CN112853744A - 一种缓释Ca2+调控土壤中Cd活性的复合材料的制备和应用方法 - Google Patents
一种缓释Ca2+调控土壤中Cd活性的复合材料的制备和应用方法 Download PDFInfo
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- CN112853744A CN112853744A CN201911181823.8A CN201911181823A CN112853744A CN 112853744 A CN112853744 A CN 112853744A CN 201911181823 A CN201911181823 A CN 201911181823A CN 112853744 A CN112853744 A CN 112853744A
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- Prior art keywords
- soil
- composite material
- woven fabric
- calcium
- release
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- 239000002131 composite material Substances 0.000 title claims abstract description 85
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 title claims abstract description 61
- 229910001424 calcium ion Inorganic materials 0.000 title claims abstract description 61
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- IXPNQXFRVYWDDI-UHFFFAOYSA-N 1-methyl-2,4-dioxo-1,3-diazinane-5-carboximidamide Chemical compound CN1CC(C(N)=N)C(=O)NC1=O IXPNQXFRVYWDDI-UHFFFAOYSA-N 0.000 claims abstract description 17
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- 238000005067 remediation Methods 0.000 claims abstract description 11
- 238000001179 sorption measurement Methods 0.000 claims abstract description 11
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- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 7
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- 241000199919 Phaeophyceae Species 0.000 description 1
- 229910008051 Si-OH Inorganic materials 0.000 description 1
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- 230000009471 action Effects 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229920001586 anionic polysaccharide Polymers 0.000 description 1
- 150000004836 anionic polysaccharides Chemical class 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000012620 biological material Substances 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
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- 239000002734 clay mineral Substances 0.000 description 1
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- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
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- 229910052742 iron Inorganic materials 0.000 description 1
- DALUDRGQOYMVLD-UHFFFAOYSA-N iron manganese Chemical compound [Mn].[Fe] DALUDRGQOYMVLD-UHFFFAOYSA-N 0.000 description 1
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- Organic Chemistry (AREA)
- Environmental & Geological Engineering (AREA)
- Processing Of Solid Wastes (AREA)
Abstract
本发明公开了一种缓释Ca2+调控土壤中Cd活性的复合材料的制备和应用方法。配制硅酸钠、海藻酸钠和羧甲基壳聚糖的混合物水溶液，将该混合物水溶液涂覆到表面接枝羧基的无纺布纤维膜上，然后浸泡到可溶性钙盐水溶液中交联，得到负载硅酸钙/海藻酸钙/羧甲基壳聚糖的无纺布复合材料。将该复合材料埋置到土壤中，硅酸钙与土壤中的氢离子反应提高土壤的pH值，同时释放Ca2+，生成介孔SiO2。海藻酸钙吸附Cd2+，并且缓释Ca2+，较高浓度的Ca2+抑制了农作物对Cd2+的吸收，降低土壤中Cd活性。本发明的复合材料能同时降低Cd活性并提高土壤pH值，羧甲基壳聚糖的抑菌作用使材料可长期使用，作为载体的无纺布方便土壤修复的实际操作，具有良好的应用前景。
Description
技术领域
本发明涉及一种缓释Ca2+调控土壤中Cd活性的复合材料的制备和应用方法，属于环境功能材料和土壤修复领域。
本发明涉及土壤修复、土壤调控、复合材料、重金属污染治理等技术领域。具体涉及一种缓释Ca2+调控土壤中Cd活性的复合材料的制备和应用方法。
背景技术
长江两岸土壤是重金属镉元素的相对富集区，镉严重超标已影响到某些食用植物的卫生安全，同时也影响了一些地区农产品的出口创汇。镉是自然界中广泛存在的一种致癌、致畸胎和致病变的有毒重金属元素，它使人体中多种酶系统的有效态受到抑制，从而使肝、肾等组织中的酶系统正常功能受损，同时还干扰铜、钴和锌在体内的代谢，产生毒性【Environmental Health Perspectives,2012,120(2):284-289】。镉极易在土壤中富集，镉进入土壤后主要集中于土壤表层，一般在0-15cm。镉在土壤中的存在形态有水溶态、可交换态、碳酸盐态、有机结合态、铁锰氧化态及硅酸态等6种形态。土壤镉按来源可分为内源镉和外源镉两部分，内源镉主要以有机结合态为主，而外源镉主要以残渣态和交换态为主【农业环境科学学报,2003,22(5):541-545】。影响镉在土壤中转化的因素很多，土壤pH值和钙是影响镉形态的主要因素。
土壤pH值对土壤镉形态的影响主要表现在3个方面：第一，土壤pH值直接影响镉在土壤中的形态；第二，pH值影响土壤对镉的吸附与解吸；第三，pH值影响土壤溶液中重金属元素离子活度。水溶态和交换态镉含量随着酸度变化原因主要是：(1)pH值升高，土壤中的黏土矿物、水合氧化物和有机质表面的负电荷增加，对重金属离子的吸附力加强；(2)土壤有机质-金属络合物的稳定性随pH值的升高而增大，导致溶液中Cd2+浓度降低；(3)Cd2+在氧化物表面的吸附随pH值的升高而增强；(4)pH值升高,土壤溶液中多价阳离子和氢氧根离子的离子积增大，生成该元素的Cd(OH)2沉淀的机会增大，致使其在溶液中的浓度降低；(5)随着pH值升高，土壤溶液中铁、铝、镁离子浓度减小，使土壤有利于吸附Cd2+。Cd2+的理论浓度随着土壤pH值的上升而下降，因此，可通过调节土壤的酸碱度，达到控制土壤溶液Cd2+浓度的目的【Chinese Journal of Ecology,2015,34(1):130-137】。
外源钙在植物抵抗外界逆境胁迫中具有重要的作用，它可以减轻重金属对植物所造成的伤害。镉离子与钙离子的半径接近，二者的化学性质类似，Ca2+和Cd2+能够同时被植物的根系吸收，存在着竞争关系，尤其在Ca2+浓度较高的情况下，Cd2+的吸收就会明显受到抑制。钙提高植物耐镉性的机制可能有两个方面：一是钙使植物细胞的结构更加稳固；二是钙间接影响细胞的保护系统，使有效态氧等有害自由基的代谢保持平衡，钙信使系统可能参与了植物耐镉基因表达的调控。尽管Ca2+能显著减轻镉对植物的毒害效应，但是直接加入Ca2+容易造成局部盐浓度过高，土壤板结，且Ca2+易流失。目前主要通过加入硅酸钙、碳酸钙、熟石灰、硅酸镁钙等。这些物质不仅能提高土壤钙含量，还可以提高土壤pH值。其中施用熟石灰成本最低，对降低植物的镉含量具有较好效果，但施入石灰会使土壤不适于种植多作物，且上述物质不能吸附有效态Cd，对土壤保湿效果差，且钙离子释放不可控。如何在增加土壤Ca提升pH的同时高效去除活性Cd是调控土壤环境质量的关键问题。
海藻酸来源于褐色海藻，是一种天然阴离子多糖类天然高分子。其分子链段由β-1，4-甘露糖醛酸(M)和α-1，4-L-古洛糖醛酸(G)无规排列而构成。海藻酸钠通常情况下为白色或淡黄色粉末，易溶于水，吸湿性强，持水性能好，可生物降解；其稳定性在pH值为6至11时较好，pH值低于5时会形成海藻酸凝胶。海藻酸钠具有很高的离子交换功能，分子链中的G段能够和二价阳离子如钙离子发生络合反应，形成水凝胶，该凝胶在水中能够发生溶胀，释放钙离子。海藻酸钙水凝胶可以通过离子交换作用结合去除重金属离子。海藻酸钠与二价金属离子的结合能力顺序如下：Pb2+>Cu2+>Ba2+>Cd2+>Ca2+>Co2+>Ni2+>Zn2+>Mn2+>Mg2+。
海藻酸钙对溶液中的Cd2+具有较好的去除效果，且在离子交换的同时释放出来钙离子。海藻酸钙水凝胶过滤膜对ppm浓度的重金属离子具有接近100％的去除率【Waterscience and technology,2017,75(10):2322-2330】。但是由于海藻酸钙水凝胶的溶胀性能不可控，造成修复效果的稳定性较差。
硅酸钙已被证明可以有效降低土壤的pH，硅酸钙结构中硅-氧键在外界H+的作用下断裂，Ca2+通过质子交换释放到溶液中，在硅酸钙表层形成Si-OH硅胶层【ActaBiomaterialia,2009,5:1686-1696】。CaSiO3/CaAlg复合水凝胶膜制备和应用方法简单，绿色环保，没有用到任何有机溶剂，可望用于土壤中的镉污染修复。
本发明公开了一种缓释Ca2+调控土壤中Cd活性的复合材料的制备和应用方法。配制硅酸钠、海藻酸钠和羧甲基壳聚糖的混合物水溶液，将该混合物水溶液涂覆到表面接枝羧基官能团的无纺布纤维膜上，然后浸泡到可溶性钙盐水溶液中交联，得到负载硅酸钙/海藻酸钙/羧甲基壳聚糖的无纺布复合材料。将该复合材料埋置到土壤中，硅酸钙与土壤中的氢离子反应提高土壤的pH值，同时释放Ca2+，生成介孔SiO2。海藻酸钙吸附Cd2+，并且缓释Ca2 +，较高浓度的Ca2+抑制了农作物对Cd2+的吸收，降低土壤中Cd活性。本发明的复合材料能同时降低Cd活性并提高土壤pH值，羧甲基壳聚糖的抑菌作用使材料可长期使用，作为载体的无纺布方便土壤修复的实际操作，具有良好的应用前景。
发明内容
针对现有技术的不足，本发明拟解决的技术问题是镉严重超标、钝化材料难以长期使用、土壤中Cd活性调控困难等问题。
本发明解决所述镉严重超标、钝化材料难以长期使用、土壤中Cd活性调控困难等问题的技术方案是提供一种缓释Ca2+调控土壤中Cd活性的复合材料的制备和应用方法。
本发明提供了一种缓释Ca2+调控土壤中Cd活性的复合材料的制备和应用方法，其特征是包括以下步骤：
a)首先对无纺布纤维膜整理改性，得到接枝羧基的无纺布纤维膜；
b)配制质量百分比浓度0.1％-15％的硅酸钠、质量百分比浓度0.2％-10％的海藻酸钠和质量百分比浓度0.2％-10％的羧甲基壳聚糖的混合物水溶液；
c)配制质量百分比浓度0.2％-10％的可溶性钙盐水溶液；
d)将步骤b)得到的混合物水溶液涂覆到步骤a)得到的接枝羧酸功能团的无纺布纤维膜上，然后立即放入步骤c)得到的可溶性钙盐水溶液浸泡10-600min，钙离子同时交联海藻酸钠上的羧基，无纺布纤维膜上的羧基和羧甲基壳聚糖上的羧基，得到接枝在无纺布上的水凝胶；同时钙离子与步骤b)得到的混合物水溶液中的硅酸钠反应生成硅酸钙，得到一种缓释Ca2+调控土壤中Cd活性的复合材料，将其冷冻干燥保存；
e)在土壤修复使用前，先将步骤d)得到的冷冻干燥后的缓释Ca2+调控土壤中Cd活性的复合材料浸泡在去离子水中使该复合材料充分吸水软化，这样方便操作，避免直接使用冷冻干燥后的复合材料因太脆造成破损；
f)将步骤e)得到的充分吸水软化的复合材料埋置到Cd污染的土壤中，复合材料中的硅酸钙与土壤中的氢离子反应提高土壤的pH值，同时释放Ca2+，在复合材料表面生成介孔硅胶；海藻酸钙吸附Cd2+，并且缓释Ca2+，较高浓度的Ca2+抑制了农作物对Cd2+的吸收，从而降低土壤中Cd活性；羧甲基壳聚糖具有抑菌作用，避免了复合材料在土壤中被微生物降解，从而使复合材料可长期修复土壤的Cd污染；而作为载体的接枝羧基的无纺布纤维膜方便土壤修复的实际操作；
g)土壤修复后将埋置在土壤中的复合材料取出，将从土壤中吸附的活性Cd从土壤中彻底去除，从根本上降低了Cd的污染。
本发明所述的无纺布纤维膜的材质为聚酯、聚乙烯、聚丙烯和聚丙烯腈的任意一种或两种及以上混合物；所述的可溶性钙盐为氯化钙、硝酸钙、磷酸二氢钙、葡萄糖酸钙中的任意一种或两种及以上混合物。
本发明中土壤修复材料的制备和应用方法简单，原料及制备过程绿色环保，得到的一种缓释Ca2+调控土壤中Cd活性的复合材料方便实际应用，在修复重金属污染的土壤过程中具有广阔的应用前景。
具体实施方式
下面介绍本发明的具体实施例，但本发明不受实施例的限制。
实施例1.
a)首先对聚酯材质的无纺布纤维膜整理改性，得到接枝羧基的聚酯材质的无纺布纤维膜；
b)配制质量百分比浓度0.1％的硅酸钠、质量百分比浓度0.2％的海藻酸钠和质量百分比浓度0.2％的羧甲基壳聚糖的混合物水溶液；
c)配制质量百分比浓度0.2％的氯化钙水溶液；
d)将步骤b)得到的混合物水溶液涂覆到步骤a)得到的接枝羧酸功能团的聚酯材质的无纺布纤维膜上，然后立即放入步骤c)得到的氯化钙水溶液浸泡10min，钙离子同时交联海藻酸钠上的羧基，聚酯材质的无纺布纤维膜上的羧基和羧甲基壳聚糖上的羧基，得到接枝在无纺布上的水凝胶；同时钙离子与步骤b)得到的混合物水溶液中的硅酸钠反应生成硅酸钙，得到一种缓释Ca2+调控土壤中Cd活性的复合材料，将其冷冻干燥保存；
e)在土壤修复使用前，先将步骤d)得到的冷冻干燥后的缓释Ca2+调控土壤中Cd活性的复合材料浸泡在去离子水中使该复合材料充分吸水软化，这样方便操作，避免直接使用冷冻干燥后的复合材料因太脆造成破损；
f)将步骤e)得到的充分吸水软化的复合材料埋置到Cd污染的土壤中，复合材料中的硅酸钙与土壤中的氢离子反应提高土壤的pH值，同时释放Ca2+，在复合材料表面生成介孔硅胶；海藻酸钙吸附Cd2+，并且缓释Ca2+，较高浓度的Ca2+抑制了农作物对Cd2+的吸收，从而降低土壤中Cd活性；羧甲基壳聚糖具有抑菌作用，避免了复合材料在土壤中被微生物降解，从而使复合材料可长期修复土壤的Cd污染；而作为载体的接枝羧基的聚酯材质的无纺布纤维膜方便土壤修复的实际操作；
g)土壤修复后将埋置在土壤中的复合材料取出，将从土壤中吸附的活性Cd从土壤中彻底去除，从根本上降低了Cd的污染。
实施例2.
a)首先对聚丙烯材质的无纺布纤维膜整理改性，得到接枝羧基的聚丙烯材质的无纺布纤维膜；
b)配制质量百分比浓度15％的硅酸钠、质量百分比浓度10％的海藻酸钠和质量百分比浓度10％的羧甲基壳聚糖的混合物水溶液；
c)配制质量百分比浓度10％的硝酸钙水溶液；
d)将步骤b)得到的混合物水溶液涂覆到步骤a)得到的接枝羧酸功能团的聚丙烯材质的无纺布纤维膜上，然后立即放入步骤c)得到的硝酸钙水溶液浸泡600min，钙离子同时交联海藻酸钠上的羧基，聚丙烯材质的无纺布纤维膜上的羧基和羧甲基壳聚糖上的羧基，得到接枝在无纺布上的水凝胶；同时钙离子与步骤b)得到的混合物水溶液中的硅酸钠反应生成硅酸钙，得到一种缓释Ca2+调控土壤中Cd活性的复合材料，将其冷冻干燥保存；
e)在土壤修复使用前，先将步骤d)得到的冷冻干燥后的缓释Ca2+调控土壤中Cd活性的复合材料浸泡在去离子水中使该复合材料充分吸水软化，这样方便操作，避免直接使用冷冻干燥后的复合材料因太脆造成破损；
f)将步骤e)得到的充分吸水软化的复合材料埋置到Cd污染的土壤中，复合材料中的硅酸钙与土壤中的氢离子反应提高土壤的pH值，同时释放Ca2+，在复合材料表面生成介孔硅胶；海藻酸钙吸附Cd2+，并且缓释Ca2+，较高浓度的Ca2+抑制了农作物对Cd2+的吸收，从而降低土壤中Cd活性；羧甲基壳聚糖具有抑菌作用，避免了复合材料在土壤中被微生物降解，从而使复合材料可长期修复土壤的Cd污染；而作为载体的接枝羧基的聚丙烯材质的无纺布纤维膜方便土壤修复的实际操作；
g)土壤修复后将埋置在土壤中的复合材料取出，将从土壤中吸附的活性Cd从土壤中彻底去除，从根本上降低了Cd的污染。
实施例3.
a)首先对聚丙烯腈材质的无纺布纤维膜整理改性，得到接枝羧基的聚丙烯腈材质的无纺布纤维膜；
b)配制质量百分比浓度8％的硅酸钠、质量百分比浓度6％的海藻酸钠和质量百分比浓度5％的羧甲基壳聚糖的混合物水溶液；
c)配制质量百分比浓度6％的磷酸二氢钙水溶液；
d)将步骤b)得到的混合物水溶液涂覆到步骤a)得到的接枝羧酸功能团的聚丙烯腈材质的无纺布纤维膜上，然后立即放入步骤c)得到的磷酸二氢钙水溶液浸泡400min，钙离子同时交联海藻酸钠上的羧基，聚丙烯腈材质的无纺布纤维膜上的羧基和羧甲基壳聚糖上的羧基，得到接枝在无纺布上的水凝胶；同时钙离子与步骤b)得到的混合物水溶液中的硅酸钠反应生成硅酸钙，得到一种缓释Ca2+调控土壤中Cd活性的复合材料，将其冷冻干燥保存；
e)在土壤修复使用前，先将步骤d)得到的冷冻干燥后的缓释Ca2+调控土壤中Cd活性的复合材料浸泡在去离子水中使该复合材料充分吸水软化，这样方便操作，避免直接使用冷冻干燥后的复合材料因太脆造成破损；
f)将步骤e)得到的充分吸水软化的复合材料埋置到Cd污染的土壤中，复合材料中的硅酸钙与土壤中的氢离子反应提高土壤的pH值，同时释放Ca2+，在复合材料表面生成介孔硅胶；海藻酸钙吸附Cd2+，并且缓释Ca2+，较高浓度的Ca2+抑制了农作物对Cd2+的吸收，从而降低土壤中Cd活性；羧甲基壳聚糖具有抑菌作用，避免了复合材料在土壤中被微生物降解，从而使复合材料可长期修复土壤的Cd污染；而作为载体的接枝羧基的聚丙烯腈材质的无纺布纤维膜方便土壤修复的实际操作；
g)土壤修复后将埋置在土壤中的复合材料取出，将从土壤中吸附的活性Cd从土壤中彻底去除，从根本上降低了Cd的污染。
实施例4.
a)首先对聚乙烯/聚丙烯材质的无纺布纤维膜整理改性，得到接枝羧基的聚乙烯/聚丙烯材质的无纺布纤维膜；
b)配制质量百分比浓度12％的硅酸钠、质量百分比浓度8％的海藻酸钠和质量百分比浓度4％的羧甲基壳聚糖的混合物水溶液；
c)配制质量百分比浓度3％的硝酸钙和葡萄糖酸钙水溶液；
d)将步骤b)得到的混合物水溶液涂覆到步骤a)得到的接枝羧酸功能团的聚乙烯/聚丙烯材质的无纺布纤维膜上，然后立即放入步骤c)得到的硝酸钙和葡萄糖酸钙水溶液浸泡500min，钙离子同时交联海藻酸钠上的羧基，聚乙烯/聚丙烯材质的无纺布纤维膜上的羧基和羧甲基壳聚糖上的羧基，得到接枝在无纺布上的水凝胶；同时钙离子与步骤b)得到的混合物水溶液中的硅酸钠反应生成硅酸钙，得到一种缓释Ca2+调控土壤中Cd活性的复合材料，将其冷冻干燥保存；
e)在土壤修复使用前，先将步骤d)得到的冷冻干燥后的缓释Ca2+调控土壤中Cd活性的复合材料浸泡在去离子水中使该复合材料充分吸水软化，这样方便操作，避免直接使用冷冻干燥后的复合材料因太脆造成破损；
f)将步骤e)得到的充分吸水软化的复合材料埋置到Cd污染的土壤中，复合材料中的硅酸钙与土壤中的氢离子反应提高土壤的pH值，同时释放Ca2+，在复合材料表面生成介孔硅胶；海藻酸钙吸附Cd2+，并且缓释Ca2+，较高浓度的Ca2+抑制了农作物对Cd2+的吸收，从而降低土壤中Cd活性；羧甲基壳聚糖具有抑菌作用，避免了复合材料在土壤中被微生物降解，从而使复合材料可长期修复土壤的Cd污染；而作为载体的接枝羧基的聚乙烯/聚丙烯材质的无纺布纤维膜方便土壤修复的实际操作；
g)土壤修复后将埋置在土壤中的复合材料取出，将从土壤中吸附的活性Cd从土壤中彻底去除，从根本上降低了Cd的污染。
Claims (4)
1.一种缓释Ca2+调控土壤中Cd活性的复合材料的制备和应用方法，其特征是包括以下步骤：
a)首先对无纺布纤维膜整理改性，得到接枝羧基的无纺布纤维膜；
b)配制质量百分比浓度0.1％-15％的硅酸钠、质量百分比浓度0.2％-10％的海藻酸钠和质量百分比浓度0.2％-10％的羧甲基壳聚糖的混合物水溶液；
c)配制质量百分比浓度0.2％-10％的可溶性钙盐水溶液；
d)将步骤b)得到的混合物水溶液涂覆到步骤a)得到的接枝羧酸功能团的无纺布纤维膜上，然后立即放入步骤c)得到的可溶性钙盐水溶液浸泡10-600min，钙离子同时交联海藻酸钠上的羧基，无纺布纤维膜上的羧基和羧甲基壳聚糖上的羧基，得到接枝在无纺布上的水凝胶；同时钙离子与步骤b)得到的混合物水溶液中的硅酸钠反应生成硅酸钙，得到一种缓释Ca2+调控土壤中Cd活性的复合材料，将其冷冻干燥保存；
e)在土壤修复使用前，先将步骤d)得到的冷冻干燥后的缓释Ca2+调控土壤中Cd活性的复合材料浸泡在去离子水中使该复合材料充分吸水软化，这样方便操作，避免直接使用冷冻干燥后的复合材料因太脆造成破损；
f)将步骤e)得到的充分吸水软化的复合材料埋置到Cd污染的土壤中，复合材料中的硅酸钙与土壤中的氢离子反应提高土壤的pH值，同时释放Ca2+，在复合材料表面生成介孔硅胶；海藻酸钙吸附Cd2+，并且缓释Ca2+，较高浓度的Ca2+抑制了农作物对Cd2+的吸收，从而降低土壤中Cd活性；羧甲基壳聚糖具有抑菌作用，避免了复合材料在土壤中被微生物降解，从而使复合材料可长期修复土壤的Cd污染；而作为载体的接枝羧基的无纺布纤维膜方便土壤修复的实际操作；
g)土壤修复后将埋置在土壤中的复合材料取出，将从土壤中吸附的活性Cd带出来，从根本上降低了Cd的污染。
2.如权利要求1所述一种缓释Ca2+调控土壤中Cd活性的复合材料的制备和应用方法，其特征是所述的无纺布纤维膜的材质为聚酯、聚乙烯、聚丙烯和聚丙烯腈的任意一种或两种及以上混合物。
3.如权利要求1所述一种缓释Ca2+调控土壤中Cd活性的复合材料的制备和应用方法，其特征是所述的可溶性钙盐为氯化钙、硝酸钙、磷酸二氢钙、葡萄糖酸钙中的任意一种或两种及以上混合物。
4.如权利要求1所述一种缓释Ca2+调控土壤中Cd活性的复合材料的制备和应用方法，其特征是制备和应用方法简单，原料及制备过程绿色环保，得到的一种缓释Ca2+调控土壤中Cd活性的复合材料在修复重金属污染的土壤过程中具有广阔的应用前景。
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