零价铁-氧化剂联合降解土壤中硝基氯苯及土壤性质变化

硝基氯苯是重要的化工原料和中间体,其在土壤中的不断积累对生态环境和人体健康构成了严重威胁.高级氧化修复技术可以将有机污染物直接或间接矿化为CO_2和H_2O,从而成为近年来研究的重点.本文针对南京某化工厂搬迁遗留的硝基氯苯污染的场地土壤,研究了零价铁还原与氧化剂氧化的联合体系对硝基氯苯的降解率,并对反应过程的中间产物和动力学进行了分析,研究了降解后土壤性质的变化.结果表明,当采用KMnO_4、Fenton试剂、30%H_2O_2和Na_2S_2O_44种氧化剂直接氧化时,土壤中硝基氯苯的降解率分别为75.0%、62.9%、58.1%和41.5%;经零价铁还原1 h后,再施加氧化剂氧化处理,硝基氯苯降解率大幅提高,分别达到91.5%、88.5%、87.4%和70.4%.零价铁还原体系中间产物氯代苯胺浓度4 h时达到最大,施加氧化剂后迅速下降,4 h后下降至最低并维持较稳定水平;硝基氯苯氧化反应在单一氧化剂反应体系符合一级动力学方程,但在零价铁与氧化剂联合反应体系符合二级动力学方程;降解后的土壤性质有较大变化,CEC、TOC和土壤养分显著下降,Eh和EC显著增加,土壤pH除施加Na2S2O4下降显著外,施加KMnO_4、Fenton试剂、30%H_2O_2时下降较小,但同时添加零价铁土壤pH下降显著;土壤全N、全P、全K变化不显著,这些可为修复后土壤的再利用提供数据参考.     

噻吩磺隆降解菌Staphylococcus sp.的分离及其降解特性与途径

采用富集培养技术从磺酰脲类除草剂污染土壤中筛选得到1株降解噻吩磺隆的细菌,命名为ZWS13.经形态特征和16S rRNA基因序列分析,初步鉴定为葡萄球菌属(Staphylococcus sp.).采用HPLC研究了初始底物浓度、温度、接种量、pH等因素对菌株ZWS13降解噻吩磺隆的影响.结果表明,菌株ZWS13对噻吩磺隆的降解具有较广的底物浓度范围,在7 d内对初始浓度5.0~100.0 mg·L~(-1)噻吩磺隆的降解率达到60%以上;菌株ZWS13降解噻吩磺隆的较适pH为8.0,较适温度为40℃,较适接种量为1%;其中,菌株培养温度为40℃时,菌株在10 d内对50.0mg·L~(-1)噻吩磺隆的降解率达到99%以上.降解谱测定结果表明,菌株对烟嘧磺隆、吡嘧磺隆和甲磺隆亦具有良好的降解效果.采用HPLC-MS分析确定了菌株对噻吩磺隆的5个降解产物,推测菌株对噻吩磺隆的降解途径主要为磺酰脲桥C—N键的断裂、脱甲基作用或脱酯作用的甲基丢失及三嗪环的开裂.研究表明,菌株ZWS13能够有效地降解噻吩磺隆,具有生物修复噻吩磺隆污染的潜力.     

感应电芬顿降解二甲基砷的效果与机理研究

二甲基砷作为甲基砷的主要种类之一,主要由含砷废水的排放和农药滥用进入环境水体,进而严重威胁着人类的健康.通过改进电芬顿反应中Fe~(2+)的投加方式,构建了以铁棒为感应阳极、RuO_2/Ti网为阳极、2个活性炭纤维为双阴极的感应电芬顿体系.为探究感应电芬顿体系对二甲基砷的降解效果与机理,考察了反应过程中初始pH、电流密度、反应物初始浓度等因素对二甲基砷去除效果的影响.结果表明,在初始pH值为3,电流密度为2 m A·cm~(-2),二甲基砷初始浓度为5 mg·L~(-1)的最佳条件下,经感应电芬顿反应240 min后,二甲基砷去除率高达94.4%.在此体系中,感应铁电极不断释放的Fe~(2+)与阴极产生的H_2O_2发生电芬顿反应产生羟基自由基将二甲基砷降解为一甲基砷、As(Ⅲ)和As(V),同时,铁离子水解生成的铁的羟基络合物将二甲基砷、一甲基砷、As(III)和As(V)吸附在其表面,从而达到二甲基砷的高效去除.     

甲硫醇降解菌群筛选及其降解特性研究

从处理甲硫醚(DMS)和丙硫醇(PT)混合废气的生物滴滤塔中富集出一组能够有效降解甲硫醇(MT)的混合菌群,并对其特性进行了系列研究.结果表明,该混合菌群能有效降解MT,菌群较为适宜的生长和降解条件为30℃、p H=7.0,在该条件下能将初始浓度为20 mg·L~(-1)的MT在70 h内降解完全.添加酵母膏(YE)后,MT降解速率进一步提高,降解所需时间缩短10 h.利用高通量测序技术分析混合菌群的群落结构,发现其中优势菌属为Pseudomonas sp.、Thiobacillus sp.和Acinetobacter sp.,所占比例分别为33.78%、21.91%和17.01%.中间产物检测结果表明,混合菌群降解MT的过程中产生了甲醛、H_2S、二甲基二硫醚(DMDS)等物质,推断MT的降解途径可能有如下2条:(1)MT在MT氧化酶作用下形成甲醛和H2S,随后氧化为SO_4~(2-);(2)MT依次转化为DMDS、DMS、二甲基亚砜(DMSO)和二甲基砜(DMSO_2),最后经甲基磺酸(MSA)可生成SO_4~(2-).     

电子束辐照降解水中氯霉素的研究

本研究对氯霉素(CAP)在不同条件下的电子束辐照降解进行了研究.结果表明,电子束辐照可有效去除水中CAP,低浓度CAP在酸性条件下的辐照降解更为显著,且降解过程符合准一级动力学模型.通过添加不同的自由基清除剂,发现HO·在CAP降解中起关键作用,此外,CAP分子也会吸收辐照而发生分解.水中共存的阴离子和腐殖酸(HA)对CAP辐照降解均有抑制作用,这跟其与HO·的反应速率常数大小有关,并且反应速率越大,其抑制能力越强.CAP在去离子水中的去除率高于其他实际水体,但辐照剂量为4 k Gy时,污水厂污水过滤水和胶体浓缩液中的CAP也可分别去除89.1%和81.7%.利用GC-MS检测到辐照后溶液中有6种中间产物,主要是通过脱水、不对称中心断键和脱酰胺作用形成.此外,IC检测有Cl-、NO-3和NO-2的产生,并且TOC在一定程度上降低,说明部分CAP被矿化.     

Process of rice straw degradation and dynamic trend of pH by the microbial community MC1

The process of the rice straw degradation in the fermentor with aeration at 290 ml/h was studied. The results of dissolved oxygen （DO） indicated that the optimum DO during cellulose degradation by microbial community MC1 ranged from 0.01 to 0.12 mg/L. The change model ofpH values was as follows： irrespective of the initial pH of the medium, pH values decreased rapidly to approximate 6.0 after being inoculated within 48 h when cellulose was strongly degraded, and then increased slowly to 8.0--9.0 until cellulose was degraded completely. During the degradation process, 15 kinds of organic compounds were checked out by GC-MS. Most of them were organic acids. Quantity analysis was carried out, and the maximum content compound was ethyl acetate which reached 13.56 g/L on the day 4. The cellulose degradation quantity and ratio analyses showed that less quantity （under batch fermentation conditions） and longer interval （under semi-fermentation conditions） of rice straw added to fermentation system were contributed to matching the change model of pH, and increasing the quantity and ratio of rice straw degradation during cellulose degrading process. The highest degradation ratio was observed under the condition office straw added one time every five days （under semi-fermentation conditions）.     

Degradation of polyacrylamide (PAM) and methane production by mesophilic and thermophilic anaerobic digestion: Effect of temperature and concentration

• PAM degradation in thermophilic AD in comparison with mesophilic AD. • PAM degradation and its impact on thermophilic and mesophilic AD. • Enhanced methane yield in presence of PAM during thermophilic and mesophilic AD. • PAM degradation and microbial community analysis in thermophilic and mesophilic AD. Polyacrylamide (PAM) is generally employed in wastewater treatment processes such as sludge dewatering and therefore exists in the sludge. Furthermore, it degrades slowly and can deteriorate methane yield during anaerobic digestion (AD). The impact or fate of PAM in AD under thermophilic conditions is still unclear. This study mainly focuses on PAM degradation and enhanced methane production from PAM-added sludge during 15 days of thermophilic (55°C) AD compared to mesophilic (35°C) AD. Sludge and PAM dose from 10 to 50 g/kg TSS were used. The results showed that PAM degraded by 76% to 78% with acrylamide (AM) content of 0.2 to 3.3 mg/L in thermophilic AD. However, it degraded only 27% to 30% with AM content of 0.5 to 7.2 mg/L in mesophilic AD. The methane yield was almost 230 to 238.4 mL/g VSS on the 8th day in thermophilic AD but was 115.2 to 128.6 mL/g VSS in mesophilic AD. Mechanism investigation revealed that thermophilic AD with continuous stirring not only enhanced PAM degradation but also boosted the organics release from the sludge with added PAM and gave higher methane yield than mesophilic AD.     

Eco-Environmental Degradation in the Source Region of the Yellow River, Northeast Qinghai-Xizang Plateau

The Yellow River is the second longest river in China and the cradle of the Chinese civilization. The source region of the Yellow River is the most important water holding area for the Yellow River, about 49.2% of the whole runoff comes from this region. However, for the special location, it is a region with most fragile eco-environment in China as well. Eco-environmental degradation in the source region of the Yellow River has been a very serious ecological and socially economic problem. According to census data, historical documents and climatic information, during the last half century, especially the last 30 years, great changes have taken place in the eco-environment of this region. Such changes are mainly manifested in the temporal-spatial changes of water environment, deglaciation, permafrost reduction, vegetation degeneracy and desertification extent, which led to land capacity decreasing and river disconnecting. At present, desertification of the region is showing an accelerating tendency. This paper analyzes the present status of eco-environment degradation in this region supported by GIS and RS, as well as field investigation and indoor analysis, based on knowledge, multi-source data is gathered and the classification is worked out, deals with their natural and anthropogenic causes, and points out that in the last half century the desertification and environmental degradation of this region are mainly attributed to human activities under the background of regional climate changes. To halt further degradation of the environment of this region, great efforts should be made to use land resources rationally, develop advantages animal agriculture and protect the natural grassland.     

Changes Of Hydrological Environment And Their Influences On Coastal Wetlands InThe Southern Laizhou Bay, China

The structure and function of the coastal wetland ecosystem in the southern Laizhou Bay have been changed greatly and influenced by regional hydrological changes. The coastal wetlands have degraded significantly during the latest 30 years due to successive drought, decreasing of runoff, pollution, underground saline water intrusion, and aggravating marine disasters such as storm tides and sea level rising. Most archaic lakes have vanished, while artificial wetlands have been extending since natural coastal wetlands replaced by salt areas and ponds of shrimps and crabs. The pollution of sediments in inter-tidal wetlands and the pollution of water quality in sub-tidal wetlands are getting worse and therefore “red tides” happen more often than before. The biodiversity in the study area has been decreased. Further studies are still needed to protect the degraded coastal wetlands in the area.     

Spatial Characterization and Prioritization of Heavy Metal Contaminated Soil-Water Resources in Peri-Urban Areas of National Capital Territory (NCT), Delhi

Due to rapid industrialization and urbanization during last two decades, contamination of soils by heavy metals is on an increase globally. Lands under peri-urban agriculture are the worst affected. In NCT, Delhi about 14.4% of land area is chemically degraded. In order to take care of this problem, recently the Supreme Court of India ordered to shift various non-confirming (about 39,000 units) industries to regions outside NCT, Delhi. However in spite of this, there have been several reports and parliamentary debates on the phyto-toxicity and extensive accumulation of heavy metals in the region. Literature review revealed that the basis of these debates is a few studies on some point locations in/around Delhi. It was further observed that information on the distribution and extent of heavy metal pollution problem in the region was completely missing. The present study was thus basically aimed at assessing the spatial distribution/extent and type of heavy metal pollution in the study area, for enabling future designing of appropriate site-specific management measures by the decision makers.For this, detailed spatial information on bio-available heavy metal concentrations in the soils and surface/sub-surface waters of NCT (Delhi) was generated through actual soil/water surveys, standard laboratory methods and GIS techniques. The study showed that concentration of all micronutrients (viz. Zn: 0.05–0.18 ppm; Cu: in traces; Fe: 0–0.5 ppm; and Mn: 0–1.2 ppm) and most heavy metals (viz. Ni: 0–0.7 ppm; Pb: 0–0.15 ppm and Cd: in traces) in the surface/sub-surface irrigation waters were well within permissible limits. However Cr concentrations in irrigation waters of Alipur and Shahdara blocks were far above their maximum permissible limit of 1 ppm. It was further observed that Ni and Cr concentrations in the drinking waters of almost entire test area were far above maximum permissible levels of 0.02 and 0.01 ppm, respectively. Bio-available concentrations of several heavy metals (viz. Pb: 0.1–2 ppm; Cd: traces; Ni: 0.05–2 ppm and Cr: 0–0.4 ppm) in the study area soils were also observed to be well within the maximum permissible limits. However there were point Cu contaminations (5–10 ppm) in the sewage-sludge amended soils of vegetable growing areas near south Shahdara block. This was attributed to increased Cu availability due to oxidized acidic conditions generated by over-irrigation of agricultural lands. Available Mn concentrations in Kanjhawala, western Najafgarh and Alipur soils were also observed to be above maximum permissible limit of 10 ppm. This was observed to be mainly due to the geology (i.e. presence of Mn rich sedimentary rocks) and prevalence of reduced acidic conditions, due to paddy cultivation, in these areas. It was further observed that there is acute zinc (Zn) deficiency (< 0.6 ppm) in paddy growing soils of north Kanjhawala, Alipur and some parts of Najafgarh and Shahdara blocks due to extensive leaching of available Zn fractions to lower soil horizons. Similar available Zn deficiencies in high pH (8.5) soils of areas around Bamnoli village in E-Najafgarh block were also observed.