Preparation of alumina-coated magnetite nanoparticle for extraction of trimethoprim from environmental water samples based on mixed hemimicelles solid-phase extraction

In this study, a new type of alumina-coated magnetite nanoparticles (Fe₃O₄/Al₂O₃ NPs) modified by the surfactant sodium dodecyl sulfate (SDS) has been successfully synthesized and applied for extraction of trimethoprim (TMP) from environmental water samples based on mixed hemimicelles solid-phase extraction (MHSPE). The coating of alumina on Fe₃O₄ NPs not only avoids the dissolving of Fe₃O₄ NPs in acidic solution, but also extends their application without sacrificing their unique magnetization characteristics. Due to the high surface area of these new sorbents and the excellent adsorption capacity after surface modification by SDS, satisfactory concentration factor and extraction recoveries can be produced with only 0.1 g Fe₃O₄/Al₂O₃ NPs. Main factors affecting the adsolubilization of TMP such as the amount of SDS, pH value, standing time, desorption solvent and maximal extraction volume were optimized. Under the selected conditions, TMP could be quantitatively extracted. The recoveries of TMP by analyzing the four spiked water samples were between 67 and 86%, and the relative standard deviation (RSD) ranged from 2 to 6%. Detection and quantification limits of the proposed method were 0.09 and 0.24 μg L⁻¹, respectively. Concentration factor of 1000 was achieved using this method to extract 500 mL of different environmental water samples. Compared with conventional SPE methods, the advantages of this new Fe₃O₄/Al₂O₃ NPs MHSPE method still include easy preparation and regeneration of sorbents, short times of sample pretreatment, high extraction yields, and high breakthrough volumes. It shows great analytical potential in preconcentration of organic compounds from large volume water samples.     

Preparation of a chitosan-coated C18-functionalized magnetite nanoparticle sorbent for extraction of phthalate ester compounds from environmental water samples

Novel superparamagnetic chitosan-coated C₁₈-functionalized magnetite nanoparticles (MNPs) were successfully synthesized and applied as an effective sorbent for the preconcentration of several typical phthalate ester compounds from environmental water samples. The MNPs were 20 nm in diameter and had a high magnetic saturation value (52 emu g⁻¹), which endowed the sorbent with a large surface area and the convenience of isolation from water samples. Phthalate esters could be extracted by the interior octadecyl groups through hydrophobic interaction. The hydrophilic porous chitosan polymer coating promoted the dispersion of MNPs in water samples, and improved the anti-interference ability of the sorbent without influencing the adsorption of analytes. The main factors affecting the adsorption of phthalate esters, including the pH of the solution, humic acid, sample loading volume, adsorption time, and desorption conditions, were investigated and optimized. Under the conditions selected (pH 11, adsorption time 20 min, elution with 10 mL of acetonitrile, and concentration to 0.5 mL), concentration factors of 1,000 were achieved by extracting 500 mL of several environmental water samples with 0.1 g of MNP sorbent. The method detection limits obtained for di-n-propyl phthalate, di-n-butyl phthalate, dicyclohexyl phthalate, and di-n-octyl phthalate were 12.3, 18.7, 36.4, and 15.6 ng L⁻¹, respectively. The recoveries of spiked samples ranged from 60 to 100%, with a low relative standard deviation (1–8%), which indicated good method precision.     

Extraction of phenolic compounds from environmental water samples using oil-in-water emulsions

A fast, sensitive and simple oil-in-water emulsion (OWE) method was developed for extraction of four phenolic pollutants in environmental water samples followed by gas chromatography and flame ionization detection. In this method, the density of a binary organic solvent (one heavier and one lighter than the sample) was balanced with the density of the sample solution. A stable emulsion was formed at room temperature under vigorous stirring using a Teflon-coated magnetic stirring bar. After addition of 10 µL of the heavier organic solvent and centrifugation, phase separation occurred. The influence of several important parameters on the extraction efficiency of phenolic compounds was evaluated. Under optimized experimental conditions, the calibration graphs were linear in the concentration range 0.025–20 mg L^?1 with coefficients of determination more than 0.9994. The limits of detection and quantification were in the range 19.2–76.0 and 64.1–251.0 μg L^?1, respectively. Intra-day and inter-day precisions were less than 5.0 %. The procedure was used for the determination of phenolic compounds in spiked water samples with good results. Recoveries range from 96.5 to 103.0%, and relative standard deviations are <2.5% (for n?=?3).     

Preparation of functionalized magnetic nanoparticulate sorbents for rapid extraction of biphenolic pollutants from environmental samples

A new solid-phase extraction coupled with magnetic carrier technology was developed for extraction of bisphenol A (BPA) and diethylstilbestrol (DES) from water samples. The SPE sorbents, functionalized magnetic nanoparticles (Fe₃O₄@SiO₂/β-CD, core/shell), were synthesized in a two-stage system. The material was characterized by Fourier transform infrared spectroscopy, transmission electron microscopy, and a vibrating sample magnetometer. SPE extraction parameters, such as volume and pH of sample, adsorption time, and desorption conditions were optimized. Under selected conditions: 250 mL of water sample, 0.1 g of sorbents and elution with methanol (3 mL with 1% acetic acid), the extraction was completed in 25 min. SPE followed by HPLC was employed to determine BPA and DES in environmental samples. The developed method provided spiked recoveries of 80–105%, relative standard deviations of less than 7%, and LOD of BPA (20.0 ng/L) and DES (23.0 ng/L), respectively. The proposed method offered easy preparation of sorbents, rapid analysis, high enrichment yields, and reliable quantitative assay.     

Preparation of cyano-functionalized multiwalled carbon nanotubes as solid-phase extraction sorbent for preconcentration of phenolic compounds in environmental water

In the present work, we showed a novel method to synthesize cyano-functionalized multiwalled carbon nanotubes (MWCNTs-CN) and utilize it as a solid-phase extraction sorbent for preconcentration of phenolic compounds in environmental water samples. MWCNTs-CN was synthesized through surface functionalization of multiwalled carbon nanotubes (MWCNTs). The functional groups on the surface of modified MWCNTs were characterized by Fourier transform infrared spectroscopy, thermogravimetric analysis and scanning electron microscopy. The analytical procedure was based on a conventional solid-phase extraction step for which 100 mg of MWCNTs-CN were packed in a 3 mL polypropylene cartridge. Analytes were thus isolated and preconcentrated from the pretreated samples and subsequently detected on high-performance liquid chromatography-ultraviolet detection. The results showed the proposed method exhibited good sensitivity and precision for the extraction and elution of analytes. The limit of detections (S/N = 3) of the method were 0.45, 0.09, 0.08, and 3.00 ng mL(-1) for p-chlorophenol, 1-naphthol, 2-naphthol, and 2,4-dichlorophenol, respectively. The mean relative recoveries (n = 3) were between 80.28 and 103.13%, and the repeatability (RSD ≤ 5.10%) and reproducibility (RSD ≤ 7.68%) were accepted. This developed method was applied to determine phenolic compounds in environmental water samples. There is a positive result only for 2-naphthol with concentration of 0.38 ng mL(-1) in seawater sample.     

Method for rapid tritiated water extraction from environmental samples

We have developed a thermal vacuum desorption process to rapidly extract water from environmental samples for tritium analysis. Thermal vacuum desorption allows for extraction of the moisture from the sample within a few hours in a form and quantity suitable for liquid scintillation counting and allows detection of tritium at the levels of <2 Bq/l of milk, <0.5 Bq/g of vegetation, and <0.5 Bq/g of soil. We developed a prototype unit that can process batches of twenty or more samples within 24 hours. Early data shows that a high percentage of water is extracted reproducibly without enrichment or depletion of the tritium content. The quench coefficient of the extracted water is low allowing for accurate, direct liquid scintillation counting. In most samples, good comparison has been observed with results using freeze-dry lyophilization as the water extraction method     

Two polydimethylsiloxane rod extraction methods for the sensitive determination of phenolic compounds in water samples

Simple, precise, and low‐cost methods for the simultaneous determination of phenolic endocrine disrupting compounds such as bisphenol A, trichlorophenol, pentachlorophenol, 4‐nonylphenol, and 4‐octylphenol in water samples were developed. The Direct, in situ derivatization methods are based on polydimethylsiloxane rod extraction followed by liquid desorption and chromatographic analysis by liquid chromatography and diode array detection. Several parameters affecting the extraction and desorption of the phenolic compounds and their acetylated derivates were studied, as well as the chromatographic and detection conditions. For the direct method, determination coefficients (r²) > 0.990 and LODs in the 0.6–2 μg/L range were obtained for all compounds except bisphenol A (9.5 μg/L). With the derivatization‐based method, based on in situ acetylation, lower limits of detection (0.3–0.9 μg/L) were obtained for all the compounds with r² > 0.988 and RSDs in the 2–9% range. The developed methods were applied to the analysis of spiked water samples obtaining recoveries of between 60.2 and 131.7% for the direct method, and of between 76.6 and 108.2% for the derivatization‐based method. The results demonstrate the feasibility of using these two methods for determining bisphenol A, trichlorophenol, pentachlorophenol, 4‐nonylphenol, and 4‐octylphenol in water.     

Preparation of a graphene-based magnetic nanocomposite for the extraction of carbamate pesticides from environmental water samples

A graphene-based magnetic nanocomposite was synthesized and used for the first time as an effective adsorbent for the preconcentration of the five carbamate pesticides (metolcarb, carbofuran, pirimicarb, isoprocarb and diethofencarb) in environmental water samples prior to high performance liquid chromatography-diode array detection. The properties of the magnetic nanocomposite were characterized by scanning electron microscopy and X-ray diffraction. This novel graphene-based magnetic nanocomposite showed great adsorptive ability towards the analytes. The method, which takes the advantages of both nanoparticle adsorption and magnetic phase separation from the sample solution, could avoid some of the time-consuming experimental procedures related to the traditional solid phase extraction. Various experimental parameters that could affect the extraction efficiencies have been investigated. Under the optimum conditions, the enrichment factors of the method for the analytes were in the range from 474 to 868. A linear response was achieved in the concentration range of 0.1-50 ng mL(-1). The limits of detection of the method at a signal to noise ratio of 3 for the pesticides were 0.02-0.04 ng mL(-1). Compared with the dispersive liquid-liquid microextraction and the ultrasound-assisted surfactant-enhanced emulsification microextraction, much higher enrichment factors and sensitivities were achieved with the developed method. The method has been successfully applied for the determination of the carbamate pesticides in environmental water samples.     

Hemimicelle-based solid-phase extraction of estrogens from environmental water samples

Hemimicelles and admicelles of sodium dodecyl sulfate (SDS) on alumina and cetyltrimethyl ammonium bromide (CTAB) on silica were evaluated for the concentration and purification of the priority estrogens estrone (E(1)), 17beta-estradiol (E(2)) and ethynylestradiol (EE(2)) from sewage and river samples. Retention was based on analyte-sorbent hydrophobic and cation-pi interactions. Parameters affecting the SPE of estrogens on both types of sorbents were comparatively investigated. Adsolubilization was quantitative for SDS hemimicelles/admicelles and CTAB admicelles. SDS hemimicelle-coated alumina was the sorbent selected on the basis of the lower elution volume required and the higher sample flow rate allowed. Combination of estrogen adsolubilization-based SPE with liquid chromatography-diode array/fluorescence detection permitted the quantification of the target compounds with detection limits ranging from 20 to 100 ng l(-1). The relative standard deviation ranged from 3 to 8%. The approach developed was applied to the determination of estrogens in raw and treated sewage and river samples. The recovery found for estrogens in these environmental matrices was between 85 and 105%.     

Extraction of phenolic compounds from water samples by dispersive micro‐solid‐phase extraction

In this article, the use of magnetically separable sorbent polyaniline/silica‐coated nickel nanoparticles is evaluated under a dispersive micro‐solid‐phase extraction approach for the extraction of phenolic compounds from water samples. The sorbent was prepared by in situ chemical polymerization of aniline on the surface of silica‐modified nickel nanoparticles and was characterized by Fourier transform infrared spectroscopy, transmission electron microscopy, X‐ray powder diffraction, scanning electron microscopy, energy‐dispersive X‐ray spectrometry, and vibrating sample magnetometry. Effective variables such as amount of sorbent (milligrams), pH and ionic strength of sample solution, volume of eluent solvent (microliters), vortex, and ultrasonic times (minutes) were investigated by fractional factorial design. The significant variables optimized by a Box–Behnken design were combined by a desirability function. Under the optimized conditions, the calibration graphs of analytes were linear in a concentration range of 0.02–100 μg/mL, and with correlation coefficients more than 0.999. The limits of detection and quantification were in the ranges of 10–23 and 33–77 μg/L, respectively. This procedure was successfully employed in the determination of target analytes in spiked water samples; the relative mean recoveries ranged from 96 to 105%.     

Preparation of polymer based sorbents for solid phase extraction of polyphenolic compounds

This article discusses the preparation of different polymeric sorbents for solid phase extraction. Various monomers like acrylamide, methacrylic acid and 4-vinylpyridine (VP), cross-linkers such as divinylbenzene (DVB) and ethyleneglycoldimethacrylate (EDMA), porogens like tetrahydrofuran (THF) and dimethylsulphoxide (DMSO) / acetonitrile (ACN) with different ratios were investigated in order to optimize recoveries. Resulting polymers were characterized through scanning electron microscope (SEM) and compared with Oasis HLB (Waters, MA, USA) and Strata-X (Phenomenex, Torrance, USA) on the basis of extraction performance, recovery efficiency and loading capacity. Sample applied was a mixture of flavonoid standards (rutin, myricetin, luteolin, quercetin, apigenin and kaempferol). HPLC hyphenated with PDA was used for the analysis of samples. Results showed that among the prepared SPE materials, 4-VP-co-EDMA produced best results. Comparison of the produced polymers with of Oasis HLB and Strata-X resulted in comparable efficiencies; especially the polymer 4-VP-co-EDMA gave almost similar results for all analytes to those of commercially available SPE materials. A general trend of decrease in retention efficiency with increase in polarity has been observed in both synthesized and already available SPE materials. The newly synthesized polymeric materials can be employed as SPE sorbents for efficient extraction of polyphenolic compounds especially for flavonoid aglycons.     

Preparation of flower-like molybdenum disulfide for solid-phase extraction of N-nitrosoamines in environmental water samples

In this paper, a flower-like molybdenum disulfide material was prepared by hydrothermal method and was first used as adsorbents in the solid-phase extraction process for enriching N-nitrosoamines. Molybdenum disulfide exhibited three-dimensional petal-like microspheres with about 500 nm in diameter. The relevant analyte extraction and elution parameters (sample volumes, solution pH, washing solvents, elution solvents, and elution volumes) were optimized to improve the solid-phase extraction efficiency. The solid-phase extraction process coupled with high-performance liquid chromatography-tandem mass spectrometry for determining N-nitrosoamines in environmental water samples was established. The limits of detection were in the range of 0.01–0.05 ng/mL. The satisfactory recoveries (68.9–106.1%) were obtained at three different spiked concentrations (2, 5, and 8 ng/mL) in water samples, and the relative standard deviations were between 1.96 and 8.38%. This proposed method not only showed high sensitivity and good reusability but also provided a new adsorbent for enriching trace N-nitrosoamines in environmental water samples.     

Magnetic titanium oxide nanoparticles for hemimicelle extraction and HPLC determination of organophosphorus pesticides in environmental water

We report on a method for the extraction of organophosphorus pesticides (OPPs) from water samples using mixed hemimicelles and magnetic titanium dioxide nanoparticles (Fe₃O₄@TiO₂) modified by cetyltrimethylammonium. Fe₃O₄@TiO₂ nanoparticles were synthesized by a hydrothermal process and then characterized by scanning electron microscopy and Fourier transform IR spectrometry. The effects of the quantity of surfactant, extraction time, desorption solvent, pH value, extraction volume and reuse of the sorbent were optimized with respect to the extraction of OPPs including chlorpyrifos, dimethoate, and trichlorfon. The extraction method was applied to analyze OPPs in environmental water using HPLC along with UV detection. The method has a wide linear range (100–15,000 ng L^?1), good linearity (r?>?0.999), and low detection limits (26–30 ng L^?1). The enrichment factor is ~1,000. The recoveries (at spiked levels of 100, 1,000 and 10,000 ng L^?1) are in the range of 88.5–96.7 %, and the relative standard deviations range from 2.4 % to 8.7 %.

Solid-phase extraction of several phthalate esters from environmental water samples on a column packed with polytetrafluoroethylene turnings.

A method for the determination of several phthalate esters in water samples using solid-phase extraction coupled to high-performance liquid chromatography was developed. A polytetrafluoroethylene turnings packed column was used as a SPE adsorbent material. The analytes were sorbed on polytetrafluoroethylene turnings, from which they were eluted by a small amount of acetonitrile, followed by a RP-HPLC-UV analysis. Detection limits (3sigma) of 4.7, 3.1, 3.6, 4.3, and 5.8 ng mL(-1) for di-n-butyl-phthalate, di-cyclohexyl-phthalate, di-n-octyl-phthalate, di-n-nonyl-phthalate and di-iso-decyl-phthalate, respectively, were achieved. Acceptable recovery results (92.1-127.5%) were obtained on five phthalate esters spiked samples.     

Molecularly imprinted polymer surfaces as solid-phase extraction sorbents for the extraction of 2-nitrophenol and isomers from environmental water

The novel surface molecularly imprinted polymer (MIP) with 2‐nitrophenol (2‐NP) as the template has been prepared and used as the adsorbent for the solid‐phase extraction (SPE). The selectivity of the polymer was checked toward several selected nitrophenols (NPs) such as 2‐NP, 3‐nitrophenol (3‐NP), 4‐nitrophenol (4‐NP) and 2,4,6‐trichlorophenol (2,4,6‐TCP). Under the optimized conditions, high sensitivity (detection limits: 0.07–0.12 ng/mL) and good reproducibility of analytes (2.3–4.8% for four cycles) were achieved. Then, the method was applied for the analysis of selected phenols in spiked tap, lake and river water samples. High recoveries (>83.3%) for nitrophenols (NPs) were obtained, but lower recoveries (<63.4%) were achieved for 2,4,6‐TCP. The method was found to be linear in the range of 1–300 ng/mL with correlation coefficients (R²) greater than 0.99 and repeatability relative standard deviation (RSD) below 7.2% in all cases. For analysis of 120 mL water samples, the method detection limits (LODs) ranged from 0.10 to 0.22 ng/mL and the limit of quantification (LOQs) from 0.33 to 0.72 ng/mL. These results showed the suitability of the MIP‐SPE method for the selective extraction of a group of structurally related isomeric compounds.     

Improvement of on-line solid-phase extraction for determining phenolic compounds in water

Summary Modifying the most common design for the on-line coupling of a precolumn to reversed phase LC with diode array detection has resulted in reduction of the broadening of the peaks which results when the compounds of interest are strongly retained by a highly hydrophobic sorbent. The modification consists of the desorption of the analytes trapped on the precolumn solely by the organic solvent used to modify the solvent strength of the mobile phase. Results obtained using this design were compared with those obtained with the conventional design, with C₁₈ and PLRP-S precolumns. The performance of the system was also tested with a highly cross-linked styrene-divinylbenzene copolymer (ENVI-chrom P) precolumn for the determination of phenolic compounds in real samples. The advantages and disadvantages are discussed. Ion-pair solid phase extraction is used in order to increase the breakthrough volumes of more polar compounds, mainly phenol. The use of the new design enables phenolic compounds to be determined at the low μg L⁻¹ level with limits of detection ranging between 0.1 and 2 μg L⁻¹ in tap water when a 10 mL sample was analyzed.     

固相萃取-微乳液相色谱法测定环境水体中的3种酚类化合物

建立了固相萃取-微乳液相色谱法同时测定环境水体中的苯酚、双酚A (BPA)、2,4-二氯苯酚3种酚类化合物的检测方法。水样加酸酸化后,经C18固相萃取小柱富集净化,用微乳液相色谱法测定3种目标物的含量。在Inertsil C18色谱柱(150 mm×4.6 mm, 5 μm)上以微乳(3.0%十二烷基硫酸钠(SDS)-6.0%正丁醇-0.8%正庚烷-90.2%(水+0.5%HAc))和乙腈作为流动相进行梯度洗脱,流速1.0 mL/min,检测波长280 nm。结果表明,苯酚、双酚A、2,4-二氯苯酚的检出限(S/N=3)依次为0.74、8.0、8.0 μg/L,线性范围在0.1~10 mg/L范围内,相关系数(r)均大于0.999。将3种酚类化合物定量加到空白水样中,苯酚、双酚A、2,4-二氯苯酚的加标回收率分别为82.7%、87.8%、82.6%,其RSD均小于5%(n=6)。对环境水样的酚类化合物分析也取得了良好的加标回收率,其值均在85.7%~113.2%之间。结果表明,该方法准确可靠、灵敏度高,适用于环境水体中酚类化合物的检测。     

Optimisation of stir bar sorptive extraction and in-tube derivatisation-thermal desorption-gas chromatography-mass spectrometry for the determination of several endocrine disruptor compounds in environmental water samples

The analysis of organic pollutants in environmental water samples requires a pre-concentration step. Pre-concentration techniques such as stir bar sorptive extraction (SBSE) have gained popularity since they minimise the use of toxic organic solvents and can be considered as green analytical techniques. Similar to other pre-concentration techniques, one of the problems when SBSE is used is the matrix effect, which often occurs during the analysis of environmental water samples such as estuarine or wastewater samples. The present work studied the matrix effect during SBSE coupled to in-tube derivatisation–thermal desorption (TD)–gas chromatography–mass spectrometry for the determination of several endocrine disruptor compounds, such as alkylphenols, bisphenol A, estrogens and sterols, in environmental water samples, after optimisation of the major variables affecting the determination. Variables such as the addition of methanol or an inert salt to the donor phase, the extraction temperature, the volume of the donor phase, the stirring rate and the extraction time were studied during the SBSE optimisation. In the case of the in-tube derivatisation and TD step, the volume of the derivatisation reagent (N,O-bis(trimethylsilyl)triufloroacetamide with 1% of trimethylchlorosilane (BSTFA + 1% TMCS)) and the cryo-focusing temperature were fixed (2 μL and −50 °C, respectively) according to a consensus between maximum signal and optimal operation conditions. Good apparent recovery values (78–124%) were obtained for most of the analytes in Milli-Q water, except for 4-tert-octylphenol (4-tOP), which showed apparent recovery values exceeding 100%. Precision (n = 4) was in the 2–27%, and method detection limits were in the low nanogrammes per litre level for most of the analytes studied. The matrix effect was studied using two different approaches. On the one hand, Milli-Q water samples were spiked with humic acids, and apparent recovery values were studied with and without correction with the corresponding deuterated analogue. On the other hand, estuarine water and wastewater samples were spiked with known concentrations of target analytes, and apparent recoveries were studied as explained above. In general, the matrix effect could be corrected with the use of deuterated analogues, except for 4-tOP and nonylphenols for which [²H₄]-n-nonylphenol did not provide good corrections.     

Preparation of Fe3O4@C@PANI magnetic microspheres for the extraction and analysis of phenolic compounds in water samples by gas chromatography-mass spectrometry

In this work, core-shell structure Fe(3)O(4)@C@polyaniline magnetic microspheres were synthesized using simple hydrothermal reactions. The carbon-coated magnetic microspheres (Fe(3)O(4)@C) were first synthesized by a hydrothermal reaction, and then aniline was polymerized on the magnetic core via another hydrothermal reaction. Then, the obtained Fe(3)O(4)@C@polyaniline magnetic microspheres were applied as magnetic adsorbents for the extraction of aromatic molecules due to π-π interactions between polyaniline shell and aromatic compounds. In our study, five kinds of phenols including phenol, 2,4-dichlorophenol (DCP), 2,4,5-trichlorophenol (TCP), pentachlorophenol (PCP) and bisphenol A (BPA) were selected as the model analytes to verify the extraction ability of Fe(3)O(4)@C@PANI microspheres. After derivatization, the phenols were detected using gas chromatography-mass spectrometry (GC-MS). The dominant parameters affecting enrichment efficiency were investigated and optimized. Under the optimal conditions, the proposed method was evaluated, and applied to the analysis of phenols in real water samples. The results demonstrated that our proposed method based on Fe(3)O(4)@C@polyaniline magnetic microspheres had good linearity (r(2)>0.991), and limits of quantification (2.52-29.7 ng/mL), high repeatability (RSD<13.1%) and good recovery (85.3-110.6%).