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ENGI 9609/ENVS 6007 Environmental Risk Assessment

Lecture 5
Fate and Transport of
Risk Agents in Environment I

Yinchen Ma
yinchen.ma@mun.ca

Winter 2018
Faculty of Engineering & Applied Science
Outline

1. Basic Concepts

2. Chemical Distribution among Phases

3. Pollutant Interaction with Biota

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1. Basic Concepts

Contaminant
Any physical, chemical, biological or radiological substance
or matter that has an adverse effect on air, water or soil.
- US EPA

A substance in the environment that is capable of causing


adverse human health, ecological, or aesthetic effects.
 Result of either natural processes or human activities
1) Naturally occurring contaminants
 Airborne particulate matter and gases
 Waterborne metals (arsenic, mercury, or uranium decay products)
2) Anthropogenic contaminants
 Ozone and related photochemical oxidants in air
 Chlorinated hydrocarbons in air and water
 Radionuclides from nuclear reactors
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1. Basic Concepts
Contaminant Releases Resulting in Adverse Human Health or Ecological Impacts
Location Date Contaminant Effect
London 1852 Human waste Cholera
Ducktown, TN 1900s SO2 from a smelter Death of vegetation
Donora, PA 1948 SO2 and particulate matter from 20 immediate deaths;
various industries 5910 cases of respiratory distress in a
population of 14,000
Minimata, 1950s Methyl mercury Dead fish, birds and cats; nervous disorders
Japan and birth defects in humans
Seveso, Italy 1976 Dioxin Chloracne, death of farm animals, high
female/male birth ratio
Bhopal, India 1984 Methyl isocyanate released in an 3800 immediate deaths;
accident at a chemical plant other effects (lungs, eyes, stillbirths) in
170,000 survivors
Ukraine & 1986 Radioactivity released from the 31 immediate deaths;
Belarus Chernobyl accident increased thyroid cancer in children
Sweden & 2000s Acid rain due to oxides of nitrogen Widespread damage to forest ecosystems
Northeastern and sulfur in the atmosphere from and freshwater fish habitats
US
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1. Basic Concepts

Buried waste

Human Exposures
Facility release
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1. Basic Concepts

Transport and Food Chains


Media
• Solid Transformation • Product
• Air
Source • Liquid • Beef
• Soil
Emission • Gases • Fish
• Surface water
• Aerosols • Dairy
• Groundwater
• Mother’s

Exposure Pathways Exposure Pathways


Risk Characterization
• Ingestion • Ingestion
• Carcinogenic
• Inhalation • Inhalation
• Non-carcinogenic
• Dermal contact • Dermal contact

Source
Fate and Transport and Risk Assessment
Modification

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2. Chemical Distribution among Phases
 Environment consists of a number of connected Phases in each
compartment (medium):
o Atmosphere contains air, water and suspended solids
o Surface water contains water, solid particles, and gas bubbles
o Soil contains air, solid and water
 It is important to understand how pollutants will be distributed among
air, water and solid phases in different compartments (their movement,
concentration and behaviour)
 Terminologies:
o Gas phase = pure air;
o Aqueous phase = pure water;
o Solid phase = solid grain, solid particles;
o Non-aqueous phase liquid (NAPL) = an immiscible liquid (e.g. oil
slick)

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2. Chemical Distribution among Phases
 Solubility
Concentration of chemicals dissolved in water at equilibrium and
water is in contact with the pure chemical/pollutant

Strongly dependent on
chemical structure

Polarity increase 
Solubility increase

Please check page 4-9 and 25-27


in the Reference Material for
properties of chemicals

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2. Chemical Distribution among Phases
 Vapor Pressure
The pressure exerted by the vapor of pure liquid chemical at
saturation conditions at a certain temperature

Gas concentration Gas pressure Ideal Gas Law

Henry’s Law Constant

)
=
)
,
=
,
. / )
=
. / )

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2. Chemical Distribution among Phases
 Octanol-Water Partitioning Coefficient ( )
Represents the degree to which a contaminant prefers organic materials to water

,
=
,
, Equilibrium concentration of chemical in octanol (mass of A / L octanol)
, Equilibrium concentration of chemical in water (mass of A / L water)

Example 1
A stoppered flask at 25 oC contains 250 ml water, 200 ml octanol, and
50 ml of air. An unknown amount of o-xylene is added to the flask and
allowed to partition among the phases. After equilibrium has been
established, 5.0 mg of o-xylene are measured in the water.
What is the total mass of o-xylene present in the flask?
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3. Pollutant Interaction with Biota

3.1 Aquatic Organism


 3.1.1 Affection Factors/Processes
 Factors affecting the uptake and absorption of pollutants by
Aquatic Organism (i.e. fish, shrimp)
1) Physiological process, such as ingestion, respiration and excretion
2) Passive physical exchange of pollutants between the lipid content
of the biota and the surrounding water
 Processes affecting the concentration of particle-bound
chemicals in aquatic organisms (i.e. fish tissue)
1) Bioaccumulation (chemical become stored in organism)
2) Bioconcentration (chemical conc. in aquatic organism > in water)
3) Biomagnification (chemical conc. change with trophic level)
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3. Pollutant Interaction with Biota

 3.1.2 Bioaccumulation
A process that results in an organism having a higher concentration
of a substance than is in its surrounding environmental media.
 Bioconcentration Factors (BCFs)
 Used to relate pollutant residues in aquatic organisms
to the pollutant concentration in ambient waters
• For surface water, BCF is the ratio of a chemical
concentration in an organism to the chemical aqueous
concentration
• Merely a ratio, does not explain about the mechanics of
chemical accumulation

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3. Pollutant Interaction with Biota
 3.1.3 Models for Bioaccumulation Processes
1) Partitioning Model
• Assume equilibrium state between organisms and environment
• Suitable for hydrophobic chemicals (accumulation >>
excretion/metabolization)
• Suitable only for aquatic organisms
,
Biota-water Partitioning Coefficient ( ) =
,
, Equilibrium chemical concentration in biota (mass of A / L biota)

, Equilibrium chemical concentration in water (mass of A / L water)

Summary of Partitioning Coefficients


, , , ,
= = = =
, , , ,

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3. Pollutant Interaction with Biota

Example 2

Three (3) moles of pesticide of molecular mass 200 g/mol is


applied to a closed system consisting of 20 m3 of water, 10 m3 of
air, 1 m3 of sediment, and 0.001 m3 of fish.

Determine the concentration and amount in both grams and


mole units in air, water, sediment and fish in equilibrium
condition if the partitioning coefficients are: air/water = 0.1,
sediment/water = 50, and fish/water = 200

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3. Pollutant Interaction with Biota

Example 3

A circular lake of 2 km diameter and 10 m deep contains


suspended solids (SS) with volume fraction of 10-5 (i.e. 1 m3
of suspended solids per 105 m3 of water) and biota (such as
fish) at a concentration of 1 mg/L.
Assuming specific density of biota as 1, and SS/water
partitioning coefficient as 100. Assume any data not given.
Calculate the deposition and concentration of 1.5 kg of
polychlorinated biphenyl (PCB) in this system.

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3. Pollutant Interaction with Biota

2) Physiologically-based Pharmacokinetic Models


 Pharmacokinetics
Study of absorption, distribution, metabolism, and elimination
of chemicals in human and animals
 Organisms in the surface water ecosystems may
 Ingest food containing a particular chemical
 Absorb the chemical from the water
 Organisms subject to elimination or transformation through
excretion, metabolism, etc.
 Require considerable information on the rate of uptake,
transformation and excretion processes.
 Suitable for terrestrial systems
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3. Pollutant Interaction with Biota
 3.1.4 First-order Kinetics and Half-life

= or =

Half-time of the pollutant (t1/2) when


Ct/C0 = 0.5 =

or 0.5 = ⁄

0.693
or ⁄ =
C: The concentration of the pollutant [M/L3]
t: The time [T]
k: The rate constant [T-1]
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3. Pollutant Interaction with Biota

Example 4

The first order reaction rate constant of a herbicide is 0.002 h-1.


A lake of 100,000 m3 volume is treated with 12 mole of
herbicide.
1) What will be the concentration after 2 days and 20 days ?
Assuming no further input.
2) What is the half-life of the chemical?

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3. Pollutant Interaction with Biota

3.2 Fruits and Vegetables


 Direct deposition onto plant surface, then foliar uptake
 Uptake from soil via roots
 Uptake from air via foliage
For ALL uptake pathways, we need BCF for vegetation

Correlation between BCF and Kow


Log BCF = 1.5888 – 0.578 Log Kow
Or BCF is inversely proportional to 1/Kow0.5

Check Table 7 (Page 40) in Reference Material for soil-to-plant BCFs


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