Rapid analytical method for the determination of organic and inorganic species in tomato samples through HPLC-ICP-AES coupling.

A HPLC-inductively coupled plasma atomic emission spectrometer (ICP-AES) hyphenation technique was used to determine the concentration of some organic (i.e., carbohydrates, carboxylic acids) as well as inorganic (metals and anions) compounds in tomato samples. A high efficiency nebulizer (HEN) coupled to a low inner volume cyclonic spray chamber (Cinnabar) was used to interface both techniques. The HPLC-ICP-AES chromatograms for organic compounds were obtained by plotting the 193.03nm carbon emission intensity versus time. In the present work, it was also possible to obtain information about the concentration of several metals in foodstuffs. Finally, by registering the intensity at the sulphur and phosphorous emission wavelengths, the content of anions such as sulphate and phosphate was determined. In general terms, the results obtained with HPLC-ICP-AES did not differ significantly from those found with a refractive index detector. Due to the huge amount of information provided by this hyphenation, it was possible to apply it to the discrimination among different samples of native tomato cultivars.

Development of novel and sensitive methods for the determination of sulfide in aqueous samples by hydrogen sulfide generation-inductively coupled plasma-atomic emission spectroscopy.

Two new, simple and accurate methods for the determination of sulfide (S(2-)) at low levels (microgL(-1)) in aqueous samples were developed. The generation of hydrogen sulfide (H(2)S) took place in a coil where sulfide reacted with hydrochloric acid. The resulting H(2)S was then introduced as a vapor into an inductively coupled plasma-atomic emission spectrometer (ICP-AES) and sulfur emission intensity was measured at 180.669nm. In comparison to when aqueous sulfide was introduced, the introduction of sulfur as H(2)S enhanced the sulfur signal emission. By setting a gas separator at the end of the reaction coil, reduced sulfur species in the form of H(2)S were removed from the water matrix, thus, interferences could be avoided. Alternatively, the gas separator was replaced by a nebulizer/spray chamber combination to introduce the sample matrix and reagents into the plasma. This methodology allowed the determination of both sulfide and sulfate in aqueous samples. For both methods the linear response was found to range from 5microgL(-1) to 25mgL(-1) of sulfide. Detection limits of 5microgL(-1) and 6microgL(-1) were obtained with and without the gas separator, respectively. These new methods were evaluated by comparison to the standard potentiometric method and were successfully applied to the analysis of reduced sulfur species in environmental waters.

A new continuous calibration method for inductively coupled plasma spectrometry.

A new calibration method was developed and applied to inductively coupled plasma atomic emission spectrometry. External calibration was performed as follows. A container was filled with a given volume of deionized (V(p)) water. Then a concentrated standard was introduced at a controlled rate (Q(e)) into the tank by means of a peristaltic pump. The resulting solution was stirred throughout the experiment. Simultaneously, the solution inside the tank was pumped from the vessel to the plasma at a given rate (Q(s)). The signal was continuously recorded. The variation of the concentration of the solution leaving the tank with time was determined by applying a basic equation of stirred tanks. The representation of the emission intensity versus the time and the further conversion of the time scale into a concentration scale gave rise to the calibration line. The best results in terms of linearity were achieved for V(p)=15 cm3, Q(e)=0.6-0.75 ml min(-1) and Q(s)=1-1.2 ml min(-1). Graphs with more than 40 standards were obtained within about 10 min. The results found were not statistically different from those afforded by the conventional calibration method. In addition, the new method was faster and supplied better linearity and precision than the conventional one. Another advantage of the stirred tank was that procedures such as dynamic calibration and standard additions could be easily and quickly applied, thus shortening the analysis time. A complete analysis following these procedures based on the measurement of 30 standards took about 5 min. Several synthetic as well as certified samples (i.e., bovine liver, mussel tissue and powdered milk) were analyzed with the stirred tank by applying four different calibration methodologies (i.e., external calibration, internal calibration, standard additions and a combination of internal standardization and standard additions), with the combination of internal standardization and standard additions being the method that provided the best results. The element concentrations obtained were not significantly different from the actual or certified values.

Evaluation of several pneumatic micronebulizers with different designs for use in ICP-AES and ICP-MS. Future directions for further improvement.

This paper reports characterization of the behavior of five pneumatic micronebulizers based on slightly different designs in inductively coupled plasma atomic-emission spectrometry and mass spectrometry (ICP-AES and ICP-MS). Two nebulizers were used as reference nebulizers, a high-efficiency nebulizer (HEN) and a micromist (MM). They were compared with a commercially available PFA (tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer) nebulizer and with two new prototypes called the polymeric pneumatic concentric nebulizer (PMN) and the high-solids micronebulizer (HSM). The dimensions of the nebulizers, the gas back-pressure, and the free liquid uptake rates were measured. The study also included tertiary aerosol drop-size distributions, analyte transport rate, and analytical figures of merit, i.e. sensitivities and limits of detection, both in ICP-AES and ICP-MS. Recoveries for two food solid reference materials were also determined. Overall, the results indicated that the PFA and the HEN nebulizers provided the best results. These two nebulizers delivered a higher mass of analyte to the plasma and showed better sensitivies giving lower limits of detection than the PMN, HSM and MM. The results revealed that the liquid prefilming effect occurring before aerosol production in the PFA nebulizer promoted more efficient interaction of liquid and gas, thus affording good results even though gas back-pressure values could be maintained below 3 bar. In contrast, the HEN had to be operated at about 7 bar under the same conditions. Nebulizer design did not have a relevant effect on the recovery, which confirmed that the spray chamber plays an important role in terms of non-spectroscopic interferences.

Comparison of several spray chambers operating at very low liquid flow rates in inductively coupled plasma atomic emission spectrometry.

Four different spray chambers were evaluated in ICP-AES at very low liquid flow rates: a double-pass (Scott type), a conventional cyclonic, and two low-volume cyclonic-type spray chambers (i.e., Cinnabar and Genie). A glass concentric pneumatic micro nebulizer (Atom Mist) was used in conjunction with all four chambers. The liquid flow rate was varied from 10 to 160 microL min(-1). The conventional cyclonic spray chamber gave rise to coarser tertiary aerosols, higher analyte and solvent transport rates, higher sensitivity and lower limits of detection than the remaining ones. The low-volume spray chambers afforded analytical figures of merit similar to the double-pass one, despite their very different designs. However, these spray chambers exhibited shorter wash-out times. The matrix effects were significant only for the double-pass. This fact allowed the analysis of reference samples by employing aqueous standards at a minimum level of sample consumption. The recoveries obtained for the cyclonic spray chambers and several certified samples were close to 100%, being always lower in the case of the double-pass spray chamber.

Determination of metals in lubricating oils by flame atomic absorption spectrometry using a single-bore high-pressure pneumatic nebulizer.

The behaviour of a single-bore high-pressure pneumatic nebulizer (SBHPPN) as a tool for the analysis of lubricating oils by flame atomic absorption spectrometry (FAAS) was investigated. The effects of the sample oil content [from 10% to 100% (w/w) oil in 4-methylpentan-2-one, IBMK] and the carrier nature (IBMK and methanol) on the characteristics of the aerosols generated, on the analyte transport efficiency and on the analytical figures of merit in FAAS were studied. A pneumatic concentric nebulizer (PCN) was used for comparison. Increasing the oil content increases the viscosity of the sample. With the PCN this gives rise to coarser aerosols, making it impossible to nebulize samples with an oil content higher than 70% (w/w). Using the SBHPPN, the viscosity of the sample scarcely affects the characteristics of the primary aerosols. Hence, the SBHPPN is able, by using the appropriate carrier, to nebulize pure lubricating oils. Among the carriers tested, IBMK is the most advisable because it is fully miscible with all the oil samples. The SBHPPN provides higher sensitivities and lower limits of detection than the PCN. Compared with a method based on organic dilution, the use of the SBHPPN for the direct analysis of lubricating oils by FAAS makes it possible, in addition to increasing the analysis throughput, to detect elements at lower concentrations. Moreover, the SBHPPN provides similar results to those obtained using a previous acid digestion step.

A microwave-powered thermospray nebulizer for liquid sample introduction in inductively coupled plasma atomic emission spectrometry.

A new thermospray nebulizer based on the absorption of microwave radiation (MWTN) by aqueous solutions of strong acids is presented for the first time. To this end, a given length of the sample capillary is placed inside the cavity of a focused microwave system. A small piece of a narrower capillary tubing is connected at the tip of the sample capillary, outside the microwave cavity, to build up pressure. Drop size distributions of primary aerosols are exhaustively measured in order to evaluate the influence of several experimental variables (microwave power, liquid flow, irradiation length, inner diameter of the outlet capillary, nature and concentration of the acid) on the characteristics of the primary aerosol that are related to the emission signal. These experiments have been performed mainly to increase our understanding of the microscopic process of this new type of aerosol generation. A standard Meinhard nebulizer was employed for comparison. Under the best conditions the entire aerosol volume is contained in droplets smaller than 20 µm compared with 45% of the volume of the aerosol generated by the Meinhard. Hence, higher analyte and aerosol transport rates are to be expected for the MWTN compared with the Meinhard nebulizer. As any highly efficient nebulizer, MWTN requires a desolvation unit. For solutions 0.75 M in strong acid, the new nebulizer improves sensitivity (1.0-2.8 times), limits of detection (1.2-3.0 times), and background equivalent concentration (0.9-2.0 times) as compared to the standard Meinhard nebulizer, features many of the advantages of the conventional thermospray nebulizer, and overcomes some of its drawbacks (MWTN does not show corrosion problems and works at lower pressure, the aerosol characteristics are not modified when the PTFE capillary is replaced).

A system for the direct determination of the nonvolatile organic carbon, dissolved organic carbon, and inorganic carbon in water samples through inductively coupled plasma atomic emission spectrometry.

A new system has been developed for the determination of total organic carbon (TOC) and inorganic carbon (IC) or total inorganic carbon (TIC) in waters. Only nonvolatile organic compounds can be detected through the present method. The system presented in this work is based on the measurement of the carbon atomic emission intensity in inductively coupled plasma atomic emission spectrometry (ICP-AES). This way, the organic matter does not undergo any preoxidation step. A semiautomatic accessory connected to the spectrometer separates the different carbon fractions (i.e., organic and inorganic). Because most of the solutions used in the present work did not contain suspended solid particles, the actual parameter that was determined was the dissolved organic carbon (DOC). The present system exhibits good sensitivities compared to those provided by conventional TOC and IC determination methods. The limits of detection obtained in the present work have been 0.07 and 0.0007 mg/L C in terms of TOC and IC, respectively. Furthermore, the system is able to handle high-salt-content solutions. This fact suggests that it would be possible to analyze seawater samples, avoiding some of the problems encountered with conventional methods, such as system blocking or interferences. The TOC and IC values found for natural samples are very close to those measured using conventional methods. The ICP-AES method has been successfully used in two interesting applications: (i) monitoring the efficiency of a water treatment plant and (ii) determining the contents of dissolved carbon dioxide, on one hand, and that of carbonate and bicarbonate, on the other, in the same sample.