate a production process?

Does the labproduce materials

for commercial use?

Cannot use lab standard

Cannot use lab standard

Laboratory Scale1910.1450(b)

Laboratory Use1910.1450(b)

OK to use Lab Standard

Are multiple chemicals or

procedures used?

Are protective practices and

equipment available?

Hazard & Risk

What is a Hazard?› Simply stated, a hazard is a potential for harm

› It can be a condition or an activity

› Broadly grouped this includes natural phenomena, chemicals, processes, sources of energy, situations and events

› Hazards left uncontrolled can result in injury, illness, loss of property, and/or environmental damage – these are consequences

› A hazard is an intrinsic property of the agent, condition, or activity

What is Risk?

› Risk is the probability or likelihood of an adverse consequence occurring from an existing hazard

› Risk is not an intrinsic property

› There are 3 components to consider– Likelihood

– Exposure

– Consequence severity

Risk (cont.)

› Probability or likelihood - a measure of how likely the occurrence of a complete sequence of events leading up to a consequence is upon exposure to a hazard. – This component is often associated with descriptors such as: rare;

unlikely; possible; likely; almost certain

› Exposure must consider the nature of the chemical and use– Route of entry, chemical form, length of exposure, etc.

› Severity of consequence – first aid to death / $ $

The terms hazard and risk are not synonymous.Because hazards are an intrinsic property of asubstance or condition, they cannot be reducedexcept by elimination.

By implementing appropriate controls, the riskassociated with identified hazards can be reduced oreliminated.

Globally Harmonized System

GHS

A system designed to alert those who useand transport chemicals to their hazardswhile providing helpful information toreduce the risk associated with thehazards

GHS

› GHS is a system for classification and labeling of chemicals

› The development of the GHS was prompted by an International Mandate in 19921

– “A globally harmonized hazard classification an compatible labelling system, including material safety data sheets and easily understandable symbols, should be available, if feasible, by the year 2000.”

› While the US, EU, CA, and the UN had quite extensive systems in place, this was a way to provide a foundation for all countries to develop comprehensive national programs which could ensure the safe use of chemicals

› Sixty seven countries have implemented or are in the process of implementation2

What is GHS?

2UNECE1The Purple Book

› …enhance the protection of human health and the environment by providing an internationally comprehensible system for hazard communication;

› …provide a recognized framework for those countries without an existing system;

› …reduce the need for testing and evaluation of chemicals; and

› …facilitate international trade in chemicals whose hazards have been properly assessed and identified on an international basis.

Specific Anticipated Benefits of Implementation

2003 GHS 1st Edition

What’s New?

Traditional Definitions GHS Definitions

Gas Takes both the shape and volume of its container [particles are far apart with much empty space]

…a gas is a substance or mixture which at 50°C (122°F) has a vapor pressure greater than 300 kPa (2.96 atm); or is completely gaseous at 20°C (68°F) and a standard pressure of 101.3 kPa (1 atm).

Liquid Has definite volume, but takes the shape of its container [particles are close, but can move past one another]

…a liquid is a substance or mixture that is not a gas and which has a melting point or initial melting point of (68°F) or less at standard pressure of 101.3 kPa (1 atm).

Solid Rigid, posses definite shape and volume [particles tightly packed and cannot move]

…a solid is a substance or mixture that does not meet the definitions of a liquid or a gas.

STATES OF MATTER

http://www.grc.nasa.gov/WWW/K-12/airplane/state.html

http://sites.tenafly.k12.nj.us/~shilfstein/phase_diagrams.htm

Physical Hazards

There are 16 recognized classes of physical hazards in GHS

RECOGNIZED HAZARDS

Health & Environmental

There are 10 health hazards

GHS does not require that manufacturers include environmental hazards, but most do.

RECOGNIZED HAZARDS

The Hazard Ranges

Range - Highest hazard to Lowest hazard Explosives Unstable Explosive > Div 1.1 > Div 1.2 > Div 1.3 > [1.4 ? 1.5] > 1.6

Flammable Gases

(+Chemically Unstable)

Category 1 > Category 2

Category A > Category B

Flammable Aerosols Category 1 > Category 2 > Category 3

Oxidizing Gases Category 1

Gasses Under Pressure

(classified by physical state when packaged)

Compressed gases, Liquefied gases, Refrigerated liquefied gases, Dissolved

gases

Flammable Liquids Category 1 > Category 2 > Category 3 > Category 4

Flammable Solids Category 1 > Category 2

Self-Reactive Substances Type A > Type B > Types C & D > Types E & F> Type G

Pyrophoric Liquids Category 1

Pyrophoric Solids Category 1

Self-Heating Substances Category 1 > Category 2

Substances which, in contact with water emit flammable gases Category 1 > Category 2 > Category 3

Oxidizing Liquids Category 1 > Category 2 > Category 3

Oxidizing Solids Category 1 > Category 2 > Category 3

Organic Peroxides Type A > Type B > Types C & D > Types E & F> Type G

Corrosive to Metals Category 1

Acute Toxicity (oral, dermal, inhalation) Category 1 > Category 2 > Category 3 > Category 4 > Category 5

Skin Corrosion/Irritation Category 1 > Category 1A > Category 1B > Category 1C > (Skin Corrosion)

Category 2 > Category 3 (Irritation)

Serious Eye Damage/Eye Irritation Category 1 (Serious Eye Damage)

Category 2A > Category 2B (Eye Irritation)

Respiratory or Skin Sensitization Category 1 (substance is classified as)

Sub-Category 1A > Sub-Category 1B

Germ Cell Mutagenicity Category 1 (A & B) > Category 2

Carcinogenicity Category 1 (A & B) > Category 2

Reproductive Toxicology Category 1 (A & B) > Category 2 > Additional Category

Target Organ Systemic Toxicity – Single Exposure Category 1 > Category 2 > Category 3

Target Organ Systemic Toxicity – Repeated Exposure Category 1 > Category 2

Aspiration Toxicity Category 1 > Category 2

Hazardous to the Aquatic Environment Short-Term (Acute) - Category 1 > Category 2 > Category 3

Long-Term (Chronic - Category 1 > Category 2 > Category 3 > Category 4

http://www.unece.org/trans/danger/publi/ghs/ghs_rev05/05files_e.html

What does it really mean to say that the hazard is a Category 1 or Category 4?

This depends on which hazard you are talking about and the range from high to low for that hazard

Manufacturers have to designate their chemicals into a category for each hazard based on known information

SOME EXAMPLES

GHS Classification in accordance with 29 CFR 1910 (OSHA HCS)

Isopropyl alcohol; CAS 67-63-0

Range (worst is lowest #) What does it mean?

Flammable liquids

Category 2

Range 1 to 4

Flash point* ≥ 23°C (73°F)

and ≤ 60°C (140°F)

Eye irritation

Category 2A

Range 1, to 2(A,B)

(2) Reversible adverse effects

on cornea, iris, conjunctiva

(A) Irritant

Subcategory 2A

Reversible in 21 days

Specific target organ toxicity -

single exposure - Central

nervous system

Category 3

Range 1 to 3

Transient target organ effects

- Narcotic effects

*Flash Point – The lowest temperature at which a combustible liquid or solid produces sufficient

vapor near its surface to generate an ignitable mixture with air.

GHS Classification in accordance with 29 CFR 1910 (OSHA HCS)

Nitric acid; CAS 7697-37-2

Range (worst is lowest #) What does it mean?

Oxidizing liquids

Category 3

Range 1 to 3

Any substance or mixture

which, in the 1:1 mixture, by

mass, of substance and

cellulose exhibits a pressure of

rise time ≤ that of a 1:1

mixture of 65% HNO3(aq) and

cellulose

Skin corrosion

Category 1A

Range 1, 1A to 1C

(2) Reversible adverse effects

on cornea, iris, conjunctiva

(A) Irritant

Subcategory 2A

Reversible in 21 days

Serious eye damage

Category 1

Range 1 to 2

Transient target organ effects

- Narcotic effects

GHS uses “Label Elements” and astandard format for “Safety DataSheets (SDSs)” to communicatehazards

› Use the 16 section American National Standards Institute (ANSI) format

› OSHA Brief

Safety Data Sheets

› Product Identifier

› Supplier Information

› Pictogram

› Signal Word

› Hazard Statements

› Precautionary Statements

Label Elements

› The product identifier refers to how the hazardous chemical is identified– Can be (but not limited to), the chemical name, a code such as the

CAS number, or some other code as defined by the manufacturer. The assigned identifier must match on the label and in Section 1 of the Safety Data Sheet.

› The supplier identification must include– The name, address, and phone number of the manufacturer,

distributor, or importer.

Product Identifier & Supplier Identification

Pictograms

› The purpose of the signal words is to provide the user with an immediate indication of the severity of the hazard

› In GHS, there are only two signal words – “Danger” and “Warning”

› Each label will carry only one signal word based on the greatest hazard associated with the chemical

Signal Words

› There are 72 individual and 17 combined Hazard statements that indicate a chemical has either a physical, a health or an environmental hazard.

› Each statement has been assigned a unique alphanumerical code which consists of one letter and three numbers as follows

– Each code carries the letter "H" for hazard statement

– The number designates the type of hazard

› "2" for physical hazards

› "3" for health hazards

› "4" for environmental hazards

› Two numbers corresponding to the sequential numbering of hazards arising from the intrinsic properties of the substance or mixture, such as explosive properties (codes from 200 to 210), flammability (codes from 220 to 230), etc.

› Each hazard code has an associated signal word, pictogram, and set of precautionary statements. There are a few codes listed as “EUH” which are leftover from the European Union.

Hazard Statements

› There are 116 individual and 33 combined Precautionary statements that tell the user how to protect themselves and the environment from the related hazard(s).

› Each statement has been assigned a unique alphanumerical code which consists of one letter and three numbers– The letter "P" designates precautionary statement– The first number designates the type of precautionary statement

› "1" for general precautionary statements› "2" for prevention precautionary statements› "3" for response precautionary statements› "4" for storage precautionary statements› "5" for disposal precautionary statements

– two numbers (corresponding to the sequential numbering of precautionary statements)

Precautionary Statements

4 Class 1A materials, or those which will vaporize and/or disperse and burn readily in air

3 Class 1B and 1C materials, also readily ignited liquids and solids

2 Class II and IIIA materials, also solids and semi-solids that readily emit flammable vapors.

1 Class IIIB materials. Almost all combustible vapors. Materials that must be preheated before combustion

0 Materials that will not burn when exposed to temperature of 1500o F for > 5 minutes

Flash Point°C(°F)

Boiling Point °C(°F) NFPA 30 Class NFPA 704 Flammability

GHS Flammable Liquids

GHS

<23 (73) <38 (100) ≤ 35 (95) IA 4 1

<23 (73) ≥38 (100) > 35 (95) IB 3

2

≥23 (73)& <38 (100) any any IC

3≥38(100) & <60 (140) any any II

2≥60 (140) & <93 (199) any any IIIA 4

≥93 (199) any any IIIB 1 Not flammable

Information on Classification of Flammable Solvents

NFPA 704

From the Sigma Aldrich SDS for lead (II)nitrate

Quiz

› Let’s take a moment to review some important concepts covered so far. We have some poll questions for you to participate in.

Segregation Based on Hazard Classes

› Flammables (red)

› Oxidizers (yellow)

› Corrosives (blue)– Acids

– bases

› Highly Reactive (yellow, white)

› Extreme Toxics/Regulated Materials (blue, green)*

› Low Hazard (black)

*Be careful with color schemes – they can vary from company to company or lab to lab

Steps to Classification

› Check the label first to see what GHS is telling me. If it is an older bottle, find a GHS SDS and check the Hcodes. Sigma Aldrich has very good SDS sheets

› Note any special storage conditions based on incompatibilities given in Section 10

› If more information is needed on compatibility, check NOAA’s site – CAMEO Chemicals [Complete instructions on Computer Aided Management of Emergency Operations can be found here]

› Yet more information can be found at ChemIDPlus Advanced

Flammables

Organic Acids

OxidizersHigh Toxicity

ethanol

silver nitrate

methanol

calcium nitrate

nitric acid*

Inorganic Acids

Corrosives

AcidsBases

sulfuric acid

hydrochloric acid

potassium hydroxide

sodium hydroxide

acetic acid

lead(II) nitrate

aluminum chloride

magnesium

copper(II) sulfate

copper(II) chloride

barium chloride

ammonium chloride

calcium chloride

magnesium sulfate

zinc

W

Wood

General Storage

*nitric acid on the DHS list

lead(II) nitrate

aluminum chloridecopper(II) chloridecopper(II) sulfatehydrochloric acidMagnesiumzinccalcium chloridesilver nitrateammonium chloridecalcium nitratebarium chloridelead(II) nitratemagnesium sulfateacetic acidpotassium hydroxidenitric acidsulfuric acidethanolmethanolsodium hydroxide

In General…

› Store chemicals in containers made from compatible materials

› Store chemicals in cool rooms – locked!

› Store chemicals with secondary containment when possible

› Label secondary containers well***

› Do not store chemicals in direct sunlight

› Check containers on a regular basis

› Maintain an up-to-date inventory and SDSs

› Do not store flammables in domestic refrigerators

› Do not store chemicals above eye level

› Do not buy more than you can use in a reasonable timeframe

› Do not accept chemical “donations” from the public

Need Help?

› National Institute for Occupational Health & Safety (NIOSH) -School Chemistry Laboratory Safety Guide

› American Chemical Society – Committee on Chemical Safety

› American Chemical Society – Chemical Health and Safety Resources

› American Chemical Society – Guide for Chemical Spill Response Planning in Laboratories

› American Chemical Society – Division of Chemical Health & Safety (DCHAS)

› To encourage K-12 teachers learn more about chemical safety and allow them greater access to the DCHAS Workshops presented at the ACS National Meetings, the DCHAS Executive Committee has agreed to allow any K-12 teacher who is also an active AACT member to attend a DCHAS workshop for a reduced registration rate of $99

› Details will be available on the DCHAS Workshop page soon

Professional Development

After the Rainbow

Statement of CSB Chairperson Rafael Moure-Eraso Statement of CSB Chairperson Rafael Moure-Eraso Warning Against Use of Methanol During Laboratory and Classroom Combustion Demonstrations, in the Wake of Reno, Nevada, Museum Fire

Quiz

› The 3 large groupings of recognized hazards are _______, _______, and ______________.

› There are ____ pictograms.

› There are ___ signal words.

› H260 indicates some type of __________ hazard.

› The product identifier on the chemical label must exactly match the one in Section ___ of the SDS.

› Section 2 of the SDS gives the________________ for the chemical.

physicalenvironmentalhealth

9

2

physical

1

hazard information

› http://ow.ly/BzfMO

› http://ow.ly/BzgV4

› sigmannsb@appstate.edu

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