A comparative investigation of NdSrCu_(1-x) Co_x O_(4-δ) and Sm_(1.8) Ce_(0.2) Cu_(1-x) Co_x O_(4-δ) (x:0–0.4) for NO decomposition

A series of single-phase T-structured NdSrCu 1-x Co x O 4-δ with oxygen vacancies and T -structured Sm 1.8 Ce 0.2 Cu 1-x Co x O 4-δ (x: 0–0.4) with oxygen excess were prepared using ultrasound-assisted citric acid complexing method, and characterized by means of techniques such as thermogravimetric analysis and NO temperature-programmed desorption (NO-TPD). The catalytic activities of these materials were evaluated for the decomposition of NO. It was found that the NdSrCu 1-x Co x O 4-δ catalysts were of oxygen vacancies whereas the Sm 1.8 Ce 0.2 Cu 1-x Co x O 4-δ ones possessed excessive oxygen (i.e., over-stoichiometric oxygen); with a rise in Co doping level, the oxygen vacancy density of NdSrCu 1-x Co x O 4-δ decreased while the over-stoichiometric oxygen amount of Sm 1.8 Ce 0.2 Cu 1-x Co x O 4-δ increased. The NO-TPD results revealed that NO could be activated much easier over the oxygen-deficient perovskite-like oxides than over the oxygen-excessive perovskite-like oxides, with the NdSrCuO 3.702 catalyst showing the best efficiency in activating NO molecules. Under the conditions of 1.0% NO/helium, 2800 hr -1 , and 600–900°C, the catalytic activity of NO decomposition followed the order of NdSrCuO 3.702 NdSrCu 0.8 Co 0.2 O 3.736 NdSrCu 0.6 Co 0.4 O 3.789 Sm 1.8 Ce 0.2 Cu 0.6 Co 0.4 O 4.187 Sm 1.8 Ce 0.2 Cu 0.8 Co 0.2 O 4.104 Sm 1.8 Ce 0.2 CuO 4.045 , in concord with the sequence of decreasing oxygen vacancy or oxygen excess density. Based on the results, we concluded that the higher oxygen vacancy density and the stronger Cu 3+ /Cu 2+ redox ability of NdSrCu 1-x Co x O 4-δ account for the easier activation of NO and consequently improve the catalytic activity of NO decomposition over the catalysts.     

Metal chlorides loaded on activated carbon to capture elemental mercury

Activated carbon (AC) was considered to be an effective sorbent to control mercury in combustion systems. However, its capture capacity was low and it required a high carbon-to-mercury mass ratio. AC loaded with catalyst showed a high elemental mercury (Hg0) capture capacity due to large surface area of AC and high oxidization ability of catalyst. In this study, several metal chlorides and metal oxides were used to promote the sorption capacity of AC. As a result, metal chlorides were better than metal oxides loaded on AC to remove gaseous mercury. X-ray diffractometer (XRD), thermogravimetric analyzer (TGA) and specific surface area by Brunauer- Emmett-Teller method (BET) analysis showed the main mechanisms: first, AC had an enormous surface area for loading enough MClx; second, Cl and MxOy were generated during pyrogenation of MClx; finally, there were lots of active elements such as Cl and MxOy which could react with elemental mercury and convert it to mercury oxide and mercury chloride. The HgO and HgCl2 might be released from AC’s porous structure by thermo regeneration. A catalytic chemisorption mechanism predominates the sorption process of elemental mercury. As Co and Mn were valence variable metal elements, their catalytic effect on Hg0 oxidization may accelerate both oxidation and halogenation of Hg0. The sorbents loaded with metal chlorides possessed a synergistic function of catalytic effect of valence variable metal and chlorine oxidation.     

华北平原玉米-小麦轮作农田N2O交换通量的研究

以华北地区冬小麦-夏玉米轮作农田为研究对象,运用静态箱法对正常施肥及正常施肥结合秸秆还田农田N2O交换通量进行了连续1 a对比研究.正常施肥及正常施肥结合秸秆还田样地N2O全年的累积排放量分别为7.61 kg.hm-2和12.6kg.hm-2,其中秸秆还田引起N2O排放明显增加主要发生在玉米生长季节.两种处理样地在玉米季N2O的排放量占全年累积排放的57%～86%,表明华北玉米-小麦轮作体系中N2O排放主要集中在玉米季.各次施肥后10 d内N2O的累积排放量约占全年总排放量的71%～88%,显然现有化肥极大促进了华北农田N2O排放.     

Fe-MnOx-CeO2/ZrO2低温催化还原NO性能研究

以纳米ZrO2为载体,用浸渍法制备出Fe-MnOx-CeO2/ZrO2催化剂,考察了活性组分配比和助剂负载量对催化剂低温NH3选择性催化还原NO活性的影响,并对催化剂进行了XRD、SEM、EDS和BET表征;探讨了温度、H2O和SO2对Fe-MnOx-CeO2/ZrO2催化剂低温下NH3选择性催化还原NO的影响,结果表明,无SO2和H2O条件下,8%Fe-10%MnOx-CeO2/ZrO2催化剂具有良好的催化活性和稳定性.120℃时,催化剂的脱硝效率为85.23%,当温度升至180℃时,脱硝效率可达到92.0%.SO2和H2O共存条件下,催化剂易失活,采用傅立叶变换红外光谱对各反应阶段的催化剂进行了表征,对其失活机制进行深入研究,结果表明,催化剂失活的主要原因是催化剂表面硫酸铵盐的沉积和催化剂本身活性成分的硫酸盐化.     

双季稻田CH4和N2 O排放特征及品种筛选研究

通过大田小区实验,采用静止箱-气相色谱法对早晚两季水稻品种CH4与N2O排放通量进行了观测.结果表明,早稻CH4排放季节变化呈单峰模式,N2O排放呈双峰模式;晚稻CH4与N2O排放季节变化均呈单峰模式.CH4、N2O季节平均排放通量品种间均存在显著差异(P<0.05).早稻品种CH4、N2O季节平均排放通量极差分别为0.58 mg.(m2.h)-1、5.89μg.(m2.h)-1,晚稻为4.06 mg.(m2.h)-1、5.70μg.(m2.h)-1;早稻品种温室气体排放的增温潜势、单位产量增温潜势极差分别为2.92 kg.hm-2、0.097 kg.kg-1,晚稻分别为2 256 kg.hm-2、0.28 kg.kg-1.增温潜势、单位产量增温潜势比较,常规稻>超级杂交稻>杂交稻.早稻无水稻种植区CH4、N2O季节排放通量分别是水稻种植区的27.1%～31.8%、33.6%～88.3%;晚稻分别是23.8%～28.8%、38.6%～45.3%.早稻适宜种植品种为陆两优819、金优402、湘早籼24号,晚稻品种为岳优9113、湘晚籼12号.     

Shellac-coated iron oxide nanoparticles for removal of cadmium(II) ions from aqueous solution

This study describes a new effective adsorbent for cadmium removal from aqueous solution synthesized by coating a shellac layer, a natural biodegradable and renewable resin with abundant hydroxyl and carboxylic groups, on the surface of iron oxide magnetic nanoparticles. Transmission Electron Microscopy (TEM) imaging showed shellac-coated magnetic nanoparticle (SCMN) adsorbents had a core-shell structure with a core of 20 nm and shell of 5 nm. Fourier Transform Infrared Spectroscopic analysis suggested the occurrence of reaction between carboxyl groups on the SCMN adsorbent surface and cadmium ions in aqueous solution. Kinetic data were well described by pseudo second-order model and adsorption isotherms were fitted with both Langmuir and Freundlich models with maximum adsorption capacity of 18.80 mg/g. SCMN adsorbents provided a favorable adsorption capacity under high salinity conditions, and cadmium could easily be desorbed using mild organic acid solutions at low concentration.     

Differences in nitrous oxide fluxes from red soil under different land uses in mid-subtropical China

Red soil may play an important role in nitrous oxide (N₂O) emissions due to its recent land use change pattern. To predict the land use change effect on N₂O emissions, we examined the relationship between soil N₂O flux and environmental determinants in four different types of land uses in subtropical red soil. During two years of study (January 2005-January 2007), biweekly N₂O fluxes were measured from 09:00 to 11:00 a.m. using static closed chamber method. Objectives were to estimate the seasonal and annual N₂O flux differences from land use change and, reveal the controlling factors of soil N₂O emission by studying the relationship of dissolved organic carbon (DOC), microbial biomass carbon (MBC), water filled pore space (WFPS) and soil temperature with soil N₂O flux. Nitrous oxide fluxes were significantly higher in hot-humid season than in the cool-dry season. Significant differences in soil N₂O fluxes were observed among four land uses; 2.9, 1.9 and 1.7 times increased N₂O emissions were observed after conventional land use conversion from woodland to paddy, orchard and upland, respectively. The mean annual budgets of N₂O emission were 0.71-2.21 kg N₂O-N ha⁻¹ year⁻¹ from four land use types. The differences were partly attributed to increased fertilizer use in agriculture land uses. In all land uses, N₂O fluxes were positively related to soil temperature and DOC accounting for 22-48% and 30-46% of the seasonal N₂O flux variability, respectively. Nitrous oxide fluxes did significantly correlate with WFPS in orchard and upland only. Nitrous oxide fluxes responded positively to MBC in all land use types except orchard which had the lowest WFPS. We conclude that (1) land use conversion from woodland to agriculture land uses leads to increased soil N₂O fluxes, partly due increased fertilizer use, and (2) irrespective of land use, soil N₂O fluxes are under environmental controls, the main variables being soil temperature and DOC, both of which control the supply of nitrification and denitrification substrates.     

氢氧化钽对水体中磷酸盐的吸附去除作用

采用氢氧化钽为吸附剂,对水中磷酸盐的吸附性能进行了研究,考察了吸附时间、pH值、磷酸盐的初始浓度、反应温度对吸附量的影响。实验结果表明:pH值越小,氢氧化钽对磷酸盐的吸附量越大,当pH值为2时氢氧化钽对磷酸盐的吸附性能优,并且pH值对磷酸盐的吸附量影响较大;磷酸盐的初始浓度越大,吸附量越大,吸附平衡时间越短;氢氧化钽对磷酸盐的吸附量和吸附速率都随着温度的升高而增加。在25℃、pH=2、初始浓度为200 mg/L、吸附30 min时达到平衡时最大吸附量为76.69 mg/g。吸附后的氢氧化钽红外谱图在1066 cm-1处出现特征峰,该峰恰好是吸附磷酸盐的伸缩振动峰,并且在638 cm-1与670 cm-1之间Ta-O键由于磷酸盐的吸附发生了蓝移。采用6 mol/L的NaOH对吸附了磷酸盐的氢氧化钽进行解吸,当pH=12时解吸率为52.45%。研究结果表明,氢氧化钽能够有效的去除水溶液中磷酸盐的吸附剂。     

FeⅡ(EDTA)络合协同RDB去除NO废气效能及过程分析

为进一步提高一氧化氮(NO)的去除效率,在新型生物转鼓反应器(rotating drum biofilter,RDB)中,以FeⅡ(EDTA)络合协同RDB生物转鼓的耦合技术强化难水溶性NO的气液传质速率,提高生物还原效能为目标进行了研究.结果表明,适量FeⅡ(EDTA)被添加到RDB底部营养液后,能迅速吸收气相中的NO并生成FeⅡ(EDTA)-NO络合物,进而可通过反硝化实现同步脱氮和络合剂再生.在转速0.5 r.min-1、空床停留时间(EBRT)57.7 s、温度30℃、pH 7～8的实验条件下,RDB的净化效能随络合剂的投加而显著改善;FeⅡ(EDTA)质量浓度从0增至500 mg.L-1后,NO去除率从61.1%提高到97.6%,去除负荷从16.2 g.(m3.h)-1上升到26.7 g.(m3.h)-1.分析了FeⅡ(EDTA)络合协同净化NO的反应过程,建立了NO净化效率与FeⅡ(EDTA)添加浓度的关联方程,可较好地拟合实验数据.     

胶州湾及邻近海域表层海水中一氧化氮浓度分布及其影响因素探讨

2011年2～3月利用化学发光法对胶州湾及邻近海域表层海水中一氧化氮(NO)浓度进行了监测.结合水文、化学和生物等要素的同步观测资料,对该海域NO浓度分布及其影响因素进行了探讨.结果表明,胶州湾内表层海水中NO浓度为0.080～0.493 nmol.L-1,平均值为(0.292±0.146)nmol.L-1,胶州湾外NO浓度为未检出～0.435 nmol.L-1,平均值为(0.160±0.130)nmol.L-1.总体来说,胶州湾表层海水中NO浓度呈现出自湾内向湾外递降的分布趋势,陆地径流和人为活动可能对NO浓度的分布造成一定程度的影响.胶州湾及邻近海域表层海水中NO浓度比开阔大洋高1个数量级.周日变化研究表明,NO浓度具有一定的变化特征,最大值出现在15:00,这可能主要受光照的影响.影响NO浓度分布的因素比较复杂,可能主要受亚硝酸盐、光强和pH等因素的影响.结果表明,2011年春季胶州湾及邻近海域表层海水是大气NO的源,通量约为1.09×10-15 mol.(cm2.s)-1.