GdFeO3上CO氧化的Redox机理动力学

ＧｄＦｅＯ３用柠檬酸络合制备。用ＸＲＤ测定ＧｄＦｅＯ３为钙钛矿结构。用ＣＯ还原脉冲及用Ｏ２再氧化脉冲证实在ＧｄＦｅＯ３上ＣＯ氧化为Ｒｅｄｏｘ机理。用外循环流动无梯度反应顺研究了ＣＯ氧化稳态动力学。用正交设计法估计动力学方程中的参数。还原催化剂再氧化为控制步骤。     

Influence of no-tillage on the distribution and lability of phosphorus in Finnish clay soils

No-tillage (NT) is a method adopted to reduce erosion and particulate phosphorus (P) load from arable land to watercourses. However, it has been found to increase the loss of dissolved P with surface runoff, but the reasons for that have rarely been examined in detail. The objective of the present study was to determine the chemical factors explaining this response by investigating the impact of NT on the type and distribution of P reserves as well as on organic carbon (C) in the 0–35 cm topsoil layer of clay soil profiles (Vertic Cambisols). Soil samples were taken from two experimental fields (Jokioinen and Aurajoki) at 0–5, 5–20 and 20–35 cm depths in conventionally tilled (CT) and non-tilled (for 4–5 years) plots. The plots had been cultivated and fertilized according to the common field practices in Finland (15–18 kg P and 100–128 kg N ha⁻¹ year⁻¹).Inorganic and organic P reserves characterized by a modified Chang and Jackson fractionation procedure were not significantly affected by the cultivation methods. However, in the uppermost soil layer (0–5 cm) in NT of the Jokioinen field, the labile P determined by water extraction (P_w) increased significantly, whereas the increase in P extracted with acid ammonium acetate (P_AAC) remained statistically insignificant. The increase in labile P coincided with a significant increase in organic carbon (C), which supports the theory that competition between organic anions and phosphate for the same sorption sites on oxide surfaces will enhance the lability of soil P. In the Aurajoki field with distinct soil cracking, P_w and P_AAC were not affected by NT in the uppermost soil layer, but they increased in the deepest soil layer (20–35 cm) concomitantly with an increase in Al-bound P and organic C. However, the increases were not statistically significant. In both fields, soil acidification due to the repeated application of N fertilizers at a shallow soil depth as well as the accumulation of organic C lowered pH of the uppermost soil layer in NT compared to the deeper soil layers. The results indicated that even short-term NT can increase the labile P in clay soil. However, further studies are needed to assess the long-term changes in lability of surface soil P and, consequently, the possible need for readjustment of the fertilization level in NT.     

无砾石微孔管地下渗滤系统试验研究

针对传统无砾石管式地下渗滤系统存在的处理性能差,渗滤通量低两个问题,通过去掉包裹织物,提高渗滤管开孔率、改变开孔方式,设计了无砾石微孔管地下渗滤系统。通过实验研究表明,无砾石微孔管地下渗滤系统对COD、氨氮的去除率比传统管式系统分别提高了10.8%、12.7%,总磷去除率并无显著差异,ORP值提高约85 mV,渗滤通量提高26.8%。在3.3 cm/d的水力负荷下,无砾石微孔管地下渗滤系统出水COD、氨氮、总磷平均浓度分别为19 mg/L,0.62 mg/L,0.048 mg/L。渗滤管下10 cm的土壤层去除了约70%的COD,80%的氨氮和91%的总磷,向下随着土壤深度的增加,单位厚度的土壤层去除的污染物量呈显著下降趋势。     

填埋场中铁的生物化学循环对反硝化的影响

在模拟填埋体系中,以填埋场稳定的垃圾为接种物,通过控制有机物和硝氮负荷,研究了铁的生物化学循环对反硝化的影响.结果表明,垃圾填埋场内蕴藏着能实现铁的厌氧氧化还原并同步还原硝氮的复合功能菌群.通过改变有机物和硝氮的负荷,可使得填埋场内持续进行着铁的氧化还原循环和同步氮素转化.从氮素转化产物来看,铁的循环体系中氨氮浓度比传统的反硝化体系低4 mmol·L-1.填埋场内铁的生物化学循环过程对于原位脱氮具有极大贡献.     

产品的振动冲击响应设计

在抗振缓冲设计中,人们通常按标准、合同中的要求进行设计,本文认为要按产品受振动与冲击后的响应进行设计,及如何按振动与冲击后的响应进行设计。     

铬渣秸秆共热解产物铬稳定性研究

生物质铬渣共热解工艺是新型的铬渣处理工艺,该工艺能有效地将铬渣中的Cr(Ⅵ)还原为Cr(Ⅲ).而由于共热解产物总铬含量较高,因此考察了铬渣与秸秆共热解过程中铬稳定性.通过考察共热解产物成分及形态分析、pH影响实验、淋洗实验及长期稳定性实验,对共热解铬渣的铬环境安全性进行评估.结果表明:(1)共热解温度对铬渣形态有较大影响,可交换态及碳酸盐结合态铬含量随共热解温度升高而逐渐降低,800℃时候可交换态铬降至＜0.1％(质量分数,下同),碳酸盐结合态铬为1.2％;共热解后最稳定的残渣态铬含量随共热解温度升高而逐渐升高.(2)当pH＞7时,两种共热解产物总铬溶出量极低,基本都小于6mg/kg;当pH≤7时,总铬的溶出量显著增加,最高超过500 mg/kg.但由于解毒铬渣的酸中和能力极强,因此铬释放风险较低.(3)共热解产物的总铬累积溶出量极低,根据拟合结果计算出其100年填埋时间的总铬溶出量不超过1.3 mg/kg.长期稳定性实验表明,自然堆置过程中共热解产物的Cr(Ⅵ)含量逐渐降低.     

不同氧化还原条件下土壤中Cd/Zn/Cu共运移特征及数值模拟

以重金属离子镉（Cd）、锌（Zn）、铜（Cu）为研究对象,通过室内土柱混合置换实验和数值模拟方法,分析了5种不同氧化还原电位（E_h）对Cd、Zn、Cu在土壤中运移的影响.结果表明,不同E_h下,Cu的竞争吸附能力均大于Cd和Zn,移动性较小;并产生了“滚雪球效应”,导致出流液中Cd和Zn的浓度大于输入浓度.与原土相比,E_h的增加或降低均促进了Zn、Cd的迁移速率,但对实验周期内回收率的影响不同;E_h的增加促进了Cu的迁移.两点非平衡模型（TSM）和单点非平衡吸附模型（OSM）较好地模拟了重金属的迁移,且进一步表明了土壤对重金属的吸附受吸附反应速率的限制（f<0.7）.在复合污染土壤评价和防治中,不仅要考虑E_h的影响,还要关注由竞争吸附所产生的浓度叠加效应,避免低估重金属的污染风险.     

大气气溶胶酸度和酸化缓冲能力研究

为了掌握大气气溶胶与酸性降水的关系 ,分析和研究了中国北方和南方不同观测点可吸入颗粒物 (PM10 )的酸度 ,并利用微量酸碱滴定的方法测定了其酸化缓冲能力。结果表明大气气溶胶具有一定的酸度 ,同时对酸化的缓冲能力非常低 ,甚至可以促进降水的酸化 ,这种污染特征也是上述观测点发生酸性降水的重要原因之一。     

Photocatalytic mechanisms of indoleamine destruction by the quinalphos metabolite 2-hydroxyquinoxaline: a study on melatonin and its precursors serotonin and N-acetylserotonin

The redox-active quinalphos main metabolite, 2-hydroxyquinoxaline, is particularly effective under excitation by light. We have studied the photocatalytic destruction of melatonin and its precursors, because the cytoprotective indoleamine has been detected in high quantities in mammalian skin. In photooxidation reactions, in which melatonin, N-acetylserotonin and serotonin are destroyed by 2-hydroxyquinoxaline, the photocatalyst is virtually not consumed. Rates of melatonin and serotonin destruction are not changed by the singlet oxygen quencher 1,4-diazabicyclo-(2,2,2)-octane, indicating that this oxygen species is not involved in the primary reactions, so that the persistence of 2-hydroxyquinoxaline has to be explained by redox cycling. This should imply formation of an organic radical, presumably the quinoxaline-2-oxyl radical, from which 2-hydroxyquinoxaline is regenerated by electron abstraction from indolic radical scavengers. Electron donation by 2-hydroxyquinoxaline is demonstrated by reduction of the 2,2′-azino-bis-(3-ethylbenzthiazolinyl-6-sulfonic acid) cation radical under ultrasound excitation. The compound 2-hydroxyquinoxaline interacts with the specific superoxide anion scavenger Tiron. Formation of oligomeric products from melatonin and serotonin is strongly inhibited by sodium dithionite. Products from photocatalytic indolamine conversion are predominantly dimers and oligomers. No kynuramines were detected in the case of serotonin oxidation, and melatonin's otherwise prevailing oxidation product N ¹-acetyl-N ²-formyl-5-methoxykynuramine, another cytoprotective metabolite, is only formed in relatively small quantities. The proportion between products from melatonin is changed by 1,4-diazabicyclo-(2,2,2)-octane: singlet oxygen, also formed under the influence of excited 2-hydroxyquinoxaline, only affects secondary reactions.     

Effects of WOx modification on the activity, adsorption and redox properties of CeO2 catalyst for NOx reduction with ammonia

A series of WO₃/CeO₂ (WOx/CeO₂) catalysts were synthesized by wet impregnation of ammonium metatungstate on a CeO₂ support. The resulting solid acid catalysts were characterized by X-ray diffraction (XRD), UV-Vis spectroscopy (UV-Vis), Raman spectroscopy (Raman), in-situ Fourier transform infrared spectroscopy (in-situ FT-IR) of ammonia adsorption, NH₃-TPD, H₂ temperature-programmed reduction (H₂-TPR), NH₃/NO oxidation and activity measurements for NOx reduction by NH₃ (NH₃-SCR). The results show that polytungstate (WOx) species are the main species of tungsten oxide on the surface of ceria. The addition of tungsten oxide enhances the Brönsted acidity of ceria catalysts remarkably and decreases the amount of surface oxygen on ceria, with strong interaction between CeO₂ and WOx. As a result, the N₂ selectivity of NH₃ oxidation and NH₃-SCR at high temperatures (> 300℃) is enhanced. Therefore, a wide working temperature window in which NOx conversion exceeds 80% (NOx conversion > 80%) from 200 to 450℃, is achieved over 10 wt.% WOx/CeO₂ catalyst. A tentative model of the NH₃-SCR reaction route on WOx/CeO₂ catalysts is presented.