Effects of time and temperature on the bioavailability of Cd and Pb from sludge-amended soils

A pot experiment was conducted to compare the behaviour and bioavailability of Cd and Pb from two soils mixed with sewage sludge at three rates (0, 50 and 150 t ha^?1) and maintained at two contrasting ambient temperatures (15°C and 25°C) over a period of one year following the treatments. Ryegrass (Lolium perenne) accumulated Cd and Pb in the sewage sludge treated soils, although accumulation was significantly lower in the soils treated at the high rate (150 t ha^?1) compared to the low rate (50 t ha^?1). Ryegrass grown in the warm environment (25°C) accumulated significantly higher levels of Cd and Pb than that grown in cooler conditions (15°C). Samples of the soils spiked with nitrate salts of Cd and Pb at equivalent rates of metal loading resulted in the ryegrass accumulating much higher levels of both the metals than on the sludge treated soils. Metal uptake by the ryegrass from the sludge treatments increased over successive harvests while that from metal salt treatments decreased. The observed trend of increasing plant metal uptake over time coincided with a trend of decreasing pH in the sludge treatments. However, the concentrations of Cd and Pb extracted by DTPA failed to predict the changes in plant metal uptake. The importance of sewage sludge as both a source and a sink of pollutant metals and the trend of increasing bioavailability over time shown by this experiment are discussed.     

Determination of the Residual Metal Binding Characteristics of Soils Polluted by Cd and Pb

Four soils contaminated by Pb-Zn mining, Pb-Zn smelting, sewage sludge application, and clay pigeon shooting, respectively, were evaluated for their ability to attenuate relatively high concentrations of supplied Cd and Pb. The retention characteristics of the polluted soils and ‘background’-unpolluted soils for Cd and Pb, were assessed by batch adsorption experiments and equilibrium dialysis titration of the soil organic component. From the sorption data it was observed that the mining polluted and sewage sludge treated soils showed no significant change in Cd affinity when compared to the unpolluted soils. However, for Pb, the reduction in the slopes in the isotherms of the sludge treated and shot over soils were significant when compared to the background soils – indicating a reduced affinity for Pb. The Cd and Pb complexation capacities of the organic component were reduced in the mining, smelter and shot over soil compared to their respective background soils. However, the complexation capacity for Cd of the sludged soil increased from 1.01 µmol Cd g^-1 of organic matter to 4.38 µmol Cd g^-1 of organic compared to the background soil, but, the stability constant of the organo-metal complex formed was lower (6.05 cf. 6.85).     

Trace metal analysis of sewage sludge and soils in Bahrain

Trace metals such as Pb, Zn, Cu, Ni, Cd and Fe were determined in sewage sludge produced at a sewage treatment plant in Bahrain (Tubli) and soils. The soils, both untreated and treated with the sludge, are used for agricultural purposes in Bahrain. The Trace-metals level showed the following range (μg g^?1 dry weight); Pb, 242 to 609; Zn, 704 to 836, Cu, 329 to 512; Ni, 23 to 41; Cd, 1.8 to 3.9 and Fe, 1867 to 4284. The data show the degree to which untreated soils have already been contaminated with trace elements. The level of trace-elements found in sludge showed the following range (μg g^?1 dry weight); Pb, 140 to 186; Zn, 597 to 836; Cu, 348 to 449; Ni, 47 to 53; Cd 5.7 to 9.2 and Fe, 5950 to 8520. Mean levels were generally close or lower than mean concentration reported in the United Kingdom and the United States for sludge. They were also lower than the suggested concentration limits for application of sludge on agricultural land, which is one of the most cost effective and attractive techniques for sludge disposal. Soils treated with this sludge (after 1 yr) were also analyzed and showed substantial enhancement of the available level of trace elements in the soil. This eventually will lead to an increase in the trace-element level in plants grown for human or animal consumption. This could have phytotoxic effects, and the possibility of toxic effects on live-stocks and human beings.     

The sorption of Cd and Zn by different soils in the presence of dissolved organic matter from sludge

Dissolved organic matter (DOM) is one of the important factors affecting metal mobility and phytotoxicity in the soils receiving sewage sludge. The aim of this study was to investigate the effects of DOM from anaerobically digested dewatered sludge on Cd and Zn sorption by three different soil types (calcareous clay loam, calcareous sandy loam and acidic sandy loam) of different physico-chemical properties through batch studies. The addition of DOM significantly reduced the Cd and Zn sorption capacity by a factor of 2.1–5.7 for Cd and 2.3–13.7 for Zn for these three soils as seen by their K values in the Freundlich equation compared to the control receiving no DOM, suggesting that DOM had a stronger inhibitory effect on Zn sorption than that of Cd. The reduction in metal sorption caused by DOM was very apparent in the pH range of 5 to 8, with a maximum inhibition on metal sorption occurring at pH 7–7.5 especially for Zn but the effect was minimal at lower pH. At a DOM concentration of < 200 mg C l^− 1, Cd and Zn sorption by all the three soils decreased with an increase in DOM concentration. At each given DOM concentration, the inhibition of metal sorption of the different soil types increased in the following order: acidic sandy loam < calcareous sandy loam < calcareous clay loam. DOM derived from sludge would significantly reduce metal sorption and increase its mobility through the formation of soluble DOM–metal complexes and poses risk of metal leaching and phytotoxicty in near-neutral and alkaline soils.     

Effect of sewage sludge on some chemical properties of calcareous sandy soils

Abstract

City sewage sludge was applied to the surface layer (0–10 cm) of two sandy soils, slightly calcareous with 8.9% CaCO₃ and moderately calcareous with 26.7% CaCO₃, at the rates of 0, 25, 50, 75, and 100 Mg ha^‐1. The effects of sewage sludge and its rates on total soluble salts, pH of soils and concentration and movement of some heavy metals within soils were investigated. Soil samples were packed at bulk density of 1.5 g cm^‐3 in PVC columns and incubated for 19 weeks. The results indicated that total soluble salts (EC) of the treated layer increased with increasing sewage sludge rates. Soluble salts also increased with an increase in soil depth for both soils. The pH values of treated layers in two soils decreased with increasing sewage sludge rates. With increasing sewage sludge rates, concentrations of heavy metals [cobalt (Co), nickel (Ni), cadmium (Cd), and leaf (Pb)] increased in the treated layers compared to the untreated layers and their mobility was restricted mostly to the upper 30‐cm depth. Movement of Co and Pb in both the soils was predominately limited up to a depth of 40 cm for Co and 5 cm for Pb below the treated soil layer. Nickel and Cd movement was mostly limited to a depth of 10 cm in slightly calcareous soil and 5 cm in moderately calcareous soil. Metal movement in the respective soils is ranked as Co>Ni=Cd>Pb and Co>Ni=Cd>Pb. The low concentrations of heavy metals and the restricted mobility with soil depth, suggest that this material may be used for agricultural crop production without any toxic effect on plants.     

Soil Organic Matter Quality and Zinc and Lead Sorption as Affected by a Sewage Sludge Or a Sewage Sludge Compost Application

Sewage sludge (SS) or sewage sludge compost (SSC) were applied to soil under controlled conditions, at rates of 0 or 200 Mg ha^?1, to investigate changes in dissolved organic matter (DOM), humic acids (HA), and Pb and Zn sorption in the soil. Infrared spectroscopy, visible spectrophotometry, and sorption isotherms (mono-metal and competitive sorption systems) methods were used to assess the changer. The E₄/E₆ ratio (λ at 465 / λ at 665 nm) and the infrared spectra of DOM and HA showed aromatic behaviour in compost-soil (SSC-S); in contrast sewage sludge-soil (SS-S) showed an aliphatic behaviour. Application of either SS or SSC increased the Pb and Zn sorption capacity of soil. The Pb and Zn sorption increased in soil and soil mixtures with a competitive metal system. The metal affinity sequence for soil, SS-S, and SSC-S was compared with the predicted affinity sequences obtained from metal properties. Poor correspondence was observed between the metal affinity sequence and the metal affinity sequence predicted by ionic potential, indicating that metals bonding to soils were not predominantly electrostatic. An affinity sequence based on Pearson's theory agreed with the metal affinity sequences for soils. A statistical analysis showed that the bands assigned to esters (1080 cm^?1) of DOM, phenolic OH (1420 cm^?1), amide I (1650 cm^?1), carboxyl and carbonyl C=O stretches of different nature, C=O stretch of aromatic esters, aliphatic cetone, aldehyde (1720 cm^?1), ethers and esters (1230 cm^?1), aliphatic alcohols (1125 cm^?1), and lignin (1380 cm^?1) of HA were correlated with Zn constants of Langmuir adsorption isotherm (P < 0.05).     

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.     

Competitive sorption of cadmium and lead in acid soils of Central Spain

The bioavailability and ultimate fate of heavy metals in the environment are controlled by chemical sorption. To assess competitive sorption of Pb and Cd, batch equilibrium experiments (generating sorption isotherms) and kinetics sorption studies were performed using single and binary metal solutions in surface samples of four soils from central Spain. For comparisons between soils, as well as, single and binary metal solutions, soil chemical processes were characterized using the Langmuir equation, ionic strength, and an empirical power function for kinetic sorption. In addition, soil pH and clay mineralogy were used to explain observed sorption processes. Sorption isotherms were well described by the Langmuir equation and the sorption kinetics were well described by an empirical power function within the reaction times in this study. Soils with higher pH and clay content (characterized by having smectite) had the greatest sorption capacity as estimated by the maximum sorption parameter (Q) of the Langmuir equation. All soils exhibited greater sorption capacity for Pb than Cd and the presence of both metals reduced the tendency for either to be sorbed although Cd sorption was affected to a greater extent than that of Pb. The Langmuir binding strength parameter (k) was always greater for Pb than for Cd. However, these k values tended to increase as a result of the simultaneous presence of both metals that may indicate competition for sorption sites promoting the retention of both metals on more specific sorption sites. The kinetic experiments showed that Pb sorption is initially faster than Cd sorption from both single and binary solutions although the simultaneous presence of both metals affected the sorption of Cd at short times while only a minor effect was observed on Pb. The estimated exponents of the kinetic function were in all cases smaller for Pb than for Cd, likely due to diffusion processes into micropores or interlayer space of the clay minerals which occurs more readily for Cd than Pb. Finally, the overall sorption processes of Pb and Cd in the smectitic soil with the highest sorption capacity of the studied soils are slower than in the rest of the soils with a clay mineralogy dominated by kaolinite and illite, exhibiting these soils similar sorption rates. These results demonstrate a significant interaction between Pb and Cd sorption when both metals are present that depends on important soil properties such as the clay mineralogy.     

肥料重金属含量状况及施肥对土壤和作物重金属富集的影响

本文对肥料中重金属的含量状况以及施肥对土壤和农作物重金属累积影响的研究进展进行了系统分析和总结。过磷酸钙中锌（Zn）、 铜（Cu）、 镉（Cd）、 铅（Pb）含量高于氮肥、 钾肥和三元复合肥,有机-无机复混肥料中的Pb含量高于其他化肥。有机肥如畜禽粪便、 污泥及其堆肥中的重金属含量高于化肥,猪粪中的Cu、 Zn、 砷（As）、 Cd含量明显高于其他有机废弃物,鸡粪中铬（Cr）含量高;污泥和垃圾堆肥中Pb或汞（Hg）含量高。商品有机肥Zn、 Pb和镍（Ni）含量高于堆肥,Hg含量高于畜禽粪便。多数研究表明,氮磷钾配施与不施肥相比土壤Cd和Pb含量增加,施用有机肥比不施肥提高土壤Cu、 Zn、 Pb、 Cd含量。施用化肥对农作物重金属富集的影响不明确,而施用有机肥可提高作物可食部位Cu、 Zn、 Cd、 Pb 的含量,影响大小与有机肥种类、 用量、 土壤类型和pH以及作物种类等有很大关系。在今后的研究中应着重以下几个方面, 1）典型种植体系下土壤重金属的投入/产出平衡; 2）不同种植体系下长期不同施肥措施对土壤重金属含量、 有效性影响的动态趋势; 3）典型种植体系和施肥措施下土壤对重金属的最高承载年限; 4）现有施肥措施下肥料中重金属的最高限量标准。     

Sorption of lead,copper, zinc,and cadmium by soils: effect of nitriloacetic acid on metal retention

Abstract

Laboratory experiments were carried out to evaluate lead (Pb), copper (Cu), zinc (Zn), and cadmium (Cd) sorption‐desorption by three soils of contrasting characteristics. Talamanca (silt loam, montmorillonite, Calcic Haploxeralfs), Mazowe (clay, kaolinite, Rhodic Kandiustalf), and Realejos (sandy silt loam, allophane, Typic Hapludands). A second objective was to study the effect of nitriloacetic acid (NTA) on the sorption process. The Talamanca soil, which had a native pH of 6.4 and presented the highest effective cation exchange capacity (ECEC), sorbed more of each of the metal tested than did the other two soils. When the other two soils were compared metal sorption was also related to pH and ECEC. The very low sorption capacity showed by Realejos may be attributed to the low net surface negative charge density of this soil, arising from its allophanic nature. A common feature of the three soils was the relative strong sorption of both Pb and Cu relative to Cd and Zn with Pb showing the highest sorption levels. The selectivity sequences of metals retention were Pb>Cu>Zn>Cd for Talamanca soil, Pb>Cu>Zn≈Cd for Mazowe, and Pb>Cu>Cd>Zn for Realejos. Metal desorption values were low. The order of metal desorption (Cd≈Zn>Cu>Pb) was the same for the three soils studied. Quantitative differences observed in the extractability of the sorbed metals between the soils (Realejos>Mazowe>Talamanca) indicated that soil properties which enhanced metal sorption contributed at the same time to slow down the backward reaction. The addition of NTA to the soil suspension significantly depressed metal sorption by the three soils investigated. Compared with the free ligand system Pb, Cu, Zn, and Cd sorption in the presence of NTA decreased roughly 50%.     

Influence of prolonged use of sewage effluent in irrigation on heavy metal accumulation in soils and plants

Total content of Fe, Mn, Zn, Cu, Pb, Cd, Ni and Co in soils irrigated with sewage effluent increased with increasing years of using sewage effluent in irrigation. Iron and Co applied to the soil from sewage effluent were immobilized mainly in unavailable form; Pb, Cd, and Ni in moderately available form; and Mn, Zn, and Cu in highly available form. The concentrations of Fe, Mn, Zn and Cu in tops of alfalfa and leaves of corn grown on these soils increased substantially with increased levels of available metal content of the soil, while those of other metals were little affected. As for orange, continuous increase in leaves metal content with time was found for Fe, Mn, Zn, Co and Cd. The concentrations of Cd, Co, Ni and Pb in corn grains and orange fruits were several times higher than normal, and this reduces their suitability for human consumption.     

施用污泥后石灰性土壤中铜、锌、镉的植物有效性

The toxicity of trace elements (TEs), such as copper (Cu), zinc (Zn), and cadmium (Cd), often restrict land application of sewage sludge (SS) and there was little information about soil-plant transfer of TEs in SS from field experiments in China. In this study pot and field experiments were carried out for 2 years to investigate the phytoavailability of TEs in calcareous soils amended with SS. The results of the pot experiment showed that the phytoavailability of Zn and Cu in the SS was equal to 53.4%-80.9% and 54.8%-91.1% of corresponding water-soluble metal salts, respectively. The results from the field experiment showed that the contents of total Zn, Cu, and Cd in the soils increased linearly with SS application rates. With increasing SS application rates, the contents of Zn and Cu in the wheat grains initially increased and then reached a plateau, while there was no significant change of Cd content in the maize grains. The bioconcentration factors of the metals in the grains of wheat and maize were found to be in the order of Zn > Cu > Cd, but for the straw the order was Cd > Cu > Zn. It was also found that wheat grains could accumulate more metals compared with maize grains. The results will be helpful in developing the critical loads of sewage sludge applied to calcareous soils.     

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.     

Comparative availability to wheat of metals from sewage sludge and inorganic salts

A greenhouse experiment was conducted to evaluate the availability of metals from sewage sludge and inorganic salts, and the effect of pH and soil type on yield and metal (Zn, Cu, Cd and Ni) uptake by wheat (Triticum aestivum L. var. ‘holly’). Soils used in this study were Hartsells sandy loam (fine-loamy, siliceous Thermic Typic Hapludult) and Decatur silty clay loam (Clayey, kaolinitic, Thermic Rhodic Paleudult). Two treatments of sewage sludge containing metals were applied at the rate of 20 and 100 mt ha^?1. Inorganic Salts of Zn, Cu, Cd, and Ni were applied (as sulfate salts) at concentrations equivalent to those found in the 20 and 100 mt ha^?1 sludge. One treatment consisted of inorganic metals plus sewage at the 20 Mg ha^?1 rate. Two soil pH levels, one at field pH (below 6.0) and another pH adjusted between 6.5 and 7.0 were used. Wheat plants were harvested four weeks after germination. Two more subsequent harvests were made at four week intervals. For each harvest, dry matter yield increased as the rate of sludge application increased for both soil types. The soil pH also influenced the dry matter yield. High yield was observed when the pH was adjusted between 6.5 to 7.0 for both soils. An increase in yield was also observed at each subsequent harvest for most of the treatments. Inorganic salt treatments produced lower dry matter yields when compared with the sludge. Both sludge application and metal salts increased plant tissue concentration of Zn, Cu, Cd, and Ni at field pH for both soils. However, increasing the pH of the soil for both sludge and inorganic salt treatments generally decreased the tissue concentration of the above metals.     

The adsorption characteristics of soils and removal of cadmium and nickel from wastewaters

The interactions between the adsorption characteristics of 27 experimental soils and the sorption of Cd and Ni from the municipal wastewaters were investigated in this study. The removal of these elements from soil solution was followed for 50 days. All the adsorption characteristics, except cation exchange capacity and organic matter, were significantly correlated to the sorption of Cd after one day shaking. After 7 days of shaking, none of the soil adsorption characteristics except free CaCO₃ was significantly correlated to Cd removal from wastewater. The soil saturated paste pH and suspension pH were strongly correlated to Cd sorption throughout this experiment. The behavior of Ni in soils was different from that of Cd. Surface area, total Fe, and total Al were significantly correlated to Ni sorption. The correlation between Ni removal and pH was the strongest than any other parameter studied. After 7 days shaking, clay content and total Ca were not significantly correlated to Ni sorption. The cation exchange capacity of the soils was not significantly correlated to Cd or Ni sorption in this experiment. It seems that in the experimental soils, concentration of Cd and Ni were probably not controlled by adsorption process. The precipitation process was probably playing a major role in the removal of these elements from the municipal wastewaters. As observed in this experiment, the cation exchange capacity of experimental soils was a poor parameter to define sorption capacity of these soils for Cd and Ni. The guidelines for determining the soil sludge load, which are mainly based on the cation exchange capacity of soils, should be revised.     

Adsorption isotherms of some heavy metals under conditions of their competitive adsorption onto highly calcareous soils of southern Iran

Recently, application of sewage sludge or effluents resulted in raising the concentrations of some heavy metals in some agricultural soils of Iran. Experiments were conducted to evaluate the competitive adsorption of lead (Pb), copper (Cu), zinc (Zn), and cadmium (Cd) on six calcareous soils. Adsorption characteristics were evaluated by equilibration of 1 g of each soil sample with 20 ml of 0, 10, 20, 30, 40, 50, 100, or 200 mg L^?1 of their nitrate solutions and 0.01 M NaNO₃ as background electrolyte. Furthermore, solid/liquid distribution coefficients (K_d) of studied metals, as an index of soil capacity to resist a change of the soil solution concentration, were calculated. Results indicated that amounts of adsorbed Pb, Cu, Zn, and Cd increased with increase in their concentrations in the contact solutions, but this trend was more pronounced for Pb and Cu than the others. For all studied soils and metals, Langmuir equation described the adsorption behavior fairly well. Furthermore, Langmuir and Freundlich equation parameters were positively correlated to cation exchange capacity (CEC) and smectite contents; whereas, they were negatively correlated to sand content. Considering K_d values, the selectivity sequence of the metal adsorption was Pb > Cu > Zn > Cd. Therefore, the risk of leaching and also plant uptake of Zn and Cd will be higher as compared to those of the other elements.     

复垦沉积池土壤中镍、铅、锌的吸附

The wastes used to amend soils sometimes have high concentrations of metals such as nickel (Ni), lead (Pb) and zinc (Zn). To determine the capacity of soils to retain these metals, the sorption capacities of different mine soils with and without reclamation treatments (tree vegetation and waste amendment) for Ni, Pb and Zn in individual and competitive situations were evaluated using the batch sorption technique. The untreated settling pond soil had low capacity for Ni, Pb and Zn retention. The site amended with wastes (sewage sludges and paper mill residues) increased the sorption capacity most, probably because of the higher concentrations of soil components with high retention capacity such as carbon and clay fraction. No significant competition was observed between metals in the competitive sorption experiment, indicating that the maximum of sorption was not achieved by adding 0.5 mmol L^-1 of metal. We can conclude that, despite the possible additions of Ni, Pb and Zn from wastes to degraded soils, sewage sludges and paper mill residues have a high sorption capacity that would prevent the metals from being in a mobile form.     

Speciation of Metals in Sewage Sludge and Sludge-amended Soils

This study is aimed at ascertaining the chemical partitioning ofCu, Zn, Pb, Ni, Cr and Cd in sewage sludge and agricultural soils repeatedly amended with sludge. The operationally determined speciation was investigated by using selective five steps sequential extraction method for partitioning these metals into different chemicalforms, likely to be released in solution under various environmental conditions. It provides qualitative evidence regarding the form of the association of metals and indirectly of their bioavailability. It can help to explain the process by which metals are eliminated from sewagesludge and also indicate the impact of the use of sludge on agriculturalsoils, as amendments. Data obtained by extraction procedure showed different metal distribution trend among the fractions in sewage sludgeand sludge-amended soils. Comparison of distribution pattern of metals in sludge and sludge-applied soils shows that there is possible redistribution of metals among the different phases. The sum of the metal content in the fractions compared well with the total metal content in sewage sludge, the ratios averaging 1.02, 1.04, 1.07, 0.94, 1.06, and 1.12 for Cu, Zn, Pb, Ni, Cr, and Cd, respectively. The metal recovery efficiency in sludge-amended soils was found to be: 108±6%, 102±5%, 115±8%, 111±4%, 104±7%and 124±28% for Cu, Zn, Pb, Ni, Cr and Cd, respectively.     

Comparative evaluation of residual and total metal analyses in polluted soils

Abstract

Two digestion procedures, employing aqua regia‐HF (ARHF) and HNO₃‐HCIO4‐HF (HHH), were used to analyze residual metals (following a chemical fractionation scheme) and total metal content of two soils, one moderately polluted by municipal sludge applications and the other a grossly‐contaminated sample (20.8% Pb) from a battery recycling site. Although commonly used in sequential extraction analyses, the ARHF method solubilized only 53% (significant at p = 0.05) of the HHH‐determined residual Pb in the battery soil. For the sludge‐amended soil, residual Cd, Pb, and Zn were not statistically different by the two methods. For the battery soil, a single ARHF extraction also underestimated total Pb and Cu relative to HHH, but both methods gave statistically‐similar total Cd, Cu, Pb, and Zn for the sludge‐amended soil. As the sample metal concentration increased, the ability of ARHF to solubilize HHH‐equivalent metal quantities generally decreased. Since the degree of contamination is often unknown for environmental samples, the HHH method is more reliable for assessing residual and total metals in polluted soils     

Predicting Metal Uptake and Risk to the Human Food Chain from Leaf Vegetables Grown on Soils Amended by Long-Term Application of Sewage Sludge

The success of risk assessment of metal contaminated soils depends on how precisely one can predict the bio-availability of metals in soil and transfer to the human food chain. In the present investigation, we tested several formulations of the ‘free-ion activity model (FIAM)’ to predict uptake of Cd, Zn and Cu by perpetual spinach (Beta vulgaris, Cicla) grown on a range of soils amended with sewage sludge. The model was parameterised using data measured on samples of pore water extracted by centrifugation and with porous Rhizon samplers installed within the rhizosphere of the growing plants. Free ion activities (M²⁺) were estimated following speciation of solution data using version 6 of the ‘Windermere Humic Aqueous Model (WHAM-VI). For all three metals, the best formulation of the FIAM appeared to require only one hypothetical root sorption site without competition from protons. Values of (M²⁺) could also be predicted satisfactorily from a pH-dependent Freundlich relation. Thus, from a combined FIAM–Freundlich relation and population dietary information, it was possible to estimate risk (hazard quotients) to consumers from very simple soil measurements: extractable metal content (0.05 M EDTA (Zn and Cu) or 1 M CaCl₂ (Cd)), soil humus content and pH. The role of increased soil organic matter content and soil pH, in reducing risk to consumers, is illustrated for Cd in a hypothetical soil at the current UK statutory Cd limit for sludge application to agricultural land.