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Source and fate of pollutants
3504ENV Marine Ecotoxicology
How many contaminants?
>130 million registered chemicals
(18,000 since the last lecture!!)
1060 possible chemicals
100,000 used daily
10,000 in environmental samples
45 priority chemicals
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Types of contaminants
Slot
Week 7
Week 8
Mon 1
1. Dioxins
10. Lead
Mon 2
2. PCBs
11. Mercury
Mon 3
3. Flame retardants
12. Cadmium
Wed 1
4. Insecticides
13. Arsenic
Wed 2
5. Herbicides
14. Nanoparticles
Wed 3
6. Hydrocarbons
15. Radioactive isotopes
Wed 4
7. Pharmaceuticals
16. Surprise guest
Wed 5
8. Personal care products
17. Surprise guest
Wed 6
9. Disinfection by-products
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What types of contaminants??
Others??
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Detergents and surfactants
GMOs
Plastics
Inorganic ions
Essential elements (Cu, Se, Zn, etc)
Natural toxins
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Detergents and surfactants
Detergent: water-soluble
cleansing agent
» Contain surfactants and other
additives
Surfactant: common additive
to reduce surface tension
» Environmental issues:
endocrine disruption, disruption
of mucosal membrane,
eutrophication, disruption of
photosynthesis
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GMOs
Genetically modified organism
» DNA altered in a non-natural way
Insect resistant crops:
» Reduce the need for insecticides
» BUT, toxic to non target insects
(e.g. bees, butterflies)
» Reduced biodiversity (monocrop,
fewer weed flowers)
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Plastics
Plastics
» Macro (plastic bags, rubbish)
» Micro (< 5mm; plastic beads in
cosmetics, broken down
macroplastic)
Direct ‘toxicity’
» Entanglement, interference with feeding
Indirect toxicity
» Plastic chemicals leaching from ingested plastic
» Plastics adsorb chemicals from environment and
transfer following ingestion
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Inorganic ions
Phosphorus and Nitrogen:
» Excess use from fertilizers can lead to eutrophication
Carbon dioxide (CO2):
» Greenhouse gas › global warming, ocean acidification
Nitrous oxide (NOx):
» Potent greenhouse gas, also leads to eutrophication
Sulfur compounds (S):
» Sulfuric acid and acid rain
Fluoride (F):
» A fine line between essentiality and toxicity
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Essential elements
Non-essential elements:
» Cd, Hg, Pb, etc
» No function in the body
» Can be toxic at low concs
Health
Essential elements:
» Copper, selenium, chromium, zinc, etc
» Important biological functions
» Toxicity above and below essential range
» Bio-regulated
Dose
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Natural toxins
Animal sources (venoms, poisons, etc)
» Specific to ‘prey’
Bacteria (e.g. cyanotoxin) dinoflagellate (e.g. brevitoxin) and
algae (e.g. saxitoxin) sources
» Not technically pollutants, but nutrient pollution can exacerbate these
Low O2
Nutrients
Harmful algal bloom
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Fish kills
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Sources of contaminants
Natural
» Fires (dioxins), weathering of bedrock (metals)
Deliberate release
» Pesticide use
Industrial operation
» Coal plants, wastewater discharge
Accidental
» Oil spills, shipwrecks
Secondary
» Land fill leachate
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http://community.titantv.com/blogs/lizadeguia/gyre.gif
Even the most remote parts of
the Earth…
http://www.independent.co.uk/independent.co.uk/editorial/p1Ima
ges/20080205_p1_big.jpg
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Point source vs diffuse sources
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Pulse vs press release
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Pulse disturbance
Transient in time and space
http://www.theartofdredging.com/rainbowing.htm
The Age
Dredging plume due to sand extraction,
Port Philip Bay
‘Rainbowing’
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Press disturbance
Can still have some daily periodicity in
discharge intensity (e.g. sewage outfall)
Sewage outfall at Luggage Point, Brisbane
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Environmental factors?
N pollution from sewage treatment plants
September 1997
February 1998
3504ENV - Source and fate of pollutants
Costanzo et al. (2011)
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Fate of contaminants
Transport & Migration
Remobilization
Degradation
Degradation
Bioaccumulation -magnification
Sequestration
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Fate of contaminants
Depends on properties of the chemical
» Lipophilicity
» Persistence
» Volatility
Depends on prevailing environmental
conditions
» Temperature
» pH
» Wind speed and direction
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Persistence
Highly persistent contaminants:
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Do not degrade or metabolise easily
Can be present for years, decades, centuries
Can undergo many transport cycles during their lifetime
Accumulate to higher concentrations over time
Measured in half-life (in soil, air, water):
» e.g., in soil
>365 days: very persistent
100-365:
persistent
30-100:
moderately persistent
permanent fishing ban throughout Sydney Harbour
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Dioxins in Moreton Bay
• Dioxin
concentrations
relatively high
• Distribution
influenced by
sediment
movement,
bathymetry,
hydrology, benthic
cover
•Brisbane
pg/g PCDD/F dry weight
7
2000
8100
Hermanussen et al 2004
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Dioxins & PCBs in marine turtles
West
West2
East
100
Moreton Bay
80
60
Shoalwater
PCDD/F TEQ (pg/g lipid)
120
40
20
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Pesticides and herbicides in GBR
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Pesticides and herbicides in GBR
A focus on
chemical analysis
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Methods for chemical analysis
Grab samples
» 1L water samples collected in bottles
» “Snapshot”: 1 point in time
» Solid phase extraction
Passive samplers
» Time integrated (e.g. Empore disks)
» 1-3 months deployment
Quantification by GC/LC/HPLC-MS/FID
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Sampling
Routine and
event based
sampling
Passive sampling
at all sites
Snapshot
sampling during
events (flood)
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Snap-shot sampling (temporal)
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Snap-shot sampling (spatial)
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Passive sampling
Time weighted average
Biologically available (dissolved)
Days or months
DGT
Chemcatcher
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SPMD
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Chemical analysis
Many ways to do this
GC/FID
LC/MS
GC/MS
Essentially 2 steps:
HPLC/MS
LC/FID
» Separation (chromatography)
» Detection
You only find what you
are looking for
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Chemical analysis
120
Concentration
100
80
60
40
20
0
Contaminant
Low contaminant
concentrations
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Bioassays
Cytotoxicity
Assess the mixtures
Oxidative stress
DNA damage
Endocrine disruption
Bioassay
extraction
Blood extract
(chemical mixture)
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Bioassays
100.0
% effect
75.0
55.0
50.0
25.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
0.0
Backhaus et al. (2008) in Kummerer (Ed.) Pharmaceuticals in the Environment, pp. 257-276
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Bioassays
Mode of
toxicity
Endpoint
Mechanism
Bioassay
Non-specific
Basal cytotoxicity
Cytotoxicity to gastro-intestinal cells
Caco2-NRU
Basal immunotoxicity
Cytotoxicity to white blood cells
WIL2NS TOX
Basal hepatotoxicity
Cytotoxicity to liver cells
HepaTOX
Mutagenicity
Mutagenic potential
Ames TA98 and TA100
Genotoxicity
Micronucleus formation
WIL2NS FCMN
Hepatotoxicity
MFO induction in liver cells
HepCYP1A2
Endocrine
interference
Estrogenic and anti-estrogenic activity
ERα-CALUX
Endocrine
interference
Androgenic and anti-androgenic activity
AR-CALUX
Endocrine
interference
Glucocorticoid-like activity
GR-CALUX
Neurotoxicity
Inhibition of acetylcholinesterase
AChE assay
Reactive
Specific
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But…..
What are the effects of these contaminants????
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Take-home message
Types of contaminants (more coming in the student
presentations)
Source of contaminants
Fate of contaminants
» Sequestration and decomposition
» Bioaccumulation and biomagnification
» Transport
Chemical pollution in Australia
Measuring pollution
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..000 vodafone AU
9:51 pm
bblearn.griffith.edu.au
Mon 2
Mon 3
Wed 1
Wed 2
Wed 3
Wed 4
2. PCBs
3. Flame retardants
4. Insecticides
5. Herbicides
6. Hydrocarbons
7. Pharmaceuticals
8. Personal care products
9. Disinfection by-products
11. Mercury
12. Cadmium
13. Arsenic
14. Nanoparticles
15. Radioactive isotopes
16. Surprise guest
17. Surprise guest
Wed 5
Wed 6
UNIVERSITY
3504ENV. Feedback + presentations
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Example structure for your talks
Scene setting / context
What is it? Where does it come from? When was it
discovered to present a environmental problem?
• Environmental occurrence
>> How much of it is there in the environment? What is its
fate? How can it be removed?
» How does it affect living organisms?
• Case studies
» Provide a few cases studies, and put it into context of our
modern society
. The take home message is ...
Griffith
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3504ENV - Feedback + presentations
UNIVERSITY
Research
.
• NOT Wikipedia!!
Google Scholar (recent)
• Journal databases (e.g. Scopus)
- Use primary references (and reviews)