A low-cost flame atomic absorption spectrometry method for determination of trace metals in aqueous samples

A simple and fast method for the extraction into xylene of sub mug l(-1) concentrations of metals using ammonium diethyldithiophosphate (DDTP) as a complexing reagent and their subsequent determination by flame atomic absorption spectrometry is described. The method was tested in sea water spiked with Au at a concentration of 3.0 mug l(-1). The extraction was carried out until the aqueous to organic phase ratio achieved a 1000-fold preconcentration of metal. Optimisation of extraction parameters and the effect of Fe interference was investigated. Sea water samples spiked with Au produced an average recovery of 95% and the detection limit (3sigma) in deionized water was 2.9 ng l(-1). High enrichment factors could be obtained due to the small final volume (mul) of organic solvent.     

Miniaturized membrane-assisted solvent extraction combined with gas chromatography/electron-capture detection applied to the analysis of volatile organic compounds

A new module of membrane-assisted solvent extraction (MASE) with miniaturized membrane bags was applied to the determination of seven volatile organic compounds (VOCs): chloroform, 1,1,1-trichloroethane, trichloroethylene, 1,1,2-trichloroethane, tetrachloroethene, 1,1,1,2-tetrachloroethane, 1,1,2,2-tetrachloroethane with boiling points between 61 and 147 degrees C in aqueous samples. Different from the known procedure the new, shortened membrane bags were filled with 100 microl of an organic solvent. The membrane bags were placed in a 20 ml headspace vial and filled with 15 ml of the aqueous sample. The vial was transferred into an autosampler where it was stirred for a definite time at elevated temperature. After the extraction, 1 microl of the organic extract was transferred into the spilt/splitless injector of a GC system equipped with an electron-capture detector. This work included optimization of the membrane device, the determination of the optimized extraction conditions such as stirring rate, extraction time and the impact of salt addition. The validation of the method involved repeatability, recovery and detection limit studies, followed of its application towards real water samples. The repeatability, expressed as the relative standard deviation of the peak areas of six extractions was below 10%. The detection limits (LODs) were between 5 ng/l (tetrachloroethene) and 50 ng/l (chloroform). Calibration was performed in a range from 5 ng/l to 150 microg/l, since the concentration in the aqueous samples was expected quite various in this concentration range. Five river water samples of Bitterfeld, Saxony-Anhalt, Germany were analyzed with miniaturized-MASE and the results were compared with those obtained with Headspace-Analysis. The method can be fully automated and moreover, it allows the simultaneous determination of volatile and semi volatile compounds.     

Extracting syringe for extraction of phthalate esters in aqueous environmental samples

The use of the extracting syringe (ESy), a fully automated membrane-based extraction technique, for analysis of phthalate esters in complex aqueous samples has been investigated. The ESy, working as an autosampler that combines the extraction process and injection into the gas chromatograph (GC) in one single step, is placed on top of the GC equipped with a flame ionisation detector. The aqueous samples are loaded in a tray and automatically extracted by employing microporous membrane liquid-liquid extraction principle. After the extraction, the extract is directly injected into the GC's programmable temperature vaporisation injector. Six different phthalate esters were used as model compounds. Four extraction solvents were tested and the addition of sample organic modifier was examined.Toluene was the optimal solvent to use for extraction. Due to the large variation in polarity of phthalate esters, 50% methanol as organic modifier had to be added to the samples so as to extract the most nonpolar phthalate esters; di-2-ethylhexylphthalate and di-n-octylphthalate, whereas the other four relatively polar phthalate esters were extracted from unmodified samples. No significant difference between extraction of river water, leachate water from a landfill and reagent water was noted, except for minor deviations. The extraction time was 20 min for extraction of a 1-mL sample, resulting in a good linearity for all aqueous media investigated, good enrichment factors (54-110 folds) and low LOD values (0.2-10 ng mL⁻¹) and relative standard deviation (%R.S.D.; 0.9-3.7%).     

Polymer-coated hollow-fiber microextraction of estrogens in water samples with analysis by gas chromatography-mass spectrometry

A novel sorbent, dihydroxylated polymethylmethacrylate (DHPMM), coated on hollow-fiber membrane, is used for the polymer-coated hollow-fiber microextraction of trace amounts of natural and synthetic estrogens, such as diethylstilbestrol, estrone, 17beta-estradiol and 17alpha-ethynylestradiol, in aqueous samples. In this procedure, estrogens were extracted using the functionalized polar DHPMM polymer with derivatization using N-methyl-N-(trimethylsilyl)trifluoroacetamide followed by gas chromatography-mass spectrometric analysis. The detection limits for estrogens in aqueous sample were between 0.03 and 0.8 ng l(-1) and the calibration curves were linear over the concentration range 0.05-10 microgl(-1) and had correlation coefficients of >0.994. The relative standard deviations (RSDs) were <15% (n = 3). This simple, accurate, sensitive and selective analytical method is applicable to the determination of trace amounts of estrogens in reservoir and potable water samples.     

Membrane-assisted solvent extraction of polychlorinated biphenyls in river water and other matrices combined with large volume injection-gas chromatography-mass spectrometric detection

Membrane-assisted solvent extraction was applied to the determination of polychlorinated biphenyls (PCBs) in aqueous samples. The apparatus of membrane-assisted solvent extraction consisted of a 20 ml headspace vial which was filled with 15 ml of the aqueous sample. The membrane bag was placed into the vial and the extraction took place in an agitator. After extraction, the analytes were transferred into the inlet of a gas chromatograph by large volume injection. A mass-selective detector was used. The whole procedure was fully automated. The work included optimization of the extraction conditions (stirring rate and extraction time) and the influence of matrix effects like salt addition and the presence of organic solvents was studied. Calibration was performed using injection volumes of 100 and 400 microl. Several parameters like linearity and reproducibility of the procedure were determined. At optimized conditions detection limits in the ng/l range were achieved. The effectiveness of the method towards real samples was tested by analyzing river water, white wine and apple juice.     

Optimisation of solvent desorption conditions for chemical warfare agent and simulant compounds from Porapak Q using experimental design. Part 2: Extraction of sulphur mustard from steel and glass Porapak tubes

The ion-pair solid-phase extraction (SPE) of 4-alkylphenols followed by derivatization with pentafluoropyridine is demonstrated. Under alkaline conditions, the 4-alkylphenols could be efficiently adsorbed on a C18 SPE cartridge conditioned with an ion-pair reagent, tetra-n-hexylammonium bromide. The ion pairs, ammonium phenolates, formed on the C18 solid phase, were eluted with a solvent containing the derivatizing reagent, pentafluoropyridine, and completely derivatized during the elution. After optimization of the adsorption and derivatization, we established a method for the determination of the 4-alkylphenols in water samples. The method showed good linearity between 20 and 1000 ng (200-10,000 ng for nonylphenol). By processing 20-ml samples, the method detection limits (MDL) were in the range of 5.2-8.9 ng/l for the 4-alkylphenols (76 ng/l for nonylphenol). To evaluate its applicability to a real aqueous matrix, several river water samples were analyzed.     

Development of a simple hollow fibre supported liquid membrane extraction method to extract and preconcentrate dinitrophenols in environmental samples at ng L(-1) level by liquid chromatography

An easy and rapid hollow-fibre supported liquid membrane method (HFSLM) has been developed to extract and determinate the total concentration of four dinitrophenols in environmental water at ng L(-1) level. This extraction method provides a high selectivity, short extraction time and very low cost for real samples. It is a three-phase system, aqueous-organic-aqueous, where the organic solvent is held into the fibre pores, being in contact with the two other phases. The organic phase is formed by two different organic solvents, with two different polarities, n-undecane and toluene (1:1). The optimization step was performed using a three-variable Doehler design, involving three factors, stirring speed, fibre length and sample volume. The organic phase composition, as well as the pH of the acceptor and donor phases was also optimized. The extraction equilibrium was reached after 30 min, after which essentially the total amount (90-80%) of the four dinitrophenolic compounds were extracted from the sample. Better repeatability and reproducibility at the expense of lower enrichment factors was obtained compared with other methods, employing incomplete extraction during a fixed time. The matrix effect was tested by performing extractions from leachate water and river water. This method is linear in the range 0.1-100 microgL(-1) in different matrices, with detection limit around 100 ng L(-1), after extraction of 6 mL of sample and using high performance liquid chromatography for final analysis.     

Extraction and determination of polybrominated diphenyl ethers in water and urine samples using solidified floating organic drop microextraction along with high performance liquid chromatography

We have developed a method, termed solidification of floating organic drop microextraction (SFOME), for the extraction of polybrominated diphenyl ethers (PBDEs) in water and urine samples, this followed by quantification via HPLC. This method requires very small quantities of organic solvent consumption. It is based on exposing a floating solidified drop of an organic solvent on the surface of aqueous solution in a sealed vial. The organic drop is easily collected with a spatula, molten (at ambient temperature), and then submitted to HPLC. Experimental parameters including extraction solvent and its volume, disperser solvent and its volume, extraction time, ionic strength, stirring speed and extraction temperature were optimized. The enrichment factors of analytes are in the range from 921 to 1,462, and acceptable extraction recoveries (92%–118%) are obtained. The dynamic linear range for five PBDE congeners is in the range of 0.5–75?μg.L^?1 and from 5 to 500?μg.L^?1 for BDE 209. The correlation coefficients range from 0.9960 to 0.9999. The limits of detection (at S/N?=?3) for PBDE congeners vary between 0.01 and 0.04?μg.L^?1. This method has been successfully applied to detecting PBDEs in two environmental waters and in human urine.

Analysis of polycyclic aromatic hydrocarbons in water and beverages using membrane-assisted solvent extraction in combination with large volume injection-gas chromatography-mass spectrometric detection

Membrane-assisted solvent extraction (MASE) in combination with large volume injection-gas chromatography-mass spectrometry (LVI-GC-MS) was applied for the determination of 16 polycyclic aromatic hydrocarbons (PAHs) in aqueous samples. The MASE conditions were optimized for achieving high enrichment of the analytes from aqueous samples, in terms of extraction conditions (shaking speed, extraction temperature and time), extraction solvent and composition (ionic strength, sample pH and presence of organic solvent). Parameters like linearity and reproducibility of the procedure were determined. The extraction efficiency was above 65% for all the analytes and the relative standard deviation (RSD) for five consecutive extractions ranged from 6 to 18%. At optimized conditions detection limits at the ng/L level were achieved. The effectiveness of the method was tested by analyzing real samples, such as river water, apple juice, red wine and milk.     

Determination of polybrominated diphenyl ethers in domestic dust by microwave-assisted solvent extraction and gas chromatography-tandem mass spectrometry

In this paper, a rapid and simple method for the analysis of polybrominated diphenyl ethers (PBDEs) in house dust samples based on microwave-assisted solvent extraction (MASE) and gas chromatography-tandem mass spectrometry (GC-MS/MS) is presented. Extraction conditions were optimized using a multifactorial experimental design approach. The use of an aqueous NaOH phase in combination with a non-polar organic phase (hexane) to extract the target analytes from dust allowed an efficient extraction and reduced chromatographic background. The final hexane extracts could be analyzed after a simple one-step cleanup procedure using Florisil. The validation of the method was performed in terms of accuracy, linearity, and repeatability. The limits of detection (LODs) ranged from 0.29 to 0.55 ng/g for all compounds. The target PBDEs were found in several real dust samples collected in urban and rural houses of Northwestern Spain.     

Analysis of organochlorine pesticides in wine by solvent bar microextraction coupled with gas chromatography with tandem mass spectrometry detection

A solvent bar microextraction (SBME) technique combined with gas chromatography/tandem mass spectrometry (GC/MS/MS), for the determination of selected organochlorine pesticides (OCPs) in wine samples, is described. In this work the OCPs were extracted and dissolved in a 2-microL aliquot of organic extraction solvent (n-tetradecane) confined within a 1.7-cm length of hollow fiber. Both ends of the hollow fiber (solvent bar) were sealed, and it was placed in an aqueous sample solution for extraction. The effects of solvent selection, sample agitation, extraction time, extraction temperature, and salt concentration on the SBME performance were optimized. The influence of aqueous sample/organic solvent phase ratio was further investigated in detail. High enrichments (1900-7100-fold) could be obtained at an aqueous sample/organic solvent volume ratio of 20 mL/2 microL in this study. Good extraction reproducibility was obtained with relative standard deviation (RSD) values below 12.6%. Comparisons of sensitivity and precision between SBME and dynamic hollow-fiber liquid-phase microextraction were also investigated.     

Determination of organophosphorus pesticides using membrane-assisted solvent extraction combined with large volume injection-gas chromatography-mass spectrometric detection

Eight organophosphorus pesticides (parathion-methyl, fenitrothion, malathion, fenthion, bromophos, bromophos-ethyl, fenamiphos and ethion) in aqueous samples were analysed by means of membrane-assisted solvent extraction. First a 20 ml extraction vial was filled with 15 ml of aqueous sample. Then the membrane bag consisting of nonporous polypropylene was put into the vial and filled with 800 microl of organic solvent. The analytes were separated from the aqueous layer by transporting them through the membrane material into the small amount of solvent. The technique was fully automated and successfully combinable with large volume extraction and GC-MS. To achieve an optimum performance several extraction conditions were investigated. Cyclohexane was chosen as acceptor phase. Then the impact of salt, methanol, pH value, as well as working parameters like stirring rate of the agitator and extraction time, were studied. Moreover, the influence of matrix effects was examined by adding different concentrations of humic acid sodium salt. Detection limits in the ng/l level were achieved using large volume injection with the injecting volume of 100 microl. The recovery values ranged from 47 to 100% and the relative standard deviation for three standard measurements was between 4 and 12% (except for bromophos-ethyl: 22%). The linear dynamic range was between 0.001 and 70 microg/l. The applicability of the method to real samples was tested by spiking the eight organophosphorus pesticides to red wine, white wine and apple juice samples.     

Hollow fiber supported liquid membrane extraction coupled with thermospray flame furnace atomic absorption spectrometry for the speciation of Sb(III) and Sb(V) in environmental and biological samples

A new method of hollow fiber supported liquid membrane extraction (HF-SLME) coupled with thermospray flame furnace atomic absorption spectrometry (TS-FF-AAS) for the speciation of Sb(III) and Sb(V) in environmental and biological samples has been developed. The method is based on the complex of Sb(III) with sodium diethyldithiocarbamate (DDTC). The formed hydrophobic complex is subsequently extracted into the lumen of hollow fiber, whereas Sb(V) is remained in aqueous solutions. The extraction organic phase was injected into TS-FF-AAS for the determination of Sb(III). Total Sb concentration was determined after reduction of Sb(V) to Sb(III) in the presence of l-cysteine and the extraction procedure mentioned above. Sb(V) was calculated by subtracting of Sb(III) from the total Sb. DDTC was used as complexing reagent. 1-Octanol was immobilized in the pores of the polypropylene hollow fiber as liquid membrane and also used as the acceptor solution. Some parameters that influenced extraction and determination were evaluated in detail, such as concentration of sodium diethyldithiocarbamate (DDTC), type of organic solvent, pH of samples, stirring rates, extraction time, as well as interferences. Under optimized conditions, a detection limit of 0.8 ng mL⁻¹ and an enrichment factor of 160 were achieved. The relative standard deviation (RSD) was 6.2% for Sb(III) (50 ng mL⁻¹, n = 5). The proposed method was successfully applied to the speciation of Sb(III) and Sb(V) in environmental and biological samples with satisfactory results.     

Laser induced-thermal lens spectrometry in combination with dispersive liquid-liquid microextraction for trace analysis

An ultrasound-assisted surfactant-enhanced emulsification microextraction (UASEME) was developed as a new approach for the extraction of organophosphorus pesticides (OPs) in water samples prior to high-performance liquid chromatography with diode array detection (HPLC-DAD). The use of a surfactant as an emulsifier in the UASEME method could enhance the dispersion of water-immiscible extraction solvent into aqueous phase and is favorable for the mass-transfer of the analytes from aqueous phase to the organic phase. Several variables that affect the extraction efficiency, including the kind and volume of the extraction solvent, the type and concentration of the surfactant, salt addition, ultrasound emulsification time and temperature, were investigated and optimized. Under the optimum experimental conditions, the calibration curve was linear in the concentration range from 1 to 200 ng mL(-1) for the seven OPs (isocarbophos, phosmet, parathion, parathion-methyl, fenitrothion, fonofos and phoxim), with the correlation coefficients (r) varying from 0.9973 to 0.9998. High enrichment factors were achieved ranging from 210 to 242. The established UASEME-HPLC-DAD method has been successfully applied for the determination of the OPs in real water samples. The limits of detection were in the range between 0.1 and 0.3 ng mL(-1). The recoveries of the target analytes over the three spiked concentration levels of the compounds (10, 50, and 100 ng mL(-1), respectively) in rain, reservoir and well water samples were between 83% and 106% with the relative standard deviations varying from 3.3% to 5.6%.     

超声微波协同萃取/气相色谱法测定土壤中的多溴联苯醚

建立了同时测定土壤中7种多溴联苯醚(PBDEs)的超声微波协同萃取/气相色谱测定方法.考察了萃取溶剂的种类和用量、微波功率、萃取时间等因素对模拟土壤中PBDEs回收率的影响,得到了最佳萃取条件:萃取剂为50 mL正己烷-丙酮(1:1),微波辐射功率为90W,萃取时间为10 min.在最佳条件下,PB-DEs在10～40...     

State of the art of environmentally friendly sample preparation approaches for determination of PBDEs and metabolites in environmental and biological samples: A critical review

Green chemistry principles for developing methodologies have gained attention in analytical chemistry in recent decades. A growing number of analytical techniques have been proposed for determination of organic persistent pollutants in environmental and biological samples. In this light, the current review aims to present state-of-the-art sample preparation approaches based on green analytical principles proposed for the determination of polybrominated diphenyl ethers (PBDEs) and metabolites (OH-PBDEs and MeO-PBDEs) in environmental and biological samples. Approaches to lower the solvent consumption and accelerate the extraction, such as pressurized liquid extraction, microwave-assisted extraction, and ultrasound-assisted extraction, are discussed in this review. Special attention is paid to miniaturized sample preparation methodologies and strategies proposed to reduce organic solvent consumption. Additionally, extraction techniques based on alternative solvents (surfactants, supercritical fluids, or ionic liquids) are also commented in this work, even though these are scarcely used for determination of PBDEs. In addition to liquid-based extraction techniques, solid-based analytical techniques are also addressed. The development of greener, faster and simpler sample preparation approaches has increased in recent years (2003–2013). Among green extraction techniques, those based on the liquid phase predominate over those based on the solid phase (71% vs. 29%, respectively). For solid samples, solvent assisted extraction techniques are preferred for leaching of PBDEs, and liquid phase microextraction techniques are mostly used for liquid samples. Likewise, green characteristics of the instrumental analysis used after the extraction and clean-up steps are briefly discussed.     

Supported liquid membrane work-up in combination with liquid chromatography and electrochemical detection for the determination of chlorinated phenols in natural water samples

Summary A sample preparation method has been developed for the determination of chlorinated phenols in water. The method is based on a supported liquid membrane extraction system connected on-line to liquid chromatography with electrochemical detection. The supported liquid membrane technique utilizes a porous PTFE membrane. The membrane is impregnated with an organic solvent which forms a barrier between two aqueous phases and enables selective extraction. The technique can easily be coupled in a flow system. In this investigation five chlorinated phenols (1–5 chlorine atoms) were extracted from natural water samples. Extraction for 30 minutes resulted in detection limits of approximately 25 ng L^–1.     

Determination of ivermectin and transformation products in environmental waters using hollow fibre-supported liquid membrane extraction and liquid chromatography-mass spectrometry/mass spectrometry

A simple and easy-to-use extraction method for aqueous samples based on hollow fibre-supported liquid membrane (HF-SLM) followed by liquid chromatography-mass spectrometry/mass spectrometry (LC-MS/MS) was developed to determine ivermectin and transformation products, the monosaccharide (TP1) and the aglycon of ivermectin (TP2). The proposed method attained enrichment factors up to 80, after optimising parameters, such as fibre length, organic solvent, stirring speed, salt level, pH in samples/fibre, extraction time and fibre emptying technique. Method validation with tap and lake water samples provided good linearity and detection limits of 0.2, 1.6 and 0.9 microg/l for ivermectin, TP1 and TP2 in lake water with RSD below 15%.     

Extracting Syringe for determination of organochlorine pesticides in leachate water and soil-water slurry: a novel technology for environmental analysis

The Extracting Syringe (ESy), a novel membrane-based sample preparation technique directly coupled as an autosampler to gas chromatography, has been employed for the analysis of organochlorine pesticides (OCPs) in raw leachate water. The ESy has also been applied for extraction of OCPs from contaminated soil samples and its performance has been compared to liquid-solid extraction (LSE) and accelerated solvent extraction (ASE). Extraction of 3-mL leachate sample at the optimised conditions resulted in enrichment factors from 32 (Endrin aldehyde) to 242 (Endrin) and detection limits from 1 to 20 ng/L. The inter-day and intra-day repeatability (% RSD) at 100 and 500 ng/L were <6% and <24%, respectively. The relative recovery at 100 and 500 ng/L ranged from 68% (Aldrin) to 116% (Endrin aldehyde); except Heptachlor that showed 51 and 60%, respectively. The ESy extraction of the slurry-made soil samples revealed occurrence of Endosulfan I (18.2 microg/g soil), 4,4'-DDE (2.6 ng/g soil), Endosulfan II (8.7 microg/g soil) and Endosulfan sulfate (1.1 microg/g soil); showing good agreement with LSE results. The total ESy consumption of organic solvents was 4.2 mL from which only 0.6 mL n-undecane was used during the extraction step (7 microL for the extraction per se), while in the LSE and ASE, it was 420 and 18.1 mL, respectively. The ESy extraction time (0.5 h) was comparable to the ASE time (0.6 h); and the time required for the LSE was 3.75 h. To sum up, the ESy has shown its competency to LSE and ASE technologies, demonstrating its applicability for environmental analysis of organic pollutants, towards green techniques for green environment.     

Determination of n-octanol–water partition coefficients by hollow-fiber membrane solvent microextraction coupled with HPLC

A novel direct method has been developed for determination of n-octanol–water partition coefficients by hollow-fiber membrane solvent microextraction (HFMSME) combined with high-performance liquid chromatography (HPLC). The compound of interest is dissolved in water with sonication and a hollow fiber containing octanol inside is placed in the sample solution to perform microextraction. After microextraction the concentrations in both the aqueous and n-octanol phases are analyzed by HPLC with UV detection. The method was evaluated with ten reference compounds and shown to be suitable for determination of the partition coefficients of organic compounds accurately, cheaply, simply, and quickly. Previously unknown n-octanol–water partition coefficients have been obtained for other compounds by use of the hollow-fiber membrane solvent-microextraction technique. Figure Schematic diagram of equipment used for hollow-fiber solvent microextraction. (1) hollow cone-shaped support; (2) aqueous sample; (3) porous hollow-fiber membrane tube (PHFMT); (4) n-octanol phase; (5) sealed end of PHFMT; (6) container (15 mL); (7) stir bar; (8) magnetic stirrer