Simultaneous determination of 31 endocrine disrupting chemicals in fish plasma by solid-phase extraction coupled with ultra-performance liquid chromatography-tandem mass spectrometry.

Solid phase extraction combined with ultra-performance liquid chromatography-tandem mass spectrometry was developed for the simultaneous determination of 31 endocrine-disrupting chemicals in fish plasma. The strong anion exchange/primary-secondary amine cartridge and the mixed cation exchange cartridge were used in tandem instead of using a single mixed cation exchange cartridge for sample purification. Suitable eluents were selected for each of the two cartridges: 4.5% ammonia/acetonitrile solution for cartridges in tandem and acetone:n-hexane (V:V = 3:7) for the strong anion exchange/primary-secondary amine cartridge alone. With this optimized Solid phase extraction method, the recoveries of 31 endocrine disrupting chemicals were between 43.0% and 131.3%, the method detection limits were 0.45 to 1.35 ng/ml, and the limits of quantitation were 1.50-4.50 ng/ml. The innovative pretreatment method that connects two cartridges in tandem is well positioned to mitigate the matrix effects of fish plasma, thereby improving the accuracy of multiclass endocrine-disrupting chemicals determination. The significance of this method is to facilitate the application of the fish plasma model for the environmental risk assessment of endocrine-disrupting chemicals.

Correction to: Occurrence of 25 pharmaceuticals in Taihu Lake and their removal from two urban drinking water treatment plants and a constructed wetland.

The article Occurrence of 25 pharmaceuticals in Taihu Lake and their removal from two urban drinking water treatment plants and a constructed wetland, written by Xia-Lin Hu, Yi-Fan Bao, Jun-Jian Hu, You-Yu Liu and Da-Qiang Yin, was originally published electronically on the publisher's internet portal.

Simultaneous determination of 29 pharmaceuticals in fish muscle and plasma by ultrasonic extraction followed by SPE-UHPLC-MS/MS.

A confirmatory method for the simultaneous detection of 29 pharmaceuticals in fish muscle and plasma was developed by using solid-phase extraction combined with ultra-high performance liquid chromatography and tandem mass spectrometry. Fish samples were extracted with methanol and enriched using Oasis HLB solid-phase extraction columns in one step. Twenty-nine target pharmaceuticals were quantified by the internal standard method and the calibration curves showed good linearity in a wide range with determination coefficients of greater than 0.913. The detection limits of the pharmaceuticals ranged from 0.01 to 2.00 µg/kg (µg/L). The applicability of the method was checked by precision and recovery experiments. The average recoveries of the 29 pharmaceuticals were between 61 and 111%, and all the relative standard deviations were below 25%. Our reported method has been demonstrated to be sensitive, convenient, rapid, and reliable for the simultaneous determination of 29 pharmaceuticals in fish muscle and plasma. Real sample determination showed that 25 and 9 of the 29 compounds were detected in fish muscle and plasma, respectively.

Occurrence of 25 pharmaceuticals in Taihu Lake and their removal from two urban drinking water treatment plants and a constructed wetland.

Pharmaceuticals in drinking water sources have raised significant concerns due to their persistent input and potential human health risks. The seasonal occurrence of 25 pharmaceuticals including 23 antibiotics, paracetamol (PAR), and carbamazepine (CMZ) in Taihu Lake was investigated; meanwhile, the distribution and removal of these pharmaceuticals in two drinking water treatment plants (DWTPs) and a constructed wetland were evaluated. A high detection frequency (>70%) in the Taihu Lake was observed for nearly all the 25 pharmaceutics. Chlortetracycline (234.7 ng L-1), chloramphenicol (27.1 ng L-1), erythromycin (72.6 ng L-1), PAR (71.7 ng L-1), and CMZP (23.6 ng L-1) are compounds with both a high detection frequency (100%) and the highest concentrations, suggesting their wide use in the Taihu Basin. Higher concentrations of chloramphenicols, macrolides, PAR, and CMZP were observed in dry season than in wet season, probably due to the low flow conditions of the lake in winter and the properties of pharmaceuticals. The overall contamination levels of antibiotic pharmaceutics (0.2-74.9 ng L-1) in the Taihu Lake were lower than or comparable to those reported worldwide. However, for nonantibiotic pharmaceutics, PAR (45.0 ng L-1) and CMZP (14.5 ng L-1), significantly higher concentrations were observed in the Taihu Lake than at a global scale. High detection frequencies of 25 pharmaceuticals were observed in both the two DWTPs (100%) and the wetland (>60%) except for florfenicol and sulfapyridine. The removal efficacies of the studied pharmaceuticals in DWTP B with advanced treatment processes including ozonation and granular activated carbon filtration (16.7-100%) were superior to DWTP A with conventional treatment processes (2.9-100%), except for sulfonamides. Wetland C with the constructed root channel technology was efficient (24.2-100%) for removing most pharmaceuticals. This work suggests that the application of cost-effective technologies such as constructed wetlands should be considered as an efficient alternative for removing pharmaceuticals from water supply sources.

Simultaneous solid phase extraction coupled with liquid chromatography tandem mass spectrometry and gas chromatography tandem mass spectrometry for the highly sensitive determination of 15 endocrine disrupting chemicals in seafood.

This study aimed to develop a sensitive and reliable multi-residue method for the determination of trace amounts of endocrine disrupting chemicals including five phthalate esters (PAEs), five monoalky phthalate esters (MPEs), four alkylphenols (APs) and bisphenol A (BPA) in seafood. Ultrasonic liquid extraction was selected for extraction based on acetonitrile, instead of frequently-used n-hexane, due to its lower background of PAEs. Application of solid phase extraction (SPE) with primary secondary amine (PSA, 1g/6 mL) cartridge achieved the relatively low matrix effects for MPEs and BPA in seafood. To our knowledge, it is the first study reporting about simultaneous extraction and purification of PAEs, MPEs, APs and BPA in biota samples. To obtain the maximum sensitivity, both liquid chromatography tandem mass spectrometry (LC-MS/MS) and gas chromatography tandem mass spectrometry (GC-MS/MS) were applied for analysis. This method was validated and tested on fish, mollusk and prawn. Sufficient linearity was verified by Mandel's fitting test for the matrix-matched calibrations used in this study for MPEs, APs and BPA, between 0.5 ng/g and 200 ng/g or 400 ng/g. And correlation coefficients of all calibrations suppressed 0.99 for all analytes. Good recoveries were obtained, ranging from 60% to 127% for most compounds. The sensitivity was good with method detection limits (MDLs) of 0.015-2.2 ng/g wet weight (ww) for all compounds. Most MDLs are much lower than those in previous reports. The sensitive method was then applied on real fish, mollusk and prawn samples from the Yangtze River Delta sea area (China), and all the target compounds were detected with the maximum concentrations of PAEs, MPEs, APs and BPA up to 219.3 ng/g ww, 51.4 ng/g ww, 62.0 ng/g ww and 8.6 ng/g ww, respectively.

Synthesized magnetic nanoparticles coated zeolite for the adsorption of pharmaceutical compounds from aqueous solution using batch and column studies.

The contamination of fresh water with pharmaceutical and personal care products (PPCPs) has risen during the last few years. The adsorption of some PPCPs namely, Diclofenac-Na, Naproxen, Gemfibrozil and Ibuprofen from aqueous solution has been studied, magnetic nanoparticles coated zeolite (MNCZ) has been used as the adsorbent. Batch adsorption experiment was conducted to study the influences of different adsorption parameters such as contact time, solution pH and PPCPs concentrations in order to optimize the reaction conditions. The removal was favored at low pH values. Thus, as pH turns from acidic to basic conditions these compounds were less efficiently removed. The initial concentration does not appear to exert a noticeable effect on the removal efficiency of the studied PPCPs at low concentrations, but it showed less removal efficiency during high concentration of PPCPs especially for Ibuprofen. The removal of Diclofenac-Na was independent on time, while the contact time was of significant effect on the adsorption of Naproxen, Gemfibrozil and Ibuprofen even though these compounds were removed up to 95% during 10 min using MNCZ. From the isotherm adsorption study, the adsorption of PPCPs studied on MNCZ was best fitted with Freundlich isotherm equation. Pseudo-second order model providing the best fit model with the experimental data. Column adsorption study was conducted to compare the removal efficiency of MNCZ with other processes used at drinking water treatment plants (DWTPs), MNCZ showed high removal efficiency (>99%) than other used processes at DWTPs.

The distributions, removals and estrogenic effects of selected endocrine disrupting chemicals in two drinking water factories in China.

The distributions and effects of 31 selected endocrine disrupting chemicals (EDCs) in two drinking water factories were analyzed in this study. The distributions of EDCs were analyzed by solid phase extraction (SPE) combined with liquid chromatography tandem mass spectrometry (LC-MS/MS). The concentrations of these EDCs were from lower than the LOD (limit of detection) to 23.13 ng L (- 1) in the samples; most of them were lower than 1 ng L (- 1). The highest concentration (23.13 ± 1.45 ng L (- 1)) was detected in the raw water. Twenty-six chemicals were found in the raw water and only five in the finished water of drinking water factory A, while 25 chemicals were detected in the raw water and two in the finished water of drinking water factory B. The results indicate that most of the EDCs can be removed by the water treatment process. In the advanced treatment process, the ozonation processes have the highest removal efficiency. Separate analyses in May and September show similar results. Apart from the chemical analysis, yeast strain transformed when the estrogen receptor α (ERα) gene was employed to test the estrogenic effects of the water samples. Due to the low concentrations of these EDCs, no significant estrogenic effects were found from the samples.

MCX based solid phase extraction combined with liquid chromatography tandem mass spectrometry for the simultaneous determination of 31 endocrine-disrupting compounds in surface water of Shanghai.

A novel analytical method employing MCX (mixed-mode cationic exchange) based solid phase extraction (SPE) coupled with liquid chromatography tandem mass spectrometry (LC-MS/MS) was developed to detect 31 endocrine-disrupting compounds (EDCs) in surface water samples simultaneously. The target EDCs belong to five classes, including seven estrogens, eight androgens, six progesterones, five adrenocortical hormones and five industrial compounds. In order to simultaneously concentrate the target EDCs and eliminate matrix interferences in the water samples, MCX SPE cartridges were employed for SPE, and then followed by a simple and highly efficient three-step sequential elution procedure. Two electrospray ionization (ESI) detection modes, positive (ESI+) and (ESI-), were optimized for HPLC-MS/MS analysis to obtain the highest sensitivity for all the EDCs. The limits of detection (LODs) were 0.02-1.9 ng L(-1), which are lower than or comparable to these reported in references. Wide linear ranges (LOD-100 ng L(-1) for ESI+ mode, and LOD-200 ng L(-1) for ESI- mode) were obtained with determination coefficients (R(2)) higher than 0.99 for all the compounds. With five internal standards, good recoveries (84.4-103.0%) of all the target compounds were obtained in selected surface water samples. The developed method was successfully applied to investigate the EDCs occurrence in the surface water of Shanghai by analyzing surface water samples from 11 sites. The results showed that nearly all the target compounds (30 in 31) were present in the surface water samples of Shanghai, of which three industrial compounds (4-t-OP, BPA, and BPF) showed the highest concentrations (median concentrations were 11.88-23.50 ng L(-1)), suggesting that industrial compounds were the dominating EDCs in the surface water of Shanghai, and much more attention should be paid on these compounds. Our present research demonstrated that SPE with MCX cartridges combined with HPLC-MS/MS was convenient, efficient and reliable for multiclass analysis of EDCs in surface water.

Development of molecular docking-based binding energy to predict the joint effect of BPA and its analogs.

A general proposal for predicting the joint effect of endocrine disrupting chemicals by examining binding energy models was developed in this study. 2,2-bis(4-hydroxyphenyl)propane (BPA) and 11 of its analogs were chosen, and the estrogenic activity of each compound was measured by determining its EC50 value using a recombinant gene yeast assay. Binding energies (BEs) were calculated using Surflex-Docking software. The analysis of the relationship between EC50 values and BEs showed that there is a linear correlation between the BEs and EC50 values. Furthermore, the analysis of the given binary and quaternary mixtures of BPA and three of its analogs showed that the joint effects of the mixtures were affected by the proportions of the chemicals in each mixture and their relative binding energy. The correlation between the joint effects of mixtures and the binding energy of the individual compounds has been described using one formula, which can be used to predict the joint effects of other mixtures.

Hollow fiber supported ionic liquid membrane microextraction for determination of sulfonamides in environmental water samples by high-performance liquid chromatography.

By using ionic liquid as membrane liquid and tri-n-octylphosphine oxide (TOPO) as additive, hollow fiber supported liquid phase microextraction (HF-LPME) was developed for the determination of five sulfonamides in environmental water samples by high-performance liquid chromatography with ultraviolet detection The extraction solvent and the parameters affecting the extraction enrichment factor such as the type and amount of carrier, pH and volume ratio of donor phase and acceptor phase, extraction time, salt-out effect and matrix effect were optimized. Under the optimal extraction conditions (organic liquid membrane phase: [C(8)MIM][PF(6)] with 14% TOPO (w/v); donor phase: 4mL, pH 4.5 KH(2)PO(4) with 2M Na(2)SO(4); acceptor phase: 25microL, pH 13 NaOH; extraction time: 8 h), low detection limits (0.1-0.4microg/L, RSDor=0.999) were obtained for all the analytes. The presence of humic acid (0-25mg/L dissolved organic carbon) and bovine serum albumin (0-100microg/mL) had no significant effect on the extraction efficiency. Good spike recoveries over the range of 82.2-103.2% were obtained when applying the proposed method on five real environmental water samples. These results indicated that this present method was very sensitive and reliable with good repeatabilities and excellent clean-up in water samples. The proposed method confirmed hollow fiber supported ionic liquid membrane based LPME to be robust to monitoring trace levels of sulfadiazine, sulfamerazine, sulfamethazine, sulfadimethoxine and sulfamethoxazole in aqueous samples.

Ionic liquids in sample preparation.

Due to their unique properties, their good extractabilities for various target analytes, and the fact that many compounds are highly soluble in them, room-temperature ionic liquids (ILs) are used as promising alternatives to the traditional organic solvents employed in sample preparation. ILs have been used as extraction solvents for a wide range of analytes, from environmental contaminates to biomacromolecules and nanomaterials, and as dissolution solvents for various detection techniques. In this paper, the main applications of ILs in sample preparation are reviewed, and the problems and challenges in this area are described.

Direct determination of chlorophenols in environmental water samples by hollow fiber supported ionic liquid membrane extraction coupled with high-performance liquid chromatography.

The 1-octyl-3-methylimidazolium hexafluorophosphate ([C8MIM][PF6]) ionic liquid was immobilized in the pores of a polypropylene hollow fiber for hollow fiber-protected liquid-phase microextraction. Analytes including 4-chlorophenol (4-CP), 3-chorophenol (3-CP), 2,4-dichlorophenol (2,4-DCP) and 2,4,6-trichlorophenol (2,4,6-TCP) were extracted into this ionic liquid membrane, and back extracted into 10microL sodium hydroxide acceptor solution in the lumen of the hollow fiber. Then, the acceptor solution was withdrawn into the high-performance liquid chromatography (HPLC) microsyringe connected to the hollow fiber, and directly injected into the HPLC system for analysis. Some parameters that might affect the extraction efficiency were optimized, and low detection limits (0.5microgL(-1) for 4-CP, 3-CP, DCP and 1.0microgL(-1) for TCP) were obtained. Good repeatability was achieved because of the stability of the hollow fiber-supported ionic liquid membrane. The proposed procedure was applied for direct determination of the four chlorophenols in some real water samples including groundwater, river water, wastewater and tap water. All of the four chlorophenols in these water samples were under the limits of determination, and the recoveries were in the range of 70.0-95.7% at 5microgL(-1) spiked level.

Equilibrium sampling of freely dissolved alkylphenols into a thin film of 1-octanol supported on a hollow fiber membrane.

A new negligible depletion extraction procedure was proposed for equilibrium sampling of 4-tert-octylphenol (OP) and 4-nonylphenol (NP) into a thin film of 1-octanol supported on a hollow fiber membrane. This thin liquid film extraction technique was directed at the determination of (1) freely dissolved concentrations, (2) distribution coefficients to 1-octanol (D(ow)), and (3) binding to dissolved organic matter (DDOC). The sampling device was prepared by dipping pieces of polypropylene microporous hollow fiber membrane (10-mm length, 30-microm wall thickness, 240-microm inner diameter) into 1-octanol for a few seconds to impregnate the pores of the hollow fiber wall. After stirring in 100 mL of sample solution for 24 h, the sampling device was harvested and desorbed with 30 microL of methanol, of which 20 microL was injected for HPLC analysis. With the measured D(ow) of a chemical and its equilibrium concentration in the 1-octanol sampling phase (C(octanol)), the freely dissolved concentration (Cfree) was calibrated based on Cfree = C(octanol)/D(ow). Measured log Dow values of OP (4.32 +/- 0.06) and NP (4.79 +/- 0.02) were independent of the chemical concentration, only minimally affected by the environmentally relevant pH, buffering capacity, and salinity of samples, and agreed well with reported values. Log DDOC values of OP (4.89 +/- 0.43) and NP (5.14 +/- 0.37), determined in Aldrich humic acid solution, agreed with reported partition coefficients to organic carbon (log Koc) for particles in river water and effluent wastewater. Short equilibration times and high enrichment factors were obtained for both analytes due to the high surface to volume ratio of the new sampler. The technique was successfully applied to determine Cfree of OP and NP in real water samples and to study their association with humic acids and bovine albumin.

Evaluating the impacts of some environmentally relevant factors on the availability of bisphenol A with negligible-depletion SPME.

The effect of some environmentally relevant factors including salinity, pH, and humic acids on the availability of bisphenol A (BPA) was evaluated by using the negligible-depletion solid-phase microextraction (nd-SPME) biomimetic method. With the variation of salinity (0-500 mM NaCl) and pH (5.0-8.5) of aqueous solutions, the partition coefficients of BPA between the nd-SPME fiber and the aqueous solution varied in the range of logD=3.55-3.86, which indicates that the salinity and pH can influence the availability of BPA. By using Acros humic acid as model dissolved organic matter (DOM), it was also demonstrated that the environmental factors such as salinity and pH could affect the partitioning of BPA between DOM and aqueous solutions. The determined partition coefficients of BPA between dissolved organic carbon (DOC) and aqueous solutions were in the range of logD(DOC)=4.03-5.60 for Acros humic acid solutions with 1-50 mg l(-1) DOC. The influence of salinity and pH on logD(DOC) was more significant at low concentration (0-5 mg l(-1)) of DOC.