Henryk
Matusiewicz
* and
Magdalena
Krawczyk
Politechnika Poznańska, Department of Analytical Chemistry, 60-965, Poznań, Poland. E-mail: Henryk.Matusiewicz@put.poznan.pl
First published on 5th October 2007
The analytical performance of non-chromatographic coupled hydride generation, integrated atom trap (HG-IAT) atomizer flame absorption spectrometry (FAAS) systems were evaluated for the speciation analysis of antimony in environmental samples. Antimony, using formation of stibine (SbH3) vapors were atomized in an air–acetylene flame-heated IAT. A new design of HG-IAT-FAAS hyphenated technique that would exceed the operational capabilities of existing arrangements (a water-cooled single silica tube, double-slotted quartz tube or an “integrated trap”) was investigated. For the estimation of Sb(III) and Sb(V) concentrations in samples, the difference between the analytical sensitivities of the absorbance signals obtained for antimony hydride without and with previous treatment of samples with L-cysteine can be used. The concentration of Sb(V) was calculated by the difference between total Sbtot and Sb(III). A dramatic improvement in detection limit was achieved compared with that obtained using either of the atom trapping techniques, presented above, separately. This novel approach decreases the detection limit down to low pg mL–1 levels. The concentration detection limit, defined as 3 times the blank standard deviation (3sigma), was 0.2 ng mL–1. For a 120 s in situ pre-concentration time (sample volume of 2 mL), sensitivity enhancement compared to flame AAS, was 550 fold for Sb, using hydride generation-atom trapping technique. The sensitivity can be further improved by increasing the collection time. The precision, expressed by RSD, was 8.0% (n = 6) for Sb. The designs studied include slotted tube, water-cooled single silica tube and integrated atom traps. Reference and real sample materials were analyzed. The accuracy of the method was verified by the use of certified reference materials (NIST SRM 2704 Buffalo River Sediment, SRM 2710 Montana Soil, SRM 1633a Coal Fly Ash, SRM 1575 Pine Needles, SRM 1643e Trace Elements in Water) and by aqueous standard calibration technique (solutions). The measured Sb content, in reference materials, were in satisfactory agreement with the certified values. The hyphenated technique was applied for antimony determinations in soil, sediment, coal fly ash, sewage and river water.
The flame has been developed over the past decades into a powerful tool for elemental analysis by atomic absorption spectrometry (FAAS). Despite its widespread use, FAAS remains limited in routine applications by normal sample introduction methods which are insufficiently sensitive to permit direct quantitative determination of trace or ultratrace concentrations of some elements, such as hydride forming elements. Therefore, in most cases a pre-concentration stage, before the elements can be determined, is essential.
It is well established that significant improvements in the limits of detection of flame atomic absorption spectrometry (FAAS) and graphite furnace atomic absorption spectrometry (GF-AAS) may be achieved by chemical vapor generation, mostly hydride generation (HG) and in-atomizer (silica or graphite tube) trapping (pre-concentration) as reviewed4,5 for the determination of As, Bi, Ge, In, Pb, Sb, Se, Sn, Te and Tl (as well as Hg).
Hydride generation combined with AAS detection (HG-AAS) is one of the most powerful analytical methods for the determination of total Sb. Initially, AAS using different atomization devices was the most employed technique.6–10 Rondón et al.6 described the continuous flow hydride generation system AAS for the determination of Sb using a T-quartz cell tube heated by a conventional 10 cm path length air–acetylene flame. Krachler et al.7 suggested a flow injection method for the determination of trace amount of Sb by HG-AAS using a quartz tube atomizer. Petit de Penaet al.8 studied the performance of flow injection hydride generation system AAS in the determination of Sb in liver tissue and whole blood. Calixto de Campos et al.9 developed a method for the determination of Sb by HG-AAS using an electrically heated quartz cell. Marlon de Moraes Flores et al.10 described the generation of Sb(III) with atomization in a flame AAS using a quartz cell atom trap.
One way to determine antimony species in samples is to use a chromatographic speciation method. Hyphenated techniques using chromatographic separation coupled to atomic spectrometers have been widely utilized in the speciation of antimony in different matrices.11 A possible non-chromatographic alternative method is HG-AAS; antimony speciation analysis is based on the slow kinetics of hydride formation from the pentavalent state.12,13 In recent years, hydride generation has also been employed to selectively measure antimony species in natural waters, liver tissue, whole blood, samples of injectable drugs, etc.,6,8,10,14 as different antimony species have different hydride generation activity, e.g., inorganic Sb(III) species may form hydrides while Sb(V) does not when reacting with NaBH4.
Unfortunately, none of these studies reported a successful HG-AAS determination of Sb at the ultratrace levels in real samples. In addition, the reported limits of detection are not so low as those currently achievable by the use of an in situ atom trapping technique.
In situ trapping permits a significant enhancement in sensitivity for batch and continuous hydride generation approaches used in the ultra-trace determination of volatile hydride species. Due to its importance, in situ trapping, which allows the coupling of hydride generation to integrated atom trap (IAT),15–19 was chosen for this study.
An analytical system was developed to trap and pre-concentrate Bi from the vapor phase stream. Bismuthine formed by sodium tetrahydroborate reduction was trapped on a tungsten coil previously heated to 270 °C. The analyte species were re-volatilized by increasing the coil temperature to 1200 °C and then transported to an externally heated silica T-tube by using a mixture of argon and hydrogen as the carrier gas.20 Korkmaz et al.21 investigated the nature of re-volatilization from atom trap surfaces in flame by AAS. Analytes Au, Bi, Cd, Mn and Pb were trapped on a water-cooled, U-shaped silica trap or a slotted silica tube trap and re-volatilized by organic solvent aspiration. They concluded that, although heating was not necessarily associated with re-volatilization, direct contact between the flame and the active silica surface was required. Recently,22 the analytical performance of three trap systems (water-cooled U-shaped silica trap, water-cooled U-shaped silica trap combined with slotted silica tube and slotted tube trap) for flame AAS were evaluated for determination of Cd and Pb in waters. Guo and Guo23 reported SeH2 collection at gold wire heated to 200 °C situated in a quartz tube atomizer (atomic fluorescence spectrometry (AFS) or AAS detection) with a separate inlet for argon. A successful trapping of PbH4 in a bare quartz tube was announced by Korkmaz et al.,24 who also suggested that the same trap could be used also for other hydrides. Recently, a preliminary evaluation of a quartz tube trap for collection of SbH3 and for volatilization of trapped analyte with subsequent atomization in a multiple microflame quartz tube atomizer for AAS was presented.25 Kratzer and Dědina extended their investigation of stibine trapping in quartz tube traps26 to stibine collection (and subsequent analyte atomization) in conventional quartz tube atomizers.25 They employed the simplest possible experimental arrangement; just the commercially available externally heated quartz tube atomizer without any trap or additional heating device. Further, a modification of the externally heated quartz tube atomizer, making possible in situ trapping of bismuthine and subsequent analyte atomization for Bi was described.27 Krejči et al.28 investigated the collection of Sb and Bi on a molybdenum foil strip situated in a laboratory-made quartz T-tube, single-slot burner head, following hydride generation. Recently,29 the analytical performance of a miniature quartz trap coupled with electrochemical hydride generator for antimony determination was described. A portion of the inlet arm of the conventional quartz tube atomizer was used as an integrated trap medium for on-line pre-concentration of electrochemically generated hydrides. Very recently,30 a novel quartz device has been designed to trap arsine and selenium hydride and subsequently to volatilize the collected analyte and atomize it for AAS detection. The device is actually the multiple microflame quartz-tube atomizer with inlet arm modified to serve as the trap and to accommodate the oxygen-delivery capillary used to combust hydrogen during the trapping step.
This work has been mainly aimed at improving analytical performance of antimony conventional hydride generation flow system by combining this approach for in situ trapping technique with an integrated atom trap system for flame AAS that is applicable to determination of Sb in real and reference materials. In this work, the non-chromatographic speciation HG-IAT-FAAS method was developed to selectively measure the total and inorganic forms of antimony species exclusive of organic antimony (to distinguish between inorganic Sb(III)- and Sb(V)-species) in samples. The hydride generation technique brings the FAAS method closer to the detection limits of HG-GF-AAS (in situ trapping technique).31–34 Finally, in order to check the accuracy of the proposed system, analyses of standard reference materials were performed.
Parameter | Setting |
---|---|
a Nebulizer uptake rate, 5 mL min–1. b Air flow rate 475 L h–1, acetylene flow rate 50 L h–1 (fuel-lean flame); 10 cm slot burner. | |
Wavelength/nm | 217.6 |
Spectralband pass/nm | 0.2 |
Lamp current/mA | 7 |
Flame typea | Air–C2H2 |
Flame conditionsb | Lean |
Silica tube obscuration (%) | ca. 30 |
Coolant water/L min–1 | ca. 2 |
Window of measurements/s | 15 |
Read time/s | 7 |
Smoothing | No |
Signal measurement | AA (Peak area) |
Even though the hydride generation cells served as gas–liquid separators, in an attempt to completely reduce water vapor, a quartz gas–liquid separator identical to that described earlier36 was installed between the chemifolds and the nebulizer/spray chamber.
The operating conditions for batch and continuous-flow hydride generation atomic absorption spectrometry are summarized in Table 2. A schematic diagram of the batch and continuous-flow HG-IAT-FAAS system with in situ pre-concentration in the IAT unit is shown in Fig. 1.
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Fig. 1 Schematic diagram of the HG-IAT-FAAS system. |
Parameter | Batch hydride generation | Continuous-flow hydride generation | ||
---|---|---|---|---|
Sbtot | Sb(III) | Sbtot | Sb(III) | |
a In 0.5% (m/v) NaOH solution. b Ref. 39 | ||||
NaBH4 concentrationa (% (m/v)) | 1.0 | 1.0 | 1.0 | 2.0 |
NaBH4 solution flow rate/mL min–1 | 2.5 | 2.5 | 1.0 | 1.0 |
HCl concentration/mol L–1 | 2.0 | — | 3.0 | — |
Oxalic acid concentration (% (m/v)) | — | 5.0 | — | 6.0 |
L-cysteine concentration (% (m/v)) | 5.0 | — | 4.0 | — |
Reduction time (L-cysteine)/min | 30 | — | 30 | — |
Sample flow rate/mL min–1 | — | — | 1.0 | 1.0 |
Sample volume/mL | 10 | 10 | 2 | 2 |
Carrier air flow rate/mL min–1 | 75 | 75 | 100 | 100 |
Gas–liquid separator | As described in the literature.34 | |||
PVC/PTFE peristaltic tubes | 40 cm × 1.9 mm i.d. × 3.9 mm o.d. | |||
Trapping time/s | 120 | |||
Trapping temperature/°C | <100 (373 K) | |||
Atomization temperatureb/°C | ca. 1330 (1600 K) |
A double-slotted quartz tube atom trap (STAT) was installed on a standard 10 cm air–acetylene burner. The design permits changeover from analysis with the IAT15 to that for a conventional flame in a few seconds.
A water-cooled single silica tube atom trap (WCAT) was arranged, as previously described,15 and mounted on a 10 cm burner in such a manner in order to permit the system to be vertically and laterally adjusted to the flame. The tubes were of an o.d. 3 mm and an i.d. of 1 mm for water cooling.
An integrated atom trap (IAT) was designed and constructed in this laboratory,13 it consisted of a combination of a WCAT and a STAT (see Fig. 1 in ref. 15). The IAT system was mounted over an air–acetylene burner on a mounting bracket, which permitted calibrated movement both vertically and horizontally.
A modified cooling system was used for cooling the water16 (see Fig. 1 in ref. 16). The continuously flowing cooling water kept the surface of the silica tube at the temperature below 100 °C. This allowed the analyte atoms to condense on the surface of the tube.
The single silica and slotted quartz tubes were coated with lanthanum to prevent devitrification and to improve the silica surface properties (increasing the surface area) by continuous aspiration via the burner nebulizer of 1.0% lanthanum solution, for 15 min. The tubes were re-coated after approximately 100–200 runs.
Standard solutions of Sb(III) were prepared from a 1000 mg mL–1Sb(III) atomic absorption standards (Titrisol grade, Merck, Darmstadt, Germany). Standard solutions of Sb(V) were prepared from potassium hexahydroxoantimonate(V) (Riedel-de-Haën). All working standard solutions of Sb(III) and Sb(V) were prepared daily to prevent any possible species change, by diluting appropriate aliquots of the stock solution in high-purity water.
Sodium tetrahydroborate(III) and potassium tetrahydroborate(III), used as reducing solutions, were prepared daily, or more frequently if required, by dissolving proper amounts of NaBH4 and KBH4 (pellets) (Alfa Inorganics, Ward Hill, USA) in high-purity water and stabilized with 0.1% (m/v) NaOH (Suprapur, Merck, Darmstadt, Germany) solution to decrease its rate of decomposition, and was used without filtration.
Thiourea was prepared by dissolving the powder (Fluka, Buchs, Switzerland) in water to yield a 1 mol L–1 solution.
A 5% (m/v) potassium iodide (Merck) and a 5% (m/v) ascorbic acid (Fluka) solution were prepared in water.
Oxalic acid (Fluka) was prepared by dissolving the powder in water to yield a 10% (m/v) solution.
A 9% (m/v) L-cysteine (Merck) solution was prepared in water as a pre-reductor agent.
Citric and picolinic acids (Fluka) and sodium dithionite (Merck) were prepared fresh daily.
The lanthanum chloride solution, used to coat the quartz tubes (1.0% (m/v)) was prepared from a 10% (m/v) lanthanum chloride solution supplied by Alfa Inorganics (Ward Hill, MA, USA) as a releasing agent for the use in atomic absorption.
All mineral acids (HNO3, HCl, HF) and hydrogen peroxide 30% (v/v) of the highest quality (Suprapur, Merck, Darmstadt, Germany) were used. High-purity water: deionized water (model DEMIWA 5 ROSA, Watek, Czech Republic), and doubly distilled water (quartz apparatus, Bi18, Heraeus, Hanau, Germany) were used throughout the experiments.
The following samples were used in this study: the untreated waste water and coal fly ash was sampled from Poznań Coal-fired Power Plant in Poland, soil from Silesia, sediment from Dębina lake in Poznań (Poland) and water from Warta river (Poznań, Poland).
To ensure homogeneity, it was necessary to grind the real, solid samples. This was achieved without difficulty in an agate pestle and mortar by manual grinding for coal fly ash and soil, and by a vibrational mixer mill Model S (Testchem, Pszów, Poland) equipped with 30 mL grinding chamber and rod (6 cm diameter), all made of tungsten carbide.
Approximately 300 mg of powdered inorganic reference materials and samples (Soil, River Sediment, Coal Fly Ash) were placed in the TFM-PTFE vessel (“bomb”) of the microwave digestion system and moistened by 1 mL of 30% H2O2; then 3 mL of concentrated HNO3 and 1 mL of concentrated HF were added. The samples were heated for 15 min at 150 W. After dissolution, the clear digested solution was transferred into 10 mL calibrated flask and diluted to volume with water. When working with organic material (Pine Needles), approximately 300 mg of sample was first moistened by 1 mL of 30% H2O2, then 3 mL of concentrated HNO3 was used. The sample was heated for 10 min at 100 W. Before further analysis these were appropriately diluted depending on the concentration level of the elements. In all cases, a corresponding blank was also prepared according to the above microwave-assisted digestion procedure.
Parameter (variable) | Boundary limits of parameters, range | Continuous-flow system | Batch mode | ||
---|---|---|---|---|---|
Univariate method | Simplex method | Univariate method | Simplex method | ||
a Response, peak area of the antimony absorption intensity of 217.6 nm. | |||||
HCl/mol L–1 | 0.5–3.5 | 3.0 | 2.7 | 2.0 | 2.4 |
NaBH4 (% (m/v)) | 0.5–5.0 | 1.0 | 2.0 | 1.0 | 1.5 |
L-cysteine (% (m/v)) | 1.0–6.0 | 4.0 | 3.5 | 5.0 | 4.5 |
Oxalic acid (% (m/v)) | 0.5–7.0 | 6.0 | 6.4 | 5.0 | 5.2 |
Air carrier flow rate/mL min–1 | 50–150 | 100 | 108 | 75 | 85 |
Sample and reductant uptake rate/mL min–1 | 0.5–5.0 | 1.0 | 1.5 | 1.0 | 1.3 |
Simplex optimization experiments were performed using a software package obtained from the University of Plymouth. The optimization was carried out using aqueous standard solutions of element (antimony) determined. The net S/B ratio was taken as the criterion of merit. Some preliminary univariate experiments (searches) were performed prior to the simplex optimization in order to establish the boundaries of the values of each parameter. Three measurements for each variable were conducted at the factor of interest. Between each experiment, a blank corrective experiment was run to ensure stable and repeatable results.
The optimum conditions obtained from this procedure were then used to run standard antimony solutions and quantify the antimony present in the samples.
Continuous-flow generation measurements of volatile antimony hydrides (SbH3) were studied using the system shown schematically in Fig. 1. A 2 mL aliquot sample: 0.6 mL volume of 32% HCl solution, 0.8 mL volume of 9% (m/v) L-cysteine solution and 0.6 mL volume of water, were placed in a quartz vessel. The mixture was stored for 30 min before the hydride generation procedure was carried out. This allowed determination of the total content of antimony in the sample [Sb(III) + Sb(V)] as Sb(III)viahydride generation (ensures complete reaction to Sb(III)). The PVC/PTFE transfer line from the reaction cell was placed in the nebulizer/burner system. The Sb sample was being continuously introduced at a rate of 1 mL min–1 to merge with a 1.0% (m/v) solution of NaBH4 (flow rate 1.0 mL min–1). The merging solution feeds the gas–liquid separator to the IAT system. Hydrogen antimony that evolved was transferred (carrier air flow rate, 100 mL min–1) to the IAT system, where analyte species (SbH3) were trapped and collected onto the quartz tube surface. A continuous flow of cooling-water permitted Sb volatile species to condense on the surface of the tube during hydrides collection. The liquid phase was being continuously removed to waste after neutralization with 0.1% NaOH solution.
Hydride generation was also accomplished using the batch system; the application of this generator has been described in a previous paper.38 In brief, the hydrides were generated in batch mode and were introduced into the IAT system by the carrier gas (air) during the hydride-trapping step of the atomizer temperature program only; this step was 120 s in duration in all experiments.
Hydrides were generated from 10 mL volume of samples (batch mode). The NaBH4 solution (1.0% (m/v)) was pumped for 60 s and the hydrides that evolved were transferred (carrier air flow rate, 75 L h–1) to the IAT system, where they were collected onto the quartz tube. The merging solution feeds the gas–liquid separator to the IAT system. A continuous flow of cooling water permitted analyte atoms to condense on the surface of the tube during hydrides collection; a further 60 s air purge of the generator completed the transfer process.
The amount of Sb(V) is determined from the arithmetic difference between the responses of total inorganic antimony obtained using the total antimony procedure and Sb(III) obtained using the antimony(III) procedure.
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Fig. 2 Influence of (a) NaBH4 and (b) KBH4 concentration on the peak area signals of Sbtot (30 ng mL–1) and Sb(III) (30 ng mL–1) in continuous-flow system. The experimental conditions employed are detailed in the Experimental. |
The hydride vapor generation systems (two laboratory-made systems described in the Experimental) that we were using for these investigations allowed us to select from two basic modes of operation, a continuous-flow and a batch mode. Preliminary experiments were performed by FAAS using aqueous standard solutions of antimony. It was determined that the generation efficiency of the volatile Sb species did not greatly depend on the modes and the type of reactors used. However, the continuous-flow system appeared to offer some advantages, such as easy automation and, in combination with trapping of the generated antimony vapor in an IAT, the use of an almost unlimited sample volume simply by pumping sample solution for a correspondingly long period of time, increasing the sensitivity accordingly. In addition, continuous-flow hydride generation ensures rapid, efficient mixing of the sample and reductant, thereby reducing the required reaction time, so lengthy purge times are not necessary as the system is a closed one. Traditional “batch” type HG methods require large purge and/or reaction times to ensure the system is flushed of air and an efficient hydrogenation reaction.
The absorption characteristics of major lines for Sb (217.6; 261.4; 283.3 nm) were investigated by the HG-FAAS method. As a consequence, the Sb 217.6 nm line giving the largest S/B was used throughout as analytical line.
The stability of the flame is obviously controlled by the gas flow rate, it is therefore essential to keep the flame stable in the section of the atomizer. The effects of flame conditions on the trapping and release of the antimony were studied by varying the fuel flow rate. The influence of the flame condition on the signal intensity was investigated by fixing the air flow rate (475 L h–1) and altering the acetylene flow rate. The result of our experiment showed that the best sensitivity was obtained by using a 50 L h–1 of flow rate (lean flame) for acetylene. The absorbance of Sb was not very different for collecting or releasing in a lean, full-rich and stoichiometric flame. Therefore, the air flow rate of 475 L h–1 and acetylene flow rate of 50 L h–1 were used for further experiments during the collection and release cycles.
The water-cooled silica tube trap position was not optimized in our experiments, but was selected based upon previous experience.16 The optimum position of the trap tube (single silica tube and STAT) corresponded to the distance (gap) of 5 mm above the burner, and the position of the silica tube corresponded to obscuration of about one-fourth of the light beam by the upper part of the tube. No significant differences were found in the absorbances when a coolant water flow rate of 1–4 L min–1 were used during the collection cycle of Sb hydrides.
The trapping time is one of the most important factors concerning the sensitivity of HG-IAT-FAAS. In a time-based pre-concentration system the sample loading time value indicates the pre-concentration time of the method and reflects the enrichment factor. It was demonstrated (although not shown) that, although the relationship is not in general linear, a longer trapping time increased the analytical signal. A reasonable trapping time per sample in a routine laboratory would be about 2 min, in order to ensure, with greater certainty, that all of the Sb hydrides had been stripped from the solution and transferred into the atomizer and as a compromise between medium sample consumption, high sensitivity and sufficient sampling frequency. This time was chosen to investigate the analytical performance of the HG-IAT-FAAS system with respect to linearity, sensitivity, precision and detection limit.
To optimize the sample and reductant flow rate for antimony determination, first the optimum flow for Sb was estimated in the range of 0.5–5 mL min–1 (Fig. 3(a)). It was observed that when the flow rate was low (0.5–1 mL min–1), the absorbance increased with the flow rate; when the flow rate went up to 1 mL min–1, the absorbance reached maximum; however, with the further increase of the flow rate (above 2 mL min–1), the absorbance decreased for antimony. Therefore, in this study a 1 mL min–1 sample and reductant flow rate was chosen.
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Fig. 3 Influence of (a) sample and reductant uptake rate; (b) L-cysteine concentration; (c) pre-reduction time; (d) HCl concentration and (e) flow rate of carrier air on the peak area signals of Sbtot (30 ng mL–1) and Sb(III) (30 ng mL–1) in continuous flow system. The experimental conditions employed are detailed in the Experimental. |
The continuous hydride generation system was optimized by varying the concentration of NaBH4, HCl, L-cysteine, oxalic acid and the air carrier flow that regulate volatilization and transport. However, substantial optimization of the generation parameters for the antimony hydrides was not undertaken, as this information was readily available from a review paper4 (and references cited therein) pertaining to trace element detection by atom trapping and in situ pre-concentration for FAAS and on our own observations. All of the factors show a more or less significant effect.
A pre-reduction step is needed to overcome possible errors in total antimony determination, because the efficiency to produce SbH3 depends on the state of oxidation of the element. In the present work, the use of L-cysteine, potassium iodide and thiourea was evaluated. A most efficient pre-reduction of Sb(V) was obtained when L-cysteine was used. Therefore, L-cysteine could be efficiently used as a pre-reducing agent for the reduction of Sb(V) to the lower oxidation state Sb(III), and has been proposed as effective pre-reducer of Sb(V). In addition, oxalic acid is one of the chelating agents that have been used to mask the interference from transition metals (i.e., Co2+, Cu2+, Fe3+, Ni2+); the effect is to prevent the reduction of the interfering metals. It should, therefore, be particularly well suited to the masking of transition metals. The results in Fig. 3(b) and (c) shows that the analytical signal increased with increasing L-cysteine concentration and contact time up to 3.5% (m/v) and 30 min, respectively, but above these values the signal reached a plateau. A concentration of 3.5% (m/v) of L-cysteine and a contact time of 30 min were selected for further experiments as convenient for the pre-reduction of all antimony species. At the same time, this concentration does not affect the determination of Sb(III). It is known that Sb(III) may be reduced to the hydride form in the presence of Sb(V) in some acid media. The efficiency of the generation of antimony hydrides in hydrochloric acid and nitric acid was investigated. When using HNO3 the Sb signals were found to be about 20 to 30% lower than those obtained with HCl. Therefore, it was confirmed that HCl is the most appropriate acid to use. HCl was found to have a plateau of absorbance at a concentration range of 3–3.5 mol L–1. Thus, a 3 mol L–1 portion of HCl was chosen for the generation of Sbtothydride vapors (Fig. 3(d)). Although, when 3 mol L–1HCl was used very few Sb(III) species formed hydride products. The concentration of NaBH4 has been recognized as one of the most critical variables in HG, so was also a parameter of importance for Sb hydride generation. Concentrations in the range 0.5–5.0% of NaBH4 were assayed using 3 mol L–1HCl (Fig. 2(a)). It was observed that the higher its concentration the higher the signal, so the faster should be the reaction and more active intermediates should be formed, but relative standard deviations also increased. On the other hand, higher NaBH4 concentrations than 2% (m/v) would result in a violent reaction (more hydrogen gas was generated) in the gas–liquid separator (generator) and eventually lead to an unstable signal. High NaBH4 concentrations had to be avoided and an optimum value of 2% was chosen for further experiments. The concentration of NaOH used for the stabilization of NaBH4 was also found to have a significant effect on the analytical signal. The highest HG efficiency was obtained when the concentration of NaOH was 0.5% (m/v); therefore, that stabilizer was added in an effort to maintain, in addition, the reagent blank as low as possible.
The air carrier gas flow through the apparatus is one of the basic parameters influencing the transport of the stybine into the trap-flame system, and also the mixing effect of hydride-forming reaction solutions, and thus it can affect the determination of Sb(III) markedly. The hydrides were stripped from the hydride generator and were trapped in the silica tube (atomizer) at air flow rates in the range of 50–150 mL min–1 with a 120 s collection time. It was evident that the use of low carrier gas (air) flow can successfully reduce high analyte losses caused by sorption on the inner surfaces of the apparatus (transport tubing), so such use leads to a slight improvement in the analytical signals. This may be connected with the more efficient separation of the hydrides from the reaction solution. On the other hand, higher carrier gas flow rates (>100 mL min–1) can result in a slight decrease in trapping efficiency (higher flow rates reduces peak areas). The decrease observed is probably due to the diluting effect of the air flow. An air flow of 100 mL min–1 was used throughout the experiments, independent of the Sb oxidation state, in order to transport the hydrides completely (Fig. 3(e)). In the atomization step, a signal with regular shape was observed for trapping temperature and was not significantly influenced by sample introduction time in the tested range between 1 and 3 min. It should be stressed that multiple absorption peaks were not observed. In order to be more illustrative, a recorded peak shape after pre-concentration is shown in Fig. 4 (the signals in Fig. 4 were obtained using a computer).
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Fig. 4 Typical analytical signal shape (profile). 25 ng mL–1Sb, 2 min collection. |
The length of the transfer tubing (between the reaction vessel and the nebulizer/burner IAT system) was not optimized in our experiments, but was selected based upon previous experience.17 Therefore, for practical reasons, a transport tubing length of 30 cm was selected for this study.
Sample | Antimony species | Certified value | |||
---|---|---|---|---|---|
Sb(III) | Sb(V) | Sbtot | Sb(III) | Sbtot | |
a Standard deviation for 6 parallel determinations. b Information (uncertified) value. c Concentration in µg L–1. | |||||
NIST SRM 2704 (Buffalo River Sediment) | — | — | 3.55 ± 0.26a | — | 3.79 ± 0.15 |
NIST SRM 2710 (Montana Soil) | — | — | 36.30 ± 2.65a | — | 38.40 ± 3.01 |
NBS SRM 1633a (Coal Fly Ash) | — | — | 6.71 ± 0.50a | — | 7b |
NBS SRM 1575 (Pine Needles) | — | — | 0.27 ± 0.02a | — | 0.2b |
NIST SRM 1643e (Trace Elements in Water) | 4.55 ± 0.30c | 51.85 ± 3.79c | 56.40 ± 4.12c | — | 58.30 ± 0.61c |
Sample preparation is without any doubt a critical stage in Sb determination in biological and environmental samples. Microwave-assisted acid digestion in closed pressurized PTFE vessels is a well-established tool for sample decomposition and/or dissolution prior to trace element determination. The Sb concentrations in the certified reference materials were determined using HNO3 and H2O2 reagents (for organic samples) and HNO3, H2O2 and HF reagents (for inorganic samples). These “classical” procedures have been considered well suited to Sb determination by HG-FAAS. Almost quantitative recoveries were obtained (in general, better than 96%) when certified reference materials were subject to a high pressure treatment in a TFM-PTFE vessel at high temperature. The results likely indicate that a high pressure and temperature must be employed to destroy completely the stable organic molecules (anionic and cationic species) contained in the samples: in particular, the temperature is the determining parameter; the higher the temperature, the better the quality of decomposition. The high pressure–temperature focused microwave heated digestion system40 allows an effective digestion temperature up to 300 °C, essential to assuring the quantitative oxidation of antimony in samples.
Antimony speciation is carried out by the determination of Sb(III) or Sb(V) and the total antimony, which is determined by the oxidation of Sb(III) to Sb(V) or the reduction of Sb(V) to Sb(III) depending on the method used. A method was developed for the speciation of antimony by reducing Sb(V) into Sb(III) by pre-reductant.
Dissolution procedure has been applied, with control of the reaction conditions, for the speciation of Sb based on direct generation of SbH3 from solutions and the total reduction of Sb(V) to Sb(III) by addition of oxalic acid as a complexing agent. Data in Table 4 summarize the results found for the sample (Trace Elements in Water) under study. In the determination of total Sb, the mean obtained falls within the certified interval in this case.
Hydride generation system | Element | Flame AAS | STAT | WCAT b | IAT b | HG-IATb | In situ trapping | ||||||||
---|---|---|---|---|---|---|---|---|---|---|---|---|---|---|---|
QAT-HG-AAS | HG-GF-AAS | ||||||||||||||
DL | X c | DL | X c | DL | X c | DL | X c | DL | X c | DL | X c | DL | X c | ||
a Detection limit defined by 3 blank criterion (n = 6). b 2 min collection time. c Enhancement (improvement) factor. d Ref. 29. e Ref. 31. f Ref. 32. g Ref. 33. h Ref. 34. | |||||||||||||||
Continuous | Sb(III) | 110.0 | 1.0 | 35.0 | 3.1 | 16.0 | 6.9 | 8.0 | 13.8 | 0.2 | 550 | 0.009d | 12 222 | 0.005e | 22 000 |
Sbtot | 110.0 | 1.0 | 35.0 | 3.1 | 16.0 | 6.9 | 8.0 | 13.8 | 1.1 | 100 | — | — | 0.02f | 5500 | |
Batch | Sb(III) | 110.0 | 1.0 | 35.0 | 3.1 | 16.0 | 6.9 | 8.0 | 13.8 | 0.5 | 220 | — | — | 0.014g | 7860 |
Sbtot | 110.0 | 1.0 | 35.0 | 3.1 | 16.0 | 6.9 | 8.0 | 13.8 | 0.7 | 157 | — | — | 0.005h | 22 000 |
The analytical performance characteristics were evaluated for antimony. The limit of detection (LOD), calculated using the IUPAC recommendation (based on a 3σblank criterion), was obtained by use of optimized operating conditions. Since no detection limits obtained by identical techniques are available, the results are compared to the quartz atom trap and electrochemical hydride generation atomic absorption spectrometry (QAT-HG-AAS) (in situ trapping) and to the HG-GF-AAS (in situ trapping) technique (Table 5). From Table 5, it can be seen that the detection limits of the developed procedure are evidently better, as compared with other atom traps. Detection limits obtained with a 120 s collection time were in the ppt (pg mL–1) range and are the best ones; they are low enough to suggest that this procedure provide a viable alternative to the use of QAT-HG-AAS and HG-GF-AAS (in situ trapping) methodology for the determination of this hydride forming trace element. The achieved limit of detection (LOD): 0.2 ng mL–1 for Sb (sensitivity enhancement compared to FAAS is 550 fold), is at least ten times worse than the LOD achieved for Sbin situ trapping in a quartz surface reported by Menemenlioglu et al.,29 and in commercial graphite furnace with subsequent detection reported by other authors.31–34 Six replicate measurements of the total procedure (reagent) blank solution were carried out and the relative standard deviation (RSD) of the background values for the raw, unsmoothed data were calculated. Precision was in the range of 8.0% (Sb, evaluated as peak area); this reflects the cumulative imprecision of all of the sample handling, hydride generation, trapping, atomization and detection steps. The peak height precision was always slightly, but significantly, worse.
Sample | HG-IAT-FAAS procedure | ||
---|---|---|---|
Sb(III) | Sb(V) | Sbtot | |
a Standard deviation for 6 parallel determinations. b Below detection limit. c Concentration in µg mL–1. | |||
Coal fly ash | — | — | 8.89 ± 0.72a |
Soil | — | — | 0.42 ± 0.03a |
Sediment | — | — | 3.15 ± 0.30a |
Sewage | 0.09 ± 0.01c | 0.19 ± 0.02c | 0.28 ± 0.02c |
River water | <DLb | — | 0.0015 ± 0.0001c |
The proposed experimental speciation approach offers an interesting perspective and good prospects for the determination of other hydride forming elements, in the range of pg mL–1, e.g., Ge and Sn. This is the subject of on-going research. The use of the atom trapping technique is attractive for laboratories not equipped with any graphite furnace apparatus. Although time required for each measurement is longer than that required for the classic hydride generation technique.
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