Electrochemical sensing platform with gold nanoparticles capped by PDDA for benzyl alcohol determination.

An electrochemical sensor has been developed, by modifying screen-printed carbon devices (SPCE) with photochemically synthesized gold nanoparticles (AuNP), to determine benzyl alcohol, a preservative widely used in the cosmetic industry. To obtain the AuNP with the best properties for electrochemical sensing applications, the photochemical synthesis was optimized using chemometric tools. A response surface methodology based on central composite design was used to optimize the synthesis conditions, as irradiation time, and the concentrations of metal precursor and the capping/reducing agent (poly(diallyldimethylammonium) chloride, PDDA). The anodic current of benzyl alcohol on SPCE modified with the AuNP was used as response of the system. The best electrochemical responses were obtained using the AuNP generated by irradiating for 18 min a 7.20 [Formula: see text] 10-4 mol L-1 AuCl4--1.7% PDDA solution. The AuNP were characterized by transmission electron microscopy, cyclic voltammetry and dynamic light scattering. The nanocomposite-based sensor formed by the optimal AuNP (AuNP@PDDA/SPCE) was used to determine benzyl alcohol by linear sweep voltammetry in 0.10 mol L-1 KOH. The anodic current at + 0.017 ± 0.003 V (vs. AgCl) was used as analytical signal. Detection limit obtained under these conditions was 2.8 µg mL-1. The AuNP@PDDA/SPCE was applied to determine benzyl alcohol  in cosmetic samples.

An environmentally friendly approach for the characterization of construction materials: determination of trace, minor, and major elements by slurry sampling high-resolution continuum source graphite furnace atomic absorption spectrometry.

A slurry sampling method was developed for the fast determination of Pb, Ni, Fe, and Mn in construction materials by high-resolution continuum source graphite furnace atomic absorption spectrometry (HR-CS GFAAS). For sample introduction into the GF, stable slurries were prepared by sonicating 10 mg of ground solid sample in 10.0 mL of 1% (v/v) Triton X-100 and 1% (v/v) HNO3 solution for 1.0 min. The determination of the four elements was carried out in three measurement runs, with Ni and Fe being determined simultaneously. The HR-CS GFAAS measurements were performed using analytical lines with adequate sensitivity, considering the content of each element in the material: Pb at 283.306 nm (42%), Mn at 403.080 nm (6.7%), Ni at 232.003 nm (100%) and Fe at 232.036 nm (1.4%). The pyrolysis and atomization temperatures and the use of chemical modifiers were optimized using both aqueous standards and slurry samples. At optimal conditions, samples with concentrations of Pb from 1.5 to 80 µg g-1, Ni from 4.0 to 75 µg g-1, Mn from 2.0 to 600 µg g-1, and Fe from 0.15 to 60 mg g-1 could be determined using a unique sample suspension. To assess the validity of the method, a fly ash certified reference material (CRM) was analysed using the slurry sampling HR-CS GFAAS method; this CRM and the construction material samples were also analysed by HR-CS GFAAS after the digestion of the samples. The obtained results using both methods were statistically comparable (Student's paired t-test for two independent methods at a 95% confidence level) demonstrating the suitability of the proposed method.

A MWCNTs-COOH/PSS nanocomposite-modified screen-printed electrode for the determination of synthetic phenolic antioxidants by HPLC with amperometric detection.

New sensing platforms based on screen-printed carbon electrodes modified with composites based on polystyrene sulfonate and oxidized multi-walled carbon nanotubes (PSS/MWCNTs-COOH/SPCE) have been used to develop a novel HPLC method with electrochemical detection (ECD) for the determination of the most used synthetic phenolic antioxidants in cosmetics: butylhydroxytoluene (BHT), butylhydroxyanisole (BHA), tert-butylhydroquinone (TBHQ) and propyl gallate (PG). Optimal separation conditions were achieved using methanol: 0.10 mol L-1 acetate solution at pH 6 as mobile phase with a gradient elution program from 60 to 90% of methanol percentage in 15 min. The electrochemical detection was carried out in amperometric mode using the PSS/MWCNTs-COOH/SPCE at + 0.80 V vs. Ag. Under these optimal separation and detection conditions, the limits of detection (LOD) were between 0.11 and 0.25 mg L-1. These LOD values were better, especially for BHT, than those previously published in other HPLC methods. Linear ranges from 0.37 mg L-1, 0.83 mg L-1, 0.69 mg L-1 and 0.56 mg L-1 to 10 mg L-1 were obtained for PG, TBHQ, BHA and BHT, respectively. RSD values equal or lower than 5% and 8% were achieved for repeatability and reproducibility, respectively. The HPLC-ECD method was successfully applied to analyze different cosmetic samples. Recovery values within 83-109% were obtained in the validation studies.

Disposable screen-printed carbon-based electrodes in amperometric detection for simultaneous determination of parabens in complex-matrix personal care products by HPLC.

Parabens are chemicals widely used as preservatives in different types of industrial products. In recent years, the concern about the safety of these compounds has increased due to their endocrine disrupting activity. For this reason, their use is highly regulated and even some of them have already been banned. Thus, methods for the sensitive and selective detection of these compounds are required to control their presence in food, cosmetic, and pharmaceutical products. This paper presents an HPLC method with electrochemical detection using disposable screen-printed electrodes (SPE) for simultaneous determination of 6 different parabens in personal care products. Electrochemical behaviour of parabens was studied on SPE with different carbon-based materials as working electrode: carbon, ordered mesoporous carbon and graphene. From these studies, pH, detection potential, and the most adequate SPE were chosen. Due to the wide range of textures and viscosities (e.g., liquid, solid, and semi-solid) of personal care products, adequate sample pretreatments are required before chromatographic measurement. Here, a fast ultrasound-assisted extraction method was applied to simultaneously extract 6 parabens (methyl-, ethyl-, isopropyl-, propyl-, butyl-and benzyl-paraben) from different complex-matrix cosmetic products. Instrumental limits of detection between 20 and 115 µg L-1 were obtained applying +1.0 V (vs. Ag) as detection potential on carbon-based SPE. The total analysis time, including sample extraction and HPLC run, was shorter than 35 min. The proposed method is more versatile and faster than the current available methods and has been successfully applied to determine parabens in commercial samples such as shampoos, body creams, facial tonics, and toothpastes.

Methylisothiazolinone response on disposable electrochemical platforms modified with carbon, nickel or gold-based nanomaterials.

Screen-printed carbon electrodes (SPCE) were modified with nanocomposite membranes based on polystyrene sulfonate (PSS) or poly(diallyldimethylammonium) (PDDA) matrices and different nanomaterials. Carbon nano-powders (CnP), carbon nano-fibers (CnF) and multi-walled carbon nano-tubes (MWCNTs) were incorporated on PSS matrix. Nickel was incorporated by ion exchange in PSS-CnP composite membranes. Gold nanoparticles (AuNp) were photochemically and electrochemically synthesised and introduced into PDDA membranes. The electrochemical behaviour of methylisothiazolinone (MIT) using these modified electrodes was studied by cyclic voltammetry in 0.1 mol L-1 NaOH. No electrochemical response is obtained on PSS-nanocarbon transducers at the assayed conditions. The nickel-based transducers allow the MIT identification but not quantification. Using AuNp-based electrochemical transducers, it is observed that in presence of MIT, the electron transfer for AuNp reduction is inhibited, and an oxidation peak appears at + 0.45 V, indicating an interaction between MIT and AuNp on the electrode surface. These facts support the usefulness of the AuNp-based electrodes for the determination of MIT. The intensity of the anodic peak observed at + 0.45 V vs. Ag/AgCl was used as analytical signal for MIT determination. A linear relationship between anodic peak current and MIT concentration is observed in the range 8.7 to 36 mg L-1 using the transducer prepared by incorporating gold into the PDDA membrane by ion exchange and synthesising AuNp electrochemically. For this electrode, the limit of detection is 2.6 mg L-1 and the reproducibility, expressed as relative standard deviation (RSD), is lower than 7%. Graphical abstractSchematic representation of the preparation of gold nanoparticles (AuNp) and poly(diallyldimethylammonium) (PDDA)-based platforms and methylisothiazolinone (MIT) electrochemical response on these nanostructured platforms.

Micro-sampling method based on high-resolution continuum source graphite furnace atomic absorption spectrometry for calcium determination in blood and mitochondrial suspensions.

A micro-sampling and straightforward method based on high resolution continuum source atomic absorption spectrometry (HR-CS AAS) was developed to determine extracellular and intracellular Ca in samples of interest in clinical and biomedical analysis. Solid sampling platforms were used to introduce the micro-samples into the graphite furnace atomizer. The secondary absorption line for Ca, located at 239.856nm, was selected to carry out the measurements. Experimental parameters such as pyrolysis and atomization temperatures and the amount of sample introduced for the measurements were optimized. Calibration was performed using aqueous standards and the approach to measure at the wings of the absorption lines was employed for the expansion of the linear response range. The limit of detection was of 0.02mgL-1 Ca (0.39ng Ca) and the upper limit of linear range was increased up to 8.0mgL-1 Ca (160ng Ca). The proposed method was used to determine Ca in mitochondrial suspensions and whole blood samples with successful results. Adequate recoveries (within 91-107%) were obtained in the tests performed for validation purposes.

Determination of essential elements in beverages, herbal infusions and dietary supplements using a new straightforward sequential approach based on flame atomic absorption spectrometry.

A simple method based on FAAS was developed for the sequential multi-element determination of Cu, Zn, Mn, Mg and Si in beverages and food supplements with successful results. The main absorption lines for Cu, Zn and Si and secondary lines for Mn and Mg were selected to carry out the measurements. The sample introduction was performed using a flow injection system. Using the choice of the absorption line wings, the upper limit of the linear range increased up to 110mgL-1 for Mg, 200mgL-1 for Si and 13mgL-1 for Zn. The determination of the five elements was carried out, in triplicate, without the need of additional sample dilutions and/or re-measurements, using less than 3.5mL of sample to perform the complete analysis. The LODs were 0.008mgL-1 for Cu, 0.017mgL-1 for Zn, 0.011mgL-1 for Mn, 0.16mgL-1 for Si and 0.11mgL-1 for Mg.

Electrochemical sensor based on polystyrene sulfonate-carbon nanopowders composite for Cu (II) determination.

A differential pulse anodic stripping voltammetric (DPASV) method, with an open circuit (OC) approach in the pre-concentration step has been developed for copper ion determination at very low concentration level using a sensor based on a polystyrene sulfonate-carbon nanopowders (PSS-CnP) composite. This composite material is easily prepared from ultrasonic assisted dispersions of CnP in aqueous solution of PSS. For preparation of sensor devices, a reproducible and inexpensive drop coating procedure of the surface of home-made pencil graphite electrodes (PGEs) using a CnP dispersion in PSS was performed. At the optimal conditions for accumulation (0.01molL(-1) KNO3 at pH 3) and measurement steps (a reduction potential of -0.5V for 60s and then, an anodic DPV scan) and using a pre-concentration time of 300s, the limit of detection was 0.11µgL(-1) (1.73nM). This OC-DPASV method using the PSS-CnP-PGE sensor was successfully employed for Cu(II) determination in mineral, river and sea water samples.

Fast sequential multi-element determination of major and minor elements in environmental samples and drinking waters by high-resolution continuum source flame atomic absorption spectrometry.

The fast sequential multi-element determination of 11 elements present at different concentration levels in environmental samples and drinking waters has been investigated using high-resolution continuum source flame atomic absorption spectrometry. The main lines for Cu (324.754 nm), Zn (213.857 nm), Cd (228.802 nm), Ni (232.003 nm) and Pb (217.001 nm), main and secondary absorption lines for Mn (279.482 and 279.827 nm), Fe (248.327, 248.514 and 302.064 nm) and Ca (422.673 and 239.856 nm), secondary lines with different sensitivities for Na (589.592 and 330.237 nm) and K (769.897 and 404.414 nm) and a secondary line for Mg (202.582 nm) have been chosen to perform the analysis. A flow injection system has been used for sample introduction so sample consumption has been reduced up to less than 1 mL per element, measured in triplicate. Furthermore, the use of multiplets for Fe and the side pixel registration approach for Mg have been studied in order to reduce sensitivity and extend the linear working range. The figures of merit have been calculated and the proposed method was applied to determine these elements in a pine needles reference material (SRM 1575a), drinking and natural waters and soil extracts. Recoveries of analytes added at different concentration levels to water samples and extracts of soils were within 88-115% interval. In this way, the fast sequential multi-element determination of major and minor elements can be carried out, in triplicate, with successful results without requiring additional dilutions of samples or several different strategies for sample preparation using about 8-9 mL of sample.

Sensitive and selective determination of phenolic compounds from aromatic plants using an electrochemical detection coupled with HPLC method.

INTRODUCTION: Phenolic compounds contained in essential oils from plants are responsible for their anti-oxidant capacity. The natural extract from each aromatic plant is characterised by a typical ratio of phenolic components, so each one of the essential oils shows different properties. OBJECTIVE: The development of a simple reversed-phase high-performance liquid chromatographic (RP-HPLC) method for the determination of phenolic compounds from aromatic plants using spectrophotometric detection with a diode-array and electrochemical detection with amperometric and coulometric detectors. METHODS: Chromatographic conditions are optimised to separate vanillin, eugenol, thymol and carvacrol using spectrophotometric detection. Acetonitrile and methanol are studied as mobile-phase organic modifiers. The hydrodynamic curves are obtained for both electrochemical detection modes and the principal values of merit are calculated. The proposed methodology is applied to determine the four analytes in real samples. RESULTS: The shortest elution times and the highest electrochemical signals are achieved using 65% methanol solution in 0.1 mol/L acetic acid-acetate buffer as the mobile phase. Potential values of 0.925 V for amperometric detection and 0.500 V for coulometric detection are chosen as working potentials. The limits of detection (LOD) for the compounds studied ranged between 9.7-17 µg/L and 0.81-3.1 µg/L in amperometric and coulometric detection modes, respectively. In general, the obtained LODs are better than those previously reported. CONCLUSION: The low LODs obtained using coulometric detection make this methodology very competitive and adequate for quality control of these phenolic compounds in comparison with others, such as GC-MS, that are more expensive and complicated to use than the RP-HPLC method with coulometric detection.

Simultaneous and direct determination of iron and nickel in biological solid samples by high-resolution continuum source graphite furnace atomic absorption spectrometry.

The simultaneous and direct determination of nickel and iron in plants and lichens has been investigated using high-resolution continuum source graphite furnace atomic absorption spectrometry. The primary resonance line for nickel at 232.003 nm and the adjacent secondary line for iron at 232.036 nm have been used for this purpose. The optimization of the experimental conditions was performed using a pine needles certified reference material (SRM 1575a). The influence of pyrolysis and atomization temperatures, the amount of solid sample introduced into the graphite furnace and the use of aqueous or solid standard for calibration were studied. The spectral interferences caused by absorption of the concomitants of the solid sample were detected and corrected using a least square algorithm. Aliquots of 0.1-1mg of the solid samples were weighed onto the solid sampling platforms and analyzed directly, without addition of any reagents. The limits of detection were 25 µg kg(-1) for nickel and 0.40 mg kg(-1) for iron and the precision, expressed as the relative standard deviation, ranged from 7% to 12%. The proposed method was used to determine both metals in different bioindicator samples with successful results.

The performance of natural clay as a barrier to the diffusion of municipal solid waste landfill leachates.

In this paper, the diffusion of solutes in natural clay from a concentrated solution consisting primarily of ammonium, sodium and chloride ions at a pH level of 8 was studied and was based on an existing 20-year-old landfill. Contaminant transport through clay liners was predicted using transport and reaction geochemical codes to help explain the experimental data. The model predicted the chloride anion diffusion and cation exchange processes for three different experiments: (1) small-scale interactions in compacted clay, (2) 1:1 European Union (EU) Directive demonstration experiments (0.5-m-thick clay barrier), and (3) analysis of a bore hole with core recovery drilled in an old landfill located above a similar type of clay as that studied in (1) and (2). Orders of magnitude between 10(-10) and 10(-9) m(2) s(-1) were used for the apparent diffusion coefficient to fit the chloride profiles at the different scales; however, at larger space and time scales, diffusion was retarded due to the presence of more consolidated, non-mechanically disturbed clay materials at large depths in a natural clay-rock emplacement.

Direct and rapid determination of ultratrace heavy metals in solid plant materials by ET-AAS ultrasonic-assisted slurry sampling.

INTRODUCTION: Plants can be used as bioindicators in the study of contamination processes by heavy metals. Most of the analytical methodologies used for determination of metals in plants are based on atomic techniques with previous wet digestion of the solid samples. Methodologies that allow direct metal measurements in solid samples are very attractive alternatives. OBJECTIVE: To develop a new procedure for direct analysis of copper, nickel, cadmium and lead at very low concentration levels in leaves based on electrothermal atomic absorption spectroscopy (ET-AAS) with introduction of samples as a slurry. METHODOLOGY: In order to obtain accurate and precise results even at very low concentrations, the different parameters that influence the sample slurry preparation such as acid percentage, presence of stabilising agents and ultrasonic probe operation were studied. Instrumental parameters such as chemical modifier and temperature and times for drying, pyrolysis and atomisation steps that influence ET-AAS measurement were optimised. RESULTS: Optimal slurry conditions for copper and nickel determination were 0.5% Tween 85 with 5% nitric acid. For lead and cadmium analysis the best results were obtained in 5% nitric acid without stabilising agents. The achieved detection limits were 0.023 mg/kg for copper, 0.018 mg/kg for nickel, 0.0002 mg/kg for cadmium and 0.009 mg/kg for lead. For validation purposes, the method was applied to metal analysis in a pine needles reference material. CONCLUSION: According to our knowledge, the detection limits obtained are the best reported in the literature. The methodology was successfully used in metal determinations in actual leaf samples.

Screen-printed sensor for batch and flow injection potentiometric chromium(VI) monitoring.

A disposable screen-printed electrode was designed and evaluated for direct detection of chromium(VI) in batch and flow analysis. The carbon screen-printed electrode was modified with a graphite-epoxy composite. The optimal graphite-epoxy matrix contains 37.5% graphite powder, 12.5% diphenylcarbohydrazide, a selective compound for chromium(VI), and 50% epoxy resin. The principal analytical parameters of the potentiometric response in batch and flow analysis were optimized and calculated. The screen-printed sensor exhibits a response time of 20 +/- 1 s. In flow analysis, the analytical frequency of sampling is 70 injections per hour using 0.1 M NaNO(3) solution at pH 3 as the carrier, a flow rate of 2.5 mL.min(-1), and an injection sample volume of 0.50 mL. The sensor shows potentiometric responses that are very selective for chromium(VI) ions and optimal detection limits in both static mode (2.1 x 10(-7) M) and online analysis (9.4 x 10(-7) M). The disposable potentiometric sensor was employed to determine toxicity levels of chromium(VI) in mineral, tap, and river waters by flow-injection potentiometry and batch potentiometry. Chromium(VI) determination was also carried out with successful results in leachates from municipal solid waste landfills.

Chromium(III) determination without sample treatment by batch and flow injection potentiometry.

A new and easy device for direct detection of chromium(III) in batch and flow analysis without previous oxidation/reduction or preconcentration steps of samples is designed and evaluated. For this purpose a potentiometric sensor with solid state membrane based on carbon paste matrix is developed. The sensor is modified with di(2-hydroxyphenylimino)ethane and the principal analytical parameters of the potentiometric response in batch and flow analysis are optimized and calculated. Optimal detection limits (1.4 x 10(-7)M in static mode and 5.4 x 10(-7)M in on-line analysis) and selectivity to trivalent chromium are obtained in both analysis modes. The use of this device to direct detection of chromium(III) in real samples is tested using a sediment Certified Reference Material. Chromium(III) determination is also carried out with successful results in environmental samples such as extracts from soils used as barriers in landfills and industrial samples such as waste waters from electroplating industries.

Flow and batch systems for copper(II) potentiometric sensing.

A new carbon paste electrode modified with tetramethyl thiuram disulfide is prepared to use as copper potentiometric sensor in batch and flow analysis. The influence of pH and carbon paste composition on the potentiometric response is studied. The principal parameters of the flow system are optimized and the detection limits and the selectivity coefficients of the potentiometric sensor are calculated for static and flow mode. In both cases, the sensor shows high selectivity to copper ions but in flow analysis this selectivity is higher. The obtained detection limits are 4.6 x 10(-8) M for batch measurements and 2.0 x 10(-7) M for on-line analysis. The potentiometric sensor is applied to copper(II) determination in real samples in static and flow measurements. In both analysis modes, successful results are obtained.

Potentiometric carbon paste sensors for lead(II) based on dithiodibenzoic and mercaptobenzoic acids.

Dithiodibenzoic (DTB) acid and mercaptobenzoic (MB) acid were studied to characterize their abilities as modifier agents for lead(II) sensors. For both sensors, the best results were obtained with modified carbon paste electrodes with 24.1% of ligand. The pH influence on the potentiometric response was studied. The selectivity coefficients for both modified electrodes were tabulated. A potentiometric sensor based on DTB acid exhibited a more sensitive and selective response to lead ions than an MB electrode. The limits of detection for the DTB and MB electrodes were very similar, 5.01 x 10(-8) M and 3.98 x 10(-8) M, respectively, for lead(II) activity. The DTB sensor was applied to lead(II) ion determination in real samples and as an indicator electrode in potentiometric titrations. Natural and commercial humic acids were titrated using the DTB electrode to estimate the stability constant between these organic compounds and the lead(II) ions with successful results.

Study of metal fractionation in river sediments. A comparison between kinetic and sequential extraction procedures.

The extraction kinetic of trace metals (Cd, Cu, Pb, and Zn) in river sediments by four extraction agents was studied. As extractants ammonium acetate, acetic acid, hydroxylamine and EDTA solutions were assayed. These reagents can leach the metals more or less selectively from several metal compartments of sediments. The metal leaching kinetic model permits classification of the metal species in labile and moderately-labile ones. The combination of two or more non specific reagents permits a high characterisation of metal distribution and leachability. The results obtained with this model in four river sediments were compared with data obtained by the SM&T sequential extraction procedure, in order to characterise the chemical nature of leached metal.

Study of fractionation and potential mobility of metal in sludge from pyrite mining and affected river sediments: changes in mobility over time and use of artificial ageing as a tool in environmental impact assessment.

Sludge from mining exploitation can be a source of land and water contamination in the adjacent zone. Accidents such as the break of waste mining pools in the Aznalcollar Mine (Seville, Spain) in 1998 produce important ecological disasters. In this work is presented a study of the evolution of aqua regia leachable concentration and mobility of metals in sediment samples of Guadiamar River basin from the accident date up to 2001. The application of BCR standard extraction procedures provides valuable information about the mobility and toxicity of the spill and the metal mobility in Guadiamar River polluted sediments. As a rule, themobility of several metals in the initial sludge (sulphides) is low, except for copper. Otherwise, the results of aqua regia leachable concentration and mobility of metal obtained for sediments samples indicate that the cleaning and inertisation works carried out in the zone have been adequate but insufficient, being the metal levels observed in the zone are higher than natural levels. To establish the initial impact of the spill and the mobility changes with time, mineralogical composition of the pyritic sludge and its evolution after the natural weathering and after the induction, of accelerated ageing processes by light and temperature was studied in the laboratory. Oxidation of initial sulphides to sulphates was observed. Both environmental and laboratory oxidation of the metallic sulphides increase the mobility of all metals, especially of copper, zinc and lead. The proposed laboratory procedure allows to predict the changes in mobility and therefore in toxicity that can occur at short or long term after exposure of sludge at environ-mental conditions. The mobility results in sludge and sediment samples are interpreted in terms of the mineral composition of the samples.