CHEMICAL MANAGEMENT

Christian RantzauChemical Specialist Adviser

Health and Safety Unit

2

Course outline

Objectives

Assessment

Legal requirements

Chemical classification (DGs, haz subst, poisons, GHS & comp with DG)

PPE (brief)

MSDS – maybe need one more slide on MSDS sections

MSDS – how to find in chemwatch

Labelling – Chemwatch; generic/online

Risk assessments (identify, assess, control, review)

- Triggers (included because of Worksafe)

Hierarchy of control

Safe Storage (incudes segregation table; quantity table)

Safe Handling (includes incident images)

Spill Management (needs to be edited); spill kits

Waste management

Summary and review

Chemical management guidelines

ObjectivesAt the completion of this unit, you should have a good understanding of:

• Legal requirements

• Chemical classifications

• MSDS (or SDS)and labels

• Risk Assessment

• Safe storage and handling

• Spill management

• Waste disposal

Assessment

Assessment

Assessment

Assessment

Legal Requirements• OHS Regulations 2007 (VIC) – Chapter 4

– Classifications of hazardous substances

– Provision of correct MSDS

– Correct labelling

– Register

– Training

• Dangerous Goods (Storage and Handling) Regulations 2012– Safe storage and handling compatibility

– Manifest

– Spill Control

– Training

• Drugs, Poisons and Controlled Substances Regulations 2006– Permit – Each area must comply with its permit

– Locked storage and other administrative controls, i.e. recording

Chemical ClassificationsDangerous GoodsA chemical that meets the classification criteria of the Australian Dangerous Goods Code (adapted from a United Nations publication).

The criteria are based on the physicochemical properties of the substances.

Hazardous SubstanceA chemical meets the human toxicity criteria as published in the List of Designated Hazardous Substances.Published by WorkSafe Australia and based on a EEC document.

Chemical Classifications1. Hazardous SubstancesSubstances that can harm the health of people. Unsafe use and handling of hazardous substances can cause cancer, skin disease, poisoning and respiratory illness.

They are classified according to their immediate or long–term health effects. E.g. Iodine (Xn), Papain (Xn).Hazard Category: • Toxic (by inhalation, ingestion or in contact with skin)• Harmful / Corrosive (can cause burn)• Flammable• Irritant (to eye or skin)• Sensitiser (to skin, respiratory)

Chemical Classifications1. Hazardous Substances

refer to:

http://www.worksafe.vic.gov.au/safety-and-

prevention/health-and-safety-topics/hazardous-

substances/about-the-problem/scheduled-carcinogens

Note Worksafe Victoria website is not up to date

Carcinogenic substances:

- Require a licence for use in the laboratory

Chemical Classifications1. Hazardous Substances

Chemical Classifications1. Hazardous Substances

Victorian Workcover Authority: Occupational Health and Safety

Amendment Regulations, June 2014

https://www.worksafe.vic.gov.au/__data/assets/pdf_file/0003/166674/O

HS-Amendment-Regulations-June-2014.pdf

Schedule 1 carcinogenic substance and Schedule 2 carcinogenic

substance are defined by reference to the National Model Regulations

for the Control of Scheduled Carcinogenic Substances.

Are now defined by reference to new Schedules 5A and 5B of the OHS

Amendment Regulations.

Chemical Classifications1. Hazardous Substances

PROHIBITED CARCINOGENIC SUBSTANCES

Occupational Health and Safety Regulations 2007

Schedule 5A (were Schedule 1)

1. 2-Acetylaminofluorene [53-96-3]

2. Aflatoxins

3. 4-Aminodiphenyl [92-67-1]

4. Benzidine [92-87-5] (including benzidine dihydrochloride [531-85-1])

5. bis(Chloromethyl) ether [542-88-1]

6. Chloromethyl methyl ether [107-30-2] (technical grade which contains

bis(chloromethyl) ether)

7. 4-Dimethylaminoazobenzene [60-11-7] (Dimethyl Yellow)

8. 2-Naphthylamine [91-59-8]

9. 4-Nitrodiphenyl [92-93-3]

Chemical Classifications1. Hazardous SubstancesPROHIBITED CARCINOGENIC SUBSTANCES

Schedule 5B (were Schedule 2)

1. Acrylonitrile [107-13-1]

2. Benzene [71-43-2] when used as a (fuel) feedstock containing more than

50% of benzene by volume

3. 3 3,3'-Dichlorobenzidine [91-94-1] and its salts (including 3,3'-

Dichlorobenzidine dihydrochloride [612-83-9])

4. Diethyl sulfate [64-67-5]

5. Dimethyl sulphate [77-78-1]

6. Ethylene dibromide [106-93-4] when used as a fumigant

7. 7 4,4'-Methylene bis(2-chloroaniline) [101-14-4] MOCA

8. 3-Propiolactone [57-57-8] (Beta-propiolactone)

9. o-Toluidine [95-53-4] and o-Toluidine hydrochloride [636-21-5]

10. Vinyl chloride monomer [75-01-4]

Hazardous substances...

They are identified from the labels and MSDS (or SDS) with:

Statement on label and MSDS: Signal Word eg Danger

Hazardous substances...

The risk phrases (eg R35 – Causes severe burn) and safety phrases (eg S25 – Avoid contact with eyes) are still operating in Victoria –likely to change in due course.We will then have Hazard Statements (as you will see on the MSDS):

Chemical Classifications2. Dangerous Goods (DG)

DGs are substances that:• may be hazardous to people, property or the environment• may cause accidents with significant consequences due to

their immediate physical or chemical properties• are corrosive, flammable, explosive, spontaneously

combustible, toxic, oxidising or water-reactive. Eg Petrol, paints, acids, bases, flammables

Ethanol Sodium hydroxide FLAMMABLE

LIQUID

3

CORROSIVE

8

Remember:

Acids and bases (alkaline) are incompatible require segregation!

Examples: Hydrochloric acid, sodium hydroxide, acetic acid.

Segregation / Incompatibility

http://safety.unimelb.edu.au/docs/dangerous-goods-segregation-and-

storage-requirements.pdf

Segregation / IncompatibilityRun a report from your database in Chemwatch GoldFFX (separate training module)

Chemical Classifications

3. Scheduled Poisons Some substances are classified as poisons or controlled substances. E.g. Ampicillin (Sch. 4), Gentamicin (Sch. 4).

Remember:

Scheduled poisons do not necessarily have toxic diamonds –different Regulations.

Chemical ClassificationsScheduled PoisonsFor more information, go to the chemical management tab on the safety website

Chemical ClassificationsScheduled Poisons

Chemical Classifications3. Scheduled Poisons

Chemical Classifications3. Scheduled Poisons

http://safety.unimelb.edu.au/hazard-topics/chemical-management

How to check a Scheduled Poison ?

What are controlled substances?

Controlled substances are substances that are controlled by particular legislation:• prescription medicines;• pharmacy-only medicines;• drugs of dependence; and • many household, industrial and agricultural chemicals

Controlled substances are classified into Schedules 1-9, which each have different restrictions associated with them. The broad definition of these schedules appears in the Chemical Management Guidelines.

The list of controlled substances that fall into each schedule is a combination of the Poisons Code (Vic) and the Poisons Standard.

The Poisons Standard is the legal title of the Standard for the Uniform Scheduling of Medicines and Poisons (SUSMP).

http://www.tga.gov.au/publication/poisons-standard-susmp#electronic

Scheduled Poisons....Regulated Permit Compliance

• Permit to obtain Sch 4, 7 (listed regulated), 8, 9– Store in locked cupboard

– Restricted access

– Administrative control log book

– Disposal requirement (for schedule 8 & 9)

• Get APPROVAL your Supervisor/Lab head, prior purchasing:– Schedule 4 – ampicillin, neomycin, chloroform (anaesthetic), lignocaine,

some vaccines

– Schedule 7 – arsenic, cyanides, chlorine gas, benzene, bromine

– Schedule 8 – ketamine, morphine, pethidine, some barbitones

– Schedule 9 – Prohibited substances (heroin, cannabis etc)

Haz subs vs DG vs Sch.Poison

New Global Harmonisation System (GHS) will be implemented – expect to see new pictograms:

Separate training module for GHS

Equivalent pictograms

under the ADG Code

and GHS(Dangerous Goods Act 1985 Code of practice for

the storage and handling of dangerous goods)

Appendix 8

Type of dangerous goods ADG Code GHS

Flammable gases

Class 2.1

FLAMMABLE GAS

2

FLAMMABLE GAS

2

Non-flammable,

non-toxic gases

Class 2.2

Toxic gases

Class 2.3

NON-FLAMMABLE NON-TOXIC

GAS

2

NON-FLAMMABLE

NON-TOXIC GAS

2

TOXIC GAS

2

Flammable liquids

Class 3

FLAMMABLE LIQUID

3

FLAMMABLE LIQUID

3

Flammable solids, self-reactive

substances and solid desensitized

explosives

Class 4.1

Substances liable to spontaneous

combustion

Class 4.2

FLAMMABLE SOLID

4

SPONTANEOUSLY

COMBUSTIBLE

4

Substances which in contact with water

emit flammable gases

Class 4.3

DANGEROUS WHEN WET

4

DANGEROUS WHEN WET

4

Equivalent pictograms

under the ADG Code

and GHS(Dangerous Goods Act 1985 Code of practice for

the storage and handling of dangerous goods)

Equivalent pictograms

under the ADG Code

and GHS(Dangerous Goods Act 1985 Code of practice for

the storage and handling of dangerous goods)

ADG classes and packing group (PG) GHS categories

Class 2.1 Flammable gases Category 1

Flammable aerosols Category 1 and 2

Class 2.2 Oxidising gases Category 1

Gases under pressure

• Compressed gases

• Liquefied gases

• Refrigerated liquefied gases

• Dissolved gases

Class 2.3 Acute toxicity: inhalation categories 1-4

(Note: Category 4 only up to LC of 5000 ppmV)

Skin corrosion/irritation categories 1A-C

Class 3 PG I Flammable liquids Category 1

Class 3 PG II Flammable liquids Category 2

Class 3 PG III Flammable liquids Category 3

Class 4.1 self-reactive substances types A-G Self reactive substances type A-F.

Type G are not classified under model work health and

safety regulations as hazardous chemicals.

Class 4.1 PG II Flammable solids Category 1

Class 4.1 PG III Flammable solids Category 2

Class 4.2 PG I Pyrophoric liquids Category 1

Pyrophoric solids Category 1

Class 4.2 PG II Self-heating substances Category 1

Class 4.2 PG III Self-heating substances Category 2

Class 4.3 PG I Substances and mixtures which in contact with water emit

flammable gases, Category 1

Class 4.3 PG II Substances and mixtures which in contact with water emit

flammable gases, Category 2

Class 4.3 PG III Substances and mixtures which in contact with water emit

flammable gases, Category 3

Class 5.1 PG I Oxidising solids, oxidising liquids, Category 1

Class 5.1 PG II Oxidising solids, oxidising liquids, Category 2

Class 5.1 PG III Oxidising solids, oxidising liquids, Category 3

Class 5.2 organic peroxides types A-G Organic peroxides types A-F.

Type G are not classified under model work health and

safety regulations as hazardous chemicals.

Equivalent pictograms under the ADG Code and GHS(Dangerous Goods Act 1985 Code of practice for the storage and handling of dangerous goods)

Class 6.1 PG I Acute toxicity: oral Category 1

Acute toxicity: dermal Category 1

Acute toxicity: inhalation Category 1 (dusts, mists, vapours)

Class 6.1 PG II Acute toxicity: oral Category 2

Acute toxicity: dermal Category 2

Acute toxicity: inhalation Category 2 (dusts, mists, vapours)

Class 6.1 PG III Acute toxicity: oral Category 3

Acute toxicity: dermal Category 3

Acute toxicity: inhalation Category 3 (dusts, mists, vapours)

Class 8 PG I Skin corrosion Category 1A

Class 8 PG II Skin corrosion Category 1B

Class 8 PG III Skin corrosion Category 1C

Corrosive to metals Category 1

Class 9 Class 9 dangerous goods are not classified under the work

health and safety laws

Goods too dangerous to be transported Self reactive substances type A

Organic peroxides type

A Unstable explosives

C1 combustible liquids (flash point 60-93°C) Flammable liquids Category 4

(flash point 60-93°C)

Chemical Hazard

https://en.wikipedia.org/wiki/Karen_Wetterhahn

https://www.youtube.com/watch?v=h049Hgfk-BI

Dimethyl Mercury- A few drops from a pipette onto the latex glove.- Glove not removed, but cleaned up the area and spill.- Dimethylmercury can penetrate the glove and skin in 15 secs- 5 months after exposure, noticed neurological problems- In hospital – urinary mercury at 234 ug/L; - Toxic >50ug/L; normal is 1-4 ug/L- Use multilayered neoprene gloves

Hydrofluoric acid or hydrogen fluoride- Have calcium gluconate gel available

https://www.youtube.com/watch?v=OzG6xNzyj8k

https://www.youtube.com/playlist?list=PLNhVwA0XZE27h8uh8ug8k

X3362W2CAvai

Personal Protective Equipment

Personal Protective EquipmentTRIFLUOROMETHANESULPHONIC ACID 98% (TRIFLIC ACID)

Separate PPE training module

Personal Protective Equipment

MSDS or SDS• MSDS – Material Safety Data Sheet (or Safety Data Sheet)

• Contains safety information data on whether a given material is a hazardous substance, dangerous good and/or scheduled poison;

• Contains risk and safety phrases, first aid measures, exposure limits, etc;

• How to store and dispose properly;

• What to do in case of a spillage;

• In case of emergency provide proper handling procedure Hazchem code, appropriate extinguisher, PPE, etc.

MSDS must be from the supplier, current (within 5 years), and be compliant with the Australian format the Law.

MSDS - AccessUoM Safety Access GoldFFX

Separate Chemwatch training moduleSuggest you use Firefox (not Internet Explorer)

http://safety.unimelb.edu.au/hazard-topics/chemical-management

For Emergency & Quick reference

Or.... you can access Manufacturer MSDS

Sample - Manufacturer’s MSDS

MSDS - Verification

http://safety.unimelb.edu.au/hazard-topics/chemical-management

GoldFFX - Reporting

GoldFFX – Reporting – Health Surveillance

Labelling

• All hazardous substances must be labelled properly according to the legislation.– Hazard category

– Risk Phrases

– Safety Phrases

• This includes: decanted chemicals, diluted chemicals (if they are still classified as hazardous) and mixtures.

Labelling

Labelling

Labelling

Full Chemical name

Hazardous

Substance

Yes □

No □ Concentration

Risk Phrase/s

Safety Phrase/s

DG Class 3 6 8 Other

DG Sub-risk Other

Researcher

Date Disposal

Date

Labelling of decanted/diluted/mixed substances

Labelling of decanted/diluted/mixed substances

Contractor -

Methylated spirits

In a coke bottle – unlabelled.

Chid care centre

Risk AssessmentWhere we use chemicals, we must;

Identify the hazards

• flammable, toxic, corrosive, mutagenic, irritant, etc

Assess the risk

• injury or illness from any of the listed hazards

Control the risk

• use the hierarchy of control and ensure this is communicated to all persons who are exposed

Review• control measures & monitor effectiveness

By law we must conduct these assessments

Risk AssessmentTrigger points:http://www.oshrisk.org/videos/

Risk sources and events

that give rise to risk

Risk assessment

Risk Assessment

Trigger points:• indicators that a risk has occurred or is about to occur.

• best triggers tell you well in advance that a problem will occur.

• to identify triggers:o talk with the people who are most likely to cause the risk to occur and

those who are most likely to feel its impact. Ask them how they would know that the problem is occurring. Start with how they would know that the problem has already occurred, and then work backward to determine how they would know before the problem actually occurred.

• create a watchlist:o shows the possible triggers, when they are likely to occur, and who

should watch for the trigger.

http://acqnotes.com/Attachments/Risk%20Assessment%20Worksheet%20and%20Management%20Plan.pdf

Risk AssessmentSuggested triggers for chemical risk assessments include:

• a new process is being initiated

• new staff or students are working in the laboratory

• a new chemical is being used

• the chemical process has changed

• the properties of the chemical changes with time

• the chemical is toxic

• the chemical is dangerous

• the chemical undergoes change during a process

• the chemical exposure limits are low

• spillage of the chemical will result in a serious incident

• changes in Legislation or local provisions

http://acqnotes.com/Attachments/Risk%20Assessment%20Worksheet%20and%20Management%20Plan.pdf

Control measures

Use a less hazardous chemical

Use Class II cab or fume hood

SOPs training and review

Glasses, coat, gloves, mask etc

National Institute for Occupational Safety and Health

- From the CDC web site

- http://www.cdc.gov/niosh/topics/hierarchy/

Risk Assessment

Risk AssessmentWhen things go wrong:

Nickel hydrazine perchlorate

Preston Brown. Texas Tech University

https://www.youtube.com/watch?v=sjDdl_d8br8 (go to 1.50’)

And

https://www.youtube.com/watch?v=OzG6xNzyj8k

Safe Storagehttp://safety.unimelb.edu.au/docs/chemical-storage-and-handling-for-minor-

quantities-in-laboratories.pdf

Safe storage• Check MSDS for proper storage

• Segregate incompatible chemicals (according to the DG classification)

Class 2.3 toxic gases from all other classesClass 3 flammable liquids and Class 5 oxidisersClass 3 and Class 8 corrosives sub-risk Class 5 oxidisersClass 4.3 dangerous when wet from all other classesClass 5.2 organic peroxides from all other classesClass 7 radioactive from all other classesClass 8 corrosives – separate acids and bases

• Provision of spill trays and secondary containers• Scheduled Poisons (4, 7-restricted regulated, 8, 9) –

locked cupboard

Safe storage

Safe storage

Safe storage• Review storage

• Review incompatibility

http://safety.unimelb.edu.au/docs/chemical_storage_handling_for_minor

_quantities_quick_reference.pdf

Storage example

Remember:

Fume cupboard is not

for storage purpose!

Remember: Fume cupboard is not for storage purpose!

(Feb 2016)

Safe Handling

• Check MSDS Working condition, additional precautions, PPE required, etc

• Implement control measures Use in fume cupboard, wear proper PPE

• For transporting Use canisters

Working in Fume Cupboard – sash down!

When things go wrong

RMIT 2013

• Small amount of metallic sodium

fell into the sump of the cabinet.

• Slowly reacted then caught fire

When things go wrongMarch 2016

• organic chemistry lab in Shanghai.

• student was using sodium metal.

He put the residue waste into

petroleum ether (this is not good,

should quench with ethanol).

• It is said that the water content of

the petroleum ether is too high, the

sodium waste ignite the solvent.

• The student used sands trying to

put out the fire (this is right).

However, petroleum ether fire

spilled out.

• The lab was not tidy and the spilled

fire ignite other inflammable

material (not mention what,

possibly waste solvent).

• And then the fire is completely out

of control.

When things go wrong

When things go wrong

Dec 2015

Beijing: Tsinghua University.

Postdoc research fellow (32 yo Meng

Xiangjian) was killed by blast in a lab

when an organic catalytic reaction

went out of control.

Few further details……..

When things go wrong

Spill ManagementBe familiar with substances you handle in your area

The nature of the spill• Organic spill (ethanol, acetone can be flammable, vapour can be toxic

• Acid/bases spill (HCl, bleach) corrosion, burn to skin

• Biohazard (blood based, microorganism, virus) contamination and may lead to infection

• Aerosols/droplets Contamination

inhalation of hazardous materials

• Non hazardous spill (water, non hazardous solution) physical risks, i.e. slips

• Quantity & Location– Quantity depends on the nature of spill– Location – near waterways, equipment, other work area

Most of spills safety and environmental risks

Spill Management Procedure

1. Assessment– Assess the hazards, e.g. nature of spill, quantity, location

of spill– Consult with MSDS (if applicable)– Ensure area is safe and ventilation is adequate

Only attempt to clean up if you feel confident to do soOtherwise, seek assistance

Spill Management Procedure

2. Control and containment• Stop at source – turn the container upright, turn off

valve/pump• Control and contain flow – block drains, absorbent socks

around the drain

• Correct choice of spill kit and wear proper PPE

Spill Management Procedure3. Clean up and disposal

Principles:– Do not handle any sharps with hand, use rigid disposable material,

such as cardboard

– Absorb liquid into solid

– Do not leave any slip hazards

– Double contained absorbents and all contaminated materials

– Chemical spill dispose as chemical waste

Clean up and disposal.....

• Biohazard spill– Soak spilled area and its surroundings with active disinfectant for 30 mins

– Clean up according to spill management procedure

– Decontaminate the spill kit equipment properly

– Discard all waste as biohazard waste and autoclave is necessary.

• Aerosols– If there is a risk of aerosol/droplet formation, evacuate area and wait for

at least 30 mins

– Put up a sign to inform others, include the time

– Clean up according to spill management procedure

Spill Management Procedure

4. Record and Report• Report any spill incident to your supervisor

• Record the spill incident in the incident reporting system

5. Restock• Restock items used to get it ready for next use.

Spill Management Procedure

Spill kits – samples

Simple spill kit Chemical spill kit

Mercury spill kit Biohazard spill kit

Chemical Waste DisposalWaste Minimisation

Purchasing controls

Inventory controls

Operational Controls

Chemical Waste Disposal

Chemical Waste DisposalPicric acid (Trinitrophenol)

Class 4.1 (flammable solid when wetted

with >30% water to mass)

Class 1.1 (explosive when dry)

Chemical Waste Disposal

~10-20g dry salts

Chemical Waste Disposal

3g of trinitrophenol is ignited with a charge

Chemical Waste Disposal

DisasterDevastation of Halifax on Halifax harbour in 1917 following the explosion of the vessel SS Mont-

Blanc (carrying TNT, benzole, picric acid and gun cotton).

Over 2000 people killed and 9000 injured.

Chemical Waste DisposalConsult with your Supervisor/Lab Manager• managed locally

• Review your SOP

For departments located in UoM precinct, this is managed by the Health & Safety unit:

See http://safety.unimelb.edu.au/support/waste/

And email hazardouswaste-info@unimelb.edu.au

Waste manifest:

• Fill out the form

• Label the waste container properly with information: – Chemical name/mixture,

– Department number and name,

– DG Class diamond, Packing Group, Type of waste, volume

• Monthly pick up

Chemical Waste Disposal

Chem Eng store March 2016

Important Principles – for ALL

• All chemicals are still classified as DG/Haz.Sub even when they are waste Proper label, segregation, bunding and spill control procedure in place

• Use rigid and leak proof containers – no glass (if possible)

• Do not mixed unknown chemicals or incompatible chemicals if unsure, separate the waste

• Store in designated and secured area restricted access

• Dispose through approved waste contractor

• Additional controls are required if disposing Scheduled Poisons 8 and 9

Your duties:Before Ordering:• Check MSDS – (or SDS):

– Classification

– Restrictions

– If Permit is required prior to ordering

• Permission to order is required

Once it arrives:• Store in proper storage area

• Update your Chemical inventory in Chemwatch

Once you finish:• Dispose properly

• Update inventory

What else?

Additional steps for chemical safety:

- Good house keeping

- Store chemicals appropriately

- Chemical inventory update

- Dispose of unused chemicals

- Lab inspection (every 3 months)

- Complete your role in the cyclical check list

Further readinghttp://safety.unimelb.edu.au/docs/chemical_management_guidelines_V2_0.pdf

Questions??