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。     

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.     

处理含硫废水的新型催化剂

合成了适合处理含硫废水的固相催化剂,考察了催化剂的稳定性、活性及对实际废水的处理效果,开了含硫废水处理的一条新途径。     

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.     

Enhanced U(VI) bioreduction by alginate-immobilized uranium-reducing bacteria in the presence of carbon nanotubes and anthraquinone-2,6-disulfonate

Uranium-reducing bacteria were immobilized with sodium alginate, anthraquinone-2, 6-disulfonate (AQDS), and carbon nanotubes (CNTs). The effects of different AQDS-CNTs contents, U(IV) concentrations, and metal ions on U(IV) reduction by immobilized beads were examined. Over 97.5% U(VI) (20 mg/L) was removed in 8 hr when the beads were added to 0.7% AQDS-CNTs, which was higher than that without AQDS-CNTs. This result may be attributed to the enhanced electron transfer by AQDS and CNTs. The reduction of U(VI) occurred at initial U(VI) concentrations of 10 to 100 mg/L and increased with increasing AQDS-CNT content from 0.1% to 1%. The presence of Fe(III), Cu(II) and Mn(II) slightly increased U(VI) reduction, whereas Cr(VI), Ni(II), Pb(II), and Zn(II) significantly inhibited U(VI) reduction. After eight successive incubation-washing cycles or 8 hr of retention time (HRT) for 48 hr of continuous operation, the removal efficiency of uranium was above 90% and 92%, respectively. The results indicate that the AQDS-CNT/AL/cell beads are suitable for the treatment of uranium-containing wastewaters.     

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.     

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.     

不同制备温度的水稻生物炭电子交换能力研究

为探究不同热解温度下生物炭的电子交换能力,通过限氧升温炭化法,利用水稻秸秆在不同热解温度条件下制备生物炭,与氧气、铁氰化钾氧化剂和柠檬酸钛还原剂进行氧化还原反应,对生物炭的得电子能力（EAC）和失电子能力（EDC）进行定量分析.结果显示,热解温度对生物炭的电子交换能力有较大影响,随热解温度升高至500℃时,生物炭的EAC和EDC达到最大,分别为3.86,1.72mmol/g高于500℃后,随着温度的增加,EAC和EDC逐渐减小,这是由于生物炭的醌类和酚类官能团的结构改变以及持久性自由基强度变化的联合作用.此外,柠檬酸钛和连二硫酸钠两种氧化还原电位不同的还原剂进一步证实了还原剂电位对生物炭EAC的影响.且生物炭具有氧化还原的可逆性,可逆的EAC与EDC之和近似等于生物炭的电子储存能力.     

Effect of natural organic matter on arsenic release from soils and sediments into groundwater

Arsenic (As) contamination in groundwater has received significant attention recently. Natural and anthropogenic sources contribute to the worldwide occurrence of As contamination. As speciation is an important factor related to its toxic and mobile behavior. The release of As from soils and sediments into groundwater is governed by several geophysicochemical processes, of which, As sorption behavior is of principle significance. This review paper summarizes existing information regarding the effects of natural organic matter (NOM) on the fate and mobility of As species in the environment. NOM may enhance the release of As from soils and sediments into the soil solution, thereby facilitating As leaching into the groundwater. The main influencing mechanisms include competition for available adsorption sites, formation of aqueous complexes, and/or changes in the redox potential of site surfaces and As redox speciation. NOM may also serve as binding agents, thereby reducing As mobility. However, comparably little research has been performed on this aspect. Since most investigations have been done on purified minerals under laboratory conditions, further research involving various geological materials under natural environmental conditions is required. Development of proper geochemical conceptual models may provide means of predicting the role of NOM in arsenic leaching and/or immobilization.