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Title: Extraction and Quantitative Analysis of Iodine in Solid and Solution Matrixes

Abstract

129I is a contaminant of interest in the vadose zone and groundwater at numerous federal and privately-owned facilities. Several techniques have been utilized to extract iodine from solid matrices; however, all of them rely on two fundamental approaches: liquid extraction or chemical/heat facilitated volatilization. While these methods are typically chosen for their ease of implementation, they do not totally dissolve the solid. Because some of the iodine partitions onto the soil, extraction methods that do not result in total sample dissolution could underestimate the total iodine content of solid samples. We defined a method that produces complete solid dissolution and conducted laboratory tests to assess its efficacy to completely extract iodine from solid matrices. Testing consisted of potassium nitrate/potassium hydroxide fusion of the sample, followed by sample dissolution in a mixture of sulfuric acid and sodium bisulfite. Direct analysis of the dissolved sample was performed via inductively coupled plasma mass spectrometry (Perkin Elmer Elan DRC II) using a tertiary amine (Spectrasol CFA-C) carrier solution. The fusion extraction method resulted in complete sample dissolution of all solid matrices tested: sediment, glass samples containing low-levels of iodine, as well as tank waste material collected from the Hanford Site. Quantitative analysis of iodinemore » (127I and 129I) showed better than ? 10% accuracy for certified reference standards, with the linear operating range extending more than three orders of magnitude (0.005 to 5 ug/L). Extraction and analysis of four replicates of standard reference material (San Joaquin Soil) from the National Institute of Standards and Technology, Gaithersburg, MD, resulted in an average recovery of 98% with a relative percent deviation of 6%. This simple and cost-effective technique can be applied to solid samples of varying matrices with little or no adaptation.« less

Authors:
; ;
Publication Date:
Research Org.:
Pacific Northwest National Lab. (PNNL), Richland, WA (United States)
Sponsoring Org.:
USDOE
OSTI Identifier:
860414
Report Number(s):
PNNL-SA-45389
830403000; TRN: US0504910
DOE Contract Number:
AC05-76RL01830
Resource Type:
Journal Article
Resource Relation:
Journal Name: Analytical Chemistry; Journal Volume: 77; Journal Issue: 21
Country of Publication:
United States
Language:
English
Subject:
38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEAR CHEMISTRY; IODINE 129; EXTRACTION; QUANTITATIVE CHEMICAL ANALYSIS; SAMPLE PREPARATION; MATRIX MATERIALS; DISSOLUTION; Iodine; fusion; ICP-MS; extraction; analysis

Citation Formats

Brown, Christopher F., Geiszler, Keith N., and Vickerman, Tanya S.. Extraction and Quantitative Analysis of Iodine in Solid and Solution Matrixes. United States: N. p., 2005. Web. doi:10.1021/ac050972v.
Brown, Christopher F., Geiszler, Keith N., & Vickerman, Tanya S.. Extraction and Quantitative Analysis of Iodine in Solid and Solution Matrixes. United States. doi:10.1021/ac050972v.
Brown, Christopher F., Geiszler, Keith N., and Vickerman, Tanya S.. Tue . "Extraction and Quantitative Analysis of Iodine in Solid and Solution Matrixes". United States. doi:10.1021/ac050972v.
@article{osti_860414,
title = {Extraction and Quantitative Analysis of Iodine in Solid and Solution Matrixes},
author = {Brown, Christopher F. and Geiszler, Keith N. and Vickerman, Tanya S.},
abstractNote = {129I is a contaminant of interest in the vadose zone and groundwater at numerous federal and privately-owned facilities. Several techniques have been utilized to extract iodine from solid matrices; however, all of them rely on two fundamental approaches: liquid extraction or chemical/heat facilitated volatilization. While these methods are typically chosen for their ease of implementation, they do not totally dissolve the solid. Because some of the iodine partitions onto the soil, extraction methods that do not result in total sample dissolution could underestimate the total iodine content of solid samples. We defined a method that produces complete solid dissolution and conducted laboratory tests to assess its efficacy to completely extract iodine from solid matrices. Testing consisted of potassium nitrate/potassium hydroxide fusion of the sample, followed by sample dissolution in a mixture of sulfuric acid and sodium bisulfite. Direct analysis of the dissolved sample was performed via inductively coupled plasma mass spectrometry (Perkin Elmer Elan DRC II) using a tertiary amine (Spectrasol CFA-C) carrier solution. The fusion extraction method resulted in complete sample dissolution of all solid matrices tested: sediment, glass samples containing low-levels of iodine, as well as tank waste material collected from the Hanford Site. Quantitative analysis of iodine (127I and 129I) showed better than ? 10% accuracy for certified reference standards, with the linear operating range extending more than three orders of magnitude (0.005 to 5 ug/L). Extraction and analysis of four replicates of standard reference material (San Joaquin Soil) from the National Institute of Standards and Technology, Gaithersburg, MD, resulted in an average recovery of 98% with a relative percent deviation of 6%. This simple and cost-effective technique can be applied to solid samples of varying matrices with little or no adaptation.},
doi = {10.1021/ac050972v},
journal = {Analytical Chemistry},
number = 21,
volume = 77,
place = {United States},
year = {Tue Nov 01 00:00:00 EST 2005},
month = {Tue Nov 01 00:00:00 EST 2005}
}
  • A collaborative study was conducted, with 14 laboratories participating, to determine the method accuracy and precision of the proposed U.S. Environmental Protection Agency Methods 3560 and 8440. These methods involve the extraction of petroleum hydrocarbons from solid matrixes with supercritical carbon dioxide at 340 atm and 80 degrees C for 30 min (dynamic), collection of the extracted materials in tetrachloroethene (Method 3560), and analysis of the extracts by infrared (IR) spectrometry (Method 8440). The study design was based on the AOAC blind replicate design with balanced replicates. The study samples consisted of 4 solid matrixes that had petroleum hydrocarbon contentsmore » ranging from 614 to 32,600 mg/kg. Each of the 4 matrixes was extracted in triplicate, and the extracts were analyzed with 2 different IR spectrometers. In addition, each of the participating laboratories extracted a sample of unspiked clay soil, the same clay soil spiked with corn oil and reference oil at 1000 mg/kg each, and the same clay soil wetted to 30% water content and spiked with motor oil at 10,000 mg/kg (the latter 3 samples were extracted only once). Results indicated that the overall method accuracy for concentrations ranging from 614 to 32,600 mg/kg was 82.9%; the mean recoveries of petroleum hydrocarbons for each of the 4 solid matrixes ranged from 77.9 to 107% for analyses performed with the Perkin-Elmer Fourier transform IR spectrometer and from 75.9 to 101% for analyses performed with the Buck-Scientific IR spectrometer; the differences between the 2 instruments on a sample-by-sample basis were less than 17% for the total petroleum hydrocarbon determinations. The interlaboratory method precisions (RSDR) appeared to be matrix-dependent and ranged from 17.3 to 45.4% for analyses performed with the Perkin-Elmer Fourier transform IR spectrometer and from 16.7 to 47.9% for the Buck-Scientific IR spectrometer.« less
  • A method for the quail-quantitative evaluation of pentachlorophenol (PCP) in solid matrixes has been developed. The procedure is based on solid-liquid extraction of solid samples (leather or wood), followed by purification on a cyanopropyl column and determination of the preservative by second derivative UV spectroscopy considering the PCP A peak-through value (304-297 nm). The method allows rapid PCP determination in the concentration range 1-40 micrograms/mL; any matrix interference is avoided by the purification step and recoveries of the preservative were 99.12% (RSD% 0.13) for the leather matrix and 98.03 (RSD% 0.17) for the wood matrix.
  • Twenty-one water-soluble acid dyes, including eleven azo, five triphenylmethane four xanthene, one naphthol derivatives, used at practical concentrations for food coloration, were quantitatively extracted from water and various carbonated beverages into a 0.1 M quinine-chloroform solution in the presence of 0.5 M boric acid by brief shaking. Quantitative extraction of these dyes was also accomplished by the 0.1 M quinine-chloroform solution made conveniently from chloroform, quinine hydrochloride, and sodium hydroxide added successively to water or beverages containing boric acid. Quinine acted as a countercation on the dyes having sulfonic and/or carboxylic acid group(s) to form chloroform-soluble ion-pair complexes. The diacidicmore » base alkaloid interacted with each acid group of mono-, di-, tri-, and tetrasulfonic acid dyes approximately in the ratio 0.8-0.9 to 1. The dyes in the chloroform solution were quantitatively concentrated into a small volume of sodium hydroxide solution also by brief shaking. The convenient quinine-chloroform method was applicable to the quantitative extraction of a mixture of 12 dyes from carbonated beverages, which are all currently used for food coloration. A high-pressure liquid chromatographic method is also presented for the systematic separation and determination of these 12 dyes following their concentration into the aqueous alkaline solution. The chromatogram was monitored by double-wavelength absorptiometry in the visible and ultraviolet ray regions.« less