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Soil organic matter (SOM) turnover models predict changes in SOM due to management and environmental factors. Their initialization remains challenging as partitioning of SOM into different hypothetical pools is intrinsically linked to model assumptions. Diffuse reflectance mid-infrared Fourier transform spectroscopy (DRIFTS) provides information on SOM quality and could yield a measurable pool-partitioning proxy for SOM. This study tested DRIFTS-derived SOM pool partitioning using the Daisy model. The DRIFTS stability index (DSI) of bulk soil samples was defined as the ratio of the area below the aliphatic absorption band (2930 cm−1) to the area below the aromatic–carboxylate absorption band (1620 cm−1). For pool partitioning, the DSI (2930 cm−1 ∕ 1620 cm−1) was set equal to the ratio of fast-cycling ∕ slow-cycling SOM. Performance was tested by simulating long-term bare fallow plots from the Bad Lauchstädt extreme farmyard manure experiment in Germany (Chernozem, 25 years), the Ultuna continuous soil organic matter field experiment in Sweden (Cambisol, 50 years), and 7 year duration bare fallow plots from the Kraichgau and Swabian Jura regions in southwest Germany (Luvisols). All experiments were at sites that were agricultural fields for centuries before fallow establishment, so classical theory would suggest that a steady state can be assumed for initializing SOM pools. Hence, steady-state and DSI initializations were compared, using two published parameter sets that differed in turnover rates and humification efficiency. Initialization using the DSI significantly reduced Daisy model error for total soil organic carbon and microbial carbon in cases where assuming a steady state had poor model performance. This was irrespective of the parameter set, but faster turnover performed better for all sites except for Bad Lauchstädt. These results suggest that soils, although under long-term agricultural use, were not necessarily at a steady state. In a next step, Bayesian-calibration-inferred best-fitting turnover rates for Daisy using the DSI were evaluated for each individual site or for all sites combined. Two approaches significantly reduced parameter uncertainty and equifinality in Bayesian calibrations: (1) adding physicochemical meaning with the DSI (for humification efficiency and slow SOM turnover) and (2) combining all sites (for all parameters). Individual-site-derived turnover rates were strongly site specific. The Bayesian calibration combining all sites suggested a potential for rapid SOM loss with 95 % credibility intervals for the slow SOM pools' half-life being 278 to 1095 years (highest probability density at 426 years). The credibility intervals of this study were consistent with several recently published Bayesian calibrations of similar two-pool SOM models, i.e., with turnover rates being faster than earlier model calibrations suggested; hence they likely underestimated potential SOM losses.

Soil organic carbon (SOC) losses under a changing climate are driven by the temperature sensitivity of SOC mineralization (usually expressed as Q10, the multiplier of activity with 10 °C temperature increase). The activation energy theory (AET) suggests that, due to higher activation energies, the more complex the carbon, the higher is mineralization Q10. However, studies on Q10 have been inconsistent with regard to AET. Measurements of potential soil enzymes activity Q10 even contradicted AET: Phenoloxidase (representing complex carbon) had consistently lower Q10 than the more labile xylanase and glucosidase. This study used two approaches of examining Q10 in SOC modeling: 1) Bayesian calibration (BC) and 2) using different measured enzyme Q10 as proxies for mineralization Q10 of different SOC pools. The SOC model was DAISY (S. Hansen et al., 2012). BC informed Q10 by field measured data, while the second approach tested if directly using enzyme Q10 (of phenoloxidase, glucosidase and xylanase) for DAISY pools improved simulation results. Both approaches used the temperature sensitive measurements of CO2 evolution and soil microbial biomass. The measured enzyme Q10 were from field manipulation experiments with bare fallow and vegetated plots in the two regions of Kraichgau and Swabian Jura in Southwest Germany. The enzyme-derived Q10 were used for modelling those fields and furthermore for in‑situ litterbag decomposition experiments at 20 sites in the same region. Two further laboratory experiments with temperature manipulation were included: an incubation of the field residues into soil and an incubation of bare soil from the start and year 50 of a long duration bare fallow (from Ultuna). The BC made use of CO2 and microbial data to inform about the range of Q10 of different carbon pools for the individual experiments and combined data.The BC of the residue incubation experiment constrained Q10 for metabolic (~3) and structural litter (~2). Estimated 95% credibility intervals did not overlap. The BC for Ultuna could constrain the slow and fast SOC pool with Q10 ~2.8 and ~3, respectively, but credibility intervals of both pools overlapped. The Q10 of field experiments, which had most abundant data, could not be constrained by BC, probably because their annual temparature variability was too low. However, the model errors of the field experiment could be reduced by the second approach, when the Q10 of phenoloxidase was used for to the structural litter pool as well as for the fast and slow SOC pools. Thus regional enzyme Q10 improved the model fit but only for regional simulations. Therefore, they could be useful proxies when natural temperature range is too small to inform temperature sensitivity by BC. Any trends found in this study contradicted AET, both from measured enzymes and BC of the incubation experiments. This calls for alternative Q10 hypotheses and the need for individual Q10 values for different SOC pool rather than a general one. BC approaches would benefit from a wider temperature range of field experiments and understanding what causes variable enzyme Q10 could help to improve future SOC models.

The initialization of soil organic matter (SOM) turnover models has been a challenge for decades. Instead of using laborious and error prone size-density fractionation SOM pool partitioning, we propose the inexpensive, rapid, and non destructive Diffuse reflectance mid infrared Fourier transform spectroscopy (DRIFTS) technique on bulk soil samples to gain information on SOM pool partitioning from the spectra. Specifically, the DRIFTS stability index, defined as the ratio of aliphatic C-H (2930 cm−1) to aromatic C=C (1620 cm−1) stretching vibrations, was used to divide SOM into fast and slow cycling pools in the soil organic module of the DAISY model. Long-term bare fallow plots from Bad Lauchstädt (Chernozem, 25 years) and the Ultuna frame trial in Sweden (Cambisol, 50 years) were combined with bare fallow plots of 7 years duration in the Kraichgau and Swabian Jura region in Southwest Germany (Luvisols). All fields had been in agricultural use for centuries before fallow establishment, so classical theory would suggest an initial steady state of SOM, which was hence used to compare the performance of DAISY initializations against the newly established DRIFTS stability index. The test was done using two different published parameter sets (2.7 × 10−6 d−1, 1.4 × 10−4 d−1, 0.1 compared to 4.3 × 10−5 d−1, 1.4 × 10−4 d−1, 0.3 for the turnover rates of slow pool, fast pool and humification efficiency, respectively). The DRIFTS initialization of SOM pools significantly reduced model errors of poor performing model runs assuming steady state, irrespective of the turnover rates used, but the faster turnover parameter set fit better to all sites except Bad Lauchstädt. This suggests that soils under long-term agricultural use were not necessarily at steady state. A Bayesian calibration was applied in a next step to identify the best-fitting turnover rates for the DRIFTS stability index in DAISY, both for each site individually and for a combination of all sites. The two approaches which significantly reduced parameter uncertainty and equifinality were: (1) the addition of the physico-chemically based DRIFTS stability index, and (2) combining several sites into one Bayesian calibration, as derived turnover rates can be strongly site specific. The combination of all four sites showed that SOM is likely lost at relatively fast turnover rates with the 95 % credibility intervals of the slow SOM pools half life ranging from 278 to 1095 years, with 426 years as a value of highest probability density. The credibility intervals of this study were consistent with several recently published Bayesian calibrations of similar SOM models, all turnover rates were considerably faster than earlier models suggested. It is therefore likely that published turnover rates understimate the potential loss of SOM.

The direction and magnitude of change of soil organic carbon (SOC) stocks due to global warming depend strongly on the temperature sensitivity (e.g., Q10) of carbon mineralization. To date, most multi-pool SOC models assume a general Q10 of 2 despite experimental evidence suggesting different Q10 for different carbon fractions. The aim of this study was to test if the use of experimentally derived pool specific Q10 values improves the performance of SOC models. Five contrasting data sets from three field experiments and two laboratory incubations were used to study the link between carbon pool recalcitrance and Q10 using two different approaches: a) Bayesian calibration of the Daisy SOC model parameters to infer Q10 of SOC and crop-litter pools, and b) using measured Q10 values of carbon degrading enzymes as proxies for Q10 of different Daisy pools. Namely β-glucosidase (median Q10 of 1.82) was assigned to metabolic litter and phenol/peroxidase (1.35) to structural litter and both SOC pools. To partition litter-carbon and SOC into model pools, the lignin-to-nitrogen ratio and the ratio of aliphatic/aromatic-carboxylate carbon were used, respectively. Measurements included soil microbial biomass, soil carbon dioxide (CO2) evolution and remaining carbon in soils and crop-litter. In the Bayesian calibration, strong differences in inferred Q10 values of the same pools between experiments suggested that intrinsic substrate recalcitrance was not the main driver of temperature sensitivity. For field experiment simulations, both the Q10 values derived by Bayesian calibration and measured enzyme Q10 were centered around values below 2, contrasting with high Q10 values for mineralization under laboratory incubations (close to 3). Furthermore, assigning measured phenol/peroxidase Q10 values to the slow crop-litter as well as both SOC pools and β-glucosidase to the fast crop-litter pool (approach b), could significantly improve model performance compared to using the default Q10 value of 2 for all pools. Root-mean-squared-deviation reductions were between 3 and 10% for field experiments, with no change in the laboratory experiments. Thus, site specific Q10 values of soil enzymes show potential as proxies for pool specific Q10. We present a new conceptual framework to explain the observed differences in temperature sensitivities between experiments as a result of two fundamental driving factors classified in a) state variables, that fluctuate in time, and b) soil properties, that are constant over decades. Measured enzyme Q10 values were interpreted as a proxy incorporating both factors. More than intrinsic substrate recalcitrance, the state variables such as physical protection, substrate abundance and unfavorable conditions for microorganisms control temperature sensitivity of mineralization. To reduce the uncertainty in global SOC simulations under a changing climate, their relative contributions should be disentangled and then implemented into SOC models.

Peak area (PA) integration of diffuse reflectance mid infrared Fourier transform spectroscopy (DRIFTS) spectra is useful to study soil organic matter (SOM) quality and as a potential modelling proxy. Residual water of soil samples after drying affects DRIFTS spectra, mainly in the region >2500 cm−1. Therefore, SOM quality related PA at different wavenumbers should be influenced to varying degrees. We studied how absolute, normalized and relative PA related to SOM functional groups (at 2930, 1620, 1530 and 1159 cm−1), as well as their ratios were influenced by oven drying of soil samples at increasing temperatures (from 32 °C to 105 °C). All organic and even mineral associated PA significantly increased with drying temperature. The PA of aliphatic C H stretching (2930 cm−1), located on the shoulder of the broad O H stretching PA, was influenced most strongly. Our results indicate that using 105 °C as drying temperature and storing samples in a desiccator is the best way to minimize water interference. These findings apply to relative PA and ratios of organic compounds, while no effect of drying temperatures on PA correlations to C or N were found.