Description: Bulk organic parameters and stable and radiocarbon isotope compositions of organic carbon (δ13COC and Δ14COC) as well as various biomarkers (lignin phenols, plant waxes etc.) have been used to investigate the biogeochemical characteristics of organic carbon in the Amazon River system. However, the source, concentration and distribution pattern of lignin on the Amazon shelf and fan has not been assessed so far. In particular, the compound-specific stable carbon isotope compositions (δ13C) of lignin phenols have not been characterized in the Amazon River system. In order to study the distribution of lignin in the lower Amazon basin and its dispersal on the shelf and fan, we used riverbed sediments from the Amazon mainstream and its main tributaries and marine surface sediments on the Amazon shelf and fan. The samples were analyzed for particulate organic carbon content (POC), δ13COC, lignin phenol compositions and compound-specific δ13C of individual lignin phenols. The concentrations of aluminium and silicon (Al/Si) were used as a proxy for grain size[1]. The POC content in the main tributaries ranged from 0.13 to 3.99 wt-% and increased with Al/Si ratio in each tributary. δ13COC varied from -26.1‰ to -29.9‰ VPDB in riverbed sediments. Lignin content (represented by Λ8, sum of eight lignin phenols in OC, expressed as mg/100mg OC) ranged from 0.73 to 6.91 and is positively related with Al/Si ratio in the main tributaries except for the Xingu River, in which Λ8 decreased with Al/Si. Ratios of syringyl to vanillyl (S/V) and cinnamyl to vanillyl (C/V) varied from 0.70 to 1.51 and 0.08 to 0.47, respectively, suggesting that the dominant source of lignin is non-woody angiosperm tissue. The ratios of vanillic acid to vanillin (Ad/Al)v (0.26-0.71) and syringic acid to syringaldehyde (Ad/Al)s (0.15-0.57) indicated relatively fresh, non-degraded lignin. In marine sediments, the δ13COC ranged from -18.6‰ to -26.7‰ and is correlated with the Λ8 value (0.04-2.01). The decreasing Λ8 value along the coast from the Amazon River mouth towards the northwest implies that lignin is distributed by the North Brazil Current. A main plant source of non-woody angiosperm tissue was indicated by the S/V (0.59-1.62) and C/V (0.10-0.43) ratios on the marine samples. The agreement between riverbed and marine sediments suggests that processing of POC during transport from the basin to offshore does not change the plant source information of lignin. Highly degraded lignin on the Amazon fan and the southeast shelf is indicated by (Ad/Al)v (0.49-0.99). δ13C of lignin phenols of 9 marine sediments ranged from -28.6‰ to -33.3‰ and were consistently lower than δ13COC (-19.7‰ to -26.7‰). Depleted δ13C of lignin phenols indicate that the POC produced by the terrestrial biosphere is mainly derived from higher plants using C3 photosynthesis. References Bouchez, J., Galy, V., Hilton, R.G., Gaillardet, J., Moreira-Turcq, P., Pérez, M.A., France-Lanord, C., Maurice, L., 2014. Source, transport and fluxes of Amazon River particulate organic carbon: Insights from river sediment depth-profiles. Geochemica et Cosmochimica Acta 133, 280-298

Description: Compound-specific radiocarbon (14C) dating often requires working with small samples of 〈 100 µg carbon (µgC). This makes the radiocarbon dates of biomarker compounds very sensitive to biases caused by extraneous carbon of unknown composition, a procedural blank, which is introduced to the samples during the steps necessary to prepare a sample for radiocarbon analysis by accelerator mass spectrometry (i.e., isolating single compounds from a heterogeneous mixture, combustion, gas purification and graphitization). Reporting accurate radiocarbon dates thus requires a correction for the procedural blank. We present our approach to assess the fraction modern carbon (F14C) and the mass of the procedural blanks introduced during the preparation procedures of lipid biomarkers (i.e. n-alkanoic acids) and lignin phenols. We isolated differently sized aliquots (6–151 µgC) of n-alkanoic acids and lignin phenols obtained from standard materials with known F14C values. Each compound class was extracted from two standard materials (one fossil, one modern) and purified using the same procedures as for natural samples of unknown F14C. There is an inverse linear relationship between the measured F14C values of the processed aliquots and their mass, which suggests constant contamination during processing of individual samples. We use Bayesian methods to fit linear regression lines between F14C and 1/mass for the fossil and modern standards. The intersection points of these lines are used to infer F14Cblank and mblank and their associated uncertainties. We estimate 4.88 ± 0.69 μgC of procedural blank with F14C of 0.714 ± 0.077 for n-alkanoic acids, and 0.90 ± 0.23 μgC of procedural blank with F14C of 0.813 ± 0.155 for lignin phenols. These F14Cblank and mblank can be used to correct AMS results of lipid and lignin samples by isotopic mass balance. This method may serve as a standardized procedure for blank assessment in small-scale radiocarbon analysis.