The use of electrothermal vaporizer coupled to the inductively coupled plasma mass spectrometry for the determination of arsenic, selenium and transition metals in biological samples treated with formic acid.

A fast method for the determination of As, Co, Cu, Fe, Mn, Ni, Se and V in biological samples by ETV-ICP-MS, after a simple sample treatment with formic acid, is proposed. Approximately 75 mg of each sample is mixed with 5 mL of formic acid, kept at 90°C for 1 h and then diluted with nitric acid aqueous solution to a 5% (v/v) formic acid and 1% (v/v) nitric acid final concentrations. A palladium solution was used as a chemical modifier. The instrumental conditions, such as carrier gas flow rate, RF power, pyrolysis and vaporization temperatures and argon internal flow rate during vaporization were optimized. The formic acid causes a slight decrease of the analytes signal intensities, but does not increase the signal of the mainly polyatomic ions ((14)N(35)Cl(+), (14)N(12)C(+), (40)Ar(12)C(+), (13)C(37)Cl(+), (40)Ar(36)Ar(+), (40)Ar(35)Cl(+), (35)Cl(16)O(+), (40)Ar(18)O(+)) that affect the analytes signals. The effect of charge transfer reactions, that could increase the ionization efficiency of some elements with high ionization potentials was not observed due to the elimination of most of the organic compounds during the pyrolysis step. External calibration with aqueous standard solutions containing 5% (v/v) formic acid allows the simultaneous determination of all analytes with high accuracy. The detection limits in the samples were between 0.01 (Co) and 850 µg kg(-1) (Fe and Se) and the precision expressed by the relative standard deviations (RSD) were between 0.1% (Mn) and 10% (Ni). Accuracy was validated by the analysis of four certified reference biological materials of animal tissues (lobster hepatopancreas, dogfish muscle, oyster tissue and bovine liver). The recommended procedure avoids plasma instability, carbon deposit on the cones and does not require sample digestion.

Ambient mass spectrometric detection of organometallic compounds using direct analysis in real time.

The present work describes the mass spectrometric detection of organometallic compounds following their atmospheric pressure ionization using a commercial direct analysis in real time (DART) ion source. Several organometallic compounds of As, Fe, Hg, Pb, Se, and Sn were examined, and their corresponding mass spectra as well as induced fragmentation patterns were recorded. Gas phase sampling of the pure organometallic compounds or their solutions prepared in toluene generated temporally stable signals. For the majority of the compounds, the molecular ion or protonated molecule was detected; noticeable exceptions are the tetra-substituted compounds for which their less-substituted species dominated. The organometallic species were used as model compounds for a systematic investigation of the impact of operating parameters of the DART source, including gas temperature and electrode voltages. In general, results have shown that powering the electrodes designed to remove ions from the DART gas stream results in a reduction in signal intensity for most of the compounds investigated, suggesting that charged species from the plasma play an important role in the ionization process of the test analytes.

Simultaneous determination of Cd, Cu, Mn, Ni, Pb and Zn in nail samples by inductively coupled plasma mass spectrometry (ICP-MS) after tetramethylammonium hydroxide solubilization at room temperature: comparison with ETAAS.

A simple method is described for the determination of Cd, Cu, Mn, Ni, Pb and Zn in nails by using inductively coupled plasma mass spectrometry (ICP-MS) or electrothermal atomic absorption spectrometry (ETAAS). Prior to analysis, 10-20 mg of nail samples were accurately weighed into (15 mL) conical tubes. Then, 1 mL of 25% (w/v) tetramethylammonium hydroxide (TMAH) solution was added to the samples, incubated at room temperature overnight and then further diluted to 10 mL with 1% (v/v) HNO(3). After that, samples were directly analyzed. Rhodium was used as internal standard for ICP-MS analysis. Method detection limits (3 s, n=20) were 0.1, 3.0, 1.0, 4.5, 1.5, 5.0 ng g(-1) for Cd, Cu, Mn, Ni, Pb and Zn, respectively for ICP-MS, and 24, 26, 30, 143, 130 and 1000 ng g(-1), respectively for ETAAS. The key issue addressed here is the elimination of the acid digestion prior to analysis. Moreover, with the use of the proposed method there is a considerable improvement in the sample throughput comparing to the traditional methods using microwave-assisted acid sample digestion prior to analysis. For validation purposes, six ordinary nail samples were solubilized and then directly analyzed by ICP-MS and ETAAS, with no statistical difference between the two techniques at 95% level on applying the t-test.

Single drop micro-extraction with O,O-diethyl dithiophosphate for the determination of lead by electrothermal atomic absorption spectrometry.

Lead was extracted as the O,O-diethyldithiophosphate (DDTP) complex from aqueous solution into a drop of CHCl(3) immersed in the solution. Unlike previously reported procedures using single drop micro-extraction (SDME) for the extraction of inorganic analytes, the complexation reaction was conducted in the aqueous phase, as the ammonium salt of DDTP is soluble in water. The concentration of DDTP was optimized as 0.01% (m/v). Experimental parameters such as extraction time (7min) and organic drop volume (3microL) were optimized and selected as a compromise between sensitivity and stability of the organic drop in the aqueous solution. The sensitivity with electrothermal atomic absorption spectrometry (ET AAS) was low, probably due to infiltration of the organic drop into the totally pyrolytic graphite platform. To overcome this problem, tungsten (400microg) was thermally deposited onto the platform surface. A short pyrolysis stage at 700 degrees C was included to reduce background absorption. Under these conditions, five certified reference materials with different characteristics were analyzed using calibration against aqueous standards submitted to the SDME procedure, resulting in good agreement between certified and found concentration values at a 95% confidence level. Two real water samples have also been analyzed, with recoveries ranging from 85 to 92% after enrichment with Pb. An enhancement factor of 52 allowed a detection limit of 0.2microg L(-1) or 0.04microg g(-1), demonstrating the high detection capability of the proposed procedure, with a relative standard deviation typically below 4%.

Determination of Co, Cu, Fe, Mn, Ni and V in diesel and biodiesel samples by ETV-ICP-MST.

This work presents the determination of Co, Cu, Fe, Mn, Ni and V in diesel and biodiesel samples by ETV-ICP MS using emulsion sample preparation. The emulsion composition was: 1.0 g of the diesel or biodiesel sample, 2.0 mL of a 5% m/v Triton X-100 solution, 0.5 mL of HNO3 and deionized water to a 10 mL final volume. The optimized parameters were mass of carrier/modifier (1.0 microg Pd), RF power (1100 W), carrier gas flow rate (0.95 L min(-1)) and inner ETV gas flow rate (0.15 L min(-1)). The determinations were performed against aqueous solutions using 10 microg L(-1) Rh as internal standard. The accuracy of the method was verified through the analysis of the NIST 1634c reference residual fuel oil, recovery tests and comparison of the results with those obtained by GF AAS. The results were in agreement according to the t-test at a 95% confidence level. The RSD values were lower than 20%, the recoveries were between 80 and 120% and the LOD values were in the order of ng g(-1), showing the good accuracy and sensitivity of the method.

Determination of total mercury and methylmercury in biological samples by photochemical vapor generation.

Cold vapor atomic absorption spectrometry (CV-AAS) based on photochemical reduction by exposure to UV radiation is described for the determination of methylmercury and total mercury in biological samples. Two approaches were investigated: (a) tissues were digested in either formic acid or tetramethylammonium hydroxide (TMAH), and total mercury was determined following reduction of both species by exposure of the solution to UV irradiation; (b) tissues were solubilized in TMAH, diluted to a final concentration of 0.125% m/v TMAH by addition of 10% v/v acetic acid and CH(3)Hg(+) was selectively quantitated, or the initial digests were diluted to 0.125% m/v TMAH by addition of deionized water, adjusted to pH 0.3 by addition of HCl and CH(3)Hg(+) was selectively quantitated. For each case, the optimum conditions for photochemical vapor generation (photo-CVG) were investigated. The photochemical reduction efficiency was estimated to be approximately 95% by comparing the response with traditional SnCl(2) chemical reduction. The method was validated by analysis of several biological Certified Reference Materials, DORM-1, DORM-2, DOLT-2 and DOLT-3, using calibration against aqueous solutions of Hg(2+); results showed good agreement with the certified values for total and methylmercury in all cases. Limits of detection of 6 ng/g for total mercury using formic acid, 8 ng/g for total mercury and 10 ng/g for methylmercury using TMAH were obtained. The proposed methodology is sensitive, simple and inexpensive, and promotes "green" chemistry. The potential for application to other sample types and analytes is evident.

Determination of mercury in biological samples by cold vapor atomic absorption spectrometry following cloud point extraction with salt-induced phase separation.

Method development for the pre-concentration of mercury in human hair, dogfish liver and dogfish muscle samples using cloud-point extraction and cold vapor atomic absorption spectrometry is demonstrated. Before the extraction, the samples were submitted to microwave-assisted digestion in a mixture of H(2)O(2) and HNO(3). Cloud point extraction was carried out using 0.5% (m/v) ammonium O,O-diethyldithiophosphate (DDTP) as the chelating agent and 0.3% (m/v) Triton X-114 as the non-ionic surfactant. Phase separation was induced after the addition of Na(2)SO(4) to a final concentration of 0.2 mol L(-1). Aliquots of the final extract were transferred to PTFE tubes and NaBH(4) and HCl were added. The mercury vapor was driven to a non-heated quartz tube for measuring the absorbance. The results obtained with salt-induced phase separation were in good agreement with the certified values at a 95% confidence level. An enrichment factor of 10 allowed a detection limit of 0.4 ng g(-1) to be obtained, which demonstrates the high sensitivity of the proposed procedure for the determination of mercury at trace levels.

Contrasting effects of age on the plasma/whole blood lead ratio in men and women with a history of lead exposure.

We examined the effect of age and sex on the relationship between the concentrations of Pb in blood (Pb-B) and in plasma (Pb-P) in an adult population with a history of lead exposure. Pb-P was determined by inductively coupled plasma mass spectrometry (ICP-MS) and Pb-B by graphite furnace atomic absorption spectrometry (GF AAS). We studied 154 adults (56 men and 98 women) from 18 to 60-year old. Pb-B levels varied from 10.0 to 428.0 microg/L, with a mean of 76 microg/L. Blood lead levels varied from 10.0 to 428.0 microg/L in men (mean, 98.3 microg/L) and from 10.0 to 263.0 microg/L (mean, 62.8 microg/L) in women. Corresponding Pb-Ps were 0.02-2.9 microg/L (mean, 0.66 microg/L) and 0.02-1.5 microg/L (mean, 0.42 microg/L) in men and women, respectively. The relationship between Pb-B and Pb-P was found to be curvilinear (r = 0.757, P < 0.001 Spearman's correlation). The two quantities are related by the line y = 0.0006x(1492) (y = Pb-P, and x = Pb-B). The %Pb-P/Pb-B ratio ranged from 0.03% to 1.85%. A positive association was found between %Pb-P/Pb-B ratio and Pb-B levels. When data were separated by sex, this association was also relevant for men (y = 0.0184x(0.702)) and women (y = 0.0534x(0.5209)) (y = %Pb-P/Pb-B and x = Pb-B). Moreover, we found an interesting positive correlation between Log (Pb-P/Pb-B) and age for women (r = 0.31, P < 0.0001) and a negative correlation for men (r = -0.164, P = 0.07). Taken together, these results suggest contrasting effects of age on the plasma/whole blood lead ratio in men and women with a history of lead exposure. Moreover, sex might play an important role in the metabolism of lead, implying further consideration on the kinetic models constructed of lead toxicity.

Determination of cadmium in coal using solid sampling graphite furnace high-resolution continuum source atomic absorption spectrometry.

This work describes the development of a method to determine cadmium in coal, in which iridium is used as a permanent chemical modifier and calibration is performed against aqueous standards by high-resolution continuum source atomic absorption spectrometry (HR-CS AAS). This new instrumental concept makes the whole spectral environment in the vicinity of the analytical line accessible, providing a lot more data than just the change in absorbance over time available from conventional instruments. The application of Ir (400 microg) as a permanent chemical modifier, thermally deposited on the pyrolytic graphite platform surface, allowed pyrolysis temperatures of 700 degrees C to be used, which was sufficiently high to significantly reduce the continuous background that occurred before the analyte signal at pyrolysis temperatures <700 degrees C. Structured background absorption also occurred after the analyte signal when atomization temperatures of >1600 degrees C were used, which arose from the electron-excitation spectrum (with rotational fine structure) of a diatomic molecule. Under optimized conditions (pyrolysis at 700 degrees C and atomization at 1500 degrees C), interference-free determination of cadmium in seven certified coal reference materials and two real samples was achieved by direct solid sampling and calibrating against aqueous standards, resulting in good agreement with the certified values (where available) at the 95% confidence level. A characteristic mass of 0.4 pg and a detection limit of 2 ng g(-1), calculated for a sample mass of 1.0 mg coal, was obtained. A precision (expressed as the relative standard deviation, RSD) of <10% was typically obtained when coal samples in the mass range 0.6-1.2 mg were analyzed.