Dissolved organic matter has been recognized as mobile, thus crucial to translocation of metals, pollutants but also of nutrients in soil. We present a conceptual model of the vertical movement of ...dissolved organic matter with soil water, which deviates from the view of a chromatographic stripping along the flow path. It assumes temporal immobilization (sorptive or by co-precipitation), followed by microbial processing, and re-release (by desorption or dissolution) into soil water of altered compounds. The proposed scheme explains well depth trends in age and composition of dissolved organic matter as well as of solid-phase organic matter in soil. It resolves the paradox of soil organic matter being oldest in the youngest part of the soil profile – the deep mineral subsoil.
► Improved conceptual model of DOM movement in soil. ► Physico-chemical immobilization by sorption and/or co-precipitation. ► Microbial processing of sorbed/co-precipitated matter, subsequent re-release (desorption/dissolution) of altered compounds. ► DOM mirrors soil organic matter. ► Model explains changes in soil organic matter properties with depth.
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GEOZS, IJS, IMTLJ, KILJ, KISLJ, NUK, OILJ, PNG, SAZU, SBCE, SBJE, UL, UM, UPCLJ, UPUK, ZRSKP
Ferric iron (FeIII) solid phases serve many functions in soils and sediments, which include providing sorption sites for soil organic matter, nutrients, and pollutants. The reactivity of Fe solid ...phases depends on the mineral structure, including the overall crystallinity. In redox-active soils and sediments, repeated reductive dissolution with subsequent exposure to aqueous ferrous iron (Fe2+) and oxidative re-precipitation can alter Fe phase crystallinity and reactivity. However, the trajectory of Fe mineral transformation under redox fluctuations is unclear and has been reported to result in both increases and decreases in Fe phase crystallinity. Several factors such as water budget, organic matter input, redox dynamics as well as the initial Fe phase composition might play a role. The objective of our study was to examine if Fe minerals in soils that differ in porosity-dependent water leaching rate and initial Fe phase crystallinity, demonstrate distinct mineral transformations when subjected to redox fluctuations. We sampled paired plots of two soil types under similar management but with different water leaching rates and contrasting Fe oxide crystallinity — an Alisol rich in crystalline Fe phases and an Andosol rich in short-range-ordered (SRO) Fe phases. The two soils were either exposed to several decades of redox fluctuations during rice paddy cultivation (paddy) or to predominantly oxic conditions in neighboring vegetable gardens (non-paddy). Paddy soils are uniquely suited for this type of study because they are regularly submerged and develop regular redox fluctuations. We also incubated the non-paddy soils in the laboratory for one year through eight anoxic/oxic cycles and monitored the aqueous soil geochemistry. Mössbauer spectroscopy was then used to evaluate Fe mineral speciation in field soils (paddy and non-paddy) and laboratory incubations. In the field soils, we found that redox fluctuation had contrasting effects on Fe oxide crystallinity, with crystallinity being lower in the Alisol paddy soil and higher in the Andosol paddy soil than in their corresponding non-paddy controls. In the laboratory incubation experiment, Eh, pH and dissolved Fe2+ responded as anticipated, with elevated Fe2+ concentrations during the anoxic periods as well as low Eh and high pH. Mössbauer measurements suggest the fluctuating redox incubation was beginning to alter Fe oxide crystallinity along the same trajectory as observed in the field, but the changes were within the range of fitting errors. We propose that reductive dissolution of crystalline Fe oxides prevails in the soil rich in crystalline Fe oxides (Alisol) and that re-precipitation as SRO Fe oxides is favored by constrained leaching, which leads to the observed decrease in Fe oxide crystallinity. In the soil rich in SRO Fe phases (Andosol), preferential reductive dissolution of SRO Fe oxides coupled with stronger leaching of dissolved Fe2+ causes the observed relative increase in crystallinity of the remaining Fe oxides. The observed increase in Fe oxide crystallinity may further be a result of Fe(II)-catalyzed re-crystallization of SRO Fe oxides. These findings indicate that, besides other factors, the Fe mineral composition of the initial soil or sediment as well as the leaching rate likely influence the trajectory of Fe oxide evolution under alternating redox-conditions.
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GEOZS, IJS, IMTLJ, KILJ, KISLJ, NLZOH, NUK, OILJ, PNG, SAZU, SBCE, SBJE, UL, UM, UPCLJ, UPUK, ZRSKP
Dissolved organic matter (DOM) is often considered the most labile portion of organic matter in soil and to be negligible with respect to the accumulation of soil C. In this short review, we present ...recent evidence that this view is invalid. The stability of DOM from forest floor horizons, peats, and topsoils against microbial degradation increases with advanced decomposition of the parent organic matter (OM). Aromatic compounds, deriving from lignin, likely are the most stable components of DOM while plant-derived carbohydrates seem easily degradable. Carbohydrates and N-rich compounds of microbial origin produced during the degradation of DOM can be relatively stable. Such components contribute much to DOM in the mineral subsoil. Sorption of DOM to soil minerals and (co-)precipitation with Al (and probably also with Fe), especially of the inherently stable aromatic moieties, result in distinct stabilization. In laboratory incubation experiments, the mean residence time of DOM from the Oa horizon of a Haplic Podzol increased from <30 y in solution to >90 y after sorption to a subsoil. We combined DOM fluxes and mineralization rate constants for DOM sorbed to minerals and a subsoil horizon, and (co-)precipitated with Al to estimate the potential contribution of DOM to total C in the mineral soil of a Haplic Podzol in Germany. The contribution of roots to DOM was not considered because of lack of data. The DOM-derived soil C ranges from 20 to 55 Mg ha⁻¹ in the mineral soil, which represents 19%-50% of the total soil C. The variation of the estimate reflects the variation in mineralization rate constants obtained for sorbed and (co-)precipitated DOM. Nevertheless, the estimates indicate that DOM contributes significantly to the accumulation of stable OM in soil. A more precise estimation of DOM-derived C in soils requires mineralization rate constants for DOM sorbed to all relevant minerals or (co-)precipitated with Fe. Additionally, we need information on the contribution of sorption to distinct minerals as well as of (co-)precipitation with Al and Fe to DOM retention.
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BFBNIB, FZAB, GIS, IJS, KILJ, NLZOH, NUK, OILJ, SAZU, SBCE, SBMB, UL, UM, UPUK
Clay minerals and pedogenic metal (oxyhydr)oxides are the most reactive soil mineral constituents controlling the long-term persistence of organic carbon (OC) in terrestrial ecosystems. However, ...their co-occurrence in most soils complicates direct assessment of their individual contribution to OC persistence. Making use of unique mineralogical combinations in soils located in the East Usambara Mountains of Tanzania, we disentangled the contribution of clay-sized aluminous minerals (kaolinite, gibbsite) and pedogenic Fe (oxyhydr)oxides (predominant goethite and hematite) on OC storage and stabilization under natural forests and croplands. Topsoil samples, varying in contents but not types of aluminous clays and pedogenic Fe (oxyhydr)oxides, were identified by selective extractions, X-ray diffraction, and Mössbauer spectroscopy. Associated abundance of particulate and mineral-associated organic matter (OM) was quantified by density fractionation and their changes during land-use conversion were determined as a measure of OC persistence. Additionally, we assessed the resistance of OC to chemical oxidation as well as microbial decomposition in a 50-day laboratory incubation. We found that the ratio of pedogenic Fe to aluminous clay is more consequential for OC storage and stabilization than their individual contents, despite the fact that Fe (oxyhydr)oxides generally exert a stronger impact on OC than aluminous clays. Conjunction of large amounts of Fe (oxyhydr)oxides with low aluminous clay contents caused the strongest accumulation of mineral-associated OC, a low soil respiration, high OC stability against chemical oxidation, and high OC persistence during land-use change. Our study suggests that certain mineralogical combinations in the humid tropics alleviate OM losses during land conversion because of the strong and selective mineral control on OC stabilization, particular if the weight ratio of pedogenic Fe to aluminous clay exceeds the threshold range of 0.44‒0.56.
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IZUM, KILJ, NUK, PILJ, PNG, SAZU, UL, UM, UPUK
Lignin is a main component of plant litter. Its degradation is thought to be critical for litter decomposition rates and the build-up of soil organic matter. We studied the relationships between ...lignin degradation and the production of dissolved organic carbon (DOC) and of CO
2
during litter decomposition. Needle or leaf litter of five species (Norway spruce, Scots pine, mountain ash, European beech, sycamore maple) and of different decomposition stage (freshly fallen and up to 27 months of field exposure) was incubated in the laboratory for two years. Lignin degradation was followed with the CuO method. Strong lignin degradation occurred during the first 200 incubation days, as revealed by decreasing yields of lignin-derived phenols. Thereafter lignin degradation leveled off. This pattern was similar for fresh and decomposed litter, and it stands in contrast to the common view of limited lignin degradation in fresh litter. Dissolved organic carbon and CO
2
also peaked in the first period of the incubation but were not interrelated. In the later phase of incubation, CO
2
production was positively correlated with DOC amounts, suggesting that bioavailable, soluble compounds became a limiting factor for CO
2
production. Lignin degradation occurred only when CO
2
production was high, and not limited by bioavailable carbon. Thus carbon availability was the most important control on lignin degradation. In turn, lignin degradation could not explain differences in DOC and CO
2
production over the study period. Our results challenge the traditional view regarding the fate and role of lignin during litter decomposition. Lignin degradation is controlled by the availability of easily decomposable carbon sources. Consequently, it occurs particularly in the initial phase of litter decomposition and is hampered at later stages if easily decomposable resources decline.
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BFBNIB, FZAB, GIS, IJS, INZLJ, KILJ, NLZOH, NMLJ, NUK, OILJ, PNG, SAZU, SBCE, SBMB, UL, UM, UPUK, ZRSKP
In soils, dissolved organic matter (DOM) is probably the most bioavailable fraction of soil organic matter, since all microbial uptake mechanisms require a water environment. Bioavailability ...describes the potential of microorganisms to interact with DOM. It is a prerequisite for biodegradation and can be restricted, if DOM is present in small pores or within soil aggregates and therefore not accessible for microorganisms. DOM biodegradation is defined as the utilisation of organic compounds by soil microorganisms quantified by the disappearance of DOM or O
2 or by the evolution of CO
2. The controlling factors for DOM biodegradability can be divided into three groups, namely, intrinsic DOM quality parameters, soil and solution parameters and external factors. DOM characteristics that generally enhance its biodegradability are high contents of carbohydrates, organic acids and proteins for which the hydrophilic neutral fraction seems to be a good estimate. In contrast, aromatic and hydrophobic structures that can also be assessed by UV absorbance decrease DOM biodegradability, either due to their recalcitrance or due to inhibiting effects on enzyme activity. Effects of solution parameters such as Al, Fe, Ca and heavy metal concentrations on DOM biodegradability have been documented in various studies, however with different, sometimes conflicting results. Inhibitory effects of metals are generally attributed to toxicity of the organic complexes or the free metal ions. In contrast, the enhanced degradability observed in the presence of metal ions may be due to flocculation, as larger structures will provide better attachment for microbial colonies. As degradation is dependent on microbial activity, the composition and density of the microbial population used in the degradation studies also influence biodegradation. Site-specific factors, such as vegetation, land use and seasonality of meteorological parameters control DOM composition and soil and soil solution properties and therefore also affect its biodegradability. The major obstacle for a better understanding of the controls of DOM biodegradability is the lack of a standardised methodology or at least systematic comparisons between the large number of methods used to assess DOM biodegradability.
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GEOZS, IJS, IMTLJ, KILJ, KISLJ, NUK, OILJ, PNG, SAZU, SBCE, SBJE, UL, UM, UPCLJ, UPUK
Although bacteria play key roles in aquatic food webs and biogeochemical cycles, information on the seasonal succession of bacterial communities in lakes is still far from complete. Here, we report ...results of an integrative study on the successional trajectories of bacterial communities in a seasonally stratified lake with an anoxic hypolimnion. The bacterial community composition of epilimnion, metalimnion, and hypolimnion diverged during summer stratification and converged when the lake was mixed. In contrast, bacterial communities in the sediment remained relatively stable over the year. Phototrophic
and heterotrophic
and
were abundant in the aerobic epilimnion,
(mainly
) dominated in the metalimnion, and
, and
were abundant in the anoxic sulfidic hypolimnion. Anoxic but nonsulfidic conditions expanded to the surface layer during fall turnover, when the epilimnion, metalimnion and upper hypolimnion mixed. During this period, phototrophic sulfur bacteria (
and
) disappeared,
(
) and
(
) spread out from the former meta- and hypolimnion to the surface layer, and
dominated in the bottom water layer.
and
regained dominance in early spring, after the oxygen concentration was restored by winter mixing. In total, these results show large spatio-temporal changes in bacterial community composition, especially during transitions from oxic to anoxic and from sulfidic to nonsulfidic conditions.
•Plaggic Anthrosols and reference soils have similar OC concentrations, radiocarbon age, and SOM composition.•OC in Plaggic Anthrosols is not explained by charred OM from historic plaggen ...amendments.•Sandy agricultural soils in NW and Central Europe accumulate organic matter beyond saturation levels based on organo-mineral associations.•Sandy Plaggic Anthrosols contain high concentrations of OC, likely from specific former vegetation, but stability under current conditions is uncertain.
Carbon sequestration in Plaggic Anthrosols is most often investigated by bulk soil carbon inventories, without considering the form in which the carbon is stored (e.g., particulate or mineral-associated organic matter (OM), its capacity, or its chemical composition). Here, we focus on the unusual high organic carbon (OC) accumulation in sandy Plaggic Anthrosols and adjacent reference soils under agricultural use. In these soils, the mineral fraction ≤20 µm which is commonly assumed to be the major factor for OC stabilization, are very low in mass proportion. Soil organic matter (SOM) physical fractionation was done to evaluate the quantity and quality of OC in the topsoil (Ap horizon). For the fraction ≤20 µm (medium and fine silt-, and clay-sized particles), we measured the concentration of OC and calculated its OC storage capacity and contribution. The OC of the fraction ≤20 µm was radiocarbon-dated and analyzed for its chemical composition by solid-state 13C NMR spectroscopy. The highly sandy (∼90 % sand and coarse silt) soils showed an accumulation of OC much higher than the conventionally calculated saturation level controlled by the proportion of the fraction ≤20 µm. Unexpectedly, Plaggic Anthrosols and the respective reference soils showed similar fractional OC concentrations, radiocarbon ages, and OM composition. The isolated fraction ≤20 µm contained, on average, 81 % of the total soil OC in only 9 % of the corresponding soil mass. All soil fractions ≤20 µm are characterized by a high mean OC concentration in the topsoil (reference soils: 226 ± 66.5 mg OC g−1, Plaggic Anthrosols: 202 ± 59.0 mg OC g−1) with a C/N ratio of 15 on average for both soils. The OM composition of the fraction ≤20 µm was specifically rich in alkyl-C, with unusually low proportions of O-alkyl-C and low contents of aryl-C. The radiocarbon concentration (F14C) indicated that topsoil OM of the ≤20 µm fraction is stored for long time periods with high mean conventional radiocarbon ages (14C) not only for Plaggic Anthrosols (F14C: 0.92 ± 0.04; 14C: 639 yBP) but also for the reference soils (F14C: 0.93 ± 0.04; 14C: 575 yBP) and received low inputs of OC derived from recent photosynthesis. Our data indicate the existence of specific SOM accumulation processes in the investigated sandy agricultural soils, resulting particularly large SOM stocks which cannot be explained by mechanistic association of OM with mineral surfaces. It is not clear, if this inherited OM is stable under present-day soil and management conditions.
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GEOZS, IJS, IMTLJ, KILJ, KISLJ, NUK, OILJ, PNG, SAZU, SBCE, SBJE, UL, UM, UPCLJ, UPUK
While soil organic carbon (C) is the foundation of productive and healthy ecosystems, the impact of the ecology of microorganisms on C-cycling remains unknown. We manipulated the diversity, applied ...here as species richness, of the microbial community present in similar soils on two contrasting land-covers—an adjacent pasture and forest—and observed the transformations of plant detritus and soil organic matter (SOM) using stable isotope (
13
C) tracing coupled with a novel nuclear magnetic resonance (NMR) experiment. The amount of detritus-C degraded was not affected by the microbial diversity (p > 0.05), however the fate of detritus- and SOM-C across the diversity gradient was complex and land cover-dependent. For example, in the pasture soil, higher diversity led to lower CO
2
production (p = 0.001), a trend driven solely by SOM-C mineralization. There was no relationship between diversity and detritus-C mineralization or production of new mineral-associations after one year (p > 0.05). In contrast, in the forest soil higher diversity resulted in increased detritus-C (p = 0.01) and SOM-C (p = 0.0008) mineralization and decreased mineral-associated organic matter formation (p = 0.02). In both land cover types, retention efficiency—a measure that integrates both microbial physiology and the ability of the ecosystem to retain C—explained C loss and transformation trends. Overall, this demonstrates that the trajectory of C gained and lost is altered by land management-induced changes to microbial communities, soil structure, and chemical characteristics underlying SOM persistence.
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DOBA, EMUNI, FZAB, GEOZS, IJS, IMTLJ, IZUM, KILJ, KISLJ, MFDPS, NUK, OILJ, PILJ, PNG, SAZU, SBCE, SBJE, SBMB, SBNM, UILJ, UKNU, UL, UM, UPUK, VKSCE, ZAGLJ
Mineral-associated organic matter (OM) represents a large reservoir of organic carbon (OC) in natural environments. The factors controlling the extent of the mineral-mediated OC stabilization, ...however, are poorly understood. The protection of OM against biodegradation upon sorption to mineral phases is assumed to result from the formation of strong bonds that limit desorption. To test this, we studied the biodegradation of OM bound to goethite (α-FeOOH), pyrophyllite, and vermiculite via specific mechanisms as estimated from OC uptake in different background electrolytes and operationally defined as ‘ligand exchange’, ‘Ca
2+ bridging’, and ‘van der Waals forces’. Organic matter extracted from an Oa forest floor horizon under Norway spruce (
Picea abies (L.) Karst) was reacted with minerals at dissolved OC concentrations of ∼5–130
mg/L at pH 4. Goethite retained up to 30.1
mg OC/g predominantly by ‘ligand exchange’; pyrophyllite sorbed maximally 12.5
mg OC/g, largely via ‘van der Waals forces’ and ‘Ca
2+ bridging’, while sorption of OM to vermiculite was 7.3
mg OC/g, mainly due to the formation of ‘Ca
2+ bridges’. Aromatic OM components were selectively sorbed by all minerals (goethite
≫
phyllosilicates). The sorption of OM was strongly hysteretic with the desorption into 0.01
M NaCl being larger for OM held by ‘Ca
2+ bridges’ and ‘van der Waals forces’ than by ‘ligand exchange’. Incubation experiments under aerobic conditions (initial pH 4; 90 days) revealed that OM mainly bound to minerals by ‘ligand exchange’ was more resistant against mineralization than OM held by non-columbic interactions (‘van der Waals forces’). Calcium bridges enhanced the stability of sorbed OM, especially for vermiculite, but less than the binding via ‘ligand exchange’. Combined evidence suggests that the extent and rate of mineralization of mineral-associated OM are governed by desorption. The intrinsic stability of sorbed OM as related to the presence of resistant, lignin-derived aromatic components appears less decisive for the sorptive stabilization of OM than the involved binding mechanisms. In a given environment, the type of minerals present and the solution chemistry determine the operating binding mechanisms, thereby the extent of OM sorption and desorption, and thus ultimately the bioavailability of mineral-associated OM.
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GEOZS, IJS, IMTLJ, KILJ, KISLJ, NUK, OILJ, PNG, SAZU, SBCE, SBJE, UL, UM, UPCLJ, UPUK
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