Fractionation of residual cadmium,copper, nickel,lead, and zinc in previously sludge‐amended soil

Abstract

The fractionation of heavy metals in previously sludge‐amended soil is important to evaluate their behavior in the environment in terms of mobility and availability to crop plants. A surface soil that received two types of sludges at two different rates, plus fertilizer only and no treatment (control), having been fallow for nine years, was used in this study. The contents of cadmium (Cd), copper (Cu), nickel (Ni), lead (Pb), and zinc (Zn) fractions in previously sludge‐amended soils were governed by the total content of these metals in the sludges applied and by the rate of sludge application. The contents of these metals were higher for soils that received the Chicago sludge as compared to that receiving the Huntsville sludge. Furthermore, soils that received 20 Mg/ha/yr of sludge for five years generally had higher levels of these metals than those receiving a single dose at the 100 Mg/ha application rate. The percentage of the total content in the water soluble and exchangeable forms was very low (≤1%) regardless of sludge application. The application of sludges tended to reduce the residual fraction and to increase the organic and carbonate fractions. Overall, the predominant forms of the metals in the sludges were as the Cd‐, Ni‐, Pb‐, and Zn‐carbonate and Cu‐organic fractions.     

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.     

Availability of cobalt‐60 to corn and bean seedlings as influenced by soil type,lime, and DTPA

Abstract

Uptake of Co by corn (Zea mays) and bush beans (Phaseolus vulgaris) seedlings was affected by plant species, soil type and soil amendment. Bean leaves preferentially accumulated ⁶⁰Co in comparison with corn leaves. Both the DTPA and (lime and DTPA) treatments enhanced ⁶⁰Co uptake by both plant species, notably in the Troup soil which had lower cation exchange capacity (CEC) and lower soil fertility in comparison with Dothan soil. Conversely, soils with lime but without the chelating agent suppressed ⁶⁰Co uptake. This dictates that farming practices should be closely evaluated if crops for livestock and human consumption are to be raised in fields contaminated by radionuclides.     

Critical soil phosphorus of a low‐P loess‐derived soil as affected by storage temperature

Abstract

Overwintering soil temperature may influence crop response to phosphorus (P) and indices of P availability in the humid, temperate, transitional climate of Tennessee. The effects of P fertilization and soil incubation temperature on sorghumsudangrass (Sorghum bicolor x S. Sudanese) grown on a Typic Hapludalf was investigated in a greenhouse study. In order to determine the effect of temperature on P availability, soils were incubated prior to cropping, at a constant temperature of 6°C or an average diurnal temperature of 24 and 36°C. Reagent grade Ca(H₂PO₄)₂.H₂O was used as the fertilizer source and applied at rates of 0, 10, 20, and 30 mg P kg^‐1 for the first test and 0, 20, 40, 60, and 80 mg P kg_‐ ¹ for the second test. Critical P concentration in the shoots for optimum yield was found to be 1.3 mg g‐¹, corresponding to soil solution and labile P concentrations of 5.5 μmol L^‐1 and 167 μg g^‐1, respectively. Optimum yield occurred for applications of >65 mg P kg^‐1 and was unaffected by soil incubation temperature. Applied P rates affected extractable P by five chemical extractants (Bray I, Bray II, Mehlich I, Mehlich III, and Mississippi), but soil incubation temperature had no affect. The extractants, however, were poorly correlated to plant P uptake and no one extractant appeared preferable to the others as an indicator of P availability.     

Distribution of Total and DTPA‐Extractable Zinc,Copper, Manganese,and Iron in Vertisols of India

Abstract

Vertisols of India are developed over isohyets of 600 to 1500 mm, and their chemical cycles are set by drainage, landforms, and particle size, which results in variable pedogenic development within the otherwise homogeneous soils. The purpose of this study was to identify pedogenic processes in the distribution of total and DTPA‐extractable zinc (Zn), copper (Cu), manganese (Mn), and iron (Fe). The soils are developed over basaltic parent material of Cretaceous age. Soil samples were drawn from genetic horizons of the 13 benchmark profiles and analyzed by using HF–HClO₄ acid for total and DTPA extraction. Correlation coefficients were calculated taking all samples together. The total concentration varied from 24 to 102 mg kg^?1 for Zn, 21 to 148 mg kg^?1 for Cu, 387 to 1396 mg kg^?1 for Mn, and 2.36 to 9.50% for Fe. Their variability was proisotropic and haplodized, and their concentrations increased with advancing isohyets. Within the isohyets, hindrance in drainage caused retention of Zn and Cu but loss of Fe. The piedmont soils had more Fe than alluvium soils. The spatial distribution of total contents of Zn, Cu, and Fe was influenced by the pedogenic processes associated with Haplusterts but not with provenance materials. Surface concentrations of the elements by biotic lifting and/or harvest removal were negated by the pedoturbation that further contributed to the irregular distribution of the elements in the profiles. Total Zn and total Cu had positive coefficients of correlations with coarse clay, whereas total Mn and total Fe were positively correlated with fine clay. The DTPA‐extractable forms were functions of isohyets and drainage and showed association with organic carbon content and coarse clay.     

Effects of extraction period and soil.‐solution ratio on the amount of zinc extracted from soils by different extractants

Abstract

Investigations have examined the effects of extraction period and soil:solution ratio on the extraction of zinc from some New Zealand soils by EDTA, DTPA, HCl, Ca(NO₃)₂ and CH₃COONH₄. A high proportion of the zinc extracted by EDTA, DTPA, HCl, and Ca(NO₃)₂ was extracted rapidly, within the first 0.5 h, followed by small increases over the next 15 h. An exception occurred with a soil containing iron/manganese concretionary material. In this soil, with both EDTA and DTPA, there were significant increases in the amount of zinc extracted between 1 and 8 h. The amounts of zinc extracted by CH₃COONH₄ increased gradually with the time of extraction up to approximately 4 h.

Substantial increases in the amounts of zinc extracted with HCl, Ca(NO₃)₂ and CH₃COONH₄ were obtained by increasing the soil:solution ratio from 1:2.5 to 1:10. However, soil:solution ratio has little effect on the amounts of zinc extracted by EDTA or DTPA.     

Changes in organic matter and enzymatic activity of an agricultural soil amended with metal‐contaminated sewage sludge compost

Abstract

The effect of organic amendment with sewage sludge composts of varying heavy metal content on the organic matter content and enzymatic activity of an agricultural soil supporting barley (Hordeum vulgare L.) or lettuce (Lactuca sativa L.) crops was studied. The organic amendments did not improved lettuce growth, the contaminated composts having a negative effect on yield. However, all organic amendments improved barley straw yields although they did not affect grain yields. The addition of the organic materials increased the total carbohydrate content of the soil although this content decreased with cultivation. There was a clearly observed effect of crop type and the degree of heavy metal contamination of the amendment on the most labile carbon (C) fractions (water‐soluble C, carbohydrates, and polyphenolics). In general, soil enzymatic activities were stimulated by addition of sewage sludge compost with low heavy metal content. The compost containing high level of cadmium (Cd), copper (Cu), nickel (Ni), and zinc (Zn) inhibited protease‐BAA activity with respect to the other composts. After cultivation, urease activity increased in soil amended with the high dose of composts, regardless their degree of metallic contamination. Both crop type and metallic contamination contained in the organic materials added influenced phosphatase and ß‐glucosidase activity.     

Distribution of DTPA‐extractable Fe,Zn, and cu in soil particle‐size fractions

Abstract

To examine the distribution of DTPA‐extractable Fe, Zn, and Cu in clay, silt, and sand fractions; surface soils were collected from cultivated fields of North Dakota, South Dakota, West Virginia, Iowa, Ohio, and Illinois. Clay, silt, and sand fractions were separated after sonic dispersion of soil water suspension and analyzed for DTPA‐extractable Fe, Zn, and Cu. In general, clay had the highest and sand the lowest amount of DTPA‐extractable metals. Consequently, clay had the highest and sand the lowest intensity and capacity factors for these metals since DTPA micronutrient test measures both these factors.     

Effect of cultivated plants on physico‐chemical characteristics of humic substances of soils amended by sewage sludge

Abstract

Humic substances were extracted from raw sewage sludge samples as well as an alluvial slightly alkaline soil [Typic Xerofluvent (So)], a clay loam soil [Calcixerollic Xerochrept (M)] and the corresponding field plots amended with different rates of sewage sludge and cultivated with corn and cotton respectively, in a two‐year field experiment. These substances have been characterized by chemical and spectroscopic methods. The chemical analyses showed that humic acids (HAs) and fulvic acids (FAs), were effected by the cultivated plant. Humic substances extracted from field plots with cotton showed higher carbon, but less nitrogen (N), total acidity and carboxylic groups content, as compared with those under corn. Generally HAs and FAs extracted from the fields plots amended with sewage sludge had higher N content, lower values of total acidity, carboxylic groups and carbon contents than those from the unamended soils. The FT‐IR spectra of humic (HAs) and fulvic (FAs) acids extracted from sewage sludge indicated the presence of high percentage of aliphatic carbon, polysaccharides and proteinaceous materials. The spectra of the humic matter in the field plots showed less aliphatic but increased amide stretch in comparison with the sludge. The absorption due to C=O in carboxylic groups of the FAs was not pronounced, though the presence of polysaccharides and protein decomposition products was clearly indicated.     

Residual effects of sewage‐sludge application on plant and soil‐profile chemical composition

Abstract

Long‐term effects on plant and soil‐profile chemical composition imposed by a residential sewage sludge were studied on an Oxisol from Hawaii. Sludge was applied at 0, 45, 90, and 180 Mg/ha in 1983. An NPK‐fertilized treatment was included for comparison. Sudangrass (Sorghum bicolorL. Moench) was grown as a test crop in the 1983–84 and 1986–87 seasons. Soil samples for chemical analysis were taken in 1987 at three depths: 0–23 cm, 23–46 cm, and 46–69 cm.

Beneficial effects of sludge, measured 3 years after application (beginning of the 1986's planting), were evident by large yield increases on sludge‐amended soils relative to the unamended and the NPK‐fertilized soils. The first cutting produced approximately 5 Mg/ha of dry matter from the sludge treatments, regardless of rate, as compared with 3 and 1.5 Mg/ha from the NPK and the 0 treatments. Regrowths showed similar effect, though less dramatic; average yields were 2.6 Mg/ha with sludge and 1.6 Mg/ha without.

Heavy‐metal concentrations in plants were generally unaffected by sludge applications; probably because (i) heavy‐metal contents of the sludge were low, and (ii) soil pH was increased by sludge.

Remarkable increases in pH, exchangeable Ca and extractable P, and resultant decreases in exchangeable Al, in all three soil layers of sludge‐amended soils suggest that surface application of a low heavy‐metal sludge could serve to correct subsoil acidity and enhance subsoil P availability.     

Temporal and spatial distributions of nitrate‐nitrogen in two furrow‐irrigated semiarid soils amended for sludge and fertilizer

Abstract

A statistical comparison of data collected from two cotton production fields with a history of either commercial fertilizer or sludge amendments showed significantly different nitrate‐nitrogen (N) concentrations in time and space. The sludge‐amended field had high nitrate concentrations in the root zone (1.5 m) throughout the season. Whereas, the fertilized field showed low nitrate‐N concentrations during the same period. Both fields showed significant increases in nitrate‐N following pre‐plant irrigation events, and significant decreases of nitrate‐N in the root zone during the growing season. Following harvest, the sludge‐amended field had very large reserve of nitrate‐N in the profile. The spatial variabilities, as determined by the % coefficients of variations (CVs) of eight cores per sampling event, of nitrate‐N distributions where large in both fields, 69% and 90% for the sludge and fertilizer field, respectively. The estimated nitrate‐N leaching losses were much higher in the sludge‐amended than the fertilized field. Significant leaching losses in the sludge‐amended field were likely the result of year‐to‐year sludge residue accumulations that mineralize and release nitrate‐N in the zone of incorporation (0–30 cm).     

Association of cadmium,zinc, copper,and nickel with components in naturally heavy metal‐rich soils studied by parallel and sequential extractions

Abstract

In this study, a new parallel and sequential extraction procedure was proposed to investigate the solubility of metals [cadmium (Cd), zinc (Zn), copper (Cu), and nickel (Ni)] and their association with soil components in naturally metal‐rich soils of Norway. Two different soils, alum shale (clay loam) and moraine (loam), developed on alum shale minerals were used. Each soil had two pH levels. For parallel and successive extractions, H₂O, 0.1M NH₄OAc (soil pH), 0.3M NH₄OAc (soil pH), 1M NH₄OAc (soil pH), and 1M NH₄OAc (pH 5.0) were used. A significant amount of Cd was extracted by NH₄O Ac related to concentration of NH₄OAc in the extracting solution. The amounts of Zn, Cu, and Ni extracted by these reagents were almost negligible except with 1M NH₄OAc (pH 5.0). Thus these metals were strongly bound to soil components. A seven step sequential extraction procedure was applied to evaluate the association of metals with soil constituents. The extractions were performed sequentially by extracting the soil with reagents having an increasing dissolution strength: 1M NH₄OAc (soil pH), 1M NH₄OAc (pH 5.0), 1M NH₂OH.HCl (in 25% HOAc), 1M NH₂OH.HCl (in 0.1M HNO₃), 30% H₂O₂ (in 0.1M HNO₃), 30% H₂O₂ (1M HNO₃), and aqua regia. In both soils at both pH levels investigated, appreciable percentages of total Cd (20–50%) were found associated with the NH₄OAc extractable fraction (mobile fraction). For Zn, Cu, and Ni, the percentage of total metal extracted with NH₄OAc was low (<4%), but it increased significantly by introducing a reducing agent (NH₂OH.HCl). The NH₂OH.HCl‐extractable fraction was the greatest fraction (>60%) for all four metals examined. These results suggest that among the metals studied, only Cd was easily desorbed from soil and should be considered mobile and potentially bioavailable. Other metals (Zn, Cu, and Ni) were strongly associated with the soil components and should be considered less available to plants. Using the sequential fractionation technique as a measure of availability, mobility and potential bioavailability of these four metals in the alum shale soils were: Cd>Zn>Ni>Cu.     

A preliminary comparison of the ammonium acetate‐edta soil phosphorus extraction method to the bray‐1 and olsen soil phosphorus extraction methods

Abstract

The ammonium acetate (NH₄OAc)‐EDTA soil phosphorus (P) extraction method was compared to either the Bray‐1 soil P extraction method for non‐calcareous soils or the Olsen soil P extraction method for calcareous soils to predict com and wheat plant tissue P concentration and grain yield responses. The NH₄OAc‐EDTA method predicted yield and tissue P concentration responses to P fertilizer applications more accurately than the Olsen method at three of five sites. Both the Bray‐1 and NH₄OAc‐EDTA methods were successful in predicting corn and wheat yield responses to P fertilizer applications in non‐ calcareous soils in many locations. However, a direct comparison of extracted soil P levels showed that the NH₄OAc‐EDTA method extracted soil P at levels which were more closely related to the Bray‐1 method than the Olsen method.     

Chemical fractions of copper and zinc in organic‐rich particles from aqueous extracts of a metal‐contaminated granite soil

Abstract

Chemical fractions of copper (Cu) and zinc (Zn) in the organic‐rich particles collected from filtered aqueous extracts (<20 μm) of an acid soil were determined. A sequential extraction procedure was used to partition the particulate Cu and Zn into four operationally defined chemical fractions: adsorbed (ADS), iron (Fe) and manganese (Mn) oxides bound (FeMnOX), organic matter bound (OM) and residual (RESD). Total extractable concentrations of Cu and Zn in the fine particles were higher than their total concentrations in the original bulk soil. The concentration of particulate Cu was usually much higher than that of particulate Zn. Addition of lime stabilized sewage sludge cake and/or inorganic metal salts markedly increased the concentrations of particulate Cu and Zn in aqueous extracts, especially from limed soil. The proportional distributions of particulate Cu and Zn were quite similar. The two particulate metals were present predominantly in the ADS and FeMnOX fractions, with less (about 20%) in the OM and RESD fractions. Some of the ADS metal fraction was associated with dissolved organic substances. The concentrations of particulate Cu and Zn in the various extractable fractions were significantly affected by the application of lime, lime stabilized sewage sludge cake, or inorganic metal salts.     

Deep‐freezing pretreatment and time of extraction of soil samples for inorganic nitrogen determination

Abstract

Soil samples for inorganic nitrogen (N) determination are usually deep‐frozen to prevent microbial transformations of N between sampling and analysis. For analysis, frozen soils are thawed, which may also lead to transformations of N. A specially manufactured mill for grinding frozen soil was tested to minimize these transformations. Whether the time of extraction of the samples could be extended to 20 hr to better accomondate routine work and to make the clay aggregates to disperse better during extraction was also investigated. Freezing of the samples did not produce different results to fresh soils from ammonium nitrogen (NH₄ ⁺‐N) or nitrate nitrogen (NO₃ ^‐‐N) determination. Thawing of the samples increased the concentration of NO₃ ^‐‐N in the extracts and grinding increased that of NH₄ ⁺‐N. When either thawing or grinding was applied, the total inorganic nitrogen concentration was about the same. Thawing of the ground samples increased concentrations of NO₃’‐N and NH₄ ⁺‐N in the extracts. Extending the time of extraction from 0.5 or 1 hr to 20 hr increased the concentration of NH₄ ⁺‐N in the extracts, while NO₃ ^‐‐N content was also increased slightly. It was concluded that sample pretreatment may cause serious errors in the determination of inorganic N even by methods which have proven most successful to prevent microbial transformations of nitrogen, unless the soils are extracted immediately after sampling. The period of extraction should not exceed two hours.     

Cadmium sulfate application to sludge‐amended soils: II. Extraction of Cd,Zn and Mn from solid phases

Abstract

Cadmium, Zn and Mn in eleven paired soils (one which had a history of sludge application and a control from adjacent land where sludge had not been used) were partitioned into five fractions: exchangeable, adsorbed, organically bound, carbonate bound and sulfide, by the use of KNO₃, H₂0, NaOH, EDTA and HNO₃, respect‐ively. The data indicate that the major portion of the total metals was found in the carbonate, sulfide and organic fractions. Addition of CaCO₃caused an increase in the exchangeable + soluble fractions of added Cd in the soils, but had little effect on native or sludge derived Cd.     

Loss‐on‐ignition as an estimator of soil organic carbon in a‐horizon forestry soils

Abstract

The determination of soil organic matter by wet digestion techniques is a slow and laborious analysis. Loss‐on‐ignition (LOI) provides a simple alternative technique for the estimation of soil organic carbon in non‐calcareous A horizon soils of the Natal midlands and Zululand forestry regions. Using multiple regressional techniques, the relationships between loss‐on‐ignition, Walkley organic carbon and soil texture for 55 soils were determined over a range of ignition temperatures. The relationships hold best for soil samples with relatively low organic carbon contents (< 5%). The optimum temperature for ignition was found to occur at 450°C and resulted in the relationship: Soil organic carbon = 0.284*LOI percent. No advantage is gained through ignition at higher temperatures due to the loss of clay mineral structural water, even if the soil texture is accurately known.     

Breakdown of azadirachtin A in a tropical soil amended with neem leaves and animal manures

A field investigation was conducted to assess the breakdown of azadirachtin A in a tropical coastal savanna soil amended with neem leaves （NL） combined with poultry manure （PM） or cow dung （CD） using gas chromatography. Samples in polythene bags 15 cm long and 4.8 cm in diameter were randomly placed to a depth of 14 cm in the soil, and azadirachtin A concentration was assessed on days 0, 14, 28, 42, 56, 70, and 84. Azadirachtin A degradation in the soil followed first-order reaction kinetics with different half-lives obtained for varying combinations of the amendments. Higher neem amendment levels of 100 g gave shorter half-lives of azadirachtin A than the lower levels of 50 g. Within the 50 g NL group the additions of the poultry manure and the cow dung gave significantly shorter （P 〈0.05） half-lives of azadirachtin A than the sole neem amendment, whereas in the 100 g NL group only additions of 10 g CD and 10 g PM were significantly less （P 〈 0.05） than the sole neem amendment. Different changes resulting from the kind and quantity of animal manure added were observed in the half-lives of azadirachtin A. The 100 g NL group had significantly higher （P 〈0.05） moisture content, which, coupled with the likely differeaces in microbial biomass, could be the major factor responsible for variations in the half-llfe of the compound. Therefore, the quantity of the neem leaves applied and the addition of animal manure affected the breakdown of azadirachtin A in the soil amended with neem leaves.     

Influence of air drying and soil gas‐phase carbon dioxide on DTPA‐extractable iron in calcareous soils

Abstract

The extraction of a field‐moist soil with DTPA will result in a level of extractable iron (Fe) lower than that of the air‐dried soil. Soil gas‐phase carbon dioxide (CO₂) levels may be considerably higher than ambient atmospheric levels, especially in wet soils in the field. This study was undertaken to determine whether gas‐phase CO₂ level influences the quantity of Fe extracted by DTPA. Three moist calcareous soils were incubated for 21 days, each at three different partial pressures of CO₂, after which the moist soils were extracted with DTPA. A sample of each soil was also air dried, and was subsequently extracted with DTPA. In each case, DTPA‐extractable Fe from the moist sample was lower than that from the air‐dried sample; however, DTPA‐extractable Fe increased with increasing CO₂ partial pressure of in the moist soils. DTPA‐extractable Fe concentration for a given soil following air drying was not significantly influenced by the CO₂ partial pressure during incubation of the originally field‐moist soil. DTPA‐extract pH of the moist soils followed the same trend as soil‐solution pH (i.e., as CO₂ concentration of the soil gas‐phase increased, soil solution pH and DTPA extract pH both decreased); however, the slope of the pH versus log P_CO2 curve was less pronounced in the DTPA extract due to the buffering capacity of the triethanolamine. From this study, it is concluded that elevated soil gas‐phase CO₂ partial pressure does not contribute to the lower level of DTPA‐extractable Fe observed when the extraction is performed on a field‐moist versus an air‐dried soil; increased CO₂ partial pressure actually resulted in a slight increase in concentration of DTPA‐extractable Fe obtained from a field‐moist soil.