Sampling High-resolution Continuum Source Graphite Research Articles

Determination of thallium in water samples via solid sampling HR-CS GF AAS after preconcentration on chromatographic paper

A method for determining thallium in water samples via solid sampling high-resolution continuum source graphite furnace atomic absorption spectrometry (SS HR-CS GF AAS) after preconcentration using chromatographic filter paper as a solid support was proposed. The effects of pH, stirring time, and sample volume in the analyte preconcentration step were studied. The presence of potential interferences in the sample and the type of masking agent were also examined. In the proposed procedure, the sample was placed in contact with the solid phase in a polypropylene tube, and after stirring for 3 min, thallium determination was performed via HR-CS GF AAS directly on chromatographic filter paper. A preconcentration factor of 55, a precision of 9.4% (n = 10; 10 μg L−1), a limit of detection of 0.018 μg L−1, and a limit of quantification of 0.059 μg L−1 were achieved. Analyte addition and recovery tests were performed, and the results ranged from 91% to 110%. The accuracy of the method was evaluated by analyzing a water reference material. The procedure was used to determine thallium in water samples collected in Barreiras, Bahia, Brazil. The results were compared with those obtained using inductively coupled plasma‒mass spectrometry (ICP‒MS). Thallium concentrations in the analyzed samples ranged from <0.059 to 0.80 μg L−1.

An environmentally friendly approach for the characterization of construction materials: determination of trace, minor, and major elements by slurry sampling high-resolution continuum source graphite furnace atomic absorption spectrometry.

A slurry sampling method was developed for the fast determination of Pb, Ni, Fe, and Mn in construction materials by high-resolution continuum source graphite furnace atomic absorption spectrometry (HR-CS GFAAS). For sample introduction into the GF, stable slurries were prepared by sonicating 10 mg of ground solid sample in 10.0 mL of 1% (v/v) Triton X-100 and 1% (v/v) HNO3 solution for 1.0 min. The determination of the four elements was carried out in three measurement runs, with Ni and Fe being determined simultaneously. The HR-CS GFAAS measurements were performed using analytical lines with adequate sensitivity, considering the content of each element in the material: Pb at 283.306 nm (42%), Mn at 403.080 nm (6.7%), Ni at 232.003 nm (100%) and Fe at 232.036 nm (1.4%). The pyrolysis and atomization temperatures and the use of chemical modifiers were optimized using both aqueous standards and slurry samples. At optimal conditions, samples with concentrations of Pb from 1.5 to 80 μg g-1, Ni from 4.0 to 75 μg g-1, Mn from 2.0 to 600 μg g-1, and Fe from 0.15 to 60 mg g-1 could be determined using a unique sample suspension. To assess the validity of the method, a fly ash certified reference material (CRM) was analysed using the slurry sampling HR-CS GFAAS method; this CRM and the construction material samples were also analysed by HR-CS GFAAS after the digestion of the samples. The obtained results using both methods were statistically comparable (Student's paired t-test for two independent methods at a 95% confidence level) demonstrating the suitability of the proposed method.

Sequential and Simultaneous Determination of Cd, Fe and Ni in Toothpastes Employing Slurry Sampling High-Resolution Continuum Source Graphite Furnace Atomic Absorption Spectrometry

Here is reported an analytical method for the multielemental determination of Cd, Fe and Ni in toothpaste employing slurry sampling high-resolution continuum source electrothermal atomic absorption spectrometry (HR-CS ET AAS). Using a single sample aliquot, Cd was determined at 228.802 nm, and, sequentially, Fe (232.036 nm) and Ni (232.003 nm) were simultaneously determined. Pyrolysis and atomization temperatures were 800 and 1500 °C for Cd, respectively. An atomization temperature of 2600 °C was used for Fe and Ni. A Pd and Mg mixture was used as the chemical modifier for standards and samples. The procedure for the slurry preparation was optimized using multivariate methodology with a multiple response function while employing a sample mass of about 250 mg. The optimized conditions were: 0.8 mol L−1 HNO3, 0.5% (m/v) Triton X-100 and a sonication time of 15 min. Using aqueous standards for the calibration, limits of detection and quantification were of 3.2 and 10.8 ng g−1 for Cd, 2.2 and 7.4 µg g−1 for Fe, and 0.044 and 0.148 µg g−1 for Ni. The precision estimated as relative standard deviation (n = 5) was 6.1% for Cd, 3.5% for Fe and 4.4% for Ni. The method accuracy was evaluated by standard addition and recovery tests and the recoveries varied from 93 to 114%. The method was applied for the analysis of five toothpaste samples of different brands. The concentrations ranged from 52.0 to 73.6 µg g−1 for Fe, and < 0.148 to 0.227 µg g−1 for Ni. For Cd, the concentrations were below the limit of detection.

Simultaneous determination of Fe and Zn in dried blood spot by HR-CS GF AAS using solid sampling

Dried Blood Spot (DBS) was evaluated as a solid sampling (SS) strategy for the simultaneous determination of Fe and Zn in blood samples by Solid Sampling High-Resolution Continuum Source Graphite Furnace Atomic Absorption Spectrometry (SS HR-CS GF AAS). The alternative lines of Fe and Zn at 307.572 and 307.589 nm, respectively, were evaluated. A good correlation between the area of DBS (in mm2) and volume of blood (in µL) was observed up to 200 µL of blood. A 3.4 mm diameter paper disk, equivalent 3.86 ± 0.13 µL, was punched from the DBS and employed for blood analysis. Random sampling through the area of the paper circle produced by 50 μL blood samples showed no chromatographic effects. The upside of the solid sampling 'boat type' graphite platform was coated with a W-based film. This coating allowed around 350 firings. The use of 3 µL of 15% v/v H2O2 solution as chemical modifier improved both the thermal stability and peak profile of Zn for aqueous medium (standard solution deposited onto Whatman paper), possibly because of the weakening of Zn-paper interactions or even by the formation of thermally more stable Zn oxides. Solid standards used for calibration in the 0.1–3.0 µg Fe and 5.0–50.0 ng Zn ranges were prepared with Whatman 903® paper discs impregnated with standard solutions of the analytes. Results for Fe and Zn determined by the proposed SS HR-CS GF AAS method were in agreement at a 95% confidence level (paired t-test) with those obtained by the comparative method (except for one sample) based on microwave-assisted acid digestion of blood and High-Resolution Continuum Source Flame Atomic Absorption Spectrometry (HR-CS F AAS). The limits of quantification were 10.2 mg/L (0.04 µg) for Fe and 1.2 mg/L (4.6 ng) for Zn. The relative standard deviation was < 10% (n = 12) for a sample containing 516 mg/L Fe and 8.7 mg/L Zn, and the sample throughput was equivalent to ca. 90 s per measurement.

Fast-sequential determination of cadmium and copper in milk powder and infant formula by direct solid sampling high-resolution continuum source graphite furnace atomic absorption spectrometry

A sequential and direct solid sampling (SS) method to determine cadmium (Cd) and copper (Cu) in milk powders and infant formulas was developed using a high-resolution continuum source graphite furnace atomic absorption (HR-CS GFAA) spectrometer. The analysis was performed using a unique sample aliquot and in one measurement run. Absorbance measurements were carried out at the main analytical lines for Cd (228.802 nm) and Cu (324.754 nm). Experimental conditions were optimized using aqueous standards and a skimmed milk powder certified reference material (ERM®–BD150). Palladium was added as chemical modifier in standards and samples. For Cd determination, a pyrolysis temperature of 900 °C and an atomization temperature of 1400 °C were used. Afterwards, the wavelength was automatically changed, and Cu was determined from the same aliquot of sample using an atomization temperature of 2200 °C. Calibration was performed using aqueous standards. Using three pixels (CP ± 1) for the quantification of both elements and a sample mass of 0.9 mg, the limits of quantification (LOQs) and the upper limits of the linear range (ULLRs) were 2.1 µg kg−1 and 56 µg kg−1 for Cd (1.9 to 50 pg), and 0.021 mg kg−1 and 1.7 mg kg−1 for Cu (0.019 to 1.5 ng), respectively. The linear response of Cu was expanded up to 4.7 mg kg−1 (4.2 ng) by using the approach of measuring at the wings of the absorption line. The developed methodology was applied to analyse different commercial milk powder and infant formula samples with successful results.

The use of dried matrix spot for determination of Pb and Ni in automotive gasoline by solid sampling high-resolution continuum source graphite furnace atomic absorption spectrometry

In this work a simple and practical method for the determination of Pb and Ni in automotive gasoline by solid sampling high-resolution continuum source graphite furnace atomic absorption spectrometry was investigated. In the proposed method, disks of filter paper were used to pre-concentrate and store Pb, Ni and other trace elements from automotive gasoline samples. For this, a volume of sample was deposited and dried out on a filter paper disk previously adapted into a polytetrafluoroethylene mold, and then the gasoline-embedded filter paper was either cut into small pieces or pulverised and introduced directly into the graphite furnace for trace element determination. Temperature program, use of chemical modifier, chromatographic effect and volume of sample were investigated. Calibration curves using organic and inorganic standards of the analytes as well as external and internal calibration methods were evaluated. Using optimised conditions, characteristic masses and limits of detection of 6 and 11 pg, and 0.5 and 2.1 μg L-1 were found for Pb and Ni, respectively. The accuracy of the method was evaluated with spike-recovery tests and a certified reference material of wear lubricant oil. The spike-recovery tests were accomplished for 9 samples and the best results were obtained with the pulverised filter paper. A second method that employs a transversely heated filter atomiser was applied as a comparative one. The filter paper was shown to be a simple and inexpensive tool for storage and transportation of gasoline samples, and it allowed the pre-concentration of the analytes, since a larger volume of sample can be dried out on it.

Method development for the determination of cadmium in lipsticks directly by solid sampling high-resolution continuum source graphite furnace atomic absorption spectrometry

A practical and fast method was developed for the determination of cadmium in lipstick by high-resolution continuum source graphite furnace atomic absorption spectrometry with solid sampling. Since digestion step was not applied, the method was fast, simple, cheap and environmentally friendly. In addition, the risks of contamination and/or analyte loss prior to analysis were eliminated. Lipstick samples were put on the platform around 1.0 to 2.5 mg, Pd was injected as a modifier and introduced to the furnace by means of manual solid sampler. Interference-free determination of cadmium was carried out using aqueous standards for calibration applying 850 °C for pyrolysis and 1600 °C for atomization. The aqueous cadmium standard added on a solid lipstick was quantitatively recovered. The limit of detection and characteristic mass were 5.0 pg and 2.8 pg, respectively. Finally, the cadmium concentrations in various kinds of lipsticks were determined applying the optimized conditions developed in this study. Additionally, micro-scale heterogeneity of cadmium distribution in the samples were determined.

Determination of gold and cobalt dopants in advanced materials based on tin oxide by slurry sampling high-resolution continuum source graphite furnace atomic absorption spectrometry

A novel approach is developed for the determination of Co and Au dopants in advanced materials based on tin oxide using high-resolution continuum source graphite furnace atomic absorption spectrometry (HR CS GFAAS) with direct slurry sampling. Sodium carboxylmethylcellulose (Na-CMC) is an effective stabilizer for diluted suspensions. Use Na-CMC allows to transfer the analytes into graphite furnace completely and reproducibly. The relative standard deviation obtained by HR CS GFAAS was not higher than 4%. Accuracy was proven by means inductively coupled plasma mass spectrometry (ICP-MS) in solutions after decomposition as a comparative technique. To determine Au and Co in the volume of SnO2, the acid decomposition conditions (HCl, HF) of the samples were suggested by means of an autoclave in a microwave oven.

Solid sampling high-resolution continuum source graphite furnace atomic absorption spectrometry for gold determination in geological samples after preconcentration onto carbon nanotubes

A novelty method for the determination of gold in geological samples by solid sampling high-resolution continuum source graphite furnace atomic absorption spectrometry (SS HR CS GF AAS) after solid-phase extraction onto modified carbon nanotubes (CNT) was described. The methodology developed is based on solid phase extraction of Au(III) ions from digested samples to eliminate strong interference caused by iron compounds and problems related to inhomogeneities of the samples. The use of aqueous or solid standard for calibration was studied and the slope of calibration curve was the same for both of these modes. This statement indicates the possibility to perform the calibration of the method using aqueous standard solutions. Under optimum conditions the absolute detection limit for gold was equal to 2.24·10−6μgg−1 while the adsorption capacity of modified carbon nanotubes was 264mgg−1. The proposed procedure was validated by the application of certified reference materials (CRMs) with different content of gold and different matrix, the results were in good agreement with certified values. The method was successfully applied for separation and determination of gold ions in complex geological samples, with precision generally better than 8%.

Effect of different precursors on generation of reference spectra for structural molecular background correction by solid sampling high-resolution continuum source graphite furnace atomic absorption spectrometry: Determination of antimony in cosmetics

Different precursors were evaluated for the generation of reference spectra and correction of the background caused by SiO molecules in the determination of Sb in facial cosmetics by high-resolution continuum source graphite furnace atomic absorption spectrometry employing direct solid sample analysis. Zeolite and mica were the most effective precursors for background correction during Sb determination using the 217.581nm and 231.147nm lines. Full 23 factorial design and central composite design were used to optimize the atomizer temperature program. The optimum pyrolysis and atomization temperatures were 1500 and 2100°C, respectively. A Pd(NO3)2/Mg(NO3)2 mixture was employed as the chemical modifier, and calibration was performed at 217.581nm with aqueous standards containing Sb in the range 0.5–2.25ng, resulting in a correlation coefficient of 0.9995 and a slope of 0.1548s ng−1. The sample mass was in the range 0.15–0.25mg. The accuracy of the method was determined by analysis of Montana Soil (II) certified reference material, together with addition/recovery tests. The Sb concentration found was in agreement with the certified value, at a 95% confidence level (paired t-test). Recoveries of Sb added to the samples were in the range 82–108%. The limit of quantification was 0.9mgkg−1 and the relative standard deviation (n=3) ranged from 0.5% to 7.1%. From thirteen analyzed samples, Sb was not detected in ten samples (blush, eye shadow and compact powder); three samples (two blush and one eye shadow) presented Sb concentration in the 9.1−14.5mgkg−1 range.

Simultaneous determination of iron and nickel in fluoropolymers by solid sampling high-resolution continuum source graphite furnace atomic absorption spectrometry

This paper reports the development of a method of simultaneous determination of iron and nickel in fluoropolymers by high-resolution continuum source graphite furnace atomic absorption spectrometry (HR-CS GF AAS) with direct solid sampling. In order to carry out simultaneous measurements, both the main resonance line of nickel (232.003nm) and the adjacent secondary line of iron (232.036nm) were monitored in the same spectral window. The proposed method was optimized with a perfluoroalkoxy (PFA) sample and was applied to the determination of iron and nickel in fluorinated ethylene propylene (FEP) and modified polytetrafluoroethylene (PTFE-TFM) samples. Pyrolysis and atomization temperatures, as well as the use of Pd and H2 (during pyrolysis) as chemical modifiers, were carefully investigated. Compromise temperatures for pyrolysis and atomization of both analytes were achieved at 800 and 2300°C, respectively, using only 0.5Lmin−1 H2 as chemical modifier during pyrolysis. Calibration curves were performed with aqueous standards by using a single solution which contained both analytes. Limits of detection were 221 and 9.6ngg−1 for iron and nickel, respectively. Analyte concentrations in all samples ranged from 3.53 to 12.4µgg−1 for iron and from 37 to 78ngg−1 for nickel, with relative standard deviation less than 19%. Accuracy was evaluated by comparing these results with those obtained by inductively coupled plasma mass spectrometry after sample digestion by microwave-induced combustion and no significant statistical difference was observed.

Determination of Mercury in Istanbul Airborne Particles Using Solid Sampling High-Resolution Continuum Source Graphite Furnace Atomic Absorption Spectrometry

ABSTRACTA method for the determination of mercury in airborne particles by solid sampling high-resolution continuum source graphite furnace atomic absorption spectrometry is reported. Fine urban airborne particles were collected every month on quartz filters using a high-volume sampler (500 L/min) in Istanbul, Turkey. The filters loaded with airborne particles were directly introduced into the graphite furnace so that analyte losses during digestion were eliminated. Moreover, to prevent analyte losses in the furnace, no pyrolysis step was taken and silver and gold nanoparticles were used as novel modifiers. The effects of graphite furnace program, pyrolysis and atomization temperature, and mass of sample introduced into the furnace were characterized. The limits of detection in the absence of any modifier, in the presence of silver nanoparticles, and in the presence of gold nanoparticles were 0.52, 0.38, and 0.19 µg/L, respectively. The mercury concentrations in the air particulates were between 0.74 ± 0.10 and 3.65 ± 0.33 µg/L.

Determination of Cd, Ni and V in Spices by Solid Sampling High-Resolution Continuum Source Graphite Furnace Atomic Absorption Spectrometry

This work describes a procedure for determination of Cd, Ni and V in spices by high-resolution continuum source graphite furnace atomic absorption spectrometry (HR-CS GF AAS) using direct solid sampling (SS). The use of Pd/Mg(NO3)2 as modifier for Cd, and an additional air-assisted pyrolysis step allowed the use of aqueous calibration for all analytes. Accuracy was checked by analysis of certified reference materials (CRMs) and the results were in agreement to certified values at 95% confidence level (t-test). Eight samples of spices were analyzed by the proposed procedure and by inductively coupled plasma mass spectrometry (ICP-MS). The found concentrations were 88-233 ng g-1 Cd , 113-2842 ng g-1 Ni and 154-1007 ng g-1 V, with precision generally better than 12%. Results obtained by the proposed procedure were in agreement with those obtained by microwave-assisted digestion and ICP-MS determination. The limits of detection were 0.2, 18 and 7 ng g-1 for Cd, Ni and V, respectively.

Direct determination of lead in plastic toys by solid sampling high resolution-continuum source graphite furnace atomic absorption spectrometry

Lead concentrations in various plastic toys were determined directly by solid sampling high resolution continuum source graphite furnace atomic absorption spectrometry.

Determination of Manganese in Leisure Foods by Incomplete Digestion-Microemulsion Sampling-High Resolution Continuum Source Graphite Furnace Atomic Absorption Spectrometry

A fast and effective method was developed for determination of Mn in leisure foods by incomplete digestion-microemulsion sampling-high resolution continuum source graphite furnace atomic absorption spectrometry (HR-CS GFAAS). Microemulsions were prepared with digestive liquor and n-butyl alcohol as an auxiliary emulsifier after incomplete digestion treatment. The factors influencing determination were investigated by single factor experimental design. The optimal determination conditions were found as follows: the tartaric acid (1 mg/mL) was added as a chemical modifier with the volume of 4 μL; pyrolysis temperature 1100°C; atomization temperature 2000°C. The results showed that the correlation coefficient was better than 0.996, the characteristic concentration was 0.09 μg/L, the precision (RSD) for 6 replicate measurements of Mn was 2.8% and the average of recoveries was 97.3%. F-test and t-test (95% confidence level) in between the proposed method and the microwave digestion-HR-CS GFAAS method had no significant difference. Therefore, the proposed method was accurate and stable with a high practical value. It provided scientific basis for determination of metal elements in food.

Determination of Lead in Lipstick by Direct Solid Sampling High-Resolution Continuum Source Graphite Furnace Atomic Absorption Spectrometry: Comparison of Two Digestion Methods

A new analytical procedure for the determination of lead in lipstick has been developed using direct solid sampling high resolution continuum source graphite furnace atomic absorption spectrometry (SS HR CS GFAAS). The performance of this method has been compared to acid digestion methods for sample preparation, with or without hydrofluoric acid (HF) with inductively coupled plasma mass spectrometry (ICP-MS) detection. Good reliability was obtained for all three methods; the results obtained for certified reference materials with concentrations between 1 and 20 ppm were in agreement with the certified values. However, for materials with complex matrices, such as pearl or Ca-Na borosilicate, only ICP-MS with HF sample digestion or AAS with direct solid sampling allowed complete recovery of lead. To avoid the use of hazardous acids, the development of SS HR CS GFAAS is an interesting alternative. With the AAS method, a characteristic mass of 13.2 pg of lead was obtained, and the limit of detection was 0.005 µg/g. The performance of the method was evaluated by determining lead in lipstick. The use of the solid sampling technique constitutes a good alternative for accurate and rapid determination of lead content in lipstick and cosmetic raw materials, with a suitable limit of detection and a reduced risk of contamination or of analyte loss. Another alternative would be to use ICP-MS determination in conjunction with microwave-assisted acid digestion without the use of HF, which implies accepting a quantification of “nearly total” lead, closer to a “bio-extractible” fraction.

Direct determination of bromine in plastic materials by means of solid sampling high-resolution continuum source graphite furnace molecular absorption spectrometry

This work investigates the potential of high-resolution continuum source graphite furnace molecular absorption spectrometry for the direct determination of bromine in polymers, which could be interesting in view of the current regulations restricting the use of organobrominated compounds. The method developed is based on the addition of Ca (300μg) and Pd (30μg) to favor the formation of CaBr, which is monitored at the main molecular “lines” (rotational spectra) found in the vicinity of 625.315nm.It was found that accurate results could be obtained for all the samples investigated (polyethylene, polypropylene and acrylonitrile butadiene styrene certified reference materials) using any of the lines studied and constructing the calibration curve with aqueous standards. Furthermore, the combined use of the main four CaBr lines available in the spectral area simultaneously monitored permits to easily expand the linear range up to 2000ng, provides a limit of detection of 1.8ng (1.8μgg−1 for a mass of 1mg) and further improves precision to values between 3–7% RSD. Overall, the method proposed seems suited for the fast and simple control of these types of samples (approximately 10min for sample are required), circumventing the traditional problems associated with sample digestion (e.g., losses of volatile compounds), and providing sufficient sensitivity to easily comply with regulations.

Determination of Total Sulfur in Food Samples by Solid Sampling High-Resolution Continuum Source Graphite Furnace Molecular Absorption Spectrometry

The determination of sulfur in food samples via the rotational molecular absorption of carbon monosulfide (CS) was performed using a solid sampling high-resolution continuum source electrothermal atomic absorption spectrophotometer (SS-HR-CS-ETAAS). In the presence of plenty of carbon in the graphite furnace as well as in food samples, CS was formed in the gas phase without the addition of any molecule forming element externally. The effects of the wavelength selected to detect CS, graphite furnace program, amount of sample, coating of the graphite tube and platform with Ir, and the use of a Pd modifier on the accuracy, precision, and sensitivity were investigated and optimized. Sulfur was determined in an iridium-coated graphite tube/platform at 258.056 nm by applying a pyrolysis temperature of 1000 °C and a molecule forming temperature of 2400 °C. The calibration curve prepared from Na2S was linear between 0.01 μg (LOQ) and 10 μg of S. The accuracy of the method was tested by analyzing certified reference spinach and milk powder samples by applying a linear calibration technique prepared from aqueous standard. The results were in good agreement with certified values. The limit of detection and characteristic mass of the method were 3.5 and 8.1 ng of S, respectively. By applying the optimized parameters, the concentrations of S in onion and garlic samples were determined.

Simultaneous determination of Co, Fe, Ni and Pb in carbon nanotubes by means of solid sampling high-resolution continuum source graphite furnace atomic absorption spectrometry

This work explores the possibilities of solid sampling high-resolution continuum source graphite furnace atomic absorption spectrometry for the direct analysis of carbon nanotubes. In particular, the simultaneous determination of Co, Fe, Ni and Pb is intended, as these elements are typically found in these samples as impurities. The results demonstrate that it is possible to find spectral (monitoring of the region between 283.168 and 283.481 nm), furnace (2500 °C for atomization; use of 100 ng Pd as a chemical modifier) and detector (use of side pixels to expand the linear range) conditions that permit the development of a fast and straightforward method for the simultaneous determination of the target elements at the levels at which they are typically found (mg g−1 for Co, Fe and Ni; μg g−1 for Pb) in carbon nanotubes. Limits of detection of 23 pg (Pb), 6 ng (Fe), 65 ng (Ni) and 86 ng (Co) were obtained, which are suitable for this type of sample. In this way, it was feasible to carry out the analysis of the samples investigated (one candidate reference material and three commercially available samples) and achieve accurate results when constructing the calibration curve with aqueous standards. Precision values for 5 solid sample replicates varied between 7 and 15% RSD in most cases. Overall, the proposed method shows important benefits for the cost-effective analysis of such complex samples in routine labs.

A dried urine spot test to simultaneously monitor Mo and Ti levels using solid sampling high-resolution continuum source graphite furnace atomic absorption spectrometry

Home-based collection protocols for clinical specimens are actively pursued as a means of improving life quality of patients that require frequent controls, such as patients with metallic prosthesis, for whom monitoring the evolution of Mo and Ti in biological fluids may play a decisive role to detect prosthesis mal-functioning. The collection of biological fluids on clinical filter papers provides a simple way to implement these protocols.This work explores the potential of solid sampling high-resolution continuum source graphite furnace atomic absorption spectrometry for the simultaneous and direct determination of Mo and Ti in urine, after its deposition onto clinical filter paper, giving rise to a dried urine spot. The approach used for depositing the sample was found crucial to develop a quantitative method, since the filter paper acts as a chromatographic support and produces a differential distribution of the target analytes. Furthermore, the high spreading of urine onto a filter paper results in a small amount of urine per surface unit, and thus, ultimately, in lack of sensitivity. In order to circumvent these problems, the use of an alternative approach based on the use of pre-cut 17×19mm filter paper pieces onto which larger amounts of sample (500μL) can be retained by single deposition was proposed and evaluated. In this way, an approximately 12-fold increase in sensitivity and a more homogeneous distribution of the target analytes were obtained, permitting the development of a quantification strategy based on the use of matrix-matched urine samples of known analyte concentrations, which were subjected to the same procedure as the samples. Accuracy of this method, which provides LODs of 1.5μgL−1 for Mo and 6.5μgL−1 for Ti, was demonstrated after analysis of urine reference materials. Overall, the performance of the method developed is promising, being likely suitable for determination of other analytes in dried urine spots.