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TPSA 2019Pesticide Storage and
Compatibility
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Nightmare Scenario
General Mattis on “Face the Nation”
What keeps you awake at night?
“Nothing. I keep other people awake at night.”
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Apex North Carolina
Root cause determined to be oxygen generators from aircraft maintenance
Stored with pool chemicals from Household Hazardous Waste (HHW) collection
Spread to adjacent storage bay with flammable liquids in drums
Local fire officials determined best to let the fire burn itself out
Result – Big Smoking Hole
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BSH
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Emergency Planning and Community Right to Know Act of 1986
Significant amendment to CERCLA Established in response to Bhopal, India MIC incident. ‘Extremely Hazardous Substances’, ‘Hazardous Chemicals’ and
‘Toxic Chemicals’
Established State Emergency Response Commissions (SERC) and Local Emergency Planning Committees (LEPC) NOTE: OSHA has Hazard Communication Standard (‘Worker
Right to Know’) EPCRA is Emergency Responder and Local Community ‘Right to
Know’
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EPCRA Reporting requirements
Ongoing (forward looking) obligations Notify SERC of any EHS above TPQ (Threshold Planning
Quantities), within 60 days exceeding TPQ. Notify LEPC. Notify LEPC and SERC in case of RQ releases of hazardous
substances Submit complete set of SDS or chemical list organized by hazard
category for OSHA hazardous chemicals >10,000 lbs NOTE: Notifications should trigger invitations to participate in
LEPC. Always be on good relationships with local FD and any HazMat team
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In Summary
Manufacture, Handling, Use, Transportation and Disposition of Hazardous Materials is comprehensively regulated by USEPA and States. Local involvement as well
Patchwork quilt of statutes and regulatory programs Different purposes, different lists, overlapping
requirements, revolving around protecting Human Health, Worker Health and Safety, Environmental Media (air, water, and land) and providing information to Regulatory Agencies, Local Emergency Responders, Communities and other Stakeholders
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This Photo by Unknown Author is licensed under CC BY
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General Categories of Chemical Hazards
FACTOR Flammable (and Combustible) EPA nomenclature D001
ignitable Corrosive EPA nomenclature D002 corrosive Toxic (or) EPA nomenclature D004-D042 (Toxic) or multiple
listed wastes on the F-, K-, U-, and P-lists Reactive EPA nomenclature D003 reactive Also, compressed gases, including aerosols
Aerosol propellants may pose different hazards than contents.
Common household chemicals and chemical hazards at home
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Acute vs. Chronic Hazards
Acute – single exposure or exposure occurring over a short period of time
Sub-chronic – intermediate exposures between acute and chronic (up to 90 days)
Chronic – multiple or constant exposure to small concentrations that would not elicit an acute toxic response
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Flammable and Combustible Materials
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Introduction
Two primary hazards explosion and fire
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Flashpoint
Minimum temperature at which a liquid gives off enough vapor to form an ignitable mixture
Generally, the lower the flashpoint, the greater the hazard
Flammable liquids have flashpoints < 100°F, and are more dangerous than combustible liquids, since they may be ignited at room temperature
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Flashpoint
Combustible liquids have flashpoints at or above 100°F
Combustible liquids have higher flashpoints than flammable liquids and can pose serious fire and/or explosion hazards when heated
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Flash Point
Lower Flash Point, easier to catch fire
Chemical Flash Point (º F)
Gasoline -50
Benzene -4
Acetone 3
MEK 21
Ethyl Alcohol 54
Mineral Spirits 100
Kerosene 110
Motor Oil 300
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Explosive Limits
Flammable Range Lower explosive limit (LEL) to the upper explosive limit (UEL) Expressed as a percent of fuel vapor in air Mixture below LEL is too lean to burn UEL is the maximum percentage of the material in air that will
still burn Mixture above the UEL is too rich to burn
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Explosive LimitsChemical LEL UELBenzene 1.2 7.8Gasoline 1.7 7.6Methane 5.0 15.0Acetone 2.5 12.8
Hydrogen Sulfide 2.5 12.8Ammonia 15.0 28.0Acetylene 2.5 100
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Fire Tetrahedron
Oxygen Fuel (vapor) Ignition Chemical Reaction
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Vapor Characteristics
Vapor pressure – force exerted by containerized gas on the side
Tendency for a solid or liquid to evaporate (ie, the boiling point)
Higher the vapor pressure, the more likely the material is to enter the atmosphere as a gas creating potential fire or inhalation hazard
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Vapor Characteristics
Vapor density – the weight of a vapor or gas relative to air (air=1)
Greater than 1, the vapor or gas is heavier than air and will tend to accumulate in low-lying areas
Less than 1, the vapor or gas will rise
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Classes of Flammableand Combustible Liquids
IIIA
II
IC
IA IB
200
140
10073
Flas
h Po
int (
o F)
100Boiling Point (oF)
Combustible(FP > 100oF)
Flammable(FP < 100oF)
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Sources of Ignition
Open flames Smoking Static electricity Cutting and welding Hot surfaces Electrical and mechanical sparks Lightning
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Static Electricity
Generated when a fluid flows through a pipe or from an opening into a tank
Difference in “charge” between two objects Main hazards are fire and explosion from sparks
containing enough energy to ignite flammable vapors
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Bonding
Physically connect two conductive objects together with a bond wire to eliminate a difference in static charge potential between them
Must provide a bond wire between containers during flammable liquid filling operations, unless a metallic path between them is otherwise present
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Grounding
Eliminates a difference in static charge potential between conductive objects and ground
Although bonding will eliminate a difference in potential between objects, it will not eliminate a difference in potential between these objects and earth unless one of the objects is connected to earth with a ground wire
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Ventilation
Always provide adequate ventilation to reduce the potential for ignition of flammable vapors.
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Safety Cans for Storage and Transfer
Approved container of not more than 5 gallons capacity
Spring-closing lid and spout cover
Safely relieves internal pressure when exposed to fire
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Flame Arrester Screen
Prevents fire flashback into can contents
Double wire-mesh construction
Large surface area provides rapid dissipation of heat from fire so that vapor temperature inside can remains below ignition point
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Transferring Flammable Liquids
OSHA allows 4 methods for transferring these materials: Through a closed piping system From safety cans By gravity through an approved self-closing safety faucet By means of a safety pump
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Self-Closing Safety Faucet
Bonding wire between drum and container
Grounding wire between drum and ground
Safety vent in drum
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Safety Pump
Faster and safer than using a faucet
Spills less likely No separate safety vents in drum
required Installed directly in drum bung
opening Some pump hoses have integral
bonding wires
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Waste and Residue
Waste drum with disposal funnel
Safety disposal can Oily-waste can (self-closing lid)
Combustible waste and residue must be kept to a minimum, stored in covered metal
receptacles and disposed of daily.
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Fire Control
Suitable fire control devices like a portable fire extinguisher must be available where flammable or combustible liquids are stored
Open flames and smoking must not be permitted in these storage areas
Materials which react with water must not be stored in the same room with flammable or combustible liquids
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General Chemistry
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Periodic Table
Source: http://www.biochem.wisc.edu/medialab/clipart.html
Noble G
asesR
eact
ive
Met
als
Metals
Radioactives
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Compounds
Substance consisting of 2 or more different elements in a fixed ratio
Can be reduced to pure elements by chemical reactions
Physical and chemical properties different from pure element
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Compound Symbols
The chemical symbol for a compound has the symbols for each element and the number of each element in the compound.
For example, Benzene has 6 Carbon atoms and 6 Hydrogen atoms.
The chemical symbol is C6H6.
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Compounds
Image Source: http://www.worldofmolecules.com/solvents/benzene.htm
Benzene (C6H6)
Ibuprofen (Advil® or Motrin ®)
(C13H18O2)
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Compounds - Example
NaCl – table salt Sodium: Na – soft white metal,
reacts violently with water Chlorine: Cl – pale green corrosive
gas
Image Source: http://nobel.scas.bcit.ca/resource/ptable/na.htm
Sodium in water
Chlorine gas
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Organic vs Inorganic
Organic compounds: Must have carbon in the molecular structure, Usually have hydrogen (hydrocarbons) Sugar, paper, gasoline, natural gas, etc.
Inorganic compounds: Metals, salts, silica, alumina, etc.
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Organic Compounds
Defined as chemical compound whose molecules contain both: Carbon Usually Hydrogen
Entire subject of study called Organic Chemistry.
Typically have BTU value and can be used as fuels
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Organic Compounds
Examples of organic compounds include: Gasoline and Diesel Soaps/Surfactants Alcohols Plastics Mineral Spirits Oils/Petroleum products Cough syrup Methanol Most pesticides
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Inorganic Compounds
For our purposes, all other compounds
Includes: Salts Acids Bases Metals
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Specific Gravity (Density)
Density is mass of a unit volume of some material. Water has a density of 8.345
lbs/gallon
The specific gravity of a material is its density compared to water Specific Gravity of water is 1 Corn
Syrup
Canola Oil
Water
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Special Hazards Posed by Chemical Oxidizers
What are Oxidizers: A class of chemical compounds that can act as an oxygen source.
Oxidizers can readily cause combustion of organic materials.
The resulting chemical fires are very difficult to extinguish.
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Oxidizer Examples
Peroxides Chlorites Nitrates Nitrites Chromates Permanganates Pool chemicals/chlorine Airplane oxygen generators Some acids Nitric Sulfuric Perchloric
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Oxidizer Labels and Markings
DOT Oxidizers yellow 5.1 “burning O”
NFPA labels “OXY” in the lower
Reactivity box
Pictogram
OXY
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Oxidizers – What You Should Know
Pose severe fire hazards Are intended to react quickly under controlled
conditions Enter into violent chemical reactions when
uncontrolled Found: Many fertilizers Universities and laboratories Manufacturing facilities Household Hazardous Waste events
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Oxidizers – What You Should Know
Need to be segregated from incompatible materials flammables combustibles organic materials strong reducing agents finely divided metals
Segregate from incompatibles during transportation, storage, and processing
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Hazards of Corrosives
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What Is a Corrosive?
Can be solid, liquid, or gas
Material that causes destruction to human tissue or other materials
The two forms of corrosives are Acids, pH < 7.0 Bases, pH > 7.0
A material with a pH = 7 is neutral.
Corrosive bases are called caustics (i.e., caustic soda)
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pH
A pH of 1 is very acidic A pH of 14 is very alkaline Because of the very large range in
the values of pH, a special scale has been created. On it a change in pH of one unit (for
example 3 to 4) represents a 10-fold change in acidity or alkalinity.
Hydrogen ion concentration (pH) is used to determine if a substance is an acid or base.
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Corrosive Hazards
Attack skin, eyes, and tissue
Attack other materials Contribute to fire
hazards Generate hydrogen gas Generate toxic gases Create heat Health hazard when
breathed
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pH
Measurement of H+ ions.
Ranges from 0-14 7 is neutral <7 is an acid >7 is a base (a.k.a.
caustic) Measured by meter, pH
paper, other means pH between 4 and 10
are not that corrosive
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Acids
Corrosive to metal and skin. pH < 7 Lower the number, the stronger the acid. Created from burning halogens, phosphorus, or
sulfur. Common acids: hydrochloric, hydrofluoric,
phosphoric, formic, and acetic.
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Examples
Strong Acids Nitric Acid Perchloric Acid Hydrochloric Acid Sulfuric Acid
Weak Acids Acetic Acid Carbonic Acid Hydrocyanic Acid
Image Source: http://www.easy2source.com/products/473/474/520/523/524/
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Bases/Caustics
Bases are also called Caustics
Corrosive to aluminum and skin
Produces a pH of >7 Higher the number, the
stronger the base. Typically hydroxides,
but also amines. Ammonia Sodium Hydroxide
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Warning Labels and Signs
Warning signs DOT Label HMIS® Labels NFPA Labels Read the labels HazComm Pictograms
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Engineering Controls
Enclose corrosive operations
Use ventilation and exhaust systems
Select compatible materials
Minimize operating pressures
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Storage
Store corrosives away from production areas
Most corrosives are incompatible
Storage areas should be corrosion resistant
Have spill and leak containment
Areas must be well ventilated
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Emergency Equipment
First-aid kit Spill-response
supplies Safety showers Eyewash stations Fire extinguishers
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Handling Corrosives
Do not add water to strong acids or alkalis Do not contact with bare skin Wash off quickly if exposed
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Dispensing Corrosives
Reduce vapors, mists, dusts Use caution when pouring into small containers Use pumps Never pressurize a container Use scoops for solids Close containers when done
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LDR PROGRAM
Purpose Predominantly groundwater
protection Untreated hazardous waste can
leach into groundwater
Implementation Reduce toxicity Destruction Removal/Separation
Reduce leachability Immobilization
40 CFR 268
Groundwater Protection Strategy
1. LDR2. LDU3. Groundwater Monitoring
Multiple layers of protections
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Use of Enabling Technologies
Organics Inorganics TypePhysical Treatment Yes Yes Separation
Chemical Treatment Yes Yes Separation/destruction
Stabilization No Yes Immobilization
Incineration Yes No (except CN) Destruction
Fuels Blending Yes No (limited exceptions) Destruction
Landfill No untreated waste No untreated waste Immobilization
Note: Common hazardous wastes can be treated using Heritage owned technologies and facilities.
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General Sequence of Treatment
Generally, organics are treated first, as some inorganics can be handled with organic treatment methods
Remaining inorganics (typically metals) are treated after organics removed.
Incineration Stabilization Landfill
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General Sequence of Treatment
Examples Organic industrial wastes (other than plant trash) are typically
treated by biological or thermal means (or by recovery in specific situations) Spent solvents or paints or inks, etc. get recycled or blended into
supplemental fuels Inorganic industrial wastes typically treated by
physical/chemical means (or thermal methods) Acids and caustics get neutralized, metals get precipitated or
stabilized in hydroxide and/or sulfide forms Separation technology
Scrap metal and used batteries go to metals recycling
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Aci
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Acids X X X X XBases/Caustics/Alkalies
X X
Chlorinated Solvents
X X X X
Class 9/AqueousCyanides X X XFlammables/Combustibles1
X X
StrongOxidizers
X X X X
Use of Table: Waste categories use DOT-defined terms. A combination with an "X" denotes an incompatibility. Do not consolidate waste-combinations noted by an "X".1 Non-chlorinated solvents and oils.
EPA’s Incompatibility Chart, Improved by Heritage
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Incompatibles
Oxidizers and flammable/combustibles Strong acids and strong bases Acids and cyanides Acids and sulfides Finely divided metals, including zinc, magnesium,
aluminum, and even Iron swarf, etc. With Air With Combustibles
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Incompatibles
Chemicals that will liberate toxic gases under the ‘wrong conditions’ Nitric Acid Ammonia solutions Cyanide solutions Nitrate-containing wastes Other
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Incompatibles
Empirical incompatibilities (wastestreams we know that require specialized handling, regardless of EPA codes or DOT labels) Aluminum paints Nitrocellulose coatings Nitrocellulose films Metal machining wastes/swarf, including iron particles Shock Sensitives (picric acid, ethyl ethers, MEK peroxides, etc.)
– place here or later in the outline?? Catalysts Lithium and air
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Questions?