Pollution of Lakes and Rivers
Chapter 9:
Persistent organic pollutants:
industrially synthesized chemicals
‘hopping’ across the planet
Copyright © 2008 by DBS
Contents
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The threat from persistent organic pollutants (POPs)
Estimating the accumulation, inventory, and diagenesis of chlorinated hydrocarbons in lake
Ontario
Historical trends in organochlorides in river basins: reading the records of influent river water
quality left in reservoir sediments
Ecological effects of deliberate releases of toxaphene to lakes
Determining the sources and pathways of PAH contamination of Lake Michigan
Tracking long-term contamination of PAHs: an example from a fluvial environment
The Global Distillation Hypothesis: long-range transport of organic contaminants to arctic and
alpine regions
Determining the distribution of PCB contamination from a local Arctic source
Persistent Organic Pollutants
The Threat from POPs
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POP – organic substances that persist
Relatively insoluble, resistance to breakdown, and potential to biomagnify
e.g. organochlorines, organobromines, perfluorinated acids, polycyclic
aromatic hydrocarbons.
Carpenter interview (6 mins):
http://www.loe.org/shows/segments.htm?programID=06-P1300050&segmentID=2
Persistent Organic Pollutants
The Threat from POPs
Convert 1000 mg L-1 to ppm (assume ρ = 1.00 g mL-1)
 1.00 g pollutant
1000 mg pollutant /L of H 2O
1000 mg

1 mg L-1 = 1 ppm
1 μg L-1 = 1 ppb
1 ng L-1 = ppt
  1.00 L H 2O  1000 g pollutant
 =
 
= 0.001 g/g x 106 / 106  1000 ppm
6
10 g H 2O
  1000 g H 2O 
Persistent Organic Pollutants
The Threat from POPs
Four defining characteristics:
1. Persistence – how long do they last and in what form?
2. Bioaccumulation and other biological processes –
how do POPs change, concentrate and magnify through food chains?
3. Toxicity – dose and response for acute or chronic affects
4. Volatility – transport pathways and degree of transport
Biomagnification and
Bioaccumulation
A chemical whose concentration
increases along a food chain is said
to be biomagnified
DDT concentration in Lake Ontario Trout
Biomagnification results from a
sequence of bioaccumulation steps
Persistent Organic Pollutants
The Threat from POPs
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Lake Ontario food web
Lake water PCB level is below level
of detection ~ppb
Gull egg PCB estimated X million
Persistent Organic Pollutants
The Threat from POPs
Persistent Organic Pollutants
The Threat from POPs
Legacy POPs
PCBs – polychlorinated biphenyls
DDT, DDD, DDE – dichlorodiphenyl_chloroethanes
Emerging POPs
PBDEs – polybrominated diphenyl ethers
PCNs – polychlorinated napthalenes
PFOS – perfluorooctanesulfonate
PFCs – perfluorinated compounds
Since quantitative data for POPs in
water supplies prior to late 1980s
is not available paleolimnological
studies are very useful
Persistent Organic Pollutants
The Threat from POPs
• 2004 Stockholm convention
• Outlaw the use of 9, limit and restrict use of 3
Source: EPA
Which lake is the terminal lake of the Gt. Lakes system?
Persistent Organic Pollutants
Lake Ontario
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POPs
Lake Ontario
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PCBs
DDT
Wong et al (1995) studied
PCBs and OCs in 5 cores
Four classes of POPs
Compared to 1989 work
peaks are now deeper
and broader (diffusion)
All decline after
1970 ban
Variation among cores
Mirex
HCB
Persistent Organic Pollutants
Lake Ontario
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POP inventories – vertically integrated sediment inventories (ng cm-2)
Normalize against 210Pb - suggests differences amongst sites is due to
accumulation rates
Implies only one source of POPs and/or POPs are distributed evenly throughout
the lake
White columns –
significant variation
among 5 cores
Black columns –
when normalized to
210Pb variation reduces
Persistent Organic Pollutants
Lake Ontario
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Compared to 1981 peaks are now deeper and broader (diffusion)
1981 study underestimates
PCBs
1990 study shows further
burial of PCB peak
POPs
Historical Trends in
Organochlorides in River Basins
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Rivers are difficult to study
(fast moving)
Use downstream reservoirs
Higher sedimentation rates
– finer temporal resolution
e.g. Van Metre (1997)
DDT ban 1972
Chlordane
ban 1988
Except for
termites
southwestern USA
Persistent Organic Pollutants
Ecological Effects
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Toxaphene:
Mixture of hundreds of similar substances (produced from chlorinated
camphene- pine tree product) was widely used after DDT ban in 70s
– purposefully applied since 1949 to extirpate undesirable fish
– extremely toxic
– restrictions were placed in 1982 and a total ban in 1990
Persistent Organic Pollutants
Ecological Effects of Deliberate Releases
Toxaphene to Lakes
Highest of
Treatment
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Undesirable effects
on non-target organisms –
assemblage shifted from smaller
to larger bodied taxa
e.g. water flea species ‘Bosmina’
drops since dec in fish lead to
increase in invertebrate predators
e.g. presence of C. americanus can
be used to infer fish decline
Miskimmin and Schindler (1994)
Alberta (Canada))
Persistent Organic Pollutants
Determining Sources + Pathways of PAH Contamination - Lake Michigan
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Sources: combustion,
oil tankers, refineries,
offshore drilling,
aluminum smelters,
creosote (railway ties)
Typically ng L-1
Larger PAH’s bioaccumulate
Carcinogens
PAH’s, PCBs and Mirex
implicated in devastation of
beluga Whales in the
St. Lawrence River
Persistent Organic Pollutants
Determining Sources + Pathways of PAH Contamination - Lake Michigan
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Lake Michigan
Major industry in SW
corner
N-S transect
Showed increase from
1900, decrease due to
shift in energy
(from coal to oil and gas
(site 70m showed sig. mixing
non-linear 210Pb plot so
should not be considered)
Simcik et al
(1996)
Higher accumulation rates in N basin due
to S to N particle transport
Persistent Organic Pollutants
Determining the Sources + Pathways of PAH Contamination - Lake Michigan
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210Pb
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Clear similarity between PAH
use and coal use supports
conclusion that PAH’s in
Lake Michigan are primarily
derived from coke and steel
production
normalized (focus
corrected) inventories
showed one major source
Persistent Organic Pollutants
Tracking Long-term Contamination of PAHs: an Example from a Fluvial
Environment
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Saguenay River/Saguernay Fjord junction (Quebec)
One of the worlds largest aluminum producers
Persistent Organic Pollutants
Tracking Long-term Contamination of PAHs: an Example from a Fluvial
Environment
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Saguenay River/Saguernay Fjord junction (Quebec)
One of the worlds largest aluminum producers
1926 1st smelter
1971 landslide
Smith and Levy (1990)
1950s expansion
Persistent Organic Pollutants
The Global Distillation Hypothesis
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Compounds concentration should be highest near point of release
– not true for POPs
Global fractionation (distillation) of pollutants
Deposited in different locations depending on physical properties
Hot Regions
– Since vapor pressure increases with temperature evaporation
increases in tropical areas
Cold Regions
– Condensation and adsorption onto atmospheric particles is favored
– Final resting places for mobile pollutants
Persistent Organic Pollutants
Wania and Mackay,(1993)
The Global Distillation Hypothesis
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VOC’s tend to move towards
cold climates as a result of their
lower vapour pressure at colder
temperatures
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POPs with higher volatilities and
lower temperatures of condensation
(Tc) should be transported farthest
Due to seasonal
temperature variations
most molecules undergo
successive cycles of
evaporation and
condensation
‘The Grasshopper Effect’
http://www.literacynet.org/polar/pop/html/project-pops.html
Persistent Organic Pollutants
Biological Funnels and Biovectors
Blais et al (2007)
Persistent Organic Pollutants
Summary
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A large number of man-made organic chemicals have been released into
the environment during the last 200 years
Many of these compounds have potentially serious side-effects
Environmental damage caused by these compounds has been increased
due to their ability to:
(i) biomagnify
(ii) be transported over large distances
Sediments allow us to track the trajectories and patterns of deposition long
before technology was available to measure them
References
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Betts-Piper, A.A. (2001) Chrysophyte stomatocyst-based paleolimnological investigations
of environmental changes in arctic and alpine environments. MSc Thesis, Department of
Biology, Queen’s University, Kingston.
Blais, J.M., Schindler, D.W., Muir, D., Kimpe, L., Donald, D. and Rosenberg, B. (1998)
Accumulation of persistent organochlorine compounds in mountains of western Canada.
Nature, Vol. 395, pp. 585-588.
Blais, J.M. and Muir, D.C.G. (2001) Paleolimnological methods and applications for
persistent organic pollutants. In Last, W.M. and Smol, J.P. (eds.), Tracking Environmental
Change Using lake Sediments, Volume 2, Physical and geochemical Methods. Kluwer
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Blais, J.M, Kimpe, L.E., McMahon, D. et al (2005) Arctic seabirds transport marine-derived
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Blais, J.M, Macdonald, R.W., Mackay, D., Webster, E., Harvey, C. and Smol, J.P. (2007)
Biologically mediated transport of contaminants to aquatic ecosystems. Environmental
Science and Technology, Vol. 41, pp. 1075-1084.
References
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Carignan, R., Lorrain, S. and Lum, K.(1994) A 50-year record of pollution by nutrients,
trace metals and organic chemicals in the St. Lawrence River. Canadian Journal of
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Christensen, E. and Zhang, X. (1993) Sources of polycyclic aromatic hydrocarbons to lake
Michigan determined from sediment records. Environmental Science and Technology, Vol.
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Christensen et al (2005)
de Wit (2006)
Eisenreich, S., Capel, P., Robbins, J. and Bourbonniere, R. (1989) Accumulation and
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Environment Canada and U.S. Environmental Protection Agency (1995) The Great
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References
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Evenset et al 2004 2005
Fernández, P., Vilanova, R.M., Martínez, C., Appleby, P.G. and Grimalt, J.O. (2000) The
historical record of atmospheric pyrolytic pollution over Europe in the sedimentary PAH
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Finney et al (2000)
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References
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Li and Macdonald (2005)
Liu et al (2005)
Lipiatou et al (1996)
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Macdonald et al (1998)
Miskimmin, B.M. and Schindler , D.W. (1994) Long-term invertebrate community response
to toxaphene treatment in two lakes: 50-yr records reconstructed from lake sediments.
Canadian Journal of Fisheries and Aquatic Sciences, Vol. 51, pp. 923-932.
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References
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Neff, J.M. (1985) Polycyclic aromatic hydrocarbons. In Rand, G.M. and Petrocelli, S.R.
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References
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Smith, J.N. and Levy, E.M. (1990) Geochronology for polycyclic aromatic hydrocarbon
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