Ultrasonic energy enhanced the efficiency of advance extraction methodology for enrichment of trace level of copper in serum samples of patients having neurological disorders.

An innovative dual dispersive ionic liquid based on ultrasound assisted microextraction (UDIL-µE), for the enrichment of trace levels of copper ion (Cu2+), in serum (blood) of patients suffering from different neurological disorders. The enriched metal ions were subjected to flame atomic absorption spectrometry (FAAS). In the UDIL-µE method, the extraction solvent, ionic liquid, 1-butyl-3-methylimidazolium hexafluorophosphate [C4mim][PF6], was dispersed into the aqueous samples using an ultrasonic bath. The(PAN) 1-(2-pyridylazo)-2-naphthol was used as ligand for the complexation of Cu ion in IL (as extracting solvent). The various variables such as sonication time, pH, concentration of complexing agent, time and rate of centrifugation, IL volume that affect the extraction process were optimized. The enhancement factor (EF) and detection limit (LOD) was found under favorable condition was 31 and 0.36µgL-1, respectively. Reliability of the proposed method was checked by relative standard deviation (%RSD), which was found to be <5%. The accuracy of developed procedure was assured by using certified reference material (CRM) of blood serum. The developed procedure was applied successfully to the analysis of concentration of Cu ion in blood serum of different neurological disorders subjects and referents of same age group. It was observed that the levels of Cu ion was two folds higher in serum samples of neurological disorders patients as related to normal referents of same age group.

Estimation of Nickel in Different Smokeless Tobacco Products and Their Impact on Human Health of Oral Cancer Patients.

It has been extensively investigated that the chewing of smokeless tobacco (SLT) products may enhance the inflammation of the oral cavity. The aim of the present study is to evaluate the relationship between nickel (Ni) exposure via different SLT products with oral cancer (different sites) incidence in the population of Sindh, Pakistan. The different brands of SLT products (mainpuri, gutkha, and moist snuff) commonly consumed by the studied population were analyzed for Ni contents. The biological samples of oral cancer patients and noncancerous control subjects of both genders, who have or have not consumed SLT products, were collected. The concentration of Ni in biological samples and SLT products were measured by electrothermal atomic absorption spectrophotometer after microwave-assisted acid digestion. The validity and accuracy of the methodology were checked by using certified reference materials. The results of this study showed that the Ni level was significantly higher in scalp hair and blood samples of oral cancer patients compared to controls (P < 0.01). The study suggested that exposure of Ni as a result of chewing different SLT products may be synergistic with risk factors associated with oral cancer.

Evaluation of the fate of arsenic-contaminated groundwater at different aquifers of Thar coalfield Pakistan.

In present study, the ground water at different aquifers was evaluated for physicochemical parameters, iron, total arsenic, total inorganic arsenic and arsenic species (arsenite and arsenate). The samples of groundwater were collected at different depths, first aquifer (AQ1) 50-60 m, second aquifer (AQ2) 100-120 m, and third aquifer (AQ3) 200-250 m of Thar coalfield, Pakistan. Total inorganic arsenic was determined by solid phase extraction using titanium dioxide as an adsorbent. The arsenite was determined by cloud point extraction using ammonium pyrrolidinedithiocarbamate as a chelating reagent, and resulted complex was extracted by Triton X-114. The resulted data of groundwater were reported in terms of basic statistical parameters, principal component, and cluster analysis. The resulted data indicated that physicochemical parameters of groundwater of different aquifers were exceeded the World Health Organization provisional guideline for drinking water except pH and SO4(2-). The positive correlation was observed between arsenic species and physicochemical parameters of groundwater except F(-) and K(+), which might be caused by geochemical minerals. Results of cluster analysis indicated that groundwater samples of AQ1 was highly contaminated with arsenic species as compared to AQ2 and AQ3 (p > 0.05).

Variation in the Levels of Aluminum and Manganese in Scalp Hair Samples of the Patients Having Different Psychiatric Disorders with Related to Healthy Subjects.

There is very limited information available on the role of trace elements in psychiatric disorders (PSD). Immense pieces of evidence support the idea that exposure to trace and toxic metals, such as aluminum (Al) and manganese (Mn), may be factors or cofactors in the etiopathogenesis of a variety of psychiatric disorders. The aim of our study was to assess the Al and Mn in scalp hair samples of 102 patients having different types of psychiatric disorder PSD diseases together with 120 referent subjects of male patients in the age group of 45-60 years. The understudy elements in scalp hair samples were assessed by the flame atomic absorption spectrophotometry after microwave-assisted acid digestion method .The validity of methodology was checked by the certified human hair reference material (NCS ZC81002). The recovery of studied elements was found in the range of 98.1-99.2 % of certified reference material. The results of this study showed that the mean values of Al and Mn were significantly higher in scalp hair samples of all types of PSD as compared to referents subjects. The resulted data indicated a significant increase in the contents of Mn and Al in scalp hair samples of psychiatric patients than that of its control counterpart, which may provide prognostic tool for the diagnosis of the mental disorders. However, further work is suggested to examine the exact correlation between trace elements level and the degree of disorder.

Estimation of lead in biological samples of oral cancer patients chewing smokeless tobacco products by ionic liquid-based microextraction in a single syringe system.

Several studies have reported that the chewing habit of smokeless tobacco (SLT) has been associated with oral cancer. The aim of the present study was to evaluate the trace levels of lead (Pb) in biological samples (blood, scalp hair) of oral cancer patients and referents of the same age group (range 30-60 years). As the concentrations of Pb are very low in biological samples, so a simple and efficient ionic liquid-based microextraction in a single syringe system has been developed, as a prior step to determination by flame atomic absorption spectrometry. In this procedure, the hydrophobic chelates of Pb with ammonium pyrrolidinedithiocarbamate (APDC) were extracted into fine droplets of 1-butyl-3-methylimidazolium hexafluorophosphate [C4MIM][PF6] within a syringe while using Triton X-114 as a dispersant. Factors influencing the microextraction efficiency and determination, such as pH of the sample, volume of [C4MIM][PF6] and Triton X-114, ligand concentration, and incubation time, were studied. To validate the proposed method, certified reference materials were analyzed and the results of Pb(2+) were in good agreement with certified values. At optimum experimental values of significant variables, detection limit and enhancement factor were found to be 0.412 µg/L and 80, respectively. The coexisting ions showed no obvious negative outcome on Pb preconcentration. The proposed method was applied satisfactorily for the preconcentration of Pb(2+) in acid-digested SLT and biological samples of the study population. It was observed that oral cancer patients who consumed different SLT products have 2-3-fold higher levels of Pb in scalp hair and blood samples as compared to healthy referents (p < 0.001). While 31.4-50.8% higher levels of Pb were observed in referents chewing different SLT products as compared to nonconsumers (p < 0.01).

Comparative evaluation of essential and toxic elements in the blood of kidney failure patients and healthy referents.

The aim of the present study was to evaluate the comparative distribution, correlation, and apportionment of selected elements-aluminum (Al), calcium (Ca), cadmium (Cd), potassium (K), magnesium (Mg), sodium (Na), and lead (Pb)-in the blood samples of male kidney failure patients (KFP) and healthy subjects of age ranged 30-60 years. The blood samples were digested with nitric acid and perchloric acid mixture (2:1), followed by the quantification of elements by atomic absorption spectrometry. The concentration of essential elements in blood samples of KFP were found in the range of Ca (97-125), Mg (18-36), Na (2971-3685), and K (177-270) mg/L while, the levels of Al, Cd, and Pb were found in the range of (475-1275), (0.9-9.9), and (211-623) µg/L, respectively. In the healthy referents, concentration of electrolytes in blood samples was lower than KFP, but difference was not significant (p > 0.05). While the levels of toxic elements in blood samples of referents were three- to sixfold lower than KFP (p < 0.01). Principal component analysis (PCA) and cluster analysis (CA) of the element data manifested diverse apportionment of the selected elements in the blood sample of the KFP compared with the healthy counterparts.

Arsenic in coal of the Thar coalfield, Pakistan, and its behavior during combustion.

The aim of the current study is to evaluate the occurrence of arsenic in coal collected from Thar coalfield, Pakistan, and its behavior during the combustion. Fractionation of arsenic (As) in coal samples was carried out by Community Bureau of Reference sequential extraction scheme (BCR-SES) and single-step-based BCR method (BCR-SS). These methods are validated using the certified reference material of sediment BCR 701 and standard addition method. The stepwise fractions of As in laboratory-made ash (LMA) have been also investigated. The extractable As content associated with different phases in coal and LMA samples were analyzed by electrothermal atomic absorption spectrophotometer. The extraction efficiency of As by BCR-SS was slightly higher than BCR-SES, while the difference was not significant (p < 0.05). The BCR-SS method is a time-saving method because it can reduce the extraction time from 51 to 22 h. The As contents in LMA revealed that during combustion of the coal, >85 % of As may be released into atmosphere. The relative mobility of As in the coal samples was found in increasing order as follows: oxidizable fraction < reducible fraction < acid soluble fraction. The total and extractable As obtained by BCR-SES and BCR-SS were higher in coal samples of block III as compared to block V (p > 0.05).

Temperature controlled ionic liquid-based dispersive micro-extraction using two ligands, for determination of aluminium in scalp hair samples of Alzheimer's patients: a multivariate study.

A green and sensitive temperature controlled dispersive liquid-liquid microextraction (TIL-DLLME) methodology based on the application of ionic liquid 1-butyl-3-methylimidazolium hexafluorophosphate, [C4mim][PF6], as an extractant solvent was proposed for the preconcentration of trace levels of aluminium (Al(3+)) in scalp hair samples of Alzheimer's (AD) patients, prior to analyzing by flame atomic absorption spectrometry (FAAS). The Al(3+) was complexed with 8-hydrooxyquinoline (oxine) (L1) and 3,5,7,2'-4' pentahydroxy flavone (morin) (L2) separately and then extracted by IL at temperature (50±2.0°C). Some effective factors that influence the TIL-DLLME efficiency such as pH, ligands concentrations, volume of IL, ionic strength, and incubation time were investigated and optimized by multivariate analysis. In the optimum experimental conditions, the limit of detection (3s) and enhancement factor were 0.56 µg L(-1), 0.64 µg L(-1) and 85, 73 for both ligands, respectively. The relative standard deviation (RSD) for six replicate determinations of 100 µg L(-1) Al(3+) complexed with oxine and morin were found to be 3.88% and 4.74%, respectively. The developed method was validated by the analysis of certified reference material of human hair (NCSZC81002).and applied satisfactorily to the determination of Al(3+) in acid digested scalp hair samples of AD patients and healthy controls. The resulted data shows significant higher level in scalp hair samples of AD male patients with related to referents of same age and socioeconomic status.