First Results for Dioxins andFirst Results for Dioxins andFirst Results for Dioxins and First Results for Dioxins and Furans under the StockholmFurans under the Stockholm

Convention on POPsConvention on POPs

Heidelore FiedlerUNEP/DTIE Ch i l B hUNEP/DTIE Chemicals Branch11-13, chemin des Anémones

CH-1219 Châtelaine (GE), SwitzerlandE-mail: heidelore.fiedler@unep.org

Entered into force on

17 May 2004yToday, has 170

partiesparties

www.pops.int

Started with twelve initial POPs;

was amended to list nine new chemicals at

22

nine new chemicals at COP-4

DDT R iDDT R iDDT RegisterDDT Register1. Botswana (2004) 9. Mozambique (2007)1. Botswana (2004)2. China (2005): Production

and use

9. Mozambique (2007)10. Myanmar (2006)11. Senegal (2006)

3. Ethiopia (2006): Productionand use

4. India (2006): Production (1

12. South Africa (2004)13. Swaziland (2006)14 U d (2008)4. India (2006): Production (1

manufacturer) and use5. Madagascar (2007)

14. Uganda (2008) 15. Venezuela (2009)16 Yemen (2005)

6. Marshall Islands (2004)7. Mauritius (2004)8 Morocco (2005)

16. Yemen (2005)17. Zambia (2008)

33

8. Morocco (2005)

All are potential users; few producers

R i f S ifi E iR i f S ifi E iRegister for Specific ExemptionsRegister for Specific ExemptionsPOP Activity Specific exemption Party Expiry date Estimated quantity Comments

Production As allowed for China May 2009 Ca 500 tons For termiticide use; capability for 9 enterprises; 6Chlordane Production As allowed for Parties listed

China May 2009 Ca. 500 tons annually

For termiticide use; capability for 9 enterprises; 6 producing

Termiticide China May 2009 400-500 tons consumption

95% used in structures of houses, 4% in dams, 1% in underground cable boxes to control termites.

T. in buildings, d

Botswana 17/05/2009 Used in construction industry. Research on l i

Chlordane CAS No: 57-74-9 Use

dams alternativesT. in buildings, dams and roads

Zambia 17/05/2009 5,000 liters annually

For termicide use; no cost-efficient alternatives

Intermediate in production of dicofol

China May 2009 80% as intermediate in production of dicofol. 6 enterprises having capability, of these 4 are producing. Dicofol as miticide in fruits,

Production DDT

p g ,vegetables, crops; 60% in non-closed-systems

India May 2009 150,000 kg Manufacture of dicofol. One public sector unit as acaricide in tropical and sub tropical agriculture

Use Intermediate India May 2009 150,000 kg Manufacture of Dicofol Production As allowed for the

P ti li t dChina May 2009 10-30 tons

ll5 enterprises having capability to produce, 3

i d dMirex CAS N Parties listed annually enterprises produced

Termiticide Australia 17/05/2009 Used under licence in northern Australia as a bait control for the giant termite (Mastotermes darwiniensis).

CAS No: 2385-85-5 Use

China May 2009 10-30 tons annually

20-30% of mirex is used to control termites in structures of houses, dams and underground cable

44

y , gboxes.

All requested exemptions were withdrawn at COP4 register closed for ”old” POPs

http://chm.pops.int/Programmes/BATBEP/Progress/tabid/190/language/en-US/Default.aspx#LiveContent[BBGUIDE]p [ ]

55

G id li BAT/BEPG id li BAT/BEPSource According to Annex C Performance Level

(ng WHO TEQ /Nm³)

Guidelines on BAT/BEPGuidelines on BAT/BEP(ng WHO1998-TEQDF/Nm³)

Part II categories(a) Waste incinerators <0.1 (b) Cement kilns co-firing hazardous waste <0.1 ( ) g(d) Thermal processes in the metallurgical industry

- Sinter plants in iron and steel industry <0.2- Sec. copper, sec. aluminium, sec. zinc production <0.5

Part III Categories(b) Other sources in the metallurgical industry, i.e.,

- Sec. lead smelting, prim. aluminium, sec steel production prim base metals smelting <0 1sec. steel production, prim. base metals smelting <0.1

(d) Fossil-fuel fired utility and industrial boilers <0.1 (e) Firing installations for wood and other biomass <0.1 (g) Crematoria <0.1

66

(g) Crematoria <0.1(i) Destruction of animal carcasses <0.1

Methodology to Methodology to establish complete, establish complete,

comparable comparable ppPCDD/PCDF PCDD/PCDF InventoriesInventoriesInventoriesInventories

(250 pages + EXCEL file)(250 pages + EXCEL file)( p g )( p g )

Updating and review process p g pmandated by Conference of the Parties, started in 2006

77http://www.chem.unep.ch/pops/pcdd_activities/default.htm

Di i I i 1995Di i I i 1995 20052005Dioxin Inventories: 1995 Dioxin Inventories: 1995 vsvs. 2005. 2005• 1995 emissions:• 1995 emissions:

— 15 developed countries = ca. 10,500 g TEQ per year emitted— Emissions to air predominantlyp y

• 2005/2008 releases:— ca. 20 developed countries - 800 million population p p p

= ca. 14,700 g TEQ per year to air= ca. 16,500 g TEQ per year in total

60 ( t) d l i t i 2 6 billi l ti— ca. 60 (most) developing countries - 2.6 billion population= ca. 22,300 g TEQ per year to air= ca. 48,000 g TEQ per year in total

88TEQ not specified, for PCDD/PCDF only

S Di t ib ti C tS Di t ib ti C tSource Distribution per CountrySource Distribution per CountryPCDD/PCDF (TEQ), Reference year around 1995; developed countries included

80%

100%

Others

60%

OthersMineral Prod.Road TransportWaste Incin.Small Comb. Units

40%

Ind. Comb. PlantsPower PlantsNon-ferr. MetalsIron&Steel

20%

99

0%

A

AU

S B

CH

CAN D

DK F

HGK

HU

N

JPN NL

NZ S

SK UK

USA

Release to Air (TEQRelease to Air (TEQDFDF))Contrib tionContrib tion Categor in 58 Co ntriesCategor in 58 Co ntriesContribution Contribution perper Category in 58 CountriesCategory in 58 Countries

1010

T lki U d d R iT lki U d d R iToolkit Update and ReviewToolkit Update and Review• Category 6 of the UNEP Dioxin Toolkit addressesCategory 6 of the UNEP Dioxin Toolkit addresses

— Open burning of biomass (forest fires, sugarcane burning, etc.)— Open burning of municipal waste

i i i i i i• Often >60% in national release inventories in developing countries ( high activities or relatively high emission factors in the Toolkit););

• Open Burning of Waste project includes:— Characteristic domestic waste from developing countries

B h fi ld i— Burn huts vs. field experiments— First field samplings for open burning of waste

• Overall objective:

1111

j— Propose scientifically sound emission factors— Propose best environmental practices

Rural waste in China

Chi hi h h t t

Urban waste in Mexico

China, high ash content

xxx

1212

New sampler developed forNew sampler developed for sampling fumes from open burn events:

High-volume sampler with sampling head downwards; filter and PUF cartridgefilter and PUF cartridge

1313

1414

1515Mexico Rural waste; poor combustion

1616Mexico urban industrial, very good combustion

USEPA CSIRO/UQ CSIRO/UQ

‘Burn huts’ ‘In-field using mobile Semi-controlled on bricks sampler using mobile sampler

(i.e., to assess role of transport and fuel

repositioning)

2 x sugarcane standing2 x sugarcane piled2 x forest litter piled

4 x open forest (‘Duke forest’)

4 x sugarcane (‘Florida’)

4 x open forest fuels2 x sugarcane

2 x forest litter piled2 x grass piled

2 x pine needles piled

1717Sugarcane piled

S C All d tS C All d tSugar Cane: All dataSugar Cane: All data200)

60

90100200

d bi

omas

s

Suggest EF for sugar cane combustion of 4 g TEQ /ton burned

2 0

30

60EF for impacted Ag burn (30)

EF Grassland and Moor (5)

on b

urne

d 4 g TEQDF/ton burned

d C d t i

0.00.51.01.52.0

EF for Ag burn nonimpact (0.5)EF (u

g/to

In Field

On Bric

k in N

C

BHut stan

ding

Burn hut p

iled

lian Fiel

d dataBH-Florid

a

sLAB ar

tefac

tBH-H

awai

1818

On B BAustr

ali

Aus.

EF f O B i (C 6)EF f O B i (C 6)EFs for Open Burning (Cat. 6)EFs for Open Burning (Cat. 6)Sub-categories Potential Release Route (µg TEQt-1)

Cat. Subcat. Class New Old New Old6 Open Burning Processes

a Fires/burnings - biomass1 Forest fires 1 5 0.15 4

Air Land

1 Forest fires 1 5 0.15 42 Grassland and moor fires 0.5 5 0.15 43 Sugar cane 4 0.05

4 Agricultural residue burning (in field), impacted, poor combustion conditions 30 30 1 10

i l l id l b i (i fi ld)5 Agricultural residue, cereal crop burning (in field) not impacted 0.5 0.5 0.05 10

b Fires, waste burning, landfill fires, industrial fires, accidental fires

1 Waste dump fires 100 1000 300 600p2 Accidental fires in houses, factories 400 400 400 4003 Uncontrolled domestic waste burning 40 300 300 6004 Accidental fires in vehicles (per vehicle) 94 94 18 185 Open burning of wood (construction/demolition) 60 60 10 10

1919

EFs for 6(a) biomass: based on mass burnedEFs for 6(b) waste: based on total mass of waste present at site (and not on

combustible fraction)

Gl b l M it iGl b l M it iGlobal Monitoring Global Monitoring of POPs (GMP)of POPs (GMP)of POPs (GMP)of POPs (GMP)

• Guidelines developed and approved for three core matrices: - ambient air, ,- mothers’ milk, human

blood;Regional reports presented atRegional reports presented at

COP-4 (5/2009) Updating for new POPs

2020www.pops.int

http://www.chem.unep.ch/Pops/GMP/default.htm

Egypt, Ethiopia, Kenya, Mauritius, Uganda, Zambia

Fiji, Kiribati, Niue, Palau, DR Congo, Ghana, Mali, Nigeria, Senegal, Togo

jSamoa, Solomon Islands, Tuvalu (Marshall Islands)

CubaBahamas, Barbados, Haiti

Antigua&Barbuda, Brazil, Chile, Ecuador, Jamaica, Mexico, Peru, Uruguay

2121

UNEP/GEF Project on POPs AnalysisUNEP/GEF Project on POPs Analysis

Annex in SC GMP Guidance

2222

P i O i P ll (POP ) f A l iPersistent Organic Pollutants (POPs) for AnalysisChemical Parent POPs Transformation productsAldrin aldrinAldrin aldrinChlordane cis- and trans-chlordane cis- and trans-nonachlor,

oxychlordaneDDT 4,4’-DDT, 2,4’-DDT 4,4’-DDE, 2,4’-DDE,

4 4’ DDD 2 4’ DDD4,4’-DDD, 2,4’-DDDDieldrin dieldrinEndrin endrinHexachlorobenzene HCBHexachlorobenzene HCBHeptachlor heptachlor -heptachlorepoxideMirex mirexPCB ΣPCB7 (7 congeners: 28, 52, 101,PCB ΣPCB7 (7 congeners: 28, 52, 101,

118, 138, 153, and 180)PCB with WHO98-TEFs (12 congeners):

77, 81, 105, 114, 118, 123, 126 156 157 167 169 189

Dioxin-like compounds

2323

126, 156, 157, 167, 169, 189PCDD/PCDF 2,3,7,8-substituted PCDD/PCDF (17 congeners)Toxaphene congeners P26, P50, P62

compounds (TEQ)

N POP bN POP b M i dM i d DRAFTDRAFTNew POPs to be New POPs to be Monitored Monitored -- DRAFTDRAFTAir Human Milk/Blood

Chlordecone chlordecone chlordecone-, -, -HCH -, -, -HCH -, - , -HCH Hexabromobiphenyl PBB 153 PBB 153

optional: PBB 138Pentachlorobenzene PeCBz PeCBzPBDE BDE 47, 99, 153, 154, 175/183 (co-eluting)

ti l BDE 17 28 100 ti l BDE 100optional: BDE 17, 28, 100 optional: BDE 100PFOS/PFOSF precursor compounds PFOS anion

(linear plus branched together)

Candidate POPs under ReviewHBCD -, -, -HBCD -, -, -HBCDSCCP (C10-C13)

2424

SCCP (C10 C13) Endosulfan -, -endosulfan -, -endosulfan;

endosulfan sulfate endosulfan sulfate

R d d I iR d d I iRecommended InstrumentationRecommended InstrumentationTier 1: High resolution gas chromatograph + High resolution mass spectrometerg g g p g p

Instrumentation capable to analyze PCDD/PCDF and dioxin-like PCB in addition to the lipophilic basic POPs

Tier 2: High resolution gas chromatograph + Low resolution mass spectrometerg g g p pInstrumentation capable to analyze all POPs (some at high concentrations only)

Tier 3: High resolution gas chromatograph + Electron capture detectorg g g p pInstrumentation capable to analyze all lipophilic POPs without PCDD/PCDF and dl-PCBtwo GC columns of different polarity needed

Tier 5: LC + Low resolution mass spectrometer (+LRMS)Instrumentation capable to analyze polar POPs (e.g., PFOS)

No other instrumentation is recommended

2525

POPs in Ambient Air (PAS)POPs in Ambient Air (PAS)

PROCEDIMIENTO

PARA EL

MONTAJE DE CAPTADORES PASIVOS

Hoja 1 de 12

Rev. 2

(PAS)

PUF disk sampler

2626

PUF disk sampler - GAPS

XAD-based

GAPS Network – PCB

2727Courtesy: Dr. Tom Harner, Environment Canada

PAS Africa 2008 - DDTs

2828Klanova et al. (2008): Masaryk University, Brno, CZR, ISBN 978-80-210-4739-6

PAS Africa 2008 – PCDD/PCDF

2929Klanova et al. (2008): Masaryk University, Brno, CZR, ISBN 978-80-210-4739-6

Mother’s MilkMother’s Milk

UNEP/WHO cooperation UNEP/WHO cooperation d th WHO/UNEPd th WHO/UNEPand the WHO/UNEP and the WHO/UNEP

Reference Laboratory Reference Laboratory (Dr. Rainer Malisch (Dr. Rainer Malisch (CVUA Freiburg):(CVUA Freiburg):44thth and 5and 5thth round of round of human milk surveyhuman milk survey

3030

human milk surveyhuman milk survey

P ti i t t 3P ti i t t 3 dd 44thth d 5d 5ththParticipants at 3Participants at 3rdrd, 4, 4thth, and 5, and 5thth

Rounds of Human Milk StudiesRounds of Human Milk StudiesRounds of Human Milk StudiesRounds of Human Milk Studies

5

8

2000-2003 (26)

3131

2000-2003 (26)

2005-2007 (14)2008-2009 (22) 2009-2010 plan

POP i M h ’ MilkPOP i M h ’ MilkPOPs in Mothers’ MilkPOPs in Mothers’ Milk

3232Malisch et al. (2008), Organohalogen Compd 70, 228-232 (Dioxin2008)

PCDD/PCDF in Mothers’ Milk Worldwide M th ’Mothers’

Milk Study b WHOby WHO

DDT in Mothers’ Milk

Source: 3Source: 3rdrd Round of WHO Round of WHO

DDT in Mothers’ Milk

Sou ce: 3Sou ce: 3 ou d o W Oou d o W OHuman Milk Study (2001)Human Milk Study (2001)

WHO Reference laboratoryWHO Reference laboratory

3333

Courtesy: Courtesy: Rainer Malisch, CVUA Freiburg, Germany

WHO/UNEP M h ’ MilkWHO/UNEP M h ’ Milk TEQTEQWHO/UNEP Mothers’ Milk WHO/UNEP Mothers’ Milk –– TEQTEQ15

ght

6.91

9.73

7.18

10

EQ/g

lipi

d w

eig

4.274.023.2 3.12

3.75

2.372.87

2.36

5.324.44

2.88

5

pg W

HO

-TE

0Ghana Nigeria Senegal Korea Antigua and Chile Uruguay

3434

Barbuda

Dioxins & furans PCBs Ref. COP4/INF.31

First Worldwide UNEPFirst Worldwide UNEPFirst Worldwide UNEP First Worldwide UNEP Intercalibration Study onIntercalibration Study onIntercalibration Study on Intercalibration Study on

Persistent Organic PollutantsPersistent Organic Pollutants20092009--20112011

3535

3636

UNEP WWPISUNEP WWPIS A i (A i ( 2)2)UNEP WWPISUNEP WWPIS--Asia (z Asia (z < < ±± 2)2)n=37n=37

3737

C i iC i i ifi Ob iifi Ob iContaminationContamination--specific Observationsspecific ObservationsLargest deviation from assigned value for OCPs;Largest deviation from assigned value for OCPs;• OCPs - 62 % of data had satisfactory z-score• dl PCB 79 % satisfactorily• dl-PCB - 79 % satisfactorily• PCDD/PCDF - 82 %Potential root causes for OCP problems:Potential root causes for OCP problems:• Decomposition in injector, dirty liner

C l ti bi d ith l ti ECD d t ti• Co-elution combined with non selective ECD detection• Laboratories still use sulphuric acid to remove lipids disintegration of some OCPs

3838

disintegration of some OCPs.

A l i f PCDD/PCDF dlA l i f PCDD/PCDF dl PCBPCBAnalysis of PCDD/PCDF, dlAnalysis of PCDD/PCDF, dl--PCBPCB• Most laboratories used GC-HRMS; three used GC-LRMS;Most laboratories used GC HRMS; three used GC LRMS;• Most labs used three columns to clean up the samples after

extraction, a multi layer silica, an alumina oxide (Alox) or Florisil column and a carbon based column;Florisil column and a carbon based column;

• Several labs used automated clean up system;• A few GC-HRMS labs omitted Alox or carbon column in

sample clean-up;• Fly ash samples often treated with acid before (warm) Soxhlet

or pressurized extraction systems;or pressurized extraction systems;• Most labs used toluene (-based mixtures); one lab used

dichloromethane (ash);• GC HRMS used to analyse OCPs interesting development

3939

• GC-HRMS used to analyse OCPs interesting development especially in Asian region where GC-HRMS capacity seems to be available.

UNEP I t lib ti A h (TEQ)UNEP I t lib ti A h (TEQ)UNEP Intercalibration Ash (TEQ)UNEP Intercalibration Ash (TEQ)

4040

WWPIS A iWWPIS A i RSD V lRSD V lWWPIS Asia WWPIS Asia –– RSD ValuesRSD Values Ash Sediment Fish Milk Standard RSD n n n RSD n n TEQPCDD/PCDF 18% 22 19% 19 18% 13 16% 11 8% 28 TEQPCB 19% 15 22% 17 19% 12 22% 11 16% 24 TEQtotal 19% 17 17% 16 18% 12 13% 11 8% 23TEQtotal 19% 17 17% 16 18% 12 13% 11 8% 23 PCB7 91%* 9 35%* 16 57%* 12 14% 10 12% 22 D i 227%* 40% 29% 15%Drins - - 227%* 4 40% 8 29% 10 15% 22Chordanes - - 99% 8 26% 8 46% 9 17% 19 DDTs - - 29% 16 30% 9 31% 10 14% 20 HCB - - 26% 14 30% 9 25% 9 14% 22 Mirex - - 22% 5 29% 9 29% 9 9% 18 * Italic, no outliers removed.

UNEP uses a RSD of 12 5% for intercalibration studies to

IVM VU Amsterdam and MTM Örebro University

4141

UNEP uses a RSD of 12.5% for intercalibration studies to achieve the GMP goals demonstrating 50% decline in POPs concentrations over 10 years.

D tt d li t 1 th SD d 2 th RSD th lid d

4242

Dotted lines represent 1x the SD and 2x the RSD, the solid red lines represent the 12.5% and 25% UNEP criteria

C ll b iC ll b iCollaborationCollaboration• POPs Monitoring/analysis projects financed through:• POPs Monitoring/analysis projects financed through:

- GEF (with cash co-financing from SSC, Australia)- SAICM QSP- Intercalibration study in Asia with funds from Norway;- Intercalibration study in Asia with funds from Norway;

• Technical backstopping and execution:- Dr. Esteban Abad, Dr. Josep Rivera (CSIC Barcelona)

D J b d B (IVM VU A t d )- Dr. Jacob de Boer (IVM VU Amsterdam)- Dr. Gunilla Lindström, Dr. Bert van Bavel (MTM Örebro Univ.)- Dr. Rainer Malisch (CVUA Freiburg)

D E i R i (M E O t i T t )- Dr. Eric Rainer (MoE Ontario, Toronto)- Dr. Minghui Zheng (RCEES, Beijing), Dr. Zongwei Cai (HKBU);- Dr. Tom Harner (Env Canada), Dr. Ivan Holoubek (Recetox)

D F k W i (U i T t )

4343

- Dr. Frank Wania (Univ. Toronto)• Private sector through spares/consumables, analytical standards.

ThankThankThank Thank youyouyouyou

4444