Biosorptive removal of inorganic arsenic species and fluoride from aqueous medium by the stem of Tecomella undulate.

Simultaneous removal of fluoride (F(-)), inorganic arsenic species, As(III) and As(V), from aqueous samples has been performed using an economic indigenous biosorbent (Stem of Tecomella undulata). The inorganic As species in water samples before and after biosorption were determined by cloud point and solid phase extraction methods, while F(-) was determined by ion chromatography. Batch experiments were carried out to evaluate the equilibrium adsorption isotherm studies for As(III), As(V) and F(-) in aqueous solutions. Several parameters of biosorption were optimized such as pH, biomass dosage, analytes concentration, time and temperature. The surface of biosorbent was characterized by SEM and FTIR. The FTIR study indicated the presence of carbonyl and amine functional groups which may have important role in the sorption/removal of these ions. Thermodynamic and kinetic study indicated that the biosorption of As(III), As(V) and F(-) were spontaneous, exothermic and followed by pseudo-second-order. Meanwhile, the interference study revealed that there was no significant effect of co-existing ions for the removal of inorganic As species and F(-) from aqueous samples (p > 0.05). It was observed that the indigenous biosorbent material simultaneously adsorbed As(III) (108 µg g(-1)), As(V) (159 µg g(-1)) and F(-) (6.16 mg g(-1)) from water at optimized conditions. The proposed biosorbent was effectively regenerated and efficiently used for several experiments, to remove the As(III), As(V) and F(-) from real water sample collected from endemic area of Pakistan.

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).

Co-exposure of arsenic and cadmium through drinking water and tobacco smoking: risk assessment on kidney dysfunction.

The combined exposure of arsenic (As) and cadmium (Cd) causes more pronounced renal toxicity. The study aimed to evaluate the level of As and Cd in biological samples (blood and urine) of adults males, age ranged (30-50 years) exposed referent (ER) and exposed kidney patients (EKP), consumed contaminated drinking water of lake and smoking local cigarettes manufactured by tobacco plants grown on agricultural soil, irrigated with contaminated lake water. For comparative purpose age matched nonexoposed referent (NR) and nonexposed kidney patient (NKP), consumed municipal treaded water and smoking branded cigarette were also selected. The As and Cd levels in drinking water, biological samples, tobacco of branded and nonbranded cigarettes were analyzed using electrothermal atomic absorption spectrometry. The As and Cd concentrations in lake water were higher than the permissible limit recommended by the World Health Organization for drinking water. The As and Cd levels in local cigarette tobacco were found to be 3- to 4-folds higher than branded cigarettes. The biochemical parameters especially urinary N-acetyl-ß-glucosaminidase (NAG) of ER, EKP, ER, and EKP subjects were studied as a biomarkers of renal dysfunction. The NAG values were found to be higher in EKP as compared to NKP (p < 0.01). The linear regressions showed higher correlations between As and Cd concentrations in water versus blood and urine samples of EKP (r = 0.71-0.78 and 0.68-0.72), as compared to NKP (p < 0.05).

Fluoride and arsenic exposure through water and grain crops in Nagarparkar, Pakistan.

The aim of present study was to simultaneously estimate the arsenic (As) and fluoride (F(-)) concentrations in irrigated surface water, soil and grain crops of Nagarparkar, Pakistan during 2010-2012. The As and F(-) were analyzed by hydride generation atomic absorption spectrometer and ion selective electrode, respectively. Total arsenic (As(T)) and F(-) in irrigated surface water samples were found in the range of 360-683 µg L(-1) and 18.5-35.4 mg L(-1), respectively. While As(T) and F(-) concentrations in agriculture soil samples were observed in the range of 110-266 and 125-566 mg kg(-1), respectively. The water extractable As and F(-) were found 3-4% of total concentration of these in soils. The As(T) concentration was higher in kidney been (KB) as compared to pearl millet (PM) and green gram (GG), whereas GG had higher F(-) levels as compared to other two grain crops (p<0.05). The KB samples grown in nine sites shows BCF of As in the range of 0.018-0.038. The GG has higher BCF of F(-) as compared to KB and PM (p<0.05) grown in all sites. The exposure dose and risk factor of As and F(-) were obtained by estimated daily intake (EDI) and hazardous index (HI). It was found that all understudy age groups were at the severe risk of arsenicosis and fluorosis, but the severity is higher in younger age group (7-15 years) as compared to elder groups (p<0.05).

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.

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.

Speciation of heavy metals in sediment by conventional, ultrasound and microwave assisted single extraction methods: a comparison with modified sequential extraction procedure.

Sequential extraction procedure proposed by the European Standards, Measurements and Testing (SM&T) Program, formerly the Community Bureau of Reference (BCR), has been applied for the heavy metals (HMs) partitioning in fresh water lake sediment samples. The results obtained by conventional sequential extraction BCR method (SEB) for Cd, Cu, Cr, Ni, Pb and Zn were compared with those estimated from three alternative single extractions, conventional (CSE), ultrasonic (USE) and microwave assisted (MSE), using identical operating conditions applied in each individual BCR fraction and validated by the CRM BCR 701. Extractable HMs contents obtained by all compared methodologies were measured by atomic absorption spectrometery. With the use of compromised sonication and microwave conditions, steps 1-3 of the sequential extraction (excluding the hydrogen peroxide digestion in step 3) could be completed between 15-30 min using ultrasonic bath, while 60-120 s were required for MSE. The total extractable metal contents obtained by three single extractions ranged from 75.1% to 114.0% except Cr in first step, which was extracted (125.3%) by MSE method as compared to those obtained by SEB procedure. The precision of the proposed BCR single extraction methods (expressed as RSD%) was found in the range of (3.99-9.6%) for all metals.