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1.

Purpose

This study aimed at investigating the rhizosphere effects of Populus euramericana Dorskamp on the mobility of Zn, Pb and Cd in contaminated technosols from a former smelting site.

Materials and methods

A rhizobox experiment was conducted with poplars, where the plant stem cuttings were grown in contaminated technosols for 2 months under glasshouse conditions. After plant growth, rhizosphere and bulk soil pore water (SPW) were sampled together. SPW properties such as pH, dissolved organic carbon (DOC) and total dissolved concentrations of Zn, Pb and Cd were determined. The concentrations of Zn, Pb and Cd in plant organs were also determined.

Results and discussion

Rhizosphere SPW pH increased for all studied soils by 0.3 to 0.6 units compared to bulk soils. A significant increase was also observed for DOC concentrations regardless of the soil type or total metal concentrations, which might be attributed to the plant root activity. For all studied soils, the rhizosphere SPW metal concentrations decreased significantly after plant growth compared to bulk soils which might be attributed to the increase in pH and effects of root exudates. Zn, Pb and Cd accumulated in plant organs and the higher metal concentrations were found in plant roots compared to plant shoots.

Conclusions

The restricted transfer of the studied metals to the plant shoots confirms the potential role of this species in the immobilization of these metals. Thus, P. euramericana Dorskamp can be used for phytostabilization of technosols.
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2.

Purpose

The main objectives of the study were to (1) develop a one-step facile procedure for synthesizing a new chemical amendment agent with three chelating groups for solidifying multiple heavy metals, called sixthio guanidine acid (SGA), using guanidine hydrochloride and carbon disulfide as raw reactants and (2) assess its biodegradability, solidification effectiveness, and leachability in remedying soils contaminated with multiple heavy metals of various concentrations compared with other traditional amendment agents.

Materials and methods

Polluted soil samples were collected near a metalliferous mining site of Qixiashan in the southeast of Nanjing, China. Their concentrations were determined at 22.15–320 mg kg?1 for As, 3.30–29.31 mg kg?1 for Cd, 115.66–158.65 mg kg?1 for Ni, 165.04–1677.06 mg kg?1 for Pb, and 355.6–2426.91 mg kg?1 for Zn. Biodegradability of SGA was assessed in accordance with GB/T 21831-2008 and OECD-301D. Total concentration of heavy metals was determined according to ISO11466:1995. A modified three-step sequential Community Bureau of Reference (BCR) extraction procedure was used to examine speciation of heavy metals in the soil sample, and concentrations of heavy metals were measured by using inductively coupling plasma optical emission spectrometry (ICP-OES). Leachate extraction tests were carried out before and after the soil sample was solidified with different amendments in accordance with HJ/T 557-2009.

Results and discussion

It is found that the optimal conditions for SGA synthesis are a molar ratio of 4:1, a reaction temperature of 40 °C, and a reaction time of 2 h. Under such conditions, SGA yield is achieved as high as 91.5 %. The bioavailability and mobility of As, Cd, Ni, Pb, and Zn in highly contaminated soils can be reduced via using SGA. Our results indicate that SGA is nonbiodegradative and much more effective than other traditional chemical amendment agents in that it is highly effective in comprehensively solidifying As, Cd, Ni, and Pb.

Conclusions

SGA has the potential for comprehensive in situ remediation of soils contaminated with several heavy metal elements of various concentration levels, and such findings may be used as a guide to design new chemical amendment agents for rehabilitating soils contaminated with heavy metals.
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3.

Purpose

Soil contamination with arsenic (As) is an increasingly worldwide concern. Immobilization is a potentially reliable, cost-effective technique for the reclamation of As-contaminated soils. The aim of this study is to develop new soil amendments with high As immobilization efficiency, cost-effective, environmental-friendly, and without soil acidification for As-contaminated soil remediation.

Materials and methods

Biosynthesis of schwertmannite by Acidithiobacillus ferrooxidans has been conducted, and two types of biogenetic schwertmannites SCH and A-SCH were prepared and characterized by X-ray diffraction (XRD), transmission electron microscopy (TEM), Fourier transform infrared spectroscopy (FTIR), etc. The A-SCH was formed through pretreating SCH by acidic and alkaline activation. The potential of SCH and A-SCH in As immobilization in contaminated soil was evaluated. The effect of ferrous sulfate and A-SCH on soil pH and immobilization of NaHCO3-extractable As were also investigated for comparison.

Results and discussion

The chemical formula of SCH and A-SCH can be expressed as Fe8O8(OH)4.89(SO4)1.55 and Fe8O8(OH)5.19(SO4)1.41, respectively. Compared to SCH, A-SCH exhibits much higher specific surface area of 74.99 m2 g?1 and contains more hydroxyl groups and inner-sphere sulfate complexes. Immobilization efficiency of water-soluble As above 99.5 % can be achieved with A-SCH dosage of 5 % and SCH dosage of 10 %, respectively. The immobilization percentages of NaHCO3-extractable As increased from 31.5 to 90.4 % and from 40.2 to 93.8 % with increasing dosage from 0.5 to 10 wt % for SCH and A-SCH, respectively. In general, both SCH and A-SCH immobilize As in contaminated soil effectively, and the immobilization performance of A-SCH was better than that of SCH, especially at lower dosage.

Conclusions

Biogenetic schwertmannite could be used as a potential effective soil amendment for As immobilization in contaminated soil. Our findings in this study also have important implications for in situ immobilization of As in contaminated soils, especially the soils related to acidic iron and sulfate-rich environments.
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4.

Purpose

Phosphate (P) fertilizers are being widely used to increase crop yield, especially in P-deficient soils. However, repeated applications of P could influence trace element bioaccumulation in crops. The effects of 5-year P enrichment on trace element (Cu, Zn, Cd, Pb, As, and Hg) accumulation in Oryza sativa L. were thus examined.

Materials and methods

Two paddy soils with different initial P availabilities were amended with and without P fertilizer from 2009 to 2013. Trace elements and P levels in rice and soils were analyzed.

Results and discussion

In soil initially with limited P, P amendment enhanced grain Pb, As, and Hg concentrations by 1.8, 1.5, and 1.4-fold, respectively, but tended to decrease the grain Cd level by 0.73-fold, as compared to the control. However, in soil initially with sufficient P, P amendment tended to reduce accumulation of all examined elements in rice grain.

Conclusions

Phosphate amendment in initially P-limited and P-sufficient soils had different effects on trace element availability in soil (as reflected by extractable element) and plant physiology (growth and metal translocation), resulting in contrasting patterns of trace element accumulation in rice between the two types of soils. Our study emphasized the necessity to consider the promoting effects of P on Pb, As, and Hg accumulation in grain in initial P-deprived soil.
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5.

Purpose

The presence of high copper (Cu) and cadmium (Cd) contamination in soils around mining areas has raised serious health concerns. Improving hydroxyapatite (HAP) adsorption capacity for Cu and Cd is important if its application potential in heavily contaminated soils is to expand.

Materials and methods

The micro/nanostructured HAP (mnHAP) was synthesized using a template-induced method to improve the HAP immobilization of Cu and Cd in contaminated soils. Commercial and synthetic HAPs were evaluated as amendments in Cu and Cd remediation tests with 1.5 and 3.0 % addition level for 90 days, and soils without HAP materials (0.0 %) were designated as the controls; each treatment was repeated three times. The materials were characterized by X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FTIR), N2 adsorption, and scanning electron microscopy (SEM)-energy-dispersive spectra (EDS) and then quantitatively determined the Cu and Cd contents by inductively coupled plasma (ICP) and inductively coupled plasma mass spectrometry (ICP-MS).

Results and discussion

The mnHAP was more effective in immobilizing Cu and Cd than the two commercial HAPs. After treatment with mnHAP at the 3.0 % addition level for 90 days, the contaminated soils showed 55.2 and 84.8 % reductions in Cu and Cd concentrations in the toxicity characteristic leaching procedure (TCLP) leaching procedure, respectively. The experimental data indicated that the enhanced Cu and Cd immobilization by mnHAP was due to the increases of surface area and the improvement of structure and newly introduced carboxylate groups on its surface.

Conclusions

These findings show that regulating the structure and surface properties of HAP can enhance Cu and Cd immobilization in soils.
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6.

Purpose

Anthropic activities induce severe metal(loid)s contamination of many sites, which is a threat to the environment and to public health. Indeed metal(loid)s cannot be degraded, and thus accumulate in soils. Furthermore, they can contaminate surrounding ecosystems through run-off or wind erosion. This study aims to evaluate the phytostabilization capacity of Salix viminalis to remediate As and Pb highly contaminated mine site, in a biochar-assisted phytoremediation context and to assess biochar particle size and dose application effects.

Materials and methods

To achieve this, mesocosm experiments were conducted using the contaminated technosol and four different size fraction of one biochar as amendment, at two application rates (2 and 5%). Non-rooted cuttings of Salix viminalis were planted in the different mixtures. In order to characterize the mixtures, soil pore waters were sampled at the beginning and at the end of the experiment and analyzed for pH, electrical conductivity, and metal(loid) concentrations. After 46 days of Salix growth, roots, stems, and leaves were harvested and weighed, and As and Pb concentrations and distributions were measured.

Results and discussion

Soil fertility improved (acidity decrease, electrical conductivity increase) following biochar addition, whatever the particle size, and the Pb concentration in soil pore water decreased. Salix viminalis did not grow on the non-amended contaminated soil while the biochar amendment permitted its growth, with a better growth with the finest biochars. The metal(loid)s accumulated preferentially in roots.

Conclusions

Fine biochar particles allowed S. viminalis growth on the contaminated soil, allowing this species to be used for technosol phytostabilization.
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7.

Purpose

Previous studies show that application of biochar can reduce the bioavailability of heavy metals in soil. A plant growth experiment was carried out to evaluate the effect of tobacco stalk- and dead pig-derived biochars on the extractability and redistribution of cadmium (Cd) and zinc (Zn) in contaminated soil, and the impact on tobacco (Nicotiana tabacum L.) plant growth.

Materials and methods

The top 20 cm of a soil contaminated with Cd and Zn was used in this study. Biochars derived from tobacco stalk and dead pig were applied to the soil at four application rates (0, 1, 2.5, and 5 %), and tobacco plants were grown. After 80-days growth, the pH, electrical conductivity (EC), CaCl2-extractable heavy metals and fractions of heavy metals in soil samples, as well as the plant biomass and the concentrations of heavy metals in the plant were determined.

Results and discussion

The plant growth experiment demonstrated that tobacco stalk biochar and dead pig biochar significantly (P?<?0.05) increased the pH, but had no significant effect on the electrical conductivity (EC) of the soil. The CaCl2-extractable Cd and Zn content decreased as the application rates increased. The concentration of extractable Cd and Zn decreased by 64.2 and 94.9 %, respectively, for the tobacco stalk biochar treatment, and 45.8 and 61.8 %, respectively, for the dead pig biochar treatment at 5 % application rate. After biochar addition, the exchangeable Cd was mainly transformed to fractions bound to carbonates and Fe-Mn oxides, while the Zn was immobilized mainly in the fraction bound to Fe-Mn oxides. Tobacco stalk biochar increased the tobacco plant biomass by 30.3 and 36.2 % for shoot and root, respectively at the 5 % application rate. Dead pig biochar increased the tobacco plant biomass by 43.5 and 40.9 % for shoot and root, respectively, at the 2.5 % application rate. Both biochars significantly (P?<?0.05) decreased the Cd and Zn accumulation by tobacco plant.

Conclusions

As a soil amendment, tobacco stalk biochar was more effective at removing Cd, whereas dead pig biochar was more effective at removing Zn, and a higher application rate was more effective than a lower application rate. Overall, biochar derived from tobacco stalk was more effective, than dead pig biochar, at remediating soil contaminated with Cd and Zn, as well as promoting tobacco growth.
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8.

Purpose

Biochar can be used to reduce the bioavailability and leachability of heavy metals, as well as organic pollutants in soils through adsorption and other physicochemical reactions. The objective of the study was to determine the response of microbial communities to biochar amendment and its influence on heavy metal mobility and PCBs (PCB52, 44, 101, 149, 118, 153, 138, 180, 170, and 194) concentration in application of biochar as soil amendment.

Materials and methods

A pot (macrocosm) incubation experiment was carried out with different biochar amendment (0, 3, and 6 % w/w) for 112 days. The CaCl2-extractable concentration of metals, microbial activities, and bacterial community were evaluated during the incubation period.

Results and discussion

The concentrations of 0.01 M CaCl2-extractable metals decreased (p?>?0.05) by 12.7 and 20.5 % for Cu, 5.0 and 15.6 % for Zn, 0.2 and 0.5 % for Pb, and 1.1 and 8.9 % for Cd, in the presence of 3 and 6 % of biochar, respectively, following 1 day of incubation. Meanwhile, the total PCB concentrations decreased from 1.23 mg kg?1 at 1 day to 0.24 mg kg?1 at 112 days after 6 % biochar addition, representing a more than 60 % decrease relative to untreated soil. It was also found out that biochar addition increased the biological activities of catalase, phosphatase, and urease activity as compared with the controls at the same time point. Importantly, the Shannon diversity index of bacteria in control soils was 3.41, whereas it was 3.69 and 3.88 in soils treated with 3 and 6 % biochar soil. In particular, an increase in the number of populations with the putative ability to absorb PCB was noted in the biochar-amended soils.

Conclusions

The application of biochar to contaminated soils decreased the concentrations of heavy metals and PCBs. Application of biochar stimulated Proteobacteria and Bacteroides, which may function to absorb soil PCB and alleviate their toxicity.
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9.

Purpose

The objectives of this study were (1) to investigate the effects of manure compost and earthworms on Cd mobility in Cd-contaminated soil, (2) to test whether the bioturbation of earthworms reduces the immobilization effect of the manure compost when they are combined, and (3) to explore the distribution of Cd in aggregates formed by earthworms with corresponding fractionation analysis.

Materials and methods

A laboratory experiment was conducted to evaluate the effect of either or both application of manure compost and the earthworms Eisenia fetida into cadmium historically contaminated soil on cadmium mobility. Soil characteristics and metal concentrations in earthworms and soil were measured, and soil aggregates in the mesocosms were separated for Cd fraction analysis based on four steps sequential extraction.

Results and discussion

Manure compost reduced mobile Cd based on CaCl2 extraction and Toxicity Characteristic Leaching Procedure (TCLP) test by 60–95 and 25–30 %, respectively. However, earthworm application alone increased Cd mobility by 9–15 %. Besides, in the presence of manure compost, earthworms further immobilized cadmium to a slight extent. The interaction effect of manure compost and earthworms combined on Cd immobilization suggested that earthworms promoted the formation of large macroaggregates (>2 mm) and the redistribution of Cd concentration in soil aggregates. Additionally, earthworms reduced carbonate fraction of Cd from 42.3–49.6 to 6.3–19.5 % in different aggregates, respectively. And, residual fraction of Cd increased from 33.9–42.2 to 63.9–77.5 % simultaneously. The results may be due to the thorough mixture of phosphates and organic matter with cadmium during bioturbation on account of the available form of phosphorus, nitrogen, and cadmium changing to the more recalcitrant form.

Conclusions

Manure compost addition increased the soil pH, phosphorus, nitrogen, and organic carbon content, and decreased Cd mobility. The application of earthworms and manure compost combined exhibited higher efficiency for cadmium immobilization, which can be used for Cd remediation due to the redistribution of Cd concentration in soil aggregates and the transformation of soluble Cd to the residual precipitate fraction.
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10.

Purpose

Biochar application has been shown to be effective in improving soil fertility and sequestering soil contaminants. However, the impact of biochar amendments on the environmental fate of pesticides and the bioavailability of pesticides to living organisms in the soil environment is still not fully understood.

Materials and methods

Dissipation of fomesafen and its bioavailability to corn (Zea mays L.) and the earthworm Eisenia fetida in an agricultural soil amended with three different rates of rice hull biochar (0.5, 1, and 2 % (w/w)) under laboratory conditions was investigated.

Results and discussion

Biochar amendment significantly increased the DT50 of fomesafen from 34 days in unamended soil to 160 days in 2 % biochar-amended soil. Furthermore, biochar amendment decreased fomesafen concentration in soil pore water resulting in lower plant uptake of the pesticide. In this case, total plant residue and soil pore water concentrations of fomesafen in 2 % biochar-amended soil decreased to 0.29 % and 0.28–45 % of that in the control, respectively. Similar results were obtained for bioavailability of fomesafen in earthworms, as the earthworm residue and soil pore water concentration of fomesafen in 2 % biochar-amended soil declined to 0.38–45 and 0.47–0.50 % compared to the level of the control, respectively.

Conclusions

As biochar could markedly reduce the concentration of fomesafen in soil pore water and subsequently reduce plant and earthworm uptake of fomesafen from contaminated soil, biochar amendment could be considered an appropriate option for immobilizing fomesafen in soils, protecting nontarget organisms from fomesafen contamination.
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11.

Purpose

In situ immobilization of heavy metal-contaminated soils with the repeated incorporation of amendments can effectively reduce the bioavailability of soil heavy metals. However, the long-term application of amendments would lead to the destruction of soil structure and accumulation of soil toxic elements, ultimately affecting food security and quality. Thus, the sustainability of the amendments in a heavy metal-contaminated soil was evaluated from 2010 to 2012.

Materials and methods

Batch field experiments were conducted in the soils, which were amended with apatite (22.3 t ha?1), lime (4.45 t ha?1), and charcoal (66.8 t ha?1), respectively. The amendments were applied only one time in 2009, and ryegrass was sown each year. Ryegrass and setaria glauca (a kind of weed) were harvested each year. Concentrations of copper (Cu) and cadmium (Cd) were determined by batch experiments. Five fractions of Cu and Cd were evaluated by a sequential extraction procedure.

Results and discussion

Ryegrass grew well in the amended soils in the first year, but it failed to grow in all the soils in the third year. However, setaria glauca could grow with higher biomass in all the amended soils. The treatment of apatite combined with plants was more effective than lime and charcoal treatments in removing Cu and Cd from the contaminated soils by taking biomass into account. Apatite had the best sustainable effect on alleviating soil acidification. The Cu and Cd concentrations of CaCl2-extractable and exchangeable fractions decreased with the application of amendments. Moreover, apatite and lime could effectively maintain the bioavailability of Cu and Cd low.

Conclusions

Apatite had a better sustainable effect on the remediation of heavy metal-contaminated soils than lime and charcoal. Although all the amendment treated soils did not reduce soil total concentrations of Cu and Cd, they could effectively reduce the environmental risk of the contaminated soils. The findings could be effectively used for in situ remediation of heavy metal-contaminated soils.
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12.

Purpose

Water management has a strong influence on Cd solubility in agricultural soils, affecting Cd uptake in crops. In the process, sulfur interaction with other metals such as zinc may play an important role. A pot experiment was carried out to investigate the effects of water management coupled with zinc and sulfate amendment on Cd uptake by the leafy vegetable amaranth with a strong Cd accumulation tendency in its edible parts.

Materials and methods

The soils were amended with Cd, Cd+SO4 and Cd+SO4+Zn with no amendment as control. Then, the soils were flooded for 1 month, after which amaranth was grown with soil kept saturated (wet cultivation). In the succeeding planting, soils were tilled to aeration condition under which amaranth was grown again (dry cultivation). Soil and crop samples were collected and analysed for various parameters.

Results and discussion

The readily exchangeable quantities of Cd and Zn in the soil decreased under wet cultivation, increasing again under dry cultivation but to levels lower than those in the initial soil. Wet cultivation enhanced plant Cd concentration but reduced Zn accumulation compared to dry cultivation. Zn bioavailability was strongly affected by soil water status but failed to reduce Cd uptake by amaranth. Irreversible or slowly reversible changes occurred in Cd and Zn solubility and phytoavailability as soil water-saturated status was altered by periodic flooding events.

Conclusions

Dry cultivation with lower soil water content ensured high production with low Cd in the edible part of this leaf vegetable and so remains the recommended irrigation regime.
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13.

Purpose

The study aimed at comparing the effects of different water managements on soil Cd immobilization using palygorskite, which was significant for the selection of reasonable water condition.

Materials and methods

Field experiment was taken to discuss the in situ remediation effects of palygorskite on Cd-polluted paddy soils, under different water managements, using a series of variables, including pH and extractable Cd in soils, plant Cd, enzyme activity, and microorganism number in soils.

Results and discussion

In control group, the pH in continuous flooding was the highest under three water conditions, and compared to conventional irrigation, continuous flooding reduced brown rice Cd by 37.9%, and brown rice Cd in wetting irrigation increased by 31.0%. In palygorskite treated soils, at concentrations of 5, 10, and 15 g kg?1, brown rice Cd reduced by 16.7, 44.4, and 55.6%; 13.8, 34.5, and 44.8%; and 13.1, 36.8, and 47.3% under continuous flooding, conventional irrigation, and wetting irrigation (p < 0.05), respectively. The enzyme activity and microbial number increased after applying palygorskite to paddy soils.

Conclusions

Continuous flooding was a good candidate as water management for soil Cd stabilization using palygorskite. Rise in soil enzyme activity and microbial number proved that ecological function regained after palygorskite application.
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14.

Purpose

Extensive deposition of Pb, As, and Cs in soils may damage ecosystems and human’s health. Soil washing is the most conventional remediation method, and its efficiency depends on metal solubility in soil. This study aims to optimize operating variables of electro-kinetic field (EKF)-enhanced soil washing procedures.

Materials and methods

Soil samples from a Mississippi River Delta rice field were homogeneously spiked with Pb, As, and Cs, and contaminated soil was aged for 3 months. The remediation involved a first stage electro-kinetic process, followed by a soil washing procedure. Soil pH changes under EKF were studied. Effects of citric acid and reversed EKF were investigated for alleviating possible alkaline precipitation. In the washing procedure, soil washing time and cycles with different extractants were examined. The overall EKF-enhanced soil washing efficiencies were discussed as well.

Results and discussion

The implement of EKF offered an acidic soil environment around the anode areas for solubilizing metal(loid)s. Combined with EKF, citric acid was more conductive to desorb metal(loid)s. In addition, the reversed EKF effectively alleviated metal(loid) precipitation caused by alkalization in the first stage cathode areas. The EKF significantly enhanced metal(loid) extractions in the anode area of soils using Na2EDTA, CaCl2, and citric acid at pH of 2. The most preferable removal of Pb (80–98 %), As (48–63 %), and Cs (10–13 %) was achieved with three extractants. CaCl2 and citric acid were proved to be suitable alternatives to Na2EDTA for Pb extraction. A washing process of 2 h extraction with double washing cycles was optimized.

Conclusions

Soil washing time and cycles were major factors governing the metal(loid) removal from soil. Washing process of 2 h extraction with double cycles was optimized for further extraction based on higher washing efficiency. The EKF effectively improved washing efficiency while some electrical parameters need further studies for cost performance consideration.
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15.

Purpose

Soil contamination with heavy metals, such as Cd and Pb, has caused severe health and environmental risks all over the world. Possible eco-friendly solutions for Cd and Pb immobilization were required to reduce its mobility through various cost-effective amendments.

Materials and methods

A laboratory incubation study was conducted to assess the efficiency of biochar (BC), zeolite (ZE), and rock phosphate (RP) as passivators for the stabilization of Cd and Pb in paddy soil as well as soil microbial biomass. Various extraction techniques were carried out: a sequential extraction procedure, the European Community Bureau of Reference (BCR), toxicity characteristic leaching procedure (TCLP) test, and single extraction with CaCl2. The impact of passivators on soil pH, dissolved organic carbon (DOC), and microbial biomass (carbon, nitrogen, and phosphorus) was examined in the metal contaminated soil.

Results and discussion

The results showed that the exchangeable portion of Cd in soil was significantly reduced by 34.8, 21.6, and 18.8% with ZE, RP, and BC at a 3% application rate, respectively. A similar tendency of reduction in Pb soluble portion was observed by ZE (9.6%), RP (20%), and BC (21.4%) at a 3% application rate. Moreover, the TCLP leachate of Cd and Pb was apparently reduced by 17 and 30.3% with BC at a 3% application dose, respectively, when compared to the control. Soil pH, nutrients, and microbial biomass C, N, and P were significantly increased with the addition of BC, RP, and ZE passivators.

Conclusions

The results showed that the incorporation of BC, ZE, and RP significantly reduced the Cd and Pb mobility in paddy soil as well as enhanced soil nutrients and microbial biomass. Overall, among all the amendments, rice straw derived-BC performed better for Cd and Pb immobilization in paddy soil.
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16.

Purpose

This study was aimed to investigate the potential of biochar (BC), a waste byproduct of a bioenegy industry, Sri Lanka, as a soil amendment to immobilize and reduce the phytotoxicity of Cr in tannery waste-polluted soil (TWS).

Materials and methods

The TWS and bioenergy waste BC were characterized for physio-chemical parameters. A pot experiment was conducted by adding three BC application rates, 1, 2.5, and 5 % (w/w) to investigate the immobilizing capacity and bioaccumulation of chromium (Cr) in tomato plants (Lycopersicon esculentum L.). Soils and plants were digested via microwave digestion and analyzed for total Cr. Further, sequential extraction was conducted to assess the fractionation of Cr before and after the application of bioenergy waste BC on TWS.

Results and discussion

The total Cr concentration in TWS was 12,285 mg/kg. The biomass of tomato plants grown in the 5 % BC amendment doubled compared to the biomass in BC-unamended soil. Bioaccumulation of Cr in plants grown in 5 % BC-amended TWS showed a decrease by 97 % compared to that of the BC-unamended soil. The CaCl2 extractability of Cr indicated that the bioavailability of Cr in the 5 % BC amendment has decreased by 68 % compared to the control. Sequentially extracted Cr in the exchangeable fraction decreased by 98 % in the 5 % BC amendment.

Conclusions

Pore diffusion, and adsorption via π-π electron donor-acceptor interactions were the primary mechanisms to be involved in the Cr retention in BC. Results suggested that the addition of BC to TWS reduces the mobility, bioavailability, and phytotoxicity of Cr in tomato plants.
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17.

Purpose

Remediation of metal contaminated soil with biochar is attracting extensive interest in recent years. Understanding the significance of variable biochar properties and soil types helps elucidating the meticulous roles of biochar in immobilizing/mobilizing metals/metalloids in contaminated soils.

Materials and methods

Six biochars were produced from widely available agricultural wastes (i.e., soybean stover, peanut shells and pine needles) at two pyrolysis temperatures of 300 and 700 °C, respectively. The Pb-, Cu-, and Sb-contaminated shooting range soils and Pb-, Zn-, and As-contaminated agricultural soils were amended with the produced biochars. The mobility of metals/metalloids was assessed by the standard batch leaching test, principal component analysis and speciation modeling.

Results and discussion

The changes in soil properties were correlated to feedstock types and pyrolysis temperatures of biochars based on the principal component analysis. Biochars produced at 300 °C were more efficient in decreasing Pb and Cu mobility (>93 %) in alkaline shooting range soil via surface complexation with carboxyl groups and Fe-/Al-minerals of biochars as well as metal-phosphates precipitation. By contrast, biochars produced at 700 °C outperformed their counterparts in decreasing Pb and Zn mobility (100 %) in acidic agricultural soil by metal-hydroxides precipitation due to biochar-induced pH increase. However, Sb and As mobility in both soils was unfavorably increased by biochar amendment, possibly due to the enhanced electrostatic repulsion and competition with phosphate.

Conclusions

It is noteworthy that the application of biochars is not equally effective in immobilizing metals or mobilizing metalloids in different soils. We should apply biochar to multi-metal contaminated soil with great caution and tailor biochar production for achieving desired outcome and avoiding adverse impact on soil ecosystem.
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18.

Purpose

A preliminary study was carried out in Rome (Italy) to assess the potential role of atmospheric deposition in trace element contamination in urban vegetable gardens relative to human health risk from crop consumption.

Materials and methods

Two sites were selected on the basis of previously known contamination issues. Atmospheric deposition, parent material, soils properties affecting trace element mobility, and various anthropogenic inputs were considered. Soil samples were taken at depth from two points in each garden, within 5 cm of sampled crops. Inputs and crops were sampled and analysed for As and Pb content. A rain and dust gauge was set up in each garden for the duration of 93 days (late spring to late summer) for atmospheric deposition sampling.

Results and discussion

Atmospheric deposition influx was high at both sites (2.22 and 2.32 As and 2.67 and 3.42 Pb μg m?3 day?1). Soil pH was between 6.70 and 7.57 and texture varied from loamy sand to clay loam (3.4 to 31.9 % clay content). CEC ranged between 21.6 and 54.2 meq/100 g within rooting depth, rising almost commensurately with soil organic carbon (SOC) content (1.87–8.37 %). Somewhat high total soil Pb content (80.8–522.7 ppm) contrasted with negligible exchangeability and crop content (<0.01 ppm). Total soil As (17.0–32.0 ppm) corresponded with exchangeable and crop As for one site in one of the gardens. Leaves evinced high As accumulation levels (16.0–41.2 ppm) in all crops. High amounts of atmospheric Pb combined with negligible amounts of extractable Pb and Pb plant tissue content point to particulate inhalation and ingestion as a main health threat in the case of Pb. In contrast, food intake seems to be of greater concern relative to high As contamination. Greater soil As solubility may be explanatory, but the mostly low amounts of extractable As and the high atmospheric As suggest an airborne route being playing an important role.

Conclusions

Preliminary results suggest that research on trace element contamination in urban gardens should consider atmospheric deposition as a major contributing source.
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19.

Purpose

Cobalt (Co) is a toxic metal to the environment and human’s health. The purpose of the study is to achieve an investigation into the efficacy of calcium carbonate and cow dung for Co immobilization in fluvo-aquic soil, as well as their effects on the antioxidant system in plants.

Materials and methods

Calcium carbonate and cow dung were incorporated with the Co-polluted fluvo-aquic soil where pakchois (Brassica chinensis L.) were grown. Co concentration, superoxide dismutase (SOD) activity, catalase (CAT) activity, and malondialdehyde (MDA) concentration in the shoots of the mature plants were inspected.

Results and discussion

As calcium carbonate concentration rose (0 to 12 g kg?1), Co concentration in shoots of the plants decreased firstly and then increased again (P < 0.05), while the accumulation level of Co kept decreasing with cow dung concentration rising (P < 0.05). Under the amendment treatments, the SOD activity, CAT activity, and MDA concentration in the shoots were all positively correlated to the Co concentration in the plant tissue (r = 0.792, 0.904, and 0.807, P < 0.01), indicating the antioxidant system receptivity to the Co accumulation. The amendments in soil can alleviate the oxidative stress in pakchois owing to Co pollution. As calcium carbonate concentration ranged from 5.64 to 7.86 g kg?1, the parameters reached a maxima (minimum), respectfully.

Conclusions

Calcium carbonate and cow dung in fluvo-aquic soil are effective for Co immobilization and mitigating any pertinent oxidative stress in pakchoi plants. Calcium carbonate concentration within a range of 5.64 to 7.86 g·kg?1 will achieve optimum efficacy.
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20.

Purpose

Heavy metal distribution in soils is affected by soil aggregate fractionation. This study aimed to demons trate the aggregate-associated heavy metal concentrations and fractionations in “sandy,” “normal,” and “mud” soils from the restored brackish tidal marsh, oil exploitation zone, and tidal mudflat of the Yellow River Delta (YRD), China.

Materials and methods

Soil samples were sieved into the aggregates of >2, 0.25–2, 0.053–0.25, and <0.053 mm to determine the concentrations of exchangeable (F1), carbonate-bound (F2), reducible (F3), organic-bound (F4), and residual fraction (F5) of Cd, Cr, Cu, Ni, Pb, and Zn.

Results and discussion

The 0.25–2 mm aggregates presented the highest concentrations but the lowest mass loadings (4.23–12.18 %) for most metal fractions due to low percentages of 0.25–2 mm aggregates (1.85–3.12 %) in soils. Aggregates <0.053 mm took majority mass loadings of metals in sandy and normal soils (62.04–86.95 %). Most soil aggregates had residual Cr, Cu, Ni, Zn, and reducible Cd, Pb dominated in the total Cd, Cr, Cu, Ni, Pb, and Zn concentrations. Sandy soil contained relatively high F4, especially of Cu (F4) in 0.25–2 mm aggregates (10.22 mg kg?1), which may relate to significantly high organic carbon contents (23.92 g kg?1, P?<?0.05). Normal soil had the highest total concentrations of metals, especially of Cu, Ni, and Pb, which was attributed to the high F3 and F5 in the <0.053 mm aggregates. Although mud soil showed low total concentrations of heavy metals, the relatively high concentrations of bioavailable Cd and Cu resulted from the relatively high Cd (F2) and Cu (F2) in the >2 mm aggregates indicated contribution of carbonates to soil aggregation and metal adsorption in tidal mud flat.

Conclusions

Soil type and aggregate distribution were important factors controlling heavy metal concentration and fractionation in YRD wetland soil. Compared with mud soil, normal soil contained increased concentrations of F5 and F3 of metals in the 0.053–0.25 mm aggregate, and sandy soil contained increased concentrations of bioavailable and total Cr, Ni, and Zn with great contribution of mass loadings in the <0.053 mm aggregate. The results of this study suggested that oil exploitation and wetland restoration activities may influence the retention characteristics of heavy metals in tidal soils through variation of soil type and aggregate fractions.
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