模拟海洋全浸区环境下A517海工钢的腐蚀机理研究

目的 探究 A517 海工钢在海洋全浸区环境下的腐蚀机理。方法 通过模拟海洋全浸区腐蚀环境,利用失重法、SEM、EDS、XRD、电化学等测试技术,分析A517钢的腐蚀行为历程,并探讨其在全浸区的腐蚀机理。结果A517钢在厚度方向上的最大电位差为 13 mV,小于发生电偶腐蚀的最小电位差50mV,说明材料在厚度方向上的腐蚀敏感性一致。随浸泡时间的延长,腐蚀质量损失量逐渐增加,平均腐蚀速率先降低、后升高、最后趋于稳定,腐蚀速率约为 0.127 mm/a。结论 腐蚀动力初期主要是由溶解氧的极限扩散控制,后期则是腐蚀产物的氧化还原电荷转移控制。腐蚀首先在 Al₂O₃、MgO 等夹杂物处萌生扩展,腐蚀产物出现明显的分层现象,外锈层主要是疏松易脱落的γ-FeOOH,内锈层主要是致密均匀的 Fe₃O₄,同时锈层中还检测到了β-FeOOH和α-FeOOH的存在。锈层中存在大量微裂纹,削弱了产物膜的保护作用,促进了腐蚀的进行。     

土壤反硝化田间原位测定方法的研究进展

土壤中的反硝化作用由于直接影响到肥料氮的利用率和环境问题,仍然是氮素研究领域的热点和难点之一,而反硝化作用研究的进展在很大程度上依赖与土壤反硝化的田间测定方法的建立。文章就目前反硝化研究领域常用的15N平衡差值法、15N示踪气体通量法、乙炔抑制气室法、乙炔抑制土柱法的原理、气体样的采集、测定和计算作了综述,以期为土壤反硝化的研究提供依据。     

Analysis of Products Generated from the Thermal and Catalytic Degradation of Pure and Waste Polyolefins using Py-GC/MS

The possibility of transforming waste plastics into valuable hydrocarbons via catalytic cracking and reforming is attracting increasing interest. Pyrolysis coupled with Gas Chromatographic separation and Mass Spectrometry detection (Py-GC/MS) has been used in this work to study the product selectivity of various catalysts in the conversion of pure and residual polyethylene samples into hydrocarbon products. Five acid solids of comparable aluminium contents but different textural and acid properties were tested as catalysts, including three zeolites (standard ZSM-5, nanocrystalline n-ZSM-5 and Beta) and two mesostructured solids (Al-MCM-41 and Al-SBA-15). Thermal cracking of the pure and residual polymers generated a similar range of products to each other, with a high proportion of linear paraffins and olefins of varying lengths. The presence of zeolitic materials resulted in complete elimination of heavy linear products, an increase in the light hydrocarbon fraction and a marked selectivity towards the formation of single-ring aromatic species, particularly benzene, toluene and xylene. Aromatic formation was particularly notable with the small crystal size n-ZSM-5 (aromatic selectivity up to 53.9%) and less marked in the case of standard ZSM-5 (up to 36.4%) and Beta zeolite (up to 35.0%). Mesostructured catalysts like Al-MCM-41 and Al-SBA-15 favoured the production of light C₂–C₅ hydrocarbons (up to 57.9%) while the formation of aromatic products was significantly lower than with zeolitic materials. The paper examines the extent and the causes for this product selectivity and discusses its connection with the acid and textural properties of each catalyst. It was also observed that, under the experimental conditions employed, the products generated were not significantly affected by the nature and origin of the polymers employed.     

利用根箱法解析水稻根际土壤中氮的行为

为研究水田土壤中氮的行为,施给15NH4 或15NO3-标记的硝胺(NH415NO3或15NH4NO3)的沙壤土(Shirasu soil)添充在根箱里,对Japonica水稻(品种Hinohikari)进行温室栽培6周.收割后,水稻植株分地上部和根部,对各自的全氮,15N atom％进行测定.根箱各区域的土壤按着鲜土形态进行采取后,对此全氮,NO3-N,水溶性NH4-N,KCl抽出NH4-N和其各自的15N atom％进行测定.研究结果表明,土壤全氮含量与栽培前相比,在非根际明显降低,但在根际比非根际要高,保持了与栽培前相同的水平.土壤NO3-N浓度从非根际到根际递增,但与其栽培前相比显著地降低,在整个根箱里,施给NO3-N的79％为因脱氮而损失.土壤中NO3-N的大部分来自于土壤氮化合物,来自施肥的比例却较低,尤其是在根际.反而,施给NO3-N的残存率约仅为16％左右,但其中有机态氮所占的比率在非根际里55％～86％,在根际却达到了93％.土壤水溶性NH4-N和KCl抽出NH4-N浓度靠近根际逐渐降低,而且在非根际两者匀由1∶10的比例存在,但在根际里水溶性NH4-N没被检索到.在非根际里,土壤KCl抽出NH4-N的35％～66％为来自施肥,但其比例在根际里却降到15％左右.在土壤中残存的来自施给NH4-N的氮化合物之中,有机态氮所占的比例在非根际里约为11％～65％,但在根际却达到了92％.以上结果表明,在水稻根际,氮的无机化和有机化的活性比非根际显著.     

Low-temperature (NO + O2) adsorption performance of alkaline earth metal-doped C-FDU-15

To improve the removal capacity of NO + O₂ effectively, the alkaline earth metal-doped order mesoporous carbon (A-C-FDU-15(0.001) (A = Mg, Ca, Sr and Ba)) and Mg-C-FDU-15(x) (x = 0.001?0.003) samples were prepared, and their physicochemical and NO + O₂ adsorption properties were determined by means of various techniques. The results show that the sequence in (NO + O₂) adsorption performance was as follows: Mg-C-FDU-15(0.001) (93.2 mg/g) > Ca-C-FDU-15(0.001) (82.2 mg/g) > Sr-C-FDU-15(0.001) (76.1 mg/g) > Ba-C-FDU-15(0.001) (72.9 mg/g) > C-FDU-15 (67.1 mg/g). Among all of the A-C-FDU-15(0.001) samples, Mg-C-FDU-15(0.001) possessed the highest (NO + O₂) adsorption capacity (106.2 mg/g). The species of alkaline earth metals and basic sites were important factors determining the adsorption of NO + O₂ on the A-C-FDU-15(x) samples, and (NO + O₂) adsorption on the samples was mainly chemical adsorption. Combined with the results of (NO + O₂)-temperature-programmed desorption ((NO + O₂)-TPD) and in situ diffused reflectance infrared Fourier transform spectroscopy (DRIFTS) characterization, we deduced that there were two main pathways of (NO + O₂) adsorption: one was first the conversion of NO and O₂ to NO₂ and then part of NO₂ was converted to NO₂^? and NO₃^?; and the other was the direct oxidation of NO to NO₂^? and NO₃^?.     

森林地区PM2.5中氨基酸的水平、来源及转化

在春季采集了南昌森林地区(28.75°N,115.71°E)大气PM_2.5样品,测定了其结合氨基酸(CAAs)和游离氨基酸(FAAs)的浓度以及甘氨酸(Gly)的氮同位素.结果表明,大气气溶胶中总CAAs的浓度为272.8~4761.5pmol/m³,总FAAs浓度为56.4~494.0pmol/m³.通过分析PM_2.5中氨基酸的百分比组成,得出CAAs中Pro、Gly、Glu、Leu和Ala为主要氨基酸,分别占总CAAs的(19.5±12.0)%, (19.4±10.6)%, (15.3±4.9)%, (12.8±5.4)%和(9.1±1.6)%.在FAAs中,Gly为最丰富的氨基酸,占总FAAs的(71.1±9.2)%,其他单个FAAs的百分比却很小(占比范围为0.1%~14.3%).FAAs中的中性氨基酸百分占比明显高于其在CAAs中的百分占比,这可能与远距离传输过程中氨基酸的光化学反应有关.通过氨基酸浓度与O₃、NO₂和温度的相关性分析,发现森林地区气溶胶中FAAs形成与大气光化学过程和热反应有关.气溶胶中δ¹⁵N_C-Gly值(-1.0‰~+17.5‰)和δ¹⁵N_F-Gly值(-5.5‰~+13.0‰)均接近于土壤源的δ¹⁵N_Gly值,说明森林地区PM_2.5中氨基酸可能主要来源于土壤源.     

柴油加氢装置关键换热器管束腐蚀机理研究

目的明确兰州石化柴油加氢装置某换热器管束(主要材质为15Cr Mo钢和321不锈钢)的腐蚀失效原因。方法采用高温高压釜试验和模拟铵盐结晶试验研究15Cr Mo钢和321不锈钢在服役介质中的腐蚀机理。结果 15Cr Mo钢的腐蚀失效形式表现为铵盐结晶下的快速均匀腐蚀和其他部位的点蚀;而321不锈钢的腐蚀失效形式则相反,主要表现为铵盐结晶下的点蚀。结论为避免铵盐结晶引起的腐蚀穿孔,建议提高换热器出口温度到230℃以上,将换热器出口的注水工艺改为注中和缓蚀剂,在加氢反应器出口增设脱氯罐。     

伊乐藻-固定化脱氮微生物技术对入贡湖河道脱氮机制的影响

采用无扰动的入贡湖亲水河底泥柱芯以及上覆水进行实验,探究了伊乐藻与固定化脱氮微生物技术对受污染的入贡湖湾河道的生态修复效果.运用稳定性15N同位素配对技术和基于16S rRNA高通量测序技术探讨了伊乐藻与固定化脱氮微生物联用技术(E-INCB)对亲水河底泥的反硝化速率、厌氧氨氧化速率以及脱氮微生物群落多样性的影响.结果表明,添加了伊乐藻与固定化脱氮微生物以后,亲水河水质得到明显改善,TN、NH+4-N、NO-3-N的去除率分别为72.03%、46.67%、76.65%,同时,添加了伊乐藻和固定化脱氮微生物以后,泥水界面的反硝化细菌和厌氧氨氧化细菌表现出协同作用关系,与对照组相比,反硝化速率和厌氧氨氧化速率增加量分别为165μmol·(m2·h)-1和269.7μmol·(m2·h)-1.反硝化细菌与厌氧氨氧化细菌的群落多样性明显增加,变形菌门(Proteobacteria)、浮霉菌门(Planctomycetes)、酸杆菌门(Acidobbacteria)和拟杆菌门(Bacteroidetes)均具有优势增长.沉水植物与固定化脱氮微生物联用技术增强了河道底泥中的脱氮微生物多样性,进一步提高了亲水河的氮素脱除能力.     

C8-SBA-15新型介孔涂层SPME-HPLC联用测定水样中的芘

以辛基键合SBA- 15为固相微萃取(SPME)的吸附涂层,考察了吸附和解吸时间、萃取温度、搅拌速率对SPME效率的影响.该方法的线性范围为3.0-320μg/L,检出限为0.5μg/L,依据此方法测定了环境水样中芘,具有灵敏度高和精密度好的特点.     

Binding of trinitrotoluene (TNT) to water extractable humus

Solid-state ¹⁵N NMR was applied to the aqueous extracts of a ¹³C-enriched plant slurry (Lolium perenne), anaerobically incubated with ¹⁵N₃-trinitrotoluene (TNT). Almost all ¹⁵N₃-TNT transformation products became covalently bound to the plant-derived organic material extractable with water. DCPMAS ¹⁵N ¹³C NMR revealed a three-step reaction scheme. After reduction of TNT, the aryl amines are acetylated. Subsequent alkylation of the resulting amides strengthens the incorporation of TNT-transformation products into humic material. Comparable results have been recently obtained under aerobic conditions, which indicates that this pathway is a common process during biological TNT transformation.