title: Vortex-assisted ionic liquid-based dispersive liquid-liquid microextraction for assessment of chromium species in artificial saliva extract of different chewing tobacco products.
abstract: A novel dispersive liquid-liquid microextraction (ILDLLμE) method using an extracting solvent (ionic liquid) and dispersant (Triton X-114) was developed for the separation and preconcentration of hexavalent chromium (Cr6+) in artificial saliva extract (ASE) of chewing tobacco products, gutkha, and mainpuri (n = 23). In the proposed method, the extraction of Cr6+was accomplished by using ammonium pyrrolidinedithiocarbamate (APDC) as complexing agent and 1-butyl-3-methylimidazolium hexafluorophosphate [C4MIM] [PF6] as extracting solvent. The tiny droplet of metal chelate was then dispersed into TX-114 emulsion, using vortex mixer. Various parameters such as concentration of APDC, pH of the solution, volume of [C4MIM] [PF6], and TX-114 as well as extraction time were studied. Under the most favorable conditions, the limit of detection was found to be 0.068 μg/L with the relative standard deviation <5 %. The enrichment factor of developed method was found as 62.5, and method has been effectively applied for the analysis of Cr species in artificial saliva extract of gutkha and mainpuri products. The Cr6+was quantitatively recovered (<97 %) under optimal conditions, while the recovery of trivalent specie (Cr3+), at the same experimental conditions, was observed to be <5 %. The Cr3+was determined by the difference of total Cr and Cr6+in artificial saliva extract of selected STP. Health risks associated with the intake of total Cr in gutkha and mainpuri were assessed in terms of estimated daily intake, such as carcinogenic and noncarcinogenic risks. Estimated daily intake of Cr via chewing 10 g/day of gutkha and mainpuri was found to be below the maximum tolerable daily intake, whereas the calculated risk of cancer for Cr was observed in the acceptable range of 10E-6-10E-4, except some brands of gutkha. Graphical Abstract ᅟ.
authors.affiliation: National Centre of Excellence in Analytical Chemistry, University of Sindh, Jamshoro, 76080, Pakistan. 2k10chem21@gmail.com.
authors.forename: Asma
authors.initials: A
authors.lastname: Akhtar
authors.affiliation: National Centre of Excellence in Analytical Chemistry, University of Sindh, Jamshoro, 76080, Pakistan.
authors.forename: Tasneem Gul
authors.initials: TG
authors.lastname: Kazi
authors.affiliation: National Centre of Excellence in Analytical Chemistry, University of Sindh, Jamshoro, 76080, Pakistan.
authors.forename: Hassan Imran
authors.initials: HI
authors.lastname: Afridi
authors.affiliation: H. E.J. Research Institute of Chemistry, University of Karachi, Karachi, 75270, Pakistan.
authors.forename: Syed Ghulam
authors.initials: SG
authors.lastname: Musharraf
authors.affiliation: National Centre of Excellence in Analytical Chemistry, University of Sindh, Jamshoro, 76080, Pakistan.
authors.forename: Farah Naz
authors.initials: FN
authors.lastname: Talpur
authors.affiliation: National Centre of Excellence in Analytical Chemistry, University of Sindh, Jamshoro, 76080, Pakistan.
authors.forename: Noman
authors.initials: N
authors.lastname: Khan
authors.affiliation: National Centre of Excellence in Analytical Chemistry, University of Sindh, Jamshoro, 76080, Pakistan.
authors.forename: Muhammad
authors.initials: M
authors.lastname: Bilal
authors.affiliation: National Centre of Excellence in Analytical Chemistry, University of Sindh, Jamshoro, 76080, Pakistan.
authors.forename: Mustafa
authors.initials: M
authors.lastname: Khan
mesh_terms: D002857:Chromium / Q000032:analysis*; D004781:Environmental Exposure / Q000032:analysis*; D006801:Humans; D007093:Imidazoles; D052578:Ionic Liquids; D059627:Liquid Phase Microextraction / Q000379:methods*; D017830:Octoxynol; D011092:Polyethylene Glycols; D011759:Pyrrolidines; D018570:Risk Assessment; D012464:Saliva, Artificial; D013859:Thiocarbamates; D014030:Tobacco, Smokeless / Q000032:analysis*
chemical_list: C412621:1-butyl-3-methylimidazolium hexafluorophosphate; D007093:Imidazoles; D052578:Ionic Liquids; D011759:Pyrrolidines; D012464:Saliva, Artificial; D013859:Thiocarbamates; D002857:Chromium; C074702:chromium hexavalent ion; C020972:pyrrolidine dithiocarbamic acid; D011092:Polyethylene Glycols; D017830:Octoxynol; C010615:Nonidet P-40
keywords: Flame atomic absorption spectroscopy; Risk assessment; Smokeless tobacco products; Vortex assisted ionic liquid dispersive microextraction method