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<pre>Aluminium alkyl compounds
(CAS No: 97-93-8, 100-99-2, 96-10-6, 563-43-9)
Health-based Reassessment of Administrative
Occupational Exposure Limits
Committee on Updating of Occupational Exposure Limits,
a committee of the Health Council of the Netherlands
No. 2000/15OSH/043, The Hague, 31 October 2002
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<pre>Preferred citation:
Health Council of the Netherlands: Committee on Updating of Occupational
Exposure Limits. Aluminium alkyl compounds; Health-based Reassessment of
Administrative Occupational Exposure Limits. The Hague: Health Council of
the Netherlands, 2002; 2000/15OSH/043
all rights reserved
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<pre>1     Introduction
      The present document contains the assessment of the health hazard of
      aluminium alkyl compounds by the Committee on Updating of Occupational
      Exposure Limits, a committee of the Health Council of the Netherlands. The
      first draft of this document was prepared by AAE Wibowo, Ph.D. (Coronel
      Institute of the Academic Medical Centre, Amsterdam, the Netherlands).
            Literature was retrieved from the databases Medline, Chemical Abstracts,
      and Embase (starting from 1966, 1970, and 1988, respectively), and Poltox
      (Toxline, Cambridge Sc Abst, FSTA; from 1994 backwards), HSEline, and
      NIOSHTIC (from 1997 backwards), using the following key words:
      trialkylaluminum, alkylaluminum, triethylaluminum, triisobutylaluminum,
      chlorodiethylaluminum, dichloroethylaluminum. The final literature search was
      carried out in December 1997.
            In February 1999, the President of the Health Council released a draft of the
      document for public review. The committee received no comments.
            An additional literature search in May 2002 did not result in information
      changing the committee's conclusions.
2     Identity
      The group of aluminium alkyl compounds includes trialkylaluminium
      compounds (R3Al), alkylaluminium halides ([RnAlX3-n]2, n=1, 2), and
      alkylaluminium sesquihalides (R3Al2X3).
      The industrially most important compounds are:
       name                                   formula                CAS number
       triethylaluminium                      (C2H5)3Al              97-93-8
       triisobutylaluminium                   [(CH3)2CHCH2]3Al       100-99-2
       chlorodiethylaluminium                 (C2H5)2-AlCl           96-10-6
       (synonym: diethylaluminium chloride)
       dichloroethylaluminium                 C2H5AlCl2              563-43-9
       (synonym: ethylaluminium dichloride)
      Data from Bud89.
043-3 Aluminium alkyl compounds
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<pre>3     Physical and chemical properties
      The following physical and chemical properties are reported (Bud89):
       compounds                         molecular weight    boiling point (oC) melting point (oC)
       triethylaluminium                 114.17              194                -
       triisobutylaluminium              198.33              at 1.3 kPa: 86     6
       chlorodiethylaluminium            120.56              at 6.5 kPa: 127    -
       dichloroethylaluminium            126.95              at 6.5 kPa: 113    32
      The partition coefficients (log Poctanol/water) of these compounds are not known.
      At room temperature, the trialkylaluminium compounds are colourless liquids;
      the triethyl derivative exists as a dimer, the triisobutyl derivative primarily as a
      monomer. Chlorodiethyl- and dichloroethylaluminium are a colourless volatile
      liquid and a solid, respectively, strongly associated forming dimers, held
      together by bridging halogen bonds. The aluminium alkyl compounds are
      highly reactive compounds. They react violently with water and are sensitive to
      oxidation and hydrolysis in air. The compounds ignite spontaneously in air
      (Bud89). Miura et al. reported that the vapour of triethylaluminium ignites at
      less than the freezing point at concentrations of more than 0.15 ppm in air
      (Miu72).
4     Uses
      Aluminium alkyl compounds are used as catalysts, with compounds of early
      transition metals as Ziegler-Natta polymerisation catalysts and as intermediates
      in organic synthesis.
5     Biotransformation and kinetics
      The committee did not find data on the (toxico)kinetics of aluminium alkyl
      compounds.
043-4 Health-based Recommended Occupational Exposure Limits
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<pre>6     Effects and mechanism of action
      Human data
      The committee did not find data on effects in humans due to exposure to
      aluminium alkyl compounds.
      Animal data
      There is only one paper available describing inhalation experiments with
      triethylaluminium in mice, rats, and rabbits (Miu72). However, the results can
      not be used for determining a health-based occupational exposure limit because
      the administered vapour consisted of various unknown combustion products of
      triethylaluminium due to the reactivity of the compound.
      The committee did not find data from repeated-dose toxicity studies, including
      carcinogenicity and reproduction toxicity, or on genotoxicity or mutagenicity
      studies on aluminium alkyl compounds.
7     Existing guidelines
      The current administrative occupational exposure limit (MAC) of aluminium
      alkyl compounds in the Netherlands is 2 mg/m3 as Al, 8-hour TWA.
           Existing occupational exposure limits for this substance in some European
      countries and in the USA are summarised in the annex.
8     Assessment of health hazard
      There are no human data and the only animal study performed can not be used
      for recommending a health-based occupational exposure limit due to the
      presence of unknown combustion products of triethylaluminium.
           In fact, the committee is of the opinion that an occupational exposure limit
      for aluminium alkyl compounds is irrelevant because, in practice, there will be
      no exposure to airborne aluminium alkyl compounds. These compounds are so
      highly reactive that they ignite spontaneously in air. Therefore, aluminium alkyl
      compounds are stored in airless, inert, and stable atmospheres, and are not kept
      in open air. In case of instigating an air monitoring program, the committee
043-5 Aluminium alkyl compounds
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<pre>       recommends to measure aluminium oxide levels in air which is the product of
       ignition.
       The committee considers the toxicological database on aluminium alkyl
       compounds too poor to justify recommendation of a health-based occupational
       exposure limit.
       The committee concludes that there is insufficient information to comment on
       the level of the present MAC-value.
       References
ACG02a American Conference of Governmental Industrial Hygienists (ACGIH). Guide to occupational
       exposure values - 2002. Cincinnati OH, USA: ACGIH®, Inc, 2002: 5.
ACG02b American Conference of Governmental Industrial Hygienists (ACGIH). 2002 TLVs® and BEIs®.
       Threshold Limit Values for chemical substances and fysical agents. Biological Exposure Indices.
       Cincinnati OH, USA: ACGIH®, Inc, 2002: 14.
Arb00a Arbejdstilsynet. Grænseværdier for stoffer og materialer. Copenhagen, Denmark: Arbejdstilsynet,
       2000; At-vejledning C.0.1.
Arb00b Arbetarskyddsstyrelsen. Hygieniska gränsvärden och åtgärder mot luftföroreningar. Solna, Sweden:
       Arbetarskyddsstyrelsen, 2000; Ordinance AFS 2000:3.
Bud89  Budavari S, O'Neil MJ, Smith A, et al, eds. In: The Merck Index. An encyclopedia of chemicals,
       drugs, and biologicals. Rahway NJ, USA: Merck & Co, Inc, 1989: 54-5.
CEC00  Commission of the European Communities (CEC). Commission Directive 2000/39/EC of 8 June
       2000 establishing a first list of indicative occupational exposure limit values in implementation of
       Council Directive 98/24/EC on the protection of the health and safety of workers from the risks
       related to chemical agents at work. Official Journal of the European Communities 2000; L142
       (16/06/2000): 47-50.
DFG02  Deutsche Forschungsgemeinschaft (DFG): Senatskommission zur Prüfung gesundheitsschädlicher
       Arbeitsstoffe. MAK- und BAT-Werte-Liste 2002. Maximale Arbeitsplatzkonzentrationen und Bio-
       logische Arbeitsstofftoleranzwerte. Weinheim, FRG: Wiley-VCH, 2002; rep no 38.
HSE02  Health and Safety Executive (HSE). EH40/2002. Occupational exposure limits 2001. Sudbury
       (Suffolk), England: HSE Books, 2002.
Miu72  Miura T, Nakajima T, Hara I, et al. Studies on the toxicity of triethylaluminum (TEA). Intern Arch
       Arbeitsmed 1972; 29: 189-200.
SZW02  Ministerie van Sociale Zaken en Werkgelegenheid (SZW). Nationale MAC-lijst 2002. The Hague,
       the Netherlands: Sdu, Servicecentrum Uitgevers, 2002: 16.
043-6  Health-based Recommended Occupational Exposure Limits
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<pre>TRG00 TRGS 900. Grenzwerte in der Luft am Arbeitsplatz; Technische Regeln für Gefahrstoffe. BArbBl
      2000; 2.
043-7 Aluminium alkyl compounds
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<pre>              Annex
Occupational exposure limits for aluminium alkyl compounds in various countries.
country                             occupational exposure         time-weighted type of exposure noteb       referencec
-organisation                       limita                        average         limit
                                    ppm           mg/m3
the Netherlands
-Ministry of Social Affairs         -             2               8h              administrative             SZW02
and Employment
Germany
-AGS                                -             -                                                          TRG00
-DFG MAK-Kommission                 -             -                                                          DFG02
Great-Britain
-HSE                                -             2               8h              OES                        HSE02
Sweden                              -             -                                                          Arb00b
Denmark                             -             2               8h                                         Arb00a
USA
-ACGIH                              -             2               8h              TLV                        ACG02b
-OSHA                               -             -                                                          ACG02a
-NIOSH                              -             2               10 h            REL                        ACG02a
European Union                                                                                               CEC00
-SCOEL                              -             -
a
     In all cases, exposures are measured as Al.
b
     S = skin notation; which mean that skin absorption may contribute considerably to body burden; sens = substance can
     cause sensitisation.
c
     Reference to the most recent official publication of occupational exposure limits.
043-8         Health-based Recommended Occupational Exposure Limits
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