Catalytic removal of phenol from gas streams by perovskite-type catalysts

Three perovskite-type catalysts prepared by citric acid method are applied to remove phenol from gas streams with the total flow rate of 300 mL/min, corresponding to a GHSV of10,000/hr. LaMnO_3 catalyst is first prepared and further partially substituted with Sr and Cu to prepare La_(0.8)Sr_(0.2)MnO_3 and La_(0.8)Sr_(0.2)Mn_(0.8)Cu_(0.2)O_3, and catalytic activities and fundamental characteristics of these three catalysts are compared. The results show that phenol removal efficiency achieved with La_(0.8)Sr_(0.2)Mn_(0.8)Cu_(0.2)O_3 reaches 100% with the operating temperature of 200°C and the rate of mineralization at 300°C is up to 100%, while the phenol removal efficiencies achieved with La_(0.8)Sr_(0.2)MnO_3 and LaMnO_3 are up to 100% with the operating temperature of 300°C and 400°C, respectively. X-ray photoelectron spectroscopy(XPS) analysis shows that the addition of Sr and Cu increases the lattice oxygen of La_(0.8)Sr_(0.2)Mn_(0.8)Cu_(0.2)O_3, and further increases mobility or availability of lattice oxygen. The results indicate that La_(0.8)Sr_(0.2)Mn_(0.8)Cu_(0.2)O_3 has the best activity for phenol removal among three catalysts prepared and the catalytic activity of phenol oxidation is enhanced by the introduction of Sr and Cu into LaMnO_3. Apparent activation energy of 48 k J/mol is calculated by Mars–Van Krevelen Model for phenol oxidation with La_(0.8)Sr_(0.2)Mn_(0.8)Cu_(0.2)O_3 as catalyst.     

长三角地区春季臭氧污染特征及其对冬小麦产量的影响

春季是长三角地区对流层O₃污染的高峰期之一,高浓度的O₃暴露会影响冬小麦生长导致减产.利用长三角地区各城市2014年春季逐时ρ（O₃）观测数据,研究了长三角地区春季O₃污染特征,并结合O₃暴露指数（M7指数和AOT40指数）和剂量-响应关系模型,详细评估了长三角地区O₃污染对冬小麦产量的影响.结果表明:长三角地区春季ρ（O₃）空间上总体呈南低北高的分布,长三角地区北部江苏和上海的ρ（O₃）明显高于南部的浙江地区,在浙江北部、江苏和上海等地区,整个春季日最大8 h ρ（O₃）平均值超过107 μg/m3,最高值出现在5月,超过128 μg/m3;一半以上的城市ρ（O₃）超标[超过GB 3095-2012《环境空气质量标准》中8 h滑动平均ρ（O₃）的二级标准限值（160 μg/m3）]日数在10 d以上,其中南京和扬州超标日数最多,分别为27和20 d;相应地,O₃暴露指数也呈南低北高的分布,其中苏北地区O₃暴露指数最高,导致长三角地区平均冬小麦相对损失达5.7%（M7）~25.5%（AOT40）,造成的产量损失为7.85×105 t（M7）~4.49×106 t（AOT40）,其中,苏北地区为5.8%（M7）~25.9%（AOT40）,造成的产量损失为6.77×105 t（M7）~3.86×106 t（AOT40）,占长三角地区冬小麦产量损失的86%以上.研究显示,当前长三角地区O₃污染及其对冬小麦产量的影响已相当严重,特别是对苏北地区,而苏北地区是我国重要的冬小麦产地之一,因此,应当科学有效地治理O₃污染以缓解粮食安全问题.      

东中国海表层海水137Cs分布的影响因素

采集山东半岛附近海域表层海水样品,分析137Cs分布特征,并结合东中国海137Cs比活度数据,探讨影响表层海水137Cs分布的因素。结果表明:（1）山东半岛附近海域表层海水137Cs比活度在0.60±0.18~1.21±0.19 Bq/m3之间,平均值为0.90±0.17 Bq/m3。沿岸137Cs比活度较离岸小,主要受沿岸流影响。（2）东中国海各海域137Cs空间分布受大气不均匀沉降,沿岸流,河流冲淡水等因素影响;随时间变化,整个东中国海表层137Cs活度降低,切尔诺贝利核事故对东中国海影响不大。（3）渤海表层137Cs海水析出速率为0.046/a,高于黄海（0.032/a）和东海（0.027/a）,与较高的颗粒物质吸附能力和水体横纵向混合过程有关。     

秸秆还田对外源氮在土壤中转化及其微生物响应的影响

秸秆还田是农业生产上提高土壤肥力的重要措施,而秸秆中较高的碳氮比,使秸秆碳的利用率较低,温室气体排放较高,因此配施无机氮磷肥能够调控土壤中元素计量比,增加微生物活性和元素利用率,促进土壤肥力提升.本研究选择在模拟秸秆还田条件下,添加¹⁵ N标记的无机氮肥,研究不同养分肥料添加对土壤中外源氮转化与分配的影响,以及微生物响应特征.结果表明,秸秆添加增加了土壤和土壤溶液中铵态氮和总氮含量;秸秆与无机氮肥配施条件下,土壤中¹⁵ N-TN在100 d培养时期内基本保持在28~33 μg,¹⁵ N-NH₄⁺在前30 d培养时期内逐渐增加,而后逐渐降低;施P增加了土壤中¹⁵ N-TN和¹⁵ N-NH₄⁺的含量,却使土壤溶液中¹⁵ N量降低了28%.无机氮肥在土壤中的分配表明,¹⁵ N在土壤中的比例基本保持在52%~61%,磷肥的添加使¹⁵ N在土壤中的分配比例最大提高了16.5%,而土壤溶液中¹⁵ N的比例由第5 d的36%降低至100 d时30%,使外源¹⁵ N损失量减少了1.2倍.秸秆添加促进了微生物活性,显著提高了土壤MBN的量;而无机肥料的添加进一步促进了土壤微生物的活性,100 d培养实验后,秸秆与无机氮、磷肥同时添加使MBN增加到对照处理的2.0和2.2倍.磷肥添加促进了微生物对¹⁵ N的利用,使¹⁵ N-微生物生物量氮（¹⁵ N-MBN）的量比添加秸秆和氮肥处理的提高了1.5倍.对土壤氮转化酶活性（β-1,4-N-乙酰葡糖氨糖苷酶,NAG）的研究结果表明,氮肥降低了土壤酶活性和底物亲和性,而氮磷肥同时添加时,酶活性较单加秸秆处理提高了48.1%.本研究可为深入了解稻田土壤生态系统氮循环、实现农田土壤肥力提升和温室气体减排提供理论依据.     

粤北某铀矿周边地表水放射性与重金属污染状况研究

以粤北某铀矿周边地表水为研究对象,用ICP-MS对21个样本进行放射性和重金属元素分析,采用内梅罗法对水质进行评价,为矿区地表水污染现状提供科学数据支持。结果表明:1)矿区周边地表水超标元素为U、TI、Pb、As,其中U含量为4.194~114.7μg/L,最高超标1倍多。2)铀矿开采的污染来源主要有矿井水、碎矿废水、废石堆放场产生的废水,此外农田、养殖场废水也不容忽视。3)该铀矿周边地表水污染状况整体良好,Ⅱ号水体较Ⅰ号水体污染状况严重,其中20号采样点评价等级较低。     

Pu在处置库地下水中的种态模拟及影响特征

采用PHREEQC对Pu在西南某低放废物处置库、甘肃北山高放处置库五一检测井和三号井地下水中的种态及影响进行对比分析,并探讨了pH、pE和离子浓度对Pu在地下水溶液中的影响分布。结果表明:Pu在地下水中主要以Ⅳ价的Pu(OH)_4和Pu(OH)_3~+为主,其次有少量Ⅴ价的PuO_2~+存在。pE和pH对Pu在地下水中的种态存在影响较大,强酸环境中溶液主要以Pu(Ⅲ)存在,中性及碱性环境中,溶液主要以Pu(Ⅳ)存在。离子浓度对Pu在地下水中的种态有一定影响,主要原因是CO_3~(2-)和SO_4~(2-)易与Pu结合形成新的络合物。因此,放射性废物处置库选址与安全评价工作等需要充分考虑周边地下水溶液的离子浓度、pH和pE等影响因素。     

降温过程中生物膜CANON反应器的运行特征

本文以低温高氨氮废水为着眼点,通过不断地调节运行工况,探讨降温过程中全程自养脱氮(CANON)工艺的运行特征,以探索出低温环境下进水NH_4~+-N浓度较高时,CANON工艺获得稳定短程硝化和良好脱氮效果的方法.结果表明:①相较于直接将生物膜CANON反应器的温度条件由中温转变为低温(30℃±1℃→19℃),逐步降温驯化更有利于脱氮功能菌适应低温环境,且每次降温的幅度应尽量减小,同时还应配合运行工况的调节;②温度经25 d逐步降低至19℃左右,18 d后又继续降至15℃左右,NH_4~+-N和TN去除率均能分别长期稳定在90%、70%以上,甚至当温度下降至12℃时,TN去除率与去除负荷仍能分别达到72. 52%、0. 78 kg·(m~3·d)~(-1);③降温过程中驯化生物膜CANON污泥时,应优先考虑短程硝化控制.可通过维持一定的剩余NH_4~+-N浓度并严格控制DO浓度,以抑制NOB的活性,从而获得稳定的短程硝化效果.     

有机污染物生物有效性的评价方法

环境中有机污染物的生物有效性评价对生物修复、生态毒性和环境风险研究有着重要的意义.本文概括了影响有机污染物生物有效性的因素,综述了近年来有机污染物生物有效性评价方法的发展与应用,并对该领域的研究趋势进行了展望.     

苍耳子的化学成分

苍耳子(Fructus Xanthii)是常用中药,主要用于慢性鼻炎的治疗,有一定的毒性.为明确苍耳子产生生物活性的物质基础,通过溶剂萃取、正、反相反复硅胶柱色谱及MCI柱色谱等方法,对苍耳子80%甲醇提取物进行分离纯化,用质谱、核磁共振谱等方法进行结构鉴定.从正丁醇萃取物中分离鉴定7个化合物:阿魏酸(1)、咖啡酸(2)、绿原酸(3)、4-O-咖啡酰奎宁酸甲酯(4)、6,7-二甲基-1,4-二氢-2,3-喹喔啉二酮(5)、咖啡酸胆碱酯(6)和4′-O-二氢红花菜豆酸钠盐-β-D-葡萄糖苷(7).其中,化合物4~7为首次从该植物中分离得到.图1参10     

Accumulation and remobilization of metals in superficial sediments in Tianjin, China

The concentrations of Cr, Ni, Cu, Zn, Cd, and Pb in superficial sediment samples collected from three representative sites (Yuqiao Reservoir, Haihe River, and Haihe River Estuary) in Tianjin, North China, were analyzed using various single extraction and sequential extraction procedures to determine their remobilization, extractability, and distribution patterns. Sediments from the Haihe River had higher metal concentrations and geo-accumulation indices, especially for Cd and Zn, than sediments from the other two sites, suggesting that the Haihe River has been heavily influenced by anthropogenic activities. In addition, over 31% and 28.2% of the total Cd in the Haihe River and the Yuqiao Reservoir, respectively, and 18.2% of the total Zn in the Haihe River were found to be associated with the exchangeable form, indicating the significant remobilization of Cd and Zn when compared with Cr and Ni. However, over 98% of the Ni and 78% of the Cr were most closely associated with the residue and oxidizable fractions, which resulted in their becoming environmentally immobile. Based on the Environmental Protection Agency method 3050B, Cd and Zn had the greatest extraction efficiency when a single extraction procedure using 0.5-mol L^???1 HCl, 0.43-mol L^???1 HAcO, and 0.05-mol L^???1 ethylene-diamine-tetra-acetic acid was conducted, with extraction yields of up to 72%, 68%, and 56% for Cd and 50%, 49%, and 29% for Zn, respectively, being obtained for the Haihe River sediments. This was followed by the yields of Cu and Pb and, finally, those of unpolluted metals such as Cr and Ni. HCl and acetic acid extraction provided equivalent information for predicting Cd and Zn mobility in the sediments studied and produced suitable results for quick screening.