Modelling low molecular weight organic acid dynamics in forest soils

Low molecular weight organic acids such as citrate and oxalate have been hypothesized to play a key role in rhizosphere ecology and pedogenesis. A mathematical site-specific model, DYNLOW, was constructed to describe the temporal and spatial dynamics of these organic acids in coniferous forest soils using the modelling software STELLA^®. Experimentally derived values for biodegradation, adsorption, and daily values of soil temperature, moisture and hydrological flow were used to parameterize the model. The model describes the dynamics and downward movement of oxalate and citrate through the horizons (O, AE, E, Bhs, Bs) of three podzolic soil profiles in Sweden. After calibration, the model predicted average soil solution organic acid concentrations ranging from <1 to 90 μM, which was in agreement with experimental measurements (<1 to 116 μM). The model results indicated that microbial degradation of organic acids was in quantitative terms the biggest process regulating soil solution concentrations. Primary production rates of organic acid in the soil were predicted to be high (<1 to 1250 nmol g⁻¹ soil d⁻¹) in comparison to the amount present at steady state in the soil solution pool (<0.1 to 240 nmol g⁻¹ soil). The downward transfer of organic acids between soil horizons due to mass flow was predicted to be a small flux (<0.1 to 3% of the total loss) compared to that lost by microbial biodegradation. The model predicted that the amount of basal soil respiration that could be attributable to the microbial turnover of organic acids was on average 19±22% of the basal CO₂ production across all sites and horizons for citrate and 7±7% for oxalate. The model results are discussed in the context of pedogenesis, forest soil respiration and organic matter production.     

暗棕壤中低分子有机酸的吸附与生物降解研究

低分子有机酸在森林生态系统中普遍存在,在根际和多种成土过程中发挥重要作用,但有机酸发挥作用的能力和效率与其在土壤中的吸附与降解等行为关系密切。本文研究了草酸、柠檬酸和苹果酸等低分子有机酸在森林暗棕壤A1层和B层的吸附及生物降解行为,结果表明,低分子有机酸加入到暗棕壤后迅速被土壤固相颗粒所吸附,其中对草酸的吸附远强于柠檬酸和苹果酸,三种低分子有机酸在暗棕壤A1层的吸附率强于B层;草酸、柠檬酸和苹果酸加入到森林暗棕壤后还能迅速被微生物降解,其中对草酸的降解远低于柠檬酸和苹果酸,暗棕壤对草酸较强的吸附作用可能是其生物降解率较低的主要原因,且三种低分子有机酸在A1层暗棕壤中的生物降解率高于B层。     

几种有机酸对可变电荷和恒电荷土壤吸附镉的影响

The objectives of this study were to illustrate the reaction processes, to identify and quantify the precipitates formed, and to estimate the porosity losses in order to eliminate drawbacks during remediating monochlorobenzene （MCB） and trichloroethylene （TCE）-contaminated aquifers using the ORC-GAC-Fe^0-CaCO3 system. The system consisted of four columns （112 cm long and 10 cm in diameter） with oxygen-releasing compound （ORC）, granular activated carbon （GAC）, zero-valent iron （Fe^0）, and calcite used sequentially as the reactive media. The concentrations of MCB in the GAC column effluent and TCE in the Fe^0 column effluent were below the detection limit. However, the concentrations of MCB and TCE in the final calcite column exceeded the maximum contaminant level （MCL） under the Safe Drinking Water Act of the US Environmental Protection Agency （US EPA） that protects human health and environment. These results suggested that partitioning of MCB and TCE into the gas phase could occur, and also that transportation of volatile organic pollutants in the gas phase was important. Three main precipitates formed in the ORC-GAC-Fe^0-CaCO3 system： CaCO3 in the ORC column along with Fe（OH）2 and FeCO3 in the Fe^0 column. The total porosity losses caused by mineral precipitation corresponded to about 0.24% porosity in the ORC column, and 1% in the Fe^0 column. The most important cause of porosity losses was anaerobic corrosion of iron. The porosity losses caused by gas because of the production and entrapment of oxygen in the ORC column and hydrogen in the Fe^0 column should not be ignored. Volatilization, precipitation and porosity losses were considered to be the main drawbacks of the ORC-GAC-Fe^0-CaCO3 system in remediating the MCB and TCE-contaminated aquifers. Thus, measurements such as using a suitable oxygen-releasing compound, weakening the increase in pH using a buffer material such as soil, stimulating biodegradation rates and minimizing the plugging caused by the relatively high dissolved oxygen levels should be taken to eliminate the drawbacks and to improve the efficiency of the ORC-GAC-Fe^0-CaCO3 system.     

七种钾释放动力学方程的比较和动力学参数的应用

Batch equilibrium experiments were conducted to investigate cadmium （Cd） sorption by two permanent-charge soils, a yellow-cinnamon soil and a yellow-brown soil, and two variable-charge soils, a red soil and a latosol, with addition of selected organic acids （acetate, tartrate, and citrate）. Results showed that with an increase in acetate concentrations from 0 to 3.0 mmol L^-1, Cd sorption percentage by the yellow-cinnamon soil, the yellow-brown soil, and the latosol decreased. The sorption percentage of Cd by the yellow-clnnamon soil and generally the yellow-brown soil （permanent-charge soils） decreased with an increase in tartrate concentration, but increased at low tartrate concentrations for the red soil and the latosol. Curves of percentage of Cd sorption for citrate were similar to those for tartrate. For the variable-charge soils with tartrate and citrate, there were obvious peaks in Cd sorption percentage. These peaks, where organic acids had maximum influence, changed with soil type, and were at a higher organic acid concentration for the variable-charge soils than for the permanent charge soils. Addition of cadmium after tartrate adsorption resulted in higher sorption increase for the varlable-charge soils than permanent-charge soils. When tartrate and Cd solution were added together, sorption of Cd decreased with tartrate concentration for the yellow-brown soil, but increased at low tartrate concentrations and then decreased with tartrate concentration for the red soil and the latosol.     

The carbon we do not see—the impact of low molecular weight compounds on carbon dynamics and respiration in forest soils: a review

Dissolved organic matter (DOM), typically quantified as dissolved organic carbon (DOC), has been hypothesized to play many roles in pedogenesis and soil biogeochemical cycles, however, most research to date concerning forest soils has focussed on the high molecular weight (HMW) components of this DOM. This review aims to assess the role of low molecular weight (LMW) DOM compounds in the C dynamics of temperate and boreal forest soils focussing in particular on organic acids, amino acids and sugars. The current knowledge of concentrations, mineralization kinetics and production rates and sources in soil are summarised. We conclude that although these LMW compounds are typically maintained at very low concentrations in the soil solution (<50 μM), the flux through this pool is extremely rapid (mean residence time 1-10 h) due to continued microbial removal. Due to this rapid flux through the soil solution pool and mineralization to CO₂, we calculate that the turnover of these LMW compounds may contribute substantially to the total CO₂ efflux from the soil. Moreover, the production rates of these soluble transitory compounds could exceed HMW DOM production. The possible impact of climate change on the behaviour of LMW compounds in soil is also discussed.     

Organic acid concentrations in soil solution: effects of young coniferous trees and ectomycorrhizal fungi

Organic acids may play a key role in rhizosphere and pedogenic processes. The effects of young trees and ectomycorrhizas on the soil solution concentrations of low molecular weight organic acids (LMWOAs) were studied in soil columns (E horizon) in the presence or absence of Pinus sylvestris and Picea abies with or without three ectomycorrhizal fungi. Several LMWOAs were identified at concentrations ranging from <0.1 to 11 μM. Compared to soil columns without tree seedlings, the presence of non-mycorrhizal or mycorrhizal tree seedlings sometimes resulted in small but statistically significant increases in citrate, formate, malonate and oxalate concentration. The general nutrient concentration and low P had little short-term effect on soil solution organic acid concentrations. The results suggest that biodegradation rather than production may be the major factor regulating soil solution organic acid concentrations.     

Fast turnover of low molecular weight components of the dissolved organic carbon pool of temperate grassland field soils

Large amounts of low molecular weight (LMW;<250 Da) carbon (C) are lost from roots into the rhizosphere as a consequence of root turnover and exudation. Their rates of turnover after release into the soil remain poorly understood. We extracted soil solution from a temperate grassland Eutric Cambisol, isotopically labeled the glucose and amino acid components, and then re-injected the solution back into the soil. We followed the subsequent evolution of ¹⁴CO₂ and incorporation of the LMW C into the soil microbial biomass or grasses for 48 h. The experiments were performed both on grazed and un-grazed swards in the field, and in the laboratory. In the field, we showed that glucose and amino acids had short half-lives (t_1/2) in soil solution (t_1/2=20-40 min), but that they persisted in soil microbes for much longer. A first-order double exponential model fitted the experimental data well and gave rate constant (k) values of 1.21-2.14 h⁻¹ for k₁ and 0.0025-0.0048 h⁻¹ for k₂. Only small amounts of the added ¹⁴C were recovered in plant biomass (<5% of total added to soil) indicating that plant roots are poor competitors for LMW dissolved organic C (DOC) in comparison to soil microorganisms. The first phase of glucose and amino acid mineralization in the laboratory was slower (t_1/2=40-60 min) than measured in the field reinforcing the importance of making flux measurements in situ. Whilst grazing stimulated below-ground respiration, it exerted only a small influence on the turnover of LMW DOC suggesting that the increase in respiration was due to increased root respiration and not turnover of soil organic matter (SOM). Our results suggest that some components of the LMW DOC pool are turned over extremely rapidly (ca. 4000 times annually).     

Biodegradation of low molecular weight organic acids in rhizosphere soils from a tropical montane rain forest

Root exudation of organic acids could be an important strategy for plant acquisition of phosphorus (P) from P-deficient soils in tropical rain forests. However, the efficacy of organic acids on P mobilization in the rhizosphere could be reduced due to their rapid biodegradation by rhizosphere microorganisms. To assess the dynamics and function of organic acids in the rhizosphere soils in tropical rain forests, we examined the concentrations of oxalate, citrate, and malate in soil solution and the mineralization kinetics of ¹⁴C-radiolabelled oxalate and citrate in the rhizosphere and bulk soil fractions. We compared two tropical montane rain forests from Mt. Kinabalu, Borneo that share similar parent material (i.e., sedimentary rocks) and climate but differ in terms of soil age. The older soil (Tertiary age materials) was affected by podzolization and had less inorganic labile P compared to the younger soil (Quaternary colluvial deposits). In the P-deficient older soil, the rhizosphere soil solution contained markedly higher concentrations of oxalate, citrate, and malate than did the bulk soil, whereas in the P-rich younger soil, the levels of organic acids in the rhizosphere were lower. The higher levels of organic acids in the rhizosphere of P-deficient soils are caused by greater root exudation and the lower sorption capacity for organic acids. The results of mineralization kinetics showed that oxalate and citrate in soil solution were rapidly mineralized in both rhizosphere and bulk fractions of both P-rich and P-deficient soils, having short mean residence times (2.3–13.1 h for oxalate and 0.8–1.6 h for citrate). The mineralization rates of oxalate and citrate were highest in the rhizosphere fraction of the P-deficient soil, where the pool of organic acids was largest and rapidly replenished by root exudation. Our data indicate that consumption as well as production of organic acids in the rhizosphere could be enhanced in P-deficient soil. The efficacy of organic acids on P mobilization in the rhizosphere in tropical montane rain forests appears to vary depending on the level of soil P availability and the anion sorption capacity, attributable to soil aging with podzolization.     

Immobilized-S, microbial biomass-S and soil arylsulfatase activity in the rhizosphere soil of rape and barley as affected by labile substrate C and N additions

Bulk and rhizosphere soil of rape and barley grown in a calcareous soil were pre-incubated for 7 days at 20 °C with Na₂³⁵SO₄ to partially label soil organic S. The soils were then incubated for 7 days more with increasing levels of two C sources as organic acids (succinic and malic acids) and as glucose (from 0 to 640 mg C kg⁻¹ soil) with or without increasing levels of N (from 0 to 15 mg N kg⁻¹ soil) in the form of ammonium nitrate, in order to mimic rhizodeposition inputs into soil. A second incubation experiment with a single highest dose of the used substrates was undertaken and two destructive soil samplings on days 17 and 35 were carried out. Both incubation experiments showed the intensities of S immobilization in the order: barley rhizosphere>rape rhizosphere>bulk soil. Glucose addition generated positive S priming effects in all studied soils after one week of incubation. Significant correlation coefficients were observed between immobilized-S and microbial biomass-S (r=0.95,p<0.001), arylsulfatase activity (ARS) and microbial biomass-S (r=0.65,p<0.05) on day 17 but not on day 35, whereas significant correlation coefficients were found between arylsulfatase activity and immobilized-S at both days 17 (r=0.79,p<0.01) and 35 (r=0.75,p<0.01). A marked decline of biomass-S noted in substrate-amended treatments at day 35 suggests a quick turnover of this compartment followed by its incorporation into the organic S. Finally, with organic acids high values of ARS per unit of biomass-S were recorded over the two studied dates in the rhizosphere soil of rape. It is concluded that the rhizosphere microbial biomass under rape exhibited more efficient arylsulfatase activity and hence greater turnover of organic S than that under the barley rhizosphere soil.     

Chemical composition of young and old carbon pools throughout Cambisol and Luvisol profiles under forests

The long-term storage of soil organic matter (SOM) in forest soils is still poorly understood. In this study, particle size fractionation in combination with accelerator mass spectroscopy (AMS) and solid state ¹³C nuclear magnetic resonance (NMR) spectroscopy was applied to investigate organic carbon (OC) stabilisation in Cambisol and Luvisol profiles under spruce (Picea abies) and beech (Fagus sylvatica L.) forests. In most samples, OC was preferentially associated with <2 μm fractions. Throughout soil profiles the contribution of OC in the clay fraction to the total OC increased from 27%-53% in A horizons to 44-86% in E, B and EB horizons. The 200-2000 μm fractions from all sites and all depths showed a percentage of modern C (pmC)>100. They were enriched in ¹⁴C owing to high inputs of recent material from leaves and roots. Clearly less active material was associated with <2 and 2-20 μm fractions. This demonstrated that the particle size fractionation procedure applied to our study was capable to isolate a young OC fraction in all samples. The pmC values were strongly decreasing with depth but the decrease was much more pronounced in the fine fractions. The <2 and 2-20 μm fractions of B, E and EB horizons revealed radiocarbon ages between 512 and 4745 years before present which indicated that the SOM in those horizons was little affected by the recent vegetation. The major components of labile and stable SOM pools in topsoils and subsoils were always O/N-alkyl C (28-53%) and alkyl C (14-48%) compounds. NMR spectra of bulk soils and particle size fractions indicated that high alkyl C and O/N-alkyl C proportions throughout the soil profile are typical of Cambisols and Luvisols which were not subjected to regular burning. A relation between radiocarbon age and chemical composition throughout soil profiles was not observed. This suggests that the long-term stabilisation of SOM is mainly controlled by the existence of various mechanisms of protection offered by the soil matrix and soil minerals but not by the chemical structure of SOM itself.     

Empirical modelling of the kinetics of phosphate sorption to macropore materials in aggregated subsoils

Preferential transport of phosphate through macropores increases the significance of phosphate sorption to macropore wall materials compared with bulk soil materials. Therefore we studied the kinetics of phosphate sorption to soil bulk materials from the Ap and Btg horizons, from the iron oxide-poor (Albic) centres and from iron oxide-rich (Red) exteriors of the fractures in a clayey pseudogley in batch at initial phosphate concentrations (P₀) up to a maximum of 650 μm and at sampling times up to 7 days. Uptake of phosphate was least in the phosphate-rich Ap, and the Albic material also adsorbed little. By contrast the Red material sorbed phosphate strongly. By plotting the logarithm of the solution phosphate concentration against log time, two or three different kinetic regions could be distinguished: a fast reaction within the first minute of reaction; a lag period at intermediate to large initial values of phosphate concentration (P₀); and a steady slow reaction. The lag phase cannot be described satisfactorily by the well-known adsorption models. The Langmuir equilibrium expression produced rather good fits at any fixed time of reaction, but the estimated adsorption maximum increased steadily with time. Empirical models were fitted to the data, among them a ‘lag-linear’ model developed to include the lag phase. The relative contribution of the fast reaction to total adsorption during 7 days decreased from 50 to 80% at small P₀ to less than 10% at large P₀ values. The fraction of fast-adsorbed phosphate followed the order Red > Btg > Albic > Ap regardless of P₀; the slow reaction is, by a log–log rate, ranked Albic ? Btg > Red > Ap for P₀ < 20 μm and Red > Btg > Albic > Ap at larger initial concentrations. The Albic material does not minimize the risk of phosphate leaching through macropores, as demonstrated by its small P sorption capacity, the relatively slow adsorption rate and its small actual P content.     

低分子量有机酸对可变电荷土壤铝活化动力学的影响

从动力学角度研究了几种低分子量有机酸对2种酸性土壤中铝的活化和活化铝在土壤固/液相之间分配的影响。结果表明:对于络合能力弱的醋酸和乳酸,主要通过质子作用活化铝,且活化作用明显小于盐酸。而络合能力较强的苹果酸、草酸和柠檬酸,主要通过络合作用促进铝的释放,且这种作用随有机酸根阴离子络合能力的增强而增加。在氧化铁含量较高的砖红壤中,苹果酸、草酸和柠檬酸通过专性吸附增加土壤表面负电荷,从而增加土壤交换态铝;但在氧化铁含量较低的红壤中,草酸和柠檬酸主要通过形成可溶性铝络合物降低交换态铝。活化铝在土壤固/液相间的分配主要决定于溶液中有机阴离子与土壤固相表面对铝离子的竞争。醋酸和乳酸活化的铝主要以交换态铝存在;而草酸和柠檬酸活化的铝主要以有机酸-铝络合物存在于溶液中,特别是在氧化铁低的红壤中,这将促进铝在土壤-水体中的迁移。     

Effect of Low Molecular Weight Organic Anions on Adsorption of Aluminum by Variable Charge Soils

To examine the effect of organic anions on adsorption of Al by variable charge soils at different pH values, the adsorption by three soils in the presence of three low-molecular-weight aliphatic carboxylic acids was investigated. The results showed that the effect depended on pH, the type of organic anions and their concentration. The presence of citrate and oxalate led to an increase in the adsorption of Al at low pH and low concentration of organic anions, with citrate showing a stronger effect than oxalate. For example, the maximum increments of Al adsorption in the presence of citrate were 131.9, 104.8 and 32.9% in the Hyper-Rhodic Ferralsol, the Rhodic Ferralsol and the Ferric Acrisol, respectively, whereas in the presence of oxalate it was 36.1% in the Rhodic Ferralsol. At high pH or high concentration of organic anions, they showed an inhibiting effect on the adsorption of Al. For example, citrate caused the increase in Al adsorption by 164.0, 131.0 and 61.0% at pH3.85 and the decrease in Al adsorption by 15.2, 19.5 and 45.6% at pH 4.8 for the Hyper-Rhodic Ferralsol, the Rhodic Ferralsol and the Ferric Acrisol, respectively. In the citrate and oxalate systems, the adsorption of Al increased with the increase in the concentration of organic anions, reaching a maximum values at about 0.4 mmol L^?1, and then decreased. When the concentration of organic anions was higher than about 1.0 mmol L^?1, both citrate and oxalate inhibited the adsorption of Al. The ability of organic anions in increasing the adsorption at low pH and decreasing the adsorption at high pH followed the same order: citrate > oxalate > acetate. The increase of Al adsorption at low pH is caused by the increase in soil negative surface charge as a result of the adsorption of organic anions by variable charge soils, while the decrease of Al adsorption at high pH and high concentration of organic anions is related to the competition of organic ligands for aluminum ions with soil surface. After the removal of free iron oxides from the soil, Al adsorption decreased in the presence of citrate, the anion species most strongly adsorbed by variable charge soils and complexed with aluminum ions. For example, for the Rhodic Ferralsol and the Ferric Acrisol, the removal of free iron oxides caused a decrease in the adsorption of Al in the presence of citrate at pH4.4 by 26.2 and 21.9%, respectively.     

Distribution of exogenous phytase activity in soil solid–liquid phases and their effect on soil organic P hydrolysis

The bioavailability and stability of organic phosphorus (P) in the soil may be affected by exogenous phytase (EPase) activity and distribution, but remain poorly understood. The distribution of EPase activity and hydrolysis ability of EPase on organic P in soil solid‐liquid phases was investigated. The EPase addition to soil suspension (1:20, w/v) from three soil types (red soil, brown soil, and cinnamon soil) under three treatments (untreated soil, removing clay from soil, and removing organic matter from soil) with different characters in the solution and solid phases was assayed. The results showed that the disappearance pattern of EPase activity from solution was similar for all soils, whereas the enzyme activity on the solid phase was dependent on soil types and treatments with the greatest in red soil and untreated soil. When EPase was added to soils, the adsorption ratio of organic matter and clay was 10 to 25% and 3 to 7%, respectively, with sorption capacity of organic matter being significantly (p < 0.05) stronger than that of clay. Additionally, soil dehydrogenase activity, which is the indicator of overall soil microbial activities, increased after EPase addition and the two enzymes showed significant negative relation in the soil suspension and solution. At the same time, the organic P decreased significantly (p < 0.05) after the addition of EPase in the soil solid, which had a varied rate under –40% after incubating 192 h, whereas organic P in the solution phase increased significantly (p < 0.05). This study demonstrated that organic matter had a strong protective and adsorptive effect on EPase effectiveness and microbes mightbe directly affect EPase longevity and decay. This finding suggests that EPase activity in the solid phase played a more important role in organic P hydrolysis.     

Phosphatase activity does not limit the microbial use of low molecular weight organic-P substrates in soil

Plant roots and soil microorganisms contain significant quantities of low molecular weight (MW) phosphorylated nucleosides and sugars. Consequently, upon death these can represent a significant input of organic-P to the soil. Some of these organic-P substrates must first be dephosphorylated by phosphatases before being assimilated by the soil microbial community while others can be taken up directly from soil solution. To determine whether sorption or phosphatase activity was limiting the bioavailability of low MW organic-P in soil we compared the microbial uptake and C mineralization of a range of ¹⁴C-labeled organic-P substrates [glucose-6-phosphate, adenosine monophosphate (AMP), adenosine diphosphate (ADP) and adenosine triphosphate (ATP)] to that of the parent compounds (adenosine and glucose). In a fertile grassland soil we showed that at low organic-P substrate concentrations (<0.5 mM) phosphatase activity did not limit microbial uptake or mineralization in comparison to their non-phosphorylated counterparts. However, at high substrate concentrations (1-10 mM) the mineralization of the organic-P compounds was significantly lower than that of the non-phosphorylated compounds suggesting that phosphatase activity or microbial transporter capacity limited bioavailability. Sorption to the solid phase followed the series glucose<adenosine<G-6-P<AMP<ADP=ATP. However, sorption of the organic-P compounds to the solid phase did not appear to greatly affect bioavailability. The high adenosine mineralization capacity of the microbial biomass suggests that nucleosides may represent a significant source of C and N to the soil microbial biomass. We conclude that at low organic-P substrate concentrations typical of those in soil, neither phosphatase activity nor sorption greatly limits their bioavailability.     

Recent (<4 year old) leaf litter is not a major source of microbial carbon in a temperate forest mineral soil

Microbial communities in soil A horizons derive their carbon from several potential sources: organic carbon (C) transported down from overlying litter and organic horizons, root-derived C, or soil organic matter. We took advantage of a multi-year experiment that manipulated the ¹⁴C isotope signature of surface leaf litter inputs in a temperate forest at the Oak Ridge Reservation, Tennessee, USA, to quantify the contribution of recent leaf litter C to microbial respiration and biomarkers in the underlying mineral soil. We observed no measurable difference (<∼40‰ given our current analytical methods) in the radiocarbon signatures of microbial phospholipid fatty acids (PLFA) isolated from the top 10 cm of mineral soil in plots that experienced 3 years of litterfall that differed in each year by ∼750‰ between high-¹⁴C and low-¹⁴C treatments. Assuming any difference in ¹⁴C between the high- and low-¹⁴C plots would reflect C derived from these manipulated litter additions, we estimate that <∼6% of the microbial C after 4 years was derived from the added 1-4-year-old surface litter. Large contributions of C from litter < 1 year (or >4 years) old (which fell after (or prior to) the manipulation and therefore did not differ between plots) are not supported because the ¹⁴C signatures of the PLFA compounds (averaging 200-220‰) is much higher that of the 2004-5 leaf litter (115‰) or pre-2000 litter. A mesocosm experiment further demonstrated that C leached from ¹⁴C-enriched surface litter or the O horizon was not a detectable C source in underlying mineral soil microbes during the first eight months after litter addition. Instead a decline in the ¹⁴C of PLFA over the mesocosm experiment likely reflected the loss of a pre-existing substrate not associated with added leaf litter. Measured PLFA Δ¹⁴C signatures were higher than those measured in bulk mineral soil organic matter in our experiments, but fell within the range of ¹⁴C values measured in mineral soil roots. Together, our experiments suggest that root-derived C is the major (>60%) source of C for microbes in these temperate deciduous forest soils.     

Effect of low-molecular-weight organic acids on Cl- adsorption by variable charge soils

Low-molecular-weight (LMW) organic acids exist widely in soils and have been implicated in many soil processes.The objective of the present paper was to evaluate effect of two LMW organic acids, citric acid and oxalic acid, on Cl^- adsorption by three variable charge soils, a latosol, a lateritic red soil and a red soil, using a batch method. The results showed that the presence of citric acid and oxalic acid led to a decrease in Cl- adsorption with larger decreases for citric acid. Among the different soils Cl- adsorption in the lateritic red soil and the red soil was more affected by both the LMW organic acids than that in the latosol.     

Physical protection and biochemical quality of organic matter in mediterranean calcareous forest soils: a density fractionation approach

Physical protection is one of the most important ways for stabilization of organic carbon (OC) in soils, and in order to properly manage soils as a sink for carbon, it is necessary to know how much OC a given soil could protect. To this end, we studied individual horizons taken from 16 soil profiles under Quercus rotundifolia stands, all over calcareous parent materials. Horizons were subjected to a sequential extraction using solutions of sodium polytungstate (NaPT) of increasing density: (i) NaPT d=1.6, using slight hand agitation, to obtain the free light fraction (FL); (ii) NaPT d=1.6 and ultrasonic dispersion, to obtain the Occluded Fraction I (Ocl I); (iii) NaPT d=1.8, to obtain the Occluded Fraction II (Ocl II); and (iv) NaPT d=2.0, to obtain the Occluded Fraction III (Ocl III). The fraction of density>2.0 are taken as dense fraction (DF). The free organic matter was further divided into FL>50 (retained by a 50 μm mesh: coarse organic fragments) and FL<50 (non-retained: fine organic fragments). The fractions FL>50 and FL<50 were taken together as free organic matter. The rest of the fractions are taken together as protected organic matter. The obtained fractions were analyzed for total OC, total N, and carbohydrate content. The percentage of non-hydrolyzable OC and N in each fraction was taken as an indicator of OC and N recalcitrance, respectively.For both OC and N, the fractions FL>50 and DF are dominant; the rest of the fractions are of much lower quantitative importance. In H horizons and in most A horizons, most of the OC and N are free, whereas in B horizons both OC and N are mostly protected. Overall, the percentages of free OC and N are very high and are currently amongst the highest ever recorded.Organic matter recalcitrance is lowest in the two most protected fractions (Ocl III and especially DF), and highest in the first occluded fractions (Ocl II and especially Ocl I). The free organic matter (FL>50 fraction) has an intermediate quality: it includes recognizable plant fragments, but the indicators tested (recalcitrance, carbohydrate content, cellulose to total carbohydrates ratio) suggest that it is not always the most fresh and non-decomposed fraction.There are clear maxima for both protected OC and N, which can be approached by curve fitting. By exponential fit, the obtained maxima are 84.1 g of OC and 7.7 g of N kg⁻¹ of mineral particles <20 μm. These maxima are much higher than the upper limits obtained by other authors. Differences in the sampling approach are suggested as the reason for such discrepancies.     

Loss of low molecular weight dissolved organic carbon (DOC) and nitrogen (DON) in H2O and 0.5 M K2SO4 soil extracts

Soil extracts are routinely used to quantify dissolved organic nutrient concentrations in soil. Here we studied the loss and transformation of low molecular weight (LMW) components of DOC (¹⁴C-glucose, 1 and 100 μM) and DON (¹⁴C-amino acid mixture, 1 and 100 μM) during extraction of soil (0-6 h) with either distilled water or 0.5 M K₂SO₄. The extractions were performed at 20 °C, at 4 °C, or in the presence of an inhibitor of microbial activity (HgCl₂ and Na-azide). We showed that both glucose and amino acids became progressively lost from solution with increasing shaking time. The greatest loss was observed in H₂O extracts at 1 μM for both substances (>90% loss after 15 min). Lower temperature (4 °C) and presence of K₂SO₄ both resulted in reduced loss rates. The presence of microbial inhibitors effectively eliminated the loss of glucose and amino acids. We conclude that microbial transformation of LMW-DOC and DON during H₂O or K₂SO₄ extraction of soil may affect the estimation of their concentrations in soil. This finding has significant implications for methods that rely on chemical extractions to estimate LMW-C components of DOC and DON.     

Organic matter in density fractions of water-stable aggregates in silty soils: Effect of land use

The location of soil organic matter (SOM) within the soil matrix is considered a major factor determining its turnover, but quantitative information about the effects of land cover and land use on the distribution of SOM at the soil aggregate level is rare. We analyzed the effect of land cover/land use (spruce forest, grassland, wheat and maize) on the distribution of free particulate organic matter (POM) with a density <1.6 g cm⁻³ (free POM_<1.6), occluded particulate organic matter with densities <1.6 g cm⁻³ (occluded POM_<1.6) and 1.6-2.0 g cm⁻³ (occluded POM_1.6-2.0) and mineral-associated SOM (>2.0 g cm⁻³) in size classes of slaking-resistant aggregates (53-250, 250-1000, 1000-2000, >2000 μm) and in the sieve fraction <53 μm from silty soils by applying a combined aggregate size and density fractionation procedure. We also determined the turnover time of soil organic carbon (SOC) fractions at the aggregate level in the soil of the maize site using the ¹³C/¹²C isotope ratio. SOM contents were higher in the grassland soil aggregates than in those of the arable soils mainly because of greater contents of mineral-associated SOM. The contribution of occluded POM to total SOC in the A horizon aggregates was greater in the spruce soil (23-44%) than in the grassland (11%) and arable soils (19%). The mass and carbon content of both the free and occluded POM fractions were greater in the forest soil than in the grassland and arable soils. In all soils, the C/N ratios of soil fractions within each aggregate size class decreased in the following order: free POM_<1.6>occluded POM_<1.6-2.0>mineral-associated SOM. The mean age of SOC associated with the <53 μm mineral fraction of water-stable aggregates in the Ap horizon of the maize site varied between 63 and 69 yr in aggregates >250 μm, 76 yr in the 53-250 μm aggregate class, and 102 yr in the sieve fraction <53 μm. The mean age of SOC in the occluded POM increased with decreasing aggregate size from 20 to 30 yr in aggregates >1000 μm to 66 yr in aggregates <53 μm. Free POM had the most rapid rates of C-turnover, with residence times ranging from 10 yr in the fraction >2000 μm to 42 yr in the fraction 53-250 μm. Results indicated that SOM in slaking-resistant aggregates was not a homogeneous pool, but consisted of size/density fractions exhibiting different composition and stability. The properties of these fractions were influenced by the aggregate size. Land cover/land use were important factors controlling the amount and composition of SOM fractions at the aggregate level.