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Part I - Benzene, Ethylbenzene and Isopropylbenzene This Report Was Requested by the Commission of the European Communities

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Part I - Benzene, Ethylbenzene and Isopropylbenzene This Report Was Requested by the Commission of the European Communities UPDATING OF DATA CONCERNING THE IMPACT ON THE AQUATIC ENVIRONMENT OF CERTAIN DANGEROUS SUBSTANCES, SECOND PART Part I - Benzene, ethylbenzene and isopropylbenzene This report was requested by the Commission of the European Communities. Any views expressed in this report do not necessarily reflect the views of the Commission of the European Communities. Cataloguing data can be found at the end of this publication. Luxembourg: Office for Official Publications of the European Communities, 1993 Part 1: ISBN 92·826·5894·5 Parts I-IV: ISBN 92·826-5893-7 © ECSC-EEC-EAEC, Brussels • Luxembourg, 1993 Reproduction is authorized, except for commercial purposes, provided the source is acknowledged. Printed In Belgium Ji'-11'1, 3JI @ 2 ~ J9 csr;· ~ COMMISSION OF THE EUROPEAN COMMUNITIES DIRECTORATE-GENERAL Environment, Nuclear Safety and Civil Protection XI/A/3 _updating of data concerning the impact on the aquatic environment of certain dangerous substances, 2nd pa-!_ Part I Benzene, ethylbenzene and isopropylbenzene May, 1992 ./r bkh consulting engineers - 1 - PREFACE The Commission of the European Communities, Directorate-General for Environment, Nuclear Safety and Civil Protection has commissioned BKH Consulting Engineers to carry out Study Contract B6612-90-006688: Updating of data concerning the impact on the aquatic environment of certain dangerous substances, 2nd part: benzenes. The study deals with the following dangerous substances which belong or should belong to List I of Directive 76/464/EEC: benzene (7) ethylbenzene (79) isopropylbenzene (87) chlorobenzene (20, 53, 54, 55, 109, 117, 118) chloronitrobenzene (27, 28, 29, 30, 63) chloroanilines (17, 18, 19, 52) The study updates information on the description of the substances, the level of contamination of the aquatic environment, the persistence of the substances in the aquatic environment and other media, the toxicity (mainly in the aquatic environ­ ment) and bioaccumulation. On the basis of the available data, water quality standards are proposed. The study is presented in four parts: Part I Benzene, ethylbenzene and isopropylbenzene Part II Chlorinated benzenes Part ill Chloronitrobenzenes and 4-chloro-2-nitroaniline Part IV Chloroanilines The study has been carried out by F. Balk, P.C. Okkerman, M. Hof, A. van de Bovekamp and J.W. Dogger. Critical remarks of J. Blok were greatly appreciated. - 11 - SUMMARY The impact of benzene, ethylbenzene and isopropylbenzene on the aquatic environment is evaluated in order to provide a toxicological basis to derive a proposal for water quality criteria. This evaluation is an update of two earlier reports to EC (Persoone and Vanhaecke, 1982 and Chambon, 1984). Data on physical and chemical properties, degradability, toxicity, chemical detection and environmental concentrations have been reviewed. The availability of data on the different subjects is summarized in Table i. Benzene, ethylbenzene and isopropylbenzene are widely used for a variety of products in the chemical industry; they may be used as solvents; benzene and isopropylbenzene are components of gasoline. Total production in the EC in 1987 of benzene, ethylbenzene and isopropylbenzene 3 3 3 is estimated at >440* 10 , 2900* 10 and < 1370* 10 tons/year, respectively. Benzenes can be chemically analyzed by infrared spectroscopy and by gas chroma­ tography. Generally the substances are detected by GC-MS or GC-FID. Detection limits depend on the technique and on the complexity of the sample, but may be less than 1 ng/1. Recent data on measured concentrations in air, water and soil are lacking. Common concentration of benzene in river water were 0.2 to 3 J.Lg/1. Mean concentrations of ethylbenzene in the river Rhine were 0.3 1-1g/l with peaks to 2 1-1g/l. Concentrations in contaminated areas may rise to > 5 mg/kg soil or to > 5 1-1g/l in groundwater. As·the log ~w is low, accumulation on sediment and in animal tissue is low, . The bioconcentration factor of benzene for Daphnia pulex is 200 and for fish < 10. The chemical reactivity of benzenes in the aquatic environment is low, due to the high stability of the benzene ring system. Benzene and isopropylbenzene are classified as readily biodegradable and also ethylbenzene is completely biodegradable under aerobic conditions. Biodegradation is an important route of elimination from the aquatic system. Another important route of elimination is volatilization. Calculated half-lives for volatilization from a "standard water system" were less than 6 hours. In air they will degrade rapidly by indirect photolysis with radicals. Aquatic toxicity data for benzene shows a large variation, with as extremes acute LC50 of 5.3 and 420 mg/1 for two fish species. The reproducibility of test results is low: the LC50 in two tests with Daphnia pulex differed by a factor 20. The variability in test results may be due, at least partly, to the high volatility of benzene. Information on chronic toxicity is lacking. Studies on early life stages of two marine species showed that embryo development was affected already at 0.05 mg/1. The acute toxicity of ethylbenzene is comparable to the toxicity of benzene. No chronic toxicity studies were found. Toxicity data for isopropyl are limited to a mollusc and two crustacean species. The same variability in test results is observed and the toxicity seems to be comparable to the toxicity of ethylbenzene. QSAR estimations of the toxicity based on log Kow did not predict the toxicity of ethylbenzene very well, and therefore the QSAR was not considered to be sufficiently reliable to estimate the toxicity of isopropylhenzene. - Ill - The NOECecosystem was estimated by the modified EPA method: the lowest NOEC for benzene was divided by 10 to arrive at a maximum tolerable concentration of 0.005 mg/1. The toxic effects of benzene, ethylbenzene and isopropylbenzene are expected to be additive. Therefore a water quality criterion of 5 J.Lg/1 is proposed for the sum of the three benzenes. This level comes close to the environmental levels cited in the earlier reports as "not uncommon" in river water for benzene and ethylbenzene. Standards proposed by the USA and Canada for benzene and ethylbenzene range between 2.4 and 5 J.Lg/1 and are comparable with the proposed water quality standards (5 J.Lg/1). Data on mammalian toxicity are incomplete. A tentative "Tolerable Daily Intake" of 170 J.Lg/kg body weight/day was proposed for benzene and 136 · J.Lg/kg body weight/day for ethylbenzene. Benzene is considered to have genotoxic properties; it shows carcinogenic activity in man. For ethylbenzene and isopropylbenzene no data are available. Based on the proposed water quality standard of 5 J.Lg/1 a maximum daily intake by man is estimated at 0.33 J.Lg/kg bodyweight/day, which is far below the above mentioned tolerable daily intake levels. - IV- Table i Information available for benzene, ethylbenzene and isopropylbenzene on the different subjects. Subject: BENZENE ETHYL-BENZENE ISOPROPYL-BENZENE 1. PHYSICO-CHEMICAL CHARACTERISTICS + + + Production levels + + + 2. ANALYTICAL DETECTION TECHNIQUES Detection methods + + + Detection levels + + + 3. ENVIRONMENTAL LEVELS Residues in the atmosphere :! :! Residues in soil and groundwater _,_+·+ -;- I Residues in surface water and sediment +·-_, _,+·+ _ -;- Residues in aquatic organisms + Residues in terrestrial organisms 4. PERSISTENCE AND DEGRADATION PATHUAYS Abiotic degradation :! :! :! Biological degradation and metabolism + + + 5. DISTRIBUTION BETUEEN ENVIRONMENTAL COMPARTMENTS Volatization + + + Sorption + + + Bioaccunulation: Aquatic organisms + Terrestrial organisms Biomagnification + :! ! 6. TOXICITY Aquatic toxicity: Acute toxicity (freshwater; marine) +·+,_ +;+ _,_+·+ Chronic toxicity (freshwater; marine) -;- . -;- Quantitative structure activity relations (QSARs) + + + Toxicity to terrestrial organisms (semi)field studies Toxicity to mammals (acute; chronic) +·+,_ +·+ +·+,_ Carcinogenic, mutagenic and teratogenic effects +·+·-,_, -;-;-·- -;-;- + data available ! insufficient data available - no data available - v- ZUSAMMENFASSUNG Die Wirkung von Benzol, Ethylbenzol und Isopropylbenzol auf die aquatische Umwelt wurde ermittelt mit der Absicht eine toxikologische Grundlage zu beschaffen auf welcher ein Vorschlag fur WasserqualiUitskriterien abgeleitet werden konnte. Dieser Studie stellt eine Aufwertung dar von zwei friiheren Berichten an die EG (Persoone und Vanhaecke, 1982 und Chambon, 1984). Werte beziiglich physischen und chemischen Eigenschaften, Abbaubarkeit, ToxiziHit, chemischer Determinierung und Umweltkonzentrationen wurden untersucht. In Tafel i sind die Ergebnissen dargestellt tiber die verfiigbare Daten der verschiedenen Gegenstande. Benzol, Ethylbenzol und Isopropylbenzol finden eine breite Anwendung fur einen Vielfalt von Produkten der chemischen Industrie; sie konnen verwendet werden als· LOsungsmittel; Benzol, Ethylbenzol und Isopropylbenzol sind Komponenten von Benzin. Die totale Produktion von Benzol, Ethylbenzol und lsopropylbenzol in der 3 3 EG wird eingseschatzt auf >440*10 , 2900*10 und 1370*1Ql Tonne/Jahr in 1987. Benzole konnen chemisch analysiert werden mittels Infrarot-Spektroskopie und durch Gaschromatografie. Im Allgemeinen werden die Stoffen determiniert durch GC-MS oder GC-FID. Die Determinierungsgrenzwerte sind abhangig von der Anwendungstechnik und von der Komplexizitat des Probemusters, konnen aber weniger als 1 ng/L betragen. Rezente Werte von gemessenen Konzentrationen in Luft, Wasser und Boden fehlen. Ubliche Konzentrationen von Benzol in Flusswassern
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