Novel solvent-free microwave-assisted extraction coupled with low-density solvent-based in-tube ultrasound-assisted emulsification microextraction for the fast analysis of organophosphorus pesticides in soils.

A novel and rapid solventless microwave-assisted extraction coupled with low-density solvent-based in-tube ultrasound-assisted emulsification microextraction has been developed for the efficient determination of nine organophosphorus pesticides in soils by GC analysis with microelectron capture detection. A specially designed, homemade glass tube inbuilt with a scaled capillary tube was used as an extraction device to collect and measure the separated extractant phase easily. Parameters affecting the efficiencies of the developed method were thoroughly investigated. From experimental results, the following conditions were selected for the extraction of organophosphorus pesticides from 1.0 g of soil sample to 5 mL of aqueous solution under 226 W of microwave irradiation for 2.5 min followed by ultrasound-assisted emulsification microextraction with 20 µL toluene for 30 s and then centrifugation at 3200 rpm for 3 min. Detections were linear in the range of 0.25-10 ng/g with detection limits between 0.04 and 0.13 ng/g for all target analytes. The applicability of the method to real samples was assessed on agricultural contaminated soils and the recoveries ranged between 91.4 and 101.3%. Compared to other methods, the present method was shown to be highly competitive in terms of sensitivity, cost, eco-friendly nature, and analysis speed.

Determination of ammonium in aqueous samples using new headspace dynamic in-syringe liquid-phase microextraction with in situ derivitazation coupled with liquid chromatography-fluorescence detection.

A new simultaneous derivatization and extraction method for the preconcentration of ammonia using new one-step headspace dynamic in-syringe liquid-phase microextraction with in situ derivatization was developed for the trace determination of ammonium in aqueous samples by liquid chromatography with fluorescence detection (LC-FLD). The acceptor phase (as derivatization reagent) containing o-phthaldehyde and sodium sulfite was held within a syringe barrel and immersed in the headspace of sample container. The gaseous ammonia from the alkalized aqueous sample formed a stable isoindole derivative with the acceptor phase inside the syringe barrel through the reciprocated movements of plunger. After derivatization-cum-extraction, the acceptor phase was directly injected into LC-FLD for analysis. Parameters affecting the ammonia evolution and the extraction/derivatization efficiency such as sample matrix, pH, temperature, sampling time, and the composition of derivatization reagent, reaction temperature, and frequency of reciprocated plunger, were studied thoroughly. Results indicated that the maximum extraction efficiency was obtained by using 100µL derivatization reagent in a 1-mL gastight syringe under 8 reciprocated movements of plunger per min to extract ammonia evolved from a 20mL alkalized aqueous solution at 70°C (preheated 4min) with 380rpm stirring for 8min. The detection was linear in the concentration range of 0.625-10µM with the correlation coefficient of 0.9967 and detection limit of 0.33µM (5.6ng mL(-1)) based on SN(-1)=3. The method was applied successfully to determine ammonium in real water samples without any prior cleanup of the samples, and has been proved to be a simple, sensitive, efficient and cost-effective procedure for trace ammonium determination in aqueous samples.

Development of one-step hollow fiber supported liquid phase sampling technique for occupational workplace air analysis using high performance liquid chromatography with ultra-violet detector.

In this study, a simple and novel one-step hollow-fiber supported liquid-phase sampling (HF-LPS) technique was developed for enriched sampling of gaseous toxic species prior to chemical analysis for workplace air monitoring. A lab-made apparatus designed with a gaseous sample generator and a microdialysis sampling cavity (for HF-LPS) was utilized and evaluated to simulate gaseous contaminant air for occupational workplace analysis. Gaseous phenol was selected as the model toxic species. A polyethersulfone hollow fiber dialysis module filled with ethylene glycol in the shell-side was applied as the absorption solvent to collect phenol from a gas flow through the tube-side, based on the concentration distribution of phenol between the absorption solvent and the gas flow. After sampling, 20 µL of the extractant was analyzed by high performance liquid chromatography with ultraviolet detection (HPLC-UV). Factors that influence the generation of gaseous standards and the HF-LPS were studied thoroughly. Results indicated that at 25 °C the phenol (2000 µg/mL) standard solution injected at 15-µL/min can be vaporized into sampling cavity under nitrogen flow at 780 mL/min, to generate gaseous phenol with concentration approximate to twice the permissible exposure limit. Sampling at 37.3 mL/min for 30 min can meet the requirement of the workplace air monitoring. The phenol in air ranged between 0.7 and 10 cm³/m³ (shows excellent linearity) with recovery between 98.1 and 104.1%. The proposed method was identified as a one-step sampling for workplace monitoring with advantages of convenience, rapidity, sensitivity, and usage of less-toxic solvent.

Determination of alachlor and its metabolite 2,6-diethylaniline in microbial culture medium using online microdialysis enriched-sampling coupled to high-performance liquid chromatography.

In this study, a simple and novel microdialysis sampling technique incorporating hollow fiber liquid phase microextraction (HF-LPME) coupled online to high-performance liquid chromatography (HPLC) for the one-step sample pretreatment and direct determination of alachlor (2-chloro-2',6'-diethyl-N -(methoxymethyl)acetanilide) and its metabolite 2,6-diethylaniline (2,6-DEA) in microbial culture medium has been developed. A reversed-phase C-18 column was utilized to separate alachlor and 2,6-DEA from other species using an acetonitrile/water mixture (1:1) containing 0.1 M phosphate buffer solution at pH 7.0 as the mobile phase. Detection was carried out with a UV detector operated at 210 nm. Parameters that influenced the enrichment efficiency of online HF-LPME sampling, including the length of the hollow fiber, the perfusion solvent and its flow rate, the pH, and the salt added in sample solution, as well as chromatographic conditions were thoroughly optimized. Under optimal conditions, excellent enrichment efficiency was achieved by the microdialysis of a sample solution (pH 7.0) using hexane as perfusate at the flow rate of 4 µL/min. Detection limits were 72 and 14 ng/mL for alachlor and 2,6-DEA, respectively. The enrichment factors were 403 and 386 (RSD < 5%) for alachlor and 2,6-DEA, respectively, when extraction was performed by using a 40 cm regenerated cellulose hollow fiber and hexane as perfusion solvent at the flow rate of 0.1 µL/min. The proposed method provides a sensitive, flexible, fast, and eco-friendly procedure to enrich and determine alachlor and its metabolite (2,6-DEA) in microbial culture medium.

Determination of pyrethroid metabolites in human urine using liquid phase microextraction coupled in-syringe derivatization followed by gas chromatography/electron capture detection.

Metabolites of synthetic pyrethroids such as cis-3-(2,2-dibromovinyl)-2,2-di-methylcyclo-propane-1-carboxylic acid, cis- and trans-3-(2,2-dichlorovinyl)-2,2-dimethylcyclopropane-1-carboxylic acid), 3-phenoxybenzoic acid (3-PBA), and 4-fluoro-3-PBA are biomarkers for exposure to phenothrin, tetramethrin, cyfluthrin, cypermethrin, deltamethrin, and permethrin. In this study, the pyrethroid metabolites in workers' urine samples were monitored for the first time with a novel sample pretreatment process combining hollow fiber liquid phase microextraction (HF-LPME) and in-syringe derivatization (ISD) followed by gas chromatography-electron capture detector (GC-ECD) analysis. A micro-syringe pre-filled with derivatizing agents and syringe needle connected to an extracting solvent impregnated hollow fiber segment was used as the LPME probe. Pyrethroid metabolites were extracted and enriched simultaneously from urine samples by HF-LPME sampling and acid hydrolysis at 70 °C for 10 min. After sampling, the ISD was performed by mixing the extracting solution and derivatizing agents through plunger movements, followed by GC-ECD analysis. Parameters influencing the HF-LPME efficiency and ISD were investigated and optimized. Under optimum conditions, the method provided enrichment factors of 69.8-154.6, repeatability from 5.0 to 12% (n = 5), and good linearity (R(2) = 0.9980-0.9998) for interested analytes spiked in urine samples. The method detection limits ranged from 1.6 to 17 ng/mL. A comparison was performed between the proposed method and conventional methods. The proposed method was applied to analyze pyrethroid metabolites in the urine samples collected from workers of pesticide formulation plants. The results suggested that the proposed HF-LPME coupled ISD method was a rapid, simple, efficient, and eco-friendly technique in the biomonitoring of metabolites of pyrethroids in workers' urine.

Application of microwave-assisted desorption/headspace solid-phase microextraction as pretreatment step in the gas chromatographic determination of 1-naphthylamine in silica gel adsorbent.

Pretreatment of silica gel sample containing 1-naphthylamine by microwave-assisted desorption (MAD) coupled to in situ headspace solid phase microextraction (HS-SPME) has been investigated as a possible alternative to conventional methods prior to gas chromatographic (GC) analysis. The 1-naphthylamine desorbs from silica gel to headspace under microwave irradiation, and directly absorbs onto a SPME fiber located in a controlled-temperature headspace area. After being collected on the SPME fiber, and desorbed in the GC injection port, 1-naphthylamine is analyzed by GC-FID. Parameters that influence the extraction efficiency of the MAD/HS-SPME, such as the extraction media and its pH, the microwave irradiation power and irradiation time as well as desorption conditions of the GC injector, have been investigated. Experimental results indicate that the extraction of a 150mg silica gel sample by using 0.8ml of 1.0M NaOH solution and a PDMS/DVB fiber under high-powered irradiation (477W) for 5min maximizes the extraction efficiency. Desorption of 1-naphthylamine from the SPME fiber in GC injector is optimal at 250 degrees C held for 3min. The detection limit of method is 8.30ng. The detected quantity of 1-naphthylamine obtained by the proposed method is 33.3 times of that obtained by the conventional solvent extraction method for the silica gel sample containing 100ng of 1-naphthylamine. It provides a simple, fast, sensitive and organic-solvent-free pretreatment procedure prior to the analysis of 1-naphthylamine collected on a silica gel adsorbent.

Determination of aniline in silica gel sorbent by one-step in situ microwave-assisted desorption coupled to headspace solid-phase microextraction and GC-FID.

Microwave-assisted desorption (MAD) coupled to in situ headspace solid-phase microextraction (HS-SPME) was first proposed as a possible alternative pretreatment of samples in absorbent collected from workplace monitoring. Aniline collected on silica gel was investigated. Under microwave irradiation, the aniline was desorbed from silica gel and directly absorbed onto the SPME fiber in the headspace. Having been sampled on the SPME fiber, and desorbed in the GC injection port, aniline was analyzed using a GC-FID system. Parameters that affect the proposed extraction efficiency, including the extraction media and its pH, the microwave irradiation power and the irradiation time as well as desorption parameters of the GC injector, were investigated. Experimental results revealed that the extraction of a 150-mg silica gel sample using a 0.8-ml aqueous solution (pH 12) and a PDMS/DVB fiber under medium-high-powered irradiation (345W) for 3min maximized the efficiency of extraction. Desorption of aniline from the SPME fiber was optimal at 230 degrees C held for 3min. The detection limit was 0.09ng. The proposed method provided a simple, fast, and organic solvent-free procedure to analyze aniline from a silica gel matrix.