A Novel Glass Fiber Coated with Sol–Gel Poly-Diphenylsiloxane Sorbent for the On-Line Determination of Toxic Metals Using Flow Injection Column Preconcentration Platform Coupled with Flame Atomic Absorption Spectrometry

A novel simple and sensitive, time-based flow injection solid phase extraction system was developed for the automated determination of metals at low concentration. The potential of the proposed scheme, coupled with flame atomic absorption spectrometry (FAAS), was demonstrated for trace lead and chromium(VI) determination in environmental water samples. The method, which was based on a new sorptive extraction system, consisted of a microcolumn packed with glass fiber coated with sol–gel poly (diphenylsiloxane) (sol–gel PDPS), which is presented here for the first time. The analytical procedure involves the on-line chelate complex formation of target species with ammonium pyrrolidine dithiocarbamate (APDC), retention onto the hydrophobic sol–gel sorbent coated surface of glass fibers, and finally elution with methyl isobutyl ketone prior to atomization. All main chemical and hydrodynamic factors, which affect the complex formation, retention, and elution of the metal, were optimized thoroughly. Furthermore, the tolerance to potential interfering ions appearing in environmental samples was also explored. Enhancement factors of 215 and 70, detection limits (3 s) of 1.1 μg·L⁻¹ and 1.2 μg·L⁻¹, and relative standard deviations (RSD) of 3.0% (at 20.0 μg·L⁻¹) and 3.2% (at 20.0 μg·L⁻¹) were obtained for lead and chromium(VI), respec tively, for 120 s preconcentration time. The trueness of the developed method was estimated by analyzing certified reference materials and spiked environmental water samples.     

Lab-In-Syringe with Bead Injection Coupled Online to High-Performance Liquid Chromatography as Versatile Tool for Determination of Nonsteroidal Anti-Inflammatory Drugs in Surface Waters

We report on the hyphenation of the modern flow techniques Lab-In-Syringe and Lab-On-Valve for automated sample preparation coupled online with high-performance liquid chromatography. Adopting the bead injection concept on the Lab-On-Valve platform, the on-demand, renewable, solid-phase extraction of five nonsteroidal anti-inflammatory drugs, namely ketoprofen, naproxen, flurbiprofen, diclofenac, and ibuprofen, was carried out as a proof-of-concept. In-syringe mixing of the sample with buffer and standards allowed straightforward pre-load sample modification for the preconcentration of large sample volumes. Packing of ca. 4.4 mg microSPE columns from Oasis HLB^® sorbent slurry was performed for each sample analysis using a simple microcolumn adapted to the Lab-On-Valve manifold to achieve low backpressure during loading. Eluted analytes were injected into online coupled HPLC with subsequent separation on a Symmetry C18 column in isocratic mode. The optimized method was highly reproducible, with RSD values of 3.2% to 7.6% on 20 µg L⁻¹ level. Linearity was confirmed up to 200 µg L⁻¹ and LOD values were between 0.06 and 1.98 µg L⁻¹. Recovery factors between 91 and 109% were obtained in the analysis of spiked surface water samples.     

Application of Bar Adsorptive Microextraction for the Determination of Levels of Tricyclic Antidepressants in Urine Samples

This work entailed the development, optimization, validation, and application of a novel analytical approach, using the bar adsorptive microextraction technique (BAμE), for the determination of the six most common tricyclic antidepressants (TCAs; amitriptyline, mianserin, trimipramine, imipramine, mirtazapine and dosulepin) in urine matrices. To achieve this goal, we employed, for the first time, new generation microextraction devices coated with convenient sorbent phases, polymers and novel activated carbons prepared from biomaterial waste, in combination with large-volume-injection gas chromatography-mass spectrometry operating in selected-ion monitoring mode (LVI-GC-MS(SIM)). Preliminary assays on sorbent coatings, showed that the polymeric phases present a much more effective performance, as the tested biosorbents exhibited low efficiency for application in microextraction techniques. By using BAμE coated with C₁₈ polymer, under optimized experimental conditions, the detection limits achieved for the six TCAs ranged from 0.2 to 1.6 μg L⁻¹ and, weighted linear regressions resulted in remarkable linearity (r² > 0.9960) between 10.0 and 1000.0 μg L⁻¹. The developed analytical methodology (BAμE(C18)/LVI-GC-MS(SIM)) provided suitable matrix effects (90.2–112.9%, RSD ≤ 13.9%), high recovery yields (92.3–111.5%, RSD ≤ 12.3%) and a remarkable overall process efficiency (ranging from 84.9% to 124.3%, RSD ≤ 13.9%). The developed and validated methodology was successfully applied for screening the six TCAs in real urine matrices. The proposed analytical methodology proved to be an eco-user-friendly approach to monitor trace levels of TCAs in complex urine matrices and an outstanding analytical alternative in comparison with other microextraction-based techniques.     

Ultrasound assisted supramolecular liquid phase microextraction procedure for Sudan I at trace level in environmental samples

A method based on supramolecular liquid phase microextraction has been developed for the preconcentration and determination of trace levels of Sudan I. 1-decanol and tetrahydrofuran were used as supramolecular solvent components. Trace levels of Sudan I were extracted into the extraction solvent phase at pH = 4.0 Analytical parameters such as pH value, supramolecular solvent volume, ultrasonication, centrifugation, model solution volume, matrix effects have been optimized. The limit of detection and the limit of quantification values for Sudan I were calculated as 1.74 μg L⁻¹ and 5.75 μg L⁻¹, respectively. In order to determine the accuracy of the method, addition and recovery studies were carried out to environmental samples.     

Simultaneous Preconcentration of Triazole Fungicide Residues Using In-Situ Coacervative Extraction Based on a Double-Solvent Supramolecular System Prior to High Performance Liquid Chromatographic Analysis

An in situ coacervative extraction (IS-CAE) based on a double-solvent supramolecular system coupled to liquid–liquid microextraction is investigated for extraction and enrichment of triazole fungicides. The formation of a double-solvent supramolecular system was generated by in situ formation and used as an extraction solvent for the coacervative extraction method. No disperser solvent was required. This new double-solvent supramolecular system has a higher extraction ability than any of its components alone. The different factors that could affect the extraction capability were studied and optimized, including the type of double extractant and its volume, salt addition, vortex time, and centrifugation time. Under optimum extraction conditions, this method provides high enrichment factors (EFs) of 73–318 with low limits of detection (LODs) of 0.3–1 μg L⁻¹ and limits of quantitation (LOQs) of 1–3 μg L⁻¹. In addition, the proposed method was prosperously applied for the determination of triazole fungicides in water, fruit juice, and soy milk samples.     

On-line separation and preconcentration of inorganic arsenic and selenium species in natural water samples with CTAB-modified alkyl silica microcolumn and determination by inductively coupled plasma-optical emission spectrometry

A new, simple, and selective method has been presented for the separation and preconcentration of inorganic arsenic (As(III)/As(V)) and selenium (Se(IV)/Se(VI)) species by a microcolumn on-line coupled with inductively coupled plasma-optical emission spectrometry (ICP-OES). Trace amounts of As(V) and Se(VI) species were separated and preconcentrated from total As and Se at desired pH values by a conical microcolumn packed with cetyltrimethylammonium bromide (CTAB)-modified alkyl silica sorbent in the absence of chelating reagent. The species adsorbed by CTAB-modified alkyl silica sorbent were quantitatively desorbed with 0.10 ml of 1.0 mol l⁻¹ HNO₃. Total inorganic arsenic and selenium were similarly extracted after oxidation of As(III) and Se(IV) to As(V) and Se(VI) with KMnO₄ (50.0 μmol l⁻¹). The assay of As(III) and Se(IV) were based on subtracting As(V) and Se(VI) from total As and total Se, respectively. All parameters affecting the separation/preconcentration of As(V) and Se(VI) including pH, sample flow rate and volume, eluent solution and volume have been studied. With a sample volume of 3.0 ml, the sample throughput was 24 h⁻¹ and the enrichment factors for As(V) and Se(VI) were 26.7 and 27.6, respectively. The limits of detection (LODs) were 0.15 μg l⁻¹ for As(V) and 0.10 μg l⁻¹ for Se(VI). The relative standard deviations (RSDs) for nine replicate determinations at 5.0 μg l⁻¹ level of As(V) and Se(VI) were 4.0% and 3.6%, respectively. The calibration graphs of the method for As(V) and Se(VI) were linear in the range of 0.5–1000.0 μg l⁻¹ with a correlation coefficient of 0.9936 and 0.9992, respectively. The developed method was successfully applied to the speciation analysis of inorganic arsenic and selenium in natural water samples with satisfactory results.     

Unmodified Multi-Walled Carbon Nanotubes as Sorbent Material in Flow Injection on-Line Sorbent Extraction Preconcentration System for Cadmium Determination by Flame Atomic Absorption Spectrometry

Unmodified multi-walled carbon nanotubes (MWCNTs) were demonstrated as hydrophobic sorbent material for flow injection on-line microcolumn preconcentration coupled with flame atomic absorption spectrometry for cadmium determination in natural water samples. The method was based on on-line chelate complex formation between the analyte with sodium diethyldithiocarbamate and retention onto the surface of MWCNTs. Quantitative elution of the analyte was achieved with methanol which was whereupon delivered to the FAAS nebulizer for atomization and measurement. The microcolumn was packed with a mixture of MWCNTs and silica beads in order to minimize the generated back-pressure in the flow system which arises from the nano dimensions of MWCNTs. All factors affecting the performance of the proposed method were studied thoroughly. For a 180 s preconcentration time the enhancement factor was 54, the detection limit (3s) was 0.24 µg L^?1, and the precision as relative standard deviation at a 5.0 µg L^?1 Cd(II) concentration level was 3.2%. The method was applied to the analysis of environmental water samples and the accuracy evaluated via certified reference material and recovery experiments.     

An In Situ Formation of Ionic Liquid for Enrichment of Triazole Fungicides in Food Applications Followed by HPLC Determination

An in situ formation of ionic liquid was used for preconcentration of four triazole fungicides in food samples. The microextraction method was used for the first time in the literature for preconcentration of triazole fungicides. In the developed method, tributylhexadecylphosphonium bromide ([P₄₄₄₁₂]Br) and potassium hexafluorophosphate (KPF₆) were used for the formation of hydrophobic ionic liquid. After centrifugation, the fine microdroplets were produced in one step, providing the extraction step in a quick and environmentally friendly manner. The functional group of the hydrophobic ionic liquid was investigated using FT-IR. Various extraction parameters were studied and optimized. In the extraction method, 0.01 g of [P₄₄₄₁₂]Br and 0.01 g of KPF₆, centrifugation at 4500 rpm for 10 min were used. The optimized technique provided a good linear range (90–1000 μg L⁻¹) and high extraction recovery, with a low limit of detection (30–50 μg L⁻¹). Methods for the proposed in situ formation of ionic liquid were successfully applied to honey, fruit juice, and egg matrices. The recoveries were obtained in a satisfactory range of 62–112%. The results confirmed the suitability of the proposed microextraction method for selective extraction and quantification of triazole fungicides.     

Reversed phase StrataTM-X resin as sorbent for automatic on-line solid phase extraction atomic absorption spectrometric determination of trace metals: comparison of polymeric-based sorbent materials

A novel on-line flow injection solid phase extraction method for the preconcentration of trace toxic metals prior determination by flame atomic absorption spectrometry (FI-SPE-FAAS) was developed. The potential application of the hydrophobic reversed phase co-polymer sorbent Strata^TM-X packed into an on-line microcolumn for the quantification of Cd(II), Pb(II), Cu(II) and Cr(VI) was demonstrated for the first time. The method was based on the on-line formation of metal complexes using sodium diethyl-dithiocarbamate (DDTC) and on the subsequent retention of them onto the sorbent material. The target analytes were completely eluted by methanol and, subsequently, directed to FAAS for quantification. All chemical and flow variables affecting the performance of the developed method were thoroughly studied and optimised. For a preconcentration time of 90 s and a sampling frequency of 28 h^?1, enhancement factors of 72, 140, 185, 63 and detection limits of 0.18, 1.6, 0.20 and 1.2 μg L ^?1 were obtained for Cd(II), Pb(II), Cu(II) and Cr(VI), respectively. The accuracy of the FI-SPE-FAAS method was evaluated by analysing certified reference materials as well as spiked environmental water samples. Furthermore, a comparative study of the analytical characteristics, the properties as well as the chemical structures of commercial polymeric based sorbent materials was employed. Strata-X sorbent was compared against Hypersep^TM SCX, Bond Elut® Plexa^TM PCX, Oasis-HLB^TM and Nobias^TM PA-1, regarding the adaptation in on-line FI-SPE-FAAS systems for metal determination, and herein presented.     

Synthesis of amberlite XAD-2-PC resin for preconcentration and determination of trace elements in food samples by flame atomic absorption spectrometry

A new chelating sorbent has been developed using Amberlite XAD-2 resin anchored with pyrocatechol through –N=C– group. This sorbent, characterised by elemental analysis and infrared (IR) spectra, was used as packing for the minicolumn in an on-line system preconcentration system for cadmium, cobalt, copper and nickel determination. Metal ions were sorbed in the minicolumn, from which it could be eluted directly to the nebulizer–burner system of the flame atomic absorption spectrometer (FAAS). Elution of all metals from minicolumn can be made with 0.50 mol L^− 1 HCl or HNO₃. The enrichment factors obtained were 16 (Cd), 24 (Co), 15 (Cu) and 19 (Ni), for 60 s preconcentration time, and 39 (Cd), 69 (Co), 36 (Cu) and 41 (Ni), if used 180 s preconcentration time. Under the optimum conditions, the proposed procedure allowed the determination of cadmium, cobalt, copper and nickel with detection limits of 0.31, 0.32, 0.39 and 1.64 μg L^− 1, respectively, when used preconcentration periods of 180 s. The accuracy of the developed procedure was sufficient and evaluated by the analysis of the certified reference materials NIST 1515 apple leaves and NIST 1570a spinach leaves. The method was applied to the analysis of food samples (spinach, black tea and rice flour).     

Determination of Nickel after Online Sorbent Preconcentration by FI-FAAS Using Dimethylglyoxime as a Complexing Agent

Dimethylglyoxime (DMG) has been tested as a complexing agent for the determination of nickel after online preconcentration on RP-C₁₈ in a microcolumn using flow injection coupled with a flame atomic absorption spectrometry system (FI-FAAS). The Ni–DMG complexes formed online can be adsorbed on the C₁₈ sorbent. Various parameters affecting the online Ni–DMG complex formation and its subsequent adsorption in the microcolumn as well as its elution into the nebulizer of the FAAS were optimized. A 10⁻³ mol/L solution of DMG in 4% ethanol was mixed online with an aqueous sample solution acidified to 0.1% (v/v) nitric acid and flowed for 30 s through the microcolumn. The adsorbed Ni–DMG complex in the microcolumn was eluted with ethanol containing 1% HNO₃ into the nebulizer of the FAAS in 10 s. A good precision (RSD = 1.7%, n = 14), high enrichment factor (21), and high sample throughput (90 h⁻¹) with detection limit (3ς) 3 μg/L were obtained. The method was applied to standard reference materials, i.e., NBS-362, NBS-364 (special low-alloy steel), and mussel (GBW 08571), for the determination of nickel and the results were in good agreement with certified values. Nickel recovery from seawater and high-purity magnesium oxide in the range 98–100% can be obtained by this method.     

On-Line Preconcentration and Simultaneous Determination of Cu and Mn in Water Samples Using a Minicolumn Packed with Sisal Fiber by MIP OES

An on-line preconcentration system for the simultaneous determination of Copper (Cu) and manganese (Mn) in water samples was developed and coupled to a microwave-induced plasma optical emission spectrometer (MIP OES). The flow injection system was designed with a minicolumn packed with sisal fiber (Agave sisalana). A multivariate experimental design was performed to evaluate the influence of pH, preconcentration time, and eluent concentration. Optimal conditions for sample preparation were pH 5.5, preconcentration time was 90 s, and HCl 0.5 mol L⁻¹ was the eluent. The main figures of merit were detection limits 3.7 and 9.0 µg L⁻¹ for Cu and Mn, respectively. Precision was expressed as a relative standard deviation better than 10%. Accuracy was evaluated via spiked recovery assays with recoveries between 75–125%. The enrichment factor was 30 for both analytes. These results were adequate for water samples analysis for monitoring purposes. The preconcentration system was coupled and synchronized with the MIP OES nebulizer to allow simultaneous determination of Cu and Mn as a novel sample introduction strategy. The sampling rate was 20 samples/h. Sisal fiber resulted an economical biosorbent for trace element preconcentration without extra derivatization steps and with an awfully time of use without replacement complying with the principles of green analytical methods.     

Ion Chromatography with Pulsed Amperometric Detection for Determining Cyanide in Urine and Meconium Samples

The parents’ addictions and eating habits have a significant influence on the child’s growth. The first stool of a newborn baby provides a large amount of information about xenobiotics transmitted by the mother’s body. The analytical technique used in the study is ion chromatography with pulsed amperometric detection (IC-PAD). The biological samples, which were obtained from women staying in a maternity ward and their partners, revealed cyanide concentrations in urine samples spanning 1.30–25.3 μg L⁻¹. Meanwhile, the results of the meconium samples were in the range of 1.54 μg L⁻¹ to 24.9 μg L⁻¹. Under the optimized chromatographic conditions, the IC-PAD system exhibited satisfactory repeatability (R < 3%, n = 3) and good linearity in the range of 1–100 μg L⁻¹. Thus, it proved to be an effective tool for monitoring trace cyanide concentration in a series of human body fluid matrices, including meconium. Based on the literature review, this is the first application of the IC-PAD analytical technique for the determination of cyanide ions in meconium samples.     

Hybrid Materials Formed with Green Metal-Organic Frameworks and Polystyrene as Sorbents in Dispersive Micro-Solid-Phase Extraction for Determining Personal Care Products in Micellar Cosmetics

Hybrid materials based on polystyrene (PS) and green metal-organic frameworks (MOFs) were synthesized, characterized, and evaluated as potential sorbents in dispersive micro-solid-phase extraction (µ-dSPE). Among the resulting materials, the hybrid PS/DUT-67(Zr) was selected as the adequate extraction material for the monitoring of six personal care products in micellar cosmetic samples, combining the µ-dSPE method with ultra-high performance liquid chromatography (UHPLC) coupled to ultraviolet/visible detection (UV/Vis). Univariate studies and a factorial design were performed in the optimization of the microextraction procedure. The compromise optimum extraction conditions included 20 mg of PS/DUT-67(Zr) for 10 mL of sample, 2 min of extraction time, and two desorption steps using 100 µL of acetonitrile and 5 min assisted by vortex in each one. The validated μ-dSPE-UHPLC-UV/Vis method presented limits of detection and quantification down to 3.00 and 10.0 μg·L⁻¹, respectively. The inter-day precision values were lower than 23.5 and 21.2% for concentration levels of 75 μg·L⁻¹ and 650 μg·L⁻¹, respectively. The hydrophobicity of the resulting PS/DUT-67(Zr) material was crucial for the improvement of its extraction capacity in comparison with its unitary components, showing the advantages of combining MOFs with other materials, getting new sorbents with interesting properties.     

Attapulgite modified with 2-hydroxy-1-naphthaldehyde as selective solid-phase extractant for determination of copper(II) in environmental samples by ICP-OES

Attapulgite modified with 2-hydroxy-1-naphthaldehyde was prepared and applied to the separation, preconcentration and determination of Cu(II) in aqueous solutions by inductively coupled plasma optical emission spectrometry. Experimental conditions for effective adsorption of trace levels of Cu(II) were optimized using batch and column procedures. The optimum pH value for the separation of Cu(II) on the newly sorbent was 4.0 and complete elution of Cu(II) from the sorbent surface was carried out using 2 mL of 0.01 mol L^?1 HCl. The adsorption capacity for Cu(II) was 25.13 mg g^?1. The detection limits of the method defined by IUPAC were found to be 0.24 μg L^?1 with enrichment factor of 150. The method has been applied to the determination of Cu(II) in certified reference materials and natural water samples with satisfactory results.     

Multi‐Walled Carbon Nanotubes as Sorbent for Flow Injection On‐Line Microcolumn Preconcentration Coupled with Flame Atomic Absorption Spectrometry for Determination of Cadmium and Copper

Abstract

Multi‐walled carbon nanotubes (MWNTs) were used as sorbent for flow injection (FI) on‐line microcolumn preconcentration coupled with flame atomic absorption spectrometry (FAAS) for determination of trace cadmium and copper in environmental and biological samples. Effective preconcentration of trace cadmium and copper was achieved in a pH range of 4.5–6.5 and 5.0–7.5, respectively. The retained cadmium and copper were efficiently eluted with 0.5 mol L^?1 HCl for on‐line FAAS determination. The MWNTs packed microcolumn exhibited fairly fast kinetics for the adsorption of cadmium and copper, permitting the use of high sample flow rates up to at least 7.8 mL min^?1 for the FI on‐line microcolumn preconcentration system without loss of the retention efficiency. With a preconcentration time of 60 sec at a sample loading flow rate of 4.3 mL min^?1, the enhancement factor was 24 for cadmium and 25 for copper at a sample throughput of 45 h^?1. The detection limits (3σ) were 0.30 and 0.11 µg L^?1 for Cd and Cu, respectively. The precision (RSD) for 11 replicate measurements was 2.1% at the 10‐µg L^?1 Cd level and 2.4% at the 10‐µg L^?1 Cu level. The developed method was successfully applied to the determination of trace Cd and Cu in a variety of environmental and biological samples.     

Chemically-modified activated carbon with ethylenediamine for selective solid-phase extraction and preconcentration of metal ions

A new method that utilizes ethylenediamine-modified activated carbon (AC-EDA) as a solid-phase extractant has been developed for simultaneous preconcentration of trace Cr(III), Fe(III), Hg(II) and Pb(II) prior to the measurement by inductively coupled plasma optical emission spectrometry (ICP-OES). The new sorbent was prepared by oxidative surface modification. Experimental conditions for effective adsorption of trace levels of Cr(III), Fe(III), Hg(II) and Pb(II) were optimized with respect to different experimental parameters using batch and column procedures in detail. The optimum pH value for the separation of metal ions simultaneously on the new sorbent was 4.0. Complete elution of absorbed metal ions from the sorbent surface was carried out using 3.0 mL of 2% (%w/w) thiourea and 0.5 mol L⁻¹ HCl solution. Common coexisting ions did not interfere with the separation and determination of target metal ions. The maximum static adsorption capacity of the sorbent at optimum conditions was found to be 39.4, 28.9, 60.5 and 49.9 mg g⁻¹ for Cr(III), Fe(III), Hg(II) and Pb(II), respectively. The time for 94% adsorption of target metal ions was less than 2 min. The detection limits of the method was found to be 0.28, 0.22, 0.09 and 0.17 ng mL⁻¹ for Cr(III), Fe(III), Hg(II) and Pb(II), respectively. The precision (R.S.D.) of the method was lower 4.0% (n = 8). The prepared sorbent as solid-phase extractant was successfully applied for the preconcentration of trace Cr(III), Fe(III), Hg(II) and Pb(II) in natural and certified samples with satisfactory results.     

Development and Validation of an Automated Zone Fluidics-Based Sensor for In Vitro Dissolution Studies of Captopril Using Total Error Concept

In the present research, a zone fluidics-based automated sensor for the analysis of captopril in in vitro dissolution samples is reported. Captopril is reacted under flow conditions with Ni(II) (10 mmol L⁻¹) in alkaline medium (0.15% v/v NH₃) to form a stable derivate, which is monitored spectrophotometrically at 340 nm. The chemical and instrumental parameters were carefully investigated and optimized. The validation of the developed method was performed in the range of 5 to 120% of the expected maximum concentration using the accuracy profiles as a graphical decision-making tool. The β-expectation tolerance intervals did not exceed the acceptance criteria of ±10%, which means that 95% of future results will be encompassed in the defined bias limits. The variation of the relative bias ranged between −2.3% and 3.5% and the RSD values for repeatability and intermediate precision were lower than 2.3% in all cases. The limit of detection (LOD), and the lower and the upper limit of quantification (LLOQ, ULOQ) were satisfactory and found to be 1%, 5% and 120% (corresponding to 0.6, 2.78 and 66.67 μg mL⁻¹ in dissolution medium). The developed method was successfully applied for the analysis of captopril in dissolution tests of two commercially available batches.     

On-line solid phase extraction system using 1,10-phenanthroline immobilized on surfactant coated alumina for the flame atomic absorption spectrometric determination of copper and cadmium

An on-line solid phase extraction (SPE) preconcentration system coupled to flame atomic absorption spectrometer (FAAS) was developed for determination of copper and cadmium at μg L⁻¹ level. The method is based on the on-line retention of copper and cadmium on a microcolumn of alumina modified with sodium dodecyl sulfate (SDS) and 1,10-phenanthroline and subsequent elution with ethanol and determination by FAAS. The effect of chemical and flow variables that could affect the performance of the system was investigated. The relative standard deviation (n = 6) at 20 μg L⁻¹ level for copper and cadmium were 1.4 and 2.2% and the corresponding limits of detection (based on 3σ) were 0.04 and 0.14 μg L⁻¹, respectively. The method was successfully applied to determination of copper and cadmium in human hair and water samples.     

Use of modified rice husks as a natural solid adsorbent of trace metals: characterisation and development of an on-line preconcentration system for cadmium and lead determination by FAAS

The use of rice husks as an alternative adsorbent in an on-line preconcentration system for Cd (II) and Pb (II) determination by flame atomic absorption spectrometry (FAAS) is described. The potential of rice husks as a natural adsorbent was evaluated as a material modified with 0.75 mol l⁻¹ NaOH solution and in the unmodified form. For this task, several techniques such as spectroscopy and thermogravimetry were used for elucidation of possible functional groups responsible for the uptake of Cd (II) and Pb (II). Furthermore, based on adsorption studies and adsorption isotherms applied to the Langmüir model, it was possible to verify that modified rice husks present a higher adsorption capacity for both metals. After establishing this material as a promising natural adsorbent, it was used for on-line preconcentration of Cd (II) and Pb (II) metals. The multivariate optimisation of chemical and flow variables was performed by using a full factorial design (2⁴) including the following factors: preconcentration time, preconcentration flow rate, concentration and volume of eluent. The optimum pH values used for on-line preconcentration were taken from prior univariate experiments. Under optimised conditions for Cd (II) determination (4 min of preconcentration at a 6 ml min⁻¹ preconcentration flow rate, in which comprises 24 ml of preconcentration volume, 200 μl elution volume and 1.0 mol l⁻¹ HNO₃ solution as eluent), the system achieved a detection limit of 1.14 μg l⁻¹ and an enrichment factor of 72.4. Similar conditions were used for Pb (II) determination (4 min of preconcentration, 6 ml min⁻¹ preconcentration flow rate, 300 μl elution volume and 1.0 mol l⁻¹ HNO₃ solution as eluent) from which a detection limit of 14.1 μg l⁻¹ and enrichment factor of 46.0 were achieved. Also, rice husks have been shown to be a homogeneous and stable adsorbent in which more than 100 preconcentration/elution cycles provide a relative standard deviation (RSD) of less than 6.0% on the analytical signal. The satisfactory accuracy of the method developed was obtained by using spiked water samples (mineral water and lake water) and spiked red wine samples. These values were confirmed by electrothermal atomic absorption spectrometry (ETAAS). The certified reference material [pig kidney (CRM 186)] and the reference material [beech leaves (CRM 100)] were also used.