几种有机、无机钝化剂对铜污染土壤的钝化效果研究

利用石灰、棉花秆生物炭、玉米秆生物炭和阴离子聚丙烯酰胺作为钝化剂,对3种浓度梯度的铜污染土壤进行处理。采用Tessier形态分级试验对钝化能力和效果进行评价,并以此研究土壤中铜的形态变化。结果发现,石灰(0.2%)、棉花秆生物炭(1%)和玉米秆生物炭(1%)和阴离子聚丙烯酰胺2‰对Cu污染土壤治理均具有较为良好的效果。在铜浓度为50 mg/kg的试验组中,石灰、棉花秆生物炭、玉米杆生物炭和阴离子聚丙烯酰胺可分别将有效态铜含量降低为6.73%、7.92%、8.16%、8.83%。Tessier形态分级试验结果表明:1)随着时间延长,水溶态+交换态铜含量自然降低;2)加入钝化剂的试验组,有效态Cu含量明显降低,缓和态和无毒态的Cu含量有不同程度地增加。说明施用钝化剂促进Cu由有效态向缓和态和无毒态转化是土壤原位修复的重要机制。     

Spectroscopic studies of dye-surfactant interactions with the co-existence of heavy metal ions for foam fractionation

The interaction between a cationic dye Methylene Blue (MB) and an anionic surfactant sodium dodecyl sulfate (SDS) with the presence of Cd²⁺ was investigated spectrophotometrically in a certain concentration range. The spectrophotometric measurements of dye-metal ion-surfactant system were carried out. The results indicated that the SDS concentration had a significant influence on the dye spectrum, while the addition of Cd²⁺ hardly caused change of the maximum value of absorbance. According to this observation, we concluded that electrostatic and hydrophobic interaction between dye and surfactant occurred up to a certain level, and the homo-ions Cd²⁺ almost exerted no effect on the dye-surfactant complexation, establishing a theoretical foundation for simultaneous removal of organic dye and heavy metal using foam fractionation. Meanwhile, the effects of their interaction on foam performance were investigated. The results showed that the addition of Cd²⁺ favored the tendency to ameliorate foam properties just contrary to MB. The feasibility of foam separation for dye and heavy metal removal from simulated wastewater was also confirmed using a continuous foam fractionator. In the simultaneous removal process, with the initial SDS concentration ranging from 0.5 to 5.0 mmol/L, the maximum removal efficiencies of MB and Cd²⁺ were obtained as 99.69% and 99.61%, respectively. The enrichment ratios were reduced from 24.34 to 7.65 for MB and from 22.01 to 3.35 for Cd²⁺.     

光照厌氧条件下沼泽红假单胞菌对砷的抗性及其机制

采用UV-Vis和HPLC-ICP-MS分析方法,在光照厌氧条件下研究了沼泽红假单胞菌(Rhodopseudomonas palustris CQV97)对砷(As)的抗性和机制.结果表明,As(Ⅴ)与As(Ⅲ)对R.palustris CQV97的半数效应浓度(EC50)分别为2.3mmol·L-1和0.9mmol·L-1;该菌株能够将As(Ⅴ)还原为As(Ⅲ),不能将As(Ⅲ)转化为As(Ⅴ)或甲基砷;在含有0.1mmol·L-1As(Ⅴ)的培养基中培养80h,细胞积累的总As可达1.32mg·g-1(以干重计),其中,9.8%存在于细胞质中,4.9%与细胞膜的脂质相结合,其余被认为吸附在细胞表面;全细胞、细胞质、细胞膜所含的As(Ⅲ)和As(Ⅴ)的相对比例分别为16.3%和83.7%、12.1%和87.9%、16.5%和83.5%.静息细胞砷吸附结果表明,与0℃孵育细胞相比,25℃孵育细胞对As(Ⅴ)和As(Ⅲ)吸附量较高;灭活细胞对As(Ⅴ)的吸附量进一步提高,而对As(Ⅲ)的吸附量则降低.因此,光照厌氧条件下,R.palustrisCQV97对As具有较强的抗性和吸附特性,对As(Ⅴ)的抗性和吸附性均明显高于As(Ⅲ);其抗砷机制为细胞质As(Ⅴ)的还原途径,具体为在细胞内将As(Ⅴ)还原为As(Ⅲ),继而As(Ⅲ)被转运至细胞外,维持胞内As的含量在较低水平.本研究可为深入理解光合细菌对无机砷的抗性机制、砷的地球化学循环及砷的环境污染和生物修复提供理论参考.     

An approach for arsenic in a contaminated soil: Speciation, fractionation, extraction and effluent decontamination

The fractionation and speciation of As in a contaminated soil were investigated, and a remediation strategy was tested. Regarding speciation, we found that As(V) prevails over As(III) whereas more than 40% of total arsenic is in organic form. The fractionation of As was investigated with two sequential extraction methods: a low mobility was found. Then we tested the possibility of using phosphoric acid to extract As from the soil and cleaning the washing effluents by sorption onto montmorillonite. The efficiency of the extraction and of the adsorption onto the clay were also investigated for Cr, Cu, Fe, Mn, Ni, Pb and Zn, whose total concentrations and fractionation in the soil are reported here. The extraction percentages for As and metals ranged from 30 to 65%; the residual proportions in the soil are presumably in very unreactive forms. Montmorillonite showed a good uptake capacity towards the investigated pollutants.     

Surface protection method for the magnetic core using covalent organic framework shells and its application in As(III) depth removal from acid wastewater

Fe₃O₄-based materials are widely used for magnetic separation from wastewater. However, they often suffer from Fe-leaching behavior under acidic conditions, decreasing their activity and limiting sustainable practical applications. In this study, covalent organic frameworks (COFs) were used as the shell to protect the Fe₃O₄ core, and the Fe₃O₄@COF core-shell composites were synthesized for As(III) removal from acid wastewater. The imine-linked COFs can in situ grow on the surface of the Fe₃O₄ core layer by layer with [COFs/Fe₃O₄]_mol ratio of up to 2:1. The Fe-leaching behavior was weakened over a wide pH range of 1-13. Moreover, such composites keep their magnetic characteristic, making them favorable for nanomaterial separation. As(III) batch adsorption experiments results indicated that, when COFs are used as the shell for the Fe₃O₄ core, a balance between As(III) removal efficiencies and the thickness of the COF shell exists. Higher As(III) removal efficiencies are obtained when the [COFs/Fe₃O₄]_mol ratios were < 1.5:1, but thicker COF shells were not beneficial for As(III) removal. Such composites also exhibited better As(III) removal performances in the pH range of 1–7. Over a wide pH range, the zeta potential of Fe₃O₄@COF core-shell composites becomes more positive, which benefits the capture of negative arsenic ions. In addition, thinner surface COFs were favorable for mass transfer and facilitating the reaction of Fe and As elements. Our study highlights the promise of using COFs in nanomaterial surface protection and achieving As(III) depth removal under acidic conditions.     

Accumulation and Chemical Fractionation of Heavy Metals in Andisols after a Different, 6-year Fertilization Management (8 pp)

Goal, Scope and Background Andisols are widespread in Japan and have some special properties such as high anion exchange capacity, low bulk density, and high organic matter content, which might influence the accumulation or chemical fractionation of heavy metals. However, few such data exist in Japanese andisols. The primary objective of this study was to investigate the distribution and chemical fractions of Cu, Zn, Ni, and Cr in the soil profiles and subsequently to assess their potential environmental hazard. Materials and Methods Soil samples were taken from a field experiment conducted on Japanese andisols, which had received either swine compost or chemical fertilizers for 6 years. Concentrations of Cu, Zn, Ni, and Cr were determined for all of the obtained extract solutions by ICP-AES. Results and Discussion Considerably higher total concentrations of Cu and Zn were observed in the top 20 cm layer of the compost-amended soil, relative to the unfertilized soil, while chemical fertilizers had little effect. Application of the swine compost increased the concentrations of Cu and Zn, but not Ni and Cr, in all fractions in the top 20 cm layer. The greatest increase in the organically bound fraction (OM) Cu and dilute acid-exchangeable fraction (DAEXCH) Zn was observed. This suggests that Cu and Zn are potentially bioavailable and mobile in the andisol profiles after 6-year consecutive applications of the swine compost. On the other hand, distribution of Cu, Zn, Ni and Cr among various soil fractions was generally unaffected by chemical fertilizers. Conclusions We observed that 6-year consecutive applications of the swine compost led to an increase in total metals of Cu and Zn, as well as their all-chemical fractions, in the top 20 cm soil layers. Potential hazard of heavy metals, especially of Cu and Zn, as a result of the use of swine compost on andisols, must be taken into account. Recommendations and Outlook The long-term effect of the accumulation of heavy metals, particularly Cu and Zn, in various plant tissues and soils, as well as their potential risk to surface water via runoff and groundwater via leaching, needs to be carefully considered. Further investigations in the long-term experiments are therefore necessary. - Abbreviations. EXCH, exchangeable fraction of metals; DAEXCH, dilute acid-exchangeable fraction of metals; FeMnOX, iron and manganese-oxide-bound fraction; OM, organically-bound fraction; RESD, residual fraction. COMPOST, SRNF, RANF, and CONTROL stand for compost (from swine wastes), slow-release nitrogen fertilizer (coated urea), readily available nitrogen fertilizer (including NH4-N, P, and K fertilizers), and no fertilizer application, respectively.     

Dissipation of S-metolachlor and butachlor in agricultural soils and responses of bacterial communities: Insights from compound-specific isotope and biomolecular analyses

The soil dissipation of the widely used herbicides S-metolachlor(SM) and butachlor(BUT)was evaluated in laboratory microcosms at two environmentally relevant doses(15 and 150 μg/g) and for two agricultural soils(crop and paddy).Over 80% of SM and BUT were dissipated within 60 and 30 days,respectively,except in experiments with crop soil at 150 μg/g.Based on compound-specific isotope analysis(CSIA) and observed dissipation,biodegradation was the main process responsible for the observed decrease of SM and BUT in the paddy soil.For SM,biodegradation dominated over other dissipation processes,with changes of carbon isotope ratios(Δδ~(13)C) of up to 6.5‰ after 60 days,and concomitant production of ethane sulfonic acid(ESA) and oxanilic acid(OXA) transformation products.In crop soil experiments,biodegradation of SM occurred to a lesser extent than in paddy soil,and sorption was the main driver of apparent BUT dissipation.Sequencing of the 16 S rRNA gene showed that soil type and duration of herbicide exposure were the main determinants of bacterial community variation.In contrast,herbicide identity and spiking dose had no significant effect.In paddy soil experiments,a high(4:1,V/V) ESA to OXA ratio for SM was observed,and phylotypes assigned to anaerobic Clostridiales and sulfur reducers such as Desulfuromonadales and Syntrophobacterales were dominant for both herbicides.Crop soil microcosms,in contrast,were associated with a reverse,low(1:3,V/V)ratio of ESA to OXA for SM,and Alphaproteobacteria,Actinobacteria,and Bacillales dominated regardless of the herbicide.Our results emphasize the variability in the extent and modes of SM and BUT dissipation in agricultural soils,and in associated changes in bacterial communities.     

Titanium nanoparticles attenuates arsenic toxicity by up-regulating expressions of defensive genes in Vigna radiata L

Arsenic(As)-toxicity is recognized as one of the major environmental problems,affecting productivity of crops worldwide,thereby threatening sustainable agriculture and food security.Progression in nanotechnology and its impacts have brought up concerns about the application of engineered nanoparticles(NPs) in various sectors of the economy,including the field of agronomy.Among various NPs,there has been a rising amount of interest regarding the effects of titanium NPs(TiNPs) on plants growth and development,and their fate of abiotic stress tolerance.Hence,the present study was aimed to assess the ameliorative potentialities of chemically and biologically/green synthesized TiNPs to alleviate As-induced toxic responses in Vigna radiata L.The results revealed that exposure to As hindered the growth indices(radicle length and biomass) and membrane integrity,while were improved with the application of chemical and green synthesized TiNPs.In addition,treatment of As provoked the accretion of reactive oxygen species(superoxide and hydrogen peroxide) and malondialdehyde(a lipid per oxidized product),but were diminished by the supplementation of chemical and green manufactured TiNPs.The experimental data also signified that exogenous application of chemical and green synthesized TiNPs conferred tolerance to As-induced oxidative injuries via perking-up the expressions of antioxidant genes and enzyme systems viz;superoxide dismutase and catalase.Therefore,the present study inferred that chemically and green synthesized TiNPs,particularly green manufactured,effectively mitigated the adverse impacts of As by augmenting antioxidant machinery,thereby proving its potentiality in the alleviation of As-toxicity,at least in Vignaradiata L.     

高原喀斯特土壤有机碳短期稳定的温度作用机制

探明有机碳稳定的温度作用机制,是评估全球变化背景下土壤碳源/汇演变趋势的关键.应用土壤密度分组和酸水解技术,采用红外线辐射增温法,对比研究不同升温情景下高原喀斯特土壤及其物理和生化组分中有机碳密度的短期(4a)变化特征.升温情景包括不升温(对照)、对称升温(全年同步升温2.0℃)和非对称升温(冬春/夏秋季升温幅度为2.5℃/1.5℃、3.0℃/1.0℃、3.5℃/0.5℃和4.0℃/0℃,低度、中度、高度和极端非对称升温),其中中度非对称升温与该区域多年升温情景类似.结果表明,不同升温情景下表层(0~15 cm)土壤有机碳密度在1.95~2.02 kg·m-2之间,其差异不显著,且与对照(1.94 kg·m-2)差异不显著.升温处理间土壤轻组和重组碳密度、重组顽固性碳密度差异不显著,且与对照差异不显著.5个升温处理轻组顽固性碳平均密度是对照的1.18倍,其中对称升温、低度和中度非对称升温处理显著高于对照.轻组顽固性碳密度和轻组顽固性碳指数随升温的非对称性增加而降低,其中对称升温处理均显著高于中度、高度和极端非对称升温.亚表层(15~30 cm)土壤及其物理和生化组分中有机碳密度对短期升温均不敏感.研究揭示:短期内,升温提高了高原喀斯特土壤非保护组分中有机碳顽固性.基于对称升温情景并不一定会误估全球变暖对土壤有机碳数量和土壤碳物理保护能力的影响,但可能会高估表层土壤(0~15 cm)非保护组分有机碳顽固性.