Factorial design optimization of experimental variables in the on-line separation/preconcentration of copper in water samples using solid phase extraction and ICP-OES determination.

An on-line preconcentration procedure using solid phase extraction (SPE) for the determination of copper in different water samples by inductively coupled plasma optical emission spectrometry (ICP-OES) is proposed. The copper was retained on a minicolumn filled with ethyl vinyl acetate (EVA) at pH 8.0 without using any complexing reagent. The experimental optimization step was performed using a two-level full factorial design. The results showed that pH, sample loading flow rate, and their interaction (at the tested levels) were statistically significant. In order to determine the best conditions for preconcentration and determination of copper, a final optimization of the significant factors was carried out using a central composite design (CCD). The calibration graph was linear with a regression coefficient of 0.995 at levels near the detection limit up to at least 300 µg L(-1). An enrichment factor (EF) of 54 with a preconcentration time of 187.5 s was obtained. The limit of detection (3σ) was 0.26 µg L(-1). The sampling frequency for the developed methodology was about 15 samples/h. The relative standard deviation (RSD) for six replicates containing 50 µg L(-1) of copper was 3.76%. The methodology was successfully applied to the determination of Cu in tap, mineral, river water samples, and in a certified VKI standard reference material.

Preconcentration and speciation of chromium in drinking water samples by coupling of on-line sorption on activated carbon to ETAAS determination.

An on-line flow injection (FI) preconcentration-electrothermal atomic absorption spectrometry (ETAAS) method is developed for trace determination of chromium in drinking water samples by sorption on a conical minicolumn packed with activated carbon (AC) at pH 5.0. The chromium was removed from the minicolumn with 1.0% (v/v) nitric acid. An enrichment factor (EF) of 35-fold for a sample volume of 10ml was obtained. The detection limit (DL) value for the preconcentration method proposed was 3.0ngl(-1). The precision for 10 replicate determinations at the 0.5mugl(-1) Cr level was 4.0% relative standard deviation (R.S.D.), calculate with the peak heights obtained. The calibration graph using the preconcentration system for chromium was linear with a correlation coefficient of 0.9992 at levels near the detection limits up to at least 50mugl(-1). The method was successfully applied to the determination of Cr(III) and Cr(VI) in drinking water samples.

On-line preconcentration/determination of copper in parenteral solutions using activated carbon by inductively coupled plasma optical emission spectrometry.

A method for the on-line preconcentration of copper using a minicolumn packed with activated carbon and its subsequent determination by inductively coupled plasma optical emission spectrometry (ICP-OES) coupled with flow injection (FI) was studied. In order to determinate the copper concentration present in parenteral solutions; it was retained on activated carbon (AC) at pH 9.5. A sensitivity enrichment factor of 30-fold was obtained with respect to the copper determination by ICP-OES without preconcentration. The detection limit for the preconcentration of 25 ml of sample was 0.1 microgl(-1). The precision for the ten replicate determinations at the 2.5 microgl(-1) Cu level was 3.0% relative standard deviation (R.S.D.), calculated with the peak heights. The calibration graph using the preconcentration method for cooper species was linear with a correlation coefficient of 0.9996 at levels near the detection limits up to at least 200 microgl(-1). The method was successfully applied to the determination of copper in parenteral solutions.

Optimization of the preconcentration system of cadmium with 1(2-thiazolylazo)-p-cresol using a knotted reactor and flame atomic absorption spectrometric detection.

The present paper proposes an on-line preconcentration procedure for cadmium determination in drinking water samples. It is based on the precipitation of cadmium(II) ions on a knotted reactor (KR) using 1(2-thiazolylazo)-p-cresol (TAC) as complexing reagent. The optimization step was performed using a full factorial design involving the variables: pH, eluent concentration (nitric acid) and TAC concentration. The results of this experiment demonstrated that these variables at chosen levels are not statistically significant. Under optimized experimental established conditions, analytical parameters for the preconcentration method were: a detection limit of 40.0 ng/l, precision as relative standard deviation (RSD) of 1.2 and 1.0%, for cadmium concentration of 2.5 and 20.0 microg/l, respectively. The preconcentration factor considering the slopes of the analytical curves with and without preconcentration is 23 for a sample volume of 10 ml. This system shows a sampling frequency of 25 h(-1). In order to check the accuracy, the standard reference material, NIST SRM 1643d trace elements in water was analyzed. A comparison, using t-test demonstrates that there is not significant difference among the achieved results with proposed method and the certified values. The addition/recovery experiments in the samples analyzed demonstrated the accuracy and applicability of the system developed for cadmium determination in water samples.

On-line preconcentration and determination of nickel in natural water samples by flow injection-inductively coupled plasma optical emission spectrometry (FI-ICP-OES).

An on-line nickel preconcentration and determination system implemented with inductively coupled plasma optical emission spectrometry (ICP-OES) associated to flow injection (FI) was studied. Trace amounts of nickel were preconcentrated by sorption on a conical minicolumn packed with activated carbon (AC) at pH 5.0. The nickel was removed from the minicolumn with 20% nitric acid. An enrichment factor of 80-fold for a sample volume of 50 ml was obtained. The detection limit (DL) value for the preconcentration method proposed was 82 ng l(-1). The precision for ten replicate determinations at the 0.5 microg l(-1) Ni level was 3.0% relative standard deviation (R.S.D.), calculated from the peak heights obtained. The calibration graph preconcentration method for nickel was linear with a correlation coefficient of 0.9997 at levels near the detection limits (DL) up to at least 100 microg l(-1). The method was successfully applied to the determination of nickel in natural water samples.

On-line preconcentration system for bismuth determination in urine by flow injection hydride generation inductively coupled plasma atomic emission spectrometry.

An on-line bismuth preconcentration and determination system implemented with hydride generation inductively coupled plasma atomic emission spectrometry (HG-ICP-AES) associated to flow injection (FI) was studied. Quinolin-8-ol and Amberlite XAD-7 were used for the retention of bismuth, at pH 4.5. The bismuth complex was removed from the micro-column with nitric acid. The detection limit value for the preconcentration of 100 ml of aqueous solution was 0.02 ng ml(-1) with a relative standard deviation (R.S.D.) of 3.5%, calculated from the peak heights obtained. The calibration graph using the preconcentration system for bismuth was linear with a correlation coefficient of 0.999 at levels near the detection limits up to at least 100 ng ml(-1). The method was successfully applied to the determination of bismuth in human urine samples.

On-line complexation of zinc with 5-Br-PADAP and preconcentration using a knotted reactor for inductively coupled plasma atomic emission spectrometric determination in river water samples.

An on-line zinc preconcentration and determination system implemented with inductively coupled plasma atomic emission spectrometry (ICP-AES) associated with flow injection (FI) was studied. The zinc was retained as zinc-2-(5-bromo-2-pyridylazo)-5-diethylaminophenol (Zn-(5-Br-PADAP)) complex at pH 9.2. The zinc complex was removed from the knotted reactor (KR) with 30% v/v nitric acid. An enrichment factor of 42 was obtained for the KR system with respect to ICP-AES using pneumatic nebulization. The detection limit for the preconcentration of 10 mL of aqueous solution was 0.09 microg/L. The precision for 10 replicate determinations at the 5 microg/L Zn level was 2.3% relative standard deviation (RSD), calculated with the peak heights obtained. The calibration graph using the preconcentration system for zinc was linear with a correlation coefficient of 0.9997 at levels near the detection limits up to at least 100 microg/L. The method was succesfully applied to the determination of zinc in river water samples.