{'fraction_non_alphanumeric': 0.035631024043982044, 'fraction_numerical': 0.02634051289188907, 'mean_word_length': 4.756058481874624, 'pattern_counts': {'":': 0, '<': 0, '<?xml version=': 0, '>': 0, 'https://': 0, 'lorem ipsum': 0, 'www.': 0, 'xml': 0}, 'pii_count': 0, 'substrings_counts': 0, 'word_list_counts': {'cursed_substrings.json': 1, 'profanity_word_list.json': 0, 'sexual_word_list.json': 0, 'zh_pornsignals.json': 0}}
Study on the performance of micro-flow injection preconcentration method on-line coupled to thermospray flame furnace AAS using MWCNTs wrapped with polyvinylpyridine nanocomposites as adsorbent

This work describes the synthesis and characterization of a new adsorbent nanocomposite based on multi-walled carbon nanotubes (MWCNTs) and polyvinylpyridine and its use in the development of a highly sensitive micro-flow injection preconcentration method coupled to TS-FF-AAS for the determination of very low levels of Cd. The characterization of the nanocomposite was performed by FT-IR, TGA, SEM, TEM and textural data measurements using the BET and BJH methods. The optimized conditions of the micro-flow injection preconcentration method involved a preconcentrated sample (8.8 mL) at pH 8.0 flowed through 50.0 mg of nanocomposite packed into a mini-column at a flow rate of 4.4 mL min−1. The on-line elution of Cd(II) ions towards the TS-FF-AAS detector was carried out in countercurrent at a flow rate of 0.6 mL min−1 using 1.0 mol L−1 HCl. The analytical curve ranged from 0.12 to 6.0 μg L−1 (r = 0.997), and an enhancement factor of 19.5, sample throughput of 15 h−1 and consumptive index of 0.45 mL were achieved. In terms of sensitivity, the uniquely high adsorption capacity of the nanocomposite was confirmed by the low limit of detection (36 ng L−1) achieved after implementing the preconcentration step in TS-FF-AAS. In terms of selectivity, the proposed method was shown to be tolerable to several foreign ions and applicable to different kinds of waters (tap, mineral, lake, and synthetic seawater), cigarettes, a food sample (powder chocolate), a medicinal herb (Ginkgo biloba) and a certified reference material (fish protein DORM-3).


Introduction
Cd (Cd) is a very toxic element for animals and humans, even at low concentrations, and acts as a human carcinogen. 1,2 Due to the increase in human activities, the transfer of Cd into human beings has become increasingly common and occurs through food, plants, drinking water and air. 3 Therefore, due to its toxic characteristics, the maximum level of Cd in potable water has been set as 5.0 mg L À1 by the US Environmental Protection Agency (US EPA) 4 and Brazilian Health Surveillance Agency (ANVISA). 5 Another well-known source of Cd uptake by humans beings is from cigarette smoke since tobacco leaves accumulate high levels of Cd. 6 Some reports have demonstrated that medicinal herbs such as Gingko biloba as well as chocolate, mainly chocolate rich in cocoa, might be a signicant source of Cd ingestion. 7,8 Thus, the determination of Cd in different kinds of samples is of particular interest for quality control and environmental monitoring. However, due to the very low Cd content along with the differences between matrices in the samples, the development of reliable methods capable of directly analyzing Cd in different kinds of samples is usually a difficult task. 9 Hence, the pretreatment of samples using preconcentration methods is highly recommended for reliable analysis, especially if one considers the use of analytical techniques with high sensitivity, such as ame atomic absorption spectrometry (FAAS). [10][11][12] Among the preconcentration methods including solid phase extraction (SPE), co-precipitation and micro liquid-liquid extraction, the rst is still the most used method for metal ion extraction and is mainly used in combination with atomic spectrometric techniques. 13,14 The advantages of SPE stem from its simplicity to perform on-line or off-line, high preconcentration factor and exibility due to the availability of commercial adsorbents such as octadecyl-C 18 -silica, Amberlite XAD-2, polyurethane foam, Amberlyst 36, Amberlite XAD-16, Chromosorb-106. 15 Although widely used, these adsorbents suffer from some drawbacks, such as lack of selectivity, the need to use auxiliary chelating agents, low chemical stability in a large pH range, swelling effect in different uids, low regeneration ability and the need for toxic organic solvents as eluents in the preconcentration system. [16][17][18] Therefore, many efforts in the eld of separation science have been made to synthesize new adsorbent materials with better adsorptive and selective features towards metal ion adsorption. Carbonaceous nanoadsorbent materials, including carbon nanotubes, 19 carbon black 20 and graphene; 21 metal-organic frameworks (MOFs); 22 nanostructured ionimprinted polymers (IIPs); 23 inorganic nanoadsorbents; 24 nanostructured mixed oxides; 25 magnetic adsorbents; 26 and nanocomposites based on nanocarbonaceous materials and polymers 27 represent a class of materials that has been widely investigated for metal ion adsorption. The basic advantage of these nanoadsorbents is that most of the binding sites responsible for the high chemical activity and adsorption capacity towards metal ions are on the surface of the nanomaterial. 25 Carbon nanotubes (CNTs) are one class of carbonaceous nanoadsorbent materials that is currently considered the most exploited for metal ion adsorption; however, the adsorption properties of these materials depend upon their functional groups, dispersibility in aqueous media, site density and surface area. 27 From this perspective, nanocomposite materials based on CNTs and chelating polymers are promising for solving these drawbacks by improving the dispersion of the carbonaceous phase and enhancing the ratio of polymer binding sites to volume due to the nanoscale polymers synthetized on the surface of the carbonaceous phase. 28,29 Furthermore, the preparation of CNT/polymer nanocomposites may overcome the poor accessibility of the analyte to the binding sites of the polymer and the slow dynamic adsorption compared to bulk polymer. 30 Although very interesting, the studies dedicated to combining CNTs and polymers have been performed mostly to improve the mechanical strength of the polymer in the nanocomposite; 31 few have examined metal adsorption. To the best of our knowledge, the few studies reported on this subject involve the use of CNT/polyaniline (PANI) and poly(3,4dioxythiophene) (PEDOT) nanocomposites for Au adsorption, 32 CNT/PAMAN for Ni, Zn, As and Co adsorption, 27 CNT/ poly(2-amino thiophenol) for Cd and Pb adsorption, 33 and CNT/polypyrrole for Pb, Ni, and Cd adsorption. 28 Additionally, one should note that no preconcentration studies have been reported from the analytical point of view on the assessment of the performance of CNT/polymer composites as adsorbents for Cd ions using micro-ow injection as a preconcentration method.
Therefore, in this study, we have developed a CNT/ polyvinylpyridine nanocomposite for the preconcentration of Cd using a micro-ow injection method on-line coupled to thermospray FAAS (TS-FF-AAS). Polyvinylpyridine was chosen as the chelating polymer due to the presence of nitrogen in the pyridine ring, which has a strong ability to bind Cd ion. 34 Moreover, apart from its intrinsic sensibility for volatile metal ions, the interest in the on-line coupling of the preconcentration method with TS-FF-AAS results from its low ow rate. Therefore, micro-column packed with CNT/polyvinylpyridine nanocomposite seems to be very interesting for operating at low ow rates.
The nanocomposite was characterized by FTIR, TGA, SEM, TEM and textural data measurements using the BET and BJH methods, and the analytical performance of the proposed method for real analysis was checked by the analysis of different kinds of samples (water, chocolate, medicinal herbs, and cigarettes) and a certied reference material (sh protein DORM-3).

Apparatus
Absorption measurements were performed using a Shimadzu AA-7000 ame atomic absorption spectrometer (Kyoto, Japan) equipped with a hollow cathode lamp for Cd and a deuterium lamp for background correction. The hollow cathode lamp was operated at 8.0 mA, and the wavelength was set at 229.0 nm. The ame composition was operated with an acetylene ow rate of 2.0 L min À1 and an airow rate of 10.0 L min À1 . The ow adsorbent preconcentration system was constructed using a peristaltic pump (Gilson Minipuls evolution; Middleton, USA) furnished with Tygon® tubes to propel all samples and reagent solutions. A homemade minicolumn made of polyethylene (3.0 cm in length and 0.5 cm in internal diameter at the top) packed with 50.0 mg of nanocomposite was coupled to a homemade injector commutator for preconcentration and elution procedures. A piece of cotton was xed at the extremities of the minicolumn by inserting the upper end of a conical tip into the minicolumn cylindrical edge to avoid the loss of material. The TS-FF-AAS apparatus included a ceramic capillary (10 cm) nickel tube made of non-porous Al 2 O 3 ceramic (Friatec, Mannhein, Germany) and a nickel tube (Inconel 600 tube with 72% Ni, 14-17% Cr, 6-10% Fe, 0.15% C, 1% Mn, and 0.5% SI; Camacam, Brazil) with a length of 10 cm and an i.d. of 1.0 cm and containing six holes with i.d. ¼ 2.5 mm. Scanning electron microscopy (SEM) analyses were performed using a Model Quanta 200-Philips-FEI microscope (Amsterdam, Netherlands), and the samples were coated with a thin layer of carbon to minimize charging under the incident electron beam. For transmission electron microscopy (TEM), a JEOL® JEM-1400 microscope with an accelerating voltage of 120 kV was used. For TEM sample treatment, the material was dispersed in ethanol by sonication for 20 min, and the suspension was dried under vacuum on copper grids.
A Shimadzu FTIR 8300 spectrometer (Kyoto, Japan) operating in transmission mode between 4000 and 400 cm À1 was used to elucidate the functional groups present in the nanocomposites. The surface area and average pore diameter were obtained by the multipoint BET and BJH methods, respectively, based on nitrogen adsorption experiments using a physical adsorption method with a Quantachrome Model Nova 1200e automatic nitrogen gas adsorption instrument (Boynton Beach, FL, USA). Thermogravimetric analysis (TGA) was carried using a 4000 Perkin Elmer thermobalance (Waltham, USA). For TGA analysis, $10 mg of sample was heated from 30 C to 900 C at a rate of 10 C min À1 under a nitrogen ow of 20 mL min À1 . The digestion of a certied reference material and cigarette samples was carried out using a microwave laboratory system (Microwave Milestone).

Synthesis of MWCNT-polyvinylpyridine nanocomposites
To create hydroxyl groups on the MWCNT surface capable of reacting with vinyltriethoxysilane, MWCNTs were oxidized according to the literature with minor modications. 11 For this task, 1000 mg of MWCNT were mixed with 133.3 mL of a HNO 3 / H 2 SO 4 (3 : 1, v/v) mixture and reuxed at 65 C for 2 h. Aerwards, the oxidized MWCNTs were successively washed with deionized water (pH 7.0) to remove acid excess, dried at 60 C and stored at room temperature. Subsequently, 500.0 mg of oxidized MWCNTs were dispersed in 40.0 mL of toluene in a three-neck, round-bottom ask and kept in an ultrasonic bath (40 kHz) for 20 min. Then, 12.4 g of vinyltrimethoxysilane previously dissolved in 67.0 mL of toluene containing 0.12 g of hydroquinone was slowly added to the mixture under stirring. One of the three necks was sealed, the central neck was coupled to a reux condenser, and the other neck was purged with nitrogen (N 2 ) for 10 min. Aerwards, the neck was sealed, and the mixture was heated at 100 C in an oil bath for 6 h under reux. The obtained functionalized MWCNTs were washed with ethanol and dried at 50 C for 6 h. For the synthesis of nanocomposite, 40.0 mg of functionalized MWCNTs were dispersed in 15.0 mL of DMF in a at-bottomed ask and kept in an ultrasonic bath (40 kHz) for 20 min. In the next step, 800 mL of the functional monomer 4-vinylpyridine (7.42 mmol), 800 mL of crosslinking agent (TRIM; 2.51 mmol) and 80.0 mg of the radical initiator (AIBN; 0.48 mmol) were added to the mixture. The mixture was transferred to a round-bottom ask, purged with N 2 for 10 min, sealed, and heated at 60 C for 24 h under constant stirring. Aer synthesis, the nal material was removed from the ask, rinsed with Milli-Q water to remove excess reagent, and dried at 50 C for 24 h. Fig. 1 shows a schematic representation of the synthesis of MWCNT and polyvinylpyridine nanocomposites.

System of preconcentration for Cd(II) on-line coupled to TS-FF-AAS
The on-line preconcentration system was based on loading 8.8 mL of sample buffered with 0.01 mol L À1 ammoniacal buffer (pH 8.0) through 50.0 mg of MWCNT-polyvinylpyridine nanocomposite packed into a mini-column (3.0 cm in length and 0.5 cm in upper internal diameter) made of polyethylene at a ow rate of 4.4 mL min À1 (Fig. 2). To build the homemade cylindrical mini-column, a small piece of cotton tissue was placed at each end of the mini-column to hold the nanocomposite. The pieces of cotton tissue were xed at the extremities of the mini-column by inserting the upper end of a conical tip into the mini-column cylindrical edge. The on-line elution step was coupled to the TS-FF-AAS detector and performed in countercurrent at a ow rate of 0.6 mL min À1 using 1.0 mol L À1 HCl.

Sample preparation
Tap and mineral waters were acquired from the Campus of State University of Londrina and a local supermarket, respectively. Aer sampling, the pH of the sample was adjusted to 8.0 with 0.01 mol L À1 ammoniacal buffer, and the sample was immediately analyzed by the proposed method. Synthetic seawater was prepared according to ref. 35, and lake water samples were collected from Igapó Lake and treated according to our previous publication. 34 For the digestion of solid samples, cigarette (500 mg), powdered chocolate (50% cocoa; 700 mg), leaves of Ginkgo biloba (210 mg) and a certied reference material (sh protein DORM-3; 173 mg) were weighted into Teon asks and decomposed with 10.0 mL of concentrated HNO 3 and 4.0 mL 30% (v/v) H 2 O 2 . The mixture was kept overnight followed by digestion in a closed microwave with the following sequence: heat to 80 C for 6 min; maintain for 6 min at this temperature; heat from 80 C to 120 C for 7 min; maintained for 5 min at 120 C; heating to 210 C for 15 min; and maintain for 20 min at 210 C. 34 The digested samples were then heated on a hot plate to near dryness and cooled at room temperature. The samples were transferred to 50 mL volumetric asks and then diluted to the appropriate concentration with ammoniacal buffer (pH 8.0). Fig. 3a and b show the FT-IR spectra of MWCNTs (pristine, oxidized and functionalized) along with MWCNT-polyvinylpyridine and polyvinylpyridine. As can be seen from Fig. 3a, the spectra of pristine and oxidized MWCNTs are similar, except for the band at 1046 cm À1 attributed to dCH. The band at 3450 cm À1 is assigned to O-H stretching vibrations. 11 The signals at 2920 and 2830 cm À1 correspond to symmetric and asymmetric C-H stretching, the band at 1630 cm À1 can be assigned to the C]C stretching of the carbon nanotube backbone, and the band at 1390 cm À1 may be attributed to C-C bond stretching. 36 For MWCNTs functionalized with VTMS, the bands at 3190 and 3150 cm À1 , which are assigned to the ]CH bonds, and the band at 1390 cm À1 were signicantly diminished, indicating the graing process of VTMS on the carbon nanotube backbone. Additional evidence of the graing process is provided by the presence of the band at 1080 cm À1 in the spectrum of functionalized MWCNTs, which is characteristic of Si-O-Si stretching, and the bands at 780 and 650 cm À1 , which are assigned to Si-O stretching. 11 As shown in Fig. 3b, the spectral prole of MWCNTpolyvinylpyridine is similar to that of polyvinylpyridine. The band at 1715 cm À1 can be assigned to C]O stretching from crosslinking reagent (TRIM). 34 The signal at 1630 cm À1 can be attributed to overlapping bands of C]C stretching from vinyl groups, OH deformation (water) or C]N stretching from the pyridine ring. The band at 1380 cm À1 is ascribed to C-N stretching from the pyridine ring, which indicates the presence of the organic monomer 4-vinylpyridine in the polymeric matrix. 37 Furthermore, the signal at 1460 cm À1 is ascribed to C]C stretching from the 4vinylpyridine ring. The intense band at 1150 cm À1 is attributed to C-O stretching from the ester group in the TRIM structure. 29 Fig . 4 shows the TGA curves of the MWCNTs (pristine, oxidized and functionalized), MWCNT-polyvinylpyridine composite and polyvinylpyridine. It is possible to observe similar thermal prole for MWCNTs with high thermal stability. A weight loss of about 13% was noted at 900 C, demonstrating that the graing of VTMS occurred but not a polymerization reaction based on polycondensation. 38 For the MWCNT-polyvinylpyridine composite and polyvinylpyridine, the observed 20% and 4% weight losses, respectively, in the 30-100 C temperature range are attributed to moisture loss.

Characterization of MWCNTs and nanocomposites
The TGA curve of polyvinylpyridine demonstrated that the polymer was stable to 294 C, when the polymeric chain was degraded. A signicant weight loss was observed starting at 347 C for the MWCNT-polyvinylpyridine composite; this is attributed to the degradation of the polymeric chain, indicating a protective effect of MWCNTs on the thermal stability of the polymeric chain.
The SEM images of MWCNTs are shown in Fig. 5. The images of the pristine and oxidized MWCNTs are similar and show highly tangled nanotubes. This indicates that MWCNT  fragmentation did not occur, and that the cylindrical structures of the MWCNTs were not open-ended, corroborating the FT-IR data. This result was expected since the treatment with oxidizing agents in this study was employed primarily to create hydroxyl groups in the MWCNTs. On the other hand, the functionalization of MWCNTs with VTMS gives rise to strong aggregation attributed to graing process.
SEM images of the MWCNT-polyvinylpyridine nanocomposite and polyvinylpyridine are shown in Fig. 6. The linkage of polyvinylpyridine on the MWCNTs can be clearly seen by the tubular shapes of the CNTs impregnated into the polyvinylpyridine network. The image of polyvinylpyridine (Fig. 6b) shows that the particles are more cohesive with a higher degree of aggregation, which is not favorable for adsorption.
The TEM images conrm the bonding of polyvinylpyridine with MWCNT, where polymer spots wrap some sections of MWCNT (Fig. 7). Additionally, it can be observed that the polymerization reaction of polyvinylpyridine also occurred in solution and in addition to surface polymerization. Table 1 shows the textural data obtained for the materials. As expected, the surface areas of the pristine and functionalized MWCNTs are higher than those of polyvinylpyridine and the nanocomposite. The lower surface area of the nanocomposite resulted from the low pore volume, which can be explained by the penetration of MWCNTs into the polyvinylpyridine network to occupy the pores of the polymer. On the other hand, the textural data of polyvinylpyridine are similar to those of other polymers synthesized by bulk methods, 39 and the particles have irregular shapes with rough surfaces.
Although polyvinylpyridine shows a higher surface area than the MWCNT-polyvinylpyridine nanocomposite, it should be noted that the nanocomposite adsorbs higher amounts of Cd, as will be demonstrated from the sensitivity of analytical curves. This suggests that the binding sites of the polyvinylpyridine network that interact with Cd ions are dispersed in the nanocomposite and are much more available on the surface of material; in contrast, in polyvinylpyridine, the binding sites are most likely to be inside the polymeric network.

Optimization of the micro-ow injection preconcentration method on-line coupled to TS-FF-AAS
The parameters that play an important role in the preconcentration system, including sample pH (4.5-9.0), preconcentration ow rate (1.4-4.4 mL min À1 ), concentration and type of buffer solution were investigated.
To study the effect of pH, 26.8 mL of Cd solution at a concentration of 5.0 mg L À1 were preconcentrated in the nanocomposite at a ow rate of 6.7 mL min À1 . The elution step was performed with 1.0 mL L À1 HCl at a ow rate of 0.6 mL   min À1 . Fig. 8 shows that the optimal pH for Cd preconcentration in the nanocomposite is 8.0. According to literature data, the pK a of the monomer 4-vinylpyridine is 5.46, 40 while the pK a of polyvinylpyridine determined by potentiometric titration in aqueous medium is 4.0. 41 Therefore, in acidic medium, the nitrogen from the pyridine ring is protonated, leading to electrostatic repulsion with the surface of the material. On the other hand, at pH 9.0, the adsorption in the material decreases, most likely due to the precipitation of Cd ions in the hydroxide form. Thus, for further experiments, pH 8.0 was used.
Aer establishing the best pH for Cd adsorption, the effects of different kinds of buffer solutions (ammoniacal, phosphate and Tris-HCl) were evaluated.
A signicant effect was noticed when phosphate was used as a buffer; this result can be rationalized on the basis of the strong interaction of phosphate salt with Cd ions. For ammoniacal and Tris-HCl buffers, higher analytical signals were observed, and no differences were noticed. Ammoniacal buffer was chosen over Tris-HCl due to its lower cost.
The results regarding the effect of buffer concentration (0.001-0.5 mol L À1 ) showed that 0.01 and 0.1 mol L À1 provide adequate buffer capacity and the best analytical signals for Cd ions. For very low (0.001 mol L À1 ) and high (0.5 mol L À1 ) buffer concentrations there was a signicant decrease in the analytical signal due to the reduced buffer capacity and strong interaction between ammoniacal buffer and Cd ions. Therefore, 0.01 mol L À1 was chosen for subsequent experiments.
The preconcentration ow rate is a very important parameter to optimize when kinetics exert an inuence on adsorption; this variable is strongly related to the sensitivity and sample throughput of the method. In this experiment, 8.8 mL aliquots of Cd solution were preconcentrated in the nanocomposite under the optimized conditions. Lower preconcentration ow rates (1.4 and 2.8 mL min À1 ) resulted decreased analytical signal, indicating the poor accessibility of Cd ions due to hydrodynamic limitation. On the other hand, the preconcentration increased with the highest ow rate (4.4 mL min À1 ), which clearly also suggest fast kinetic of mass transfer of Cd toward adsorbent surface. Additionally, the higher the sample ow rate, the greater the sample throughput for the method. Thus, a ow rate of 4.4 mL min À1 was chosen as the optimum value. The elution ow rate using 1.0 mol L À1 was chosen as 0.6 mL min À1 as the best value to produce a stable and continuous aerosol.

Effect of potentially interfering ions
To discover the degree to which the proposed method is prone to concomitant ions and macromolecules (humic acid), experiments were carried out in the presence of Ca(II), Mg(II), Zn(II), Pb(II), Cu(II), Fe(II), Hg(II), Co(II), Ca(II) and Mg(II). Binary solutions containing different ratios of analyte to interferent [1 : 1, 1 : 10, 1 : 50, 1 : 100 and 1 : 500 (w/w)] were subjected to the proposed method with a Cd concentration of 5.0 mg L À1 . The inuence of humic acid was studied at concentrations up to 5.0 mg L À1 , the normal concentration of humic substances in natural water samples, 26 to simulate dissolved organic matter in natural waters. Interference was dened to be signicant when a relative error of AE10% in the analytic signal was observed. No interference was observed for the analyte: interferent ratios    This journal is © The Royal Society of Chemistry 2017 investigated, indicating that Cd preconcentration can be carried free of interference in a complex matrix.

Analytical characteristics of the proposed method
The analytical curves obtained by TS-FF-AAS without preconcentration and with preconcentration step using the MWCNT-polyvinylpyridine nanocomposites or polyvinylpyridine are illustrated in Fig. 9 and represented by the following linear equations: Without preconcentration: With preconcentration using polyvinylpyridine: Abs ¼ 0.0037 + 0.0620(AE3.27 Â 10 À3 ) [Cd(II), mg L À1 ]; and With preconcentration using MWCNT-polyvinylpyridine: A comparison of the curves shows that the sensitivity of the method was sharply enhanced by the preconcentration step, particularly when the MWCNT-polyvinylpyridine nanocomposite was used as the adsorbent. The enhancement factors (EFs) were determined as the ratio of the slopes of the analytical curves built with and without the preconcentration step. The EFs obtained using the MWCNT-polyvinylpyridine nanocomposite and polyvinylpyridine were 19.5 and 7.46, respectively. These results show that the insertion of MWCNTs into the polymeric network of polyvinylpyridine improves the sensitivity for Cd ion determination by 2.6 times. This result can be considered satisfactory because only 40 mg of MWCNTs were used in the synthesis, which exalts the synergic effect of MWCNTs and the polymeric matrix in the nanocomposite. The sensitivity could be increased by using a larger adsorbent mass and a higher preconcentration volume. For 8.8 mL of sample, the limit of detection (LOD) and limit of quantication (LOQ), determined according to IUPAC recommendations, 42 were found to be 36 and 121 ng L À1 , respectively. Other important parameters in the development of solid-phase preconcentration methods, such as consumption index (CI), which is dened as the volume required to attain a unit of EF, and the concentration efficiency (CE), dened as the EF obtained by operating the preconcentration system for 1 min, were also calculated. 43 CI and CE were found to be 0.40 mL and 9.76 min À1 , respectively. The sample throughput of the proposed method was 15 h À1 . The intra-day precision was evaluated by  preconcentrating (n ¼ 10) Cd solutions at 1.0 and 5.0 mg L À1 , giving rise to relative standard deviations (RSDs) of 2.10% and 1.81%, respectively. The inter-day precision for three consecutive working days using ten independent measurements yielded RSD values of 0.61% and 1.60% for the same concentrations of 1.0 and 5.0 mg L À1 , respectively. Compared with other solid-phase preconcentration methods for Cd with TS-FF-AAS determination using Amberlite XAD-4 modied with 3,4-dihydroxybenzoic acid, 44 fullerene modied with APDC, 45 Amberlite XAD-2 modied with TAN, 46 polyurethane foam modied with DDTP, 47 oxidized MWCNTs 48 and poly(2amino thiophenol)/MWCNT nanocomposites, 33 the proposed method does not require toxic organic solvents in the ow system, presents low sample consumption, has high sample throughput, and provides a similar LOD.

Application and accuracy in real samples
The preconcentration method was applied to Cd determination in different kinds of water, cigarettes, a food sample (powder chocolate) and a medicinal herb (Ginkgo biloba), as shown in Tables 2 and 3. As Cd was not found in the analyzed water samples, a procedure to spike the samples with known amounts of Cd was implemented. According to the recovery values, which ranged from 91% to 109%, the proposed method allows interference-free Cd determination, even for samples containing high salt contents.
The feasibility of applying this method for the determination of trace levels of Cd in different kinds of solid samples (cigarettes, powder chocolate, and medicinal herbs) subjected to acid digestion is assured by the high recovery values (90-105%; Table 3). As expected, Cd was found in cigarettes, 49 powder chocolate 8 and Gingko biloba 7 samples, which represent sources of Cd uptake by human beings. The accuracy of the method was also veried by the analysis of a certied reference material DORM-3 (sh protein); the result achieved by the proposed method was statistically equal to the certied value based on a t-test at a condence level of 95% (Table 3).

Conclusions
The synthesis of a nanocomposite and its application in analytical preconcentration was reported herein for the rst time. The results demonstrate the great benets of incorporating MWCNTs into the polymeric network of polyvinylpyridine as an adsorbent material for metal ions, which is of paramount importance for obtaining new analytical preconcentration methodologies. The preconcentration method on-line coupled to TS-FF-AAS has good accuracy and repeatability, low sample consumption, high sample throughput, no need for toxic organic solvents in the ow system, and broad applicability for different types of samples for the determination of trace levels of Cd.