Evaluate the Work-Related Exposure of Vanadium on Scalp Hair Samples of Outdoor and Administrative Workers of Oil Drilling Field: Related Health Risks.

Petrochemical facilities, including oil well drilling, are discharging resources of extensive noxious waste into the environment. The workers in different sections might be exposed to vanadium (V) through different routes (groundwater and soil), which is linked with extensive physiological disorders, hypertension, respiratory disorders, anemia, skin, and gastrointestinal disorders. This study determined the contents of V in a biological sample (scalp hair) of workers of different categories (outdoor and office workers) in an oil drilling field in Sindh, Pakistan. The environmental samples, groundwater, bottled mineral water, and soil samples were also analyzed for V. For comparative purposes, the scalp hair of age-matched male subjects residing in domestic areas of Hyderabad city, Pakistan, was also analyzed. Generally, the concentrations of V in groundwater near the oil drilling field and drilled soil illustrated significant variations. The results show that the vanadium concentration in the scalp hair of non-exposed referents (controls) and office workers (exposed referents) was 62% and 45% lower than those observed for outdoor drilling and cleaning mud workers. It was observed that high exposure to V in outdoor workers might be linked with different physiological disorders such as anemia, eye problems, and bronchial disorders.

Elemental Concentration in the Biological Samples of Pakistani Male Breast Cancer Patients.

BACKGROUND: Breast cancer is an uncommon (rare) disease in men, approximately 1% of the total breast cancer cases in the world. By reason of the rare occurrence, there is no clinical or hospital study giving the information about the essential trace and toxic elements in the biological samples of male breast cancer patients. METHODS: The aim of current study was to estimate association among essential trace {zinc (Zn), iron (Fe) and copper (Cu)} and toxic {cadmium (Cd) and lead (Pb)} elements in human biological samples particularly blood, serum, scalp hair, of male breast cancer patients (n = 14, age range 52 - 58 years) residents of Hyderabad, Pakistan. For comparative purposes, the biological samples of referent persons (n = 37) of the same age groups were also be analyzed. Microwave oven mediated digestion method was employed, and digestion of samples was carried out with the help of 2:1 mixture solution of HNO3 (65%) and H2O2 (30%). Atomic absorption spectrometry was employed for the determination of elemental concentrations from the microwave oven employed digested samples. RESULTS: The found average of essential elements (zinc, iron, and copper) in samples of male breast cancer patients was found to be lower, while cadmium and nickel were found to be higher, when compared with samples from referents (p < 0.001). CONCLUSIONS: These data will be helpful for treatment of male breast cancer patients to improve his health and life.

Adverse impact of occupational exposure on Laborers of cement industry have scalp psoriasis and Pityriasis amiantacea with deficiency of zinc and selenium: impact of mineral supplement.

The relationship between occupational exposure and different skin diseases including scalp psoriasis and Pityriasis amiantacea has been studied. The information about imbalance of essential trace elements in psoriatic patients is still scarce. In the present follow-up study, the scalp hair and blood samples of patients (labors of cement factory) have different skin disorders (plaque's psoriasis and Pityriasis amiantacea) and were analyzed for zinc (Zn) and selenium (Se) before and after treatment with mineral supplements. For comparative purposes, both biological samples of referents who do not have any skin disease (office workers and labors of cement industry) were also analyzed for Zn and Se using an atomic absorption spectrometer. The result indicates a significant decrease in the concentrations of Se and Zn in both biological samples of patients with scalp psoriasis and P. amiantacea as compared with referents/controls, whereas the referent labor has not any skin disease with 15-25% lower values of both essential trace elements as compared to office worker, possibly due to poor diet.

Exposure of heavy metals in coal gangue soil, in and outside the mining area using BCR conventional and vortex assisted and single step extraction methods. Impact on orchard grass.

It was investigated that toxic metals (cadmium and lead) enhanced in coal gangue soil used for the reclamation of soil, creates adverse impacts on atmosphere. Presently the chemical fractionation of toxic metals in coal, inner and outer coal gangue soil samples of Lakhra coalfield were studied along with the impact on the orchard grass grown on coal gangue soil in a subside land of the coal mining area. The BCR sequential extraction scheme (BCR-SES) was carried out to determine the different chemical profiles of heavy metals in coal and coal gangue soil samples. For comparative purpose time saving conventional single step extraction (CSE) and vortex assisted single step extraction (VSE) schemes based on same working setting used BCR extraction scheme. The all three procedures were validated by a certified soil sample (BCR 483) and standard addition method in real samples. The total Cd and Pb in coal, soil and grass samples were determined prior to oxidize by acid mixture. The separation of each fraction of Cd, and Pb in all types of environmental samples by VSE could be completed in 30-120 s. The extracted Cd and Pb concentrations in reducible fractions by CSE and VSE extraction procedure were 2.5-5% higher than those values gained through BCR-SES. About 71 and 50% of Cd and Pb in coal samples were observed in acid soluble, reducible and oxidizable fraction, respectively, whilst rest of Cd and Pb (29 and 50%) were found in residual phase. The orchard grass (Dactylis glomerata) grown on land reclaimed with OSG was analysed, the bioaccumulate Cd and Pb may create adverse impacts on grazing cattle.

Evaluate the effect of cadmium on levels of zinc in scalp hair and blood samples of smoker and nonsmoker psoriatic patients at different stage.

Psoriasis, a skin inflammatory disease, originates from dysregulated interactions of the immune system and environmental factors. In the present study, cadmium (Cd) and zinc (Zn) were analyzed in biological samples (blood and scalp hair) of smoker and nonsmoker males who have mild and severe psoriasis. The patients were evaluated according to criteria based on the standard clinical diagnosis and classified into mild and severe psoriasis groups using the Psoriasis Area Severity Index (PASI) score. Both elements were determined by atomic absorption spectrometry after matrix oxidation. In smoker psoriatic patients, the level of Cd in biological samples was significantly increased. The Zn was significantly decreased in smoker mild and severe psoriatic patients as related to nonsmokers' referents and patients. The resulted data indicated that the levels of Zn in smoker referents were about 5.0% lower than nonsmoker's referents. While the concentrations of Zn in blood samples of nonsmoker's mild and severe psoriatic patients have 17.8 to 33.3% lower than nonsmoker's referents. The results indicate that the level of Cd in blood samples of referent smokers has ≥ 25% than nonsmokers, whereas the psoriatic patients at different stages have two- to threefold higher Cd in both biological samples.

Volatilization of toxic elements from coal samples of Thar coal field, after burning at different temperature and their mobility from ash: Risk assessment.

In present study, the volatilization of arsenic (As), cadmium (Cd), mercury (Hg) and lead (Pb) by the burning of coal samples in the electric furnace was evaluated. The coal samples were obtained from different blocks of newly developed Thar coal field, Pakistan. The replicate coal samples were heated/burned in an electric furnace at laboratory scale for three temperature intervals (200, 400 and 900 °C). The ash obtained after each temperature intervals were analyzed for selected toxic elements. The resulted data indicated that the total contents of As, Cd, and Pb in coal samples of block X and XI were found in the range of 16.8-18.5, 4.21-4.72, and 14.2-18.8 mg/kg, respectively. Whereas, 67.8-79.7%, 34.3-36.8% and 9.89-10.8% of As, Cd, and Pb, respectively, were volatized out after combustion of coal samples at 900 °C. The total contents of Hg in selected coal samples of block X and XI were observed in the range of 0.985-1.46 and 0.992-1.41 mg/kg, respectively. The contents of Hg volatilized out via burning in a furnace at 200 °C and 400 °C, were observed in the range of 32.0-36.5% and >91.0% of its total contents, respectively, whereas at 900 °C, it was not detected in ash. The partitioning and mobility of studied toxic elements in residue termed as (laboratory made ash) obtained after burning at 900 °C, was carried out by three-step sequential extraction scheme. The resulted data of present study will give a better knowledge about the quality of coal and its burning product, which may help to take measure to reduce the adverse effects on the environment in future.

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.

Vortex-Assisted Modified Dispersive Liquid-Liquid Microextraction of Trace Levels of Cadmium in Surface Water and Groundwater Samples of Tharparkar, Pakistan, Optimized by Multivariate Technique.

A simple vortex-assisted modified dispersive liquid-liquid microextraction procedure is proposed for the enrichment of cadmium (Cd+2) in surface (stored rainwater) and groundwater of the Tharparkar district in Pakistan, before analysis by flame atomic absorption spectrometry. Ammonium pyrrolidinedithiocarbamate was used as a ligand to make a hydrophobic complex of Cd+2, which was extracted in an ionic liquid (1-butyl-3-methylimidazolium hexafluorophosphate), and the nonionic surfactant Triton X-114 was applied as a dispersing medium. The contents of tubes were shaken for different time intervals on a vortex mixer to enhance extraction efficiency. A multivariate strategy was used to simultaneously evaluate seven factors including, concentration of the complexing reagent, pH, amounts of ionic liquid and Triton X-114, vortex shaking time, centrifugation time and extracting solution for their influence on the percentage recovery of the analyte. The important variables were further optimized by central composite design. The preconcentration factor and LOD were observed as 76.9 and 0.048 µg/L, respectively. The Certified Reference Material SRM1643e was used to check the validity of the developed method, and the RSD was found to be 4.02%. The proposed technique was successfully applied for the enrichment of Cd+2 in groundwater and surface water samples from the southeastern part of Pakistan. The observed results revealed that the concentration of Cd+2 in groundwater was higher than the World Health Organization recommended value of 3 µg/L for drinking water. For adults weighing approximately 60 kg, consumption of groundwater for drinking and other domestic purposes would provide levels of Cd+2 that are 2- to 3-fold higher than the provisional maximum tolerable daily intake.

Ultrasonic-energy enhance the ionic liquid-based dual microextraction to preconcentrate the lead in ground and stored rain water samples as compared to conventional shaking method.

An efficient preconcentration technique based on ultrasonic-assisted ionic liquid-based dual microextraction (UA-ILDµE) method has been developed to preconcentrate the lead (Pb+2) in ground and stored rain water. In the current proposed method, Pb+2 was complexed with a chelating agent (dithizone), whereas an ionic liquid (1-butyl-3-methylimidazolium hexafluorophosphate) was used for extraction purpose. The ultrasonic irradiation and electrical shaking system were applied to enhance the dispersion and extraction of Pb+2 complex in aqueous samples. For second phase, dual microextraction (DµE phase), the enriched Pb+2 complex in ionic liquid, extracted back into the acidic aqueous solution and finally determined by flame atomic absorption spectrometry. Some major analytical parameters that influenced the extraction efficiency of developed method, such as pH, concentration of ligand, volume of ionic liquid and samples, time of shaking in thermostatic electrical shaker and ultrasonic bath, effect of back extracting HNO3 volume, matrix effect, centrifugation time and rate were optimized. At the sample volume of 25mL, the calculated preconcentration factor was 62.2. The limit of detection of proposed procedure for Pb+2 ions was found to be 0.54µgL-1. The validation of developed method was performed by the analysis of certified sample of water SRM 1643e and standard addition method in a real water sample. The extraction recovery of Pb+2 was enhanced≥2% with shaking time of 80s in ultrasonic bath as compared to used thermostatic electrical shaker, where for optimum recovery up to 10min was required. The developed procedure was successfully used for the enrichment of Pb+2 in ground and stored rain water (surface water) samples of an endemic region of Pakistan. The resulted data indicated that the ground water samples were highly contaminated with Pb+2, while some of the surface water samples were also have higher values of Pb+2 than permissible limit of WHO. The concentration of Pb+2 in surface and ground water samples was found in the range of 17.5-24.5 and 25.6-99.1µgL-1 respectively.

Interaction of Lead with Calcium, Iron, and Zinc in the Biological Samples of Malnourished Children.

Interaction between toxic and essential elements is of particular interest, because the deficiency of essential element can dramatically increase the absorption rate of toxic metals inside the body. This study was conducted to evaluate the possible correlation of lead (Pb) with calcium (Ca), iron (Fe), and zinc (Zn) in biological samples (whole blood and scalp hair) of malnourished children (MNC). For comparative purposes, age-matched, well-nourished children (WNC) were selected. The concentrations of understudy elements were analyzed by atomic absorption spectrophotometry after microwave acid digestion. The accuracy of the methodology, as well as its its validity and efficiency, was checked through certified reference material of whole blood and scalp hair. The result indicates that the MNC have a twofold higher level of Pb, while the levels of essential elements (Ca, Fe, and Zn) were onefold to twofold lower as compared to the WNC (p < 0.05). Significant negative correlations of Pb with Ca, Fe, and Zn were found in the studied malnourished population at p < 0.05. Further research studies are required to elucidate the role of these metals and the mechanism of interaction inside the body.

Ultrasonic energy enhanced the efficiency of advance extraction methodology for enrichment of trace level of copper in serum samples of patients having neurological disorders.

An innovative dual dispersive ionic liquid based on ultrasound assisted microextraction (UDIL-µE), for the enrichment of trace levels of copper ion (Cu2+), in serum (blood) of patients suffering from different neurological disorders. The enriched metal ions were subjected to flame atomic absorption spectrometry (FAAS). In the UDIL-µE method, the extraction solvent, ionic liquid, 1-butyl-3-methylimidazolium hexafluorophosphate [C4mim][PF6], was dispersed into the aqueous samples using an ultrasonic bath. The(PAN) 1-(2-pyridylazo)-2-naphthol was used as ligand for the complexation of Cu ion in IL (as extracting solvent). The various variables such as sonication time, pH, concentration of complexing agent, time and rate of centrifugation, IL volume that affect the extraction process were optimized. The enhancement factor (EF) and detection limit (LOD) was found under favorable condition was 31 and 0.36µgL-1, respectively. Reliability of the proposed method was checked by relative standard deviation (%RSD), which was found to be <5%. The accuracy of developed procedure was assured by using certified reference material (CRM) of blood serum. The developed procedure was applied successfully to the analysis of concentration of Cu ion in blood serum of different neurological disorders subjects and referents of same age group. It was observed that the levels of Cu ion was two folds higher in serum samples of neurological disorders patients as related to normal referents of same age group.

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).

Temperature controlled ionic liquid-based dispersive micro-extraction using two ligands, for determination of aluminium in scalp hair samples of Alzheimer's patients: a multivariate study.

A green and sensitive temperature controlled dispersive liquid-liquid microextraction (TIL-DLLME) methodology based on the application of ionic liquid 1-butyl-3-methylimidazolium hexafluorophosphate, [C4mim][PF6], as an extractant solvent was proposed for the preconcentration of trace levels of aluminium (Al(3+)) in scalp hair samples of Alzheimer's (AD) patients, prior to analyzing by flame atomic absorption spectrometry (FAAS). The Al(3+) was complexed with 8-hydrooxyquinoline (oxine) (L1) and 3,5,7,2'-4' pentahydroxy flavone (morin) (L2) separately and then extracted by IL at temperature (50±2.0°C). Some effective factors that influence the TIL-DLLME efficiency such as pH, ligands concentrations, volume of IL, ionic strength, and incubation time were investigated and optimized by multivariate analysis. In the optimum experimental conditions, the limit of detection (3s) and enhancement factor were 0.56 µg L(-1), 0.64 µg L(-1) and 85, 73 for both ligands, respectively. The relative standard deviation (RSD) for six replicate determinations of 100 µg L(-1) Al(3+) complexed with oxine and morin were found to be 3.88% and 4.74%, respectively. The developed method was validated by the analysis of certified reference material of human hair (NCSZC81002).and applied satisfactorily to the determination of Al(3+) in acid digested scalp hair samples of AD patients and healthy controls. The resulted data shows significant higher level in scalp hair samples of AD male patients with related to referents of same age and socioeconomic status.

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).