Determination of chlorobenzenes in water samples based on fully automated microextraction by packed sorbent coupled with programmed temperature vaporization–gas chromatography–mass spectrometry

A fully automated method consisting of microextraction by packed sorbent (MEPS) coupled directly to programmed temperature vaporizer–gas chromatography–mass spectrometry (PTV–GC–MS) has been developed to determine the 12 chlorobenzene congeners (chlorobenzene; 1,2-, 1,3-, and 1,4-dichlorobenzene; 1,2,3-, 1,2,4-, and 1,3,5-trichlorobenzene; 1,2,3,4-, 1,2,3,5-, and 1,2,4,5-tetrachlorobenzene; pentachlorobenzene; and hexachlorobenzene) in water samples. The effects of the variables on MEPS extraction, using a C18 sorbent, and the instrumental PTV conditions were studied. The internal standard 1,4-dichlorobenzene d4 was used as a surrogate. The proposed method afforded good reproducibility, with relative standard deviations (RSD %) lower than 12 %. The limits of detection varied between 0.0003 μg L^?1 for 1,2,3,4-tetrachlorobenzene and 0.07 μg L^?1 for 1,3- and 1,4-dichlorobenzene, while those of quantification varied between 0.001 μg L^?1 and 0.2 μg L^?1 for the same compounds. Accuracy of the proposed method was confirmed by applying it to the determination of chlorobenzenes in different spiked water samples, including river, reservoir, and effluent wastewater.

Electrochemically controlled solid-phase micro-extraction of proline using a nanostructured film of polypyrrole, and its determination by ion mobility spectrometry

We report on a fast, simple and accurate method for the determination of proline in urine samples by employing a nanostructured film of conducting polypyrrole for electrochemically controlled solid-phase microextraction, and ion mobility spectrometry (IMS) for detection. This method has the advantages of simple sample preparation and a sensitivity of IMS to proline that is higher than that for other amino acids. The calibration curve is linear in the range of 0.5–60 μg L^?1 (4–521 nmol L^?1), and the detection limit is 0.2 μg L^?1. The electrochemical potentials for uptake and release were optimized. The method was successfully applied to the clean-up and quantitation of trace amounts of proline in urine samples.

A highly sensitive caffeine immunoassay based on a monoclonal antibody

A new immunoassay has been developed based on a commercially available anti-caffeine monoclonal antibody and a de novo synthesized tracer, using horseradish peroxidase and UV–visible detection. Caffeine, which is frequently found in surface waters, can be quantified with a relative error lower than 20% for concentrations above 0.025 μg L^?1 (limit of quantitation, direct analysis). The limit of detection is 0.001 μg L^?1 and can be reduced by solid-phase extraction (SPE). Moreover, with minor adaptations, the assay can be used to quantify caffeine in several beverages, shampoo, and caffeine tablets. The results obtained by ELISA correlate well with those from liquid chromatography–tandem mass spectrometry (LC–MS–MS) for the tested matrices. Several surface waters from Berlin were analysed and all tested positive for caffeine, with concentrations higher than 0.030 μg L^?1. In one run 66 samples can be analysed within 2 h.

Highly sensitive SERS probe for mercury(II) using cyclodextrin-protected silver nanoparticles functionalized with methimazole

We have developed a surface-enhanced Raman scattering (SERS) probe for the determination of mercury(II) using methimazole-functionalized and cyclodextrin-coated silver nanoparticles (AgNPs). These AgNPs in pH 10 solution containing sodium chloride exhibit strong SERS at 502 cm^?1. Its intensity strongly decreases in the presence of Hg(II). This effect serves as the basis for a new method for the rapid, fast and selective determination of trace Hg(II). The analytical range is from 0.50 μg L^?1 to 150 μg L^?1, and the limit of detection is 0.10 μg L^?1. The influence of 11 metal ions commonly encountered in environmental water samples was found to be quite small. The method was applied to the determination of Hg(II) in spiked water samples and gave recoveries ranging from 98.5 to 105.2 % and with relative standard deviations of <3.5 % (n?=?5). The total analysis time is <10 min for a single sample.

Sensitive detection of trace hemoglobin using fluorescence method based on functionalized quantum dots

The fluorescence quenching of quantum dots by hemoglobin has been demonstrated to depend on surface functionalization, and this property has been utilized to construct a novel fluorescent method for rapid, sensitive, and selective detection of trace hemoglobin in urine at microgram level. This method shows low interference and high selectivity for hemoglobin with a limit of detection of 4.3 μg L^?1 in water and 66.1 μg L^?1 in urine, which are lower than those of currently used methods in labs and clinics. Spike and recovery tests in raw, acidified, and alkalized urine samples exhibit good recovery rates for the spiked concentrations close to the limit of detection.

Determination of Pt and Pd in particles emitted from automobile exhaust catalysts using ion-exchange matrix separation and voltammetric detection

We report on the ion-exchange separation of Pt and Pd from the main elements emitted from catalysts of gasoline-fueled cars by exploiting the selective chelating ion exchanger Lewatit MonoPlus TP-214. Pt and Pd were then eluted with a recovery of 92% and 96%, respectively, using an acidified solution of thiourea, and the eluent was analyzed by sequential voltammetry. The detection limits are 0.04 μg L^?1 and 1 μg L^?1 for Pt and Pd, respectively, and the relative standard deviation is about 4.0% (for n?=?10). The procedure was successfully applied to particles emitted from automobile exhaust catalysts of four capacity engine vehicles. Graphite furnace atomic absorption spectrometry was also employed for reasons of comparison. Emission by four vehicles with 1400, 2600, 3200, and 4800 cc engines, respectively, ranged from 19 to 28 ng km^?1 for Pt, and from 102 to 150 ng km^?1 for Pd.

Ultra-sensitive spectrophotometric determination of nickel after complexation and membrane filtration

We report on a simple, sensitive and selective method for the spectrophotometric determination of Ni²⁺ in water samples. The analyte ions were collected on a membrane filter in the form of their red complex with 1-(2-pyridylazo)-2-naphthol (PAN), and the absorption spectra of the colored membrane filters were acquired. Effects of pH value, sample volume, and amount of PAN were examined in order to optimize sensitivity. The interference by common other ions was eliminated using appropriate masking agents. The absorbance is linearly related to the concentration of Ni²⁺ in the ranges from 0.3 to 1.5 μg L^?1, and from 2 to 10 μg L^?1, respectively, the correlation coefficients (R²) being 0.9871 and 0.9954. Under the optimal conditions, the detection limit is 0.1 μg L^?1. The recoveries in case of spiked samples are between 95.0% and 101.5%, and the relative standard deviations range from 2.8% to 4.1%.

An automated headspace solid-phase microextraction followed by gas chromatography–mass spectrometry method to determine macrocyclic musk fragrances in wastewater samples

A fully automated method has been developed for determining eight macrocyclic musk fragrances in wastewater samples. The method is based on headspace solid-phase microextraction (HS-SPME) followed by gas chromatography–mass spectrometry (GC-MS). Five different fibres (PDMS 7 μm, PDMS 30 μm, PDMS 100 μm, PDMS/DVB 65 μm and PA 85 μm) were tested. The best conditions were achieved when a PDMS/DVB 65 μm fibre was exposed for 45 min in the headspace of 10 mL water samples at 100 °C. Method detection limits were found in the low ng L^?1 range between 0.75 and 5 ng L^?1 depending on the target analytes. Moreover, under optimized conditions, the method gave good levels of intra-day and inter-day repeatabilities in wastewater samples with relative standard deviations (n?=?5, 1,000 ng L^?1) less than 9 and 14 %, respectively. The applicability of the method was tested with influent and effluent urban wastewater samples from different wastewater treatment plants (WWTPs). The analysis of influent urban wastewater revealed the presence of most of the target macrocyclic musks with, most notably, the maximum concentration of ambrettolide being obtained in WWTP A (4.36 μg L^?1) and WWTP B (12.29 μg L^?1), respectively. The analysis of effluent urban wastewater showed a decrease in target analyte concentrations, with exaltone and ambrettolide being the most abundant compounds with concentrations varying between below method quantification limit (<MQL) and 2.46 μg L^?1.

Determination of microcystin-LR with a glassy carbon impedimetric immunoelectrode modified with an ionic liquid and multiwalled carbon nanotubes

We report on a sensitive, simple, label-free impedance-based immunoelectrode for the determination of microcystin-LR (MCLR). The surface of the electrode was modified with a composite made from multiwalled carbon nanotubes and an ionic liquid, and with immobilized polyclonal antibody against MCLR. Cyclic voltammetry and impedance spectroscopy were applied to characterize the modified electrode. It is found that the multi-walled carbon nanotubes act as excellent mediators for the electron transfer between the electrode and dissolved hexacyanoferrate redox pair, while the ionic liquid renders it biocompatible. The method exhibits a wide linear range (0.005 μg?L-1 to 1.0 μg?L-1), a low detection limit (1.7 ng?L-1) and a long-term stability of around 60 days. The ionic liquid 1-amyl-2,3-dimethylimidazolium hexafluorophosphate gave the best impedimetric response. The new immunoelectrode is sensitive, stable, and easily prepared. It has been successfully applied to the determination of MCLR in water samples.

Emulsification based dispersive liquid microextraction prior to flame atomic absorption spectrometry for the sensitive determination of Cd(II) in water samples

We report on the application of emulsification-based dispersive liquid microextraction (EB-DLME) to the preconcentration of Cd(II). This procedure not only possesses all the advantages of routine DLLME, but also results in a more stable cloudy state which is particularly useful when coupling it to FAAS. In EB-DLME, appropriate amounts of the extraction solvent (a solution of dithizone in chloroform) and an aqueous solution of sodium dodecyl sulfate (SDS; acting as a disperser) are injected into the samples. A stable cloudy microemulsion is formed and Cd(II) ion is extracted by chelation. After phase separation, the sedimented phase is subjected to FAAS. Under optimized conditions, the calibration curve for Cd(II) is linear in the range from 0.1 to 25 μg L^?1, the limit of detection (at S/N?=?3) is 30 pg L^?1, the relative standard deviations for seven replicate analyses (at 0.56 μg L^?1 of Cd(II)) is 4.6 %, and the enrichment factor is 151. EB-DLME in our opinion is a simple, efficient and rapid method for the preconcentration of Cd(II) (and most likely of many other ions) prior to FAAS determination.

A magnetic metal-organic framework as a new sorbent for solid-phase extraction of copper(II), and its determination by electrothermal AAS

We report on the synthesis of Fe₃O₄-functionalized metal-organic framework (m-MOF) composite from Zn(II) and 2-aminoterephthalic acid by a hydrothermal reaction. The magnetic composite is iso-reticular and was characterized by FTIR, X-ray diffraction, SEM, magnetization, and TGA. The m-MOF was then applied as a sorbent for the solid-phase extraction of trace levels of copper ions with subsequent quantification by electrothermal AAS. The amount of sorbent applied, the pH of the sample solution, extraction time, eluent concentration and volume, and desorption time were optimized. Under the optimum conditions, the enrichment factor is 50, and the sorption capacity of the material is 2.4 mg g^?1. The calibration plot is linear over the 0.1 to 10 μg L^?1 Cu(II) concentration range, the relative standard deviation is 0.4 % at a level of 0.1 μg L^?1 (for n?=?10), and the detection limit is as low as 73 ng L^?1. We consider this magnetic MOF composite to be a promising and highly efficient material for the preconcentration of metal ions.

Separation and preconcentration of trace quantities of copper ion using modified alumina nanoparticles, and its determination by flame atomic absorption spectrometry

We report on a sensitive, reliable and relatively fast method for separation, preconcentration and determination of trace quantities of copper(II) ion. It is making use of nanometer-sized γ-alumina nanoparticles modified with sodium dodecyl sulfate (SDS). The adsorptive potential was assessed via a Langmuir isotherm and the maximal sorption capacity was found to be 138 mg g^-1. The effects of pH values, amount of ligand, flow rate, type of eluting agent, volume of eluent, and the volume of sample were examined. The effects of interfering ions on the recovery of the analyte were also investigated. Copper ion was then determined by flame atomic absorption spectrometry. The relative standard deviation for five replicate determinations (at 50 μg L^?1 of copper) is 3.3%. The detection limit (at 3 s) is 2.5 μg L^?1. This method was validated with a certified reference material of oyster tissue (NIST SRM 1566b) and the results coincided well with the certified values. The procedure was successfully applied to the determination of Cu in water and food samples.

Simultaneous determination of sixteen underivatized biogenic amines in human urine by HPLC-MS/MS

The broad group of biogenic amines includes polyamines and catecholamines, whose presence in human tissues and biological fluids can give important diagnostic information and act as marker of many pathologies. In particular, polyamines are involved in cancer cell growth while catecholamines act as neurotransmitters and hormones. Their simultaneous determination in biological tissues and fluids is therefore an important task. A high-performance liquid chromatography tandem mass spectrometry method is presented here for the simultaneous determination in urine of 16 biogenic amines: adrenaline (epinephrine), agmatine, cadaverine, dopamine, histamine, 3-methoxytyramine, noradrenaline (norepinephrine), norephedrine, octopamine, 2-phenylethylamine, putrescine, serotonin, spermidine, spermine, tryptamine, and tyramine. The method does not require any derivatization step. To guarantee the maximum of sensitivity, the mass spectrometer works in selected reaction monitoring mode, monitoring for each analyte the two most intensive transitions. Method validation includes the evaluation of limits of detection (that range from 0.3 to 6.6 μg L^?1), limits of quantitation (that range from 1.0 to 21.9 μg L^?1), linearity range (three orders of magnitude), recovery, intra- and inter-day precision on both concentration, and retention time. Recovery (R) is shown not to depend on the analyte concentration: the average R percent ranges from 72.9 to 100.0 %. Particular attention is devoted to the matrix effect and the correlated phenomena of ion enhancement or suppression in mass spectrometry detection.

Ligandless temperature-controlled ionic liquid-phase microextraction of lead(II) ion prior to its determination by FAAS

We describe the application of temperature-controlled ionic liquid based microextraction (TC-IL-ME) of lead(II) ion. The method does not require the use of an organic solvent or a ligand. Rather, the IL is directly added to the aqueous sample containing Pb(II) in a centrifuge tube, and the mixture is heated to 80 °C for 4 min. After cooling at 0 °C, the solution turns cludy due to the formation of fine droplets of the IL containing Pb(II). The IL is separated by centrifugation, acidified, and directly submitted to FAAS by microinjection. The effects of pH value, volume of IL, extraction time, temperature, sample volume and matrix were optimized to result in a preconcentration factor of 30, a detection limit of 5.8 μg L^?1, and a limit of quantification of 19.3 μg L^?1. The method was validated by analyzing a certified reference material (NCSZC81002B; hair). A recovery test performed with spiked samples gave values between 102 % and 105 %. The method was also used to determine Pb(II) in hair samples.

Ultrasound-assisted emulsification–microextraction for the sensitive determination of ethyl carbamate in alcoholic beverages

A method based on ultrasound-assisted emulsification–microextraction (USAEME) was proposed in this contribution for the determination of ethyl carbamate (EC) in alcoholic beverages using gas chromatography coupled to triple quadrupole mass spectrometry. To achieve the determination of EC in alcoholic beverages, the influences on the extraction efficiency of type and volume of extraction solvent, temperature, ionic strength, alcohol content, and extraction time were studied, once the extraction solvent had been selected. The optimized conditions were 200.0 μL of chloroform at 30 °C during 5 min with 15 % (m/v) sodium chloride addition. The detection limit, relative standard deviations, linear range, and recoveries under the optimized conditions were 0.03 μg L^?1, 4.2–6.1 %, 0.1–50.0 μg L^?1, and 80.5–87.9 %, respectively. Moreover, the feasibility of the present method was also validated by real samples. To the best of our knowledge, this is the first time that USAEME has been applied to determine a strongly hydrophilic compound in alcoholic beverages.

Polythiophene-coated Fe3O4 nanoparticles as a selective adsorbent for magnetic solid-phase extraction of silver(I), gold(III), copper(II) and palladium(II)

We have developed a fast method for sensitive extraction and determination of the metal ions silver(I), gold(III), copper(II) and palladium(II). Fe₃O₄ magnetic nanoparticles were modified with polythiophene and used for extraction the metal ions without a chelating agent. Following extraction, the ions were determined by flow injection inductively coupled plasma optical emission spectrometry. The influence of sample pH, type and volume of eluent, amount of adsorbent, sample volume and time of adsorption and desorption were optimized. Under the optimum conditions, the calibration plots are linear in the 0.75 to 100 μg L^?1 concentration range (R²?>?0.998), limits of detection in the range from 0.2 to 2.0 μg L^?1, and enhancement factors in the range from 70 to 129. Precisions, expressed as relative standard deviations, are lower than 4.2 %. The applicability of the method was demonstrated by the successful analysis of tap water, mineral water, and river water.

Rapid determination of melamine in milk and milk powder by surface-enhanced Raman spectroscopy and using cyclodextrin-decorated silver nanoparticles

We have synthesized silver nanoparticles (AgNPs) decorated with α-cyclodextrin (CD) by using the traditional silver mirror reaction in the presence of CD. The CD-AgNPs were used as substrate in surface-enhanced Raman spectroscopy (SERS) for determining melamine. The intensity of the Raman band of melamine at 704 cm^?1 was used to determine melamine in milk and milk powder. The use of CD-AgNPs as the SERS substrate rather than classical silver nanoparticles makes the method more sensitive in giving an enhancement by a factor of up to?~?10⁶ in scattering efficiency. The effects of the volume of solutions (of CD-AgNPs, NaCl, NaOH, melamine) and of mixing time were optimized. The standard addition method was employed for quantitative analysis. The correlation coefficient of the calibration plot is 0.9995, and the limit of detection is 3.0 μg L^?1. The method was successfully applied to the determination of melamine in milk and milk powder, with relative standard deviations of <10 % and recoveries between 89 and 104 %.

A molecular imprint-coated stirrer bar for selective extraction of caffeine, theobromine and theophylline

We have prepared a novel caffeine imprinted polymer on a stir bar that can be used for selective extraction of caffeine, theobromine and theophylline from beverages. The polymerization time and quantities of reagents (template, cross-linker, porogenic solvent) were optimized. The morphology of the molecularly imprinted polymer-coating was studied by scanning electron microscopy and Fourier transform IR spectroscopy. A rapid and sensitive method was worked out for the extraction of caffeine, theobromine and theophylline from beverages by using the molecularly imprinted stir bar followed by HPLC analysis. The effects of extraction solvent, stirring speed, desorption solvent, adsorption and desorption time were optimized. The method displays a linear response in the 5–150 μg L^?1 caffein concentration range, with a correlation coefficient of >0.9904. The recoveries for three analytes in tea, carbonated and functional beverages were 91–108 %, 90–110 % and 93–109 %, with relative standard deviations ranging from 3.6–5.7 %, 3.5–7.9 % and 3.2–7.9 %, respectively.

Speciation of Cr(III) and Cr(VI) ions using a β-cyclodextrin-crosslinked polymer micro-column and graphite furnace atomic absorption spectrometry

A sensitive and selective method for the speciation of Cr(III) and Cr(VI) in water samples was developed. It is based on the selective binding of the complex formed between Cr(III) and 4-(2-pyridylazo)resorcinol adsorbed on a cross-linked polymer modified with β-cyclodextrin and placed in a micro-column. Graphite furnace atomic absorption spectrometry (GFAAS) was used to quantify chromium. Cr(VI) ion is not adsorbed but remains in the aqueous sample phase. Thus, an in-situ separation of Cr(VI) and Cr(III) is accomplished. The concentration of Cr (VI) was calculated by subtracting the value for Cr(III) from that for total chromium. Under optimum conditions, the limit of detection of Cr(III) is 0.056 μg L^?1, and the linear range is from 2.0 to 160.0 μg L^?1. The relative standard deviation is 2.5% (n?=?3, at 30.0 μg L^?1). The preconcentration factor is 25. The method was applied to the speciation of chromium in water samples, and recoveries in spiked real samples range from 101.9% to 104.5%. A reference water sample (GBW(E)080642) also was analyzed, and the results were in good agreement with the certified values.

Determination of lewisite metabolite 2-chlorovinylarsonous acid in urine by use of dispersive derivatization liquid-liquid microextraction followed by gas chromatography–mass spectrometry

The purpose of this study was to develop a sensitive and simple method, based on dispersive derivatization liquid-liquid microextraction–gas chromatography–mass spectrometry (DDLLME–GC–MS) in scanning and selected-ion-monitoring (SIM) modes, for detection of 2-chlorovinylarsonous acid (CVAA) as a hydrolysis product and urinary metabolite of lewisite in urine samples. Chloroform (65 μL), methanol (500 μL), and ethanedithiol (10 μL) were used as extraction solvent, dispersive solvent, and derivatizing reagent, respectively. Critical conditions of the proposed method were optimized. The nucleophilic reactions of dithiol and monothiol compounds with CVAA were also studied using a competitive method. In view of the high affinity of trivalent arsenic for sulfhydryl groups, the interaction between CVAA and bis(2-chlorovinyl)arsonous acid (BCVAA) and free cysteine (Cys) was also investigated using liquid chromatography–electrospray ionization mass spectrometry (LC–ESI-MS). The interference of Cys, present in human urine, with the detection of CVAA was evaluated using dithiol and monothiol chemicals as derivatization agents. The developed method provided a preconcentration factor of 250, and limits of detection of 0.015 and 0.30 μg L^?1 in SIM and scanning modes, respectively. The calibration curves were linear over the concentration range of 1–400 μg L^?1 in full-scan mode. The relative standard deviation (RSD) values were calculated to be 5.5 and 3.2 % at concentrations of 20 and 100 μg L^?1, respectively. Collision-induced dissociation studies of the major electron-impact (EI) ions were performed to confirm the proposed fragment structure of CVAA-dithiols derivatives. Results indicated that the developed method for analysis of CVAA is suitable not only for verification of human exposure to lewisite, but also for quantification of CVAA in urine samples.