A liposome immune lysis assay for enrofloxacin in carp and chicken muscle

A homogenous complement-mediated liposome immune lysis assay (LILA) was developed for the determination of enrofloxacin (ENRO) in carp and chicken muscle. ENRO was covalently coupled to DPPE, and then immobilized onto the surface of liposomes by reverse-phase evaporation method. The performed liposome would be specifically lysed by the sequential additions of anti-ENRO monoclonal antibody (MAb) and guinea pig complement. Through a competitive assay format, the performed liposome can be used to detect ENRO in a range of 5.0-20 ng mL⁻¹ in assay buffer. The limit of detection of ENRO in carp and chicken muscle was 1 ng g⁻¹ and the limit of quantification was 2 ng g⁻¹. Recoveries ranged from 58.3% to 65.2% for carp and 55.6-63.8% for chicken muscle at spiked levels of 2-8 ng g⁻¹, with intra-assay and inter-assay variations 5.6-12.3% and 7.1-19.2%, respectively.     

Dispersive liquid-liquid microextraction combined with high performance liquid chromatography-fluorescence detection for the determination of carbendazim and thiabendazole in environmental samples

A rapid and sensitive method for the determination of carbendazim (methyl benzimidazole-2-ylcarbamate, MBC) and thiabendazole (TBZ) in water and soil samples was developed by using dispersive liquid-liquid microextraction (DLLME) coupled with high performance liquid chromatography with fluorescence detection. The water samples were directly used for the DLLME extraction. For soil samples, the target analytes were first extracted by 0.1 mol L⁻¹ HCl. Then, the pH of the extract was adjusted to 7.0 with 2 mol L⁻¹ NaOH before the DLLME extraction. In the DLLME extraction method, chloroform (CHCl₃) was used as extraction solvent and tetrahydrofuran (THF) as dispersive solvent. Under the optimum conditions, the enrichment factors for MBC and TBZ were ranged between 149 and 210, and the extraction recoveries were between 50.8 and 70.9%, respectively. The linearity of the method was obtained in the range of 5-800 ng mL⁻¹ for water sample analysis, and 10-1000 ng g⁻¹ for soil samples, respectively. The correlation coefficients (r) ranged from 0.9987 to 0.9997. The limits of detection were 0.5-1.0 ng mL⁻¹ for water samples, and 1.0-1.6 ng g⁻¹ for soil samples. The relative standard deviations (RSDs) varied from 3.5 to 6.8% (n = 5). The recoveries of the method for MBC and TBZ from water samples at spiking levels of 5 and 20 ng mL⁻¹ were 84.0-94.0% and 86.0-92.5%, respectively. The recoveries for soil samples at spiking levels of 10 and 100 ng g⁻¹ varied between 82.0 and 93.4%.     

Determination of fluoroquinolone antibiotics in environmental water samples based on magnetic molecularly imprinted polymer extraction followed by liquid chromatography-tandem mass spectrometry

A simple method based on magnetic separation for selective extraction of fluoroquinolones (FQs) from environmental water samples has been developed using magnetic molecularly imprinted polymer (MMIP) as sorbent. The MMIP has been prepared using ciprofloxacin as template molecule, methacrylic acid as functional monomer, ethylene glycol dimethacrylate as cross-linking agent and Fe₃O₄ magnetite as magnetic component. The polymer has been characterized by scanning electron microscopy, Fourier-transform infrared spectrometry and vibrating sample magnetometry. Various parameters affecting the extraction efficiency were evaluated in order to achieve optimal concentration and reduce non-specific interactions. The analytes desorbed from the polymers were determined by liquid chromatography-tandem mass spectrometry. The matrix effect was evaluated by using different washing solvents for removing interfering compounds from the MMIPs after sample loading. Under the optimal conditions, the linearity of the method obtained is in the range of 20-2000 ng L⁻¹. The detection limits of FQs are in the range of 3.2-6.2 ng L⁻¹. The relative standard deviations of intra- and inter-day tests ranging from 2.5 to 7.2% and from 3.6 to 9.1% are obtained. In all three spiked levels (20, 100 and 200 ng L⁻¹), the recoveries of FQs are in the range of 76.3-94.2%. The proposed method was successfully applied to determine FQs including ciprofloxacin, enrofloxacin, lomefloxacin, levofloxacin, fleroxacin and sparfloxacin in different water samples, such as lake water, river water, primary and final sewage effluent. Ciprofloxacin and fleroxacin were found in primary and final sewage effluent samples with the contents in the range of 26-87 ng L⁻¹.     

Determination of the antibacterial enrofloxacin by differential-pulse adsorptive stripping voltammetry

Two new methods for the determination of enrofloxacin in commercial formulations and canine urine samples, based on adsorptive stripping voltammetry (AdSV), are proposed. One of the proposed method uses univariate calibration to analyse enrofloxacin in commercial formulations and the other applies principal component regression (PCR) to the voltammetric measurements to determine enrofloxacin in the presence of its metabolite ciprofloxacin. The linear concentration ranges of application were 4-25 and 18-55 ng ml⁻¹ by using an accumulation potential of −0.3 V and a 180 or 60 s accumulation time, respectively for the univariate method. The first concentration range was used for the multivariate method. Both methods were successfully applied to the analysis of commercial formulations and spiked canine urine samples, respectively.     

Development of a method for the analysis of seven banned azo-dyes in chilli and hot chilli food samples by pressurised liquid extraction and liquid chromatography with electrospray ionization-tandem mass spectrometry

An automated, confirmatory and sensitive procedure has been developed and validated for the determination of Sudan (I-IV), Sudan Orange G, Sudan Red 7B and Para Red in hot chilli food samples. The proposed method includes pressurised liquid extraction (PLE) with acetone, gel permeation chromatography (GPC) clean-up and detection by liquid chromatography (LC) coupled to electrospray ionization in positive mode tandem mass spectrometry (ESI-MS-MS). The main parameters affecting the performance of the different ionization sources and PLE parameters were previously optimised using statistical design of experiments (DOE). The method was in-house validated on chilli powder and chilli meat. Linear calibrations were obtained with correlation coefficients R² > 0.999. The limits of detection (LOD) and quantification (LOQ) of the method were in the ranges of 0.002-0.012 ng g⁻¹ and 0.006-0.036 ng g⁻¹, respectively for chilli powder. The decision limit and detection capability were between 0.005-0.022 ng g⁻¹ and 0.007-0.026 ng g⁻¹, respectively for chilli meat. Recoveries ranged from 94% to 105%. The applicability of the method to the determination of azo-dyes in hot chilli products was demonstrated.     

Determination of pharmaceuticals in soils and sediments by pressurized liquid extraction and liquid chromatography tandem mass spectrometry

The present work describes the development of a sensitive analytical method based on pressurized liquid extraction (PLE) and pre-concentration by solid-phase extraction (SPE), followed by liquid chromatography–electrospray tandem mass spectrometry (LC–ESI-MS/MS) for the determination of seventeen pharmaceuticals in soils and sediments. The method is based on sample homogenisation using Na₂–EDTA washed sand and extraction with water at 90 °C. Special emphasis was placed on the optimization of the extraction procedure to develop a green method that reduces, at a maximum, the use of organic solvents in order to eliminate matrix components during the clean-up. The proposed method was linear in a concentration range from 0.3 to 333 ng g⁻¹, with correlation coefficients higher than 0.993. Method detection (MDLs) and quantification (MQLs) limits ranged from 0.1 to 6.8 ng g⁻¹ and from 0.25 to 23 ng g⁻¹, respectively. Absolute recoveries were analyte dependent, varying between 50% and 105% at the MQL level, except for fenofibrate (40%) and diclofenac (34%). The intra-day and inter-day precision was given by RSD values from 0.7% to 7.9% and from 1.6% to 14.5%, respectively. Acetaminophen, carbamazepine, ciprofloxacin, clofibric acid, codeine, diazepam, fenofibrate, metropolol, ofloxacin and propanolol were detected at concentrations from MDL to 35.62 ng g⁻¹ in soils and sediments from marsh areas. Due to the low recoveries, results for fenofibrate and diclofenac can only be considered as semi-quantitative. The method was fully suitable for the other 15 pharmaceuticals.     

Multiresidue method for the determination of 13 pesticides in three environmental matrices: water, sediments and fish muscle

Pesticides residues in aquatic ecosystems are an environmental concern which requires efficient analytical methods. In this study, we proposed a generic method for the quantification of 13 pesticides (azoxystrobin, clomazone, diflufenican, dimethachlor, carbendazim, iprodion, isoproturon, mesosulfuron-methyl, metazachlor, napropamid, quizalofop and thifensulfuron-methyl) in three environmental matrices. Pesticides from water were extracted using a solid phase extraction system and a single solid-liquid extraction method was optimized for sediment and fish muscle, followed by a unique analysis by liquid chromatography coupled with tandem mass spectrometry (LC-MS/MS). Limits of quantification were below 5 ng L⁻¹ for water (except for fluroxypyr and iprodion) and ranged between 0.1 ng g⁻¹ and 57.7 ng g⁻¹ for sediments and regarding fish, were below 1 ng g⁻¹ for 8 molecules and were determined between 5 and 49 ng g⁻¹ for the 5 other compounds. This method was finally used as a new routine practice for environmental research.     

Ultrasound-assisted leaching-dispersive solid-phase extraction followed by liquid-liquid microextraction for the determination of polybrominated diphenyl ethers in sediment samples by gas chromatography-tandem mass spectrometry

Ultrasound-assisted leaching-dispersive solid-phase extraction followed by dispersive liquid-liquid microextraction (USAL-DSPE-DLLME) technique has been developed as a new analytical approach for extracting, cleaning up and preconcentrating polybrominated diphenyl ethers (PBDEs) from sediment samples prior gas chromatography-tandem mass spectrometry (GC-MS/MS) analysis. In the first place, PBDEs were leached from sediment samples by using acetone. This extract was cleaned-up by DSPE using activated silica gel as sorbent material. After clean-up, PBDEs were preconcentrated by using DLLME technique. Thus, 1 mL acetone extract (disperser solvent) and 60 μL carbon tetrachloride (extraction solvent) were added to 5 mL ultrapure water and a DLLME technique was applied. Several variables that govern the proposed technique were studied and optimized. Under optimum conditions, the method detection limits (MDLs) of PBDEs calculated as three times the signal-to-noise ratio (S/N) were within the range 0.02-0.06 ng g⁻¹. The relative standard deviations (RSDs) for five replicates were <9.8%. The calibration graphs were linear within the concentration range of 0.07-1000 ng g⁻¹ for BDE-47, 0.09-1000 ng g⁻¹ for BDE-100, 0.10-1000 ng g⁻¹ for BDE-99 and 0.19-1000 ng g⁻¹ for BDE-153 and the coefficients of estimation were ≥0.9991. Validation of the methodology was carried out by standard addition method at two concentration levels (0.25 and 1 ng g⁻¹) and by comparing with a reference Soxhlet technique. Recovery values were ≥80%, which showed a satisfactory robustness of the analytical methodology for determination of low PBDEs concentration in sediment samples.     

Europium-sensitized luminescence determination of oxytetracycline in catfish muscle

An europium-sensitized time-resolved luminescence (TRL) method was developed to determine oxytetracycline (OTC) in cultivated catfish muscle. Extraction of OTC from fish muscle was performed with pH 4.0 ethylenediaminetetraacetic acid (EDTA)-McIlvaine buffer and clean up with hydrophilic-lipophilic balanced copolymer solid phase extraction (SPE) cartridges. The eluate was used without further concentration for TRL measurement in pH 9.0 micellar tris(hydroxylmethyl)aminomethane (TRIS) buffer. Cetyltrimethylammonium chloride (CTACl) was used as surfactant and EDTA as a co-ligand. The excitation and emission wavelengths were set at 388 and 615 nm, respectively. The linear dynamic range was 0-1000 ng g⁻¹ (R²=0.9995). The recovery was 92-112% in the fortification range of 50-200 ng g⁻¹ and the limits of detection (LOD) ranged from 3 to 7 ng g⁻¹. Incurred catfish samples were used to demonstrate the performance of the method around 100 ng g⁻¹, the European Union maximum residue level.     

Method development and optimization for the determination of selenium in bean and soil samples using hydride generation electrothermal atomic absorption spectrometry

The present investigation is the first part of an initiative to prepare a regional map of the natural abundance of selenium in various areas of Brazil, based on the analysis of bean and soil samples. Continuous-flow hydride generation electrothermal atomic absorption spectrometry (HG-ET AAS) with in situ trapping on an iridium-coated graphite tube has been chosen because of the high sensitivity and relative simplicity. The microwave-assisted acid digestion for bean and soil samples was tested for complete recovery of inorganic and organic selenium compounds (selenomethionine). The reduction of Se(VI) to Se(IV) was optimized in order to guarantee that there is no back-oxidation, which is of importance when digested samples are not analyzed immediately after the reduction step. The limits of detection and quantification of the method were 30 ng L⁻¹ Se and 101 ng L⁻¹ Se, respectively, corresponding to about 3 ng g⁻¹ and 10 ng g⁻¹, respectively, in the solid samples, considering a typical dilution factor of 100 for the digestion process. The results obtained for two certified food reference materials (CRM), soybean and rice, and for a soil and sediment CRM confirmed the validity of the investigated method. The selenium content found in a number of selected bean samples varied between 5.5 ± 0.4 ng g⁻¹ and 1726 ± 55 ng g⁻¹, and that in soil samples varied between 113 ± 6.5 ng g⁻¹ and 1692 ± 21 ng g⁻¹.     

Headspace solid-phase microextraction using a dodecylsulfate-doped polypyrrole film coupled to ion mobility spectrometry for the simultaneous determination of atrazine and ametryn in soil and water samples

A simple and rapid headspace solid-phase microextraction (HS-SPME) based method is presented for the simultaneous determination of atrazine and ametryn in soil and water samples by ion mobility spectrometry (IMS). A dodecylsulfate-doped polypyrrole (PPy-DS), synthesized by electrochemical method, was applied as a laboratory-made fiber for SPME. The HS-SPME system was designed with a cooling device on the upper part of the sample vial and a circulating water bath for adjusting the sample temperature. The extraction properties of the fiber to spiked soil and water samples with atrazine and ametryn were examined, using a HS-SPME device and thermal desorption in injection port of IMS. Parameters affecting the extraction efficiency such as the volume of water added to the soil, pH effect, extraction time, extraction temperature, salt effect, desorption time, and desorption temperature were investigated. The HS-SPME-IMS method with PPy-DS fiber, provided good repeatability (RSDs < 10 %), simplicity, good sensitivity and short analysis times for spiked soil (200 ng g⁻¹) and water samples (100 and 200 ng mL⁻¹). The calibration graphs were linear in the range of 200-4000 ng g⁻¹ and 50-2800 ng mL⁻¹ for soil and water respectively (R² > 0.99). Detection limits for atrazine and ametryn were 37 ng g⁻¹ (soil) and 23 ng g⁻¹ (soil) and 15 ng mL⁻¹ (water) and 10 ng mL⁻¹ (water), respectively. To evaluate the accuracy of the proposed method, atrazine and ametryn in the three kinds of soils and two well water samples were determined. Finally, comparing the HS-SPME results for extraction and determination of selected triazines using PPy-DS fiber with the other methods in literature shows that the proposed method has comparable detection limits and RSDs and good linear ranges.     

A monoclonal antibody-based time-resolved fluoroimmunoassay for chloramphenicol in shrimp and chicken muscle

A time-resolved fluoroimmunoassay (TR-FIA) for determination of chloramphenicol (CAP) in shrimp and chicken muscle was developed. The method was based on a direct competitive immunoassay using europium-labeled anti-CAP monoclonal antibody (MAb) and CAP-ovalbumin as coated antigen. The limit of detection was 0.05 ng g⁻¹ and limit of quantification was 0.1 ng g⁻¹. Recoveries ranged from 101.2 to 112.5% for shrimp and 104.9 to 115.3% for chicken muscle at spiked levels of 0.1-5 ng g⁻¹, with intra-assay and inter-assay variations 8.7-14.6 and 9.6-17.8%, respectively. The results obtained by the TR-FIA and ELISA correlated well. The established TR-FIA was validated for the determination of incurred shrimp samples and confirmed by gas chromatography with microcell electron capture detector (GC-μECD).     

On-line coupling of dynamic microwave-assisted extraction to solid-phase extraction for the determination of sulfonamide antibiotics in soil

A rapid technique based on dynamic microwave-assisted extraction (DMAE) coupled on-line with solid-phase extraction (SPE) was developed for the determination of sulfonamides (SAs) including sulfadiazine, sulfameter, sulfamonomethoxine and sulfaquinoxaline in soil. The SAs were first extracted with acetonitrile under the action of microwave energy, and then directly introduced into the SPE column which was packed with neutral alumina for preconcentration of analytes and clean-up of sample matrix. Subsequently, the SAs trapped on the alumina were eluted with 0.3% acetic acid aqueous solution and determined by liquid chromatography-tandem mass spectrometry. The DMAE parameters were optimized by the Box-Behnken design. Maximum extraction efficiency was achieved using 320 W of microwave power; 12 mL of extraction solvent and 0.8 mL min⁻¹ of extraction solvent flow rate. The limits of detection and quantification obtained are in the range of 1.4-4.8 ng g⁻¹ and 4.6-16.0 ng g⁻¹ for the SAs, respectively. The mean values of relative standard deviation of intra- and inter-day ranging from 2.7% to 5.3% and from 5.6% to 6.7% are obtained, respectively. The recoveries of SAs obtained by analyzing four spiked soil samples at three fortified levels (20 ng g⁻¹, 100 ng g⁻¹ and 500 ng g⁻¹) were from 82.6 ± 6.0% to 93.7 ± 5.5%. The effect of standing time of spiked soil sample on the SAs recoveries was examined. The recoveries of SAs decreased from (86.3-101.9)% to (37.6-47.5)% when the standing time changed from one day to four weeks.     

Determination of tetrabromobisphenol-A,tetrachlorobisphenol-A and bisphenol-A in soil by ultrasonic assisted extraction and gas chromatography–mass spectrometry

In this work, an isotope dilution method for the determination, in agricultural and industrial soil samples, of tetrabromobisphenol-A, tetrachlorobisphenol-A and bisphenol-A by gas chromatography–mass spectrometry was developed. The compounds were extracted from soil by sonication assisted extraction in small columns (SAESC) with a low volume of ethyl acetate as extraction solvent. For dirty soil samples, such as industrial soils, a simultaneous clean-up on an acidified Florisil–anhydrous sodium sulfate mixture was carried out to remove interferences. After extraction, solvent was evaporated and analytes were derivatized with N,O-bis(trimethylsilyl)trifluoroacetamide (BSTFA) and determined by isotope dilution gas chromatography with electron impact mass spectrometric detection in the selected ion monitoring mode (GC–MS–SIM), using ¹³C₁₂ labeled compounds as internal standards. Recoveries from spiked samples were between 88% and 108% and the estimated limits of detection (S/N = 3) varied from 30 pg g⁻¹ to 90 pg g⁻¹. The response obtained with this method was linear over the range assayed, 5–300 ng ml⁻¹, with correlation coefficients equal or higher than 0.999. The validated method was used to investigate the levels of these phenolic compounds in soil samples collected from different locations in Spain. Bisphenol-A was detected in all samples at concentrations from 0.7 ng g⁻¹ to 4.6 ng g⁻¹ in agricultural soils and from 1.1 ng g⁻¹ to 44.5 ng g⁻¹ in industrial soils. Tetrabromobisphenol-A was found in various soil samples at levels in the range of 3.4–32.2 ng g⁻¹ in industrial soils and at 0.3 ng g⁻¹ in one agricultural soil, whereas tetrachlorobisphenol-A was not detected.     

Enantiomer-specific determination of hexabromocyclododecane in fish by supramolecular solvent-based single-step sample treatment and liquid chromatography–tandem mass spectrometry

A single-step, environmentally friendly sample treatment was developed and used in combination with liquid chromatography–tandem mass spectrometry (LC–MS/MS) for the quantitation of hexabromocyclododecane (HBCD) stereoisomers in fish. It was based on the microextraction of the stereoisomers with a supramolecular solvent (SUPRAS) made up of reverse aggregates of decanoic acid (DeA). The procedure involved the stirring of the fish sample (750 mg) with 600 μL of SUPRAS for five minutes, subsequent centrifugation for extract separation from matrix components and direct analysis of the extract after dilution 1:1 with methanol. Individual enantiomers of α-, β- and γ-HBCD were separated on a chiral stationary phase of β-cyclodextrin and quantified by monitoring of the [M−H]⁻ → Br⁻ transition at m/z 640.9→80.9. Driving forces for the microextraction of HBCD in the SUPRAS involved both dispersion and dipole–dipole interactions. Quantitation limits for the determination of individual HBCD enantiomers in hake, cod, sole, panga, whiting and sea bass were within the intervals 0.5–3.4 ng g⁻¹, 0.9–2.5 ng g⁻¹, 0.6–1.4 ng g⁻¹, 1.0–5.6 ng g⁻¹, 0.8–1.3 ng g⁻¹ and 0.5–3.5 ng g⁻¹, respectively. Recoveries for fish samples fortified at the ng g⁻¹ level ranged between 87 and 114% with relative standard deviations from 1 to 10%. The sample treatment proposed greatly simplifies current procedures for extraction of HBCD stereoisomers and is a useful tool for the development of a large scale database for their presence in fish.     

Determination of mercury in airborne particulate matter collected on glass fiber filters using high-resolution continuum source graphite furnace atomic absorption spectrometry and direct solid sampling

A study has been undertaken to assess the capability of high-resolution continuum source graphite furnace atomic absorption spectrometry for the determination of mercury in airborne particulate matter (APM) collected on glass fiber filters using direct solid sampling. The main Hg absorption line at 253.652 nm was used for all determinations. The certified reference material NIST SRM 1648 (Urban Particulate Matter) was used to check the accuracy of the method, and good agreement was obtained between published and determined values. The characteristic mass was 22 pg Hg. The limit of detection (3σ), based on ten atomizations of an unexposed filter, was 40 ng g^− 1, corresponding to 0.12 ng m^− 3 in the air for a typical air volume of 1440 m³ collected within 24 h. The limit of quantification was 150 ng g⁻¹, equivalent to 0.41 ng m⁻³ in the air. The repeatability of measurements was better than 17% RSD (n = 5). Mercury concentrations found in filter samples loaded with APM collected in Buenos Aires, Argentina, were between < 40 ng g⁻¹ and 381 ± 24 ng g⁻¹. These values correspond to a mercury concentration in the air between < 0.12 ng m⁻³ and 1.47 ± 0.09 ng m⁻³. The proposed procedure was found to be simple, fast and reliable, and suitable as a screening procedure for the determination of mercury in APM samples.     

Cold vapour atomic fluorescence determination of mercury in milk by slurry sampling using multicommutation

A highly sensitive mechanized method has been developed for the determination of mercury in milk by atomic fluorescence spectrometry (AFS). Samples were sonicated for 10 min in an ultrasound water bath in the presence of 8% (v/v) aqua regia, 2% (v/v) antifoam A and 1% (m/v) hydroxilamine hydrochloride, and after that, they were treated with 8 mmol l⁻¹ KBr and 1.6 mmol l⁻¹ KBrO₃ in an hydrochloric medium. Atomic fluorescence measurements were made by multicommutation, which provides a fast alternative in quality control analysis, due to the easy treatment of a large number of samples (approximately 70 h⁻¹), and is an environmentally friendly procedure, which involves a waste generation of only 94.5 ml h⁻¹ as compared with the 605 ml h⁻¹ obtained by using continuous AFS measurements. The limit of detection found was 0.011 ng g⁻¹ Hg in the original sample. The method provided a relative standard deviation of 3.4% for five independent analysis of a sample containing 0.30 ng g⁻¹ Hg. To validate the accuracy of the method, a certified reference material NIST-1459 (non-fat milk powder) containing 0.3±0.2 ng g⁻¹ Hg was analysed and a value of 0.27±0.06 ng g⁻¹ Hg was found. A comparison made between data found by the developed procedure and those obtained by microwave-assisted digestion and continuous AFS measurements evidenced a good comparability between these two strategies. Results obtained for commercially available milk samples varied between 0.09 and 0.61 ng g⁻¹ Hg depending on the type of sample and its origin. The confluence of the analytical waste with a 6 mol l⁻¹ NaOH allowed us to reduce the waste generation in a working session from 1 l to 5 g solid residue with a matrix of Fe(OH)₃ which contributes to the deactivation of traces of heavy metals presents in the samples that does not form volatile hydrides.     

Non-chromatographic speciation of toxic arsenic in fish

A rapid, sensitive and economic method has been developed for the direct determination of toxic species of arsenic present in fish and mussel samples. As(III), As(V), dimethylarsinic acid (DMA), and monomethylarsonic acid (MMA) were determined by hydride generation-atomic fluorescence spectrometry using a series of proportional equations without the need of a chromatographic previous separation. The method is based on the extraction of arsenic species from fish through sonication with HNO₃ 3 mol l⁻¹ and 0.1% (m/v) Triton and washing of the solid phase with 0.1% (m/v) EDTA, followed by direct measurement of the corresponding hydrides in four different experimental conditions. The limit of detection of the method was 0.62 ng g⁻¹ for As(III), 2.1 ng g⁻¹ for As(V), 1.8 ng g⁻¹ for MMA and 5.4 ng g⁻¹ for DMA, in all cases expressed in terms of sample dry weight. The mean relative standard deviation values (R.S.D.) in actual sample analysis were: 6.8% for As(III), 10.3% for As(V), 8.5% for MMA and 7.4% for DMA at concentration levels from 0.08 mg kg⁻¹ As(III) to 1.3 mg kg⁻¹ DMA. Recovery studies provided percentages greater than 93% for all species in spiked samples. The analysis of SRM DORM-2 and CRM 627 certified materials evidenced that the method is suitable for the accurate determination of arsenic species in fish.     

Multi-analyte method for the analysis of various organohalogen compounds in house dust

In the present study, a novel analytical approach for the simultaneous determination of 27 brominated flame retardants (BFRs), namely polybrominated diphenyl ethers (PBDEs), isomers of hexabromocyclododecane (HBCD), tetrabromobisphenol A (TBBPA) and several novel BFRs (NBFRs), together with 18 perfluoroalkyl substances (PFASs) in indoor dust was developed and validated. To achieve integrated isolation of analytes from the sample and their fractionation, a miniaturized method based on matrix solid phase dispersion (MSPD) was employed. Principally, after mixing the dust (<0.1 g) with the Florisil^®, the mixture was applied on the top of a sorbent (Florisil^®) placed in glass column and then analytes were eluted using solvents with different polarities. For the identification/quantification of target compounds largely differing in polarity, complementary techniques represented by gas and liquid chromatography coupled to tandem mass spectrometry (GC–MS/MS and LC–MS/MS) were used. The results of validation experiments, which were performed on the SRM 2585 material (for PBDEs, HBCDs and TBBPA), were in accordance with the certified/reference values. For other analytes (NBFRs and PFASs), the analysis of an artificially contaminated blank dust sample was realized. The method recoveries for all target compounds ranged from 81 to 122% with relative standard deviations lower than 21%. The quantification limits were in the range of 1–25 ng g⁻¹ for BFRs and 0.25–1 ng g⁻¹ for PFASs. Finally, 18 samples (6 households × 3 sampling sites) were analyzed. The high variability between concentrations of PFASs and BFRs in the dust samples from various households as well as collecting sites in a respective house was observed. The total amounts of PFASs and BFRs were in the range of 1.58–236 ng g⁻¹ (median 10.6 ng g⁻¹) and 39.2–2320 ng g⁻¹ (median 325 ng g⁻¹), respectively. It was clearly shown that dust from the indoor environment might be a significant source of human exposure to various organohalogen pollutants.     

Stir bar sorptive extraction-gas chromatography-mass spectrometry analysis of tetramethylene disulfotetramine in food: Method development and comparison to solid-phase microextraction

A stir bar sorptive extraction-gas chromatography-mass spectrometry (SBSE-GC-MS) method for the determination of tetramethylene disulfotetramine is presented. The limits of detection (LOD) of the optimized method was 0.2 ng g⁻¹ for extractions from water and 0.3-2.1 ng g⁻¹ for extractions from foods. Recovery was highly matrix dependent (36-130%) and quantification required standard addition calibrations. Standard addition calibration lines had high linearity (R² > 0.97) and replicate extractions had good reproducibility (R.S.D. = 4.4-9.8%). A comparison of the SBSE method and a previously developed headspace (HS)-solid-phase microextraction (SPME) method was performed. Generally, SBSE provided higher sensitivity with decreased analysis time.