Extraction of water‐soluble organic matter from mineral horizons of forest soils

Dissolved organic matter (DOM) is involved in many important biogeochemical processes in soil. As its collection is laborious, very often water‐soluble organic matter (WSOM) obtained by extracting organic or mineral soil horizons with a dilute salt solution has been used as a substitute of DOM. We extracted WSOM (measured as water‐soluble organic C, WSOC) from seven mineral horizons of three forest soils from North‐Rhine Westphalia, Germany, with demineralized H₂O, 0.01 M CaCl₂, and 0.5 M K₂SO₄. We investigated the quantitative and qualitative effects of the extractants on WSOM and compared it with DOM collected with ceramic suction cups from the same horizons. The amounts of WSOC extracted differed significantly between both the extractants and the horizons. With two exceptions, K₂SO₄ extracted the largest amounts of WSOC (up to 126 mg C kg^–1) followed by H₂O followed by CaCl₂. The H₂O extracts revealed by far the highest molar UV absorptivities at 254 nm (up to 5834 L mol^–1 cm^–1) compared to the salt solutions which is attributed to solubilization of highly aromatic compounds. The amounts of WSOC extracted did not depend on the amounts of Fe and Al oxides as well as on soil organic C and pH. Water‐soluble organic matter extracted by K₂SO₄ bore the largest similarity to DOM due to relatively analogue molar absorptivities. Therefore, we recommend to use this extractant when trying to obtain a substitute for DOM, but as WSOM extraction is a rate‐limited process, the suitability of extraction procedures to obtain a surrogate of DOM remains ambiguous.     

Quantification of long‐chain fatty acids in dissolved organic matter and soils

The objective was to develop and adapt a versatile analytical method for the quantification of solvent extractable, saturated long‐chain fatty acids in aquatic and terrestrial environments. Fulvic (FA) and humic (HA) acids, dissolved organic matter (DOM) in water, as well as organic matter in whole soils (SOM) of different horizons were investigated. The proposed methodology comprised extraction by dichloromethane/acetone and derivatization with tetramethylammonium hydroxide (TMAH) followed by gas chromatography/mass spectrometry (GC/MS) and library searches. The C_10:0 to C_34:0 methyl esters of n‐alkyl fatty acids were used as external standards for calibration. The total concentrations of C_14:0 to C_28:0 n‐alkyl fatty acids were determined in DOM obtained by reverse‐osmosis of Suwannee river water (309.3 μg g^—1), in freeze‐dried brown lake water (180.6 μg g^—1), its DOM concentrate (93.0 μg g^—1), humic acid (43.1 μg g^—1), and fulvic acid (42.5 μg g^—1). The concentrations of the methylated fatty acids (n‐C_16:0 to n‐C_28:0) were significantly (r² = 0.9999) correlated with the proportions of marker signals (% total ion intensity (TII), m/z 256 to m/z 508) in the corresponding pyrolysis‐field ionization (FI) mass spectra. The concentrations of terrestrial C_10:0 to C_34:0 n‐alkyl fatty acids from four soil samples ranged from 0.02 μg g^—1 to 11 μg g^—1. The total concentrations of the extractable fatty acids were quantified from a Podzol Bh horizon (26.2 μg g^—1), Phaeozem Ap unfertilized (48.1 μg g^—1), Phaeozem Ap fertilized (57.7 μg g^—1), and Gleysol Ap (66.7 μg g^—1). Our results demonstrate that the method is well suited to investigate the role of long‐chain fatty acids in humic fractions, whole soils and their particle‐size fractions and can be serve for the differentiation of plant growth and soil management.     

Stabilization of organic matter by soil minerals — investigations of density and particle‐size fractions from two acid forest soils

We tested the hypothesis whether organic matter in subsoils is a large contributor to organic carbon (OC) in terrestrial ecosystems and if survival of organic matter in subsoils is the result of an association with the soil mineral matrix. We approached this by analyzing two forest soil profiles, a Haplic Podzol and a Dystric Cambisol, for the depth distribution of OC, its distribution among density and particle‐size fractions, and the extractability of OC after destruction of the mineral phase by treatment with hydrofluoric acid (HF). The results were related to indicators of the soil mineralogy and the specific surface area. Finally, scanning electron microscopy combined with energy dispersive X‐ray spectroscopy (SEM‐EDX) was used to visualize the location of OC at mineral surfaces and associations with elements of mineral phases. The subsoils (B and C horizons) contained 40—50% of the soil OC including the organic forest floor layers. With increasing depth of soil profiles (1) the radiocarbon ages increased, and (2) increasing portions of OC were either HF‐soluble, or located in the density fraction d >1.6 g cm^—3, or in the clay fraction. The proportions of OC in the density fraction d >1.6 g cm^—3 were closely correlated to the contents of oxalate and dithionite‐citrate‐bicarbonate‐extractable Fe (r² = 0.93 and 0.88, P <0.001). SEM‐EDX analyses suggested associations of OC with aluminum whereas silicon‐enriched regions were poor in OC. The specific surface area and the microporosity of the soil mineral matrix after destruction of organic matter were less closely correlated to OC than the extractable iron fractions. This is possibly due to variable surface loadings, depending on different OC inputs with depth. Our results imply that subsoils are important for the storage of OC in terrestrial ecosystems because of intimate association of organic matter with secondary hydrous aluminum and iron phases leading to stabilization against biological degradation.     

Compositional changes of selected amino acids,organic acids,and soluble sugars in the xylem sap of N,P, or K‐deficient tomato plants

Xylem sap plays a major role in long‐distance transport of water, nutrients, and metabolites. However, there is little information on the behavior of metabolites in mineral‐deficient xylem sap. For this reason, the time‐dependent changes in selected metabolites (amino acids, organic acids, and soluble sugars) from tomato xylem sap in response to nitrogen (N), phosphorus (P), or potassium (K)‐deficient condition were investigated. Tomato plants (Solanum lycopersicum L.) were grown hydroponically in liquid culture under three different mineral regimes: N‐deficient [0.5 mM Ca(NO₃)₂ and 0.5 mM KNO₃], P‐deficient (0.05 mM KH₂PO₄), and K‐deficient (0.5 mM KNO₃), respectively. Xylem sap was collected at 10:00 am after 1, 5, 15, and 30 d, and the selected metabolites were analyzed with liquid chromatography. All N, P, or K deficiencies led to a substantial increase in metabolites in the xylem sap. The predominant amino acid in the xylem sap was glutamine and, interestingly, all mineral deficiencies resulted in a substantial amount of γ‐aminobutyric acid (GABA). Additionally, organic acids (citrate and malate) and soluble sugars were strongly increased in all mineral deficiencies, and, in particular, the level of shikimate was greatly affected by N deficiency. Based on these data, it is necessary to clearly elucidate an unknown event taking place in xylem loading in a variety of environmental impacts, and we are now studying to expand our knowledge on metabolic and proteomic responses using GC‐MS and LC‐MS.     

Nitrous oxide emissions from arable soils in Germany — An evaluation of six long‐term field experiments

In this study emissions of N₂O from arable soils are summarized using data from long‐term N₂O monitoring experiments. The field experiments were conducted at six sites in Germany between 1992 and 1997. The annual N‐application rate ranged from 0 to 350 kg N ha^—1. Mineral and organic N‐fertilizer applications were temporarily split adapted to the growth stage of each crop. N‐fertilizer input and N‐yield by the crops were used to calculate the In/Out‐balance. The closed chamber technique was applied to monitor the N₂O fluxes from soil into the atmosphere. If possible, plants were included in the covers. Annual N₂O emission values were based on flux rate measurements of an entire year. The annual N₂O losses ranged from 0.53 to 16.78 kg N₂O‐N ha^—1 with higher N₂O emissions from organically fertilized plots as compared to minerally fertilized plots. Approximately 50% of the total annual emissions occurred during winter. No significant relationship between annual N₂O emissions and the respective N‐fertilization rate was found. This was attributed to site‐ and crop‐specific effects on N₂O emission. The calculation of the N₂O emission per unit N‐yield from winter cereal plots indicates that the site effect on N₂O emission is more important than the effect of N‐fertilization. From unfertilized soils at the sites Braunschweig and Timmerlah a N‐yield of 60.0 kg N ha^—1 a^—1 and N₂O emissions of 2 kg N ha^—1 a^—1 were measured. This high background emission was assigned to the amount and turnover of soil organic matter. For a crop rotation at the sites Braunschweig and Timmerlah the N In/Out‐balance over a period of four years was identified as a suitable predictor of N₂O emissions. This parameter characterizes the efficiency of N‐fertilization for crop production and allows for N‐mineralization from the soil.     

Droplet infiltration and organic matter composition of intact crack and biopore surfaces from clay‐illuvial horizons

The organic matter (OM) in biopore walls and aggregate coatings may be important for sorption of reactive solutes and water as well as for solute mass exchange between the soil matrix and the preferential flow (PF) domains in structured soil. Structural surfaces are coated by illuvial clay‐organic material and by OM of different origin, e.g., earthworm casts and root residues. The objectives were to verify the effect of OM on wettability and infiltration of intact structural surfaces in clay‐illuvial horizons (Bt) of Luvisols and to investigate the relevance of the mm‐scale distribution of OM composition on the water and solute transfer. Intact aggregate surfaces and biopore walls were prepared from Bt horizons of Luvisols developed from Loess and glacial till. The mm‐scale spatial distribution of OM composition was scanned using diffuse reflectance infrared Fourier transform (DRIFT) spectroscopy. The ratio between alkyl and carboxyl functional groups in OM was used as potential wettability index (PWI) of the OM. The infiltration dynamics of water and ethanol droplets were determined measuring contact angles (CA) and water drop penetration times (WDPT). At intact surfaces of earthworm burrows and coated cracks of the Loess‐Bt, the potential wettability of the OM was significantly reduced compared to the uncoated matrix. These data corresponded to increased WDPT, indicating a mm‐scaled sub‐critical water repellency. The relation was highly linear for earthworm burrows and crack coatings from the Loess‐Bt with WDPT > 2.5 s. Other surfaces of the Loess‐Bt and most surfaces of the till‐derived Bt were not found to be repellent. At these surfaces, no relations between the potential wettability of the OM and the actual wettability of the surface were found. The results suggest that water absorption at intact surface structures, i.e., mass exchange between PF paths and soil matrix, can be locally affected by a mm‐scale OM distribution if OM is of increased content and is enriched in alkyl functional groups. For such surfaces, the relation between potential and actual wettability provides the possibility to evaluate the mm‐scale spatial distribution of wettability and sorption and mass exchange from DRIFT spectroscopic scanning.     

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.     

The significance of organic‐anion exudation for the aluminum resistance of primary triticale derived from wheat and rye parents differing in aluminum resistance

Eight primary octoploid triticale genotypes (xTriticosecale Wittmack) derived from four wheat cultivars (Triticum aestivum L.) and two rye inbred lines (Secale cereale L.) differing in aluminum (Al) resistance were investigated with respect to their response to Al supply. Aluminum‐induced inhibition of root elongation (48 h, 25 µM Al supply), callose formation, and the accumulation of Al in root tips (4 h, 25 µM Al supply) were used as parameters to assess Al resistance. Using these parameters, the existing information on Al resistance of the wheat and rye cultivars was generally confirmed. The triticale cultivars showed a wide range of Al resistance amongst the Al‐sensitive wheat and the Al‐resistant rye cultivars. The rye parents and the Al‐resistant wheat parent Carazinho were characterized by Al‐induced exudation particularly of citrate but also of malate from whole root systems of 14 d old seedlings (8 h, 50 µM Al supply). Regression analysis revealed that the degree of Al resistance of the triticale genotypes was closely related to the Al‐induced citrate exudation, which was mainly controlled by the Al resistance of the wheat parent.