EDTA-2Na/Fe(Ⅱ)对自养生物体系下硝酸盐还原过程的影响

采用厌氧序批式生物膜反应器(ASBBR),以固定浓度的硝酸盐和硫酸亚铁为基质,按不同梯度条件添加EDTA-2Na,进行长时间的培养驯化,研究铁盐脱氮的启动过程,同时探究不同EDTA-2Na/Fe (Ⅱ)对铁自养反硝化过程以及硝酸盐异化还原为铵(DNRA)的影响.结果表明:经过65d的培养驯化,反应器成功稳定运行.当EDTA-2Na/Fe (Ⅱ)<1.50时,反应器只进行铁自养反硝化过程,NO₃^-—N去除率最高仅为71.70%;当EDTA-2Na/Fe (Ⅱ)≥ 1.50时,反应器同时进行铁自养反硝化与DNRA过程,NO₃^-—N去除率最高为99.70%.值得注意的是,在EDTA-2Na/Fe (Ⅱ)=1.50时,铁自养反硝化速率达到最大值1.63mg/(L·h)的同时,DNRA的产氨量也达到最大值9.75mg/L.Visual MINTEQ模拟结果表明:EDTA-2Na与Fe (Ⅱ)的摩尔比会影响进水中EDTA-2Na与Fe (Ⅱ)的存在形态,物质的量比越大,FeEDTA^2-浓度越高,Fe (Ⅱ)的生物可利用性越强.通过对不同样本进行微生物种群分析,发现优势菌属有Brucella、Castellaniella、Ochrobactrum、Pseudomonas、Citrobacter,前4种菌属均与反硝化过程有关,Citrobacter菌属与DNRA过程有关,且该菌属只在EDTA-2Na/Fe (Ⅱ)=1.50和1.75两个条件下出现.上述研究结果可为更深入探究DNRA与反硝化之间的作用关系提供参考.     

Characterization of peroxyacetyl nitrate (PAN) under different PM2.5 concentration in wintertime at a North China rural site

As a secondary pollutant of photochemical pollution, peroxyacetyl nitrate (PAN) has attracted a close attention. A four-month campaign was conducted at a rural site in North China Plain (NCP) including the measurement of PAN, O₃, NO_x, PM_2.5, oxygenated volatile organic compounds (OVOCs), photolysis rate constants of NO₂ and O₃ and meteorological parameters to investigate the wintertime characterization of photochemistry from November 2018 to February 2019. The results showed that the maximum and mean values of PAN were 4.38 and 0.93 ± 0.67 ppbv during the campaign, respectively. The PAN under different PM_2.5 concentrations from below 75 μg/m³ up to 250 μg/m³, showed different diurnal variation and formation rate. In the PM_2.5 concentration range of above 250 μg/m³, PAN had the largest daily mean value of 0.64 ppbv and the fastest production rate of 0.33 ppbv/hr. From the perspective of PAN's production mechanism, the light intensity and precursors concentrations under different PM_2.5 pollution levels indicated that there were sufficient light intensity and high volatile organic compounds (VOCs) and NO_x precursors concentration even under severe pollution level to generate a large amount of PAN. Moreover, the bimodal staggering phenomenon of PAN and PM_2.5 provided a basis that PAN might aggravate haze through secondary organic aerosols (SOA) formation.     

黄土高塬沟壑区典型城郊流域地表水硝酸盐来源示踪

随着工农业的快速发展,地表水硝酸盐污染已成为黄土高原地区严重的环境问题之一.以黄土高塬沟壑区典型城郊流域砚瓦川为研究区,采用水化学分析方法和氮氧双稳定同位素技术,并结合SIAR模型,定量识别旱季和雨季研究区地表水硝酸盐不同污染源的贡献率,阐明不同污染源季节性差异的主要原因.结果表明,流域地表水无机氮主要以NO₃^--N和NO₂^--N形态存在,NO₃^--N和NO₂^--N雨季浓度平均值均高于旱季,而NH₄⁺-N则呈现相反特征;流域内地表水硝酸盐的转化过程主要以硝化作用为主,雨季其主要来源是粪肥污水,而旱季主要为粪肥污水和土壤氮淋溶,铵肥次之;不同污染源对流域地表水硝酸盐的贡献比例具有显著的季节性差异,旱季与雨季城镇污水排放的贡献比例均为最高,分别为31.40%和65.66%,且雨季污水排放对NO₃^-的影响远高于旱季,夏季居民用水增加导致大量污水排放至流域内是引起这一现象的主要原因.     

Estimation of Nonpoint Source Nitrate Concentrations in Indiana Rivers Based on Agricultural Drainage in the Watershed

Subsurface tile‐drained agricultural fields are known to be important contributors to nitrate in surface water in the Midwest, but the effect of these fields on nitrate at the watershed scale is difficult to quantify. Data for 25 watersheds monitored by the Indiana Department of Environmental Management and located near a U.S. Geological Survey stream gage were used to investigate the relationship between flow‐weighted mean concentration (FWMC) of nitrate‐N and the subsurface tile‐drained area (DA) of the watershed. The tile DA was estimated from soil drainage class, land use, and slope. Nitrate loads from point sources were estimated based on reported flows of major permitted facilities with mean nitrate‐N concentrations from published sources. Linear regression models exhibited a statistically significant relationship between annual/monthly nonpoint source (NPS) nitrate‐N and DA percentage. The annual model explained 71% of the variation in FWMC of nitrate‐N. The annual and monthly models were tested in 10 additional watersheds, most with absolute errors within 1 mg/l in the predicted FWMC. These models can be used to estimate NPS nitrate for unmonitored watersheds in similar areas, especially for drained agricultural areas where model performance was strongest, and to predict the nitrate reduction when various tile drainage management techniques are employed.     

Agricultural Chemicals in the Alluvial Aquifer of a Typical County of the Arkansas Delta

Statistical methods and a Geographic Information System (GIS) were used to investigate potential indicators of ground water vulnerability to agricultural chemical contamination in a representative area of the Mississippi River alluvial aquifer. A total of 47 wells were sampled for analysis of nitrate, phosphorus, potassium, and 13 pesticides commonly-used in the area. Ten soil and hydrogeologic variables and five ground water vulnerability indices were examined to explain the variations of chemical concentrations. The results showed that no individual soil or hydrogeologic variables or their linear combinations could explain more than 25% of the variation of the chemical concentrations. A quadratic response surface model with the values of confining unit thickness, slope, soil permeability, depth to ground water, and recharge rate accounted for 62% of the variation of nitrate, 43% of P, and 83% of K, suggesting that the interactions among soil and hydrogeologic variables were significant. Observed trends of decreasing nitrate and P concentrations with increasing well depth and/or depth to ground water seemed to correlate with carbonate equilibrium in the aquifer and more reduced environment with depth. In view of uncertainties involved, it was recognized that the limitations associated with input data resolution used in GIS and the formulation of leaching indices limited their use for predicting ground water vulnerability. Misuse of pesticides could be another factor that would complicate the relationships between pesticide concentrations and the vulnerability indices.     

厌氧氨氧化电子受体的研究

在无机条件下,以该课题组已经培养出来的厌氧氨氧化污泥作为接种污泥,分别以硫酸盐、硝酸盐和亚硝酸盐为电子受体来研究氨的氧化反应。从去除速率的角度来看,以NO2--N、NO3--N和SO42--S为电子受体的反应器,分别在运行的第24.5天、40天和31天时达到0.030 0 kg/(m.3d)NH4+-N去除速率,则氧化氨的能力由大到小依次是:亚硝酸盐>硫酸盐>硝酸盐;从标准吉布斯自由能变化来看,3种反应都是可以发生的;以亚硝酸盐为电子受体的反应过程是一个消耗酸度的生物过程,而以硫酸盐为电子受体的反应过程是一个消耗碱度的生物过程。     

长江上游典型农业源溪流溶存氧化亚氮(N2O)浓度特征及影响因素

随着农业非点源氮（N）污染的加剧,农田周边溪流成为重要的活性N汇和潜在的氧化亚氮（N₂O）排放源.为查明长江上游农业源溪流中溶存N₂O浓度的全年动态变化特征,于2014年12月~2015年10月开展紫色土丘陵区典型农田源头溪流N₂O浓度的连续采样观测,采用水-气顶空平衡-气相色谱法测定顶空气体中N₂O浓度,根据相关参数计算出本研究水体中的溶存N₂O浓度,并同步测定溪流水体物理化学指标,分析水中溶存N₂O浓度的主要影响因素.结果表明,长江上游紫色土丘陵区的典型农业源溪流的硝态氮（NO₃^--N）是最主要的活性N赋存形态（年均1.45 mg·L^-1）,溪流水体溶存N₂O质量浓度（以N计）全年平均为0.57 μg·L^-1（范围0.26~1.28 μg·L^-1）,冬、春、夏和秋季的均值分别为0.63、0.45、0.53和0.64 μg·L^-1,但季节间无显著差异.溪流水体溶存N₂O浓度全年都处于过度饱和状态（饱和度年平均为203.9%,范围109.7%~546.5%）,可见,农业源溪流全年均为潜在的N₂O释放源.溪流溶存N₂O浓度的变化主要由水体NO₃^--N浓度决定,N₂O的主要产生机制为反硝化作用;溪流季节平均N₂O饱和度在夏、秋季显著高于冬、春季,水中溶存N₂O饱和度的变化主要受水温和NO₃^--N浓度的共同影响.研究还发现农业源溪流中溶存N₂O浓度在4~10月（湿润季节）间波动明显,较强降雨可促使其水中NO₃^--N浓度在雨后短期内升高,进而促进水体反硝化作用,导致雨后溪流中溶存N₂O浓度的增加.     

基于水化学和氮氧双同位素的地下水硝酸盐源解析

为定性及定量识别地下水中氮的污染来源,比例及迁移转化特征,对河北省张家口市宣化区洋河北岸主要供水区的地下水进行取样分析.基于土地利用类型,综合利用水化学分析方法耦合δ¹⁵N-NO₃^-,δ¹⁸O-NO₃^-双同位素示踪技术对研究区地下水硝酸盐污染来源,贡献率及迁移转化规律进行判断.研究结果表明：研究区氮污染以NO₃^-为主,12处采样点4次采样过程中约77%超出世界卫生组织标准（10mg/L）的限值,其污染在2018年8月（夏季）较为严重,空间浓度插值结果显示硝酸盐呈现出沿河及远岸点位浓度相对较低,中间较为稳定区域浓度较高的空间特征,并表现出不同土地利用类型上污染程度的差异性：旱地浓度最高,城镇次之.稳定同位素模型（SIAR）显示地下水硝氮污染来源中粪肥及生活污水占45.37%,土壤氮来源为41.39%,降水和化肥中NH₄⁺来源占13.24%,与研究区以城镇和耕地为主的土地利用现状较为一致.此外,同位素特征值结果显示氮的迁移转化过程以硝化作用为主.文可为地下水氮的污染来源解析提供更加精准,全面的分析方法进而为污染的防治提供优先治理建议.     

千岛湖水体氮的垂向分布特征及来源解析

选取千岛湖水深0.2,5,10,20,30和40m处水样进行分析,利用氮氧同位素和稳定同位素模型（SIAR）研究千岛湖水体氮（N）的垂向分布特征,分析水体N的来源并计算各N源的贡献率.结果表明,硝酸盐（NO₃^-）和溶解性有机氮（DON）是千岛湖水体总溶解氮（TDN）的主要形式,分别占溶解态N的57.9%和39.7%.千岛湖水体δ¹⁵N-NO₃^-和δ¹⁸O-NO₃^-的平均值分别为4.5‰和4.3‰.上层水体（0~10m）中,硝化作用和浮游植物的同化作用共同控制水体N的形态组成和氮氧同位素值（δ¹⁵N-NO₃^-和δ¹⁸O-NO₃^-）的变化.中层水体（10~30m）中,硝化作用是主要的生物地球化学过程,使得水体NO₃^-含量增加而δ¹⁸O-NO₃^-值减小.底层水体（30~40m）受到硝化作用、底泥N释放和反硝化作用的共同影响.化肥是千岛湖水体NO₃^-的最主要来源,在S1和S2处的贡献率分别为51.9%和30.6%.新安江上游的农业面源污染使得S1处化肥贡献率远高于S2.土壤N是仅次于化肥的第二大水体NO₃^-来源,在S1和S2处的贡献率分别为17.8%和27.8%.此外,底泥对底层水体NO₃^-的贡献不可忽视.     

利用氮氧同位素解析赤水河流域水体硝酸盐来源及其时空变化特征

赤水河流域作为长江上游重要的水源涵养区,其生态环境状况及水环境质量备受关注。为了了解流域河水氮素来源,本次研究利用硝酸盐稳定同位素(~(15)N、~(18)O)示踪技术并结合流域土地利用类型空间分布分析了赤水河流域丰水期与枯水期干流及主要支流河水硝酸盐来源与转化过程。结果表明,流域水体NO_3~-浓度具有明显的时空变化,其中丰水期NO_3~-浓度要高于枯水期,喀斯特区域的NO_3~-浓度要高于非喀斯特区域。流域干、支流水体δ~(15)N-NO_3~-、δ~(18)O-NO_3~-季节性差异明显,丰水期支流δ~(15)N-NO_3~-差异较大,干流差异较小,而枯水期支流δ~(15)N-NO_3~-差异较小,干流差异较大。结合氮氧同位素和土地利用信息发现,丰水期支流NO_3~-受其土地利用方式的影响,其来源具有多样性;干流NO_3~-浓度则主要受支流混合作用影响。枯水期干流NO_3~-受流域人为活动影响较为显著,点源输入造成水体氮同位素分布范围较宽,主要来源表现为生活污水和土壤有机氮;而支流NO_3~-多表现为土壤有机氮来源,部分支流受流域内城镇影响,生活污水对河流NO_3~-贡献较大。流域水体氮污染控制应以农业面源氮流失为主,同时严格控制点源污染的输入。