E2 In Wastewater Research Articles

Molecularly Imprinted Polymers Electrochemical Sensing: The Effect of Inhomogeneous Binding Sites on the Measurements. A Comparison between Imprinted Polyaniline versus nanoMIP-Doped Polyaniline Electrodes for the EIS Detection of 17β-Estradiol.

Molecularly imprinted polymers (MIPs) are synthetic receptors made by template-assisted synthesis. MIPs might be ideal receptors for sensing devices, given the possibility to custom-design selectivity and affinity toward a targeted analyte and their robustness and ability to withstand harsh conditions. However, the synthesis of MIP is an inherently random process that produces a statistical distribution of binding sites, characterized by a variety of affinities. This is verified both for bulk MIP materials and for MIP's thin layers. In the present work, we aimed at assessing the effects of inhomogeneous versus homogeneous imprinted binding sites on electrochemical sensing measurements, and the possible implications on the sensor's performance. In the example of an Electrochemical Impedance Spectroscopy (EIS) sensor for the 17β-estradiol (E2) hormone, the scenario of inhomogeneous binding sites was studied by modifying electrodes with an E2-MIP polyaniline (PANI) thin layer, called the "Imprinted PANI layer". In contrast, the condition of discrete and uniform binding sites was epitomized by electrodes modified with a thin PANI layer purposedly doped with E2-MIP nanoparticles (nanoMIPs), which were referred to as "nanoMIP-doped PANI". The behaviors of the two EIS sensors were compared. Interestingly, the sensitivity of the nanoMIP-doped PANI was almost twice with respect to that of the imprinted PANI layer, strongly suggesting that the homogeneity of the binding sites has a fundamental role in the sensor's development. The nanoMIP-doped PANI sensor, which showed a response for E2 in the range 36.7 pM-36.7 nM and had a limit of detection of 2.86 pg/mL, was used to determine E2 in wastewater.

Molecular imprinting based sensor system developed using polymeric nanoparticles for detecting 17β‐estradiol in agricultural wastewater

AbstractMicro pollutants pose a significant issue in water ecosystems. Particularly high concentrations of 17β‐estradiol (E2) have been identified in agricultural wastewater, which poses harmful effects on aquatic organisms and disrupts ecosystem balance. Therefore, effective determination of E2 from water sources is crucial. This study developed a biosensor capable of detecting E2 in wastewater using specific polymer nanoparticle synthesis through molecular imprinting. Est‐imp‐poly(multi‐walled carbon nanotubes‐glycidyl methacrylate [MWCNT‐GMA]) polymer nanoparticles were synthesized using a surfactant‐free emulsion polymerization method, and their characterization was conducted using FTIR and scanning electron microscopy (SEM) technologies. The Qmax value for Est‐imp‐poly(MWCNT‐GMA) nanoparticles in a 1 mg/mL E2 solution was determined to be 140 ppm. Comparing adsorption capacities, the molecularly imprinted nanoparticles (MIP) showed nearly five times higher E2 adsorption compared to non‐imprinted polymers (NIP). The Est‐imp‐poly(MWCNT‐GMA)‐Nafion/screen‐printed electrode (SPE) system was employed for analyzing wastewater samples. The current measurements taken at various concentrations in the wastewater consistently matched the E2 concentration calibration curve. The limit of detection (LoD) and limit of quantification (LoQ) were determined to be 0.042 and 0.12 μM, respectively. The biosensor demonstrated a linear working range from 0.12 to 50 μM, with a high correlation coefficient (R2 = 0.9927). These results highlight the potential of the developed biosensor for detecting E2 in real samples.

Mechanism for removing 17beta-estradiol by bio-nanocomposite FJ1@rGO based on integration of adsorption and biodegradation

17beta-estradiol (E2) is classified as an endocrine disruptor and it poses a significant threat to the environment. Despite our previous work on the preparation of green-reduced graphene immobilized Ochrobactrum sp. FJ1(FJ1@rGO) to achieve high efficiency in removing E2, the functions of strain FJ1 and rGO, as well as their removal mechanism of E2, remain not well understood. In this study, FJ1@rGO was used to remove E2 to comprehend the removal mechanism where efficiency was found to be 93.74% after 10 days of removal compared to only rGO (43.82%). This indicated that E2 degradation was based on the integration of adsorption using rGO and biodegradation through strain FJ1, as evidenced by HPLC-UV. Additionally, results confirmed that the E2 removal process by FJ1@rGO conforms to first-order degradation kinetics and pseudo-second-order kinetics, further demonstrating the synergistic effect of physical adsorption and biodegradation. LC-Q/TOF-MS analysis identified the primary degradation products as estrone (E1), 4-OH-E1, and catechol. Combining characterization analysis, rGO facilitates the transfer of electrons between cells and E2, improving the strain's tolerance of environmental changes. Finally, the assessment of various wastewaters showed that the removal efficiency was 99.76%, 96.89%, and 78.09%, respectively. Overall, the mechanism by FJ1@rGO to remove E2 was proposed here, providing new insights into green and sustainable technology for treating E2 in wastewater.

Capture-SELEX of DNA Aptamers for Estradiol Specifically and Estrogenic Compounds Collectively.

Estrogenic compounds such as estrone (E1), 17β-estradiol (E2), and 17α-ethynylestradiol (EE2) are serious environmental contaminants due to their potent biological activities. At least six selections were previously reported to obtain DNA aptamers for E2, highlighting its environmental importance. A careful analysis revealed that the previous aptamers either are too long or do not bind optimally. Herein, a series of new aptamers were obtained from the capture-SELEX method with dissociation constants down to 30 nM as determined by isothermal titration calorimetry (ITC). Two aptamers were converted to structure-switching fluorescent biosensors, which achieved a limit of detection down to 3.3 and 9.1 nM E2, respectively. One aptamer showed similar binding affinities to all the three estrogens, while the other aptamer is more selective for E2. Both aptamers required Mg2+ for binding. The proposed sensors were successfully applied in the determination of E2 in wastewater. Moreover, comparisons were made with previous aptamers based on primary sequence alignment and secondary structures. Among previously reported truncated aptamers, ITC showed binding only in one of them. The newly selected aptamers have the combined advantages of small size and high affinities.

Electrochemical Sensor Based on Poly-L-Tyrosine/AuNCs/PDA-CNTs Nanocomposites for the Detection of 17β-Estradiol in Wastewater

Achieving direct electrochemical detection of 17β-estradiol (E2) at low concentrations remains a challenge due to the weak electrochemical activity of E2. In this study, we report a simple, cheap and sensitive electrochemical sensor based on nanocomposite for the direct detection of E2 in wastewater. The nanocomposite sensing electrode was developed by electrochemical in situ polymerization. Due to the π–π stacking and hydrogen bonding between poly-L-tyrosine (P(L-tyr)) with E2, we prepared P(L-tyr) electrode based on dopamine-modified multi-walled carbon nanotubes (PDA-CNTs) and gold nanoclusters (AuNCs). Then P(L-tyr)/AuNCs/PDA-CNTs/GCE sensing system was obtained. Meanwhile, the synergistic effect of fast electron transfer of AuNCs and the signal amplification effect of PDA-CNTs enables sensitive and direct detection of E2. The results showed that P(L-tyr)/AuNCs/PDA-CNTs/GCE sensor had a linear response to E2 concentration from 0.05 to 10 μmol·l−1 with a detection limit of 7.1 nmol·l−1. Then, the trace amount of E2 in pharmaceutical wastewater samples can be directly detected against several interferences from complex matrix, with recoveries from 91.0 to 107.5%. P(L-tyr)/AuNCs/PDA-CNTs/GCE showed good stability when placed at room temperature. Therefore, it can meet the requirements of the sensitive detection of E2 in complex matrix.

Removal of 17β-Estradiol Using Persulfate Synergistically Activated Using Heat and Ultraviolet Light

Among all female sex hormones, 17β-estradiol (E2) has been most often detected in discharge water from animal farms. The objectives of this study were to evaluate the performance of UV/heat-activated persulfate to degrade E2 and the technical feasibility to use this system for treating real wastewater. As an individual persulfate (PS) homogeneous activator, UV-activated PS removed E2 better than using low heat (40 °C) and solar irradiation to activate PS. When both UV and heat (25–65 °C) were used to activate PS, the Arrhenius equation represented well the observed rate constant, with activation energy of 118.07 kJ mol−1. Inorganic ion concentrations increased the degradation rate. These ions included Cl− (3500 mg L−1), which increased rates by 18.1%, HCO3− (250 mg L−1) by 4.6%, and NO3− (5 mg L−1) by 7.9%. However, lesser impacts on degradation kinetics were observed at higher concentrations for all constituents due to SO4·− scavenging by the formed radicals such as Cl2·−, Cl·, HCO3·, CO3·−, and NO3·. The E2 degradation observed rate constant (kobs) was highest at pH 3. Although both synthetic wastewater and real wastewater showed inhibitory effects due to UV blocking from turbidity and the existence of the –COOH and –OH functional groups that acted as radical scavengers, E2 degradation was still observed. The overall results provided proof-of-concept that UV/heat-activated PS can be applied to treat E2 in wastewater containing a high organic content and can minimize the chemical and operating costs, as solar irradiation provides the heating source.

Research on 17β-Estradiol Degradation Bacteria Isolated from Activated Sludge and its Degrade Characteristics

17β-estradiol(E2) has estrogenic activity at very low concentrations and are emerging as a major concern for water quality. Great endeavors have been done on the removal of E2 in wastewater. This article was mainly researched the isolated of E2 degradation bacteria from activated sludge and its degradation characteristics of the bacteria were also researched. According to its physiological biochemical results analysis, this strain was identified as K.pnem. pneumoniae .This strain can use E2 as sole carbon and energy source for growth. The optimal temperature, pH for the bacterial growth and degradation of E2 was 30°C,7.0, respectively, meanwhile degradation rate reached to 86% and 87%; degradation rate and bacterial growth increased along with E2 concentration increasing, 81% E2 was degraded when E2 concentration is 30mg/L, degradation rate decreased when E2>50mg/L; metal ions such as Fe2+ and Zn2+ almost have no effect on E2 degradation and bacterial growth; Mn 2+ can promote growth of strain and degradation, while, metal ions such as Hg2+ ,Ag+ ,Cu 2+ have negative effect on bacterial growth and degradation. The degradation process for E2 with initial concentration of 1mg/L indicated that the degradation rate of E2 by strain within 7days was 98%.

Development of a highly sensitive, second antibody format chemiluminescence enzyme immunoassay for the determination of 17β-estradiol in wastewater

In the present work, a highly sensitive chemiluminescence enzyme immunoassay (CLEIA) method for the determination of 17β-estradiol (E2) in the wastewater was developed, which used the fluorescein- iso-thiocyanate (FITC)–anti-FITC system as solid phase and the biotin–streptavidin system as signal amplification system, with the highly sensitive 4-methoxy-4-(3-phosphatephenyl)-spiro-(1,2-dioxetane-3,2′-adamantane) (AMPPD)–alkaline phosphatase (ALP) system as chemiluminescence detection system. The specific polyclonal antibody was produced against a conjugate of estradiol–bovine serum albumin (BSA), biotinoyl–diaminodioxaoctane–estradiol conjugate was synthesized. The specificity of anti-E2 antibody was also studied. The results showed that anti-E2 antibody has no cross-reactions for estriol, ethinyl E2, estrone commonly coexisting with E2 in the wastewater. Samples were prepared with solid-phase extraction using C 18 cartridges for the removal of matrix effects. The linear range was 2.5–1600 pg ml −1 and detection limit was 1.5 pg ml −1. As our known of knowledge, the method was more sensitive for the determination of E2 in water compared with other immunoassay methods. Recoveries were in the range of 80–110% in spiked tap water and wastewater. This method has been successfully used for the detection of E2 in wastewater, compared with the commercially radioimmunoassay (RIA) kit, the correlation was good.

Determination of Steroid Estrogens in Wastewater by Immunoaffinity Extraction Coupled with HPLC−Electrospray-MS

A new method, based on immunoaffinity extraction coupled with liquid chromatography/electrospray mass spectrometry (LC/ESI-MS) is described for the determination of the steroid estrogens beta-estradiol (E2), estrone (E1), and alpha-ethynylestradiol (E2) in wastewater. The use of highly selective immunosorbents in sample preparation prior to analysis allows the removal of interfering sample matrix compounds present in the wastewater extracts that would otherwise cause severe ionization suppression of the estrogens during the electrospray process. In addition, immunoextraction removes much of the isobaric noise from the selected ion monitoring chromatograms, increasing the signal-to-noise ratios for analytes, and contributing to the low detection limits (0.18 and 0.07 ng/L for E2 and E1, respectively) achieved by the current method. The method was applied to analysis of estrogens in two wastewater effluents. Recoveries of E2 and E1 were excellent (>90%), while the nonimmunogen (but structurally related) analyte EE2 was not retained (recovery <2%) from effluent extracts by the immunosorbent. This illustrates the extreme selectivity of the immunoextraction purification step. Precision of the method was high, with relative standard deviations below 5%. Concentrations of E2 in wastewater varied from 0.77 to 6.4 ng/L, while concentrations of E1 were greater (1.6-18 ng/L).