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1.
The processes governing the (im)mobilization of Al, Fe and dissolved organic matter (DOM) in podzols are still subject to debate. In this study we investigated the mechanisms of (im)mobilization of Al, Fe and organic matter in the upper and lower B horizons of two podzols from the Netherlands that are in different stages of development. We equilibrated batches of soil material from each horizon with DOM solutions obtained from the Oh horizon of the corresponding soil profiles. We determined the amount of (im)mobilized Al, Fe and DOM after addition of Al and Fe at pH 4.0 and 4.5 and initial dissolved organic carbon (DOC) concentrations of 10 mg C litre?1 or 30 mg C litre?1, respectively. At the combination of pH and DOC concentrations most realistic for the field situation, organic matter was retained in all horizons, the most being retained in the lower B horizon of the well‐developed soil and the least in the upper B horizon of the younger profile. Organic matter solubility seemed to be controlled mainly by precipitation as organo‐metal complexes and/or by adsorption on freshly precipitated solid Al‐ and Fe‐phases. In the lower B horizons, at pH 4.5, solubility of Al and Fe appeared to be controlled mainly by the equilibrium with secondary solid Al‐ and Fe‐phases. In the upper B horizons, the solubility of Al was controlled by adsorption processes, while Fe still precipitated as inorganic complexes as well as organic complexes in spite of the prevailing more acidic pH. Combined with a previous study of eluvial horizons from the same profiles, the results confirm the important role of organic matter in the transport of Al and Fe to create illuvial B horizons initially and subsequently deepening and differentiating them into Bh and Bs horizons.  相似文献   

2.
We have investigated the speciation and distribution of iron (Fe) and aluminium (Al) between minerals and organic species in A and B horizons of two Aluandic Andosols with X‐ray diffraction, thermal analyses, visible diffuse reflectance and Fourier transform infrared (FTIR) spectroscopies, together with selective and total chemical extractions. The two Aluandic Andosols of the Nilgiri Highlands (south India) have formed at the expense of intensively weathered lateritic formations of the Eocene. Data revealed that Al and Fe were predominantly stored in end‐weathering products of laterites, mainly as gibbsite and Fe (hydr)oxides in B horizons of the Aluandic Andosols. These secondary minerals are gradually replaced by organo‐metallic complexes in the topsoil A horizons exhibiting andic properties. We then indicate that formation of the organo‐metallic complexes results from weathering of the dominant crystalline Al‐ and Fe‐(hydr)oxides mediated by the organic ligands and complexation of the polyvalent metals following the accumulation of organic matter. Such weathering and complexation mechanisms are therefore similar to those recently ascribed to deferralitization and the formation of freely drained Umbric Podzols (Humus‐Podzols) in the upper Amazon Basin. In the present case, large supplies of both Al‐ and Fe‐bearing minerals provide large metal:carbon ratios that prevent the mobility of the organo‐metallic complexes and induce the formation of Aluandic Andosols rather than Podzols.  相似文献   

3.
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.  相似文献   

4.
The pH buffering and aluminium solubility characteristics of acid soil are important in determining the soil's response to changes in precipitation acidity. The chemistry of soil organic matter (humic substances) plays a key role in both processes, yet is complex and still poorly understood. Nevertheless, models of humic substance chemistry have been developed, one of which is WHAM–S, which contains a model (Model V) of proton and metal binding at discrete sites on humic substances and considers electrostatic effects on the binding strength. Here we have tested the ability of WHAM–S to model solution pH and Al using batch titration studies on organic and mineral soil horizons from forested sites in Norway, Germany and Spain, with ambient pH values from 3.73 to 5.73. We optimized the model predictions by adjusting the amounts of soil aluminium and humic substances within defined limits, taking the contents of copper chloride‐extractable Al and the base‐extractable organic matter as starting values. The model simulated both pH and dissolved Al well with optimized amounts of aluminium and humic substances within the defined limits (root mean squared error for pH from 0.01 to 0.22, for p[Al]aq (total dissolved Al) from 0.03 to 0.49, five data points). Control of dissolved Al by dissolved organic matter was important particularly at above‐ambient pH. In two mineral horizons we improved the fits by assuming that Al could precipitate as Al(OH)3. The optimized model also gave reasonable predictions of pH and dissolved Al in supernatants obtained by repeated leaching of the soil horizons. The results show that humic substances dominate the control of pH and dissolved Al in most of the horizons studied. Control by Al(OH)3 occurs but is the exception.  相似文献   

5.
Abstract. The aluminium (Al), iron (Fe) and Dissolved Organic Carbon (DOC) contents of the soil solution were monitored in two upland grassland and afforested podzol soils in Mid-Wales. Al organo-metallic complexes predominated in the O horizon leachates of the grassland soil, whereas inorganic monomeric Al forms dominated in the lower mineral horizons. Dissolved organic matter determines the chemistry, solubility, and transport of Al and Fe in the O horizon, and these are under strong biological control. The distributions of organic-Al, Fe and DOC within the soil profile were consistent with traditional podzolization theory. Observed increases in the molar ratios of Al:DOC in solution in the lower soil horizons may be responsible for the small solubility of Al organo-metallic complexes in those horizons. Afforestation increased the concentrations of organic-Al and Fe in the soil solution as compared with the concentrations observed for the grassland soil. Clearcutting further significantly mobilized Al and Fe from the upper soil horizon, primarily by increasing the DOC concentration in the soil water.  相似文献   

6.
Depositions originating from a central Slovak Al smelter may increase metal solubility in adjacent soils because they contain F (mainly HF). The reason for fluoro‐mobilization of metals may be the formation of soluble fluoro‐metal complexes or the mobilization of organic matter and subsequent formation of organo‐metal complexes. The objectives of our work were (1) to assess the extent of metal mobilization by fluoride in a Slovak Lithic Eutrochrept affected by the emissions of an Al smelter and (2) to model the dissolved metal species with the help of a chemical equilibrium model (MINEQL+). The O (Moder), A, and B horizons were equilibrated with solutions at F concentrations of 0, 0.9, 2.7, and 9.0 mmol l—1. In the extracts, the concentrations of Al, Ca, Cd, Cr, Cu, Fe, K, Mg, Mn, Ni, Pb, Zn, dissolved organic carbon (DOC), free and complexed F, and the pH and electrical conductivity (EC) were determined. The heavy metal concentrations in the O horizon (Cd: 0.99, Cr: 18.0, Cu: 44, Ni: 26, Pb: 110, and Zn: 84 mg kg—1) were 2.5 to 9 times larger than those in the A and B horizons. The concentrations of H2O‐soluble F decreased from the O (261 mg kg—1) to the A (103 mg kg—1) and B horizon (92 mg kg—1). In batch experiments increasing addition of F increased the equilibrium concentrations of Al, Cr, Cu, Fe, Ni, Pb, and DOC in all samples, of Cd in the A, and of K in the B horizon. At the same time the concentrations of complexed F and pH increased whereas EC decreased. Chemical equilibrium modelling indicated that the mobilizing effect of F resulted from the formation of fluoro‐Al complexes and organo‐complexes of all other metals.  相似文献   

7.
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.  相似文献   

8.
The aim of this study was to investigate the relationship between dissolved organic matter and chemical constituents of percolation water collected at 5, 20 and 40 cm depths from 13 ionbalance sampling plots located along lines extending through Finnish Lapland from Cu-Ni smelters in the Kola Peninsula, Russia. All the monitoring plots have as uniform as possible stand and site characteristics. The plots were located in Scots pine stands on dry and dryish sites with genetic horizons characteristic of Fe-humus podsols. The soil type on most of the sites was sorted fine sand or sand. Significant positive correlations were found between dissolved organic matter (DOM) and total dissolved Al concentrations at 5 and 20 cm, but not at 40 cm. A significant negative correlation was found between DOM and pH at 5 cm, but not at 20 or 40 cm. The anion deficit was positively correlated with DOM at 5 cm in the percolation water. Organic matter thus plays an important role as an anioh in percolation water, and regulates water pH in the surface soil. A high proportion of dissolved Al was in the form of organic complexes. Total dissolved Al levels were well below the toxic limits for pine.  相似文献   

9.
To better understand the behavior of metals in soil–plant systems, their physicochemical forms in rhizosphere soil should be elucidated. The dissolved organic matter (DOM) in a soil solution influences the mobility and bioavailability of metals in soil. The present study examined the effects of plant growth on DOM–metal complexes in a rhizosphere soil solution using size exclusion chromatography combined with an inductively coupled plasma-mass spectrometer system (SEC–ICP-MS) and an ultrafiltration technique. Humus-rich volcanic ash soil from the surface of an agricultural field was used in a pot cultivation experiment. Brassica rapa nothovar. was cultivated in a pot in which rhizosphere soil (R) was separated by a nylon net screen from non-rhizosphere soil (NR). Soil solutions were collected using a high-speed centrifugation method 3 weeks after sowing and analyzed using SEC–ICP-MS. Some peaks of DOM with a high molecular size were detected in the ultraviolet-absorbing chromatograph (280 nm) of the soil solution samples. Their concentrations were much higher in the R solution than in the NR solution. Metals including Al, Fe, Cu, Zn, Pb, Y, La and U were detected at the ultraviolet peak positions of the DOM. The ultrafiltration experiment showed that the size distributions of the organic materials to which the metals were combined differed between the R and NR soil solutions. These results suggest that plant growth enhanced the dissolution of metals adsorbed with organic matter from the solid phase in rhizosphere soil.  相似文献   

10.
This paper discusses the effects of different horizons and soil solution compositions on dissolved organic matter retention in a moorland podzol and compares the results with previous studies of forest podzols. Adsorption isotherms were constructed for each of the major horizons of a freely draining, upland, moorland, humic podzol from north-east Scotland, to investigate processes of retention and release of dissolved organic matter (DOM). Carbon retention of a range of solute types was studied, and phthalate was chosen as a model compound to measure carbon retention at three different pH values (3, 4.5 and 6). Retention and release of DOM was related to chemical, physical and mineralogical characteristics of the different soil horizons. All the mineral horizons retained DOM, with the Bs horizon most retentive. Solution pH did not significantly affect DOM retention in the O and A horizons. At pH 3 and 4.5 organic matter was weakly retained in the Bhs horizon, but strongly retained in the Bs and the Cx horizons. At pH 6 reversal of surface charge occurred in the Bs and Cx horizons resulting in the release of similar amounts of organic matter to that released from the O horizon at the same pH. The results demonstrate how podzols act as a ‘valve’ in controlling the input of dissolved organic compounds into surface and ground water, and how sensitive the controlling mechanisms are to pH change.  相似文献   

11.
Because dissolved organic matter (DOM) plays an important role is terrestrial C-, N- and P-balances and transport of these three components to aquatic environments, there is a need to include it in models. This paper presents the concept of the newly developed DOM modules implemented in the DAISY model with focus on the quantification of DOM sorption/desorption and microbial-driven DOM turnover. The kinetics of DOM sorption/desorption is described by the deviation of the actual DOM concentration in solution from the equilibrium concentration, Ceq. The Ceq is soil specific and estimated from pedotransfer functions taking into account the soil content of organic matter, Al and Fe oxides. The turnover of several organic matter pools including one DOM pool are described by first-order kinetics.The DOM module was tested at field scale for three soil treatments applied after cultivating grass–clover swards. Suction cups were installed at depths 30, 60 and 90 cm and soil solution was sampled for quantification of dissolved organic C (DOC) and dissolved organic N (DON). In the topsoil, the observed fluctuations in DOC were successfully simulated when the sorption/desorption rate coefficient k was low. In the subsoil, the observed concentrations of DOC were steadier and the best simulations were obtained using a high k. The model shows that DOC and DON concentrations are levelled out in the subsoils due to soil buffering. The steady concentration levels were based on the Ceq for each horizon and the kinetic concept for sorption/desorption of DOC appeared a viable approach. If Ceq was successfully estimated by the pedotransfer function it was possible to simulate the DOC concentration in the subsoil. In spite of difficulties in describing the DOC dynamics of the topsoil, the DOM module simulates the subsoil concentration level of DOC well, and also—but with more uncertainty—the DON concentration level.  相似文献   

12.
The precipitation of dissolved organic matter (DOM) by aluminum (Al) results in a stable soil organic matter (OM) fraction. Extracellular enzymes can also be removed from soil solution by sorption or precipitation, but whether this affects their activity and their importance for carbon (C) mineralization is largely unknown. We studied the activity of eight extracellular enzymes, precipitated by Al together with DOM, in relation to C mineralization of the precipitated OM. Dissolved OM was obtained from the Oi and Oa horizon of two forest soils and precipitated at different Al : C ratios and pH values to achieve a large variation in composition and C mineralization of precipitated OM. All eight enzymes were present in a functional state in precipitated OM. On average 53% of DOM was precipitated, containing on average 17%–41% of the enzyme activity (EA) involved in C degradation (chitinase, cellobiohydrolase, β‐glucosidase, glucuronidase, lacasse, and xylosidase) previously present in soil solution. In contrast, on average only 4%–7% of leucine‐aminopeptidase and acid‐phosphatase activity was found in precipitated OM. The EA found in precipitates significantly increased the percentage of C mineralized of precipitated OM, with a stronger influence of C‐degrading enzymes than enzymes involved in N and P cycling. However, after 8 weeks of incubation the correlations between EA and C mineralization disappeared, despite substantial EA being still present and only 0.5%–7.7% of C mineralized. Thus, degradation of precipitated OM seems to be governed by EA during the first degradation phase, but the long‐term stability of precipitated OM is probably related to its chemical properties.  相似文献   

13.
Sorption on the mineral matrix is an important process restricting the movement of dissolved organic matter (DOM) in soils. In this study, we aimed to identify the chemical structures responsible for the retention of DOM by sorption experiments with total DOM and acidic humic substances (AHS), containing humic and fulvic acids, on soil samples and minerals (goethite, ferrihydrite, and amorphous Al(OH)3). The AHS remaining in solution after sorption were studied by 13C nuclear magnetic resonance (NMR) analysis, and total DOM and AHS for bed on the surfaces of minerals by diffuse reflectance Fourier-transform infrared (DRIFT) spectroscopy. The soil samples were taken from strongly sorbing Bw horizons of two Inceptisols rich in pedogenetic Fe (29 and 35 g kg ?1) and containing little C (7 and 22 g kg?1). The 13C-NMR spectra showed that sorption causes a preferential removal of aromatic and carboxyl C from the solution, whereas alkyl-C accumulates in the solution. No change was observed for O-alkyl C. The DRIFT spectra of sorbed total DOM and AHS showed a relative increase of the band intensity of carboxyl groups compared to DOM in the initial solution, confirming the importance of those groups for the sorption to mineral surfaces. The spectra also indicated reactions of carboxyl groups with metals at the mineral surfaces. The extent to which the carboxyl groups are bound depended on the surface coverage with DOM and the type of mineral.  相似文献   

14.
Morphological, geochemical and mineralogical studies were carried out in a representative soil catena of the low‐elevation plateaux of the upper Amazon Basin to interpret the steps and mechanisms involved in the podzolization of low‐activity clay soils. The soils are derived from Palaeozoic sandstones. They consist of Hydromorphic Podzols under tree savannah in the depressions of the plateaux and predominantly of Acrisols covered by evergreen forest elsewhere. Incipient podzolization in the uppermost Acrisols is related to the formation of organic‐rich A and Bhs horizons slightly depleted in fine‐size particles by both mechanical particle transfer and weathering. Weathering of secondary minerals by organic acids and formation of organo‐metallic complexes act simultaneously over short distances. Their vertical transfer is limited. Selective dissolution of aluminous goethite, then gibbsite and finally kaolinite favour the preferential cheluviation of first Fe and secondly Al. The relatively small amount of organo‐metallic complexes produced is related to the quartzitic parent materials, and the predominance of Al over Fe in the spodic horizons is due to the importance of gibbsite in these low‐activity clay soils. Morphologically well‐expressed podzols occur in strongly iron‐depleted topsoils of the depression. Mechanical transfer and weathering of gibbsite and kaolinite by organic acids is enhanced and leads to residual accumulation of sands. Organo‐metallic complexes are translocated in strongly permeable sandy horizons and impregnate at depth the macro‐voids of embedded soil and saprolite materials to form the spodic Bs and 2BCs horizons. Mechanical transfer of black particulate organic compounds devoid of metals has occurred later within the sandy horizons of the podzols. Their vertical transfer has formed well‐differentiated A and Bh horizons. Their lateral removal by groundwater favours the development of an albic E horizon. In an open and waterlogged environment, the general trend is therefore towards the removal of all the metals that have initially accumulated as a response to the ferralitization process and have temporarily been sequestrated in organic complexes in previous stages of soil podzolization.  相似文献   

15.
Al chemistry was studied in two acidic watersheds, one with a podzol, the other with an acid brown soil, in the Vosges mountains (N.E. France), by analysing both leaching and centrifugation soil solutions and spring waters over 3 yr. In the podzol, Al was mobilized in the eluvial horizons under the predominant influence of organic acidity, then leached down the profile as organic and F-bound Al. Strong undersaturation with respect to proto-imogolite and imogolite showed that the proto-imogolite theory of podzolization could not apply. Al was transferred from the soil to spring water mostly as Al3+ and Al-F. Al3+, as well as additional minor species (AlOH2+, AlSO4 +), originated from the redissolution of the top of the spodic horizons under the influence of both soil solution acidity and the occurrence of mobile anions derived from atmospheric deposition. Conversely, in the acid brown soil, Al mobilization was regulated by nitrate and occurred mainly as Al3+. Most of Al was retained in the deep soil and only traces of monomeric Al reached spring water. In the podzol eluvial horizons, soil solutions were undersaturated with respect to all relevant mineral phases and their chemical composition agree with the concept of a mobilization of Al from the solid soil organic Al and a control of Al3+ activity by complexation reaction with the solid and soluble soil organic matter and F. In the acid brown soil, soil solutions were found to be in equilibrium with natural alunite, and the formation of this mineral, if confirmed, would account for the occurrence of 'open' vermiculites instead of the expected hydroxy-Al interlayered vermiculites. Al solubility control in surface water of both watersheds remains unclear. The Al-F species in both watersheds and the likely control of Al solubility by alunite in the acid brown soil emphasize the influence of acid deposition on Al chemistry in acid watersheds.  相似文献   

16.
Soluble organic matter derived from exotic Pinus species has been shown to form stronger complexes with iron (Fe) than that derived from most native Australian species. It has also been proposed that the establishment of exotic Pinus plantations in coastal southeast Queensland may have enhanced the solubility of Fe in soils by increasing the amount of organically complexed Fe, but this remains inconclusive. In this study we test whether the concentration and speciation of Fe in soil water from Pinus plantations differs significantly from soil water from native vegetation areas. Both Fe redox speciation and the interaction between Fe and dissolved organic matter (DOM) were considered; Fe – DOM interaction was assessed using the Stockholm Humic Model. Iron concentrations (mainly Fe2+) were greatest in the soil waters with the greatest DOM content collected from sandy podosols (Podzols), where they are largely controlled by redox potential. Iron concentrations were small in soil waters from clay and iron oxide‐rich soils, in spite of similar redox potentials. This condition is related to stronger sorption on to the reactive clay and iron oxide mineral surfaces in these soils, which reduces the amount of DOM available for electron shuttling and microbial metabolism, restricting reductive dissolution of Fe. Vegetation type had no significant influence on the concentration and speciation of iron in soil waters, although DOM from Pinus sites had greater acidic functional group site densities than DOM from native vegetation sites. This is because Fe is mainly in the ferrous form, even in samples from the relatively well‐drained podosols. However, modelling suggests that Pinus DOM can significantly increase the amount of truly dissolved ferric iron remaining in solution in oxic conditions. Therefore, the input of ferrous iron together with Pinus DOM to surface waters may reduce precipitation of hydrous ferric oxides (ferrihydrite) and increase the flux of dissolved Fe out of the catchment. Such inputs of iron are most probably derived from podosols planted with Pinus.  相似文献   

17.
Field and laboratory studies combined with destructive and nondestructive analytical methods were used to characterize dissolved organic matter (DOM) in acid forest soils. DOM is produced in significant amounts in the forest canopy and in the forest floor. A major part of the organic solutes are lignocellulose-degradation products being strongly microbially altered in the course of ligninolysis. The release of lignin-derived moieties into the soil solution is controlled by their degree of biooxidation. Microorganisms contribute also directly to the organic solutes through the release of microbial metabolites. DOM released from the forest floor passes the upper mineral soil almost conservatively, whereas in the subsoil most DOM is removed from solution. Immobilization of DOM is mainly due to sorption on Fe and Al oxides. The highly oxidized lignin-derived moieties are preferentially removed from the soil solution whereas the saccharides are relatively enriched. We conclude that DOM in the forest soil output to the hydrosphere is a result of (1) the release of microbially degraded lignocellulose compounds and of microbial metabolites into the forest floor solution and (2) selective sorptive removal of the lignin-derived constituents in the subsoil.  相似文献   

18.
Prediction of the fate of metals in soil requires knowledge of their solid–liquid partitioning. This paper reviews analytical methods and models for measuring or predicting the solid–liquid partitioning of metals in aerobic soils, and collates experimental data. The partitioning is often expressed with an empirical distribution coefficient or Kd, which gives the ratio of the concentration in the solid phase to that in the solution phase. The Kd value of a metal reflects the net effect of various reactions in the solid and liquid phases and varies by orders of magnitude among soils. The Kd value can be derived from the solid–liquid distribution of added metal or that of the soil‐borne metal. Only part of the solid‐phase metal is rapidly exchangeable with the solution phase. Various methods have been developed to quantify this ‘labile’ phase, and Kd values based on this phase often correlate better with soil properties than Kd values based on total concentration, and are more appropriate to express metal ion buffering in solute transport models. The in situ soil solution is the preferred solution phase for Kd determinations. Alternatively, water or dilute‐salt extracts can be used, but these may underestimate in situ concentrations of dissolved metals because of dilution of metal‐complexing ligands such as dissolved organic matter. Multi‐surface models and empirical models have been proposed to predict metal partitioning from soil properties. Though soil pH is the most important soil property determining the retention of the free metal ion, Kd values based on total dissolved metal in solution may show little pH dependence for metal ions that have strong affinity for dissolved organic matter. The Kd coefficient is used as an equilibrium constant in risk assessment models. However, slow dissociation of metal complexes in solution and slow exchange of metals between labile and non‐labile pools in the solid phase may invalidate this equilibrium assumption.  相似文献   

19.
We summarize progress with respect to (1) different approaches to isolate, extract, and quantify organo‐mineral compounds from soils, (2) types of mineral surfaces and associated interactions, (3) the distribution and function of soil biota at organo‐mineral surfaces, (4) the distribution and content of organo‐mineral associations, and (5) the factors controlling the turnover of organic matter (OM) in organo‐mineral associations from temperate soils. Physical fractionation achieves a rough separation between plant residues and mineral‐associated OM, which makes density or particle‐size fractionation a useful pretreatment for further differentiation of functional fractions. A part of the OM in organo‐mineral associations resists different chemical treatments, but the data obtained cannot readily be compared among each other, and more research is necessary on the processes underlying resistance to treatments for certain OM components. Studies using physical‐fractionation procedures followed by soil‐microbiological analyses revealed that organo‐mineral associations spatially isolate C sources from soil biota, making quantity and quality of OM in microhabitats an important factor controlling community composition. The distribution and activity of soil microorganisms at organo‐mineral surfaces can additionally be modified by faunal activities. Composition of OM in organo‐mineral associations is highly variable, with loamy soils having generally a higher contribution of polysaccharides, whereas mineral‐associated OM in sandy soils is often more aliphatic. Though highly reactive towards Fe oxide surfaces, lignin and phenolic components are usually depleted in organo‐mineral associations. Charred OM associated with the mineral surface contributes to a higher aromaticity in heavy fractions. The relative proportion of OC bound in organo‐mineral fractions increases with soil depth. Likewise does the strength of the bonding. Organic molecules sorbed to the mineral surfaces or precipitated by Al are effectively stabilized, indicated by reduced susceptibility towards oxidative attack, higher thermal stability, and lower bioavailability. At higher surface loading, organic C is much better bioavailable, also indicated by little 14C age. In the subsurface horizons of the soils investigated in this study, Fe oxides seem to be the most important sorbents, whereas phyllosilicate surfaces may be comparatively more important in topsoils. Specific surface area of soil minerals is not always a good predictor for C‐stabilization potentials because surface coverage is discontinuous. Recalcitrance and accessibility/aggregation seem to determine the turnover dynamics in fast and intermediate cycling OM pools, but for long‐term OC preservation the interactions with mineral surfaces, and especially with Fe oxide surfaces, are a major control in all soils investigated here.  相似文献   

20.
Aluminium (Al) is abundant in soils, but the influence of Al on the mineralization of dissolved organic carbon and thus on carbon sequestration in soil is only poorly understood. We investigated the extent and rate of mineralization of dissolved organic carbon at various Al/C ratios. Dissolved organic carbon extracted from Oi and Oa layers under coniferous and deciduous forest was incubated with initial molar Al/C ratios from < 0.004 to 0.44 for 130 days. Mineralization was quantified by measurement of CO2. Rapidly and slowly mineralizable pools of dissolved organic C and their decomposition rate constants and half‐lives (as a measure of labile and stable C) were modelled with a double exponential equation. Increasing initial Al/C ratios up to 0.1 led to a considerable decrease in mineralization (up to 50% compared with control samples). The half‐life of the stable C pool increased up to 4‐fold, whereas the half‐life of the labile C pool was unaffected. Ratios of Al/C > 0.1 did not further decrease the mineralization, but led to increasing concentrations of free Al3+ in solution, and to increasing Al/C ratios in the precipitate, indicating that the Al complexation capacity of dissolved organic C was exceeded. Decrease in mineralization as well as formation of particulate organic matter (up to 56% of initial dissolved organic C) affected mainly the stable pool. Mineralization of dissolved organic C can be predicted from UV absorption by use of exponential regressions, but adding an Al variable did not improve the prediction significantly. We conclude that Al influences substantially the biodegradability of dissolved organic C percolating into the mineral soil, which may have consequences for the carbon sequestration in the soil. Declining Al concentrations would increase the mineralization of dissolved organic C only if the Al/C ratio becomes less than the ‘threshold value’ in the range of the Al complexation capacity of the dissolved organic C.  相似文献   

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