Endocrine Disrupting Chemicals In Water Research Articles

Cyano-functionalized porous hyper-crosslinked cationic polymers for efficient preconcentration and detection of phenolic endocrine disruptors in fresh water and fish

Sensitively analyzing phenolic endocrine-disrupting chemicals (EDCs) in environmental substrates and aquatic organisms provides a significant challenge. Here, we developed a novel porous hyper-crosslinked ionic polymer bearing cyano groups (CN-HIP) as adsorbent for the highly efficient solid phase extraction (SPE) of phenolic EDCs in water and fish. The CN-HIP gave an excellent adsorption capability for targeted EDCs over a wide pH range, and the adsorption capacity was superior to that of several common commercial SPE adsorbents. The coexistence of electrostatic forces, hydrogen bond, and π-π interactions was confirmed as the main adsorption mechanism. A sensitive quantitative method was established by coupling CN-HIP based SPE method with high-performance liquid chromatography for the simultaneously determining trace bisphenol A, bisphenol F, bisphenol B and 4-tert-butylphenol in fresh water and fish. The method afforded lower detection limits (S/N = 3) (at 0.03–0.10 ng mL−1 for water and 0.8–4.0 ng g−1 for fish), high accuracy (the recovery of spiked sample at 88.0%–112 %) and high precision (the relative standard deviation < 8.5 %). This work provides a feasible method for detecting phenolic EDCs, and also opens a new perspective in developing functionalized cationic adsorbent.

Distribution, migration patterns, and food chain human health risks of endocrine-disrupting chemicals in water, sediments, and fish in the Xiangjiang River

Exposure to endocrine-disrupting chemicals (EDCs) in freshwater systems has garnered increasing attention. A comprehensive analysis of the migration patterns, bioaccumulation, and consumer health risk of EDCs along the Xiangjiang River due to fish consumption from the river ecosystem was provided. Twenty natural and synthetic target EDCs were detected and analyzed from the water, sediments, and fish samples collected along the Xiangjiang River. There were significant correlations between the EDC concentrations in fish and the sediments. This revealed that EDCs in sediments play a dominant role in the uptake of EDCs by fish. The bioaccumulation factor and biota-sediment accumulation factor were calculated, with the highest values observed for nonylphenol. Pearson's correlation analysis showed that bisphenol A is the most reliable biological indicator of EDC contamination in fish. Furthermore, based on the threshold of toxicological concerns and the health risk with dietary intake, crucian carp and catfish from the Xiangjiang River pose a certain risk for children and pregnant women compared to grass carp. The Monte Carlo simulation results indicated a certain risk of cumulative ∑EDC exposure for local residents due to fish consumption.

Preparation of ionic porous polymers for extraction of four phenolic endocrine disrupting chemicals from fish and water samples

In this paper, series of ionic polymers were synthesized by crosslinking alkyl quaternary ammonium salts with 1,4-bis(chloromethyl)benzene. Among them, hyper-crosslinked polymer fabricated with dodecyl dimethyl benzyl ammonium chloride (HCP-DD) as monomer delivered superior adsorption performance for endocrine disrupting chemicals (EDCs). The adsorption mechanism mainly includes π-π stacking, hydrophobic and electrostatic interaction. With HCP-DD as solid phase extraction sorbent, a high performance liquid chromatography-diode array detection method was developed for the detection of four phenolic EDCs in water and fish samples. The detection limits of the method were 0.005–0.02 ng mL−1 for water samples and 3–30 ng g−1 for fish samples. The recoveries of EDCs in water samples and fish samples were 80–119% and 81.3–117% (relative standard deviations <4.4%), respectively. The study not only provides a route for preparation ionic porous polymers, but also highlights the applications of ionic polymers as efficient adsorbent to enrich organic pollutants.

Determination of four phenolic endocrine-disrupting chemicals in water by dispersive solid-phase extraction-ultra performance liquid chromatography-tandem mass spectrometry based on metal-organic skeleton porous carbon materials

Phenolic endocrine-disrupting chemicals (EDCs) are exogenous substances that interfere with the endocrine system and disrupt normal cell functions upon entering a living organism, leading to reproductive and developmental toxicity. Therefore, the development of a rapid and efficient analytical method for detecting phenolic EDCs in environmental waters is crucial. Owing to the low concentration of phenolic EDCs in environmental water, appropriate sample pretreatment methods are necessary to remove interferences caused by the sample matrix and enrich the target analytes before instrumental analysis. Dispersive solid-phase extraction (DSPE) has gained considerable attention as a simple and rapid sample pretreatment method for environmental-sample analysis. In this method, an adsorbent material is uniformly dispersed in a sample solution and the target analytes are extracted through processes such as vortexing. Compared with traditional solid-phase extraction (SPE), DSPE increases the contact area between the adsorbent and sample solution, reduces the required amounts of adsorbent and organic solvents, and improves the extraction efficiency. The adsorbent material plays a critical role in DSPE because it determines the extraction efficiency of the method. Metal-organic frameworks (MOFs) are porous framework materials composed of metal clusters and multifunctional organic ligands. They possess many excellent properties such as tunable pore sizes, large surface areas, and good thermal and chemical stability, rendering them ideal adsorbent materials for sample pretreatment. MOF-derived porous carbon materials obtained through high-temperature carbonization not only increase the density of MOF materials for better separation but also retain the advantages of a large surface area, highly ordered porous structure, and high porosity. In this study, a porous carbon material derived from an MOF, named as University of Oslo-66-carbon (UiO-66-C), was synthesized using a solvothermal method and applied as an adsorbent to enrich four phenolic EDCs (bisphenol A, 4-tert-octylphenol, 4-nonylphenol, and nonylphenol) in water. A method combining DSPE with ultra performance liquid chromatography-tandem mass spectrometry (UPLC-MS/MS) was established to analyze these phenolic EDCs in water. The UiO-66-C dosage, pH of water sample, adsorption time, eluent type and volume, elution time, and ion strength were optimized. Gradient elution was performed using methanol-water as the mobile phase. The target analytes were separated on an ACQUITY UPLC BEH C18 column (100 mm×2.1 mm, 1.7 μm), and multiple reaction monitoring (MRM) was conducted in negative electrospray ionization mode. The method exhibited a linear correlation within the range of 0.5-100 μg/L for the four phenolic EDCs. The limits of detection (LODs) and quantification (LOQs) of the four phenolic EDCs were 0.01-0.13 μg/L and 0.03-0.42 μg/L, respectively. The precision of the method was evaluated through intra- and inter-day relative standard deviations (RSDs), with values ranging from 1.5% to 10.6% and from 6.1% to 13.2%, respectively. When applied to the detection of phenolic EDCs in tap and surface water, the spiked recoveries of the four phenolic EDCs were 77.1%-116.6%. Trace levels of 4-nonylphenol and nonylphenol were detected in surface water at levels of 1.38 and 0.26 μg/L, respectively. The proposed method exhibits good accuracy and precision; thus, it provides a new rapid, efficient, and sensitive approach for the detection of phenolic EDCs in environmental water.

Sulfate-radicals Advanced Oxidation Processes by Biochar-based Catalysts and Applications in the Degradation of Endocrine Disrupting Chemicals in Wastewater: A Review

Increasing input of endocrine disrupting chemicals (EDCs) has been increasing rapidly nowadays. Various wastewater treatment technologies have been studied to remove EDCs in water and wastewater. Due to its high oxidation potential and other benefits over other tertiary wastewater treatments, the establishment of advanced oxidation processes based on sulfate radicals (SR-AOP) has been of attention in recent years. There are numerous activation methods to produce sulfate radicals from peroxymonosulfate (PMS) and peroxydisulfate (PDS) such as ultrasound, transition metals, and the use of carbon catalysts. This review manuscript focuses to provide the latest overview of different methods of PDS and PMS activation and different utilization of this technology focusing on water and wastewater treatment. Besides that, this article also focused on the utilization of carbon-based catalysts as a substitute for metal catalysts as an activator in the SR-AOP process. This review also aims to discuss the perspectives for the biochar-based catalyst application and expand their potential for removing organic pollutants.

Hydroxyl-rich carbon nitride microspheres with carbon doping for visible-light driven photocatalytic degradation of endocrine disrupting chemicals

Removal of endocrine-disrupting chemicals (EDCs) in water remains a big challenge and it is important to have an additional option to increase the degradation ability of the current water treatment system. In recent years, carbon nitride has demonstrated a potential application for photocatalytic degradation of EDCs in water. However, its performance is limited by restricted visible-light harvesting capacity and ready recombination of photogenerated charge carriers. In this work, hydroxyl-rich carbon nitride microspheres with carbon doping have been successfully synthesized through a simple one-step solvothermal method. The photocatalysts are characterized by XR, FT-IR, solid-state NMR, BET, SEM, UV-Vis DRS, XPS, Mott-Schottky plot, etc. Characterization results reveal that the as-prepared photocatalysts exhibit narrowed bandgap and faster separation of photogenerated charge carriers, allowing effective visible-light harvesting and improved performance in the photocatalytic degradation of EDCs. In addition, the band structures of the photocatalysts and degradation mechanisms of the EDCs are studied and postulated, elucidating that superoxide radicals are the main active species involved in the degradation process of the EDCs.

Removal of endocrine-disrupting chemical mixtures in water using chlorination and photolysis

Abstract Micropollutants have been continuously detected in freshwater. In parallel, the potential adverse effects of human exposure to endocrine-disrupting chemicals (EDCs) through drinking water have been gaining the attention of researchers and health authorities. Given this fact, this study aimed to evaluate the effectiveness of chlorination and photolysis to remove the estrogenic activity caused by mixtures of EDCs in water: estrone (E1: 100 ng L−1), 17β-estradiol (E2: 100 ng L−1), ethinylestradiol (EE2: 50 ng L−1), and nonylphenol (NP: 1,000 ng L−1) under operating conditions applicable for water treatment plants. The tests were performed using freshwater spiked with the following mixtures: E1 + E2, E1 + E2 + EE2, E1 + E2 + NP, and E1 + E2 + EE2 + NP). Removal efficiencies of up to 99.7% were achieved at a chlorine dose of 2.75 mg L–1 and 30 min of contact time. In photolysis, estrogenic activity removal was higher than 99.9% at a UV dose of 186 mJ cm–2. Results indicated that both chlorination and photolysis can be efficient to remove the estrogenic activity caused by the tested EDC mixtures in water. Furthermore, experiments suggested that EDC mixtures can be efficiently removed at feasible water disinfection operating conditions.

Mixed oxidation of aqueous nonylphenol and triclosan by thermally activated persulfate: Reaction kinetics and formation of co-oligomerization products

As two representative endocrine disrupting chemicals (EDCs), nonylphenol (NP) and triclosan (TCS) often coexist in water and wastewater. In this study, the mixed elimination of aqueous NP and TCS in thermally activated persulfate system was investigated in detail. The effects of the initial oxidant dosage, initial pH, and reaction temperature, as well as the presence of humic acid and coexisting anions and the water matrix on NP and TCS removal were evaluated. The results showed that the pseudo-first-order reaction rate constant of NP was higher than that of TCS in every case. In addition, the presence of TCS enhanced NP conversion, whereas the latter hindered the degradation of the former. A total of 23 intermediates were identified, and four pathways including hydroxylation, sulfate addition, cleavage of an ether bond and the single-electron coupling reaction were elucidated. Furthermore, numerous polymerization products formed by the self- and cross-coupling reactions of NP and TCS were discovered, and their abundance could be further improved under acidic conditions. Based on the density functional theory calculation, the energy barrier (ΔG) values of hydrogen atom extraction by OH from NP and TCS molecules to generate phenoxy radicals were just 4.37 and 12.70 kJ mol−1, respectively, which was significantly lower than those of the other reaction pathways. Combined with the results of quenching tests, we proposed a single-electron coupling reaction induced by OH as the dominant route in the mixed system. These findings can provide useful information for the elimination of mixed EDCs in water and wastewater.

Seasonal variation and the distribution of endocrine-disrupting chemicals in various matrices affected by algae in the eutrophic water environment of the pearl river delta, China

The seasonal variation and distribution among different matrices of endocrine-disrupting chemicals (EDCs) were investigated in the eutrophic water ecosystem of the Pearl River Delta, Guangdong, China. The chlorophyll a (Chl a) levels were generally higher in summer than in spring; however, the concentrations of 4-tert-octylphenol (OP), 4-nonylphenol (NP), and bisphenol A (BPA) in surface water were generally higher in spring (oligotrophic) than in summer (eutrophic). The levels of EDCs in SPM were lower in spring than in summer, a pattern seen in the seasonal variation of Chl a and particulate organic carbon (POC). The seasonal variations of EDCs in water bodies with different levels of eutrophication were analyzed in several dimensions including sediment, POC, algae and fish bile. The log Koc for SPM/water was higher in summer than in spring. The log Koc values for NP, OP, and BPA exhibited the following trends between matrices: colloid/water > sediment/water > SPM/water > algae/water, colloid/water > sediment/water > algae/water > SPM/water, and colloid/water > algae/water > sediment/water > SPM/water. The EDCs levels were different in fish tissues with the order bile > liver > muscle, with the concentrations being an order of magnitude higher in bile than in liver and an order of magnitude higher in liver than in muscle. The sequence of the bioconcentration factor (log BCF) for bile/water and liver/water was NP < OP < BPA in eutrophic conditions, but NP > OP > BPA in oligotrophic conditions. The order in eutrophic conditions was the same as the log BCF and log Koc for algae/water, indicating that the accumulation of EDCs in water bodies could be affected by algae, which could be one of the reasons of the seasonal variation of EDCs in water.

Synthesis of magnetic amino-functionalized microporous organic network composites for magnetic solid phase extraction of endocrine disrupting chemicals from water, beverage bottle and juice samples

In this work, the magnetic amino-functionalized microporous organic network composites (Fe3O4@MON-NH2) were rational designed and facile synthesized for magnetic solid phase extraction (MSPE) of endocrine disrupting chemicals (EDCs), followed by their analysis with high-performance liquid chromatography. The incorporation of amino groups (hydrogen bonding sites) into hydrophobic MON-NH2 networks led to their good enrichment for four typical EDCs bisphenol A (BPA), 4-alpha-cumylphenol (4-α-CP), 4-tert-octylphenol (4-t-OP) and 4-nonylphenol (4-NP) relying on the pre-designed hydrogen bonding, π-π and hydrophobic interactions. The combination of MON-NH2 shell and magnetic Fe3O4 core provided a fast extraction of BPA, 4-α-CP, 4-t-OP and 4-NP from matrix solution. Under the optimal conditions, the developed method offered good linearity (R2 > 0.990) in the range of 0.05–1000 μg L−1, low limits of detection (S/N = 3) of 0.015–0.030 μg L−1 and large enrichment factors of 172–197 for the studied EDCs. The maximum adsorption capacities of BPA, 4-α-CP, 4-t-OP and 4-NP were 124.1, 105.6, 116.6 and 117.9 mg g−1, respectively. The Fe3O4@MON-NH2 gave larger selectivity for other polar phenols than non-polar polycyclic aromatic hydrocarbons, revealing the dominant role of hydrogen bonding interaction during the extraction and the potential of Fe3O4@MON-NH2 for other polar phenols. The developed method was successfully applied for the analysis of EDCs in water, orange juice and beverage bottle samples with the recoveries of 80.3–109.5%. These results revealed the potential of functional MONs as efficient adsorbents in sample pretreatment.

Adsorptive Properties of Poly(1-methylpyrrol-2-ylsquaraine) Particles for the Removal of Endocrine-Disrupting Chemicals from Aqueous Solutions: Batch and Fixed-Bed Column Studies

The adsorptive properties of poly(1-methylpyrrol-2-ylsquaraine) (PMPS) particles were investigated in batch and column adsorption experiments as alternative adsorbent for the treatment of endocrine-disrupting chemicals in water. The PMPS particles were synthesised by condensing 3,4-dihydroxycyclobut-3-ene-1,2-dione (squaric acid) with 1-methylpyrrole in butanol. The results demonstrated that PMPS particles are effective in the removal of endocrine disrupting chemicals (EDCs) in water with adsorption being more favourable at an acidic pH, and a superior sorption capacity being achieved at pH 4. The results also showed that the removal of EDCs by the PMPS particles was a complex process involving multiple rate-limiting steps and physicochemical interactions between the EDCs and the particles. Gibbs free energy of −8.32 kJ/mole and −6.6 kJ/mol, and enthalpies of 68 kJ/mol and 43 kJ/mol, were achieved for the adsorption E2 and EE2 respectively The removal efficiencies of the EDCs by PMPS particles were comparable to those of activated carbon, and hence can be applied as an alternative adsorbent in water treatment applications.

Fabrication of a polymeric ionic liquid-based adsorbent for multiple monolithic fiber solid-phase microextraction of endocrine disrupting chemicals in complicated samples

A multiple monolithic fiber solid-phase microextraction (MMF-SPME) utilizing polymeric ionic liquid-based adsorbent was prepared. The adsorbent was obtained by in situ copolymerization of an ionic liquid, 1-trimethyl-(4-vinylbenzyl) aminium chloride and dual cross-linkers (divinylbenzene and ethylenedimethacrylate). The effect of preparation conditions including the content of ionic liquid and porogen in the polymerization mixture on extraction performance was studied in detail. Infrared spectroscopy, elemental analysis, scanning electron microscopy and mercury intrusion porosimetry were used to inspect the physicochemical properties of the new adsorbent. The applicability of the new MMF-SPME was demonstrated by the extraction of trace endocrine disrupting chemicals (EDCs). Results indicated that the prepared MMF-SPME could extract EDCs effectively through multi-interactions such as ion-exchange, π-π and hydrophobic interactions. After optimization of extraction parameters, a method of MMF-SPME coupled to high performance liquid chromatography/diode array detection was conducted to detect trace EDCs in complicated samples including environmental water and human urine. The limits of detection (S/N=3) and quantification (S/N=10) for targeted compounds were 0.011–0.065μg/L and 0.036–0.21μg/L, respectively. Satisfactory precision was also achieved by evaluating the repeatability and intermediate precision with relative standard deviations (RSDs) of less than 9% and 10%, respectively. At the same time, the proposed method was successfully applied for the determination of EDCs in water and human urine with spiking recoveries ranged from 70.6% to 119%.

Phenolic endocrine disrupting chemicals in an urban receiving river (Panlong river) of Yunnan–Guizhou plateau: Occurrence, bioaccumulation and sources

The objectives of this study were to track the occurrence, bioaccumulation and sources of phenolic endocrine disrupting chemicals (EDCs) in a representative urban river (Panlong River) of Yunnan–Guizhou Plateau. It provided more comprehensive fundamental data for risk assessment and contamination control of phenolic EDCs in aquatic environments. Phenolic EDCs, such as nonylphenol-di-ethoxylate (NP2EO), nonylphenol-mono-ethoxylate (NP1EO), 4-nonylphenol (4-NP), bisphenol A (BPA), 4-cumylphenol (4-CP) and 4-tert-octylphenol (4-t-OP), were ubiquitously present in Panlong River. The distribution of phenolic EDCs in the water and sediment tended to assume a shape like an inverted letter “W”. The residual levels of phenolic EDCs increased dramatically in certain areas. The concentrations of NP2EO, NP1EO, 4-NP, BPA, 4-CP, 4-t-OP and the total phenolic EDCs (ΣPEDCs) were up to 202, 154, 17, 79, 3.3, 4.6 and 429ng/L in water, and were up to 352, 316, 124, 18, 14, 4.8 and 813ng/g in sediment, respectively. However, the concentrations of 4-NP, BPA, 4-CP, 4-t-OP and ΣPEDCs in the three predominant fish species (Carassius auratus, Cyprinus carpio and Anabarilius alburnops) were up to 63, 113, 12, 14 and 201ng/g, respectively. Distribution characteristics of phenolic EDCs in water were significantly similar to those found in sediment, but different in fish. Occurrence, bioaccumulation and sources of phenolic EDCs were mainly subjected to the distribution characteristics of industry, agriculture and residential areas in Panlong catchment. Moreover, the bioconcentration factors (BCFs) were closely related to the octanol-water partition coefficients (logKow) of phenolic EDCs. Without direct input, the redissolution of phenolic EDCs from sediments seems conceivable. The concentrations of phenolic EDCs in the sections of urban areas were remarkably higher than those in suburban sections, since there could exist a potential risk to aquatic organisms and even to human.

Development and characterization of a nanodendritic silver-based solid-phase extraction sorbent for selective enrichment of endocrine-disrupting chemicals in water and milk samples

In this study, 4-[4-phenylazo-phenoxy] butyl-1-thiol (AzSH) functionalized nanodendritic silver (AzS@AgNDs) materials were prepared as a solid-phase extraction (SPE) sorbent for the selective extraction of estrogens. AzS@AgNDs possess an extremely large surface-to-volume ratio and a small average particle size. The performance of the material was evaluated by selective enrichment of hexestrol, diethylstilbestrol, dienestrol and bisphenol A in water and milk samples followed by rapid ultra-performance liquid chromatography–electrospray ionization mass spectrometry (UPLC–ESI–MS) analyses. The results exhibited that AzS@AgNDs had excellent adsorption capability for the targeted estrogens. The limits of detection of the four estrogens ranged from 0.1 to 5.0 pg/mL. The recoveries of the estrogens spiked into tap water were over the range of 83.6–105.3% with relative standard deviations of 2.8–6.0%. The results indicated the capability of this method for the rapid determination of estrogens in milk and other environmental water samples. In addition, this method would be useful for the determination of human exposure and health risk assessments trace level of endocrine-disrupting compounds (EDCs) in drinking water.

One-step site-specific modification of native proteins with 2-pyridinecarboxyaldehydes.

The chemical modification of proteins is an enabling technology for many scientific fields, including chemical biology, biophysics, bioengineering and materials science. These methods allow the attachment of strategically selected detection probes, polymers, drug molecules and analysis platforms. However, organic reactions that can proceed under conditions mild enough to maintain biomolecular function are limited. Even more rare are chemical strategies that can target a single site, leading to products with uniform properties and optimal function. We present a versatile method for the selective modification of protein N termini that does not require any genetic engineering of the protein target. This reaction is demonstrated for 12 different proteins, including the soluble domain of the human estrogen receptor. The function of this protein was confirmed through the binding of a fluorescent estrogen mimic, and the modified protein was explored as a prototype for the detection of endocrine-disrupting chemicals in water.

Development and characterization of magnetic molecularly imprinted polymers for the selective enrichment of endocrine disrupting chemicals in water and milk samples.

Analyses of four endocrine disrupting chemicals (EDCs) in water and milk samples were undertaken by using magnetic molecularly imprinted polymers (MMIPs). These were prepared via the surface molecular imprinting technique using super paramagnetic core-shell nanoparticle as support. Diethylstilbestrol (DES), which is a typical EDC, was employed as the template molecule. The obtained MMIPs were characterized using transmission electron microscope, Fourier transform infrared, X-ray diffraction, and vibrating sample magnetometer. Accordingly, the adsorption capacity and selectivity of prepared MMIPs were investigated. The binding isotherms were obtained for DES and fitted by the Freundlich isotherm model. A corresponding analytical method to determine four EDCs was developed. The recoveries of the spiked samples in pond water and pure milk range from 67.8 to 93.2% and from 65.3 to 92.5%, respectively. Coupled with high-performance liquid chromatography analysis, the prepared MMIPs were successfully applied to the analysis of EDCs in water and milk samples.

Occurrence and fate of selected endocrine-disrupting chemicals in water and sediment from an urban lake.

Occurrence of five endocrine-disrupting chemicals (EDCs)-bisphenol-A (BPA), triclosan (TCS), 17α-ethinyl estradiol (EE2), benzophenone-3, and 4-methylbenzylidene camphor-were monitored in East Lake, the largest urban lake in China. Other than EE2, all selected EDCs were detected at least once in the lake water with concentrations ≤89.1 ng/L. EDCs were detected with greater occurrence in spring than in other seasons. In lake sediment, TCS was detected at the greatest concentration (30.9 ng g(-1)), whereas BPA and EE2 were not detected. Spatial distribution of the EDCs in the lake water and the lake sediment showed similar patterns, and greater EDC residuals were found from those sites with known wastewater input. The linear adsorption coefficients (K d) varied from 17.9 to 1,017 L kg(-1) and were related to the octanol-water partition coefficient (K ow) values of the compounds. Photodegradation was a major process removing the EDCs from the lake water, and the presence of dissolved organic material and NO3 (-) in the lake water can accelerate the photodegradation process. Degradation of the EDCs in the lake sediment was relatively slow and occurred mainly due to the microbial processes. All compounds were found more persistent under anoxic conditions than under oxic conditions.

Removal of estrone (E1), 17β-estradiol (E2), and 17α-ethinylestradiol (EE2) from wastewater by liquid–liquid extraction

• Huge concerns about occurrence of endocrine disrupting chemicals (EDCs) in water. • EDCs have tendency to distribute to organic solvents. • Decamethylcyclopentasiloxane was effective to extract E1, E2 and EE2. • The distribution coefficients were not affected by pH up to pH 9.5. • Liquid–liquid extraction was effective to remove estrogenic potency from water. With the recent wide spread concerns of the environmental and public health effects of endocrine disrupting chemicals (EDCs), it is becoming important to develop new techniques to remove these substances from wastewater. EDCs find their way to the environment mainly via effluents from WWTPs. They are often cited as moderately hydrophobic, hence they have tendency to distribute to organic solvents and can then be removed using liquid–liquid extraction (LLE) techniques. However, despite being a mature chemical engineering unit operation, LLE has not been studied for the removal of EDCs in water. This study investigated the removal of three EDCs of concerns including estrone (E1), 17β-estradiol (E2), and 17α-ethinylestradiol (EE2) using decamethylcyclopentasiloxane (D5) as an extraction solvent in three water matrix types (Milli-Q, tap water, and a secondary treated wastewater). The study showed that all three EDCs were distributed to D5 but at varying distribution coefficients: K E1 = 2.66, K E2 = 0.61 and K EE2 = 1.67 ± 5% at pH 6 and 20 °C. Due to the high p K a values of the three EDCs, pH had no significant effect on K EDCs up to about pH 9.5 but higher pHs reduced the distribution ratios up to almost zero at pH 12. Van’t Hoff equation described the effect of temperature on K EDCs and showed that the process was endothermic. The overall estrogenic potency of the three EDCs in mixtures was quantified with an E2 equivalent potency, which was found to distribute well into the solvent at a K E2EQ = 1.43. The study suggests that LLE is an effective method to remove estrogenic potency of wastewater.

Occurrence and Partitioning of Phenolic Endocrine-Disrupting Chemicals (EDCs) Between Surface Water and Suspended Particulate Matter in the North Tai Lake Basin, Eastern China

Concentrations and distribution of octylphenol (OP), nonylphenol (NP), and bisphenol A (BPA) in surface water and suspended particulate matter (SPM) from the north Tai Lake basin, China were studied. Aqueous and particulate (dry weight) concentrations for OP, NP, and BPA varied from 10.5-1,175 ng/L to <1.52-5,365 ng/g, respectively. The spatial distribution of endocrine-disrupting chemicals (EDCs) in dissolved and particulate phases showed that the amount of EDCs in water that were adsorbed to SPM gradually increased from upstream to downstream. There were good correlations between particulate EDCs and particulate organic carbon, with correlation coefficients of 0.46-0.57. Regression analysis of in situ SPM-water partition coefficients (log K' oc) and log K ow for EDCs indicated that the hydrophobicity of chemicals greatly contributed to their SPM-water partitioning. Strong positive correlations (r = 0.68-0.82) among in situ log K' oc of OP, NP, and BPA and flow velocity of water were observed, indicating the critical importance of riverine hydrodynamics on the sorption of these compounds.

Development of Molecularly Imprinted Polymers – from Environmental Sensors to Biotechnology Applications

Many researchers have concentrated on the development of new methods for rapid determination of endocrine disrupting chemicals (EDCs) that are widely detected in environmental waters. Exposure to EDCs is associated with an earlier onset of puberty, decreased fecundity or fertility, altered sexual behavior, and increased incidence of abnormalities or cancers of the reproductive tract in humans [1]. The findings of a new study suggest that some endocrine disruptors may play a role in the obesity epidemic [2]. Direct determination of EDCs in water remains a challenging problem due to their low concentrations (ng/L to μg/L), which is further complicated by the presence of numerous other compounds (pharmaceuticals, personal care products, detergents and natural organic matter). Such matrix effects are formidable even when sophisticated instrumental techniques are used [3,4].