Effects of humic substances on iron nutrition of lupin

Poorly crystalline Fe oxides and organic matter are two important factors affecting Fe nutrition of plants. The main objective of this work was to study the contribution of humic substances to Fe nutrition of a typical Fe-chlorosis sensitive plant (white lupin, Lupinus albus L.). An experiment was performed involving two growing media (siliceous and calcareous) and different Fe sources: control without additional Fe added to the growing media, ferrihydrite (FH), FH + humic substances (HS, at two rates, 0.1 and 0.3 g C kg⁻¹ growing media), Fe complexed to humic substances (Fe–HS), and Fe–EDDHA (as an effective Fe source in calcareous media). Chlorophyll meter readings and dry matter production (DM) were significantly greater with Fe–EDDHA and Fe–HS when compared with the other treatments in calcareous media. The positive effect of complexed Fe (to EDDHA or HS) on Fe nutrition can be, at least partially, related to an increase in Fe(III)-reducing capacity by roots, which seems to be improved by an enhanced root development. No positive effect on Fe nutrition was observed with the application of HS in a ferrihydrite enriched growing media (FH + HS) at 4 weeks, particularly with the application of HS at 0.3 g C kg⁻¹ in calcareous media. Thus, the effect of HS on Fe availability was only positive if some Fe is complexed to HS. The efficiency of HS with Fe complexed (Fe–HS) in preventing Fe chlorosis was found to be similar to Fe–EDDHA. This is important not only for the knowledge of factors affecting Fe availability in soils, but also with a view of using Fe–HS complexes as effective products to correct this nutritional problem.     

ADVERSE EFFECTS OF HUMIC SUBSTANCES FROM DIFFERENT ORIGIN ON LUPIN AS RELATED TO IRON SOURCES

Humic substances improve the efficiency of different iron (Fe) sources overcoming Fe deficiency chlorosis of plants. However, applied at high rates, they can promote negative effects on plants. The main objective of this work was to study the potential adverse effect of three humic acids from different origin when they were applied with two effective Fe sources for plants: Fe- ethylenediaminedihydroxyphenylacetic acid (EDDHA) and Vivianite. To this end, an experiment with lupin (Lupinus albus L.) was performed involving two factors: (i) Fe source, and (ii) humic substances from three different origin (composted cork, leonardite, and compost obtained from a mixture of olive husk with cotton gin trash) applied at 0, 0.1, and 0.5 g organic carbon (C) kg^?1 of growing media. At the rates used, humic substances promoted adverse effects on plant development, chlorophyll meter readings, and Fe content in lupin grown in calcareous media. Overall, the effect on dry matter and Fe content in plants was more relevant when Fe was supplied with Vivianite, the effect on chlorophyll meter readings being more significant when Fe was applied as Fe-EDDHA. Differences were also observed depending on the source of humic substances, those from leonardite promoting the greatest decrease in dry matter in roots and shoots. These humic substances possessed the highest values of spectroscopy index for aromaticity (A₂₅₄ ). On the other hand, the application of humic substances from olive husk compost, which exhibited the lower aromaticity index, resulted in the smallest decrease in dry matter production and chlorophyll meter readings. Dry matter in roots decreased logarithmically with increased values of the estimates of the amounts of aromatic compounds accumulated in the growing media (R² = 0.92; P < 0.01) with Vivianite as Fe source. Thus, the effects decreasing dry matter production, particularly in roots, and chlorophyll meter readings can be ascribed at least partially to the presence of phytotoxic aromatic compounds in humic substances.     

Effectiveness of Vivianite to Prevent Lime-Induced Iron Deficiency in Lemon Trees Grown on Highly Calcareous Soil

The short-term effectiveness of three application rates of vivianite [(Fe₃(PO₄)₂·8H₂O)] in preventing lime-induced iron (Fe) chlorosis in Eureka lemon (Citrus lemon L.) cuttings grafted on sour orange (Citrus aurantium L.) was investigated and compared with the commonly applied iron ethylenediaminedi(o-hydroxyphenylacetic) acid (FeEDDHA). Treatments were suspension of vivianite injected into the soil at three rates (0.5, 1.0, and 2.0 g kg^?1 soil), 417 mg FeEDDHA per plant, and untreated plants. Chlorophyll concentration index (CCI) of the youngest fully expanded leaves was estimated. Growth vigor and leaf Fe concentration were also measured. Vivianite, particularly at the greatest two rates, resulted in significantly greater growth vigor and leaf Fe concentration and exhibited greater CCI values compared to untreated plants similar to FeEDDHA. However, if excessive growth vigor is not favorable, the 0.5 g vivianite kg^?1 soil is recommended for farmers. Vivianite is a potential environmentally safe alternative to the expensive FeEDDHA to prevent Fe chlorosis in lemon.     

Iron and/or acid foliar spray versus soil application of Fe-EDDHA for prevention of iron deficiency in Valencia orange grown on a calcareous soil

A two-year experiment was conducted in an iron(Fe)-deficient orchard with calcareous soil to find out an alternate method for soil application of Fe ethylenediamine-N,N'-bis(2-hydroxyphenylacetic acid) (Fe-EDDHA) in orange trees. Foliar sprays of Fe-EDDHA (5 g l^?1, pH = 7.8), sulfuric acid (pH = 3), citric acid (5 g l^?1, pH = 2.4), Fe (II) sulfate solutions (250, 500, and 750 mg Fe l^?1) with their initial pH (6.5, 6.35, and 6.12) and reduced ones to pH of 3 were compared with soil applied (75 g tree^?1) Fe-EDDHA and a control test. Although optimum chlorophyll content, leaf Fe concentration, fruit quantitative and qualitative attributes were resulted from soil application of Fe-EDDHA, repeated sprays of Fe-EDDHA or acidified Fe solutions created suitable results. Acidification of Fe solutions made them more effective in alleviation of leaf Fe concentration and Fe chlorosis, probably due to remobilization of inactive Fe within the plant and prevention of Fe oxidation and precipitation in foliar solutions.     

Iron Chlorosis in Gerber as Related to Properties of Various Types of Compost used as Growing Media

Abstract

Nutrient deficiencies in crop plants may be influenced by a number of properties of the growing media. Some peat‐substitute substrates can promote iron (Fe) chlorosis in sensitive plants, which has traditionally been ascribed to the elevated pH of growing media. To identify the origin of this problem in various types of composted organic residues used as growing media and possible corrections, a complete randomized experiment on gerber (Gerbera jamesonii Adlam) as an Fe‐chlorosis sensitive crop involving three factors (growing medium, medium acidification, and the medium treatment with Fe) was performed.

Although the Fe content in plants decreased with increasing pH in the growing medium, the chlorophyll content as measured using a chlorophyll meter (Minolta Soil Plant Analysis Development, SPAD) was not significantly related to pH. The SPAD readings and Fe concentrations in plants, dry matter, and flower production were not significantly related to diethylenetriaminepentaacetic acid (DTPA)–extractable Fe in the growing media. The addition of Fe‐chelate significantly increased yield (P<0.01), and SPAD at 65 and 96 days after planting (P<0.001 and P<0.01, respectively). However, the effect of the acid treatment was, different depending on the growing media. When the acidification promoted a positive effect on SPAD readings, this was nonsignificantly different than that obtained with the application of Fe‐chelate. The estimated amount of available Fe in the growing media was not relevant, which explains the incidence of chlorosis as physiological factors related to pH.     

Glufosinate and ammonium sulfate inhibit atrazine degradation in adapted soils

The co-application of glufosinate with nitrogen fertilizers may alter atrazine cometabolism, thereby extending the herbicide’s residual weed control in adapted soils. The objective of this study was to assess the effects of glufosinate, ammonium sulfate, and the combination of glufosinate and ammonium sulfate on atrazine mineralization in a Dundee silt loam exhibiting enhanced atrazine degradation. Application of glufosinate at rates of 10 to 40 mg kg⁻¹ soil extended the lag phase 1 to 2 days and reduced the maximum degradation rate by 15% to 30%. However, cumulative atrazine mineralization averaged 85% 21 days after treatment and was independent of treatment. Maximum daily rates of atrazine mineralization were reduced from 41% to 55% by application of 1 to 8 g kg⁻¹ of ammonium sulfate. Similarly, cumulative atrazine mineralization was inversely correlated with ammonium sulfate rates ranging from 1.0 to 8 g kg⁻¹ soil. Under the conditions of this laboratory study, atrazine degradation was relatively insensitive to exogenous mineral nitrogen, in that 8 g (NH₄)₂SO₄ per kilogram soil repressed but did not completely inhibit atrazine mineralization. Moreover, an additive effect on reducing atrazine mineralization was observed when glufosinate was co-applied with ammonium sulfate. In addition, ammonium fertilization alters the partitioning of ¹⁴C-atrazine metabolite accumulation and nonextractable residues, indicating that ammonium represses cleavage of the triazine ring. Consequently, results indicate that the co-application of glufosinate with N may increase atrazine persistence under field conditions thereby extending atrazine residual weed control in adapted soils.     

Effect of Trichoderma asperellum strain T34 on iron nutrition in white lupin

The production of chelating compounds (siderophores) by microorganisms increases Fe availability to plants. The main objective of this work was to study the effect of Trichoderma asperellum strain T34, a commercially available biocontrol agent, on Fe availability to white lupin (Lupinus albus L). To this end, experiments involving three factors [viz. growing medium (siliceous or calcareous), Fe supply (ferrihydrite enrichment and no enrichment), and inoculation with T34] were performed.Chlorophyll meter readings and concentration and total content of Fe in plants grown on the siliceous medium were decreased by T34, but only in the absence of ferrihydrite. This suggests a potential competition between plants and T34 for Fe under conditions of restricted availability. By contrast, T34 increased the Fe concentration in the aerial parts of lupin plants grown on the calcareous medium. In ferrihydrite-enriched calcareous media, T34 decreased chlorophyll content of the plants. This cannot be ascribed to depressed Fe nutrition or other nutrient deficiency. Inoculation with T34 increased peroxidase (ferrihydrite-enriched calcareous media and siliceous media without ferrihydrite) and catalase activities, but decreased the peroxidase to catalase activity ratio. This effect on the activities of Fe-containing enzymes, which was not the sole result of increased Fe availability to plants, accounts for the disparate relationship between SPAD meter readings and Fe concentrations in plants in inoculated and non-inoculated media. Based on them, a higher Fe concentration in aerial parts was required for similar SPAD meter readings in plants with T34 than in those without T34. This may have resulted from an increased activity in Fe-containing enzymes (particularly catalase) reducing the availability of free Fe for chlorophyll synthesis, which is consistent with the significantly decreased SPAD readings by the effect of T34 in ferrihydrite-enriched calcareous media.     

Dynamic of organic matter in the heavy fraction after abandonment of cultivated wetlands

The abandonment of cultivated wetland soil increased the contents of light fraction organic matter (LFOM), heavy fraction organic matter (HFOM) and soil organic matter (SOM). The LFOM and HFOM content increased to 13.3 g kg⁻¹ and 62.4 g kg⁻¹ after 5 years whereas they were 8.4 and 47.9 g kg⁻¹ after 9 years of cropping, respectively. Fourteen years after abandonment, HFOM content increased to 104.3 g kg⁻¹. LFOM was positively correlated with HFOM (p < 0.001). A Langmuir equation was used to calculate the highest HFOM value. The value for the natural wetland soil was closed to this theoretical value (140.8 g kg⁻¹). After 14 years of abandonment, the HFOM maximum (HFOM_Max) value was lower than the equilibrium value suggesting that a further increase in HFOM can occur after abandonment. Assuming a linear accumulation (3.87 Mg C ha⁻¹yr⁻¹), it would take approximately 24 years after the abandonment to reach the HFOM_Max value.     

Crop residues and fertilizer nitrogen influence residue decomposition and nitrous oxide emission from a Vertisol

Crop residues with high C/N ratio immobilize N released during decomposition in soil, thus reducing N losses through leaching, denitrification, and nitrous oxide (N₂O) emission. A laboratory incubation experiment was conducted for 84 days under controlled conditions (24°C and moisture content 55% of water-holding capacity) to study the influence of sugarcane, maize, sorghum, cotton and lucerne residues, and mineral N addition, on N mineralization–immobilization and N₂O emission. Residues were added at the rate of 3 t C ha⁻¹ to soil with, and without, 150 kg urea N ha⁻¹. The addition of sugarcane, maize, and sorghum residues without N fertilizer resulted in a significant immobilization of soil N. Amended soil had significantly (P < 0.05) lower NO₃⁻–N, which reached minimum values of 2.8 mg N kg⁻¹ for sugarcane (at day 28), 10.3 mg N kg⁻¹ for maize (day 7), and 5.9 mg N kg⁻¹ for sorghum (day 7), compared to 22.7 mg N kg⁻¹ for the unamended soil (day 7). During 84 days of incubation, the total mineral N in the residues + N treatments were decreased by 45 mg N kg⁻¹ in sugarcane, 34 mg kg⁻¹ in maize, 29 mg kg⁻¹ in sorghum, and 16 mg kg⁻¹ in cotton amended soil compared to soil + N fertilizer, although soil NO₃⁻–N increased by 7 mg kg⁻¹ in lucerne amended soil. The addition of residues also significantly increased amended soil microbial biomass C and N. Maximum emissions of N₂O from crop residue amended soils occurred in the first 4–5 days of incubation. Overall, after 84 days of incubation, the cumulative N₂O emission was 25% lower with cotton + N fertilizer, compared to soil + N fertilizer. The cumulative N₂O emission was significantly and positively correlated with NO₃⁻–N (r = 0.92, P < 0.01) and total mineral N (r = 0.93, P < 0.01) after 84 days of incubation, and had a weak but significant positive correlation with cumulative CO₂ in the first 3 and 5 days of incubation (r = 0.59, P < 0.05).     

The Roles of Diethylenetriamine Pentaacetate (DTPA) and Ethylenediamine Disuccinate (EDDS) in Remediation of Selenium from Contaminated Soil by Brussels Sprouts (Brassica oleracea var. gemmifera)

The objective of this study was to investigate the effects of adding different rates of diethylenetriamine pentaacetate (DTPA) at different concentrations (0, 0.5, 1, and 5 mmol kg⁻¹) and ethylenediamine disuccinate (EDDS) at 0, 5, 7.5, and 10 mmol kg⁻¹ on the capacity of Brussels sprouts plants to take up Se from soils contaminated with 0, 5, 10, and 15 mg kg⁻¹ NaSeO₄, under a greenhouse conditions. Results indicated that the application of DTPA and EDDS to Se-contaminated soils significantly affect plant Se concentration, Se uptake, and dry matter yield of plants. Se concentration in the plant leaves, stems, and roots increased with increase in DTPA and EDDS application doses, but total Se uptake increased from 0 to 1.0 and 7.5 mmol kg⁻¹ DTPA and EDDS application doses, respectively, and decreased after those levels due to toxic Se concentration for plant. Most plant available fractions and the carbonate, metal oxide, and organic matter-bound fractions increased linearly with Se application. At all DTPA and EDDS application rates, the Se concentrations in the leaves were about two to three times higher than those in the roots and about three to four times higher than those in the stems. This study suggests that the above-ground organs like leaf and shoots of Brussels sprouts can effectively be used in the removal of Se from soils contaminated with Se. Under the conditions in this experiment, Brussels sprouts were capable of removing 0.9–1.8 mg Se pot⁻¹ when harvested at maturity without any chelating agent take into consideration one growing season per year. Based on the data of present experiment, it would be necessary to approximately 57–67 growing seasons without EDDS and EDTA to remove all total Se from polluted soil. Selenium removal can be further increased 12- to 20-fold with 7.5 mmol kg⁻¹ EDDS and 1.0 mmol kg⁻¹ DTPA application, respectively.     

EVALUATION OF DIFFERENT IRON SOURCES FOR IRON CHLOROSIS RECOVERY IN LOW-CHILL PEACH CULTIVARS

An experiment was conducted with iron chlorosis affected low-chill peach cultivars such as ‘Shaharanpur Prabhat’, ‘Shan-e-Punjab’, and ‘Pratap’ to examine the recovery upon foliar application of three iron sources namely iron (Fe)-sulfate, Fe-citrate and Fe ethylenediaminetetraacetic acid (EDTA). All the iron sources significantly increased the SPAD meter value, physiologically active (Fe²⁺) iron and total iron content of the leaves over control. However, highest values were noted with foliar spray of 1.0% Fe-sulfate. The low-chill peach cultivar ‘Saharanpur Prabhat’ responded best with iron resupply treatment. Significant correlations (at P ≤ 0.01) were obtained between SPAD meter readings with both physiologically active iron (Fe²⁺) and total iron content of leaves in all peach cultivars. Among the sources, the correlations between SPAD meter readings, physiologically active iron (Fe²⁺) and total iron contents were significant at P ≤ 0.01 for only Fe-sulfate and Fe-citrate. The regression analysis showed that the SPAD meter reading accounted 78.2 to 88.0% variation in physiologically active iron (Fe²⁺) and 65.0 to 73.7% variation in the total iron content in the low-chill peach cultivars. The SPAD readings could be used for management of iron chlorosis in peach orchard.     

Phosphorus uptake and rhizosphere properties of intercropped and monocropped maize, faba bean, and white lupin in acidic soil

Little information is available on phosphorus (P) uptake and rhizosphere processes in maize (Zea mays L.), faba bean (Vicia faba L.), and white lupin (Lupinus albus L.) when intercropped or grown alone in acidic soil. We studied P uptake and soil pH, carboxylate concentration, and microbial community structure in the rhizosphere of maize, faba bean, and white lupin in an acidic soil with 0–250 mg P (kg⁻¹ soil) as KH₂PO₄ (KP) or FePO₄ (FeP) with species grown alone or intercropped. All plant species increased the pH compared to unplanted control, particularly faba bean. High KP supply (>100 mg P kg⁻¹) significantly increased carboxylate concentration in the rhizosphere of maize. The carboxylate composition of the rhizosphere soil of maize and white lupin was significantly affected by P form (KP or FeP), whereas, this was not the case for faba bean. In maize, the carboxylate composition of the rhizosphere soil differed significantly between intercropping and monocropping. Yield and P uptake were similar in monocropping and intercropping. Monocropped faba bean had a greater concentration of phospholipid fatty acids in the rhizosphere than that in intercropping. Intercropping changed the microbial community structure in faba bean but not in the other corps. The results show that P supply and P form, as well as intercropping can affect carboxylate concentration and microbial community composition in the rhizosphere, but that the effect is plant species-specific. In contrast to previous studies in alkaline soils, intercropping of maize with legumes did not result in increased maize growth suggesting that the legumes did not increase P availability to maize in this acidic soil.     

Nitrogen mineralization and CO2 and N2O emissions in a sandy soil amended with original or acidified pig slurries or with the relative fractions

The following six pig slurries obtained after acidification and/or solid/liquid separation were used in the research: original (S) and acidified (AS) pig slurry, nonacidified (LF) and acidified (ALF) pig slurry liquid fraction, and nonacidified (SF) and acidified (ASF) pig slurry solid fraction. Laboratory incubations were performed to assess the effect of the application of these slurries on N mineralization and CO₂ and N₂O emissions from a sandy soil. Acidification maintained higher NH₄ ⁺-N contents in soil particularly in the ALF-treated soil where NH₄ ⁺-N contents were two times higher than in LF-treated soil during the 55–171-day interval. At the end of the incubation (171 days), 32.9 and 24.2 mg N kg⁻¹ dry soil were mineralized in the ASF- and SF-treated soils, respectively, but no mineralization occurred in LF- and S-treated soils, although acidification decreased N immobilization in ALF- (−25.3 mg N kg⁻¹ soil) and AS- (−12.7 mg N kg⁻¹ soil) compared to LF- (−34.4 mg N kg⁻¹ soil) and S-treated (−18.6 mg N kg⁻¹ soil) soils, respectively. Most of the dissolved CO₂ was lost during the acidification process. More than 90% of the applied C in the LF-treated soil was lost during the incubation, indicating a high availability of the added organic compounds. Nitrous oxide emissions occurred only after day 12 and at a lower rate in soils treated with acidified than nonacidified slurries. However, during the first 61 days of incubation, 1,157 μg N kg⁻¹ soil was lost as N₂O in the AS-treated soil and only 937 in the S-treated soil.     

Glutathione foliar fertilisation prevents lime‐induced iron chlorosis in soil grown Medicago scutellata

It has been proposed that glutathione can relieve the effects of Fe deficiency. This study tested the effects of glutathione foliar treatments to prevent Fe chlorosis, using as positive controls soil and foliar Fe fertilisation. Medicago scutellata plants were grown in soil (5.7% CaCO₃) supplemented or not with 4 and 8% CaCO₃. Two Fe(III)‐EDDHA soil treatments (5 and 10 mg Fe kg^?1), and three foliar treatments (three applications each of 2.14 mM Fe(III)‐EDDHA, 1 mM glutathione, and the previous two combined) were applied. Measurements include leaf chlorophyll and Fe concentrations, biomass, leaf enzymatic and non‐enzymatic antioxidant systems and carboxylates. The addition of CaCO₃ caused typical Fe deficiency symptoms, including changes in chlorophyll, Fe, antioxidant systems and carboxylates, which were prevented by soil and foliar Fe fertilisation. The foliar treatment with glutathione also led to higher chlorophyll, leaf extractable Fe and root Fe, as well as decreases in some antioxidant systems, whereas leaf Fe concentrations decreased. The combined foliar application of glutathione and Fe was even more efficient in preventing chlorosis. Including glutathione in foliar fertilisation programs should be considered as an option for Fe chlorosis prevention, especially when relatively large leaf total Fe concentrations occur in the so called chlorosis paradox.     

A critical assessment of soil amendments (slaked lime/acidic fertilizer) for the phytomanagement of moderately contaminated shooting range soils

Purpose  

The effects of the addition of an acidic fertilizer solution and/or slaked lime (5.5 g Ca(OH)₂ kg⁻¹) on a slightly acidic shooting range soil (pH 6.1, % organic carbon 5.4) with moderate metal (e.g., 620 mg kg⁻¹ Pb) and metalloid (17 mg kg⁻¹ Sb) concentrations on metal and Sb solubility and plant accumulation were investigated.     

The Effect of Former Mining Activities on Contamination Dynamics in Sediments,Surface Water and Vegetation in El Avenque Stream,SE Spain

This work aims to identify and characterize heavy metal contamination in a fluvial system from Cartagena–La Unión mining district (SE Spain). In order to assess the dynamics of transport and the accumulation of heavy metals, sediments, surface water and vegetation, samples along “El Avenque” stream were collected. The former direct dumps of wastes and the presence of tailing ponds adjacent to the watercourse have contributed to the total contamination of the stream. Total Cd (103 mg kg⁻¹), Cu (259 mg kg⁻¹), Pb (26,786 mg kg⁻¹) and Zn (9,312 mg kg⁻¹) in sediments were above the limits of European legislation, being highest where tailing ponds are located. Bioavailable metals were high (3.55 mg Cd kg⁻¹, 6.45 mg Cu kg⁻¹, 4,200 mg Pb kg⁻¹ and 343 mg Zn kg⁻¹) and followed the same trend than total contents. Metals in water were higher in sampling points close to ponds, exceeding World Health Organization guidelines for water quality. There is a direct effect of solubilisation of sediment metals in water with high contents of SO₄²⁻, product of the oxidation of original sulphides. The mobility of metals varied significantly with shifts in pH. Downstream, available and soluble metals concentrations decreased mainly due to precipitation by increments in pH. As a general pattern, no metal was bioaccumulated by any tested plant. Thus, native vegetation has adopted physiological mechanisms not to accumulate metals. This information allows the understanding of the effect of mining activities on stream contamination, enforcing the immediate intervention to reduce risks related to metals’ mobility.     

Use of Minolta SPAD‐502 chlorophyll meter to quantify the effectiveness of mid‐summer trunk injection of iron on chlorotic pear trees

The severity of leaf chlorosis in iron (Fe)‐deficient fruit trees is often characterized using a semi‐quantitative visual rating index that is subject to evaluator bias. Analytical instruments are now available that provide a quantitative measure of leaf green color that could substitute for visual ratings. We injected limbs of mature chlorotic pear trees (Pyrus communis L. cv. Bartlett) with distilled water or a solution of 0.1% Fe (w/v) as FeSO₄‐7H₂O on 17 July 1995. Treatments were replicated eight‐fold. On 18 August 1995, a Minolta SPAD‐502 chlorophyll meter was used to measure the green color of 30 randomly sampled leaves located above the point of injection on each injected limb. Average leaf green color was higher in the Fe‐injected tree than in the water‐injected tree of each experimental block. Leaf green color (mean±SD) averaged 34.7±3.8 SPAD units for the Fe‐injected trees and 27.3±3.8 SPAD units for the water‐injected trees. The absolute increase in mean leaf color of 7.4 SPAD units was equivalent to a relative increase of 27%. Iron injection also induced more negative skewness and increased kurtosis in the frequency distribution curve for leaf SPAD meter readings. These results suggest that the SPAD meter can provide an unbiased quantitative measure of the severity of leaf chlorosis associated with Fe deficiency, and confirm that mid‐summer trunk injection of Fe can partially ameliorate Fe‐chlorosis symptoms.     

Zn and Pb release of sphalerite (ZnS)-bearing mine waste tailings

Background, aim, and scope  Contaminated mine drainage water has become a major hydrogeological and geochemical problem. Release of soluble metal contaminants and acidity from mining sites can pose serious chemical risks to surface and groundwater in the surrounding environment, and it is an important socio-economic factor addressed by working groups like SUITMA Morel and Heinrich (J Soils Sediments 8:206–207, 2008). The release of Zn and Pb from sulfide-bearing flotation residues of a small scale mine in Western Germany is investigated with focus on metal transfer to soil solution. Total contents of the soil material as well as soil water sampled with suction cups were analyzed. The influence of pH on leaching behavior was investigated with pH_stat tests. Isotopic analyses helped assessing seepage water velocity. The aim of this study was the assessment of the environmental behavior of zinc and lead caused by the weathering of sulfide-bearing mine tailings. Especially, we address in this paper the dissolution of sphalerite (ZnS) in contrast to the well-known dissolution processes of pyrite (FeS₂). Materials and methods  Total metal contents of the soil samples were analyzed by energy-dispersive X-ray fluorescence spectroscopy, total C concentration was measured using a CHNS elemental analyzer. X-ray diffraction (XRD) spectra were recorded from powdered soil samples. Soil water was sampled in nylon suction cups. Electrical conductivity (EC), pH, and temperature of the soil water samples were measured in the field immediately after sampling. Major anions (F, Cl, NO₂, NO₃, SO₄) were analyzed by ion chromatography, major cations (Ca, Na, K, Li) were analyzed by flame photometry, heavy metals (Zn, Pb, Fe, Mn, and Mg) by flame atomic absorption spectrometry. Tritium was analyzed by liquid scintillation counting (LSC), ¹⁸O and ²H were analyzed by isotope ratio mass spectrometry (IRMS). pH_stat tests were performed at four different pH values between 2 and 5. Results  Total Zn contents of the soil samples averaged 10 g kg⁻¹, Pb contents averaged 2.5 g kg⁻¹, Fe 22 g kg⁻¹, S 8.0 g kg⁻¹, and total carbon 4.0 g kg⁻¹. Below 2-m depth, soil samples had neutral pH values. Toward the surface, pH decreased down to pH 5.4 in P1 and P3, and to pH 5.9 in core P2, respectively. Dissolved contents of major ions (Mg, Ca, K, SO₄, and HCO₃) in the soil solution increased with depth. Metal concentrations (Fe, Mn, Zn) decreased with depth. The solution pH was neutral to slightly alkaline in samples below 2 m and slightly acidic (pH 6) at 1 m depth. Tritium values are around 7 TU and correspond to modern rain, i.e., after 1975. Stable isotope values plot on the global meteoric water line. The pH_stat tests provide two kinds of information, the acid neutralization capacity after 24 h (ANC24) and the release of metals depending on pH. The ANC24 increases linearly with decreasing pH from about 60 mmol(eq) kg⁻¹ at pH 5 to about 460 mmol(eq) kg⁻¹ at pH 2. Zn and Fe release show a strong increase with decreasing pH to 126 and 142 mmol(eq) kg⁻¹, respectively. Pb release increases at pH <4 and Mn release at pH <5, both to about 10 mmol(eq) kg⁻¹. Discussion  With an average of 10 g kg⁻¹, this field site is highly enriched in Zn. In the oxidized topsoil, Zn concentrations are significantly lower than in the anoxic subsoil. The distribution pattern of total Zn contents and soil pH values indicate that the topsoil, which is prone to oxidation and acidification, is already depleted in Zn. Only in soil core P2, Zn (and Fe) contents in the topsoil were higher than in the subsoil. Oxidation of the sulfidic material leads to redistribution into mobilizable species. High soil water concentrations (10 to 15 mg L⁻¹) can be found at acidic pH. The dominant Zn species in the soil solution is Zn²⁺. At neutral pH, Zn concentrations are below 0.001 mg L⁻¹. During the soil passage, the contaminated seepage water enters the anoxic subsoil with pH buffering carbonates. Results indicate that Zn is immobilized there. However, when the acid neutralization capacity is exhausted, a breakthrough of dissolved Zn to the groundwater has to be expected. Lead averages 2.5 g kg⁻¹ inside the flotation dump. In contrast to Zn, the first centimeters of the oxidized topsoil with high TOC contents show higher Pb contents than the anoxic subsoil. About 80% of the cation exchange capacity in the topsoil is occupied by Pb. In contrast to Zn, Pb is not abundant as aqueous species at slightly acidic pH. Values lower than pH 4 are necessary to mobilize Pb in higher amounts, as pH_stat experiments confirm. Hence, Pb is not expected to be leached out until the buffer capacity of the soil is exhausted. Conclusions  The environmental fate and behavior of Zn and Pb in the flotation dump is strongly depending on pH and redox conditions. Oxidation of sphalerite leads to a transfer of Zn from immobile to easily mobilizable species. Sulfide oxidation leads to an acidification of the topsoil where the buffer capacity is already exhausted due to the leaching of carbonates. At acidic pH, Zn is transferred to the aqueous phase and leached to the subsoil where soil pH is neutral. Electron supply and the buffer capacity of the material are found to be the main factors controlling the mobility of Zn. In contrast, the transfer of comparable amounts of Pb to the aqueous phase requires pH values <4. Since Pb is enriched in the topsoil, not leaching to the groundwater, but direct uptake (e.g., children, animals) and uptake by plants is the highest environmental risk. If the acidification of the soil proceeds with the same rate as in the last 40 years, it will reach the bottom of the tailing in about 200 years and a breakthrough of metals to the groundwater has to be expected. Recommendations and perspectives  The behavior of the different metals and their environmental impact depends on the different metal properties as well as on external conditions, e.g. pH, redox conditions, buffer capacity, and groundwater recharge. To assess the future release of metals from a flotation dump it is crucial to determine the main processes leading to acidification, the buffer capacity, and heavy metal binding forms. The release of heavy metals to the groundwater could be prevented by liming or other buffering techniques de Andrade et al. (J Soils Sediments 8:123–129, 2008). Electronic supplementary material  The online version of this article (doi:) contains supplementary material, which is available to authorized users.     

Growth,P uptake in grain legumes and changes in rhizosphere soil P pools

In soils with low P availability, several legumes have been shown to mobilise less labile P pools and a greater capacity to take up P than cereals. But there is little information about the size of various soil P pools in the rhizosphere of legumes in soil fertilised with P although P fertiliser is often added to legumes to improve N₂ fixation. The aim of this study was to compare the growth, P uptake and the changes in rhizosphere soil P pools in five grain legumes in a soil with added P. Nodulated chickpea (Cicer arietinum L.), faba bean (Vicia faba L.), white lupin (Lupinus albus L.), yellow lupin (Lupinus luteus L.) and narrow-leafed lupin (Lupinus angustifolius L.) were grown in a loamy sand soil low in available P to which 80 mg P kg⁻¹ was added and harvested at flowering and maturity. At maturity, growth and P uptake decreased in the following order: faba bean > chickpea > narrow-leafed lupin > yellow lupin > white lupin. Compared to the unplanted soil, the depletion of labile P pools (resin P and NaHCO₃-P inorganic) was greatest in the rhizosphere of faba bean (54% and 39%). Of the less labile P pools, NaOH-P inorganic was depleted in the rhizosphere of faba bean while NaOH-P organic and residual P were most strongly depleted in the rhizosphere of white lupin. The results suggest that even in the presence of labile P, less labile P pools may be depleted in the rhizosphere of some legumes.     

Fixation and defixation of ammonium in soils: a review

Fixed NH₄⁺ (NH₄⁺ _f) and fixation and defixation of NH₄⁺ in soils have been the subject of a number of investigations with conflicting results. The results vary because of differences in methodology, soil type, mineralogical composition, and agro-climatic conditions. Most investigators have determined NH₄⁺ _f using strong oxidizing agents (KOBr or KOH) to remove organic N and the remaining NH₄⁺ _f does not necessarily reflect the fraction that is truly available to plants. The content of native NH₄⁺ _f in different soils is related to parent material, texture, clay content, clay mineral composition, potassium status of the soil and K saturation of the interlayers of 2:1 clay minerals, and moisture conditions. Evaluation of the literature shows that the NH₄⁺ _f-N content amounts to 10–90 mg kg⁻¹ in coarse-textured soils (e.g., diluvial sand, red sandstone, granite), 60–270 mg kg⁻¹ in medium-textured soils (loess, marsh, alluvial sediment, basalt) and 90–460 mg kg⁻¹ in fine-textured soils (limestone, clay stone). Variable results on plant availability of NH₄⁺ _f are mainly due to the fact that some investigators distinguished between native and recently fixed NH₄⁺ while others did not. Recently fixed NH₄⁺ is available to plants to a greater degree than the native NH₄⁺ _f, and soil microflora play an important role in the defixation process. The temporal changes in the content of recently fixed NH₄⁺ suggest that it is actively involved in N dynamics during a crop growth season. The amounts of NH₄⁺ defixed during a growing season varied greatly within the groups of silty (20–200 kg NH₄⁺-N ha⁻¹ 30 cm⁻¹) as well as clayey (40–188 kg NH₄⁺-N ha⁻¹ 30 cm⁻¹) soils. The pool of recently fixed NH₄⁺ may therefore be considered in fertilizer management programs for increasing N use efficiency and reducing N losses from soils.