Geological Institute , ETHZ , Sonneggstrasse 5 , 8092 Zurich , Switzerland.
Laboratory of Ion Beam Physics , ETHZ , Otto-Stern-Weg 5 , 8093 Zurich , Switzerland.
Anal Chem. 2019 Feb 5;91(3):2042-2049. doi: 10.1021/acs.analchem.8b04491. Epub 2019 Jan 14.
We examine instrumental and methodological capabilities for microscale (10-50 μg of C) radiocarbon analysis of individual compounds in the context of paleoclimate and paleoceanography applications, for which relatively high-precision measurements are required. An extensive suite of data for C-free and modern reference materials processed using different methods and acquired using an elemental-analyzer-accelerator-mass-spectrometry (EA-AMS) instrumental setup at ETH Zurich was compiled to assess the reproducibility of specific isolation procedures. In order to determine the precision, accuracy, and reproducibility of measurements on processed compounds, we explore the results of both reference materials and three classes of compounds (fatty acids, alkenones, and amino acids) extracted from sediment samples. We utilize a MATLAB code developed to systematically evaluate constant-contamination-model parameters, which in turn can be applied to measurements of unknown process samples. This approach is computationally reliable and can be used for any blank assessment of small-size radiocarbon samples. Our results show that a conservative lower estimate of the sample sizes required to produce relatively high-precision C data (i.e., with acceptable errors of <5% on final C ages) and high reproducibility in old samples (i.e., FC ≈ 0.1) using current isolation methods are 50 and 30 μg of C for alkenones and fatty acids, respectively. Moreover, when the FC is >0.5, a precision of 2% can be achieved for alkenone and fatty acid samples containing ≥15 and 10 μg of C, respectively.
我们考察了在古气候和古海洋学应用背景下,对 10-50μg 的 C 进行微量(微区)放射性碳分析的仪器和方法学能力,这些应用需要相对高精度的测量。为了评估特定分离程序的重现性,我们编译了一整套无碳和现代参考物质的数据,这些数据是使用不同的方法处理的,并使用苏黎世联邦理工学院的元素分析仪-加速器质谱仪(EA-AMS)仪器设置获得。为了确定处理后化合物测量的精度、准确性和重现性,我们探索了参考物质以及从沉积物样品中提取的三类化合物(脂肪酸、烯酮和氨基酸)的结果。我们利用一种开发的 MATLAB 代码来系统地评估常数污染模型参数,该方法反过来可以应用于未知过程样品的测量。这种方法在计算上是可靠的,可用于任何小尺寸放射性碳样品的空白评估。我们的结果表明,使用当前的分离方法,为了在旧样品中产生相对高精度的 C 数据(即最终 C 年龄的误差<5%可接受)和高重现性,分别需要 50μg 和 30μg 的 C 来获得烯酮和脂肪酸的相对高的精度。此外,当 FC>0.5 时,对于含有≥15μg 和 10μg 的 C 的烯酮和脂肪酸样品,可以分别实现 2%的精度。