Enhancement of phosphorus sorption onto light expanded clay aggregates by means of aluminum and iron oxide coatings

Phosphorus (P) loading from non-point or point sources increases the eutrophication risk of natural waters. The functioning of constructed wetlands (CWs) used as natural water treatment systems can be improved by means of additional materials adsorbing soluble P. In this study, light expanded clay aggregates (LECA) and LECA coated with aluminum (Al) oxide (Al-LECA) or iron (Fe) oxide (Fe-LECA) were tested for their efficiency as P sorbents in the pH range 3–8. The oxide coatings duplicated the actual sorption capacity calculated from the sorption isotherms at the P concentration in the equilibrium solution of 20 μg L⁻¹, assumed to be the allowable P level in purified water. In the oxide-coated LECAs the sorption was fast and followed both the first- and second-order Lagergren kinetic models, suggesting that the formation of a binuclear surface complex was feasible. In LECA, sorption was markedly slower and followed the first-order kinetic model, indicating that retention occurred through a monodentate attachment. These findings were in harmony with the degree of P saturation (DPS) of the sorbent surfaces at the highest P addition level (200 μg L⁻¹), DPS being decisively higher for LECA than for the oxide-coated sorbents. Accordingly, at higher pH values the competition by hydroxyl ions diminished the sorption in LECA relatively more than that in the coated sorbents. In agreement with the acidity of Al³⁺ being 100 times lower than that of Fe³⁺, at elevated pH the sorption by Al-LECA proved to be less reversible than that by Fe-LECA. The results provide evidence that in CWs Al-coated sorbents are superior to Fe-coated ones that are also redox-sensitive and may lose their sorption properties in anoxic conditions.     

Emissions of gaseous nitrogen species from manure management: a new approach

A procedure for the assessment of emissions of nitrogen (N) species (ammonia, nitrous oxide, nitric oxide, di-nitrogen) from the manure management system is developed, which treats N pools and flows including emissions strictly according to conservation of mass criteria. As all relevant flows in the husbandry of mammals are depicted, the methodology is considered a Tier 3 approach in IPCC terminology or a detailed methodology in UN ECE terminology. The importance of accounting for all N species is illustrated by comparing emission estimates obtained using this approach with those obtained from the application the present detailed/Tier 2 methodology.     

柴油/甲醇组合燃烧发动机的氮氧化物排放研究

在增压共轨发动机上采用柴油/甲醇组合燃烧(DMCC)方式进行了氮氧化物排放特性研究.对DMCC模式下NO x、NO、NO2等排放与纯柴油模式的对比分析表明:DMCC模式下的NO x排放比原机模式平均下降10%以上,NO平均下降幅度超过40%;采用DMCC模式后,NO2排放量都有明显大幅度的升高,并且NO2/NO比值呈现显著增大,平均高达100%以上.     

羟基化石墨烯氧化NO脱硝反应机理研究

石墨烯氧化物(GO)通常是羟基化石墨烯(Hy G)和羧基化石墨烯(Cy G)负载金属或金属氧化物,作为催化剂可以有效地催化烟气脱硝,对环境保护具有重要意义.本文采用密度泛函理论(DFT)计算来评估Hy G与NO之间的相互作用,以揭示Hy G的氧化活性.首先基于5×5×1、6×6×1、7×7×1、8×8×1和9×9×1周期性石墨烯超晶胞中的碳空位能和OH—结合能来优选Hy G模型,并对优化后的Hy G的电子特性(包括前沿轨道、状态密度)进行研究.进而通过NO和Hy G之间的相互作用,揭示Hy G氧化NO的反应机理,并利用过渡态理论估算关键步骤的速率常数,进行动力学建模以确定羟基化石墨烯氧化NO脱硝反应特性.研究结果表明,无缺陷的羟基化石墨烯氧化NO的活性高于有缺陷的羟基化石墨烯,这为GO基催化材料的设计提供了理论指导.     

The selective catalytic reduction of NO over Ce0.3TiOx-supported metal oxide catalysts

A Ce_(0.3)TiO_xoxide carrier was synthesized via a sol–gel process,and Ce_(0.3)TiO_xsupported metal(M=Cd,Mn,Fe,W,Mo)oxide catalysts were prepared by the method of incipient-wetness impregnation.The catalysts were characterized by means of X-ray diffraction(XRD),Brunauer–Emmett–Teller(BET)analysis,scanning electron microscopy(SEM),transmission electron microscopy(TEM),Fourier transform infrared(FT–IR)spectroscopy,UV–Visdiffusereflectancespectroscopy(UV–VisDRS),and Temperature-programmed reduction with H_2(H_2-TPR).The catalytic activities for de-NO_(x )were evaluated by the NH_3-SCR reaction.Among all the catalysts tested,the 2 wt.%Cd/Ce_(0.3)TiO_xcatalyst exhibited the best NH_3-SCR performance,with a wide temperature window of 250–450°C for NO conversion above 90%.Moreover,the catalyst showed N_2 selectivity greater than 99%from 200 to 450°C.     

基于g-C3N4纳米片/氧化石墨烯复合材料电化学传感器检测水体中左氧氟沙星研究

近年来,随着抗生素的滥用和不加控制的排放,水体中抗生素的检测已经成为环境分析的一个重要研究领域.本文采用简单的超声方法将超薄石墨相氮化碳纳米片（g-C₃N₄Ns）固定在氧化石墨烯（GO）的表面,形成g-C₃N₄Ns/GO纳米复合材料,制备了一种基于石墨相氮化碳/氧化石墨烯的新型电化学传感器,用于环境水样中左氧氟沙星（LEV）的检测.在优化的实验条件下,利用差分脉冲伏安法（DPV）对LEV进行检测,线性范围为0.25～90μmol·L^-1,检出限为0.073μmol·L^-1.该传感器具有良好的稳定性、灵敏度、抗干扰能力和制备简单等优势,并成功地用于测定河水和自来水样中的LEV,具有良好的回收率,为左氧氟沙星的灵敏检测提供了一种可行的方案.     

铁锰氧化物在不同水分条件下对土壤As的稳定化作用

本文以铁锰氧化物(Fe-Mn,FM)为研究对象,评估其在不同水分条件下对我国南方3种砷(As)污染土壤的稳定化修复效果.结果表明,添加一定比例(质量分数30%)水分对于抑制土壤As的毒性浸出具有积极作用,但水分过高(淹水条件)则会引发As的大量活化释放.淹水条件下,FM对As污染土壤具有明显的应用优势,能使韶关、河池和常德这3种土壤毒性浸出质量浓度均显著下降99. 00%以上,使其土壤有效态As含量分别显著降低55. 40%、40. 05%和16. 92%,并增加专性和非专性吸附态As向水合铁铝氧化物结合态的稳定化. FM能使韶关、河池和常德土壤有效态磷(P)含量分别降低0. 60%～6. 67%、15. 74%～50. 00%和32. 48%～40. 39%,这有可能会限制缺P区域农产品对酸性或中性土壤的P摄取. FM对3种供试土壤p H值影响的变化幅度仅为0. 04～0. 07,对土壤环境的影响非常小. FM在我国淹水As污染土壤稳定化修复领域具有较好的应用前景.     

铁碳微电解填料对人工湿地温室气体排放的影响

随着全球气候变暖的问题日益严重,人工湿地中温室气体的减排措施也受到越来越多的关注.铁碳微电解填料对废水处理效果良好且具备温室气体减排的潜力,为探究铁碳微电解对间歇曝气人工湿地温室气体排放的影响,本研究构建了以铁碳微电解填料+砾石（湿地Ⅰ）、铁碳微电解填料+沸石（湿地Ⅱ）、沸石（湿地Ⅲ）以及砾石（湿地Ⅳ）为基质的4组人工湿地,并利用间歇曝气技术对湿地系统进行了增氧.结果表明,铁碳微电解填料显著提高了间歇曝气人工湿地的脱氮效果,且具备对人工湿地温室气体的减排作用.与湿地Ⅳ相比,湿地Ⅰ、Ⅱ和Ⅲ的CH₄排放通量分别平均降低了32.81%（P<0.05）、52.66%（P<0.05）和54.50%（P<0.05）,其中沸石对CH₄的减排效果较优,能显著降低曝气段和非曝气段人工湿地CH₄的排放.铁碳微电解填料明显减少了N₂O的排放,与湿地Ⅳ相比,湿地Ⅰ和Ⅱ分别实现N₂O减排30.29%~60.63%（P<0.05）和43.10%~73.87%（P<0.05）.各组湿地系统在典型周期内排放的CH₄和N₂O引起的综合GWP（以CO₂-eq计）分别为（85.21±6.48）、（49.24±3.52）、（127.97±11.44）和（137.13±11.45）g·m^-2,铁碳微电解填料与沸石的联合使用有效实现了人工湿地温室气体的减排.总体而言,湿地Ⅱ在间歇曝气的条件下对污水净化效果最好,温室气体的减排效果最佳.     

不同晶型铁氧化物Fenton和UV-Fenton降解橙Ⅱ的催化性能

选取了磁铁矿、赤铁矿和针铁矿3种不同晶型的铁氧化物,用XRD和BET进行了表征。将3种铁氧化物作为催化剂用于Fenton和UV-Fenton(254 nm UVC)降解偶氮染料橙II,测定了染料降解过程中溶液中铁离子浓度的变化规律,用于分析3种铁氧化物的催化过程。用单位比表面积反应速率常数(k/Ssur)评价了3种铁氧化物UV-Fenton催化降解橙Ⅱ的能力,以揭示UV-Fenton体系中铁氧化物晶型与催化性能的关系。结果表明,Fenton体系中,磁铁矿能通过表面固有的2价铁催化产生羟基自由基降解橙Ⅱ,其催化能力高于针铁矿和赤铁矿;UV-Fenton体系中,磁铁矿、赤铁矿和针铁矿催化降解橙Ⅱ的单位比表面积反应速率常数分别为0.048 8 g/(m2·min)、0.023 4 g/(m2·min)和0.001 0 g/(m2·min),可见磁铁矿的催化能力明显高于针铁矿和赤铁矿;UV-Fenton体系中,磁铁矿以多相反应为主,针铁矿以均相反应为主,而赤铁矿则是两者共同作用。研究表明,磁铁矿是多相铁氧化物UV-Fenton催化剂的理想晶型,同时也是合成新型多相光助-芬顿催化剂理想的活性组分。     

生物滤床中一氧化氮的好氧去除过程研究

以美国Ultramet公司生产的Carbon-Foam为滤料,应用生物滤床处理NO模拟废气,研究了生物滤床在好氧条件下对NO的处理效果,并对NO去除过程的作用机理进行了探讨.研究结果表明,NO的去除效率随空床停留时间(EBRT)的增加而增加,在EBRT为6min、进口NO浓度为107.14mg.m-3时,NO去除效率为63%;随着进口浓度的提高,NO去除效率降低,而NO消除负荷增加.生物滤床中NO的去除过程由微生物硝化和化学氧化共同作用完成,其中以微生物硝化作用为主.化学氧化作用包括气相过程和液相过程2部分,当EBRT<4.6min时,液相中的化学氧化作用大于气相;当EBRT>4.6min时,气相中的化学氧化作用大于液相.当EBRT≤2min时,传质是NO去除过程的控制步骤,此时,微生物硝化作用和液相中的化学氧化作用均受传质过程控制.