Updating the Inventory on Unintentional POPs (With new Toolkit for Dioxin and Furans)

Roland WeberPOPs Environmental Consulting, Göppingen, Germanyroland.weber10@web.de

Enabling Activities to Review and Update the

National Implementation Plan for the Stockholm Convention

on Persistent Organic Pollutants

4-5 March 2013, Antalya, Turkey

1

• Methodology to Establish Comparable Dioxin Inventories with the UNEP Dioxin Toolkit

• Updating and Revising Source Inventories and Release Estimates

• Examples of Updating and Revising Inventories

• Some Conclusions for Inventory Update

Content of Presentation

Methodology to EstablishComparable Dioxin Inventorieswith the UNEP Dioxin Toolkit

• Inventory of Dioxin/UPOP sources are developed to identify, quantify and prioritize source of releases

• The inventory is the basis for the development of strategies with measures, timelines and goals to minimize these releases (Action plan under the NIP).

Stockholm Convention - Article 5 (a) (i) -Inventory and action plan development

TOOLKIT FOR IDENTIFICATION AND QUANTIFICATION OF RELEASES OF DIOXINS, FURANS, AND OTHER UNINTENTIONAL POPs

• Aim to assist parties in establishing release inventories that are consistent in format and content, ensuring that it is possible to compare results, identify priorities, mark progress and follow changes over time at the country level, as well as regional and global levels. (http://toolkit.pops.int/)

• Emission Factor Methodology for Identification and Quantification of Releases of Dioxins, Furans and other Unintentional POPs

Part I General Guidance• Data Quality and QA/QC of inventory results• Guidance on updating and revising source inventories• Reporting of inventory results

Part II Default Emission Factors• New/revised dioxin emission factors• Guidance on estimating activity rates, classification of sources

and assigning appropriate emission factors

Part III Annexes and Example Inventories• Complementary information on the derivation of EF• PCB & HCB emission factors for sources with available data• Example inventories for each source group

Updated Toolkit for Identification and Quantification of Releases of Dioxins, Furans,

and Other Unintentional POPs

http://toolkit.pops.int/

Calculation of Source Strength (Dioxin release/year):The basic principle is to gather “activity statistics” which describe the quantity of a process (e.g., tons incinerated; tons steel produced per year), and use “Emission Factors” (EF) which describe release of pollutant to each medium per unit of activity (e.g., µg I-TEQ/ton). Multiplying EF and Activity Rate yields annual releases of a Source (Source Strength). Annual PCDD/PCDF emission estimate:Source Strength (gram TEQ Dioxin emission per year) = Emission Factor x Activity Rate (1)(Emission factor = amount PCDD/PCDF/UPOP per ton of feed processed or product produced).

Toolkit Calculation Methodology

For a country or region: Total annual PCDD/PCDF release = annual releases from all source groups & over all release vectors

Activity rates (Amount/Flux from a activity per year: – tonnes produced; waste burned; or m3 emitted):

• “non-dioxin-like”

• Country-specific

• Economic data, statistics

• the data the task team will gather!

Emission factors (gram TEQ Dioxin/t product or; /m3):

• identical for similar technology

• default emission factors (provided in Toolkit)

• own measured data (quality requirement !)

Toolkit Calculation Methodology

3. Obtain information on individual sources to classify these and select emission factors;

4. Quantify identified sources by applying default/measured emission factors;

5. Apply nation-wide to establish full inventory.

1. Use Screening Matrix as a guide to identify Source Groups present in the country;

2. Use Source Category list to identify specific activities in the country’s Source Group;

5-Step Approach for Establishmentof a PCDD/PCDF Inventory

No. Main Source Categories Air Water Land Prod.Residue

1 Waste Incineration X X2 Ferrous/Non-Ferrous Metal Prod X X3 Power Generation and Heating X X X4 Production of Mineral Products X5 Transport X6 Uncontrolled Combustion Proc. X X X X7 Prod./Use Chem.Cons. Goods X X X8 Miscellaneous X X X X9 Disposal X X X X10 Identification of Potential Hot-Spots XSequence does not imply any ranking of Main Source Categories (importance of individual sources will vary from country to country);

Step 1: Main Source CategoriesThe first step is checking and identifying the Main Source Categories present in Turkey.

Toolkit Source Groups and Associated Source Categories

Source Group 1. Waste Incineration2. Ferrous and Non-Ferrous Metal

Production3. Heat and Power

Generation4. Production of Mineral

Products5. Transport

Source Categories

a Municipal solid waste incineration Iron ore sintering Fossil fuel power plants Cement production 4-Stroke engines

b Hazardous waste incineration Coke production Biomass power plants Lime production 2-Stroke engines

c Medical waste incinerationIron/steel production;

foundriesLandfill, biogas combustion Brick production Diesel engines

d Light-fraction shredder waste incineration Copper production Household heating and cooking

(biomass) Glass production Heavy oil fired engines

e Sewage sludge incineration Aluminum production Domestic heating (fossil fuels) Ceramics production

f Waste wood and waste biomass incineration Lead production Asphalt mixing

g Destruction of animal carcasses Zinc production Oil Shale Processingh Brass and bronze productioni Magnesium production

jOther non-ferrous metal

productionk Shreddersl Thermal wire reclamation

Source Group 6. Open Burning Processes7. Production and Use of

Chemicals and Consumer Goods8. Miscellaneous 9. Disposal and Landfill 10. Contaminated Sites and Hotspots

Source Categories

a Biomass burning Pulp and paper production Drying of biomassLandfills, Waste Dumps and Landfill Mining Sites used for the production of chlorine

b Waste burning and accidental fires Chlorinated inorganic chemicals Crematoria

Sewage and sewage treatment

Production sites of chlorinated organics and related deposits

c Chlorinated aliphatic chemicals Smoke houses Open water dumpingApplication sites of PCDD/PCDF containing pesticides and chemicals

d Chlorinated aromatic chemicals Dry cleaning Composting Timber manufacture and treatment sites

eOther chlorinated and non-chlorinated chemicals Tobacco smoking

Waste oil treatment (non-thermal) Textile and leather factories

f Petroleum refining Use of PCB

g Textile productionUse of chlorine for production of metals and inorganic chemicals

h Leather refining Waste incineratorsi Metal industriesj Fire Accidents

KDredging of sediments; contaminated flood plains

LOther dumps/landfills of wastes from source groups 1-9

m Kaolin or ball clay sites

Step 2: Identify for each Source Group the source categories/activities in the country

Potential Release RouteSource categories of source group 1 Air Water Land Product

Residue

1 Waste Incineration X Xa Municipal solid waste incineration X (x) xb Hazardous waste incineration X (x) xc Medical waste incineration X (x) xd Light-fraction shredder incineration X xe Sewage sludge incineration X (x) xf Waste wood/biomass incineration X xg Destruction of animal carcasses X x

Step 2: Identification of Source Categories: Category 1 – Waste Incineration

For each of the source categories present in the country an estimate of the activity rate need to be made.

Potential Release Route

No.Subcategories of Main Category Air Water Land Product Residue

2 Ferrous and Non-Ferrous Metal Production X X

a Iron ore sintering X x

b Coke production X x x x x

c Iron/steel production and foundries X xd Copper production X xe Aluminum production X x

f Lead production X x

g Zinc production X x

h Brass and bronze production X xi Magnesium production x x x

j Other non-ferrous metal production x x x

k Shredders X x

l Thermal wire reclamation X (x) x x

Step 2: Identification of Source Categories: Category 1 – Ferrous/Non-Ferrous Metal Production

Around steel plant in Italy PCDD/F & PCB contamin. meat & milk (sheep/goat).

(Diletti et al, Giua et al; Org. Hal Compounds 71; 2009)

1600 sheeps and goats needed to be slaughtered

Dioxin/PCB contamination of meat/milk around EU sinter plant

2012: 20 km restriction zone for cattles.High cancer rates in area

Air emissions of a steel plant (non-BAT; EU E-PRTR data)

Release air (per year)

PCDD/PCDF 99.6 g TEQPCB 0.13 tonsBenzene 237 tonsPAH 33.6 tonsLead and compounds 79.2 tonsChromium 3.87 tonsMercury 1.5 tonsCadmium &compounds 0.4 tons Nickel 0.6 tons PM10 5380 tonsHCN 3.94 tonsSOx 40,800 tonsNOx 28,100 tonsHF 568 tonsCarbon dioxide 11,300,000 tonsCarbon monoxide 569,000 tonsAmmonia 33.5 tons

Capacity:10-12 Mio tons

Care have to be taken that reduction measures do not focus only on dioxins/UPOPs but that other substances and emissions are considered and reduced together.

Necessity of integrated pollution prevention & control

Air Residues

Low Technology combustion; No APC 35,000 9,000

Controlled combustion, min. APCD 350 900

Controlled combustion, good APCD 10 450

High Tech. combustion, soph. APCD 0.75 30

For each source category, a range of default emission factors is given reflecting different levels of technology or other parameters controlling Dioxin/UPOP releases.

Emission Factors - g TEQ/t waste

Step 3: Selection of Emission Factors

Category 1b Hazardous Waste Incineration

Source Category EF Air (µg/t) Flux (t/a) g TEQ/a1a) Municipal Waste Incineration 22No control 3,500 5,000 17.5Low technology 350 10,000 3.4Good comb, APC 30 20,000 0.6

1c) Hospital Waste Incineration 433Batch, no APC 40,000 10,000 400Control. batch, APC 3,000 10,000 30Controlled, APC 525 5,000 2.6

Total release from Waste Incineration to Air 455

Step 4: Calculation of Releases from Source Categories

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PCDD/F Inventory Turkey (2007)

• The baseline release estimate is the first inventory of sources and releases of Annex C POPs elaborated by a Party, usually as part of the National Implementation Plan developed under Article 7

• This serves as a baseline against which subsequent updated release estimates are assessed in order to establish trends in releases over time and evaluate efficacy/effectiveness of the strategies adopted

Baseline Release Estimates

Updating and Revising Source Inventories and Release Estimates

FACTORS TRIGGERING THE NEED TO REVISE INITIAL/PREVIOUS INVENTORIES, e.g.:

• Toolkit EF have been changed or new EF added• Approach has been changed (e.g.

assumptions/expert judgment)• Activities/sources:

were not identified in the baseline were incorrectly classified

CONSISTENT TIME TRENDS

FACTORS INFLUENCING CHANGES IN RELEASES OVER TIME, e.g.:

• Economic/demographic growth

• Changes in technology e.g. phasing in BAT&BEP

• Building, reconstruction, or close down of production facilities

• Substitution of fuels and/or raw material

• Introduction or reconstruction of abatement techniques

Updating of the inventory (for a particular reference year)1. Examine initial/ previous inventory

Identify the approach:•Classification of

sources and EF used

2. Review changes in data as compared with initial/ previous inventory

•Check for factors influencing changes in releases over time

3. Calculate releases

•If sources are reclassified and/or EF have been revised: assign new EF accordingly

Revision ofthe initial/previous inventory

1. Correct and/or adjust initial/previous inventory

•Include missing information/ fill gaps

NEED TO REVISE

NEED TO

REVISE

•Information sources on activity rates

•Assumptions and expert judgment applied to fill the gaps

•Establish activity rates for the reference year

•Reclassify sources according to the present situation

•Use the revised set of EF for computing releases / apply the same assumptions/expert judgment as in the updated inventory

•Multiply EF with new activity rates

•If source classification unchanged: use the same EF

•Check for revised/new Toolkit EF

Establishing Trends in POPs Releases Over Time

Source: Stockholm Convention Secretariat

Examples of Updating and Revising Inventories

95% decrease

Baseline inventory[2003 data, Toolkit 2005]

Source group: Open burningSource category: Waste burningSource class: Uncontrolled domestic waste burning

Activity rate [2003]: 60’000 t/yrEFAir [Toolkit 2005]: 300 µg TEQ/t

Release to air from open burning of waste: 18 g TEQ/yr

Updated inventory[2010 data, Toolkit 2013]

Source group: Open burningSource category: Waste burningSource class: Uncontrolled domestic waste burning

Activity rate [2010]: 20’000 t/yrEFAir [Toolkit 2013]: 40 µg TEQ/t

Release to air from open burning of waste: 0.8 g TEQ/yr

Revised inventory[2003 data, Toolkit 2013]

Source group: Open burningSource category: Waste burningSource class: Uncontrolled domestic waste burning

Activity rate[2003]: 60’000 t/yrEFAir [Toolkit 2011]: 40 µg TEQ/t

Release to air from open burning of waste: 2.4 g TEQ/yr

Incorrect assessment

Example 1: Revised Emission Factor

Source: Stockholm Convention Secretariat

66% actual decrease

3

Baseline inventory[2003 data, Toolkit 2005]

Source group: Open burningSource category: Biomass burningSource class: Agricultural residue burning, impacted

Activity rate [2003]: 4’000’000 t/yrEFAir [Toolkit 2005]: 30 µg TEQ/t

Release to air from agricultural residue burning: 120 g TEQ/yr

Updated inventory[2010 data, Toolkit 2013]

Source group: Open burningSource category: Biomass burnSource class: Agricultural residue burning, impacted

Activity rate [2010]: 2’000’000 t/yrEFAir [Toolkit 2013]: 30 µg TEQ/t

Release to air from agricultural residue burning: 60 g TEQ/yr

New source class: sugarcane burning

Activity rate [2010]: 2’000’000 t/yrEFAir [Toolkit 2013]: 4 µg TEQ/tRelease to air from sugarcane burning: 8 g TEQ/yr

Revised inventory[2003 data, Toolkit 2013]

Source group: Open burningSource category: Biomass burnSource class: Agricultural residue burning, impacted

Activity rate [2003]: 3’000’000 t/yrEFAir [Toolkit 2013]: 30 µg TEQ/t

Release to air from agricultural residue burning: 90 g TEQ/yr

New source class: sugarcane burning

Activity rate [2003]: 1’000’000 t/yrEFAir [Toolkit 2013]: 4 µg TEQ/tRelease to air from sugarcane burning: 4 g TEQ/yr

increase +8 g TEQIncorrect

assessment

increase +4 g TEQ

Example 2: Additional Class

Source: Stockholm Convention Secretariat

Baseline inventory[2003 data, Toolkit 2005]

Source group: Waste incinerationSource category: Destruction of animal carcasses

-no information-releases considered negligible

Updated inventory[2010 data, Toolkit 2013]

Source group: Waste incinerationSource category: Destruction of animal carcassesSource class: Old facility, no APCSNew information discoveredActivity rate [2010]: 1’000 t/yrEFAir [Toolkit 2013]: 500 µg TEQ/t

Release to air from destruction animal carcasses: 0.5 g TEQ/yr

Revised inventory[2003 data, Toolkit 2013]

Source group: Waste incinerationSource category: Destruction of animal carcassesSource class: Old facility, no APCS

Activity rate [2003]: 2’000t/yrEFAir [Toolkit 2013]: 500 µg TEQ/t

Release to air from destruction of animal carcasses: 1 g TEQ/yr

increase +0.5 g TEQ

Incorrect assessment

decrease -0.5 g TEQ

Example 3: Missing Sources 1st Inventory

Source: Stockholm Convention Secretariat

• Same approach needs to be applied consistently in all release estimates to:• Ensure results comparable over time• Enable assessment of consistent time trends

• If the approach changes, previous inventories need to be revised by applying the same approach to estimate releases in the reference years

Conclusion – Step forward

• Turkey has a good PCDD/PCDF inventory (2007)

• Update activity rates of the source categories present

• Reclassify sources according to the present situation (appropriate selection of emission factors)

• Assess which of new source categories in the new Toolkit are present in Turkey (in particular modifications in category 7)

• More elaboration of source group 10 (hot sport). In the first NIP only PCB hot spots were addressed.

Conclusion – Steps forward Turkey

Tesekkür EderimQuestions ?

http://www.pops.int ssc@pops.int

Turkey Dioxin Inventory 2007

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PCDD/F Inventory Turkey (2007)

PCDD/F Inventory Turkey (2006)Cat. 3: Ferrous/Non-Ferrous Metal Production

PCDD/F Inventory Turkey (2006)Category 3: Heat and Power Generation

PCDD/F Inventory Turkey (2006)Category 4: Production of Mineral Products

PCDD/F Inventory Turkey (2006)Category 6: Open Burning

PCDD/F Inventory Turkey (2006)Category 7: Chemicals & Consumer Goods

Secondary metal industry is an important part of waste management for each county and a key for recycling of valuable materials.

A considerable part of materials processed in the metal industry is hazardous waste (scrap metals containing Pb, Cd, Hg, PCB, E-waste containing BFR)

In this sector you have a grey zone between hazardous waste and valuable material.

Finally hazardous waste streams (contaminated fly ashes and slags).

Example of contaminated site from metal recycling in Germany (Fahlbusch/Rastatt):

Secondary copper and zinc smelter contaminated residential area by air emission and water pollution (Dioxins and heavy metals) over decades.

Impact on residential areas (houses and gardens). Remediation and securing cost 70 million $. Local government had to pay part of the remediation

cost since they gave permissions for the operation. Waste management and emission control

Industrial activities having potentially resulted in Dioxin/uPOPs contaminated sites in Turkey (cost):

Production of EDC/VCM for PVC production Production of chlorine (Chloralkali process) Production of chlorinated pesticides/other organochlorine Application of organochlorines (e.g. PCP for wood

preservation; leather treatment) Secondary metal recycling (Al, Cu, Fe, Zn, E-waste etc.) Hazardous landfills HarboursWaste management is the key to avoid contaminated sites!Series in ESPR: http://www.scientificjournals.com/sj/espr/Pdf/aId/11084http://www.scientificjournals.com/sj/espr/Pdf/aId/10649

Hazardous waste management of e.g. PCB waste oils is one key for protection of Turkish food industry from Dioxin and PCB contamination with potential heath impact and possible financial losses in food export if a contamination is discovered e.g. by EU alert system.

Chemical/hazardous landfills need to be considered as constructions built for a limited time which need to be supervised (especially for ground water contamination) and potentially repaired or remediated.

Thermal waste treatment facilities (incinerator, gasification, cement killn) are today a key to destroy hazardous waste.

Releases from these thermal waste treatment facilities (air emission and solid residues!) need to be controlled not to contaminate environment or create contaminated sites from releases.

Care has to be taken to understand waste output of processes/factories and the potential use of waste as products.

Information can be found:POPs and UPOPs inventoryhttp://www.chem.unep.ch/popshttp://www.pops.int

PRTR inventoryhttp://www.prtr.net/prtr/index_e.cfm

http://www.unece.org/env/pp/prtr.htm

http://www.unitar.org/cwm/prtr/

http://www.chem.unep.ch/prtr/

0

2000

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MWI IWI

Small Combusters Crematories

Electric Arc Sinter

Zink Aluminum

Other Sources Cigaretts

Traffic

Masunaga et al. 1998

1958 1963 1968 1973 1978 1983 1988 19930

10000

20000

30000

40000

50000

60000

70000g TEQ/Jahr

PCDD/PCDF in PCPPCDD/PCDF in CNPco-PCB

Other ChlororganicsIndustrial Waste IncinerationMunicipal Waste Incineration

PCP

CNP

co-PCB

IWIIWIMWIMWI

In developed countries mainly emission to air were measured and included in the inventories.

Japan was the first country to set general law regulation for emission to water. Most other countries do not have PCDD/F limit for water.

Japan also has emission limits for fly ashes from incineration (3 ng TEQ/g). Most other countries do not have regulations for solids.

Provisional low POPs limit Basel C (15 ng TEQ/g).

EU has PCDD/F in PRTR (air & water). However only very few reportings.

Toolkit Revisions

The Toolkit has Undergone Several Revisions

Main Modifications In Toolkit 2013 in Relation to Toolkit 2005

Main Modifications In Toolkit 2013 in Relation to Toolkit 2005

• Several changes in Emission Factors, based on new scientific and technical literature

• Level of Confidence added for each class

• Better description on several classes and guidance on activity rates

• Inclusion of new categories and new classes

• Example inventories for each source group

• Source Group 1 – Waste Incineration

No changes to EF, nor to source classification

• Source Group 2 - Ferrous and Non-ferrous Metal Production:

Several important changes in EFs; category “m” renamed category “l” and its title renamed “Thermal wire reclamation and e-waste recycling”. New class added on category “l”: Class 2 - Open burning of circuit boards; classes 2 and 3 renamed class 3 and class 4 respectively.

Modifications by Source Group

• Source Group 3 - Heat and Power Generation: changes in EFs, inclusion of ten new classes

• Source Group 4 – Production of Mineral Products: changes in EFs in one category (Brick Production)

Modifications by Source Group

• Source Group 5 – Transport:

Added EF for 4-stroke engines unleaded gasoline with catalyst

New class created: “Ethanol with catalyst”

New class also on diesel vehicles: “Biodiesel”

New EF for heavy oil fired engines

Modifications by Source Group - continued

• Source Group 6 - Open Burning Processes:

- inclusion of a new class (sugarcane burning) with specific EFs; important changes in EFs e.g. Forest fire, grassland and savannah fires, fires at waste dumps, open burning of domestic waste.

Modifications by Source Group - continued

This group has undergone the most substantial changes.

Category a: Pulp and paper mills: change in EFs and inclusion of a new class of power boilers (Power boilers fueled with salt-laden wood)

Modifications on Source Group 7 - Production and Use of Chemicals and

Consumer Goods

Category b: Chemical industry: was split into four categories with new EFs-Cat. b: Chlorinated inorganic chemicals. And a new class added (chloralkali production using titanium electrodes)-Cat. c: Chlorinated aliphatic chemicals. ECD/VCM/PVC production was split into four subcategories (vent and liquid-vent combustors, spent catalyst residue, production processes according to technology used, and PVC only)

Modifications on Source Group 7 - continued

- Cat. d: Chlorinated aromatic chemicals. It was split into several subcategories according to substance/product produced. It was eliminated some chemicals production and added new ones. EFs were changed in several cases.

- Cat. e: Other chlorinated and non-chlorinated chemicals. New chemicals were added (TiCl4 and TiO2; Caprolactam)

Modifications on Source Group 7 – continued

Category c – Petroleum industry (refineries) renamed category f – Petroleum refining. A new subcategory added (Production processes) split in three classes (Catalytic reforming unit; Coking unit; Refinery-wide wastewater treatment )

Category d – Textile Production renamed category g and a new class added (mid range technology)

Category e – Leather refining renamed category h

Modifications on Source Group 7 – continued

Category a: Drying of biomass includes changes in classes, according to fuel condition (contamination degree) with new EFs.

Category e: Tobacco smoking ; Activity rates basis altered to “per million items” instead of “per item”, and EFs unity changed accordingly, in order to maintain uniformity in the Toolkit.

Modifications on Source Group 8 Miscellaneous

Modifications on Source Group 9Disposal/Landfill

Changes in EFs, and one more class added in Category a - Landfills, Waste Dumps and Landfill MiningNew description on almost all classes in order to make it more clear. Elimination of one class in Category d – Composting, together with changes in EFs on the two classes left.

FACTORS TRIGGERING THE NEED TO REVISE INITIAL/PREVIOUS INVENTORIES, e.g.:

• Toolkit EF have been changed or new EF added• Approach has been changed (e.g.

assumptions/expert judgment)• Activities/sources:

were not identified in the baseline were incorrectly classified

CONSISTENT TIME TRENDS

FACTORS INFLUENCING CHANGES IN RELEASES OVER TIME, e.g.:

• Economic/demographic growth

• Changes in technology e.g. phasing in BAT&BEP

• Building, reconstruction, or close down of production facilities

• Substitution of fuels and/or raw material

• Introduction or reconstruction of abatement techniques

Updating of the inventory (for a particular reference year)1. Examine initial/ previous inventory

Identify the approach:•Classification of

sources and EF used

2. Review changes in data as compared with initial/ previous inventory

•Check for factors influencing changes in releases over time

3. Compute releases

•If sources are reclassified and/or EF have been revised: assign new EF accordingly

Revision ofthe initial/previous inventory

1. Correct and/or adjust initial/previous inventory

•Include missing information/ fill gaps

NEED TO REVISE

NEED TO

REVISE

•Information sources on activity rates

•Assumptions and expert judgment applied to fill the gaps

•Establish activity rates for the reference year

•Reclassify sources according to the present situation

•Use the revised set of EF for computing releases / apply the same assumptions/expert judgment as in the updated inventory

•Multiply EF with new activity rates

•If source classification unchanged: use the same EF

•Check for revised/new Toolkit EF

Establishing Trends in POPs Releases Over Time

Source: Stockholm Convention Secretariat