Ultra-Microscale (5–25 μg C) Analysis of Individual Lipids by 14C AMS: Assessment and Correction for Sample Processing Blanks

Abstract

Measurements of the natural abundance of radiocarbon in biomarker molecules can be used to elucidate the biogeochemical roles of marine bacteria and archaea in the oceanic water column. However, the relatively low concentration of biomass, especially below the euphotic zone, inevitably results in small sample sizes for compound-specific analyses. In ultra-microscale Δ14C measurements, which we define as measurements on samples smaller than 25 μg C, the process of isolating pure compounds and preparing them for measurement adds significant background carbon. This additional blank carbon can contribute up to 40% of the total sample mass; therefore, it is necessary to quantify all components of the processing blank in order to make appropriate corrections. Complete propagation of error is critical in order to report the correct analytical uncertainty. The carbon blank is composed of at least 3 different sources: i) those that scale in proportion to the mass of the sample; ii) sources that contribute a constant mass of blank, e.g. closed-tube combustion; and iii) contaminants from vacuum lines and/or other aspects of sample handling that are difficult to quantify. We approached the problem of correcting for the total sample processing blank by deriving a 4-part isotopic mass balance based on separating the 3 exogenous components from the sample. Subsequently, we derived the appropriate equations for the full propagation of error associated with these corrections. Equations for these terms are presented. Full treatment of a set of raw data is demonstrated using compound-specific Δ14C data from the North Central Pacific water column.