Contaminants: Budgets and Behaviours

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Contaminants Budgets and Behaviours Contaminant
passage through the land-ocean interface as seen
by ELOISE and IMPACTS
Kevin Barrett, Knut Breivik, Torunn Berg Jozef
Pacyna Norwegian Institute for Air Research
(NILU)
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1. Introduction

• Anthropogenic and biogenic contaminants

• 4 broad contaminant groups have been considered
• 1. Persistent organic pollutants (PCBs) and
  hydrocarbons
• 2. Mercury
• 3. Heavy metals
• 4. Biogenic gases

• 3 principle transport pathways in and out of
  coasts
• 1. Rivers
• 2. Atmosphere
• 3. Ground and sediment water

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2. Fluvial Supply of contaminants to the coast
COMETEUROCAT
EROS-21
TOROS, METROMED

Metal contamination, Mediterranean - S. Spain
Metal contamination, North Sea
Contaminants in Black Sea
Metal mining legacy

• Mercury concentrations into the Bay of Cadiz -10x
  greater than those transported by the Seine to
  the Normandy coast.
• Rio Tinto much more heavily metal laden river
  than mine impacted rivers in UK.

• Chronic release (2500 years)
• Mine drainage
• Phosphogypsum waste runoff
• Acute discharge

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3. Atmospheric pathways of contaminants from
land to sea
Even where there are high river loads of metals,
the atmosphere is a major pathway. (TOROS
project)
Deposition across the air-sea interface is the
main route of supply of persistent organic
pollutants (POPs). (POPCYCLING-Baltic project)
Relative importance () of riverine and
atmospheric supply of lindane ( y-HCH) to various
parts of the Baltic Sea (Breivik Wania, 2002)
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3. Atmospheric pathways of contaminants from sea
to land
? Marine emissions of sulphur to the atmosphere
are as dimethylsulphide (DMS). ? Phytoplankton
are primary determinants of DMS concentrations in
seawater. ? ELOISE projects imply greater coastal
contribution to emissions than previous estimates
Potential for coastal emissions of
dimethylsulphide to the atmosphere.
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5. Ground and sediment waters
The attention to groundwater flows by ELOISE and
IMPACTS has been restricted, but illuminating
SUBGATE Project

• Contaminant deposits to terrestrial surfaces can
  emerge many decades later in coastal waters
  after transmission through groundwaters.
• CFCs used as tracers and observed in groundwaters
  below the Kiel Bight suggest re-emergence of
  waters of terrestrial origin in the Baltic after
  over 50 years.

EROS-21 Project

• Examined the transfer of compounds from sediments
  to the water column, and further to shelf
  sediments and to the deep water sediments.

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Case Study 1 PCBs in coastal zones (1)

• Polychlorinated biphenyls (PCBs)
• Group of halogenated organic substances.
• Frequently assigned to larger group of
  persistent organic pollutants (POPs).
• Commercially produced for various applications
  since the 1930s.
• Known global mass production of PCBs virtually
  ceased in 1984.
• Production in the former Soviet Union, which
  ended in 1993.
• Worldwide, gt 1.3 million tonnes of PCBs have
  been intentionally produced (Breivik et al.
  (2002a)).
• PCBs are of great environmental concern
• They are lipophilic (bioaccumulative).
• Occur to a significant extent in the gas phase
  and condensed states (semi-volatile) are toxic as
  well as persistent.

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Case Study 1 PCBs in coastal zones (2)

• Issues of concern
• Human exposure to PCBs tends to be significantly
  controlled by consumption of seafood, such as
  fatty fish.
• Potential remobilisation of PCBs from
  contaminated sediments. (Larsson, 1985)
• Potential threat for further uptake in biota for
  decades to come because of the long response time
  of sediments to loading reductions.

Breivik et al. (2002a)
Estimated cumulative usage of PCBs in tonnes
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Case Study 1 PCBs in coastal zones (3)
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Case Study 1 PCBs in coastal zones (4)
Environmental cycling and fate of PCBs in the
coastal environment

• Sources, fate and transformation of PCBs in the
  NW Black Sea studied by Maldonado
• Bayona (2002).
• Found that PCBs introduced to surface waters tend
  to be taken up by phytoplankton, with
  consecutive rapid sinking in sorbed state and
  degradation along the water column.

POPCYCLING- Baltic model

• Multi-compartmental model to describe the fate of
  PCBs in the Baltic Sea. Wania et al. (2001)
• Provides invaluable insight into the complex set
  of interactions that determine the overall fate
  of POPs in the Baltic Sea drainage basin but
  which are inaccessible to measurements.

Quantifcation of the pathways of POPs from
terrestrial environment to marine environment via
atmosphere and rivers (Wania et al. (2000)).
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Case Study 2 Mercury in the Mediterranean (1)

• Mercury
• Occurs naturally as elemental mercury as
  organic and inorganic species.
• About half of worlds mercury resources are
  located in the Mediterranean area.
• High levels of mercury are found in
  Mediterranean tuna anchovy sardines.
• A large fraction of mercury is strongly bound
  to sediments and organic matter
• thus unavailable to organisms.
• Microorganisms can transfer inorganic mercury
  to methylmercury.
• Methymercury
• Fat soluble.
• Able to pass cell membranes.
• Accumulates in animals.
• Biomagnifies in the food web.

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Case Study 2 Mercury in the Mediterranean (2)
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Case Study 2 Mercury in the Mediterranean (3)
Sources of mercury in the Mediterranean

• Cinnabar represents the principal ore containing
  mercury.
• Mercury from Almaden (Spain), Idrja (Slovenia)
  and Monte Amiata (Italy) has been exploited
  since ancient times for gold and silver
  extraction.
• A significant increase in mercury emission to the
  atmosphere occurred during the industrial
  revolution due to fossil fuel combustion and
  other human activities.
• Main anthropogenic sources today
• ? Processing of mineral resources at high
  temperatures
• ? combustion of fossil fuels
• ? roasting and smelting of ores
• ? kiln operations in cement industry
• ? incineration of wastes and production of
  certain chemicals.
• (Pacyna et al. (2001) Pirrone et al. (2003))

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Case Study 2 Mercury in the Mediterranean (4)
MAMCS MOE Projects
Observed concentrations of total gaseous mercury
(TGM), particulate mercury (TPM), and reactive
gaseous mercury (RGM) were generally slightly
higher in the Mediterranean region than in
Northwest Europe (Wangeberg et al. (2001)).
Med-Oceanor Project
Studied for the spatial and temporal
distributions of mercury species along a 6000 km
cruise path in the western and eastern sector of
the Mediterranean Sea.
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Key references (1)
Breivik et al. (2002a) Towards a global
historical emission inventory for selected PCB
congeners a mass balance approach. 1. Global
production and consumption. The Science of the
Total Environment 290 181-198. Breivik Wania,
(2002) Mass Budgets, Pathways, and Equilibrium
States of Two Hexachlorocyclohexanes in the
Baltic Sea Environment. Environmental Science
Technology 36 1024-1032. Larsson, 1985
Contaminated sediments of lakes and oceans act as
sources of chlorinated hydrocarbons for release
to water and atmosphere. Nature 317 (26)
347-349. Maldonado Bayona (2002)
Organochlorine Compounds in the Western Black
Sea.- distribution and water column processes.
Estuarine Coastal and Shelf Science 54 (3)
527-540. Pacyna et al. (2001) European emissions
of atmospheric mercury from anthropogenic sources
in 1995. Atmospheric Environment 35
2987-2996. Pirrone et al. (2003) Dynamic
Processes of Mercury Over the Mediterranean
Region Results from the Mediterranean
Atmospheric Mercury Cycle System (MAMCS) Project.
ELOISE Special Issue. Atmospheric Environment
37(S1)21-39.
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Key references (2)
Wangeberg et al. (2001) Atmospheric Mercury
Distribution In Northern Europe and in the
Mediterranean Region. Atmospheric Environment 35
3019-3025. Wania et al. (2000) The
POPCYCLING-Baltic Model. A Non-Steady State
Multicompartment Mass Balance Model of the Fate
of Persistent Organic Pollutants in the Baltic
Sea Environment. NILU OR 10/2000. ISBN
82-425-1159-4 Kjeller, Norway. 81 pp. Wania et
al. (2001) A multi-compartmental, multi-basin
fugacity model describing the fate of PCBs in the
Baltic Sea. In Wulff F., Larsson P., Rahm L
(eds.). A System Analysis of the Changing Baltic
Sea. Springer-Verlag, Heidelberg. pp 417-447.