Low-level (submicromole) environmental 14C metrology

Abstract

Accelerator mass spectrometry (AMS) measurements of environmental 14C have been employed during the past decade at the several micromole level (tens of μg carbon), but advanced research in the atmospheric and marine sciences demands still higher (μg) sensitivity, an extreme example being the determination of 14C in elemental or “black” carbon (BC) at levels of 2–10 μg per kg of Greenland snow and ice (Currie et al., 1998). A fundamental limitation for 14C AMS is Poisson counting statistics, which sets in at about 1 μg modern-C. Using the small sample (25 μg) AMS target preparation facility at NOSAMS (Pearson et al., 1998), and the microsample combustion–dilution facility at NIST, we have demonstrated an intrinsic modern-C quantification limit ( m Q) of ca. 0.9 μg, based on a 1-parameter fit to the empirical AMS variance function. (For environmental 14C, the modern carbon quantification limit is defined as that mass ( m Q) corresponding to 10% relative standard deviation (rsd) for the fraction of modern carbon, σ( f M)/ f M.) Stringent control, required for quantitative dilution factors (DL), is achieved with the NIST on-line manometric/mass spectrometry facility that compensates also for unsuspected trace impurities from vigorous chemical processing (e.g., acid digestion). Our current combustion blank is trivial (mean: 0.16 ± 0.02 μg C, n=13) but lognormally distributed (dispersion [σ]: 0.07 ± 0.01 μg). An iterative numerical expression is introduced to assess the quantitative impacts of fossil and modern carbon blank components on m Q; and a new “clean chemistry” BC processing system is described for the minimization of such blanks. For the assay of soot carbon in Greenland snow/ice, the overall processing blank has been reduced from nearly 7 μg total carbon to less than 1 μg, and is undetectable for BC.