Simplex optimisation of conditions for the determination of antimony in environmental samples by using electrothermal atomic absorption spectrometry

Analysis of the total antimony in plant material was unsuccessful using the electrothermal atomic absorption spectrometry (ETAAS) conditions recommended by the instrument manufacturer. For this reason, an optimisation procedure utilising the Plackett-Burman method, simplex optimisation and visualisation of the generated response surface via principal components analysis, was carried out. The Plackett-Burman method was used to eliminate four of the initial variables chosen. Four variables (atomisation temperature, atomisation time, ash temperature and modifier concentration) were subsequently optimised using the composite modified simplex method and the results were visualised as a contour diagram, after reduction to two principal components. The optimised conditions were used for the analysis of both an acid digested pine needle standard reference material (NIST 1575) and a pond weed sample, collected from a contaminated site at Yellowknife Bay, Yellowknife, NWT, Canada. The total concentration of antimony present in the pine needles was statistically indistinguishable from the non-certified value, as was the value for the pond weed sample, compared with a value determined by neutron activation analysis (NAA). The results for the analysis of the pond weed sample by ETAAS agreed with those obtained from a subsequent analysis by inductively coupled plasma-mass spectrometry.     

Determination of lead in plants in controlling phytoremediation processes using slurry sampling electrothermal atomic absorption spectrometry

The comparative determination of lead in plant samples by two atomic spectrometric techniques is reported. At first, slurry sampling electrothermal atomisation atomic absorption spectrometry (ETAAS) was applied. The results obtained were compared with those found after a wet digestion procedure by flame atomic absorption spectrometry (FAAS) or ETAAS. The accuracy of the studied methods was checked using a certified reference material (CL???1 CRM, Cabbage Leaves). The recovery of lead was 90% for slurry sampling ETAAS, and 86.6% for liquid sampling ETAAS. The advantages of the slurry sampling ETAAS method are the simplicity of sample preparation and very good sensitivity.     

Determination of trace elements in biological materials using tetramethylammonium hydroxide for sample preparation

A method to prepare milk powder, bovine liver and bovine muscle samples for analysis by electrothermal atomic absorption spectrometry (ETAAS) is proposed. Samples are mixed with a small amount of tetramethylammonium hydroxide (TMAH) and a stable and homogeneous slurry is produced in ca. 2 h with heating at 60–70 °C. After such sample preparation and dilution with water, trace elements are determined in certified reference materials. Pyrolysis and atomisation temperatures are optimised for each element, and several modifiers are investigated. External calibration is used for every analyte. Limits of detection (LODs), precision and accuracy are reported for Cd, Pb, Ni, Cr, Cu and Ag and compared with those obtained after conventional acid digestion. The main advantages of the proposed method are the simplicity of sample preparation and the longer lifetime of the graphite tube.     

Multivariate optimisation of hydride generation procedures for single element determinations of As, Cd, Sb and Se in natural waters by electrothermal atomic absorption spectrometry

Continuous flow hydride generation procedures for As(III), total inorganic As, Cd, total inorganic Sb, Se(IV) and total inorganic Se from sea and hot-spring water samples were optimised by experimental designs. Ir-coated graphite tubes were used as preconcentration and atomisation medium of the hydrides generated. Several factors affecting the hydride generation efficiency were studied. Results obtained from Plackett-Burman designs suggest that sodium borohydride flow rate and reduction coil length, are significant factors for total inorganic arsenic hydride generation. For cadmium hydride generation the significant factors are hydrochloric acid concentration, hydrochloric acid and sodium borohydride flow rates and reduction coil length. For total inorganic antimony hydride generation the factors affecting the hydride generation procedure are hydrochloric acid and potassium iodide concentrations and reduction coil length; finally, pre-reduction coil length and oven temperature for the pre-reduction step are statistically significant factors for total inorganic selenium hydride generation. In addition, the factors studied for the arsenic and selenium hydride generation from As(III) and Se(IV) are not significant. From these studies, the significant variables were optimised by central composite designs. Validation carried out analysis on three reference materials: SLRS-4 (Riverie water), CASS-3 (seawater) and NIST-1643d.     

Bismuth determination in environmental samples by hydride generation-electrothermal atomic absorption spectrometry

A hydride generation procedure, via flow injection, coupled to electrothermal atomic absorption spectrometry was optimised for Bi determination in sea water and hot-spring water and acid extracts from coal, coal fly ash and slag samples. The effects of several variables such as hydrochloric acid and sodium tetrahydroborate concentrations, hydrochloric acid and sodium tetrahydroborate flow rates, reaction coil length, trapping and atomisation temperatures, trapping time and the Ar flow rate have been investigated by using a 2⁹*3/128 Plackett-Burman design. From these studies, certain variables (sodium tetrahydroborate concentration and trapping time) showed up as significant, and they were optimised by a 2²+star central composite design. In addition, a study of the bismuthine trapping and atomisation efficiency from graphite tubes (GTs) permanently treated with uranium, tantalum, lanthanum oxide, niobium, beryllium oxide, chromium oxide and tantalum carbide were investigated. The results obtained were compared with those achieved by iridium and zirconium-treated GTs. The best analytical performances, with characteristic mass of 35 pg and detection limit of 70 ng l⁻¹, were achieved by using U-treated GTs. Accuracy were checked using several reference materials: 1643d (Trace Elements in Water), TM-24 (Reference Water), GBW-07401 (Soil) and 1632c (Trace Elements in Coal).     

Chemometric investigation of systematic error in the analysis of biological materials by flame and electrothermal atomic absorption spectrometry

Systematic errors observed when using flame atomic absorption spectrometry (FAAS) and electrothermal atomic spectrometry (ETAAS) for the analysis of biological solid materials (seafood products) were evaluated. The effect of the sample pre-treatment method (microwave-assisted acid digestion, ultrasound-assisted acid leaching and slurry sampling) as well as the number of times that a certain pre-treatment process is repeated, were two factors evaluated. They give information about the effect of the sample pre-treatment on the uncertainty in the analysis. In addition, the number of measurements (i.e., number of times that an acid digest, an acid leachate or aqueous slurry are analysed) and the calibration technique used (aqueous calibration method or standard addition technique) were other two variables taken into account. This last factor gives information about the effect of the calibration on the results, while the replicate measurements showed the repeatability. A fifth variable named as sample matrix tests the influence of the matrix sample on the systematic error through the use of different reference materials. This variable allows the study of the effect of the trace element concentrations on the uncertainty because the trace elements contents are different in each reference material. Experimental design and principal component analysis approaches were used as chemometric tools. It has been found that the use of the slurry sampling technique in ETAAS and FAAS and the determination of high element concentrations by ETAAS have led to poor precision.     

Determination of vanadium in water by electrothermal atomisation atomic absorption spectrometry after extraction with 8-hydroxyquinoline in isobutyl methyl ketone

A sensitive method for the determination of vanadium in water by electrothermal atomisation atomic absorption spectrometry (ETAAS) is described. The vanadium is chelated with 8-hydroxyquinoline in isobutyl methyl ketone and determined by ETAAS after pre-heating the pyrolytic graphite coated graphite tube of a graphite furnace atomiser before injection. The effects of the pH and amount of reagent required for the extraction were studied. The precision, accuracy and interferences of the method were also investigated. The proposed method allows concentrations of vanadium of 0.16 microgram l-1 to be detected.     

Headspace single-drop microextraction with in situ stibine generation for the determination of antimony (III) and total antimony by electrothermal-atomic absorption spectrometry

A headspace-single drop microextraction method combined with electrothermal atomic absorption spectrometry (ETAAS) is developed for the extraction and preconcentration of antimony(III) and total antimony into a Pd(II)-containing aqueous drop after hydride generation. Experimental variables such as hydrochloric acid and sodium tetrahydroborate concentrations, sample volume, Pd(II) concentration in the acceptor phase and microextraction time were optimized. A 2^6-2 _IV factorial fractional design was initially used for screening the effect of the variables, followed by an univariate approach. The method showed a great freedom from interferences caused by hydride-forming elements and transition metals. The detection limit of Sb(III) was 25 pg mL^?1. A preconcentration factor of 176 is achieved in 3 min. The repeatability, expressed as relative standard deviation, was 4.7%. The method was validated against two certified reference materials (NWRI-TM 27.2 and NIST 2711) and applied to the determination of Sb(III) and total Sb in waters.     

Arsenic extraction in marine biological materials using pressurised liquid extraction

A pressurised liquid extraction (PLE) procedure, by using methanol/water mixture, was developed for extracting arsenical species from marine biological material (mussel and fish) and standard reference materials (CRMs). A Plackett-Burman 2⁸ × 3/64 designs (PBD) was used as a multivariate strategy for the evaluation of the effects of several variables (MeOH/H₂O solvent mixture, temperature, static time, extraction steps, pressure, mean particle size and diatomaceous earth (DE) mass/sample mass ratio) on the extracting procedure. Electrothermal atomic absorption spectrometry (ETAAS) was used to determine the total As concentration on the methanolic extracts. The accuracy of the optimised extraction procedure was verified by analysing several CRMs (GBW-08751, BCR-278R and DORM-2). The precision obtained (between 4.5 and 6.2%) was adequate. The extracted arsenic species (mainly arsenobetaine (AsB)) were analysed by high performance liquid chromatography coupled to ultraviolet cracking and hydride generation-atomic fluorescence spectrometry (HPLC-UV-HG-AFS). The analytical performances obtained were adequate for the arsenic speciation in marine biological samples; LOD between 10 and 35 ng g⁻¹. The accuracy was verified for AsB using DORM-2. Finally, the proposed method (PLE followed by HPLC-UV-HG-AFS) was applied to mussel and fish samples.     

Sample pre-treatment methods for the trace elements determination in seafood products by atomic absorption spectrometry

Different sample pre-treatments for seafood products have been compared with determine trace elements (As, Cd, Cr, Cu, Fe, Mg, Mn, Ni, Pb, Se and Zn) by flame atomic absorption spectrometry (FAAS) and electrothermal atomic absorption spectrometry (ETAAS). Classic pre-treatments as microwave assisted-acid digestion and the slurry sampling technique were compared with new procedures such as microwave energy or ultrasound energy assisted-acid leaching process and enzymatic hydrolysis methodologies based on the use of pronase E. The methods were applied to DORM-1 and DOLT-1 reference materials with certified contents for the studied elements. The Student-Newman-Keuls (SNK) method was used to compare with element concentration means obtained with each sample pre-treatment and also the certified concentration means in both reference materials. Multivariate techniques such as principal components analysis (PCA) was also applied to comparative purposes.     

Direct determination of lead at sub-ppb levels in secondary coolants of pressurized water reactor by electrothermal atomic absorption spectrometry with multiple injections

The method of incorporating in-situ pre-concentration technique via multiple injections followed by electrothermal atomic absorption spectrometry (ETAAS) is described for the direct determination of lead at sub-ppb levels in secondary coolants of pressurized water reactor (PWR). Prior to ETAAS measurement, water samples were concentrated by means of multiple injections (9×90 ml) and evaporation in a pyrocoated graphite tube. Optimization of the in-situ pre-concentration via multiple injections with ETAAS analysis was investigated. The feasibility of the proposed method was tested for direct determination of lead in secondary coolants of pressurized water reactor. A SRM 1643c certified reference water sample has been used for quality control. The result are in good agreement with the certified value. By the use of 0.81 ml sample volume 0.012 ppb detection limit was obtained.     

Application of experimental design in a method for screening sediments for global determination of organic tin by electrothermal atomic absorption spectrometry (ETAAS)

An experimental design was developed to obtain a simple procedure for global determination of organic tin compounds in sediment. Sediment was extracted by a two-phase method and tin was determined in the organic extract by electrothermal atomic absorption spectrometry (ETAAS), with palladium as chemical modifier. A Plackett-Burman design for screening and a fractional central composite design (CCD) for optimizing were used for evaluation of the effects of several variables. The results showed that sediment mass, volume and concentration of extracting acid, pyrolysis and atomization temperatures, and modifier concentration affect the determination. Reference material PACS-2 was analyzed to evaluate the procedure. It was possible to extract 82% of the organotin content certified in the reference sediment. The limit of detection (LOD) was 0.08 microg g(-1) and the relative standard deviation was 4%. The method was applied to the analysis of estuarine superficial sediments from Gipuzkoa (Spain). The organotin content of these samples ranged from 0.7 to 7.7 microg g(-1), as tin, on a dry-weight basis.     

Determination of Trace Elements in Arsenic and Antimony Minerals by Atomic Absorption Spectrometry and k0-Instrumental Neutron Activation Analysis After Removal of As and Sb

The content of trace elements in arsenic and antimony minerals from the Allchar mine, Macedonia, was determined by electrothermal atomic absorption spectrometry (ETAAS) and k₀-instrumental neutron activation analysis (k₀-INAA) after removal of arsenic and antimony. Their direct determination by ETAAS or k₀-INAA in arsenic (realgar and orpiment) and antimony (stibnite) minerals is limited by strong matrix interferences from As and Sb. Successful elimination of both elements was realized by the extraction of their iodide complexes into toluene. It was found that the optimal conditions were triple extraction of arsenic into toluene from 6mol·L^–1 HCl with addition of KI. Triple extraction of antimony was most successful in the system 4.5mol·L^–1 H₂SO₄ and KI into toluene. In both cases, trace elements (Cd, Co, Cr, Cu, Fe, Mn, Ni, Pb and Zn) were then detected in the aqueous phase by ETAAS. The proposed procedures with ETAAS were checked by the method of standard additions and Cd, Co, Cr, Cu, Fe, Mn, Ni, Pb and Zn determined in realgar, orpiment and stibnite. Using k₀-INAA the trace elements Ba, Ce, Co, Cr, Cs, Fe, Hg, Sc, Tb, Th, U and Zn in realgar and orpiment were determined before and after As and Sb removal from the same aliquot of sample. The removal of both elements with KI into toluene was higher than 99.8% and no losses of trace elements were observed.     

Solidified floating organic drop microextraction–electrothermal atomic absorption spectrometry for ultra trace determination of antimony species in tea, basil and water samples

Solidified floating organic drop microextraction was applied as a separation/preconcentration step prior to the electrothermal atomic absorption spectrometric (ETAAS) determination of ultra trace of antimony species. The method was based on the formation of an extractable complex between Sb(III) and ammonium pyrrolidinedithiocarbamate at pH ~ 5, while Sb(V) was remained in the aqueous phase. The antimony extracted into 1-undecanol was determined by ETAAS. Total antimony was determined after the reduction of Sb(V) to Sb(III) with potassium iodide and ascorbic acid. The amount of Sb(V) was determined from the difference of concentration of total antimony and Sb(III). Under the optimum conditions an enhancement factor of 437.5 and a detection limit of 5.0 ng L^?1for the preconcentration of 25 mL of sample was achieved. The relative standard deviation at 300 ng L^?1 of antimony was found to be 3.5 % (n = 6). The proposed method was successfully applied to the determination of antimony in tea, basil and natural water samples.     

Determination of silicon in biological samples by ICP-OES after non-oxidative decomposition under alkaline conditions.

A non-oxidative alkaline sample digestion procedure using tetramethylammonium hydroxide and a high pressure, microwave assisted autoclave digestion system was developed. The silicon concentrations of the digested samples were measured by inductively coupled axial plasma optical emission spectrometry (ICP-OES). Details of the digestion conditions as well as the optimised instrumental parameters for ICP-OES are described. The method was developed and tested using silicon-spiked ascorbic acid and applied to samples of animal tissue and organs. The total silicon content of two different reference materials, NIST 1577b Bovine liver and BCR 184 Bovine Muscle having neither certified nor informational values for Si was determined. The results obtained are compared with the results of independent methods such as wavelength dispersive x-ray fluorescence spectrometry (WDXRF) and solid sampling electrothermal atomic absorption spectrometry (ETAAS). The method described achieves a limit of detection of 2 mg kg(-1) using 100 mg of solid biological or organic material and covers a concentration range of up to 500 mg kg(-1).     

Detection of silver nanoparticles in parsley by solid sampling high-resolution–continuum source atomic absorption spectrometry

In this work, we present a fast and simple approach for detection of silver nanoparticles (AgNPs) in biological material (parsley) by solid sampling high-resolution–continuum source atomic absorption spectrometry (HR-CS AAS). A novel evaluation strategy was developed in order to distinguish AgNPs from ionic silver and for sizing of AgNPs. For this purpose, atomisation delay was introduced as significant indication of AgNPs, whereas atomisation rates allow distinction of 20-, 60-, and 80-nm AgNPs. Atomisation delays were found to be higher for samples containing silver ions than for samples containing silver nanoparticles. A maximum difference in atomisation delay normalised by the sample weight of 6.27?±?0.96 s mg^?1 was obtained after optimisation of the furnace program of the AAS. For this purpose, a multivariate experimental design was used varying atomisation temperature, atomisation heating rate and pyrolysis temperature. Atomisation rates were calculated as the slope of the first inflection point of the absorbance signals and correlated with the size of the AgNPs in the biological sample. Hence, solid sampling HR-CS AAS was proved to be a promising tool for identifying and distinguishing silver nanoparticles from ionic silver directly in solid biological samples.

Improvements in the methylmercury extraction from human hair by headspace solid-phase microextraction followed by gas-chromatography cold-vapour atomic fluorescence spectrometry

Improvements in the methylmercury extraction from human hair by solid-phase microextraction followed by gas chromatography coupled to cold-vapour atomic fluorescence spectrometry (GC-CVAFS) have been carried out. They consisted in the optimisation of the digestion step prior to the aqueous-phase ethylation and in the GC-CVAFS interface set-up. The main digestion parameters such as acid type, concentration, temperature and time have been optimised for hair sample analysis, thereby avoiding methylmercury degradation. Moreover, the stability of the digested samples was evaluated to improve the sample throughput.     

Simultaneous extraction of several persistent organic pollutants in sediment using focused ultrasonic solid-liquid extraction

Focused ultrasonic solid-liquid extraction (FUSLE) has been optimised for simultaneous analysis of polycyclic aromatic hydrocarbons (PAHs), polychlorinated biphenyls (PCBs), phthalate esters (PEs), and nonylphenols (NPs) in sediment samples. Optimisation was performed using naturally polluted freeze-dried sediment samples. The variables studied during the optimisation process were: percentage of maximum power (10-60%), extraction time (10-300 s), number of cycles (1-9), composition of the extraction solvent (acetone-n-hexane, 10:90-90:10), and sample mass (0.1-1 g). The volume of the extractant was constant (10 mL) and the extraction was performed at 0 degrees C in an ice-bath during the optimisation process. All these variables were studied using an experimental design approach by means of The Unscrambler software. The extraction time and the operational variables (number of cycles and power) had no statistically significant effect in the extraction and they were held at 2 min, 20% power, and seven cycles, respectively. The mass and the addition of non-polar solvent (n-hexane) had a negative effect in the extraction yield and, thus, the mass was held at 0.5 g and pure acetone was used as extraction solvent. After those variables were optimised, the effect of the extraction temperature (0 degrees C or room temperature) was also studied. The validation of the extraction method was performed using NIST-1944 reference material in the case of PAHs and PCBs. Because no certified reference sediment is available for PEs and NPs, the results obtained for FUSLE were compared with those obtained for microwave-assisted extraction (MAE) under conditions optimised elsewhere. In all the cases the analysis were performed by gas chromatography-mass spectrometry (GC-MS). Good accuracy were achieved in all cases. The limits of detection (LODs) obtained were between 0.10 and 1.70 ng g(-1) for PAHs (except for naphthalene 5.33 ng g(-1)), 0.02 and 0.16 ng g(-1) for PCBs, 46 and 188 ng g(-1) for PEs, and 0.6 and 12.4 microg g(-1) for NPs. The precision was around 5-10% for most of the PAHs and PCBs and around 2-10% for most of the PEs and NPs.     

Application of flow injection on-line electrothermal atomic absorption spectrometry to the determination of rhodium

A fully automated procedure for the determination of rhodium has been developed using flow injection (FI) on-line microcolumn preconcentration coupled with electrothermal atomic absorption spectrometry (ETAAS). The proposed FI manifold and its operation make possible the introduction of the total eluate volume into the graphite atomizer, avoiding the necessity for optimisation of subsampling the eluate. Rhodium is adsorbed on a microcolumn packed with 1,5-bis(di-2-pyridyl)methylene thiocarbohydrazide immobilized on silica gel (DPTH-gel). Under the optimum conditions, using a 60 s preconcentration time, a sample flow rate of 3.5 mL min(-1) and an injection volume of eluent of 50 microL, a linear calibration graph was obtained from 1 to at least 40 ng mL(-1) and the detection limit was 1 ng mL(-1). The proposed method has been successfully applied to the analysis of samples. Its performance was investigated against certified reference catalyst sample SRM-2557 and by recovery measurements on spiked samples (soil, foods and beverages).     

Direct determination of Ge in hot spring waters and coal fly ash samples by hydride generation-ETAAS

A method for Ge determination in hot spring water and acid extracts from coal fly ash samples involving hydride generation, trapping and atomisation of the hydride generated from Ir-treated graphite tubes (GTs) has been developed. Hydride was generated from hydrochloric acid medium using sodium tetrahydroborate. Several factors affecting the hydride generation, transport, trapping and atomisation efficiency were studied by using a Plackett-Burman design. Results obtained from Plackett-Burman designs suggest that trapping and atomisation temperatures are the significant factors involved on the procedure. The accuracy was studied using NIST-1633a (coal fly ash) reference material. The detection limit of the proposed method was 2.4 μg l⁻¹ and the characteristic mass of 233 pg was achieved. The Ge concentrations in fly ash and hot spring samples were between 6.25-132 μg g⁻¹ and 12.84-36.2 μg l⁻¹.