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Workshop Chemical Safety and Security  Yogyakarta, Indonesia  Yogyakarta, Indonesia April 2011

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Workshop Chemical Safety and Security

 Yogyakarta, Indonesia Yogyakarta, Indonesia

April 2011

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2

Chemical Safety and Security

Overview

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3

Why worry about chemical safety?

� Chemicals used everyday in

labs and factories can be

hazardous.

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4

- Shorter life spans, more disease

Hoar, S. K. et al, J. Occup. Med,. 23, 485 (1981)

- Higher cancer incidence

Dement J.M. & Cromer J.R.,  A ppl. Ocup. Environ. Hyg ., 7,120 (1992)

- Higher suicide rate (females)

Walrath J. et al,  Amer. J. Pub. Health, 35, 883 (1985)

Studies indicate lab chemists may have:

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Possible chemical health problems

Chemicals

� Vinyl chloride

� Asbestos

� Carbon tetrachloride

� Mercury

� Lead

� Thalidomide

� Methanol� CO, CS2

Diseases

� Liver cancer 

� Mesothelioma

� Hepatotoxin ( jaundice)

� Neurotoxin, CNS, narcosis

� Reprotoxin, birth defects

� Reprotoxin, developmental

defects

� Blindness, death

� Hematopoietic,

hemoglobin, cynanosis

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6

But disease depends on many factors«

� Genetics

� Specific chemical

�P

rotection controls used� Dose

� Concentration

� Duration

� Life style

� Environment

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77

University of California Santa Cruz: Fire

� January 11, 2002:about 5:30 am, 4th floor of Sinsheimer Lab building,Dept. of Molecular, Cell andDevelopmental Biology.

 ± Firefighters responded to alertfrom heat-detection system inbuilding.

 ± Controlled by noon.

 ± Up-to-date inventory of 

hazardous materials allowedfirefighters to enter buildingand contain fire.

 ± Building did not haveautomatic sprinkler system.

http://ehs.ucsc.edu/emergency/pubs/sinshfire2.htm

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8

University of California

Santa Cruz: Fire, cont¶d.

� Professors and students lostequipment, notes, materials,samples.

� Other labs in building closedfor weeks to months.

 ± Water and smoke damage

� Burned labs took 2 years toreopen.

� Cause never determined.

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9

Environmental hazards

California StateU

niv. Northridge: Earthquake

� Several fires in sciencebuildings allowed to burnbecause firemen worriedabout chemical hazards

� Professors and studentslost equipment, notes,materials, samples

Images courtesy: P.W. Weigand, California State University Northridge Geology Department,

Image source: Earth Science World Image Bank http://www.earthscienceworld.org/images

� Magnitude 6.7

� January 17, 1994 ± 4:31 am

� 57 deaths, 11000 injuries

� Epicenter a few km

from California

State University

Northridge campus

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10

University lab chemical accidents

Incident ± Chemical

� Fire and one death ± t-butyl lithium + pentane

� Dartmouth, wrong gloves ± methyl mercury

� Wroclaw Poland, explosion ± dry perchlorates

� Australia, skin absorption ± hydrofluoric acid

� Okazaki Japan, explosion ± peroxide by-products in synthesis

� OSU, US cylinder explosion ± liquid nitrogen cylinder 

� Material science engineering lab explosion ± nitric acid + ethanolexplosion

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11

Bhopal: Pesticide plant chemical release

� One of the greatest chemical disasters in history,December 1984

� Union Carbide plant making Sevin released ~40 tonnesof methyl isocyanate in the middle of the night

� Low local demand for pesticides meant the plant wasonly partially running

� Some hardware was broken or turned off, includingsafety equipment

 ± Safety measures and equipment far below USstandards

� Plant in heavily populated area

* ³The Bhopal disaster and its aftermath: a review´, Edward Broughton, Environmental Health: A Global Access

Science Source 2005, 4:6, http://www.ehjournal.net/content/4/1/6, accessed 12/07

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12

Safety Video: Reactive Hazards

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13

Major industrial chemical disasters

Accident/location

� ~1912 Toyama Japan

� 1921 Oppau Germany

� 1930 Gauley Bridge WV USA� 1968 Yusho Japan

� 1974 Flixborough UK

� 1976 Seveso Italy

� 1984 Bhopal India

� 1986 Chernobyl Ukraine

� 2005 Texas City USA

� 2005 Jilin China

Chemical product & exposure

� itai-itai disease/cadmium

� ammonium nitrate

� silica� rice oil/PCB,PDDF

� cyclohexane

� herbicide production/TCDD

� methyl isocyanate

� ionizing radiation

� hydrocarbon production

� benzene/aniline

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14

Chemical accidents are now under 

stricter control and scrutiny

� Better individual country regulations

� Better international regulations

 ± IATA

 ± GHS ± REACH

� Environmental problems after natural disasters

 ± Earthquakes, cyclones, hurricanes, floods

� Increased public awareness

� Increased media coverage

� Less public tolerance

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15

Why worry about chemical safety?

� Health of the workers

� Safety of the workers

� Safety of the community

� Safety of the environment

«I t¶s the right thing to do! 

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16

Aum Shinrikyo:

Matsumoto and Tokyo, Japan

� Sarin attack on Judges in Matsumoto, June 1994

 ± Sarin sprayed from truck at night

 ± 7 deaths, 144 injuries

� Sarin attack on Tokyo subway, March 1995

 ± 11 bags with 600 g each on3 main subway lines

 ± 12 deaths, 3938 injuries

� Hydrogen cyanide attacks onTokyo subway, May 1995

 ± Bags of NaCN and sulfuricacid

 ± No deaths, 4 injuries

Photo of wanted poster from Wikipedia

commons

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� Recruited young scientists from top Japanese universities.

� Produced sarin, tabun, soman,VX.

� Purchased tons of chemicals

through cult-owned companies.

� Motives: proof of religious

prophecy, kill opponents, interferewith legal proceedings and police

investigations.

Aum Shinrikyo:

Matsumoto and Tokyo, Japan, cont¶d.

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18

Iraq

� Many incidents in whichchlorine gas cylinders areblown up with explosives

 ± Chlorine probablystolen/diverted from water purification plants or oilindustry

 ± Many civilians and non-combatants injured

� Chlorine first used in WWI

as a chemical weapon

On March 23, 2007, police in Ramadi's Jazeera district seized a truck filled with "five

1000-gallon barrels filled with chlorine and more than two tons of explosives"

From http://www.longwarjournal.org/archives/2007/03/al_qaedas_chlorine_w.php downloaded Jan 2008.

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19

Chemical Security

"Now, the chemical sector certainly stands as one of the

principal areas of infrastructure about which we have to be

concerned. If you look back at the whole history of the way alQaeda has conducted its operations, where possible, they

have always tried to leverage our own technology against

ourselves. They've turned jets, commercial jets, into

weapons. They've tried to use our own chemicals and our 

own products as means of exploding devices against us. And

obviously, one of the areas we have to be concerned aboutare parts of our infrastructure which house chemicals which

could, if properly ignited, create a huge amount of havoc in a

populated area ± whether it be because of a large explosion or 

whether it's because of toxic inhalation..."

US Homeland Security Secretary Michael Chertoff told

the American Chemistry Council, March 21, 2006:

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Why worry about chemical security?

� Health and safety of people and environment

� Community relationships

� Reduce chance of accidental chemical release

� Avoid loss and damage to labs and equipment

� Prevent criminals and terrorists from getting dangerous

chemicals

 ± Wide variety of chemicals have been used

 ± Wide variety of motivations for actions

� A deliberate attack on a chemical facility could release a

large amount of hazardous chemicals

 ± Injure or kill people in nearby areas

 ± Eliminate jobs and economic assets

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21

Safety and Security Issues are similar 

Protect

� Workers

� Facility

� Community

� Environment

Variables

� Many different chemicals with:

 ± different properties

 ± different hazard

 ± different applications

� Many different ways to misuse

chemicals

 ± chemical weapons

 ± poisons

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22

Government regulations: Chemical security

� Differ from country to country

� Legislation needed to fulfillrequirements under the Chemical

Weapons Convention ± Each country passes appropriate

laws

 ± Each country must declare andtrack certain chemicals

�UN Resolution 1540

� Other export control legislation

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23

How does your country regulate and control

chemical safety and security?

«Is it effective?

«Could it be improved?

«How?

Important Questions:

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2424

Fundamentals of Fundamentals of 

Chemical Laboratory SafetyChemical Laboratory Safety

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2525

References

³Safety in Academic Laboratories, Vol.1 & 2,´

American Chemical Society, Washington DC,

2003, also available online:http://membership.acs.org/c/ccs/publications.htm

³Prudent Practices in the Laboratory: Handling

and Disposal of Chemicals,´ National Academy

Press, 1995, also available online:

http://www.nap.edu/catalog.php?record_id=4911

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26

Definitions

26

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Chemical Laboratory Safety

 ± T he control of exposure to potentially 

hazardous substances to attain an acceptably 

low risk of exposure

27

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Hazard ± the potential to har m

Risk ± the probability that har m will result 

Chemical Laboratory Safety

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� Chemical hazards

 ± dusts, fumes, mists, vapors, gases

� Physical hazards

 ± fire, electrical, radiation, pressurevibration, temperatures, noise

� Ergonomic hazards

 ± repetitive motion (pipetting), lifting,

work areas (computers, instruments)� Biological hazards

 ± pathogens, blood or body fluids

Chemical Laboratory Hazards

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30

Chemical Laboratory Safety

based on the principle of 

Industrial Hygiene

 ± The anticipation, recognition, evaluation and control 

of healt h hazards i n t he w ork env i ronment  to prot ec t  

w ork ers healt h and well-bei ng  and  to saf eguard  t he

c ommuni ty  and  t he env i ronment 

30

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3131

Industrial Hygiene Principles

Anticipation

Recognition

Evaluation

Control

Chemical hazards

Physical hazards

Ergonomic hazards

Biological hazards

Chemical Laboratory Safety

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32

Anticipation

S afety First ! 

To consider safety in the beginning is:

« and it saves you ti me ! 

32

Easier,

Cheaper,

Safer,

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3333

Anticipation

Advance Experiment Planning:

Outline proposed experiment

Acquire safety information(M)SDS, REACH

Consult with CSSO?

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3434

Anticipation

Risk Analysis

� Which chemicals?

� How much?� Special equipment needed?

� Who does the work?

� Staff properly trained?

� Can the experiment go wrong?

� Do you have an emergency plan?

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3535

Recognition

Types of lab hazards:

chemical toxicity

fire / explosionphysical hazards

biohazards

radiation

special substances

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3636

Recognition & Evaluation

What are the anticipated risks?

 ± Are the equipment & facilities adequate?

 ± Are staff properly and sufficiently trained?

 ± Risks if experiment goes wrong?

 ± Is there a plan for this?

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3737

Control

How are the risks controlled?

� Engineering controls:

 ± enclosure / isolation ± ventilation / hoods

� Emergency Plan

� Personal Protective Equipment (PPE)

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3838

Evaluation & Control

 ± Administrative practices

organizational policies

 ± Operational practices

work practices

 ± Engineering controls

ventilation, barriers

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3939

Administrative Practices

organizational safety policies

that apply to everyone

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4040

Lab Safety Policies

Have a Safety Manual

Never work alone, especially after hours.

Specify when eye protection & PPE is required.

Specify operations that require hood use.

Specify required training.

No mouth pipetting.

No long hair or dangling attire.

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4141

Lab Safety Policies

� No eating, drinking, smoking inlaboratories

� Label all chemical containers

� Label refrigerators, No Food

� Label explosion safe refrigerators

� Require periodic fire drills

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4242

Lab Safety Policies

Schedule routine, periodic maintenance

and inspection of hoods.

Schedule routine, periodic maintenance

of safety showers and eye wash stations.

Post restricted areas with proper signs: ± radiation, biosafety, carcinogen, high voltage, lasers,

authorized personnel only, etc.

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4343

Operational Practices

Safe Laboratory Procedures:

� Packages opened only in labs, not receiving

� Receiving staff trained to look for signs of breakageand/or leaking shipments

� Receiving area has spill kits

� Mailroom/receiving alert for suspicious shipments

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4444

Safe Laboratory Procedures

Schedule routine maintenance, calibration and

inspection of all hoods and safety equipment.

Schedule and participate in routine fire drills.

Train personnel in emergency response.

Wear PPE properly, don¶t just have it.

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Safe Laboratory Procedures

Use hoods properly:

-Work 6´ (15 cm) in from sash

- In center of hood-Work with hood sash at ~18´

(45 cm) high

-Close sash when not in use

- Don¶t use for storage

4545

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4646

Safe Laboratory Procedures

Safely transport chemicals:

� Use container in a container concept

� Label all containers

� Inform driver of hazards

� Provide contact names, phone numbers

� Provide MSDS

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4747

Transfer Chemicals Properly

�Some flammable liquids accumulate a

static electric charge, which can

release a spark that ignites the liquid

�Always bond metal dispensing and

receiving containers together before

pouring

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4848

Control of Static

Bond wire necessary except where containers are inherently

bonded together, or arrangement is such that fill stem is always

in metallic contact with receiving container during transfer.

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4949

Safe Laboratory Procedures

Housekeeping:

� label all containers

� clean-up spills

� eliminate trips hazards

� proper storage

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5050

Dangerous Housekeeping

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5151

Engineering Controls

SOURCE

RECEIVER

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5252

Laboratory Containment Principles

C oncept 

Source Path Receiver  

C ontrol U sed 

Engineering Operational PPEControl Practices

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5353

Engineering Controls

1. Change the process

eliminate the hazard

2. Substitution

non-hazardous substance for hazardous

(e.g. - toluene for benzene)

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5454

Engineering Controls

3. Isolate or enclose the process or worker 

Use a barrier 

4. Ventilation

Dilution (general ventilation) - Not good

Local exhaust ventilation (LEV) - Preferred

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5555

Engineering Controls

Dilution (general)

ventilation

not good 

Local exhaust

ventilation preferred 

G

QIN QOUT

CV

Q = flux, C = contaminant conc.

V = velocity, G = generation rate

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Properly functioning

& used correctly!

Laboratory hoods and

ventilation are the

basis of engineering

controls.

Engineering Controls

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5757

Laboratory Hoods

Must be used and maintained properly.

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5858

Engineering Controls

Local exhaust

ventilationincludes:

snorkels

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5959

Engineering Controls

Local exhaust ventilation includes:vented enclosures

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Engineering Controls

Local exhaustincludes:

special containment 

devices

(e.g. - glove boxes)

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6161

Engineering Controls

Local exhaustincludes:

special containment 

devices

(e.g. - isolationchambers)

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Engineering Controls

Local exhaust includes:

biological safety 

cabinets

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6363

Engineering Controls

Special barrier facilities

clean rooms, carcinogen

rooms, weighing rooms

Safety shields

radiation shields, hood sashes,

splash guards

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6464

Hood exhaust should not be blocked or deflected

downward, but should exhaust straight up

Engineering Controls

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6565

Avoid

re-entrainment

Disperse

emissions

straight upward

and downwind!

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6666

Avoid Recirculation!

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6767

Personal Protective Equipment

PPE includes:

eye protection,

gloves,

laboratory coats. etc.,

respirators,

appropriate foot protection

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6868

Personal Protective Equipment

Eye protection -

specific to the hazard 

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6969

Personal Protective Equipment

Gloves -

must be chemical specific 

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7070

Personal Protective Equipment

� Laboratory coats

� Aprons

� Other protective clothing

P l P t ti E i t

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7171

Personal Protective Equipment

Respiratory Protection

Requires:

training &

fit-testing

Can provide afalse sense of security.

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7272

Personal Protective Equipment

Foot Protection

Steel toe-safety shoes are not necessary for 

laboratory work unless there is a serious risk

from transporting or handling heavy objects.

However,

open toe shoes

should NOT be worn in labs.

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7373

Have an evacuation plan and POST IT!

Emergency Planning & Response

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7474

Emergency Planning & Response

Never usehallways for 

storage

Dangerous!!

Blocks passageand emergency

exits

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7575

Emergency Planning & Response

Have routine, unannounced evacuation drills.

Designate a person for each area to ensure

bathrooms, etc. are evacuated.

Locate outside staging areas at sufficient distance

from the building.

Test and maintain alarms.

Post a person to meet/direct emergency vehicles.

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7676

Alarm systems need to be properlylocated, maintained,

and serviced regularlyand

be suitable for all disabled workers.

Emergency Planning & Response

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7777

Emergency Planning & Response

All hoods should have low flow alarms.

Chemical specific toxicityalarms may be needed

in certain areas.

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7878

Emergency Planning & Response

Centrally locate and maintain fireextinguishers and alarms.

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7979

Emergency Planning & Response

If employees are expected to useextinguishers, they must be trained!

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80

Emergency Planning & Response

Post each room with:

Emergency phone numbers

 After hour phone numbers

Person(s) to be contacted

 Alternate person(s)

Unique procedures to be followed

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8181

Emergency Planning & Response

Label and keep all exits clear,

unlocked or equipped with panic bars.

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8282

Chemical Exposures to Eyes or Skin

� Remove contaminated

clothing

� Thoroughly flush withwater 

� Follow chemical specific

procedures (i.e.. HF)

� Seek medical assistance

Centrally locate equipment

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8383

Chemical SpillsChemical Spills

Clean-up spill only if you know the chemical hazards,

have appropriate equipment and are trained to do so!

� Alert colleagues and secure area

� Assess ability to clean-up spill

� Find spill kit

�U

se appropriatePP

E and sorbent material� Protect sinks and floor drains

� Clean-up spill, collect/label waste for disposal

� Report all spills

Centrally locate spill kits for quick access

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8484

Emergency Planning & Response

Backup power:Does power switch-

over automatically?

How long will it run?How much fuel do you

have?

What areas will it

support?

How often is it tested

And maintained?

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8585

Emergency Planning & Response

Centrally locate, inspect and maintain:

� First aid kits

� Special chemical antidotes, if necessary

� Respirators

� Specially train emergency personnel, if necessary

� Post date of last inspection on equipment,including hoods.

A Q ti ?

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Any Questions?