Ministerie van Verkeer en Waterstaat Directoraat-Generaal Rijkswaterstaat Rijksinstituut voor Kust en Zee/RIKZ Chemical study on alkylphenols Report: RIKZ/2001.029 1 juli 2001 Authors: BKH Consulting Engineers drs. C.P. Groshart drs. P.C. Okkerman drs. W.B.A. Wassenberg RIKZ drs. A.M.C.M. Pijnenburg BKH Consulting Engineers P.O. Box 5094 2600 GB Delft Tel. 31 15 2625299 Fax 31 15 1619326 RIKZ Kortenaerkade 1 P.O. Box 20907 2500 EX Den Haag Tel. 31 70 3114311 Fax 31 70 3114330 _____________________________________ Chemical study on alkylphenols 1 _____________________________________ Chemical study on alkylphenols 2 Contents . .. Preface 5 Summary 6 1 Introduction 13 1.1 Backgrounds 13 1.2 Objectives 13 1.3 Limitations 14 2 Physical chemical properties 15 2.1 Identification 15 2.1.1 Octylphenols 15 2.1.2 Nonylphenols 16 2.1.3 Alkylphenolethoxylates 17 2.2 Physico-chemical characterisation 17 2.3 References 19 3 Production and use 21 3.1 General 21 3.2 Major producers 21 3.2.1 Alkylphenols 21 3.2.2 Nonylphenol ethoxylates 22 3.3 Production processes 23 3.3.1 Nonylphenol 23 3.3.2 Nonylphenol ethoxylates 24 3.4 Major applications 24 3.4.1 Nonylphenol 24 3.4.2 Nonylphenol ethoxylates 25 3.5 Demands in the EU 28 3.5.1 Nonylphenol 28 3.5.2 Nonylphenol ethoxylates 28 3.6 Demands in the Netherlands 31 3.6.1 Nonylphenol 31 3.6.2 Nonylphenol ethoxylates 32 3.7 Waste disposal 33 3.7.1 Nonylphenol 33 3.7.2 Nonylphenol ethoxylates 34 3.8 Potential alternatives 34 3.8.1 Nonylphenol 34 3.8.2 Nonylphenol ethoxylates 34 3.9 Conclusions and recommendations 35 3.10 References 36 4 Emissions to aquatic environment 39 4.1 Industrial sources 39 4.1.1 Production 39 4.1.2 Use as an industrial intermediate 39 4.2 Formulation 40 4.2.1 Nonylphenol 40 4.2.2 Nonylphenol ethoxylates 40 4.3 Captive use and service life 40 _____________________________________ Chemical study on alkylphenols 3 4.4 Transboundary emissions 42 4.4.1 Atmospheric deposition 42 4.4.2 Hydrological transport 42 4.5 Evaluation 42 4.5.1 Basic production and use data 42 4.5.2 Emission factors 43 4.6 Conclusions and recommendations 43 4.7 References 43 5 Behaviour in the aquatic environment 44 5.1 Introduction 44 5.2 Solubility and volatilisation 44 5.2.1 Octylphenol and octylphenol ethoxylates 44 5.2.2 Nonylphenol and nonylphenol ethoxylates 44 5.3 Sorption 46 5.3.1 Octylphenol and octylphenol ethoxylates 46 5.3.2 Nonylphenol and nonylphenol ethoxylates 47 5.4 Transformations in freshwater and marine environments 49 5.4.1 Hydrolysis 49 5.4.2 Photolysis 49 5.4.3 Biodegradation and mineralisation 50 5.5 Bioconcentration 60 5.5.1 Octylphenol and octylphenol ethoxylates 60 5.5.2 Nonylphenol and nonylphenol ethoxylates 60 5.6 Distribution in water systems 65 5.7 Conclusions and recommendations 67 5.8 References 68 6 Occurrence in the aquatic environment 73 6.1 Analytical techniques 73 6.2 Occurrence in freshwater environment 74 6.2.1 Surface water 74 6.2.2 Sediment 76 6.2.3 Wastewater treatment and sewage sludge 79 6.2.4 Organisms 81 6.2.5 Groundwater 82 6.2.6 Rainwater 82 6.3 Occurrence in marine environment 82 6.3.1 Surface water 82 6.3.2 Sediment 82 6.3.3 Organisms 83 6.4 Conclusions 83 6.5 References 83 7 Toxity in the aquatic environment 87 7.1 Mechanism of toxicity 87 7.1.1 Metabolism 87 7.2 Toxic effects in the aquatic environment 87 7.2.1 General 87 7.2.2 Toxic effects in freshwater aquatic environment 88 7.2.3 Effects observed in the environment 94 7.2.4 Estrogenic potencies 97 7.2.5 Comparing exposure concentrations to environmental criteria 97 7.2.6 Toxic effects in marine aquatic environment 98 7.3 Standards and derivation of iMPCs 102 _____________________________________ Chemical study on alkylphenols 4 7.4 Human toxicity 107 7.5 Conclusions 108 7.6 Recommendations 109 7.7 References 109 8 Policy overview 120 8.1 National environmental policy 120 8.1.1 Netherlands 120 8.1.2 Other country specific policy 120 8.2 European Commission 122 8.3 International policy 122 8.3.1 OSPAR 122 8.4 References 122 Annex 1 Abbreviation list Annex 2 List of commercially used products Annex 3 Degradation of nonylphenol and nonylphenol ethoxylates Annex 4 Background information on aquatic toxicity _____________________________________ Chemical study on alkylphenols 5 _____________________________________ Chemical study on alkylphenols 6 Preface . In the framework of the project “Investigating for chemicals in the future”, the North Sea Directorate has put the department of Rijkswaterstaat Institute for Coastal and Marine Management (RIKZ) in charge, to start a study on unknown chemicals. The object of this project is to identify the most important contaminants, which present a threat to the North Sea and the identification of gaps in policy, management and knowledge. In the project monitoring data are evaluated and a number of “new” substances are proposed as a potential threat for the North Sea. On 30th of June 2000 BKH Consulting Engineers has received the order to make a study on a selection of the Alkylphenols. This study will be directed on the whole track of octyl, nonyl and decylphenols in the environment. From production and emission to immission, waste and effects. The project is co-ordinated by Mrs drs A.M.C.M. Pijnenburg of RIKZ. The project- leader of BKH is Mrs drs C.P. Groshart. The authors of the report are: Mr drs P.C. Okkerman, W.B.A. Wassenberg and Mrs drs C.P. Groshart. _____________________________________ Chemical study on alkylphenols 7 _____________________________________ Chemical study on alkylphenols 8 Summary . General Alkylphenols are mainly used as raw material in the production of a variety of industrial products such as surfactants, detergents, phenolic resins, polymer additives and lubricants. Private and commercial use of alkylphenols does not occur. Current world demand is estimated at approximately 400,000 tonnes/y, with nonylphenol as the most widely used compound (market share: 80- 90%). Octyl-, dibutyl-, decyl- and dodecylphenols are produced in total quantities of 60,000 tonnes/year. Nonylphenol production in Western Europe amounts to 75,000- 80,000 tonnes/year. Octylphenol production is estimated at approx. 7,000 tonnes/year. In the Netherlands, there are no production sites for alkylphenols. Nonylphenol demand in The Netherlands is estimated at 1300- 1400 tonnes/year. For the next few years, world demand will grow 1-2 % per year. Alkylphenol ethoxylates are primarily used as surfactants, detergents and emulsifiers in a wide range of applications in the industry (auxiliaries) and as commercial product (cleaning agents, wetting agents, dispersants, lubricants, etc) in many end use sectors. Current world demand is estimated at 600,000 tonnes/y, with nonylphenol (85%) and octylphenol ethoxylates (15%) as most widely used compounds. World demand growth is estimated at 2-3 %/year. In the EU, due to voluntary and regulatory initiatives, the use of these substances is to be limited in order to minimise alkylphenol emissions to the environment. In Western Europe, nonylphenol ethoxylates production is about 120,000 tonnes/year. Demand in the EU varies from 65,000 to 80,000 tonnes, while export amounts to 35,000- 45,000 tonnes/year. In the Netherlands, there is no production of alkylphenol ethoxylates. Annual nonylphenol ethoxylates demand in 1997 was estimated at approx. 1,500 tonnes, coming down from 4,900 tonnes/year in 1986. Sources and emissions Nonylphenol emissions due to use in the chemical and polymer industry in the Netherlands (<15 kg/ year) are negligible compared to emissions from nonylphenol ethoxylates degradation in municipal wastewater (14.1 tonnes/year; see table 1). Nonylphenol ethoxylates emissions to surfacewater in the Netherlands are estimated at 45 tonnes (1997). From table 1 can be seen that the first 6 use sectors are responsible for the total nonylphenol and nonylphenol ethoxylates emissions to surfacewater. On European scale, emissions of nonylphenol and nonylphenol ethoxylates amount to 1065 and 3400 tonnes/year. Environmental characteristics and toxicity in aquatic systems Environmental characteristics Alkylphenols are characterised by low solubility in water (< 15 mg/l) and low vapour pressures (< 10 Pa). Log Kow values vary from 4.1 for octylphenol to 4.5 for nonylphenol. Octyl- and nonylphenol will be non-volatile and will adsorb strongly onto solids. Alkylphenol ethoxylates with many ethoxylate groups (n>10), are very soluble in water, making these compounds potentially mobile. However, once released in water, they are easily hydrolysed to compounds with few ethoxylate groups (n<3), which behave more or less the same as the core alkylphenol compounds (strong adsorption to solids). _____________________________________ Chemical study on alkylphenols 9 Environmental data for nonylphenol indicate that this compound is strongly concentrated in freshwater algae and fish. (BCF = 6000- 7000 and 200- 600 l/kg respectively). Nonylphenol was not found to bio-accumulate in the food chain. BCF values for short chained nonylphenol ethoxylates (n<3) show the same tendency to accumulate in aquatic biota, but BCF values are somewhat lower (1000- 5000 l/kg for algae and 80- 150 l/kg for fish). Half-life for excretion from fish is short (< 1 day). BCF data in marine biota were found to be in the same range as for freshwater organisms. Table 1: Nonylphenol (NP) and nonylphenol ethoxylates (NPEO) emissions (1997) The Netherlands European Union NPEO Emissions to water NPEO Emissions to water Use use NPEO NP NPEO NP Agrochemicals 95 9.5 3.0 5000 500 155 Various niche applications 235 15.3 4.8 12300 800 250 Industrial cleaning 180 11.6 3.6 23000 1500 470 Leather processing 60 3.8 1.2 3100 200 65 Metal processing 50 3.4 1.1 2000 45 14 Pulp and paper industry 15 1.0 0.3 800 55 18 Chemical industry 470 0.2 0.07 7000 3 0.9 Paints & lacquer manufacture 235 0.1 0.03 4000 2 0.6 Domestic use of paints 60 0.1 0.03 3200 5 1.6 Textile processing - - - 4800 290 90 Total 1400 45.0 14.1 65200 3400 1065 Nonylphenol is resistant to hydrolysis but is susceptible to photolysis in water.