Sadaf Sadia Arain

Evaluation of high levels of fluoride, arsenic species and other physicochemical parameters in underground water of two sub districts of Tharparkar, Pakistan: A multivariate study

In present study total arsenic, inorganic arsenic species and fluoride ion contaminations in underground water of Diplo and Chachro sub district of Tharparkar, Pakistan were investigated. The concentrations of total As, inorganic As species, F(-) and others physicochemical parameters were reported in terms of basic statistical parameters, principal component analysis, cluster analysis, sodium absorption ratio and saturation indices. The As(3+) was determined by cloud point extraction using ammonium pyrrolidinedithiocarbamate (APDC) as complexing reagent, and complex was 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 HNO(3) in methanol. While total inorganic arsenic (iAs) was determined by solid phase extraction using titanium dioxide (TiO(2)) as an adsorbent, after centrifugation, the solid phase was prepared to be slurry for determination. The extracted As species were determined by electrothermal atomic absorption spectrometry. The concentration of As(5+) in the water samples was calculated by the difference of the total iAs and As(3+), while F(-) and other anions were determined by ion chromatography. The positive correlation of F(-) and As species with Na(+) and HCO(3)(-) showed that the water with high salinity and alkalinity stabilized the As species and F(-) in the groundwater. The positive correlation (r = 0.640, p = 0.671) was observed between total As and it species with F(-). Results showed that underground water samples of these two areas of Tharparkar were severely contaminated with arsenic and fluoride ion, which are exceeded the World Health Organization (WHO) provisional guideline value, and United States Environmental Protection Agency, maximum contaminant level of 0.01 mg/L and 1.5 mg/L, respectively.

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).

Simultaneous preconcentration of toxic elements in artificial saliva extract of smokeless tobacco product, mainpuri by cloud point extraction method.

It has been extensively investigated that smokeless tobacco chewing can lead mainly to inflammation of oral cavity. In present study, the total and artificial saliva extracted toxic elements, arsenic, cadmium, nickel and lead were estimated in smokeless tobacco product, mainpuri. Cloud point extraction has been used for the preconcentration of arsenic, cadmium, nickel and lead in artificial saliva extract, using complexing reagent, ammonium pyrrolidinedithiocarbamate. Total and extractable toxic elements were measured by electrothermal atomic absorption spectrometry. The chemical variables of cloud point extraction were optimized. The validity of methodology was tested by simultaneously analyzing certified reference material (Virginia tobacco leaves) and spike recovery test. The artificial saliva extractable levels of arsenic, cadmium, nickel and lead ranged from 15-22, 45-70, 35-58, and 18-32%, respectively, of total elemental contents in mainpuri samples. It was estimated that intake of 10g of different brands of mainpuri contributing the 5.88, 55.0, 45.0 and 40.3% of the provisional maximum tolerable daily intake for arsenic, cadmium, nickel and lead, respectively for adults of ~60kg.

Exposure of children to arsenic in drinking water in the Tharparkar region of Sindh, Pakistan

Humans can be exposed to arsenic (As) through air, drinking water, and food. The aim of this study was to calculate the hazard quotient (HQ) of As, based on its concentration in drinking water and the scalp hair of children (males) belonging to two age groups (5-10 and 11-14 years) who consumed water contaminated with different concentrations of As. The water samples were collected from As-exposed and nonexposed areas, which were classified as low-exposed (LE), high-exposed (HE), and nonexposed (NE) areas. The total concentration of inorganic As (iAs) and its species (As(III) and As(V)) in water samples of all selected areas was determined by advanced extraction methods. For purposes of comparison, the total As level was also determined in all water samples. The resulting data indicated that the predominant inorganic As species in groundwater samples was arsenate (As(V)). The As concentrations in drinking water of LE and HE areas were found to be 2.6-230-fold higher than the permissible limit for drinking water established by the World Health Organization (2004). However, the As levels in drinking water of the NE area was within the permissible limit (<10 μg/L). The As levels in the scalp hair samples from boys of NE, LE, and HE areas ranged from 0.16 to 0.36, 0.36 to 0.83, and 11.5 to 31.9 mg/kg, respectively. A significant, positive correlation was observed between the As levels in drinking water and scalp hair samples of children from the HE area, compared with the other two groups (p>0.01). The As toxicity risk assessment based on HQ for the NE, LE, and HE areas corresponded to <10, ≥ 10, and >10, respectively. These HQ values indicated the noncarcinogenic, less carcinogenic, and highly carcinogenic exposure risks faced by children from the NE, LE, and HE areas, respectively. It can be concluded that children consuming the groundwater of the LE (Khairpur Mirs) and HE (Tharparkar) areas of Pakistan are at a potential risk of chronic As toxicity.

Determination of nickel in blood and serum samples of oropharyngeal cancer patients consumed smokeless tobacco products by cloud point extraction coupled with flame atomic absorption spectrometry

AbstractOropharyngeal cancer is a significant public health issue in the world. The incidence of oropharyngeal cancer has been increased among people who have habit of chewing smokeless tobacco (SLT) in Pakistan. The aim of present study was to evaluate the concentration of nickel (Ni) in biological samples (whole blood, serum) of oral (n = 95) and pharyngeal (n = 84) male cancer patients. For comparison purposes, the biological samples of healthy age-matched referents (n = 150), who consumed and did not consumed SLT products, were also analyzed for Ni levels. As the Ni level is very low in biological samples, a preconcentration procedure has been developed, prior to analysis of analyte by flame atomic absorption spectrometry (FAAS). The Ni in acid-digested biological samples was complexed with ammonium pyrrolidinedithio carbamate (APDC), and a resulted complex was extracted in a surfactant Triton X-114. Acidic ethanol was added to the surfactant-rich phase prior to its analysis by FAAS. The chemical variables, such as pH, amounts of reagents (APDC, Triton X-114), temperature, incubation time, and sample volume were optimized. The resulted data indicated that concentration of Ni was higher in blood and serum samples of cancer patients as compared to that of referents who have or have not consumed different SLT products (p = 0.012–0.001). It was also observed that healthy referents who consumed SLT products have two to threefold higher levels of Ni in both biological samples as compared to those who were not chewing SLT products (p < 0.01). Figureᅟ

Temperature-controlled ionic liquid-based ultrasound-assisted microextraction for preconcentration of trace quantity of cadmium and nickel by using organic ligand in artificial saliva extract of smokeless tobacco products.

A new approach was developed for the preconcentration of cadmium (Cd) and nickel (Ni) in artificial saliva extract of dry snuff (brown and black) products using temperature-controlled ionic liquid-based ultrasound-assisted dispersive liquid-liquid microextraction (TIL-UDLLμE) followed by electrothermal atomic absorption spectrometry (ETAAS). The Cd and Ni were complexed with ammonium pyrrolidinedithiocarbamate (APDC), extracted in ionic liquid drops, 1-butyl-3-methylimidazolium hexafluorophosphate [C4MIM][PF6]. The multivariate strategy was applied to estimate the optimum values of experimental variables influence the % recovery of analytes by TIL-UDLLμE method. At optimum experimental conditions, the limit of detection (3s) were 0.05 and 0.14μgL(-1) while relative standard deviations (% RSD) were 3.97 and 3.55 for Cd and Ni respectively. After extraction, the enhancement factors (EF) were 87 and 79 for Cd and Ni, respectively. The RSD for six replicates of 10μgL(-1) Cd and Ni were 3.97% and 3.55% respectively. To validate the proposed method, certified reference material (CRM) of Virginia tobacco leaves was analyzed, and the determined values of Cd and Ni were in good agreement with the certified values. The concentration of Cd and Ni in artificial saliva extracts corresponds to 39-52% and 21-32%, respectively, of the total contents of both elements in dry brown and black snuff products.

Preconcentration and determination of manganese in biological samples by dual-cloud point extraction coupled with flame atomic absorption spectrometry

An efficient, innovative preconcentration method using dual-cloud point extraction (d-CPE) was developed for the analysis of trace levels of manganese (Mn2+) in biological samples (scalp hair) prior to coupling with flame atomic absorption spectrometry (FAAS). In the first step of d-CPE, Mn2+ was complexed with 1-(2-pyridylazo)-2-naphthol (PAN), which was subsequently entrapped in a nonionic surfactant (Triton X-114). In the second step, the entrapped metal complex in the surfactant-rich phase was treated with aqueous nitric acid solution and heated; the studied metal ions were back-extracted again into aqueous phase. The aqueous phase was subjected to FAAS using conventional nebulization. The validity of the proposed method was verified by the analysis of Mn2+ in a certified sample of scalp hair (CRM) by both d-CPE and conventional CPE procedures. The enhancement factor of Mn2+ was found to be 46. The proposed method was successfully applied to the determination of Mn2+ in acid-digested scalp hair samples of Parkinsons patients and healthy referents.

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-β-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).

Exposures of lead to adolescent workers in battery recycling workshops and surrounding communities

In the present study, the environmental and occupational exposure of lead (Pb) has been assessed by analyzing the whole-blood samples of early adolescents (boys) aged 12–15 years working for the past 1–3 years in battery recycling workshops (BRW). For comparative purpose, boys of the same age group residing in the vicinity of BRW (exposed non-workers) and who lived in domestic areas devoid of any industrial activity (referents boys) were selected. The blood samples were analyzed for Pb, along with biochemical parameters of blood. Both biological samples were oxidized by acid in a microwave oven before determination of Pb by graphite furnace atomic absorption spectrometry. The mean value of Pb concentration in blood samples of working boys was threefold higher as compared with referent boys. The significant negative correlations of blood Pb level with % Hb (r=−0.862) were observed in working boys.

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.