Application of magnetic graphitic carbon nitride nanocomposites for the solid‐phase extraction of phthalate esters in water samples

Magnetic graphitic carbon nitride nanocomposites were successfully prepared in situ and used to develop a highly sensitive magnetic solid‐phase extraction method for the preconcentration of phthalate esters such as di‐n‐butyl phthalate, butyl phthalate, dihexyl phthalate, and di‐(2‐ethyl hexyl) phthalate from water. The adsorption and desorption of the phthalate esters on magnetic graphitic carbon nitride nanocomposites were investigated and the parameters affecting the partition of the phthalate esters, such as adsorption, desorption, recovery, were assessed. Under the optimized conditions, the proposed method showed excellent sensitivity with limits of detection (S/N = 3) in the range of 0.05–0.1 μg/L and precision in the range of 1.1–2.6% (n = 5). This method was successfully applied to the analysis of real water samples, and good spiked recoveries over the range of 79.4–99.4% were obtained. This research provides a possibility to apply this nanocomposite for adsorption, preconcentration, or even removal of various carbon‐based ring or hydrophobic pollutants.     

One-step in-syringe dispersive liquid–liquid microextraction and GC-FID determination of trace amounts of di(2-ethylhexyl) phthalate and its metabolite in human urine samples

Di(2-ethylhexyl) phthalate (DEHP) is used as plasticizer in polyvinylchloride (PVC) plastics. Its metabolites and the parent phthalates are considered toxic. As the DEHP plasticizers are not chemically bound to PVC, they can migrate, evaporate or be leached into indoor air and atmosphere, foodstuff, and other materials. We have reported a novel, easy and available analytical method for the determination of DEHP and its metabolite, mono(2-ethylhexyl) phthalate (MEHP) in human urine samples by the in-syringe dispersive liquid–liquid microextraction method coupled with gas chromatography with flame ionization detector. The limits of detection and precision (RSD) were 2.5 μg/L and 1.4% for DEHP and 1.1 μg/L and 3.0% for MEHP, respectively. This method could be utilized for routine monitoring of the trace DEHP and MEHP in urine of human exposure to plasticizers.     

Determination of phthalates in beverages using multiwalled carbon nanotubes dispersive solid‐phase extraction before HPLC–MS

A microdispersive solid‐phase extraction method has been developed using multiwalled carbon nanotubes of 110–170 nm diameter and 5–9 μm length for the extraction of a group of nine phthalic acid esters (i.e., bis(2‐methoxyethyl) phthalate, bis‐2‐ethoxyethyl phthalate, dipropyl phthalate, butylbenzyl phthalate, bis‐2‐n‐butoxyethyl phthalate, bis‐isopentyl phthalate, bis‐n‐pentyl phthalate, dicyclohexyl phthalate, and di‐n‐octyl phthalate) from tap water as well as from different beverages commercialized in plastic bottles (mineral water, lemon‐ and apple‐flavored mineral water, and an isotonic drink). Determination was carried out by high‐performance liquid chromatography coupled to mass spectrometry. The extraction procedure was optimized following a step‐by‐step approach, being the optimum extraction conditions: 50 mL of each sample at pH 6.0, 80 mg of sorbent, and 25 mL of acetonitrile as elution solvent. To validate the methodology, matrix‐matched calibration and a recovery study were developed, obtaining determination coefficients >0.9906 and absolute recovery values between 70 and 117% (with relative standard deviations < 17%) in all cases. The limits of quantification of the method were between 0.173 and 1.45 μg/L. After the evaluation of the matrix effects, real samples were also analyzed, finding butylbenzyl phthalate in all samples (except in apple‐flavored mineral water), though at concentrations below its limit of quantification of the method.     

A porous carbon derived from amino‐functionalized material of Institut Lavoisier as a solid‐phase microextraction fiber coating for the extraction of phthalate esters from tea

In this work, a porous carbon derived from amino‐functionalized material of Institut Lavoisier (C‐NH₂‐MIL‐125) was prepared and coated onto a stainless‐steel wire through sol–gel technique. The coated fiber was used for the solid‐phase microextraction of trace levels of phthalate esters (diallyl phthalate, di‐iso‐butyl ortho‐phthalate, di‐n‐butyl ortho‐phthalate, benzyl‐n‐butyl ortho‐phthalate, and bis(2‐ethylhexy) ortho‐phthalate) from tea beverage samples before gas chromatography with mass spectrometric analysis. Several experimental parameters that could influence the extraction efficiency such as extraction time, extraction temperature, sample pH, sample salinity, stirring rate, desorption temperature and desorption time, were investigated. Under the optimal conditions, the linearity existed in the range of 0.05–30.00 μg/L for green jasmine tea beverage samples, and 0.10–30.00 μg/L for honey jasmine tea beverage samples, with the correlation coefficients (r) ranging from 0.9939 to 0.9981. The limits of detection of the analytes for the method were 2.0–3.0 ng/L for green jasmine tea beverage sample, and 4.0–5.0 ng/L for honey jasmine tea beverage sample, depending on the compounds. The recoveries of the analytes for the spiked samples were in the range of 82.0–106.0%, and the precision, expressed as the relative standard deviations, was less than 11.1%.     

Validation of a new high‐throughput method to determine urinary S‐phenylmercapturic acid using low‐temperature partitioning extraction and ultra high performance liquid chromatography–mass spectrometry

A new highly sensitive and environmentally friendly analytical method, using low‐temperature partition extraction and ultra‐high‐performance liquid chromatography with tandem mass spectrometry, without the use of a labeled analyte, was developed and validated to determine and quantify urinary S‐phenylmercapturic acid in urine samples. The World Health Organization, in its guidelines for air quality in Europe, recognizes that benzene is carcinogenic to humans and there is no safe level of exposure. Urinary S‐phenylmercapturic acid is a sensitive and specific biological marker of exposure to benzene. The new analytical method, extraction, and analysis, were linear in the working range between 0.1 and 200.0 μg/L, precise (relative standard deviation lower than 6.0%), accurate (97.0–105.0%), and sensitive. The method's limits of detection and quantification were 0.02 and 0.084 μg/L, respectively. The recovery with the low‐temperature partition extraction was 96.1%, with relative standard deviation less than 3.8%. The method is simple, accurate, and reproducible, and has been successfully applied in the evaluation of nonoccupational exposure to benzene, by urinary S‐phenylmercapturic acid in urine samples.     

Gas chromatography with mass spectrometry for the determination of phthalates preconcentrated by microextraction based on an ionic liquid

A new procedure is proposed for the analysis of migration test solutions obtained from plastic bottles used in the packaging of edible oils. Ultrasound‐assisted emulsification microextraction with ionic liquids was applied for the preconcentration of six phthalate esters: dimethylphthalate, diethylphthalate, di‐n‐butylphthalate, n‐butylbenzylphthalate, di‐2‐ethylhexylphthalate, and di‐n‐octylphthalate. The enriched ionic liquid was directly analyzed by gas chromatography and mass spectrometry using direct insert microvial thermal desorption. The different factors affecting the microextraction efficiency, such as volume of the extracting phase (30 μL of the ionic liquid) and ultrasound application time (25 s), and the thermal desorption step, such as desorption temperature and time, and gas flow rate, were studied. Under the selected conditions, detection limits for the analytes were in the 0.012–0.18 μg/L range, while recovery assays provided values ranging from 80 to 112%. The use of butyl benzoate as internal standard increased the reproducibility of the analytical procedure. When the release of the six phthalate esters from the tested plastic bottles to liquid simulants was monitored using the optimized procedure, analyte concentrations of between 1.0 and 273 μg/L were detected.     

Solid‐phase extraction based on chloromethylated polystyrene magnetic nanospheres followed by gas chromatography with mass spectrometry to determine phthalate esters in beverages

An ultrasound‐assisted magnetic solid‐phase extraction procedure with chloromethylated polystyrene‐coated Fe₃O₄ nanospheres as magnetic adsorbents has been developed to determine eight phthalate esters (bis(4‐methyl‐2‐pentyl) phthalate, dipentyl phthalate, dihexyl phthalate, benzyl butyl phthalate, bis(2‐butoxyethyl) phthalate, dicyclohexyl phthalate, di‐n‐octyl phthalate, and dinonyl phthalate) simultaneously in beverage samples, in combination with gas chromatography coupled to tandem mass spectrometry for the first time. Several factors related to magnetic solid‐phase extraction efficiencies, such as amount of adsorbent, extracting time, ionic strength, and desorption conditions were investigated. The enrichment factors of the method for the eight analytes were over 2482. A good linearity was observed in the range of 10–500 ng/L for bis(2‐butoxyethyl) phthalate and 2–500 ng/L for the other phthalate esters with correlation coefficients ranging from 0.9980 to 0.9998. The limits of detection and quantification for the eight phthalate esters were in the range of 0.20–2.90 and 0.67–9.67 ng/L, respectively. The mean recoveries at three spiked levels were 75.8–117.7%, the coefficients of variations were <11.6%. The proposed method was demonstrated to be a simple and efficient technique for the trace analysis of the phthalate esters in beverage samples.     

A rapid method for the quantification of urinary phthalate monoesters: A new strategy for the assessment of the exposure to phthalate ester by solid‐phase microextraction with gas chromatography and tandem mass spectrometry

In the following work, a new method for the analysis of the phthalate monoesters in human urine was reported. Phthalate monoesters are metabolites generated as a result of phthalate exposure. In compliance with the dictates of Green Analytical Chemistry, a rapid and simple protocol was developed and optimized for the quantification of phthalate monoesters (i.e., monoethyl phthalate, monoisobutyl phthalate, mono‐n‐butyl phthalate, mono‐(2‐ethylhexyl) phthalate, mono‐n‐octyl phthalate, monocyclohexyl phthalate, mono‐isononyl phthalate) in human urine, which entails preceding derivatization with methyl chloroformate combined with the use of commercial solid phase microextraction and the analysis by gas chromatography‐triple quadrupole mass spectrometry. The affinity of the derivatized analytes toward five commercial coatings was evaluated, and in terms of analyte extraction, the best results were reached with the use of the divinylbenzene/carboxen/polydimethylsiloxane fiber. The multivariate approach of experimental design was used to seek for the best working conditions of the derivatization reaction and the solid phase microextraction, thus obtaining the optimum response values. The proposed method was validated according to the guidelines issued by the Food and Drug Administration achieving satisfactory values in terms of linearity, sensitivity, matrix effect, intra‐ and inter‐day accuracy, and precision.     

Simple determination of betaine,l‐carnitine and choline in human urine using self‐packed column and column‐switching ion chromatography with nonsuppressed conductivity detection

A sequential online extraction, clean‐up and separation system for the determination of betaine, l ‐carnitine and choline in human urine using column‐switching ion chromatography with nonsuppressed conductivity detection was developed in this work. A self‐packed pretreatment column (50 × 4.6 mm, i.d.) was used for the extraction and clean‐up of betaine, l ‐carnitine and choline. The separation was achieved using self‐packed cationic exchange column (150 × 4.6 mm, i.d.), followed by nonsuppressed conductivity detection. Under optimized experimental conditions, the developed method presented good analytical performance, with excellent linearity in the range of 0.60–100 μg mL⁻¹ for betaine, 0.75–100 μg mL⁻¹ for l ‐carnitine and 0.50–100 μg mL⁻¹ for choline, with all correlation coefficients (R²) >0.99 in urine. The limits of detection were 0.15 μg mL⁻¹ for betaine, 0.20 μg mL⁻¹ for l ‐carnitine and 0.09 μg mL⁻¹ for choline. The intra‐ and inter‐day accuracy and precision for all quality controls were within ±10.32 and ±9.05%, respectively. Satisfactory recovery was observed between 92.8 and 102.0%. The validated method was successfully applied to the detection of urinary samples from 10 healthy people. The values detected in human urine using the proposed method showed good agreement with the measurement reported previously.     

Acrylamide‐functionalized graphene micro‐solid‐phase extraction coupled to high‐performance liquid chromatography for the online analysis of trace monoamine acidic metabolites in biological samples

Monoamine acidic metabolites in biological samples are essential biomarkers for the diagnosis of neurological disorders. In this work, acrylamide‐functionalized graphene adsorbent was successfully synthesized by a chemical functionalization method and was packed in a homemade polyether ether ketone micro column as a micro‐solid‐phase extraction unit. This micro‐solid‐phase extraction unit was directly coupled to high‐performance liquid chromatography to form an online system for the separation and analysis of three monoamine acidic metabolites including homovanillic acid, 5‐hydroxyindole‐3‐acetic acid, and 3,4‐dihydroxyphenylacetic acid in human urine and plasma. The online system showed high stability, permeability, and adsorption capacity toward target metabolites. The saturated extraction amount of this online system was 213.1, 107.0, and 153.4 ng for homovanillic acid, 5‐hydroxyindole‐3‐acetic acid, and 3,4‐dihydroxyphenylacetic acid, respectively. Excellent detection limits were achieved in the range of 0.08–0.25 μg/L with good linearity and reproducibility. It was interesting that three targets in urine and plasma could be actually quantified to be 0.94–3.93 μg/L in plasma and 7.15–19.38 μg/L in urine. Good recoveries were achieved as 84.8–101.4% for urine and 77.8–95.1% for plasma with the intra‐ and interday relative standard deviations less than 9.3 and 10.3%, respectively. This method shows great potential for online analysis of trace monoamine acidic metabolites in biological samples.     

Capillary electrophoresis chemiluminescence assay of naphthol isomers in human urine and river water using Ni(IV) complex‐luminol system

A capillary electrophoresis method involving online indirect chemiluminescence (CL) detection was used to determine naphthol (NAP) isomers. The method was based on the quenching effect of 1‐ and 2‐NAP on a new CL reaction of luminol with Ni(IV) complex in an alkaline medium. Separation was conducted with a 25.0 mM sodium borate buffer containing 0.8 mmol/L luminol. Under optimized conditions, 1‐ and 2‐NAP were baseline separated and detected in less than 8 min. The limits of detection of 1‐ and 2‐NAP were 3.1 and 2.7 μg/L, respectively (S/N = 3), with a linear range of 4.0–80.0 μg/L (r > 0.995). Analysis of real samples demonstrated that the spiked recoveries were in the range of 89.2–107.5% (n = 3). The proposed method was successfully used to determine 1‐ and 2‐NAP contents in three environmental water samples and 14 human urine samples. No derivatization or tedious pretreatment was required in the analysis. The proposed method is a potential approach for routine tests of naphthol isomers in a facile CE–CL system.     

Simultaneous determination of seven phthalic acid esters in beverages using ultrasound and vortex‐assisted dispersive liquid–liquid microextraction followed by high‐performance liquid chromatography

A sensitive, rapid, and simple high‐performance liquid chromatography with UV detection method was developed for the simultaneous determination of seven phthalic acid esters (dimethyl phthalate, dipropyl phthalate, di‐n‐butyl phthalate, benzyl butyl phthalate, dicyclohexyl phthalate, di‐(2‐ethylhexyl) phthalate, and di‐n‐octyl phthalate) in several kinds of beverage samples. Ultrasound and vortex‐assisted dispersive liquid–liquid microextraction method was used. The separation was performed using an Intersil ODS‐3 column (C₁₈, 250 × 4.6 mm, 5.0 μm) and a gradient elution with a mobile phase consisting of MeOH/ACN (50:50) and 0.2 M KH₂PO₄ buffer. Analytes were detected by a UV detector at 230 nm. The developed method was validated in terms of linearity, limit of detection, limit of quantification, repeatability, accuracy, and recovery. Calibration equations and correlation coefficients (> 0.99) were calculated by least squares method with weighting factor. The limit of detection and quantification were in the range of 0.019–0.208 and 0.072–0.483 μg/L. The repeatability and intermediate precision were determined in terms of relative standard deviation to be within 0.03–3.93 and 0.02–4.74%, respectively. The accuracy was found to be in the range of –14.55 to 15.57% in terms of relative error. Seventeen different beverage samples in plastic bottles were successfully analyzed, and ten of them were found to be contaminated by different phthalic acid esters.     

In silico methods for predicting metabolism and mass fragmentation applied to quetiapine in liquid chromatography/time‐of‐flight mass spectrometry urine drug screening

Current in silico tools were evaluated for their ability to predict metabolism and mass spectral fragmentation in the context of analytical toxicology practice. A metabolite prediction program (Lhasa Meteor), a metabolite detection program (Bruker MetaboliteDetect), and a fragmentation prediction program (ACD/MS Fragmenter) were used to assign phase I metabolites of the antipsychotic drug quetiapine in the liquid chromatography/time‐of‐flight mass spectrometry (LC/TOFMS) accurate mass data from ten autopsy urine samples. In the literature, the main metabolic routes of quetiapine have been reported to be sulfoxidation, oxidation to the corresponding carboxylic acid, N‐ and O‐dealkylation and hydroxylation. Of the 14 metabolites predicted by Meteor, eight were detected by LC/TOFMS in the urine samples with use of MetaboliteDetect software and manual inspection. An additional five hydroxy derivatives were detected, but not predicted by Meteor. The fragment structures provided by ACD/MS Fragmenter software confirmed the identification of the metabolites. Mean mass accuracy and isotopic pattern match (SigmaFit) values for the fragments were 2.40 ppm (0.62 mDa) and 0.010, respectively. ACD/MS Fragmenter, in particular, allowed metabolites with identical molecular formulae to be differentiated without a need to access the respective reference standards or reference spectra. This was well exemplified with the hydroxy/sulfoxy metabolites of quetiapine and their N‐ and O‐dealkylated forms. The procedure resulted in assigning 13 quetiapine metabolites in urine. The present approach is instrumental in developing an extensive database containing exact monoisotopic masses and verified retention times of drugs and their urinary metabolites for LC/TOFMS drug screening. Copyright © 2009 John Wiley & Sons, Ltd.     

Mesoporous Silica‐coated Magnetic Nanoparticles for Mixed Hemimicelles Solid‐phase Extraction of Phthalate Esters in Environmental Water Samples with Liquid Chromatographic Analysis

To extract, preconcentrate and determine the trace level of environmental contaminants, a novel mixed hemimicelles solid‐phase extraction (MHSPE) method based on mesoporous silica‐coated magnetic nanoparticles (Fe₃O₄/meso‐SiO₂ NPs) as adsorbent was developed for extraction of phthalate esters from water samples. The Fe₃O₄/meso‐SiO₂ NPs were synthesized by using a combination of hydrothermal method and sol‐gel method. The obtained Fe₃O₄/meso‐SiO₂ NPs possessed a large surface area (570 m²/g), superparamagnetism, and uniform mesopores (2.8 nm). MHSPE parameters, such as the amount of surfactant, pH of sample, shaking and separation time, eluent and breakthrough volume that may influence the extraction of analytes greatly, were further investigated. Under the optimized conditions, the extraction was completed in 20 min and a concentration factor of 500 was achieved by extracting 250 mL water sample. Detection limits obtained of butyl‐benzyl phthalate (BBP), di‐n‐butyl phthalate (DnBP), di‐(2‐ethylhexyl) phthalate (DEHP) and di‐n‐cotyl phthalate (DnOP) were 12, 21, 12, and 32 ng/L, respectively. The proposed method exhibited high extraction efficiency and relatively short time for extracting the target compounds.     

Simultaneous quantification of antofloxacin and its major metabolite in human urine by HPLC–MS/MS,and its application to a pharmacokinetic study

This study presents a high‐performance liquid chromatography–tandem mass spectrometry (HPLC–MS/MS) method for the simultaneous determination of antofloxacinin and its main metabolite – N ‐demethylated metabolite (N‐ DM) – in human urine. Ornidazole was used as the internal standard. This was a clinical urine recovery study, in which 10 healthy Chinese volunteers were intravenously administered a single 200 mg dose of antofloxacin hydrochloride. Compounds were extracted by albumen precipitation, after which samples were isocratically eluted using a Poroshell 120 SB‐C₁₈ column, and were analysed using HPLC–MS/MS under electronic spray ionization positive ion mode. The method was successfully applied in a urine pharmacokinetic study of antofloxacinin, with a detection range of 0.02/0.01 to 200/100 μg/mL (for antofioxacin/N‐ DM).The average percentages of antofioxacin/N‐ DM measured in urinary excretion frp, 10 volunteers were 54.9 ± 5.7/8.2 ± 2.5% in 120 h duration.     

多功能离子液体分散液液微萃取结合高效液相色谱法检测人尿中5种邻苯二甲酸酯代谢物

将多功能离子液体与分散液液微萃取（DLLME）技术相结合，建立了测定尿液中5种邻苯二甲酸酯类（PAEs）物质代谢产物的高灵敏度新方法。对影响DLLME效率的各单因素进行了优化，包括萃取剂的种类及体积、分散剂的种类及体积、萃取温度、超声时间、冷却时间、离心时间和盐效应等条件，经过严格的优化，最佳的萃取条件分别为：萃取剂[C₈MIM]PF₆]35 μL，分散剂[BSO₃HMIm]OTf]30 μL和[C₄MIM]BF₆]120 μL，萃取温度为35℃，超声时间5 min，冷却时间5 min，离心时间5 min，盐析剂NH₄PF₆ 0.1 g。在最佳的萃取条件下，5种PAEs代谢物在0.5~1000 μg/L范围内具有良好的线性关系，决定系数（R²）均大于0.9955，方法检出限为0.16~0.19 μg/L，尿液中添加低中高水平（5、20、100 μg/L）的PAEs代谢物，其回收率为92.9%~105.0%，日内精密度及日间精密度的相对标准偏差（RSD）均小于5.96%，方法学验证各指标及稳定性均符合分析要求。对所采集的10份糖尿病患者的尿液进行检测，并对该人群PAEs代谢物的暴露水平进行评价。结果表明，各PAEs代谢物均有检出，其中邻苯二甲酸单（2-乙基己基）酯（MEHP）的检出率为100%。总之，该方法萃取过程中未添加有毒的有机试剂，均使用多功能离子液体作为萃取剂、分散剂和盐析剂，萃取过程绿色环保，简单高效；方法的灵敏度较高，稳定性较好，适用于人体尿液中痕量PAEs代谢物的检测。     

Synthesis of molecularly imprinted polymers by atom transfer radical polymerization for the solid‐phase extraction of phthalate esters in edible oil

Novel molecularly imprinted polymers of phthalate esters were prepared by atom transfer radical polymerization using methyl methacrylate as functional monomer, cyclohexanone as solvent, cuprous chloride as catalyst, 1‐chlorine‐1‐ethyl benzene as initiator and 2,2‐bipyridyl as cross‐linker in the mixture of methanol and water (1:1, v/v). The effect of reaction conditions such as monomer ratio and template on the adsorption properties was investigated. The optimum condition was obtained by an orthogonal experiment. The obtained polymers were characterized using scanning electron microscopy. The binding property was studied with both static and dynamic methods. Results showed that the polymers exhibited excellent recognition capacity and outstanding selectivity for ten phthalate esters. Factors affecting the extraction efficiency of the molecularly imprinted solid‐phase extraction were systematically investigated. An analytical method based on the molecularly imprinted coupled with gas chromatography and flame ionization detection was successfully developed for the simultaneous determination of ten phthalate esters from edible oil. The method detection limits were 0.10–0.25 μg/mL, and the recoveries of spiked samples were 82.5–101.4% with relative standard deviations of 1.24–5.37% (n = 6).     

Determination of phthalate esters from environmental water samples by micro‐solid‐phase extraction using TiO2 nanotube arrays before high‐performance liquid chromatography

We describe a highly sensitive micro‐solid‐phase extraction method for the pre‐concentration of six phthalate esters utilizing a TiO₂ nanotube array coupled to high‐performance liquid chromatography with a variable‐wavelength ultraviolet visible detector. The selected phthalate esters included dimethyl phthalate, diethyl phthalate, dibutyl phthalate, butyl benzyl phthalate, bis(2‐ethylhexyl)phthalate and dioctyl phthalate. The factors that would affect the enrichment, such as desorption solvent, sample pH, salting‐out effect, extraction time and desorption time, were optimized. Under the optimum conditions, the linear range of the proposed method was 0.3–200 μg/L. The limits of detection were 0.04–0.2 μg/L (S/N = 3). The proposed method was successfully applied to the determination of six phthalate esters in water samples and satisfied spiked recoveries were achieved. These results indicated that the proposed method was appropriate for the determination of trace phthalate esters in environmental water samples.     

Simultaneous detection of three antiviral and four antibiotic compounds in source‐separated urine with liquid chromatography

An analytical method for the simultaneous screening of three antiviral agents (nevirapine, zidovudine, lamivudine), four antibiotics (sulfamethoxazole, trimethoprim, ciprofloxacin, rifampicin) and one reference compound (carbamazepine) in human urine was developed. Separation was achieved with a Kinetex XB‐C₁₈ (75 × 4.6 mm, 2.6 μm) column after the extraction of pharmaceuticals from urine with SPE. Gradient elution with a mobile phase consisting of acetonitrile and 10 mM KH₂PO₄ (pH 2.5), and diode array detection with monitoring at 210 and 264 nm was applied. The developed method was validated in terms of selectivity, linearity, stability and sensitivity. Repeatability (n = 3) and between‐day precision (n = 3) revealed RSD <5%. The detection limits were estimated as 0.02–0.54 g/L (depending on compound). The method was validated for human urine and successfully applied to the simultaneous quantification of selected compounds. Strata‐X cartridges provided good recoveries ranging from 81 to 109%. The limits of detection for urine varied between 0.04 and 1.61 g/L. The method is suitable for the fast determination of selected pharmaceuticals from source‐separated urine samples for further environmental risk assessment and degradation potential evaluation. It provides a way to enhance safe nutrient recycling from wastewater streams and promotes the safe use of urine as fertiliser.     

Simultaneous determination of nine anticoagulant rodenticides in soil and water by LC–ESI‐MS

A new and sensitive analytical method is presented to determine nine anticoagulant rodenticide (chlorophacinone, bromadiolone, pindone, diphacinone, warfarin, coumatetralyl, brodifacoum, floucomafen, and difenacoum) residues in water and soil samples by LC–ESI‐MS. Rodenticides were extracted from soil using a methanol and ammonium formate 30 mM mixture, while ethyl acetate was employed in the water samples. A Gemini 5 μm C₁₈ column was employed, and a mobile phase comprising a mixture of ammonium formate 30 mM and di‐n‐butylamine 30 mM in water (pH 3.5), ammonium formate 30 mM and di‐n‐butylamine 20 mM in water (pH 4.4), ammonium formate 30 mM in water (pH 6.5), and methanol in a gradient elution mode was selected. The method was fully validated and it was found to be selective and precise in terms of linearity and accuracy. Extraction recoveries ranged from 90 to 104% for the compounds studied, while the detection and quantification limits were between 0.09 and 2.2 μg/kg in soil or 0.08 and 1.7 μg/L in water. The method was applied to simultaneously measure these compounds in water and soil samples.