Marta Costas

Microvolume turbidimetry for rapid and sensitive determination of the acid labile sulfide fraction in waters after headspace single-drop microextraction with in situ generation of volatile hydrogen sulfide.

In this work, we demonstrate the feasibility of applying headspace single-drop microextraction with in-drop precipitation for the quantitative determination of the acid labile sulfide fraction (H2S, HS-, and S2- (free sulfide), amorphous FeS and some metal sulfide complexes-clusters as ZnS) in aqueous samples by microvolume turbidimetry. The methodology lies in the in situ hydrogen sulfide generation and subsequent sequestration into an alkaline microdrop containing ZnO(2)(2-) and exposed to the headspace above the stirred aqueous sample. The ZnS formed in the drop was then determined by microvolume turbidimetry. The optimum experimental conditions of the proposed method were: 2 microL of a microdrop containing 750 mg L(-1) Zn(II) in 1 mol L(-1) NaOH exposed to the headspace of a 20-mL aqueous sample stirred at 1600 rpm during 80 s after derivatization with 1 mL of 6 mol L(-1) HCl. An enrichment factor of 1710 was achieved in only 80 s. The calibration graph was linear in the range of 5-100 microg L(-1) with a detection limit of 0.5 microg L(-1). The repeatability, expressed as relative standard deviation, was 5.8% (N = 9). Finally, the proposed methodology was successfully applied to the determination of the acid labile sulfide fraction in different natural water samples.

Evaluation of ultrasound-assisted extraction as sample pre-treatment for quantitative determination of rare earth elements in marine biological tissues by inductively coupled plasma-mass spectrometry.

In this work, the determination of rare earth elements (REEs), i.e. Y, La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb and Lu in marine biological tissues by inductively coupled-mass spectrometry (ICP-MS) after a sample preparation method based on ultrasound-assisted extraction (UAE) is described. The suitability of the extracts for ICP-MS measurements was evaluated. For that, studies were focused on the following issues: (i) use of clean up of extracts with a C18 cartridge for non-polar solid phase extraction; (ii) use of different internal standards; (iii) signal drift caused by changes in the nebulization efficiency and salt deposition on the cones during the analysis. The signal drift produced by direct introduction of biological extracts in the instrument was evaluated using a calibration verification standard for bracketing (standard-sample bracketing, SSB) and cumulative sum (CUSUM) control charts. Parameters influencing extraction such as extractant composition, mass-to-volume ratio, particle size, sonication time and sonication amplitude were optimized. Diluted single acids (HNO(3) and HCl) and mixtures (HNO(3)+HCl) were evaluated for improving the extraction efficiency. Quantitative recoveries for REEs were achieved using 5 mL of 3% (v/v) HNO(3)+2% (v/v) HCl, particle size <200 μm, 3 min of sonication time and 50% of sonication amplitude. Precision, expressed as relative standard deviation from three independent extractions, ranged from 0.1 to 8%. In general, LODs were improved by a factor of 5 in comparison with those obtained after microwave-assisted digestion (MAD). The accuracy of the method was evaluated using the CRM BCR-668 (mussel tissue). Different seafood samples of common consumption were analyzed by ICP-MS after UAE and MAD.

Ultrasound-assisted emulsification of cosmetic samples prior to elemental analysis by different atomic spectrometric techniques.

In this work, ultrasound-assisted emulsification with a probe system is proposed as a rapid and simple sample treatment for atomic spectrometric determinations (Electrothermal Atomic Absorption Spectrometry, Inductively Coupled Plasma Optical Emission Spectrometry, Flame Atomic Absorption Spectrometry and Cold Vapour Atomic Absorption Spectrometry) of trace elements (As, Cd, Cr, Cu, Hg, Mg, Mn, Ni, Sr and Zn) in cosmetic samples such as shampoos, gel (hair gel), crèmes (body milk, hair conditioner) and oil (body oil). The type of dispersion medium, the sample mass-to-dispersion medium volume ratio, as well as the parameters related to the ultrasound-assisted emulsification (sonication amplitude and treatment time) were exhaustively studied. Only 1 min of ultrasonic shaking and a dispersion medium containing 0.5% (w/v) of SDS+3% (v/v) of HNO(3) or HCl allows obtaining a stable emulsion at least for 3 months. Thermal programs, nebulization of emulsions, speed of pumps and concentration of reagents used in cold vapour generation were optimized. Calibration using aqueous standards was feasible in all cases. Calibration by the standard addition method and recovery studies was also applied for validation. Microwave-assisted digestion and Inductively Coupled Plasma Mass Spectrometry were used for comparison purposes. Relative standard deviations from analysis of five independent emulsions were less than 9% in all cases.

Fast method for multielemental analysis of plants and discrimination according to the anatomical part by total reflection X-ray fluorescence spectrometry

Fast and reliable analytical methodologies are required for quality control of plants in order to assure human health. Ultrasound-assisted extraction in combination with total reflection X-ray fluorescence is proposed as a fast and simple method for multielemental analysis of plants on a routine basis. For this purpose, five certified reference materials have been analysed for the determination of P, K, Ca, Cr, Mn, Fe, Ni, Cu, Zn and Pb. Different extractant media (acids and oxidants) were tried. A mixture of diluted HNO(3)+HCl+HF, was selected as the best option for the achievement of complete extractions. Accurate and precise results can be reached in most cases along with a high sample throughput. Different plants (i.e., herbs, spices and medicinal plants) were analysed. Linear discriminant analysis together with the elemental concentrations allowed the differentiation of commercial preparations corresponding to flower, fruit and leaf.

Directly suspended droplet microextraction in combination with microvolume UV-vis spectrophotometry for determination of phosphate.

A miniaturized methodology for the determination of phosphate in waters has been developed by combining directly suspended droplet microextraction (DSDME) with microvolume spectrophotometry. The method is based on the extraction of the ion pair formed between 12-molybdophosphate and malachite green onto a microdrop of methyl isobutyl ketone and subsequent spectrophotometric determination with no dilution. An enrichment factor of 325 was obtained after 7.5 min of microextraction. The detection limit was 6.1 nM phosphate and the repeatability, expressed as relative standard deviation, was 2.7% (n=6). The method was successfully applied to the determination of dissolved reactive phosphorus in different freshwater samples.

Dispersive liquid-liquid microextraction combined with microvolume spectrophotometry to turn green the 5530 APHA standard method for determining phenols in water and wastewater.

In this work, a new method based on the combination of dispersive liquid-liquid microextraction (DLLME) with microvolume spectrophotometry has been developed as a greener and miniaturized alternative to the 5530 APHA standard method for determining phenols in water and wastewater. The method relies on the oxidative coupling of phenols with 4-aminoantipyrine (4-AAP). In order to preconcentrate the dye formed, the classical liquid-liquid extraction used in the 5530 APHA method (involving 500 mL of sample and 50 mL of trichloromethane) has been replaced by DLLME (with 5 mL of sample, 50 μL of trichloromethane and 200 μL of acetonitrile). After optimization, the method yielded limits of detection and quantification (0.8 and 2.5 μg L(-1), respectively) that were comparable with those obtained by the 5530 APHA standard method. Repeatability, expressed as relative standard deviation, was 5.2% (N=6), and the enrichment factor (EF) was 700. The proposed method was applied to the determination of phenols in different water samples and a wastewater with recoveries in the range 90-99%. The greenness profile was established in accordance with the suggestions made by the NEMI (National Environmental Methods Index). The absence of PBT (persistent bioaccumulative and toxic chemicals) and corrosive reagents and a drastic reduction of generated wastes can be emphasized.

Land–ocean contributions of arsenic through a river–estuary–ria system (SW Europe) under the influence of arsenopyrite deposits in the fluvial basin

Water was sampled monthly from September 2005 to August 2006 at 14 stations distributed throughout the coastal system of Anllóns-Laxe, from where 30 surface sediment samples were also taken. After filtration through 0.22 μm polycarbonate filters, dissolved inorganic and total arsenic (UV oxidation) concentration was determined by HG-AFS. After microwave digestion, the arsenic in SPM and sediment was determined by AAS. Ultra-clean procedures were adopted during sampling, handling and analysis and the analytical accuracy was checked using certified reference material. Spatial distribution of As in water (0.2-4.0 μg L(-1)), SPM (21-169 mg kg(-1)) and sediment of the river reservoir was altered by the presence of arsenopyrite deposits in the middle fluvial basin that increases 2.1±0.5 and 1.7±0.5 times the concentrations of inorganic dissolved (DI-As) and particulate (P-As) arsenic, respectively. At the termination fluvial zone As fluxes can be calculated to be: [DI-As]=7.09·Q(-0.69). The Anllóns River exports to its estuary 460 kg a(-1) of dissolved (<7% as organic) arsenic annually. It is higher (i.e. 0.83 kgs(-1) km(-2) of DI-As) than that of most of European rivers. In the estuary reservoir, the influence of arsenopyrite is also evident as the river concentration of DI-As, which was lower than in seawater during the wet season and higher during the dry season. Arsenic has non-conservative behaviour, as in other European estuaries, but the Anllóns shows an ambivalent pattern: as it usually gains DI-As during the wet season and loses it during the dry season, whilst P-As seems to behave contrary to the DI-As. When the fluvial arsenic reaches the ria its concentration varies due to the estuarine processes. In the wet season DI-As increases its concentration by one third whilst in the dry season it decreases by one fifth and the annual contribution to the ria is 10% higher than the fluvial output. In the case of P-As more data are necessary to quantify its behaviour; however, the estuarine sediments are contaminated by arsenic. In the ria reservoir DI-As levels were similar to those of the ocean, DO-As comprises 9-22% of the inorganic, P-As ranges from 3 to 40 mg kg(-1), and As-sedimentary can be classified as uncontaminated (4-18 mg kg(-1)), except in the fishing ports. The ria circulation, reinforced by upwelling favours the exportation of arsenic to the ocean. In the Anllóns-Laxe system as a whole, the freshwater-saline interface processes do not lead to a decrease in the dissolved fluvial arsenic flux to the ocean.

Elemental fingerprinting of tumorous and adjacent non-tumorous tissues from patients with colorectal cancer using ICP-MS, ICP-OES and chemometric analysis

Tumorous and adjacent non-tumorous paired biopsies from 38 patients with colorectal cancer were analyzed by inductively coupled plasma mass spectrometry and inductively coupled plasma optical emission spectrometry after low-volume microwave digestion. 18 elements were investigated: Ag, Al, Ca, Cd, Co, Cr, Cu, Fe, K, Mg, Mn, Mo, Ni, P, Pb, S, Se and Zn. Different chemometric tools were used for data evaluation: Wilcoxon signed rank test, Hieratical clustering analysis, principal component analysis (PCA) and linear discriminant analysis (LDA). With the exception of Al, tumours were observed to have significantly more elevated concentrations of essential elements as compared to non-tumours. On the contrary, elements considered potentially carcinogenic such as Cr, Ni, Mo or Co do not display significant differences. When PCA was applied, different components were obtained for tumorous and non-tumorous tissues. When LDA was applied for the elements studied (including essential and non-essential elements) about 90% of cases were correctly classified.

On-line UV photoreduction in a flow-injection/stopped-flow manifold for determination of mercury by cold vapour-atomic absorption spectrometry.

Photo-chemical vapour generation has been applied in a flow-injection system under stopped-flow conditions for determination of Hg by atomic absorption spectrometry. The system allows mercury vapour generation without the need for conventional reduction reactions based on sodium/potassium tetrahydroborate (III) or tin chloride in acid medium. The photo-induced reaction is accomplished by applying ultraviolet irradiation (UV) to the sample solution containing Hg(II) in the presence of an organic acid (i.e., acetic, citric, oxalic, ethylendiaminetetraacetic) as precursor of reducing species. A remarkable improvement in sensitivity is observed with acetic acid when stopped-flow is employed as compared to continuous operation, meaning that kinetics play an important role in the photo-induced reaction. A detection limit of 0.3 μg L−1 can be obtained, which represents a 6-fold improvement in respect to that obtained without stopped-flow. The repeatability expressed as relative standard deviation was about 2.7% (n = 15) for a 50 μg L−1 Hg standard. The effect of potential interferences on the photo-generation of Hg vapour was investigated. In the UV-photo-induced CVG, both inorganic Hg and organomercury species can be reduced to elemental mercury with the same efficiency. The method was applied to determination of Hg in several enriched natural water samples and recoveries of MeHg+, Thiomersal, EtHg+ and PhHg+ were in the range 97% to 102%.

Simultaneous ultrasound-assisted emulsification–derivatization as a simple and miniaturized sample preparation method for determination of nitrite in cosmetic samples by microvolume UV–vis spectrophotomety

A simple and miniaturized approach based on ultrasound-assisted emulsification-derivatization is proposed for the determination of nitrite in cosmetic samples by UV-vis micro-spectrophotometry. Oil/water emulsions were formed using 15 mg of cosmetic sample and 1 mL of an aqueous medium containing 0.5% w/v SDS and 1% v/v acetic acid. When powerful sonication systems were used to make emulsions, i.e. probe or cup-horn sonoreactor, stable and transparent emulsions were obtained in one or half minute per sample, respectively. The Griess reaction in these special conditions (i.e. sonication and the presence of an organized medium) was investigated. The absence of matrix effects allows external calibration with aqueous standards for nitrite quantification. Analytical features were compared to those of the European official method 82/434/EEC. Detection limit, sample throughput and reagent consumption were significantly improved.