Environmental risk limits for polycyclic aromatic hydrocarbons (PAHs) For direct aquatic, benthic, and terrestrial toxicity RIVM report 607711007/2012 E.M.J. Verbruggen National Insitute for Public Health and the Environment P.O. Box 1 | 3720 BA Bilthoven www.rivm.com Environmental risk limits for polycyclic aromatic hydrocarbons (PAHs) For direct aquatic, benthic, and terrestrial toxicity RIVM Report 607711007/2012 RIVM Report 607711007 Colophon © RIVM 2012 Parts of this publication may be reproduced, provided acknowledgement is given to the 'National Institute for Public Health and the Environment', along with the title and year of publication. E.M.J. Verbruggen Contact: Eric Verbruggen Expertise Centre for Substances (SEC) [email protected] This investigation has been performed by order and for the account of Ministry of Infrastructure and Environment (I&M), within the framework of Soil Quality, Prevention and Risk Assessment Page 2 of 337 RIVM Report 607711007 Abstract Environmental risk limits for polycyclic aromatic hydrocarbons (PAHs) For direct aquatic, benthic, and terrestrial toxicity RIVM derived maximum permissible concentrations (MPCs) and serious risk concentrations (SRC) for ecosystems for the 16 well-known polycyclic aromatic hydrocarbons (PAHs). This is done for all individual PAHs for water, sediment and soil. Data on the toxic effects were collected for each PAH in water, soil and sediment organisms. For this study, the methodology of the framework ‘International and national environmental quality standards for substances in the Netherlands’ (INS) is used. This method is nationally recognized and where possible, based on European directives. Alternative research method for environmental risk limits PAHs In this study the environmental risk limits were also derived in an alternative way. For this goal, the knowledge was used from previous research on the environmental risk limits of mineral oil that was suitable for PAHs as well. The environmental risk limits are derived based on the calculated concentration of substances in the organisms after they have taken up the substances from the water (for sediment and soil: water in sediment or soil moisture). This method is based on the assumption that certain effects of all 16 PAHs occur at the same concentrations in organisms that live in water, soil and sediment. Because PAHs cause effects in the same way, the concentrations can be added together. This provides insight into the effect of all PAHs simultaneously, as they occur in the environment (toxic unit aproach). Difference in internal and external concentrations The internal effect concentration of PAHs does not differ between organisms in soil, water and sediment. In contrast, large differences between the effect concentrations of the substances outside the organisms were observed. Especially the effect concentrations between soil or sediment on the one hand and water on the other hand were different, and also the effect concentrations of individual PAHs in water. The harmful effects of the substances are thus largely determined by the extent to which a substance is partitioned between water, soil and sediment, and is taken up from water (equilibrium partitioning). As an example, soil binds a substance strongly, so less will end up in soil moisture and eventually in soil organisms. Measurements of concentrations of substances in the environment would thus be better based on concentrations in water. Keywords: naphthalene, acenaphthene, acenaphthylene, fluorene, phenanthrene, anthracene, pyrene, fluoranthene, chrysene, benz[a]anthracene, benzo[k]fluoranthene, benzo[b]fluoranthene, benzo[a]pyrene, benzo[ghi]perylene, dibenz[a,h]anthracene, indeno[1,2,3-cd]pyrene Page 3 of 337 RIVM Report 607711007 Page 4 of 337 RIVM Report 607711007 Rapport in het kort Milieurisicogrenzen voor polycyclische aromatische koolwaterstoffen (PAK’s) Voor directe aquatische, benthische en terrestrische toxiciteit Het RIVM heeft de maximaal toelaatbare risiconiveaus (MTR) en ernstige risisconiveaus (ER) voor ecosystemen afgeleid voor de 16 bekendste polycyclische aromatische koolwaterstoffen (PAK’s). Dit is voor alle afzonderlijke PAK’s gedaan voor water, sediment en bodem. Hiervoor zijn gegevens verzameld over de giftige effecten van elke PAK op water-, bodem- en sedimentorganismen. Voor het onderzoek is de methodologie van het kader ‘(Inter)nationale normen stoffen’ (INS) gebruikt. Deze methode is nationaal erkend en waar mogelijk gebaseerd op Europese richtlijnen. Alternatieve onderzoekswijze voor milieurisicogrenzen PAK’s In dit onderzoek zijn de milieurisicogrenzen ook op een alternatieve manier afgeleid. Hiervoor is de kennis gebruikt van eerder uitgevoerd onderzoek naar de milieurisicogrenzen van minerale olie die ook geschikt bleek voor PAK’s. De milieurisicogrenzen zijn afgeleid op basis van de berekende concentratie van stoffen in organismen nadat zij de stoffen via het water hebben opgenomen (voor sediment en bodem: water in sediment of bodemvocht). Deze methode is gebaseerd op de aanname dat bepaalde effecten van alle 16 PAK’s optreden bij dezelfde concentraties in organismen die leven in water, bodem en sediment. Omdat de PAK’s op dezelfde manier effecten veroorzaken, mogen de concentraties bij elkaar opgeteld worden. Hierdoor wordt inzicht verkregen in het effect van alle PAK’s tegelijkertijd, zoals ze ook in het milieu voorkomen (toxic unit aproach). Verschil inwendige en externe concentraties De inwendige effectconcentratie van PAK’s blijkt bij organismen in bodem, water en sediment niet te verschillen. Daarentegen zijn grote verschillen tussen de effectconcentraties van de stoffen aangetroffen als deze buiten de organismen werden waargenomen. Vooral de effectconcentraties tussen bodem of sediment enerzijds en water anderszijds verschilden, evenals de effectconcentraties van de individuele PAK’s in water. De schadelijke effecten van de stoffen worden dus in grote mate bepaald door de mate waarin een stof zich verdeeld tussen water, bodem en sediment en wordt opgenomen vanuit water (evenwichtspartitie). Zo bindt de bodem een stof sterk aan zich waardoor er minder in bodemvocht en uiteindelijk in bodemorganismen terechtkomt. Metingen van concentraties van stoffen in het milieu zouden daardoor beter gebaseerd kunnen worden op concentraties in water. Trefwoorden: naftaleen, acenafteen, acenaftyleen, fluoreen, fenantreen, antraceen, pyreen, fluoranteen, chryseen, benz[a]antraceen, benzo[k]fluoranteen, benzo[b]fluoranteen, benzo[a]pyreen, benzo[ghi]peryleen, dibenzo[a,h]antraceen, indeno[1,2,3-cd]pyreen Page 5 of 337 RIVM Report 607711007 Page 6 of 337 RIVM Report 607711007 Contents Summary—9 1 Introduction—11 1.1 Project framework—11 1.2 Selection of substances—11 1.3 Reading guide to the report—12 2 Methods—13 2.1 Guidance followed for this project—13 2.2 Trigger values—14 2.3 Data collection and evaluation—16 2.4 Additional methodology and deviations from the guidance—18 3 Derivation of environmental risk limits—21 3.1 Naphthalene—21 3.2 Acenaphthylene—28 3.3 Acenaphthene—30 3.4 Fluorene—34 3.5 Phenanthrene—37 3.6 Anthracene—43 3.7 Pyrene—48 3.8 Fluoranthene—54 3.9 Chrysene—63 3.10 Benz[a]anthracene—65 3.11 Benzo[k]fluoranthene—68 3.12 Benzo[b]fluoranthene—71 3.13 Benzo[a]pyrene—72 3.14 Benzo[ghi]perylene—78 3.15 Dibenz[a,h]anthracene—80 3.16 Indeno[1,2,3-cd]pyrene—82 4 Summary and analysis of data—85 4.1 Overview of derived risk limits—85 4.2 Environmental risk limits on the basis of internal lipid residues—91 References—103 Appendix. Detailed ecotoxicity data—127 Notes—321 Page 7 of 337 RIVM Report 607711007 Page 8 of 337 RIVM Report 607711007 Summary In this report maximum permissible concentrations for ecosystems (MPCs ), eco maximum acceptable concentrations for aquatic ecosystems (MAC ), and eco,water serious risk concentrations for ecosystems (SRCs ) are derived for polycyclic eco aromatic hydrocarbons (PAHs). These environmental risk limits (ERLs) are derived using data on ecotoxicology and environmental chemistry, and represent the potential risk of substances to the ecosystem. They are the scientific basis for environmental quality standards (EQSs) set by the Ministry of Infrastructure and the Environment. Polycyclic aromatic hydrocarbons are substances that have both natural and anthropogenic origins. They can be formed as a result of combustion, and are constituents of many petroleum products as well. PAHs have different physicochemical and environmental properties (e.g. log K , log K , solubility ow oc and BCF). The PAHs that have been considered in this report are the 16 PAHs that were selected by the US Environmental Protection Agency (EPA). These 16 PAHs are also considered in the European Risk Assessment Report (RAR) on coal tar pitch, high temperature (European Commission, 2008). This work forms the basis of the derivation of the environmental risk limits as presented in this report. Additional data that were retrieved after the completion of the RAR, were added to this data set. For each of the individual PAHs environemental risk limits for direct ecotoxicity were derived for water, soil, and sediment. The methodology used for this derivation was that of the project ‘International and national environmental quality standards for substances in the Netherlands’ (INS). Environmental quality standards should be protective for direct ecotoxicity, secondary poisoning of predators such as birds and mammals, and human toxicology through indirect exposure of humans. However, in this report only the route of direct ecotoxicity is addressed. Thus, the derived risk limits cannot be considered directly as proposals for environmental quality standards. All cited ecotoxicity studies were collected and carefully evaluated for their usefulness and reliability. Because of the volatility of especially the lower PAHs and the adsorptive behaviour especially for the higher PAHs, only studies in which the exposure concentrations were verified were considered reliable. An overview of the derived risk limits for each individual PAH is given in Table 94. Contrary to earlier reports on derivation of risk limits for PAHs a substantial amount of terrestrial and benthic ecotoxicity data was retrieved. Therefore, the number of risk limits for individual PAHs that is derived by equilibrium partitioning is substantially lower. Although many more data were retrieved in comparison with earlier risk limit derivations, and consequently lower assessment factors were applied, the values are in general not higher than, but comparable with the existing risk limits. Apart from the derivation of risk limits for each PAH individually, an approach is presented in which the risk limits are derived based on internal residues. This method has been developed and applied for the derivation of risk limits for total petroleum hydrocarbons (TPH) before. It is assumed that toxicity of all PAHs is similar and possibly caused by narcosis, for which the total concentration of compounds in the cell membrane is the key parameter. This means that toxicity of different PAHs differs only as a consequence of different accumulation potential. However, effects are equal on molar basis expressed as residues in the cell membranes. Further, because of similar action, the sum of the internal Page 9 of 337
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