2019, Vol. 38
土壤镉和砷污染钝化修复材料及科学计量研究
1. 中国农业大学资源与环境学院, 北京 100193;
2. 教育部植物-土壤相互作用重点实验室, 北京 100193;
3. 农业部华北耕地保育重点实验室, 北京 100193;
4. 农业农村部环境保护科研监测所, 天津 300191
2. 教育部植物-土壤相互作用重点实验室, 北京 100193;
3. 农业部华北耕地保育重点实验室, 北京 100193;
4. 农业农村部环境保护科研监测所, 天津 300191
摘要: 使用Web of Science（WOS）核心合集数据库统计了5年内（2014—2018年）关于土壤镉（Cd）和砷（As）单一污染的情况，发现土壤Cd和As污染依然受到人们的广泛关注，且我国在该领域发文最多。利用CiteSpace软件分析发现施用钝化修复材料是土壤Cd和As污染治理的热点修复技术之一。基于此，本文综述了常见的钝化修复材料及其钝化机理，并分别对钝化修复材料的室内研究和修复实践进行总结，发现无机类钝化修复材料中石灰类主要通过调节土壤pH值改变重金属有效性；磷酸盐类分别通过共沉淀和点位竞争机制钝化重金属；金属及其氧化物类通过表面络合和还原作用对重金属的钝化效果更好；黏土矿物中海泡石和坡缕石廉价绿色且具有较大的比表面积，对重金属的钝化效果较好。有机类钝化剂中生物炭类为研究热点材料之一，因表面拥有丰富的官能团和较大的比表面积，其对重金属表现出良好的钝化修复效果；有机废弃物含高度腐殖化的有机质和微生物，对重金属钝化效果较好。此外，对国内外典型的Cd和As污染实践修复工程进行介绍，发现金属及其氧化物、堆肥、生物炭以及廉价易获得的石灰和黏土矿物施用较广。最后，讨论了钝化修复材料施用中亟需解决的问题。
关键词:
重金属 镉 砷 钝化材料
Immobilization materials for cadmium and arsenic contaminated soil remediation and their scientific metrology research
1. College of Resource and Environment, China Agricultural University, Beijing 100193, China;
2. Key Laboratory of Plant-Soil Interactions, Ministry of Education, Beijing 100193, China;
3. Key Laboratory of Arable Land Conservation(North China), Ministry of Agriculture, Beijing 100193, China;
4. Agro-Environmental Protection Institute, Ministry of Agriculture and Rural Affairs, Tianjin 300191, China
2. Key Laboratory of Plant-Soil Interactions, Ministry of Education, Beijing 100193, China;
3. Key Laboratory of Arable Land Conservation(North China), Ministry of Agriculture, Beijing 100193, China;
4. Agro-Environmental Protection Institute, Ministry of Agriculture and Rural Affairs, Tianjin 300191, China
Abstract: This paper used the Web of Science (WOS)core collection database to gather statistics on soil cadmium and arsenic single contamination during 2014 to 2018. It was found that cadmium and arsenic contamination in soil were still widely concerned, and China published the most articles in this field. By using CiteSpace software, we found that application of immobilization materials was one of the most popular technologies for soil cadmium and arsenic remediation. Based on this, this paper summarized the common immobilization materials and mechanism, and the indoor research and remediation practice related to immobilization materials were summarized, respectively. For inorganic immobilization materials, lime changes the effectiveness of heavy metals mainly by regulating soil pH; phosphates immobilize heavy metal through co-precipitation and site competition mechanism; metal oxides showed a good remediation effect on heavy metal by surface complexation and reduction; sepiolite and palygorskite were cheap and green, and had large specific surface areas, and showed significant amendment effect on heavy metal. For organic immobilization materials, biochar shows significant immobilization effect on heavy metal due to its rich functional group and high surface area. Organic waste contained large quantity of humic substances, organic matter, and microorganisms, and showed significant effect on heavy metal immobilization. In addition, the typical field remediation projects of cadmium/arsenic contaminated soil in China and other areas of the world were introduced. Overall, it is found that the metal and its oxides, compost, biochar, lime and clay minerals are applied widely in the world. To provide the guidance for cadmium and arsenic contaminated soil remediation, we finally discussed the urgent problems that need to be solved in the application of immobilization materials.
Keywords:
heavy metals cadmium arsenic amendment materials
随着社会经济的高速发展和人类活动的高强度进行，农药、抗生素、除草剂、肥料和化石燃料的消耗与日俱增[1]，这些都会导致重金属等污染物进入土壤，使土壤污染面积不断扩大[2]，生态环境日益恶劣。据2014年公布的《全国土壤污染状况调查公报》显示，我国土壤污染主要以无机类污染为主，无机污染点位超标率为21.7%，其中镉（Cd）和砷（As）污染占比分别为7.0%和2.7%，均属无机污染物中污染最严重的元素[3]。因重金属污染具有隐蔽性、滞后性和不可逆转性等特点[4]，在控制重金属进入土壤的同时，加强重金属污染土壤修复刻不容缓。
目前修复土壤重金属污染有物理、化学和生物的方法，但已证明化学钝化和植物修复对土壤破坏最小[5]，且为使植物正常生长需添加化学物质调节土壤酸碱度以降低重金属的有效性，故施用钝化修复材料是目前修复Cd和As污染的有效措施之一[6]。土壤中Cd主要以Cd（Ⅱ）阳离子的形式存在[7]，As通常以砷酸盐（Ⅴ）或亚砷酸盐（Ⅲ）阴离子的形式存在，且三价砷的毒性更大[8]。施用钝化剂可以改变Cd和As在土壤中的赋存形态[9]，降低它们的生物有效性和在环境中的迁移性[10-11]。本文主要对常用的Cd和As污染钝化修复材料及钝化机制进行总结，同时对国内外典型的Cd和As污染土壤田间修复工程进行了介绍，由于Cd和As复合污染情况复杂，其受土壤pH和氧化还原状况的影响更加复杂，实际修复效果通常顾此失彼，已单独做了整理总结，在此不再详述。
1 近5年土壤Cd和As污染论文发表情况图 1和图 2数据来源于Web of Science（WOS）的核心合集数据库，以“soil and cadmium”或“soil and arsenic”为主题，检索时间跨度为2014年1月—2018年12月，并利用WOS数据库自带工具分析。图 1显示，在检索时间范围内，2014—2016年文章发表量持续上涨，2017年有所下降，2018年又有所回升且与2016年基本持平。2016年的文章发表量最高为6497篇，2018年文章发表量为6422，表明Cd和As污染土壤依然受到人们的广泛关注。
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图 1 2014年1月—2018年12月土壤Cd和As污染年度发文量 Figure 1 Annual publication amount of soil Cd and As contaminants from January 2014 to December 2018 |
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图 2 世界各国在2014年1月—2018年12月土壤Cd和As污染发文总量 Figure 2 The total publication amount of soil Cd and As contaminants published in different countries from January 2014 to December 2018 |
图 2为近5年世界各国在土壤Cd和As污染方面发表文章总量示意图，由图可知发文量前10名的国家依次为中国、美国、印度、伊朗、韩国、波兰、法国、意大利、西班牙和德国。中国在此研究方向发文量最多，共发表 5864篇文章，占检索结果的28%；美国发文量为3815篇，占12%；印度发文量为1644篇，占9%；10国以外的其他国家累计发文量为4107篇，占24%。中国和美国对土壤Cd和As污染研究较多，可见我国在土壤Cd和As污染领域的研究占有重要地位，间接说明我国对目前土壤Cd和As污染问题的重视。
使用CiteSpace（5.3.R4）软件对图 1检索数据中的“keyword”进行分析，2014年1月—2018年12月土壤Cd和As污染领域“keyword”共现关系如图 3所示。图中每个节点（圆）的大小和两节点间连线的粗细，表示“keyword”出现的频次和共现强度的高低[12]。图 3显示，Cd和As的节点较大，均与“soil”相连接，表明Cd和As对土壤污染存在普遍性，其中Cd节点更大、连线更粗，说明重金属污染土壤中Cd的研究最多，这与《全国土壤污染状况调查公报》研究一致[3]。通过“soil”、“contamination”和“China”的连接，表明中国更关注土壤污染问题。Cd与Cu、Zn、Pb、Cr和Hg节点连接，表明Cd与其他重金属协同污染研究比较广泛。土壤Cd和As污染主要是通过钝化剂固定（passivation节点）或植物修复技术（accumulation和phytoremedation节点）修复，但植物修复技术通常不会单独使用，而是需要添加一定的化学物质保证植物的正常生长[6]，降低土壤中Cd和As的生物有效性。图中出现的钝化剂种类有氧化物类纳米颗粒（nanoparticle节点）、生物炭（biochar节点）和氧化石墨烯（graphene oxide节点）等，但我们常见的钝化材料石灰类、磷酸盐类和黏土矿物类并没有出现，说明近5年生物炭类和新型钝化剂的研究较多。“adsorption”等节点与Cd和As节点相连接，表明在水溶液中对Cd和As进行吸附实验较多，以此探究钝化材料的修复机理，集中在配体交换反应（ligand节点）和络合反应（complex节点），这会在后续的总结中作详细的讨论。
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图 3 2014年1月-2018年12月国际土壤Cd和As污染期刊论文关键词共现关系 Figure 3 Co-occurrence of key words in international journal papers on soil Cd and As contaminants from January 2014 to December 2018 |
通过以上科学计量分析结果发现，土壤Cd和As污染仍然受到世界范围内的广泛关注和研究，其中化学钝化修复材料的开发及其机理探究为研究热点，下面整理总结了不同类型钝化修复材料及其作用机理，旨在为我国土壤Cd和As污染修复工作的扎实推进提供一定的科学支撑。
2 土壤Cd和As钝化修复材料类型重金属的生物有效性与其存在形态有关[9]，化学修复是指在土壤中添加钝化修复材料[10]，改变重金属的赋存状态[11]，降低其在土壤中的迁移性和生物有效性，从而达到修复污染土壤的目的。目前，常用的钝化修复材料主要有无机类和有机类钝化剂，以下分别对这些材料的修复效果进行探讨，从而为土壤Cd和As污染修复提供参考。
2.1 无机类 2.1.1 石灰类石灰类钝化剂有生石灰和熟石灰，能有效提高土壤pH值，改变土壤CEC和氧化还原电位等，影响重金属在土壤中的吸附和沉淀[13]。熊礼明[14]发现，当土壤pH值≥6时，施用石灰能有效提高红壤对Cd的吸附量并降低吸附态Cd的解吸量。Woldetsadik等[15]发现施用石灰使土壤有效态Cd含量降低82%~91%。除石灰的单施外，与其他钝化材料配施研究也较多。朱奇宏等[16]发现石灰与海泡石配施比单施效果好，稻作条件下土壤酸提取态Cd降低10%~15%，可还原态和残渣态Cd比例分别增加6%~10%和3%~4%。刘维涛等[17]发现石灰、鸡粪和过磷酸钙配施，使土壤pH值增加了2.5，土壤有效态Cd含量降低44%，白菜生物量增加83%。Wang等[18]通过添加蛇纹石和石灰发现土壤Cd的生物有效性与pH值呈显著负相关，有效态Cd含量降低14%~37%。Chen等[19]发现水稻田在淹水条件下，石灰和泥炭配施比二者单施对Cd钝化的效果更好。
2.1.2 磷酸盐类磷酸盐类钝化剂主要包括磷酸盐、羟基磷灰石、磷矿粉、磷石膏和磷肥等，其修复机理主要是通过形成难溶性磷酸盐沉淀以及其对重金属的表面吸附作用[20]。吴宝麟[20]研究表明，在Ca（H2PO4）2和Fe2（SO4）3最佳复配比为[Fe3+]/[PO43-]=2.16:1时能同时修复Cd和As污染土壤，且分步加入Ca（H2PO4）2和Fe2（SO4）3对Cd和As的钝化效果优于二者同时加入。殷飞等[21]发现在土壤中加入20%磷矿粉后（钝化剂与土壤质量比），土壤中可交换态Cd含量显著降低，钙型As含量增加，这可能是磷矿粉中的Ca对As起到了钝化修复效果，显著降低了As的生物有效性。
2.1.3 金属及其氧化物类金属及其氧化物主要指零价铁及含Fe、Mn和Al的氧化物，其钝化机理主要是吸附和共沉淀作用[22]。这类钝化材料有零价铁、水铁矿、赤铁矿、磁铁矿、针铁矿、硫酸亚铁和赤泥等[23]。金属及其氧化物对Cd和As的钝化效果如表 1所示，其中对As的总结多集中在实践钝化修复部分。
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表 1 金属及其氧化物对Cd和As的钝化作用 Table 1 Effect of metals and their oxides immobilization on Cd and As |
黏土矿物是一类含硅酸盐类物质，主要包括海泡石、膨润土和凹凸棒土等，它们通过吸附、离子交换和配位反应等钝化重金属[31]。孙约兵等[32]在红壤中添加海泡石，使有效态Cd含量降低4%~44%，菠菜中Cd含量降低18%~300%。王林等[33]发现酸改性海泡石比海泡石施用下油菜产量更高。谭科艳[34]发现，凹凸棒土与土壤的质量比为1:20时，可将土壤pH值由原来的3~5提高到5~8，对Cd污染土壤的修复率达到35%，并有效减少蔬菜对Cd吸收。Sun等[35]发现添加膨润土后，土壤中交换态Cd含量降低11%~43%，残渣态Cd增加3%~54%，幼芽Cd含量降低17%~44%。高瑞丽等[36]施用1%、2%和5%的蒙脱石，发现5%施加量下土壤中弱酸提取态的Cd含量降低了19%。
2.2 有机类 2.2.1 生物炭类生物炭指生物质在缺氧或无氧条件下热裂解得到的一类含碳的、稳定的、高度芳香化的固态物质[37]，可与土壤重金属发生吸附、络合、沉淀和离子交换等一系列反应使之钝化[38]。但随着研究的深入人们发现生物炭对土壤中重金属的修复能力具有局限性，故生物炭改性技术应运而生。改性后的生物炭比表面积极大提高，官能团极大丰富，吸附能力进一步增强，使其具有更高效的环境修复潜力[39]。不同生物炭材料对Cd和As的钝化效果如表 2所示。
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表 2 不同生物炭材料对Cd和As的钝化效果 Table 2 Immobilization effect of different biochar materials on Cd and As |
有机废弃物即利用动物粪便、生物固体、城市和农村固体废物进行堆肥[51]。其含有高度腐殖化的有机质和微生物，能与重金属发生吸附、氧化还原、有机络合等反应。王立群等[24, 52]发现新鲜蒜苗、油菜、大葱等富含巯基的植物残体可与Cd有效螯合，降低土壤可交换态Cd含量20%~25%。李扬等[53]发现蚯蚓粪会显著降低土壤中重金属的生物有效性。陈春霞等[54]发现添加1%的骨粉，能显著提高菜地土壤pH值和CEC，并降低菜地和蔬菜中Cd含量。黎大荣等[55]发现蚕沙和熟石灰能有效降低蔬菜大棚土壤中Cd含量，且单施蚕沙效果最好，土壤有效态Cd含量降低39%。刘秀珍等[56]在石灰性褐土上施用猪粪、羊粪和鸡粪，土壤可交换态Cd含量分别降低23%、21%和18%，残留态Cd含量分别增加42%、40%和35%。Kwiatkowska等[57]发现在褐煤、褐煤制剂和农家肥试验中，褐煤处理下Cd的生物有效性最低，冬小麦籽粒的生物累积指数最低为0.2。
近年来，一些研究表明有机酸可以有效钝化重金属[58-59]，同时也存在重新活化重金属的风险[60-63]。有研究表明酒石酸等对Cd有较明显的解毒作用，能有效抑制植株各部位对Cd的吸收[59]。Chen等[64]发现有机酸和氨基酸浓度相对低时有利于Cd的钝化。Wang等[65]发现天冬氨酸、半胱氨酸和琥珀酸pH值在3或5时促进As的钝化，而pH值在7以上则会增强As的迁移性。Boechat等[66]发现富里酸使土壤pH值下降0.7个单位，形成有机配体促进土壤中Cd和As的钝化。Alozie等[67]发现在柠檬酸、草酸和苹果酸存在下，软木生物炭表面发生质子化反应，有利于As的吸附，但不利于土壤中Cd的吸附。除了有机酸本身对Cd和As的钝化效果，植物根系分泌的有机酸也具有一定的重金属活化作用。Taghipour等[68]研究发现有机酸（柠檬酸和草酸）的存在，会促进黏土矿物（膨润土、沸石）和纳米颗粒（MgO、TiO2和ZnO）对Cd的吸附，且纳米颗粒的吸附量比黏土矿物的多。由于有机酸对针铁矿、蒙脱石和生物炭吸附的Cd均表现出一定的活化作用，故使用黏土矿物和生物炭钝化剂时要考虑土壤中植物根系分泌物重新活化重金属的风险。
除上述常见钝化修复材料外，有些材料具有较高吸附性能，且无需大量施用就能获得较好的修复效果，如功能膜材料[69]、介孔材料[70]、植物多酚类物质[71]和石墨烯材料等[72]。
3 土壤Cd和As污染钝化修复机制由于不同钝化修复材料对Cd、As的钝化过程差别很大，反应机制也十分复杂，因此明确钝化修复材料对Cd和As在土壤中的钝化机制对于评价钝化修复材料的效果和持久性具有十分重要的意义。
3.1 Cd污染钝化修复机制 3.1.1 离子交换作用离子交换作用是指钝化剂中某些高价离子在一定的条件下与重金属发生交换，如生物炭表面的官能团或盐基离子可与Cd交换[73]；沸石具有的Si-O四面体和Al-O八面体结构及其含有的K、Na和Ca等离子与晶格并非紧密结合，使得沸石对Cd产生较强的离子交换[74]。
3.1.2 络合作用有机官能团能与Cd形成稳定的有机络合物，减小其可移动性和生物毒性[75]。有机质中硫醇基（RS-）和羧基（RCOO-）可与Cd发生络合反应[76]。此外生物炭的芳香化基团产生阳离子π作用，与Cd的d轨道发生络合作用[77-78]，降低Cd的生物有效性。
3.1.3 沉淀作用在土壤pH值较高的情况下，含氧根阴离子（SO42-、CO32-、OH-、HPO42-）含量高时，Cd在土壤中主要以沉淀方式被固定[79-80]。常见钝化材料石灰类、黏土矿物类、金属及其氧化物类以及生物炭类都会提高土壤pH值，例如施用石灰促使Cd形成氢氧化物或碳酸盐结合态沉淀[80]。硅酸根也能与Cd形成硅酸盐类化合物沉淀[81]。
3.1.4 点位竞争机制点位竞争机制是重金属离子与溶液离子对吸附点位的竞争，在同族元素之间竞争效果更加显著[39]。例如Fe（Ⅱ）和Zn（Ⅱ）会与Cd（Ⅱ）竞争二价离子的吸附位点[82]，从而降低Cd的生物有效性。此外施用硅肥可促进铁膜的形成[83]，而Fe（Ⅱ）与Cd（Ⅱ）有一定的拮抗竞争作用[84-85]。
3.2 As污染钝化修复机制 3.2.1 络合作用和点位竞争As主要是与金属氧化物发生离子交换和沉淀作用。砷酸根与铁铝氧化物表面的OH-交换，在氧化物表面形成稳定的双齿双核结构的复合物[86]。As也可以被双金属氧化物（氧化铝和氧化镁）固定在层间或表面[30]。此外，磷酸盐和硅酸盐能与砷酸根或亚砷酸根竞争活性吸附位点[87]。
3.2.2 氧化还原作用As容易受氧化还原反应的影响，As（Ⅲ）易迁移、活性和毒性都远高于As（Ⅴ），所以将As（Ⅲ）氧化为As（Ⅴ）是钝化As的途径之一。例如使用含氧化铁的污泥进行As的田间修复，发现其施用后土壤中As主要以As（Ⅴ）的形式存在[88]。此外在土壤中As作为微生物新陈代谢的电子终端接受者，会将As（Ⅲ）氧化为As（Ⅴ）[89]。
3.2.3 甲基化与去甲基化甲基化指通过生物或化学机制将土壤中As转化为甲基衍生物而蒸发去除[90]。有机废弃物中含高度腐殖化的有机质和微生物，微生物在土壤中是生物甲基化的主导者，有机物质提供甲基源。甲基化的衍生物很容易从细胞中排泄出来，且具有挥发性，促进As形成毒性较小的有机砷[61]。
4 国内外土壤Cd和As钝化修复实践前文总结的土壤Cd和As污染钝化修复研究多数集中在实验室规模，能够较快地对钝化材料进行筛选从而用于实地修复，但实验室条件难以代表田间实际情况，以下对近年来国内外土壤Cd和As污染钝化修复材料的修复实践效果进行探讨。
4.1 国外土壤Cd和As钝化修复实践国外用于钝化修复实践的材料主要集中在石灰类、磷酸盐类、有机废弃物类以及黏土矿物和金属氧化物类。Hong等[91]施用2、4、8 t·hm-2的Ca（OH）2后，发现随Ca（OH）2使用量的增大，土壤和玉米中NH4OAc提取态Cd含量降低。Basta等[92]发现磷酸二铵能降低Cd的迁移能力，且施用量为5.3 t·hm-2时，土壤与Cd的结合能力最强，达到95%。Qayyum等[93]发现磷酸氢二铵和石膏对Cd的钝化残效仍较显著，且石膏残效优于磷酸氢二铵。Placek等[94]发现施用污泥提高了土壤中有机质含量和CEC，辅助松树和云杉可以修复Cd污染的土壤。Gruter等[95]发现长期施用堆肥，土壤有机碳、CEC和pH值较高，且有效降低小麦籽粒中Cd的积累。Zotiadis等[96]发现施用凹凸棒土7个月后土壤pH保持稳定，调节土壤含水量达到饱和状态1个月后，可浸出的Cd和As分别降低41%和18%。Hartley等[97]发现，施用绿色垃圾堆肥能有效固定土壤中的As，防止As向地下水中迁移。Xie等[98]将Fe（Ⅱ）和NaClO注入田间As污染含水层，促进铁氧化物或氢氧化物的形成，使As（Ⅲ）转化为As（Ⅴ）。Ko等[99]施用含氧化铁的污泥后，发现土壤孔隙水中As浓度由11.6 μg·L-1下降到4.9 μg·L-1，且通过XANES分析发现土壤和稻米中As主要以As（Ⅴ）的形式存在，Ko等[100]还施用含针铁矿的采矿污泥，发现Fe（OH）3对As的去除率为50%，针铁矿污泥对As的去除率为30%。
4.2 我国土壤Cd和As钝化修复实践目前，我国已经在Cd和As污染土壤修复方面开展了一定的工作，主要的钝化修复材料有石灰、黏土矿物类、磷酸盐类、有机堆肥类和生物炭类。黄益宗等[101]在水稻田中施用硅钙肥和石灰，稻谷增产50%~51%，糙米中Cd含量降低57%~64%，示范区排水Cd浓度降低55%。韩君等[102]发现20 t·hm-2坡缕石和23 t·hm-2海泡石处理后的土壤pH值显著提高，糙米中Cd含量显著降低，最大降幅分别为55%和74%。Yin等[103]发现天然海泡石显著降低水稻土中Cd含量，糙米、稻壳、稻草和根系分别降低55%~74%、44%~63%、27%~67%和37%~47%。此外，相关研究发现赤泥、骨炭、海泡石和石灰等可显著降低Cd和As的生物有效性[104-108]。Wang等[109]比较磷酸盐、钙镁磷肥和过磷酸钙钝化土壤Cd的效果发现，钙镁磷肥效果更好，Cd由1.7 mg·kg-1降到1.4 mg·kg-1，白菜吸收的Cd含量与土壤pH值呈负相关，而非与土壤水溶态和TCLP态Cd，故应谨慎评价磷肥对Cd的钝化效果。Li等[110]施用27~54 t·hm-2的鸡粪堆肥，小麦茎和种子中Cd的含量分别降低70%~75%和10%~18%，土壤pH值、总磷和有机质含量显著提高，土壤微生物特性如生物量碳、转化酶、蛋白酶、脲酶和过氧化氢酶等显著提高0.2~3.5倍。Bian等[111]添加20~40 t·hm−2的小麦秸秆生物炭，稻米中Cd含量降低20%~90%，达到安全水平0.4 mg·kg-1以下；Bian等[112]又探究了生物炭残效，发现其对Cd的钝化效果好于氢氧化钙和硅渣，土壤pH值和有机质含量变大，水稻各组织中Cd含量显著降低。Zhang等[113]发现施用1.5 t·hm-2和3.0 t·hm-2污泥生物炭，稻米中Cd含量由对照的1.4 mg·kg-1均下降到0.8 mg·kg-1。Yan等[114]发现施用纳米零价铁，水溶态As减少70%，铁铝氧化物结合态最大增加51%，并显著降低植物三七中As含量49%~63%。吴晓云等[115]以废弃稀土抛光粉为原料加入一定量的H2SO4和NaOH制成As钝化剂，2%质量比的钝化剂添加到土壤1~3 d后，土壤中As的生物有效量均降至15 mg·kg-1以下。赵宁亚[116]在硫酸根和As污染的土壤中，加入2%的氧化钙，As的稳定化率在94%以上。
用于田间修复的钝化修复材料，多集中在废弃物的再利用，如堆肥、生物炭以及廉价易获得的石灰和黏土矿物等。对于Cd的钝化，石灰的施用最广，其次为海泡石，生物炭表现出良好的施用前景，而金属及其氧化物多用于As的钝化。
5 问题和展望基于以上分析总结，作者对今后的研究工作提出几个问题：
（1）成本问题。田间修复Cd污染的土壤，成本较高，因此积极探寻廉价的钝化材料及最佳施用量或选择当地废弃物作为钝化材料以降低运输费用；
（2）安全性问题。有些钝化修复材料组分复杂，本身还可能含有一定量的重金属元素，过量施用可能带来一定的环境风险，应寻求更高效和环境友好的新型钝化修复材料；
（3）长效性问题。化学钝化修复技术是通过改变Cd和As的生物有效性，而非直接将其从土壤中去除，所以要检测钝化剂的长效性；
（4）综合措施问题。化学钝化修复技术虽然有效，但不应只局限于此，联合运用化学、物理、生物以及农艺措施，探究它们之间的作用原理，进而增强钝化修复效果。
总之，需因地制宜地根据不同的土壤，采用适宜的土壤钝化修复材料和管理措施，兼顾产量和品质，使土地得到合理利用，使经济和生态效益最大化。
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