Water from La Pampa, Argentina, was used for washing and cooking rice to examine the in-situ impact of using naturally-contaminated water for food preparation on the elemental dietary intake. Whilst washing with the control tap water (28 μg/L As) reduced the concentration of As in rice by 23%, the use of different well waters (281–1144 μg/L) increased As levels significantly (48–227%) in comparison with the original concentration in the rice (0.056 µg/g). Cooking the rice at a low water-to-rice ratio (2:1) using modern methods increased the levels of As in the cooked samples by 2–3 orders of magnitude for both pre-washed and un-washed rice. Similar trends were observed for vanadium. Although the levels of manganese, iron, copper, zinc and molybdenum in rice were reduced during washing and cooking for most water samples, the molybdenum concentration in the cooked rice doubled (2.2–2.9 µg/g) when using water containing >1 mg/L Mo.

A green and innovative eutectic solvent based extraction method was proposed for the determination of trace level vanadium in water and food samples by graphite furnace atomic absorption spectrometry. In this extraction technique magnetic stirrer was used for preparation of eutectic solvent by mixing of zinc chloride and acetamide at different molar ratios. Extraction capability of eutectic solvent was increased by adding a non ionic surfactant (Triton X-114) to enhanced phase transfer ratio, to significantly increase the recovery of hydrophobic complex of vanadium with ammonium pyrrolidine dithiocarbamate. A multivariate technique was applied to evaluate the important extraction parameters, which plays important role for optimum recovery of the targeted analyte by proposed extraction method. Multivariate techniques such as (factorial design and central composite design) were applied to screening out the most significant extraction parameters and optimized them. Under optimized extraction conditions, limit of detection and enhancement factor were found to be 0.01 µg L⁻¹ and 64.6, respectively. The relative standard deviation for the determination of trace level vanadium at 0.32 µg L⁻¹ concentration, was achieved to be <3.0% (n = 10). Validity and accuracy of the proposed extraction method was checked by analysis of certified reference materials of Canadian lake water and tomato leaves with % age recovery >98%. The eutectic solvent extraction method was successfully applied for the determination of the trace level vanadium in real water samples of different sources and acid digested food samples, collected from different locations of Tokat city, Turkey.

A new dispersive liquid–liquid microextraction, magnetic stirrer induced dispersive ionic-liquid microextraction (MS-IL-DLLME) was developed to quantify the trace level of vanadium in real water and food samples by graphite furnace atomic absorption spectrometry (GFAAS). In this extraction method magnetic stirrer was applied to obtained a dispersive medium of 1-butyl-3-methylimidazolium hexafluorophosphate [C4MIM][PF6] in aqueous solution of (real water samples and digested food samples) to increase phase transfer ratio, which significantly enhance the recovery of vanadium – 4-(2-pyridylazo) resorcinol (PAR) chelate. Variables having vital role on desired microextraction methods were optimised to obtain the maximum recovery of study analyte. Under the optimised experimental variables, enhancement factor (EF) and limit of detection (LOD) were achieved to be 125 and 18ngL−1, respectively. Validity and accuracy of the desired method was checked by analysis of certified reference materials (SLRS-4 Riverine water and NIST SRM 1515 Apple leaves). The relative standard deviation (RSD) for 10 replicate determinations at 0.5μgL−1 of vanadium level was found to be <5.0%. This method was successfully applied to real water and acid digested food samples.

A preconcentration procedure based on cloud point extraction and back-extraction (CPE-BE) was proposed for speciation of inorganic vanadium (V⁴⁺ and V⁵⁺) followed by determination by inductively coupled plasma-optical emission spectrometry (ICP-OES). Two consecutive steps are used in this technique. The traditional CPE technique was applied as a first step, V⁵⁺ reacts with bis(3,4-dihydroxybenzylidene)isophthalohydrazide (DHBIP) forming a hydrophobic complex at pH 7.0. The formed complex is then entrapped in a surfactant-rich phase of Triton X-114, while V⁴⁺ kept in the aqueous phase. Following this stage, a back-extraction step was performed to minimize the deteriorating effect of the organic matrix on the plasma performance. For this purpose, the surfactant-rich phase containing the analyte was incubated at 45 °C with 1.0 mL of 1.0 mol L⁻¹ of HNO₃ solution for 15 min. Finally, the analyte in the aqueous phase was determined by ICP-OES. The total vanadium was determined as V⁵⁺ after oxidation of V⁴⁺ by using hydrogen peroxide. The calibration graph is linear from 0.4–750.0 μg L⁻¹ for V⁵⁺ at the optimum conditions (pH 7.0, 10⁻⁴ mol L⁻¹ DHBIP, 0.1 % (v/v) Triton X-114 and 45 °C). The detection and quantification limits of V⁵⁺ were 0.12 μg L⁻¹and 0.40 μg L⁻¹, respectively, with an enrichment factor of 49.5, and the relative standard deviation was less than 2.5 % (n = 7, c = 10 μg L⁻¹). The method has been used for speciation of inorganic V in water samples and determination of total V in cabbage, carrots, mint, and tomato samples with satisfactory results.

A new and practical sample enrichment method termed ionic liquid-based ultrasound-assisted in situ solvent formation microextraction (IL-UA-ISFME) was combined with electrothermal atomic absorption spectrometry (ETAAS) for preconcentration and trace determination of vanadium in real samples. In this sample enrichment methodology, a hydrophilic ionic liquid (IL) ([Hmim][BF₄]) was added to the aqueous media containing an ion-exchange reagent (NaPF₆), in order to obtain a hydrophobic IL ([Hmim][PF₆]) as the microextraction solvent. The hydrophobic extraction solvent formed under these conditions was completely dispersed into the sample solution using ultrasonic radiation. Vanadium was complexed with N-benzoyl-N-phenylhydroxylamine (BPHA), and extracted into the IL phase during the dispersion of the hydrophobic IL. Main variables affecting the recommended method was studied in details and optimized. Under the optimum conditions, the combined methodology provided a linear dynamic range of 15–2,500 ng l⁻¹, a limit of detection (LOD) of 4.7 ng l⁻¹ and a relative standard deviation (RSD) of 4.0 %. The accuracy and validity of the method was checked by analyzing a certified standard reference material of water (SRM-1643e). Finally, the developed method was utilized for quantitation of vanadium in real water and milk samples.