Article(id=1241049973807174017, tenantId=1146029695717560320, journalId=1234093305789726721, issueId=1241049962679694215, articleNumber=null, orderNo=null, doi=null, pmid=null, cstr=null, oa=null, hot=null, price=null, onlineType=0, articleFormat=0, articleType=null, articleTypeStr=null, receivedDate=1717344000000, receivedDateStr=2024-06-03, revisedDate=null, revisedDateStr=null, acceptedDate=null, acceptedDateStr=null, onlineDate=1773818971349, onlineDateStr=2026-03-18, pubDate=1737302400000, pubDateStr=2025-01-20, doiRegisterDate=null, doiRegisterDateStr=null, onlineIssueDate=1773818971349, onlineIssueDateStr=2026-03-18, onlineJustAcceptDate=null, onlineJustAcceptDateStr=null, onlineFirstDate=null, onlineFirstDateStr=null, sourceXml=null, magXml=null, createTime=1773818971349, creator=13701087609, updateTime=1773818971349, updator=13701087609, issue=Issue{id=1241049962679694215, tenantId=1146029695717560320, journalId=1234093305789726721, year='2025', volume='45', issue='1', pageStart='1', pageEnd='592', issueExtLink='null', onlineDate='null', pubDate='null', beforeIssueId=null, nextIssueId=null, price=null, status=1, issueComplete=1, articleOrder=1, issueType=-1, specialIssue=null, createTime=1773818968696, creator=13701087609, updateTime=1773819749443, updator=13701087609, preIssue=null, nextIssue=null, ext={EN=IssueExt(id=1241053237428671382, tenantId=1146029695717560320, journalId=1234093305789726721, issueId=1241049962679694215, language=EN, specialIssueTitle=, coverIllustrator=null, specialIssueEditor=, specialIssueAbout=), CN=IssueExt(id=1241053237428671383, tenantId=1146029695717560320, journalId=1234093305789726721, issueId=1241049962679694215, language=CN, specialIssueTitle=, coverIllustrator=null, specialIssueEditor=, specialIssueAbout=)}, issueFiles=null}, startPage=175, endPage=184, ext={EN=ArticleExt(id=1241049974310490512, articleId=1241049973807174017, tenantId=1146029695717560320, journalId=1234093305789726721, language=EN, title=Bioretention cells with epoxy resin modified loess to remove runoff pollutants, columnId=1234106386360103680, journalTitle=China Environmental Science, columnName=Water Pollution Control, runingTitle=null, highlight=null, articleAbstract=

This paper chose epoxy resin modified loess as the primary filler for the biological retention tank. It tested 48 different raw material types with varying parameters to improve the ratio of epoxy resin to loess as the benchmark (greater than 2mm/min). The corresponding epoxy resin content is 5% (b5), 10% (b10), 5% (b5d1), and 10% (b10d1). The adsorption capability of the four enhanced materials for NH4+ -N and phosphate was stronger than that of conventional fillers. After the biological retention tank was filled, b5d1had the best average removal of NH4+ -N and COD, reaching 93.97% and 77.5%, respectively. b5also removed NO3- -N(76.6%), TN (62.4%), and TP (98%) more successfully than the other two. Through microbial investigation, b5was found to contain more organisms including Chloroflexi and Steroidobacter that are engaged in the flora process. The NH4+ -N, NO3- -N, TN, TP, and COD can all be efficiently removed by an enhanced loess packed biological tank. According to studies, loess enhanced with epoxy resin has a wide range of promotional uses, may be utilized as biological tank packing, and effectively filters contaminants in runoff rainfall.

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选用环氧树脂改良黄土材料作为生物滞留池主要填料,试验设计了48种不同参数的原料配比,以有效改善湿陷性黄土的低渗透性为基准(大于2mm/min)筛选出满足要求的4种环氧树脂与黄土的配比方案,分别是环氧树脂含量5%(b5)、环氧树脂含量10%(b10)、5%环氧树脂+1%造孔剂(b5d1)和10%环氧树脂+1%造孔剂(b10d1).相比传统填料,4种改良材料均对NH4+-N和磷酸盐展现出了更强的吸附能力.其中b5d1用于生物滞留池填料后对NH4+-N和COD的平均去除效果最好,分别达到了93.97%和77.5%,b5能更有效的去除NO3--N(76.6%)、TN(62.4%)和TP(98%).通过微生物分析可知b5含较多参与脱氮过程的菌群如Chloroflexi和Steroidobacter.改良黄土填料生物滞留池可以有效去除NH4+-N、NO3--N、TN、TP和COD.研究表明,环氧树脂改良黄土可以用作生物滞留池填料,能够有效净化径流雨水中的污染物,具有广泛的推广价值.

, correspAuthors=熊家晴, authorNote=null, correspAuthorsNote=
*责任作者,教授,
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周航(2000-),女,陕西汉中人,硕士研究生,主要研究方向为海绵城市生物滞留池..

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周航(2000-),女,陕西汉中人,硕士研究生,主要研究方向为海绵城市生物滞留池..

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周航(2000-),女,陕西汉中人,硕士研究生,主要研究方向为海绵城市生物滞留池..

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Water Research2017119:267-275., articleTitle=Phosphorus (P) recovery coupled with increasing influent ammonium facilitated intracellular carbon source storage and simultaneous aerobic phosphorus & nitrogen removal, refAbstract=null)], funds=[Fund(id=1241050005868434108, tenantId=1146029695717560320, journalId=1234093305789726721, articleId=1241049973807174017, awardId=52070152, language=CN, fundingSource=国家自然科学基金资助项目(52070152), fundOrder=null, country=null)], companyList=[AuthorCompany(id=1241049985286984539, tenantId=1146029695717560320, journalId=1234093305789726721, articleId=1241049973807174017, xref=null, ext=[AuthorCompanyExt(id=1241049985299567451, tenantId=1146029695717560320, journalId=1234093305789726721, articleId=1241049973807174017, companyId=1241049985286984539, language=EN, country=null, province=null, city=null, postcode=null, companyName=null, departmentName=null, remark=Key Lab of Northwest Water Resource, Environment and Ecology, School of Environmental and Municipal 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figureFileSmall=a7kAqyGwzzNH8iwFsvjTRQ==, figureFileBig=wIs8BQ9lNQ5xpbUCFd5TXQ==, tableContent=null), ArticleFig(id=1241050002391355958, tenantId=1146029695717560320, journalId=1234093305789726721, articleId=1241049973807174017, language=CN, label=图11, caption=不同干旱期3组生物滞留柱对COD的去除效率, figureFileSmall=a7kAqyGwzzNH8iwFsvjTRQ==, figureFileBig=wIs8BQ9lNQ5xpbUCFd5TXQ==, tableContent=null), ArticleFig(id=1241050002668180046, tenantId=1146029695717560320, journalId=1234093305789726721, articleId=1241049973807174017, language=EN, label=Fig.12, caption=Relative abundance of different packing microbial communities at the phylum and genus levels, figureFileSmall=bdr85g8aG/fuqnlGYeLPjg==, figureFileBig=qfwUW35oI/6xAAkMS5wrSg==, tableContent=null), ArticleFig(id=1241050002802397785, tenantId=1146029695717560320, journalId=1234093305789726721, articleId=1241049973807174017, language=CN, label=图12, caption=不同填料微生物群落在门和属水平的相对丰度, figureFileSmall=bdr85g8aG/fuqnlGYeLPjg==, figureFileBig=qfwUW35oI/6xAAkMS5wrSg==, tableContent=null), ArticleFig(id=1241050003012113003, tenantId=1146029695717560320, journalId=1234093305789726721, articleId=1241049973807174017, language=EN, label=Table 1, caption=

Table of packing compositions of different bioretention cells

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编号BC1BC2BC3
种植植物麦冬麦冬麦冬
填料层100%黄土+5%环氧树脂(b5)100%黄土+5%环氧树脂+1%碳酸氢铵(b5d1)100%黄土+10%环氧树脂+1%碳酸氢铵(b10d1)
砾石层粒径0.8cm~1.2cm的鹅卵石
), ArticleFig(id=1241050003276354166, tenantId=1146029695717560320, journalId=1234093305789726721, articleId=1241049973807174017, language=CN, label=表1, caption=

不同生物滞留池填料组成表

, figureFileSmall=null, figureFileBig=null, tableContent=
编号BC1BC2BC3
种植植物麦冬麦冬麦冬
填料层100%黄土+5%环氧树脂(b5)100%黄土+5%环氧树脂+1%碳酸氢铵(b5d1)100%黄土+10%环氧树脂+1%碳酸氢铵(b10d1)
砾石层粒径0.8cm~1.2cm的鹅卵石
), ArticleFig(id=1241050003544789635, tenantId=1146029695717560320, journalId=1234093305789726721, articleId=1241049973807174017, language=EN, label=Table 2, caption=

Data of adsorption isotherms of different materials to NH4+-N and PO43--P

, figureFileSmall=null, figureFileBig=null, tableContent=
物质材料LangmuirFreundlich
QmKLR2KfnR2
NH4+-Nb55.281±2.5870.002±0.0010.9860.0186±0.0051.167±0.0820.989
b5d18.266±7.670.001±0.0010.9740.016±0.0051.132±0.0920.979
b101.907±0.7510.003±0.0020.9760.011±0.0041.23±0.1350.972
b10d12.526±2.0330.002±0.0020.9620.007±0.0031.148±0.1490.961
PO43--Pb53.579±0.3680.095±0.0440.8560.758±0.1052.996±0.3070.971
b5d112.158±14.490.002±0.0030.9730.041±0.0151.164±0.1210.979
b104.086±1.8080.007±0.0030.9910.038±0.0071.161±0.0760.992
b10d11.14±0.3250.014±0.0060.9720.029±0.0051.404±0.0860.99
), ArticleFig(id=1241050003695784597, tenantId=1146029695717560320, journalId=1234093305789726721, articleId=1241049973807174017, language=CN, label=表2, caption=

不同材料对NH4+-N和PO43--P的吸附等温线拟合数据

, figureFileSmall=null, figureFileBig=null, tableContent=
物质材料LangmuirFreundlich
QmKLR2KfnR2
NH4+-Nb55.281±2.5870.002±0.0010.9860.0186±0.0051.167±0.0820.989
b5d18.266±7.670.001±0.0010.9740.016±0.0051.132±0.0920.979
b101.907±0.7510.003±0.0020.9760.011±0.0041.23±0.1350.972
b10d12.526±2.0330.002±0.0020.9620.007±0.0031.148±0.1490.961
PO43--Pb53.579±0.3680.095±0.0440.8560.758±0.1052.996±0.3070.971
b5d112.158±14.490.002±0.0030.9730.041±0.0151.164±0.1210.979
b104.086±1.8080.007±0.0030.9910.038±0.0071.161±0.0760.992
b10d11.14±0.3250.014±0.0060.9720.029±0.0051.404±0.0860.99
), ArticleFig(id=1241050003813225121, tenantId=1146029695717560320, journalId=1234093305789726721, articleId=1241049973807174017, language=EN, label=Table 3, caption=

Adsorption kinetic parameters of different materials for NH4+-N and PO43--P

, figureFileSmall=null, figureFileBig=null, tableContent=
物质材料准一级动力学方程准二级动力学方程
QeKR2QekR2
NH4+-Nb50.385±0.0141.42±0.1880.9570.405±0.0205.190±1.3420.934
b5d10.459±0.011.216±0.1030.9740.504±0.0153.187±0.5090.969
b102.55±0.01350.132±18.880.7320.261±0.01303.168±98.560.869
b10d10.331±0.00519.045±1.4110.960.341±0.004101.906±9.6750.98
PO43--Pb54.822±0.1850.049±0.0060.9886.431±0.4520.007±0.0010.984
b5d14.079±0.2340.05±0.0070.9785.426±0.4990.008±0.0020.976
b104.841±0.0850.047±0.0020.9976.499±0.2890.006±9.390.991
b10d13.81±0.1250.023±0.0010.9965.451±0.3280.003±6.1120.993
), ArticleFig(id=1241050005381894832, tenantId=1146029695717560320, journalId=1234093305789726721, articleId=1241049973807174017, language=CN, label=表3, caption=

不同材料对NH4+-N和PO43--P的吸附动力学参数

, figureFileSmall=null, figureFileBig=null, tableContent=
物质材料准一级动力学方程准二级动力学方程
QeKR2QekR2
NH4+-Nb50.385±0.0141.42±0.1880.9570.405±0.0205.190±1.3420.934
b5d10.459±0.011.216±0.1030.9740.504±0.0153.187±0.5090.969
b102.55±0.01350.132±18.880.7320.261±0.01303.168±98.560.869
b10d10.331±0.00519.045±1.4110.960.341±0.004101.906±9.6750.98
PO43--Pb54.822±0.1850.049±0.0060.9886.431±0.4520.007±0.0010.984
b5d14.079±0.2340.05±0.0070.9785.426±0.4990.008±0.0020.976
b104.841±0.0850.047±0.0020.9976.499±0.2890.006±9.390.991
b10d13.81±0.1250.023±0.0010.9965.451±0.3280.003±6.1120.993
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环氧树脂改性黄土作为生物滞留池填料净化径流污染物
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周航 , 周佳佳 , 熊家晴 * , 徐艳玮
中国环境科学 | 水污染与控制 2025,45(1): 175-184
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中国环境科学 | 水污染与控制 2025, 45(1): 175-184
环氧树脂改性黄土作为生物滞留池填料净化径流污染物
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周航 , 周佳佳, 熊家晴* , 徐艳玮
作者信息
  • 西安建筑科技大学环境与市政工程学院,西北水资源与环境生态教育部重点实验室,陕西 西安 710055
  • 周航(2000-),女,陕西汉中人,硕士研究生,主要研究方向为海绵城市生物滞留池..

通讯作者:

*责任作者,教授,
Bioretention cells with epoxy resin modified loess to remove runoff pollutants
Hang ZHOU , Jia-jia ZHOU, Jia-qing XIONG* , Yan-wei XU
Affiliations
  • Key Lab of Northwest Water Resource, Environment and Ecology, School of Environmental and Municipal Engineering, Xi'an University of Architecture and Technology, Xi'an 710055, China
出版时间: 2025-01-20
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选用环氧树脂改良黄土材料作为生物滞留池主要填料,试验设计了48种不同参数的原料配比,以有效改善湿陷性黄土的低渗透性为基准(大于2mm/min)筛选出满足要求的4种环氧树脂与黄土的配比方案,分别是环氧树脂含量5%(b5)、环氧树脂含量10%(b10)、5%环氧树脂+1%造孔剂(b5d1)和10%环氧树脂+1%造孔剂(b10d1).相比传统填料,4种改良材料均对NH4+-N和磷酸盐展现出了更强的吸附能力.其中b5d1用于生物滞留池填料后对NH4+-N和COD的平均去除效果最好,分别达到了93.97%和77.5%,b5能更有效的去除NO3--N(76.6%)、TN(62.4%)和TP(98%).通过微生物分析可知b5含较多参与脱氮过程的菌群如Chloroflexi和Steroidobacter.改良黄土填料生物滞留池可以有效去除NH4+-N、NO3--N、TN、TP和COD.研究表明,环氧树脂改良黄土可以用作生物滞留池填料,能够有效净化径流雨水中的污染物,具有广泛的推广价值.

生物滞留池  /  黄土  /  环氧树脂  /  水质净化  /  原位建设

This paper chose epoxy resin modified loess as the primary filler for the biological retention tank. It tested 48 different raw material types with varying parameters to improve the ratio of epoxy resin to loess as the benchmark (greater than 2mm/min). The corresponding epoxy resin content is 5% (b5), 10% (b10), 5% (b5d1), and 10% (b10d1). The adsorption capability of the four enhanced materials for NH4+ -N and phosphate was stronger than that of conventional fillers. After the biological retention tank was filled, b5d1had the best average removal of NH4+ -N and COD, reaching 93.97% and 77.5%, respectively. b5also removed NO3- -N(76.6%), TN (62.4%), and TP (98%) more successfully than the other two. Through microbial investigation, b5was found to contain more organisms including Chloroflexi and Steroidobacter that are engaged in the flora process. The NH4+ -N, NO3- -N, TN, TP, and COD can all be efficiently removed by an enhanced loess packed biological tank. According to studies, loess enhanced with epoxy resin has a wide range of promotional uses, may be utilized as biological tank packing, and effectively filters contaminants in runoff rainfall.

bioretention cell  /  loess  /  epoxy resin  /  pollutant purification  /  in-situ construction
周航, 周佳佳, 熊家晴, 徐艳玮. 环氧树脂改性黄土作为生物滞留池填料净化径流污染物. 中国环境科学, 2025 , 45 (1) : 175 -184 .
Hang ZHOU, Jia-jia ZHOU, Jia-qing XIONG, Yan-wei XU. Bioretention cells with epoxy resin modified loess to remove runoff pollutants[J]. China Environmental Science, 2025 , 45 (1) : 175 -184 .
生物滞留池作为典型的低影响开发设施之一,已被广泛应用于海绵城市建设中[1-3].填料是影响生物滞留设施污染物去除效果和径流滞留的主要因素,也是影响生物滞留设施建造成本的关键[4].
传统生物滞留池的填料主要选择砂石或沙壤土,砂石开采和运输成本高,且过度开采天然砂会引起生态的破坏[5],而且已经有国家针对非法采砂出台了刑事处罚政策[6].为减少传统砂石填料的使用,提出采用黄土作为黄土地区生物滞留池的填料主体进行原位建造.天然黄土强度高,孔隙结构大,吸水性强[7].但其强度行为容易受水的影响[8-9],土壤被水淹没后体积会突然大幅减小[10].大量水分渗入黄土后,会破坏黄土颗粒之间的结构[11].此时,在自身重力荷载和水的重力荷载的作用下,黄土出现整体沉降和崩塌,无法满足生物滞留池填料的渗水要求[12-13].考虑对天然黄土进行改性,使其满足生物滞留设施的渗透要求.环氧树脂因其较强的韧性、高粘附强度、出色的热稳定性和低廉的成本[14],而被普遍应用于各种工业产品[15-16].且固体环氧树脂作为一种新型的无溶剂环保型环氧树脂已得到广泛关注[17].本研究选用双酚A型环氧树脂作为黄土改性剂,使改性黄土满足生物滞留池渗透性要求.造孔剂的添加会影响填料的比表面积和孔隙率[18],进而影响到材料的渗透性能.碳酸氢铵来源广泛、价格低廉.同时沸点低、易挥发,分解产物全为气体,以其作为造孔剂加热后能够实现产物完全脱除[19].
本研究评估了环氧树脂添加量对改性黄土填料生物滞留池的径流污染物净化效果,通过模拟不同干旱时长的降雨事件,确定不同降雨工况下改良黄土生物滞留系统对雨水中污染物的净化特征,论证了添加定量环氧树脂后的改性黄土作为生物滞留池填料的可行性.
改良材料主要由天然黄土、双酚A型环氧树脂和碳酸氢铵混合而成.改良材料方式如图1所示.添加环氧树脂和碳酸氢铵比例的不同,会对黄土颗粒产生不同的支撑作用和不同面积的孔隙.本次试验设置了不同比例的环氧树脂(5%,10%,15%,20%,25%,30%,35%,40%)和造孔剂(0,1%,3%,5%,10%,20%).黄土取自陕西省西安市,双酚A型环氧树脂购自南昌市辰方胶粘制品有限公司.
根据达西定律采用恒定水头法对填料的渗透性能进行评估,计算公式见式(1).采用傅里叶红外光谱(FTIR)对混合材料表面的官能团进行定性分析.同时,通过X射线衍射(XRD)分析改良黄土内部原子或分子的结构形态等信息.并且根据BET来测定改性填料的孔径分布和比表面积,再由扫描电镜来分析改性填料的微观结构特征.
式中:K为渗透系数,mm/min;Q为渗透流量,mL;L为土壤介质厚度,cm;t为渗透时间,min;A为试验柱截面积,cm2h为水头差,cm.
通过等温吸附实验和吸附动力学实验来分析改良黄土的NH4+-N和磷酸盐吸附特性.
将不同浓度(5,10,15,20,25,30,35,40mg/L)的NH4Cl溶液加入称有1g改良黄土的50mL离心管中(磷酸盐吸附实验加入KH2PO4溶液),并且设置空白和平行样,进行25℃等温吸附实验,采用Langmuir模型见式(2),Freundlich模型见式(3).
式中:Qe为平衡状态下每克吸附材料的吸附量,mg/g;Qm为饱和吸附容量,mg/g;Ce为吸附平衡浓度,mg/L;KLKF分别为Langmuir吸附常数和Freundlich吸附常数,L/mg.
在25℃时的实验条件下,称取1g改良黄土填料于50mL离心管中,加入浓度为10mg/L的NH4Cl溶液(磷酸盐吸附实验加入KH2PO4溶液).然后在振荡0.5,1,2,4,6,8,12,24,48,72h后取离心管内上清液,用分光光度计测定NH4+-N或PO43--P的浓度.采用准一级动力学模型和准二级动力学模型来模拟材料的吸附曲线,其方程分别见式(4)和式(5)
式中:Qe表示平衡时NH4+-N或PO43--P的吸附量,mg/g;Qt表示t时刻时NH4+-N或PO43--P的吸附量,mg/g;Kk分别为准一级和准二级的速率常数.
试验设置3个高65cm、内径10cm的生物滞留柱,依次编号为BC1、BC2、BC3,其对应的填料组成见表1.从上向下,各生物滞留池的结构分层为溢流层(5cm)、种植层(5cm)、填料层(50cm)和砾石层(5cm).出流高度距底部30cm,在填料层与砾石层中间铺设土工布隔离层,种植层种植麦冬.试验装置如图2所示.
本试验采用人工配水.参考西安市城市道路径流污染浓度分布特征[20],模拟径流营养物主要由葡萄糖(C6H12O6)、氯化铵(NH4Cl)、硝酸钾(KNO3)和磷酸二氢钾(KH2PO4)混合而成,污染物浓度分别为COD(100mg/L)、NH4+-N(8mg/L)、NO3--N(8mg/L)和磷(2mg/L).干旱期分别设定为1,2,4 8d,进水流速为11.38mL/min,单次降雨历时为2h.
将每个生物滞留池在单次降雨过程中的出水分别收集至桶内.待出水结束后,取容器中的混合水样作为此次降雨事件的出水样本.取样结束后立即对污染物进行测定.其中COD浓度测定采用快速消解分光光度法;NH4+-N浓度采用纳氏试剂光度法;紫外分光光度法测定NO3--N浓度;碱性过硫酸钾消解紫外分光光度法测定TN浓度;TP浓度采用钼锑抗分光光度法测定.
渗透系数过大会使入渗径流在土壤介质中滞留时间减少,不利于污染物净化,过小的渗透系数又会阻碍径流在填料中的入渗.天然黄土的渗透系数范围在0.18~0.36mm/min[21],达不到生物滞留池的滞渗要求(3~6mm/min)[22-24].环氧树脂的添加可以使黄土的渗透性能提高4倍以上,当环氧树脂的含量大于15%时,改良黄土填料的渗透系数均在15mm/min左右,甚至大于20mm/min,虽然可以满足生物滞留池的渗水要求,但过高的渗透系数会造成生物滞留池水质净化效果变差.研究显示渗透系数大于10mm/min除污效率处于最低值范围[25].为了同时满足渗透与净化的要求,在不同改良材料配比的初始选择中,选择渗透系数在2~10mm/min范围内的改良黄土进行进一步的研究.最终决定选择了环氧树脂含量为5%或10%(b5/b10)、环氧树脂和造孔剂含量分别为5%和1%(b5d1)以及环氧树脂和造孔剂含量分别为10%和1%(b10d1)的改性黄土,不同配比改性剂条件下改良黄土填料渗透系数如图3所示.
烷烃的C-H弯曲振动(1449cm-1)、烯烃的C-H弯曲振动(1032cm-1)和N-H的伸缩振动(873cm-1)在天然黄土和改良黄土中都存在(图4(a)、(b)).由于被固化后的环氧树脂含有环氧基、醚键和羟基等基团,改良黄土在3423,2971,1793和1641cm-1处出现了吸收峰,分别属于羟基的伸缩振动、C-H的拉伸振动、C=C的拉伸振动和羧酸C=O的拉伸振动.其中b10d1的烷烃C-H具有更高的强度.除此之外b10、b10d1和未改良黄土还在777cm-1处出现了芳烃的C-H振动.且相比之下,b10d1吸收峰的宽度和强度更大,具有丰富的官能团结构.
尽管添加改性剂会使黄土的主要成分—二氧化硅的衍射峰有一定程度的减弱(图4(c)、(d)),但改良前后黄土所含主要晶体物质类似,都主要包含Al、Si、Ca的氧化物与矿物质珍珠云母.说明改性剂的添加对天然黄土的结晶行为没有影响,不会引起其主要物质成分的改变,这与环氧树脂具有半无定形特性[26]有关.
环氧树脂的添加使黄土的平均孔径从40nm缩小为32nm左右(图5(a)),添加造孔剂后粒径又扩张为36nm左右,这与环氧树脂的强粘合性和碳酸氢铵的受热挥发有关.在低倍镜下黄土表面颗粒(图6(a))较大并呈现团状聚集,颗粒间紧密连接,颗粒呈不规则排列,具有丰富的孔隙结构和大的比表面积.在高倍镜下(图6(b)),黄土颗粒表面粗糙,有较多的凸起,说明它具备较高的比表面积(13.27m2/g).相比未改良黄土,只加入环氧树脂的材料(图6(c)-6(g))其颗粒呈较规则排列,团状聚集规律也更明显,且间距减小.其中b10的颗粒接触最为紧密,与其比表面积最小(2.39m2/g)、平均粒径最小(13.5nm)相符.说明环氧树脂的添加能提供一定的支撑作用,有利于改善黄土的大孔隙结构,降低黄土遇水崩塌的可能.在高倍数下看出添加了造孔剂的改良黄土表面发生了显著变化.颗粒之间以片状连接代替团状聚集,且颗粒以狭长的条状为主,与图6(a)相比表面更加光滑平整.相较于只加环氧树脂材料,添加造孔剂使颗粒之间更加松散,这是碳酸氢铵分解产生气体的缘故.
b5对NH4+-N(1.3mg/g)和PO43--P(3.5mg/g)均展现出较大吸附容量(图7),比其余3种填料平均高出5.8%~86.1%.通过比较相关系数,Langmuir和Freundlich模型均能较好的描述4种材料的NH4+-N吸附过程,而PO43-P只适用Freundlich模型描述.说明改良材料对NH4+-N的多层吸附和单层吸附都存在,而对PO43--P属于表面多层不均匀吸附[27].4种材料Freundlich等温线系数n值均大于1(表2),说明改良黄土可以有效吸附氮磷[26].其中b10最易吸附NH4+-N,b5最易吸附PO43--P.环氧树脂的过量添加不利于氮磷的吸附,b5/b5d1对氮磷的吸附量比b10/b10d1高61.4%~87.4%.结合BET结果分析,环氧树脂的强流动性和高粘合性使其入渗到黄土孔隙中,材料孔径缩小,比表面积减小从而减少了材料能提供的吸附位点.
两种动力学模型拟合下改良黄土对氮磷的Qe均大于砂子[28]表3),说明改良黄土对氮磷吸附能力远大于生物滞留池传统填料(砂子).对比动力学模型对NH4+-N吸附的R2,b5/b5d1更符合准一级动力学模型,其吸附机制主要受分子间作用力引起,b10/b10d1更符合准二级动力学模型,主要受化学作用控制[29].b5/b5d1在前1h内呈快速吸附阶段且饱和时间较b10/b10d1滞后(图8a),说明NH4+-N的吸附迁移过程所受阻力较少,材料显示出更大的吸附容量.相同环氧树脂添加量下,加入造孔剂的改良黄土显示出更大的吸附容量.因为碳酸氢铵挥发产生的孔隙增加了材料的比表面积,为NH4+-N提供更多吸附位点.
4种材料对PO43--P的两种动力学模型R2相近.根据试验数据由准一级动力学模型计算出的NH4+-N理论吸附量与实际吸附量接近,确定改良黄土对PO43--P的吸附更受颗粒传质阻力影响的物理作用控制而非与电子转移有关的化学控制[30],这可能与环氧树脂的绝缘性有关.综上,选择b5、b5d1和b10d1进行后续模拟雨水试验.
不同干旱期后,改良黄土对NH4+-N去除率比传统填料高出约5%~8%[31].环氧树脂的添加使黄土的吸附性能强于砂石.随着干旱天数的增加,改良材料的NH4+-N去除效率逐步提升至90%左右.长期干旱使更多氧气进入生物滞留池促进硝化反应,NH4+-N的转化使材料空出更多吸附位点.相同干旱期下,三组生物滞留柱的NH4+-N去除率均达到了83%以上,其中BC2最高达到了93.97%.这是因为b5d1有较大NH4+-N吸附容量,与2.2中结论相符.
随着干旱期的延长,三种材料NO3--N去除率均增加.较长的干旱期导致雨水停留时间的增加,会促进反硝化作用.这一结果与黎雪然等[32]的研究结论一致.三种材料的生物柱在干8d时NO3--N仍有淋出,分析其原因可能是干旱期间由NH4+-N转化而来的NO3--N导致填料中NO3--N总负荷增大,无法被反硝化细菌完全降解,故出现淋出的情况.尽管如此,BC1仍有高达76.6%的NO3--N去除率.TN的去除规律(图9i~l)与NO3--N相似,BC1的TN去除率最高(62.4%).TN的去除与NH4+-N和NO3--N直接相关.NH4+-N平均去除率整体较高,TN的去除率更多依赖于NO3--N的去除效果,说明NO3--N是生物滞留设施出水中的主要氮形式.
改良黄土生物滞留池的TP去除率均在98%以上(图(10)),比传统填料高出约30%左右[33].尽管三个生物柱在干旱8d后净化能力有所降低,但波动范围在2%以内,说明改良黄土对TP的去除基本不受干旱期的影响.BC1的除磷性能受干旱影响最小(97.9%~99.9%),生物滞留池中磷的去除主要依赖于填料的吸附[34],与2.2中b5对磷有更强的吸附性能的结论相符.
在干1d时,BC3对COD的平均去除率最高(86.6%),其次是BC2(83.0%)和BC1(80.2%).对比相同淹没区和降雨条件下的传统生物滞留池有机物去除效果[33],改良黄土更加有效.受干旱期影响,BC3、BC2和BC1对COD平均去除率分别降为76.1%、77.5%和71.1%,说明BC2展示出更加稳定的有机物去除能力.随着干旱期的延长,三种材料COD利用率下降.但是整体而言去除率都在60%~90%之间,而传统填料生物滞留池的COD去除率最高仅达到60%左右[31].因此改良黄土的COD去除能力较强.COD去除率的高低依赖于微生物对有机物的降解能力,微生物可以利用有机物完成自身生长繁殖.较长干旱期不利于生物滞留池对有机物的去除[35],这是因为长时间干燥会使微生物生长受限.
BC1和BC2有较好去除营养盐效果,针对两者进行门水平的细菌群落结构评估(图12(a)).Proteobacteria(57.70%~60.02%)、Bacteroidetes(8.70%~14.63%)、Verrucomicrobia(5.47%~7.81%)、Acidobacteria(7.37%~4.40%)4种门群在两种填料中都普遍存在.b5的Chloroflexi门群丰度更大,Chloroflexi门群中多为兼性厌氧性细菌,这与b5材料低孔隙度所创造的厌氧环境相契合,它与亚硝酸盐氧化有关[36],可以提高脱氮的效率[37].b5d1的Firmicutes(4.39%)和Nistrospirae(3.68%)具有优势.Firmicutes是革兰氏阳性菌之一,可在好氧或缺氧环境下进行代谢,参与硝化和反硝化过程[38],且在可用底物环境较差时会占据主要地位[39];Nistrospirae与好氧条件下的自养硝化作用有关[40].
为进一步了解细菌特征,对填料的微生物群落结构进行更细致划分(图12(b)).两种改性材料的优势属群有差异,b5的优势属群有Sphingobium(5.17%~17.29%)和Steroidobacter(6.23%~7.36%),占其细菌总数的43.01%.其中Sphingobium可以降解有机物[41-42]Steroidobacter是一种反硝化细菌,可以在厌氧条件下有效去除氮[41-43],这解释了BC1的NO3--N净化效果较好的原因.PseudomonasNitrospira是b5d1的优势属,两者占其细菌总数的28.21%.其中Pseudomonas是一种兼性厌氧菌,可以参与聚磷过程[44]Nitrospira可以氧化亚硝酸盐,在硝化作用中扮演重要角色[40].分析表明改良黄土具有多种有利于脱氮除磷的微生物群落结构,用作生物滞留池填料能提供高效的营养盐去除效果.
3.1 添加环氧树脂可以有效改善黄土的低渗透性,但添加量不宜超过10%.
3.2 环氧树脂的添加改变了黄土原有的大孔隙结构,对天然黄土颗粒能提供一定的支撑作用,使其颗粒排列更加规则,间距更紧凑.
3.3 不同比例改性剂与造孔剂的添加在生物滞留池中去除效果有所不同:b5d1对NH4+-N和COD的平均去除效果较好,分别达到了93.97%和77.5%.而b5去除NO3--N(76.6%)、TN(62.4%)、和TP(98%)的效果较佳.
3.4 b5和b5d1有丰富的微生物群落结构,且更有利于脱氮细菌(如ChloroflexiNitrospiraSteroidobacterPseudomonas)的生长,从而达到更好的营养盐去除效果.
  • 国家自然科学基金资助项目(52070152)
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  • 接收时间:2024-06-03
  • 首发时间:2026-03-18
  • 出版时间:2025-01-20
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  • 收稿日期:2024-06-03
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国家自然科学基金资助项目(52070152)
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    西安建筑科技大学环境与市政工程学院,西北水资源与环境生态教育部重点实验室,陕西 西安 710055

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2种不同金属材料的力学参数

Family
属数
Number of
genus
种数
Number of
species
占总种数比例
Percentage of
total species (%)

Genus
种数
Number of
species
占总种数比例
Percentage of total
species (%)
鹅膏菌科Amanitaceae 2 11 5.26 鹅膏菌属 Amanita 10 4.78
小菇科 Mycenaceae 2 12 5.74 丝盖伞属 Inocybe 5 2.39
多孔菌科 Polyporaceae 8 14 6.70 蜡蘑属 Laccaria 5 2.39
红菇科 Russulaceae 3 23 11.00 小皮伞属 Marasmius 6 2.87
小菇属 Mycena 11 5.26
光柄菇属 Pluteus 5 2.39
红菇属 Russula 17 8.13
栓菌属 Trametes 5 2.39
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