The influence of land management on concentrations of dissolved organic carbon and its effects on the mobilization of aluminium and iron in podzol soils in Mid-Wales

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.     

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.     

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.     

Forms and buffering potential of aluminum in tropical and subtropical acid soils cultivated with Pinus taeda L

Purpose

Several interactions between Al and the solid phase of soil influence Al buffering in soil solution. This work evaluated soils cultivated with Pinus taeda L. to determine Al forms in organic and mineral horizons using various extraction methods and to relate acidity with clay mineralogy.

Materials and methods

Organic and mineral horizons of 10 soil profiles (up to 2.1 m deep) in southern Brazil were sampled. Organic horizons were separated into fresh, aged, and fermented/humified litter. The following Al extraction methods were utilized: 0.5 mol L^?1 pH 2.8 CuCl₂–Al complexed in organic matter; 1.0 mol L^?1 KCl–exchangeable Al; water–Al soluble in soil solution; HF concentrated?+?HNO₃ concentrated?+?H₂O₂ 30% (v/v)–total Al. Six sequential extractions were carried out to isolate different forms of amorphous minerals that can buffer Al on soil solution: 0.05 and 0.1 mol L^?1 sodium pyrophosphate; 0.1 and 0.2 mol L^?1 ammonium oxalate; 0.25 and 0.5 mol L^?1 NaOH. Samples of clay were also analyzed by XRD.

Results and discussion

There was a clear effect of litter age on increasing total Al concentration. In the aged litter and fermented and/or humified litter, levels of total Al were 1.4 to 3.8 and 1.5 to 7.8 times greater than in fresh litter, respectively. The CuCl₂ method had higher Al extraction capacity than the KCl method for litter. The lowest Al–pyrophosphate values were observed in the Oxisol, which also had a predominance of gibbsite and the lowest levels of Al–KCl and Al–CuCl₂. There was an inverse relationship between degree of soil weathering and soluble and exchangeable Al in soils. Available Al increased with higher Si proportion in minerals of the clay fraction (2:1?>?1:1?>?0:1).

Conclusions

The worst scenario was soils with the combination of high soluble and exchangeable Al levels and high concentrations of amorphous forms of Al minerals. The best predictors of Al accumulation in the youngest litter horizon were extractions of amorphous minerals with pyrophosphate and NaOH. These extractors are normally used to predict the level of Al buffering in soils. Organic matter had less influence on Al dynamics in soils.

     

Surface analysis of soil material by X-ray photoelectron spectroscopy

The surface composition of particles present in the fine earth (< 2 mm) of 50 soil horizons differing in composition and pedogenetic origin (13 soil profiles) was analysed by X‐ray photoelectron spectroscopy (XPS) to assess the capability and limitations of this technique and to gain better knowledge of the soil samples. The surfaces were systematically enriched in carbon, sometimes up to 1000 times, indicating that the soil particle surfaces are coated with organic substances, even in horizons where the bulk organic content is less than 0.1 g kg^?1. The distribution of carbon in the various oxidation states was 0.569 ± 0.008 C^[0], 0.275 ± 0.004 C^[+1], 0.089 ± 0.003 C^[+2] and 0.066 ± 0.002 C^[+3] for most horizons (mean ± standard error, 69 data). Only Andosol surface horizons systematically had surface organic matter in a more oxidized state. After correcting the results for the presence of organic coatings, we found that Si was generally depleted and Al enriched at the surface of soil particles, while Fe was either depleted or enriched depending on the sample considered. However, the coating of the coarser soil particles by the finer ones and their differential composition explained this observation and limits the interest of XPS for characterizing the surface enrichment of inorganic elements in crude soil samples. These limitations should be considered when interpreting XPS results in future work. Nevertheless, XPS can analyse the adsorbed organic matter and its functional composition of carbon without the need for any chemical or physical extraction that might alter the structure and composition of the organic molecules.     

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.     

The response of soil organic matter to manure amendments in a long-term experiment at Ultuna, Sweden

In a long-term field experiment started in 1956 on a clay loam soil at Uppsala, Sweden, changes of organic carbon in the topsoils receiving various organic amendments at the rate of 200 kg C ha^'1 year^'1 were studied to determine soil organic matter characteristics, variations of δ¹³C in the soil and to estimate a carbon balance. Fallow and mineral fertilizer without N led to a significant decrease of soil organic matter (SOM) in the soil, green manure maintained the SOM content, and animal manure and peat increased the SOM content significantly. The stable portion of the added organic materials after 37 years of continuous input was 12·8, 27·3, and 56·7%, for green manure, animal manure and peat, respectively. This was reflected by half-lives of organic carbon originating from the amendments between 3·0 (green manure) and 14·6 years (peat). The isotopic composition of SOM changed both due to mineralization (continuous fallow) and the addition of amendments is topically different from soil humus (green manure, animal manure). The isotopic effect was used to calculate the percentage of carbon derived from animal manure present for the year 1993. This value (55·4%) was larger than that derived from the carbon balance, which indicated a priming effect of the animal manure on the initial soil humus. Mineralization of microbially available organic substances led to an increase in the degree of humification on plots not receiving organic amendments. Adding peat and animal manure resulted in a decrease of the humification index due to the continuous input of poorly humified material. The extinction ratio (E₄/E₆) and ratio of fulvic acid to humic acid changed considerably in the peat treated plots. Fourier transform infrared (FTIR)-measurements of the extracts showed that peat characteristics can be detected in peat treated soils. The other amendments did not alter the characteristics of the extractable humic substances.     

Incipient podzolization processes in Humic Acrisols of southern Spain

Soils with morphological evidence of podzolization occur in Sierra Morena (southern Spain). Six soils, identified as Humic Acrisols, were sampled for detailed study. Distribution of oxalate- and EDTA-extractable Al in Fe in the profiles indicated that substantial amounts of both elements had been translocated from the A to the incipient podzolic B horizons. Part of the Al, but almost no Fe, was present as organic complexes, suggesting that these two elements were transported to, or remobilized in the B horizons by different mechanisms. Allophane was present, albeit in small amounts, in two soils. Both inorganic and organic theories of podzolization were able to explain the Fe and Al distribution data.     

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.     

Soil podzolization induced by reforestation as shown by sequential and kinetic extractions of Fe and Al

The impact of 60‐year‐old reforestation on soil evolution was studied by following the evolution of Fe and Al distribution as an indicator of early podzolization. We determined the distribution of Al and Fe in soils by combining sequential and kinetic extractions. We extracted the soil sequentially with: 1 mol litre^?1 sodium acetate at pH 5.5 (stage 1); twice with 0.1 mol litre^?1 sodium pyrophosphate at pH 10 (stage 2 and 2b); and with 1 mol litre^?1 hydroxylamine in 4.3 mol litre^?1 acetic acid solution at 90°C (stage 3). For each, we drew a kinetic‐extraction curve. We show that no re‐adsorption, precipitation or complexation with dissolved organic matter occurred for the reaction times recommended in this procedure, that is 6 hours for stage 1, 1.5 hours for stage 2 and 2b and 3 hours for stage 3. For a given extraction, the kinetic curves have the same shape for all samples, that is their behaviour is similar for a given reagent. Sequential extraction can therefore be used to compare the speciation of metals in different samples taken from the same soil. In addition, 60 years after reforestation by beech, a decrease of 12 and 17% is noted in the total Fe and Al contents, respectively, in the 0–10 cm layer, accompanied by a re‐distribution of these elements within the different soil compartments: a decrease of the Fe and Al bound to oxy‐hydroxide in favour of organic complexes and more soluble forms. Sequential extraction is therefore a good indicator of the first pedogenetic modifications induced by human intervention through reforestation.     

VERTICAL DISTRIBUTION OF EXTRACTABLE IRON AND ALUMINIUM IN SOIL PROFILES FROM A BROWN EARTH-PEATY PODZOL ASSOCIATION

Fe and Al extractable by 3 per cent oxalic acid and by 0.1M potassium pyrophosphate at pH 10 have been determined in horizon samples of two soil profiles of each of three subgroups (Brown Earth, Brown Podzolic Soil, and Peaty Podzol) developed in North Wales on parent materials derived from Silurian shales. The vertical distribution of Fe and Al together with the relationship between pyrophosphate-extractable (‘fresh’ hydrous oxides) and oxalic-extract-able Fe or Al (‘fresh’+‘aged’ hydrous oxides) can assist classification and interpretation of the course of podzolization in these soils. If podzolization is defined as sesquioxide transport, then its degree of development in the soils studied differs according to whether Al or Fe are used as the index element. The evidence supports continued recognition of soils of Brown Podzolic type as an intergrade subgroup.     

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.     

Poorly crystalline mineral phases protect organic matter in acid subsoil horizons

Soil minerals are known to influence the biological stability of soil organic matter (SOM). Our study aimed to relate properties of the mineral matrix to its ability to protect organic C against decomposition in acid soils. We used the amount of hydroxyl ions released after exposure to NaF solution to establish a reactivity gradient spanning 12 subsoil horizons collected from 10 different locations. The subsoil horizons represent six soil orders and diverse geological parent materials. Phyllosilicates were characterized by X-ray diffraction and pedogenic oxides by selective dissolution procedures. The organic carbon (C) remaining after chemical removal of an oxidizable fraction of SOM with NaOCl solution was taken to represent a stable organic carbon pool. Stable organic carbon was confirmed as older than bulk organic carbon by a smaller radiocarbon (¹⁴C) content after oxidation in all 12 soils. The amount of stable organic C did not depend on clay content or the content of dithionite–citrate-extractable Fe. The combination of oxalate-extractable Fe and Al explained the greatest amount of variation in stable organic C (R² = 0.78). Our results suggest that in acid soils, organic matter is preferentially protected by interaction with poorly crystalline minerals represented by the oxalate-soluble Fe and Al fraction. This evidence suggests that ligand exchange between mineral surface hydroxyl groups and negatively charged organic functional groups is a quantitatively important mechanism in the stabilization of SOM in acid soils. The results imply a finite stabilization capacity of soil minerals for organic matter, limited by the area density of reactive surface sites.     

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.     

Der Einfluß der natürlichen organischen Substanzen auf die Metallverteilung zwischen Boden und Bodenlösung in einem sauren Waldboden

The influence of organic matter in the translocation of metals between soil and soil solution of an acid forest soil Water extracts were prepared from soil samples which were collected from a soil profile showing very little variation in the texture down to a depth of 120 cm and thus only little translocation of clay in the soil profile. The aim of the study was to describe the distribution between soil and soil solution of several metals like Cu, Pb, Cd, Zn, Al and Mn as a function of humic substances, electrolyte concentration and pH. From the experimental results the following hypothesis on the reaction mechanisms involving metals and humus derived substances has been deduced. The metals Cu, Fe, Al and Pb are mobilized through complexation by soluble humus substances in addition to the usual pH dependent desorption and dissolution of hydroxides. This mobilization determines the solution concentration of Cu and Fe at pH > 3.7 and Al and Pb at pH > 4.2. Al, Fe and Pb are complexed selectively by high molecular weight humus derived substances which undergo adsorption on soil mineral surfaces. Cu interacts with low molecular weight humus derived substances which are not easily adsorbed by the mineral surfaces. Zn, Cd and Mn primarily undergo sorption and are thus controlled by pH and electrolyte concentration of solutions because their complexation with humus derived substances seems to be weak or nonexistant. It is further postulated that the humus derived substances mobilize Al³⁺ and Fe³⁺ ions. By this, other metals like Cd, Zn, Mn, Ca and Mg can occupy the free exchange sites.     

Influence of afforestation on soil genesis,morphology and properties in glacial till deposits

A study of soil morphological, physical and chemical properties was performed in woodland of different ages, in which spruce (Picea abies), aspen (Populus tremula) and birch (Betula pendula) growing stocks have colonized former agricultural land. The aim of the study was to clarify changes in soil genesis, morphology and properties due to the afforestation of abandoned agricultural land in glacial till deposits. The research showed that soil in these deposits (loamy sand, loam, clay) retains the morphological properties of agricultural land for up to 100 years. Secondary podzolization features in the soil profiles were observed within 100 years of the start of afforestation, whereas the diagnostic properties of Albic and Spodic horizons had not developed in the soil profile after 200 years. This study demonstrated that the morphological and physico-chemical properties of forest litter horizons, including the accumulation of organic substances, are dependent on forest age; however, changes in the properties of mineral soil horizons are mainly related to woodland age. Following the afforestation of agricultural lands, changes in soil pH_KCl, organic matter content and extractable Al and Fe concentrations occur more rapidly than changes in soil diagnostic properties and profile formation.     

Trace element distributions in soils developed in loess deposits from northern France

A pedo‐geochemical survey was carried out in the Nord‐Pas de Calais region (France) on soils developed in loess deposits. Total concentrations of Al, Fe and 18 trace elements, as well as common soil characteristics, were determined in samples from 52 surface and 97 deep horizons developed in these loess deposits. The Pb isotopic composition was determined in two sola. The composition of deep horizons, compared with that of the upper continental crust, with that of horizons developed from 21 other sedimentary rocks from the region and with that of loess from various parts of the world, confirms that loess from the Nord‐Pas de Calais region derives from multi‐recycled and well‐mixed ancient sedimentary rocks. Correlation analysis shows that least mobile (i.e. ionic potential (Z/r) is between 3 and 7) geogenic elements (Bi, Co, Cr, Cu, In, Ni, Pb, Sn, Tl, V, Zn) are associated with the fraction <2 µm (which we define as ‘lutum’). More mobile elements (As, Cd, Hg, Mn, Mo, Sb, Se) are less associated with this fraction. Cadmium is particularly linked to Mn. The distribution of [trace element]/([Al] or [Fe]) in the French loess gives the background content for soils developed from most sedimentary materials in northwestern Europe. Topsoils are enriched with all the trace elements examined, except Co, Cr and Ni. Enrichments with Cd, Cu, Mn and Zn are greater in cultivated soils than in forest soils. Enrichments with Pb and with Cu, Hg, Mo, Sb, Se and Sn are mainly due to human contamination through atmospheric fallout. Organic matter seems to act as a sink for all the exogenous trace elements.     

Effect of Organic Matter and Salinity on Ethylenediaminetetraacetic Acid–Extractable and Solution Species of Cadmium and Lead in Three Agricultural Soils

Abstract

A study was conducted to investigate the chemical speciation of added cadmium (Cd) and lead (Pb) and their availability as influenced by fresh organic matter (OM) and sodium chloride (NaCl) in three agricultural soils. The soils were treated with 20 mg Cd/kg as cadmium nitrate [Cd(NO₃)₂ · 4H₂O], 150 mg Pb/kg as lead nitrate [Pb(NO₃)₂], 20 g/kg alfalfa powder, and 50 mmol/kg of NaCl and then incubated for 3 months at 60% water‐holding capacity (WHC) and constant temperature (25 °C). Subsamples were taken after 1, 3, 6, and 12 weeks of incubation, and electrical conductivity (EC), pH, dissolved organic carbon (DOC), and concentrations of cations and anions were determined in the 1:2.5 soil/water extract. Available Cd and Pb were determined in 0.05 M ethylenediaminetetraacetic acid (EDTA) extract. Concentrations of organic and inorganic species of Cd and Pb in soil solution were also predicted using Visual Minteq speciation program. The most prevalent species of dissolved Pb and Cd in the soils were Pb‐DOC and Cd²⁺ species, respectively. Salinity application increased the available and soluble Cd significantly in the acid and calcareous soils. It, however, had little effect on soluble Pb and no effect on available Pb. Organic‐matter application decreased availability of added Pb significantly in all soils. In contrast, it raised soluble Pb in all soils except for the acid one and approximated gradually to the added Pb with time. Impact of OM on available Cd was somewhat similar to that of Pb. Soluble Cd increased by OM application in the calcareous soil, whereas it decreased initially and then increased with time in the other soils.