Fact sheets on production, use and release of priority substances in the WFD, Royal Haskoning
Nonylphenol, Final draft
For official use only
Draft version: final draft (previous version: 3.3)
Status date: 15 Oktober 2002
Comments:
- Changed format
- Remarks of EU letter ENV B.1/PMM/JD’E/ipD (2002) 310893 (30-702) incorporated
- Measures added
SUBSTANCE: NonylphenolI Chemical identity
CAS number:25154-52-3
Chemical group:Organic compounds of oxygen
Chemical formula:C15-H24-O
Homologues:Not relevant
Synonyms:Nonylphenol, isomerenchemisch, phenol, nonyl, nonylfenol, NP
Technical mixtures:Not relevant
II Physical properties
Water solubility:3 mg/l [Hüls, 1995c in EU RAR, 2001]
3.63 mg/l (seawater) [Roy F. Weston Inc., 1991 in EU RAR, 2001]
5.43 mg/l at 20°C [Ahel, 1987 in EU RAR, 2001]
6.237 mg/l at 25°C and PH7 [Roy F. Weston Inc., 1990c in EU RAR, 2001]
11 mg/l [Hüls, 1994 in EU RAR, 2001]
Vapour pressure:100 Pa (20 °C)
Log Kow:4.2 – 4.7 [ICI, 1995 in EU RAR, 2001]
3.28 [Hüls 1989a in EU RAR, 2001]
>3.8 to >4.77 [Roy F. Weston Inc., 1990b in EU RAR, 2001]
4.48 [Ahel 1994 in EU RAR, 2001]
III Production and use in 15 EU member states and accession states
- Way of production/Process description:
There are three main processes used to manufacture nonylphenol. The process varies between producers. [EU RAR, 2001]
-Phenol and mixed nonens are reacted in the presence of a catalyst in a batch process. The catalyst used is montmorillonite clay/fulcat and phosphoric acid.
-Phenol and mixed nonens are reacted in the presence of a sulphonated ion exchange resin in a batch process. The catalyst/precoat system can be reused for between 40-500 batches.
-Phenol and mixed nonens are reacted in the presence of a fixed bed ion exchange resin in a continuous process. The catalyst has a life of about three months.
- Fields of application:
-Nonylphenol ethoxylates
-Resins, plastics, stabilisers etc.
-Phenolic oximes, used as a reagent for the extraction and purification of copper from ore [EU RAR, 2001]
Use of nonylphenol ethoxylates within the EU [EU RAR, 2001]:
- Captive use
- Electrical engineering industry
- Industrial and institutional cleaning
- Textile auxiliaries
- Leather auxiliaries
- Agriculture
- Emulsion polymerisation
- Speciality paints
- Pulp and paper
- Metal industry
- Other niche markets
- Production volume:
EU production of NP was 73,500 tonnes/y in 1997, produced by four companies. Additionally, 8,500 tonnes were imported and 3,500 tonnes/y exported [Environment Agency, 1999c in RPA, 2000].
Production of nonylphenol in Germany is decreased from 17,000 tonnes (1985) to 10,000 tonnes (1995)
The worldwide production capacity of NP in 1996 was approximately 450,000 tonnes of which 110,000 tonnes in Western Europe. A third of this West-European production is exported. [Leisewitz and Schwarz, 1997]
- Number of production sites and locations of production:
Producers and capacities in Western Europe, 1995/96 (in tonnes) [Leisewitz and Schwarz, 1997]
PlantCapacity
Hüls AG, D-Marl40,000
EniChem, I-Mantovia24,000
SISA (Societa Italiana Serie Acetica Sintetica), I-Pioltello15,000
ICI, GB-Wilton20,000
Berol (Akzo Nobel Surfac Chemistry), S-Mölndal10,000
Total109,000
- Use volume:
Production and usage of Nonylphenol in Western Europe in 1995 (in tonnes)[Leisewitz and Schwarz, 1997]
Production capacity109,000
Production77,000
Import5,000
Export18,000
Usage64,000
Various use volumes in Sweden in 1996 (in tonnes): [Swedish EPA, 2001]
ProductImportProductionExport
Hardener to plastic- colour-
and building industry1021
Binding agent6
Colours22
Floor board, moisture barrier<11
Others214
- Relative use volumes in various applications:
Use of Nonylphenol within the EU (1994, 1997) [EU RAR, 2001]
VolumePercentage of tonnage (use)
1994199719941997
Production of nonylphenol ethoxylates42,35047,0005460
Production of resins, plastics, stabilisers etc.33,75029,0004337
Production of phenolic oximes2,4002,50033
Total78,50078,500100100
Industrial use categories for NPEO in the EU (1994) [EU RAR, 2001]
Cat.nr.Industrial useMain.catNPEO(t/a)%aNP (t/a)b
1Agricultural industry44,9197.571.774
2Chemical industry: basic chemicals930.1428
3Chemical industry:
Chemicals used in synthesis(1)/24,5887.011,641
4Electrical/electronic engineering ind.3/2930.1428
5Personal domestic3,6705.651,566
6Public domain19.28629.677,194
7Leather processing industry2/36,2749.622,462
8Metal extraction, refining and
Processing industry2/3930.1428
9Mineral oil and fuel industry3/4930.1428
10Photographic industry2/3930.1428
11Polymers industry24,6797.21,899
12Pulp, paper and board industry2/38021.23276
13Textile processing industry2/37,73411.91,576
14Paints, lacquers and vanishes ind.2/3/43,9976.1528
15Engineering ind., civil & mechanical930.143,065
0Other8,50013.0728
Total (include imports)65,00724,560
Exports35,400
a% refers to the percentage of total ethoxylates used.
bNonylphenol refers to estimated amount of nonylphenol used to produce the ethoxylate.
Functional use categories for nonylphenol ethoxylates in the EU (1994) [CEFIC, 1996 in EU RAR, 2001]
Use cat.nr.Functional usePercentage
9Cleaning/washing agents44.7
13Construction materials and additives1.4
15Cosmetics1.5
16Dust binding agents1.4
23Flotation agents1.7
25Foaming agents2.8
33Intermediates0.2
38Plant protection products, agricultural0.1
50 Surface active agents46.1
0Others0.1
Use of nonylphenol ethoxylates within the EU (1997) [EU RAR, 2001] [OSPAR, 2001]
Volume (tonnes)
NPEO production118,000
NPEO imports5,600
NPEO exports46,000
Total EU Use77,600
EU15 UseAs percentage of EU use
Captive use7,0009
Industrial and institutional cleaning23,00030
Textile auxiliaries8,00010
Leather auxiliaries6,0008
Agriculture5,0006
Emulsion polymerisation9,00012
Paints4,0005
Pulp and paper1,0001
Metal industry2,0003
Other niche markets7,0009
Total72,00093
Difference use and EU use5,6001)
1)The volume used does not appear to take account of the import volume of 5,600 tonnes. Industry thinks this volume is probably divided among the other applications.
- Existing regulation in member states or associated member states:
The following international agreements/reporting systems concern NP/NPE specifically, or as part of more general commitments on hazardous substances, such as:
NSC – Talking concerted action within component international forums (EU) to substitute the use (cf. ED Annex 2, §4.1 (viii).
PARCOM Recommendation 92/8 on Nonylphenol-Ethoxylates. According to this recommendation, the use of nonylphenol-ethoxylates as cleaning agents (for industrial uses) should be phased out by the year 2000. Virtually all domestic uses of NPE as cleaning agents have been phased out according to information from the OSPAR countries.
National voluntary agreements with the trade association SPT (soap, perfume, technical chemical products) e.g. to phase-out their use of nonylphenolethoxylates in cleaning products.
- Industrial associations to be addressed:
IV Releases to environment
- General way of entrance and schematic picture:
If NP/NPE reach the marine environment they will generally do so via industrial wastewater from different industry activities e.g. production of NP and NPE, when using NP and NPE in the formulation of other chemical products and articles and via municipal wastewater and via incineration of wastes. [OSPAR, 2001]
The release to waste water treated by sewage treatment plant gives a generic residue of 2.5% NP in the effluent and 19.5% NP in the sludge. The total regional release to surface water is then diluted homogeneously in the generic flow through the hypothetical region (6.9 x 107 m3/d). The concentration in water is corrected for equilibrium partition to suspended solids. [EU RAR, 2001]
- Atmospheric cycle:
- Industrial Point Sources to the air
50 producers in the EU produce phenol/formaldehyde resins. Twenty are thought to routinely use NP. Releases to air are estimated to be:
Local 0.09 kg/day (average) 0.15 kg/day (worst case)
Regional 0.06 kg/day; Continental 0.56 kg/day [EU RAR, 2001]
Epoxy Resins (NOSE 105.09.89)
In the production process of epoxy resins the following releases to air are given:
Local 0.0026 kg/day; Regional 0.04 kg/day; Continental 0.36 kg/day. [EU RAR, 2001]
- Municipal Collective Sources to the air:
- Diffuse sources to air and deposition
- Aquatic releases:
- Industrial Point Sources to the aquatic environment
The UK draft risk assessment contains a row of release estimations. In summary they indicate the following continental releases of NPs and NPE in the EU: [OSPAR, 2001]
-2856 kg/day of NPs to surface water. Which means 0.1 kg/day from production of NP, 165.1 kg/day from NPE-production, 0.55 kg/day from production of resins, plastics, stabilisers and from different use categories using NPE 2690 kg/day
-80.45 kg/day of NPs to wastewater. Which means 78.3 kg/day from production of NPE and 2.15 kg/day from production of resins, plastics and stabilisers.
-20980 kg/day absorbed to sewage sludge, due to treatment in wastewater treatment plants.
UK estimations of contribution to the continental burden of NP attributed to various industry sources of NPE in Western Europe in 1997. [OSPAR, 2001]
Category% total NP Burden
Industrial & institutional & domestic cleaning44.7
Other niche markets & Unaccounted for23.7
Textile auxiliaries14.7
Leather auxiliaries6.1
NPE production5.8
Emulsion polymerisation; Pulp&Paper;
Metal industry; Agriculture, Paints etc.5.0
Total100
Phenolic oximes (NOSE 104.09/ 105.09)
One company uses NP to manufacture phenolic oximes. 94 kg/year of this NP is discharged to waste water. Emissions to air and soil are zero. [EU RAR, 2001]
Nonylphenol/formaldehyde resins (NOSE 105.09.89)
50 producers in the EU produce Phenol/formaldehyde resins. 20 Are thought to routinely use NP. Releases to water are estimated to be:
Local 0.09 kg/day (average) 0.15 kg/day (worst case)
Regional 0.06 kg/day; Continental 0.56 kg/day
The release fraction of NP to effluent is 0.000008 by an average use volume of 650 t per year and production of 70 days/year.
Epoxy Resins (NOSE 105.09.89)
In the production process of epoxy resins the following releases to water are given:
Local 0.0026 kg/day; Regional 0.04 kg/day; Continental 0.36 kg/day. [EU RAR, 2001]
- Municipal Collective Sources to the aquatic environment:
- Diffuse sources to water
- Overall Releases and Summary:
Total continental releases of NPEs: [OSPAR, 2001]
-107,602 kg/day of NPEs to wastewater. This from different uses of products containing NPE.
-2,273 kg/day of NPEs emissions to air, due to treatment in wastewater treatment plants.
The calculation of the continental (European) emission from NPEO users and other NP users is based on the fraction of the use volume for that category, times the release fraction to water. The following figures are used [Blok, 2001]:
Use categoryRelease fraction water kg/kgContinental emission kg NPEO/d
Formulation3 x 10-3533
Synthesis Chem. Ind.7 x 10-3120
Electr. Eng.5 x 10-31.15
Ind. Cleaning
Publ. Domain0.951,041
Leather processing0.96,962
Metal extr.0.321,402
Min. oil & fuels1 x 10-410
Photogr, ind.0.8183
Polymers1 x 10-42.22
Pulp & paper11,973
Textile0.8516,767
Paints manuf.5 x 10-349.3
Paints use5 x 10-3160
Civil & mech. eng.1 x 10-122.9
Other ind. cleaning0.927,074
TOTAL107,602
Other NP users
Formaldehyde resins1 x 10-50.56
Epoxy resins1 x 10-40.36
Plastic stabilisers5 x 10-41.23
TOTAL2.15
Based on a residue of 2.5% NP from NPEO use, the continental NP emission to water will be 2,690 kg/d, and a 10% regional value would be 269. It can be concluded that the recalculated emission from NP producers of 0.87 kg/d is very low in comparison to the emission of the NPEO users. From the survey it is clear that 105,219 kg/d out of 107,604 or 98% of the NPEO emission is from the following use categories [Blok, 2001]:
Use categoryContinental emission kg NPEO/daynumber of sites
Industrial cleaning in public domain51,041>5,000
Leather processing6,9621,000
Metal extraction1,40250
Pulp & Paper1,9731,300
Textile16,767>1,000
Other industrial cleaning27,074>10,000
Total105,219
V Environmental fate of releases to environment
- Adsorption to solids (sediment, sludge, soil):
ParameterSoil 1Soil 2Soil 3
Cation exchange capacity (meq/100 g)28.446.224.6
Exchangeable bases (meq/100 g)27.845.817.2
Exchangeable acids (meq/100 g)0.60.47.4
Total organic carbon (%)0.8210.28.6
pH7.17.36.4
Kpsoil (l/kg) 4,0092,3015,164
- Volatilisation:
- Degradation:
NP released to the atmosphere is likely to be degraded by reaction with hydroxyl radicals. The rate constant has been estimated using AOP program (Syracuse, 1991) to be 5.4x10-11 cm3.molec-1.s-1.
The reaction rate is such that NP is unlikely to be transported far from its emissions source. It is unlikely to move from the atmosphere to the stratosphere and contribute to ozone depletion. NP is not thought to contribute to low level ozone formation. [EU RAR, 2001]
Aquatic
Abiotic:
Hydrolysis and photolysis are thought to be negligible removal for NP in the aquatic environment.
Biodegradation:
The primary biodegradation of nonylphenol ethoxylates appears to occur rapidly during wastewater treatment, especially with acclimated micro-organisms. The first step for NPnEO (where n>3) appears to be rapid removal of the ethoxylate groups to form NP1EO and NP2EO. Once formed these can then be oxidised to form the carbonates (NP1EC and NP2EC) or are degraded to nonylphenol or other degradation products where the aromatic ring is broken, leading to complete mineralisation. Under aerobic conditions, oxidation of NP1EO and NP2EO to NP1EC and NP2EC appears to be favoured over formation of nonylphenol. However, under anaerobic conditions, much larger amounts of nonylphenol appear to be formed from NP1EO and NP2EO. [EU RAR, 2001]
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, 2001]
- Partition to compartments:
- Behaviour:
VI Evaluation
- Relevant NOSE-codes of point sources:
110.06Use of pesticides and limestone
113.01Household consumption and similar processes (batteries and other
lead containing products)
107.01Paint application6.7
111.02Vehicle service centres and petrol stations
111.03.03Veterinary clinics (medicines)
111.04.01Small scale photographic processors
112.01Cleaning activities
112.02Machines and equipment maintenance and operations
104.04/105.04Characteristic processes in the manufacture of textiles and textile
products6.2
104.05/105.05Characteristic processes in the manufacture of leather and leather
products6.3
104.07/105.07Characteristic processes in the manufacture of pulp, paper and
paper products, publishing and printing6.1
104.09/105.09Characteristic processes in the manufacture of chemicals, chemical
products and man made fibres (polymer/plastics)4.1
105.01.03Electroplating
105.09.89Other polymer, resin and glue manufacturing
105.09.93Pigment manufacture4.1
105.09.95Pesticides4.4
104.11/105.11Characteristic processes in the manufacture of other non-metallic
mineral products (ceramic products)3.1-5
104.12/105.12Characteristic processes in the manufacture of basic metals and
fabricated metal products, involving fuel combustion (ferrous metals
processing)2
106Extraction and distribution of fossil fuels and geothermal energy
(incl. Refineries and offshore activities)
109Pollution control, treatment and waste disposal
109.02Municipal wastewater (incl. Storm water runoff and sludge)5.3, 5.4
107.03.07Paints manufacture4.1
113.01Consumer use
[OSPAR/EC, 2001]
- Evaluation of emission data:
- Emission to water
Municipal:1337 kg/d
Point sources:1623 kg/d
Diffuse sources:871 kg/d
1
Point sources (42%)
Category% NP Burden
Textile auxiliaries14.7
Leather auxiliaries6.1
NPE production5.8
Emulsion polymerisation; Pulp&Paper; Metal industry; Paints etc.4
Other niche markets & Unaccounted for23.7
Total54.3
Municipal sources (35%)
Municipal sources consist for 100% of domestic, institutional and industrial cleaning.
Diffuse sources (23%)
Deposition contributes for 95% of the diffuse sources to surface water. The rest is agricultural use
- Emission to air
- Deposition
- Gaps and questions:
VII Measures
- Measures at production level:
- Contribution to water at production level
- Relevant IPPC sector, documents and available emission criteria
-2. Production and processing of metals;
-3.1 Installations for the production of cement clinker in rotary kilns;
-4.1 Chemical installations for the production of basic organic chemicals;
-4.4 Chemical installations for the production of basic plant health products and biocides;
-5 Waste management;
-5.3 Installations for the disposal of non-hazardous waste;
-5.4 Landfills (receiving more than 10 tonnes per day);
-6.1 Industrial plants for the production of pulp and paper;
-6.2 Plants for the pre-treatment or dyeing of fibres and textiles;
-6.3 Plants for the tanning of hides and skins.
BAT are mentioned in the following BREF documents of the IPPC sector:
-Pulp and paper industry;
-Tanning of hides and skins;
-Textiles industry.
- Voluntary agreements
- Substitution
- Process control, modifications
- Effluent treatment
-research in Spain to investigate the removal of nonylphenol (-ethoxylates) from waste water in communal biological treatment plant;
- Measures at use level:
- Contribution to water at use level
- Use by IPPC sectors
-Avoid use of nonylphenol ethoxylates;
BAT in textiles industry
-The use of alkylphenol ethoxylates-free auxiliaries as substitute for nonylphenol (and other alkylphenol) ethoxylates.
BAT in tanning of hides and skins:
-use of alcohol ethoxylates as surfactant as substitution of nonylphenol ethoxylates;
- Use by SME groups
- Use by consumers
- Use in agriculture
- Measures at community level:
- Sewage treatment
- Waste disposal
- Incineration
- Recycling
- Measures at regulatory level:
- EU level: IPPC emission control
- EU level: Substitution or outphasing
- EU level: Limitations of use in certain applications
- Other regulatory and/or national policy measures
The following international agreements/reporting systems concern NP/NPE specifically, or as part of more general commitments on hazardous substances, such as:
NSC – Talking concerted action within component international forums (EU) to substitute the use (cf. ED Annex 2, §4.1 (viii).
PARCOM Recommendation 92/8 on Nonylphenol-Ethoxylates. According to this recommendation, the use of nonylphenol-ethoxylates as cleaning agents (for industrial uses) should be phased out by the year 2000. Virtually all domestic uses of NPE as cleaning agents have been phased out according to information from the OSPAR countries.
VIII Literature