nan Naeemullah

Cloud point extraction for determination of lead in blood samples of children, using different ligands prior to analysis by flame atomic absorption spectrometry: A multivariate study

The phase-separation phenomenon of non-ionic surfactants occurring in aqueous solution was used for the extraction of lead (Pb(2+)) from digested blood samples after simultaneous complexation with ammonium pyrrolidinedithiocarbamate (APDC) and diethyldithiocarbamate (DDTC) separately. The complexed analyte was quantitatively extracted with octylphenoxypolyethoxyethanol (Triton X-114). The multivariate strategy was applied to estimate the optimum values of experimental factors. Acidic ethanol was added to the surfactant-rich phase prior to its analysis by flame atomic absorption spectrometer (FAAS). The detection limit value of Pb(2+) for the preconcentration of 10 mL of acid digested blood sample was 1.14 μg L(-1). The accuracy of the proposed methods was assessed by analyzing certified reference material (whole blood). Under the optimized conditions of both CPE methods, 10 mL of Pb(2+) standards (10 μg L(-1)) complexed with APDC and DDTC, permitted the enhancement factors of 56 and 42, respectively. The proposed method was used for determination of Pb(2+) in blood samples of children with kidney disorders and healthy controls.

Evaluating the accumulation of arsenic in maize (Zea mays L.) plants from its growing media by cloud point extraction

A cloud point extraction has been developed for the determination of As in maize (Zea mays L.) and adjoining agriculture soil. The different parts of maize (grains, shoots and roots) and soil were subjected to microwave assisted digestion in a mixture of nitric acid and hydrogen peroxide (2:1 ratio). The trace amounts of As was pre-concentrated by cloud point extraction, as prior step to its determination by electrothermal atomic absorption spectrometry. The main factors affecting cloud point extraction efficiency, such as pH of sample solution, concentration of ammonium pyrrolidine dithiocarbamate and Triton X-114, equilibration temperature and time period for shaking were investigated in detail. For validation of proposed method a certified reference material of whole meal flour BCR 189 was used. No significant difference p>0.05 was observed between the experimental results and the certified values of CRM (paired t-test). The translocation of total As in different parts of maize were found in the order of, Root>Shoot>Grain.

Magnetic stirrer induced dispersive ionic-liquid microextraction for the determination of vanadium in water and food samples prior to graphite furnace atomic absorption spectrometry.

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 18 ng L(-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 0.5 μg L(-1) of vanadium level was found to be <5.0%. This method was successfully applied to real water and acid digested food samples.

Pressure-assisted ionic liquid dispersive microextraction of vanadium coupled with electrothermal atomic absorption spectrometry

A simple and new liquid–liquid dispersive microextraction termed pressure-assisted ionic liquid dispersive microextraction (PILDME) was developed for the concentration of trace levels of vanadium in real water samples followed by its quantification by graphite furnace atomic absorption spectrometry (GFAAS). We performed a pressure-induced dispersion of 1-butyl-3-methylimidazolium hexafluorophosphate [C4mim][PF6] into the aqueous sample. Chloroform was used to decrease the dissolution and increase hydrophobicity of the ionic liquid to entrap vanadium in a labile hydrophobic chelate with 8-hydroxyqunioline (8-HQ). Several variables playing a vital role in the prescribed procedure were studied and optimized. With optimum experimental values of significant variables, the detection limit (LOD) and the enhancement factor (EF) were observed to be 20 ng L−1 and 100, respectively. The precision of the method was checked by detection of the relative standard deviation (RSD) as 4.5% at a vanadium concentration of 0.5 μg L−1. The validity and accuracy of the applied method were tested by vanadium extraction and quantification of the standard reference material “SLRS-4 Riverine water”, and the results were found to be in good agreement with the certified values. The method was satisfactorily applied to real water samples.

Simultaneous preconcentration of toxic elements in artificial saliva extract of smokeless tobacco product, mainpuri by cloud point extraction method.

It has been extensively investigated that smokeless tobacco chewing can lead mainly to inflammation of oral cavity. In present study, the total and artificial saliva extracted toxic elements, arsenic, cadmium, nickel and lead were estimated in smokeless tobacco product, mainpuri. Cloud point extraction has been used for the preconcentration of arsenic, cadmium, nickel and lead in artificial saliva extract, using complexing reagent, ammonium pyrrolidinedithiocarbamate. Total and extractable toxic elements were measured by electrothermal atomic absorption spectrometry. The chemical variables of cloud point extraction were optimized. The validity of methodology was tested by simultaneously analyzing certified reference material (Virginia tobacco leaves) and spike recovery test. The artificial saliva extractable levels of arsenic, cadmium, nickel and lead ranged from 15-22, 45-70, 35-58, and 18-32%, respectively, of total elemental contents in mainpuri samples. It was estimated that intake of 10g of different brands of mainpuri contributing the 5.88, 55.0, 45.0 and 40.3% of the provisional maximum tolerable daily intake for arsenic, cadmium, nickel and lead, respectively for adults of ~60kg.

A new solid phase microextraction method using organic ligand in micropipette tip syringe system packed with modified carbon cloth for preconcentration of cadmium in drinking water and blood samples of kidney failure patients

A simple and efficient miniaturized solid phase microextraction (M-SPμE) in a syringe system was developed for preconcentration of cadmium (Cd) in environmental and biological samples, followed by flame atomic absorption technique. The syringe system contains the micropipette tip packed with activated carbon cloth, coated with modified magnetic nanoparticles of iron oxide Triton X114 (ACC-NPs). Scanning electron microscopy and energy dispersive spectroscopy used for characterization of the size, morphology and elemental composition of ACC-NPs. The sample solution treated with a complexing reagent 8-hydroxyqunilone (8-HQ), and drawn into the syringe, filled with ACC-MNPs and dispensed manually for 2-10 drawing/discharging cycles. The analyte retained on ACC-NPs in micropipette tip-syringe system were then eluted with different volume of 1.5molL(-1) HCl by 1-5 drawing/discharging cycles. The syringe system directly couple with FAAS for analysis. The influence of different variables on the extraction efficiency of Cd, including adsorbent dosage, pH, sample volume, eluent volume and drawing/discharging cycles of syringe system were optimized. At optimized extraction conditions, the method showed good linearity in the range of 5-250μgL(-1), with a limit of detection 0.15μgL(-1). Repeatability of the extraction (%RSD) was <5%, n=5. The validity and accuracy of the method was checked by the certified reference materials. The proposed method was successfully applied for the determination of Cd in different drinking water and biological samples of kidney failure patients and healthy controls.

Application of dual-cloud point extraction for the trace levels of copper in serum of different viral hepatitis patients by flame atomic absorption spectrometry: a multivariate study.

An efficient, innovative preconcentration method, dual-cloud point extraction (d-CPE) has been developed for the extraction and preconcentration of copper (Cu(2+)) in serum samples of different viral hepatitis patients prior to couple with flame atomic absorption spectrometry (FAAS). The d-CPE procedure was based on forming complexes of elemental ions with complexing reagent 1-(2-pyridylazo)-2-naphthol (PAN), and subsequent entrapping the complexes in nonionic surfactant (Triton X-114). Then the surfactant rich phase containing the metal complexes was treated with aqueous nitric acid solution, and metal ions were back extracted into the aqueous phase, as second cloud point extraction stage, and finally determined by flame atomic absorption spectrometry using conventional nebulization. The multivariate strategy was applied to estimate the optimum values of experimental variables for the recovery of Cu(2+) using d-CPE. In optimum experimental conditions, the limit of detection and the enrichment factor were 0.046μgL(-1) and 78, respectively. The validity and accuracy of proposed method were checked by analysis of Cu(2+) in certified sample of serum (CRM) by d-CPE and conventional CPE procedure on same CRM. The proposed method was successfully applied to the determination of Cu(2+) in serum samples of different viral hepatitis patients and healthy controls.

Development of a new green non-dispersive ionic liquid microextraction method in a narrow glass column for determination of cadmium prior to couple with graphite furnace atomic absorption spectrometry.

Easy and innovative non-dispersive ionic liquid based microextraction (NDILME) has been developed for preconcentration of trace level of cadmium (Cd) in aqueous real surface water samples prior to couple with graphite furnace atomic absorption spectrometry (GFAAS). A 200 cm long narrow glass column containing aqueous solution of standard/sample was used to increase phase transfer ratio by providing more contact area between two medium (aqueous and extractive), which drastically improve the recoveries of labile hydrophobic chelate of Cd ammonium pyrrolidinedithiocarbamate (APDC), into ionic liquid 1-butyl-3-methylimidazolium hexafluorophosphate [C4mim][PF6]. Different aspect of the desire method have been investigated and optimized. Under the optimized key experimental variables, limit of detection (LOD) and enhancement factor (EF) were achieved to be 0.5 ng L(-1) and 150, respectively. Reliability of the model method was checked by relative standard deviation (%RSD), which was found to be <5%. Validity and accuracy of the developed method was checked by analysis of certified reference water samples (SLRS-4 Riverine water) using standard addition method. Application of the model method was productively performed by analysis of Cd in real surface water samples (tap and sea).

Simple and green switchable dispersive liquid–liquid microextraction of cadmium in water and food samples

A green, switchable water dispersive liquid–liquid microextraction (SWDLL-ME) method is introduced for the first time as a preconcentration/separation tool for measuring trace levels of cadmium (Cd) in real water and food samples. In the present study, a switchable aqueous solution of polar organic solvent (acetonitrile) was reversibly switched (on and off) from miscible monophasic to immiscible biphasic in aqueous medium by exposure to an anti-solvent trigger (CO2). The developed SWDLL-ME was successfully applied as an extraction method for the extraction of a Cd–PAN complex (1-(2-pyridylazo)-2-naphthol) in polar organic solvent (PS). The solvent enriched phase containing Cd–PAN was separated from the switchable water (SW) and treated with 200 μL of 0.1 mol L−1 HNO3 with ethanol (1 : 1, v/v) in order to reduce its viscosity, and it was then easily injected into a GFAAS for analysis. The SW was reused for the next assay after the removal of CO2. The switching phenomenon of the SW from low to high polarity was confirmed by FTIR spectroscopy and conductivity measurements. The enrichment factor and limit of detection of the proposed method were 22 and 0.38 ng L−1, respectively. Validation of the developed method was carried out by analyzing certified reference materials (SLRS-4 Riverine water and NIST SRM 1515 Apple leaves).

Temperature-controlled ionic liquid-based ultrasound-assisted microextraction for preconcentration of trace quantity of cadmium and nickel by using organic ligand in artificial saliva extract of smokeless tobacco products.

A new approach was developed for the preconcentration of cadmium (Cd) and nickel (Ni) in artificial saliva extract of dry snuff (brown and black) products using temperature-controlled ionic liquid-based ultrasound-assisted dispersive liquid-liquid microextraction (TIL-UDLLμE) followed by electrothermal atomic absorption spectrometry (ETAAS). The Cd and Ni were complexed with ammonium pyrrolidinedithiocarbamate (APDC), extracted in ionic liquid drops, 1-butyl-3-methylimidazolium hexafluorophosphate [C4MIM][PF6]. The multivariate strategy was applied to estimate the optimum values of experimental variables influence the % recovery of analytes by TIL-UDLLμE method. At optimum experimental conditions, the limit of detection (3s) were 0.05 and 0.14μgL(-1) while relative standard deviations (% RSD) were 3.97 and 3.55 for Cd and Ni respectively. After extraction, the enhancement factors (EF) were 87 and 79 for Cd and Ni, respectively. The RSD for six replicates of 10μgL(-1) Cd and Ni were 3.97% and 3.55% respectively. To validate the proposed method, certified reference material (CRM) of Virginia tobacco leaves was analyzed, and the determined values of Cd and Ni were in good agreement with the certified values. The concentration of Cd and Ni in artificial saliva extracts corresponds to 39-52% and 21-32%, respectively, of the total contents of both elements in dry brown and black snuff products.