Preconcentration and Determination of Metal Ions in Commercial Ethanol Used as Fuel for Automotive Engines

Abstract

The present investigation reports the synthesis, characterization, and adsorption properties of a new nanomaterial based on organomodified silsesquioxane nanocages. The adsorption isotherms for CuCl₂, CoCl₂, ZnCl₂, NiCl₂, and FeCl₃ from ethanol solutions were performed by using the batchwise method. The equilibrium condition is reached very quickly (3 min), indicating that the adsorption sites are well exposed. The results obtained in the flow experiments, showed a recovery of ca. 100% of the metal ions adsorbed in a column packed with 2 g of the nanomaterial, using 5 mL of 1.0 mol L^?1 HCl solution as eluent. The sorption‐desorption of the metal ions made possible the development of a method for preconcentration and determination of metal ions at trace level in commercial ethanol, used as fuel for car engines. The values determined by recommended method for plants 1, 2, and 3 indicated an amount of copper of 51, 60, and 78 µg L^?1, and of iron of 2, 15, and 13 µg L^?1, respectively. These values are very close to those determined by conventional analytical methods. Thus, these similar values demonstrated the accuracy of the determination by recommended method.     

Determination of Cd(II), Co(II), Cu(II), Ni(II), and Pb(II) Ions by FAAS after Separation/Preconcentration using Amberlite XAD‐1180 Chelating Resin Chemically Modified with o‐Aminophenol

Abstract

The use of a newly synthesized chelating resin with an o‐aminophenol–type functional groups and Amberlite XAD‐1180–type supporting material for separation/preconcentration of trace metal ions from various water samples was described. Amberlite XAD‐1180‐o‐aminophenol chelating resin (XAD‐o‐AP) was synthesized using Amberlite XAD‐1180 resin as solid support and o‐aminophenol as the chelating ligand. The determination of Cd(II), Co(II), Cu(II), Ni(II), and Pb(II) ions was made by flame atomic absorption spectrometry (FAAS). Studying with model solutions for the optimization of the method was based on the measurement of recovery values (between 92–106%) of the analyte elements. Some analytical parameters such as pH (6.0), volume of the sample (～250 mL), effect of matrix ions, flow rates of the sample (2.5 mL min^?1) and elution solutions (2.5 mL min^?1), concentration, type and volume of the eluent (4 mol L^?1 HNO₃, 20 mL) were investigated. The detection limit (3s/b, n=20) and the relative standard deviation (n=7) of the method were found to be in the range 0.9–4.3 µg L^?1 and 4.4–5.5%, respectively. The proposed method was successfully applied to the real samples such as wastewater, boiler feeding water and a certified reference material (Estuarine water, LGC 6016).     

Development of micellar solid-phase microextraction fiber based on CTAB-templated mesoporous silica electrochemically assisted self-assembled on wire: Application to chromatographic determination of polycyclic aromatic hydrocarbons

This paper describes the development of a new micellar solid-phase microextraction fiber based on cetyltrimethylammonium bromide-templated mesoporous silica electrochemically assisted self-assembled on copper wire for sensitive determination of polycyclic aromatic hydrocarbons by HPLC. After optimization of experimental parameters, non-polar analytes of PAHs were successfully determined in water samples after microextraction by CTAB/MCM-41 copper fiber as micellar organic platform. The proposed method indicated good linearity in the range 0.01–82.5 µg L^?1 and limits of detection in the range 3–46 ng L^?1. Relative standard deviations of the method were obtained in the range 3.1–8.3%.     

Solid Phase Extraction and Determination of Ultra Trace Amounts of Copper using Activated Carbon Modified by N,N′‐Bis(Salicylidene)‐1,2‐Phenylenediamine

Abstract

N,N′‐bis(salicylidene)‐1,2‐phenylenediamine(salophen) modified activated carbon was prepared and used as an effective sorbent for solid phase extraction of Cu(II) ions from aqueous solutions. The salophen modified activated carbon showed a high sorption affinity for Cu(II). In this method a column mode was used for preconcentration of copper(II) in the pH range 3.5–6.5. The retained copper was eluted with 0.1 mol l^?1 EDTA and determined by atomic absorption spectrometry. The calibration graph was linear over the copper concentration in the range 0.05–1.5 µg ml ^?1. Five replicate determination of 0.4 µg ml^?1 of copper(II) gave a mean absorbance of 0.385 with a relative standard deviation of 1.35%. The detection limit was 0.0133 µg ml^?1. The interference of a large number of anions and cations has been studied and the optimized conditions developed were utilized for determination of copper in various real samples.     

Homogeneous Liquid–Liquid Extraction and Determination of Cobalt,Copper, and Nickel in Water Samples by Flame Atomic Absorption Spectrometry

Abstract

A simple and effective homogeneous liquid–liquid extraction method has been used for the simultaneous extraction and preconcentration of cobalt, copper, and nickel after the formation of complex with 4‐benzylpiperidinedithiocarbamate potassium salt (K‐4‐BPDC), and later they were determined by flame atomic absorption spectrometry (FAAS) using (water/tetrabutylammonium ion (TBA⁺)/chloroform) as a ternary component system. The phase separation phenomenon occurred by an ion‐pair formation of TBA⁺ and perchlorate ion. After the optimization of complexation and extraction conditions ([K‐4‐BPDC]=2.0×10^?4 mol l^?1, [TBA⁺]=2.0×10^?2 mol l^?1, [CHCl₃]=60.0 µl, [ClO₄ ^?]=2.0 ×10^?2 mol l ^?1 and pH=6.0), a preconcentration factor of 200 was obtained for only 10 ml of the sample.

The analytical curves were linear in the range of 20–1500, 15–2000, 35–1600 µg l^?1 and the limits of detection were 10, 5, and 15 µg l^?1 for Co²⁺, Cu²⁺, and Ni²⁺, respectively. The proposed method was applied for the extraction and determination of Co²⁺, Cu²⁺, and Ni²⁺ in natural water samples with satisfactory results.     

Vibrating screen printed electrode of gold nanoparticle-modified carbon nanotubes for the determination of arsenic(III)

A linear sweep anodic stripping voltammetric method using a carbon nanotube–gold nanoparticle-modified vibrating screen printed electrode for the determination of arsenic(III) is reported. The experiments were conducted with a 0.1 mol L^?1 solution of H₂SO₄ in order to estimate the electrode area related to gold oxide formation. The results showed a clear reduction peak at approximately +0.85 V corresponding to the reduction of the gold surface oxide with a superficial area of 0.089 cm². A vibrating motor was attached to the screen printed electrode to create a portable and autonomous system with enhanced mass transfer. The repeatability of the measurements was 2.4 % (n = 10) at the level of 0.5 mg L^?1 of arsenic(III) under the best instrumental operating conditions. The peak current was linearly dependent on the arsenic(III) concentration, thus allowing the construction of a linear analytical curve in the range from 10 to 550 μg L^?1 with the equation: ?I_p (μA) = 0.05 + 134.59 [As(III) (μg L^?1)], R² = 0.99. The obtained detection and quantification limits were 0.5 (3 SD) and 1.5 (10 SD) μg L^?1, respectively, using 120 s as the deposition time. It was shown that Cu(II) does not interfere in the detection of As(III) using the proposed method.     

Development of dispersive liquid-liquid microextraction based on deep eutectic solvent using as complexing agent and extraction solvent: application for extraction of heavy metals

ABSTRACT

A green and efficient dispersive liquid-liquid microextraction method based on a new deep eutectic solvent has been developed for the preconcentration and extraction of cobalt and nickel ions. The deep eutectic solvent is formed by mixing choline chloride (hydrogen bond acceptor) and 4-aminophenol (hydrogen bond donor). Then, it is used as a chelating agent as well as extraction solvent. Under the optimum experimental conditions, the linear ranges for Ni(II) and Co(II) were 0.80–50 and 0.50–50 µgL^?1, respectively, by flame atomic absorption spectrometry. The obtained detection limits were 0.30 and 0.22 µg L^?1 for Ni(II) and Co(II), respectively.     

A simple vortex-assisted graphene oxide nanosheets dispersive micro-solid phase extraction combined with high-performance liquid chromatography for UV-Vis detection of tramadol in biological samples

This study developed a simple, rapid and sensitive method that utilizes vortex-assisted graphene oxide nanosheets dispersive micro-solid phase extraction of tramadol hydrochloride from biological samples. The data obtained from scanning electron microscopy, X-ray diffraction and Fourier transform infrared spectroscopy confirmed the characteristics of graphene oxide nanosheets (GONSs). In order to increase the extraction efficiency, a vortex was applied in the extraction process. In this study, parameters affecting the extraction efficiency were identified and discussed. The optimal experimental parameters were as follows: pH, amount of GONSs, type and volume of desorption solvent, vortexing time, and addition of NaCl. Under optimized conditions, this method allowed the determination of tramadol in the range of 5–300 µg l^?1 and the limit of detection was 0.16 µg l^?1. The intra-day and inter-day precisions obtained were 2.4% and 3.8%, respectively. This method can be used as an analytical technique for the determination of tramadol in biological samples.     

Synthesis,Characterization, and Application of Zn–Al Layered Double Hydroxide as a Nano-Sorbent for the Removal of Direct Red 16 from Industrial Wastewater Effluents

In this research, nano-structured zinc–aluminum layered double hydroxide (Zn–Al LDH) was successfully synthesized by a co-precipitation method and followed by thermal treatment. The structure and morphology of the obtained material was characterized by X-ray diffraction, transmission electron microscopy, nitrogen-adsorption–desorption isotherms, and Fourier transform infrared spectroscopy. The as-prepared LDH was applied as a solid phase extraction (SPE) sorbent for the removal of direct red 16 (DR16) from aqueous solutions. A spectrophotometric method was used for monitoring of the extracted DR16 at λ = 548 nm. The effect of several parameters such as pH, sample flow rate, amount of nano-sorbent, elution conditions, and sample volume on the removal percentage was investigated. The results showed that DR16 could be retained by Zn–Al(NO₃^?) LDH at pH 6 and stripped by 2.5 mL of 1.0 mol L^?1 NaOH. In the optimum experimental conditions, the limit of detection and relative standard deviation were 0.003 µg mL^?1 and 1.2%, respectively. The calibration graph using the presented SPE system was linear in the range of 0.01–2.00 µg mL^?1 of DR16 with a correlation coefficient of 0.9994. The method was successfully applied for the removal of DR16 from several industrial wastewater effluents.     

Development of an ultrasonic-assisted restricted access supramolecular solvent-based liquid phase microextraction (UA-RAS-LPME) method for separation-preconcentration and UV-VIS spectrophotometric detection of curcumin

ABSTRACT

Environment-responsive long chain acid (C7–C14)-based supramolecular solvents (SUPRAs) were produced and their potential usage for microextraction of curcumin was assessed in the presented work. The SUPRAs were prepared by mixing of decanoic acid with tetrahydrofuran. The ultrasonic-assisted restricted access supramolecular solvent liquid phase microextraction of curcumin was achieved at pH 6 by 200 µL of using SUPRAs. Various parameters including pH, solvent volume, ultrasonication time, and sample volume were optimized. The limit of detection, limit of quantification, relative standard deviation %, and preconcentration factor were 5.3 µg L^?1, 17.5 µg L^?1, 2.2%, and 50, respectively. The accuracy of method was checked by additional-recovery experiments.     

Urban Stream Vulnerability Toward PAHs and n-Alkanes and Their Source Identification

Monjolinho River is an important water body located in the central urban region of São Paulo State in southeast Brazil. The present work reports a 4-year study related to spatio-temporal distribution and source identification of polycyclic aromatic hydrocarbons (PAHs) and n-alkanes in surface water and sediment samples of Monjolinho River. A total of 25 sampling campaigns for water, and 10 sampling campaigns for sediment collection, were performed from 2011 to 2014. In sediment samples, total PAHs were found in the range of 2.25 µg kg^?1–26,253.87 µg kg^?1, while n-alkane concentrations ranged from 0.01 to 165.64 µg kg^?1. Total PAHs' concentration in surface water was in the range of 0.17–1,348.35 ng L^?1, while n-alkanes were detected in the range of 6.17–316.15 µg L^?1. Principal component analysis was used as a statistical tool for summarizing and interpreting a huge quantity of data. It was observed that concentrations of contaminants increased along the river course in urban zone. Distribution indexes were calculated to identify possible sources of carbon pool that pointed towards petrogenic, pyrogenic, and biogenic sources. The overall concentrations of PAHs and n-alkanes were low compared to many previous studies done elsewhere and were mostly below the threshold effects level except in very few occasional cases, while probable effect level was violated in 1 sample during 4 years. Although adverse impacts are unexpected due to overall low contaminant concentrations, unexpected industrial, and sewage discharges make it risky for safer use as a drinking water resource, especially in dry conditions.     

Biological removal of 17α‐ethinylestradiol (EE2) in an aerated nitrifying fixed bed reactor during ammonium starvation

BACKGROUND: Conventional wastewater treatment plants (WWTPs) tend to partially remove recalcitrant chemicals, such as pharmaceuticals. Among these, the synthetic estrogen 17α‐ethinylestradiol (EE2) is of great environmental concern. In this work a continuously aerated submerged fixed bed bioreactor was used for the biological removal of EE2 at µg L^?1 levels. RESULTS: Removal efficiencies higher than 96% were obtained at a hydraulic retention time (HRT) of 4.3 days and a volumetric loading rate (B_v) of 11 µg EE2 L^?1 d^?1. Increasing the B_v up to 40 and 143 µg EE2 L^?1 d^?1 led to slightly lower removal efficiencies, 81 and 74%, respectively. Nitrification was confirmed to be the main biological mechanism involved in EE2 removal. Most interestingly, the elimination of EE2 was not affected by the absence of ammonium in the feed, suggesting that ammonia‐oxidizing bacteria (AOB) were able to maintain their population density and their activity, even after several months of starvation. CONCLUSION: The concept of an aerated submerged fixed bed bioreactor, capable of removing estrogens in a sustainable and biological way, shows great potential as an effluent polishing step for existing WWTPs. Copyright © 2008 Society of Chemical Industry     

Determination of Copper,Iron, Nickel,and Zinc in Ethanol Fuel by Flame Atomic Absorption Spectrometry Using On‐Line Preconcentration System

Abstract

In this work, an on‐line system for preconcentration and determination of copper, iron, nickel, and zinc at µg L^?1 level by flame atomic absorption spectrometry (FAAS) has been developed. Amberlite XAD‐4 functionalized with 3,4‐dihydroxybenzoic acid packed in a minicolumn was used as metal sorbent. The retained metals can be quickly eluted from sorbent material, with the eluent stream consisting of hydrochloric acid solution, directly to the nebulizer burner system of the FAAS. Analytical parameters were evaluated and the results demonstrated that all studied metals can be determined, using borate buffer to adjust the sample pH at 8.0. The results showed that the proposed method is simple and rapid. The limits of detection were estimated as 2.3, 5.0, 7.8, and 0.1 µg L^?1 for copper, iron, nickel, and zinc, respectively, using a preconcentration time of 60 s and a sample flow rate of 5.5 mL min^?1. Enrichment factors of 22, 15, 12, and 54 and coefficients of variations of 3.5, 4.4, 4.4, and 3.2% were obtained in the determination of copper, iron, nickel, and zinc, respectively. The system presented an analytical throughput of 10 samples per hour and was successfully applied in the determination of metals in ethanol fuel.     

Macromolecular Chelator‐Amberlite XAD‐16 Anchored with 2,3‐Dihydroxypyridine (DHP) for Enrichment of Metal Ions before their Determination by Flame Atomic Absorption Spectrometry

Abstract

2,3‐Dihydroxypyridine (DHP) was loaded onto Amberlite XAD‐16 via azo linker and the resulting resin AXAD‐16‐DHP explored for enrichment of Zn(II), Mn(II), Ni(II), Pb(II), Cd(II), Cu(II), Fe(III), and Co(II) in the pH range 4.0–6.5. The sorption capacity was found in the range 120–512 µmol g^?1 and the preconcentration factor from 200 to 300. Tolerance limits for foreign species are reported. The kinetics of sorption is fast, as t_1/2 is generally ≤2 min. The chelating resin can be reused for fifty cycles of sorption‐desorption without any significant change (≤2.0%) in its sorption capacity. The limit of detection values (blank + 3s) are 2.90, 3.80, 5.17, 7.02, 1.91, 1.63, 4.59, and 5.02 µg L^?1 for Zn, Mn, Ni, Pb, Cd, Cu, Fe, and Co respectively. The corresponding limit of quantification (blank + 10 s) values are 5.30, 6.20, 8.38, 9.54, 4.22, 4.17, 8.62, and 9.86 µg L^?1, respectively. The enrichment on AXAD‐16‐DHP coupled with monitoring by flame atomic absorption spectrometry (FAAS) is used to determine these metal ions in river and synthetic water samples, Co in vitamin tablets, and Zn in milk samples. AXAD‐16‐DHP has been found to perform better than DHP loaded cellulose and Amberlite XAD‐2.     

Effects of butyric acid stress on anaerobic sludge for hydrogen production from kitchen wastes

BACKGROUND: Anaerobic digestion is an alternative technology to achieve the dual benefits of hydrogen production and waste stabilization from kitchen wastes. In this work, the butyric acid stress on anaerobic sludge was investigated in order to improve the tolerance of sludge against organic acids, and to enhance hydrogen accumulation. RESULTS: The tolerance of butyric acid in anaerobic sludge increased with the stress concentration, however, it decreased at concentrations greater than of 4.0 g L^?1. The maximum hydrogen yield reached 63.72 mL g^?1 VS at 4.0 g L^?1 stress, representing an increase of 114% compared with the control group. The concentration of volatile solids (VS) of the sludge and SCOD increased steadily with time up to 20 h. At 4.0 g L^?1 butyric acid stress, the maximum activity of β‐glucosidase, BAA‐hydrolysing protease and dehydrogenase enzyme were 14912.1 µmol PNP g^?1 TS h^?1, 134.14 µmol NH₄‐N g^?1 TS h^?1 and 7316.42 µg TF g^?1 TS h^?1, which were 2.78, 1.90 and 2.01 times that of the control, respectively. CONCLUSIONS: The feasibility of butyric acid stress on anaerobic sludge to increase hydrogen production from kitchen wastes was demonstrated. Remarkably, 4.0 g L^?1 butyric acid stress was found to be favorable for improving the tolerance of butyric acid in sludge as well as hydrogen yield in the experiment. Copyright © 2010 Society of Chemical Industry     

THIOCYANATE-ASSISTED SOLID PHASE ENRICHMENT OF Cu(II) USING PYRIDINE DERIVATIVE WITH X-RAY CRYSTALLOGRAPHIC EVIDENCE

Equimolar mixture of pyridine-2,6-dimethanol (PDM), and thiocyanate ion immobilized on silica serves as an efficient sorbent for selective retention of Cu(II) from other associated metal ions at µg g^?1 level. The maximum sorption capacity for Cu(II) was found as 2.44 mmol g^?1 at pH 6.0. The sorbed Cu(II) was completely eluted with 3 mol L^?1 HNO₃ and measured with a flame atomic absorption spectrometer (FAAS). The structure of the extracted Cu(II) complex was confirmed by single-crystal X-ray structure analysis and Fourier transform-infrared (FT-IR) spectroscopy. Thermogravimetric analysis (TGA) of the isolated Cu(II) complex was performed to determine its thermal stability at the extraction temperature. The three sigma detection limit (N = 15) of the method is 0.6 µ g mL^?1 with a relative standard deviation (RSD) of 0.1% (N = 15). Pre-concentration factor of the method is 133. Slight interference from Mn²⁺ ion was eliminated by prior oxidation with potassium periodate. The developed method was tested for trace level separation and estimation of Cu(II) in certified reference materials and environmental samples.

[Supplementary materials are available for this article. Go to the publisher's online edition of Chemical Engineering Communications for the following free supplemental resources: two tables providing details of the bond lengths and bond angles of the Cu(II) complex.]     

CORN GLUTEN HYDROLYSIS BY ALCALASE: KINETICS OF HYDROLYSIS

In the present study, the reaction kinetics of corn gluten hydrolysis by Alcalase, a bacterial protease produced by Bacillus licheniformis, was investigated. The reactions were carried out for 10 min in 0.1 L of aqueous solutions containing 10, 20, 30, 40, and 50 g protein L^?1 corn gluten at various temperature and pH values. The amount of enzyme added to the reaction solution was 0.25% (v/v). Also, to determine decay and product inhibition effects for Alcalase, a series of inhibition experiments were conducted with the addition of various amounts of hydrolysate. For each experimental run, both the amount of hydrolysis (meqv L^?1) and the soluble protein amount (g L^?1) were investigated with respect to time, and the initial reaction rates were determined from the slopes of the linear models that fitted to these experimental data. The kinetic parameters, K_m and V_max were estimated as 53.77 g L^?1 and 5.94 meqv L^?1min^?1. The type of inhibition for Alcalase was determined as uncompetitive, and the inhibition constant, K_i, was estimated as 44.68% (hydrolysate/substrate mixture).     

Construction and Performance Characteristics of Modified Screen Printed and Modified Carbon Paste Sensors for Selective Determination of Cu(II) Ion in Different Polluted Water Samples

Four new ion-selective electrodes (ISEs), based on N,N′-bis(salicylaldehyde)-p-phenylene diamine (SPD) as ionophore, are constructed for the determination of copper(II) ion. The modified carbon paste (MCPEs; electrodes I and II) and modified screen-printed sensors (MSPEs; electrodes III and IV) exhibit good potentiometric response for Cu(II) over a wide concentration range of 1.0 × 10^?6 – 1.0 × 10^?2 mol L^?1 for electrodes (I and II) and 4.8 × 10^?7–1.0 × 10^?2 mol L^?1 for electrodes (III and IV) with a detection limit of 1.0 × 10^?6 mol L^?1 for electrodes (I and II) and 4.8 × 10^?7 mol L^?1 for electrodes (III and IV), respectively. The slopes of the calibration graphs are 29.62 ± 0.9 and 30.12 ± 0.7 mV decade^?1 for electrode (I) (tricresylphosphate (TCP) plasticizer) and electrode (II) (o-nitrophenyloctylether o-NPOE plasticizer), respectively. Also, the MSPEs showed good potentiometric slopes of 29.91 ± 0.5 and 30.70 ± 0.3 mV decade^?1 for electrode (III) (TCP plasticizer) and electrode (IV) (o-NPOE plasticizer), respectively. The electrodes showed stable and reproducible potentials over a period of 60, 88, 120, and 145 days at the pH range from 3 to 7 for electrodes (II), (III), and (IV) and pH range from 3 to 6 for electrode (I). This method was successfully applied for potentiometric determination of Cu(II) in tap water, river, and formation water samples in addition to pharmaceutical preparation. The results obtained agree with those obtained with the atomic absorption spectrometry (AAS).     

Equilibrium and dynamic studies of the removal of As(III) and As(V) from contaminated aqueous systems using a functionalized biopolymer

BACKGROUND: A study of the removal of arsenic from a sample of actual groundwater using crosslinked xanthated chitosan is described. RESULTS: Removal of As(III) and As(V) was studied at pH 7.5 under equilibrium and dynamic conditions. The equilibrium data were fitted to Langmuir and Freundlich adsorption models and the various model parameters evaluated. The monolayer adsorption capacity from the Langmuir model for xanthated chitosan flakes (XCF) (As(V) 20.0 ± 0.56 mg g^?1; As(III) 33.0 ± 0.32 mg g^?1) were lower than obtained for xanthated chitosan granules (XCB) (As(V) 36.0 ± 0.52 mg g^?1; As(III) 48.0 ± 0.45 mg g^?1). Adsorption of As (V) was unaffected by the presence of other anions while in the case of As(III) the presence of sulfate and silicate caused a 26.5–50.9% decrease in adsorption. A sample (940 bed volumes) of a groundwater spiked with 200 µg L^?1 As(V) treated with XCF in column experiments reduced the arsenic concentration to < 10 µg L^?1. The adsorbent was also successfully applied for the removal of total inorganic arsenic down to < 10 µg L^?1 from real samples of arsenic‐contaminated groundwater. CONCLUSION: Xanthated chitosan was an efficient adsorbent for the removal of both forms of arsenic from groundwater under near neutral conditions. The presence of sulfur and the amino groups resulted in increased adsorption capacity of the sorbent. Copyright © 2012 Society of Chemical Industry     

Applicability of a magnetic bucky gel for microextraction of mercury from complicated matrices followed by cold vapor atomic absorption spectroscopy

ABSTRACT

A new eco-friendly bucky gel nano sorbent consisting of magnetic grapheneoxide (MGO) and an ionic liquid (IL) was used based on dispersive extraction technique followed by cold vapor atomic absorption spectroscopy for determination of mercury in river water, milk, omega-3 supplements, and lipstick. The optimum conditions for extraction were 50 mg of sorbent (mass ratio IL/MGO: 26), 8 min vortexing, acetate buffer pH = 4, and for desorption 3 min vortexing of HNO₃ (1 mL). The limits of detection, quantification, preconcentration factor and extraction recovery were found at 0.57, 1.88 µg L^?1, 21 and 84%. Relative standard deviation (RSD) was 6.5% (n = 3).