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Occurrence and Fate of Hormone Steroids in the Environment

Authors:
  • Guangzhou Institute of Geochemistry

Abstract and Figures

Hormone steroids are a group of endocrine disruptors, which are excreted by humans and animals. In this paper, we briefly review the current knowledge on the fate of these steroids in the environment. Natural estrogenic steroids estrone (E1), 17beta-estradiol (E2) and estriol (E3) all have a solubility of approximately 13 mg/l, whereas synthetic steroids 17alpha-ethynylestradiol (EE2) and mestranol (MeEE2) have a solubility of 4.8 and 0.3 mg/l, respectively. These steroids have a moderate binding on sediments and are reported to degrade rapidly in soil and water. Estrogenic steroids have been detected in effluents of sewage treatment plants (STPs) in different countries at concentrations ranging up to 70 ng/l for E1, 64 ng/l for E2, 18 ng/l for E3 and 42 ng/l for EE2. E2 concentrations in river waters from Japan, Germany, Italy and the Netherlands ranged up to 27 ng/l. In addition, E2 concentrations ranging from 6 to 66 ng/l have also been measured in mantled karst aquifers in northwest Arkansas. This contamination of ground water has been associated with poultry litter and cattle manure waste applied on the land. Although hormone steroids have been detected at a number of sources worldwide, currently, there is limited data on the environmental behaviour and fate of these hormone steroids in different environmental media. Consequently, the exposure and risk associated with these chemicals are not adequately understood.
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Review article
Occurrence and fate of hormone steroids in the environment
Guang-Guo Ying
a,
*, Rai S. Kookana
a
, Ying-Jun Ru
b
a
CSIRO Land and Water, Adelaide Laboratory, PMB 2, Glen Osmond, SA 5064, Australia
b
SARDI Livestock Systems, Roseworthy Campus, Roseworthy, SA 5371, Australia
Received 24 May 2002; accepted 6 September 2002
Abstract
Hormone steroids are a group of endocrine disruptors, which are excreted by humans and animals. In this paper, we briefly review the
current knowledge on the fate of these steroids in the environment. Natural estrogenic steroids estrone (E1), 17h-estradiol (E2) and estriol
(E3) all have a solubility of approximately 13 mg/l, whereas synthetic steroids 17a-ethynylestradiol (EE2) and mestranol (MeEE2) have a
solubility of 4.8 and 0.3 mg/l, respectively. These steroids have a moderate binding on sediments and are reported to degrade rapidly in soil
and water. Estrogenic steroids have been detected in effluents of sewage treatment plants (STPs) in different countries at concentrations
ranging up to 70 ng/l for E1, 64 ng/l for E2, 18 ng/l for E3 and 42 ng/l for EE2. E2 concentrations in river waters from Japan, Germany, Italy
and the Netherlands ranged up to 27 ng/l. In addition, E2 concentrations ranging from 6 to 66 ng/l have also been measured in mantled karst
aquifers in northwest Arkansas. This contamination of ground water has been associated with poultry litter and cattle manure waste applied
on the land. Although hormone steroids have been detected at a number of sources worldwide, currently, there is limited data on the
environmental behaviour and fate of these hormone steroids in different environmental media. Consequently, the exposure and risk associated
with these chemicals are not adequately understood.
D2002 Elsevier Science Ltd. All rights reserved.
Keywords: Steroids; Sorption; Degradation; Endocrine disruptors; Effluent; Animal waste
1. Introduction
Steroid hormones are a group of biologically active
compounds that are synthesized from cholesterol and have
in common a cyclopentan-o-perhydrophenanthrene ring.
Natural steroids are secreted by the adrenal cortex, testis,
ovary and placenta in human and animal, and include
progestogens, glucocorticoids, mineralocorticoids, andro-
gens and estrogens (Raven and Johnson, 1999). Estrogens
(estradiol, estrone and estriol) are predominantly female
hormones, which are important for maintaining the health
of the reproductive tissues, breasts, skin and brain. Proges-
togens (progesterone) can be thought of as a hormonal
balancer, particularly of estrogens. Androgens (testosterone,
dehydroepiandrosterone and androstenedione) play an
important role in tissue regeneration, especially the skin,
bones and muscles. Glucocorticoids (cortisol) are produced
by the adrenal glands in response to stressors such as
emotional upheaval, exercise, surgery, illness or starvation.
All the steroid hormones exert their action by passing
through the plasma membrane and binding to intracellular
receptors. In addition, there are some synthetic steroids such
as ethynylestradiol (EE2) and mestranol (MeEE2) used as
contraceptives.
All humans as well as animals can excrete hormone
steroids from their bodies, which end up in the environment
through sewage discharge and animal waste disposal. Those
steroids have been detected in effluents of sewage treatment
plants (STPs) and surface water (e.g. Desbrow et al., 1998;
Kuch and Ballschmiter, 2001; Ternes et al., 1999a). They
may interfere with the normal functioning of endocrine
systems, thus affecting reproduction and development in
wildlife (Jobling et al., 1998). The steroids of concern for
the aquatic environment due to their endocrine disruption
potential are mainly estrogens and contraceptives, which
include 17h-estradiol (E2), estrone (E1), estriol (E3), 17a-
ethynylestradiol (EE2) and mestranol (MeEE2) (Fig. 1).
Vitellogenesis (plasma vitellogenin induction) and femi-
nisation in male fish have been observed in British rivers and
are attributed to the presence of these estrogenic compounds
0160-4120/02/$ - see front matter D2002 Elsevier Science Ltd. All rights reserved.
PII: S 0160-4120(02)00075-2
* Corresponding author. Fax: +61-9-83038565.
E-mail address: guang-guo.ying@csiro.au (G.-G. Ying).
www.elsevier.com/locate/envint
Environment International 28 (2002) 545 – 551
(Desbrow et al., 1998; Jobling et al., 1998). Concentrations as
low as 1 ng/l of E2 led to induction of vitellogenin in male
trout (Hansen et al., 1998; Purdom et al., 1994). Hormone
steroids in the environment may affect not only wildlife and
humans but also plants (Shore et al., 1995b; Lim et al., 2000).
Alfalfa irrigated with sewage effluent, which contained
hormone steroids, was observed to have elevated levels of
phytoestrogens (Shore et al., 1995b).
In addition to estrogenic steroids, there is also a concern
about the use of steroid drugs used as growth promoters in
livestock (Schiffer et al., 2001). However, little research has
been conducted on the fate of these steroids excreted by
animals and their effect on wildlife and human health.
In this brief review, we provide an overview of sources,
environmental concentrations in surface and ground water,
and summarize the current knowledge on fate and behaviour
of these steroid compounds.
2. Physicochemical properties
Natural estrogens, namely estradiol, estrone and estriol,
have solubilities of approximately 13 mg/l. Synthetic estro-
genic steroids have much lower solubilities of 4.8 mg/l for
EE2 and 0.3 mg/l for mestranol (Lai et al., 2000). All these
steroids have very low vapor pressures ranging from
2.3 10
10
to 6.7 10
15
mm Hg (Table 1), indicating
low volatility of these compounds. The log K
ow
values of
natural steroids are 2.81 for E3, 3.43 for E1 and 3.94 for E2.
Synthetic steroids have higher log K
ow
values, 4.15 for EE2
and 4.67 for mestranol. From the physicochemical proper-
ties of these steroids, it can be seen that estrogens are
hydrophobic organic compounds of low volatility. It is
expected that the sorption on soil or sediment will be a
significant factor in reducing aqueous phase concentrations.
3. Levels in the environment
3.1. Wastewater
The presence of estrogenic compounds in the environ-
ment has become a concern because they may interfere with
the reproduction of man, livestock and wildlife. The hor-
mones 17h-estradiol and estrone are naturally excreted by
women (2 12 and 3 –20 Ag/person/day, respectively) and
female animals, as well as by men (estrone 5 Ag/person/day)
(Gower, 1975). Based on the survey and previous measure-
ments of human estrogen excretion, Johnson et al. (2000)
estimated the daily excretion of estrogens from males and
females (Table 2). Males were excreting 1.6 Ag/day of E2,
3.9 Ag/day of E1 and 1.5 Ag/day of E3 in their urine.
Menstruating females were excreting 3.5 Ag/day of E2, 8
Ag/day of E1 and 4.8 Ag/day of E3 in their urine. The
menopausal women were taken as excreting 2.3 Ag/day of
E2, 4 Ag/day of E1 and 1 Ag/day of E3. Pregnant women
were excreting 259 Ag/day E2, 600 Ag/day of E1 and 600
Ag/day of E3. After reviewing the quantity of EE2 in the
oral contraceptive pills, 35 Ag/day was estimated as the
Fig. 1. Structures of hormone steroids.
Table 1
Physicochemical properties of steroids
a
Chemical
name
Molecular
weight
Water
solubility
(mg/l at 20 jC)
Vapour
pressure
(mm Hg)
log
K
owb
Estrone
(E1)
270.4 13 2.3 10
10
3.43
17h-Estradiol
(E2)
272.4 13 2.3 10
10
3.94
Estriol
(E3)
288.4 13 6.7 10
15
2.81
17a-Ethynylestradiol
(EE2)
296.4 4.8 4.5 10
11
4.15
Mestranol
(MeEE2)
310.4 0.3 7.5 10
10
4.67
a
Lai et al. (2000).
b
Octanol – water partition coefficient.
Table 2
Daily excretion (Ag) of estrogenic steroids in humans
a
Category E2 E1 E3 EE2
Males 1.6 3.9 1.5
Menstruating females 3.5 8 4.8
Menopausal females 2.3 4 1
Pregnant women 259 600 6000
Women – 35
a
Johnson et al. (2000).
G.-G. Ying et al. / Environment International 28 (2002) 545–551546
daily excretion of EE2. Based on daily excretion of estro-
gens by humans, dilution factor and previous measurements,
ng/l levels of estrogens are expected to be present in
aqueous environmental samples from English rivers (John-
son et al., 2000).
Estrogenic steroids have been detected in influents and
effluents of sewage treatment plants in different countries
(Baronti et al., 2000; Belfroid et al., 1999; Desbrow et al.,
1998; Kuch and Ballschmiter, 2001; Nasu et al., 2000;
Snyder et al., 1999; Ternes et al., 1999a). Average concen-
trations of estrogenic steroids (E3, E2, E1 and EE2) in
influents of six Italian activated sludge STPs were 80, 12,
52 and 3 ng/l, respectively (Baronti et al., 2000). However,
E3 was rarely reported to occur in such a high concentration
(80 ng/l). E3 was not detected in most of the influents
studied. In the raw sewage of the Brazilian STPs, estrogenic
steroids E2, E1 and EE2 were detected with average con-
centrations of 21, 40 and 6 ng/l, respectively (Ternes et al.,
1999a). Estrogen levels were lower with average concen-
trations of 15, 27 and 1.4 ng/l for E2, E1 and EE2,
respectively (Ternes et al., 1999a,b). Estrogenic steroids
were detected in three Dutch STPs with concentrations
ranging from < LOD to 48 ng/l for E2, from 11 to 140 ng/
l for E1 and from < 0.2 to 8.8 ng/l for EE2 (Johnson et al.,
2000). The concentrations of E2 in influents of Japanese
STPs ranged from 30 to 90 ng/l in autumn and from 20 to 94
ng/l in summer (Nasu et al., 2000).
The concentrations of estrogenic steroids in the effluents
ranged from below detection limit (LOD) to 64 ng/l for E2,
from < LOD to 82 ng/l for E1, from 0.43 to 18 ng/l for E3 and
from < LOD to 42 ng/l for EE2 (Table 3). From the table, it
can be seen that E2 was present at higher concentrations in the
effluents from STPs in Canada, UK and Japan than those
from other countries. E2 was detected in Japanese STP
effluent samples with concentrations ranging from 3.2 to 55
ng/l in summer and from 2.8 to 30 ng/l in autumn (Tabata et
al., 2001). The average concentrations in the effluents were
18 and 12 ng/l, respectively. Nasu et al. (2000) also measured
estrogenic steroids in effluents of Japanese STPs with similar
concentration ranges. In British STPs, the concentrations of
E1 in the effluents varied widely from 1.4 to 76 ng/l, while E2
concentrations lie in a similar range to that of Japanese STPs
(Desbrow et al., 1998). However, EE2 was only found in 7 of
21 effluent samples from domestic STPs in UK, with con-
centrations ranging from < LOD to 7 ng/l. In Canadian STPs,
E1 and E2 were determined with maximum concentrations of
48 and 64 ng/l, respectively. EE2 was detected in 9 of 10
effluent samples with a maximum concentration of 42 ng/l
(Ternes et al., 1999a). In comparison, the concentrations of
E2 in the effluents from German, Italian, Dutch, Swedish and
American STPs were lower, ranging from < LOD to 5.2 ng/l
(Baronti et al., 2000; Belfroid et al., 1999; Kuch and Ballsch-
miter, 2001; Larsson et al., 1999; Snyder et al., 1999; Ternes
et al., 1999a,b). However, Spengler et al. (2001) recently
reported a maximum concentration of 15 ng/l for E2 in
effluents of STPs in SE Germany, and they also detected
mestranol with a maximum concentration of 2.7 ng/l. The
levels of estrone in the effluents from different countries are
quite comparable. Estriol (E3) was only reported in Italian
STP influents and effluents (Baronti et al., 2000).
3.2. Animal waste
The other major source of hormone steroids is livestock
waste. Livestock such as sheep, cattle, pigs and poultry, as
well as other animals, excrete hormone steroids. In poultry
waste, a concentration ranging from 14 to 533 ng/g dry
waste with an average of 44 ng/g for E2 was reported by
Table 3
Concentration of hormones in effluents of sewage treatment plants (STPs)
Location Sampling date Sample no. Concentration (ng/l)
a
Reference
b
Estrone 17h-Estradiol Estriol Ethynylestradiol
Italy 10/99 – 03/00 30 2.5 – 82.1 (9.3) 0.44 – 3.3 (1.0) 0.43 – 18 (1.3) < LOD – 1.7 (0.45) 1
Netherlands 10/97, 12/97 6 < 0.4 – 47 (4.5) < 0.1 – 5.0 ( < LOD)
c
< 0.2 –7.5 ( < LOD) 2
Germany 11/97 16 < LOD – 70 (9) < LOD – 3 ( < LOD) <LOD – 15 (1) 3
Canada 11/97 10 < LOD 48 (3) < LOD– 64 (6) <LOD –42 (9) 3
UK 05/95 – 01/96 21 1.4 – 76 (9.9) 2.7– 48 (6.9) < LOD – 7 ( < LOD) 4
Japan 07/98– 03/99 27 3 3.2 – 55 (14)
d
––5
< LOD – 43 (13)
e
0.3 – 30 (14)
f
USA 05/97, 10/97 5 0.477 – 3.66 (0.9) < LOD– 0.759 (0.248) 6
Germany 06 – 10/00 16 < 0.1– 18 (1.5) < 0.15 – 5.2 (0.4) < 0.10 – 8.9 (0.7) 7
a
Concentration range and median in parentheses.
b
References: (1) Baronti et al. (2000), (2) Belfroid et al. (1999), (3) Ternes et al. (1999a), (4) Desbrow et al. (1998), (5) Nasu et al. (2000), (6) Snyder et al.
(1999), (7) Kuch and Ballschmiter (2001).
c
LOD = limit of detection.
d
Summer sampling.
e
Autumn sampling.
f
Winter sampling.
G.-G. Ying et al. / Environment International 28 (2002) 545–551 547
Shemesh and Shore (1994) and Shore et al. (1988, 1995a).
The E2 concentration in urine of cattle was found to be 13
ng/l on average by Erb et al. (1977).
Steroid drugs are frequently used in cattle as well as other
livestock, which control the oestrous cycle, treat reproduc-
tive disorders and induce abortion (Refsdal, 2000). This
could greatly increase the generation of hormone steroids in
urine of livestock (Callantine et al., 1961). Many cattle in
United States are also fed muscle-building androgens such
as trenbolone acetate (TbA) and melengestrol acetate
(MGA) (Schiffer et al., 2001). Manure from cattle treated
with TbA and MGA were collected and found to contain 5 –
75 ng/g TbOH and 0.3 8 ng/g MGA (Schiffer et al., 2001).
After 4.5 5.5 months of storage, levels up to 10 ng/g
trenbolone and 6 ng/g MGA were detected with a half-life
of 267 days for trenbolone.
3.3. Surface water
There are some reports on the levels of estrogenic
steroids in surface waters (Baronti et al., 2000; Belfroid
et al., 1999; Kuch and Ballschmiter, 2001; Tabata et al.,
2001).Tabata et al. (2001) conducted an extensive survey
of estrogenic steroids in 109 Japanese rivers and found E2
in 222 of 256 samples in summer with a mean concen-
tration of 2.1 ng/l and in 189 of 261 samples in autumn
with a mean concentration of 1.8 ng/l (Table 4). Estrone
(E1) was detected in 7 of 11 Dutch coastal/estuarine and
freshwater samples with a median concentration of 0.3 ng/l,
while E2 and EE2 were only detected in 4 and 3 of 11
samples, with most of the concentrations below the quanti-
fication limit of < 1 ng/l (Belfroid et al., 1999).The
measurements in Germany resemble the situation in the
Netherlands (Belfroid et al., 1999; Kuch and Ballschmiter,
2001). Estrogenic steroids were also detected in some
drinking water samples from southern Germany with an
average concentration of 0.4, 0.7 and 0.35 ng/l, respectively
(Kuch and Ballschmiter, 2001). E3 was found in Tiber river
water in Italy with a concentration of 0.33 ng/l, while E2
and E1 were 0.11 and 1.5 ng/l in the river water, respec-
tively (Baronti et al., 2000).
3.4. Ground water
Recent studies have shown that disposal of animal manure
to agricultural land could lead to movement of estrogenic
steroids into surface and ground water (Bushe
´e et al., 1998;
Nichols et al., 1997, 1998; Peterson et al., 2001; Shore et al.,
1995a). E2 has been found mobile and detected in runoff from
manured land (Nichols et al., 1997, 1998).Nichols et al.
(1998) determined an average E2 concentration of 3500 ng/l
in the runoff from a pastural land applied with 5 Mg/ha of
manure (poultry litter). Ground water has been reported to be
contaminated with E2 (Peterson et al., 2001; Shore et al.,
1995a).Shore et al. (1995a) believed that a constant E2
concentration of about 5 ng/l in spring waters was caused by
infiltration of E2 through the soil profile to the ground water.
Peterson et al. (2001) measured E2 concentrations ranging
from 6 to 66 ng/l in mantled karst aquifers in northwest
Arkansas. The observed E2 concentration trends imitated the
changes in stage over the recharge event. The contamination
was associated with poultry litter and cattle manure waste
applied on the area.
4. Fate in the environment
4.1. Sorption
The distribution and partitioning of estrogenic steroids in
the environment are determined by their physicochemical
properties and site-specific environmental conditions. Wil-
liams et al. (1999) estimated the likely distribution of the
steroid estrogens, E1, E2 and EE2, in three English rivers and
predicted that the concentrations of these steroids under
average conditions varied between 0.21 and 0.37 ng/l for
E2, 0.27 and 0.44 ng/l for E1 and 0.024 and 0.038 ng/l for
EE2. Bed sediments were shown to account for between 13%
Table 4
Concentration of hormone steroids in surface water
Location Sample type Concentration (ng/L)
a
Reference
b
estrone 17h-estradiol estriol ethynylestradiol
Japan 109 major rivers < LOD – 27 (2.1)
c,d,e
1
< LOD – 24 (1.8)
c,f
Germany river water 0.10 – 4.1 (0.40) 0.15 – 3.6 (0.3) 0.10 – 5.1 (0.4) 2
Italy Tiber river water 1.5 0.11 0.33 0.04 3
The Netherlands coastal/estuarine water and rivers (11 locations) < 0.1 – 3.4 (0.3) < 0.3 – 5.5 ( < 0.3) < 0.1 – 4.3 ( < 0.1) 4
a
Concentration range and median in parentheses.
b
References: (1) Tabata et al. (2001), (2) Kuch and Ballschmiter (2001), (3) Baronti et al. (2000), (4) Belfroid et al. (1999).
c
Arithmetic mean ( Fstandard deviation) in parentheses.
d
LOD = limit of detection.
e
Summer sampling.
f
Autumn sampling.
G.-G. Ying et al. / Environment International 28 (2002) 545–551548
and 92% of the chemical loads in the river system. Lai et al.
(2000) measured sorption coefficients of E1, E2, E3, EE2 and
MeEE2 on a sediment and the log K
f
values were 1.71, 1.56,
1.33, 1.72 and 2.26, respectively. They found the sorption on
sediments was nonlinear with sorption constants ranging
from 0.57 to 0.83, thus the log K
oc
values were not defined.
However, in Table 5, we converted the log K
f
values into K
oc
values, which ranged from about 1900 to 16 000. This data
indicates that estrogenic steroids adsorb moderately onto
sediment. The sorption of estrogens correlated with the
presence of organic carbon content and also increased with
salinity in water (Lai et al., 2000). Although the K
oc
values
from this study, as well as K
ow
values of these estrogenic
steroids in Table 1, suggest their hydrophobic nature and high
binding with sediment/soil particles, these compounds have
been widely reported not only in surface water but also in
ground water. Clearly, there is a need to better understand
their behaviour in different environmental media.
4.2. Degradation
In humans and animals, estrogens undergo various trans-
formations mainly in the liver. They are frequently oxidized,
hydroxylated, deoxylated and methylated prior to the final
conjugation with glucuronic acid or sulphate. 17h-Estradiol
is rapidly oxidized to estrone, which can be further con-
verted into estriol, the major excretion product. Many other
polar metabolites like 16-hydroxy-estrone, 16-ketoestrone
or 16-epiestriol are formed and can be present in urine and
faeces. The contraceptive ingredient mestranol is converted
after administering into 17a-ethynylestradiol by demethy-
lation (Ternes et al., 1999a).17a-Ethynylestradiol is mainly
eliminated as conjugates, whereas other metabolic trans-
formations occur, but are of minor relevance. Therefore,
estrogens are excreted mainly as inactive conjugates of
sulphuric and glucuronic acids. Although steroid conjugates
do not possess a direct biological activity, they can act as
precursor hormone reservoirs able to be reconverted to free
steroids by bacteria in the environment (Baronti et al., 2000;
Ternes et al., 1999a). Due to the presence of microorganisms
in raw sewage and STPs, these inactive conjugates of
estrogenic steroids are cleaved, and active estrogenic ste-
roids are released to the environment (Baronti et al., 2000;
Ternes et al., 1999a).
In an aerobic batch experiments with activated sludge,
E2 was oxidized to E1, which was further eliminated with-
out any degradation products observed (Ternes et al.,
1999b). The contraceptive EE2 was principally persistent
under selected aerobic conditions, where mestranol was
rapidly eliminated and small portions of EE2 were formed
by demethylation. In another experiment (Layton et al.,
2000), 70 80% of added E2 was mineralized to CO
2
within
24 h by biosolids from wastewater treatment plants, whereas
the mineralization of EE2 was 25 75-fold less. EE2 was
also reported to be degraded completely within 6 days by
nitrifying activated sludge and resulted in the formation of
hydrophilic compounds (Vader et al., 2000).
The half-lives of estrogenic steroids were estimated to be
2 6 days in water and sediment (Williams et al., 1999).
Microorganisms in water samples from English rivers were
capable of transforming E2 to E1 with half-lives of 0.2 9
days when incubated at 20 jC, and E1 was then further
degraded at similar rates (Ju
¨rgens et al., 2002). E2 could
also be degraded when incubated with aerobic and anaero-
bic riverbed sediments. Compared to E2, EE2 was much
more resistant to biodegradation in water from English
rivers (Ju
¨rgens et al., 2002).
Removal during sewage treatment is used as a collective
term to describe the disappearance of chemicals due to
processes such as biodegradation and adsorption on sludges.
It depends on the plant performance and input of wastes. By
comparing influent and effluent estrogen concentrations,
Baronti et al. (2000) calculated that removal rates of E3,
E2, EE2 and E1 from wastewater in activated STPs were
95%, 87%, 85% and 61%, respectively. Low removal rates
for E1 may be related to transformations of estradiol in
STPs. In the Brazilian STPs, the observed removal rates
ranged from 64% to 78% for EE2, from 67% to 83% for E1
and from 92% to 99.9% for E2 (Ternes et al., 1999a).
However, in German STPs, the removal rates were very low,
e.g. only 64% for E2. In the Japanese STPs, the removal
rates were reported to be more than 99% in autumn and
from 7% to >99% in summer (Nasu et al., 2000). The reason
behind this large difference in removal rates is still unclear.
Johnson and Sumpter (2001) recently reviewed the removal
of endocrine-disrupting chemicals in activated sludge treat-
ment works and suggested that the activated sludge treat-
ment process can consistently remove over 85% of E2, E3
and EE2, but the removal performance for estrone (E1)
appears to be less and is more variable.
In many countries, biosolids, recycled water and animal
waste, which contain hormone steroids are often applied to
agricultural land. The persistence of estradiol, estrone and
17a-ethynylestradiol in soils was examined recently in
laboratory incubations (Colucci and Topp, 2001; Colucci
et al., 2001). E2 was rapidly removed in the agricultural
soils incubated under a range of conditions. At 30 jC,
following 3 days incubation, more than 56% of E2 applied
Table 5
Sorption and half-lives of steroids
Chemical name Sorption constant
a
(K
oc
) Half-life
b
(days)
Estrone (E1) 4882 2 –3
17h-Estradiol (E2) 3300 2 – 3; 0.2 – 9
c
Estriol (E3) 1944 NR
17a-Ethynylestradiol (EE2) 4770 4 – 6
Mestranol (MeEE2) 16 542 NR
NR = not reported; Williams et al. (1999).
a
Lai et al. (2000).
b
Half-life in river water (days).
c
Ju
¨rgens et al. (2002).
G.-G. Ying et al. / Environment International 28 (2002) 545–551 549
(1 mg/kg) in three agricultural soils with a moisture content
of 13% was non-extractable with its half-life of less than 0.5
days in all cases (Colucci et al., 2001). E2 was abiotically
transformed into estrone (E1) in both sterile and nonsterile
soils. In contrast, E1 and EE2 were found to be microbially
degraded (Colucci and Topp, 2001; Colucci et al., 2001).
The dissipation half-life of EE2 ranged from 7.7 days at 4
jC to 3 days at 30 jC(Colucci and Topp, 2001). However,
the behaviour and persistence of E1 in the soils studied were
unknown.
5. Summary and recommendations
Hormone steroids excreted by humans and animals enter
the environment through the discharge of domestic sewage
effluents and disposal of animal waste. These compounds
could affect wildlife and human health by disrupting their
normal endocrine systems. Hormone steroids have been
detected in wastewater effluents and surface water as well
as ground water at various levels. The behaviour and fate of
these hormone steroids in the environment depend on their
physiochemical properties and environmental media.
Natural estrogenic steroids (E1, E2 and E3) have higher
solubilities than synthetic steroids 17a-ethynylestradiol
(EE2) and mestranol (MeEE2). Limited studies indicated
that they all have moderate sorption on sediments and short
half-lives in soils and water. These natural and synthetic
steroids undergo rapid transformations in sewage treatment
plants. Their removal rates in STPs are dependent on the
plant design and waste load.
There have been limited reports on the occurrence of
hormone steroids in the environment. Detailed surveys are
necessary to understand the distribution of hormone steroids
in the environment, especially in STPs effluents, soils,
surface water and ground water. Animal waste and biosolids
as well as recycled wastewater have been increasingly
applied to agricultural land; therefore, it is vital to estimate
the input of steroids and their possible movement into
surface and ground water through runoff and leaching.
There is also a scarcity of data on daily excretion of steroids
from different domestic animals, which could be used to
calculate the steroid loads on agricultural land.
Although estrogenic steroids were reported to degrade
rapidly in soil and water in laboratory incubations, more
research is needed to investigate the dissipation and path-
ways of these steroids in different media such as river water,
seawater and ground water as well as sediments and soils.
Factors (biotic and abiotic) influencing their degradation
need to be explored further. In addition, most of the studies
in the literature focused on estrogenic steroids; little research
has been conducted on androgens. Steroid growth promoters
are widely used in livestock in some countries and have
become a recent public concern. Persistence of these steroid
drugs in the environment and their possible effects on
wildlife and human health still remain unclear.
Acknowledgements
The authors would like to thank Dr. A. Juhasz and Dr. A.
Kumar for their valuable comments.
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