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.

Inorganic arsenic speciation in groundwater samples using electrothermal atomic spectrometry following selective separation and cloud point extraction.

A method has been developed for speciation of total, total inorganic and organic arsenic (As) species in groundwater samples. The inorganic species of As((III,V)) were separated from organic forms by adsorbing on alumina (Al(2)O(3)) whereas the organic As was eluted out. The retained inorganic As species was eluted by 0.2 M HCl. Then eluent As(III) and As(V) were formed as complexes with ammonium pyrrolidinedithiocarbamate (APDC) and molybdate, respectively. Then As(III)-PDC and As(V)-molybdate complexes were quantitatively extracted into a non-ionic surfactant Triton X-114. The total As was determined by conventional preconcentration procedures. The resulting solutions of each method were determined by ETAAS with modifier. The main factors affecting the separation and cloud point extraction (CPE) were investigated in detail. The limits of detection values were found as 0.04 and 0.20 µg L(-1) for As(III) and As(V), respectively, whereas limits of quantification were observed as 0.13 and 0.33 µg L(-1) for As(III) and As(V), respectively. Standard addition method confirmed the accuracy. The recoveries of As(III) and As(V) were found in the range of 98 - 99%. The proposed method was applied to groundwater samples collected from different areas of Sukkur district.

Evaluation of arsenic levels in grain crops samples, irrigated by tube well and canal water.

The aim of this study was to evaluate the uptake of arsenic (As) by grain crops (wheat, maize and sorghum) grown on agricultural soil irrigated with tube well water (SIT) as test samples and for comparative purposes, same grain crop samples grown on agricultural soil irrigated with fresh canal water (SIC) were marked as control samples, collected simultaneously from three sub-districts of Khairpur, Pakistan. Moreover, this paper demonstrated the total and EDTA (0.05 M) extractable As in both understudied soils that correlate with the respective total As in the edible parts of the studied grain crops. A significantly high accumulation of As was found in grains grown on SIT as compared to those grown on SIC. This study highlights the increased danger of growing food crops in the agricultural land continuously irrigated by As contaminated ground water.

Optimization of ultrasonic-assisted acid extraction of mercury in muscle tissues of fishes using multivariate strategy.

A simple and rapid ultrasound-assisted extraction procedure was developed for the determination of total mercury (Hg) in muscle tissues of freshwater fish species. A Plackett-Burman experimental design was used as a multivariate strategy for the evaluation of the effects of variables, such as presonication time (without ultrasonic stirring), sonication time, ultrasonic bath temperature, nitric acid concentration, hydrochloric acid concentration, and sample mass of muscle tissues. Some variables showed a significant effect on recovery, and they were further optimized by a 2(3) + star central composite design that involved 16 experiments. The validation was carried out by analysis of certified reference material DORM-2 (dog fish muscles); for comparative purposes, an acid digestion induced by microwave energy was used. Cold vapor atomic absorption spectrometry was used for the determination of total Hg. No significant differences were established between the analytical results and the certified values (paired t-test at P > 0.05). The LOD and LOQ of Hg were 0.133 and 0.445 microg/kg, respectively, which demonstrated the high sensitivity of the proposed procedure for the determination of Hg at trace levels. The Hg concentrations in the muscle tissues of 10 freshwater fish species were found in the range of 35.3-67.8 microg/kg on a dried basis, which were within the permissible limit of the World Health Organization.

Optimization of cloud point extraction and solid phase extraction methods for speciation of arsenic in natural water using multivariate technique.

The simple and rapid pre-concentration techniques viz. cloud point extraction (CPE) and solid phase extraction (SPE) were applied for the determination of As(3+) and total inorganic arsenic (iAs) in surface and ground water samples. The As(3+) was formed complex with ammonium pyrrolidinedithiocarbamate (APDC) and 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(-1) HNO(3) in methanol. While total iAs in water samples was adsorbed on titanium dioxide (TiO(2)); after centrifugation, the solid phase was prepared to be slurry for determination. The extracted As species were determined by electrothermal atomic absorption spectrometry. The multivariate strategy was applied to estimate the optimum values of experimental factors for the recovery of As(3+) and total iAs by CPE and SPE. The standard addition method was used to validate the optimized methods. The obtained result showed sufficient recoveries for As(3+) and iAs (>98.0%). The concentration factor in both cases was found to be 40.

Determination of toxic elements in infant formulae by using electrothermal atomic absorption spectrometer.

In present work concentrations of toxic elements (TEs), aluminum (Al), cadmium (Cd), and lead (Pb) in seventeen imported samples of infant milk-based (IMF) and infant soy-based formulae (ISF), were measured, to evaluate whether the intakes of understudy TEs accomplished within recommended permissible levels. The TEs were analyzed by electrothermal atomic absorption spectrometer, prior to microwave induced acid digestion. The validity of methodology was tested by simultaneously analyzing certified reference material and standard addition method. It was observed that ISF contains higher concentration of understudy toxic analytes as compared to IMF. The all three TEs, Al, Cd and Pb were detected in different branded infant formulae, in the range of (1070-2170), (10.5-34.4), and (28.7-119) microg/kg, respectively. The estimated intakes of TEs as microg/kg/week for infants (>1year) through milk formulae are well below the recommended tolerable levels of these elements.

Evaluation of an ultrasonic acid digestion procedure for total heavy metals determination in environmental and biological samples.

In this study, a sample preparation method based on ultrasonic assisted acid digestion (UAD) has been evaluated for total heavy metals (Cd, Cr, Ni and Pb) determination in different environmental (soil, sediment and sewage sludge), and biological (fish muscles, vegetables and grains) samples, using electrothermal atomic absorption spectrometry (ETAAS). The investigated parameters influencing UAD such as presonication time, sonication time, temperature of ultrasonic bath, and different acid mixtures were fully optimized, whereas power was maintained constant at 100% of nominal power of ultrasonic bath. Six different sets of above parameters were applied on six certified reference materials (CRMs) having different matrices. The accuracy of the method was also tested by comparing the results with those obtained from conventional hot plate assisted acid digestion method on same CRMs. Analytical results for HMs by both methods showed no significant difference at 95% confidence limit (p<0.05). Recoveries of HMs ranging from 96.2% to 102% and 96.3% to 98.6% were obtained from biological and environmental samples, respectively. The average relative standard deviation of UAD method varied between 3.5% and 8.2%, depending on the analyte.

Improved extraction method for the determination of iron, copper, and nickel in new varieties of sunflower oil by atomic absorption spectroscopy.

A simple and fast procedure is proposed for the extraction of iron (Fe), copper (Cu), and nickel (Ni) in 16 varieties of sunflower seed oil samples using an ultrasonic bath. The experimental parameters of the ultrasonic-assisted extraction (UAE) method were optimized to improve the sensitivity and detect the metals at trace levels in minimum time. Conventional wet acid digestion method was used for comparative purposes. The optimum recovery of all 3 metals was obtained by UAE for 7 min, while the separation of aqueous and organic phases after extraction using centrifugation (UAE-2) required 3 min, as compared to the conventional equilibration method (UAE-1) that required 90 min. The respective recoveries of Cu, Fe, and Ni obtained with UAE-2 were in the range of 95.8-97.5, 93.5-98.3, and 95.6-98.2%, respectively, for different varieties of sunflower oil samples. Accuracy was determined by the standard addition method. Under the optimum operating conditions, the limits of detection obtained from the standard addition curves were 21.7, 20.4, and 35.6 ng/mL for Fe, Cu, and Ni, respectively. The fact that all varieties of sunflower oil contain significant amounts of Fe, Cu, and Ni indicates the deterioration of sunflower oil quality immediately after extraction from seeds, which poses a threat to oil quality and human health.

Ultrasound-assisted pseudodigestion for toxic metals determination in fish muscles followed by electrothermal atomic absorption spectrophotometry: multivariate strategy.

A simple and efficient procedure for the determination of arsenic (As), cadmium (Cd), and lead (Pb) in the edible parts of freshwater fish by ultrasonic-assisted acid pseudodigestion (USD) was developed. A Plackett-Burman experimental design was used as a multivariate strategy for the evaluation of the effects of several variables at once. Five variables--sonication time, sample mass of muscle tissue, temperature of the ultrasonic bath, mL of nitric acid, and mL of a mixture of acid and oxidant--were regarded as factors. From these studies, certain variables showed up as significant, and they were optimized by a 23+star central composite design, which involved 16 experiments. Optimum values of the variables were selected for the development of USD to determine the contents of As, Cd, and Pb in fish muscles used as pollution bioindicators from Lake Manchar (Sindh, Pakistan). The determination of the 3 toxic metals under study was performed by electrothermal atomic absorption spectrometry. The accuracy of the optimized procedure was evaluated by analysis of certified reference materials BCR 185R bovine liver and by comparison with conventional wet acid digestion methodology. The result obtained by the optimized method showed good agreement with the certified values and sufficiently high recovery. No significant differences were observed for P = 0.05. Relative standard deviation values (average of 10 separate determinations) were 1.21, 5.52, and 5.32% for As, Cd, and Pb, respectively.

Determination of cadmium and lead in biological samples by three ultrasonic-based samples treatment procedures followed by electrothermal atomic absorption spectrometry.

The development of 3 different ultrasonic-based sample treatment methods, ultrasonic probe-assisted acid extraction, ultrasonic-assisted acid slurry, and ultrasonic-assisted acid pseudodigestion is presented. These methods were compared for the determination of Cd and Pb by electrothermal atomic absorption spectrometry in biological samples (blood and scalp hair) and validated by using certified materials BCR 397 human hair and BCR 185R bovine liver. The sample amounts chosen to perform the analysis were 100 mg and 0.5 mL for solids (human hair and bovine liver) and blood samples, respectively. An acid digestion induced by microwave energy was used to obtain the total metal concentrations and for comparative purposes. The best results were obtained with the ultrasonic-assisted acid pseudodigestion, with which it was possible to perform accurate and precise determination of the Cd and Pb contents in 2 certified reference materials and biological samples of 50 normal males of ages 25-40 years. The precision of the methods, together with their efficiency, rapidity, low cost, and environmental acceptability, make them good alternatives for the determination of trace metals from biological samples. The precision of the methods for accuracy evaluation, resulting in good agreement according to the t-test for a 95% confidence level, and the relative standard deviations were lower than 10% (n=10) for all determinations.

Speciation of heavy metals in untreated domestic wastewater sludge by time saving BCR sequential extraction method.

In this work the modified three-stage sequential extraction procedure developed within the Standards, Measurement and Testing Programme (formally the Community Bureau of Reference BCR) of the European Commission, was applied for the fractionation of Cd, Cr, Cu, Ni, Pb and Zn in the untreated domestic wastewater sludge (DWS) collected from the Hyderabad city of Pakistan. The aim of our study was to evaluate the impact of different time intervals for shaking, and sample mass of sewage sludge on optimal recovery of all metals under study. Analyses of the extracts were performed by flame atomic absorption spectrometry (FAAS) and electrothermal atomic absorption spectrometry (ETAAS). The precision and accuracy of the proposed procedure was evaluated by using a certified reference material of soil amended with sewage sludge BCR 483. The maximum recoveries for Cd and Zn were observed for all three steps of BCR protocol at 26 hours (h) total shaking period, while Cr, Cu, Ni and Pb were achieved at 32 hours instead of previously reported 51 hours, with (p < 0.05). The maximum level of all heavy metals was achieved in samples mass 0.2-0.4 g, where as the extractant-sample mass ratio was kept according to the optimized BCR method. The results of the sequential extraction study of untreated DWS indicates that more easily mobilized forms (acid exchangeable) were found to be 31.0, 3.1, 2.5, 7.6, 2.6 and 8.4% of total contents of Cd, Cr, Cu, Ni, Pb and Zn, respectively. The oxidizable fraction is dominant for all the heavy metals, except Cd. The lixiviation tests (DIN 38414-S4) were used to evaluate the leaching of heavy metals from sewage sludge used for agricultural purposes.

Effect of ultrasound agitation on the release of heavy elements in Certified Reference Material of human hair (CRM BCR 397).

An ultrasonic-assisted leaching procedure was developed for the determination of heavy elements (As, Cu, Cd, Pb, and Zn) in Certified Reference Material of human hair (CRM 397) provided from the Community Bureau of Reference (BCR) of the Commission of the European Community. Concentrated nitric acid-30% hydrogen peroxide (2 + 1) was used for the leaching method. The effects of different factors on acid leaching of elements, such as presonication time (without ultrasonic stirring), sonication or exposure time to ultrasound, and temperature of the ultrasonic bath have been investigated. Optimum values of these parameters were selected for the maximum extraction of heavy metals from CRM BCR 397 and human scalp hair samples of normal healthy males. To check the validity of the proposed method, a wet acid digestion method was used to obtain the total elemental concentration in CRM BCR 397 and scalp hair samples. Cu and Zn in leachate and digests were measured by flame atomic absorption spectrometry using a conventional air/acetylene flame, while As, Cd, and Pd were determined by electrothermal atomic absorption spectrometry. Under optimized conditions, the recovery for Zn, Cd, Pd, As, and Cu was 98, 98.5, 97.5, 98.2, and 95%, respectively, of those obtained with the wet acid digestion method.

Evaluation of essential and toxic metals by ultrasound-assisted acid leaching from scalp hair samples of children with macular degeneration patients.

BACKGROUND: The causes of night blindness in children are multifactorial and particular consideration has been given to childhood nutritional deficiency, which is the most common problem found in underdeveloped countries. Such deficiency can result in physiological and pathological processes that in turn influence hair composition. METHOD: An ultrasonic-assisted acid leaching procedure was developed as a sample pretreatment for the determination of Zn, Cu, Cd, As and Pb in human scalp hair samples of night blindness male children with age between 5 to 15 y and compared with the children without vision anomalies that lived in the same localities. The effects of different factors on acid leaching of metals, such as preintensification time (without ultrasonic stirring) after treatment of acid mixture, exposure time to ultrasound and temperature of the ultrasonic bath have been investigated. The proposed method was validated by certified reference samples of scalp hair CRM 397. The wet acid digestion method was used to obtain the total metal concentration in both scalp hair and CRM samples. Cu and Zn in leachates and digests were measured by flame atomic absorption spectrometry (FAAS) using a conventional air/acetylene flame, while Cd and Pb were determined by electrothermal atomic absorption spectrometry (ETAAS) under optimized conditions. RESULTS: It was observed that at optimal conditions, the recovery for Zn, Cd, Pb, As and Cu were 98%, 98.5%, 96%, 97.2% and 94% respectively. The mean values of Zn and Cu in scalp hair samples of children having night blindness were significantly lower as compared to normal healthy children (p for Zn<0.001 and Cu<0.003), while the level of toxic metals As, Cd and Pb were significantly higher in children having ocular problems as related to normal children (p As<0.0074, Cd<0.001 and lead<0.004). CONCLUSION: These data present guidance to clinicians and other professional investigating deficiency of essential trace metals and excessive level of toxic metals in biological samples.

Evaluation of toxic metals in biological samples (scalp hair, blood and urine) of steel mill workers by electrothermal atomic absorption spectrometry.

The determination of toxic metals in the biological samples of human beings is an important clinical screening procedure. This study aimed to assess the possible influence of environmental exposure on production workers (PW) and quality control workers (QCW) of a steel mill, all male subjects aged 25-55 years. In this investigation, the concentrations of Pb, Cd, Ni and Cr were determined in biological samples (blood, urine and scalp hair samples) from these steel mill workers in relation to controlled unexposed healthy subjects of the same age group. After pre-treatment with nitric acid-hydrogen peroxide, the samples were digested via a microwave oven, and for comparison purposes, the same samples were digested by the conventional wet acid digestion method. The samples digested were subjected to graphite furnace atomic absorption spectrometry (GFAAS). To assess the reliability of these methods, critical factors, such as detection limit(s), calibration range(s), accuracy and precision, were studied. Quality control for these procedures was established with certified sample of human hair, urine and whole blood. The results indicate that the level of lead, cadmium and nickel in scalp hair, blood and urine samples were significantly higher in both groups of exposed workers (QW and PW) than those of the controls. The possible connection of these elements with the etiology of disease is discussed. The results also show the need for immediate improvements in workplace ventilation and industrial hygiene practices.