Online preconcentration in capillary electrophoresis with contactless conductivity detection for sensitive determination of sorbic and benzoic acids in soy sauce

A sensitive method of online preconcentration followed by capillary electrophoresis with capacitively coupled contactless conductivity detection (CE-C⁴D) is evaluated as a novel approach for the determination of benzoic acid and sorbic acid in soy sauce. The online preconcentration technique, namely field-enhanced sample injection, coupled with CE-C⁴D were successfully developed and optimized. In order to reduce the complex matrix interference resulting from the constituents of soy sauce, a suitable sample clean-up procedure was also investigated for real sample pretreatment. Under optimized conditions, sorbic acid and benzoic acid were well separated within 10 min, and the detection limits were 0.05 μM (5.6 μg L⁻¹) and 0.08 μM (9.8 μg L⁻¹), respectively. The accuracy was tested by spiking 10.0 mg L⁻¹ and 100.0 mg L⁻¹ of standards in the soy sauce samples, and the recoveries were 95-99%, respectively. Results of this study show a great potential for the proposed method as a tool for the fast screening of benzoic acid and sorbic acid in a complex matrix.     

Fast liquid chromatography-tandem mass spectrometry for the analysis of bisphenol A-diglycidyl ether, bisphenol F-diglycidyl ether and their derivatives in canned food and beverages

In this work a fast liquid chromatography coupled with tandem mass spectrometry (LC–MS/MS) method using a C18 Fused Core™ column, was developed for the simultaneous analysis of bisphenol A diglycidyl ether (BADGE), bisphenol A (2,3-dihydroxypropyl) glycidyl ether (BADGE·H₂O), bisphenol A bis(2,3-dihydroxypropyl) ether (BADGE·2H₂O), bisphenol A (3-chloro-2-hydroxypropyl) glycidyl ether (BADGE·HCl), bisphenol A bis(3-chloro-2-hydroxypropyl) ether (BADGE·2HCl) and bisphenol A (3-chloro-2-hydroxypropyl)(2,3-dihydroxypropyl ether) (BADGE·HCl·H₂O) and bisphenol F diglycidyl ether (BFDGE), bisphenol F bis(2,3-dihydroxypropyl) ether (BFDGE·2H₂O), bisphenol F bis(3-chloro-2-hydroxypropyl) ether (BFDGE·2HCl). The LC method was coupled with a triple quadrupole mass spectrometer, using an ESI source in positive mode and using the [M+NH₄]⁺ adduct as precursor ion for tandem mass spectrometry experiments. The method developed was applied to the determination of these compounds in canned soft drinks and canned food. OASIS HLB solid phase extraction (SPE) cartridges were used for the analysis of soft drinks, while solid canned food was extracted with ethyl acetate. Method limits of quantitation ranged from 0.13 μg L⁻¹ to 1.6 μg L⁻¹ in soft drinks and 1.0 μg kg⁻¹ to 4.0 μg kg⁻¹ in food samples. BADGE·2H₂O was detected in all the analyzed samples, while other BADGEs such as BADGE·H₂O, BADGE·HCl·H₂O, BADGE·HCl and BADGE·2HCl were also detected in canned foods.     

Silver nanoparticles fluorescence enhancement effect for determination of nucleic acids with kaempferol-Al(III)

Nucleic acids can greatly enhance fluorescence intensity of the kaempferol (Km)-Al(III) system in the presence of silver nanoparticles (AgNPs). Based on this, a novel method for the determination of nucleic acids is proposed. Under studied conditions, there are linear relationships between the extent of fluorescence enhancement and the concentration of nucleic acids in the range of 5.0 × 10⁻⁹ to 2.0 × 10⁻⁶ g mL⁻¹ for fish sperm DNA (fsDNA), 7.0 × 10⁻⁹ to 2.0 × 10⁻⁶ g mL⁻¹ for salmon sperm DNA (smDNA) and 2.0 × 10⁻⁸ to 3.0 × 10⁻⁶ g mL⁻¹ for yeast RNA (yRNA), and their detection limits are 2.5 × 10⁻⁹ g mL⁻¹, 3.2 × 10⁻⁹ g mL⁻¹ and 7.3 × 10⁻⁹ g mL⁻¹, respectively. Samples were satisfactorily determined. And the system of Km-Al(III)-AgNPs was used as a fluorescence staining reagent for sensitive DNA detection by DNA pattern of agarose gel electrophoresis analysis. The results indicate that the fluorescence enhancement should be attributed to the formation of Km-Al(III)-AgNPs-nucleic acids aggregations through electrostatic attraction and adsorption bridging action of Al(III) and the surface-enhanced fluorescence effect of AgNPs.     

Carbon nanofibers extracted from soot as a sorbent for the determination of aromatic amines from wastewater effluent samples

The isolation and characterization of carbon nanofibers from soot obtained by burning natural oil is reported. The fibers were extracted from the soot with tetrahydrofuran followed by sonication. The carbon nanofibers were mixed with poly(vinyl alcohol) and electrospun to get the nanofiber mat. The extraction ability of electrospun nanofibers for the separation and preconcentration of aromatic compounds such as 3-nitroaniline, 4-chloroaniline, 4-bromoaniline and 3,4-dichloroaniline were tested and efficiently evaluated using high performance liquid chromatography. Under optimized conditions, the method showed good linearity in a range of 0.5–50 μg L⁻¹ with correlation coefficient ranging from 0.989 to 0.998. High precision of the extraction with RSD values of 4.5–5.8% and low LOD value in a range of 0.009–0.081 μg L⁻¹ for all aniline compounds were achieved. The proposed microextraction method offers advantages such as easy operation, high recovery, fast extraction, minimal use of organic solvent and elimination of tedious solvent evaporation and reconstitution steps.     

Effective indirect enrichment and determination of nitrite ion in water and biological samples using ionic liquid-dispersive liquid-liquid microextraction combined with high-performance liquid chromatography

An ionic liquid dispersive liquid–liquid microextraction high-performance liquid chromatography (IL-DLLME-HPLC) method for effective enrichment and determination of nitrite ion in water and biological samples was developed. The method was based on the reaction of nitrite ion with p-nitroaniline in the presence of diphenylamine in acid media and IL-DLLME of azo product. The optimization of reaction and extraction conditions, such as kind and concentration of acid, reaction time, volume of reaction solvent, temperature, kind of extraction and dispersive solvent, volume of extraction and dispersive solvent, addition of salt, extraction and centrifugal time were studied. Under the optimal conditions, 1-octyl-3-methylimidazolium bis[(trifluoromethyl)sulfonyl]imide IL-DLLME procedure provided high enrichment factor of 430 and good extraction recovery of 91.7% for nitrite ion. The linearity was observed in the range of 0.4–500.0 μg L⁻¹ with good correlation coefficient (r² = 0.9996). The relative standard deviations (RSDs) for five replicate measurements varied between 1.5% and 4.8%. The limit of detection of the method (S/N = 3) was 0.05 μg L⁻¹. The interference effect of some anions and cations was also tested. The developed method allowed achieving an excellent enrichment factor, yielding a lower LOD in comparison with other methods. Moreover, the proposed method was able to analyze nitrite ion in water and biological samples with satisfactory recovery ranged from 96.5% to 107.3%.     

Determination of refractory elements in atmospheric particulates using slurry sampling electrothermal vaporization inductively coupled plasma optical emission spectrometry and inductively coupled plasma mass spectrometry with polyvinylidene fluoride as chemical modifier

Electrothermal vaporization (ETV) inductively coupled plasma optical emission spectrometry (ICP-OES) and inductively coupled plasma mass spectrometry (ICP-MS) with polyvinylidene fluoride (PVDF) as chemical modifier are critically compared for the determination of refractory elements in coal fly ash and airborne particulates. The atmospheric particulates that collected on a PVDF filter were introduced into the graphite furnace in the form of a slurry by dissolving the filter in dimethylformamide, and the dissolved filter PVDF, along with additional added PVDF powder, was used as a chemical modifier for subsequent ETV-ICP-OES and ETV-ICP-MS determination. The vaporization behaviors of analytes (Ti, Zr, V, Mo, Cr, La) in ETV-ICP-OES/MS were studied in detail, and the optimal ETV operating parameters were obtained. Under the optimized operating conditions, the detection limits of target elements were 0.08-2.7 ng m(-3) for ETV-ICP-OES and 0.5-50 pg m(-3) for ETV-ICP-MS, respectively, with analytical precisions of 3.5-7.3% for ETV-ICP-OES and 3.9-9.6% for ETV-ICP-MS, respectively. The tolerable amounts of matrix elements for ETV-ICP-OES are higher than for ETV-ICP-MS. Both ETV-ICP-OES and ETV-ICP-MS were used to directly determine the trace refractory elements in coal fly ash and airborne particulates and the analytical results are comparable.     

Determination of sibiromycin and its natural derivatives using new analytical and structural approaches

A new separation and quantification method using ultra high-performance liquid chromatography (UHPLC) with UV detection was developed for the detection of sibiromycin in fermentation broth of Streptosporangium sibiricum. The solid phase extraction method based on cation-exchange was employed to pre-concentrate and purify fermentation broth containing sibiromycin prior to UHPLC analysis. The whole assay was validated and showed a linear range of detector response for the quantification of sibiromycin in a concentration from 3.9 to 250.0 μg mL⁻¹, with correlation coefficient of 0.999 and recoveries ranging from 71.66 ± 3.55% to 74.76 ± 5.18%. Method limit of quantification of the assay was determined as 0.18 μg mL⁻¹ and was verified with resulting RSD of 9.6% and accuracy of 97.6%. The developed assay was used to determine the sibiromycin production in 12 different fermentation broths. Moreover, several natural sibiromycin analogues/derivatives were described with pilot characterization using off-line mass spectrometry: the previously described dihydro-sibiromycin (DH-sibiromycin) and tentative bis-glycosyl forms of sibiromycin and its dihydro-analogue.     

Solvent (ionic liquid) impregnated resin-based extraction coupled with dynamic ultrasonic desorption for separation and concentration of four herbicides in environmental water

A new method was developed for the determination of monolinuron, propazine, linuron, and prebane in environmental water samples. The solvent (ionic liquid) impregnated resin (IL-SIR)-based extraction coupled with dynamic ultrasonic desorption (DUSD) was applied to the separation and concentration of the analytes. The high performance liquid chromatography (HPLC) was applied to the determination of the analytes. The ionic liquid [C₆MIM][PF₆] was immobilized on Diaion HP20 resin by immersing the resin in ethanol solution containing [C₆MIM][PF₆]. The effect of extraction parameters, including pH value of sample solution, salt concentration in sample and extraction time, and elution conditions, including the concentration of ethanol in elution solvent, the flow rate of elution solvent and the ultrasonic power, were examined and optimized. The limits of detection and quantification for the analytes were in the range of 0.15-0.29 μg L⁻¹ and 0.51-0.98 μg L⁻¹, respectively. Some environmental water samples were analyzed and the analytical results were satisfactory.     

Application of fast ultrasound water-bath assisted enzymatic hydrolysis--high performance liquid chromatography-inductively coupled plasma-mass spectrometry procedures for arsenic speciation in seafood materials

Enzymatic hydrolysis of seafood materials for isolating arsenic species (As(III), As(V), DMA and AsB) has been successfully performed by assisting the procedure with ultrasound energy (35 kHz) supplied by an ultrasound water-bath. The use of pepsin, as a proteolytic enzyme, under optimized operating conditions (pH 3.0, temperature 40 °C, enzyme to sample ratio of 0.3) led to an efficient assistance of the enzymatic process in a short period of time (from 4.0 to 30 min). The enzymatic extract was then subjected to a clean-up procedure based on ENVI-Carb™ solid phase extraction (SPE). An optimized anion exchange high performance liquid chromatography (HPLC) coupled to inductively coupled plasma-mass spectrometry (ICP-MS) permitted the fast separation (less than 15 min) of six different arsenic species (arsenite, As(III); arsenate, As(V); dimethylarsinic acid, DMA; and arsenobetaine, AsB; as well as monomethylarsonic acid, MMA; and arsenocholine, AsC) in a single run. Relative standard deviations (n = 11) of the over-all procedure were 7% for AsB and DMA, 11% for As(III) and 9% for MMA. HPLC–ICP-MS determinations were performed using aqueous calibrations covering arsenic concentrations of 0, 5, 10, 25, 100 and 200 μg L⁻¹ (expressed as arsenic) for As(III), As(V), MMA, DMA and AsC; and 0, 125, 250, 500, 750, 1000 and 2000 μg L⁻¹ (expressed as arsenic) for AsB. Germanium (5 μg L⁻¹) was used as an internal standard. Analytical recoveries from the anion exchange column varied from 96 to 105% (enzymatic digests spiked with low target concentrations), from 97 to 104% (enzymatic digests spiked with intermediate target concentrations), and from 98 to 103% (enzymatic digests spiked with high target concentrations). The developed method was successfully applied to two certified reference materials (CRMs), DORM-2 and BCR 627, which offer certified AsB and DMA contents, and also to different seafood samples (mollusks, white fish and cold water fish). Good agreement between certified and found AsB concentrations was achieved when analyzing both CRMs; and also, between certified and found DMA concentrations in BCR 627. In addition, the sum of the different arsenic species concentrations found in most of the analyzed samples was statistically similar to the assessed total arsenic concentrations after a total sample matrix decomposition treatment.     

A novel reusable ionic liquid chemically bonded fused-silica fiber for headspace solid-phase microextraction/gas chromatography-flame ionization detection of methyl tert-butyl ether in a gasoline sample

A novel ionic liquid (IL) bonded fused-sil-ica fiber for headspace solid-phase microextraction (HS-SPME)/gas chromatography-flame ionization detection (GC-FID) of methyl tert-butyl ether (MTBE) in a gasoline sample was prepared and used. The new proposed chemically bonded fiber has better thermal stability and durability than its corresponding physically coated fiber. Another advantage is that no spacer was used for the purpose of bonding the IL to the surface of the fused-silica. The latter advantage makes the preparation of these fibers easier with lower cost than those prepared using sol–gel method. The ionic liquid 1-methyl-3-(3-trimethoxysilyl propyl) imidazolium bis(trifluoromethylsulfonyl) imide was synthesized and cross linked to the surface of the fused-silica fiber. Then, the chemically IL-modified fibers were applied to the headspace extraction of MTBE. The chemically IL-modified fibers showed improved thermal stability at temperatures up to 220 °C relative to the physically IL-modified fibers (180 °C). The chemically bonded IL film on the surface of the fused-silica fiber was durable over 16 headspace extractions without any significant loss of the IL film. The calibration graph was linear in a concentration range of 2–240 μg L⁻¹ (R² = 0.996) with the detection limit of 0.1 μg L⁻¹ level. The reproducibility (RSD %, n = 6) of the new IL bonded fused-silica fiber (8.9%) was better than the physically coated fiber (12%) suggesting that the proposed chemically IL-modified fiber is more robust than the physically IL-modified fiber. The optimum extraction conditions were the followings: 40 °C extraction temperature, 12 min extraction time, 30 s desorption time and sample agitation at 200 rpm.     

Determination of geosmin and 2-methylisoborneol in water and wine samples by ultrasound-assisted dispersive liquid-liquid microextraction coupled to gas chromatography-mass spectrometry

A fast, simple and environmentally friendly ultrasound-assisted dispersive liquid–liquid microextraction (USADLLME) procedure has been developed to preconcentrate geosmin and 2-methylisoborneol (MIB) from water and wine samples prior to quantification by gas chromatography–mass spectrometry (GC–MS). A two-stage multivariate optimization approach was developed by means of a Plackett–Burman design for screening and selecting the significant variables involved in the USADLLME procedure, which was later optimized by means of a circumscribed central composite design. The optimum conditions were: solvent volume, 8 μL; solvent type: tetrachloroethylene; sample volume, 12 mL; centrifugation speed, 2300 rpm; extraction temperature 20 °C; extraction time, 3 min; and centrifugation time, 3 min. Under the optimized experimental conditions the method gave good levels of repeatability with coefficient of variation under 11% (n = 10). Limits of detection were 2 and 9 ng L⁻¹ for geosmin and MIB, respectively. Calculated calibration curves gave high levels of linearity with correlation coefficient values of 0.9988 and 0.9994 for geosmin and MIB, respectively. Finally, the proposed method was applied to the analysis of two water (reservoir and tap) samples and three wine (red, rose and white) samples. The samples were previously analyzed and confirmed free of target analytes. Recovery values ranged between 70 and 113% at two spiking levels (0.25 μg L⁻¹ and 30 ng L⁻¹) showing that the matrix had a negligible effect upon extraction. Only red wine showed a noticeable matrix effect (70–72% recovery). Similar conclusions have been obtained from an uncertainty budget evaluation study.     

A new analytical methodology for a fast evaluation of semi-volatile polycyclic aromatic hydrocarbons in the vapor phase downstream of a diesel engine particulate filter

A new sampling method was developed to collect vapor-phase polycyclic aromatic compounds (PAHs) downstream of a diesel engine equipped with a diesel particulate filter (DPF). This configuration allowed us to collect separately the particulate phase, which was trapped inside the DPF, and the vapor phase, which was sampled downstream of the DPF. PAHs, which were not predominantly absorbed into the poor organic fraction of the diesel soot, but were rather physically sorbed on high energetic adsorption sites, should be extracted using very drastic extraction conditions Microwave-assisted extraction using solvent mixtures composed of pyridine and diethylamine were used to desorb particulate PAHs, and the total PAH amounts corresponded to a very low value, i.e., 8 μg g⁻¹ or 0.24 μg km⁻¹, with a predominance of low weight PAHs. For collection of the vapor phase, gas bubbling in an aqueous medium was preferred to conventional methods, e.g., trapping on solid sorbents, for several reasons: aqueous trapping allowed us to use a solid phase enrichment process (SPE) that permitted PAH sampling at the sub-picogram levels. Consequently, low volume sampling was possible even if the sampling duration was very short (20 min). Additionally, the amount of time saved for the analysis was considerable when coupling SPE to the analytical system (liquid chromatography with fluorimetric detection). Solvent consumption for the overall sampling and analytical processes was also drastically reduced. Experiments on a diesel engine showed that vapor phase samples collected downstream of the DPF contained all of the 15 target priority PAHs, even the heaviest ones. The total vapor-phase PAH amount was 6.88 μg N m⁻³ or 10.02 μg km⁻¹, which showed that the gaseous fraction contains more PAHs than the particulate fraction. Partitioning coefficients (K_p) were estimated showing the predominance in the vapor phase of all the PAHs. However, the DPF technology effects a considerable decrease in the total PAH emission when compared to non-equipped diesel vehicles.     

New developments in the analysis of fragrances and earthy-musty compounds in water by solid-phase microextraction (metal alloy fibre) coupled with gas chromatography-(tandem) mass spectrometry

Fragrances are widespread aquatic contaminants due to their presence in many personal care products used daily in developed countries. Levels of galaxolide and tonalide are commonly found in surface waters, urban wastewaters and river sediments. On the other hand, earthy-musty compounds confer bad odour to drinking water at levels that challenge the analytical capabilities. The combined determination of earthy-musty compounds and fragrances in water would be a breakthrough to make the traditional organoleptic evaluation of the water quality stricter and safer for the analyst. Two approaches were attempted to improve the analytical capabilities: analyte pre-concentration with a newly developed PDMS-DVB solid-phase microextraction fibre on metal alloy core and sensitive detection by tandem mass spectrometry (MS/MS). The optimization of SPME parameters was carried out using a central composite design and desirability functions. The final optimum extraction conditions were: headspace extraction at 70 °C during 40 min adding 200 g L⁻¹ of NaCl. The detection limits in tandem MS (0.02-20 ng L⁻¹) were marginally lower compared to full scan except for geosmin and trichloroanisol which go down to 0.1 and 0.02 ng L⁻¹, respectively.The analysis of different water matrices revealed that fragrances and earthy-musty compounds were absent from ground- and drinking waters. Surface waters of river Leça contained levels of galaxolide around 250 ng L⁻¹ in the 4 terminal sampling stations, which are downstream of WWTPs and polluted tributaries. Geosmine was ubiquitously distributed in natural waters similarly in rivers Leça and Douro at concentrations <7 ng L⁻¹.     

Determination of linuron in water and vegetable samples using stripping voltammetry with a carbon paste electrode

A carbon paste electrode was used for the electrochemical determination of linuron concentrations in water and vegetable extracts. Optimal conditions were established with respect to electrode activation (electrochemical pretreatment), time accumulation, potential accumulation, scan rate, and pH. The limit of detection achieved with a pre-concentration step was 23.0 μg L⁻¹. Recovery measurements in vegetable extract and natural water samples were in the range of 98-103%, indicating that the proposed electrochemical method can be employed to analyze linuron in these matrices. The determination results were in good agreement with HPLC results.     

Titania immobilized polypropylene hollow fiber as a disposable coating for stir bar sorptive extraction-high performance liquid chromatography-inductively coupled plasma mass spectrometry speciation of arsenic in chicken tissues

The bottleneck of applying stir bar sorptive extraction (SBSE) to elemental speciation analysis is lack of suitable extraction phases with good affinities to different elemental species. In this paper, a newly high polar extraction phase of titania immobilized polypropylene hollow fiber (TiO₂-PPHF) was prepared by sol–gel immersion and low temperature hydrothermal process and the obtained TiO₂-PPHF inherits the adsorption properties of TiO₂ and the toughness of PPHF. With a suitable size of stainless steel magnetic bar inserted into the prepared TiO₂-PPHF, a disposable TiO₂-PPHF coating stir bar was obtained. The prepared TiO₂-PPHF was characterized by X-ray diffraction spectrometry and scanning electron microscopy and the significant parameters affecting the extraction efficiency of different arsenic species were studied. Based on the above facts, a new method of SBSE combined with high performance liquid chromatography (HPLC)–inductively coupled plasma mass spectrometry (ICP-MS) was developed for the speciation of phenyl arsenic compounds and their possible transformation products in chicken tissues. Under the optimal conditions, limits of detection (LODs) of the developed method for eight target arsenic species were in the range of 11.4–64.6 ng L⁻¹ with enrichment factors of 8.5–22.3 (theory enrichment factor was 50), and the relative standard deviations (RSDs) were varying from 6.3 to 12.6% (c_AsIII/V = 5 μg L⁻¹, c_{MMA,DMA,p-ASA,4-OH,3-NHPAA,PA,4-NPAA} = 10 μg L⁻¹, n = 7). The proposed method was successfully applied to the speciation of arsenic in chicken meat/liver samples and the recoveries for the spiked samples were in the range of 78.5–120.4%. In order to validate the accuracy of the proposed method, a certified reference material of BCR-627 tuna fish tissue was analyzed and the determined values were in good agreement with the certified values. The TiO₂-PPHF was demonstrated to be a highly selective coating for the target arsenic species, and could be easily prepared in batches with low cost. In addition, with the disposable coating, the carry-over effect commonly encountered in conventional SBSE was avoided.     

Potentiometric detection of citrate in beverages using a graphite carbon electrode

The development, evaluation and application of a simple and low-cost graphite carbon electrode for the direct determination of citrate in food samples are described here. The electrode exhibits a linear response with a slope of −29.0 ± 1.0 mV decade⁻¹ in a concentration range of 0.07-7.0 mmol L⁻¹ in 0.1 mol L⁻¹ KCl/1.0 mmol L⁻¹ phosphate buffer solution with a limit of detection of 3.0 μmol L⁻¹. The electrode is easily constructed at a relatively low cost and has a fast time response (within 120 s) with no significant changes in its performance characteristics. The performance of the graphite sensor was tested to determine citrate in beverage samples (juices and an isotonic drink), and the results were validated against a reference procedure. The proposed method is quick, inexpensive, selective and sensitive, and is based entirely on conventional instrumentation.     

Asymmetrical flow field-flow fractionation technique for separation and characterization of biopolymers and bioparticles

Field-flow fractionation (FFF) is one of the most versatile separation techniques in the field of analytical separation sciences, capable of separating macromolecules in the range 10³–10¹⁵ g mol⁻¹ and/or particles with 1 nm–100 μm in diameter. The most universal and most frequently used FFF technique, flow FFF, includes three types of techniques, namely symmetrical flow FFF, hollow fiber flow FFF, and asymmetrical flow FFF which is most established variant among them. This review provides a brief look at the theoretical background of analyte retention and separation efficiency in FFF, followed by a comprehensive overview of the current status of asymmetrical flow FFF with selected applications in the field of biopolymers and bioparticles.     

Pesticide residue analysis of fruit juices by LC-MS/MS direct injection. One year pilot survey

For this work, thirteen types of fruit juices (orange, pineapple, peach, apple, multifruit, mango, strawberry, tomato, pear, mandarin, grape, banana and grapefruit) were selected to develop an analytical method for the analysis of 53 pesticides by direct injection in LC-MS/MS. The preparation of the samples was very simple: an aliquot of the juice was centrifuged and it was ten-times diluted prior to analysis, which allowed reducing considerably the time and cost of the analyses. Besides, dilution of the samples permits reducing the amount of matrix going into the system, and thus, decreasing the matrix effects, so common in this type of commodities, opening the possibility to perform quantification with solvent based standards. Validation of the method was carried out in accordance with EU guidelines. Calibration curves covering three orders of magnitude were performed, and they were linear over the concentration range studied for all the matrices (from 0.1 to 100 μg L⁻¹). Practical limits of quantification were in the low μg L⁻¹ range, far below the maximum residue levels (MRLs) of the EU regulations, which do not set specific MRLs for juices, and in this cases of processed food, MRLs of the raw product are applied. Repeatability of the instrumental method was studied in all matrices, obtaining good intra- and inter-day relative standard deviations (RSDs). The proposed method was applied to 106 real fruit juice samples purchased in different local markets during a one-year survey in order to validate the suitability for routine analysis. 43% of the analysed samples gave positive results (higher than the practical limits of quantification).     

用ETV-ICP-MS研究Cr、Ni、Zr、Nb、Yb在石墨炉中的蒸发/原子化机理

本文以电热蒸发电感耦合等离子体质谱（ETV-ICP-MS）为手段,探讨了Cr、Ni、Zr、Nb和Yb在石墨炉中的蒸发/原子化机理;比较了不同化学改进剂存在条件下,Cr、Ni、Zr、Nb和Yb的蒸发行为和在石墨炉原子吸收（GFAAS）中的原子化行为;考察了石墨炉温度和ICP功率等实验参数对上述元素发射强度及轮廓的影响.结果表明,Pd和Mg化合物的存在对Cr、Ni、Zr、Nb和Yb的蒸发/原子化行为没有明显的化学改进作用;然而,以聚四氟乙烯（PTFE）为化学改进剂时,可显著改善Cr、Ni、Zr、Nb和Yb的蒸发行为,避免难熔碳化物的形成,降低待测物的蒸发温度;对Cr和Ni的GFAAS信号强度略有增强;但是,由于Yb、Nb和Zr氟化物的离解键能很高,难以离解/原子化,PTFE的存在反而降低了Yb、Nb和Zr在GFAAS中的信号强度.     

Development of a stir bar sorptive extraction and thermal desorption-gas chromatography-mass spectrometry method for determining synthetic musks in water samples

This study presents the development of an analytical method for determining 9 synthetic musks in water matrices. The developed method is based on stir bar sorptive extraction (SBSE), coated with polydimethylsiloxane, and coupled with a thermal desorption–gas chromatography–mass spectrometry system (TD–GC–MS). SBSE can efficiently trap and desorb the analytes providing low limits of detection (between 0.02 ng L⁻¹ and 0.3 ng L⁻¹). Method validation showed good linearity, repeatability and reproducibility for all compounds. Furthermore, the limited manipulation of the sample required in this method implies a significant decrease of the risk of external contamination of the samples. The performance of the method in real samples was evaluated by analysing biological wastewater treatment plant (WWTP) influent and effluent samples, reverse osmosis treatment plant effluents and river waters. The most abundant musk was galaxolide with values up to 2069 ng L⁻¹ and 1432 ng L⁻¹ in the influent and effluent of urban WWTP samples, respectively. Cashmeran, Pantolide and Tonalide were also detected in all the matrices with values up to 94 ng L⁻¹, 26 ng L⁻¹ and 88 ng L⁻¹, respectively. Although in Europe the use of nitromusks in cosmetics is prohibited, musk xylene and musk ketone were detected both in the WWTP and in the river samples. As far as we know, this is the first time than a SBSE method coupled with TD is applied for the determination of synthetic musks in water samples.