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We describe the modification of the porphyrin method for low-level determination of the speciation of dissolved Mn in seawater. First, an investigation of sensitivity of the method versus the salinity, the reagent composition and the type of ligands present is described for a few micromolar of dissolved Mn. Then, using certified seawater reference standards, we demonstrate the accuracy of the method for total concentrations of manganese between 1 and 10 nM. To this aim, we report the reactivity of solutions made of Mn(II) and Mn(III) bound to Tiron and DFOB with our optimized porphyrin reagent which includes adding excess Cd2+, and compare these results with data from representative natural seawater samples. This work describes an improved method that gives the opportunity for future work to investigate Mn speciation at nanomolar concentration in the open ocean.

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A simple, rapid, and efficient ultrasound-assisted dispersive liquid-liquid microextraction (US-DLLME) method was developed for extraction of tetracycline residues from egg supplement samples, with subsequent determination by flow injection analysis (FIA) coupled to a liquid waveguide capillary cell (LWCC) and a controlled temperature heating bath. Tetracyclines react with diazotized p-sulfanilic acid, in a slightly alkaline medium, to form azo compounds that can be measured at 435 nm. The reaction sensitivity improved substantially (5.12-fold) using an in-line heating temperature of 45 °C. Multivariate methodology was used to optimize the factors affecting the extraction efficiency, considering the volumes of extraction and disperser solvents, sonication time, extraction time, and centrifugation time. Good linearity in the range 30-600 µg L(-1) was obtained for all the tetracyclines, with regression coefficients (r) higher than 0.9974. The limits of detection ranged from 6.4 to 11.1 µg L(-1), and the recoveries were in the range 85.7-96.4 %, with relative standard deviation lower than 9.8 %. Analyte recovery was improved by approximately 6 % when the microextraction was assisted by ultrasound. The results obtained with the proposed US-DLLME-FIA method were confirmed by a reference HPLC method and showed that the egg supplement samples analyzed were suitable for human consumption.

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A rapid and simple screening method was developed for the determination of sulfonamides in honey samples by flow injection analysis (FIA) coupled to a liquid waveguide capillary cell. The proposed method is based on the reaction between sulfonamides and p-dimethylaminocinnamaldehyde (p-DAC) in the presence of sodium dodecylsulate (SDS) in dilute acid medium (hydrochloric acid), with the reaction product being measured spectrophotometrically at λ(max) = 565 nm. Experimental design methodology was used to optimize the analytical conditions. The proposed technique was applied to the determination of sulfonamides (sulfaquinoxaline, sulfadimethoxine, and sulfathiazole) in honey samples, in a concentration range from 6.00 × 10(-3) to 1.15 × 10(-1)mg L(-1). The detection (LOD) and quantification (LOQ) limits were 1.66 × 10(-3) and 5.54 × 10(-3)mg L(-1), respectively. Positive and false positive samples were also analyzed by a confirmatory HPLC method. The proposed system enables the screening of sulfonamides in honey samples with a low number of false positive results, with fast response therefore offers a new tool for consumer protection.

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Macronutrient elements (C, N and P) and micronutrient elements (Fe, Co, Cu, Zn and Mn) are widely measured in their various physico-chemical forms in open ocean, shelf sea, coastal and estuarine waters. These measurements help to elucidate the biogeochemical cycling of these elements in marine waters and highlight the ecological and socio-economic importance of the oceans. Due to the dynamic nature of marine waters in terms of chemical, biological and physical processes, it is advantageous to make these measurements in situ and in this regard flow injection analysis (FIA) provides a suitable shipboard platform. This review, therefore, discusses the role of FIA in the determination of macro- and micro-nutrient elements, with an emphasis on manifold design and detection strategies for the reliable shipboard determination of specific nutrient species. The application of various FIA manifolds to oceanographic nutrient determinations is discussed, with an emphasis on sensitivity, selectivity, high throughput analysis and suitability for underway analysis and depth profiles. Strategies for enhancing sensitivity and minimizing matrix effects, e.g. refractive index (schlieren) effects and the important role of uncertainty budgets in underpinning method validation and data quality are discussed in some detail.

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A multisyringe flow injection analysis system using a liquid waveguide capillary cell (MSFIA-LWCC) has been used for the spectrophotometric determination of titanium (Ti) in marine environmental samples. Samples were previous digested using potassium peroxodisulfate (K2S2O8). The method showed to be linear over a range up to 1 µM with a detection limit of 9.2 nM. The analysis consumes little reagent (250 µL) and sample (600 µL). It had an adequate accuracy with high repeatability (RSD of 1.8%) for all marine samples. The proposed method was used to evaluate the concentration of Ti in natural samples collected in the coastal area of the Majorca Island (Western Mediterranean Sea). We report average concentrations of Ti in coastal surface microlayer of 510.7 ± 267.2 nM, in surface sediments of 2.72 ± 1.84 µmol/g, and in rhizomes and leaves of Posidonia oceanica of 310 ± 295 nmol/g and 157 ± 132 nmol/g, respectively.

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