TPSA 2019Pesticide Storage and

Compatibility

Nightmare Scenario

General Mattis on “Face the Nation”

What keeps you awake at night?

“Nothing. I keep other people awake at night.”

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

BSH

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’

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

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

This Photo by Unknown Author is licensed under CC BY

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

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

Flammable and Combustible Materials

Introduction

Two primary hazards explosion and fire

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

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

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

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

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

Fire Tetrahedron

Oxygen Fuel (vapor) Ignition Chemical Reaction

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

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

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)

Sources of Ignition

Open flames Smoking Static electricity Cutting and welding Hot surfaces Electrical and mechanical sparks Lightning

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

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

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

Ventilation

Always provide adequate ventilation to reduce the potential for ignition of flammable vapors.

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

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

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

Self-Closing Safety Faucet

Bonding wire between drum and container

Grounding wire between drum and ground

Safety vent in drum

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

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.

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

General Chemistry

Periodic Table

Source: http://www.biochem.wisc.edu/medialab/clipart.html

Noble G

asesR

eact

ive

Met

als

Metals

Radioactives

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

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.

Compounds

Image Source: http://www.worldofmolecules.com/solvents/benzene.htm

Benzene (C6H6)

Ibuprofen (Advil® or Motrin ®)

(C13H18O2)

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

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.

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

Organic Compounds

Examples of organic compounds include: Gasoline and Diesel Soaps/Surfactants Alcohols Plastics Mineral Spirits Oils/Petroleum products Cough syrup Methanol Most pesticides

Inorganic Compounds

For our purposes, all other compounds

Includes: Salts Acids Bases Metals

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

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.

Oxidizer Examples

Peroxides Chlorites Nitrates Nitrites Chromates Permanganates Pool chemicals/chlorine Airplane oxygen generators Some acids Nitric Sulfuric Perchloric

Oxidizer Labels and Markings

DOT Oxidizers yellow 5.1 “burning O”

NFPA labels “OXY” in the lower

Reactivity box

Pictogram

OXY

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

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

Hazards of Corrosives

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)

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.

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

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

http://www.yellowtang.org/images/ph_scale_c_la_784.jpg

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.

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/

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

Warning Labels and Signs

Warning signs DOT Label HMIS® Labels NFPA Labels Read the labels HazComm Pictograms

Engineering Controls

Enclose corrosive operations

Use ventilation and exhaust systems

Select compatible materials

Minimize operating pressures

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

Emergency Equipment

First-aid kit Spill-response

supplies Safety showers Eyewash stations Fire extinguishers

Handling Corrosives

Do not add water to strong acids or alkalis Do not contact with bare skin Wash off quickly if exposed

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

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

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.

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

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

Aci

ds

Bas

es/

Cau

stic

s/A

lkal

ies

Ch

lori

nat

ed

Sol

ven

ts

Cla

ss 9

/ A

qu

eou

s

Cya

nid

es

Fla

mm

abl

es and

C

omb

ust

ible

s1

Str

ong

Oxi

diz

ers

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

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

Incompatibles

Chemicals that will liberate toxic gases under the ‘wrong conditions’ Nitric Acid Ammonia solutions Cyanide solutions Nitrate-containing wastes Other

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

Questions?