Theoretical study on the reaction mechanism of ozone addition to the double bonds of keto-limonene

The reaction mechanism of ozone (O₃) addition to the double bonds of gas phase keto-limonene was investigated using ab initio methods. Two different possibilities for O₃ addition to the double bond were considered and two corresponding van derWaals complexes (Complex 1 and Complex 2) were found for 1-endo and 2-endo. The rate constants were calculated using the transition state theory at the CCSD(T)/6-31G(d) + CF//B3LYP/6-31G(d,p) level. The high-pressure limit of the total rate constant at 298 K was 3.51 × 10^-16 cm³/(molecule sec), which was in a good agreement with the experimental data.     

Ammonia volatilization and availability of Cu, Zn induced by applications of urea with and without coating in soils

Ammonia volatilization and the distribution of Cu and Zn were investigated in two types of soil treated with coated and uncoated urea. The rate of ammonia volatilization in two weeks after fertilizing with coated urea was 8% in soil 1 (soil derived from river alluvial deposits in Dongting Lake Plain) and 5.15% in soil 2 (red soil derived from quaternary red clay), about half the rates observed when fertilizing with common urea, implying that the hydrolysis speed of the coated urea was lower than for common urea, and that the coated urea can increase nitrogen use efficacy. As for the availability of Cu and Zn, their concentrations decreased in the first week after fertilization, and then increased, which was contrary to the effect of treatment on soil pH. For example, when the pH was 7.99, there was 0.79 mg/kg exchangeable Cu and 0.85 mg/kg exchangeable Zn in the soil derived from river alluvial deposits in Dongting Lake Plain. However, the concentrations of exchangeable Cu and Zn were generally lower for the common urea treatments than those with the coated urea because the peak pH for the common urea treatment was greater. The concentrations of these elements correlated well with pH in the range 4-8 in second order polynomial fits.     

柱型水力旋流器对硅切割废砂浆分离性能的研究

为了研究废砂浆中碳化硅粉和硅粉的分离情况,选用混合模型对柱型水力旋流器多相流流场进行数值模拟。模拟结果表明:柱型水力旋流器的分离效率与入口速度、进口浓度等因素有关,并分析出一定条件下当主、次相的入口速度均为1.1m/s时颗粒分离效果较好,分离效率较高,实验检测分离性能较好,为进一步实验研究提供一定的指导。     

Mechanism of lead immobilization by oxalic acid-activated phosphate rocks

Lead (Pb) chemical fixation is an important environmental aspect for human health. Phosphate rocks (PRs) were utilized as an adsorbent to remove Pb from aqueous solution. Raw PRs and oxalic acid-activated PRs (APRs) were used to investigate the effect of chemical modification on the Pb-binding capacity in the pH range 2.0-5.0. The Pb adsorption rate of all treatments above pH 3.0 reached 90%. The Pb binding on PRs and APRs was pH-independent, except at pH 2.0 in activated treatments. The X-ray diffraction analysis confirmed that the raw PRs formed cerussite after reacting with the Pb solution, whereas the APRs formed pyromorphite. The Fourier Transform Infrared spectroscopy analysis indicated that carbonate (CO₃^2-) in raw PRs and phosphate (PO₄^3-) groups in APRs played an important role in the Pb-binding process. After adsorption, anomalous block-shaped particles were observed by scanning electron microscopy with energy dispersive spectroscopy. The X-ray photoelectron spectroscopy data further indicated that both chemical and physical reactions occurred during the adsorption process according to the binding energy. Because of lower solubility of pyromorphite compared to cerussite, the APRs are more effective in immobilizing Pb than that of PRs.     

Seasonal trend of ambient PCDD/Fs in Tianjin City, northern China using active sampling strategy

The spatial concentrations, seasonal trends, profiles and congener pairs of ambient polychlorinated dibenzo-p-dioxins (PCDDs) and polychlorinated dibenzofurans (PCDFs) were investigated within a seasonally active sampling scheme during Jun 2008 and Jan 2009 in Tianjin City, northern China. The PCDD/F concentrations ranged 14.2-172 fg I-TEQ/m³ (average 69.3 fg I-TEQ/m³) in summer and (89.8-1.01) × 10³ fg I-TEQ/m³ (average 509 fg I-TEQ/m³) in winter, respectively, except for the E-waste dismantling site where much higher values were observed (1.04 × 10³ fg I-TEQ/m³ in summer and 7.123 × 10³ fg I-TEQ/m³ in winter). The results indicated a significantly seasonal trend with higher TEQ values in winter as compared with summer, which could be related to increased emission sources and seasonal variations of the atmospheric boundary layer height. 2,3,4,7,8-PeCDF was the dominant contributor to the total PCDD/F toxic equivalents, and 2,3,7,8-TCDD was detected at almost all the sampling sites in winter. Most of the similarly substituted PCDD/F congener pairs exhibited high correlations, suggesting that they might have similar environmental fate or sources. But different seasonal and spatial distributions of PCDD/F concentrations indicated that the emission sources might be intermittent.     

MBR活性污泥培养驯化过程中生物多样性研究

以MBR反应器启动调试阶段的活性污泥为主要研究对象,系统考察了传统活性污泥法(Conventional activated sludge,CAS)污泥接种至MBR反应器内污泥培养驯化过程中生物多样性情况及微生物群落结构的演变规律.同时,在传统污水污泥检测指标的基础上,对各阶段污泥中总细菌基因组DNA进行提取,应用PCR-DGGE分子生物学技术获得了相应的凝胶电泳图谱并进一步分析了菌群间的相似性.结果表明,以CAS污泥为接种污泥在MBR反应器内培养驯化过程中微生物的多样性变化突出,细菌群落结构演替明显,不同阶段菌群间的相似性说明了各阶段菌群的演变关系:污泥培养驯化是一个逐步有序的过程,微生物随反应器内不同时期及环境的变化而调整,逐渐演变成适应MBR工艺的群落结构.     

异位稳定化技术处理重金属复合污染土壤的工程应用研究

异位稳定化技术处理重金属污染土壤在国内外已有应用,但鲜有大规模工程应用时的控制关键及操作要求的报道。本研究根据异位稳定化处理技术的特点,采用该技术处理重金属复合污染且修复时间有限的目标污染场地,通过合理控制稳定剂投加量、土壤理化性质、施工工艺及养护条件等各项影响因素,取得了很好的处理效果,可为类似污染场地提供借鉴和经验。     

道路交通噪声不同预测模型之比较

目前,我国在进行道路交通噪声环境影响评价工作中主要使用的预测模型有2009声导则模型、2006规范模型,此外,也有部分噪声评价工作采用了德国的CadnaA软件。因各种模型在使用条件和参数选取等方面存在不同,导致预测结果存在差异。如何选取合适的预测模型,一直是国内学者不断研究想解决的问题。本文对已有道路交通噪声进行现场实测,通过设计不同的预测模式进行模型验证,将预测结果与实测值进行比较,结果表明这五种噪声预测模式中,模式一、模式四、CadnaA软件的噪声预测值与实际情况最相符,模式一绝对预测误差昼间在3.3-6.0 dB(A)之间,夜间在-3.4-0.2 dB(A)之间。使用2009声导则模型、2006规范模型相结合的预测模式更为准确。     

不同能量电子辐照下星用瑞侃导线性能退化研究

目的研究卫星上外露导线在空间辐射环境下的耐受能力。方法通过分析GEO轨道下在轨10年航天器外露瑞侃导线的辐照环境,研究低能和高能电子对导线性能的影响,地面模拟试验参数选择能量分别为45 keV和1 MeV,注量率均为8.3×10^10 e/(cm^2·s),总注量均为2×10^16 e/cm^2。考察瑞侃导线力学性能(断裂伸长率、拉伸强度)和电性能(击穿电压)的退化情况,并用XPS和SEM测试分析手段,对其电子辐照损伤机理进行研究。结果在不同能量电子辐照下,瑞侃导线的力学性能均略有下降,没有显著区别,而电学性能严重退化,且低能电子较高能电子对其电学性能影响更为严重,其击穿电压分别下降了100%和50%。结论通过剂量-深度分布计算,45 keV入射电子能量全部沉积在样品表层下数微米的深度范围内,完全被导线外皮吸收,对样品的损伤较大;而1 MeV入射电子能量绝大部分穿透表皮沉积在样品铜芯中,因而其性能退化情况相对低能电子较小。进一步的,通过SEM和XPS测试和分析发现,电子辐照造成瑞侃导线分子链降解,形成自由基以及气体,自由基的再交联是造成瑞侃导线损伤的重要机理。     

基于好氧甲烷氧化菌的反硝化效能及微生物群落研究

采用气体循环序批式生物膜反应器（gcSBBR）,构建反硝化型甲烷好氧氧化（AME-D）系统.考察了进水氮负荷的影响,发现氮负荷为0.075kg/（m³·d）时,硝酸盐氮去除率达到98.93%,其反硝化速率为74.25mg/（L·d）,系统的甲烷日平均消耗量为35.91%（初期为50%）;扫描电子显微镜（SEM）分析结果显示,系统中的微生物主要以短杆菌（12~18 μm）为主,并存在少量的丝状菌（长150~200μm）;16S rRNA高通量测序结果显示,该系统中的甲烷氧化菌为Methylocaldum、Methylomonas、Methylococcus和Methylococcaceae_unclassified,反硝化菌为Denitratisoma、Hydrogenophaga、Azoarcus、Thiobacillus和Rhodobacter,其中主要的功能微生物为Methylocaldum、Denitratisoma和Hydrogenophaga,系统对氮的去除是由好氧甲烷氧化菌与反硝化菌协同实现.此外,系统中存在大量以甲醇和甲基胺类物质为生长基质的Methylophilaceae_uncultured（30.4%）.