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17[alpha]-ethinylestradiol: an endocrine disrupter of great concern. analytical methods and removal processes applied to water purification. a review

17a-Ethinylestradiol: AnEndocrine Disrupter of GreatConcern. Analytical Methodsand Removal Processes Appliedto Water Purification. A ReviewLudiwine Clouzot,a Benoıˆt Marrot,a Pierre Doumenq,b Nicolas Rochea a LM2P2, UMR CNRS 6181, Laboratoire de Me´canique, Mode´lisation et Proce´de´s Propres, Universite´ PaulCe´zanne Aix-Marseille 3, Europoˆle de l’Arbois, Baˆt Lae¨nnec hall C BP 80, 13545 Aix-en-provenceCedex 4; [email protected] (for correspondence) b SCC-F-QE, UMR 6171, Laboratoire de Chimie Analytique de l’Environnement, Universite´ Paul Ce´zanneAix-Marseille 3, Europoˆle de l’Arbois, Baˆt Villemin, BP 80, 13545 Aix-en-provence Cedex 4 Published online 16 June 2008 in Wiley InterScience ( DOI 10.1002/ep.10291 The xenobiotic 17a-ethinylestradiol, an oral con- ing microorganisms that are responsible for EE2 bio- traceptive component, is an endocrine disrupter degradation. Among bioprocesses, i.e., AS, membrane (EDC) of great concern, with fish feminization bioreactors (MBRs), biofilm reactors, and sequencing induced for concentrations as low as ng L21. EE2 batch reactors, MBR technology appears as a hopeful occurrence in the aquatic environment can be linked solution for the improvement of EDCs removal, and, to insufficient removal in wastewater treatment more precisely, EE2. Alternative treatments such as plants. The focus of this review is to consider opti- mum treatment processes for removal of EE2. The MnO2, and sand reactor or ozonation were tested in main problem of EE2 is concentrations often below the laboratory and were shown to be inadequate.
authors’ limits of detection. Consequently, it is impor- Ó 2008 American Institute of Chemical Engineers Environ tant to fully understand the advantages and disad- vantages of different analytical techniques as this will Keywords: estrogen, EDC, EE2, wastewater, mem- determine confidence in comparison of the efficiency of different treatment processes. Solid-phase extrac-tion followed by chromatography is widely used butalternative methods, such as solid-phase microextrac- tion, stir bar sorptive extraction, or passive samplers, In the European workshop on the Impact of Endo- appear as promising tools. During the conventional crine Disrupters on Human Health and Wildlife, Wey- activated sludge (AS) process, the incomplete sludge bridge, UK, 1996, an endocrine disrupting chemical settlement results in lost of biomass, which means loss (EDC) was defined as ‘‘an exogenous substance that of EE2 adsorbed, and in low SRT, unsuited to nitrify- causes adverse health effects in an intact organism, orits progeny, secondary to changes in endocrine func- Ó 2008 American Institute of Chemical Engineers tion.’’ An EDC is likely to cause disruption in vivo if Environmental Progress (Vol.27, No.3) DOI 10.1002/ep it has at least one of the following characteristics: (i)it is present in environment at high concentrations,(ii) it is persistent and bioaccumulative, or (iii) it isconstantly released into environment [1]. Endocrinedisruptions were highlighted in wildlife, e.g., fishes,mammals, birds, reptiles, amphibians, and inverte-brates [2–4]. Estrogenic responses were first observedin caged trout exposed to sewage effluents [5]. Subse-quently, among many fish species, feminization proc-esses such as testes malformation or intersex fish,with oocytes in the testes, were detected downstreamof municipal sewage effluents: flounder [6–8], Medi-terranean swordfish [9, 10], Rainbow trout [11], roach[12, 13], or cyprinids [14, 15]. Therefore, endocrinedisruptions in the aquatic ecosystem can be linked to Figure 1. Endocrine disruptions in Medaka and Fat- EDCs release from waste water treatment plants head minnow by hormones and alkylphenols. LOEC, lowest tested concentration at which noted effect EDCs are composed of a wide range of molecules occurred; left, testis-ova in Medaka; right, vitellogenin such as chlorinated pesticides, phthalates, alkylphe- (VTG) synthesis in fathead minnow. Medaka, adapted nols, natural and synthetic hormones. EDCs impact from [21]; Fathead minnow: EE2 [22]; E1 and E2 [23]; on fish populations were previously reviewed by Mills and Chichester [16]. Laboratory experimentsdemonstrated EDCs in mainly estrogenic. In surface water, natural estrogenssuch as estrone (E1), 17a-estradiol (E2), estriol (E3), doses (1–1000 lg kg21) of EE2 in male Rainbow trout showed VTG synthesis until 720 times more than E2 (EE2), widely used in human oral contraceptives, [5]. Besides, concentrations as low as 0.1 ng L21 of were detected in the low ng L21 range. Despite trace EE2 were shown to cause significant rise in plasma concentrations, hormones contribute largely to the VTG. A food-web model of aquatic organisms in river surface water estrogenicity [17], with 35–50% due to systems also suggests bioaccumulation of EE2 by the xenobiotic EE2 [18]. Natural steroids have relative fishes [27]. Ecotoxicologic studies classified EE2 as at potency about one million times more than pesticides least R51/53 that means ‘‘toxic to aquatic organisms and 300,000 times more than p-nonylphenol (NP) and may cause long-term effects in the aquatic envi- [19]. Male Rainbow trouts (Oncorhynchus mykiss), undergoing sexual maturation, were exposed at 3 EE2 occurrence in the aquatic environment comes weeks to EE2, NP, and octylphenol (OP) [20]. While from WWTP effluents, due to insufficient removal fish exposed to 30 lg L21 of NP and OP showed sig- during water purification. With regard to endocrine nificant reduction in testicular growth, males exposed disruptions caused by EE2, the focus of this review is to 2 ng L21 of EE2 showed some disruption. Intersex to consider optimum treatment processes for removal gonads (testis-ova) were observed in male Medakas of the synthetic hormone from sewage effluent dis- (Oryzias latipes) exposed at 100 days post-hatch to charges. The major issue of EE2 is its occurrence at EE2, E1, E2, E3, and bisphenol A (BA) (see Figure 1).
trace concentrations, which raises problems about the The lowest tested concentration at which the noted analytical method. Endocrine disruptions observed effect occurred (LOEC) was observed for hormones with EE2 were mainly at concentrations below the EE2 and E2; E3 and BA induced intersex gonads for authors’ limit of detection (LOD). Consequently, it is concentration 100 times more than EE2 and E2. Syn- important to fully understand the advantages and dis- thesis of the female protein vitellogenin (VTG) by advantages of different analytical techniques as this male or juvenile fish is commonly used as an indica- will determine confidence in comparison of the effi- tor of exposure to estrogenic EDCs. Adult Fathead ciency of different treatment processes.
minnows (Pimephales promelas) were exposed at 3weeks to EE2, E1 and E2, NP (see Figure 1), and BA[25]. Alkylphenols induced VTG production in male Fathead minnow from the highest concentrations,with 160 lg L21 for BA. In contrast, only 1 ng L21 of From EE2 Synthesis to its Release into Environment EE2 was sufficient to synthesize VTG. Therefore, Synthetic estrogen EE2 is engineered from natural estrogens, particularly EE2, were shown to be the hormone E2 (see Figure 2). Steroid estrogens are most potent EDCs. With regard to the results cited defined by aromatic ring with hydroxyl group at the previously, EE2 induced endocrine disruptions from C-3 position. For the xenobiotic EE2, additional the lowest concentrations. Impact studies on Danio ethinyl group at C-17 results in a hormone that is rerio demonstrated sex ratio changes toward females much more resistant to biodegradation than natural from 50 ng L21 E1, 54 ng L21 E2, and 21.7 lg L21 E3, ones. Prior to human excretions in feces and urine, whereas 6 ng L21 EE2 were sufficient to obtain 100% EE2 is metabolized to biologically inactive form by of females [26]. Intramuscular injections of varying hydroxylation of an aromatic ring followed by conju- Environmental Progress (Vol.27, No.3) DOI 10.1002/ep Figure 2. 17a-ethinylestradiol engineered from the natural hormone 17b-estradiol.
gation with sulphate or glucuronide at C-3 and/or C- WWTPs discharge but can be dispersed in the whole 17. Johnson and Williams [29] developed a model in aquatic environment. EE2 removal during waste which EE2 fate in body and its excretion were esti- water treatment seems insufficient to avoid any endo- mated to predict subsequent inputs into WWTPs; crine perturbations in the aquatic ecosystem.
inputs were assumed to be the sum of EE2 excretedfrom different groups of human population. EE2 ingested was estimated at 26 lg d21: 43% was pre- Chemical properties of EE2 and natural hormones dicted to be metabolized within the body, 27% come in useful to understand the behavior of estro- excreted as conjugated molecules, and 30% as free gens in environment (Table 2). All estrogens are non- form. EE2 was detected in WWTP effluents in active volatile organic compounds, with vapor pressures form, suggesting a de-conjugation pathway between between 9 3 10213 and 3 3 1028 Pa. Octanol-water human excretions and WWTP outlets [30, 31]. Esche- partition coefficient (log Kow) is an indicator of richia coli, largely excreted in feces, is presumed re- hydrophobicity. With a log Kow of more than 3, EE2 sponsible for estrogens de-conjugation because of is considered liposoluble. Additionally, EE2 with the their important b-glucuronidase enzyme activity.
highest log kow demonstrated the highest factor of EE2 as a free molecule was measured in WWTP bioaccumulation [27]. It was also shown that sorption influents/effluents and in surface water (Table 1). In- to sediments was related to hydrophobicity; the great- dependently of analytical method used, lowest con- est sorption is observed for the most hydrophobic centrations were often below authors LODs (from compound, EE2 [43]. The synthetic hormone has the 0.02 ng L21 to 1.6 ng L21), which limits the discus- lowest water solubility and the highest log Kow, sug- sion about EE2 removal during water purification and gesting that sorption will be a significant factor in EE2 impact on the ecosystem at environmental con- reducing EE2 concentrations in the aqueous phase centrations. Some endocrine disruptions, such as [39, 44]. A further parameter, log Koc, defines organic intersex fish or VTG induction, occur below these carbon sorption. It is suggested that in the absence of LODs. Even though, it is possible to conclude that EE2 is released at concentrations that could induce closely depends on organic content in soil or sedi- feminization processes in fish during laboratory stud- ment. Sorption of EE2 on aquifer material was stud- ies. With regard to highest concentrations (from 0.76 ied and log Koc was shown to be 3.7, which demon- ng L21 to 42 ng L21), there is a decrease between strates significant sorption abilities [39]. Colloidal or- influents and effluents, from 37 to 87% [18, 35, 37, ganic carbon seems to be implicated in estrogens 38]. To make a link with removal rate, measures in transport [45]. Indeed, up to 60% of EE2 may be asso- influents and effluents have to be made exactly at the same time in same conditions. Besides, given the val- Consequently, due to its lowest biodegradability ues below LODs, only highest concentrations were (ethinyl group at C-17) and its highest potential sorp- taken into account, which limit good interpretation.
tion ability, the synthetic hormone is the most persis- The tested surface waters presented in Table 1 tent estrogen in the natural environment. Under aero- were in urbanized areas generally receiving WWTP bic conditions, EE2 has a half-life between 20 and 40 effluents. Owing to the dilution of effluents in the days, whereas it is 1 day for E2 [46, 47]. In contrast to river, concentrations in surface water are lower than natural steroids, EE2 sorption plays a more significant in effluents, but values still remain above those that role than biodegradation [48]. Even if adsorption could induce endocrine disruptions. EE2 dissipation processes result in estrogenicity decrease, due to downstream of WWTPs was studied up to 100 km lower EE2 concentrations in aqueous phase, sedi- away from plants [40–42]. For instance, in the Lower ments are an EE2 trap [49]. Hormones adsorbed on Jordan River, concentrations above 1.5 ng L21 were sediments are not bioavailable, but they can be measured up to 100 km downstream of WWTPs [40].
released into the aquatic environment and, thus, Therefore, EE2 contamination is not limited to become bioavailable. EE2 persistence in anoxic sedi- Environmental Progress (Vol.27, No.3) DOI 10.1002/ep Table 1. EE2 concentrations in WWTPs influents/effluents and in surface water.
Effluent: 2.7–4.5 (3.8)Surface water: 1.1–2.9 (1.5) Effluent: <1.1†Surface water: <0.4†–1 *[Solid-phase extraction (SPE): C18, SDB-XC, Ethinylbenzene-DVB, OASIS] Analysis (gas or liquid chromatogra- phy (GC or LC)/mass spectrometry or tandem spectrometry (MS or MS-MS)).
ments is emphasized by nonbiodegradability under analyzed. Owing to the high sorption ability of EE2, anerobic conditions [39, 47, 50]. On sunny spring in WWTPs, a fraction is adsorbed on sludge. To com- days, EE2 degradation can be amplified by photoly- pare waste water treatments for EE2 removal, the sis, reducing its half-life from about 20 to 1.5 days degraded fraction has to be discriminated from the [51, 52]. Therefore, EE2 persistence in the aquatic adsorbed one. Thus, for grab sampling, EE2 should environment can be likened to a possible perpetua- be extracted from suspended solids [53, 54]. During tion of endocrine disruption in wildlife.
EE2 extraction, polar solvents are generally used;coextraction of many interferents is then induced, resulting in heterogeneous extract [55]. Given the complex matrix and trace concentrations, EE2 extrac- aquatic environment at concentrations below the tion from sludge is a critical step in terms of selectiv- authors’ LODs, it seems essential to choose an appro- ity and loss of target analytes. Soxhlet extraction in priated analytical method. Indeed, analysis of trace methanol can be used, but it is time consuming and elements in complex matrix with particles, colloids, high quantities of solvent are required [56]. The and organic matter raises problems about analytical extraction of estrogens using ultrasonics with metha- specificity and sensitivity. Therefore, a discussion nol-acetone (50:50, v/v) showed recoveries above about optimum treatment for EE2 removal during 70% [57]. With microwave-assisted extraction (30 W, waste water purification requires first a review about 5 min, methanol), EE2 recovery was 72% 6 6% [41], the advantages and disadvantages of different analyti- whereas simple extraction with ethyl acetate allowed EE2 recoveries of 95% 6 3.7% and 96% 6 0.6% [39,47]. In a newer technique, the accelerated solvent extraction (ASE), the centrifugation step after extrac- Traditional sampling methods for the analysis of tion is avoided. ASE performed at 1008C and 2000 psi trace pollutants consist of collecting large volumes with acetone-methanol (50:50, v/v) showed a recov- (about 1L for single analysis). The samples are stored at 48C in dark to minimize any modification. In the The main problem of traditional monitoring pro- lab, the samples are then concentrated with chemical grams is that they the measured contaminants present extraction, purified to remove any interferences, and only at the time of sampling. Alternative methods are Environmental Progress (Vol.27, No.3) DOI 10.1002/ep Table 2. Chemical properties of natural and synthetic oestrogens (adapted from [27]).
passive samplers; they allow average concentrations cleaning steps are laborious and numerous [32]. The to be measured that take account of the temporal var- OASIS copolymer with hydrophilic-lipophilic balance iation in chemical concentration in natural waters and (HLB) enables greater clean-up selectivity and sensi- effluents [59]. The purpose of passive sampling tech- tivity than C18; EE2 recoveries are amongst the high- niques is to sample as well as concentrate; which is est [37, 41]. Difference in recovery between the two well adapted to trace pollutants such as EE2. Another Oasis HLB presented in Table 3 can be explained by advantage is to biomimic the exposure of aquatic the influence of operational conditions: effluents organisms to contaminants. A novel passive sampler, were not exactly the same and elution/cleaning steps are different. To conclude, the breadth of C18 use can (POCIS), consists of a sequestration medium enclosed be explained by broad selectivity, which gives the within a hydrophilic microporous polyethersulfone opportunity to compare a wide range of contami- membrane [60]. The POCIS were applied successfully nants with a single extraction technique. Another to environmental estrogens and compared with grab possible reason is polymeric SPE, such as Oasis-HLB, sampling and bioaccumulation tests [61]. The POCIS which is newer than C18 and the cartridge cost is provided results similar to those obtained with repeated grab samples and appeared to accumulate Alternative extraction methods have recently been estrogens very similar to brown trout. Therefore, the developed: solid-phase microextraction (SPME) and POCIS is a meaningful method to analyze EE2 in stir bar sorptive extraction (SBSE) (Table 3). These WWTP effluents undergoing variable inputs and eco- techniques are defined by an equilibrium based on systems with dynamic hydrological conditions.
partitioning of the solutes between a silicone phase Given the trace concentrations of EE2, the syn- and the aqueous matrix. Compared with SPE, less thetic hormone has to be concentrated prior to analy- sample volumes are required (1–50 mL versus 1L for sis. Grab water samples or extracts from sludge SPE), higher selectivity is achieved, and automation is undergo the same type of analytical method, which is possible. SPME and SBSE are solvent-free technolo- chemical extraction followed by analysis. Concerning gies that are easier, quicker, and economical. Fully passive sampling techniques, EE2 is directly analyzed.
automated SPME with the capillary column as anextraction device showed low recoveries: 38.6% for10 ng L21 of EE2 [68]. However, extraction with a stir bar resulted in higher recoveries: 89% of recovery for Liquid-liquid extraction is not applied to EE2 EE2 with LOD in the same range of those obtained because of high volumes of organic solvents and la- with SPE methods (Table 3). Generally, coated with borious clean-up steps [62]. Solid-phase extraction polydimethylsiloxane (PDMS), SPME was demon- (SPE) with organic solid phase is generally preferred.
strated better for EE2 with polyacrylate [64, 69]. The SPE was applied to EE2 in WWTPs effluents (Table phase amount can also influence recovery; SBSE, 3); a high recovery (75–96%) and good accuracy (rel- coated with higher amount of phase than SPME (24– ative standard deviation (RSD) 0–8%) were obtained.
126 lL for SBSE versus < 0.5 lL for SPME), showed Retention ability and selectivity of SPE can be linked the highest recoveries (>95%) [65, 70]. Therefore, to the nature of the extractive phase. The octadecyl SPME and SBSE appear as useful tools for EE2 analy- siloxane (C18) is the most commonly used for reversed-phase SPE due to its broad selectivity; C18has also been used widely for estrogens analysis [18,48, 66, 67]. However, when compared with the other SPEs, C18 cartridges have the lowest recoveries (Table Functional analysis, based on estrogenic activity, 3). Indeed, given to a less selective nature, interfer- can be used to measure EE2 in the aquatic environ- ents for analysis are extracted. Besides, because of an ment. In vitro biotests have been developed for increase number of conditioning and cleaning steps, screening estrogenicity in WWTP effluents and conta- SPE with C18 is time consuming. The carbograph 4 minated surface water: the yeast estrogen screening (C4) cartridge is easier in the cleaning step and assay (YES) [17, 71] and the proliferation test with showed higher recovery for EE2 but stronger solvents human MCF-7 breast cancer cells [18, 72]. For the (less polar) are necessitated [35, 38]. The polystyrene YES, the human estrogen receptor is expressed in a divinylbenzene extraction disc SDB-XC was character- recombinant yeast strain. Upon binding, an active ized by higher recovery for EE2 than C18 and C4 but ligand, namely, an estrogenic compound, the reporter Environmental Progress (Vol.27, No.3) DOI 10.1002/ep gene Lac-Z is expressed and b-galactosidase, the secreted enzyme, metabolizes the yellow chlorophe- product, measured by absorbance at 540 nm. Con- cerning the proliferation test, MCF-7 cells transfected with an estrogen-regulated luciferase gene (MELN cells) are used; luciferase induction reveals estrogen activity. These biotests are useful for detecting estro-genic compounds but chemical analysis is preferred to quantify a specific EDC, such as EE2. Chemical analysis makes researchers more confident in the comparison of waste water treatments efficiency.
Radioimmunassay (RIA) was the first method tested for hormones analysis [33]. The principle is to measure radioactivity associated with antigen-anti- body immune reaction. Owing to the radioactivity use, enzyme-linked immunosorbent assay (ELISA), based on enzymatic reaction instead of radioactivity,was then proposed [70]. However, with the environ- mental matrix, cross-reactions result in overestimation of estrogens concentrations [73, 74]. Given the increased concern of the scientific community about EDCs removal in WWTPs, chromatographic methods have next been developed and used more and more.
High-performance liquid chromatography (HPLC), applied to river samples, showed lower LODs with electrochemical detector (0.07 lg L21) than with UV detector (0.4 lg L21) [75]. Fluorometric detectors allowed higher sensitivity, with LODs in the environ- mental range (1.6–4 ng L21) [33, 76]. HPLC is advan- tageous, in comparison with gas chromatography–mass spectrometry, (GC/MS) with an inexpensive de-tector and lower maintenance costs. However, in environmental samples, the analysis is subject to po- lar interferences. Consequently, for EE2 analysis in WWTP effluents, HPLC is not commonly used. Dur- ing studies on EE2 removal in WWTPs, liquid chro- matography–mass spectrometry (LC/MS) and GC/MS are preferred because of low LODs (0.3–4.1 ng L21) (Table 3). It can be noted that the lowest LODs were obtained with tandem spectrometry (MS-MS). Selec-tivity with MS-MS is more adapted to environmental matrices such as WWTP effluents; GC revealed a sen- sitivity 10 times higher with MS-MS than MS [32]. LC- MS analysis was shown to be highly influenced by matrix effects [77]. Coelution of matrix components is a critical aspect of LC-MS because it results in ion suppression or enhancement of target analyte. Given their less sensitivity to matrix effects than LC, GC/MS or GC/MS-MS are used more often to analyze EE2 in WWTPs effluents [17, 18, 66, 67, 78]. To optimize GC/ MS, a derivatization step is generally performed prior to analysis; optimal sensitivity and resolution are obtained because of derivatives with higher polarity, enhanced volatility, and increased thermal and cata- lytic stability [62, 79–81]. Two main problems with EE2 derivatization were highlighted: (1) difficult syli- lation of the hydroxyl group at the C17 position [62] (2) EE2 conversion into estrone (E1), resulting in overestimation of E1 and underestimation of EE2 [79].
EE2 derivatization was shown to be complete withtemperature under 758C, pyridine as solvent, N,O-bis- (trimethylsilyl)-trifluoroacetamide (BSTFA) as reagent Environmental Progress (Vol.27, No.3) DOI 10.1002/ep Table 4. EE2 removal efficiencies of various water purifications at different initial concentrations.
*Estradiol equivalents (estrogenicity).
and trimethylschlorosilane (TMCS) as catalyst [81].
5%) [85]. EE2 removal during the AS process is largely However, recent work showed that pyridine led to variable, ranging from 34% to 98% (Table 4). The AS secondary products that disrupt chromatographic pat- process can be characterized by the sludge retention terns, whereas dimethyl formamide avoided EE2 con- time (SRT). The higher the SRT, the more efficient is version without any disruption [80].
the pollutant biodegradation. For instance, when SRT Chromatographic methods are powerful analytical is above 20 days, the biodiversity is higher with techniques, but for EE2 analysis in WWTPs effluents broader physiological abilities than sludge with SRT or rivers, sensitivity and selectivity need to be below 20 days. Conventional AS processes are widely enhanced. LODs should be lessened because endo- used despite some problems such as the low settling crine disruptions in the aquatic ecosystem occur at ability of the sludge that results in low SRTs, often concentrations below the authors’ LODs obtained at below 20 days. The whole sludge does not settle in the moment. Nowadays, researchers need to focus on the clarifier, resulting in biomass in the effluent and optimizing the analysis conditions; for instance, reduction of the matrix effects for LC/MS or optimiza- The second bioprocesses frequently used for water tion of derivatization conditions for GC/MS analysis.
purification are biofilm reactors, such as trickling andupflow biological filters or fluidized beds. In compar- ison with suspended cultures, the fixed beds arecharacterized by higher biomass concentration. How- ever, fixed beds raise problems about fouling and It has been seen previously that EE2 is released dead space [71]. With regard to EE2, the AS system from WWTPs at concentrations inducing endocrine has a higher removal rate (Table 4). Another biofilm disruptions in aquatic environment (> 0.1 ng L21) reactor, the rotating biodisc, can also be used during (Table 1). Consequently, EE2 removal during waste- wastewater treatment [86, 87]. Control of the biofilm water treatment seems to be insufficient. Auriol et al.
thickness is easier and aeration is more effective [82] reviewed EDCs removal at each step of water pu- because of direct contact of the biofilm and air dur- rification. First, EE2 undergoes physical removal by ing rotation. However, one of the main drawbacks is adsorption on particles [83]. For instance, in activated the limited surface area of discs for biofilm formation sludge process, between 60% and 80% of EE2 were due to 40% immersion in wastewater [87]. Alternative shown to be adsorbed on sludge and thus eliminated bioprocesses have been studied for wastewater treat- from the aqueous phase [48, 84, 85]. Chemical treat- ment. Granular sludge, characterized by good settling ment such as precipitation with aluminium sulphate, ability, can be developed in sequencing batch reac- ferric chloride, and lime were shown to be inefficient tors (SBRs) [88, 89]. Periodic processes exert a strong pressure on microbial populations, thus establishing Biological treatments are more suited to removal selection in favor of more adaptable biomass [89].
of organic matter such as EDCs. The activated sludge The improvement of settlement, in comparison with (AS) process is the most widespread process for sew- AS systems, can be explained by selection of floc- age treatment. For natural estrogens, removal rate by forming microorganisms over filamentous ones. In the AS process is generally more than 75%, whereas application to EDCs removal or more precisely to EE2 elimination is more often lower than 80% [18, 35, EE2, SBRs have not yet been shown to be better than 67]. Mineralization studies with 14C-labeled estrogens demonstrated that the percent mineralization of 14C- Alternative treatments for EE2 elimination have EE2 (20.2% 6 11%) was considerably less than the been investigated during laboratory experiments.
mineralization of the natural one, 14C-E2 (75.2% 6 First, photodegradation induced by a high-pressure Environmental Progress (Vol.27, No.3) DOI 10.1002/ep mercury lamp (k  313, 250 W) and catalysed by Biodegradation processes can undergo two path- Fe31 or algae Anabaena cylindrical eliminated 40% ways, either xenobiotic utilization for growth or com- of EE2 at initial concentrations between 2.5 and 15 etabolism, in which a compound is modified but not mg L21 [90]. Unfortunately, this process has not been used for growth. EE2 biodegradation is suggested by tested with environmental EE2 concentrations, and some authors to be a cometabolism [94, 95]. Monoox- the AS process remains the most effective in term of ygenase enzymes are known to cometabolize many removal rate (Table 4). Adsorption on granulated acti- organic compounds. The nitrifying bacterium Neutro- vated carbon (GAC), often used because of high somonas europaea produces ammonium monooxy- sorption capacities, revealed complete elimination for genase (AMO), catalyzing the ammonium oxidation EE2 concentrations in the lg L21 range [91]. For EE2 to nitrite. Biodegradation studies with N. europaea concentration about 13.8 lg L21, the adsorption demonstrated that AMO inhibition resulted in EE2 capacity was shown to be 163.5 lg g21, whereas for persistence [94]. Thus, EE2 biodegradation by comet- concentrations below 10 ng L21, sorption ability was abolism with AMO was validated. However, N. euro- only 1 lg g21. Consequently, at environmental con- paea degraded EE2 with accumulation of unknown centrations, GAC will have a very short bed lifetime, polar products characterized by a phenolic group leading to a costly process. With manganese oxide [94]. Contrary to AS, N. europaea conducted to (MnO2) reactor, EE2 removal was significant at 5 and incomplete degradation of EE2. Therefore, in AS bio- 20 lg L21 (Table 4) but at 0.1 lg L21, reduction abil- reactor, complex consortia of microorganisms, includ- ity was 100 times lower than at 10 lg L21 [91]. There- ing or not AMO, are probably involved in the degra- fore, MnO2 reactor needs improvement for applica- tion to environmental concentrations of EE2. Sand re- Bacterial strains with EE2 degradation abilities actor allowed only 17.3% of EE2 removed for were previously isolated [93, 94, 96]. A first strain Fu- concentrations in the lg L21 range (Table 4). By con- sarium proliferatum, isolated from a cowshed sam- trast, ozonation allowed more complete elimination ple, removed 97% of EE2 at an initial concentration than did the AS process. The sum of the estrogenic of 25 mg L21 [97]. However, unknown products of activity of intermediates was shown to be 200 times EE2 degradation, more polar with a phenolic group, lower than the estrogenicity of the original EE2 [92].
were accumulated. Additionally, three other strains, Therefore, this process could be considered for EE2 removing between 80% and 96% of EE2 at an initial removal, but its high cost explains that it is only used concentration of 100 mg L21, were isolated from AS for drinking water. Economically, wastewater treat- [96]. Byproducts were not identified, but they were ments used to protect the aquatic ecosystem need to shown to have no estrogenic activity. A last strain be cheaper than treatments used to produce drinking Sphingobacterium sp. JCR5, isolated from the WWTPs water. This observation explains partially why the AS AS of an oral contraceptives factory, metabolized up process is generally used for water purification.
to 87% of 30 mg L21 EE2 [93]. The identified catabolicpathway ended with carbon dioxide formation. Com-pared to isolated bacterial strains, AS system is com- EE2 Removal During the Activated Sludge Process posed of diverse biomass with complementary abil- During the AS process, nitrifying biomass was shown to be responsible for EE2 degradation [36, 48, During the AS process, EE2 is biodegraded by 93–96]. Nitrification reaction is divided into two steps, nitrifying biomass but the xenobiotic is also adsorbed the ammonia conversion to nitrite and the subse- on sludge. For initial ammonia concentrations below quent oxidation to nitrate. Nitrifying biomass is not 50 mg L21, sorption was shown to be predominant diverse, with mainly two genus represented, Nitroso- (up to 60%) because of low cometabolic activity but monas and Nitrobacter. Nitrifying microorganisms are for higher concentrations, biodegradation became autotrophs, using inorganic carbon as source for more important (up to 50%) [98]. Therefore, EE2 re- growth. Besides, they are characterized by slow moval during the AS process depends not only on its growth. Therefore, nitrifying AS in WWTPs require biodegradation activity but also on the sorption abil- Only few studies were done on EE2 removal by nitrifying AS. During preliminary experiments, nitrify- Membrane Bioreactors (MBRs) as Alternative Treatment ing biomass of 1 g L21 did not succeed in eliminating It has been explained previously that the main 1 lg L21 and 1 ng L21 of EE2 [36]. Thus, higher EE2 drawback of AS process is the low SRT, due to concentrations were tested. Nitrifying AS, at concen- incomplete retention of the biomass in the clarifier.
trations of 1 g L21, with a nitrifying capacity of 50 mg An alternative solution to enhance the removal of NH41 g DW21 h21, were able to remove 50 lg L21 pollutants is the use of membrane processes that of EE2 in 6 days [95]. These results were confirmed allow complete retention, which means higher bio- by some other experiments with 2.7 g L21 of biomass mass concentrations in the bioreactor and higher SRT.
and 1 mg L21 of EE2 [94]. De Mes et al. [83] reviewed This process is named the membrane bioreactor first-order degradation constants for AS at concentra- (MBR), combination of a bioreactor with membrane tions of EE2 from 100 ng L21 to 25 mg L21. There- filtration [99]. Research on MBR technology began fore, EE2 removal by nitrifying biomass is proved, more than 30 years ago. Since the last 10 years, a but it has to be confirmed with environmental con- near linear increase in research outputs has been centrations, in the low ng L21 range.
observed around the world [100]. Replacing the sec- Environmental Progress (Vol.27, No.3) DOI 10.1002/ep ondary clarifier in WWTPs by membranes, SRT and terms of concentration reduction and endocrine dis- biomass concentrations will be increased and the plant size will be lessened [101, 102]. The MBR Analysis of trace elements in a complex matrix advantage is easier control of high SRT, which is raises problems about specificity and sensitivity. SPE required for nitrifying biomass growth and thus for followed by chromatography appears as a widespread EE2 removal. Wastewater treatment with MBRs was analytical method for estrogens. However, in many investigated, and this process proved a reduction in studies, EE2 can not be quantified because of high about 99% for hormones [103]. Estrogens removal LODs. Recently, SPME and SBSE have been shown as rate with MBRs ranged from 81.9% to 100%, whereas a good alternative of SPE, due to higher recovery and for AS the values were between 59.4% and 100% accuracy. During monitoring programs, passive sam- [104]. Few studies have been conducted on EE2 re- plers appear as promising tools to quantify EE2 moval during wastewater treatment with MBRs. The because of LODs being lower than SPE and average biological degradation model showed higher EE2 re- measures which take account of temporal variations.
moval activity for nitrifying sludge from MBR (SRT 30 One of the research priorities should be the develop- days) than from AS (SRT 11 days) [105]. The higher ment of these analytical methods. Diminution of endo- removal activity in MBRs can first be explained by crine disruptions by improvement of EE2 removal in smaller flocs size, resulting in greater exposed surface wastewater requires reliable comparison of processes area. For the moment, it is unknown where estrogen and, thus, reliable analytical methods.
degradation took place: (i) throughout the floc (ii) on The synthetic hormone is much more resistant to the floc surface or (iii) in the bulk medium. Sludge biodegradation than natural ones, but its high hydro- from MBR had higher hydrophobicity values (68%) phobic nature makes sorption a significant removal than those from SBR (22–35%), which means EE2 factor in WWTPs. During conventional AS, the incom- sorption will be higher in MBR [98]. Polysaccharides, plete sludge settlement results in loss of biomass, strongly correlated with EE2 sorption, were shown to which means that loss of EE2 adsorbed, and in low be preferentially accumulated in MBR (30% 6 8% of SRT, unsuited to nitrifying micro-organisms which are the total organic carbon), compared with the AS responsible for EE2 biodegradation. Among biopro- process (19% 6 3%) [45]. The problem is polysaccha- cesses, such as AS, MBR, biofilm reactors and SBR, rides were also shown to be responsible for mem- MBR technology allows the highest SRT and, thus, brane fouling [106]. Membrane fouling can explain the growth of nitrifying biomass, which results in the slow commercialization of MBR technology [100, sludge with the highest sorption ability. Owing to 107–109]. Other membrane application is the use of more stringent effluent regulations, research and appropriate cutoff to retain xenobiotics directly with commercial application of MBRs are advancing rap- high molecular weight, e.g., estrogens [110, 111].
idly around the world for municipal wastewater treat- Therefore, membrane processes appear as hopeful ment. The scientific community agrees that MBR tech- solutions to enhance EE2 removal in WWTPs. First, nology is the alternative process for WWTPs. This membranes can be considered as improvement of the technology appears as a hopeful solution for the AS system because of more diversified biomass, due improvement of EDCs removal during wastewater to higher SRT. With regard to EE2, the nitrifying bio- treatment and should be studied for this.
mass will be able to grow and thus enhance biode- Alternative wastewater treatments, such as photo- gradation of the synthetic estrogen. The other advant- degradation, GAC, MnO2, and sand reactor or ozona- age is the retention of pollutants, directly or adsorbed tion, were tested in laboratory to improve EE2 re- on particles. As during ultrafiltration were shown to moval but at the present time they seem to be too develop a dynamic membrane that the improved costly or not suitable for environmental concentrations.
retention of natural hormones [112]. Natural hor- Therefore, future studies are necessary to develop mones can also be retained by adsorption on the these alternative solutions and to reduce their cost.
membrane polymer [113, 114]. Compared with naturalhormones, EE2 has higher molecular weight andsorption ability, which means that the synthetic hor- mone could be removed more easily by membranes.
1. Tyler, C.R., Jobling, S., & Sumpter J.P. (1998). En- docrine disruption in wildlife: A critical review ofthe evidence, Critical Reviews in Toxicology, 28,319–361.
2. Harrison, P.T.C., Holmes P., & Humfrey C.D.N.
Given to high relative potency and fish feminiza- (1997). Reproductive health in humans and wild- tion induced at concentrations as low as a few ng life: Are adverse trends associated with environ- L21, the xenobiotic EE2 appears as an EDC of great mental chemical exposure? Science of the Total concern. EE2 concentration in WWTPs influent/efflu- ent and in surface water were often below the 3. Iguchi, T., Watanabe, H., & Katsu, Y. (2001). De- authors’ LODs, which makes the discussion about velopmental effects of estrogenic agents on mice, EE2 impact on aquatic environment and EE2 removal fish, and frogs: A mini-review, Hormones and during wastewater treatment difficult. Therefore, an analytical technique appears to be very important to 4. Taylor, M.R., & Harrison P.T.C. (1999). Ecological determine the optimum treatment for EE2 removal, in effects of endocrine disruption: Current evidence Environmental Progress (Vol.27, No.3) DOI 10.1002/ep and research priorities, Chemosphere, 39, 1237– 16. Mills, L.J., & Chichester, C. (2005). Review of evi- dence: Are endocrine-disrupting chemicals in the 5. Purdom, C.E., Hardiman, P.A., Bye, V.J., Eno, aquatic environment impacting fish populations? C.R., Tyler, C.R., & Sumpter, J. (1994). Estrogenic Science of the Total Environment, 343, 1–34.
effects of effluents from sewage treatment works, 17. Desbrow, C., Routeldge, E., Brighty, G., Sumpter, J., & Waldock, M. (1998). Identification of estro- 6. Allen, Y., Matthiessen, P., Scott, A.P., Haworth, S., genic chemicals in STW effluent. 1. Chemical Feist, S., & Thain, J.E. (1999). The extent of oes- fractionation and in vitro biological screening, trogenic contamination in the UK estuarine and marine environments—Further surveys of floun- der, The Science of the Total Environment, 233, 18. Cargouet, M., Perdiz, D., Mouatassim-Souali, A., Tamisier-Karolak, S., & Levi, Y. (2004). Assess- 7. Hashimoto, S., Bessho, H., Hara, A., Nakamura, ment of river contamination by estrogenic com- M., Iguchi, T., & Fujita, K. (2000). Elevated serum pounds in Paris area (France), Science of the vitellogenin levels and gonadal abnormalities in wild male flounder (Pleuronectes yokohamae) 19. Daston, G.P., Gooch, J.W., Breslin, W.J., Shuey, from Tokyo Bay, Japan, Marine Environmental D.L., Nikiforov, A.I., Fico, T.A., & Gorsuch, J.W.
(1997). Environmental estrogens and reproduc- 8. Lye, C.M., Frid, C.L.J., Gill, M.E., & McCormick, tive health: A discussion of the human and envi- D. (1997). Abnormalities in the reproductive ronmental data, Reproductive Toxicology, 11, health of flounder Platichthys flesus exposed to effluent from a sewage treatment works, Marine 20. Jobling, S., Sheahan, D., Osborne, J., Matthies- sen, P., & Sumpter, J.P. (1996). Inhibition of tes- 9. Cristina Fossi, M., Casini, S., Ancora, S., Mosca- ticular growth in rainbow trout (Oncorhynchus telli, A., Ausili, A., & Notarbartolo-di-Sciara, G.
mykiss) exposed to estrogenic alkylphenolic chemicals, Environmental Toxicology and Chem- threaten Mediterranean swordfish? Preliminary results of vitellogenin and Zona radiata proteins in 21. Metcalfe, C.D., Metcalfe, T.L., Kiparissis, Y., Koe- Xiphias gladius, Marine Environmental Research, nig, B.G., Khan, C., Hughes, R.J., Croley, T.R., Timothy, R., March, R.E., & Potter, T. (2001). Es- 10. De Metrio, G., Corriero, A., Desantis, S., Zubani, trogenic potency of chemicals detected in sew- D., Cirillo, F., Deflorio, M., Bridges, C.R., Eicker, age treatment plant effluents as determined by J., de la Serna, J.M., Megalofonou, P., & Kime, in vivo assays with Japanese medaka (Oryzias D.E. (2003). Evidence of a high percentage of latipes), Environmental Toxicology and Chemis- intersex in the Mediterranean swordfish (Xiphias gladius L.), Marine Pollution Bulletin, 46, 358–361.
22. Pawlowski, S., van Aerle, R., Tyler, C.R., & 11. Harries, J.E., Sheahan, D.A., Jobling, S., Matthies- Braunbeck, T. (2004). Effects of 17a-ethinylestra- sen, P., Neall, P., Sumpter, J., Taylor, T., & diol in a fathead minnow (Pimephales promelas) Zaman, N. (1997). Estrogenic activity in five gonadal recrudescence assay, Ecotoxicology and United Kingdom rivers detected by measurement Environmental Safety, 57, 330–345.
of vitellogenesis in caged male trout, Environ- 23. Panter, G.H., Thompson, R.S., & Sumpter, J.P.
mental Toxicology and Chemistry 16, 534–542.
(1998). Adverse reproductive effects in male fat- 12. Jobling, S., Nolan, M., Tyler, C.R., Brighty, G., & head minnows (Pimephales promelas) exposed Sumpter, J. (1998). Widespread sexual disruption to environmentally relevant concentrations of the in wild fish. Environmental Science and Technol- 13. Rodgers Gray, T.P., Jobling, S., Morris, S., Kelly, 24. Harries, J.E., Runnalls, T., Hill, E., Harris, C.A., C., Kirby, S., Janbakhsh, A., Harries, J.E., Wal- Maddix, S., Sumpter, J.P., & Tyler, C.R. (2000).
dock, M.J., Sumpter, J.P., & Tyler, C.R. (2000).
Development of a reproductive performance test Long-term temporal changes in the estrogenic for endocrine disrupting chemicals using pair- composition of treated sewage effluent and its breeding fathead minnows (Pimephales prome- biological effects on fish, Environmental Science las), Environmental Science and Technology, 34, 14. Sole´, M., Alda, M.J.L., Castillo, M., Porte, C., 25. Sohoni, P., Tyler, C.R., Hurd, K., Caunter, J., Ladegaard Pederson, K., & Barcelo, D. (2000).
Hetheridge, M., Williams, T., Woods, C., Evans, Estrogenicity determination in sewage treatment M., Toy, R., Gargas, M., & Sumpter, J.P. (2001).
plants and surface waters from the catalonian Reproductive effects of long-term exposure to area (NE Spain), Environmental Science and bisphenol a in the fathead minnow (Pimephales promelas), Environmental Science and Technol- 15. Vigano, L., Arillo, A., Bottero, S., Massari, A., & Mandich, A. (2001). First observation of intersex 26. Holbech, H., Kinnberg, K., Petersen, G.I., Jack- cyprinids in the Po River (Italy), The Science of son, P., Hylland, K., Norrgren, L., & Bjerregaard, the Total Environment, 269, 189–194.
P. (2006). Detection of endocrine disrupters: Environmental Progress (Vol.27, No.3) DOI 10.1002/ep Evaluation of a fish sexual development test docrine disrupting chemicals in sewage treatment (FSDT), Comparative Biochemistry and Physiol- plants and natural waters, Analytica Chimica ogy Part C: Toxicology & Pharmacology, 144, 38. Baronti, C., Curini, R., D’ Ascenzo, G., Di Corcia, 27. Lai, K.M., Scrimshaw, M.D., & Lester, J.N. (2002).
A., Gentili, A., & Samperi, R. (2000). Monitoring Prediction of the bioaccumulation factors and natural and synthetic estrogens at activated body burden of natural and synthetic estrogens in sludge sewage treatment plants and in a receiv- aquatic organisms in the river systems, The Sci- ing river water, Environmental Science and Tech- ence of the Total Environment, 289, 159–168.
28. Carlsson, C., Johansson, A.-K., Alvan, G., Berg- 39. Ying, G.-G., Kookana, R.S., & Dillon, P. (2003).
man, K., & Kuhler, T. (2006). Are pharmaceuti- Sorption and degradation of selected five endo- cals potent environmental pollutants? Part I: crine disrupting chemicals in aquifer material, Environmental risk assessments of selected active pharmaceutical ingredients, Science of the Total 40. Barel-Cohen, K., Shore, L.S., Shemesh, M., Wen- zel, A., Mueller, J., & Kronfeld-Schor, N. (2006).
29. Johnson, A.C., & Williams, E.L. (2004). A model Monitoring of natural and synthetic hormones in to estimate influent and effluent concentrations a polluted river, Journal of Environmental Man- of estradiol, estrone, and ethinylestradiol at sew- age treatment works, Environmental Science and 41. Labadie, P., & Budzinski, H. (2005). Determina- tion of steroidal hormone profiles along the Jalle 30. D’Ascenzo, G., Di Corcia, A., Gentili, A., Mancini, d’Eysines river (near Bordeaux, France), Environ- R., Mastropasqua, R., Nazzari, M., & Samperi, R.
mental Science and Technology, 39, 5113–5120.
(2003). Fate of natural estrogen conjugates in 42. Williams, R.J., Johnson, A.C., Smith, J.J.L., & municipal sewage transport and treatment facili- Kanda, R. (2003). Steroid estrogens profiles along ties, Science of the Total Environment, 302, 199– river stretches arising from sewage treatment works discharges, Environmental Science and 31. Panter, G.H., Thompson, R.S., Beresford, N., & Sumpter, J.P. (1999). Transformation of a non- 43. Lai, K.M., Johnson, K.L., Scrimshaw, M.D., & Les- oestrogenic steroid metabolite to an oestrogeni- ter, J.N. (2000). Binding of waterborne steroid cally active substance by minimal bacterial activ- estrogens to solid phases in river and estuarine systems, Environmental Science and Technology, 32. Belfroid, A.C., Van der Horst, A., Vethaak, A.D., Schafer, A.J., Rijs, G.B.J., Wegener, J., & Cofino, 44. Shareef, A., Angove, M.J., Wells, J.D., & Johnson, W.P. (1999). Analysis and occurrence of estro- B.B. (2006). Sorption of bisphenol A, 17a-ethyny- genic hormones and their glucuronides in sur- lestradiol and estrone to mineral surfaces, Journal face water and waste water in The Netherlands, of Colloid and Interface Science, 297, 62–69.
Science of the Total Environment, 225, 101–108.
45. Holbrook, R.D., Love, N.G., & Novak, J.T. (2004).
33. Snyder, S.A., Keith, T.L., Verbrugge, D.A., Snyder, Sorption of 17b-estradiol and 17a-ethinylestra- E.M., Gross, T.S., Kannan, K., & Giesy, J.P.
diol by colloidal organic carbon derived from bi- (1999). Analytical methods for detection of ological wastewater treatment systems, Environ- selected estrogenic compounds in aqueous mix- mental Science and Technology, 38, 3322–3329.
tures, Environmental Science and Technology, 46. Jurgens, M.D., Holthaus, K.I.E., Johnson, A.C., & Smith, J.J.L. (2002). The potential for estradiol 34. Kuch, H.M., & Ballschmitter, K. (2001). Determi- and ethynylestradiol degradation in English riv- nation of endocrine-disrupting phenolic com- ers, Environmental Toxicology and Chemistry, pounds and estrogens in surface and drinking water by HRG-(NCI)-MS in the picogram per liter 47. Ying, G.-G., & Kookana, R.S. (2003). Degradation range, Environmental Science and Technology, of five selected endocrine-disrupting chemicals in seawater and marine sediment, Environmental 35. Johnson, A.C., Belfroid, A., & Di Corcia, A.
Science and Technology, 37, 1256–1260.
(2000). Estimating steroid oestrogen inputs into 48. Johnson, A.C., & Sumpter, J. (2001). Removal of activated sludge treatment works and observa- tions on their removal from the effluent, Science sludge treatment works. Environmental Science of the Total Environment, 256, 163–173.
36. Ternes, T.A., Stumpf, M., Mueller, J., Haberer, K., 49. Colucci, M.S., & Topp, E. (2001). Persistence of Wilken, R.D., & Servos, M. (1999). Behavior and estrogenic hormones in agricultural soils. II. 17a- occurrence of estrogens in municipal sewage Ethynylestradiol, Journal of Environmental Qual- treatment plants—I. Investigations in Germany, Canada and Brazil, Science of the Total Environ- 50. Czajka, C.P., & Londry, K.L. (2006). Anaerobic biotransformation of estrogens. Science of the 37. Lagana, A., Bacaloni, A., De Leva, I., Faberi, A., Fago, G., & Marino, A. (2004). Analytical meth- 51. Segmuller, B.E., Armstrong, B.L., Dunphy, R., & odologies for determining the occurrence of en- Oyler, A.R. (2000). Identification of autoxidation Environmental Progress (Vol.27, No.3) DOI 10.1002/ep and photodegradation products of ethynylestra- 63. Ingrand, V., Herry, G., Beausse, J., & de Roubin, diol by on-line HPLC-NMR and HPLC-MS, Jour- M.-R. (2003). Analysis of steroid hormones in nal of Pharmaceutical and Biomedical Analysis, effluents of wastewater treatment plants by liquid chromatoraphy-tandem mass spectrometry, Jour- 52. Zuo, Y., Zhang, K., & Deng, Y. (2006). Occur- nal of Chromatography A, 1020, 99–104.
rence and photochemical degradation of 17a- 64. Carpinteiro, J., Quintana, J.B., Rodriguez, I., ethinylestradiol in Acushnet River Estuary, Chem- Carro, A.M., Lorenzo, R.A., & Cela, R. (2004).
Applicability of solid-phase microextraction fol- 53. Gomes, R.L., Avcioglu, E., Scrimshaw, M.D., & lowed by on-fiber silylation for the determination Lester, J.N. (2004). Steroid-estrogen determina- of estrogens in water samples by gas chromatog- tion in sediment and sewage sludge: A critique raphy-tandem mass spectrometry, Journal of of sample preparation and chromatographic/ mass spectrometry considerations, incorporating 65. Kawaguchi, M., Ishii, Y., Sakui, N., Okanouchi, a case study in method development, Trends in N., Ito, R., Inoue, K., Saito, K., & Nakazawa, H.
Analytical Chemistry, 23, 737–744.
(2004). Stir bar sorptive extraction with in situ 54. Kuster, M., Jose Lopez de Alda, M., & Barcelo, D.
derivatization and thermal desorption-gas chro- (2004). Analysis and distribution of estrogens and matography-mass spectrometry in the multi-shot progestogens in sewage sludge, soils and sedi- mode for determination of estrogens in river ments, Trends in Analytical Chemistry, 23, 790–798.
water samples, Journal of Chromatography A, 55. Gabet, V., Miege, C., Bados, P., & Coquery, M.
(2007). Analysis of estrogens in environmental 66. Johnson, A.C., Aerni, H.R., Gerritsen, A., Gibert, matrices, Trends in Analytical Chemistry, 26, M., Giger, W., Hylland, K., Jurgens, M., Nakari, T., Pickering, A., & Suter, M.J.F. (2005). Compar- 56. Petrovic, M., Eljarrat, E., Lopez de Alda, M.J., & ing steroid estrogen, and nonylphenol content Barcelo, D. (2001). Analysis and environmental across a range of European sewage plants with levels of endocrine-disrupting compounds in different treatment and management practices, freshwater sediments, Trends in Analytical Chem- 57. Lopez de Alda, M.J., & Barcelo, D. (2001). Use of Jurkovic, A., McInnis, R., Neheli, T., Schnell, A., solid-phase extraction in various of its modalities Seto, P., Smyth, S.A., & Ternes, T.A. (2005). Distri- for sample preparation in the determination of bution of estrogens, 17b-estradiol and estrone, in estrogens and progestogens in sediment and water, Canadian municipal wastewater treatment plants, Journal of Chromatography A, 938, 145–153.
Science of the Total Environment, 336, 155–170.
58. Noppe, H., Verslycke, T., De Wulf, E., Verhey- 68. Mitani, K., Fujioka, M., & Kataoka, H. (2005).
den, K., Monteyne, E., Van Caeter, P., Janssen, Fully automated analysis of estrogens in environ- C.R., & De brabander, H.F. (2007). Occurrence of mental waters by in-tube solid-phase microex- estrogens in the Scheldt estuary: A 2-year survey.
traction coupled with liquid chromatography-tan- Ecotoxicology and Environmental Safety, 66, 1–8.
dem mass spectrometry, Journal of Chromatogra- 59. Vrana, B., Mills, G., Allan, I., Dominiak, E., Svensson, K., Knutsson, J., Morrison, G., & 69. Braun, P., Moeder, M., Schrader, S., Popp, P., Greenwood, R. (2005). Passive sampling techni- Kuschk, P., & Engewald, W. (2003). Trace analy- ques for monitoring pollutants in water, Analyti- sis of technical nonylphenol, bisphenol A and 17a-ethinylestradiol in wastewater using solid- 60. Alvarez, D., Stackelberg, P., Petty, J., Huckins, J., phase microextraction and gas chromatography- Furlong, E., Zaugg, S., & Meyer, M. (2005). Com- mass spectrometry, Journal of Chromatography parison of a novel passive sampler to standard water-column sampling for organic contaminants 70. Almeida, C., & Nogueira, J.M.F. (2006). Determi- associated with wastewater effluents entering a nation of steroid sex hormones in water and New Jersey stream, Chemosphere, 61, 610–622.
urine matrices by stir bar sorptive extraction and liquid chromatography with diode array detec- Suter, M., & Burkhardt-Holm, P. (2005). Charac- tion, Journal of Pharmaceutical and Biomedical terization of environmental estrogens in river water using a three pronged approach: Active 71. Svenson, A., Allard, A.-S., & Ek, M. (2003). Re- and passive water sampling and the analysis of moval of estrogenicity in Swedish municipal accumulated estrogens in the bile of caged fish, sewage treatment plants, Water Research, 37, 72. Korner, W., Bolz, U., Sumuth, W., Hiller, G., 62. Mol, H.G.J., Sunarto, S., & Steijger, O.M. (2000).
Schuller, W., Hanf, V., & Hagenmaier, H. (2000).
Determination of endocrine disruptors in water Input/output balance of estrogenic active com- after derivatization with N-methyl-N-(tert-butyldi- pounds in a major municipal sewage plant in methyltrifluoroacetamide) using gas chromatog- Germany, Chemosphere, 40, 1131–1142.
raphy with mass spectrometric detection, Journal 73. Li, Z., Wang, S., Alice Lee, N., Allan, R.D., & Ken- nedy, I.R. (2004). Development of a solid-phase Environmental Progress (Vol.27, No.3) DOI 10.1002/ep extraction–enzyme-linked immunosorbent assay 17a-ethynylestradiol in STPs for domestic waste- method for the determination of estrone in water, Environmental Science and Biotechnology, water, Analytica Chimica Acta, 503, 171–177.
74. Schneider, C., Scholer, H.F., & Schneider, R.J.
84. Andersen, H.R., Hansen, M., Kjlholt, J., Stuer- (2004). A novel enzyme-linked immunosorbent Lauridsen, F., Ternes, T., & Halling-Srensen, B.
assay for ethynylestradiol using a long-chain (2005). Assessment of the importance of sorption biotinylated EE2 derivative, Steroids, 69, 245– for steroid estrogens removal during activated sludge treatment, Chemosphere, 61, 139–146.
75. Penalver, A., Pocurull, E., Borrull, F., & Marce, 85. Layton, A.C., Gregory, B.W., Seward, J.R., Schultz, R.M. (2002). Method based on solid-phase micro- T.W., & Sayler, G.S. (2000). Mineralization of ste- extraction-high-performance liquid chromatogra- roidal hormones by biosolids in wastewater treat- phy with UV and electrochemical detection to ment systems in tennessee USA, Environmental determine estrogenic compounds in water sam- Science and Technology, 34, 3925–3931.
ples, Journal of Chromatography A, 964, 153– 86. Colmenarejo, M.F., Rubio, A., Sanchez, E., Vicente, J., Garcia, M.G., & Borja, R. (2006). Evaluation of 76. Matsumoto, K., Tsukahara, Y., Uemura, T., Tsu- municipal wastewater treatment plants with differ- noda, K., Kume, H., Kawasaki, S., Tadano, J., & ent technologies at Las Rozas, Madrid (Spain), Jour- nal of Environmental Management, 81, 399–404.
resolved fluorometric determination of estrogens 87. Kargi, F., & Eker, S. (2002). Comparison of per- formances of rotating perforated tubes and rotat- using a b-diketonate europium chelate, Journal ing biodiscs biofilm reactors for wastewater treat- of Chromatography B: Analytical Technologies in ment, Process Biochemistry, 37, 1201–1206.
the Biomedical and Life Sciences, 773, 135–142.
88. Dangcong, P., Bernet, N., Delgenes, J.-P., & 77. Benijts, T., Dams, R., Lambert, W., & De Leenh- Moletta, R. (1999). Aerobic granular sludge—A eer, A. (2004). Countering matrix effects in envi- case report, Water Research, 33, 890–893.
89. Dionisi, D., Majone, M., Tandoi, V., & Beccari, M.
ionization tandem mass spectrometry water anal- (2001). Sequencing batch reactor: Influence of ysis for endocrine disrupting chemicals, Journal periodic operation on performance of activated of Chromatography A, 1029, 153–159.
78. Nakamura, S., Hwee Sian, T., & Daishima, S.
Industrial and Engineering Chemistry Research, (2001). Determination of estrogens in river water by gas chromatography-negative-ion chemical- 90. Liu, X.L., Wu, F., & Deng, N.S. (2003). Photode- ionization mass spectrometry, Journal of Chro- gradation of 17a-ethynylestradiol in aqueous so- lution exposed to a high-pressure mercury lamp 79. Shareef, A., Parnis, C.J., Angove, M.J., Wells, J.D., (250 W), Environmental Pollution, 126, 393–398.
& Johnson, B.B. (2004). Suitability of N,O-bis(tri- 91. Rudder, J.D., Wiele, T.V.D., Dhooge, W., Comh- methylsilyl)trifluoroacetamide and N-(tert-butyldi- aire, F., & Verstraete, W. (2004). Advanced water methylsilyl)-N-methyltrifluoroacetamide as deri- treatment with manganese oxide for the removal vatization reagents for the determination of the of 17a-ethynylestradiol (EE2), Water Research, estrogens estrone and 17a-ethinylestradiol by gas chromatography-mass spectrometry, Journal of 92. Huber, M.M., Ternes, T.A., & Gunten, U.V.
(2004). Removal of estrogenic activity and forma- 80. Shareef, A., Angove, M.J., & Wells, J.D. (2006).
tion of oxidation products during ozonation of Optimization of silylation using N-methyl-N-(tri- 17a-Ethinylestradiol, Environmental Science and methylsilyl)-trifluoroacetamide, N,O-bis-(trimeth- 93. Haiyan, R., Shulan, J., Ud din Ahmad, N., Dao, W., & Chengwu, C. (2007). Degradation charac- determination of the estrogens estrone and 17a- teristics and metabolic pathway of 17a-ethynyles- tradiol by Sphingobacterium sp. JCR5, Chemo- spectrometry, Journal of Chromatography A, 94. Shi, J., Fujisawa, S., Nakai, S., & Hosomi, M.
81. Zhang, Z.L., Hibberd, A., & Zhou, J.L. (2006).
(2004). Biodegradation of natural and synthetic Optimisation of derivatisation for the analysis of estrogens by nitrifying activated sludge and am- estrogenic compounds in water by solid-phase extraction gas chromatography-mass spectrome- paea, Water Research, 38, 2323–2330.
try, Analytica Chimica Acta, 577, 52–61.
95. Vader, J.S., van Ginkel, C.G., Sperling, F.M.G.M., de Jong, J., de Boer, W., de Graaf, J.S., van der Adams, C.D., & Surampalli, R.Y. (2006). Endo- Most, M., & Stokman, P.G.W. (2000). Degradation crine disrupting compounds removal from waste- of ethinyl estradiol by nitrifying activated sludge, water, a new challenge, Process Biochemistry, 96. Yoshimoto, T., Nagai, F., Fujimoto, J., Watanabe, 83. De Mes, T., Zeeman, G., & Lettinga, G. (2005).
K., Mizukoshi, H., Makino, T., Kimura, K., Saino, Occurence and fate of estrone, 17b-estradiol and H., Sawada, H., & Omura, H. (2004). Degrada- Environmental Progress (Vol.27, No.3) DOI 10.1002/ep optimization, Environmental Science and Tech- Rhodococcus equi isolates from activated sludge in wastewater treatment plants, Applied Microbi- 106. Le-Clech, P., Marselina, Y., Ye, Y., Stuetz, R.M., & ology and Biotechnology, 70, 5283–5289.
Chen, V. (2007). Visualisation of polysaccharide 97. Shi, J.H., Suzuki, Y., Lee, B.D., Nakai, S., & fouling on microporous membrane using differ- Hosomi, M. (2002). Isolation and characterization ent characterisation techniques, Journal of Mem- of the ethynylestradiol-biodegrading microorgan- Fusarium proliferatum strain HNS-1, Water 107. Lyko, S., Wintgens, T., Al-Halbouni, D., Baum- Science and Technology, 45, 175–179.
garten, S., Tacke, D., Drensla, K., Janot, A., Dott, 98. Yi, T., Harper, J.W., Holbrook, R., & Love, N.
W., Pinnekamp, J., & Melin, T. (2008). Long-term (2006). Role of particle size and ammonium oxi- monitoring of a full-scale municipal membrane dation in removal of 17a-ethinyl estradiol in bio- reactors, Journal of Environmental Engineering, operational performance, Journal of Membrane 99. Marrot, B., Barios-martinez, A., Moulin, P., & 108. Metzger, U., Le-Clech, P., Stuetz, R.M., Frimmel, Roche, N. (2004). Industrial wastewater treatment F.H., & Chen, V. (2007). Characterisation of poly- in a membrane bioreactor: A review, Environ- meric fouling in membrane bioreactors and the effect of different filtration modes, Journal of 100. Yang, W., Cicek, N., & Ilg, J. (2006). State-of-the- art of membrane bioreactors: Worldwide research 109. Wang, X.-M., Li, X.-Y., & Huang, X. (2007). Mem- and commercial applications in North America, brane fouling in a submerged membrane bio- Journal of Membrane Science, 270, 201–211.
reactor (SMBR): Characterisation of the sludge 101. Clara, M., Strenn, B., Gans, O., Martinez, E., cake and its high filtration resistance, Separation Kreuzinger, N., & Kroiss, H. (2005). Removal of and Purification Technology, 52, 439–445.
selected pharmaceuticals, fragrances and endo- 110. Bodzek, M., & Dudziak, M. (2006). Elimination crine disrupting compounds in a membrane bio- of steroidal sex hormones by conventional water reactor and conventional wastewater treatment treatment and membrane processes, Desalina- plants, Water Research, 39, 4797–4807.
102. Cicek, N., Winnen, H., Suidan, M.T., Wrenn, B.E., 111. Yoon, Y., Westerhoff, P., Snyder, S.A., Wert, E.C., Urbain, V., & Manem, J. (1998). Effectiveness of & Yoon, J. (2007). Removal of endocrine disrupt- the membrane bioreactor in the biodegradation ing compounds and pharmaceuticals by nanofil- of high molecular weight compounds, Water tration and ultrafiltration membranes, Desalina- 103. Kim, S.D., Cho, J., Kim, I.S., Vanderford, B.J., & 112. Scha¨fer, A.I., Mastrup, M., & Lund Jensen, R.
Snyder, S.A. (2007). Occurrence and removal of (2002). Particle interactions and removal of trace pharmaceuticals and endocrine disruptors in waters, Water Research, 41, 1013–1021.
113. Chang, S., Waite, T.D., Scha¨fer, A.I., & Fane, A.G.
104. Lyko, S., Wintgens, T., & Melin, T. (2005). Estro- (2002). Adsorption of trace steroid estrogens to genic trace contaminants in wastewater—Possi- hydrophobic hollow fibre membranes, Desalina- 114. Nghiem, L.D., Scha¨fer, A.I., & Elimelech, M.
105. Joss, A., Andersen, H., Ternes, T., Richle, P.R., & (2004). Removal of natural hormones by nanofil- Siegrist, H. (2004). Removal of estrogens in mu- tration membranes: Measurement, modeling and nicipal wastewater treatment under aerobic and mechanisms, Environmental Science and Tech- anaerobic conditions: Consequences for plant Environmental Progress (Vol.27, No.3) DOI 10.1002/ep


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