Trace determination of lead, chromium and cadmium in herbal medicines using ultrasound-assisted emulsification microextraction combined with graphite furnace atomic absorption spectrometry.

INTRODUCTION: The World Health Organization (WHO) recommends that medicinal plants should be checked for the presence of heavy metals. A preconcentration and separation technique for trace amounts of heavy metals from plant matrix is necessary in order to increase the sensitivity and precision of their determination. OBJECTIVE: Lead, chromium and cadmium contaminations in herbal medicines were monitored using ultrasound-assisted emulsification microextraction (USAEME) combined with graphite furnace atomic absorption spectrometry (GF-AAS). METHODS: In this work, the metal ions in the aqueous solution were complexed with ammonium pyrrolidine dithiocarbamate (APDC) and were extracted into 45 µL of toluene that was sonically dispersed in the aqueous phase. The emulsion formed was centrifuged and 20 µL of separated toluene was injected into a GF-AAS for analysis. Several factors including the kind of extraction solvent and its volume, sample pH, ionic strength and concentration of APDC were optimised. RESULTS: The linear dynamic range (LDR) values were in the range of 0.05 to 20 µg/L and the limit of detection values were in the range of 0.002-0.03 µg/L for target heavy metals. Enrichment factors were obtained in the range of 70-500. The precision of the proposed method was ≤ 8% (n = 5). The obtained amounts of Pb, Cr and Cd in selected herbal medicines were in the standard range, according to the WHO reports. CONCLUSION: The USAEME with GF-AAS procedure was shown to be an efficient, rapid, inexpensive and eco-friendly method for the determination of lead, chromium and cadmium in herbal medicines. Application of the USAEME method leads to an increased extraction efficiency with satisfactory precision in a short time using an extraction solvent volume at the microlitre level.

Hollow fiber liquid phase microextraction followed by high performance liquid chromatography for determination of ultra-trace levels of Se(IV) after derivatization in urine, plasma and natural water samples.

In the present work, a simple and high sensitive method based on hollow fiber liquid phase microextraction (HF-LPME) was developed followed by high performance liquid chromatography (HPLC) for determination of ultra-trace amounts of Se(IV) after derivatization in biological and natural water samples. Se(IV) was complexed with o-phenylenediamine to form piazselenol. The formed piazselenol was extracted into 20 microL of 1-octanol located in the lumen of a hollow fiber and the solution was injected into HPLC-UV for analysis. Using the Taguchi method, an orthogonal array design (OAD), OA(16) (4(5)) was employed to optimize the HF-LPME of piazselenol. The effect of five experimental factors (each factor at four levels) including the volume of the organic phase, extraction time, pH of the solution, stirring rate and ionic strength on the extraction efficiency of piazselenol was studied and optimized. The maximum extraction efficiency of piazselenol was obtained at 20 microL of 1-octanol as the extracting solvent, 30 min extraction time, pH 2, stirring rate of 500 rpm and 30% (w/v) NaCl. Under the optimum conditions, preconcentration factors up to 130 were achieved and the relative standard deviation (%RSD) of the method was <3.7% for different concentrations of Se(IV). The calibration curves were obtained in the ranges of 0.2-100 and 0.05-10 microgL(-1) for the 11 and 50 mL of the sample volumes with reasonable linearity, respectively (r(2)> 0.995). The limits of detection (LOD) were 0.1 and 0.02 microgL(-1) for the 11 and 50 mL sample volumes, respectively (S/N - 3). Finally, the applicability of the proposed method was evaluated by the extraction and determination of Se(IV) in the plasma, urine and water samples.

Taguchi OA16 orthogonal array design for the optimization of cloud point extraction for selenium determination in environmental and biological samples by tungsten-modified tube electrothermal atomic absorption spectrometry.

Orthogonal array design (OAD) was applied for the first time to optimize cloud point extraction (CPE) conditions for Se(IV) determination by electrothermal atomic absorption spectrometry (ETAAS) in environmental and biological samples. Selenium was reacted with o-phenylenediamine to form piazselenol in an acidic medium (pH 2). Using Triton X-114, as surfactant, piazselenol was quantitatively extracted into small volume (about 30 microL) of the surfactant-rich phase after centrifugation. Five relevant factors, i.e. surfactant concentration, pH, ionic strength, equilibrium time and temperature were selected and the effects of each factor were studied at four levels on the extraction efficiency of Se(IV) and optimized. The statistical analysis revealed that the most important factors contributing to the extraction efficiency are ionic strength, pH and percent of surfactant. Based on the results obtained from the analysis of variance (ANOVA), the optimum conditions for extraction were established as: pH 6; vial temperature=50 degrees C; extraction time=7 min and 0.3% (w/v) of Triton X-114. The method was permitted to obtain a detection limit of 0.09 ng mL(-1) and two linear calibration ranges from 0.6 to 1.0 and 1.0 to 80.0 ng mL(-1) Se. The precision (%RSD) of the extraction and determination for the six replicates of Se at 20 ng mL(-1) was better than 3.6% and the enrichment factor of 63.5 was achieved. The studied analyte was successfully extracted and determined with high efficiency using cloud point extraction method in water and biological matrices.