Rapid and simultaneous detection of cadmium and mercury in foods based on solid sampling integrated electrothermal vaporization technique.

This work presents an innovative solid sampling (SS) integrated electrothermal vaporization (ETV) approach for simultaneous determination of Cd and Hg based on differentiated elemental vaporization and transportation behavior characteristics. A miniature N2/H2 generator, only consuming electricity and H2O, was utilized to yield reducing atmosphere for Cd vaporization; MgO filler was modified to absorb matrix interferent and keep Hg and Cd transportation via 1st catalytic pyrolysis furnace (CPF); and a gearing was employed to move 2nd CPF to receive and trap (amalgamation) the vaporized Hg from ETV and then thermo-release them for simultaneous detection. Under optimized conditions, the limits of detection of Cd and Hg reached 0.02-0.04 ng/g using 0.4 g sample size. The linearities (R2) exceeded 0.998 and recoveries were 85.0-111.9%, indicating favorable analysis precision and accuracy within ∼3 min without sample digestion process. The proposed HgCd analyzer is suitable for rapid monitoring food with simplicity, green and safety.

A portable solid sampling visualization nano-sensor for soil Cd based on "three-phase transforming" technique.

Direct analysis of solid samples is always challenging for ionic sensors due to solidified elemental presence and matrix interference. In this work, a "three-phase transforming" technique was first established to make solid sampling elemental sensors and visual detection possible in the future. For Cd transforming from soil samples, a metal ceramic heater (MCH) electrothermal vaporizer (ETV) coupled with a dielectric barrier discharge quartz trap (DBD-QT) was first utilized to fulfill the solid sampling and preconcentration of Cd in soil; for on-site analysis, a colorimetric sensor based on the trithiocyanuric acid (TMT) functionalized gold nanoparticles (AuNPs) was chosen as a chromogenic analysis model. The portable and miniature ETV-DBD apparatus directly introduced Cd from soil and then captured Cd, consuming only <130 W and 4.5 kg weight; finally, only 200 µL water was injected as eluent to dissolve Cd for the following colorimetric detection. Herein, the Cd analyte underwent a "three-phase transforming" from solid (Cd compounds in soil), to aerosol (vaporization and transportation), to solid (Cd oxides trapped on quartz surface) and to liquid (Cd2+ in eluate). Under optimized conditions, the method limit of detection (LOD) reached 0.04 mg/kg Cd (50 mg sample), fulfilling fast monitoring of Cd contamination in soil, with <20 % relative standard deviations (RSDs). The analysis time was <10 min excluding sample digestion and acid application, as well as the interference of Pb2+ on the AuNPs sensor can be eliminated via the "three-phase transforming" process, proving an excellent anti-interference for solid analysis. This "three-phase transforming" processing technique coupled with colorimetric sensor holds a great potential for direct and on-site analysis in solid samples without complicated handling, providing a fantastic methodology for the application of ionic sensors and making solid sampling elemental sensor and visual detection possible.

Direct Analysis of Bio-Molecules in Solid Materials Using Electrospray Ionisation Mass Spectrometry Coupled with Laser Ablation and a Liquid Sampling Technique.

In situ and rapid analysis of organic compounds using a combination of a newly-developed laser ablation in liquid (LAL) sampling technique combined with electrospray ionisation mass spectrometry (ESI-MS) is reported. The LAL is a technique that allows laser ablation to be conducted in a liquid medium containing organic compounds that were effectively extracted from solid materials into the liquid medium. Three organic compounds (valine, caffeine, and benzyl butyl phthalate (BBP)) were subjected to analysis. The LAL sampling was conducted in the fast-laser scanning mode using Galvanometric optics, and the total ablation time required for the sampling from a 1 mm2 area was about 3 s, thus providing rapid sampling. The resulting sample solution was directly introduced into the ESI-MS system, without the need for any chromatographic separation. To evaluate the analytical capability of the LAL technique coupled with ESI-MS, both the overall transmission efficiencies of analytes from solid materials to the ion detector, and the repeatabilities of the measurements were rigorously tested. This involved the use of synthetic, in-house prepared standard materials containing the analytes. The overall ion yields were about 1.1×10-3% for valine, 8.7×10-3% for caffeine, and 6.7×10-4% for BBP. By comparing the ion yields obtained by the injection of an analyte solution and a standard solution through the mass spectrometer, the recoveries through the LAL sampling were approximately 31% for valine, 45% for caffeine, and 37% for BBP. In addition, the analytical repeatabilities for all analytes were better than 6%. The analytical repeatabilities were mainly affected by either the heterogeneity of the in-house standard materials or changes in the plasma temperature by coexisting, laser-induced sample particles. It should be noted that not only water-soluble compounds (caffeine and valine), but also non-soluble compound (BBP) could be measured by the LAL-ESI-MS, which is one of the great advantages over the conventional liquid extraction surface analysis technique. The data obtained here clearly demonstrate that the LAL-ESI-MS has the potential for being a fast and user-friendly analytical technique for the in-situ detection for both the water-soluble and water-insoluble molecules.

Rapid and Portable Detection of Hg and Cd in Grain Samples Based on Novel Catalytic Pyrolysis Composite Trap Coupled with Miniature Atomic Absorption Spectrometry.

As toxic metals, Hg and Cd are a concern for food safety and human health; their rapid and portable analysis is still a challenge. A portable and rapid Hg-Cd analyzer constructed from a metal-ceramic heater (MCH)-based electrothermal vaporizer (ETV), an on-line catalytic pyrolysis furnace (CPF), a composite Pt/Ni trap, and a homemade miniature atomic absorption spectrometer (AAS) was proposed for grain analysis in this work. To enhance sensitivity, a new folded light path was designed for simultaneous Hg and Cd analysis using charge coupled device (CCD) in AAS. To eliminate the grain matrix interference, a catalytic pyrolysis furnace with aluminum oxide fillers was utilized to couple with a composite Pt/Ni trap. The method limits of detection (LODs) were 1.1 µg/kg and 0.3 µg/kg for Hg and Cd using a 20 mg grain sample, fulfilling the real sample analysis to monitor the grain contamination quickly; linearity R2 > 0.995 was reached only using standard solution calibration, indicating the sample was free of grain matrix interference. The favorable analytical accuracy and precision were validated by analyzing real and certified reference material (CRM) grains with recoveries of 97-103% and 96-111% for Hg and Cd, respectively. The total analysis time was less than 5 min without sample digestion or use of any chemicals, and the instrumental size and power consumption were <14 kg and 270 W, respectively. Compared with other rapid methods, this newly designed Hg-Cd analyzer is proven to be simple, portable, and robust and is, thus, suitable to quickly monitor Hg and Cd contamination in the field to protect grain and food safety.

Solid Sampling Pyrolysis Adsorption-Desorption Thermal Conductivity Method for Rapid and Simultaneous Detection of N and S in Seafood.

In this work, a rapid method for the simultaneous determination of N and S in seafood was established based on a solid sampling absorption-desorption system coupled with a thermal conductivity detector. This setup mainly includes a solid sampling system, a gas line unit for controlling high-purity oxygen and helium, a combustion and reduction furnace, a purification column system for moisture, halogen, SO2, and CO2, and a thermal conductivity detector. After two stages of purging with 20 s of He sweeping (250 mL/min), N2 residue in the sample-containing chamber can be reduced to <0.01% to improve the device's analytical sensitivity and precision. Herein, 100 s of heating at 900 °C was chosen as the optimized decomposition condition. After the generated SO2, H2O, and CO2 were absorbed by the adsorption column in turn, the purification process executed the vaporization of the N-containing analyte, and then N2 was detected by the thermal conductivity cell for the quantification of N. Subsequently, the adsorbed SO2 was released after heating the SO2 adsorption column and then transported to the thermal conductivity cell for the detection and quantification of S. After the instrumental optimization, the linear range was 2.0−100 mg and the correlation coefficient (R) was more than 0.999. The limit of detection (LOD) for N was 0.66 µg and the R was less than 4.0%, while the recovery rate ranged from 95.33 to 102.8%. At the same time, the LOD for S was 2.29 µg and the R was less than 6.0%, while the recovery rate ranged from 92.26 to 105.5%. The method was validated using certified reference materials (CRMs) and the measured N and S concentrations agreed with the certified values. The method indicated good accuracy and precision for the simultaneous detection of N and S in seafood samples. The total time of analysis was less than 6 min without the sample preparation process, fulfilling the fast detection of N and S in seafood. The establishment of this method filled the blank space in the area of the simultaneous and rapid determination of N and S in aquatic product solids. Thus, it provided technical support effectively to the requirements of risk assessment and detection in cases where supervision inspection was time-dependent.

Portable and miniature mercury analyzer using direct sampling inbuilt-metal ceramic electrothermal vaporization.

In this work, a small-size inbuilt-metal ceramic heater (IMCH) was for the first time utilized as a solid sampling electrothermal vaporizer (ETV), and then a novel direct sampling mercury analyzer coupled with a miniature atomic absorption spectrometer was thereby fabricated for sensitive determination of mercury in soil. The mercury analyzer is mainly composed of an IMCH-ETV, a catalytic pyrolysis furnace (CPF) using Al2O3 particles as a new filler, an atomic absorption spectrometer (AAS) and a miniature air pump for carrier gas; herein, the mostly used gold amalgamation was canceled. The IMCH with 30 W heating fulfills the 100% vaporization of mercury from up to 80 mg soil samples using 0.1 L min-1 air carrier. Under the optimized conditions, the method detection limit (LOD) was 0.4 ng g-1 for a 50 mg sample and the RSD of 11 repeated measurements of GSS-3a soil certified reference material (CRM) was 4%. Furthermore, the measured Hg values in various soil CRMs and real soil samples were within their certified values and consistent with that using the Chinese standard method (solid sampling catalytic pyrolysis AAS with gold amalgamation); and the recoveries were 85-113%, which proved favorable analytical accuracy and precision. This fabricated instrumentation only occupies 5 kg and 200 W power consumption vs. more than 25 kg and 1000 W for the traditional Hg analyzer. Therefore, the proposed IMCH-ETV-AAS method is very suitable for portable and rapid detection of mercury in soil.

Fast Detection of Cadmium in Chocolate by Solid Sampling Electrothermal Vaporization Atomic Absorption Spectrometry and Its Application on Dietary Exposure Risk Assessment.

In this work, a rapid detection method using solid sampling electrothermal vaporization atomic absorption spectrometry (SS-ETV-AAS) was established for cadmium in chocolate. The instrumental system includes a solid sampling ETV unit, a catalytic pyrolysis furnace, an AAS detector, and a gas supply system with only an air pump and a hydrogen generator. Herein, MgO material with 1.0−1.5 mm particle size was first employed to replace the kaolin filler previously used to further shorten the peak width and to thereby improve the sensitivity. With 350 mL/min of air, a chocolate sample was heated for 25 s from 435 to 464 °C to remove water and organic matrices; then, after supplying 240 mL/min hydrogen and turning down air to 120 mL/min, a N2/H2 mixture gas was formed to accelerate Cd vaporization from chocolate residue under 465 to 765 °C. Under the optimized conditions, the detection limit (LOD) was obviously lowered to 70 pg/g (vs. previous 150 pg/g) with R2 > 0.999; the relative standard deviations (RSD) of repeated measurements for real chocolate samples ranged from 1.5% to 6.4%, indicating a favorable precision; and the Cd recoveries were in the range of 93−107%, proving a satisfied accuracy. Thus, the total analysis time is less than 3 min without the sample digestion process. Thereafter, 78 chocolate samples with different brands from 9 producing countries in China market were collected and measured by this proposed method. Based on the measured Cd concentrations, a dietary exposure assessment was performed for Chinese residents, and the target hazard quotient (THQ) values are all less than 1, proving no significant health risk from intaking chocolate cadmium for Chinese residents.

Application of SS-CS-HR-AAS measurements for the detection of Ag nanoparticles in marine invertebrates.

The present study describes the development of a fit-for-purpose analytical procedure for the detection of Ag NPs in different marine organisms by Solid Sampling Continuous Source High Resolution Atomic Absorption Spectrometry (SS-CS-HR-AAS). The detection is based on the observation of the Ag absorption peak and its atomization delay tad which is different for ionic Ag and Ag NPs. The temperature program was optimized in order to achieve the maximum difference between the t ad (Δtad ). The method was first developed using biota CRMs spiked with different Ag NPs standard solutions or Ag+ , at the same concentration. Then, laboratory exposure experiments were performed on mussels and marine sponges. The results showed that the developed methodology is suitable for the detection of Ag NPs for both groups of organisms, showing Δtad up to 3.1 s. The developed method is therefore a promising tool to assess the presence of AgNPs in marine invertebrates.

A solid sampling approach for direct determination of Cl and S in flour by an elemental analyzer.

Direct analysis of flour was proposed for the determination of Cl and S by an elemental analyzer for the first time. The main operational conditions of the direct solid sampling elemental analysis (DSS-EA) were optimized and calibrated by standard solutions, rather than by certified reference material (CRM). Accuracy was evaluated by the analysis of CRM of rice flour and by comparison with analyte determination by independent techniques, i.e., ion chromatography and inductively coupled plasma optical emission spectrometry; both were carried out after microwave-induced combustion. Sample mass from 0.5 to 260 mg was used and limits of quantification of 1.2 µg g-1 for Cl and 0.2 µg g-1 for S were achieved. Wheat, whole wheat, potato and corn flour were analyzed by DSS-EA. Concentrations of Cl and S ranged from 4.8 to 685 µg g-1 and from 13 to 1328 µg g-1, respectively.

Direct solid sampling for speciation of Zn2+ and ZnO nanoparticles in cosmetics by graphite furnace atomic absorption spectrometry.

The application of nanoparticles (NPs) in science and technology is a fast growing field. Therefore, reliable and straightforward analytical methods are required for their fast determination in different types of samples. This work investigates a method that enables the determination of ZnO NPs, discriminating them from ionic zinc in cosmetic samples. The method is based on direct solid sampling high-resolution continuum source electrothermal atomic absorption spectrometry (SS-HR-CS-GFAAS), and has been applied to determination of ZnO NPs, Zn2+ and total Zn in eye shadow samples. In this work the deconvolution of the atomization peak and the calibration by standard additions have been done in order to discriminate and quantify ionic zinc and ZnO NPs. A Zn wavelength with low sensitivity was selected. The proper optimization of the graphite furnace temperature program, minimizing the mineralization of the sample matrix, enables different atomization profiles between the different chemical species of the analyte. Two multiple response surface designs have been used in order to optimize the adequate furnace program to achieve our aims. All the optimization experiments were performed using a sample of eye shadow. Further, a method for the determination of total Zn by direct solid sampling with calibration by aqueous standards, was also optimized. The optimized method was successfully applied to the determination of ionic Zn and ZnO NPs in different eye shadow samples, and has been validated by recovery assays, obtaining recovery percentages between 80 and 125%. Total Zn concentration in the solid samples was validated by the determination of total Zn by direct solid sampling and by the analysis of the same eye shadow samples digested in microwave oven.

Feasibility of DS-GF AAS for the determination of metallic impurities in raw material for polymers production.

A new procedure is proposed for the determination of metal contaminants (Cr, Fe, Mg, Mn, Na and Ni) in polymeric diphenylmethane diisocyanate (PMDI), a raw material used to produce polyurethane polymers. The feasibility of using Zeeman-effect background correction graphite furnace atomic absorption spectrometry (GF AAS) and direct sampling (DS) was evaluated. Calibration using aqueous standard solutions was feasible and chemical modifiers as well as reference materials for this purpose were unnecessary. Relatively high sample masses (up to 23 mg) were used allowing very low limits of detection ranging from 0.06 ng g-1 to 1 ng g-1 (Fe and Mg) up to 3  ng g-1 (Ni), with relative standard deviation lower than 15%. The following parameters were evaluated: pyrolysis and atomization temperatures , sample mass, as well as the use of low sensitivity conditions (Zeeman effect background correction magnetic field strength adjustment and the use of a secondary wavelength for Fe and Na determinations, respectively). Results were compared with those obtained by microwave-assisted digestion and microwave-induced combustion with subsequent analytes determination by inductively coupled plasma optical emission spectrometry (ICP-OES) and by inductively coupled plasma mass spectrometry (ICP-MS). No significant difference was observed between the results obtained by DS-GF AAS, ICP-MS and ICP-OES after both digestion systems. The proposed DS-GF AAS method allowed the determination of six elements in PMDI (which is considered as a complex matrix) with limits of detection lower than those achieved by other methods. This new procedure can be used as quality control of polyurethanes industry for ultra-trace inorganic impurities.

On-line microplasma decomposition of gaseous phase interference for solid sampling mercury analysis in aquatic food samples.

In this work, dielectric barrier discharge (DBD) was first utilized to eliminate gaseous phase interference from complicated solid sample. So, a novel solid sampling Hg analyzer was first designed using a coaxial DBD reactor to replace catalytic pyrolysis furnace for sensitive mercury determination in aquatic food samples. The Hg analyzer mainly comprised an electrothermal vaporizer (ETV), a DBD reactor to decompose gaseous interfering substances including volatile organic compounds (VOCs), a gold-coil Hg trap to eliminate matrix interference and an atomic fluorescence spectrometer (AFS) as detector. These units were connected by a manifold integrating air and Ar/H2 (v/v = 9 : 1), fulfilling on-line decomposition of up to 12 mg dried aquatic food powder at ambient temperature. The proposed method detection limit (LOD) was 0.5 µg/kg and the relative standard deviations (RSDs) were within 5% for Hg standards as well as within 10% for real samples, indicating adequate analytical sensitivity and precision. In addition, the on-line DBD reactor consumes only 40 W, which is obviously lower than that (>300 W) of the commercial Hg analyzers; including the sample pre-treatment, the overall analysis could be completed within 5 min. This method is easier, greener and safer for Hg analysis in real samples obviating chemical reagents. The new DBD apparatus can facilitate the miniaturization and portability with low power consumption and instrumental size revealing its promising potential in direct Hg analysis instrumentation development.

Determination of cadmium in lichens by solid sampling graphite furnace atomic absorption spectrometry (SS-GF-AAS).

The determination of trace metal contents directly from a solid sample is a trend in modern atomic spectrometry. The aim of this study was to develop an analytical method for the routine determination of Cd in lichens using solid sampling graphite furnace atomic absorption spectrometry (SS-GF-AAS). For the determination of Cd, the temperature program of the graphite furnace was optimized using a mixed matrix modifier (Pd + Mg (NO3)2 + Triton X-100). The limit of detection and the limit of quantification were 0.9 µg/kg and 3 µg/kg, respectively. The analytical method for Cd determination in the plant matrix was verified by the analysis of certified reference materials of lichens, seaweed, and rye grass. The developed procedure was applied to the study of Cd distribution in thalli of Usnea antarctica lichen from James Ross Island, Antarctica. The SS-GF-AAS analytical method is particularly suited for use in environmental studies and plant physiology (the microanalysis of anatomical structures).

A handling-free methodology for rapid determination of Cu species in seawater based on direct solid micro-samplers analysis by high-resolution continuum source graphite furnace atomic absorption spectrometry.

A very simple, sensible and advanced new methodology for the determination of copper species in seawater has been developed. The method consisted of two steps: first a separation/preconcentration of copper species by using liquid phase microextraction-based solvent bars followed by the direct analysis of these solid polymeric micro-samplers in an atomic absorption spectrometer provided with a device for direct analysis. For liquid microextraction, di-2-pyridylketone benzoylhydrazone (dPKBH) dissolved in octan-1-ol was selected as the extracting agent due to its ability to transport inorganic Cu species from seawater samples. The optimum chemical and physical conditions for copper micro-extraction were sample pH 8, a dPKBH concentration of 0.010 mol L-1, a stirring speed of 800 rpm and an extraction time of 10 min. A graphite furnace temperature program was optimised to assure the complete elimination of the solvent bar matrix, and the atomisation step took place at 2200 °C. The method exhibited a limit of detection of 0.026 µg L-1 of copper and a linear range up to 1.50 µg L-1, showing great repeatability and reproducibility (4.07% and 4.43%, respectively). Suitability of the method was confirmed by analysing a certified reference material (CASS-4) under optimum conditions, being the first time ever that a direct solid analysis-based method has been used for the determination of total dissolved copper concentration in seawater. Furthermore, the method was applied to the determination of the operationally defined transportable Cu fraction in seawater samples at natural conditions and the results were compared with theoretical data provided by Visual MINTEQ® 3.1 software. A mathematical model that permits to estimate total dissolved copper concentration was obtained, and the non-transportable copper fraction was calculated by difference.

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.

Solid Sampling in Analysis of Various Plants Using Two-Jet Plasma Atomic Emission Spectrometry.

The possibility of two-jet plasma atomic emission spectrometry for analysis of different plants using solid sample preparation and unified calibration samples was investigated. The certified reference materials of wheat, maize, rice, potato, grass mix, birch leaves, and Elodea canadensis were used for analysis. On the basis of the behavior of these plants in the plasma, they were divided into two groups: starch-containing materials (cereal and root crops) and leaves/grass. It was found that the previous sample carbonization should be used for analysis of starch-containing plants while leaves and grass could be analyzed by the direct technique. Carbonization was only applied for determining low concentrations of trace elements in leaves and grass. The calibration samples based on graphite powder and simple sample preparation, dilution of powdered sample with a spectroscopic buffer, were used for both direct analysis and analysis after carbonization. Such an approach allowed estimation of B, Ba, Be, Cd, Co, Cr, Cu, Ga, Fe, Mn, Ni, Pb, Si, Sr, V, and Zn in different plants. The limits of detection (LODs) provided by the direct technique were at the level of (µg·g-1): n × 0.1 for Cd, Cu, and Mn; n for B, Ba, Co, Cr, Fe, Ga, Ni, Pb, Sr, V, and Zn; n × 10 for Si. Carbonization allowed improving LODs of elements several times depending on the thermal stability and mineral composition of plants. The LODs of elements in plants obtained after carbonization are the following (µg·g-1): n × 0.01 for Be, Cd, Cu, and Mn; n × 0.1 for Co, Cr, Fe, Ga, Ni, Pb, Sr, V, Zn; and n for Si. The techniques suggested are fast, easily workable, and do not require harmful chemical reagents. In some cases, the influence of variable matrices and different element species on analytical signal of elements was not completely suppressed; the deviation of element concentrations from the true values was discussed.

Solid sampling ETV-ICPOES coupled to a nebulization/pre-evaporation system for direct elemental analysis of glutinous rice by external calibration with standard solutions.

Because glutinous rice flour is consumed by millions of individuals around the world, its analysis is essential to ensure its safety. Solid sampling electrothermal vaporization (ETV) coupled to inductively coupled plasma optical emission spectrometry (ICPOES) allows for a quick analysis, precluding the need for time-consuming acid digestion that may also lead to analyte loss or contamination. However, the amount of sample that can be introduced without extinguishing the plasma is limited to about 4mg. The increase in plasma robustness resulting from the concurrent introduction of pre-evaporated water aerosol allows the introduction of 8mg of solid sample without extinguishing the plasma. This modified set-up was compared to conventional ETV for the determination of several elements in three different brands of glutinous rice flour. Not only are detection limits improved, but dried aqueous standard solutions can be used for external calibration, thereby significantly increasing the applicability of solid sampling ETV-ICPOES.

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.

Solid sampling determination of total fluorine in baby food samples by high-resolution continuum source graphite furnace molecular absorption spectrometry.

This study describes the applicability of solid sampling technique for the determination of fluorine in various baby foods via molecular absorption of calcium monofluoride generated in a graphite furnace of high-resolution continuum source atomic absorption spectrometry. Fluorine was determined at CaF wavelength, 606.440nm in a graphite tube applying a pyrolysis temperature of 1000°C and a molecule forming temperature of 2200°C. The limit of detection and characteristic mass of the method were 0.20ng and 0.17ng of fluorine, respectively. The fluorine concentrations determined in standard reference sample (bush branches and leaves) were in good agreement with the certified values. By applying the optimized parameters, the concentration of fluorine in various baby foods were determined. The fluorine concentrations were ranged from

Spectrometric estimation of sample amount in aliquot for a direct solid sampling system and its application to the determination of trace impurities in silver nanoparticles by ETV-ICP-OES.

A method based on a tungsten boat furnace vaporiser, tungsten sample cuvettes, and an inductively coupled plasma (ICP) optical emission spectrometer has been developed for the direct determination of silicon, phosphorus, and sulphur in silver nanoparticles. The important point in the proposed method is that the entire sample in each batch is vaporised, which enables simultaneous measurement of the emission of not only the analyte but also the silver matrix. Furthermore, since the silver nanoparticles are sufficiently pure, the contribution of impurities to the sample amounts will be negligible. Therefore, this estimation is suitable for measuring the sample amount in each aliquot instead of the conventional weighing procedure using a microbalance; therefore, no tedious weighing procedures for estimating the sample amount introduced into the ETV device are needed. An additional advantage is that pretreatment and/or predigestion are unnecessary. The sample throughput is approximately 35 batches per hour. The detection limits of silicon, phosphorus, and sulphur in the silver nanoparticles (dry powder) are 15, 4.2, and 62 µg g(-1), respectively. Analytical results for various silver nanoparticles as both dry particles and in suspended solutions are described, and these values are compared to those obtained by conventional weighing with a microbalance. This methodology is useful for rapid screening and accurate analysis of silver nanoparticles, especially for industrial applications.