新型绿色化学反应介质的研究进展

综述了绿色化学在反应介质方面的研究进展。新型的有机合成反应介质主要包括离子液体、超临界流体、水溶剂及微波无溶剂技术。这些新型反应介质不仅可以取代传统的挥发性有毒有害有机溶剂,同时还可提高反应的活性和选择性,加速反应的进行,且有利于催化剂的回收利用及产品的分离。新型绿色化学反应介质是实现有机合成绿色化的重要途径。     

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.     

大孔强碱阴树脂去除饮用水中微量有机物

比较了大孔强碱阴树脂和颗粒活性炭在饮用水的深度处理中对有机物的去除效果。结果表明：(1)大孔强碱阴树脂的吸附容量比颗粒活性炭的大。在pH为8时,大孔强碱阴树脂对TOC的去除率最高。pH6～8时,对TOC的去除率没有明显的区别,而颗粒活性炭在pH为2时。对TOC的去除率最高;水温低能提高2种吸附材料的吸附容量。(2)在动态实验条件下。当流速相同,大孔强碱阴树脂的穿透时间明显比颗粒活性炭的长,大孔强碱阴树脂的制水量约是吸附床的10000倍。而颗粒活性炭却只有吸附床的4000倍。在饮用水的深度处理中,大孔强碱阴树脂可作为活性炭的最佳替代品。     

延河沉积物的石油污染调查与分析

对延河干流和两条支流受石油污染河段的沉积物的取样分析结果表明 ,研究河段内的沉积物都不同程度的受到了石油污染。干流河段沉积物的石油污染负荷一般为 40～ 80mg/kg ,上游河段和污染支流汇入段负荷较高 ,平均为390mg/kg,最高可达 784mg/kg ;支流上的坪桥川和杏子河河段沉积物污染负荷为 6 0～ 2 5 0mg/kg。干流中下游及杏子河支流河段的污染沉积物主要来源于雨期流域表层污染土壤径流入河后的沿程沉积 ,而非雨期岸边油井的直接排污则是造成干流上游和坪桥川支流沉积物石油污染的主要原因     

Microbial cycling of iron and sulfur in acidic coal mining lake sediments

Lakes caused by coal mining processes are characterized by low pH, low nutrient status, and high concentrations of Fe(II) and sulfate due to the oxidation of pyrite in the surrounding mine tailings. Fe(III) produced during Fe(II) oxidation precipitates to the anoxic acidic sediment, where the microbial reduction of Fe(III) is the dominant electron-accepting process for the oxidation of organic matter, apparently mediated by acidophilic Acidiphilium species. Those bacteria can reduce a great variety of Fe(III)-(hydr)oxides and reduce Fe(III) and oxygen simultaneously which might be due to the small differences in the redox potentials under low pH conditions. Due to the absence of sulfide, Fe(II) formed in the upper 6 cm of the sediment diffuses to oxic zones in the water layer where itcan be reoxidized by Acidithiobacillus species. Thus, acidic conditions are stabilized by the cycling of iron which inhibits fermentative and sulfate-reducing activities. With increasing sediment depth, the amount of reactive iron decrease, the pH increases above 5, and fermentative and as yet unknown Fe(III)-reducing bacteria are also involved in the reduction of Fe(III). Sulfate is reduced apparently by the activity of spore-forming sulfate reducers including new species of Desulfosporosinus that have their pH optimum similar to in situconditions and are not capable of growth at pH 7. However, generation of alkalinity via sulfate reduction is reduced by the anaerobic reoxidation of sulfide back to sulfate. Thus, the microbial cycling of iron at the oxic-anoxic interface and the anaerobic cycling of sulfur maintains environmental conditions appropriate for acidophilic Fe(III)-reducing and acid-tolerant sulfate-reducing microbial communities.     

Quantitative Assessment of the Intertidal Environment of Kuwait I: Integrated Environmental Classification

Quantitative analysis of physical, chemical and biological data of the intertidal zone in Kuwait was undertaken to develop an integrated basis for assessing and protecting this sensitive coastal ecosystem. Cluster analyses were performed to determine the resemblance between the sampling stations based on the sediment composition, the benthic macrofauna and the physico-chemical characteristics of the intertidal sediment/water. Five distinct sub-environments were delineated within the intertidal zone of Kuwait. Each sub-environment was described in terms of number of taxa, mean density of organisms, sediment type, tidal level and dominant organisms. The physico-chemical parameters investigated were found to be unimportant in the distribution of the intertidal benthic macrofauna. On the other hand, sediment type was found to be a major factor in the overall composition of the benthic community. The benthic fauna and related characteristics of the sub-environments could be used as indicators to monitor changes in the intertidal ecosystem and as guides to protection and management of the different coasts. The approach described in this paper could also be adopted elsewhere to provide a sound basis for evaluating environmental impacts and for developing sustainable coastal management.     

生物净化挥发性有机化合物(VOCs)的研究进展

有机废气中大多含有低浓度的苯、甲苯、苯乙烯、多环芳烃等挥发性有机化合物(VOCs)。这类挥发性有机化合物会对人体健康和生态环境造成危害。治理VOCs污染是大气污染治理的重要部分。生物法处理有机废气具有运行费用低、没有二次污染等优点。常用的生物处理技术主要有生物过滤池、生物滴滤池和生物洗涤塔。20世纪80年代生物法在欧洲得到快速发展,我国于90年代以后也开始了生物处理VOCs废气的研究,并取得了一定的成就。     

Rapid amino acid cycling in arctic and antarctic soils

Amino acids constitute one of the largest inputs of organic nitrogen (N) to most polar soils and have been hypothesized to be important in regulating vegetational succession and productivity in Arctic ecosystems. Our understanding of amino acid cycling in these soils, however, is poor. The aim of this study was to investigate the size and rate of turnover of the amino acid pool in a range of Arctic and Antarctic soils. Our results indicate that in polar soils with either high or low ornithogenic inputs the amino acid pool is small in comparison to the inorganic N pool (NO^–₃ and NH⁺₄). The free amino acid pool constituted only a small proportion of the total dissolved organic nitrogen (DON) pool in these soils. Here we show that these low concentrations may be due to rapid use by the soil microbial community in both Arctic and Antarctic soils. The turnover of the amino acid pool in soil was extremely rapid, with a half-life ranging from 2 to 24 h, indicating that this N pool can be turned over many hundred times each summer when polar soils are frequently unfrozen. The implications of amino acids in N cycling and plant and microbial nutrition are discussed.     

Impact of Land Use on Soluble Organic Nitrogen in Soil

Although it has been hypothesized that soluble organic nitrogen (SON) plays a central role in regulating productivity in some terrestrial ecosystems, the factors controlling the size of the SON pool in soil remain poorly understood. Therefore our principal aim in this work was to assess the impact of seven different land use systems (rough and managed grassland, deciduous and coniferous woodland, heathland, wetland and tilled land) on the size of the SON and inorganic N (NO ₃ ^– , NH ₄ ⁺ ) pools in the surface soil layer (0–15 cm). After extraction with deionised water, we found that in most cases the size of the water extractable organic N (WEON) pool was similar in size to the inorganic N pool. In contrast, the KCl extractable organic N (KClEON) pool constituted the dominant form of soluble N in soils under all land uses, perhaps indicating that significant amounts were held on the soil exchange phase. In contrast to inorganic N, which varied significantly with land use, the size of the KClEON and WEON pool was similar for all land uses with the exception of KClEON in tilled land, where significantly lower amounts were observed. We conclude that SON constitutes an important soil N pool in a broad range of land uses, and that its role in microbial N assimilation, plant nutrition and ecosystem responses to atmospheric N deposition warrants further attention. SAFRD, University of Newcastle, Newcastle-upon-Tyne, NE1 7RU, U.K.     

改进型石灰混凝法去除城市污水二级出水中有机物的研究

将石灰混凝处理后的沉淀泥渣进行回流，对石灰混凝法进行改进，研究改进后的石灰混凝法对城市污水二级出水中有机物的去除效果。结果表明，活性泥渣回流有利于提高石灰混凝法对城市污水二级出水中有机物的去除。回流位置在石灰投加前、复合絮凝剂投加后，最佳回流量为新泥渣产生量的100％～200％，活性泥渣回流的最佳pH为11．0～11．5；活性泥渣中CaCO3、Mg(OH)2、Fe(OH)3等沉淀物以及有机高分子絮体均有助于提高其对有机物的去除效果，其中Mg(OH)2沉淀物起主导作用；含循环泥渣的活性污泥回流，对有机物的去除效果无明显影响。