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.     

Mobility of Pb, Cu, and Zn in the phosphorus-amended contaminated soils under simulated landfill and rainfall conditions

Phosphorus-bearing materials have been widely applied in immobilization of heavy metals in contaminated soils. However, the study on the stability of the initially P-induced immobilized metals in the contaminated soils is far limited. This work was conducted to evaluate the mobility of Pb, Cu, and Zn in two contrasting contaminated soils amended with phosphate rock tailing (PR) and triple superphosphate fertilizer (TSP), and their combination (P?+?T) under simulated landfill and rainfall conditions. The main objective was to determine the stability of heavy metals in the P-treated contaminated soils in response to the changing environment conditions. The soils were amended with the P-bearing materials at a 2:1 molar ratio of P to metals. After equilibrated for 2 weeks, the soils were evaluated with the leaching procedures. The batch-based toxicity characteristic leaching procedure (TCLP) was conducted to determine the leachability of heavy metals from both untreated and P-treated soils under simulated landfill condition. The column-based synthetic precipitation leaching procedure (SPLP) were undertaken to measure the downward migration of metals from untreated and P-treated soils under simulated rainfall condition. Leachability of Pb, Cu, and Zn in the TCLP extract followed the order of Zn?>?Cu?>?Pb in both soils, with the organic-C- and clay-poor soil showing higher metal leachability than the organic-C- and clay-rich soil. All three P treatments reduced leachability of Pb, Cu, and Zn by up to 89.2, 24.4, and 34.3 %, respectively, compared to the untreated soil, and TSP revealed more effectiveness followed by P?+?T and then PR. The column experiments showed that Zn had the highest downward migration upon 10 pore volumes of SPLP leaching, followed by Pb and then Cu in both soils. However, migration of Pb and Zn to subsoil and leachate were inhibited in the P-treated soil, while Cu in the leachate was enhanced by P treatment in the organic-C-rich soil. More than 73 % P in the amendments remained in the upper 0–10 cm soil layers. However, leaching of P from soluble TSP was significant with 24.3 % of P migrated in the leachate in the organic-C-poor soil. The mobility of heavy metals in the P-treated soil varies with nature of P sources, heavy metals, and soils. Caution should be taken on the multi-metal stabilization since the P amendment may immobilize some metals while promoting others’ mobility. Also, attention should be paid to the high leaching of P from soluble P amendments since it may pose the risk of excessive P-induced eutrophication.     

Immobilization of lead in shooting range soils by means of cement, quicklime, and phosphate amendments

BACKGROUND, AIM, AND SCOPE: Lead (Pb) contamination at shooting range sites is increasingly under environmental concern. Controlling Pb leachability from shooting range soil media is an important step to minimize Pb exposure to the surrounding environment. This study investigated stabilization of Pb in shooting range soils treated with cement, quicklime, and phosphate. MATERIALS AND METHODS: Two soils were used and collected from two shooting ranges, referred to as SR1 and SR2. The treatment additives were applied to the soils at rates from 2.5% to 10% (w/w). The effectiveness of each treatment was evaluated by Pb (w/w). The effectiveness of each treatment was evaluated by Pb leachability, measured by the Toxicity Characteristic Leaching Procedure (TCLP). The possible mechanisms for Pb immobilization were elucidated using X-ray powder diffraction (XRPD). RESULTS: Cement and quicklime treatments were effective in immobilizing Pb in SR1 soil, with reduction of Pb concentration in TCLP leachate (TCLP-Pb) to be below the U.S. EPA non-hazardous regulatory limit of 5 mg L(-1) at application rates of > or =5% and 28-d incubation. By contrast, cement and quicklime amendments were less effective for Pb stabilization in SR2 soil because the TCLP-Pb levels in the treated soil were still higher than the limit of 5 mg L(-1) at all application rates, although they were significantly reduced in comparison with the untreated soil. Phosphate application was most effective in reducing Pb leach ing in both soils. Even at an application rate as low as 5% and 1-d incubation, phosphate could reduce TCLP-Pb to be below the limit of 5 mg L(-1) in both soils. DISCUSSION: Immobilization of Pb in the SR1 soil amended with cement and quicklime was attributed to the formation of pozzolanic minerals (e.g., calcium silicate hydrate C-S-H and ettringite) that could encapsulate soil Pb. The pozzolanic reaction was limited in the SR2 soil upon the application of cement and quicklime. Reduction of the TCLP-Pb might result from complexation of Pb on the surface of the formed calcite. Phosphate-induced Pb immobilization was mainly attributed to formation of less soluble PbHPO4. CONCLUSIONS: The results indicate that effectiveness of cementitious treatments (cement and quicklime) in immobilizing Pb varies in two soils, being effective in SR1 soil but less in SR2 soil. For one given soil, no difference was observed of the effeciveness between cement and quicklime treatments, whereas phosphate amendment emerges as a most effective treatment means for stabilizing Pb in both two soils, and it also shows a faster immobilization process and little effect on the soil acid buffering capacity. Recommendations and Perspectives. Overall, our study reveals that immobilizing Pb can be one of the best management practices for Pb contamination at shooting range sites. Phosphate amendment is most effective in immobilizing Pb in any kind of the soil ranges to minimize negative Pb impacts on the shooting range sites.     

Thermal Immobilization of Lead Contaminants in Soils Treated in a Fixed- and Fluidized-Bed Incinerator at Moderate Temperatures

Abstract

Artificially lead-contaminated soils with different lead contents (200, 450, 600, and 900 ppm) were thermally immobilized in both fixed-bed and fluidized-bed modes at moderate treating temperatures (less than 500 °C) for various retention times. Cement powder and brick powder were added to the artificially contaminated soils to enhance lead immobilization. Results indicate that increasing treating temperature and time increases the extent of lead immobilization, as determined by the U.S. Environmental Protection Agency's (U.S. EPA) Toxicity Characteristics Leachability Procedure (TCLP). The percentage of lead leached from the soil/ cement mixtures was in the range of less than 0.251%, compared with the range between 13.6% and 40.7% for the corresponding soil/brick mixtures. As the amount of brick dust added to the Pb-doped soil was increased, the specific Pb immobilization effectiveness increased from 0.0675 to 0.149 mg Pb/g brick (for the 20- and 50-gram brick addition, respectively). An increase in air flow rate from 2 to 40 L/min caused a slight decrease in the Pb leaching percentage from 14.96% to 11.59%. Both the Freundlich and Langmuir isotherms give a satisfactory fit (r = 0.945 ~ 0.998) for the data derived from a TCLP test of the thermally-treated soil samples (105 °C and 500 °C) that contained lead contaminants. Sorption of lead contaminants in soil and sorbent matrices was the primary type of chemisorption. The kinetic results indicated that the Pb-doped soil system was too complicated to be described by a simple calculation.     

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.     

Investigations of ash topography/morphology and their relationship with heavy metals leachability

The leachability of heavy metals such as chromium (Cr), lead (Pb) and cadmium (Cd) from the ash material obtained from waste combustion was studied. The effects of ash surface topography and morphology on the leachability of these elements were examined using atomic force microscopy (AFM) and scanning electron microscopy (SEM). The AFM (scan size 10 x 10 microns) and SEM images of the simulated ash pellet obtained at various operating temperatures (1000, 1400 and 1500 degrees C) showed significant microstructural and topographical changes. Ash pellets treated at 1000 degrees C contain porous and non-continuous surface. On the other hand, the ash pellet obtained at higher temperature (1500 degrees C) was found to contain a smooth, continuous and non-porous surface. The AFM height profile studies indicated that the top surface variation of the ash pellet at 1000, 1400 and 1500 degrees C were found to be -40.0 to 25.5, -3.7 to 4.7 and -0.10 to 0.66 nm respectively. The SEM analyses also confirmed the presence of smooth, non-porous outer surface of ash formed at 1500 degrees C. In addition, it also showed the presence of compact and rigid interior for the same ash pellet. The leachability of the heavy metals was determined using standard toxicity characteristic leaching procedure (TCLP) test and the samples were analysed using atomic absorption spectroscopy. The results showed that the TCLP leaching ratios of the heavy metals were Cr = 0.30, Pb = 0.05 and Cd = 0.09 at 1000 degrees C. However, the ash obtained at 1400 degrees C showed negligible heavy metals leaching ratio while at 1500 degrees C no leachability was detected (TCLP concentration dropped to nondetectable levels). The use of high temperature treatment enabled the immobilization of heavy metals in the ash preventing their leaching. Such ash can be considered as a non-hazardous material for reuse or safe disposal.     

Contents and Leachability of Heavy Metals (Pb,Cu, Sb,Zn, As) in Soil at the Pantex Firing Range,Amarillo, Texas

ABSTRACT

Pantex firing range soil samples were analyzed for Pb, Cu, Sb, Zn, and As. One hundred ninety-seven samples were collected from the firing range and vicinity area. There was a lack of knowledge about the distribution of Pb in the firing range, so a random sampling with proportional allocation was chosen. Concentration levels of Pb and Cu in the firing range were found to be in the range of 11-4675 and 13-359 mg/kg, respectively. Concentration levels of Sb were found to be in the range of 1-517 mg/kg. However, the Zn and As concentration levels were close to average soil background levels. The Sn concentration level was expected to be higher in the Pantex firing range soil samples. However, it was found to be below the neutron activation analysis (NAA) detection limit of 75 mg/kg.

Enrichment factor analysis showed that Pb and Sb were highly enriched in the firing range with average magnitudes of 55 and 90, respectively. Cu was enriched ~6 times more than the usual soil concentration levels. Tox-icity characteristic leaching procedure (TCLP) was carried out on size-fractionated homogeneous soil samples. The concentration levels of Pb in leachates were found to be ~12 times higher than the U.S. Environmental Protection Agency (EPA) regulatory concentration level of 5 mg/L. Sequential extraction (SE) was also performed to characterize Pb and other trace elements into five different fractions. The highest Pb fraction was found with organic matter in the soil.     

Properties of biochars from conventional and alternative feedstocks and their suitability for metal immobilization in industrial soil

In contaminated soils, excessive concentrations of metals and their high mobility pose a serious environmental risk. A suitable soil amendment can minimize the negative effect of metals in soil. This study investigated the effect of different biochars on metal (Cu, Pb, Zn) immobilization in industrial soil. Biochars produced at 300 and 600 °C from conventional (MS, maize silage; WP, wooden pellets) and alternative (SC, sewage sludge compost; DR, digestate residue) feedstocks were used as soil amendments at a dosage of 10 % (w/w). The type of feedstock and pyrolysis temperature affected the properties of the biochars and their ability to immobilize metal in soil. Compared to production at 300 °C, all biochars produced at 600 °C had higher pH (6.2–10.7), content of ash (7.2–69.0 %) and fixed carbon (21.1–56.7 %), but lower content of volatile matter (9.7–37.2 %). All biochars except DR biochar had lower dissolved organic carbon (DOC) content (1.4–2.3 g C/L) when made at 600 °C. Only MS and SC biochars had higher cation exchange capacity (25.2 and 44.7 cmol/kg, respectively) after charring at 600 °C. All biochars contained low concentrations of Cd, Cu, Ni, Pb and Zn; Cd was volatilized to the greatest extent during pyrolysis. Based on FTIR analysis and molar ratios of H/C and O/C, biochars had a greater degree of carbonization and aromaticity after charring at 600 °C. The efficiency of the biochars in metal immobilization depended mainly on their pH, ash content, and concentration of DOC. SC and DR biochars were more effective for Cu and Zn immobilization than MS and WP biochars, which makes them attractive options for large-scale soil amendment.     

Stabilization and Solidification of Metal-Laden Wastes by Compaction and Magnesium Phosphate-Based Binder

ABSTRACT

Bench-scale and full-scale investigations of waste stabilization and volume reduction were conducted using spiked soil and ash wastes containing heavy metals such as Cd, Cr, Pb, Ni, and Hg. The waste streams were stabilized and solidified using chemically bonded phosphate ceramic (CBPC) binder, and then compacted by either uniaxial or harmonic press for volume reduction. The physical properties of the final waste forms were determined by measuring volume reduction, density, porosity, and compressive strength. The leachability of heavy metals in the final waste forms was determined by a toxicity characteristic leaching procedure (TCLP) test and a 90-day immersion test (ANS 16.1). The structural composition and nature of waste forms were determined by X-ray diffraction (XRD) and scanning electron microscopy (SEM), respectively.

CBPC binder and compaction can achieve 80-wt % waste loading and 39-47% reduction in waste volume. Compressive strength of final waste forms ranged from 1500 to 2000 psi. TCLP testing of waste forms showed that all heavy metals except Hg passed the TCLP limits using the phosphate-based binder. When Na₂S was added to the binder, the waste forms also passed TCLP limits for Hg. Long-term leachability resistance of the final waste forms was achieved for all metals in both soil and ash wastes, and the leachability index was ~14. XRD patterns of waste forms indicated vermiculite in the ash waste was chemically incorporated into the CBPC matrix. SEM showed that waste forms are layered when compacted by uniaxial press and are homogeneous when compacted by harmonic press.     

Contents and leachability of heavy metals (Pb, Cu, Sb, Zn, As) in soil at the Pantex firing range, Amarillo, Texas.

Pantex firing range soil samples were analyzed for Pb, Cu, Sb, Zn, and As. One hundred ninety-seven samples were collected from the firing range and vicinity area. There was a lack of knowledge about the distribution of Pb in the firing range, so a random sampling with proportional allocation was chosen. Concentration levels of Pb and Cu in the firing range were found to be in the range of 11-4675 and 13-359 mg/kg, respectively. Concentration levels of Sb were found to be in the range of 1-517 mg/kg. However, the Zn and As concentration levels were close to average soil background levels. The Sn concentration level was expected to be higher in the Pantex firing range soil samples. However, it was found to be below the neutron activation analysis (NAA) detection limit of 75 mg/kg. Enrichment factor analysis showed that Pb and Sb were highly enriched in the firing range with average magnitudes of 55 and 90, respectively. Cu was enriched approximately 6 times more than the usual soil concentration levels. Toxicity characteristic leaching procedure (TCLP) was carried out on size-fractionated homogeneous soil samples. The concentration levels of Pb in leachates were found to be approximately 12 times higher than the U.S. Environmental Protection Agency (EPA) regulatory concentration level of 5 mg/L. Sequential extraction (SE) was also performed to characterize Pb and other trace elements into five different fractions. The highest Pb fraction was found with organic matter in the soil.     

Stabilization and solidification of metal-laden wastes by compaction and magnesium phosphate-based binder

Bench-scale and full-scale investigations of waste stabilization and volume reduction were conducted using spiked soil and ash wastes containing heavy metals such as Cd, Cr, Pb, Ni, and Hg. The waste streams were stabilized and solidified using chemically bonded phosphate ceramic (CBPC) binder, and then compacted by either uniaxial or harmonic press for volume reduction. The physical properties of the final waste forms were determined by measuring volume reduction, density, porosity, and compressive strength. The leachability of heavy metals in the final waste forms was determined by a toxicity characteristic leaching procedure (TCLP) test and a 90-day immersion test (ANS 16.1). The structural composition and nature of waste forms were determined by X-ray diffraction (XRD) and scanning electron microscopy (SEM), respectively. CBPC binder and compaction can achieve 80-wt% waste loading and 39-47% reduction in waste volume. Compressive strength of final waste forms ranged from 1500 to 2000 psi. TCLP testing of waste forms showed that all heavy metals except Hg passed the TCLP limits using the phosphate-based binder. When Na2S was added to the binder, the waste forms also passed TCLP limits for Hg. Long-term leachability resistance of the final waste forms was achieved for all metals in both soil and ash wastes, and the leachability index was approximately 14. XRD patterns of waste forms indicated vermiculite in the ash waste was chemically incorporated into the CBPC matrix. SEM showed that waste forms are layered when compacted by uniaxial press and are homogeneous when compacted by harmonic press.     

Assessment of natural and calcined starfish for the amelioration of acidic soil

Quality improvement of acidic soil (with an initial pH of approximately 4.5) with respect to soil pH, exchangeable cations, organic matter content, and maize growth was attempted using natural (NSF) and calcined starfish (CSF). Acidic soil was amended with NSF and CSF in the range of 1 to 10 wt.% to improve soil pH, organic matter content, and exchangeable cations. Following the treatment, the soil pH was monitored for periods up to 3 months. The exchangeable cations were measured after 1 month of curing. After a curing period of 1 month, the maize growth experiment was performed with selected treated samples to evaluate the effectiveness of the treatment. The results show that 1 wt.% of NSF and CSF (700 and 900 °C) were required to increase the soil pH to a value higher than 7. In the case of CSF (900 °C), 1 wt.% was sufficient to increase the soil pH value to 9 due to the strong alkalinity in the treatment. No significant changes in soil pHs were observed after 7 days of curing and up to 3 months of curing. Upon treatment, the cation exchange capacity values significantly increased as compared to the untreated samples. The organic content of the samples increased upon NSF treatment, but it remains virtually unchanged upon CSF treatment. Maize growth was greater in the treated samples rather than the untreated samples, except for the samples treated with 1 and 3 wt.% CSF (900 °C), where maize growth was limited due to strong alkalinity. This indicates that the amelioration of acidic soil using natural and calcined starfish is beneficial for plant growth as long as the application rate does not produce alkaline conditions outside the optimal pH range for maize growth.     

Amelioration of acidic soil using various renewable waste resources

In this study, improvement of acidic soil with respect to soil pH and exchangeable cations was attempted for sample with an initial pH of approximately 5. Acidic soil was amended with various waste resources in the range of 1 to 5 wt.% including waste oyster shells (WOS), calcined oyster shells (COS), Class C fly ash (FA), and cement kiln dust (CKD) to improve soil pH and exchangeable cations. Upon treatment, the soil pH was monitored for periods up to 3 months. The exchangeable cations were measured after 1 month of curing. After a curing period of 1 month, a maize growth experiment was conducted with selected-treated samples to evaluate the effectiveness of treatment. The treatment results indicate that in order to increase the soil pH to a value of 7, 1 wt.% of WOS, 3 wt.% of FA, and 1 wt.% of CKD are required. In the case of COS, 1 wt.% was more than enough to increase the soil pH value to 7 because of COS's strong alkalinity. Moreover, the soil pH increases after a curing period of 7 days and remains virtually unchanged thereafter up to 1 month of curing. Upon treatment, the summation of cations (Ca, Mg, K, and Na) significantly increased. The growth of maize is superior in the treated samples rather than the untreated one, indicating that the amelioration of acidic soil is beneficial to plant growth, since soil pH was improved and nutrients were replenished.     

Sorption kinetics and leachability of heavy metal from the contaminated soil amended with immobilizing agent (humus soil and hydroxyapatite)

Release of heavy metals onto the soil as a result of agricultural and industrial activities may pose a serious threat to the environment. This study investigated the kinetics of sorption of heavy metals on the non-humus soil amended with (1:3) humus soil and 1% hydroxyapatite used for in situ immobilization and leachability of heavy metals from these soils. For this, a batch equilibrium experiment was performed to evaluate metal sorption in the presence of 0.05 M KNO(3) background electrolyte solutions. The Langmuir isotherms applied for sorption studies showed that the amount of metal sorbed on the amended soil decreased in the order of Pb(2+)>Zn(2+)>Cd(2+). The data suggested the possibility of immobilization of Pb due to sorption process and immobilization of Zn and Cd by other processes like co-precipitation and ion exchange. The sorption kinetics data showed the pseudo-second-order reaction kinetics rather than pseudo-first-order kinetics. Leachability study was performed at various pHs (ranging from 3 to 10). Leachability rate was slowest for the Pb(2+) followed by Zn(2+) and Cd(2+). Out of the metal adsorbed on the soil only 6.1-21.6% of Pb, 7.3-39% of Zn and 9.3-44.3% of Cd leached out from the amended soil.     

Increased bioavailability of metals in two contrasting agricultural soils treated with waste wood-derived biochar and ash

Recycled waste wood is being increasingly used for energy production; however, organic and metal contaminants in by-products produced from the combustion/pyrolysis residue may pose a significant environmental risk if they are disposed of to land. Here we conducted a study to evaluate if highly polluted biochar (from pyrolysis) and ash (from incineration) derived from Cu-based preservative-treated wood led to different metal (e.g., Cu, As, Ni, Cd, Pb, and Zn) bioavailability and accumulation in sunflower (Helianthus annuus L.). In a pot experiment, biochar at a common rate of 2 % w/w, corresponding to ～50 t ha^?1, and an equivalent pre-combustion dose of wood ash (0.2 % w/w) were added to a Eutric Cambisol (pH 6.02) and a Haplic Podzol (pH 4.95), respectively. Both amendments initially raised soil pH, although this effect was relatively short-term, with pH returning close to the unamended control within about 7 weeks. The addition of both amendments resulted in an exceedance of soil Cu statutory limit, together with a significant increase of Cu and plant nutrient (e.g., K) bioavailability. The metal-sorbing capacity of the biochar, and the temporary increase in soil pH caused by adding the ash and biochar were insufficient to offset the amount of free metal released into solution. Sunflower plants were negatively affected by the addition of metal-treated wood-derived biochar and led to elevated concentration of metals in plant tissue, and reduced above- and below-ground biomass, while sunflower did not grow at all in the Haplic Podzol. Biochar and ash derived from wood treated with Cu-based preservatives can lead to extremely high Cu concentrations in soil and negatively affect plant growth. Identifying sources of contaminated wood in waste stream feedstocks is crucial before large-scale application of biochar or wood ash to soil is considered.     

Gas permeability of biochar-amended clay: potential alternative landfill final cover material

Compacted biochar-amended clay (BAC) has been proposed as an alternative landfill final cover material in this study. Biochar has long been proposed to promote crop growth, mitigate odor emission, and promote methane oxidation in field soils. However, previous studies showed that soil-gas permeability was increased upon biochar application, which will promote landfill gas emission. The objective of the present study is to investigate the possibility of using compacted BAC as an alternative material in landfill final cover by evaluating its gas permeability. BAC samples were prepared by mixing 425-μm-sieved peanut shell biochar with kaolin clay in different ratios (0, 5, 10, and 15 %, w/w) and compacting at different degrees of compactions (DOC) (80, 85, and 90 %) with an optimum water content of 35 %. The gas permeability of the BACs was measured by flexible wall gas permeameter and the microstructure of the BACs was analyzed by SEM with energy-dispersive x-ray spectroscopy (EDX). The results show that the effects of biochar content on BAC gas permeability is highly dependent on the DOC. At high DOC (90 %), the gas permeability of BAC decreases with increasing biochar content due to the combined effect of the clay aggregation and the inhibition of biochar in the gas flow. However, at low DOC (80 %), biochar incorporation has no effects on gas permeability because it no longer acts as a filling material to the retard gas flow. The results from the present study imply that compacted BAC can be used as an alternative final cover material with decreased gas permeability when compared with clay.     

In situ immobilization of Cu(II) in soils using a new class of iron phosphate nanoparticles

This study tested the feasibility of using a new class of iron phosphate (vivianite) nanoparticles synthesized using sodium carboxymethyl cellulose (NaCMC) as a stabilizer for in situ immobilization of Cu(II) in soils. Transmission electron microscopy measurements demonstrated that the particle size was about 8.4+/-2.9 nm. Batch tests showed that nano-sized vivianite particles can effectively reduce the leachability and in vitro bioaccessibility of Cu(II) in three representative soils (calcareous, neutral, and acidic) at the low doses of 0.61 and 3.01 mg PO(4) g(-1) soil. The Cu leachability was evaluated by the toxicity characteristic leaching procedure and in vitro bioaccessibility was evaluated by the physiological based extraction test. In the case of soil amendment with nanoparticles in 3.01 mg PO(4) g(-1) soil, Cu leachability reduced 63-87% and Cu concentrations in TCLP extract decreased from 1.74-13.33 mg l(-1) to 0.23-2.55 mg l(-1) after those soils were amended for 56 d. Meanwhile, the bioaccessibility of Cu was reduced by 54-69%. Sequential extraction procedures showed the significant decrease of water soluble/exchangeable Cu(II) and carbonate bound fractions and concomitant increase of Cu residual fraction after the soils were amended with the nanoparticles, suggesting that the formation of copper phosphate minerals through precipitation and adsorption was probably responsible for the decrease of Cu availability in soils. Visual MINTEQ modeling further revealed that Cu(3)(PO(4))(2) and Cu(5)(PO(4))(3)OH were formed in the vivianite-solid Cu(II) system, resulting in the decreased solubility of the Cu(II) in the acidic pH range.     

Leaching behavior of Cr(III) in stabilized/solidified soil

The leaching behavior of chromium was studied using batch leaching tests, surface complexation modeling and X-ray absorption near edge structure (XANES) spectroscopy. A contaminated soil sample containing 1330 mg-Cr kg(-1) and 25600 mg-Fe kg(-1) of dry soil was stabilized/solidified (S/S) with 10% cement, 25% cement, 10% lime and a mixture of 20% flyash and 5% lime. The XANES analysis showed that Cr(III) was the only Cr species in untreated soil and S/S-treated samples. The leachate Cr concentration determined using the toxicity characteristic leaching procedure (TCLP) was reduced from 5.18 mg l(-1) for untreated soil to 0.84 mg l(-1) for the sample treated with 25% cement. The Cr leachability in untreated and treated soil samples decreased dramatically as the pH increased from 3 to 5, remained at similar levels in the pH range between 5 and 10.5, and further decreased at pH>10.5. Modeling results indicated that the release of Cr(III) was controlled by adsorption on iron oxides at pH<10.5, and by precipitation of Ca(2)Cr(2)O(5).6H(2)O at pH>10.5.     

Arsenic leachability and speciation in cement immobilized water treatment sludge

Arsenic leachability and speciation in cement immobilized water treatment sludge were investigated with leaching tests and X-ray absorption near edge structure (XANES) spectroscopy. The As leachability in the sludge determined with the toxicity characteristic leaching procedure (TCLP) and the waste extraction test (WET) was 283 and 7490 microgl(-1), respectively. Extractions with a lower liquid to solid ratio, under anaerobic conditions, and using citric acid buffer solution dramatically increased the leachate As concentration. XANES results showed that the As(III) composition was reduced from 51.1% of the total As content in the sludge to 16.3% in the cement treated sample with 28 days of cure. When the cement treated sample was cured for two years, the As(III) composition was decreased to 7.4%. The cement treatment reduced the As leachability. The leachate As(III) and total As concentrations were of the same order of magnitude in the samples cured for 28 days as for 2yr. However, consistently lower concentrations were detected in samples with longer cure time. The results of this study improve our understanding of arsenic speciation and leachability in the cement matrix after long cure times.     

Phosphate-induced metal immobilization in a contaminated site

To assess the efficiency of P-induced metal immobilization in soils, a pilot-scale field experiment was conducted at a metal contaminated site located in central Florida. Phosphate was applied at a P/Pb molar ratio of 4.0 with three treatments: 100% of P from H3PO4, 50% of P from H3PO4+ 50% of P from Ca(H2PO4)2, and 50% of P from H3PO4+5% phosphate rock in the soil. Approximately 1 year after P application, soil and plant samples were collected to determine mobility and bioavailability of selected metals (Pb, Zn, and Cu) using sequential extraction procedure and mineralogical characterization using X-ray diffraction (XRD) and scanning electron microscope-energy dispersive X-ray (SEM-EDX) analysis. Phosphorus distribution and soil pH effects were also evaluated. Phosphate was more effective in transforming soil Pb (to 53%) from the non-residual to the residual phase than soil Zn (to 15%) and soil Cu (to 13%). This was because Pb was immobilized by P via formation of an insoluble pyromorphite-like mineral in the surface and subsurface of the soil, whereas no phosphate mineral Zn or Cu was identified. While P amendment enhanced metal uptake in the roots of St. Augustine grass (Stenotaphrum secundatum), it significantly reduced metal translocation from root to shoot, especially Pb via formation of a pyromorphite-like mineral on the membrane surface of the root. A mixture of H3PO4 and phosphate rock was effective in metal immobilization, with less soil pH reduction and less soluble P. Although H3PO4 was effective in immobilizing Pb, its use should be limited to minimize soil pH reduction and potential eutrophication risk.