Determination of total selenium in pharmaceutical and herbal supplements by hydride generation and graphite furnace atomic absorption spectrometry.

The total selenium (Se) was determined in herbal and pharmaceutical supplements used for liver diseases. The total Se contents were determined in different pharmaceutical and herbal supplements by hydride generation atomic absorption spectrometry (HGAAS) and graphite furnace atomic absorption spectrometry (GFAAS) after microwave-assisted acid digestion. The accuracy of the techniques was evaluated by using certified reference material and the standard addition method. The recoveries of total Se were 99.4 and 99.0% for HGAAS and GFAAS, respectively. The precision of the techniques expressed as RSD were 2.34 and 4.54% for HGAAS and GFAAS measurements, respectively. The LOD values for HGAAS and GFAAS were 0.025 and 0.052 pglg, respectively. The concentrations of Se in pharmaceutical and herbal supplements were found in the range of 19.2-53.8 and 25.0-42.5 pg/g, respectively, corresponding to 35-76% and 45-76% of the total recommended dose of Se for adults.

Effects of selenium and zinc status in biological samples of hepatitis C patient after herbal and pharmaceutical supplements.

The use of natural remedies and pharmacological mineral supplements for liver disease treatment has a long history. In present study, the levels of selenium (Se) and zinc (Zn) were determined in biological samples (serum and whole blood) of female hepatitis C patients (n = 132), age ranged 30-45 years, before and after 30 days treatment with herbal/pharmaceutical supplements. For comparative study, 128 age-matched female subjects, residing in the same residential areas and have socioeconomic status, were selected as referents. The Se and Zn in supplements, blood, and sera were determined by atomic absorption spectrometry. It was observed that Zn and Se in blood and serum samples of viral hepatitis C (HCV) patients were reduced in the range of 28.6-39 % and 24-36 %, respectively, as compared to those of referents. After herbal/pharmaceutical supplementations, 20.6-25.0 and 9.15-13.2 % of Zn and 10.6-12.1 and 19.6-21.4 % of Se were enhanced in sera and blood samples of HCV patients, respectively. The resulted data indicated that the levels of Se and Zn in addition to some biochemical parameters were improved in HCV patients after herbal/pharmaceutical supplementation. The effects of both supplements were not significantly different (p > 0.05).

Development of extraction methods for speciation analysis of selenium in aqueous extracts of medicinal plants.

Advanced extraction methods have been developed for direct speciation of dissolved inorganic and organic selenium (Se) species in aqueous extracts of medicinal plants (MPs). The inorganic species of Se (SeIV and SeVI) were separated from organic forms by adsorbing inorganic Se on alumina, while the organic Se was not retained. The retained inorganic Se species was eluted with 10 mL 0.2 M HCl. The total inorganic Se species was determined after prereduction of SeVI into SeIV with concentrated HCl. The SeIV in the eluent and total inorganic Se species were then complexed with diethyldithiocarbamate. The resultant complexes were entrapped in the nonionic surfactant Triton X-114. The total Se, organic Se, total inorganic Se, and SeIV species were determined by electrothermal atomic absorption spectrometry with a modifier. The SeVI concentration was obtained by subtracting SeIV from total inorganic Se contents. The main factors affecting the methodologies were investigated in detail. Under the optimized experimental conditions, the LOD for SeIV was 50 microg/L. Among dissolved inorganic and organic Se species in aqueous extracts of MPs, organic Se species were present in the range of 74-84%, SeIV 3.62-7.47%, and SeVI 12.4-18.57% of total Se contents.

Evaluation of selenium in biological sample of arsenic exposed female skin lesions and skin cancer patients with related to non-exposed skin cancer patients.

The antagonistic effects between selenium (Se) and arsenic (As) suggest that low Se status plays an important role in arsenism development. The objective of present study was to assess Se contents in biological samples of As exposed females have skin lesions and cancer with related to non-exposed skin cancer patients. The biological samples (blood and scalp hair) of As exposed group comprises, female skin cancer (ESC) patients admitted in cancer hospitals have skin lesions (ESL) and exposed referents have not both diseases (ER), belongs to As exposed area of Pakistan. For comparative purposes, age matched female skin cancerous patient (RP) and non-cancerous females (NER) belong to non-exposed areas were also selected. The As and Se in acid digests of biological samples were pre-concentrated by complexing with chelating agent (ammonium pyrrolidinedithiocarbamate), and resulted complexes were extracted into non-ionic extractant (Triton X-114), prior to analysis by electrothermal atomic absorption spectrometry. The enhancement factor of about 25 was obtained by pre-concentrating 10 mL of sample solutions. The accuracy of the optimized procedure was evaluated by using certified reference material (BCR 397) with certified values for Se and As and standard addition method at three concentration levels in real samples. No significant differences was observed (p>0.05) when comparing the values obtained by the proposed method, added and certified values of both elements. The biological samples of ESC patients had 2-3 folds higher As and lower Se levels as compared to RP (p<0.001). Understudied exposed referents have high level of As and lower Se contents as compared to referents subjects of non-exposed area (p<0.01). The higher concentration of As and lower levels of Se in biological samples of cancerous patients are consisted with reported studies.

Inorganic arsenic speciation in groundwater samples using electrothermal atomic spectrometry following selective separation and cloud point extraction.

A method has been developed for speciation of total, total inorganic and organic arsenic (As) species in groundwater samples. The inorganic species of As((III,V)) were separated from organic forms by adsorbing on alumina (Al(2)O(3)) whereas the organic As was eluted out. The retained inorganic As species was eluted by 0.2 M HCl. Then eluent As(III) and As(V) were formed as complexes with ammonium pyrrolidinedithiocarbamate (APDC) and molybdate, respectively. Then As(III)-PDC and As(V)-molybdate complexes were quantitatively extracted into a non-ionic surfactant Triton X-114. The total As was determined by conventional preconcentration procedures. The resulting solutions of each method were determined by ETAAS with modifier. The main factors affecting the separation and cloud point extraction (CPE) were investigated in detail. The limits of detection values were found as 0.04 and 0.20 µg L(-1) for As(III) and As(V), respectively, whereas limits of quantification were observed as 0.13 and 0.33 µg L(-1) for As(III) and As(V), respectively. Standard addition method confirmed the accuracy. The recoveries of As(III) and As(V) were found in the range of 98 - 99%. The proposed method was applied to groundwater samples collected from different areas of Sukkur district.

Determination of arsenic in scalp hair of children and its correlation with drinking water in exposed areas of Sindh Pakistan.

This study was focused on the analysis of arsenic (As) levels in scalp hair of children (age, <10 years) collected from two towns of Khairpur, Pakistan, to evaluate the effects of As-contaminated groundwater. For comparative purposes, scalp hair samples of children were also collected from that area having low levels of As (<10 µg/L) in drinking water. Groundwater and scalp hair samples of children were collected and analyzed by electrothermal atomic absorption spectrometry prior to microwave-assisted acid digestion. The average As concentrations in groundwater samples of two towns, Thari Mirwah and Gambat, were found to be 28.5 and 98.3 µg/L, respectively. The range of As concentrations in scalp hair samples of children who belong to Thari Mirwah and Gambat was 1.25-1.61 µg/g and 1.73-3.63 µg/g, respectively. Twenty percent of the total children who belong to Gambat have skin lesions on their hands and feet. A positive correlation coefficient (R = 0.91-0.99) was obtained between As contents in drinking water and scalp hairs of children of both towns.

Evaluation of arsenic levels in grain crops samples, irrigated by tube well and canal water.

The aim of this study was to evaluate the uptake of arsenic (As) by grain crops (wheat, maize and sorghum) grown on agricultural soil irrigated with tube well water (SIT) as test samples and for comparative purposes, same grain crop samples grown on agricultural soil irrigated with fresh canal water (SIC) were marked as control samples, collected simultaneously from three sub-districts of Khairpur, Pakistan. Moreover, this paper demonstrated the total and EDTA (0.05 M) extractable As in both understudied soils that correlate with the respective total As in the edible parts of the studied grain crops. A significantly high accumulation of As was found in grains grown on SIT as compared to those grown on SIC. This study highlights the increased danger of growing food crops in the agricultural land continuously irrigated by As contaminated ground water.

Zinc and iron determination in serum and urine samples of thyroid patients using cloud point extraction.

A simple and rapid cloud point extraction method was applied for preconcentration of trace quantities of zinc (Zn) and iron (Fe) in biological samples (serum and urine) of thyroid patients prior to determination by flame atomic absorption spectrometry. The metals in serum and urine samples were complexed with 1-(2-thiazolylazo)-2-naphthol and entrapped in the surfactant octylphenoxypolyethoxyethanol (Triton X-114). After centrifugation, the surfactant-rich phase was diluted with 0.1 M HNO3 in methanol. For optimum recovery of analytes, the influences of the analytical parameters, including pH and amounts of complexing and surfactant reagents, were investigated. Enrichment factors of 66.4 and 70.2 were obtained for the preconcentration of Zn(II) and Fe(III), respectively. The obtained results showed sufficient recoveries (>98%) for Zn(II) and Fe(III) in certified reference materials (CRMs). The proposed method was applied to the determination of Zn(II) and Fe(III) in biological (serum and urine) samples and CRMs.

Cloud point extraction of vanadium in pharmaceutical formulations, dialysate and parenteral solutions using 8-hydroxyquinoline and nonionic surfactant.

A cloud point extraction (CPE) method has been developed for the determination of trace quantity of vanadium ions in pharmaceutical formulations (PF), dialysate (DS) and parenteral solutions (PS). The CPE of vanadium (V) using 8-hydroxyquinoline (oxine) as complexing reagent and mediated by nonionic surfactant (Triton X-114) was investigated. The parameters that affect the extraction efficiency of CPE, such as pH of sample solution, concentration of oxine and Triton X-114, equilibration temperature and time period for shaking were investigated in detail. The validity of CPE of V was checked by standard addition method in real samples. The extracted surfactant-rich phase was diluted with nitric acid in ethanol, prior to subjecting electrothermal atomic absorption spectrometry. Under these conditions, the preconcentration of 50 mL sample solutions, allowed raising an enrichment factor of 125-fold. The lower limit of detection obtained under the optimal conditions was 42 ng/L. The proposed method has been successfully applied to the determination of trace quantity of V in various pharmaceutical preparations with satisfactory results. The concentration ranges of V in PF, DS and PS samples were found in the range of 10.5-15.2, 0.65-1.32 and 1.76-6.93 microg/L, respectively.

Biosorption studies on powder of stem of Acacia nilotica: Removal of arsenic from surface water.

In present study a biomass derived from the stem of Acacia nilotica has been investigated to remove As ions from surface water samples of different origins (lake, canal and river). The effects of various parameters viz. pH, biosorbent dosage, contact time and temperature on the biosorption processes were systematically studied. Experimental data were modeled by Langmuir, Freundlich and Dubinin-Radushkevich (D-R) isotherms. It was observed that As biosorption best fitted to the Langmuir and Freundlich isotherms. The mean sorption energy (E) calculated from D-R model, indicated physico-chemical biosorption. Study of thermodynamic parameters revealed the endothermic, spontaneous and feasible nature of biosorption process. The pseudo-second-order rate equation described better the kinetics of As biosorption with good correlation coefficients than pseudo-first-order equation. The biomass of A. nilotica was found to be effective for the removal of As with 95% sorption efficiency at a concentration of <200 microg/L of As solution, and thus uptake capacity is 50.8 mg As/g of biomass. The A. nilotica biomass could be used as a low-cost biosorbent for As ion removal.

Separation and preconcentration of trace amounts of aluminum ions in surface water samples using different analytical techniques.

A separation/preconcentration of aluminum (III) (Al(3+)) has been developed to overcome the problem of high matrix species, which may interfere with the determination of trace quantity of Al(3+) in natural water samples. The separation of Al(3+) in water samples was carried out from interfering cations by complexing them with 2-methyle 8-hyroxyquinoline (quinaldine) on activated silica. Whereas the separated trace amounts of Al(3+) was preconcentrated by cloud point extraction (CPE), as prior step to its determination by spectrofluorimetry (SPF) and flame atomic absorption spectrometry (FAAS). The Al(3+) react with 8-hydroxyquinoline (oxine) and then entrapped in non-ionic surfactant Triton X-114. The main factors affecting CPE efficiency, such as pH of sample solution, concentration of oxine and Triton X-114, equilibration temperature and time period for shaking were investigated in detail. The validity of separation/preconcentration of Al(3+) was checked by certified reference material of water (SRM-1643e). After optimization of the complexation and extraction conditions, a preconcentration factor of 20 was obtained for Al(3+) in 10 mL of natural water samples. The relative standard deviation for 6 replicates containing 100 microg L(-1) of Al(3+) was 5.41 and 4.53% for SPF and FAAS, respectively. The proposed method has been applied for determination of trace amount of Al(3+) in natural water samples with satisfactory results.

Separation and preconcentration of aluminum in parenteral solutions and bottled mineral water using different analytical techniques.

A new method is reported for the separation of aluminum ions [Al(III)] from interfering elements in parenteral and pharmaceutical solutions (PS) and bottled mineral water (BMW) samples, through solid-phase extraction with 2-methyl-8-hydroxyquinoline (quinaldine) adsorbed onto activated silica gel. While the enrichment step of separated Al(III) was carried out by cloud point extraction (CPE) using 8-hydroxyquinoline as complexing reagent, the resulted complex was entrapped in a non-ionic surfactant octylphenoxypolyethoxyethanol (Triton X-114). The enriched Al(III) in sample solutions were determined by spectrofluorometry (SPF) at lambda(excitation) 370 nm and lambda(emission) 510 nm, and flame atomic absorption spectrometry (FAAS) for comparative purpose. The variables affecting the complexation and extraction steps were studied and optimized. The validity of methodology was checked with certified reference material of water and standard addition method. The enrichment factor and detection limit of Al(III) for the preconcentration of 50 ml of PS and BMW were found to be 100 and 0.25 microg/L, respectively. The proposed method has been applied for the determination of trace amount of Al(III) in PS and BMW samples with satisfactory results. In PS the levels of Al(III) are above than permissible limit (25 microg/L).