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LAPORAN PENELITIAN HIBAH BERSAING TAHUN ANGGARAN 2009

PENGEMBANGAN METODE SPESIASI KROMIUM, ARSEN, SELENIUM SECARA OTOMATIS MENGGUNAKAN MINI KOLOM GANDA DAN

COMPUTER CONTROLLED - AUTOMATED PRETREATMENT SYSTEM (CC-APS)

Ir. Adam Wiryawan, MS Dr. Akhmad Sabarudin Dr. Barlah Rumhayati

Dibiayai oleh Direktorat Jenderal Pendidikan Tinggi, Departemen Pendidikan Nasional Melalui DIPA Universitas Brawijaya Nomor: 0174.0/023-04.2/XV/2009

Tanggal 31 Desember 2008 dan berdasarkan SK Rektor Nomor: 147/SK/2009

UNIVERSITAS BRAWIJAYA

NOVEMBER 2009

BIDANG : MIPA (Kimia)

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RINGKASAN DAN SUMMARY

Spesiasi kromium (Cr), arsen (As), dan selenium (Se) merupakan hal yang sangat penting. Cr (III) merupakan mikro-nutrien yang diperlukan oleh tubuh, sedangkan Cr (VI) bersifat toksik dan sebagai agen yang dapat menyebabkan kanker. Sementara itu, As (III) dan As (V) jauh lebih berbahaya dan beracun dibandingkan bentuk organiknya. Pada penelitian ini dikembangkan metode spesiasi Cr (III) dan Cr (VI), As (III) dan As (V), serta Se (IV) dan Se (VI) dalam sampel air minum kemasan yang beredar di pasaran dan air sungai secara otomatis (fully automatic) menggunakan mini kolom ganda (4 cm x 2 mm. i.d) yang diisi dengan selective chelating material. Mini-kolom ganda sebagai jantung spesiasi diletakkan pada Computer Controlled – Automated Preteratment System (CC-APS). Dengan sistem ini, maka spesiasi Cr (III) dan Cr (VI), As (III) dan As (V), serta Se (IV) Se (VI) dilakukan secara fully automatic, mudah pengoperasiannya, less reagent consumption, less waste. Pada tahun pertama dilakukan spesiasi kromium melalui ekstraksi fase padat dengan resin pengkelat Analig Cr-02 dan ME-02. Parameter sistem yang dioptimasi adalah pH sampel, kecepatan alir sampel dan eluen, serta volume dan konsentasi eluen. Sistem yang telah dioptimasi diaplikasikan untuk spesiasi kromium dari sampel air. Dari hasil penelian menunjukkan bahwa spesiasi Cr III dan Cr VI dapat dilakukan dengan menggunakan mini kolom dengan sistem CC-APS. Kondisi optimum meliputi: pH 3,5; flow rate sampel 30 ml/detik; konsentrasi eluen 2 mol/L; volume eluen HNO3 2 M 0,5 mL; flow rate eluen untuk Cr III 50 ml/detik; flow rate eluen utuk Cr VI 30 ml/detik. Metode spesiasi yang dikembangkan ini mempunyai tingkat ketepatan yang tinggi dan tidak dipengaruhi oleh adanya kation serta anion lain yang biasa ada dalam sampel air.

Speciation of chromium (Cr), arsenic (As) and selenium (Se) are important to be performed. For chromium spesies, Cr III is micro nutrient for living organism while Cr VI is toxic and cancer agent in environment. In addition, As III and As V inorganic are more toxic than its organic forms. This research develops a fully automatic speciation method for Cr III-Cr VI; As III-As V; and Se IV – Se VI in packed and river waters by using a double mini-column filled with selective chelating material. The column was placed in the computer controlled-automated pretreatment system (CC-APS). By using the system, spesiation could be fuly automatic carried out, easy for operation, less reagent consumption and less waste. For the first year of research, it has been developed a method for chromium speciation through solid phase extraction on the chelating resins of Analig Cr-02 and ME-02. System optimation was conducted on sampel pH, flow rate of sample and eluen; volume and concentration of eluen. Results showed that the system was optimum at sampel pH 3.5; sample flow rate of sample was 30 ml/second; eluent concentration was 2 mol/L, volume of 2 M HNO3 was 0.5 ml; flow rate of eluent for Cr III and Cr VI were 50 ml/second and 30 ml/second, respectively. The developed method has high accuracy and was not influenced by other commonly available of cations or anions in water sample.

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DAFTAR PUSTAKA

1. Anonymous. 2001. Assessing the Impact of Chromium in the Environment.

www.ccaresearch.org/tag12/present/CR_spec_Presentation_Jul-2001.ppt

2. Anonymous. 2006. Introduction to speciation analysis. www.appliedspeciation.com

3. Ali, A. and Aboul-Enein, H.Y. 2006. Instrumental methods in metals ion speciation. CRC Press. 4. Hu, W., Zheng, F., Hu, B., 2007, Simultaneous separation and speciation of inorganic As(III)/As(V) and Cr(III)/Cr(VI) in natural waters utilizing capillary microextraction on ordered mesoporous Al2O3 prior to their on- line determination by ICP-MS, Journal of Hazardous Materials, Vol. 151, p. 58-64 5. Nriagu, J.O. and Nieboer, E. 1998. Chromium in the natural and human enviroments. John Wiley and Sons.

6. Lin, T.S., 2007, Inorganic selenium speciation in groundwaters by solid phase extraction on Dowex 1X2, J. Hazardous Materials, Vol. 149, p. 80- 85

7. Sabarudin, A., Oshita, K., Oshima, M., Motomizu, S., 2005, Synthesis of chitosan resin possessing 3,4-diamino benzoic acid moiety for the collection/concentration of arsenic and selenium in water samples and their measurement by inductively coupled plasma-mass spectrometry, Analytica Chimica Acta, Vol. 542, p. 207-215

8. Sabarudin, A., Lenghor, N., Liping, Y., Furusho, Y., Motomizu, S., 2006,

Automated on-line preconcentration system for the determination of trace amounts of lead using Pb-selective resin and inductively coupled plasma-atomic emission spectrometry, Spectroscopy Letter, Vol. 39, p. 669-682

9. Sabarudin, A., Lenghor, N., Oshima, M., Hakim, L., Takayanagi, T., Gao, Y.H.,

Motomizu, S., 2007, Sequential-injection on-line preconcentration using chitosan resin functionalized with 2-amino-5-hydroxy benzoic acid for the determination of trace elements in environmental water samples by inductively coupled plasma-atomic emission spectrometry, Talanta, Vol. 72, p. 1609-1627

10. Sabarudin, A., Oshima, M., Motomizu, S. 2007, Advanced research on

development of computer-controlled fully automated online preconcentration system and its application to determination of trace element by ICP-AES using chitosan resins functionalized with 2-amino-5-hydroxy benzoic acid and 4-hydroxy phthalic acid moieties, Annual Research Report, Research Center for Advanced Technology (RCAT), Okayama University, Japan

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11. Sabarudin, A., Furusho, Y., Oshima, M., Wiryawan, A., Motomizu, S., 2007,

Automated Pretreatment System in Combination with Chitosan-Based Chelating Resins for Speciation of Cr (III) and Cr (VI) by ICP-AES, 14th International Conference on Flow Injection Analysis, Berlin, Germany.

12. Sulistyarti, H., Wiryawan, A., Rumhayati, B., Sulistyo, E., 2002, Pengembangan

metode analisis otomatis melalui pemberdayaan sell difusi gas dan teknik injeksi alir (gas diffusion-flow injection) untuk penentuan sianida dan tiosianat secara simultan, Laporan Penelitian Hibah Bersaing X/1 (No: 220/J10.2/PG/2002).

13. Sumida, T., Sabarudin, A., Oshima, M., Motomizu, S., 2006, Speciation of

chromium in seawater by ICP-AES with dual mini-columns containing chelating resin, Analytical Sciences., Vol. 22, p. 161-164.

14. Wiryawan, A., 1997, Flow Injection Analysis – Atomic Absorption

Spectrophotometry (FIA – AAS) for determination of Arsen in River water, NATURAL, Vol.1, p.57-63.

15. Wiryawan, A., 1999, Spectrophotometric method for determination of selenium

(Se) by catalytic system, NATURAL, Vol.3, p. 110-118

16. Wiryawan, A., 2000, Use of Flow Injection Analysis for continuous monitoring of River water quality, Laboratory Robotics and Automation, Vol. 12, p. 142 – 148.