Monitoring of total antimony and its species by ICP-MS and on-line ion chromatography in biological samples from patients treated for leishmaniasis

Results from a study are reported in which patients with leishmaniasis were monitored by whole blood, blood plasma, urine, and hair analysis, before, during, and after intramuscular administration of N-methyl meglumine antimoniate. Quadrupole ICP-MS was used for the detection of antimony and on-line ion chromatography for the separation of its species. After typically 30 consecutive daily injections of 5 mg antimony per kg of body weight, Sb concentrations of up to 250 microg L(-1) in whole blood and plasma, and 60 mg of Sb per gram of creatinine in urine, were measured 24 h after drug administration. Antimony in hair samples of these patients showed concentrations of up to 24 microg g(-1). Speciation studies of Sb5+ and Sb3+ in drug, urine, and plasma samples were performed by ion chromatography using a Hamilton PRP-100X anion exchange column and EDTA (2 or 20 mM, pH 4.7) as the mobile phases. Repeatability of elution time and peak area measurements for a 0.125 ng spike were <1.2% and <3.5%, respectively. Method detection limits for both species, using a 1:10 diluted urine or plasma sample, were typically 1.6 microg L(-1). The procedure was capable of separating the very intense drug peak from its inorganic species, thus permitting the first studies on the bio-transformation of N-methyl meglumine antimoniate to Sb5+ and Sb3+ in the human body.     

Simultaneous determination of arsenic and antimony in environmental samples by radiochemical neutron activation analysis

A radiochemical separation procedure using an inorganic exchanger, tin dioxide (TDO), for the separation of arsenic from antimony is reported here. This separation avoids the interference of 564 keV gamma-ray of¹²²Sb in the measurement of the 559 keV gamma-ray of⁷⁶As in neutron activation analysis. Environmental samples, after neutron irradiation and digestion, are taken up in 1M HCl–0.1M HF and passed through a TDO column which selectively retains arsenic. The effluent from the TDO column, after proper conditioning, is passed through an anion exchange column for quantitative retention of antimony. The procedure has been utilized for arsenic and antimony determination in NBS Orchard Leaves and NBS Albacore Tuna.     

Spectrophotometric procedure using rhodamine B for determination of submicrogram quantities of antimony in rocks

A spectrophotometric procedure using Rhodamine B is given for the determination of antimony in mineralized rocks after its separation as stibine. A study of the Rhodamine B reaction points to the importance of the order of addition of reagents in enhancing sensitivity and increasing the stability of the system. The tolerance of some 26 elements is established for the overall procedure. Although the limit of determination is approximately 0.5 ppm Sb in a 0.2-g sample, the procedure is intended primarily for screening samples containing more than 1 ppm Sb. In pure solutions 0.1 mug of antimony can be determined with a relative standard deviation of 25%. For >0.2 mug of antimony a relative standard deviation of 15% or less can be expected.     

Biological monitoring of arsenic in semiconductor workers

In the manufacture of integrated circuits involving semiconductors, various hazardous materials including arsenic compounds are used. This paper present an evaluation of the biological monitoring of arsenic in the urine, blood and hair of semiconductor workers. Eighty-two blood samples were obtained from research and development workers in a semiconductor factory. Thirty-one samples of urine were obtained from the same group of worker before and after a work period (one shift). Seventy-three hair samples were similarly obtained from the workers. The concentration of arsenic in each sample was determined by arsine (AsH₃) generation flame atomic absorption spectrometry after wet ashing of the sample. The mean concentration of arsenic in hair in these semiconductor workers was significantly higher than that of controls. The mean concentration of arsenic in hair from workers with a longer employment duration was higher than from those with a shorter employment duration. The mean concentration of arsenic in hair from workers engaged in epitaxial growth processes was higher than from workers engaged in other processes. The concentrations of arsenic in hair from semiconductor workers correlated with the duration of their employment. The mean concentration of arsenic in urine before a work a period (shift) was not significantly different from that of controls. The mean concentration of arsenic in urine after a work period was in fact lower than that of controls. The mean concentration of arsenic in blood was not significantly different from that of controls. The determination of arsenic in hair is therefore considered useful for the evaluation of relatively long-term exposure to arsenic in semiconductor workers.     

Removal of exogenously bound elements from human hair by various washing procedures and determination by inductively coupled plasma mass spectrometry

A review of the literature shows that a variety of washing procedures to remove external contamination from hair have been proposed, but as yet no standardised procedures are available. In this study, methods for the pre-treatment and determination of antimony, arsenic, cadmium, chromium, lead, mercury and selenium in human hair by inductively coupled plasma mass spectrometry (ICP-MS) are developed.Investigations of various washing procedures to remove external contaminants show that in unexposed hair samples cadmium, lead and mercury are significantly removed from hair using a 0.1 M HCl wash, with 87, 73 and 5%, respectively being washed-off. The removal of antimony, arsenic and chromium from unexposed hair is, however, more efficient with 1% (v/v) sodium lauryl sulphate (SLS), with 43, 40 and 13% of each element, respectively being washed-off. Selenium is not removed from the hair by any of the washing methods studied. For the digestion of hair samples a digestion mixture of nitric acid and hydrogen peroxide is used.Experiments with simulated sweat spiked with each of these elements show that exogenously bound chromium, cadmium and lead are removed after washing with 0.1 M HCl. In contrast, antimony, arsenic, selenium and mercury irreversibly bind and, thus, are not removed with any of the washing solutions investigated. This work also compares hair levels of these elements in an unexposed and exposed group using the method developed.     

Instrumental neutron activation analysis of the hair of metallurgical workers

Hair samples were collected from 20 metallurgical workers (10 males and 10 females) and from 59 control subjects (32 males and 27 females), whose jobs do not indicate a specific occupational exposure. The concentrations of ten minor and trace elements (Al, Co, Cu, Fe, Mg, Mn, Sb, Se, V and Zn) were determined by instrumental neutron activation analysis (INAA). The statistical data distributions, the sex and age influences in these elemental concentrations and the average values obtained for the control group were compared with published data. The effect of occupational exposure to the metallic elements was reflected in elemental composition of hair by significant higher concentration levels of Al, Co, Cu, Fe, Mg, Mn, Sb, V and Zn in the hair of the exposed group, when compared with the control group.     

Speciation of antimony using chromosorb 102 resin as a retention medium.

The selective retention of the Sb(III) chelate with ammonium pyrrolidine dithiocarbamate (APDC) on a column of Chromosorb 102 resin from a buffered sample solution including Sb(V) was used for the determination of Sb(III). The retained antimony was eluted with acetone. The retention of the Sb(III)-iodide compounds with sodium iodide on the Chromosorb 102 resin column from the same solution after reducing Sb(V) to Sb(III) by iodide in acidic solution was used to preconcentrate the total antimony. The retained antimony was eluted with 0.25 mol l(-1) HNO3. The antimony in the effluent was determined by flame atomic-absorption spectrometry. Also, the total antimony was determined directly by graphite-furnace atomic absorption spectrometry. The Sb(V) concentration could be calculated by the difference. The recoveries were > or = 95%. The detection limits of a combination of the column procedure and flame AAS for antimony were 6 - 61 microg l(-1) and comparable to 4 microg l(-1) for a direct GFAAS measurement. The relative standard deviations were <6%. The procedure was applied to the determination of Sb(III) and Sb(V) in spiked tap water, waste-water samples and a certified copper metal with the satisfactory results.     

Microcolumn sorption of antimony(III) chelate for antimony speciation studies

Selective sorption of the Sb(III) chelate with ammonium pyrrolidine dithiocarbamate (APDC) on a microcolumn packed with C₁₆-bonded silica gel phase was used for the determination of Sb(III) and of total inorganic antimony after reducing Sb(V) to Sb(III) by l-cysteine. A flow injection system composed of a microcolumn connected to the tip of the autosampler was used for preconcentration. The sorbed antimony was directly eluted with ethanol into the graphite furnace and determined by AAS. The detection limit for antimony was significantly lowered to 0.007 μg l⁻¹ in comparison to 1.7 μg l⁻¹ for direct injection GFAAS. This procedure was applied for speciation determinations of inorganic antimony in tap water, snow and urine samples. For the investigation of long-term stability of antimony species a flow injection hydride generation atomic absorption spectrometry with quartz tube atomization (FI HG QT AAS) and GFAAS were used for selective determination of Sb(III) in the presence of Sb(V) and total content of antimony, respectively. Investigations on the stability of antimony in several natural samples spiked with Sb(III) and Sb(V) indicated instability of Sb(III) in tap water and satisfactory stability of inorganic Sb species in the presence of urine matrix.     

Solidified floating organic drop microextraction–electrothermal atomic absorption spectrometry for ultra trace determination of antimony species in tea, basil and water samples

Solidified floating organic drop microextraction was applied as a separation/preconcentration step prior to the electrothermal atomic absorption spectrometric (ETAAS) determination of ultra trace of antimony species. The method was based on the formation of an extractable complex between Sb(III) and ammonium pyrrolidinedithiocarbamate at pH ~ 5, while Sb(V) was remained in the aqueous phase. The antimony extracted into 1-undecanol was determined by ETAAS. Total antimony was determined after the reduction of Sb(V) to Sb(III) with potassium iodide and ascorbic acid. The amount of Sb(V) was determined from the difference of concentration of total antimony and Sb(III). Under the optimum conditions an enhancement factor of 437.5 and a detection limit of 5.0 ng L^?1for the preconcentration of 25 mL of sample was achieved. The relative standard deviation at 300 ng L^?1 of antimony was found to be 3.5 % (n = 6). The proposed method was successfully applied to the determination of antimony in tea, basil and natural water samples.     

Speciation Analysis of Antimony (III) and Antimony (V) by Flame Atomic Absorption Spectrometry After Separation/Preconcentration With Cloud Point Extraction

A sensitive and simple method for flame atomic absorption spectrometry (FAAS) determination of antimony species after separation/preconcentration by cloud point extraction (CPE) has been developed. When the system temperature is higher than the cloud point extraction temperature, the complex of antimony (III) with N-benzoyl-N-phenyhydroxylamine (BPHA) can enter the surfactant-rich phase, whereas the antimony (V) remains in the aqueous phase. Antimony (III) in surfactant-rich phase was analyzed by FAAS and antimony (V) was calculated by subtracting of antimony (III) from the total antimony after reducing antimony (V) to antimony (III) by L-cysteine. The main factors affecting the cloud point extraction, such as pH, concentration of BPHA and Triton X-114, equilibration temperature and time, were investigated systematically. Under optimized conditions, the detection limits (3σ) were 1.82 ng mL⁻¹ for Sb(III) and 2.08 ng mL⁻¹ for Sb(total), and the relative standard deviations (RSDs) were 2.6% for Sb(III) and 2.2% for Sb(total). The proposed method was applied to the speciation of antimony species in artificial seawater and wastewater, and recoveries in the range of 95.3–106% were obtained by spiking real samples. This technique was validated by means of reference water materials and gave good agreement with certified values.     

Antimony speciation by inductively coupled plasma mass spectrometry using solid phase extraction cartridges

A novel and simple method for inorganic antimony speciation is described based on selective solid phase extraction (SPE) separation of antimony(III) and highly sensitive inductively coupled plasma mass spectrometric (ICP-MS) detection of total antimony and antimony(V) in the aqueous phase of the sample. Non-polar SPE cartridges, such as the Isolute silica-based octyl (C8) sorbent-containing cartridge, selectively retained the Sb(III) complex with ammonium pyrrolidine dithiocarbamate (APDC), while the uncomplexed Sb(V) remained as a free species in the solution and passed through the cartridge. The Sb(III) concentration was calculated as the difference between total antimony and Sb(V) concentrations. The detection limit was 1 ng L(-1) antimony. Factors affecting the separation and detection of antimony species were investigated. Acidification of samples led to partial or complete retention of Sb(V) on C8 cartridge. Foreign ions tending to complex with Sb(III) or APDC did not interfere with the retention behavior of the Sb(III)-APDC complex. This method has been successfully applied to antimony speciation of various types of water samples.     

Hair as a monitor for environmental pollution

Variations in concentration of elements with different washing methods of hair-EDTA Method and Acetone Method-and different lead work employees (lead processing workers and lead glass-making workers) were studied by nondestructive neutron activation analysis. The EDTA Method removed not only the external, elements bound by surface adhesion but also the internal elements, such as Mg and Ca, existing in hair. With the Acetone Method, Zn, As and Sb concentrations in hair of lead processing workers show very high values (>2) and Cd and Co concentrations in hair of both groups show high values (1<<2), except for Pb. This suggests the effect of environmental pollution in that factory.     

Contents of arsenic, mercury and other trace elements in Napoleon's hair determined by INAA using the k0-method

Two samples of Napoleon's hair were received for determination of arsenic, mercury and other trace elements by INAA. Before sample irradiation, the hairs were washed following the IAEA washing procedure. Two standard reference materials of GBW09101 (human hair) and NIST/SRM1572 (citrus leaves) were analyzed along with Napoleon's hair for quality control. Standardization was conducted by applying the k ₀-method implemented in the program MULTINAA. The contents of arsenic and mercury as well as three additional elements chromium, antimony and zinc in Napoleon's hair are reported. Compared to the present normal levels, all of the determined elements in Napoleon's hair, except the mercury, are found to be irregular.     

Preparation of Hair and Nail Samples for Trace Element Analysis

Abstract

The method of washing of human hair and nail samples is examined by neutron activation and γ-ray analysis. The amounts of Na, K, Br, Au, Zn and La that are removed by successive washings determine the optimum number of washing for removing these trace elements as surface contaminants. A total solution contact time with the nails is 5 minutes, and leaching effects are observed after 6 washings.     

Nuclear Activation Methods in the Estimation of Environmental Pollution and the Assessment of the Industrial Plant Impact on the Citizens of Gdansk (Poland)

Neutron Activation Analysis (NAA) is a sensitive analytical technique useful for performing both qualitative and quantitative multi-element analysis of major, minor, and trace elements in samples from almost every conceivable field of scientific or technical interest. The NAA method was applied to estimate the atmospheric air quality assessment based on the analytical investigation of rainwater composition in comparison to a moss biomonitoring study performed in selected urban areas of Gdańsk, Poland, during the half-year of exposure. The main objectives of this project were: comparison of dry and alive moss abilities to bioaccumulate inorganic pollutants; and, detection and identification of natural and anthropogenic pollutant sources in this region. An impact of Gdansk Phosphatic Fertilizer Plant “Fosfory,” Poland, on occupational staff and citizens living near the plant has also been examined. The elements, Al, As, Au, Br, Ca, Cl, Cu, Dy, I, In, K, La, Mg, Mn, Mo, Na, S, Sb, Sm, U, V, and Zn, have been determined by instrumental neutron activation analysis (INAA) in the indoor workplace air; in urine, hair, and toenails collected from workers and persons living in a neighborhood near the plant; and from people from the control group not connected with the plant in any way. Analyses of hair and nails was performed at the Interfaculty Reactor Institute in Delft, The Neatherlands, at a 2MW swimming-pool nuclear reactor and at the Joint Institute for Nuclear Research, Dubna, Russia. The essential differences in concentrations of elements for workers and control group were evaluated using non-parametric Mann-Whitney U-tests. Significant differences between workers/citizens of the factory neighborhood and the control group were found for some elements (i.e., Mg, Sb, S, and V), but in the base of these differences, it is hard to define if the factory impact exists. An impact of Federeal-Mogul BIMET S.A. in Gdansk, the biggest manufacturer of slide bearings in Poland, on occupational staff has been also examined. The concentrations of Cu and Pb are much higher in samples taken from workers then from the control group. These results also indicated that hair and toenail samples are useful in the evaluation of that impact. Workers of the slide bearing factory are occupationally exposed to elements, which can be harmful to their health.     

Arsenic pollution in the Yellowknife Area from gold smelter activities

Gold has been mined on a large scale at Yellowknife located in the sub-arctic North West Territories of Canada since 1938. The gold is associated with arsenopyrite ores, with necessitates the oxidation of the arsenic and sulphur by roasting at two Yellowknife smelters. Other metals are also present in the ore, notably antimony. As₂O₃ and SO₂ are emitted into the atmosphere. Large quantities of arsenic were liberated in the past and despite improvements in emission control, significant emission still occur. In order to assess the amount and extent of arsenic contamination in the local environment and the potential exposures and sources to man, soil samples and samples of the native vegetation were collected in and around the town of Yellowknife and the two smelters. Arsenic and antimony analyses were done by instrumental neutron activation analysis using the SLOWPOKE facility at University of toronto. Air-dried plant samples were bombarded at a neutron flux of 1·10¹²n cm²s and soil samples at 2.5·10¹¹n cm²s for 6 minute periods. The¹²²Sb and⁷⁶As-ray emissions at 559 keV were analysed after decay periods of 24–48 hours and compared with standard solutions and NBS standards. Zinc, copper, lead and cadmium analyses were done by atomic absorption spectrophotometry. Arsenic was found to be accumulated in the soils in the vicinity of the two smelters to levels of several thousand ppm. Concentrations greater than 500 ppm occurred in the soil of Yellowknife townsite, and greater than 50 ppm occurred at all sites sampled within 15 km of the town. Antimony levels were about 10% of arsenic and were highly correlated with arsenic. Zinc occurred to 500 ppm around the smelters. Compared with background levels, the foliage of several native species showed substantial arsenic accumulation, up to several hundred ppm in birch. Only 5–25% of this arsenic could be removed by careful washing. Evidence suggests the arsenic is taken up from the soil creating an ongoing arsenic contamination problem. Soil arsenic levels are also sufficiently high to inhibit root growth in soils over a very extensive area.     

Speciation analysis of antimony in marine biota by HPLC-(UV)-HG-AFS: Extraction procedures and stability of antimony species

Speciation analysis of antimony in marine biota is not well documented, and no specific extraction procedure of antimony species from algae and mollusk samples can be found in the literature. This work presents a suitable methodology for the speciation of antimony in marine biota (algae and mollusk samples). The extraction efficiency of total antimony and the stability of Sb(III), Sb(V) and trimethylantimony(V) in different extraction media (water at 25 and 90 °C, methanol, EDTA and citric acid) were evaluated by analyzing the algae Macrosystis integrifolia (0.55 ± 0.04 μg Sb g⁻¹) and the mollusk Mytilus edulis (0.23 ± 0.01 μg Sb g⁻¹). The speciation analysis was performed by anion exchange liquid chromatography (post-column photo-oxidation) and hydride generation atomic fluorescence spectrometry as detection system (HPLC-(UV)-HG-AFS). Results demonstrated that, based on the extraction yield and the stability, EDTA proved to be the best extracting solution for the speciation analysis of antimony in these matrices. The selected procedure was applied to antimony speciation in different algae samples collected from the Chilean coast. Only the inorganic Sb(V) and Sb(III) species were detected in the extracts. In all analyzed algae the sum of total antimony extracted (determined in the extracts after digestion) and the antimony present in the residue was in good agreement with the total antimony concentration determined by HG-AFS. However, in some extracts the sum of antimony species detected was lower than the total extracted, revealing the presence of unknown antimony species, possibly retained on the column or not detected by HPLC-(UV)-HG-AFS. Further work must be carried out to elucidate the identity of these unknown species of antimony.     

Factorial discriminant analysis of occupational exposure in metallurgy using INAA of hair samples

A multivariate statistical technique-factoral discriminant analysis (FDA)-has been used to evaluate the occupational esposure of a group of metallurgy workers using the elemental composition of their scalp hair, as compared with a control group. The initial variables were the concentrations of ten minor and trace elements Al, Co, Cu, Fe, Mg, Mn, Sb, Se, V, and Zn determined in hair samples by using instrumental neutron activation analysis (INAA). A good discrimination between exposed and control subjects has been achieved after the normalization of the data (by log-transforming the initial variables) and considering sex-matched groups. To measure the accuracy of the classification and the predictive ability a cross-validation procedure was used.     

Preconcentration and XRF-determination of heavy metals in hair from Sudanese populations

Energy-dispersive X-ray fluorescence analysis was applied for the analysis of hair. The hair samples were digested in a mixture of nitric and perchloric acid and the heavy metals were precipitated with ammonium pyrrolidine dithiocarbamate. The accuracy, precision and recovery of the method for the elements Fe, Ni, Cu, Zn and Pb were evaluated through the analysis of a standard hair sample. The procedure was applied to the analysis of hair from an occupationally exposed group of Sudanese workers and a control group. The hair of the exposed group showed a range of 80–550 ppm Fe, 6–12 ppm Cu, 57–190 ppm Zn and 70–3700 ppm Pb, while that of the control group had a range of 60–310 ppm Fe, 7–22 ppm Cu, 89–170 ppm Zn and 3–17 ppm Pb.     

Determination of As and Sb in iron and steel by neutron activation analysis with multiple gamma-ray detection

Recycled steel products demands a new technique for determining tramp elements in steel. In this paper, As and Sb in iron certified reference materials were determined by neutron activation analysis with the multiple gamma-ray detection method. The determined values are in good agreement with certified and reference values. The lower determination limits (LDL) for As and Sb in high purity iron are 0.012 and 0.0025 ppm, respectively. As the demanded LDL for As and Sb is 0.1 ppm, the method described in this work is suitable for determining As and Sb in recycled steel.