C and N NMR spectroscopy as a tool in soil organic matter studies

Nuclear magnetic resonance (NMR) is a valuable tool for the characterization of soil organic matter and humification processes in soils. This review highlights soil organic matter studies based mainly on solid-state ¹³C and ¹⁵N NMR spectroscopy and some emerging applications, that may provide significant progress in our knowledge on soil organic matter. A major advantage of Nmr spectroscopy is that it can be used as a non-invasive method for solid soil samples or soil fractions. Although resolution is limited, one can obtain an overview on the organic matter structures present in the soil sample. Application of ¹³C and ¹⁵N NMR to soils has, for a long time, been confined to the study of bulk soils or humic extracts for structural characterization. The transformations of soil organic C and N are now being investigated after addition of ¹³C- and ¹⁵N-labelled parent materials to the soil and following their evolution in different C and N pools. With labelling techniques it is also possible to study the interaction of organic pollutants with soil organic matter. Contamination of a soil with man-made additives, such as soot or brown coal dust, can also be detected in soils or individual soil fractions.     

Content and composition of free and occluded particulate organic matter in a differently textured arable Cambisol as revealed by solid‐state 13C NMR spectroscopy

The composition of functional light soil organic matter pools of arable Cambisols with a gradient in clay content was investigated. Soil texture differences originate from increasing loess admixture to the parent material (coarse‐grained tertiary sediments). Using density fractionation in combination with ultrasonic dispersion, two types of particulate organic matter (POM) were obtained: (1) free POM and (2) POM occluded in soil aggregates. Both POM fractions were analyzed by elemental analysis (C, N) and CPMAS ¹³C NMR spectroscopy. With increasing clay content the amount of organic carbon stored in the occluded POM fraction increased considerably, whereas the amounts of free POM were not related to the soil clay content. With increasing soil clay contents increasing proportions of O‐alkyl C and decreasing proportions of aryl C were found for both POM fractions. The occluded POM fraction showed a higher degree of degradation as indicated by lower amounts in O‐alkyl carbon. A lower degree of POM degradation was associated with higher clay contents. Higher soil clay contents promoted the conservation of POM with a low degree of alteration. This effect of soil texture was found to be highly significant when the aryl C : O‐alkyl C ratio was used as indicator for POM decomposition rather than the alkyl C : O‐alkyl C ratio.     

Near‐infrared spectroscopy can predict the composition of organic matter in soil and litter

The usefulness and limitations of near‐infrared reflectance spectroscopy (NIRS) for the assessment of several soil characteristics are still not sufficiently explored. The objective of this study was to evaluate the ability of visible and near‐infrared reflectance (VIS‐NIR) spectroscopy to predict the composition of organic matter in soils and litter. Reflectance spectra of the VIS‐NIR region (400–2500 nm) were recorded for 56 soil and litter samples from agricultural and forest sites. Spectra were used to predict general and biological characteristics of the samples as well as the C composition which was measured by ¹³C‐CPMAS‐NMR spectroscopy. A modified partial least‐square method and cross‐validation were used to develop equations for the different constituents over the whole spectrum (1st to 3rd derivation). Near‐infrared spectroscopy predicted well the C : N ratios, the percentages of O‐alkyl C and alkyl C, the ratio of alkyl C to O‐alkyl C, and the sum of phenolic oxidation products: the ratios of standard deviation of the laboratory results to standard error of cross‐validation (RSC) were greater than 2, the regression coefficients (a) of a linear regression (measured against predicted values) ranged from 0.9 to 1.1, and the correlation coefficients (r) were greater than 0.9. Satisfactorily (0.8 ≤ a ≤ 1.2, r ≥ 0.8, and 1.4 ≤ RSC ≤ 2.0) assessed were the contents of C, N, and production of DOC, the percentages of carbonyl C and aromatic C and the ratio of alkyl C to aromatic C. However, the N‐mineralization rate and the microbial biomass were predicted unsatisfactorily (RSC < 1.4). The good and satisfactory predictions reported above indicate a marked usefulness of NIRS in the assessment of biological and chemical characteristics of soils and litter.     

Chemical characteristics of glomalin-related soil protein (GRSP) extracted from soils of varying organic matter content

Glomalin is described in the literature as a N-linked glycoprotein and the putative gene product of arbuscular mycorrhizal fungi (AMF). Since the link between glomalin and various protein fractions in soil is not yet clearly defined, glomalin-related soil protein (GRSP) more appropriately describes glomalin's existence in natural organic matter (NOM). The objective of this study was to examine the chemical characteristics of GRSP present in several mineral and organic soils of varying organic carbon content. GRSP was isolated using high temperature sodium citrate extraction followed by either trichloroacetic acid (TCA) or hydrochloric acid (HCl) precipitation. GRSP was characterized by quantitative solid-state ¹³C DPMAS NMR, infrared (IR) spectroscopy, elemental analysis, and the Bradford assay for protein content. GRSP accounted for 25% and 52% of total C in the mineral soils and organic soil, respectively. Molar C/N and H/C ratios reveal that GRSP has less nitrogen than bovine serum albumin (BSA), and that GRSP extracted from the Pahokee peat soil possessed a more unsaturated, and thus aromatic character relative to the mineral soil GRSP, respectively. GRSP's high aromatic (42-49%) and carboxyl (24-30%) carbon contents and low aliphatic (4-11%) and carbohydrate-type carbon contents (4-16%) suggests that GRSP does not resemble a typical glycoprotein. In fact, the NMR spectra of GRSP closely resemble that of humic acid. GRSP extracted from mineral and organic soils possessed the same NMR fingerprint regardless of the precipitation method used (i.e., either TCA or HCl). It is likely that the current GRSP extraction methods, because of their similarity to the method used to extract humic acid, are coextracting both materials.     

Long‐term effects of liming on microbial biomass and activity and soil organic matter quality (13C CPMAS NMR) in organic horizons of Norway spruce forests in Southern Germany

Long‐term effects of liming on microbial biomass and activity and soil organic matter (SOM) were investigated in samples from organic horizons (Of/Oh) in spruce forests at Adenau, Höglwald, Idar‐Oberstein, and Schluchsee (Southern Germany) where plots have been manually treated 7 to 13 years ago with dolomitic limestone. At all sites, pH values were markedly increased after liming. The contents of C and N in the organic horizons of the limed plots appeared to be lower with the greatest decrease at Höglwald (Dystric Luvisol) where liming has affected the soil properties for the longest time of all sites. Catalase activity was promoted after liming at Adenau (Cambic Podzol). This was also the case for the Dystric Luvisol where liming resulted also in higher basal respiration. Biomass‐C was higher in samples from the limed plot at Idar‐Oberstein (Dystric Cambisol). The ¹³C CPMAS NMR spectra of organic horizons from the control plots indicate no differences in the gross carbon composition of SOM. Furthermore, spectra from the limed Cambic Podzol, Dystric Cambisol, and Haplic Podzol (Schluchsee) were remarkably similar. However, for the Dystric Luvisol, the lime‐induced promotion of microbial activity resulted in lower O‐alkyl‐C intensity. The observed patterns of microbial biomass and activity were site‐dependent rather than a result of liming. Obviously liming had only small long‐term effects on the humus quality in the organic horizons, as far as detectable by CPMAS NMR spectroscopy. More sensitive techniques like pyrolysis‐GC/MS should be applied to analyze differences in C composition.     

Differences in structure of organic matter in two soils as demonstrated by 13C cross polarisation nuclear magnetic resonance spectroscopy with magic angle spinning

Spectra of two whole soils have been recorded by cross polarisation n.m.r. spectroscopy with magic angle spinning. Magic angle spinning allows detailed structural comparisons between the types of organic carbon in whole soils to be made. Sufficient resolution is achieved to show that the two soils differ considerably in polysaccharide content.     

Determination of refractory organic matter in marine sediments by chemical oxidation, analytical pyrolysis and solid-state 13C nuclear magnetic resonance spectroscopy

Seeking to quantify the amount of refractory organic matter (ROM), which includes black carbon‐like material (BC), in marine sediments, we have applied a two‐step procedure that consists of a chemical oxidation with sodium chlorite of the demineralized sediments followed by integration of the aromatic C region in the remaining residues by solid‐state ¹³C nuclear magnetic resonance (NMR) spectroscopy. The efficacy for lignin removal was tested by analytical pyrolysis in the presence of tetramethyl ammonium hydroxide (TMAH). Riverine, estuarine and offshore marine sediment samples were collected from the southwest Atlantic coast of Spain, a site of geological and environmental interest. Measured contents of BC‐like material ranged between 3.0 and 45.7% of the total organic carbon. Greater relative BC contents were found in riverine sediments close to urban areas, which show an elevated input of anthropogenic organic material. The contents of BC‐like material in offshore marine sediments (5.5–6.1%) were similar to those previously reported for these kinds of samples. However, NMR and pyrolysis‐GC/MS of the isolated ROM reveals that abundant refractory aliphatic organic material remains in most of the marine samples after chlorite oxidation. We suggest that this pool of aliphatic carbon may play an important role as a stable carbon pool within the global C cycle.     

Decomposition of plant tissue submerged in an extremely acidic mining lake sediment: phenolic CuO-oxidation products and solid-state C NMR spectroscopy

In extremely acidic mining sediments of the Lusatian mining district, the alkalinisation process relies on organic C, which can serve as electron donor for microbially induced sulfate reduction. Plant material of the pioneer plant Juncus bulbosus is an important organic matter source in lake sediments. Therefore, decomposition of the plant tissue was assessed during the exposure of litterbags for 30 months in the 0-5 cm layer of waterlogged mining sediments, which have a pH between 2.5 and 3. The ash free dry weight (AFDW) and elemental content of the plant tissue were recorded several times during the exposure. Changes in chemical structure were analyzed by solid-state ¹³C cross polarization magic angle spinning nuclear magnetic resonance (CPMAS NMR) spectroscopy and the lignin component characterized by wet-chemical CuO oxidation. The AFDW accounted for about 34% of initial biomass after field exposure for 30 months. Mass loss of biomass occurred in two phases with decomposition rates varying between 30 and 430 mg AFDW d⁻¹. The mass loss increased considerably after 5-7 months when litterbags were invaded by fresh J. bulbosus plants. With respect to higher mass loss, ¹³C CPMAS NMR spectroscopy, showed slight changes of the bulk chemical composition after 11 months, indicating that microorganisms present in the sediments or in the rhizosphere degrade plant material as a whole, rather than selectively. During the second phase from about 11 months until the end of the exposure period, contribution of O-alkyl C most probably assignable to easily degradable polysaccharides decreased. In contrast, the contribution of alkyl, aromatic and carboxyl C increased. CuO oxidation showed that the lignin component of J. bulbosus is degraded oxidatively during field exposure. Our results indicate that the exposed plant material is decomposed in the sediment due to changes in sediment conditions that followed plant invasion of the litterbags. It is suggested that the rhizosphere of J. bulbosus by its influence on the redox potential, pH and the microbial component plays a crucial role in organic matter degradation in acidic mining sediments.     

Use of mid‐infrared spectroscopy in the diffuse‐reflectance mode for the prediction of the composition of organic matter in soil and litter

Mid‐infrared spectroscopy (MIRS) is assumed to be superior to near‐infrared spectroscopy (NIRS) for the prediction of soil constituents, but its usefulness is still not sufficiently explored. The objective of this study was to evaluate the ability of MIRS to predict the chemical and biological properties of organic matter in soils and litter. Reflectance spectra of the mid‐infrared region including part of the near‐infrared region (7000–400 cm^–1) were recorded for 56 soil and litter samples from agricultural and forest sites. Spectra were used to predict general and biological characteristics of the samples as well as the C composition which was measured by ¹³C CPMAS‐NMR spectroscopy. A partial least‐square method and cross‐validation were used to develop equations for the different constituents over selected spectra ranges after several mathematical treatments of the spectra. Mid‐infrared spectroscopy predicted well the C : N ratio: the modeling efficiency EF was 0.95, the regression coefficient (a) of a linear regression (measured against predicted values) was 1.0, and the correlation coefficient (r) was 0.98. Satisfactorily (EF ≥ 0.70, 0.8 ≤ a ≤ 1.2, r ≥ 0.80) assessed were the contents of C, N, and lignin, the production of dissolved organic carbon, and the contents of carbonyl C, aromatic C, O‐alkyl C, and alkyl C. However, the N mineralization rate, the microbial biomass and the alkyl–to–aromatic C ratio were predicted less satisfactorily (EF < 0.70). Limiting the sample set to mineral soils did generally not result in improved predictions. The good and satisfactory predictions reported above indicate a marked usefulness of MIRS in the assessment of chemical characteristics of soils and litter, but the accuracies of the MIRS predictions in the diffuse‐reflectance mode were generally not superior to those of NIRS.     

Long‐term effects of tillage,nutrient application and crop rotation on soil organic matter quality assessed by NMR spectroscopy

Crop and land management practices affect both the quality and quantity of soil organic matter (SOM) and hence are driving forces for soil organic carbon (SOC) sequestration. The objective of this study was to assess the long‐term effects of tillage, fertilizer application and crop rotation on SOC in an agricultural area of southern Norway, where a soil fertility and crop rotation experiment was initiated in 1953 and a second experiment on tillage practices was initiated in 1983. The first experiment comprised 6‐yr crop rotations with cereals only and 2‐yr cereal and 4‐yr grass rotations with recommended (base) and more than the recommended (above base) fertilizer application rates; the second experiment dealt with autumn‐ploughed (conventional‐till) plots and direct‐drilled plots (no‐till). Soil samples at 0–10 and 10–30 cm depths were collected in autumn 2009 and analysed for their C and N contents. The quality of SOM in the top layer was determined by ¹³C solid‐state NMR spectroscopy. The SOC stock did not differ significantly because of rotation or fertilizer application types, even after 56 yr. However, the no‐till system showed a significantly higher SOC stock than the conventional‐till system at the 0–10 cm depth after the 26 yr of experiment, but it was not significantly different at the 10–30 cm depth. In terms of quality, SOM was found to differ by tillage type, rate of fertilizer application and crop rotation. The no‐till system showed an abundance of O‐alkyl C, while conventional‐till system indicated an apparently indirect enrichment in alkyl C, suggesting a more advanced stage of SOM decomposition. The long‐term quantitative and qualitative effects on SOM suggest that adopting a no‐tillage system and including grass in crop rotation and farmyard manure in fertilizer application may contribute to preserve soil fertility and mitigate climate change.     

Chemistry of soil organic matter as related to C : N in Norway spruce forest (Picea abies(L.) Karst.) floors and mineral soils

Due to high nitrogen deposition in central Europe, the C : N ratio of litter and the forest floor has narrowed in the past. This may cause changes in the chemical composition of the soil organic matter. Here we investigate the composition of organic matter in Oh and A horizons of 15 Norway spruce soils with a wide range of C : N ratios. Samples are analyzed with solid‐state ¹³C nuclear magnetic resonance (NMR) spectroscopy, along with chemolytic analyses of lignin, polysaccharides, and amino acid‐N. The data are investigated for functional relationships between C, N contents and C : N ratios by structural analysis. With increasing N content, the concentration of lignin decreases in the Oh horizons, but increases in the A horizons. A negative effect of N on lignin degradation is observed in the mineral soil, but not in the humus layer. In the A horizons non‐phenolic aromatic C compounds accumulate, especially at low N values. At high N levels, N is preferentially incorporated into the amino acid fraction and only to a smaller extent into the non‐hydrolyzable N fraction. High total N concentrations are associated with a higher relative contribution of organic matter of microbial origin.     

Assessing management impacts on soil organic matter quality in subtropical Australian forests using physical and chemical fractionation as well as C NMR spectroscopy

Successful soil organic matter (SOM) quality assessment is needed to improve our ability to manage forest soils sustainably. Our objective was to use a multivariate data set to determine whether the land use conversion from native forest (NF) to hoop pine plantation and the following rotation and site preparation practices had altered SOM quality at three adjacent sites of NF, first (1R) and second rotation (2R, including tree planting row (2R-T) and windrow of harvest residues (2R-W)) of hoop pine plantations in southeast Queensland, Australia. Cross-polarization magic angle spinning ¹³C nuclear magnetic resonance (CPMAS ¹³C NMR) spectroscopy and sequential hot water and acid hydrolysis were conducted on SOM fractions separated by wet-sieving and density fractionation procedures to characterize SOM quantitative and qualitative relevant parameters, including carbon (C) functional groups, C and nitrogen (N) contents, C/N ratios, and C and N recalcitrant indices. Analysis of variance (ANOVA) and principal component analysis (PCA) of these multivariate parameters together indicated a complicated interaction between physical protection and biochemical recalcitrance, making the land use and management induced changes of SOM quality more complex. Knowledge of PCA based on the refined set of 41 SOM quantitative and qualitative parameters identified that principal component 1 (PC1), which explained 55.7% of the total variance, was most responsible for the management induced changes in soil processes. This was reflected by the dynamics of SOM regarding the aspects of total stock, soil basal and substrate induced respirations, gross and net N mineralization and nitrification, and microbial biomass, microbial diversity of C utilization patterns. Further, the macroaggregates (F_{250-2000 μm}) and the C/N ratio of acid extracts of SOM physical fractions, which represented the most informative and unique variables loading on PC1, might be the most promising physical and chemical measures for SOM quality assessment of land use and management impacts in subtropical Australian forests.     

Wildfires influence on soil organic matter in an Atlantic mountainous region (NW of Spain)

The principal aim of this research was to determine the influence of wildfires on soil organic matter (SOM) content and composition in soils located on the northern slope of the Cantabrian Cordillera, an Atlantic mountainous region in the North West of Spain, where wildfires are frequent. Samples from soils with similar aspect, slope, elevation and vegetation characteristics, but with different wildfires histories were collected. Total organic carbon and total nitrogen contents were determined as well as the C/N ratio. Furthermore, a qualitative characterization of the soil organic carbon (SOC) was carried out by ¹³C variable amplitude cross polarization magic angle spinning (VACP/MAS) Nuclear Magnetic Resonance (NMR) spectroscopy. Our results show that, on the one hand, all the sampled soils can be considered important pools of carbon in this Atlantic mountainous region, especially in the heath areas. On the other hand, the fire-affected soils present higher SOM contents than their unburnt counterparts. This could be attributed to an important reaccumulation of fresh vegetal material, which is probably a consequence of the decrease of SOM decomposition rates after fire. Moreover, charred organic compounds are not found in all the burnt soils, which could be due to the long time since the last fires events took place, to different fire severities, or to different post-fire erosion processes in the studied soils.     

The effects of compost in a rice–wheat cropping system on aggregate size,carbon and nitrogen content of the size–density fraction and chemical composition of soil organic matter,as shown by 13C CP NMR spectroscopy

We investigated whether the long‐term application of compost from agricultural waste improved soil physical structure, fertility and soil organic matter (SOM) storage. In 2006, we began a long‐term field experiment based on a rice–wheat rotation cropping system, having a control without fertilizer (NF) and three treatments: chemical fertilizers (CF), pig manure compost (PMC) and a prilled mixture of PMC and inorganic fertilizers (OICF). Following the harvest of wheat in 2010, the mean‐weight diameter (MWD) of water‐stable aggregates and the concentration of C and N in bulk soil (0–20 cm; <2 mm fraction) were significantly greater (P < 0.05) in PMC and NF plots than in CF or OICF plots. Pig manure compost significantly increased the proportion of >5‐mm aggregates, whereas CF significantly increased the proportion of 0.45‐ to 1‐mm aggregates. The C and N contents of all density fractions were greater in PMC than in other treatments with levels decreasing in the following order: free particulate organic matter (fPOM) >occluded particulate organic matter (oPOM) > mineral‐combined SOM (mineral–SOM). Solid‐state ¹³C CPMAS NMR spectra showed that alkyl C/O‐alkyl C ratios and aromatic component levels of SOM were smaller in PMC and OICF plots than in CF plots, suggesting that SOM in PMC and OICF plots was less degraded than that in CF plots. Nevertheless, yields of wheat in PMC and NF plots were smaller than those in CF and OICF plots, indicating that conditions for producing large grain yields did not maintain soil fertility.     

Detection of primary and secondary oxidation products by Fourier transform infrared spectroscopy (FTIR) and 1H nuclear magnetic resonance (NMR) in sunflower oil during storage

The oxidation of sunflower oil, stored in closed receptacles at room temperature for a period of 10 years, was monitored using Fourier transform infrared spectroscopy (FTIR) and 1H nuclear magnetic resonance (NMR). The objective was to understand the evolution of the oxidation process in sunflower oil under the conditions above mentioned. These techniques provide information about the oxidative status of several oil samples and the primary and some of the secondary oxidation products formed in the oxidation process. The results obtained show that, under these conditions, sunflower oxidation takes place in a different way to that at higher temperatures with aeration. The 1H NMR spectra show that in the first oxidation stages of the process only hydroperoxides supporting cis, trans-conjugated double bonds are formed and that at more advanced stages hydroperoxides having trans, trans-conjugated double bonds are generated, with the latter always being in a smaller proportion than the former. In addition, the presence of hydroxy derivatives supporting cis, trans-conjugated double bonds among the primary oxidation compounds is shown for the first time. Also, from early oxidation stages onward and unlike the process at 70 degrees C with aeration, it is noticeable that 4-hydroxy- trans-2-alkenals are formed in much higher proportions than 4-hydroperoxy- trans-2-alkenals. This fact could be associated with the presence of hydroxy derivatives with cis, trans-conjugated double bonds among the primary oxidation products and the limited concentration of oxygen during the oxidation. Furthermore, relationships between some oxidation conditions and the oxidation level of the samples were statistically analyzed.     

Soil organic matter dynamics in lands continuously cultivated with maize and soybean in Heilongjiang Province,Northeast China: Estimation from natural 13C abundance

Abstract

Northeast China is the main production area of maize and soybean in China. In the present study, the rates of decomposition and replacement of soil organic carbon (SOC) were estimated using the soil inventory collected since 1991 from long-term maize and soybean cultivation plots in Heilongjiang Province, Northeast China, to evaluate the sustainability of the present cultivation system. The total carbon (C) content in soil was stable without any significant changes in the plots (approximately 28.5 g C kg^?1). The δ¹³C value of soil organic matter under continuous maize cultivation increased linearly with an annual increment of 0.07 from ?23.9 in 1991, which indicated that approximately 13% of the initial SOC was decomposed during the 13-year period of maize cultivation, with a half-life of 65 years. Slow decomposition of SOC was considered to result from the low annual mean temperature (1.5°C) and long freezing period (170–180 days year^?1) in the study area. In contrast, the amount of organic C derived from maize increased in the soil with a very slow annual increment of 0.17 g C kg^?1, probably because of the removal of all the plant residues from the plots. Based on the soil organic matter dynamics observed in the study plots, intentional recycling/maintenance of plant residues was proposed as a way of increasing soil fertility in maize or soybean cultivation.     

森林生态系统中土壤有机质组分的固态13C核磁共振波谱表征

Forest management practices such as prescribed burning and thinning in forest ecosystems may alter the properties of soil organic matter (SOM).In this study,surface soils from field plots in the Bankhead National Forest,Alabama,USA,were used to investigate possible SOM transformations induced by thinning and burning.Elemental analysis and solid-state 13C cross polarization magic angle spinning nuclear magnetic resonance (13C CPMAS NMR) spectroscopy were used to characterize SOM fractions in whole soils,humic substances,and density fractions.Our data revealed that the changes in SOM fractions due to the repeated burning carried out in the forest ecosystem studied were involved mainly with alkyl C,O-alkyl C,and carbohydrate functional groups,implying that most prominent reactions that occurred involved dehydrogenation,de-oxygenation,and decarboxylation.In addition,burning and thinning might have also affected the distribution and composition of free and occluded particulate SOM fractions.The limited structural changes in SOM fractions suggested that low-intensity prescribed fire in the forest ecosystem studied will not create major structural changes in SOM fractions.     

Storage and stability of organic matter and fossil carbon in a Luvisol and Phaeozem with continuous maize cropping: A synthesis

Quantitative information about the amount and stability of organic carbon (OC) in different soil organic‐matter (OM) fractions and in specific organic compounds and compound‐classes is needed to improve our understanding of organic‐matter sequestration in soils. In the present paper, we summarize and integrate results performed on two different arable soils with continuous maize cropping (a) Stagnic Luvisol with maize cropping for 24 y, b) Luvic Phaeozem with maize cropping for 39 y) to identify (1) the storage of OC in different soil organic‐matter fractions, (2) the function of these fractions with respect to soil‐OC stabilization, (3) the importance and partitioning of fossil‐C deposits, and (4) the rates of soil‐OC stabilization as assessed by compound‐specific isotope analyses. The fractionation procedures included particle‐size fractionation, density fractionation, aggregate fractionation, acid hydrolysis, different oxidation procedures, isolation of extractable lipids and phospholipid fatty acids, pyrolysis, and the determination of black C. Stability of OC was determined by ¹³C and ¹⁴C analyses. The main inputs of OC were plant litter (both sites) and deposition of fossil C likely from coal combustion and lignite dust (only Phaeozem).