Isotope dilution – high efficiency nebulization-ICP-MS: The coupling of accuracy and sensitivity

If sample pretreatment, nebulization and method of calibration are suitably adapted to each other the performance of inductively coupled plasma - mass spectrometry ICP-MS can be greatly increased. High accuracy is obtained by high precision and low bias. For a given concentration higher sensitivity means higher count rates and therefore higher precision. Systematic errors are minimized by employing a definitive method of calibration. Increased sensitivity is obtained by introducing higher amounts of sample into the measurement system via high efficiency nebulizers (ultrasonic nebulizer, hydraulic-high pressure nebulizer according to Berndt and concentric high efficiency nebulizer according to Meinhard). Because this means also higher matrix effects a combination of ion chromatographic (IC-TMS) and thermal trace-matrix-separation by aerosol desolvation (T-TMS) is introduced. Isotope dilution (ID) proves to be the calibration most suitable to achieve the highest accuracy. First applications on the analysis of refractory metals (e.g. Ti, V, Nb, Ta) and non-metals (e.g. P, S, As, Se) showed recoveries of 60-105%, an imprecision of the recoveries of 2-50%, but an overall inaccuracy of only 0.1 to 4%.     

High efficiency nebulization for helium inductively coupled plasma mass spectrometry

A pneumatically-driven, high efficiency nebulizer is explored for helium inductively coupled plasma mass spectrometry. The aerosol characteristics and analyte transport efficiencies of the high efficiency nebulizer for nebulization with helium are measured and compared to the results obtained with argon. Analytical performance indices of the helium inductively coupled plasma mass spectrometry are evaluated in terms of detection limits and precision. The helium inductively coupled plasma mass spectrometry detection limits obtained with the high efficiency nebulizer at 200 μL/min are higher than those achieved with the ultrasonic nebulizer consuming 2 mL/min solution, however, precision is generally better with high efficiency nebulizer (1–4% vs. 3–8% with ultrasonic nebulizer). Detection limits with the high efficiency nebulizer at 200 μL/min solution uptake rate approach those using ultrasonic nebulizer upon efficient desolvation with a heated spray chamber followed by a Peltier-cooled multipass condenser.     

Microwave extraction of phthalate esters from marine sediment and soil

Summary As part of an on-going ASEAN⁺⁾-Canada Cooperative Programme on Marine Science, microwave-assisted solvent extraction has been employed for the extraction of six phthalate esters from marine sediment and soil samples. Five of the six esters studied are among the United States Environmental Protection Agency's list of top priority pollutants. The effects of extraction solvent, extraction temperature, duration of extraction and extraction volume on the mean recoveries of the six phthalate esters were quantitatively evaluated by means of an analysis of variance, followed by testing the differences among the level means for each condition with least significant difference method. Microwave-assisted solvent extraction allowed comparable or higher recoveries of the six phthalate esters (70.1–91.0%) in comparison with conventional soxhlet (65.5–89.5%) and sonication (64.6–88.6%). The precision of results by microwave-assisted solvent extraction was improved significantly compared to the conventional techniques. The microwave extraction system has many advantages over the soxhlet and sonication extraction, e.g., no laborious clean-up procedure, lower usage of hazardous organic solvent, and larger sample throughput. The technique has been employed for the analysis of native marine sediment and soil samples in Singapore.     

Determination of Nickel after Online Sorbent Preconcentration by FI-FAAS Using Dimethylglyoxime as a Complexing Agent

Dimethylglyoxime (DMG) has been tested as a complexing agent for the determination of nickel after online preconcentration on RP-C₁₈ in a microcolumn using flow injection coupled with a flame atomic absorption spectrometry system (FI-FAAS). The Ni–DMG complexes formed online can be adsorbed on the C₁₈ sorbent. Various parameters affecting the online Ni–DMG complex formation and its subsequent adsorption in the microcolumn as well as its elution into the nebulizer of the FAAS were optimized. A 10⁻³ mol/L solution of DMG in 4% ethanol was mixed online with an aqueous sample solution acidified to 0.1% (v/v) nitric acid and flowed for 30 s through the microcolumn. The adsorbed Ni–DMG complex in the microcolumn was eluted with ethanol containing 1% HNO₃ into the nebulizer of the FAAS in 10 s. A good precision (RSD = 1.7%, n = 14), high enrichment factor (21), and high sample throughput (90 h⁻¹) with detection limit (3ς) 3 μg/L were obtained. The method was applied to standard reference materials, i.e., NBS-362, NBS-364 (special low-alloy steel), and mussel (GBW 08571), for the determination of nickel and the results were in good agreement with certified values. Nickel recovery from seawater and high-purity magnesium oxide in the range 98–100% can be obtained by this method.     

Evaluation of the analytical performance of flow injection—Flame atomic absorption spectrometry

Analytical performance of flow injection—flame atomic absorption spectrometry was evaluated in terms of precision and sensitivity. For direct aqueous-solution introduction and alcoholic-eluate introduction after on-line sorbent extraction, the influence of the interfacing parameters was investigated, including the nebulizer uptake rate, sample-introduced flow rate and coupling tube length. High sensitivity could be achieved by the exploitation of the synergetic effect of both sample pumping and aspirating processes. A low nebulizer uptake rate combined with a high flow rate of the introduced sample zone produced the optimum precision better than 2% for peak-height measurements, the optimum rates being dependent on the nebulization characteristics of the solvent used. Precision and sensitivity deteriorate with increasing length of the coupling tube.     

A simple ion chromatography method for inorganic anion analysis in edible seaweeds

A new, simple, fast and sensitive ion chromatography (IC) method, for the simultaneous analysis of fluoride, chloride, nitrite, bromide, nitrate, phosphate and sulphate in edible seaweeds was developed and reported for the first time. The validation of the analytical method was studied in terms of linearity, sensitivity, precision and accuracy. All standard calibration curves showed very good correlation between anion peak area and concentration (r > 0.999). Limits of detection and quantitation ranged between 0.002-0.05 mg/L and 0.01-0.1 mg/L, respectively and indicated the high sensitivity of the method. Relative standard deviation values of repeatability and inter-day precision for standard anions with the same sample were less than 2%. Anion recoveries ranged from 97 to 113% for chloride and from 87 to 105% for sulphate, respectively and showed the fairly good accuracy of the method. The method was applied to the analysis of inorganic anions in brown and red edible seaweeds. Brown seaweeds were characterized by higher chloride content up to 33.7-36.9%, while red seaweeds were characterized by higher sulphate content (45-57%). Sulphate content in seaweeds is related to the presence of sulphated polysaccharides of biological importance. The method developed was well applicable to mineral anion analysis in edible seaweeds and shows suitability and reliability of use in other food samples of nutritional importance.     

Preconcentration and Determination of Tin in Water Samples by Using Cloud Point Extraction and Graphite Furnace Atomic Absorption Spectrometry

A method based on cloud point extraction and graphite furnace atomic absorption spectrometry (GFAAS) was developed for the analysis of trace tin in water samples. After cloud point extraction, the tin in the water samples was preconcentrated and successfully separated from most interferents. During the procedure, 8-hydroxyquinoline (8-HQ) was used as chelating reagent, and Triton X-114 was added as surfactant. The parameters affecting the sensitivity and the extraction efficiency, such as solution pH, concentration of 8-HQ and Triton X-114, equilibration temperature and centrifuge time, were evaluated and optimized. Under the optimum conditions, a preconcentration factor of 96.2 was obtained for a 20 mL water sample. The detection limit (LOD) was as low as 0.012 ng mL⁻¹, and the analytical curve was linear in the range of 0.05–2.0 ng mL⁻¹ with satisfactory precision (RSD <4.1%). The proposed method was successfully applied to the determination of trace tin in water samples with recoveries in the range of 85.0–112.0%.     

Determination of trace elements in biological samples treated with formic acid by inductively coupled plasma mass spectrometry using a microconcentric nebulizer

A simple and fast method for the determination of As, Ba, Cd, Co, Cu, Fe, Ga, Mn, Mo, Ni, Pb, Rb, Se, Sr, Tl, U, V and Zn in biological samples by inductively coupled plasma mass spectrometry (ICP-MS), after sample solubilization with formic acid and introduction by a microconcentric nebulizer, is proposed. The sample is mixed with formic acid, kept at 90 °C for one hour and then diluted with nitric acid aqueous solution to a 50% v/v formic acid and 1% v/v nitric acid final concentrations. The final sample solution flow rate for introduction into the plasma was 30 μL min⁻¹. The optimized and adopted nebulizer gas flow rate was 0.7 L min⁻¹ and RF power was 800 W. These conditions are very different than those normally used when a conventional nebulizer is employed. Rodhium was used as internal standard. External calibration against aqueous standard solutions, without formic acid, could be used for quantification, except for As, Se and Zn. However, external calibration with 50% formic acid allows the determination of all analytes with high accuracy and it is recommended. The detection limits were between 0.0005 (Tl) and 0.22 mg kg⁻¹ (Fe) and the precision expressed by the relative standard deviations (RSD) were between 0.2% (Sr) and 3.5% (Ga). Accuracy was validated by the analysis of four certified reference biological materials of animal tissues, comparing the results by linear regressions and by the t-test at a 95% confidence level. The recommended procedure avoids plasma instability and carbon deposit on the cones.     

Simultaneous determination of 64 pesticides in river water by stir bar sorptive extraction and thermal desorption-gas chromatography-mass spectrometry

A method for determining 68 pesticides in river water using stir bar sorptive extraction (SBSE)-thermal desorption (TD)-gas chromatography-mass spectrometry (GC-MS) is described. SBSE sampling was optimized for sample solution pH, salting-out and methanol addition. Although salting-out enhanced the ability of the method to extract most of the pesticides with low absolute recoveries, the absolute recoveries of four pesticides were not improved by salting-out. The detection limits of the method for the pesticides ranged from 0.2 to 20 ng/l. Analyte recoveries from a river water sample spiked with standards at 10 and 100 ng/l were 58.5–132.0% (RSD: 1.8–15.8%) and 61.0–121.3% (RSD: 1.4–20.2%), respectively.     

Fast spectrophotometric determination of titanium in rocks with 3,4-dihydroxybenzoic acid

A fast Spectrophotometric method has been developed for titanium determination in geological matrices, based on the mixture of the sample solution with an exact volume of a single chromogenic solution containing acetate buffer, ascorbic acid and 3,4-dihydroxybenzoic acid DHB, which forms with titanium(IV) ions a yellow complex with absorption maximum at 380 nm. The following parameters were studied: complex stability, pH effect, amount of DHB, amount of acetate buffer, obedience to Beer's law, amount of ascorbic acid and iron masking. The results demonstrated that titanium can be determined in the pH range 4.0–5.0, with a molar absorptivity of 1.43 × 10⁴ 1·mol^–1 cm^–1 and a limit of detection of 2.3 ng/ml. The methodology that allows analysis of 30 samples per hour. Common anions and cations do not interfere, even when present in large amounts. Iron(III) interference can be easily eliminated by reduction to iron(II) using ascorbic acid. Analytical characteristics of the proposed procedure, such as calibration sensitivity, analytical sensitivity, limit of detection and coefficient of variation, were determined. The procedure was applied for titanium determination in various standard geological matrices, with results of satisfactory accuracy and precision (RSD<1%).