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大量含氮废水的排放会造成水体富营养化现象。从成本和去除效果考虑,生物脱氮是公认的最佳脱氮方法[1-3]。厌氧氨氧化(anaerobic ammonium oxidation,Anammox)工艺可以解决传统硝化反硝化存在的剩余污泥产量高、碳源和能源消耗等问题[4]。在缺氧条件下,厌氧氨氧化菌利用亚硝酸盐氮(NO2−-N)为电子受体,将氨氮(NH4+-N)转化为氮气,其具有节约碳源、能耗和污泥产量少等优点[5-6]。在与Anammox组合的工艺中,如何高效稳定地获取NO2−-N是工艺运行的关键。短程硝化[7-8]、短程反硝化(partial denitrification,PD)[9]工艺等可为厌氧氨氧化工艺提供NO2−-N。从反应路径和节省物耗能耗等方面来讲,短程硝化是提供亚硝酸盐氮的最佳方法。但其在实际应用中抑制亚硝酸盐氧化菌(nitrite oxidizing bacteria,NOB)难度大,控制要求高,很难高效稳定的实现NO2−-N积累[4,10-13]。
PD工艺是指通过调控相关条件,将全程反硝化(NO3−-N→NO2−-N→NO→N2O→N2)控制在NO2−-N阶段[14]。PD工艺的关键在于以NO2−-N为产物的反硝化菌属的富集[15-16]。目前影响PD工艺NO2−-N积累的主要因素有C/N、pH、反应时间、反应器类型、碳源类型以及温度等。CAO等[17]在长期运行研究中发现,上流式厌氧污泥床反应器的亚硝酸盐积累率(nitrite accumulation rate,NAR)仅为51.0%,而序批式反应器(sequencing batch reactor,SBR)中的NAR稳定高于80%。袁怡等以乙酸钠为唯一碳源进行研究,发现高NAR通常发生在低C/N条件下。DU等[18]发现,C/N对高NAR的短程反硝化污泥影响不大,认为系统富集的Thauera菌是只能还原NO3−-N为NO2−-N的短程反硝化菌。基于此,不少研究者均实现了稳定的亚硝酸盐氮累积率[19-22]。在PD工艺的研究中,既有以硝酸钠作为NO3−-N来源[23-24],也有以硝酸钙作为NO3−-N来源[25-26],但两者对PD快速启动以及微生物变化的影响却鲜有报道。此外,关于磷元素添加对PD工艺的反硝化性能及微生物种群的影响也需进一步研究。
因此,本研究以乙酸钠为碳源,在SBR中通过硝酸钠和硝酸钙的交替投加、微量元素的投加量以及C/N比的改变,考察了不同条件对反硝化的性能及NO2−-N积累的影响,并分析了反应器微生物种群演替特征,以期为短程反硝化的快速启动及稳定运行提供参考。
不同阳离子和碳氮比对反硝化性能及亚硝酸盐氮积累的影响
Effects of different cations and C/N on denitrification performance and nitrite accumulation
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摘要: 在序批式反应器(SBR)中,采用乙酸钠为碳源,通过硝酸钠和硝酸钙的交替投加、微量元素的投加以及碳氮比(COD/NO3−-N)的改变,探究了不同控制条件对反硝化性能及NO2−-N积累的影响,并分析了反应器中微生物种群演替特征。结果表明,在以乙酸钠为碳源的SBR中,Ca2+浓度过高会抑制反硝化。以NaNO3为NO3−-N来源时,硝酸盐氮还原率维持在50%左右;相同条件下,以Ca(NO3)2为NO3−-N来源时,硝酸盐氮还原率仅有20%。反应器中补充适量磷元素后,硝酸盐氮还原率提高至62%,同时有少量的亚硝酸盐氮积累。当C/N比提高为4后,硝酸盐氮还原率大于98%,长期运行下亚硝酸盐氮积累率平均为83.8%。高通量测序分析结果表明,变形菌门和拟杆菌门在系统中占主导地位。NO2−-N积累的关键功能菌属是Thauera菌属,其最高占比为17.25%。以Ca(NO3)2为NO3−-N来源时,Thauera菌属占比仅为0.14%。以上研究结果为短程反硝化的快速启动和稳定运行提供参考。Abstract: Sodium acetate was used as the carbon source in a sequencing batch reactor (SBR), and the effects of different control conditions on denitrification performance and NO2−-N accumulation were investigated by alternate dosing of sodium nitrate and calcium nitrate, the dosing of trace elements and the change of C/N ratio, and the characteristics of microbial population succession in SBR were also analyzed. The results showed that high Ca2+ concentration inhibited denitrification performance in the SBR reactor with sodium acetate as the carbon source. The nitrate nitrogen reduction rate was maintained at about 50% when NaNO3 was used as the NO3−-N source; under the same conditions, the nitrate nitrogen reduction rate was only 20% when Ca(NO3)2 was used as the NO3−-N source. When SBR was supplemented with appropriate amount of phosphorus, the nitrate reduction rate could increase to 62%, while the accumulation of a small amount of nitrite occurred. When the carbon to nitrate ratio (COD/NO3−-N) increased to 4, the nitrate reduction rate was greater than 98%, and the nitrite accumulation rate was 83.8% on average under long-term operation. High-throughput sequencing analysis showed that Proteobacteria and Bacteroidetes dominated the system, the key functional genus for NO3−-N accumulation was Thauera, which had the highest percentage of 17.25%. The percentage of Thauera was only 0.14% when Ca(NO3)2 was used as the source of NO3−-N. These results provide a theoretical support for the rapid start-up and stable operation of partial denitrification.
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Key words:
- partial denitrification /
- cation /
- COD/NO3−-N /
- microbial community
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表 1 短程反硝化SBR运行阶段
Table 1. Operation stage of partial denitrification SBR
阶段 时间/d 反应时间/min COD/N 换水比/% Ⅰ 1~36 360 3 70 Ⅱ 37~61 480 3 70 Ⅲ 62~76 480 3 70 Ⅳ 77~80 480 4 70 81~84 120~300 4 70 85~111 70 4 70 -
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