Environmental Chemistry Eneg 2052 Credits/Ects Credits 3/6: by Kenatu Angassa (PHD)

Environmental Chemistry
EnEg 2052
Credits/ECTS Credits 3/6
By Kenatu Angassa (PhD)
Chapter 5
Chemistry of Hazardous waste
• Introduction to chemistry of hazardous waste
• Classification of hazardous substance
• Properties of hazardous waste
• Transport, effects and fates of hazardous waste
12/02/2021 Kenatu Angassa (PhD) 1

Introduction to chemistry of hazardous waste
Definitions
 Dissolved oxygen (DO) is a measure of how
much oxygen is dissolved in the water - the amount of oxygen available to
living aquatic organisms
 Contaminant - a substance present in greater than the usual (normal)

concentration
◦ It is a pollutant when it exerts detrimental effect on human health
 Pollutant - a contaminant which has a detrimental effect upon its
environment
◦ If the concentration of a substance already present in nature is
increased to unrequired ratio due to human activity, which ultimately
has a detrimental effect on the environment then it is known as a
pollutant (eg. SO4 , CO, Pb, Hg, excess heat, sound etc.)
Definitions
 Source - every pollutant originates from a source

◦ Identifying the source is very important since the most efficient
remediation can usually be achieved at this location
 Receptor - anything that the pollutant acts upon

◦ A receptor may be anything which is affected by the pollutant. For
example, man is a receptor of contaminated water because cholera
and gastroenteritis are caused by it
 Reservoir or Compartment - a region or unit within the

environment in which a substance resides & mixes
◦ For example atmosphere, oceans & other water bodies

Definitions
 Sink-a longer term reservoir in which a substance is essentially immobilized

◦ The oceans & ocean sediments are a sink for many of the dissolved species
present in freshwater
 Explosive-A chemical that causes a sudden, almost instantaneous release of

pressure, gas, and heat when subjected to sudden shock, pressure, or high
temperature
 Residence time–is the average amount of time a substance spends in a

particular compartment or reservoir
◦ Residence time = steady-state amount of substance in the reservoir/rate of

inflow to (or outflow from) reservoir
Definitions
 Hazard is any source of potential damage, harm or adverse health

effects on something or someone
◦ For example any substance, material, process, practice that has the
ability to cause harm or adverse health effect to a person or property
 The hazard presented by a chemical has two components

◦ (I) Hazard is inherent capacity to do harm by virtue of its toxicity,
flammability, explosiveness, corrosiveness, etc.; and
◦ (II) the simplicity with which the chemical can come into contact with
a person or other object of concern

Definitions
 Risk is the chance or probability that a person will be harmed or

experience an adverse health effect if exposed to a hazard
◦ For example: "cigarette smokers are 12 times more likely to die

of lung cancer than non-smokers",
 Not all chemicals are considered hazardous
 Examples of non hazardous chemicals include pH neutral buffers, sugars,

starches, agar, and naturally occurring amino acids
 This chapter will focus on hazardous chemicals

A. Chemical hazards, including the following

◦ i. Flammability
◦ ii. Explosiveness
◦ iii. Reactivity
B. Health hazards, including chemicals that are:

◦ 1) Toxins (both acute and long-term)
◦ 2) Carcinogens
◦ 3) Reproductive Toxins
◦ 4) Teratogens
◦ 5) Mutagens
◦ 6) Neurotoxins
 A substance is considered hazardous if it exhibits any characteristics of
I. Flammable:
◦ Substances that readily catch fire (e.g., gasoline and alcohol)
II. Corrosive
◦ Substances that corrode storage tanks & equipment
◦ Most corrosives belong to at least one of the four following chemical
classes: strong acids, strong bases, oxidants, & dehydrating agents

III. Explosive:
◦ Substances that may cause an explosion (e.g., trinitrotoluene or TNT)
IV Reactive
◦ Substances that are chemically unstable & may explode or create toxic
fumes when mixed with water e.g., explosives, elemental phosphorus, &
concentrated sulfuric acid
 Toxic is substances injurious to health when ingested or inhaled (e.g.,

chlorine, ammonia, pesticides, and formaldehyde)
 A hazardous pollutant is thus defined by its toxicity and impact on
human health or its negative effects on organisms in ecosystems
How to Determine if a Chemical is “Hazardous”

 Any chemical that is classified as
◦ a physical hazard,
◦ a health hazard,
◦ combustible dust
◦ pyrophoric gas,
◦ hazard not otherwise classified is considered a hazardous chemical
 Physical hazard means a chemical that is classified as posing one of the

following Hazardous effects
◦ Explosive (gases, aerosols, liquids, or solids)
◦ Flammable (gases, aerosols, liquids, or solids)
◦ Oxidizer (gases, liquids, or solids)
◦ self-reactive
◦ Pyrophoric (liquids, or solids)
◦ self-heating;
◦ organic peroxide;
◦ corrosive to metal;
◦ gas under pressure; or in contact with water emits flammable gas

 Health hazard means a chemical that is classified as posing

one of the following hazardous effects:
◦ Acute toxicity (any route of exposure);
◦ Skin corrosion or irritation;
◦ Serious eye damage or eye irritation;
◦ Respiratory or skin sensitization;
◦ Germ cell mutagenicity;
◦ Carcinogenicity;
◦ Reproductive toxicity;
◦ Specific target organ toxicity12/02/2021
(single or repeated exposure);
Kenatu Angassa (PhD) 11
 Exposure usually occurs through
◦ Inhalation,
◦ Skin contact
◦ Ingestion
 Adverse health effects can be

◦ Acute (short-term)
 Example: headaches, nausea or vomiting, and skin corrosion,
◦ Chronic (long-term)
 Example: asthma, dermatitis, nerve damage, or cancer

 Therefore, the management of hazardous wastes has become a specialized
discipline because of the complex nature of the problem & the solutions
available to humanity
 The management process hazardous waste is based on
◦ the definition & classification of the different wastes
◦ their toxic effects on human
◦ the application of risk management to control human health &

environmental impacts
 Hazardous waste management deals with minimizing harmful effects on

humans & environment by applying special techniques of handling, storage,
transportation, treatment, & disposal of hazardous wastes

Source of Hazardous waste

I. Industrial wastes
◦ Non‐hazardous (Large in volume )
◦ Hazardous components (small in volume)
 It was identified as hazardous waste when proceeds toxicity test,
corrosively test, ignitability test, & some special character test
II. Household waste

◦ Small quantities of hazardous wastes
◦ Examples: oil‐based paints, paint thinners, wood preservatives,

pesticides, insecticides, household cleaners, used motor oil, antifreeze, &
batteries

III. Biomedical waste
◦ some of hazardous medical & dental wastes
 Infectious waste
◦ contain pathogens: bacteria, viruses, fungi, or parasites to cause disease
 Pathological waste
◦ Including tissue, organs, body parts, human fetuses, & animal bodies,
blood & body fluids
 Sharps
◦ syringes, needles, scalpels, saws, infusion sets, knives, blades, etc
 Pharmaceutical waste
◦ It covers expired, unused, spilt, drugs, vaccines, etc.

 Genotoxic waste
◦ cytostatic drugs, vomit, urine, or feces from the patients treated with
cytotoxic drugs, chemicals,& radioactive materials
 Chemical waste
◦ It should be considered as hazardous if it is toxic, corrosive,

inflammable, or reactive
 Waste with high content of heavy metals:
◦ Mercury (thermometers, blood pressure gauges, amalgam),
◦ Cadmium (discarded batteries),
◦ Lead (radiation proofing in radiology department)

IV. Radioactive waste
◦ Radioactive waste, arising from civilian nuclear activities as well as from
weapon activities,
◦ It poses a potential problem for handling & saving the environment for
coming generations
◦ It can be classified as
 Low‐/intermediate‐level radioactive waste
 High‐level radioactive waste

Classification of Hazardous Waste
 The EPA has identified four main categories in which hazardous wastes can
be classified
 With each categorization comes different risks & disposal methods
 That is why it is necessary to understand the main classification
 The four identifiable classifications are
◦ Listed wastes
◦ Characteristic wastes
◦ Universal wastes
◦ Mixed wastes

A) Listed Wastes
 There are four sub-types of listed wastes: F-list, K-list, P-list & U-list
a) F-List Wastes
 Includes any wastes that have a nonspecific source, but are produced from
manufacturing & industrial processes
 F-list wastes can be divided into seven groups depending on the operations that
produce the wastes
◦ 1. Dioxin-bearing wastes
◦ 2. Wood-preserving wastes
◦ 3. Spent solvent wastes
◦ 4. Petroleum refinery wastewater treatment sludges
◦ 5. Chlorinated aliphatic hydrocarbons production
◦ 6. Multisource leachate
◦ 7. Electroplating and other metal finishing wastes
b) K-List Wastes
7. Primary aluminium production
 K-list wastes are specific wastes that
8.Organic chemicals manufacturing
have specific industry sources
9. Pesticides manufacturing
 The top 13 industries that generate K-
10. Coking (processing of coal to
lists are
produce coke)
1.Iron and steel production
11. Inorganic chemicals manufacturing
2. Petroleum refining
12. Wood preservation
3. Inorganic pigment manufacturing
13. Secondary lead processing
4. Explosives manufacturing
5. Ink formulation
6.Veterinary pharmaceuticals
manufacturing

 F-lists & K-lists wastes are identified by an EPA-assigned code depending
on if they contain any of the following codes
◦ Toxic Waste (T)
◦ Acute Hazardous Waste (H)
◦ Ignitable Waste (I)
◦ Corrosive Waste (C)
◦ Reactive Waste (R )
◦ Toxicity Characteristic Waste (E)

c) P-List & U-List Wastes
 They are specific commercial chemical products that are disposed of, but
unused
 To be considered as one of these wastes, they must meet certain criteria

& be commercial grade formulations of specific unused chemicals
◦ It must contain one of the chemicals identified in the P or U list
◦ The waste’s chemical must be unused
◦ The waste must be in a commercial chemical product form

B) Characteristic Wastes
 They follow the identification process depending on the four
characteristics
1. Ignitability
◦ Any waste that is flammable and can create fires
2. Corrosivity
◦ Any waste (acids & bases) that can rust & decompose & has the ability
to melt through steel materials
3. Reactivity
◦ Any waste that is explosive, unstable under normal conditions
4. Toxicity
◦ Any waste that is fatally poisonous when ingested or absorbed

C) Universal Wastes
 Include bulbs, mercury-containing equipment, pesticides & batteries
 They are of the more commonly produced & identified as “dangerous goods”
 There are 9 classifications with universal wastes
◦ Class 1: Explosives
◦ Class 2: Gases
◦ Class 3: Flammable Liquids
◦ Class 4: Flammable Solids or Substances
◦ Class 5: Oxidizing Substances and Organic Peroxides
◦ Class 6: Toxic and Infectious Substances
◦ Class 7: Radioactive
◦ Class 8: Corrosive Substances
◦ Class 9: Miscellaneous Dangerous Substances & Articles
D) Mixed Wastes
 These are wastes that contain both hazardous as well as radioactive
components
 Because they involve hazardous & radioactive materials, their treatment &
disposals are vary
 According to the US they are identified as one of 3 types of mixed waste
◦ Low-level mixed waste (LLMW)
◦ High-level mixed waste (HLW)
◦ Mixed transuranic waste (MTRU)

Properties of Hazardous Waste
Environmental Chemistry of Hazardous Wastes
 Based upon the definition of environmental chemistry, Hazardous wastes
are considered in five aspects
◦ Origins, Transport, Reactions, Effects & Fates
 It is also useful to consider the five environmental spheres with
hazardous wastes:
◦ Anthrosphere, Geosphere, Hydrosphere, Atmosphere & Biosphere

Properties of Hazardous Waste
 Almost Hazardous materials are originate in the anthrosphere, are often
discarded into the geosphere, are frequently transported through the
hydrosphere or the atmosphere
 The greatest concern for their effects is usually on the biosphere,

particularly human beings
 Hazardous wastes enter into the environment through
 Emission of Hazardous gases & particulate matter into the atmosphere
 Discharging Hazardous wastewater into land or water bodies
 Hazardous wastes store in the landfill into geosphere
 Evaporation & wind erosion of Hazardous wastes into atmosphere
 Hazardous waste dumps & leached into groundwater or surface waters

Transport, effects and fates of hazardous waste
Transport of hazardous wastes
 The factor affects the transportation of hazardous wastes are
◦ Their physical properties,
◦ The physical properties of their surrounding matrix,
◦ The physical conditions to which they are subjected,
◦ Chemical factors
For example:
 Highly volatile wastes are obviously more likely to be transported through the
atmosphere, & more soluble ones to be carried by water
 Wastes will move faster in porous, sandy formations than in denser soils
 Volatile wastes are more mobile under hot, windy conditions, & soluble ones
during periods of heavy rainfall
 Wastes that are more chemically & biochemically reactive will not move
so far as less reactive wastes before breaking down
Fates of Hazardous Wastes
 The fate of a hazardous waste material is a function of its physical

properties & surroundings
For example:
 The fate of a hazardous waste substance in water is a function of the

substance’s Solubility, Density, Biodegradability, & Chemical reactivity
Hazardous Wastes in the Anthrosphere
 Most hazardous wastes may come from manufacturing, transportation

activities, agriculture, & any activities in the anthrosphere
 The releases of hazardous wastes from the anthrosphere commonly occur

through incidents such as spills of liquids, accidental discharge of gases or
vapors, fires, and explosions
 To minimizing risk & increasing the safety of the transport of hazardous
substances through the anthrosphere the clear system of documentation
was designed to accomplish the following goals
◦ Acts as a tracking device to establish responsibility for the generation,

movement, treatment, & disposal of the waste
◦ to provides information regarding appropriate actions to take during

emergencies such as collisions, spills, fires, or explosions
◦ Acts as the basic documentation for recordkeeping & reporting
 Example
◦ Corrosion of materials
◦ Fire & explosion of hazardous materials

Hazardous Wastes in the Geosphere
 Hazardous wastes can enter into groundwater through
◦ Leachate from a landfill
◦ Leaks of Sewers & pipelines
◦ Wastes leaching from disposal site
 The movement of hazardous waste constituents into the geosphere is

largely by the action of flowing water in a waste plume
 The speed & degree of waste flow depends upon
◦ Hydrologic factors such as water gradient
◦ permeability of the solid formations through which the waste plume

moves are important

Hazardous wastes in the hydrosphere
 Hazardous waste substances enter the hydrosphere through
◦ Leachate from waste landfills
◦ drainage from waste ponds
◦ Seepage from sewer lines, or runoff from soil
◦ Deliberate release into water bodies
 Hazardous waste species undergo a number of physical, chemical, &

biochemical processes which strongly influence their effects & fates
 Hydrolysis reactions are those in which a molecule is cleaved with addition

of a molecule of H2O

Hazardous Wastes in the Atmosphere
 Hazardous waste can enter the atmosphere through
◦ evaporation from hazardous waste sites
◦ wind erosion
◦ direct release
 An important characteristic of a hazardous waste material that enters the
atmosphere is
◦ Its pollution potential
◦ Its residence time
◦ Its dissolution
 A significant number of hazardous waste substances leave the atmosphere
through
◦ Dissolution
◦ Adsorption onto particles,
◦ Dry deposition, meaning that chemical processes must be involved
Hazardous Wastes in the Biosphere
 Microorganisms, bacteria, fungi & protozoa may act metabolically on
hazardous wastes substances in the environment
 Most of these substances are anthropogenic & most are classified as xenobiotic
molecules that are foreign to living systems
 Xenobiotic compounds are degradation resistant & can be at least partially

degraded by various microorganisms
 Bioaccumulation occurs in which wastes are concentrated in the tissue of

organisms
 Biodegradation is conversion hazardous waste by biological processes to

simpler molecules
 Detoxification is the production of a less toxic product by biochemical
processes
Microbial Metabolism in Waste Degradation
 Biotransformation is the enzymatic change of a substance by
microorganisms
 Metabolism is the biochemical process by which biotransformation is

carried out
 Catabolism is an enzymatic process by which more complex molecules

are broken down into less complex ones
 Anabolism is an enzymatic process by which simple molecules are

assembled into more complex biomolecules
 Two major biochemical metabolism that operate on hazardous waste are
◦ Aerobic processes
◦ Anaerobic processes

Microbial Metabolism in Waste Degradation

 Most xenobiotic compounds are acted upon by cometabolism process
which occurs concurrently with normal metabolic processes
 The susceptibility of a xenobiotic hazardous waste compound to

biodegradation depends upon its physical & chemical characteristics
 Important physical characteristics include
◦ water solubility,
◦ hydrophobicity (hate to water),
◦ volatility
◦ lipophilicity (affinity for lipids)

Hazardous wastes management
 Waste management is an important component of environmental policy
all over the world
 Priority of hazardous solid waste for environmental protection is

formulated on source reduction & reuse, recycling, treatment, and
landfilling

End of Chapter 5

Environmental Chemistry Eneg 2052 Credits/Ects Credits 3/6: by Kenatu Angassa (PHD)

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Environmental Chemistry

12/02/2021 Kenatu Angassa (PhD) 1

 Contaminant - a substance present in greater than the usual (normal)

 Source - every pollutant originates from a source

 Receptor - anything that the pollutant acts upon

 Reservoir or Compartment - a region or unit within the

◦ For example atmosphere, oceans & other water bodies

 Sink-a longer term reservoir in which a substance is essentially immobilized

 Explosive-A chemical that causes a sudden, almost instantaneous release of

 Residence time–is the average amount of time a substance spends in a

◦ Residence time = steady-state amount of substance in the reservoir/rate of

 Hazard is any source of potential damage, harm or adverse health

 The hazard presented by a chemical has two components

 Risk is the chance or probability that a person will be harmed or

◦ For example: "cigarette smokers are 12 times more likely to die

 Examples of non hazardous chemicals include pH neutral buffers, sugars,

 This chapter will focus on hazardous chemicals

12/02/2021 Kenatu Angassa (PhD) 6

A. Chemical hazards, including the following

B. Health hazards, including chemicals that are:

◦ Substances that corrode storage tanks & equipment

◦ Most corrosives belong to at least one of the four following chemical

classes: strong acids, strong bases, oxidants, & dehydrating agents

 Toxic is substances injurious to health when ingested or inhaled (e.g.,

How to Determine if a Chemical is “Hazardous”

 Physical hazard means a chemical that is classified as posing one of the

◦ Explosive (gases, aerosols, liquids, or solids)

◦ Flammable (gases, aerosols, liquids, or solids)

◦ Oxidizer (gases, liquids, or solids)

◦ Pyrophoric (liquids, or solids)

◦ gas under pressure; or in contact with water emits flammable gas

 Health hazard means a chemical that is classified as posing

 Adverse health effects can be

 Example: headaches, nausea or vomiting, and skin corrosion,

12/02/2021 Kenatu Angassa (PhD) 12

 The management process hazardous waste is based on

◦ the definition & classification of the different wastes

◦ their toxic effects on human

◦ the application of risk management to control human health &

 Hazardous waste management deals with minimizing harmful effects on

12/02/2021 Kenatu Angassa (PhD) 13

Source of Hazardous waste

II. Household waste

◦ Examples: oil‐based paints, paint thinners, wood preservatives,

12/02/2021 Kenatu Angassa (PhD) 14

◦ contain pathogens: bacteria, viruses, fungi, or parasites to cause disease

◦ syringes, needles, scalpels, saws, infusion sets, knives, blades, etc

◦ It covers expired, unused, spilt, drugs, vaccines, etc.

cytotoxic drugs, chemicals,& radioactive materials

◦ It should be considered as hazardous if it is toxic, corrosive,

 Waste with high content of heavy metals:

◦ Mercury (thermometers, blood pressure gauges, amalgam),

◦ Cadmium (discarded batteries),

◦ Lead (radiation proofing in radiology department)

12/02/2021 Kenatu Angassa (PhD) 16

 Low‐/intermediate‐level radioactive waste

 High‐level radioactive waste

12/02/2021 Kenatu Angassa (PhD) 17

 With each categorization comes different risks & disposal methods

 That is why it is necessary to understand the main classification

 The four identifiable classifications are

12/02/2021 Kenatu Angassa (PhD) 18