Selenium speciation in tea by dispersive liquid–liquid microextraction coupled to high‐performance liquid chromatography after derivatization with 2,3‐diaminonaphthalene

Selenium is an important element for human health, and it is present in many natural drinks and foods. Present study described a new method using dispersive liquid–liquid microextraction prior to high‐performance liquid chromatography with a UV variable wavelength detector for the determination of the total selenium, Se(IV), Se(VI), and total organoselenium in tea samples. In the procedure, 2,3‐diaminonaphthalene was used as the chelating reagent, 400 μL acetonitrile was used as the disperser solvent and 60 μL chlorobenzene was used as the extraction solvent. The complex of Se(IV) and 2,3‐diaminonaphthalene in the final extracted phase was analyzed by high‐performance liquid chromatography. The factors influencing the derivatization and microextraction were investigated. Under the optimal conditions, the limit of detection was 0.11 μg/L for Se(IV) and the linearity range was in the range of 0.5–40 μg/L. This method was successfully applied to the determination of selenium in four tea samples with spiked recoveries ranging from 91.3 to 100%.     

A new and rapid method for the determination of nicarbazin residues in poultry feed, eggs and muscle tissue using supercritical fluid extraction and high performance liquid chromatography

A simple and rapid method, using supercritical fluid extraction (SFE) with off-line high-performance liquid chromatography for the isolation and determination of nicarbazin, a popular broad-spectrum coccidiostatic drug used principally in poultry, is described. Results show good repeatability with a minimum quantification level of 0.4 microgram g-1 and mean 'spiked' recoveries of 98%, 100% and 99% using poultry feeds (n = 18), eggs (n = 28) and chicken tissue (n = 20), respectively. SFE using carbon dioxide is proposed as an alternative isolation method to the current Association of Official Analytical Chemists (AOAC) procedure which involves the use of large volumes of a harmful solvent (dimethylformamide) and requires a long tedious separation and clean-up regime (6 h) prior to its determination.     

Combination of ultrasound-assisted ionic liquid dispersive liquid-phase microextraction and high performance liquid chromatography for the sensitive determination of benzoylureas pesticides in environmental water samples

This paper describes a new method for rapid and sensitive determination of diflubenzuron, flufenoxuron, triflumuron and chlorfluazuron in water samples by ultrasound-assisted ionic liquid dispersive liquid-phase microextraction in combination with HPLC. Ionic liquid 1-hexyl-3-methylimidazolium hexafluorophosphate ([C(6)MIM][PF(6)]) was used as the extraction solvent for the enrichment of four benzoylurea (BU) pesticides. Factors such as volume of [C(6)MIM][PF(6)], sonication time, sample pH, extraction time, centrifuging time and salting-out effect were systematically investigated. Under the optimum conditions, an excellent linear relationship was achieved in the range of 1.0-100?μg/L. The detection limits varied from 0.21 to 0.45?μg/L and the precision of the method was below 6.9% (RSD, n=6). The proposed method was successfully applied for the determination of these BU pesticides in water samples and excellent spiked recoveries were achieved. All these results demonstrated that this procedure provided a new simple, rapid, easy to operate, efficient and sensitive method for the analysis of BU pesticides in aqueous samples.     

Appraisal of “classic” and “novel” extraction procedure efficiencies for the isolation of polycyclic aromatic hydrocarbons and their derivatives from biotic matrices

In this study the extraction efficiency of pressurized liquid extraction (PLE), employing different extraction solvent mixtures under different extraction conditions, was compared with extraction efficiencies of commonly used procedures, Soxhlet extraction and extraction enhanced by sonication. Spruce needles and fish tissue were selected as test samples. Purification of obtained extracts was carried out by gel permeation chromatography (GPC) employing gel Bio-Beads S-X3. Identification and quantitation of target PAHs was performed by high-performance liquid chromatography with fluorescence detection (HPLC–FLD).

Within optimisation of PLE conditions, temperature of extraction, type of solvent, duration and number of static cycles as well as the influence of sample pre-treatment (drying, homogenisation, etc.) were tested. Comparison of the extraction efficiency of PLE with the efficiencies of the other techniques was done under the optimised conditions, i.e. sample slurry obtained by desiccation with anhydrous sodium sulphate, extracted at 100 °C in 1 cycle lasting 5 min. Hexane:acetone (1:1, v/v) was chosen as the most suitable extraction solvent for isolation of analytes from test samples.

Comparison of mentioned isolation techniques with respect to the amount of co-extracts, procedure blank levels and time and solvent volume demands was also done.     

Determination of diflubenzuron and chlorbenzuron in fruits by combining acetonitrile‐based extraction with dispersive liquid–liquid microextraction followed by high‐performance liquid chromatography

In this study, a simple and low‐organic‐solvent‐consuming method combining an acetonitrile‐partitioning extraction procedure followed by “quick, easy, cheap, effective, rugged and safe” cleanup with ionic‐liquid‐based dispersive liquid–liquid microextraction and high‐performance liquid chromatography with diode array detection was developed for the determination of diflubenzuron and chlorbenzuron in grapes and pears. Ionic‐liquid‐based dispersive liquid–liquid microextraction was performed using the ionic liquid 1‐hexyl‐3‐methylimidazolium hexafluorophosphate as the extractive solvent and acetonitrile extract as the dispersive solvent. The main factors influencing the efficiency of the dispersive liquid–liquid microextraction were evaluated, including the extractive solvent type and volume and the dispersive solvent volume. The validation parameters indicated the suitability of the method for routine analyses of benzoylurea insecticides in a large number of samples. The relative recoveries at three spiked levels ranged between 98.6 and 109.3% with relative standard deviations of less than 5.2%. The limit of detection was 0.005 mg/kg for the two insecticides. The proposed method was successfully used for the rapid determination of diflubenzuron and chlorbenzuron residues in real fruit samples.     

Isolation, purification and determination of 4-n-nonylphenol and 4-tert-octylphenol in aqueous and biological samples

The aim of the present study was to attempt to describe the procedure of isolation, purification, enrichment and determination of 4-n-nonylphenol (4-n-NP) and 4-tert-octylphenol (4-t-OP) in water and biological samples (fish tissue). There were five procedures of solid phase extraction (SPE) tested using different sorbents for the isolation of analytes from water samples. Moreover, we isolated these chemicals from biological matrices with the aid of various extraction methods. The purpose of it was to perform an optimisation of ultrasonic bath, accelerated solvent extraction (ASE) and solid phase extraction process of alkylphenols from biological samples, through the choice of selective sorbents (octadecyl, octadecyl end-capped and amine) and search solvents (methylene chloride, methanol, hexane). Reversed-phase HPLC with diode array detection was used for the determination of 4-n-NP and 4-t-OP in water and fish tissue samples. Sensitivity was evaluated by determining the limit of detection (LOD=0.06 and 0.04ng microL(-1)) and limit of quantification (LOQ=0.18 and 0.16ng microL(-1)) of 4-NP and 4-t-OP, respectively. A series of standard solutions for 4-n-NP and 4-t-OP provided the basis for plotting an analytical curve and obtaining a linear dependence in the range of approximately 1-25ng microL(-1). The best efficiencies obtained for 4-n-NP and 4-t-OP in water samples were 76.65% (+/-1.49) and 83.08% (+/-3.73), respectively. In the case of fish tissue, different situation was observed because the obtained values were considerably lower, being 68.32% for 4-t-OP using hexane (program 1) as solvent and 72.35% (program 2) for 4-n-NP using acetonitrile.     

Determination of phenols in waters by stir membrane liquid-liquid-liquid microextraction coupled to liquid chromatography with ultraviolet detection

A simple and rapid method for the determination of eleven phenols in water samples is presented. The target analytes are isolated by stir membrane liquid-liquid microextraction working under the three-phase mode. An alkaline aqueous solution is used as extractant phase while octanol is selected as supported liquid membrane solvent. The target analytes are separated and determined by liquid chromatography (LC) with ultraviolet detection (UV). All the variables involved in the extraction process have been studied in depth. Low detection limits (in the range from 82.1 ng/L for phenol to 452 ng/L for 2,4,5-trichlorophenol) were obtained. The repeatability, expressed as relative standard deviation (RSD), varied between 1.3% (for 4-nitrophenol) and 8.0% (for 4-chlorophenol). The enrichment factors were in the range from 168 (for 2,4,5-trichlorophenol) to 395 (for 3-chlorophenol). The proposed procedure was applied for the direct determination of the eleven phenols in some real water samples including river, well and tap waters. The accuracy was evaluated by means of a recovery study, the results being in the range of 87-120%.     

Accelerated solvent extraction combined with dispersive liquid–liquid microextraction before gas chromatography with mass spectrometry for the sensitive determination of phenols in soil samples

A method combining accelerated solvent extraction with dispersive liquid–liquid microextraction was developed for the first time as a sample pretreatment for the rapid analysis of phenols (including phenol, m‐cresol, 2,4‐dichlorophenol, and 2,4,6‐trichlorophenol) in soil samples. In the accelerated solvent extraction procedure, water was used as an extraction solvent, and phenols were extracted from soil samples into water. The dispersive liquid–liquid microextraction technique was then performed on the obtained aqueous solution. Important accelerated solvent extraction and dispersive liquid–liquid microextraction parameters were investigated and optimized. Under optimized conditions, the new method provided wide linearity (6.1–3080 ng/g), low limits of detection (0.06–1.83 ng/g), and excellent reproducibility (<10%) for phenols. Four real soil samples were analyzed by the proposed method to assess its applicability. Experimental results showed that the soil samples were free of our target compounds, and average recoveries were in the range of 87.9–110%. These findings indicate that accelerated solvent extraction with dispersive liquid–liquid microextraction as a sample pretreatment procedure coupled with gas chromatography and mass spectrometry is an excellent method for the rapid analysis of trace levels of phenols in environmental soil samples.     

Development of a simultaneous extraction and cleanup method for pyrethroid pesticides from indoor house dust samples

An efficient and reliable analytical method was developed for the sensitive and selective quantification of pyrethroid pesticides (PYRs) in house dust samples. The method is based on selective pressurized liquid extraction (SPLE) of the dust-bound PYRs into dichloromethane (DCM) with analysis by gas chromatography/mass spectrometry. Various adsorbents and combinations of extraction solvents and temperatures were evaluated to achieve a high-throughput sample preparation that eliminates the post-extraction cleanup step. The final method used sulfuric acid-impregnated silica (acid silica) and neutral silica together in the extraction cell with the dust sample to provide both extraction and cleanup simultaneously. The optimal ratio of dust/acid silica/silica was 1:0.8:8. The extraction was performed at 2000 psi, at 100 °C with DCM for 5 min in three cycles. Method precision and accuracy were evaluated by the analysis of triplicate aliquots of the dust samples and the samples fortified with the target PYRs. The accuracy measured as the recoveries of the PYRs in the fortified samples ranged from 85% to 120%. The precision measured as the relative standard deviation of replicate samples was within ±25%. The SPLE method was applied to 20 house dust samples collected from households that participated in two field studies regarding exposures to pesticides and other pollutants. Similar concentrations of target PYRs were obtained for the SPLE and a stepwise extraction/cleanup procedure. The SPLE procedure reduces organic solvent consumption and increases the sample throughput when compared with a traditional stepwise extraction and cleanup procedure. This study demonstrates that the SPLE procedure can be applied to complex dust matrices for analysis of PYRs for large scale exposure or environmental monitoring studies.     

Solid‐based disperser liquid–liquid microextraction for the preconcentration of phthalate esters and di‐(2‐ethylhexyl) adipate followed by gas chromatography with flame ionization detection or mass spectrometry

A new approach for the development of a dispersive liquid–liquid microextraction followed by GC with flame ionization detection was proposed for the determination of phthalate esters and di‐(2‐ethylhexyl) adipate in aqueous samples. In the proposed method, solid and liquid phases were used as the disperser and extractant, respectively, providing a simple and fast mode for the extraction of the analytes into a small volume of an organic solvent. In this method, microliter levels of an extraction solvent was added onto a sugar cube and it was transferred into the aqueous phase containing the analytes. By manual shaking, the sugar was dissolved and the extractant was released into the aqueous phase as very tiny droplets to provide a cloudy solution. Under optimized conditions, the proposed method showed good precision (RSD less than 5.2%), high enrichment factors (266–556), and low LODs (0.09–0.25 μg/L). The method was successfully applied for the determination of the target analytes in different samples, and good recoveries (71–103%) were achieved for the spiked samples. No need for a disperser solvent and higher enrichment factors compared with conventional dispersive liquid–liquid microextraction and low cost and short sample preparation time are other advantages of the method.     

New procedure for the examination of the degradation of volatile organonitrogen compounds during the treatment of industrial effluents

We present a new procedure for the determination of 32 volatile organonitrogen compounds in samples of industrial effluents with a complex matrix. The procedure, based on dispersive liquid–liquid microextraction followed by gas chromatography with nitrogen‐phosphorus and mass spectrometric detection, was optimized and validated. Optimization of the extraction included the type of extraction and disperser solvent, disperser solvent volume, pH, salting out effect, extraction, and centrifugation time. The procedure based on nitrogen‐phosphorus detection was found to be superior, having lower limits of detection (0.0067–2.29 μg/mL) and quantitation as well as a wider linear range. The developed procedure was applied to the determination of content of volatile organonitrogen compounds in samples of raw effluents from the production of bitumens in which 13 compounds were identified at concentrations ranging from 0.15 to 10.86 μg/mL and in samples of effluents treated by various chemical methods.     

A new procedure for determination of nickel in some fake jewelry and cosmetics samples after dispersive liquid–liquid microextraction by FAAS

A new, simple and cheap dispersive liquid–liquid microextraction (DLLME) procedure was optimized for the preconcentration of trace amounts of Ni(II) as a prior step to its determination by flame atomic absorption spectrometry (FAAS). It is based on the microextraction of nickel, where appropriate amounts of the extraction solvent (CHCl₃), disperser solvent (ethanol) and chelating agent, name 5‐[(Z)‐isoxazol‐3‐yl‐diazenyl]‐2‐methyl‐quinolin‐8‐ol (MMD), were firstly synthesized/characterized and used. Various parameters that affect the extraction procedure such as pH, centrifugation rate and time, the chelating agent (MMD) concentration and sampling volume on the recovery of Ni(II) were investigated. The preconcentration of a 20 ml sample solution was thus enhanced by a factor of 80. The resulting calibration graph was linear in the range of 0.24–10 mg L⁻¹ with a correlation coefficient of 0.9998. The limit of detection (3 s/b) obtained under optimal conditions was 1.00 μg L⁻¹. The relative standard deviation for certified reference material determinations was 1.2%. The accuracy of the method was verified by the determination of Ni(II) in the certified reference material of wastewater (Waste water CWW TMD). The proposed procedure was successfully applied to the determination of Ni(II) in some fake jewelry and cosmetics samples.     

Radioanalytical determination of actinoids in refractory matrices by alkali fusion

In this work a method used conventionally for ICP-MS measurements have been modified and readapted for the determination of actinides (U and Th isotopes) in refractory samples by alpha-spectrometry. The method is based in a total dissolution of the sample by alkali fusion. In the first stages of our studies, we try to digest refractory samples by leaching with aqua regia followed by the application of a liquid–liquid solvent extraction process for the sequential isolation of the uranium and thorium isotopes from the dissolved fraction. These actinides were finally electroplated in stainless steel discs and measured in an alpha-spectrometer using PIPS detectors. On the other hand, gamma measurements were carried out in aliquots of the same samples in order to check the results produced by alpha spectrometry. Clear disagreements were found between the results obtained by both techniques. This problem was solved by the application of an alkali fusion technique where a total dissolution of the sample is performed. It was found in addition that the alkali fusion is easily applicable, less time-consuming, needs less reagents than leaching and it does not require sophisticated apparatus to be executed. In this paper the whole procedure for U and Th determination in refractory samples by alpha-spectrometry with alkali fusion is presented and validated.     

Determination of Tetrachloroethylene and Other Volatile Halogenated Organic Compounds in Oil Wastes by Headspace SPME GC–MS

Oil wastes and slops are complex mixtures of hydrocarbons, which may contain a variety of contaminants including tetrachloroethylene (perchloroethylene, PCE) and other volatile halogenated organic compounds (VHOCs). The analytical determination of PCE at trace levels in petroleum-derived matrices is difficult to carry out in the presence of large amounts of hydrocarbon matrix components. In the following study, we demonstrate that headspace solid-phase microextraction (HS-SPME) combined with GC–MS analysis can be applied for the rapid measurement of PCE concentration in oil samples. The HS-SPME method was developed using liquid paraffin as matrix matching reference material for external and internal calibration and optimisation of experimental parameters. The limit of quantitation was 0.05 mg kg⁻¹, and linearity was established up to 25 mg kg⁻¹. The HS-SPME method was extended to several VHOCs, including trichloroethylene (TCE) in different matrices and was applied to the quantitative analysis of PCE and TCE in real samples.     

Applications of ethylammonium and propylammonium nitrate solvents in liquid-liquid extraction and chromatography

Ethyl- and propylammonium nitrate are novel ionic solvents, liquid at room temperature, suitable for use as selective solvents for the isolation of analytes containing proton donor functional groups (alcohols, amines, phenols, carboxylic acids, etc.) by liquid-liquid distribution. These solvents form immiscible solvent pairs with non-polar aliphatic and aromatic hydrocarbons, ethers and alkyl halide solvents (e.g., methylene chloride, chloroform). Analytes can be recovered from the ionic solvents by back-extraction into ah organic solvent after dilution with water or pH buffer or, preferably, by extractive derivatization when gas chromatography is used for the analyses, avoiding the accumulation of salt on the column that results in poor baseline stability. Alkylation, acylation and particularly silylation are suitable methods for extractive derivatization using standard reaction conditions. Applications are presented for the isolation of polar analytes from an urban dust, shale oil and urine samples and for the determination of low-molecular-weight alcohols in gasahol and glycerol in soap. Liquid-liquid chromatographic systems with the liquid organic salt as stationary phase can be used to predict distribution constants for a particular separation and for the separation of polar solutes, particularly isomeric compounds possessing a proton donor functional group.     

New procedure for the control of the treatment of industrial effluents to remove volatile organosulfur compounds

We present a new procedure for the determination of volatile organosulfur compounds in samples of industrial effluents using dispersive liquid–liquid microextraction and gas chromatography with flame photometric detection. Initially, the extraction parameters were optimized. These included: type and volume of extraction solvent, volume of disperser solvent, salting out effect, pH, time and speed of centrifugation as well as extraction time. The procedure was validated for 30 compounds. The developed procedure has low detection limits of 0.0071–0.49 μg/L and a good precision (relative standard deviation values of 1.2–5.0 and 0.6–4.1% at concentrations of 1 and 10 μg/L, respectively). The procedure was used to determine the content of volatile organosulfur compounds in samples of effluents from the production of bitumens before and after chemical treatment, in which six compounds were identified, including 2‐mercaptoethanol, thiophenol, thioanisole, dipropyl disulfide, 1‐decanethiol, and phenyl isothiocyanate at concentrations ranging from 0.47 to 8.89 μg/L. Problems in the determination of organosulfur compounds related to considerable changes in composition of the effluents, increase in concentration of individual compounds and appearance of secondary pollutants during effluent treatment processes are also discussed.     

Pressurized liquid extraction versus other extraction techniques in micropreparative isolation of pharmacologically active isoflavones from Trifolium L. species

As a new sample preparation technique, pressurized liquid extraction (PLE), in combination with reversed-phase liquid chromatography (RP-LC) and photodiode-array (PDA) detection were used for the isolation and determination of phytoestrogenic isoflavones in hydrolyzed extracts obtained from aerial parts of five Trifolium L. (clover) species. To optimize the effectiveness of PLE procedure, variable extraction parameters: methanol and acetone (or their 75% aqueous solutions), as extraction solvents, temperatures (75, 100 and 125 °C) and the changeable number of static extraction cycles were tested. Additionally, two other micropreparative techniques: ultrasound-assisted extraction (UAE), and conventional solvent extraction (CSE), under optimized conditions, were also used and compared. Optimum extraction efficiency, expressed in the highest yield of biochanin A, formononetin, daidzein and genistein from plant material, with PLE, using methanol-water (75:25, v/v) as an extraction solvent, an oven temperature of 125 °C and three 5-min static extraction cycles, was obtained.     

Determination of bisphenol A and bisphenol B in canned seafood combining QuEChERS extraction with dispersive liquid–liquid microextraction followed by gas chromatography–mass spectrometry

A new simple and reliable method combining an acetonitrile partitioning extractive procedure followed by dispersive solid-phase cleanup (QuEChERS) with dispersive liquid–liquid microextraction (DLLME) and further gas chromatography mass spectrometry analysis was developed for the simultaneous determination of bisphenol A (BPA) and bisphenol B (BPB) in canned seafood samples. Besides the great enrichment factor provided, the final DLLME extractive step was designed in order to allow the simultaneous acetylation of the compounds required for their gas chromatographic analysis. Tetrachloroethylene was used as extractive solvent, while the acetonitrile extract obtained from QuEChERS was used as dispersive solvent, and anhydride acetic as derivatizing reagent. The main factors influencing QuEChERS and DLLME efficiency including nature of QuEChERS dispersive-SPE sorbents, amount of DLLME extractive and dispersive solvents and nature and amount of derivatizing reagent were evaluated. DLLME procedure provides an effective enrichment of the extract, allowing the required sensitivity even using a single quadropole MS as detector. The optimized method showed to be accurate (>68?% recovery), reproducible (<21?% relative standard deviation) and sensitive for the target analytes (method detection limits of 0.2?μg/kg for BPA and 0.4?μg/kg for BPB). The screening of several canned seafood samples commercialized in Portugal (total?=?47) revealed the presence of BPA in more than 83?% of the samples with levels ranging from 1.0 to 99.9?μg/kg, while BPB was found in only one sample at a level of 21.8?μg/kg.     

High-performance liquid chromatographic procedure for the determination of di-(2-ethylhexyl)phthalate in human blood specimens. Problems of variable-extraction yield and the use of standard addition for calibration

A high-performance liquid chromatographic procedure was developed for the determination of di-(2-ethylhexyl)phthalate (DEHP) concentrations in human whole blood samples. The solvent extraction of DEHP was found to be highly variable between samples obtained from different subjects (coefficient of variation of 30.4%). The recovery of DEHP following extraction with ethyl acetate was negatively correlated with serum lipid content, as expressed by the sum of serum cholesterol and triglyceride concentrations (r = -0.864). The technique of standard addition of DEHP allowed a single-point calibration of DEHP extractability in individual blood samples, and provided an accurate estimation of DEHP concentration (coefficient of variation of approximately 6% in replicate samples). The potential for intersample variability in the solvent extraction of other highly lipid-soluble compounds should be considered.     

Trace analysis of antibacterial tylosin A, B, C and D in honey by liquid chromatography-electrospray ionization-mass spectrometry

A new LC-ESI-MS method was developed for the determination of residues of the antibacterial tylosins A, B, C and D in honey. The procedure employed an SPE on polymeric cartridges for the isolation of tylosins from diluted honey. Chromatographic separation of the tylosins was performed on a C18 column (150 x 4.60 mm2 ID, 5 microm) using a ternary gradient made of formic acid 1% in water (solvent A), methanol (solvent B) and ACN (solvent C) as mobile phase, at 30 degrees C and at a flow rate of 0.8 mL/min. Average analyte recoveries for the studied compounds ranged from 89 to 106% in replica sets of fortified honey samples. The detection limits for the four drugs studied were between 2 and 3 microg/kg. The developed method has been applied to the analysis of tylosin residues in honey from veterinarian treated beehives fed with the technical product, which contains the four compounds and is a new candidate antibiotic to treat American foulbrood disease of honey bee colonies.