Multi-commutated flow system for inorganic selenium speciation in infusion tea samples by chemical vapor generation atomic fluorescence spectrometry.

This work proposes an automated strategy for the inorganic selenium speciation in infusion tea samples, employing an MSFIA-CVG-AFS system and sodium tetrahydroborate for chemical vapor generation. The selenium total is determined after an online prereduction step of selenium (VI) to selenium (IV) in alkaline media, using a UV reactor with a 15 W Hg lamp. Selenium (IV) is quantified directly on the sample, and selenium (VI) is determined by the difference between the total selenium and selenium (IV) concentrations. The optimization of the chemical parameters: hydrochloric acid - hydrobromide acid solution concentration, potassium iodide concentration, sodium hydroxide concentration, and sodium tetrahydroborate concentration was performed using a (24-1) two-level fractional factorial design. The validation parameters were determined for total selenium and selenium (IV), and the results found were: limits of detection and quantification of 0.05 and 0.18 µg L-1, respectively; a linear range of 0.18-5.0 µg L-1, precision expressed as the relative standard deviation of 2.1% for a sample number of 10, for both analytes. The system allows the speciation analysis with an injection throughput of 15 injections per hour. This analytical method was applied for inorganic selenium speciation in nine infusions of tea samples purchased commercially in supermarkets in Palma de Mallorca City, Spain. The concentrations of selenium (IV) and total selenium varied from 0.2 to 0.6 µg L-1 and 0.4-2.0 µg L-1, respectively. The accuracy method was evaluated using spike tests, and the recoveries achieved varied from 91 to 111%.

Fully-automated in-syringe dispersive liquid-liquid microextraction for the determination of caffeine in coffee beverages.

A novel fully-automated magnetic stirring-assisted lab-in-syringe analytical procedure has been developed for the fast and efficient dispersive liquid-liquid microextraction (DLLME) of caffeine in coffee beverages. The procedure is based on the microextraction of caffeine with a minute amount of dichloromethane, isolating caffeine from the sample matrix with no further sample pretreatment. Selection of the relevant extraction parameters such as the dispersive solvent, proportion of aqueous/organic phase, pH and flow rates have been carefully evaluated. Caffeine quantification was linear from 2 to 75mgL(-1), with detection and quantification limits of 0.46mgL(-1) and 1.54mgL(-1), respectively. A coefficient of variation (n=8; 5mgL(-1)) of a 2.1% and a sampling rate of 16h(-1), were obtained. The procedure was satisfactorily applied to the determination of caffeine in brewed, instant and decaf coffee samples, being the results for the sample analysis validated using high-performance liquid chromatography.

In-syringe extraction using dissolvable layered double hydroxide-polymer sponges templated from hierarchically porous coordination polymers.

Herein we report the use of cobalt porous coordination polymers (PCP) as intermediates to prepare advanced extraction media based on layered double hydroxides (LDH) supported on melamine polymer foam. The obtained dissolvable Ni-Co LDH composite sponges can be molded and used as sorbent for the in-syringe solid-phase extraction (SPE) of phenolic acids from fruit juices. The proposed sorbent is obtained due to the surfactant-assisted self-assembly of Co(II)/imidazolate PCPs on commercially available melamine foam, followed by the in situ conversion of the PCP into the final dissolvable LDH coating. Advantageous features for SPE are obtained by using PCPs with hierarchical porosity (HPCPs). The LDH-sponge prepared using intermediate HPCPs (HLDH-sponge) is placed in the headspace of a glass syringe, enabling flow-through extraction followed by analyte elution by the dissolution of the LDH coating in acidic conditions. Three phenolic acids (gallic acid, p-hydroxybenzoic acid and caffeic acid) were extracted and quantified using high performance liquid chromatography. Using a 5mL sample volume, the obtained detection limits were 0.15-0.35µgL(-1). The proposed method for the preparation of HLDH-sponges showed a good reproducibility as observed from the intra- and inter-day RSD's, which were <10% for all analytes. The batch-to-batch reproducibility for three different batches of HLDH-sponges was 10.6-11.2%. Enrichment factors of 15-21 were obtained. The HLDH-sponges were applied satisfactorily to the determination of phenolic acids in natural and commercial fruit juices, obtaining relative recoveries among 89.7-95.3%.

Submicrometric Magnetic Nanoporous Carbons Derived from Metal-Organic Frameworks Enabling Automated Electromagnet-Assisted Online Solid-Phase Extraction.

We present the first application of submicrometric magnetic nanoporous carbons (µMNPCs) as sorbents for automated solid-phase extraction (SPE). Small zeolitic imidazolate framework-67 crystals are obtained at room temperature and directly carbonized under an inert atmosphere to obtain submicrometric nanoporous carbons containing magnetic cobalt nanoparticles. The µMNPCs have a high contact area, high stability, and their preparation is simple and cost-effective. The prepared µMNPCs are exploited as sorbents in a microcolumn format in a sequential injection analysis (SIA) system with online spectrophotometric detection, which includes a specially designed three-dimensional (3D)-printed holder containing an automatically actuated electromagnet. The combined action of permanent magnets and an automatically actuated electromagnet enabled the movement of the solid bed of particles inside the microcolumn, preventing their aggregation, increasing the versatility of the system, and increasing the preconcentration efficiency. The method was optimized using a full factorial design and Doehlert Matrix. The developed system was applied to the determination of anionic surfactants, exploiting the retention of the ion-pairs formed with Methylene Blue on the µMNPC. Using sodium dodecyl sulfate as a model analyte, quantification was linear from 50 to 1000 µg L(-1), and the detection limit was equal to 17.5 µg L(-1), the coefficient of variation (n = 8; 100 µg L(-1)) was 2.7%, and the analysis throughput was 13 h(-1). The developed approach was applied to the determination of anionic surfactants in water samples (natural water, groundwater, and wastewater), yielding recoveries of 93% to 110% (95% confidence level).

A critical comparison of constant and pulsed flow systems exploiting gas diffusion.

Considering the beneficial aspects arising from the implementation of pulsed flows in flow analysis, and the relevance of in-line gas diffusion as an analyte separation/concentration step, influence of flow pattern in flow systems with in-line gas diffusion was critically investigated. To this end, constant or pulsed flows delivered by syringe or solenoid pumps were exploited. For each flow pattern, two variants involving different interaction times of the donor with the acceptor streams were studied. In the first one, both the acceptor and donor streams were continuously flowing, whereas in the second one, the acceptor was stopped during the gas diffusion step. Four different volatile species (ammonia, ethanol, carbon dioxide and hydrogen sulfide) were selected as models. For the flow patterns and variants studied, the efficiencies of mass transport in the gas diffusion process were compared, and sensitivity, repeatability, sampling frequency and recorded peak shape were evaluated. Analysis of the results revealed that sensitivity is strongly dependent on the implemented variant, and that flow pattern is an important feature in flow systems with in-line gas diffusion.

On-line lab-in-syringe cloud point extraction for the spectrophotometric determination of antimony.

Most of the procedures for antimony determination require time-consuming sample preparation (e.g. liquid-liquid extraction with organic solvents), which are harmful to the environment. Because of the high antimony toxicity, a rapid, sensitive and greener procedure for its determination becomes necessary. The goal of this work was to develop an analytical procedure exploiting for the first time the cloud point extraction on a lab-in-syringe flow system aiming at the spectrophotometric determination of antimony. The procedure was based on formation of an ion-pair between the antimony-iodide complex and H(+) followed by extraction with Triton X-114. The factorial design showed that the concentrations of ascorbic acid, H2SO4 and Triton X-114, as well as second and third order interactions were significant at the 95% confidence level. A Box-Behnken design was applied to obtain the response surfaces and to identify the critical values. System is robust at the 95% confidence level. A linear response was observed from 5 to 50 µg L(-1), described by the equation A=0.137+0.050C(Sb) (r=0.998). The detection limit (99.7% confidence level), the coefficient of variation (n=5; 15 µg L(-1)) and the sampling rate was estimated at 1.8 µg L(-1), 1.6% and 16 h(-1), respectively. The procedure allows quantification of antimony in the concentrations established by environmental legislation (6 µg L(-1)) and it was successfully applied to the determination of antimony in freshwater samples and antileishmanial drugs, yielding results in agreement with those obtained by HGFAAS at the 95% confidence level.

A portable multi-syringe flow system for spectrofluorimetric determination of iodide in seawater.

A miniaturized analyzer encompassing a poly(methyl methacrylate) chip with integrated spectrofluorimetric detection and solutions propelling by a multi-syringe module is proposed. Iodide was determined through its catalytic effect on the reaction between Ce(IV) and As(III). Matrix isopotential synchronous fluorescence was explored to set the excitation and emission wavelengths. A two-level full factorial design allowed to evaluate the significance of variables (Ce(IV), As(III) and H2SO4 concentrations) and their interaction effects in the experimental domain. A Doehlert Matrix was applied to identify the critical values. The optimized procedure showed a linear response from 1 to 100 µg L(-1) (S=53.7+2.61C, in which S is the net fluorescence and C is iodide concentration in µg L(-1)). Detection limit, coefficient of variation (n=6) and sampling rate were estimated at 0.3 µg L(-1), 0.8% and 20 h(-1), respectively. Recoveries within 90-117% were estimated for iodide spiked to seawater samples. The proposed procedure stands out because of the portability, robustness, and simplicity for in-field analysis of iodide in seawater.

An improved approach for flow-based cloud point extraction.

Novel strategies are proposed to circumvent the main drawbacks of flow-based cloud point extraction (CPE). The surfactant-rich phase (SRP) was directly retained into the optical path of the spectrophotometric cell, thus avoiding its dilution previously to the measurement and yielding higher sensitivity. Solenoid micro-pumps were exploited to improve mixing by the pulsed flow and also to modulate the flow-rate for retention and removal of the SRP, thus avoiding the elution step, often carried out with organic solvents. The heat released and the increase of the salt concentration provided by an on-line neutralization reaction were exploited to induce the cloud point without an external heating device. These innovations were demonstrated by the spectrophotometric determination of iron, yielding a linear response from 10 to 200 µg L(-1) with a coefficient of variation of 2.3% (n=7). Detection limit and sampling rate were estimated at 5 µg L(-1) (95% confidence level) and 26 samples per hour, respectively. The enrichment factor was 8.9 and the procedure consumed only 6 µg of TAN and 390 µg of Triton X-114 per determination. At the 95% confidence level, the results obtained for freshwater samples agreed with the reference procedure and those obtained for digests of bovine muscle, rice flour, brown bread and tort lobster agreed with the certified reference values. The proposed procedure thus shows advantages in relation to previously proposed approaches for flow-based CPE, being a fast and environmental friendly alternative for on-line separation and pre-concentration.

A multi-pumping flow-based procedure with improved sensitivity for the spectrophotometric determination of acid-dissociable cyanide in natural waters.

An analytical procedure with improved sensitivity was developed for cyanide determination in natural waters, exploiting the reaction with the complex of Cu(I) with 2,2'-biquinoline 4,4'-dicarboxylic acid (BCA). The flow system was based on the multi-pumping approach and long pathlength spectrophotometry with a flow cell based on a Teflon AF 2400(®) liquid core waveguide was exploited to increase sensitivity. A linear response was achieved from 5 to 200µg L(-1), with coefficient of variation of 1.5% (n=10). The detection limit and the sampling rate were 2µg L(-1) (99.7% confidence level), and 22h(-1), respectively. Per determination, 48ng of Cu(II), 5µg of ascorbic acid and 0.9µg of BCA were consumed. As high as 100mg L(-1) thiocyanate, nitrite or sulfite did not affect cyanide determination. Sulfide did not interfere at concentrations lower than 40 and 200µg L(-1) before or after sample pretreatment with hydrogen peroxide. The results for natural waters samples agreed with those obtained by a fluorimetric flow-based procedure at the 95% confidence level. The proposed procedure is then a reliable, fast and environmentally friendly alternative for cyanide determination in natural waters.

An automatic flow injection analysis procedure for photometric determination of ethanol in red wine without using a chromogenic reagent.

An automatic reagentless photometric procedure for the determination of ethanol in red wine is described. The procedure was based on a falling drop system that was implemented by employing a flow injection analysis manifold. The detection system comprised an infrared LED and a phototransistor. The experimental arrangement was designed to ensure that the wine drop grew between these devices, thus causing a decrease in the intensity of the radiation beam coming from the LED. Since ethanol content affected the size of the wine drop this feature was exploited to develop an analytical procedure for the photometric determination of ethanol in red wine without using a chromogenic reagent. In an attempt to prove the usefulness of the proposed procedure, a set of red wines were analysed. No significant difference between our results and those obtained with a reference method was observed at the 95% confidence level. Other advantages of our method were a linear response ranging from 0.17 up to 5.14 mol L(-1) (1.0 up to 30.0%) ethanol (R = 0.999); a limit of detection of 0.05 mol L(-1) (0.3%) ethanol; a relative standard deviation of 2.5% (n = 10) using typical wine sample containing 2.14 mol L(-1) (12.5%) ethanol; and a sampling rate of 50 determinations per hour.