Fate and removal of selected endocrine‐disrupting compounds in sewage using activated sludge treatment

The variation and fate of four endocrine‐disrupting compounds (EDCs) composed of 4‐n‐nonylphenol (4‐n‐NP), bisphenol A (BPA), 17β‐estradiol (E2) and 17α‐ethinylestradiol (EE2) were investigated along treatment units in a sewage treatment plant (STP), China with anaerobic, anoxic and aerobic activated sludge processes. The mean concentrations were 64.8 ng/L (E2), 115.3 ng/L (4‐n‐NP), 171.5 ng/L (EE2), and 920.7 ng/L (BPA) in the influents, and 22.8 ng/L (E2), 50.9 ng/L (4‐n‐NP), 49.9 ng/L (EE2), and 84.3 ng/L (BPA) in the effluents. The biological treatment was more effective in removing NP, BPA and E2 from the aqueous phase than the primary treatment, while the latter could effectively remove EE2. Their possible removal mechanisms during the biological treatment with activated sludge were further explored through spiked batch experiments under three oxygen‐supplying conditions (anaerobic, anoxic and aerobic). The batch experiments showed that 4‐n‐NP, E2 and BPA were removed from the aqueous phase through biodegradation. The combination of sludge sorption and biodegradation accounted for the removal of EE2. Anoxic activated sludge showed the most rapid degradation of 4‐n‐NP, while E2 could be removed most effectively by aerobic activated sludge, and sludge sorption had a remarkable effect on its removal within the initial 15 min of the experiments under three oxygen‐supplying conditions.     

Assessment of river contamination by estrogenic compounds in Paris area (France)

Wastewater treatment plants (WWTPs) receive a large spectrum of endocrine disrupting compounds (EDCs) that are partially eliminated during treatment processes and discharged into rivers. Given the lack of information in France about river contamination by EDCs, we chose to examine estrogenic potential of WWTP influents, effluents and receiving waters in Paris and its suburbs. Water samples were analyzed using gas chromatography coupled with mass spectrometry for quantifying natural and synthetic estrogens combined with an in vitro estrogenicity bioassay associated to a high pressure liquid chromatography fractionation. The four estrogens investigated, Estrone (E1), 17beta-Estradiol (E2), Estriol (E3) and 17alpha-Ethinylestradiol (EE2) were found in all WWTP and river samples at concentrations ranging from 2.7 to 17.6 ng/l and 1.0 to 3.2 ng/l, respectively. The synthetic estrogen EE2 seems more resistant to biodegradation in WWTPs and thus accounted for 35-50% of the estimated estrogenic activity in rivers. However, fractionation of samples and differences between concentrations of E1, E2, E3 and EE2 and the estrogenic activity measured by the in vitro bioassay suggested a complexity of mechanisms underlying the biological response that could not be attributed only to the investigated molecules.     

北京污水厂进、出水中内分泌干扰物的分布

以三种酚类化合物(4-OP、4-n-NP、BPA)、五种雌激素(E1、E2、E3、17α-E2、EE2)为目标物,对其在北京市三个污水处理厂进、出水中的浓度及工艺流程中的分布、迁移进行了研究.结果表明,污水处理厂出水中浓度最高的物质是BPA、EE2,分别为(56～140)、(78～115)ng/L.BPA和天然雌激素(17α-E2除外)主要被生物降解去除,而对EE2的去除主要发生在初级处理过程,去除率约为63%.两种烷基酚在污水处理厂并不能被有效去除.与欧美国家、日本等相比,北京市污水处理厂进、出水中的内分泌干扰物浓度偏高,尤其是出水中的雌激素浓度较高,具有一定的环境风险.     

Contribution of known endocrine disrupting substances to the estrogenic activity in Tama River water samples from Japan using instrumental analysis and in vitro reporter gene assay

To quantitatively characterize the substances contributing to estrogenic activity in river water, in vitro bioassay using MVLN cells and instrumental analysis using liquid chromatograph–mass spectrometer (LC/MS) or liquid chromatograph–tandem mass spectrometer (LC/MS/MS) were applied to river water extracts taken from various locations in the Tama River, Japan. Tama River water samples were extracted using solid phase extraction and the crude extracts were fractionated by high-performance liquid chromatography (HPLC) into 10 fractions. The sixth fraction contained nonylphenol (NP) and octylphenol (OP) at concentrations in the range of 51.6–147 and 6.9–81.9 ng/L, respectively (concentrations corresponding to the original sample volumes). No estrogenic activity, expressed as 17β-estradiol equivalents (E2-EQ_B), however, was observed in this fraction (<0.6 ng-E2eq/L). Instrumentally determined estrogenic activity (E2-EQ_C), which is the concentrations of NP and OP multiplied by their corresponding relative potency, was below the detection limit of the MVLN cell bioassay. Estrogenic activities were detected only in HPLC fraction nos. 7, 8 and 9. Estrone (E1), estradiol (E2) and bisphenol A (BPA) were detected in these fractions. Estriol (E3) and ethynylestradiol (EE2) were not detected (<0.2 ng/L) in these fractions. The calculated E2-EQ_C for BPA was below the detection limit of bioassay. The E2-EQ_C for E1 and E2 were on the same order as the estrogenic activity determined by the bioassay (E2-EQ_B). The ratios of E2-EQ_C and E2-EQ_B for E1 and E2 in the three factions collectively (nos. 7–9) were 0.49–0.97 and 0.29–1.12, respectively. Above results indicated that the major causal substances to the estrogenic activity in the Tama River were E1 and E2.     

HPLC-fluorescence detection and adsorption of bisphenol A, 17beta-estradiol,and 17alpha-ethynyl estradiol on powdered activated carbon

The adsorption of three estrogenic compounds (bisphenol A (BPA), 17beta-estradiol (E2), and 17alpha-ethynyl estradiol (EE2)) on several powdered activated carbons (PAC) was investigated. Without preconcentration, method detection limits (MDL) using high-performance liquid chromatography (HPLC) with fluorescence detection at an excitation wavelength of 280 nm and an emission wavelength of 310 nm were 0.88, 1.15, and 0.96 nM for BPA, E2, and EE2, respectively. Compound recoveries were >90% in raw drinking water matrices. PAC screening studies (six PAC brands) indicated all three compounds were removed by PAC, but the percentage removal ranged from 31% to >99% based upon PAC type/dosage and presence/absence of natural organic matter. The order of removal (E2>EE2>BPA) corresponded with logK(ow) values for the compounds (3.1-4.0, 3.7-3.9, 3.3, respectively). Kinetic and PAC dose-response experiments were conducted with the two best performing PACs. Increasing contact time and PAC dose improved compound removal. Freundlich isotherm parameters were fit to the experimental data. This study confirms that PAC treatment is feasible for >99% removal of three estrogenic compounds from raw drinking waters that may be at risk for containing such compounds, at least at initial concentration of 500 ng/l and higher.     

Removal of selected pharmaceuticals and personal care products (PPCPs) and endocrine-disrupting chemicals (EDCs) during sand filtration and ozonation at a municipal sewage treatment plant

We investigated the efficiencies of removal of 24 pharmaceutically active compounds (PhACs) during sand filtration and ozonation in an operating municipal sewage treatment plant (STP). The target compounds were 2 phenolic antiseptics (thymol, triclosan), 5 acidic analgesics or anti-inflammatories (ibuprofen, naproxen, ketoprofen, fenoprofen, mefenamic acid), 4 amide pharmaceuticals (propyphenazone, crotamiton, carbamazepine, diethyltoluamide), 7 antibiotics (sulfapyridine, sulfamethoxazole, trimethoprim, azithromycin, erythromycin anhydride, clarithromycin, roxithromycin), 3 phenolic endocrine-disrupting chemicals (EDCs) (nonylphenol:NP, octylphenol:OP, bisphenol A:BPA) and 3 natural estrogens (17 beta-estradiol:E2, estrone:E1, estriol:E3). Ozonation removed approximately 80% or more of the phenolic antiseptics, crotamiton, sulfonamide and macrolide antibiotics, and 17 beta-estradiol. Their removal is discussed in terms of chemical structure. The study ascertained the validity of ozonation mechanisms proposed by previous studies in an actually running STP. Compounds with a CC double bond or an aromatic structure with electron donors (e.g., phenol, alkyl, methoxy, or non-protonated amine) were susceptible to ozonation. Compounds with amide structures were resistant. Removal of the PhACs during sand filtration was generally inefficient, probably because of their low hydrophobicities. The combination of ozonation and sand filtration with activated sludge treatment gave efficient removal (>80%) of all the target compounds except carbamazepine and diethyltoluamide. Among all the steps in the plant, ozonation contributed substantially to overall removal of naproxen, ketoprofen, triclosan, crotamiton, sulfapyridine, macrolide antibiotics, and estrone.     

Advanced water treatment with manganese oxide for the removal of 17alpha-ethynylestradiol (EE2)

Municipal wastewater is supposed to be one of the most important sources of endocrine-disrupting compounds (EDCs) in water. Therefore, advanced treatments and cost-efficient techniques should be developed to prevent the spread of this type of pollution into the environment. In this view, experiments were conducted in which the removal of 17alpha-ethynylestradiol (EE2), a synthetic and persistent estrogen, from water was monitored in three upstream bioreactors (UBRs), filled with, respectively, sand, granulated activated carbon (GAC) and MnO(2) granules. Tap water, spiked with 15,000ngEE2/L was filtered through the reactors with a hydraulic retention time of approximately 1h. The removal of EE2 in the sand, GAC and MnO(2) reactors was, respectively, 17.3%,>99.8% and 81.7%. The removal in the GAC reactor was mainly due to adsorption. The MnO(2) reactor, however, removed significantly more EE2 than could be predicted from its adsorption capacity, probably thanks to its catalytic properties. These catalytic properties could make it a cost-efficient technique for the removal of EE2, but further research at more environmentally relevant concentrations is needed.     

Comparison of natural estrogen removal efficiency in the conventional activated sludge process and the oxidation ditch process

The presence of natural estrogens, 17beta-estradiol (E2), estrone (E1) and estriol (E3), as well as estrogenic activity in wastewater influents and secondary effluents were investigated in 20 full-scale wastewater treatment plants in Japan. In all of the influent samples, natural estrogens were detected at concentrations above the minimum limits of detection (0.5ng/L). The concentrations of natural estrogens detected in the effluent of oxidation ditch plants were generally lower than previously reported values. On the other hand, in the conventional activated sludge plants, increments of E1 during biological treatment were frequently observed although E2 and E3 were removed effectively in the process. The removal rates of natural estrogens or estrogenic activity show no observed statistical relationship with the solids retention time (SRT) and the hydraulic retention time (HRT). However, the plants with high SRT or HRT generally showed high and stable removal of both natural estrogens and estrogenic activity.     

Study on the treatment of the sulfite pulp CEH bleaching effluents with the coagulation-anaerobic acidification-aeration package reactor

The coagulation-anaerobic acidification-aeration package reactor was designed for the treatment of pulp CEH bleaching effluents, the efficiencies in CODcr, BOD(5), AOX and toxicity removal achieved were 88.1%, 81.0%, 98.4% and 92.0%, respectively, with 15 h HRT. The toxicity and AOX were removed mainly through coagulation and anaerobic process, while the COD and BOD(5) were removed mainly through coagulation and aerobic process. The pretreatment of coagulation precipitation decreased the following organic load, which decreased the following treatment retention time and increased the stability of the system.The results of GC-MS showed: pollutants of wastewater were mainly chlorinated organics, most of AOX and the toxicity were removed by reductive dechlorination and acidified hydrolysis in anaerobic unit, the high COD removal in aerobic unit showed further degradation of pollutants. Chlorine atoms in the ortho position were preferentially dechlorination, that in para position were difficult to remove from chlorinated phenols during biological treatment.     

Hydroxyapatite-supported Ag-TiO2 as Escherichia coli disinfection photocatalyst

A series of hydroxyapatite (HAP), 1wt% Ag-TiO(2) (AT1), 1wt% Ag-HAP and 5wt% AT1/HAP composite catalysts were prepared by incipient wetness and mechanical mixing methods. They were characterized by X-ray diffraction (XRD), FT-IR, SEM and ESCA analyses and their photocatalytic bactericidal activities were measured in suspension using Escherichia coli (E. coli), a water pollutant indicator. The surface analysis revealed that the Ag/Ti ratio is found to be ca. 0.0273 and also it indicated that the titania is present in the form of Ti(4+) and Ag is present as metallic silver. Both the XRD and ESCA analyses confirmed the phase of metallic Ag particles, which played a significant role on the bactericidal activity of the Ag doped TiO(2) catalysts. The FT-IR analysis of HAP revealed that the peak intensity is due to the absorbance of surface PO(4)(3-) group centered at wave number 1030cm(-1) and is drastically decreased upon exposure to UV for 1h. The HAP displayed high amount of bacteria adsorption, ca. 80% during the dark experiments compared to other catalytic systems tested. The cumulative photocatalytic properties of AT1/HAP catalytic system resulted in 100% E. coli bacteria reduction within 2min.     

Detection of microsporidia in drinking water, wastewater and recreational rivers

Diarrhea is the main health problem caused by human-related microsporidia, and waterborne transmission is one of the main risk factors for intestinal diseases. Recent studies suggest the involvement of water in the epidemiology of human microsporidiosis. However, studies related to the presence of microsporidia in different types of waters from countries where human microsporidiosis has been described are still scarce. Thirty-eight water samples from 8 drinking water treatment plants (DWTPs), 8 wastewater treatment plants (WWTPs) and 6 recreational river areas (RRAs) from Galicia (NW Spain) have been analyzed. One hundred liters of water from DWTPs and 50 L of water from WWTPs and RRAs were filtered to recover parasites, using the IDEXX Filta-Max® system.Microsporidian spores were identified by Weber’s stain and positive samples were analyzed by PCR, using specific primers for Enterocytozoon bieneusi, Encephalitozoon intestinalis, Encephalitozoon cuniculi, and Encephalitozoon hellem. Microsporidia spores were identified by staining protocols in eight samples (21.0%): 2 from DWTPs, 5 from WWTPs, and 1 from an RRA. In the RRA sample, the microsporidia were identified as E. intestinalis.To the best of our knowledge, this is the first report of human-pathogenic microsporidia in water samples from DWTPs, WWTPs and RRAs in Spain. These observations add further evidence to support that new and appropriate control and regulations for drinking, wastewater, and recreational waters should be established to avoid health risks from this pathogen.     

Direct photolysis of estrogens in aqueous solutions

Direct photolysis of two estrogens 17beta-estradiol (E2) and estrone (E1) in aqueous solutions radiated by UV-light and UV-Vis-light was studied preliminarily. The results suggest that the photolysis of E2 in aqueous solutions occurs under irradiation with UV disinfection lamp (lambda = 254 nm, 30 W), while E1 can also undergo photolysis under irradiation with a high-pressure mercury lamp (lambda > or = 365 nm, 125 W). The photolysis reactions of E2 and E1 at the concentration of 3.0-20 mgl(-1) in aqueous solutions were all in accordance with pseudo-first-order law. The photolysis rate of estrogens in aqueous solutions reached the lowest value at pH approximately 5.0, while the highest at pH 8.0 over the range of 2.0-8.0. The higher the initial concentration of the two estrogens, the lower the rate of photolysis.     

Combined exposure to cyanobacterial biomass, lead and the Newcastle virus enhances avian toxicity

Under environmental conditions, wild birds can be exposed to multiple stressors including natural toxins, anthropogenic pollutants and infectious agents at the same time.This experimental study was successful in testing the hypothesis that adverse effects of cyanotoxins, heavy metals and a non-pathogenic immunological challenge combine to enhance avian toxicity. Mortality occurred in combined exposures to naturally occurring cyanobacterial biomass and lead shots, lead shots and Newcastle vaccination as well as in single lead shot exposure. Mostly acute effects around day 10 were observed. On day 30 of exposure, there were no differences in the liver accumulation of lead in single and combined exposure groups. Interestingly, liver microcystin levels were elevated in birds co-exposed to cyanobacterial biomass together with lead or lead and the Newcastle virus. Significant differences in body weights between all Pb-exposed and Pb-non-exposed birds were found on days 10 and 20. Single exposure to cyanobacterial biomass resulted in hepatic vacuolar dystrophy, whereas co-exposure with lead led to more severe granular dystrophy. Haematological changes were associated with lead exposure, in particular. Biochemical analysis revealed a decrease in glucose and an increase in lactate dehydrogenase in single and combined cyanobacterial and lead exposures, which also showed a decreased antibody response to vaccination.The combined exposure of experimental birds to sub-lethal doses of individual stressors is ecologically realistic. It brings together new pieces of knowledge on avian health. In light of this study, investigators of wild bird die-offs should be circumspect when evaluating findings of low concentrations of contaminants that would not result in mortality on a separate basis. As such it has implications for wildlife biologists, veterinarians and conservationists of avian biodiversity.     

Photodegradation of estrone and 17beta-estradiol in water

The TiO(2)-assisted photodegradation of two natural female hormones, estrone (E1) and 17beta-estradiol (E2), was investigated in two UV-photo-reactors, followed by solid-phase extraction and analysis by gas chromatography-mass spectrometry (GC-MS). The degradation of E1 and E2 in both reactors followed the pseudo-first-order kinetics. In reactor 1 (150W), 97% of compounds were degraded within 4h of irradiation. Even more rapid degradation was observed in reactor 2 (15W) where 98% of both compounds disappeared within 1h, due to the shorter wavelength of UV-light in reactor 2 (fixed at 253nm) than reactor 1 (238-579nm). The influences of different initial chemical concentrations, pH value, the presence of dissolved organic matter and hydrogen dioxide, and the catalyst concentration on the degradation rate of E1 and E2 in aqueous solutions were investigated. The results show that the extent of photo-induced degradation of E1 and E2 strongly depends on the water constituents in solution. The degradation rate was increased when pH value was increased from 2 to 7.6, beyond which the degradation rate started to decrease. The presence of humic acid enhanced the degradation of E1 and E2 in both reactors as a result of photosensitisation effect of humic acid chromophore. The degradation rate increased with an increase in H(2)O(2) concentration. The degradation rate was also enhanced by increasing catalyst concentration up to 2g/l. The findings therefore suggest that photocatalysis can be a very effective method of rapidly removing certain EDCs from water.     

Effect of photochemical treatment on the biocompatibility of a commercial nonionic surfactant used in the textile industry

The degradability of surfactants is a frequent and complex issue arising both at domestic as well as industrial treatment facilities. The present paper describes a laboratory study conducted to elucidate the photochemical and biochemical treatability of a nonionic, alkyl polyethylene ether-based surfactant formulation commonly used in the textile preparation stage. The application of H(2)O(2)/UV-C advanced photochemical oxidation appeared to be a suitable treatment alternative and 90% COD removal (COD(0) approximately 500 mg/L) could be achieved under optimized process conditions. A significant COD removal efficiency (74%) could also be reached after biodegradation (final COD=135 mg/L) of the surfactant; however, necessitated an acclimation period of at least 6 weeks for the achievement of steady-state conditions. H(2)O(2)/UV-C treatment efficiency was seriously retarded upon elevation of the initial COD to around 1000 mg/L, resulting in 46% COD and 38% TOC removal after 120 min photochemical oxidation (H(2)O(2,0)=1020 mg/L; pH(0)=9.1). The BOD(5)/COD ratio increased from 0.23 to 0.31 after the application of H(2)O(2)/UV-C revealing that photochemical pretreatment may have a positive effect on the ultimate biodegradation of the nonionic surfactant. Although the time required for activated sludge treatment to reach steady-state conditions could be reduced to 3 weeks for the photochemically pretreated surfactant formulation biochemical COD removal efficiency dramatically decreased from 74% to 39% for the nonionic surfactant being subjected to H(2)O(2)/UV-C pretreatment (ultimate COD after activated sludge treatment=265 mg/L).     

Simultaneous abiotic reduction-biotic oxidation in a microbial-MnO2-catalyzed Fenton-like system

The possibility of simultaneous activity of superoxide-mediated transformations and heterotrophic aerobic bacterial metabolism was investigated in catalyzed H₂O₂ propagations (CHP; i.e., modified Fenton's reagent) systems containing Escherichia coli. Two probe compounds were used: glucose for the detection of heterotrophic metabolism of E. coli, and tetrachloromethane (CCl₄) for the detection of superoxide generated in a MnO₂-catalyzed CHP system. In the MnO₂-catalyzed CHP system without bacteria, only CCl₄ loss was observed; in contrast, only glucose degradation occurred E. coli systems without CHP reagents. In combined microbial-MnO₂ CHP reactions, loss of both probes was observed. Glucose assimilation decreased and CCl₄ transformation increased as a function of H₂O₂ concentration. Central composite rotatable experimental designs were used to determine that the conditions providing maximum simultaneous abiotic-biotic reactions were a biomass level of 10⁹ CFU/mL, 0.5 mM H₂O₂, and 0.5 g MnO₂. These results demonstrate that bacterial metabolism can occur in the presence of superoxide-mediated transformations. Such coexisting reactions may occur when H₂O₂ is injected into MnO₂-rich regions of the subsurface as a microbial oxygen source or for in situ oxidation; however, process control of such coexisting transformations may be difficult to achieve in the subsurface due to heterogeneity. Alternatively, hybrid abiotic reduction-biotic oxidation systems could be used for the treatment of industrial effluents or dilute solvent wastes that contain traces of highly halogenated compounds.     

Impact of salinity and pH on the UVC/H2O2 treatment of reverse osmosis concentrate produced from municipal wastewater reclamation

While reverse osmosis (RO) technology is playing an increasingly important role in the reclamation of municipal wastewater, safe disposal of the resulting RO concentrate (ROC), which can have high levels of effluent organic pollutants, remains a challenge to the water industry. The potential of UVC/H₂O₂ treatment for degrading the organic pollutants and increasing their biodegradability has been demonstrated in several studies, and in this work the impact of the water quality variables pH, salinity and initial organic concentration on the UVC/H₂O₂ (3 mM) treatment of a municipal ROC was investigated. The reduction in chemical oxygen demand and dissolved organic carbon was markedly faster and greater under acidic conditions, and the treatment performance was apparently not affected by salinity as increasing the ROC salinity 4-fold had only minimal impact on organics reduction. The biodegradability of the ROC (as indicated by biodegradable dissolved organic carbon (BDOC) level) was at least doubled after 2 h UVC/H₂O₂ treatment under various reaction conditions. However, the production of biodegradable intermediates was limited after 30 min treatment, which was associated with the depletion of the conjugated compounds. Overall, more than 80% of the DOC was removed after 2 h UVC/3 mM H₂O₂ treatment followed by biological treatment (BDOC test) for the ROC at pH 4-8.5 and electrical conductivity up to 11.16 mS/cm. However, shorter UV irradiation time gave markedly higher energy efficiency (e.g., EE/O 50 kWh/m³ at 30 min (63% DOC removal) cf. 112 kWh/m³ at 2 h). No toxicity was detected for the treated ROC using Microtox^® tests. Although the trihalomethane formation potential increased after the UVC/H₂O₂ treatment, it was reduced to below that of the raw ROC after the biological treatment.     

Photocatalytic degradation of non-steroidal anti-inflammatory drugs with TiO2 and simulated solar irradiation

The aim of this work is to evaluate and compare the degradation achieved for three non-steroidal anti-inflammatory drugs (NSAIDs) by heterogeneous TiO2 photocatalytic means in aqueous solution at laboratory scale. The selected pharmaceutical compounds were diclofenac (DCF), naproxen (NPX) and ibuprofen (IBP). These compounds were used in their sodium salt chemical form. Previous experiments (adsorption, photolysis and thermodegradation) were developed to evaluate non-catalytic degradation for each NSAID. Photocatalytic experiments were carried out in a Xe-lamp reactor in order to study the influences of different operational conditions (catalyst load, temperature and dissolved oxygen concentration). These results showed that the optimum amount of TiO2, to achieve maximum degradation, of IBP was 1g/L. In contrast, the maximum degradation for DCF or NPX was observed at a TiO2 loading of 0.1g/L. Temperature had a significant effect only for NPX degradation, achieving almost 99% phototransformation. No significant differences were observed for DCF and IBP at 20, 30 and 40 degrees C. Dissolved oxygen concentration was an important parameter to increase the degradation for NPX and IBP. However, it was observed that its rate of mineralization did not increase. Intermediate metabolites were detected in all cases. Hydroxyl metabolites were the most important residual compounds after the photocatalytic treatment of IBP. The inhibition percentage of bioluminescence from Vibro fischeri--as a toxicity parameter--increased during the irradiation time due to the residual concentration of the hydroxyl metabolites generated. However, after 120 min, in experiments with 40 mg/L of dissolved oxygen, a decrease of the % inhibition was observed. Only photocatalytic treatment of IBP drives to a satisfactory biodegradability index BOD5/COD (between 0.16 and 0.42) and, only in this case, a post-biological treatment could be suggested.     

Oxidative removal of aqueous steroid estrogens by manganese oxides

This study investigated the oxidative removal of steroid estrogens from water by synthetic manganese oxide (MnO₂) and the factors influencing the reactions. Using 1 × 10⁻⁵ M MnO₂ at pH 4, estrone (E1), 17β-estradiol (E2), estriol (E3) and 17α-ethinylestradiol (EE2), all at 4 × 10⁻⁶ M, were rapidly removed within 220 min, indicating the effectiveness of MnO₂ as an oxidizing agent towards estrogens. E2 removal increased with decreasing pH over the tested range of 4-8, due most likely to increased oxidizing power of MnO₂ and a cleaner reactive surface in acidic solutions. Coexisting metal ions of 0.01 M (Cu(II), Zn(II), Fe(III) and Mn(II)) and Mn(II) released from MnO₂ reduction competed with E2 for reactive sites leading to reduced E2 removal. Observed differential suppression on E2 removal may be related to different speciations of metals, as suggested by the MINTEQ calculations, and hence their different adsorptivities on MnO₂. By suppressing the metal effect, humic acid substantially enhanced E2 removal. This was attributed to complexation of humic acid with metal ions. With 0.01 M ZnCl₂ in solutions containing 1 mg l⁻¹ humic acid, the binding of humic acid for Zn(II) was determined at 251 mmol g⁻¹. An in vitro assay using human breast carcinoma MCF-7 cells indicated a near elimination of estrogenic activities without secondary risk of estrogen solutions treated with MnO₂. Synthetic MnO₂ is therefore a promising chemical agent under optimized conditions for estrogen removal from water. Metal chelators recalcitrant to MnO₂ oxidation may be properly used to further enhance the MnO₂ performance.