Field flow fractionation online with ICP-MS as novel approach for the quantification of fine particulate carbon in stream water samples and soil extracts

Abstract

Reliable and efficient analytical techniques are required for quantitative size-resolved carbon determination of nanoparticles and colloids in complex sample matrices due to the key role of carbon in biological and environmental processes. Field flow fractionation (FFF) online with inductively coupled plasma mass spectrometry (ICP-MS) is a powerful technique for identification and quantification of particle bound metals, but has not been applied for quantitative determination of particulate carbon, yet, due to several challenges. Therefore, our study explores the potential of online particulate carbon detection by ICP-MS to overcome limitations of previously used UV detection or offline total organic carbon measurements. A novel organic carbon detector (OCD) was used as independent sensitive carbon detector to validate the ICP-MS results. Basic validation of organic carbon detection by offline quadrupole and sector-field ICP-MS was performed for fresh water samples using OCD as reference achieving recoveries of 107 ± 16% with Q-ICP-MS and 122 ± 22% with SF-ICP-MS. Limits of detection were 0.6 mg L⁻¹ for Q-ICP-MS, 0.3 mg L⁻¹ for SF-ICP-MS and 0.04 mg L⁻¹ for OCD. The main focus was on comparison of FFF-ICP-MS and FFF-OCD for quantification of particulate carbon in fresh water samples, soil extracts as well as in bovine serum albumin (BSA) as candidate reference standard. Recoveries obtained by FFF-Q-ICP-MS with a flow-injection calibration approach were in a range from 90 to 113% for replicate analyses of fresh water samples compared to FFF-OCD and from 87 to 107% with an alternative post-channel calibration strategy.