Evaluate the aluminum concentrations in whey milk samples of cows from different areas using deep eutectic solvent-based ultrasound-assisted dispersive liquid-liquid microextraction method.

This study investigates the contamination of cow milk with aluminum (Al) and its potential health implications, particularly for children. Cow milk samples were collected from both nonexposed and exposed areas in Sindh, based on the source of livestock drinking water (fresh canals and groundwater). An environmental friendly deep eutectic solvent (DES) was used with ultrasonic-assisted dispersive liquid-liquid microextraction (UDLLµE) to enrich trace amounts of Al in whey milk and water samples. The enriched samples were then analyzed using inductively coupled plasma optical emission spectrometry. Certified reference materials were employed to validate the methodology, and the experimental results exhibited acceptable conformity. The DES-based dispersive liquid-liquid microextraction method was environmental friendly, devoid of acids and oxidizing agents, and used safe and inexpensive components for routine trace metal analysis in diverse samples. The resulting data revealed that Al in whey milk samples was observed in the range of 31-45 %, corresponding to (160-270) µg L-1 and (700-1035) µg L-1 in nonexposed and exposed whole cow milk samples, respectively. Additionally, it was observed that milk boiling in Al utensil for 10-20 min enhanced the Al levels from 3 to 8% of its total contents in milk samples.

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.

Determination of toxic elemental levels in whey milk of different cattle and human using an innovative digestion method: risk assessment for children < 6.0 months to 5 years.

In present study, the toxic elements, arsenic (As), cadmium (Cd), and lead (Pb), were determined in whey milk samples obtained from various cattle (cow, goat, buffalo, sheep, camel) and human subjects of different areas of Sindh, Pakistan, based on consuming drinking water (exposed area) and surface water (control/non-exposed area). The whey milk was separated from casein by lowering the pH, and heating in an ultrasonic bath at 60 °C for 5 min and centrifuged. The whey milk samples were treated with deep eutectic solvent, prepared from choline chloride-oxalic acid (ChCl-Ox) at different mole ratio. Effects of different parameters on digestion efficiency of whey milk samples, including time and temperature of electric hot plate, mole ratio, and volumes of deep eutectic solvent were examined. The total levels of all selected toxic elements were also detected in whole milk samples of all exposed and nonexposed cattle and human, after acid digestion method. The validity of the proposed method was established by a conventional acid digestion method of selected whey milk samples and spiked certified standards in replicate real whey milk samples. The resulted elements obtained after proposed and conventional heating system were determined by inductively coupled plasma-optical emission spectrometry. The % of all three toxic elements found in whey milk samples were 24 to 50% of their total content in milk samples of different cattle and human. The As, Cd, and Pb contents in cattle and human milk consumed contaminated groundwater was significantly higher (2- to 3-fold) than those values observed for milk samples of cattle, who receive drinking water from fresh canal water (p < 0.01). Estimating the daily intake, hazard quotient and carcinogenic risk for <6 month to 5 years old children, based on the concentrations of toxic elements in milk samples of different cattle and human..

Chemical association of copper and selenium in coals of Sindh by time saving single step strategy and their impact on groundwater.

The aim of the present study is to estimate the different chemical fractionations of copper (Cu) and selenium (Se) in coal samples of different coal mining areas. The Cu and Se bound to various chemical fractions of coal collected from two mining fields of Sindh, Pakistan, have been determined by BCR sequential extraction scheme (BCR-SES). The long duration of the BCR sequential scheme (51 h) was reduced by a time-saving shaking device (ultrasonic bath) termed as ultrasonic-assisted extraction (USE) depending on the same operating conditions and extracting solutions used for BCR sequential extraction scheme. The both trace elements were determined in aquifer water, sampled from different depth of both coal mining fields. In addition, the groundwater of dug well in the vicinity of coal mining areas were also analyzed for Cu and Se using reported extraction methodologies. The partitioning of Cu and Se bound with different chemical fractions of coal was successfully made by proposed USE, within 2 h as compared to long duration of BCR-SES (51 h). The Cu and Se concentrations in acid-soluble fractions of coal samples were > 10%, enhanced by USE extraction procedure than those values gained via BCR-SES (p < 0.01). About 67 to 69% of Cu were found in the first three fractions, whereas their remaining amount corresponding to 31 to 33%, respectively bound with crystalline/residual fraction, while up to 66.1 to 71.1% of total Se contents extracted in three extractable phases, followed up to 28.9 to 33.8% of it was bound with residual phase. The concentrations of Cu and Se in groundwater of different aquifers were found in decreasing order as AQ1 > AQII > AQIII; the same trend was observed for two aquifers of Lakhra coal mining, whereas the groundwater samples have two to three folds higher levels of Se than WHO limit. The Cu levels in water samples were significantly lower than the recommended limit of WHO for drinking water (p < 0.01).

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.

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.