Alkylphenol ethoxylates (APEOs – often called alkyphenols or alkylphenyls) are surfactants which have an emulsifying and dispersing action, so they have good wetting, penetration, emulsification, dispertion, solubilizing and washing characteristics. This makes them suitable for a very large variety of applications: they've been used for over 50 years in a wide variety of products. In the textile industry, they are used in detergents and as scouring, coating, or waterproofing agents, in printing pastes and adhesives, and in dyeing. The most important APEO or alkylphenol ethoxylates for the textile industry are NPEO (nonylphenol ethoxylates) and OPEO (octylphenol ethoxylates) due to their detergent properties.
The three critical issues in making APEOs and NPEOs in the environment of particular concern are:
- They are everywhere. They're in receipts, canned foods and couches, paint and spot cleaners. They're in the dust in our homes, our blood and urine, in breast milk and in the cord blood of newborns. Concentrations of NP and its parent compound NPEO have been measured worldwide in surface waters, sediments, sewage, the atmosphere, aquatic organisms, and even in typical human food products. And most disturbingly, these concentrations of APEOs are on the rise.1 The U.S. EPA has noted rising levels of alkylphenols in water samples taken from streams and rivers throughout the U.S.
- The life cycles indicate long term, continued environmental contamination. APEOs are slow to biodegrade and they tend to bioaccumulate. They also move up the food chain and ultimately to us. Though APEOs themselves are not carcinogenic, teratogenic (A teratogen is any agent that can disturb the development of an embryo or fetus), or mutagenic, research has shown that when they do degrade, their byproducts have a higher toxicity, estrogenic activity, persistence and tendency to bioaccumulate than APEOs themselves.2
They have been shown to be toxic to aquatic organisms and an endocrine disruptor in higher animals, and therefore they pose a risk to humans. As an environmental hormone disruptor, these new substances can invade the human body through a variety of channels, with estrogen-like effects, and are harmful to normal hormone secretion, leading to reduced sperm count in men. Research published in the September 2006 edition of Toxicological Sciences shows that the human placenta responds to alkylphenyls in the first trimester.3 The result may be early termination of pregnancy and fetal growth defect.4
Think of using fish to replace the proverbial canary in the coal mine. Because most mills do not treat their wastewater, the effluent containing these APEOs is discharged directly into our groundwater, where it is a major source of hormone disruption in fish species. The classic example is intersex attributes in fish (suppression of testes growth in males), with other reproductive effects and anomalies. In one study, egg production of zebrafish, exposed to wastewater effluent contaminated with APEOs, was reduced by up to 89.6%5. Other studies found a reduced percentage of fertilized eggs, reduced embroyo survival, and abnormal embroyos6. These results and other studies indicate that the reproductive potential of native fishes may be compromised in wastewater-dominated streams due to the presence of these chemicals7. Other studies have determined that fish, when exposed to these environmental estrogens, cannot regulate their internal homeostasis, called osmoregulation, which is related to the ability of fish to prevent dehydration or waterlogging, and buffers them against the effect of fresh or sea water) These studies of APEOs in US rivers have led scientists to conclude that fish are currently being impacted – they're our canaries.
Researchers at UC Davis found that offspring of fish in the San Francisco estuary had underdeveloped brains, inadequate energy supplies and dysfunctional livers. They grew slower and were smaller than offspring of hatchery fish raised in clean water.
Wastewater treatment facilities theoretically have the capabilities of effectively breaking down APEOs, but they are often not designed to remove them from the effluent. Most often sewer sludge contains these APEOs.
In the U.S., these chemicals are unregulated. There are no restrictions on their use. The US Environmental Protection Agency (EPA) has focused research efforts on determining acceptable levels of these compounds in water and identified NPEs as well as the chemical nonylphenol (NP) for further study because of concern about their impact on the environment and us.
Why has nothing been done? Because as you might imagine, this is big business, and the chemical lobby has not only impeded regulation but has even tried to block research.8 The lack of action on the part of environmental regulators in the United States stems largely in part from the research conducted by the Alkylphenol and Ethoxylate Research Council formed by the Chemical Manufacturers Association to conduct studies on APEO (APE Research Council, 2001). To date this panel has disputed all claims that NP concentrations in waterways of the United States are above concentrations where a significant effect would be realized. The Alkylphenol and Ethoxylate Research Council also contests the estrogenic potential of NP (APE Research Council, 2001).9
In Europe, the use of NPEO has been banned or voluntarily restricted since 1986. In 2002, Norway directed the phasing out of APEOs completely.10 Since 1998, the use of APEO in detergents has been forbidden in Germany – and since January 2005 the European Union directive 2003/53/EG has forbidden the use of NPEO in higher concentrations than 0.1% in product formulations. However, it will take years before there is progress as these chemcials are persistent and bio-accoumulative.
Although forbidden in the European Union (EU), many companies have production sites or suppliers outside Europe, where the use of NPEO is not forbidden. Textile eco-labels such as the EU flower and Oeko-Tex have also forbidden the use of APEOs.
But voluntary certifications and the prohibition in some countries is not enough to stem the tide, as Greenpeace found recently. Their Detox Campaign was designed to expose the links between clothing brands, their suppliers and toxic water pollution around the world. The Greenpeace studies found that these NPEs aren't just expelled into wastewater – they also remain in the finished textile. The chemicals found in the finished clothing of top name brands (Calvin Klein, Levi's and Victoria's Secret, among others) included nonylphenol ethoxylates (NPEs). Concentrations of NPEOs were found in 89 garments (just under two thirds of those tested) at levels ranging from just above 1 part per million up to 45000 parts per million in the top name brand items tested (Calvin Klein, Levi's, Victoria's Secret, H&M, Gap among others)11; over 20% of the items tested had more than 100 parts per million.
To see the PBS series on Frontline entitled "Poisoned Waters:"
1Zoller, Uri, "Endocrine disrupting APEOs in Isreal/Palestinian water resrouces: What should it take to prevent future pollution?", http://www.researchgate.net/publication/228493491
2Wessels, Denise, "Policy Brief: Endocrine Disrupters in Wastewater Alkylphenol Ethoxylates and the City of Indianapolis Combined Sewer System",
3Bechi, N., Estrogen-Like Response to p-Nonylphenol in Human First Trimester Placenta and BeWo Choriocarcinorna Cells, Toxicological Sciences, 93(1), 75-8 1 (September, 2006). http:lltoxsci.oxford~ournals.org/cgi/content~full/93/1l75.
4Potential adverse effects of NP and NPEs on human health is also discussed in Vazquez-Duhalt, Nonylphenol, an integrated vision of a pollutant, Applied Ecology and Environmental Research 4(1): 1-25 ISSN1589 1623, http:lIwww.ecology.kee.hu~pdf/O401~001025.pdf. Widespread exposure of the U.S. population to NP has been demonstrated. Calafat, A., Kuklenyik Z., Reidy J., Cauhll S., Ekong J., Needham L. 2005. Urinary Concentrations of Bisphenol A and 4-Nonylphenol in a Human Reference Population. Environmental Health Perspectives Vol. 113, p. 391. NP at high doses has been llnked to breast cancer in mice. BBC News. 2005. Chemical Link to Breast Cancer: http:llnews.bbc.co.uW1/hl/healthl676129.strnin 612005.
5Tyler, C.R. and Routledge, E.J., "Oestrogenic effects in fish in English rivers with evidence of their causation", Dept. of Biology and Biochemistry, Brunel University, UK, Pure and Applied Chemistry, Vol 70, No. 9 pp. 1796-1804, 1998.
6Dickey, Philip, "Troubling Bubbles: Alkylphenol ethoxylate surfactants", Washington Toxics Coalition
7"Response to comments submitted by the Alkylphenols and ethoxylates research council", by Victoria Whitney, Deputy Director, Division of Water Quality, State Water Resources Control Board, Sacramento, California, June 20, 2011 ALSO SEE: Tyler, C.R. and Routledge, E.J., "Oestrogenic effects in fish in English rivers with evidence of their causation", Dept. of Biology and Biochemistry, Brunel University, UK, Pure and Applied Chemistry, Vol 70, No. 9 pp. 1796-1804, 1998.
8Kristof, Nicholas, "Warnings from a Flabby Mouse", New York Times, January 19, 2013.
9Porter, A. and Hayden, N., "Nonylphenol in the Environment: A Critical Review", Dept of Civil and Encironmental Engineering, University of Vermont.
10Norris, David and Carr, James, "Endocrine Disruption: Biological Bases for Health Effects in Wildlife and Humans", Oxford University Press, 2006