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w w w. e l s e v i e r. c o m / l o c a t e / s c i t o t e n v

Review

Removal mechanisms for endocrine disrupting compounds


(EDCs) in wastewater treatment physical means,
biodegradation, and chemical advanced oxidation: A review

Ze-hua Liu, Yoshinori Kanjo, Satoshi Mizutani


Department of Urban Engineering, Graduate School of Engineering, Osaka City University, Sugimoto 3-3-138, Sumiyoshi-Ku,
Osaka 558-8585, Japan

AR TIC LE D ATA ABSTR ACT

Article history: Endocrine disrupting compounds (EDCs) are pollutants with estrogenic or androgenic
Received 15 March 2008 activity at very low concentrations and are emerging as a major concern for water quality.
Received in revised form 8 August 2008 Within the past few decades, more and more target chemicals were monitored as the source
Accepted 29 August 2008 of estrogenic or androgenic activity in wastewater, and great endeavors have been done on
Available online 6 November 2008 the removal of EDCs in wastewater. This article reviewed removal of EDCs from three
aspects, that is, physical means, biodegradation, and chemical advanced oxidation (CAO).
Keywords: 2008 Elsevier B.V. All rights reserved.
Endocrine disrupting compounds
(EDCs)
Biodegradation
Physical means
Chemical advanced oxidation (CAO)
Review

Contents

1. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 732
2. Removal of EDCs by physical methods . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 733
2.1. Absorption by activated carbon . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 733
2.2. Rejection by membranes. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 735
3. Removal of EDCs by biodegradation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 735
3.1. Removal of EDCs by existing wastewater treatment systems. . . . . . . . . . . . . . . . . . . . . . . . . . . 735
3.2. Removal of EDCs in lab-scale experiments . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 738
4. EDCs removal by chemical advanced oxidation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 739
5. Conclusions. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 744
Acknowledgements . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 744
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 744

Corresponding authors. Tel./fax: +81 6 6605 3048.


E-mail address: liuzehua78@yahoo.co.jp (Z. Liu).

0048-9697/$ see front matter 2008 Elsevier B.V. All rights reserved.
doi:10.1016/j.scitotenv.2008.08.039
732 SC IE N CE OF T H E TOT AL E N V I RO N ME N T 4 0 7 ( 2 00 9 ) 7 3 17 48

water, surface waters, sediments, groundwater, and even


1. Introduction drinking water (Ternes et al., 1999a; Befenati et al., 2003;
Petrovic et al., 2003; Snyder et al., 2003, Vethaak et al., 2005;
Endocrine disrupting compounds (EDCs) are chemicals with Durhan et al., 2006; Fernandez et al., 2007). Wastewater
the potential to elicit negative effects on the endocrine sys- treatment plants have been studied as a major source for
tems of humans and wildlife. In the past few decades, research EDCs (Kolpin et al., 2002; Legler et al., 2002; Snyder et al., 2003;
efforts to combat this problem have grown immensely. Key to Nakada et al., 2006; Tan et al., 2007). Being EDCs exist in
the solution for this problem is the identification of EDCs, the extremely low concentration ( g/L or ng/L), highly sensitive
accurate measurement of their presence in aquatic systems, measurement of EDCs is necessary, including chemical
and development of methods for their elimination from the monitoring, such as liquid chromatography-tandem mass
environment. spectrometry (LC-MS/MS), gas chromatography-tandem mass
Various natural and synthetic chemical compounds have spectrometry (GC-MS/MS), high performance liquid chromato-
been identified that induce estrogen-like responses; including graphy (HPLC) and bioassay (both in vitro and in vivo). Detailed
pharmaceuticals, pesticides, industrial chemicals, and heavy information may be found in Flemming and Bent (2003) and
metals (Giesy et al., 2002). The US Environmental Protection Karin (2003).
Agency (USEPA) defines an EDC as: An exogenous agent that EDCs have been attributed as a cause of reproductive
interferes with the synthesis, secretion, transport, binding, disturbance in humans and wildlife (Hayes et al., 2002; Oak
action, or elimination of natural hormones in the body that are et al., 2004; Samir et al., 2006; Campbell et al., 2006). Human
responsible for the maintenance of homeostasis, reproduc- exposure to these chemicals in the environment is a critical
tion, development, and/or behavior. (USEPA, 1997) concern with unknown long-term impacts. Natural and
This broad class of chemicals includes natural estrogens, synthetic EDCs are released into the environment by humans,
such as estrone (E1),17-estradiol (E2), and estriol (E3) (Blair animals and industry; mainly through sewage treatment
et al., 2000; Nishihara et al., 2000; Folmar et al., 2002; Zhu et al., systems before reaching the receiving bodies (soil, surface
2006); natural androgens such as testosterone (T), dihydrotes- water, sediment and ground water), EDCs' main distribution in
tosterone (DHT), and androsterone (A) (Bauer et al., 2000; Fang the environment is illustrated in Fig. 1. (Flemming and Bent,
et al., 2003); artificial synthetic estrogens or androgens, such as 2003). EDCs are a latent crisis to humans and the environment.
ethynylestradiol (EE2), Norgestrel (N), and Trenbolone (Tr) Theoretically this crisis could be easily controlled, if EDCs
(Blair et al., 2000; Bauer et al., 2000); phytoestrogens including can be completely removed from sewage at sewage treat-
isoflavonoides and coumestrol (Bacaloni et al., 2005; Stopper ment plants before final release into the environment. EDCs
et al., 2005) as well as other industrial compounds such as removal methods fall into three categories; physical removal,
bisphenol A, nonylphenol (Mocarelli et al., 1996; Ramamoorthy biodegradation and chemical advanced oxidation (CAO). This
et al., 1997; Howdeshell et al., 1999; Ying et al., 2002). Such article will focus on the latest progress of these removal
chemicals as those above have been found existing in waste- methods.

Fig. 1 EDCs distribution in the environment.


S CIE N CE OF T H E TOT AL E N V I RO N ME N T 4 0 7 ( 2 00 9 ) 7 3 17 48 733

influence factors of the physicochemical properties of the


2. Removal of EDCs by physical methods EDCs and the types of AC produced from different materials.
In a study by Abe (1999), absorbability of about 70 EDCs by AC
2.1. Absorption by activated carbon was estimated from their chemical structures, and then their
adsorption by AC was proven effective for their removal from
Use of activated carbon (AC) is a well-known process for wastewater. Five alkylphenols were used to evaluate the AC
removing various organic contaminants. AC is most com- removal performance, in which AC was prepared from coco-
monly applied as a powdered feed (powder activated carbon, nut shells under different activation times. Results denoted
PAC) or in a granular form (granular activated carbon, GAC) in that adsorption capability increased with activation time. As
packed bed filters. Several authors have demonstrated the activation time increases, micropore volume and specific
efficiency of AC, both as PAC and GAC, for the removal of trace surface area increase (Iwasaki et al., 2001); Removal perfor-
organic pollutants from water (Matsui et al., 2002a,b; Asada mances for three EDCs (amitrol, nonylphenol, and bisphenol
et al., 2004; Westerhoff et al., 2005; Zhou et al., 2007). In the A) were studied by using a GAC fixed bed on lab-scale. Data
past few years, many researchers have demonstrated that showed EDCs with high Kow (octanolwater partition coeffi-
AC also has a strong capability of removing a broad range cient) values could be effectively removed, the authors
of representative EDCs for artificial and real waste water in the also found that activated carbon types and service life have
laboratory and pilot and full-scale plants (Nakanishi et al., different performances on EDCs removal. Adsorption capacity
2002; Iwasaki et al., 2001; Zha and Wang, 2005; Choi et al., 2005; decreased with the total years of operation, and among
Fukuhara et al., 2006; Tsai et al., 2006; Snyder et al., 2007). the three activated carbon types, the coal-based carbon was
Studies on EDCs removal by AC mainly focus on the found more effective than the other two due to its larger pore
removal efficiency of EDCs in different water systems and the volume, which was proven here more correlative on AC's

Table 1 Physicochemical properties of EDCs studied for membrane processes and their corresponding rejection
Compounds Molecular weight Water solubility logKow pKa Rejection References
(g/mol) (mg/L) (%) a

Estrone (E1) 270.4 30 3.13 10.5 4695% Chang et al. (2003)


1095% Nghiem et al. (2004)
4244% Yoon et al. (2007)
N 95% Cartinella et al. (2006)
17-Estradiol (E2) 272.4 3.6 4.01 10.71 2090% Nghiem et al. (2004)
2983% Kimura et al. (2004)
840% Yoon et al. (2007)
N 95% Cartinella et al. (2006)
Estriol (E3) 288.4 441 2.45 10.4 38% Yoon et al. (2007)
17-ethynylestradiol (EE2) 296.4 11 3.67 10.4 3460% Yoon et al. (2007)
Bisphenol A (BPA) 228.9 120 3.32 9.6 2196.6% Agenson and Urase (2007)
93.4% Gomez et al. (2007)
1883% Kimura et al. (2004)
4599% Kimura et al. (2003)
99.8 to N 99.9% Agenson et al. (2003)
Bisphenol F (BPF) 200.2 N.A b N.A N.A 59.5% Gomez et al. (2007)
Triethyleneglycol dimethacrylate 286.3 N.A N.A N.A 63.4% Gomez et al. (2007)
(TEGDMA)
Testosterone 288.2 23 3.32 17.4 3060% Yoon et al. (2007)
Progesterone 314.2 8.8 3.87 N.A 5465% Yoon et al. (2007)
Androstenedione 286.2 58 2.75 N.A 3058% Yoon et al. (2007)
Alkyphenol
4-ethylphenol 122.2 N.A 2.41 N.A 1070% Jung et al. (2007)
4-n-butylphenol 150.2 N.A 3.76 N.A 1582% Jung et al. (2007)
92.3 to N 99.9% Agenson et al. (2003)
2-tert-butylphenol 150.2 N.A 3.55 N.A 1582% Jung et al. (2007)
4-tert-butylphenol 150.2 N.A 3.31 N.A 1582% Jung et al. (2007)
2-phenylphenol 170.2 N.A 3.09 N.A 2290% Jung et al. (2007)
4-n-pentylphenol 164.3 N.A 4.06 N.A 2290% Jung et al. (2007)
4-n-heptylphenol 192.3 N.A 4.15 N.A 3593% Jung et al. (2007)
4-tert-octylphenol 206.3 N.A 5.14 N.A 4295% Jung et al. (2007)
4-n-octylphenol 206.3 N.A 5.16 N.A 4295% Jung et al. (2007)
4-n-nonylphenol 220.4 N.A 5.66 10.2 5095% Jung et al. (2007)

EDCs physicochemical properties were concluded from references (Jung et al., 2007; Yoon et al., 2007; Gomez et al., 2007; Kimura et al., 2003, 2004;
Agenson et al., 2003; Campbell et al., 2006).
a
Many data values were taken from references' diagrams without specific values.
b
Not available.
734 SC IE N CE OF T H E TOT AL E N V I RO N ME N T 4 0 7 ( 2 00 9 ) 7 3 17 48

absorbability other than its specific area (Choi et al., 2005); Compared to artificial EDCs wastewater, a great difference in
Representative endocrine substances, Estrone (E1) and17- EDCs removal by AC adsorption between simulated wastewater
estradiol (E2) were also used to evaluate the removal and real wastewater was observed. Fukuhara et al. (2006)
performance on absorption, the effects of some fundamental observed that the amount of E2 adsorbed in river water and in
environmental parameters including adsorbent concen- secondary effluent was about one-thousandth of that in pure
tration, pH, salinity and the presence of humic acid and water solution. Severe deterioration of adsorption capacity was
surfactant on adsorption were studied. The results showed also found in the effluent of WWTPs by Snyder et al. (2007),
that adsorption capacity of AC was decreased with an increase when the EDCs removal efficiencies of effluent of WWTPs were
in adsorbent concentration and by the presence of surfactant compared to those of surface water. To overcome the problem of
and humic acid (Zhang and Zhou, 2005). deterioration of AC adsorption on complex wastewater systems,

Table 2 Physicochemical properties and estrogenic (androgenic) activity of target EDCs


Name of EDCs Main category CAS Mol wt. Water LogKOW RBA RBA Estrogenic Estrogenic
(g/mol) solubility (AR) a (ER) a potency (YES) b potency
(mg/L) (E-screen) c

Estrone (E1) Natural estrogen 53-16-7 270.4 30 3.13 1.3e 3 0.44 0.38 d,1 0.01
17-estradiol (E2) Natural estrogen 50-28-2 272.4 3.6 4.01 0.66 1 1 d,1 1
17-Estradiol (E2) Natural estrogen 57-91-0 272.4 e 4.01 d 8.85e 4 0.801 0.3 d,0.075 0.1
Estriol (E3) Natural estrogen 50-27-1 288.4 441 2.45 3.2e 4 0.33 0.024 d,0.001 0.3
Ethynylestradiol (EE2) Pharmaceutical 57-63-6 296.4 116 3.67 4.82e 3 1.4 1.19 d,1.5 1.25
2-Hydroxyestrone Natural estrogen 362-06-1 286.3 0.04 g 2.6e 3 f
(2-OHE1)
16-Hydroxyestrone Natural estrogen 566-76-7 286.3 5.5e 4 0.065
(-OHE1)
Equilin Natural estrogen 474-86-2 268.4 1.14 h 3.35 h 1.05e 3 0.289
17-dihydroequilin Natural estrogen 651-55-8 270.4 0.18 g
(d-equilin)
Testosterone (Te) Natural androgen 58-22-0 288.4 30 3.32 0.685 b e 5 f e 5
Androstenedione (An) Natural androgen 734-32-7 286.4 58 2.41e 3 i
Androsterone (A) Natural androgen 53-41-8 290.4 12 3.69 5.7e 4
Progesterone (PR) Natural androgen 57-83-0 314.5 8.84 3.87 0.0359
Norethindrone (N) Androgenic 68-22-4 298.4 7.04 2.97 0.146 1.53e 3 2.8e 4 f
pharmaceutical
Tamoxifen Estrogenic 10540-29-1 371.5 1.65e 4 0.47 b 2e 8 4e 5
pharmaceutical
17-trenbolone Androgenic 10161-33-8 270.4 1.09 j
(-Tr) pharmaceutical
17-trenbolone Androgenic 80657-17-6 270.4 0.045 j
(-Tr) pharmaceutical
Genistein Phytoestrogen 446-72-0 270.2 258 2.84 3.6e 5 i 1.2e 3 0.002
Coumestrol Phytoestrogen 479-13-0 268.2 2.64e 3 6.7e 4
Daidzein Phytoestrogen 486-66-8 254.2 1.8e 3 2e 6
Equol Phytoestrogen 531-95-3 242.3 4.1e 5 2e 5
Biochanin A Phytoestrogen 491-80-5 284.3 1.26e 5 b 2e 6
Formononetin Phytoestrogen 485-72-3 268.3 2.65e 4
BPA Industrial chemical 80-05-7 228.3 120 3.32 3.01e 4 2e 3 6.7e 4 3e 5
Nonylphenol Industrial chemical 25154-52-3 220.3 3000 3.28 1.26e 4 1.4e 3 b 2e 7 8e 5
(NP)
Octylphenol (OP) Industrial chemical 140-66-9 206.3 5 1.4 1.25e 4 1.24e 3 b 2e 7 6e 5

Unlabelled data in Table 2 was adapted from NITE (2008).


a
RBA: relative binding affinity determined by estrogen receptor (ER) ligand competitive binding assay (ER-binding assay) or androgen receptor
(AR) ligand competitive binding assay (AR-binding assay).
b
Estorgenic potency determined by yeast estrogen screen (YES), from Nishihara et al. (2000).
c
Estrogenic potency determined by E-Screen, from Tan (2006) cited from others.
d
Rutishauser et al. (2004) cited by Teske and Arnold (2008).
e
Not available or not binding (response).
f
Bovee et al. (2004).
g
Zhu et al. (2006).
h
Yalkowsky and Dannenfelser (1992) cited by Robert et al. (2007).
i
Fang et al. (2003).
j
Bauer et al. (2000).
S CIE N CE OF T H E TOT AL E N V I RO N ME N T 4 0 7 ( 2 00 9 ) 7 3 17 48 735

one effective alternative is its combination with membrane for reverse osmosis under conditions of organic fouling.
filtration (to be discussed below). For nano-membranes, rejection of BPA increased with fouled
membranes compared to virgin membranes, from 21%
2.2. Rejection by membranes (virgin), to 29% (fouled by leachate), to 60.8% (fouled by
activated sludge), while for reverse osmosis, rejection
The membrane process is gaining wide use for contaminant decreased from 96.6% (virgin) to 85% (fouled by leachate), to
removal in advanced water and wastewater treatment. 82% (fouled by activated sludge). For organic solute influence,
Compared to conventional processes, its remarkable advan- rejection of E1 was examined by Chang et al. (2003) in buffer
tage is the high quality of effluent, including extremely low solution, surface water and secondary effluent. Rejection
organic concentration, and removal of microbes and viruses decreased both in surface water and secondary effluent.
without chemical disinfection. There is much research data Studies on rejection of EDCs by the membrane process
on membrane processes for the effective removal of organic were based only on chemical analyses, no bioassay methods
micro-pollutants; from pesticides to pharmaceuticals to were seen among references. Removal of EDCs by physical
personal care chemicals (Van der et al., 1998; Snyder et al., means is not like biodegradation or chemical oxidation, as no
2007). In recent years, research on EDC removal by the byproducts or metabolites are newly produced. Thus, the
membrane process has greatly increased. This research can removal effectiveness in laboratory studies with simulated
be sorted to three categories: (1) EDCs' physicochemical pro- wastewater can be completely evaluated by chemical analysis.
perties on the effective rejection by membrane, (2) influence However, when research is based on real wastewater, removal
of membrane module on the rejection of EDCs, and (3) other effectiveness of many unknown EDCs in wastewater may not
influence factors such as the membrane fouling or the pre- be covered by a chemical analysis, therefore, it is still
sence of organic solutes in removal water. necessary to apply bioassays to evaluate the removal proper-
Studies have discovered that the rejection efficiency of ties of EDCs by physical means. Among the studies referenced
EDCs by membranes strongly depended on EDCs' physico- here, there is only one (Zha and Wang, 2005), in which an
chemical properties, such as molecule weight, Kow, water in vivo assay was used to evaluate the removal effect of
solubility, electrostatic property and so on. According to our different means on EDCs, in that case a combination of ultra-
knowledge, a limited range of chemicals (natural estrogen and membrane and reverse membrane process was proven more
estrogenic chemicals) was studied in regards to the membrane effective than solely ultra-membrane or reverse membrane.
process. These chemicals' physicochemical properties are
summarized in Table 1, where rejection efficiencies are also
drawn from references. 3. Removal of EDCs by biodegradation
From Table 1, we see that EDCs rejection by the membrane
processes has a very wide range, from 10% to greater than 99.9%. 3.1. Removal of EDCs by existing wastewater treatment
The reason for this is that apart from the EDCs' physicochemical systems
properties, the rejection has a strong direct relationship with
membrane types. EDCs retention by the membrane processes is The objective of wastewater treatment systems is to remove
mainly due to size exclusion, charge repulsion and adsorption. organic substances, phosphorus and nitrogen from waste-
In comparing membrane types over most cases, EDCs rejection water, but research has discovered that EDCs can also be
rate by reverse osmosis is the highest, followed by nano- reduced by wastewater treatment systems. Among waste-
membrane types, then ultra-membranes, with the rejection of water treatment systems, the activated sludge process is the
micro-membranes as the lowest. Chang et al. (2002, 2003) most widely used in the world, and as the proportion of
studied the E1 rejection by a micro-membrane, and high removal by primary settling, chemical precipitation, aerating
rejection results were attained for all cases of buffer solution, volatilization and sludge absorption was small, the majority
surface water and secondary effluent. However, rejection de- of EDCs in wastewater is regarded as removed by biodegra-
creased with the increasing of permeation (filtering time), the dation (Svenson et al., 2003; Andersen et al., 2003; Braga et al.,
same phenomenon was also observed by others (Nghiem et al., 2005).
2004; Kimura et al., 2003,2004; Zhang et al., 2006a,b). Because With the progress of chemical analysis of EDCs and endless
the pore size of the micro-membrane tested was several orders endeavor by environmental researchers, research on the
of magnitude larger than the estrone molecules, rejection was occurrence and fate of target EDCs in WWTPs has increased
regarded as a result of adsorption rather than membrane greatly, and more and more target EDCs are monitored and
sieving, and the rejection was found to be reversible. detected. Physicochemical properties of 26 of these target
Salt rejection is often used to quantify the rejection proper- EDCs are shown in Table 2, including their relative binding
ties of reverse osmosis by membrane manufacturers, which was affinity and estrogenic potency. Removal performances of
found inappropriate to indicate potential rejection of EDCs by these target EDCs by existing WWTPs are listed in Table 3.
Kimura et al. (2004). Compared to salt rejection, molecule weight From Table 3, it is clear that most of the EDCs were not
cut-off (MWCO) was suggested as more useful for rough completely removed by existing WWTPs and they remained
prediction of EDCs rejection properties, especially for alkylphe- with fluctuating concentrations in effluent, and discharge of
nols, in which the case a linear relationship between rejection such effluent may be the main reason for the wide distribution
and MWCO was proven (Jung et al., 2007). and occurrence of EDCs in surface waters, ground waters, and
Regarding membrane fouling, Agenson and Urase (2007) even in drinking waters (Table 3). Incomplete removal of EDCs
studied membrane performances for nano-membranes and by existing WWTPs not only results from the fluctuation
736 SC IE N CE OF T H E TOT AL E N V I RO N ME N T 4 0 7 ( 2 00 9 ) 7 3 17 48

Table 3 Examples of occurrence and fate of target EDCs in various water systems at ng/L concentration
Target EDCs Surface Ground Drinking WWTPs Reference
water water water
Influent Effluent Removal (%)

E1 b 0.13.4 [1] n.d120 [2] 0.20.6 [11] 25132 2.582 22 to 95 Baronti et al. (2000)
0.26.6 [3] n.d4.5 [13] 44 17 61 (mean) D'Ascenzo et al. (2003)
b 0.37.2 [4] n.d1.6 [16] 29670 n.d a72 111 to 100 Clara et al. (2005)
512 [5] 1978 196 55 to 98 Servos et al. (2005)
1.412.9 [6] 20130 b 0.311 b Vethaak et al. (2005)
b 1738 [7] n.d18.3 n.d6.7 64100 Tan (2006)
n.d7.4 [15] 57.883.3 6.349.1 4189 Robert et al. (2007)
n.d4.6 [16] 433 0147 Fernandez et al. (2007)
1.13.0 [17] 230510 n.d 100 Ito (2008)
E2 b 0.35.5 [1] n.d45 [2] 0.22.1 [11] 4.025 0.353.5 5998 Baronti et al. (2000)
0.61.0 [3] 666 [9] 2.6 [12] 11 1.6 85 (mean) D'Ascenzo et al. (2003)
b 0.81.0 [4] 1380 [10] n.d2.6 [15] 35125 n.d30 44100 Clara et al. (2005)
26 [5] n.d0.79 [16] 2.426 0.214.7 18.5 to 98.8 Servos et al. (2005)
n.d-8.8 [6] 17150 b 0.8 Vethaak et al. (2005)
b 0.71.7 [7] 22.0 0.95 96 (mean) Braga et al. (2005)
1.615.5 [8] n.d161.6 n.d5.4 5299 Robert et al. (2007)
n.d3.8 [15] 011 0158 Fernandez et al. (2007)
17-E2 b 0.13.0 [1] n.d0.21 [16] 0.3 [11] b 0.715 b 0.4 Vethaak et al. (2005)
b 0.30.4 [4] n.d1 n.d38 Fernandez et al. (2007)
n.d25 [7] n.d n.d Robert et al. (2007)
0.152.0 [11]
n.d0.31 [16]
E3 25 [5] n.d0.16 [16] 24188 0.4318 7799 Baronti et al. (2000)
n.d3.3 [6] 72 2.3 97 (mean) D'Ascenzo et al. (2003)
n.d3.1 [14] 2348 n.d1 96.7 (mean) Lagana et al. (2004)
n.d1.7 [15] 23660 n.d275 18100 Clara et al. (2005)
n.d1.9 [16] 138381 b 14.9 N7 Drewes et al. (2005)
1.02.5 [17] 222 029 Fernandez et al. (2007)
EE2 b 0.14.3 [1] n.d0.94 [16] 0.150.5 [11] 0.4013 n.d1.7 52100 Baronti et al. (2000)
b 0.30.4 [4] 4.97.1 2.74.5 3345 Cargouet et al. (2004)
n.d1 [5] b 0.35.9 b 0.32.6 Vethaak et al. (2005)
5.730.8 [8] 370 n.d5 33.3100 Clara et al. (2005)
0.15.1 [11] b 0.714.4 b 0.74.1 7193 Drewes et al. (2005)
n.d4.6 [15] n.d1.2 n.d0.6 55 Robert et al. (2007)
1.12.9 [17] 02 0178 Fernandez et al. (2007)
2-OHE1 n.d14 Xiao et al. (2001)
15 n.d 100 Gentili A et al. (2002)
-OHE1 27 n.d 100 Gentili A et al. (2002)
n.d5 Ternes et al. (1999a)
3671 1315 79.179.6 Jiang et al. (2005)
9.590 2.414 6482 Schlusener (2005)
Equilin b 147 [18] n.d n.d Robert et al. (2007)
b 1055 [19]
D-equilin n.d23.8 n.d23.6 1 Robert et al. (2007)
Te n.d1.8 [6] 19.4143 b 14.9 8199 Drewes et al. (2005)
b 214 [18] n.d95 n.d21 Fernandez et al. (2007)
b 10 [19] n.d11 n.d 100 Ito (2008)
0.42.4 [20]
An n.d5.3 [6] 21100 n.d 100 Ito (2008)
b 10 [19]
40 [21]
0.280.46 [22]
A n.d [22] b 12400 b 126.4 NYAS (2008) c
3601300 n.d 100 Ito (2008)
11021441 Chang et al. (2008)
PR 1.44.2 [6] n.d14 n.d 100 Ito (2008)
b 199 [18] 3.110 0.310.37 9096.3 Chang et al. (2008)
b 10 [19]
2060 [21]
N b 872 [18] 26224 0159 Fernandez et al. (2007)
b 10 [19] n.d n.d Chang et al. (2008)
n.d3 [23] 53205 Viglino et al. (in press)
S CIE N CE OF T H E TOT AL E N V I RO N ME N T 4 0 7 ( 2 00 9 ) 7 3 17 48 737

Table 3 (continued)
Target EDCs Surface Ground Drinking WWTPs Reference
water water water
Influent Effluent Removal (%)

Tamoxifen 27212 [24] 143215 146369 158 to 7 Robert and Tomas (2006)
b 10 [25]
b 471 [26]
-Tr 1020 [27] n.d n.d Chang et al. (2008)
-Tr b 10120 [27]
Genistein 35 [28] 195384 716 87.8 (mean) Lagana et al. (2004)
47 [29] 962 222 97 (mean) Bacaloni et al. (2005)
b 2.6507.1 [30]
Coumestrol 12 [28] 923 n.d19 66100 Bacaloni et al. (2005)
Daidzein 24 [28] 75120 716 87.9 (mean) Lagana et al. (2004)
23 [29] 1874 n.d22 69100 Bacaloni et al. (2005)
b 3526 [30]
Equol n.d22 [29]
Biochanin A 13 [28] 818 35 73.3 (mean) Lagana et al. (2004)
12 [29] 1476 n.d21 6790 Bacaloni et al. (2005)
b 8.460.2 [30]
n.d12 [31]
Formononetin n.d21 [31] n.d10 n.d Bacaloni et al. (2005)
BPA b 8.81000 [4] n.d7 [32] 0.52.0 [11] 332339 1336 90 (mean) Lagana et al. (2004)
0.514 [11] n.d930 [16] 5 [33] 2505620 b 434090 92 (mean) Vethaak et al. (2005)
n.d600 [16] 7202376 161840 1099 Clara et al. (2005)
1529 [32] 2813642 650 9098 Drewes et al. (2005)
65295 [33] 88438 111054 Fernandez et al. (2007)
n.d5.7 [34] 4503300 610710 5355 Ito (2008)
NP b 1104100 [4] n.d3.1e6 [2] 2.516 [11] 41948768 11202235 75 (mean) Lagana et al. (2004)
6.7134 [11] n.d1500 [16] 24019000 5501500 50 (mean) Vethaak et al. (2005)
n.d890 [16] 157027,411 4264926 3394 Drewes et al. (2005)
12891466 [32] 14,72841,207 n.d90,043 Fernandez et al. (2007)
1.321.3 [34] 21004500 300400 8493 Ito (2008)
OP b 504300 [4] n.d42 [16] 0.24.9 [11] 183321 281358 96 to 13 Korner et al. (2000)
0.854 [11] b 27013000 b 4501300 0 (mean) Vethaak et al. (2005)
n.d41 [16] 300 N 6704 37.5180 5598 Drewes et al. (2005)
0.041.1 [34] n.d796 n.d240 11 to 100 Leusch et al. (2006)

[1] Belfroid et al. (1999); [2] Swartz et al. (2006); [3] Isobe et al. (2003); [4] Vethaak et al. (2005); [5] Lagana et al. (2004); [6] Kolok et al. (2007); [7]
Kolodziej and Sedlak (2007); [8] Shen et al. (2001); [9] Peterson et al. (2000); [10] Wicks et al. (2004) cited by Campbell et al. (2006); [11] Kuch and
Ballschmiter (2001); [12]Roefer et al. (2000) cited by Nghiem et al. (2004); [13] Fine et al. (2003); [14] Xiao et al. (2001); [15] Morteani et al. (2006); [16]
Hohenblum et al. (2004); [17] Cargouet et al. (2004); [18] Kolpin et al. (2002); [19] Vogel et al. (2005); [20] Shore et al. (2004); [21] Jenkins et al. (2003);
[22] Chang et al. (2008); [23] Viglino et al. (in press); [24] Robert and Tomas (2006); [25] Hilton and Thomas (2003); [26] Thomas and Hilton (2004);
[27] Durhan et al. (2006); [28]Bacaloni et al. (2005); [29] Lagana et al. (2004); [30] Ribeiro et al. (in press); [31] Erbs M et al. (2007); [32] Lagana et al.
(2004); [33] Rodriguez-Mozaz et al. (2004); [34] Beck et al. (2005).
a
Not detected.
b
Not available.
c
The New York Academy of Science.

of EDC levels in the influent, but the processes of the WWTPs, Andersen et al. (2003) investigated the fate of E1, E2 and EE2 at
and as well as operational conditions. one German sewage treatment plant. They observed that an
As early as 1999, EDCs removal by activated sludge process overall elimination efficiency of E1 and E2 was above 98%, while
was studied in Germany, Canada and Brazil, in which they EE2 elimination was slightly lower. About 90% of E1 and E2 were
were evaluated by GC-MS/MS. The removal efficiency for E1, found to be degraded in the activated sludge system while EE2
E2 and EE2 was 83%, 99.9% and 78%, respectively (Ternes et al., primarily was degraded only in the nitrifying tank. This was
1999a); In 2003, 20 wastewater treatment plants with us of no proven by Yi and Harper (2007), in which the biotransformation
biological unit (chemical precipitation), activated sludge rate of EE2 had a linear relationship with the NH3-N biotrans-
process and trickling filter were studied using a YES bioassay formation rate in a series of batch experiments. Clara et al. (2005)
in Sweden. Results denoted that the activated sludge process found that the solids retention time (SRT) was a suitable de-
got the highest estrogenic removal, and trickling filters were sign parameter to evaluate the capacity of wastewater treat-
better than chemical precipitation. The corresponding mean ment plants to remove EDCs as well as other micro-pollutants,
removal rates were 81%, 28% and 18% (Svenson et al., 2003). while Servos et al. (2005) found that SRT has no substantial
The same tendency can be found in the references by Servos relationship with EDCs removal, which was measured both by
et al. (2005) and Johnson et al. (2007). chemical analysis and bioassay. In many occasions, E1
738 SC IE N CE OF T H E TOT AL E N V I RO N ME N T 4 0 7 ( 2 00 9 ) 7 3 17 48

concentration in effluent was higher than in influent (Baronti concentration. It is also feasible to change environmental factors
et al., 2000; Joss et al., 2004; Johnson et al., 2007), which was like DO, Hydraulic Retention Time (HRT), Sludge Retention Time
explained as the biotransformation of E2 into E1 (Johnson and (SRT) and other influencing conditions. Therefore, to gain further
Sumpter, 2001). Environmental conditions such as dissolved knowledge on EDCs removal under different conditions and
oxygen (DO) is also an important factor, generally EDC removal biodegradation mechanisms of EDCs, lab-scale experiments are
efficiency in aerobic conditions was higher than in anaerobic necessary. There are many experiments on degradation of both
condition (Furuichi et al., 2006; Ermawati et al., 2007). natural hormones such as E1, E2 and synthetic chemicals
Except for chemical analyses, bioassays were also widely including EE2, Bisphenol A (BPA), Nonylphenol (NP) under
used to evaluate the occurrence and fate of EDCs in the process aerobic and anaerobic conditions using artificial wastewater or
of WWTPs. Reports on EDCs removal of WWTPs evaluated by real wastewater. Table 5 shows the summary of some studies on
bioassays are listed in Table 4, where removal efficiencies biodegradation of E2, BPA and NP on the lab-scale.
differed with different reports. Apart from the research on Ternes et al. (1999b) investigated the aerobic biological
occurrence and fate of EDCs in WWTPs, the links between reactions of natural and synthetic estrogens in contact with
chemical analyses and bioassays were also discussed by many activated sludge collected from an actual sewage treatment
researchers. Nakada et al. (2004) studied some effluent samples plant. In batch experiments using commercial standard
of WWTPs in Japan, and results denoted that E1 and E2 estrogenic substances, they found that E2 is converted rapidly
represented more than 98% of the total estrogen equivalent to E1, E1 removal is slower than oxidation of E2 to E1, and
concentration (EEQ) by using YES assay. Similar results from conjugates of the estrogens in contact with activated sludge
Nelson et al. (2007) suggested that about 95% of the total EEQ were cleaved. Suzuki and Maruyama (2006) studied aerobic
were derived from E1, E2 and E3 in municipal WWTPs effluents batch experiments using municipal sewage and activated
by using the same bioassay. However, Salste et al. (2007) found sludge, in which different conditions such as sludge concen-
that the calculated EEQ of E1, E2, E3 and EE2 in wastewater tration, reaction temperature, low- and high-load sludge were
effluent was only about 7% of the values from the biolumines- compared. Results discovered that E1 and E2 were initially
cent yeast assay. Tan (2006) compared both influent and effluent absorbed by activated sludge at a very fast speed, then
results of five WWTPs by using GC-MS analysis and E-screen, biodegraded by activated sludge within a few hours. In the
and chemical derived values ranged from about 0.1%1340% experiment at a lower temperature, the activity of activated
of those from E-screen. Results from Ito (2008) suggested that sludge was markedly decreased, and dissolved organic carbon
chemically-derived estrogenic activities of two WWTPs were (DOC) removal and nitrification were limited, but E2 and E1
about 1.283.8% of those measured by ER ligand competitive were as effectively removed as they were in the case of higher
binding assay. Bioassays can provide direct information of temperature. The results suggested that the removal of
the activities of EDCs in environmental samples irrespective of natural estrogens such as E2 and E1 by activated sludge was
the causative compounds, and for large-scale monitoring, bio- independent of the general DOC decomposition and nitrifica-
assays seem most appropriate due to their low cost and high tion. Czajka and Londry (2006) investigated the anaerobic
throughput capability, as important as Chemical Oxygen biotransformation of EE2 and E2, in which cultures were
Demand (COD) and Biological Oxygen Demand (BOD) which established using lake water and sediment under methano-
are widely used to appraise the pollution index of wastewater. genic, sulfate-, iron- and nitrate-reducing conditions. The
However, to date no bioassay can be universally accepted as a anaerobic degradation of EE2 was not observed in multiple
standard method. trials over long incubation periods, E2 was transformed to E1
under all four above anaerobic conditions and the oxidation of
3.2. Removal of EDCs in lab-scale experiments E2 was not inhibited by the presence of E1. Reversible inter-
conversion of E2 and E1 was also observed on some occasions.
Compared to large-scale wastewater treatment systems, studies Chang et al. (2005) found that the addition of yeast extract
on removal of EDCs by lab-scale experiments have some or some surfactants could enhance the degradation rate of NP.
advantages such as controllable wastewater constitute or Sulfate-reducing bacteria, methanogen, and eubacteria were

Table 4 EDCs removal of WWTPs evaluated by different bioassays


Num Wastewater type WWTP type In vitro assay Removal (%) Reference

1 Domestic AS ER-binding 73 Ito (2008)


2 Swine UASB + filter E-screen 8393 Shappell et al. (2007)
3 Swine Wetland MVLNa 4499 Furuichi et al. (2006)
4 Domestic AS ER-binding 90 N 99 Leusch et al. (2006)
5 Domestic AS E-screen N 95 Leusch et al. (2005)
6 Domestic AS YES 0100 Servos et al. (2005)
7 Domestic AS MVLN 6197 Cargouet et al. (2004)
8 Domestic AS YES 58 to N 99 Svenson et al. (2003)
9 Domestic AS YES 5167 Holbrool et al. (2002)
10 Domestic AS E-screen 91 Korner et al. (2000)
11 Domestic AS YES 92 Matsui et al. (2000)
a
MCF-7 human breast carcinoma cell line, stably transfected with an estrogen-regulated luciferase gene.
S CIE N CE OF T H E TOT AL E N V I RO N ME N T 4 0 7 ( 2 00 9 ) 7 3 17 48 739

also proven to have a role in the degradation of NP. Ogawa Table 6 Redox potentials of some oxidizers used in
et al. (2005) studied the degradation of E2, BPA and NP in wastewater treatment
aerobic and anaerobic sludge, both degradation efficiency and Oxidizer Reaction E/V Reference
degrading dynamics were given.
Cl2 Cl2 (g) + 2e 2Cl 1.358 Jiang and Lloyd (2002)
ClO + H2O + 2e Cl + 0.841 Jiang and Lloyd (2002)
2OH
4. EDCs removal by chemical advanced oxidation ClO2 ClO2 (aq) + e ClO2 0.954 Jiang and Lloyd (2002)
O3 O3 + 2H+ + 2e O2 + H2O 2.076 Jiang and Lloyd (2002)
Within the past few years, there have been numerous studies on H2O2 H2O2 + 2H+ + 2e 2H2O 1.776 Jiang and Lloyd (2002)
the removal of EDCs through the use of different chemical FeO2
4 FeO24 + 8H+ + 3e Fe3+ + 2.20 Jiang and Lloyd (2002)
4H2O
oxidants, known as chemical advanced oxidation (CAO). The
S2O2
4 S2O2
4 (aq) + 2e 2SO4
2
2.01 House (1962)
essential mechanisms of CAO are mineralization of pollutants
in wastewater to CO2 or transference of pollutants to some other
metabolite products by some strong oxidizers through oxida-
tionreduction reactions. Therefore the key point for CAO is the redox potential can give better results. Thus CAO is generally
choice of oxidizer. Redox potentials of some wastewater referred to as the combination means in a narrow sense.
treatment oxidizers are listed and compared in Table 6. Here, Research on the removal of EDCs by CAO can be divided to
the strength order of redox potential is FeO2 4 N O3 N S2O4 N
2
three categories: (1) removal effectiveness and optimization of
H2O2 N Cl2 N ClO2.To increase the removal effect, some operational conditions for CAO; (2) degradation dynamics
combinations such as UV/O3, UV/H2O2, UV/Fenton were widely research on EDCs removal by CAO; and (3) degradation
applied to the removal of EDCs. These methods are character- pathways of EDCs by CAO. Results of removal of EDCs by
ized by the generation of the hydroxyl radical (OHU), for which CAO are summarized in Table 7, where most of the results are
the redox potential is 2.80V (Lei and Wang, 2001), and the higher from lab research based on artificial sewage. Jiang et al. (2005)

Table 5 Summary of some studies on biodegradation of E2, BPA and NP in lab-scale experiments
EDCs Initial Experimental conditions Degradation Reference
concentration efficiency
Aerobic or Inoculation Experimental Temp (%)
anaerobic period (C)

E2 1 mg/L Aerobic Activated sludge 13h Unknown N 95 Ternes et al. (1999b)


1 g/L (MLSS 2600 mg/L)
200 g/L Aerobic Supernatant of activated 24h 21 88 Lee and Liu (2002)
sludge
Anaerobic 7days 50
0.4 mg/L Aerobic Nitrosomonas europaea 187h 30 N 95 Shi et al. (2002a)
1 mg/L Aerobic Activated sludge 2h 30 98 Shi et al. (2002b)
(MLSS 2700 mg/L)
333 mg/L Aerobic Activated sludge 14days 25 60 Fuji et al. (2002)
(MLSS unknown)
1 g/g Aerobic Aquifer material 2days 20 50 Ying et al. (2003)
Anaerobic 107days
0.030.1 g/L Aerobic Activated sludge 72h 25 9699 Ogawa et al. (2005)
(MLSS N 2580 mg/L)
Anaerobic SS3500 mg/L 30days 1638
5ng/L Aerobic Activated sludge 4h 20 N 80 Suzuki and
(MLSS500 mg/L) Maruyama (2006)
3 mg/L Aerobic Isolated bacteria 7days 30 N 75 Yu et al. (2007)
100 g/L Aerobic Activated sludge 28days 20 N 90 Ren et al. (2007)
(MLSS220 mg/L)
BPA 100 mg/L Aerobic River water 14days 30 100 Chen et al. (1996)
1 g/g Aerobic Aquifer material 70days 20 50 Ying et al. (2003)
3 mg/L Aerobic Chemical plant treated 4days 2225 N 90 Dorn et al. (1987)
effluent
0.0510 g/L Aerobic Activated sludge 72h 25 7299 Ogawa et al. (2005)
(MLSS N 2750 mg/L)
Anaerobic SS3300 mg/L 30days 922
NP 1 g/g Aerobic Aquifer material 7days 20 50 Ying et al. (2003)
350388 mg/L Aerobic Isolated bacteria 13days 28 9899 Tanghe et al. (1999)
5 mg/L Anaerobic SS1800 mg/L 84days 30 N 85.5 Chang et al. (2005)
150 g/L Aerobic Activated sludge 72h 25 5990 Ogawa et al. (2005)
(MLSS N 2530 mg/L)
Anaerobic SS3030 mg/L 30days 1721
740
Table 7 Research on EDCs removal by CAO
EDCs Wastewater CAO Operational Analyses Main conclusions Reference
condition

E2 Aqueous NaClO pH 7.5; T = 25C; LC-MS 1) estrogenic activity of aqueous solution decreased [1]
solution C a = 1.46 mg/L; Two hybrid with the increase of chlorination time, activity of
C bI = 50 g/L yeast assay chlorinated solution at 120min was about 40% of that
before chlorination, subsequent chlorination yielded
no further significant decrease in the activity of the solution;
2) seven byproducts of chlorinated solution were identified,
those byproducts were all proved to possess estrogenic activity
by using YES, among them estrogenic strength of one
byproducts is equal to E1;

SC IE N CE OF T H E TOT AL E N V I RO N ME N T 4 0 7 ( 2 00 9 ) 7 3 17 48
3) degradation pathways of E2 by chlorination were proposed.
BPA Aqueous NaClO pH7.5; T = 25C; LC-MS 1) thirteen byproducts of chlorinated solution were identified [2]
solution C = 1.46 mg/L; NMR a, c and BPA degradation pathways by chlorination were proposed;
CI = 500 g/L NMR a, c 2) estrogenic activity of chlorinated solution evaluated by
Two hybrid ER-binding assay at 60min was 24 times that before chlorination,
yeast assay; corresponding activity measured by yeast two hybrid assay before
ER-binding assay and after chlorination showed almost no change.
E1, E2, Aqueous NaClO pH = 3.512; HPLC 1) except for PR, the other five EDCs exhibited a pseudo-first order [3]
E3, EE2, solution T = 20 2C; dependence on the EDCs concentration, their apparent second order
NP, PR C 35mol/L; rate constants suggest pH dependence, minimal at about pH = 5,
CI = 1mol/L maximal at pH between 8 and 10;
2) apparent second order rate constants were calculated for ionized
EDCs, neutral EDCs and acid-catalyzed reaction with neutral EDCs,
and at pH = 7 the apparent second order rate constants were
calculated to range from 12.6 to 131.1M 1- s 1;
3) at pH = 7, for a total chlorine concentration of 1 mg/L,
the corresponding half-life time for NP was about 65min,
and was 68min for the other EDCs.
BPA, EE2, Surface water or K2FeO4 pH = 8; T = 25C; HPLC 1) when concentration of Fe(VI) was above 1 mg/L and reacting for [4]
E2 effluent of WWTPs CI = 0.15mol/L 30min, removal efficiency of spiked EDCs in surface water or effluent
of WWTPS was over 99%
2) the apparent second order rate constants were determined and
their values were between 640 and 730M 1 s 1
E1, E2, Municipal K2FeO4 pH = 78, GC-MS Removal efficiency was between 30.7% and 96.2% for target EDCs and [5]
BPA, NP wastewater Fe(VI) = 1020 mg/L removal efficiency of COD was 40% after a reaction of 20min
BHAb, d Aqueous solution UV/S2O2
8 pH = 7; LC-MS/MS 1) pseudo pseudo-first order rate constants were determined at [6]
T = 23 2C = 2 mmol/L; different pH and BHA can be completely removed within
CI = 0.3 mmol/L 20min by UV/S2O2 8 ;
2) degradation pathways were proposed in acidic condition and at other pH level;
3) in terms of mineralization and moderate efficiency in removing
BHA, the optimum condition was suggested as neutral pH.
E 1, Effluent of WWTPs O3 O3/UV O3/H2O2 CO3 = 515 mg/L; LC-MS 1) target EDCs could be 100% removed at concentration of 5 to 15 mg/L O3; [7]
Caffeine water quality: GC-MS/MS 2) compared to applying only O3, a combination of O3/UV
pH 7.2; DOC = 23 mg/L; could improve the disinfecting effect.
COD = 30 mg/L;
SS = 4.5 mg/L
EE2 Pure water and O3 UV/H2O2 CO3 = 0.12.0 mg/L; HPLC 1) for pure water EE2 solution, apparent second order [8]
surface water CI = 0.5umol/L rate constant was 7 109M 1 s 1 at O3 condition and was
9.8 109M 1 s 1 at O3/H2O2 condition
2) removal effect differed greatly for different water solutions
at the same reaction condition, the half-life time for lake water
was 4min, however, for river water, the corresponding
value was 75min.
E2, EE2, Distill water O3 T = 20C, HPLC All target EDCs could be 100% removed and the estrogenic activity [9]
BPA reaction time: E-screen could be also reduced.
1120min,
CO3 = 1.5 mg/L,
CI = 100nmol/L

S CIE N CE OF T H E TOT AL E N V I RO N ME N T 4 0 7 ( 2 00 9 ) 7 3 17 48
EE2 Pure water O3 CI = 1 or 10mol/L, LC-MS/MS; 1) removal efficiency of estrogenic activity could be 98.5% when O3 [10]
CO3 = 0.520 mg/L, GC-MS;YES adding concentration was 1.9 times of EE2 initial concentration;
pH = 8, T = 10 or 20C 2) five byproducts were identified in degraded solution.
E1, E2, Pure water O3 pH = 2.510.5; HPLC 1) the apparent second order rate constants increased with the [11]
E3, EE2, T = 20 2C increasing of pH, value reached minima at pH b 5, and maxima at pH N 10.
BPA, NP 2) the apparent second order rate constants were determined as
1.066.83 109M 1 s 1 for ionized EDCs, and 1.68 104 to 2.21 105
for neutral EDCs, the former was 104105 times higher than the latter.
E1, E2, Effluent O3 Pilo-scale experiment. LC-MS/MS 1) removal efficiency of EDCs was over 90% when O3 concentration was [12]
EE2 of WWTPs Q = 2m3/h; above 2 mg/L;
HRT = 8.4min; 2) SS in wastewater had no influence on removal efficiency of EDCs
LO3 = 200L/h, when SS was below 20 mg/L.
CI = 0.5 or 1 g/L
E2, BPA Aqueous O3 O3/UV CO3 = 7.5615.89 LC-MS 1) combination of O3 and UV could increase the degradation rate and [13]
solution mol/min; improve removing efficiency, the degradation rate of BPA with O3
CI = 0.1 mmol/L was lower than that of E2 with O3;
2) metabolites of E2 degradation solution were detected by LC-MS
and two possible degradation pathways were proposed.
e Effluent O3 EEQ = 10002000ng E2/L; YES 1) estrogenic activity was completely removed; [14]
of WWTPS CO3 = 0.010.02 mg/L 2) in the process of O3 oxidation, COD and TOC hardly decreased,
but color index decreased.
E2, E3, Effluent O3 TOCc0 TOC f0 = LC-MS, 1) E2, E3 and BPA in wastewater could be quickly decreased to below [15]
BPA, NP of primary 27.248.6 mg/L; ER-binding 10ng/L, but degradation of NP was relatively lower just from 800ng/L
settling tank CO3 = 0.4mg O3/TOC0 assay to 100ng/L, then remained constant with extended ozonation;
2) estrogenic activity of wastewater evaluated by ER-binding assay
could be degraded quickly to below 10ng/L.
EE2 Aqueous O3 CO3 = 0.711.6mol/L HPLC GC-MS 1) operational conditions such as EE2 initial concentration, [16]
solution O3 concentration, pH and conductivity on the removal of EE2 was studied;
2) about 53.9% of EE2 was mineralized when the wastewater reacted
with O3 for 20min and degradation pathways of EE2 were proposed.
PR Aqueous O3 CO3 = 20mol/L; HPLC; 1) apparent second order rate constant was determined, the mean value [17]
solution CI = 1mol/L; LC-MS/MS was 480 30M 1 s 1 for pH ranging between 2.0 and 8.0;
T = 18 1C 2) two degradation metabolites of progesterone were identified
and possible degradation pathways were suggested.

(continued on next page)

741
742
SC IE N CE OF T H E TOT AL E N V I RO N ME N T 4 0 7 ( 2 00 9 ) 7 3 17 48
Table 7 (continued)
EDCs Wastewater CAO Operational Analyses Main conclusions Reference
condition

BPA Aqueous Fenton/UV CI = 10 mg/L; GC-MS 1) influence factors of pH, Fe(II) concentration, H2O2 concentration and [18]
solution T = 25 1C UV strength were studied and in optimal condition, removal of BPA reached
above 90% at 9min by oxidation of Fenton/UV;above 90% of BPA could be
mineralized to CO2 by oxidation of Fenton/UV and degradation mechanism
of BPA was proposed.
2) above 90% of BPA could be mineralized to CO2 by oxidation of
Fenton/UV and degradation mechanism of BPA was proposed.
BPA Aqueous Ultrasound UV/Fe(II) CI = 118mol/L HPLC-MS 1) BPA could be completely removed after 90min treated by ultrasound, [19]
solution Ultrasound/UV/Fe(II) but at least 80% TOC and 50% COD remained in the treated solution;
2)combination of ultrasound with UV or Fe(II) could improve TOC and COD,
and combination of Ultrasound/Fe(II)/UV could attain the best removal result,
which was also the most efficient in energy consumption.
BPA, E2, Aqueous UV; UV/H2O2 pH 6.8 HPLC 1) removal efficiency could be improved by increasing the strength of UV, [20]
EE2 solution and by adding of 15 mg/LH2O2, removal efficiency of EDCs could be increased
from 20% to above 90%.
2) apparent second order rate constants were given and a degradation model
was also established.
BPA Aqueous UV; UV/H2O2 CI = 60mol/L HPLC;YES; 1) BPA could not be effectively removed by UV, but by adding H2O2, removal [21]
solution in vivo efficiency could be improved greatly;
2) degradation solution of BPA was evaluated by both in vitro assay and
in vivo assay, results suggested UV/H2O2 was useful for removing of BPA.
E2, EE2, Deionized UV/H2O2 CI = 20040,000ng/L YES; in vivo 1) degradation of estrogenic activity of solution suggested pseudo-first order [22]
BPA, NP water or river rate dynamics, degradation rate of mixed EDCs in water solution was much
water slower than sole target chemical in water solution; of hydroxyl radical with target
EDCs was calculated, data differed from 0.13%10.71% with different water solution;
2) reaction percentage of hydroxyl radicals with target EDCs was calculated,
data differed from 0.13%10.71% with different water solutions.
E2, EE2 Pure water or UV; UV/H2O2 CI = 10nmol/L HPLC, YES 1) EDCs oxidation rate and rate of estrogenic activity were given and compared [23]
surface water under several strength conditions of UV;
2) removal efficiency of estrogenic activity in water solution
was evidently better under UV/H2O2 condition than that of UV,
other components in solution decrease their degradation rate;
3) reaction model of degradation of estrogenic activity was established.
Equilin, Aqueous Ultrasound CI = 10 g/L GC-MS 1) removal efficiency was 8090% treated 4060min by ultrasound; [24]
E1, E2, solution 2) first-order degradation rate constants were given and energy
E3 etc. efficiency was also compared.
E1, E2, Aqueous Fe-TAML g; Fe-TAML/ CI = 80mol/L LC-MS/MS 1) degradation rate could be improved by H2O2,and removal [25]
E3, etc solution H2O2 efficiency of EDCs could be above 95% at 15min under Fe-TAML/H2O2 condition;

S CIE N CE OF T H E TOT AL E N V I RO N ME N T 4 0 7 ( 2 00 9 ) 7 3 17 48
TAML/ 2) first order degradation constants were given.
H 2O 2

[1] Hu et al. (2003); [2] Hu et al. (2002); [3] Deborde et al. (2004); [4] Lee et al. (2005); [5]Jiang et al. (2005); [6] Lau et al. (2007); [7] Huber et al. (2003); [8] Ternes et al. (2003); [9] Alum et al. (2004); [10] Huber et al.
(2004); [11] Deborde et al. (2005); [12] Huber et al. (2005); [13] Irmak et al. (2005); [14] Ermawati et al. (2007); [15] Zhang et al. (2008); [16] Zhang et al. (2006a,b); [17] Barron et al. (2006); [18] Katsumata et al.
(2004); [19] Torres et al. (2007); [20] Rosenfeldt and Linden (2004); [21] Chen et al. (2006); [22] Chen et al. (2007); [23] Rosenfeldt et al. (2007); [24] Suri et al. (2007); [25] Shappell et al. (2008).
a
C: oxidizer concentration.
b
CI: initial concentration of target EDCs.
c
Butylated hydroxyanisole.
d
Nuclear magnetic resonance.
e
Not measured by chemical analysis.
f
TOC initial concentration before CAO.
g
An iron-tetraamidomacrocyclic ligand.

743
744 SC IE N CE OF T H E TOT AL E N V I RO N ME N T 4 0 7 ( 2 00 9 ) 7 3 17 48

investigated the removal effects by Ferrate (VI) based on advanced oxidation was discussed here. All of these are the
municipal wastewater. Results showed that Ferrate (VI) could subject of numerous ongoing studies. Control of all micro-
reduce BPA, NP, E2 and E1, and COD of wastewater could also pollutants, not only EDCs, in wastewaters is urgent and neces-
be reduced. However, the operational conditions were not dis- sary. However, in this time of a growing energy crisis and
cussed nor were the degradation dynamics done on the com- concerns over the greenhouse effect, removal efficiency can-
plex wastewater. not be the only objective. Sustainable development on the
Chlorine is a good disinfectant, which is widely used in tap whole must to be considered.
water or effluent of biological wastewater treatment process.
Hu et al. (2002, 2003) studied the chlorination process regarding
the removal of BPA and E2. In the studies, many byproducts Acknowledgements
were measured and possible degradation pathways were also
proposed, but results evaluated on YES denoted the reaction by This work has been partly supported by the Institute of Osaka
chlorination was incomplete. Especially for BPA, the estrogenic International House Foundation, Osaka, Japan. The authors
activity of the water solution was hardly decreased after would like to thank the Institute of Osaka International House
chlorination. Compared to chlorination, O3, UV/H2O2 and other Foundation, Osaka, Japan, for the scholarship support to over-
combination methods yield more effective results. Rosenfeldt seas students. The authors would also like to thank CRAIG
and Linden (2004) showed that the removal efficiencies of BPA, Farnham, Graduate School of Engineering, Osaka City Univer-
E2 and EE2 in aqueous solution were all above 90% by UV/H2O2. sity, who helped to correct the English of the manuscript.
The high removal effectiveness of UV/H2O2 was further proven
by Chen et al. (2006, 2007), who studied the removal rates of
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