Nonylphenols

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Exemplary structural formula of a para- nonylphenol (simplified without information on stereochemistry )

The nonylphenols ( NP ) are a mixture of numerous structural isomeric and stereoisomeric chemical compounds . The molecular formula (C 15 H 24 O) and molar mass (220.35 Da) of the individual compounds are the same. Each individual compound consists of an aromatic ring with a hydroxyl group and an alkyl radical made up of nine carbon atoms, mostly in the para position to the phenolic hydroxyl group. The isomer with a linear side chain is known as n -nonylphenol and is of only minor industrial importance. Nonylphenols be to the group of long-chain alkyl phenols - LCAPs ( English long chain alkyl penols counted and not occur naturally in the environment -). Because of their estrogenic , persistent and toxic properties, nonylphenols are counted among the priority hazardous substances in the EU Water Framework Directive. In June 2013, nonylphenol, both linear and branched chain, was added to ECHA's list of substances of very high concern. Previously, at the request of the Federal Office for Chemicals, the dossier was submitted for inclusion in the REACH candidate list, the NP categorized according to Art. 57 (f).

Manufacturing

The synthesis takes place catalytically from phenol and nonene (on an industrial scale from a mixture of nonene isomers which are trimerized from propene). The resulting mixture of isomers consists of a large number of isomers which have alkyl chains with different branches. The commercial form contains 85% para -nonylphenol, 10% ortho -nonylphenol and other dialkylated alkylphenols . Theoretically, up to 211 constitutional isomers of NP are possible, the number of which increases to 550 with all stereoisomers.

properties

The nonylphenols are yellowish liquids with a slightly phenol-like odor. Their melting point is −8 ° C, the boiling range between 290 and 320 ° C. The solubility in water is 6 mg / 100 ml at 20 ° C for NP.

use

Nonylphenols are mainly used for the production of nonylphenol ethoxylates (NPEO), which are used as nonionic surfactants e.g. B. used in washing solutions. It is also found in fungicides , pharmaceuticals , plasticizers for cellulose esters , paints and varnishes and in polymers and adhesives. Nonylphenols are among the priority substances of the European Union and have not been approved since December 2003 for certain uses in which the mixture of substances can get into sewage or come into direct contact with humans. According to a study by the Swedish nature conservation association SNF, nonylphenols also reach EU countries via imported textiles from countries such as China, India or Turkey.

Environmental behavior

The main entry route into the environment is the treatment of sewage water contaminated with NPEO. The resulting nonylphenol is not easily biodegradable. Microbiological degradation plays an important role in removal from the environment. Calculated half-lives are around 0.3 days in the air and around 30 days in water and soil. Due to the high bioaccumulation of the NP, it accumulates in the environment. Despite measures taken so far, nonylphenols can still be detected and are already ubiquitous in many matrices.

Biological effect

Comparison of estradiol with nonylphenol
(schematic representation)
Estradiol
Estradiol
Nonylphenol isomer
Nonylphenol isomer

Nonylphenols are as Xenoestrogen e hormonally active substances and interact with the estrogen receptor . So this can be done e.g. B. in male juvenile fish trigger the vitellogenin synthesis, which is only relevant for female fish . The estrogenicity could be shown in various in- vivo and in- vitro studies, the estrogenicity of the respective nonylphenol isomers differing considerably.

When looking at estrogenic activity, an isomer-specific perspective is therefore of great importance. The estrogenic effect is very strongly influenced by the branching of the nonyl side chain. Enantioselective aspects also play a role. Studies have shown that ( S ) and ( R ) enantiomers have different estrogenic potential.

The nonylphenols have a toxic effect on many organisms - for example on numerous types of fish (e.g. pollack) as well as freshwater mussels, water fleas, green algae, crabs and lobsters. The LD 50 values ​​are in the order of 0.1–1 mg / l. As Australian ecologists working with Ashley Ward from the University of Sydney found out, nonylphenols influence the cohesive behavior of fish. Even small amounts of only 0.5 micrograms of nonylphenols are enough to mask the fish's own odor, which means that they keep a greater distance from one another.

The Danish Institute for Safety and Toxicology calculated a preliminary TDI value of 5 µg / day / kg body weight.

In a study with 60 different foods that are commercially available, NPs were found in all foods in a concentration of 0.1 to 19.4 µg / kg. From these data, a daily intake of 7.5 µg / day NP for an adult and from breast milk or baby food of 0.2 and 1.4 µg / day NP could be calculated.

Biodegradation

In general, it can be said that the linear nonylphenol is broken down very quickly, while the branched compounds behave much more persistently. In addition to many unsuccessful experiments, there are also some articles that report on the breakdown of branched nonylphenols in soil and water. These experiments also show that the composition of the nonylphenol mixture changes as a result of the degradation. For the investigation, nonylphenol isomers were systematically synthesized and their microbiological degradation investigated.

In the case of the NPEO, the ethoxylate chain is first shortened several times by units of two carbon atoms each until only one or two ethoxy groups are left. Depending on the environment ( aerobic or anaerobic ), the corresponding carboxylic acids can also be formed. The shorter the ethoxylate chain, the more durable and hormonally effective the substances become. In branched nonylphenols, nonylphenol ethoxylates ultimately reach their end product, which is hardly biodegradable and which is also more hormonally effective than the original substance or intermediate products.

Analytics

Various techniques are described in the literature to separate the individual isomers from one another. Not only are capillary gas chromatographic techniques with mass spectrometric detection (GC-MS) used, but also two-dimensional GCxGC measurements with time-of-flight mass spectrometric detection ( GCxGC-ToF-MS ). Furthermore, the NPs can also be separated from one another using high-performance liquid chromatography (HPLC). Separations of nonylphenol enantiomers can be carried out with special enantioselective capillary columns on a GC-FID system. Nonylphenols have already been detected in many environmentally relevant samples. For example in food, drinking water and human samples. ISO / EN / DIN 18857-2 has been available since 2006 for detection in surface water or wastewater samples.

Web links

Individual evidence

  1. ↑ Directive 2000/60 / EC of the European Parliament and of the Council of October 23, 2000 on the creation of a framework for Community measures in the field of water policy , accessed on November 7, 2016
  2. ↑ European Chemicals Agency, Committee for Risk Assessment (RAC): Nonylphenol and nonylphenol ethoxylates. Technical report. 2. ECHA, 2014, accessed November 4, 2016 .
  3. ↑ Todd F. Wheeler, John R. Heim, Maria R. LaTorre, A. Blair Janes: Mass Spectral Characterization of p-Nonylphenol Isomers Using High-Resolution Capillary GC-MS . In: Journal of Chromatographic Science . tape 35 , no. 1 , January 1, 1997, p. 19–30 , doi : 10.1093 / chromsci / 35.1.19 ( chromsci.oxfordjournals.org [accessed November 7, 2016]).
  4. ↑ Bjoern Thiele, Volkmar Heinke, Einhard Kleist, Klaus Guenther: Contribution to the Structural Elucidation of 10 Isomers of Technical p-Nonylphenol . In: Environmental Science & Technology . tape 38 , no. 12 , 2004, p. 3405-3411 , doi : 10.1021 / es040026g .
  5. ↑ Alexander S. Ruß, Ralph Vinken, Ingolf Schuphan, Burkhard Schmidt: Synthesis of branched para-nonylphenol isomers: Occurrence and quantification in two commercial mixtures . In: Chemosphere . tape 60 , no. 11 , September 1, 2005, pp. 1624-1635 , doi : 10.1016 / j.chemosphere.2005.02.046 .
  6. ^ Klaus Guenther, Einhard Kleist, Bjoern Thiele: Estrogen-active nonylphenols from an isomer-specific viewpoint: a systematic numbering system and future trends . In: Analytical and Bioanalytical Chemistry . tape 384 , no. 2 , December 10, 2005, p. 542-546 , doi : 10.1007 / s00216-005-0181-8 .
  7. ↑ a b Entry on nonylphenol, isomers in the GESTIS substance database of the IFA , accessed on August 21, 2017(JavaScript required) .
  8. ↑ Nonylphenol and nonylphenol ethoxylates, Tricresyl phosphates and Benzoic acid, Danish Environmental Protection Agency. (No longer available online.) In: www.statensnet.dk. Archived from the original on November 7, 2016 ; Retrieved November 7, 2016 . Info: The archive link was inserted automatically and has not yet been checked. Please check the original and archive link according to the instructions and then remove this notice. @1@ 2Template: Webachiv / IABot / www.statensnet.dk
  9. ↑ Directive 2003/53 / EC of the European Parliament and of the Council of June 18, 2003 on the 26th amendment to Directive 76/769 / EEC on restrictions on the placing on the market and use of certain dangerous substances and preparations (nonylphenol, nonylphenol ethoxylate and cement) , accessed November 6, 2016 .
  10. ↑ Reinhard Wolff: Dirty cloths . In: The daily newspaper . September 13, 2007, p. 8 ( taz.de ).
  11. ↑ P.-C. Lee, W. Lee: In vivo estrogenic action of nonylphenol in immature female rats . In: Bull Environ Contam Toxicol . tape 57 , 1996, pp. 341-348 .
  12. ↑ J. Odum, PA Lefevre, S. Tittensor, D. Paton, EJ Routledge, NA Beresford, JP Sumpter, J. Ashby: The rodent uterotrophic assay: critical protocol features, studies with nonyl phenols, and comparison with a yeast estrogenicity assay . In: Reg Toxicol Pharmacol . tape 25 , 1997, pp. 176-188 .
  13. ^ Thomas G. Preuss, Jacqueline Gehrhardt, Kristin Schirmer, Anja Coors, Mascha Rubach: Nonylphenol Isomers Differ in Estrogenic Activity . In: Environmental Science & Technology . tape 40 , no. 16 , 2006, pp. 5147-5153 , doi : 10.1021 / es060709r .
  14. ↑ Klaus Guenther, Volkmar Heinke, Bjoern Thiele, Einhard Kleist, Hartmut Prast: Endocrine Disrupting Nonylphenols Are Ubiquitous in Food . In: Environmental Science & Technology . tape 36 , no. 8 , 2002, p. 1676-1680 , doi : 10.1021 / es010199v .
  15. ↑ a b Yun-Seok Kim, Takao Katase, Sayaka Sekine, Tadashi Inoue, Mitsuko Makino: Variation in estrogenic activity among fractions of a commercial nonylphenol by high performance liquid chromatography . In: Chemosphere . tape 54 , no. 8 , February 1, 2004, p. 1127–1134 , doi : 10.1016 / j.chemosphere.2003.09.024 .
  16. ↑ a b Ismail-Hakki Acir, Matthias Wüst, Klaus Guenther: Enantioselective separation of defined endocrine-disrupting nonylphenol isomers . In: Analytical and Bioanalytical Chemistry . tape 408 , no. 20 , May 28, 2016, pp. 5601-5607 , doi : 10.1007 / s00216-016-9661-2 .
  17. ↑ Haifeng Zhang, Sebastian Zuehlke, Klaus Guenther, Michael Spiteller: Enantioselective separation and determination of single nonylphenol isomers . In: Chemosphere . tape 66 , no. 4 , January 1, 2007, p. 594-602 , doi : 10.1016 / j.chemosphere.2006.08.012 .
  18. ↑ Haifeng Zhang, Iris M. Oppel, Michael Spiteller, Klaus Guenther, Gabriele Boehmler: Enantiomers of a nonylphenol isomer: Absolute configurations and estrogenic potencies . In: Chirality . tape 21 , no. 2 , February 1, 2009, p. 271-275 , doi : 10.1002 / chir.20556 .
  19. ↑ Nonylphenol affects cohesion. In: The world. October 25, 2007, accessed November 6, 2016 .
  20. ↑ Communication from the University of Sydney: Aquarium experiment with nonylphenol. October 26, 2007, accessed November 6, 2016 .
  21. ^ A b K. Guenther, V. Heinke, B. Thiele, E. Kleist, H. Prast, T. Raecker: Endocrine disrupting nonylphenols are ubiquitous in food . In: Environ Sci Technol. No. 36 , 2002, p. 1676-80 .
  22. ↑ T. Tanghe, W. Dhooge, W. Verstraete: Isolation of a bacterial strain able to degrade branched nonylphenol. In: Appl. Environ. Microbiol . tape 65 , no. 2 , 1999, p. 746-751 .
  23. ↑ Zhijiang Lu, Rubén Reif, Jay Gan: Isomer-specific biodegradation of nonylphenol in an activated sludge bioreactor and structure-biodegradability relationship . In: Water Research . tape 68 , January 1, 2015, p. 282–290 , doi : 10.1016 / j.watres.2014.09.050 .
  24. ↑ Roswitha M. Boehme, Thomas Andries, Karl Heinz Dötz, Bjoern Thiele, Klaus Guenther: Synthesis of defined endocrine-disrupting nonylphenol isomers for biological and environmental studies . In: Chemosphere . tape 80 , no. 7 , August 1, 2010, p. 813-821 , doi : 10.1016 / j.chemosphere.2010.03.064 .
  25. ^ Frédéric LP Gabriel, Edwin J. Routledge, Andy Heidlberger, Daniel Rentsch, Klaus Guenther, Walter Giger, John P. Sumpter, Hans-Peter E. Kohler: Isomer-specific degradation and endocrine disrupting activity of nonylphenols. In: Environ Sci Technol . tape 42 , no. 17 , 23 July 2008, p. 6399-6408 , doi : 10.1021 / es800577a .
  26. ^ W. Giger, E. Stephanou, C. Schaffner: Persistent organic chemicals in sewage effluents: I. Identifications of nonylphenols and nonylphenol ethoxylates by glass capillary gas chromatography / mass spectrometry . In: Chemosphere . 10th edition. 1981, p. 1253-1263 .
  27. ↑ TF Wheeler, JR Heim, MR LaTorre, AB Janes: Mass spectral characterization of p-nonylphenol isomers using high-resolution capillary GC-MS . In: J. Chromatogr. Sci. 35th edition. 1997, p. 19-30 .
  28. ^ M. Moeder, C. Martin, J. Harynuk, T. Górecki, R. Vinken: Identification of isomeric 4-nonylphenol structures by gas chromatography – tandem mass spectrometry combined with cluster analysis . In: Journal of Chromatography A . tape 1102 , no. 1-2 , January 13, 2006, pp. 245-255 , doi : 10.1016 / j.chroma.2005.10.031 .
  29. ↑ Robert P. Eganhouse, James Pontolillo, Richard B. Gaines, Glenn S. Frysinger, Frédéric Gabriel LP: Isomer-Specific Determination of 4-nonylphenol Using Comprehensive Two-Dimensional Gas Chromatography / Time-of-Flight Mass Spectrometry . In: Environmental Science & Technology . tape 43 , no. 24 , December 15, 2009, p. 9306-9313 , doi : 10.1021 / es902622r .
  30. ↑ B. Thiele, K. Guenther, MJ Schwuger: Alkylphenol ethoxylates: trace analysis and environmental behavior. In: Chem Rev. 97th edition. 1997, p. 3247-3272 .
  31. ↑ Torsten Raecker, Bjoern Thiele, Roswitha M. Boehme, Klaus Guenther: Endocrine disrupting nonyl- and octylphenol in infant food in Germany: Considerable daily intake of nonylphenol for babies . In: Chemosphere . tape 82 , no. 11 , March 1, 2011, p. 1533-1540 , doi : 10.1016 / j.chemosphere.2010.11.065 .
  32. ↑ Nathan G. Dodder, Keith A. Maruya, P. Lee Ferguson, Richard Grace, Susan Klosterhaus: Occurrence of contaminants of emerging concern in mussels (Mytilus spp.) Along the California coast and the influence of land use, storm water discharge, and treated wastewater effluent . In: Marine Pollution Bulletin (=  US Coastal Monitoring: NOAA's Mussel Watch investigates Contaminants of Emerging Concern ). tape 81 , no. 2 , April 30, 2014, p. 340–346 , doi : 10.1016 / j.marpolbul.2013.06.041 .
  33. ↑ Silvia Maggioni, Patrick Balaguer, Claudia Chiozzotto, Emilio Benfenati: Screening of endocrine-disrupting phenols, herbicides, steroid estrogens, and estrogenicity in drinking water from the waterworks of 35 cities Italian and from PET-bottled mineral water . In: Environmental Science and Pollution Research . tape 20 , no. 3 , July 21, 2012, p. 1649-1660 , doi : 10.1007 / s11356-012-1075-x .
  34. ^ Fulvio Ferrara, Nicoletta Ademollo, Maria Antonietta Orrù, Leopoldo Silvestroni, Enzo Funari: Alkylphenols in adipose tissues of Italian population . In: Chemosphere . tape 82 , no. 7 , February 1, 2011, p. 1044-1049 , doi : 10.1016 / j.chemosphere.2010.10.064 .
  35. ↑ Mo Chen, Zhanlan Fan, Fanrong Zhao, Fumei Gao, Di Mu: Occurrence and Maternal Transfer of Chlorinated Bisphenol A and Nonylphenol in Pregnant Women and Their Matching Embryos . In: Environmental Science & Technology . tape 50 , no. 2 , 2016, p. 970-977 , doi : 10.1021 / acs.est.5b04130 .
  36. ↑ DIN EN ISO 18857-2 Water quality - Determination of selected alkylphenols - Part 2: Gas chromatographic-mass spectrometric determination of alkylphenols, their ethoxylates and bisphenol A for non-filtered samples using solid phase extraction and derivatization (ISO 18857-2: 2009); German version EN ISO 18857-2: 2011.