SURFACTANT CHEMISTTRY &

TECHNOLOGY

Nonylphenol Ethoxylate Surfactants

History, Use, and Safety

University of Technology
Vietnam National University Ho Chi Minh City

2023
Introduction

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Introduction

nonylphenol ethoxylate (NPE) is the most important alkylphenol ethoxylate (APE).

NPE accounts for approximately 82% of alkylphenol ethoxylate production

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Uses

•Industrial Processing (70) •Industrial Cleaning (20)

•Textiles •Industrial and institutional cleaning
•Pulp and paper products
•Agricultural chemicals/pesticides •Industrial and institutional laundry
•Metal processing products
•Lube oils and fuels •Household Cleaning (10)
•Plastics processing •Laundry detergents
•Emulsion polymers/paints/coatings •Hard surface cleaners
•Personal Care (lt1)
•Pharmaceuticals
•Cosmetics
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Uses

Công nghiệp (54%)

Tẩy rửa CN và văn

phòng (30%)
Homecare &
Personalcare(15%)
Khác (1%)

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Uses

Công nghiệp (54%)

Tẩy rửa CN và văn

phòng (30%)
Homecare &
Personalcare(15%)
Khác (1%)

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Use and Disposal Patterns

• Disposal practices
• Down the drain to treatment plant
• On-site treatment or pre-treatment
• Remain encapsulated
• Sprayed onto foliage and soil
Application
• Institutional and household cleaning products
• Industrial processing aids
• Paints and coatings
• Pesticide formulations

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Degradation

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Degradation
APEn (n=9)

1 2 3
Ether
APs APEn carboxylates
(n=1÷4) Akylphenoxy
NP, OP,… acetic acid,
Akylphenoxy
ethoxy acetic
acid
NPEs may degrade into nonylphenol. During degradation NPEs’ ethylene oxide
units are cleaved off the ethylene oxide chain until only short-chain NPE remain,
typically mono- and diethylene oxides.
NP is not readily biodegradable. 9
State of the Science Environmental Exposure

•NP and NPE are not known to exist in nature.

•NP is released to the environment from production and use as a
chemical intermediate, in the polymer industry, and as nonylphenol itself.
The major part (95%) is released to water. The proportion released to air
is low (1%), while approximately 4% is released to soil. Further, NP is
released from NPE. NP has a low vapour pressure, a low water solubility,
and has a strong tendency to adsorb to soils and sediments.
•NPE is primarily released to the environment as a result of use. As for
NP, the major part (85%) is released to water, while the release to soil
amounts to 13%, and to air 2.5% (EU-RAR 1998).

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State of the Science Environmental Exposure
Air
NP: NP has not been measured in the atmosphere (EU-RAR 1998).
NPE: No data have been found.
Water
NP has been found in surface water, sea water, and ground water (data from
Switzerland, United Kingdom, USA, and Croatia). A typical value was 1 mg/l, and the
highest value measured was 180 mg/l (River Aire, UK) (EU-RAR 1998).
NPEs have been found in European surface water in concentrations
ranging from below the limit of detection to 59mg/l (Talmage 1994).
Soil
In sludge from waste water treatment plants, concentrations of NP in the order of
gram per kg dry weight have been found. In soil treated with sludge, 4.7 mg/kg has
been found (EU-RAR 1998).
In river sediments, NPE concentrations of the order of mg per kg dry weight have
been measured (Talmage 1994).
Foodstuffs
NP was detected in raw beef samples, concentration not stated (HSDB 1997).

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State of the Science Environmental Exposure
Bioaccumulation
NP bioconcentrates to a significant extent in aquatic species. Excretion
and metabolism is rapid (EU-RAR 1998).
No data have been found for NPE.

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State of the ScienceEnvironmental Effects

•Aquatic studies with NP dozens of species covering fish,

amphibians, mollusks, insects, annelids, crustaceans, algae,
protozoa, and microorganisms
•Mechanisms of toxicity (VTG, blood steroids, transitory
changes in growth), acute and longterm mortality, growth
and reproduction
•Aquatic and terrestrial studies with NPE and NPEC
•acute and chronic data for fish, crustaceans, and birds

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Human exposure

The routes of human exposure to NP and NPEs are dermal contact and
inhalation by workers involved in manufacture and use, dermal and
inhalation exposure of consumers from household pesticide products,
dermal contact to cleaning products and cosmetics, mucous membrane
contact to spermicides; and exposure via the environment through
drinking water, air, and food.

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Toxicokinetics

After oral administration, absorption of NP in humans may be significant.

Limited data indicate that first pass metabolism may account for
inactivation by conjugation of a major part of the NP present in
blood.
The main part of NP and NPE metabolites are believed to be Glucuronic
acid conjugates, which are excreted via the kidney. No data exist
regarding inhalation or dermal exposure, but it is assumed that
absorption will occur.

Human toxicity
There are no data on human oral or inhalatory toxicity of NP or NPE.

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Animal toxicity -single exposure
The LC50 of NP and NPE by inhalation is unknown. For NP, no data have
been found. NPEs with 4 or 7 ethylene oxide units caused no mortality in
concentrations up to 20 mg/l, indicating a low acute toxicity of NPE by
inhalation.
Oral LD50 values for NP mostly in the range of 1200 - 2400 mg/kg have
been reported indicating a low order of acute oral toxicity of NP. For
various NPEs (number of ethylene oxide units 4-10, 12, 13, 15 or 20)
oral LD50 values between 1000 and more than 5000 mg/kg have been
reported. Acute oral toxicity seems to be independent of NPE ethylene
oxide chain length.
A dermal LD50 of 2031 mg/kg NP in rabbits has been reported. The acute
dermal toxicity of NPEs with 4, 5, 7, 9,10, 12, 13 and 40 ethylene oxide
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Animal toxicity- local effects

The sensory irritation potential of nonylphenol has been investigated in

mice in a respiratory depression test. At 3636 mg/m3 a mean respiratory
rate depression of about 25% was found during exposure. However, at
267 mg/m3 there were no changes in the respiratory rate. These results
suggest that nonylphenol can cause mild sensory irritation to the respiratory
tract at high exposure levels.
NP is corrosive on contact with skin and is a severe eye irritant.
Exposure to the saturated vapour may lead to mild sensory irritation of the
Respiratory tract.31 units is low, as LD50 values varying between 2000
mg/kg and 5-10,000 mg/kg have been reported.

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Animal toxicity- repeated exposure
The lowest toxicity was found for NPEs with ethylene oxide chain lengths of 20 or
more. Toxic effects included retarded growth and increased liver weight, for some
compounds necrosis of liver cells.
In dogs, similar effects have been found. Dose-response relations seem comparable.
However, in this species a specific toxic effect of certain NPEs on the heart has been
found, related to ethoxylene oxide chain lengths of 15, 17.5, and 20 (but not for NPEs
with chains outside this range). The cardiac effect is focal myocardial necrosis,
sometimes lethal.
The NOAEL for cardiotoxicity in the dog is not known, nor is the mechanism. Guinea
pigs also seem to develop this type of lesion, while cats, rats, and rabbits do not.
In rats, reduced weight gain was observed after administration of NPE with 4 EO. In
dogs, increased relative liver weight without accompanying histopatho-
32 logical findings, but with elevated serum alkaline phosphatase level was
observed.
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Animal toxicity- repeated exposure
For NE:
In a multigeneration study in rats increased incidence of renal tubular degeneration
and/or dilatation were found in both sexes and across all generations. There was no
dose level without effect.

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Animal toxicity- Reproductive and developmental effects
NP has been shown to mimic the effects of oestrogen via activation of the oestrogen
receptor.
NP has shown oestrogenic effect in fish, daphnids, and in human breast tumour cells.
In uterotrophic assays NP has shown oestrogenic effect in immature Wistar rats, in
immature Sprague-Dawley rats, and in ovariectomised Sprague-Dawley rats.

hormone-mimicking

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Animal toxicity- Reproductive and developmental effects
Research with rainbow trout:
For male fish: Reduces
Vitellogenin prefix and testicle
size. (Jobling and Sumpter 1993)
For female fish: reduces egg
quantity, reduces fetal viability,
increases the number of
teratogens (Japanese Medaka)
(Gronen et al. 1999)

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Animal toxicity- Reproductive and developmental effects

Minimum concentration of NP that causes effects on aquatic organisms

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Animal toxicity- Reproductive and developmental effects

OP can break down some proteins

in turtles (Trudeau et al. 2002).

For tadpoles of Leopard frogs, OP

combined with UV rays can
disrupt their normal metabolism
(Crump et al., 2002).

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Animal toxicity- Reproductive and developmental effects

OP & OPE reduced testicular size and

semen production in rats when applied for
21 days (Sharp et al. 1996)

NP stimulates Estrogen, causing the

vagina of adult female mice to become
keratinized (Bodds and Lawson 1938).

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Animal toxicity- Genotoxicity & Carcinogenicity

Genotoxicity
The existing mutagenicity studies of NP are not of sufficient quality to
allow a proper evaluation of mutagenic potential. NPEs with 9 or 30
ethylene oxide units were negative in the Ames test.
Carcinogenicity
For NP, no data have been found.
NPEs with 4 or 9 ethylene oxide units have been administered in 2-
year studies. However, because of an insufficient number of animals,
the studies do not allow a proper evaluation of carcinogenic potential.

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Human
NP has shown oestrogenic effect in human breast tumour cells.

Able to "mimic" the body's hormone Oestradiol.

1µg NP =300,000 µg Oestradiol
1991: NPEs increase MCF-7 → cause breast cancer
NPEs also cause genital disorders and reduce sperm count in
men.

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Human

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Human

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Human

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Solution

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Solution

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