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.

     

Sustainability of in situ remediation of Cu- and Cd-contaminated soils with one-time application of amendments in Guixi,China

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.

     

Eisenia fetida growth inhibition by amended activated carbon causes less bioaccumulation of heavy metals

Purpose

Activated carbons (ACs) were applied to evaluate the effects of surface oxidation on bioavailability and bioaccumulation of cadmium (Cd) and copper (Cu) in freshwater sediment along with Eisenia fetida biomass change.

Materials and methods

A modified sequential extraction procedure was conducted to measure the changes in bioavailable fractions of heavy metals 6 weeks after the addition of nitric acid-oxidized AC. Bioaccumulation of heavy metals in E. fetida was analyzed after 2 weeks of exposure to AC-amended contaminated sediments. Changes in biomass of earthworms caused by AC amendments were observed over 2 weeks of exposure to clean sand.

Results and discussion

Surface oxidation of AC caused little impact on AC surface properties except for oxygen contents leading to enhanced sorption capacity for heavy metals. Bioavailable fractions of the heavy metals increased after 6 weeks, and less was bioavailable with various ACs than without AC. The earthworms were exposed to the sediments mixed with ACs for 6 weeks. After 2 weeks of exposure, bioaccumulation of Cd and Cu decreased drastically. More than 76 % of Cd and 80 % of Cu reductions were observed with each type and dose of AC. Weight loss of E. fetida incubated in clean sand for 13 days after AC amendments was observed, but was not affected by surface oxidation.

Conclusions

Inhibited growth of E. fetida due to AC could be responsible for the reduced bioaccumulation of Cd and Cu in the earthworms as AC inhibited the movement of earthworms, leading to less bioturbation and decreased consumption of nutrients.     

Sorption isotherms and kinetics of Sb(V) on several Chinese soils with different physicochemical properties

Purpose

Sorption of antimony on soils is the primary factor that influences its immobilization and migration in the environment. In the present study, the sorption of Sb(V) onto seven Chinese soils with different physicochemical properties was investigated for exploring the relationship between the sorption capacity of Sb(V) and the physicochemical properties of the soils.

Materials and methods

Sorption isotherms and kinetics experiments were performed to ascertain the sorption capacity and the kinetic rate, respectively. The relationship between the sorption capacity of Sb(V) and the physicochemical properties of the soils was analyzed by multiple linear regressions.

Results and discussion

The results showed that the sorption isotherms fitted with both the Langmuir and Freundlich equations very well (R ²?=?0.936–0.997), and the sorption kinetic of Sb(V) onto the seven Chinese soils followed a pseudo-second-order reaction. The maximum sorption capacity of Sb(V) on the soils ranged from 134 to 1,333 mg?kg^?1. Nearly 94 % of the variability in maximum sorption of Sb(V) modeled by Freundlich equation could be described by Fe_DCB (dithionite–citrate–bicarbonicum extractable), and nearly 98 % of the variability could be described by Fe_DCB and Al_DCB.

Conclusions

Multiple linear regressions can be successfully applied to analyzing the relationship between sorption capacity and soil properties. Fe_DCB and Al_DCB played important roles in Sb(V) sorption onto soils. It would be useful to understand the environmental behaviors of Sb and for the implementation of risk assessment management and remediation strategies of Sb.     

Influence of plant species and phosphorus amendments on metal speciation and bioavailability in a smelter impacted soil: a case study of food-chain contamination

Purpose

The present research aimed to assess the influence of two phosphorous (P) amendments on metal speciation in rhizosphere soil and the soil–plant transfer of metals.

Materials and methods

Complementary experiments were performed: field experiments on a contaminated cultivated soil and laboratory experiments on an uncultivated contaminated soil to highlight the mechanisms involved in metal-phosphorous interactions. In laboratory experiment, P amendments were added at 120 mg P/kg of soluble KH₂PO₄ amendment and 9,000 mg P/kg of solid Ca₅(PO₄)₃OH amendment.

Results and discussion

Field-culture results showed the possible food-chain contamination due to Pb, Cd, Cu, and Zn phytoaccumulation by pea and mustard plants from a cultivated agricultural soil. Moreover, P-metal complexes were observed by microscopy in the rhizosphere soil. In laboratory experiments, the application of P amendments significantly increased Pb and Zn level in rhizosphere soil compared to control. Phosphate amendments significantly increased metal-P fraction and decreased “oxides” and “organic matter” fractions of Pb and Zn. Soluble-P amendment was more effective than solid P amendment in changing Pb and Zn speciation. The changes in metal speciation are higher in the rhizosphere soil of pea than tomato. Application of P amendments increased Pb and Zn TF root/soil but decreased TF shoot/root.

Conclusions

The effectiveness of in situ metal immobilization technique varies with the type and quantity of applied P amendment as well as plant and metal type.     

Simultaneous immobilization of lead,cadmium, and arsenic in combined contaminated soil with iron hydroxyl phosphate

Purpose

Combined contamination of lead (Pb), cadmium (Cd), and arsenic (As) in soils especially wastewater-irrigated soil causes environmental concern. The aim of this study is to develop a soil amendment for simultaneous immobilization of Pb, Cd, and As in combinative contaminated soil.

Materials and methods

A soil amendment of iron hydroxyl phosphate (FeHP) was prepared and characterized, and its potential application in simultaneous immobilization of Pb, Cd, and As in combined contaminated soil from wastewater-irrigated area was evaluated. The effects of FeHP dosage, reaction time, and soil moisture on Pb, Cd, and As immobilization in the soil were examined.

Results and discussion

The immobilization efficiencies of Pb, Cd, and As generally increased with the increasing of FeHP dosage. With FeHP dosage of 10 %, the immobilization percentages of NaHCO₃-extractable As and DTPA-extractable Pb and Cd reached 69, 59, and 44 %, respectively. The equilibrium time required for immobilization of these contaminants was in the following order: NaHCO₃-extractable As (0.25 days) < DTPA-extractable Cd(3 days) < DTPA-extractable Pb (7 days). However, the immobilization efficiencies of Pb, Cd, and As have not changed much under soil moisture varied from 20 to 100 %. According to the results of the sequential extraction, the percentages of Pb, Cd, and As in residual fractions increased after the application of FeHP amendment, while their percentages in exchangeable fractions decreased, illustrating that FeHP can effectively decrease the mobilities and bioavailabilities of Pb, Cd, and As in the soil. Moreover, the application of FeHP will not have soil acidification and soil structure problem based on the soil pH measurements and soil morphology.

Conclusions

FeHP can immobilize Pb, Cd, and As in the combinative contaminated soil from wastewater irrigation area simultaneously and effectively. Thus, it can be used as a potential soil amendment for the remediation of Pb, Cd, and As-combined contaminated soil.

     

Fractionation of Cd and Zn in Cd-contaminated soils amended by sugarcane waste products from an ethanol production plant

Purpose

Sugarcane waste products (boiler ash, filter cake, and vinasse) from an ethanol production plant were used as soil amendments by adding 3 % (w/w) in single and/or in combination, with a research focus towards stabilization of cadmium (Cd) and zinc (Zn) in contaminated soils. The objective of this laboratory study was to evaluate the effects of adding these sugarcane waste products on bioavailability of Cd and Zn over time (aging) in Cd- and Zn-contaminated agricultural soils of Thailand.

Materials and methods

Two agricultural contaminated soils of low (<3 mg kg^?1) and high (10–15 mg kg^?1) Cd concentrations were collected from Tak Province, Northwest Thailand. Fourteen treatments were sampled at 2-week intervals for 84 days for metal bioavailability using BCR extraction procedures (proposed by The Standards, Measurements and Testing Programme of the European Union, SM&T) that determined exchangeable (BCR1), reducible (BCR2), oxidizable (BCR3), and residual (BCR4) fractions, and total concentration was determined using aqua regia digestion and microwave digestion.

Results and discussion

Cd was potentially bioavailable, predominantly in exchangeable (BCR1) and reducible (BCR2) fractions, while the higher contribution of Zn was more prevalent in refractory fractions (BCR2 and BCR4). Aging had an influence on fractionation of Cd and Zn, most notably in the first two fractions (BCR1 and BCR2) of BCR sequential extraction, which resulted in reduction of exchangeable Cd during the first few weeks of incubation (T?=?0 to 28 days). At the end of pot experiment, the exchangeable Cd fraction in the low Cd (LCdS) soil was reduced from 2.3 to 4.7 % and 9.4 to 39.9 % in low and high Cd (HCdS)-contaminated soils, respectively, as compared to nonamended soils.

Conclusions

The observed reduction in exchangeable Cd (BCR1) in the amended soils at the 3 % (w/w) application rate, the low total metal concentrations, and the significant amount of essential plant nutrients (N, P, and K) within these waste products highlight the benefits of amending metal-rich soils with them.     

Fractions of Cu, Cd, and enzyme activities in a contaminated soil as affected by applications of micro- and nanohydroxyapatite

Purpose

With the rapid development of nanotechnology, hydroxyapatite-based nanoparticles have been applied in wastewater and soil remediation. However, limited studies have been conducted on the remediation of heavy metal-contaminated soils by microhydroxyapatite (MHA) and nanohydroxyapatite (NHA). Thus, we investigated the effects of MHA and NHA on soil pH values and fractions of copper (Cu) and cadmium (Cd). The changes of soil enzymes with application of MHA and NHA were also evaluated.

Materials and methods

Pots contained 200 g of the soil with MHA and NHA ranging from 1 % to 5 % incubated for 60 days under greenhouse condition, and maintained at 60 % of soil water holding capacity by adding deionized water. Soil pH, catalase, urease, and acid phosphatase were analyzed at incubation times of 7, 14, 30, and 60 days by chemical assays. The fractions of Cu and Cd were analyzed after 60 days by a sequential extraction procedure.

Results and discussion

Application of MHA and NHA significantly increased soil pH values. Especially, we found for the first time that soil pH values with 3 % (pH?>?7.90) and 5 % (pH?>?8.83) application rates of MHA were larger than that of MHA itself (pH?=?7.71). MHA was more effective than NHA in immobilizing Cu and Cd by significantly decreasing exchangeable fractions of Cu and Cd and transforming them from active to inactive fractions. Soil catalase and urease significantly increased, but acid phosphatase apparently decreased with increasing application rates of MHA. However, three enzymes activities changed slightly for NHA treatments.

Conclusions

MHA was more effective than NHA in immobilizing Cu and Cd. MHA had a more positive effect on soil catalase and urease activities than NHA. Furthermore, Pearson’s correlation coefficients showed that soil pH value was a key factor to influence the bioavailability of Cu and Cd and the activity of soil enzymes. The results of this study provided an efficient method for the remediation of heavy metal-contaminated soils.     

Evaluation and source identification of trace element contamination of soils in the Qixia lead-zinc mining area,Jiangsu, China

Purpose

The Qixia mine is one of the largest lead-zinc mines in Eastern China and has been operational for approximately 60 years. Source identification for trace element contamination of soils in the Qixia mining area has been lacking. This report details the evaluation and source identification of trace element contamination (including Cu, Zn, Pb, Cd, Hg, Cr, As, and Ni) of soils in this area.

Materials and methods

Thirty-three soil samples from roadsides and fields in the study area were collected and analyzed. The index of geo-accumulation (I _geo) was employed to evaluate contamination. Methods of multivariate statistical analysis were used to determine the probable sources of the pollutants.

Results and discussion

The analysis showed that the levels of contamination ranked in the following order: Cd > Pb/Zn> > As/Cu> > Hg > Cr/Ni. In the sampling area nearest the mine, soil samples collected from roadsides showed much higher levels of contamination than those collected from fields away from the roadways. Trace element contamination decreased as the distance from the mine increased. Contamination extended to a distance of approximately 700 m from mineral transportation routes, with the area of greatest impact at 200 m or less. Multivariate statistical analysis and ore composition data suggest that the Cu, Zn, Pb, Cd, and As found in the soil samples originate from anthropogenic sources. Ni and Cr are considered to be at natural background concentrations.

Conclusions

This study distinguished between natural and anthropogenic sources of trace element contamination in the soils of the Qixia mining area. The contamination of Cu, Zn, Pb, Cd, and As is linked to the mining activities and is likely due to the transportation of ore concentrates and tailings.     

Mechanisms of metal-phosphates formation in the rhizosphere soils of pea and tomato: environmental and sanitary consequences

Purpose

At the global scale, soil contamination with persistent metals such as lead (Pb), zinc (Zn), and copper (Cu) induces a serious threat of entering the human food chain. In the recent past, different natural and synthetic compounds have been used to immobilize metals in soil environments. However, the mechanisms involved in amendment-induced immobilization of metals in soil remained unclear. The objective of the present work was therefore to determine the mechanisms involved in metal-phosphates formation in the rhizospheric soils of pea and tomato currently cultivated in kitchen gardens.

Materials and methods

Pea and tomato were cultivated on a soil polluted by past industrial activities with Pb and Zn under two kinds of phosphate (P) amendments: (1) solid hydroxyapatite and (2) KH₂PO₄. The nature and quantities of metal-P formed in the rhizospheric soils were studied by using the selective chemical extractions and employing the combination of X-ray fluorescence micro-spectroscopy, scanning electron microscopy, and electron microprobe methods. Moreover, the influence of soil pH and organic acids excreted by plant roots on metal-P complexes formation was studied.

Results and discussion

Our results demonstrated that P amendments have no effect on metal-P complex formation in the absence of plants. But, in the presence of plants, P amendments cause Pb and Zn immobilization by forming metal-P complexes. Higher amounts of metal-P were formed in the pea rhizosphere compared to the tomato rhizosphere and in the case of soluble P compared to the solid amendment. The increase in soil-metal contact time enhanced metal-P formation.

Conclusions

The different forms of metal-P formed for the different plants under two kinds of P amendments indicate that several mechanisms are involved in metal immobilization. Metal-P complex formation in the contaminated soil depends on the type of P amendment added, duration of soil-plant contact, type of plant species, and excretion of organic acids by the plant roots in the rhizosphere.     

Biochars immobilize soil cadmium, but do not improve growth of emergent wetland species Juncus subsecundus in cadmium-contaminated soil

Purpose

An addition of biochar mixed into the substrate of constructed wetlands may alleviate toxicity of metals such as cadmium (Cd) to emergent wetland plants, leading to a better performance in terms of pollutant removal from wastewater. The objective of this study was to investigate the impact of biochars on soil Cd immobilization and phytoavailability, growth of plants, and Cd concentration, accumulation, and translocation in plant tissues in Cd-contaminated soils under waterlogged conditions.

Materials and methods

A glasshouse experiment was conducted to investigate the effect of biochars derived from different organic sources (pyrolysis of oil mallee plants or wheat chaff at 550 °C) with varied application amounts (0, 0.5, and 5 % w/w) on mitigating Cd (0, 10, and 50 mg kg^?1) toxicity to Juncus subsecundus under waterlogged soil condition. Soil pH and CaCl₂/EDTA-extractable soil Cd were determined before and after plant growth. Plant shoot number and height were monitored during the experiment. The total root length and dry weight of aboveground and belowground tissues were recorded. The concentration of Cd in plant tissues was determined.

Results and discussion

After 3 weeks of soil incubation, pH increased and CaCl₂-extractable Cd decreased significantly with biochar additions. After 9 weeks of plant growth, biochar additions significantly increased soil pH and electrical conductivity and reduced CaCl₂-extractable Cd. EDTA-extractable soil Cd significantly decreased with biochar additions (except for oil mallee biochar at the low application rate) in the high-Cd treatment, but not in the low-Cd treatment. Growth and biomass significantly decreased with Cd additions, and biochar additions did not significantly improve plant growth regardless of biochar type or application rate. The concentration, accumulation, and translocation of Cd in plants were significantly influenced by the interaction of Cd and biochar treatments. The addition of biochars reduced Cd accumulation, but less so Cd translocation in plants, at least in the low-Cd-contaminated soils.

Conclusions

Biochars immobilized soil Cd, but did not improve growth of the emergent wetland plant species at the early growth stage, probably due to the interaction between biochars and waterlogged environment. Further study is needed to elucidate the underlying mechanisms.     

Speciation of 90Sr and other metal cations in artificially contaminated soils: the influence of bone sorbent addition

Purpose

The influence of bone sorbent addition onto distribution of ⁹⁰Sr in artificially contaminated soil was preliminary studied to assess the possibility of biogenic apatite utilization for reduction of ⁹⁰Sr mobility and availability. Simultaneously, the disruption of soil micro- (Cd, Zn, Co, Cu, Cr, and Ni,) and macroelements (Al, Fe, Mn, K, Mg, and Ca) upon Sr contamination and sorbent addition was monitored.

Materials and methods

The model soil was contaminated by inactive Sr, in the form of Sr(NO₃)₂ solution. As a soil additive, sorbent obtained by annealing bovine bones at 400 °C (B400) was applied. Both the uncontaminated and Sr-contaminated soils were mixed with 1, 3, 5, and 10 % of sorbent, suspended in distilled water (initial pH?5; solid/solution ratio, 1:2), and equilibrated for 15 days on a rotary shaker. Solid residues were subjected to modified Tessier five-step sequential extraction analysis, and the amounts of chosen metals in each fraction were determined by inductively coupled plasma–optical emission spectroscopy.

Results and discussion

In the original soil, Sr was mainly found in exchangeable (61 %) and carbonate phase (16 %), whereas after contamination, the content of Sr in exchangeable phase raised to 94 %. With the addition of B400, the decrease in Sr amounts in exchangeable fraction was detected, whereas increase occurred mainly in operationally defined carbonate phase and in the residual. High level of Sr contamination caused the increase in Zn, Ni, Co, Cu, Cd, and Mn and decrease in Ca content in exchangeable phase. Sorbent addition resulted in a migration of these cations to less soluble fractions. This effect was observed even for major soil elements such as Fe, Al, and Mn, regardless of the excessive amounts of Sr in the soil.

Conclusions

Mixing the soil with B400 resulted in reduced Sr mobility and bioavailability. B400 acted as a stabilizing agent for heavy metals, as well. Apatite distinguished selectivity towards heavy metals may interfere with the Sr immobilization and disrupt original cation distribution. Further studies should include more realistic (lower) Sr concentrations in the soil, different soil types, pH, and longer incubation times.     

Contents and chemical forms of heavy metals in school and roadside topsoils and road-surface dust of Beijing

Purpose

The concentration of human activities in urban systems generally leads to urban environmental contamination. Beijing is one of ancient and biggest cities on the world. However, information is limited on Beijing’s soil contamination, especially for roadside and campus soils. Thus, the aims of this study were to investigate the contents and chemical forms of toxic heavy metals Cd, Cr, Cu, Ni, Pb, and Zn in the road-surface dust, roadside soils, and school campus soils of Beijing. In addition, enrichment and spatial variation of these toxic heavy metals in the soils and dust were assessed.

Materials and methods

Topsoil samples were collected from the schools and roadside adjacent to main ring roads, and dust samples were collected from the surface of the main ring roads of Beijing. These samples were analyzed for total contents and chemical forms of Cd, Cr, Cu, Ni, Pb, Sc, Zn, Al, and Fe. Enrichment factors (EFs, relative to the background content) were calculated to evaluate the effect of human activities on the toxic heavy metals in soils.

Results and discussion

Heavy metal contents in the road dust ranged from 0.16 to 0.80, 52.2 to 180.7, 18.4 to 182.8, 11.9 to 47.4, 23.0 to 268.3, and 85.7 to 980.9 mg kg^?1 for Cd, Cr, Cu, Ni, Pb, and Zn, respectively. In the roadside soil and school soil, Cd, Cr, Cu, Ni, Pb, and Zn contents ranged from 0.13 to 0.42, 46.1 to 82.4, 22.7 to 71.6, 20.7 to 29.2, 23.2 to 180.7, and 64.5 to 217.3 mg kg^?1, respectively. The average EF values of these metals were significantly higher in the dust than in the soils. In addition, the average EF values of Cd, Cu, Pb, and Zn in the soils near second ring road were significantly higher than those near third, fourth, and fifth ring roads. Anthropogenic Cd, Pb, and Zn were mainly bound to the carbonates and soil organic matter, while anthropogenic Cu was mainly bound to oxides. The mobility and bioavailability of these metals in the urban soils of Beijing generally decreased in the following order: Cd?>?Zn?>?Pb?>?Cu?>?Ni?>?Cr; while in the dust, they decreased in the following order: Zn, Cu, and Cd?>?Pb?>?Ni?>?Cr.

Conclusions

Both EF and chemical forms documented that Cr and Ni in the soils and dust mainly originated from native sources, while Cd, Cu, Pb, and Zn partially originated from anthropogenic sources. In overall, Beijing’s road dust was significantly contaminated by Cd and Cu and moderately contaminated by Cr, Pb, and Zn, while Beijing’s roadside soil and school soil were moderately contaminated by Cd and Pb. However, the maximal hazard quotients (HQs) for individual Cd, Cr, Cu, Ni, Pb, and Zn and comprehensive hazard index (HI) of these metals in the dust and soil were less than 1, indicating that the heavy metals in the dust and soil generally do not pose potential health effects to children, sensitive population.     

The influence of compost addition on heavy metal distribution between operationally defined geochemical fractions and on metal accumulation in plant

Purpose

Metal distribution patterns among geochemical fractions are informative for metal phytoavailability. Compost added to polluted soils may adsorb metals on the less phytoavailable fractions. A bioassay experiment was conducted to establish possible correlations between metal concentrations in different soil fractions and metal contents in edible plant parts and to investigate the influence of different compost loads on heavy metal availability to plants.

Materials and methods

Chinese cabbage plants were grown in pots with sandy and clayey soils and soils mixed with different doses of biosolid compost spiked with soluble heavy metal salts (Cd, Cu, and Pb). The metals’ distribution pattern in the soil and mixed samples was determined by sequential extraction procedure (modified BCR protocol). The studied fractions, from most to least bioavailable, were water-extractable (WE), exchangeable-adsorbed (EXC), associated with carbonates and acetic acid-soluble forms (CARB), occluded by reducible (hydro)oxides of Fe and Mn (RO), and associated with organic matter (OM) and a residual fraction (RES). Metal concentrations in soil extracts and in the digested plant tissue were measured by ICP-AES.

Results and discussion

The highest compost doses (72 and 115 Mg ha^?1) enhanced cabbage yield significantly. No excessive phytoaccumulation of metals was observed in plants grown in the clayey soil or its mixtures with compost. The compost dose of 72 Mg ha^?1 was optimal in decreasing Cu accumulation by plants grown in sandy soil, and 28.8 Mg ha^?1 was found to be effective in reducing Cd and Pb uptake. Metals were accumulated in plants primarily from the WE, EXC, and CARB fractions, whereas other fractions decreased phytoaccumulation. Compost addition suppressed heavy metal mobility, but different fractions were active in pollutant sorption, depending on soil type and metal.

Conclusions

Compost addition increased metal proportions in the RO and OM fractions, reducing metal phytoavailability. This is especially important for sandy soils with low adsorption ability and higher vulnerability to metal pollution than clayey soils. A compost dose of 20% v/v (or 28.8 Mg ha^?1) effectively reduced plant accumulation of Cd and Pb. We propose using the first three steps of the modified BCR protocol as a three-step sequential-extraction procedure for the most phytoavailable fractions of heavy metal: WE, EXC, and CARB.     

The bioaccumulation of Cd in rice grains in paddy soils as affected and predicted by soil properties

Purpose

The area of cadmium (Cd)-contaminated soil in China is increasing due to the rapid development of the Chinese economy. To ensure that the rice produced in China meets current food safety and quality standards, the current soil quality standards for paddy soils urgently need to be updated.

Materials and methods

We conducted a pot experiment with 19 representative paddy soils from different parts of China to study the effects of soil properties on bioaccumulation of Cd in rice grains. The experiment included a control, a low treatment concentration (0.3 mg kg^–1 for pH?<?6.5 and 0.6 mg kg^–1 for pH?≥?6.5), and a high treatment concentration (0.6 mg kg^–1 for pH?<?6.5 and 1.2 mg kg^–1 for pH?≥?6.5) of Cd salt added to soils.

Results and discussion

The results showed that the Cd content in grains of the control and low and high Cd treatments ranged from 0.021 to 0.14, 0.07 to 0.27, and 0.12 to 0.33 mg kg^–1, respectively. Stepwise multiple regression analysis indicated that soil pH and organic carbon (OC) content could explain over 60 % of the variance in the (log-transformed) bioaccumulation coefficient (BCF) of Cd in grains across soils. Aggregated boosted trees analysis showed that soil pH and OC were the main factors controlling Cd bioavailability in paddy soils. Validation of the models against data from recent literature indicated that they were able to accurately predict the BCF in paddy soils.

Conclusions

These quantitative relationships between the BCF of Cd in grains and soil properties are helpful for developing soil-specific guidance on Cd safety threshold value for paddy soils.     

Nitrification,acidification, and nitrogen leaching from subtropical cropland soils as affected by rice straw-based biochar: laboratory incubation and column leaching studies

Purpose

Few studies have examined the effects of biochar on nitrification of ammonium-based fertilizer in acidic arable soils, which contributes to NO₃ ^? leaching and soil acidification.

Materials and methods

We conducted a 42-day aerobic incubation and a 119-day weekly leaching experiment to investigate nitrification, N leaching, and soil acidification in two subtropical soils to which 300 mg N kg^?1 ammonium sulfate or urea and 1 or 5 wt% rice straw biochar were applied.

Results and discussion

During aerobic incubation, NO₃ ^? accumulation was enhanced by applying biochar in increasing amounts from 1 to 5 wt%. As a result, pH decreased in the two soils from the original levels. Under leaching conditions, biochar did not increase NO₃ ^?, but 5 wt% biochar addition did reduce N leaching compared to that in soils treated with only N. Consistently, lower amounts of added N were recovered from the incubation (KCl-extractable N) and leaching (leaching plus KCl-extractable N) experiments following 5 wt% biochar application compared to soils treated with only N.

Conclusions

Incorporating biochar into acidic arable soils accelerates nitrification and thus weakens the liming effects of biochar. The enhanced nitrification does not necessarily increase NO₃ ^? leaching. Rather, biochar reduces overall N leaching due to both improved N adsorption and increased unaccounted-for N (immobilization and possible gaseous losses). Further studies are necessary to assess the effects of biochar (when used as an addition to soil) on N.     

Effect of Sodium Chloride-induced Salinity on Phyto-availability and Speciation of Cd in Soil Solution

A greenhouse experiment with two levels of Cd (0.5 and 10 mg Cd kg^?1, in the form of CdCl₂), and five salinity levels of irrigation water (0, 8.6, 17.1, 34.2 and 68.4 mM NaCl) in triplicate was conducted to determine the effect of NaCl-induced salinity on the solubility and availability of Cd in clay loam and sandy calcareous soils. Corn seeds (Zea mays L.) were sown in pots. Forty-five days after planting, the shoots were harvested, and their Cd concentration was determined. The post-harvest electrical conductivity (EC_e), pH, and concentrations of cations and anions were determined in soil saturation paste extracts. Increasing irrigation water salinity resulted in significant increases in the total soluble Cd concentration in both studied soils. A positive correlation was found between the total soluble Cd and the chloride concentration in the soil solution.Solution speciation, calculated with MINEQL+ (a chemical equilibrium modeling system), predicted that Cd was present mainly as free Cd²⁺ ions followed by CdCl⁺ and $ {\text{CdSO}}^{0}_{4} $ in the soils irrigated with deionized water. However, Cd species in the soil solution were significantly altered by increasing chloride concentration, with Cd–chloro complexes becoming the dominant Cd species in the soil solution. Increasing the salinity level resulted in significant decreases in the shoot dry matter and increases in the shoot Cd concentration. Shoot Cd concentration was positively correlated with both the total Cd and Cd–chloro complexes in the soil solution.     

Optimization of arsenic and pentachlorophenol removal from soil using an experimental design methodology

Purpose

In this study, a soil-washing process was investigated for arsenic (As) and pentachlorophenol (PCP) removal from polluted soils. This research first evaluates the use of chemical reagents (HCl, HNO₃, H₂SO₄, lactic acid, NaOH, KOH, Ca(OH)₂, and ethanol) for the leaching of As and PCP from polluted soils.

Materials and methods

A Box–Behnken experimental design was used to optimize the main operating parameters for soil washing. A laboratory-scale leaching process was applied to treat four soils polluted with both organic ([PCP] _i ?=?2.5–30 mg kg^?1) and inorganic ([As] _i ?=?50–250 mg kg^?1, [Cr] _i ?=?35–220 mg kg^?1, and [Cu] _i ?=?80–350 mg kg^?1) compounds.

Results and discussion

Removals of 72–89, 43–62, 52–68, and 64–98 % were obtained for As, Cr, Cu, and PCP, respectively, using the optimized operating conditions ([NaOH]?=?1 N, [cocamidopropylbetaine] _i ?=?2 % w w^?1, t?=?2 h, T?=?80 °C, and PD?=?10 %).

Conclusions

The use of NaOH, in combination with the surfactant, is efficient in reducing both organic and inorganic pollutants from soils with different levels of contamination.     

Sorption of copper(II) from synthetic oil sands process-affected water (OSPW) by pine sawdust biochars: effects of pyrolysis temperature and steam activation

Purpose

Remediate metal contamination is a fundamental step prior to reclaim oil sands tailing ponds, and copper (Cu(II)) is the most abundant metal in the tailings water or oil sands process-affected water (OSPW). Biochars produced at four pyrolysis conditions were evaluated for sorption of Cu(II) in synthetic OSPW to explore different biochar potentials in removing Cu(II) from the contaminated water.

Materials and methods

Pine sawdust biochars pyrolyzed at 300 and 550 °C with and without steam activation were investigated by batch sorption experiments. Isotherm and kinetic studies were conducted to compare the sorption capacities of the four biochars and to examine potential mechanisms involved.

Results and discussion

For all the biochars, Langmuir and pseudo-second order models were the best-fit for isotherm and kinetic studies, respectively. According to the Langmuir parameters, the maximum adsorption capacities of the biochars produced at 550 °C were around 2.5 mg Cu(II)?g^?1, which were 30-folds higher than those produced at 300 °C. However, steam activation did not cause any significant difference in the biochars’ sorption performance. The kinetic study suggested that chemisorption involving valence forces was the limiting factor of the sorption. In addition, ion exchange and precipitation were likely the primary mechanisms for Cu(II) sorption which outweigh complexation with functional groups on the biochars’ surface.

Conclusions

Pine sawdust biochar produced at 550 °C without steam activation could be utilized as a sustainable and cost-effective material to remove Cu(II) from the OSPW.

     

Sorption of polycyclic aromatic hydrocarbons to soils enhanced by heavy metals: perspective of molecular interactions

Purpose

Combined pollution by polycyclic aromatic hydrocarbons (PAHs) and heavy metals are commonly found in industrial soils. This study aims to investigate the effect of the coexistence of heavy metals on the sorption of PAHs to soils. We focused specifically on the relationship of the sorption capacity with the estimation of the binding energy between PAHs and heavy metals.

Materials and methods

The sorption of typical PAHs (naphthalene, phenanthrene, and pyrene) to soils coexisting with heavy metals (Cu(II), Pb(II), and Cr(III)) was characterized in batch sorption experiments. The binding energy between PAHs and heavy metals in aqueous solution was estimated by quantum mechanical (QM) method using density functional theory (DFT) at the M06-2x/def2svp level of theory.

Results and discussion

Sorption capacity and nonlinearity of the PAHs to the soils were enhanced by the coexisting heavy metals. The extent of increment was positively associated with the hydrophobicity of the PAHs and the electronegativity and radius of the metal cations: Cr(III)?>?Pb(II)?>?Cu(II). The cation-π interaction was revealed as an important noncovalent binding force. There was a high correlation between the binding energies of the PAHs and K _f ′ (K _f adjusted after normalizing the equilibrium concentration (C _e) by the aqueous solubility (C _s)) (R ²?>?0.906), indicating the significant role of the cation-π interactions to the improved PAH sorption to soils.

Conclusions

In the presence of heavy metals, the sorption capacities of naphthalene, phenanthrene, and pyrene to soils were enhanced by 21.1–107 %. The improved sorption capacity was largely contributed from the potent interactions between PAHs and heavy metals.