1 st open nomiracle workshop, june 2006, ispra emission estimates for industrial chemicals as...

1st Open NoMiracle workshop, June 2006, Ispra

Emission estimates for industrial chemicals as driving factor for scenario selection

- Area distributed emission profiles for industrial chemicals

Patrik Fauser Estimating and mapping emissions of industrial chemicals at the European Scale

- Emission estimates are the logical starting point in risk assessment of chemicals

- Emissions occur during all stages, from production, processing, use and disposal

- Emissions vary greatly for different chemicals, due to chemical properties, production processes, products, use patterns and disposal

- Especially for the industrial chemicals (semi-VOCs and VOCs) the variety of chemicals is very large

- Emission estimates are often the most uncertain link in a risk assessment



1) Definition of chemicals to be included2) Quantification of production and use amounts3) Distribution of chemicals to products and activities4) Quantification of emission factors for each chemical and use5) Specify location of releases, and mapping

A ”complete” emission inventory includes:


Choice of chemicals

A risk chemical can be defined as a chemical that occurs in concentrations that may cause unwanted effects on humans and/or the environment, analogous to the PEC/PNEC approach.

Choice of chemicals is an important output of scenario selection procedure, and to make any subjective pre-selection would overrule an important objective in NoMiracle; Not be restricted by existing assumptions and judgements.

However! Important and thorough work has already been done that contain very detailed knowledge, and this knowledge may be extrapolated to many more chemicals.




Choice of chemicals:

Risk Assessment Reports (RARs)made for existing chemicals:

1) Produced and used amount of specific chemical in the EU 2) Names (locations) of producers and importers. No link is available between company name and produced/processed amount of chemicals3) Products and uses that the chemicals are associated with. The use is categorised as “use in closed systems”, “use resulting in inclusion into or onto matrix”, “non-dispersive use” and “dispersive use”4) Releases to wastewater, air, soil, surface water, sea/estuaries and landfills on a local scale (non-dispersive and wide-dispersive), regional and continental scale5) PECs for the same compartments and spatial scales as above6) Physico/chemical properties7) Ecotoxicological and human toxicological parameters

Four priority lists 141 chemicals, 77 RARs, 35 are used as training chemicals in NoMiracle



AChemical

BCAS no.

DTotal annual use

EUse in closed industrialprocesses Non-dispersive use

FUse as intermediate Use in closed systems, or inclusion into onto matrix

Gsolvent (househ., professional trade etc.)

Hsolid products (fixed or dissolved in matrix)

Idetergents (househ., professional trade etc.)

Jclothing, textiles,leather

Kcosmetics

Lother

Mformed by natural/industrial processes

NWide dispersive use(sum column G to M)

Ofuel (traffic)

chloro alkanes, c10-13

85535-84-8 15000 9430 1845 1310 573 50 3778

benzene, c10-13 alkyl derivs

67774-74-7 450000 0 278600 1400 1400

4,4'-methylenedianiline 101-77-9 432000 0 432000 4000 0 4000

2-(2-butoxyethoxy)ethano

l 112-34-5 46600 0 2330 16800 27500 44300

edetic acid (EDTA) 60-00-4 53900 6989 0 13304 3,195 756 14247,2

aniline 62-53-3 530000 0 547739 760 1940 0 2811

benzene 71-43-2 7247000 0 7247000 1410000 1410000

acetonitrile 75-05-8 10000 9300 700 119391,5 120091,5

trichloroethylene 79-01-6 138000 63140 45000 29860 29860

acrylamide 79-06-1 100000 0 100,1 100,1

acrylic acid 79-10-7 810000 41500 415000 1527,2 539,5 166 2232,7

methyl acetate 79-20-9 30000 0 4800 11188,8 5594,4 16783,2

naphthalene 91-20-3 200000 0 137000 2000 3351,5 25351,5 20000

methacrylic acid 79-41-4 40000 0 24275,7 121 30 151

3,4-dichloroaniline 95-76-1 12000 0 10746 0

cumene 98-82-8 4100000 0 3310750 205000 205000

styrene 100-42-5 3743000 0 3740006 1993,8 1993,8

2-ethylhexyl acrylate 103-11-7 70000 0 89982 16,2 1,8 18

1,4-dichlorobenzene 106-46-7 25500 100 7118,23 35,77 7240 0 7275,77

Buta-1,3-diene 106-99-0 1892000 0 1816308 11,98771 3784 75691,99 71896

Used amounts, use in industry and consumer products, ECB reports. Units are in tonnes per year.



Chemical CAS no. wastewater air Soil

local non-disp

release1)

(kg/d)

local wide-disp

release2) (kg/d)

regional3)

(kg/y)EU

(kg/y)local non-

disp release1)

(kg/d)

local wide-disp

release2) (kg/d)

regional3)

(kg/y)EU

(kg/y)local non-

disp release1)

(kg/d)

local wide-disp

release2) (kg/d)

regional3)

(kg/y)EU(kg/y)

chloro alkanes, c10-13 85535-84-8 52,308 174102,9 1738799 0,512 39,39 393,9

benzene, c10-13 alkyl derivs 67774-74-7 0,15 108040 2000200

4,4'-methylenedianiline 101-77-9 0,78 283 2550

2-(2-butoxyethoxy)ethanol 112-34-5 134,4 32,7 1941800 17483500 5,63 166,4 711750 6424000

edetic acid (EDTA) 60-00-4 560,5 2 2895000 26059000 0,0242 582000 5239000

aniline 62-53-3 6,193544 260 2300 10,25117 16000 146000

benzene 71-43-2 903 2585000 23262000 1413 18291000 1,65E+08 362 65500 590000

acetonitrile 75-05-8 2776,7 0 31201 4496800 1528,2 10060400 99954290

trichloroethylene 79-01-6 13,03 0,096 522467 4660587 3451,15 19,87 6373080 48196910 2,44 7300 60400

acrylamide 79-06-1 0,501859 9120 84000 0,200167 66 103

acrylic acid 79-10-7 323,4833 0,335 218000 973000 21,9 0,205 54000 277000

methyl acetate 79-20-9 313,27 3,55 45000 402000 14618 17876 1328000 11958000

naphthalene 91-20-3 21,39 12077,1 46007,7 16,113 3608906 32119658 0 9137,76 40367,7

methacrylic acid 79-41-4 1086,133 80000 325000 3333 4000 37000 0 0

3,4-dichloroaniline 95-76-1 2,833333 22,66667 204 0,061667 0,012333 0,111 0 0 0

cumene 98-82-8 2500 615000 6150000 2183 1242300 12423600 33,3 8190 81900

styrene 100-42-5 839,2667 252000 1038030 1836,033 2010000 16944000 0 0 0

2-ethylhexyl acrylate 103-11-7 701,1998 38170 13710 33,333 10600 51780

1,4-dichlorobenzene 106-46-7 5,942556 45450 423450 255,3333 782500 7258200 0,05

buta-1,3-diene 106-99-0 476,2667 120240 1074490 3750,667 1435300 12496400

Measured and estimated releases for three selected training chemicals, ECB reports. Surface water, sea/estuaries and landfills are omitted for clarity reasons.



Chemical CAS no. vp(kPa)

logKow watsol (mg/l)

chloro alkanes, c10-13 85535-84-8 2,13E-05 6 0,47

benzene, c10-13 alkyl derivs 67774-74-7 0,0013 8,31 0,041

4,4'-methylenedianiline 101-77-9 2,87E-09 1,59 1,25

2-(2-butoxyethoxy)ethanol 112-34-5 0,0027 0,56 1000000

edetic acid (EDTA) 60-00-4 -5,01 400

aniline 62-53-3 0,04 0,9 35000

benzene 71-43-2 9,97 2,13 1800

acetonitrile 75-05-8 9,864 -0,34 139000

trichloroethylene 79-01-6 8,6 2,29 1100

acrylamide 79-06-1 0,0009 -1 2155

acrylic acid 79-10-7 0,38 0,46 1000000

methyl acetate 79-20-9 21,7 0,18 272000

naphthalene 91-20-3 0,0072 3,55 30

methacrylic acid 79-41-4 0,09 0,93 89000

3,4-dichloroaniline 95-76-1 0,000184 2,7 580

cumene 98-82-8 0,496 3,55 50

styrene 100-42-5 0,667 3,02 300

2-ethylhexyl acrylate 103-11-7 0,0155 3,89 9,6

1,4-dichlorobenzene 106-46-7 160 3,38 65

buta-1,3-diene 106-99-0 240 1,99 735

Physico/chemical parameters, ECB reports (IUCLID).



Analysing data with decision trees

Example: Predicting local emissions to wastewater treatment plants (Rlocalwwtpnondisp) with RAR data



Predicting emissions of not tested chemicals

Define chemicals of interest Compile phys/chemical, production and use parameters for selected chemicals

Run regression analysis for training set for a selected target parameter. Identify predictor parameters

Use predictor parameters for chemicals of interest to identify target parameter value

Important to note that the predicted values are based on best available existing information. The method will suggest candidates for more in-depth emission inventories



Required data:

- Use amount = produced + imported – exported

(information on national basis as well as on EU scale from EUROSTAT)

- Use patterns of chemical and/or products

(information from Nordic Products Database, SPIN)

- Physico/chemical properties

(information from e.g. IUCLID)



Used amounts, use in industry and consumer products for formaldehyde (EUROSTAT and SPIN). Units are in tonnes per year

AChemical

BCAS no.

DTotal annual

use

EUse in closed

industrialprocesses

Non-dispersive

use

FUse as

intermediate

Use in closed

systems, or inclusion into onto

matrix

Gsolvent

(househ., professional trade etc.)

Hsolid

products (fixed or

dissolved in matrix)

Idetergents (househ.,

professional trade etc.)

Jclothing,

textiles,leather

Kcosmetics

Lother

Mformed by

natural/industrial processes

NWide

dispersive use

(sum column G to

M)

Ofuel (traffic)

formaldehyde 50-00-0 4118000 1400120 1812253 905960 2718213

Calculated mean releases formaldehyde (decision tree analysis). Surface water, sea/estuaries and landfills are not included

ChemicalCAS no. wastewater air soil

local non-disp release

(kg/d)

local wide-disp release

(kg/d)

regional(kg/y)

EU(kg/y)


(kg/d)


(kg/d)

regional(kg/y)

EU(kg/y)


(kg/d)


(kg/d)

regional(kg/y)

EU(kg/y)

formaldehyde 50-00-0 2500 32,7 284022 2574994 4142 148 877832 8215811 3,58 9184 83103

blank spaces: missin training set values

Physico/chemical parameters (IUCLID)

6 CAS no. vp(kPa)

logKow watsol (mg/l)

formaldehyde

50-00-0 0,75 -0,78 550000

Example Formaldehyde



Spatial patterns of emission

Real location of industrial emissions are not given in RARs due to confidentiality

Emissions from industrial emissions are assigned to randomly selected ”Basic Organic Chemicals” locations stated in European Pollution Emission Register (EPER)



Local non-dispersive release Local wide-dispersive release Regional release1)

Chemical industriesEPER

“Basic organic chemicals”

Population density orCORINE land cover (urban categories)

Other industrial activities

EPER site orCORINE land cover

(industrial/commercial land uses)

included in regional release

Population density orCORINE land cover

(industrial/commercial land uses)

Households included in regional release Population density

Urban areas and professional workers

included in regional releaseCORINE land cover (urban categories)

Transportation included in regional release Traffic density

Assignment of emissions

Example of mapping emission to wastewater

Chemical CAS no. Local non-dispersive release to wastewater

(kg/d)

Local wide-dispersive release to wastewater

(kg/d)

Regional release to wastewater(kg/y)

benzene, c10-13 alkyl derivates

67774-74-7

108040population density

styrene 100-42-5839

random EPER“Basic organic chemicals”

252000equal distribution between

population density and industrial areas



Examples of mapping emissions to wastewater

Styrene is exclusively used as a monomer in the production of various polymer products, such as polystyrene. Contrary to the other two chemicals styrene is incorporated in a solid matrix in products used for packaging, building, transport and even clothing. The content of styrene residuals in polymers and copolymers is approximately 0,04% of the used monomer amount. Releases are predominantly associated with the local scale in the vicinity of the processing industries, where high releases to air and wastewater can be found.

C10-13 alkyl derivatives of benzene, are only used as intermediates in the production of linear alkylbenzene sulphonate (LAS), that is used as a household detergent, and is released to wastewater. The use is wide-dispersive.

1 st open nomiracle workshop, june 2006, ispra emission estimates for industrial chemicals as...

Documents

existing chemicals

variety of chemicals

distribution of chemicals

different chemicals

training chemicals

definition of chemicals

ispra choice of chemicals

risk assessment of chemicals