The objective of the present study was to develop sequential extraction procedures for the major carotenoids -beta-carotene and lycopene from agro-industrial waste materials -tomato skin, tangerine and orange peels using the ultrasound-assisted extraction and the supercritical fluid extraction techniques. A rapid, effective and selective high performance liquid chromatographic method for quantitative determination of beta-carotene and lycopene in organic extracts solutions was developed and validated with respect to robustness, specificity, linearity-range, accuracy, precision, limit of detection (LOD) and quantitation (LOQ) as well. The effect of the operating pressure, the temperature, the extraction time, the flow rate of supercritical fluid, the sample size, the ultrasound power and the solvent nature used was investigated. The optimal conditions for extraction were found. The LOD and the LOQ are 0.0081µg/mL and 0.00405 µg/mL for beta-carotene, 0.034 µg/mL and 0.0085 µg/mL for lycopene, respectively. No interference was observed. The content of betacarotene per 1 g of dried agro-industrial waste material varies 8.39 -12.75 µg (tomato skin), 25.65 -32.18 µg (tangerine peel), 41.66 -59.16 µg (orange peel) and the content of lycopene -165.11 -179.56 µg (tomato skin), 11.12 -17.91 µg (tangerine peel), 8.37 -10.65 µg (orange peel).
Residual antibiotics pollution has become one of the most severe environmental problems today. Antibiotics from hospitals and drug factories represent a potential risk for human and ecological health. Therefore, it has been a high exigency to develop some efficient and cost-effective treatment methods and technologies for antibiotics removal from industrial and household contaminated water. Adsorption is one of the most utilised techniques and has many competitive advantages such as the unique properties of flexibility, effectiveness, superior performance and the robustness for consecutive cycles. The present research concerns the adsorption of two frequently used fluoroquinolone antibiotics - moxifloxacin and norfloxacin on natural zeolite - clinoptilolite and its acid-modified form from aqueous solutions. For the first time, the adsorption of the antibiotics mentioned above on the selected natural zeolite was investigated under static and dynamic conditions. Adsorption experiment under dynamic conditions carried out using the specially constructed dynamic type of laboratory equipment. The effect of the inlet concentration, the flow rate and the pH value of the antibiotic solution, also, the contact time of system zeolite/antibiotic solution on the adsorption process were examined and evaluated using the Langmuir and Freundlich adsorption models. The results showed that the highest static adsorption capacities were observed at low initial concentration - 0.2 mg/mL of antibiotic solution for both adsorbents; the highest dynamic adsorption capacities - at low flow rate - 1.5 mg/mL and low inlet concentration - 0.2 mg/mL of antibiotic solution for both adsorbents. The static adsorption capacity was up to 2.71 mg/g for moxifloxacin hydrochloride; 4.14 mg/g for norfloxacin and the dynamic adsorption capacity was up to 1.20 mg/g for moxifloxacin hydrochloride; 2.10 mg/g for norfloxacin at a neutral pH value and constant temperature of 200°C. Each antibiotic was determined quantitatively in sample solutions using the developed and validated HPLC methods with a limit of quantitation - 0.05 µg/mL. Hence, this study demonstrates and proves that natural zeolite could be an effective adsorbent for the removal of the selected antibiotics from wastewaters.
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