含油污泥清洗剂的合成及其性能评价

含油污泥已作为危险废物列入《国家危险废物名录》（HW08），其处理问题已成为环保领域研究的热点。热洗技术是含油污泥处理的主流技术，而清洗药剂作为该技术的核心，直接影响含油污泥的处理指标与效率。目前，适合热洗处理的化学药剂很少，迫切需要开发专用药剂技术。针对含油污泥清洗效率的难题，本文合成了一种新型高效的含油污泥清洗剂。 本文以甲基丙烯酸（MAA）、丙烯酸丁酯（BA）和苯乙烯（St）为混合单体，偶氮二异丁腈（AIBN）为引发剂，通过溶液聚合的方法探索合成了一种高分子聚合物（命名为MBS）。分析讨论了MBS关键单体的选择、合成设计及方法，检测了MBS有关物理化学性能，考察了单体、引发剂用量及清洗条件对MBS脱油性能的影响，探讨了MBS对含油污泥中原油不同组分的去除效率，并用红外光谱证实了MBS结构的官能团。 MBS在单体质量比为MAA：BA：St=21：62：17，引发剂AIBN为单体总量的1.2%时，含油污泥脱油率可达84%以上。MBS对于含油污泥中芳烃去除率最高，为93.0%；其次是烷烃，去除率为87.4%；沥青质、胶质最低，去除率为71.8%，具有良好的处理效果。 本文还针对目前国内尚无评价含油污泥清洗剂的标准方法，对清洗剂性能评价进行了初探，采用统一标准的模拟含油污泥进行清洗剂性能评价，并提出了制备方法，同时验证了在此基础上所建立的性能评价方法。结果证明，模拟含油污泥能够真实体现清洗剂的脱油性能，所建立的评价方法可以作为一种通用规范的含油污泥清洗剂性能评价的基本方法。

典型粘土矿物吸附原油的清洗技术研究

含油污泥是危险废物，已列入《国家危险废物名录》。目前，热水清洗法是含油污泥处理的核心技术之一，但因含油污泥来源不同，成分性质各异，含油污泥清洗技术的普适性及规律性差。粘土矿物作为含油污泥泥质的主要成分，其吸附原油的清洗是含油污泥清洗技术的关键环节，因此，从粘土矿物性质、原油组分、清洗剂性质三个方面对粘土矿物吸附原油的清洗技术进行研究，分析其内在的规律性，是获得普适性含油污泥清洗技术的突破口。 本文结合含油污泥的理化性质分析，选取粒径范围为0～100µm高岭石、蒙脱石、绿泥石和伊利石四种粘土矿物，在优化工艺条件的基础上，研究其吸附原油在不同表面活性剂作用下的解吸规律，分析原油中不同族组分的脱附特性，筛选了针对典型粘土矿物吸附原油的高效清洗剂。 四种粘土矿物吸附原油解吸效率的大小顺序为伊利石>蒙脱石>高岭石>绿泥石。不同表面活性剂对粘土矿物吸附原油清洗效率的大小顺序为阴离子表面活性剂>非离子表面活性剂>阳离子表面活性剂。粘土矿物吸附原油中三个族组分的脱附难易顺序为饱和烃>芳烃>胶质沥青质，饱和烃的脱附效率是控制粘土矿物吸附原油总体清洗效率的最重要参数。Dodec-MNS和NPS-10是良好的粘土矿物吸附原油清洗剂，NPS–10对含油率为18.32%和29.68%的含油污泥的脱附效率分别为78.43%和84.11%。 本文同时还针对含油污泥清洗技术中清洗剂复配，提出根据含油污泥族组分特性，选取亲油基性质与对应族组分性质接近的表面活性剂进行复配的方法，方法经实验验证可行，可作为一种含油污泥清洗剂复配的基本方法。

Wettability designing by ZnO periodical surface textures

A facile and effective aqueous chemical synthesis approach towards well control of periodical ZnO textures in large-scale areas is reported, by which considerable adjusting of surface wettability can be realized. With the assistance of polystyrene spheres monolayer template and morphology control agent, we succeeded in preparing a series of ordered ZnO microbowls with different sag height. It was found that the contact angle could be well adjusted by changing geometry of microbowl. Such novel, ordered arrays are expected to exploit the great potentiality in waterproof or self-cleaning micro/nanodevices, and even microfluidic devices. (C) 2010 Elsevier Inc. All rights reserved.

超声与磁粉强化含单宁废水生物处理研究

单宁是一种典型的有毒难降解污染物，在制革、造纸、制药、印染等行业废水中广泛存在，对水环境造成污染并且影响废水生物处理效果。本研究针对含单宁废水生物处理效率低、较高浓度时微生物受抑制且污泥容易膨胀等问题，采用超声和磁粉来强化含单宁废水生物处理，研究超声和磁粉对微生物活性、污染物去除及污泥沉降性能的影响，并对其作用机理进行了分析和探讨。 研究结果表明，活性污泥系统中单宁酸容积负荷可以达到1.8kgCOD/(m3·d)，单宁酸和COD去除率分别达到85.2%和79.6%，但如果负荷进一步增大则微生物活性迅速降低。系统在pH 5~8、温度20~35℃、DO>1 mg/L的条件下具有较好的单宁酸降解效果和处理稳定性。单宁降解动力学参数为：μmax =0.208h-1；Ks=226mg/L；Ki=522mg/L；kd=0.0092h-1；Y =0.594。 磁粉对系统处理效果和污泥沉降性能有一定的促进作用，且效果要优于外磁场。适宜的磁粉粒径和投加量分别为0.05~0.15mm和1.0g/L，COD去除率比对照系统提高6.4%，SVI降低28.6%，污泥絮体结构紧密。磁粉强化主要是通过其对污泥菌胶团的凝聚、吸附作用以及对微生物活性的强化作用实现。 在适当强度（0.4W/cm2）和辐照时间（20min）的超声作用下污泥絮体和细胞膜通透性增大，酶分泌也增多，系统的COD去除率比对照提高了8.8%，单宁酶酶活提高了11%。但超声也使污泥絮体结构松散，沉降性能下降，SVI比对照系统升高9.3%。 由于污泥流失加剧导致污泥浓度相对较低，声磁联合强化系统相对于磁粉强化系统其处理效果并没有提高。但相对于单纯活性污泥系统，声磁联合作用下系统处理效果、污泥沉降性能以及系统运行稳定性都得到明显改善。本研究为难降解废水的生物处理提供了一个新的思路。 Tannins are typical refractory and toxic pollutants that commonly exist in wastewater from dye, medicine, paper and leather industries and cause many problems associated with environmental pollution and biological treatment of wastewater. Biological treatment efficiency of tannin-containing wastewater is usually low owing to its biological toxicity and low biodegradability, microbes are usually inhibited under high tannin concentration and sludge bulking frequently occurs. In this study, ultrasound and magnetic powder were used to improve the biological treatment performance of simulated tannic acid-containing wastewater. The effects of ultrasonic irradiation and magnetic powder on microbial activity, tannic acid degradation rate and sludge sedimentation were investigated. The augmentation mechanisms were analyzed and discussed. The experimental results showed that the microbes were prominently inhibited under high tannic acid concentration, but moderate degradation efficiency can be maintained under a tannic acid load of up to 1.8kgCOD/(m3·d), with the tannic acid degradation and COD removal percentage of 85.2% and 79.6% respectively. The highest degradation rates and treatment stability were achieved at pH range of 5~8, temperature range of 20~35℃ and DO concentration of above 1mg/L. The kinetic parameters were estimated, including: μmax =0.208h-1；Ks=226mg/L；Ki=522mg/L；kd=0.0092h-1；Y =0.594. The microbial activity, tannic acid degradation rate and sludge sedimentation were improved by adding Fe3O4 magnetic powder, and the augmentation performance was better than external magnetic field. The appropriate particle size and dosage of magnetic powder were found to be 0.05~0.15mm and 1.0g/L, respectively, under which the COD removal percentage was improved by 6.4% and SVI value decreased by 28.6%, and compact floc structure was observed. This was mainly caused by the flocculation and adsorption effects of magnetic powder against sludge floc and the stimulation of microbial activity under appropriate magnetic field. Under appropriate ultrasonic irradiation (ultrasonic intensity 0.4W/cm2, ultrasonic irradiation time 20min), the permeability of floc and cell membrane are improved, transfer of substrate and oxygen were reinforced; meanwhile, more enzyme were produced by microbes under the slight damage caused by ultrasound. However, the floc structure became loose under ultrasonic irradiation, leading to relatively poor sedimentation, with the SVI value 9.3% higher than the control system. Although the magnetic powder-ultrasonic irradiation combined augmentation system showed no improvement in treatment performance compared with sole magnetic augmentation system owing to its relatively low sludge concentration, it guaranteed the stable operation of system, meanwhile the tannic acid degradation and sludge sedimentation were significantly improved compared with sole activated sludge system. This study gives a new idea for biological treatment of refractory wastewater.

Determination and identification of isoflavonoids in Radix astragali by matrix solid-phase dispersion extraction and high-performance liquid chromatography with photodiode array and mass spectrometric detection

The isoflavonoids in Radix astragali were determined and identified by HPLC-photodiode array detection-MS after extraction employing matrix solid-phase dispersion (MSPD). As a new sample preparation method for R. astragali, the MSPD procedure was optimized, validated and compared with conventional methods including ultrasonic and Soxhlet extraction. The amounts of two major components in this herb, formononetin (6) and ononin (2), were determined based on their authentic standards. Four major isoflavonoids, formononetin (6), ononin (2), calycosin (5) and its glycoside (1), and three minor isoflavonoids, (6aR,11aR)-3-hydroxy-9, 10-dimethoxypterocarpan (7), its glycoside (3), and (3R)-7,2'-dihydroxy-3',4'-dimethoxyisoflavone-7-O-beta-D-glycoside (4), were identified based on their characteristic two-band UV spectra and [M + H](+), [aglycone + H](+) and [A1 + H](+) ions, etc. The combined MSPD and HPLC-DAD-MS method was suitable for quantitative and qualitative determination of the isoflavonoids in R. astragali. (C) 2003 Elsevier B.V. All rights reserved.

Methods for physical separation and characterization of soil organic matter fractions

Turnover of soil organic matter (SOM) is coupled to the cycling of nutrients in soil through the activity of soil microorganisms. Biological availability of organic substrate in soil is related to the chemical quality of the organic material and to its degree of physical protection. SOM fractions can provide information on the turnover of organic matter (OM), provided the fractions can be related to functional or structural components in soil. Ultrasonication is commonly used to disrupt the soil structure prior to physical fractionation according to particle size, but may cause redistribution of OM among size fractions. The presence of mineral particles in size fractions can complicate estimations of OM turnover time within the fractions. Densiometric separation allows one to physically separate OM found within a specific size class from the heavier-density mineral particles. Nutrient contents and mineralization potential were determined for discrete size/density OM fractions isolated from within the macroaggregate structure of cultivated grassland soils. Eighteen percent of the total soil C and 25% of the total soil N in no-till soil was associated with fine-silt size particles having a density of 2.07-2.21 g/cm3 isolated from inside macroaggregates (enriched labile fraction or ELF). The amount of C and N sequestered in the ELF fraction decreased as the intensity of tillage increased. The specific rate of mineralization (mug net mineral N/mug total N in the fraction) for macroaggregate-derived ELF was not different for the three tillage treatments but was greater than for intact macroaggregates. The methods described here have improved our ability to quantitatively estimate SOM fractions, which in turn has increased our understanding of SOM dynamics in cultivated grassland systems.

石油污染土壤的生物修复技术

The soil contaminated by petroleum hydrocarbons and main methods of cleaning the pollutants were dealt with in the paper.The key principles,technological types, effect factors ,consolidation of the technology,present situation and development of the bioremediation of the soil contaminated by petroleum hydrocarbons were presented.