Development of a novel, fast, sensitive method for chromium speciation in wastewater based on an organic polymer as solid phase extraction material combined with HPLC–ICP-MS

• On-line preconcentration of chromium speices by SPE–HPLC–ICP-MS was developed
• Functionalized poly(chloromethyl styrene) was synthesized and used as adsorbent.
• The analytes were eluted rapidly with a very low concentration of TBAH.
• The preconcentration and detection procedure could be finished within 7 min.
• A very high enrichment factor has been obtained.

Speciation analysis of inorganic chromium in wastewater is of great significance for the monitoring of environmental pollution. In this work, N,N-bis(2-aminoethyl)ethane-1,2-diamine functionalized poly(chloromethyl styrene-co-styrene) was synthesized, characterized and used as the adsorbent to preconcentrate chromium species in environmental waters by on line solid-phase extraction (SPE). The trace speciation analysis of Cr(III) and Cr(VI) in wastewater has been used by short-column high-performance liquid chromatography hyphenated to inductively coupled plasma spectrometry (HPLC–ICP-MS) after on-line SPE. Cr(III) and Cr(VI) have been adsorbed on the anion exchange column after transforming the cationic Cr(III) to an anionic [Cr(III)–EDTA]− complex devoid of re-dox reagent, and then eluted rapidly (within seconds) with a very low concentration of tetrabutylammonium hydroxide (TBAH) solution. This method provides a reliable on-line preconcentration method and detection coupled technique. Under the optimized conditions, high enrichment factors have been obtained for Cr(VI) and [Cr(III)–EDTA]− with 30 mL sample solution up to 105 and 128, respectively. The low detection limits of 0.0068 ng mL−1 and 0.0041 ng mL−1, with the relative standard deviations (RSDs) of 4.3% and 3.6% were obtained for Cr(VI) and [Cr(III)–EDTA]−, respectively. The developed method was validated by analyzing Certified Reference Materials GSBZ50027-94, and the spike tests were also performed. At the same time, thanks to the merit of simple operation, rapid adsorption/desorption dynamics, high enrichment and low LODs, the established method was applied to analyze three wastewater samples from different discharge port.

N,N-bis(2-aminoethyl)ethane-1,2-diamine functionalized poly(chloromethyl styrene-co-styrene) was synthesized, characterized and used as the adsorbent to preconcentrate chromium in environmental waters by on line solid-phase extraction (SPE). Thus, a novel, simple and on-line SPE-HPLC-ICP-MS method has been established.Figure optionsDownload as PowerPoint slide