Lab Assessment Exercise

Keday, Malaysia
30 April 4 May 2012

Part 1: Lab Layout and Safety Controls

SAND No. 2009-8395P

Sandia is a multiprogram laboratory operated by Sandia Corporation, a Lockheed Martin Company,
for the United States Department of Energys National Nuclear Security Administration
under contract DE-AC04-94AL85000.

Protect the Workers

Enable the Work
Secure the Facility
Protect the Environment
Comply
p y with Regulations
g

Provide a safe/secure workplace

Facilitate workplace activities

Efficient

Cost Effective

Cost
Poor
Communication
P
C
i i
Lack of Scientific Knowledge
Complicated Project
Trade
Trade-offs
offs
Personalities
Maintenance

Chemical Containment Concept

Based on:

Environment

Chemistry
Knowledge

Containment
Maximize Containment

Environment

Facility

Facility
Minimize Contamination

Redundancy is the Key

Storage

Facility

Personnel
Engineering Controls

Environment
7

Operations

Facility
8

Environment

Chemistry Knowledge
Workers must have knowledge and
understanding

Construction
How well the facility is built

Containment
Safe/Secure Storage
Proper Work Practices
Good Engineering Controls

10

Architects
Engineers
Administrators
Builders
EHS Professionals
P f
i
l

Laboratory Users

11

12

Major US Standards & Guidelines

Definition
(problems and needs)

ANSI Z9.5
American National Standards Institute,
Z 9.5
95L
Laboratory
b
t
Ventilation
V til ti Standard
St d d

(iterativeprocess)

NFPA

Interpretation
(of requirements into design criteria)

BOCA

(iterativeprocess)

ASHRAE 110

Design

National Fire Protection Association

Building Officials Code Association
American Society of Heating, Refrigeration and Air
Conditioning Engineers
Engineers, Standard 110 for Testing and
Evaluating Laboratory Hoods

(translates specifications into pragmatic reality)

Construction
(to accomplish goal)

Others
-

National Electrical Code

American Chemical Society, Green Chemistry Institute

www.acs.org/greenchemistry

13

14

Architectural Features Include:

-

Layout of buildings and laboratories

S
Space
requirements
i
t

Spatial arrangement of equipment and benches

Emergency egress

Storage requirements

Waste requirements

Access controls

Security features

15

Spatial

Floor
Fl
plan
l
Location of rooms and equipment
Traffic flow of people and equipment
Access control

Ventilation
Utilities
Effl
Effluent controll
Control and monitoring

Mechanical

Safety and Security

16

Factors in Laboratory Design

General Information Needed

Number of occupants and their technical

qualifications

HVAC*

Space and storage requirements

Safety and Security

Utilities needed

Fire

Equipment needs

Emergencies

Time/duration of occupancy

E
Exposures

A
Anticipated
ti i t d changes
h
iin research/programs
h/

Access/exit control (facility, chemicals, equipment)

Sustainability (environmental, green initiatives)

Security needs

Architectural

(* heating, ventilation, and air conditioning)

17

Safety/Security Information
Needed for Lab Design
Type
yp of Work/Research
Type of Hazards
Type of Wastes
Chemical
Biological
Radiation
High Voltage

19

18

Safety/Security Information
Needed for Lab Design, contd.
Types of Chemicals
(based on physical state and properties)
Flammable
Corrosive (acid or base)
Reactive
Acutely Toxic (poisons)
Regulated
g
Chronically Toxic (e.g.,carcinogens, repro-toxins)
Chemicals of security concern
Controlled Drugs
Wastes
20

Sample preparation and storage area

Segregate
sample
using
acidS
l digestion
di
i
i
id
specialized laboratory hoods
Segregate solvent extraction to reduce
vapor contamination
Proper eyewash placement
Adequate egress
Waste storage area
Gas bottle storage

Zones or control areas may

have different:

Types and degree of hazards

Amounts of hazardous
chemicals

Allows better control over:

Personnel access
Hazards using

Equipment
PPE
Administrative procedures

Examples: Fire safety zones,

HVAC zones, Building floors

21

22

Best practice is to
separate movement of:

General population
Laboratory personnel
Chemicals and laboratory
materials.

Internal service
corridors between labs

Allow transport of
chemicals away from public
Provide access to utilities
and other support
equipment
Provide additional lab exits
with emergency doors to
main corridors

General
Lab

23

Staff
Office

Chemical
Free

Utility
Corridor

Good safety: two or more

exits from each
lab/room/building
Good security: control
who can enter a
lab/room/building
Emergency exit doors:
Lack handles
handles, or are locked
on outside
Have panic bar on inside
May set off alarm when
opened

24

Multiple, specialized
stockrooms rather than one
centrall storeroom

Teaching stockroom

High traffic
Only keep ~1 week supply
of chemicals needed for
student experiments

Chemicals dispensed across

counter
Access restricted to
stockroom personnel
Locked when unattended

Install tanks
outside building
and pipe into lab

Long-term, frequent
use of same gas
Highly hazardous gases
Restrict access
Out
Out-building
building or
outdoors, depending on
conditions

Central Stockroom
Wide variety of chemicals
and materials
Additional controls and
containment for regulated
regulated,
attractive, or dual-use
chemicals

Chemicals stored in
compatible groups
25

26

Tanks inside labs

Wide variety of gases

Low use rates
Strap to wall or
bench
Transport safely

Large volumes of
chemical
h i l waste
should be stored in
areas with fewer
people

Access restricted to
responsible personnel
Locked when unattended
Divided into chemically
compatible groups
Provide safety
equipment and alarms

27

28

Waste
collection
area in
W
ll i
i
teaching/research labs:

Convenient student use

Emptied/moved
frequently
Divided into chemically
compatible groups
Provide safety equipment

Uses standard size and layout of benches,

equipment and utility connections
Customize layout for specific applications
Allows for:
Cheaper lab design
Easier lab modifications
Easier lab renovations

29

30

Consider using both or having connected access:

Closed Laboratory

Open Laboratory

31

C
Closed laboratories

Open laboratories
Support team work
Facilitates communication
Shared:
Equipment
Bench space
Support staff
Adaptable and flexible
Easier to monitor
Cheaper to design, build and
operate
The trend since mid 90s

32

Specialized, dedicated work

More expensive
Less flexible
Easier to control access
Needed for specific work
NMR
Mass spec
High hazard materials
Dark rooms
Lasers

Energy Conservation Issues

Design leading to
increased
productivity
Energy conservation
and efficiency
Centralized heatgenerating
equipment
i
Manifolded hoods
and ventilation

Reduction/elimination
of harmful substances
and waste
Efficient use of
materials and resources
Recycling and reuse

Vented Enclosures
Ductless Hoods
Diversity
Manifolded Systems
Recirculation of Room Exhaust Air
Variable Air Volume Systems
Automatic Sash Closers
Air Change per Hour
Low Flow Hoods

33

Ventilation Considerations
- Heating and cooling needs
- Maintaining directional airflow

34

General Laboratory Hood

Considerations
Determine minimum exhaust
requirements.

- Type of hoods

Communicate hood
limitations to users.

- Single vs. manifolded hoods

Label restrictions e.g., no

perchloric acid.
Alarm systems
Consider future needs.

35

36

Ventilation Design:
Avoid Exhaust Recirculation
Avoid re-entrainment
Disperse emissions
straight upward and
downwind!

37

38

Try to locate hoods, utilities and

safety equipment in the same
relative position in all labs.
Locate sinks centrally
Space between benches should
allow people to pass each other
(1.5 m).
Details on these topics given in
later presentations:

Construction materials should

be appropriate for chemicals

Lab hoods
Safety showers / eyewashes
Chemical management

39

Benchtops
B
h
Cabinets & shelving
Flooring
Avoid metal drainpipes

Store chemicals and waste

securely not easily spilled or
knocked over.
Keep bulk chemicals in
stockroom - not lab.
Control access to labs,
especially during off-hours

40

Higher occupancy than

research labs

Need easy movement of

people around lab
Two safe exits
Benches in Islands
2m distance between
benches so students can
work back-to-back
Locate instruments, sinks,
supply areas away from
hoods to minimize traffic in
front of them

Floor space required per student

3.0 m2 absolute minimum
6.5 m2 allowing space for utilities,
storage, cleanup, etc.

41

Conclusion:
Together we can design, build,

43

Room (floor, ceiling, walls)

Furniture
Equipment and fixtures
Plumbing system
HVAC ductwork

42

and operate safe/secure

laboratories!

When a laboratory is modified or vacated,

ensure that:
Chemicals have been safely moved to another
lab, returned to the stockroom, or properly
disposed of.
Any contamination has been removed from
the:

Prudent Practices in the Laboratory: Handling and

Disposal of Chemicals, National Academy Press, 1995,
ISBN 0-309-05229-7
0 309 05229 7 also available online:
http://www.nap.edu/catalog.php?record_id=4911
Laboratory Design, Construction, and Renovation:
Participants, Process, and Product, National Academies
Press, 2000, ISBN 0-309-06633-6, Also available
online:
http://www.nap.edu/catalog.php?record_id=9799
Handbook of Chemical Health and Safety, Robert J.
Alaimo, Ed., Oxford University Press, 2001, ISBN 08412
3670 4
8412-3670-4
Guidelines for Laboratory Design: Health and Safety
Considerations, 3rd edition Louis J. DiBerardinis, et al.,
Wiley, 2001, ISBN 0-471-25447-9

44

Hazardous Exposure

Hazardous Exposure

SOURCE

SOURCE

SOURCE

RECEIVER

RECEIVER

RECEPTOR

Enclose the Source

47

Illustration courtesy, Tom Smith, ECT Technologies, Cary NC USA

48

Reminder:
Prioritization of Controls

Ventilation

Engineering controls
Administrative controls &

Operational work practices

P
Personall protective
t ti

equipment
Safe Worker
Illustration courtesy, Tom Smith, ECT Technologies, Cary NC USA

49

Uses of Ventilation
Keep gas / vapor concentration below OEL
Air
Ai movementt tto reduce
d
heat
h t stress
t
Keep toxic contaminants below OEL
Confined space entry

50

Limitations of Ventilation
May require large amounts of air (expensive)
Outdoor air may create problems
Need tempering
Heat, cool, dehumidify, humidify
May be contaminated

System design

Limit CO2 buildup

Control clean room or hospital

environments
OEL = Occupational Exposure Limit

51

Remove contaminate from breathing zone

Insufficient air velocity or volume

Contaminant cleanup or discharge

Users need training

52

Engineering Ventilation Controls

General dilution ventilation

For Control of:

Temperature
Harmless Substances
Nuisances
Odors

Local exhaust ventilation

53

54

Use Local Exhaust

Ventilation (LEV):

To enclose and contain

When contaminant is toxic

Employee works near the contamination

When complete containment/enclosure

is not feasible

55

Local Exhaust Ventilation

56

Definitions

LEV Principles

Enclose source
Capture contaminant near source
Keep contaminant out of breathing zone
Provide adequate make-up air
Discharge away from air intake

Hood includes any suction device,

regardless of shape
shape, that encloses
encloses, captures
or removes contaminants.
Dilution Ventilation moves room air
around by a fan that is sometimes exhausted
to the outside.
Local Ventilation (LEV) ventilation system
that captures and removes emitted
contaminants.

57

58

System Characteristics

System Components

Discharge

Q3 = Q1 + Q2

Hood
Duct Work

Q2

Air Cleaning
System

Branch

Optional Air Cleaning

Devices
Fan
Discharge

Fan
Capture Hood
Conservation of Mass

Q = vA

Q1

Where:
Q = volumetric flow rate (m3/s)
v = velocity (m/s)
A = Cross Sectional Area (m2)
Dip Tank
59

60

Volumetric Flow Rate

Q = vA
Q = volumetric flow rate of air ((m3/s))

Q = vA

v = velocity of air through an area (m/s)

A = cross
c oss sectional
sec o a area
a ea air
a flows
o s
through (m2)

61

System Losses

Q = Volumetric Flow Rate, m3/s

v = Average Velocity, m/s
A = Cross-sectional Area, m2
62

Press Room Ventilation System

Friction Loss
- Rougher surfaces lead to higher velocity
- FL LV2/d
- FL units of pipe length
Dynamic Loss
- Turbulence from elbows or cross-sectional area
changes or transition
- Turbulence at hood entry
Coefficient of Entry Ce measures efficiency of
hood entry
- DL increases with abruptness of elbow or transition
- DL units of equivalent pipe length or fraction of VP
Pressure losses from system devices
- Fans, air cleaners, etc.
63

64

Local Exhaust Hoods

Canopy Hood Machine Shop

P = Hood perimeter
D

SLOT HOOD

CANOPY HOOD

65

Portable Welding Hood

67

66

Traditional Laboratory
Chemical Hood

68

Design Goals for

Balance Enclosures

Flow at Exit and Entry

Capture of contaminant at
entry is only effective within
one (1) duct diameter

High level of containment

30 Duct Diameters

Duct

Stable balance readings

Ergonomic design, visibility,
comfort
Task specific flexibility
Energy efficient
- 0.6 m enclosure (~2) = 0.047 m3/s air (100
CFM)
- 1.8 m hood (~6) = 0.566 m3/s air (1200 CFM)
- 0.566 m3/s (1200 CFM) = $5K/yr.

Air

Air

Exhaust at exit is
effective to thirty
(30) duct diameters
Duct Diameter

69

70

Hood Capture Velocities

Hood Capture Velocities

Air

Equal Velocity Zones

Air

% Hood Capture Velocity

~100%

Air

Air

% Hood Capture Velocity

~100%

Hood
Air

~60%
~30%

Air

Equal Velocity Zones

Air

Duct

~30%

~15%

Hood

Air

~60%
Duct

~15%

~7.5%
Air

Air

~7.5%
Air
Air

Hood Diameter

71

Air

Flanged Hood

Air

Hood Diameter

72

Recommended Capture Velocities

CONDITION

EXAMPLES

CAPTURE VELOCITY
m/s
(fpm)

No velocity,
Quiet air

Evaporation from tanks,

degreasers

0.25 0.5
(50 100)

Low velocity, moderately

still air

Spray booths, container

filling, welding, plating

0.5 1.0
(100 200)

Active generation into

rapid air motion

Spray painting (shallow

booths), crushers

1.0 2.5
(200 500)

High initial velocity into

very rapid air motion

Grinding, abrasive
blasting, tumbling

2.5 10.1
(500 2000)

73

Hood Exhaust

Fan Speed and Air Flow

Fan rated to deliver 5.0 m3/s of air running at 400 RPM.
If fan speed increases by 25% to 500 RPM, what is the
new air flow?

Q RPM
RPM2
Q2 = Q1 RPM
1
Q2 = 5

500
400

= 6.25 m3/s
74

Avoid Capping Exhaust Stacks

Height
Discharge velocity
Configuration

75

76

Engineering Controls:
Avoid Exhaust Recirculation

Designs deal with rain without capping

Hood
Exhaust

Air Intake

78

77

Engineering Controls:
Avoid Exhaust Recirculation

78

Potential Issues
Insufficient air volume
Too much air flow
Wrong location

High
Hazard
Hood
Exhaust

Wrong configuration
Bad hood design
Duct velocity too low
Insufficient make up air

Air Intake

Clogged system
Noise
79

79

80

Any Questions?

Tom Smith, Exposure Control Technologies,

C
Cary
NC USA http://www.labhoodpro.com/
h
//
l bh d
/
Nelson Couch, PhD, CIH, CSP, Triangle Health
& Safety Inc., Durham, NC USA
ncouch@earthlink.net
Ray R
Ra
Ryan,
an Flo
Flow Sciences International,
International Leland
NC, USA http://www.flowsciences.com

81

82

Improper Hood Use

84

Control Concept
Also called a fume hood or fume cupboard
g
p
Designed
to limit exposure
to hazardous or
unpleasant aerosols
First used by alchemists 500 years ago

SOURCE
RECEIVER

85

86

LEV Implementation

Identify/Characterize Contaminant
Characterize Air Movement
Identify Alternative Controls
Choose Most Effective Control
Implement Control
Evaluate Control
Maintain Control
87

LEV Capture Ability

Hood configuration (type of hood)

Extent of enclosure

(e.g., glove boxes completely enclose)

Air movement in hood

(smooth, laminar, non-turbulent)
88

Duct Design

Provide adequate capture velocity

Duct Design, contd.

- ii.e.,
e equalize supply and return air
- match airflows among manifolded hoods

Usually
U
ll 0.4
0 4 - 0.6
0 6 m/s
/ (80
(80-120
120 ffpm))

M i t i duct
Maintain
d t transport
t
t velocity
l it

Keep system balanced,

Minimize power consumption

- i.e., conserve energy
y
- save money

For chemical laboratories 1.2 m3/s

(~2500 cfm)
http://www.clf.rl.ac.uk/facilities/AstraWeb/images/Photo7/Air_duct_TA3.JPG

89

LEV Hood Design Requirements

Capture emissions close to source.

Move contamination away from
breathing zone.
Consider existing air movement when
locating hood.
Minimize air movement in source area.
Should not interfere with work.
91

90

Laboratory Hoods
Laboratory hoods and ventilation are the basis of engineering controls.
B t th
But
they mustt be
b properly:
l selected,
l t d located,
l
t d used,
d and
d maintained.
i t i d

92

As near to contamination source as possible

So contamination moves away from operator
Minimize cross-drafts
Dont place near windows and doors
Dont place near air conditioning/heater
diffuser
D
iinterfere
f
i h other
h workers
k
Doesnt
with
Locate out of traffic flow
Place near rear of laboratory

93

Enclose as much of the operation as possible

Place utility
y controls (g
(gas,, electric)) outside or as near
hood front as possible
Hood lights should be vapor tight
Mount hood motor outside building and away from
building air intakes
Dont use hoods for uses not intended (e.g., perchloric
acid digestion, radioisotopes)
Ensure duct material compatible with exhausts
Dont use without indication it is working properly

94

Dont put your head in the hood.

Use proper PPE (gloves
(gloves, eyewear
eyewear, etc)
Place large equipment above surface
on 5 cm blocks to allow uniform air
flow
Lower sash height to 30 - 50 cm
during operation
Keep sash fully closed when not in
use
Use liner or tray inside hood to
contain spills
http://www.news.harvard.edu/gazett
e/daily/0403/photos/03meltonstem_1.jpg

95

96

Work in the center of hood and 15 cm in from

hood sash.
sash
Dont store chemicals or equipment in hood.
Dont block baffles (slots).
Maintain hood regularly (check fan belt,
lubricate motor).
Regularly
g
y evaluate hood (flow
(
rate,, mark
operating sash height).
Reports problems, concerns, malfunctions
immediately.

Perchloric acid (with water wash down)

Radiological (with special filters)
Floor level (improperly called walk-in)
Distillation/California hoods (0.5m or ~1.5 ft
above floor)
Canopy hoods (not suitable for most lab
operations)
Slot hoods
Ductless
l
ffume hoods
h d
Vented enclosures or special purpose hoods
Glove Boxes (complete enclosure)
Biological Safety Cabinets (BSC)

97

ADA Hood

98

Glove Box

Floor Hood

Canopy Hood

Chemical weighing station

99

Bulk powder transfer station

100

Biological Safety Cabinets (BSC)

Ductless Hoods
Should only be used in
laboratories with:
Small quantities of known non-

volatile substances.
Only with HEPA filters
Never with volatile substances
Unless breakthrough time for the
specific chemical being used is
known, carbon filters are
unreliable.

101

102

Hood Problems and Pitfalls

Face velocity
- Recommended
R
d d 0.4
0 4 - 0.5
0 5 m/s
/ (80 - 100 ffpm))
Air changes/hour
- Recommended 6 10 / hour

Hood Evaluation

Face Velocity, a necessary but

not sufficient condition.

Anemometer/velometer

Smoke Tubes, Candles,

Incense

Neither of these measurements can

guarantee hood capture or containment.
103

104

Ensuring laboratory hood safety

depends on many factors including:
Hood design
Hood use
g
Lab design
System operation

105
105

106

Tom Smith ECT,

ECT Inc.,
Inc Cary NC USA
University of North Carolina, Chapel
Hill NC USA
Texas A & M University
Flow Sciences Inc, Leland NC USA
Knutson Ventilation
Ventilation, Edina MN USA
AirClean Inc, Raleigh NC USA

107

108

Chemical Management is a Best

Practice for Safety and Security
Reduces hazardous waste
Reduces
R d
cost

Receipt

Storage

Disposal

Use

Waste
New
Chemical

New purchases
Waste disposal
More efficient

Improves security
Insider threat
Outsider threat

Facilitates
F ilit t environmental
i
t l compliance
li
Improves quality of research
Improves quality of lab instruction

111

112

Chemical Management Elements

Source reduction
Procedure for chemical ordering and
disposal
Inventory and tracking
Storage in stockrooms
Access control
Recycling of chemicals, containers
and packages

What chemicals are needed?

How much is needed?
How will the chemicals be handled?
What are the reaction products?
How will the chemical be stored?
How will disposal take place?

113

Less is Better !
Order only what you need

Reduce size of experiment

It cost less to store

It cost less to dispose

114

Citrus based solvents for xylene in

histology lab
Peracetic acid for formaldehyde for
cleaning kidney dialysis machines

CH3

Non mercury thermometers

Enzyme and peroxide based cleaners
for chromerge (NoChromix)
When purchasing automated
equipment think of chemical waste

Less is Better: Guide to minimizing waste in laboratories, Task Force on Laboratory Environment,
Health and Safety, American Chemical Society, 2002.
http://portal.acs.org/portal/acs/corg/content?_nfpb=true&_pageLabel=PP_SUPERARTICLE&node_id
=2230&use_sec=false&sec_url_var=region1&__uuid=ef91c89e-8b83-43e6-bcd0-ff5b9ca0ca33

115

CH3

116

O
H3C
O

OH

Database helps safely track and

report chemical storage and use
Database or Spreadsheets are tools to track
the
th chemical
h i l inventory
i
t

Barcoding can be used

Chemicals can be found easily
Chemical ages can be tracked
Chemical standards maintain traceability
Disposal can be documented

Physical reconciliation
Assures accuracy of database
Provides visual inspection of chemical condition

Searches and Reports:

Find an (M)SDS
Chemical Inventory Search Menu
Chemical Regulatory Reports Search Menu
Find Chemical Storage Locations
Transfers, Removal, Verification and Inventory Entry:
Transfer or Remove a Bar-coded Chemical from the Inventory
Verify Chemical Inventory Menu
Add Chemical Inventory
Ch i l E
Chemical
Exchange
h
M
Menu
Procedures, Forms and Links:
See Inventory procedures, forms and other documents
See Other Chemical Related Links

117

118

Query for toluene: barcode, location,

department, quantity and order date
Chemical or tradename search
CAS number search
Ingredient search
Location/organization search
Location owner search
Requester search
Barcode search

UNIT

Purchase
Date

1725 1

10/24/2006

1111 100

mL

11/20/2006

NM/518/1302

1131 1

8/8/2006

AQ00602186

NM/518/1302

1131 100

mL

11/20/2006

AQ00602187

NM/518/1302

1131 100

mL

11/20/2006

AQ00582307

NM/518/1302

1131 4

8/8/2006

BARCODE

LOCATION

AQ00600682

NM/518/1111

AQ00602185

NM/518/1123

AQ00582298

DEPT

QUANTITY

(M)SDS and Certificates of Analysis may also be included

119

120

Excess chemicals made available

to others & can be searched
ACIDS
Acetic acid (glacial)
Hydrochloric acid
S lf i acid
Sulfuric
id

SOLVENTS
Dichloromethane (methylene chloride),
Acetone Chloroform, Ethyl acetate, Glycerol,
Hexanes Isopropyl alcohol, Methanol,
Petroleum ether Toluene, Xylenes

OXIDIZERS
Bromine, Potassium chlorate
Bromine
chlorate, Potassium
dichromate, Silver nitrate

CHEMICAL
NAME

MSDS

QTY

STATE

PURCHASE
DATE

OPEN?

DEVCON 5 MINUTE
EPOXY KIT

NL203800

73.9
mL

Liquid

07/25/2001

Not
Open

5 MINUTE EPOXY KIT

NL203800

73.9
mL

Liquid

08/06/2003

Not
Open

TOLUENE

OHS23590

500.0
mL

Liquid

03/25/1999

Not
Open

TOLUENE

OHS23590

500.0
mL

Liquid

03/25/1999

Not
Open

POISONS
Indicators, Iodine (solid or solution) Metals
(powders, dust, shot)
Sodium, calcium, silver, and potassium salts
121

122

Less is Better !
Its Safer!

It may be cheaper to order diethyl

in large containers

123

Some chemicals degrade

over time
rotate stock
label & date

ether

But, if its opened for a long time

peroxides can form!

How old are your chemicals?

Chemical assays have

expiration dates

124

It is important not to let peroxide forming chemicals evaporate

to dryness or accumulate under screw caps.

Examples:

Peroxide
Peroxide-forming
forming - ethers
Perchlorate-forming perchloric acid
Water/moisture sensitive Na, K, Li, LAlH,
flammable metals

Control measures:

-R-O-O-RR O O R

Peroxide Forming
Chemicals

Even with inhibitors they can become

dangerous over time
- discard or test if unsure
- label & date when received,
when opened, and
provide expiration date

Inventory controll
SOPs, inspections

Peroxide test kits and strips should

be available
125

Peroxides can explode

when
h exposed
d to
t thermal
th
l
or mechanical shock
Examples: ethers, dioxane,
tetrahydrofuran

References:
Th
ll t websites
b it on peroxide
id
There
are excellent
forming chemicals and their hazards,
use, storage, and disposal. For example,
see:
http://www.med.cornell.edu/ehs/updates/p
eroxide_formers.htm
127

126

Protect chemicals during normal

operations
Protect chemicals during unexpected
events

Floods
Tidal waves
Earthquakes
T
h
Typhoons
Hurricanes

128

Separate incompatible chemicals

Separate flammables/explosives from
ignition sources
Use flammable storage cabinets for large
quantities of flammable solvents

S
Separate
t alkali
lk li metals
t l ffrom water
t

Separate acids and bases

129

Store nitric acid separately

Store large containers on bottom shelves

Lock up drugs, chemical surety agents, highly

toxic chemicals
Do not store food in refrigerators with chemicals

130

Secure (chain/clamp) and separate gas

cylinders
Screw down cylinder caps
Store in well-ventilated area
Separate & label empty cylinders
Store empty cylinders separately
Separate flammable from
reactive/oxidizing gases

131

132

Damage from Gas Cylinder Fire

An Accident Waiting to Happen

133

134

Limit access

Label Authorized
Authorized Personnel
Only
Lock area/room/cabinets when
not in use

Be sure area is cool and well

ventilated
Secure storage shelves to
wall or floor
Shelves should have a
front lip
In earthquake territory, have a
rod several inches above shelf

135

136

Separate
incompatible
chemicals

on top of cabinets
on floor
in hoods
with food or drinks
in refrigerators used for
food
where
h
there
h
are wide
d
variations in temperature,
humidity or sunlight

Organize chemicals
by compatible
groups
Alphabetize
chemicals only
y
within compatible
groups

137

Do Not Store Chemicals

138

Dont use chemical containers for

food
Dont use food containers for
chemicals
Be sure all containers are properly
closed
Wipe-off outside of container
b f
t
i
tto storage
t
before
returning
area
Transport/carry all containers safely

Never use hallways

for storage
Safety Hazard!!
Blocks exit path in
emergencies!!!

Preferably use outer protective container

139

140

Acids, anhydrides
Alcohols,
Al h l amides,
id
amines

Epoxies, isocyanates

Azides, peroxides

Aldehydes, esters,
hydrocarbons

Ethers, ketones,
halogenated
hydrocarbons

Nitriles, sulfides,
sulfoxides
Cresols, phenols

Metals, hydrides

Halides, halogens,
phosphates, sulfates,
sulfides

Amides, azides, nitrates,

nitrites

Carbonates, hydroxides,
oxides
oxides, silicates

Chlorates, chlorites,
perchlorates,
perchlorates peroxides
Arsenates, cyanides,
cyanates
Borates, chromates,
manganates
Acids
Arsenics, phosphorus,
h
h
sulfur

From: School Chemistry Laboratory Safety Guide, US NIOSH Publication 2007-107

From: School Chemistry Laboratory Safety
Guide, US NIOSH Publication 2007-107
141

142

References
Proper training of chemical handling personnel

Less is Better, American Chemical Society,

Washington DC, 2003, available online:

O
Only
l trained
t i d and
d approved
d personnell
have access to stock room and keys
administrative privileges to inventory and
database

http://portal.acs.org/portal/acs/corg/content?_nfpb=true&_pageLabel=PP_
SUPERARTICLE&node_id=2230&use_sec=false&sec_url_var=region1&__u
uid=ef91c89e-8b83-43e6-bcd0-ff5b9ca0ca33

Locked doors and cabinets for controlled

substances
Radioactive materials
Drugs and consumable alcohol
Explosives (special handling facility)
Dual use chemicals
Hazardous waste - high toxicity chemicals

143

School Chemistry Laboratory Safety Guide, US NIOSH

Publication 2007-107, Cincinnati, OH, 2006,
available on-line:
http://www.cpsc.gov/CPSCPUB/PUBS/NIOSH2007107.pdf
Prudent Practices in the Laboratory: Handling and
Disposal of Chemicals, National Academy Press, 1995,
available online:
http://www.nap.edu/catalog.php?record_id=4911

144

Find one or two partners

Use the hazard and compatibility information to optimize
g
chemical storage
Rules:
4 bottles per shelf maximum
Note that only one cabinet has a vent
Only one cabinet can be secured (padlock)

You may have to make some compromises or hard choices

When finished, discuss the following and write comments

i your workbook:
in
kb k
Was there one perfect way to store the chemicals?
Did you have to make compromises? What were they?
In making compromises, what were your main priorities?

146

Conclusions
Can make chemical storage safer and more
secure

Safe and secure chemical storage requires

Space
Time
Training
Equipment

Difficulties may be mitigated by operational

controls
Substitution
Scale Down

147

Conditions, besides chemical, biological or radiological

conditions or circumstances, that can cause injury,
ill
illness
and
d death:
d th

Fire/Asbestos
Centrifuges
Cryogenics
Ergonomic
Offi
Office
Physical stress/strain
Construction

Noise
Heat/cold
Sunlight
Non-ionizing
radiation
Mechanical
Electrical
Housekeeping
Spills/trips

Gloves

Lab hoods

Lab
bb
benches
h

149

150

151

152

Uses
Hazards
Control of hazards

Only authorized users can use equipment

Users must be trained
A
Assign
i
responsibility
ibilit tto llab
b ttech
h
Include in periodic lab inspections

153

154

Centrifuge Safety

Dont overload

Rotor
Drive Shaft
Motor
155 varying degrees of protection
Cabinet provides

Keep rotor and

centrifuge clean

Check rotor for cracks

Set it upright
156

 Store cryogenics separately from other

chemicals
Store cryogenics (liquid nitrogen) & dry ice
in well ventilated areas
Use proper PPE (including eye protection)
when handling & moving cryogenics
Do not use cryogenics in closed areas

157

158

159

160

What are they?

Uses
U
Hazards
Control
training
inspection

Cyrogen Storage

What is dry ice?

Uses

Hazards

Control measures

Exploding liquid nitrogen

cylinder ruins lab.
161

Open-toed shoes
should not be
allowed in
laboratories.

162

Working Alone

Avoid!
Murphys
M
h Law
L
will
ill get you!!
(Anything that can go wrong, will go wrong!)
Use the Buddy System

Unattended Operations/Reactions

Employees should
not wear gloves
gloves, lab
coats or other PPE
outside the lab.

Caution! Prime sources of fires, spills and explosions

Check periodically!
Fail-safe
Fail safe provisions
Leave the lights on to indicate the presence of an
unattended activity

Post appropriate signs and emergency phone #s

Notify those potentially impacted by malfunction
163

164

Can be a significant problem

Hazards

Control

listing,
Frayed cords,
cords no UL
UL-listing
overloaded circuits
Static electricity

Check to see that all outlets are grounded

and that the polarity is correct.
correct

Fires, electrical shock, power

outages
Inspect, act immediately, education

165

166

Storage should be at least

panels,,
1 m from electrical p
mechanical rooms, air ducts,
heaters, light fixtures.
Dont store combustibles in
mechanical rooms or electrical
closets
closets.
In emergencies it may be necessary
to access these panels quickly.
167

168

U
Uses

Hazards

Unshielded rheostats

Precautions

Control measures

No dry ice in
freezers!
Improper storage
PPE

169

Potential Hazards

170

Ergonomics
E
i
High temperature
Broken glassware
Improper use

Control

Inspection
Training

Beware of contaminated
Glassware, especially if broken!
171

172

Ultra low temperatures

-20C, -80C
Upright vs. walk-in
Emergency power
Labels

Experiments carried out at pressures above 1

atmosphere (~1bar
( 1bar, ~100
100 kPa
kPa, 760 Torr)
Torr).
Use of supercritical fluids (CO2)

Hazards

Explosions, equipment failure

Control Measures

SOPs, training, engineering controls,

inspection
Dry runs
173

174

Vacuum Work
Uses
- Aspiration
p

Hazards
- Injury due to glass breakage
- Toxicity of chemical
contained in vacuum
- Fire following flask breakage
- Contaminated pump oil

Control Measures

Mechanical hazards
lik open drive
like
d i belts
b lt
with pinch points
must have shields
and guards.
Oil pumps need drip
pans to contain oil.

- SOPs, inspection, education

175

176

Elevated noise levels can

be a problem.
problem
Potential Hazards
Examples: bone-cutting
saws, mechanical water
aspirators, sonicators,
pumps.

Uses NMR, MRI

Hazards

Control Measures

Control Measures

Inspections, PPE,
warning labels, training.

Magnetic field
High voltage
Cryogenic liquids
- e.g., nitrogen, helium
Other hazardous materials in lab
Control access to area
Training
Warning signs

177

178

IONIZING RADIATION

Particulate or electromagnetic
Charged () or uncharged (, X, n)
Causes ionization of atoms or molecules

NON-IONIZING RADIATION
Electromagnetic (UV, IR, MW, RF)
Can not ionize atoms or molecules

179

ray

Types

Hazards

Control of hazard

SEM, TEM
X-rays

Periodic maintenance
C
Conduct
d
radiation
di i
survey
Include in personnel radiation safety
program

180

Shielding Materials

Protect yourself by:

TIME Limit time near source

Paper
Alpha

Plastic
Lead or concrete

DISTANCE Stay away

d1 2
)
I 2 = I 1(
d2

Gamma & X-Rays

0n

Neutron

SHIELDING Absorb energy

Beta

Water

CONTAMINATION CONTROL
181

UV, Visible, IR, Lasers

Hazards

182

Skin erythema
Eye injuries

Control Measures

Training, PPE, warning signs and

labels, interlocks
183

184

Uses

Hazards

Cataracts, sterility
Arcing use of metal in microwave
Superheating of liquids
Explosion of capped vials

Control Measures

Free-moving parts
Struck by injuries

RF ovens and furnaces

Noise
Lasers
Aerosol
Generation

SOPs, education, inspection

185

186

Housekeeping
Hazards

Needle sticks
Cuts
Contamination

Control Measures

187

SOPs
Training
Modify work practices
Engineering Controls
188

Most common injuries

Causes

Chemical spills and leaks

Improper work practices

Control Measures

SOPs, proper equipment,

effective communication,
engineering controls

189

190

Whats Wrong With This Picture?

191

Think!
Develop SOPs, safety manual, policies

reviewed and approved by management

Research protocol review

Install engineering controls
Provide PPE
Provide training
Conduct inspections
inspections, routine &
unannounced with lab supervisor
Document and follow-up
Take action
192

193

195

196

Routes of Exposure
Breathing Zone
Inhalation*
a at o

Eyes

Absorption
Ingestion
Injection

*Most important route

of entry
197

Respiratory System

198

The Lungs
Defense Mechanisms
Cilia
Macrophages
Mucus
M
traps
t
dirt
di t and
d
Special
S
i l mobile
bil cells
ll
foreign particles.
that eat up toxins in
the airways and
Little hairs (cilia) beat
lungs .
back and forth in the
airways to move mucus Requirements:
and dirt up where it can Regular supply of
be expelled by
air with O2
coughing.
Open, clear airways

199

200

Gas Exchange Region

About 70 m2 the serving area
of a tennis court
court.
Consists of alveolar duct and
alveoli with surfactant to keep
open.
Close contact with capillaries to
exchange O2 for CO2 and exhale
other gases/vapors.
201

Aerosol Penetration into the

Lung
Size (micrometers)
> 20
10 20
5.0 10
0.1 5.0

% Deposition
100% in upper airways
80% upper, 0+ alveoli
50% upper, 50% alveoli
0+ upper, 90+ alveoli

Common Respiratory Issues

Chronic
Bronchitis

Emphysema

Normal elasticity destroyed

Forcefully blow the air out,
pressure on the airways
Excessive coughing

Cells inflamed
Airway narrow and clogged

202

Certain Effects of Chemicals

on the Lungs
Irritations acid mists ((HCl))
Edema phosgene (COCl2)
Emphysema smoke (esp. tobacco)
i silicon
ili
di
id (SiO2)
Fib
Fibrosis
dioxide
Cancer asbestos (mesothelioma)

203

204

Asphyxiant/Suffocating
Asphyxiant
/Suffocating Agent

Skin Thickness

Physical dilute oxygen in air to below

10%, non-irritant gases methane, N2,
CO2, Freon
Chemical displace oxygen on
hemoglobin cyanide, carbon monoxide

205

The Eyes

206

Routes of Exposure
Ingestion (mouth)
Rare,
Rare but contamination can = intake
mucociliary action of respiratory tract

Stomach GI tract bloodstream

Absorbed - systemic injury
Liver, kidney; Detoxification process
Inflammation
cirrhosis - fibrotic liver disease
malignant tumors

Factors: physical state, duration

207

208

Routes of Exposure
Injection
Directly into bloodstream
sharps, needles, broken glassware
skin puncture or injuries

Bypasses protective mechanisms

Usually rare in workplace
primarily associated with
bloodborne pathogens (biomedical
facilitates)
especially hazardous in health care
industry
209

210

Terminology

The World of Chemicals

Universe of Chemicals > 5 Million
Industrial Inventories ~ 55,000
Regulated Occupationally ~ 600

Toxica
T
i
nts
Toxins
Poisons

211

Substances that produce adverse biological effects of

any
y nature
May be chemical or physical in nature
Effects may be of various types (acute, chronic, etc.)
Specific proteins produced by living organisms
(Mushroom toxin or tetanus toxin)
Most exhibit immediate effects

Toxicants that cause immediate death or illness

when experienced in very small amounts

212

Toxicology
Poisons - the adverse effects of substances on living

All chemicals have the capacity to be toxic

systems.
systems

All substances are poisons; There is none which is

not a poison. The right dose differentiates a poison
from a remedy

Paracelsus (1493-1541)
(
)

Chemical Toxicology The potential adverse effects and

control of chemicals in the workplace.

All chemicals act in the body according to the

principles of chemistry, physics and biology
Natural chemicals are not inherently harmless
Synthetic chemicals are not inherently
hazardous

213

214

LD50 (mg/kg)

Agent

Chemical

Beneficial Dose

Toxic Dose

Aspirin

300-1000 mg

1000-30,000mg

Vitamin A

500 units/d

50,000 units/d

Oxygen

20% in air

50-100% in air

215

Ethyl Alcohol
Sodium Chloride
Naphthalene
Ferrous Sulfate
Aspirin
Formaldehyde
Ammonia
Dextromethorphan Hydrobromide
Caffeine
Phenobarbital
hl
h
l
Chlorpheniramine
Maleate
DDT
Strychnine Sulfate
Nicotine
Dioxin
Botulinus Toxin
216

7060
3000
1760
1500
1000
800
350
350
192
150
118
100
2
1
0.0001
0.00001

There are no harmless

substances.
Only harmless ways of using
substances.

Chemical Toxicology

The study of the effect the chemical has

on the body.

Pharmacology

The study of the effect the body has on

the chemical
chemical.

217

Concentration of toxin
Duration and frequency of exposure
Route of exposure
Environmental factors temperature,
humidity, atmospheric pressure
(diffic lt and
Chemical combinations (difficult
expensive to test)

219

218

Age
g
Gender and hormonal status
Genetic makeup
State of healthpresence of
disease or stress
Nutrition
Lifestyle

220

Toxicity Testing Assumptions

Effects seen in
Eff
i animals
i l apply
l to
humans
High doses in animals are needed
to predict possible hazard to humans

Duration of Exposure

Acute

1 to 5 days

Subchronic

Chronic
h

14 to 90 days
6 months
h to lifetime
lf

221

222

DoseDose
-Response Relationship
This relationship is unique for each chemical

With increasing dose,

dose there is an increase
in the number affected and/or an increase
in the intensity of the effect: e.g., mortality;
cancer; respiratory depression; liver
pathology
Dose = (Concentration) x (Time)

100
E
f
f
e
c
t

50

5
LD5 LD50

Threshold
(NOEL: No Observable Effects Level)
223

224

Dose (mg/kg)

Dose and Dosage

Fundamental concept in toxicology

The relationship between the
degree of exposure (dose) and the
magnitude of the effect (response)
Provides basis for evaluating a
chemicals relative toxicity

Dose is quantity (mg, mL)

Dosage includes frequency (10 mg, 4
times/day)

Exposure dose quantity administered

Absorbed dose Actual quantity absorbed

225

TDlo Toxic dose low - lowest dose for effect

LD10 Lethal dose 10% - dose that causes death in
10% of the test population
LD50 Lethal dose 50% - dose that causes death in
50% of the test population
TClo Toxic concentration low - used to express toxic
concentration via inhalation
LC10 Lethal concentration 10% - dose that causes death in
10% of the test population via inhalation
LC50 Lethal concentration 50% - concentration that
causes death in 50% of the test population via
inhalation

227

226

Mass per weight or surface area of

subject:

Quantity per unit mass (mg/kg)

Q
Quantity
i per unit
i area off skin
ki surface
f
(mg/m2)

228

Additive Effect
Combined effect of 2 chemicals equals sum
of each agent alone(2 + 3 = 5)
Synergistic Effect
Combined effect of 2 chemicals is greater
than sum of each agent alone(2 + 3 = 20)

Potentiation
One substance does not have toxic effect
on certain organ or system, but when
added to another chemical, it makes the
latter more toxic(0 + 2 = 10)
Antagonism
2 chemicals
chemicals, when given together
together,
interfere with each others actions or one
interferes with the action of the other
chemical(4 + 6 = 8)

229

230

Target Organs for Chemicals

Local

Effects occurring
g at site of first contact
between biologic system and toxicant
Ingestion of caustic substances
Inhalation of irritant materials

Systemic

Require absorption and distribution of

toxicant to a site distant from entry point
where effects are produced; most
substances produce systemic effects
CCl4 effects on the liver
231

Toxins

Target organ

Si
Signs
&
Symptoms

HEPATOTOXIN

LIVER

JAUNDICE

NEPHROTOXINS

KIDNEY

NEUROTOXINS
HEMATOPOIETIC
SYSTEM

CNS

EDEMA
NARCOSIS
BEHAVIOR

HEMOGLOBIN

CYANOSIS

CO, CS2

COUGH,CHEST
TIGHTNESS

SILICA, ASBESTOS

LUNG AGENTS
REPRODUCTION
TOXIN

PULMONARY TISSUE

Examples
CCl4
HALOGENATED
HYDROCARBONS
MERCURY

REPRODUCTIVE
SYSTEM

BIRTH DEFECTS

LEAD

CUTANEOUS AGENTS

SKIN

RASHES; IRRITAION

EYE HAZARDS

EYES

CONJUCTIVITIS

KETONE
ORGANIC
SOLVENTS

232

Skin Diseases

Liver Diseases

TDI toluene 2,4-diisocyanate

Fatty liver carbon tetrachloride

Sensitization chemical allergy

Cirrhosis ethanol

Oil/coal tar acne chloroacne

PCBs-polychlorinatedbiphenyls

Liver cancer vinyl chloride and

chlorinated solvents/pesticides

Contact dermatitis fat soluble solvents

Leukoderma (depigmentation) H202

Allopecia (loss of hair) - thallium

233

Reproductive and Developmental Disorders

Concern for spermatogenesis, hormonal
status, maternal toxicity, and embryo
or fetal toxicity.

234

Spermatogenesis

235

Rarely destroys the testes.

Usually blocks sperm development.
EGME (ethylene glycol monoethyl ether)
Completely reversible after exposure ends.

236

Developmental Effects:

y
Maternal Toxicity:

Lethality resorptions/stillbirths

Toxicity body weight/behavioral effects

Teratogenicity malformations (thalidomide)

Delayed development/structural
anomalies/variations

The ovary is more protected than the testes.

So, it is not toxicity, but changes in hormonal
regulation that is upset
Endocrine modulation,, DDT,, and raptor
p
eggs,
gg ,
ovulation, gestation

237

Nervous System:

238

Circulatory System:

CNS depression many organic solvents

Cholinesterase inhibition
organophosphorus & carbamate pesticides
Nerve conduction velocity myelin sheath,
peripheral nerve destruction nhexane
239

Hemoglobin CN and CO

Red cells lysis or lead poisoning

Leukemia benzene

Arterial blockage cholesterol, HDL/LDL

240

Halogenated Hydrocarbons
(low flammability, excellent solvents)

Acute CNS depression,

depression defatting skin,
skin myocardium

Chronic liver, kidney

Chlorinated solvents (CNS/skin/cancer)
CCl4-carcinogenic, liver, kidney

B
Brominated
i
d ffumigant,
i
solvents
l
(CNS/
(CNS/skin)
ki )

Fluorinated refrigerants (ozone layer/myocardium)

241

242

Structure Affects Activity

Aromatic Hydrocarbons

Useful, but dangerous i.e.,

Useful
i e guilty by association
association,
e.g., C4F8

Branched chain isomer lethal @ 0.5ppm

Linear isomer lethal @ 6,100ppm in 4 hr

Cyclic isomer essentially non-toxic

243

Benzene C
CNS
S depression,
p
, leukemia
Toluene CNS depression (glue sniffers)
Styrene dermatitis, CNS depression
Poly-aromatic hydrocarbons doxin, PCBs, biphenyls
liver/thyroid/skin
Nitrobenzene CNS, jaundice (liver effect),
methemoglobin - blue lips & fingernails
Ph
ki effects
ff t
Phenoll CNS
CNS, li
liver, kid
kidney, skin
(absorbed readily through skin)

244

Aliphatic Alcohols

Glycol Ethers

Methanol alcohol dehydrogenasebl d

blindness-treat
with
h ethanol
h
l

Ethylene glycol monomethyl ether (EGME) CH3OCH2CH2OH

1. Disrupts sperm development
2. Developmental toxin day 7,8-neural tube;
day 10-11-digit/paw effects, brain, liver, and kidney

Ethanol CNS depression, fetal alcohol

syndrome, liver cirrhosis

Ethylene glycol monoethyl ether (EGEE) CH3CH2OCH2CH2OH

1. Testicular degeneration
2. Reproductive/developmental toxins, but less severe

Isopropanol CNS depression, gastritis

Propylene glycol monomethyl ether (PGME)

Not a reproductive/developmental toxin

245

246

Ketones

Acetone (dimethyl ketone) CNS, skin

effects
Methyl ethyl ketone CNS, skin,
reproductive and developmental effects
Methyl
y butyl
y ketone CNS and p
peripheral
p
nervous system effects

Pesticides

247

Organophosphates cholinesterase inhibitor;

parathion, dursban, dichlorvos,
Organochlorine CNS; DDT, aldrin, kepone,
mirex
Carbamates reversible cholinesterase inhibitor;
sevin
Chlorophenoxy liver, kidney, CNS; 2,4-D,
agent orange, 2,4,5-T
Pyrethrins CNS effects; resmethrin
248

Lab Assessment Exercise

Part 2: Physical & Other Hazards

250