Determining Cr(III) and Cr(VI) levels in water

Collection and preservation of environmental samples

As Cr(VI) is a powerful oxidant, particularly under acidic conditions, care must be taken to avoid reduction/oxidation reactions from occurring when preparing samples for speciation analysis. Refrigeration of the samples (4oC) as well as minimal sample handling and storage (< 24 hours) is generally accepted as the best protocol for maintaining the integrity of water samples and extracts from the digestion of soil and air filter samples. US EPA (Environmental Protection Agency) methods 7199 (1996) and 218.6 (1994) specify adjustment to a pH of 9-9.5 with an ammonium sulphate- ammonium hydroxide buffer for the preservation of Cr(VI) in drinking waters, groundwaters and industrial effluents. Where necessary, samples should be filtered through a 0.45m filter prior to preservation and analysis.

Analytic measurement techniques for dissolved chromium in water and liquid extract samples
To distinguish between Cr(III) and Cr(VI) in wastewater, the metals must be separated. This also limits interference of other metals. The most widely used techniques for chromium speciation in waters and liquid extracts involve prior separation and isolation of Cr(VI) by 1. Ion chromatography (ASTM method D5281- 98 (2005); 2. Borai (2002); DIONEX methods TC 23 (1996), AN 80 (2000) and AU 144 (2003); 3. ISO DIS 16740 (2003); NIOSH methods 7604 (1994) and 7605 (2003); Michalski (2004); 4. OSHA method ID-215 (2006); 5. Posta et al (1996); 6. US EPA methods 218.6 (1994) and 7199 (1996)) 7. anion exchange (Hazelwood et al (2004); Marlow et al (2000) 8. NIOSH method 7703 (2003); Sahayam et al (2005); Wang et al (1999)) 9. Other separation techniques that have been used for isolating dissolved Cr(VI) include HPLC (Li & Zou (1999); Milacic et al (1992)), selective precipitation (US EPA method 7195 (1986)) and liquid-liquid extraction (El-Shahawi et al (2005); Orescanin et al (2004); US EPA method 7197 (1992)). Methods to quantify Chromium 1. 1,5 diphenylcarbazide spectrophotometric method- most popular 2. (ASTM method D5281-98 (2005) 3. DIONEX methods TC 26 (1996), AN 80 (2000) and AU 144 (2003) 4. German DIN 19734 (1999) and 38405 Part 24 (1987) 5. ISO DIS 16740 (2003) 6. NIOSH methods 7600 (1994),7605 (2003) and 7703 (2003) 7. OSHA method ID-215 (2006); 8. US EPA methods 7196A (1992); 218.6 (1994); 7199 (1996)). 9. Instrumental techniques 1. electrothermal atomic adsorption spectrometry (Sahayam et al (2005) 2. US EPA method 7191 (1986)) inductively coupled plasma coupled with optical emission spectroscopy (German DIN 38414 Part 7 (1983); 3. Menegrio et al (2005) 4. Posta et al (1996) 5. Rdel & Terytze (1999)) 6. mass spectroscopy (Inoue et al (1995); Posta et al (1996)) all offer very low detection limits and are also commonly used for the determination of both Cr(III) and pre-separated Cr(VI) in water and liquid extract samples.

Recent emphasis has been on the development of methods for the determination of Cr(III)/Cr(VI) or Cr(T)/Cr(VI) in a single step. Many of these techniques combine conventional (Malaudzi et al (2002)) or novel pre-separation and/or detection techniques (Menegrio et al (2005); Orescanin et al (2004)) with flow injection analysis (FIA) or sequential injection analysis (SIA) systems for automated on-line analysis. FIA and SIA techniques minimize sample handling and offer the possibilities for rapid, automatic routine laboratory or field-portable analysis.