Use of an aminated Amberlite XAD-4 column coupled to flow injection cold vapour generation atomic absorption spectrometry for mercury speciation in water and fish tissue samples.

An aminated Amberlite XAD-resin as a solid phase extractant was tested for speciation of inorganic mercury, Hg(II) and methylmercury, MeHg(I) in water and fish tissue samples. It was found that Hg(II) and MeHg(I) ions could be simultaneously retained by a column filled with AAXAD-4 resin at pH 4 and the sequential quantitative elutions of Hg(II) and MeHg(I) were achieved using 10 mL of 0.1%(m/v) thiourea in 3%(v/v) HCl and 10 mL of 6 mol L-1 HCl, respectively. Hg(II) in the eluent was directly determined and MeHg(I) in the second eluent is quantified using FI-CVG-AAS after its oxidative digestion with KMnO4. The limits of detection for Hg(II) and MeHg(I) ions were found to be 0.148 and 0.157 µg L-1, respectively. The method was validated by analysing a certified reference material. The relative errors for Hg(II), MeHg(I) and T-Hg were in range of -1.8% and -3.2%.

Chromium Speciation Using an Aminated Amberlite XAD-4 Resin Column Combined with Microsample Injection-Flame Atomic Absorption Spectrometry.

Amberlite XAD-4 resin (AXAD-4) was chemically modified to an aminated Amberlite XAD-4 (AAXAD-4) resin and characterized by infrared spectroscopy. AAXAD-4 resin was used as an efficient solid phase for the preconcentration and speciation of Cr(III) and Cr(VI) ions by column technique. The concentration of chromium species was determined by microsample injection system-flame atomic absorption spectrometer (MIS-FAAS). Selective retention of Cr(III) ions was achieved at pH 8.0 and eluted using 1.0 mL of 3.0 mol L-1 HCl and 1.0 mL of 2.0 mol L-1 NaOH, successively, at the flow rate of 5.0 mL min-1. The maximal sorption capacity of AAXAD-4 resin for Cr(III) ions was found to be 67.0 mg g-1. The limit of detection (LOD) and limit of quantitation (LOQ) for Cr(III) ions were found to be 0.041 and 0.131 ∆g L-1, respectively, with preconcentration factor (PF) of 375 and relative standard deviation (RSD) of 3.75% (n = 11). The method was validated using certified reference materials (CRMs) and successfully applied to the real samples, spiked with Cr(III) and Cr(VI) ions.

Solid Phase Extraction Preconcentration Method for Simultaneous Determination of Cadmium, Lead, and Nickel in Poultry Supplements.

A new simple, selective, and economical preconcentration method was developed for the determination of Cd, Pb, and Ni in poultry antibiotics and supplements. The proposed preconcentration procedure is based on SPE using 8-hydroxyquinoline and Amberlite IRC-50 resin as complex and adsorbent, respectively. The determination was carried out by microsample injection system (MIS) flame atomic absorption spectroscopy (FAAS). Several analytical parameters were examined, including pH, type of resin, amount of resin, type of eluent, eluent volume, flow rate, sample volume, and interference of diverse ions. Under optimum experimental conditions, LODs and LOQs were 0.017 and 0.055, 0.016 and 0.53, and 0.074 and 0.248 µg/L for Cd, Pb, and Ni, respectively, with RSDs < 2.50%. The accuracy of SPE-MIS-FAAS was successfully tested by the standard addition method, with obtained recoveries >99%. The proposed method was successfully applied for the determination of Cd, Pb, and Ni in poultry supplement and antibiotic samples.

Determination of total chromium at ultratrace levels in water and soil samples by coprecipitation microsample injection system flame atomic absorption spectrometry.

A simple, robust, and novel analytical procedure was developed for determination of total chromium (Cr) by carrier element coprecipitation (CECP) coupled microsample injection system with flame atomic absorption spectrometry. For this method, Cr(III) was oxidized by Ce(SO4)2 in acidic media, and the resulting solution formed coprecipitates with ammonium pyrrolidine dithiocarbamate in the presence of Ce(III). The effective parameters of the developed method have been optimized and studied in detail. The LOD and enrichment factor of CECP were 2.13 µg/L and 100 ± 2.8, respectively, with 40 mL initial volumes. The RSD values (n = 6) were <5%. The applicability and accuracy of CECP were estimated by the analysis of total Cr in industrial effluent wastewater by the standard addition method (recoveries > 96%). The accuracy of total Cr by CECP after microwave acid digestion was checked by using a certified reference material (GBW 07309 Stream Sediment). The difference between the found and certified values was not significant (P > 0.05). The proposed method was successfully applied to natural drinking water, industrial effluent wastewater, and the exchangeable fraction of garden soil from Denizli, Turkey.

Solid-phase chelate extractive preconcentration of heavy metal ions prior to their ultratrace determination by microsample injection system coupled flame atomic absorption spectrometry.

Chromosorb-105 resin/1-(2-pyridylazo)-2-naphthol (PAN) system was developed for solid phase chelate extractive preconcentration of heavy metal ions. The metal ions on Chromosorb-105 resin column were eluted with 3.0 mL of 2.0 mol L-1 HNO3 and determined by microsample injection system coupled flame atomic spectrometry (MIS-FAAS) using 75.0 µL of sample solution for single element determination. The influence of pH, resin amount, reagent amount, flow rate and volume of eluent and sample solution was optimized. The quantitative recoveries (≥95%) of Fe(III), Zn(II), Cu(II) and Pb(II) ions were achieved at pH 9; resin amount, 700 mg; reagent amount, 6.0 µmol; flow rate of eluent and sample solution, 1.0 mL min-1 and 5.0 mL min-1, respectively. The limit of detection and limit of quantification of understudied analytes were found to be 0.17-1.74 µg L-1 and 0.40-2.98 µg L-1, respectively with preconcentration factor of 150-300. The proposed method was validated by analysis of waste water (BCR-715) as a certified reference material. The method was applied successfully for ultratrace determination of studied metal ions in tap water and hot spring water samples.

Ultratrace Determination of Cr(VI) and Pb(II) by Microsample Injection System Flame Atomic Spectroscopy in Drinking Water and Treated and Untreated Industrial Effluents.

Simple and robust analytical procedures were developed for hexavalent chromium (Cr(VI)) and lead (Pb(II)) by dispersive liquid-liquid microextraction (DLLME) using microsample injection system coupled with flame atomic absorption spectrophotometry (MIS-FAAS). For the current study, ammonium pyrrolidine dithiocarbamate (APDC), carbon tetrachloride, and ethanol were used as chelating agent, extraction solvent, and disperser solvent, respectively. The effective variables of developed method have been optimized and studied in detail. The limit of detection of Cr(VI) and Pb(II) were 0.037 and 0.054 µg/L, respectively. The enrichment factors in both cases were 400 with 40 mL of initial volumes. The relative standard deviations (RSDs, n = 6) were <4%. The applicability and the accuracy of DLLME were estimated by the analysis of Cr(VI) and Pb(II) in industrial effluent wastewater by standard addition method (recoveries >96%). The proposed method was successfully applied to the determination of Cr(VI) and Pb(II) at ultratrace levels in natural drinking water and industrial effluents wastewater of Denizli. Moreover, the proposed method was compared with the literature reported method.

Determination of cobalt, nickel and iron at trace level in natural water samples by in-column chelation-reversed phase high-performance liquid chromatography.

This paper reports the utilization of 4-(2-pyridylazo) resorcinol (PAR) as a chelating reagent for in-column derivatization and the determination of trace Co, Fe, and Ni ions by reversed-phase high-performance liquid chromatography with photodiode array detector. A good separation of Co, Fe, and Ni chelates were achieved by using an Inertsil ODS-3 column and a mobile phase, consisted of methanol-THF-water mixture (50:5:45) containing ammonium acetate buffer (pH 5.0) and PAR. After full optimization, good repeatability of retention times (relative standard deviation (RSD) < 0.05%) and peak areas (RSD < 1.7%) was achieved as well as a good linearity (r (2) > 0.9991). The detection limits (S/N = 3), expressed as micrograms per liter, were 0.50 (Co), 9.07 (Fe), and 2.00 (Ni). The applicability and the accuracy of the developed method were estimated by the analysis of spiked water samples and certified reference material BCR 715 wastewater-SRM.

Solid-phase extraction of some heavy metal ions on a double-walled carbon nanotube disk and determination by flame atomic absorption spectrometry.

A new preconcentration method was developed for the determination of trace amounts of Cu(II), Fe(III), Pb(II), Ni(II), and Cd(II) on a double-walled carbon nanotube disk. 4-(2-Thiazolylazo) resorcinol was used as a complexing reagent. The effects of parameters, including pH of the solutions, amounts of complexing reagent, eluent type, sample volume, flow rates of solutions, and matrix ions were examined for quantitative recoveries of the studied analyte ions. The retained metal ions were eluted by 2 M HNO3. The LOD values for the analytes were in the range of 0.7-4.4 microg/mL. Natural water samples and standard reference materials were analyzed by the presented method.

Selective preconcentration of thallium species as chloro and iodo complexes on Chromosorb 105 resin prior to electrothermal atomic absorption spectrometry.

A selective preconcentration method was described for the determination of inorganic thallium species by electrothermal atomic absorption spectrometry (ETAAS). Thallium(III) and thallium(I) as chloro and iodo complexes were selectively retained by a column containing 0.5 g of Chromosorb 105 resin and quantitatively eluted by 10 mL of pure acetone. The calibration graph was linear with a correlation coefficient of 0.997 at levels near the detection limit and up to at least 0.8 µg L(-1). The detection limits for the determination of total thallium and thallium(III) employing the proposed method by ETAAS were estimated as three values of the standard deviations, 0.050 µg L(-1) and 0.034 µg L(-1), respectively. Verification of the accuracy was carried out by the analysis of standard reference materials (GBW 07402 soil, NIST 2710 Montana soil, GBW 07309 and GBW 07310 stream sediments). The relative errors were found to be in the range of -7.7% to +4.8%. The relative standard deviations were generally found to be below 10%. The effect of potential interfering ions on the determination was studied. The proposed method was successfully applied to the determination of total thallium in five different brand cements, soils around two cement plants and metallic zinc samples. The speciation of thallium(I) and thallium(III) was applied to synthetic solutions.

Solid phase extractive preconcentration coupled to gas chromatography-atomic emission detection for the determination of chlorophenols in water samples.

Solid-phase extraction (SPE) followed by derivatization and gas chromatography-atomic emission detection (GC-AED) was evaluated for the determination of five chlorophenols (CPs) in water samples. The derivatization was based on the esterification of phenolic compounds with ferrocenecarboxylic acid. The determination of the derivatized phenols was performed by GC-AED in the iron selective detection mode at 302 nm. The described method was tested on spiked water samples.The overall method gave detection limits of 1.6-3.7 ng L(-1) and recoveries of 90.9-104.5% for the examined mono- to trichlorophenols in 10 mL water samples. The CPs extracted from a 10 mL water sample with SPE were concentrated into 100 µL of organic solvent, a preconcentration factor of 100. The method was applied to lake and tap water samples, and CP contents between 6 and 51 ng L(-1) in lake water and between below the detection limit and 8 ng L(-1) in tap water were found for different CPs. The method is quick, simple and gives excellent recoveries, limits of detection and standard deviations.

Determination of some organophosphorus and azole group pesticides in water samples by dispersive liquid-liquid microextraction coupled with GC/MS.

A dispersive liquid-liquid microextraction (DLLME) procedure coupled with GC/MS detection is described for preconcentration and determination of some organophosphorus and azole group pesticides from water samples. Experimental conditions affecting the DLLME procedure were optimized by means of an experimental design. A mixture of 60 microL chlorobenzene (extraction solvent) and 750 microL acetonitrile (disperser solvent), 3.5 min extraction time, and 7.5 mL aqueous sample volume were chosen for the best recovery by DLLME. The linear range was 1.6-32 microg/L. The LOD ranged from 48.8 to 68.7 ng/L. The RSD values for organophosphorus and azole group pesticides at spiking levels of 3, 6, and 9 microg/L in water samples were in the range of 1.1-12.8%. The applicability and accuracy of the developed method were determined by analysis of spiked water samples, and the recoveries of the analyzed pesticides from artesian, stream, and tap waters at spiking levels of 3, 6, and 9 microg/L were 89.3-105.6, 89.5-103.0, and 92.0-111.3%, respectively.

New use of polypyrrole-chloride for selective preconcentration of copper prior to its determination of flame atomic absorption spectrometry.

Polypyrrole-chloride was studied as a new sorbent for preconcentration of copper(II) using solid-phase extraction prior to determination by flame atomic absorption spectrometry. The sorbent showed an extremely high selectivity towards copper(II) as an anionic chelate, i.e. Cu (pyrocatechol violet)(2)(2-) in the pH range of 4-7. Copper(II) as Cu (pyrocatechol violet)(2)(2-) was selectively retained on a column containing 1.0 g of polypyrrole-chloride and quantitatively eluted by 3 mL of 2.0 mol L(-1) nitric acid. The calibration graph was linear with a correlation coefficient of 0.999 at levels near the detection limit and up to at least 50 microg L(-1). When applied for preconcentration and determination of copper in tap water, waste water and hot spring water, the recoveries were found to be 96, 101 and 95%, respectively, with high precision (% relative standard deviation <4%) and low detection limit (0.87 microg L(-1)). Verification of the accuracy was carried out by the analysis of a standard reference material (BCR 715 wastewater-SRM). The relative error was +3.33%. The proposed method was successfully applied to the determination of copper in tap water, waste water and hot spring water samples.

Development of a coprecipitation system for the speciation/preconcentration of chromium in tap waters.

A method for the speciation of chromium(III), chromium(VI) and determination of total chromium based on coprecipitation of chromium(III) with dysprosium hydroxide has been investigated and applied to tap water samples. Chromium(III) was quantitatively recovered by the presented method, while the recovery values for chromium(VI) was below 10%. The influences of analytical parameters including amount of dysprosium(III), pH, centrifugation speed and sample volume for the quantitative precipitation were examined. No interferic effects were observed from alkali, earth alkali and some transition metals for the analyte ions. The detection limits (k=3, N=15) were 0.65 microg/L for chromium(III) and 0.78 microg/L for chromium(VI). The validation of the presented method was checked by the analysis of certified reference materials.

Selective extraction of chromium(VI) using a leaching procedure with sodium carbonate from some plant leaves, soil and sediment samples.

Speciation of chromium in some plant leaves, soil and sediment samples was carried out by selective leaching of Cr(VI) using a sodium carbonate leaching procedure. Total chromium from the samples was extracted using aqua regia and oxidative acid digestion, respectively. The concentrations of chromium species in the extracts were determined using by graphite furnace atomic absorption spectrometry (GFAAS). Uncoated graphite furnace tubes were used as an atomizer. Due to the presence of relatively high amounts of Na(2)CO(3) in the resulting samples, the possible influences of Na(2)CO(3) on the absorbance signals were checked. There is no interference of Na(2)CO(3) on the chromium absorbance up to 0.1 mol L(-1) Na(2)CO(3). A limit of detection (LOD) for determination of Cr(VI) in 0.1 Na(2)CO(3) solution by GFAAS was found to be 0.93 microg L(-1). The procedure was applied to environmental samples. The relative standard deviation, R.S.D. as precision for 10 replicate measurements of 20 microL(-1) Cr in processed soil sample was 4.2%.

Extractable trace metals content of dust from vehicle air filters as determined by sequential extraction and flame atomic absorption spectrometry.

A modified four-step sequential extraction procedure developed within the Standards, Measurement, and Testing Program (formally the Community Bureau of Reference) of the European Commission was applied to determine the distribution of Cd, Cu, Fe, and Mn in air filter dust samples collected from vehicles. The four fractions were acid-soluble, reducible, oxidizable, and residual. These fractions have the advantage of providing better insight into the mechanism of association of metals in the dust. The determination of trace metals in dust samples was performed by flame atomic absorption spectrometry. The results obtained after applying the sequential extraction scheme indicated that Cu was the most abundant metal in the organic and residual fractions of the dust matrix. Fe was found mainly in the residual fraction, and the major amounts of Mn and Cd were present in the acid-soluble and bound-to-carbonate fraction. The mean values of Cd, Cu, Fe, and Mn were found to be 15.58, 33.54, 1625, and 180 microg/g, respectively. The results obtained are in agreement with data reported in the literature.

Factorial design for multivariate optimization of preconcentration system for spectrophotometric phosphorus determination.

The present paper proposes a preconcentration procedure for phosphorus determination by using ultraviolet-visible spectrophotometer. It is based on the formation of phosphomolybdate and its reduction to molybdenum blue. Phosphorus extraction as phosphomolybdenum blue complex was performed onto Amberlite XAD-4. The optimization step was carried out using two-level full factorial design. Three variables (resin amount, sample volume, flow rate) were regarded as factors in the optimization. The relative standard deviation was 2% at 0.08 microg mL(-1). The limit of detection was found to be 2.23 microg L(-1) (N=15). The proposed solid-phase extraction procedure was applied to phosphorus in some fruit leaves, natural waters, and a standard reference material (SRM 1515 apple leaves).

Carrier element-free coprecipitation with 3-phenly-4-o-hydroxybenzylidenamino-4,5-dihydro-1,2,4-triazole-5-one for separation/preconcentration of Cr(III), Fe(III), Pb(II) and Zn(II) from aqueous solutions.

A separation/preconcentration procedure, based on the coprecipitation of Cr(3+), Fe(3+), Pb(2+) and Zn(2+) ions using a new organic coprecipitant, 3-phenly-4-o-hydroxybenzylidenamino-4,5-dihydro-1,2,4-triazole-5-one (POHBAT) without adding any carrier element has been developed. The method, thus, has been called carrier element-free coprecipitation (CEFC). The resultant concentrated elements were determined by flame atomic absorption spectrometric determinations. The influences of some analytical parameters including pH of the solution, amount of the coprecipitant, standing time, centrifugation rate and time, sample volume and diverse ions were investigated on the quantitative recoveries of analyte ions. The validation of the present preconcentration procedure was performed by the analysis of two certified reference materials. The recoveries of understudy analytes were found in the range of 93-98%, while the detection limits were calculated in the range of 0.3-2.0 microg L(-1). The precision of the method evaluated as relative standard deviation (R.S.D.), was in the range of 3-7% depend on the analytes. The proposed method was successfully applied to environmental samples for the determination of the analytes.

Determination of lead in wine and rum samples by flow injection-hydride generation-atomic absorption spectrometry.

A method for direct determination of lead in wine and rum samples was developed, using a flow injection hydride generation system coupled to an atomic absorption spectrometer with flame-quartz atomizer (FI-HG-AAS). Lead hyride (PbH(4)) was generated using potassium ferricyanide (K(3)Fe(CN)(6)), as oxidant and sodium tetrahydroborate (NaBH(4)) as reductant. Samples were acidified to 0.40% (v/v) HCl for wine and to 0.30% (v/v) HCl for rum, which were then mixed on-line with 3% (m/v) K(3)Fe(CN)(6) solution in 0.03% (v/v) HCl prior to reaction with 0.2% (m/v) alkaline NaBH(4) solution. Lead contents of a rum and two different red wine samples were determined by FI-HG-AAS agreed with those obtained by ICP-MS. The analytical figures of merit of method developed were determined. The calibration curve was linear up to 8.0 microg L(-1) Pb with a regression coefficient of 0.998. The relative error was lower than 4.58%. The relative standard deviation (n=7) was better than 12%. A detection limit of 0.16 microg L(-1) was achieved for a sample volume of 170 microL.

Simultaneous preconcentration of Co(II), Ni(II), Cu(II), and Cd(II) from environmental samples on Amberlite XAD-2000 column and determination by FAAS.

A new method for the preconcentration of some trace metals (Co, Ni, Cu, and Cd) as complexed with ammonium pyrrolidynedithiocarbamate (APDC) was developed using a mini-column filled with Amberlite XAD-2000 resin. Metal contents were determined by flame atomic absorption spectrometry (FAAS) after the metal complexes accumulated on the resin were eluted with 1M HNO(3) in acetone. The effects of the analytical parameters such as sample pH, quantity of complexing agent, eluent type, resin quantity, sample volume, sample flow rate, and matrix ions were investigated on the recovery of the metals from aqueous solutions. The relative standard deviation (R.S.D.) of the method was <6%. The validation of the method was confirmed using two certified reference materials (CRM TMDW-500 Drinking Water and CRM SA-C Sandy Soil C). The method was successfully applied to some stream waters and mushroom samples from Eastern Black Sea Region (Trabzon city) of Turkey.

On-line preconcentration of copper as its pyrocatechol violet complex on Chromosorb 105 for flame atomic absorption spectrometric determinations.

An on-line solid phase extraction method for the preconcentration and determination of Cu(II) by flame atomic absorption spectrometry (FAAS) has been described. It is based on the adsorption of copper(II) ion onto a home made mini column of Chromosorb 105 resin loaded with pyrocatechol violet at the pH range of 5.0-8.0, then eluted with 1 mol L(-1) HNO(3). Several parameters, such as pH of the sample solution, amount of Chromosorb 105 resin, volume of sample and eluent, type of eluent, flow rates of sample and eluent, governing the efficiency and throughput of the method were evaluated. The concentration of the copper ion detected after preconcentration was in agreement with the added amount. At optimized conditions, for 15 min of preconcentration time (30 mL of sample volume), the system achieved a detection limit of 0.02 microg L(-1), with relative standard deviation 1.1% at 0.03 microg mL(-1) copper. The present method was found to be applicable to the preconcentration of Cu(II) in natural water samples.