镉同位素分馏在土壤-植物体系中的研究进展

镉污染土壤因其导致粮食作物超标以及通过食物链对居民健康构成威胁,引起了人们的高度关注。土壤镉的迁移转化、植物根部对镉的吸收、植物体内对镉的装载转运和贮存是土壤-植物体系镉生物地球化学循环的重要过程。近年来,稳定同位素分馏技术被广泛应用于土壤-植物系统中镉的迁移和储存,为研究镉在不同土壤库和植物部位中的迁移和转化提供了新的思路和视角。本文首先介绍了镉同位素组成分析的基本原理和方法;其次对土壤矿物溶解、共沉淀、吸附和有机质螯合配位等四个关键过程引起的镉同位素分馏方向和程度进行综述,并重点针对植物根部对镉的吸收、根部-地上部转运和籽粒储存等三个关键过程阐述植物体内镉同位素分馏机制;最后基于目前研究现状,展望了土壤-植物体系镉同位素分馏尚需解决的科学问题和未来的研究方向。有助于深入理解镉在土壤-植物体系中的生物地球化学过程与机制,以期为镉污染土壤的安全利用与治理修复、农产品减毒脱毒等应用技术的研发提供科学依据。     

土壤有机质对镉污染土壤修复的影响

镉是生物非必需具生物毒性元素,有机质作为修复镉污染土壤的重要改良剂之一而备受关注。土壤有机质通过对土壤理化性质、对镉的吸附-解析、络合作用、生物有效性作用影响镉污染土壤修复效果。主要阐述了土壤有机质对镉污染土壤修复的影响作用机制,探讨了有机质的适用条件、影响因子,分析了工程应用过程存在的问题,以期为重金属污染土壤修复技术研究提供新的思路。     

影响土壤中镉的植物有效性的因素及镉污染土壤的植物修复

阐述了镉的来源及其对人类的危害,并对影响土壤中镉的植物有效性的土壤因素中的pH、氧化还原电位(Eh)、有机物质、营养物质浓度对镉的植物有效性的作用作了详细的阐述。此外对其它如EDTA、淤泥等对土壤中镉的植物有效性的影响和镉污染土壤的植物修复等方面也进行了综述,并对镉污染土壤的修复治理与趋势进行了展望。     

巯基膨润土钝化修复镉污染水稻土的研究

通过田间种植水稻试验,探究了巯基膨润土（Bent-SH）对镉污染土壤的修复效果及钝化机理。结果表明:添加Bent-SH对土壤理化性质的影响很小,土壤有效态镉含量随Bent-SH添加量的增加逐渐降低,与对照相比,其最大下降率为48.57%。添加Bent-SH降低了土壤镉的迁移能力,降低了大米、秸秆对土壤镉的吸收,其最大下降率分别为72.73%、70.97%。土壤离子交换态镉（EX-Cd）含量最大下降率为54.17%,而铁锰氧化物结合态镉（FMO-Cd）和强有机质结合态镉（SO-Cd）含量最大增长率分别为117.40%和75.00%。Bent-SH添加量与土壤有效态镉、大米镉、秸秆镉含量呈极显著负相关,与土壤FMO-Cd、SO-Cd含量呈显著正相关,与土壤EX-Cd含量呈显著负相关。结果表明Bent-SH可以使土壤中的镉由EX向FMO和SO转化,有效降低镉的活性和生物可利用性,从而实现了镉污染土壤的钝化修复。     

不同有机肥对镉污染土壤镉形态及小麦抗性的影响

为了探讨有机肥钝化修复镉污染土壤对小麦生理抗性及小麦体内镉含量的响应,通过盆栽试验研究了不同有机肥对镉污染土壤Cd形态、小麦体内脯氨酸、丙二醛及小麦各部位镉含量的影响。结果表明:在镉污染土壤上施用有机肥后土壤可交换态Cd与碳酸盐结合态Cd含量有所下降,铁锰氧化物结合态Cd、有机结合态Cd和残留态Cd含量有所增加。施用羊粪、鸡粪的处理SH、CHSM、CMSL、CL。施用猪粪的处理PMPHPL。施用有机肥后小麦体内脯氨酸、丙二醛含量和小麦各部位Cd含量显著下降,施用羊粪、鸡粪的处理随施肥量的增加小麦体内脯氨酸、丙二醛含量和Cd含量明显降低,施用猪粪的PM处理的小麦脯氨酸、丙二醛含量和小麦根、茎、叶、籽粒中的Cd含量显著低于其他处理,其综合效果猪粪羊粪鸡粪。有机肥可通过改变污染土壤中的重金属形态而降低其生物有效性,可用于重金属污染土壤修复。     

南方典型镉污染稻田土壤有效态镉预测模型研究

为了更好地指导重金属镉污染稻田实施土壤修复、管控土壤镉毒害风险,以我国南方典型镉污染稻田为研究对象,基于316个监测点位的土壤镉及理化性质指标测定,分析土壤有效态镉含量与土壤理化因子间的相互关系,并通过逐步多元回归方程,建立稻田土壤有效态镉的预测模型。结果表明,土壤总镉、有效锌、有效硫、有效磷及有效铜是影响南方稻田土壤有效态镉含量的主要因素。通过区域调研,借助逐步回归分析得到南方稻田土壤有效态镉含量的预测模型方程:Cdext=-0.006+0.371(Cdtot)+0.014(A-Zn)+0.001(A-S)-0.001(A-P)+     

无瓣蔊菜对镉的积累特性研究

为从农田杂草中筛选出镉超富集植物用于镉污染农田的修复,本研究以无瓣蔊菜为试验材料,通过模拟不同浓度镉胁迫条件,探究不同镉浓度处理对无瓣蔊菜生长量、光合色素含量以及镉富集特性的影响,揭示无瓣蔊菜对镉污染土壤的修复能力。结果表明,随着土壤镉浓度的增加,无瓣蔊菜的生长受到抑制但无毒害症状,当土壤镉浓度≤75 mg·kg-1时,无瓣蔊菜的叶绿素含量有所降低,但与对照间无显著性差异;当土壤镉浓度达到75 mg·kg-1时,无瓣蔊菜地上部分镉含量为112.77 mg·kg-1,根系镉含量为69.87 mg·kg-1,且植株根系和地上部分对镉的富集系数(BCF)和转运系数(TF)均大于1,说明无瓣蔊菜是一种镉富集植物。转运量系数(TAF)以及镉积累量与土壤镉浓度的回归分析表明,镉在无瓣蔊菜中的分布规律为地上部分根系。当土壤镉浓度≤50mg·kg-1时,镉元素从根系到地上部分的转运能力增强,有利于无瓣蔊菜富集镉。综上所述,无瓣蔊菜对镉有很强的耐性,可吸收土壤中的镉,并转运积累到地上部分,收获后将其迁移出土壤,以达到修复镉污染的目的。无瓣蔊菜适用于镉污染浓度在75 mg·kg-1以内的农田修复。本研究为筛选优良超镉富集植物材料提供了相关的科学依据。     

成都平原不同种植模式下重金属镉污染风险和经济效益评价

为了评估成都平原常规粮油种植模式下的重金属镉污染风险和经济效益,寻求稳定、高产且利于推广的安全种植模式。选取成都平原最常见的6种粮油作物,设置了小麦-玉米轮作、油菜-玉米轮作、小麦-红苕轮作、油菜-红苕轮作、小麦-大豆轮作、油菜-大豆轮作、小麦-水稻轮作、油菜-水稻轮作8种种植模式,在轻中度污染农田开展了两年田间试验,对各个种植模式的产量、经济产出,以及收获物、秸秆和土壤的重金属镉含量进行测定。结果表明,当前试验区最广泛使用的小麦-水稻种植模式下的小麦和水稻籽粒镉含量均超标,存在极大的生产风险。玉米-油菜种植模式的籽粒镉含量最低,均未超标,能够实现安全生产,但经济产出较小麦-水稻轮作模式显著降低。油菜-水稻轮作模式的农田产出效益最大。相比种植小麦,种植油菜后,后茬水稻对应的重金属镉含量降低70.2%。综合生产和环境效益,将小麦-水稻种植模式更换为油菜-水稻模式是目前既能保证农民收益又能有效降低重金属镉污染风险的最佳措施。     

膨润土和沸石在镉污染土壤治理中的应用

采用通过盆栽试验,研究了膨润土和沸石对镉污染土壤的治理效果。结果表明,施加膨润土后不同污染程度土壤的交换态、碳酸盐结合态镉的质量分数都有所下降,铁锰氧化物结合态、有机结合态和残渣态镉的质量分数则有所上升。沸石和膨润土对轻度、中度镉污染土壤都表现出钝化作用,对重度镉污染土壤,膨润土对镉的钝化效果明显,而沸石却起到了激活镉的作用。在不同程度镉污染土壤上,膨润土可增加乌塌菜的生物量,并可抑制其对镉的吸收,降低乌塌菜植株体内镉的浓度,对乌塌菜的生长具有显著的促进作用。沸石对轻度和中度镉污染土壤均可降低乌塌菜植株体内镉的浓度,促进乌塌菜的生长并增加其生物量;对重度镉污染土壤,沸石对乌塌菜的生长影响较小,乌塌菜植株体内镉的积累显著增加。     

地球化学工程技术修复农田土壤重金属污染研究进展

随着我国农田土壤重金属污染的加剧,传统的物理、化学和生物修复方法不能完全满足农田土壤修复的要求,亟待寻找高效稳定、成本低廉且无二次污染的农田土壤修复技术。地球化学工程技术即是遵循这一理念的修复技术之一。本文就地球化学工程技术在农田土壤修复中的应用现状与阶段性成果进行了回顾,着重概述了地球化学材料固定与钝化,地球化学工程阻隔,地球化学转化、吸收与浓集以及地球化学自然降解与衰减等4类技术在土壤修复中的研究进展和实践成果。并在此基础上讨论了应用地球化学工程技术进行农田土壤修复的优势和不足,展望了地球化学工程技术修复农田土壤的应用前景和发展趋势,提出注重多种修复技术的联合使用、开发功能化纳米材料与磁性纳米复合材料进行修复及加快土壤修复理论成果转化的研究方向。     

Plant- and microbe-assisted biochar amendment technology for petroleum hydrocarbon remediation in saline-sodic soils: A review

Soil degradation through salinization and pollution by toxic compounds such as petroleum hydrocarbons(PHCs) in the coastal wetlands has become a significant threat to ecosystem health, biodiversity, and food security. However, traditional remediation technologies can generate secondary pollutants, incur high operating costs, and consume significant quantities of energy. Bioremediation, using plants, biochar, and microbes, is an innovative and cost-effective option to remediate contaminated soils. Biochar, as a plant/microbe growth enhancer, is a promising green approach for the sustainable phytoremediation of PHCs in salinized soils. This review therefore summarizes the effect of plant-and microbe-assisted biochar amendment technology for the remediation of PHCs and salinization. Plant-microbe interactions mediated rhizodegradation despite increasing hydrocarbon sorption. Overall, microbial respiration is more active in biochar amendments, due to faster biodegradation of PHCs and improved soil properties. The use of biochar, plants, and microbes is recommended,as it offers a practical and sustainable option, both ecologically and economically, for the remediation of PHCs and excess salinity. Further development of new green technologies is to be encouraged.     

我国稻田土壤镉污染现状及安全生产新措施

水稻是我国重要的粮食作物,由于受重金属污染威胁日益增大,其安全生产问题备受关注。通过综述我国稻田土壤及稻米镉污染现状、镉污染土壤改良剂研究进展以及稻米对镉富集的品种间差异,认为在土壤中镉的去除修复技术无法在短时间内实现的前提下,镉排异型水稻品种的筛选与利用是实现其安全生产的一个新的有效措施。在此基础上,配合一些污染土壤改良剂的使用,会进一步增强其安全生产水平。     

土壤有机污染物电化学修复技术研究进展

综述了有机污染土壤的电动力修复和微生物电化学修复的最新研究进展。分析了电动力修复中电极材料、运行条件等因素对污染物去除效果的影响,总结了添加表面活性剂、引入具有降解能力的基质、与化学或生物联合等方式对土壤修复效果的强化作用,阐述了微生物电化学修复的效果、影响因素和微生物群落演变的规律。电化学技术能够有效去除土壤中的有机污染物,且电动力较微生物电化学具有更好的去除效果。为了实现电化学技术在污染土壤修复中的应用,未来需要从土壤导电性、电极材料以及反应器构型等方面优化以提高修复效果;此外,电化学修复技术的机理、功能微生物的群落特征研究等也是下一步研究的重点。     

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.

     

水化氯铝酸钙与传统钝化剂降低土壤镉生态及健康风险的对比研究

针对红壤、棕壤、褐土、黑土4种中国典型的Cd污染土壤,应用Ca(OH)2、Ca(H2PO4)2以及层状双金属氢氧化物（Layered Double Hydroxides,LDHs）、水化氯铝酸钙（CaAl-Cl LDH）开展钝化修复,并从土壤Cd的生态风险和健康风险角度进行修复效果对比研究。分析钝化剂对土壤pH值、土壤Cd的赋存形态以及土壤Cd直接经口摄入的生物可给性的影响,并对修复机理进行深入探究。结果表明,在Ca(OH)2、Ca(H2PO4)2和CaAl-Cl LDH各自相对最优施用量下,3种钝化剂均可显著降低土壤Cd的活性系数（P<0.05）,平均降幅分别为16.1%、56.9%和29.2%,可降低土壤Cd的作物吸收量及Cd对周边生态环境的风险。此外,施用CaAl-Cl LDH能显著且更为有效地降低土壤Cd的生物可给性（P<0.05）及Cd对人体的健康风险,在胃和小肠阶段的平均降幅为19.2%和33.0%,其中胃阶段分别达到施用Ca(OH)2和Ca(H2PO4)2的3.11和1.99倍,小肠阶段为5.99和2.72倍。该研究为Cd污染土壤钝化修复剂的开发、改进和选择提供了科学依据和参考。     

石灰组配土壤改良剂抑制污染农田水稻镉吸收

为达有效地调控污染稻田水稻糙米对Cd吸收,该研究选取湖南省长株潭地区的湘潭、醴陵和株洲3处不同Cd污染程度田块,研究石灰配施海泡石、钙镁磷肥、有机肥对水稻Cd吸收和累积的影响。结果表明,施用石灰及其组配改良剂均可明显提高土壤pH值,有效降低土壤中酸提取态Cd含量和水稻中Cd含量。与不施用改良剂相比,石灰配施海泡石或有机肥、配施海泡石和有机肥,Cd污染稻田土壤pH值平均升高1.08,0.96和0.93个单位,酸提取态Cd质量分数分别平均降低20.6%,15.6%和21.2%。石灰配施海泡石、有机肥或钙镁磷肥处理下在轻度Cd污染田块中糙米Cd含量较对照分别显著降低了48.3%,46.7%和34.2%,石灰配施有机肥、钙镁磷肥或钙镁磷肥和有机肥处理下在中度Cd污染田块中糙米Cd含量较对照分别显著降低了52.8%,47.8%和37.5%,石灰配施钙镁磷肥和有机肥、有机肥或海泡石处理下在重度Cd污染田块中糙米Cd含量较对照分别显著降低了51.2%,44.6%和42.5%,均低于食品安全国家标准中糙米限量值0.2 mg/kg(GB2762-2017)。相关分析表明,土壤中酸提取态Cd含量与水稻根、茎叶和糙米中Cd含量呈显著正相关关系(P0.05),说明土壤酸提取态Cd含量是影响糙米对Cd吸收的关键因素之一。上述结果说明,石灰配施海泡石、有机肥或钙镁磷肥+有机肥可有效调控污染稻田土壤中Cd进入水稻,实现水稻安全生产。     

Fertilizer amendment for improving the phytoextraction of cadmium by a hyperaccumulator <Emphasis Type="Italic">Rorippa globosa</Emphasis> (Turcz.) Thell

Purpose  

Two main pathways of phytoremediation of heavy metal-contaminated soils are phytostabilization and phytoextraction. Some soil amendments can strengthen phytostabilization or phytoextraction through either reducing heavy metal bioavailability in soil or increasing the heavy metal accumulation capacity of the hyperaccumulator (enhancing heavy metal concentration or shoot biomass of the hyperaccumulator). Urea and chicken manure are often used as fertilizers. This research will explore their effects on a newly found hyperaccumulator, Rorippa globosa (Turcz.) Thell., phytoremediating cadmium (Cd).     

配施硫基肥对夏玉米镉铅累积的阻控效应

该文以府河流域污灌区农田为研究对象,通过田间小区试验研究了5种施肥措施对土壤重金属镉(Cd)、铅(Pb)有效性以及夏玉米(Zea mays L.)对Cd、Pb富集和转运能力的影响。结果表明:与农民常规施肥(CK)相比,尿素、磷酸二铵和氯化钾配施(N-P-K)以及腐殖酸复合肥、尿素和磷酸二铵配施(HA-N-P)的表层土壤Cd、Pb有效性以及夏玉米对Cd、Pb的富集和迁移能力差异均不显著(P0.05)。然而,腐殖酸复合肥、硫酸铵和磷酸二铵配施(HA-S-P)以及硫酸铵、磷酸二铵和硫酸钾配施(S-P-K)2种施肥措施的表层土壤有效Cd含量分别比CK降低了10.60%和6.36%,表层土壤有效Pb含量分别比CK降低了11.49%和6.00%。此外,HA-S-P处理和S-P-K处理夏玉米Pb转运系数分别比CK降低了50.33%和77.10%,且夏玉米籽粒Pb含量分别比CK降低了59.75%和80.43%(P0.05),但各处理间夏玉米对Cd的转运和富集能力差异并不显著,这说明施用硫基肥可有效抑制夏玉米对Pb的富集和转运,但并未影响其对Cd的富集和转运。综上所述,该污灌区轻度Cd、Pb复合污染农田土壤种植夏玉米建议硫酸铵、磷酸二铵和硫酸钾配施,或者腐殖酸复合肥、硫酸铵和磷酸二铵配施。     

Evaluation of fly ash,apatite and rice straw derived-biochar in varying combinations for in situ remediation of soils contaminated with multiple heavy metals

ABSTRACT

In

-situ sorbent amendment is a relatively low-cost, low-impact approach for remediation of soil contaminated with heavy metals (HMs), and thus is considered a way to be favored in developing countries. In this study, materials of non-hazardous, alkaline agronomic and industrial by-products were used as sorbents to explore their capacity of in situ immobilization of multiple HMs in mining-impacted arable soil. These sorbents included fly ash (FA), biochar (BC) and apatite (AP) and they were implemented with varying ratios of combinations. Results of soil microcosm tests showed that after incubation for 90 days, concentrations of Pb, Zn, and Cd in their exchangeable forms determined by a sequential extraction method significantly decreased in amended soils, as opposed to the unamended control. Of the five sets of amendments, the composite of FA, BC, and AP resulted in the maximum reduction (up to 80%) in the mobility of Pb, Zn, and Cd in soils. The mechanisms underlying the immobilization of HMs in amended soils might involve processes of surface precipitation, ion exchange and complexation, in which the physicochemical properties of sorbent materials played an important role. The immobilization efficacy of sorbent amendments on HMs in soil was further supported by pot experiments in which significant inhibition of HM accumulation in the belowground and aboveground tissues of maize was observed after 50-day cultivation in amended soils as compared with control soil. Together, these results suggest that the application of cost-saving and environmentally friendly materials derived from wastes as sorbents to remediate soils contaminated with multiple HMs is promising for developing countries like Vietnam.     

改良剂对镉污染酸性水稻土的修复效应与机理研究

为探明田间条件下施用石灰、钙镁磷肥、海泡石和腐殖酸等改良剂对Cd污染酸性水稻土的修复效应和作用机理, 通过在Cd污染区建立田间小区试验, 研究了改良剂单施和与石灰配施对Cd污染酸性水稻土中Cd作物有效性的影响。结果表明, 施用改良剂有效地改变了土壤中Cd的存在形态, 除腐殖酸外, 其他改良剂均使土壤酸提取态Cd不同程度地转化为可还原态Cd和残渣态Cd; 施用改良剂可使0.1 mol·L^-1 NaNO₃和 0.01 mol·L^-1CaCl₂提取态Cd 降低26%~97%, 降低效果为石灰+海泡石>海泡石>石灰+钙镁磷肥>钙镁磷肥>石灰>石灰+腐殖酸>腐殖酸; 改良剂使水稻地上部分的Cd吸收量降低6%~49%。试验结果还显示, 施用改良剂提高土壤pH是引起土壤中Cd作物有效性降低的主要原因之一。根据田间试验的结果, 海泡石可推荐作为Cd污染酸性水稻土的改良剂, 而腐殖酸则不宜使用。