Zaccone,C., Casiell,G., Longobardi,F., Bragazza,L., Sacco,A. and Miano,T.M.(2011): Evaluating the ‘conservative’ behavior of stable isotopic ratios (δ13C, δ15N, and δ18O) in humic acids and their reliability as paleoenvironmental proxies along a peat sequence. Chemical Geology, 285, 124-132.

『フミン酸の安定同位体比(δ13Cとδ15Nとδ18O)の「保守的な」挙動ならびに泥炭層に沿った古環境プロキシ(代理)としてのそれらの信頼性を評価する』


Abstract
 Although several studies have used bogs in order to reconstruct paleoclimatic conditions and the historical trends of pollutants, scientific literature is still rather controversial about the role of ombrotrophic bogs as reliable record of past environmental changes. Consequently, understanding whether all vegetational and climatic “information” are effectively preserved in peat deposit during humification becomes an essential aspect to be tested before using bogs as natural archives.
 The present work focuses on stable isotopic ratios, i.e., 13C/12C (δ13C), 15N/14N (δ15N) and 18O/16O (δ18O), and is based on the assumption that , if bogs are consistent archives of environmental changes, these types of “information” should be recorded also into humic acids (HA), i.e. the fraction of peat more recalcitrant and refractory to degradation.
 Thus, an 81-cm long peat core, covering the last 2000 years, was collected from the Etang de la Gruere(最初のeの頭に`) bog (Jura Mountains, Switzerland), cut into 3 cm slices, and HA were isolated from each age dated layer. Stable isotopic ratios (δ13C, δ15N and δ18O) were then determined in bulk peat and corresponding HA samples.
 As increase in the humification degree and a decrease of the C/N ratio were observed along the profile. The δ13C of both peat and HA showed a significantly similar trend with depth (p = 0.0001), and the same significant correlation was observed for the δ15N (p<0.0001). Also the ratio between δ13C and δ15N closely resembled the C/N ratio observed in the peat and in HA (p<0.0001), thus underlining that the trend of these isotopic ratios is preserved along the studied bog profile. Consequently, our data seem to support both the role of HA as recalcitrant, stable molecules with a long-term residence time, and the potential of ombrotrophic bogs to be used as “archives” of vegetational changes occurring (at least) in the last 2000 years. Although a certain relationship (p<0.05) between peat and corresponding HA was found also for δ18O, our data did not allow the solving of the issue of its reliability as paleoenvironmental proxy.

Keywords: C/N ratio; Humification; Isotopic signature; Natural archives; Ombrogenic bogs; Paleovegetation and paleoclimate changes』

1. Introduction
2. Material and methods
 2.1. Sampling site features
 2.2. Sample collection
 2.3. Humic acids isolation and humification degree indices
 2.4. Elemental composition
 2.5. Determination of stable isotopic ratios
 2.6. Statistical analyses
3. Results and discussion
 3.1. Peat humification degree with depth
 3.2. δ13C and δ15N signature
 3.3. δ18O signature
 3.4. Implications for paleovegetational and paleoclimatic reconstructions
4. Conclusions
Acknowledgments
References


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