Phytoavailability of phosphate adsorbed on ferrihydrite,hematite, and goethite

Poorly crystalline Fe in soil has been shown to affect Fe and P availability. Oxalate extractable Fe, a measure of poorly crystalline Fe oxides, has not been compared to soil test methods for Fe and P in rice soils. Twenty eight soils used for rice production were incubated under aerobic and anaerobic soil conditions and extracted for Fe and P with ammonium oxalate, ammonium acetate-EDTA (AA-EDTA), ammonium bicarbonate-DTPA (AB-DTPA) and DTPA. Citrate-dithionite extractable Fe and Fe content of rice plants in a greenhouse experiment were also determined. Soils used in this experiment had a large amount of poorly-crystalline Fe oxide. In some soils, poorly-crystalline Fe constituted 60% of the citrate-dithionite extractable Fe. The amount of extractable Fe and P increased significantly under anaerobic conditions. The relationships between extractants showed that DTPA Fe was highly correlated to AB-DTPA Fe and oxalate Fe was highly correlated to AA-EDTA Fe. There was no relationship between Fe and P extracted by AB-DTPA, while there was a better relationship with ammonium oxalate and AA-EDTA extractants. Poorly-crystalline Fe and P extracted by ammonium oxalate were correlated.     

The use of soil extractants to estimate plant-available molybdenum and selenium in potentially toxic soils

Summary Uptake of Mo and Se by plants growing on soils with larger than normal concentrations of these elements cannot be predicted from soil content alone.Results of the chemical extraction of Mo and Se from soils in the laboratory have been compared with plant uptake of Mo and Se from the same soils in greenhouse experiments. Plant uptake of Mo and Se is correlated with the EDTA-extractable Mo and Se in the soil and uptake of Mo with the ammonium acetate-extractable soil.The role of pH, organic matter, and other soil properties are discussed with regard to Mo and Se availability and to the interpretation of results obtained by laboratory extractions.     

Iron- and aluminium-induced depletion of molybdenum in acidic environments impedes the nitrogen cycle

Anthropogenic nitrate contamination is a serious problem in many natural environments. Nitrate removal by microbial action is dependent on the metal molybdenum (Mo), which is required by nitrate reductase for denitrification and dissimilatory nitrate reduction to ammonium. The soluble form of Mo, molybdate (MoO₄²⁻), is incorporated into and adsorbed by iron (Fe) and aluminium (Al) (oxy) hydroxide minerals. Herein we used Oak Ridge Reservation (ORR) as a model nitrate-contaminated acidic environment to investigate whether the formation of Fe- and Al-precipitates could impede microbial nitrate removal by depleting Mo. We demonstrate that Fe and Al mineral formation that occurs as the pH of acidic synthetic groundwater is increased, decreases soluble Mo to low picomolar concentrations, a process proposed to mimic environmental diffusion of acidic contaminated groundwater. Analysis of ORR sediments revealed recalcitrant Mo in the contaminated core that co-occurred with Fe and Al, consistent with Mo scavenging by Fe/Al precipitates. Nitrate removal by ORR isolate Pseudomonas fluorescens N2A2 is virtually abolished by Fe/Al precipitate-induced Mo depletion. The depletion of naturally occurring Mo in nitrate- and Fe/Al-contaminated acidic environments like ORR or acid mine drainage sites has the potential to impede microbial-based nitrate reduction thereby extending the duration of nitrate in the environment.     

Nickel bioavailability in an ultramafic toposequence in the Vosges Mountains (France)

A serpentinised harzburgite outcrop located in the Vosges Mountains hosts a population of the Ni-hyperaccumulator Thlaspi caerulescens J. & C. Presl. A complete study was undertaken to relate the variability of Ni availability along the ultramafic toposequence to pedogenesis, soil mineralogy and functioning with X-Ray Diffraction, Transmission Electron Microscope observations coupled with Isotopic Exchange Kinetics and diethylenetriamine pentaacetic acid extraction of Ni. The soil profiles ranging from Dystric Cambisol to Hypermagnesic Hypereutric Cambisol were distributed unevenly along the toposequence probably due to geochemical variability of the bedrock and also complex quaternary erosion features. The richest soils were characterised by slight mineral weathering leading to Ni, Cr and Fe accumulation in the B horizons whereas the lowest saturated soils had very low-metal contents. Most soil minerals were inherited from the parent materials and there were only few traces of formation of secondary minerals. Primary minerals (e.g. serpentine, chlorite) contained low Ni concentrations (0.2%) whereas neoformed goethite, mainly in the B horizons of the richest soils, contained up to 4.3% Ni. Ni was probably sorbed onto amorphous Fe oxy−hydroxide particles (oxalate extraction) rather than incorporated within the crystal lattice of goethite. Ni availability in the B horizon of Hypereutric Cambisols was extremely high and so was the oxalate extractable Fe. At the toposequence level, there was a high level of Ni availability in the least weathered soils and a very low-availability level in the more intensively weathered soils (strongly acidic pH). Ni availability was unexpectedly positively correlated to pH and was controlled by soil mineralogy and Ni-bearing mineral phases. Ni hyperaccumulation (above 1,000 mg kg⁻¹) by native T. caerulescens was only reached in the Ni-rich soils as a consequence of the local edaphic factors. Ni uptake by T. caerulescens is strongly regulated by Ni availability in soils and therefore related to pedogenesis.     

Copper concentration in plants and in the rhizosphere as influenced by the iron status of tomato (Lycopersicon esculentum L.)

Changes of metal concentration that occur in the rhizosphere may arise from several processes including variation in the concentration of complexing ligands, pH or redox potential that can be influenced by the Fe status of the plant. The aim of this study was to assess for both acidic and calcareous, Cu-contaminated soils how Cu concentration in plants and in the rhizosphere was affected by the Fe status of a strategy I plant species. The change of soil solution pH, total solution Cu concentration and soil redox potential was monitored for 8 days in the rhizosphere of tomato (Lycopersicon esculentum L.) in response to contrasting Fe supply. The concentration of Cu in roots was enhanced under Fe deficiency in the acidic soils. Shoot Cu however did not vary with the Fe status of the plant. The plant Fe status had little effect on rhizosphere pH, redox potential or Cu concentration in solution in either acidic or calcareous soils. Marked differences in pH and solution Cu concentration were observed between rhizosphere and uncropped soils. Roots induced an increase in pH of acidic soils and a decrease in solution Cu concentration in all soils. The decrease in solution Cu concentration in acidic soils may be explained by the increase in rhizosphere pH. The proposed device provided new data on the fate of Cu in the rhizosphere and showed a positive correlation for the four soils considered together between the total Cu concentration in soil solution and root Cu concentration.     

Innovative methods for soil DNA purification tested in soils with widely differing characteristics

Seven methods of soil DNA extraction and purification were tested in a set of 14 soils differing in bedrock, texture, pH, salinity, moisture, organic matter content, and vegetation cover. The methods introduced in this study included pretreatment of soil with CaCO(3) or purification of extracted DNA by CaCl(2). The performance of innovated methods was compared to that of the commercial kit Mo Bio PowerSoil and the phenol-chloroform-based method of D. N. Miller, J. E. Bryant, E. L. Madsen, and W. C. Ghiorse (Appl. Environ. Microbiol. 65:4715-4724, 1999). This study demonstrated significant differences between the tested methods in terms of DNA yield, PCR performance, and recovered bacterial diversity. The differences in DNA yields were correlated to vegetation cover, soil pH, and clay content. The differences in PCR performances were correlated to vegetation cover and soil pH. The innovative methods improved PCR performance in our set of soils, in particular for forest acidic soils. PCR was successful in 95% of cases by the method using CaCl(2) purification and in 93% of cases by the method based on CaCO(3) pretreatment, but only in 79% by Mo Bio PowerSoil, for our range of soils. Also, the innovative methods recovered a higher percentage of actinomycete diversity from a subset of three soils. Recommendations include the assessment of soil characteristics prior to selecting the optimal protocol for soil DNA extraction and purification.     

Bioavailability and crop uptake of trace elements in soil columns amended with sewage sludge products

In order to assess the potential impact of long-term sewage sludge application on soil health, the equivalent of about 25 years of agronomic applications of low-metal (`EQ') sewage sludge products were made to greenhouse soil columns. After a 6-year period of `equilibration', during which time successive crops were grown with irrigation by simulated acid rain, the plant-available quantities of trace elements were estimated in the soils by extraction with 0.01 M CaCl₂ at 90 °C, and measured directly by uptake into a crop of red clover (Trifolium pratense L.). Soil pH had a strong influence on the level of extractable and plant-available metals, and because the tested sludge products affected soil pH differently, pH was directly factored into the comparison of different sludge treatments with controls. CaCl₂-extractable levels of several metals (Cu, Zn, Mo), sulfur and phosphorus were found to be higher in the soils amended with organic-rich sludge products than in the control soils. However, extractable Cd and Ni were not significantly elevated by the sludge amendments, presumably because of the low total loading of these metals. Copper, Zn and Mo applied in the form of sludge ash had low soil extractability, suggesting that these trace metals were trapped in high-temperature mineral phases formed during sludge incineration, and resisted subsequent weathering in the soil environment. Extractable soil metals in the alkaline-stabilized sludge treatment were also generally low. Phytotoxicity from the sludge metal loadings (Zn≤125, Cu≤135 kg/ha), was not clearly indicated as long as soil pH was maintained in the 6–7 range by lime amendment. Nevertheless, unexplained depressions in yield were noted with some of the sludge products applied, particularly the dewatered and composted materials. On limed soil columns, the most consistent effect of sludge product amendment on red clover composition was a marked increase in plant Mo.     

南京市城乡公路蜀桧叶片中金属元素和氮、硫含量分析

通过对南京市城乡公路(城市干线、绕城公路和城郊公路)和相对清洁对照点植物园环境中土壤和蜀桧叶片中金属元素和N、S含量的测定,研究了环境元素在土壤植物大气之间的转移.结果表明,在城市干线、绕城公路和城郊公路环境中生长的蜀桧叶片中,10种金属元素中有Al、Fe、Mo、Zn、Cd、Pb、As和Cr含量明显超过对照点,其中尤以Al、Fe、Mo和Zn最显著.公路环境蜀桧叶片中,Fe、Zn和As在土壤植物间的相关性显著,说明蜀桧可能是Fe、Zn和As的良好指示植物;蜀桧叶片中Al、Mo、Cu、Pb、Cd和Cr在土壤植物间相关性不显著,说明公路环境中其含量较高可能是受大气污染的影响.城市干线和绕城公路蜀桧叶片中的N和S含量高于对照点,而城郊公路则接近对照.相关分析表明,公路土壤含N量在土壤植物间呈负相关,低于对照,含S量在土壤植物间呈正相关,高于对照.因此,公路环境蜀桧叶片中较高的N含量可能是汽车尾气排放的NOx影响的结果,而较高的S含量则主要来自土壤.     

Copper,manganese and iron concentration in berseem (Trifolium Alexandrinum) and coppermolybdenum ratio as affected by molybdenum in two types of soil

Summary The effect of Mo on Cu, Mn and Fe; and Cu: Mo ratio in berseem was studied in a normal cultivated and recently reclaimed saline-sodic soil. Mo application decreased Cu, Mn and Fe content in berseem in both the soils. Cu, Mn and Fe content in plant tissue grown in recently reclaimed soil was less than normal cultivated soil. Mo decreased Cu: Mo ratio whereas S application increased Cu: Mo ratio in plant. Cu: Mo ratio from animal nutrition point of view was in the safe range if Mo was not applied in the berseem crop.     

Evaluation of toxic conditions associated with oranging symptoms of rice in a flooded Oxisol in Sumatra,Indonesia

The toxic conditions of Oxisol soils attributed to oranging symptoms of rice grown in the Sitiung Transmigration area, Sumatra, Indonesia were evaluated in the laboratory. Changes of pH and Eh of flooded soils, and concentrations of nutrients in the soils and in the rice plants were measured. The soils were clayey, kaolinitic, isohyperthermic, Typic Haplorthox. It was found that Eh of the soils sharply decreased from an average value of +460 ± 150 mV to –217 ± 15 mV following 60 days of flooding (DF). During the same period of flooding, soil pH increased from an average value of 5.2 ± 0.6 to 6.6 ± 0.2. Concentrations of NaOAc extractable Fe, Mn, Zn, Cu, Mo, Ca, Mg, P, and K, but not Al, increased markedly whereas their water-soluble form, except Fe, decreased slightly following 60 DF. Leaf tissue analyses indicated that 13, 51 and 58% of the rice plant samples contained potentially toxic level of Mn, Fe and Al, respectively, as their contents were higher than the assumed threshold toxicity levels of 2500, 300, and 300 mg kg^–1. Thirteen, 16, 2, and 3% of the leaf tissue also contained potentially deficient levels of P, K, Ca, and Mg, respectively. The oranging symptom in the rice leaf tissue appeared to be due to indirect toxicity of Fe, Mn, and Al, i.e., Fe-induced, Mn-induced, and Al-induced deficiency of P, K, Ca and Mg. As a result of the relatively high concentrations of NaOAc extractable Fe, Mn, and Al in the soil solution, root growth was limited and coated with iron and manganese oxides thereby reducing the root's capacity to absorb nutrients from the soils.The work was supported by USAID Grant No. DPE-5542-G-SS-4055-00 (3.F-10). Contribution from the Wetland Biogeochemistry Institute, Louisiana State University, Baton Rouge, LA 70803-7511, USA.     

Iron availability in plant tissues-iron chlorosis on calcareous soils

The article describes factors and processes which lead to Fe chlorosis (lime chlorosis) in plants grown on calcareous soils. Such soils may contain high HCO₃ ^- concentrations in their soil solution, they are characterized by a high pH, and they rather tend to accumulate nitrate than ammonium because due to the high pH level ammonium nitrogen is rapidly nitrified and/or even may escape in form of volatile NH₃. Hence in these soils plant roots may be exposed to high nitrate and high bicarbonate concentrations. Both anion species are involved in the induction of Fe chlorosis.Physiological processes involved in Fe chlorosis occur in the roots and in the leaves. Even on calcareous soils and even in plants with chlorosis the Fe concentration in the roots is several times higher than the Fe concentration in the leaves. This shows that the Fe availability in the soil is not the critical process leading to chlorosis but rather the Fe uptake from the root apoplast into the cytosol of root cells. This situation applies to dicots as well as to monocots. Iron transport across the plasmamembrane is initiated by Fe^III reduction brought about by a plasmalemma located Fe^III reductase. Its activity is pH dependent and at alkaline pH supposed to be much depressed. Bicarbonate present in the root apoplast will neutralize the protons pumped out of the cytosol and together with nitrate which is taken up by a H⁺/nitrate cotransport high pH levels are provided which hamper or even block the Fe^III reduction.Frequently chlorotic leaves have higher Fe concentrations than green ones which phenomenon shows that chlorosis on calcareous soils is not only related to Fe uptake by roots and Fe translocation from the roots to the upper plant parts but also dependent on the efficiency of Fe in the leaves. It is hypothesized that also in the leaves Fe^III reduction and Fe uptake from the apoplast into the cytosol is affected by nitrate and bicarbonate in an analogous way as this is the case in the roots. This assumption was confirmed by the highly significant negative correlation between the leaf apoplast pH and the degree of iron chlorosis measured as leaf chlorophyll concentration. Depressing leaf apoplast pH by simply spraying chlorotic leaves with an acid led to a regreening of the leaves.     

The effect of limestone,molybdenum and incubation upon the extractable molybdenum in soils of eastern Canada

Summary An incubation experiment was conducted on 3 soils with 3 levels of lime-stone and 2 levels of Mo in the laboratory. There was no change in the amount of exchangeable Mo in Culloden and O'Leary soils as affected by the various pH levels after different incubation periods. On Acadia soil, the amount of exchangeable Mo increased after 4 weeks; however, the lime levels had no effect. There was an increase in extractable Mo in response to added Mo. Contribution No.206, Research Branch, Canada Department of Agriculture, Box 1210, Charlottetown, P. E. I., Canada.     

Reductive Reactivity of Iron(III) Oxides in the East China Sea Sediments: Characterization by Selective Extraction and Kinetic Dissolution

Reactive Fe(III) oxides in gravity-core sediments collected from the East China Sea inner shelf were quantified by using three selective extractions (acidic hydroxylamine, acidic oxalate, bicarbonate-citrate buffered sodium dithionite). Also the reactivity of Fe(III) oxides in the sediments was characterized by kinetic dissolution using ascorbic acid as reductant at pH 3.0 and 7.5 in combination with the reactive continuum model. Three parameters derived from the kinetic method: m ₀ (theoretical initial amount of ascorbate-reducible Fe(III) oxides), k′ (rate constant) and γ (heterogeneity of reactivity), enable a quantitative characterization of Fe(III) oxide reactivity in a standardized way. Amorphous Fe(III) oxides quantified by acidic hydroxylamine extraction were quickly consumed in the uppermost layer during early diagenesis but were not depleted over the upper 100 cm depth. The total amounts of amorphous and poorly crystalline Fe(III) oxides are highly available for efficient buffering of dissolved sulfide. As indicated by the m ₀, k′ and γ, the surface sediments always have the maximum content, reactivity and heterogeneity of reactive Fe(III) oxides, while the three parameters simultaneously downcore decrease, much more quickly in the upper layer than at depth. Albeit being within a small range (within one order of magnitude) of the initial rates among sediments at different depths, incongruent dissolution could result in huge discrepancies of the later dissolution rates due to differentiating heterogeneity, which cannot be revealed by selective extraction. A strong linear correlation of the m ₀ at pH 3.0 with the dithionite-extractable Fe(III) suggests that the m ₀ may represent Fe(III) oxide assemblages spanning amorphous and crystalline Fe(III) oxides. Maximum microbially available Fe(III) predicted by the m ₀ at pH 7.5 may include both amorphous and a fraction of other less reactive Fe(III) phases.     

Trace elements extractable by 2-ketogluconic acid from soils and their relationship to plant contents

Summary Trace element levels extractable by 2-ketogluconic acid (2-KG), ammonium acetate, acetic acid, EDTA, and DTPA were determined in three different soils of the Tarves association. The 2-ketogluconic acid was derived from 2-litre batch cultures of a soil bacterium,Erwinia sp. Pasture grasses and clovers growing on these soils were also analysed. At the same pH, 2-KG extracted more Co, Ni and Zn and considerably more Fe, Ti and V than ammonium acetate. The quantities of Cu, Mn, Mo, Ni and Zn extracted by 2-KG from the three soils generally reflected, in a similar way to the other extractants, the contents of these elements in grasses and clovers growing on the soils.     

Sulfur and molybdenum fractionation in marine and riverine alluvium paddy soils

Intermittently submergence and drainage status of paddy fields can cause alterations in morphological and chemical characteristics of soils. We conducted a sequential fractionation study to provide an insight into solubility of Sulfur (S) and Molybdenum (Mo) in flooded alluvial paddy soils. The samples (0–15 and 15–30 cm) were taken from marine and riverine alluvial soils in Kedah and Kelantan areas, respectively, and were sequentially extracted with NaHCO₃, NaOH, HCl, and HClO₄–HNO₃. Total S in upper and lower layers of Kedah and Kelantan ranged between 273 and 1121 mg kg^?1, and 177 to 1509 mg kg^?1, respectively. In upper layers and subsoil of Kedah, average total Mo were 0.34 and 0.27 mg kg^?1, respectively. Average total Mo in Kelantan were 0.25 mg kg^?1 (surface layer) and 0.28 mg kg^?1 (subsoil). Cation exchange capacity (CEC) was positively correlated with plant available amounts of Mo in upper layers of Kedah area. Also, total and medium-term plant-available S was correlated with total carbon (C) at lower layers of Kelantan soil series. But in surface layers of Kelantan soil series, CEC was strongly correlated with total and medium-term plant-available S. Our results indicates that the influence of flooding conditions on soil S and Mo contents in paddy fields may cause long-term changes in S and Mo chemical reactivities.     

The effects of flooding for rice culture on soil chemical properties and subsequent maize growth

Summary The effects of flooding and lowland rice culture on soil chemical properties and subsequent maize growth were investigated in two contrasting rice soils of S.E. Australia. The effects of incorporating rice straw, either during or after flooding were also studied. The experiment was conducted in a glasshouse with the use of large intact soil cores.Previous flooding markedly reduced maize growth, leaf P concentration and P uptake, despite the application of a large quantity of P fertilizer after drainage. Soil analyses showed that previous flooding increased the Langmuir sorption terms for maximum P sorption and bonding energy. The availability of P was more closely related to the bonding energy between soil and P than to the capacity of the soils to sorb P. The increases, in the P sorption parameters, were associated with decreases in the crystallinity of the free iron oxides as determined by their oxalate solubility. It was concluded that depressed P supply to maize sown in previously flooded soils was due to stronger P sorption by the drained soils, rather than to P immobilization during flooding.Rice plants grown during flooding reduced the amount of N available to the subsequent maize crop, but did not significantly affect P availability. Rice straw added during flooding did not affect subsequent maize growth, but when added after flooding caused microbial immobilization of N.Salts, Fe or Mn from previous flooding did not affect maize growth.     

Association with pedogenic iron and aluminum: effects on soil organic carbon storage and stability in four temperate forest soils

Soil organic carbon (SOC) can be stabilized via association with iron (Fe) and aluminum (Al) minerals. Fe and Al can be strong predictors of SOC storage and turnover in soils with relatively high extractable metals content and moderately acidic to circumneutral pH. Here we test whether pedogenic Fe and Al influence SOC content and turnover in soils with low Fe and Al content and acidic pH. In soils from four sites spanning three soil orders, we quantified the amount of Fe and Al in operationally-defined poorly crystalline and organically-complexed phases using selective chemical dissolution applied to the soil fraction containing mineral-associated carbon. We evaluated the correlations of Fe and Al concentrations, mean annual precipitation (MAP), mean annual temperature (MAT), and pH with SOC content and ¹⁴C-based turnover times. We found that poorly crystalline Fe and Al content predicted SOC turnover times (p < 0.0001) consistent with findings of previous studies, while organically-complexed Fe and Al content was a better predictor of SOC concentration (p < 0.0001). Greater site-level MAP (p < 0.0001) and colder site-level MAT (p < 0.0001) were correlated with longer SOC turnover times but were not correlated with SOC content. Our results suggest that poorly crystalline Fe and Al effectively slow the turnover of SOC in these acidic soils, even when their combined content in the soil is less than 2% by mass. However, in the strongly acidic Spodosol, organo-metal complexes tended to be less stable resulting in a more actively cycling mineral-associated SOC pool.     

Copper,Lead, Cadmium,and Zinc Sorption By Waterlogged and Air-Dry Soil

Competitive sorption of copper (Cu), lead (Pb), cadmium (Cd), and zinc (Zn) was studied in three soils of contrasting chemical and physical properties under air-dry and waterlogged conditions. Competitive sorption was determined using the standard batch technique using six solutions, each with Cu, Pb, Cd, and Zn concentrations of approximately 0, 2.5, 5, 10, 20, and 50?mg L^?1Waterlogged soils tended to sorb higher amounts of added Cu, Pb, Zn and Cd relative to soils in the air-dry condition; however, this increase in sorption was generally not statistically (p<0.05) significant. The magnitude of sorption under both waterlogged and air-dry conditions was affected by the type and amount of soil materials involved in metal sorption processes, and competition between other metals for the sorption sites. Metal sorption was closely correlated with soil properties such as cation exchange capacity, organic carbon, and Fe and Mn hydrous oxides. Exchangeable Al may have markedly reduced metal sorption due to its strong affinity for the sorption sites, while increases in exchangeable Mn may have enhanced Zn and Cd sorption. Heavy metal sorption was best described as a combination of both specific and nonspecific interactions. The extractability of Cu, Pb, Cd, and Zn under waterlogged and air-dry conditions was also studied. Three solutions containing these metals were mixed with each soil to achieve a final concentration of 0, 50, and 500?mg kg^?1. Each soil was extracted every 7 days using 1?M MgCl₂ (pH 7) to determine metal extractability. Metal extractability initially decreased then increased due to waterlogging. The increased extractability of added metals was closely related to increased solubility of Fe and Mn suggesting that dissolution of Fe and Mn, oxides under reducing conditions caused a release of previously sorbed Cu, Pb, Cd, and Zn.     

Prediction of reducible soil iron content from iron extraction data

Soils contain various iron compounds that differ in solubility, reducibility and extractability. Moreover, the contribution of the various iron compounds to total iron (Fe) and total Fe concentrations differs highly among soils. As a result, the total reducible Fe content can also differ among soils, and so does the dynamics of iron reduction. These factors complicate the prediction of reducible Fe based on Fe extraction data and hamper the application of process-based models for reduced or waterlogged soils where redox processes play a key-role. This paper presents a theoretical analysis relating reducible to extractable Fe reported in the literature. Predictions made from this theoretical analysis were evaluated in soil incubations using 18 rice paddy soils from all over the world. The incubation studies and the literature study both show that reducible Fe can be related to Fe from some selected, but not all, iron extractions. The combination of measurements for labile Fe(III)oxides (derived from oxalate-extractable Fe) and stabile Fe(III)oxides (derived from dithionite-citrate-extractable Fe) shows highly significant correlations with reducible Fe with high coefficients of determination (r² = 0.92–0.95 depending on the definition of stabile Fe(III)oxides). Given the high diversity in rice soils used for the incubations, these regression equations will have general applicability. Application of these regression equations in combination with soil database information may improve the predictive ability of process-based models where soil redox processes are important, such as CH₄ emission models derived for rice paddies or wetlands.     

Multiple roles of siderophores in free-living nitrogen-fixing bacteria

Free-living nitrogen-fixing bacteria in soils need to tightly regulate their uptake of metals in order to acquire essential metals (such as the nitrogenase metal cofactors Fe, Mo and V) while excluding toxic ones (such as W). They need to do this in a soil environment where metal speciation, and thus metal bioavailability, is dependent on a variety of factors such as organic matter content, mineralogical composition, and pH. Azotobacter vinelandii, a ubiquitous gram-negative soil diazotroph, excretes in its external medium catechol compounds, previously identified as siderophores, that bind a variety of metals in addition to iron. At low concentrations, complexes of essential metals (Fe, Mo, V) with siderophores are taken up by the bacteria through specialized transport systems. The specificity and regulation of these transport systems are such that siderophore binding of excess Mo, V or W effectively detoxifies these metals at high concentrations. In the topsoil (leaf litter layer), where metals are primarily bound to plant-derived organic matter, siderophores extract essential metals from natural ligands and deliver them to the bacteria. This process appears to be a key component of a mutualistic relationship between trees and soil diazotrophs, where tree-produced leaf litter provides a living environment rich in organic matter and micronutrients for nitrogen-fixing bacteria, which in turn supply new nitrogen to the ecosystem.