Effect of wheat (Triticum aestivum L.) rhizosphere and sewage sludge application on zinc desorption with dilute citric acid

Rhizosphere processes have a major impact on Zn desorption and Zn uptake by plant. However, information about Zn desorption characteristics in the rhizosphere of wheat is limited. Therefore, a greenhouse experiment was performed to determine Zn desorption characteristics in the bulk and rhizosphere soil of wheat (Triticum aestivum L.) of 10 soils amended and un-amended with municipal sewage sludge using rhizoboxes. The kinetics of Zn desorption was determined by successive extraction with 10 mM citric acid in a period of 1–504 h at 25 ± 1°C in the bulk and rhizosphere of un-amended and amended soils. The results showed that the Zn amount extracted after 504 h in the rhizosphere soils was significantly (p < 0.01) higher than the bulk soils. The mean of Zn desorption in the bulk and rhizosphere of un-amended soils were 10.4 ± 0.34 and 11.4 ± 0.43 mg kg^?1, respectively, while the mean of Zn desorption in the bulk and the rhizosphere of amended soils were 13.2 ± 0.48 and 14.8 ± 0.67 mg kg^?1, respectively. Desorption kinetics of Zn conformed fairly well to the first-order, parabolic diffusion, power function, and zero-order equations. The results of Zn fractionation indicated that exchangeable Zn and Zn associated with organic matter decreased and Zn associated with iron-manganese oxides and residual Zn increased in the rhizosphere soils compared to the bulk soils. Zinc desorption after 504 h and residual Zn in the bulk and rhizosphere of un-amended and amended soils were significantly positively correlated (p < 0.05). Therefore, residual Zn was the main Zn pool that controlled Zn desorption after 504 h in the bulk and rhizosphere soils studied.     

Rhizosphere effects on Cu availability and fractionation in sewage sludge‐amended calcareous soils

Rhizosphere processes have a major impact on copper (Cu) availability and its fractions in soils. A greenhouse experiment with wheat was performed to investigate availability (using seven chemical procedures) and fractionation of Cu in the rhizosphere of ten agricultural soils (Typic Calcixerepts) amended with sewage sludge (1% w/w) using rhizoboxes. The results show that available Cu concentrations in rhizosphere soils were significantly (P < 1%) lower than in bulk soils. In comparison with the bulk soils, in the rhizosphere soils the concentration of Cu associated with organic matter and residual Cu increased by 24 and 4%, respectively, whereas exchangeable Cu, Cu associated with iron‐manganese oxides, and Cu associated with carbonate decreased by 20, 14, and 12%, respectively. Dissolved organic carbon (DOC) and Cu associated with iron‐manganese oxides and Cu associated with organic matter in the rhizosphere and bulk soils were significantly correlated (P < 5%). The results show that the differences between rhizosphere and bulk soils in chemical conditions such as DOC concentrations can change the proportion of soil Cu fractions and, therefore, Cu availability for wheat in calcareous soils amended with sewage sludge. The results show that the wheat root‐induced modifications of chemical and biological soil conditions do not only lead to Cu depletion in mobile soil Cu fractions, but also to modification in soil Cu fractions which are commonly considered as more stable.     

Effect of Bean (Phaseolus vulgaris L.) Rhizosphere on Zinc-Release Kinetics

The primary factor that influences release of zinc (Zn) for plants is the rhizosphere. However, information about Zn-desorption characteristics in the rhizosphere is limited. A greenhouse experiment was performed to determine Zn-release characteristics in the bulk and the rhizosphere soils using a rhizobox. The kinetics of Zn release was determined by successive extraction with diethylenetriaminepentaacetic acid (DTPA)– triethanolamine (TEA) in a period of 1 to 504 h at 25 ± 1 °C in the bulk and the rhizosphere soils. Moreover, Zn extracted by using three extractants [DTPA-TEA, ammonium bicarbonate (AB)-DTPA, and Mehlich 3] in the bulk and the rhizosphere soils. The results showed that Zn extracted in the rhizosphere soils were significantly (P < 0.01) lower than the bulk soils. The mean of Zn release in the bulk and the rhizosphere soils were 5.31 and 4.91 mg kg^?1, respectively. Release kinetics of Zn conformed fairly well to power function, first order, parabolic diffusion, and simplified Elovich equations. The results of kinetics study indicated that release-rate coefficients decreased in the rhizosphere soils compare to the bulk soils. The correlation studies showed that Zn release after 504 h was significantly correlated (P < 0.05) with Zn extracted by using DTPA-TEA, AB-DTPA, and Mehlich 3 in the bulk and the rhizosphere soils. The results of this research showed that Zn-release characteristics in the bean rhizosphere soils were different from the bulk soils.     

The Effects of Cow Manure and Vermicompost on Availability and Desorption Characteristics of Zinc in a Loamy Calcareous Soil

The application of organic fertilizers in soils not only increases soil organic matter but also introduces essential nutrients to soil. Therefore, applying these fertilizers can affect the availability and desorption characteristics of nutrients. The main objective of this research is to study the effects of cow manure (CM) and vermicompost (VC) on availability and desorption characteristics of zinc (Zn) in a loamy calcareous soil. In this study, concentration of available Zn (using DTPA-TEA, AB-DTPA, and Mehlich 3) and desorption characteristics of Zn (using successive extraction with DTPA-TEA For 1–504 h at 25 ± 1°C) in amended soil with 0, 0.5, and 1% (w/w) of CM and VC were investigated in a completely randomized design. Results of this research showed that concentration of Zn extracted by using three methods was higher in amended soils with 1% CM and VC than those with 0.5% of these fertilizers. Furthermore, the difference between concentration of available Zn in amended soils with CM and VC was not found to be significant (p > 0.05). The results of kinetics study illustrated that the effect of organic fertilizers on Zn desorbed after 504 h was found to be significant (p < 0.01). Amount of cumulative of Zn desorbed in amended soils was significantly (p < 0.05) higher than unamended soil. Concentration of Zn desorbed after 504 h in 0.5 and 1% of CM and VC compared with unamended soil increased 26, 54, 12, and 46%, respectively. In addition, Zn desorption rate in amended soils with CM was higher than those with VC. It can be concluded that organic fertilizers applied to loamy calcareous soils enhance source of available Zn for the plant. Moreover, the results of this study showed that the ability of amended soils with VC to supplying Zn for plants was lower than those with CM.     

Prediction of available heavy metals by six chemical extractants in a sewage sludge‐amended soil

Abstract

In a field experiment conducted during three years in a sandy‐loam, calcareous soil, one aerobically digested sewage sludge (ASL) and another anaerobically digested sewage sludge (ANSL) were applied at rates of 400, 800, and 1,200 kg N/ha/year, and compared with mineral nitrogen fertilizer at rates of 0, 200, 400, and 600 kg N/ha/year in a cropping sequence of potato‐corn, potato‐lettuce, and potato, the first, second, and third year, respectively. Results showed that the highest values of soil extractable metals were obtained with aqua regia, whereas the lowest levels with DTPA. All metal (Zn, Cu, Cd, Ni, Pb, and Cr) gave significant correlations between metal extracted with the different extractants and metal loading applied with the sludges. The metal extractable ion increased over the control for Zn, Cu, Cd, Ni, Pb, and Cr extracted with DTPA, EDTA (pH 8.6) and 0.1 N HC1, for Zn, Cd, Ni, Pb, and Cr extracted with EDTA (pH 4.65) and AB‐DTPA, and for Zn, Cd, Ni, and Cr extracted with aqua regia. The level of metal‐DTPA extractable resulted highly correlated with that obtained by the other methods, except the Ni‐aqua regia extractable. The soil extractable elements which showed significant correlations with metals in plant were: Zn, Cu, Cd, and Ni in potato leaves, Cd, Ni, and Pb in corn grain, and Zn and Cd for lettuce wrapper leaves. In general, all the chelate based extractants (DTPA, EDTA pH 4.6, EDTA pH 8.6, AB‐DTPA) were equally useful as indicator of plant available metals in the soil amended with sludge.     

Ammonium bicarbonate‐DTPA extraction of elements from waste‐amended calcareous soil

Abstract

Use of soil testing for both nutrient and heavy metal interpretations could prove to be a readily available tool for management of calcareous soils amended with solid waste products. The ammonium bicarbonate‐DTPA (di‐ethylenetriaminepentaacetic acid) [AB‐DTPA] extradant was used in this study, based on its successful use in other calcareous regions, and existence of interpretations for both nutrients and selected heavy metals. In southern Florida, addition of large volumes of composted waste products to shallow agricultural soils formed from crushed Oolitic limestone appears to be a viable disposal alternative to rapidly expanding lanfills or incineration. For two years, the effects of processed wastes (PW) on selected, AB‐DTPA‐extractable soil mineral element concentrations were determined for tomato (Lycospresicon esculentum Mill.) and squash (Cucurbita maxima Duch. Ex Lam.) grown with three different irrigation rates (3.78, 2.53, or 1.25 L/min). The PW composts were added at supplier‐recommended rates for soil addition, resulting in a range of loading rates varying with source, with which the AB‐DTPA extradant could be evaluated. The PW composts were: i) Agrisoil Compost (processed municipal garbage and yard clippings) applied at 48 Mg/ha, ii) Daorganite (processed sewage sludge) applied at 16 Mg/ha, and iii) Eweson Compost (processed municipal garbage and sewage sludge) applied at 24 Mg/ha, and iv) no PW (control). There were no significant interactions between irrigation and PW treatment or effects of irrigation treatment on any of the soil‐extracted elements following either crop, with the exception of AB‐DTPA‐extractable copper (Cu) following squash in 1991. Treatment with Agrisoil resulted in the greatest increase in mineral element accumulation in the soil followed by Daorganite and Eweson sources for both crops during each year. Although there was variability among crops and years, mineral element concentrations, particularly manganese (Mn), lead (Pb), nickel (Ni), and Cu, were generally higher in the Agrisoil‐amended soil than in the other treatments. These observations could be traced to loading rates of individual elements. The lowest mineral element concentrations were in the non‐amended soil. The results of this study indicate that nutrients and selected heavy metals can be monitored successfully using the AB‐DTPA extractant. Accumulation of nutrients, including metals, in PW‐amended soil was minimal when supplied to the soil at manufacturers’ recommended rates, which were well below the U.S. Environmental Protection Agency's maximum loading rates.     

Comparison of four extractants and chemical fractions for assessing available zinc and copper in soils of India

Abstract

Relative suitability of different extraction procedures for estimating available zinc (Zn) and copper (Cu) in soils was assessed using DTPA, 0.1 N HCl, ammonium acetate+EDTA, and double acid (HCl+ H₂SO₄) as extractants and rice as a test crop in Neubauer experiment. The relationships between Zn concentration and uptake of Zn by rice plants and Zn extracted by the different methods showed that DTPA‐TEA, pH 7.3, could very suitably be used to assess Zn availability in soils. However, 0.1 N HCl was better for assessing the Cu availability in soils to the rice plants. Water‐soluble and exchangeable fractions of Zn and Cu had significant positive correlations with Zn and Cu concentrations, respectively obtained by all the four extractants tested. The results also showed that DTPA and ammonium acetate+EDTA extracted organically bound Zn, whereas DTPA, 0.1 N HCl and ammonium acetate+EDTA extracted organically bound Cu. Water‐soluble, exchangeable and organic matter bound fractions exhibited significant relationships with Zn and Cu concentrations, their uptake and rice dry matter yield.     

Kinetics of Copper Desorption from Highly Calcareous Soils

Abstract

Desorption of copper (Cu) is an important factor in determining Cu availability in calcareous soils. Kinetics of native and added Cu desorption by DTPA (diethylene‐triaminepentaacetic‐acid) from 15 highly calcareous soils of southern Iran were studied in a laboratory experiment. Our results showed that two constant‐rate, Elovich, simple Elovich, and parabolic‐diffusion equations were the best‐fitted equations among eight kinetic models used. The copper desorption pattern based on the parabolic‐diffusion equation revealed that the rate of native Cu desorption was higher in the first 2 h followed by a slower release rate, which suggests that two different mechanisms are involved. The trend may describe why the DTPA soil test has been considerably successful in predicting Cu availability in calcareous soils. Stepwise multiple regression equations indicated that CCE (calcium carbonate equivalent), CEC (cation exchange capacity), and clay content are the most important soil characteristics that predict the rate constants of the kinetic models. Mean extractant recovery percentage (ERP) of the soils was only 20%, which indicated that after 20 days, DTPA extracted only one‐fifth of added Cu. Regression equations indicated that as soil OM (organic matter) content increased, the value of ERP decreased. From results reported herein it seems that CCE, CEC, and clay are the most important factors controlling Cu release from highly calcareous soils of southern Iran. However, the initial soil Cu desorption rate is probably controlled by CEC.     

Characterizing phosphorus availability in waste products by chemical extractions and plant uptake

Background: The fertilizer value of phosphorus (P) in waste products relies heavily on its availability to the subsequent crop. Aim: We studied the link between extractable P in waste products and apparent P recovery (APR, i.e., difference in plant P uptake between P amended and un‐amended soils divided by the amount of P added) using spring barley grown on three sandy soils. Methods: The products included sewage sludge, biomass ash, struvite, compost, meat and bone meal, biochar from sewage sludge, and industrial sludge. Soft rock phosphate and triple‐superphosphate (TSP) were included for comparison. Availability of P was characterized by extraction with water and solutions of sodium bicarbonate, citric acid, oxalic acid, hydrochloric acid, ammonium acetate, ammonium fluoride and anion exchange resin membranes. TSP was used to establish mineral‐fertilizer‐equivalents (MFE). Water and bicarbonate extractions were also applied to products incubated with soil before extraction. Results: The APR ranged 26 to 31% for TSP and 0 to 30% for waste products. APR correlated most strongly with bicarbonate extractable P. The correlation increased when products were incubated with soil before extraction. Conclusions: We conclude that bicarbonate extraction is a good indicator of potential P availability. However, interactions between waste products and soil properties modify P availability.     

Extractability and plant uptake of heavy metals in alum shale soils

Abstract

Fifty soil samples (0–20 cm) with corresponding numbers of grain, potatoes, cabbage, and cauliflower crops were collected from soils developed on alum shale materials in Southeastern Norway to investigate the availability of [cadmium (Cd), copper (Cu), zinc (Zn), lead (Pb), nickel (Ni), and manganese (Mn)] in the soil and the uptake of the metals by these crops. Both total (aqua regia soluble) and extractable [ammonium nitrate (NH₄NO₃) and DTPA] concentrations of metals in the soils were studied. The total concentration of all the heavy metals in the soils were higher compared to other soils found in this region. Forty‐four percent of the soil samples had higher Cd concentration than the limit for application of sewage sludge, whereas the corresponding values for Ni, Cu, and Zn were 60%, 38%, and 16%, respectively. About 70% the soil samples had a too high concentration of one or more of the heavy metals in relation to the limit for application of sewage sludge. Cadmium was the most soluble of the heavy metals, implying that it is more bioavailable than the other non‐essential metals, Pb and Ni. The total (aqua regia soluble) concentrations of Cd, Cu, Zn, and Ni and the concentrations of DTPA‐extractable Cd and Ni were significantly higher in the loam soils than in the sandy loam soils. The amount of NH₄NCyextractable metals did not differ between the texture classes. The concentrations of DTPA‐extractable metals were positively and significantly correlated with the total concentrations of the same metals. Ammonium nitrate‐extractable metals, on the other hand, were not related to their total concentrations, but they were negatively and significantly correlated to soil pH. The average concentration of Cd (0.1 mg kg^‐1 d.w.) in the plants was relatively high compared to the concentration previously found in plants grown on the other soils. The concentrations of the other heavy metals Cu, Zn, Mn, Ni, and Pb in the plants were considered to be within the normal range, except for some samples with relatively high concentrations of Ni and Mn (0–11.1 and 3.5 to 167 mg kg‘¹ d.w., respectively). The concentrations of Cd, Cu, Zn, Ni, and Mn in grain were positively correlated to the concentrations of these respective metals in the soil extracted by NH₄NO₃. The plant concentrations were negatively correlated to pH. The DTPA‐extractable levels were not correlated with plant concentration and hence DTPA would not be a good extractant for determining plant availability in these soils.     

Zinc Release Characteristics from Calcareous Soils using Diethylenetriaminepentaacetic Acid and Other Organic Acids

Adsorption and desorption reactions of zinc (Zn) in soils control its availability to plants. In the present investigation, time-dependent Zn release was evaluated using three organic acids [diethylenetriaminepentaacetic acid (DTPA), citric acid, and maleic acid] to depict the Zn fraction controlling Zn release rate from slightly calcareous to calcareous soils. Eight surface and two subsoil samples of selected soil series varied in their physicochemical properties, amount of Zn held in different chemical pools, and Zn-retention capacities (21–61%). Each soil was extracted for a total period of 24 h at 1:10 soil/extractant suspension ratio using 0.005 M DTPA. The time-dependent parabolic diffusion model best described the Zn release in six consecutive extractions. Soils differed in cumulative Zn extracted (1.09–3.81 mg kg^?1 soil) and Zn release rate. Under similar conditions, three soils differing in Zn-retention capacities were also extracted with five different concentrations (0.01–0.0001 M) of citric and maleic acids. Although both maleic and citric acids released soil Zn at greater rates and in greater amounts than DTPA, maleic acid was more efficient. Soil Zn bound to amorphous iron (Fe) + manganese (Mn) oxides was the main Zn pool that controlled Zn release characteristics.     

Comparison of routine soil tests and EPA method 3050 as extractants for heavy metals in Delaware soils

Abstract

Agricultural use of sewage sludges can be limited by heavy metal accumulations in soils and crops. Information on background levels of total heavy metals in soils and changes in soil metal content due to sludge application are; therefore, critical aspects of long‐term sludge monitoring programs. As soil testing laboratories routinely, and rapidly, determine, in a wide variety of agricultural soils, the levels of some heavy metals and soil properties related to plant availability of these metals (e.g. Cu, Fe, Mn, Zn, pH, organic matter, texture), these labs could participate actively in the development and monitoring of environmentally sound sludge application programs. Consequently, the objective of this study was to compare three soil tests (Mehlich 1, Mehlich 3, and DTP A) and an USEPA approved method for measuring heavy metals in soils (EPA Method 3050), as extractants for Cd, Cu, Ni, Pb and Zn in representative agricultural soils of Delaware and in soils from five sites involved in a state‐monitored sludge application program.

Soil tests extracted less than 30% of total (EPA 3050) metals from most soils, with average percentages of total metal extracted (across all soils and metals) of 15%, 32%, and 11% for the Mehlich 1, Mehlich 3, and DTPA, respectively. Statistically significant correlations between total and soil test extractable metal content were obtained with all extractants for Cu, Pb, and Zn, but not Cd and Ni. The Mehlich 1 soil test was best correlated with total Cu and Zn (r=0.78***, 0.60***, respectively), while the chelate‐based extractants (DTPA and Mehlich 3) were better correlated with total Pb (r=0.85***, 0.63***). Multiple regression equations for the prediction of total Cu, Ni, Pb, and Zn, from soil test extractable metal in combination with easily measured soil properties (pH, organic matter by loss on ignition, soil volume weight) had R² values ranging from 0.41*** to 0.85***, suggesting that it may be possible to monitor, with reasonable success, heavy metal accumulations in soils using the results of a routine soil test.     

An evaluation of chemical methods for extracting copper from rice soils

Abstract

Rice (Oryza sativaL. CV. Lemont) was grown on 19 soils, and eight extractants were evaluated for determining the availability of Cu to rice plants. Correlation analyses were employed as criteria for evaluating methods that would provide the best index of Cu availability. The order of removal of Cu from soils was: 0.5NHC1 + 0.05NA1C1₃> 0.5NHNO₃> 0.5 N HC1 > EDTA + NH₄OAc > 0.1NHC1 > EDTA + (NH₄)₂CO₃? DTPA‐TEA, pH 7.3 >>> 1 N NH₄0Ac, pH 4.8.

Uptake of Cu by rice plants was significantly correlated with soil Cu. Among the eight extractants evaluated, Cu extracted with DTPA‐TEA, pH 7.3 was better related to the concentration (r = 0.563 ) and uptake (r = 0.673 ) of Cu by rice plants grown on the soils with different chemical and physical properties.

A significant negative correlation was found between the concentration of Cu in rice plants and the organic matter content of the soils. Each one percent increase in the organic matter of the soils resulted in a corresponding decrease of approximately one mg/kg in the concentration of Cu in the rice‐plant tissue. Multiple regressions of extractable Cu by eight methods with soil organic matter content accounted for from 53.4 to 70.0% of the variations in the prediction of the concentration of Cu in the rice plants. Combinations of other soil chemical properties measured with extractable Cu did not significantly improve the predictability     

Effect of sewage sludge application on cotton yield and contamination of soils and plant leaves

Abstract

In a two‐year field experiment, dry sewage sludge was applied to fields plots at rates of 0,26,42,58, or 77 tons ha^‐1 year^‐1 on a clay loam soil (calcixerrolic xerochrept), well drained with a pH value of 8.15. Cotton was the cultivated plant (Gossypiumhirsutum variety korina). Sequential extraction was used to separate the different forms of the metals (exchangeable, organically bound, carbonates and residual) in the soil‐sludge mixtures. Cotton yield increased in the second year of experimentation compared with the control treatment (without fertilization and no application of sewage sludge). Most of the metals studied [cadmium (Cd), zinc (Zn), copper (Cu), and nickel (Ni)] were found in the organically bound, carbonate or residual forms. From the elements in the soil fractions, only Zn in the residual form was correlated with the Zn content of cotton leaves. The diethylenetriaminepentaacetic acid (DTPA) extraction of the plant‐available levels of the elements showed only for Cd a simple linear correlation, between concentration in soils and cotton leaves.     

Zinc,copper, and nickel availabilities as determined by soil solution and DTPA extraction of a sludge‐amended soil

Abstract

Extracting sludge‐amended soil with DTPA does not always give a reliable measure of plant‐available heavy metals. The major purpose of this greenhouse pot study was to help explain why. Two anaerobically digested sludges from sewages treated with either Ca(OH)₂or FeCl₃were applied to 3‐kg samples of a Mollic Albaqualf previously limed with Ca(OH)₂rates of 0, 2.5, and 10g/pot that resulted in pHs in the check pots of 5.4, 6.2, or 7.7 after the first harvest. Sludge rates provided 0, 200, 40, 800, and 1600 mg Zn kg^‐1of soil. Two consecutive crops of soybeans (Glycine MaxL.) were grown for 42 d each in the greenhouse. DTPA‐extractable, soil‐solution, and plant concentrations of Cu²⁺, Ni²⁺, and Zn²⁺were measured.

Dry matter yields were depressed due to salt toxicity, while DTPA‐extracted Cu²⁺correlated with plant uptake of Cu²⁺for both sludges. DTPA‐extracted Ni²⁺also correlated with plant Ni²⁺from the Ca(OH)₂‐sludge‐amended soil, although DTPA‐extracted Ni²⁺did not correlate with plant uptake of Ni²⁺from the FeCl₃‐sludge‐amended soil, DTPA‐extracted Zn did not correlate with plant uptake of Zn²⁺from any sludge‐amended soil. Soil‐solution composition correlated with plant uptake of Cu²⁺and Ni²⁺in both sludges; it also correlated with plant uptake of Zn²⁺from FeCl₃‐sludge‐amended soil but not from Ca(OH)₂‐sludge‐amended soil. DTPA extraction probably failed with Ni²⁺and Zn²⁺because of (i) its ineffectiveness at low pH, (ii) the inability of DTPA to buffer each soil extract near pH 7.3, and (iii) increased amounts of soluble chelated micronutrients at higher sludge rates and higher soil pHs. Soil‐solution composition seemed to fail only where micronutrient cations in solution probably were present largely as organic chelates     

Soil Test to Predict the Copper Availability in Pasture Soils

Abstract

The proportion of copper (Cu) that can be extracted by soil test extractants varied with the soil matrix. The plant‐available forms of Cu and the efficiency of various soil test extractants [(0.01 M Ca(NO₃)₂, 0.1 M NaNO₃, 0.01 M CaCl₂, 1.0 M NH₄NO₃, 0.1 M HCl, 0.02 M SrCl₂, Mehlich‐1 (M1), Mehlich‐3 (M3), and TEA‐DTPA.)] to predict the availability of Cu for two contrasting pasture soils were treated with two sources of Cu fertilizers (CuSO₄ and CuO). The efficiency of various chemical reagents in extracting the Cu from the soil followed this order: TEA‐DTPA>Mehlich‐3>Mehlich‐1>0.02 M SrCl₂>0.1 M HCl>1.0 M NH₄NO₃>0.01 M CaCl₂>0.1 M NaNO₃>0.01 M Ca(NO₃)₂. The ratios of exchangeable: organic: oxide bound: residual forms of Cu in M1, M3, and TEA‐DTPA for the Manawatu soil are 1:20:25:4, 1:14:8:2, and 1:56:35:8, respectively, and for the Ngamoka soil are 1:14:6:4, 1:9:5:2, and 1:55:26:17, respectively. The ratios of different forms of Cu suggest that the Cu is residing mainly in the organic form, and it decreases in the order: organic>oxide>residual>exchangeable. There was a highly significant relationship between the concentrations of Cu extracted by the three soil test extractants. The determination of the coefficients obtained from the regression relationship between the amounts of Cu extracted by M1, M3, and TEA‐DTPA reagents suggests that the behavior of extractants was similar. But M3 demonstrated a greater increase of Cu from the exchangeable form and organic complexes due to the dual activity of EDTA and acids for the different fractions and is best suited for predicting the available Cu in pasture soils.     

Initial results from long-term field studies at three sites on the effects of heavy metal-amended liquid sludges on soil microbial activity

In a long‐term study of the effects on soil fertility and microbial activity of heavy metals contained in sewage sludges, metal‐amended liquid sludges each with elevated Zn, Cu or Cd concentrations were applied over a 3‐year period (1995–1997) to three sites in England. The experiments were sited adjacent to experimental plots receiving metal‐rich sludge cakes enabling comparisons to be made between the effects of heavy metal additions in metal‐amended liquid sludges and sludge cakes. The liquid sludge additions were regarded as ‘worst case’ treatments in terms of likely metal availability, akin to a long‐term situation following sewage sludge additions where organic matter levels had declined and stabilised. The aim was to establish individual Zn (50–425 mg kg^?1), Cu (15–195 mg kg^?1) and Cd (0.3–4.0 mg kg^?1) metal dose–response treatments at each site, but with significantly smaller levels of organic matter addition than the corresponding sludge cake experiments. There were no differences (P > 0.05) in soil respiration rates, biomass carbon concentrations or most probable numbers of clover Rhizobium between the treatments at any of the sites at the end of the liquid sludge application programme. Soil heavy metal extractability differed between the metal‐amended liquid sludge and metal‐rich sludge cake treatments; Zn and Cd extractabilities were higher from the liquid sludge additions, whereas Cu extractability was higher from the sludge cake application. These differences in metal extractability in the treated soil samples reflected the contrasting NH₄NO₃ extractable metal contents of the metal‐amended liquid sludges and sludge cakes that were originally applied.     

Assessment of Heavy Metals in Spinach (Spinacia oleracea L.) Grown in Sewage Sludge–Amended Soil

The assessment of heavy metals in spinach (Spinacia oleracea) grown in sewage sludge–amended soil was investigated. The results revealed that sewage sludge significantly (P < 0.01) increased the nutrients and heavy metals such as cadmium (Cd), chromium (Cr), copper (Cu), manganese (Mn), and zinc (Zn) in the soil. The contents of metals were found to be below the maximum levels permitted for soils in India. The most agronomic performance and biochemical components of S. oleracea were found at 50% concentrations of sewage sludge in both seasons. The contents of Cd, Cr, Cu, Mn, and Zn in S. oleracea were increased from 5% to 100% concentrations of sewage sludge in both seasons. The order of contamination factor (Cf) of different heavy metals was Mn > Cd > Cr > Zn > Cu for soil and Cr > Cd > Mn > Zn > Cu for S. oleracea plants after application of sewage sludge. Therefore, use of sewage sludge increased concentrations of heavy metals in soil and S. oleracea.     

Initial results from a long-term, multi-site field study of the effects on soil fertility and microbial activity of sludge cakes containing heavy metals

In a long‐term study of the effects on soil fertility and microbial activity of heavy metals contained in sewage sludges, metal‐rich sludge cakes each with high Zn, Cu or Cd concentrations were applied annually for 4 years (1994–1997) to nine sites throughout Britain. These sites were selected to represent agricultural soils with a range of physical and chemical properties, typical of those likely to be amended with sewage sludge. The aim was to establish individual total Zn (approx. 60–450 mg kg^?1), total Cu (approx. 15–200 mg kg^?1) and total Cd (approx. 0.2–4 mg kg^?1) metal dose–response treatments at each site. Sludges with low metal concentrations were added to all treatments to achieve as constant an addition of organic matter as possible. Across the nine sites, soil pH was the single most important factor controlling Zn (P < 0.001; r² = 92%) and Cd extracted with 1 m NH₄NO₃ (P < 0.001; r² = 72%), and total iron content the most important factor controlling Cu extracted with 1 m NH₄NO₃ (P < 0.001; r² = 64%). There were also positive relationships (P < 0.001) between soil organic carbon (C) concentrations and soil biomass C and respiration rates across the nine sites. Oxidation of sludge C following land application resulted in approximately 45% of the digested sludge cake C and approximately 64% of the ‘raw’ sludge cake C being lost by the end of the 4‐year application period. The sludge cake applications generally increased soil microbial biomass C and soil respiration rates, whilst most probable numbers of clover Rhizobium were generally unchanged. Overall, there was no evidence that the metal applications were damaging soil microbial activity in the short term after the cessation of sludge cake addition.     

Metal accumulation by bermudagrass grown on four diverse soils amended with secondarily treated sewage effluent

Land treatment is increasingly being utilized as a method of waste disposal for both sewage effluent and sludges. While there has been considerable attention directed toward the fate of metallic constituents of sewage sludges, there have been fewer studies of the fate and mobility of metals appled to soils in sewage effluent. This study was undertaken utilizing secondarily treated sewage effluent amended to contain less than 1 mg l^?1 each of Cd, Cu, Ni, Pb, and Zn. The effluent was applied weekly for a period of 1 yr on large undisturbed monoliths of four diverse soils enclosed in lysimeters and sprigged to common bermudagrass (Cynodon dactylon L.). Soil samples were collected periodically and extracted with DTPA to measure plant available metals. Vegetation was harvested, weighed, subsampled and analyzed for total metal content. Total plant uptake of Cd, Cu, Pb, and Ni during the year was less than 1% of that applied. Vegetative uptake of Zn was as high as 2%. Metal uptake was greatest in the soil with the lowest initial pH. Heavy metal concentrations in plant tissue exhibited a cyclic trend. A similar increasing cyclic trend was evident in the DTPA extractable metals in the surface 0 to 12.5 cm of the treated soils. Decreases in plant and DTPA extractable metals occurred when the soils dried, allowing O₂ to enter. Vegetative concentrations of Cd, Cu, and Ni exceeded normal ranges of 0.2 to 0.8, 4 to 15, and 1.0 mg kg^?1, respectively, for vegetation while Pb and Zn were near normal. Only Cd concentration of vegetation posed a threat to grazing animals.