自然生境中厌氧氨氧化功能微生物生态学研究进展

自然生境中发生的厌氧氨氧化过程是继反硝化和好氧氨氧化后的又一条氮损失途径,对全球生态系统氮循环具有重要意义,但不同自然生态系统中存在不同种类的厌氧氨氧化微生物.通过阐述厌氧氨氧化反应发生的生理机制,并对不同自然环境中发现的厌氧氨氧化功能微生物进行梳理,分析了厌氧氨氧化菌分布的空间异质性成因.结果表明,适量的无机氮可以促进厌氧氨氧化的发生,有机碳含量低和低氧条件更有利于厌氧氨氧化菌的生存且厌氧氨氧化的活性较高,这与厌氧氨氧化菌的化能自养代谢途径有着紧密的联系,低养分条件下反硝化菌的活性受到短暂抑制,促进了厌氧氨氧化的发生.同时,适当的高盐环境会提高厌氧氨氧化活性并促进厌氧氨氧化菌群落结构转变,高盐度环境下Scalindua属占优势,低盐度环境下Brocadia属更占优势.厌氧氨氧化菌对温度变化有很好的适应性,大部分厌氧氨氧化菌（如Scalindua属、Kuenenia属和Brocadia属）对于极端环境均有较强的环境适应性;此外,悬浮颗粒物浓度、含水量等因素也会影响厌氧氨氧化菌的分布及其代谢活性.建议今后从基因组学、蛋白组学和转录组学相结合的角度对自然环境中的厌氧氨氧化菌开展生理生态机理的研究,并探明厌氧条件下Fe3+、Mn4+、SO₄2-等电子受体与厌氧氨氧化过程的生物化学联系,以更好地应用于工程技术研究,并为生态环境修复提供理论依据.      

西北生态脆弱区畜禽粪污处理技术综合评价

畜禽粪污处理技术在不同地区适用性有较大差异。为全面、客观、科学地筛选出适宜西北地区的畜禽粪污处理技术,将生命周期评价、费用效益评价与层次分析法耦合,从技术、经济、气候、直接环境影响与间接环境影响5个方面,建立了包含18项指标的西北生态脆弱区畜禽粪污处理技术评价体系;以兰州市畜禽粪污处理技术为例,分析好氧堆肥、厌氧发酵、垫料利用3种处理技术的适用性。结果表明：兰州市畜禽粪污处理技术适用性综合排序为垫料利用（72.21分）>好氧堆肥（71.55分）>厌氧发酵（68.79分）,垫料利用技术更适宜在西北地区推广;垫料利用技术环境友好性明显优于厌氧发酵和好氧堆肥技术;使用好氧堆肥和厌氧发酵技术处理畜禽粪污可为养殖场增加额外收益。该研究可为西北地区畜禽粪污处理技术模式构建和优化提供指导。

     

焦化污染场地土壤多环芳烃的生物强化协同降解工艺研究

以某废弃焦化厂的多环芳烃（PAHs）污染土壤为研究对象,通过耦合表活淋洗、生物降解、化学氧化等技术设计了4种修复工艺,并进行了试验验证。结果表明：针对该实际焦化污染土壤,单一的生物泥浆降解工艺21 d后PAHs可实现58.64%的降解率;采用表活增溶＋化学氧化＋生物泥浆的降解工艺,26 d降解率可达到65.68%,但前置的化学氧化会抑制生物降解效果;采用干筛分+表活分批淋洗+化学氧化的降解工艺降解率可达到85.36%,有效缩短降解时间到13 d内,但土壤中残留的PAHs与土壤颗粒结合紧密,化学氧化降解率仍难以满足大于90%的要求;采用湿筛分+表活分批淋洗+生物泥浆+化学氧化的生物强化协同降解工艺,29 d降解率可达到95.32%,实现了土壤的修复目标。生物强化协同降解工艺路线,综合了多种修复技术的优点,实现了修复技术组合优化,为焦化污染土壤中多环芳烃降解修复提供了可行的工艺路径。

     

Promotional effect of cobalt doping on catalytic performance of cryptomelane-type manganese oxide in toluene oxidation

The cryptomelane-type manganese oxide (OMS-2)-supported Co (xCo/OMS-2; x = 5, 10, and 15 wt.%) catalysts were prepared via a pre-incorporation route. The as-prepared materials were used as catalysts for catalytic oxidation of toluene (2000 ppmV). Physical and chemical properties of the catalysts were measured using the X-ray diffraction (XRD), Fourier transform infrared spectroscopic (FT-IR), scanning electron microscopic (SEM), X-ray photoelectron spectroscopy (XPS), and hydrogen temperature-programmed reduction (H₂-TPR) techniques. Among all of the catalysts, 10Co/OMS-2 performed the best, with the T_90%, specific reaction rate at 245°C, and turnover frequency at 245°C (TOF_Co) being 245°C, 1.23 × 10⁻³ mol_toluene/(g_cat·sec), and 11.58 × 10⁻³ sec⁻¹ for toluene oxidation at a space velocity of 60,000 mL/(g·hr), respectively. The excellent catalytic performance of 10Co/OMS-2 were due to more oxygen vacancies, enhanced redox ability and oxygen mobility, and strong synergistic effect between Co species and OMS-2 support. Moreover, in the presence of poisoning gases CO₂, SO₂ or NH₃, the activity of 10Co/OMS-2 decreased for the carbonate, sulfate and ammonia species covered the active sites and oxygen vacancies, respectively. After the activation treatment, the catalytic activity was partly recovered. The good low-temperature reducibility of 10Co/OMS-2 could also facilitate the redox process accompanied by the consecutive electron transfer between the adsorbed O₂ and the cobalt or manganese ions. In the oxidation process of toluene, the benzoic and aldehydic intermediates were first generated, which were further oxidized to the benzoate intermediate that were eventually converted into H₂O and CO₂.     

Comparison of UV-based advanced oxidation processes for the removal of different fractions of NOM from drinking water

This study examined the effectiveness for degradation of hydrophobic (HPO), transphilic (TPI) and hydrophilic (HPI) fractions of natural organic matter (NOM) during UV/H₂O₂, UV/TiO₂ and UV/K₂S₂O₈ (UV/PS) advanced oxidation processes (AOPs). The changing characteristics of NOM were evaluated by dissolved organic carbon (DOC), the specific UV absorbance (SUVA), trihalomethanes formation potential (THMFP), organic halogen adsorbable on activated carbon formation potential (AOXFP) and parallel factor analysis of excitation–emission matrices (PARAFAC-EEMs). In the three UV-based AOPs, HPI fraction with low molecular weight and aromaticity was more likely to degradate than HPO and TPI, and the removal efficiency of SUVA for HPO was much higher than TPI and HPI fraction. In terms of the specific THMFP of HPO, TPI and HPI, a reduction was achieved in the UV/H₂O₂ process, and the higest removal rate even reached to 83%. UV/TiO₂ and UV/PS processes can only decrease the specific THMFP of HPI. The specific AOXFP of HPO, TPI and HPI fractions were all able to be degraded by the three UV-based AOPs, and HPO content is more susceptible to decompose than TPI and HPI content. UV/H₂O₂ was found to be the most effective treatment for the removal of THMFP and AOXFP under given conditions. C1 (microbial or marine derived humic-like substances), C2 (terrestrially derived humic-like substances) and C3 (tryptophan-like proteins) fluorescent components of HPO fraction were fairly labile across the UV-based AOPs treatment. C3 of each fraction of NOM was the most resistant to degrade upon the UV-based AOPs. Results from this study may provide the prediction about the consequence of UV-based AOPs for the degradation of different fractions of NOM with varied characteristics.     

Experimental and theoretical studies on NO selective catalytic oxidation over α-MnO2

Based on the experimental and theoretical methods, the NO selective catalytic oxidation process was proposed. The experimental results indicated that lattice oxygen was the active site for NO oxide over the $\mathrm{\alpha }$-MnO₂(110) surface. In the theoretical study, DFT (density functional theory) and periodic slab modeling were performed on an $\mathrm{\alpha }$-MnO₂(110) surface, and two possible NO oxidation mechanisms over the surface were proposed. The non-defect $\mathrm{\alpha }$-MnO₂(110) surface showed the highest stability, and the surface O_s (the second layer oxygen atoms) position was the most active and stable site. O₂ molecule enhanced the joint adsorption process of two NO molecules. The reaction process, including O₂ dissociation and O=N-O-O-N=O formation, was calculated to carry out the NO catalytic oxidation mechanism over $\mathrm{\alpha }$-MnO₂(110). The results showed that NO oxidation over the $\mathrm{\alpha }$-MnO₂(110) surface exhibited the greatest possibility following the route of O=N-O-O-N=O formation. Meanwhile, the formation of O=N-O-O-N=O was the rate-determining step.     

Promotional catalytic activity and reaction mechanism of Ag-modified Ce0.6Zr0.4O2 catalyst for catalytic oxidation of ammonia

Ce_1-xZr_xO₂ composite oxides (molar, x = 0-1.0, interval of 0.2) were prepared by a cetyltrimethylammonium bromide-assisted precipitation method. The enhancement of silver-species modification and catalytic mechanism of adsorption-transformation-desorption process were investigated over the Ag-impregnated catalysts for low-temperature selective catalytic oxidation of ammonia (NH₃-SCO). The optimal 5 wt.% Ag/Ce_0.6Zr_0.4O₂ catalyst presented good NH₃-SCO performance with >90% NH₃ conversion at temperature (T) ≥ 250°C and 89% N₂ selectivity. Despite the irregular block shape and underdeveloped specific surface area (∼60 m²/g), the naked and Ag-modified Ce_0.6Zr_0.4O₂ solid solution still obtained highly dispersed distribution of surface elements analyzed by scanning electron microscope-energy dispersive spectrometer (SEM-EDS) (mapping), N₂ adsorption-desorption test and X-ray diffraction (XRD). H₂ temperature programmed reduction (H₂-TPR) and X-ray photoelectron spectroscopy (XPS) results indicated that Ag-modification enhanced the mobility and activation of oxygen-species leading to a promotion on CeO₂ reducibility and synergistic Ag⁰/Ag⁺ and Ce⁴⁺/Ce³⁺ redox cycles. Besides, Ag⁺/Ag₂O clusters could facilitate the formation of surface oxygen vacancies that was beneficial to the adsorption and activation of ammonia. NH₃-temperature programmed desorption (NH₃-TPD) showed more adsorption-desorption capacity to ammonia were provided by physical, weak- and medium-strong acid sites. Diffused reflectance infrared Fourier transform spectroscopy (DRIFTS) experiments revealed the activation of ammonia might be the control step of NH₃-SCO procedure, during which NH₃ dehydrogenation derived from NH_x-species and also internal selective catalytic reduction (i-SCR) reactions were proposed.     

Decomplexation of Cu-1-hydroxyethylidene-1,1-diphosphonic acid by a three-dimensional electrolysis system with activated biochar as particle electrodes

The feasibility of decomplexation removal of typical contaminants in electroplating wastewater, complexed Cu(II) with 1-hydroxyethylidene-1,1-diphosphonic acid (Cu-HEDP), was first performed by a three-dimensional electric reactor with activated biochar as particle electrodes. For the case of 50 mg/L Cu-HEDP, Cu(II) removal (90.7%) and PO initial pH 7, acid-treated almond shell biochar (AASB) addition 20 g/L, and reaction time 180 min, with second-order rate constants of 1.10 × 10⁻³ and 1.94 × 10⁻⁵ min⁻¹respectively. The growing chelating effect between Cu(II) and HEDP and the comprehensive actions of adsorptive accumulation, direct and indirect oxidation given by particle electrodes accounted for the enhanced removal of Cu-HEDP, even though the mineralization of HEDP was mainly dependent on anode oxidation. The performance attenuation of AASB particle electrodes was ascribed to the excessive consumption of oxygen-containing functionalities during the reaction, especially acidic carboxylic groups and quinones on particle electrodes, which decreased from 446.74 to 291.48 µmol/g, and 377.55 to 247.71 µmol/g, respectively. Based on the determination of adsorption behavior and indirect electrochemical oxidation mediated by in situ electrogenerated H₂O₂ and reactive oxygen species (e.g., •OH), a possible removal mechanism of Cu-HEDP by three-dimensional electrolysis was further proposed.     

滇池周边浅层地下水硝酸盐来源及转化过程识别

明确硝酸盐的主要来源及转化过程对地下水氮污染防治和水资源开发利用具有重要意义.为了探明滇池周边浅层地下水中硝酸盐污染现状及来源,于2020年雨季（10月）和2021年旱季（4月）在滇池周边共采集73个浅层地下水样,运用水化学和氮氧同位素（δ¹⁵N-NO₃^-、δ¹⁸O-NO₃^-）识别浅层地下水中硝酸盐的空间分布、来源及转化过程,并结合同位素混合模型（SIAR）定量评价不同来源氮对浅层地下水硝酸盐的贡献.结果表明,旱季浅层地下水中有40.5%的采样点ρ（NO₃^--N）超过地下水质量标准（GB/T 14848）Ⅲ类水质规定的20 mg·L^-1,雨季超过47.2%的采样点ρ（NO₃^--N）超过20 mg·L^-1.氮氧同位素和SIAR模型分析结果证明了土壤有机氮、化肥氮、粪肥和污水氮是浅层地下水硝酸盐的主要来源,以上氮源对旱季浅层地下水中硝酸盐的贡献率分别为13.9%、11.8%和66.5%,对雨季的贡献率分别为33.7%、31.1%和25.9%,而大气氮沉降贡献率仅为8.5%,对该区浅层地下水中硝酸盐来源贡献较小.硝化作用是旱季浅层地下水中硝态氮转化的主导过程,雨季以反硝化作用为主,且反硝化作用雨季比旱季明显.     

固体推进剂老化过程影响因素及化学反应机理研究进展

基于固体推进剂的贮存老化,以NEPE推进剂和以HTPB推进剂为代表,综述了近年来固体推进剂老化进程中所受的各种影响因素、作用机制及化学反应机理研究进展。总结了温湿度、应力和环境气氛为代表的外部环境因素,配方性质、组分变化和添加剂等内部影响因素对推进剂老化及贮存失效期限的影响。分别从微观和宏观角度出发,分析了内外部各种影响因素加速或减缓固体推进剂老化进程的作用机制。此外,针对黏合剂、氧化剂、防老剂等化学组分,总结了固体推进剂贮存老化期间发生的氧化交联、分解、降解断链等主要化学反应,并分析了各个反应发生的机理及原因。最后,展望了未来固体推进剂老化影响因素研究的发展趋势,并为今后固体推进剂老化机理及失效模式研究提供了研究思路。