Residual Cd Research Articles

Change in phytoextraction of Cd by rapeseed (Brassica napus L.) with application rate of organic acids and the impact of Cd migration from bulk soil to the rhizosphere

Adding exogenous low-molecular weight organic acids is an effective technique to improve phytoremediation of Cd-contaminated soil and has been well documented, but how acid application rate affects remediation efficiency and its underlying limiting factors remains elusive. We investigated this using pot experiments with rapeseed (Brassica napus L.) as the model plant. Plastic pots packed with a sandy loam contaminated by Cd at 4.838 mg/kg were amended with acetic acid, oxalic acid, citric acid, malic acid and tartaric acid, respectively, at an application rate gradient varying from 0.0 to 12.0 mmol/kg. Plants in each pot were harvested after growing for five months, and we then measured the exchangeable, carbonate, Fe–Mn oxide, organic and residual Cd in the rhizosphere, as well as Cd in both roots and shoots. The results showed that all organic acids improved plant uptake of Cd and, compared with the control without acid addition, they could improve Cd uptake by more than 100%. The enhanced Cd extraction was due to the increase in exchangeable Cd in the rhizosphere. Plant Cd was weakly correlated to the amount of Cd lost from a unit volume of the rhizosphere due to root extraction (R2 = 0.06), but a good negative correlation was found between them after normalizing the lost Cd by root biomass (R2 = 0.36). Mass balance analysis revealed that the average Cd content in soil (rhizosphere and bulk soils combined) was much higher than the Cd content in the rhizosphere, and the improved Cd mobility after acid addition was thus due to the increased chelation. As diffusion of ligands in water is one order in magnitude smaller than diffusion of Cd ions, our results suggested that Cd migration from the bulk soil into the rhizosphere was a major factor limiting Cd phytoextraction by rapeseed after adding the exogenous organic acids.

Effects of Water Management on Soil Properties and Cd Behavior of Typical Paddy Soils

To explore the effects of water management mode on Cd environmental behavior in different parent-material-developed paddy soils, two parent-material-developed paddy soils (yellow clayey soil and granitic sandy soil) under three exogenous Cd levels (0.5, 2.0, and 5.0 mg·kg-1) with different water management modes (long-term flooding, moistening irrigation, and wet-dry rotation) were cultured in this study. The soil redox potential (Eh value), pH value, Cd concentration in soil solution, and Cd fractionation were also determined. The results showed that water management mode had different effects on the pH and Eh values of soils developed from different parent materials. The change rates of soil pH value were as follows:long-term flooding:-2.61% (yellow clayey soil), 2.25% (granitic sandy soil); alternation of dry and wet:-1.96% (yellow clayey soil); 0.52% (granitic sandy soil); wet irrigation:-4.08% (yellow clayey soil) and -0.52% (granitic sandy soil). The Eh value of the soils was negatively correlated with the pH value. The influence pattern of water management model on Cd mass concentration of soil solutions in two parent-material soils was consistent. The Cd mass concentration of soil solutions in granitic sandy soil was higher than that in yellow clayey soil. The mean values of Cd concentration were 1.03 μg·L-1 for yellow clayey soil and 1.07 μg·L-1 for granitic sandy soil. Water management mode had no significant effect on the proportions of organic bound Cd or Fe-Mn bound Cd in two different parent-material-developed soils. The long-term flooding mode promoted the transformation of exogenous Cd to residual Cd, and this promotion in yellow clayey soil was higher than that in granitic sandy soil. In conclusion, during the process of regulating soil Cd bioavailability through water management, the role of soil parent materials needs to be considered.

Reduction mechanism of Cd accumulation in rice grain by Chinese milk vetch residue: Insight into microbial community

Chinese milk vetch is an efficient approach to reduce Cd accumulation in rice, nevertheless, its reduction mechanism is not well understood. In this study, we investigated the rice grain Cd, soil properties and microbial community in a Cd-polluted paddy field amended with milk vetch residue (MV) or without (CK) during rice growth period. We found that milk vetch residue averagely decreased the Cd content in rice grain by 45%. Decrease of Cd in rice mainly attributed to the inhibition of Cd activation by milk vetch residue at heading stage probably by the formation of HA-Cd (Humic Acid) and CdS. Increased pH and organic matter (OM) promoted the reduction of available Cd. In addition, nonmetric multidimensional scaling (NMDS) analysis revealed that microbial community structure was significantly different between MV and CK treatment (r = 0.187, p = 0.002), and the core functions of differentially abundant genera were mainly associated with N-cycling, organic matter degradation and sulfate-reducing. The application of milk vetch residue increased the abundance of sulfate-reducing bacteria (SRB) by 8–112% during the rice growth period, which may involve in promoting the transformation of Cd to a more stably residual Cd (CdS). Canonical correspondence analysis (CCA) and mantel test analysis indicated that available K (p = 0.004) and available N (p = 0.005) were the key environmental factors of shaping the SRB. Altogether, changes in soil properties affected microbial structure and functional characteristics, especially the response of SRB in MV treatment would provide valuable insights into reducing the bioavailability of Cd in soil.

Mitigation of Cd accumulation in rice with water management and calcium-magnesium phosphate fertilizer in field environment.

Pollution of Cd has seriously threatened environmental safety and human health. The field experiment was conducted to investigate the effects of calcium-magnesium phosphate fertilizer and water management on bioavailability of Cd in soils and its accumulation in rice. The results revealed that continuous flooding has enhanced soil pH from 5.10 to 5.72 and reduced soil redox potential (Eh) from 164 to - 60mV. Application of calcium-magnesium phosphate fertilizer has significantly raised soil pH from 5.10 to 6.45 (P < 0.05). The treatment of calcium-magnesium phosphate fertilizer and continuous flooding has reduced available content of Cd in soils by 28.57%. The content of Cd in brown rice was significantly diminished by 51.36% (P < 0.05). The continuous flooding has promoted formation of residual Cd in soil with application of calcium-magnesium phosphate fertilizer. The biomass and grain production of rice was not significantly decreased compared with control.

Effects of biochar on heavy metals migration and fractions changes with different soil types in column experiments

Effects of biochar on different soil types were studied in soil column experiments. The results showed that the biochar decreased filtrate heavy metals concentration by 89.0% to 95.7% (Cd) and 93.2% to 99.3% (Pb) compared with the control. The biochar application changed 2.3% to 9.84% of the exchangeable Cd fraction Pb to residual fractions, so the bioavailable Cd and Pb were reduced by 4.48% to 10.69% (Cd) and 11.74% to 16.42% (Pb) in surface soil (0 to 4 cm). Through increasing the soil ratio, the concentration of bioavailability of Cd and Pb was decreased 13.84% to 16.15% and 4.02% to 13.40% in 4 to 8 cm soil. With sandy soil, the application of biochar effectively reduced the down migration of heavy metals, and accomplished the conversion of 100.0% and 95% exchangeable Cd and Pb fractions into 13.1 to 43.9% residual Cd and 11.6 to 100.0% residual Pb. The SOM and pH also increased 1.2 to 2.3 g kg-1 and 0.01 to 0.31 with biochar application. The biochar effectively increased the SOM content, and stabilized heavy metals, then reduced the migration of Cd and Pb.

Effects of Nano-magnesium Hydroxide on the Forms of Cadmium in Different Types of Soil

The effects of nano-magnesium hydroxide and common magnesium hydroxide (100, 200, and 300 mg·kg-1) on the forms of cadmium in different types of cadmium contaminated soils (1, 5, 10, and 15 mg·kg-1) were studied under 28 days of continuous culture experiment. In the neutral soil, during the 28 days of culture, soil exchange Cd (EX-Cd) form distribution ratio (FDC) decreased at first and then increased with the culture time increasing under treatment of 1, 5, 10, and 15 mg·kg-1 Cd. The minima of soil EX-Cd FDC were found on the 14th day under 1 mg·kg-1 Cd and 5 mg·kg-1 Cd treatments, whereas the minima of soil EX-Cd FDC were observed on the 4th day under 10 mg·kg-1 Cd and 15 mg·kg-1 Cd treatments. The FDC of soil carbonate bound Cd (CAB-Cd), iron manganese oxidized Cd (FeMn-Cd), and organic bound Cd (OM-Cd) increased at first, then decreased, and finally, became stable, and the maxima of soil CAB-Cd, FeMn-Cd, and OM-Cd FDC were found on the 4th day, whereas the minima of soil CAB-Cd, FeMn-Cd, and OM-Cd FDC were observed on the 14th day. Soil residual Cd (RES-Cd) FDC increased gradually and then tended to becomes stable during the 28 days of culture. The soil EX-Cd FDC was 66.7%-81.8% at 1, 5, 10, and 15 mg·kg-1 Cd treatments, which was the main form of the soil. The FDC of soil Cd forms was in the order of EX-Cd > CAB-Cd > RES-Cd > FeMn-Cd > OM-Cd. Soil EX-Cd FDC reached the lowest value on the 14th Day. Soil EX-Cd FDC was reduced by nano-magnesium hydroxide and common magnesium hydroxide, and it decreased with the increase of the amount of magnesium hydroxide. During 0-28 days of culture, the soil EX-Cd FDC decreased by 11.4%-67.7%, 7.8%-37.2%, 7.7%-36.4%, 5.0%-28.8% (nano-magnesium hydroxide) and 0.5%-49.5%, 0.6%-15.0%, 1.0%-18.1%, 0.7%-14.6% (ordinary magnesium hydroxide) at 1, 5, 10, and 15 mg·kg-1 Cd treatments, respectively. The EX-Cd content of alkaline soil reached the lowest value on the 7th day of culture, and the EX-Cd content of acidic soil reached the lowest value on the 21st day under 1, 5, and 10 mg·kg-1 Cd treatments. The content of EX-Cd in neutral, acidic, and alkaline soils decreased with the increase of magnesium hydroxide content, and the content of EX-Cd in soil decreased with the increase of magnesium hydroxide amount. At the same amount, the effect of passivating soil EX-Cd under nanometer magnesium hydroxide treatment was superior to ordinary magnesium hydroxide treatment.

Evaluation of Different Types and Amounts of Amendments on Soil Cd Immobilization and its Uptake to Wheat.

Using amendments is a cost-effective method to soil cadmium (Cd) remediation, whereas knowledge about how different amendments and rates affect remediation efficiency remains limited. This study aimed to evaluate the impacts of different types and amounts of amendments on soil Cd immobilization and its uptake by plants. Biochar (BC), zeolite (ZE), humic acid (HA), superphosphate (SP), lime (L), and sodium sulfide (SS) were applied at three rates (low, medium, and high) ranging from 0.5 to 5%. The concentration of CaCl2-extractable Cd was considerably affected by the amendments, except HA, and the high doses achieved better immobilization effects than the low doses did. The addition of amendments decreased weak acid soluble Cd by 4.1-44.0% but slightly increased the fractions of oxidizable and residual Cd. These amendments (except BC and HA dose of 1%) decreased Cd accumulation in grains by 1.3-68.8% and (except SP) in roots by 16.3-65.5% compared with the control. The SP efficiently immobilized Cd but posed a potential soil acidification risk. Moreover, SS treatment increased the soil electrical conductivity (EC) value and restricted the growth of wheat, possibly due to high-salt stress. BC, ZE, and L exerted significant effects on the reduction in available Cd as the application rate increased. These amendments enhanced Cd immobilization mainly by changing Cd availability in soil and influencing its redistribution in different fractions in soil and root uptake by plants. This study concluded that BC-5%, ZE-1%, and L-0.5% can be used for Cd immobilization in acidic or neutral soils.

Influence of silicon on cadmium availability and cadmium uptake by rice in acid and alkaline paddy soils

The aim of this research was to study the inhibiting effects of cadmium uptake into plants by exogenous silicon between acid and alkaline paddy soils, especially, the effects of silicon without the differentiation of pH and accompanying ions. Therefore, without the interference of pH and accompany ions (Na+), the mechanisms of soil chemistry on cadmium (Cd) transformation and accumulation by Si application in the soil-plant system were examined. The acid and alkaline soils for the experiment were collected from the upper soil layer (0~20 cm) from two paddy fields. The Cd solution as CdNO3 and different levels of SiO2 as Na2SiO3 solutions were applied in the potted soils. To eliminate differences of nitrate and sodium among the treatments, 6.8, 6.8, and 1.7 g sodium nitrate was added into the CK, Si0Cd5, and Si90Cd5 treatments, respectively. The soil redox potential and pH during the experiments were determined. After harvest, changes in Cd concentrations in rice grains, stems, and roots were measured. Soil samples in close proximity to the rice roots were collected at harvest. The sequential extraction was employed to estimate the chemical speciation of Cd in the treated soils. The Si applications reduced Cd accumulation in rice plants, thereby increasing the rice yield. With increase of the dosages, the ratios of Cd contents in root, stem, and grain decreased significantly. The Eh and pH of the Si treatments were higher than application of Cd only. In the alkaline soil, Cd contents in the soil solutions of the Si treatments were higher than the Si0Cd5 treatment. In contrast, in the acid soil, the Cd contents in the soil solution of the Si treatments were lower than that Si0Cd5 treatment. In the acid soil, Si application improved the Cd adsorption by soil and alleviated Cd uptake by plants. Therefore, the alkaline soil reduced Cd phytoavailability by forming Si-Cd water-soluble complex, which could not be taken up by rice plants. The Si application significantly increased yield of rice and decreased Cd concentrations in the roots, stems, and grains of rice plants. In the alkaline soil, Cd and Si formed the Si-Cd water-soluble complex, which could not be taken up by the rice plants. In both soils, Si reduced the concentrations of acid extractable Cd and reducible Cd while promoting the formation of oxidable Cd and residual Cd, resulting in low soil Cd bioavailability.

Alkali-catalyzed supercritical water gasification of sewage sludge: effect of liquid residue reuse as homogenous catalyst

Conventional supercritical water gasification (SCWG) of sewage sludge produces liquid residues with organic pollutants, heavy metals and others. In order to reduce liquid residues released into the environment, this study investigated the reuse of liquid residues as feed water in subsequent SCWG. We also evaluated the effect of wastewater reuse on syngas production and fate of heavy metal. The experiment was performed in a 500-ml-capacity Hastelloy reactor at 400 °C and above 25 Mpa for 60 min with a 4:1 ratio of 10% dry wt. of solid (mixture of sludge and empty fruit bunch) and 90% wt. of liquid feed. The use of recycled liquid increased the concentration of K and Na in the solution from 26 mg/L and 91 mg/L to 49 mg/L and 290 mg/L, respectively. Subsequently, syngas production increased from 9.4 to 14.1 mol/kg organic matter. In addition, H2 production increased by 30%. The increase in syngas generation could be attributed to the alkaline salts which act as homogenous catalysts and to the organic matter in the liquid residue. In addition, the total mass of As, Cr, Cd, Cu, Pb and Zn in the liquid residues reduced from 57.36 to 47.34 µg. Thus, experimental results imply that the recycling of liquid residues in SCWG will not only improve the syngas production efficiency of the system, but also enable the accumulation of heavy metals in the solid residue to prevent pollution risk.

Trace Metal and Cd Isotope Systematics of the Basal Datangpo Formation, Yangtze Platform (South China) Indicate Restrained (Bio)Geochemical Metal Cycling in Cryogenian Seawater

The behaviour of bioavailable trace metals and their stable isotopes in the modern oceans is controlled by uptake into phototrophic organisms and adsorption on and incorporation into marine authigenic minerals. Among other bioessential metals, Cd and its stable isotopes have recently been used in carbonate lithologies as novel tracer for changes in the paleo primary productivity and (bio)geochemical cycling. However, many marine sediments that were deposited during geologically highly relevant episodes and which, thus, urgently require study for a better understanding of the paleo environment are rather composed of a mixture of organic matter (OM), and detrital and authigenic minerals. In this study, we present Cd concentrations and their isotopic compositions as well as trace metal concentrations from sequential leachates of OM-rich shales of the Cryogenian basal Datangpo Formation, Yangtze Platform (South China). Our study shows variable distribution of conservative and bioavailable trace metals as well as Cd isotope compositions between sequential leachates of carbonate, OM, sulphide, and silicate phases. We show that the Cd isotope compositions obtained from OM leachates can be used to calculate the ambient Cryogenian surface seawater of the restricted Nanhua Basin by applying mass balance calculations. By contrast, early diagenetic Mn carbonates and sulphides incorporated the residual Cd from dissolved organic matter that was in isotopic equilibrium with deep/pore waters of the Nanhua Basin. Our model suggests that the Cd isotopic composition of surface seawater at that time reached values of modern oxygenated surface oceans. However, the deep water Cd isotope composition was substantially heavier than that of modern fully oxygenated oceans and rather resembles deep waters with abundant sulphide precipitation typical for modern oxygen minimum zones. This argues for incomplete recycling of Cd and other bioavailable metals shortly after the Sturtian glaciation in the redox stratified Cryogenian Nanhua Basin. Our study highlights the importance of sequential leaching procedures when dealing with impure authigenic sediments such as OM-rich carbonates, mudstones, or shales to achieve reliable trace metal concentrations and Cd isotope compositions as proxies for (bio)geochemical metal cycling in past aquatic systems.

Manganese-modified biochar for highly efficient sorption of cadmium.

In this study, corn stalk was modified by manganese (Mn) before (MBC1) and after (MBC2) pyrolysis at different temperatures (400~600°C) under anaerobic conditions for Cd sorption in both water and soil. Batch experiments in aqueous solution were conducted to evaluate the optimum sorption capability by biochar with and without manganese-modified. Both types of manganese modification can improve the sorption capacity of Cd(II) on biochar, which is superior to the corresponding pristine biochar without modification, especially, pyrolyzed at 500°C with 5:1 modification ratio. Under the optimal preparation conditions, the sorption percentage on MBC2 was 11.01% higher than that of MBC1. The maximum sorption capacity of MBC2 was 191.94mgg-1 calculated by isotherm model. The performance of MBC2 was also verified in soil stabilization experiments in Cd-contaminated soil. We can conclude from the results of BCR extraction that all the application rates of MBC2 (1%, 2%, and 3%) can reduce the mild acid-soluble fraction Cd. The reducible, oxidizable, and residual fraction Cd showed an upward trend, thus controlling the migration, transformation, and enrichment of Cd in soil. The characteristic analysis showed biochar has more irregular fold and more particle-aggregated surface after modification. The main components of these aggregated particles are manganese oxides (MnOx) with high sorption capacity, such as the MnOx crystal structure loaded on MBC2 is a mixed structure of δ-MnO2 and MnO. However, these particles may block the biochar pores, or some of the pores may collapse at high temperatures during the modification process. The specific surface area was reduced, even if the sorption effect of MBC was strongly enhanced. Meanwhile, under the action of the secondary pyrolysis of MBC2 modification process, the MBC2 has a higher degree of aromatization with more potential active sorption sites for Cd. The study concluded that the MBC2 could be a promising amendment for Cd in both water and soil real field applications.

Effects of biochar on cadmium (Cd) uptake in vegetables and its natural downward movement in saline-alkali soil

ABSTRACT The focus was to assess the effects of biochar on Cd uptake by various vegetables and its downward movement in saline-alkali soil and carried out in polluted pots experiment. The results showed that the biomass of vegetables increased significantly by 16.9% to 519.9% while the Cd concentration in green pepper and eggplant fruits was decreased by 6.8% to 11.5% and 15.1% to 15.4% with the biochar application. The Cd in contaminated soil profile was transferred from topsoil (0-6 cm) to subsoil (6-12 cm) that was observed as 14.30 ± 4.17 mg kg-1. The concentrations of Cd in soil with different fractions like exchangeable, reducible and oxidizable and the Cd uptake by vegetables were reduced. The release of residual Cd was decreased by 0.3 to 20.1% over time with biochar application (0-12 cm). The biochar was effective in mitigating the soil Cd pollution by preventing the vertical Cd leaching.

Bioaccumulation of Cadmium Affects Development, Mating Behavior, and Fecundity in the Asian Corn Borer, Ostrinia furnacalis.

Heavy metal pollution is becoming an increasingly serious problem in agricultural ecosystems. Heavy metals such as cadmium (Cd) accumulate in the food chain and may lead to detrimental effects on the physiological functions of living organisms, including herbivorous insects. One such example is the Asian Corn Borer, Ostrinia furnacalis (Lepidoptera: Pyralidae). However, how Cd can affect the development and reproduction of O. furnacalis is largely unknown. In this study, we exposed larvae of O. furnacalis to a diet containing Cd and investigated the effects of Cd on the development, mating behavior, and fecundity of the insect. We showed that Cd accumulates in the larvae and inhibits development by extending larval and pupal duration and decreasing the survival rate. The excretion of Cd through multiple routes during the larval and pupal stages resulted in low levels of residual Cd in the adult insects, which were not fed with Cd. However, the mating behavior and fecundity of these insects were significantly affected, compared to control insects. This suggests that the bioaccumulation of heavy metals such as Cd has long lasting and detrimental effects on O. furnacalis over the entire life cycle, affecting fecundity, even when specimens are only exposed at an early life stage.

Pyrolysis of various phytoremediation residues for biochars: Chemical forms and environmental risk of Cd in biochar

Various phytoremediation residues (PMRs), including Brassica napus L. (BN), Pennisetum sinese (PS) and Lolium perenne L.(LP), were pyrolyzed at 400, 500, 600 and 700 °C, respectively. A series of sequential and single extractions were employed to analyze the chemical speciation and potential environmental risk of Cadmium (Cd) in different phytoremediation residues-derived biochars (PMBs). The results showed that the exchangeable Cd fraction decreased but the residual Cd fraction increased, indicating the inhibition of bioavailability of Cd and low potential ecological risk index of PMBs. When the temperature was over 600 °C, the Cd in biochar was acceptable to the environment and the leaching concentration of Cd extracted by the three extraction methods (distilled water, SPLP and TCLP) were all under the standard limit. Findings from this study illustrated that the treatment of pyrolysis was feasible for the three kinds of PMRs at 600 °C with acceptable environment risk.

The influence of thermal maturity on the stable isotope compositions and concentrations of molybdenum, zinc and cadmium in organic-rich marine mudrocks

The concentrations and isotopic compositions of molybdenum (Mo), zinc (Zn) and cadmium (Cd) in organic-rich marine mudrocks may be used to characterize ocean chemistry in the geological past. These approaches rely on the rarely tested assumption that the geochemical signatures of these metals are not affected by the thermal maturation of the organic matter with which they are associated. We have conducted a series of artificial maturation experiments on two well-known immature organic-rich mudrocks, the Kimmeridge Blackstone Band (Late Jurassic age), and the Posidonia Shale (Early Jurassic age). These pyrolysis experiments allow us to trace changes in the composition of organic matter through varying stages of maturation, and the concentration and isotopic compositions of metals in rock residues and evolved organic fluids. Our results indicate that the thermal maturation of organic matter does not result in significant alteration of the isotopic compositions of Mo, Zn and Cd in the rock residues, which thus retain primary palaeodepositional information. Systematic increases in the concentrations of Mo, Zn and Cd in rock residues with progressively higher thermal maturity are attributed to the loss of substrate mass in the form of fluids released during pyrolysis-induced cracking of kerogen, and to the relatively low concentrations of Mo, Zn and Cd in these fluids. The Mo-isotope compositions of fluids produced during pyrolysis are isotopically similar to the bulk rock; in contrast the isotopic composition of Zn in organic fluids is ∼0.4–0.6‰ lighter than the bulk rock. The progressive loss of organic matter from rock residues during maturation coupled with the increases in metal concentrations leads to an increase of metal/TOC ratios, which may be up to double their original (syn-depositional) value in thermally mature rocks. This observation must be taken into account when using metal/TOC ratios as proxies for oceanic metal inventories throughout geological time. Finally, calculations using the mass of asphaltenes recovered during the pyrolysis experiments suggest that organically bound Mo, Zn and Cd account for several percent of the total rock metal inventory.

Evaluation of the effects of mandarin (Citrus reticulate) by-products containing citric acid on immobilization of cadmium in arable soils

In a pilot study, we observed cadmium (Cd) immobilization with citric acid (CA) and suggested that mandarin by-products (MB), which contain CA at ca. 1.65%, can be used as soil amendments that reduce Cd bioavailability. In the present study, we (1) elucidated mechanisms of Cd immobilization by CA and (2) evaluated the use of MB as a soil amendment for Cd immobilization. In Experiment 1, CA was mixed with Cd contaminated soil at 0 and 3.5 mmol kg−1. We then added MB to Cd-spiked soil at 10, 20, and 40 g kg−1. Addition of CA decreased F2 (surface adsorbed Cd fraction) contents by 2.64 mg kg−1 compared with the control but was associated with increases in Cd fractions F1 (bioavailable Cd fraction) and F5 (residual Cd fraction) of 1.04 and 1.49 mg kg−1, respectively. Addition of CA enhanced the concentration of fraction F5, likely reflecting Cd precipitation from soil solutions with increased HCO3− concentrations. However, although this treatment immobilized Cd, it also led to increasing residual and bioavailable Cd fractions. Unlike CA treatments, MB increased non-bioavailable Cd fractions without increasing the bioavailable Cd fraction. Moreover, at 40 g kg−1, MB decreased F1 contents by 8% compared with the control, but increased F2, F3, and F5 contents by 3.6%, 0.7%, and 4.5%, respectively. Cd may be immobilized by MB through HxCO3− mediated precipitation as CdCO3 following decomposition of CA and concomitant increases in the negative charge of soil due to the organic matter in MB. MB also improved the chemical properties of soils, with increased nutrient concentrations and cation exchange capacities.

Characterization of phosphorus engineered biochar and its impact on immobilization of Cd and Pb from smelting contaminated soils

Biochar has been used as an amendment to immobilize toxic metals (TMs) and increase nutrient content in the contaminated soil. In this study, Ca(H2PO4)2-engineered swine manure biochar (PSMB) and swine manure biochar (SMB) were prepared and investigated to evaluate their effects on the availability of toxic metals (Cd and Pb) and soil nutrient content in Fengxian (FX)- and Kunming (KM)-contaminated soils through incubation experiment. The soil samples were collected at 0–20 cm depth from two contaminated farmlands close to abandoned Pb smelters, which are located in FX and KM. Swine manure was obtained from the rural hog lot in Yangling, China. Each biochar (SMB and PSMB) was mixed with the air-dried soil samples (FX and KM) at a dosage of 1% and 3% w/w, respectively. Then, a portion of 3 kg of the mixture was placed in plastic pots and incubated for 30 days in a greenhouse. After the soil incubation experiment, pot experiments were performed in a greenhouse of Northwest A&F University, Yangling, China. Adding PSMB at a rate of 3% maximally decreased the concentrations of DTPA-extractable Cd (34.02 and 47.73%) and Pb (18.70 and 24.58%) in FX and KM soil. The BCR data revealed that the percentage of acid-soluble Cd and Pb fraction in FX and KM soils remarkably decreased whereas the percentages of residual Cd fraction and reducible Pb fraction in FX and KM soils significantly increased in all the biochar-amended soils compared with control. To confirm these results, a pot experiment was conducted to investigate the effects of amendments on growth and uptake of toxic metals in Chinese cabbage (Brassica rapa L. spp. pekinensis). The results showed that the addition of PSMB3% significantly (P < 0.05) increased the biomass of plants and reduced the absorption of toxic metals in plant. The results revealed that the dry biomass increased and the absorption of toxic metals decreased in plants. All treatments of biochar were beneficial and application of PSMB 3% was most effective in enhancing plant biomass and reducing the accumulation of toxic metals in the plants.

A field experiment on stabilization of Cd in contaminated soils by surface-modified nano-silica (SMNS) and its phyto-availability to corn and wheat

Cd-contaminated soil is a common environmental problem. Stabilization is an effective way of in situ remediation for Cd contamination in soils, but there is a lack of information about the influences of the amendments on soil ecosystems and Cd uptake by crops, especially under field conditions. In this study, surface-modified nano-silica (SMNS) was used to stabilize a Cd-contaminated soil under field condition within one year. SMNS was mixed with Cd-contaminated soil at the dosage of 0%, 0.2%, 0.4%, 0.6%, 0.8%, and 1%, respectively. After that, corn and wheat were sown within one year. DTPA extraction and sequential extraction were used to evaluate stabilization efficiency of SMNS to Cd. The influences of SMNS on crop yield, soil enzyme activities, and Cd accumulation in crops were also analyzed. The DTPA-extractable Cd in soil was reduced by 61.14% when the dosage of SMNS was 1%. SMNS transferred Cd to more stable fractions, with the organic-bound and residual Cd increased 148.11% and 90.52%, respectively. The addition of SMNS decreased soil dehydrogenase slightly, but its influences on soil urease, catalase, and yields of corn and wheat were negligible. More importantly, at the dosage of 1%, SMNS reduced 42.87% and 47.95% of Cd contents in corn and wheat grains, respectively. SMNS was effective in reducing the mobility of Cd in contaminated soils. These results suggest that SMNS has a great potential in the remediation of Cd-contaminated agricultural soils.

Effect of humic acid on the stabilization of cadmium in soil by coprecipitating with ferrihydrite

Coprecipitation of humic acid (HA) with ferrihydrite (Fh) has been proposed to reduce the activity of heavy metals in aqueous solutions. The effect of the amount of HA added to the coprecipitates on the stabilization of Cd in soil is unclear. In this research, five different Fh-HA coprecipitates were synthesized to study the impact of different HA additions on the fractionation of Cd in the soil and the optimal addition ratio of C/Fe. Characterization technique as Fourier transform infrared spectroscopy (FT-IR), X-ray diffraction (XRD), specific surface area analyzer, and scanning electron microscopy (SEM) was used in order to test and analyze of the microstructure and physicochemical property of the coprecipitates. The results showed that the Fh-HA coprecipitate is mainly combined by the coordination exchange of -OH on the surface of the Fh with the carboxyl group of the HA. Adding HA could stabilize Fh and increase its surface roughness. Changes in the fractionation of the Cd were used to evaluate the stabilization effect of the coprecipitate. Before treatment, Cd in different contaminated soils was existed only a small amount of residual fraction. After the addition of the Fh-HA coprecipitate, the proportion of residual Cd in each contaminated soil increased. When the C/Fe ratio was 1.5, the maximum residual fraction were 62.94%, 55.67%, and 52.99% respectively. Residual Cd could remain relatively stable indicating that the Fh-HA coprecipitate is a promising amendment for repairing Cd-contaminated soil. The addition of HA has strengthened the active role of Fh on stabilizing heavy metals.

Effect of iron nanoparticles on passivation of cadmium in the pig manure aerobic composting process.

Cadmium (Cd) is a toxic metal ion in pig manure impacting on the ecosystem, and hence the immobilization of Cd by green synthesis of iron nanoparticles (G-nFe) is a potential approach. In this study, transformation of Cd (II) during the pig manure thermophilic aerobic composting process in the presence of G-nFe was investigated. The results show that the addition of G-nFe promoted the composting process and release of available phosphorus (AP). In all six experiments, obvious passivation of Cd occurred during 15 days' composting. Particularly when 500 mL kg-1 of G-nFe was added and Cd (II) was added at 0.6%(w/w%), residual Cd increased from 0.0016% to 55.70% and exchangeable Cd decreased from 98.54% to 7.21%. Batch experiments revealed that the G-nFe promoted the transformation of Cd into a larger passivation fraction. X-ray photoelectron spectroscopy (XPS), X-ray diffraction (XRD), SEM-Mapping and Fourier transform infrared (FTIR) analysis was used to characterize residual samples, where indicated that the passivation of Cd in compost was highly correlated with the increase of P, it can be concluded that fixing with compost resulted in the formation of Cd phosphate precipitation or co-precipitation with other phosphates.