WELCOME TO BASIC HAZARD CATEGORIZATION Hazard Categorization Case Studies Why you should know this...
Transcript of WELCOME TO BASIC HAZARD CATEGORIZATION Hazard Categorization Case Studies Why you should know this...
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WELCOME TO BASIC HAZARD
CATEGORIZATION
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U.S. EPA Region 7
Emergency Response & Removal Program
On-Scene Coordinator:
Randy Schademann 913-551-7331
Doug Ferguson 913-551-7221
Introductions
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Basic Hazard Categorization Basic Hazard Categorization
Case StudiesCase StudiesWhy you should know this stuff…..
You da man!
You da only man!
Contractors, you can’t live without ‘em!
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2pm on a Friday afternoon2pm on a Friday afternoon
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Quick categorizationQuick categorization
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EPA may be the last or best optionEPA may be the last or best option
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Utilized the HazMat ID
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Traditional Drum SitesTraditional Drum Sites
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Monitoring contractor activitiesMonitoring contractor activities
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Maintain project controlMaintain project control
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Identify containers with like contentsSegregate based on hazardSample based on screening results
Hazard Categorization UsesHazard Categorization Uses
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Field Screening
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Mvi_0784.avi
DOT Hazard Classes Explained
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OBJECTIVES
• Become familiar with the major chemical families
• Understand why field screening is used• Become familiar with the field screening
tests• Use field screening results to determine
general hazards or identity of a material
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HAZARDOUS MATERIALS INCIDENT’S CLUES:
Occupancy, Location, Container Size & Shape, Placards, Labels &
Markings, and Senses(careful)
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Application Notes
• HazcatTM
Need to ID chemicalPure material (not real
good for wastes)Must know tests very
wellOthers?
• Field Screening
General “physical”hazards
Works well for wastesFurther TestingOthers?
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Identifying Unknowns
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Chemicals of Concern by Incidents:
• Combustible liquids 20,492
• Adhesive, Resin, Tar: 13,335
• Waste Water : 11, 315• Paint & Related: 10,660• Sulfuric Acid: 7,505• Anh. Ammonia: 7, 350• Antifreeze: 6,436
• PCB: 6,221• Hydrochloric Acid: 5,952• Sodium Hydroxide: 5,233• Chlorine: 3,800• Sulfur Dioxide: 3,652• Gas (NOS): 3,566• Resin Solution: 3, 056• Manufactured Gas: 3,428• Petroleum Dist: 2,957
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The Periodic Tablemetals
non-metalsnoble gases
1 2
3 4 5 6 7 8 9 10
11
1
H He
B C N O F Ne13
Al14
Si15
P16
S17
Cl18
Ar
H
Li Be
Na Mg
K Ca19 20
12
37
Rb38
Sr
Cs55
Ba56 57
La
58
Ce59
Pr60
Nd61
Pm62
Sm63
Eu64
Gd65
Tb66
Dy67
Ho68
Er69
Tm70
Yb71
Lu
87
Fr88
Ra89
Ac
90
Th91
Pa92
U93
Np94
Pu95
Am100
Fm101
Md102
No103
Lr96
Cm97
Bk98
Cf99
Es
21
Sc22
Ti23
V24
Cr25
Mn26
Fe27
Co28
Ni29
Cu30
Zn31
Ga32
Ge33
As34
Se35
Br36
Kr39
Y40
Zr41
Nb42
Mo43
Tc44
Ru45
Rh46
Pd47
Ag48
Cd49
In50
Sn51
Sb52
Te53
I54
Xe72
Hf73
Ta74
W75
Re76
Os77
Ir78
Pt79
Au80
Hg81
Tl82
Pb83
Bi84
Po85
At86
Rn104
Rf105
Db106
Sg107
Bh108
Hs109
Mt
1.008
6.941
22.9897
39.0983
85.4678
132.905
(223)
9.012
24.3050
40.078
87.62
137.327
(226)
44.9559
88.9058
138.90
(227)
47.867
91.224
178.49
(261)
50.9415
92.906
180.947
(262)
51.9961
95.94
183.84
(263)
54.938
(98)
186.207
55.845
101.07
190.23
58.9332
102.905
192.217
58.6934
106.42
195.078
63.546
107.868
196.966
65.39
112.411
200.59
10.811
26.9815
69.723
114.818
204.383
12.0107
28.0855
72.61
118.710
207.2
14.00
30.9737
74.921
121.760
208.980
15.9994
32.066
78.96
127.60
(209)
18.9984
35.4527
79.904
126.904
(210)
4.0026
20.1797
39.948
83.80
131.29
(222)
1.007
140.116
232.0381
140.90765
231.03588
144.24
238.0289
(145)
(237)
150.36
(244)
151.964
(243)
157.25
(247)
158.92534
(247)
162.50
(251)
164.93032
(252)
167.26
(257)
168.93421
(258)
173.04
(259)
174.967
(262)
(262) (265) (266)
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Chem Fam
Oxidizers
-ClO3-NO3
Fire Gases
SOX NOX
Organic
peroxides
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FIELD SCREENING TESTS
• EXPLOSIVE?• CORROSIVE?• WATER SOLUBLE?• WATER REACTIVE?• CYANIDE?• OXIDIZER?
• HALIDE?• OTHER TESTS• DESCRIPTION• SULFIDE?• FLAMMABILITY?
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EXPLOSIVES
• High rate of burning• Use hairpin test• If positive for
explosives STOP!!
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What are explosives/explosions?
Explosive: chemical that can produce the extremely rapid release of gas and/or heat.
Explosion: sudden, violent release of mechanical, chemical, or nuclear energy
Four Basic Types:• Pressure Relief• Rapid Oxidation• Runaway
Polymerization• Molecule
Decomposition
Oppdbs.av
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DOT Classes
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1.1 Explosives with mass explosion hazard1.2 Explosives with a projection hazard1.3 Explosives with predominantly a fire hazard1.4 Explosives with no significant blast hazard1.5 Very insensitive explosives; blasting agents1.6 Extremely insensitive detonating articles
CLASS 1: EXPLOSIVES
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Explosive?
• Consult ERG• Hair pin test• Other references• Orange DOT label• Nitro- compounds• Explosives kits
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CORROSIVE
• pH paper• 0-6 Acid• 7 Neutral• 8-14 Base
• Bleach?• High concentrations?
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pH of Common Items14.0 Strong Bases: NaOH, KOH, Ca(OH)2
12.5 RCRA haz. waste
BASIC 12.0 Household ammonia10.0 Detergents and Baking Soda8.0 Seawater7.4 Blood
NEUTRAL 7.0 Pure water6.0 Rain4.0 Beer3.0 Orange juice, vinegar, wine, acid rain
ACIDIC 2.0 RCRA haz. waste/lemon juice, stomach acid1.0 Strong acids: HCl, HF, HI, H2SO4, HNO3
0.0 Very acidic
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CLASS 8: CORROSIVE MATERIALS
• Corrosive = a liquid or solid that causes full thickness destruction of human skin at the site of contact with in 14 days or
• exhibit a corrosion rate on steel or aluminum exceeding 1/4 inch per year
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Copper Metal and Acid
Cu(s) + HNO3(aq) CuNO3(aq) + H2(g)Cu(s) + HCl(aq) No Reaction
Cu_acid.mov
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Recognition of Common CorrosivesACIDS• Begin with Hydrogen “H”• End in non-metal or
nonmetal oxide• Exceptions: Organic
Acids (end in COOH), Phenol
• Examples: HCl, H2SO4, CH3COOH, HF, HNO3
• Usually liquids or a gas dissolved in water
BASES• Metal + Hydroxide (OH)• Metal + Oxygen• Active Metal (column 1-2
on periodic table)• Exceptions: Ammonia
(NH3), Amines, Carbonates• Examples: NaOH, K2O, Li,
KOH, Ca(OH)2, NaHCO3
• Usually solids or solids dissolved in water
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WATER SOLUBILITY• DISSOLVES (Y/N)• FLOAT (hydrocarbons)• SINK (halogenated hydrocarbons)• EMULSIFY (coffee creamer)• REACTIVE—
– HEAT – BUBBLES (flammable, toxic?)
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Potassium (K) + Water (H2O)
Kpond.avi
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REACTIVES• Normally unstable-reacts violently• Mixes with water to form toxic or flammable
gases• Capable of detonation at STP or if heated in
confinement• Contains cyanide or sulfide and generates toxic
gases, vapors, or corrosive fumes
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Preparing Acid Test Solution• Directly purchase 3N HCl
solution• Add 250ml of 12N HCl to
750ml of distilled water• Dropper bottle preferable—
watch contamination• One of the more frequently
used tests
water
HCl
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CYANIDE• Only if pH is greater than 7• Use cyanide test by adding
solid cyanide test test 2 to a test tube with 1/4 inch cyanide test 1
• Add a pea size (or ¼ inch) amount of the unknown
• Add 3-5 drops of Acid Test solution
• Deep Prussian blue indicates cyanide
Before After
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TOXICITY
• Toxicity Characteristic Leaching Procedure (TCLP) identifies 39 chemicals to test for in wastes for their ability to leach out and contaminate ground water
• Acutely hazardous wastes: (1) Oral LD50less than 50 mg/kg, (2) a dermal LD50 of less than 200 mg/kg, or (3) an inhalation LC50 of less than 2 mg/kg.
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Preparing Cyanide Tests
• Cyanide Test #2 –Use directly crystals of ferrous ammonium sulfate
• Cyanide Test #1– 20g ferrous ammonium citrate in 100ml of water
• Saturated Solution—takes a while to dissolve
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OXIDIZER TEST
• Use Potassium Iodide (KI) paper
• Acidify KI paper with 2-3 drops of acid test
• Hold paper over then touch unknown with paper
• Blue/black or purple color indicates an oxidizer
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CLASS 5: OXIDIZERS AND ORGANIC PEROXIDES
5.1 Oxidizers-a material that may, generally by yielding oxygen, cause or enhance the combustion of other materials
5.2 Organic peroxides-an organic compound containing the bivalent -O-O- structure
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Zn(s) + I2 (s) ZnI2(s)
Zni.mov
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SULFIDE TEST• Wet Sulfide Test
Paper (Lead Acetate) with a few drops of water
• Touch paper to acidified unknown on watch dish
• Color change from white to brown indicates sulfide (lead may cause a black or silver color)
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FLAMMABILITY
• Place a pool the size of a 50 cent piece on watch dish
• Bring a lit match slowly towards the watch dish
• Ignites B4 the edge• Ignites when touched• Match acts as wick
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CLASS 3: FLAMMABLE & COMBUSTIBLE LIQUIDS
• Flammable Liquid = flash point between 100oF and 141oF
• Combustible Liquid = flash point above 141oF and below 200oF
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HALIDE TEST
• Only if not water soluble• Clean off copper wire in
flame until only red/yellow flame
• cool wire• place a few drops of sample
on the coil and heat in flame• green color = organo halide(~ 125-1000ppm MDL)
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Copper Wire Test
• Curve one end of an 8 inch piece of 10 gauge wire.
• Strip 6 inches of insulation off the other end of the 10 gauge wire
• Wrap the the bottom inch of the stripped end with 20 gauge wire
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OTHER TESTS• CGI - Combustible Gas
Indicator• PID - Photoionization
Detector• FID - Flame Ionization
Detector• Colorimetric Indicator
(Drager) Tubes• Oxygen Sensor
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Colorimetric Indicator Tubes
• Measures: Compounds or Family of Compounds
• Units: PPM or % for Quantitative Measurements
• Range: Varies; Example: 1 Compound - 5 Different Tubes With Different Ranges
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Photoionization Detector• Measures: Organic and
Inorganic Air Contaminants (Must have an Ionization Potential Below the Measuring Probe)
• Units: Indicates in PPM• Range: .5 to 2000 ppm• Probes: Hnu: 9.6eV,
10.2eV, and 11.7eV
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Flame Ionization Detector
• Measures: Organic Atmospheric Contaminants (Compounds That Will Burn In a Flame)
• Units: Indicates in PPM
• Range: .5 to 1000 ppm
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Chemical Weapons Identification• M8/M9/M256• Colorimetric• PID/FID• APD 2000• AP2Ce• SensIR• Hapsite• SaphaIRe
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Travel IRSensIR—Solid/Liquid ID of Covalently bonded (non-metals) compounds (mainly organics)
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AP2CeAP2Ce—Simultaneous V,G, & H 10 X Sensitive as APD for G5 X Sensitive as APD for H
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SAMPLE DESCRIPTION
• Physical and Chemical Properties
• Solid (crystals?), liquid, gas
• Color• Odor• Viscosity• Other?
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Information Resources
• Compare observed properties of the unknown material to the properties of a likely match or matches
• Test a few unique properties of the material to confirm or deny the identity
• Compound specific references are necessary, preferably more than one
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WHAT IS IT?• Category versus
identity?• Apply knowledge of
chemical families• Narrow the range of
possibilities • Major Hazard
Group
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WHY FIELD SCREENING?
• Hazards• Bulking• Disposal• Transport• Storage• Mixtures
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Chemical Segregation
• Use specific information on MSDS, NIOSH, etc.
• DOT Chart (note: acids and bases are both Class 8 (corrosives) but, they should be stored seperately.
• Summary
idiots mix stuff.wmv
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Notes: O = Must have a separation between the materials
X = Must not be shipped in the same vehicle
* = See Compatibility Table for Class 1 (Explosive) Materials
A = Ammonium Nitrate and ammonium nitrate fertilizer may be loaded or stored with Division 1.1 or 1.5 materials
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Summary
• Separate into the 9 DOT Classes• Separate acids and bases• Separate oxyacids from non-oxyacids• Separate oxidizers from flammables• Separate water reactives from water based
solutions• Multiple Classes are a separate class
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FIELD IDENTIFICATION OF UNKNOWN
MATERIALS
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OBJECTIVES
• Become familiar with the major tests on the HazCat (TM) flowchart
• Interpret the results of the major tests on the HazCat (TM) flowchart
• Apply HazCat(TM) flowchart and manual to identify unknowns
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Unknown liquid (top)
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Unknown liquid (bottom)
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Oxidizer/Acid Test• Same oxidizer test
as in field screening
• Acid test determines if the unknown reacts (bubbles, fizzes, boils, pops, etc.)
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Iodine Crystal Test Results
Hexane Toluene Acetone Methanol Gasoline Diesel MineralOil
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Unknown solid (top)
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Unknown solid (bottom)
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CONCLUSION
• If properly applied the HazCat(TM) flowchart can assist in identifying materials in the field
• The large number of compounds and mixtures makes it difficult to always identify the unknown material
• Reference materials can also assist in the identification of materials in the field
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QUESTIONS?
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LABORATORY SAFETY
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Case Studies
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LABORATORY SAFETYPlanning
• Primary and secondary exits• Emergency equipment
– Eyewash– Shower
• Keep access to emergency equipment and exits clear
• Keep aisles clear
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LABORATORY SAFETYBehavior
• Listen to & follow directions• Read & follow instructions• Read all of the test steps before starting the
actual test• Think about why each test is being
completed
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LABORATORY SAFETYBehavior
• Pipette materials onto test papers/wires– Do not place tests into test tubes
• Think about test results– Do they make sense?
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LABORATORY SAFETYBehavior
• Treat unknowns as hazardous• Avoid practical jokes• Always wear PPE• Be careful with glassware - avoid injury• Inspect glassware for damage
– Remove if chipped, cracked, or badly etched
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LABORATORY SAFETYBehavior
• Point heated test tubes away from all personnel
• Use tongs or special gloves to move hot glassware
• Clean up broken glassware immediately• Do not pick up broken glass with bare
hands
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LABORATORY SAFETYBehavior
• Be careful of slips, trips, and falls• No pouring or shaking of test tubes• Use small amounts of unknown• Scoop or pipette materials• BE ALERT
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LABORATORY SAFETYBehavior
• Point all flames away from personnel• Do not dispose of any hot materials in trash• Do Char Hairpin test before doing the Char
test!!!!• Add the unknown to water • Follow instructions
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LABORATORY SAFETYClean Up
• Keep work areas clean and uncluttered
• Keep work surfaces clean and cleared
• Decon all non-disposable PPE