CN103496835B - 多环芳烃类化合物污染沉积物的原位修复剂及其修复方法 - Google Patents

多环芳烃类化合物污染沉积物的原位修复剂及其修复方法 Download PDF

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CN103496835B
CN103496835B CN201310461562.1A CN201310461562A CN103496835B CN 103496835 B CN103496835 B CN 103496835B CN 201310461562 A CN201310461562 A CN 201310461562A CN 103496835 B CN103496835 B CN 103496835B
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许玫英
孙国萍
郭俊
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Institute of Microbiology of Guangdong Academy of Sciences
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Guangdong Institute of Microbiology
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Abstract

发明公开了一种多环芳烃类化合物污染沉积物的原位修复剂及其修复方法。包括质量比为100~1000:200~2000:1~10:100~2000的Ca(NO3)2·4H2O、C6H5O7Fe·5H2O、聚丙烯酰胺和水。通过向受PAHs污染的沉积物中间歇式地投加可缓慢释放的多环芳烃类化合物污染沉积物的原位修复剂,以提高沉积物中土著微生物的丰度和降解活性,促进PAHs的原位降解,实现污染沉积物的治理。该技术的操作简单,不需要额外建设处理场地,所需治理费用低,效果显著,不产生二次污染,在PAHs污染沉积物整治中具有广阔的应用前景。

Description

多环芳烃类化合物污染沉积物的原位修复剂及其修复方法
技术领域:
本发明属于环境污染治理工程、生态工程以及环境生物工程技术领域,具体涉及多环芳烃类化合物污染沉积物的原位修复剂及其修复方法。
背景技术:
随着经济社会的发展及社会工业化进程的加快,越来越多的多环芳烃类化合物(PAHs)被释放到环境中。由于它们具有高毒性、持久性、生物蓄积性、亲脂憎水性等特点,很容易吸附于颗粒物中,并大量积累在水体沉积物中,进而通过生物富集作用,危害人类健康和生态安全。目前国内外对于PAHs污染沉积物的修复技术主要包括物理、化学和生物修复技术。相对于物理、化学的沉积物修复技术,生物修复技术因为其投入少、无二次污染、治理效果持久而受到越来越多的青睐。根据处理场所划分,又可分为异位修复技术和原位修复技术两大类。原位修复技术可以在不需要搬动沉积物、不额外建设处理场地、基本不破坏水体沉积物自然环境条件下,在原地实现污染物的减量和消除,操作简单、且运行成本低。大部分PAHs的生物降解过程需要电子受体的参与。然而,沉积物环境中溶解氧浓度往往较低,维持微生物正常呼吸的电子受体浓度相当馈乏,这也是影响沉积物中PAHs生物降解效率的重要因素。因此,研究和开发可显著提高PAHs污染沉积物中微生物的呼吸活性,且简便、价廉的原位修复技术,是加速PAHs污染沉积物净化的重要提前。
发明内容:
本发明的第一个目的是提供一种多环芳烃类化合物污染沉积物的原位修复剂,其特征在于,包括Ca(NO3)2·4H2O、C6H5O7Fe·5H2O、聚丙烯酰胺和水,Ca(NO3)2·4H2O、C6H5O7Fe·5H2O、聚丙烯酰胺和水的质量比为100~1000:200~2000:1~10:100~2000。
本发明的多环芳烃类化合物污染沉积物的原位修复剂的制备方法为:将Ca(NO3)2·4H2O、C6H5O7Fe·5H2O、聚丙烯酰胺和水按照上述质量比混合均匀。
本发明的多环芳烃类化合物污染沉积物的原位修复剂是一种可缓慢释放的微生物厌氧呼吸调控剂,能够提高沉积物中土著微生物的丰度和降解活性,促进PAHs的原位降解,实现污染沉积物的治理。
本发明的第二个目的是提供一种多环芳烃类化合物污染沉积物的原位修复方法,其特征在于,对于PAHs的总含量高于1000μg/kg的污染沉积物,每立方米的沉积物中每次注射多环芳烃类化合物污染沉积物的原位修复剂1~5L,每个月注射一次,直至沉积物中PAHs的总含量低于600μg/kg;对于PAHs的总含量介于200~600μg/kg的污染沉积物,每立方米的沉积物中注射多环芳烃类化合物污染沉积物的原位修复剂0.5~5L,每两个月注射一次,直至沉积物中PAHs的总含量低于200μg/kg;对于PAHs的总含量低于200μg/kg的污染沉积物,每立方米的沉积物中注射多环芳烃类化合物污染沉积物的原位修复剂0.1~1L,每三个月注射一次,直至沉积物中PAHs的总含量低于10μg/kg。
所述的注射,优选采用注射器注射。
优选,每次注射时,将多环芳烃类化合物污染沉积物的原位修复剂分五份注于泥层表面以下40cm处。
本发明的多环芳烃类化合物污染沉积物的原位修复剂及其修复方法,是以微生物呼吸理论为指导,结合环境工程和生态工程技术,通过向受PAHs污染的沉积物中间歇式地投加可缓慢释放的多环芳烃类化合物污染沉积物的原位修复剂来调控微生物的厌氧呼吸,以提高沉积物中土著微生物的丰度和降解活性,促进PAHs的原位降解,实现PAHs的原位减量,从而达到治理被PAHs污染的沉积物的目的。
本发明操作简单,不需要额外建设处理场地,所需治理费用低廉,效果显著,不产生二次污染,在PAHs污染沉积物整治中具有广阔的应用前景。
具体实施方式:
以下实施例是对本发明的进一步说明,而不是对本发明的限制。
实施例1:广东省佛山市某黑臭河涌沉积物的原位修复
广东省佛山市某黑臭河涌2#和3#监测点的沉积物中均检出16种美国环保署(EPA)优先控制的PAHs,即萘(Nap)、苊烯(Acy)、苊(Ace)、芴(Flu)、菲(Phe)、蒽(Ant)、荧蒽(Fla)、芘(Pyr)、苯并[a]蒽(Baa)、苣(Chr)、苯并[b]荧蒽(Bbf)、苯并[ik]荧蒽(Bkf)、苯并[a]芘(Bap)、茚并(1,2,3-cd)芘[In(1,2,3-cd)p]、二苯并(a,h)蒽[D(a,h)a]、苯并(g,h,i)苝(二萘嵌苯)[B(g,h,i)p]。这两个监测点沉积物中PAHs的总含量均超过2000μg/kg,其中2#为2589.366μg/kg,3#为3187.358μg/kg污染相当严重。
将Ca(NO3)2·4H2O、C6H5O7Fe·5H2O、聚丙烯酰胺和水按照100:200:1:2000的质量比混合均匀,得到多环芳烃类化合物污染沉积物的原位修复剂。
每立方米的沉积物中每次注射多环芳烃类化合物污染沉积物的原位修复剂1L,分五份注于泥层表面以下40cm处,每个月注射一次,注射两个月后,2#和3#监测点沉积物中PAHs的去除率分别达到91.3%和92.7%。
当PAHs的总含量在200~600μg/kg时,每立方米的沉积物中注射多环芳烃类化合物污染沉积物的原位修复剂0.5L,分五份注于泥层表面以下40cm处,每两个月注射一次,注射两次后,2#和3#监测点沉积物中PAHs的去除率分别达到94.4%和95.7%。
当PAHs的总含量低于200μg/kg时,每立方米的沉积物中注射多环芳烃类化合物污染沉积物的原位修复剂0.1L,分五份注于泥层表面以下40cm处,每三个月注射一次,注射两次后,2#和3#监测点中的PAHs含量均低于10μg/kg。
实施例2:上海市某黑臭河道沉积物的原位修复
上海市某黑臭河道沉积物中检出16种美国环保署(EPA)优先控制的PAHs,平均PAHs总含量为1800.345μg/kg,以4环以上[苯并[b]荧蒽、苯并[ik]荧蒽、苯并[a]芘、茚并(1,2,3-cd)芘、二苯并(a,h)蒽、苯并(g,h,i)苝]芳烃为主。
将Ca(NO3)2·4H2O、C6H5O7Fe·5H2O、聚丙烯酰胺和水按照1000:2000:10:100的质量比混合均匀,得到多环芳烃类化合物污染沉积物的原位修复剂。
每立方米的沉积物中每次注射多环芳烃类化合物污染沉积物的原位修复剂5L,分五份注于泥层表面以下40cm处,每个月注射一次,注射三个月后,沉积物中PAHs的去除率达到88.3%。
当PAHs的总含量在200~600μg/kg时,每立方米的沉积物中注射多环芳烃类化合物污染沉积物的原位修复剂5L,分五份注于泥层表面以下40cm处,每两个月注射一次,注射两次后,沉积物中PAHs的去除率达到93.3%。
当PAHs的总含量低于200μg/kg时,每立方米的沉积物中注射多环芳烃类化合物污染沉积物的原位修复剂1L,分五份注于泥层表面以下40cm处,每三个月注射一次,注射两次后,沉积物中PAHs总含量低于10μg/kg。
实施例3:广州市某黑臭河道沉积物的原位修复
广州市某黑臭河道沉积物中检出16种美国环保署(EPA)优先控制的PAHs,平均PAHs总含量为2830.215μg/kg,以2~3环(萘、苊烯、苊、芴、蒽)芳烃为主。
将Ca(NO3)2·4H2O、C6H5O7Fe·5H2O、聚丙烯酰胺和水按照100:180:1:190的质量比混合均匀,得到多环芳烃类化合物污染沉积物的原位修复剂。
每立方米的沉积物中每次注射多环芳烃类化合物污染沉积物的原位修复剂2.5L,分五份注于泥层表面以下40cm处,每个月注射一次,处理两个月后,沉积物中PAHs的去除率达到95.3%。
当PAHs的总含量低于200μg/kg时,每立方米的沉积物中注射多环芳烃类化合物污染沉积物的原位修复剂0.5L,分五份注于泥层表面以下40cm处,每三个月注射一次,处理六个月后,沉积物中PAHs总含量低于10μg/kg。

Claims (4)

1.一种多环芳烃类化合物污染沉积物的原位修复剂,其特征在于,包括Ca(NO3)2·4H2O、C6H5O7Fe·5H2O、聚丙烯酰胺和水,Ca(NO3)2·4H2O、C6H5O7Fe·5H2O、聚丙烯酰胺和水的质量比为100~1000:200~2000:1~10:100~2000。
2.一种多环芳烃类化合物污染沉积物的原位修复方法,其特征在于,对于PAHs的总含量高于1000μg/kg的污染沉积物,每立方米的沉积物中每次注射权利要求1的多环芳烃类化合物污染沉积物的原位修复剂1~5L,每个月注射一次,直至沉积物中PAHs的总含量低于600μg/kg;对于PAHs的总含量介于200~600μg/kg的污染沉积物,每立方米的沉积物中每次注射权利要求1的多环芳烃类化合物污染沉积物的原位修复剂0.5~5L,每两个月注射一次,直至沉积物中PAHs的总含量低于200μg/kg;对于PAHs的总含量低于200μg/kg的污染沉积物,每立方米的沉积物中每次注射权利要求1的多环芳烃类化合物污染沉积物的原位修复剂0.1~1L,每三个月注射一次,直至沉积物中PAHs的总含量低于10μg/kg;
所述的PAHs为多环芳烃类化合物。
3.根据权利要求2所述的多环芳烃类化合物污染沉积物的原位修复方法,其特征在于,采用注射器进行注射。
4.根据权利要求2所述的多环芳烃类化合物污染沉积物的原位修复方法,其特征在于,每次注射时,将多环芳烃类化合物污染沉积物的原位修复剂分五份注于泥层表面以下40cm处。
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Application publication date: 20140108

Assignee: Liuzhou Tengtu Environmental Protection Technology Co.,Ltd.

Assignor: Institute of Microbiology, Guangdong Academy of Sciences

Contract record no.: X2023980045213

Denomination of invention: In situ remediation agents and methods for polycyclic aromatic hydrocarbon compounds contaminated sediment

Granted publication date: 20150520

License type: Common License

Record date: 20231031

Application publication date: 20140108

Assignee: Liuzhou Renjia Biotechnology Co.,Ltd.

Assignor: Institute of Microbiology, Guangdong Academy of Sciences

Contract record no.: X2023980045212

Denomination of invention: In situ remediation agents and methods for polycyclic aromatic hydrocarbon compounds contaminated sediment

Granted publication date: 20150520

License type: Common License

Record date: 20231031

Application publication date: 20140108

Assignee: Beihai anfeigao Environmental Protection Technology Co.,Ltd.

Assignor: Institute of Microbiology, Guangdong Academy of Sciences

Contract record no.: X2023980045197

Denomination of invention: In situ remediation agents and methods for polycyclic aromatic hydrocarbon compounds contaminated sediment

Granted publication date: 20150520

License type: Common License

Record date: 20231031

Application publication date: 20140108

Assignee: Guangzhou Kelang Medical Technology Co.,Ltd.

Assignor: Institute of Microbiology, Guangdong Academy of Sciences

Contract record no.: X2023980045194

Denomination of invention: In situ remediation agents and methods for polycyclic aromatic hydrocarbon compounds contaminated sediment

Granted publication date: 20150520

License type: Common License

Record date: 20231031

Application publication date: 20140108

Assignee: Hezhou Tongyun Environmental Protection Technology Co.,Ltd.

Assignor: Institute of Microbiology, Guangdong Academy of Sciences

Contract record no.: X2023980045190

Denomination of invention: In situ remediation agents and methods for polycyclic aromatic hydrocarbon compounds contaminated sediment

Granted publication date: 20150520

License type: Common License

Record date: 20231031

Application publication date: 20140108

Assignee: Foshan shangxiaoyun Technology Co.,Ltd.

Assignor: Institute of Microbiology, Guangdong Academy of Sciences

Contract record no.: X2023980045186

Denomination of invention: In situ remediation agents and methods for polycyclic aromatic hydrocarbon compounds contaminated sediment

Granted publication date: 20150520

License type: Common License

Record date: 20231031

EE01 Entry into force of recordation of patent licensing contract
EE01 Entry into force of recordation of patent licensing contract

Application publication date: 20140108

Assignee: Chongqing Longjinsheng Biotechnology Group Co.,Ltd.

Assignor: Institute of Microbiology, Guangdong Academy of Sciences

Contract record no.: X2023980048318

Denomination of invention: In situ remediation agents and remediation methods for polycyclic aromatic hydrocarbon contaminated sediments

Granted publication date: 20150520

License type: Common License

Record date: 20231124

Application publication date: 20140108

Assignee: Senhai Environmental Protection Group Co.,Ltd.

Assignor: Institute of Microbiology, Guangdong Academy of Sciences

Contract record no.: X2023980048263

Denomination of invention: In situ remediation agents and remediation methods for polycyclic aromatic hydrocarbon contaminated sediments

Granted publication date: 20150520

License type: Common License

Record date: 20231124

Application publication date: 20140108

Assignee: Shandong Qianhui Environmental engineering Co.,Ltd.

Assignor: Institute of Microbiology, Guangdong Academy of Sciences

Contract record no.: X2023980048253

Denomination of invention: In situ remediation agents and remediation methods for polycyclic aromatic hydrocarbon contaminated sediments

Granted publication date: 20150520

License type: Common License

Record date: 20231124

Application publication date: 20140108

Assignee: Shandong Chunjing Environmental Protection Technology Co.,Ltd.

Assignor: Institute of Microbiology, Guangdong Academy of Sciences

Contract record no.: X2023980048247

Denomination of invention: In situ remediation agents and remediation methods for polycyclic aromatic hydrocarbon contaminated sediments

Granted publication date: 20150520

License type: Common License

Record date: 20231124