Ultra-Preconcentration and Determination of Multiple Pesticide Residues in Water Samples Using Ultrasound-Assisted Dispersive Liquid–Liquid Microextraction and GC-FID

In this study, a simple and efficient method has been developed to analyze pesticides in water samples using ultrasonic-assisted dispersive liquid–liquid microextraction (UA-DLLME) combined with gas chromatography-flame ionization detection (GC-FID). Several parameters, including type and volume of extractant and dispersant, extraction time, and amount of salt on extraction performance, were optimized in detail. A mixture of acetonitrile (1.0 mL, dispersant) and carbon tetrachloride (15 μL, extractant) was used for extraction. Under optimal conditions, enrichment factors were obtained between 315 and 1153. The linearity of the method ranged from 1 to 100 μg L⁻¹ with correlation coefficients ≥0.9990. Limits of detection (S/N = 3) ranged between 0.09 and 0.57 μg L⁻¹, depending on the compounds. Relative standard deviations were <8.0 % (n = 5) for both intra- and inter-day analyses. The proposed method was successfully applied for the preconcentration and determination of pesticides in water samples (river water, tap water, and lake water) with recoveries that varied from 90.5 to 107.7 %.

     

Determination of morpholinium ionic liquid cations in environmental water samples: development of solid-phase extraction method and ion chromatography

An ion chromatography and solid-phase extraction method has been applied for the separation and detection of morpholinium cations in environmental water samples. The water samples were purified and enriched by a UF-SCX sulfonic acid extraction column and eluted with 0.5 mol L⁻¹ phosphoric acid/sodium dihydrogen phosphate buffer solution/55% methanol. The target compounds were separated on a carboxylic acid cation exchange column with 5.0 mmol L⁻¹ methane sulfonic acid/2% acetonitrile as the mobile phase and direct conductivity detection. The method has been successfully applied to extract morpholinium cations from spiked water samples of Songhua River, Hulan River, East Lake, and Mopanshan Reservoir in China with the recoveries ranging from 75.0% to 98.3%. The relative standard deviations of intraday precision and interday precision are 2.1% and 5.9% or less, respectively. Using this method it is possible to preconcentrate water samples to 0.01–0.04 mg L⁻¹. The results show that the method is applicable to detection of morpholinium ionic liquid cations in environmental water samples and provides a new approach for monitoring ionic liquids in environmental water.

The analysis procedure of morpholinium ionic liquids in environmental water samples.

     

An On-line Admicellar SPE-HPLC System Using CTAB-Modified Zeolite NaY as Sorbent for Determination of Carbamate Pesticides in Water

Zeolite NaY modified with cetyltrimethylammonium bromide (CTAB) was considered for extraction/preconcentration of carbamate pesticides using an on-line SPE-HPLC system. The simultaneous determination of carbamate pesticides, including aldicarb, carbofuran, carbaryl, isoprocarb, methiocarb and promecarb, was performed by HPLC–UV using a LichroCART RP-18 column with gradient elution of methanol and 0.1 % acetic acid. The sorbent presented admicelles of CTAB on its surfaces and exhibited a sorption capacity of 180–18,600 mg kg⁻¹ sorbent, which could be re-modified for at least five extraction cycles. The quantitative retention of target pesticides on the admicellar sorbent involved hydrophobic and π-cation interaction, while pesticides were eluted from the admicellar SPE column using only 750 μL of methanol. LODs and LOQs of the proposed method were 0.005–140 and 0.02–600 μg L⁻¹, respectively. The analytes were effectively concentrated with the enrichment factors between 5 and 551. The developed on-line admicellar SPE-HPLC system was successfully applied to the determination of carbamate pesticides in ten environmental water samples from different sources. Recoveries of spiked samples at a concentration of 0.1–5 mg L⁻¹ ranged from 77 to 111 %.

     

Fe3O4纳米粒子修饰多壁碳纳米管的制备及在水和蜂蜜样品中痕量菊酯类农药分析中的应用

通过化学共沉淀法使Fe₃O₄纳米粒子负载于酸化多壁碳纳米管(AMWNTs)表面,得到Fe₃O₄/AMWNTs磁性纳米材料。该材料具有很好的磁响应度和分散性,将其用于富集痕量拟除虫菊酯类农药残留,结果证明该复合材料对菊酯类农药的吸附性能良好。通过对影响萃取性能的几种因素如离子强度、萃取时间和解吸时间依次进行优化,在最优条件下,建立了Fe₃O₄/AMWNTs磁性分散固相萃取-气相色谱测定6种菊酯类农药残留的分析方法。线性范围在0.5~50 μg/L之间,相关系数(R²)大于0.990,检出限为0.07~0.20 μg/L,精密度为3.8%~8.1%。该方法用于河水、鱼塘水和两种市售蜂蜜中菊酯类农药的残留分析,回收率高于78.4%。该方法操作简便、灵敏度高,能够满足环境水样及蜂蜜样品中痕量菊酯农药残留的分析需求。     

Effective liquid–liquid extraction method for analysis of pyrethroid and phenylpyrazole pesticides in emulsion-prone surface water samples

The distribution of pyrethroid and phenylpyrazole pesticides in the water environment has raised public concerns because of their potential risks to ecosystem and human health. However, co-extraction of emulsifier type compounds (by liquid–liquid extraction, LLE) present in environmental samples can present a challenge for quantifying typically low concentrations of pesticides. Several methods were evaluated for breaking emulsions in problematic environmental surface water samples extracted by LLE using methylene chloride. Target pesticides included 11 typical pyrethroid and phenylpyrazole pesticides commonly used in agricultural and landscape insect pest control. The most effective method was selected for validation in fortification studies with GC-ECD analysis. The average recoveries of spiked pyrethroid and phenylpyrazole pesticides were 88.2–123.4% for water samples with moderate emulsions and 93.0–117.4% for water samples with severe emulsions. Recoveries of the pesticides ranged 81.0–126.4% (water samples with moderate emulsions) and 95.9–110.6% (water samples with severe emulsions) for lowest fortification level (5–20 ng L⁻¹), 88.2–123.4% (water samples with moderate emulsions) and 93.0–117.4% (water samples with severe emulsions) for middle fortification level (10–40 ng L⁻¹), and 90.2–119.9% (water samples with moderate emulsions) and 91.2–105.9% (water samples with severe emulsions) for highest fortification level (50–200 ng L⁻¹). Relative standard deviations of pesticide recoveries were usually <10%. Results indicate that this method is a robust and reproducible option for LLE of pyrethroid and phenylpyrazole pesticides from emulsion-prone surface water samples.     

Rapid Determination of DDT and Its Metabolites in Environmental Water Samples with Mixed Ionic Liquids Dispersive Liquid–Liquid Microextraction Prior to HPLC-UV

In this paper, a novel mixed ionic liquids-dispersive liquid–liquid microextraction method was developed for rapid enrichment and determination of environmental pollutants in water samples. In this method, two kinds of ionic liquids, hydrophobic ionic liquid and hydrophilic ionic liquid, were used as extraction solvent and disperser solvent, respectively. DDT and its metabolites were used as model analytes and high-performance liquid chromatography with ultraviolet detector for the analysis. Factors that may affect the extraction recoveries, such as type and volume of extraction solvent (hydrophobic ionic liquid) and disperser solvent (hydrophilic ionic liquid), extraction time, sample pH and ionic strength, were investigated and optimized. Under the optimum conditions, the linear range was 1–100 μg L⁻¹, limits of detection could reach 0.21–0.49 μg L⁻¹, and relative standard deviation was 6.01–8.48 % (n = 7) for the analytes. Satisfactory results were achieved when the method was applied to analyze the target pollutants in environmental water samples with spiked recoveries over the range of 85.7–106.8 %.

     

Determination of Pyrethroid Pesticides in Environmental Waters Based on Magnetic Titanium Dioxide Nanoparticles Extraction Followed by HPLC Analysis

A simple and fast method based on magnetic separation for extraction of pyrethroid pesticides including beta-cyfluthrin, cyhalothrin and cyphenothrin from environmental water samples has been established. Magnetic titanium dioxide was used as sorbent, which was synthesized by coating TiO₂ on Fe₃O₄ in liquid-state co-precipitation method. The sorbent has been characterized by scanning electron microscopy and Fourier-transform infrared spectrometry, and the magnetic properties were investigated with physical property measurement system. Various parameters affecting the extraction efficiency were evaluated to achieve optimal condition and decrease ambiguous interactions. The analytes desorbed from the sorbent were detected by high performance liquid chromatography. Under the optimal condition, the linearity of the method is in the range of 25–2,500 ng L^?1. The detection limits and quantification limits of pyrethroid pesticides are in the range of 2.8–6.1 ng L^?1 and 9.3–20.3 ng L^?1, respectively. The relative standard deviations of intra- and inter-day tests ranging from 2.5 to 7.2 % and from 3.6 to 9.1 % were obtained. In all three spiked levels (25, 250 and 2,500 ng L^?1), the recoveries of pyrethroid pesticides were in the range of 84.5–94.1 %. The proposed method was successfully applied to determine pyrethroids in three water samples. Cyphenothrin was found in one river water near farmlands, and its concentration was 52 ng L^?1.     

气相色谱法测定地表水中拟除虫菊酯类农药残留

建立了气相色谱检测地表水样中痕量氯氟氰菊酯、氯氰菊酯、氰戊菊酯和溴氰菊酯农药残留的分析方法。水样经环己烷液液萃取、无水硫酸钠过滤,再用N-丙基乙二胺和无水硫酸镁净化,用氮气吹干浓缩,再用正己烷溶解,离心分离后取上清液进样,以气相色谱法测定4种拟除虫菊酯的含量。4种拟除虫菊酯化合物的质量浓度在5~200μg/L范围内与色谱峰面积成良好的线性关系,相关系数均大于0.999,方法检出限为0.03~0.09μg/L,模拟水样的平均加标回收率为98.0%~104.5%,相对标准偏差为0.89%~6.44%(n=6)。该方法操作方便、快速,结果准确、可靠,有机溶剂用量少,适用于水中拟除虫菊酯类农药残留的测定。     

Enrichment and determination of polybrominated diphenyl ethers in environmental water samples by magnetic solid‐phase extraction with core–shell magnetic carbon microspheres before gas chromatography with mass spectrometry

Core–shell magnetic carbon microspheres were synthesized by a simple hydrothermal method and used as a novel magnetic solid‐phase extraction adsorbent for the sensitive determination of polybrominated diphenyl ethers in environmental water samples. Gas chromatography with negative chemical ionization mass spectrometry was adopted for the detection. Box–Behnken design was used to investigate and optimize important magnetic solid‐phase extraction parameters through response surface methodology. Under the optimal conditions, low limits of detection (0.07–0.17 ng·L^?1), a wide linear range (1–1000 ng·L^?1), and good repeatability (0.80–4.58%) were achieved. The developed method was validated with several real water samples, and satisfactory results were obtained in the range of 72.8–97.9%. These results indicated that core–shell magnetic carbon microspheres have great potential as an adsorbent for the magnetic solid‐phase extraction of polybrominated diphenyl ethers at trace levels from environmental water samples.     

Modification of Carbon Paste Electrode Based on Molecularly Imprinted Polymer for Electrochemical Determination of Diazinon in Biological and Environmental Samples

The wide use of pesticides can lead to environmental and human adverse effects. Diazinon, as an organophosphorous pesticide, is used in agriculture because of its low cost and high efficiency on insects. Due to the increasing application of pesticides, accurate analytical methods are necessary. The aim of this work was modification of carbon paste electrode composition and applying it as a sensor for determination of diazinon in biological and environmental samples. Multi‐walls carbon nanotubes and a molecularly imprinted polymer were used as modifiers in the sensor composition. A molecularly imprinted polymer and a non‐imprinted polymer were synthesized for applying in the electrode. After optimization of electrode composition, it was used to determine the analyte concentration. Instrumental parameters affecting the square wave voltammetric response were adjusted to obtain the highest current intensity. The modified electrode with MIP showed very high recognition ability compared to the electrode containing NIP. The obtained linear range was 5×10⁻¹⁰ to 1×10⁻⁶ mol L⁻¹. The detection limit of the sensor was 1.3×10⁻¹⁰ mol L⁻¹ and the relative standard deviation for analysis of target molecule by the proposed sensor was 2.87 %. This sensor was used to determine the diazinon in real samples (human urine, tap, and river water samples) without special sample preparation before analysis. The optimization of electrode composition containing mentioned modifiers improved its response considerably.     

Development of magnetic dispersive microsolid-phase extraction using lanthanum phosphate nanoparticles doped on magnetic graphene oxide as a highly selective adsorbent for pesticide residues analysis in water and fruit samples

Magnetic graphene oxide/lanthanum phosphate nanocomposite (MGO@LaP) was synthesized and used as an efficient adsorbent for magnetic dispersive microsolid-phase extraction (MD-µ-SPE) of pesticides before gas chromatography–electron capture detector (GC–ECD) analysis. The adsorbent was thoroughly characterized with scanning electron microscopy, vibrating sample magnetometer, energy-dispersive X-ray spectroscopy, and Fourier transform infrared spectroscopy. Optimized extraction conditions were investigated concerning extraction time, adsorbent amount, sample pH, and salt amount as well as desorption conditions (type and volume of desorption solvent and desorption time). Under the optimal conditions, the method demonstrated good linearity (3–1500 µg L^?1) with satisfactory determination coefficients of >?0.997 and low detection limits for both chlorpyrifos (0.67 µg L^?1) and hexaconazole (0.89 µg L^?1). Finally, the method showed high analyte relative recoveries in the range of 78–120% for the determination of the selected pesticides in water and fruit juice samples.

     

Determination of BTEX Compounds by Dispersive Liquid–Liquid Microextraction with GC–FID

Rapid, inexpensive, and efficient sample-preparation by dispersive liquid–liquid microextraction (DLLME) then gas chromatography with flame ionization detection (GC–FID) have been used for extraction and analysis of BTEX compounds (benzene, toluene, ethylbenzene, and xylenes) in water samples. In this extraction method, a mixture of 25.0 μL carbon disulfide (extraction solvent) and 1.00 mL acetonitrile (disperser solvent) is rapidly injected, by means of a syringe, into a 5.00-mL water sample in a conical test tube. A cloudy solution is formed by dispersion of fine droplets of carbon disulfide in the sample solution. During subsequent centrifugation (5,000 rpm for 2.0 min) the fine droplets of carbon disulfide settle at the bottom of the tube. The effect of several conditions (type and volume of disperser solvent, type of extraction solvent, extraction time, etc.) on the performance of the sample-preparation step was carefully evaluated. Under the optimum conditions the enrichment factors and extraction recoveries were high, and ranged from 122–311 to 24.5–66.7%, respectively. A good linear range (0.2–100 μg L⁻¹, i.e., three orders of magnitude; r ² = 0.9991–0.9999) and good limits of detection (0.1–0.2 μg L⁻¹) were obtained for most of the analytes. Relative standard deviations (RSD, %) for analysis of 5.0 μg L⁻¹ BTEX compounds in water were in the range 0.9–6.4% (n = 5). Relative recovery from well and wastewater at spiked levels of 5.0 μg L⁻¹ was 89–101% and 76–98%, respectively. Finally, the method was successfully used for preconcentration and analysis of BTEX compounds in different real water samples.

     

Determination of nine emerging pesticides at trace level in aqueous samples using fully automated on-line solid phase extraction coupled with liquid chromatography-mass spectrometry

On-line solid phase extraction (SPE) coupled to liquid chromatography-mass spectrometry (LC-MS) offers an easy and fast strategy to analyze the organic contaminants in environmental samples with high sensitivity and selectivity. This paper described an in-house designed on-line SPE system and an on-line SPE-LC-MS method for the determination of pesticides at trace levels in water samples. The system was assembled from an eight-position valve, a piston pump, a six-port valve and a C18 SPE column, and significantly reduced analysis time by achieving full automation. Moreover, the use of a large enrichment volume (50?mL) significantly enhanced method sensitivity. Using this on-line SPE system, an on-line SPE-LC-MS method was developed for the determination of nine pesticides at trace levels in lake water and seawater sample. Under optimized conditions, method detection limits (MDLs) were 1.00–10.0?ng?L^?1.     

Behaviour of semipermeable membrane devices in neutral pesticide uptake from waters

The application of semipermeable membrane devices (SPMDs) has been evaluated as a passive sampler for the collection of multiresidue pesticides in continental waters. Seven chlorinated, five organophosphorus, six carbamate, nine pyrethroid and ten other pesticides were tested in order to estimate which compounds can be retained with these devices. The effect of water parameters, such as temperature, pH, ionic strength and organic matter content, were evaluated for their effect on the retention of the pesticides by the SPMDs. Studies of uptake from water were performed in a glass beaker containing 2 L distilled water spiked with 50 ng L⁻¹ of each pesticide investigated. A SPMD was put in the beaker, under turbulent conditions, and analysed after 2 days’ extraction. The contents of each SPMD were microwave-assisted-extracted twice with 30 mL hexane–acetone, to 90 °C for 10 min, and this was followed by a cleanup based on acetonitrile partitioning and solid-phase extraction. Gas chromatography with tandem mass spectrometry detection was employed for determination of pesticides, and provided low limits of detection from 0.5 to 7 ng per SPMD. Higher absorption rates were observed for pyrethroid, organophosphorus and chlorinated compounds than for carbamates. Pesticide uptake rates were independent of the water composition and decreased at low temperature. Electronic supplementary material The online version of this article contains supplementary material, which is available to authorized users.     

Optimization and Simultaneous Determination of Alkyl Phenol Ethoxylates and Brominated Flame Retardants in Water after SPE and Heptafluorobutyric Anhydride Derivatization followed by GC/MS

A gas chromatography–mass spectrometry (GC–MS) method was investigated for the simultaneous analysis of two types of endocrine disrupting compounds (EDCs), i.e., alkylphenol ethoxylates and brominated flame retardants (BFRs), by extraction and derivatization followed by GC–MS. Different solid phase extraction (SPE) cartridges (Cleanert PestiCarb, C₁₈, Cleanert-SAX and Florosil), solvents (toluene, tetrahydrofuran, acetone, acetonitrile and ethyl acetate) and bases (NaHCO₃, triethylamine and pyridine) were tested and the best chromatographic analysis was achieved by extraction with Strata-X (33 μm, Reverse Phase) cartridge and derivatization with heptafluorobutyric anhydride at 55 °C under Na₂CO₃ base in hexane. It was observed that APE together with lower substituted PBBs (PBB1, PBB10, PBB18 and PBB49), HBCD and TBBPA can be determined simultaneously under the same GC conditions. This simple and reliable analytical method was applied to determining trace amounts of these compounds from wastewater treatment plant samples. The recoveries of the target compounds from simulated water were above 60 %. The limit of detection ranged from 0.01 to 0.15 μg L⁻¹ and the limit of quantification ranged from 0.05 to 0.66 μg L⁻¹. There were no appreciable differences between filtered and unfiltered wastewater samples from Leeuwkil treatment plant although concentration of target analytes in filtered influent was slightly lower than the concentration of target analytes in unfiltered influent water. The concentrations of the target compounds from the wastewater treatment were determined from LOQ upwards.

     

Comparison of supercritical fluid extraction and liquid-liquid extraction for isolation of selected pesticides stored in freeze-dried water samples

Summary The stability of freeze-dried water samples spiked with eight agrochemicals (atrazine, simazine, linuron, carbaryl, propanil, fenitrothion, parathion and fenamiphos) were examined to evaluate their suitability as candidate reference materials for their determination in water samples. In addition, two different extraction procedures, liquid-liquid and supercritical fluid extraction, were compared for the isolation and trace enrichment of target analytes from freeze-dried water samples. Final analytical determinations were by gas chromatography-nitrogen phosphorus detection and electronic impact mass spectrometry, and by liquid chromatography-diode array detection. The whole methodology developed in this paper permitted the determination of pesticides spiked in water at levels varying from 0.03 to 6.9 g L^–1.     

A Sensitive Method for Methyl tert-Butyl Ether Analysis in Water Samples by a New HS-SPME Vial and GC

In this study, a new sample vial has been designed for the extraction and determination of methyl tert-butyl ether (MTBE) in water samples by headspace solid-phase microextraction method. The special feature of this new vial is cooling the HS above the aqueous sample by cold water stream for maximum analyte absorption on SPME fiber coating. The analysis was by a gas chromatograph equipped with flame ionization detector and a capillary column (CP-sil 13 CB). Some significant variables affecting the extraction procedure were optimized. By use of divinylbenzene/carboxen/polydimethylsiloxane fiber, a sample volume of 10 mL, stirring rate of 1,000 rpm, salt concentration of 24%, extraction time of 15 min and extraction temperature of 83 °C, detection limit of 0.022 μg L⁻¹ and a good linearity (R ² = 0.998) in a calibration range of 0.1–400 μg L⁻¹ were achieved. The relative standard deviation for triplicate runs ranged between 6 and 8%. The method could be applied to the analysis of trace levels of MTBE in various water samples.

     

SPME and SPE comparative study for coupling with microwave-assisted micellar extraction in the analysis of organochlorine pesticides residues in seaweed samples

Solid-phase microextraction (SPME) and solid-phase extraction (SPE) procedures were coupling with microwave-assisted micellar extraction for organochlorine pesticides residues determination in seaweed samples. They were optimized, compared and discussed.Preliminary experiments were performed in order to study experimental conditions for the extraction of pesticides from spiked seaweed samples with microwave-assisted micellar extraction (MAME) using a non-ionic surfactant (Polyoxyethylene 10 Lauryl Ether). After that, SPME and SPE were used to clean-up and preconcentrate MAME extract prior the analysis by liquid chromatography with photodiode array (PDA) detection.Excellent results were obtained for both procedures. Average pesticide recoveries between 80.5 and 104.3% for MAME-SPME and between 73.9 and 111.5% for MAME-SPE were obtained. Relative standard deviations (RSDs) were lower than 10.3% and 5.3% respectively for all recoveries tested, and LOD between 138–348 ng g^− 1 for MAME-SPME and 2–38 ng g^− 1 for MAME-SPE were obtained. The method was validated using Soxhlet extraction procedure.Both methods were applied to analyse target organochlorine pesticides in several seaweed samples and results were compared. These results show the great possibilities of combining MAME-SPE-HPLC-UV for the analysis of seaweed samples, improving the selectivity and sensitivity in the determination of organochlorine pesticides analysis for this kind of samples.     

Application of Double-Phase Liquid Phase Microextraction in the Determination of Partition Coefficients and Analysis of Pesticides in Water Samples

A simple and solvent-minimized sample preparation technique based on two-phase hollow fiber-protected liquid-phase microextraction has been developed and used for the determination of partition coefficient and analysis of selected pesticides in environmental water samples. The analysis was performed by gas chromatography–electron capture detector. Three pesticides namely hexaconazole, quinalphos, and methidathion were considered as target analytes. Extraction conditions such as solvent identity, salt concentration, stirring speed, extraction time, length of the hollow fiber, and volume of donor phase were optimized. The analytes were extracted from a donor phase (water sample) through 3 μL of an organic solvent immobilized in the pores of a porous polypropylene hollow fiber and then into the acceptor phase present inside the hollow fiber. Excellent extractions of the analytes were achieved under the optimized conditions, with relative standard deviations of 4.6–7.9%, correlation coefficients (r ²) of 0.9954–0.9986 and limits of detection of 3–7 ng L^?1. The proposed method provided good average enrichment factors of up to 250-fold. The partition coefficients of the analytes determined were found to be directly correlated with the enrichment factor. The present methodology also confirms the robustness of microextraction for monitoring trace levels of pesticides in environmental water samples.     

GC–MS Determination of Antioxidants in Ground Water Contaminated with JP-8

Accidental spills and leaks of kerosene-based fuel require the differentiation of the exact fuel type between kerosene and JP-8. The detection of the antioxidants, 2,6-Di-tert-butylphenol (DTBP) and 2,4-dimethyl-6-tert-butylphenol (DMTBP) in ground water can be an important clue to distinguish between the two. We have developed a method to determine trace phenolic antioxidants in ground water without derivatization by a gas chromatography–mass spectrometry, and then applied it to distinguish JP-8 from kerosene. 25 ground water samples were collected from 25 monitoring wells in an area contaminated with kerosene-based fuel. The antioxidants from ground water were extracted with methylene chloride. Solid phase extraction (SPE) was compared to liquid extraction (LLE), but LLE was selected due to poorer reproducibility and recovery of SPE. Extraction of the compounds from ground water gave recoveries of about 90% and a detection limit of 0.02 μg L⁻¹. The method was used to analyze groundwater samples contaminated with fuel. DMTBP was detected in concentrations of 0.05–4.65 μg L⁻¹ in 12 of the samples. Since DMTBP is the only antioxidant used in JP-8 in Korea, this suggests that the fuel in the contaminated samples is JP-8.