Abstract

Abstract. Changes in global soil carbon stocks have considerable potential to influence the course of future climate change. However, a portion of soil organic carbon (SOC) has a very long residence time (> 100 years) and may not contribute significantly to terrestrial greenhouse gas emissions during the next century. The size of this persistent SOC reservoir is presumed to be large. Consequently, it is a key parameter required for the initialization of SOC dynamics in ecosystem and Earth system models, but there is considerable uncertainty in the methods used to quantify it. Thermal analysis methods provide cost-effective information on SOC thermal stability that has been shown to be qualitatively related to SOC biogeochemical stability. The objective of this work was to build the first quantitative model of the size of the centennially persistent SOC pool based on thermal analysis. We used a unique set of 118 archived soil samples from four agronomic experiments in northwestern Europe with long-term bare fallow and non-bare fallow treatments (e.g., manure amendment, cropland and grassland) as a sample set for which estimating the size of the centennially persistent SOC pool is relatively straightforward. At each experimental site, we estimated the average concentration of centennially persistent SOC and its uncertainty by applying a Bayesian curve-fitting method to the observed declining SOC concentration over the duration of the long-term bare fallow treatment. Overall, the estimated concentrations of centennially persistent SOC ranged from 5 to 11 g C kg−1 of soil (lowest and highest boundaries of four 95 % confidence intervals). Then, by dividing the site-specific concentrations of persistent SOC by the total SOC concentration, we could estimate the proportion of centennially persistent SOC in the 118 archived soil samples and the associated uncertainty. The proportion of centennially persistent SOC ranged from 0.14 (standard deviation of 0.01) to 1 (standard deviation of 0.15). Samples were subjected to thermal analysis by Rock-Eval 6 that generated a series of 30 parameters reflecting their SOC thermal stability and bulk chemistry. We trained a nonparametric machine-learning algorithm (random forests multivariate regression model) to predict the proportion of centennially persistent SOC in new soils using Rock-Eval 6 thermal parameters as predictors. We evaluated the model predictive performance with two different strategies. We first used a calibration set (n = 88) and a validation set (n = 30) with soils from all sites. Second, to test the sensitivity of the model to pedoclimate, we built a calibration set with soil samples from three out of the four sites (n = 84). The multivariate regression model accurately predicted the proportion of centennially persistent SOC in the validation set composed of soils from all sites (R2 = 0.92, RMSEP = 0.07, n = 30). The uncertainty of the model predictions was quantified by a Monte Carlo approach that produced conservative 95 % prediction intervals across the validation set. The predictive performance of the model decreased when predicting the proportion of centennially persistent SOC in soils from one fully independent site with a different pedoclimate, yet the mean error of prediction only slightly increased (R2 = 0.53, RMSEP = 0.10, n = 34). This model based on Rock-Eval 6 thermal analysis can thus be used to predict the proportion of centennially persistent SOC with known uncertainty in new soil samples from different pedoclimates, at least for sites that have similar Rock-Eval 6 thermal characteristics to those included in the calibration set. Our study reinforces the evidence that there is a link between the thermal and biogeochemical stability of soil organic matter and demonstrates that Rock-Eval 6 thermal analysis can be used to quantify the size of the centennially persistent organic carbon pool in temperate soils.

Highlights

  • Soils exert a key regulation on atmospheric greenhouse gas concentrations on a decadal timescale through the net carbon source and sink status of their organic carbon reservoir (Amundson, 2001; Eglin et al, 2010)

  • The uncertainty in CPSOC concentration was lower at Rothamsted and Versailles than at Ultuna and Grignon

  • High uncertainties were found for high values of CPSOC proportion, with a modulation by the site-specific CPSOC concentration uncertainty (Grignon > Ultuna > Versailles > Rothamsted; Table 1), as expected from Eq (6) (Fig. S2)

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Summary

Introduction

Soils exert a key regulation on atmospheric greenhouse gas concentrations on a decadal timescale through the net carbon source and sink status of their organic carbon reservoir (Amundson, 2001; Eglin et al, 2010). A portion of the soil organic carbon (SOC) reservoir may not contribute significantly to the net exchange of CO2 and CH4 between atmosphere and land during the century because its residence time exceeds 100 years and its rate of carbon input is low (Trumbore, 1997; He et al, 2016). The amount of centennially persistent organic carbon in soils is highly uncertain as it cannot be estimated accurately by current analytical methods (Post and Kwon, 2000; von Lützow et al, 2007; Bruun et al, 2008). The general lack of information on the size and turnover rate of measurable SOC pools hampers the initialization of SOC pools in dynamic models, questioning their predictions of the evolution of the global SOC reservoir (Falloon and Smith, 2000; Luo et al, 2014; Feng et al, 2016; He et al, 2016; Sanderman et al, 2016). Luo et al (2016) and He et al (2016) recently claimed that optimizing parameter estimations with global datasets on SOC pools and fluxes was the highest priority to reduce biases among Earth system models

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