Characterization of Al/Fe—humus complexes in dystrandepts through comparison with synthetic forms

The Al/Fe—humus complexes in A₁ horizons of Dystrandepts from several parts of Japan were compared with synthetic complexes prepared from hydroxy ions and from two kinds of humic substances and at several pH values. Samples represented 26 A₁ horizons of soils differing in age, including some that had been buried. The comparisons were based chiefly on extractions of the synthetic complexes and the soil samples with solutions of sodium hydroxide-tetraborate and sodium pyrophosphate.The Al—humus complexes in the Dystrandept samples appeared to be similar to those of synthetic complexes prepared at pH 4–5. Those have OH/Al molar ratios of 0.7–2.5 1. Distribution of the data for the soil samples suggested further that the proportions of polymeric hydroxy Al ions increased as soils became older and also if they were buried. The Fe—humus complexes in the soil samples seemed to be like the synthetic complexes prepared with Fe and humus at pH 4–5 for the most part.     

Sodium hydroxide-tetraborate in comparison with sodium pyrophosphate as an extractant of “complexes” characteristic of spodic horizons

Sodium hydroxide-tetraborate at pH 9.7 was found not to be a suitable extractant of the amorphous substances characteristic of podzolic B horizons as defined in Canada. Similarly, it does not appear to be a useful basis of a criterion for differentiating spodic horizons as defined in the United States. Hydroxide-tetraborate extracted very little Al and Fe from about half of the podzolic B horizons tested. Compared with pyrophosphate, it extracted from 2 to 50% as much Fe and from 10 to 70% as much Al. Furthermore, hydroxide-tetraborate extracted only small proportions of the Fe and Al from synthetic Fe- and Al-fulvic acid products tested.Evidence regarding the relative specificaties for organic-complexed Al and Fe of hydroxide-tetraborate and sodium pyrophosphate is considered. Deductions about the genesis of podzolic soils based upon experiments with hydroxide-tetraborate are discussed in relation to other evidence.     

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.     

Colloidal stability in some tropical soils of southeastern Nigeria as affected by iron and aluminium oxides

The stability of microaggregates in soils as opposed to its dispersion is a very important soil phenomenon that checks degradation arising from unguided tillage and soil erosion. Ten soils from southeastern Nigeria were sampled from their typical A and B horizons for the study. The aim was to identify the extent of colloidal stability of the soils and the forms of Fe and Al oxides in the soils contributing to their stability. The soils are mostly Ultisols and Inceptisols formed on sandstones and shale parent materials. The soils are low in soil basic cations including the soil organic carbon (SOC). The major clay mineral is kaolinite while the soil is acid in reaction. The various forms of soil Fe and Al oxides are high with the total forms of Fe and Al being most dominant and > dithionite extracted Fe and Al > oxalate extracted Fe and Al > pyrophosphate extracted Fe and Al. The water-dispersible clay and silt (WDC) and (WDSi) which are index of dispersion in most soils are low to medium thus reflecting in the low to medium dispersion ratio (DR). The clay flocculation index (CFI) and aggregated silt + clay (ASC) were moderate to high implying the high potential stability of the soils. Soil organic carbon did not seem to be contributing much to the stability of the microaggregates while oxalate and pyrophosphate extractable Fe (Fe_ox, Fe_p) and to some extent total Al (Al_t) were among the different forms of oxides that act as aggregating agents. We propose here that rather than SOC acting as a disaggregating agent in the soils, it might have acted in association with these oxides in a linkage or bridge such as C–P–OM–C to ensure stability of the soils.     

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.     

SIZE FRACTIONATION, DISSOLUTION ANALYSIS, AND INFRA-RED SPECTROSCOPY OF HUMUS COMPLEXES IN ANDO SOILS

Eight samples of Ando soil A₁ and buried A₁ horizons of different ages were fractionated into clay-, silt-, and sand-size separates, and the yields and carbon contents of these separates were determined. The clay-size separates were subjected to two series of successive extractions, 1) 0.1 M Na₄ P₂ O₇/2% Na₂ CO₃/0.5 M NaOH and 2) dithionite-citrate/2% Na₂ CO₃/0.5 M NaOH; and to difference infra-red spectroscopy for identification of the extracted constituents. The result indicated that humus evolves from forms with a very low complexing ability for Al and Fe into forms that complex Al and Fe in the A₁ horizon, and that humus further interacts with allophane-like constituents, allophane and imogolite in the buried A₁ horizon. These reactions between humus and inorganic constituents result in formation of silt- and sand-size aggregates which are stable to sonic wave treatment, but are broken down into finer particles upon boiling with H₂ O₂.     

Soil aluminum and iron fractions and their relationships with P immobilization and other soil properties in andisols of costa rica and panama

Abstract

The immobilization of P is a significant fertility limitation of Andisols in Central America. It is believed that soil Al and Fe fractions have an important influence on P availability. This study was conducted to obtain information on the various forms of Al and Fe in ten pedons derived from volcanic ash in Panama and Costa Rica. Correlations between these Al and Fe fractions and P immobilization were measured by different methods.

The Al and Fe fractions, extracted by acid ammonium oxalate, 4M KOH, sodium pyrophosphate and dithionite‐citrate, were determined, and the correlations between these fractions, P immobilization, and other soil properties made.

It was observed that oxalate extractable Al correlated significantly with P immobilization, which had values of over 85% by the New Zealand method and 96% by the isotherm method. The Al concentration corresponding to this immobilization was over 2%. The difference between oxalate extractable Al and pyrophosphate extractable Al (inorganic Al fraction) correlated with P immobilization also. The pyrophosphate extractable Al fraction had the lowest concentrations and did not correlate with P immobilization. The NaF‐pH and dithionite‐citrate extractable Al correlated significantly with P immobilization.

Oxalate extractable Fe correlated with the P retained by the isotherm method, but dithionite‐citrate extractable Fe was negatively correlation with P immobilized. No correlations were found between the pyrophosphate extractable Fe and other soil properties.     

An assessment of EDTA as an extractant of organic-complexed and amorphous forms of Fe and Al in soils

EDTA solutions proposed as selective extractants of amorphous and organic forms of Fe and Al in soils and synthetic materials were tested. Extraction of Fe and Al from some soil samples continued at a decreasing rate beyond 120 days. For some soil samples and synthetic materials the amounts of Fe and Al extractable by EDTA (90 days) were markedly lower than those extractable by acid ammonium oxalate (2 h). Extraction of samples for 1 h with EDTA was shown to release amounts of Fe and Al far below those considered to be complexed with organic matter. The EDTA extraction procedures tested should not replace either acid ammonium oxalate for estimating amorphous forms of Fe and Al or pyrophosphate for estimating organic forms of Fe and Al in soils.     

RELATIONSHIPS BETWEEN NET REDISTRIBUTION OF Al AND Fe AND EXTRACTABLE LEVELS IN PODZOLIC SOILS DERIVED FROM LOWER PALAEOZOIC SEDIMENTARY ROCKS

Examination of the translocation and net redistribution of Al and Fe in podzolic soils on Lower Palaeozoic sedimentary rocks has shown marked differences in behaviour between the two elements. Iron exhibits the classical pattern of eluviation and illuviation, the consequences of which are closely correlated with amounts of ‘active’ Fe extracted with pyrophosphate. On the other hand Al rarely accumulates in B horizons enriched in Fe. In addition pyrophosphate-extractable Al is unrelated to its net redistribution pattern. Stagnopodzols on Lower Palaeozoic sediments are strongly acidic throughout and show a characteristic trend in oxidation/reduction conditions with depth. It is the differential response of Al and Fe to the combination of these properties, particularly in relation to their effect on illuviation, which accounts for the observations.     

Phosphorus sorption by Andepts from the Southern Highlands of Papua New Guinea

P sorption curves (18 hours, 0.01 M CaCl₂) were determined for various A, AB, B and C horizons of six Andepts. Two of these soils were formed in alluvially sorted and redeposited volcanic ash. P buffer capacity (PBC) and equilibrium solution P concentration (EPC) were derived from the curves. PBC was high for all samples indicating large sorption capacities. Soils formed in alluvial ash had lower PBC than those developed in airfall ash. In the latter soils, PBC was affected by degree of weathering. Multiple regression indicated that most variation in PBC was accounted for by citrate-dithionite minus pyrophosphate extractable Al, oxalate minus pyrophosphate extractable Al, and pyrophosphate extractable Fe. This suggests that allophane, crystalline and non-crystalline aluminium hydrous oxides, and Fe associated with organic matter, account for the predominant P-sorbing sites. The low EPC figures, which were correlated with Olsen extractable P, indicate potential P deficiency as a limitation to crop production.     

Mobilization of dissolved organic matter, aluminium and iron in podzol eluvial horizons as affected by formation of metal-organic complexes and interactions with solid soil material

Interactions with dissolved organic matter (DOM) are generally believed to play a crucial role in the translocation of Al and Fe in acid sandy soils. Binding of Al and Fe to DOM affects their mobility in soils by altering sorption equilibria of charged sites on solid soil material, inducing precipitation of organo‐metallic complexes and preventing the formation of inorganic Al and Fe phases. The relative importance of the different processes, especially with respect to the translocation of Al, Fe and organic matter in podzols, remains unresolved. We determined the effect of the presence of solid soil material from the eluvial (AhE and AE, respectively) horizons of a Fimic Anthrosol and a Haplic Podzol on the metal‐to‐organic carbon (M/C) ratio in solution and the formation of dissolved organic Al and Fe complexes. Furthermore, we assessed the resulting influence on the mobilization of Al, Fe and DOM. Even under considerable metal loading, the M/C ratios and ‘free’ metal fractions in solution remained low and relatively constant, due to an apparent buffering by the solid phase and the formation of organo‐metal complexes in solution. The M/C ratios remained so low that significant precipitation of organo‐metal complexes due to saturation with metals was not found. The apparent buffering by the solid phase can be explained by a strong release of organic matter from solid soil material and adsorption of non‐complexed Al and Fe on solid organic matter upon metal addition. Adsorption of organo‐metal complexes most likely played only a minor role. The observations confirm the expected mobilization of Al, Fe and DOM in eluvial horizons and seem to indicate that even under fluctuating input of Al, Fe and DOM the soil solution will have a constant composition with respect to M/C ratios and percentage of Al and Fe present in dissolved organo‐metal complexes.     

Iron oxyhydroxides in soils developed from Lower Palaeozoic sedimentary rocks in mid-Wales and implications for some pedogenetic processes

Lepidocrocite and goethite are pedogenetic crystalline Fe oxyhydroxides in the soils of mid-Wales. Lepidocrocite is more abundant and widespread, occurring in brown earths (Denbigh series) as well as morphological gleys. It is commonly dominant in horizons intermediate in depth. Goethite occurs in subsoils and was found to be dominant in the subsoil of surface water gleys (Cegin series). Apart from the Cegin series, a large proportion of the total free Fe occurs in non-crystalline forms. This amounted to 50–80% of the free Fe in organic and eluvial horizons of podzols. Despite lower proportions of non-crystalline Fe in Bs horizons, amounts were similar to those in eluvial horizons. Data on the distribution of crystalline and non-crystalline free Fe together with correlations observed between Fe and C extracted by pyrophosphate suggest that transformation and translocation of Fe in the podzols examined are governed by its association with organic fractions.     

Rheological Properties of Automorphic and Semihydromorphic Cryometamorphic Northern Taiga Soils in Northeastern European Russia (Komi Republic)

Soil pastes at the water content corresponding to the maximum swelling of samples from different genetic horizons of cryometamorphic soils―surface-gleyic iron-illuvial svetlozem (Folic Albic Stagnosol) and peaty and peat humus-impregnated gleyic svetlozems (Histic Gleyic Stagnosols)―have been studied with an MCR-302 modular rheometer (Anton Paar, Austria). It has been found that the strongest interparticle bonds are formed in the horizons of cryometamorphic soils characterized by high contents of humic substances and organomineral Al–Fe–humus compounds. These are horizons of podzol microprofile (Eg and BHF) in iron-illuvial svetlozem and a humus-impregnated horizon (ELhi,g) in peaty and peat svetlozems. Organomineral Al–Fe–humus compounds, as well as the seasonal freezing of soils, determine the elastic-brittle character of interparticle interactions. The contents of clay fractions, exchangeable bases, and organic and organomineral substances impart viscoelastic properties to these contacts. An enhancement of elastic-brittle properties of soil is observed under the impact of gleying and freezing. The threefold decrease of the structural interaction parameter (∫Z) when going from automorphic to semihydromorphic conditions indicates a decrease in the resistance of peaty and peat svetlozems to mechanical loads under increasing hydromorphism compared to iron-illuvial svetlozems.     

Movement of aluminium as an inorganic complex in some podzolised soils,New Zealand

Chemical and mineralogical data are presented for three Spodosols (podzols) and a related Inceptisol (yellow-brown loam). Allophane with an Al/Si atomic ratio close to two is identified in the B horizons of all four soils, and minor amounts of imogolite are present in association with allophane in all but one soil where small-particle gibbsite occurs. Parent materials for these soils are essentially non-vitric. Allophane (Al/Si = 2) has been estimated quantitatively in all soils using oxalate-extractable Si (Si₀) and is selected clay fractions using both Si₀ and infrared spectroscopy. Maximum concentrations of allophane (Al/Si = 2) range from 5% to 18% of fine earth (< 2 mm) fractions and all occur in B horizons. Fe₀ values are low relative to Al₀ values except for the upper horizons of the Inceptisol. Al₀ values peak in B horizons and the ratio pyrophosphate-extractable Al to Al₀ decreases from about 1 in A and upper B horizons to 0.1–0.4 in lower B horizons.An interpretation of the data is consistent with recent proposals that the movement of Al in podzolisation is due primarily to the formation of inorganic complexes with Si. Chemical criteria for spodic horizons should be consistent with the total illuviation of Al and Fe (and perhaps Si), rather than just the organic-bound fraction of Al and Fe in these horizons as indicated by amounts in extractants such as pyrophosphate.     

Land-use/cover change effects and carbon controls on volcanic soil profiles in highland temperate forests

The stabilization of SOM by Al–humus complexes and non-crystalline minerals is a key issue to explain the soil-C variability and the biogeochemical processes that determine the fate of soil C following land-use/cover change (LUCC) in volcanic landscapes. In an altitudinal gradient of volcanic soils (2550–3500 masl), we quantified the total soil C (C_T) concentrations and stocks in soil pits sampled by genetic horizons. We performed analyses at landscape and local scales in order to identify and integrate the underlying environmental controls on C_T and the effects of LUCC. We selected four sites, two on the upper piedmont, one on the lower mountain slope and one on the middle mountain slope at Cofre de Perote volcano (eastern central Mexico) where temperate forests are the natural vegetation. At each site we selected three to five units of use/cover as a chronosequence of the LUCC pathways. In each soil horizon chemical characteristics (i.e. N, C/N ratio, pH, exchangeable bases) were determined and mineralogical properties were estimated from selective Al, Fe and Si oxalate and pyrophosphate extractions (i.e. the Alp/Alo ratio, the active Al related to non-crystalline minerals as Al_o ? Al_p, the allophane concentration, and the non-crystalline Al and Fe minerals as Al_o + 1/2Fe_o). At landscape scale, the Al–humus complexes were strongly related to the C_T concentration in topsoil (A horizons) but this relationship decreased with depth. In turn, the non-crystalline minerals and the C/N ratio explained the variability of the C_T concentrations in C horizons. At local scale, C_T concentrations and stocks were depleted after conversion of forest to agriculture in Vitric Andosols at the upper piedmont but this was not observed in Silandic Andosols. However, in Vitric Andosols the reduction of the C_T stocks is partially recovered throughout the regeneration/reforestation processes. The results suggest that the lower vulnerability of Silandic Andosols than Vitric Andosols to changes in the C_T after LUCC is due to the higher levels of SOM stabilized by Al–humus complexes and non-crystalline minerals in the Silandic soils. Furthermore, the importance of the allophane to explain the C_T stocks in the Silandic Andosols of the middle slopes suggests that the C_T stabilized by this mineral fraction in the subsoil adds an important fraction of the C_T to the estimates of the stocks.     

Crop use and profile distribution of phosphorus in soils that developed on mafic rocks in southern Portugal

The phytoavailability of soil phosphorus (P) depends on the different forms in which it occurs and how these forms change after the application of P fertiliser to the soil. Forms of P in the A, B and C horizons of eleven pedons that developed on mafic rocks were characterised by a fractionation method before and after fertilisation with single superphosphate, and a micropot experiment was conducted to assess the short-term use of P fertiliser by rye (Secale cereale L.). The main sources of P to the crop were (i) phosphate adsorbed on mineral surfaces and pedogenic Fe, Al or Ca phosphates in the A horizon and (ii) Ca-phosphates in B and C horizons. In the C horizons, poor in Fe/Al phases and clay, the precipitated Ca-P showed low solubility, resulting in a reduction in shoot biomass. The apparent P recovery by rye was similar in the A (36%) and B (29%) but decreased in the C (15%) horizons. The partial factor productivity (g g^?1) decreased from the A (58) to B (11) and C (5) horizons. P phytoavailability decreased with increasing profile depth because the transformation of P fertiliser to poorly soluble Ca-P forms increased with depth.     

Variation in soil macro-fauna diversity in seven humus orders of a Parrotio-Carpinetum forest association on Chromic Cambisols of Shast-klateh area in Iran

Soil biodiversity includes organisms which spend a part or all of their life cycle on or in the soil. Among soil-dwelling animals, macro-fauna as an important group of animals have important effects on the dynamics of soil organic matter and litter decomposition process. The humus forms interact with the climatic conditions, flora, as well as soil fauna, and microbial activity. In new humus form classifications, soil organisms play an important role in separation of humus horizons from one another. The subject of this study was to determine the diversity of macro fauna for different humus forms. We determined humus forms using morphological classification, and then 69 random samples were taken from plots of 100 cm² in area, and soil macro-fauna species were collected by hand sorting method. Two classes of humus forms, including Mull (with three humus orders, namely Dysmull, Oligomull, and Mesomull,) and Amphi (with four humus orders, namely Leptoamphi, Eumacroamphi, Eumesoamphi, and Pachyamphi) were identified. A number of 13 macro-fauna orders were identified using identification key. Among the humus orders, Shannon diversity, Simpson evenness and Margalef richness indices were the highest in Pachyamphi order. Arthropod diversity in Pachyamphi humus order was higher than those of Mull. These results showed that diversity of soil macrofauna increase by increasing the thickness of the organic horizons (OL, OF, OH), especially OH horizon.     

Composition and Characteristics of Organo—Mineral Complexes of Red Soils in South China

The objective of the present study is to reveal the composition and characteristics of organo-mineral complexes in red soils (red soil,lateritic red soil and latosol) of south China in terms of chemical dissolution and fractional peptization methos.In the combined humus,most of the extractable humus could dissolve in 0.1 M NaOH extractant and belonged to active humus (H1),and there was only a small amount of humus which could be further dissolved in 0.1 M Na4P2O7 extractant at pH 13 and was stably combined humus (H2).The H1/H2 ratio ranged from 3.3 to 33.8 in red soils,and the proportions of both H1 and total extractable organic carbon (H1 H2) in total soil organic carbon and the ratios of H1 to H2 and H1 to (H1 H2) were all higher in lateritic red soil and latosol than in red soil.The differences of combined humus composition in various red soils were directly related to the content of Fe and Al oxides.In organo-mineral complexes,the ratio of Na-dispersed fraction (G1) to Na-ground-dispersed fraction (G2) was generally smaller than 1 for red soils,but there was a higher G1/G2 ratio in red soil than in lateritic red soil and latosol.G1 fraction had a higher content of fulvic acid (FA),but G2 fraction had a higher content of humic acid (HA).The ratios of H1 to H2 and HA to FA were higher in G2 than in G1.The differences in the composition and activity of humus between G1 and G2 fractions were related to the content of free Fe and Al oxides.The quantities of complex Fe and Al,the Fe/C and Al/C atomic ratios were higher in G2 than in G1,and the ratio of Al/C was much higher than that of Fe/C.It may be deduced that aluminum plays a more important role than iron in the formation process of organo-mineral complexes in red soils.     

Transfer of dissolved Al, Fe and Si in two Amazonian forest environments in Brazil

The balance of Si, Fe and Al in the soil solution determines more or less the course of soil formation in the tropics. We have tried to improve understanding of the processes by studying fluxes of dissolved Si, Fe and Al from the atmosphere, through the canopy and the soil, and to the groundwater, in two distinct Amazonian ecosystems, one a typical rainforest, developed on a Ferralsol, the other a so-called ‘Campinarana’ forest, developed on a Podzol. The Si, Fe and Al in the rain and the throughfall and the stemflow were measured throughout a year, and the leaching of Si, Fe and Al through the upper soil and at the groundwater level were estimated. The annual balance showed that stemflow inputs were negigible compared with the contributions from throughfall and rain. The inputs of Fe, Al and Si to the topsoil from the rain and from dust and biological release in the canopy were small but not negligible. These sources contributed more aluminium in the Campinarana than in the rainforest. The rainfall constituted the main input of dissolved Fe and Al to the topsoil in both ecosystems. The element balances in the soil horizons confirmed that the present functioning of the Ferralsol results in aluminization and desilicification. We also found that the elements are transported in micropore flow and on translocated particles, as well as in freely percolating water.     

Potentially Mobile Lead Fractions in Montane Organic-Rich Soil Horizons

Anthropogenic emissions during the 20th century resulted in global lead (Pb) contamination of soils. Recent studies have demonstrated that the organic horizons of temperate montane Spodosols in the northeastern United States retain Pb on timescales of 50 to 150 years. The precise mechanism(s) of this strong Pb partitioning to organic-rich soil material remain elusive, but a detailed understanding of Pb retention by organic layers and mineral topsoils is critical for predicting the fate of pollutants deposited on ecosystems. Here we use selective extractions to quantify potentially mobile pools of Pb in the surface horizons of relatively remote montane Spodosols from New Hampshire and Vermont. Using 10 consecutive rinses of water, we extracted a total of 1 to 5% of the carbon, and 4 to 12% of the Pb. Dialysis equilibration experiments demonstrate that this Pb is >5,000 molecular weight, and not truly dissolved as Pb²⁺. When soil was extracted with a single rinse of 0.02 M HCl (pH 1.7), 5 to 11% of the Pb was mobilized. However, hydroxylamine hydrochloride in 0.02 M HCl (a reducing agent) extracted 30 to 40% of the Pb. Repeated rinses with sodium hydroxide and sodium pyrophosphate, which target organic matter but may extract other soil phases removed 16 to 75% and 60 to 100% of the Pb, respectively. We show that significant Fe, Pb, and Al can be released from soils under reducing conditions, and that this fraction can be underestimated if sodium pyrophosphate is used in a previous step for leaching the organic-metal phase, as is typically done in sequential extraction schemes. Our results indicate that inorganic phases play an important role in determining Pb mobility and bioavailability, even in surface soil horizons dominated by organic matter.