Microbial Induced Carbonate Precipitation and Its Application for Immobilization of Heavy Metals: a Review
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摘要: 生物矿化已受到化学、物理、生物、材料、医学、生命及环境等多学科的广泛关注,其中,以尿素为底物的MICP(微生物诱导碳酸盐沉淀)技术是生物矿化领域的研究热点之一.在分析MICP过程中的酶解机理和生物大分子在微生物矿化过程中的作用基础上,通过对重金属离子的矿化产物和碳酸盐矿化菌的成矿因素分析,揭示MICP矿化产物的特征及形成条件.碳酸盐矿化菌主要产生脲酶分解尿素,增加土壤CO32-饱和度,其代谢产生的胞外聚合物具有多种功能团组合和键能连接,起着调控生物矿化的作用.MICP技术可用于固定土壤和水体中的Cu、Pb、Zn、Cd、Cr、As等重金属,重金属主要以共沉淀的形式被固定,阴阳离子型重金属以类质同象置换方式分别占据方解石中的CO32-位和Ca2+位,从而促使污染土壤中的可交换态重金属向碳酸盐结合态转移.但是,MICP技术主要针对减少重金属的生物可利用性,不能满足以全量来计算的现行土壤环境质量标准,且MICP技术在长期有效性、生物安全性和土壤理化性质等方面存在诸多隐患.因此,由试验条件转向实际应用具有一定挑战.建议寻找更稳定的方法以阻止碳酸盐矿物中的重金属溶出,且有必要将开发高效的土著微生物复合菌剂作为未来MICP研究的方向之一.Abstract: Biomineralization has attracted much attention from chemistry, physics, biology, material, medicine, life and environment sciences. Microbial induced carbonate precipitation (MICP) using urea as the substrate is one of the hot topics. Herein, we reviewed the enzymatic mechanism of MICP and the function of biomacromolecule in the progress of biomineralization. Previous studies showed that the concentration of soil carbonate increases due to the decomposition of urea which can be enhanced in the presence of urease produced by ureolytic bacteria. Meanwhile, the extracellular polymer substance (EPS) secreted by the bacteria, possessing varied functional groups and chemical bonding, can regulate the biomineralization. The results demonstrated that MICP can remediate heavy metals pollution, such as Cu, Pb, Zn, Cd, Cr and As both in soil and solution. Co-precipitation is the dominant mechanism for the heavy metals immobilization, via cation → Ca2+/anion → CO32- substitution, resulting in carbonate-bound heavy metals. Therefore, MICP is useful to reduce the bioavailability of heavy metals. However, it does not change the soil quality according to the current standards which base on the total concentration of heavy metals. Furthermore, there are potential risks on several topics, such as long-term validity, biological safety and change of physical or chemical properties, which challenge the application of MICP to immobilize heavy metals in soil. The technique should be further developed to re-immobilize the released heavy metals due to the dissolution of carbonate minerals. Meanwhile, multiple native microbial communities should be developed to insure the effectiveness of MICP in varied environments.
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Key words:
- microbial mineralization /
- heavy metals /
- carbonate precipitation /
- urease
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图 2 不同微生物通过MICP对溶液中重金属的去除率
注:根据文献[28]修改.
Figure 2. The removal rates of various aqueous heavy metals by isolated bacterial strains through MICP
表 1 MICP固定重金属研究实例
Table 1. The examples of MICP in immobilization of heavy metal
重金属 细菌 不同介质中重金属的生物修复率 数据来源 Cu 黄色考克氏菌(Kocuria flava CR1) 95%(ic=340 mg/kg,土壤) 文献[23] 97%(ic=1 000 mg/L,溶液) 文献[23] 碳酸盐矿化菌剂 74%(ic=12.95 mg/kg,土壤) 文献[24] 土壤芽孢八叠球菌(Sporosarcina soli B-22) 61.8%(ic=128 mg/L,溶液) 文献[25] 朝鲜芽孢八叠球菌(Sporosarcina koreensis UR47) 93.2%(ic=945 mg/L,溶液) 文献[28] Pb 黄色考克氏菌(Kocuria flava) 83.4%(ic=100 mg/kg,土壤) 文献[26] 阴沟肠杆菌(Enterobacter cloacae KJ-46) 68%(ic=7.2 mg/L,溶液) 文献[27] 朝鲜芽孢八叠球菌(Sporosarcina koreensis UR47) 99%(ic=1.49 g/L,溶液) 文献[28] 施氏假单胞菌(Pseudomonas stutzeri) 97%(ic=103.5 mg/L,溶液) 文献[29] 碳酸盐矿化菌剂 75%(ic=4.95 mg/kg,土壤) 文献[24] 蜡状芽孢杆菌(Bacillus cereus Pb21) 90%(ic=2 g/L,溶液) 文献[30] Zn 芽孢八叠球菌(Sporosarcina sp. R-31323 UR31) 99%(ic=0.96 g/L,溶液) 文献[28] 碳酸盐矿化菌剂 50%(ic=33.46 mg/kg,土壤) 文献[24] Cd 微杆菌(Exiguobacterium undae) 84%(ic=100 mg/L,溶液) 文献[31] 微杆菌(Exiguobacterium undae) 90%(ic=100 mg/kg,土壤) 文献[31] 球形芽孢杆菌(Lysinibacillus sphaericus) 99.95%(ic=0.82 g/L,溶液) 文献[32] 肿大地杆菌(Terrabacter tumescens) 99%(ic= 1.23 g/L,溶液) 文献[28] 碳酸盐矿化菌剂 52%(ic=0.64 mg/kg,土壤) 文献[24] 芽孢杆菌GZ-22(Bacillus sp. GZ-22) 60.72%(ic=10 mg/L,溶液) 文献[33] Cr 芽孢杆菌(Bacillus sp. CS8) >68%(ic=124.8 mg/kg,镉渣) 文献[34] 蜡状芽孢杆菌(Bacillus cereus YR5) 92%(ic=100 mg/kg,土壤) 文献[35] As 芽孢八叠球菌(Sporosarcina ginsengisoli) 96%(ic=10 mg/L,溶液) 文献[36] 芽孢八叠球菌(Sporosarcina ginsengisoli) 99.8% (ic=500 mg/kg,土壤) 文献[36] 碳酸盐矿化菌剂 83%(ic=14.01 mg/kg,土壤) 文献[24] Sr 盐单胞菌(Halomonas sp.) 86%(ic=100 mg/kg,石英砂) 文献[37] 芽孢杆菌(Bacillus pasteurei) 95%(ic=87.6 mg/L,溶液) 文献[38] 巴氏芽孢八叠球菌(Sporosarcina pasteurii) 59%(ic=210 mg/L,多孔介质流) 文献[39] 巴氏芽孢八叠球菌(Sporosarcina pasteurii WJ-2) 80%(ic=7 mg/kg,石英砂) 文献[40] 注:ic指土壤或溶液中重金属的初始浓度. -
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