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RIVM Rapport 601501024 Environmental Risk Limits For RIVM report 601501024/2005 Environmental Risk Limits for several phosphate esters, with possible application as flame retardant E.M.J. Verbruggen, J.P. Rila, T.P. Traas, C.J.A.M. Posthuma-Doodeman and R. Posthumus This investigation has been performed for the account Directorate-General for Environmental Protection, Directorate for Chemicals, Waste and Radiation, in the context of the project ‘International and National Environmental Quality Standards for Substances in the Netherlands’, RIVM-project no. 601501. Contact: E.M.J. Verbruggen Expert Centre for Substances E-mail: [email protected] National Institute for Public Health and the Environment, PO Box 1, 3720 BA Bilthoven, the Netherlands. Tel. 31-30-2749111, fax. 31-30-2742971 page 2 of 118 RIVM report 601501024 RIVM report 601501024 page 3 of 118 Rapport in het kort Milieurisicogrenzen voor enkele fosfaatesters, met mogelijke toepassing als brandvertrager Voor een aantal fosfaatesters, die mogelijk als vlamvertrager gebruikt worden, zijn Maximaal Toelaatbaar Risiconiveaus (MTR), Verwaarloosbaar Risiconiveaus (VR) en Ernstig Risiconiveaus (EReco, Engelse afkorting SRCeco) afgeleid. Deze milieurisicogrenzen zijn afgeleid voor de compartimenten water, bodem, en lucht en zijn gebaseerd op ecotoxicologische gegevens voor met name het aquatische milieu. Het gaat om de volgende stoffen: TCEP (tris(2-chloorethyl)fosfaat), TCPP (tris(1-chloor-2-propyl)fosfaat), TDCP (tris(1,3-dichloor-2-propyl)fosfaat), TBP (tri-n-butyl fosfaat), TiBP (tri-iso-butyl fosfaat), TEP (triethyl fosfaat), TBEP (tris(butoxyethyl) fosfaat), TEHP (tris(2-ethylhexyl) fosfaat), TPP (trifenylfosfaat) en TCP (tricresylfosfaat). Meetgegevens voor Nederland (1989, 1999-2004) laten zien dat voor de meeste fosfaatesters de concentraties in oppervlaktewater rond het VR liggen. Alleen voor TPP blijkt dat concentraties in oppervlaktewater af en toe het MTR overschrijden. Trefwoorden: milieurisicogrenzen; fosfaatesters; vlamvertragers; maximaal toelaatbaar risiconiveau; ernstig risiconiveau, verwaarloosbaar risiconiveau page 4 of 118 RIVM report 601501024 RIVM report 601501024 page 5 of 118 Abstract Environmental Risk Limits for several phosphate esters, with possible application as flame retardant Maximum Permissible Concentrations (MPC), Negligible Concentrations (NC) and Serious Risk Concentrations (SRCeco) are derived for a number of phosphate esters that are possibly used as flame retardant. These environmental risk limits were derived for the compartments water, soil, and sediment on basis of ecotoxicological data for the aquatic environment in particular. The substances that were evaluated in this study were: TCEP (tris (2-chloroethyl) phosphate), TCPP (tris(2-chloro-1-methylethyl) phosphate), TDCP (tris(1,3-dichloro-2- propyl) phosphate), TBP (tri-n-butyl phosphate), TiBP (tri-iso-butyl phosphate), TEP (triethyl phosphate), TBEP (tris(2-butoxyethyl) phosphate), TEHP (tris(2-ethylhexyl) phosphate), TPP (triphenyl phosphate), and TCP (tricresyl phosphate). Monitoring data for the Netherlands (1989, 1999-2004) show that for most phosphate esters the concentrations in surface water are around the NC values. It appears that only concentrations of TPP sometimes exceed the MPC value. Keywords: environmental risk limits; phosphate esters; flame retardants; maximum permissible concentration; serious risk concentration page 6 of 118 RIVM report 601501024 RIVM report 601501024 page 7 of 118 Contents Samenvatting____________________________________________________________________________ 9 Summary ______________________________________________________________________________ 11 1. Introduction _______________________________________________________________________ 13 2. Substance properties and use _________________________________________________________ 17 2.1 Physicochemical properties _______________________________________________________ 17 2.1.1 Halogenated phosphates _______________________________________________________ 17 2.1.2 Alkyl phosphates _____________________________________________________________ 20 2.1.3 Aryl phosphates______________________________________________________________ 24 2.2 Flame retardant properties ________________________________________________________ 26 2.3 Use, production and discharge _____________________________________________________ 27 2.3.1 Halogenated phosphates _______________________________________________________ 27 2.3.2 Alkyl phosphates _____________________________________________________________ 29 2.3.3 Aryl phosphates______________________________________________________________ 31 3. Methods __________________________________________________________________________ 35 3.1 Literature search and data selection _________________________________________________ 35 3.2 Derivation of environmental risk limits ______________________________________________ 36 3.2.1 Derivation of maximum permissible concentrations (MPCs) ___________________________ 36 3.2.2 Derivation of serious risk concentrations (SRCseco) __________________________________ 36 3.2.3 Derivation of negligible concentrations (NCs) ______________________________________ 36 3.3 Equilibrium Partitioning (EqP) ____________________________________________________ 36 3.4 Secondary poisoning ____________________________________________________________ 37 4. Toxicity data and derivation of ERLs __________________________________________________ 39 4.1 Derivation of ERLs for water______________________________________________________ 39 4.1.1 Halogenated phosphate esters___________________________________________________ 39 4.1.2 Alkyl phosphate esters_________________________________________________________ 40 4.1.3 Aryl phosphate esters _________________________________________________________ 42 4.2 Derivation of ERLs for soil _______________________________________________________ 45 4.2.1 Halogenated phosphate esters___________________________________________________ 45 4.2.2 Alkyl phosphate esters_________________________________________________________ 47 4.2.3 Aryl phosphate esters _________________________________________________________ 48 4.3 Derivation of ERLs for sediment ___________________________________________________ 48 4.3.1 Halogenated phosphate esters___________________________________________________ 48 4.3.2 Alkyl phosphate esters_________________________________________________________ 48 4.3.3 Aryl phosphate esters _________________________________________________________ 49 4.4 Summary of derived ERLs________________________________________________________ 49 5. Preliminary risk analysis ____________________________________________________________ 51 6. Conclusions and recommendations ____________________________________________________ 55 Acknowledgements ______________________________________________________________________ 57 References _____________________________________________________________________________ 59 Appendix 1. Selected toxicity data used for derivation of ERLs__________________________________ 71 Appendix 2. Aquatic toxicity data __________________________________________________________ 77 Appendix 3. Terrestrial toxicity data ______________________________________________________ 111 Appendix 4. Bioconcentration factors ______________________________________________________ 115 page 8 of 118 RIVM report 601501024 RIVM report 601501024 page 9 of 118 Samenvatting In dit rapport zijn Maximaal Toelaatbaar Risiconiveaus (MTRs), Verwaarloosbaar Risiconiveaus (VRs) en ecotoxicologische Ernstig Risiconiveaus (ERecos ) afgeleid voor fosfaatester verbindingen, die mogelijk gebruikt worden als vlamvertragers. De genoemde milieurisicogrenzen zijn afgeleid op basis van ecotoxicologische en milieuchemische data en vormen aansluitend de wetenschappelijke basis voor milieukwaliteitsnormen die worden vastgesteld door de Stuurgroep Stoffen. De onderzochte stoffen zijn: TCEP (tris(2-chloorethyl)fosfaat), TCPP (tris(1-chloor-2- propyl)fosfaat), TDCP (tris(1,3-dichloor-2-propyl)fosfaat), TBP (tri-n-butyl fosfaat), TiBP (tri-iso-butyl fosfaat), TEP (triethyl fosfaat), TBEP (tris(butoxyethyl) fosfaat), TEHP (tris(2- ethylhexyl) fosfaat), TPP (trifenylfosfaat) en TCP (tricresylfosfaat). Alleen toxiciteitsstudies met eindpunten die gerelateerd zijn aan overleving, groei of reproductie zijn in beschouwing genomen. Voor sediment, en meestal ook voor het compartiment bodem, zijn geen toxiciteitsgegevens gevonden die bruikbaar zijn voor het afleiden van EReco en MTR- waarden. In dat geval zijn de ERbodem/sediment en MTRbodem/sediment afgeleid met behulp van de evenwichtspartitiemethode. Tabel 1 en tabel 2 tonen de afgeleide milieurisicogrenzen voor de groep fosfaatesters. Meetgegevens voor Nederland laten zien dat voor de gechloreerde en alkylfosfaatesters de concentraties in oppervlaktewater rond het VR liggen. Alleen voor de arylfosfaatester TPP blijkt dat concentraties in oppervlaktewater af en toe het MTR overschrijden. Tabel 1. Milieurisicogrenzen voor fosfaatesters in zoet oppervlaktewater en zeewater (marien). EReco, opgelost EReco, totaal MTRopgelost MTRtotaal VRopgelost VRtotsal MTRmarien [mg/L] [mg/L] [μg/L] [μg/L] [μg/L] [μg/L] [μg/L] TCEP 8,6 8,6 a a a a a TCPP 6,5 6,5 a a a a a TDCP 0,52 0,54 a a a a a TBP 1,1 1,1 66 66 0,66 0,66 6,6 TiBP 3,4 3,4 11 11 0,11 0,11 1,1 TEP 110 110 1600 1600 16 16 160 TBEP 2,9 2,9 13 13 0,13 0,13 1,3 TEHP b b b b b b b TPP 0,060 0,062 0,16 0,17 0,0016 0,0017 0,016 TCP 0,031 0,031 0,032 0,033 0,00032 0,00033 0,0032 Opmerkingen: a: MTR
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