固定化细胞膜生物反应器脱除地下水中硝酸盐的研究
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摘要
山东省章丘市村镇地下水普遍存在硝酸盐浓度过高的现象,这对当地居民的饮用水安全构成了极大威胁,将地下水中硝酸盐浓度降到安全水平显得尤为重要。
本课题结合固定化细胞技术与膜技术,构建新型膜生物反应器,脱除地下水中的硝酸盐。首先,以脱氮效果为主要指标,对固定化细胞膜的制备条件进行了探索；然后,构建新型膜生物反应器,采用两种不同模式,探索碳源种类、C/N、初始硝态氮浓度、温度、pH等条件对脱氮效果的影响；再者,考察了碳源投加方式的改变及碳源重复利用对反硝化的影响；最后,对反应器两种不同模式的脱氮性能进行了比较,并评估了固定化细胞膜的使用稳定性。
研究结果表明：(1)固定化细胞膜适宜的制备条件为细菌接种量2%(w/v)、膜的厚度4mm、冷冻-解冻次数4次；(2)乙醇为较适宜的反硝化碳源,硝酸盐降解速率与C/N、初始硝态氮浓度及温度正相关,适宜的脱氮条件为C/N=8、T=30℃、pH=7-8；(3)采用分批投加碳源的方式可以有效降低亚硝酸盐与CODMn的积累,碳源重复利用可以节约外加碳源的消耗；(4)新型膜生物反应器的两种不同模式在脱氮效果方面各有优劣,固定化细胞膜具有较好的使用稳定性及较长的使用寿命。
The nitrate concentration is generally high in the groundwater of Zhangqiu City, Shandong province. It poses a threat to drinking water safety of local residents. So it is especially important to reduce the nitrate concentration to the safe level.
The immobilized-cell process and membrane filtration process was combined together in this research, and a new membrane bioreactor was developed for removing nitrate from groundwater. First, the making conditions of immobilized-cell membrane were explored. Second, two new membrane bioreactors were designed and constructed, and the effect of carbon source types, C/N, initial nitrate concentration, temperature and pH on denitrification process were investagted in these two bioreactors. Then, the effect of carbon source dosing manner and residual carbon source reusing on denitrification were studied. Finally, the denitrification performance of the two different operation modes was compared, and the stability of immobilized-cell membrane was evaluated.
The results showed:(1)The suitable making conditions of immobilized cell membrane were 2%(w/v)of bacterial inoculum,4mm of membrane thickness,4 times of frozen-thawed cycle; (2) Ethanol is a suitable denitrification carbon source. The degradation rate of nitrate is proportional to C/N, initial nitrate concentration, temperature(10℃-30℃), and the suitable C/N ratio, temperature, pH value are 8,30℃and 7-8, respectively; (3) Relative to the single dose of external ethanol, the two-dose supplementation produced better treatment results as evidenced by the lower concentrations of NO2--N and ethanol (as measured by CODMn) of the effluent, and for saving carbon source the residual carbon source could be reused; (4)The two different modes of the new membrane bioreactor showed different advantages during denitrification processes, and the operational system remained stable for about 10 months.
本课题结合固定化细胞技术与膜技术,构建新型膜生物反应器,脱除地下水中的硝酸盐。首先,以脱氮效果为主要指标,对固定化细胞膜的制备条件进行了探索；然后,构建新型膜生物反应器,采用两种不同模式,探索碳源种类、C/N、初始硝态氮浓度、温度、pH等条件对脱氮效果的影响；再者,考察了碳源投加方式的改变及碳源重复利用对反硝化的影响；最后,对反应器两种不同模式的脱氮性能进行了比较,并评估了固定化细胞膜的使用稳定性。
研究结果表明：(1)固定化细胞膜适宜的制备条件为细菌接种量2%(w/v)、膜的厚度4mm、冷冻-解冻次数4次；(2)乙醇为较适宜的反硝化碳源,硝酸盐降解速率与C/N、初始硝态氮浓度及温度正相关,适宜的脱氮条件为C/N=8、T=30℃、pH=7-8；(3)采用分批投加碳源的方式可以有效降低亚硝酸盐与CODMn的积累,碳源重复利用可以节约外加碳源的消耗；(4)新型膜生物反应器的两种不同模式在脱氮效果方面各有优劣,固定化细胞膜具有较好的使用稳定性及较长的使用寿命。
The nitrate concentration is generally high in the groundwater of Zhangqiu City, Shandong province. It poses a threat to drinking water safety of local residents. So it is especially important to reduce the nitrate concentration to the safe level.
The immobilized-cell process and membrane filtration process was combined together in this research, and a new membrane bioreactor was developed for removing nitrate from groundwater. First, the making conditions of immobilized-cell membrane were explored. Second, two new membrane bioreactors were designed and constructed, and the effect of carbon source types, C/N, initial nitrate concentration, temperature and pH on denitrification process were investagted in these two bioreactors. Then, the effect of carbon source dosing manner and residual carbon source reusing on denitrification were studied. Finally, the denitrification performance of the two different operation modes was compared, and the stability of immobilized-cell membrane was evaluated.
The results showed:(1)The suitable making conditions of immobilized cell membrane were 2%(w/v)of bacterial inoculum,4mm of membrane thickness,4 times of frozen-thawed cycle; (2) Ethanol is a suitable denitrification carbon source. The degradation rate of nitrate is proportional to C/N, initial nitrate concentration, temperature(10℃-30℃), and the suitable C/N ratio, temperature, pH value are 8,30℃and 7-8, respectively; (3) Relative to the single dose of external ethanol, the two-dose supplementation produced better treatment results as evidenced by the lower concentrations of NO2--N and ethanol (as measured by CODMn) of the effluent, and for saving carbon source the residual carbon source could be reused; (4)The two different modes of the new membrane bioreactor showed different advantages during denitrification processes, and the operational system remained stable for about 10 months.
引文
[1]Pontius FW. Nitrate and cancer:is there a link[J]J.AWWA.1993,85(4):12-14
[2]Bouchard DC,Willams MK,Suranpalli RY.Nitrate contamination of groundwater sources and potential health effects[J].J.Am.Water Assoc..1992,84(9):85-90
[3]Abdulrahman I,Alabdula'Aly.Nitrate concentrations in Riyadh, Saudi Arabia drinking water supplies[J]. Environ. Monit. Assess..1997,47:315-324
[4]孙景云,左犀.地下水饮用水源地的保护[J].环境科学.1996,17(5)：20-24
[5]孙彭力,王慧君.氮素化肥的环境污染[J].环境污染与防治.1995,17(1)：38-41
[6]Bernard TN,Jeffrey DS.Nutrients in groundwater of the conterminous United States 1992-1995[J].Environ.Sci.Technol.2000,34:1156-1165
[7]Hiscock KM,Lloyd JW,Lemer DN,et al.An engineering solution to the nitrate problem of a Borehole at Swafham,Norfolk,UK[J] Journal of Hydrology.1989(107):267-281
[8]Spalding RF,Exner ME.Occurrence of nitrate in groundwater-a review[J].J.Environ. Qual.. 1993(22):392-402
[9]Canter LW.Nitrates in Groundwater[M].Lewis publishers,New York.1997
[10]World Health Organization, Guidelines for drinking water quality. World Health Organization. Geneva,1996
[11]Costa JL,Massone H,Martinez D, et al.Nitrate contamination of aquifer and accumulation in the unsaturated zone[J].Agricultural Water Management.2002,57:33-47
[12]Van Maanen J,Van Dijk A, Mulder K,et al.Consumption of drinking water with high nitrate levels causes hypertrophy of the thyroid[J].Toxicol.Lett.1994,72:365-374
[13]Elmidaoui A,Elhannouni F,Mebkouchi Sahli MA,et al. Pollution of nitrate in Moroccan groundwater:removal by electrodialysis[J]. Desalination.2001,136:325-332
[14]徐芳香,陆雍森.我国地下水中硝酸盐污染防治及水源保护区划分[J].污染防治技术.1999,12(1)：20-23
[15]毕二平,李政红.石家庄市地下水中氮污染分析[J].水文地质工程.2001,28(2)：31-34
[16]戴启,莫美仙,陈海宁.昆明盆地北部浅层地下水硝酸盐污染分析[J].云南地质.2009,28(4)：437-444
[17]赵同科,张成军,杜连凤等.环渤海七省(市)地下水硝酸盐含量调查[J].农业环境科学学报.2007,26(2)：779-783
[18]金赞芳,王飞儿,陈英旭等.城市地下水硝酸盐污染及其成因分析[J].土壤学报.2004,41(2)：252-257
[19]European Chemical Industry Ecology&Toxicology Center.Technical Report 27:Nitrate and Drinking Water.European Chemical Industry Ecology& Toxicology Center,Belgium. 1988
[20]Fan AM,Steinberg V.Nitrate in drinking water:Methemoglobinmia and reproductive/ developpmental toxicity[J].Toxicologist.1995,15 (1):36
[21]刑林.去除地下水中硝酸盐的方法研究[D].合肥工业大学.2007
[22]Kostraba JN,Gay EC,Reviewrs M, et al.Nitrate levels in community. Drinking water sand risk of IDDM[J].Diabetes Care.1992,15:1505-1508
[23]Law G,Parslow R,Mickinney P, et al.Non-Hodgkin's lymphoma and nitrate in dringking water:a study in Yorkshire,United Kingdom[J].Epidemiology Community Health.1999, 53:383-384
[24]Jan MS,Maaxen V,Alberin HJ, et al.Nitrate in drinking waters and risk of childhood diabetes in the Netherlands[J]. Diabetes Care.1999,22(10):1750
[25]Janos S,Istvan K,Orsolya F, et al.Association between gastric cancer mortality and nitrate content of drinking water:Ecologocal Study on small area in equalities[J]. European Jounral Epidemiology.2001,17:443-447
[26]Jennifer HB,Roger CP,Patricia AM, et al.Nitrate in drinking water and the incidence of gastric,esophageal,and brain cancer in York shire, England[J].Cancer causes and control.1998,9:153-159
[27]Steiridorf K,Schlehofer B,Becher H, et al.Nitrate in drinking water:A case control study on primary brain tumours with an embedded drinking water survey in Germany[J]. International Journal Epidemiology.1994,23:451-457
[28]Nolan BT,Ruddy BC,Hitt KJ,et al.Risk of nitrate in groundwaters of the United States-a national perspective [J]. Environ. Sci. Technol.1997,31(8):2229-2236
[29]刘兆昌,张兰生等编著.地下水系统的污染与控制[M].中国环境科学出版社,北京.1991
[30]减家业.东海北部海水中硝酸盐(NO3--N)的分布及其成因[J].黄渤海海洋.1999,17(3)：50-56
[31]余瑞兰,菠湘平,魏泰莉等.分子氮和亚硝酸盐对鱼类的危害及其对策[J].中国水产科学.1999,6(3)：73-77
[32]World Health Organization(WHO).Guidelines for Drinking Water Quality. Recommen-dations.1984,2,Geneva:290-292
[33]Environmental Protection Agency(EPA)1989.National Primary and Secondary Drinking water Regulations;Proposed Rule,Fed.Reg..54:22077
[34]Health Canada.Guidelines for Canadian Drinking Water Quality,6thed.Ministry of health, Ottawa.1996
[35]European Community,Council directive of July 1980 relating to the quarry of water intended for human consumption,Official J.European Community, Brussels, Belgium. 1980,23(L229):11-29
[36]Williams AE,Lund LJ,Johnson JA,et al.Natural and anthropogenic nitrate contamination of groundwater in a rural community.California[J].Environ.Sci.Technol..1998,32(1):32-39
[37]Keeney DR.Sources of nitrate to groundwater [J].Critical Reviews in Environmental Control.1986,16(3):257-304
[38]Canter L.W..Nitrates in Groundwater[M].CRC Press,Boca Raton,FL.1997
[39]易秀.氮肥的渗漏性研究[J].农业环境保护.1991,10(5)：223-226
[40]冯绍元,郑耀泉.农田氮素的转化与损失及其对水环境的影响[J].农业环境保护.1996,5(6)：277-280
[41]Belgiorno V,Napoll RM.Groundwater quality monitoring[J].Water Sci.Technol.. 2000, 42(1-2):37-41
[42]武志杰.化学肥料与生物圈[J].农业环境保护.1994,13(6)：279-282
[43]史静,张乃明,褚素贞等.溪泡流域地下水硝酸盐污染特征及影响因素研究[J].农业环境科学学报.2005,24(增刊)：103-107
[44]张维理,田哲旭,张宁等.我国北方农用氮肥造成地下水硝酸盐污染的调查[J].植物营养与肥料学报.1995,1(2)：80-87
[45]姜桂华,王文科,杨晓婷等.关中盆地潜水硝酸盐污染分析及防治对策[J].水资源保护.2002(2)：6-8
[46]Haruvy N,Hadas A,Ravina I,et al.Cost assessment of groundwater pollution [J]. Water Sci. Technol..2000,42(1-2):135-140
[47]金速.辽宁省地下水硝酸盐污染成因分析及其防治对策探讨[J].基础地质.1997,1：63-69
[48]朱济成.关于地下水硝酸盐污染原因的探讨[J].北京地质.1995,(2)：20-26
[49]童桂华.去除地下水硝酸盐PRB介质试验研究—离子交换树脂的选择与电再生[D].中国海洋大学.2008
[50]Rautenbach R,Kopp W,Van Opbergen G,et al.Nitrate reduction of well water by reverse osmosis and electrodialysis studies on the plant performance and cost[J].Desalination. 1987,65:241-258
[51]Roveri C,Genon G,Giacosa D,et al. Ground water nitrate removal:Comparison between reverse osmosis and heterotrophic bacterial process[J].Water Supply.2000,18:400-404
[52]Burke JE,Michley M,Truesdally J,et al.Usefulness of networking in membrane plant design and operation[J].Desalination.1995,102:77-80
[53]Kapoor A,Viraraghavan T.Nitrate removal from drinking water-review[J].J. Environ. Eng..1997,123(40):371-380
[54]黄民生,刘遂庆.饮用水中硝酸盐氮去除技术的研究与应用[J].污染防治技术.1996,9(1)：21-23
[55]Clifford D,Liu X.Biological denitrification of spent regenerant brine using a sequencing batch reactor[J].Water Res..1993,27(9):1477-1484
[56]Ozturk N,Bektas TE.Nitrate removal from aqueous solution by adsorption onto various materials[J].J.Hazard.Mater..2004,112(1):155-162
[57]Lame CF.The chemical reduction of nitrate in aqueous solution[J].Coord.Chem. Rev.. 2000,199:159-179
[58]郝志伟,李亮,马鲁铭.零价铁还原法脱除地下水中硝酸盐的研究[J].中国给水排水. 2008,24(17)：36-39
[59]Choe S,Chang YY,Hwang KY,et al.Kinetics of reductive denitrification by nanoscale zero valentiron [J]. Chemosphere.2000,41:1307-1314
[60]张燕,陈英旭,刘宏远.地下水硝酸盐污染的控制对策及去除技术[J].农业环境保护.2002,21(2)：182-184
[61]孟凡生,王业耀,薛咏海.饮用水中硝酸盐的去除[J].净水技术.2005.24(3)：33-37
[62]John M,James RB.Photochemistry of nitrite and nitrate in aqueous solution:a review [J]. J.Photochem.Photobiol.,A.1999,128:1-13
[63]沈梦蔚.地下水硝酸盐去除方法的研究[D].浙江大学.2004
[64]毕二平,张翠云,张胜等.地下水硝酸盐污染原位微生物修复技术研究进[J].水资源保护.2009,25(3)：1-5
[65]刘玲花,王占生,王志石.硫/石灰石滤柱去除地下水中硝酸盐的研究[J].环境工程.1995,13(3)：11-15
[66]张彦浩,钟佛华,夏四清.利用氢自养反硝化菌处理硝酸盐污染地下水的研究[J].水处理技术.2009,35(5)：75-78
[67]曲久辉,范斌,刘锁祥等.电解产氢自养反硝化去除地下水中硝酸盐氮的研究[J].环境科学.2001,22(6)：49-52
[68]王海燕,曲久辉,雷鹏举.电化学氢自养与硫自养集成去除饮用水中的硝酸盐[J]环境科学学报.2002,22(6)：711-715
[69]金赞芳,陈英旭,小仓纪雄.以棉花为碳源去除地下水硝酸盐的研究[J].农业环境科学学报.2004,23(3)：512-515
[70]金赞芳,李文腾,潘志彦等.地下水硝酸盐去除方法[J].水处理技术.2006,32(8)：34-37
[71]McCleaf PR,Schroeder ED.Denitrification using a membrane immobilized biofilm[J]. J.AWWA.1995,87(3):77-86
[72]Bruce OM, Edward DS.Biological denitrification in continuous flow membrane reactor [J].Water Res..1999,33:1845-1850
[73]Bruce OM, Edward DS.Hydrogenotrophic denitrification in a microporous membrane reactor[J].Water Res..2002,36:4683-4690
[74]曹敬华,郑西来,潘明霞等.萃取膜生物反应器去除地下水硝酸盐[J].西安建筑科技大学学报(自然科学版).2006,38(4)：574-579
[75]Crespo JG,Reis AM,Fonseca AD,et al.Ion exchange membrane bioreactor for denitrify-cation of water[J].1999,Portuguese National Patent No.102385N
[76]Anabela DF,Joao GC,Jonas SA, et al.Drinking water denitrification using a novel ion-exchange membrane bioreactor[J].Environ. Sci. Technol..2000,34 (8):1557-1562
[77]Velizarov S.,Rodrigues CM,Reis MA, et al.Mechanism of charged pollutants removal in an ion exchange memebrane bioreactor:Drinking water denitrification[J]. Biotechnol. Bioeng..2001,71:245-254
[78]Matos CT,Velizarov S.,Crespo JG, et al.Simultaneous removal of perchlorate and nitrate from drinking water using the ion exchange memebrane bioreactor concept[J]. Water Res..2006,40:231-240
[79]于霞,柴立元,甘雪萍.细胞固定化技术及其在废水处理中的应用研究[J].工业水处理.2001,21(10);9-12
[80]陈铭,周晓云.固定化细胞技术在有机废术中的应用与前景[J].水处理技术.1997,23(2)：98
[81]谭佑铭.反硝化菌固定化技术及饮用水脱氮研究[D].华中科技大学医学院.2002：30-31
[82]袁林江.聚乙烯醇(PVA)固定化反硝化菌的脱氮特性[J].中国环境科学.1998,18(2)：189-191
[83]Kim YS,Nakano K, Lee TJ,et al.On-site nitrate removal of groundwater by an immobilized psychrophilic denitrifier using soluble starch as a carbon source [J]. Biotechnol. Bioeng..2002,93(3):303-308
[84]Uemotoa H,Suzukib M,Moritaa M,et al.Simplified denitrification system using ethanol released from non-porous polyethylene-film bag[J].Biochem.Eng.J..2009,45:35-40
[85]Lemoine D,Jouenne H, Junter GM.Biological denitrification of water in a two-chambered immobilized-cell bioreactor[J].Appl Microbiol.Biotechnol..1991,36:257-264
[86]Hashimoto S,Furukawa K.Immobilization of activated sludge by PVA-boric acid method [J].Biotechnol.Bioeng..1987,30:52-59
[87]Chen KC,Lin YF.Immobilization of microorganisms with phosphorylated polyvinyl alcohol(PVA)gel[J].Enzyme Microb.Technol.1994,16:79-83
[88]Okazaki M,Hamada T,Fujii H,et al.Development of polyvinyl alcohol hydrogel for wastewater cleaning.Study of polyvinyl alcohol gel as a carrier for immobilizing microorganisms[J]. J. Appl. Polym. Sci..1995,58:2235-2241
[89]Ariga O,Takagi H,Nishizawa H,et al.Immobilization of microorganisms with PVA burdened by iterative freezing and thawing[J].J. Ferment Technol..1987,65:651-658
[90]曹国民,赵庆祥,孙贤波等.固定化细胞膜的制备及其特性研究[J].中国环境科学.2001,21(3)：207-211
[91]曹国民,赵庆祥,孙贤波等.氨氮、硝酸盐氮和亚硝酸盐氮在PVA凝胶膜中的扩散性能[J].环境科学.2002,23(2)：65-68
[92]水和废水监测分析方法(第四版)[M].中国环境科学出版社,北京.2002
[93]谭佑铭,罗启芳.固定化反硝化菌去除水中硝酸盐的研究[J].环境与健康.2001,18(6)：371-373
[94]Kuo-Cheng Chen,Shihn-Chang Lee,Sheng-Chi Chin,et al.Simultaneous carbon-nitrogen removal in wastewater using phosphorylated PVA-immobilized microorganisms[J]. Enzyme Microb. Technol..1998,23:311-320
[95]Patrick G.H,Terry AM,Kyoung SR, et al.Denitrification of agricultural drainage line water via immobilized denitrification sludge[J]. J. Environ. Sci. Health., Part A.2008, (43):1077-1084
[96]曹国民,赵庆祥,龚剑丽等.单级生物脱氮的特性研究[J].环境科学.2002,21(3)：40-43
[97]Nilsson I,Ohlson S.Columnar denitrification of water by immobilized pseudomonas denitrificans cells[J]. Eur.J.Appl. Microb. Biotechnol..1982(14):86-90
[98]Nilsson I,Ohlson S,Haggstrom L,et al.Denitrification of Water Using Immobilized pseudomonas denitrificans Cells [J].Eur.J.Appl.Microb. Biotechnol.. 1980(10):261-274
[99]田晋红,熊平,董莉仙等.固定化反硝化细菌脱氮的研究[J].西南农业大学学报(自然科学版).2004,26(3)：318-321
[100]挥发性脂肪酸(VFA)的测定.豆丁网.http://www.docin.com/p-57202034.html
[101]Wang QH,Feng CP,Zhao YX,et al.Denitrification of nitrate contaminated groundwater with a fiber-based biofilm reactor[J]. Bioresour. Technol..2009 (100):2223-2227
[102]闫博.高效反硝化菌的分离及其在水体中脱氮规律的研究[D].天津大学.2002
[103]Hunter WJ.Accumulation of nitrite in denitrifying barriers when phosphate is limiting [J]. J.Contam. Hydrol..2003(66):79-91
[2]Bouchard DC,Willams MK,Suranpalli RY.Nitrate contamination of groundwater sources and potential health effects[J].J.Am.Water Assoc..1992,84(9):85-90
[3]Abdulrahman I,Alabdula'Aly.Nitrate concentrations in Riyadh, Saudi Arabia drinking water supplies[J]. Environ. Monit. Assess..1997,47:315-324
[4]孙景云,左犀.地下水饮用水源地的保护[J].环境科学.1996,17(5)：20-24
[5]孙彭力,王慧君.氮素化肥的环境污染[J].环境污染与防治.1995,17(1)：38-41
[6]Bernard TN,Jeffrey DS.Nutrients in groundwater of the conterminous United States 1992-1995[J].Environ.Sci.Technol.2000,34:1156-1165
[7]Hiscock KM,Lloyd JW,Lemer DN,et al.An engineering solution to the nitrate problem of a Borehole at Swafham,Norfolk,UK[J] Journal of Hydrology.1989(107):267-281
[8]Spalding RF,Exner ME.Occurrence of nitrate in groundwater-a review[J].J.Environ. Qual.. 1993(22):392-402
[9]Canter LW.Nitrates in Groundwater[M].Lewis publishers,New York.1997
[10]World Health Organization, Guidelines for drinking water quality. World Health Organization. Geneva,1996
[11]Costa JL,Massone H,Martinez D, et al.Nitrate contamination of aquifer and accumulation in the unsaturated zone[J].Agricultural Water Management.2002,57:33-47
[12]Van Maanen J,Van Dijk A, Mulder K,et al.Consumption of drinking water with high nitrate levels causes hypertrophy of the thyroid[J].Toxicol.Lett.1994,72:365-374
[13]Elmidaoui A,Elhannouni F,Mebkouchi Sahli MA,et al. Pollution of nitrate in Moroccan groundwater:removal by electrodialysis[J]. Desalination.2001,136:325-332
[14]徐芳香,陆雍森.我国地下水中硝酸盐污染防治及水源保护区划分[J].污染防治技术.1999,12(1)：20-23
[15]毕二平,李政红.石家庄市地下水中氮污染分析[J].水文地质工程.2001,28(2)：31-34
[16]戴启,莫美仙,陈海宁.昆明盆地北部浅层地下水硝酸盐污染分析[J].云南地质.2009,28(4)：437-444
[17]赵同科,张成军,杜连凤等.环渤海七省(市)地下水硝酸盐含量调查[J].农业环境科学学报.2007,26(2)：779-783
[18]金赞芳,王飞儿,陈英旭等.城市地下水硝酸盐污染及其成因分析[J].土壤学报.2004,41(2)：252-257
[19]European Chemical Industry Ecology&Toxicology Center.Technical Report 27:Nitrate and Drinking Water.European Chemical Industry Ecology& Toxicology Center,Belgium. 1988
[20]Fan AM,Steinberg V.Nitrate in drinking water:Methemoglobinmia and reproductive/ developpmental toxicity[J].Toxicologist.1995,15 (1):36
[21]刑林.去除地下水中硝酸盐的方法研究[D].合肥工业大学.2007
[22]Kostraba JN,Gay EC,Reviewrs M, et al.Nitrate levels in community. Drinking water sand risk of IDDM[J].Diabetes Care.1992,15:1505-1508
[23]Law G,Parslow R,Mickinney P, et al.Non-Hodgkin's lymphoma and nitrate in dringking water:a study in Yorkshire,United Kingdom[J].Epidemiology Community Health.1999, 53:383-384
[24]Jan MS,Maaxen V,Alberin HJ, et al.Nitrate in drinking waters and risk of childhood diabetes in the Netherlands[J]. Diabetes Care.1999,22(10):1750
[25]Janos S,Istvan K,Orsolya F, et al.Association between gastric cancer mortality and nitrate content of drinking water:Ecologocal Study on small area in equalities[J]. European Jounral Epidemiology.2001,17:443-447
[26]Jennifer HB,Roger CP,Patricia AM, et al.Nitrate in drinking water and the incidence of gastric,esophageal,and brain cancer in York shire, England[J].Cancer causes and control.1998,9:153-159
[27]Steiridorf K,Schlehofer B,Becher H, et al.Nitrate in drinking water:A case control study on primary brain tumours with an embedded drinking water survey in Germany[J]. International Journal Epidemiology.1994,23:451-457
[28]Nolan BT,Ruddy BC,Hitt KJ,et al.Risk of nitrate in groundwaters of the United States-a national perspective [J]. Environ. Sci. Technol.1997,31(8):2229-2236
[29]刘兆昌,张兰生等编著.地下水系统的污染与控制[M].中国环境科学出版社,北京.1991
[30]减家业.东海北部海水中硝酸盐(NO3--N)的分布及其成因[J].黄渤海海洋.1999,17(3)：50-56
[31]余瑞兰,菠湘平,魏泰莉等.分子氮和亚硝酸盐对鱼类的危害及其对策[J].中国水产科学.1999,6(3)：73-77
[32]World Health Organization(WHO).Guidelines for Drinking Water Quality. Recommen-dations.1984,2,Geneva:290-292
[33]Environmental Protection Agency(EPA)1989.National Primary and Secondary Drinking water Regulations;Proposed Rule,Fed.Reg..54:22077
[34]Health Canada.Guidelines for Canadian Drinking Water Quality,6thed.Ministry of health, Ottawa.1996
[35]European Community,Council directive of July 1980 relating to the quarry of water intended for human consumption,Official J.European Community, Brussels, Belgium. 1980,23(L229):11-29
[36]Williams AE,Lund LJ,Johnson JA,et al.Natural and anthropogenic nitrate contamination of groundwater in a rural community.California[J].Environ.Sci.Technol..1998,32(1):32-39
[37]Keeney DR.Sources of nitrate to groundwater [J].Critical Reviews in Environmental Control.1986,16(3):257-304
[38]Canter L.W..Nitrates in Groundwater[M].CRC Press,Boca Raton,FL.1997
[39]易秀.氮肥的渗漏性研究[J].农业环境保护.1991,10(5)：223-226
[40]冯绍元,郑耀泉.农田氮素的转化与损失及其对水环境的影响[J].农业环境保护.1996,5(6)：277-280
[41]Belgiorno V,Napoll RM.Groundwater quality monitoring[J].Water Sci.Technol.. 2000, 42(1-2):37-41
[42]武志杰.化学肥料与生物圈[J].农业环境保护.1994,13(6)：279-282
[43]史静,张乃明,褚素贞等.溪泡流域地下水硝酸盐污染特征及影响因素研究[J].农业环境科学学报.2005,24(增刊)：103-107
[44]张维理,田哲旭,张宁等.我国北方农用氮肥造成地下水硝酸盐污染的调查[J].植物营养与肥料学报.1995,1(2)：80-87
[45]姜桂华,王文科,杨晓婷等.关中盆地潜水硝酸盐污染分析及防治对策[J].水资源保护.2002(2)：6-8
[46]Haruvy N,Hadas A,Ravina I,et al.Cost assessment of groundwater pollution [J]. Water Sci. Technol..2000,42(1-2):135-140
[47]金速.辽宁省地下水硝酸盐污染成因分析及其防治对策探讨[J].基础地质.1997,1：63-69
[48]朱济成.关于地下水硝酸盐污染原因的探讨[J].北京地质.1995,(2)：20-26
[49]童桂华.去除地下水硝酸盐PRB介质试验研究—离子交换树脂的选择与电再生[D].中国海洋大学.2008
[50]Rautenbach R,Kopp W,Van Opbergen G,et al.Nitrate reduction of well water by reverse osmosis and electrodialysis studies on the plant performance and cost[J].Desalination. 1987,65:241-258
[51]Roveri C,Genon G,Giacosa D,et al. Ground water nitrate removal:Comparison between reverse osmosis and heterotrophic bacterial process[J].Water Supply.2000,18:400-404
[52]Burke JE,Michley M,Truesdally J,et al.Usefulness of networking in membrane plant design and operation[J].Desalination.1995,102:77-80
[53]Kapoor A,Viraraghavan T.Nitrate removal from drinking water-review[J].J. Environ. Eng..1997,123(40):371-380
[54]黄民生,刘遂庆.饮用水中硝酸盐氮去除技术的研究与应用[J].污染防治技术.1996,9(1)：21-23
[55]Clifford D,Liu X.Biological denitrification of spent regenerant brine using a sequencing batch reactor[J].Water Res..1993,27(9):1477-1484
[56]Ozturk N,Bektas TE.Nitrate removal from aqueous solution by adsorption onto various materials[J].J.Hazard.Mater..2004,112(1):155-162
[57]Lame CF.The chemical reduction of nitrate in aqueous solution[J].Coord.Chem. Rev.. 2000,199:159-179
[58]郝志伟,李亮,马鲁铭.零价铁还原法脱除地下水中硝酸盐的研究[J].中国给水排水. 2008,24(17)：36-39
[59]Choe S,Chang YY,Hwang KY,et al.Kinetics of reductive denitrification by nanoscale zero valentiron [J]. Chemosphere.2000,41:1307-1314
[60]张燕,陈英旭,刘宏远.地下水硝酸盐污染的控制对策及去除技术[J].农业环境保护.2002,21(2)：182-184
[61]孟凡生,王业耀,薛咏海.饮用水中硝酸盐的去除[J].净水技术.2005.24(3)：33-37
[62]John M,James RB.Photochemistry of nitrite and nitrate in aqueous solution:a review [J]. J.Photochem.Photobiol.,A.1999,128:1-13
[63]沈梦蔚.地下水硝酸盐去除方法的研究[D].浙江大学.2004
[64]毕二平,张翠云,张胜等.地下水硝酸盐污染原位微生物修复技术研究进[J].水资源保护.2009,25(3)：1-5
[65]刘玲花,王占生,王志石.硫/石灰石滤柱去除地下水中硝酸盐的研究[J].环境工程.1995,13(3)：11-15
[66]张彦浩,钟佛华,夏四清.利用氢自养反硝化菌处理硝酸盐污染地下水的研究[J].水处理技术.2009,35(5)：75-78
[67]曲久辉,范斌,刘锁祥等.电解产氢自养反硝化去除地下水中硝酸盐氮的研究[J].环境科学.2001,22(6)：49-52
[68]王海燕,曲久辉,雷鹏举.电化学氢自养与硫自养集成去除饮用水中的硝酸盐[J]环境科学学报.2002,22(6)：711-715
[69]金赞芳,陈英旭,小仓纪雄.以棉花为碳源去除地下水硝酸盐的研究[J].农业环境科学学报.2004,23(3)：512-515
[70]金赞芳,李文腾,潘志彦等.地下水硝酸盐去除方法[J].水处理技术.2006,32(8)：34-37
[71]McCleaf PR,Schroeder ED.Denitrification using a membrane immobilized biofilm[J]. J.AWWA.1995,87(3):77-86
[72]Bruce OM, Edward DS.Biological denitrification in continuous flow membrane reactor [J].Water Res..1999,33:1845-1850
[73]Bruce OM, Edward DS.Hydrogenotrophic denitrification in a microporous membrane reactor[J].Water Res..2002,36:4683-4690
[74]曹敬华,郑西来,潘明霞等.萃取膜生物反应器去除地下水硝酸盐[J].西安建筑科技大学学报(自然科学版).2006,38(4)：574-579
[75]Crespo JG,Reis AM,Fonseca AD,et al.Ion exchange membrane bioreactor for denitrify-cation of water[J].1999,Portuguese National Patent No.102385N
[76]Anabela DF,Joao GC,Jonas SA, et al.Drinking water denitrification using a novel ion-exchange membrane bioreactor[J].Environ. Sci. Technol..2000,34 (8):1557-1562
[77]Velizarov S.,Rodrigues CM,Reis MA, et al.Mechanism of charged pollutants removal in an ion exchange memebrane bioreactor:Drinking water denitrification[J]. Biotechnol. Bioeng..2001,71:245-254
[78]Matos CT,Velizarov S.,Crespo JG, et al.Simultaneous removal of perchlorate and nitrate from drinking water using the ion exchange memebrane bioreactor concept[J]. Water Res..2006,40:231-240
[79]于霞,柴立元,甘雪萍.细胞固定化技术及其在废水处理中的应用研究[J].工业水处理.2001,21(10);9-12
[80]陈铭,周晓云.固定化细胞技术在有机废术中的应用与前景[J].水处理技术.1997,23(2)：98
[81]谭佑铭.反硝化菌固定化技术及饮用水脱氮研究[D].华中科技大学医学院.2002：30-31
[82]袁林江.聚乙烯醇(PVA)固定化反硝化菌的脱氮特性[J].中国环境科学.1998,18(2)：189-191
[83]Kim YS,Nakano K, Lee TJ,et al.On-site nitrate removal of groundwater by an immobilized psychrophilic denitrifier using soluble starch as a carbon source [J]. Biotechnol. Bioeng..2002,93(3):303-308
[84]Uemotoa H,Suzukib M,Moritaa M,et al.Simplified denitrification system using ethanol released from non-porous polyethylene-film bag[J].Biochem.Eng.J..2009,45:35-40
[85]Lemoine D,Jouenne H, Junter GM.Biological denitrification of water in a two-chambered immobilized-cell bioreactor[J].Appl Microbiol.Biotechnol..1991,36:257-264
[86]Hashimoto S,Furukawa K.Immobilization of activated sludge by PVA-boric acid method [J].Biotechnol.Bioeng..1987,30:52-59
[87]Chen KC,Lin YF.Immobilization of microorganisms with phosphorylated polyvinyl alcohol(PVA)gel[J].Enzyme Microb.Technol.1994,16:79-83
[88]Okazaki M,Hamada T,Fujii H,et al.Development of polyvinyl alcohol hydrogel for wastewater cleaning.Study of polyvinyl alcohol gel as a carrier for immobilizing microorganisms[J]. J. Appl. Polym. Sci..1995,58:2235-2241
[89]Ariga O,Takagi H,Nishizawa H,et al.Immobilization of microorganisms with PVA burdened by iterative freezing and thawing[J].J. Ferment Technol..1987,65:651-658
[90]曹国民,赵庆祥,孙贤波等.固定化细胞膜的制备及其特性研究[J].中国环境科学.2001,21(3)：207-211
[91]曹国民,赵庆祥,孙贤波等.氨氮、硝酸盐氮和亚硝酸盐氮在PVA凝胶膜中的扩散性能[J].环境科学.2002,23(2)：65-68
[92]水和废水监测分析方法(第四版)[M].中国环境科学出版社,北京.2002
[93]谭佑铭,罗启芳.固定化反硝化菌去除水中硝酸盐的研究[J].环境与健康.2001,18(6)：371-373
[94]Kuo-Cheng Chen,Shihn-Chang Lee,Sheng-Chi Chin,et al.Simultaneous carbon-nitrogen removal in wastewater using phosphorylated PVA-immobilized microorganisms[J]. Enzyme Microb. Technol..1998,23:311-320
[95]Patrick G.H,Terry AM,Kyoung SR, et al.Denitrification of agricultural drainage line water via immobilized denitrification sludge[J]. J. Environ. Sci. Health., Part A.2008, (43):1077-1084
[96]曹国民,赵庆祥,龚剑丽等.单级生物脱氮的特性研究[J].环境科学.2002,21(3)：40-43
[97]Nilsson I,Ohlson S.Columnar denitrification of water by immobilized pseudomonas denitrificans cells[J]. Eur.J.Appl. Microb. Biotechnol..1982(14):86-90
[98]Nilsson I,Ohlson S,Haggstrom L,et al.Denitrification of Water Using Immobilized pseudomonas denitrificans Cells [J].Eur.J.Appl.Microb. Biotechnol.. 1980(10):261-274
[99]田晋红,熊平,董莉仙等.固定化反硝化细菌脱氮的研究[J].西南农业大学学报(自然科学版).2004,26(3)：318-321
[100]挥发性脂肪酸(VFA)的测定.豆丁网.http://www.docin.com/p-57202034.html
[101]Wang QH,Feng CP,Zhao YX,et al.Denitrification of nitrate contaminated groundwater with a fiber-based biofilm reactor[J]. Bioresour. Technol..2009 (100):2223-2227
[102]闫博.高效反硝化菌的分离及其在水体中脱氮规律的研究[D].天津大学.2002
[103]Hunter WJ.Accumulation of nitrite in denitrifying barriers when phosphate is limiting [J]. J.Contam. Hydrol..2003(66):79-91