Immobilization of potentially toxic metals using different soil amendments

The in situ stabilization of potentially toxic metals (PTMs), using various easily available amendments, is a cost-effective remediation method for contaminated soils. In the present study, we investigated the effectiveness of apatite and a commercial mixture of dolomite, diatomite, smectite basaltic tuff, bentonite, alginite and zeolite (Slovakite) on Pb, Zn, Cu and Cd stabilization by means of decreasing their bioavailability in contaminated soil from an old lead and zinc smelter site in Arnoldstein, Austria. We also investigated the impact of 5% (w/w) apatite and Slovakite applications on soil functionality and quality, as assessed by glucose-induced soil respiration, dehydrogenase, acid and alkaline phosphatase and β-glucosidase activity. Both amendments resulted in increased soil pH and decreased PTM potential bioavailability assessed by diethylenetriamine pentaacetic acid extraction and by sequential extractions in the water-soluble and exchangeable fractions. The efficiency of stabilization was reflected in the soil respiration rate and in enzymatic activity. The β-glucosidase activity assay was the most responsive of them.     

Transport of chlorinated dioxins and furans in soil columns: modeling pentachlorophenol pole-treating oil influence

Column experiments were conducted to validate a screening model predicting the influence of pentachlorophenol (PCP) pole-treating oil on the vertical migration of its impurities, chlorinated dioxins and furans (PCDD/Fs). PCP pole-treating oil (15 mL d⁻¹) and water (20 mL d⁻¹) were added daily to the top of sand and organic soil columns during 35 d. Column soil samples were analyzed to determine concentrations of hydrocarbons and PCDD/Fs at several depths in the columns (0-30 cm) and their evolution in time (7, 14, 21 and 35 d).The model predicted a significant vertical migration of PCDD/Fs due to the presence of oil as a free phase and PCDD/Fs were found in the different column layers at concentrations consistent with model predictions (same order of magnitude). Measured PCDD/Fs concentrations are in total disagreement with literature data and with model prediction in the absence of oil free phase, which implies PCDD/F properties alone cannot be used to predict their fate in the current context: the influence of PCP pole-treating oil must be accounted for to properly explain their migration.     

Long-term sustainability of metal immobilization by soil amendments: Cyclonic ashes versus lime addition

A soil column leaching experiment was used to gain insight into the long-term metal immobilization capacity of cyclonic ashes (CAH) compared to lime (LIME). Twenty six years of rainfall were simulated. Initially, all amended soils were brought to an equal soil pH. This was done to obtain optimal conditions for the detection of metal immobilization mechanisms different from just a pH effect. During the simulation period, soil pH in all treatments decreased in parallel. However, the evolution of metal mobility and phytoavailability showed a clearly distinct pattern. The strong reduction in metal immobilizing efficiency observed in the lime treatment at the end of the simulation period was much less pronounced, or even absent, in the CAH treatments. Moreover, metal accumulation in plants grown on the CAH amended soil was significantly lower compared to the untreated and the lime treated soil. CAH + SS treatment delivered the strongest reductions in metal mobility and bioavailability.     

改良剂对土壤中Cu形态变化的影响

采用恒温连续培养的方法,以褐煤、腐殖酸、鸡粪为改良剂,探讨其对土壤中Cu形态变化的影响。结果表明,改良剂的加入均不同程度地改变了土壤pH值及有机质的含量。添加改良剂后土壤中Cu-WAE的含量降低,Cu-RES的含量升高,且Cu各种形态的分配比例发生了变化。相关性分析表明,各种Cu形态之间存在一定的相互关系,土壤中Cu-RED、Cu-RES受pH值影响较大,Cu-WAE、Cu-OXI受有机质影响较大。由再分配系数U可知,经褐煤、鸡粪处理后土壤中各种形态的Cu之间相互稳定,而经腐殖酸处理后各种形态的Cu之间不稳定,将会有较多的Cu-WAE进入到更稳定的形态中。添加改良剂的土壤中Cu的IR值大于CK中Cu的IR值,表明经过改良剂处理后的土壤中有较大比例的Cu结合在较稳定的形态中。3种改良剂对土壤都有较好的改良效果,有利于Cu的固定,降低了Cu的生物毒性。     

Influence of soil moisture on the sequestration of organic compounds in soil

A study was conducted as a part of continuing investigation of the effect of soil moisture on the sequestration of organic compounds aged in the soil. Here, experiments focused on the effects of moisture changes within the soil before, during, and after contaminant addition. The extractability of aged (68 d) phenanthrene was greater from soil that had been subjected to wetting and drying cycles prior to solute addition as compared to soil initially maintained at constant moisture. The recovery of phenanthrene added to moist soil was increased relative to extractability from soil that was air-dried at the time of the contaminant addition. Repeated wetting and drying of soil after the addition of atrazine or phenanthrene resulted in decreased extractability of the compounds as compared to samples maintained at constant moisture. A method for rapidly sequestering contaminants is proposed and may be useful in limiting the time required for laboratory studies involving “aged” contaminants. These data build upon the findings of earlier work from our laboratory and indicate that changes in the moisture conditions of soil can affect the availability of sequestered contaminants possibly through alterations in the structure of the natural solid.     

Effects of amendments on the uptake and distribution of DDT in Cucurbita pepo ssp pepo plants

The effects of soil amendments on the phytoextraction of ∑DDT (DDT + DDD + DDE) from soil ([∑DDT] ∼ 1500 ng/g) by a pumpkin variety of Cucurbita pepo ssp pepo were tested and the patterns of ∑DDT storage throughout the plant shoot were examined. The soil amendments did not increase the total amount of ∑DDT extracted into plant shoots, but new information about ∑DDT distribution in the plants was obtained. As observed previously, the ∑DDT concentration in plant leaves (mean 290 ng/g) was significantly lower than in plant stems (mean 2600 ng/g). Further analysis revealed that ∑DDT composition was consistent throughout the plant shoot and that ∑DDT concentration in leaves and stems decreased exponentially as distance from the root increased, which was previously unknown. This new information about the patterns of ∑DDT uptake and translocation within pumpkin plants highlights the need for appropriate plant sampling strategies in future POPs phytoextraction research.     

Relative bioavailability to laying hens of indicator polychlorobiphenyls present in soil

Transfer of indicator polychlorobiphenyls (PCBs) from soil into hen eggs may occur in hens reared outdoor, which ingest significant amounts of soil. This transfer depends on the bioavailability of the ingested compounds. The impact of soil on the bioavailability of indicator PCBs was assessed by means by a relative bioavailability (RBA) trial, in which their deposition in egg yolk and in abdominal fat, in response to their ingestion through contaminated-soil and through spiked-oil were compared. A sandy soil (709 μg indicator PCBs kg⁻¹ dry matter) was collected in the vicinity of a former fire involving treated wood. Twenty-eight laying hens were individually housed and fed one of the seven experimental diets during 14 d. The seven experimental diets were an uncontaminated control diet, three diets in which contaminated soil was introduced at levels of 3%, 6% and 9% and three diets in which spiked oil was introduced to achieve similar levels and profile of contaminants. Yolk, abdominal fat and liver were collected at the end of exposure. Indicator PCBs were extracted by ASE (Accelerated Solvent Extraction) and analyzed by GC-HMRS. Within each ingested matrix, the concentration of indicator PCBs in yolk and in abdominal fat linearly increased with the amount of indicator PCB ingested (P < 0.001). Except for PCB 28, the slopes of the responses to soil and to oil could not be differentiated (P > 0.1). RBA estimates did not differ from 1 for all indicator PCBs except for PCB 28, for which it was 0.58-0.59. Measurements performed on liver confirm these conclusions.     

Mortality of US pentachlorophenol production workers through 2005

A cohort of 2122 US pentachlorophenol (PCP) production workers from four plants in the National Institute for Occupational Safety and Health Dioxin Registry was exposed to PCP and to polychlorinated dibenzo-p-dioxin and dibenzofuran contaminants of PCP production. A subcohort of 720 was also exposed to 2,3,7,8-tetrachlorodibenzodioxin, a contaminant of trichlorophenol (TCP) while using TCP or a TCP derivative. PCP and several production contaminants have been implicated as animal carcinogens. A priori hypotheses were that the cohort would have elevated standardized mortality ratios (SMRs) for aplastic anemia, soft-tissue sarcoma, and non-Hodgkin lymphoma, as suggested by human studies, and for leukemia and liver, adrenal, thyroid, and parathyroid cancer, as suggested by animal studies. From 1940 to 2005 1165 deaths occurred with an overall SMR of 1.01 [95% confidence limits (CI), 0.95-1.07]. Overall cancer mortality (326 deaths, SMR 1.17, CI 1.05-1.31) was in statistically significant excess. There were excess deaths for trachea, bronchus and lung cancers (126 deaths, SMR 1.36, CI 1.13-1.62), non-Hodgkin lymphoma (17 deaths, SMR 1.77, CI 1.03-2.84), chronic obstructive pulmonary disease (63 deaths, SMR 1.38, CI 1.06-1.77), and medical complications (5 deaths, SMR 3.52, CI 1.14-8.22). In race- and sex-specific analyses, white males had increased non-Hodgkin lymphoma mortality (17 deaths, SMR 1.98, CI 1.15-3.17) and males of other races had increased leukemia mortality (four deaths, SMR 4.57, CI 1.25-11.7). The excess of cancers of a priori interest, non-Hodgkin lymphoma and leukemia, provide some support for the carcinogenicity of PCP, however, further studies with more detailed exposure assessment are needed.     

Use of amendments to reduce leaching loss of phosphorus and other nutrients from a sandy soil in Florida

Goal, Scope and Background Transport of P from agricultural land contributes to the eutrophication of surface waters. Soil amendment is considered one of the best management practices (BMPs) to reduce P loss from sandy soils. Laboratory column leaching experiments were conducted to evaluate the effectiveness of different soil amendments in reducing P leaching from a typical sandy soil in Florida. Methods The tested amendments were CaCl₂, CaCO₃, Al(OH)₃, cellulose, and mill mud, and applied at the rate of 15 g/kg for a single amendment and each 7.5 g/kg if two amendments were combined. Leaching was conducted every four days for 32 days, 250 mL of deionized water being leached for each column per leaching event. Leachates were collected from each leaching event and analyzed for reactive P, PO₄-P, and macro and micro-elements. Results and Discussion Except for the soils amended with CaCl₂, or CaCl₂+CaCO₃, reactive P and PO₄-P leaching losses mainly occurred in the first three leaching events. Phosphorus leaching from the soils amended with CaCl₂ or CaCl₂+CaCO₃ was less but more persistent than that of other amendments. Reactive Pleaching loss was reduced by 36.0% and 40.4% for the amendments of CaCl₂, and CaCl₂+CaCO₃, respectively, as compared with chemical fertilizer alone, and the corresponding values for PO₄-P were 70.8% and 71.9%. The concentrations of K, Mg, Cu, and Fe in leachate were also decreased by CaCl₂ or CaCl₂+CaCO₃ amendment. Among the seven amendments, CaCl₂, CaCO₃, or their combination were most effective in reducing P leaching from the sandy soil, followed by cellulose and Al(OH)₃, the effects of mill mud and mill mud + Al(OH)₃ were marginal. Conclusions These results indicate that the use of CaCl₂, CaCO₃, or their combination can significantly reduce P leaching from sandy soil, and should be considered in the development of BMPs for the sandy soil regions. Recommendations and Outlook Most agricultural soils in south Florida are very sandy with minimal holding capacities for moisture and nutrients. Repeated application of fertilizer is necessary to sustain desired yield of crops on these soils. However, eutrophication of fresh water systems in this area has been increasingly concerned by the public. Losses of P from agricultural fields by means of leaching and surface runoff are suspected as one of the important non-point contamination sources. The benefits and effectiveness of soil amendment in reducing P losses from cropping production systems while sustaining desired crop yield need to be demonstrated. Calcium chloride, CaCO₃, or their combination significantly reduce Pleaching from sandy soil, and should be considered in the development of BMPs for the sandy soil regions.     

Influence of organic amendments on diuron leaching through an acidic and a calcareous vineyard soil using undisturbed lysimeters

The influence of different organic amendments on diuron leaching was studied through undisturbed vineyard soil columns. Two composts (A and D), the second at two stages of maturity, and two soils (VR and Bj) were sampled. After 1 year, the amount of residues (diuron + metabolites) in the leachates of the VR soil (0.19-0.71%) was lower than in the Bj soil (4.27-8.23%), which could be explained by stronger diuron adsorption on VR. An increase in the amount of diuron leached through the amended soil columns, compared to the blank, was observed for the Bj soil only. This result may be explained by the formation of mobile complexes between diuron and water-extractable organic matter (WEOM) through the Bj soil, or by competition between diuron and WEOM for the adsorption sites in the soil. For both soils, the nature of the composts and their degree of maturity did not significantly influence diuron leaching.     

Characterization of an adsorbed humin-like substance on an allophanic soil formed via catalytic polycondensation between catechol and glycine, and its adsorption capability to pentachlorophenol

An allophanic soil (AS) catalyzed the formation of dark-colored polymers via polycondensation reactions between catechol and glycine. The organic carbon content of the AS was increased from 0.16% to 1.3%, indicating that some of the dark-colored polymers had been adsorbed to the AS. The characteristics of the dark-colored polymers adsorbed on the AS were similar to those of a humin that is not extractable with an aqueous alkaline solution. Such a humin-like substance (HuLS) was separated from the AS by treatment with a mixture of HF and HCl. The HuLS and humic acid-like substance (HaLS), comprising the acid-insoluble fraction in the reaction mixture, were characterized by elemental analysis, size exclusion chromatography, pyrolysis-GC/MS and ¹³C NMR. However, the structural features of HaLS and HuLS had many points in common. These results suggest that HuLS-AS can be regarded as an organo-clay complex formed by the strong adsorption of HaLS to the AS. The adsorption of pentachlorophenol (PCP) to AS and HuLS-AS was examined at pH 5.5. At this pH, the zeta potential of the HuLS-AS showed a negative value. It would, therefore, be expected that pentachlorophenolate anions would adsorb with difficulty to HuLS-AS because of electrostatic repulsion. Nevertheless, the adsorption coefficient for PCP to HuLS-AS, as estimated by the Freundlich isotherm, was seven times larger than that for AS. These results show that HuLS, when adsorbed on the AS surface, has the capability to enhance the adsorption of PCP.     

Effect of soil ageing on in vivo arsenic bioavailability in two dissimilar soils

Arsenic (As) bioavailability in spiked soils aged for up to 12 months was assessed using in vitro and in vivo methodologies. Ageing (natural attenuation) of spiked soils resulted in a decline in in vivo As bioavailability (swine assay) of over 75% in soil A (Red Ferrosol) but had no significant effect on in vivo As bioavailability even after 12 months of ageing in soil B (Brown Chromosol). Sequential fractionation, however, indicated that there was repartitioning of As within the soil fractions extracted during the time course investigated. In soil A, the As fraction associated with the more weakly bound soil fractions decreased while the residual fraction increased from 12% to 35%. In contrast, little repartitioning of As was observed in soil B indicating that natural attenuation may be only applicable for As in soils containing specific mineralogical properties.     

调理剂和通风方式对污泥生物干化效果的影响

采用了自主设计的污泥生物干化实验室模拟系统,研究了调理剂、物料配比和通风方式等实验条件对脱水污泥生物干化的影响效果。研究结果表明,与锯末相比,秸秆有利于反应物料温度的上升,含水率下降程度更大;利用秸秆调节污泥初始含水率在60%和65%的实验条件下时,物料的平均含水率分别下降了7%和6%,当初始含水率65%时,生物堆体的温度和含水率没有明显的变化;与连续通风相比较,间歇通风的实验条件有利于生物堆体的温度的升高和干化效果;在该实验中,最佳的生物干化条件是以秸秆为调理剂,初始含水率调至65%以下,以间歇方式进行通风。     

Soil pH and Anion Abundance Affects on Copper Adsorption

Abstract

Copper (Cu) input to agricultural soils results from Cu containing pesticides and/or that in soil amendments, such as manure or sewage sludge. Soil and soil solution properties influence the adsorption and desorption of Cu by the soil, which in turn determines its plant availability and/or phytotoxicities. Effects of different anion enrichment in the equilibrium solution on Cu adsorption by different soils (pH range of 6.2–9.9) were investigated in this study over a range of Cu concentrations. With Cu concentrations in the range of 0–100 mg L^?1 in the equilibration solution, 95–99% of applied Cu was adsorbed by all three soils. The adsorption of Cu was similar regardless of using either 0.01 M CaCl₂ or Ca(NO₃)₂ as the equilibration solution. When the Cu concentration in the equilibration solution was further increased in the range of 500–2000 mg L^?1, the adsorption of Cu decreased from 60 to 24% of applied Cu in two soils with pH 6.2–7.9. In a high pH soil (pH = 9.9), the Cu adsorption decreased from 77 to 34%. Addition of incinerated sewage sludge (ISS) to a Palouse silt loam soil (pH = 6.2) increased the Cu adsorption as compared to that by unamended soil. This was, in part, due to an increase in the soil suspension pH with ISS amendment.     

EDTA and HCl leaching of calcareous and acidic soils polluted with potentially toxic metals: remediation efficiency and soil impact

The environmental risk of potentially toxic metals (PTMs) in soil can be diminished by their removal. Among the available remediation techniques, soil leaching with various solutions is one of the most effective but data about the impact on soil chemical and biological properties are still scarce. We studied the effect of two common leaching agents, hydrochloric acid (HCl) and a chelating agent (EDTA) on Pb, Zn, Cd removal and accessibility and on physico-chemical and biological properties in one calcareous, pH neutral soil and one non-calcareous acidic soil. EDTA was a more efficient leachant compared to HCl: up to 133-times lower chelant concentration was needed for the same percentage (35%) of Pb removal. EDTA and HCl concentrations with similar PTM removal efficiency decreased PTM accessibility in both soils but had different impacts on soil properties. As expected, HCl significantly dissolved carbonates from calcareous soil, while EDTA leaching increased the pH of the acidic soil. Enzyme activity assays showed that leaching with HCl had a distinctly negative impact on soil microbial and enzyme activity, while leaching with EDTA had less impact. Our results emphasize the importance of considering the ecological impact of remediation processes on soil in addition to the capacity for PTM removal.     

Migration of heavy metals in soil as influenced by compost amendments

Soils contaminated with heavy metals can pose a major risk to freshwaters and food chains. In this study, the success of organic and inorganic intervention strategies to alleviate toxicity in a highly acidic soil heavily contaminated with As, Cu, Pb, and Zn was evaluated over 112 d in a mesocosm trial. Amelioration of metal toxicity was assessed by measuring changes in soil solution chemistry, metal leaching, plant growth, and foliar metal accumulation. Either green waste- or MSW-derived composts increased plant yield and rooting depth, reduced plant metal uptake, and raised the pH and nutrient status of the soil. We conclude that composts are well suited for promoting the re-vegetation of contaminated sites; however, care must be taken to ensure that very short-term leaching pulses of heavy metals induced by compost amendment are not of sufficient magnitude to cause contamination of the wider environment.     

Release of pentachlorophenol from black carbon-inclusive sediments under different environmental conditions

To investigate the feasibility of using black carbon (BC) in the control of hydrophobic organic contaminants (HOCs) in sediment, we added BCs from various sources (rice straw charcoal (RC), fly ash (FC) and soot (SC)) to sediment to create different BC-inclusive sediments and studied the release of pentachlorophenol (PCP) in the sediments under different condition. Different pH values had no obvious effect on the release of PCP in BC-inclusive sediment, but solid/liquid ratio, temperature, salinity and dissolved organic matter (DOM) content had significant influences on the release of PCP in all sediments except the RC-inclusive sediment. Adding 2% RC to sediment resulted in a 90% decrease in PCP release, which was a greater decrease than observed with FC- and SC-inclusive sediments. Therefore, from the standpoint of HOC release, the application of RC is feasible for organic pollution control in the water environment.     

钝化剂在烟草植物修复铅镉污染土壤中的作用

重金属钝化剂可以改变土壤中重金属的形态,降低其在土壤中的有效浓度、植物毒性及生物有效性,影响污染土壤中植物的生长及其对重金属的吸收。在温室盆栽条件下研究了施加羟基磷灰石（HA）、纳米羟基磷灰石（nHA）、纳米零价铁（nFe0）和纳米TiO2（nTiO2）对烟草植物修复铅镉污染土壤的作用。结果表明,HA降低土壤中Ph、cd的有效性、促进烟草生长、增加了烟草叶、茎、根中cd的吸收量和根系中Pb的吸收量,有利于Ph、cd的钝化和植物修复。nHA也可以降低土壤中Pb、cd的有效性,增加了烟草叶中cd的吸收量,有利于Pb、cd的钝化和cd的植物提取。nFe0和nTiO2：对于土壤Pb和cd的钝化作用和植物修复均没有显著影响。综合来看,HA最适合应用于烟草植物修复铅镉污染土壤。     

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.     

钝化剂在烟草植物修复铅镉污染土壤中的作用简

重金属钝化剂可以改变土壤中重金属的形态,降低其在土壤中的有效浓度、植物毒性及生物有效性,影响污染土壤中植物的生长及其对重金属的吸收。在温室盆栽条件下研究了施加羟基磷灰石（HA）、纳米羟基磷灰石（nHA）、纳米零价铁（nFe⁰）和纳米TiO₂（nTiO₂）对烟草植物修复铅镉污染土壤的作用。结果表明,HA降低土壤中Pb、Cd的有效性、促进烟草生长、增加了烟草叶、茎、根中Cd的吸收量和根系中Pb的吸收量,有利于Pb、Cd的钝化和植物修复。nHA也可以降低土壤中Pb、Cd的有效性,增加了烟草叶中Cd的吸收量,有利于Pb、Cd的钝化和Cd的植物提取。nFe⁰和nTiO₂对于土壤Pb和Cd的钝化作用和植物修复均没有显著影响。综合来看,HA最适合应用于烟草植物修复铅镉污染土壤。