冬季雨雪的酸度及化学组份的对比

分析了１９８５－１９９１年冬季雨雪的酸度及化学组份资料。结果表明，降雪的酸雪频率各年均有不同，但都比同季中降雨的酸雨频率低；降雪酸度也比降雨纸；降雪中弱酸性的酸雪出现次数最多，占总次数的４成；在酸雪中酸度值与电导率呈现显著的负相关。分析降雪的化学组份发现，降雪中ＳＯ４＾２－含量越来越高，Ｃｌ＾－含量呈下降趋势。阳离子中以ＮＨ４＾＋为主。     

中国西南典型地区酸雨形成过程研究

本文根据云水和雨水化学特性的观测和雨水酸化模式的模拟计算，研究了中国西南地区酸雨的形成过程。结果表明:在重庆和贵阳等重污染城市，云下过程对雨水的酸化起主要作用，在污染较轻的中小城镇和乡村地区，雨水酸度主要决定于云内过程。 但是云下过程对雨水中的主要酸碱离子浓度都有不可忽视的明显影响。雨水的酸化主要是由于SO2与H2O2和O3的氧化，气溶胶起较弱的缓冲碱化作用。在重庆和贵阳等地，当地SO2浓度已高达饱和，其值增减50％，都不会对该地雨水酸度有明显影响，起控制作用的是氧化剂浓度。     

Rapid change in nitrate and sulfate concentrations observed in early stage of precipitation and their deposition processes

The concentrations of H⁺, nitrate (NO₃ ^-), and sulfate (SO₄ ^2-) in rainwater and their temporal changes were analyzed on the basis of continuous observation from 1 July 1991 to 30 June 1992 at a suburb of Nagoya, Japan. The yearly average for pH was 4.4. In general, an increasing pH with increase in precipitation amount was observed for rain events. Relatively high pH rainwater was sometimes observed at the beginning of rainfall, even though high concentrations of NO₃ ^- and SO₄ ^2- were involved. The high pH values were considered to be caused by the neutralization process with particulate matter containing cations. The yearly averaged ratio of equivalent concentration of nitrate to sulfate (N/S) in rainwater was 0.58. In the early stage of rain, the N/S value was usually more than 1.0 due to the difference of scavenging process between NO₃ ^- and SO₄ ^2-. High values of N/S ranging from 5 to 10 were found under the atmospheric conditions of calm winds and low humidity, during which it is possible that atmospheric particles float for a long time in the air before a rain event. The adsorption of NO₃ ^- in the early stage of rainfall by particulate matter was suggested from the difference in scavenging processes of NO₃ ^- and SO₄ ^2-. A possible scavenging process, called limb cloud scavenging, is presented to explain the interaction of particles and nitrate ions at the early stage of rain. In limb cloud scavenging, the repeated migration of cloud particles or raindrops between the inside and outside of clouds increases the absorption of ions to a highly condensed level, thus increasing the N/S value of rainwater. The influence of global scale seasonal phenomena with large amounts of particulates, such as typhoons or Asian dust storms, was also studied.     

Ground Based FTIR Measurements of Stratospheric Species from Harestua, Norway During Sesame and Comparison with Models

Vertical columns of HF, HCl, HNO3, ClONO2, N2O, ClO and COF2 were measured at Harestua, Norway (60.22° N, 10.75° E, Elevation 600 a.s.l.) beginning on 24 November 1994 and concluding on 1 May 1995 during Phase-III of the SESAME (Second European Stratospheric Arctic and Mid-latitude Experiment) measurement campaign. The vertical columns of HCl, HNO3 and ClONO2 measured on 81 days were compared with columns calculated by the 3-D Cambridge model SLIMCAT. In addition the results were also interpreted by comparison with a photochemical trajectory model. Good agreement was seen for HCl while the nitrogen compounds showed larger discrepancies, especially for ClONO2. Evidence for chlorine activation was seen with 65% reduction of the chlorine reservoirs (HCl + ClONO2) while the levels of ClO were greatly enhanced. Interpretation of the loss with the trajectory model indicated condensation of chlorine on PSCs. The vertical column ratio of COF2 and HF was measured to 0.21 outside the vortex and a factor of two lower inside. The recovery of ClONO2 was seen to be much faster than that of HCl in the early spring.     

上海地区酸雨气候特征及成因分析

基于宝山及浦东两个气象站的酸雨历史观测资料,分析了上海地区酸雨长期变化的气候特征及其形成原因,并对比分析降水酸度的空间分布差异。宝山站降水总体上呈弱酸性,多年平均pH值为5.21,酸雨率为24%。降水pH值年际变化仅呈现微弱下降趋势,电导率K值呈明显地逐年上升变化,平均每年增加2.0 μs·cm^-1,而酸雨率波动较大,由2004年8%增至2009年48%。降水pH值在冷季较低,暖季较高,电导率K值正相反。浦东酸雨平均pH值4.38,低于宝山的5.08,酸雨率浦东79.5%,远高于宝山的33%。大气污染物SO₂、NO₂及PM₁₀浓度与酸雨pH值呈负线性相关,而与电导率K值呈正相关。大气颗粒物含量、污染物化学组成、降水量、风向等对降水pH值及酸雨率变化具有重要的影响作用。     

NaCl Aerosol Particle Hygroscopicity Dependence on Mixing with Organic Compounds

Organic compounds in the atmosphere can influence the activation, growth and lifetimes of haze, fog and cloud droplets by changing the condensation and evaporation rates of liquid water by these aqueous aerosol particles. Depending on the nature and properties of the organic compounds, the change can be to enhance or reduce these rates. In this paper we used a tandem differential mobility analyzer (TDMA) to examine the effect of tetracosane, octanoic acid, and lauric acid on the hygroscopic properties of NaCl aerosol particles at relative humidities (RH) between 30 and 95%. These organic compounds have been identified in ambient aerosol particle samples. A slight lowering of the deliquescence relative humidity (DRH) and suppression of hygroscopic growth for the NaCl-organic compound mixtures were observed when compared to pure NaCl particles. The growth of pure NaCl particles was 2.25 in diameter at 85% RH while the growth of the mixed particles was 1.3 to 1.7 in particle diameter at 85% RH with organic mass fraction of 30–50%. This shows that these organic compounds have to be present in rather large mass fractions to effect the hygroscopic behavior to a similar degree observed for ambient aerosol during field measurements. Despite the mixing of the organic material with NaCl, hysteresis was observed for decreasing RH histories, suggesting the formation of metastable droplets. These laboratory results are strikingly similar to ambient field results. For example, if the total organic mass fraction of the particles is between 0.30 and 0.50, the particle growth at 85% RH is about a factor of 1.4 for the laboratory and field measurements. Such reduction in growth compared to the pure inorganic salt is in contradiction to speculations concerning significant effects by organic compounds on cloud condensation nuclei and thus formation on clouds.     

酸性气体对混凝土耐久性的影响及研究进展

归纳认为酸性气体对混凝土腐蚀主要有三方面：碳化作用、硫酸盐的腐蚀和酸腐蚀；并通过几个典型实验及实地样品检测简要介绍了国内外迄今为止的主要实验研究手段及重要的实验研究成果；还介绍了目前研制出的用于腐蚀速度预测的两个数学表达式和两个较典型的数值模拟模型（Mehta整体模型及Saetta有限元模型）；最后概述这方面研究所需的主要的测试手段和应该采取的各种有效预防措施。最后认为虽然酸性气体或酸雨对混凝土的腐蚀研究取得一些进展，但该领域的研究尚属起步阶段，在腐蚀程度的评价、硫酸盐的应力腐蚀、腐蚀速度预测模型研究等方面还十分欠缺。建议尽快加强这些方面的研究。     

吸力路径对非饱和土力学性质的影响

基质吸力的存在使得土的工程性状变得十分复杂.非饱和土的力学性质,不仅受基质吸力及竖向荷载等应力状态的影响,吸力路径也起着不可忽视的作用.为了探讨不同吸力路径对非饱和土应力-应变关系和强度的影响,采用非饱和土直剪仪对不同吸力路径固结平衡的非饱和土样进行直剪试验,获得其固结量及应力-应变关系,得到了不同吸力路径对非饱和土抗剪强度的影响规律.试验结果表明:在相同的竖向荷载条件下,非饱和土的抗剪强度随着吸力的增加明显增大.在相同吸力及竖向荷载条件下,经历过较高吸力历史的试样固结量和前期剪切强度明显增大.     

常压密闭微波消解-电感耦合等离子体发射光谱法测定锑矿石中的锑

采用王水溶解锑矿石常出现溶矿不彻底、提取过程中锑水解的问题,导致测定结果偏低;虽然原子荧光光谱法广泛应用于锑的测定,但是该方法由于仪器线性范围窄,对于高含量锑(5%)的测定容易引入较大稀释误差。本文对样品采用氢氟酸-硝酸-盐酸混合酸溶后,在提取过程中加入酒石酸与锑络合,充分抑制了锑的水解。实验结果表明:采用氢氟酸、硝酸、盐酸混合酸体系的溶矿方式,能够有效分解矿石中的硅酸盐组分,使溶解更加彻底,锑的测定结果优于王水溶矿,且检出限更低(1.10μg/g);通过酒石酸与锑的络合及盐酸对锑水解的抑制,锑的测定结果优于王水介质及盐酸介质的结果,且方法精密度(RSD,n=6)为0.11%～1.11%,较其他介质更稳定。在ICP-OES分析中通过对锑元素分析谱线的优选,可以获得更宽的线性范围,从而实现了对较高含量锑的准确测定。本方法能快速、有效溶解锑矿石并避免锑元素水解,经国家一级标物验证,所得结果与认定值相符,适用于分析锑矿石中含量范围在0.7%～40%的锑。     

酸碱滴定法测定天然石膏中碳酸盐的不确定度评定

对酸碱滴定法测定天然石膏中碳酸盐的结果进行不确定度评定。测量过程中的不确定度主要来源于样品制备过程引入的不确定度、滴定导致的不确定度、标定NaOH标准滴定溶液和HCl标准溶液引起的不确定度及重复性实验引起的不确定度等。合成各不确定度分量,并乘以扩展因子2得到扩展不确定度。对于CO₂平均含量为8.66%（质量分数）的天然石膏样品,其扩展不确定度为0.17%。