A new insight into the straw decomposition associated with minerals: Promoting straw humification and Cd immobilization.

Organic matter (OM) derived from the decomposition of crop residues plays a key role as a sorbent for cadmium (Cd) immobilization. Few studies have explored the straw decomposition processes with the presence of minerals, and the effect of newly generated organo-mineral complexes on heavy metal adsorption. In this study, we investigated the variations in structure and composition during the rice straw decomposition with or without minerals (goethite and kaolinite), as well as the adsorption behavior and mechanisms by which straw decomposition affects Cd immobilization. The degree of humification of extracted straw organic matter was assessed using excitation-emission matrix (EEM) fluorescence and Ultraviolet-visible spectroscopy (UV-vis), while employing FTIR spectroscopy and XPS to characterize the adsorption mechanisms. The spectra analysis revealed the enrichment of highly aromatic and hydrophobic components, indicating that the degree of straw decomposition and humification were further intensified during incubation. Additionally, the existence of goethite (SG) accelerated the humification of OM. Sorption experiments revealed that the straw humification increased Cd adsorption capacity. Notably, SG exhibited significantly higher adsorption performance compared to the organic matter without minerals (RS) and the existence of kaolinite (SK). Further analysis using FT-IR spectroscopy and XPS verified that the primary mechanisms involved in Cd immobilization were complexion with -OH and -COOH, as well as the formation of Cd-π binds with aromatic C=C on the surface of solid OMs. These findings will facilitate understanding the interactions of the rice straw decomposing with soil minerals and its remediation effect on Cd-contaminated farmland.

[Effect of Chelating Agents and Organic Acids on Remediation of Cadmium and Arsenic Complex Contaminated Soil Using Xanthium sibiricum].

In order to improve the phytoextraction efficiency of Xanthium sibiricum on farmland soil that had been contaminated by Cd and As, this study explored the effects of chelating agents and organic acids (EDTA, SAP, CA, and MA) on the extraction of Cd and As heavy metals using X. sibiricum. The results showed that the four different chelating agents and organic acids had little effect on the biomass of the roots, stems, and leaves of X. sibiricum. However, they had different effects on the concentrations and accumulation of Cd and As in various organs of X. sibiricum. Compared with the those in the CK treatment, EDTA, SAP, CA, and MA significantly increased the Cd concentrations in the leaves of X. sibiricum by 44.1%, 32.4%, 41.2%, and 38.2% and the As concentrations in the roots of X. sibiricum by 89.6%, 7.4%, 94.8%, and 61.5%, respectively. The four treatments (EDTA, SAP, CA, and MA) improved the total Cd accumulation of X. sibiricum, with increasing ranges, respectively, of 70.2%, 29.4%, 28.9%, and 33.1%, and the As accumulation increased by 67.0%, 19.6%, 81.9%, and 40.8%, respectively, compared with that of the CK treatment. The four chelating agents and organic acids had different effects on the Cd and As bioconcentration factor and transfer factor of various organs of X. sibiricum. Treatments with EDTA, SAP, CA, and MA resulted in a decrease of 32.7%-38.2% in soil Cd concentrations and a decrease of 14.6%-20.5% in soil As concentrations. These four chelating agents can be used for enhancing the efficiency of extraction Cd and As heavy metals by X. sibiricum.

[Adsorption of Cadmium and Arsenic by Corn Stalk Biochar Solidified Microorganism].

Immobilization of bacteria on biochar can improve the performance of the soil complex polluted with cadmium (Cd) and arsenic (As). In this study, bacteria (Delftia sp. B9, B9), biochar (corn stalks biochar, CSB), and biochar-bacteria complexes (B-CSB) were used as adsorption materials to explore the adsorption characteristics of Cd and As. The effects of pH on the adsorption performance of Cd and As and the ion removal from the aqueous solution were investigated, and the adsorption behaviors were simulated using an isothermal adsorption model. The changes in Cd and As speciation with the addition of B9, CSB, and B-CSB to As and Cd-contaminated soil were explored. The results showed that the Cd-saturated adsorption capacities of B9, CSB, and B-CSB were 49.43, 82.68, and 75.38 mg ·g-1, respectively; the As-saturated adsorption capacities were 24.67, 42.92, and 34.03 mg ·g-1, respectively. The concentration of available Cd and As significantly decreased, whereas the residual fraction increased after the addition of B-CSB. B-CSB was shown to be an effective material for the remediation of soil complexes polluted with Cd and As.

Mechanistic insights into the enhanced removal of roxsarsone and its metabolites by a sludge-based, biochar supported zerovalent iron nanocomposite: Adsorption and redox transformation.

Roxarsone is a phenyl-substituted arsonic acid comprising both arsenate and benzene rings. Few adsorbents are designed for the effective capture of both the organic and inorganic moieties of ROX molecules. Herein, nano zerovalent iron (nZVI) particles were incorporated on the surface of sludge-based biochar (SBC) to fabricate a dual-affinity sorbent that attracts both the arsenate and benzene rings of ROX. The incorporation of nZVI particles significantly increased the binding affinity and sorption capacity for ROX molecules compared to pristine SBC and pure nZVI. The enhanced elimination of ROX molecules was ascribed to synergetic adsorption and degradation reactions, through π-π* electron donor/acceptor interactions, H-bonding, and As-O-Fe coordination. Among these, the predominate adsorption force was As-O-Fe coordination. During the sorption process, some ROX molecules were decomposed into inorganic arsenic and organic metabolites by the reactive oxygen species (ROS) generated during the early stages of the reaction. The degradation pathways of ROX were proposed according to the oxidation intermediates. This work provides a theoretical and experimental basis for the design of adsorbents according to the structure of the target pollutant.

[Effect of Conditioning Agent Combined with Flooding Measures on Absorption and Accumulation of Cadmium in Rice].

In order to evaluate the effects and mechanisms of flooding measures, soil conditioner, silicon mineral fertilizer and sprayed foliar fertilizer, gypsum powder, and their multiple treatments for reducing Cd accumulation in rice grown in Cd-contaminated soil. A plot experiment was conducted in three different Cd-contaminated soils. The results showed that flooding measures, a single application of conditioning agents, and combined application and flooding treatment can reduce soil-available Cd and the Cd content in various organs of rice with 6.58%-30.01% reduction in soil available-Cd and 12.64%-68.68% reduction in Cd content in brown rice, respectively. The Cd reduction decreased in the following order:comprehensive treatment (T6) > basic application of gypsum powder (T5) > base Xiangrunbang state soil conditioner (T3) > mineral silicon fertilizer and spray foliar fertilizer (T4) > flood treatment (T2). In addition, the average value of the reduction effect of the Cd content in brown rice was calculated. The five treatments in the experiment reduced the enrichment of various parts of the rice, which is a main reason for the decrease in Cd content in the brown rice. According to the field plot test, the combined application of the basic conditioning agent, mineral silicon fertilizer, and sprayed foliar fertilizer, and gypsum powder and flooding measures can be used as an effective method for Cd pollution control in Cd-contaminated cultivated rice.

Application of economic plant for remediation of cadmium contaminated soils: Three mulberry (Moms alba L.) varieties cultivated in two polluted fields.

In order to study the role of mulberry (Moms alba L) as an economic crop for remediation of cadmium (Cd) contaminated soil, the transport of Cd from mulberry to silkworm were investigated. Three varieties of mulberry (Yuesang-11, Nongsang-14, and Qiangsang-1) with three planting densities were cultivated in two heavy metal-contaminated fields named Dongkou in Shaoyang city and Linxiang in Yueyang city in Hunan province respectively. The both field soils were contaminated by heavy metals, especially by Cd. The potential risks of heavy metals in Linxiang's soil were higher than those in Dongkou's because of higher concentrations of Cd. Since the promotion of Cd concentrations in aerial parts (stem, branch and leaf) resulted from the increase of planting density, the method of high planting density is beneficial to improve the efficiency of the remediation of Cd contaminated soil. The percentages of average Cd contents of mulberry in Dongkou accounted for 44%, 20%, 18% and 16% in roots, stems, branches and leaves respectively, while the Cd contents were 38%, 27%, 19% and 16% distributed in roots, stems, branches and leaves respectively. Mulberry leaves from contaminated soils was applied in food source of silkworms in this study. Although there is Cd uptake occurred in silkworm growth and its products (cocoons and chrysalis), Cd contents in cocoons are lower than the national standard (100 µg*kg-1) for textile industry of China. Therefore, mulberry can be regarded as an economical crop to control soil contamination with Cd.

Mitigating arsenic accumulation in rice (Oryza sativa L.) from typical arsenic contaminated paddy soil of southern China using nanostructured α-MnO2: Pot experiment and field application.

Manganese oxides are naturally occurring powerful oxidants and scavengers, which can control the mobility and bioavailability of arsenic (As). However, the effect of synthetic nanostructured manganese oxides on the mobilization and transportation of As at actual paddy soils are poorly understood, especially in soils with low or medium background Mn concentration. In the present study, a novel nano manganese oxide with superior reactivity and surface area has been synthesized. A 90-d soil incubation experiment combined with pot and field rice cultivation trials were designed to evaluate the effectiveness of exogenous α-MnO2 nanorods on the mobilization and transportation of As in soil-rice systems. Our results proved that the addition of α-MnO2 nanorods can effectively control the soil-to-solution partitioning of As under anaerobic conditions. After treatment with different amounts of α-MnO2 nanorods, the content of effective As decreased, offset by an increase in residual As and insoluble binding As (Ca-As and Fe-As). Enhancing the oxidation of As(III) into As(V), the α-MnO2 nanorods increased the adsorption of As onto indigenous iron (hydr)oxides which greatly reduced the soil porewater As content. In addition, pot experiments and field applications revealed that the influx of As into the aerial parts of rice plants (stems, husk and leaves) was strictly prohibited after treatments with different amount of α-MnO2 nanorods; more interestingly, significantly negative correlations have been observed between As and Mn in rice, which indicated that as Mn is increased in soil, As in brown rice decreases. Our results demonstrated that the use of α-MnO2 nanorods in As polluted paddy soil containing low levels of background Mn oxides can be a promising remediation strategy.

[Major Factors Influencing the Cd Content and Seasonal Dynamics in Different Land Cover Soils in a Typical Acid Rain Region].

Understanding the seasonal variations in active heavy metal components and sensitive impact factors is of importance for the ecological risk reduction during the agricultural production processes. Paddy fields, vegetable lands, and hilly forests were selected as three main land cover types to assess the seasonal characteristics of Cd bioavailability and reveal how or to what extent it was affected by the physiochemical parameters of soils, under different land-use types in a typical Cd-contaminated watershed in the middle and lower reaches of Xiangjiang River. One-year in situ monitoring results showed that natural rainfall pH in winter and spring was lower than in summer and autumn in the study region. The total Cd content of paddy soils was significantly higher than that of the vegetable soil, while the hilly forest soil showed the lowest total Cd value. Similar seasonal variations in total Cd content were found in three soil types with slightly lower summer and autumn concentrations than spring and winter values, but no obvious correlation was detected between the total and the available Cd components. The paddy soil available Cd concentration during the 5-9-month crop growth season was significantly lower than the other months of the year, while vegetable cultivation and hilly forest soils showed the opposite trend. Eh was the key factor that had a positive influence on the Cd activity in paddy soil. Soil TOC concentration was negatively correlated with soil activity in vegetable soil. TOC, water soluble organic carbon, showed a significant positive correlation with Cd effectiveness. The results provide scientific references for Cd contamination control and safe agricultural production.

Interactive effects of cadmium and Microcystis aeruginosa (cyanobacterium) on the growth, antioxidative responses and accumulation of cadmium and microcystins in rice seedlings.

Cadmium pollution and harmful cyanobacterial blooms are two prominent environmental problems. The interactive effects of cadmium(II) and harmful cyanobacteria on rice seedlings remain unknown. In order to elucidate this issue, the interactive effects of cadmium(II) and Microcystis aeruginosa FACHB905 on the growth and antioxidant responses of rice seedling were investigated in this study, as well as the accumulation of cadmium(II) and microcystins. The results showed that the growth of rice seedlings was inhibited by cadmium(II) stress but promoted by inoculation of M. aeruginosa FACHB905. cadmium(II) stress induced oxidative damage on rice seedlings. Inoculation of M. aeruginosa FACHB905 alleviated the toxicity of cadmium(II) on rice seedlings. The accumulation of cadmium(II) in rice seedlings was decreased by M. aeruginosa FACHB905, but the translocation of cadmium(II) from root to shoot was increased by this cyanobacterium. The accumulation of microcystins in rice seedlings was decreased by cadmium(II). Results presented in this study indicated that cadmium(II) and M. aeruginosa had antagonistic toxicity on rice seedlings. The findings of this study throw new light on evaluation of ecological- and public health-risks for the co-contamination of cadmium(II) and harmful cyanobacteria.

[Cd Runoff Load and Soil Profile Movement After Implementation of Some Typical Contaminated Agricultural Soil Remediation Strategies].

Owing to the strong ability to immobilize and hyperaccumulate some toxic heavy metals in contaminated soils, the biochar, lime and such as hyperaccumulator ramie received increasing interests from crops and environment safety in recent years. Outdoor pot experiment was conducted to compare the impacts of lime and biochar addition in paddy rice treatment, hyperaccumulator ramie and ramie combined with EDTA of plant Phytoremediation methods on soil available Cd dynamics in rainfall runoff and the mobility along soil profile, under both natural acid precipitation and acid soil conditions. The results showed that, biochar addition at a 2% mass ratio application amount significantly increased soil pH, while ramie with EDTA application obviously decreased soil pH compared to ramie monoculture. Within the same rainfall events, water soluble Cd concentration in surface runoff of ramie treatments was significantly higher than those of waterlogged rice treatments, and Cd concentration in runoff was obviously increased after EDTA addition, whereas lime at a 0.3% mass ratio application amount as additive had no obvious impact on soil pH and Cd speciation change, which may be due to the low application amount. During the whole experimental period , water soluble Cd concentration of rainfall runoff in spring was higher than that in summer, showing the same seasonal characteristics in all treatments. Biochar addition could significantly decrease available Cd content in 0-20 cm soil layer and with certain preferable persistency effects, whereas EDTA addition treatment obviously increased available Cd of 0-20 cm soil layer compared to other treatments, and obvious Cd element activation phenomenon in 20-40 cm soil layer was observed after EDTA addition. In conclusion, lime and biochar as environmental and friendly alkaline Cd immobilization materials showed lower environment risk to surface and ground receiving water, but attention should be paid to phytoremediation enhanced with EDTA or other organic acid before promotion and field application for heavy metals removal from contaminated soils.

Mitigating heavy metal accumulation into rice (Oryza sativa L.) using biochar amendment--a field experiment in Hunan, China.

A field experiment was conducted to investigate the effect of bean stalk (BBC) and rice straw (RBC) biochars on the bioavailability of metal(loid)s in soil and their accumulation into rice plants. Phytoavailability of Cd was most dramatically influenced by biochars addition. Both biochars significantly decreased Cd concentrations in iron plaque (35-81 %), roots (30-75 %), shoots (43-79 %) and rice grain (26-71 %). Following biochars addition, Zinc concentrations in roots and shoots decreased by 25.0-44.1 and 19.9-44.2 %, respectively, although no significant decreases were observed in iron plaque and rice grain. Only RBC significantly reduced Pb concentrations in iron plaque (65.0 %) and roots (40.7 %). However, neither biochar significantly changed Pb concentrations in rice shoots and grain. Arsenic phytoavailability was not significantly altered by biochars addition. Calculation of hazard quotients (HQ) associated with rice consumption revealed RBC to represent a promising candidate to mitigate hazards associated with metal(loid) bioaccumulation. RBC reduced Cd HQ from a 5.5 to 1.6. A dynamic factor's way was also used to evaluate the changes in metal(loid) plant uptake process after the soil amendment with two types of biochar. In conclusion, these results highlight the potential for biochar to mitigate the phytoaccumulation of metal(loid)s and to thereby reduce metal(loid) exposure associated with rice consumption.

[Non-point loads of soluble cadmium by in situ field experiment with different landuses, in central Hunan province mining area].

Non-point source loads of heavy metals from contaminated soil has increasingly become the major cause of heavy metal concentrations of rivers and lakes surpassed the limitation value, while only few studies had focused on quantitative monitoring of soil heavy metal transportation to water, in situ field conditions. As reported, agricultural farmland heavy metal contamination was the major contamination problem, especially for cadmium (Cd) pollution in middle and downstream of Xiangjiang River. This study selected the typical Cd polluted agricultural watershed for a case study, three typical landuse types of rice, dry farmland and unused grassland with three replicate quadrates were carried out for natural rainfall runoff hydrology processes monitoring, from 2011-2012. Results showed that, precipitation pH value increased from spring to summer, soluble Cd concentration of spring runoff was significantly higher than that of summer rainfall runoff, which presented an obviously seasonal heterogeneity and had a negative correlation with rainfall pH value, and rainfall pH value can obviously impact soil soluble Cd transportation into surface runoff charge. In the same rainfall event, soluble Cd concentration and non-point load of rice were significantly lower than those of dry land and unused grassland, while no obviously seasonal trend was found for non-point load of Cd from three typical landuse types because of the rainfall depth variance, which needs more researches and concerns in the future. These results can provide valuable data and scientific supports for watershed scale's heavy metal non-point source load quantitative estimation and water environment management and water quality diagnosis and early warning.

An arsenic-contaminated field trial to assess the uptake and translocation of arsenic by genotypes of rice.

Compared to other cereals, rice has particular strong As accumulation. Therefore, it is very important to understand As uptake and translocation among different genotypes. A field study in Chenzhou city, Hunan province of China, was employed to evaluate the effect of arsenic-contaminated soil on uptake and distribution in 34 genotypes of rice (including unpolished rice, husk, shoot, and root). The soil As concentrations ranged from 52.49 to 83.86 mg kg(-1), with mean As concentration 64.44 mg kg(-1). The mean As concentrations in rice plant tissues were different among the 34 rice genotypes. The highest As concentrations were accumulated in rice root (196.27-385.98 mg kg(-1) dry weight), while the lowest was in unpolished rice (0.31-0.52 mg kg(-1) dry weight). The distribution of As in rice tissue and paddy soil are as follows root ≫ soil > shoot > husk > unpolished rice. The ranges of concentrations of inorganic As in all of unpolished rice were from 0.26 to 0.52 mg kg(-1) dry weight. In particular, the percentage of inorganic As in the total As was more than 67 %, indicating that the inorganic As was the predominant species in unpolished rice. The daily dietary intakes of inorganic As in unpolished rice ranged from 0.10 to 0.21 mg for an adult, and from 0.075 to 0.15 mg for a child. Comparison with tolerable daily intakes established by FAO/WHO, inorganic As in most of unpolished rice samples exceeded the recommended intake values. The 34 genotypes of rice were classified into four clusters using a criteria value of rescaled distance between 5 and 10. Among the 34 genotypes, the genotypes II you 416 (II416) with the lowest enrichment of As and the lowest daily dietary intakes of inorganic As could be selected as the main cultivar in As-contaminated field.

[Effects of urea and coated urea on harmful gases concentrations in plastic greenhouse].

With simulation test and plastic greenhouse experiment, this paper studied the effects of urea and minerals- coated urea on the soil pH and harmful gases concentrations in plastic greenhouse. The results showed that under simulated condition, the application of these'two N fertilizers led to an initial increase of soil pH, which reached the maximum (an increment of > 50%) within the first week and dropped to the initial level by the end of the fifth week. In plastic greenhouse, applying urea and coated urea resulted in the increase of NH3, NO2 and O3 concentrations. The daily volatilization amount of NH3 and NO2 was higher in urea treatment than in coated urea treatment, and the highest value in urea treatment was 42.36 microg x m(-3) x d(-1) for NH3, 41.95 microg x m(-3) x d(-1) for NO2, and 86.00 microg x m(-3) x d(-1) for O3. The volatilization intensity of NH3 and NO2 was influenced by temperature and sunlight, while the O3 concentration was influenced by sunlight.