[Effect of copper supplementation on lipid profile of Venezuelan hyperlipemic patients]. / Efecto de la suplementación oral con cobre en el perfil lipídico de pacientes Venezolanos hiperlipémicos.

It has been assumed that most Western diets satisfy the requirement of copper/day because of ubiquitous presence of this element in most foods. Recent studies have shown that dietary copper (Cu) may often fall below the estimated daily requirements, what could determine a deficiency of this trace element. This deficiency is associated with hypercholesterolemia and hypertrigliceridemia, both in human and experimental animals. In the present intervention study was examined the effect of the administration of 5 mg of Cu/day in 73 patients (treated group), of both genders, with ages between 26 and 48 years, with high serum levels of total cholesterol and triglycerides without pharmacological treatment and compared with 73 hyperlipemic subjects non-treated with copper (control group) who were matched by gender, age, body weight, smoking habits, calories and fat intake, and physical activity. Before copper administration, a sample of blood was obtained for serum determinations of copper, zinc and lipids. At the end of the experimental period (45 days), a new sample of blood was taken for the corresponding determinations. The results suggest the existence of a marginal deficiency of the trace element in 38% of the subjects and demonstrate that copper supplementation decreases (p < 0.05) serum levels of total cholesterol (r = -0.976), triglycerides (r = -0.972), LDL-cholesterol (r = -0.961) and zinc (r = -0.980) with a slight increment (r = 0.894) of HDL-cholesterol. These findings demonstrate that copper can be used in the treatment of the patients with hypercholesterolemia and hypertriglyceridemia. The mechanisms by which Cu determines these changes are not known.

HPLC determination of Vitamin D(3) and its metabolite in human plasma with on-line sample cleanup.

A HPLC method with automated column switching and UV-diode array detection is described for the simultaneous determination of Vitamin D(3) and 25-hydroxyvitamin D(3) (25-OH-D(3)) in a sample of human plasma. The system uses a BioTrap precolumn for the on-line sample cleanup. A sample of 1ml of human plasma was treated with 2ml of a mixture of ethanol-acetonitrile (2:1 (v/v)). Following centrifugation, the supernatant was evaporated to dryness under a stream of dry and pure nitrogen. The residue was reconstituted in 250muL of a solution of methanol 5mmoll(-1) phosphate buffer, pH 6.5 (4:1 (v/v)), and a 200mul aliquot of this solution was injected onto the BioTrap precolumn. After washing during 5min with a mobile phase constituted by a solution of 6% acetonitrile in 5mmoll(-1) phosphate buffer, pH 6.5 (extraction mobile phase), the retained analytes were then transferred to the analytical column in the backflush mode. The analytical separation was then performed by reverse-phase chromatography in the gradient elution mode with the solvents A and B (Solvent A: acetonitrile-phosphate buffer 5mmoll(-1), pH 6.5; 20:80 (v/v); solvent B: methanol-acetonitrile-tetrahydrofuran, 65:20:15 (v/v)). The compounds of interest were detected at 265nm. The method was linear in the range 3.0-32.0ngml(-1) with a limit of quantification of 3.0ngml(-1). Quantitative recoveries from spiked plasma samples were between 91.0 and 98.0%. In all cases, the coefficient of variation (CV) of the intra-day and inter-day-assay precision was

[Effect of cooper supplementation on blood pressure values in patients with stable moderate hypertension]. / Efecto de la suplementación con cobre sobre los valores de presión arterial en pacientes con hipertensión moderada estable.

Copper (Cu) deficiency is associated with changes in arterial pressure. The effect depends of the age of initiation of the copper-deficient diet. Copper deficiency started at a young age causes hypotension. When initiated in older or adult animals, copper deficiency can cause hypertension. A case-control study was carried out to investigate the effect of administrating 5 mg Cu/d in 60 subjects, both genders, with mild stable hypertension, pharmacologically untreated (treated group) and compared with 60 hypertensives (control group) who were matched by gender, age, body weight, smoking habits, calories, fat and salt intake (NaCl), and physical activity. Hypertension was diagnosed when the blood pressure was > 150/95 mm Hg. Mean age, mean corporal weight and risk factors were similar in both groups. The results suggested the existence of a marginal deficiency of the trace element in 62% of subjects and demonstrated that Cu decreases systolic (r = -0.963) and diastolic (r = -0.981) blood pressures in treated group (p < 0.05). Control patients did not show significant changes in their arterial pressures. These findings indicate a functional alteration in human blood pressure regulation during mild copper depletion and suggest that Cu could be used in the treatment of stable moderate arterial hypertension. Further investigation is needed to determine the extent of this influence.

Efecto de la suplementación con cobre sobre los valores de presión arterial en pacientes con hipertensión moderada estable / Effect of cooper supplementation on blood pressure values in patients with stable moderate hypertension

Copper (Cu) deficiency is associated with changes in arterial pressure. The effect depends of the age of initiation of the copper-deficient diet. Copper deficiency started at a young age causes hypotension. When initiated in older or adult animals, copper deficiency can cause hypertension. A case-control study was carried out to investigate the effect of administrating 5 mg Cu/d in 60 subjects, both genders, with mild stable hypertension, pharmacologically untreated (treated group) and compared with 60 hypertensives (control group) who were matched by gender, age, body weight, smoking habits, calories, fat and salt intake (NaCl), and physical activity. Hypertension was diagnosed when the blood pressure was > 150/95 mm Hg. Mean age, mean corporal weight and risk factors were similar in both groups. The results suggested the existence of a marginal deficiency of the trace element in 62 per cent of subjects and demonstrated that Cu decreases systolic (r = -0.963) and diastolic (r = -0.981) blood pressures in treated group (p < 0.05). Control patients did not show significant changes in their arterial pressures. These findings indicate a functional alteration in human blood pressure regulation during mild copper depletion and suggest that Cu could be used in the treatment of stable moderate arterial hypertension. Further investigation is needed to determine the extent of this influence.

Determination of paraquat in human blood plasma using reversed-phase ion-pair high-performance liquid chromatography with direct sample injection.

This report describes the determination of paraquat (PQ) in human blood plasma samples by a direct-injection reversed-phase ion-pair chromatographic method. Blood plasma filtrate was injected directly into the LiChrospher(R) RP-18 alkyl-diol silica (ADS) precolumn integrated in a column switching system using a mixture of 3% 2-propanol and 10 mM sodium octane sulfonate (SOS) in a 0.05 M phosphate buffer (pH 2.8). After washing with this phase, the ADS precolumn was back-flushed with the analytical mobile phase consisting of 40% of methanol and 10 mM SOS in a 0.05 M phosphate buffer (pH 2.8) at a flow rate of 1.0 ml min(-1), in order to carry the analyte to a conventional reversed-phase analytical column, where the separation of PQ was achieved and finally detected by UV at 258 nm. The recoveries of PQ from human blood plasma samples ranged between 95.0 and 99.5% at nine different concentrations (from 0.05 to 3.00 microg of PQ ml(-1)) with coefficients of variation <2.5% (n=3). The precision expressed as relative standard deviation was below 3.5% for between-day and below 4.3% for within-day measurements (n=5). The detection limit (signal-to-noise ratio, S/N>3) was 0.005 microg ml(-1) with an injection volume of 200 microl. The proposed method is promising for the identification and quantification of PQ at low concentration levels and is suitable for its analysis in human blood plasma samples from intentional or accidental poisonings cases with a sample throughput of 5 samples per hour.

Flow analysis-hydride generation-Fourier transform infrared spectrometric determination of antimony in pharmaceuticals.

In this work, a flow analysis system with hydride generation and Fourier transform infrared (FTIR) spectrometric detection has been developed for the determination of antimony in pharmaceuticals. The method is based on the on-line mineralization/oxidation of the organic antimonials present in the sample and pre-reduction of Sb(V) to Sb(III) with K(2)S(2)O(8) and KI, respectively; prior to the stibine generation. The gaseous SbH(3) is separated from the solution in a gas phase separator, and transported by means of a nitrogen carrier into a short pathway (10 cm) IR gas cell, where the corresponding FTIR spectrum is acquired by accumulating 3 scans in a continuous mode. The 1893 cm(-1) band was used for the quantification of the antimony. The procedure is carried out in a closed system, which reduces sample handling and makes possible the complete automation of the antimony determination. The figures of merit of the proposed method (linear range: 0-600 mg l(-1), limit of detection (3sigma)=0.9 mg l(-1), limit of quantification (10sigma)=3 mg Sb l(-1), precision (R.S.D.) less than 1% and sample frequency=28 h(-1)), are appropriate for the designed application. Furthermore, precise and accurate results were found for the analysis of different antimonial pharmaceutical samples, indicating that the methodology developed represents a valid alternative for the determination of antimony in pharmaceuticals, which could be suitable for the routine control analysis.

Column-switching high-performance liquid chromatographic analysis of carbamazepine and its principal metabolite in human plasma with direct sample injection using an alkyl-diol silica (ADS) precolumn.

In this paper, the on-line coupling of solid-phase extraction, based on a restricted-access support with high-performance reverse phase chromatography for the analysis of carbamazepine (CBZ) and carbamazepine-10,11-epoxide (CBZ-E) in human plasma samples is described. A precolumn packed with 25 mum C(18) alkyl-diol support is used for direct plasma injection. Using column-switching techniques, the analytes were enriched on the precolumn by a 5 mM phosphate buffer (pH 7) with 2% of methanol solution at a flow-rate of 0.8 ml min(-1), while proteins and endogenous hydrophilic substances in plasma were washed off to waste. The enriched analytes were then back-flushed onto the analytical C(18) column, separated by a mixture of 10 mM phosphate buffer (pH 7) acetonitrile (70:30 v/v) solution at a flow-rate of 1.0 ml min(-1) and detected by the ultraviolet absorbance set at 212 and 285 nm and without transfer loss. Linear calibration graphs were obtained for sample injection volumes of 50 (0.2-4.0 of mug of CBZ ml(-1) and 0.1-5.0 mug of CBZ-E ml(-1), respectively), and 20 mul (5.0-20.0 mug of CBZ ml(-1)); in either case the r-value was >0.9963. Recoveries from spiked plasma samples were quantitative for both analytes and the coefficients of variation were below 3.83%. The lowest samples concentrations that can be quantified with acceptable accuracy and precision was 0.2 mug CBZ ml(-1) and 0.1 mug CBZ-E ml(-1) when a sample volume of 50 mul was injected. Concentrations of 0.08 and 0.05 mug ml(-1) of CBZ and CBZ-E were considered the limit of detection for a signal-to-noise ratio of 3. Furthermore, the developed column-switching method was successfully applied to the determination of CBZ and CBZ-E in plasma samples of patients submitted to CBZ therapy.

A flow injection-ETAAS system for the on-line determination of total and dissolved silica in waters.

In this work total (Si-tot) and 'soluble' or reactive (Si-sol) concentrations of silicon in natural and tap waters were sequentially determined by electrothermal atomic absorption spectrometry (ETAAS). First, samples were on-line diluted based on the merging-zone principle in order to allow the determination of Si-tot within the 300-1000 mugSil(-1) range. After the dilution process, a sub-sample was collected in the capillary of a sampling arm assembly (SAA). Thereafter, samples were subject to a precipitation/dissolution process in order to allow the determination of Si-sol within the 280-850 mugSil(-1). Si-sol was precipitated with ammonium chloride and collected on the walls of a knotted coil. The precipitate was dissolved with ammonium molybdate in an acidic medium (HNO(3)) and a sub-sample was then collected in the SAA. In both cases, 10 mul volumes of the sub-sample were injected into the atomizer with the previous introduction of 20 ng of Eu as chemical modifier (10 mul) by the spectrometer autosampler. The recovery values obtained with natural waters spiked samples were over 46% and the agreement between observed and certified samples values was good. The proportion of Si-sol in comparison with the Si-tot was high (85-95%) in most natural waters. The precision of the method was 2.4-3.5 and 4.5-6.2% (n=10) for the determination of Si-tot and Si-sol, respectively.

An on-line flow-injection microwave-assisted mineralization and a precipitation/dissolution system for the determination of molybdenum in blood serum and whole blood by electrothermal atomic absorption spectrometry.

An on-line flow injection (FI) precipitation-dissolution system with microwave-assisted sample digestion has been developed for the electrothermal atomic absorption spectrometry (ETAAS) determination of trace or ultratrace amounts of molybdenum in human blood serum and whole blood samples. After the exposure of the sample to microwave radiation, the on-line precipitation of molybdenum was achieved by the merging-zone of a 0.5-ml plug of sample with a plug of potassium ferrocyanide, which were carried downstream with a solution of 0.5 mol l(-1) of HNO(3). The interfering effects of iron and copper were minimized by the introduction of a flow of a 5% (w/v) sodium potassium tartrate (for iron) and 2% (w/v) of thiourea (for copper and zinc) in a 5% (v/v) ammonia and 2% (v/v) ammonium chloride solution previous to the precipitation reaction. The reddish-brown precipitate of molybdenyl ferrocyanide was collected on the walls of a knotted reactor. The precipitate was dissolved with the introduction of 1 ml of a 3.0 mol l(-1) NaOH solution and the best performance in terms of detection limit and precision was achieved when a sub-sample of 140 mul was collected in a capillary of a sampling arm assembly, to introduce 20 mul volumes into the atomizer by means of positive displacement with air through a time-based injector. A detection limit (3sigma) of 0.1 mug Mo l(-1) using an aqueous standard solution was obtained. The method is quantitative and is applied over the range 0.2-20.0 mug Mo l(-1). The precision of the method evaluated by ten replicate analyses of aqueous standard solutions containing 0.5 and 1.0 mug Mo l(-1) was 2.8 and 3.1% (relative standard deviation, RSD) (for n=5), respectively. Whereas, the precision evaluated by five replicate analysis of a serum and a whole blood sample were 3.3 and 3.8% RSD. An enrichment factor of ca. 3.5 was achieved with the introduction of 0.5 ml aqueous standard solutions at a sample flow rate of 1.0 ml min(-1). Recoveries of spiked molybdenum in blood serum and whole blood were in the ranges 96-102 and 94-98%, respectively. The results obtained for two human whole blood certified reference materials were in good agreement with the indicative values.

On-line determination of antimony(III) and antimony(V) in liver tissue and whole blood by flow injection - hydride generation - atomic absorption spectrometry.

A new analytical procedure for the speciation of antimony in liver tissues is presented here. For this purpose, a flow injection system has been developed for the treatment of samples and the determination of antimony by hydride generation - atomic absorption spectrometry. The method involves the sequential and the on-line extraction of antimony(III) and antimony(V) from solid lyophilized blood and hamsters liver tissues, with 1.5 mol l(-1) acetic acid and 0.5 mol l(-1) sulfuric acid for Sb(III) and Sb(V), respectively. Reduction of Sb(V) to Sb(III) for stibine generation is effected by the on-line pre-reduction with l-cysteine. The linear ranges were 2.5-20 and 1.0-25 mug l(-1) of Sb(III) and Sb(V), respectively. The detection limits (3sigma) were 1.0 mug l(-1) for Sb(III) and 0.5 mug l(-1) for Sb(V). The relative standard deviation values for fifteen independent measurements were 2.1 and 1.8% for Sb(III) and Sb(V), respectively. The recovery studies performed with samples of cattle liver provided results from 98 to 100% for Sb(III) and from 100 to 103% for Sb(V) for samples spiked with single species. For samples spiked with both Sb(III) and Sb(V), the recovery varied from 97 to 103% for Sb(III) and from 101 to 103% for Sb(V).

Endocrine effects of lithium carbonate in healthy premenopausal women: relationship with body weight regulation.

The mechanisms involved in Li-induced weight gain remain unclear. The higher frequency of obesity in women than in men under Li treatment, suggests a role for reproductive hormones. The serum levels of the following hormones were evaluated in healthy young women at diverse stages of a control menstrual cycle, and during Li carbonate (900 mg/day) or placebo administration: prolactin, luteinizing hormone, follicle-stimulating hormone, 17-1 estradiol, progesterone, thyroxine, thyrotropin, cortisol, dehidroepiandrosterone sulfate, free testosterone, leptin and an oral glucose tolerance test, in order to measure the areas under the glucose and insulin curve. The body weight was assessed the day before and the last day of treatment. The Li serum levels 15 hours after the last dose were 0.31 +/- 0.1 mEq/L. No significant changes in body weight and in the normal fluctuations of the reproductive hormones along the menstrual cycle were observed during Li administration. An increase in the serum levels of thyrotropic hormone ( p = 0.0001) was the only significant effect of Li, which may predispose to excessive weight gain after prolonged administration of the cation. The remarkable lack of effects of Li on these hormones, question the pertinence of studies conducted in healthy volunteers for the comprehension of the obesity observed in psychiatric patients who may be particularly prone to gain weight under prolonged treatment with high dose of Li.

Determination of beryllium in natural and waste waters using on-line flow-injection preconcentration by precipitation/dissolution for electrothermal atomic absorption spectrometry.

A flow injection (FI) on-line precipitation-dissolution was developed for electrothermal atomic absorption spectrometry (ETAAS) determination of (ultra)trace amounts of beryllium in water samples. Beryllium was precipitated quantitatively with NH(4)OH+NH(4)Cl and collected in a knotted tube of Tygon without using a filter, while the other matrix components flowed downstream to waste. The precipitate was dissolved with nitric acid and a sub-sample was collected in a capillary of a sampling arm assembly, to introduce 10 mul volumes into the graphite tube by means of positive displacement with air through a time-based injector. This sequence was timed to synchronize with the previous introduction of 6 mug of Lu (in 20 mul) by the spectrometer autosampler. The effect of a number of possible cations on the beryllium precipitation process was studied. While, the addition of Ba(2+), Sr(2+), Ca(2+), Mg(2+), Mn(2+), Zn(2+), Co(2+) and Ni(2+) did not produce any perceptible precipitate on the reaction coil walls, the addition of Al(3+), Cr(3+) and Fe(3+) produced large precipitated particles. However, their tolerance limit was well above the levels at which theses species are commonly found in most natural waters. The detection limit (3sigma) of 25 ng l(-1) in the sample solution was obtained. The precision of the method, evaluated by ten replicate analyses of solutions containing 20 and 200 pg of beryllium were 4.8 and 4.0% (n=5), respectively. Enrichment factors from 7.0 to 10.3 and from 10.5 to 13.8 were obtained for precipitation times from 25 to 38 s and from 43 to 50 s for waste and tap waters, respectively. These results indicate that the enrichment factor was limited by the interference of some matrix metals which could precipitate as hydroxides (or related species) and be retained in the reaction coil. The integrated system permits fully automated operation, avoiding time-consuming manual work and enhancing the reproducibility and precision of the determination of beryllium. The results obtained for the determination of beryllium in certified reference materials (trace elements in water), together with the good recovery of spiked analytes, demonstrate the applicability of the procedure to the analysis of natural waters.

Sequential determination of Se(IV) and Se(VI) by flow injection-hydride generation-atomic absorption spectrometry with HCl/HBr microwave aided pre-reduction of Se(VI) to Se(IV).

In this study a flow injection (FI) system used in conjunction with hydride generation (HG), atomic absorption spectrometry (AAS) and microwave (MW) aided pre-reduction of selenite (Se(IV)) to selenate (Se(IV)) with HCl:HBr has been developed in order to differentiate both inorganic selenium species. As full control of the MW reduction step is possible, the experimental approach allows the use of milder acidic conditions (10% v/v of HCl and HBr) than those conventionally accomplished with hydrochloric acid alone (>/=50% v/v). Experimental parameters were optimized by the univariate optimization method. In either case, the linear range was from 1.0 to 30 mug l(-1). The detection limits based on 3sigma of the blank signal were 0.25 mug l(-1) for Se(IV) and 0.30 mug l(-1) for Se(VI). The reproducibility, about 3% RSD and recoveries of different amounts of Se(VI) and Se(IV) added to water and orange juice samples (97-103%) were good. The main advantage of the proposed method is that the sequential determination of Se(IV) and Se(VI) is performed at a high sampling frequency (ca. 50 samples per h) in a closed system without Se losses, and with a minimum sample waste, operator attention, and sample manipulation.

The use of emulsions for the determination of methylmercury and inorganic mercury in fish-eggs oil by cold vapor generation in a flow injection system with atomic absorption spectrometric detection.

An on-line time based injection system used in conjunction with cold vapor generation atomic absorption spectrometry and microwave-aided oxidation with potassium persulfate has been developed for the determination of the different mercury species in fish-eggs oil samples. A three-phase surfactant-oil-water emulsion produced an advantageous flow when a peristaltic pump was used to introduce the highly viscous sample into the system. The optimum proportion of the oil-water mixture ratio was 2:3 v/v with a Tween 20 surfactant concentration in the emulsion of 0.008% v/v. Inorganic mercury was determined after reduction with sodium borohydride while total mercury was determined after an oxidation step with persulfate prior to the reduction step to elemental mercury with the same reducing agent. The difference between total and inorganic mercury determined the organomercury content in samples. A linear calibration graph was obtained in the range 0.1-20 micrograms l-1 of Hg2+ by injecting 0.7 ml of samples. The detection limits based on 3 sigma of the blank signals were 0.11 and 0.12 microgram l-1 for total and inorganic mercury, respectively. The relative standard deviation of ten independent measurements were 2.8 and 2.2% for 10 micrograms l-1 and 8.8 and 9.0% for 0.1 microgram l-1 amounts of total and inorganic mercury, respectively. The recoveries of 0.3, 0.6 and 8 micrograms l-1 of inorganic and organic mercury added to fish-eggs oil samples ranged from 93.0 to 94.8% and from 100 to 106%, respectively. Good agreement with those values obtained for total mercury content in real samples by electrothermal atomic absorption spectrometry was also obtained, differences between mean values were < 7%. With the proposed procedure, 22 proteropterous catfish-eggs oil samples from the northwestern coast of Venezuela were measured; while the organic mercury lay in the range 2.0 and 3.3 micrograms l-1, inorganic mercury was not detected.

Serum trace elements and fat-soluble vitamins A and E in healthy pre-school children from a Venezuelan rural community.

Zn (SZn), Cu (SCu), Fe (SFe), vitamin A (SVA) and vitamin E (SVE) were measured in blood serum samples of 85 healthy pre-school children aged 2-6 yr. from the rural community of Canaguá, Mérida State, Venezuela. The relationship between these biochemical indexes was also investigated. The mean serum concentrations of zinc, copper, iron, vitamin A and vitamin E were 0.74 +/- 0.25, 1.18 +/- 0.30, 0.76 +/- 0.20, 0.30 +/- 0.15 and 5.87 +/- 0.43 mg/L, respectively. There was a tendency for SZn to increase with age, whereas SCu and SVA decreased. There was no significant difference in serum trace elements and fat-soluble vitamin concentration between males and females in the different age groups. SFe tended to be lower than that reported in the literature. However, the age groups studied showed no statistically significant sex- and age-related differences. The present study shows that there is a complex interaction between SZn, SCu, SFe, SVA, SVE and age of the children. Multiple regression analysis showed serum zinc was strongly related to serum copper, and serum iron. Serum vitamin A was strongly related to serum zinc and serum vitamin E, whereas serum vitamin E was strongly related to serum zinc, serum copper, and serum vitamin A. On the other hand, our observations also suggest that more detailed studies of these metals and fat-soluble vitamins should be carried out, and that the study should include nutritional surveys, metabolic balances and associations between SZn, SCu, SFe, SVA and SVE and anthropometric variables (height, weight, body mass index and skinfold thickness).

Determination of bismuth in biological samples using on-line flow-injection microwave-assisted mineralization and precipitation/dissolution for electrothermal atomic absorption spectrometry.

An on-line automated flow injection system with microwave-assisted sample digestion for the electrothermal atomic absorption spectrometric determination of bismuth in biological materials is described. After the exposure of the sample to microwave radiation, the analyte was subject to a precipitation/dissolution process. Bismuth was precipitated with the stannite ion in basic medium and collected on the walls of a knotted coil, while the other matrix components flowed downstream to waste. The precipitate was dissolved with nitric acid and a sub-sample was collected in a capillary of a sampling arm assembly, to introduce 20 mul volumes into the graphite tube by means of positive displacement with air through a time-based injector. The analytical figures of merit were first evaluated by filling the sampling arm with a standard solution of bismuth and thereafter injecting aliquots of this solution into the atomizer. The calibration graph was linear from the detection limit (8 pg) to 1.2 ng of bismuth. The sensitivity was of 26.8 mug l(-1) for 0.2 A-s and the characteristic mass (m(o)) was of 11.8 pg/0.0044 A-s. The precision of the method, evaluated by replicate analyses of solutions containing 20 and 200 pg of bismuth, were 5.5 and 3.0% (n=10), respectively. When solutions were introduced in the flow system here described, the calibration graph was linear in the range 0.04-6.0 mug l(-1), which means that a preconcentration factor of 10 was obtained for bismuth. The precision slightly deteriorated, e.g. the replicate analysis of solutions containing 1 and 10 pg of bismuth were 7.1 and 5.3% (n=10), respectively. However, the recoveries values obtained with urine and whole blood bismuth spiked samples were over 96.5% and the agreement between observed and certified values was good.

Determination of methylmercury and inorganic mercury in whole blood by headspace, cryofocusing gas chromatography and atomic absorption spectrometry.

A method for the determination of different mercury species in whole blood is described. Inorganic mercury (InHg) was determined in 2 ml of standard solutions or blood samples using head space (HS) injection coupled to atomic absorption spectrometry (AAS) after treatment with concentrated sulfuric and tin(II) chloride as a reductant agent in a closed HS vial. After stirring, the InHg was converted to elementary mercury and carried with a nitrogen flow through a quartz cell heated at 200 degrees C and the absorbance signal was evaluated by AAS. For the determination of methylmercury (MeHg), 2 ml of a standard solution or a blood sample were treated with 10 mg of iodoacetic acid and 0.4 ml of concentrated H2SO4. Then, the MeHg species were HS-injected into a gas chromatograph (GC), separated on a semicapillary column (AT-1000) with a flow of helium, then carried to the quartz cell heated at 1000 degrees C and detected by AAS. The high content of salts in blood samples, where sodium chloride is the major component (0.14 mol l-1), affected the gas-liquid distribution coefficient of both mercury species in the HS vial. A linear calibration graph was obtained in the ranges 1-20 and 1-125 micrograms Hg l-1 added as InHg and MeHg, respectively. The detection limits for InHg and MeHg were 0.6 and 0.2 microgram Hg l-1, respectively. The relative standard deviations for eleven independent measurements were 5% for both mercury species. Recovery values ranging from 98 to 106% for InHg and from 95 to 105% for MeHg and from 93 to 95% for ethylmercury (EtHg) were obtained. The accuracy of the proposed method was also established by the analysis of certified whole blood samples for InHg and MeHg. No difference between the sum of these two species determined by our procedure and the recommended total mercury concentrations in the certified samples was observed. Results for the determination of MeHg and InHg in 30 controls and 30 dentists are presented to illustrate the practical utility of the proposed method.

Determination of nickel in saliva by electrothermal atomic absorption spectrometry using various chemical modifiers with Zeeman-effect background correction.

The profile of nickel signal using electrothermal atomic absorption spectrometry with deuterium and Zeeman-effect background correction is presented. The Zeeman effect system of background correction offered definitive advantages and therefore was used for the determination of nickel in saliva in the presence of various isomorphous metals. The highest nickel absorbance values corresponded at 200, 300, 300, 300, 600, and 200 ng of Tb, Mg, Sm, Lu, Tm, and Pd, respectively. On the other hand, the addition of Eu, Er, and Ho decreased the nickel signal. The presence on each modifier alone does not eliminate the matrix interference. However, the use of 200 ng of Pd in conjuction with 300 ng of Lu has a higher sensitivity, offers an advantage against interference from the background of saliva matrix and produces good recoveries (98 to 102% from unspiked and spiked saliva samples). The limit of detection was 0.11 micrograms/L for a characteristic mass of 16.6 pg of nickel using Pd-Lu as modifier. The within-batch precision varied between 0.8 and 1.5% relative standard deviations. The analysis of thirty samples of whole saliva gave an average of 0.81 +/- 0.30 of micrograms/L of Ni (range from 0.5 to 2.0 micrograms/L of Ni). The agreement between the observed and certified values obtained from a Seronorm Blood Serum Standard Reference Material was good.

On-line cryogenic trapping with microwave heating for the determination and speciation of arsenic by flow injection/hydride generation/atomic absorption spectrometry.

An on-line flow injection-hydride generation/atomic absorption spectrometry method was developed for the preconcentration and selective determination of inorganic arsenic [As(III) and As(V)] and its methylated species. The separation of the arsenic species was performed by an automated pH-selective arsines generation technique, using sodium tetrahydroborate(III) as reductant. Each arsine was cryogenically trapped in a PTFE coil, knotted and sealed inside another wider diameter tube, through which liquid nitrogen was suctioned by negative pressure. Then, based on their different boiling points, the arsine species were selectively liberated by using a heating cycle of microwave radiation, followed by atomic absorption detection. A sample solution aliquot mixed with 1% citric acid was used for the determination of As(III) alone, while a second sample aliquot mixed with 2 mol l(-1) nitric acid was used for the quantitative determination of total inorganic arsenic, monomethylarsonic acid and dimethylarsinic acid. Based on 10 ml sample, the detection limits lie within the range 20-60 ng As l(-1), which are sufficiently low to detect the arsines-forming species in natural waters. These values are negatively affected by the reagents purity and background noise due to flame flickering, but the sensitivity can substantially be improved by increasing sample size or running several consecutive reactions.