Akhmad Sabarudin

A chitosan resin possessing a phenylarsonic acid moiety (phenylarsonic acid type chitosan resin) was developed for the collection and concentration of trace uranium prior to inductively coupled plasma (ICP) atomic emission spectrometry (AES) measurement. The adsorption behavior of 52 elements was systematically examined by packing it in a minicolumn and measuring the elements in the effluent by ICP mass spectrometry. The resin could adsorb several cationic species by a chelating mechanism, and several oxo acids, such as Ti(IV), V(V), Mo(VI), and W(VI), by an anion-exchange mechanism and/or a chelating mechanism. Especially, U(VI) could be adsorbed almost 100% over a wide pH region from pH 4 to 8. Uranium adsorbed was easily eluted with 1 M nitric acid (10 mL), and the 25-fold preconcentration of uranium was achieved by using a proposed column procedure, which could be applied to the determination of trace uranium in seawater by ICP-AES. The limit of detection was 0.1 ng mL−1 for measurement by ICP-AES coupled with 25-fold column preconcentration.

A new chelating resin using chitosan as a base material was synthesized. Functional moiety of 2-amino-5-hydroxy benzoic acid (AHBA) was chemically bonded to the amino group of cross-linked chitosan (CCTS) through the arm of chloromethyloxirane (CCTS-AHBA resin). Several elements, such as Ag, Be, Cd, Co, Cu, Ni, Pb, U, V, and rare earth elements (REEs), could be adsorbed on the resin. To use the resin for on-line pretreatment, the resin was packed in a mini-column and installed into a sequential-injection/automated pretreatment system (Auto-Pret System) coupled with inductively coupled plasma-atomic emission spectrometry (ICP-AES). The sequential-injection/automated pretreatment system was a laboratory-assembled, and the program was written using Visual Basic software. This system can provide easy operation procedures, less reagent consumption, as well as less waste production.Experimental variables considered as effective factors in the improvement sensitivity, such as an eluent concentration, a sample and an eluent flow rate, pH of samples, and air-sandwiched eluent were carefully optimized. The proposed system provides excellent on-line collection efficiency, as well as high concentration factors of analytes in water samples, which results in highly sensitive detection of ultra-trace and trace analysis. Under the optimal conditions, the detection limits of 24 elements examined are in the range from ppt to sub-ppb levels. The proposed method was validated by using the standard reference material of a river water, SLRS-4, and the applicability was further demonstrated to the on-line collection/concentration of trace elements, such as Ag, Be, Cd, Co, Cu, Ni, Pb, U, V, and REEs in water samples.

ABSTRACT A novel chitosan-based resin functionalized with threonine moiety was synthesized, and applied to the collection/concentration of Mo, V and Cu in environmental water samples, followed by their determination using inductively coupled plasma-atomic emission spectrometer (ICP-AES). The synthesized resin, cross-linked chitosan-threonine (CCTS-Thr), showed good adsorption behavior toward trace amounts of Mo, V and Cu in a wide pH range. The adsorbed elements can be easily eluted using 2molL(-1) of nitric acid, and their recoveries were found to be 90-100%. The CCTS-Thr was packed in a mini-column, which was then installed in a computer-controlled auto-pretreatment system (Auto-Pret System) for on-line trace elements collection and determination by ICP-AES. Experimental parameters related to the improvement of sensitivity and reproducibility were optimized. The limits of detection (LODs) for target metals were found to be in sub-ppb level. The proposed method with CCTS-Thr resin was successfully applied to the determination of Mo, V and Cu in environmental water samples. The recovery test showed that common matrices which exist in environmental water samples did not interfere with the determination.

Chitosan resin functionalized with 3,4-dihydroxy benzoic acid (CCTS-DHBA resin) was used as a packing material for flow injection (FI) on-line mini-column preconcentration in combination with inductively coupled plasma-atomic emission spectrometry (ICP-AES) for the determination of trace elements such as silver, bismuth, copper, gallium, indium, molybdenum, nickel, uranium, and vanadium in environmental waters. A 5-mL aliquot of sample (pH 5.5) was introduced to the minicolumn for the adsorption/preconcentration of the metal ions, and the collected analytes on the mini-column were eluted with 2 M HNO3, and the eluates was subsequently transported via direct injection to the nebulizer of ICP-AES for quantification. The parameters affecting on the sensitivity, such as sample pH, sample flow rate, eluent concentration, and eluent flow rate, were carefully examined. Alkali and alkaline earth metal ions commonly existing in river water and seawater did not affect the analysis of metals. Under the optimum conditions, the method allowed the determination of metal ions with detection limits of 0.08 ng mL−1 (Ag), 0.9 ng mL−1 (Bi), 0.07 ng mL−1 (Cu), 0.9 ng mL−1 (Ga), 0.9 ng mL−1 (In), 0.08 ng mL−1 (Mo), 0.09 ng mL−1 (Ni), 0.9 ng mL−1 (U), and 0.08 ng mL−1 (V). By using 5 mL of sample solution, the enrichment factor and collection efficiency were 8–12 fold and 96–102%, respectively, whereas the sample throughput was 7 samples/hour. The method was validated by determining metal ions in certified reference material of river water (SLRS-4) and nearshore seawater (CASS-4), and its applicability was further demonstrated to river water and seawater samples.

A simple method to estimate the amounts of ultra-trace metal impurities in nitric acid reagents has been developed. The determination of sixty-four metals in nitric acid was accomplished by direct measurements of 0.1 M nitric acids accurately diluted with ultrapure water by ICP-MS. Though accurate metal concentration could not be obtained for all of the elements, we could effectively evaluate the nitric acid quality by comparing the ion counts of the samples, ultrapure water and standard metal solutions for a calibration prepared with Ultrapur nitric acid.

A chitosan resin derivatized with 3,4-dihydroxybenzoic acid moiety (CCTS-DHBA resin) was newly synthesized for the collection/concentration of trace uranium by using cross-linked chitosan (CCTS) as base material, and the adsorption behavior of uranium as well as 60 elements on the resin was examined by passing the sample solutions through a mini-column packed with the resin. After the elution of the collected elements on the resin with 1 M HNO3, the eluates were measured by inductively coupled plasma-mass spectrometry (ICP-MS).The CCTS-DHBA resin can adsorb several metal cations and several oxoanionic elements at appropriate pH. Among these metal ions, uranium shows an excellent adsorption behavior on this resin. Uranium as UO22+ species can be adsorbed on the resin by chelating mechanism with adsorption capacity of 330 mg g−1 resin. Through the column treatment, the complete removal of large amounts of alkali and alkaline earth matrices without any loss of adsorption efficiency over prolonged usage were achieved with this resin.The CCTS-DHBA resin was applied to the adsorption/collection of uranium in tap water, river water and seawater samples with satisfactory results. The validation of the proposed method was carried out by analyzing uranium in the standard reference materials of SLRS-4, CASS-4, and NASS-5 after passing through the CCTS-DHBA resin, and the results showed good agreement with the certified values.