Jones Kevin

Is the Stockholm Convention working?
Observations from temporal and spatial
trend studies
Kevin C Jones
Lancaster Environment Centre,
Lancaster University,
Lancaster, UK
Acknowledge collaborators…
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Lancaster team, past and present
Luca Nizzetto, Knut Breivik & Eiliv Steinnes, Norway
Jordi Dachs & Joan Grimalt, Spain
Tom Harner, Don Mackay, Terry Bidleman, Canada
Antonio Di Guardo, Italy
Rainer Lohmann, USA
Matt MacLeod & Martin Scheringer, Thomas Bucheli, Sweden and
Switzerland
Euripides Stephanou & Manolis Mandolakis, Greece
Till Gocht, Ralf Ebinghaus & colleagues, Germany
Ivan Holoubek & Jana Klanova, Czech Republic
Shinsuke Tanabe, Japan
Gan Zhang, Jun Li, Xiaoping Wang, Paromita Chakraborti, Chinese
Academy Sciences, China
Outline of the talk
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Conventions, POPs and Stockholm
Some observations on past trends (time)
What are they telling us?
Current global picture (space)
What about the future?
Future challenges
Some comments on controls
• Controls on pollutants and emissions can be
‘voluntary’ with industry, guidelines, national
regulations, international (e.g. European), or
global
• Global issues – examples:
– CFCs and ozone depletion; Montreal
– Carbon dioxide, greenhouse gases; discussions Kyoto and Copenhagen
– POPs; Stockholm
• Motivated to reduce emissions, levels, impacts
GLOBAL CFC PRODUCTION
Note CFC production stopped quickly….
Montreal protocol
1987
1989
Changes in ozone : past, present and
the future with Montreal
From Newman et al Atmos. Chem. Phys., 2009
Antarctic ozone hole
(millions of square km))
35
30
Montreal protocol
1987
1989
With
Montreal:
recovery
by 20502080
25
20
15
10
5
0
1970
1980
1990
2000
2010
Global agreements can
solve global problems!
Work doesn’t stop on
signing
BLUE= low
ozone
UNEP – Stockholm Convention on POPs
May 17, 2004
Obligations – inventories and ‘effectiveness’ of reductions
• monitoring data
• regional and global environmental transport
How do we know if a Convention is working?
‘Effectiveness evaluation’
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Requires good quality trend data
An understanding of past and present levels
Key media – air, biota/humans, waters?
Need to be able to say ‘what is the trend’, against ‘noise’
We need to know if actions are working or not, as a
research community and as the policy makers - this
informs decision-making!
• Need to be able to interpret the trends (or lack of
them…) we see (Frank W)
It sounds simple, but why is it
complicated?
• POPs analysis is difficult; we have not been
measuring POPs well enough for long enough
• Looking back in time is subject to sampling/alteration
artefacts
• Change can be slow because POPs are POPs
• Very few good quality long-term trend sets exist but
they are so important (and are of limited
geographical spread)
• These (largely) rely on national monitoring budgets
for continuity and/or dedicated researchers
What would we expect to happen if the
SC is working?
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A fascinating question – very complicated
Timing and magnitude of changes in sources/stocks?
Differences between media? Air, water, soil, biota…
Differences between chemicals?
Differences between locations?
Lag phases between ‘action’ and ‘response’?
Expect a faster rate of change (decline) than before
the SC (although even this could be disputed)
As the world moves from ‘primary
source controlled’ to ‘secondary
source controlled’ – would we see
different rates of change?
Control will be a function of
environment (location) and
chemical properties
LAND
OCEAN
ARCTIC
The key science issue for regulators…
Primary Sources
Major Point
Sources Controllable
Diffuse Sources
Secondary Sources
Legacy Usage /
Dumps/Contam
Land ‘Old’ sources
Pool of POP which
re-cycles (hops)
through the environment
‘Recent’ sources
?
Predatory bird monitoring since 1960s
Marine, freshwater and terrestrial food chains
VERY important – early warning of effects on eggshells; first detection of PCBs
Trends of old POPs & archive for new POPs
PM examination
liver concentration (µg/g)
Volunteer submission
10
DDE
Data analysis and publication
note ‘plateau’
8
6
4
2
0
1960
1970
1980
1990
2000
Sample archive
Chemical analysis
10000
sum PCB-TEQ (pg/g wet wt.)
congener sum (µg/g wet wt.)
10
1
0.1
1970
1980
1990
2000
2010
1000
100
10
1
0.1
0.01
ND
1995
2000
2005
2010
Year
100
10
mercury (µg/g dry wt.)
sum Paris 10 PCBs (µg/g wet wt.)
Year
10
1
0.1
0.01
ND
1
0.1
1995
2000
2005
Year
2010
1970
1980
1990
2000
Long-term trends in liver congener sum PCB, Paris 10 PCB, sum PCB-TEQ and HgYear
concentrations in
Eurasian sparrowhawk (Accipiter nisus). Dots are concentrations in individual livers, and the triangles
are annual median values with a connecting line. Congener sum concentrations prior to 1999 are
estimated based on Total PCB concentrations
2010
Rothamsted Agricultural Station, UK
Experiment started in 1856
Removing samples
for analysis 1930
Harvesting in 1941
PCDD/F s – temporal trend
3000
3000
2500
2500
2000
2000
1500
1500
1000
1000
500
500
0
0
Studies showed:
Stockholm Convention
PCDD/Fs pre-date the ‘chlorine industry’
Sources have varied over time
Trends put recent levels in context
Important data during European discussions about ‘zero emissions and exposure’
PCDD/Fs in air
fg TEQ m-3
TOMPS average air concentrations
19
0
19 3
3
19 0
4
19 0
5
19 0
6
19 0
6
19 1
6
19 2
6
19 3
6
19 4
6
19 5
6
19 6
6
19 7
6
19 8
6
19 9
7
19 0
7
19 1
7
19 2
7
19 3
7
19 4
7
19 5
7
19 6
7
19 7
7
19 8
7
19 9
8
19 0
8
19 1
8
19 2
8
19 3
8
19 4
8
19 5
8
19 6
8
19 7
8
19 8
8
19 9
9
19 0
9
19 1
9
19 2
9
19 3
9
19 4
9
19 5
9
19 6
9
19 7
9
19 8
9
20 9
0
20 0
0
20 1
0
20 2
0
20 3
0
20 4
0
20 5
0
20 6
07
PCDD/Fs in herbage in
fg TEQ g-1
(21)
Herbage concentrations (Hassanin et al. 2006)
Toxic Organic Micro-Pollutants program
Middlesbrough
1993 - 2008
Hazelrigg
1993 - ongoing
Manchester
1991 - ongoing
High Muffles
1999 - ongoing
Stokes Ferry
1999 - 2007
London
1991 - ongoing
High volume air
samplers at six
urban & rural sites
monitoring
PCBs
PCDD/Fs
PAHs
PCB concentrations – UK air
Monitoring started 1990
9
y = -0.2133x + 432.06
R² = 0.6876
y = -0.1089x + 222.95
R² = 0.5705
Stokes Ferry
y = -0.1401x + 284.39
R² = 0.6437
High Muffles
8
Hazelrigg
Middlesbrough
7
Manchester
London
6
log SPCB
5
Half-live trends not significantly
different between sites
4
UK atmospheric clearance of
PCBs with an average half-life is
4.7 ± 1.6 years
3
2
1
0
1990
-1
y = -0.2092x + 421.92
R² = 0.3896
1995
y = -0.2366x + 476.96
R² = 0.4529
2000
y = -0.1791x + 361.95
R² = 0.5938
2005
2010
Rate of decline not changed
Hites – Great Lakes = 18 years.
PCB concentrations – temporal trend
Trends on herbage for
1965 – 1989 not
different to trends for air
data for 1991 – 2008
10000
Herbage
Air
1000
Declines started from
late 1960s – with
voluntary bans (after
reports in birds of prey
etc)
log SPCB
100
10
Has Stockholm made any
difference?
1
Rate of decline
controlled by release
from stocks? Advection?
0.1
0.01
1960
1970
1980
1990
Year
2000
2010
Passive Air Sampling in
space and time…
Transect UK and Norway, 50 – 70N, important
results…
All PCB congeners at all sites, decline at same rate.
Fractionation pattern with latitude
remained consistent over time
Interpretation…
1994 – 1996
PRIMARY SOURCES
AND FRACTIONATION
WITH DISTANCE
FROM SOURCES
EXPLAINS RESULTS
1998 – 2000
2000 – 2002
2002 – 2004
2004 – 2006
2006 – 2008
Jaward et al - Europe
Zhang et al - Asia
Klanova, Holoubek et al
– E and C Europe
GAPS
Global Atmospheric
Passive Sampling
Study
Harner, Pozo et al - GAPS
Major regional and global scale sampling campaigns
Development of cheap passive sampling methods
Many groups are ‘data gathering’ now
Antarctica
Updated : August 2006 (Tom)
DDT…
Primary Sources
Major Ongoing
Sources Controllable
YES
Diffuse Sources
Secondary Sources
Legacy Usage /
Dumps
‘Old’ sources
Pool which re-cycles
through the environment
‘Recent’ sources
YES
?
PCBs…
Primary Sources
Major Point
Sources Controllable
Secondary Sources
Diffuse Sources
Legacy Usage /
Dump ‘Old’ sources
Pool which re-cycles
through the environment
‘Recent’ sources
YES
YES
YES
?
HCB…
Primary Sources
Major Point
Sources Controllable
Diffuse Sources
Secondary Sources
Legacy Usage /
Dump ‘Old’ sources
Pool which re-cycles
through the environment
‘Recent’ sources
YES
YES
?
Shifting attention – China and India
Chinese Academy of Sciences (Knut Breivik presentation)
Shifting our attentions – China and India
Chinese Academy of Sciences (Knut Breivik presentation)
‘Factories of the world’
Extensive receivers and handlers of waste
Chemicals management here will have global impacts
Trying to assess time trends here too – are they different from Europe?
Tanabe’s group – Japan, also other regions of Asia
SHIPYARDS
A typical merchant ship to be dismantled for scrap contains
between 250 kg – 800 kg of PCBs, which is found principally in
the paint as well as in the vessel machinery
India is growing at an exponential rate in terms of electronic
waste, generating approximately 150,000 t/year, much of which
is stockpiled or poorly managed
Soil sampling in the UK and Norway in 1998 and 2008
PCB loads on soil organic matter (SOM)
Soil sampling in the UK and Norway in 1998 and 2008
Enantiomer fraction (EFs) for PCB 95 and PCB 149
for 2008 soil samples and 2006-2008 air data
1
0.8
EF PCB 149 (+) in Soil
EF PCB 95 (E1) in Soil
EF PCB 149 (+) in Air
EF PCB 95 (E1) in Air
EF
0.6
racemic
0.4
0.2
0
1
2
3
4
5
6
7
8
Passive air sampling site
9
10
11
Soil sampling in the UK and Norway in 1998 and 2008
Idealized plots of log PCB against log SOM for the homologue groups
for 1998 and 2008 highlighting the deviation for the slopes in 1998
1
4CBs in WL 1998
Log PCB
0.8
0.6
0.4
0.2
60% SOM
0
-1
-0.8
-0.6
-0.4
Log SOM
-0.2
0
Soil sampling in the UK and Norway in 1998 and 2008
Idealized plots of log PCB against log SOM for the homologue groups
for 1998 and 2008 highlighting the deviation for the slopes in 1998
1
4CBs in WL 1998
8CBs in WL 1998
Log PCB
0.8
0.6
0.4
0.2
40% SOM
60% SOM
0
-1
-0.8
-0.6
-0.4
Log SOM
-0.2
0
Soil sampling in the UK and Norway in 1998 and 2008
Idealized plots of log PCB against log SOM for the homologue groups
for 1998 and 2008 highlighting the deviation for the slopes in 1998
1
4CBs in WL 1998
8CBs in WL 1998
all PCBs in WL 2008
Log PCB
0.8
0.6
0.4
0.2
40% SOM
60% SOM
0
-1
-0.8
-0.6
-0.4
Log SOM
-0.2
0
Carlson et al., 2010 …
… reported a change in
temporal trends of the
decline of persistent
organic pollutants (POPs)
in lake trout observed by
the Great Lakes Fish
Monitoring Program
(GLFMP).
Concentration [ng/g wet weight]
[log scale]
From the 1980s half-lives start increasing
PCB and DDT half-lives
until 1980s:
from 1980s on:
3 – 6 years
~ 15 years
What does this reflect? Move towards secondary source controls?
Condition of ‘temporal remote state’ – Scheringer group in Zurich
Such data is very important to continue and to understand!
Effectiveness evaluation – so far
• Long times for POPs to decline…
• All started before Stockholm with steady declines
• Some POPs (e.g. pesticides) – use can be banned
and there is an environmental stock (e.g. soil) which
controls global trends
• Others (e.g. PCBs) have stocks from past uses and
wastes which disappear very slowly
• Others (e.g. PCDD/Fs; PAHs) have long-term past
sources and continuing ‘difficult to control sources’
• As with Montreal/CFCs - control, regulate and wait?
Some thoughts
• Clear science need - good data, long-term trends, Biobanks
and archives
– Few exist – Sweden, Germany, UK, Japan, US, Canada - many
under financial pressures - very important that more are
established
• All show declines occur before Stockholm came into force…
• How is Stockholm affecting other parts of the world – not
Europe and North America…? This is critical and we just
don’t know enough to say.
• Knowledge of processes is essential – not just monitoring
Some (more) thoughts
• ‘Early warning’ of problems was essential – voluntary bans
and national controls were effective
• Need to be able to explain the ‘added value’ of Stockholm?
• When have scientists and regulators ‘done enough’?
• Chemicals management has a much broader range of
challenges and perspectives – resource management,
sustainability agenda, impacts.
Acknowledgements
Many research group members and
international collaborators
The Chemicals and Nanotechnologies
Division of Defra - UK for funding