Interactions of fulvic acid with aluminium and a proto‐imogolite sol: the contribution of E‐horizon eluates to podzolization

The podzolization process is examined in the light of measurements of the solubility characteristics of aluminium fulvate, the extent of dissolution of a proto‐imogolite sol by fulvic acid, the adsorption capacity of proto‐imogolite for fulvic acid and aluminium fulvate, and published evidence. Fulvic acid at 500 mg l^?1 acting on a proto‐imogolite (PI) preparation containing 0.95 mmol l^?1 Al as PI did not bring enough Al into solution at pH 4.5–5.0 over 4–15 months to cause significant precipitation of the fulvic acid. As allophanic Bs horizons of podzols typically have pH ≥ 4.8, fulvic acids entering them in drainage water cannot be quantitatively precipitated by dissolution of Al from the allophane. They are, however, strongly absorbed on the allophane, and this must be the mechanism that removes most of the fulvic acid at the top of the Bs horizon, and which contributes, along with colloidal humus and root decomposition, to the formation of a Bh horizon. We conclude that fulvic acid plays no active role in podzolization, but only recycles Al and Fe, that have been transferred by biological processes to the O horizon, back to the Bh horizon. The podzolization process, which leads to the formation of an allophanic Bs horizon underlying a progressively deepening E horizon, requires the dissolution of Al‐humate and allophanic precipitates at the Bh–Bs interface as well as progressive attack on the more readily weatherable minerals. Inorganic acids, particularly episodic fluxes of nitric acid, could play a major role in this, as well as attack by readily metabolized complexing acids such as oxalic and citric acids released by roots and fungi. In addition to throwing light on the podzolization process, the experimental results provide an explanation of the lower limit to C:Al ratios reported in natural waters, and a check on the applicability of the WHAM chemical equilibrium model to Al–fulvate–proto‐imogolite equilibria. In Ca‐containing fulvate solutions, Al‐fulvate begins to precipitate when C:Al falls below 50, which is also the limiting ratio observed in natural waters. WHAM calculations overestimate by 70–85% the amount of Al‐fulvate formed over 4 months at pH 4.5–5.0 in Ca‐containing fulvate–imogolite systems.     

Water-soluble organic matter in incipient podzols: accumulation in B horizons or in fibres?

To elucidate the mechanism of podzolization in its first stages we studied the fate of the water-soluble organic matter (WSOM) in incipient podzols in sandy soils by comparing the composition of the WSOM from L, F and H horizons with that in the bulk of the Bh horizons and fibres of three profiles. The WSOM appeared to consist significantly of ligno-cellulose and proteins, but these biopolymers were hardly present in the Bh horizons. The material of the fibres, however, greatly resembled the WSOM composition, thereby suggesting that in these soils most of the WSOM is transported through the B horizon and accumulates hardly changed in thin bands where the water stops moving. This implies that in the early steps of podzolization, accumulation of organic matter in the B horizon is not likely to be caused by water-soluble material.     

Retention and release of dissolved organic matter in Podzol B horizons

The main objectives were to study the effects of pH on the retention and release of organic matter in acid soil, and to determine the main differences in results obtained from batch experiments and experiments in columns. We took soil material from the B horizons of a Podzol at Skånes Värsjö (southern Sweden). In batch experiments, soil was equilibrated with solutions varying in pH and concentration of dissolved organic C. In Bh samples, the release of dissolved C gradually increased with increase in pH. In the Bs1 material there was a minimum at pH 4.1, and in the Bs2 soil the minimum occurred at pH 4.6. The ability to retain added dissolved C increased in the order Bh < Bs1 < Bs2. The column experiment was run for 160 days under unsaturated flow conditions. Columns were packed with Bh, Bh + Bs1 or Bh + Bs1 + Bs2 samples to calculate mass balances for each horizon. Solutions either without any dissolved organic C or ones containing 49 mg C dm^?3 with pH of 4.0 or 3.6 were used to leach columns. The pH of input solutions only little affected the concentration of dissolved C in the effluent. Relative proportions of hydrophobic substances decreased with increasing column length and decreasing pH. For input solutions containing dissolved C, near steady state was achieved for both the Bs1 and Bs2 horizons with approximately 25% dissolved organic matter retention. Thus, no maximum sorption capacity for dissolved C could be defined for these horizons. This behaviour could not have been predicted by batch data, showing that column experiments provide useful additional information on interactions between organic compounds and solid soil material.     

Mechanisms controlling the mobility of dissolved organic matter, aluminium and iron in podzol B horizons

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.     

Podzolization as a deferralitization process: a study of an Acrisol–Podzol sequence derived from Palaeozoic sandstones in the northern upper Amazon Basin

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.     

A reassessment of podzol formation processes

Translocated (oxalate-soluble) Al and Fe are present predominantly in inorganic forms in the B₂ horizons of the five pcdzol profiles examined: A1 as imogolite and proto-imogolite allophanes, and Fe as a separate oxide phase. Below the top few cm of the B₂ horizon, over 75 per cent of the extractable (acid-plus alkali-soluble) organic matter is present as Al-fulvates, largely sorbed on allophanic material. The Bh horizons of the Iron Humus Podzol and Iron Podzol intergrades are distinguished by very high levels of organically bound Fe (soluble in EDTA solution), five to ten times more than in immediately adjacent A₂ or B₂ horizons, and also by larger humic acid contents than in comparable B₂, levels in typical Iron Podzols. Inorganic forms of translocated Al and Fe are probably absent from two of the three Bh horizons examined, and also from the Bhg horizon overlying the thin iron pan in the Peaty Podzol. The organic matter in this Bhg horizon is saturated with Al rather than Fe. Chemical and physical processes which could lead to evolution of a profile along the genetic sequence, Iron Podzol, Iron Humus Podzol, Peaty Podzol, are postulated. During the formation of an Iron Podzol, positively charged inorganic sols carry aluminium, silicon and iron from the A₂ and deposit them in the B₂ horizon; subsequently, with the development of an H layer, colloidal humus migrates through the A₂ and precipitates on the positive colloids at the top of the B₂ horizon to form a Bh horizon, in which remobilized ferric species are trapped by the organic matter. In higher rainfall areas, occasional waterlogging above the oxide-impregnated B₂ leads to a thin iron pan, separating permanently oxidizing conditions below from seasonally waterlogged and reducing conditions above.     

13C/12C Ratios of soil organic matter as indicators of vegetation changes in the congo

The ¹³C/¹²C ratios were determined for the organic matter of all horizons of a podzol profile and of the A₁ horizons of some ferrallitic soils, in some grass shoots and in a fossil root fragment from the B_2h horizon of the podzol. The isotope ratio in the organic matter of the A₁ horizon of the podzol matches those in grass shoots from the present savanna vegetation. The ratios in the lower horizons match those of organic matter in the A₁ horizons of soils under forest and that of the fossil root fragment in the B_2h horizon. The ratios thus demonstrate that the humus enrichment of the B_2h horizon of the podzol occurred while it was under forest vegetation and that the present grass vegetation did not take part in the podzolization process. The differences also indicate that savanna replaced forest vegetation after the profile had been formed.     

Bodenentwicklung am Rande oligotropher Moore im Raum Berlin

Soil development in the surrounding of oligotrophic mires in the Berlin region Polygenetic soils, surrounding oligotrophic kettle hole mires in the valley and aeolian sand areas of the Berlin region, were investigated. The typical soil catena is formed by the sequence of Ombric Histosol (Niedermoor), Ombric Histosol/Albi‐gleyic Podzol (Moor‐Podsol‐Gley), Albi‐gleyic Podzol (Nasspodsol‐Gley), Gleyic Podzol (Podsol‐Gley), and Dystri‐gleyic Arenosol (Gley‐Podsol‐Braunerde) (German soil classifications in parenthesis). Field and laboratory work showed, that the investigated soils were strongly related to each other and that their development depends on the trophy of the mire and groundwater fluctuations during the Holocene. Compared with the Bh‐horizon of terrestrial soils the Gh‐horizon is nearly free of Fe and Mn, but very rich in pedogenic Al‐oxides and rich in organic matter. The genesis of the soils is explained as follows: 1. The development of different Gleyic Podzols was due to rise of groundwater. Consequently the Bh and Bs horizons of Podzols surrounding the mire were converted to Gh and Gr horizons. 2. Humic substances and Al in the Gh and Gr horizons were not re‐mobilized due to the rise of groundwater, whereas Fe and Mn were reduced and removed by groundwater. 3. At the periphery of the mire Fe was enriched in the Go horizon of the Gley‐Podzols but not Mn. 4. The fact that the mire is completely surrounded by Podzol‐Gleys, indicates, that movement of the groundwater from the central parts of mires towards the periphery is an essential pedogenetic factor.     

Pyrolysis methylation—mass spectrometry of whole soils

In-source pyrolysis field ionization mass spectrometry (Py-FIMS) and Curie–point pyrolysis gas chromatography/mass spectrometry (Py-GC/MS) have been applied to the characterization of whole soils methylated off–line and on–line by two methylation reagents. Samples of a gleysolic Ap–horizon and a podzolic Bh horizon (C_org concentrations 2–3%) were investigated by conventional on–line and developed off–line methylation with tetramethylammonium hydroxide (TMAH) and by off–line methylation with diazomethane. For the first method, the soils were dried, milled and pretreated with TMAH for 10 min at 250°C at ambient pressure outside the pyrolyzers. For the second method, the dried and milled soils were methylated with an ether solution of diazomethane for 12 h at room temperature (～20°C). Pyrolysis methylation with TMAH enabled aliphatic C₂–C39 monocarboxylic acid methyl esters, C4–C₃₀ dicarboxylic acid dimethyl esters and benzenecarboxylic acid methyl esters to be detected. Methoxybenzenes from phenols, benzenediols and benzenetriols, methoxybenzenecarboxylic acid methyl esters from phenolic acids and furancarboxylic acid methyl esters from carbohydrates were also identified. Nitrogen–containing compounds in soil organic matter were obtained as N,N–dimethylamides. Using diazomethane as methylation reagent, distinct Py-FIMS signals were observed for aliphatic C₂–C₃₂ monocarboxylic acid methyl esters and C₃–C₂4 dicarboxylic acid dimethyl esters. Additionally, methoxybenzenes originating from lignins, methoxybenzenecarboxylic acid methyl esters from phenolic acids and N,N–dimethylamides from amides were detected. The more acid podzolic Bh horizon showed higher relative intensities for dicarboxylic acid dimethyl esters and methylated phenolic acids compared to the gleysolic Ap horizon. Similarly, benzenecarboxylic acids are connected mainly by ester linkages to the macromolecular network of soil organic matter. Both methylation procedures support conventional Py-FIMS and Py-GC/MS and give valuable additional information on the occurrence of aliphatic and aromatic carboxylic acids, substituted phenols, benzenediols, benzenetriols, phenolic acids and amides in soil organic matter.     

Organic matter retention in an upland humic podzol; the effects of pH and solute type

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.     

Chemical and mineralogical properties of sandy and loamy-sandy ochreous brown earths in relation to incipient podzolization in a brown earth—podzol evolutive sequence

Chemical and mineralogical properties of ochreous brown earths have been studied with particular reference to: (1) the distribution within the profiles of Fe and Al compounds; (2) the occurrence of smectite-like clay minerals in surface horizons. Ochreous brown earths studied belong to a developmental sequence of forest soils, from acid brown earths to ferric podzols, developed on sandy or loamy-sandy acid parent materials. In such a soil sequence, both selective chemical and mineralogical data show clearly that podzolization is already active in ochreous brown earths, whereas such an incipient podzolization is quite undetectable by direct morphological observations. The distribution patterns of amorphous Fe and Al hydrous oxides and organic associations, clearly show the intergrade character of ochreous brown earths, when compared with the vertical distribution of Fe and Al forms in acid brown earths and podzolized soils. The Fe/Al ratio of both an NH₄-oxalate extract and an NaOH/Na-tetraborate extract buffered at pH 9.7, measured in the A₁B diagnostic horizon of ochreous brown earths, is a particularly appropriate and useful genetic criterion for the detection of incipient podzolization. Moreover, the presence of expansible clay minerals (degradation smectites) in the clay-sized fraction of the surface horizons of ochreous brown earths (A₁ and A₁B) can be considered as supplementary evidence of incipient podzolization.     

Podzol development with time in sandy beach deposits in southern Norway

The coastal areas of SE Norway provide suitable conditions for studying soil development with time, because unweathered land surfaces have continuously been raised above sea level by glacio‐isostatic uplift since the termination of the last ice age. We investigated Podzol development in a chronosequence of six soils on sandy beach deposits with ages ranging from 2,300 to 9,650 y at the W coast of the Oslofjord. The climate in this area is rather mild with a mean annual temperature of 6°C and an annual precipitation of 975 mm (Sandefjord). The youngest soil showed no evidence of podzolization, while slight lightening of the A horizon of the second soil (3,800 years) indicated initial leaching of organic matter (OM). In the 4,300 y–old soil also Fe and humus accumulation in the B horizon were perceptible, but only the 6,600 y–old and older soils exhibited spodic horizons. Accumulation of OM in the A horizons reached a steady state in <2,300 y, while in the B horizons OM accumulated at increasing rates. pH dropped from 6.6 (H₂O)/5.9 (KCl) in the recent beach sand to 4.5 (H₂O)/3.8 (KCl) within approx. 4,500 y (pH_H2O)/2,500 y (pH_KCl) and stayed constant thereafter, which was attributed to sesquioxide buffering. Base saturation showed an exponential decrease with time. Progressive weathering was reflected by increasing Fe_d and Al_d contents, and proceeding podzolization by increasing amounts of pyrophophate‐ and oxalate‐soluble Fe and Al with soil age. These increases could be best described for most Fe and Al fractions by exponential models. Only the increasing amounts of Fe_p could be better described by a power function and those of Fe_o by a linear model.     

Distribution of allophane and organic matter in podzol B horizons: reply to Buurman & Van Reeuwijk

The macromorphology, micromorphology and chemical nature of illuvial material in podzol B horizons and subsoils can be explained by contributions from two different migrating species: (a) a positively-charged mixed Al₂O₃-Fe₂O₃-SiO₂-H₂O sol incorporating minor amounts of adsorbed organic matter and silicate clay, and (b) negatively charged organic sols and solutions, carrying minor amounts of Al, Fe and clay. These species can also be generated within B horizons of high root activity. An alternative theory, that requires allophane to be formed in situ in the B horizon by microbial decomposition of precipitated organic complexes, fails to predict the observed distribution of allophane.     

Cold and hot water–extractable organic matter as indicators of litter decomposition in forest soils

Mild extractions were used as indicators of easily decomposable organic matter (OM). However, the chemical composition of extracted OM often remained unclear. Therefore, the composition of cold and hot water–extractable OM was investigated in the O horizons (Oi, Oe, Oa) of a 170 y old beech stand (Fagus sylvatica) in the Ore Mtns., SE Germany. To simulate litter decomposition, the O horizon samples were incubated for 1 week under defined conditions. Cold‐ and hot‐water extracts were analyzed and chemically characterized by pyrolysis–field ionization mass spectrometry (Py‐FIMS). The C and N concentrations were always lower in the cold‐(C: 2.69 to 3.95 g kg^–1; N: 0.14 to 0.29 g kg^–1) than in the hot‐water extracts (C: 13.77 to 15.51 g kg^–1; N: 0.34 to 0.83 g kg^–1). The C : N ratios of both extracts increased with increasing depth. Incubation increased the concentrations of C and N in all water extracts, while C : N ratios of extracts decreased. The molecular‐chemical composition of cold and hot water–extracted OM revealed distinct differences. Generally, cold water–extracted OM was thermally more stable than hot water–extracted OM. The mass spectra of the hot water–extracted organic matter revealed more intensive signals of carbohydrates, phenols, and lignin monomers. Additionally, the n‐C₂₈ fatty acid and the n‐C₃₈–to–n‐C₅₂ alkyl monoesters clearly distinguished the hot‐ from the cold‐water extract. A principle‐component analysis visualized (1) alterations in the molecular‐chemical composition of cold‐ and hot‐water extracts due to previous incubation of the solid O horizon samples and (2) a decomposition from the Oi to the Oh horizon. This provides evidence that the macromorphological litter decomposition was reflected by the chemical composition of water extracts, and that Py‐FIMS is well‐suited to explain at the molecular level why OM decomposability is correlated with water‐extracted C.     

Mineralogic evolution in hydromorphic sandy soils and podzols in “landes du médoc”, France

Soils of the nearly level “Landes du Médoc” in southwestern France have a pattern of alternating bodies of hydromorphic podzols (Haplaquods) and low humic hydromorphic soils (Psammaquents). The soils are formed in a sedimentary mantle of coarse, quartzose sands with a slight microrelief consisting of low, elongated ridges and shallow, intervening troughs. The water table is at shallow depths throughout the plain, even at the surface in places. The podzols on the crests of the low ridges have distinct A₂ and cemented B₂ h horizons. Podzols persist down the sides of ridges but going downslope first lose the A₂ horizon and then the cementation of the Bh horizon. Soils in the shallow troughs have A₁ and Cg horizons without B horizons.The fine silt (2–20 μm) and clay (0–2 μm) fractions of the parent sand contain primary trioctahedral chlorite, mica, feldspars, and quartz, with the last mineral predominant. During soil development, the first three minerals undergo weathering at different rates and to different extents. Chlorite is most strongly weathered, followed in order by plagioclases and K-minerals. In the fine silt fraction, weathering seems to occur mostly by fragmentation of particles. In the clay fraction, the phyllosilicates successively form irregularly interstratified minerals with contractible but not expandable vermiculitic layers, interstratified minerals with contractible and expandable smectitic layers, and finally smectites.The extent to which the silicate minerals are weathered becomes progressively greater from the low humic hydromorphic soils to the podzols with friable Bh horizons to the podzols with cemented Bh horizons. Smectite is present only in the A₂ horizons of these last podzols.The aluminum release by weathering of silicate minerals is translocated in part in the form of organo-metal complexes into the Bh horizons of the podzols. Greatest concentrations of Al are associated with coatings of monomorphic organic matter on mineral grains in the cemented Bh horizons, in which some Al has also crystallized into gibbsite. That mineral was not detected in friable B horizons of podzols nor in the low humic hydromorphic soil. Contrary to expectations, the mobile Al did not enter interlayer spaces of expanding 2:1 clay minerals.     

Über die Sorptionseigenschaften von Waldböden bezüglich gelöster organischer Substanzen

About the sorption of dissolved organic matter to forest soils This investigation characterizes the major forest soils of the temperate climatic zones (leptosols, vertisols, cambisols, luvisols, podzols, stagnosols, gleysols) as sorbents for dissolved organic matter (DOM). Sorption isotherms were obtained for 135 soil horizons from 36 profiles. When solutions containing no DOC were added, the release of dissolved organic carbon (DOC) was highest for horizons rich in organic C (A and Bh horizons). In subsoil horizons DOC release was much lower. Most of the investigated top soils (A and E horizons) and Bh, Bg, and C horizons showed a weak DOC sorption. This was caused by low contents of sorbents (clay and sesquioxides) and/or high contents of organic C. Organic C seems to reduce the DOC sorption by occupying binding sites. Subsoils rich in clay and sesquioxides like Bs, Bt, and Bw horizons showed a strong retention of DOC. Under the aerobic conditions of the experiments, some of the subsoils of stagnosols and gleysols also showed a strong sorption of DOC. However, in sorption experiments conducted after an anaerobic incubation, the DOC sorption decreased significantly.     

IMOGOLITE AND PROTO-IMOGOLITE ALLOPHANE IN SPODIC HORIZONS: EVIDENCE FOR A MOBILE ALUMINIUM SILICATE COMPLEX IN PODZOL FORMATION

Examination by infrared spectroscopy and electron microscopy of the fine clays (<0.5 μm) dispersed at pH 3.5 from H₂O₂-treated soil indicates that imogolite and proto-imogolite allophanes are concentrated in podzolic B₂ and B₃ horizons, and make up at least 6 percent of one B₂ horizon soil, which contains virtually no layer silicate clays. It is argued here that imogolite-type components are the principal source of extractable aluminium and silicon in such horizons, that they may act as cementing agents in indurated horizons, and that proto-imogolite, a soluble aluminium-silicate complex, is the predominant mobile form in which aluminium is transported to B₂ and lower horizons of podzols. Comparison of the amounts of aluminium extracted by acetic acid with those extracted by EDTA indicates that extractable aluminium in Bhg, Bh, and organic-rich A₂ horizons is present principally in organic complexes. It is proposed that the aluminium fulvates concentrated in these horizons are formed in situ.     

The solubility of aluminium in two Swedish acidified forest soils: An evaluation of lysimeter measurements using batch titration data

This paper presents aluminium (Al)-solubility data for two acid forest soils (Inceptisol and Spodosol), obtained in connection with lysimeter measurements (tension-cup and zero-tension lysimeters) and batch equilibrium experiments. The solubility of Al obtained in the batch experiments was used as a reference to test whether Al³⁺in soil solutions collected by the lysimeters was in equilibrium with secondary forms of solid-phase Al (Al(OH)₃or organically bound Al). The relation between pH and Al³⁺activity found for the zero-tension lysimeter solutions collected from the Inceptisol agreed well with that obtained in the batch experiment. This suggests that Al³⁺in the lysimeter solutions were in, or close to, equilibrium with the solid phase, whether this was organically bound Al (A horizon) or an Al(OH)₃phase (B horizon). For the tension-cup lysimeters, solutions obtained from the Inceptisol B and Spodosol Bs1 horizons were generally close to equilibrium with respect to secondary solid-phase Al (apparently Al(OH)₃; average ion activity product was 10^9.3and 10^8.8, respectively), whereas the Inceptisol A and Spodosol Bh solutions were not. The Al solubility in Inceptisol A and Spodosol Bh horizons was consistently higher than that obtained in the batch equilibrium experiment, indicating that the sampled solution partly originated from the underlying horizons. Thus, tension-cup lysimeters should be used with care in soils (or in parts of soil profiles) having steep solute concentration gradients because the soil volume from which the sample is drawn with this lysimeter type seems to be poorly defined.     

Nature and Origin of Lipids in Clay Fractions from a Fluvisol in a Sewage Sludge Deposition Field

Few studies on free lipids in total solvent extracts from soil clay fractions directly measured by gas chromatography–mass spectrometry (GC/MS) have been reported so far. In this study, we aimed to examine the free lipids in the clay fraction separated from a Fluvisol profile on which sewage sludge was deposited 6 years ago and provide information on the sources, diagenetic processes and organic pollutants derived from the sludge. Clay fractions were separated from the four horizons of a Fluvisol and analysed for the biochemically stable lipid pool. The GC/MS analysis of the lipid fraction showed that lipid signatures were dominated by alkanes (C₁₇–C₃₃), alkanoic acids (C₁₂–C₁₈), alkanols (C₁₄–C₃₀), aromatic acids and phthalate esters. Sources of lipids show predominant bacterial contribution as shown by the alkane, fatty acids and n-alkanol distributions. The preservation of lipids of microbial origin in the clay fraction was revealed by the presence of even number, branched alkanes and short-chain and branched fatty acids. These results imply that similar pedogenic processes took place in this soil profile affected by hydromorphic conditions with some quantitative changes in the clay lipid compositions between different soil horizons. Some aromatic acids and xenobiotics such as phthalates were detected in the lipid extracts of the clay fractions in depth (0–85 cm) of the soil profile, which has implications for pollution of soils and ground waters in situations of sewage sludge deposition.