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.

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.

Optimization of ultrasonic-assisted acid extraction of mercury in muscle tissues of fishes using multivariate strategy.

A simple and rapid ultrasound-assisted extraction procedure was developed for the determination of total mercury (Hg) in muscle tissues of freshwater fish species. A Plackett-Burman experimental design was used as a multivariate strategy for the evaluation of the effects of variables, such as presonication time (without ultrasonic stirring), sonication time, ultrasonic bath temperature, nitric acid concentration, hydrochloric acid concentration, and sample mass of muscle tissues. Some variables showed a significant effect on recovery, and they were further optimized by a 2(3) + star central composite design that involved 16 experiments. The validation was carried out by analysis of certified reference material DORM-2 (dog fish muscles); for comparative purposes, an acid digestion induced by microwave energy was used. Cold vapor atomic absorption spectrometry was used for the determination of total Hg. No significant differences were established between the analytical results and the certified values (paired t-test at P > 0.05). The LOD and LOQ of Hg were 0.133 and 0.445 microg/kg, respectively, which demonstrated the high sensitivity of the proposed procedure for the determination of Hg at trace levels. The Hg concentrations in the muscle tissues of 10 freshwater fish species were found in the range of 35.3-67.8 microg/kg on a dried basis, which were within the permissible limit of the World Health Organization.

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.

Optimization of cloud point extraction and solid phase extraction methods for speciation of arsenic in natural water using multivariate technique.

The simple and rapid pre-concentration techniques viz. cloud point extraction (CPE) and solid phase extraction (SPE) were applied for the determination of As(3+) and total inorganic arsenic (iAs) in surface and ground water samples. The As(3+) was formed complex with ammonium pyrrolidinedithiocarbamate (APDC) and extracted by surfactant-rich phases in the non-ionic surfactant Triton X-114, after centrifugation the surfactant-rich phase was diluted with 0.1 mol L(-1) HNO(3) in methanol. While total iAs in water samples was adsorbed on titanium dioxide (TiO(2)); after centrifugation, the solid phase was prepared to be slurry for determination. The extracted As species were determined by electrothermal atomic absorption spectrometry. The multivariate strategy was applied to estimate the optimum values of experimental factors for the recovery of As(3+) and total iAs by CPE and SPE. The standard addition method was used to validate the optimized methods. The obtained result showed sufficient recoveries for As(3+) and iAs (>98.0%). The concentration factor in both cases was found to be 40.

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).

Determination of toxic elements in infant formulae by using electrothermal atomic absorption spectrometer.

In present work concentrations of toxic elements (TEs), aluminum (Al), cadmium (Cd), and lead (Pb) in seventeen imported samples of infant milk-based (IMF) and infant soy-based formulae (ISF), were measured, to evaluate whether the intakes of understudy TEs accomplished within recommended permissible levels. The TEs were analyzed by electrothermal atomic absorption spectrometer, prior to microwave induced acid digestion. The validity of methodology was tested by simultaneously analyzing certified reference material and standard addition method. It was observed that ISF contains higher concentration of understudy toxic analytes as compared to IMF. The all three TEs, Al, Cd and Pb were detected in different branded infant formulae, in the range of (1070-2170), (10.5-34.4), and (28.7-119) microg/kg, respectively. The estimated intakes of TEs as microg/kg/week for infants (>1year) through milk formulae are well below the recommended tolerable levels of these elements.

Heavy metal accumulation in different varieties of wheat (Triticum aestivum L.) grown in soil amended with domestic sewage sludge.

The concentrations of heavy metals (HMs) in plants served to indicate the metal contamination status of the site, and also revealed the abilities of various plant species to take up and accumulate them from the soil dressed with sewage sludge. A study to comprehend the mobility and transport of HMs from soil and soil amended with untreated sewage sludge to different newly breaded varieties of wheat (Anmol, TJ-83, Abadgar and Mehran-89) in Pakistan. A pot-culture experiment was conducted to study the transfer of HMs to wheat grains, grown in soil (control) and soil amended with sewage sludge (test samples). The total and ethylenediaminetetraaceticacid (EDTA)-extractable HMs in agricultural soil and soil amended with domestic sewage sludge (SDWS) and wheat grains were analysed by flame atomic absorption spectrometer/electrothermal atomic absorption spectrometer, prior to microwave-assisted wet acid digestion method. The edible part of wheat plants (grains) from test samples presented high concentration of all HMs understudy (mgkg(-1)). Significant correlations were found between metals in exchangeable fractions of soil and SDWS, with total metals in control and test samples of wheat grains. The bio-concentration factors of all HMs were high in grains of two wheat varieties, TJ-83 and Mehran-89, as compared to other varieties, Anmol and Abadgar grown in the same agricultural plots.

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.

Speciation of heavy metals in untreated sewage sludge by using microwave assisted sequential extraction procedure.

A fast microwave assisted extraction procedure was developed and optimized for their eventual exploitation in the three-stage sequential extraction procedure proposed by modified BCR protocol (the community Bureau of Reference now the European Union "Measurement and Testing Programme"). The effects of the microwave treatment on the extraction of Cd, Cr, Cu, Ni, Pb and Zn from untreated sewage sludge collected from Hyderabad city (Pakistan) were compared with those obtained from sequential BCR extraction procedure. In sequential BCR method, each extraction step takes 16 h, where as with the use of compromised microwave conditions, extraction steps could be completed in about 120 s, for each step, respectively. Extractable Cd, Cr, Pb and Ni obtained by both comparable methodologies were measured by electrothermal atomic absorption spectrometry (ETAAS), while for Cu and Zn flame atomic absorption spectrometry (FAAS) was used. The validations of both extraction techniques were compared by the analysis of certified reference material of soil amended with sewage sludge (BCR 483). The results of the partitioning study of untreated waste water sewage sludge, indicate that more easily mobilized forms (step 1) were predominant for Cd, Ni and Zn (28.3, 28.4 and 43.7%), in contrast, the largest amount of Cd and Pb (66.4 and 72.8%) was associated with the iron/manganese oxide while Cr and Ni (71.2 and 38.7%) in organic matter/sulphide fractions. The overall metal recoveries in steps 1-3 (excluding residual step) were 95.3-104% of those obtained with the sequential BCR protocol. The accuracy of the proposed microwave extraction method (expressed as %R.S.D.) was lower than 10% for all metals.