On‐line Solid Phase Extraction of Copper in Water Samples with Flow Injection Flame Atomic Absorption Spectrometry

An on‐line solid phase extraction method for the preconcentration and determination of Cu(II) by flame atomic absorption spectrometry has been described. The procedure is based on the retention of Cu(II) ions at pH 6.0 on a minicolumn packed with Amberlite XAD‐1180 resin impregnated with chrome azurol S. After preconcentration, Cu(II) ions adsorbed on the impregnated resin were eluted by 1 mol L^?1 HNO₃ solution. Several parameters, such as pH, type of eluent, flow rates of sample and eluent solutions, amount of resin were evaluated. At optimized conditions, for 3.5 min of preconcentration time, the system achieved a detection limit of 1.0 µg L^?1, and a relative standard deviation of 1.2% at 0.2 µg mL^?1 copper. An enrichment factor of 56‐fold was obtained with respect to the copper determination. The proposed method was successfully validated by the analysis of standard reference material (TMDA 54.4 lake water) and recovery studies. The method was applied to the preconcentration of Cu(II) in natural water samples.     

Selective Separation/Preconcentration of Silver Ion in Water by Multiwalled Carbon Nanotubes Microcolumn as a Sorbent

The present paper proposes the application of multiwalled carbon nanotubes (MWCNTs) as a solid adsorbent for selective separation/preconcentration of silver(I) in water samples prior to flame atomic absorption spectrometry. The procedure is based on the solid phase extraction of Ag(I)–2‐mercaptobenzothiazole chelate on MWCNTs. The elution step is carried out with 5 mL of 2 mol L^?1 HNO₃ in acetone solution at a flow rate of 1.0 mL min^?1. The influences of the various analytical parameters including pH of the solution, eluent type, sample volume, flow rates of eluent, matrix ions were investigated for optimization of the presented procedure. Tests of addition/recovery for analyte ion in real samples were performed with satisfactory results. Preconcentration factor and limit of detection for Ag(I) were 160 and 0.21 µg L^?1, respectively. The synthesized MWCNT exhibited excellent stability in eluent solution and its adsorption capacity was 5.4 mg of silver per gram of sorbent. The proposed method was successfully applied to trace silver determination in a variety of environmental water samples.     

Coprecipitation with Cu(II)‐4‐(2‐Pyridylazo)‐resorcinol for Separation and Preconcentration of Fe(III) and Ni(II) in Water and Food Samples

The coprecipitation method is widely used for the preconcentration of trace metal ions prior to their determination by flame atomic absorption spectrometry (FAAS). A simple and sensitive method based on coprecipitation of Fe(III) and Ni(II) ions with Cu(II)‐4‐(2‐pyridylazo)‐resorcinol was developed. The analytical parameters including pH, amount of copper (II), amount of reagent, sample volume, etc., were examined. It was found that the metal ions studied were quantitatively coprecipitated in the pH range of 5.0–6.5. The detection limits (DL) (n = 10, 3s/b) were found to be 0.68 µg L^?1 for Fe(III) and 0.43 µg L^?1 for Ni(II) and the relative standard deviations (RSD) were ≤4.0%. The proposed method was validated by the analysis of three certified reference materials (TMDA 54.4 fortified lake water, SRM 1568a rice flour, and GBW07605 tea) and recovery tests. The method was successfully applied to sea water, lake water, and various food samples.     

Preparation,Characterization of a Novel Chelating Resin Functionalized with o‐Hydroxybenzamide and Its Application for Preconcentration of Trace Metal Ions

A stable extractor of metal ions was synthesized through azo linking of o‐hydroxybenzamide (HBAM) with Amberlite XAD‐4 (AXAD‐4) and was characterized by elemental analyses, IR spectral, and thermal studies. Its water regain value and hydrogen ion capacity were found to be 12.93 and 7.68 mmol g^?1, respectively. The optimum pH range (with the half‐loading time [min], t_1/2) for Cu(II), Cr(III), Ni(II), Co(II), Zn(II), and Pb(II) ions were 2.0–4.0 (5.5), 2.0–4.0 (7.0), 2.0–4.0 (8.0), 4.0–6.0 (9.0), 4.0–6.0 (12.0), and 2.0–4.0 (15.0), respectively. Comparison of breakthrough and overall capacities of the metals ascertains the high degree of column utilization (>70%). The overall sorption capacities for Cu(II), Cr(III), Ni(II), Co(II), Zn(II), and Pb(II) ions were found to be 0.29, 0.22, 0.20, 0.16, 0.13, and 0.11 mmol g^?1 with the corresponding preconcentration factor of 400, 380, 380, 360, 320, and 320, respectively. The limit of preconcentration was in the range of 5.0–6.3 ng mL^?1. The detection limit for Cu(II), Cr(III), Ni(II), Co(II), Zn(II), and Pb(II) were found to be 0.39, 0.49, 0.42, 0.59, 0.71, and 1.10 ng mL^?1, respectively. The AXAD‐4‐HBAM has been successfully applied for the analysis of natural water, multivitamin formulation, infant milk substitute, hydrogenated oil, urine, and fish.     

Preconcentration by Coprecipitation of Copper and Nickel with Mo(VI)/Triazole Derivative System and Their Determinations by Flame Atomic Absorption Spectrometry in Food and Water Samples

A new separation and preconcentration technique based on coprecipitation of Cu(II) and Ni(II) ions by the aid of Mo(VI)/di‐tert‐butyl{methylenebis[5‐(chlorobenzyl)‐4H‐1,2,4‐triazol‐3,4‐diyl]}biscarbamate (BUMECTAC) precipitate has been established. The Mo(VI)/BUMECTAC precipitate was dissolved by concentrated HNO₃ and the solution was completed to 5.0 mL with distilled/deionized water. The levels of the analyte ions were determined by flame atomic absorption spectrometer. The effects of experimental conditions like HNO₃ concentration, amount of BUMECTAC and Mo(VI), sample volume, etc. and also the influences of some foreign ions were investigated in detail on the quantitative recoveries of analyte ions. The preconcentration factors were found to be 40 for Cu(II) and 100 for Ni(II) ions. The detection limits for Cu(II) and Ni(II) ions based on 3σ (N:10) were 0.43 and 0.70 µg L^?1, respectively. The relative standard deviations were found to be lower than 4.0% for both analyte ions. The accuracy of the method was checked by spiked/recovery tests and the analysis of two certified reference materials (Environment Canada TM‐25.3 and CRM‐SA‐C Sandy Soil C). The procedure was successfully applied to sea water and stream water as liquid samples and baby food as solid sample in order to determine the levels of Cu(II) and Ni(II) ions.     

A Multi‐Element Ion‐Pair Extraction for Trace Metals Determination in Environmental Samples

A multi‐element ion‐pair extraction method was described for the preconcentration of Cd(II), Co(II), Cr(III), Cu(II), Fe(III), Mn(II), Ni(II), Pb(II), and Zn(II) ions in environmental samples prior to their determinations by flame atomic absorption spectrometry (FAAS). As an ion‐pair ligand 2‐(4‐methoxybenzoyl)‐N′‐benzylidene‐3‐(4‐methoxyphenyl)‐3‐oxo‐N‐phenyl‐propono hydrazide (MBMP) was used. Some analytical parameters such as pH of sample solution, amount of MBMP, shaking time, sample volume, and type of counter ion were investigated to establish optimum experimental conditions. No interferences due to major components and some metal ions of the samples were observed. The detection limits of the proposed method were found in the range of 0.33–0.9 µg L^?1 for the analyte ions. Recoveries were found to be higher than 95% and the relative standard deviation (RSD) was less than 4%. The accuracy of the procedure was estimated by analyzing the two certified reference materials, LGC6019 river water and RTC‐CRM044 soil. The developed method was applied to several matrices such as water, hair, and food samples.     

Novel Polymeric Resin for Solid Phase Extraction and Determination of Lead in Waters

Interest in preconcentration techniques for the determination of metals at ultratrace levels still continues increasingly because of some disadvantages of flameless atomic absorption spectrometry and the high costs of other sensitive methods in compared to flame atomic absorption spectrometry (FAAS). Among preconcentration techniques, solid‐phase extraction is the most popular because of a number of advantages. In this work, thiol‐containing sulfonamide resin was synthesized, characterized, and applied as a new sorption material for solid phase extraction and determination of lead in natural water samples. The optimization of experimental conditions was performed using the parameters including pH, contact time, and volumes of initial and elution solutions. After preconcentration procedure, FAAS was used for determinations. The synthesized resin exhibits the superiority in compared to the other adsorption reagents because of the fact that there is no necessity of any complexing reagent as well as high sorption capacity. Consequently, 280‐fold improvement in the sensitivity of analytical scheme was achieved by combining the slotted tube atom trap‐atomic absorption spectrometry (STAT‐FAAS) and the developed preconcentration method. The limit of detection was found to be 0.15 ng mL^?1. The Pb²⁺ concentrations in the studied water samples were found to be in the range of 0.9–6.7 ng mL^?1.     

Preconcentration of trace multi-elements in water samples using Dowex 50W-x8 and Chelex-100 resins prior to their determination using inductively coupled plasma atomic emission spectrometry (ICP-OES)

This work presents a solid phase extraction (SPE) method for simultaneous preconcentration of trace elements in water samples prior to their ICP-OES determination. Dowex 50W-x8 and Chelex-100 resins were used as SPE sorbent materials for preconcentration of trace Cd, Co, Cr, Cu, Fe, Ni, Pb and Zn. The optimum sample pH, eluent concentration and sample flow rates were found to 6, 3.0 mol L⁻¹ and 3.0 mL min⁻¹, respectively. In terms of multi-element preconcentration capabilities, Dowex 50W-x8 appeared to be a better sorbent. The recoveries for all the tested analytes were >95%. However, Chelex-100 showed a better performance in terms of recovery (>95%) towards Cu, Fe and Zn. Under optimized conditions using Dowex 50W-x8, the relative standard deviations for different metals were <3%. The limits of detection and limits of quantification ranged from 0.01–0.39 μg L⁻¹ and 0.05–0.1.3 μg L⁻¹, respectively. The accuracy of the preconcentration method was confirmed by spike recovery test and the analysis of certified reference materials. The SPE method was applied for preconcentration of the analyte ions in tap water, bottled water and wastewater samples.     

Preparation of Nano‐Lepidocrocite and an Investigation of Its Ability to Remove a Metal Complex Dye

Lepidocrocite (γ‐FeOOH) nanoparticles were synthesized from iron(II) sulfate solution and characterized using X‐ray diffraction (XRD), transmission electron microscopy (TEM), Fourier transform‐IR (FT‐IR), nitrogen adsorption, and point of zero charge pH (pH_PZC) analyses. TEM, XRD, and FT‐IR analyses proved the synthesis of nano‐lepidocrocite. Surface area and pH_PZC of the synthesized lepidocrocite were 68.1 m² g^?1 and 4.8, respectively. Utilization of the synthesized lepidocrocite in the adsorption of Lanacron brown S‐GL (LBS‐GL) from aqueous solutions was investigated, and the effect of lepidocrocite dosage, pH, temperature, and contact time on this process were optimized and modeled using response surface methodology approach. The lepidocrocite dosage of 0.015 g, pH 3.5, temperature of 38°C, and contact time of 100 min were determined as optimum adsorption conditions. Isotherm and kinetics of the adsorption process were analyzed at the optimum conditions. The equilibrium data were fitted well to the Langmuir isotherm model. The maximum monolayer adsorption capacity was 528.21 mg g^?1. The adsorption process was described by the pseudo‐second‐order kinetic model. Furthermore, the effect of pH on the desorption of LBS‐GL was investigated. High LBS‐GL desorption efficiency was achieved at a high pH value.     

Cercis siliquastrum Tree Leaves as an Efficient Adsorbent for Removal of Ag(I): Response Surface Optimization and Characterization of Biosorption

The Cercis siliquastrum tree leaves are introduced as a low cost biosorbent for removal of Ag(I) from aqueous solution in a batch system. FT‐IR, XRD analysis, and potentiometric titration illustrate that the adsorption took place and the acidic functional group (carboxyl) of the sorbent was involved in the biosorption process. In addition, it was observed that the pH beyond pH_pzc 4.4 is favorable for the removal procedure. The effect of operating variables such as initial pH, temperature, initial metal ion concentration, and sorbent mass on the Ag(I) biosorption was analyzed using response surface methodology (RSM). The proposed quadratic model resulting from the central composite design approach (CCD) fitted very well to the experimental data. The optimum condition obtained with RSM was an initial concentration of Ag(I) of 85 mg L^?1, pH = 6.3 and sorbent mass 0.19 g. The applicability of different kinetic and isotherm models for current biosorption process was evaluated. The isotherm, kinetic, and thermodynamic studies showed the details of sorbate‐sorbent behavior. The competitive effect of alkaline and alkaline earth metal ions during the loading of Ag(I) was also considered.     

Kinetics,Mechanistic and Thermodynamics of Zn(II) Ion Sorption: A Modeling Approach

Biosorption potential of Cedrus deodara sawdust (CDS) in terms of sorption of Zn(II) ion across liquid phase has been evaluated in the present investigation. The surface of the CDS biomass before the sorption of Zn(II) ions seemed to be more porous, non‐crystalline and heterogeneous. The maximum uptake capacity of CDS was 97.39 mg g^?1. Sorption of Zn(II) ion on the surface of CDS sawdust was maximum at pH 5, temperature 45°C, initial concentration of Zn(II) ion 100 mg L^?1, biomass dose 1 g L^?1, contact time 150 min, and agitation rate 160 rpm. Pseudo second‐order kinetics with the highest linear regression coefficient (R² = 0.99), and lowest values of error functions, i.e., chi (χ²) and sum of square errors (SSE) against pseudo first‐order rate kinetics showed that the sorption of Zn(II) ion on the surface of CDS was mediated by chemosoprtive forces of attraction rather than physical adsorption. Mechanistically, relatively higher proportion of sorption of Zn(II) ion in early phase of contact time was profoundly explained by Bangham's equation and film diffusivity (D^f). Intraparticle or pore diffusion (D_p) of Zn(II) ion inside the pores of CDS was rate limiting step at the later stage of contact time. Furthermore, the thermodynamic study on sorption of metal ion delineated the fact that the Zn(II) sorption on the surface of CDS was spontaneous, endothermic together with increased entropy at solid liquid interface.     

Removal of Copper,Nickel, and Zinc Ions from Electroplating Rinse Water

Removal of copper, nickel, and zinc ions from synthetic electroplating rinse water was investigated using cationic exchange resin (Ceralite IR 120). Batch ion exchange studies were carried out to optimize the various experimental parameters (such as contact time, pH, and dosage). Influence of co‐existing cations, chelating agent EDTA on the removal of metal ion of interest was also studied. Sorption isotherm data obtained at different experimental conditions were fitted with Langmuir, Freundlich, Redlich–Peterson, and Toth models. A maximum adsorption capacity of 164 mg g^?1 for Cu(II), 109 mg g^?1 for Ni(II), and 105 mg g^?1 for Zn(II) was observed at optimum experimental conditions according to Langmuir model. The kinetic data for metal ions adsorption process follows pseudo second‐order. Presence of EDTA and co‐ions markedly alters the metal ion removal. Continuous column ion exchange experiments were also conducted. The breakeven point of the column was obtained after recovering effectively several liters of rinse water. The treated rinse water could be recycled in rinsing operations. The Thomas and Adams–Bohart models were applied to column studies and the constants were evaluated. Desorption of the adsorbed metal ions from the resin column was studied by conducting a model experiments with Cu(II) ions loaded ion exchange resin column using sulfuric acid as eluant. A novel lead oxide coated Ti substrate dimensionally stable (DSA) anode was prepared for recovery of copper ions as metal foil from regenerated liquor by electro winning at different current densities (50–300 A cm^?2).     

Selective Separation and Preconcentration of Fe(III) and Zn(II) Ions by Solvent Extraction Using a New Triketone Reagent

A simple, rapid, and accurate method was developed for separation and preconcentration of trace levels of iron(III) and zinc(II) ions in environmental samples. Methyl‐2‐(4‐methoxy‐benzoyl)‐3‐(4‐methoxyphenyl)‐3‐oxopropanoylcarbamate (MMPC) has been proposed as a new complexing agent for Fe(III) and Zn(II) ions using solvent extraction prior to their determination by flame atomic absorption spectrometry (FAAS). Fe(III) and Zn(II) ions can be selectively separated from Fe(II), Pb(II), Co(II), Cu(II), Mn(II), Cr(III), Ni(II), Cd(II), Ag(I), Au(III), Pd(II), Cr(VI), and Al(III) ions in the solution by using the MMPC reagent. The analytical parameters such as pH, sample volume, shaking time, amount of MMPC reagent, volume of methyl isobutyl ketone (MIBK), effect of ionic strength, and type of back extractant were investigated. The recovery values for Fe(III) and Zn(II) ions were greater than 95% and the detection limits for Fe(III) and Zn(II) ions were 0.26 and 0.32 µg L^?1, respectively. The precision of the method as the relative standard deviation changed between 1.8 and 2.1%. Calibration curves have a determination coefficient (r²) of at least 0.997 or higher. The preconcentration factor was found to be 100. Accuracy of the method was checked by analyzing of a certified reference material and spiked samples. The developed method was applied to several matrices such as water, hair, and food samples.     

Response Surface Modeling of Cu(II) Removal from Electroplating Waste by Adsorption: Application of Box–Behnken Experimental Design

The use of kaolinite‐based clay minerals as a low‐cost natural adsorbent for the removal of Cu(II) from electroplating waste leachate was studied. Batch experiments were conducted to determine the effects of varying adsorbent loading, initial pH, adsorbent dosage, and contact time. Box–Behnken design with three variables like initial pH, adsorbent dosage, and contact time at three different levels was studied to identify a significant correlation between the effects of these variables to the amount of Cu(II) adsorbed. The methodology identifies the principal experimental variables, which have the greatest effect on the adsorption process. After optimizing the input variables by using Simplex algorithm, the adsorption of Cu(II) was maximal (99.9% with a maximum (positive) standard deviation of 9.4) at pH 6.24, adsorbent dosage of 0.83 g L^?1, and contact time of 97 min, respectively. Furthermore, the experimental values are in good agreement with predicted values, the correlation coefficient and adjusted correlation coefficients were found to be 0.96 and 0.87, respectively.     

Determination of Cu,Fe, and Ni in Spices after Preconcentration on Diaion‐HP 20 Resin as Their Zincon Complexes

In this work, a new separation–preconcentration method was developed for the determination of trace amounts of Cu(II), Ni(II), and Fe(III) by flame atomic absorption spectrometry (FAAS). Analytes were complexed by using zincon (2‐[2‐[alpha(2‐hydroxy‐5‐sulfophenylazo) benzylidene] hydrazino] benzoic acid sodium salt). The analyte ions were quantitatively adsorbed on a Diaion HP‐20 resin at pH 5. The retained metal ions on the resin were eluted by acetone. The analytical parameters such as pH of the sample, eluent type and volume, sample volume, and flow rates of the solution and the eluent were investigated. The influences of concomitant ions on the recoveries of the analytes were also examined. The instrumental detection limits for the analytes after application of the presented solid‐phase extraction procedure were in the range of 0.72–1.41 µg/L. The validation of the presented procedure was checked by analyzing certified reference material of SRM1515 Apple Leaves. The procedure was performed by analyzing some spice samples.     

Determination of Copper in Water Samples after Solid‐phase Extraction Using Dimethylglyoxime‐modified Silica

This work describes the modification of silica gel with dimethylglyoxime, in order to prepare an effective sorbent for the preconcentration and determination of copper. The sorption capacity of dimethylglyoxime‐modified silica‐gel (DMGMS) was 71.37 mg g^–1 and the optimum pH for the quantitative recovery of copper was found to be 5.0. The optimum flow rate, sorbent amount, and sample volume were 1 mL min^–1, 300 mg, and 50 mL, respectively. 10 mL of 0.1 mol L^–1 HCl was the most suitable eluent. The detection limit of copper was 6.0 ng mL^–1. The recommended method, for the determination of copper, is simple and reliable, without any notable matrix effect and can be successfully applied to environmental water samples. Copper recovery in the range from 99–100% was obtained from seawater and thermal spring water using this method. The method was applied to standard reference materials, NIST‐1515 (apple leaves) and NIST‐1643e (simulated fresh water), for the determination of copper and the results were in good agreement with certified values.     

Experimental Designs Applied to Desorption of Dichromate Ions after Separation and Preconcentration from Natural and Industrial Water by Modified Nano‐Alumina

Nano‐alumina modified by 9‐aminoacridine was used as a sorbent for separation and determination of dichromate ions from water. Statistical method, based on surface response design, has been used for the optimization of dichromate ions elution from 9‐aminoacridine nano‐alumina. The adsorbed dichromate ions were found to be eluted quantitatively with 0.8 mol L^?1 KCl in 1.6 mol L^?1 NaOH which optimized by response surface design. Under optimum conditions, the accuracy, precision (relative standard deviation, RSD%) and R‐square of the method were calculated as >98, <3, and >94%, respectively. Remarkable agreement between experimental and theoretical data was confirmed the predicted assumption. The method was applied to the simultaneous determination of dichromate in natural and industrial water samples. We also examined the retention of dichromate anions in the presence of Cl^?, , and anions at pH 3.     

Separation and Preconcentration of Cobalt Using a New Schiff Base Derivative on Amberlite XAD‐7

In this study, a new solid‐phase extraction procedure has been developed for preconcentration and determination of Co ions in different water samples by flame atomic absorption spectrometry (FAAS). Cobalt was preconcentrated as N,N′‐bis(pyridine‐2‐yl‐methyl)benzene‐1,4‐diamine (Co‐BPMBDA) from sample solutions using a column containing Amberlite XAD‐7 and was determined. In order to achieve the best performance for the method, effects of several parameters such as pH, concentrations of ligand, sample flow rate, eluent, and matrix ions on the method efficiency were investigated. Under optimum conditions, the preconcentration factor was found to be 200 for 1000 mL waters samples. Detection limit based on the 3S_b criterion was calculated as 0.24 µg/L for 100 mL of sample solution and relative standard deviation was found to be 1.8%. The method was applied to determine the trace amounts of cobalt in water samples.     

Determination of Trace Levels of Nickel and Manganese in Soil,Vegetable, and Water

A simple and reliable method for rapid and selective extraction and determination of trace levels of Ni²⁺ and Mn²⁺ was developed by ionic liquid (IL) based dispersive liquid–liquid microextraction coupled to flame atomic absorption spectrometry (FAAS) detection. The proposed method was successfully applied to the preconcentration and determination of nickel and manganese in soil, vegetable, and water samples. After preconcentration, the settled IL‐phase was dissolved in 100 µL of ethanol and aspirated into the FAAS using a home‐made microsample introduction system. Injection of 50 µL of each analyte into an air–acetylene flame provided very sensitive spike‐like and reproducible signals. Effective parameters such as pH, amount of IL, volume of the disperser solvent, concentration of the chelating agent, and effect of salt concentration were inspected by a (2^5‐1) fractional factorial design to identify the most important parameters and their interactions. Under optimum conditions, preconcentration of 10 mL sample solution permitted the detection of 0.93 µg L^?1 Ni²⁺ and 0.52 µg L^?1 Mn²⁺ with enrichment factors 77.2 and 82.6 for Ni²⁺ and Mn²⁺, respectively. The accuracy of the procedure was evaluated by analysis of a certified reference material (CRM TMDW‐500, drinking water).     

Dispersive Liquid–Liquid Microextraction for Preconcentration and Determination of Nickel in Water

A method for the determination of nickel in water was developed. The procedure involves preconcentration of nickel by using dispersive liquid–liquid microextraction. The Ni(II) ions were extracted in chloroform in the form of complex with the reagent 2‐(2′‐benzothiazolylazo)‐p‐cresol. Ethanol was used as the disperser solvent. After injection of the extracting mixture in a solution of nickel, a cloudy mixture was observed. A quick centrifugation induces phase separation and thus the settling of rich phase. The nickel content in the rich phase is measured by flame atomic absorption spectrometry. Under optimal conditions, the limit of detection and quantification obtained were 1.4 and 4.7 µg L^?1, respectively. Some parameters used to characterize preconcentration systems, such as enrichment factor and consumption index were calculated and resulted in 29 and 0.34 mL, respectively. After optimization of variables and determination of analytical characteristics, the method was used for the analysis of certified reference materials (BCR‐713: wastewater, effluent and BCR‐414: plankton) and real water samples.