Bioaccumulation of arsenic and fluoride in vegetables from growing media: health risk assessment among different age groups.

The current study was conducted to evaluate the arsenic (As) and fluoride (F-) concentrations in growing media (stored rainwater and soil), of district Tharparkar, Pakistan. The bioaccumulation/transportation of As and F from growing media to different types of vegetables (wild cucumis, Indian squish and cluster bean) was evaluated. Total concentrations of As and F- in stored rainwater samples were observed up to 585 µg/L and 32.4 mg/L, respectively, exceeding many folds higher than WHO provisional guideline values. The As and F- contents in soil samples of nine agricultural sites were found in the range of 121-254 mg/kg and 115-478 mg/kg, respectively. The highest contents of As and F- were observed in wild cucumis as compared to Indian squish and cluster bean (p < 0.05), grown in the same agricultural field. The bioaccumulation factors of As and F- were to be > 4.00, indicating the high rate of transportation of As and F- from growing media to vegetables. A significant positive correlation of As and F- in vegetables with their concentrations in soil and water was observed (r > 0.60 with p < 0.05). The risk assessment elucidated that the population of different age group consuming local vegetables and drinking water contaminated with As and F- may have adverse health effects.

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).

Correlation of Arsenic Levels in Smokeless Tobacco Products and Biological Samples of Oral Cancer Patients and Control Consumers.

It has been extensively reported that chewing of smokeless tobacco (SLT) can lead to cancers of oral cavity. In present study, the relationship between arsenic (As) exposure via chewing/inhaling different SLT products in oral cancer patients have or/not consumed SLT products was studied. The As in different types of SLT products (gutkha, mainpuri, and snuff) and biological (scalp hair and blood) samples of different types of oral cancer patients and controls were analyzed. Both controls and oral cancer patients have same age group (ranged 30-60 years), socio-economic status, localities, and dietary habits. The concentrations of As in SLT products and biological samples were measured by electrothermal atomic absorption spectrophotometer after microwave-assisted acid digestion. The validity and accuracy of the methodology were checked by certified reference materials. The resulted data of present study indicates that the concentration of As was significantly higher in scalp hair and blood samples of oral cancer patients than those of controls (p<0.001). It was also observed that the values of As were two- to threefolds higher in biological samples of controls subjects, consuming SLT products as compared to those have none of these habits (p>0.01). The intake of As via consuming different SLT may have synergistic effects, in addition to other risk factors associated with oral cancer.

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).

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).

Evaluated the levels of lead and cadmium in scalp hair of adolescent boys consuming different smokeless tobacco products with related to controls.

The present study was aimed to evaluate the cadmium (Cd) and lead (Pb) levels in the scalp hair samples of adolescent boys age ranged 12-15 years, chewing different smokeless tobacco (SLT) products. For comparative purpose, boys of the same age group who did not consume any SLT products were selected as referents. The concentrations of Cd and Pb in SLT products and the scalp hair samples were measured by electrothermal atomic absorption spectrophotometer (ETAAS) after microwave-assisted acid digestion. The validity and accuracy of the methodology were checked by certified reference materials (CRMs). The difference between experimental and certified values of both elements was not significant (p > 0.05). The resulted data indicated that the adolescent boys who consumed different SLT products have two- to threefold higher levels of Cd and Pb in the scalp hair samples as compared to the referent boys (p < 0.01). The adolescent chewing different SLT products have 82.2-110 and 60.6-94.5% higher levels of Cd and Pb, respectively, in their scalp hair as related to the referents.

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).