Micro/nanostructured hydroxyapatite structurally enhances the immobilization for Cu and Cd in contaminated soil

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.

     

Heavy metal distribution in different soil aggregate size classes from restored brackish marsh,oil exploitation zone,and tidal mud flat of the Yellow River Delta

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.

     

Effects of biochar on copper immobilization and soil microbial communities in a metal-contaminated soil

Purpose

Copper (Cu) contamination has been increasing in land ecosystems. Biochars (BCs) and arbuscular mycorrhizal fungi (AMF) are known to bind metals, and metallophyte can remove metals from soils. Will BC in combination with AMF contain the Cu uptake by a metallophyte growing in a metal-contaminated soil? The objective of this study was to investigate the effects of BCs on the Cu immobilization and over soil microbial communities in a metal-contaminated soil in the presence of AMF and metallophyte.

Materials and methods

Two BCs were produced from chicken manure (CMB) and oat hull (OHB). A Cu-contaminated sandy soil (338 mg kg^?1) was incubated with CMB and OHB (0, 1, and 5 % w/w) for 2 weeks. Metallophyte Oenothera picensis was grown in pots (500 mL) containing the incubated soils in a controlled greenhouse for 6 months. A number of analyses were conducted after the harvest. These include plant biomass weight, microbial basal respiration, and dehydrogenase activity (DHA), AMF root colonization, spore number, and glomalin production; changes in fungal and bacterial communities, Cu fractions in soil phases, and Cu uptake in plant tissues.

Results and discussion

The BCs increased the soil pH, decreased easily exchangeable fraction of Cu, and increased organic matter and residual fraction of Cu. The BCs provided favorable habitat for microorganisms, thereby increasing basal respiration. The CMB increased DHA by ～62 and ～574 %, respectively, for the low and high doses. Similarly, the OHB increased soil microbial activity by ～68 and ～72 %, respectively, for the low and high doses. AMF root colonization, spore number, and total glomalin-related soil protein (GRSP) production increased by ～3, ～2, and ～3 times, respectively, in soils treated with 1 % OHB. Despite being a metalophyte, O. picensis could not uptake Cu efficiently. Root and shoot Cu concentrations decreased or changed insignificantly in most BC treatments.

Conclusions

The results show that the BCs decreased bioavailable Cu, decreased Cu uptake by O. picensis, improved habitat for microorganisms, and enhanced plant growth in Cu-contaminated soil. This suggests that biochars may be utilized to remediate Cu-contaminated soils.

     

Pollution assessment and spatial variation of soil heavy metals in Lixia River Region of Eastern China

Purpose

The effect of soil heavy metals on crops and human health is an important research topic in some fields (Agriculture, Ecology et al.). In this paper, the objective is to understand the pollution status and spatial variability of soil heavy metals in this study area. These results can help decision-makers apportion possible soil heavy metal sources and formulate pollution control policies, effective soil remediation, and management strategies.

Materials and methods

A total of 212 topsoil samples (0–20 cm) were collected and analyzed for eight heavy metals (Cd, Hg, As, Cu, Pb, Cr, Zn, and Ni) from agricultural areas of Yingbao County in Lixia River Region of Eastern China, by using four indices (pollution index (PI), Nemerow pollution index (PI_N), index of geo-accumulation (I _geo), E _i /risk index (RI)) and cluster analysis to assess pollution level and ecological risk level of soil heavy metals and combining with geostatistics to analyze the concentration change of heavy metals in soils. GS+ software was used to analyze the spatial variation of soil heavy metals, and the semi-variogram model is the main tool to calculate the spatial variability and provide the input parameters for the spatial interpolation of kriging. Arcgis software was used to draw the spatial distribution of soil heavy metals.

Results and discussion

The result indicated that the eight heavy metals in soils of this area had moderate variations, with CVs ranging from 23.51 to 64.37 %. Single pollution index and Nemerow pollution index showed that about 2.7 and 1.36 % of soil sampling sites were moderately polluted by Cd and Zn, respectively. The pollution level of soil heavy metals decreased in the order of Cd?>?Zn?>?Pb?>?As?>?Cu?>?Cr?>?Ni?>?Hg. The I _geo values of heavy metals in this area decreased in the order of Zn?>?Cd?>?As?>?Pb?>?Cu?>?Cr?>?Hg?>?Ni. According to the E _i index, except Cd that was in the moderate ecological risk status, other heavy metals in soils were in the light ecological risk status, and the level of potential ecological risk (RI) of soil sampling sites of the whole area was light.

Conclusions

The results of four indices and the analysis of spatial variation indicated that the contents of Cd and Zn were contributed mainly by anthropogenic activities and located in the south-east of this study area. However, the contents of Hg, As, Cu, Pb, Cr, and Ni in soils were primarily influenced by soil parent materials.

     

A novel heavy metal chelating agent sixthio guanidine acid for in situ remediation of soils contaminated with multielements: its synthesis,solidification, biodegradability,and leachability

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.

     

Mixed chelators of EDTA,GLDA, and citric acid as washing agent effectively remove Cd,Zn, Pb,and Cu from soils

Purpose

Soil washing with chelators is a viable treatment alternative for remediating multi-contaminated soils. The aim of this study was to investigate the removal efficiencies of Cd, Zn, Pb, and Cu in alkaline and acid multi-metal-contaminated soils by washing with the mixed chelators (MC).

Materials and methods

The batch experiments were carried out to evaluate the removal efficiencies of heavy metals in contaminated soils by the MC with different molar ratios of EDTA, GLDA, and citric acid, and evaluated the washing factors, including contact time, pH, MC concentration, and single and multiple washings at the same MC dose, on the removal efficiencies.

Results and discussion

Results showed that the removal efficiencies for Cd, Zn, Pb, and Cu by the MC (the molar ratio of EDTA, GLDA, and citric acid was 1:1:3) were as much as those of the only EDTA washing from both soil at the same application dose of total chelators; moreover, the application dose of EDTA decreased by 80%. For the alkaline-contaminated soil, the removal efficiencies of Cd, Zn, Pb, and Cu decreased with the increasing of the solution pH, which was opposite to acid-contaminated soil. This was attributed to that the metal-ligand complex could be obviously re-adsorbed on the soil surface sites, particularly in low pH values. The removal efficiencies of Cd, Zn, Pb, and Cu depended on MC concentration. A higher MC concentration led to a more effective removal of Cd, Zn, Pb, and Cu in alkaline-contaminated soil; however, their changes were slightly increased in acid-contaminated soil. At the same dose of MC, single washing with higher MC concentration might be favorable to remove heavy metals, moreover, with much less wastewater generation.

Conclusions

The MC (the molar ratio of EDTA, GLDA, and citric acid was 1:1:3) may be a useful, environmentally friendly, and cost-effective chelators to remediate heavily multi-metal-contaminated soil.

     

Immobilization of Cu and Cd in a contaminated soil: one- and four-year field effects

Purpose

Many amendments have been applied to immobilize heavy metals in soil. However, little information is available on the changes of immobilization efficiencies of heavy metals in contaminated soils over time. This work investigated the immobilization efficiencies of copper (Cu) and cadmium (Cd) in contaminated soils in situ remediated with one-time application of three amendments for 1 year and 4 years.

Materials and methods

Apatite, lime, and charcoal were mixed with the topsoil of each plot with the amounts of 22.3, 4.45, and 66.8 t/ha, respectively. Soil chemical properties and fractions of Cu and Cd were examined after in situ remediation for 1 year and 4 years. Soil sorption and retention capacities and desorption proportions for Cu and Cd were investigated by batch experiments.

Results and discussion

The addition of amendments significantly increased soil pH, but decreased exchange acid and aluminum (Al). The amendments significantly decreased the CaCl₂ extractable Cu and Cd and transformed them from active to inactive fractions. After the application of amendments for 1 year, the maximum sorption capacities ranged from 35.6 to 38.8 mmol/kg for Cu and from 14.4 to 17.0 mmol/kg for Cd, which were markedly higher than those of the application of amendments for 4 years (Cu, 29.6–34.7 mmol/kg; Cd, 10.9–16.4 mmol/kg). Desorption proportions (D) of Cu and Cd using three extractants followed the order of \( {D}_{{\mathrm{NaNO}}_3}<{D}_{{\mathrm{CaCI}}_2}<{D}_{{\mathrm{MgCI}}_2} \) . Moreover, the retention capacities (R) of Cu and Cd both increased and followed the order of R _apatite?>?R _lime?>?R _charcoal, resulting in higher Cu and Cd in the amended soils than the untreated soil.

Conclusions

Apatite, lime, and charcoal increased the soil sorption and retention capacities of Cu and Cd and resulted in higher immobilization efficiencies in the amended soils than the untreated soil. However, the immobilization efficiencies of Cu and Cd decreased with the decrease of sorption capacities after 4 years. It was concluded that apatite had the best effect on the long-term stability of immobilized Cu and Cd and can be applied to immobilize heavy metals in contaminated soils.     

Dry cultivation enhances cadmium solubility in contaminated soils but minimizes cadmium accumulation in a leafy vegetable

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.

     

Evaluation of palygorskite for remediation of Cd-polluted soil with different water conditions

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.

     

Effect of the size of variable charge soil particles on cadmium accumulation and adsorption

Purpose

The size of soil particles strongly affects the accumulation and adsorption of heavy metals which partly controls the co-transport of heavy metals by soil colloids. However, the effect of the size of soil particles on the accumulation and adsorption of heavy metals in the colloidal dimension has seldom been studied. In this study, variable charge soils were selected and separated into five size fractions to elucidate the effect of the size of soil particles on Cd accumulation and adsorption.

Materials and methods

Five soil particle size fractions (>10, 10–1, 1–0.45, 0.45–0.2 and <0.2 μm) were obtained from Cd-contaminated soil by natural sedimentation and fractional centrifugation. The concentrations and species of Cd were measured in various sized soil particles. Batch adsorption experiments of Cd on the obtained soil particles were conducted under different pH values and concentrations of NaCl.

Results and discussion

Generally, the concentration of Cd increased with decreasing soil particle sizes, and the Cd proportion of exchangeable and carbonate fraction decreased from 43.84 to 17.75% with decreasing particle size. The soil particles with a size of 10–1 and <0.2 μm possessed a stronger adsorption ability than the other fractions in most cases. Moreover, the Cd adsorption capacities of the soil particles increased with increasing pH values and decreasing concentrations of NaCl, especially for soil particles containing more organic matter (OM) and variable charge minerals.

Conclusions

Smaller soil particles are more capable of accumulating Cd and make Cd more stable. The adsorption capability of Cd is negatively related to the particle size and NaCl concentration and is positively related to the pH. The effects of the size of variable charge soil particles on Cd accumulation and adsorption are attributed to the differences in the physicochemical properties among various soil particle size fractions. This study contributes to the understanding of the co-transport of heavy metals in soil by soil colloids.

     

Chicken-manure-derived biochar reduced bioavailability of copper in a contaminated soil

Purpose

Copper (Cu) contamination has been increasing in land ecosystems due to economic development activities. Excessive amount of Cu in soils is toxic to both plants and microorganisms. Biochar (BC) is known to immobilize soil Cu. The objectives of this research were to investigate the effects of chicken-manure-derived BC (CMB) on Cu immobilization, and growth of native metallophyte Oenothera picensis in a Cu-contaminated soil.

Materials and methods

A Cu-contaminated sandy soil (338 mg Cu kg^?1) was spiked and equilibrated with additional Cu (0, 100, and 500 mg Cu kg^?1). The spiked soil was then amended with CMB (0, 5, and 10 % w/w) and incubated for 2 weeks. The metallophyte was grown on these treatments under greenhouse conditions for 3 months. Pore water solutions were collected from the plant pots every 30 days. After the harvest, soil and pore water pH, soil Cu fractions, pore water Cu concentration, soil microbial activity, plant biomass weight, and Cu concentration in plant parts were determined.

Results and discussion

The CMB increased the pH of soils and soil pore water, and probably also soil major nutrients. It reduced the exchangeable fraction of Cu but increased its organic matter and residual fractions. At the same time, it decreased the Cu concentration in the soil pore water. The CMB increased basal respiration and dehydrogenase activity. The CMB application produced up to three and seven times more root and shoot biomass, respectively. In addition, shoots accumulated lesser Cu than control but roots did more. Plants survived in soil that was spiked with 500 mg Cu kg^?1, only when CMB dose was 10 %.

Conclusions

The CMB affected the Cu uptake in plant by altering the mobility, bioavailability, and spatial distribution of Cu in soils. The increase in available nutrients and decrease in Cu toxicity facilitated plant growth. The increased microbial activity probably also promoted the plant growth and reduced the Cu bioavailability. Therefore, CMB can be used to remediate Cu-contaminated soils.

     

Source identification and apportionment of soil cadmium in cropland of Eastern China: a combined approach of models and geographic information system

Purpose

Cadmium (Cd) is regarded as one of the most toxic heavy metals in the environment and can undermine the ecosystem function and human health at trace level due to its high toxicity. In order to reduce the anthropogenic Cd input into agricultural soil, it is of utmost importance to pinpoint the sources of Cd in soils and apportion their respective contributions.

Materials and methods

One hundred twenty-seven topsoil samples and 21 subsoil samples were collected from croplands of Meishan Basin, Changxing County, Zhejiang Province, Eastern China, and analyzed for concentrations of Cd and other heavy metals. Finite mixture distribution model (FMDM) was employed to fit the data to obtain the local soil Cd threshold value, a critical indicator to assess soil heavy metal contamination. Then, principal component analysis (PCA) and geographic information system (GIS) were used to identify the potential sources of Cd. Finally, positive matrix factorization (PMF) was applied to apportion the source contributions.

Results and discussion

Among the 127 topsoil samples, 71 were subject to Cd contamination with a mean concentration of 0.66 mg kg^?1 while the others were considered as background with a lower mean concentration of 0.145 mg kg^?1, close to the local background concentration of 0.142 mg kg^?1. Further, three components were extracted by PCA and interpreted as natural background, lead-acid battery manufacturing plants, and construction material associated activities, respectively. Additionally, most of the topsoil samples around the lead-acid battery manufacturing plants, construction material plants, and limestone/marble quarries were classified as Cd contaminated. However, PMF failed to get a successful portioning.

Conclusions

Lead-acid battery manufacturing plants and construction material associated activities were the main anthropogenic sources of soil Cd contamination. With the help of FMDM, it is possible to distinguish the contaminated soil and estimate the contribution of anthropogenic sources to soil Cd. The apportionment by PMF was not successful in this paper due to the high skewness or outliers of Cd concentration in sampling sites and violation of the assumption that all samples have the same sources.

     

Protective mechanism of the soil–plant system with respect to heavy metals

Purpose

The aim of this work was to select and assess the efficiency of different amendments applied to ordinary chernozems artificially contaminated with heavy metals (Zn and Pb).

Materials and methods

The effect of different amendments on ordinary chernozem contaminated with Zn and Pb acetate salts was studied in a long-term 3-year field experiment. Glauconite, chalk, manure, and their combinations were chosen as ameliorating agents. Spring barley (Hordeum sativum) was used as test culture for three successive years. The heavy metal concentration in all the soil samples decomposed by HF?+?HClO₄ was determined by atomic absorption spectrophotometry (AAS). One normal concentration of CH₃COONH₄ at pH 4.8 was used to estimate the actual mobility of metals. The compounds of heavy metals extracted by 1 N HCl are regarded as mobile compounds. The concentration of metals in the plants was determined using the dry combustion in a mixture of HNO₃ and HCl at 450 °C. The content of heavy metals in extracts from soil and plant samples was determined by AAS.

Results and discussion

The content of weakly bound metal compounds increased upon the contamination of the soil with Pb and Zn salts, which led to a low quality of barley grown in these soils. Metal concentrations in the barley grain exceeded the maximum permissible concentrations (MPCs). The content of Zn and Pb in grains was higher than the MPC for at least 3 years after the soil pollution. The application of amendments significantly decreased the mobility of metals, and the simultaneous application of chalk and manure was most significant. The share of weakly bound metal compounds in the contaminated soils decreased to the level typical for the clean soils or even below.

Conclusions

The combined application of chalk and manure to Zn- and Pb-contaminated ordinary chernozems decreased the content of weakly bound metal compounds in the soil and lowered their concentrations in barley plants. The polyfunctional properties of the soil components with respect to their capacity for metal fixation were established. The decrease in the intensity of Zn accumulation in grains of barley shows the presence of a barrier at the root–stalk and stalk–grain interfaces.

     

The change of heavy metals fractions during hydrochar decomposition in soils amended with different municipal sewage sludge hydrochars

Purpose

This study was to investigate the changes of heavy metals in the soils amended with different municipal sewage sludge hydrochars.

Materials and methods

Sewage sludge hydrochars prepared at either 190 or 260 °C, for 1, 6, 12, 18, or 24 h, respectively, were added to soil samples and then incubated for 60 days. Water-extractable organic carbon (WEOC) and CO₂ evolution were determined during the incubation. The total quantities of heavy metals and their different fractions were analyzed by inductively coupled plasma spectrometry (ICP).

Results and discussion

Hydrochar-amended soils had much higher water-extractable carbon and more CO₂ evolution than control soil, indicating that the added hydrochars contained a significant amount of WEOC and could be decomposed during the incubation. Hydrochar addition immediately and significantly increased the total heavy metals of the soil. Moreover, both oxidizable and residual fractions of all heavy metals were significantly higher in all the hydrochar-added soils than those in control soil. Both oxidable and residual fractions of heavy metals decreased in the hydrochar-amended soils during 60-day incubation. In contrary, both acid soluble and reducible fractions of heavy metals increased in the hydrochar-amended soils during incubation. It is thus obvious that the heavy metals in both oxidable and residual fractions may be released during hydrochar decomposition and then be adsorbed by soil matrix such as carbonates, iron oxides, and clays.

Conclusions

Municipal sewage sludge can be readily carbonized into hydrochar. However, it is watchful of applying the hydrochar into soil since hydrochar addition increases in both total and bioavailable heavy metals in soil. More work is particularly required to investigate the long-term impacts on soil and environment.

     

Spatial distribution and source apportionment of the heavy metals in the agricultural soil in a regional scale

Purpose

Understanding the spatial distribution and sources of soil heavy metals (HMs) in a large city helps prevent and control soil pollution. This study aimed to investigate the spatial patterns of soil HMs and identify their main sources in a regional scale.

Materials and methods

A total of 110 topsoil samples were collected from Tai’an City, China. Cd, Cr, Cu, Hg, Ni, Pb, and Zn concentrations in each soil sample were determined. Geostatistics, geographic information system (GIS), and positive matrix factorization (PMF) were used to explore the spatial distribution of seven soil HMs and to reveal the main sources of soil HMs in Tai’an City, respectively.

Results and discussion

Soil Cd, Cr, Pb, and Zn generally showed slight pollution levels in the study area. However, soil Hg and Cu contents reached moderate to heavy pollution levels in some areas. Soil Hg content increased from north to south across the city, and the highest Hg concentration was detected in Ningyang County. Soil Cd, Cu, and Zn distributions exhibited a similar pattern, and their contents increased from west to east; the highest Cd, Cu, and Zn concentrations were found in Xintai County. The highest soil Ni concentration was obtained in the northeast of Feicheng and Xintai counties. PMF analysis revealed the following four potential sources of agricultural soil HMs in Tai’an City: industrial and mining activities, agricultural activities, residential living activities, and business activities. Soil Hg mainly originated from residential living activities, which accounted for 75.3% of the total source. The main sources of soil Ni were residential living activities, agricultural activities, and industrial and mining activities, which account for 38.2, 27.50, and 25.1% of the total source, respectively. Soil Cu was mainly produced by agricultural activities (36.6%), followed by residential living activities (29.8%) and industrial and mining activities (25.8%).

Conclusions

PMF combined with GIS could be effectively applied to determine the main sources of HMs in agricultural soils in a regional scale.

     

Response of CaCl<Subscript>2</Subscript>-extractable heavy metals,polychlorinated biphenyls,and microbial communities to biochar amendment in naturally contaminated soils

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.

     

Plant growth and heavy metal bioavailability changes in a loess subsoil amended with municipal sludge compost

Purpose

The effects of municipal sludge compost (MSC) as a soil amendment are often studied in agricultural soil or topsoil contaminated with heavy metals. However, little is known about the effects of MSC amendments on plant growth and heavy metal bioavailability in subsoil. This study was conducted to investigate the effects of MSC application on plant growth and the mobility and bioavailability of Cd, Cu, and Zn in an amended soil-plant system.

Materials and methods

A pot experiment was performed to evaluate the translocation of heavy metals to broad bean (Vicia faba L.) grown in loess subsoil previously amended with different application rates of MSC. The subsoil and MSC were homogeneously mixed to achieve six soil-amended treatments (total weight of 8 kg in each pot) in 0, 0.5, 2, 6, 15, and 30% mass ratios (MSC/total). Soil samples amended with MSC were aged for 60 days before sowing. Soil and plant samples were collected after 120 days of growth. Plant height was periodically measured until harvest. The total quantities of heavy metals and their different fractions were analyzed by using graphite furnace atomic absorption spectroscopy (GF-AAS).

Results and discussion

Compared with the control soil (0% treatment), the average biomass growth rates from the 0.5 to 30% treatments ranged from 14.5 to 170.4% (increasing order), respectively. Cd (0.42–1.85 mg kg^?1) and Cu (14.95–23.01 mg kg^?1) mainly concentrated in the plant roots, and Zn (22.06–36.48 mg kg^?1) mainly concentrated in the plant stems and leaves. Fortunately, the metal concentrations in the edible plant parts (0.03–0.1 mg kg^?1) remained below the Chinese national standard thresholds (0.2 mg kg^?1), possibly because of the alkaline soil pH (8.60–7.74), organic matter (7.4–65.9 g kg^?1) bound to metals, and translocation of less metal to the edible plant parts by biochemical modulation.

Conclusions

MSC can enhance subsoil fertility and promote plant development, especially in the 30% treatment. The mobility and bioavailability of heavy metals suggest that Cd is the element needing to be monitored during MSC application. High organic matter content and alkaline pH are the most important factors for controlling Cd levels. More work is required to determine the long-term impacts of sludge amendment on the soil and environment.

     

Regulation of macro,micro, and toxic element uptake by <Emphasis Type="Italic">Salix</Emphasis> × <Emphasis Type="Italic">smithiana</Emphasis> using liming of heavily contaminated soils

Purpose

Willow cultivation in soils heavily contaminated by risk elements is a challenging issue due to phytotoxic effects that restrict plant growth. Liming reduces the mobility of some risk elements in contaminated soils and therefore can be a suitable measure for contaminated soils but can also affect availability of nutrients for planted willows. We investigate how liming affects concentrations of macro, micro, and toxic elements in the organs of willows planted in contaminated soils.

Materials and methods

We established a 3-year pot experiment with Salix × smithiana planted in weakly acid and alkaline soils anthropogenically seriously contaminated by As, Cd, Pb, and Zn. Soils were both untreated and treated with two doses of lime and dolomite in the first year before planting. We determined biomass production, mortality, and the concentration of macro- and micronutrients and toxic elements in the willows’ aboveground organs.

Results and discussion

Lime application increased biomass production in both soils; dose of lime played an important role for its increase only in alkaline soil. Lime in a higher dose was incompatible with the vitality of just-planted willows in both soils. Doses of dolomite significantly affected the biomass production and mortality of willows, where lower doses caused a permanent decrease of biomass production and mortality in weakly acid soil. The toxicity of Cd and Zn in leaves was recorded in both untreated soils; the latent deficiency of P and deficiency of Fe in leaves was only recorded in weakly acid untreated soil.

Conclusions

Lime application irrespective of dose with foliar Fe application seemed to be the most suitable measure for increasing biomass production and decreasing toxic elements, especially Cd and Zn, without decreasing the macro- and micronutrients in the aboveground organs of willows in weakly acid soil. In alkaline soil, only higher doses of lime had a positive effect on the studied parameters. Dolomite application is not a suitable measure for planting willows in both contaminated soils. Dolomite in a lower dose impairs the growth of willows in weakly acid soil.

     

Effects of biomass ash,bone meal,and alkaline slag applied alone and combined on soil acidity and wheat growth

Purpose

The purpose of this study is to examine the effects of combined application of biomass ash (BA), bone meal (BM), and alkaline slag (AS) on soil acidity, nutrient contents, uptake of the nutrients by wheat, and wheat growth.

Materials and methods

A pot experiment with an Ultisol collected from Anhui province, China, was conducted to compare the effects of BA, BM, and AS applied alone and combined on soil acidity; soil nutrient contents; uptake of N, P, K, Ca, and Mg by wheat, and wheat growth.

Results and discussion

Application of BA, BM, and AS alone and combined increased soil pH and decreased soil exchangeable Al³⁺. BA + BM + AS showed the greatest ameliorating effect on soil acidity, and soil pH of the treatment increased by 1.24 units compared with control. Application of BA + BM + AS reduced soil exchangeable Al³⁺ and increased soil exchangeable calcium and magnesium to a greater extent than BA + BM and single application of the amendments. The BM-containing amendments substantially increased soil available phosphorous by 66–93% compared with control. Application of the amendments alone and combined enhanced the uptake of N, P, K, Ca, and Mg by wheat and thus promoted wheat growth and increased yield of wheat grains. Application of BA + BM + AS and BA + BM showed greater effects on nutrient uptake and wheat growth than single application of the amendments. Wheat straw weights of the two treatments were 11.1 and 10.1 times greater than that of control. The data were 2.7, 4.8, and 5.6 times for the treatments of BA, AS, and BM. The contents of Cd, Cr, Zn, and Cu in wheat grains were lower than standard limits, except for the single BA treatment.

Conclusions

BA + BM + AS is the best choice for amelioration of acid soils and promotion of crop production.

     

Temporal and spatial variation and risk assessment of soil heavy metal concentrations for water-level-fluctuating zones of the Three Gorges Reservoir

Purpose

This study aimed to reveal the temporal and spatial variation of soil heavy metal concentrations in the Three Gorges Reservoir area (TGR) water-level-fluctuating zone (WLFZ) and evaluated its pollution status and potential ecological risks and provide scientific basis for ecological risk prevention and ecological restoration of the TGR.

Materials and methods

This study was based on long-term monitoring of soil heavy metals (Cu, Pb, Cd, and Cr) before water level fluctuation (2008) and after 1 (2009), 4 (2012), or 7 (2015) cycles of water level fluctuation at the altitude of 155–172 m in the Wushan (WS) and Zigui (ZG) sections of the TGR, and pollution status and potential ecological risks of each heavy metal element were evaluated by index of geoaccumulation and potential ecological risk index.

Results and discussion

The Cd concentration increased with the increase in the number of reservoir water level fluctuations, whereas the concentrations of Cu, Cr, and Pb varied with the monitoring site. The Cd showed clear horizontal transfer characteristics. Moreover, with the increase of the frequency of water level fluctuations the Cd concentration at ZG (near the dam) were higher than those at WS (away from the dam). After 7 cycles of water level fluctuation, the concentrations of most soil heavy metal were not obvious differences between soil layers (except Pb). Before and after the reservoir water level fluctuation, Cd contamination level changed from pollution-free to strong or extremely polluted, Cu contamination level changed from pollution-free to moderately polluted, and Cr and Pb were pollution-free. Before the fluctuation of the reservoir water level, the potential ecological risk of Cd in the WS reached a classification of strongly polluted, whereas pollution at ZG was considered to be low level. However, after 4 cycles of water level fluctuation the Cd pollution level increased to a very high level, whereas Cu, Cr, and Pb remained consistently low.

Conclusions

There is an obvious temporal and spatial variation of heavy metal concentrations for WLFZ of TGR. Cd concentration increased with the increase in the number of reservoir water level fluctuations. Heavy metal concentrations changed from WS > ZG to WS < ZG after the impact of water level fluctuations. After 7 cycles of water level fluctuation, the distribution of heavy metals in different soil layers tends to be uniform (except Pb). Cd pollution is more serious, and there is a strong potential ecological risk.