船舶排放及不确定性对中国空气质量的影响

船舶排放是我国沿海地区重要的人为排放源,但现有的船舶排放评估研究大多只关注区域尺度的影响分析,而且忽视了排放清单的不确定性,这在一定程度上削弱了评估结果的可靠性.为此,本文利用WRF-SMOKE-CAMQ空气质量模型,定量评估了船舶排放及其不确定性对我国七大沿海港口城市夏季空气质量的影响,结果表明：船舶排放对我国主要沿海港口城市的SO₂、NO_x和PM_2.5浓度贡献范围分别为16.5%~62.5%、21.9%~72.9%和5.9%~26.0%,尤其对宁波、青岛和深圳等港口城市空气质量的影响显著,主要是由于港口较高的船舶排放以及气象传输两方面原因造成的;如果考虑船舶排放清单的总量不确定性,船舶排放对沿海港口城市夏季SO₂、NO_x和PM_2.5的影响分别呈现1.0~3.1,2.1~5.5,0.3~0.9μg/m³的波动;考虑船舶排放清单的时空分配不确定性,船舶排放对沿海港口城市夏季SO₂、NO_x和PM_2.5的影响分别呈现1.9~15.7,5.1~29.3,0.6~2.5μg/m³的波动.可见,船舶排放清单的不确定性对沿海城市船舶排放贡献影响量化有明显的影响.所以在评估船舶排放对港口城市空气质量的影响时,要考虑船舶排放清单的不确定性,尤其是时空分配的不确定性.而合理的时空分配能够提高船舶排放清单的质量和对沿海空气质量模拟的准确性.     

DOC+CDPF对国III重型柴油货车实际道路排放的影响

利用便携式车载排放测试系统（PEMS）对2辆加装氧化催化转化器（DOC）和催化型柴油颗粒捕集器（CDPF）与否的国III重型柴油货车进行实际道路排放测试.结果表明,2辆改造重型柴油车的CO、THC、固态颗粒物粒数（SPN）和黑碳（BC）实际道路排放因子分别为（1.31±0.37）g/（kW×h）、（0.20±0.03） g/（kW×h）、（7.13×10¹⁰±5.27×10¹⁰）个/（kW×h）和（0.69±0.06）mg/（kW×h）,相对于原始排放（拆除DOC+CDPF）分别降低52.48%、55.69%、99.91%和99.22%.从低速、中速到高速,CO和THC减排比例呈现上升趋势,然而运行工况对SPN和BC减排比例则无显著影响.加装DOC+CDPF会导致NO₂在NO_x中的占比升高,且从低速、中速到高速涨幅依次增大,但对NO_x无明显减排效益,其排放因子为9.53~9.83g/（kW×h）,远高于实验室排放限值.     

Density functional theory (DFT) studies of vanadium-titanium based selective catalytic reduction (SCR) catalysts

Based on density functional theory (DFT) and basic structure models, the chemical reactions on the surface of vanadium-titanium based selective catalytic reduction (SCR) denitrification catalysts were summarized. Reasonable structural models (non-periodic and periodic structural models) are the basis of density functional calculations. A periodic structure model was more appropriate to represent the catalyst surface, and its theoretical calculation results were more comparable with the experimental results than a non-periodic model. It is generally believed that the SCR mechanism where NH₃ and NO react to produce N₂ and H₂O follows an Eley-Rideal type mechanism. NH₂NO was found to be an important intermediate in the SCR reaction, with multiple production routes. Simultaneously, the effects of H₂O, SO₂ and metal on SCR catalysts were also summarized.     

Effect of substituents in hydroxyl radical-mediated degradation of azo pyridone dyes: Theoretical approaches on the reaction mechanism

Understanding the degradation behavior of azo dyes in photocatalytic wastewater treatment is of fundamental and practical importance for their application in textile-processing and other coloration industries. In this study, quantum chemistry, as density functional theory, was used to elucidate different degradation pathways of azo pyridone dyes in a hydroxyl radical (HO^?)-initiated photocatalytic system. A series of substituted azo pyridone dyes were synthesized by changing the substituent group in the para position of the benzene moiety, ranging from strong electron-donating to strong electron-withdrawing groups. The effect of dye molecular structure on the photocatalytic degradation reaction mechanism was analyzed and quantification of substituent effects on the thermodynamic and kinetics parameters was performed. Potential energy surface analysis revealed the most susceptible reaction site for the HO^? attack. The calculated reaction barriers are found to be strongly affected by the nature of substituent group with a good correlation using Hammett σ_p constants and experimentally determined reaction rates. The stability of pre-reaction complexes and transition state complexes were analyzed applying the distortion-interaction model. The increased stability of the transition state complexes with the distancing from the substituent group has been established.     

随机振动响应峰值因子的预计理论研究

简要介绍了超越概率理论、超越频次理论、损伤等效理论和功率谱密度(PSD)的时域拟合理论等4种常见的峰值因子预计理论,并基于三角级数提出了一种新的预计理论。结合试飞加速度数据样本,对比分析超越频次理论、PSD时域拟合理论和三角级数理论的预估精度。研究表明,上述4种常见的预计理论本质上属于统计学理论;PSD时域拟合理论预计的峰值因子波动较大,峰值因子与归一化次数满足高斯分布;三角级数理论的预估精度较高,但缺乏离散峰个数的合理判据。     

旅游目的地网络空间结构及其复杂性研究——野三坡旅游地案例实证

复杂性是旅游目的地网络化发展的必然趋势,是认识旅游地网络空间结构与组织特征的重要研究手段。论文以河北省野三坡旅游地为例,通过构建旅游联系强度模型,建立旅游地空间网络,并运用TOP网络空间分析以及复杂网络理论,揭示旅游地网络空间结构与组织的复杂性特征。研究发现：1）旅游地网络具有空间集聚性,形成了以核心景区为中心,由中心城镇、乡村社区和特色园区共同构成的空间集聚单元,并体现出“邻近连接”与“择优连接”的双重特性;2）旅游地网络服从幂律分布,具有无标度网络特性;3）每个节点的前三名和前五名旅游联系强度网络（Top3和Top5网络）具有较小的平均路径长度、较大的集聚系数,呈现出典型的“小世界网络”特征;4）旅游地网络是典型的异配型网络,度-度呈负相关,而网络节点的集聚系数与其度值之间存在近似的倒数关系,因此具有层次性。     

考虑边界条件不确定性的地下水污染风险分析

为分析边界条件不确定性对地下水污染质运移数值模拟模型输出结果的影响,运用Monte Carlo方法对一算例进行阐明,并从污染风险预报方面对模拟结果进行分析.为减少重复调用模拟模型产生的大量计算负荷,将边界条件（第一类边界条件-水头值）作为随机变量,建立地下水污染质运移数值模拟模型的Kriging替代模型,在保证较高精度的同时,实现了Monte Carlo模拟.结果表明：边界条件的不确定性,对地下水污染质运移数值模拟模型预报的结果有很大影响,考虑与未考虑边界条件不确定性得到的研究区污染羽分布差别较大.对地下水污染质运移数值模拟模型的Monte Carlo模拟结果进行统计与分析,可以评估研究区观测井1,2,3污染物浓度预报结果的可靠程度,并且可以预报出研究区观测井1,2,3遭受不同程度污染的风险.     

微波消解-ICP-OES联合测AZ61镁合金中Zn、Mn、Al的不确定度分析

目的研究AZ61镁合金中合金元素成分分析过程中的不确定度因素,以提高分析结果的准确性。方法采用微波消解仪消解样品,以电感耦合等离子体发射光谱仪(ICP-OES)测定AZ61镁合金中锌、锰、铝元素的含量。分析测试过程中产生不确定度的因素,并且进行评定和计算。结果采用微波消解-ICP-OES法测定镁合金中锌、锰、铝元素的含量时,测量不确定度主要由样品溶液稀释、移液枪、标准曲线以及测试的重复性引起,AZ61镁合金主要的合金成分为锌(1.1270%±0.0433%)、锰(0.1797%±0.0064%);铝(6.4468%±0.2029%)。结论对分析过程中产生的不确定度因素进行分析及评定,可以确保分析结果的可靠性以及准确性,从而更好地控制镁合金的性能,提高镁合金的装备环境适应性。     

铝合金的实验室盐雾试验腐蚀行为图像特征提取

目的提取铝合金材料在盐雾箱试验中可以表征腐蚀程度的表面形貌图像特征量。方法首先,对采集于表面化学清洗过的试样原始图像进行图像增强等预处理,突出腐蚀部位;其次,基于数字图像处理的分形和小波分解方法提取出分形维数和小波能量特征值。结果与以质量损失量为基础的腐蚀深度特征值进行相关性对比,基于图像分析的特征提取法的准确度和精度比较高。结论该方法可以应用于对试样的腐蚀程度进行定性和定量分析,判断并预测试样的腐蚀速度。     

Development of monitoring technology for airborne particulate matter

Particulate matter suspended in the air has adverse effects onhuman health. Its level of concentration is an important parameter in evaluating the degree of hazard it poses to the atmosphere. Conventional methods used in measuring particulatematter are often filter-based, which indicates some disadvantagesbecause such a base requires labor and time. In this study, to achieve real-time measurements, a new electrical method was developed for measuring PM10 and PM2.5 concentrations. The basicprinciple is to electrically charge particles passing through thePM inlet using a corona charger and measure the currents createdby charged particles to obtain the number concentration of particulate matter. A new type inlet based on the particle cupimpactor configuration was designed and its performance was evaluated. A unipolar diffusion charger was developed and thecharger's efficiency was determined experimentally in terms ofPn, which represents the penetration through the charger,P, times the average charge number acquired by a particle,n, for different particle sizes. The correlation was constructed between the PM10 (or the PM2.5) mass concentrationsand the electrical currents due to particles, which were chargedby the diffusion charger.