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The Environmental Behavior of Methylene-4,4′-dianiline

  • Thomas Schupp
  • Hans Allmendinger
  • Christian Boegi
  • Bart T. A. Bossuyt
  • Bjoern Hidding
  • Summer Shen
  • Bernard Tury
  • Robert J. West
Chapter
Part of the Reviews of Environmental Contamination and Toxicology book series (RECT, volume 246)

Abstract

Methylene-4,4′-dianiline (MDA, CAS-No. 101–77-9) is a high production volume intermediate that is mainly processed to diisocyanates and finally polyurethanes. This review summarizes available data concerning the environmental behavior. When released into the environment, MDA distributes into water and subsequently sediment and soil compartments; the air is of little relevance, owed to the low vapor pressure and short atmospheric half-life, which renders MDA non-critical for long-range transport. Biodegradation data present a diverged picture; in some tests, MDA is not readily biodegradable or even not inherent biodegradable; in other tests, MDA turned out to be readily biodegradable (but failing the 10-d window). The history and composition of the inoculum used for testing seem to play an important role, which is underlined by good test results with adapted inoculum. In soil, initially a rapid mineralization is observed, which slows down within the first days due to competitive chemical absorption. The latter results in degradation rates comparable to that of natural organic matter. Under anaerobic conditions, mineralization is poor. Irreversible chemisorption occurs unless soils/sediments are highly reduced. Half-lives due to primary decay do not indicate MDA to be persistent according to the regulatory guidance used in then EU, Canada, or the USA; in Japan, however, due to test results in MITI degradation tests, MDA would be regarded as persistent. The identification of microbial MDA metabolites deserves further research. MDA is not bioaccumulative, but it is toxic to aquatic organisms and mammals. MDA in pore water of soils is rapidly adsorbed on the surface of plant roots. Test runs were too short to draw a final conclusion with regards to transport to stem, leaves, and fruits. Data from structurally similar compounds indicate that such transport would account for less than 1% of the root-adsorbed material.

Keywords

4,4′-Diaminodiphenylmethane Abiotic degradation Anaerobic biodegradation Bioaccumulation Biodegradation in sediment Biodegradation in soil Biodegradation simulation test Covalent binding Distribution Environmental modeling Inherent biodegradability Koc Kow MDA Methylene-4,4′-dianiline NER Non-extractable residues Persistency Photodegradation Primary aromatic amines Ready biodegradability Soil absorption Soil adsorption Soil organic matter Soil reactivity Soil–water distribution 

Notes

Acknowledgement

This work was sponsored by the International Isocyanate Institute, Inc. The views presented in this paper are those of the authors and not necessarily those of the sponsor.

Conflict of Interest

T. Schupp worked for BASF, an MDA producer, until 2012.

H. Allmendinger is a consultant for Currenta GmbH & Co. OHG.

S. Shen is working for Dow, an MDA producer.

B. T. A. Bossuyt is working for Huntsman, an MDA producer.

C. Boegi and B. Hidding are working for BASF, an MDA producer.

B. Tury and R. J. West have been employed by the International Isocyanate Institute, Inc.

References

  1. Alport DC, Gilbert DS, Outterside SM (eds) (2003) MDI and TDI: safety, health, and the environment – a source book and practical guide. Wiley, West SussexGoogle Scholar
  2. BASF (1981) Biologische Eliminierbarkeit im Zahn-Wellens-Test. BASF-SE, Experimental Toxicology and Ecology, Report No. 87/0892. Robust summary: http://apps.echa.europa.eu/registered/data/dossiers/DISS-9c7b34e3-c5c4-7414-e044-00144f67d249/AGGR-acfea30d-ad97-4274-b8ce-aabd18d556da_DISS-9c7b34e3-c5c4-7414-e044-00144f67d249.html
  3. Baumann W (1985) Report on the test for ready biodegradability of TK10504 in the modified Sturm test (OECD Guideline No. 301B, Paris 1981). Ciba-Geigy Ltd, Basel, report R-1066.K.247; project no. 850729. 12.09.1985. Robust summary: http://apps.echa.europa.eu/registered/data/dossiers/DISS-9c7b34e3-c5c4-7414-e044-00144f67d249/AGGR-acfea30d-ad97-4274-b8ce-aabd18d556da_DISS-9c7b34e3-c5c4-7414-e044-00144f67d249.html
  4. Baumann W (1986) Report on the bioelimination test on TK 10504 in the simulation test – aerobic sewage OECD Coupled Units Test No. 303 A. Ciba-Geigy Ltd, Basel. Project-no. 860630. Archive R-1066.K2.47. 15.10.1986. Robust summary: http://apps.echa.europa.eu/registered/data/dossiers/DISS-9c7b34e3-c5c4-7414-e044-00144f67d249/AGGR-acfea30d-ad97-4274-b8ce-aabd18d556da_DISS-9c7b34e3-c5c4-7414-e044-00144f67d249.html
  5. Becker KH, Bastian V, Klein T (1988) The reaction of OH radicals with toluene diisocyanate, toluenediamine and methylenedianiline under simulated atmospheric conditions. J Photochem Photobiol A Chem 45:195–205CrossRefGoogle Scholar
  6. Bollag J-M, Minard RD, Liu S-Y (1983) Cross-linkage between anilines and phenolic humus constituents. Environ Sci Technol 17:72–80CrossRefGoogle Scholar
  7. Bollag J-M, Myers CJ, Minard RD (1992) Biological and chemical interactions of pesticides with soil organic matter. Sci Total Environ 123/124:205–217CrossRefGoogle Scholar
  8. Bongartz R (2012) MDA: uptake by plants in a hydroponic culture. III Report No. 11635. International Isocyanate Institute, Manchester. Robust summary: http://apps.echa.europa.eu/registered/data/dossiers/DISS-9c7b34e3-c5c4-7414-e044-00144f67d249/AGGR-acfea30d-ad97-4274-b8ce-aabd18d556da_DISS-9c7b34e3-c5c4-7414-e044-00144f67d249.html
  9. Briggs GG, Olgivie SY (1971) Metabolism of 3-chloro-4-methoxyaniline and some N-acyl derivatives in soil. Pest Sci 2:165–168CrossRefGoogle Scholar
  10. Burge WD (1972) Microbial populations hydrolyzing propanil and accumulation of 3,4-dichloroaniline and 3,3′,4,4′-tetrachloro-azobenzene in soil. Soil Biol Biochem 4:379–386CrossRefGoogle Scholar
  11. Campbell K (2017) [14C]-methylenedianiline: generation of transformation products in aerobic aquatic sediment systems for identification by LC-MS/MS. Unpublished Report No. 11688 of the International Isocyanates Institute, BoontonGoogle Scholar
  12. Carvajal-Diaz J (2015) IHS chemical economics handbook: aniline. IHS, EnglewoodGoogle Scholar
  13. Caspers N, Hamburger B, Kanne R, Klebert W (1986) Ecotoxicity of toluene diisocyanate (TDI), diphenylmethane diisocyanate (MDI), toluene diamine (TDA), diphenylmethanediamine (MDA). III Report No. 10417. International Isocyanate Institute, Manchester. Available from: British Library Document Supply Centre, Boston Spa, Wetherby, West Yorks. Robust summary: http://apps.echa.europa.eu/registered/data/dossiers/DISS-9c7b34e3-c5c4-7414-e044-00144f67d249/AGGR-acfea30d-ad97-4274-b8ce-aabd18d556da_DISS-9c7b34e3-c5c4-7414-e044-00144f67d249.html
  14. CITI (1992) 4-Methylphenylene-1,3-diamine (CAS-No. 95-80-7) & 4,4′-diaminodiphenylmethane (CAS-No. 101-77-8) [Acute toxicity, biodegradability and bioaccumulation data]. In: Biodegradation and bioaccumulation data of existing chemicals based on the CSCL Japan. Chemical Inspection and Testing Institute Japan, Japan Chemical Industry Ecology-Toxicology and Information Center, Tokyo, pp 3–24, 4–6. ISBN 4-89074-101-1Google Scholar
  15. Cowen WF, Gastinger AM, Spanier CE, Buckel JR, Bailey RE (1996) Sorption and microbial degradation of toluene diamines and methylene dianiline in soil under aerobic and anaerobic conditions. III Report No. 11230. International Isocyanate Institute, Manchester. Robust summary: http://apps.echa.europa.eu/registered/data/dossiers/DISS-9c7b34e3-c5c4-7414-e044-00144f67d249/AGGR-acfea30d-ad97-4274-b8ce-aabd18d556da_DISS-9c7b34e3-c5c4-7414-e044-00144f67d249.html
  16. Cowen WF, Gastinger AM, Spanier CE, Buckel JR (1998) Sorption and microbial degradation of toluenediamines and methylendianiline in soil under aerobic and anaerobic conditions. Environ Sci Technol 1998;32:598–603CrossRefGoogle Scholar
  17. Deng Y, Xu L, Sun X, Cheng L, Liu G (2015) Measurement and correlation of the solubility for 4,4′-diaminodiphenylmethane in different solvents. J Chem Eng Data 2015;60(7):2028–2034CrossRefGoogle Scholar
  18. ECHA (2014a) 4,4′-Methylenedianiline [REACh Dossier]. European Chemicals Agency, Helsinki. https://echa.europa.eu/de/registration-dossier/-/registered-dossier/15201. Accessed 21 June 2014
  19. ECHA (2014b) Formaldehyde, oligomeric reaction products with aniline [REACH Dossier]. European Chemicals Agency, Helsinki. https://echa.europa.eu/de/registration-dossier/-/registered-dossier/14114. Accessed 21 June 2014
  20. Ekici P, Leupold G, Parlar H (2001a) Degradability of selected azo dye metabolites in activated sludge systems. Chemosphere 44:721–728CrossRefGoogle Scholar
  21. Ekici P, Angerhoefer D, Parlar H (2001b) Photoinduced reactions of selected azo dye metabolites in water. Fresenius Environ Bull 10(3):245–256Google Scholar
  22. European Union (2001) European Union risk assessment report, 4,4′-methylenedianiline, CAS-No. 101-77-9, EINECS-No. 202-974-4. Office for Official Publications of the European Union, Luxembourg. ISBN: 92-894-0484-1Google Scholar
  23. European Union (2016) Joint Research Center: the European Union System for the Evaluation of Substances (EUSES). https://ec.europa.eu/jrc/en/scientific-tool/european-union-system-evaluation-substances. Accessed 29 Dec 2016
  24. Frank R, Kloepffer W (1988) Spectral solar photon irradiation in Central Europa and the adjacent North Sea. Chemosphere 17(5):985–994CrossRefGoogle Scholar
  25. Government of Canada (2014) Draft screening assessment for methylenediphenyl diisocyanates and methylenediphenyl diamines, August 2014. Government of Canada, Chemicals Management Plan Division, Gatineau. http://www.chemicalsubstanceschimiques.gc.ca/group/diisocyanate-eng.php
  26. Graveel JG, Sommers LE, Nelson DW (1985) Sites of benzidine, α-naphthylamine and p-toluidine retention in soil. Environ Toxicol Chem 4: 607–613CrossRefGoogle Scholar
  27. Han X, Nabb DL, Mingoia RT, Yang C-H (2007) Determination of xenobiotic intrinsic clearance in freshly isolated hepatocyte from rainbow trout (Oncorhynchus mykiss) and rat and its application in bioaccumulation risk assessment. Environ Sci Technol 41:3269–3276CrossRefGoogle Scholar
  28. Harms H, Langenbartels C (1986) Standardized plant cell suspension test systems for an ecotoxicologic evaluation of the metabolic fate of xenobiotics. Plant Sci 45: 157165CrossRefGoogle Scholar
  29. Hellpointer E (1997) Determination of the quantum yield and assessment of the environmental half-life of the direct photodegradation of 4,4′-methylenedianiline in water. III Report No. 11265. International Isocyanate Institute, Manchester. Available from: British Library Document Supply Centre, Boston Spa, Wetherby, West Yorks. Robust study summary: http://apps.echa.europa.eu/registered/data/dossiers/DISS-9c7b34e3-c5c4-7414-e044-00144f67d249/AGGR-acfea30d-ad97-4274-b8ce-aabd18d556da_DISS-9c7b34e3-c5c4-7414-e044-00144f67d249.html
  30. Howard PH, Boethling RS, Jarvis WF, Meylan WM, Michalenko EM (eds) (1991) Handbook of environmental degradation rates. Lewis Publishers, ChelseaGoogle Scholar
  31. Hsu T-S, Bartha R (1974) Biodegradation of chloroaniline-humus complexes in soil and in culture solution. Soil Sci 118:213–220CrossRefGoogle Scholar
  32. Kajbaf M, Sepai O, Lamb JH (1992) Identification of metabolites of 4,4′-diaminodiphenylmethane (methylene dianiline) using liquid chromatographic and mass spectrometric techniques. J Chromat B 583:63–76CrossRefGoogle Scholar
  33. Karabunarliev S, Dimitrov S, Pavlov T, Nedelcheva D, Mekenyan O (2012) Simulation of chemical metabolism for fate and hazard assessment. IV. Computer-based derivation of metabolic simulators from documented metabolism maps. SAR QSAR Environ Res 23:371–387CrossRefGoogle Scholar
  34. Kaufman DD, Plimmer JR, Klingebiel UI (1973) Microbial oxidation of 4-chloroaniline. J Agric Food Chem 21(1):127–132CrossRefGoogle Scholar
  35. Kim M-N, Jang J-C, Lee I-M, Lee H-S, Yoon J-S (2002) Toxicity and biodegradation of diamines. J Environ Sci Health B 37(1):53–64CrossRefGoogle Scholar
  36. Li H, Lee LS, Jafvert CT, Graveel JG (2000) Effect of substitution on irreversible binding and transformation of aromatic amines with soils in aqueous systems. Environ Sci Technol 34:36743680CrossRefGoogle Scholar
  37. Li H, Lee LS, Schulze DG, Guest CA (2003) Role of manganese in the oxidation of aromatic amines. Environ Sci Technol 37:2686–2693CrossRefGoogle Scholar
  38. Mei C-F, Liu Y-Z, Long W-N, Sun G-P, Zeng G-Q, Xu M-Y, Luan T-G (2015) A comparative study of biodegradability of a carcinogenic aromatic amine (4,4′-diaminodiphenylmethane) with OECD 301 test methods. Ecotoxicol Environ Saf 111:123–130CrossRefGoogle Scholar
  39. Morgott DA (1984) The in vivo biotransformation and acute hepatotoxicity of methylene dianiline. Dissertation, University of MichiganGoogle Scholar
  40. Nabb DL, Mingoia RT, Yang CH, Han X (2006) Comparison of basal level metabolic enzyme activities of freshly isolated hepatocytes from rainbow trout (Oncorhynchuss mykiss) and rat. Aquat Toxicol 80:52–9CrossRefGoogle Scholar
  41. NITE (Japan National Institute of Technology and Evaluation) (2007) 4,4-MDA risk assessment report. http://www.nite.go.jp/chem/chrip/chrip_search/dt/pdf/CI_02_001/risk/pdf_hyoukasyo/340riskdoc.pdf
  42. NTP (2018) Methylenedianiline (101-77-9). Chemical Effects in Biological Systems (CEBS). Research Triangle Park, NC (USA): National Toxicology Program (NTP). https://manticore.niehs.nih.gov/cebssearch/test_article/101-77-9. Accessed 14 Mar 2018
  43. Ononyne AI, Graveel JG (1994) Modelling the reaction of 1-napthylamine and 4-methylaniline with humic acids: spectroscopic investigations of the covalent linkages. Environ Toxicol Chem 13(4):537–541CrossRefGoogle Scholar
  44. Parris GE (1980) Covalent binding of aromatic amines to humates. 1. Reactions with carbonyls and quinones. Environ Sci Technol 14(9):1099–1106CrossRefGoogle Scholar
  45. Pemberton D, Tury B (2008) Prediction of atmospheric half-lives for MDI, TDI, MDA and TDA using the AOPWIN™ model. GIL Report No. 2008/C. Global Isocyanates, Manchester. Robust study summary: http://apps.echa.europa.eu/registered/data/dossiers/DISS-9c7b34e3-c5c4-7414-e044-00144f67d249/AGGR-acfea30d-ad97-4274-b8ce-aabd18d556da_DISS-9c7b34e3-c5c4-7414-e044-00144f67d249.html
  46. Pillai P, Helling CS, Dragun J (1982) Soil-catalyzed oxidation of aniline. Chemosphere 11(3):299–317CrossRefGoogle Scholar
  47. Saxena A, Bartha R (1983) Microbial mineralization of humic acid – 3,4-dichloroaniline complexes. Soil Biol Biochem 15(1): 59–62CrossRefGoogle Scholar
  48. Schaefer EC, Carpenter K (2013) 4,4′-MDA: aerobic mineralization in surface waters. III Report No. 11652. International Isocyanate Institute, Manchester. Robust study summary: http://apps.echa.europa.eu/registered/data/dossiers/DISS-9c7b34e3-c5c4-7414-e044-00144f67d249/AGGR-acfea30d-ad97-4274-b8ce-aabd18d556da_DISS-9c7b34e3-c5c4-7414-e044-00144f67d249.html
  49. Schaefer EC, Ponizovsky A (2013) 4,4′-MDA: aerobic and anaerobic transformation aquatic sediment systems. III Report No. 11646. International Isocyanate Institute, Manchester. Robust study summary: http://apps.echa.europa.eu/registered/data/dossiers/DISS-9c7b34e3-c5c4-7414-e044-00144f67d249/AGGR-acfea30d-ad97-4274-b8ce-aabd18d556da_DISS-9c7b34e3-c5c4-7414-e044-00144f67d249.html
  50. Schupp T, Allmendinger H, Bossuyt BTA, Hidding B, Tury B, West RJ (2016) Review of the ecotoxicological properties of the methylenedianiline substances. Rev Environ Contam Toxicol 241: 39–72Google Scholar
  51. Schwarz H (2009) MDA determination of the ready biodegradability according to OECD Test Guideline 301B. III Report No. 11567. International Isocyanate Institute, Manchester. Robust study summary: http://apps.echa.europa.eu/registered/data/dossiers/DISS-9c7b34e3-c5c4-7414-e044-00144f67d249/AGGR-acfea30d-ad97-4274-b8ce-aabd18d556da_DISS-9c7b34e3-c5c4-7414-e044-00144f67d249.html
  52. Suidan MT, Campo P, Platten W, Chai Y, Davis JD (2011) Aerobic biodegradation of amines in industrial saline wastewaters. Chemosphere 85:1199–1203CrossRefGoogle Scholar
  53. US EPA (2004) Appendix C to 40 CFR Part 63 - determination of the fraction biodegraded (Fbio) in a biological treatment unit. Fed Regist 69:39383–39392Google Scholar
  54. Voorman R, Penner D (1986a) Fate of MBOCA [4,4′-methylene-bis(2-chloroaniline)] in soil. Arch Environ Contam Toxicol 15: 595–602CrossRefGoogle Scholar
  55. Voorman R, Penner D (1986b) Plant uptake of MBOCA [4,4′-methylene-bis(2-chloroaniline)]. Arch Environ Contam Toxicol 15: 589–593CrossRefGoogle Scholar
  56. Weber EJ, Spidle DL, Thorn KA (1996) Covalent binding of aniline to humic substances. 1: kinetic studies. Environ Sci Technol 30:2755–2763CrossRefGoogle Scholar
  57. Weber EJ, Colon, D, Baughman, GL (2002) Sediment-associated reactions of aromatic amines. 2. QSAR development. Environ Sci Technol 36:2443–2450Google Scholar
  58. West RJ (2007) Evaluation of the intrinsic anaerobic biodegradability of MDA and TDA in soil-free enrichment cultures. III Report No. 11530. International Isocyanate Institute, Manchester. Robust study summary: http://apps.echa.europa.eu/registered/data/dossiers/DISS-9c7b34e3-c5c4-7414-e044-00144f67d249/AGGR-acfea30d-ad97-4274-b8ce-aabd18d556da_DISS-9c7b34e3-c5c4-7414-e044-00144f67d249.html
  59. West RJ, Tury B (2006) PBT categorization analysis for TDI, MDI, TDA and MDA. III Report No. 11522. International Isocyanate Institute, Manchester. Robust study summary: http://apps.echa.europa.eu/registered/data/dossiers/DISS-9c7b34e3-c5c4-7414-e044-00144f67d249/AGGR-acfea30d-ad97-4274-b8ce-aabd18d556da_DISS-9c7b34e3-c5c4-7414-e044-00144f67d249.html
  60. West RJ, Davis JW, Bailey RE (2002) Sorption and biodegradation of 2,4-TDA, 2,6-TDA and 4,4′-MDA in soils under anaerobic conditions: second study. III Report No. 11463. International Isocyanate Institute, Manchester. Robust study summary: http://apps.echa.europa.eu/registered/data/dossiers/DISS-9c7b34e3-c5c4-7414-e044-00144f67d249/AGGR-acfea30d-ad97-4274-b8ce-aabd18d556da_DISS-9c7b34e3-c5c4-7414-e044-00144f67d249.html
  61. Yakabe Y (1994) The study of the environmental fate of TDA, MDA and oligoureas of MDI and TDI: biodegradability test of 2,4-diaminotoluene and 4,4′-diaminodiphenylmethane. III Report No. 11170. International Isocyanate Institute, Manchester. Robust study summary: http://apps.echa.europa.eu/registered/data/dossiers/DISS-9c7b34e3-c5c4-7414-e044-00144f67d249/AGGR-acfea30d-ad97-4274-b8ce-aabd18d556da_DISS-9c7b34e3-c5c4-7414-e044-00144f67d249.html

Copyright information

© Springer International Publishing AG, part of Springer Nature 2018

Authors and Affiliations

  • Thomas Schupp
    • 1
  • Hans Allmendinger
    • 2
  • Christian Boegi
    • 3
  • Bart T. A. Bossuyt
    • 4
  • Bjoern Hidding
    • 5
  • Summer Shen
    • 6
  • Bernard Tury
    • 7
  • Robert J. West
    • 8
  1. 1.Faculty of Chemical EngineeringMuenster University of Applied ScienceSteinfurtGermany
  2. 2.Currenta GmbH & Co. OHGLeverkusenGermany
  3. 3.BASF SE, FEP/PA - Z570LudwigshafenGermany
  4. 4.Huntsman EuropeEverbergBelgium
  5. 5.BASF SE, RB/TC - Z570LudwigshafenGermany
  6. 6.Dow Chemical (China) Investment Limited CompanyShanghaiChina
  7. 7.(former) International Isocyanate Institute Inc.BoontonUSA
  8. 8.International Isocyanate Institute Inc.BoontonUSA

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