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伴随着我国城镇化进程的加快,市政污水的处理需求在快速上升。由于我国现代化建设起步较晚,污水排放管网建设多采用合流制[1],致使管道除了承接生活污水之外,还容纳了工业废水及雨水等[2]。当前我国市政污水总体呈现出有机污染物含量低、水质水量变化大、污染物成分复杂等特点[3],导致在污水处理中,生物脱氮的实际效果不佳,出水水质不达标。污水中的大量氮源若不能达到排放标准就进入自然水体,势必加剧河道和湖泊水体的富营养化[4]。因此,解决低碳氮比市政污水含碳量不足的问题,是提高市政污水处理高效脱氮的重要方向。
常规的生物脱氮主要由氨化作用、硝化作用和反硝化作用3个部分完成。根据氮的存在形态,功能微生物菌群在特定微环境下相互协作,共同完成脱氮过程[5]。当前生物脱氮多采用悬浮生长系统为主的缺氧/好氧、厌氧/缺氧/好氧、序批式活性污泥法、氧化沟等传统工艺。但这些传统生物脱氮工艺存在多种缺点,例如:因活性污泥在水中的形态多为絮体状,导致反应装置的水力停留时间和污泥停留时间难以控制;污泥内的自养菌生长周期长,易随出水流出;活性污泥抗环境胁迫能力较差等[6-8]。
为克服上述缺点,以填料为载体的悬浮生长系统正在被广泛采用。其中代表性工艺包括生物接触氧化、生物转盘、及生物滤池等[6,9]。不过,常规填料上附着的活性生物膜厚度一般不超过2 mm。受传质阻力和水力冲击的作用,生物膜较易脱落,因而影响水处理效能。近来有研究在单一反应器中引入改性玄武岩纤维(modified basalt fiber, MBF)做填料。这种新型生物载体可快速吸附活性污泥,形成一种有别于传统生物膜的微生物聚集体(生物巢)[10]。通常,生物巢尺寸可达10 cm以上。其生物量虽然巨大,但并不影响传质和生物活性,因而可实现不同类型污/废水的高效脱氮除碳[11]。相对于传统填料,新型改性玄武岩纤维更适合做生物载体。其能够富集大量的功能微生物菌群,尤其是生长缓慢的氨氧化细菌、亚硝酸盐氧化菌以及异养硝化-好氧反硝化(heterotrophic nitrifying aerobic denitrifying, HN-AD)菌等[12-13]。尽管从材料改性的角度可以优化功能微生物的富集,但功能微生物的生长通常受到生理条件如C/N比的限制。在传统的生物脱氮过程中,生物反硝化需要大量的有机碳源作为电子供体。而我国的市政污水的碳氮比普遍较低,导致反硝化菌生长受到抑制。为了降低出水中含氮污染物的浓度,现有工艺通常通过外加碳源来提高污水的碳氮比。不过,使用外加碳源一方面会增加污水厂的运行成本,另一方面由于实际废水进水的水质水量具有较大的波动性,碳源投加量难以精确控制[14]。
在此背景下,解决市政污水中碳源有效利用的问题就成了当前污水处理领域的研究热点之一。考虑到在偏中性和碱性环境中NO3−/NO2−电对的氧化还原电位高于Fe(II)/Fe(III),研究人员尝试在复杂菌群中投加铁氧化物介导种间电子传递,以实现有机底物氧化与硝酸盐还原的耦合。纳米级铁氧化物如赤铁矿(α-Fe2O3)、磁赤铁矿(γ-Fe2O3)、磁铁矿(Fe3O4)作为半导体和导体材料具有良好的生物亲和性。微生物可以利用这些纳米材料作为电子介体实现电子传递[15]。据报道Geobacter sulfurreducens可以氧化乙酸盐但不能还原NO3−,而Thiobacillus denitrificans能够还原NO3−但不能氧化乙酸盐。两者的共培养并不能实现有机物氧化和硝酸盐还原的耦合发生,但当添加α-Fe2O3或Fe3O4纳米颗粒时共培养体系能成功实现共代谢[16]。此外,研究还发现氢自养反硝化菌的外膜细胞色素对α-Fe2O3具有高度亲和性,借助α-Fe2O3可加速电子向胞内硝酸盐还原酶的传递,从而促进反硝化的进行[17]。因此,铁氧化物介导的种间电子传递为菌群共代谢提供了一种有效途径[18]。此外,对于一些具有跨膜电子转移能力的反硝化菌,进入细胞内部的α-Fe2O3有可能在周质空间直接介导NADH(还原性辅酶I)等电子供体与硝酸盐还原酶之间的电子传递。因此,这种胞内电子传递促进机制也为碳源有效利用提供了新的途径。但是,目前尚未有关于投加铁氧化物以解决市政污水碳源不足问题的研究报道。
为此,本研究选用MBF作为生物载体,在生物接触氧化池中培养生物巢,借助于生物巢独特的好氧-缺氧-厌氧微环境,富集各种与氮转化相关的功能微生物。同时,在池体中投加纳米氧化铁(α-Fe2O3),考察其介导种间或胞内电子转移机制对脱氮效能的刺激作用,并解析氮转化的代谢通路。本研究旨在探索α-Fe2O3介导下碳源有效利用的可行性及潜在的机制,为提高低碳氮比市政污水的高效脱氮提供一种新的策略。
纳米Fe2O3强化MBF生物巢脱氮的机制
Augmentation of nitrogen removal by MBF bio-nests supplemented with nano-Fe2O3
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摘要: 针对我国市政污水C/N比偏低的问题,本研究旨在探讨纳米氧化铁在MBF生物巢反应器中对低C/N比市政污水处理的强化脱氮效果及其机理。将纳米氧化铁添加到MBF生物巢反应器中,处理实际低C/N比市政污水,通过监测脱氮效率和碳源利用情况,结合微生物群落结构和功能基因表达量的分析,评价其处理效果。结果表明,纳米氧化铁的加入可显著提高反应器的脱氮效率,脱氮率提升了58%。微生物群落结构分析结果表明,纳米氧化铁影响了特定脱氮微生物的相对丰度。功能基因表达量分析结果表明,纳米氧化铁下调了微生物外膜上电子转移蛋白的表达,减少了种间电子传递,从而提高了胞内电子的有效利用率。以上结果表明,纳米氧化铁通过调节微生物群落结构和功能基因表达,可提高碳源的利用效率,进而实现对低C/N比市政污水的有效脱氮,可为市政污水处理提供技术途径参考。Abstract: Addressing the issue of low C/N ratio in municipal wastewater in China, this study aims to investigate the enhanced nitrogen removal efficacy and its mechanism of nano-iron oxide in an MBF bio-nest reactor treating municipal wastewater with low C/N ratio. As nano-iron oxide was added to the MBF bio-nest treating actual municipal wastewater with low C/N ratio, the nitrogen removal efficiency and carbon source utilization were monitored, and the microbial community structure and functional gene expression levels were also analyzed, then the performance on treating wastewater with low C/N ratio was evaluated. The results showed that addition of nano-iron oxide significantly increased the nitrogen removal efficiency of the reactor by 58%. Microbial community structure analysis revealed that nano-iron oxide affected the relative abundance of specific nitrogen-removing microorganisms. Functional gene expression analysis found that nano-iron oxide downregulated the expression of electron transfer proteins on the outer membrane of microorganisms, reducing interspecies electron transfer and thereby enhancing the effective utilization of electrons within the cells. Above results indicated that nano-iron oxide increased the efficiency of carbon source utilization and effectively removed nitrogen from municipal wastewater with low C/N ratio through regulating microbial community structure and functional gene expression. This provides a new technical approach for municipal wastewater treatment.
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表 1 原始泥样和反应器中的MLSS和MLVSS及其比值
Table 1. MLSS, MLVSS and their ratios in the raw sludge and reactors
样品 MLSS MLVSS MLSS/MLVSS 原始泥样 4 000 2 211 0.552 对照组 4 125 2 283 0.553 实验组 5 239 2 599 0.496 -
[1] ZHEN Y Z, JIAN Z, GEORGE Z. Transformation of water resource management: A case study of the South-to-North Water Diversion project[J]. Journal of Cleaner Production, 2015, 163: 136-145. [2] 栗清静. 中国水资源利用与水环境保护探析[J]. 绿色环保建材, 2020, 160(6): 56-57. [3] 王仲杰. 探析市政污水处理存在的问题及对策[J]. 皮革制作与环保科技, 2022, 3(20): 179-181. [4] CHEN X J, YUAN L J, ZHAO B B. Capturing influent organic substrate for endogenous denitrification to enhance nitrogen removal in low C/N ratio municipal wastewater[J]. Journal of Water Process Engineering, 2022, 50: 103240. doi: 10.1016/j.jwpe.2022.103240 [5] 王冰, 杨琳, 孙冰, 等. 生物脱氮工艺的原理及研究发展[J]. 建筑与预算, 2020, 295(11): 5-7. [6] 姜瑞, 于振波, 李晶, 等. 生物接触氧化法的研究现状分析[J]. 环境科学与管理, 2013, 38(5): 61-63. doi: 10.3969/j.issn.1673-1212.2013.05.014 [7] 刘亚琴. 基于沸石吸附/再生的改良型A/O脱氮工艺研究[D]. 镇江: 江苏大学, 2018. [8] 刘平. 生活污水A/O处理系统运行优化改造研究[D]. 武汉: 武汉科技大学, 2008. [9] 徐亚同, 史家梁, 张大鹏. 废水处理 第五篇 废水好氧生物处理的方法(一)——活性污泥法[J]. 上海化工, 1998(17): 39-42. [10] NI H C, ZHOU X T, ZHANG X Y, et al. Feasibility of using basalt fiber as biofilm Carrier to construct bio-nest for wastewater treatment[J]. Chemosphere, 2018, 212: 768-776. doi: 10.1016/j.chemosphere.2018.08.136 [11] 倪慧成. 基于改性玄武岩纤维(MBF)填料的污/废水处理技术及其应用研究[D]. 镇江: 江苏大学, 2022. [12] 张倩. 新型玄武岩纤维填料在生活污水处理中的结构组合研究[D]. 镇江: 江苏大学, 2019. [13] 席海朋. 厌氧/好氧折流板反应器强化生活污水脱氮的研究[D]. 镇江: 江苏大学, 2021. [14] 廖宏翔, 肖安琪. 城镇污水处理厂外加碳源分析和可降耗措施探究[J]. 四川化工, 2023, 26(02): 49-51+56. [15] ZHI M W, WEI J L, ZHENG Q Y, et al. Denitrification mechanism in oxygen-rich aquatic environments through long-distance electron transfer[J]. Npj Clean Water, 2022, 5: 61. doi: 10.1038/s41545-022-00205-x [16] SOUICHIRO K, KAZUHITO H, KAZUYA W. Microbial interspecies electron transfer via electric currents through conductive minerals[J]. Proceedings of the National Academy of Sciences of the United States of America, 2012, 109(25): 10042-10046. [17] WANG S Y, YANG X Y, MENG H S, et al. Enhanced denitrification by nano ɑ-Fe2O3 induced self-assembled hybrid biofilm on particle electrodes of three-dimensional biofilm electrode reactors[J]. Environment International, 2019, 125: 142-151. doi: 10.1016/j.envint.2019.01.060 [18] CAROLINA V C, SIMONA R, STEFANO F, et al. Magnetite particles triggering a faster and more robust syntrophic pathway of methanogenic propionate degradation[J]. Environmental Science Technology, 2014, 48(13): 7536-7543. doi: 10.1021/es5016789 [19] ZHANG L H, WANG S J. Bacterial community diversity on in-shell walnut surfaces from six representative provinces in China[J]. Scientific Reports, 2017, 7(1): 10054. doi: 10.1038/s41598-017-10138-y [20] LU J, BREITWIESER F P, THIELEN P, et al. Bracken: estimating species abundance in metagenomics data[J]. Peerj Computer Science, 2017, 3(1): e104. [21] COTILLARD A, KENNEDY S P, KONG L C, et al. Dietary intervention impact on gut microbial gene richness[J]. Nature, 2013, 500(7464): 585. doi: 10.1038/nature12480 [22] 郭欣. 生物透射电镜样品制备过程中常易遇到的问题以及解决办法[J]. 科技信息, 2011, 376(20): 539-540. doi: 10.3969/j.issn.1001-9960.2011.20.468 [23] LI Y, LIU S J, CHEN F M, et al. Development of a dynamic feeding strategy for continuous-flow aerobic granulation and nitrogen removal in a modified airlift loop reactor for municipal wastewater treatment[J]. Science of the Total Environment, 2020, 714: 136764. doi: 10.1016/j.scitotenv.2020.136764 [24] 郑力, 江鹰, 程晓夏. 铁屑耦合固相反硝化对低碳氮比废水中总氮的处理[J]. 环境工程学报, 2022, 16(11): 3716-3727. [25] 杨浩, 张国珍, 杨晓妮, 等. 16S rRNA高通量测序研究集雨窖水中微生物群落结构及多样性[J]. 环境科学, 2017, 38(04): 1704-1716. [26] SOLISIO C, LODI A, CONVERTI A, et al. The effect of acid pre-treatment on the biosorption of chromium(III) by Sphaerotilus natans from industrial wastewater[J]. Water Research, 2000, 34(12): 3171-3178. doi: 10.1016/S0043-1354(00)00059-2 [27] MIGUEL S, LEA W, Sara H, et al. Differential expression of clade I and II N2O reductase genes in denitrifying Thauera linaloolentis 47LolT under different nitrogen conditions[J]. FEMS Microbiology Letters, 2020, 367(24): 205. [28] XU T, YAN L Y, YONG W L, et al. Quantitative ecology associations between heterotrophic nitrification-aerobic denitrification, nitrogen-metabolism genes, and key bacteria in a tidal flow constructed wetland[J]. Bioresource Technology, 2021, 337: 125449. doi: 10.1016/j.biortech.2021.125449 [29] ZHOU X T, ZHAO L, WANG X, et al. Organic and inorganic nitrogen removals by an ureolytic heterotrophic nitrification and aerobic denitrification strain Acinetobacter sp. Z1: elucidatingits physiological characteristics and metabolic mechanisms[J]. Bioresource Technology, 2022, 362: 127792. doi: 10.1016/j.biortech.2022.127792 [30] BAYER B, SAITO M A, MCILVIN M R, et al. Metabolic versatility of the nitrite-oxidizing bacterium Nitrospira marina and its proteomic response to oxygen-limited conditions[J]. The ISME Journal, 2020, 15(4): 1025-1039. [31] GONZÁLEZ C J, LOZA-TAVERA H. Alicycliphilus: current knowledge and potential for bioremediation of xenobiotics[J]. Journal of applied microbiology, 2019, 126(6): 1643-1656. doi: 10.1111/jam.14207 [32] SONDOS A, LAURENS W, BEN A, et al. Denitrification of nitrate and nitrite by ‘Candidatus Accumulibacter phosphatis’hosphatIC[J]. Water Research, 2016, 105: 97-109. doi: 10.1016/j.watres.2016.08.061 [33] GOLUBEV S N, MURATOVA A Y. , PANCHENKO L V , et al. Mycolicibacterium sp. strain PAM1, an alfalfa rhizosphere dweller, catabolizes PAHs and promotes partner-plant growth[J]. Microbiological Research, 2021, 253: 126885. [34] SONG Y, JIANG Y C, LIANG Z L, et al. Casimicrobium huifangae gen. nov. , sp. nov. , a Ubiquitous “Most-Wanted” Core Bacterial Taxon from Municipal Wastewater Treatment Plants[J]. Applied and Environmental Microbiology, 2019, 86(4): 1183-1195. [35] LIANG Y F, PAN Z R , FENG H B, et al. Biofilm coupled micro-electrolysis of waste iron shavings enhanced iron and hydrogen autotrophic denitrification and phosphate accumulation for wastewater treatment[J]. Journal of Environmental Chemical Engineering, 2022, 10(6): 108959. [36] ZHEN J Y, OEHMEN A, WEI W, et al. Synergism and physiological characteristics of glycogen accumulating organisms (GAOs) in anaerobic ammonia oxidation based (anammox-based) systems: Mechanisms and prospects[J]. Chemical Engineering Journal, 2023, 478: 147316. doi: 10.1016/j.cej.2023.147316 [37] BERNARD S L, MARIE-NOËLLE M, GRIMONT P A D, et al. Description of Afipia birgiae sp. nov. and Afipia massiliensis sp. nov. and recognition of Afipia felis genospecies A.[J]. International Journal of Systematic and Evolutionary Microbiology, 2002, 52(5): 1773-1782. [38] NEYROLLES O, FERRIS S, BEHBAHANI N, et al. Organization of Ureaplasma urealyticum urease gene cluster and expression in a suppressor strain of Escherichia coli[J]. Journal of Bacteriology, 1996, 178(9): 2725. doi: 10.1128/jb.178.9.2725-2725.1996 [39] SPANAKI C, PLAITAKIS A. The role of glutamate dehydrogenase in mammalian ammonia metabolism.[J]. Neurotoxicity Research, 2012, 21(1): 117-127. doi: 10.1007/s12640-011-9285-4 [40] LI L , DONG Y H, QIAN G S, et al. Performance and microbial community analysis of bio-electrocoagulation on simultaneous nitrification and denitrification in submerged membrane bioreactor at limited dissolved oxygen[J]. Bioresource Technology, 2018, 258: 168-176. [41] BERGAUST L, VAN S R J M, FROSTEGÅRD Å, et al. Expression of nitrous oxide reductase in Paracoccus denitrificans is regulated by oxygen and nitric oxide through FnrP and NNR[J]. Microbiology, 2012, 158(Pt3): 826-834. [42] BJÖRN S, JULIAN S , GUNNAR S , et al. Investigation of the electron transport chain to and the catalytic activity of the diheme cytochrome c peroxidase CcpA of Shewanella oneidensis. [J]. Applied and Environmental microbiology, 2011, 77(17): 6172-80. [43] WANG Z X, WANG X P, SUN Y, et al. Fe(OH)3 induced the Anammox system to perform extracellular electron transfer for enhancement of NH4+ removal[J]. Chemical Engineering Journal, 2023, 460: 141768. doi: 10.1016/j.cej.2023.141768 [44] CHEN S T, ZHOU B H, CHEN H L, et al. Iron mediated autotrophic denitrification for low C/N ratio wastewater: A review[J]. Environmental Research, 2023, 216: 114687. doi: 10.1016/j.envres.2022.114687