Determination of photoirradiated high polar benzoylureas in tomato by HPLC with luminol chemiluminescence detection

This study reports the first analytical application of luminol chemiluminescence reaction for the sensitive detection of two benzoylurea insecticides (diflubenzuron and triflumuron). Off-line experiments demonstrated that previously irradiated traces of these benzoylurea insecticides largely enhanced the chemiluminescence emission yielded from the oxidation of luminol in methanol:water mixtures, by potassium permanganate in alkaline medium, the enhancement being proportional to the concentration of both pesticides. The two benzoylureas were determined in tomato samples by coupling liquid chromatography with post-column photoderivatization and detection based on this chemiluminescence reaction. Tomato samples were extracted using the QuEChERS method based on extraction with acetonitrile and dispersive solid-phase clean-up using primary and secondary amine (PSA). Interferences due to matrix effect were overcome by using matrix-matched standards. The optimised method was validated with respect to linearity, limits of detection and quantification, precision and accuracy. Under the optimised conditions, calibrations graphs were linear between 0.05 and 0.50 μg mL⁻¹ for diflubenzuron and between 0.10 and 1.00 μg mL⁻¹ for triflumuron. Method detection limits were 0.0025 and 0.0131 μg mL⁻¹ (equivalent to 0.0005 and 0.0026 mg kg⁻¹) and quantification limits were 0.05 and 0.10 μg mL⁻¹ (equivalent to 0.01 and 0.02 mg kg⁻¹) for diflubenzuron and triflumuron, respectively. In both cases, quantification limits were lower than the maximum residue levels (MRLs) established by the European legislation. The relative standard deviation of intra-day precision was below 10% and recoveries were between 79.7% and 94.2% for both pesticides.     

Development of a miniature dielectric barrier discharge–optical emission spectrometric system for bromide and bromate screening in environmental water samples

Dielectric barrier discharge (DBD) at atmospheric pressure provides an efficient radiation source for the excitation of bromine and it is used for the first time for optical emission spectrometric (OES) detection of bromide and bromate. A portable DBD–OES system is developed for screening potential pollution from bromide and bromate in environmental waters. Bromide is on-line oxidized to bromine for in-situ generation of volatile bromine. Meanwhile, a helium stream carries bromine into the DBD micro-plasma for its excitation at a discharging voltage of 3.7 kV and optical emission spectrometric detection with a QE65000 charge-coupled device (CCD) spectrometer in the near-infrared spectral region. Similarly, the quantification of bromate is performed by its pre-reduction into bromide and then oxidized to bromine. The spectral characteristics and configuration of the DBD micro-plasma excitation source in addition to the oxidation vapor generation of bromine have been thoroughly investigated. With a sampling volume of 1 mL, a linear range of 0.05–10.0 mg L⁻¹ is obtained with a detection limit of 0.014 mg L⁻¹ by measuring the emission at 827 nm. A precision of 2.3% is achieved at 3 mg L⁻¹ bromide. The system is validated by bromine detection in certified reference material of laver (GBW10023) at mg L⁻¹ level, giving rise to satisfactory agreement. In addition, it is further demonstrated by screening trace bromide and bromate as well as spiking recoveries in a series of environmental water samples.     

Validation of a qualitative screening method for pesticides in fruits and vegetables by gas chromatography quadrupole-time of flight mass spectrometry with atmospheric pressure chemical ionization

A wide-scope screening method was developed for the detection of pesticides in fruit and vegetables. The method was based on gas chromatography coupled to a hybrid quadrupole time-of-flight mass spectrometer with an atmospheric pressure chemical ionization source (GC-(APCI)QTOF MS). A non-target acquisition was performed through two alternating scan events: one at low collision energy and another at a higher collision energy ramp (MS^E). In this way, both protonated molecule and/or molecular ion together with fragment ions were obtained in a single run. Validation was performed according to SANCO/12571/2013 by analysing 20 samples (10 different commodities in duplicate), fortified with a test set of 132 pesticides at 0.01, 0.05 and 0.20 mg kg⁻¹. For screening, the detection was based on one diagnostic ion (in most cases the protonated molecule). Overall, at the 0.01 mg kg⁻¹ level, 89% of the 2620 fortifications made were detected. The screening detection limit for individual pesticides was 0.01 mg kg⁻¹ for 77% of the pesticides investigated. The possibilities for identification according to the SANCO criteria, requiring two ions with a mass accuracy ≤±5 ppm and an ion-ratio deviation ≤±30%, were investigated. At the 0.01 mg kg⁻¹ level, identification was possible for 70% of the pesticides detected during screening. This increased to 87% and 93% at the 0.05 and 0.20 mg kg⁻¹ level, respectively. Insufficient sensitivity for the second ion was the main reason for the inability to identify detected pesticides, followed by deviations in mass accuracy and ion ratios.     

Determination of monomers and oligomers in polyethylene terephthalate trays and bottles for food use by using high performance liquid chromatography-electrospray ionization-mass spectrometry

The types and contents of monomers and oligomers in polyethylene terephthalate (PET) food containers were analyzed using HPLC-ESI-MS after being extracted with 50% acetonitrile or dichloromethane using an accelerated solvent extraction unit. The types of cyclic oligomers were classified into first and second series. The first series represented a type of [TG]n composed of terephthalic acid (TPA; T) and monoethylene glycol (EG; G) at a ratio of 1:1. The second series showed a type of [TG]nG in which a single G unit was substituted by diethylene glycol (DEG; GG). The oligomer level extracted using dichloromethane was measured at 4024–11576 mg kg^?1. The first series cyclic oligomers, second series cyclic oligomers and linear oligomers constituted 83.0–90.6%, 7.8–14.7% and 1.3–2.8%, of the total extracted oligomers, respectively. The extracted amounts of TPA, monohydroxyethyl terephthalate and bishydroxyethyl terephthalate using 50% acetonitrile were 3.0–28.2 mg kg^?1, 16.8–118.2 mg kg^?1 and 3.9–26.7 mg kg^?1, respectively. The A2, A3, S2 and S3 groups as modified oligomers were detected as 42.9–221.4 mg kg^?1, 17.2–250.3 mg kg^?1, 1.1–48.1 mg kg^?1 and 1.0–19.8 mg kg^?1, respectively. The results of this study demonstrate an advanced analytical approach to determine the residual oligomers and monomers in PET products for food use and imply their potential migration to foodstuffs.     

A new quantitative and low-cost determination method of nitrate in vegetables, based on deconvolution of UV spectra

A new UV-spectrophotometric method for the determination of nitrate in vegetables is presented. The method is based on the spectral deconvolution: UV spectrum of a sample is considered as a linear combination of absorption spectra, named reference spectra. The combination of a small number of spectra of reference allows to reconstitute the shape of UV spectrum of an unknown sample. There have been several fresh vegetables (lettuce, curly lettuce, oak-leaf lettuce), as well as frozen spinaches that have been tested. The results obtained were comparable to those obtained with the reference HPLC method (official European reference method for the determination of nitrate in foodstuffs). The nitrate content varied from 377 to 3240 mg kg⁻¹ of fresh vegetables, and 545 to 1190 mg kg⁻¹ of frozen spinach. The recovery of added nitrate ranged from 91 to 99%. The results were obtained with a laboratory spectrophotometer and also with a dedicated field-type spectrophotometer. This method does not require almost any consumable, is quantitative and very fast reading with easy and low maintenance.     

Fast quantitation of 5-hydroxymethylfurfural in honey using planar chromatography

An approach for rapid quantitation of 5-hydroxymethylfurfural (HMF) in honey using planar chromatography is suggested for the first time. In high-performance thin-layer chromatography (HPTLC) the migration time is approximately 5 min. Detection is performed by absorbance measurement at 290 nm. Polynomial calibration in the matrix over a range of 1:80 showed correlation coefficients, r, of ≥ 0.9997 for peak areas and ≥ 0.9996 for peak heights. Repeatability in the matrix confirmed the suitability of HPTLC–UV for quantitation of HMF in honey. The relative standard deviation (RSD, %, n = 6) of HMF at 10 ng/band was 2.9% (peak height) and 5.2% (peak area); it was 0.6% and 1.0%, respectively, at 100 ng/band. Other possible detection modes, for example fluorescence measurement after post-chromatographic derivatization and mass spectrometric detection, were also evaluated and can coupling can be used as an additional tool when it is necessary to confirm the results of prior quantitation by HPTLC–UV. The confirmation is provided by monitoring the HMF sodium adduct [M + Na]⁺ at m/z 149 followed by quantitation in TIC or SIM mode. Detection limits for HPTLC–UV, HPTLC–MS (TIC), and HPTLC–MS (SIM) were 0.8 ng/band, 4 ng/band, and 0.9 ng/band, respectively. If 12 μL honey solution was applied to an HPTLC plate, the respective detection limits for HMF in honey corresponded to 0.6 mg kg⁻¹. Thus, the developed method was highly suitable for quantitation of HMF in honey at the strictest regulated level of 15 mg kg⁻¹. Comparison of HPTLC–UV detection with HPTLC–MS showed findings were comparable, with a mean deviation of 5.1 mg kg⁻¹ for quantitation in SIM mode and 6.1 mg kg⁻¹ for quantitation in TIC mode. The mean deviation of the HPTLC method compared with the HPLC method was 0.9 mg kg^-1 HMF in honey. Re-evaluation of the same HPTLC plate after one month showed a deviation of 0.5 mg kg⁻¹ HMF in honey. It was demonstrated that the proposed HPTLC method is an effective method for HMF quantitation in honey.      

Rapid surface plasmon resonance immunobiosensor assay for microcystin toxins in blue-green algae food supplements

A surface plasmon resonance (SPR) immunobiosensor assay was developed and validated to detect microcystin toxins in Spirulina and Aphanizomenon flos-aquae blue-green algae (BGA) food supplements. A competitive inhibition SPR-biosensor was developed using a monoclonal antibody to detect microcystin (MC) toxins. Powdered BGA samples were extracted with an aqueous methanolic solution, centrifuged and diluted in HBS-EP buffer prior to analysis. The assay was validated in accordance with the performance criteria outlined in EU legislation 2002/657/EC. The limit of detection (LOD) of the assay was calculated from the analysis of 20 known negative BGA samples to be 0.561 mg kg⁻¹. The detection capability (CCβ) of the assay was determined to be ≤0.85 mg kg⁻¹ for MC-LR. The biosensor assay was successfully applied to detect MC-LR toxins in BGA samples purchased on the Irish retail market. MC-LR was detected in samples at levels ranging from <0.5 to 2.21 mg kg⁻¹. The biosensor results were in good agreement with an established LC-MS/MS assay. The assay is advantageous because it employs a simple clean-up procedure compared to chemical assays and allows automated unattended analysis of samples unlike ELISA.     

Spectrophotometric determination of triclosan in personal care products

A spectrophotometric method for the determination of triclosan in personal care products was proposed. It was based on the reaction of sodium nitrite with p-sulfanilic acid in an acidic medium to form diazonium ion, with which triclosan further formed an azo compound in an alkaline medium. The resulting yellow colored product has a maximum absorption at 452 nm. A good linear relationship (r = 0.9999) was obtained in the range of 0–30 mg L⁻¹ triclosan. A detection limit of 0.079 g L⁻¹ was achieved and the relative standard deviation was 0.24% (n = 11) at 14 mg L⁻¹ triclosan. The proposed method has been applied to the analyses of triclosan in several personal care products and the results were in good agreement with those obtained by high-performance liquid chromatography.     

Development of an optical surface plasmon resonance biosensor assay for (fluoro)quinolones in egg, fish, and poultry meat

The aim of this study was to develop an optical biosensor inhibition immunoassay, based on the surface plasmon resonance (SPR) principle, for use as a screening test for 13 (fluoro)quinolones, including flumequine, used as veterinary drugs in food-producing animals. For this, we immobilised various quinolone derivatives on the sensor chip and tested binding of a range of different antibodies (polyclonal and one engineered antibody) in the presence and absence of free (fluoro)quinolones. The main challenge was to detect flumequine in an assay giving good results for the other compounds. One antigen–antibody combination proved satisfactory: polyclonal antibodies raised against a dual immunogen and, on the sensor chip, a fluoroquinolone derivative. It was the first time that this concept of the bi-active antibody was described in the literature.The assay, optimised for detection in three matrices (poultry muscle, fish, and egg), was tested on incurred samples prepared by liquid extraction followed by two washing steps. This rapid, simple method proved adequate for detecting at least 13 (fluoro)quinolones at concentrations below established maximum residue levels (MRLs). The reference molecule norfloxacin could be detected in the range of 0.1–10 μg kg⁻¹ in extracts of egg and poultry meat and in the range of 0.1–100 μg kg⁻¹ in extracts of fish. The determined midpoints of these calibration curves were about 1, 1.5 and 3 μg kg⁻¹ in poultry meat, egg and fish, respectively.     

Determination of arsenic (III) and arsenic (V) in freshwater biological samples from Thailand by solvent extraction and neutron activation

Neutron activation analysis (NAA) methods were employed for the determination of total arsenic, and water soluble As(III) and As(V) compounds in freshwater fish/shellfish and plant samples from Southern Thailand. Total arsenic concentrations varied from 0.05 to 425 mg kg⁻¹. Water soluble arsenic species were separated by solvent extraction using ammonium pyrrolidinedithiocarbamate (APDC)/methylisobutylketone (MIBK) followed by NAA. The water soluble As(III) and As(V) levels varied from 0.07 to 26.4 and 0.03 to 22.9 mg kg⁻¹, respectively. The As(III) and As(V) detection limits were 0.007 for fish/shellfish, 0.005 for As(III) and 0.006 mg kg⁻¹ for As(V) in plants. This separation method allows for the determination of water soluble As(III) and As(V) using commonly available and inexpensive laboratory equipment and chemicals, which can be coupled to a variety of quantification techniques.     

Homogeneous liquid-liquid extraction combined with gas chromatography-electron capture detector for the determination of three pesticide residues in soils

In this study, a new method was developed for analyzing malathion, cypermethrin and lambda-cyhalothrin from soil samples by using homogeneous liquid–liquid extraction (HLLE) and gas chromatography with electron capture detector (GC–ECD). Acetone was used as extraction solvent for the extraction of target pesticides from soil samples. When the extraction process was finished, the target analytes in the extraction solvent were rapidly transferred from the acetone extract to carbon tetrachloride, using HLLE. Under the optimum conditions, linearity was obtained in the range of 0.05–40 μg kg⁻¹ for malathion, 0.04–10 μg kg⁻¹ for lambda-cyhalothrin and 0.05–50 μg kg⁻¹ for cypermethrin, respectively. Coefficients of correlation (r²) ranged from 0.9993 to 0.9998. The repeatability was carried out by spiking soil samples at concentration levels of 2.5 μg kg⁻¹ for lambda-cyhalothrin, and 10 μg kg⁻¹ for malathion and cypermethrin, respectively. The relative standard deviations (RSDs) varied between 2.3 and 9.6% (n = 3). The limits of detection (LODs), based on signal-to-noise ratio (S/N) of 3, varied between 0.01 and 0.04 μg kg⁻¹. The relative recoveries of three pesticides from soil A1, A2 and A3 at spiking levels of 2.5, 5 and 10 μg kg⁻¹ were in the range of 82.20–91.60%, 88.90–110.5% and 77.10–98.50%, respectively. In conclusion, the proposed method can be successfully applied for the determination of target pesticide residues in real soil samples.     

Interfacial reaction using particle-immobilized reagents in a fluidized reactor. Determination of glycerol in biodiesel

A novel fluidized beads strategy for utilization of particle-immobilized reagents in flow analysis was developed in this study. The performance of the suggested strategy was demonstrated by the determination of glycerol in biodiesel. This analytical task was used as a proof-of-concept example. The method is based on on-line extraction of glycerol from biodiesel into aqueous stationary phase of extraction-chromatographic column, followed by elution and spectrophotometric determination in the form of copper glycerate formed in a fluidized reactor of stepwise injection system. The floating of cation exchange resin Dowex^® 50WX4, saturated with Cu(II) ions in liquid phase, was accomplished by air-bubbling. The linear range was from 100 to 1000 mg kg⁻¹, and the limit of detection, calculated as 3s of a blank test (n = 5), was found to be 30 mg kg⁻¹. The method was successfully applied to the analysis of biodiesel and biodiesel-blend (B 20) samples.     

Determination of bromide ions in seawater using flow system with chemiluminescence detection

A simple flow-based procedure with chemiluminescence (CL) detection is proposed for bromide ion determination in seawater. The procedure was based on the oxidation of bromide to bromine by chloramine-T followed by the reaction of bromine with luminol resulting in CL emission. Since no significant reaction within chloramine-T and luminol was observed, the detection was carried out without bromine extraction from the oxidant medium. The proposed flow system had a sampling rate of 40 determinations per hour, reagents consumption of 100 μg luminol and 60 μg chloramine-T per determination, a limit of detection of 0.5 mg l⁻¹ bromide ions, a linear concentration range (r = 0.999 and n = 7) between 0 and 100 mg l⁻¹, and a coefficient of variance better than 2.5% (for 10 measurements of a 10 mg l⁻¹ Br⁻ solution) were achieved. The analytical system was applied for the determination of bromide in seawater and estuarine-water samples, obtaining an analyte recovery ranging from 94 to 102% and comparing the results with a reference spectrophotometric method no significant difference was observed in 95% confidence level.     

Comparison of neutron activation analysis with conventional detection techniques for the evaluation of trace elemental contamination in Mallard (<Emphasis Type="Italic">Anas platyrhynchos</Emphasis>) feathers

Instrumental neutron activation analysis (INAA) was used to determine trace elemental contamination in bird feathers. Primary feathers from twelve mallard (Anas platyrhynchos) ducks, migrating through the Thousand Islands region of Ontario, Canada, were analyzed for selenium, mercury, chromium, arsenic and antimony. Certified reference materials were used to assess the quality of the analytical procedure. Quantification of chemical elements was performed using Ortec Gamma Vision software. Five chemical elements were quantified, with corresponding analytical uncertainties of less than 20%. Results indicated the presence of As (max = 0.13 mg kg⁻¹), Cr (max = 2.6 mg kg⁻¹), Hg (max = 7.7 mg kg⁻¹), Sb (max = 0.31 mg kg⁻¹) and Se (max = 1.31 mg kg⁻¹). To assess the validity of using INAA as a quantitative analytical technique for feather samples, two standard reference materials were examined and mercury results were compared to those obtained from both direct mercury analysis (DMA) and cold vapour atomic absorption spectroscopy (CVAAS). Several CVAAS results differed significantly from the INAA results; in many instances CVAAS appeared to under-report when compared to INAA, with relative percent difference values as high as 126%. Conversely, results obtained using DMA compared favourably with INAA. For all samples, RPD values were within 30%. This is the first study to use INAA to examine feather contamination in Canadian migratory waterfowl and the first to corroborate INAA feather results by comparing them to those obtained using CVAAS and DMA.     

Accelerated solvent-based extraction and enrichment of selected plasticisers and 4-nonylphenol, and extraction of tin from organotin sources in sediments, sludges and leachate soils

Enrichment techniques have become an important feature in the trace analysis of oestrogen mimicking chemicals in the environment. Recent developments such as accelerated solvent extraction (ASE) have improved extraction recoveries in a wide variety of solid matrices including sediments, sludges and leachate soils. Such samples taken from the Irish Midlands Shannon Catchment region during the winter of 2004/5 and suspected to contain certain xenooestrogens or hormonally active agents were extracted using this technique, which was then coupled with high performance liquid chromatography (HPLC) for quantification purposes. ASE was thus employed to both isolate and pre-concentrate targeted analytes using the minimum amount of solvent hence making extractions more conservational. Two simple, yet extremely sensitive liquid chromatographic methods were developed based on UV detection; one for phthalates and one for alkylphenols, with recoveries reaching up to 92.0%. Acid digestion was used for the extraction of the tin and organotin compounds with analysis by polarography. In river sediment, levels of up to 24.4 mg kg⁻¹ phthalate, 1.14 mg kg⁻¹ 4-nonylphenol and 118 mg kg⁻¹ tin were found. In leachate sediments, values up to 49.8 mg kg⁻¹ phthalate, 1.57 mg kg⁻¹ 4-nonylphenol, and 36.0 mg kg⁻¹ tin were determined. In sludge, values up to 174 mg kg⁻¹ phthalate and 22.8 mg kg⁻¹ 4-nonylphenol were quantified. The highest value of tin (118 mg kg⁻¹) was found present in an area of high leisure craft activity. Typical sediment levels of tin at other river locations ranged between 1.20 and 37.5 mg kg⁻¹.     

Determination of iodine in biological materials by pseudo-cyclic epithermal INAA using anti-coincidence gamma-ray spectrometry and estimation of expanded uncertainties

Epithermal instrumental neutron activation analysis (EINAA) technique in conjunction with anti-coincidence gamma-ray spectrometry (AC) has been applied for the determination of ppm to ppb levels of iodine in biological materials containing high levels of Al, Br, Cl, K, Mn, and Na. Both conventional EINAA-AC and pseudo-cyclic EINAA-AC (PC-EINAA-AC) methods using a combination of Cd and B filters have been developed using Dalhousie University SLOWPOKE-2 reactor (DUSR) facility. The expanded uncertainties (EU), at about 95% confidence level, for iodine in biological materials by EINAA-AC varied between 6 and 10%. The advantages of the non-destructive PC-EINAA-AC method has been successfully demonstrated by analyzing the NIST Pine Needles (SRM 1575) containing a low amount of iodine in presence of high quantities of Mn and other interfering elements where an iodine content of 92.8 μg kg⁻¹ with an EU of 6.1 μg kg⁻¹ and a detection limit of 40 μg kg⁻¹ has been obtained at the end of fourth cycle.     

Triptycene-based porous photoluminescent polymers with dual role: efficient capture of carbon dioxide and sensitive detection of picric acid

Design and synthesis of unique photoluminescent triptycene-based porous polymers (TBP-OH and TBP-NH₂) bearing active functional groups is described herein. Pd catalyzed Sonogashira cross-coupling reaction was utilized to obtain these polymeric networks that are nanoporous and strongly fluorescent in THF. In solid state, these polymers demonstrated CO₂ uptake up to 92 mg g^?1 at 273 K/1bar and H₂ up to 16 mg g^?1 at 77 K/1bar which may be attributed to the presence of 3D robust triptycene and CO₂-philic groups –OH and –NH₂ in their polymeric framework. TBP-OH and TBP-NH₂ also selectively capture CO₂ over nitrogen and methane. CO₂ capture by TBP-OH and TBP-NH₂ is a physisorption process and hence reversible in nature. Suspensions of TBP-OH and TBP-NH₂ in THF are strongly fluorescent and are also capable of detecting picric acid (an environmental pollutant and explosive) in trace amounts. The Stern–Volmer quenching constants (K_sv) for detection of picric acid (PA) are in the order of 10⁵ M^?1.     

Development of a rapid method for the quantitative determination of deoxynivalenol using Quenchbody

Quenchbody (Q-body) is a novel fluorescent biosensor based on the antigen-dependent removal of a quenching effect on a fluorophore attached to antibody domains. In order to develop a method using Q-body for the quantitative determination of deoxynivalenol (DON), a trichothecene mycotoxin produced by some Fusarium species, anti-DON Q-body was synthesized from the sequence information of a monoclonal antibody specific to DON. When the purified anti-DON Q-body was mixed with DON, a dose-dependent increase in the fluorescence intensity was observed and the detection range was between 0.0003 and 3 mg L⁻¹. The coefficients of variation were 7.9% at 0.003 mg L⁻¹, 5.0% at 0.03 mg L⁻¹ and 13.7% at 0.3 mg L⁻¹, respectively. The limit of detection was 0.006 mg L⁻¹ for DON in wheat. The Q-body showed an antigen-dependent fluorescence enhancement even in the presence of wheat extracts. To validate the analytical method using Q-body, a spike-and-recovery experiment was performed using four spiked wheat samples. The recoveries were in the range of 94.9–100.2%. The concentrations of DON in twenty-one naturally contaminated wheat samples were quantitated by the Q-body method, LC-MS/MS and an immunochromatographic assay kit. The LC-MS/MS analysis showed that the levels of DON contamination in the samples were between 0.001 and 2.68 mg kg⁻¹. The concentrations of DON quantitated by LC-MS/MS were more strongly correlated with those using the Q-body method (R² = 0.9760) than the immunochromatographic assay kit (R² = 0.8824). These data indicate that the Q-body system for the determination of DON in wheat samples was successfully developed and Q-body is expected to have a range of applications in the field of food safety.     

Chitosan–magnetite nanocomposites (CMNs) as magnetic carrier particles for removal of Fe(III) from aqueous solutions

This research focuses on removal of Fe(III) from aqueous solution using chitosan–magnetite nanocomposites as potential sorbent. The presence of nanosized magnetic particles within the nanocomposites was confirmed by TEM and SAED analysis. The particles with diameter 508 μm and 84 μm, follow Frendlich sorption isotherm at 30 °C, and the Frendlich constants (K_F, 1/n) have been found to be 5.974 mg g⁻¹, 2.66 and 35.98 mg g⁻¹, 1.385, respectively. Out of various kinetic models, the experimental data for dynamic uptake of Fe(III) is best fitted on ‘pseudo-second order’ kinetic model. The linear nature of plots between log (% sorption) and log (time) is indicative of intra-particle diffusion. For the particles with diameters 508 μm and 84 μm, the value of k_id was found to be 1.78 mg l⁻¹ min^−0.5 and 2.13 mg l⁻¹ min^−0.5. The sorption mean free energy from the Dubinin–Radushkevic isotherm was found to be 7.04 kJ mol⁻¹ indicating chemical nature of sorption. The increase in chitosan content in sorbent particles is found to enhance the Fe(III) uptake. The various thermodynamic parameters have also been evaluated. Finally, the presence of Cu²⁺ ions in the sorbate is found to decrease the uptake of Fe(III).     

Determination of aminoglycosides in honey by capillary electrophoresis tandem mass spectrometry and extraction with molecularly imprinted polymers

A new analytical method based on capillary zone electrophoresis-tandem mass spectrometry is proposed and validated for the identification and simultaneous quantification of nine aminoglycosides in honey samples. Detection using an ion trap mass analyzer operating in the multiple reaction monitoring mode was used. Different parameters were optimized in order to obtain an adequate separation combined with the highest sensitivity. In order to achieve high selectivity in the sample treatment, a commercially-available molecularly imprinted polymer has been used for the solid phase extraction of the analytes. Under optimum conditions, recoveries for fortified samples ranged from 88.2 to 99.8%, with relative standard deviations lower than 8%. The limits of detection ranged from 0.4 to 28.5 μg kg⁻¹. Furthermore, the decision limit and the detection capability were evaluated, ranging from 3.5 to 60.5 μg kg⁻¹ and from 6.0 to 103.1 μg kg⁻¹, respectively, demonstrating the sensitivity and applicability of this fast and simple method.