农用改性硝酸铵拒爆机理及工业化可行性研究

对农用硝铵作改性处理,通过筛选和优化实验确定了改性硝酸铵配方。结果表明,当硝酸铵中添加3%的改性剂GXJ1,10%的改性剂GXJ2时,产品在1mm铁皮管约束下的雷管感度试验条件下具有拒爆特性。改性硝酸铵总养分与普通硝酸铵相当,并且颗粒强度高,不易粉化、结块和吸潮,具有优良的肥料品质。同时还利用X射线衍射分析、扫描电子显微镜分析对改性硝铵的拒爆机理作初步探讨。最终,建立了改性硝酸铵的脱水性能、流动性能、凝固性能、颗粒强度的评价方法,并进行了工业化可行性研究。     

阿什河水系枯水期氮污染特征与同位素源解析

在阿什河水系设置20个采样点,采用水质监测技术和稳定氮同位素示踪技术,研究了枯水期阿什河氮污染特征和硝酸盐氮污染来源。结果表明:(1)阿什河枯水期大部分采样点氨氮浓度较低,大部分区域达到或优于《地表水环境质量标准》(GB3838—2002)中Ⅲ类。上游河段硝酸盐氮浓度较低,中游河段较高,到下游河段略有降低。总氮浓度较高,最高达19.4mg/L。(2)阿什河水系采样点15 N的丰度(δ15 N)主要处于0.11%~0.21%、0.42%~0.78%、0.83%~0.88%和1.09%~1.26%。稳定15 N同位素示踪解析阿什河硝酸盐氮污染来源表明,阿什河上游污染源主要为大气沉降、土壤有机氮和人工化肥;中游主要受畜禽养殖污水和生活污水污染;下游主要受城镇生活污水和工业废水影响。     

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。     

Seasonal and diurnal variations of atmospheric peroxyacetyl nitrate, peroxypropionyl nitrate, and carbon tetrachloride in Beijing

Atmospheric peroxyacetyl nitrate(PAN), peroxypropionyl nitrate(PPN), and carbon tetrachloride(CCl4) were measured from September 2010 to August 2011 in Beijing. PAN exhibited low values from mid-autumn to early spring(October to March) with monthly average concentrations ranging from 0.28 to 0.73 ppbV, and increased from early spring to summer(March to August), ranging from 1.37–3.79 ppbV. The monthly variation of PPN was similar to PAN, with low values(below detection limit to 0.18 ppbV) from mid-autumn to early spring, and a monthly maximum in September(1.14 ppbV). The monthly variation of CCl4was tightly related to the variation of temperature, exhibiting a minimum in winter(69.3 pptV) and a maximum of 180.6 pptV in summer. Due to weak solar intensity and short duration, PAN and O3showed no distinct diurnal patterns from morning to night during winter, whereas for other seasons, they both exhibited maximal values in the late afternoon(ca. 15:00 to 16:00 local time) and minimal values during early morning and midnight. Good linear correlations between PAN and PPN were found in autumn(R = 0.91), spring(R = 0.94), and summer(R = 0.81), with slopes of 0.130, 0.222, and 0.133, respectively, suggesting that anthropogenic hydrocarbons dominated the photochemical formation of PANs in Beijing. Positive correlation between PAN and O3 in summer with the low slopes( O3 / PAN) ranging from 9.92 to 18.0 indicated serious air pollution in Beijing, and strong negative correlation in winter reflected strong O3consumption by NO titration and less thermal decompositin of PAN.     

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.     

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.     

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。     

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.     

硝酸钙对河流底泥中含硫化合物嗅味原位控制

以硝酸钙作为氧化剂,对深圳河污染底泥典型嗅味物质AVS（酸挥发性硫化物）和GEM（土臭素）及2 MIB（2 甲基异莰醇）进行原位控制. 结果表明,当硝酸钙投加量（以单位质量AVS所需NO3- N质量计）为1.68 g/g,AVS去除率达到92%,且可有效避免硝酸钙向上覆水释放,适合工程应用. 但是,硝酸钙对河流底泥GEM和2 MIB等典型嗅味物质的原位控制效果较差. 硝酸钙能够引起底泥中微生物多样性增加,16S rDNA指纹图谱显示,优势菌株包括去除AVS的脱氮硫杆菌(Thiobacillus thioparus),反硝化细菌(Simplicispira sp.和Rhodanobacter sp).以及降解有机物的菌株(Simplicispira sp.、Lysobacter sp.、Pseudoxanthomonas sp.)等.      

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.