reminder to the audience - confex...8/1/2011 6 typical statements of acute hazard schc spring...

8/1/2011

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Changes are Happening with

Chemical Hazard Communication

© 2011 Product Safety Solutions, LLC

Reminder to the Audience

• It is presumed that– You have heard of the ANSI Label and MSDS standards.

– You know about the Globally Harmonized System (GHS)If you don’t know what GHS, you will miss several points.

– You know the basic requirements of the current OSHA Hazard Communication Standard

AHMP National Meeting ‐ Austin, TX Aug., 2011 2

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The Combined Safety Data Sheet

& Labeling Standard

AHMP National Meeting ‐ Austin, TX Aug., 2011

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ANSI ‘hazcom’ Standards

Label Standard Z129.1• 1976• 1982• 1988• 1994• 2000• 2006

MSDS Standard Z400.1

• 1993• 1998• 2004

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Combined - 2010


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ANSI STANDARD• The labeling standard has been combined with the MSDS standard– for Hazardous Workplace Chemicals – Hazard Evaluation and Safety Data Sheet and Precautionary Labeling Preparation

• Consensus• Organized logical system• Consistency• Legal significance


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Overview• The combined standard is set up similar to the way we write SDSs and labels.

• Hazard evaluations– Physical, health, environmental

• Write the SDS (MSDS)– Standard focus on SDS structure and information needs

• Write the label– Standard focus on appropriate statements for the potential hazards.

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Z400.1/129.1‐20101. General2. Scope, purpose and application3. Hazard Evaluation4. Physical Hazards5. Health Hazards6. Environmental Hazards7. Hazard Communication Principles8. Safety Data Sheets (SDS)

7AHMP National Meeting ‐ Austin, TX Aug., 2011

Z400.1/129.1‐2010

9. Sections of the Safety Data Sheet10. Labels and Labeling11. Preparing Precautionary Labeling12. Review of Documents13.Tables of Hazard Criteria and Precautionary

Label Text14. Resources• Annexes


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Physical hazards • Fire hazard chemical

– Flammable gas– Flammable liquid

• Extremely flammable• Flammable• Combustible • Static accumulating flammable

liquids– Flammable solid

• Flammable solid• Combustible dust

– Flammable aerosols• Oxidizer• Organic peroxide• Pyrophoric chemical• Pressure generating chemical

• Water reactive chemical• Compressed gas• Cryogenic liquids• Unstable reactive• Corrosive to metal

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Health hazards Immediate/delayed effects

• Immediate effects– Corrosive– Irritant– Inhalation

• Highly toxic/poison• Toxic• Asphyxiant

– Dermal• Highly toxic/poison• Toxic• Harmful

– Oral• Highly toxic/poison• Toxic• Harmful• Aspiration

– Allergic reactions/sensitizer

• Delayed effects– Target organ effects– Carcinogenicity/cancer– Reproductive, developmental

and teratogenic– Mutagenicity


Some Changes• Industrial chemicals are now called ‘workplace chemicals’

• First aid section updated to current standards• Signal word(s) assigned to aspiration hazard• Two examples of SDSs and labels for the same chemical products

• Hazard communication ‘workflow’ is explained– Modeled on the GHS purple book by including the concept of classification and how to communicate the hazards via SDS preparation and labeling in one reference


ANSI SDSs

• Although the title of the standard uses the term “material safety data sheet” the standard consistently uses the term “safety data sheet”.

• Like previous standards, each section is discussed.– Purpose– Audience– Scope and content

• Examples give throughout the discussion of SDS section.


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Typical ANSI‐GHS Label w/ DOT

WARNING! Methyl EnigmaFLAMMABLE LIQUID AND VAPORCAUSES SKIN AND EYE IRRITATIONKeep away from heat/ sparks/ open flame/hot surfaces. – No smoking. Keep container tightly closed.Wear protective gloves/eye protection.Wash thoroughly after handling.First Aid:.........................................In case of fire:.................................In case of spill:............................... Environmental Hazards?? Storage and Handling:..................Disposal Considerations or prohibitions??For additional information, see SDS.Phantom Chemical‐ Kneecap, AL.

UN 3321


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Label Elements

• Identification of the chemical product• Identification of its hazards components• Name, address• Telephone number of the manufacturer, importer or other responsible party

• Signal word (danger, warning or caution)• Statements of Hazard• Precautionary measures

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Label Elements cont.

• Instruction in case of contact or exposure (first aid)• Antidotes and note to physicians• Instruction in case of fire• Instruction in case of spill or leak• Instructions for container handling and storage• Reference(s) to additional labeling/other documents (such as SDS).


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Typical Statements of Acute Hazard

16SCHC Spring Meeting D. Levine 3-30-2011

Typical Statements of Chronic Hazard


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ANSI 2010 Tables• Table A – Physical hazards (see Section 4.2)• Table B – Health hazards: Skin corrosion/irritation (see Sections

5.1.1.1 and 5.1.1.2)• Table C – Health hazards: Eye corrosion/Eye irritation (see Sections

5.1.1.1 and 5.1.1.2)• Table D – Health hazards: Respiratory irritation (see Sections 5.1.1.1

and 5.1.1.2)• Table E – Health hazards: Sensitization (see Section 5.1.2)• Table F – Health hazards: Inhalation toxicity (see Section 5.1.1.3)• Table G – Health hazards: Dermal toxicity (see Section 5.1.1.4)• Table H – Health hazards: Oral toxicity (see Section 5.1.1.5)


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ANSI 2010 Tables• Table I • Part 1 – Examples of optional hazard warning statements

• Physical hazards• Immediate health hazards• Delayed health hazards

• Part 2 – Environmental hazard warning statements

• Table J – Additional optional precautionary measure statements– Prevention– First Aid– Fire fighting– Spill procedures– Handling and storage– Disposal– Container handling/storage


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ANSI Tables• The tables are the “heart of the standard and provide guidance in choosing text.

• For tables A through H

Physical Hazards Health Hazards

Hazard Hazard

Criteria Criteria

Description Description

Signal Word Signal Word

Statement of Hazard Statement of Hazard

Precautionary Measures Precautionary Measures

Instructions in case of contact or exposure


OSHA Proposal• OSHA published NPRM on 9/30/2009. • Comments were due in December, 2009.• 4‐day public hearing in DC held in early March, 2010.

• About 150 comments received prior to public meetings.

• About 50 written comments received after public meetings.

• Final publication estimated for September.


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OSHA Proposal• This will change the HCS and will also affect several OSHA regulations:

• OSHA Hazcom Standard (29CFR1910.1200)• Flammable Storage Classes (29CFR1910.106)• Substance‐specific rules: For example….

– Lead 29CFR1910.1025– Vinyl Chloride 29CFR1910.1017– etc.

• PSM (29 CFR 1910.119) e.g. definition of flammable comes from Hazcom rule.


OSHA Proposal• Proposed regulatory text is similar but not the same as the

HCS– (a) Purpose– (b) Scope and Application– (c) Definitions– (d) Hazard Classification– (e)Written Hazard Communication Program– (f) Labels and Other Forms of Warning– (g) Safety Data Sheets– (h) Employee Information and Training– (i)Trade Secrets– (j) Effective Dates


OSHA Proposal

• Definitions of hazard move to appendices along with other elements

• A. Health Hazard Criteria (Mandatory, new)• B. Physical Hazard Criteria (Mandatory, new)• C. Allocation of Label Elements (Mandatory, new)• D. Safety Data Sheets (Mandatory, new)• E. Definition of “Trade Secret” (Mandatory)• F. Guidance for Hazard Classifications e.g.:

Carcinogenicity (Non‐Mandatory, new)


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OSHA Proposal

• Some language changes – MSDSs are now SDSs– Hazard determination now called the hazard classification.

– Hazard classes divided into hazard categories– Hazardous chemical can refer to both substances and to mixtures


GHS will unify things

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CPSC/FHSAOSHA HCSANSI Label

HF

HF

Flammable

Flammable

Flammable

Combustible

Combustible

Combustible

Flammability of liquids

GHSHF Flammable CombustibleE F

GHS will unify things

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CPSC/FHSAOSHA HCSANSI Label Harmful

HT

HT

HT

Toxic

Toxic

Toxic

Oral toxicity of liquids

GHS 1 2 3 Category 4 Category 5


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OSHA Proposal


OSHA Proposal


Some Proposal Impacts• Acute Toxicity definition is broader.

Oral Toxicity to Rat

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Existing HCS Proposed StandardHighly Toxic: LD50 < 50 mg/kg

Category 1:LD50 < 5 mg/kg

Category 2: LD50 > 5 mg/kg & 50 mg/kg &

< 500 mg/kg

Category 3:LD50 > 50 mg/kg & 300 mg/kg &

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Some Proposal Impacts• Acute Toxicity definition is broader.

Dermal Toxicity to Rabbit

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Existing HCS Proposed StandardHighly Toxic: LD50 < 200 mg/kg

Category 1:LD50 < 50 mg/kg

Category 2: LD50 > 50 mg/kg & < 200 mg/kg

Toxic: LD50 > 200 mg/kg &

< 1000 mg/kg

Category 3:LD50 > 200 mg/kg & < 1000 mg/kg

Category 4LD50 > 1000 mg/kg & < 2000 mg/kg


Some Proposal Impacts

Inhalation Toxicity to Rat (gases)

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Existing HCS Proposed StandardHighly Toxic: LC50 (1 hr) < 200 ppm

LC50 (4 hr) < ~100 ppm

Category 1: LC50 (4 hr) < 100 ppm

Category 2: LC50 (4 hr) > 100 ppm &< 500 PPM

Toxic: LC50 (1 hr) > 200 ppm &

< 2000 ppmLC50 (4 hr) > 100 ppm &

< 1000 ppm

Category 3:LC50 (4 hr) > 500 ppm &

< 2500 ppm

Category 4LC50 (4 hr) > 2500 ppm &

< 20000 ppmThe conversion factor from 1 hr to 4hr is to divide by 2 for gases



Inhalation Toxicity to Rat (dust/mist)

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Existing HCS Proposed StandardHighly Toxic: LC50 (1 hr) < 2 mg/l

LC50 (4 hr) < ~0.5 mg/l

Category 1: LC50 (4 hr) < 0.05 mg/l

Category 2: LC50 (4 hr) > 0.05 mg/l &< 0.5 mg/l

Toxic: LC50 (1 hr) > 2 mg/l &

< 20 mg/lLC50 (4 hr) > 0.5 mg/l &

< ~5 mg/l

Category 3:LC50 (4 hr) > 0.5 mg/l &

< 1.0 mg/l

Category 4LC50 (4 hr) > 1.0 mg/l &

< 5 mg/lThe conversion factor from 1 hr to 4hr is to divide by 4 for gases


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Inhalation Toxicity to Rat (vapor)

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Existing HCS Proposed StandardHighly Toxic: LC50 (1 hr) < 200 ppm

LC50 (4 hr) < ~100 ppm

Category 1: LC50 (4 hr) < 0.5 mg/l

Category 2: LC50 (4 hr) > 0.5 mg/l &< 2 mg/l

Toxic: LC50 (1 hr) > 200 ppm &

< 2000 ppmLC50 (4 hr) > 100 ppm &

< ~1000 ppm

Category 3:LC50 (4 hr) > 2 mg/l &

< 10.0 mg/l

Category 4LC50 (4 hr) > 10.0 mg/l &

< 20 mg/lA direct comparison is not possible.

mg/l = (ppm) x (MW)/(24,450)


Some Proposal Impacts• List of IARC, NTP, OSHA carcinogens replaced by carcinogenicity criteria.

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Criteria Known to cause human cancers

Animal carcinogen & limited human evidence

Limited evidence in animals & humans

IARC 1 – Human Carcinogen

2a – Probable Carcinogen

2b – Suspect Carcinogen

NTP Known Carcinogen Suspect CarcinogenOSHA carcinogens

Cancer Agent Suspect Cancer Agent

OSHA Proposal

1A – Known Carcinogen

1B – Presumed Carcinogen

2 – Suspect Carcinogen

These translated categories are approximate. The study results should be reviewed to determine the actual classification under the proposed standard.


OSHA Proposal Impacts• OSHA will cover hazards not yet defined by GHS… Unclassified Hazard– E.g., combustible dusts…– Pyrophoric gases

• Formulators cannot rely exclusively upon supplier SDSs if the chemical identity is available….


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Classifying mixtures under GHS is more time‐consuming.

• Use of OSHA’s 1% and 0.1% “bright lines” not valid for the GHS.

• GHS requires the use of various ‘bridging’ techniques and of an additive formula and concentration limits for certain ‘end points’.


What is used in hazard classification?

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Hazard Endpoint Existing HCS Proposed HCSAcute Toxicity 1% > 1% or 1% or 1% or 0.1% Cat. 1

> 0.1% Cat.. 1A> 1% Cat. 1B

Respiratory Sensitization 1% > 0.1% Cat. 1> 0.1% Cat. 1A

> 1% [> 0.2% for gases] Cat. 1BMutagenicity 1% > 0.1% Cat. 1 SDS/Label

> 1% Cat. 2 SDS/LabelCarcinogenicity 0.1% > 0.1% Cat. 1 SDS/Label

> 0.1% & 1% Cat. 2 SDS/Label

Reproductive Toxicity 1% > 0.1% Cat. 1 SDS/Label> 1% Cat. 2 SDS/Label

STOT (Spec. Target Organ Tox.) 1% > 1% Cat. 1 SDS/Label> 1% Cat. 2 SDS/Label

20% additive Cat. 3 suggestedAspiration 1% > 10% Cat. 1 & kinematic viscosity < 20.5

mm2/s @ 40°CAHMP National Meeting ‐ Austin, TX Aug., 2011

Classifying Mixtures (toxicity)

• Testing• Bridging criteria such as

– dilution, – interpolation of high, low data

• Calculation by formula– Acute toxicity

= in i

i

mix ATEC

ATE100


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Classifying Mixtures (toxicity)

More than 10% of mixture has unknown toxicity value….

Your mixture calculates to a more toxic value if data is not available.

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in i

i

mix ATEC

ATE100‐(Σ Cunknown)


Mixtures – Corrosivity/Irritation

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Sum of ingredients classified as:(where effects are additive)

Concentrations triggering classification of a mixture as

Skin Corrosive Skin Irritant

Category 1 Category 2 Category 3

Skin category 1 > 5% > 1% but 10% > 1% but 10%

(10 x Skin category 1) + Skin category 2

> 10% > 1% but 10%


Mixtures – Corrosivity/Irritation

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Ingredient:(where effects are not additive)

Concentration Mixture Classified as: (Skin)

Acid with pH < 2 > 1% Category 1

Base with pH > 11.5 > 1% Category 1

Other corrosive (category 1) ingredients for which additivity does not apply

> 1% Category 1

Other corrosive (category 2/3) ingredients for which additivity does not apply, including acids and bases

> 3% Category 2


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OSHA Proposal• Labels:

–HCS required identity, hazards, supplier name and address.

–GHS requires identity, signal word, hazards, precautions, hazard symbols, supplier name, address and phone number.


OSHA Proposal• Safety Data Sheets (SDSs)

–HCS did not specify form of safety data sheet.

–GHS specifies the 16 section format with data fields for each section as per the GHS requirements.


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Labels will look different.. Current OSHA

Methyl EnigmaFLAMMABLE LIQUID AND VAPORCAUSES SKIN AND EYE IRRITATION

Phantom Chemical- Kneecap, AL.

OSHA Label Requirements

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Labels will look different.. Current ANSI

WARNING! Methyl EnigmaFLAMMABLE LIQUID AND VAPORCAUSES SKIN AND EYE IRRITATIONAvoid sources of ignition.Avoid contact with skin and eyes.Wash thoroughly after using.First Aid:.........................................In case of fire:.................................In case of spill:............................... Environmental Hazards………….. Storage and Handling:..................Disposal Considerations or prohibitions??For additional information, see MSDS.Phantom Chemical- Kneecap, AL.

Typical ANSI Label

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Under OSHA Proposal

WARNING! Methyl EnigmaFLAMMABLE LIQUID AND VAPORCAUSES SKIN AND EYE IRRITATIONKeep container tightly closed. Avoid ignition sources.Wear protective glove and eye protection.Wash thoroughly after using.First Aid:.........................................In case of fire:.................................In case of spill:............................... Environmental Hazards…………..Storage and Handling:..................Disposal Considerations or prohibitions??For additional information, see MSDS.Phantom Chemical- Kneecap, AL.

Typical ANSI Label Modified for GHS

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SDSs Requirements


• Section 1 Minimum Information– Product identity (same as on label)– Other means of identity– Product use and restriction on use– Name, address and phone number of responsible party

– Emergency phone number

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SDSs Requirements


• Section 2 Minimum Information– Classification of chemical according to new criteria– Signal word, hazard statements, precautionary statements, symbols (either graphic or words)

– Unclassified hazards (e.g. combustible dusts)– Where an ingredient is present at 1% or more with unknown toxicity…..statement indicating percentage of unknown toxicity

SDSs Requirements


• Section 3 Minimum Information– For Substances

• Chemical name and common name (synonyms)• CAS Number or other unique identifier• Any impurity that contributes to product hazard

– For Mixtures• Chemical name and common name (synonyms)• CAS Number or other unique identifier• Concentration or concentration range for each hazardous ingredient

SDSs Requirements


• Section 4 Minimum Information– First aid measures by route of entry– Most important symptoms (immediate and delayed)– Indication of immediate medical attention or other special steps to be taken

• Section 5 Minimum Information– Suitable (and unsuitable) extinguishing media– Special hazards presented by the chemical or mixture– Special protective equipment necessary for fire fighters

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SDSs Requirements


• Section 6 Minimum Information– PPE, protective equipment and emergency procedures

– Methods of cleanup and containment• Section 7

– Precautions for safe handling– Conditions for safe storage and incompatibilites

SDSs Requirements


• Section 8 Minimum Information– OSHA PELs and any other exposure value developed or used by the responsible party

• ACGIH is not mandatory unless this is what you use (wise choice….)

– Engineering controls (e.g. ventilation)– Personal Protective Equipment

SDSs Requirements


• Section 9 Minimum Information– Mandatory headings for ……appearance, odor, odor threshold, physical state, pH, melting/freezing point, initial boiling point and boiling range, flash point, evaporation rate, flammability (solid, gas), upper/lower flammability (explosive) limits, vapor pressure, vapor density, specific gravity, solubility, partition coefficient (n‐octanol/water), auto‐ignition temperature and decomposition temperature, viscosity.

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SDSs Requirements


• Section 10 Minimum Information– Reactivity– Chemical stability– Possibility of hazardous reactions– Incompatible materials– Hazardous decomposition products

SDSs Requirements


• Section 11 Minimum Information– Information on likely routs of exposure– Symptoms related to exposure by route– Delayed and immediate effects of short term exposure

– Chronic effects from long term exposure– Numerical measures of toxicity (e.g., LD50’s)

SDSs Requirements


• Section 12 Minimum Information– Ecotoxicity (aquatic, terrestrial when available)– Persistence and degradability– Bioaccumulative potential– Mobility in soil– Other adverse effects (e.g., effect on ozone layer)

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SDSs Requirements


• Section 13 Minimum Information– Description of waste residues and information on safe handling and methods of disposal (including packaging).

• Section 14 Minimum Information– UN number– UN shipping name– Transport hazard class– Packing group– Marine pollutant and other environmental hazards– Transport or bulk quantities

SDSs Requirements


• Section 15 Minimum Information– Safety, health and environmental regulations specific to the product

• Section 16 Minimum Information– Date of preparation and/or last revision
