Flow injection online spectrophotometric determination of uranium after preconcentration on XAD-4 resin impregnated with nalidixic acid

In this work, spectrophotometer was used as a detector for the determination of uranium from water, biological, and ore samples with a flow injection system coupled with solid phase extraction. In order to promote the online preconcentration of uranium, a minicolumn packed with XAD-4 resin impregnated with nalidixic acid was utilized. The system operation was based on U(VI) ion retention at pH 6 in the minicolumn at flow rate of 15.2 mL min^?1. The uranium complex was removed from the resin by 0.1 mol dm^?3 HCl at flow rate of 3.2 mL min^?1 and was mixed with arsenazo III solution (0.05 % solution in 0.1 mol dm^?3 HCl, 3.2 mL min^?1) and driven to flow through cell of spectrophotometer where its absorbance was measured at 651 nm. The influence of chemical (pH and HCl (as eluent and reagent medium) concentration) and flow (sample and eluent flow rate and preconcentration time) parameters that could affect the performance of the system as well as the possible interferents was investigated. At the optimum conditions for 60 s preconcentration time (15.2 mL of sample volume), the method presented a detection limit of 1.1 μg L^?1, a relative standard deviation (RSD) of 0.8 % at 100 μg L^?1, enrichment factor of 30, and a sample throughput of 42 h^?1, whereas for 300 s of the preconcentration time (76 mL of sample volume), a detection limit of 0.22 μg L^?1, a RSD of 1.32 % at 10 μg L^?1, enrichment factor of 150, and a sampling frequency of 11 h^?1 were reported.     

Solid phase extraction and determination of Cr(III) by spectrophotometry using cefaclor as a complexing reagent and FAAS

The present study reports on the application of modified groundnut shell as a new, easily prepared, and stable sorbent for the extraction of trace amount of Cr(III) in aqueous solution. 2-Hydroxybenzaldiminoglycine was immobilized on groundnut shells in alkaline medium and then used as a solid phase for the column preconcentration of Cr(III). The elution was carried out with 3 mL of 2 mol?L^?1 HCl. The amount of eluted Cr(III) was determined by spectrophotometry using cefaclor as a complexing reagent and by flame atomic absorption spectrometry (FAAS). Different experimental variables such as pH, amount of solid sorbent, volume and concentration of eluent, sample and eluent flow rate, and interference of other metal ions on the retention of Cr(III) were studied. Under the optimized conditions, the calibration curves were found to be linear over the concentration range of 13–104 and 10–75 μg?L^?1 with a detection limit of 3.64 and 1.24 μg?L^?1 for spectrophotometric method and FAAS, respectively. An enrichment factor of 200 and RSD of ±1.19–1.49 % for five successive determinations of 25 μg?L^?1 were achieved. The column preconcentration was successfully applied to the analysis of tap water and underground water samples.     

FIA-coupled spectrophotometric method for determination of Cr (VI) traces in natural waters: application of in-line dissolution of 1,5-diphenylcarbazide after heat treatment and activated alumina as adsorbent for preconcentration

This work proposes the quantification of Cr (VI) ions in natural waters in trace level, using activated alumina (Al₂O₃) as preconcentration support, controlled in-line dissolution of the solidified chromophore diphenylcarbazide after heat treatment and spectrophotometric detection. The manifold ensures high sensitivity of analytical response, good repeatability, and stability. In this work, optimization of experimental conditions of a flow injection system was chosen as the parameters for greater sensitivity and better selectivity. The selected optimized conditions were 0.30 mol L^?1 for H₂SO₄ concentration, system flow rate as 0.40 mL min^?1, sample injection volume of 192.50 μL, 2 min for preconcentration time, and 0.10 mol L^?1 for eluent concentration. The analytical curves obtained for real sample analysis show linear range from 0.192 to 0.961 μM, linear correlation coefficient R?=?0.9997 and LOD?=?0.024 μM. The preconcentration factor of about four times was obtained through the passage of 800 μL of a standard solution containing 0.961 μM of Cr (VI) through mini-column of preconcentration followed by elution at 192.5 μL of NH₄OH 0.1 mol L^?1 solution. The solid chromogenic reagent presented high durability (weeks in daily use with mass of 0.0993 g) and good reproducibility in analytical signal. The reactivation of the mini-column of alumina should be executed after ten injections of eluent, using 800 μL of HCl 0.02 mol L^?1 solution in flow through the same. Each cycle of injection and elution of the sample takes about 5 min on the proposed terms. Despite the length of each cycle still be high, low concentrations can be detected using a technique of relatively low cost. This is due in part, the association dissolution of the chromogenic reagent directly in the line and the preconcentration step. Another important factor is the economy of reagent chromogenic, low generation of reject contributing to better quality of the environment, and the high potential for applications to work in field.     

Monitoring of trace amounts of heavy metals in different food and water samples by flame atomic absorption spectrophotometer after preconcentration by amine-functionalized graphene nanosheet

We are introducing graphene oxide modified with amine groups as a new solid phase for extraction of heavy metal ions including cadmium(II), copper(II), nickel(II), zinc(II), and lead(II). Effects of pH value, flow rates, type, concentration, and volume of the eluent, breakthrough volume, and the effect of potentially interfering ions were studied. Under optimized conditions, the extraction efficiency is >97 %, the limit of detections are 0.03, 0.05, 0.2, 0.1, and 1 μg L^?1 for the ions of cadmium, copper, nickel, zinc, and lead, respectively, and the adsorption capacities for these ions are 178, 142, 110, 125, and 210 mg g^?1. The amino-functionalized graphene oxide was characterized by thermogravimetric analysis, transmission electron microscopy, scanning electron microscopy, and Fourier transform infrared spectrometry. The proposed method was successfully applied in the analysis of environmental water and food samples. Good spiked recoveries over the range of 95.8–100.0 % were obtained. This work not only proposes a useful method for sample preconcentration but also reveals the great potential of modified graphene as an excellent sorbent material in analytical processes.     

The efficiency of Amberlite XAD-4 resin loaded with 1-(2-pyridylazo)-2-naphthol in preconcentration and separation of some toxic metal ions by flame atomic absorption spectrometry

A selective method has been developed for the determination of trace amount of metal ions after preconcentration on 1-(2-pyridylazo)-2-naphthol loaded Amberlite XAD-4 resin. The chelating resin was characterized on the basis of infra red spectra, thermal and chemical stability, and hydrogen ion capacity. High preconcentration factor of 160?C400 up to a low preconcentration limit of 10 ??g L^???1 has been achieved for almost all the metals. The chelating resin was highly selective even in the presence of large concentrations of alkali and alkaline earth metals and various matrix components. Chromatographic separation of metal ions in binary mixtures has been accomplished. The analytical utility of the resin for metal ions was explored by analyzing natural water and standard reference materials.     

Determination of Pb(II), Zn(II), Cd(II), and Co(II) ions by flame atomic absorption spectrometry in food and water samples after preconcentration by coprecipitation with Mo(VI)-diethyldithiocarbamate

A new, simple, and rapid separation and preconcentration procedure, for determination of Pb(II), Cd(II), Zn(II), and Co(II) ions in environmental real samples, has been developed. The method is based on the combination of coprecipitation of analyte ions by the aid of the Mo(VI)–diethyldithiocarbamate–(Mo(VI)-DDTC) precipitate and flame atomic absorption spectrometric determinations. The effects of experimental conditions like pH of the aqueous solution, amounts of DDTC and Mo(VI), standing time, centrifugation rate and time, sample volume, etc. and also the influences of some foreign ions were investigated in detail on the quantitative recoveries of the analyte ions. The preconcentration factors were found to be 150 for Pb(II), Zn(II) and Co(II), and 200 for Cd(II) ions. The detection limits were in the range of 0.1–2.2 μg L^?1 while the relative standard deviations were found to be lower than 5 % for the studied analyte ions. The accuracy of the method was checked by spiked/recovery tests and the analysis of certified reference material (CRM TMDW-500 Drinking Water). The procedure was successfully applied to seawater and stream water as liquid samples and baby food and dried eggplant as solid samples in order to determine the levels of Pb(II), Cd(II), Zn(II), and Co(II) ions.     

The use of silica gel modified with allyl 6-methyl-4-phenyl-2-thioxo-1,2,3,4-tetrahydropyrimidine-5-carboxylate for selective separation and preconcentration of lead in environmental samples

The aim of the present work is the assessment of a new sorbent, prepared using silica gel coated with a pyrimidine derivative (allyl 6-methyl-4-phenyl-2-thioxo-1,2,3,4-tetrahydropyrimidine-5-carboxylate), for extraction and preconcentration trace amount of lead from different samples prior to determination by flame atomic absorption spectrometry. Common coexisting ions did not interfere with the separation and determination of lead at pH?6, so that lead ion completely adsorbed on the column. The limit of detection based on three times the standard deviation of the blank was found to be 0.53 ng?mL^?1 in original solution. Obtained sorption capacity for 1 g sorbent was 5.0 mg Pb. The linearity was maintained in the concentration range of 0.1–30.0 ng?mL^?1 for the concentrated solution. Eight replicate determinations of 2.0 μg?mL^?1 of lead in the final solution gave relative standard deviation of ±2.6 %. The proposed method was successfully applied to the determination trace amounts of lead in the environmental samples such as carrot, rice, zardchoobe, and real water samples.     

Determination of ultra-trace amounts of cadmium by ET-AAS after column preconcentration with a new sorbent of modified MWCNTs

The present research reports on the application of modified multiwalled carbon nanotubes as a new, easily prepared, and stable solid sorbent for the column preconcentration of ultra-trace amounts of cadmium in aqueous solution. Multiwalled carbon nanotubes were oxidized with concentrated HNO₃ and modified with 2-(5-bromo-2-pyridylazo)-5-diethylaminophenol and then were used as a solid phase for the column preconcentration of Cd(II). Elution was carried out with 0.5 mol?L^?1 HNO₃. The amount of eluted Cd(II) was measured using electrothermal atomic absorption spectrometry. Various parameters such as pH, sample and eluent flow rate, eluent concentration, breakthrough volume, and interference of a great number of anions and cations on the retention of analyte on sorbent were studied. Under the optimized conditions, the calibration graph was linear in the range of 0.67 ng?L^?1 to 5.0 μg?L^?1 and the detection limit (3S_b, n?=?7) was 0.14 ng?L^?1 in initial solution. A preconcentration factor of 300 and relative standard deviations of ±3.6 % for seven successive determinations of 3 ng of Cd(II) were achieved. The column preconcentration was successfully applied to the analysis of river water, waste water, and Persian Gulf water sample.     

Rapid spectrophotometric determination of trace amounts of palladium in water samples after dispersive liquid–liquid microextraction

A simple, rapid, and efficient dispersive liquid–liquid microextraction method, followed by UV–Vis spectrophotometry was developed for the preconcentration and determination of Pd ions in water samples. Pd ions react with α-furildioxime (chelating agent) to form a hydrophobic complex. Various parameters were altered to study and optimize their effects on the extraction efficiency, such as pH, ligand concentration, the type and volume of extraction and dispersive solvents, extraction time, and salt concentration. Under optimized conditions, the method exhibited an enrichment factor (C _org/C _aq) of 25 and recovery more than 98 % within a very short extraction time. The linearity of the method ranged from 10 to 200 μg?L^?1. The limit of detection was 1.1 μg?L^?1. The relative standard deviation for the concentration of 100 μg?L^?1 of Pd was 2.3 % (n?=?10). Finally, the developed method was successfully applied to the extraction and determination of Pd in tap, river, mineral, and sea water samples.     

Preconcentration of metal ions through chelation on a synthesized resin containing O, O donor atoms for quantitative analysis of environmental and biological samples

Nascent Amberlite XAD-4 has been used as the polymeric support for the synthesis of a stable extractor of metal ions, by incorporating phthalic acid through azo bridging. Elemental analyses and infra-red spectral and thermal studies were carried out for its characterization. The water regain value and hydrogen ion capacity were found to be 12.50 and 5.75 mmol g^?1, respectively. The optimum pH range for the maximum sorption of Ni(II), Mn(II), Cu(II), Zn(II), Cd(II), Cr(III), and Co(II) was observed at pH 5.5–8.0 with the corresponding half-loading time (t _1/2) of 9, 5, 9, 9, 3, 9, and 5 min, respectively. The preconcentration factor for Ni(II), Mn(II), Cu(II), Zn(II), Cd(II), Cr(III), and Co(II) are 190, 190, 190, 180, 180, 160, and 160, with the corresponding limit of preconcentration in the range of 5.25–6.25 μg L^?1. The detection limits, for flame atomic absorption spectrophotometry, were found to be 0.62, 0.60, 0.65, 0.75, 0.72, 0.84, and 0.85 μg L^?1, respectively. Method has been successfully applied to the analysis of water samples, multivitamin formulations, infant food substitutes, hydrogenated oil, and fishes.     

Solid phase extraction of Cd,Pb, Ni,Cu, and Zn in environmental samples on multiwalled carbon nanotubes

A simple and sensitive solid phase extraction (SPE) method on multiwalled carbon nanotubes (MWCNTs) is presented for the determination of cadmium, lead, nickel, copper, and zinc at trace levels combined with flame atomic absorption spectrometry. The effects of parameters like pH, sample volume, sample and eluent flow rates, eluent concentration, and volume and type of eluent on the recovery of trace elements was examined. The metals retained on the nanotube at pH 6.5 as α-benzoin oxime complexes were eluted by 10 mL 2 M HNO₃ in acetone. The influence of matrix ions on the developed method was also evaluated. The preconcentration factor of the method was found to be 50. The detection limits for Cd(II), Pb(II), Ni(II), Cu(II), and Zn(II) were found as 1.7, 5.5, 6.0, 2.3, and 2.4 μg L^?1, respectively. To test the accuracy of the method, the method was applied to TMDA-70 fortified lake water and Spinach 1570A standard reference materials. Addition recovery studies were applied to tap water and cracked wheat samples, and determination of the analyte elements was carried out in some food samples with good results.     

2-Nitroso-1-naphthol as a selective reagent for preconcentration of cobalt by vortex assisted combined with solidification of organic droplet and its determination by flame atomic absorption spectrometry

Highly rapid and selective vortex-assisted liquid–liquid microextraction based on solidification of organic drop has been used for determination of cobalt ion. 2-Nitroso-1-naphthol (2N1N) was used as a selective complexing agent to form stable cobalt–2N1N complex which can be extracted with 1-undecanol at a short time by the assistance of vortex agitator system followed by its determination using flame atomic absorption spectrometry. In vortex assisted, vigorous vortex stream as well as the vibrant effect of vortex system cause very fine droplets of extraction solvent to be produced and extraction occurred at a short time. Some parameters influencing the extraction process such as pH of samples, concentration of 2-nitroso-1-naphthol, extraction solvent volume, extraction time, ionic strength and surfactant addition, as well as interferences were evaluated in detail and optimum conditions were selected. At the optimum conditions, the calibration curve was linear in the range of 15 to 400 μg L^?1 of cobalt ions. The relative standard deviation based on ten replicate analysis of sample solution containing 50 μg L^?1 of cobalt was 3.4 %. The detection limit (calculated as the concentration equivalent to three times of the standard deviation of the blank divided by the slope of the calibration curve after preconcentration) was 5.4 μg L^?1. The accuracy of the proposed method was successfully evaluated by the analysis of certified reference materials. This selective and highly rapid method was used for determination of cobalt ions in different water samples.     

The use of rapidly synergistic cloud point extraction for the separation and preconcentration of trace amounts of Ni (II) ions from food and water samples coupling with flame atomic absorption spectrometry determination

A novel improved preconcentration method known as rapidly synergistic cloud point extraction (RS-CPE) was established for nickel preconcentration and determination prior to its determination by flame atomic absorption spectrometry. In this work, the traditional CPE pattern was changed and greatly simplified in order to be applicable in metal extraction and detection. This method was accomplished in room temperature in 1 min. Non-ionic surfactant Triton X-114 was used as extractant. Octanol worked as cloud point revulsant and synergic reagent. The various parameters affecting the extraction and preconcentration of nickel such as sample pH, 2,2′-Furildioxime concentration, amounts of octanol, amounts of Triton X-114, type of diluting solvent, extraction time, and ionic strength were investigated and optimized. Under optimal conditions, the calibration curve showed an excellent linearity in the concentration range of 2–200 μg L^?1, and the limit of detection was 0.6 μg L^?1 for nickel. The developed method was successfully applied for the determination of nickel in food and water samples. The results showed that, the proposed method can be used as a cheap, rapid, and efficient method for the extraction and preconcentration of nickel from real samples.     

Novel solid-phase extractor based on functionalization of multi-walled carbon nano tubes with 5-aminosalicylic acid for preconcentration of Pb(II) in water samples prior to determination by ICP-OES

New solid-phase extractor (MWCNTs-5-ASA) was synthesized via covalent immobilization of 5-aminsalicylic acid onto multi-walled carbon nanotubes (MWCNs). The success of the functionalization process was confirmed using Fourier transform infrared spectroscopy, scanning electron microscope, and surface coverage determination. Batch experiments were conducted as a function of pH to explore MWCNTs-5-ASA efficiency to extract several metal ions viz., Cr(III), Fe(III), Co(II), Ni(II), Cu(II), Zn(II), Cd(II) and Pb(II). It was found that Pb(II) exhibits the highest extraction percentage with maximum adsorption capacity 32.75 mg g^?1. Its binding performance was well fitted with Langmuir sorption isotherm. On the other hand, the selective separation and preconcentration of trace Pb(II) under dynamic conditions prior to determination by inductively coupled plasma-optical emission spectrometry was investigated under different parameters. These included the rate of flow and volume of sample solution, in addition to the type of the eluate, its volume and concentration. The effect of a variety of foreign ions on the recovery percentage was also evaluated. Trace Pb(II) ions present in 500 mL aqueous solution adjusted to pH 4.0 were retained on 50 mg of MWCNTs-5-ASA and completely eluted using 4.0 mL of 2 M HNO₃. The limit of detection and the precision of the method were 0.25 ng mL^?1 and 2.8 %, respectively (N?=?5). This methodology has been applied for the determination of Pb(II) in water samples with good results.     

Distribution of natural radionuclides in surface soils in the vicinity of abandoned uranium mines in Serbia

The activity concentrations of natural radionuclides in soils from the area affected by uranium mining at Stara Planina Mountain in Serbia were studied and compared with the results obtained from an area with no mining activities (background area). In the affected area, the activity concentrations ranged from 1.75 to 19.2 mg kg^?1 for uranium and from 1.57 to 26.9 mg kg^?1 for thorium which is several-fold higher than those in the background area. The Th/U, K/U, and K/Th activity ratios were also determined and compared with data from similar studies worldwide. External gamma dose rate in the air due to uranium, thorium, and potassium at 1 m above ground level in the area affected by uranium mining was found to be 91.3 nGy h^?1, i.e., about two-fold higher than that in background area. The results of this preliminary study indicate the importance of radiological evaluation of the area and implementation of remedial measures in order to prevent further dispersion of radionuclides in the environment.     

Simultaneous quantification of Bi(III) and U(VI) in environmental water samples with a complicated matrix containing organic compounds

Trace amounts of bismuth(III) and uranium(VI) can be simultaneously determined in a single scan by adsorptive cathodic stripping voltammetry in the presence of cupferron as a complexing agent. Optimal conditions were found to be: 0.1 mol?L^?1 acetate buffer (pH 5.3), 5?×?10^?5?mol?L^?1 cupferron, accumulation potential of ?0.25 V, and accumulation time of 30 s. The linear range of Bi(III) and U(VI) was observed over the concentration range from 2?×?10^?9 to 2?×?10^?7?mol?L^?1 and from 1?×?10^?8 to 5?×?10^?7?mol?L^?1, respectively. The influence of the main components of real water samples such as foreign ions and organic substances (surface active substances, humic substances) was precisely investigated. The method was applied to the simultaneous measurements of bismuth and uranium in natural water samples.     

Spectrophotometeric determination of trace amounts of Al3+ ion in water samples after cloud point extraction using quinizarin as a complexing agent

In this study, cloud point extraction was used for the preconcentration of Al³⁺ ion after the complex formation with 1,4-dihydroxy-9,10-anthraquinone (Quinizarin [QUIN]), and subsequent analysis by spectrophotometeric method, using Triton X-114 as surfactant. The optimal extraction and reaction conditions were studied (i.e., pH?=?5.5, 0.1 mM QUIN, Triton X-114?=?0.1 % (w/v)), and the analytical characteristics of the method (e.g., limit of detection, linear range, preconcentration, and enrichment factors) were obtained. Linearity was obeyed in the range of 3.33–166.67 ng ml^?1 of Al³⁺ ion. The detection limit of the method was 2.09 ng ml^?1 for Al³⁺ ion. The interference effect of some anions and cations was also tested. The method was applied to determine Al³⁺ ion in water samples.     

Silica glass modified with flavonoid derivatives for preconcentration of some toxic metal ions in water samples and their determination with ICP-MS

Quercetin (3,3^′,4^′,5,7-pentahydroxyflavone) chemically bonded through pyran rearrangement on modified controlled pore silica glass (QCPSG) with a capacity 0.213 mmol/g was used for solid phase extraction of some toxic metal and metalloid ions. The newly designed QCPSG quantitatively sorbs As(V), Cd(II), Hg(II), and Pb(II) at the pH range 7.5–8.5 after 10 min of stirring. HCl (1 mol L^???1) instantaneously elutes all the metal ions. The sorption capacity of the ion collector is 0.42, 0.46, 0.53, and 0.49 mmol g^???1 for As(V), Cd(II), Hg(II), and Pb(II), respectively, whereas the preconcentration factor is 200. The effect of NaCl, Na₂SO₄, NaF, NaBr, Na₃PO₄, and other interfering salts on the sorption of metal ions (50 μg L^???1) was reported. Analytical detection limits of As(V), Cd(II), Hg(II), and Pb(II) were 4.18, 2.44, 15.86, and 25.00 pg mL^???1, respectively. QCPSG was used in the separation of the investigated metal ions from some natural water samples collected from diverse origins followed by determination by inductively coupled plasma–mass spectrometry. The data were compared with those obtained by the standard methods of determination using atomic absorption (hydride generation, HGAAS and after solvent extraction with ammonium pyrolidine dithiocarbamate/methyl isobutyl ketone). The suggested solid phase extraction method was found accurate with no random error.     

Evaluation of surface water quality in aquatic bodies under the influence of uranium mining (MG, Brazil)

The quality of the water in a uranium-ore-mining area located in Caldas (Minas Gerais State, Brazil) and in a reservoir (Antas reservoir) that receives the neutralized acid solution leaching from the waste heaps generated by uranium mining was investigated. The samples were collected during four periods (October 2008, January, April and July 2009) from six sampling stations. Physical and chemical analyses were performed on the water samples, and the data obtained were compared with those of the Brazilian Environmental Standards and WHO standard. The water samples obtained from waste rock piles showed high uranium concentrations (5.62 mg L^?1), high manganese values (75 mg L^?1) and low average pH values (3.4). The evaluation of the water quality at the point considered the limit between the Ore Treatment Unit of the Brazilian Nuclear Industries and the environment (Consulta Creek) indicated contamination by fluoride, manganese, uranium and zinc. The Antas reservoir showed seasonal variations in water quality, with mean concentrations for fluoride (0.50 mg L^?1), sulfate (16 mg L^?1) and hardness (20 mg L^?1) which were low in January, evidencing the effect of rainwater flowing into the system. The concentrations for fluoride, sulfate and manganese were close or above to the limits established by current legislation at the point where the treated mining effluent was discharged and downstream from this point. This study demonstrated that the effluent discharged by the UTM affected the quality of the water in the Antas reservoir, and thus the treatments currently used for effluent need to be reviewed.     

On-site solid-phase extraction and application to in situ preconcentration of heavy metals in surface water

An on-site solid-phase extraction, consisting of the sorption, the separation and the elution function units, was designed for in situ preconcentration of heavy metals ions. The D401 resin powder was employed as sorbent to capture Pb²⁺, Cu²⁺, Zn²⁺, Cd²⁺, Co²⁺, and Ni²⁺, and then they desorbed with 2 mol/L nitric acid as eluent. Under the optimized conditions, these heavy metals ions in West Lake, Taihu Lake, and Yangtze River of China were captured and then determined by ICP-OES with the recovery of 92.5% to 111.5%. The on-site solid-phase extraction achieved a quick preconcentration of heavy metals to avoid the transport and storage of a large volume water sample. It is suitable for in situ monitoring of water quality in mountains, tablelands or other remote areas.