SUBSTANCE: PENTACHLOROBENZENE - …€¦ · Web viewStatus date: 30 September, 2002. Comments: changed format. remarks of EU letter ENV B.1/PMM/JD’E/ipD (2002) 310893 (30-7-02)

Fact sheets on production, use and release of priority substances in the WFD, Royal HaskoningDi(2-ethylhexyl)phthalate, Final draft For official use onlyDraft version: final draft (previous version: 3.3)

Status date: 30 September, 2002

Comments: changed format remarks of EU letter ENV B.1/PMM/JD’E/ipD (2002) 310893 (30-7-02) incorporated section measures completed

SUBSTANCE: Di(2-ethylhexyl)phthalate (DEHP)

I Chemical identity

CAS number: 117-81-7 (DEHP)

Chemical group: Phthalate (esters)

Molecular Formula: C24H38O4

Homologues: no homologues

Synonyms: bis-2-ethylhexyl phthalate, DEHP, DOP, 1,2-benzenedicarboxylic acid bis(2-ethylhexyl)ester, phthalic acid bis(2-ethylhexyl)ester, 1,2- benzenedicarboxylic acid bis(ethylhexyl)ester, bis(2-ethylhexyl)1,2-benzenedicarboxylate, bis(2-ethylhexyl) ester of phathalic acid, bis(2-ethylhexyl) phthalate, di(2-ethylhexyl)ortho-phthlate, di(ethylhexyl) phthalate, dioctyl phthalate, ethylhexyl phthalate, 2-ethylhexyl phthalate, octyl phthalate, di-sec-octyl phthalate, phthalic acid dioctyl ester [IPCS, 1992]

Technical mixtures: FLEXOL Plasticizer DOP Union carbide [EU RAR, 2001]Essochem DOP ESSO Palatinol AH BASF AG Palatinol AH-L (med.) (99.5%) BASF AGGenomoll 100 (99.7%) Hoechst AGVestinol AH (99.5%) Hüls AG 1994a

II Physical properties

Water solubility: 0.23 *10-4 mg/l [Thornthon et al., 2001]0.3-0.4 mg/l [IPCS, 1992] (Collodial)0.0045 mg/l (20°C) [IPCS, 1992] (uncollodial)0.003 mg/l [EU RAR, 2001] (uncollodial)

Vapour pressure: 0.60 * 10-5 Pa [Thornthon et al., 2001]8.6*10-4 Pa [IPCS, 1992]

°C Pa Comment [EU RAR, 2001]10 0.000010*15 0.000023 20 0.000034* used in EUSES / fugacity30 0.00013*40 0.00047*50 0.0016*60 0.005770 0.011 max. indoor car (BUA 1986)80 0.03990 0.10100 0.29110 0.76120 1.9140 4.5*160 2.4* injection moulding, PVC180 80*203 287210 389216 511

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Fact sheets on production, use and release of priority substances in the WFD, Royal HaskoningDi(2-ethylhexyl)phthalate, Final draft For official use only

* Extrapolated values

Log Kow: 4.88 [Thornthon et al., 2001]6-7 [EU RAR, 2001]

III Production and use in 15 EU member states and accession states

1. Way of production/Process description:

DEHP is produced by a reaction of ortho-phthalic acid and tere phthalic acid with an appropriate alcohol. [Ligthart et al., 2001]The first reaction step, alcoholysis of phthalic anhydride to give the mono-ester, is rapid and goes to completion. The reaction generally starts at elevated temperatures and proceeds exothermically. The second step is the conversion of the mono-ester to a di-ester with the formation of water. This is a reversible reaction and proceeds more slowly than the first. To shift the equilibrium towards the di-ester the reaction water is removed by distillation or by addition of another chemical to form an azeotrope, which can be removed, and, after purification steps, recycled. The reaction rate is accelerated by means of a catalyst and high temperature. Depending on the used catalyst the temperature is in the range from 140 °C up to 250 °C. [IUCLID, 2000]

2. Fields of application:

For the convenience the industrial use and end –use of DEHP can be divided into three main product groups: [EU RAR, 2001]

I) PVC (94-95% --> ±435.000 tpa)II) non-PVC polymers (2-3% --> ±13.000 tpa)III) non-polymers (3% --> 14.280 tpa)

Phthalate acid esters are the most widely used plasticisers for the production of PVC products. Amount of plasticiser in PVC is 0-50%. [KemI, 1997]. DEHP as plasticiser for PVC is used in the following branches: leather and textile coating, leather and shoe industry, plastics industry, construction industry, sealing material, cable industry, leisure and sporting articles, carpet coating and seals and hoses. [Northrine-Westfalia State Environmental Agency, 2000]Of the total of this amount of PVC it is estimated that 78% is used indoors, and approx. 22% in outdoor applications. [EU RAR, 2001]Main use of DEHP is as plasticiser in PVC for use in products like flooring, insulation, electric wiring cables, sheeting, medical devices, synthetic leather and toys. [Ligthart et al.,2001]DEHP is used as flexibilisation in the dye and lacquer branch and in the glue industry. [Northrine-Westfalia State Environmental Agency, 2000]It is also common to use DEHP as antifoaming agent in paper production, emulsifier for cosmetics, in perfumes and pesticides, they aid in the production of different synthetic materials such as di-electric in condensers, and substitute for substances such as PCBs and pump oil. DEHP is used in flame retardant compositions in textiles, plastics as well as in other products. [Thornthon et al., 2001]Non-polymer applications of DEHP are adhesives and sealant, lacquers and paints, printing inks for paper and plastic, printing inks for textiles, rubber and ceramics for electronic purposes. [EU RAR, 2001]

3. Production volume:

The production of DEHP has been increasing since it was first used commercially in 1949. During the period 1950-1954, the production in the USA was 106 x 103 tonnes, and by the period 1965-1969 the level had risen to 650 x 103 tonnes [IPCS, 1992]

1*106 tonnes of DEHP was produced in 1985 world-wide. 1/3 is produced in the USA and 1/3 in Europe. DEHP is the most widely used plasticiser, comprising 50% of all phthalate ester plasticisers (333.000 tonnes of DEHP used in Europe). [IPCS, 1992]

In Western Europe about 1 million tonnes of phthalates are produced each year. [Ligthart et al.,2001]European production of DEHP in 1997 was 595.000 tonnes. [EU RAR, 2001]

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In 1997, 93% of the PVC plasticisers were phthalates from which some were DEHP. In recent years use of DEHP has decreased. [EC, 2000]

Available national release data:

Germany:In Germany the total production of DEHP in 1988 was 234.000 tonnes. [Brüggermann, 1988 in Thornthon et al., 2001]

German production of DEHP/total phthalates (tonnes) [Kaiser et al., 1998]1982 1990 1991 1992 1993 1994

DEHP 217.700 222.496 214.124 202.652 259.410 251.506Total 339.700 373.142 360.629 353.556 408.074 413.745

Netherlands:24.000 tonnes of phthalates were produced each year since the ’80. [Kapteijns, 1997]

Sweden:In 1995, 52,000 ton was produced. [Swedish EPA, 2001]

4. Number of production sites and locations of production:

Number of production sites is 18 different factories: [EU RAR, 2001]

* from ECPI, 1998a** from SISAS, 1999# from ECPI, 20001 Name changed from Hoechst AG in 19972 Name changed from Hüls AG in 19973 Name changed from Alusuisse in 19944 Name changed from UCB in 19955 Lonza is carrying on production of DEHP at the Enichem plant at Porto Marghera6 Sintetica SpA is now the SISAS plant at Piotello and it closed 1996

5. Use volume:

In Western Europe 900.000 tonnes of phthalates are used each year as plasticiser for PVC of which 50% is DEHP (450.000 tonnes). [Ligthart et al.,2001]The mean annual plasticiser use 1990-1995 in W-Europe was about 970.000 tonnes/y: Of this 894.000 tonnes was phthalates. For the entire plasticiser use in W-Europe approximately 90% are used in PVC. [EU RAR, 2001]

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Fact sheets on production, use and release of priority substances in the WFD, Royal HaskoningDi(2-ethylhexyl)phthalate, Final draft For official use onlyEurope is significant producer and exporter of plasticisers. In 1993 Europe produced 46% of the world demand and consumed 37% (calculated with production of 1997 this would be a use of 479 tonnes in that year) [EU RAR, 2001]European use in 1997 of DEHP was 476.000 tonnes [Cardigan, 2000] For the use of DEHP in the past 30 years there are no specific use data for this period. However, data on the amounts of DEHP and DOIP together during the period 1979 and 1998 show yearly use between 350,000 en 500,000 tonnes. [EU RAR, 2001]

Import is calculated : Import= Use + Export – Production = 476.000+186.000-595.000=67.000 tonnes/y. [EU RAR, 2001]

The use amount of DOP (di-octyl phthalates including DEHP) has been relatively constant during the period from 1979 to 1998. In 1973 a consumption of 311.000 tonnes for 7 of the present EU countries could be calculated (NL,IR,UK,FR,DK,FRG,BEL) [EU RAR, 2001]

About 100.000 tonnes of PVC are currently being recycled in the EU. This is about 3% of the total production. [EC, 2000]


Netherlands:Estimated amount of DEHP used as PVC plasticiser in 1985 was 26.400 tonnes this was about 58% of the total amount of plasticiser used. This amount of DEHP was more than 95% of the total amount of DEHP used in the Netherlands. [Kapteijns, 1997]

Denmark:Estimated consumption of phthalates in Denmark was in 1992 about 10.000 tonnes (90% used in soft PVC) in 1995 this was 11.000 tonnes. [Thornthon et al., 2001]

Germany:Consumption of DEHP in 1994/1995 (tonnes) [Kaiser et al., 1998]Import: 30.043 Export: 167.581 Used: 113.968

Sweden:In 1996, 6,100 ton was imported as raw material. An unknown amount was exported as raw material[Swedish EPA, 2001].

For 1996 (in tonnes):Product Import Production Export Colours 1 289Raw material for plastic-and rubber production 59 29Glues 7 <1Filler agents 6 2Others 26 1 100

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6. Relative use volumes in various applications:

Estimated amounts of DEHP for different applications and processes and the number of customers buying neat DEHP for each application in Western Europe 1997. [EU RAR, 2001]

Process Application Use of % of total Number DEHP DEHP of

(tpa) in costumerspolymers

Calendering Film/sheet and coated products 71,400 15.0 74Flooring, Roofing, Wall covering 34,748 7.3 20(Total, calendering) 106,148 22.3 94

Extrusion Hose and profile 57,120 12.0 82Wire and cable 80,920 17.0 62Subtotal 138,040 29.0Compounding1 85,680 18.0 83(Total extrusion) 223,720 47.0 227

Injection Footwear and miscellaneous 83,680 17.6 ?moulding and extrusion (from compound)Spread Flooring 39,032 21Coating General (coated fabric,wall- 76,160 16.0 115

covering, coil coating etc)(Total spread coating) 115.19 0.0 136

Other Car undercoating 7,140 1.5 11plastisols Slush/rotational moulding, 9,520 2.0 27

Dip coating(Total other plastisols) 16,660 3.5 38

Non- Adhesives/sealant, rubber 11,142 2.3polymerapplications*

Lacquers and paints 1,448 0.3 10Printing ink (paper and plastics) 1,661 0.3 10Ceramics 29 0.0Total, non-polymer applications 14,280 3.0

* There are 20 sites that produce lacquers and paint and printing ink. It is assumed this is equally distributed. The textile industry uses 210 tpa this is added to the amount of printing ink.

The figures show that film/sheet and coated products, wire and cable, footwear and miscellaneous and coated fabric etc. are among the most important applications of DEHP.

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Fact sheets on production, use and release of priority substances in the WFD, Royal HaskoningDi(2-ethylhexyl)phthalate, Final draft For official use onlyMaterial types containing DEHP based on industry data (Industry, 1999). The polymer applications for outdoor use are divided in the different uses. [EU RAR, 2001]

Material DistributionDEHP (tpa) Indoor uses Outdoor uses

(approx.78%) (approx.22%)Polymer – total 97% 462 362 100

Roofing material 1Roofing (coil coating) 5

Cables 20Coated fabric 21

Hoses & Profiles 6Car under-coating 7

Shoe soles 40Non-polymers 3%

14,28 ******** No data available in project databank.


GermanyIn Germany about 90% of DEHP is used in PVC and about 10% in lacers and paints. [Thornthon et al., 2001]

Sweden:Amount of phthalates used in PVC in Sweden (tonnes). [KemI, 1997]

Production ConsumptionFloor and wall covering <12.000 <8.000Cable 7.300 5.900Profiles 125 125Coated steel sheet, plastisol 1.500 1.000Sheeting 3.900 4.200Coated fabric including textile print 710 510Undercoating 0 <500Medical products 0 <1.000Food packaging 0 0

7. Existing regulation in member states or associated member states:

According to Regulation 793/93 on existing substances, risk assessment is carried out on DEHP that is expected to be completed in 2000. [EC, 2000]

On the 7 December 1999 The Commission has adopted a decision under the emergency procedure of Directive 92/59/EC in order to ban the use of phthalates in certain toys and childcare articles intended to be put in the mouth. [EC, 2000]

8. Industrial associations to be addressed:

European council for Plasticisers and Intermediates (ECPI) [CEFIC, 1999]

IV Releases to environment

1. General way of entrance and schematic picture:

Relevant main routes of release to the environment are given in appendix 2 and summarised as follows:

Atmospheric deposition: Industrial use: A5/A6/A9 S2, S3.2 and S4.2Consumer use: A4 Waste (incineration)(uncertain) A7 Buildings A3

Industrial use: S8.4, S9.2.1, S10.1 or S10.2

Consumer use: S8

Only 10% of the DEHP dumped at a landfill will enter the aquatic environment by leaching some is lost

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Fact sheets on production, use and release of priority substances in the WFD, Royal HaskoningDi(2-ethylhexyl)phthalate, Final draft For official use onlyby volatilisation to the atmosphere. DEHP in the atmosphere then either falls as dry deposition or is “washed out” via rainfall. As in a landfill anaerobic condition prevail, deposition will be minimal. [IPCS, 1992]The main pathway is wet deposition. [Northtine-Westfalia state environmental agency, 2000]

Release will occur during production, transportation, formulation and processing of PVC and non-polymers. Because the chemical isn’t bound to the matrix in the material some of the plasticiser will be lost during service life of the final product. [Ligthart et al.,2001] Transportation into the air and leaching out from certain applications seem to be the major routes by which phthalates enter the environment. [EC, 2000]Major transport route for DEHP to the environment is by air. From the atmosphere DEHP either falls as deposition or is washed out via rainfall. [IPCS, 1992]It is estimated that about 45% of the DEHP in the air is particle bound. [Kaiser et al., 1998]

2. Atmospheric cycle

a. Industrial Point Sources to the air

Release route: A5 and A6:. Production (NOSE 104.09/105.09)

By the production of DEHP the emission to the air is about 0.001% of the total production. [Kaiser et al., 1998]

. Softening of PVC (NOSE 104/105/107)Emission from the softening of PVC is about 0.8% of the total production of which 90% is lost to the atmosphere. [Kaiser et al., 1998]

. Different Processes (NOSE 104/105/107)Emissions of DEHP for three processes used in PVC-processing (g DEHP/kg PVC) [Ligthart et al.,2001]

Emission to air (g.kg-1) NOSE-CodeBlow moulding of PVC foils(Netherlands) 0.02Injection moulding of PVC(Netherlands) 0.01Extrusion of PVC profiles 0.02

Available national release data

. Germany (NOSE 104/105/107)Emissions of di(2-ethylhexyl)phthalate in the Federal Republic of Germany from 3 different sources [Kollotzek et al.,1998]Reach of emissions Quantity (tonnes/year) Production 5.2 (of which 2.6 in wastewater) [UBA der GDCH 1990 in Kollotzek et al., 1998]Production 2.5-3.5 [Balzer 1991 in Kollotzek et al., 1998]Production 2.2 (of which 1 in wastewater) [Giderakos 1993 in Kollotzek et al., 1998]Application 1,000 (1993) [UBA der GDCH 1990 in Kollotzek et al., 1998]Application 900 (1983) [UBA der GDCH 1990 in Kollotzek et al., 1998]Application 800 (1983) [Giderakos 1993 in Kollotzek et al., 1998]

b. Municipal Collective Sources to the Air:

Release from buildings (Release route: A3). Flooring/Wall covering (NOSE 112.01)

By decomposition of DEHP, 2-ethylhexanol is formed that can be derived from PVC flooring. In view of the slow hydrolysis this may be explained by the use of specific cleaning agents, on how it’s laid and on what surface. Emission of 2-ethylhexanol amounted at most to about 2000 µg/m²h. Emission of DEHP is 0,828µg/m²h at 25 ºC if the quantity of plasticiser unit area is estimated to be 0.45 kg/m². Total PVC flooring in W-Europe has been estimated to be 2.3*10^9 m². This would lead to an emission to the air of 16.6 ton DEHP/year (excluding 2-ethylhexanol). [KemI, 1997]

• Interior usage of soft-PVC products in floor covering and wall covering leads to an emission to air between 0.6 and 1.1 g/h per square meter (25C). [Kapteijns, 1997]


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. The NetherlandsAn emission of 800 kg/y has been calculated from floor covering in the Netherlands. There are more extreme values for exterior usage because of micro- bacteriological effects, UV-radiation and frost. Percentages can turn out higher. [Kapteijns, 1997]

Release from waste disposal (release route: A7)

. Land filling (NOSE 109.06.11)Due to the low solubility in water it is not very likely that the leaching of DEHP out of the product at a landfill is a major route. It is more likely that Indiscriminate dumping will lead to volatilisation of phthalates to the atmosphere rather than the aquatic environment. [IPCS, 1992]

. Releases from incineration of phthalates (NOSE 109.03)At high temperatures phthalates combustion is nearly complete. If combustion is uncontrolled and occurs at low temperature, a large percentage of the DEHP may be lost to the atmosphere compartment. [IPCS, 1992]

c. Diffuse sources to air and deposition

Deposition from rainfall (release route: S3.3 / S4.3)

Indication of a rapid photo degradation of DEHP [EU RAR, 2001].

No relevant data available concerning deposition.


. GermanyAverage deposition of phthalates due to rainfall (µg/m²/mm) [Kaiser et al., 1998]Düsseldorf 1991 0,67Düsseldorf 1992 0,46St. Tönis 1992 0.38Bocholt 1992 0,56

• Estimated yearly DEHP deposition on soil in BRD with 700 mm of rainfall (1993) is 380 tonnes with a deposition of 1.150 tonnes of total phthalates (0.4% of total German annual usage). Relative low amount of DEHP due to low vapour pressure of DEHP. [Kaiser et al., 1998]

3. Aquatic releases:

a. Industrial Point Sources to the aquatic environment:

Production, formulation and industrial use (release route: S8.4/S9)

. Production (NOSE 104.09/105.09)By the production of DEHP the emission to the water compartment is about 0.001% of the total production. [Kaiser et al., 1998]

. Processing (NOSE 104/105/107)Emission from the softening of PVC is about 0.8% of the total production of which only 10 % is lost to the water compartment. [Kaiser et al., 1998]

. Different Processes (NOSE 104/105/107)Emissions of DEHP for three processes used in PVC-processing (g DEHP/kg PVC) [Ligthart et al.,2001]

Emission to water (g.kg-1) NOSE-CodeBlow moulding of PVC foils(Netherlands) -Injection moulding of PVC(Netherlands) -Extrusion of PVC profiles 0.001

. Transportation (NOSE 201/202)Approximately 1 kg product will be released during transportation by truck. This will lead to an emission of 8 tonnes annually. Approximately 50% will be emitted to air and 50% will be discharged

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to water. Approximately 0.5% product will be discharged to surface water during transportation by ship. This results in 16 tonnes of discharges to surface water. [Kapteijns, 1997]

Release from industrial WWT (release route: S9.2.1)

. Release from production after WWT (NOSE 109.02.41)The emission during phthalates production in W-Europe ”for a production of 877.00 tonnes/y” is 1.500 tonnes before and 220 tonnes after WWT. [Kaiser et al., 1998]

b. Municipal Collective Sources to the aquatic environment:

Release from WWT/STP (release route S7, S8.4 and S9.2)

• Summary of the distribution in tonnes (total in EU) of DEHP emission to the wastewater compartment during the total life cycle. [EU RAR, 2001]

. Removal of DEHP in STP [EU RAR, 2001] (NOSE 109.02)

. DEHP concentrations in the effluent from WWTPs. (NOSE 109.02)

• For trace organic pollutant concentrations in sludge are given. These concern only the residues after degradation. The fractions degraded and found in the effluent are not given. [Thornthon et al., 2001]

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• Survey of organic pollutants in sewage sludge: mg/kg DS DEHP [Thornthon et al., 2001] Country Mean Median Min. Max. Years of surveyDEHP Austria 23.4 34.4 (11)Bis-(2ethyl- Germany 20-60 1991-1996(13)Hexyl) <2.4 320 (7)Phthalates DEHP Denmark 38 25 3.9 170 (28)Bis-(2ethyl- Sweden 6.7 28 (29)Hexyl)PhthalatesBis-(2ethyl- Canada 68 11 959 (3)Hexyl)PhthalatesDEHP USA 110 17 891 1988(30/31)Limit proposed for sewage sludge in EU is 100 mg/kg DS

Wastewater treatment of DEHP (NOSE 109.02). Survey of organic pollutants in Urban WW and WW Treatment Systems [Thornthon et al., 2001]Country (Year) Influent (µg/l) Effluent (µg/l)Austria (2000) 4.4 0.3Germany (1985) 122 (7-232) 15 (5.6-184)

. GermanyConcentration of DEHP in German sewage sludge was 50-130 mg/kg in 1988/1989 and 20-60 mg/kg in 1991/1996. [Thornthon et al., 2001]

Release from waste disposal (release route: S10)

. Land filling (109.06.11)Due to the low solubility in water it is not very likely that the leaching of DEHP out of the product at a landfill is a major route. It is more likely that Indiscriminate dumping will lead to volatilisation of phthalates to the atmosphere rather than the aquatic environment. [IPCS, 1992]

c. Diffuse sources to water

DEHP emission in EU from diffuse sources is estimated on 3,140 ton/y which includes 2,399 ton/y due to waste remaining in the environment.

4. Overall Releases and Summary

. Total emission of DEHP in the EU according to the EU RAR DEHP and the releases estimated above: [EU RAR, 2001]Diffuse source Emissions to surface Emission to waste Discharges to the Discharges with

water from diffuse water aquatic environment river water intoSources the sea

Transportation (NOSE 201) 0 50Polymer production (NOSE 104/105) 0 4.3Non-polymer production(NOSE 104/105) 0 0.82End-product use

Washing clothes with PVC printing 0 99 (NOSE 111.04.02/113)

Washing and abrasion of polymer floors 0 1,212 *(NOSE112.01)Car undercoating (NOSE 201) 23 46Roofing material 24.4 0Coils coating (NOSE 107.01.05) 261 0Fabric coating (NOSE 107.03.13) 219 0Cables & wires – air 62.6 0Hoses & profiles 15.6 0Shoe soles 36.6 0Sealant, adhesives etc. (NOSE 107.04.05) 28.7 57.3

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Lacquers & paint (NOSE 107.01) 69.9 139.8Printing ink 0 9.8

Waste Municipal landfills (leakage water) 0 15.0 (NOSE 109.06.11)Waste remaining in the environment** 2,399* 0

Other sourcesCar wash 49Textile wash 46Household (assumed to incl. textile wash) 643Storm water overflow 231 347WWTP emissions 585Rivers (based on monitoring data) 7,464 Rivers (based on PECregional) 1,705

Sum 3,140 2,604 930 1,700-7,500* High total emission is largely due to these 2 sources** OSPAR 2001 assumes that polymer residue in the environment (buried DEHP like DEHP in cable) give a leaching to the water. Due to large degradation of DEHP in the soil and absorption to the soil this seems unlikely.

. Release of DEHP from PVC About 1% of the total amount of DEHP in PVC is emitted over a year in service life to the water compartment and atmosphere due to weathering or washing out of the product. [Kaiser et al., 1998]

. DEHP emissions from 12 production sites in EU 1998 [EU RAR, 2001]

. Cleaning (NOSE 112.01)During cleaning of vinyl floors a percentage of 0.015% phthalates can be lost per treatment. [Kapteijns, 1997]

. Overall EU release of phthalates to all compartmentsEmission of phthalates in Western Europe (EU15), t/y: [Ligthart et al.,2001]

*: *: Release to the environment is 220 ton/y of which 90% to the water compartment, loss to the atmosphere is minimal.**: Also includes transportation: losses due to pumping from and to road tanker or ship may occur. Estimated maximum emission is 80 ton/y. during formulation and processing of PVC and non-polymers: in the dryblending process emissions are very small 0.013 mg DEHP / kg PVC. In further processing emitted air is often incinerated so phthalates are broken down to water and CO2. Estimated emission is 950 ton/y during processing.***: From the Dutch Emission registration data it’s clear that phthalates are at least emitted to both the air and water compartment. These are probably related to both service life and final disposal stage. [Ligthart et al.,2001]

. Releases of phthalates in the environment to all compartments in Western Europe and in the former Federal Republic of Germany in 1990. Including NOSE-code. (Data of Western Europe are extrapolated from the data of Germany) [Kollotzek et al.,1998]

Process/ Usage Western Europe Germany Production (104.09/105.09) 220 51

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Transport (201) 80 18PVC-additives (104.10/105.10) 950 226Usage in Buildings (S6*) 640 153Usage in open systems (S6*) 5,600 1,333Waste stage (109) 250 59 Total 7,740 1,840* See detailed scheme of sources


. Netherlands:Average emission of DEHP to the different compartments in the Netherlands in the years 1990, 1995, 1997 and 1998 roughly estimated from figures: [Ligthart et al.,2001]Soil: 0 ton/y ; water 20 ton/y ; air: 49 ton/y

For DEHP in particular the emission to air/water in % in the Netherlands is as followes: [Kapteijns, 1997]

Estimated annual Dutch emissions of phthalates to air and water (total production was 220.000 tonnes/year [Kapteijns, 1997]

Emission to air (ton/y) Emission to water (ton/y)Production 0.4 1.0Distribution 4 20Processing 24 -Interior usage 4 0.8Exterior usage 4.8 240Incineration 0 0Cable combustion 0 0Landfill 0 10Total 37.2 271.8

. Denmark:

Emissions of DEHP occurs from the use of finished products. Major outputs are floor and wall coverings and textile with PVC prints. [Thornthon et al., 2001]

DEHP emissions in Denmark [Thornthon et al., 2001]Product Phthalate used Emission to air Emission to air Release to waste-

(t/y) during production (t/y) during use (t/y) water during use (t/y)Cars 1,000 - 0.1-1 2-10Floor andwall coverings 2,000 - 0.2 1-5Textiles withPVC prints 5-15 - - 2-13

. Sweden

In Sweden domestic contribution to phthalates emission was equivalent to approximately 70% of the total volume of phthalates measured at Gothenburg WWTS. [Thornthon et al., 2001]

. Germany

Emissions of di(2-ethylhexyl)phthalate in the Federal Republic of Germany from 3 different sources [Kollotzek et al.,1998]Reach of emissions Quantity (tonnes/year) Total emission 10,000 – 15,000 [Rippen 1988 in Kollotzek et al., 1998]Total emission 700 [Balzer 1991, in Kollotzek et al., 1998]Total emission 16,000 (of which 10,000 in wastewater) [Giderakos 1993 in Kollotzek et al., 1998]

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Estimation of phthalates emission in Germany in 1995 was 1000-2000 tonnes. [Kaiser et al., 1998]

In 1988 German emission of DEHP was about 1% of the total production (1% of 234,000 Tonnes of DEHP). This emission was discharged to the surface and groundwater compartment. [Brüggermann, 1988 in Thornthon et al., 2001]

V Environmental fate of releases to environment1. Adsorption to solids (sediment, sludge, soil):

Due to high n-octanol-water partition coefficient, low solubility and the “van der waals” type bonding with the natural soil minerals the equilibrium of DEHP between the water and an organic rich soil or sediment will be very much in favour of the soil or sediment. [IPCS, 1992]. DEHP is almost entirely unaffected by anaerobic conditions which accounts for its accumulation. Background concentrations remains constant over a long time period. [Northtine-Westfalia state environmental agency, 2000]

2. Volatilisation:

DEHP has a vapour pressure of 3.4 * 10-5 Pa (20-25°C), which indicates a low evaporation rate from its pure state. The evaporation is also dependent on the nature of the matrix of the product. The evaporation from a polymer matrix is <1% /year. High concentrations are observed in indoor environment. The temperature probably is a key factor to understand these evaporation patterns. In the environment high peak temperatures occur during sun light radiation (up to 70°C). The vapour pressure is 320 times higher at 70ºC compared to 20oC.

3. Degradation:

Long chain length phthalates have a low biodegradability under normal conditions and are only partly degraded in usual leachates and sewage treatment plants. [EC, 2000] The main phthalate sources are phthalate-containing plastics. Even after use and after being discarded, these plastic materials are sources of phthalate pollution. This is primarily because of vaporisation and elution of the compounds into the environment. Phthalates are degraded in surface water down to a certain background concentration. [Northtine-Westfalia state environmental agency, 2000]Degradation in the airAtmospheric photo degradation of DEHP is rapid but its chemical hydrolysis into the environment is Practically non-existent. [IPCS, 1992]Half-life of DEHP as a result of atmospheric photo degradation is less than 1 day. Chemical hydrolysis of DEHP is practically non-existent. [IPCS, 1992]Degradation in waterHalf-life of DEHP in water was found to be 146 days, although theoretically only 25 days were calculated.The half-life is >100 years in water at pH 8 and 30 °C. Aerobic degradation of DEHP has been found with several micro-organisms at a rate of 40-95% over 10-35 days. [IPCS, 1992]Degradation in WWTP DEHP is not removed by conventional anaerobic conditions of sludge. Phthalate esters are rapidly destroyed under aerobic conditions, biological wastewater treatment can usually achieve >90% removal in 24 hours. [Thornthon et al., 2001] In a type of preliminary study of the wastewater monitoring-programme, some untreated wastewater samples were analysed. It was observed that even very high phthalate charges are degraded or separated within the sewage sludge. [Northtine-Westfalia state environmental agency, 2000]Degradation in soilIn soil, the reported half-life of DEHP is <50 days. Biodegradation is temperature dependent. Below 10 °C little biodegradation takes place. At higher temperatures biodegradation proceeds in the upper layers of the soil but is virtually non existent deeper down where conditions are anaerobic. [IPCS, 1992]

4. Partition to compartments:

Although the solubility of DEHP in water is low, the amount present in surface water may be higher due to adsorption onto organic particles and interaction with dissolved organic matter. It is adsorbed particular by small particles, and adsorption is enhanced in salt water. [IPCS, 1992]

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5. Behaviour:

Solubility for uncolloidal DEHP in water is low (45µg/l at 20 degrees). However DEHP may form collodial dispersions, which lead to higher values for solubility (285-360 µg/l at 20-25 degrees). These higher values are probably more realistic in the environment. [IPCS, 1992]DEHP is found regularly in municipal wastewater and, because of its lipophilic properties, it concentrates in sewage sludge. [Thornthon et al., 2001]

VI Evaluation1. Relevant NOSE-codes of point sources

NOSE-code Sources IPPC-code 104.04/105.04 Manufacture of textiles and textile products 6.2104.05/105.05 Manufacture of leather and leather products 6.3104.07/105.07 Manufacture of pulp, paper and paper products, publishing and printing 6.1104.09/105.09 Manufacture of chemicals, chemical products and man-made fibres 4.1104.10/105.10 Manufacture of rubber and plastic products104.11/105.11 Manufacture of other non-metallic mineral products 3.1/3.3107 Processes including use of solvents and other products 6.7107.01 Paint application107.01.05 Paint application : coil coating107.03 Chemical products manufacturing or processing 4.1/6.7107.03.13 Textile finishing107.04.05 Application of glues and adhesives107.04.08 Domestic solvent use (other than paint application) 6.7109.02 Wastewater Treatment109.02.41 Wastewater Treatment in industry109.03 Waste incineration and pyrolysis109.06.04 Sludge spreading109.06.11 Land filling 5.1/5.2111.04.02 Industrial laundries112.01 Cleaning and washing without solvents201 Road transport

2. Evaluation of emission data

a. Emission to water

Source Release Info[EU RAR, 2001] 5987 t/y to wastewater Production+use+losses. 2413 t/y from outdoor losses.

This is the only source that names this release1634 t/y to wastewater3140 t/y to surface water Including 2399 t/y due to leeching from

cables*[Ligthart et al.,2001] 2020 t/y total to water** including 1629 t/y due to service life[Kollotzek et al.,1998] 3901 t/y total to water** Calculated using 60% (based on production volumes

EU-RAR and Ligthart) of total phthalates (7740 t/y) is DEHP and 84% is lost to the watercompartment. [Kapteijns, 1997]

Remarks* According to the OSPAR document 2399 t/y is released to water as a result of leaching from soil

where plastics are burried (pipeline, cables, etc.). This route is very unlikely because DEHP is (slowly) degradable in aerobic soil and adsorbs strongly to soil.

** Fractions to surface water are not clear because:• Total amount to water includes wastewater that may, or may not be treated.• Stormwater may enter sewers or may be discharged directly or as a overflow. The release

routes S8.1-4 are not specified and will differ per country.

b. Emission to airSource Release Info [Ligthart et al.,2001] 5701 t/y Of which 4596 t/y Service life[Kollotzek et al.,1998] 7740 t/y total phtalates 0.6 x 16% [EU RAR, 2001] [Ligthart et al.,2001] = 743 tonnes

DEHP per year

Remarks• Emission to air is not clear. There are multiple contradictory estimations.

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c. Deposition

• Deposition on land will be aerobically degraded or adsorbed. Leaching to water is unlikely to occur.• Deposition to water will be aerobically degraded.• Photodegradation is relatively fast: a half-life is given of less than one day.

3. Gaps and questions

- Release to water as a result of leaching from soil is questionable;- Data (Ligthart et al.,2001], [Kollotzek et al.,1998) on release to surface water do not take into account the

treatment of wastewater and therefore will overestimate the total amount;- Emission to air is not clear.

VII Measures1. Measures at production level:

a. Contribution to water at production level

Total contribution to water (due to wastewater before treatment) is 682 ton/y on a total amount of 5987 ton/y. [EU RAR, 2001]

b. Relevant IPPC sector, documents and available emission criteria

The relevant IPPC sectors are:- 3.1 Production of cement clinker in rotary kilns- 3.3 Manufacture of glass including glass fibre- 4.1 Chemical installations for the production of basic organic chemicals- 5.1 Installations for the disposal or recovery of hazardous waste- 5.2 Installations for the incineration of municipal waste- 6.1 Production of pulp and paper- 6.2 Pre-treatment or dyeing of fibres or textiles- 6.3 Tanning of hides and skins- 6.7 Surface treatment of substances, objects or products using organic solvents (dressing, coating,

etc).

DEHP nor phthalates are mentioned in existing IPPC BREF documents.

Emission criteria (on EU level) don’t exist.

c. Voluntary agreements

The European PVC industry (PVC Industry, European Council of Vinyl Manufacturers (ECVM), theEuropean Stabilisers Producers Association (ESPA), the European Council for Plasticisers andIntermediates (ECPI), and European Plastics Converters (EuPC)) published avoluntary commitment in March 2000 to set out a programme of precautionarymeasures to address potential risks and help the industry meet the challenge ofsustainable development.

d. Substitution

Substitution of PVC plastics or substitution of DEHP as plasticizers in PVC are both possibilities (and already brought into practice) to substitute DEHP in the wide range of industries using PVC [KemI, 1997]

e. Process control, modifications

Not relevant.

f. Effluent treatment

The release from industrial processes can be reduced by adequate treatment. Biological oxidation is a suitable process and can be optimised by extended aeration, addition of powdered activated carbon or polishing in sand filters or effluent ponds.

2. Measures at use level:

a. Contribution to water at use level

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Fact sheets on production, use and release of priority substances in the WFD, Royal HaskoningDi(2-ethylhexyl)phthalate, Final draft For official use onlyWastewater before treatment contains 343 ton/y due to IPPC sectors and SME groups together. Contribution due to use by consumers is 4,888 ton/y (total amount is 5,987 ton/y). [EU RAR, 2001]

b. Use by IPPC sectors

DEHP releases via air and wastewater can be treated locally due to air and wastewater treatment.

c. Use by SME groups

Release of DEHP due to use by SME groups and consumers as well, have to be treated at community level (see paragraph 3).

d. Use by consumers

See 2c (use by SME groups).

The release via diffuse sources to air followed by atmospheric deposition is not properly quantified. It is not feasible to reduce this release without a significant restriction of the use.

e. Use in agriculture

Not relevant.

3. Measures at community level:

a. Sewage treatment

The release from in- and outdoor use by consumer via sewers and sewage treatment is now estimated as 916 tonnes/y. This is based on the assumption that 70 % of the urban wastewater is treated and 30 % is not treated. The current release from outdoor use is released for a significant part via stormwater overflow and this is included in the 30 % not treated. Thus altogether only 40 % is removed.

Reduction of the release to surface water may be achieved by three types of measures:- The fraction of housholds connected to adequate sewers with sewage treatment will increase to

90 % by implementation of Directive 91/271 concerning the treatment of municipal wastewater.- The efficacy of removal in the treatment plants may be increased to 95% by process

improvements such as extended aeration.- The release of stormwater may be reduced by optimisation of sewers, infiltration systems and

holding reservoirs. Some 5 % direct release via stormwater overflow may be the best available practice.

Altogether the removal could be increased to 80 % and the release is then 458 t/y

The release to the sewer from indoor use is mainly caused by floor cleaning. A reduction of this release is difficult to realise, moreover it is questionable if a reduction in the influent concentration will lead to a lower effluent concentration.

b. Waste disposal

The release via sludge of STP’s to agricultural soil will not give a release to surface water. The DEHP will be degraded in the top soil or absorbed to the organic fractions in soil.

The route via leachate of landfills can be reduced by appropriate treatment of the leachate. This type of treatment may be expected to become BAT for landfills. Assuming an efficacy of 95%, this would leave 120 tonnes/year for the EU.

The emission from waste remaining in the environment as mentioned in the EU RAR results from a series of assumptions. The main reason is a loss of 2 – 50% of the outdoor use as particulate. From these particulate 100 % of the DEHP content is released to the environment. The DEHP is then distributed over water and soil with 25 % to water. This source is diffuse and no end of pipe measure is possible.

The assumption that during the leaching of DEHP from particulate polymer (a slow release), no degradation take place and 25 % of the DEHP will reach the surface water is a worst case assumption. Biodegradation will occur by micro-organisms that concentrate in a biofilm around these particles that lay on soil. The real contribution of this source to surface water will therefore be almost zero

c. Incineration

Not relevant because DEHP will be completely incinerated without trace elements.

d. Recycling

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See 2b and 2c for measures at the primary use level, which will be effective at the recycling phase too.

4. Measures at regulatory level:

a. EU level: IPPC emission control

BREF documents could be extended with a paragraph about the possibilities of treatment of DEHP and phthalate (-esters).

b. EU level: Substitution or outphasing

European Parliament Resolution on the commission Green Paper on the environmental issues of PVC (COM(2000) 469) calls on the Commission to examine the substitution of phthalates as plasticizers and suggest that the Commission and PVC Industry should look into the possibility of setting targets for reducing the use of phthalates particularly in medical equipment’s.

c. EU level: Limitations of use in certain applications

The Commission proposes (COM(2002) 70 final, Brussels, 12-02-2002) to add DEHP as a category 2 substance to Directive 76/769/EEC concerning restrictions on the marketing and use of certain dangerous substances and preparations, in this case toys and nursing articles made of PVC.

d. Other regulatory and/or national policy measures

-

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VIII LITERATURE

- Cardigan D.F., 2000. Water Framework Directive.- CEFIC, 1999. The business of Chemistry, a profile of the product

families.- EU RAR (Risk Assessment Report), 2001. Bis(2-ethylhexyl)phthalate. Final

Draft.- EC (European Commission), 2000. Green paper, Environmental issues of

PVC. COM(2000) 469.- IMO, 2001. International Convention on Control of Harmful Anti-

fouling Systems on Ships.- IPCS (International Programme on Chemical Safety), 1992. Diethylhexyl

Phthalate. Environmental Health Criteria 131. WHO. Geneva.- IUCLID, 2000. IUCLID Datasheet DEHP.- Kaiser T., Schwarz W., Frost M., 1998. Eintrage von Stoffen in Boden - eine

Abschatzung des gefahrdungspotentials. Logos Verslag. Germany. - Kapteijns A.J.F., 1997. Additieven in PVC, De milieu-aspecten

geëvalueerd. MEBO.- KemI (Swedish National Chemicals Inspectorate), 1997. Additives in PVC.

Making of PVC. Report of a Government Commission.- Kollotzek, D., Hartmann, E., Kassner, W., Kurrle, J., Lemmert-Schmitt, E., Beck,

A., 1998. Technische, analytische, organisatorische und rechtliche Maßnahmen zur Verminderung der Klärschlammbelastung mit relevanten organischen Schadstoffen, Umweltbundesamt, UBA texte 53/98. Germany.

- Ligthart T.N., R.H.J. Korenromp, G.J. Annokée, 2001. Emission of hazardous substances from finished products. Netherlands Organization for applied Scientific Research (TNO). Published by Keml (Swedish National Chemicals Inspectorate).

- Northrine-Westfalia State Environmental Agency, 2000, Analysis of Phthalates in Wastewater Effluents and Surface Water – summary report-, Federal Environmental Agency.

- Renner, R., 2000. Human phthalate study changes exposure picture. Env. Sci. Technol. 34, 451A - 452A.

- Swedish EPA (Environmental Protection Agency), 2001. Information on emission sources for priority substances. Naturvårdsverket. Sweden.

- Thornthon L., D Butler, P Docx, M Hession, C Makropoulos, M McMullen, M Nieuwenhuijsen, A Pitman, R Rautiu, R Sawyer, S Smith, D White, P Wilderer, S Paris, D Marani, C Bragugalia, J Palerm, 2001. Pollutants in urban wastewater and sewage sludge. Final report prepared by ICON IC consultants Ltd, London, UK.

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APPENDIX 1: Phthalate emission to all compartments in W-Europe in 1990 and in Sweden mainly in 1994[KemI, 1997]

Phthalate emission, t/yW-Europe Sweden

Production 220 <0,5Distribution 80 1-3Processing, total 950 13- Calendering film/sheet and flooring

290 7,1

- Spread coating 520 3- Other plastisol coating 50 0- Extrusion, injection moulding 90 1,3- Other 2Indoor use, total 640- Flooring, evaporation 20 1,3- Flooring, water extraction 100-1000 4,3 (1.7

DEHP)- Wall covering 20 0,3- Other film, sheet coating 40- Wire, Cable, profiles, hose etc. 60- Cable 1,6- Profiles 0,01- Washing of printed textiles 0,4-1,1- Coated textiles 0,1- Film and sheet 0,7Outdoor use, total 5600- Coated steelsheet / plastisol 75- Coated fabric 26- Undercoating 38- Cable- ProfilesDisposal 250 5,6

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Fact sheets on production, use and release of priority substances in the WFD, Draft 3.3 Royal HaskoningFor official use only

Appendix 2: Overview DEHP emission

* It isn’t clear if volatilisation from the landfill to the air is an emission path because of sources giving opposite information[IPCS, 1992]: It is more likely that Indiscriminate dumping will lead to volatilisation of phthalates to the atmosphere

rather than emission to the aquatic environment due to low solubility in water.[Kapteijns, 1997]: 100% of the DEHP emission from waste disposal is to the water compartment

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AIR

SURFACE WATER

SOIL

Consumer use

Buildings

Historicpollution

Agriculture Deposition

Traffic Materials

A4 A3A7A5 / A6 / A9

ProductionFormulation

Industrial use

WWT

Waste Disposal

STP

WWTGROUNDWATE

R

S9.2

S9.2.1

S9.2.2

S9.3

S10.1 S10.2

S8.4

S8.1S8.2S8.3

S7.3 S7.1

S1Erosion

&RunoffS3.2S4.2

107.01104 / 105 / 107 107.04

109.06.11

109.02.42109.02.41

109.02 Drainage S2

Documents

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