TRAINING COURSE
FOR
MULTI-MEDIA INSPECTORS
Student Manual
13INSTRU.MAK
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SECTION I MEXICAN ENVIRONMENTAL PROGRAM OVERVIEW
SECTION II HEALTH AND SAFETY FOR FIELD ACTIVITIES
SECTION in FUNDAMENTALS OF ENVIRONMENTAL COMPLIANCE
INSPECTIONS
SECTION IV WASTE WATER INPSECTIONS
SECTION V AIR POLLUTION/HAZARDOUS WASTE INSPECTIONS
SECTION VI POLLUTION PREVENTION
SECTION vn INDUSTRIAL PROCESSES
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I3INSTRU.MAN
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TABLE OF CONTENTS
Section I - Mexican Environmental Program Overview 1-1
Section n - Health and Safety for Field Activities
Chapter 1 - Preparation for Field Activities 1-1
Chapter 2 - Hazards, Exposure and Evaluation 2-1
Chapter 3 - Protective Clothing and Equipment 3-1
Chapter 4 - Respiratory Protection 4-1
Section m - Fundamentals of Environmental Compliance Inspections
Chapter 1 - Introduction to Environmental Compliance 1-1
Chapter 2 - Inspection Planning and Preparation 2-1
Chapter 3 - Entry and Opening Conference 3-1
Chapter 4 - Information Gathering and Documentation 4-1
Chapter 5 - Post-Inspection Activities 5-1
Section IV - Waste Water Inspections
Chapter 1 - General Procedures 1-1
Chapter 2 - Sampling Techniques 2-1
Chapter 3 - Treatment Technologies 3-1
Chapter 4 - Pollution Prevention Techniques 4-1
Section V - Air Pollution/Hazardous Waste Inspections
Chapter 1 - Baseline Inspection Techniques for Air Pollution Sources 1-1
Chapter 2 - Hazardous Materials/Hazardous Waste Inspection Procedures 2-1
Section VI - Pollution Prevention
Chapter 1 - Introduction to Pollution Prevention 1-1
T3INS1KUJMAN
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TABLE OF CONTENTS (Continued)
Section Vn - Industrial Processes
Chapter 1 - Petrochemical Industry 1-1
Chapter 2 - Chemical Manufacturing 2-1
Chapter 3 - Pharmaceutical Manufacturing Plants 3-1
Chapter 4 - Metallurgical Industries 4-1
Chapter 5 - Tanneries 5-1
Chapter 6 - Cement Industries 6-1
Chapter 7 - Printed Circuit Board Manufacturing 7-1
Chapter 8 - Electroplating 8-1
Chapter 9 - Lead Smelting 9-1
T3INSIRUJMAN 11
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MEXICAN ENVIRONMENTAL PROGRAM
OVERVIEW
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II
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HEALTH AND SAFETY MANUAL
FOR
FIELD ACTIVITIES
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TABLE OF CONTENTS
Chapter Page
INTRODUCTION iii
OPENING STATEMENT iv
LIST OF ABBREVIATIONS AND ACRONYMS v
1.0 PREPARATION FOR FIELD ACTIVITIES 1-1
1.1 Objective 1-1
1.2 Introduction 1-1
1.3 Pre-Field Activity Evaluation 1-1
1.4 Onsite Evaluation 1-2
2.0 HAZARDS, EXPOSURE AND EVALUATION 2-1
2.1 Objective 2-1
2.2 Introduction . 2-1
2.3 Safety Guidelines and Techniques 2-1
2.4 Heat Stress 2-5
2.5 Fire and Explosion Hazards 2-7
2.6 Selection and Use of Fire Extinguishers 2-12
2.7 Chemical Hazard Recognition and Evaluation 2-15
2.8 Effects of Toxic Chemicals in the Body 2-19
2.9 Dose-Response Curves 2-25
2.10 Evaluating Health Hazards and Toxicity Information 2-30
2.11 References 2-35
2.12 Emergency First Aid for Field Activities 2-38
3.0 PROTECTIVE CLOTHING AND EQUIPMENT 3-1
3.1 Objective 3-1
3.2 Selection of Personal Protective Clothing and Equipment (PPE) 3-1
3.3 Levels of Protection 3-6
3.4 Controlling the Transfer of Contaminants 3-6
3.5 Decontamination 3-11
3.6 Donning and Doffing Protective Clothing 3-12
3.7 Storage of Equipment 3-12
4.0 RESPIRATORY PROTECTION 4-1
4.1 Objective 4-1
4.2 Recognition of Respiratory Hazards 4-1
4.3 Types of Respirators 4-4
4.4 Respirator Selection 4-9
4.5 Respirator Use 4-11
4.6 Special Considerations 4-12
4.7 Respirator Fit Testing 4-12
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TABLE OF CONTENTS (CONTINUED)
APPENDICES
Number Page
1-A Sample Safety and Health Planning Guideline for Field Activities 1-3
3-A Performance Requirements of Protective Clothing 3-13
3-B Protective Materials 3-15
3-C Procedures for Donning and Doffing Personal Protective Clothing 3-17
TABLES
Number Page
2-1 Characteristics of Flammable Liquids 2-11
2-2 Fire Classification and Extinguishing Media 2-14
2-3 Fire Extinguisher Identification 2-14
2-4 Characteristic of Air Contaminants in Work Places 2-17
2-5 Industrial Toxicants That Produce Disease of the Respiratory Tract 2-24
2-6 Organs/Systems Affected by Chemical Exposure 2-26
2-7 Some Direct-Reading Instruments 2-33
3-1 Typical Noise Reduction Ratings (NRRs) for Common Hearing Protection
Devices 3-4
3-2 Physical Characteristics of Protective Materials 3-5
3-3 Level of Protection 3-7
4-1 Physiological Effects of Oxygen Deficiency 4-3
4-2 Relative Advantages and Disadvantages of Air-Purifying Respirators 4-6
4-3 Respirator Styles 4-6
4-4 Relative Advantages and Disadvantages of Atmosphere-Supplying Respiratory
Protective Equipment 4-7
4-5 Respirator Protection Factors 4-10
4-6 Advantages and Disadvantages of Qualitative and Quantitative Fit Testing 4-13
FIGURES
Number Page
2-1 Skin cross-section 2-20
2-2 Organs of the human respiratory system 2-21
2-3 Classic dose-response curve 2-25
2-4 Dose-response curve for a chemical with no TLV 2-26
2-5 Dose-response curve for a highly toxic chemical 2-26
3-1 The ear 3-3
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INTRODUCTION
The Basic Health and Safety section of this SEDESOL inspectors' training course has been
developed using many materials on occupational safety and health that are part of the training
for inspectors from the United States Environmental Protection Agency (EPA). Their training
is designed to protect them from many of the same hazards that you too will face. By following
the practices detailed herein, you can help ensure your own health and safety and ultimately that
of your family members as well.
In some places in your manual you will see references to standards or rules set by U.S. agencies
such as the Occupational Safety and Health Administration (OSHA) or the National Institute
for Occupational Safety and Health (NIOSH). The standards that these agencies establish for
individuals who come in contact with hazardous materials, or who work under hazardous
conditions, are based upon the best scientific estimates of conditions that are acceptable to
maintain the good health of workers. You may see reference, for example, to Permissible
Exposure Limits (PELs); it is believed that most people who are exposed to the PEL of a
harmful substance during the course of an eight-hour work day will not experience any harmful
effect from such exposure. Exceeding a PEL puts you at an increased risk to the toxic effects of
hazardous materials.
You will also see references to rating standards for protective equipment or monitoring
instruments. In the United States an independent group called Underwriters Laboratory (UL)
examines and rates electrical equipment (including monitoring equipment) for safe use under
different conditions. Inspectors are advised to look for these rating systems to help them
evaluate whether or not equipment is safe to use under the expected work conditions. For
instance, a monitoring device that is not spark proof may pose a severe risk if it is used in an
environment that has sufficient concentrations of explosive vapors or dust.
Additional information pertaining to health and safety issues can be obtained from your
instructors and the reference materials listed in this manual.
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OPENING STATEMENT
BASIC HEALTH AND SAFETY MANUAL
FOR FIELD PERSONNEL
Field inspections involve a certain degree of risk. Inspections of wastewater treatment plants,
manufacturing plants, laboratories and mines are each associated with various hazards. A safe
field inspection depends on the recognition, evaluation and control of hazards. During field
activities, it is not always possible to eliminate hazards. However, it is possible to reduce the
risk associated with these hazards, through the use of monitoring or testing equipment,
engineering controls, personal protective equipment and employee training.
This course manual is an introduction to the basic health and safety training required for
conducting field activities. The goal of this manual is to provide you with the information
necessary to make the correct health and safety decisions in the field. This manual examines
health and safety principles and identifies methods to recognize and evaluate the hazards
associated with field activities.
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LIST OF ABBREVIATIONS AND ACRONYMS
ACGIH American Conference of Governmental Industrial Hygienists
ANSI American National Standards Institute
CFR Code of Federal Regulations
CPR Cardiopulmonary Resuscitation
CHRIS Chemical Hazard Response Information System
EPA Environmental Protection Agency
IDLH Immediately Dangerous to Life or Health
LEL Lower Explosive Limit
MSHA Mine Safety and Health Administration
NFPA National Fire Protection Association
NIOSH National Institute for Occupational Safety and Health
OSHA Occupational Safety and Health Administration
PAPR Powered Air-Purifying Respirator
PEL Permissible Exposure Limit
PPE Personal Protection Equipment
REL Recommended Exposure Limit
SAR Supplied-Air Respirator
SCBA Self-Contained Breathing Apparatus
TLV Threshold Limit Value
TWA Time Weighted Average
UEL Upper Explosive Limit
USCG U.S. Coast Guard
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CHAPTER 1
1.0 PREPARATION FOR FIELD ACTIVITIES
1.1 OBJECTIVE
To identify key elements that must be considered when preparing
for field activities.
L2 INTRODUCTION
Importance of
Preplanning
Planning Process
Sources of
Information
Field personnel encounter a wide variety of potential
hazards.
Preplanning can reduce or eliminate many hazards.
Research potential hazards.
Evaluate the risks.
Select appropriate protective equipment and clothing.
Plant personnel
Agency files
Agency employees
Industry standard references
1.3 PRE-FIELD ACTIVITY EVALUATION
Planning Guide
Components of
the Planning
Guide
Prepare planning guide. (See Appendk 1-A).
Acquire pertinent medical records and other information.
Take guide and information to the site.
Leave a copy with your supervisor.
Activity location
name and address
contact name and telephone number
photographs
Historical information
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Activity schedule
Inspection personnel
names
restrictions
required training
Lodging
Hazards
transportation (distances, chemicals, supplies, test
equipment, etc.)
noise
fire/explosion
biological
weather-related
chemicals
atmospheric
thermal
radiological
confined space
drowning
physical and mechanical (height, machinery, etc.)
Vehicles
Required permits
Emergency and rescue
communication (telephone, two-way radio, etc.)
warning signals (fire, evacuation, severe weather,
etc.)
hospitals, emergency assistance personnel
Personal protective equipment and clothing
Miscellaneous
1.4 ONSITE EVALUATION
Request a health and safety briefing.
Conduct a walk-through survey.
hidden hazards
natural hazards
Record unexpected hazards, additional gear requirements.
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APPENDIX 1-A
SAMPLE SAFETY AND HEALTH PLANNING GUIDELINE
FOR FIELD ACTIVITIES
Facility/Site:
Location:
Agency files exist Yes No
If yes, list pertinent historical information
DATES AND LENGTH OF PROPOSED ACTIVITY:
SITE CONTACTS:
Name Position Tel. Number
INSPECTION TEAM:
Medical Field Respiratory Medical/Physical
Name monitoring training training restrictions
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LODGING ARRANGEMENTS: Motel/Hotel
Location
SITE ACCESS REQUIREMENTS:
Identification
Permits
Visitor's agreement
Special problems
Type of communication needed
Telephone
VEHICLE(S) AND EQUIPMENT:
Motor Vehicles
Make
Mobile laboratory
License Plate
Other (list)
Vehicle safety check made? yes no
Boat/Airplane will be used? yes no
List vehicle to be used
Boat/plane safety check made? yes no
ANTICIPATED HAZARDS TO CONSIDER:
Driving distance Biological hazards
Hauling reagents Radiological hazards
Hauling test equipment Noise
Moving hazards Heights
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Thermal hazards Confined space
Chemical hazards Weather
Flammable hazards Terrain
TOXIC SUBSTANCES (LIST):
HAZARD MONITORING EQUIPMENT:
EMERGENCY SIGNALS AND COMMUNICATION:
Fire signal is
Evacuation signal is
Severe weather signal is
Toxic release signal is _
EMERGENCY AND RESCUE:
Is first aid available in the area? yes no
Location Telephone #
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Is ambulance available? on site on call Tel. #
Nearest hospital with emergency services: Location
Telephone #
Heavy and special rescue services/equipment available: Yes/No_
Specify:
PERSONAL PROTECTIVE EQUIPMENT/CLOTHING: (Check if needed)
Eyes and Head
Safety glasses Type
Face shield Goggles
Hard hat Type
Hearing protection Type
Other
Body, Hands, Feet
Coveralls Type
Foul weather gear
Fully encapsulating gear
Safety footwear Type
Boot/shoe covers
Gloves Type
Other special equipment/clothing
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Respiratory Protection
Air-Purifying Respirator Type
Cartridge, Filters Type
SCBA Type
Emergency Escape Mask Type
Airtank Full yes no
Special Health and Safety Equipment
Life belt
Safety line
Other
Decontamination Supplies
Waste bags and ties
Cleaning solution
Disposable brushes
Disposable towels and towelettes
Disposable containment tubs
MISCELLANEOUS
Rope String Tape
Matches Food Additional Clothing
Potable Water
Note:
A copy of this summary should be taken along for reference in the event of an
emergency. A second copy should be filed with a supervisor before leaving for the site.
Such information is particularly important for visits to sites where crews may be stranded
or lost.
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CHAPTER 2
2.0 HAZARDS, EXPOSURE AND EVALUATION
2.1 OBJECTIVE
To provide information regarding general safety considerations,
how exposures to hazardous chemicals may occur, how to assess
these hazards, and how to protect oneself and others.
2.2 INTRODUCTION
Inspectors will encounter a variety of physical, biological, and
chemical hazards during inspections.
Exposure to chemicals is the most common and significant
health hazard field personnel encounter.
Chemicals may be hazardous because they are toxic,
flammable, combustible, explosive, corrosive, reactive,
radioactive, biologically active, or some combination of these
and other characteristics.
Inspectors should learn basic first aid techniques.
2.3 SAFETY GUIDELINES AND TECHNIQUES
Lifting and carrying
Ladders and climbing
Power sources and electrical equipment
Confined spaces
Mechanical hazards
Biological hazards
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Lifting and
Carrying
Ladders and
Climbing
Portable Ladders
Assess the following:
overall weight
distribution of weight
security of contents
distance
obstacles
surface conditions
visibility
Use two people.
Lift with power of leg muscles.
Do not climb ladder with heavy load.
Inspect ladders for hazards.
Position ladder base 1/4 of working length from wall.
Use only ladders with non-skid feet; be sure ladder rests on
non-slip level surface.
Wear appropriate clothing.
Do not use:
step ladders >6 m (20')
straight ladders >9 m (30')
two-section extension ladders > 15 m (48')
three-section extension ladders > 18 m (60')
Face ladder when climbing and descending.
Have someone stabilize bottom.
Do not hand carry anything up the ladder.
Prevent tools and equipment from catching on ladder or
falling.
Do not use ladder as scaffold or bridge.
Do not permit more than one person on ladder.
Do not reposition ladder while on it.
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Fixed Ladders
Working Surfaces
Power Sources/
Electrical
Equipment
Electrical
cords/plugs
Uninsulated
Electrical
Conductors or
Metal Parts
Static Electricity
Mechanical
Hazards
Minimum design load: 91 kg (200 Ibs)
Evenly spaced stepping surface < 30 cm (12")
Adequate clearance
Minimum 18 cm (7") clearance behind each rung
Safety devices or cages: >6 m (20')
Pitch: 75°-90°
Check integrity of elevated platforms before climbing up to
them.
Discontinue inspection if personal safety is jeopardized.
Shut off power where possible.
Remove highly conductive equipment if power cannot be shut
off.
Wear protective gear - hard hats, gloves, etc.
Inspect periodically and repair.
Use three-wire equipment.
Ensure continuity of grounding wire.
Ensure diameter of wires is sufficient to prevent loss of
voltage or overheating.
Ensure exposed metal parts of electrical equipment are
grounded.
Use a Ground Fault Circuit Interrupter (GFCI) in the line.
Use double-insulated power tools.
Sources include:
particulates in process stream
electrostatic precipitators
lightning
Safety precautions:
ground sampling probes
be aware of weather conditions
discontinue sampling where lightning hazard exists
use A.M. radio for weather reports/static interference
Remotely controlled vehicles
Forklifts
Potential entanglements
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Confined Space
See booklet for information on confined space entry.
Biological
Hazards
Ticks
Snakes
Spiders
Bees/wasps
Scorpions
Rabid Animals
Entering certain locations can be hazardous due to the presence of
various biological hazards.
Live in areas with tall grasses, bushes.
Burrow into skin and suck blood.
Transmit Rocky Mountain Spotted Fever, Lyme's Disease.
Wear light-colored clothing; tuck pant legs into socks.
Examine body for presence of ticks.
Seek medical help if fever, rash or bull's eye pattern
develops.
Learn to recognize poisonous varieties.
Wear knee-high, thick, leather boots and leather gloves.
Be aware of their habits.
Bring snake bite kit.
To treat snake bite:
keep victim calm
slow circulation
use snake bite kit
get immediate medical help
Learn to recognize dangerous varieties.
Get medical help for bites as soon as possible.
Tarantula bites are painful but seldom serious.
Recognize their habitats.
Carry bee-sting kit if allergic.
To treat sting:
keep victim calm
remove stinger
cool area with ice
administer cardiopulmonary resuscitation (CPR) if
necessary
seek medical help
Usually found under other objects.
Carry anti-sting kit - sting can be fatal to allergic individual.
Administer CPR if necessary.
Seek medical help if stung.
Can infect any warm-blooded animal (foxes, dogs, bats,
raccoons, skunks, squirrels).
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Micoorgamsms
Animals may exhibit lack of fear, aggressiveness, dropping
head, peculiar trotting gait, unusual behavior.
Seek immediate medical help if bitten by rabid animal;
infection nearly 100% fatal if untreated.
Harmful bacteria, viruses and fungi can be found in soil,
waste water, medical and pharmaceutical waste.
Inspectors should avoid direct contact with these materials.
2.4 HEAT STRESS
Heat production exceeds heat loss.
Often accompanied by increased:
heart rate
body temperature
respiration
perspiration
Adverse effects range from cramps to death.
Contributing factors:
ambient temperature
radiant heat
physical labor
chemical exposure
humidity
altitude
inadequate acclimatization
fatigue
alcohol consumption
cardiac and respiratory conditions
some medications
Preventing/
Reducing Heat
Stress
A92-333.1
Assess probability of heat stress.
Schedule work for cool periods of day.
Take adequate breaks.
Hoist, rather than carry, heavy loads.
Use protective heat shields, insulating materials, reflectors,
tarpaulins.
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Heat Stress
Disorders
Heat Stroke
Symptoms
Emergency
Treatment
Heat Exhaustion
Symptoms
Emergency
Treatment
Drink appropriate amounts and types of fluids: 250 ml (
cup) water every 15 minutes.
Wear head coverings and clothing.
light in color
absorbent
loose fitting
Know the symptoms, prevention and treatment of major
heat stress disorders.
Life-threatening
Sweating mechanism shuts down; body overheats.
Red or flushed skin
Hot, dry skin
Very high body temperature: 41°C (106°F)
Dizziness
Nausea
Headache
Rapid, strong pulse
Unconsciousness
Cool person rapidly - water, fan, air conditioning.
Get immediate medical care.
Allow person to sip water if conscious.
If left untreated, may progress to heat stroke.
Inadequate blood flow and dehydration.
Pale, clammy skin
Profuse perspiration
Extreme fatigue, weakness
Normal body temperature
Headache
Vomiting
Move victim to cooler location.
Have person lie down and elevate feet 20-30 cm (8-12").
Loosen clothing.
Have person drink electrolyte replacement solution or juice if
possible (every 15 minutes for one hour).
Get medical aid if condition does not improve.
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Heat Cramps
Symptoms
Treatment
Muscle pains and spasms (abdomen, legs) caused by loss of
electrolytes.
Painful muscle cramping and spasms
Heavy sweating
Vomiting
Convulsions
Alert, well-oriented, normal pulse and blood pressure
Rest quietly in cool location.
Loosen clothing.
Massage cramped muscle.
Give clear juice or electrolyte replacement solution: 250 ml
(₯i cup) every 15 minutes for one hour.
Get medical help if symptoms not relieved
Recognition of
Hazards
2.5 FIRE AND EXPLOSION HAZARDS
During your field work you may be exposed to fire and explosion
hazards from materials you may be using or encounter.
Recognizing fire and explosion hazards requires an understanding
not only of the types of materials that can catch fire or are reactive
with air or water, but also of the processes by which materials burn
or explode.
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Essential Combustible material (fuel)
Components Oxidizer (oxygen in atmosphere)
Ignition energy (heat)
Combustible Those posing greatest concern are dusts, vapors, and gases that can be
Materials ignited easily and burn rapidly or explosively;
Gases - diffuse and mix readily with oxygen.
Combustible gases - acetylene, ammonia, butane, hydrogen,
methane, propane, etc. - hazard also from containers of
combustible gases.
Solids
Must be converted to gas or vapor before they will burn.
Finely divided may be dangerous (flour, steel wool).
Combustible dusts - agricultural products, wood products,
chemicals, Pharmaceuticals, metals, and plastics.
Liquids
Must be converted to gas or vapor before they will burn.
Sprays, mists, foams, or dispersions.
Combustible liquids - liquids capable of being ignited -
includes flammable liquids.
Flammable liquids - flash point temperatures below 100°F
(38°C) - many industrial chemicals, paints, thinners, solvents,
fuels - containers of these are also hazardous. See Table 2-1.
Ignition Amount needed depends on:
Energy
state and concentration of the combustible material; and
concentration of oxygen.
Sources:
heated metal
sparks
flames
static electricity and sparks
sunlight
lasers
ionizing radiation
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Ignition temperature
Minimum temperature necessary to start the material
burning.
Varies greatly for different materials.
Based on normal concentration of oxygen (21%).
Oxidizer Is usually oxygen in air.
Peroxides, perchlorates, permanganates, sulfuric acid,
chlorine and fluorine may act as oxidizers.
Fire and Many factors contribute to the occurrence of a fire or an explosion.
Explosion
Characteristics
Flammable Flammable concentration: all concentrations at which flame
Concentration and will travel through the mixture.
Flammable Limits
Explosion Limits - range of concentrations of gases in
air which will support the explosive process is bounded
by measurable limits called explosive limits. The
upper explosive limit (UEL) and the lower explosive
limit (LEL) define the parameters of this range.
Limits are measured and published as the percentages
by volume of vapor or gas in air containing the normal
concentration of oxygen. See Table 2-1.
Lower explosive limit (LEL): minimum flammable
concentration of a material - also referred to as the
lower flammable limit (too "lean").
Upper explosive limit (UEL): maximum flammable
concentration of a material - also referred to as the
upper explosive limit (too "rich").
Vapor pressure Pressure of the vapor above the surface of the liquid in a
container; liquids with high vapor pressures are generally
more hazardous than those with low vapor pressures
(temperature dependent). See Table 2-1.
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Flash point
Specific Gravity
Vapor Density
Temperature at which a liquid will give off enough vapor to
allow flame to propagate through the vapor-air mixture;
liquids with low flash points are generally more hazardous.
See Table 2-1.
Most combustible and flammable liquids have specific
gravities less than 1.0 - will float on water; water should not
be used for firefighting.
Greater than 1.0 - will sink in water; water can be used for
firefighting.
If less than 1.0, vapor rises.
If greater than 1.0, vapor sinks.
TABLE 2-1. CHARACTERISTICS OF FLAMMABLE LIQUIDS
Liquid
Vinyl acetate
Acetone
Ethyl alcohol
Methyl ethyl
ketone
Gasoline
Kerosene
Toluene
Trichloroethylene
Xylene
Explosion Limits
(% in air)
2.6 - 13.4
2.6 - 12.8
3.3 - 19.0
1.4 - 11.4 (93°C)
1.4 - 7.6
0.6 - 5.0
1.2 - 7.1
12.5 - 90
1.1 - 7.0
Vapor Pressure
(mm Hg at STP)
115
227
50
71
?
?
30
77
10
Flash Point (°C)
-8
-18
13
-9
-43
38
4
37
29
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Preventing Fire
and Explosions
Identification of
Hazards
Control of
Ignition Sources
Instruments and
Equipment
Control of Static
Electricity
Keep ignition sources away from flammable concentrations.
Limit amount of flammable liquids taken on field activities.
Use available ventilation during transfer of liquids.
Transport flammable liquids in tightly-sealed containers
protected against impact.
Get information from Agency files, co-workers who have
inspected the site, plant personnel.
Identify materials which may be present; read reference
sources to determine hazards; take appropriate precautions.
Use direct-reading instruments to detect flammable
concentrations onsite.
Be aware of sources: matches, cigarette lighters, electrical
switches, electrical equipment, welding sparks, engines.
All electrical equipment, sampling apparatus, portable
instruments, and other possible sources of ignition must be
safe for use in atmospheres containing flammable
concentrations of dusts, vapors or gases.
Most battery-operated or line-powered field instruments are
not safe for use in flammable atmospheres.
If possible, use only equipment approved by Underwriters
Laboratory (UL) or Factory Mutual (FM) for use in specific
flammable atmospheres.
Enclose and ventilate sampling equipment which is not
approved for use in such atmospheres.
Be aware that some monitors which check flammable
concentrations will give false readings if the concentration is
above the upper flammable limit for the material.
Since static electricity (which accumulates to higher voltages in
atmospheres with low humidity and during dry weather) can provide
sufficient ignition energy to set fire to flammable concentrations of
gases and vapors, it is important to recognize what can generate
static electricity and what can be done to prevent accumulation and
discharge of this energy.
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Sources Particulates moving through a stack.
Gas issuing from a nozzle at high velocity.
Pouring or spraying nonconducting liquids or solids.
Materials flowing through pipes, hoses or ducts.
Belt running over a pulley.
Person walking across a floor.
Pouring solvents.
Working near a process that generates static electricity.
Preventing Ground probes used for stack sampling.
Accumulation or
Discharge Provide a bonding connection between metal containers when
flammable gases or liquids are transferred or poured.
Wear footwear with adequate conductivity for the conditions.
2.6 SELECTION AND USE OF FIRE EXTINGUISHERS
Fire is an oxidation process which requires three key components:
fuel, oxygen, heat. Removal of any of these three will stop the
oxidation process.
Fire Classifi- See Table 2-2.
cation/ Treatment
Fire Extinguisher See Table 2-3.
Identification
Firefighting Warn others to evacuate area.
Precautions Call Fire Department.
Evaluate ability to fight the fire.
proper type and size of extinguisher?
additional help?
obstacles?
retreat?
Contain the fire to prevent spread.
Fight the fire.
Never turn your back on the fire.
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Using a Fire
Extinguisher
Fire Hose
Soda-add
Aqueous-charged
Dry Chemical
Liquid CO2
Foam
Prepare and test extinguisher before approaching fire.
Aim at base of fire.
Stream reaches about 9 m (30').
Stand back so pressure does not scatter fire.
Turn upside down to mix chemicals and start flow.
Spread stream into fan-shape with finger if pressure is not
too great.
Usually rated "B" and "C"; some are rated "A", "B", and "C".
Use side-to-side sweeping motion.
Cover Class A fire.
Start spraying Class B fire at closest edge and continue
to far edge; do not get too close.
Low velocity discharge of CO2; need to get within 2 to 4 feet
of fire.
Flow of gas generates extreme cold and static electricity.
Aqueous foam.
Effective on Class A or B fires.
Works well on fairly large fires.
hlthsfty eng
2-13
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TABLE 2-2. FIRE CLASSIFICATION AND EXTINGUISHING MEDIA
Class
A
B
C
D
Description
ordinary
combustibles
flammable or
combustible liquid
or gases
electrical
equipment
combustible metals
that burn vigorously
and react violently
with water
Examples
wood, paper, cloth,
rubber
gasoline, fuel oil,
kitchen grease,
alcohol, propane
electrical
equipment
Na, K, Mg, Ti, Zi
Extinguishing
Media
water, Halon 1211,
baking soda
CO2, dry
chemicals, foam,
Halon 1211, Halon
1301
dry chemicals,
CO2, Halon 1211,
Halon 1301
dry powders
(graphite, NaCl,
other free-flowing
noncombustible
materials
TABLE 2-3. FIRE EXTINGUISHER IDENTIFICATION
Class Type
A
B
C
Symbol Description
Burning wastebasket and bonfire
Container pouring liquid and a fire
Electrical plug and a receptacle with
flames
httbsftyeng
2-14
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2.7 CHEMICAL HAZARD RECOGNITION AND EVALUATION
Physical
Classification
Solids
Liquids
The degree of hazard associated with a particular chemical
will depend on its toxicity, the way it is used and the
environment in which it is encountered.
The following factors must be considered in evaluating the
degree of hazard present:
physical form or classification of the chemical
physical and chemical characteristics of the chemical
warning properties
airborne concentration
mode of usage
other environmental conditions
Solids
Liquids
Aerosols
Gases and vapors
Particulates (lead, asbestos)
Sensitization (Ni)
Fumes
Sublimation
Reactivity
Degree of hazard depends on characteristics of the liquid
and how it is used
Factors influencing hazard include:
temperature
vapor pressure
toxicity
Types of hazards
skin damage
direct absorption through skin
enhanced absorption of other chemicals
splash hazard
slipping hazard
reactivity
hllhsfty.eng
2-15
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Aerosols
Gases and Vapors
Physical and
Chemical
Characteristics
Aerosols are fine particulates (solid or liquid) suspended in
air (dust, fumes, mist, fog, smoke and smog).
See Table 2-4 for characteristics of air contaminants in work
places.
Results may present inhalation, eye or skin hazards.
A gas is a state of matter in which the material has very low
density and viscosity.
Vapors are the evaporation products of chemicals that are
normally liquid at room temperature.
See Table 2-4 for gas/vapor characteristics.
Gases and vapors may present inhalation, eye and skin
hazards.
Boiling point - temperature at which liquid changes to a gas.
Melting point - temperature at which a solid changes to a
liquid.
Vapor pressure pressure of vapor immediately above the
surface of a material. Term generally applied to liquids;
however, solids have vapor pressure as well. Materials with
high vapor pressure can create high airborne exposure risks.
Solubility - maximum amount of that substance that will
completely dissolve in a given volume of another substance.
Flash point - lowest temperature at which a liquid gives off
enough vapor to form an ignitable mixture with air and
produce a flame when an ignition source is present.
Flashpoint and boiling point are used to determine the
classification of flammable liquids.
Explosion Limits - range of concentrations of gases in air
which will support the explosive process is bounded by
measurable limits called explosive limits. The upper
explosive limit (UEL) and the lower explosive limit (LEL)
define the parameters of this range. The concentration is
generally expressed in percent gas in air.
Mthsftyeng
2-16
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TABLE 2-4. CHARACTERISTICS OF AIR CONTAMINANTS IN WORK PLACES
Form
How Generated
Example/Size
(micrometers)
Concentration
Expressed As
Aerosols
Dust
Fumes
Mist
Smoke
Gases and Vapors
Gases
Vapors
From solids by
mechanical means:
- grinding
- blasting
- drilling
Condensation
products of metals
and solid organics,
welding on metal
Liquid droplets
formed by atomizing
liquids or
condensing liquids
from vapors,
entrainment
Products of
combustion of
organic materials
Occupy space of
enclosure, liquify
only under increased
pressure and
decreased
temperature
Evaporation
products of
substances normally
liquid at room
temperature
(solvents, gasoline).
Quarry dust (less
than 1 to 10)
Lead fume (less than
0.001 to 0.1)
Chromic acid mist
mg/m3(
mg/m3
mg/m3
Incinerator (less
than 0.5)
CO
mg/m3
ppm1'
Acetone
Carbon disulfide
Benzene
ppm
(1) mg/m3 - milligrams per cubic meter.
(2) ppm - parts of gas or vapor per million parts of air.
Uthsfty eng
2-17
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Warning
Properties
Odor Threshold
Eye, Nose and
Throat Irritation
Taste
Airborne
Concentration
Reactivity - refers to the likelihood of reacting, rather than
the ability to react. Most chemicals will react with some
other chemical given the right set of conditions.
May include odor, eye, nose or throat irritation and taste.
To be useful in preventing overexposure, must be evident at
a concentration below the permissible exposure limit (PEL).
Some chemicals have good warning properties (NH3) while
others have none at all (CO).
Odor threshold is airborne concentration at which a chemical
can be detected by smell.
Individuals vary.
Useful odor thresholds are well below the PEL. (NH3)
Useless odor threshold is well above PEL. (vinyl chloride)
Olfactory fatigue may influence recognition of hazard. (H2S)
PELs for many chemicals have been based on irritation when
it has been demonstrated that toxic effects are produced only-
by substantially higher concentrations. (HC1)
May be useful if a taste is produced at concentrations below
the PEL. (saccharin)
Since some chemicals do not have adequate warning
properties and because individuals vary in their sensitivities
to various substances, measurement of airborne
concentrations of chemicals may prove to be useful.
If the potential for chemical exposure is unknown you should
not enter the area unless you are properly protected or until
the chemicals have been identified and the concentrations
reliably measured or estimated.
If you find yourself in an area where an unknown exposure or
spill occurs, or where you begin to experience signs or
symptoms of exposure (headache, eye irritation, etc.), leave
the area at once.
hlthsfty.eng
2-18
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Chemical Use Degree of hazard is significantly influenced by the way a
chemical is used.
open tanks, hot chemicals, high vapor pressure, poorly
designed or malfunctioning ventilation system = high
airborne concentration
closed system = lower airborne concentrations
Other Temperature.
Environmental Relative humidity.
Factors
2.8 EFFECTS OF TOXIC CHEMICALS IN THE BODY
Toxic chemicals can affect the body in different ways, depending on
the combination of several factors:
Route of entry.
Length of exposure.
Organs or systems affected.
Absorption, distribution, storage, and elimination.
Routes of Entry Chemical substances may enter the body through the skin,
respiratory tract and gastrointestinal tract.
Exposures during field activities are most likely to occur
through skin contact or inhalation.
Skin Usually effective barrier for protecting underlying body
tissues (see Figure 2-1).
Short exposures to strong concentrations of extremely toxic
substances (e.g., organic phosphates, phenol, cyanide) can be
serious or fatal.
Potential effects of No reaction - skin acts as effective barrier
chemical contact Skin irritation or destruction of tissue
Skin sensitization
Chemical penetrates skin and enters blood stream
hlthsfty-eng 2-19
-------
hair shaft
nerve ending
(pair, receptor)
perspiration
pcre
farty layer. /
(subcutaneous)\
capillaries
muscle
oil gland
nerve ending
(pressure
receptor)
sweat gland
Sf'^SS^P^- blood vessels
\ V
connective tissue hair follicle /atcells
Figure 2-1. Skin cross-section
2-20
-------
Factors
influencing effects
Respiratory System
Skin thickness
Chemical properties
Skin condition
Duration of exposure
Most common route of entry for gases, vapors and airborne
particulates (see Figure 2-2).
Major factors influencing the toxic effects of airborne
chemicals include:
concentration in ambient air
physical and chemical properties
sites of deposition within respiratory system
body's ability to counteract effects
septum o(
nasal co»i!y
rrcuth cavity
epiglottis
larynx
esophagus
trachea
right lung
(micaie
lorje] \
\ trachea ":--
escphajj'js ' . ..-'"
rv~~^-L abdominal
\ \ covity
Figure 2-2. Organs of the human respiratory system
hlthsl'ty.cng
2-21
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Damaging Asphyxiants - gases which can deprive body tissues of oxygen.
substances
simple asphyxiants - displace oxygen and lead to
suffocation (N2, He, CH4, Ne, AT)
chemical asphyxiants - prevent oxygen utilization by
chemical interaction (H2S, CO, HCN)
Irritants - may produce inflammation of the sinuses, throat,
bronchi, and alveoli. Cell death may result, leading to edema
and secondary infection. May cause increased pulmonary
flow resistance. Examples: O3, HF, NH3, SOX.
Fibrosis producers - kill normal lung tissue and produce scar
tissue which may result in oxygen deprivation. Examples:
silicates, asbestos, beryllium.
Allergens - substances that act as an antigen upon contact
with body tissues (inhalation, ingestion, or skin absorption).
Allergens may cause allergic response in the form of
bronchoconstriction and pulmonary disease. Examples:
isocyanates, sulfur dioxide.
Carcinogens - substances that cause cancerous growth in
living tissues, such as the lungs. Examples: coke oven
emissions, asbestos, and arsenic.
Systemic Toxicants - substances that enter via the respiratory
tract, but affect other parts of the body. Examples: organic
solvents, anesthetic gases, lead, and mercury.
Table 2-5 gives a partial list of industrial toxicants that produce
respiratory tract disorders.
Gastrointestinal Chemicals may have a toxic effect on all major and accessory
System organs (e.g., liver) of the gastrointestinal tract.
Potential means of Mouth pipetting
ingestion Contaminated water or food
Contaminated smoking materials or cosmetics
Contaminated hands
Drinking from contaminated containers
Utbsftyeng 2-22
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Length of
Exposure
Acute Exposures
and Effects
Chronic
Exposures and
Effects
Organs and
Systems Affected
Toxic chemicals may affect the body in different ways, depending
not only on the route of exposure but also on the length of
exposure. Toxic effects may be produced by acute or chronic
exposure to chemical agents.
Acute, or short-term, exposures to some chemicals can cause:
acute effects (sudden onset, short duration)
permanent adverse effects
delayed effects (temporary or permanent)
chronic effects
You may not be aware of an acute exposure unless there is
an immediate reaction (pain, irritation).
Repeated or prolonged exposure to low concentrations of
some toxic chemicals can cause adverse effects of long
duration or frequent reoccurrence.
Many toxic substances are associated with specific toxic
effects on one or more organs or systems, which suggests that
there is a selective mode of action for many hazardous
substances. While chemical substances may have a broad
range of toxic effects on an organism, the effects are
sometimes so specific that they are defined in terms of the
most susceptible "target cell" or "target organ."
Eight other major organs or systems are frequent sites of
toxic response to chemical substances (see Table 2-6).
bttbsftyeng
2-23
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TABLE 2-5. INDUSTRIAL TOXICANTS THAT PRODUCE DISEASE OF THE
RESPIRATORY TRACT
Toxicant
Aluminum
Ammonia
Arsenic
Asbestos
Beryllium
Boron oxide
Cadmium oxide
Carbides of
tungsten, titanium,
and tantalum
Chlorine
Chromium VI
Site of Action
Upper airways
Upper airways
Upper airways
Lung tissue
Alveoli
Alveoli
Alveoli
Upper, lower
airways
Upper airways
Nasopharnyx, upper
airways
Acute Effect
Cough, shortness of
breath, irritation
Irritation
Bronchitis irritation,
pharyngitis
Edema, Pneumonia
Edema, hemorrhage
Cough, pneumonia
Hyperplasia,
metaplasia of
bronchial cells
Cough, irritation,
asphyxiant
Nasal irritation,
bronchitis
Chronic Effect
Fibrosis and
emphysema
Bronchitis, edema
Cancer, bronchitis,
laryngitis
Fibrosis, cancer
Fibrosis, ulceration
Emphysema
Fibrosis
Cancer
Cobalt
Lower airways
Asthma
Fibrosis, interstitial
pneumonitis
Hydrogen chloride
Iron oxides
Isocyanates
Manganese
Nickel
Upper airways
Alveoli, bronchi
Lower airways,
alveoli
Lower airways
alveoli
Nasal mucosa,
bronchi
Irritation, edema
Cough
Bronchitis,
pulmonary edema,
asthma
Pneumonia, often
fatal
Irritation
Benign
pneumoconiosis
Recurrent
pneumonia
Cancer
hltbsfty eng
2-24
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TABLE 2-5 (CONTINUED)
Toxicant
Nickel carbonyl
Nitrogen oxides
Osmium tetraoxide
Ozone
Phosgene
Phthalic anhydride
Sulfur dioxide
Site of Action
Alveoli
Bronchi, alveoli
Upper airways
Bronchi, alveoli
Alveoli
Lower airways,
alveoli
Upper airways
Acute Effect
Edema (delayed
symptoms)
Edema
Bronchitis,
bronchospasm
Irritation, edema,
hemorrhage
Edema
Bronchitis, asthma
Bronchoconstriction,
cough, tightness in
Chronic Effect
Emphysema
Bronchopneumonia
Emphysema,
bronchitis
Bronchitis, fibrosis,
pneumonia
Emphysema
Bronchitis,
nasopharyngitis
Tin
chest
Bronchioles, pleura
Widespread mottling
of x-ray without
clinical signs (benign
pneumoconiosis)
Toluene
Vanadium
Xylene
Upper airways
Upper, lower
airways
Lower airways
Bronchitis, edema,
bronchospasm
Irritation, nasal
inflammation, edema
Edema, hemorrhage
Bronchitis
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2-25
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TABLE 2-6 ORGANS/SYSTEMS AFFECTED BY CHEMICAL EXPOSURE
Organs or System
Chemicals Causing Effects
Liver and Bile Ducts
(Hepatic System)
Kidney (Renal System)
Blood and the Blood-
forming System
(Hematopoietic System)
Heart, Cardiovascular
System (CVS)
Neuroendocrine System
Immune/Allergy System
Central Nervous System
(CNS)
Vinyl Chloride, Aromatic
Hydrocarbons
Heavy Metals, Halogenated
Hydrocarbons
Benzene, Lead
Carbon Monoxide, Arsine
DDT
Triphenyltin
Pesticides, Thallium
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2-26
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2.9 DOSE-RESPONSE CURVES
A dose-response curve describes the relationship between the absorbed dose
(concentration versus time) and the biological response. The threshold limit value
(TLV) is that dose below which no significant effect is expected to occur. At higher
doses certain effects may be observed which compensate for the toxic effect. At still
higher doses, reversible damage to organs may be observed. This damage may become
irreversible at sustained or higher levels. As this dose increases to even more toxic
levels, death will occur. The shape of the curve will depend on the lexicological
properties of the material. See Figures 2-3, 2-4, and 2-5 for representative dose-response
curves.
Response
t
Dose
Threshold
Limit
Value
Death
Irreversible
Effects
Figure 2-3. Classic Dose-response Curve.
hllhslty cng
2-27
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Response
t
Dose
Irreversible
Effects
Death
Compensation
Figure 2-4. Dose-response Curve for a Chemical with no TLV.
Response
Threshold
Limit
Value
Reversible
Effects
Compensation
Dose
Irreversible
. Effects
Death
Figure 2-5. Dose-response Curve fora Highly Toxic Chemical.
2-28
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Types of Effects
Harmful Effects
Sensitization Effects
Some chemicals do not elicit such dose-response relationships.
Include toxic and lethal effects
Result from overexposure or overdose
Three major classes:
non-specific corrosive - irreversible damage to cells
and tissues, (strong acids, bases, oxidants)
specific toxicologies! effects - effects on specific target
organs or systems - usually reversible if recognized
early. (CC14 liver cell damage, HCN asphyxiation)
pathological effects - chronic, usually irreversible.
(cancer, mutations, birth defects)
Not dose-dependent
Require preconditioning exposure
Immune system affected
Allergic and hypersensitivity reactions (Ni, nitrophenols,
isocyanates, formaldehyde, etc.)
Factors
Influencing
Intensity of Toxic
Action
Route of Entry
Age
State of Health
Previous Exposure
Intensity and nature of response depends on route of
exposure: lead (inhalation vs. ingestion).
Intensity also related to the acute and chronic toxicity of a
substance: hydrogen sulfide.
Infants, children, adults, and senior citizens differ in their
circulatory and excretory systems, musculature and
metabolisms which affect the distribution and toxicity of
substances: newborns (CNS stimulants/suppressants).
Pre-existing disease may increase sensitivity to toxic agents.
Nutrition may affect responses.
Diet can change body composition, physiological and
biochemical functioning.
Tolerance
Increased sensitivity
No effect
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2-29
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Environmental
Factors
Host Factors
Temperature
Barometric pressure
Radiation
Species
Sex
Hereditary factors
2.10 EVALUATING HEALTH HAZARDS AND TOXICITY INFORMATION
Reasons to Seek
Information
Exposure Limits
Skin Contact and
Ingestion Exposure
Inhalation
Exposure Limits
Does a hazard exist?
What degree of risk?
Is air monitoring needed?
Can pre-exposure monitoring be done?
Can personal monitoring be done during the activity?
Should possible exposures be documented by medical
monitoring?
What specific protective equipment and clothing are
necessary?
How should one use such equipment and clothing?
Limits on skin contact
Permissible Exposure Limits (PELs)
Most industrial chemicals required to have precautionary
labels.
Skin and systemic toxicity information provided.
Threshold Limit Values (TLVs) - reviewed and adopted
annually by the American Conference of Governmental
Industrial Hygienists (ACGIH) - advisory, but more up-to-
date.
Permissible Exposure Limits (PELs) - adopted by the
Occupational Safety and Health Administration (OSHA) -
mandated.
hllbsfiyeng
2-30
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Categories of Time-Weighted Average (TWA) - concentration of a toxic
Exposure Limits substance to which nearly all workers may be repeatedly
exposed without adverse effect - based on eight-hour
workday, 40-hour workweek.
Short-Term Exposure Limit (STEL) - 15-minute time-
weighted average exposure which shall not be exceeded at
any time during a work day.
Ceiling (C) - concentration that should not be exceeded
during any part of the working day.
Important PELs do not represent a fine line between safe and
Information dangerous.
PELs may not be appropriate for extended shiftwork.
PELs may not protect all workers.
PELs are not a relative index of toxicity.
PELs are based on the best available information.
Signs and Since you may not know the identity of toxic chemicals to which you
Symptoms of are-being exposed, and many chemicals have inadequate warning
Overexposure properties, you must be aware of signs and symptoms of
overexposure.
Signs - observable by others
Symptoms - not observable by others
Signs of Sneezing
Inhalation Coughing
Exposure
Symptoms of Headache
Inhalation Dizziness
Exposure Nausea
Irritation of eyes, nose, throat
Increased mucus in nose and throat
Signs of Redness
Skin Contact Swelling
Dry, whitened skin
hlthsfty.eng 2-31
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Symptoms of
Skin Contact
Other Signs
and Symptoms
Evaluating
Exposure with
Instrumentation
Preparing for
Field Use of
Equipment
Charactenslics of
Air Monitoring
Instruments
Quantification of
Airborne
Contaminants
Irritation
Itching
Changes in behavior
Periods of dizziness
Muscle spasms
Irritability
Air monitoring instrumentation provides the most reliable means of
identifying and quantifying airborne contaminants. Information may
be used to help:
Determine level of worker protection needed;
Evaluate the level of exposure and, therefore, the health risk
to field personnel and the need for medical monitoring;
Assess potential environmental effects; and
Provide indicators of the effectiveness of hazard abatement
activities.
Once the appropriate equipment has been selected:
Read all instructions.
Practice using the equipment.
Calibrate the equipment before and after using it.
Portable.
Able to generate reliable and useful data.
Sensitive and selective.
Inherently safe.
Direct-reading instruments (See Table 2-7)
Flammable or explosive atmospheres
Oxygen deficiency
Certain gases and vapors
Ionizing radiation
hlthsfty eng
2-32
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TABLE 2-7. SOME DIRECT-READING INSTRUMENTS
Instrument
Application
Limitations
Combustible Gas
Indicator (CGI)
Flame lonization
Detector (FID) with
Gas
Chromatography
Option
Gamma Radiation
Survey Instrument
Portable Infrared
(IR) Spectrophoto-
meter
Measures the
concentration of
combustible gas or
vapor
In survey mode,
detects the total
concentrations of
many organic
gases and vapors.
In gas
Chromatography
(GC) mode,
identifies and
measures specific
compounds. In
survey mode, all
the organic
compounds are
ionized and
detected at the
same time. In GC
mode volatile
species are
separated.
Gamma radiation
monitor
Measures
concentration of
many gases and
vapors in air.
Designed to
quantify one- or
two-component
mixtures.
Accuracy depends, in part, on the difference between
the calibration and sampling temperatures. Sensitivity
is a function of the differences in the chemical and
physical properties between the calibration gas and
the gas being sampled. The filament can be damaged
by certain compounds such as silicones, halides
tetraethyl lead and oxygen-enriched atmospheres.
Does not provide a valid reading under oxygen-
deficient conditions.
Does not detect inorganic gases and vapors or some
synthetics. Sensitivity depends on the compound.
Should not be used at temperatures less than 40°
F(4°C). Difficult to absolutely identify compounds.
High concentrations of contaminants or oxygen-
deficient atmospheres require system modification. In
survey mode, readings can only be reported relative to
the calibration standard used.
Does not measure alpha or beta radiation.
In the field, must make repeated passes to achieve
reliable results. Requires 115-volt AC power. Not
approved for use in a potentially flammable or
explosive atmosphere. Interference by water vapor
and carbon dioxide. Certain vapors and high moisture
may attack the instrument's optics which must then be
replaced.
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2-33
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TABLE 2-7 (CONTINUED)
Instrument
Application
Limitations
Ultraviolet (UV)
Photoionization
Detector (FID)
Direct-Reading
Colorimetric
Indicator Tube
Oxygen Meter
Detects total
concentration of
many organic and
some inorganic
gases and vapors.
Some
identification of
compounds is
possible if more
than one probe is
used.
Measures
concentrations of
specific gases and
vapors. Available
for a wide variety
of chemicals.
Measures the
percentage of O2
in air.
Does not detect methane. Does not detect a
compound if the probe used has a lower energy level
than the compound's ionization potential. Responses
may change when gases are mixed. Other voltage
sources may interfere with measurements. Readings
can only be reported relative to the calibration
standard used. Response is affected by high humidity.
The measured concentration of the same compound
may vary among different manufacturers' tubes.
Many similar chemicals interfere. Greatest sources of
error are (1) how the operator judges stain's end-
point, and (2) the tube's limited accuracy. Affected
by high humidity.
Must be calibrated prior to use to compensate for
altitude and barometric pressure. Certain gases,
especially oridants such as ozone, can affect readings.
Carbon dioxide (COj) poisons the detractor cell.
Source: NIOSH/OSHA/USCG/EPA Occupational Safety and Health Guidance Manual for Hazardous
Waste Site Activities
hlthsfty.eng
2-34
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Laboratory analysis of air samples
Anions
Aliphatic amines
Asbestos
Metals
Organics
Nitrosamines
Particulates
PCBs
Pesticides
2.11 REFERENCES
Some sources which can provide information concerning the toxicity
and other potential hazards of chemicals are listed below.
Airborne
Exposure Limit
Information
Occupational Safety and Health Administration (OSHA) -
Permissible Exposure Limits (PELs) can be found in 29 CFR
1910 Subpart Z.
National Institute for Occupational Safety and Health
(NIOSH).
Recommended exposure limits (RELs) can be found
in criteria documents available from NIOSH, the
National Technical Information Service (NTIS), or, in
some cases, the EPA
Pocket Guide to Chemical Hazards - provides useful
information on regulated chemicals: PELs, TLVs,
RELs and data regarding synonyms, IDLH levels,
physical description, chemical and physical properties,
incompatibilities, measurement methods, personal
protection, respirator selection and health hazards.
Single copies available from NIOSH at no charge.
American Conference of Governmental Industrial Hygienists
(ACGIH) - Threshold Limit Values (TLVs) are reviewed
periodically and the TLV list published annually - available
from ACGIH Publications Office, 6500 Glenway Avenue,
Building D-7, Cincinnati, OH 45211-4438.
hlthsfty eng
2-35
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Material Safety
Data Sheets
Other Sources
OSHA Hazard Communication Standard requires all
chemical manufacturers and vendors to provide material
safety data sheets (MSDSs) for the products that they sell.
MSDSs contain information concerning:
hazardous ingredients
physical and chemical characteristics
acute and chronic health hazards
respiratory protection and ventilation requirements
fire and reactivity data
spill control measures
disposal requirements
labeling requirements
other requirements relevant to the safe use of the
product
Employers are responsible for obtaining or developing an
MSDS for each hazardous substance used in their workplaces
and ensuring that employees have access to this information.
NIOSH/OSHA Occupational Health Guidelines for Chemical
Hazards, U.S. Government Printing Office, Washington, DC
20402
Documentation of the Threshold Limit Values (TLVs),
ACGIH Publications Office, 6500 Glenway Avenue, Building
D-7, Cincinnati, OH 45211
CHRIS: Chemical Hazard Response Information System -
available through the National Response Center - Volume 2 -
information on hazardous waste spills and dump site cleanup.
Fire Prevention Guide on Hazardous Materials, seventh
edition, National Fire Protection Association (NFPA),
Quincy, MA 02269 - information on pure chemicals; very
little on mixtures.
The Merck Index, 10th edition (1983), Merck and Company,
Inc., Rahway, NJ 07065 - information on chemicals, drugs,
and biological substances.
bltbsflyeng
2-36
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Dangerous Properties of Industrial Materials, (current
edition), edited by N. Irving Sax, Von Nostrand Reinhold
Co., 135 W. 50th Street, New York, NY 10020 - information
and technical data on nearly 13,000 industrial and laboratory
chemicals.
Condensed Chemical Dictionary, 10th edition (1981), Gessner
G. Hawley, Von Nostrand Reinhold Co., 135 W. 50th Street,
New York, NY 10020 - concise, descriptive technical data on
thousands of chemicals and reactions.
Farm Chemicals Handbook, (1984), Richard T. Meister,
editorial director, Meister Publishing Co., 37841 Euclid
Avenue, Willoughby, OH 44094 - annual publication listing
information regarding pesticides and products.
NIOSH Registry of Toxic Effects of Chemical Substances,
(RTECS), 1980 edition, U.S. Department of Health and
Human Services, Public Health Service, Centers for Disease
Control, NIOSH, Cincinnati, OH 45226, or Government
Printing Office, Washington, DC - contains toxicity data on
nearly 40,000 chemicals and lists over 145,000 chemical
substances.
1984 Emergency Response Guidebook: Guidebook for
Hazardous Materials Incidents, 1984, U.S. Department of
Transportation, Materials Transportation Bureau, DMT-11,
Washington, DC 20036.
Emergency Handling of Hazardous Materials in Surface
Transportation, 1981, Bureau of Explosives, Association of
American Railroads, 1920 L Street, NW, Washington, DC
20036.
Handbook of Toxic and Hazardous Chemicals, 1981,
Marshall Sitting, Noyes Publications, Noyes Building, Park
Ridge, NJ 07656.
Toxic and Hazardous Industrial Chemical Safety Manual,
1982, International Technical Information Institute - available
through Laboratory Safety Supply, P.O. Box 1368, Janesville,
WI 53547-1368, and others.
hlthsfty.eng 2-37
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Data bases available to EPA personnel:
OHMTADS: Oil and Hazardous Materials Technical
Assistance Data System (developed by EPA)
HMIS: Hazardous Materials Information System
(developed by DOD, Defense Logistics Agency,
Defense General Supply Center, Richmond, VA
23297
MEDLARS
TOXLINE
TOXBACK
TOXBACK/65
2.12 EMERGENCY FIRST AID FOR FIELD ACTIVITIES
Since employees engaged in field activities are often in remote,
unaccessible areas, it is essential that they know the basics of
emergency first aid.
Every field team should have at least one member with current
training in first aid, cardiopulmonary resuscitation (CPR) and
chemical splash treatment.
Each employee should carry a wallet card with important medical
information such as blood type, allergies, current medication and
physical impairments.
The following information is very basic and does not take the place
of a first aid or CPR course. You should obtain more information
on each of the medical emergencies mentioned. The information in
this section is derived from two publications: American Red Cross:
Adult CPR and American Red Cross: Multimedia Standard First Aid.
Planning to Urgent care essential:
Provide First
Aid or Urgent - severe bleeding
Care - breathing has stopped
no pulse
hlthsBy-eng 2-38
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Preplanning
Complete a Medical Emergency Planning Checklist:
Initial
Response
Providing
First Aid or
Urgent Care
Obstructed
Airway
Conscious Person
location of nearest medical facility
emergency communication and transportation
available
risks involved in field activities
exact location of field activity
identification of first aid/urgent care providers in the
crew
Ensure that crew members complete and carry medical
information card.
Gather first aid/urgent care supplies.
Assess and prioritize treatment (breathing, bleeding).
Request help or secure transportation for victim.
Make a prompt rescue.
Ensure breathing/pulse.
Control severe bleeding.
Protect victim from unnecessary manipulation/disturbance.
Avoid or overcome chilling.
Determine injuries or cause for sudden illness.
Examine victim methodically.
Carry out appropriate first aid.
Follow specific procedures for the following:
obstructed airway
adult rescue breathing
CPR
electrical shock
wounds (severe bleeding) and shock
specific injuries to head, neck and back
chemical splashes, inhalation of toxic gas and burns
drowning
heat stress
Determine whether the person is choking (ask him!).
Have another person request medical assistance.
Perform "Heimlich Maneuver".
hlthsfty.eng
2-39
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Unconscious
Person
Adult Rescue
Breathing
Procedure
hltbsfly.eng
If you are choking, perform Heimlich Maneuver using fist or
back of chair.
Request help.
Position person on back.
Open airway.
Look, listen and feel for breathing.
Attempt to give two full breaths.
If unsuccessful, retilt head and try again.
If still unsuccessful, perform abdominal thrusts and finger
sweep to clear obstruction.
May be required due to:
allergic reactions
electric shock
oxygen-deficient atmosphere
toxic gas paralysis
obstructed airway
Check for consciousness, breathing and pulse.
Have someone get medical assistance.
Position victim onto back.
Open airway.
Check again for breathing (listen, watch chest and feel for
breath).
Give two full breaths.
If still not breathing, reposition head.
Try again.
Perform Heimlich Maneuver if airway is blocked.
2-40
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Cardiopubnonary
Resuscitation (CPR)
Electrical
Shock
Wounds
(Severe
Shock)
Check carotid pulse.
Begin rescue breathing.
one breath every five seconds (approximately 1 to l!/2
seconds/breath)
listen and feel for breath, watch chest
Recheck pulse after one minute of rescue breathing.
Continue rescue breathing until:
victim breathes;
another rescuer takes over;
emergency personnel arrive;
you can't continue.
Chest compressions and rescue breathing used together (15
compressions/two breaths).
May be needed for:
heart attack (most common)
electrical shock
chemical exposure
CPR should be administered only by personnel specially
trained in the procedure.
Can stop breathing and heart or cause heart to beat
ineffectively.
If victim still in contact with source of electricity:
shut off power; or
safely move victim away from source.
Determine need for rescue breathing/CPR.
Stop bleeding.
Protect wounds from contamination.
Prevent shock.
Get medical help.
hlthsfty.eng
2-41
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Severe
Bleeding
Shock
Head, Neck,
Back Injuries
Head, Neck
Back
Chemical
Splashes
Direct pressure/elevation.
Pressure points.
Tourniquet (sacrifice the limb!)
Comfort, quiet, soothe victim.
Keep victim lying down, normal temperature.
Standard position - feet and injury elevated.
If head wound or breathing difficulty, elevate head and
shoulders.
If fractures suspected and not splinted, or elevation is painful,
keep victim flat on back.
Bleeding from mouth, nauseous, vomiting - lie on side.
Signs of injury:
bumps, bruises, cuts
headache
dizziness
unconsciousness
unequal pupils
sleepiness
bleeding/fluid - mouth, nose, ears
paralysis
Sometimes difficult to decide - suspect injury whenever an
accident involves force.
Keep injured head, neck, spine from moving.
Keep victim lying flat (raise head, shoulders), monitor
breathing, get medical help, do not administer stimulants.
Handle victim carefully.
Administer rescue breathing without repositioning.
Flush chemicals off as quickly and thoroughly as possible (15
minutes).
hllhsfiy.eng
2-42
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Splashes of hot, concentrated or corrosive chemicals (several
hours).
Medical followup where indicated.
Eyes Irrigate thoroughly (15 minutes).
Contact lenses may aggravate chemical burns.
Do not use neutralizing solutions.
Skin Remove contaminated clothing.
Wash affected skin thoroughly.
Be aware of potential spread of contaminant.
Try to find water source whose temperature can be adjusted
for prolonged washing.
If victim is conscious, give plenty of non-alcoholic liquids to
drink.
Inhalation of Get exposed person out of toxic atmosphere.
Toxic Gas
If a toxic liquid has been splashed on victim's face, wash it
off quickly.
Administer rescue breathing.
Continue until normal breathing is restored or a resuscitator
is available.
Treat for shock.
Bums Can be life-threatening depending on location and amount of
body affected.
If bum results from chemical splash, first treat for splash,
then burn.
Stop, drop, roll.
Major objectives:
relieve pain
prevent contamination
reduce likelihood of shock
Cooling and aspirin help relieve pain.
hlthsfty.eng 2-43
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Small Shallow
Bums
Large Shallow
Bums
Deep Bums
Shock Prevention
Insect Stings
and Allergic
Reactions
Drowning
Use cool water directly on burn on unbroken skin; immerse if
possible.
Pat dry with sterile gauze.
Bandage if necessary.
Cool with water until pain subsides.
Dry gently and cover with thick, dry, sterile dressing.
Use insulated cold packs over dressing if helpful.
Do not put water on open burn to cool it.
Cover burn with thick sterile dressing and bandage.
Do not remove clothing which is sticking to a burn.
Use dry, insulated cold packs to relieve pain.
Seek medical assistance for extensive deep burns.
Have victim lie down.
Elevate burned areas (if possible).
Maintain normal body temperature.
Have victim drink water is possible.
Ensure adequate airway.
Remove stinger.
Use emergency kit.
Obtain medical attention.
Unless trained in lifesaving, do not attempt personal rescue;
use boat, life preserver, etc.
Begin rescue breathing as soon as possible.
Use proper technique to move or lift victim with suspected
head, neck or back injury.
Administer rescue breathing and CPR for lengthy time to
victim of cold water drowning: <21°C (70°F)
Victim may vomit.
hlthsfiyeng
2-44
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CHAPTER 3
3.0 PROTECTIVE CLOTHING AND EQUIPMENT
3.1 OBJECTIVE
To provide general information on selecting and using appropriate
personal protective clothing and equipment.
SELECTION OF PERSONAL PROTECTIVE CLOTHING
AND EQUIPMENT (PPE)
General
Precautions
Head Protection
Eye and Face
Protection
Proper selection of PPE requires a thorough understanding of the
hazards to be faced:
Chemical - inhalation, skin contact
Mechanical - falling objects, moving parts
Physical - noise, radiation
Thermal - heat, cold
Electrical
Use the correct type of equipment needed.
Use only properly fitting personal protective equipment.
Essential where there are overhead hazards (platforms,
scaffolding, piping)
American National Standards Institute (ANSI) standard:
impact of 400 foot-pounds and insulation against 2,200 volts.
Adjust suspension harness so there is 3 cm (1") clearance
between hat and top of head.
Can be equipped with insulation and chin strap.
Store properly.
Use whenever there is danger of flying or falling particles or
chemical splashes.
Use eye and face protection which meets ANSI Z87.1-1981
standards and OSHA requirements.
hlthsfty eng
3-1
-------
Foot Protection
Impact
Penetration
Chemicals
Ankle Twists and
Sprains
hlthsfty.eng
Ordinary prescription glasses do not meet standards.
Always carry and use your own eye protection.
Side shields, goggles and face shields may be necessary.
Contact lenses should not be worn at sites where eye and
face protection is necessary:
May complicate first aid efforts.
May absorb gases and vapors from the air and
aggravate chemical injury.
OSHA prohibits use of contact lenses when respirators
are worn.
Make selection based on hazard to be encountered:
Impact
Penetration
Chemicals
Ankle twists and sprains
Slippery surfaces
Cold
Heat
Static electricity
Use steel-toed footwear where heavy objects may drop on the
foot (ANSI Z41.1).
Metatarsal guards may be required at the site.
Where soles may be penetrated, wear safety boots with
reinforced soles.
Select footwear (boots, pullover boots, shoe covers) based on
ability to resist penetration or permeation by the chemicals.
Possible materials: neoprene, PVC, butyl rubber, natural
rubber.
Do not wear leather footwear where contamination may
occur.
Wear high-top industrial work boots where there are
hazardous walking/working surfaces.
3-2
-------
Slippery Surfaces
Slips, trips and falls are most frequent and most disabling.
Static Electricity
Hearing
Protection
Select footwear with hazard in mind - design and material of
sole is important.
Rubber-soled shoes increase the hazard.
Use special conducting shoes or other static diffusing devices.
Long-term exposure can cause permanent loss of hearing (see
Figure 3-1).
Shorter exposures may result in temporary loss.
If conversation is difficult at a distance of three feet, hearing
protection should be used.
Noise Reduction Rating (NRR): ability of hearing protector
to reduce sound levels - NRR increases as ability to protect
increases (See Table 3-1).
Choose proper hearing protector for the work environment.
Be aware of potential contamination of hearing protection.
SEMICIRCULAR
CANALS
EIGHTH NERVE
OVAL WIKOOW
External Ecr
ORGAN
ROLWO Of
W1MOO* COBTI
COCHLEA
Middle Inner
Ear Ear
Figure 3-1. The ear
hlthsfty.cng
3-3
-------
TABLE 3-1. TYPICAL NOISE REDUCTION RATINGS (NRRs) FOR COMMON
HEARING PROTECTION DEVICES
Type of Hearing Protection Device Range of NRRs
Premolded earplugs (including flanged and conical models) 16 to 27
Custom-molded earplugs 11 to 31
User-molded earplugs 16 to 26
Self-molding earplugs (expandable foam) 29 to 32
Self-molding earplugs (glass fiber) 22 to 27
Ear muffs (over the head) 19 to 29
Source: NIOSH Compendium of Hearing Protection Devices, 1984.
Hand Protection Gloves should be selected based on the probability of:
abrasions, bruises, lacerations, splinters, etc.
chilling, freezing, or burns
chemical and biological contaminants
electrical shock
Refer to the Guidelines for the Selection of Chemical
Protective Clothing (EPA Regional Health and Safety
Offices).
Liquid-proof gloves are not necessarily permeation resistant.
A variety of gloves may be necessary to provide proper
protection (wear durable over impermeable but delicate).
See Table 3-2 for information on the physical characteristics
of protective materials.
Have extra gloves available during field activities.
Skin and Body Select clothing for resistance to chemical degradation and
Protection permeation, and heat resistance.
hlthsfty eng 3-4
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TABLE 3-2. PHYSICAL CHARACTERISTICS OF PROTECTIVE MATERIALS*
Abrasion
Material Resistance
Butyl Rubber (Butyl)
Chlorinated Polyethylene (CPE)
Natural Rubber
Nitrite-Butadiene Rubber (NBR)
Neoprcne
Nitrile Rubber (Nitrite)
Nitrite Rubber & Polyvinyl
Chloride (Nitrile & PVC)
Polyethylene
Polyurethane
Polyvinyl Alcohol (PVA)
Polyvinyl Chloride (PVC)
Styrene-Butadiene Rubber (SBR)
Viton
F
E
E
E
E
E
G
F
E
F
G
E
G
Cut
Resistance
G
G
E
E
E
E
G
F
G
F
P
G
G
Flexibility
G
G
E
E
G
E
G
G
E
P
F
G
G
Heat
Resistance
E
G
F
G
G
G
F
F
G
G
P
G
G
Ozone
Resistance
E
E
P
F
E
F
E
F
G
E
E
F
E
Puncture
Resistance
G
G
E
E
G
E
G
P
G
F
G
F
G
Tear
Resistance
G
G
E
G
G
G
G
F
G
G
G
F
G
Relative
Cost
High
Low
Medium
Medium
Medium
Medium
Medium
Low
High
Very High
Low
Low
Very High
'Ratings are subject to variation depending on formulation, thickness, and whether the material is supported by fabric.
E-excellent; G-good; F-fair; P-poor
A92-333.1
3-5
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No one suit will provide appropriate protection in all
situations.
A variety of protective garments are available.
Materials are not intended for prolonged contact with
concentrated chemicals; always have extra clothing at the site.
Do not use synthetic fabric suits when contact with hot
surfaces is possible.
See Appendices 3-A and 3-B for information regarding
protective clothing and materials.
3.3 LEVELS OF PROTECTION
To aid in selecting PPE, EPA has developed a protocol consisting of
four levels of protection. Each level provides a given degree of
protection to the skin and respiratory system (See Table 3-3).
Considerations
Reasons for
Upgrading
Reasons for
Downgrading
Type, measured concentration, and toxicity of the chemical
substance in the ambient atmosphere.
Potential for exposure to airborne materials, liquid splashes,
or other materials.
Known or suspected presence of dermal hazard.
Occurrence or likely occurrence of gas or vapor emission.
Change in work task.
Personal request.
New information regarding hazard.
Change in site conditions.
Change in work task.
3.4 CONTROLLING THE TRANSFER OF CONTAMINANTS
Improper use or handling of materials can unintentionally result in
transfer of contaminants to unintended objects. Proper preparation
will minimize the potential for such contamination.
hlthsfty.eng
3-6
-------
TABLE 3-3. LEVEL OF PROTECTION
Level of Protection
Equipment
Protection Provided
Should Be Used When
Limiting Criteria
RECOMMENDED-
Pressure-demand, full-facepiece
SCBA or pressure-demand supplied-
air respirator with escape SCBA.
Fully-encapsulating, chemical-
resistant suit.
Inner chemical-resistant gloves
Chemical-resistant safety
boots/shoes.
Two-way radio communications
(intrinsically safe)
OPTIONAL:
Cooling unit
Coveralls
Long cotton underwear
Hard hat
Disposable gloves and boot covers
The highest available level of
respiratory, skin, and eye
protection.
The chemical substance has been
identified and requires the highest
level of protection for skin, eyes
and the respiratory system based
on either.
measured (or potential for)
high concentration of
atmospheric vapors, gases, or
particulates or
site operations and work
functions involving a high
potential for splash, immersion,
or exposure to unexpected
vapors, gases, or particulates of
materials that are harmful to
skin or capable of being
absorbed through the intact
skin.
Substance with a high degree of
hazard to the skin are known or
suspected to be present, and skin
contact is possible.
Operations must be conducted in
confined, poorly ventilated areas
until the absence of conditions
requiring Level A protection is
determined.
Direct reading field instruments
indicate high levels of unidentified
vapors and gases in the air.
Fully-encapsulating suit material
must be compatible with the
substance involved
A92-333.1
3-7
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TABLE 3-3 (CONTINUED)
Level of Protection
Equipment
Protection Provided
Should Be Used When
Limiting Criteria
B
RECOMMENDED:
Pressure-demand, full-facepiece
SCBA or pressure-demand supplied
air respirator with escape SCBA.
Chemical-resistant clothing (overalls
and long-sleeved jacket; hooded,
one- or two-piece chemical splash
suit; disposable chemical-resistant
one-piece suit).
Inner and outer chemical-resistant
gloves.
Chemical resistant safety
boots/shoes.
Hard hat.
Two-way radio communications
(intrinsically safe).
OPTIONAL:
Coveralls
Disposable boot covers
Face shield
Long cotton underwear
The same level of respiratory
protection as Level A but less
skin protection.
It is the minimum level
recommended for initial site
entries until the hazards have
been further identified.
The type and atmospheric
concentration of substances have
been identified and require a high
level of respiratory protection, but
less skin protection. This involves
atmospheres'
with IDLH concentrations of
specific substances that do not
represent a severe skin hazard;
or
that do not meet the criteria
for use of air-purifying
respirators.
Atmosphere contains less than
19.5 percent oxygen
Presence of incompletely
identified vapors or gases is
indicated by direct-reading
organic vapor detection
instrument, but vapors and
gases are not suspected of
containing high levels of
chemicals harmful to skin or
capable of being absorbed
through the intact skin.
Use only when the vapor or
gases present are not suspected
of containing high
concentrations of chemicals that
are harmful to skin or capable
of being absorbed through the
intact skin.
Use only when it is highly
unlikely that the work being
done will generate either high
concentrations of vapors, gases
or particulates or splashes of
material that will affect exposed
skin.
A92-333.1
3-8
-------
TABLE 3-3 (CONTINUED)
Level of Protection
Equipment
Protection Provided
Should Be Used When
Limiting Criteria
RECOMMENDED:
Full-facepiece, air-purifying,
canister-equipped respirator.
Chemical-resistant clothing (overalls
and long-sleeved jacket; hooded,
one- or two-piece chemical splash
suit; disposable chemical-resistant
one-piece suit).
Inner and outer chemical-resistant
gloves.
Chemical-resistant safety
boots/shoes.
Hard hat.
Two-way radio communications
(intrinsically safe).
OPTIONAL:
Coveralls
Disposable boot covers
Face shield
Escape mask
Long cotton underwear
The same level of skin protection
as Level B, but a lower level of
respiratory protection
The atmospheric contaminants,
liquid splashes, or other direct
contact will not adversely affect
any exposed skin.
The types of air contaminants
have been identified,
concentrations measured, and a
canister is available that can
remove the contaminant.
All criteria for the use of air-
purifying respirators are met.
Atmospheric concentration of
chemicals must not exceed
IDLH levels.
The atmosphere must contain at
least 19 5 percent oxygen.
A92-333.1
3-9
-------
TABLE 3-3 (CONTINUED)
Level of Protection
Equipment
Protection Provided
Should Be Used When
Limiting Criteria
D
RECOMMENDED:
Coveralls
Safety boots/shoes
Safety glasses or chemical splash
goggles
Hard hat
OPTIONAL:
Gloves
Escape mask
Face shield
No respiratory protection
Minimal skin protection.
The atmosphere contains no
known hazard.
Work functions preclude
splashes, immersion, or the
potential for unexpected
inhalation or contact with
hazardous levels of any
chemicals.
This level should not be worn
in highly contaminated areas
The atmosphere must contain at
least 19.5 percent oxygen.
Adapted from: NIOSH/OSHA/USCG/EPA: Occupational Safety and Health Guidance Manual for Hazardous Waste Site Activities, 1985.
A92-333.1
3-10
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Planning Disposable equipment
Onsite decontamination
Method of decontamination
Disposal
Appropriate supplies
Preventing Minimize surfaces touched.
Transfer of Avoid walking on or through chemical spills.
Contaminants Wrap contaminated equipment and containers before placing
them on a clean surface.
Control personal habits which may transfer contaminants to
clothing or exposed parts of body.
Remove protective clothing and discard properly.
Use disposable equipment and discard on site.
Decontaminate nondisposable equipment immediately after
use or package properly for later decontamination.
3.5 DECONTAMINATION
Contamination may occur even though protective clothing and
respirators are used and good work practices are followed. To
prevent transfer of contaminants into clean areas, decontamination
must be performed. This consists of physically removing
contaminants or changing their chemical nature. Use of soap and
water is often sufficient for proper decontamination.
Refer to the NIOSH/OSHA/USCG/EPA Occupational
Safety and Health Guidance Manual for Hazardous Waste
Sites, 1985, or the EPA Standard Operating Safety Guides.
Use large, thick, plastic bags for the disposal of contaminated
disposable materials.
Set up an area onsite for the decontamination of sampling
equipment, sample containers, and their carrying containers.
Wash exposed areas prior to eating, drinking, or using
tobacco products with soap and water or premoistened,
disposable towelettes. r:^ "»?/ v^-
-------
3.6 DONNING AND DOFFING PROTECTIVE CLOTHING
Achieving the complete benefits of protective clothing depends on
the techniques used for donning and doffing the clothing. In
general, care must be taken to avoid tearing or puncturing the
materials, and to avoid contaminating the inside of the garments.
Helpful Hints Pull pants of protective clothing down over the boots and
tape in place.
Tape gloves to sleeves of protective clothing in similar
fashion.
Have an assistant help when you are donning or doffing
protective clothing.
Store protective clothing where it will not become
contaminated.
See Appendix 3-C for specific donning and doffing
procedures.
3.7 STORAGE OF EQUIPMENT
Proper storage can result in:
longer life;
reduced maintenance;
increased availability of critical gear;
minimization of cross-contamination; and
prevention of punctures and tears.
A92-333.1 3-12
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APPENDIX 3-A
PERFORMANCE REQUIREMENTS OF PROTECTIVE CLOTHING
Clothing Section
Resistance to
Degradation by
Chemicals
Resistance to
Penetration by
Chemicals
Select personal protective clothing which will provide the best
possible protection against the chemicals and environment to which
you will be exposed.
Important characteristics to consider:
Strength and durability - generally proportional to thickness;
however, increased durability generally reduces flexibility.
Thermal resistance - behavior in hot/cold environments? -
melting?
Ability to be cleaned, decontaminated, or protected from
contamination.
Resistance of protective clothing to chemical damage or
degradation, mechanical penetration, and permeation
through the intact material.
A great deal of information concerning the chemical resistance of
materials from which protective gloves and clothing are made can
be obtained.
Select personal protective clothing with care; porous
materials, tears, punctures, stitched seams, button holes and
loose openings can allow penetration.
Store, transport and handle gloves and protective clothing
with care at all times.
Inspect personal protective clothing for holes before use.
Seal openings between garments, gloves and boots with
adhesive tape that will resist the hazardous material you
expect to encounter.
A92-333.1
3-13
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Resistance to Gases, liquids and some solids can diffuse through materials
Permeation by used to make protective gloves and clothing.
Chemicals
Permeation can occur without degradation or damage to the
protective material.
No protective material will resist permeation by all
chemicals.
Reduce permeation by:
minimizing concentrations in contact with protective
materials;
using thicker materials; and
avoiding prolonged exposure or contact with
chemicals.
A92-333.1 3-14
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APPENDIX 3-B
PROTECTIVE MATERIALS
Fabrics Tyvek: non-woven fabric; resists tears, punctures and
abrasion; relatively inexpensive; used for disposable
garments; resists buildup of static electricity (unless
laundered); melting point: 135°C (275°F).
Nomex: woven fabric of polyamide fibers; very durable and
acid-resistant; flame-resistant, but not noncombustible;
allows passage of gas, vapor and steam.
Elastomers Are natural or synthetic polymeric materials that exhibit good
elasticity and varying degrees of resistance to chemical degradation
and permeation.
Polyethylene: inert but permeable material that will absorb
organic solvents; sometimes used to coat Tyvek garments to
provide resistance to acids, bases and salts.
Polyvinyl chloride (PVC): resistant to acids, but somewhat
permeable and retentive of contaminant; coating for fully-
encapsulating suits made of Nomex.
Neoprene: better general protection than PVC; retains
contaminants; many respirator facepieces and breathing
hoses.
Chlorinated polyethylene (CPE or Choropel): resists
degradation by many chemicals; permeation resistance
unknown; splash suits and fully-encapsulating suits.
Butyl Rubber: highly resistant to permeation by gases; does
not resist halogenated hydrocarbons and petroleum
compounds; does not retain contaminants; boots, gloves,
splashsuits, aprons and fully-encapsulating suits.
Viton: fluoroelastomer with greater resistance to
degradation and permeation than neoprene and butyl
rubber; does not protect against some chemicals like
ketones and aldehydes; does not retain contaminants; fully-
encapsulating suits.
A92-333.1 3-15
-------
Natural rubber: resists degradation by alcohols and
caustics; used for boots and gloves.
Milled nitrite: resists petroleum products; boots and gloves.
Polyvinyl alcohol (PVA): soluble in water but protects
against aromatic and chlorinated hydrocarbons.
For additional information consult EPA's Guidelines for the
Selection of Chemical Protective Clothing, 1987.
A92-333.1 3-16
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APPENDIX 3-C
PROCEDURES FOR DONNING AND DOFFING PERSONAL
PROTECTIVE CLOTHING
Using Gloves
Gloves
Removing Gloves
Using Boots
Boots
Removing Boats
Trim fingernails and remove jewelry which may puncture
material.
Use powdered gloves if possible.
Use several layers of differing gloves if necessary.
Loosen both gloves by pulling lightly on each fingertip of
the gloves.
Do not touch your skin with the outer surface of either
glove.
Remove the first glove either by pulling on the fingertips or
by grasping it just below the cuff on the palm side and
rolling the glove off the fingers.
Remove the second glove by inserting the ungloved fingers
inside the cuff on the palm side without touching the
outside of the glove, and pushing or rolling the glove off the
fingers.
Before use, be sure shoes cannot puncture overboots.
Use layers of boots of differing capabilities if necessary.
Wear gloves unless boots are very loose.
Loosen boots by pulling them lightly with the gloved hand.
Do not allow outside of boot to contact bare skin.
Remove first boot by pulling it off the foot with a gloved
hand or a bootjack, or by inserting the ungloved fingers
inside the boot and pushing it off without touching the
outside of the boot.
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Using and
Removing Full
Body Suits
Donning the Suit
Doffing the Suit
Remove second boot in the same fashion.
Safe use of full protective equipment requires a team of
persons who are physically fit and trained and practiced in
the use of self-contained breathing apparatus and use of the
complete suits. Assistants must be prepared to:
Carry out emergency rescue if necessary.
Assist the wearers into the breathing apparatus and the
suits.
Decontaminate the outside of the suit before it is removed.
Assist the wearers in removing the suits (normal and
emergency removals).
Thoroughly inspect the suit for holes, rips, malfunctioning
closures, cracked masks or other deficiencies.
Wear a minimum of clothing beneath suit (cotton).
Use talcum powder as necessary.
Remove any extraneous or disposable clothing, boot covers,
or gloves.
Have assistant perform the following:
Loosen and remove the steel-toe and shank boots.
Open front of suit to allow access to SCBA regulator.
(Leave breathing hose attached as long as there is
sufficient pressure.)
Open suit completely and lift the hood over the head
of the wearer; rest it on top of the SCBA tank.
Remove arms, one at a time, from suit. Once arms are
free, have assistant lift suit up and away from the SCBA
backpack, avoiding any contact between the outside surface
of the suit and the wearer's body, and lay the suit out flat
behind the wearer. Leave internal gloves on.
While sitting, remove both legs from the suit.
hlthsflyeng
3-18
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After suit is removed, remove internal gloves by rolling
them off the hand, and turning them inside out.
Proceed to the clean area and follow procedure for doffing
SCBA.
Remove internal clothing and thoroughly cleanse body.
A92-333.1 3-19
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CHAPTER 4
4.0 RESPIRATORY PROTECTION
4.1 OBJECTIVE
To provide basic information on the selection, use and
maintenance of respiratory protective devices so that they may be
used in a safe and effective manner.
4.2 RECOGNITION OF RESPIRATORY HAZARDS
Respiratory hazards may be encountered during any field activity.
Respiratory protection is needed if personnel must enter any area
in which there may be either a deficiency of oxygen or a high
concentration of toxic chemicals in the air. In such atmospheres,
life or health may depend on using respiratory equipment which
can provide a supply of clean breathing air.
Hazard Locations Spill scenes
Discharge or emission sites
Mines
Industrial plants
Hazardous waste sites
Confined spaces
General Do not rely on workaday respiratory use policy.
Considerations Assume the worst conditions.
Three basic categories of hazards
oxygen deficiency
aerosols
gases and vapors
Oxygen Causes
Deficiency
displacement
oxidation
A92-333.1 4-1
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Minor to fatal effects (see Table 4-1)
< 19.5% oxygen at sea level (OSHA)
Aerosols Fine paniculate (solid or liquid) suspended in air
Physical classifications
spray
fume
fog
smoke
smog
Physiological classification
nuisance
inert pulmonary reaction
lung fibrosis
irritation
systemic poison
allergen
carcinogen
Gaseous Chemical classification
Contaminants
acidic
alkaline
organic
organometallic
hydrides
inert
Physiological classification
irritant
asphyxiant
anesthetic
systemic poison
allergen
carcinogen
A92-333.1 4-2
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TABLE 4-1. PHYSIOLOGICAL EFFECTS OF OXYGEN DEFICIENCY
Oxygen Volume at Sea Level (%) Effects
12 to 16 -Breathing volume and heart rate increase.
-Attention and coordination impaired.
10 to 14 -Loss of peripheral vision.
-Poor coordination.
-Rapid fatigue with exertion.
-Emotional upsets and faulty judgment.
-Respiration disturbed.
6 to 10 -Nausea and vomiting.
-Unable to move freely.
-Possible loss of consciousness.
Below 6 -Convulsions
-Gasping respiration immediately prior to cessation of
breathing which is followed quickly by death.
A92-333.1 4-3
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4.3 TYPES OF RESPIRATORS
Basic Types
Facepieces
Tight-fitting
Loose-fitting
Air-Purifying
Respirators
Precautions
Air-purifying
Atmosphere-supplying
Tight-fitting or loose-fitting
Quarter mask
Half mask
Full facepiece
Hoods
Helmets
Suits
Blouses
Consist of face-piece and air-purifying device.
Can remove specific airborne contaminants by
filtration;
absorption;
adsorption; or
chemical reaction.
Are approved for use only in atmospheres of certain
concentrations of chemicals (see cartridges or canisters).
Usually operate in negative-pressure mode (exception:
powered air-purifying respirators).
Cartridges in two-cartridge respirators must be of same type.
Combination cartridges may be used for protection against
more than one type of chemical.
Use air-purifying respirators when:
identify and concentration of contaminant are known;
oxygen in air is at least 19.5%;
contaminant has adequate warning properties;
approved canisters or cartridges for the contaminant
and concentration are available;
A92-333.1
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Styles
Atmosphere
Supplying
Respirators
SCBA
SAR
the Immediately Dangerous to Life or Health
(IDLH) concentration is not exceeded.
See Table 4-2 for advantages/disadvantages of air-purifying
respirators.
See Table 4-3 for styles of respirators.
Consist of facepiece (loose or tight-fitting) and device which
provides clean respirable air.
Two basic types:
self-contained breathing apparatus (SCBA)
supplied air respirator (SAR)
Carried by wearer
Consists of:
facepiece
hose
regulator
air source
Protects against most levels and types of contaminants.
Duration of use limited by amount of air carried and
breathing rate.
Increases likelihood of heat stress and fatigue due to weight.
Impairs movement.
See Table 4-4 for advantages/disadvantages of SCBAs.
Also known as air-line respirators.
Supply air to facepiece via a supply line from a stationary
source.
Source may be onsite compressor or compressed air
cylinders.
Available in positive- and negative-pressure modes.
A92-333.1
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TABLE 4-2. RELATIVE ADVANTAGES AND DISADVANTAGES OF AIR-
PURIFYING RESPIRATORS
Type of Respirator
Advantages
Disadvantages
Air-Purifying
Air-Purifying Respirator
(including powered air-
purifying respirators
(PAPRs)
Enhanced mobility
Lighter in weight than
an SCBA Generally
weighs 2 pounds (1 kg)
or less (except for
PAPRs).
Cannot be used in IDLH or oxygen-
deficient atmospheres (less than 19.5
percent oxygen at sea level).
Limited duration of protection. May be
hard to gauge safe operating time in
field conditions.
Only protects against specific chemicals
and up to specific concentrations.
Use requires monitoring of contaminant
and oxygen levels.
Can only be used (1) against gas and
vapor contaminants with adequate
warning properties, or (2) for specific
gases or vapors provided that the service
life is known and a safety factor is
applied, or if the unit has an ESLI (end-
of-service-life indicator)
Source: NIOSH/OSHA/USCG/EPA: Occupational Safety and Health Guidance Manual for Hazardous
Waste Site Activities, 1985.
TABLE 4-3. RESPIRATOR STYLES
Facepiece
Half-mask
Full-face mask
Helmet
Air-Purifying Unit
Twin
Cartridges
X
X
PAPR at Waist
X
X
X
Chin-mounted
Canister
X
Harness-
mounted
Canister
-
X
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TABLE 4-4. RELATIVE ADVANTAGES AND DISADVANTAGES OF
ATMOSPHERE-SUPPLYING RESPIRATORY PROTECTIVE
EQUIPMENT
Type of Respirator
Advantages
Disadvantages
Self-Contained Breathing
Apparatus (SCBA)
Positive Pressure Supplied-Air
Respirator (SAR) (also called
air-line respirator)
Provides the highest
available level of
protection against
airborne contaminants
and oxygen deficiency.
Provides the highest
available level of
protection under
strenuous work
conditions.
Enables longer work
periods than an SCBA.
Less bulky and heavy
than a SCBA. SAR
equipment weighs less
than 5 pounds (or
around 15 pounds if
escape SCBA
protection is included).
Protects against most
airborne contaminants.
Bulky, heavy (up to 35 pounds).
Finite air supply limits work duration.
May impair movement in confined
spaces.
Not approved for use in atmospheres
immediately dangerous to life or
health (IDLH) or in oxygen-deficient
atmospheres unless equipped with an
emergency egress unit such as an
escape-only SCBA that can provide
immediate emergency respiratory
protection in case of air-line failure.
Impairs mobility.
MSHA/NIOSH certification limits
hose length to 300 feet (90 meters).
As the length of the hose is
increased, the minimum approved air
flow may not be delivered at the
facepiece
Air line is vulnerable to damage,
chemical contamination, and
degradation. Decontamination of
hoses may be difficult.
Worker must retrace steps to leave
work area.
Requires supervision/monitoring of
the air supply line.
Source: NIOSH/OSHA/USCG/EPA
Waste Site Activities, 1985.
Occupational Safety and Health Guidance Manual for Hazardous
A92-333.1
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Precautions
Combined
SCBA/SARs
Respirator
Certification
Limitations
Assigned
Protection Factor
(APF)
Should not be used in IDLH atmospheres unless equipped
with escape SCBA.
Use of compressors limited by quality of ambient air.
Couplings must be incompatible with outlets of other gas
systems used onsite.
See Table 4-4 for advantages/disadvantages of atmosphere-
supplying respirators.
Can operate in either SCBA or SAR mode.
SCBA - entry and exit.
SAR - extended work in contaminated area
NIOSH/MSHA
Respirators and components are certified as a unit;
interchanging parts voids certification.
Air-purifying filters and cartridges approved for only certain
materials and conditions of use (organic vapor cartridge -
adequate warning properties and at least 19.5% O2).
Each type of respirator (half-mask, PAPR, etc.) is assigned
an APF.
APF = Outside Concentration/Inside Concentration.
Example - respirator with APF of 100
If outside concentration = 200 ppm, what is concentration
inside facepiece?
100 = 200 ppm/x ppm
x = 2 ppm
Can use APF and PEL or TLV to determine maximum
concentration of contaminant in which respirator can be
used.
Maximum concentration (ppm) = APF x Allowable
Exposure Limit
A92-333.1
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Example - Air-purifying, half-mask respirator: APF
Contaminant: TLV = 20 ppm
Maximum Concentration = APF x TLV
x = 10 x 20
x = 200 ppm
See Table 4-5 for assigned protection factors.
10.
4.4 RESPIRATOR SELECTION
Respirator selection is a complex process that should be performed
only by a trained industrial hygienist familiar with the actual work
environment and job tasks to be performed.
General
Considerations
Contaminant
Considerations
Respiratory
Hazards
Oxygen Deficiency
Flammable
Atmospheres
Toxic
Atmospheres
Nature of hazardous operation, process or condition
Contaminant, type of hazard, concentration, effects on body
Activities to be conducted
Time protection needed
Escape time
Available respiratory protection equipment
Service life of cartridges/canisters
Physical, chemical, toxicological properties
Odor threshold
REL, TLV, PEL
EDLH concentration
Eye irritation potential
Oxygen deficiency
Flammable atmosphere
Toxic atmospheres
SCBA/pressure-demand
SAR/auxiliary SCBA
General Policy: do not enter if > 25 % of LEL.
SCBA/pressure-demand
DDLH - SCBA/pressure-demand
Above PELs but below IDLH - APR or SAR
Below PEL - none required
A92-333.1
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TABLE 4-5. RESPIRATOR PROTECTION FACTORS
Assigned
Protection
Factor
10
25
50
1000
2000
10,000
Type of
Respirator
APR/half-
mask
APR/full-face
SAR/half-
mask/negative
PAPR/hood or
helmet
SAR/hood or
helmet/
continuous
flow
APR/full-face
PAPR/tight-
fitting
SAR/full-face/
negative
SAR/tight-
fitting/
continuous
flow
SCBA/full-
face/negative
SAR/half-
mask/positive
SAR/full-
face/positive
SCBA/full-
face/
positive
SCBA/full-
face/
positive/
auxiliary
positive
Contaminant
Particulate
X
X (any type)
X
X
X (HEPA)
X (HEPA)
X
X
X
X
X
X
Gas/Vapor
X
X
X
X
X
X
X
X
X
X
X
X
X
Combination
X
X (any type
paniculate
filter)
X
X
X (HEPA)
X (HEPA)
X
X
X
X
X
X
X
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4.5 RESPIRATOR USE
Respirator Policy
Respirator
Program
Requirements
Provide appropriate respiratory protection devices for
agency employees.
Require use of devices when necessary to protect health:
high potential for sudden release, or actual release of
toxic gases/vapors;
hazardous environments or locations (spill sites);
confined spaces;
engineering controls not feasible.
Allow employees to wear respiratory protection even when
concentrations are not expected to harm health and others
are not affected.
Keep hazardous conditions under surveillance.
Keep employee exposure or stress at safe levels.
Require standby personnel at IDLH atmospheres.
Require written Standard Operation Procedures (SOPs) for
selection and use of respiratory protective equipment.
Written program (SOPs)
Respirator selection
Training
Respirator assignment
Cleaning
Storage
Inspection and maintenance
Surveillance
Program evaluation
Physical examination
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4.6 SPECIAL CONSIDERATIONS
Facial hair
Eye glasses
Contact lenses
Facial deformities
Communication
4.7 RESPIRATOR FIT TESTING
Fit Checks
Required for negative pressure air-purifying respirators.
Varieties Two types:
qualitative
quantitative
See Table 4-6 for advantages/disadvantages of qualitative
and quantitative fit testing.
Negative Pressure Test - tests exhalation valve and facepiece
seals.
Positive Pressure Test - tests inhalation valves and facepiece
seals.
Determine sensitivity to challenge material:
banana oil (isoamyl acetate)
saccharin
irritant smoke (stannic chloride)
Select respirator.
Conduct positive/negative fit check.
Enter test chamber.
Introduce challenge material.
Qualitative Fit
Testing
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TABLE 4-6. ADVANTAGES AND DISADVANTAGES OF
QUALITATIVE AND QUANTITATIVE FIT TESTING
Fit Test
Advantages
Disadvantages
Qualitative
Fast
Inexpensive
Simple
Easily performed in the
field
Relies on wearer's subjective
response (may not be
reliable).
Quantitative
Does not rely on wearer's
subjective response
(Is recommended when the
respirator is used in highly
toxic atmospheres or those
immediately dangerous to
life and health).
Requires qualified personnel
and equipment.
Testing cannot be done on
the respirator which will be
used.
A92-333.1
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Perform test exercises (minimum of one minute each):
breathe normally
breathe deeply
turn head side to side
nod head up and down
talk aloud several minutes
jog in place
breathe normally
M
If challenge material is not detected, subject has passed test
(PF = 10).
Quantitative Fit Conduct qualitative fit test.
Testing
Follow instructions for quantitative fit testing equipment
used (fit test chamber, "Portacount").
Perform test exercises.
Determine fit factor.
A92-333.1 4-14
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Ill
-------
FUNDAMENTALS OF
ENVIRONMENTAL COMPLIANCE INSPECTIONS
-------
TABLE OF CONTENTS
Chapter Page
1.0 INTRODUCTION TO ENVIRONMENTAL COMPLIANCE 1-1
1.1 Course Objectives 1-1
1.2 Compliance Monitoring 1-1
1.3 Motivation for Compliance 1-2
1.4 The Inspector's Role 1-2
2.0 INSPECTION PLANNING AND PREPARATION 2-1
2.1 Responsibilities of the Inspection Team 2-1
2.2 Reviewing Available Information 2-1
2.3 Preparing the Inspection Plan 2-2
2.4 Preinspection Checklist 2-3
3.0 ENTRY AND OPENING CONFERENCE 3-1
3.1 Key Elements of Entry 3-1
3.2 Approaching the Facility 3-1
3.3 Entry Procedures 3-2
3.4 Opening Conference 3-2
3.5 Amending the Inspection Plan 3-3
4.0 INFORMATION GATHERING AND DOCUMENTATION 4-1
4.1 Types of Information and Documentation 4-1
4.2 Documenting Information 4-1
4.3 Techniques for Improving Information Gathering Skills 4-2
4.4 Records Inspection 4-3
4.5 Physical Sampling t 4-5
4.6 Interviews ' 4-14
4.7 Observations and Illustrations 4-17
4.8 Exit Interview 4-18
4.9 Exit Observations/Activities 4-19
5.0 POST-INSPECTION ACTIVITIES 5-1
5.1 The Inspection Report 5-1
Figures
Number Page
4-1. Sampling from a high-negative-pressure duct 4-11
-------
CHAPTER 1
1.0 INTRODUCTION TO ENVIRONMENTAL COMPLIANCE
1.1 COURSE OBJECTIVES
This section of the SEDESOL inspector's course provides a brief
overview of the course Fundamentals of Environmental Compliance
Inspections that EPA uses in training its new inspectors. It is hoped
that you will 1) gain an understanding of the policies, procedures
and techniques an EPA inspector is required to follow and 2) find
the information provided to be useful in conducting your own
environmental compliance inspections as well.
Note: All the following information represents EPA, not SEDESOL policy.
1.2 COMPLIANCE MONITORING
Purpose of To ensure that environmental requirements are being
Inspections implemented effectively, inspections are conducted to:
Assess compliance status and document violations for
enforcement action.
Provide oversight of inspection programs carried out by other
agencies such as state jurisdictions.
Gather data as part of an area/industry-wide inspection plan
to assess the need for additional controls.
Promote voluntary compliance.
Establish an enforcement presence to promote compliance.
Support the permit issuance process.
A92-333.2 1-1
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L3 MOTIVATION FOR COMPLIANCE
Motivating
Factors
Natural
Disincentives
Role of
Enforcement
Credible
Enforcement
Presence
Societal/moral factors
Short-run economic factors
Long-run economic factors
Individual property rights
Economic advantages of noncompliance
Fear of change
Expediency
Lack of knowledge on how to comply or where to get that
knowledge
Fear of detection
Assurance of fairness
Likelihood of detection
Serious consequences of detection
Swift and sure response
Fair and consistent response
1.4 THE INSPECTOR'S ROLE
The inspector plays a crucial role in motivating companies to comply
with environmental regulations, thereby protecting the people who
might otherwise be exposed to toxic chemicals and other hazardous
materials. The more effective the inspector can be, the higher the
rates of compliance will be. Higher rates of compliance mean lower
risks to human health and the environment. If an inspector does
not find and properly document a violation, there can be no
enforcement.
Inspectors must master both the "science" and the "art" of
inspections. You need not only a thorough understanding of the
technical aspects of the job - you also need to learn to ask the right
questions, follow the paper trails, and check out inconsistencies.
A92-333.2
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CHAPTER 2
2.0 INSPECTION PLANNING AND PREPARATION
Planning and preparation are essential to:
Focus the inspection on the most important issues.
Make the most efficient and effective use of time on site.
Ensure that equipment will be available when needed.
Ensure that proper procedures are followed.
2.1 RESPONSIBILITIES OF THE INSPECTION TEAM
Inspector Effective inspections begin with careful planning that includes:
Responsibilities
Reviewing available information on the facility, and
Preparing an inspection plan.
22 REVIEWING AVAILABLE INFORMATION
A review of available information will enable inspectors to:
Become familiar with the facility (personnel, size,
operations);
Learn about findings from previous inspections, including
violations;
Avoid requesting previously submitted information; and
Clarify legal and technical issues before entry.
A92-333.2 2-1
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Available The following information might be available:
Information
Facility location, geographical features;
Names of officials or representatives;
Descriptions of recordkeeping/filing systems;
Previous entry problems;
Safety requirements;
Special exemptions from requirements;
Notifications;
Prior inspection records;
Compliance problems/enforcement actions;
Complaints from citizens about the facility; and
Correspondence.
2.3 PREPARING THE INSPECTION PLAN
An inspection plan is an organized approach to guide the conduct of
the inspection. It:
States the reason for inspection;
Defines the scope of the inspection;
Specifies procedures;
Defines tasks; and
Identifies equipment and materials needed.
Inspection An inspection plan should include:
Plan Elements
Objectives and scope;
Inspection activities and field techniques;
Quality Assurance Project Plan, including a sampling plan;
Safety plan; and
Administrative requirements.
Use the preinspection checklist that follows this section or develop
one of your own to ensure that you have completed all planning
tasks for each inspection.
A92-333.2 2-2
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2.4 PREINSPECTION CHECKLIST
GENERAL EQUIPMENT
Camera
Film and flash equipment
Pocket calculator
Tape measure
Clipboard
Waterproof pens, pencils, and markers
Locking briefcase
"Confidential Business Information" stamp
Stamp pad
Pre-addressed envelopes
Plastic covers
Plain envelopes
Polyethylene bags
Disposable towels or rags
Flashlight and batteries
Pocket knife
First Aid Manual
Kneeboard
Knapsack
Rope
SAMPLING EQUIPMENT
Sampling equipment will vary by program and media. Examples of
typical sampling equipment follow.
Crescent wrench, bung opener
Siphoning equipment
Weighted bottle sampler
Bottom sediment sampler
Liquid waste samplers (e.g., glass samplers)
Auger, trowel, or core sampler
Scoop sampler
Sample bottles/containers (certified clean bottles with teflon-
lined lids)
Labeling tags, tape
Storage and shipping containers with lids
Ice chest
Container for contaminated material
2-3
-------
Hazard labels for shipping samples
Ambient air monitor
Field document records
Vermiculite or equivalent packing
Thermometer
Colorimetric gas detection tubes
pH equipment
Explosimeter
Oxygen meter
SAFETY EQUIPMENT
Safety glasses or goggles
Face shield
Ear plugs
Rubber-soled, metal-toed, non-skid shoes
Liquid-proof gloves (disposable, if possible)
Coveralls, long-sleeved
Long rubber apron
Hard hat
Plastic shoe covers, disposable
Respirators and cartridges
Self-contained breathing apparatus
Drinking water - plain and salted (1 tsp. salt/5 liters H2O)
EMERGENCY EQUIPMENT
Substance-specific first aid information
Emergency telephone numbers
First-aid kit with eyewash
Fire extinguisher
Soap, waterless hand cleaner, and towels
Supply of clean water for washing
2-4
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CHAPTERS
3.0 ENTRY AND OPENING CONFERENCE
3.1 KEY ELEMENTS OF ENTRY
Inspectors should:
Follow correct administrative procedures and requirements
failure to do so can jeopardize subsequent enforcement
actions.
Check planned inspection activities against the actual
situation at the site and make adjustments as needed.
3.2 APPROACHING THE FACILITY
The investigation begins before you reach the front door of the
facility. As you approach the facility, look for signs of potential
violations. These can include:
Dead or unhealthy vegetation
Unusual emissions from stacks
Ponds or lagoons on the property that appear to contain oily
or discolored water or sludges
Leaking containers
Uncovered piles of waste
Open burning or burn pits
Oil or discoloration of water in streams or rivers that
surround the property
A92-333.2 3-1
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Strong or noxious odors
Dust or debris on haul roads
Deposits on vehicles
Be prepared to amend your plan to focus on these potential
problems.
3.3 ENTRY PROCEDURES
Inspectors should follow proper procedures when entering a facility
so that no questions or challenges can be raised regarding the
legality of the inspection.
Arrive during normal working hours.
Use the main entrance.
Ask to see the owner or other authorized facility
representative.
Present your credentials.
Explain the inspection authority.
3.4 OPENING CONFERENCE
The inspector should use the opening conference to inform the
facility representative of planned activities, to gain an understanding
of the facility's operations and practices, and to address logistical
arrangements. Inspectors should:
Explain the anticipated inspection activities in general terms.
Identify activities and processes that occur at the site and
their environmental implications.
3-2
-------
Determine what environmental programs and controls are in
place (e.g., air monitoring, employee training, equipment
maintenance) and what records are available.
Verify the applicability of regulations or requirements.
Determine who the responsible parties are for the site.
3.5 AMENDING THE INSPECTION PLAN
Information gathered as you approach the site and during the
opening conference may lead to changes in the inspection plan. Be
prepared to add or change interviewees, sampling points, and record
reviews.
3-3
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CHAPTER 4
4.0 INFORMATION GATHERING AND DOCUMENTATION
4.1 TYPES OF INFORMATION AND DOCUMENTATION
Types of
Information
There are four types of information and documentation:
Testimonial (what you are told)
Real (physical samples you gather)
Documentary (written records you collect or copy)
Demonstrative (photographs and drawings you make)
4.2 DOCUMENTING INFORMATION
Field Logbook
An inspector's field notes/logbook:
Provides the foundation for preparing reports.
Is useful in refreshing memory.
Should contain information which is objective, factual, and
free of personal feelings or conclusions.
Should be bound and consecutively numbered.
Should list documents taken or prepared, photos taken,
unusual conditions, problems, interview notes, general
information, incidents, and administrative data.
Inspectors should:
Maintain one logbook per inspection.
Use waterproof ink.
Write legibly.
Draw a line through incorrect entries and initial them.
Make a diagonal line at the conclusion of an entry and initial
it.
A92-333.2
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4.3 TECHNIQUES FOR IMPROVING INFORMATION GATHERING SKILLS
Detecting hints of potential violations will help you focus your
inspection on the most important issues.
In interviews, listen for:
Reports of knowing violations, such as night dumping or
shutting down of pollution control equipment.
Reports of accidental releases, such as spills.
Complaints about odors, skin problems, or other health
effects that workers believe might be related to contact with
hazardous or toxic materials in the workplace.
Stories or information that conflict with written records or
reports from other workers.
During the inspection, look (and smell) for:
Excess or uncontrolled emissions.
Excess odors.
Spills, leaky containers, and generally poor housekeeping.
Inoperable equipment or equipment in a gross state of
disrepair.
Equipment that has been damaged from fire or explosion.
A92-333.2 4-2
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4.4 RECORDS INSPECTION
The two objectives of inspecting facility records are to:
Determine whether required records are being maintained;
and
Use facility records as a substantiation of compliance or
noncompliance.
Review The inspector should note the kinds of records examined and why.
Considerations When reviewing records, consider these questions:
How complete is the information?
What are alternative sources for the same information?
Has the facility tried honestly to meet recordkeeping
requirements?
Are there discrepancies or suspicious consistencies between
current reports and field data or past reports?
Are the required reports complete, accurate, and of good
quality?
Do the records comply with retention requirements?
Does information in the records seem consistent with first-
hand observations?
Targeting and As part of determining exactly what records an inspector needs to
Locating Records examine, he or she should:
List the kinds of records needed for compliance and their
retention requirements.
Become familiar with the facility's recordkeeping system.
Establish priorities for the material to be reviewed.
Request that facility personnel identify pertinent files and
sources.
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Check back-up and cross-filing systems that might make
retrieval more efficient.
Records Sampling Time constraints often prevent inspectors from examining all records
at a facility. Therefore, the inspector reviews only a sample of these
records. To increase the likelihood that problems will be detected,
it is important that the sample is "representative" of the entire
universe of records, just as it is important that a physical sample is
representative of air emissions or water effluent.
The key point in sampling is to think systematically. If the inspector
suspects a problem, the sample should be drawn from records that
are likely to document the problem. The sample could focus on a
particular time period, a specific set of employees, or specific
activities.
Sampling methods include:
Random sampling - each record has an equal chance of
being included in the sample.
Interval sampling -- every fifth, tenth, etc. record is selected
based on a random starting point.
Stratified sampling - breaks the entire population into
categories based on relevant characteristics and applies
random or interval methods within categories. A larger
sample can be drawn from categories of concern.
Block sampling - selects records only within a specific
category.
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4.5 PHYSICAL SAMPLING
Why Take Physical samples are taken during a compliance inspection to
Physical Samples substantiate that a violation occurred. Samples provide quantitative
data to assess the nature, level, and extent of pollution or
contamination that result from a violation. Physical samples may
include the results of in-situ monitoring, or later analysis of samples
of soil, water, air, wastes, sludges, and residues from a site.
Sampling may even include biological sampling to establish whether
or not contaminants have damaged or have the potential to damage
the environment or human health.
Developing A Plan In order to conduct sampling that supports the goals of an
environmental inspection, it is important to develop a plan that will
guide the selection of appropriate sampling.methods. The Plan
should:
Establish and communicate sampling objectives and data
quality requirements;
Identify levels of discharge that will be within compliance;
Make realistic projections of cost and time required for
sampling;
Establish comprehensive sampling and quality assurance
protocols; and
Identify and characterize broader site conditions to support
sampling data.
What Information
Can Be Used for
Planning?
SEDESOL Inspectors are responsible for monitoring compliance for
all potential sources of pollutants. An examination of any available
records about a site is a useful way to begin planning an inspection.
Many of the sites you will inspect may already be permitted. If this
is the case, the office with jurisdiction over the facility might
maintain a file on the permits that contains information about the
types and amounts of discharges that will be found at a site. It may
also contain reports and information on previous inspections. Your
job, here, will be to assess whether or not a site has come into
compliance or has maintained compliance.
Many of the sites that you will inspect may not have permits or
applications for permits on file. These sites may have been brought
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to your attention by citizen complaints, news reports, police reports,
or observations collected in a visit to a nearby site. You may have
little information to use in developing a plan but you will need to
identify a best approach before you go into the site to conduct an
effective compliance inspection.
Developing A A quality assurance project plan (QAPP) should be developed for
Project Plan each sampling inspection. This plan details how the inspection will
be conducted and what the objectives for the inspection are. It
should include the following:
A description of the site and project;
Identification of the data quality objectives for the study;
A description of the sampling to be done and justification for
selection of sample sites;
A description of quality assurance and quality control
methods and requirements;
A description of the analysis and sampling plans and standard
operating procedures (SOPs);
A description of sample preservation and chain of custody
requirements;
A description of documentation required to meet the
administrative and technical requirements;
A project safety plan; and
Other relevant information.
The description of the site should include any available maps that
will be useful in identifying sampling locations and points of
reference. Even for unpermitted and undocumented sites, it may be
useful to include the best available map so that probable points of
discharge, wells, and other surface features can be used to identify
probable sampling points. Samples and/or appropriate on-site
monitoring instrument analysis should be taken from every
observable aqueous discharge. Samples may also be taken from
process reactors when necessary to identify or confirm the chemical
processes occurring at a facility. Samples from pools of water near
waste drums and containers may reveal leakage from these
containers.
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Because many of the facilities that you will visit are not yet
permitted, you will often need to make decisions in the field on
what should be sampled. Let your eyes, nose, and ears be your
guide! The presence of unusual solids, scums, and corrosion near a
discharge outlet, pipes, or valves may be a good indicator that a
toxic or hazardous material has escaped into the environment. You
may want to carefully collect samples of these residues for analysis.
Samples from nearby wells may also reveal the presence of
contaminants in groundwater.
For air quality, you may want to monitor, or collect samples from
stacks, but you may also want to use monitoring equipment to check
around tank seams, pipes, valves, and tank openings to look for
fugitive emissions.
You may also want to take samples of soil surrounding process
tanks or piping if there is any indication of spillage. Similarly, soil
samples from storage depots where drums or containers of suspected
wastes are kept may confirm the nature and extent of any spills.
Soil samples can be taken from the surface or from deeper in the
ground using coring or drilling devices.
Data quality objectives (DQOs) should be identified as part of the
QAPP, prior to the actual inspection. DQOs are specifications for
what is required to establish a statistically sound characterization of
conditions at the site. DQOs will identify where and how many
samples will be taken to establish a representative picture of site
conditions. The DQO statements will also establish the statistical
requirements for detectibility, precision and accuracy in analysis or
on-site monitoring and identify what will be required to achieve
completeness in sampling. These short definitions may help you
understand these concepts associated with chemical analysis:
Detectibility - the lowest concentration of a substance that
can be measured as being present
Accuracy - the degree of agreement of a measured value and
a true value for a substance
Precision -- the degree of agreement between repeated
measurements of the same sample
How Do DQOs It has been said that "the ability to correctly determine the
Help? difference between a bull and a mouse at least 95% of the time" is a
data quality objective for selecting the right mouse trap. While this
is a very simplified picture of what DQOs do, it does illustrate how
important it is to identify what you will need to do the job correctly.
A better example of how to select DQO's might be found in
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selecting methods of chemical analysis that will be sensitive enough
to determine if the concentrations of a contaminant in a sample are
in violation or not.
When and how often you sample may also be very important and
the QAPP should identify the timing and frequency of samples. An
example of this is often seen when you are required to monitor
discharges that are part of specific industrial- process that occur only
at specific times. Unless you have a system that monitors
continuously over a period of time, you may miss the discharge
violation.
QA/QC There are a number of steps an inspector should take to provide
information about the quality of sampling and analysis. The
laboratory should provide you with information from analysis that
will allow you to assess whether or not the analytical quality
objectives were met, but you must also be prepared to assess the
quality of on-site monitoring and sample collection. The QAPP
should also include protocols and special samples (Quality
Assurance or QA Samples) that will help you assess data quality.
These steps should include:
Exact protocols on daily calibration of field monitoring
equipment such as pH meters, flow meters, UV gas detectors,
and conductivity meters. Manufacturers' manuals should be
provided to ensure correct calibration.
Protocols for quality control checks during operation of field
and laboratory instruments. Frequent use of independent
quality control check standard materials (QCCS)
(independent of calibration standards) will be necessary.
Protocols for collection of QA samples including field
duplicate samples to measure field variability; and field blank
samples - samples that are laboratory pure water (deionized
and distilled) but handled just as any other sample - are used
to check for cross-contamination between samples.
Protocols for cleaning of equipment and safe
decontamination of field equipment to avoid cross-
contamination of samples or health risks to inspectors and
technicians.
Protocols for laboratory QC sample analysis for assessment of
accuracy, precision, and detectibility.
Protocols to identify the number and types of sample
containers to be used and the volumes of samples and
preservatives required.
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Plan The Logistics Arrangements for travel and secure shipment of samples should be
made ahead of time. Make sure that the materials you will require
are collected, packed and shipped (when necessary) to a place
where they will be secure until you arrive. Checklists are often used
to verify that you will take everything you need. Use a field log
book with numbered sequential pages for maintaining observations
taken during your inspection. Make all entries directly in this book.
Do not transcribe them from other papers but take this book into
the field with you. Do not obliterate entries but place a single line
through incorrect entries, make corrections and initial corrections in
the margin of the page.
If you are taking any monitoring instruments to the inspection site,
such as pH meters, flow meters, gas detectors, etc. check them out
before you pack them to make sure they work and can be calibrated
for use. Carry fresh spare batteries for instruments that are battery-
powered as well as some alcohol and an abrasive cloth to keep
battery terminals clean.
Carry an ample supply of clean laboratory water for use as field
blanks or to make buffers and other reagents in the field. If
possible, make up standards for calibration fresh for each inspection
and refrigerate them while you are in transit.
It will be important to coordinate your activities with the laboratory
that will analyze the samples. Check requirements for sample
volumes and preservation methods with the laboratory and give
them advance warning about when and how many samples will
arrive at the laboratory. Make sure someone will be there to
receive them so that the samples will be maintained in a chain of
custody.
Identifying Inspectors should rely on the QAPP and the Sampling Plan in that
Sampling Points document to identify sites where samples are to be taken. In
permitted sites, you may find conditions that are not in agreement
with what is stated in the QAPP and you will have to use your
discretion about drawing additional samples based upon your
interview and what your eyes, ears, and nose tell you. Monitoring
instruments that you carry may extend the sensitivity of those senses
but your most important tool will be your judgment. Remember
that deviations from your Sampling Plan and QAPP will need to be
documented in your field notes and that you will need to amend
your QAPP when you return to your office to provide justification
for the change in the inspection and guidance to the next inspector
who visits that site.
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Many inspectors find it useful to photograph each sample location at
the time the sample is taken or monitoring is performed to capture
a visual image of conditions. If you can photograph the sampling,
remember to write the frame number in your field notes.
Using Monitoring If you are using monitoring instruments, you will need to check their
Equipment operation and calibrate them at the beginning of each day. Follow
the manufacturer's instructions regarding recalibration and use of
quality control check standards.
Record all instrument readings in your log book along with date,
time, and specific sample site location (for example - "air vent near
process tank on northwest corner/second floor of building #2- see
indicator on map"). Also indicate in your field notes if other
samples were also collected at the site.
Collecting Samples Samples or monitoring readings (when appropriate) should be
collected at all observed discharges for water and air effluents when
discharges are occurring. Locations that show discoloration, scums,
slimes, deposits, corrosion, and other indications of chemically
contaminated discharges should have the highest priority. Similarly,
air monitoring may be appropriate where discharges are apparent,
or where odors, visible vapors, air flow noises, or abrupt heat
differences indicate stack or fugitive emissions. Permanent
collection devices, such as bag or precipitator air cleaning devices
may be sampled as can process reactors if it is desirable to
characterize and quantify ingredient/process/waste/ product streams
for the application of mass-balance approaches to determining
wastes.
Water samples may be collected directly from flows by grab sample,
or by pump or collection bottle, taking precautions to rinse
collection devices and go from areas of lowest contamination levels
to high if possible to minimize sample cross-contamination.
Air samples are most often obtained using monitoring
instrumentation, or by the use of a pump and adsorbent system to
capture contaminants from an air stream (see Figure 4-1).
Solids such as soil can be scoop sampled, or drilled, or cored. Liquid
wastes such as solvents or chemicals in barrels are best sampled
using a dipper that is usually called a "thief.
AT ALL TIMES DURING SAMPLING, INSPECTORS SHOULD
KEEP THEIR SAFETY FOREMOST IN THEIR MIND.
INSPECTORS SHOULD NOT RISK THEIR LIVES OR
HEALTH TO COLLECT SAMPLES.
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Sample volumes vary with the media to be analyzed and the
contaminants of interest. Laboratories can advise you concerning
the types of containers that should be used for specific sampling and
the volume or weight of sample to be collected. Reference guides
such as the Water Pollution Control Federation (WPCF) Handbook
for Chemical Analysis of Freshwater can also give you guidance.
SANDING DISK
COPPER TUBE
RUBBER STOPPER
-DUCT WALL
Figure 4-1. Sampling from a high-negative-pressure duct
QA Samples Quality Assurance Samples from the field will account for about
10% of the total number of samples sent to the laboratory. They
include field blank samples to identify background levels of
contamination encountered in sampling; field duplicates to identify
site variability; and split samples (where a sample is divided in half
and put into two separate containers in the field) for estimating
variability introduced by sampling itself.
Preservation Most samples will need to be preserved to stabilize the
contaminants in the sample against thermal, chemical, or biological
decomposition. Some samples can be preserved chemically but
many will need to be refrigerated at 4 degrees Celsius for shipment
to the laboratory to retard decomposition. It is very important to
ship samples well chilled in the fastest possible way. The
temperature of the samples upon arrival at the laboratory will also
need to be recorded.
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Labels
Sealing
Chain of
Custody
Samples taken in the field need to be labeled completely and
correctly prior to shipping. Every sample label should contain:
a unique sample number;
site name;
date;
time;
analysis;
preservative used; and
inspector's name.
The sample control number should be recorded in the field log book
along with a description of the sample that includes sample location
and type as well as the dates of sampling and shipping and
conditions of shipping. Later, you will confirm the sample's
condition at the time of arrival at the laboratory and make that part
of your log entry.
Samples should be sealed with a protective band of tape that
prevents seepage that could contaminate the sample. Sealing the
sample in a plastic bag, or even two plastic bags, will help prevent
contamination of other samples. Ice that is used to cool the samples
in the cooler for shipping should also be bagged in plastic to
minimize the risk of melt-water contaminating the samples. At the
laboratory, the bags and seals should be inspected by the technicians
to confirm that no breakage, leakage, or tampering has occurred.
Once the shipping container containing the samples is full, and the
shipping temperature of the samples can be confirmed at 4 degrees
C, die cooler should be closed, sealed with packing tape, and then
sealed with a custody seal. Transfer of the cooler from inspector, to
shipping agent, to laboratory clerk should be documented with
signatures and dates on a chain-of-custody receipt that travels with
the samples. Upon arrival at the laboratory, the laboratory
technician or clerk who receives the samples should examine the
seal for tampering and certify it's integrity before opening the
shipping cooler. The technician should confirm the 4 degree C
temperature in the cooler upon opening, and store the samples in a
secure, cold location, where access is regulated and documented. In
this way sample integrity can be assured and documented to refute
any claim of tampering or mishandling that could compromise the
data. In general, samples should arrive at the laboratory within a
day or two of collection to ensure adequate refrigeration, and
samples should be packed with an equivalent weight of ice (5 liters
of samples needs 5 kilograms of ice) to ensure adequate
preservation in transit.
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Confirm Condition It is the inspector's responsibility to confirm that the samples arrived
of Samples on safely and that all samples were intact and that refrigeration was
Arrival adequate. To complete his records, the inspector should request the
chain of custody receipt form and seals be returned to him for
inclusion in the inspection file.
Evaluating the
Data
Laboratory and
Field Quality
Control Data
Quality Assurance
Maintaining
Records
Both quality control and quality assurance data need to be evaluated
before you can use the sample data with confidence. Here are some
things to look for.
Confirm that all laboratory analyses support the "accuracy"
data quality objective for each
analysis parameter.
Confirm that the laboratory has tested accuracy of analysis
using either analysis of an independent audit material,
recovery of a "spike" of the analyte of concern added to a
sample after original analysis, or in the case of analysis for
unknown organic materials, that a surrogate organic
compound of similar molecular weight and structure can be
quantified accurately.
Confirm that the laboratory has analyzed duplicates or splits
of samples and that the results are repeatable within the data
quality objective for precision.
Confirm that the laboratory has satisfactorily demonstrated
the detection limit for the analytes of interest on a regular
basis.
Examine the results of field blank analysis and confirm that
field blanks do not contain contaminant of interest in
concentrations greater than 3 times higher than the
instrument detection limit.
Examine the results of field duplicate analysis to characterize
field variability of the contaminant.
Examine the results of field split analysis - variability should
not exceed the specified data quality objective for precision.
Examine sample results data for outlier values data which
lie far below or far above the mean and standard deviation
for the rest of the field sample (don't include the blank)
results. These data may be suspect. Applying a statistical
test for outlier value (such as Grubbs outlier test) can assist
you with this evaluation.
Original copies of laboratory reports, chain of custody documents,
calculation worksheets, and your field notebook should be
maintained as part of the inspection file. These records should be
secured to avoid loss or tampering.
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4.6 INTERVIEWS
Planning the
Interview
Conducting and
Documenting
the Interview
Questioning
Techniques
As the first step in the interviewing process, planning the interview
should involve:
Identifying the interviewees who could provide information to
meet inspection objectives;
Identifying the specific reason that a particular person is to
be interviewed and information to be obtained; and
Scheduling the interview at a convenient time and place for
the interviewee, if possible.
The initial contact between inspector and interviewee sets the tone.
The main points of the interview include:
Asking the employee to explain his or her responsibilities as
they relate to the topics being reviewed in the inspection;
Asking specific and concrete questions to help answer the
compliance questions raised in the inspection plan;
Rechecking after each phase of the interview to see that all
the "unknowns" have been explored;
Rearranging the information mentally into a logical order;
and
Summarizing the interview to allow the interviewee to correct
any mistakes.
An inspector should always document an interview, either by taking
detailed notes, getting signed statements, or tape recording the
interview.
The basic questions used in interviewing are:
What happened?
When did it happen?
Where did it happen?
Why did it happen?
How did it happen?
Who was involved?
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Collecting
Written
Statements
Suggestions for improving interviews are:
Ask questions that require narrative responses rather than
"yes" or "no" answers. Yes/No questions should be used only
when summarizing or verifying information that has already
been given.
Avoid leading or suggestive questions which might bias the
interviewee's answers and detract from their objectivity.
Avoid questions that ask for two separate pieces of
information.
Order the questions from general to specific topics:
determine what was done before exploring how it was done.
Start with the known areas of information and work toward
the undisclosed information.
Work backwards in time, from the most recent events.
To help interviewees estimate quantities more accurately, use
well-known reference points, relate to commonly observed
quantities, or compare to similar items or distances at the
interview site.
Give the interviewee time to think about the response.
When taking written statements, an inspector should:
Determine the need for a statement.
Ascertain all the facts and record those which are relevant
regardless of the source.
Prepare a statement by:
Using a simple narrative style,
Narrating the facts in the words of the person making
the statement, and
Presenting the facts in chronological order.
Identify the person positively (name, address, position).
Show why the person is qualified to make the statement.
Present the pertinent facts.
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Have the person read the statements and make any necessary
corrections before signing (all mistakes that are corrected
must be initialed by the person making the statements).
Ask the person making the statement to write a brief
concluding paragraph indicating that he or she read and
understood the statement.
Have the person making the statement sign it. If the person
refuses, then ask for a statement in the person's own
handwriting stating that the statement is true, but that he or
she refused to sign it.
Give a copy of the statement to the signer if requested.
4.7 OBSERVATIONS AND ILLUSTRATIONS
Make use of all sense perceptions: sight, smell, hearing, or touch.
Make use of sketches, field notes, and photography.
Photographs as Photographs are becoming increasingly important in the
Evidence enforcement of environmental law because they are persuasive in
court proceedings and provide excellent documentation.
For these reasons it is very important that inspectors become good
photographers. Before visiting a facility inspectors should learn:
Which film type is best for the expected conditions;
How to load and unload the film;
How to insert batteries for the flash unit (if separate) and
camera;
The minimum focal distance of the camera;
How to operate the flash unit;
The maximum flash distance; and
Whether the camera has a sliding lens cover.
Although the right to photograph is part of the right to inspect,
inspectors must testify that photographs fairly and accurately
represent site conditions.
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Tips on Taking
Photos
Maintain fresh film and batteries.
Use a waterproof camera if possible.
Pay special attention to composition, including the center of
interest, background, and scale.
Use a camera which automatically records the date and time
on the film.
Drawings and
Illustrations
Document photos by noting in logbook the frame number
along with a detailed description of the subject matter.
Take a picture of your business card as the first photograph
on the film.
Record necessary information on the back of the photo when
working with an instant camera.
Place a common item next to the item of interest to indicate
size and scale.
Photograph all sides of an item if necessary to document a
violation.
Take several photographs using different settings if the light
is poor.
Take overlapping photographs to depict a wide area.
Maps showing location of facility and plot plans showing activities
within facility are useful. Use sketches to supplement photos of
equipment. Identify photo sites, sample sites, and observation sites
on a sketch map or on the original site map in your logbook.
4.8 EXIT INTERVIEW
When the inspection is complete, the inspector should conduct a
quick, concise, wrap-up interview to obtain any additional
information necessary and to convey to the facility representative
the findings of the inspection.
However, inspectors should carefully avoid conveying conclusive
compliance determinations because:
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The inspector has not had time to reflect upon and correlate
all observations;
Laboratory analyses have not been completed;
Other individuals may ultimately determine the facility's
compliance status; and
The inspection findings may represent only a portion of an
enforcement case.
If asked if any violations were found, the inspector may point out
various items the facility officials might want to recheck for
compliance purposes. Inspectors should never say "there are no
violations" at the facility.
Inspectors also should not leave a copy of field notes or checklists
with the facility representative because:
The inspector's notes or shorthand may be misunderstood;
and
The inspector may remember and write down something after
leaving the site (may result in discrepancies).
4.9 EXIT OBSERVATIONS/ACTIVITIES
Upon leaving the facility, the inspector should resurvey the site and
note whether any significant changes have occurred since the
inspection began. Such observations may better represent typical
operating conditions than what was recorded while the inspector was
on site.
The inspector should also review and complete site drawings and
chain-of-custody forms following the inspection.
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CHAPTERS
5.0 POST-INSPECTION ACTIVITIES
5.1 THE INSPECTION REPORT
The purpose of the inspection report is to present a complete,
accurate, and factual record of an inspection. It organizes all
evidence gathered in an inspection.
Elements of an Although the format and exact contents of an inspection report will
Inspection Report vary, each one should provide enough information to tell the reader:
The specific reason for the inspection;
Who participated in the inspection;
That all required notices, receipts, and other legal
requirements were met;
What actions were taken during the inspection, including the
chronology of these actions;
What statements, records, physical samples, and other
evidence were gathered during the inspection;
What observations were made during the inspection; and
The results of the sample analyses related to the inspection.
Also, most reports will contain inspection report forms, narrative
reports, and documentary support.
Writing an When writing an inspection report, it is important to relate the facts
Effective and evidence relating to the inspection simply and with the reader
Inspection Report in mind. A good inspection report exhibits:
Fairness;
Accuracy;
Conciseness;
Clarity;
Completeness;
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The source of evidence;
Exhibits (supplementary material);
Organization; and
Good writing.
Narrative Report Narrative reports, as part of an overall inspection report, should be
a concise, factual summary of observation and activities. Basic steps
involved in writing the narrative report include:
Receiving the information;
Organizing the material;
Referencing accompanying material; and
Writing the narrative report. Be sure to:
use a simple writing style;
keep paragraphs brief and to the point;
avoid repetition; and
proofread the narrative.
Despite the variations in the specific information contained in a
narrative report, most reports can follow an outline, which features
the:
Introduction
general information
summary of findings
history of the facility;
Inspection activities
entry/opening conference
records
evidence collection
physical samples
closing conference; and
Attachments
list of attachments
documents
analytical results.
Include photos, maps, and illustrations if they are available.
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IV
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WASTE WATER INSPECTIONS
-------
TABLE OF CONTENTS
Chapter Page
1.0 GENERAL WASTEWATER INSPECTION PROCEDURES 1-1
1.1 Objective 1-1
1.2 Purposes of Wastewater Inspections 1-1
1.3 Inspection Procedures 1-1
1.4 Pre-Inspection Preparation 1-2
1.5 Onsite Activities 1-4
1.6 Follow-Up Activities 1-10
2.0 WASTEWATER SAMPLING TECHNIQUES 2-1
2.1 Purposes for Sampling 2-1
2.2 Sampling Procedures 2-1
3.0 WASTEWATER TREATMENT TECHNOLOGIES 3-1
3.1 Introduction 3-1
3.2 Types of Wastewater Treatment 3-1
3.3 Flow Equalization 3-2
3.4 Typical Treatment for Metal Finishing Wastewater 3-3
3.5 Other Treatments for Metals Removal 3-6
3.6 Organics Treatment 3-7
3.7 Oil Removal 3-9
4.0 POLLUTION PREVENTION TECHNIQUES 4-1
4.1 Introduction 4-1
4.2 Process Changes 4-1
4.3 Material Substitution 4-4
4.4 Material Inventory and Storage 4-5
4.5 Waste Segregation 4-5
4.6 Good Housekeeping/Preventative Maintenance/Employee Education . . . 4-6
4.7 Product Changes 4-7
4.8 Water/Energy Conservation 4-8
4.9 Recycling 4-9
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CHAPTER 1
WASTEWATER INSPECTION PROCEDURES
1.1 OBJECTIVE
This section provides general procedures to follow when inspecting a
facility's wastewater generation and discharge.
1.2 PURPOSES OF WASTEWATER INSPECTIONS
Purposes of There are many purposes for conducting wastewater inspections at industrial
Inspections and commercial facilities. One of the primary purposes is to gather
information about the facility's processes and operations and to characterize
its discharges. This characterization should include the volume of
wastewater discharges, the types of pollutants the facility discharges or has
the potential to discharge, and whether or not the facility's discharge has
the potential to cause damage to the receiving stream or the environment.
Information gathered can be used to assess the need for pollutant controls
and to develop discharge permit conditions or other associated requirements
aimed at reducing pollutant discharges and thus reducing the negative
impacts of these discharges on the environment. If facilities are required to
submit information such as permit applications, or responses to surveys,
inspections can also serve as a means of verifying the accuracy of data and
information submitted by the facility. Once this information has been
gathered, inspections should be performed to maintain and update
information on facilities.
Information gathered during inspections can also be used to evaluate the
facility's compliance with any standards or requirements and to support any
necessary enforcement action for noncompliance. Inspections can also be
performed to verify the correction of problems and the attainment of
compliance, such as the installation of wastewater treatment equipment.
1.3 INSPECTION PROCEDURES
Inspection As with all types of inspections, a wastewater inspection consists of three
Procedures general steps; pre-inspection preparation, onsite activities, and follow-up
activities. Pre-inspection preparation is important so that an inspection is
well planned and efficient and that the inspection objectives are met. Onsite
activities are the most essential part of the insDejctipn .and may include
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meeting with facility representatives, conducting a thorough inspection of
the facility (including its operations and manufacturing processes, storage
areas, and wastewater treatment systems), and examining records. Follow-
up activities are necessary to ensure that inspection findings are properly
documented. Each of these steps will be discussed in greater detail.
1.4 PRE-INSPECTION PREPARATION
Pre-Inspection Pie-inspection preparation involves several activities including review of
Preparation facility records and literature references, development of an inspection plan,
notifying the facility (if applicable), and assembling and calibrating safety
and sampling equipment. Each of these activities will be discussed in
greater detail.
Records The inspector should begin preparation for an inspection by reviewing any
Review background information already gathered on the facility. Information to be
reviewed may include data submitted by the facility such as responses to
surveys or questionnaires or permit applications and correspondence. In
addition, reports from any previous inspections or site visits and
information relating to the facility's compliance history should be reviewed.
During this review, any unresolved compliance problems should be noted so
that the inspector can verify these problems onsite. In order to determine
compliance, the inspector must be knowledgeable about any regulatory
requirements that apply to the facility. If not familiar with these
requirements, the inspector should review all relevant requirements, such as
permit conditions prior to the inspection.
Literature To perform a thorough but efficient inspection and to establish credibility
Review with the facility, the inspector should have at least a basic working
knowledge of die facility's manufacturing process. If the inspector is
unfamiliar with the particular operation or manufacturing process performed
by the facility, applicable literature sources should be reviewed in order to
gain a better understanding of the specific process or operation.
Inspection Once the inspector is familiar with the facility's background information, an
Plan inspection plan should be developed. Basically, an inspection plan should
outline the scope and objectives of an inspection and identify how the
inspection objectives are going to be met. The objective of the inspection
will determine the scope and depth of the inspection.
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During preparation for an inspection, the inspector should note any
questions that need to be answered during the onsite activities. By
preparing a list of, the inspector can better ensure that all necessary
information to develop a
complete picture of the facility is gathered.
Facility In some cases it may be appropriate to notify the facility of an impending
Notification inspection. For instance, if a complete facility tour is desired, it may be
beneficial to notify the facility so that the appropriate representatives are
present. In other cases, such as if noncompliance is suspected or in the
event of a spill, notification may not be desirable. The inspector should
determine if notification is appropriate and, if so, should contact the facility
by telephone or by sending a letter.
In the United States three types of inspections are performedscheduled,
unscheduled, and demand.
Scheduled inspections are those that are scheduled in advance and that
the facility has been notified of the approximate date and time the
inspection will occur. Scheduled inspections are most often used for
initial or routine inspections.
Little or no advance notice is given to the facility in an unscheduled
inspection. Unscheduled inspections are useful as random spot checks
in certain cases such as the facility is suspected to be out of
compliance.
s
Demand inspections are generally conducted in response to a specific
problem or emergency situation such as a spill.
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Health and Ensuring inspector safety is very important during an inspection. Specific
Safety information on safety equipment necessary for the particular facility being
inspected should be gathered prior to the onsite activities.
This information can be obtained from previous inspection reports, talking
to people that have visited the facility in the past, or by obtaining the
information directly from the facility. If the facility is notified of an
inspection, this may be a good opportunity to inquire about safety
equipment necessary for the inspection.
Equipment The final step prior to an inspection is to prepare any equipment necessary
Preparation for the inspection. The type of equipment needed will be dependent on the
nature of the inspection and may include safety and/or sampling and flow
measurement equipment. The inspector should ensure that all equipment to
be used is calibrated and is in proper working order. The inspector may
also want to take a camera so that photographs of the facility can be taken.
1.5 ONSITE ACTIVITIES
Periphery Prior to entering, the inspector should conduct an examination of the
Inspection periphery of the facility. If an inspection has not been performed
previously, the inspector should note the general size of the facility
including the number of buildings at the site.
Any problems around the facility's perimeter such as apparent spills or
improperly stored chemicals should be noted. Environmental conditions
such as the condition of surrounding vegetation, odor problems, abnormal
stack emissions, and whether the facility has a direct discharge to a
receiving stream should be noted.
If outside chemical or waste storage areas are visible, the inspector should
note the condition of these areas, including spill containment, and any
associated problems such as leaking drums.
Finally, if located in an easily accessible area, the inspector may want to
look at the facility's discharge points to see if there are any unusual
discharges.
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If sampling is to be conducted as part of the inspection, the inspector may
want to set up the sampling equipment at this time. It may also be useful to
perform certain analyses such as pH prior to entering the facility. Doing
this may provide insight to additional problems that should be addressed
during the inspection. Any problems noted during the examination of the
facility's periphery should be addressed during the inspection.
Facility
Entry
When entering the facility, the appropriate facility representative should be
located. The inspectors should identify themselves and be familiar with and
follow applicable procedures for facility entry. Inspectors should provide a
copy of the written inspection order.
Opening It is generally a good idea to conduct an opening conference or pre-
Conference inspection meeting with facility representatives, particularly if it is the first
visit to the facility.
During this meeting the inspector should briefly state the purpose of the
inspection and inform the facility representatives of the intended schedule
and order of the inspection. By doing this, it can be better assured that the
proper facility representatives will be available to conduct the tour and
answer questions. The inspector should also identify any additional records
or information that will be needed so that the facility can gather the
necessary information while the inspector is onsite.
The inspector should use the opening conference to ask any questions
identified during the pre-inspection preparation and to obtain general
background information such as the number of employees, production rates,
wastewater flow rates, and any changes that have been made since the last
inspection. Since many manufacturing facilities are noisy, it may be
difficult for the inspector to hear during the tour. Therefore, it may be
beneficial to have facility representatives give a brief description of the
industrial processes during the opening conference, particularly if it is the
inspector's first visit to the facility. If the facility has a plant schematic, the
inspector should obtain a copy to make the tour easier to follow and to
better ensure that all areas of the facility are covered.
Inspectors should also answer any questions the facility may have. From
the start the inspector should strive to establish a good rapport with facility
representatives so that they are comfortable and will more readily answer
questions and provide the information the inspector needs.
Inspectors should also provide facility representatives with information on
applicable regulations and their associated responsibilities. If the facility
does not have copies of applicable regulations, the inspector should provide
and review these during the opening conference. General information on
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pollution reduction and pollution prevention techniques such as brochures or
guidance manuals should also be provided.
Inspectors need to remain flexible and be ready to mate changes in their
inspection plans. Based on the observations during the examination of the
facility's periphery or information obtained during the opening conference,
it may be necessary to change the objectives or order of the inspection. For
instance, if it was noted during the examination of the facility's periphery
that a sump collecting runoff from a hazardous materials storage area was
being pumped directly to the surrounding ground, this area should be
investigated as soon as possible so that the problem is not discovered and
corrected by the facility before the inspector has a chance to investigate it.
Facility After the opening conference, the inspector should conduct a full tour of the
Tour facility. Conducting a tour is very important to allow a full description and
understanding of the facility's processes and to verify information provided
by the facility. Tours also allow the inspector to identify problem areas that
can be improved through pollution reduction techniques. The tour should
focus on areas of the facility where wastestreams and/or pollutants are
produced, processed, pumped, conveyed, treated, or stored. Such areas
may include the facility's production processes, storage areas, and treatment
equipment. The inspector needs to gain a full understanding of the
facility's wastewater generation and treatment. For better understanding of
the entire process, it is best to tour the facility in order of production,
starting from raw materials and following to the finished product.
Throughout the inspection, the inspector needs to locate all sources or
potential sources of wastewater discharge. Sources may range from those
that are easily identified such as a running water rinse from a plating bath
to those more difficult to identify such as a discharge from a wet air
scrubber. A description of each discharge should be obtained. This
information should include whether the discharge is batch or continuous, the
amount of discharge, pollutants potentially in the discharge, and frequency
of each discharge. The inspector also needs to identify the destination of all
wastewater generated and all discharge points. Some wastewater may be
discharged directly to a receiving stream while some may be discharged to
the sanitary sewer with or without first going to a pretreatment system.
If possible, all wastewater flows should be measured or information on
wastewater flows from each process should be requested from facility
representative. All recirculating systems such as air conditioners should be
noted and it should be determined if these systems ever discharge.
Evaporation, use in products, and washwater should be accounted for.
Washdown of vessels and process areas can be a significant source of
wastewater. It should be determined if any batch discharges occur.
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Reactors, plating tanks, and process tanks are often periodically discharged.
The amounts and chemical nature and frequency of discharge, and treatment
and disposal should be noted.
The inspector should also gather information on the flow of incoming water
to the facility. With information on incoming water flow and wastewater
generation and flow, the inspector may be able to calculate a rough flow
balance. A flow balance compares the incoming water flow to the total
outgoing wastewater flow to ensure all water use at the facility is accounted
for. If the flow balance indicates discrepancies in flow volumes between
the incoming water and outgoing wastewater, the inspector should discuss
them with the facility representatives. Causes of the discrepancies may
include evaporation or water that is used but not discharged such as water
contained in the product used in a recirculating cooling system.
All industrial processes, raw materials, and finished products should be
evaluated to determine pollutants being used or generated. For example, at
a facility performing electroplating, quantities and types of plating and
associated chemicals used, frequency of disposal and treatment and/or
disposal methods should be noted.
Throughout the entire inspection process, inspectors should attempt to
identify areas in which the industry can decrease its use of chemicals and
reduce the amount and pollutant concentration of its discharges through
pollution reduction technologies.
The inspector should require schematics of the facility from the industry
before the first inspection. A schematic of the facility that shows the
processes, their wastewater discharges, flow through the treatment system,
and discharges points. A description and process flow diagram for each
major product line should also be provided. Then, throughout the
inspection, these schematics should be checked by the inspector to make
sure these are accurate.
The quantities and types of raw materials, finished products, and wastes
stored at the facility should be noted. The inspector should evaluate storage
areas to determine the potential for spills to occur and to enter the sanitary
sewer. The proximity of floor drains to any area where pollutants are
stored or handled such as storage and processing areas should be
determined.
If floor drains are present, the inspector should determine whether or not
the floor drains are used. The condition of a floor drain may indicate
whether or not it is used.
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For example, the floor drain may be corroded, indicating that corrosive
materials have been discharged. Floor drains that are permanently capped
or welded shut are preferable to just being plugged since these can be
removed. In cases where the floor drains are capped or plugged, but not
welded, the inspector should inspect the floor drain for evidence that the
cap or plug is simply removed when the facility wants to discharge
material. The inspector should also determine where the floor drains flow.
For example, some floor drains may flow to the wastewater treatment
system while others may discharge directly to the sanitary sewer.
Spill containment structures such as berms and dikes should also be
evaluated to determine if they are adequate to contain spills.
Inspectors should inquire as to the cleanup and disposal procedures the
facility would follow in the event of a spill. The industry should have a
spill plan on file at the facility. The inspector should evaluate the potential
for a spill to enter the sanitary sewer when the facility's procedures are
followed.
The wastewater treatment system should also be inspected to ensure that it
is properly maintained and is in good working condition. Treatment systems
may consist of physical, chemical, or biological processes that are used to
remove or treat pollutants prior to discharging wastewater. Wastewater
treatment can range from a simple oil and grease separator to a complex
chemical system designed to remove metals. The inspector should note the
type of treatment used, any associated chemicals used, and any
circumstances under which the treatment system would be shut down or
bypassed.
Information should also be obtained on any sludges or residuals generated
during the wastewater treatment process and methods by which these
sludges and residuals are disposed.
Operation and maintenance procedures implemented in the treatment system
should be discussed and appropriate documentation should be reviewed.
For example, if the facility continuously monitors pH, the pH logs should
be reviewed and the inspector should determine the frequency at which the
pH probe is calibrated, ink is added, or the paper is changed. In addition,
the inspector should verify that adequately trained staff are available to
properly operate and maintain the wastewater treatment system. It is also
helpful to develop a diagram detailing the treatment process.
Many industrial processes such as cleaning, degreasing, grinding, and
chemical wastewater pretreatment produce a sludge or other waste that must
be disposed of. For instance, vapor degreasing often produces a sludge as
well as spent solvent waste that must be disposed of. The inspector should
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determine the waste generation rates, how often disposal occurs, and the
method of disposal.
If sampling is to be conducted at the facility, the inspector may want to
identify an appropriate sampling location during the inspection.
The inspector should review any records the facility may have compiled that
relate to its discharges. These records may include analytical results of its
wastewater discharge, flow records, and treatment system operation and
maintenance records.
Although general inspection procedures have been outlined in this
presentation, questions to ask facility representatives and necessary
information to gather depends on the type of facility being inspected.
Checklists that detail questions for general industrial inspections as well as
questions for specific types of industries are included as part of the handout.
It may be useful to review these questions and take a copy of the checklist
into die field. For example, specific information to obtain during inspection
of a facility performing electroplating may include the following:
Chemicals used in plating and cleaning baths (including cyanide)
Volume of plating and cleaning baths
Frequency at which plating and cleaning baths are changed
Treatment and disposal methods of spent baths
Description of all wastewater generated and methods of treatment and
disposal
Whether any floor drains are located in process or storage areas
Whether any solvents or degreasers are used and, if so, methods of
treating and disposing of spent solvents
Whether any sludges are generated in plating baths, degreasing units,
or wastewater treatment systems and, if so, how are they treated and
disposed. The inspector should review any records or file with the
industry showing how much sludge was generated and where it was
disposed (onsite or off site). If shipped off site, the inspector should
inquire as to the final destination. If these waste tracking records do
not exist, the inspector may want the industry to start keeping records.
Whether any air pollution control equipment uses water.
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Note the ventilation system above the plating tanks. The inspector should
determine whether the collected vapors pass through a wet air scrubber.
Closing After conducting the facility inspection, the inspector should meet with
Conference facility representatives to ask for any further information or clarify any
outstanding issues. The inspector should prepare a written summary of
inspection findings. The inspector should also answer any of the facility's
questions and allow the facility to respond to the inspection findings.
1.6 FOLLOW-UP ACTIVITIES
Follow-Up In order to ensure that the inspection is documented so that information can
Activities be readily retrieved for subsequent pretreatment program activities and to
aid in any enforcement action necessary, an inspection report should be
prepared. All inspection information including inspection notes, copies of
file information, photographs, and other information should be carefully
documented. Inspectors may also need to initiate or follow-up on any
enforcement actions necessary based on the findings of the inspection.
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CHAPTER 2
2.0 SAMPLING TECHNIQUES
2.1 PURPOSES FOR SAMPLING
Purposes for Although inspections may indicate which pollutants are potentially in a
Sampling facility's discharge, they cannot conclusively determine specific pollutant
information. To determine the types and concentrations of pollutants in a
facility's discharge, it is necessary to perform sampling. This specific
pollutant information can then be used to identify which pollutants in a
facility's discharge need to be reduced. Pollutant information can also be
used to determine the significance of a particular pollutant in the discharge
so that necessary monitoring frequencies can be determined. Sampling also
provides a means to determine a facility's compliance with its discharge
limits and as a basis for supporting enforcement actions. Finally, if a
facility performs self-monitoring, sampling can be performed to verify the
accuracy of that self-monitoring.
2.2 SAMPLING PROCEDURES
Preparation It is important to be adequately prepared prior to going onsite so that all the
and Imple- equipment needed to perform the sampling is available and that personnel
mentation are properly prepared for the types of sampling required. Therefore,
of Sampling general sampling procedures should be developed and followed when
Procedures sampling at all facilities. Sampling procedures should include designation
of sample types, volumes, containers, and preservation methods to be used
for each pollutant parameter as well as sample identification and
documentation procedures. Although these general procedures apply to all
facilities, specific information on each facility should also be developed.
This information may include pollutant parameters to be sampled, sampling
location, and safety concerns. Obtaining this information prior to the
sampling trip will allow the sampler to bring the proper equipment, know
where to sample and what pollutants to sample for, and be familiar with
necessary safety precautions.
Coordination The samplers should coordinate their sampling activities with the laboratory
with Analytical that will be performing the analyses. The laboratory can provide
Laboratory information on the types and volume of samples needed for particular
pollutant parameters, sample preservation methods and holding times, and
shipping instructions. Laboratories may also provide sampling equipment
such as samplers, pH meters, sample containers, chain-of-custody forms,
sample labels, tags, and seals.
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Preparation Prior to the sampling trip, any required sampling and safety equipment
of Sampling should be assembled, cleaned, and checked to ensure that it is in proper
and Safety working order. All necessary paperwork should also be prepared prior to
Equipment the trip. This may include assembling and marking, as possible, the
required sample container labels or tags, chain-of-custody forms, and lab
request sheets. Sampling and field analytical equipment such as pH meters
should be calibrated.
When conducting sampling, samplers need to be aware of health and safety
hazards and take the proper precautions. Safety requirements can be
gathered from file information, personnel that have previously sampled the
facility, or by contacting the facility. Samplers need to be properly clothed
and have adequate safety equipment available.
Samplers should not enter confined spaces unless they are properly trained
and have the proper equipment such as rescue equipment and respirators.
Confined spaces should never be entered unless first tested for sufficient
oxygen and lack of toxic and explosive gases. Two persons should be
present, one to enter the confined space and one to be outside of the
confined space. The person entering the confined space should wear a
safety harness that is attached to a retrieval system. Use of this type of
system will allow the rescue of the person in the confined space without
requiring anyone else to enter.
Sampling Samples should be collected from a location that is representative of the
Location facility's discharge. If the facility has more than one discharge point it may
be necessary to collect samples from several locations in order to
adequately characterize the facility's entire discharge. Convenience,
accessibility, and safety should also be considered when selecting a
sampling site. Appropriate sampling sites may include manholes as shown
here. Other appropriate sites may be a process tank.
Samples should be collected from the center of flow with the container
facing upstream to avoid contamination. Samples should be collected in
areas that are turbulent and well mixed and where the chance of solids
settling is minimal. When sampling, the surface of the wastewater should
not be skimmed nor should the channel bottom be dragged. Samples should
not be collected from stagnant areas containing immiscible liquids or
suspended solids.
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Sample Types There are two basic types of samples: grab and composite samples.
Grab samples are individual samples collected over a period of time not
exceeding IS minutes and represent wastestream conditions only at the time
the sample is collected. Grab samples are usually taken manually but can
be collected using an automatic sampler. Grab samples may be appropriate
for batch discharges, constant waste conditions, to screen the discharge to
see if particular pollutants are present, or if extreme conditions such as high
pH are characteristic of the discharge. In addition, grab samples should be
collected for pollutants that tend to change or decompose during the
compositing period such as pH, cyanide, total phenols, and volatile
organics. In addition, grab samples should be collected for oil and grease
samples since the oil and grease tends to adhere to sampling equipment.
Composite samples are collected over time (either by continuous sampling
or by combining individual grab samples) and reflect the average
characteristics of wastewater during the sampling period. Composite
samples are either flow proportional or time composited:
In flow proportional sampling, the volume of sample collected is
proportional to waste flow at the time of sampling. Flow proportional
samples can be obtained by collecting various sample volumes at equal
time intervals in proportion to flow or by collecting a constant sample
volume per unit of wastewater flow.
Time composite samples consist of constant volume sample aliquots
collected in one container at equal time intervals. For example, 500
milliliters of sample collected every IS minutes over a 24-hour period.
Composite samples may be needed to determine the average characteristics
of wastestreams, particularly if the wastestream has a highly variable
pollutant concentration or flow rate. Composite samples should be
collected during the entire period the facility is operating and discharging.
For example, if the facility has processes that discharge 16 hours a day,
samples should be collected during the entire 16-hour period.
Sampling Both grab and composite samples can either be collected manually or with
Equipment automatic samplers. However, it is not recommended that automatic
samplers be used to collect samples for certain pollutants such as oil and
grease and volatile organics since oil and grease may adhere to the sides of
the sampler tubing and air may be introduced into volatile organic samples.
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Sample Sample volumes needed for analyses depend on the type and number of
Volumes analyses to be performed. The sampler should contact the person or
laboratory that will be performing the analyses to determine sample
volumes needed for a particular sampling event. Adequate sample volume
should also be collected to allow for QA/QC and for spillage
Sample Sample containers should be made of chemically resistant materials that will
Containers not affect the nature or concentration of pollutants being measured.
Containers must be large enough to hold the required sample volume.
Glass containers should be used for oil and grease, phenol, and organics
samples. Amber glass sample containers should be used for pollutants such
as iron cyanide that oxidize when exposed to sunlight. Containers with
teflon lined lids should be used when collecting volatile organics. Plastic is
easier to handle and is less likely to break, so it may be the best type of
container to use when glass is not needed. Sample containers should be
properly cleaned prior to use. The laboratory that will be performing the
sample analyses should be contacted for specific cleaning instructions.
Some laboratories may provide pre-cleaned sample containers.
Sample Preser- Many pollutants are unstable and may alter in composition prior to analysis.
vation and Therefore, to ensure that samples remain representative, they should be
Holding Times analyzed as soon as possible after collection. If immediate analysis is not
possible, samples should be preserved to minimize the changes in pollutant
concentrations between collection and analysis. There are three basic types
of preservation: cooling, pH adjustment, and chemical fixation. Cooling is
accomplished by chilling samples to 4°C by either refrigeration or by
placing on ice. Cooling suppresses biological activity and volatilization of
gases and organic substances.
If composite samples are collected, the samples should be cooled to 4°C
throughout the compositing period. Samples should also be kept cool
during transport to the analytical laboratory.
Even with proper preservation, samples should be analyzed within certain
recommended holding times. These holding times are the maximum times
allowed between the time the sample is collected and when it is analyzed.
If composite samples are collected, the holding time limitations begin when
the last aliquot is added to the sample. Performing sample analyses within
the allowable, holding times helps ensure that the analytical results are valid
and representative of the wastewater. Certain pollutant parameters such as
pH have no standard method of preservation and should be analyzed
immediately.
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CHAPTERS
3.0 WASTEWATER TREATMENT TECHNOLOGIES
3.1 INTRODUCTION
It is helpful to understand the types of wastes generated in various industrial
categories and common waste treatment and reduction techniques. The
following discussion will provide a brief description of some of the most
common types of waste treatment.
?3.2 TYPES OF WASTEWATER TREATMENT
Classification
of Treatment
Techniques
Wastewater treatment technologies can be grouped by type of treatment into
four classifications:
Physical treatment technologies modify the physical structure of the
wastewater and its pollutants or separate the wastewater into various
components. Physical treatment does not change the chemical structure of
the wastewater pollutants. Physical treatment is useful for separating
hazardous and non-hazardous components of a wastestream, separating a
wastestream into various components for different treatment operations,
conditioning a wastestream for further treatment, and removing solid
particles or objects. The most common physical treatment processes
include; equalization, screening, sedimentation, flotation, filtration,
adsorption, ultrafiltration, and stripping.
Chemical treatment technologies modify the chemical structure of the
wastewater pollutants to aid removal of these pollutants from the
wastewater. Chemical treatment technologies are usually relatively easy,
but generate a solid sludge that must be managed and disposed. The most
common chemical treatment processes include neutralization, precipitation,
oxidation/reduction, and dechlorination.
Biological treatment technologies degrade organic components of the
wastewater using microorganisms. These organics may be decomposed into
water and methane, other less toxic simpler organics, or microbial matter.
Toxic chemicals can inhibit biological treatment systems by killing the
microorganisms. Also, high concentrations of inorganics and high
temperatures can inhibit biological treatment. Also of concern, nitrogen
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and phosphorus are needed for biological activity to occur and are often not
present in industrial wastewater. The most common biological treatment
processes include stabilization, activated sludge, trickling filters, anaerobic
digestion, and aerated lagoons.
Thermal treatment processes achieve significant reductions in waste volumes
and achieve a high degree of destruction of organics. Unfortunately,
thermal treatment often generates hazardous air emissions that must be
controlled. The most common thermal treatment technologies include
incineration and evaporation.
Probably the most appropriate way to discuss treatment technologies is in
terms of the nature of pollutants to be removed (i.e., metals, organics, oil
and grease, etc.). A brief discussion of various accepted treatment
technologies for removing these pollutants follows; with a discussion of
some treatment practices common to all types of wastewater treatment
presented first.
3.3 FLOW EQUALIZATION
Flow Combining wastewater flows to dampen fluctuations in flow rates and
Equalization pollutant concentrations prior to further treatment or prior to discharge
(i.e., equalization) provides an extremely valuable performance
specification. Equalization typically occurs in tanks or basins that often
contain a large capacity to handle wastewaters for an extended period of
time. Often variable flowrates and pollutant concentrations can reduce
treatment efficiency. For example, equalization before chemical treatment
reduces the variability of flow, thereby reducing the necessary process
controls, minimizing the likelihood of over-or under-feeding of the
treatment chemicals. Equalization is useful for preventing slug loads from
inhibiting further treatment processes or for preventing excessive
concentrations in the treatment system effluent. Equalization can also act as
neutralization where both acidic and basic wastes are combined.
Another technique for equalizing wastewaters is to hold high concentration
wastes in a separate tank or basin and then bleed this waste into the more
dilute waste stream over a period of time to minimize the impact.
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3.4 TYPICAL TREATMENT FOR METAL FINISHING WASTEWATER
Chemical Metal finishing/plating/printed circuit board manufacturing facilities are one
Treatment type of facilities that most often use chemical treatment technology.
Typically, these facilities will require four types of chemical treatment for
pollutant removal; neutralization, hexavalent chromium reduction, cyanide
destruction, and chemical precipitation. A discussion of these treatment
technologies follows.
Neutralization/ Biological treatment operates most effectively at a pH of 7. Variations in
pH Control pH can have a significant impact on the treatment efficiency of biological
systems including total inhibition of microbial activity. Another reason for
pH control is for treatment performance optimization. This is especially
true for treatment to remove metals. Therefore, pH control is a crucial
component in wastewater treatment.
A pH control system typically comes in one of three forms, continuous
uncontrolled, batch controlled, and continuous controlled.
The simplest form is a continuous uncontrolled system that consists of
running acidic wastewater through a bed of limestone chips.
Another method is to batch treat a wastewater, whereby the pH is taken,
acid or base is added, the pH is reanalyzed, and the process continues until
the desired pH is achieved. At that point, the wastewater can be discharged
to the sewer or to additional treatment, if necessary.
The most advanced method of pH control is a continuous system where pH
sensors are used to measure the pH and to add the necessary treatment
chemicals. In a continuous system, a pH sensor determines the pH and
signals a pump to add neutralizing chemical, and the wastewater is mixed to
provide homogeneous chemical addition. More complex systems have
multiple pH sensors and multiple chemical addition points to further refine
chemical addition to obtain more constant pH values. Electrode
maintenance is a must for proper operation of the system as the electrodes
are prone to fouling, especially in extremely corrosive wastewaters.
Chromium Chromium is one of the most common plating metals. Wastewaters
Reduction containing hexavalent chromium are generated from chromium
electroplating, chromate conversion coating, etching with chromic acid, and
metal finishing on chromium metal. Hexavalent chromium (i.e., Cr+6) is
the soluble ion most commonly used in the plating bath and is much more
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.toxic than the trivalent form (i.e., Cr*3). Hexavalent chromium, which
includes chromic acid (H2Cr04), chromium trioxide (CrO3) and chromates,
must be reduced to the trivalent state to allow for chemical precipitation.
Some manufacturers will use a trivalent form of chromium, such as
chromium trichloride (CrCl3) or chromium sulfate (Cr2(SO4)3), in the
process baths although these chemicals are more expensive to use and may
not provide desirable qualities on the finished product that are achieved with
hexavalent chromium. Once the chromium has been reduced to its trivalent
state, it can be subjected to chemical precipitation to remove the chromium
and any other toxic metals.
Reduction is typically done using gaseous sulfur dioxide or sodium bisulfite.
Because the reaction proceeds much faster at low pH, the reduction should
be performed at a pH of 2-3. The closer this reaction is to a pH of 3, the
less sulfur dioxide will be released.
Iron or iron salts may also be used to reduce the hexavalent chromium to its
trivalent state. A third, patented process, uses small pieces of scrap steel,
adjusting the pH of the influent to a pH of 2.0-2.2, and then flowing the
wastewater through the steel scraps.
Chromium reduction is a proven technology that is easy to use and well
suited to automation. Reduction efficiencies of over 99.5 percent are easily
achieved with concentrations of 0.05 mg/1 readily attained. [Development
Document for Effluent Limitations Guidelines and Standards for the Metal
Finishing Point Source Category, June 1983] Chromium reduction
equipment is very simple and should include: a separate wastewater
collection system for wastewater that contains hexavalent chromium only (as
chemical interference is possible if mixed metal wastes are subjected to the
chromium reduction process), metering equipment, contact tanks with
agitation, and pH and oxidation-reduction potential (ORP) instrumentation.
Cyanide Cyanide may be used as a cleaning agent and a complexing agent in zinc,
Destruction cadmium, silver, copper and other plating baths. Cyanide can be destroyed
through oxidation techniques. Chlorine (elemental or hypochlorite) is the
most common oxidation chemical used to destroy cyanide. Chlorine gas
treatment is about half the cost of sodium hypochlorite treatment, but
chlorine gas is dangerous to handle and should be accounted for when
evaluating options.
The alkaline chlorination reaction, by far the most common cyanide
destruction method, is a two step process and proceeds as follows:
1) C12 + NaCN + 2NaOH = NaCNO + 2NaCl + H2O
2) 3C12 + 6NaOH + 2NaCNO = 2NaHCOj + N2 + 6NaCl + 2H2O
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The destruction typically occurs in two tanks. In the first tank, the system
is monitored to maintain a pH of 9.S-11 with an oxidation-reduction
potential of 300-400 millivolts. This is where the cyanide is oxidized to
cyanates. This is also where the metal complex is broken, thus allowing
some of the metals to precipitate. In the second tank, the desirable pH is
8.0-8.5 with an oxidation-reduction potential of 600-800 millivolts.
Since cyanide is destroyed in the first stage reaction, many facilities have
eliminated the second stage since this second stage is costly and poses a
dangerous reaction situation (hydrogen cyanide gas generation) if the first
stage is not adequately controlled.
Alkaline chlorination of cyanide wastes is a proven technology with
destruction efficiencies of over 99 percent and effluent concentrations below
detection readily available.
Very simple equipment is needed for cyanide destruction including a
separate collection system for cyanide bearing wastewaters, contact vessels
with agitation, chemical metering, and pH and ORP instrumentation.
Chemical The most common pretreatment technology for pollutant removal is
Precipitation chemical precipitation. Chemical precipitation is used to reduce the
concentration of metals in wastewater to levels below concern.
Chemical precipitation is a three step process consisting of coagulation,
flocculation, and sedimentation. Through chemical addition, the
interparticulate forces in the contaminants are reduced or eliminated thus
allowing interaction of particles through molecular motion and physical
mixing. Rapid mixing allows for dispersion of the treatment chemical
throughout the wastewater and promotes collisions of particles. Collision of
these particles causes the particles to aggregate and form larger particles,
which is known as coagulation. The chemicals added to promote this
aggregation, known as coagulants, serve two basic purposes: (1) to
destabilize the particles, thus allowing for interaction, and (2) to promote
aggregation of particles through floe strengthening.
Alum (i.e., aluminum sulfate) and lime (calcium oxide) are the two most
common coagulants used in the U.S. although organic polymer coagulants
(i.e., long-chain, water-soluble polymers) have gained widespread
acceptance. Ferric compounds also are used as coagulants although these
compounds are corrosive and difficult to dissolve in water. [Water
Treatment Principles and Design, James Montgomery Consulting Engineers,
1985.]
After a rapid mix period, mixing must be slowed to allow for formation of
larger floes. (At higher mix rates, the aggregate floe will continue to be
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destroyed through excessive physical contact.) This process is known as
flocculation. Because of the size of the particles, some mixing is required
to cause contact between solid masses and to promote larger floe formations
that will settle rapidly.
During precipitation, the solids are separated from the liquid, usually by
settling. This should result in two distinct layers, one solid and one liquid
that can be readily separated.
Typically, coagulation equipment consists of tanks with rotating impellers
for rapid mixing, but in-line blenders and pumps or baffles may be used.
Flocculation equipment consists of tanks with paddle type mixers for slow
agitation and flocculation. Sedimentation equipment usually consists of a
clarifier unit which has inclined plates (lamella separator) or tubes. These
units operate by gravity, require little space, and have minimal installation
and maintenance costs.
3.5 OTHER TREATMENTS FOR METALS REMOVAL
Ion Exchange In the ion exchange process, wastewater is passed through a container of
anionic or cationic resin particles. As the solution passes through the resin
bed, there is an exchange of innocuous ions (e.g., H+ or OH') from the
resin for the undesirable similarly charged ions (e.g., Cu2+ or CN')
dissolved in the solution. Each resin has a distinct number of ion sites that
determines the maximum number of exchanges per unit of resin. As the
resin exchanges ions, it will reach a state in which it has adsorbed its
capacity of ions. The resin must then undergo regeneration during which
the resin will be backwashed. The regeneration process results in a small
volume of backwash solution which has a very high concentration of the
removed ions.
Ion exchange units may be a batch tank, but are normally an enclosed
pressurized column. The process may be operated as a single unit, in
parallel, or in series.
The resin used in a column is selected for the constituents to be removed.
Resins can be broadly classified as strong or weak acid cation resins or as
strong or weak base anion resins. Strong acid and base resins operate
independently of pH, while the operation of weak acid and base resins
depends on the pH. Chelating cations may also be used, but are expensive.
As described above, typical ion exchange systems consist of one or more
columns operated in a continuous mode, with separate columns included for
each type of resin. Multiple columns of the same resin are used to prevent
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pass through of pollutants into the effluent after breakthrough has occurred.
Additionally, duplicate systems are often employed to allow a flow to be
diverted to a second unit during regeneration of the columns.
Reverse Osmosis is the spontaneous flow of water from a dilute solution through a
Osmosis semipermeable membrane to a more concentrated solution. Reverse
osmosis includes the application of pressure to overcome osmotic pressure
and force the flow of water through the membrane toward the more dilute
solution. This increases the concentration of pollutants in the wastewater,
but reduces the volume of contaminated water. Ions and small molecules
can be separated using this technology.
Reverse osmosis units are sensitive to the environment and must be
carefully checked for chemical attack, fouling, and plugging. Maintaining a
pH of 4 to 7.5 will help to minimize fouling and plugging. Reverse
osmosis is not effective for highly organic wastes as the organic materials
act to dissolve the membrane. Oxidizing agents, such as iron and
manganese, particulates, and oil and grease must be removed prior to
reverse osmosis. Biological growth on the membrane (which is promoted at
low organic concentrations) can also reduce unit efficiency, although
addition of chlorine or other biocides can eliminate this fouling. Operating
reverse osmosis units in series can improve the handling of variable
flowrates and pollutant concentrations.
3.6 ORGANICS TREATMENT
Organics Wastewater treatment to remove organic compounds has historically been
Treatment through biological degradation (i.e., the breakdown of compounds through
microbial digestion). While this method is quite effective for domestic type
wastes, biological treatment of industrial wastes containing organic
chemicals is not always as effective. Reasons for this ineffectiveness
include; certain organic compounds may be toxic to the microorganisms
thereby inhibiting the degradation activity, not all materials are biologically
degraded, and it is often difficult to treat down to the necessary
concentrations. As such, several techniques common to organic chemical
production have been further developed as wastewater treatment
technologies.
The treatment technologies found to be the most effective at reducing the
concentration of organic pollutants in wastewater and used regularly in the
treatment of organics include:
Carbon adsorption
Air stripping
Steam stripping
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Carbon First, definition of the term "adsorption" is helpful when understanding the
Adsorption concept of carbon treatment. Commonly, this term is confused with
"absorption." Adsorption is the taking up of a liquid, gas, or dissolved
solids onto the surface of a solid or liquid. Absorption is the taking up of a
liquid, gas, or dissolved solids into the molecular structure of the solid or
liquid. The basis for carbon adsorption is the high surface area per weight
on the activated carbon due to a very high porosity and the natural affinity
of a liquid (or gas) to be attracted to and held on the surface of a solid.
Surface areas of 100 m2/g are common.
Carbon adsorption is typically the most effective technology for removing
dilute concentrations of organic compounds from wastewater. Often it is
used as a final polishing step prior to discharge. Carbon is widely used in
the U.S. for drinking water treatment.
Two types of activated carbon application are used for wastewater
treatment, granular and powdered. Granular carbon typically is contained
in packed columns, with the wastewater flowing either up or down through
the carbon packing.
Typically, carbon columns are operated in series, with two or more
columns. This ensures that as the first column reaches its capacity and the
effluent from this column becomes more contaminated, the second column
can treat this contamination and prevent contaminated discharges to the
municipal treatment plant. New carbon can then be added to the first
column, the second column can become the first column while the old first
column is being refilled, and the old first carbon column can now become
the second column in series. A similar approach can be taken for more
than two columns as well.
Powdered activated carbon is added to water to form a slurry and then
introduced into the wastewater. This wastewater and carbon mixture is then
agitated to increase contact between the carbon and contaminants, and then
allowed to settle in a quiescent state. The treated wastewater can then be
pumped off the top with the carbon sludge hauled off for disposal or
regeneration.
Air Stripping
Air stripping defines the practice of removing volatile contaminants from
wastewater by contacting the wastewater with a steady stream of air through
a packed column (typically countercurrently). The air (which now contains
the contaminants from the wastewater) can then be released to the
atmosphere or preferably recovered or further treated using carbon
adsorption, incineration, or open flame.
In a packed column, air is drawn up through the column with fans and the
water trickles down the column. Packing materials, such as berl saddles or
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raschig rings, provide more surface area to promote mass transfer between
the air and wastewater.
The benefits of air stripping columns are that they take up little space,
operate in a continuous mode, and are inexpensive to operate. Energy costs
comprise the sole operating cost.
Air stripping is a common practice for treatment of contaminated
groundwater. Here, the water is pumped out of the ground and treated.
Steam Steam stripping operates similar to air stripping except that steam is
Stripping introduced rather than air, thereby heating the water and improving the
transfer of contaminants. This is similar to distillation of volatiles from the
wastewater. One method to improve the efficiency of a steam stripper is to
condense a portion of the vapor leaving the top of the column and return it
to the column as a liquid. In the U.S., where organic chemical plants use
stripping technology for wastewater, over 90 percent use steam stripping
rather than air stripping. Halogenated aliphatics (e.g., methylene chloride,
chloroform, and vinyl chloride) are very conducive to steam stripping
technology.
For volatile pollutants, over 99-percent removal is common. Steam
stripping is more effective than air stripping although considerably more
expensive (because of energy costs).
3.7 OIL REMOVAL
Oil Removal Many types of industrial facilities generate wastewater containing oil and
grease, the concentration of which can vary drastically. For example, a
textile manufacturer may generate wastewater with 10-50 mg/1 of oil and
grease; a food processor between 100-1,000 mg/1; a commercial laundry
between 100-2,000 mg/1; and a metal fabricator between 10,000-150,000
mg/1. [Toledo Division of Continuing Education.]
To discuss oil and grease removal, the three types of oil and grease must
first be identified. These include free oils (which rise to the surface and
can be skimmed off), emulsified oils (which must have the emulsion broken
before removal), and dissolved oils (which require biological treatment or
more sophisticated treatment techniques for removal).
The simplest form of oil removal is gravity separation. Oil-containing
wastewater is held in a quiescent state, where the free oil being lighter than
water, will float to the top and can be skimmed or pumped off. Rotating
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belts are often used to remove the oil from the surface. Solids that settle to
the bottom can also be removed.
Emulsion breaking is necessary to remove oils where the oils are present as
an emulsion (e.g., coolants applied directly to metal components or metal
fabricating equipment during operation). (Emulsified oils are often called
"soluble oils" as the oil appears to be dissolved in water; however, the oils
are actually present as tiny droplets suspended in water.) Typically,
emulsions are broken by pH adjustment or chemical addition.
Polyelectrolytes have come to be the treatment method of choice for
emulsion breaking because of the wide selection of chemicals available and
the limited volume of sludge produced (versus the older method of choice
of lime or alum addition).
After breaking the oil emulsion, the oil can be removed using air flotation
techniques; either dissolved air flotation or induced air flotation. In
dissolved air flotation, the wastewater is pressurized in the presence of air,
thereby dissolving the air in the water. When the water is discharged from
the pressure line into an open tank, small air bubbles form which carry the
free oil and suspended solids to the surface where they can be removed with
skimming apparatus. Induced air flotation consists of introducing fine
bubbles underneath a liquid and as the air rises, the bubbles collect the oils
and suspended solids lifting them to the surface where they can be removed.
(Air bubbles in induced air systems are an order of magnitude larger than in
dissolved air systems.)
Recently, ultrafUtration techniques have been used to remove oil from
wastewater. In ultrafUtration, the wastewater is pumped past a membrane
where the water and other dissolved substances flow through the membrane.
The large emulsified oil molecules are retained. Subsequent passes through
an ultrafUtration unit can further purify the contaminant oil. Reductions in
volume by 95-97 percent are achievable through ultrafiltration.
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CHAPTER 4
4.0 POLLUTION PREVENTION TECHNIQUES
4.1 INTRODUCTION
Introduction Pollution prevention techniques are considered to fall under the first two
tiers of the waste management hierarchy, that being, source reduction and
recycling. As described previously, pollution prevention techniques under
these two categories can be grouped into eight classifications. To better
understand the impacts of these eight types of pollution prevention
techniques, specific methods to reduce wastewater pollution in the
electroplating/metal finishing industry are presented and discussed in detail.
4.2 PROCESS CHANGES
Process The greatest number of pollution prevention techniques in the electroplating/
Changes metal finishing industry can be classified as process changes. As mentioned
above, process changes may affect either procedures or equipment and
influence the quantity or toxicity of wastes generated.
Considering how a metal part is electroplated, in an ideal situation, all the
water would drain off the workpiece as it is removed from the plating bath,
negating the need for rinsing. However, it is clear that this is not the case
and that even in the best of situations, a small amount of plating bath
remains on the workpiece and must be removed to stop any further
chemical action by this solution. This phenomenon leads to the first and
often the most opportunistic area for pollution prevention at a plating
facility: dragout. Dragout is the plating term for the plating solution that
is carried out of the plating bath as the workpiece is removed from the
bath. Minimizing the carryover of this dragout into subsequent rinse tanks
can drastically reduce wastewater flow rates and pollutant loads, thereby
reducing both the amount of raw materials that must be purchased and the
cost of pollution control.
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Plating Bath The first area to consider for dragout reduction is the plating bath. Several
modifications to the plating solution makeup can impact the amount of
dragout. The most common techniques include:
Increase the temperature of the bath, thereby reducing the surface
tension and viscosity of the bath (promoting quicker drainage of the
plating solution)
Decrease the concentration of metals in the plating bath such that a
more dilute solution is being carried over into the rinse tanks
Add wetting agents/surfactants to the bath to reduce the surface tension
(again promoting quicker drainage).
Plating Even if the plating bath is adjusted as described above, dragout can still be
Techniques a major source of wastewater pollutants if improper plating techniques are
used. When plating, workpieces are either hung on a rack or loaded into a
barrel (for small parts) and then submerged into the plating tank. After a
specified period of time, the parts are lifted out of the bath and transferred
to a rinse tank where the residual plating solution is cleansed off the parts.
Techniques that can minimize carrying over dragout from the plating tank
to the rinse tank include:
Design plating racks that do not have cups or pockets that could
possibly carry plating solution over into a rinse tank.
Design racks that hold the workpieces in an optimum configuration to
minimize dragout (i.e., the part should be at an angle with the smallest
surface area the last to leave the plating bath). For example, if plating
an axle, the axle should be removed from the bath near vertical rather
than horizontal.
Inspect racks regularly for worn insulation or corrosion that could form
pockets for plating solution.
Withdraw parts from the plating bath slowly and allow to drain over
plating tank for at least 10 seconds.
Install air knives over plating solution that drives the plating solution
off the workpiece and back into the plating tank as the part is
withdrawn from the plating bath.
Install a fine mist spray (fog spray) over the plating bath to spray the
plating solution off the workpiece and back into the tank. However,
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the flowrate of the spray cannot exceed the evaporation rate of the
plating solution.
Agitate the workpiece or barrel after it is removed from the plating
bath, thus promoting drainage back into the tank.
Install drain boards and drip guards between the plating tank and
subsequent rinse tanks to catch any residual drainage and return this
solution back into the plating tank.
Rinsing When designing the rinse system, several configurations are recommended,
Techniques including:
Use a static rinse (often called a dragout tank or dead rinse) as the first
rinse to cleanse off the most concentrated plating solution. After a
period of time, the concentration of plating solution in this tank will
increase to the point where it can either be fed directly back into the
plating tank or can be purified using techniques such as evaporation or
reverse osmosis and then fed back into the plating tank.
Add air or mechanical agitation to the rinse tank and all subsequent
rinse tanks to promote complete rinsing (this is especially important for
complex workpieces with a lot of angles and crevices).
Install rinsewater control hardware such as flow control meters, flow
restrictors, foot-controlled spray nozzles, and photosensors (which turn
on the rinsewater as the plated parts pass through the line of sight of
the photosensor) to minimize and control rinsewater usage
Use high-pressure spray rinses for effective cleansing with a minimal
amount of water.
Allow an adequate amount of time in the rinse tank to promote good
rinsing (for rinsing simple parts in well agitated tanks, 5-10 seconds
may be enough time, but, for complex parts in a poorly agitated rinse
tank, 10 minutes may not even be enough time).
Use multiple countercurrent rinse tanks.
Extending In addition to dragout control, several techniques can be used to minimize
Plating contamination of the plating bath as well as any precleaning baths (e.g.,
Bath Life acids or alkaline cleaners), thereby extending the useful life of the bath
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while at the same time promoting recovery/recycling techniques. These
methods include:
Preclean parts using mechanical methods, such as wiping, squeegeeing,
or shot blasting
Minimize dust and dirt in the plating room
Cover plating bath to minimize contamination
Replenish baths rather than batch dumping and replacing
Reduce dragging of pre-plating solutions (e.g., acids or alkaline
cleaners)
Install a continuous filtering system on the bath to remove impurities
Remove anodes from the plating tank when not in use.
Use of the process changes described above can save the plating shop a lot
of time and money without changing the physicochemical process.
4.3 MATERIAL SUBSTITUTION
Material The second pollution prevention category, material substitution, takes
Substitution electroplating modification one step further. In this case, a plating facility
may choose to modify the raw materials used at the facility to minimize
pollution. These modifications may include:
Use deionized water in the plating bath and dragout tank (i.e., the tank
that will eventually be recycled back into the plating tank) to remove
contaminants that will build up over time and contaminate the bath.
Use high-purity raw materials (i.e., anodes, plating chemicals, acids,
etc.) that will minimize contamination.
Change to a non-cyanide plating bath (e.g., pyrophosphate copper, acid
sulfate cadmium, or zinc chloride) to eliminate the use of toxic and
hazardous cyanide.
Use non-chelated chemicals (i.e., chemicals that do not form organic/
inorganic complexes with the toxic metals, thereby inhibiting metal
removal using conventional treatment technologies).
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Use aqueous cleaners rather than organic solvents to remove dirt and
oil.
Reuse spent acids and bases in other areas where purity is not as vital
(e.g., similar to countercurrent plating baths, countercurrent acid rinses
can minimize acid and water use)
Use treatment chemicals that minimize sludge generation (e.g.,
magnesium hydroxide rather than lime or caustic).
4.4 MATERIAL INVENTORY AND STORAGE
Material The process of electroplating requires the use of a wide variety of raw
Inventory materials, from plating chemicals, to acid/alkaline cleaners, organic
and Storage solvents, and wastewater treatment chemicals. Proper inventory and storage
of these materials can minimize pollutant loadings to the environment.
Considerations include:
Material Inventory
Use raw materials before the shelf life or expiration date (use the first-
in, first-out practice)
Buy an appropriate amount of raw materials, only buying large amounts
of materials with an unlimited shelf life (e.g., metal prices fluctuate
regularly and the quantity and time of purchase is often highly
dependent on the current price)
Purchase raw materials from suppliers that will buy back chemicals that
are out-of-date.
Material Storage
Divert storm water away from material storage (including covering raw
materials, either inside or under roof, tarp, etc).
Install spill containment around raw materials and do not store
materials outside this containment (as is often done with one drum or a
few bags of a chemical).
Store raw materials as specified by the manufacturer (e.g., proper light,
temperature, etc).
4.5 WASTE SEGREGATION
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Waste Segregation of wastes is important for two reasons: (1) regulations differ
Segregation for different wastes and by segregating, costs can be minimized, and
(2) treatment techniques often are more effectively performed on individual
wastestreams rather than on the combined wastestream. However,
oversegregation of wastes can also be a problem, causing greater
environmental release potential, repetitive equipment costs, and more
difficulty meeting environmental regulations. Therefore, segregation of
wastes should be analyzed in detail before designing wastewater
management systems and procedures. Factors that should be considered
include:
Segregating hazardous and non-hazardous wastes to keep waste
management costs to a minimum.
Using separate treatment systems for different metals to produce higher
quality sludge, thereby increasing its likelihood of reuse.
Keeping non-metallic and metallic wastes separate to eliminate
unnecessary metals treatment of nonmetallic wastes.
Keeping hexavalent chromium and cyanide wastes separate to minimize
the flow to be reduced or oxidized.
4.6 GOOD HOUSEKEEPING/PREVENTATTVE MAINTENANCE/
EMPLOYEE EDUCATION
Good
Housekeeping
Proper operation and implementation of the equipment and procedures
assure pollutant loading reductions. Good housekeeping practices that
should be employed in a plating shop include:
Use a dry floor for the plating line, rather than an overflow system
where water overflows the plating line tanks into a sump. (This
stresses the importance of keeping the plating area clean and dry and
inhibits sloppy water use practices.)
Keep area clean and dry at all times (so that if leaks, spills, or
overflows occur, the source of the problem can be easily identified and
corrected).
Preventative
Maintenance
As with any manufacturing operation, preventative maintenance is essential
if a facility intends to operate for any length of time without fear of
equipment failure or loss of product quality. In the plating shop, this type
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of situation can occur quickly if proper preventative maintenance is not
performed. Activities should include:
Install high-level alarms on tanks that could overflow and cause
environmental or safety hazards
Regularly check for leaks in tanks, valves, fittings, pumps, etc. and
repair immediately
Keep a supply of extra parts on hand for commonly replaced
components
Maintain plating racks in good condition to minimize dragout or poor
electrical conductivity
Calibrate conductivity, pH, and flow meters regularly
Inspect workplaces prior to plating to eliminate rejects before
processing through plating line.
Employee One of the most critical components of pollution prevention in a plating
Education shop (especially in a small shop where parts are manually transferred from
tank to tank), is the need for employee education and training. Throughout
the U.S., plating shops have been found to have excellent equipment and
procedures in place to minimize pollution, but for one reason or another,
the plating line operators prevented these pollutant reductions from actually
occurring. Steps that can be taken to improve employee habits include:
Provide regular training to employees on proper operating practices,
including the economic benefit of following those procedures.
Provide employee incentives for beneficial suggestions or for meeting
certain pollution prevention goals (e.g., no noncompliance events while
maintaining a low wastewater flowrate).
Educate employees on water conservation. [Water use can be a
significant concern since many plating line operators will increase rinse
rates to speed up the process, irrespective of supervisor's instructions.]
Post important information on equipment and procedures for employees
to use as a reference (e.g., dragout times and a clock, contents and
concentrations in all tanks, markings on valves as to the proper open
position, spill cleanup procedures and equipment).
4.7 PRODUCT CHANGES
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Product Similar to material substitution, the plating facility should consider product
Changes changes that can minimize pollution. For electroplaters, this could include:
Replace toxic metals with non-toxic metals (e.g., replace cadmium with
aluminum).
Replace hexavalent chromium with trivalent chromium. [Note: most
bivalent chromium formulations produce a duller plate than the shiny
plate produced by hexavalent chromium, trivalent chromium is more
expensive than hexavalent chromium, and, excluding decorative
applications, the physical and chemical properties of the trivalent
chromium may limit the applicability.]
Redesign manufactured parts to minimize pockets and cups that can
dragout plating solution (often this is done simply by designing a hole
in the location of the cup or pocket)
Evaluate the possibility of non-plated parts (e.g., powder coating).
Most often, product changes resulting from material substitutions must be
evaluated in great detail to determine the saleability of the redesigned
product. In some instances (e.g., putting holes in the legs of chrome plated
chairs and tables to promote drainage during plating), the change likely will
not effect the resale value of the pan. Conversely, a plater may be able to
use this redesign to its advantage by advertising the new chair as an
environmentally-sensitive design.
4.8 WATER/ENERGY CONSERVATION
Water/Energy Water/energy conservation is often the result of one of the other seven
Conservation pollution prevention classifications. However, several steps can be taken in
the plating shop to further minimize energy and water consumption. This
includes:
Reuse deionized rinsewater in other areas of the plating shop where
purity is not as important.
Cover tanks when not in use to reduce heat loss and evaporative losses
(e.g., the use of polypropylene balls, which float on the surface of the
bath, reduce evaporation significantly).
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Recycle once-through cooling water for rinse water or makeup water
for other baths (it is unlikely that this water is suitable for the plating
bath or the stagnant rinse tank).
Turn off rinse tanks when not in use (e.g., use of photosensors which
automatically turn the water on and off as working pieces are rinsed).
Use conductivity sensors and pH probes to control rinsewater quality,
whereby freshwater is added only when the conductivity or pH
approaches a certain unacceptable level.
4.9 RECYCLING
Recycling 1. Waste Exchange. One technique that has been increasing in popularity
in the U.S. as the cost of pollution control continues to rise is waste
exchange. This technique encourages exchanging of wastes with others for
reuse of the waste or recovery of valuable materials. Several types of
wastes in the electroplating/metal finishing industry are conducive to waste
exchange, namely metal sludges, spent plating baths, and spent acids and
alkaline cleaners. Some of the wastes suitable for exchange include
pickling wastes (i.e., sulfuric acid and ferrous sulfate) for use in fertilizer
production, sodium hydroxide from electrowinning for use in neutralization,
and reclaimed oils available for reuse as fuel.
2. Wastewater Recycling. Several technologies are commonly used to
reduce the volume of contaminated wastewater in the metal finishing
industry with the purpose of recovering the concentrated solution for reuse.
Techniques such as evaporation, ion exchange, reverse osmosis,
ultrafiltration/microfiltration, electrodialysis, and electrowinning are readily
available technologies for the recover/recycle of raw materials.
3. Evaporation. Evaporators can be used to recover a wide variety of
acidic and basic baths including; chrome plating, chromic acid etch, nickel
plating, copper sulfate, precious metals, cyanide plating (zinc, copper,
cadmium, silver), and zinc chloride. Recovery consists of boiling off water
until the concentrate can be returned to the plating bath. Vapor is
condensed and recycled for use as rinse water. Pressurized evaporation
prevents thermal degradation of plating chemicals and reduces energy costs.
Evaporation also concentrates contaminants in the plating bath which must
be removed before reuse. Technologies such as carbon filtration or ion
exchange may remove these contaminants to a sufficient concentration to
allow for reuse.
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AIR POLLUTION/HAZARDOUS WASTE
INSPECTIONS
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TABLE OF CONTENTS
Chapter Page
1 Baseline Inspection Techniques for Air Pollution Sources 1-1
1.1 Objective 1-1
1.2 Introduction 1-1
1.3 Principles of the baseline method 1-1
1.4 Levels of inspection 1-3
1.5 Level II source inspections 1-5
1.6 Components of the control system 1-6
1.7 Ancillary components 1-8
1.8 Classification of air pollution control devices 1-11
1.9 Fabric filters , 1-12
1.10 Electrostatic precipitators (ESPs) 1-17
1.11 Cyclones/Multi-cyclone collectors 1-20
1.12 Wet scrubbers 1-23
1.13 Carbon bed adsorbers 1-30
1.14 Incinerators 1-32
1.15 Condensers 1-32
2 Hazardous Materials/Hazardous Waste Inspection Procedures 2-1
2.1 Introduction 2-1
2.2 Inspection preparation 2-2
2.3 Health and safety requirements 2-3
2.4 Inspection equipment 2-4
2.5 Operations, waste handling, and record review 2-4
2.6 General inspection procedures 2-5
2.7 Inspection checklists 2-6
2.8 Waste sampling 2-7
2.9 Documentation 2-8
2.10 Field notebook 2-9
Figures
Figure Page
1-1 Typical air pollution control system 1-7
1-2 Shaker-cleaning fabric filter 1-13
1-3 An example of a large reverse-air fabric filter 1-14
1-4 Pulse-cleaning 1-16
1-5 ESP collection schematic 1-19
1-6 Electrostatic precipitator 1-19
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Figures (Cont...)
Figure Page
1-7 Single cyclone collectors 1-22
1-8 Multi-cyclone 1-22
1-9 Simple spray chamber 1-25
1-10 Tray scrubber 1-26
1-11 Countercurrent packed tower 1-27
1-12 Conventional venturi scrubber 1-28
1-13 Activated carbon adsorber 1-31
1-14 Direct-fired incinerator 1-33
1-15 Catalytic incinerator 1-33
1-16 Contact condenser 1-34
1-17 Surface condenser 1-35
Appendices
Appendix Page
1-A Safety Guidelines 1-37
1-B Recommended List of Inspection Equipment 1-39
1-C Baseline Air Pollution Quiz 1-41
2-A Hazardous Materials/Hazardous Waste Sampling Equipment 2-11
2-B General Site Inspection Information Form 2-13
2-C Waste Information Worksheet 2-15
2-D Containers Checklist 2-17
2-E Waste Piles Checklist 2-19
11
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CHAPTER 1
1.0 BASELINE INSPECTION TECHNIQUES FOR AIR POLLUTION
SOURCES
1.1 OBJECTIVE
To provide information and techniques to support inspection
personnel in conducting field inspections which are necessary to
promote compliance.
1.2 INTRODUCTION
During the period from 1970 to 1975, the majority of sources in the
U.S. installed pollution control equipment to satisfy recently
promulgated regulations. Most of these systems operated well
initially; however, as they aged, operation and maintenance problems
began to emerge. The baseline inspection method was developed to
provide agency personnel with an aid to diagnosing these emerging
problems. The ultimate goal is to be able to identify deteriorating
performance before non-compliance occurs and restore collection
efficiency to its original level.
In this chapter, information concerning the baseline method, various
types of inspections, air pollution control systems, and common air
pollution control devices is presented.
1.3 PRINCIPLES OF THE BASELINE METHOD
The baseline inspection method embodies four major principles:
1. Every source and every control device is unique.
Each control system should be approached initially as if it
performs in a manner different from other similar systems on
other similar sources. This is important, because substantial
differences in performance and vulnerability to problems have
1-1
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been noted in a number of cases where identical control systems
have been installed on identical or similar sources. With the
baseline method, a symptom of potential problems is simply a shift
in a measured or observed parameter from the value or condition
it had when the source was known or assumed to be in
compliance. It should be noted that one symptom is rarely used
alone. Rather, a combination of symptoms is analyzed to
determine if there are potential problems.
2. On-site instruments are often unreliable or unavailable.
If the control device has operation and maintenance problems, it
is very likely that the instruments are also not working properly.
Also, particularly on smaller systems, a parameter of interest may
not be measured. It is important that the inspector be aware of
this possible limitation and be prepared to either use less- than-
desirable data or to make the needed measurements with portable
instruments.
3. A counterflow inspection approach ensures that information of most
value is obtained first.
In the counterflow approach, the inspection begins at the stack
and proceeds toward the source in a direction counter to the gas
flow. One of the main advantages of this is that the scope of the
inspection can be limited to specific conditions, if any, which are
symptoms of operating problems. Thus, process equipment would
be inspected only if it had been determined that process changes
were the likely cause of control system performance shifts. In
many cases, this approach will minimize both the inspector's time
and the inconvenience to operator personnel.
4. Judgement of the inspector is the most important factor.
Effective inspection of air pollution control systems goes beyond
simply filling out a checklist. Because of the diversity of control
system designs and differences in the degree of maintenance, it is
important that the inspection procedure not be rigid. Maintaining
this flexibility requires the inspector to continually exercise
judgement, both in determining how to proceed with the
inspection and in interpreting the symptoms observed.
1-2
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1.4 LEVELS OF INSPECTION
Introduction It is desirable to conduct detailed engineering-oriented inspections at
all sources. This is obviously impractical, however, since large
numbers of air pollution sources must be inspected regularly, and
Agency manpower and resources are limited. To give control agencies
the opportunity to properly allocate limited resources, four levels of
inspections have been designed.
The levels of inspection are denoted as I through IV with the intensity
of the evaluation increasing numerically. The types of activities
normally associated with each level and the experience levels
necessary to conduct the different levels vary substantially.
The most complete and time-consuming evaluations are done only
when preliminary information indicates that there is or soon will be a
significant emission problem.
Level I inspections The Level I inspection is a field surveillance tool intended to provide
relatively frequent but very incomplete indications of source
performance. No entry to the plant grounds is usually necessary and
the inspection is never announced in advance. The inspector makes
visible emission observations on all stacks and vents which are visible
from the plant boundary and which can be properly observed given
prevailing meteorological conditions. Odor conditions are noted both
upwind and downwind of the facility. General plant operations are
observed to confirm that these conform to permit requirements.
Unusual conditions provide the stimulus for an in-plant inspection in
the near future. If the visible emission observations and/or other
observations will probably result in the issuance of a notice of
violation, the information should be transmitted to source
management personnel immediately.
Level II inspections The Level II inspection is a limited "walk through" evaluation of the
air pollutant source and/or the control device. Entry to the facility is
necessary. The inspection can be performed either in a co-current or
countercurrent fashion depending on the anticipated types of
problems. In either case, the inspection data gathered are limited to
that which can be provided by on-site, permanently-mounted
instrumentation. An important aspect of this type of inspection is the
evaluation of the accuracy of the data from this instrumentation.
1-3
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Level HI
inspections
When control devices are not in service during the plant inspection,
the Level II inspections can include checks on the internal conditions.
This is particularly useful for the evaluation of fabric filter
performance. The inspection involves observations from access
hatches and under no circumstance includes entry into the collector by
the inspector.
The more detailed and complete Level III inspection may be
conducted when the Level I data and/or the preliminary observations
during Level II inspections indicate problems. Where necessary,
portable gauges provided by the inspector are used to measure certain
operating parameters. The types of instruments generally used
include:
Level IV
inspections
static pressure gauges;
thermocouples and thermometers;
oxygen and carbon dioxide monitors;
pH meters; and
pitot tubes.
The Level III inspection includes a detailed evaluation of stack
effluent characteristics, CEM monitoring data, control device
performance parameters, and process operating conditions. Raw
material and fuel analyses may be reviewed and samples of the
scrubber liquor may be obtained for later evaluation. Failed bags or
electrostatic precipitator discharge electrodes may be obtained to
confirm that the plant has correctly identified the general type of
problem(s). In some cases, the Level III inspection will include an
evaluation of the internal portions of an air pollution control device.
This is done simply be observing conditions from an access hatch and
under no circumstances should include entry of the inspector into the
control device. The internal checks are included only when the unit is
locked off line or when one or more compartments can be safely and
conveniently isolated for evaluation.
The Level IV inspection, identical in scope to the Level III procedures,
is done explicitly to gather baseline information for use later in
evaluating the performance of the specific sources at a given facility.
This type of inspection should be done jointly by a senior inspector
and the Agency personnel who will be assigned responsibility for the
plant. Such inspections are done in conjunction with stack tests of
major sources such as large electrostatic precipitators, scrubbers, and
fabric filters. With smaller sources which are rarely tested, the Level
IV inspection is done during a period when source personnel believe
that the source is in compliance and the control device is working
properly.
1-4
-------
An important part of the Level IV inspection is the preparation of
general process and control device flowcharts. These should be
prepared in accordance with published guidelines. As a starting point,
the inspector should request the block flow diagrams or drawings for
the portions of the plants which are of interest. Specific flowcharts
should be prepared so that all of the important information
concerning process flow streams, measurement ports, locations of
vents and bypass stacks, and locations of all control devices is clearly
shown.
1.5 LEVEL II SOURCE INSPECTIONS
Introduction
General
information
A Level II inspection involves an on-site evaluation of the control
system and relies on plant instrumentation for the values of any
inspection parameters.
Since this is the type of inspection most commonly conducted by
Agency personnel, additional information is provided in this, and
subsequent sections.
The scope of the Level II inspection should be limited to
absolutely essential operating parameters and conditions necessary
to evaluate compliance status and/or to evaluate progress toward
compliance.
The Level II inspection should require a maximum of 4 hours on
site. Small sources should require less time.
The inspection form should be identical to the inspection report
form. Preparation of the report should require less than 1 hour
even for major sources.
While on site, it should be possible for inspectors to compare
inspection data against site-specific baseline data and industry
"norms". The inspection form should help inspectors determine
the follow-up information needed to evaluate the adequacy of
source operation.
The inspection procedures and inspection form should include a
checklist to help inspectors conduct a complete and consistent
inspection. However, the form must allow for flexibility so that
inspectors can exercise professional judgement while performing
the inspection.
1-5
-------
Safety
considerations
Limitations
Evaluation of the accuracy of certain on-site instruments must be
completed before data from the instruments is recorded in the
inspection notes and report.
Nothing should be done which jeopardizes the health and safety of
the inspector and/or the plant personnel.
Under no circumstances should a regulatory agency inspector
enter any air pollution control device or any process equipment.
The inspection is intended to evaluate progress toward compliance
and to identify abnormal operating conditions which may be
indicative of excessive emissions. It is not intended to provide a
definite measure of the pollutant emission rate. This can only be
determined by means of the promulgated reference method test.
Due to the complexity of interrelated performance variables and
the lack of on-site inspection time, it is generally impractical for
the inspector to positively identify the specific operating problem
causing excess emissions. The inspection is inherently limited to
the determination of the general type of problem or problems
which exist.
The inspection does not provide a specific list of repairs and/or
modifications necessary to achieve compliance with applicable
emission regulations.
The Level II inspection is limited to the observations which can be
made by the inspector and any data which can be obtained for
plant instruments. These instruments can include permanently
mounted gauges on the plant equipment or portable instruments
used by plant personnel while the inspector is present.
1.6 COMPONENTS OF THE CONTROL SYSTEM
Introduction
Control of air pollution emissions usually involves a system that
employs several components to accomplish its task. The system begins
with the collection of contaminants from the area of generation and
continues through ductwork and assorted system components until the
cleaned gas stream is discharged through a vent or stack to the
outdoor air.
1-6
-------
Components
An air pollution control system includes the following:
Contaminant capture (hoods)
Transport (ductwork)
Gas stream cleaning (control devices)
Air moving (fan)
Instrumentation (controls and monitors)
Other activities (gas cooling, chemical feeding, waste disposal,
etc.)
The components of a control system are usually divided into two
groups: (1) the air pollution control device, and (2) its ancillary
equipment.
Figure 1-1 illustrates a typical air pollution control system
Contaminated air is captured by a series of hoods located over
operations which are the source of contamination. The captured
contaminants are conveyed through a branched ductwork system to
the control device. Dampers control the flow from each hood. The
fan draws the gas flow through the hoods, ductwork and control device
and discharges it into a stack and on to the atmosphere.
Contaminant
removal
Figure 1-1. Typical air pollution control system
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1.7 ANCILLARY COMPONENTS
Containment
capture
Level II inspection
points
Transport
Level II inspection
points
The objective of this system component is to effectively capture (with
minimum air flow into the system and minimum pressure loss on
entry) the contaminants being released from a source. Optimization
of both air flow and pressure loss reduces fan horsepower and
operating costs and the size and cost of the control device and its
ancillary equipment.
Capture efficiency: visual evaluation of fugitive losses as indicated
by escaping dust or refraction lines.
Physical condition: hood modifications or damage that could
affect performance; evidence of corrosion.
Fit of "swing-away" joints: evaluation of gap distance between
hood system and duct system on movable hoods.
Hood position/cross-drafts: location of hood relative to point of
contaminant generation; effect of air currents on contaminant
capture.
The duct system transports the contaminated gas stream between
other components in the control system. The design objective is to
select duct and fitting sizes that provide optimum conveying velocities
while minimizing friction and turbulence losses.
Physical condition: indications of corrosion, erosion or physical
damage; presence of fugitive emissions.
Position of emergency dampers: emergency by-pass dampers should
be closed and not leaking.
Position of balancing dampers: a change in damper positions will
change flow rates; mark dampers with felt pen to document
position for later inspections.
Condition of balancing dampers: damper blades can erode and
change system balance; remove a few dampers to check their
condition.
1-8
-------
Air moving
Level II inspection
points
Instrumentation
Level II inspection
points
The purpose of the fan is to move the gas stream through the air
pollution control system. To do this, the fan must be sized for the
proper air flow and must be able to overcome acceleration and
entrance losses at the hoods and friction losses in the ductwork, the
control device and other system components.
The fan may be positioned upstream or downstream of the control
device. A downstream fan position creates a negative pressure at the
control device, drawing air in through any cracks or openings and
minimizing leakage of contaminants. However, if the openings are
excessive, in-leakage may diminish the required capture velocity at the
source, allowing emissions to escape. When the fan is located
upstream of the control device, a positive pressure is created that
permits contaminants to escape through cracks or holes in the casting
or connecting ductwork.
Physical condition: indications of corrosion.
Vibration: indications of balance problems due to material build-
up or wheel erosion or corrosion; severely vibrating fans are a
safety hazard.
Belt squeal: squealing belts under normal operation indicate a loss
of air volume.
Fan wheel build-up/corrosion: internal inspection of non-operating
fans.
Condition of isolation sleeves: check vibration isolation sleeves for
holes.
Rotation direction: check rotation direction with direction marked
on fan housing.
Operating controls are important to the function of the air pollution
control system and may directly affect its performance. For example,
changing the timing cycle on a fabric filter cleaning system may cause
pressure loss to increase, reducing the air flow from the fan and
allowing emissions to escape at the source.
Physical condition: indications of excessive wear, obvious signs of
failure or disconnected controls.
Set-point values: changes in set-point values for temperature, pH,
rapping intensity, air pressure and other controllers may affect
system performance.
1-9
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Other components
Level II inspection
points
Timer settings: check for changes in cleaning cycle, chemical
delivery cycle and other timer settings.
Emission monitors: evaluate general condition and siting; have
operator check zero and span values; review historical data.
There can be many other components in an air pollution control
system, including such items as chemical feed systems and catalyst
regeneration units. A component found with all of the dry collection
devices is a dust handling system. This component is responsible for
removing the collected particles from the control device and conveying
them to the final disposal site. Common to such systems are a
collection hopper, a dust transfer valve and the piping or conveying
equipment.
Many control systems capture gases that are too hot to introduce
directly to the control device. In these systems, a component for
cooling the gases will be found. This cooling may be accomplished by
diluting the hot gases with cooler air, by evaporating water into the
hot gas stream or by radiation and convection to the atmosphere.
Solids handling:
Physical condition: indications of hopper corrosion or physical
damage; condition of level detectors, heaters, vibrators,
insulation, etc.
Discharge valve: check for presence and operating status and
indications of air leakage.
Solids discharge rate: rate of solids discharge should be
reasonable.
Gas cooling:
Physical condition: indications of corrosion, erosion or
physical damage; presence of fugitive emissions.
Outlet temperature: observe plant instruments to determine
cooler effectiveness; if controller is used, compare to set-point
value.
Spray pattern/nozzle condition: indications of effective
atomization on evaporative coolers.
1-10
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Water flow rate: observe plant flow meters or pressure gauges
to evaluate changes in water flow rate on evaporative coolers.
1.8 CLASSIFICATION OF AIR POLLUTION CONTROL DEVICES
Control devices:
Separate contaminants from a gas stream and then remove
them without re-entrainment, either continuously or
intermittently, to a disposal system; or
Change the contaminant from offensive to inoffensive; or
Both separate and remove, and change contaminants from
offensive to inoffensive.
Control devices can be classified according to the contaminants they
are typically used to remove:
Particles only
Settling chamber
Fabric filter
Electrostatic precipitator
Cyclone
Gases only
Wet collector
Adsorber
Incinerator
Vapors only
Condenser
Incinerator
Particles, gases and vapors
Wet collector
Incinerator
1-11
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1.9 FABRIC FILTERS
General
information
Fabric filters remove particles by passing the contaminated gas stream
through a woven or felted fabric, usually in a cylindrical configuration.
Depending on the direction of gas flow, particles are deposited on
either the inside or outside of the cylindrical "bag". Initially, such
forces as impaction, diffusion and electrostatic attraction are primarily
responsible for particle capture by the fabric fibers. However, as the
dust coats the filter and increases in thickness, direct sieving begins to
dominate.
As the thickness of the dust-cake increases, so does the pressure lost
in moving the gases across the filter. To keep pressure loss
reasonable, it is necessary to periodically clean the fabric. The three
most popular cleaning methods are shaking, reversing air flow
direction and pulsing with compressed air.
Cleaning methods
Shaker-cleaning
A typical shaker-cleaning collector is shown in Figure 1-2. The dirty
gas stream enters the hopper area and then moves across a tube-sheet
to the inside of the filter tubes. The gas stream passes through the
filter, depositing the particles on the inside. When it is time to clean
the fabric, the collector is isolated from air flow and the bag shaken
by moving the supports from which the bags are hung. The dust drops
into the hopper where it is removed through a dust discharge valve.
Reverse-air-cleaning The reverse-air-cleaning collector (Figure 1-3) is nearly identical in
appearance to the shaker, except the bags are hung from rigid
supports. Cleaning is accomplished by isolating the collector from the
dirty gas flow and introducing clean gas flow in the reverse direction.
This reverse flow dislodges the dust which falls into the hopper. At
this point the cleaning air is quite dirty, so it is ducted to an operating
unit for cleaning. Thus, a reverse-air collector requires a minimum of
two units.
1-12
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Clean air
outlet
Dirty air
Clean air
tide
Filler bags
Cell pi,
Figure 1-2. Shaker-cleaning fabric niter
1-13
-------
Figure 1-3. An example of a large reverse-air fabric filter
(Courtesy of MikroPul Corporation).
1-14
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Pulse-cleaning
Level II inspections
Inspection activities
Figure 1-4 shows a typical pulse-cleaning collector. Cylindrical bags
are suspended from a tube-sheet located near the top of the collector,
and the dirty gas flow is directed through the outside of the bags and
up through the center to the clean gas discharge. Metal cages are
placed inside the bags to prevent collapse. Cleaning is accomplished
by directing a pulse of compressed air into the top of the bag and
against the dirty gas flow. This pulse momentarily dislodges the dust
from the outside of the bag and slowly works it down toward the
hopper. Bags are usually cleaned one row at a time without isolating
the collector from the dirty gas flow.
Method 9 observation of the baghouse discharge.
Method 9 observation of fugitive emissions from baghouse solids
handling operation (if reentrainment is occurring).
Method 9 observation of fugitive emission from process
equipment.
Counterflow checks of audible air infiltration into fan, baghouse
(solids discharge valve, access doors, shell) and ductwork. Also
check physical condition and location of hoods.
Static pressure drop across baghouse using on-site gauge; compare
with baseline data.
Comparison of compressed air pressures at baghouse reservoir
with baseline values. Check for audible leaks of compressed air at
fittings.
Check operation of diaphragm valves, record number of valves
which do not appear to be working properly.
Check inlet gas temperatures using on-site gauge.
Observe and describe corrosion of baghouse shell and hoppers.
Evaluate bag failure records, gas inlet temperature records,
pressure drop data, and other maintenance information.
1-15
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Figure 1-4. Pulse-cleaning fabric filter
1-16
-------
Performance
evaluation
Safety considerations
Visible emissions greater than 10% from the baghouse indicate
poor performance. Inspection should include evaluation of bag
problems, including but not limited to abrasion, chemical attack,
ember damage, high temperature damage, and improper cleaning.
A rip test should be done on failed bags unless quantitative fabric
tests have been performed. If conditions appear to be severe, a
Level HI inspection (primarily clean side checks) is warranted.
Fugitive emissions from all process sources should be carefully
documented. Reasons for poor capture should be investigated,
including, but not limited to, air infiltration, poor hood condition
or location, fan belt slippage (listen for squeal), fabric blinding
and poor cleaning effectiveness. The static pressure drop data and
cleaning system performance checks (compressed air pressures,
conditions of diaphragm valves and frequency of cleaning) are
very important.
The counterflow check of the entire system for air infiltration is
very important since this can generally lead to severe problems.
The Level II inspection involves some climbing and close contact
with the pulse jet baghouse. Check the integrity of all supports
and ladders. Climb ladders properly. Avoid contact with hot
ducts and roofs. Avoid downward pointing gas discharge points.
Since the inspector must enter the facility to make a
Level II inspection, all normal safety precautions apply.
1.10 ELECTROSTATIC PRECIPITATOR'S (ESPs)
General
information
Electrostatic precipitators remove particles from a contaminated gas
stream by employing the principle of attraction of opposite charges.
The particles are charged in a high voltage electric field created by a
corona discharge electrode and are then attracted to a collection plate
of opposite charge (see Figure 1-5). When the particles reach the
collection plate they slowly lose their charge through conduction,
ideally retaining just enough charge to hold the particles to the plate
but not so much that it inhibits further deposition or makes removal
difficult. Periodically, the plate is vibrated or rapped and the dust
drops into the hopper.
1-17
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Level II inspections
Inspection Activities
The electric field is powered by direct currents supplied from
transformer-rectifier (T-R) sets mounted on the roof. Each T-R set
serves one or two fields or electrical sections. Efficiency of collection
is usually highest when the voltage is highest. Most industrial ESPs
operate with a negative corona because of its stability under high
voltage conditions. Peak performance is indicated by the beginning of
sparking from electrode to plate.
The plates are generally rapped by hammer mechanisms mounted
outside on top of the housing. In some designs the rappers are
located inside the housing and cannot be seen by the inspector. Also
located on top of the housing will be vibrator units for keeping the
discharge electrodes clean.
The electrostatic precipitator looks very much like a fabric filter, i.e., a
large box-shaped structure with hoppers beneath it. However, the
ESP is distinguished by the rapping mechanisms and transformer-
rectifier sets mounted on top of the housing and by inlet/outlet
locations that are generally on the ends (see Figure 1-6).
Method 9 observation of the stack discharge.
Timing, duration and pattern of intermittent puffs.
Characteristics of any detached, condensing or reactive plumes.
Physical conditions of transmissometer transmitter and
retroreflector.
Transmissometer zero and span values, status of window lights.
Transmissometer strip chart data
Precipitator electrical set data, including plots of the secondary
voltages, secondary currents, and spark rates for each chamber
starting with the inlet field and proceeding to the outlet field.
Process operating data.
Transmissometer strip chart records and electrical set records.
1-18
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Charging fjc|J
Charged (-)
particles
Collecting
baffle
Rippen
Collection
eleeirode
Grounded (4
collecting surface
Dhchargc
electrode
tension weight
Figure 1-s. ESP collection schematic
.Transformer-rectifier ff-R)
electrode
Figure i-«. Electrostatic precipitator
1-19
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Performance
evaluation
Safety considerations
An increase of more than 5% opacity in the visible emission since
the baseline period or visible emission within 5% opacity of the
regulatory limit warrant a Level III inspection.
If the data indicate the unit is operating in moderate or high
resistivity conditions, the power input should be computed and
compared against the baseline values.
The secondary (or primary) voltages should be compared with the
baseline values.
The field-by-field electrical data plots should be compared with
baseline plots.
The transmissometer strip charts should be analyzed for
characteristic patterns of operating problems.
Inspectors should be trained in safety procedures prior to using
stack elevators to reach transmissometers mounted on stacks.
All ladders and platforms should be checked before use. Safe
ladder-climbing practices are necessary.
Poorly ventilated areas around expansion joints, flanges and other
areas must be avoided.
1.11 CYCLONES/MULTI-CYCLONE COLLECTORS
General
information
Cyclones
Single cyclones
In a cyclone, the dirty gas stream is directed into a cylindrical shell,
either through a tangential entry or through turning vanes. The result
is a confined vortex in which centrifugal forces drive the entrained
particles toward the outside wall. Particles successfully deposited slide
down the wall and into the hopper from which they are removed
through a dust discharge valve.
Cyclones can be constructed in either single or multiple configurations.
Single cyclones are generally characterized as either high efficiency or
high throughput (see Figure 1-7). High efficiency cyclones have a
narrow inlet opening in order to attain high inlet velocity, a long body
1-20
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Multi-cyclones
Level II inspections
Inspection activites
Performance
evaluation
length relative to its diameter and a small outlet diameter/body
diameter ratio. High throughput cyclones, which are inherently less
efficient, have larger inlet openings, a shorter body length and larger
gas exits.
Multi-cyclones have numerous small diameter (typically 15-23 cm (6"-
9") cyclone tubes in parallel inside a single housing (see Figure 1-8).
Each cyclone is mounted into a lower "tube-sheet" which separates the
in-coming dirty gas stream from the hopper level below. The outlet
tube from each cyclone extends up through the in-coming dirty gas
stream and into an upper tube-sheet that separates the dirty gas from
the cleaned gas.
Cyclone efficiency is very sensitive to particle size, with performance
deteriorating rapidly for particles less than about 2-5 jum diameter.
When particle size distribution and gas flow rate are relatively
constant, changes in pressure drop across a cyclone provide a good
indicator of changes in collection efficiency.
Method 9 observation of the stack for a sufficient period to fully
characterize conditions during normal process cycles.
Method 9 observation of any fugitive emissions from process
equipment, material handling operations, and stockpiles.
Air infiltration sites on collector shell, hopper, solids discharge
valve, and inlet ductwork.
Static pressure drop across collector as indicated by on-site gauge.
Inlet gas temperature as indicated by on-site gauge.
If the visible emissions have increased more than 5% opacity since
the baseline period or if the visible emissions are within 5% of the
regulatory limit, a Level II or Level III inspection is necessary.
Fugitive emissions from the process area can be at least partially
due to air infiltration into the ductwork or collector. The process
area and ductwork should be checked in any subsequent Level II
or III inspections.
1-21
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Hijjli efficiency High ihroughpul
Figure 1-7. Single cyclone collectors
Figure 1-8. Multi-cyclone
1-22
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Safety considerations
The static pressure provides an indication of the flow rate and the
resistance of gas flow. The static pressure should be checked
against baseline static pressure drops for similar process operating
rates. If the present value is higher, then pluggage is possible. If
the static pressure drop is now lower, erosion of outlet tubes and
gasket problems are likely.
Position selected for the Method 9 observations should be secure
from moving vehicles such as cars, trains, and moving machinery.
There must be secure footing. Stockpiles are not acceptable.
All climbing and walking safety procedures are very important.
Some horizontal structures may not be able to withstand the load
of accumulated solids and several people.
Contact with hot surfaces must be avoided.
Many multi-cyclone collectors are located in hot areas. Heat
stress should be avoided by limiting the time spent in the area
(moderate heat conditions) or by not entering the area (high heat
areas).
Poorly ventilated areas must be avoided.
1.12 WET SCRUBBERS
General
information
Wet collectors remove contaminants from a gas stream by transferring
them to some type of scrubbing liquid. For particles larger than about
1 urn, the dominant separation mechanism is impaction onto liquid
droplets or wetted targets. For sub-micron particles and gases, the
dominant mechanism is diffusion to liquid surfaces. Because of
incompatible requirements, wet collectors are generally designed to
perform as either a particle or a gas collector. Simultaneous
collection of both particles and gases is usually possible only when the
gas has a very high affinity for the scrubbing liquid.
Contacting the contaminated gas stream with the scrubbing liquid is
only the first stage of a wet collector. Because the contact phase
usually results in liquid entrained in the gas stream, the second stage
is some type of liquid-gas separator. Common entrainment separators
include chevron baffles, mesh pads and single-pass cyclones.
Contactors producing large droplets may require only a little low-
velocity head-space to allow the droplets time to settle back into the
unit.
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Wet collectors
Spray tower
Tray scrubber
Packed tower
Venturi scrubber
The almost endless variety of wet collectors makes it difficult to
include all types and varieties in one discussion. To illustrate the
range of designs and performance levels, four types of scrubbers will
be briefly described: (1) a spray tower, (2) a tray scrubber, (3) a
countercurrent packed tower and (4) a venturi scrubber.
A simple spray tower is illustrated in Figure 1-9. The dirty gas stream
enters at the bottom of the scrubber and flows upward at velocities
between 0.6 and 3.0 meters (2 and 10 feet) per second. The liquid
enters at the top of the unit through one or more spray headers, so
that all of the gas stream is exposed to the sprayed liquid. A spray
tower has only limited particle removal capacity, and is generally
selected for applications where the particles are larger than about 5
Mm. Spray towers can be effective gas absorbers if the contaminant
has a moderate affinity for the liquid.
A tray scrubber (see Figure 1-10) can also be used for both particle
and gas collection. The gas stream again enters at the bottom and
passes upward through holes in the trays. The liquid enters at the top
and cascades across one tray and then flows down to the next. An
overflow weir is used to maintain a liquid level on each tray.
Variations in tray design include the placing of assorted "targets"
above each hole to enhance the scrubbing action. The tray scrubber is
an effective collector of particles larger than about 1 p.m and can be
an effective gas absorber when the contaminant has a moderately low
affinity for the liquid.
Packed towers are used primarily for gas absorption because of the
large surface area created as the liquid passes over the packing
material. The beds can be either vertical or horizontal. The most
efficient arrangement is the vertical countercurrent packed tower
shown in Figure 1-11. The gas stream again enters at the bottom and
passes upward through the packing. The liquid is sprayed from the
top and flows downward in a thin film over the surface of the packing.
The packed tower is an effective gas absorber when the contaminant
has a low affinity for the liquid.
A conventional venturi scrubber is shown in Figure 1-12. The dirty
gas stream enters a converging section and is accelerated toward the
throat by approximately a factor of ten. The liquid is injected into the
scrubber just beyond the entrance to the throat, where the liquid is
shattered into droplets by the high velocity gas stream. Particles are
collected primarily by being impacted into the slower moving drops.
Following the contactor is usually a single-pass cyclone for
entrainment separation. The venturi scrubber is an effective collector
of particles down to the sub-micron range, comparable in performance
to the fabric filter or ESP, and can be an effective gas absorber when
the contaminant has a moderately high affinity for the liquid.
1-24
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Figure 1-9. Simple spray chamber
1-7S
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Clean
Plain
Dirtj
Detail of plate
Figure MO. Tray scrubber
1-26
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Clean
MLst eliminator
Water ipraji
^;.*.. Dirty
Figure Ml. Countercurrent packed tower
1-27
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Dirtj gai
Clean
Water »praji
Figure 1-12. Conventional venturi scrubber
1-28
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Level II inspections
Inspection activities
Performance
evaluation
Safety considerations
Method 9 observation of the stack for a period of not less than 6
minutes. Average opacity should be calculated. Cycles in the
average opacity should be described.
Method 9 observation of all bypass stacks and vents. Method 9
observations of any fugitive emissions from process equipment.
Presence of rainout close to the stack or mud lips at the discharge
point.
Presence of fan vibration.
The liquor flow rate indicated by on-site gauge.
Physical condition of shell and ductwork.
Recirculation pond layout and pump intake position.
Physical condition of nozzles observed through access hatch.
Means used to dispose of purged liquor should be noted.
A shift in the average opacity may be due to a decrease in the
particle size distribution of the inlet gas stream. A co-concurrent
inspection of the process operation is often advisable.
Anything which affects the nozzles will reduce performance. The
liquor turbidity is related to the vulnerability to nozzle pluggage
and erosion.
Shell and ductwork corrosion is often caused by operation at pH
levels which are lower than desirable. The liquor pH should be
measured using in-plant instruments if available.
The performance of a spray tower scrubber is dependent on the
liquor flow rate. Any problems which potentially reduce the flow
rate should be fully examined.
All ladders and platforms should be checked before use. Safe
climbing and walking practices are important, especially in cold
weather.
Poorly ventilated areas should be avoided.
Hot duct and pipes should not be touched.
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The inspection should be terminated if a severely vibrating fan is
noted in the general vicinity of the scrubber.
Under no circumstances should the inspector attempt to look
inside an operating wet scrubber.
Visible emissions observations should be made only in secure
areas.
1.13 CARBON BED ADSORBERS
General
information
Level II inspections
Physical condition
Adsorption/de-
sorption cycle times
Steam pressure/
temperature during
desorption
Adsorbers remove gaseous contaminants from an air stream by
transferring them to the surface of some high-surface-area solid
adsorbent. In air pollution control systems, adsorbers which use
activated charcoal as the adsorbent are typically employed to remove
volatile organic compounds. Adsorption is most effective when the
system temperature is about 24°C (75°F) and the compounds have
molecular weights between about 45 and 200.
The most popular cleaning method is to introduce low-pressure steam
into the bottom of the bed to raise its temperature and cause the
contaminants to desorb from the carbon. The mixed stream of
organic vapor and steam coming from the bed is condensed and the
solvent recovered by decanting or distillation. Following desorption,
the bed is allowed to cool and dry before being put back on line.
A typical multi-bed adsorption system is shown in Figure 1-13. Here,
the left two beds are on line and contaminated gas is passing vertically
down through each unit. As the system continues to operate, the on-
line beds approach saturation with the contaminants and must be
taken off line for cleaning to prevent breakthrough of the organic
contaminant. This condition is represented in the right hand corner.
Indications of corrosion or physical damage.
An increase in the interval between bed cleanings could mean
breakthrough is occurring.
A decrease in steam pressure/temperature could indicate
insufficient steam flow for regeneration.
1-30
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Adtorlicn on stream
Adsorber
Regenerating
Clean air
cxhauil
Figure 1-13. Activated carbon adsorber
1-31
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1.14 INCINERATORS
Level II inspections
Physical condition
Outlet temperature
Temperature rise
Incinerators remove gaseous contaminants from an air stream by
oxidizing them to compounds not considered to be contaminants. The
two most common types of incinerators are:
Direct-fired or thermal units, which are refractory-lined
chambers with a gas or oil burning apparatus plainly visible
(see Figure 1-14).
Cataytic units, which have the appearance of a duct heater
and are more highly instrumented (see Figure
1-15).
In both thermal and catalytic units, the principal parameter for
indicating efficiency is temperature, the value of which is dictated by
the characteristics of the contaminant to be oxidized. In thermal
units, the recommended minimum outlet temperature is 704°C
(1300T); most systems operate in the 816-982°C (1500-1800T) range.
Catalytic units are generally designed for a bed inlet temperature of
371-482°C (700-900°F).
Indications of corrosion or physical damage; indication of air
infiltration.
Decreased outlet temperature may mean reduced VOC
destruction efficiency.
Decreased temperature rise across the catalyst bed may mean
reduced VOC destruction efficiency.
1.15 CONDENSERS
Condensers remove vaporous contaminants from a gas stream by
cooling it and converting the vapor into liquid. In some instances,
control of volatile contaminants can be satisfactorily achieved entirely
by condensation. However, most applications require additional
control methods. In such cases, the use of a condenser reduces the
concentration load on downstream control equipment. The two most
common types of condensers are:
1-32
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Gaj burner
piping
Refractory lined
ihell
Refractory ring baffle
Inlet for contaminated
aintrcam
Figure M4. Direct-fired Incinerator
Hemt exchanger tuba
Figure MS. Catalytic Incinerator
1-33
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Level II inspections
Physical condition
Outlet temperature
Liquid turbidity/
settling rate
Droplet re-
entrcanment
Contact or barometric condensers, where a direct spray
contacts the vapors to cause condensation (see Figure 1-16).
The liquid leaving the condenser contains the coolant plus the
condensed vapors.
Surface condensers, such as the shell-and-tube heat exchanger
(see Figure 1-17). This device consists of a shell into which
the vapor stream flows. Inside the shell are numerous small
tubes through which the coolant flows. Vapors contact the
cool surface of the tubes, condense and are collected without
contamination by the coolant.
Indications of corrosion or physical damage.
Provides an indirect indication of the liquid flow rate and nozzle
condition; increases may indicate nozzle pluggage and lower
coolant flow rates; decreases may indicate nozzle erosion and
higher flow rates (contact-type only).
High settling rate indicates coarse solids that could plug nozzles
(contact-type only)
Droplet rainout or a mud-lip on the stack indicates a significant
demister problem.
MLst eliminator
Spray nozzle?
Figure 1-16. Contact condenser
1-34
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cliaiincl
cover
Reversing channel
Inlet
channel
RcmovaMc
channel
covxrr
Figure 1-17. Surface condenser
1-35
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THIS PAGE LEFT BLANK
1-36
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APPENDIX 1-A. SAFETY GUIDELINES
1. Do not do anything which you feel is dangerous. Do not ask plant personnel to do
anything which either you or the plant personnel believe could be unsafe.
2. Interrupt the inspection immediately whenever you feel any of the symptoms of
possible exposure to pollutants. These include, but are not limited to: headache,
nausea, dizziness, drowsiness, loss of coordination, chest pains, shortness of breath,
vomiting, and eye, nose, or throat irritation.
3. Conduct the inspection at a controlled pace. Do not hurry.
4. Avoid areas of possible risk during the inspection if the necessary personal
protection equipment is not available.
5. Do not make internal inspections of air pollution or process equipment under any
circumstance.
6. Do not wear contact lenses during the inspection unless specifically allowed by
both agency and source safety personnel.
7. Avoid areas with potentially high pollutant concentrations which could exceed PEL
levels and/or the capabilities of the available respirators. Such areas are common
around positive-pressure equipment and areas with many process stacks and vents.
8. Use only intrinsically-safe portable instruments when inspection locations are
classified as hazardous.
9. Exercise extreme caution when walking across roofs and elevated platforms.
Weak spots are not always apparent. Walk behind plant personnel. Avoid roofs
whenever possible.
10. Evaluate means for rapidly leaving elevated roofs or platforms in the event of
sudden plume downwash or process fugitive emissions of high-temperature steam
or toxic gases.
11. Do not smoke while conducting inspections.
12. Discard or wash contaminated work clothes separately from personal clothing.
13. Know the meaning of all plant warning sirens/codes and know the proper
evacuation routes.
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14. Avoid areas of dripping and/or splashing chemicals. Flush eyes for at least 15
minutes as soon as possible after contact. Get medical attention.
IS. Remove all affected clothing and shower immediately for a period of at least 15
minutes if there is contact with chemicals. Get medical attention.
16. Exit areas around severely vibrating fans immediately. Notify plant personnel
immediately of this condition.
17. Conduct plant inspections only in the company of a responsible plant
representative.
18. Wear gloves whenever climbing ladders which are possibly hot, covered with small
quantities of contaminants, or which have abrasive and/or sharp edges.
19. Do not climb unsafe ladders. Exercise care in climbing. Both hands must be free
for holding the ladder. Grasping of the foot rungs rather than the side rails is
normally recommended by industrial safety personnel.
20. Avoid all rotating equipment which is improperly shielded.
21. Use grounding and bonding cables when obtaining samples of flammable liquids.
Comply with all regulations regarding flammable liquid sampling and shipping.
22. Stand clear when plant personnel are opening any hatches.
23. Ask plant personnel to obtain any samples needed.
24. Wear splash goggles whenever dripping chemicals are possible.
25. Comply with all plant and agency safety requirements.
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APPENDIX 1-B. RECOMMENDED LIST OF INSPECTION EQUIPMENT
GENERAL EQUIPMENT
Camera, film, and flash equipment
Pocket calculator
Tape measure
Clipboard
Waterproof pens, pencils and markers
Locking briefcase
Plain envelopes
Polyethylene bags
Wind meter or Admiral Beaufort wind scale
Ruler (for use as scale in photos)
SAFETY EQUIPMENT
Safety glasses or goggles
Face shield
Coveralls, long-sleeved
Hard hat
Plastic shoe covers (disposable)
Self-contained breathing apparatus
Disposable towels or rags
Flashlight and batteries
Pocket knife
Pocket tape recorder
Level
Range finder/optical tape
measure
Compass
Stopwatch
Square
Rubber-soled, metal toed,
non-skid shoes
Liquid-proof gloves
(disposable if possible)
Long rubber apron
Respirators and cartridges
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APPENDIX 1-B. (Continued)
PAPERWORK
Proper identification Checklists
Copy of facility's inspection file, Notebook
permit, and monitoring schedule,
including: Notice of inspection (if
applicable)
- maps
- photographs Chain of custody
- enforcement actions
Field data sheets
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EXHIBIT 1-C. BASELINE AIR POLLUTION QUIZ
1. True or false? The Baseline Inspection Technique involves detailed internal 1.
inspections of the control systems.
2. True or false? Control systems designed by the same manufacturer and 2.
operated under similar conditions can be assumed to operate in a similar
manner.
3. If a canopy hood has a capture efficiency of 80 percent, the overall efficiency 3.
of the air pollution control system must be:
a. less than 80 percent.
b. no greater than 80 percent.
c. unable to be calculated.
d. at least 75 percent.
4. If the fan is located after the air pollution control device, the static pressure 4.
plot should:
a. show static pressure steadily becoming less negative with measurements
taken closer to the fan.
b. remain essentially level.
c. reflect sharp changes in pressure depending on the direction of the
ductwork.
d. become progressively more negative with measurements taken closer to
the fan.
5. Bags in a reverse air unit are cleaned in the following manner: 5.
a. bag by bag.
b. row by row.
c. compartment by compartment.
6. True or false? Both very high and very low gas inlet temperatures can 6.
contribute to excess emissions and/or bag failure rates.
7. In an ESP, are used to control the strength of the electric field 7.
generated between the discharge and collection electrodes.
a. rappers
b. transformers-rectifier sets
c. capacitors
d. adsorbers
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8. Rappers are: 8..
a. commonly used for removing dust from discharge and collection
electrodes.
b. commonly used for removing dust from collection electrodes only.
c. a type of capacitor used to store discharge electrode voltage.
9. True or false? Increases in gas velocity result in more reentrainment of 9..
particles during rapping.
10. Particle collection efficiency in a cyclone depends upon a number of factors 10.
including:
a. cyclone dimensions.
b. inlet gas velocity.
c. particle size.
d. dust concentration.
e. all of the above.
f. a, b, and c only.
11. Multi-cyclone collectors have a static pressure drop than large-diameter 11.
cyclones.
a. higher
b. lower
12. Wet scrubbers are pollution control devices that use a liquid to remove 12.
from an exhaust gas stream.
a. particles
b. pollutant gases
c. both a & b
d. none of the above
13. Symptoms of poor thermal incinerator burner performance include: 13.
a. blue smoke generation.
b. higher than normal outlet temperatures.
c. lower-than-normal outlet temperatures.
d. lower-than-normal VOC outlet concentrations.
14. When complete combustion of a gas containing only organic compounds
occurs, are the products formed. 14.
a. NO, and SO,
b. H2O2andC02
c. NO3 and H2O
d. CO2 and H2O
1-42
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CHAPTER 2
2.0 HAZARDOUS MATERIALS/HAZARDOUS WASTE
INSPECTION PROCEDURES
2.1 INTRODUCTION
Purpose
Inspector
responsibilities
The primary purpose of this section is to provide procedural and
technical guidance for performing inspections of those facilities which
use hazardous materials or generate hazardous wastes. The procedures
are general and are not intended to be prescriptive.
Inspectors should be aware of all Federal, State, local, and
international regulations a facility must meet in order to be in
compliance. No matter what the reason for the inspection, it must be
performed in a manner which is both technically and legally correct.
Flaws in either the technical or legal conduct of an inspection may
hamper, prevent, or invalidate the use of inspection results for
enforcement purposes.
Two overriding criteria must guide the conduct of inspections to insure
that inspections optimally fulfill their role in enforcement:
1. Technical accuracy and integrity
Inspections must be technically correct. Any measurements or
other data collection and analysis must be thorough, technically
proper, and appropriately documented.
2. Legal propriety
Legal requirements concerning the conduct of inspections must be
scrupulously followed.
It is important for inspectors to know current enforcement priorities
and develop the specific skills necessary to perform the inspections
required under those priorities. They also need to be aware of
changes in priorities and be flexible so such changes can be
accommodated.
In accordance with contemporary program priorities, inspectors are
frequently assigned to concentrate on inspections of a particular type
of facility or waste management practice. As a result, inspectors will
develop specialized skills in inspecting that type of facility or practice
2-1
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through training, research and experience.
It is important, however, that inspectors also maintain a good general
knowledge of the overall hazardous material/waste program so that
they can respond to new enforcement priorities or changes in
assignment which require them to inspect other types of facilities and
practices. To maintain knowledge, inspectors should review:
major new regulations as they are promulgated;
new and existing guidance on inspecting other types of facilities
and practices; and
new and existing technical guidance that could provide quick
background information on other types of facilities and
practices.
22 INSPECTION PREPARATION
Purpose
Objectives
Adequate preparation is critical to the effective performance of
hazardous materials/waste inspections. Generally, inspectors will have
only a relatively brief period of time on site in which to perform an
inspection; therefore, it is important that the inspection be properly
scoped and planned in order to use time on site as efficiently as
possible and to insure that all aspects of the facility which should be
evaluated are inspected.
When preparing for the inspection, inspectors should:
Determine the scope of objectives of the inspection.
Coordinate inspection activities with other regulatory or
enforcement personnel as necessary.
Develop a thorough understanding of the technical, regulatory,
and enforcement aspects of the facility.
Develop a plan or strategy for conducting the inspection
consistent with inspection objectives.
Determine health and safety requirements and equipment
needs.
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Activities the inspector should undertake to achieve these objectives
are discussed in the following sections.
2.3 HEALTH AND SAFETY REQUIREMENTS
Planning the
inspection
Special
considerations
Although routine inspections generally do not involve activities in
which inspectors must physically contact hazardous wastes (except
inspections involving sampling, in which incidental contact with wastes
may occur), there is always the potential for inspectors to be exposed
to hazardous wastes or substances during the course of an inspection.
Therefore, in planning the inspection, inspectors should:
Determine the nature of the chemical hazards that may be
encountered during the inspection (based on the types of
materials handled on site, as identified in the file review).
Identify and obtain proper safety equipment.
Become familiar with the proper use of safety equipment (if not
already familiar with its use), check equipment for proper
function, and perform necessary maintenance on the equipment
(if appropriate and within the technical abilities of the
inspector).
Obtain and become familiar with all applicable safety guidance
and practices.
Determine any facility-specific safety requirements by contacting
the facility (only in cases where the facility is being notified of
the inspection) or by review of previous inspection notebooks.
In some cases, the inspector will have limited information on the
facility, or may be inspecting an uncontrolled site. The inspector
should be prepared to encounter the worst conditions in such cases.
Inspectors should never proceed with inspections involving site
conditions for which they are not prepared and do not have the
proper safety equipment.
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2.4 INSPECTION EQUIPMENT
Select equipment
Ensure proper
functioning
Consider additional
equipment
The kind of equipment that the inspector takes into the field is
dependent on the kind of inspection to be performed and the type of
facility to be inspected. Inspectors should use their knowledge of the
facility, understanding of inspection objectives, training, and
experience to decide which equipment is necessary for a particular
inspection. Inspectors may wish to consult with other inspection
personnel or their supervisor in determining equipment requirements.
Inspection requirements, the availability of certain equipment, and
Regional or State policies and conditions should also be considered
when selecting equipment during inspection planning.
Appendix 2-A provides a list of equipment that is commonly used in
performing inspections. Inspectors may not need all of the equipment
listed for every inspection; however, inspectors may need additional
equipment for some inspections. The list is divided into four
categories of equipment: general equipment, safety equipment,
sampling equipment, and paperwork.
The inspector should identify and obtain the equipment necessary to
perform the inspection from the appropriate source. The inspector
should check inspection equipment to insure that it is in good working
order prior to going into the field, and should perform, or have
performed by the appropriate agency personnel, any needed
maintenance or repairs. The inspector should also insure that he or
she is familiar with the use of the equipment; generally, the use and
operation of most of the standard inspection equipment listed is
apparent.
Special circumstances may require the use of additional equipment
such as fireproof clothing or self-contained breathing apparatus. The
inspector should determine whether such additional equipment is
necessary in conjunction with his or her supervisor, and, if appropriate,
the facility's owner/operator or plant manager.
2.5 OPERATIONS, WASTE HANDLING, AND RECORD REVIEW
Initial interview
The inspector should have the facility representative describe facility
operations and waste management practices following the opening
discussion. In general, tRe inspector should be familiar with the
facility through previous review of the facility's file. Therefore, the
2-4
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Record review
purpose of this discussion will be to:
Obtain a more detailed understanding of operations.
Answer any questions the inspector may have on waste
generation, waste flow, and waste management activities.
Identify any changes in operating and/or waste management
practices.
Identify and reconcile any discrepancies between the operations
described by the facility representative and those described in
the facility file.
During the discussion, the inspector should prepare waste information
sheets on each waste managed at the facility.
After discussing facility operations and waste handling practices,
inspections usually proceed to the record review. The record review
provides the inspector with the opportunity to become thoroughly
familiar with the facility (e.g., through review of the operating record)
and formulate specific questions to be investigated during the visual
inspection of the facility. However, the record review does not have
to occur before the visual inspection. In some cases, inspection
objectives may be best served if the visual inspection occurs before the
record review. The visual inspection may be performed first for other
reasons as well (e.g., availability of facility personnel or weather
conditions).
The regulated community must address administrative requirements
for manifests, recordkeeping, and reporting; and hazardous waste
facilities must comply with technical requirements mandating plans for
waste analysis, training, contingency procedures, groundwater
monitoring, and closure.
2.6 GENERAL INSPECTION PROCEDURES
Follow inspection
plan/strategy
In general, the visual inspection of the facility should proceed in
accordance with an inspection plan or strategy developed by the
inspector during inspection planning. This plan should lay out, in the
level of detail considered appropriate by the inspector (which may
vary according to individual preferences), the operations the inspector
intends to inspect and the tentative order in which the inspection will
proceed. The inspector may, however, determine that it is appropriate
2-5
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Maintain control
Remain oriented
to modify the plan based upon information obtained during the record
review or other factors, such as the availability of specific personnel
for interviewing or the scheduled operations of waste management
units to be inspected. Inspectors should be flexible in changing their
planned approach to suit conditions encountered at the facility. Step-
by-step procedures for visually inspecting a facility will vary according
to the type of facility and the objectives of the inspection.
When planning and performing the visual inspection, it is generally
desirable that the inspection proceed in a way which allows the
inspector to evaluate and understand the waste flow within the facility
and to determine the compliance status of each segment of the
facility's waste management system. For example, in a plant which
generates hazardous waste, stores waste for off-site disposal, and treats
some waste on-site, the inspection could proceed as follows, in brief:
Inspectors should not allow facility representatives to hurry the
inspection, direct the route of the inspection, or prevent them from
asking pertinent questions of facility personnel. Inspectors should ask
relevant questions of both the facility representative guiding them
through the facility and of other personnel. Questioning diverse
personnel may identify inconsistencies in explanations of procedures or
operations that could indicate possible non-complying conditions that
should be further investigated, and can also give the inspector an
indication of the adequacy of the personnel training program.
Answers to questions and observations that are not reported on
checklists should be recorded in a field log or notebook.
Inspectors should be careful to remain oriented during the tour of the
facility so that they can accurately note locations of waste
management areas, possible releases, potential sampling locations, etc.
At larger facilities, inspectors should carry a map or plot plan in order
to note locations and maintain their orientation.
2.7 INSPECTION CHECKLISTS
Pre-inspection
activities
As previously discussed, the inspector should complete as much of the
applicable checklist(s) as possible in the facility office, generally
during the record review, prior to .visually inspecting the facility
(unless the objectives of the inspection or other reasons dictate that
the visual inspection occur before the record review). The inspector
should leave blank those sections of the checklist(s) which cannot be
answered without visual inspection.
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Inspection
activities
During the visual inspection, the inspector should complete these
sections. However, completing these sections is not the sole purpose
of the visual inspection, and it is critical that the inspector not limit
the visual inspection to only completing the checklist. Inspectors
should be aware of, and investigate, all relevant waste generation and
management activities throughout the facility, and be alert to what is
happening around them as they tour the facility. If inspectors conduct
visual inspections in ways which allow them to understand how wastes
are generated, transported, and managed at the facility (as previously
discussed), they should be able to complete the applicable checklists
easily during the inspection.
2.8 WASTE SAMPLING
Reasons for
sampling
Sampling is generally conducted to verify the identity of a waste or to
identify potential releases of hazardous wastes or constituents to the
environment.
Inspection planning If sampling is to be conducted during an inspection, the need to
sample will be determined or made known to the inspector during
inspection planning. The inspector should refer to sampling manuals
during inspection planning to obtain information on preparing
sampling plans, taking samples, preserving samples, splitting samples
with the owner/operator, and completing chain-of-custody
requirements.
On-site activities
Reasons for future
sampling
In most cases, sampling will not be performed during routine
inspections. However, the inspector should be aware of, and identify,
potential sampling requirements that may need to be fulfilled in future
inspections, particularly in cases where the inspector has identified
potentially non-complying conditions or criminal activity during the
course of the inspection. In these cases, it is possible that case
development inspections will be performed at the facility, and it is
helpful when planning these inspections to have the results of previous
inspections in which potential sampling locations and needs have been
identified based on observed conditions at the facility.
There are many possible conditions or activities which may lead the
inspector to determine that future sampling will probably be necessary.
Examples of some of these conditions include situations in which:
/
The owner/operator is handling a potentially hazardous waste
as a non-hazardous waste.
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(Sampling may be required to verify that the waste is hazardous
or non-hazardous.)
In-plant waste handling practices indicate that
mislabeling/misidentification of waste is likely to occur, or that
wastes may vary significantly in characteristic over time and be
mismanaged as a result.
(Sampling may be required to demonstrate that the facility is
mislabeling or misidentifying wastes.)
There is visible or other observable evidence of possible
releases of hazardous wastes from waste management units,
satellite storage areas, waste generating areas, etc.
(Sampling media and wastes may be required to demonstrate
that a release has occurred or is occurring.)
Wastes may be being managed improperly, i.e., in an
inappropriate treatment or disposal unit.
(Sampling may be required to verify that the correct wastes are
being managed in the facility's various waste management
units.)
Useful information Whenever such condition/activities are encountered, the inspector
for future should identify the media or wastes to be sampled, the physical
inspections locations to sample (e.g., the location of a possible release), the steps
within a treatment process to sample, the physical characteristics of
the medium to be sampled (e.g., sludge, granular solid), and other
relevant information that would be helpful in developing a sampling
plan for a future inspection.
2.9 DOCUMENTATION
General
information
Documentation refers to all printed and mechanical media produced,
copied or taken by the inspector to provide evidence of suspected
violations. It is strongly recommended that the inspector record
information collected during the inspection in only the following types
of records: field notebooks, checklists, photographs, maps, and
drawings. Recording information on other loose papers is
discouraged; loose papers may be easily misplaced and the
information on them discredited during hearings. Proper
documentation and document control are crucial to the enforcement
2-8
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system, as the Government's case in a formal hearing or criminal
prosecution often hinges on the evidence gathered by the inspector.
Therefore, it is imperative that each inspector keep detailed records of
inspections, investigations, photocopies, photographs taken, etc., and
thoroughly review all notes before leaving the site.
Document control The purpose of document control is to assure the accountability of all
documents for the specific inspection when that inspection is
completed. Accountable documents include items such as logbooks,
field data records, correspondence, sample tags, graphs, chain-of
custody records, bench cards, analytical records, and photos. To
ensure proper document control, each document should bear a
serialized number and should be listed, with the number, in a project
document inventory assembled upon completion of the inspection.
Water-proof ink should be used to record all data on serialized,
accountable documents.
2.10 FIELD NOTEBOOK
In keeping field notes, it is strongly recommended that each inspector
maintain a legible daily diary or field notebook containing accurate
and inclusive documentation of all inspection activities, conversations,
and observations. Field notes should include any comments, as well as
a record of actual or potential future sampling points, photograph
points, and areas of potential violation. The diary or field notebook
should contain only facts and observations because it will form the
basis for later written reports and may be used as documentary
evidence in civil or criminal hearings. Notebooks used for recording
field notes should be bound and have consecutively numbered pages.
A separate notebook should be used for each facility inspected.
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APPENDIX 2-A. HAZARDOUS MATERIALS/HAZARDOUS WASTE SAMPLING
EQUIPMENT
Bucket auger
Bucket
Containers
- jars
- plastic (for metals)
- organic sample containers
Bailers
Pumps
Rope '
Glass tubes
Ice
Scoops
Trowels
Tape
- labeling
- duct
- electrical
Conductivity meter
Thermometer
Dissolved oxygen meter
Steel tape measure
Sampling safety equipment
(in addition to Appendix 1-B
items)
- Tyvek suit
- booties
- gloves
- harnesses
- chemical-resistant suit
- Organic Vapor Analyzer
(OVA)
Decontamination
equipment
- buckets
- Alconox
- brushes
- grate
- deionized water
- solvents for equipment
cleaning
- steam cleaning machine
- plastic bags
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APPENDIX 2-B. GENERAL SITE INSPECTION INFORMATION FORM
A. Site Name B. Street (or other identifier)
C. City D. State
E. Site Operator Information
1. Name 2. Telephone Number
3. Street 4. City 5. State
F. Site Description
G. Type of Ownership
1. Federal 2. State 3. Municipal 4. Private
H. Site classification
1. Generator 2. Transporter 3. Treatment 4. Storage__ 5. Disposal
I. Inspector information
1. Principal Inspector 2. Organization
3. Title 4. Telephone No.
J. Inspection Participants
1 6,
1 L
1 &
£ 9,
1 1O
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APPENDIX 2-C. WASTE INFORMATION WORKSHEET
(To be filled out for each facility waste)
1. Waste Name:
2. Process generating the waste:
3. Waste classification
Hazardous (Waste code:
Non-Hazardous
4. How has the facility made this determination?
Testing
Process knowledge
5. Are any test results available?
Yes (if so, look at)
No
6. Waste generation rate:.
7. Disposal procedure:
Current
Past
8. Have manifests been used for off-site shipment?
Yes (if so, look at)
No
9. Is waste subject to land disposal restrictions? Yes No
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APPENDIX 2-D. CONTAINERS CHECKLIST
A. USE AND MANAGEMENT
1. Are containers in good condition? Yes No
B. COMPATIBILITY OF WASTE WITH CONTAINER
1. Is container made of a material that will not react
with the waste which it stores? Yes No
C. MANAGEMENT OF CONTAINERS
1. Is container always closed while holding hazardous waste? Yes No
2. Is container handled so that it will not be opened, Yes No
handled, or stored in a manner which may rupture it or
cause it to leak?
D. INSPECTIONS
1. Does owner/operator inspect containers at least weekly for
leaks and deterioration? Yes No
E. CONTAINMENT
1. Do container storage areas have a containment system? Yes No
F. IGNITABLE AND REACTIVE WASTE
1. Are containers holding ignitable and reactive waste located
at least 15m (50 ft) from facility property lines? Yes No
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APPENDIX 2-D. (Cont.)
G. INCOMPATIBLE WASTE
1. Are incompatible wastes or materials placed in the same
containers? Yes No
2. Are hazardous wastes placed in washed, clean containers
which previously held incompatible waste? Yes No
3. Are incompatible hazardous wastes separated from each
other by a berm, dike, wall, or other device? Yes No
H. CONTINGENCY PLAN AND EMERGENCY PROCEDURES
1. Is a contingency plan maintained at the facility? Yes No
If yes, does contingency plan include:
a. arrangements with local emergency response
organizations? Yes No
b. emergency coordinators' name, phone numbers,
and addresses? Yes No
c. list of all emergency equipment at facility
and description of equipment? Yes No
d. evacuation plan for facility personnel? Yes No
2. Is there an emergency coordinator on site or on call at
all times? Yes No
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APPENDIX 2-E. WASTE PILES CHECKLIST
A. DESIGN AND OPERATING REQUIREMENTS
1. Is the pile containing hazardous waste protected from
wind? Yes No
2. Does waste pile have a liner and leachate collection
system? Yes No
3. Is run-on diverted around active portion? Yes No
4. Is runoff collected and controlled? Yes No
5. Are collection and holding facilities emptied after storms? Yes No
B. WASTE ANALYSIS
1. Is a representative sample of waste from each incoming
shipment analyzed before the waste is added to the pile
to determine the compatibility of the wastes? Yes No
2. Does the analysis include a visual comparison of color
or texture? Yes No
C. CONTAINMENT
1. Is the leachate or runoff from the pile considered a
hazardous waste? Yes No
If yes, is the pile managed with the following:
a. an impermeable base compatible with the
waste? Yes No
b. run-on diversion? Yes No
c. leachate and runoff collection? Yes No
d. periodic emptying of collection and holding facilities? Yes No
OR
e. protection from precipitation and
run-on by some other means? Yes No
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APPENDIX 2-E (Cont.)
D. MONITORING AND INSPECTION
1. Are liners and covers inspected for damage during
construction? Yes No
2. Are waste piles inspected weekly for deterioration,
run-on and runoff controls, wind dispersal control, and
proper function of leachate collection system? Yes No
E. IGNITABLE OR REACTIVE WASTES
1. Are ignitable or reactive wastes placed in the pile? Yes No
If yes,
a. Does the addition of the waste result in the waste or mixture no longer
meeting the definition? Yes No
(Use narrative explanation sheet to describe procedure)
OR
b. Is the waste protected from sources of ignition or reaction? Yes No
1. If yes, use narrative explanation sheet to describe separation and
confinement procedures.
2. If no, use narrative explanation sheet to describe sources of ignition or
reaction.
F. INCOMPATIBLE WASTES
1. Are incompatible waste placed together in the pile? Yes No
2. Are incompatible waste separated from each other by a
dike, berm, or wall? Yes No
3. Is there evidence of fire, explosion, gaseous emissions,
leaching, or other discharge? (Use narrative explanation
sheet.) Yes No
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VI
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INTRODUCTION TO
POLLUTION PREVENTION
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TABLE OF CONTENTS
Section Page
1.0 Introduction to Pollution Prevention 1-1
1.1 Waste Management Hierarchy 1-1
1.2 Source Control Methods 1-3
1.3 Implementation of Pollution Prevention Techniques 1-8
1.4 Selected Pollution Prevention Case Studies 1-9
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CHAPTERl
1.0 INTRODUCTION TO POLLUTION PREVENTION
Pollution Prevention is generally defined as any in-plant process that
reduces, avoids, or eliminates the use of toxic materials and/or the
generation of pollutants and wastes so as to reduce risks to human health
and the environment and to preserve natural resources through greater
efficiency and conservation. The goal of pollution prevention is to
minimize environmental risks by reducing or eliminating the source of
risk (rather than reactively through treatment and disposal of wastes
generated).
There are significant opportunities for industry to reduce or prevent
pollution at the source through cost-effective changes in production,
operation, and raw materials use. The opportunities for source reduction
are not often realized because existing environmental regulations, and the
industrial resources they require for compliance focus upon treatment and
disposal, rather than source reduction. Source reduction is different and
more desirable than waste management and pollution control.
A logical waste management hierarchy would be based on the principal
that pollution should be prevented or reduced at the source wherever
feasible, while pollutants that cannot be prevented should be recycled in
an environmentally safe manner. In the absence of feasible prevention or
recycling opportunities, pollution should be treated. Disposal or other
release into the environment should be used as a last resort. This
hierarchy is described in more detail in the next section.
1.1 WASTE MANAGEMENT HIERARCHY
In this section, a waste management hierarchy was developed as an
approach to prioritize pollution control methods. This hierarchy assesses
four types of pollution control methods based on their effectiveness in
reducing the risks to human health and the environment from pollution.
Source Reduction The most desirable option of the hierarchy and the most effective way to
reduce risk is through source reduction. Source reduction is defined as
any method that reduces or eliminates the source of pollution entirely.
This includes any practice that:
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Recycling
Treatment
Disposal
Reduces the amount of hazardous substances, pollutants, or
contaminants entering a waste stream or otherwise released into
the environment prior to recycling, treatment, or disposal; and
Reduces hazards to public health and the environment associated
with the release of such substances, pollutants, or contaminants.
The term source reduction includes equipment or technology
modifications, process or procedure modifications, reformulation
or redesign of products, substitution of raw materials, and
improvements in housekeeping, maintenance, training, or
inventory control. It is important to note that the term source
reduction does not include any practice which alters the physical,
chemical, or biological characteristics, or the volume of a
hazardous substance, pollutant, or contaminant through a process
or activity which itself is integral to, and necessary for, the
production of a product or the provision of a service.
Where pollution cannot be prevented through source reduction methods,
the wastes contributing to the pollution should be recycled. Recycling is
the use, reuse, or reclamation of waste after it has been generated (e.g.,
recycling spent solvents).
Wastes that cannot be feasibly reduced at the source or recycled should
be minimized through treatment in accordance with environmental
standards and regulations that are designed to reduce both the hazard and
volume of waste streams (e.g., adsorption of organic vapors onto
activated carbon).
Finally, any residues remaining from the treatment of waste should be
disposed of safely to minimize their potential for release into the
environment. Disposal involves the transfer of a pollutant to the
environment in either air, solid waste, or water (e.g., landfilling metal
scrap wastes).
Pollution control techniques include all four choices in the hierarchy.
Pollution prevention techniques include only source reduction or closed-
loop recycling, the first two choices in the hierarchy. Implementation of
pollution prevention methods is the best way to reduce or control
pollution considering their potential environmental and economic
advantages which include:
Energy and resources conservation;
Raw material losses reduction;
Treatment and disposal cost reductions;
Reduction of long-term liabilities associated with environmental
waste or cleanup;
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Improved worker health and safety; and
Reduced regulatory requirements.
The waste management hierarchy establishes a set of guidelines to follow
rather than a fixed set of rules. Practices such as treatment and proper
disposal can be protective of the environment when performed properly.
Industries can be expected to balance the costs and benefits when
evaluating pollution control strategies. Specific factors which must be
evaluated will be discussed in detail in a later section.
Many countries that are adopting pollution prevention as a national
environmental program rely on voluntary efforts by industries and
government to implement pollution prevention methods. These voluntary
efforts have been quite successful due to several factors including the
increasing costs of treating wastes, the increasing costs of transferring
wastes to landfills, treatment plants, and hazardous waste management
facilities; financial liabilities; and public pressure. These non-regulatory
incentives are causing industries to realize the economic and
environmental benefits gained from adopting pollution prevention control
methods.
1.2 SOURCE CONTROL METHODS
Source control (pollution prevention) techniques can be grouped in
numerous ways (as evidenced in the many manuals and guides prepared
by EPA and other U.S. agencies). For this presentation, the techniques
are grouped into the following eight classifications:
1. Process Changes
2. Material Substitution
3. Material Inventory and Storage
4. Waste segregation
5. Good housekeeping/Preventive Maintenance/Employee
Education
6. Product changes
7. Water and energy conservation
8. Recycling/waste exchange
Process Changes Process changes consist of changing one or more processes used by the
facility, or changing the equipment used in the process(es). The changes
can result in both reduced volume and/or toxicity of the waste generated.
Process changes may not necessarily be extensive or costly to implement.
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Some examples of potentially simple and inexpensive process changes
which are considered pollution prevention techniques include:
Reducing drag-out (transfer) of pollutants from process solutions
by slowing withdrawal speed of metal parts and allowing sufficient
drainage time over process tanks (or over drip tanks). These
procedures, along with other drag-out reduction techniques can
reduce the waste of expensive chemicals, the quantity of
pollutants in rinse waters, the toxicity of waste waters, and the
quantity of sludge generated.
Adjusting production schedules or dedicating process equipment to
reduce the quantity of cleanup wastes generated (e.g., use of
dedicated tanks in the paint formulating industry to eliminate
intermediate washing).
Use of still rinse techniques to reduce the volume of waste water
generated in electroplating processes. Still rinses are static (no
inflow or outflow) and are used to rinse metal parts after plating
processes. When constituent concentrations become unacceptably
high within the rinse tank, rinse waters may be used to replenish
the upstream plating bath. Evaporative equipment may be used to
concentrate rinse waters prior to replenishing the plating baths.
Material Changes in the raw materials used in a process can result in pollutant
Substitution source reduction by reducing or eliminating the hazardous materials that
enter the production process. Examples of pollution prevention using
material substitution techniques include:
Substituting organic polyelectrolytes in place of traditional
coagulation and flocculation agents (e.g., lime, alum) to reduce
quantities of sludge generated;
Substituting alkaline cleaners or citric acid cleaners for organic
solvents; and
Replacing environmentally hazardous hexavalent chromium
electroplating solutions with trivalent chromium.
Material Inventory Proper material inventory and storage refers to the purchasing, tracking,
and Storage storage, and handling of hazardous materials. There are two facets of
material inventory and storage:
Using good inventory and tracking procedures of hazardous
materials help minimize overstocking and contamination and
reduces the need to dispose of expired or contaminated materials.
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These procedures should ensure that raw materials are purchased
only when needed and in appropriate quantities. Expiration dates
of materials should be tracked and a "first-in, first-out" (FIFO)
policy (older materials used first) should be adopted.
Developing procedures and obtaining appropriate equipment to
prevent and respond to all potential sludge discharges including
spills, leaks, bypasses, and upsets (e.g., utilizing secondary
containment around tanks and containers of hazardous materials
and process equipment to prevent discharge of hazardous materials
and to reduce the quantity of waste generated from cleanup of
' spills or leaks).
Waste Segregation Segregation of different types of wastes can be a simple and effective
pollution prevention technique applicable to a wide variety of waste
streams and industries. By segregating wastes at the source of generation
and by handling hazardous and non-hazardous wastes separately, waste
volume and management costs may be reduced. Additionally,
uncontaminated or undiluted wastes may be reusable in the production
process or may be sent off-site for recovery. Practices for segregating
wastes include the following:
Isolating hazardous waste from nonhazardous waste. Blending
such waste makes all the waste hazardous and increases treatment
or disposal costs.
Segregating different types of solvents, particularly halogenated
solvents from non-halogenated solvents, and aromatic solvent from
aliphatic solvents. Solvents are harder to recycle and reuse.
Avoiding contamination of wastes with water. Solvents and oils
that are contaminated with water are harder to recycle and reuse.
In addition, wastes and waste water that are mixed with large
amounts of storm water require additional treatment steps and
costs.
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Good These procedures are generally simple and inexpensive to implement and
Housekeeping/Pre- effectively reduce pollution at its' sources.
ventive Main-
tenance/Employee
Education
Good Housekeeping Some examples of such procedures include:
Reducing dripping and splashing from parts being dipped in
process and rinse tanks. This prevents this waste water from
entering drains to the sewer or waste water treatment system.
Maintaining adequate distances between different chemicals to
prevent cross contamination; and
Keeping containers closed except when material is being removed.
Providing runnels and other transfer equipment to reduce loss of
material during transfer.
Preventive Preventive maintenance reduces malfunctions and leaks and can also
Maintenance reduce the quantity of waste generated. Preventive maintenance consists
of regular inspection, cleaning, testing, and lubrication of process,
storage, handling, monitoring and treatment equipment. A master
preventive maintenance file which documents all maintenance work
should be kept. Also, any parts that are worn or broken should be
replaced before a problem occurs (e.g., regular replacement of seals and
gaskets to prevent leaks from pumps, joints, valves, etc.).
Employee Education Employee education may be the most basic pollution prevention technique
and yet it is often overlooked. Pollution prevention education should be
an integral part of the training normally given to employees when they
begin a job and during regular refresher training. Two of the most
important aspects of training include:
Educating employees to know and understand the company's
pollution prevention goals. It is important for employees to know
and understand the benefits of reducing hazardous materials being
handled and generated. To accomplish this task, many companies
establish a facility-wide training program to educate employees on
pollution prevention techniques used by the facility.
Product Changes
Ensuring that all employees know and practice proper and efficient
use of tools and supplies. This is especially important for cleaning
operations.
Product changes that are considered pollution prevention techniques
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Water and Energy
Conservation
Recycling/Waste
Exchange
On-site Recycling
include any changes in the composition or use of an intermediate or end
product which results in reducing waste from the manufacture, use, or
ultimate disposal of the product. A life-cycle assessment of a product can
be used as an objective tool to identify and evaluate opportunities to
reduce the environmental impacts associated with its manufacture, use, or
disposal. The three components of the assessment include:
Inventory analysisIdentification and quantifying of energy and
resource use and waste emissions;
Impact AnalysisAssessment of the consequences those wastes
have on the environment; and
Improvement AnalysisEvaluation and implementation of
opportunities to effect environmental improvements.
Water and energy conservation should be considered as part of an overall
pollution prevention strategy. Benefits to reducing water and energy use
include reduced waste water generation and associated treatment/disposal
costs and reduced pollution associated with producing potable water and
the generation of energy. Examples of water and energy conservation
techniques include:
Employing timed automatic shutoff valves on equipment using
water such as rinses on a metal finishing line. This technique is
relatively inexpensive, but can result in substantial decreases in
water use and waste water generated.
Recirculating cooling waters through a cooling tower. Water used
in cooling heavy machines, quenching hot metals, molding and
forming processes, etc. should be recirculated to significantly
reduce water use.
Utilizing heat exchangers on high temperature discharges to heat
incoming water. This practice is employed at many industrial
laundries (including those at hospitals), chemical manufacturing,
and power generating facilities.
Recycling can be used where further source reduction techniques cannot
be implemented. Recycling involves the use of a waste as an effective
substitute for a commercial product or as a raw material in the
manufacture of a product.
Recycling the waste on-site by returning the waste back to the process or
another process (e.g., the use of waste acids and bases for pH adjustment
in waste water treatment systems or the use of a small On-site still to
purify degreasing solvents for subsequent reuse).
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Off-site Recycling/
Reclamation
Waste Exchange
Recycling waste off-site by sending it to a recovery/reclamation facility
for processing (e.g., sending metal-bearing sludges from industrial waste
water treatment processes to Off-site reclamation facilities).
Advertising the sale or the availability of wastes through a private- or
government-funded organization. Waste exchanges can help bring
together generators of waste with companies that can use the waste in
their production process.
1.3 IMPLEMENTATION OF POLLUTION
PREVENTION TECHNIQUES
When industries are deciding whether to implement pollution prevention
techniques in their facilities, several items must be examined.
First, it must be determined if the pollution prevention technique will
result in cross medium transfer of pollutants. It is important to avoid
transfer of pollutants from one media to another. The three types of
media are air, land, and water. Most treatment or disposal methods
transfer pollutants from one media to another. For example, wastewater
treatment that uses coagulation and sedimentation to remove metals
generates a sludge which is usually disposed in landfills. In this case, the
metal pollutants are transferred from the waste water to the sludge placed
in the landfill. Another example is the use of air stripping to remove
volatile organic compounds (VOCs). In this case, the volatile organic
compounds are removed from the waste water and released to the air.
Pollution prevention strategies can substantially decrease pollutant loads
to the environment without transferring pollutants from one medium to
another. An example includes substituting powder paints for water-based
and solvent-based paints for example, eliminates cleanup wastes and
emissions of VOCs.
A second consideration is worker health and safety. For example, the
substitution of a coagulant chemical which generates less sludge in a
pretreatment system may be more hazardous to workers handling it.
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Finally, any pollution control technique utilized must comply with all
applicable Federal, State and local laws and regulations. Some pollution
prevention strategies may require obtaining a permit or license or making
a special notification to the appropriate regulatory agency.
1.4 SELECTED POLLUTION PREVENTION CASE STUDIES
The United States Evironmental Protection Agency has established a
voluntary pollution prevention program intiative called, the 33/50
Program. The program derives its name from its overall goals-an
interim goal of 33% in 1992 and an ultimate goal of a 50% reduction by
1995 in releases and transfers of 17 high-priority toxic chemicals, using
1988 Toxic Release Inventory (TRI) reporting as a baseline. During
1988, 1.48 billion pounds of the target chemicals were either released to
the environment on-site or transferred off-site to waste management
facilities. The aim of the 33/50 Program is to reduce this amount by at
least 50%-743 milliion pounds-by 1995, with an interim reduction target
of more than 490 million pounds by 1992.
The Program is part of a broad group of EPA activities designed to
encourage pollution prevention as the best means of achieving reductions
in toxic chemical emissions. More than 16,000 facilites have reported
33/50 Program chemicals to the Agency since 1988. By contacting the
chief executives of the parent companies of TRI facilities that report
33/50 Program chemicals, the Program seeks to instill a pollution
prevention ethic throughout the highest echelons of American businesses.
In an effort to recognize companies making significant progress in
reducing chemical releases and transfers, Company Profiles have been
developed to provide detailed information about the reduction efforts
companies have undertaken. The following case summaries represent 14
companies, of the more than 1200 companies participating in the
Program, that have added to the success of the 33/50 Program.
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PRINTED CIRCUIT BOARDS
HADCO Corporation is a manufacturer of custom printed circuit boards and backplanes for use in
electronic components. Approximately 60% of the boards produced are used in computers, and an
additional 30% are used in telecommunications equipment. The remaining 10% find end uses in
various types of instrumentation, principally in medical devices and the automotive industry.
HADCO is headquartered in Salem, New Hampshire, and operates six facilities.
From July, 1989 through August, 1990 die company implemented a $1.7 million process conver-
sion and emission control project at its Deny facility. The project's goals were to eliminate use or
minimize air emissions of chemicals used in the facility's manufacturing operations.
The cornerstone of the project was implementation of new aqueous-based chemicals in the cleaning
and dry film processes. The dry film process was modified to include carbonate based developers
instead of 1,1,1-trichloroethane, and hydroxide solutions instead of dichloromemane, A screen
cleaning use of dichloromethane was also replaced with an aqueous cleaning solution at the Owego,
NH facility.
HADCO's conversion project has resulted in the following source reduction of chemicals:
Significant reduction in dichloromethane through conversion of six of the eight dry film
and cleaning processes to water based chemistry;
Elimination of l,l,l~trichloroethane through conversion of the cleaning and dry film pro*
cesses to water based chemistry; and,
Elimination of methyl ethyl ketone as an additive to dichloromethane in cleaning (its only
use at the facility).
Certain circuit board processes could not be replaced with this new water-based technology,
however, because of user specifications. To reduce emissions of these chemicals, HADCO also in-
stalled a dual-bed activated carbon adsorption recovery system at its Deny, NH facility, which
reduced remaining emissions of the three solvents by over 99%.
As an alternative to a recovery system, HADCO replaced both 1,1,1-trichloroethane and
dichloromethane with a terpene solvent at its Owego, NH facility.
The recovery system was installed to further reduce air emissions. However, HADCO's process
conversion and emission control program achieved significantly greater reductions than required by
New Hampshire Air Toxics Regulations (adopted April, 1990). HADCO's state permit for
dichloromethane allows emissions of no more than one pound per hour; however, the company
estimates that its emissions level has been reduced to 0.3 pounds per hour. In addition, the State
tew did not require control of methyl ethyl ketone or 1,1,1-trichloroethane at the Deny site. Thus,
HADCO has reduced air emissions by more than 270,000 pounds over the state requirements.
HADCO's efforts in pollution prevention and solvent recovery allowed the company to achieve its
goals two years ahead of schedule. Company-wide releases and transfers of its' major solvents
chemicals decreased 95% between 1988 and 1992, reflecting a reduction of almost 2.2 million
pounds. In addition, according to company officials, the company achieved additional reductions in
1993 that have brought its total reductions to 99.5%.
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STEEL PRODUCTS
Acme Metals Incorporated, based in Riverdale, Illinois, is the parent company of an integrated
steelmaker and three steel fabricating subsidiaries. Although interrelated, each subsidiary is
responsible for its own environmental programs.
Acme Steel Company, an integrated producer of steel products, operates coke and ironmaking
facilities in Chicago, IL and a steelmaking plant in Riverdale, DU Acme Packaging Corporation, a
manufacturer of steel strapping tools, operates facilities located in Riverdale, IL, Leeds, AL, New
Britain, CT, and Pittsburg, CA. These two subsidiaries are responsible for virtually all releases
and transfers of selected dimn?.f-"l« and are the focus of this profile.
Acme Metals Incorporated reduced annual releases and transfers of selected chemicals by more
than 833,000 pounds by 1992 from 1988 levels.
Acme achieved an 89% reduction in releases and transfers of these chemicals from 1988 to 1992,
surpassing its pledged reduction of 70% by 1995.
Since 1988, Acme has implemented several programs aimed at further reducing releases and
transfers of these chemicals. Acme has completed the following projects at its Chicago Coke plant:
Replace cooling system. Acme replaced its contact gas cooling system with a non-
contact, wet surface air cooler b the coke byproducts recovery process. The replacement
of the cooling system resulted in reductions of releases of approximately 143,000 pounds
of benzene, 276,000 pounds of cyanide, 28,000 pounds of toluene, and 6,000 pounds of
xyleoe, as well as 1,450,000 pounds of ammonia, and 10,000 pounds of naphthalene.
Install emission collector headers. Acme installed emission collector headers to remove
volatile chemicals, such as benzene, toluene, and xylene, from the headspaces of process
units and storage tanks. This process uses steam moving under negative pressure to sweep
the volatile chemicals into the byproduct recovery system. Emission collector headers
were installed at the light oil storage tank, the wash oil decanter, and the wash oil circu-
lation tank and resulted in a 14,000 pound reduction in releases of benzene, as well as
smaller reductions of toluene and xylene.
In addition, at Acme Packaging's Riverdale facility, spent lead dross from the steel strapping
production process is now sent to an off-site recycler. Previously, the lead was landfilled. The in-
creased recycling of lead resulted in a reduction of approximately 333,000 pounds of releases and
transfers of lead. Small components of lead are still landfilled as a component of nonhazardous
sludge generated from pollution control activities.
Acme reduced releases and transfers of other selected chemicals by nearly 2,600,000 pounds (75 %)
between 1988 and 1992.
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HEALTH CARE PRODUCTS
Johnson & Johnson is the world's largest health care company, with over 80,000 employees and
manufacturing and sales locations in more man SO countries. The company manufactures toiletries
and baby care products, medical supplies, and pharmaceutical products.
To reduce releases and transfers of selected chemicals, Johnson & Johnson has
undertaken several projects at its various facilities:
» Eliminating the use of methyl ethyl katone, methyl isobutyl ketone, and xylene at the Con-
sumer Products plant in North Brunswick, NJ. These chemicals were used in the
manufacturing process for the company's Band-Aid1* Brand adhesive bandages. Vinyl
extrusion and the use of a water-based emulsion has been substituted in the manufacturing
process, resulting in a decrease of over 380,000 pounds in releases and transfers of these
three solvents between 1988 and 1992.
Equipment and procedure changes in several processes at the Noramco facility in
Wilmington, DE, resulting in a combined reduction in releases and transfers of
dichloromethane and toluene of over 131,000 pounds between 1988 and 1992. These
changes by Noramco include: using dichloromethane and toluene as the seal fluid in liquid
ring vacuum pumps, instead of water, thereby reducing wastewater transfers; imple-
menting a leak detection and repair program to reduce fugitive emissions; and eliminating
one product recovery step, further reducing dichloromethane transfers in wastewater. This
facility has achieved reductions of 51% in releases and transfers of all these chemicals be-
tween 1988 and 1992.
Material substitution at Ethicon plants in SomerviUe, NJ and San Angelo, TX, as weQ as
the Advanced Materials facility in Gainesville, G A and the Vistakon plant in Jacksonville,
PL, resulting in a decrease of over 66,500 pounds (73 %) in releases and transfers of
l,t,l-trichloroethane between 1988 and 1992. A biodegradable cleaner was substituted for
1,1,1-tnchIoroethane.
As a result of Johnson & Johnson's pollution reduction efforts, releases and transfers of selected
chemicals decreased 63% (469,981 pounds) between 1988 and 1992. The largest reductions were
for xylene and methyl ethyl ketone, which decreased by 93% and 80% respectively. These reduc-
tions were due principally to the conversion of the adhesive carrier to aqueous emulsion in the
Band-Aid1" manufacturing process.
Releases and transfers of 1,1,1-trichloroethane also fell by 74% (66,580 pounds), in conjunction
with the company's goal of eliminating the use of this chemical and other ozone depleting
substances.
Johnson & Johnson has stated that participation in a Pollution Prevention (P2) program has helped
significantly in formulating reduction initiatives and in obtaining corporate support for their
implementation. The requirement of reporting releases and transfers of hazardous chemicals to
EPA initially made the company aware of the extent of its emissions and off-site transfers. The
company began to develop strategies for reducing releases and transfers of hazardous chemicals as
figures were first compiled company-wide. The P2 focus on a distinct set of chemicals then helped
Johnson & Johnson to develop and choose among specific source reduction projects for these
targeted chemicals.
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METAL AND PLASTIC HARDWARE
Aladdin Industries Inc. is a manufacturer of metal and plastic hardware for consumer and industrial
use. Located in Nashville Tennessee, Aladdin produces a wide variety of products such as lunch
kits, thermos bottles, hospital trays, Coffee cups, lamps, and coolers.
Although Aladdin is a relatively small generator of toxic chemical emissions, the company has
stated that, as a corporate citizen, it feels an obligation to reduce any emissions generated.
Aladdin's ultimate objective is to eliminate the emissions of toxic chemicals completely, primarily
through source reduction methods. However, in cases where source reduction is not possible,
Aladdin is looking to other means of reducing emissions such as treatment and recycling.
In order to meet its goals, Aladdin designed in-house projects focusing on each of the chemicals to
be ^"""Mh**, controlled, or replaced. For each of these projects, one staff member was appointed
project leader and had primary responsibility for ensuring the project's completion. For each
project, a goal, target implementation date, base year, and method for completion were articulated.
To date, Aladdin has completed the following projects:
All trichloroethylene usage was eliminated during 1993. Trichloroethylene was required
to remove petroleum oils from metal parts during metal forming processes. Synthetic
lubricants are now used in place of petroleum oils and are removed from parts with an
aqueous alkaline cleaner. The water from the alkaline cleaning process is treated on-site.
Dichloromethane use was completely eliminated from the facility as of 1993 by replacing
the polystyrene used in trays with polypropylene. Previously, the polystyrene trays were
cut from a sheet and blemishes around the edges were removed using dichloromethane.
Since the polypropylene trays are now injection molded, there are no blemishes to remove.
Toluene and methyl isobutyl ketone were completely eliminated from the Aladdin facility
as of 1993 by replacing a thinner containing toluene and methyl isobutyl ketone with a
thinner containing 25% toluene and 75% 1,1,1-trichloroethane. This thinner was later re-
placed with a thinner containing acetone in place of the toluene. The company is currently
investigating options to eliminate the 1,1,1-trichloroethane from this formulation.
Aladdin eliminated all releases and transfers of chromium, along with phosphoric acid and
sulfuric acid as of 1992. Using a newly installed on-site waste treatment facility,
Aladdin removes toxic materials from a water mixture containing chromium, phosphoric
acid, and sulfuric acid. Fifty percent of the water is recycled, while die remainder is of
sufficient quality to discharge to the sanitary sewer. The sludge is of sufficient quality to
be considered nonhazardous and is disposed of in a landfill. Prior to the installation of the
on-site treatment facility, all of these wastes were transferred off-site for treatment or
Aladdin eliminated its lacquer painting process by switching to a dry powder coating,
thereby eliminating the use of lead, xylenes, and ketones. Small quantities of lead,
xylenes, and ketones were previously used at Aladdin in its painting process for thermos
bottles.
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RUBBER-COATED FABRICS
Aldan Rubber Company is a manufacturer of rubber-coated fabrics that are used in a wide variety
of applications, including protective clothing for fire fighting, flexible duet connectors, convertible
tops, and baby products. Aldan is located in Philadelphia, Pennsylvania.
Aldan conducted a survey to identify areas in the manufacturing process where significant emis-
sions were taking place. This allowed the company to focus reduction efforts on the largest emis-
sion sources. The survey followed the "solvent trail" through the entire manufacturing process,
from unloading of solvent from tank trucks to post-manufacture disposalof rubber scrap. After
completing the facility survey and evaluating the results, Aldan identified five major activities that
would significantly reduce chemical emissions:
Totally enclose the rubber spreader. In its 1976 project, Aldan installed a hood to cap-
ture solvent emissions over part of its spreader. The captured solvent was then routed to a
recovery unit Aldan recently enclosed the entire spreader so that all solvent emissions are
captured and recycled, rather than just those under the partial hood.
Renovate the solvent recovery system. In order to improve the efficiency of its solvent
recovery system, Aldan renovated the system put in place in 1976. As part of the renova-
tion, the recovery unit received a complete overhaul, including replacement of the carbon
recovery media, cooling coils, and old seals and valves. Aldan reported the solvent recov-
ery unit's efficiency at 98% - 99% after the renovation, an increase of approximately 20%
from the previous efficiency level.
Use an alternative cleaner for machinery clean-up. Aldan traditionally used toluene in
a hand-wipe application to clean its equipment on a periodic basis. This cleaning removes
excess rubber, dirt, and other contaminants from production machinery. To eliminate this
use of toluene, Aldan now uses a d-limonene cleaner in a similar hand-wipe application,
with reduced but satisfactory performance, and somewhat higher but still acceptable cost.
Institute an employee awareness program. Aldan recognized that a significant quantity
of solvent emissions could be eliminated simply by improving the handling of process
materials. An employee awareness program, mandatory for all employees who handle
solvents, was implemented to achieve this goal. During the program, Aldan explained to
workers the environmental problems associated with the solvent emissions and made
suggestions for reducing emissions. Company officials believe that the employee aware-
ness program has been a great success.
Improve management of rubber scrap. Aldan developed a proprietary process by which
it is able to reduce solvent emissions from rubber scrap. This process is one in which the
scrap is processed to remove excess solvent prior to scrap disposal. Aldan has found that,
not only does the process reduce emissions of solvent to the air, but it also renders the
rubber scrap nonhazardous. The scrap can then be disposed of in a municipal landfill.
As a result of the efforts described above, by 1992 Aldan Rubber had reduced releases and trans-
fers of selected chemicals by 73% from the 1988 baseline, almost reaching its goal of an 80%
reduction. Reductions for toluene alone accounted for more than 1,000,000 pounds.
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SPECIALTY FENCING PRODUCTS
Anchor Fence, Inc. is a manufacturer of high quality chain link fencing systems, gates, and
specialty fencing products. The company has one facility located in Baltimore, MD, employing
approximately 85 workers.
The company has undertaken the following activities to reduce releases of selected chemicals:
Releases of methyl ethyl ketone have been reduced 93* (113,000 pounds) through substi-
tution of wafer based formulations of primers for pipes and fittings. This action accounts
for all of the observed decrease in releases of this chemical. In addition, all solvent based
paint applications are being strictly monitored to determine which can be converted to
water based products in the future.
Improvements in the operation of the company's waste water treatment system have re-
sulted in a 50% reduction in releases of lead, nickel, and zinc compounds between 1988
and 1992. These improvements consist primarily of adjusting the pH of the system to
increase efficiency of metals removal.
Eliminating the use of dichloromethane at the plant by shifting the PVC stripping process
for off-quality products to an off-site cleaning company that uses a hot salt bath PVC
removal process. This change resulted hi cost savings for the company.
Examination of solvent based cleaning processes using toluene and methyl ethyl ketone to
determine where solvent evaporation can be reduced. The company intends to install a
water-cooled component cleaning tank to further reduce releases of the solvents.
By 1992, Anchor Fence had reduced release of these chemicals by 87$ from 1988 levels.
Virtually all of this reduction, was « result of substitution of methyl ethyl ketone-based primers with
a water-based formulation.
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STAINLESS STEEL
Carpenter Technology Corporation manufactures stainless steel and other specialty metals for a
variety of industries including aerospace, nuclear, and electronics. The company is headquartered
in Reading, Pennsylvania and has four facilities that report emissions.
Its two largest facilities are in Reading, Pennsylvania and Orangeburg, South Carolina. The
former produces a variety of bar wire and strip metal products while the latter produces fine wire.
In addition, a small plant in Fiyeburg, Maine and « plant in £1 Cajon, California also make metal
products.
In 1988, as a first step in identifying source reduction opportunities, Carpenter set up a team
dedicated to continuous environmental improvements. This team consisted of key staff from
engineering, production, and research and development. The team identified several types of
projects including solvent substitution, reduction in solvent emissions through process
modifications, increased recycling of metal-bearing waste streams, and changes in operator
procedures to reduce the amount of acid used for metal descaling.
Specific changes «n*p^>v*«>fl^ by Carpenter to reduce solvent emissions include:
Substituting mineral spirits (petroleum-based solvents) for trichloroethane for cleaning
certain types of metal parts.
Eliminating non-cleaning uses of 1,1,1-trichloroethane (e.g., as a lubricant).
Improving vapor degreaser process control to minimize the amount of solvent needed to
dean metal components, and reducing by 50% the number of vapor degreasers used.
Improving process control to minimize the amount of waste acid generated and eliminate
the need for sending acid bath wastes off-site for treatment
Two additional changes resulted in the elimination of-all releases of metals (1,608,250 pounds of
chromium and nickel) to land and a significant reduction in the amount of metals transferred off-
site for treatment:
Improving sludge drying operations and recycling rolling mill sludges, resulting in a 400%
increase in the amount of metal oxides that can be recycled. These wastes were
previously transferred off-site for treatment.
Adding chemical inhibitors to acid bath solutions to reduce the amount of dissolved metals
being transferred to the acid waste streams.
In addition, for economic reasons, the company consolidated its operations in 1989 by closing the
Bridgeport plant while maintaining similar company-wide production levels through operation of
four other plants. Through this action, Carpenter was able to achieve a 35% reduction in releases
and transfers of selected chemicals.
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SHOES
Dexter Shoe Company is a manufacturer of shoes for men, women, and children. The company is
headquartered in Dexter, Maine and has four facilities in Maine: two in Dexter, one in
Skowhegan, and one in Milo.
Both the Headquarters and Skowhegan facilities are using a three-tiered approach to meet its
reduction goals: reduction in chemical use, substitution with less hazardous chemicals, and solvent
recovery.
Hie Skowhegan facility has had particular success in substitution and solvent recovery. The
facility reports the following activities:
Replacing two solvent-based waterproofing agents with aqueous-based products. These
new products are more expensive than their solvent predecessors, but provide better cover-
age using less product.
Replacing methyl ethyl ketone as a cleaning solvent with heptane. Because heptane still
poses some risk, however, the company is continuing to investigate other alternatives.
Employing solvent recovery for cleaning solvents, such as methyl ethyl ketone and
heptane. Dexter uses solvent recovery both for reuse of individual solvents and for gener-
alized recovery of mixed cleaning solvents. Some of the solvent recovery is done within
the process for which the chemicals are used and, thus, can be considered source
reduction.
A similar progress report from Dexter's Headquarters facility describes the following .individual
reduction accomplishments:
Substituting solvents and cleaners containing methyl ethyl ketone, methylene chloride, and
toluene with water-based products.
Replacing a filler product containing 4096 acetone with a cut insert material bonded to the
upper part of the shoe with a hot melt adhesive.
Installing a solvent recovery system for reuse of cleaning solvents.
Emissions of all reported chemicals at the company's two participating facilities have already
decreased 47% from 1988 to 1992 through elimination of 209,471 pounds of emissions:
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AUTOMOBILE AND TRUCK COMPONENTS (SEAT AND TRIM)
Douglas & Lomasoo Company is a manufacturer of automobile and truck components, primarily
seat and trim parts. The company is headquartered in Farrmngton Hills, Michigan and operates 16
manufacturing facilities located in Alabama, Arkansas, California, Georgia, Iowa, Maryland,
Mississippi, Missouri, Nebraska, Tennessee, and Texas.
To meet its reduction goals, Douglas & Lomason has undertaken a number of source reduction
activities, primarily product and process reformulation. The company has completed projects to
reduce chemical use in both the molding and painting processes.
* Implementing a new mold-release agent formulation. The Havre-de-Grace, MD,
facility manufactures foam seat pads using a molding process. This process involves
applying a wax mold-release agent to the mold to facilitate the removal of the finished
molded product. Douglas & Lomason's traditional mold-release agent, which contained
1,1,1-tricbloroetbaneas a solvent, was replaced with a water-based formulation. This
substitution completely rfimimted the use of 1,1,1-trichloroelhane, a reduction of 350,000
pounds.
Using "high-solids" paint formulations. At one facility, Douglas & Lomason manufac-
tures metal trim parts which are painted. The amount of solvent, such as toluene, xylene,
and methyl ethyl ketone, used in these paints was reduced through the use of reformulated
"high-solids" paint. "High-solids* paint uses a reduced percentage of solvent in
formulating the paint, thereby increasing the percentage of solids. This approach resulted
in achieving reductions at the Phenix City, AL, facility.
Using water-based paint. At several facilities, Douglas & Lomason manufactures metal
seat frames which are painted for rust protection. The use of solvents in the paint has
been rfitnitmtad by using water-reducible paints, in which the solvents (in this case toluene
and xylene) are replaced with ethylene glycol. This approach was used at the Columbus,
NE, facility, contributing to reductions of 86,454 pounds of toluene and xylene releases
between 1988 and 1992.
Eliminating the use of paints. Solvent use has also been reduced or eliminated through
the implementation of two new processes that eliminate the need to paint certain parts.
First, the spray-application of rust inhibitors'has eliminated the need for painting, thereby
reducing and in some cases eliminating the use of solvents. A second process
implemented by Douglas & Lomason involves the chemical application of a coating to
metal parts using a process that requires no solvents. The Red Oak, 1A, facility used this
process to eliminate releases and transfers of 61,000 pounds of toluene and xylene.
As a result of these and other efforts, Douglas & Lomason has made outstanding progress in reduc-
ing its releases and transfers of selected chemicals, including surpassing its 1995 reduction goal
several years early. Douglas & Lomason succeeded in reducing its releases and transfers by 88%
between 1988 and 1992, a reduction of 525,285 pounds. This reduction in releases and transfers
was achieved despite an increase in production between 1988 and 1989.
As part of Douglas & Lomason's efforts, the Havre-de-Grace, MD, Red Oak, IA, and Columbus,
NE facilities have completely eliminated their use of selected air toxic and other chemicals. The
company as a whole has completely eliminated the use of 1,1,1-trichloroethane.
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SPECIALTY CHEMICALS AND METALS
Olin Corporation is a Fortune 200 company, headquartered in Stamford, CT, with 29 facilities
nationwide in 15 states. The company manufactures a wide variety of products, including specialty
chemicals, metals, and other materials, as weU as products for the defense, aerospace and sporting
ammunition industries. Examples of significant projects at Olin facilities that have successfully
reduced the emissions of these chemicals to me environment include:
Olin Corp., Rochester, NY* Olin's Rochester facility produces over 60 different types of specialty
chemicals - relatively low volume products tailored to the specific needs of individual customers,
including biocides (zinc or sodium pyrithione), aniline dyes, and pharmaceutical ingredients. In
1988, the facility reported air emissions of 11,540 pounds of carbon tetrachloride, which is used as
a non-reactive diluent. La order to recover carbon tetrachloride from air vents, the plant installed a
scrubber and additional process vent collection equipment, and now reuses the reclaimed material
in several of the facility's production processes. 1992 air emissions of carbon tetrachloride were
reduced to 3,437 pounds at this facility, a reduction of 70%. This facility is also investigating the
substitution of carbon tetrachloride and other chemicals with non-toxic raw materials.
Olin Ordnance, Red Lion, PA. The Red Lion facility produces various munitions for the military.
In 1988, this facility reported air emissions of 122,535 pounds of 1,1,1-trichloroethane. This
chemical is used as a multi-purpose cleaner and degreaser. The Red Lion facility took a number of
steps to reduce the use of this chemical, including: restricting access and requiring employees to
justify their use of the material; identifying material substitution options for products not required
to use the chemical (e.g., by military procurement specifications); and modifying the chiller on a
solvent degreaser to enhance vapor capture. As a result of these efforts, air emissions of 1,1,1-tri-
chloroethane were reduced to 21,700 pounds in 1992, a reduction of over 80% from 1988 levels.
The facility is currently investigating two additional actions to further reduce the use of 1,1,1-
trichloroethane: installing a parts washer which will use water-based cleaners instead of
chlorinated solvents, or altering the overall production process to completely eliminate the cleaning
process.
Bridgeport Brass Co., Indianapolis, IN. In 1988 this facility reported air emissions of 37,000
pounds of 1,1,1-trichloroethane and dichloromethane, which were used as degreasers. By 1990,
the facility had completely eliminated its use of these two chlorinated solvents by switching to the
use of water-based soaps and hot water rinsing in its metal processing and maintenance operations.
Main Plant Facility, East Alton, IL. Olin's East Alton Main Plant facility used to landfill large
quantities of lead wastes (off-site disposal of 815,853 pounds in 1988), primarily from bullets test-
fired into sand traps at the Winchester sporting ammunition plant The facility used to screen as
much lead as possible out of the sand for reuse in their own production processes, and landfill the
remaining lead-contaminated sand off-site. The facility began selling unscreened material to a
battery manufacturer, and more recently began selling it to a lead smelter. The sand/lead mixture
is used directly as a recycled raw material in the smelting process. The landfilling of lead wastes
has thus been dramatically reduced to 39,673 pounds in 1992, for an overall reduction of 95%.
Between 1988 and 1992, Olin reduced its releases and transfers of selected chemicals by 67%, a
reduction of 1,367,614 pounds. Much of this reduction was the result of eliminating or capturing
473,114 pounds of air emissions from solvents. In addition, Olin reduced off-site chemical
disposal 876,904 pounds between 1988 and 1992, including shifting 776,180 pounds of lead from
off-site disposal in a landfill to off-site recycling an action that represents a move up the
pollution prevention hierarchy.
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MOTION CONTROL PRODUCTS
Parker Hannifin Corporation manufactures a broad array of motion control products for industrial and
aerospace applications. The company is headquartered in Cleveland, OH and employs nearly 26,000
individuals "worldwide at 143 manufacturing plants and 87 administrative and sales offices, company
stores, and warehouses. Parker's Industrial segment, which accounts for 75% of the company's sales,
is comprised of five groups: Fluid Connectors, Motion & Control, Automotive & Refrigeration, Seat,
and Filtration. The company's Aerospace segment is a single group with several divisions that account
for the remaining 25% of Parker's sales.
To reduce releases and transfers of selected chemicals at its facilities in the United States, the company
undertook the following activities between 1988 and 1992:
Eliminated 756,000 pounds of releases and transfers of dichloromethane, tetrachloroethylene,
1,1,1-trichloroethane, and trichlorethylene by switching to aqueous cleaning systems for
degreasing operations. Because the aqueous cleaning process requires agitation of the parts,
part of the conversion involved redesigning the racks used to hold parts during cleaning to
accommodate agitation,
* Eliminated 453,000 pounds of releases and transfers of methyl ethyl ketone and toluene by
substituting water-based solutions for solvent solutions used to carry cements in the
manufacture of rubber hoses. This substitution required the addition of a drying step because
of the relatively slow evaporation rate of water.
Eliminated 109,000 pounds of releases and transfers of carbon tetrachloride, methyl isobutyl
ketone, &nd xylene by substituting water-based adhesives and paints for solvent-based adhe-
sives and paints.
Eliminated 30,000 pounds of releases and transfers of chromium and chromium compounds
, -used in coloring processes that are part of the metal finishing operations. This reduction was
achieved through waste minimization techniques such as counter-current rinsing, reduced
drag-out rates, and unproved quality control.
Reduced releases and transfers of cadmium and cadmium compounds by 15,000 pounds by
substituting zinc plating for all of the cadmium plating process carried out in metal finishing
operations. Cyanide releases and transfers associated with the cadmium plating operations
nave increased. This increase is due to the fact that the company switched approximately
50% of its cyanide treatment from on-site to off-site. (Waste treated on-site is reported only
for quantities not destroyed or removed, while the full quantity treated off-site is reported as
a transfer). Parker estimates, however, that releases and transfers of cyanide will be elimi-
nated by 1994 when the conversion to zinc plating will be complete at all of its facilities.
In addition to these activities, Parker is working with steel suppliers to minimize emissions of metals
during machining operations by developing raw material steel with a low or zero lead content. This
effort is currently in the development stage, but promising results are expected in the future. In the
meantime, Parker achieved reductions in metal emissions through improved scrap recovery and control
methods. However, because these reductions are relatively small, they are not measured by the
company and therefore cannot be quantified.
As a result of Parker's pollution prevention efforts, releases and transfers of selected chemicals
decreased by more than 1,350.000 pounds between 1988 and 1992. This reduction of 71 % exceeds
the company's Program goal of a 50% reduction more than three years ahead of schedule.
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PRINTED CIRCUIT BOARDS
Printed Circuit Corporation, located in Woburn, Massachusetts, is a manufacturer of printed circuit
boards. The company provides its products to companies in the electronics, instrumentation,
telecommunication, and automotive industries.
In order to meet its program goals, Printed Circuit adopted a two-step approach, first, the
company focused its efforts on eliminating all use of dichloromethane in its operations. To accom-
plish this goal, the company implemented a process that uses a water-based cleaner to strip away
excess polymer from the etched circuit boards. In addition, Printed Circuit switched all solvent
cleaning operations to l,i,l-trichloroethane. These changes eliminaffd all use of dichloromethane
at Printed Circuit by the end of 1991. As a result of the process change, the company also was
able to minimize its use of meuanoL
Although the switch to 1.1,1-trichloroethane for all solvent cleaning operations caused releases of
the chemical to increase between 1990 and 1991, Printed Circuit showed an overall reduction in
releases of selected chemicals between the two years. The company believed that by focusing its
efforts on one chemical at a time, it would be able to make more rapid progress toward reducing
emissions than if it were addressing several chemicals simultaneously.
To eliminate the use of 1,1,1-trichloroethane, the company undertook an evaluation of potential
replacements. Printed Circuit worked with six vendors nationwide over a two-year period to
identify replacements that would;
be compatible with other chemicals and materials used in production;
comply with environmental standards; and
be economically feasible.
As a result of the study, the company has replaced its use of 1,1,1-trichloroethane as a developing
agent with a water-based sodium carbonate solution. In addition, Printed Circuit now uses a mild
detergent with water tor the final cleaning of completed circuit boards, in place of dichloromethane
and 1,1,1-trichloroethane.
As a result of these efforts, Printed Circuit Corporation reduced total releases of selected chemicals
by 87% from 1988 to 1991 after the elimination of dichloromethane. Furthermore,the company
completely eliminated releases of all 17 selected chemicals by 1993 after the elimination of 1,1,1-
trichloroethane, far surpassing its goals.
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AIRCRAFT, RESIDENTIAL AND COMMERCIAL APPLIANCES
Raytheon Company is a diversified organization whose major interests include manufacturing of
aircraft, residential and commercial appliances (including refrigeration, cooking, and laundry equip-
ment), electronic? (including guidance systems, guided missiles, printed circuit boards, and
communications equipment), and energy/environmental services (including power, transportation,
logistics support, and road building equipment). Raytheon is headquartered in Lexington, Massa-
chusetts and had twenty five facilities in the United States that reported releases and transfers of
chemicals in 1988.
Raytheon's reductions of selected Chemicals were achieved as a result of several on-going projects.
Eliminate or reduce solvents in cleaning operations. Dichloromethane, 1,1,1-trichloro-
ethane, tetrachloroethylene, trichloroethylene, and CPC-113 were all targeted by
Raytheon's ODS and suspected carcinogen, phaseout goals. In 1988, these solvents were
used at 18 facilities for electronics cleaning and metal degreasing, and as general solvent
cleaners.
Terpene-based cleaners and mildly alkaline aqueous solutions were identified as alterna-
tives to these solvent cleaners, Raytheon has successfully eliminated its use of
dichloromethane, tetrachloroethylene, and CFC-113, and nas significantly reduced its use
of 1,1,1-trichloroethane and trichloroethylene as a result of the development of these alter-
nate cleaners.
Eliminate the use Of dichloromethane for paint stripping applications. At the Wichita
facility, dichloromethane was used to strip paint from aircraft. Raytheon implemented a
dry media (wheat starch) blasting system for paint stripping that completely eliminated the
need for dichloromethane at this facility.
Reduce 33/50 Program chemicals in painting and soldering applications. Lead, chromium,
toluene, and xylene are used at Raytheon facilities in painting and soldering operations.
Raytheon has identified and implemented a powder paint system in some facilities which
nas resulted in a reduction of releases and transfers of these chemicals. For applications
in which powder painting is not technically feasible, Raytheon is working with its coating
suppliers to reduce the amount of solvent used in its coatings.
As a result of these and other efforts, Raytheon's releases and transfers of selected chemicals
decreased over 2.5 million pounds between 1988 and 1992 a 65% reduction from 3,883,820
pounds to 1,360,658 pounds. The major components of this reduction were the elimination of
dichloromethane and tetrachloroethylene, and the significant reduction of releases and transfers of
1,1,1-trichloroethaneand trichloroethylene.
The phaseout of the use of dichloromethane and tetrachloroethylene resulted in a reduction of
706,701 pounds of releases and transfers of these chemicals between 1988 and 1992. These reduc-
tions account for approximately 28% of total reductions of releases and transfers of these chemicals
during that period. The replacement of 1,1,1-trichIoroedume and trichloroethylene resulted in a
reduction of 1,354,654 pounds of releases and transfers of these chemicals. This reduction
accounts for approximately 54% of total reductions from 1988 to 1992.
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INTEGRATED STEEL
U.S. Steel is a large, integrated steel manufacturer and also includes several smaller diversified
businesses. USX Corporation also is involved in the oil and natural gas businesses through its
Marathon Oil Group and Delhi Group. U.S. Steel has its headquarters in Pittsburg, Pennsylvania,
and operates six wholly-owned plants which report releases and transfers of chemicals. In
addition, U.S. Steel is involved in several joint Ventures including USS/POSCO Industries and
USS/Kobe Steel.
Four of U.S. Steel's six facilities are in Pennsylvania: The Clairton Works (Clairton), and the
Edgar Thomson (Braddock), Irvin (West Miffin), and Fairless (Forest Hills) plants on the Man
Valley Works. The other plants are the Gary (Indiana) Works and die Fairfield (Birmingham,
Alabama) Works.
U.S. Steel expected to achieve its reductions through material reuse/recycling, process modifica-
tions, and product changes. Based on its reported 1988 emissions data, the company's goal trans-
lates into an overall reduction of 2,250,952 pounds in total releases and transfers.
U.S. Steel achieved significant reductions in releases and transfers of selected Program chemicals
through source reduction and recycling initiatives at several of its facilities. Examples of specific
changes implemented by the company include:
* ^^
Installation of inert gas blanketing systems. These systems use nitrogen to confine air
emissions of volatile toxic chemicals such as benzene, cyanide, toluene, and xylene. By
maintaining a layer of bert gas over an open tank or container, toxic chemical vapors are
unable to escape from the tank. U.S. Steel has installed blanketing systems on product and
by-product storage tanks and decanters at both its Gary and Clairton plants.
Implementation of dust pelletiang process. In the Steel making operations, pollution
control dusts containing iron units and various metallic compounds are produced. Under
normal circumstances, these dusts are landfilled. Because of the recoverable iron units in the
dusts, the Edgar Thomson plant, U.S. Steel Mon Valley Operations has implemented a
pelletizing operation. The pellets are recycled back into the steel making operations.
Modification of coke quenching process. After the coke is removed from the Coke ovens,
it must be cooled rapidly. Previously, the Clairton Works used contaminated water to quench
the coke. Use of contaminated water, however, resulted in releases of 33/50 Program
chemicals such as benzene and toluene. The facility switched to clean quench water 100%
of the time, thus eliminating the releases of benzene and toluene from the quenching
operations. The contaminated water is currently treated at the facility's waste water treatment
plant where contaminants are removed to permitted levels.
As a result of these and a variety of other projects and initiatives, U.S. Steel has surpassed its goal
of a 30% reduction in releases and transfers by 1992. The company successfully reduced its overall
releases and transfers of selected chemicals by 6,582,277 pounds, amounting to a reduction of 88%
from 1988 levels. In addition, although not an explicit part of U.S. Steel's goals, the company
reduced annual releases and transfers of other selected chemicals by almost 14 million pounds from
20,148,876 pounds for a reduction of 69% since 1988.
Overall, U.S. Steel has reduced its annual releases and transfers of all chemicals by a remarkable
20,508,069 pounds since 1988. This represents a 74% reduction in all releases and transfers.
1-23
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1-24
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VII
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INDUSTRIAL PROCESSES
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INDEX
SECTION
1 Petrochemical Industry
2 Chemical Manufacturing
3 Synthesized Pharmaceutical Manufacturing Plants
4 Metallurgical Industries
5 Tanneries
6 Cement Industries
7 Printed Circuit Board Manufacturing
8 Electroplating
9 Lead Smelting
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-------
PETROCHEMICAL INDUSTRY
The petrochemical industry is a large and complex source category that is very difficult to
define because its operations are "intertwined functionally or physically with the inorganic
sector of the chemical industry, with downstream (manufacturing), fabrication or
compounding activities, or with the petroleum refining industry. (This results in) mixing of
vertical operating steps in official statistics". Petrochemical industries are involved in the
production of several chemicals which fit into one or more of the following four categories:
1. Basic raw materials
2. Key intermediates
3. Minor intermediates
4. End products
The petrochemical industry also includes the treatment of hydrocarbon streams from the
petroleum refining industry and natural gas liquids from the oil and gas production industry.
Some of the raw materials used in the petrochemical industry include petroleum, natural
gas, ethane, hydrocarbons, naphtha, heavy fractions, kerosene, and gas-oil. Natural gas and
petroleum are the main feedstocks for the petrochemical industry. That is why about 65
percent of petrochemical facilities are located at or near refineries.
The petrochemical industry produces solvents and chemicals of various grades or
specifications which are used to produce industrial organic chemicals, including benzene, the
butylenes, cresols and cresylic acids, ethylene, naphthalene, paraffins, propylene, toluene,
and xylenes. Approximately 2500 organic chemical products are produced directly or
indirectly from basic petrochemicals. The industrial organic chemicals produced from
petrochemicals are employed in downstream industries including plastics and resins,
synthetic fibers, elastomers, plasticizers, explosives, surface active agents, dyes, surface
coatings, pharmaceuticals, and pesticides.
A. PROCESS DESCRIPTION
A process converts a raw material into products, by-products, intermediate products, or
waste streams. The main processes conducted in the basic petrochemicals industry are
separation and purification. Some chemical conversion processes such as cracking,
hydrogenation, isomerization, and disproportionation are also carried out. Six groups of
related processes, termed operations, are employed by the petrochemical industry:
1. Olefins production
2. Butadiene production
3. BTX production
4. Naphthalene production
5. Production of cresols and cresylic acids
6. Separation of normal paraffins
Each operation employs several varied process lines and procedures. The production of 1,3-
butadiene will be used as an example of the types of processes used in the petrochemical
industry.
1-1
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1,3-butadiene is a high-volume, intermediate organic chemical used commercially to produce
various types of rubber, resin, and plastics. 1,3-butadiene is involved in several different
reactions, including addition, oxidation, and substitution reactions; however, its main use is
for polymerization.
Producers of 1,3-butadiene typically generate the feedstock at the same location as the 1,3-
butadiene production. Most 1,3-butadiene is used in synthetic elastomer production, and
some is used in adiponitrile production, the raw material for nylon 6,6 production. The
overall demand of 1,3-butadiene is expected to increase due to the growth of specialty uses
for 1,3-butadiene.
1,3-butadiene is produced by one of two processes:
(1) Recovery from a mixed hydrocarbon stream, and
(2) Oxidative dehydrogenation of n-butenes.
1,3-butadiene production through recovery is by far the most common approach. In this
process, a mixed hydrocarbon stream containing butadiene, reproduced in an olefins plant
during cracking of large-molecule hydrocarbons to manufacture ethylene or other alkenes
(Exhibit 1), is routed to a recovery unit where the butadiene is separated.
In an olefins plant a steam cracking furnace is used to crack the hydrocarbon feedstock.
The heavy hydrocarbons are broken into two or more fragments, forming a stream of mixed
hydrocarbons. The concentration of butadiene in this mixed hydrocarbon stream varies with
the type of feedstock. The flue gas from the cracking furnace is vented to the atmosphere.
After the cracking step, the mixed hydrocarbon stream is cooled and, if naphtha or gas oils
were the initial feedstock, the stream is sent to a gasoline fractionator. The fractionator is
used to recover heavy hydrocarbons (C5 and higher). For some olefins units the quenching
step shown occurs after gasoline fractionation. The mixed stream is then compressed prior
to removal of acid gas (hydrogen sulfide) and carbon monoxide. Acid removal usually
involves a caustic wash step. The mixed hydrocarbon stream then goes through additional
refining steps, where it is separated from olefins (Q and lower).
The mixed C4 stream may be sent directly to butadiene recovery at the same plant. Olefins
plants that do not produce finished butadiene use the by-product mixed C4 streams in the
following ways: (1) recover the crude butadiene from the stream and sell it to a butadiene
producer, (2) recirculate the stream into the front of the ethylene process, and/or (3) use
the stream to fuel the equipment (e.g., furnaces) in the ethylene process.
The second part of this butadiene production process involves recovering the butadiene from
the mixed C4 stream. The mixed C4 stream is fed from pressurized storage tanks into a
hydrogen reactor along with hydrogen to convert some of the unsaturated hydrocarbons such
as acetylene to olefins. The product C4 stream from the hydrogenator is combined with a
1-2
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EXHIBIT 1:
Process Diagram for Production of a Mixed C(4) Stream Containing Butadiene
VENT B
FEEDSTOCK
STEAM
4
1
VENT A
|\STEAM
\ CRACKING
h\ FURNACE
i
4
1
VENT A
t
CONTROL DEVICE (S)
(IF INSTALLED)
i
4
1
VENT A
DEGASSING
VENT A
4
1
FUEL
HYDROCARBONS
QUENCHING
S
1
r
fc.
w
GASOLINE
FRACTIONATION
\
r
VENT A
OLEFINS
TO RECOVERY
COMPRESSORS
1
OLEFINS
TO RECOVERY
4
STREAM TO BUTADIENE
RECOVERY PROCESS
Denotes potential location of emission source
A - Denotes process vent
B - Represents emissions after a control device
-------
solvent (typically furfural) and fed into an extractive distillation operation. In this operation,
most of the butanes and butenes are separated from butadiene, which is absorbed in the
solvent along with residual impurities. A stripping operation is then used to separate the
butadiene from the solvent.
The stream containing butadiene typically has a small amount of residuals. Some of these
residuals are alkynes that were not converted to olefins in the hydrogenation reactor. These
residuals are removed from the butadiene stream by distillation and are usually vented to
an emission control device. The bottom stream exiting the acetylenes removal operation
contains butadiene and residuals such as polymer and 2-butene. The residuals are removed
in the butadiene finishing operation and sent to a waste treatment system or recovery unit.
The finished butadiene is then stored in pressurized tanks.
In the dehydrogenation process, steam and air are combined with n-butenes and preheated,
then passed through a dehydrogenation reactor. Hydrogen is removed from the butenes
feed stream. Next, the stream is compressed and sent to a hydrocarbon absorption and
stripping process. The product is then routed to a light-ends column for further separation.
Finally, distillation and separation take place, with the finished butadiene sent to storage.
B. SOURCES OF POLLUTION
There are five main sources of pollutant emissions in the production of 1,3-butadiene:
process vent discharges,
equipment leaks,
secondary sources,
storage, and
emergency or accidental releases.
Process vent discharges can be from reactor vessels, recovery columns, and other process
vessels. Equipment leaks include pump seals, process valves, compressors, safety relief
valves, flanges, open-ended lines, and sampling connections. Secondary sources include
process and other waste streams. Emissions from storage vessels are assumed negligible
since 1,3-butadiene is stored in pressure vessels with no breathing or working losses. There
are no data available regarding emission amounts from emergency or accidental releases.
C. POLLUTANTS AND THEIR CONTROL
Exhibits 2 and 3 identify air pollutants and hazardous waste pollutants, respectively. Little
information is available regarding amounts of pollutant emissions from the entire
petrochemical industry, including 1,3-butadiene production. Many petrochemical processes
are located at or near petroleum refining operations; therefore, many of the air pollutants
and hazardous wastes generated by the petroleum industry are also present at petrochemical
facilities. It is important to note that the Exhibits represent facility-wide pollution.
1-4
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In general, the waste streams from the petrochemical industry are quite similar to those of
the petroleum refining industry. Limited data are available, but almost all assume waste
management operations and facilities are probably of the same degree of sophistication as
those of the petroleum refining industry.
Wastewater, which is a basic source of emissions, can be categorized in five ways:
(1) Wastes containing a principal raw material or product;
(2) By-products produced during reactions;
(3) Spills, leaks, washdowns, vessel cleanouts, or point overflows;
(4) Cooling tower and boiler blowdown, steam condensate, water treatment
wastes, and general washing water; and
(5) Surface runoff.
Disposal of solid wastes is a significant problem for the petrochemical industry. Waste
solids include water treatment sludges, ashes, fly ash and incinerator residue, plastics, ferrous
and nonferrous metals, catalysts, organic chemicals, inorganic chemicals, filter cakes, and
viscous solids. General methods of disposal are depicted in Exhibit 3.
Exhibit 2: Pollutant Profile of the Petrochemical Industry
Pollutants
Participates
VOC
Hydrocarbons
SOX
NO,
CO
Chemicals used or produced (benzene,
1,3-butadiene, naphthalene)
Control Device
(For gases)
Gas recovery (boiler)
- Flare
- Incinerator
Control
Efficiency (%)
99.9
98
98
r,-- 7-
1-5
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Exhibit 3: Hazardous Waste Generation From the Petrochemical Industry
Pollutant
Amount
Disposal Method
Hazardous solids
Hydrocarbons
Any hazardous chemicals used or
produced
Not available
Not available
Not available
Land disposal
Incineration
Salvage & recycle
Chemical & biological
treatment
D. REFERENCES
1. Federal Energy Administration (Office of Economic Impact). Report to Congress
on Petrochemicals. Public Law 93-275, Section 23 (no date: circa 1974).
2. Industrial Process Profiles for Environmental Use. Chapter 5 - Basic
Petrochemical Industry. EPA document 600/2-77-023, January, .1977.
3. Locating and Estimating Air Emissions from Sources of 1.3-Butadiene. EPA
document 450/2-89-021, December, 1989.
1-6
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CHEMICAL MANUFACTURING
A. PROCESS DESCRIPTION
Due to the broad expanse and complexity of the chemical manufacturing industry,
acrylonitrile manufacturing has been selected as being representative of it; however, process
procedures may vary somewhat between different chemical industries.
Nearly all of the acrylonitrile (ACN) produced in the world today is produced using the
SOHIO process for ammoxidation of propylene and ammonia. The overall reaction takes
place in the vapor phase in the presence of a catalyst. Exhibit 1 shows a typical simplified
process flow diagram for an uncontrolled SOHIO process.
The primary by-products of the process are hydrogen cyanide, acetonitrile, and carbon
oxides. The recovery of these by-products depends on such factors as market conditions,
plant location, and energy costs. Hydrogen cyanide and acetonitrile, although they carry a
market value, are usually incinerated, indicating that the production of these by-products has
little effect on the economics of producing ACN.
In the process represented in Exhibit 1, by-product hydrogen cyanide and acetonitrile are
routed to an incinerator. Variations within the SOHIO process may provide for purification,
storage, and loading facilities for these recoverable by-products. Other variations of the
SOHIO process include the recovery of ammonium sulfate from the reactor effluent to allow
for biological treatment of a wastewater stream and variations in catalysts and reactor
conditions.
In the standard SOHIO process, air, ammonia, and propylene are introduced into a fluid-
bed catalytic reactor operating at 5-30 psig and -400-510°C (750-950°F). Ammonia and air
are fed to the reactor in slight excess of stoichiometric proportions because excess ammonia
drives the reaction closer to completion and air continually regenerates the catalyst. A
significant feature of the process is the high conversion of reactants on a once-through basis
with only a few seconds residence time. The heat generated from the exothermic reaction
is recovered via a waste-heat-recovery boiler.
The reactor effluent is routed to a water quench tower, where sulfuric acid is introduced to
neutralize any unconverted ammonia. The product stream then flows through a
countercurrent water absorber-stripper to reject inert gases and recover reaction products.
The operation yields a mixture of ACN, acetonitrile, and water and then is sent to a
fractionator to remove hydrogen cyanide. The final two steps involve the drying of the ACN
stream and the final distillation to remove heavy ends. The fiber-grade ACN obtained from
the process is 99+% pure.
Several fluid-bed catalysts have been used since the inception of the SOHIO ammoxidation
process. Catalyst 49, which represents the fourth major level of improvement, is currently
recommended in the process.
2-1
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Emissions of ACN during start-up are substantially higher than during normal operation.
During start-up, the reactor is heated to operating temperature before the reactants
(propylene and ammonia) are introduced. Effluent from the reactor during start-up begins
as oxygen-rich, then passes through the explosive range before reaching the fuel-rich zone
that is maintained during normal plant operation. To prevent explosions in the line to the
absorber, the reactor effluent is vented to the atmosphere until the fuel-rich effluent mixture
can be achieved. The ACN emissions resulting from this start-up procedure have been
estimated to exceed 4500 kg (10,000 lb)/h.
The absorber vent gas contains nitrogen and unconverted oxygen from the air fed to the
reactor, propane and unconverted propylene from the propylene feed, product ACN, by-
product hydrogen cyanide and acetonitrile, other organics not recovered from the absorber,
and some water vapor.
The ACN content of the combined column purge vent gases is relatively high, about 50%
of the total VOCs emitted from the recovery, acetonitrile, light ends, and product columns.
The rest of the vent gases consist of noncondensibles that are dissolved in the feed to the
columns, the VOCs that are not condensed, and, for the columns operating under vacuum,
the air that leaks into the column and is removed by the vacuum jet systems.
For the ACN process illustrated in Exhibit 1, by-product hydrogen cyanide and acetonitrile
are incinerated along with product column bottoms. The primary pollutant problem related
to the incinerator stack is the formation of NOX from the fuel nitrogen of the acetonitrile
stream and hydrogen cyanide. Carbon dioxide and lesser amounts of CO are emitted from
the incinerator stack gas.
Other emission sources involve the volatilization of hydrocarbons through process leaks
(fugitive emissions) and from the deep well ponds, breathing and working losses from
product storage tanks, and losses during product loading operations. The fugitive and deep
well/pond emissions consist primarily of propane and propylene, while the storage tank and
product loading emissions consist primarily of ACN.
B. SOURCES OF POLLUTION
Exhibit 2 presents an emissions profile for sources in an ACN manufacturing facility, along
with pollution control options and their efficiencies. Seven points are included:
1. Absorber vent gas
2. Column purge waste gas
3. Fugitive emissions
4. Incinerator stack gas
5. Deep well/pond emissions
6. Storage tank emissions
7. Product transport loading facility vent
Wastewater for disposal is generated mainly from the wastewater and acetonitrile columns.
2-2
-------
EXHIBIT 1:
Sources of Pollution at a Typical ACN Plant
AIR
AMMONIA
U)
PROPYLENE
WASTEWATER
COLUMN
ACETONITRILE
COLUMN
DEEP HELL
POND
INCINERATOR
ACN LOADING
Air Emissions
Solid / Liquid Waste
-------
Exhibit 2: VOC and Acrylonitrile Emissions From ACN Manufacturing3
Emission Point
Absorber Vents
Column Vents
Storage Tanks
Loading"
Fugitive
Incinerator Stack
Deep Well/Pond
Emission Rate (kg/hr)
Acrylonitrile
2.05
103
13.5
3.44
9.5
Total VOC
2050
205
14.8
3.98
19.5
7.4
267
Control Method
Thermal Incineration
Catalytic Oxidation
Flare
Double Seal Floating Roof
Water Scrubber
Flare
Incinerator
Leak Detection/Maintenance
N/A
Water Scrubber
Control
Efficiency
(%)
99.9
95-97
98-99
N/A
99
98-99
99
N/A
N/A
N/A
Model plant has an annual ACN capacity of 180 million kg, and is assumed to operate 8760 hours annually
Loading into lank cars, does not include loading into barges
C. POLLUTANTS AND THEIR CONTROL
1.
Air Pollution
Absorber Vent Gas. The absorber vent gas stream contains nitrogen, oxygen, unreacted
propylene, hydrocarbon impurities from the propylene feed stream, CO, CO2, water vapor,
and small quantities of ACN, acetonitrile, and Hydrogen cyanide. Two control methods are
used to treat this stream: thermal incineration and catalytic oxidation.
The thermal incineration units have demonstrated VOC destruction efficiencies of 99.9%
or greater, while most catalytic units can achieve destruction efficiencies only in the 95-97%
range. Destruction efficiencies in the 99% and greater range can be achieved with catalytic
oxidizers, but these are not achieved on a long-term basis because of deactivation of the
catalyst by a number of causes. The advantage of catalytic oxidation is low fuel usage, but
emissions of NOX formed in the reactors and not destroyed across the catalyst can pose
problems.
2-4
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Column Waste Purge Gas. Waste gas releases from the recovery column, light-ends column,
product column, and the acetonitrile column are frequently tied together and vented to a
flare. The estimated VOC destruction efficiency of the flare is 98-99% for all streams with
a heat content of 300 Btu/scf or greater. The use of a flare is ideally suited for streams that
are intermittent and having heating values of 300 Btu/scf.
Fugitive emissions. Fugitive emissions from piping, valves, pumps, and compressors are
controlled by periodic monitoring by leak checking with a VOC detector and a directed
maintenance program.
Incinerator Stack Gas. Staged combustion and ammonia injection are used to control the
emissions of NOX from the incinerator that treats the absorber off-gas vent, the crude
acetonitrile waste gas stream, and the by-product liquid HCN stream. Staged combustion
suppresses the formation of NO, by operating under fuel-rich conditions in the flame zone
where most of the NOX is formed and oxygen-rich conditions downstream at lower
temperatures where NOX is not appreciably formed.
Ammonia injection reduces NO, by selectively reacting ammonia with NOX. The reaction
occurs at temperatures in the range of 870-980°C (1600-1800°F) and, as such, the ammonia
must be injected in the postflame zone of the combustion chamber. Residence times of 0.5-
1.0 second are required for NO, destruction efficiencies in the range of 80%, which is
compatible with the residence time required for VOC destruction.
Deep Wett/Pond Emissions. Emissions of acrolein and other odorous components in vents
from wastewater treatment steps are controlled with water scrubbers. In some cases, pond
emissions are controlled by adding a layer of a low-vapor-pressure oil on the surface of the
pond to limit volatilization.
Storage Tank Emissions. Product storage tank emissions are controlled with double-seal
floating roofs or, in some cases, water scrubbers. Field experience indicates that a removal
efficiency of 99% can be achieved with water scrubbing.
Product Transport Loading. Emissions from product transport loading vents are gathered
and sent to a flare or incinerator for VOC control. Destruction efficiencies of 98-99% are
achieved using the flare and greater than 99% using incineration.
2. Solid/Liquid Waste
Wastes include salts of hydrogen cyanide, metal cyanide complexes, and organic cyanides
(cyanohydrins) as solutions or solids. The wastewater from the wastewater column contains
ammonium sulfate and heavy hydrocarbons, while the wastewater from the acetonitrile
column mainly contains heavy bottoms. The wastewater from both these columns is typically
discharged to a deep well pond (Exhibit 3). Other methods of waste treatment include
alkaline chlorination in a recycle lagoon system, and incineration.
2-5
-------
Exhibit 3: Potentially Hazardous Wastes Generated From Acrylonitrile Production
Waste Source
Wastewater Column
Acetonitrile Column
Pollutant
Ammonium Sulfate
Heavy Hydrocarbons
Heavy Bottoms
Amount
N/A
N/A
Disposal Method
Deep well pond
Deep well pond
D. REFERENCES
1. Wilkinsin, Gary R. The Manufacture and Use of Selected Inorganic Cyanides.
Kansas City: Midwest Research Institute (for the U.S.EPA), April 2, 1976.
2. Air and Waste Management Association. Air Pollution Engineering Manual. New
York: Van Nostrand Reinhold, 1992.
2-6
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SYNTHESIZED PHARMACEUTICAL MANUFACTURING PLANTS
A. PROCESS DESCRIPTION
The synthesis of medicinal chemicals may be done in a very small facility producing only one
chemical or in a large integrated facility producing many chemicals by various processes.
Most pharmaceutical manufacturing plants are relatively small. Organic chemicals are used
as raw materials and as solvents. Nearly all products are made using batch operations. In
addition, several different products or intermediates are likely to be made in the same
equipment at different times during the year; these products, then, are made in
"campaigned" equipment. Equipment dedicated to the manufacture of a single product is
rare, unless the product is made in large volume.
Production activities of the pharmaceutical industry can be divided into the following
categories:
1. Chemical Synthesis - the manufacture of pharmaceutical products by chemical
synthesis.
2. Fermentation - the production and separation of medicinal chemicals such as
antibiotics and vitamins from microorganisms.
3. Extraction - the manufacture of botanical and biological products by the
extraction of organic chemicals from vegetative materials or animal tissues.
4. Formulation and Packaging - the formulation of bulk Pharmaceuticals into
various dosage forms such as tablets, capsules, injectable solutions, ointments,
etc., that can be taken by the patient immediately and in accurate amount.
Production of a synthesized drug consists of one or more chemical reactions followed by a
series of purifying operations. Production lines may contain reactors, filters, centrifuges,
stills, dryers, process tanks, and crystallizers piped together in a specific arrangement.
Arrangements can be varied in some instances to accommodate production of several
compounds. A very small plant may have only a few pieces of process equipment but a
large plant can contain literally hundreds of pieces.
Exhibit 1 shows a typical flow diagram for a batch synthesis operation. To begin a
production cycle, the reactor may be water washed and perhaps dried with a solvent. Air
or nitrogen is usually used to purge the tank after it is cleaned. Following cleaning, solid
reactants and solvent are charged to the glass batch reactor equipped with a condenser
(which is usually water-cooled). Other volatile compounds may be produced as product or
by-products. Any remaining unreacted volatile compounds are distilled off. After the
reaction and solvent removal are complete, the pharmaceutical product is transferred to a
holding tank. After each batch is placed in the holding tank, three to four washes of water
or solvent may be used to remove any remaining reactants and by-products. The solvent
used to wash may also be evaporated from the reaction product. The crude product may
then be dissolved in another solvent and transferred to a crystal! izer for purification. After
3-1
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EXHIBIT 1: Typical Synthetic Organic Medicinal Chemical Process
Vent
A
Vent
A
Solids
Solvent
OJ
Vent
A
Reactor
Holding
tank
Solvent
Solvent
Distillation
Crystal izer
Air emissions
Liquid waste
Water solvent
Vent
A
Batch
centrifuge
Water or solvent
Vent
A
Dryer
Product
Typical Cycle = 24 Hours
-------
crystallization, the solid material is separated from the remaining solvent by centrifugation.
While in the centrifuge the product cake may be washed several times with water or solvent.
Tray, rotary, or fluid-bed dryers may then be employed for final product finishing.
B. SOURCES OF POLLUTION
Exhibit 2 identifies pollutants from a typical pharmaceutical process. Volatile organic
compounds may be emitted from a variety of sources within plants synthesizing
pharmaceutical products. The following process components have been identified as VOC
sources and will be discussed further: reactors, distillation units, dryers, crystallizers, filters,
centrifuges, extractors, and tanks.
1. Reactors
The typical batch reactor is glass lined or stainless steel and has a capacity of 2,000 to
11,000 liters (500-3000 gallons). For maximum utility the tanks are usually jacketed to
permit temperature control of reactions. Generally, each tank is equipped with a vent which
may discharge through a condenser. Batch reactors can be operated at atmospheric
pressure, elevated pressure, or under vacuum, and may be used in a variety of ways. Besides
hosting chemical reactions, they can act as mixers, heaters, holding tanks, crystallizers, and
evaporators.
A typical reaction cycle takes place as follows. After the reactor is clean and dry, the
appropriate raw materials, usually including some solvent(s), are charged for the next
product run. Liquids are normally added first, then solid reactants are charged through the
manhole. After charging is complete, the vessel is closed and the temperature raised, if
necessary, via reactor jacket heating. The purpose of heating may be to increase the speed
of reaction or to reflux the contents for a period which may vary from 15 minutes to 24
hours. During refluxing, the liquid phase may be "blanketed" by an inert gas, such as
nitrogen, to prevent oxidation or other undesirable side reactions. Upon completion of the
reaction, the vessel may be used as a distillation pot to vaporize the liquid phase (solvent),
or the reaction products may be pumped out so the vessel can be cooled to begin the next
cycle.
2. Distillation Operations
Distillation may be performed by either of two principal methods. In the first method, the
liquid mixture to be separated is boiled and vapors produced are condensed and prevented
from returning to the still. In the second method, part of the condensate is allowed to
return to the still so that the returning liquid is brought into intimate contact with the vapors
on the way to the condenser. Either of these methods may be conducted as a batch or
continuous operation.
3-3
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Exhibit 2: Major Pollutants From Solvent Use in Pharmaceutical Production3
Pollutant
(Solvent)
Acetic anhydride
Acetone
Amyl alcohol
Benzene
Carbon tetrachloride
Dimethyl formamide
Ethanol
Ethyl acetate
Isopropanol
Methanol
Methylene chloride
Solvent B (hexanes)
Toluene
Xylene
Ultimate Disposition (%)
Air
Emissions
1
14
42
29
11
71
10
30
14
31
53
29
31
6
Sewer
57
22
58
37
7
3
6
47
17
45
5
2
14
19
Incineration
38
16
82
20
7
20
17
14
20
69
26
70
Solid
Waste
7
8
6
1
3
7
6
22
29
5
Product
42
19
10
76
45
4
Numbers are based on a survey of 26 U.S. manufacturers
3-4
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3. Separation Operations
Several separation mechanisms employed by the industry are extraction, centrifugation,
filtration, and crystallization.
Extraction is used to separate components of liquid mixtures or solutions. This process
utilizes differences in solubilities of the components rather than differences in volatilities (as
in distillation); i.e., solvent is used that will preferentially combine with one of the
components. The resulting mixture to be separated is made up of the extract which contains
the preferentially dissolved material and the raffinate which is the residual phase.
Centrifuges are used to remove intermediate or product solids from a liquid stream. Center-
slung, stainless steel basket centrifuges are most commonly used in the industry. To begin
the process, the centrifuge is started and the liquid slurry is pumped into it. An inert gas,
such as nitrogen, is sometimes introduced into the centrifuge to avoid the buildup of an
explosive atmosphere. The spinning centrifuge strains the liquid through small basket
perforations. Solids retained in the basket are then scraped from the sides of the basket and
unloaded by scooping them out from a hatch on the top of the centrifuge or by dropping
them through the centrifuge bottom into receiving carts.
Filtration is used to remove solids from a liquid; these solids may be product, process
intermediates, catalysts, or carbon particles (e.g., from a decoloring step). Pressure filters,
such as shell and leaf filters, cartridge filters, and plate and frame filters are usually used.
Atmospheric and vacuum filters have their applications too. The normal filtration
procedure is simply to force or draw the mother liquor through a filtering medium.
Following filtration, the retained solids are removed from the filter medium for further
processing.
Crystallization is a means of separating an intermediate or final product from a liquid
solution. This is done by creating a supersaturated solution, one in which the desired
compound will form crystals. If performed properly and in the absence of competing
crystals, crystallization can produce a highly purified product.
4. Dryers
Dryers are used to remove most of the remaining solvent in a centrifuged or filtered
product. This is done by evaporating solvent until an acceptable level of "dryness" is
reached. Evaporation is accelerated by applying heat and/or vacuum to the solvent-laden
product or by blowing warm air around or through it. Because a product may degrade
under severe drying conditions, the amount of heat, vacuum, or warm air flow is carefully
controlled. Several types of dryers are used in synthetic drug manufacture. Some of the
most widely used are tray dryers, rotary dryers, and fluid bed dryers.
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5. Storage and Transfer
Volatile organic compounds are stored in tank farms, 233 liter (55 gallon) drums, and
sometimes in process holding tanks. Storage tanks in tank farms range in size from about
2,000-20,000 liters (500-5,000 gallons). In-plant transfer of VOCs is done mainly by pipeline,
but also may be done manually (e.g. loading or unloading drums). Raw materials are
delivered to the plant by tank truck, rail car, or in drums.
C. POLLUTANTS AND THEIR CONTROL
1. Air Emissions
Solvents constitute the predominant VOC emission from production. Plants differ in the
amount of organics used; this results in widely varying VOC emission rates. Therefore,
some plants may be negligible VOC sources while others are highly significant. In addition,
all types of equipment previously described have the potential to emit air pollutants.
a. Reactors
Reactor emissions stem from the following causes: (a) displacement of air containing VOC
during reactor charging, (b) solvent evaporation during the reaction cycle (often VOCs are
emitted along with reaction by-product gases which act as carriers), (c) overhead condenser
venting uncondensed VOC during refluxing, (d) purging vaporized VOC remaining from a
solvent wash, and (e) opening reactors during a reaction cycle to take samples, determine
reaction end-points, etc.
Equipment options available to control emissions from reactors include surface condensers,
carbon adsorbers, liquid scrubbers, and vapor incinerators (under certain conditions).
Condensers are often included on reactor systems as normal process control equipment.
b. Distillation Operations
Volatile organic compounds may be emitted from the distillation condensers used to recover
evaporated solvents. The magnitude of emissions depends on the operating parameters of
the condenser, the type and quantity of organic being condensed, and the quantity of inerts
entrained in the organic.
Emissions from distillation condensers can be controlled through the use of aftercondensers,
scrubbers, and carbon adsorbers.
c. Separation Operations
I. Emissions from batch extraction stem mainly from displacement of vapor while
pumping solvent into the extractor and while purging or cleaning the vessel after
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extraction. Some VOCs also may be emitted while the liquids are being agitated.
A column extractor may emit VOCs while the column is being filled, during
extraction, or when it is emptied after extraction. Emissions occur not only at the
extractor itself, but also at associated surge tanks. These tanks may emit significant
amounts of solvent due to working losses as the tank is repeatedly filled and emptied
during the extraction process.
2. A large potential source of emissions is the open-type centrifuge which permits large
quantities of air to contact and evaporate solvents. The industry trend is toward
completely enclosed centrifuges and, in fact, many plants have no open-type
centrifuges. If an inert gas blanket is used, it can act as a transport vehicle for
solvent vapor. This vapor may be vented directly from the centrifuge or from a
process tank receiving the mother liquor. However, this emission source is likely to
be small because the inert gas flow is only a few cubic feet per minute.
3. If crystallization is done mainly through cooling of a solution, there will be little
VOC emission. In fact, the equipment may be completely enclosed. However, when
the crystallization is done by solvent evaporation, there is greater potential for
emissions. Emissions will be significant if evaporated solvent is vented directly to the
atmosphere. It is more likely, however, that the solvent will be passed through a
condenser or from a vacuum jet (if the crystallization is done under vacuum), thereby
minimizing emissions.
Several add-on control technologies may be used on the separation equipment
described above. Condensers, which can be applied to individual systems, are
effective and may be the least costly option. Water scrubbers also have found wide
usage in the industry. They are versatile and capable of handling a variety of VOCs
which have appreciable water solubility. Scrubbers can be either small or quite large;
thus, they can be designed to handle emissions from a single source or from many
sources (via a manifold system). Carbon adsorbers can be and have been employed
on vents from separation operations. Several vents may be ducted to an adsorber
because it is likely that emissions from a single source would not warrant the expense
of a carbon adsorption unit. Finally, in some instances, incinerators may be
applicable. They may not be a good choice, however, since the expected variability
from these emission sources might make continuous incinerator operation difficult.
4. Enclosed pressure filters normally do not emit VOCs during a filtering operation.
Emissions can occur, however, when a filter is opened to remove collected solids.
Emissions can also occur if the filter is purged (possibly with nitrogen or steam)
before cleaning. The purge gas will entrain evaporated solvent and probably be
vented through the receiving tank for the filtered liquid. The largest VOC emissions
are from vacuum drum filters which are operated by pulling solvent through a
precoated filter drum. Potential emissions are significant both at or near the surface
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of the drum and from the ensuing waste stream. These filters can be shrouded or
enclosed for control purposes.
d. Dryers
Dryers are potentially large emission sources. Emission rates vary during a drying cycle and
are greatest at the beginning of the cycle and least at the end of the cycle. Drying cycle
times can range from several hours to several days. Control options used for dryers include
condensation, wet scrubbing, adsorption, and incineration.
1. Condensers are often the first control devices selected when dealing with air
pollution from vacuum dryers. They can also be used by themselves or in series with
another device. Condensers are not typically used on air dryers because the
emissions are dilute.
2. Wet scrubbers have also been used to control many plant sources, including dryers.
They can also remove particulates generated during drying. For water soluble
compounds, VOC absorption efficiencies can be quite high (i.e. 98-99%).
3. Carbon adsorbers may also be used, especially following a condenser. Not only will
overall efficiency increase but a longer regeneration cycle can be used in the
adsorber.
4. Vapor incinerators might be viable controls although varying VOC flows to the
incinerator may present operating problems.
e. Tanks
The vapor space in a tank will in time become saturated with the stored organics. During
tank filling vapors are displaced, causing an emission or a "working loss." Some vapors are
also displaced as the temperature of the stored VOC rises, such as from solar radiation, or
as atmospheric pressure drops; these are "breathing losses." The amount of loss depends
on type of VOC stored, size of tank, type of tank, diurnal temperature changes, and tank
throughput.
Emissions from storage or process holding vessels may be reduced with varying efficacy
through the use of vapor balance systems, conservation vents, vent condensers, pressurized
tanks, and carbon adsorption.
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2. Solid and Liquid Wastes
The manufacture of the following types of pharmaceutical products can generate hazardous
wastes:
Organic medicinal chemicals
Inorganic medicinal chemicals
Antibiotics
Botanicals
Medicinals from animal glands.
The largest quantities of hazardous waste are from the production of organic medicinal
chemicals and antibiotics. Exhibit 3 identifies potential hazardous wastes from
pharmaceutical production:
Exhibit 3: Potential Hazardous Wastes from Pharmaceutical Production
Product or Operation
Organic medicinal chemicals
Inorganic medicinal chemicals
Antibiotics
Botanicals
Medicinals from animal glands
Biological products
Misc. sources
Potential Hazardous Wastes
Heavy metals
Terpenes, steroids, vitamins,
tranquilizers
Ethylene dichloride
Acetone, toluene, xylene,
benzene isopropyl alcohol,
methanol, acetonitrile
Zinc, arsenic, chromium,
copper, mercury
Selenium
Amyl acetate, butanol, butyl
acetate, MIK, acetone,
ethylene glycol, monomethyl
ether
Ethylene dichloride,
methylene chloride
Methanol, acetone, ethanol,
chloroform, heptane, naphtha,
benzene
Misc. organics
Misc. organics
Vaccines, toxoids, serum, etc.
Ethanol
Misc. solvents
Estimated U.S.
Generation (dry
metric tons/yr)1
i;7oo
13,600
3,400
23,800
2,700
200
12,000
100
100
700
800
500
300
63,900
'Hazardous waste amounts are for 1973 estimated total U.S. generation.
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D. REFERENCES
1. Control of Organic Emissions from the Manufacture of Synthesized
Pharmaceutical Products. Environmental Protection Agency, Research Triangle
Park, NC, December 1978.
2. The Handbook of Hazardous Waste Management. Metry, Amir A., Ph.D., P.E.,
Technomic Publication, January, 1980.
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METALLURGICAL INDUSTRIES
The metallurgical industries can be broadly divided into primary, secondary, and
miscellaneous metal production operations. "Primary metals" refers to the production of
metals from ore. "Secondary metals" refers to the manufacturing of alloys by utilizing metals
from scrap and salvage, as well as ingots. "Miscellaneous metal" production encompasses
industries with operations that produce or use metals for final products. Metallurgical
industries include the following:
Primary Aluminum Secondary Aluminum
Metallurgical Coke Secondary Brass and Bronze
Copper Smelting Melting Processes
Ferroalloy Industry Iron Foundries
Steel Industry Secondary Lead Smelting
Primary Lead Smelting Steel Foundries
Zinc Smelting Secondary Zinc
As a representative industry within the metallurgical classification, iron foundries have been
selected for discussion.
Method to control air pollution produced by iron foundries are selected based on the
methods of melting, the handling of sand, the types of molten metals and other materials,
and the cleaning of finished castings. Air pollutant characteristics are affected by a number
of factors, including the type of melting unit, material-handling and hooding systems, and
emission control systems. Air pollution is prevented by capturing the smoke, dust, and
fumes at the furnace and other sources, and transporting these contaminants to suitable
control devices.
A. PROCESS DESCRIPTION
1. Mold and Core Production
Molds are forms used to shape the exteriors of castings. The green sand mold, the most
common type, consists of moist sand mixed with 3-20% clay and 2-5% water, depending on
the process. To prevent casting defects materials such as seacoal (a pulverized high-
volatility, low-sulfur bituminous coal), wood or corn flour, oat hulls, or similar organic
matter may be added to the sand mixture. Cores are molded sand shapes used to form the
internal voids in castings. They are made by mixing sand with various binders, shaping it
into a core, and curing the core with a variety of processes.
2. The Melting Process
a. Electric Furnace (General)
In the electric furnace, the basic process operations are (1) furnace charging, in which metal,
scrap, alloys, carbon, and flux are added to the furnace; (2) melting, during which the
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furnace remains closed; (3) back-charging, which involves the addition of more metal and
alloys; (4) refining and treating, during which the chemical composition is adjusted to meet
product specifications; (5) slag removal; and (6) tapping molten metal into a ladle or directly
into molds.
b. Induction Furnaces
Electric induction furnaces are either horizontal or vertical, cylindrical, refractory-lined
vessels. Heating and melting occur when the charge is energized with a low-, medium-, or
high-frequency alternating current. Induction furnaces also may be used for holding and
superheating. Electric induction furnaces generally have lower emissions per ton of metal
melted than the other furnace types. As a result, in spite of a generally lower unit capacity,
induction furnaces have supplanted cupolas in many foundries.
c. Electric Arc Furnaces
Electric-arc melting furnaces are large, welded-steel cylindrical vessels equipped with a
removable roof through which three carbon electrodes are inserted. The electrodes are
energized by three-phase alternating current, creating arcs that melt the metallic charge
material. Additional heat is generated by the electrical resistance of the metal to the
current between the arc paths. The most common method of charging an arc furnace is by
removing the roof and introducing the charge material directly. Alternatives include
charging through a roof chute or side charging door. Once the melting cycle is complete,
the metal is tapped by tilting the furnace and pouring the metal into a ladle.
d. Cupola
The cupola is a vertical, cylindrical shaft furnace which may use pig iron, scrap iron, scrap
steel, and coke as the charge components. 'Melting is accomplished in the cupola by heat
released from the combustion of coke (the reaction between oxygen in the air and carbon
in the fuel) that is in direct contact with the metallic portion of the charge and the fluxes.
One of the advantages of using such a furnace is that counterflow preheating of the charge
material can occur. In a cupola, upward flowing hot gases come into close contact with the
descending burden, allowing direct and efficient heat exchange to take place. The running
or charge coke, which replenishes fuel consumed, is also preheated before it reaches the
combustion zone, thus enhancing the combustion process. Greater understanding of these
features accounts, in part, for the continued popularity of the cupola as a melting unit.
However, recent design improvements, such as cokeless, plasma-fired types that alter
emission characteristics are now encountered.
3. Casting, Cooling, and Finishing
After melting, molten metal is tapped from the furnace and poured into a ladle or directly
into molds. If poured into a ladle, the molten iron may be treated with a variety of alloying
agents selected for their desired metallurgical properties. The molten material then is
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ladled into molds which are allowed to cool in open floor space, or, (in larger, more
mechanized foundries) are conveyed automatically through a cooling tunnel before
separation of the casting from the mold (shakeout). Molding and core sand are separated
from the casting(s) either manually or mechanically. In some foundries the cooled molds
are placed on a vibrating grid to shake the mold and core sand loose from the casting.
Used sand from casting shakeout is usually returned to the sand preparation area and
cleaned, screened, and processed to make new molds. Because of process losses and
potential contamination, additional makeup sand may be required.
When castings have cooled, any unwanted appendages such as sprues, gates, and risers are
removed by an oxygen torch, abrasive saw, friction cutting tool, or hand hammer. The
castings then may be subjected to abrasive blast cleaning and/or tumbling to remove any
remaining mold sand or scale.
B. SOURCES OF POLLUTION
Exhibit 1 illustrates the operations of a typical iron foundry and emissions they generate.
Processes which produce air emissions include melting (furnace or cupola), molding, core-
making, pouring, casting shakeout, cooling/cleaning, and finishing. These are described in
greater detail in the next section.
C. POLLUTANTS AND THEIR CONTROL
Exhibit 2 summarizes the pollutant emissions from the various processes in a typical iron
foundry, and indicates appropriate types of control methods. The nature of emissions from
each source is described in this section.
1. Emission Sources
a. Mold and Core Production
The major pollutants emitted in mold and core production operations are particulates from
sand preparation, mold core forming, and curing. Volatile organic compounds (VOCs),
carbon monoxide, and particulates also may be emitted during core and mold curing or
drying.
b. Melting
The melting process begins with the handling of charge materials going into the melting
furnace. Emissions from raw material handling are fugitive particulates generated from the
receiving, unloading, storage, and conveying operations. Scrap preparation and preheating
may emit one or more of the following: fumes, organic compounds, carbon monoxide, or
coarse particulates. Scrap preparation with solvent degreasers may emit VOCs.
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EXHIBIT 1: Emission Points in a Typical Iron Foundry
FLUXES METAJ
T ^
^
/ FURN;
1 CUP
A
: i
Jl i Air Emissions
COKE |
! Solid / Liquid Haste
r ir
A
i
r !
VCE / \
OLA )
A A
i i
r ' '
pivcTTNn
MOLDING fc DOiipTNn fe, "*=>iinu
""""*"*' . ^ W --WWM.I^W ^ SHAKKOUT
A
CORE
MAKING
A A
i i
v : : ~^s
COOLING AND PTHTRHTiin FINISHED
CLEANING ~ ir.nn«i PRODUCT
-------
Exhibit 2: Emissions From Iron Foundry Processes
Emission Point
Pollutants
Control Methods
Mold and Core Production
Melting
Induction and Arc Melting
Cupola Melting
Pouring, Casting, Cooling and
Finishing
particulates
VOCs
carbon monoxide
fugitive particulates
fumes
organic compounds
carbon monoxide
VOCs
particulates (metal
oxides)
organics
dust consisting of:
iron oxide
silicon dioxide
zinc oxide
magnesium oxide
manganese oxide
calcium oxide
lead
cadmium
gases:
carbon monoxide
sulfur oxides
lead
organic emissions
particulates
magnesium oxides'
metallic fumes
carbon monoxide
organic compounds
VOCs
Wet Scrubbers
Fabric Dust
Collectors/Baghouses
Afterburners
Charcoal Absorption
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c. Induction and Arc Melting
The highest concentrations of furnace emissions occur during charging, back-charging,
alloying, slag removal, and tapping operations. These emissions are primarily particulates
(metal oxides) and possibly organics, depending on the scrap quality and pretreatment.
Typical dust loading from electric arc furnaces can range from 10 - 15 Ib/ton melted.
Electric induction furnaces, however, may emit particulates at one tenth of that value.
d. Cupola Melting
The quantity and composition of paniculate emissions vary among cupolas, and even at
intervals in the same cupola. Causes include changes in iron-to-coke ratios, air volumes per
ton melted, stack velocity, and the quality of the scrap melted. Where oily scrap is charged,
the raw emissions potentially will be greater in quantity and much more visible. Based on
a survey, the average emission from an uncontrolled cupola was approximately 13 - 17
pounds of paniculate per ton melted. Eighty-five percent of such emissions may be greater
than 10 Mm in size.
Dust amount and composition vary from cupola to cupola. Each cupola has varying airflows
at different phases in the melt process which affect the grains per standard cubic foot in
emitted stack gases if all other factors are equal. The source of the raw charge materials
also has a significant impact on dust composition and quantity. The dust can include some
or all of the following materials:
Iron oxide Silicon dioxide . Zinc oxide
Magnesium oxide Calcium oxide Cadmium
Manganese oxide Lead
In addition, other gases and organic compounds may be emitted as part of the melting
process. These include carbon monoxide, sulfur oxides, lead, and organic emissions. Both
sulfur and organic emissions are influenced by the amount of oil or grease on the scrap.
The quantity of sulfur oxides generated may be large enough to cause corrosion of air
pollution control equipment. There are a number of instances where rapid deterioration
of dust collectors on cupolas occured where corrosion protection was not considered.
Where fluorspar is used as an additive, the fluorine driven off can cause a corrosion
problem with dust collection equipment. Fluorine also has the potential to dissolve glass
bags. Carbonic acid, formed when carbon dioxide reacts with water vapor, may cause
corrosion problems as well.
e. Pre-pouring, Pouring, Cooling, and Finishing
Paniculate emissions can be generated during the treatment and inoculation of molten iron
before pouring. For example, the addition of magnesium to molten metal to produce ductile
iron causes a very violent reaction accompanied by various emissions of magnesium oxides
and metallic fumes, depending on the method of treatment. Some methods, such as the
tundish method, result in significantly lower emissions than others. Emissions from pouring
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consist of metal fumes, carbon monoxide, organic compounds, and particulates evolved when
the molten iron contacts the mold and core materials. Emissions continue as the molds cool
and during the shake-out operation, although at a much lower rate. Finishing operations,
such as the removal of burrs, risers, and gates, and shotblast cleaning, also emit particulates,
primarily iron, iron oxide, and abrasive media. The painting of castings also can lead to a
variety of VOC emissions.
2. Air Pollution Control Measures
There are two primary collection methods for foundry particulates - wet and dry. Wet
scrubbers include low- and high-energy types. Dry collection includes baghouses, mechanical
collectors, and electrostatic precipitators. In addition, to control emissions of organic
compounds, incineration or afterburners may be required. Air toxics merit special
consideration, requiring careful selection of the emission control method.
a. Wet Scrubbers
For paniculate collection, the mechanisms used in a wet-type collector are inertial impaction
and direct interception. These are used either separately or in combination. In studying
wet collector performance, independent investigators developed the contact power theory,
which states that, for a well-designed wet-scrubber, collection efficiency is a function of the
energy consumed in the air-to-water contact process and is independent of the collector
design. On this basis, well-designed collectors operating at or near the same pressure drop
can be expected to exhibit comparable performance. All wet collectors have a fractional
efficiency characteristic ~ that is, their cleaning efficiency varies directly with the size of the
particle being collected. In general, collectors operating at a very low pressure loss will
remove only medium to coarse particles. High-efficiency collection of fine particles requires
increased energy input, which will be reflected in higher collector pressure loss.
In addition to particulates, gas scrubbers may be used to control odors and toxic and sulfur
dioxide emissions. In this case, acids, bases, or oxidizing agents may have to be added to
the scrubbing liquid. Disposal of this stream is subject to effluent guidelines for metal
molding and casting.
b. Dry Collectors
The most frequently encountered equipment for the removal of solid paniculate matter from
an air stream or gas stream is the fabric dust collector or baghouse. With a mass median
size of 0.5 Aim, a collection efficiency of 98-99+% can be expected. As the filter medium
becomes coated in a fabric collector, the collection efficiency rises. However, as material
continues to build on the bag surface, higher pressure drops occur, which result in a
significant reduction in airflow. To maintain design flows, the bags must be cleaned
periodically by mechanical shaking or with pulsed air.
Filter media are now available for hot corrosive atmospheres, such as furnace emissions.
Operating inlet temperatures up to 500°F (260°C) are not uncommon. High humidity can
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be a problem if no provision is included for the condensation of free moisture. Free
moisture and acid dew point are the worst enemies of all fabric collectors. It is important
to have the following design information in order to select the proper fabric and the
quantity of bags required:
Gas flow rate
Temperature and dew point
Acid dew point
Particle size and distribution
Concentration of solids
Chemical and physical properties of solids
Teflon-coated, woven glass-fiber bags have been used on a large majority of cupola
installations because of their high temperature resistance. If fluorspar is used, Nomex bags,
which are acid-resistant, but combustible, are generally installed. The temperature of the
gases entering the baghouse then must be reduced to a maximum of 400°F (204°C). Use
of these lower-temperature bags creates a potential corrosion hazard because of the acid
dew point problem. For reverse-air and mechanical shake collectors, air-to-cloth ratios
range from 1.5-2.5:1.
Pulse-jet and cartridge collectors also can be used to collect pollutants from sand systems
and casting cleaning operations. With either type of unit, care must be taken to select the
proper air/cloth ratio (maximum of 25:1 with pulse jet and 1.5:1 with cartridge). In general,
these types of collectors will have only marginal results with furnace and inoculation
emissions. If considered, they should be employed at a very low air/cloth ratio. In addition,
moisture introduced with compressed air may be significant and cause system failure.
c Incineration
Afterburners may be used in some processes to control emissions, particularly when oily
scrap or hydrocarbons in any form are charged into the furnaces or scrap preheat systems.
Afterburning is required for below-the-door cupola emission systems. If afterburners are
not used, carbon monoxide and oil vapors may be emitted through the discharge stack of
the air pollution equipment. In order to achieve the required incineration, sufficient
retention time (a minimum of 0.6 second) and ignition temperatures must be maintained.
In general, in the selection of collection devices for all processes, moisture, temperature, and
the presence of corrosive materials must be considered. The temptation to operate at
higher air/cloth ratios in baghouses must be avoided. Similarly, claims that lower pressure
drops in scrubbers create high efficiencies have been proved to be false.
d. Absorption
Charcoal absorption has been used in conjunction with other control devices for VOC
control.
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3. Hazardous Air Pollutants From Other Metallurgical Industries
Hazardous Air Pollutants (HAPs) emitted from other metallurgical industries include both
organic and inorganic substances. Exhibits 3 and 4 identify some HAPs from process
operations at steel foundries and from aluminum production.
Exhibit 3: Hazardous Air Pollutants from Steel Foundries
HAPs
Potential Emission Sources
Potential Fugitive
Emission Sources
arsenic
beryllium
chromium
copper
lead
manganese
nickel
zinc
iron
furnaces
foundry mold and core
decomposition
converter/charging
furnace tapping
furnace charging
metal casting
Exhibit 4: Hazardous Air Pollutants from Aluminum Production
HAPs
Potential Emission Sources
Potential Fugitive
Emission Sources
fluorides
chloride
hydrogen chloride
calciner
material handling
furnaces
material crusher and mills
storage and handling areas
reduction cells
furnace tapping
furnace charging
coke quenching
D. REFERENCES
This report contains excerpts of information taken directly from the following source:
Air and Waste Management Association. Air Pollution Engineering Manual. New York:
Van Nostrand Reinhold, 1992.
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TANNERIES
A. PROCESS DESCRIPTION
Tanning involves a complex combination of mechanical and chemical processes. The heart
of the process is the tanning operation itself in which organic or inorganic materials become
chemically bound to the protein structure of the hide and preserve it from deterioration.
The substances generally used to accomplish the tanning process are chromium or extracts
from bark of trees, such as chestnut. These tanning agents give rise to the two predominant
types of tanning operations - chrome and vegetable tanning.
1. Chrome Tanning
Most leather produced is chrome tanned. Chrome tanning produces leather better suited
for certain applications, particularly for the upper parts of boots and shoes, and requires less
processing time than traditional vegetable tanning. The general steps required for chrome
tanning of leather are shown in Exhibit 1 and described briefly below. No two tanneries are
identical; each has its unique characteristics and subprocesses; some perform only some of
the processes shown and ship their goods to another tannery to complete the processing.
Hides and skins are received from meatpacking plants by truck or railroad car. Each
cattlehide is tied in a bundle weighing approximately 25 kg. The bundles are cut open and
the hides unfolded, inspected, and usually split along the backbone, producing two sides
from each hide.
Next follows a sequence of wet operations. The sides are soaked in water to return some
of the lost natural moisture. The remaining flesh or fatty substance adhering to the inside
or flesh surface of the side is removed; these fleshings are usually either rendered in the
tannery or sold. The cattlehides are then soaked in a lime and sulfide solution which either
loosens or dissolves the attached hair. In some operations, the hair is only loosened through
the caustic action of the lime, with the hair removed mechanically, followed by washing,
drying, and sale as a by-product (for carpet pads and similar uses). However, the more
common approach for hair removal is to completely dissolve the hair and discharge it to the
wastewater stream.
Following hair removal, the hides are ready to be prepared for the actual tanning operation.
The hides are placed in large rotating drums and treated in turn with an enzyme solution
and then a salt-acid solution. These operations (respectively called bating and pickling)
prepare the hide for the tanning process. While still in the drum after discharge of the
pickling solution, the hides are tanned. A chromium sulfate solution is added to the drum
and the hides and chrome solution are mixed for periods of up to 24 hours.
Following chrome tanning, all hides have a characteristic blue color caused by the chrome
tanning solution. Upon removal from the tanning drums, excess moisture is removed from
the hides through a wringing operation.
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EXHIBIT 1: Process Flow Diagram of a Typical Chrome Tannery
c.. , Bate Wr
Side soak . «,
_,. , * 1 1CK1C ~ * op
Fl6Sh Tan Sta
)
' >
V
r
in
li
IV
\
if
g
t
e
r
Retan
Color
Fat liquor
)
if
D
Cond
Fin
Tr
^
ry
lition Finished
lsh *" leather
im
Y To sanitz
landfil
i
Air emissions
Liquid waste
Solid waste
Y
To sewer
-------
Cattlehides are too thick for most purposes so the tanned hides are split using a machine
similar to a horizontal band saw. The splitting operation produces a grain side of more or
less uniform thickness. One surface of this grain side is the original outer surface of the
cattlehide and retains the natural grain. The splitting operation also yields a thin, inner
portion of the hide known as a "split" or "blue drop." Splits have no graining and are often
used for suede garments. Both the grain side and the split may be further processed to form
a piece of material of uniform thickness. This operation is called shaving and results in the
removal of small pieces of leather with a consistency similar to very coarse sawdust.
Another series of wet operations gives the leather the color and other properties desired in
the finished material. The tanned hides are placed into another drum for retanning,
coloring, and fatliquoring. Retanning is a second, shorter tanning operation normally using
a tanning agent other than chromium. After the retanning solution is discharged from the
drum, a pigment is added in order to dye the leather to the desired color. The coloring
solution is also discharged from the drum. Next a mixture of oils is added and the hides and
oil are rotated in the drum. This operation, called fatliquoring, helps to produce the desired
softness.
After removal from the retan, color, and fatliquor drum, the leather is dried and physically
conditioned. The two most common approaches to this conditioning are staking and buffing.
Staking is a form of massaging which makes the leather more pliable. Buffing is a light
sanding operation applied to either the grain surface or the underside of a piece of leather.
It is used to improve the nap of the underside or to smooth out surface imperfections on
the grain surface.
One or more of several possible finishing steps give the leather the required pattern gloss
or waterproof qualities. Usually all leather receives at least one coat of a liquid finish
material. Finishes are either rolled or sprayed onto the leather. Often three or more coats
of finish are applied to leather, each one followed by a drying cycle. Other finishing
operations include embossing, in which patterns are pressed into the leather surface.
Finally, the surface area of each piece of leather is measured electronically and the area
stamped on the underside. The leather is then packaged and stored for shipment.
2. Vegetable Tanning
Vegetable tanning employs the use of extracts from the bark of various trees as the tanning
agent. Since the introduction of chrome tanning, vegetable tanning has decreased in
importance. Soles of shoes have been traditionally vegetable tanned; however, since the
introduction of synthetic materials for shoe soles, vegetable tanning has further decreased
in importance. Vegetable tanning is also used to produce leather used in crafts.
Many of the basic steps used in the chrome tanning process are also present in vegetable
tanning. The sequence in which these steps are employed is somewhat different, and there
are few finishing operations associated with vegetable tanning. The processing of hides prior
to vegetable tanning begins with a soak in lime to loosen the hair. Hides are then removed
from the lime solution and the hair is removed mechanically. The hides are then soaked
and rinsed, and the fleshing operation is accomplished. Note that in the chrome tanning
5-3
-------
process, fleshing preceded the hair removal operation. After fleshing, the hides are trimmed
into a roughly rectangular shape and then passed through a bate and pickle operation
similar to that used in the chrome tanning process. Coloring, the next operation, is often
done utilizing a weak tanning solution. Normally vegetable tanned leather is not highly
colored. After coloring, the hides are placed into vats containing the bark extract tanning
solution and moved from a strong tanning solution to a slightly weaker one, then rinsed and
partially dried.
True splitting is not usually a part of the vegetable tanning process; however, an operation
called leveling is used to produce a uniformly thick piece of leather. Leveling removes only
the thickest portions of the underside of the hide, and no "split" is produced. Next, the hide
is oiled, which is a process similar to the fatliquoring in chrome tanning. Following oiling,
the hide is dried and then mechanically conditioned.
Virtually no finishing is done at vegetable tanneries. Few, if any, spray finishes are applied
and often the only finishing process employed is pressing to yield a smooth grain surface.
Finally, the hides are measured, packaged, and stored prior to shipment.
B. SOURCES OF POLLUTION
Typical sources of emissions include (1) solvent receiving, (2) mixing vault, (3) supply drum,
(4) spray chamber, (5) dryer, (6) receiving recycled solvents, (7) cleaning operation, (8)
waste solvent storage (See Exhibit 2 for air emissions and solid waste generation points).
C. POLLUTANTS AND THEIR CONTROL
1. Air Emissions
Typical pollutants (either solid or gaseous) from a tannery include chlorine, formaldehyde,
sulfuric acid, glycol ether EB, glycol ether PMA, methyl isobutyl ketone, toluene, xylol,
phosphoric acid, methanol, manganese sulfate, chromium III, ethylene glycol, lead, copper,
and zinc. See Exhibit 2 for a sample listing of toxic air pollutants and their amounts.
Air pollution control methods can include the use of a water fall (efficiency = 50% for
particulates and 10% for VOC), a fume incinerator for spray booth exhausts, and process
modifications (using more water-based processes and less solvent-based ones).
2. Process Liquid and Solid Wastes
Pieces of leather (containing 10 to 50% moisture) in various stages of processing, and
wastewater treatment sludges constitute the bulk of the process solid waste from tanneries.
In order to produce the quality products required by leather consuming industries, tanneries
trim off inferior portions of hides at many steps in processing. Smaller pieces of leather
wastes are produced in shaving and buffing operations. Approximately 35% of all tannery
solid waste is trimmings and shavings of various types.
5-4
-------
Exhibit 2: Emissions of Toxic Air Pollutants From a Typical Tannery
Emission Point
Solvent Receiving
Mixing Vault
Supply Drum
Spray Chamber
Dryer
Receiving Recycled Solvents
Cleaning Operation
Waste Solvent Storage
Pollutants
Methyl Ethyl Ketone
Methyl Isobutyl Ketone
Toluene
Xylol
Methyl Ethyl Ketone
Methyl Ethyl Ketone
Diacetone Alcohol
Glycol Ether EB
Glycol Ether PMA
Methyl Ethyl Ketone
Methyl Isobutyl Ketone
Toluene
Xylol
Diacetone Alcohol
Glycol Ether EB
Glycol Ether PMA
Methyl Ethyl Ketone
Methyl Isobutyl Ketone
Toluene
Xylol
Acetone
Methyl Ethyl Ketone
Toluene
Emission Rate
kg/hr
22.58
1.67
10.04
1.17
0.52
0.52
1.89
11.85
7.6
75.72
59.05
95.78
3338
1.89
11.85
7.6
75.72
59.05
95.78
33.38
0.61
0.98
0.61
Less than 1 kg/hr of each pollutant
Less than 1 kg/hr of each pollutant
Control Methods
Incineration
Process Modification
(e.g., water-based process
instead of solvent-based
process)
Another source of tannery wastes is the finishing department. Finishes are sprayed or rolled
onto leather and the residue is considered to be a solid waste since it is land disposed.
Finish residues are usually slurries containing 10 to 50% solids. Waste finishes account for
about 2% of tannery solid waste.
Wastewater treatment is the single largest source of process solid waste. Almost all
tanneries screen their wastewater. Direct dischargers and some discharging wastewater into
municipal sewers have some form of primary or secondary treatment (only direct dischargers
use secondary treatment). The screenings and sludges from these operations contain lime,
chromium compounds, pieces of leather, hair, and other protein-like substances which are
land disposed. Wastewater screenings and sludge account for about 60% of tannery solid
waste.
5-5
-------
Floor sweepings are the final source of process solid waste. These include twine used to tie
bundles of hides, salt used to preserve the hides prior to handling, and general plant debris.
Approximately 3% of tannery solid waste is floor sweepings.
Wastewater pretreatment is accomplished through sludge dewatering. Sludge dewatering
is performed using gravity (sequential settling) or mechanical means. Three mechanical
methods of sludge dewatering are used by tanneries - vacuum filters, centrifuges, and filter
presses. All three are effective; however, there seems to be a preference for filter presses
due to the slightly drier (40% solids) filter cake produced.
See Exhibit 3 for solid wastes, their amounts, and methods of disposal.
Exhibit 3: Hazardous Wastes From a typical Tannery
Waste Source
Chrome trimmings &
Shavings
Chrome fleshings
Unfinished chrome
leather trim
Buffing dust
Finishing residues
Finished leather trim
Sewer screenings
Wastewater treatment
residues (sludges)
Pollutant
Cr+3
Cr*3
Cr+3
Cu
Pb
Zn
Cr+3
Cu
Pb
Zn
Cr+3
Cu
Pb
Zn
Cr+3
Pb
Cr+3
Pb
Zn
Cr+3
Cu
Pb
Zn
Concentration Range*
(wet weight in mg/kg)
2,200 - 21,000
4,000
4,600 - 37,000
2.3-468
2.5 - 476
9.1 - 156
19 - 22,000
29 - 1,900
2-924
160
0.45 - 12,000
0.35 - 208
2.5 - 69,200
14-876
1,600 - 41,000
100 - 3,300
0.27 - 14,000
2- 110
35- 128
0.33 - 19,400
0.12 - 8,400
0.75 - 240
1.2 - 147
Disposal Method
Landfill
Dewater sludge; all
waste disposed in
certified hazardous
waste disposal facility
Landfill with leachate
collection
1 Range not shown when only one sample was analyzed for the constituent
5-6
-------
D. REFERENCES
All information on air emissions for this report was taken from Assessment of Information
Available Through State & Local Air Pollution Control Agencies to Support NESHAP
Development presented by Vi'GYAN Inc. to the U.S. EPA on February 26, 1993.
All other information for this report was taken from Assessment of Industrial Hazardous
Waste Practices in Leather Tanning and Finishing Industry presented by SCS Engineers to
the U.S. EPA in November 1976.
5-7
-------
THIS PAGE LEFT BLANK
5-8
-------
6
-------
CEMENT INDUSTRIES
A. PROCESS DESCRIPTION
Cement industries typically produce portland cement, although they also produce masonry
cement (which is also manufactured at portland cement plants). Portland cement is a fine,
typically gray powder comprised of dicalcium silicate, tricalcium silicate, tricalcium
aluminate, and tetracalcium aluminoferrite, with the addition of forms of calcium sulfate.
Different types of portland cements are created based on the use and chemical and physical
properties desired. Portland cement types I - V are the most common. Portland cement
plants can operate continuously for long time periods (i.e. > 6 months) with minimal shut
down time for maintenance. The air pollution problems related to the production, handling,
and transportation of portland cement are caused by the very fine particles in the product.
Exhibit 1 illustrates the stages of cement production at a portland cement plant:
1. Procurement of raw materials
2. Raw Milling - preparation of raw materials for the pyroprocessing system
3. Pyroprocessing - pyroprocessing raw materials to form portland cement clinker
4. Cooling of portland cement clinker
5. Storage of portland cement clinker
6. Finish Milling
7. Packing and loading
1. Raw Material Acquisition
Most of the raw materials used are extracted from the earth through mining and quarrying
and can be divided into the following groups: lime (calcareous), silica (siliceous), alumina
(argillaceous), and iron (ferriferous). Since a form of calcium carbonate, usually limestone,
is the predominant raw material, most plants are situated near a limestone quarry or receive
this material from a source via inexpensive transportation. The plant must minimize the
transportation cost since one third of the limestone 'is converted to C02 during the
pyroprocessing and is subsequently lost. Quarry operations consist of drilling, blasting,
excavating, handling, loading, hauling, crushing, screening, stockpiling, and storing.
2. Raw Milling
Raw milling involves mixing the extracted raw materials to obtain the correct chemical
configuration, and grinding them to achieve the proper particle-size to ensure optimal fuel
efficiency in the cement kiln and strength in the final concrete product. Three types of
processes may be used: the dry process, the wet process, or the semidry process. If the dry
process is used, the raw materials are dried using impact dryers, drum dryers, paddle-
equipped rapid dryers, air separators, or autogenous mills, before grinding, or in the grinding
process itself. In the wet process, water is added during grinding. In the semidry process
the materials are formed into pellets with the addition of water in a pelletizing device.
6-1
-------
EXHIBIT 1:
Basic Flow Diagram of the Portland Cement Manufacturing Process (Part 1)
iQUARRIED RAM
i MATERIALS
RAW
MATERIALS
STORAGE
NJ
PURCHASED
RAW
MATERIALS
RAW MATERIAL
PROPORTION
DRY PROCESS
A
k
A
1
1
GRINDING
MILL
DUST
COLLECTOR
AIR
SEPARATOR
Go to Part 2
on next page
WET PROCESS
GRINDING
MILL
Go to Part 2
on next page
Particulate Emissions
-------
EXHIBIT 1:
Basic Flow Diagram of -the Portland Cement Manufacturing Process (Part 2)
DRY RAW MEAL
BLENDING AND
STORAGE
DUST
COLLECTOR
SLURRY
BLENDING AND
STORAGE
DUST
COLLECTOR
KILN
Go to Part 3
on next page
Particulate Emissions
Nitrogen, Carbon Dioxide, Water, Oxygen,
Nitrogen Oxides, Sulfur Oxides, Carbon Monoxide,
and Hydrocarbons
-------
EXHIBIT 1:
Basic Flow Diagram of the Portland Cement Manufacturing Process (Part 3)
GYPSUM
4 A
i i
i i
CEMENT
STORAGE
fc
w
SHIPMENT
Particulate Emissions
-------
3. Pyroprocessing
In pyroprocessing, the raw mix is heated to produce portland cement clinkers. Clinkers are
hard, gray, spherical nodules with diameters ranging from 0.32 - 5.0 cm (1/8 - 2") created
from the chemical reactions between the raw materials. The pyroprocessing system involves
three steps: drying or preheating, calcining (a heating process in which calcium oxide is
formed), and burning (sintering). The pyroprocessing takes place in the burning/kiln
department. The raw mix is supplied to the system as a slurry (wet process), a powder (dry
process), or as moist pellets (semidry process). All systems use a rotary kiln and contain the
burning stage and all or part of the calcining stage. For the wet and dry processes, all
pyroprocessing operations take place in the rotary kiln, while drying and preheating and
some of the calcination are performed outside the kiln on moving grates supplied with hot
kiln gases.
4. Clinker Cooling
The clinker cooling operation recovers up to 30% of kiln system heat, preserves the ideal
product qualities, and enables the cooled clinker to be maneuvered by conveyors. The most
common types of clinker coolers are reciprocating grate, planetary, and rotary. Air sent
through the clinker to cool it is directed to the rotary kiln where it nourishes fuel
combustion. The fairly coarse dust collected from clinker coolers is comprised of cement
minerals and is restored to the operation. Based on the cooling efficiency and desired
cooled temperature, the amount of air used in this cooling process is approximately 1-2
kg/kg of clinker. The amount of gas to be cleaned following the cooling process is
decreased when a portion of the gas is used for other processes such as coal drying.
5. Clinker Storage
Although clinker storage capacity is based on the state of the market, a plant can normally
store 5 - 25% of its annual clinker production capacity. Equipment such as conveyors and
bucket elevators is used to transfer the clinkers from coolers to storage areas and to the
finish mill. Gravity drops and transfer points typically are vented to dust collectors.
6. Finish Milling
During the final stage of portland cement production known as finish milling, the clinker is
ground with other materials (which impart special characteristics to the finished product)
into a fine powder. Up to 5% gypsum and/or natural anhydrite is added to regulate the
setting time of the cement. Other chemicals, such as those which regulate flowability or air
entrainment, may also be added. Many plants use a roll crusher to achieve a preliminary
size reduction of the clinker and gypsum. These materials are then sent through ball or
tube mills (rotating, horizontal steel cylinders containing steel alloy balls) which perform the
remaining grinding. The grinding process occurs in a closed system with an air separator
that divides the cement particles according to size. Material that has not been completely
ground is sent through the system again.
6-5
-------
7. Packing and Loading
Once the production of portland cement is complete, the finished product is transferred
using bucket elevators and conveyors to large, storage silos in the shipping department.
Most of the portland cement is transported in bulk by railway, truck, or barge, or in 43 kg
(94 pound) multiwalled paper bags. Bags are used primarily to package masonry cement.
Once the cement leaves the plant, distribution terminals are sometimes used as an
intermediary holding location prior to customer distribution. The same types of conveyor
systems used at the plant are used to load cement at distribution terminals.
B. SOURCES OF POLLUTION
Although portland cement plants generate the same final product using similar processes,
plant layouts vary according to fuels and raw materials used, location, climate, site
topography, and the manufacturer of the equipment. The flow diagram in Exhibit 1 depicts
the manufacturing process at a portland cement plant and indicates emission points
throughout the'process.
C. POLLUTANTS AND THEIR CONTROL
This section briefly discusses the nature of the pollutants generated from, and controls used
at, several sources in the cement manufacturing process. Air pollutants are typically of
greater concern than solid or liquid wastes.
1. Air Pollutants
Air pollutants generated during the cement manufacturing process consist primarily of
particulates from the raw and finished materials, and fuel combustion by-products. Exhibit
2 indicates sources of air pollution, and differentiates between particulates and other air
pollutants.
Controlling paniculate emissions from sources other than the kiln usually entails capturing
the dust using a hood or other partial enclosure and transporting it through a series of ducts
to the collectors. The type of dust collector used is based on factors such as particle size,
dust loading, flow rate, moisture content, and gas temperature. The best disposal method
for collected dust is to send it through the kiln creating the clinker. However, if the alkali
content of the raw materials is too high, the dust must be discarded, or must be pretreated
before introduction into the kiln. The highest allowable alkali content is 0.6 percent (as
sodium oxide). Exhibit 3 summarizes the general applicability of a number of collection
systems for use by the cement industry.
Additional air pollutants emitted include such materials as sulfur oxides and nitrogen oxides
generated from the kiln and drying processes. Sulfur dioxide is generated from the sulfur
compounds in the ores and the combusted fuel and varies in amount produced from plant to
plant. The efficiency of paniculate control devices is inconclusive as the result of variables
such as feed sulfur content, temperature, moisture, and feed chemical composition, in addition
to alkali and sulfur content of the raw materials and fuel. The combustion of fuel in rotary
6-6
-------
Exhibit 2: Air Pollution and Control at Cement Production Facilities
Emission Point
Quarries
Raw Mill
Systems
Kiln System
Clinker Coolers
Finish Mill
Systems
Finish Mill
Systems
For use with
High-
Efficiency
Separators
Packing and
Loading
Departments
Pollutants
Particulates
Particulates
Particulates
Particulates
Particulates
Particulates
Particulates
Particulates
Emission Rate
(gr/acf1)
5-40
5-20
4-18
5-10
5-20
.5-100
150-300
5-40
Control Device
Fabric Filter:
Pulse Jet
Reverse Air /Shaker
Fabric Filter:
Pulse Jet
Reverse Air/Shaker
Cartridge
Dust Collectors:
Reverse Air
Precipitator
Fabric Filters:
Pulsed Plenum/Pulse Jet
Reverse Air
Precipitator
Fabric Filter:
Reverse Air/Shaker
Fabric Filters:
Pulse Jet
Pulsed Plenum
Fabric Filters:
Pulse Jet
Pulsed Plenum
Fabric Filters:
Pulse Jet
Reverse/Air Shaker
Cartridge
Percent
Efficiency
299.6
299.6
299.5
299.6
299.6
299.6
299.9
299.6
1 gr/acf = grains/actual cubic foot
6-7
-------
Exhibit 3: Applicability of Emission Control Methods
Operation
Primary
grinding
Air
separators
Mills
Storage
silos
Feeders
and belt
conveyors
Packing and
loading
Coal
dryer
Kiln
gases
Clinker
cooler
Mechanical
Collector
Unsatisfactory
efficiency
Not
applicable
Not
applicable
Not
applicable
Not
applicable
Not
applicable
Preliminary
cleaning only
Preliminary
cleaning only
Preliminary
cleaning only
Wet
Scrubber
Not
applicable
Not
applicable
Not
applicable
Not
applicable
Not
applicable
Not
applicable
Practicable
Impractical
Not
applicable
Fabric
Collector
Successful
Successful
Successful
Successful
Successful
Successful
Successful
12 x 30 Glass
Successful
Successful
Electrostatic
Not
applicable
A few
installations
A few
installations
Not
applicable
Not
applicable
Not
applicable
Not
common
Successful
Not
common
Gravel Bed
Filter
None in use
Questionable
application
Questionable
application
Impractical
Impractical
Impractical
Practicable
Practicable
Successful
6-8
-------
cement kilns generates nitrogen oxides from the nitrogen in the fuel and incoming combustion
air. The amount emitted depends on several factors including fuel type, nitrogen content, and
combustion temperature. Both sulfur dioxide and some of the nitrogen oxide react with the
alkaline cement and are removed from the gas stream.
a. Raw Material Acquisition
During raw material acquisition the primary air pollutant emitted is paniculate matter.
Paniculate matter is also emitted from the handling, loading, unloading, and transport of raw
materials purchased from another source, such as coal. In certain areas exhaust from portable
equipment may also be a consideration.
The following methods are used to control paniculate emissions generated from the
quarry and handling of purchased raw materials:
fabric filters (pulse-jet or reverse-air/shaker) equipment enclosures
water sprays (with and without surfactants) enclosures
silos (with and without exhaust venting to wind screens
fabric filters) foams
mechanical collectors bins
chemical dust suppressants paving
material storage buildings
Dust that is collected by these means is restored to the process. For quarry operations, newer
plants typically use the pulse-jet fabric filters while older plants employ the reverse-air or
shaker-type fabric filters.
b. Raw Milling
Fugitive dust is emitted from raw material feeders, stackers, blenders, reclaimers, conveyor belt
transfer points, and bucket elevators used for transferring materials to the mill department
from storage. Particulate emissions from the dry raw mills and subsequent equipment occur
during temporary failure or from improperly designed or maintained seals.
The following devices are used to collect particulate matter in the raw mill and raw mix storage
areas:
mechanical cyclones (usually used in series with another control)
fabric filters (pulse jet or reverse air/shaker)
electrostatic precipitators (rarely used)
Newer plants typically use the pulse-jet fabric filters while older plants employ the reverse-air
or shaker type fabric filters.
6-9
-------
c. Pyroprocessing
The main pyroprocessing system emissions are nitrogen, carbon dioxide, water, oxygen, nitrogen
oxides, sulfur oxides, carbon monoxide, and hydrocarbons. Cement kiln dust (CKD) is also
produced.
The cement kiln itself has been designated as best available control technology (BACT) for
the control of SO2. The highly alkaline conditions of the kiln system enable it to capture up
to 95% of the possible SO2 emissions. However, if sulfide sulfur (pyrites) is present in the kiln
feed, this absorption rate can decline to as low as 50%. Therefore, sulfur emissions can be
decreased through careful selection of raw materials.
No device to control cement kiln NOX emissions has been developed, but there are several
prospects:
stable kiln operation (reduces long term NOX emissions);
burner configurations for the rotary kiln (efficiency varies);
staged combustion for precalciner kilns;
recirculation of the flue gas (oxygen deficient air in the rotary kiln); and
alternative/low-nitrogen fuels.
Cement kiln dust (CKD) is the powder retrieved from the exiting gases and is either all or
partly returned to the operation or removed entirely. The type of system, the chemical makeup
of the raw materials and fuel, and the condition of the system operations all affect the chemical
configuration of the CKD. Portland cement specifications usually limit the amounts of sodium
and potassium. Because bypass CKD contains a large quantity of these minerals, CKD is
usually removed from the process. The CKD from a preheater tower is composed of the same
general elements as the kiln feed and therefore is returned to the process. The handling,
storage, and deposition of CKD can generate fugitive dust emissions.
The following methods are used to control paniculate emissions from the kiln system:
reverse-air fabric filters
electrostatic precipitators (ESPs)
acoustic horns (sometimes used in conjunction with the two devices above)
d. Clinker Cooling
Reciprocating grate clinker coolers most often employ fabric filters, but ESPs and gravel bed
filters are also used with a mechanical cyclone or multiclone dust collector sometimes placed
in front. Newer plants typically use pulse-jet or pulsed-plenum fabric filters and older plants
use reverse-air type fabric filters which may simply be a smaller form of a kiln fabric filter.
Gravel bed filters, which are also used by the cement industry, contain quartz granules;
contaminated gas passes through this filter and the dust settles to the bottom of the bed.
6-10
-------
& Clinker Storage
The devices used to control dust emissions from clinker storage areas are similar to those used
in the raw milling process. The paniculate emissions generated by dropping clinkers onto
storage piles can be reduced by using a rock ladder or variable-height, automatic, stacker belt
conveyor systems. Fugitive dust generated from open storage piles is tempered by rain and
snow, wind breaks, and pile covers. Clinker in open piles is moved using front-end loaders;
in storage halls overhead bucket cranes are used. Fugitive clinker dust emitted from open
storage piles is common and very difficult to control.
/ Finish Milling
Particulate matter is emitted from mill vents, air separator vents, and material-handling system
vents. Newer plants usually use pulse-jet or pulsed-plenum fabric filters with high-efficiency
separators, while older plants use reverse-air/shaker fabric filters. The cement dust collected
by the fabric filter is restored to the system. In cold weather, a plume may develop at the
baghouse vent; this may be mistaken for paniculate matter, but actually is condensed water
vapor from the cooling system.
g. Packing and Loading
In the shipping department particulate matter is emitted from the silos and the handling and
loading operations. Active and passive fabric filters are used to collect this dust. During
loading of the product, particulate emissions are controlled by a fabric filter connected to the
transport vessel; collected dust is restored to the shipment. To ensure dust-free loading onto
the transport vessel, a flexible loading spout consisting of concentric tubes is used. The outer-
most tube seals the delivery spout to the transport vehicle. The product is then delivered
through the inner tube and displaced air drawn up the outer tube to a filter. At distribution
terminals, fabric filters are again used and the collected dust is returned to the product. New
plants typically use pulse-jet fabric filters while older plants use reverse-air or shaker-type
fabric filters.
2. Liquid and Solid Wastes
The overflow from slurry concentrating equipment (i.e. thickeners) constitutes the main water
pollution problem. For new plants that process slurry, closed-cycle water systems are used to
return the overflow water to the process. Another source of waste is the stripped overburden,
which is used as a raw material or disposed of in a local landfill. An estimate of overburden
deposited in a landfill varies from 0 - 3 metric tons per metric ton of cement produced.
The combustion processes of cement kilns and rotary kilns have been used to dispose of
hazardous waste material. For the cement kiln, waste material is burned with a primary fuel.
For a wet process kiln, the raw materials are introduced into the top of the kiln and exit at the
bottom as cement clinker. The burner is located at the lower end of the kiln where the fuel
and waste are ignited. The hot gases move up the kiln and heat the raw materials, exit the
kiln, and are then cleaned in a baghouse prior to exiting through a stack. When waste is fired,
any ash generated becomes a part of the cement product.
6-11
-------
D. REFERENCES
1. Air and Waste Management Association. Air Pollution Engineering Manual. New
York: Van Nostrand Reinhold, 1992.
2. Hall, F.D. Evaluation of the Feasibility of Incinerating Hazardous Waste in High-
Temperature Industrial Process. 1984.
3. Reding, J. T., P.E. Muehlberg, and B.P. Shepherd (Dow Chemical). Industrial Process
Profiles for Environmental Use: Chapter 21. The Cement Industry, February 1977.
6-12
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-------
PRINTED CIRCUIT BOARD MANUFACTURING
A. PROCESS DESCRIPTION
Printed circuit boards are electronic circuits created by mounting electronic components on
a non-conductive board, and creating conductive connections between them. The creation
of circuit patterns is accomplished using both additive and subtractive methods. The
conductive circuit is generally copper, although aluminum, nickel, chrome, and other metals
are sometimes used. There are three basic varieties of printed circuit boards: single-sided,
double-sided, and multi-layered. The spatial and density requirement, and the circuitry
complexity determine the type of board produced. Printed circuit boards are employed in
the manufacturing of business machines and computers, as well as communication, control,
and home entertainment equipment.
Production of printed circuit boards involves the plating and selective etching of flat circuits
of copper supported on a nonconductive sheet of plastic. Production begins with a sheet of
plastic laminated with a thin layer of copper foil. Holes are drilled through the board using
an automated drilling machine. The holes are used to mount electronic components on the
board and to provide a conductive circuit from one layer of the board to another.
Following drilling, the board is scrubbed to remove fine copper particles left by the drill.
The rinsewater from a scrubber unit can be a significant source of copper waste. In the
scrubber, the copper is in a paniculate form and can be removed by filtration or centrifuge.
Equipment is available to remove this copper paniculate, allowing recycle of the rinsewater
to the scrubber. However, once mixed with other waste streams, the copper can dissolve
and contribute to the dissolved copper load on the treatment plant.
After being scrubbed, the board is cleaned and etched to promote good adhesion and then
is plated with an additional layer of copper. Since the holes are not conductive, electroless
copper plating is employed to provide a thin continuous conductive layer over the surface
of the board and through the holes. Electroless copper plating involves using chelating
agents to keep the copper in solution at an alkaline pH. Plating depletes the metal and
alkalinity of the electroless bath. Copper sulfate and caustic are added (usually
automatically) as solutions, resulting in a "growth" in volume of the plating solution. This
growth is a significant source of copper-bearing wastewater in the circuit board industry.
Treatment of this stream (and the rinsewater from electroless plating) is complicated by the
presence of chelating agents, making simple hydroxide precipitation ineffective. Iron salts
can be added to break the chelate, but only at the cost of producing a significant volume
of sludge. Ion exchange is used to strip the copper from the chelating agent, typically by
using a chelating ion exchange resin. Regeneration of the ion exchange resin with sulfuric
acid produces a concentrated copper sulfate solution without the chelate. This regenerant
can then be either treated by hydroxide precipitation, producing a hazardous waste sludge,
or else concentrated to produce a useful product.
7-1
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Growth from electroless copper plating is typically too concentrated in copper to treat
directly by ion exchange. Different methods have been employed to reduce the
concentration of copper sufficiently either to discharge the effluent directly to the sewer or
to treat it with ion exchange. One method, reported by Hewlett-Packard, replenishes growth
with formaldehyde and caustic soda to enhance its autocatalytic plating tendency, and then
mixes it with carbon granules on which the copper plates out in a form suitable for
reclaiming.
Following electroless plating, copper is electroplated on the board to its final thickness, and
a layer of tin-lead solder is plated over the copper. A photoresist material is then applied
to the board and exposed by photoimaging a circuit design. Following developing and
stripping a selected portion of the photoresist, that portion of the tin-lead plate is etched
to reveal the copper in areas other than the final desired circuit pattern.
The exposed copper is then removed by etching to reveal the circuit pattern is the remaining
copper. Ammonia-based etching solutions are most widely used. Use of ammonia
complicates waste treatment and makes recovery of copper difficult. An alternative to
ammonia etching is sulfuric acid/hydrogen peroxide etching solutions. This latter etchant
is continuously replenished by adding concentrated peroxide and acid as the copper
concentration increases to about 80 g/L At this concentration, the solution is cooled to
precipitate out copper sulfate. After replenishing with peroxide and acid, the etchant is
reused. Disadvantages of the sulfuric acid-peroxide etching solution are that it is relatively
slow when compared with ammonia, and controlling temperature can be difficult.
Exhibit 1 shows the general processes in printed circuit board manufacturing.
B. SOURCES OF POLLUTION
Wastes are generated from the following five processes that are common to the manufacture
of all types of circuit boards:
cleaning and surface preparation
catalyst application and electroless copper plating
pattern printing and masking
electroplating
etching
The wastes generated include airborne particulates, spent plating baths, and waste
rinsewater among others. Exhibit 1 indicates the sources of pollution.
C. POLLUTANTS AND THEIR CONTROL
Emissions of air pollutants from the manufacture of printed circuit boards stem primarily
from the board cleaning and preparation process; other emissions are generally of much less
significance. The majority of the emissions are acid fumes and organic vapors from the
7-2
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EXHIBIT 1: Process Flow Diagram of a Typical Printed Circuit Board
Manufacturing Plant
A
Imagine
I.IS
>..
*
Copper
electroplating
ily
>fc
Solder
electroplating
>fc
Stripping &
etching
os
>fc
*
Final
processes
Y
Air emissions
Solid/liquid waste
-------
cleaning processes. Some participates are also emitted in the drilling and finishing of the
boards. Proper ventilation and exhaust of all process baths, rinse operations, and
mechanical operations is essential to managing the air emissions of a printed circuit board
manufacturing operation and can also contribute to reduction in liquid and metal waste
generation. Exhibit 2 lists air pollutants and methods of control.
Each manufacturing process may generate multiple waste streams. Rinse water and other
rinse solutions are usually the largest streams by volume, but are generally lower in
concentration of hazardous chemicals than spent process baths. Contamination of rinse
streams can be minimized by strategies that reduce drag-out of process solutions. Treatment
and reuse of rinse streams is also effective in reducing overall waste generation.
Airborne particulates emitted from cutting, sanding, routing, drilling, beveling, and slotting
operations during board preparations are usually controlled by baghouse and cyclone
separators. The collected pollutants are then disposed of, along with other solid wastes at
landfills.
Acid fumes from acid cleaning and organic vapors from vapor degreasing are usually not
contaminated with other materials, and therefore are often kept separate for subsequent
treatment. The acid fume air stream is collected via chemical fume hoods and sent to a
scrubber where the acid is removed with water. The scrubbed air then passes on to the
atmosphere, and the absorbing solution is neutralized along with other acidic waste streams.
Similarly, organic fumes are often collected and passed through a bed of activated carbon.
The carbon bed is then regenerated with steam. In many cases, the regenerative vapor is
cooled and the condensate containing water and solvent drummed and set aside for off-site
treatment. In a few cases, the regenerative vapor is combusted in a closed fumes burner.
The spent acid and alkaline solutions from the cleaning steps are either sent off site for
disposal or neutralized and discharged to the sewer. Spent chlorinated organic solvents are
often gravity separated and recovered in-house, or hauled away for reclaiming.
Most of the remaining wastes are liquid waste streams containing suspended solids, metals,
fluoride, phosphorus, cyanide, and chelating agents. Low pH values often characterize the
wastes due to acid cleaning operations. Liquid wastes may be controlled using end-of-pipe
treatment systems, or a combination of in-line treatment and separate treatment of
segregated waste streams. A traditional treatment system for the wastes generated is often
based on pH adjustment and the addition of chemicals that will react with the soluble
pollutants to precipitate out the dissolved contaminants in a form such as metal hydroxide
or sulfate. The solid particles are removed as a wet sludge by filtration or flotation, and the
water is discharged to the sewer. The diluted sludge is usually thickened before disposal in
landfills. Recent improvements in in-line treatment technologies, such as reverse osmosis,
ion exchange, membrane filtration, and advanced rinsing techniques, increase the possibility
for the recovery and reuse of water and metallic resources.
Exhibit 3 delineates the waste streams from printed circuit board manufacturing.
7-4
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Exhibit 2: Air Emissions from Printed Circuit Board Manufacturing
Emission Point
Surface Preparation
Surface Cleaning
Pollutants
Particulates
VOC
Acid fumes
VOC
Control Device
Baghouses/Cyclone separators
Carbon adsorber
Wet scrubbers
Carbon adsorber
Exhibit 3: Waste Streams From the Manufacture of Printed Circuit Boards
WASTE SOURCE
WASTE STREAM
DESCRIPTION
WASTE STREAM
COMPOSITION
Cleaning/Surface Preparation
Spent acid/alkaline solution
Spent halogenated solvents
metals, fluoride, acids, halogenated
solvents, alkali, board materials,
sanding materials
Waste rinse water
Electroless Plating
Spent electroless copper bath
Spent catalyst solution
acids, stannic oxide, palladium,
complexed metals, chelating agents,
copper
Spent acid solution
Waste rinse water
Pattern Printing and Masking
Spent developing solution
Spent resist removal solution
vinyl polymers, chlorinated
hydrocarbons, organic solvents, alkali
Spent acid solution
Waste rinse water
Electroplating
Spent plating bath
Waste rinse water
copper, nickel, tin, tin/lead, gold,
fluoride, cyanide, sulfate
Etching
Spent etchant
Waste rinse water
ammonia, chromium, copper, iron,
acids
7-5
-------
D. REFERENCES
This report contains excerpts of information taken directly from the following sources:
1. Higgins, Thomas. Hazardous Waste Minimization Handbook. Chelsea, Michigan:
Lewis Publishers, Inc., 1991.
2. Jacobs Engineering Group, Guides to Pollution Prevention: The Printed Circuit
Board Manufacturing Industry. Pasadena, California, June 1990.
3. Kirsch, F. W., and Looby, G. P. Waste Minimization Assessment for a Manufacturer
of Printed Circuit Boards. July 1991. EPA/600/M-91/022
7-6
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8
-------
ELECTROPLATING
Electroplating is the process of depositing a coating having desirable characteristics by
means of electrolysis. The purpose of electroplating is to alter the characteristics of a base
metal's or other material's surface to provide improved appearance, ability to withstand
corrosive agents, resistance to abrasion, or other desired properties, or a combination of
them. The electroplating industry utilizes chemical and electrochemical operations to effect
these improvements. Because metal electroplating is the most prevalent type, it will be used
for process descriptions and pollutant identification.
A. PROCESS DESCRIPTION
1. Material Preparation
Base materials are generally prepared for plating by mechanical, chemical, or
electrochemical means. Metal imperfections, scales, oils, and grease must be removed from
the surface if electroplating is to be successful. Mechanical operations performed in
electroplating facilities include abrasive blast cleaning, barrel finishing, grinding, polishing,
and buffing. Chemical operations include degreasing, alkaline cleaning, acid treatments,
chromating, phosphating, passivating, bright dipping, chemical polishing, and electroless
nickel plating.
2. Plating
Electroplating operations include nickel, chromium, cadmium, zinc, copper, tin, iron, gold,
and silver plating as the most important processes. Alloys may be deposited from solutions
with compatible anions. Anodizing is used most often for aluminum plating. Each
electroplating metal is chosen for its particular characteristics. Some common electroplating
metals and their specific characteristics are:
nickel: corrosion and wear resistance, and to rebuild worn parts.
chrome: corrosion resistance, bright metallic appearance, impart improved
mechanical properties (hardness, lubricity) to base.
cadmium: corrosion protection
zinc: corrosion protection
copper: electrical conductivity properties
gold: high conductivity, inertness, aesthetic appeal.
silver: high conductivity, inertness, aesthetic appeal.
The plating cycle following the pretreatment steps can be very simple, such as a sequence
of cleaning-rinsing-plating-rinsing-drying, or very complex, requiring a number of cleaning
steps with additional steps of acid dipping, striking, activation, multiple rinses and the
deposition of more than one metal. All processing steps within a given cycle must be
arranged so that the solutions will not be contaminated. Cleaners, acid dips and strikes vary
in composition and concentration and are formulated for a particular base material.
Cleaners are generally alkaline and are used to remove the last traces of oil and grease.
8-1
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Acid dips are not intended to remove scales or oxides but are used to neutralize traces of
alkaline cleaners left on the base material after rinsing and to activate the surface to receive
the electrodeposit. Some materials require more intense activation steps than others. Each
base material must be treated differently and each metal deposited requires a specific cycle.
Thus, each electroplating operation is comprised of a number of steps of different duration,
where the products are moved in a sequence from one chemical solution to another. Two
operations used most frequently are barrel operations and rack plating.
In barrel operations small parts are electroplated while tumbling freely in
rotating barrels.
In rack plating, components held in a rack are dipped into an electroplating
solution. Rack plating is required for a large percentage of materials
electroplated. Racks are used for reasons including maintenance of shape or
surface conditions, achievement of the desired distribution of coating, or size
or shape of workpiece.
3. Alternative processes
Recent developments such as new regulations on the discharge of toxic materials, the small
number of certified landfill sites, and the rising costs of plating metals and chemicals have
given rise to alternative electroplating methods. Some of the more prevalent methods
include aluminum electroplating and ion vapor depositing.
a. Aluminum electroplating
Aluminum electroplating imparts corrosion resistance to the base material. This method
is being used as a substitute for the costly and highly toxic cadmium electroplating.
Aluminum is less costly than cadmium, and can be used at higher temperatures.
b. Ion vapor deposition
Old electroplating methods applied coating by dipping or by a metal spray. These are
inefficient since they do not impart a thin and uniform coating. Ion vapor deposition utilizes
a high-voltage system inside a vacuum to ionize the coating substance and impart a negative
charge to the parts. This charge causes the coating substance ions to electrodeposit in the
air. The air in the chamber is replaced by a low-pressure ionized gas. The substance's vapor
must interact with the ionized inert gas to attract oppositely charged parts and coat them
uniformly. Ion vapor deposition is most often used when aluminum is the coating substance.
B. SOURCES OF POLLUTION
There are several possible process paths for electroplating, each dependent on such factors
as electroplating metal type, reason(s) for electroplating, and dip tank chemical makeup.
The process diagram shown in Exhibit 1 is for a general electroplating process with acid
recovery. All sources in the electroplating process emit air pollutants, and many generate
hazardous waste. These are indicated in the exhibit.
8-2
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EXHIBIT 1: Sources of Pollution in the Electroplating Process
""WORK
PIECE
oo
SURFACE
CLEANING /
PREPARATION
AIR EMISSIONS
SOLID / LIQUID WASTE
PLATING BATH
RINSING
WASTEWATER
STORAGE
FILTERS
FINISHED
PRODUCT
DEIONIZED WATER
CARBON
FILTERS
HCL
A
CAUSTIC
SODA
CATION / ANION
BEDS
-------
c.
POLLUTANTS AND THEIR CONTROL
Exhibit 2 identifies air emissions from electroplating operations, and Exhibit 3 identifies
potentially hazardous waste generation.
Exhibit 2: Air Emissions From Different Chrome Electroplating Operations
Emission
Source
Surface Cleaning/ Preparation
Acid/alkali cleaning
Cold cleaners
Vapor degreasers
Surface Modification
Hard chromium plating
Decorative chromium
plating
Chromic acid anodizing
Pollutants
Cu, Ni, Zn, Pb
Fe
VOC
VOC
Cr+6
Emission
Rate
3 mg/1 each
36mg/l
190-560 kg/yr
9500 kg/yr
15-90 g/hr
4-66 g/hr
1.2-2.8 g/hr
Control
Device
Covers
Increased
freeboard
Refrigerated
chiller
Carbon adsorber
Demister
Wet scrubber
Chemical fume
suppressants
Control
Eff. (%)
87.9-99.7
95.4-99.4
99.5-99.8
Exhibit 3: Potentially Hazardous Wastes Generated From Electroplating Operations
Waste Source
Chemical operations
Electroplating
operations
Degreasing
Pollutant
Heavy metals
Heavy metals
Oil and grease
Asbestos
Cyanides
Solvent
Chlorinated & fluorinated hydrocarbons'
Amount
N/A
Disposal Method
Landfilling
Landfilling
N/A
'Hydrocarbons include trichloroethylene, perchloroethylene, methyl chloroform,
trichlorotrifluoroethylene, methylene chloride.
8-4
-------
Potentially hazardous wastes are found in one of three forms: (1) low-solids slurry, (2) high
solids sludge, and (3) solid waste. Treatment of the low-solids slurry is performed by
densification or densification and de water ing to produce a waste more easily disposed of to
the land. Concentrated solutions of heavy metals may alternatively be treated by
reclamation or chemical fixation and solidification. High-solids sludge and solid wastes are
sometimes treated by volume reduction processes, such as incineration, to reduce the
transportation and final disposal costs.
The increasing costs and liability of hazardous waste disposal are leading many
electroplating facilities to incorporate process modifications to reduce hazardous waste
generation. Some of these modifications include:
Reduction of drag-out. Drag-out is the liquid which clings to a part as it is
removed from a process bath.
Modification of rinsing operations that are used to remove residual drag-out.
Recovery of materials from rinsewaters.
Reducing or eliminating tank dumping.
Substituting less hazardous materials into the process (noncyanide baths,
vacuum disposition, ion vapor deposition).
D. REFERENCES
1. Assessment of Industrial Hazardous Waste Practices: Electroplating and Metal
Finishing Industries - Job Shops. EPA Hazardous Waste Management Division, 1976.
2. Hazardous Waste Minimization Handbook. 1991, pp. 75-212.
8-5
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THIS PAGE LEFT BLANK
8-6
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9
-------
LEAD SMELTING
Lead is usually found naturally as a sulfide ore containing small amounts of copper, iron,
zinc, and other trace elements. There are two major lead smelting processes: primary lead
smelting and secondary lead smelting. Primary lead smelting involves any process engaged
in the production of lead from sulfide ore concentrates through the use of pyrometallurgical
techniques. Secondary lead smelting involves the reclaiming and refining of lead from
leadbearing scrap materials in which the predominant component is lead.
A. PROCESS DESCRIPTION
1. Primary lead smelting
The processing of lead from sulfide ores involves three major phases -- sintering, reduction,
and refining.
a. Sintering
The sulfide ore is first reduced to sinter. Sinter is a coherent mass of lead formed by
heating, but not melting, the ore. The sinter machine is a continuous steel pallet conveyor
belt moved by gears and sprockets, with each pallet consisting of perforated or slotted
grates. Fans beneath the pallets create a draft, either up or down, to create the conditions
necessary for autogenous primary reactions.
The updraft sinter machine design is superior to the down-draft design for many reasons.
The sinter bed is more permeable, which permits a higher production rate. Second, the
small amounts of lead that form will solidify at their point of formation, instead of flowing
down and collecting on the grates or at the bottom of the sinter charge and causing reduced
blower capacity, as they do in a down-draft sinter machine. Also, the updraft design can
produce sinter of higher lead content. Finally, the updraft design can produce a single
strong sulfur dioxide effluent stream by the use of weak gas recirculation. This is extremely
helpful in air emissions control. To maintain a desired sulfur content of 5 to 7 wt % in the
sinter charge, limestone, silica, sinter recycle, and flue dust are often added to the sinter
mix.
b. Reduction
After sintering, lead reduction occurs in a blast furnace. The blast furnace, which is a water-
jacketed shaft furnace supported by a refractory base, is charged with a mixture of sinter,
metallurgical coke, and various recycled and cleanup materials.
Solid products from the blast furnace generally separate into four layers: speiss (the lightest
material, basically arsenic and antimony), matte (copper sulfide and other metal sulfides),
slag (primarily silicates), and lead bullion. The first three layers are collectively called slag,
9-1
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and contain most of the impurities. The slag is continuously collected and is either
processed at the smelter for its metal content or shipped to treatment facilities.
After the lead bullion leaves the blast furnace, it usually requires preliminary treatment, or
drossing, in kettles before undergoing refining operations. As the bullion is cooled, copper,
sulfur, and other metals and impurities collect on the surface as dross. The dross is
removed from the solution and may undergo some recovery methods.
c. Refining
The final smelting phase is refining, which is done in cast iron kettles. There are five
refining steps:
1. Removal of antimony, tin, and arsenic.
2. Removal of metals by Parke's process.
3. Vacuum removal of zinc.
4. Removal of bismuth by the Betterson process.
5. Removal of remaining traces of metal impurities by the addition of NaOH
and NaNO3.
The final refined lead is then cast into pigs for shipment.
2. Secondary lead smelting
Three types of furnaces are employed in the recovery of lead from scrap material, each with
different processes and emissions: reverberatory, blast, and pot furnaces. Each furnace type
also produces a different lead grade: soft, semisoft, and hard.
a. Reverberatory Furnaces
Reverberatory furnaces are used in sweating operations. Sweating heats the mix charge,
melting the metal which is tapped off at intervals as semisoft lead. This is a continuous
process, with more charge being added in such a manner as to keep a small mound of
unmelted material on top of the bath. Reverberatory furnaces are also used to reclaim lead
from oxides and drosses.
The reverberatory furnace produces semisoft lead which usually contains trace amounts of
antimony and copper.
b. Blast Furnaces
Blast furnaces, or cupolas, are similar to those used in the ferrous industry. Rerun slag,
scrap cast iron, limestone, coke, drosses, oxides, and reverberatory slags form the usual
charge in a blast furnace. Hard lead is charged into the cupola at the start of the process
9-2
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to provide molten metal to fill the crucible. The charges are added as the material metal
melts down. The limestone and iron form a flux that floats on the top of the molten lead
and retards oxidation.
Slag is tapped at intervals while the molten lead flows from the furnace at a more or less
continuous rate. Approximately 70% of the molten material is tapped off as lead and the
remaining 30% as slag. About 5% of the slag is retained for later use. The blast furnace
produces hard lead, which typically contains 5-12% antimony and trace amounts of arsenic,
tin, copper, and nickel.
c. Pot Furnaces
Pot-type furnaces are used for remelting, alloying, and refining processes. Remelting is
usually done in small furnaces using alloys in ingot form as charge. Alloying usually begins
with a metal lower in the percentage of alloying materials than desired. The required
amount is then added to the molten material. Antimony, tin, arsenic, copper, and nickel are
the most commonly used alloying elements.
The refining processes most commonly used are those for the removal of copper and
antimony to produce soft lead, and those for the removal of arsenic, copper, and nickel to
produce hard lead. Aluminum is often added to the molten lead. The aluminum reacts
with copper, antimony, and nickel to form complex compounds that can be skimmed off the
surface. A procedure known as "dry dressing", where sawdust is introduced into the agitated
mass of molten metal, is also used. During dry drossing, carbon, which aids in separating
globules of lead suspended in the dross, is formed.
Pot furnaces generally produce soft lead, a high-purity grade formed after considerable
refining has been performed. Soft lead may be designated as corroding, chemical, acid
copper, or common desilverized lead.
B. SOURCES OF POLLUTANTS
Exhibit 1 is a flow diagram of the primary lead smelting process. Both air emission points
and hazardous waste generation points are identified. Exhibit 2 identifies the air emission
points and hazardous waste generation points for the general secondary lead smelting
process.
C. POLLUTANTS AND THEIR CONTROL
Exhibits 3 and 4 identify the pollutants by source that are emitted or generated by the
various smelting processes. Exhibit 3 presents air pollutants, and identifies control devices,
if any, for primary and secondary lead smelters. Exhibit 4 presents hazardous waste
pollutants, and identifies the disposal methods, if any.
9-3
-------
EXHIBIT 1: Diagram of a Typical Primary Lead Smelting Process
A A A
' ' DROSS" '
C ^ SINTER SINTER BULLION DROSSING BULL
CONCENTRATE fc SINTER k BLAST DROSSING
1 A w' MACHlNci A ^ rURNAUE A w' Kbl ILbio
L )\ \ *t
LIMESTONE 1 PbO
SILICA 1 COKE
SINTER REYCLE
FLUE DUST
COKE _.
4 i
AMMONIA CHLORIDE
SODA ASH
SLAG SULFUR
. . FLUF, DUST
1 COKE A
' ! ^
DROSS
r
SLAG DROSS
FUMING REVERBERATORY
FURNACE FURNACE
f Zr
i
r
T >i (NATTE AND |
'° J SPEISS
ION
^ RRFTMEBV
LIMESTONE
SILICA
SOPA ASH
SULFUR
PIG IRON
PbO
COKE
REFINED LEAD
AIR EMISSIONS
-------
EXHIBIT 2: Diagram of a Typical Secondary Lead Smelting Process
PRETREATMENT
SMELTING
REFINING
PRODUCTS
DROSS AND
FINE DUST
i
i
REVERBERATORY
/ BLAST
DUST
AGGLOMERATION
ZINC
LEACHING
CASTING
REVERBERATORY _,
i
KETTLE
SOFTENING
i
i
Ventilation System to
Emission Controls
Air Emissions
Effluent Stream
Solid Residues
-------
Exhibit 3: Air Emissions From Primary and Secondary Lead Smelters
Emission
Point
Pollutants
Emission
Rate
Control Device
PRIMARY LEAD SMELTING
Ore Crushing
Sinter Machine
Blast Furnace
Dross Reverb.
Furnace
Refining
Materials
Handling
Participates
S02
Participates
SO2
POM, As, fluorides,
Sb, Pb, Hg, Se
Participates
S02
POM, As, fluorides,
Sb, Cd, Pb, Hg, Se
Participates
Participates
S02
Particulates
S02
1.0 kg/mt
No data
106.5 kg/mt
275.0 kg/mt
Trace amounts
180.5 kg/mt
22.5 kg/mt
Trace amounts
10.0 kg/mt
2.5 kg/mt
No data
Baghouse
Baghouse
ESP
Sulfuric acid plants
Baghouse
Enclosures
Water spraying
Control
Eff.(%)
95-99
95-99
95-99
>96
95-99
SECONDARY LEAD SMELTING
Reverb. Furnace
Lead Blast
-Furnace
Pot-type
Furnace
Particulates
SO2; SO3; oxides,
sulfides/sulfates of
Pb, Sn, As, Cu,
Particulates
CO
Lead oxide
Particulates
1.4-4.5 gr/ft3
Up to 4 gr/ft3
Baghouse with gas-cooling
devices & settling chambers
Hoods; Baghouse;
Afterburner
Baghouse
9-6
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Exhibit 4: Sources of Hazardous Waste in Lead Smelting Operations
Waste Source
Primary
Secondary
Blast furnace
slag
Scrubber slag
Cupola furnace
slag & matte
Reverb, furnace
slag
Pollutant
Heavy metals
(As, Cd, Cr, Cu, Hg,
Pb, Sb, Zn)
Heavy metals
(Cu, Cr, Pb, Sb, Sn,
Zn)
Cr
Cu
Mn
Ni
Pb
Sb
Sn
Zn
Cd
Cr
Cu
Mn
Pb
Sb
Zn
Cu
Mn
Ni
Pb
Sb
Sn
Zn
Cr
Cu
Mn
Pb
Sb
Sn
Zn
Amount (mt/y)1
4400
160
2
18
2
2
162
10
2
10
0.02
/ 0.001
0.001
0.005
24
0.5
0.001
41
0.4
0.4
158
4
0.4
2
0.8
0.2
1.2
8
0.1
30
0.8
Disposal Method
Land storage before recycle.
Immediate recycle.
Land storage or open dumping
of dredged sludge in unlined
lagoons.
Dumping in lined or unlined
lagoon.
Open dumping of discarded
slag.
metric tons per year
9-7
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D. REFERENCES
1. Air Pollution Engineering Manual. Air & Waste Management Association.
2. 40 CFR 60, Part R
9-8
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