RECETOX, Masaryk University, Brno, CR
holoubek@recetox.muni.cz; http://recetox.muni.cz
Ivan Holoubek
CHEMIE ŽIVOTNÍHO PROSTŘEDÍ IV
Vybrané typy environmentálních polutantů
(04/05)
Persistentní organické polutanty (POPs)
Persistentní, bioakumulativní a toxické látky (PBTs)
Persistentní toxické látky PTS
Mezinárodní úmluvy
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Stockholm Convention
Stockholm, Sweden, May 22-23, 2001
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Persistent Toxic Substances
CCl Cl
CCl3
H
 Persistent
 Bio-accumulative
 Toxic
 Transboundary movement
 POPs a sub-group
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Persistent
 Resists degradation in the environment
 Other chemicals, even though degrading faster in the
environment, are persistent due to continuous release
Stockholm Convention
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Bio-accumulative
 Concentrates in fatty tissue (lipophilic)
 Bio-accummulation factor in animals dependent on the log
Kow – a measure of the affinity of chemicals to lipids
 Chemicals to be included – log Kow > 3 but molecular weight
< 1 000 Daltons
 Chemical accummulates up the food chain
Stockholm Convention
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Toxicity
 Chemicals show chronic toxicity properties including:
developmental, reproductive, carcinogenic, immunotoxic and
neurotoxic activities in humans and wildlife
 ADI values are compared to NOEL/LOEL values to
establish risk from exposure
 Substances with acute toxicity and with continuous
release/exposure to be considered
Stockholm Convention
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Transboundary Movement
 Chemicals transported through erosion, flood plains,
water, biota etc.
 Chemicals are semi-volatile
 Evaporate over warmer regions and condense in colder
atmospheres
 Can affect regions where use is non-existent
Stockholm Convention
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The objective of the Stockholm Convention is to protect human
health and the environment from persistent organic
pollutants. It differentiates between three categories of
POPs:
 Intentionally produced POPs that are slated for elimination;
 Intentionally produced POPs are to be reduced and ultimately eliminated,
except where there is a specified “acceptable purpose,” such as disease
vector control, or exempted usage, in which case the production and/or
use of the substance is restricted; and
 POPs that are unintentionally produced as the result of human activity
and which are slated for continued minimization and, where feasible,
ultimate elimination of total releases derived from anthropogenic sources.
www.pops.int
The objective of the Stockholm Convention
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Pesticide Industrial Chemical By-product
Aldrin +
Chlordane +
DDT +
Dieldrin +
Endrin +
Heptachlor +
Mirex +
Toxaphene +
Hexachlorobenzene + + +
PCB + +
PCDD +
PCDF +
12 old Stockholm POPs
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Pesticide Industrial Chemical By-product
Chlordecone +
HBB +
a-HCH + +
b-HCH + +
g-HCH + + +
PeDBE + +
OCBDE + +
PFOS +
PeCBz + + +
Endosulfan +
10 new Stockholm POPs
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ALDRIN DIELDRIN ENDRIN
DDT CHLORDAN HEPTACHLOR
Old Stockholm POPs
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HCB MIREX TOXAPHEN
PCBs PCDDs PCDFs
Old Stockholm POPs
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POPs
Stockholm Convention
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Nástroje Stockholmské úmluvy
Národní POPs Inventura ČR – 2002
– 2009
Národní implementační plán SÚ v
ČR - 2004
Hodnocení účinnosti opatření
SÚ – Globální POPs
monitoring
Globální a regionální monitoring
POPs ve volném ovzduší
(aktivní a pasivní vzorkování;
mateřské mléko
Národní a regionální POPs Centra pro implementaci závěrů SÚ
na národní a regionální úrovni
Národní síť monitoringu
POPs ve volném
ovzduší ČR –
MONET-CZ,
MONET Region +
MONET-Europe,
MONET-Africa
POP Review Committee – hodnocení
nových kandidátských POPs
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Národní implementační plán
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162004 2006 2008 2010 2012 2014 2016 2018
“Enabling
Activities”
National Implementation
Plan
1st effectiveness
review
CoP 1
Příprava NIP – politický proces
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Hlavní strategické cíle NIP
 eliminace vstupů POPs do prostředí a snížení expozice
člověka těmito látkami;
 odstranění starých zátěží spojených s dřívější produkcí,
používáním, distribucí a odstraněním POPs;
 nezbytně nutná je podpora dobudování zařízení ke sběru
odpadů s obsahem POPs ev. dalších nebezpečných látek,
kde tyto budou shromažďovány a skladovány
environmentálně bezpečným způsobem do doby, než bude
možné zajistit jejich odstranění s maximálně možným
využitím existující sítě těchto zařízení;
 aplikace principů BAT/BEP (Best Available Techniques/
Best Environmental Practices) v rámci strategie rozvoje
průmyslu v příštích letech;
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Hlavní strategické cíle NIP
 vypracování komplexních plánů odstranění odpadů
s obsahem POPs včetně zhodnocení dopadů různých variant
na životní prostředí a zdraví lidské populace;
 získání dalších dat potřebných k objektivnímu
zjištění velikosti zatížení POPs ve vybraných oblastech –
zpracování inventur vstupů do všech složek životního
prostředí, produktů a odpadů pro všechny látky na Seznamu
Úmluvy a PAHs,
 optimalizace monitorovacích programů jednotlivých resortů
s cílem realizovat úkoly dané Úmluvou.
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Časový plán implementace
 Distribuce Národního implementačního plánu všem
zainteresovaným institucím po jeho vzetí vládou na vědomí.
 Vytvoření Národního POPs Centra a monitorovacího výboru
implementace Úmluvy do 1 roku od vzetí Národního
implementačního plánu vládou na vědomí.
 Splnění krátkodobých cílů stanovených Národním
implementačním plánem do tří let od vzetí vládou na
vědomí.
 Vyhodnocení plnění krátkodobých cílů a aktualizace
Národního implementačního plánu do září 2009.
 Splnění dlouhodobých cílů stanovených Národním
implementačním plánem do deseti let od vzetí plánu na
vědomí.
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 Destrukční kapacita
 Látky – PAHs, SCCPs, Br
Nové lokality
 Potraviny
 Vyhodnocování, práce s informacemi
 Preventivní činnost
Národní POPs priority
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Identification of
the need to
review or update
NIP
Initiate process to
review/ update
NIP
Coordinating
mechanism
and process
organization
Assessment of the
effects
of the external/
internal triggering
factors
Formulation of
revised/Updated
NIP
Endorsement
Transmission
Elaborated process for reviewing and updating NIP
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Timeline for NIP review and update
17 May 2004
Entry into force of
the Convention
17 May 2006
Due date for
transmission of
NIPs of first 50
Parties
26 August 2010
Entry into force of
amendments to
Annexes A, B and C
of the convention
26 August
2012
Due date for
transmission of
revised and
updated NIP
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Národní POPs inventura
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GENASIS 1.0 - http://www.genasis.cz
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Národní POPs Centrum
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Národní POPs Centrum ČR (NC)
Založení NC je realizováno rámcovou smlouvou mezi MŽP a MU
Brno.
Centrum je zaměřeno na realizaci úkolů NIP, implementaci SÚ a
dalších úmluv souvisejících s chemickými látkami.
NC bude úzce spolupracovat s řadou předních pracovišť ČR a sítí
externích expertů, jenž se podíleli na přípravě Národní POPs
inventury a vytvoří tak vhodnou platformu pro realizaci NIP.
NC představuje odbornou základnu, jejímž cílem je přispět
k porozumění problematice POPs v podmínkách ČR,
informování a interpretaci problémů spojených s těmito
látkami v naší zemi a zvýraznit skutečnost, že ČR má
dostatek odborných kapacit, dat i informací pro seriózní a
kvalifikovaný přístup k dané problematice.
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Komise pro hodnocení nových POPs
(POPs Review Committtee)
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Persistent Organic Pollutants Review Committee
(POPRC)
 Subsidiary body to the Convention, mandated to review
proposals submitted by Parties for listing new chemicals in
Annex A, B, or C.
 31 government-designated members
 Terms of reference, conflict of interest procedure: SC-1/7,SC-
1/8, SC-4/20
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What are the 9 new POPs?
Annex A – Elimination:
Elimination of production and use of all intentionally produced POPs
Lindane*, alpha-HCH. beta-HCH, chlordecone,
Hexabromobiphenyl, pentachlorobenzene, “tetra- and
pentabromodiphenyl ether”*, “hexa- and hepta bromodiphenyl
ether”*
*listed with use specific exemptions
Annex B - Restriction:
Restrict production and use in accordance with the provisions
PFOS**
**listed with several specific exemptions and
acceptable purposes for production and use
Annex C - Unintentional Production:
“…Continuing minimization and, where feasible, ultimate elimination of
the total releases of chemicals.”
Pentachlorobenzene
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1. Chlordecone
 Listed in: Annex A (Elimination)
 Production: No exemption
 Use: No exemption
Past use: Agricultural pesticide (banana plantation)
Used in 1966-1975 in the USA for ant and roach.
Also known as « Kepon ».
Properties similar to Mirex.
Currently: No production and use reported.
The French island of Martinique is heavily contaminated with
chlordecone.
Alternatives: Available
 Proposal: 2005, European Community
 Risk profile: UNEP/POPS/POPRC.2/17/Add.1
 Risk management evaluation: UNEP/POPS/POPRC.3/20/Add.1
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2. Hexabromobiphenyl
 Listed in: Annex A (Elimination)
 Production: No exemption
 Use: No exemption
 Proposal: 2005, European Community
 Risk profile: UNEP/POPS/POPRC.2/17/Add.3
 Risk management evaluation: UNEP/POPS/POPRC.3/20/Add.3
Past use: Flame retardants. Added to plastics used in
products such as home electrical appliances,
textiles, plastic foams, laptop cabinets, etc. to
make them difficult to burn.
Currently: No production and use reported.
Other polybrominated biphenyls are also
controlled by RoHS Directive by EU.
Alternatives: Available
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3. Pentachlorobenzene
Listed in: Annex A (Elimination) and
Annex C (Unintentional production)
Production: No exemption
Use: No exemption
 Proposal: 2006, European Community
 Risk profile: UNEP/POPS/POPRC.3/20/Add.7
 Risk management evaluation:UNEP/POPS/POPRC.4/15/Add.1
Past use: Component in PCB products, fungicide, flame retardant.
Currently: Possible continuous use as intermediate for production of quintozene
(pentachloronitrobenzene: fungicide).
Unintentional production during combustion, thermal and industrial
processes
Impurities in products e.g. solvents, pesticides.
Alternatives: Available
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4. Lindane
 Listed in: Annex A (Elimination)
 Production: No exemption
 Use: Specific exemption: Human health pharmaceutical for
control of head lice and scabies as second line treatment
 Possible additional control measures:
 Limiting the package size; appropriate label;
 Protecting vulnerable groups;
 Outreach and awareness; promoting alternatives
 Proposal: 2005, Mexico
 Risk profile: UNEP/POPS/POPRC.2/17/Add.4
 Risk management evaluation: UNEP/POPS/POPRC.3/20/Add.4
Past use: About 600 000 tons of lindane was used globally 1950-2000 as
pesticide and veterinary and human applications
Currently: Some countries are still known to produce or use lindane (e.g. for
seed dressing, control of termites, head lice, etc)
Alternatives: Exists but not readily available in some countries especially for
control of head lice and scabies
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Listed in: Annex A (Elimination)
Production: No exemption
Use: No exemption
(No production allowed for alpha- and beta-HCH
because there is no exemption for production of
lindane is allowed. )
alpha-HCH beta-HCH
5. Alpha-HCH, 6. Beta-HCH
 Proposal: 2006, Mexico
 Risk profile: UNEP/POPS/POPRC.3/20/Add.8 and Add.9
 Risk management evaluation: UNEP/POPS/POPRC.4/15/Add.3 and Add.4
Past use: High-volume by-products of lindane. The production of one ton
of lindane generates approximately up to 8 tons of alpha- and beta-
HCH.
Currently: Large stockpiles of alpha- and beta-HCH exist.
Alternatives: As there is no commercial use of alpha- and beta-HCH,
alternatives are not needed.
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GLOBAL ISSUE:
Obsolete waste of alpha-, beta-HCH and lindane
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7. Perfluorooctane sulfonic acid (PFOS), its salts
and perfluorooctane sulfonyl fluoride (PFOSF)
 Listed in Annex B (Restriction) with Specific
exemptions and Acceptable purposes
 Proposal: 2005, Sweden
 Risk profile: UNEP/POPS/POPRC.2/17/Add.5
 Risk management evaluation: UNEP/POPS/POPRC.3/20/Add.5 and
UNEP/POPS/POPRC.4/15/Add.6
Past use: PFOS is both intentionally produced and an unintended degradation
product of PFOS-related substances (PFOS precursors). Examples of
use include: electronic appliances, fire-fighting foams, water proof for
textile, leather, etc.
Currently: PFOS is still produced and used in several countries.
Alternatives: Available for some types of use but no known technically feasible
alternatives for some applications e.g. semi-conductor, photo imaging,
aviation hydraulic fluids Guidance: in preparation by POPRC
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Some past/current uses of PFOS
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Uses of PFOS identified by the POPRC
1. Uses for which no alternatives are available
– Photo imaging, photo resist and semi-conductor, photo masks in the
semiconductor and liquid crystal display (LCD) industries, aviation
hydraulic fluids, certain medical devices
2. Uses for which alternatives would need to be phased in
– Metal plating, electric and electronic parts, ant baits for control of leafcutting
ants, CCD color filters, chemically driven oil production
3. Uses for which alternatives are available in developed countries
– Firefighting foams, carpets, leather and apparel, textiles and upholstery,
paper and packaging, coatings and coating additives, cleaning products,
pesticide and insecticides, rubber and plastics
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Annex A – Elimination
 May be listed with Specific exemptions
 Parties need to register (exception: PCBs)
 Exemption open for 5 years from the date of entry into force
 When all registrations have expired, no new registrations possible
for a given exemption
Annex B – Restriction
 Listed with specific exemptions and acceptable purpose
 Specific exemptions: similar to Annex A
 Acceptable purpose: need to register but no deadline, for purpose
that has no alternatives, and the use is critical
 DDT is listed with ‘acceptable purpose’ production and use
for vector control
Difference between listing in Annex A and Annex B
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 Photo imaging,
 Photo resist and anti-reflective coatings for semi-
conductors,
 Etching agent for compound semi-conductors and
ceramic filters,
 Aviation hydraulic fluids,
 Metal plating only in closed-loop systems,
 Certain medical devices (e.g. ETFE layers, radioopaque
ETFE, in vitro diagnostic medical devices,
CCD color filters),
 Fire fighting foam,
 Insect baits for control of leaf-cutting ants.
PFOS Use: Acceptable purposes
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 Photo masks in the semiconductor and LCD industries,
 Hard metal plating,
 Decorative metal plating,
 Electric and electronic parts for some color printers and
color copy machines,
 Insecticides for control of red imported fire ants and
termites,
 Chemically driven oil production,
 Carpets,
 Leather and apparel,
 Textiles and upholstery,
 Paper and packaging,
 Coatings and coating additives,
 Rubber and plastics.
PFOS Use: Specific purposes
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End products
Chemical
producers
?
??
Upstream
Downstream
Special care needed for industrial chemicals like
PFOS because: Used in numerous processes and parts
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PFOS
photo masks
semiconductor
metal
plating
fix-unit
HDD
PWB
parts, modules
solder
dispersion
surface treatment
surface treatment
De-smearing
etching
adhesive
paintPhoto resist
anti-reflective
coating
other use
..may also affect
other industries
Special care needed for industrial chemicals like PFOS because:
Long supply-chain, involve many producers/ users
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 What types of processes use PFOS and related substances?
 What types of articles contain PFOS and related substances?
 What types of articles containing PFOS are recycled?
 What are options for alternative products or processes?
 Technical feasibility, costs, efficacy, risk, availability,
accessibility?
 Need to develop new technology? How to introduce?
Questions on PFOS contained in articles
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Originally proposed as: “Commercial mixture of
pentabromodiphenyl ether”
Mixture of brominated organic chemicals, main
components are penta- and tetra- isomers
Proposal: 2005, Norway
Risk profile:
UNEP/POPS/POPRC.2/17/Add.1
Risk management
evaluation:UNEP/POPS/POPRC.3/20/Add.1
C12H5Br4O
C12H5Br5O
8. Tetrabromodiphenyl ether and
pentabromodiphenyl ether
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Structure Congener Name Fraction
BDE-99
2,2′,4,4′,5-pentabromodiphenyl
ether
45–49 %
BDE-47
2,2′,4,4′-tetrabromodiphenyl
ether
38–42 %
BDE-85
2,2′,3,4,4′-pentabromodiphenyl
ether
2.2–3.0 %
BDE-100
2,2′,4,4′,6-pentabromodiphenyl
ether
7.8–13 %
BDE-153
2,2′,4,4′,5,5′-hexabromodiphenyl
ether
5.3–5.4 %
BDE-154
2,2′,4,4′,5,6′-hexabromodiphenyl
ether
2.7–4.5 %
Commercial mixture of pentabromodiphenyl ether
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Past use: Most commonly used as a flame retardant in flexible polyurethane foam
(PUF); also used in printed circuit boards. The annual demand worldwide
was estimated as 7,500t in 2001, (US: 7,100t, Europe 150t, and Asia 150t)
Currently: There should be no current production of commercial pentaBDE in
Europe, Japan, Canada, Australia and the US; however, it is possible that
production continues elsewhere in the world.
Alternatives: Some known alternatives e.g. triphenyl phosphate, tribromoneopentyl
alcohol, tris(1,3-dicholoro-2-propyl)phosphate
- Guidance on feasible flame-retardant alternatives to commercial
pentabromodiphenyl ether (POPRC 2008)
- Environmental Profiles of Chemical Flame-Retardant Alternatives for
Low-Density Polyurethane Foam (USEPA 2005)
8. Tetrabromodiphenyl ether and
pentabromodiphenyl ether
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DEFINITION
“Tetrabromodiphenyl ether and pentabromodiphenyl ether” means:
• 2,2',4,4'-tetrabromodiphenyl ether (BDE-47, CAS No: 40088-47-9) and
• 2,2',4,4',5-pentabromodiphenyl ether (BDE-99, CAS No: 32534-81-9) and
• other tetra- and pentabromodiphenyl ethers present in commercial
pentabromodiphenyl ether.
Listed in Annex A (Elimination)
Exemption for production: none
Exemption for use: may allow recycling of articles that (may) contain
the chemicals, and the use and final disposal of articles manufactured
from recycled materials that (may) contain the chemicals
8. Tetrabromodiphenyl ether and
pentabromodiphenyl ether
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9. Hexabromodiphenyl ether and
heptabromodiphenyl ether
Originally proposed as:
“Commercial mixture of octabromodiphenyl ether
Mixture of brominated organic chemicals, main
components are hexa- and hepta- isomers.
Proposal: 2006, EU
Risk profile: UNEP/POPS/POPRC.3/20/Add.6
Risk management
evaluation:UNEP/POPS/POPRC.4/15/Add.1
C12H5Br6O
C12H5Br7O
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Structure Congener Name Fraction
BDE-175/183
2,2′,3,4,4′,5′,6-heptabromodiphenyl
ether
2,2',3,3',4,5',6 heptabromodiphenyl
ether
13–42 %
BDE-153
BDE-154
2,2′,4,4′,5,5′-hexabromodiphenyl
ether
2,2′,4,4′,5,6′-hexabromodiphenyl
ether
0.15–8.7 %
Commercial mixture of octabromodiphenyl ether
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Past use: Most commonly used as a flame retardant in flexible polyurethane foam
(PUF); also used in printed circuit boards. The annual demand worldwide
was estimated as 7,500t in 2001, (US: 7,100t, Europe 150t, and Asia 150t)
Currently: There should be no current production of commercial pentaBDE in
Europe, Japan, Canada, Australia and the US; however, it is possible that
production continues elsewhere in the world.
Alternatives: Some known alternatives e.g. triphenyl phosphate, tribromoneopentyl
alcohol, tris(1,3-dicholoro-2-propyl)phosphate
- Guidance on feasible flame-retardant alternatives to commercial
pentabromodiphenyl ether (POPRC 2008)
- Environmental Profiles of Chemical Flame-Retardant Alternatives for
Low-Density Polyurethane Foam (USEPA 2005)
9. Hexabromodiphenyl ether and
heptabromodiphenyl ether
Research Centre for Toxic Compounds in the Environment
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DEFINITION
“Hexabromodiphenyl ether and heptabromodiphenyl ether” means:
• 2,2',4,4',5,5'-hexabromodiphenyl ether (BDE-153, CAS No: 68631-49-2),
• 2,2',4,4',5,6'-hexabromodiphenyl ether (BDE-154, CAS No: 207122-15-4),
• 2,2',3,3',4,5',6 heptabromodiphenyl ether (BDE-175, CAS No: 446255-22-7),
• 2,2',3,4,4',5',6-heptabromodiphenyl ether (BDE-183, CAS No: 207122-16-5) and
• other hexa- and heptabromodiphenyl ethers present in commercial
octabromodiphenyl ether.
Listed in Annex A (Elimination)
Exemption for production: none
Exemption for use: may allow recycling of articles that (may) contain
the chemicals, and the use and final disposal of articles manufactured
from recycled materials that (may) contain the chemicals
9. Hexabromodiphenyl ether and
heptabromodiphenyl ether
Research Centre for Toxic Compounds in the Environment
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Hazards associated with the recycling chain
Disassembly
Metallurgical
treatment
Size reduction
and separation
Removal of hazardous
components
Hg switches: Hg
Batteries: Cd, Pb, Hg
Gas discharge lamps:
Hg
CRTs: Pb, phosphors
Formation of dust
particles containing
plastics, metals,
ceramic and silica
Emission of metal
fumes, mixed
chlorinated and
brominated dioxins
and furans
(PXDD/Fs)
Hazards
Recycling chain
Shredding Smelting Incineration and
landfilling
Emission of metal
fumes, PXDD/Fs
Leaching of heavy
metals and BFRs
Final
treatment
Risks in the recycling and waste treatment process
Research Centre for Toxic Compounds in the Environment
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Samples:
- Liquid crystal display (LCD) TV, Laptop PC, Power supply unit
- Wallpaper, Curtain, Heat insulation material
Rear cover
Pulverized samples
Front cover
Chemicals in products/articles
Analysis of chemicals in new products/articles
Analytical method:
- Samples were pulverized by frost shattering using liquid N2.
- HRGC/HRMS and LC/MS methods.
Target compounds:
- Organobromine compounds (PBPhs, TBBPA, HBCDs, PBDEs)
- Phosphoester plasticizers and flame retardants (TMP, TEP, TPrP, TBP,
TClPP, TCEP, TBEP, TDCPP, TOP, TPhP, TCP)
Research Centre for Toxic Compounds in the Environment
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Printed circuit board
(power supply unit)
Printed circuit
board (LCD panel)
Printed circuit board
Pulverized samples
LCD panel
Research Centre for Toxic Compounds in the Environment
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Chemická látka Příloha Přijatelný účel/zvl.výjimka
α-hexachlorcyklohexan A výroba: žádná
použití: žádné
β-hexachlorcyklohexan A výroba: žádná
použití: žádné
chlordekon A výroba: žádná
použití: žádné
hexabrombifenyl A výroba: žádná
použití: žádné
hexa a heptabromdifenylether A výroba: žádná
použití: výrobky v souladu s ustanoveními části IV
přílohy A
γ-hexachlorcyklohexan A výroba: žádná
použití: žádné
pentachlorbenzen A a C výroba: žádná
použití: žádné
perfluoroktansulfonová kys., její soli a
perfluoroktansulfonylfluorid (PFOS)
B výroba: pro povolená použití
použití: 8 účelů, 12 výjimek
tetra a pentabromdifenylether A výroba: žádná
použití: výrobky v souladu s ustanoveními části IV
přílohy A
Situace v ČR
Research Centre for Toxic Compounds in the Environment
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Registrované výjimky ČR
 pro tetrabrombifenylether a pentabromdifenylether a pro
hexabromdifenylether a heptabromdifenylether zvláštní výjimky s
názvem „výrobky v souladu s ustanoveními části IV přílohy
A“ .
 Pro kyselinu perfluoroktansulfonovou a její soli zvláštní výjimky s
názvem „pokovování (tvrdé pokovování) a pokovování
(dekorativní pokovování)“.
 přijatelné účely s názvem „fotografické zobrazování,
fotorezistentní a protiodrazové povlaky pro polovodiče,
hydraulické kapaliny v letectví a pokovování (tvrdé
pokovování) pouze v uzavřeném systému“.
 Zvláštní výjimky registrace na dobu pěti let, tj. do 26. 8. 2015,
přijatelné účely bez omezení
Research Centre for Toxic Compounds in the Environment
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Látky projednávané v POPRC
 Na posledním POPRC nebyl předložen žádný nový návrh
 Původní záměr EK navrhnout 3 nové látky – pentachlorfenol,
hexachlorbutadien a PCNs
 (pro POPRC 7 určitě nové návrhy budou)
* seznam látek, pro jejichž výrobu, dovoz a použití je nutné povolení
Látka Pozn.
Chlorované parafíny s
krátkým řetězcem
V CLRTAP, nevstoupilo dosud v
platnost
Projednáván REACH příloha XIV*
endosulfan Projednáván v CLRTAP
hexabromcyklododekan Projednáván v CLRTAP
Projednáván REACH příloha XIV
Research Centre for Toxic Compounds in the Environment
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Možné látky k diskuzi
Látka
Pentachlorfenol (projednáván CLRTAP)
Polychlorované naftaleny (v CLRTAP nevstoupilo dosud v platnost)
Hexachlorbutadien (CLRTAP nevstoupilo dosud v platnost)
Trifluralin (projednáván CLRTAP)
Dikofol (projednáván CLRTAP)
PFOA – perfluoroktanová kyselina
Cyklické siloxany
17-alpha-ethinylestradiol
???
Research Centre for Toxic Compounds in the Environment
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Hodnocení účinnosti opatření Stockholmské
úmluvy
Research Centre for Toxic Compounds in the Environment
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Hodnocení účinnosti opatření SÚ - Globální
monitoring
Základní matrice:
- Ovzduší
- Mateřské mléko
Článek 16 SÚ - hodnocení účinností opatření úmluvy – každé 4
roky:
 Data z monitoringu
 Regionální a globální transport
Research Centre for Toxic Compounds in the Environment
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Regional monitoring reports
 Introduction, background
 Description of the region
 Regional strategy for information gathering
 Arrangements to address global and regional transport
 Methodology for sampling, analysis and handling of data
 Results
 Summary of findings and discussion
Global monitoring plan – regional organisation
Research Centre for Toxic Compounds in the Environment
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63
GMP should in each region strive for at least
Three to five stations with active high-volume sampling
A network of 10 to 15 passive sampling stations arranged in a grid with spacingof
approximately 200 x 200 km for enhancing geographical coverage .
Passive samplers should be co-located at the high volume sites for comparison
purposes.
Cumulative sampling (for 1 to 2 days every week or continuously over periodsof 1 to 2
weeks) by active high volume sampling (~0.5-1 m3/min. flowrate) at a few sites in
each region. These samples would be separated into particulate and gaseous
fractions.
Continuous, cumulative passive (diffusive) sampling for integration periods of 3
months to 1 year using passive samplers deployed at a large number of sites,
including the high volume sampling sites.
Global monitoring plan – regional organisation
Research Centre for Toxic Compounds in the Environment
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Globální POPs monitoring - ovzduší
Ovzduší:
Pasivní vzorkování jako doplněk
aktivního velkoobjemového
vzorkování:
 Není potřeba čerpadlo a proud
 Malé a laciné
 Jednoduché
UNEP - Stockholm Convention on POPs
“Effectiveness Evaluation”
Research Centre for Toxic Compounds in the Environment
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Observatoř Košetice
Regionalní monitoring POPs
$
$$
$
$
$
$
$
$
$
$
$$
NO99
Hazelrigg
Lancaster
Augsburg
DE9
DE1IS91
NO42
CZ3
FI96
SE97
SE2
air
precipitation
soil
vegetation
EMEP POPs
Network
Research Centre for Toxic Compounds in the Environment
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Integrovaný monitoring POPs – odběrová místa a
vzorkovací frekvence – observatoř Košetice – od 1988
Matrice Počet odběrových míst Frekvence vzorkování
Volné ovzduší 01 Týdně (denně)
Mokrá depozice 01 Každá srážka
Povrchové vody 02, 04, 10, 12a, 12b, 14 Ročně
Sedimenty 02, 04, 10, 12a, 12b, 14 Ročně
Půdy 01, 03, 05, 07, 08, 09, 11, 13, 15 Ročně
Opad 09 Ročně
Borové a smrkové jehličí 05, 07, 08, 09, 13, 15, 16 Ročně
Mechy 05, 07, 08, 09, 13, 15, 16 Ročně
Research Centre for Toxic Compounds in the Environment
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Držák
PUF disk
Cirkulace vzduchu
Ocelové misky
Pasivví vzorkovače –
komplementární aktivnímu
vzorkování.
 Bez pumpy a proudu
 Malý a laciný
 Jednoduchý
Pasivní vzorkovače pro stanovení POPs ve volném
ovzduší
Research Centre for Toxic Compounds in the Environment
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Pasivní vzorkovače pro stanovení POPs ve volném
ovzduší
Koncepční přístup centra RECETOX:
 Využitelnost pro monitoring na globální, regionální, lokální
úrovni
 Vývoj a založení monitorovací sítě v České republice
(MONET-CZ) a CEECs (MONET-CEECs)
 Vliv environmentálních faktorů
 Studium místních vlivů
 Studium časových a prostorových trendů
 Aplikace pro toxikologické testování
Research Centre for Toxic Compounds in the Environment
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Česká národní monitorovací síť POPs ve volném ovzduší
metodou pasivního vzorkování (MONET-CZ)
Research Centre for Toxic Compounds in the Environment
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Studium modelových zdrojů POPs a studium
lokálních vlivů
Spalovny odpadů
Spolana Neratovice DEZA Valašské Meziříčí
Cementárny
Research Centre for Toxic Compounds in the Environment
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MONET-CZ =
Czech Republic
MONET-PIs =
Pacific islands -
Fiji
MONET-CEECs
= 20 CEE
countries + 2 CA
countries
MONET-Africa
= 17 African
countries
MONET-EUROPE – 55 sampling
sites round whole Europe
RECETOX Monitoring Network
MONET = MOnitoring NETwork
NADI
NAUSORI
LAUCALA
© RECETOX 2007
Global/national POPs monitoring - MONET
Research Centre for Toxic Compounds in the Environment
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RECETOX/Národní POPs Centrum ČR –
MONET-CZ/REGION – Krajské studie
Research Centre for Toxic Compounds in the Environment
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73
MONET-EUROPE – 2009-2011 – 55 odběrových
míst
Research Centre for Toxic Compounds in the Environment
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74
launched Dec. 2004 at 50 sites!
GAPS
Global Atmospheric
Passive Sampling
Study
Updated : August 2006 (Tom)
Antarctica
Environment Canada - GAPS = Global Atmospheric
PAssive Sampling Study
T. Harner
Research Centre for Toxic Compounds in the Environment
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75
2009 sampling sites
Bukasa Island,
UgandaMt. Kenya,
Kenya
IJRC-PTS,
China
MONET
(RECETOX,
Czech Rep.)
Spain
Global Passive Air Sampling Programs
= new GAPS sites added in 2009
MONET
(RECETOX,
Czech Rep.)
Research Centre for Toxic Compounds in the Environment
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Malisch et al., Dioxin2010, San Antonio, TX
POPs v mateřském mléce, studie WHO, 2008-9 – HCB
[mg.kg-1 tuku]
Research Centre for Toxic Compounds in the Environment
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POPs v mateřském mléce, studie WHO, 2008-9 – S 6 PCBs
[mg.kg-1 tuku]
Malisch et al., Dioxin2010, San Antonio, TX
Research Centre for Toxic Compounds in the Environment
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Integrated POPs monitoring - Observatory Košetice
Superstation concept - Observatory Košetice, CR
$
$$
$
$
$
$
$
$
$
$
$$
NO99
Hazelrigg
Lancaster
Augsburg
DE9
DE1IS91
NO42
CZ3
FI96
SE97
SE2
air
precipitation
soil
vegetation
EMEP POPs Network
Comparison of existing
programmes (EMEP,
GAPS, MONET) and
approaches (active vs.
passive)
Research Centre for Toxic Compounds in the Environment
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Budoucí vývoj
Měření – monitoring – modelování
Základní informace týkající se hladin a distribuce
Nástroje pro hodnocení účinků, dopadů a rizik
Research Centre for Toxic Compounds in the Environment
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GENASIS 1.0 - http://www.genasis.cz
Research Centre for Toxic Compounds in the Environment
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81
Regionální centra SÚ
Research Centre for Toxic Compounds in the Environment
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82
REGIONAL AND SUBREGIONAL CENTRES
FOR TECHNICAL ASSISTANCE AND
CAPACITY BUILDING
Research Centre for Toxic Compounds in the Environment
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83
Stockholm Convention Centres
for capacity-building and transfer of technology
Research Centre for Toxic Compounds in the Environment
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84
RECETOX POPs Research topics and areas of
experties
Environmental occurrence of PTS
 Monitoring
 Human and ecological risk assessment
 Environmental technologies, disposal and (bio)remediation
Education, awareness raising
 University education on MSc and PhD levels in the field of
environmental chemistry, ecotoxicology and mathematical
biology
 Training courses, summer schools
 Organisation of workshops, seminars, conferences
Research Centre for Toxic Compounds in the Environment
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85
Summer Schools
Research Centre for Toxic Compounds in the Environment
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86
(c) Training for decision-makers, managers and personnel
responsible for issues related to the Convention in:
i. Persistent organic pollutants identification;
ii. Technical assistance needs identification;
iii. Project proposal writing;
iv. Legislation development and enforcement;
v. Development of an inventory of persistent organic
pollutants;
vi. Risk assessment and management of polychlorinated
biphenyls (PCBs), dioxins and furans;
vii. Evaluation of social and economic impacts;
viii. Development of pollutant release and transfer registers;
Identified areas of technical assistance and
technology transfer needs and priorities
Research Centre for Toxic Compounds in the Environment
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Další nástroje (BAT/BEP, Dioxin Toolkit, PCBs
elimination network, DDT alternatives)
Research Centre for Toxic Compounds in the Environment
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Guidance for BAT/BEP
Guidelines on best available techniques and provisional guidance
on best environmental practices relevant to Article 5 and
Annex C of the Stockholm Convention on Persistent Organic
Pollutants
Research Centre for Toxic Compounds in the Environment
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89
Následující kategorie průmyslových zdrojů mají schopnost poměrně značné
tvorby a úniku uvedených chemikálií do životního prostředí:
1. spalovny odpadů včetně spoluspalování komunálních, nebezpečných
nebo zdravotnických odpadů nebo čistírenských kalů
2. cementářské pece spalující nebezpečný odpad
3. výroba celulózy a papíru používající chlór nebo chemikálie uvolňující
chlor pro bělení
4. následující tepelné procesy v metalurgii:
• druhotná výroba mědi
• aglomerační zařízení v železářském a ocelářském průmyslu
• druhotná výroba hliníku
• druhotná výroba zinku.
Nástroje SÚ – Guidance for BAT/BEP
Research Centre for Toxic Compounds in the Environment
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Polychlorované dibenzo-p-dioxiny a dibenzofurany, hexachlorbenzen a
polychlorované bifenyly se mohou také samovolně tvořit a uvolňovat
u následujících kategorií zdrojů včetně:
• otevřeného spalování odpadu včetně hoření skládek
• tepelných procesů v metalurgickém průmyslu nezmíněných v části II
• domovních zdrojů spalování
• zařízení a průmyslových kotlů na spalování fosilních paliv
• zařízení na spalování dřeva a další biomasy
• speciálních procesů chemické výroby, při kterých se samovolně vyvíjejí
persistentní organické polutanty, zvláště při výrobě chlorfenolu a chloranilu
• krematorií
• provozu motorových vozidel, zejména při spalování olovnatého benzínu
• destrukce zvířecích zdechlin (likvidace kadáverů)
• barvení (chloranilem) a konečná úprava (s alkalickou extrakcí) textilu a kůže
• šrotovacích strojů pro zpracování vyřazených vozidel
• doutnání měděných kabelů
• rafinérií odpadových olejů.
Nástroje SÚ – Guidance for BAT/BEP
Research Centre for Toxic Compounds in the Environment
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The United Nations Environment
Programme UNEP Standardized
Toolkit for Identification and
Quantification of Dioxin and
Furan Releases is designed to cover
all source categories and processes
that are listed in Annex C, Parts II
and III of the Stockholm
Convention.
The Toolkit can be used where there
are no measured data available and
provides default emission factors
for all source categories.
Dioxin Toolkit
Research Centre for Toxic Compounds in the Environment
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GLOBAL ACTION TOWARDS THE RISK
REDUCTION OF POPs
Research Centre for Toxic Compounds in the Environment
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93
The chemicals industry is one of the largest sectors of the
world economy. Nearly every manufactured product contains
one or more of the thousands of chemicals produced.
Many are important and essential to modern
society and can be used safely,
billion US $
4,000
3,500
3,000
2,500
2,000
1,500
1,000
500
0
‘98 ’99 ’00 ’01 ’02 ’03 ’04 ’05 ’06 ’07 ‘08
Global chemical production by region
(Source: American Chemistry Council, 2009)
Africa and Middle East
Central, Eastern Europe
Latin America
North America
Western Europe
Asia and Pacific
Research Centre for Toxic Compounds in the Environment
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… but some can pose a serious threat
to human health and the environment.
Research Centre for Toxic Compounds in the Environment
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• Several multilateral agreements, Intergovernmental
Organizations and coordinating mechanisms
Global action to address the risk reduction by
Environmentally Sound Management of chemicals:
• Expanding and accelerating international assessment of chemical risks
• Harmonization of classification and labelling of chemicals
• Information exchange on toxic chemicals and chemical risks
• Establishment of risk reduction programmes
• Strengthening of national capabilities, capacities for management of chemicals
• Prevention of illegal international traffic in toxic and dangerous products
6 programme areas outlined in Agenda 21
International initiatives today:
Research Centre for Toxic Compounds in the Environment
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 How has it been evolved?
 Brief history of the POPs negotiation
 What does it do?
 Overview of the Convention
 What has been done and where to?
 Highlights on achievements and challenges
Global action towards the risk reduction of POPs
Research Centre for Toxic Compounds in the Environment
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97
How does it work?
 Eliminate or restrict the production, use, import and export of
POPs
 Reduce releases from unintentional POP production
 Promote BAT/BEP to reduce POP emissions
 Eliminate POPs stockpiles and wastes
 Target additional new POPs for action
 Mechanism for financial and technical assistance
 Information exchange by Clearing House Mechanism
Research Centre for Toxic Compounds in the Environment
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Convention at a glance DDT: Global Alliance
 Establish a clear platform and a joint leadership to address the challenges
around the development and deployment of alternatives to DDT;
 Enhance clarity on the understanding and agreement on goals and issues
while creating momentum in addressing the challenges;
 Improve coordination between individual initiatives aimed at developing
and deploying alternatives to DDT and addressing the interactions
between goals;
 Address gaps identified in existing initiatives in a proactive manner while
limiting the potential for duplication.
Research Centre for Toxic Compounds in the Environment
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Convention at a glance
PCBs: Elimination Network (PEN)
 Equal partnership
 Promote collaboration and information exchange
 Promote environmentally sound management and its
equipment
 Promote technical assistance and technology-transfer
Research Centre for Toxic Compounds in the Environment
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Lars-Otto Reiersen
Arctic Monitoring and
Assessment Programme
www.amap.no
Occurrence of POPs in the Arctic
Results from the AMAP 2004 Assessment report
Research Centre for Toxic Compounds in the Environment
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AMAP’s geographical coverage
Research Centre for Toxic Compounds in the Environment
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Alert
Storhofdi
Zeppelin
Pallas
Figure 1. Arctic Air Monitoring Station Map
Alert
Storhofdi
Zeppelin
Pallas
Alert
Storhofdi
Zeppelin
Pallas
Figure 1. Arctic Air Monitoring Station Map
Barrow
Valkarkai
Tagish
Little Fox Lake
Kinngait
Dunai
Amderma
Long-term Monitoring Stations
Satellite Stations
Nuuk
Alert
Storhofdi
Zeppelin
Pallas
Figure 1. Arctic Air Monitoring Station Map
Alert
Storhofdi
Zeppelin
Pallas
Alert
Storhofdi
Zeppelin
Pallas
Figure 1. Arctic Air Monitoring Station Map
Barrow
Valkarkai
Tagish
Little Fox Lake
Kinngait
Dunai
Amderma
Long-term Monitoring Stations
Satellite Stations
Nuuk
Alert
Storhofdi
Zeppelin
Pallas
Figure 1. Arctic Air Monitoring Station Map
Alert
Storhofdi
Zeppelin
Pallas
Alert
Storhofdi
Zeppelin
Pallas
Figure 1. Arctic Air Monitoring Station Map
Barrow
Valkarkai
Tagish
Little Fox Lake
Kinngait
Dunai
Amderma
Long-term Monitoring Stations
Satellite Stations
Long-term Monitoring Stations
Satellite Stations
Nuuk
Arctic Monitoring and Assessment Programme
(AMAP)
 5 long-term monitoring stations:
 Alert, Canada
 Zeppelin, Svalbard/Norway
 Storhofdi, Iceland
 Pallas, Finland
 Station Nord, Greenland (NEW, started
2007)
 Satellite stations:
 3 Canadian, 1 Alaskan, 3 Russian
 Contribute to AMAP POPs Assessment
Reports in 1997, 2002 and 2010
 Starting to screen for emerging
chemicals:
 Alert: PBDEs (2002-ongoing); Other
FRs, PFCs and CUPs (2006-ongoing)
 Zeppelin: PBDEs and PFCs (2006-
ongoing)
 Station Nord: PFCs, OCs (2007-
ongoing)
Station
Nord
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Pathways for POPs to the Arctic
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Long-range atmospheric transport
Persistent Organic
Pollutants (POPs)
Mainly due to LRT, but
also some regional
use and releases of
pesticides and
industrial chemicals
(e.g. PCB and
HCB)
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Global Fractionation Hypothesis
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Occurrence of POPs in the Arctic
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http://www.unece.org/env/lrtap (for general information)
http://www.unece.org/env/wgs (for documents)
UNITED NATIONS ECONOMIC COMMISSION FOR EUROPE
Convention on Long-range Transboundary Air
Pollution and its POPs Protocol
Research Centre for Toxic Compounds in the Environment
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The coverage of the Convention on Long-range
Transboundary Air Pollution (49 Parties)
Artic Ocean
Atlantic Ocean
Pacific Ocean
Slovenia
Hungary
Slovakia
Poland
Lithuania
Latvia
Estonia
Finland
Armenia
Sweden
Georgia
Norway
Belarus
Czech Rep. Ukraine
Denmark
Moldova
Germany
Yugoslavia
Austria
Bulgaria
Liechtenstein
Turkey
Italy
Monaco
Cyprus
Switzerland
Malta
Netherlands
Greece
Belgium
F.Y.R.of
Macedonia
Luxembourg
Albania
France
Bosnia and
Herzegovina
Spain
Croatia
Portugal
Ireland
United
Kingdom
Romania
Russian Federation
Iceland
Kara SeaBarents Sea
North Sea
Atlantic Ocean
Mediterranean Sea
Black Sea Caspian
Sea
Aral
Sea
Canada
of America
Kyrgyzst
an
Research Centre for Toxic Compounds in the Environment
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The Protocols in force
Geneva
1984
EMEP
Protocol
40
Parties
Cost-sharing of monitoring and evaluation work
Helsinki
1985
Sulphur
Protocol
22
Parties
Flat-rate reduction (30%) of 1980 emissions by
1993
Sofia
1988
NOx
Protocol
28
Parties
Flat-rate, stabilization of 1987 emissions by 1994,
BAT requirements
Geneva
1991
VOC
Protocol
21
Parties
Flat-rate reduction (30%) by 1999, optional base
year, stabilization for low-emission areas, BAT
requirements
Oslo
1994
2nd
Sulphur
Protocol
25
Parties
Effects-based emission ceilings (acidification),
mandatory limit values for major sources
Research Centre for Toxic Compounds in the Environment
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The new Protocols
Aarhus
1998
Heavy Metals
Protocol
36 Signatories,
17 ratifications
Stabilize emissions of
cadmium, lead and mercury;
limit values for major sources
Aarhus
1998
POPs Protocol 36 Signatories,
17 ratifications
Stabilize emissions of PAH,
dioxins/furans and HCB;
phase out selected pesticides,
limit values for major sources
Research Centre for Toxic Compounds in the Environment
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Programme
Coordinating Centre
Programme
Centre
Coordination Centre
for Effects
Main Research
Centre
Programme
Centre
Programme
Centre
Implementation Committee
ICP
Forests
TF
ICP
Integrated Monitoring
TF
ICP
Mapping
TF
ICP
Materials
TF
ICP
Vegetation
TF
ICP
Waters
TF
TF
Health
Working Group on
Effects
TF
Emissions Inventories
and Projections
TF
Measurement
and Modelling
Chemical
Coordinating
Centre
Meteorological
Synthesizing
Centre-West
Meteorological
Synthesizing
Centre-East
TF
Integrated
Assessment Modelling
Centre
Integrated
Assessment Modelling
EMEP
Steering Body
Ad hoc
expert group
on ammonia
Ad hoc
expert group
on POPs
TF
By-products
HMs and POPs
Working Group on
Strategies and Review
Executive Body
Intergovernmental bodies, expert groups and scientific
centres under the Convention
Research Centre for Toxic Compounds in the Environment
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Integrated POPs monitoring - Observatory Košetice
Superstation concept - Observatory Košetice, CR
$
$$
$
$
$
$
$
$
$
$
$$
NO99
Hazelrigg
Lancaster
Augsburg
DE9
DE1IS91
NO42
CZ3
FI96
SE97
SE2
air
precipitation
soil
vegetation
EMEP POPs Network
Comparison of existing
programmes (EMEP,
GAPS, MONET) and
approaches (active vs.
passive)
Research Centre for Toxic Compounds in the Environment
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 1992 – now
 Canada-US network
 Bi-national Steering Committee
 5 year implementation plan
 International peer-review every 5 years
 Atmospheric loadings and trends of toxic chemicals in air and
precipitation
 5 master stations
Integrated Atmospheric Deposition Network
(IADN)