Ligandless ultrasonic-assisted and ionic liquid-based dispersive liquid-liquid microextraction of copper, nickel and lead in different food samples.

A simple and rapid ultrasonic assisted-ionic liquid based-liquid-liquid microextraction (UA-IL-DLLME) method has been developed for the enrichment and separation of Cu(II), Ni(II) and Pb(II). A two level factorial design was used to determine the effect of key factors such as pH, volume of ionic liquid (IL), carbon tetra chloride (CCl4) and sonication time (St). 1-Butyl-3-methylimidazolium hexafluorophosphate ([C4MIM][PF6]) and CCl4 were used as an extractant and dispersant solvent, respectively. The accuracy of the proposed method was evaluated by analysing of SRM Apple Leaves 1515 certified reference material. The limits of detections (LODs) were 0.17 µg/L, 0.49 µg/L and 0.95 µg/L for Cu, Ni and Pb, respectively. The enrichment factor (EF) was 100. The method has been successfully applied for the analysis of the content of Cu, Ni and Pb in spice, vegetable and fruit samples by flame atomic absorption spectrometry (FAAS).

Ligandless surfactant mediated solid phase extraction combined with Fe3O4 nano-particle for the preconcentration and determination of cadmium and lead in water and soil samples followed by flame atomic absorption spectrometry: multivariate strategy.

In the present study, a microextraction technique combining Fe3O4 nano-particle with surfactant mediated solid phase extraction ((SM-SPE)) was successfully developed for the preconcentration/separation of Cd(II) and Pb(II) in water and soil samples. The analytes were determined by flame atomic absorption spectrometry (FAAS). The effective variables such as the amount of adsorbent (NPs), the pH, concentration of non-ionic (TX-114) and centrifugation time (min) were investigated by Plackett-Burman (PBD) design. The important variables were further optimized by central composite design (CCD). Under the optimized conditions, the detection limits (LODs) of Cd(II) and Pb(II) were 0.15 and 0.74 µg/L, respectively. The validation of the proposed procedure was checked by the analysis of certified reference materials of TMDA 53.3 fortified water and GBW07425 soil. The method was successfully applied for the determination of Cd(II) and Pb(II) in water and soil samples.

Assessment of water quality of polluted lake using multivariate statistical techniques: a case study.

Multivariate statistical techniques, cluster analysis (CA) and principal component analysis (PCA) were applied to the data on water quality of Manchar Lake (Pakistan), generated during 2005-06, with monitoring at five different sites for 36 parameters. This study evaluated and interpreted complex water quality data sets and apportioned of pollution sources to get better information about water quality and to design a monitoring network. The chemical correlations were observed by PCA, which were used to classify the samples by CA, based on the PCA scores. Three significant sampling locations--(sites 1 and 2), (site 4) and (sites 3 and 5)--were detected on the basis of similarity of their water quality. The results revealed that the major causes of water quality deterioration were related to inflow of effluent from industrial, domestic, agricultural and saline seeps into the lake at site 1 and also resulting from people living in boats and fishing at sites 2 and 3.

Toxic metals distribution in different components of Pakistani and imported cigarettes by electrothermal atomic absorption spectrometer.

It was extensively investigated that a significant flux of toxic metals, along with other toxins, reaches the lungs through smoking. In present study toxic metals (TMs) (Al, Cd, Ni and Pb) were determined in different components of Pakistani local branded and imported cigarettes, including filler tobacco (FT), filter (before and after normal smoking by a single volunteer) and ash by electrothermal atomic absorption spectrometer (ETAAS). Microwave-assisted digestion method was employed. The validity and accuracy of methodology were checked by using certified sample of Virginia tobacco leaves (ICHTJ-cta-VTL-2). The percentages (%) of TMs in different components of cigarette were calculated with respect to their total contents in FT of all branded cigarettes before smoking, while smoke concentration has been calculated by subtracting the filter and ash contents from the filler tobacco content of each branded cigarette. The highest percentage (%) of Al was observed in ash of all cigarettes, with range 97.3-99.0%, while in the case of Cd, a reverse behaviour was observed, as a range of 15.0-31.3% of total contents were left in the ash of all branded cigarettes understudy.

Determination of arsenic levels in lake water, sediment, and foodstuff from selected area of Sindh, Pakistan: estimation of daily dietary intake.

The aim of present study was to develop a database of arsenic (As) in lake water, ground water, sediment, soil, vegetables, grain crops and fish to evaluate the potential human health risks posed by higher level of As, in south east part of Sindh, Pakistan during 2005-2007. The total concentration of As in various samples under study was determined by electrothermal atomic absorption spectrophotometry (ETAAS). The reliability and accuracy of technique was checked by different certified reference materials. The concentration of As in lake and ground water samples exceeded the WHO guideline values. The concentration of As in lake sediment and agricultural soil samples ranged between 11.3-55.8 and 8.7-46.2 mg/kg while acid soluble As (acetic acid 0.11 mol/L) was observed in the range of 1.48-3.54 and 0.34-3.78 mg/kg, respectively. It was observed that the leafy vegetables (spinach, coriander and peppermint) contain higher As levels (0.90-1.20 mg/kg) as compared to ground vegetables (0.048-0.25) and grain crops (0.248-0.367 mg/kg) on dried weight basis. The estimated daily intake of total As in the diet was 9.7-12.2 microg/kg body weight/day.

Time saving modified BCR sequential extraction procedure for the fraction of Cd, Cr, Cu, Ni, Pb and Zn in sediment samples of polluted lake.

The mobility, availability and persistence of heavy metals (Cd, Cr, Cu, Ni, Pb and Zn) in contaminated lake sediment samples were evaluated by means of sequential extraction scheme, proposed by the Community Bureau of Reference protocol (BCR). The metal content in the extracts was measured by atomic absorption spectrometry. The precision and accuracy of the proposed procedure were evaluated by using a certified reference material BCR 701. The maximum recoveries for heavy metals (HMs) were observed for all three steps of BCR protocol at 32h total shaking period instead of previously reported 51h, with p>0.05. The lixiviation tests (DIN 38414-S4) were used to evaluate the leaching of HMs from sediment samples and it was observed that levels of water extractable HMs were low as compared to those values obtained by acid-soluble fraction of the BCR protocol.

Total dissolved and bioavailable elements in water and sediment samples and their accumulation in Oreochromis mossambicus of polluted Manchar Lake.

The concentrations of 15 elements were determined in water, sediment and tissues of fish (Oreochromis mossambicus) collected from five sampling stations of Manchar Lake in 2005 for two successive seasons, winter (WS) and summer (SS). Elements analysis was performed by atomic absorption spectrometry with flame (FAAS) and electrothermal (ETAAS) modes, using multielement standard solution. The obtained results show that, the trace and toxic elements (As, Cd, Co, Cr, Cu, Fe, Mn, Ni, Pb and Zn) and macronutrients (Al, Ca, K, Mg and Na) concentrations in lake water were above the recommended drinking water standards by WHO. Concentrations of Na detected in lake water in WS and SS, were in the range of 445.5-562.7 and 420.6-643.5 mgl(-1), respectively. While among toxic elements As concentration in both seasons, have been found in the range of 60.4-88.9 and 64.9-101.8 microgl(-1) respectively, these values are 6-10 times higher than the permissible limit of WHO. The mean concentrations of elements understudy in muscles of fish were found as 2.35, 1.39, 0.46, 2.3, 1517.9, 2.2, 2.4 and 188.9 mgkg(-1) for As, Cd, Cr, Cu, Fe, Ni, Pb and Zn, respectively. High accumulation of toxic elements in fish tissues is indicating that some of the metal contaminants are entering the food chain. Correlations among the variables were identified by multivariate analysis. The extraction of elements from sediments with EDTA, to predict the bioavailability of trace and toxic elements, has shown that among them As, Cd and Zn were the most bioavailable elements in lake sediment.

Determination of cadmium in whole blood and scalp hair samples of Pakistani male lung cancer patients by electrothermal atomic absorption spectrometer.

A large number of epidemiologic studies have been undertaken to identify potential risk factors for cancer, amongst which the association with cadmium has received considerable attention. There is compelling evidence in support of positive associations between cadmium and risk of lung cancer. In present study we measured the concentration of Cd in whole blood and scalp hair samples of 120 male lung cancer patients (smokers) and 150 controls or referents (smokers and nonsmokers) from different cities of Pakistan. Both referents and patients were of same age group (ranged 40-70 years), socio-economic status, localities and dietary habits. The scalp hair and whole blood samples were oxidized by 65% nitric acid: 30% hydrogen peroxide (2:1) ratio in microwave oven. To check the validity of the proposed method, a conventional wet acid digestion method was used to obtain total Cd concentration in certified samples of human hair BCR 397 and Clincheck control-lyophilized human whole blood. All digests were analyzed for Cd concentration by electrothermal atomic absorption spectrometer (ETAAS). The results of this study showed that the average Cd concentration was higher in the blood and scalp hair of lung cancer patients at different stages as compared to controls (p<001). The smoker referents have high level of Cd in both biological samples as compared to nonsmoker subjects. These results illustrate that the patients who continued smoking after confirmed diagnosis of lung cancer have 34.2-67.26 and 22.4-57.3% more Cd in blood samples and scalp hair than lung cancer patients who cease smoking. This study is compelling evidence in support of positive associations between cadmium, cigarette smoking and lung cancer risk.