Evaluation of fly ash,apatite and rice straw derived-biochar in varying combinations for in situ remediation of soils contaminated with multiple heavy metals

ABSTRACT

In

-situ sorbent amendment is a relatively low-cost, low-impact approach for remediation of soil contaminated with heavy metals (HMs), and thus is considered a way to be favored in developing countries. In this study, materials of non-hazardous, alkaline agronomic and industrial by-products were used as sorbents to explore their capacity of in situ immobilization of multiple HMs in mining-impacted arable soil. These sorbents included fly ash (FA), biochar (BC) and apatite (AP) and they were implemented with varying ratios of combinations. Results of soil microcosm tests showed that after incubation for 90 days, concentrations of Pb, Zn, and Cd in their exchangeable forms determined by a sequential extraction method significantly decreased in amended soils, as opposed to the unamended control. Of the five sets of amendments, the composite of FA, BC, and AP resulted in the maximum reduction (up to 80%) in the mobility of Pb, Zn, and Cd in soils. The mechanisms underlying the immobilization of HMs in amended soils might involve processes of surface precipitation, ion exchange and complexation, in which the physicochemical properties of sorbent materials played an important role. The immobilization efficacy of sorbent amendments on HMs in soil was further supported by pot experiments in which significant inhibition of HM accumulation in the belowground and aboveground tissues of maize was observed after 50-day cultivation in amended soils as compared with control soil. Together, these results suggest that the application of cost-saving and environmentally friendly materials derived from wastes as sorbents to remediate soils contaminated with multiple HMs is promising for developing countries like Vietnam.     

Application of soil amendments to contaminated soils for heavy metal immobilization and improved soil quality—a critical review

ABSTRACT

Today, soil metal pollution has become a significant environmental issue of great public concern. This is because soil is both a major sink for heavy metal(loid)s (HMs) released into the environment, by both pedogenic and anthropogenic activities; and also a major source of food chain contamination mainly through plant uptake and animal transfer. In addition, HM contamination of soil leads to negative impacts on soil characteristics and function by disturbing both soil biological and physiochemical properties (e.g. extreme soil pH, poor soil structure and soil fertility and lack of soil microbial activity). This eventually leads to decreased crop production. Various soil remediation techniques have been successfully employed to reduce the risks associated with HMs efflux into soil. Among these, the use of low-cost and environmentally safe inorganic and organic amendments for the in-situ immobilization of HMs has become increasingly popular. Immobilization agents have successfully reduced the availability of metal ions through a variety of adsorption, complexation, precipitation, and redox reactions. Soil amendments can also be a source of nutrients and thus can also act as a soil conditioner, improving the soil’s physiochemical properties and fertility, resulting in enhanced plant establishment in metal contaminated soils. This article critically reviews the use of immobilizing agents in HM contaminated agricultural and mining soils paying particular attention to metal immobilization chemistry and the effects of soil amendments on common soil quality parameters.     

Fractional and group composition of zinc and lead compounds as an indicator of the environmental status of soils

An ordinary chernozem artificially contaminated with Zn and Pb salts and reclaimed by the addition of chalk and glauconite under pot experimental conditions has been analyzed. The fractional and group composition of the metal compounds in the soil extracts have been determined according to an original combined fractionation procedure. Coefficients characterizing the changes in the environmental status of the metals under the reclamation conditions have been proposed for describing the formation tendencies of the metal composition in the soils. These are the mobility coefficients (MCs) of the heavy metals (HMs) in the soils and the stability coefficients (SCs) of the soils for the HMs. They are calculated from the analysis of the fractional and group composition of the metal compounds. The MC characterizes the environmental vulnerability of soils to the impact of HMs; the SC characterizes the environmental sustainability of soils concerning the contamination with HMs. The obtained experimental data characterize the behavior features of Zn and Pb in the studied soils. An increase in the environmental hazard has been revealed at the contamination of soils with HMs, as well as its decrease at the application of the tested ameliorants. The participation of both strongly and loosely fixed HM fractions in the development of the HM mobility in the soils and the sustainability of the soils to their impact has been shown.     

Heavy metals potentially drive co-selection of antibiotic resistance genes by shifting soil bacterial communities in paddy soils along the middle and lower Yangtze River

Heavy metals (HMs) and antibiotic resistance have become serious environmental problems affecting soil and human health. Soil microorganisms play key roles in pollutant degradation and biogeochemical cycling processes; however, the interactions among HMs, soil microbial communities, and antibiotic resistance genes (ARGs) in agricultural soils remain unclear. Using quantitative real-time polymerase chain reaction and NovaSeq sequencing, we evaluated heavy metal contents, abundances of ARGs, soil bacterial community structure and functions, and their correlations in paddy soils at 43 sampling sites along the middle and lower reaches of the Yangtze River, central and eastern China. Our results showed the co-occurrence of HMs, ARGs, and HM resistance genes across all paddy soils. Additionally, significant positive associations were detected between HMs and resistance genes. Cadmium, czcA, and int1 were positively correlated with bacterial community diversity. The Mantel test showed that bacterial community composition and functions were significantly associated with HMs and resistance genes, such as Cd, Cr, Zn, copA, czcA, int1, and sul1. Moreover, HMs and ARGs were the major factors shaping soil bacterial communities; thus, HMs triggered proliferation of HM and antibiotic resistances by influencing the mobile genetic element (int1) and soil microbial communities. Our study revealed that HMs potentially drive the co-selection of ARGs by shifting soil bacterial community structure and functions, thereby increasing the potential risks to human health as well as ecological environment in the paddy soils along the middle and lower reaches of the Yangtze River.     

Predicting the Phytoextraction Duration to Remediate Heavy Metal Contaminated Soils

The applicability of phytoextraction to remediate soils contaminated with heavy metals (HMs) depends on, amongst others, the duration before remediation is completed. The impact of changes in the HM content in soil occurring during remediation on plant uptake has to be considered in order to obtain a reliable estimate of the phytoextraction duration. To simulate the decrease in the HM content in soil and to assess the resulting decrease in the uptake of HMs by plants, contaminated soil was mixed with uncontaminated, but otherwise similar soil. Uptake of Cd, Pb, and Zn by the indicator plant Lupinus hartwegii and the Zn hyperaccumulator Thlaspi caerulescens (La Calamine ecotype) was a log-linear function of the in-situ measured HM soil solution concentrations. Over a wide range in dissolved Cd and Zn concentrations, uptake of these HMs by T. caerulescens was (much) greater than by L. hartwegii. Experimentally derived regression models describing the relationships between soil, soil solution, and plant were implemented in a HM mass balance model used to obtain estimates of the phytoextraction duration. For our target soils, estimates of the Cd phytoextraction duration using L. hartwegii or T. caerulescens increased significantly by more than 100 or 50 years when experimental soil—soil solution—plant relationships were used instead of the assumption of constant plant uptake of Cd. The two approaches gave similar results for phytoextraction of Zn by T. caerulescens.     

Humic Acids Increase the Phytoavailability of Cd and Pb to Wheat Plants Cultivated in Freshly Spiked, Contaminated Soil (7 pp)

Background, Aim and Scope   Humic acids (HAs) are the most important humified component of dissolved organic carbon (DOC) present in sewage water used for irrigation. It is well known that HAs affect the toxicity and availability of heavy metals (HMs) in soil-plant systems, and may increase the human exposure to HMs in contaminated soil through plant uptake. This study was conducted to assess the effects of HAs on HM availability, plant growth and HM uptake. Materials and Methods: With wheat (Triticum aestivum) as a test plant, a greenhouse pot experiment was conducted to investigate the effects of HAs in irrigation water on the phytoavailability of cadmium (Cd) and lead (Pb) in soil. Cd and Pb were added to the soil at concentrations of 1.5 and 150 mg/kg, respectively. Wheat seedlings grown in Cd and Pb-contaminated soil were watered with 4 levels of HA solution (0, 140, 280 and 560 mg/kg of HAs, respectively). Results: In control and Pb treatments, both plant biomass and plant HM concentrations increased with increasing concentrations of HAs in the solution. Plant biomass was markedly decreased when metal concentrations in plants increased, particularly in Cd and Cd/Pb treatments. In the soil, extractable metals, and water soluble organic carbon (WSOC) and its fractions significantly increased with increasing HA concentrations. Discussion: The results suggested that the application of HAs in barren soils may improve plant nutrition by mobilizing soil nutrients and providing plants with carbon sources. On the other hand, HAs present in sewage water may increase both the availability and transfer of HMs in the soil-plant continuum and subsequently increase human exposure to HMs in polluted soil. Conclusions. Conclusions: HA solution as irrigation water significantly increased HM availability to plants cultivated in the HM-amended soil and may increase the environmental risk of sewage irrigation. Recommendations and Perspectives: These results suggested that, when assessing the effect of sewage irrigation on soil quality, HAs contained in sewage water should be taken into consideration.     

Total soil heavy‐metal concentrations and mobile fractions after 10 years of biowaste‐compost fertilization

The accumulation of heavy metals (HMs) in soils is the most often cited potential risk of compost application. As the ecological effects of metals are related to mobile fractions rather than to total concentrations in the soil, we measured the total (aqua regia–extractable) HM concentrations, the readily available water‐soluble and the potentially bioavailable LiCl‐extractable fraction of soil HMs in a field experiment after 10 y with total applications of 95, 175, and 255 t ha^–1 biowaste compost (fresh matter). Total soil concentrations of Cd, Cr, Cu, Ni, and Pb in the compost treatments were not significantly higher than in the unfertilized control. Total Zn concentrations increased in the treatment with the highest application rate, as expected from the calculation of the Zn load in the composts. In the mobile fractions, as measured in soil saturation extract and LiCl extract, Cd and Pb were not detectable. Concentrations of Cr, Ni, and Zn were in the range published for unpolluted soils in other studies and did not show any differences according to treatment. Easily exchangeable Cu (in LiCl extract) was increased with compost fertilization, most probably due to complexation with low‐molecular organic complexants. Except for Cd and Zn, the results of the mobile HM fractions in the soil were in good agreement with plant HM concentrations. In conclusion, fertilization with high‐quality biowaste compost at such rates and after 10 y of application gives no cause for concern with regard to both total HM concentrations and available HM fractions.     

Source identification and assessment of heavy metal contamination in urban soils based on cluster analysis and multiple pollution indices

Purpose

To identify the sources and levels of contamination with anthropogenically derived heavy metals (HMs) for appropriate pollution control. We quantified anthropogenic influences with respect to HM pollution in soil, based on multiple pollution indices and cluster analysis derived from the results of an annual nationwide survey conducted in Korea.

Methods

Contamination levels of HMs in soils were quantitatively evaluated using multiple pollution indices: contamination factor (CF), geo-accumulation index (I_geo), Nemerow’s integrated pollution index (NIPI), and pollution load index (PLI). Hierarchical cluster analysis was conducted to elucidate the correlations between HMs and contamination sources. A total of 2214 HM concentration data including six contamination sources were used to evaluate the pollution state of anthropogenic effects of HMs.

Results

The CFs for Zn and Cu revealed a broad enrichment of these HMs in all pollution sources. Scrap recycling sites (SRS) had the highest likelihood of pollutant distribution in soil surfaces. NIPI and PLI varied with the extent of anthropogenic activities or land use, especially in SRS, waste disposal sites (WDS), transport maintenance sites (TMS), and industrial sites (INS), and anthropogenic sources were divided into three discrete clusters: INS-TMS-LDS (land development sites), SRS-WDS, and vicinities of industrial sites (VIS).

Conclusion

Our results confirmed that soil pollution indices combined with cluster analysis were useful to identify sources of anthropogenic HMs in urban soil, as well as to assess the levels of HM contamination.

     

Heavy‐metal displacement in chelate‐treated soil with sludge during phytoremediation

Heavy metals (HMs) in domestic sewage sludge, applied to land, contaminate soils. Phytoremediation is the use of plants to clean‐up toxic HMs from soil. Chelating agents are added to soil to solubilize the metals for enhanced uptake. Yet no studies report the displacement of HMs in soil with sludge following solubilization with chelates. The objective of this work was to determine the uptake or leaching of HMs due to a chelate added to a soil from a sludge farm that had received sludge for 25 y. The soil was placed in long columns (105 cm long; ?? 39 cm) in a greenhouse. Columns either had a plant (hybrid poplar; Populus deltoides Marsh. × P. nigra L.) or no plant. After the poplar seedlings had grown for 144 d, the tetrasodium salt of the chelating agent EDTA was irrigated onto the surface of the soil at a rate of 1 g per kg of soil. Drainage water, soil, and plants were analyzed for three toxic HMs (Cd, Ni, Pb) and four essential HMs (Cu, Fe, Mn, Zn). At harvest, extractable and total concentrations of each HM in the soil with EDTA were similar to those in soil without EDTA. The chelate did not affect the concentrations of HMs in the roots or leaves. With or without plants, EDTA mobilized all seven HMs and increased their concentrations in drainage water. Lower concentrations of Cd, Cu, Fe, Ni, and Zn in leachate from columns with EDTA and plants compared to columns with EDTA and no plants showed that poplars can reduce groundwater contamination by intercepting these HMs in the soil. But the poplar plants did not reduce Pb and Mn in the leachate from columns with EDTA. Concentrations of Cd and Pb in the leachate mobilized by EDTA remained above drinking‐water standards with or without plants. The results showed that a chelate (EDTA) should not be added to a soil at a sludge farm to enhance phytoremediation. The chelate mobilized HMs that leached to drainage water and contaminated it.     

Assessment of the migration of heavy metals in soils

Qualitative and quantitative studies of the kinetics and dynamics of technogenic migration of heavy metals (HMs) have been performed in laboratory experiments. It is shown that the redistribution of HMs applied into soils in neutral form has an impulsive pattern. Soil texture does not have a decisive influence on the migration capacity of metals. An important feature of the technogenic migration of HMs is the effect of the polymetallic contamination, upon which the migration capacity of a set of heavy metals is higher than that of separate metal compounds. An index characterizing the ratio of absolute values of migration rates of ionic forms of metals estimated from electrical conductivity values to the rate of infiltration of the soil solution (v_m/v_f) is suggested to estimate the kinetics of HM migration in soils.     

微尺度重金属土壤化学研究进展与展望

土壤重金属污染是我国面临的重要生态环境问题,有效管控与修复重金属污染土壤有必要弄清重金属与土壤固相组分的作用机制。土壤组成多样、结构复杂、空间异质,加之土壤团聚体粒径大小不一,形成微观结构和表面性质各异的土壤微域,控制着重金属的形态转化及生物有效性。因此,深入认识微尺度的重金属土壤化学对于预测和管控土壤重金属环境化学行为至关重要。同步辐射X射线微探针(Microprobe)、X射线扫描透射显微术(STXM)及纳米二次离子质谱技术(Nano SIMS)等技术具有微纳米级空间分辨率,为在环境意义尺度上探究微尺度重金属土壤化学提供了独特的支撑平台。本文从环境土壤化学发展历程及当前发展瓶颈、现代微尺度分析技术及其在微尺度重金属土壤化学中的应用进展等方面综述,并对该领域未来的发展进行了展望。     

Effects of Biochar and Biosolid on Adsorption of Nitrogen,Phosphorus, and Potassium in Two Soils

Increasing the retention of nutrients by agricultural soils is of great interest to minimize losses of nutrients by leaching and/or surface runoff. Soil amendments play a role in nutrient retention by increasing the surface area and/or other chemical processes. Biochar (BC) is high carbon-containing by-product of pyrolysis of carbon-rich feedstocks to produce bioenergy. Biosolid is a by-product of wastewater treatment plant. Use of these by-products as amendments to agricultural soils is beneficial to improve soil properties, soil quality, and nutrient retention and enhance carbon sequestration. In this study, the adsorption of NH₄-N, P, and K by a sandy soil (Quincy fine sand (QFS)) and a silty clay loam soil (Warden silty loam (WSL)) with BC (0, 22.4, and 44.8 mg ha^?1) and biosolid (0 and 22.4 mg ha^?1) amendments were investigated. Adsorption of NH₄-N by the QFS soil increased with BC application at lower NH₄-N concentrations in equilibrium solution. For the WSL soil, NH₄-N adsorption peaked at 22.4 mg ha^?1 BC rate. Biosolid application increased NH₄-N adsorption by the WSL soil while decreased that in the QFS soil. Adsorption of P was greater by the WSL soil as compared to that by the QFS soil. Biosolid amendment significantly increased P adsorption capacity in both soils, while BC amendment had no significant effects. BC and biosolid amendments decreased K adsorption capacity by the WSL soil but had no effects on that by the QFS soil. Ca release with increasing addition of K was greater by the WSL soil as compared to that by the QFS soil. In both the soils, Ca release was not influenced by BC amendment while it increased with addition of biosolid. The fit of adsorption data for NH₄-N, P, and K across all treatments and in two soils was better with the Freundlich model than that with the Langmuir model. The nutrients retained by BC or biosolid amended soils are easily released, therefore are readily available for the root uptake in cropped soils.     

Mycorrhizal association of Agrostis capillaris and Glomus intraradices under heavy metal stress: Combination of plant clones and fungal isolates from contaminated and uncontaminated substrates

The present study aimed to compare the impact of arbuscular mycorrhizal (AM) fungi on plant growth and heavy-metal (HM)-uptake when both plant and fungal symbionts originated either from contaminated or uncontaminated sites. HM-tolerance of six clones of the grass Agrostis capillaris and three isolates of the AM fungus Glomus intraradices of different origin was first tested separately. Plant clones from the vicinity of a lead smelter showed a consistently high HM-tolerance, whereas the control clones varied in their ability to cope with HMs. The AM isolate from the contaminated substrate also performed better under HM-stress than the isolates from uncontaminated soils. All A. capillaris clones were then grown in a contaminated substrate, uninoculated or inoculated either with a tolerant or non-tolerant G. intraradices isolate. Clones from the uncontaminated site accumulated considerably more HMs in their shoots and roots, regardless of inoculation. The effect of AM inoculation on plant growth and HM-uptake depended on the particular combination of plant clone and fungal isolate, without clear differences between tolerant and non-tolerant clones.     

生物炭/石灰混施对重金属复合污染土壤的稳定化效应

采用室内模拟实验,以南方砷镉铅复合污染的酸性红壤为对象,利用化学钝化原理,探讨钝化材料对重金属稳定化的技术效果及应用配方,以期为砷镉铅复合污染红壤修复与安全利用提供依据。具体做法为：选择生物炭（BC）和石灰（SH）为钝化材料,以土壤重量的1%、4%为材料添加量,单一或混合施用于砷镉铅复合污染土壤,并于恒温（25℃）条件下培养60d,在实验进行至第1天、第30天、第60天时取样,测定红壤酸碱度（pH）和水溶态（Water soluble）有效砷（As）、镉（Cd）、铅（Pb）即WSAs、WSCd、WSPb含量,以及土壤重金属As、Cd、Pb结合态含量与占比的变化,明确生物炭石灰单/混施对重金属的稳定化效应。结果表明：生物炭/石灰无论单施或混施均能不同程度地降低土壤中水溶态WSCd和WSPb含量,钝化效率分别为33.51%～78.89%和9.05%～96.24%。而材料单施（1BC、4SH）和两者混施高用量（4BC4SH）处理,均能大幅降低土壤中有效As含量,钝化效率为10.25%～55.27%,其中以两者混施高用量（4BC4SH）处理对土壤重金属As、Cd、Pb协同钝化的效果最佳,当培养实验进行至第60天时,钝化效率依次达55.27%、76.39%和96.24%。培养后土壤中As形态由易被植物吸收的非专性吸附态、专性吸附态转化为稳定的残渣态,土壤中Cd和Pb则由活性最强的酸可提取态转化为残渣态,土壤中As、Cd、Pb的稳定化效应明显,迁移系数下降;此外,生物炭/石灰的单施及混合施用,均可导致土壤酸碱度（pH）显著提升（P<0.05）,有利于南方酸化土壤的改良。总体而言,本研究中生物炭/石灰两者混施高用量水平下（4BC4SH）土壤重金属的钝化效果最优,可实现对As、Cd和Pb复合污染红壤的稳定化修复。     

Nutrient mobilization and nutrient contents of Zea mays in response to EDTA additions to heavy‐metal‐contaminated agricultural soil

Enhanced phytoextraction of heavy metals (HMs) using chelating agents and agricultural crops is widely tested as remediation technique for agricultural soils contaminated with less mobile HMs. Nutrients are complexed by chelating agents simultaneously to HMs. In this study, the effect of EDTA (ethylenediaminetetraacetic acid) application on nutrient mobility in the soil and nutrient contents of Zea mays was tested on the laboratory and on the field scale. EDTA effectively increased the mobility of total water‐soluble macronutrients (Ca, K, Mg, P) and micronutrients (Fe, Mn) in the soil solution. Thereby nutrient co‐mobilization did cause competition to target HMs during the phytoextraction process. Mobilization was caused by complexation of nutrient cations by negatively charged EDTA and by dissolution of oxides and hydroxides. Increased concentrations of negatively charged P indicate the dissolution of metal phosphates by EDTA. Higher total water‐soluble nutrient concentrations enhanced bioavailability and plant contents of all determined nutrients especially that of Fe. Mobilization of nutrients may result in leaching and loss of soil fertility.     

改良剂对镉污染酸性水稻土的修复效应与机理研究

为探明田间条件下施用石灰、钙镁磷肥、海泡石和腐殖酸等改良剂对Cd污染酸性水稻土的修复效应和作用机理, 通过在Cd污染区建立田间小区试验, 研究了改良剂单施和与石灰配施对Cd污染酸性水稻土中Cd作物有效性的影响。结果表明, 施用改良剂有效地改变了土壤中Cd的存在形态, 除腐殖酸外, 其他改良剂均使土壤酸提取态Cd不同程度地转化为可还原态Cd和残渣态Cd; 施用改良剂可使0.1 mol·L^-1 NaNO₃和 0.01 mol·L^-1CaCl₂提取态Cd 降低26%~97%, 降低效果为石灰+海泡石>海泡石>石灰+钙镁磷肥>钙镁磷肥>石灰>石灰+腐殖酸>腐殖酸; 改良剂使水稻地上部分的Cd吸收量降低6%~49%。试验结果还显示, 施用改良剂提高土壤pH是引起土壤中Cd作物有效性降低的主要原因之一。根据田间试验的结果, 海泡石可推荐作为Cd污染酸性水稻土的改良剂, 而腐殖酸则不宜使用。     

Microbial community structure and function in a soil contaminated by heavy metals: effects of plant growth and different amendments

We studied the effects of in situ remediation of a heavy metal (HM) contaminated soil on some soil chemical properties, microbial function and microbial structural diversity after 18 months. The experiment was carried out at semifield scale in containers filled with HM contaminated soil from the Aznalcóllar mine accident (Southern Spain, 1998). The remediation measures consisted of the application of different amendments and/or establishment of a plant cover (Agrostis stolonifera L.). Seven treatments were established: four organic treatments (municipal waste compost (MWC), biosolid compost (BC), leonardite (LEO) and litter (LIT)), one inorganic treatment (sugar beet lime (SL)) and two controls (control with plant cover (CTRP) and control without plant cover (CTR)). Several soil chemical (pH, soluble HM, total organic C (TOC), water-soluble C (WSC) and available-P) and biochemical properties (microbial biomass C (MBC), MBC/TOC ratio and enzyme activities) were determined. Microbial community structure was studied by means of ARDRA (amplified ribosomal DNA restriction analysis). The SL, MWC and BC treatments were the most efficient to raise soil pH and decrease soluble HM concentrations. Total organic C was increased in the organic treatments by 2 to 4-fold, whereas water-soluble C was statistically similar in the CTRP, SL and the organic treatments, probably due to the presence of a root system in all these treatments. Available-P was also increased in the BC, SL and MWC treatments due to the higher P content of the amendments applied in these treatments. Soil microbial function was generally enhanced in the amended and CTRP treatments. The MWC, BC and SL treatments were particularly efficient to increase microbial biomass C, the MBC/TOC ratio and the dehydrogenase and aryl-sulphatase enzyme activities. These results could be attributed to the amelioration of some of the soil chemical properties: increase in soil pH and water-soluble C and decrease of HM soluble concentrations. ARDRA analyses showed changes in structural diversity in both the bacterial and fungal community under the different treatments. Fingerprinting patterns of the 16S rDNA obtained with Hinf-I and of the 18S rDNA with Hpa-II revealed higher similarity percentages among samples from the same treatment compared with samples from the other treatments. In addition, a higher similarity was found between samples from all treatments under the Agrostis influence. The use of certain amendments and/or a plant cover is important for in situ remediation of HM contaminated soils, since these practices can affect soil chemical properties, as well as the microbial community function and structure.     

Speciation of Zn,Cu, and Pb in the soil depending on soil texture and fertilization with sewage sludge compost

Background, aim, and scope  Heavy metal (HM) mobility in soil depends on the HM species in it. Therefore, knowledge of the HM speciation in soil allows the prediction of HM impact on the environment. HM speciation in soil depends on the metal chemical origin, soil texture, and other factors such as the origin and level of soil contamination. Recently, the problem of organic waste utilization is of great importance as the amount of this recyclable material is continually increasing. One of the possible ways of recycling is the use of processed organic wastes for agricultural needs. In this research, aerobically composted sewage sludge was used, the utilization of which is of essential importance. But one of the most serious restrictions is HM transfer from such material to the soil. Therefore, a prediction of HM mobility in soil and its migration in the environment is an important issue when using sewage sludge compost (SSC) in agriculture. Zn, Cu, and Pb speciation was performed according to the modified methodology of Tessier et al. (Anal Chem 51:844–851, 1979) in two different (sandy and clay) soils with background HM amounts and in soil samples amended with aerobically digested SSC to find out the predominant species of the investigated HM and to predict their potential availability. Materials and methods  The modified method of sequential extraction initially proposed by Tessier et al. (Anal Chem 51:844–851, 1979) is designed for HM speciation into five species where HM mobility decreases in the order: F1—exchangeable HM (extracted with 1 M MgCl₂ at an initial pH of 7 and room temperature), F2—carbonate-bound HM (extracted with 1 M CH₃COONa buffered to pH 5 at room temperature), F3—Fe/Mn oxide-bound HM (extracted with 0.04 M NH₂OH·HCl at an initial pH of 2 at 96°C), F4—organic matter-complexed or sulfide-bound HM (extracted with 0.02 M HNO₃ and 30% (v/v) H₂O₂ at a ratio of 1:1 and an initial pH of 2 at 85°C), and F5—the residual HM (digested with HNO₃, HF, and HCl mixture). After digestion, HM amounts in solution were determined by atomic absorption spectrometry (AAS ‘Hitachi’). Mixtures of uncontaminated soils of different textures (clay and sandy) with SSC in ratios 20:1, 10:1, and 5:1 were used to simulate the land application with SSC. During a period of 7 weeks, changes in Zn, Cu, and Pb content within species were investigated and compared weekly in soil–SSC mixtures with their speciation in pure soil and in the SSC. Results  Results in the SSC showed that more HM were found as mobile species compared to the soils, and in sandy soil, more were found in the mobile species than in clay soil. But the HM speciation strongly depended on the metal chemical origin. According to the potential availability, HM ranked in the following order: Zn>Pb>Cu. Zinc generally occurred in the mobile species (F1 and F3), especially in sandy soils amended with SSC, and changes of the Zn speciation were insignificant at the end of the experiment. Pb transfer to insoluble compounds (F5) was evident in the SSC–soil mixtures. This confirms that Pb is extremely immobile in the soil. However, the observed increase of Pb amounts in the mobile species (F1 and F2) during the course of experiment shows a critical trend of Pb mobilization under anthropogenic influence. Copper in the soil–SSC mixtures had a trend to form compounds of low mobility, such as organic complexes and sulfides (F4) and nonsoluble compounds (residual fraction F5). Initially, the amounts of mobile Cu species (F1 and F2) increased in the soils amended with SSC, probably due to the influence of SSC of anthropogenic origin with lower pH and high organic matter content, but Cu mobility decreased nearly to the initial level again after 3–4 weeks. Hence, the soil has a great specific adsorption capacity to immobilize Cu of anthropogenic origin. Discussion  Zn mobility and environmental impact was greater than that seen for Cu and Pb, while mobility of both Cu and Pb was similar, but variable depending on soil texture and contamination level. The effect on the shift of HM mobility and potential availability was greater in sandy SSC-amended soils than in clay soils and increased with an increasing amount of SSC. Conclusions  Usage of SSC for land fertilization should be strictly regulated, especially regarding Pb amounts. Recommendations and perspectives  The influence of SSC on Cu and Zn mobility and potential availability was more significant only in the case of sandy soil with a higher SSC ratio. Nevertheless, this waste product of anthropogenic origin increased Pb mobility in all cases in spite of only moderate Pb mobility in SSC itself. Therefore, aerobic processing of sewage sludge must be strictly regulated, especially regarding Pb amounts, and SSC ratios must be in control regarding HM amounts when using it for on-land application.     

Efficiency of KOH-modified rice straw-derived biochar for reducing cadmium mobility, bioaccessibility and bioavailability risk index in red soil

Cadmium (Cd) pollution in agricultural soils has exerted a serious threat due to continuous application of pesticides, fertilizers, and wastewater irrigation. The present study aimed to test the efficiency of KOH-modified and non-modified rice straw-derived biochar (KBC and BC, respectively) for reducing Cd solubility and bioavailability in Cd-contaminated soil. Cadmium-contaminated soil was incubated for 60 d with 15 and 30 g kg^-1 BC and KBC. At the end of incubation, Cd mobility was estimated by the European Community Bureau of Reference sequential extraction and toxicity characteristic leaching procedure (TCLP), while bioavailability was determined using 1 mol L^-1 NH₄NO₃ extraction. The bioavailability risk index and bioaccessibility, assessed by a simple bioaccessibility extraction test, of Cd were used to examine the potential effects of Cd on living organisms. The results indicated that application of both KBC and BC significantly increased soil pH, cation exchange capacity, nutrients, and organic carbon. The soluble fraction of Cd was significantly decreased by 30.3% and 27.4%, respectively, with the addition of KBC and BC at 30 g kg^-1 compared to the control (without biochar addition). Similarly, the bioaccessible Cd was significantly decreased by 32.4% and 25.2%, respectively, with the addition of KBC and BC at 30 g kg^-1 compared to the control. In addition, both KBC and BC significantly reduced Cd leaching in the TCLP and NH₄NO₃-extractable Cd in the amended soil compared to the control. The reduction in Cd solubility and bioaccessibility by KBC and BC may be due to significant increases in soil pH and surface complexation. Overall, KBC at an application rate of 30 g kg^-1 demonstrated positive results as soil amendment for Cd immobilization, and reduced bioaccessible Cd in contaminated soil.     

Remediation of a soil contaminated with heavy metals by immobilizing compounds

The labile fraction of heavy metals (HM) in soils is the most important for toxicity for plants and microorganisms. Thus, it is crucial to reduce this fraction in contaminated soils to decrease the negative effect of HM. In a greenhouse experiment, the effects of several additives on the labile fractions of Zn, Cd, Cu, Ni, and Pb were investigated in a soil contaminated during long‐term sewage‐sludge application. The accumulation of HM was studied in the aboveground biomass of wheat (Triticum aestivum L.). The additives used were the clay minerals Na‐bentonite, Ca‐bentonite, and zeolite; the Fe oxides hematite and goethite; the phosphate fertilizers superphosphate and Novaphos. Wheat was planted three times during 5 months, allowed to grow for 7 w, and harvested. Dry matter and HM content of shoots were determined after each harvest. Soil samples were taken after the first and third harvest, and the NH₄NO₃‐extractable HM contents were determined. After the addition of 2% Na‐bentonite as well as 2% Ca‐bentonite, a strong reduction of the labile HM soil fraction and shoot HM concentration was observed. At the end of the experiment, the labile fraction was reduced due to the addition of Na‐bentonite and Ca‐bentonite by 24% and 31% for Zn, by 37% and 36% for Cd, by 41% and 43% for Cu, by 54% and 61% for Ni, and by 48% and 41% for Pb, respectively. Furthermore, the shoot HM concentrations with the exception of Zn were reduced below the phytotoxicity range. Accordingly, the shoot dry‐matter production was significantly increased. The addition of phosphate fertilizers (notably Novaphos) strongly reduced the bioavailability of Pb for wheat plants. By addition of 0.05% Novaphos, the labile fraction and the shoot concentration of Pb were lowered by 39% and 64%, respectively. However, the addition of Fe oxides and zeolite resulted only in a small reduction in HM bioavailability to wheat plants. Among the studied additives, Na‐bentonite and Ca‐bentonite have the most promising potential to reduce the bioavailability for the studied HM.