2012-2019年河北省不同气候区酸雨特征及影响因子分析

利用河北省20个酸雨观测站2012—2019年的酸雨观测日数据和2013—2019年的SO₂、CO、NO₂、O₃、PM₁₀、PM_2.5环境气象逐日数据,分析了河北省不同气候区酸雨特征及其与其他要素的关系。结果表明：(1)近8年来,强、弱酸雨日数呈逐年减少趋势。强、弱酸雨在燕山丘陵气候区与冀东平原气候区交界的东部发生概率均较其他地区高。此外,弱酸雨在太行山气候区与山前平原气候区交界的南部发生概率较高。(2)当降水级别为小雨,太行山气候区主导风向为北风、山前平原气候区主导风向为东北风、冀东平原气候区主导风向为东北风、燕山丘陵气候区主导风向为东风、冀北高原气候区主导风向为东南风,有利于河北省各气候区发生强酸雨。(3)冀北高原气候区及山前平原气候区发生大雨及以上级别的降水事件时,对SO₂、NO₂清除效果较好;燕山丘陵气候区、太行山气候区及冀东平原气候区发生中小雨级别的降水事件时,对SO₂、NO₂清除...     

外电场作用下D-甘油酸分子的结构和光谱研究

采用密度泛函（DFT） B3LYP方法在6-311G基组上优化了不同外电场作用下D-甘油酸分子的基态几何结构、电偶极矩和分子的总能量,并在此基础上利用含时密度泛函（TD-DFT）方法在相同基组下探讨了各电场情况下D-甘油酸分子前6个激发态的激发能、波长和振子强度与外电场大小的关系.结果表明：分子的几何构型在外电场F=0.003 a.u.时会发生明显的变化,当外电场强度F=0.003 a.u.时,分子总能量骤然下降,电偶极矩骤然上升,其紫外吸收峰也出现明显的红移.当电场继续增加时,上述指标重新回到正常水平,骤变消失.     

Fourier transform infrared studies of the reaction of Cl atoms with PAN,PPN, CH3OOH,HCOOH, CH3COCH3 and CH3COC2H5 at 295±2 K

The relative rate technique has been used to measure rate constants for the reaction of chlorine atoms with peroxyacetylnitrate (PAN), peroxypropionylnitrate (PPN), methylhydroperoxide, formic acid, acetone and butanone. Decay rates of these organic species were measured relative to one or more of the following reference compounds; ethene, ethane, chloroethane, chloromethane, and methane. Using rate constants of 9.29×10^–11, 5.7×10^–11, 8.04×10^–12, 4.9×10^–13, and 1.0×10^–13 cm³ molecule^–1 sec^–1 for the reaction of Cl atoms with ethene, ethane, chloroethane, chloromethane, and methane respectively, the following rate constants were derived, in units of cm³ molecule^–1 s^–1: PAN, <7×10^–15; PPN, (1.14±0.12)×10^–12; HCOOH, (2.00±0.25)×10^–13; CH₃OOH, (5.70±0.23)×10^–11; CH₃COCH₃, (2.37±0.12)×10^–12; and CH₃COC₂H₅, (4.13±0.57)×10^–11. Quoted errors represent 2 and do not include possible systematic errors due to errors in the reference rate constants. Experiments were performed at 295±2 K and 700 torr total pressure of nitrogen or synthetic air. The results are discussed with respect to the previous literature data and to the modelling of nonmethane hydrocarbon oxidation in the atmosphere.In recent discussions with Dr. R. A. Cox of Harwell Laboratory, UKAEA, we learnt of a preliminary value for the rate constant of the reaction of Cl with acetone of (2.5±1.0)×10^–12 cm³ molecule^–1 sec^–1 measured by R. A. Cox, M. E. Jenkin, and G. D. Hayman using molecular modulation techniques. This value is in good agreement with our results.     

Analysis on concentration and source rate of precursor vapors participating in particle formation and growth at xinken in the Pearl River Delta of China

Concentration and source rate of precursor vapors participating in particle formation and subsequent growth were investigated during the Pearl River Delta intensive campaign （PRD2004, October 2004） in southeastern China. Four new particle formation event days and a typical non-event day were selected for our analysis. Atmospheric sulphuric acid, the important precursor vapor in nucleation and growth, were simulated with a pseudo steady-state model based on the measurements of SO2, NOx, 03, CO, non-methane hydrocarbon （NMHC） and ambient particle number concentrations as well as modeled photolysis frequencies obtained from measurements. The maximum midday sulphuric acid concentrations vary from 4.53 × 10^7 to 2.17 × 10^8 molecules cm^-3, the corresponding source rate via reaction of OH and SO2 range between 2.37 × 10^6 and 1.16 × 10^7 molecules cm^-3 s^-1. Nucleation mode growth rate was derived from size spectral evolution during the events to be 6.8-13.8 nm h^-1. Based on the growth rate, concentration of the vapors participating in subsequent growth were estimated to vary from 1.32 × 10^8 to 2.80 × 10^8 molecules cm^-3 with corresponding source rate between 7.26 × 10^6 and 1.64 × 10^7 molecules cm^-3 s^-1. Our results show the degree of pollution is larger in PRD. Sulphuric acid concentrations are fairly high and have a close correlation with new particle formation events. Budget analysis shows that sulphuric acid alone is not enough for required growth; other nonvolatile vapors are needed. However, sulphuric acid plays an important role in growth; the contribution of sulphuric acid to growth in PRD is 12.4%-65.2%.     

悬浮生物填料床—絮凝工艺处理亚硫酸盐制浆中段水研究

针对亚硫酸盐制浆造纸废液中段水可生化降解CODB与不可生化降解CODNB各半的水质特点,采用二级好氧悬浮生物填料浮动床处理及物化絮凝处理的工艺试验,取得了有关试验数据;并根据COD容积负荷与出水残留COD的关系,探讨了利用酶反应动力学曲线预测试验稳定运行状态下出水CODB值。结果表明:利用生化—絮凝两处理技术的优势互补,可使最终排水COD与BOD同时达到国家造纸工业水污染物排放标准。     

全国酸雨观测网未知水样考核结果的统计分析

应用客观统计方法,整理分析了1992年以来全国酸雨观测站网的11次pH未知水样和2次电导率未知水样的考核结果。分析显示,采用稀释和pH调制的标准缓冲溶液作为pH未知水样,其测量偏差随pH标准值的变化不显著,历年的测量标准差均小于0.2pH单位。pH未知水样测量偏差的波动状况指示出观测台站仪器和人员的技术状态变化,对仪器更新、人员培训以及新业务规范的执行等业务建设和质量管理活动有显著的正面响应。对pH未知水样测量偏差的统计还显示,2001年后pH平均测量偏差出现负偏态分布特征,该特征在总体偏差较大时尤为明显,说明部分技术状态不良的台站往往容易出现较大的系统性负偏差。根据考核结果,按照世界气象组织(WMO)推荐的方法,计算除1992年外各次考核的pH值测量的修正绝对中值偏差为0.03～0.10pH单位,1992年和2006年电导率测量的修正绝对中值偏差为4%～5%。修正绝对中值偏差的逐年波动情况反映了全国酸雨观测网pH测量的总体偏差也明显地受台站技术状态波动的影响。     

城市酸雨预报方法及业务系统

应用欧拉酸沉降数值模式、基于主分量的神经网络预报方法、动态统计预报方法,建立了广西城市酸雨预报模型,进而根据酸雨预报业务流程,将预报方法、Sybase数据库和网页技术等有机地结合起来,研制了广西城市酸雨预报业务系统。一年多的业务应用表明,该酸雨预报系统性能稳定、技术成熟、自动化程度高。     

电导率加和性质及其在酸雨观测数据质量评估中的应用

大气降水中离子成分的电导率具有可加和性, 国际上已经普遍应用该原理对大气降水离子成分观测的数据质量进行分析和评估, 即所谓的相对电导率差 (conductance percent difference, CPD) 方法。该文应用CPD方法对我国4个大气本底观测站的电导率和降水离子成分数据进行了数据质量分析, 针对我国的降水电导率范围偏高等特点, 对国外推荐的CP D统计检验指标的适用性进行了讨论, 指出在我国应用CPD方法时宜采取pH值分组的方式, 并根据这种分组方式的统计分析, 估计4个大气本底观测站的部分pH值观测数据可能存在-0.05左右的测量误差。该文还依据降水中离子成分电导率的可加和性原理, 提出K-pH不等式方法, 可以用于中国气象局酸雨观测站网的pH值和电导率数据的现场校验和数据质量的分析评估。应用K-pH不等式方法对观测数据进行现场质量检验时, 对pH值小于5.0范围的酸性降水效果尤其显著。应用K-pH不等式方法对1992—2005年间全国酸雨观测站观测数据的统计分析显示, 部分酸雨观测站的pH值测量数据可能存在-0.1~-0.3左右的系统性负偏差。     

Methodology of analysis associating survey results by the filter-pack method with those of precipitation- Acid-base balance on acid-related and alkali-related chemical species in urban ambient air and its influence on the acidification of precipitation -

Continuous weekly monitoring on the concentration of gases and aerosols in urban ambient air by a four-stage filter-pack method was carried out for 7 years in order to study not only the acid-base balance of acid-related (HNO₃, NO₃ ⁻, and non-sea-salt-(nss-)SO₄ ²⁻) and alkali-related (NH₃, NH₄ ⁺, and nss-Ca²⁺) chemical species but also its influence on the acidification of precipitation. The concentrations of the total nitrate (= NO₃⁻ + HNO₃) and nss-SO₄²⁻ showed a similar seasonal variation: high in the summer and low in the winter. The total nitrate and nss-SO₄²⁻ accounted for 0.43 and 0.57 of the acid-related species, respectively, on an equivalent basis. The total ammonium (= NH₃ + NH₄⁺) accounted for more than 0.9 of the alkali-related species, except for a springtime nss-Ca²⁺ episodic peak. The alkali-related species were generally overabundant compared with the acid-related species in the HNO₃-NO₃⁻-nss-SO₄²⁻-NH₃-NH₄⁺-nss-Ca²⁺ system. The alkali-rich distribution was especially pronounced in the winter, but the acid-related species was comparable to the alkali-related species in the summer, which was attributed to the larger H⁺ deposition by precipitation in the summer. This study can provide a methodology to associate survey results obtained by a filter-pack method with those of precipitation.     

Distribution of nitrate over sea-salt and soil derived particles — Implications from a field study

A method for determining the distribution of supermicrometer nitrate between size-segregated sea-salt and soil derived particles is presented. The analysis is based on field data from six measurements at a coastal site in southern Finland, and on a theoretical treatment taking into account the transfer of gaseous species onto particle surfaces and their subsequent reaction. Significant amounts of nitrate were found in both the particle types, with the fraction of nitrate associated with soil particles varying from 20–50% in the 1–2 m size to near 90% in particles larger than 10 m. Overall, the nitrate accumulation followed closely the relative abundances of these two particle types. Two overlapping modes in supermicron nitrate mass size distributions could be identified. The lower mode, associated with sea-salt, was located between the surface-area and volume distribution of sodium peaking at about 2–3 m of EAD. The upper mode peaked at 3–5 m and followed more closely the surface-area distribution of calcium in all samples. At our site, the accumulation of nitrate into both particle types was shown to be limited by an effective surface reaction rate rather than by gas-phase diffusion. This rate was estimated to be considerably larger for sea-salt particles. Strong evidence in support of the saturation of nitrate in sea-salt particles were obtained.