Biochar- and phosphate-induced immobilization of heavy metals in contaminated soil and water: implication on simultaneous remediation of contaminated soil and groundwater

Long-term wastewater irrigation or solid waste disposal has resulted in the heavy metal contamination in both soil and groundwater. It is often separately implemented for remediation of contaminated soil or groundwater at a specific site. The main objective of this study was to demonstrate the hypothesis of simultaneous remediation of both heavy metal contaminated soil and groundwater by integrating the chemical immobilization and pump-and-treat methods. To accomplish the objective, three experiments were conducted, i.e., an incubation experiment was first conducted to determine how dairy-manure-derived biochar and phosphate rock tailing induced immobilization of Cd in the Cd-contaminated soils; second, a batch sorption experiment was carried out to determine whether the pre-amended contaminated soil still had the ability to retain Pb, Zn and Cd from aqueous solution. BCR sequential extraction as well as XRD and SEM analysis were conducted to explore the possible retention mechanism; and last, a laboratory-scale model test was undertaken by leaching the Pb, Zn, and Cd contaminated groundwater through the pre-amended contaminated soils to demonstrate how the heavy metals in both contaminated soil and groundwater were simultaneously retained and immobilized. The incubation experiment showed that the phosphate biochar were effective in immobilizing soil Cd with Cd concentration in TCLP (toxicity characteristics leaching procedure) extract reduced by 19.6 % and 13.7 %, respectively. The batch sorption experiment revealed that the pre-amended soil still had ability to retain Pb, Zn, and Cd from aqueous solution. The phosphate-induced metal retention was mainly due to the metal–phosphate precipitation, while both sorption and precipitation were responsible for the metal stabilization in the biochar amendment. The laboratory-scale test demonstrated that the soil amended with phosphate removed groundwater Pb, Zn, and Cd by 96.4 %, 44.6 %, and 49.2 %, respectively, and the soil amended with biochar removed groundwater Pb, Zn, and Cd by 97.4 %, 53.4 %, and 54.5 %, respectively. Meanwhile, the metals from both groundwater and soil itself were immobilized with the amendments, with the leachability of the three metals in the CaCl₂ and TCLP extracts being reduced by up to 98.1 % and 62.7 %, respectively. Our results indicate that the integrated chemical immobilization and pump-and-treat method developed in this study provides a novel way for simultaneous remediation of both metal-contaminated soil and groundwater.     

石灰干化污泥对土壤重金属稳定化处理的效果

以采自湖南省嘉禾县重金属复合污染土壤为研究对象,采用城市污水处理石灰干化污泥作为稳定剂,对污染土壤进行稳定化处理,并采用TCLP和BCR连续提取法对稳定化效果进行分析和评价。研究结果表明,单独使用石灰干化污泥,TCLP浸出浓度随着干化污泥质量分数的增加而显著减少,干化污泥的质量分数为40%时,稳定化率最大为Zn-98.92%、Cd-99.06%、Pb-96.84%;但是干化污泥的高pH值导致稳定后土壤中As的浸出增加。为了恢复植物生长功能,经过亚铁盐和磷酸调节pH后,石灰干化污泥稳定过的土壤pH有效降低,同时亚铁盐和磷酸有利于促进Pb和Zn的稳定效果;但是对Cd的稳定有负面影响;另外,亚铁盐的加入同时可以减少As的浸出浓度。经处理后土壤中重金属形态由不稳定态转为稳定态,使重金属的浸出浓度明显降低,减少了土壤重金属的浸出毒性。该研究结果表明,石灰干化污泥可以作为资源回收利用,应用于重金属污染土壤的修复中,并能改善稳定后土壤适宜植物生长的理化性质。     

Effects of phosphorus amendments and plant growth on the mobility of Pb, Cu, and Zn in a multi-metal-contaminated soil

Purpose

Phosphorus amendments have been widely and successfully used in immobilization of one single metal (e.g., Pb) in contaminated soils. However, application of P amendments in the immobilization of multiple metals and particularly investigations about the effects of planting on the stability of the initially P-induced immobilized metals in the contaminated soils are far limited.

Methods

This study was conducted to determine the effects of phosphate rock tailing (PR), triple superphosphate fertilizer (TSP), and their combination (P+T) on mobility of Pb, Cu, and Zn in a multimetal-contaminated soil. Chinese cabbage (Brassica rapa subsp. chinensis) (metal-sensitive) and Chinese kale (Brassica alboglabra Bailey) (metal-resistant) were introduced to examine the effects of planting on leaching of Pb, Cu, and Zn in the P-amended soils.

Results

All three P treatments greatly reduced CaCl₂-extractable Pb and Zn by 55.2?C73.1% and 14.3?C33.6%, respectively. The PR treatment decreased CaCl₂-extractable Cu by 27.8%, while the TSP and P+T treatments increased it by 47.2% and 44.4%, respectively. All three P treatments were effective in reducing simulated rainwater leachable Pb, with dissolved and total leachable Pb decrease by 15.6?C81.9% and 16.3?C64.5%, respectively. The PR treatment reduced the total leachable Zn by 16.8%, while TSP and P+T treatments increased Zn leaching by 92.7% and 78.9%, respectively. However, total Cu leaching were elevated by 17.8?C178% in all P treatments. Planting promoted the leaching of Pb and Cu by 98.7?C127% and 23.5?C170%, respectively, especially in the colloid fraction, whereas the leachable Zn was reduced by 95.3?C96.5% due to planting. The P treatments reduced the uptake of Pb, Cu, and Zn in the aboveground parts of Chinese cabbage by up to 65.1%, 34.3%, and 9.59%, respectively. Though P treatments were effective in reducing Zn concentrations in the aboveground parts of the metal-resistant Chinese kale by 22.4?C28.9%, they had little effect on Pb and Cu uptake.

Conclusions

The results indicated that all P treatments were effective in immobilizing Pb. The effect on the immobilization of Cu and Zn varied with the different P treatments and evaluation methods. Metal-sensitive plants are more responsive to the P treatments than metal-resistant plants. Planting affects leaching of metals in the P-amended soils, specially leaching of colloid fraction. The conventional assessment on leaching risks of heavy metals by determining dissolved metals (filtered through 0.45-??m pore size membrane) in leachates could be underestimated since colloid fraction may also contribute to the leaching.     

Dolomite phosphate rock (DPR) application in acidic sandy soil in reducing leaching of phosphorus and heavy metals—a column leaching study

A column leaching study was designed to investigate the leaching potential of phosphorus (P) and heavy metals from acidic sandy soils applied with dolomite phosphate rock (DPR) fertilizers containing varying amounts of DPR material and N-Viro soils. DPR fertilizers were made from DPR materials mixing with N-Viro soils at the ratios of 30, 40, 50, 60, and 70 %, and applied in acidic sandy soils at the level of 100 mg available P per kilogram soil. A control and a soluble P chemical fertilizer were also included. The amended soils were incubated at room temperature with 70 % field water holding capacity for 21 days before packed into a soil column and subjected to leaching. Seven leaching events were conducted at days 1, 3, 7, 14, 28, 56, and 70, respectively, and 258.9 mL of deionized water was applied at each leaching events. The leachate was collected for the analyses of pH, electrical conductivity (EC), dissolved organic carbon (DOC), major elements, and heavy metals. DPR fertilizer application resulted in elevations up to 1 unit in pH, 7–10 times in EC, and 20–40 times in K and Ca concentrations, but 3–10 times reduction in P concentration in the leachate as compared with the chemical fertilizer or the control. After seven leaching events, DPR fertilizers with adequate DPR materials significantly reduced cumulative leaching losses of Fe, P, Mn, Cu, and Zn by 20, 55, 3.7, 2.7, and 2.5 times than chemical fertilizer or control. Even though higher cumulative losses of Pb, Co, and Ni were observed after DPR fertilizer application, the loss of Pb, Co, and Ni in leachate was <0.10 mg (in total 1,812 mL leachate). Significant correlations of pH (negative) and DOC (positive) with Cu, Pb, and Zn (P?<?0.01) in leachate were observed. The results indicated that DPR fertilizers had a great advantage over the soluble chemical fertilizer in reducing P loss from the acidic sandy soil with minimal likelihood of heavy metal risk to the water environment. pH elevation and high dissolved organic carbon concentration in soils after DPR fertilizer application are two influential factors.     

Heavy metal availability,bioaccessibility, and leachability in contaminated soil: effects of pig manure and earthworms

A pot experiment and a leaching experiment were conducted to investigate the effects of earthworms and pig manure on heavy metals (Cd, Pb, and Zn) immobility, in vitro bioaccessibility and leachability under simulated acid rain (SAR). Results showed manure significantly increased soil organic carbon (SOC), dissolved organic carbon (DOC), available phosphorus (AP), total N, total P and pH, and decreased CaCl₂-extractable metals and total heavy metals in water and SAR leachate. The addition of earthworms significantly increased AP (from 0.38 to 1.7 mg kg^?1), and a downward trend in CaCl₂-extractable and total leaching loss of heavy metals were observed. The combined earthworm and manure treatment decreased CaCl₂-extractable Zn, Cd, and Pb. For Na₄P₂O₇-extractable metals, Cd and Pb were decreased with increasing manure application rate. Application of earthworm alone did not contribute to the remediation of heavy metal polluted soils. Considering the effects on heavy metal immobilization and cost, the application of 6% manure was an alternative approach for treating contaminated soils. These findings provide valuable information for risk management during immobilization of heavy metals in contaminated soils.

     

Leaching of heavy metals from contaminated soils using EDTA

Ethylenediaminetetraacetic acid (EDTA) extraction of Zn, Cd, Cu and Pb from four contaminated soils was studied using batch and column leaching experiments. In the batch experiment, the heavy metals extracted were virtually all as 1:1 metal-EDTA complexes. The ratios of Zn, Cd, Cu and Pb of the extracted were similar to those in the soils, suggesting that EDTA extracted the four heavy metals with similar efficiency. In contrast, different elution patterns were obtained for Zn, Cd, Cu and Pb in the column leaching experiment using 0.01 M EDTA. Cu was either the most mobile or among the most mobile of the four heavy metals, and its peak concentration corresponded with the arrival of full strength EDTA in the leachate. The mobility of Zn and Cd was usually slightly lower than that of Cu. Pb was the least mobile, and its elution increased after the peaks of Cu and Zn. Sequential fractionations of leached and un-leached soils showed that heavy metals in various operationally defined fractions contributed to the removal by EDTA. Considerable mobilisation of Fe occurred in two of the four soils during EDTA leaching. Decreases in the Fe and Mn oxide fraction of heavy metals after EDTA leaching occurred in both soils, as well as in a third soil that showed little Fe mobilisation. The results suggest that the lability of metals in soil, the kinetics of metal desorption/dissolution and the mode of EDTA addition were the main factors controlling the behaviour of metal leaching with EDTA.     

The effect of earthworms on the fractionation, mobility and bioavailability of Pb, Zn and Cd before and after soil leaching with EDTA

The effect of two ecologically contrasting earthworm species Eisenia fetida (epigeic) and Octolasion tyrtaeum (endogeic) on the fractionation (accessed using sequential extractions), mobility (toxicity characteristic leaching procedure, TCLP) and oral bioavailability (Ruby's physiologically based extraction test, PBET) of Pb, Zn and Cd was studied before and after soil remediation with soil leaching. Twenty-step leaching, with 2.5 mmol kg(-1) EDTA used in each step, removed 58.4%, 25.0% and 68.0% of initial soil Pb, Zn and Cd, respectively, shifted the fractionation of residual heavy metals toward less labile forms, and decreased their mobility by 83.7%, 80.3%, and 90.9%. Pb oral bioavailability was reduced by 3.1-times (in each stomach and intestinal phase). After soil leaching, both earthworm species enriched the carbonate soil fraction in their casts with residual Pb, and increased the Pb bioavailability in the simulated intestinal phase by a factor of 2.4 (E. fetida) and 2.8 (O. tyrtaeum). The concentration of Pb in TCLP leachate from E. fetida casts was 6.2-times higher than in the bulk of the remediated soil. These results indicate that the effect of biotic factors on the availability of heavy metals residual in soil after soil leaching requires consideration.     

Immobilization of lead in contaminated firing range soil using biochar

Soybean stover-derived biochar was used to immobilize lead (Pb) in military firing range soil at a mass application rate of 0 to 20 wt.% and a curing period of 7 days. The toxicity characteristic leaching procedure (TCLP) was performed to evaluate the effectiveness of the treatment. The mechanism responsible for Pb immobilization in military firing range soil was evaluated by scanning electron microscopy-energy dispersive x-ray spectroscopy (SEM-EDX) and x-ray absorption fine structure (XAFS) spectroscopy analyses. The treatment results showed that TCLP Pb leachability decreased with increasing biochar content. A reduction of over 90 % in Pb leachability was achieved upon treatment with 20 wt.% soybean stover-derived biochar. SEM-EDX, elemental dot mapping and XAFS results in conjunction with TCLP leachability revealed that effective Pb immobilization was probably associated with the pozzolanic reaction products, chloropyromorphite and Pb-phosphate. The results of this study demonstrated that soybean stover-derived biochar was effective in immobilizing Pb in contaminated firing range soil.     

Effects of alkaline and bioorganic amendments on cadmium,lead, zinc,and nutrient accumulation in brown rice and grain yield in acidic paddy fields contaminated with a mixture of heavy metals

Paddy soils and rice (Oryza sativa L.) contaminated by mixed heavy metals have given rise to great concern. Field experiments were conducted over two cultivation seasons to study the effects of steel slag (SS), fly ash (FA), limestone (LS), bioorganic fertilizer (BF), and the combination of SS and BF (SSBF) on rice grain yield, Cd, Pb, and Zn and nutrient accumulation in brown rice, bioavailability of Cd, Pb, and Zn in soil as well as soil properties (pH and catalase), at two acidic paddy fields contaminated with mixed heavy metals (Cd, Pb, and Zn). Compared to the controls, SS, LS, and SSBF at both low and high additions significantly elevated soil pH over both cultivation seasons. The high treatments of SS and SSBF markedly increased grain yields, the accumulation of P and Ca in brown rice and soil catalase activities in the first cultivation season. The most striking result was from SS application (4.0 t ha^?1) that consistently and significantly reduced the soil bioavailability of Cd, Pb, and Zn by 38.5–91.2 % and the concentrations of Cd and Pb in brown rice by 20.9–50.9 % in the two soils over both cultivation seasons. LS addition (4.0 t ha^?1) also markedly reduced the bioavailable Cd, Pb, and Zn in soil and the Cd concentrations in brown rice. BF remobilized soil Cd and Pb leading to more accumulation of these metals in brown rice. The results showed that steel slag was most effective in the remediation of acidic paddy soils contaminated with mixed heavy metals.     

Heavy metals in urban soils of East St. Louis, IL. Part II: Leaching characteristics and modeling

The city of East St. Louis, IL, has a history of abundant industrial activities including smelters of ferrous and non-ferrous metals, a coal-fired power plant, companies that produced organic and inorganic chemicals, and petroleum refineries. Following a gross assessment of heavy metals in the community soils (see Part I of this two-part series), leaching tests were performed on specific soils to elucidate heavy metal-associated mineral fractions and general leachability. Leaching experiments, including the Toxicity Characteristic Leaching Procedure (TLCP) and column tests, and sequential extractions, illustrated the low leachability of metals in East St. Louis soils. The column leachate results were modeled using a formulation developed for fly ash leaching. The importance of instantaneous dissolution was evident from the model. By incorporating desorption/adsorption terms into the source term, the model was adapted very well to the time-dependent heavy metal leachate concentrations. The results demonstrate the utility of a simple model to describe heavy metal leaching from contaminated soils.     

Heavy Metals in Urban Soils of East St. Louis,IL Part II: Leaching Characteristics and Modeling

ABSTRACT

The city of East St. Louis, IL, has a history of abundant industrial activities including smelters of ferrous and non-ferrous metals, a coal-fired power plant, companies that produced organic and inorganic chemicals, and petroleum refineries. Following a gross assessment of heavy metals in the community soils (see Part I of this two-part series), leaching tests were performed on specific soils to elucidate heavy metal-associated mineral fractions and general leachability. Leaching experiments, including the Toxicity Characteristic Leaching Procedure (TLCP) and column tests, and sequential extractions, illustrated the low leachability of metals in East St. Louis soils. The column leachate results were modeled using a formulation developed for fly ash leaching. The importance of instantaneous dissolution was evident from the model. By incorporating desorption/adsorption terms into the source term, the model was adapted very well to the time-dependent heavy metal leachate concentrations. The results demonstrate the utility of a simple model to describe heavy metal leaching from contaminated soils.     

Heavy metal immobilization in soil near abandoned mines using eggshell waste and rapeseed residue

Heavy metal contamination of agricultural soils has received great concern due to potential risk to human health. Cadmium and Pb are largely released from abandoned or closed mines in Korea, resulting in soil contamination. The objective of this study was to evaluate the effects of eggshell waste in combination with the conventional nitrogen, phosphorous, and potassium fertilizer (also known as NPK fertilizer) or the rapeseed residue on immobilization of Cd and Pb in the rice paddy soil. Cadmium and Pb extractabilities were tested using two methods of (1) the toxicity characteristics leaching procedure (TCLP) and (2) the 0.1 M HCl extraction. With 5 % eggshell addition, the values of soil pH were increased from 6.33 and 6.51 to 8.15 and 8.04 in combination with NPK fertilizer and rapeseed residue, respectively, compared to no eggshell addition. The increase in soil pH may contribute to heavy metal immobilization by altering heavy metals into more stable in soils. Concentrations of TCLP-extracted Cd and Pb were reduced by up to 67.9 and 93.2 % by addition of 5 % eggshell compared to control. For 0.1 M HCl extraction method, the concentration of 0.1 M HCl-Cd in soils treated with NPK fertilizer and rapeseed residue was significantly reduced by up to 34.01 and 46.1 %, respectively, with 5 % eggshell addition compared to control. A decrease in acid phosphatase activity and an increase in alkaline phosphatase activity at high soil pH were also observed. Combined application of eggshell waste and rapeseed residue can be cost-effective and beneficial way to remediate the soil contaminated with heavy metals.     

Leaching behaviour of Cd, Cu, Pb and Zn in surface soils derived from dredged sediments

Leaching of heavy metals from land-disposed dredged sediment spoils is a potential environmental hazard. The leaching behavior of Cd, Cu, Pb and Zn in surface soils sampled from abandoned dredged sediment disposal sites was assessed. Using simple mass-balance calculations, the significance of the leaching test results with respect to metal migration into underlying clean soil was appraised. The potential leachability, defined as the amounts released at constant pH 4, decreased in the order (% of total contents): Zn (58%) approximately equal to Cd (49%)>Cu (5%) approximately equal to Pb (2%). The kinetics of metal release were determined in a cascade shaking test using de-mineralized water acidified to pH 4 (HNO(3)). Metal concentrations in the leachates were low and metal migration was, assuming uniform convective flow, predicted to be of no environmental concern. It is emphasized that any long-term prediction of metal migration is uncertain.     

Heavy metals in urban soils of East St. Louis, IL, Part I: Total concentration of heavy metals in soils

The city of East St. Louis, IL, has a history of abundant industrial activities including smelters of ferrous and non-ferrous metals, a coal-fired power plant, companies that produce organic and inorganic chemicals, and petroleum refineries. A protocol for soil analysis was developed to produce sufficient information on the extent of heavy metal contamination in East St. Louis soils. Soil cores representing every borough of East St. Louis were analyzed for heavy metals--As, Cd, Cu, Cr, Hg, Ni, Pb, Sb, Sn, and Zn. The topsoil contained heavy metal concentrations as high as 12.5 ppm Cd, 14,400 ppm Cu, ppm quantities of Hg, 1860 ppm Pb, 40 ppm Sb, 1130 ppm Sn, and 10,360 ppm Zn. Concentrations of Sb, Cu, and Cd were well correlated with Zn concentrations, suggesting a similar primary industrial source. In a sandy loam soil from a vacated rail depot near the bank of the Mississippi River, the metals were evenly distributed down to a 38-cm depth. The clay soils within a half-mile downwind of the Zn smelter and Cu products company contained elevated Cd (81 ppm), Cu (340 ppm), Pb (700 ppm), and Zn (6000 ppm) and displayed a systematic drop in concentration of these metals with depth. This study demonstrates the often high concentration of heavy metals heterogeneously distributed in the soil and provides baseline data for continuing studies of heavy metal soil leachability.     

Heavy Metals in Urban Soils of East St. Louis,IL, Part I: Total Concentration of Heavy Metals in Soils

ABSTRACT

The city of East St. Louis, IL, has a history of abundant industrial activities including smelters of ferrous and non-ferrous metals, a coal-fired power plant, companies that produce organic and inorganic chemicals, and petroleum refineries. A protocol for soil analysis was developed to produce sufficient information on the extent of heavy metal contamination in East St. Louis soils. Soil cores representing every borough of East St. Louis were analyzed for heavy metals—As, Cd, Cu, Cr, Hg, Ni, Pb, Sb, Sn, and Zn. The topsoil contained heavy metal concentrations as high as 12.5 ppm Cd, 14,400 ppm Cu, ppm quantities of Hg, 1860 ppm Pb, 40 ppm Sb, 1130 ppm Sn, and 10,360 ppm Zn. Concentrations of Sb, Cu, and Cd were well correlated with Zn concentrations, suggesting a similar primary industrial source. In a sandy loam soil from a vacated rail depot near the bank of the Mississippi River, the metals were evenly distributed down to a 38-cm depth. The clay soils within a half-mile downwind of the Zn smelter and Cu products company contained elevated Cd (81 ppm), Cu (340 ppm), Pb (700 ppm), and Zn (6000 ppm) and displayed a systematic drop in concentration of these metals with depth. This study demonstrates the often high concentration of heavy metals heterogeneously distributed in the soil and provides baseline data for continuing studies of heavy metal soil leachability.     

Difference of lead,copper and zinc concentrations between interiors and exteriors of peds in some contaminated soils

Solute transport of elements in soils depends on the soil structural and hydraulic properties, and it is controlled by sorption and diffusion, which both limit the mobility and distribution of elements in soils. This study was conducted to compare lead (Pb), copper (Cu) and zinc (Zn) concentrations between ped exteriors and interiors of some contaminated soils. The results show that the differences of the heavy metals between exteriors and interiors decreased in the order clayey soil, clayey loam soil, loam soil. For same soils, the differences decreased from Pb to Cu to Zn. The differences in readily extractable concentrations of the three metals between ped exteriors and interiors were much larger than the differences in their total metals, this may indicate that extractable metals were more recently deposited. The higher Pb and Cu concentrations in the ped exteriors than interiors may additionally be explained by anthropogenic input, movement and downward through preferential flow.     

Spatial distribution of heavy metals in urban soils of Naples city (Italy)

Concentrations of surface and sub-surface soil Cu, Cr, Pb and Zn in the Naples city urban area were measured in 1999. Contourmaps were constructed to describe the metals spatial distribution. In the most contaminated soil samples, metals were speciated by means of the European Commission sequential extraction procedure. At twelve sites, Cu, Pb and Zn levels in soil were compared with those from a 1974 sampling. Many surface soils from the urban area as well as from the eastern industrial district contained levels of Cu, Pb and Zn that largely exceeded the limits (120, 100 and 150 mg kg(-l) for Cu, Pb and Zn, respectively) set for soils of public, residential and private areas by the Italian Ministry of Environment. Chromium values were never above regulatory limits(120 mg kg(-1)). Copper apparently accumulates in soils contiguous to railway lines and tramway. Cu and Cr existed in soil mainly inorganic forms (-68%), whereas Pb occurs essentially as residual mineral phases (77%). The considerable presence of Zn in the soluble, exchangeable and carbonate bound fraction (23%) suggests this element has high potential bioavailability and leachability through the soil. Concentrations of Cu, Pb and Zn have greatly increased since the 1974 sampling, with higher accumulation in soils from roadside fields.     

A comparison of physiologically based extraction test (PBET) and single-extraction methods for release of Cu, Zn, and Pb from mildly acidic and alkali soils

In vitro digestion test can be applied to evaluate the bioaccessibility of soil metals by measuring the solubility of the metals in synthetic human digestive tract. Physiologically based extraction test (PBET), composed of sequential digestion of gastric and intestinal phase, is one of the frequently used in vitro digestion tests. In this study, the PBET was chosen to determine the bioaccessibility of Cu, Zn, and Pb in 14 mildly acidic and alkali (pH 5.87–8.30) soils. The phytoavailability of Cu, Zn, and Pb in the same soils was also measured using six single-extraction methods (0.1 M HNO₃, 0.4 M HOAc, 0.1 M NaNO₃, 0.01 M CaCl₂, 0.05 M EDTA, and 0.5 M DTPA). The extraction efficiencies of the methods were compared. The PBET had a strong ability to extract metals from soil, which was much greater than neutral salt extraction and close to dilute acid and complex extraction in spite of the last 2 h neutral intestinal digestion. The amounts of bioaccessible Cu, Zn, and Pb in the gastric phase and in the gastrointestinal phase were both largely determined by the total content of soil Cu, Zn, and Pb. But the results of gastrointestinal digestion reflected more differences resulting from element and soil types than those of gastric digestion did. It was noticed that most of variations in the amounts of soil Cu, Zn, and Pb extracted by EDTA were well explained by the total soil Cu, Zn, and Pb, as same as the PBET. Moreover, the solubility of Cu, Zn, and Pb in the gastric phase and gastrointestinal phase were all positively linearly correlated with the results of EDTA. It was suggested that EDTA extraction can be used to predict the bioaccessibility of Cu, Zn, and Pb in mildly acidic and alkali (pH?>?5.8) soils, and the PBET and EDTA could be applied to measure, in a certain extent, the bioaccessibility and phytoavailability of Cu, Zn, and Pb in mildly acidic and alkali (pH?>?5.8) soils at the same time.     

Impact of lime-stabilized biosolid application on Cu,Ni, Pb and Zn mobility in an acidic soil

A soil column leaching study was conducted on an acidic soil in order to assess the impact of lime-stabilized biosolid on the mobility of metallic pollutants (Cu, Ni, Pb and Zn). Column leaching experiments were conducted by injecting successively CaCl₂, oxalic acid and ethylenediaminetetraacetic acid (EDTA) solutions through soil and biosolid-amended soil columns. The comparison of leaching curves showed that the transport of metals is mainly related to the dissolved organic carbon, pH and the nature of extractants. Metal mobility in the soil and biosolid-amended soils is higher with EDTA than with CaCl₂ and oxalic acid extractions, indicating that metals are strongly bound to solid-phase components. The single application of lime-stabilized biosolid at a rate ranging from 15 to 30 t/ha tends to decrease the mobility of metals, while repeated applications (2?×?15 t/ha) increase metal leaching from soil. This result highlights the importance of monitoring the movement and concentrations of metals, especially in acid and sandy soils with shallow and smaller water bodies.     

Leaching of heavy metals and alkylphenolic compounds from fresh and dried sewage sludge

Reusing sewage sludge as a soil fertiliser has become a common alternative to disposal. Although this practice has a few benefits, it may contribute to the medium- and long-term contamination of the trophic chain because sewage sludge may contain heavy metals and organic contaminants. As the leaching of contaminants may depend on the sludge pre-treatment, the leaching of heavy metals (Cu, Ni, Pb, Zn and Cr) and alkylphenolic compounds (APCs) (octylphenol (OP), nonylphenol (NP), nonylphenol-mono-ethoxylate (NP₁EO)) was investigated in five fresh and 40 °C dried sewage sludge samples from north-eastern Spain. FT-IR analyses and full-scan GC-MS chromatograms showed that sludge drying changed the nature of organic compounds leading to changes in their solubility. Moreover, sludge drying led to a higher relative contribution of dissolved organic carbon than the particulate organic carbon in the leachates. Leaching of Pb, Zn and Cr was below 5 % in both fresh and dried sludge samples, whereas Cu and Ni leached at rates up to 12 and 43 %, respectively, in some of the dried sludge samples. The leaching yields of OP, NP and NP₁EO ranged from 1.3 to 35 % for fresh samples, but they decreased from 0.8 to 3.4 % in dried samples. The decrease in the leachability of APCs observed in dried sludge samples might be attributed to the fact that these compounds are associated with particulate organic matter, with significantly lower concentration or even absent in dried sludge than in fresh sludge samples. Therefore, it is recommended to dry the sludge before its disposal.