富里酸改性FeMnNi-LDH对砷镉污染土壤的钝化修复

选用腐殖质活性组分富里酸(FA)作为铁锰镍层状双氢氧化物(FeMnNi-LDH)的修饰物,采用共沉淀法制备出稳定层状FA@Fe Mn Ni-LDH复合材料,并运用于As(Ⅲ)和Cd(Ⅱ)复合污染土壤的钝化修复.通过小白菜盆栽实验研究了在不同砷镉复合污染水平及不同初始土壤pH值条件下,复合材料对土壤As(Ⅲ)和Cd(Ⅱ)的钝化效果、各形态含量变化及对小白菜根部和地上部As(Ⅲ)和Cd(Ⅱ)转运、富集系数的影响,并进行相关性分析.结果表明,FA@Fe Mn Ni-LDH复合材料对As和Cd具有显著的同步钝化效果.当复合材料添加量由0%增加到1.0%,促进了土壤非专性吸附态和结晶铁铝氧化物结合态As向专性吸附态、无定型铁铝氧化物结合态和残渣态As转化,土壤可交换态Cd主要向残渣态、碳酸盐结合态、铁锰氧化物结合态和有机结合态Cd转化;土壤初始pH对As和Cd的钝化效果影响明显,酸性和中性土壤的pH分别增加了1.65和0.64个pH单位,土壤有效态As的降低率分别达到69.74%和63.31%,有效态Cd的降低率分别为60.25%和61.78%;小白菜的鲜重和株高随复合材料添加量的增加而提高,并...     

铈锰改性生物炭对土壤As的固定效应

利用高温热解法在600℃下制备铈锰改性生物炭(modified biochar,MBC),以3种基本性质差异较大的砷(As)污染红壤、黄壤和紫色土为研究对象,探讨了MBC的施用对土壤活性As的影响及固定效应.结果表明:改性生物炭(MBC)的施用导致3种土壤中水溶态As含量显著降低,随着施用量的增加,MBC对As的固定效率不断升高,当添加量为1%～10%时,MBC对3种土壤中活性As的固定效率为:红壤70. 59%～94. 72%,黄壤75. 24%～98. 35%,紫色土为76. 53%～99. 61%,在MBC添加量为10%时,其对3种土壤中有效As的固定效率均达到了95%以上,而未改性生物炭的施用则导致土壤As的活化效应明显.比较而言,MBC对3种土壤中有效As的固定效率大小排序为:紫色土黄壤红壤,MBC的施用导致了土壤中活性态As向稳定态转化,发生了由非专性吸附(F1)、专性吸附态(F2)向结晶水合铁铝氧化物结合态(F4)和残渣态(F5) As的转化过程,使得土壤中As的迁移性能降低,根据扫描电镜(SEM)及X射线衍射分析(XRD)的结果,MBC对As的固定作用与生物炭上铈锰氧化物的成功负载有关.因此,MBC对As污染土壤表现出良好的应用修复潜力.     

铁盐与铝盐混凝去除EDTA土壤淋洗废液中砷、锑效果对比

实验以三氯化铁和三氯化铝作为混凝剂,对比研究了混凝去除EDTA土壤淋洗废液中砷、锑的效果,重点探讨了反应终点pH、EDTA浓度、Fe/Al投加量以及共存重金属离子对砷、锑去除效果的影响。结果表明:1)对于EDTA土壤淋洗废液中As(Ⅴ)、Sb(Ⅴ)的去除,铝盐比铁盐效果更优;2)EDTA的存在不仅降低了铁盐/铝盐混凝对As(Ⅴ)、Sb(Ⅴ)的吸附去除效果,同时抑制了砷酸铁、锑酸铁等物质的生成,削弱了铁盐对As(Ⅴ)、Sb(Ⅴ)的沉淀去除。EDTA导致铁盐混凝过程中生成粒径较大、表面活性较低的稳定结晶态絮体;3)当c(EDTA)=0.05 mol/L时,在pH=5、ρ(Al)=2000 mg/L的条件下,铝盐对EDTA土壤淋洗废液中As(Ⅴ)、Sb(Ⅴ)的去除率分别高达98.00%和93.09%;4)共存重金属离子通过与EDTA络合,增加了絮体Al(OH)₃的生成量,促进了As(Ⅴ)、Sb(Ⅴ)去除。由此表明,铝盐能够有效实现EDTA土壤淋洗废液中As(Ⅴ)、Sb(Ⅴ)的去除,对于推动基于EDTA的土壤淋洗技术的广泛应用具有重要意义。     

锑矿区土壤As和Sb形态分布及生态风险评价

以晴隆锑矿区土壤为研究对象,利用连续提取法对土壤中As、Sb的形态分布和生物可利用性进行了研究,并分别利用单因子指数和生态风险指数评价了研究区土壤中As、Sb污染程度和生态危害风险。结果表明,土壤样品中As尤其Sb含量很高,不同采样点含量差别较大。土壤As、Sb的存在形态均以残渣态为主,其次是可还原态、可氧化态、弱酸提取态,水溶态很低。土壤中生物可利用态砷占0.01%~1.08%,其含量为0.001~0.347mg/kg,而土壤中生物可利用态锑占0.08%~3.26%,其含量为0.002~14.107mg/kg。从单因子污染评价看,研究区土壤Sb污染远大于As污染,且大多属于重度污染。土壤中两种金属的综合污染指数(RI)为14.59~1970.98,锑矿区总体处于轻度生态危害,部分区域Sb污染应引起重视。     

复合淋洗剂土柱淋洗法修复Cd、Pb污染土壤

选取三氯化铁和有机酸(柠檬酸、苹果酸、酒石酸)复合淋洗,采用土柱淋洗的方法对Cd、Pb污染土壤进行淋洗实验,研究了复合淋洗剂浓度配比、淋洗剂用量和淋洗次数对重金属去除效果的影响,并测定了土壤淋洗前后Cd、Pb形态的变化。结果表明:三氯化铁浓度为10 mmol/L,有机酸浓度为20 mmol/L时,淋洗率Cd为72.15%,Pb为30.26%,与使用单一淋洗剂相比均有大幅提升。复合淋洗剂能有效地去除交换态、碳酸盐结合态和氧化物结合态重金属,而对有机态和残余态部分重金属作用效果不明显;Cd比Pb容易去除是由于污染土壤中Cd的存在形态主要是可交换态、碳酸盐结合态和铁锰氧化物结合态,而Pb的存在形态主要是有机结合态和残渣态。淋洗后土壤中Cd和Pb均达到土壤环境质量标准。     

铁铈氧化物对土壤As (Ⅴ)和P的稳定化效果

本文以铁铈氧化物(Fe-Ce,FC)为研究对象,评估其对中国3种典型砷(As)污染土壤的稳定化修复效果,并通过电子扫描显微镜能散X线分析仪(SEM-EDS)和X射线光电子能谱仪(XPS)等光谱学技术探索FC对As(Ⅴ)的微观吸附特征.结果表明,FC能使土壤毒性浸出As含量显著降低84. 1%～98. 3%,且在碱性土壤中表现出较强的高p H适应性,能显著增加吸附态As(F1+F2)向水合铁铝氧化物结合态(F3+F4)的稳定化. FC能使不同类型土壤的有效态P含量显著下降47. 13%～60. 32%,不仅能缓解P竞争土壤As(Ⅴ)吸附位点,而且能有效预防周边水体的面源污染.通过SEM-EDS和XPS分析,发现As(Ⅴ)吸附产物表面均检测到Fe、Ce和As这3种元素,且As主要吸附于Fe原子表面. FC在我国土壤砷污染稳定化修复领域具有较好地应用前景.     

铁氧化物对模拟印染废水中锑的去除性能研究

含锑化合物常作为纺织工业的催化剂,易引发锑(Sb)污染问题.本文以针铁矿、四方纤铁矿与水铁矿等3种常见的铁氧化物作为吸附剂,比较了不同铁氧化物对Sb(Ⅴ)的去除性能,探究了印染废水中各类因素对锑吸附性能的影响.研究结果显示,3种铁氧化物均可使锑浓度为200μg·L-1的模拟印染废水的出水Sb(Ⅴ)浓度小于50 μg·L...     

水铁矿对不同品种水稻吸收砷镉的调控效果

为探究水铁矿(Fh)对不同品种水稻吸收砷(As)和镉(Cd)的调控效果,以常规稻黄华占(H)和杂交稻Y两优9918(Y)为供试水稻进行盆栽试验,根据是否施加Fh设置两组处理,一组为对照土壤,分别种植常规稻黄华占(H-CK)和杂交稻Y两优9918(Y-CK);另一组施加质量分数为1%的Fh,分别种植常规稻黄华占(H-Fh)和杂交稻Y两优9918(Y-Fh). 结果表明:在水稻整个生育期内Fh较稳定,不易被还原溶解,且能有效吸附孔隙水As、Cd;H-Fh处理孔隙水As和Cd浓度较H-CK处理分别降低了76.3%和31.0%,Y-Fh处理孔隙水As和Cd浓度较Y-CK处理分别降低了73.7%和57.8%. 施用Fh可促使水稻根际土壤As、Cd由非稳态向稳定态转化,且Fh对常规稻黄华占根际土壤As和Cd的稳定化效果更显著. H-Fh处理非稳态(非专性吸附态、专性吸附态和弱结晶铁氧化物结合态)As含量较H-CK处理分别降低了100.0%、30.8%、14.7%,结晶型铁氧化物结合态As含量升高了36.7%,Y-Fh处理非稳态As含量较Y-CK处理分别降低了9.9%、18.2%、14.9%,结晶型铁氧化物结合态As含量升高了29.2%;与H-CK相比,H-Fh处理可交换态Cd含量显著降低了31.5%,而Y-Fh与Y-CK处理相比,所有Cd形态的含量均无显著变化. 施加 Fh使常规稻黄华占精米As含量较其CK显著降低了44.6%,但对杂交稻Y两优9918精米As积累没有产生明显抑制,且Fh对两个水稻品种精米Cd含量均无显著影响. 因此,在对As、Cd复合污染稻田进行安全利用过程中,Fh可作为减控水稻As积累的有效投入品,但作用效果随不同水稻品种根际As有效性变化出现明显差异.      

场地土壤中有效态砷的稳定化处理及机理研究

分别以生石灰和亚铁盐作为辅助剂与稳定剂对2种砷污染的土壤进行稳定化处理,通过化学浸出、形态及结构研究,揭示土壤中有效砷的稳定效率和机理.结果表明,外源铁添加量与土壤砷含量(Fe/As)的物质的量比达到6:1~8:1,CaO投加比例为0.05%~0.1%(w/w)时,土壤中有效态砷的稳定效率超过85%.土壤有效砷的稳定化处理主要是将砷从非专性吸附态和专性吸附态转化为弱结晶的铁铝或铁锰水化氧化物结合态、结晶铁铝或铁锰水化氧化物结合态.稳定处理后2种污染土均有新物相羟砷铜矿(As2Cu5H4O12)生成.     

沸石负载纳米零价铁去除水中Sb(Ⅲ)和Sb(Ⅴ)的研究

锑矿开采和含锑化合物的应用在一定程度上会造成环境锑污染的加重,对人体健康和生态系统带来风险,为缓解这一现象,采用液相还原负载的方式制备沸石负载纳米零价铁(Z-ZVI)复合材料,探究其对Sb(Ⅲ)和Sb(Ⅴ)的去除效果;采用扫描电子显微镜(SEM)、X射线衍射(XRD)和X射线光电子能谱(XPS)对反应前后复合材料进行表征,并探究不同材料配比、溶液初始pH及无机阴离子对Sb(Ⅲ)和Sb(Ⅴ)吸附效率的影响.结果表明：(1)沸石负载后的纳米零价铁(Z-ZVI)具有较高的比表面积(54.54 m²/g)和反应活性,能够有效吸附、还原高价锑.(2)在pH=7、1.0 g/L Z-ZVI的条件下,反应4 h对20 mg/L Sb(Ⅲ)和Sb(Ⅴ)的吸附率分别达到88%和62%,吸附过程符合准二级动力学方程和Freundlich等温吸附模型.(3)Sb(Ⅲ)的去除率受pH变化的影响不大,但Sb(Ⅴ)的去除率随初始pH的升高而下降,溶液反应终点pH相比初始pH均有所上升.(4)XRD和XPS表征发现,Sb的去除过程中同时存在吸附和还原作用,Fe⁰氧化过程中...     

Immobilization of antimony in soil and groundwater using ferro-magnesium bimetallic organic frameworks

Sb(Ⅲ) is often detected in contaminated soil and groundwater. Hence, high-efficiency technology is needed. In this study, bimetallic organic frameworks were used for the first time to immobilize Sb(Ⅲ) from contaminated soil and groundwater. The materials were synthesized by the hydrothermal method. Both ends of the prepared material were hexagonal tip rods,and the length became shorter as the ratio of Fe/Mg decreased. The bimetallic organic framework with a Fe/Mg feeding ratio of 0.5 was the opt...     

VOCs相间非平衡态迁移对土壤修复效果的影响

挥发性有机物（volatile organic compounds,VOCs）普遍存在于工业污染场地,因其易迁移和难降解的特性而受到广泛关注.修复VOCs污染场地时通常存在拖尾、反弹和二次污染物释放的现象,限制了对VOCs的修复效率,这些现象均与修复过程中VOCs在相间的非平衡态迁移有关,但目前仍缺乏定量化的研究.基于此,选择四氯化碳为典型的VOCs,采用沙箱试验,探究了VOCs的相间非平衡态迁移在表面通风、土壤挖掘以及热脱附和气相抽提联用技术应用过程中对土壤修复的影响.结果表明:在表面通风和土壤挖掘过程中能产生较为显著的二次污染物释放现象;在热脱附和气相抽提联用技术的修复过程中能产生拖尾现象,而在修复结束后则会产生反弹现象,这些现象均为相间非平衡态迁移的表现形式.其中,在表面通风、土壤挖掘以及热脱附和气相抽提联用技术修复过程中,四氯化碳释放通量的最大反弹幅度分别为0.69、2.80和64.00倍,表明相间非平衡态迁移对热脱附和气相抽提联用技术产生的影响最大.研究显示,相间非平衡态迁移在不同的土壤修复工艺中均有体现,严重限制了土壤修复的效率,需要引起土壤修复工作者的高度重视.      

克拉玛依城市土壤的环境磁学特征研究

对克拉玛依市土壤环境磁学特征进行研究,并探讨土壤磁性增强的机制。结果表明:低频质量磁化率(χLF)在不同用地上依次表现为:交通运输用地>商业用地>林地>公共设施用地>未建设用地>居住用地。交通运输用地、公共设施用地较居住用地、非建设用地的土壤以低矫顽力的亚铁磁性矿物含量较高和少量不完全反铁磁性矿物,且磁性颗粒以多畴(MD)颗粒为主,含少量的单畴(SP)颗粒和稳定单畴(SSD)颗粒,与交通运输用地、公共设施用地受到汽车尾气和其他人为活动产生的污染物中含有大量的粗颗粒亚铁磁性矿物密切相关。     

采用清洗-热脱附工艺修复石蜡基与环烷基原油污染土壤

石油污染土壤修复工艺的选择及其应用效果受原油属性影响明显。选取石蜡基和环烷基2类原油污染土壤,采用清洗预处理-热脱附方法,研究耦合工艺的修复效能,重点比较清洗对土壤粒级的分离效果,表面活性剂对石油污染物的脱附效率,药剂清洗前后的土壤热脱附修复效果等。结果表明:清洗后2种土壤的砂质组分吸附的石油类脱附率约为59.83%和36.42%,远高于黏质组分。阴离子型α-十六烯基磺酸钠脱附能力更强,石蜡基和环烷基2类油源污染土壤的石油类脱附率为46.5%和39.8%。以环烷基土壤为例,将药剂清洗后分离出的黏粒土进行热脱附,与未清洗的原污染土壤相比,前者脱附所用时间更短。400℃下热脱附3 h,石油类含量降至0.26%。采取清洗-热脱附工艺开展现场试验,清洗后粗粒级砂质土壤的石油类含量为1.56%,黏粒土脱水后热脱附,石油类含量可达到0.57%,清洗-热脱附修复污染土壤能耗低于单纯热脱附工艺。     

某退役溶剂厂有机物污染场地燃气热脱附原位修复效果试验

热脱附技术一般用于土壤中有机物的异位修复,然而对于受有机物污染较深土壤的原位修复却鲜有报道.本文以某退役溶剂厂土壤中苯、氯苯和石油类为目标污染物,运用燃气热脱附技术进行原位修复.本文介绍了燃气热脱附技术的工艺设计流程,针对场地目标污染物进行燃气热脱附的工程化试验,结果显示热脱附处理后土壤中苯、氯苯和石油类最高去除率接近100%.本文还探讨了温度、停留时间、土壤含水率和土壤质地对热脱附效率的影响,发现在温度和停留时间相同情况下,含水率较小、孔隙率较大的粉砂土热脱附效果更好.试验表明,燃气热脱附原位修复技术处理场地挥发性有机污染物效果良好,可以进行大规模的实际运用.     

Molecular diversity of arbuscular mycorrhizal fungi at a large-scale antimony mining area in southern China

Arbuscular mycorrhizal fungi (AMF) have great potential for assisting heavy metal hyperaccumulators in the remediation of contaminated soils. However, little information is available about the community composition of AMF under natural conditions in soils contaminated by antimony (Sb). The objective of this study was to investigate the characteristics of AMF molecular diversity, and to explore the effects of Sb content and soil properties on the AMF community structure in an Sb mining area. Four Sb mine spoils and one adjacent reference area were selected from around the Xikuangshan mine in southern China. The association of AMF molecular diversity and community composition with the rhizosphere soils of the dominant plant species was studied by Polymerase Chain Reaction-Denaturing Gradient Gel Electrophoresis (PCR-DGGE). Results from all five studied sites showed that the diversity of AMF decreased with increasing Sb concentration. Principal component analysis (PCA) indicated that the AMF community structure was markedly different among these groups. Further redundancy analysis (RDA) showed that Sb contaminationwas the dominating factor influencing the AMF community structure in the Sb mine area. However, the multivariate analysis showed that, apart from the soil Sb content, extractable nitrogen content and organic matter content also attributed to AMF sequence distribution type. Some AMF sequences were only found in the highly contaminated area and these might be ideal candidates for improving phytoremediation efficiency in Sb mining regions. Gene sequencing analysis revealed that most species were affiliated with Glomus, suggesting that Glomus was the dominant AMF genus in the studied Sb mining area.     

Molecular diversity of arbuscular mycorrhizal fungi at a large-scale antimony mining area in southern China

Arbuscular mycorrhizal fungi (AMF) have great potential for assisting heavy metal hyperaccumulators in the remediation of contaminated soils. However, little information is available about the community composition of AMF under natural conditions in soils contaminated by antimony (Sb). The objective of this study was to investigate the characteristics of AMF molecular diversity, and to explore the effects of Sb content and soil properties on the AMF community structure in an Sb mining area. Four Sb mine spoils and one adjacent reference area were selected from around the Xikuangshan mine in southern China. The association of AMF molecular diversity and community composition with the rhizosphere soils of the dominant plant species was studied by Polymerase Chain Reaction-Denaturing Gradient Gel Electrophoresis (PCR-DGGE). Results from all five studied sites showed that the diversity of AMF decreased with increasing Sb concentration. Principal component analysis (PCA) indicated that the AMF community structure was markedly different among these groups. Further redundancy analysis (RDA) showed that Sb contamination was the dominating factor influencing the AMF community structure in the Sb mine area. However, the multivariate analysis showed that, apart from the soil Sb content, extractable nitrogen content and organic matter content also attributed to AMF sequence distribution type. Some AMF sequences were only found in the highly contaminated area and these might be ideal candidates for improving phytoremediation efficiency in Sb mining regions. Gene sequencing analysis revealed that most species were affiliated with Glomus, suggesting that Glomus was the dominant AMF genus in the studied Sb mining area.     

Molecular diversity of arbuscular mycorrhizal fungi at a large-scale antimony mining area in southern China

Arbuscular mycorrhizal fungi(AMF) have great potential for assisting heavy metal hyperaccumulators in the remediation of contaminated soils. However, little information is available about the community composition of AMF under natural conditions in soils contaminated by antimony(Sb). The objective of this study was to investigate the characteristics of AMF molecular diversity, and to explore the effects of Sb content and soil properties on the AMF community structure in an Sb mining area. Four Sb mine spoils and one adjacent reference area were selected from around the Xikuangshan mine in southern China. The association of AMF molecular diversity and community composition with the rhizosphere soils of the dominant plant species was studied by Polymerase Chain Reaction-Denaturing Gradient Gel Electrophoresis(PCR-DGGE). Results from all five studied sites showed that the diversity of AMF decreased with increasing Sb concentration. Principal component analysis(PCA) indicated that the AMF community structure was markedly different among these groups. Further redundancy analysis(RDA) showed that Sb contamination was the dominating factor influencing the AMF community structure in the Sb mine area. However, the multivariate analysis showed that, apart from the soil Sb content, extractable nitrogen content and organic matter content also attributed to AMF sequence distribution type. Some AMF sequences were only found in the highly contaminated area and these might be ideal candidates for improving phytoremediation efficiency in Sb mining regions. Gene sequencing analysis revealed that most species were affiliated with Glomus, suggesting that Glomus was the dominant AMF genus in the studied Sb mining area.     

绝缘油污染土壤微波脱附试验

采用微波-热重反应装置,针对绝缘油污染土壤进行微波热脱附试验,考察不同温度下绝缘油脱附效率以及污染土壤失重规律,并在此基础上对土壤中残余绝缘油组分及分布进行分析。结果表明:当温度达到400℃以上时,土壤中绝缘油去除效果较好,绝缘油去除率可达到98.6%,能够满足土壤修复要求。含油土壤随着温度升高主要经历水分挥发、易挥发性有机物析出、难挥发性有机物析出等阶段,在100~200℃阶段,主要是土壤中水分和部分低挥发性有机物析出;在400~500℃阶段,主要是土壤中绝缘油析出。土壤中绝缘油的成分以C12—C21烷烃类化合物和5~6环芳香烃为主,当温度达到400℃以后,绝缘油中各组分逐步被完全脱附,综合考虑脱附效率和经济性原则,绝缘油污染土壤脱附温度以400~450℃为宜。