Bioavailability Of Metals In Soils Research Articles

Evaluation of heavy metal bioavailability in soil amended with poultry manure using single and BCR sequential extractions

In the present study, three-step Community Bureau of Reference sequential extraction scheme (BCR-SES) and single extraction methods were performed to assess the mobility and availability of heavy metals (Cd, Cu, Pb, Fe and Zn) in an agricultural soil before and after amendment with poultry waste (PW).The PW samples were collected from poultry farms, situated in Hyderabad Sindh, Pakistan. The extractable heavy metals were measured by flame and electrothermal atomic absorption spectrometry. The validation of the method was carried out by analysis of a certified reference material of soil amended with sewage sludge (BCR-483). The single extractions using calcium chloride and EDTA, separately, while BCR-SESs were developed to evaluate the available heavy metals to plants and their environmental accessibility for control soil (CS), PW and soil amended with PW (SPW).The pH of the PW and SPW were found to be < 6.0, which may enhance the leaching of heavy metals to agricultural soil. The results from the partitioning study indicated that easily mobilised forms (acid exchangeable) of Cd were higher than other heavy metals. The oxidisable fractions of all heavy metals were dominant in PW and SPW as compared to found in CS samples. The EDTA- and CaCl2-extractable heavy metals correspond to 5.0 to 10 and 0.5 to 3.0%, respectively of total contents in all three solid samples. Contamination factors revealed that the retention of Pb and Zn were higher compared with Cu, Cd and Fe in CS, PW and SPW samples.

Effects of biochar and Arbuscular mycorrhizae on bioavailability of potentially toxic elements in an aged contaminated soil

Biochar pyrolyzed from corn stalks at 300 °C/500 °C and arbuscular mycorrhizae (AMF) were examined independently and in combination as possible treatments for soil remediation contaminated with Cd, Cr, Ni, Cu, Pb, Zn after 35 years following land application of sewage sludge in the 1970s. The results showed that biochar significantly decreased the heavy metal concentrations and their bioavailability for plants, and both biochars had similar such effects. AMF inoculation of corn plants had little effect on heavy metal bioavailability in either control or biochar amended soil, and no interaction between biochar and AMF was observed. Changes in DTPA extractable metals following biochar addition to soil were correlated with metal uptake by plants, whereas pore water metal concentrations were not predictive indicators. This research demonstrates positive benefits from biochar application for contaminated soil remediation, but remain ambiguous with regard to the benefits of simultaneous AMF inoculation on reduction of heavy metal bioavailability.

Interactions of Cd and Pb with Humate–Palygorskite and Humate–Sepiolite Complexes

Various geochemical studies have yielded conflicting data on whether humic coatings decrease or increase adsorption of heavy metals by soil minerals. The objective of the present study is to determine how humate pre-adsorption affects subsequent retention of Cd and Pb by palygorskite and sepiolite, as special silicate clay minerals of soil in many arid regions. For this purpose, a series of equilibrium batch experiments were conducted on the interactions of Pb and Cd with Ca–palygorskite and Ca–sepiolite before and after humate adsorption. The results showed that the Langmuir (L), Freundlich (F), Langmuir–Freundlich (LF), and Toth (T) equations satisfactorily described metal sorption data on the minerals. In the presence of humate as the pre-adsorbate, the values for sorption capacities of palygorskite and sepiolite for Cd and Pb slightly decreased. This can be attributed to the competition between humates and metal ions for mineral active sites and steric hindrance of the adsorbed humates, which reduces the access of metal ions to the mineral surface and internal channels. Humate coatings decreased the adsorption equilibrium constants of Cd, suggesting that the affinity of the organo-clays for Cd sorption is lower than those of Ca–clays. The values for the heterogeneity factor (β) generally showed an increasing trend with increasing humate coverage on palygorskite and sepiolite, which can be explained by the increased diversity of adsorption centers on humate–clay complexes. It may be concluded that the presence of humate bound on fibrous clay surfaces can influence the sorption, and hence the bioavailability and mobility of heavy metals in fibrous clay-containing arid and semiarid soils.

Heavy Metal Contamination in Urban Surface Soil of Klang District (Malaysia)

This study aimed to determine bioavailability of heavy metal concentrations (Al, Fe, Zn, Cu, Co, Cd, Pb and Cr) in 76 urban surface soil samples of Klang district (Malaysia). This study also aimed to determine health risks posed by bioavailability of heavy metals in urban soil on adults and children. For bioavailability of heavy metal concentrations, a physiologically bioavailability extraction test in vitro digestion model was used. Mean values of bioavailability heavy metal concentrations for this study were found to be the highest in Al (25.44 mg/kg) and lowest in Cr (0.10 mg/kg). Results of Spearman correlation coefficient (r) values showed significant correlations were observed for Al-Fe (r = 0.681), Cd-Co (r = 0.495), Cu-Zn (r = 0.232), Fe-Pb (r = 0.260), Fe-Zn (r = 0.239). For cluster analysis, output showed that these heavy metals could be classified into four clusters: Cluster 1 consisted of Cd, Cr, Co, and Pb; Cluster 2 consisted of Zn and Cu; Cluster 3 consisted of Fe; and Cluster 4 consisted of Al. For Clusters 1 and 2, anthropogenic sources were believed to be the sources, while for Clusters 3 and 4 the heavy metals originated from natural sources. Health risks were determined in adults and children through health risk assessment. For adults, Hazard Quotient (HQ) value was <1, indicating no non-carcinogenic risk, while for children, the HQ value was >1, indicating a non-carcinogenic risk. Meanwhile, for carcinogenic risk, heavy metal contamination in the Klang district might not pose a carcinogenic risk to adults while it may pose a carcinogenic risk to children because TR values in this study were >1.0E-04 for children. Output has identified the general health risk in the Klang district. Moreover, this study's findings will contribute to fill in the gap of knowledge on heavy metals' impacts on human health and urban development in the Klang District.

The Chemophytostabilisation Process of Heavy Metal Polluted Soil.

Industrial areas are characterised by soil degradation processes that are related primarily to the deposition of heavy metals. Areas contaminated with metals are a serious source of risk due to secondary pollutant emissions and metal leaching and migration in the soil profile and into the groundwater. Consequently, the optimal solution for these areas is to apply methods of remediation that create conditions for the restoration of plant cover and ensure the protection of groundwater against pollution. Remediation activities that are applied to large-scale areas contaminated with heavy metals should mainly focus on decreasing the degree of metal mobility in the soil profile and metal bioavailability to levels that are not phytotoxic. Chemophytostabilisation is a process in which soil amendments and plants are used to immobilise metals. The main objective of this research was to investigate the effects of different doses of organic amendments (after aerobic sewage sludge digestion in the food industry) and inorganic amendments (lime, superphosphate, and potassium phosphate) on changes in the metals fractions in soils contaminated with Cd, Pb and Zn during phytostabilisation. In this study, the contaminated soil was amended with sewage sludge and inorganic amendments and seeded with grass (tall fescue) to increase the degree of immobilisation of the studied metals. The contaminated soil was collected from the area surrounding a zinc smelter in the Silesia region of Poland (pH 5.5, Cd 12 mg kg-1, Pb 1100 mg kg-1, Zn 700 mg kg-1). A plant growth experiment was conducted in a growth chamber for 5 months. Before and after plant growth, soil subsamples were subjected to chemical and physical analyses. To determine the fractions of the elements, a sequential extraction method was used according to Zeien and Brümmer. Research confirmed that the most important impacts on the Zn, Cd and Pb fractions included the combined application of sewage sludge from the food industry and the addition of lime and potassium phosphate. Certain doses of inorganic additives decreased the easily exchangeable fraction from 50% to 1%. The addition of sewage sludge caused a decrease in fraction I for Cd and Pb. In combination with the use of inorganic additives, a mobile fraction was not detected and an easily mobilisable fraction was reduced by half. For certain combinations of metals, the concentrations were detected up to a few percent. The application of sewage sludge resulted in a slight decrease in a mobile (water soluble and easily exchangeable metals) fraction of Zn, but when inorganic additives were applied, this fraction was not detected. The highest degree of immobilisation of the tested heavy metals relative to the control was achieved when using both sewage sludge and inorganic additives at an experimentally determined dose. The sequential extraction results confirmed this result. In addition, the results proved that the use of the phytostabilisation process on contaminated soils should be supported.

Immobilization of Shewanella oneidensis MR-1 in diffusive gradients in thin films for determining metal bioavailability

Assessing metal bioavailability in soil is important in modeling the effects of metal toxicity on the surrounding ecosystem. Current methods based on diffusive gradient thin films (DGTs) and Gel-Integrated Microelectrode are limited in their availability and sensitivity. To address this, Shewanella oneidensis, an anaerobic iron reducing bacterium, was incorporated into a thin layer of agarose to replace the polyacrylamide gel that is normally present in DGT to form biologically mobilizing DGT (BMDGT). Viability analysis revealed that 16–35% of the cells remained viable within the BMDGTs depending on the culturing conditions over a 20h period with/without metals. Deployment of BMDGTs in standardized metal solutions showed significant differences to cell-free BMDGTs when cells grown in Luria Broth (LB) were incorporated into BMDGTs and deployed under anaerobic conditions. Deployment of these BMDGTs in hematite revealed no significant differences between BMDGTs and BMDGTs containing heat killed cells. Whether heat killed cells retain the ability to affect bioavailability is uncertain. This is the first study to investigate how a microorganism that was incorporated into a DGT device such as the metal reducing bacteria, S. oneidensis, may affect the mobility of metals.

High decrease in soil metal bioavailability by metal immobilization with halloysite clay

Increasing pollution by heavy metals calls for advanced methods to immobilize or extract soil metals, thus avoiding their contact with water, air and living organisms. In particular there is a need for cheap binding materials that extract metals. Here we tested the use of the halloysite clay, functionalized with silanes and non-functionalized, on metal extraction from soils. The clay was functionalized with 3-mercaptopropyl-trimethoxysilane and 3-[2-(2-aminoethylamino)ethylamino]propyltrimethoxysilane. Contaminated soils were sampled at the Glogow Copper Smelter and Refinery. Soils were sequentially extracted using the Tessier method. Metals were quantified by atomic absorption spectroscopy. Our results show that the addition of halloysite increases the metal content of the plant unavailable fraction that is the fifth fraction of the Tessier method, thus decreasing metal availability. Indeed metal contents of the fifth fraction versus total content increased from 67.64 to 157.79 mg/kg for copper, from 28.10 to 76.14 mg/kg for lead, from 41.60 to 95.78 mg/kg for zinc, from 0.77 to 1.79 mg/kg for cadmium and from 3.96 to 8.90 mg/kg for arsenic.

Bioavailability of heavy metals in soils: definitions and practical implementation--a critical review.

Worldwide regulatory frameworks for the assessment and remediation of contaminated soils have moved towards a risk-based approach, taking contaminant bioavailability into consideration. However, there is much debate on the precise definition of bioavailability and on the standardization of methods for the measurement of bioavailability so that it can be reliably applied as a tool for risk assessment. Therefore, in this paper, we reviewed the existing definitions of heavy metal bioavailability in relation to plant uptake (phytoavailability), in order to better understand both the conceptual and operational aspects of bioavailability. The related concepts of specific and non-specific adsorption, as well as complex formation and organic ligand affinity were also intensively discussed to explain the variations of heavy metal solubility and mobility in soils. Further, the most frequently used methods to measure bioavailable metal soil fractions based on both chemical extractions and mechanistic geochemical models were reviewed. For relatively highly mobile metals (Cd, Ni, and Zn), a neutral salt solution such as 0.01 M CaCl2 or 1 M NH4NO3 was recommended, whereas a strong acid or chelating solution such as 0.43 M HNO3 or 0.05 M DTPA was recommended for strongly soil-adsorbed and less mobile metals (Cu, Cr, and Pb). While methods which assessed the free metal ion activity in the pore water such as DGT and DMT or WHAM/Model VI, NICA-Donnan model, and TBLM are advantageous for providing a more direct measure of bioavailability, few of these models have to date been properly validated.

Biochar addition enhanced growth of Dactylis glomerataL. and immobilized Zn and Cd but mobilized Cu and Pb on a former sewage field soil

SummaryThe mobility and bioavailability of heavy metals in soils contaminated by irrigation with wastewater increase with increasing mineralization of accumulated organic substance and decreasing pH. In laboratory experiments addition of biochar reduced heavy metal availability to plants and enhanced plant growth. However, literature from field trials is scarce. Therefore, we conducted a 2‐year field experiment with orchard grass (Dactylis glomerata L.) to study the effects of miscanthus‐derived biochar applied to sewage field soil on biomass production and concentrations of zinc (Zn), copper (Cu), cadmium (Cd), lead (Pb) and various nutrients in plants and in the soil solution. Biochar was mixed into the contaminated topsoil (30 cm) with addition rates of 0, 1, 2.5 and 5% on a dry‐mass basis (g 100 g−1). The soil solution was collected with suction plates installed at a depth of 30 cm. Addition of biochar increased biomass production and reduced Zn and Cd concentrations in the soil solution. Zinc concentrations were also reduced in plants. This effect seems to be attributable to an increase in pH caused by biochar addition. In contrast, Pb and Cu concentrations in the soil solution generally increased and were related to the concentrations of dissolved organic carbon (DOC). Copper concentrations also increased in the plants; however, only at the beginning of the measurement period. Our data indicate that increased concentrations of DOC, Cu and Pb in the soil solution might be a transient effect. Therefore, further research is needed to determine the long‐term effect of biochar amendment on element immobilization and leaching into groundwater.

Effect of biochar on the extractability of heavy metals (Cd, Cu, Pb, and Zn) and enzyme activity in soil.

Biochar is a carbon-rich solid material derived from the pyrolysis of agricultural and forest residual biomass. Previous studies have shown that biochar is suitable as an adsorbent for soil contaminants such as heavy metals and consequently reduces their bioavailability. However, the long-term effect of different biochars on metal extractability or soil health has not been assessed. Therefore, a 1-year incubation experiment was carried out to investigate the effect of biochar produced from bamboo and rice straw (at temperatures ≥500 °C) on the heavy metal (cadmium (Cd), copper (Cu), lead (Pb), and zinc (Zn)) extractability and enzyme activity (urease, catalase, and acid phosphatase) in a contaminated sandy loam paddy soil. Three rates (0, 1, and 5%) and two mesh sizes (<0.25 and <1 mm) of biochar applications were investigated. After incubation, the physicochemical properties, extractable heavy metals, available phosphorus, and enzyme activity of soil samples were analyzed. The results demonstrated that rice straw biochar significantly (P < 0.05) increased the pH, electrical conductivity, and cation exchange capacity of the soil, especially at the 5% application rate. Both bamboo and rice straw biochar significantly (P < 0.05) decreased the concentration of CaCl2-extractable heavy metals as biochar application rate increased. The heavy metal extractability was significantly (P < 0.01) correlated with pH, water-soluble organic carbon, and available phosphorus in soil. The 5% application rate of fine rice straw biochar resulted in the greatest reductions of extractable Cu and Zn, 97.3 and 62.2%, respectively. Both bamboo and rice straw biochar were more effective at decreasing extractable Cu and Pb than removing extractable Cd and Zn from the soil. Urease activity increased by 143 and 107% after the addition of 5% coarse and fine rice straw biochars, respectively. Both bamboo and rice straw biochars significantly (P < 0.05) increased catalase activity but had no significant impact on acid phosphatase activity. In conclusion, the rice straw biochar had greater potential as an amendment for reducing the bioavailability of heavy metals in soil than that of the bamboo biochar. The impact of biochar treatment on heavy metal extractability and enzyme activity varied with the biochar type, application rate, and particle size.

Sorption of Pb(II) on palygorskite and sepiolite in the presence of amino acids: Equilibria and kinetics

The environmental mobility and bioavailability of heavy metals in soil are greatly influenced by sorption reactions on soil minerals, which are, in turn, controlled by the presence of various organic ligands, such as amino acids, in soil solution. In this study, the effects of l-cysteine (Cys) and l-histidine (His) amino acids on lead (Pb) sorption by palygorskite and sepiolite, as the specific silicate clay minerals of arid and semiarid soils, were studied using the batch method. Experimental Pb sorption data were subsequently analyzed by various isothermal and kinetic models. The equilibrium data revealed that both Langmuir and Freundlich models can describe the Pb sorption on palygorskite and sepiolite minerals. The sorption capacities of the minerals for Pb were decreased in the presence of Cys, probably because of the formation of neutral stable complexes of Pb and Cys as [ML] in the solution. The His effects, however, were different for the two minerals. Histidine reduced the Pb sorption capacity of sepiolite, but its diminishing effect was much lower than that of Cys. This result may be because of the formation of cationic soluble His–Pb complexes as [ML2H]+, which can be slightly adsorbed by the clay surfaces via electrostatic attraction. l-Histidine increased the sorption of Pb by palygorskite, probably due to formation of highly charged complexes with Pb, in the form of [ML2H2]2+ and [ML2H3]3+, or ternary surface complexation processes. The kinetics of Pb sorption by the minerals were satisfactorily described by the power, pseudo-first order, pseudo-second order and parabolic diffusion equations, among which the power function provided the best fit. The kinetics of Pb sorption by the palygorskite was rapid, approaching equilibrium within 10h. Lead sorption on the sepiolite, however, was much slower and equilibrium condition was attained after 10h. The Pb sorption rate indices, such as the initial sorption rate and diffusion rate constant, were also considerably affected by the presence of amino acids. These findings emphasize the importance of amino acids in evaluating the fate of Pb in arid soils in which fibrous silicate clay minerals are dominated in the clay fraction.

Effects of freshwater leaching on potential bioavailability of heavy metals in tidal flat soils.

Leaching experiments were conducted to investigate the effects of desalination levels and sediment depths on potential bioavailability of heavy metal (Cd, Cr, Cu, Fe, Mn, Ni, Pb, and Zn) in tidal flat soils. The data showed that both the desalination levels (p<0.001) and soil depths (p<0.001) had significant effects on the concentrations of acid-volatile sulfide (AVS). AVS concentrations generally exhibited increasing trends with an increase in depth and decreasing trends with enhanced desalination levels. The desalination levels had significant (p<0.05) effects on the concentrations of simultaneously extracted metal (SEM; Cd, Cr, Cu, Fe, Mn, Pb, and Zn). Moreover, the concentrations of SEM (Cd, Cr, Cu, Fe, Mn, Pb, and Zn) generally tended to decrease with an increase in the desalination level. The desalination treatment significantly reduced the ratios of SEM/AVS compared with control. However, the ratios of SEM/AVS increased with enhanced desalination levels in treatments. Results reveal that low desalination treatment is better for reducing toxicity to benthic organisms than high desalination treatment. Since these reclaimed tidal flats with low desalinisation are suitable for saline water aquaculture, transforming the present land use of reclaimed tidal flats from fresh water aquaculture into saline water aquaculture may reduce health risk of heavy metals remained in sediments. These results will also contribute to our understanding of the dynamic behavior of heavy metals in the reclamation of tidal flats during leaching and the role of the ratio of SEM/AVS predictions on assessing the ecological risks of reclaimed tidal flats.

Effects of time, soil organic matter, and iron oxides on the relative retention and redistribution of lead, cadmium, and copper on soils.

In order to predict the bioavailability of toxic metals in soils undergoing degradation of organic matter (OM) and iron oxides (IOs), it is vital to understand the roles of these soil components in relation to metal retention and redistribution with time. In this present work, batch competitive sorptions of Pb(II), Cu(II), and Cd(II) were investigated between 1 and 90 days. Results showed that competition affected Cd(II) sorption more than Cu(II) and Pb(II). The sorption followed the trend Pb(II) > > Cu(II) > Cd(II), irrespective of aging, and this high preference for Pb(II) ions in soils reduced with time. Removal of OM led to reduction in distribution coefficient (K d) values of ≈33% for all cations within the first day. However, K d increased nearly 100% after 7 days and over 1000% after 90-day period. The enhanced K d values indicated that sorptions occurred on the long run on surfaces which were masked by OM. Removal of IO caused selective increases in the K d values, but this was dependent on the dominant soil constituent(s) in the absence of IO. The K d values of the IO-degraded samples nearly remained constant irrespective of aging indicating that sorptions on soil components other than the IO are nearly instantaneous while iron oxides played greater role than other constituents with time. Hence, in the soils studied, organic matter content determines the immediate relative metal retention while iron oxides determine the redistribution of metals with time.

In situ stabilization remediation of cadmium (Cd) and lead (Pb) co-contaminated paddy soil using bentonite

A pot trial was conducted to evaluate the effectiveness of bentonite in immobilizing Cd and Pb in soils using a set of parameters such as biochemical and physiological characteristics, metal fractions, plant growth and heavy metal concentrations, and soil enzyme activities and microbial community. Results showed that applying bentonite to soil increased activities of superoxide dismutase (SOD) in roots and peroxidase (POD) in leaves and soluble protein (SP) contents in roots of rice seedling by 2.19–2.46, 0.18–0.34, and 0.06–2.20 times, but decreased malondialdehyde (MDA) contents in leaves and roots by up to 74.1% and 62.1%, respectively, as compared with the control. The additions of bentonite reduced the exchangeable fraction of Cd by 11.1%–42.5% and that of Pb by 20.3%–49.3%, most of which was converted into unavailable forms, resulting in 3.0%–54.3% and 6.7%–10.0% increases in residual portions, respectively. Treatments with bentonite inhibited Cd and Pb translocation from soil to the aerial parts of Oryza sativa L. Compared with the control, bentonite applications reduced concentrations of Cd and Pb in the roots by 9.4%–31.3% and 5.1%–26.7%, and by 17.4%–44.3% and 3.7%–7.8% in the shoots, respectively. The decreased catalase and increased values of invertase and urease activities and bacteria, fungi, and actinomycete population in the soil implied certain metabolic recovery and soil quality improvements by bentonite additions. These results indicate that bentonite has the potential to reduce heavy metal bioavailability in paddy soils.

Improving the relationship between soil characteristics and metal bioavailability by using reactive fractions of soil parameters in calcareous soils.

The contribution of the nature instead of the total content of soil parameters relevant to metal bioavailability in lettuce was tested using a series of low-polluted Mediterranean agricultural calcareous soils offering natural gradients in the content and composition of carbonate, organic, and oxide fractions. Two datasets were compared by canonical ordination based on redundancy analysis: total concentrations (TC dataset) of main soil parameters (constituents, phases, or elements) involved in metal retention and bioavailability; and chemically defined reactive fractions of these parameters (RF dataset). The metal bioavailability patterns were satisfactorily explained only when the RF dataset was used, and the results showed that the proportion of crystalline Fe oxides, dissolved organic C, diethylene-triamine-pentaacetic acid (DTPA)-extractable Cu and Zn, and a labile organic pool accounted for 76% of the variance. In addition, 2 multipollution scenarios by metal spiking were tested that showed better relationships with the RF dataset than with the TC dataset (up to 17% more) and new reactive fractions involved. For Mediterranean calcareous soils, the use of reactive pools of soil parameters rather than their total contents improved the relationships between soil constituents and metal bioavailability. Such pool determinations should be systematically included in studies dealing with bioavailability or risk assessment.

생분해되는 다양한 킬레이트들이 수은에 노출된 식물의 뿌리성장에 미치는 영향

Phytoextraction is a method of phytoremediation using plants to clean up metal-contaminated soils. Recently, various chelating agents were used in this method to increase the bioavailability of metals in soils. Even though phytoextraction is an economic and environmentally friendly method, this cannot be applied in highly metal-contaminated areas because plants will not normally grow in such conditions. This research focuses on identifying chelating agents which are biodegradable and applicable to highly metal-contaminated areas. Copper (Cu) as a target metal and cysteine (Cys), histidine (His), citrate, malate, oxalate, succinate, and ethylenediamine (EDA) as biodegradable chelating agents were selected. Ethylenediamine tetraacetic acid (EDTA) was used as a comparative standard. Plants were grown on agar media containing various chelating agents with Cu to analyze the effect on root growth. Cys, His, and citrate strongly diminished the inhibitory effect of Cu on root growth of plants. The effect of oxalate was weak, and malate and succinate did not show significant effects. EDTA diminished and EDA promoted the inhibitory effects of Cu on root growth. These effects of chelating agents are correlated with Cu uptake into the roots. In conclusion, as biodegradable chelating agents, Cys, His, and citrate are good candidates for highly Cu-contaminated areas, while EDA can be useful in phytoextraction for Cu.

Immobilization and phytotoxicity reduction of heavy metals in serpentine soil using biochar

PurposeSerpentine soils derived from ultramafic rocks release elevated concentrations of toxic heavy metals into the environment. Hence, crop plants cultivated in or adjacent to serpentine soil may experience reduced growth due to phytotoxicity as well as accumulate toxic heavy metals in edible tissues. We investigated the potential of biochar (BC), a waste byproduct of bioenergy industry in Sri Lanka, as a soil amendment to immobilize Ni, Cr, and Mn in serpentine soil and minimize their phytotoxicity.Materials and methodsThe BC used in this study was a waste byproduct obtained from a Dendro bioenergy industry in Sri Lanka. This BC was produced by pyrolyzing Gliricidia sepium biomass at 900 °C in a closed reactor. A pot experiment was conducted using tomato plants (Lycopersicon esculentum L.) by adding 1, 2.5, and 5 % (w/w) BC applications to evaluate the bioavailability and uptake of metals in serpentine soil. Sequential extractions were utilized to evaluate the effects of BC on bioavailable concentrations of Ni, Cr, and Mn as well as different metal fractionations in BC-amended and BC-unamended soil. Postharvest soil in each pot was subjected to a microbial analysis to evaluate the total bacterial and fungal count in BC-amended and BC-unamended serpentine soil.Results and discussionTomato plants grown in 5 % BC-amended soil showed approximately 40-fold higher biomass than that of BC-unamended soil, whereas highly favorable microbial growth was observed in the 2.5 % BC-amended soil. Bioaccumulation of Cr, Ni, and Mn decreased by 93–97 % in tomato plants grown in 5 % BC-amended soil compared to the BC-unamended soil. Sequentially extracted metals in the exchangeable fraction revealed that the bioavailabile concentrations of Cr, Ni, and Mn decreased by 99, 61, and 42 %, respectively, in the 5 % BC-amended soil.ConclusionsResults suggested that the addition of BC to serpentine soil as a soil amendment immobilizes Cr, Ni, and Mn in serpentine soil and reduces metal-induced toxicities in tomato plants.

Transformation of heavy metal fractions on soil urease and nitrate reductase activities in copper and selenium co-contaminated soil

This study aims to explore the effects of the distribution, transformation and bioavailability of different fractions of copper (Cu) and selenium (Se) in co-contaminated soils on soil enzymes, providing references for the phytoremediation of contaminated areas and agriculture environmental protection. Pot experiments and laboratory analysis were used to investigate the transformation and bioavailability of additional Cu and Se for pakchoi (Brassica chinensis) in co-contaminated soil. In the uncontaminated soil, Cu mainly existed in residual form, whereas Se was present in residual form and in elemental and organic-sulfide matter-bound form. In the contaminated soil, Cu mainly bound to Fe–Mn oxidates, whereas Se was in exchangeable and carbonates forms. After a month of pakchoi growth, Cu tended to transfer into organic matter-bound fractions, whereas Se tended to bound to Fe–Mn oxidates. The IR (reduced partition index) value of Cu decreased as the concentrations of Cu and Se gradually increased, whereas the IR value of Se decreased as the concentration of Se increased. The IR value before pakchoi planting and after it was harvested was not affected by the concentration of exogenous Cu. Soil urease and nitrate reductase activities were inhibited by Cu and Se pollution either individually or combined in different degrees, following the order nitrate reductase>urease. The significant correlation between the IR value and soil enzyme activities suggests that this value could be used to evaluate the bioavailability of heavy metals in soil. Path analysis showed that the variations in exchangeable Cu and organic-sulfide matter-bound and elemental Se had direct effects on the activities of the two enzymes, suggesting their high bioavailability. Therefore, the IR value and the transformation of metals in soil could be used as indicators in evaluating the bioavailability of heavy metals.

Effect of selenium fertilization on the accumulation of cadmium and lead in rice plants

The accumulation of cadmium and lead in rice (Oryza sativa L.) grains is a potential threat to human health. In this study, the effect of selenium fertilization on the uptake and translocation of cadmium and lead in rice plants was investigated. Rice plants were cultivated using cadmium and lead contaminated soils with selenium addition at three concentrations (0, 0.5 and 1 mg kg−1). At maturity, plants were harvested, and element concentrations in rice tissues were analyzed by using ICP-MS. Selenium application significantly increased selenium accumulation in rice grain, and markedly decreased cadmium and lead concentrations in rice tissues. In brown rice grains, selenium application reduced cadmium concentrations by 44.4 %, but had no significant effect on lead accumulation. Selenium application significantly decreased metal mobility in soils, at 0.5 mg kg−1 treatment, the translocation factor of cadmium and lead from soil to iron plaque decreased by 71 and 33 % respectively. The mechanism of selenium mitigating of heavy metal accumulation in rice could be decreasing metal bioavailability in soil. Selenium fertilization could be an effective and feasible method to enrich selenium and reduce cadmium levels in brown rice.

Impact of repeated single-metal and multi-metal pollution events on soil quality

Most frequently, soil metal pollution results from the occurrence of repeated single-metal and, above all, multi-metal pollution events, with concomitant adverse consequences for soil quality. Therefore, in this study, we evaluated the impact of repeated single-metal and multi-metal (Cd, Pb, Cu, Zn) pollution events on soil quality, as reflected by the values of a variety of soil microbial parameters with potential as bioindicators of soil functioning. Specifically, parameters of microbial activity (potentially mineralizable nitrogen, β-glucosidase and acid phosphatase activity) and biomass (fungal and bacterial gene abundance by RT-qPCR) were determined, in the artificially metal-polluted soil samples, at regular intervals over a period of 26weeks. Similarly, we studied the evolution over time of CaCl2-extractable metal fractions, in order to estimate metal bioavailability in soil. Different metals showed different values of bioavailability and relative bioavailability ([metal]bio/[metal]tot) in soil throughout the experiment, under both repeated single-metal and multi-metal pollution events. Both repeated Zn-pollution and multi-metal pollution events led to a significant reduction in the values of acid phosphatase activity, and bacterial and fungal gene abundance, reflecting the negative impact of these repeated events on soil microbial activity and biomass, and, hence, soil quality.