Removal Of Endocrine Disruptors Research Articles

Efficient removal of endocrine disruptors using nano zero-valent iron loaded organo-attapulgite: Mechanism and factors

Endocrine-disrupting pollutants have become a major problem in aquatic environments. Advanced oxidation processes are recognized as promising technologies for treating endocrine disruptor-contaminated water. Herein, a novel nanoscale zero-valent iron loaded organo-attapulgite (NZVI@OATP) was employed as a catalyst to activate persulfate (PDS) for phenanthrene (PHE) and dibutyl phthalate (DBP) degradation. NZVI@OATP with a NZVI:OATP mole ratio of 1:1 (CTAB:ATP = 1:200) exhibited 100 % PHE and 84 % DBP degradation within 30 min, and chloride was found to have a positive effect on their degradation. Radical scavenger and electron paramagnetic resonance studies revealed that the contribution of the active species follows the order of O2- ≈ 1O2>SO4- ≫ OH. The optimal degradation pathways were proposed based on the liquid chromatography-mass spectrometry and density functional theory and the possible degradation paths of PHE and DBP, including the 9,10-phenanthraquinone and phthalic acid pathways, respectively, were proposed. The toxicity estimation software tool showed that the toxicities of PHE and DBP were reduced after degradation. Moreover, 50 % PHE degradation could be achieved after five cycles, demonstrating that NZVI@OATP is a promising catalyst for endocrine disruptor treatment with PDS.

Biodegradation and sorption of nutrients and endocrine disruptors in a novel concrete-based substrate in vertical-flow constructed wetlands

Removing phosphorus and endocrine-disruptors (EDC) is still challenging for low-cost sewage treatment systems. This study investigated the efficiency of three vertical-flow constructed wetlands (VFCW) vegetated with Eichhornia crassipes onto red clay (CW-RC), autoclaved aerated concrete (CW-AC), and composite from the chemical activation of autoclaved aerated concrete with white cement (CW-AAC) in the removal of organic matter, nutrients, and estrone, 17β-estradiol, and 17α-ethinylestradiol. The novelty aspect of this study is related to selecting these clay and cementitious-based materials in removing endocrine disruptors and nutrients in VFCW. The subsurface VFCW were operated in sequencing-batch mode (cycles of 48-48-72 h), treating synthetic wastewater for 308 days. The operation consisted of Stages I and II, different by adding EDC in Stage II. The presence of EDC increased the competition for dissolved oxygen (DO) and reduced the active sites available for adsorption, diminishing the removal efficiencies of TKN and TAN and total phosphorus in the systems. CW-RC showed a significant increase in COD removal from 65% to 91%, while CW-AC and CW-AAC maintained stable COD removal (84%–82% and 78%–81%, respectively). Overall, the substrates proved effective in removing EDC, with CW-AC and CW-AAC achieving >60% of removal. Bacteria Candidatus Brocadia and Candidatus Jettenia, responsible for carrying out the Anammox process, were identified in assessing the microbial community structure. According to the mass balance analysis, adsorption is the main mechanism for removing TP in CW-AC and CW-AAC, while other losses were predominant in CW-RC. Conversely, for TN removal, the adsorption is more representative in CW-RC, and the different metabolic routes of microorganisms, biofilm assimilation, and partial ammonia volatilization in CW-AC and CW-AAC. The results suggest that the composite AAC is the most suitable material for enhancing the simultaneous removal of organic matter, nutrients, and EDC in VFCW under the evaluated operational conditions.

Study on Removal of Endocrine Disruptors in Water Bodies by Advanced Persulfate Oxidation Technology: A Review

Endocrine disruptors (EDCs), as emerging micro-contaminants, interfere with hormones secretion and are harmful to human reproductive system when entering human body. Derived from industry pollution, municipal sewage or agricultural irrigation and run-off, they are able to penetrate to groundwater or gather into surface water that finally supply humans daily use. Water quality is closely related to human health, especially drinking water, so it is necessary to remove EDCs from polluted water bodies before water is treated and put into use. It is how to efficiently and maximally remove such substances in water bodies that has been a hot issue recently, which has stirred wide attention both at home and abroad. This paper reviews the previous research achievements in this field, simply expounds the mechanism of the reaction between persulfate and EDCs, discusses the characteristics and drawbacks of different activation methods, and finally gives suggestions on how advanced persulfate oxidation technology will develop to an optimization in the future when considering low cost, high removal efficiency and zero secondary pollution.

The optimalization of photocatalytic degradation of 4-tert-octylphenol

Endocrine disruptors (EDs) are a group of organic pollutants, which have negative effect on the hormonal systems of organism. For example, they can be toxic for the hormonal systems in fish, resulting in decrease in fertility. Conventional wastewater treatment is not successful in removal of EDs, therefore heterogenous photocatalysis is studied as an effective removal tool. The aim of this study was to optimize a method of photocatalytic removal of 4-tert-octylphenol, an endocrine disruptor present in wastewater. TiO2 P25 was used as a photocatalyst, UV light was used for irradiation. Various amounts of photocatalyst in the reaction mixture as well as various irradiation intensities were applied. P25 was applied to 25 mL of 10-4 M solution of 4-OP as a free powder. The reaction mixture was irradiated using UV light (365 nm) for 5 hours. An array of concentrations of P25 (1, 2, 4, 8 and 16 mg, irradiation intensity 1.1 mW cm-2) and of irradiation intensities (1.1, 3.6, 6.7 and 8.5 mW cm-2, mass of P25 2 mg) was used. Aliquotes were taken from the reaction at time intervals and were analyzed using RP-HPLC-DAD detection. From the data obtained, it was determined that the reaction rate increases with the increasing amount of photocatalyst added in a dependence following the Langmuir-Hinshelwood kinetics. It is proposed that the reaction rate would reach a plateau when more than 16 mg of P25 is added. However, the increase of the P25 amount complicates the separation of the photocatalyst from the reaction mixture when the reaction is over–centrifugation is more difficult. Overall, 4 mg of P25 was sufficient for complete removal of 4-OP after 5 hours, 8 mg was sufficient for complete removal of 4-OP after 3 hours. When an irradiation intensity of 3.6 mW cm was used, the complete removal of 4-OP was achieved at 5 hours. When the intensity was increased to 8.5 mW, 1.5 hours was enough to completely degrade 4-OP. Overall, an ideal experiment for total degradation of 4-OP was proposed–2 mg P25 and 6.7 mW cm-2. Furthermore, experimental conditions for following the kinetics of the reaction were optimized at 2 mg P25 and 1.1 mW cm-2. In this study, a photocatalytic degradation of 4-OP was studied. The dependence of reaction rate on both the mass of photocatalyst in the reaction mixture and the irradiation intensity was examined. It was determined that the dependencies were Langmuir-Hinshelwood kinetics and linear in the studied range, respectively. These results will be further applied on optimizing experiments using immobilized photocatalysts, which is more suitable for industrial use.

Effect of W concentration in the organized Ti-W alloy oxide nanotubes array on the photoelectrocatalytic properties and its application in the removal of endocrine disruptors using real water matrix

To evaluate the tungsten content on the photoelectrocatalytic properties of self-organized nanotubes grown by anodization on Ti-xW (wt%) alloys, where x is 0.5, 2.5 or 5.0, this work investigated the phase transformation of TiO2, the tungsten oxidation states in the oxide layers and their photoelectrocatalytic performance in the degradation of estrone (E1) and 17α-ethinylestradiol (EE2). These films were employed in photocatalytic and photoelectrocatalytic removals of hormones from synthetic and real water matrices. In synthetic water, E1 and EE2 removals, reached efficiencies of 92% and 71%, respectively, after 2 min under UV–Vis photoelectrocatalysis using NT/Ti-5.0W as catalyst. About 30 times longer was needed to degrade 77% of both hormones from the real water matrix due to the presence of other high organic charge. The high performance of the NT/Ti-5.0W was associated with the combination of doping (W-doped TiO2) and WO3 (W6+) heterojunction. However, this electrode had its stability compromised under long degradation times, mainly under visible light, due to a WO3 leaching process. As for NT/Ti-0.5W, the substitutional W-doped TiO2 contributed to its greater stability and efficiency for a long time. The low performance of NT/Ti-2.5W was justified by high density of oxygen vacancy and unfavorable position of its adsorption bands.

Degradation and Detection of Endocrine Disruptors by Laccase-Mimetic Polyoxometalates.

Endocrine disruptors are newly identified water contaminants and immediately caught worldwide concern. An effort has been made to degrade endocrine disruptors in the water body by relying on laccase-assisted approaches, including laccase-mediated catalytic systems, immobilized laccase catalytic systems, and nano-catalytic systems based on atypical protein enzymes. Analogous to laccases, polyoxometalates (POMs) have a similar size as these enzymes. They are also capable of using oxygen as an electron acceptor, which could assist the removal of endocrine disruptors in water. This perspective begins with a brief introduction to endocrine disruptors and laccases, summarizes current approaches employing laccases, and focuses on the nano-catalytic systems that mimic the function of laccases. Among the inorganic nanoparticles, POMs meet the design requirements and are easy for large-scale production. The catalytic performance of POMs in water treatment is highlighted, and an example of using polyoxovanadates for endocrine disruptor degradation is given at the end of this perspective. Exploring laccase-mimetic POMs will give key insights into the degradation of emergent water contaminants.

Assessment of Conventional Full-Scale Treatment for the Removal of Endocrine Disruptors and Pharmaceuticals Present in the Tibagi River (Paraná State, Brazil)

The concentrations of 25 pharmaceuticals and endocrine disruptors were monitored in the water coming from the Tibagi River (State of Paraná, Brazil) and in a conventional water treatment plant over 13 sampling campaigns. In raw water, only 3 compounds (bisphenol A, dexamethasone and losartan) were detected with high frequency (>75%) and 4 drugs (estradiol, diclofenac, loratadine and naproxen) were found with moderate frequency (between 30 and 70%). In addition, 7 micropollutants (paracetamol, ethinylestradiol, caffeine, propanolol, diltiazem, benzafibrate and promethazine) were not detected in any of the samples analyzed and 11 other compounds were quantified at low frequency (up to 25%). The conventional treatment process employed at WTP- Jataizinho has proven to be very efficient in removing dexamethasone (∼99%), moderately efficient in reducing bisphenol A (∼47%) concentration and inefficient in removing losartan (∼22%) and loratadine (not removed). The greatest removals were observed during the water clarification stage using aluminum sulfate as coagulant. In general, the dry and rainy seasons did not influence the concentrations of pharmaceuticals and endocrine disruptors in raw water. In terms of the 5 most prevalent micropollutants in treated water (bisphenol A, losartan, dexamethasone, loratadine and naproxen), the human health risk associated with ingesting contaminated water was assessed and considered negligible.

Magnetic porous carbon nanopolyhedron modified rGO composites as recyclable sorbent for effective removal of bisphenol A from water

The effective removal of endocrine disruptors from water is important for human health. Herein, magnetic sorbents, composed of ZiF-67-derived carbon polyhedrons containing Co nanocrystals (Co-C) modified reduced graphene oxide (rGO) nanosheets (Co-C/rGO), were synthesized. The optimized Co-C/rGO-2 exhibited a high adsorption capacity of 175.1 mg g−1 for removal of bisphenol A (BPA) from water because of the optimized porous structure including micropores, mesopores and macropores as well as high surface area of 284.4 m2 g−1. In addition, the adsorption equilibrium of BPA was almost reached within 3 h and showed almost stable at pH 2–7. Existence of humic acid, Ca2+, K+, Na+ had little effect, while the Al3+ showed negative on the adsorption of BPA. Furthermore, the magnetic Co-C/rGO-2 can be easily recovered and showed high reuse performance remaining 83.7% of the initial adsorption capacity after the 4th recycling. The fixed-bed experiment indicated that the removal efficiency of BPA (10 μg L–1) from water can reach almost 100% at bed volume lower than 4000. Fourier transform infrared spectroscopy and X-ray photoelectron spectroscopy results revealed that the adsorption of BPA was mainly dominated by the π-π interaction.

Mollusk shells as adsorbent for removal of endocrine disruptor in different water matrix

Mytella falcata shells were used as adsorbent to remove 17-α-methyltestosterone from water. Preliminary tests were carried out to evaluate the affinity of the mollusk shells in their natural, pyrolyzed and calcined form in relation to the hormone. Pyrolyzed material showed the best performance. The influence of the solution pH and the adsorbent load were also evaluated. The material was characterized by thermogravimetry, Fourier Transform Infrared Spectroscopy, X-ray diffraction, Point of Zero charge and Scanning Electron Microscopy. Adsorption assays reveals better kinetic fit for pseudo second order, with mechanism follow diffusion in bulk and intraparticle, while the Sips model presented a better fit to the equilibrium experimental data. The maximum adsorption capacity reached 0.778 mg.g−1 at 50 ºC. The process takes place in an exothermic way, being governed by forces from chemical nature, as indicated by the thermodynamic parameters. The artificial neural network with one hidden layer and three neurons showed up a promising tool in predicting equilibrium relationships of the adsorptive process. The neural model was equivalent to the isotherms models found in literature used to predict the adsorption kinetics and adsorption equilibrium. In terms of removal percentage, the adsorbent showed promising results achieving 70% for ultrapure water. On the other hand, when real water matrices were applied, the lower removal occurred with lagoon water (30%), and the highest removal was achieved using mineral water (80%), indicating this waste material as good alternative for the removal of endocrine disruptors from different types of water.

Effect of electrochemically-driven technologies on the treatment of endocrine disruptors in synthetic and real urban wastewater

While it remains a challenging task, having a fundamental understanding of the influence of water matrix composition is of central importance for the removal of pollutants in electrochemical treatment processes. This work studied the effect of the complexity of different water matrices on the removal of endocrine disruptors using different electrochemical advanced oxidation processes (EAOPs) based on H2O2 electrogeneration. The study helped improve the understanding of synthetic and real urban wastewater, and the effective mechanisms for the treatment of pollutants in these effluents. The results obtained showed that, regardless of the medium applied, there was an increase in pollutants mineralization in the following order, based on the EAOPs method employed: electrochemical oxidation with H2O2 electrogeneration (EO-H2O2) < electro-Fenton (EF) < photoelectro-Fenton (PEF). Despite the slower degradation kinetics of the EO-H2O2 process, its wider pH range makes it suitable for implementation. Aside the degradation/mineralization performance of the EO-H2O2 process, a time-course analysis was conducted on the nitrogen and chloride-based ions in the solution investigated since their presence is vital for determining the final use of the treated effluents based on the parameters of water quality. These parameters include the established maximum concentration levels of the compounds in the water matrix allowed for human consumption or the legal limits of discharge for wastewater treatment facilities. The findings help shed light on the role of coexisting species in water matrix, since this affects the efficiency and competitiveness of EAOPs. Clearly, having detailed knowledge of the water matrix composition will help one to have a better understanding of EAOPs, and this will enable to obtain higher degradation levels in water treatment processes.

Electrochemical detection and simultaneous removal of endocrine disruptor, bisphenol A using a carbon felt electrode

2,2-Bis (4-hydroxyphenyl) propane (bisphenol A) is a precursor in many industrial and manufactural resins, plastics, and polycarbonate, as well as an endocrine disruptor in humans and animals. Therefore, the real-time sensing and in-situ removal of BPA are in strong demand. This study evaluated a method for the electrochemical detection of BPA using a carbon felt electrode. BPA was detected by cyclic voltammetry. During detection, the BPA was electropolymerized to a non-conductive lump and layer on the electrode surface. Simultaneously, the capacitance and electrochemical properties of the carbon felt decreased. The peak current and BPA concentration showed a linear correlation; the estimated detection limit was 4.78 × 10−7 M. The BPA-electropolymerized carbon felt could be regenerated successfully by ultrasonication. The detection and quantification of BPA in real water samples showed satisfactory recoveries of 98.4–101.0%. The carbon felt-based electrochemical analysis exhibited high sensitivity and reusability, making it applicable to the in-situ and on-site detection and removal of endocrine disruptors, such as BPA.

Reduced Graphene Oxide-Based Foam as an Endocrine Disruptor Adsorbent in Aqueous Solutions.

A stable and magnetic graphene oxide (GO) foam–polyethyleneimine–iron nanoparticle (GO–PEI–FeNPs) composite has been fabricated for removal of endocrine disruptors—bisphenol A, progesterone and norethisterone—from aqueous solution. The foam with porous and hierarchical structures was synthesized by reduction of graphene oxide layers coupled with co-precipitation of iron under a hydrothermal system using polyethyleneimine as a cross linker. The presence of magnetic iron nanoparticles facilitates the separation process after decontamination. The foam was fully characterized by surface and structural scanning electron microscopy, Fourier transform infrared spectroscopy, Raman spectroscopy and X-ray photoelectron spectroscopy. The foam exhibits a high adsorption capacity, and the maximum adsorption percentages are 68%, 49% and 80% for bisphenol A, progesterone and norethisterone, respectively. The adsorption process of bisphenol A is explained according to the Langmuir model, whereas the Freundlich model was used for progesterone and norethisterone adsorption.

Performance of ozone and peroxone on the removal of endocrine disrupting chemicals (EDCs) coupled with cost analysis.

Micropollutants such as endocrine disruptors are one of the most important groups of chemicals polluting water resources. Conventional treatment systems may not be effective for the removal of endocrine disrupting chemicals (EDCs), and the fate of these chemicals should be carefully monitored in the effluent of wastewater treatment plants (WWTPs). Additional treatment methods such as advanced oxidation processes can be used for the removal of endocrine disruptors. This study presents the existence of endocrine disruptors in 4 different effluents: (i) municipal WWTP effluent, (ii) textile industry WWTP effluent, (iii) organized industrial zone (OIZ) WWTP effluent and (iv) pharmaceutical industry discharge and also presents their removal efficiencies by ozonation and peroxone oxidation. A broad spectrum of removal efficiencies was observed for the EDCs present in the samples since the oxidation efficiency of wastewaters containing EDCs mainly depends on the wastewater matrix and on the type of the EDCs. Ozonation was found to be a lower-cost option than peroxone oxidation at the investigated conditions.

Removal of endocrine disruptors in waters by adsorption, membrane filtration and biodegradation. A review

Rising anthropogenic activities have increased waste production and, in turn, the concentration of contaminants in waters. In particular, endocrine disruptors are natural and synthetic contaminants that cause many health problems. Endocrine disruptors bioaccumulate and alter the endocrine systems of both humans and wildlife. Endocrine disruptors are health hazards even at low concentrations. Their recalcitrant properties make the current water and wastewater management system inefficient for their removal. Hence, new removal methods need to be designed and employed. Here, we review alternative technologies for the removal of endocrine disruptors from aqueous matrices, with focus on adsorption, membrane separation and biodegradation. The efficiency, materials, methods, advantages and disadvantages of these treatments are analysed and compared. The main endocrine disruptors include parabens, bisphenols, phthalates, estradiols, nonylphenols and some pesticides.

Removal of the endocrine disruptors ethinyl estradiol, bisphenol A, and levonorgestrel by subsurface constructed wetlands.

The present work aimed to evaluate the removal efficiency of the endocrine disruptors ethinyl estradiol (EE2), the progestin levonorgestrel (LNG), and bisphenol A (BPA), considered to be contaminants of major concern, by using four laboratory scale constructed wetlands (CW) - three containing gravel as support media, one cultivated with Cyperus isocladus (WL1), other with Eichhornia crassipes (WL3), and one without macrophyte (WL2). The fourth unit contained gravel and bamboo charcoal as support medium, also cultivated with Cyperus isocladus (WLC). Two hydraulic retention times (HRT) were tested, 2 and 4 days. Average removals ranged from 9.0 to 95.6% for EE2, from 29.5 to 91.2% for BPA and from 39.1 to 100.0% for LNG. The results showed that the most efficient CW for removal of EE2 and BPA was WLC, and for LNG removal was WL3. The 2 days HRT was statistically more efficient in removing EE2, and the 4 days HRT was more efficient in the LNG removal. The other endocrine disruptors and concentration ranges were not influenced by HRT. It was concluded that WLC was the most suitable CW for removal of these three compounds, and it possibly is efficient also for the removal of other endocrine disruptors with similar physical-chemical characteristics.

A new approach to obtain mesoporous-activated carbon via hydrothermal carbonization of Brazilian Cerrado biomass combined with physical activation for bisphenol-A removal

The worrying hydric crisis and the increasing water contamination by emerging pollutants around the world stimulate the development of activated carbons (AC) for the removal of endocrine disruptors, including bisphenol-A (BPA). For this reason, a new approach for the synthesis of AC from hydrochar produced through hydrothermal carbonization (HTC) of Brazilian Cerrado biomass (Magonia pubescens–Sapindaceae) and physical activation using water vapor is highlighted. Compared to the traditional method of physical activation after pyrolysis, HTC was found to be better option to develop the specific surface area, porosity, and yield of the ACs, which presented mesoporous structure and carbon content higher than 80%. The BPA adsorption was evaluated by varying the contact time, BPA concentration, and pH. The Langmuir, Freundlich, and Redlich–Peterson isotherms were used to model the adsorption behavior. In the preliminary test to verify the adsorption efficiency, the AC obtained from hydrochar treated at 180 °C presented better results compared to commercial AC. The BPA adsorption data of the best treated hydrochar correlated well with the pseudo first-order model and the Langmuir isotherm (Qmax = 21.26 mg g−1). The results of the studies indicated the combination of HTC and physical activation with steam to be an efficient way to prepare an ecologically sound adsorbent for removal of Bisphenol-A from water with lower temperature and without chemical reagents. The ACs obtained can also be potential materials for other applications, such as in the field of catalysis and environmental remediation.

Determination and Removal of Endocrine Disruptors in Wastewater by Activated Carbon

Determination and Removal of Endocrine Disruptors in Wastewater by Activated Carbon

Removal of Endocrine Disruptors from Urban Wastewater by Advanced Oxidation Processes (AOPs): A Review

Over the last years the growing presence of endocrine disrupting compounds in the environment has been regarded as a serious sanitary issue. The more and more frequent detection of these compounds in the effluents of wastewater treatment plants poses the risk associated to their persistence into the aquatic systems as well as to their adverse effects on both public health and environment. As conventional systems do not allow their efficient removal, great attention has been raised towards their possible treatment by Advanced Oxidation Processes (AOPs). They rely on the action of hydroxyl radicals, which are highly reactive species, able to oxidize recalcitrant and non-biodegradable pollutants. AOPs can either provide contaminant partial degradation or their complete removal. As their effectiveness has been proved for a wide spectrum of both organic and inorganic pollutants, they are considered a suitable option for the treatment of contaminated aqueous media, especially when combined with conventional biological processes. This paper aims at reviewing main AOPs for the removal of endocrine disruptors, in order to highlight the most important features of different technologies, thus providing their comparative assessment. To this end, a brief overview of the most frequently detected endocrine disruptor compounds was also discussed, in order to clarify their fate into the environment as well as the contamination pathways of greatest concern for human health.

Removal of Endocrine Disruptors from Urban Wastewater by Advanced Oxidation Processes (AOPs): A Review

Removal of Endocrine Disruptors from Urban Wastewater by Advanced Oxidation Processes (AOPs): A Review

Continuous removal of endocrine disruptors by versatile peroxidase using a two-stage system.

The oxidant Mn(3+) -malonate, generated by the ligninolytic enzyme versatile peroxidase in a two-stage system, was used for the continuous removal of endocrine disrupting compounds (EDCs) from synthetic and real wastewaters. One plasticizer (bisphenol-A), one bactericide (triclosan) and three estrogenic compounds (estrone, 17β-estradiol, and 17α-ethinylestradiol) were removed from wastewater at degradation rates in the range of 28-58 µg/L·min, with low enzyme inactivation. First, the optimization of three main parameters affecting the generation of Mn(3+) -malonate (hydraulic retention time as well as Na-malonate and H2 O2 feeding rates) was conducted following a response surface methodology (RSM). Under optimal conditions, the degradation of the EDCs was proven at high (1.3-8.8 mg/L) and environmental (1.2-6.1 µg/L) concentrations. Finally, when the two-stage system was compared with a conventional enzymatic membrane reactor (EMR) using the same enzyme, a 14-fold increase of the removal efficiency was observed. At the same time, operational problems found during EDCs removal in the EMR system (e.g., clogging of the membrane and enzyme inactivation) were avoided by physically separating the stages of complex formation and pollutant oxidation, allowing the system to be operated for a longer period (∼8 h). This study demonstrates the feasibility of the two-stage enzymatic system for removing EDCs both at high and environmental concentrations.