生物陶粒反应器的氢自养反硝化研究

利用氢自养反硝化生物陶粒反应器处理硝酸盐废水,探讨了生物陶粒反应器中氢自养反硝化生物脱氮的实现过程.考察了水力停留时间、进水硝氮负荷、进水pH值、温度、供氢量等因素对反应器脱氮效果的影响.结果表明,当水力停留时间为24 h和48 h时,反应器对硝酸氮的平均去除率分别达到94.54%和97.47%.在水力停留时间为5~16 h时,NO-3-N去除率随水力停留时间的缩短而降低;进水NO-3-N浓度较低时,NO-3-N的降解速率随其浓度的升高而增大,当NO-3-N浓度大于110mg·L-1时,氢自养反硝化反应受到抑制;中偏碱性环境较酸性或碱性环境更利于反应器对硝酸盐的去除;反应器有较宽的温度适应范围,最适温度为25~30℃;当反应器供氢不足时,脱氮效果明显降低,表明了氢自养反硝化菌对氢气利用的专一性.在整个运行阶段,出水中亚硝酸氮浓度一直保持在较低水平.     

高岭土负载纳米Fe/Ni同时去除水中Cu2+和NO3-

工业废水常含有不同污染物如重金属离子和无机阴离子,而如何有效去除复合污染物就成为环境科学前沿研究的挑战性课题.这些污染物因化学性质不同而导致去除机理和途径也不同.本文采用合成高岭土负载纳米双金属Fe/Ni(K-Fe/Ni)同步去除水中Cu2+和NO-3.结果表明K-Fe/Ni能有效去除水中Cu2+和NO-3,但它们的去除效果却会相互受到影响.在Cu2+浓度为200mg·L-1时,NO-3的去除率达到42.5%;而未加入Cu2+时,NO-3的去除率仅有26.9%,说明Cu2+的存在提高了NO-3降解效率.同样,水中NO-3的存在也影响Cu2+的去除(Cu2+去除率从99.7%降到96.5%).但NO-3浓度对去除Cu2+的影响小于Cu2+浓度对NO-3的影响.通过BET比表面积、X射线衍射(XRD)、扫描电镜(SEM)、X射线能量散射(EDS)和X射线光电分析(XPS)对K-Fe/Ni表征的结果显示,反应后K-Fe/Ni的表面存在铁的氧化物、Ni0和被还原的Cu0.基于以上结果,我们发现K-Fe/Ni同步去除水中Cu2+和NO-3的机理是:高岭土负载下的纳米Fe0作为还原剂,在Ni0的催化产氢作用下将Cu2+还原成Cu0并沉积在K-Fe/Ni上而形成纳米Fe/Ni/Cu三金属催化剂,从而加速催化水中NO-3降解.     

Formic acid as an alternative reducing agent for the catalytic nitrate reduction in aqueous media

Formic acid was used for the nitrate reduction as a reductant in the presence of Pd:Cu/γ-alumina catalysts. The surface characteristics of the bimetallic catalyst synthesized by wet impregnation were investigated by SEM, TEM-EDS. The metals were not distributed homogeneously on the surface of catalyst, although the total contents of both metals in particles agreed well with the theoretical values. Formic acid decomposition on the catalyst surface, its influence on solution pH and nitrate removal efficacy was investigated. The best removal of nitrate (50 ppm) was obtained under the condition of 0.75 g/L catalyst with Pd:Cu ratio (4:1) and two fold excess of formic acid. Formic acid decay patterns resembled those of nitrate removal, showing a linear relationship between kf (formic acid decay) and k (nitrate removal). Negligible amount of ammonia was detected, and no nitrite was detected, possibly due to buffering effect of bicarbonate that is in situ produced by the decomposition of formic acid, and due to the sustained release of H2 gas.     

反硝化菌株DA-1的脱氮研究

菌株DA-1被发现能在好氧和厌氧环境中将硝酸盐转化为气态氮。在以NO3-为唯一氮源的条件下研究了碳源、C/N和pH值对菌株DA-1好氧和厌氧反硝化脱氮的影响。结果表明:同等条件下,48 h内菌株DA-1的厌氧脱氮效率高于好氧脱氮率;菌株DA-1能在好氧和厌氧条件下利用乙酸、柠檬酸以及葡萄糖进行细胞增殖和反硝化。在厌氧条件下,三者作为碳源时的反硝化效率分别为(34.04±0.15)%、(22.72±0.32)%和(11.32±0.06)%,均低于好氧条件下的(25.38±0.14)%、(17.52±0.11)%和(8.06±0.01)%。2种条件下均是乙酸为碳源时反硝化效率最高。而丁二酸仅能在厌氧环境中作为电子供体参与反硝化反应。C/N越高越有利于菌株DA-1的厌氧反硝化,当C/N为10时,反硝化效率最高为(35.06±0.19)%。而在好氧条件下,菌株反硝化效率随着C/N的升高,先升高再降低,当C/N为8时,反硝化效率最高;好氧和厌氧脱氮的最适pH值为7.0。体系偏酸或者偏碱都会造成菌株DA-1脱氮效率的降低并出现亚硝酸盐累积。厌氧环境中pH=5.0时累积的亚硝酸盐浓度高达(8.95±2.05)mg/mL。     

2种生物反硝化法去除地下水中硝酸盐的研究

采用砂柱装置,在实验室研究了自养微生物和异养微生物2种生物反硝化方法对地下水中硝酸盐的去除效果。自养反硝化反应在以硫作为电子供体的硫/石灰石/细沙反应柱中进行,异养反硝化反应在石灰石/细沙反应柱中进行,进水增加乙醇作为外加碳源。实验结果用以比较2种反硝化方法在硝酸盐去除率、微生物反应动力学和反应产物三者的异同。结果表明,自养反硝化反应中NO3--N去除率达95.4%,异养反硝化反应去除率可达99.3%;分别与Monod微生物0级、1/2级和1级反应动力学方程进行拟合,2种反硝化反应均符合1/2级微生物反应动力学,适合用1/2级微生物反应方程描述;在反应结束阶段,自养反硝化主要反应产物SO42-出水浓度低于250mg/L,异养反硝化副产物CH3OO-易成为二次污染源,异养反硝化的反硝化速率明显高于自养反硝化反应。     

金佛山地区地下水硝态氮污染时空变异性研究

根据1976～1977年、2004～2006年和2009年金佛山地区23处地下水排泄点水中硝态氮的质量浓度,采用地球化学、统计学与GIS相结合的方法确定了区内地下水中硝态氮的地球化学背景值,分析了硝态氮污染的时空变异特征.结果表明,区内地下水中硝态氮的地球化学背景值为0.72～2.00 mg.L-1,正异常下限为3.20 mg.L-1;2004～2006年和2009年金佛山自然保护区内地下水硝态氮平均质量浓度为：2.08、2.67、2.59和3.92 mg.L-1;保护区外为：39.08、25.46、17.99和13.73mg.L-1;平均超标率（标准规定NO 3--N≤10 mg.L-1）为：451.64%、478.61%、331.85%和145.67%;最高浓度为：157.58、118.04、63.82和46.18 mg.L-1;最大超标率为：1 475.81%、1 080.39%、538.20%和361.78%.插值分析结果显示,区内地下水中硝态氮高值中心随时间而变化,低值区沿金佛山自然保护区分布.当地合理的环境保护政策和产业结构调整,对环境保护工作起到了积极作用.     

阿替洛尔在硝酸根溶液中的光降解研究

以氙灯为模拟太阳光光源,研究了β阻滞剂阿替洛尔(ATL)在硝酸根溶液中的光解,探讨了硝酸根离子浓度、溶液pH值、碳酸氢根离子浓度和腐殖质浓度对ATL光解的影响.结果表明,ATL在不同浓度硝酸根溶液中的光解反应符合准一级动力学规律,增大硝酸根离子浓度促进了ATL的光降解率,当硝酸根离子浓度由0增至5 mmol.L-1时其速率常数由0.002 26min-1增至0.009 4 min-1;酸性或碱性溶液有利于ATL在硝酸根溶液中的光解,碳酸氢根离子浓度对光解无明显影响,而加入Suwannee富里酸(SRFA)对光解产生抑制作用.采用异丙醇作为羟基自由基分子探针检测到.OH存在于ATL光解过程中.采用SPE-LC-MS方法鉴定了ATL在硝酸根溶液中的主要光解产物,并提出了可能的光解途径.     

稀土钇对蚯蚓的急性毒性及蚓体内蓄积研究

文章以蚯蚓为指示生物,分别采用滤纸接触法和自然土壤法研究了稀土元素钇对蚯蚓的急性毒性效应。结果表明,滤纸接触法测得钇对蚯蚓的半数致死浓度LC50为0.18 g/L;土壤法所测LC50值为1.08 g/kg。可见,稀土钇对蚯蚓具有毒性作用,但属低毒级,并且自然土壤法中蚯蚓的半数致死浓度要低于滤纸接触法中的结果。应用ICP-AES分别研究了2种实验方法中钇在蚯蚓体内的富集情况,发现硝酸钇浓度及染毒时间、蚯蚓的死亡率及速度和钇在蚯蚓体内的富集三者存在显著的相关性。     

Effects of seed aerosols on the growth of secondary organic aerosols from the photooxidation of toluene

Hydroxyl radical （.OH）-initiated photooxidation reaction of toluene was carried out in a self-made smog chamber. Four individual seed aerosols such as ammonium sulfate, ammonium nitrate, sodium silicate and calcium chloride, were introduced into the chamber to assess their influence on the growth of secondary organic aerosols （SOA）. It was found that the low concentration of seed aerosols might lead to high concentration of SOA particles. Seed aerosols would promote rates of SOA formation at the start of the reaction and inhibit its formation rate with prolonging the reaction time. In the case of ca. 9000 pt/cm^3 seed aerosol load, the addition of sodium silicate induced a same effect on the SOA formation as ammonium nitrate. The influence of the four individual seed aerosols on the generation of SOA decreased in the order of calcium chloride〉sodium silicate and ammonium nitrate〉ammonium sulfate.     

Effects of nitrate concentration in interstitial water on the bioremediation of simulated oil-polluted shorelines

Nutrient addition has been proved to be an effective strategy to enhance oil biodegradation in marine shorelines.To determine the optimal range of nutrient concentrations in the bioremediation of oil-polluted beaches,nitrate was added to the simulated shoreline models in the initial concentration of 1,5 and 10 mg/L.Whenever the NO3-N concentration declined to 70% of its original value, additional nutrients were supplemented to maintain a certain range.Results showed adding nutrients increased the oil biodegradation level,the counts of petroleum degrading bacteria(PDB)and heterotrophic bacteria (HB),and the promoted efficiency varied depending on the concentration of nitrate.Oil degradation level in 5 mg/L(NO_3-N)group reached as much as 84.3% accompanied with the consistently highest counts of PDB;while in 1 mg/L group oil removal efficiency was only 35.2%,and the numbers of PDB and HB were relatively low compared to the other groups supplemented with nutrients.Although counts of HB in the 10 mg/L group were remarkable,lower counts of PDB resulted in poorer oil removal efficiency (70.5%) compared to 5 mg/L group.Furthermore,it would need more NO_3-N(0.371 mg)to degrade 1 mg diesel oil in the 10 mg/L group than in the 5 mg/L group(0.197 mg).In conclusion, Nitrate concentration in 5 mg/L is superior to 1 and 10 mg/L in the enhancement of diesel oil biodegradation in simulated shorelines.