Studies on the effects of air pollution on limestone degradation in Great Britain

The CEGB and the Cathedrals Advisory Commission for England formed a Joint Working Party in 1985 to promote a research programme aimed at improving the understanding of the relationships between stone decay, atmospheric pollution and other factors. The programme has included exposure of limestone samples at York Minster and eight other sites in England and Scotland selected to give a mix of urban, marine and rural locations. All of the sites have comprehensive air pollution and meteorological monitoring and measurement of rainfall chemistry. At two sites samples have been fumigated with controlled levels of sulphur dioxide.Over all sites, there was a significant trend to increased weight loss with increase in average sulphur dioxide concentration, but a negative trend with total nitrogen oxides and with nitrogen dioxide. For sample exposures longer than 200 days, the sulphur dioxide dependence at the inland Liphook fumigation site was about half that found near the coast at Littlehampton. There was no significant trend to increase weight loss with total rainfall amount for the complete data set, but the analysis was dominated by the very wet Scottish site, which experienced the lowest average concentrations of air pollutants.A theoretical model for the chemical dissolution of rainwashed limestone has been derived from consideration of the ion and mass balances between the incident rain water and run-off water. The model has been fitted to the measured loss rates from the stonework field trials. With the exception of the very wet Scottish site, the difference between the stone loss rate, calculated from the model, and the mean measured loss rate for any particular exposure was generally smaller than the variation between the triplicate samples. Variation in the dry deposition velocity between sites and exposure periods does not appear to have been a very significant factor, and no residual effect due to the concentrations of nitrogen oxides was found. The natural solubility of limestone in water was the dominant term in describing the stone loss, and neutralization of the rainfall acidity the least significant. The volume of the intercepted rainfall and the variation in the pH of the run-off water with rainfall intensity have been identified as the two most significant terms which require more precise quantification. The data from the inland fumigation site used in the model predict a stone loss due to sulphur dioxide in the air of less than 1 μm yr⁻¹ surface recession per ppb SO₂.     

Effects of acidic deposition on the erosion of carbonate stone — experimental results from the U.S. National Acid Precipitation Assessment Program (NAPAP)

One of the goals of NAPAP-sponsored research on the effects of acidic deposition on carbonate stone has been to quantify the incremental effects of wet and dry deposition of hydrogen ion, sulfur dioxide and nitrogen oxides on stone erosion. Test briquettes and slabs of freshly quarried Indiana limestone and Vermont marble have been exposed to ambient environmental conditions in a long-term exposure program. Physical measurements of the recession of test stones exposed to ambient conditions at an angle of 30° to horizontal at the five NAPAP materials exposure sites range from ∼ 15 to ∼ 30 μm yr⁻¹ for marble, and from ∼ 25 to ∼ 45 μm yr⁻¹ for limestone, and are approximately double the recession estimates based on the observed calcium content of run-off solutions from test slabs. The difference between the physical and chemical recession measurements is attributed to the loss of mineral grains from the stone surfaces that are not measured in the run-off experiments. The erosion due to grain loss does not appear to be influenced by rainfall acidity, however, preliminary evidence suggests that grain loss may be influenced by dry deposition of sulfur dioxide between rainfall events. Chemical analyses of the run-off solutions and associated rainfall blanks suggest that ∼ 30% of erosion by dissolution can be attributed to the wet deposition of hydrogen ion and the dry deposition of sulfur dioxide and nitric acid between rain events. The remaining ∼ 70% of erosion by dissolution is accounted for by the solubility of carbonate stone in rain that is in equilibrium with atmospheric carbon dioxide (“clean rain”). These results are for marble and limestone slabs exposed at an angle of 30° from horizontal. The relative contribution of sulfur dioxide to chemical erosion is significantly enhanced for stone slabs having an inclination of 60° or 85°. The dry deposition of alkaline particulate material has a mitigating effect at the two urban field exposure sites at Washington, DC, and Steubenville, OH.     

石灰石脱硫反应活性的研究

脱硫剂石灰石的反应活性对流化床燃煤锅炉的脱硫效果影响很大。目前,国内外主要采用动力学方法,通过测定固态CaO的硫酸盐化程度来推断石灰石的反应活性。但是这在石灰石中含有许多其它杂质成分时是不够全面的,因为这些杂质成分对石灰石的脱硫反应活性影响很大,不能忽视。为此,通过测定流化床入口和出口的SO₂浓度变化来判断加入床中的石灰石样品的反应活性。由于凡是能引起SO₂浓度变化的物质都与石灰石的反应活性有关,从而克服了原有方法仅考虑CaO重量变化的片面性。本文也采用了动力学方法建立了石灰石反应动力学模型,并利用线性化方法对其反应速率常数Ｋ进行线性估计,建立了石灰石化学成分与活性关系的数学模型。     

二氧化硫浓度的垂直分布对云下雨水酸化的影响

用一物理化学模式讨论了云下雨水的酸化过程.参照重庆地区的实际情况,讨论了SO_2随高度指数分布和其它分布对酸化的影响及近地面层高浓度SO_2对酸化的影响.SO_2平均浓度与实际垂直分布相比较,地面雨水成份相差较小,用平均浓度代替实际垂直分布是可行的.     

SO2 oxidation in an entraining cloud model with explicit microphysics

A model of the chemical evolution of the droplets in a hill-cap cloud is presented. The chemistry of individual droplets forming on cloud condensation nuclei of differing size and chemical composition is considered, and the take-up of species from the gas phase by the droplets is treated explicity for the droplet population. Oxidation of S(IV) dissolved in cloud droplets is assumed to be dominated by hydrogen peroxide and ozone.Hydrogen peroxide is normally found to be the dominant oxidant for the oxidation of sulphur dioxide (except in the presence of substantial concentrations of ammonia gas, which increases droplet pH and the contribution made by the oxidant ozone). The entrainment of hydrogen peroxide from above the cloud top increases the amount of sulphate produced in conditions where the reaction is otherwise oxidant limited by the availability hydrogen peroxide. These conditions occur when there are high concentrations of sulphur dioxide accompanied by low cloudwater pH values.Within droplets formed on sodium chloride aerosol, reduced levels of acidity lead to an increase in sulphate production as a result of an enhanced reaction between SO₂ and the oxidant ozone. This results in an overall higher increase in cloudwater sulphate than would be expected assuming an even distribution of all reactants amongst the droplets. In addition, concentrations of the hydrogen sulphite ion predicted to occur in the cloudwater can be substantially in excess of those predicted from the bulk cloudwater pH. This is consistent with recent observations.     

第三系红层下石林的岩溶动力学特征

区域地球化学表明 ,第三系泉水及直接被第三系覆盖的灰岩泉水的SIC在雨季小于 0 ,在旱季大于 0。在祭白龙洞 ,地表被第三系覆盖洞段滴水的暂时硬度比地表无此覆盖层的滴水小 1 .6～ 3mmol/L ,pH值也较低。第三系盖层中空气CO2 浓度为 1 0 0 0 0～ 1 4 0 0 0mg/m3,随深度下降。第三系的裂隙最大渗透张量为 0 .0 2～ 0 .0 5m/d,高于石灰岩。野外溶蚀试验结果 ,第三系盖层中石灰岩的溶蚀速率为 1 .5mg/ 1 0 0d,且垂直溶蚀速率与水平溶蚀速率相当。上述特征表明 ,较高的裂隙渗透张量及随裂隙下渗的富侵蚀性的水是石芽、石林发育的两个重要因素。这也是为什么发育好的石林常常伴随残留的小面积第三系出现的原因     

Gypsum accumulation on carbonate stone

The accumulation of gypsum on carbonate stone has been investigated through exposure of fresh samples of limestone and marble at monitored sites, through examination of alteration crusts from old buildings and through laboratory experiments. Several factors contribute to gypsum accumulation on carbonate stone. Marble or limestone that is sheltered from direct washing by rain in an urban environment with elevated pollution levels is likely to accumulate a gypsum crust. Crust development may be enhanced if the stone is porous or has an irregular surface area. Gypsum crusts are a surficial alteration feature; gypsum crystals form at the pore opening-air interface, where evaporation is greatest.     

Stone degradation due to dry deposition of HCl and SO2 in a laboratory-based exposure chamber

The role of the gaseous pollutants, HCl and SO₂, has been investigated in a laboratory-based atmospheric flow rig. Using an HCl level of 25 ppm at a pollutant bulk presentation rate 10 times that found typically outdoors, a degradation acceleration factor of about 20 times was obtained, together with realistic degradation products. HCl was found to be a more reactive gas than SO₂, which was also studied at the 25 ppm level. This may be due either to factors involved in the adsorption of the gases on to the stone surfaces, or the extensive solubility of HCl, or the requirement of an extra step in the conversion of SO₂ to sulphate, which would limit the overall reaction rate. The soluble degradation product CaCl₂ is readily washed off the stone allowing continuous reaction, while the relatively insoluble CaSO₄.2H₂O can remain on, or in the stone surface regions and may inhibit or affect further reaction with SO₂.The reaction of limestone with HCl gas is mass-transport limited and greater material losses arise in locations of higher HCl concentration and deposition velocity, i.e. a close-to-source effect is highlighted due to its high solubility and reactivity, but the HCl concentration is, of course, generally about one-fiftieth of that of SO₂ outdoors. For SO₂, with lower solubility and a necessary oxidation stage to form SO₄²⁻, comparatively high deposition velocities are applicable more widely from the source. The consequences include a widespread formation of relatively insoluble CaSO₄.2H₂O and consequent crust development.     

填充式电晕法处理二氧化硫的实验研究

主要研究了电晕放电等离子体法处理二氧化硫的效果。通过电晕放电产生大量的氧化性很强的自由基 ,在它们的作用下 ,与二氧化硫发生一系列的物理和化学反应 ,从而达到去除二氧化硫的目的。同时提出加入适当电介质增强放电强度的方法 ,以达到降低成本的目的     

我国SO2减排构想与经济分析

对我国未来燃煤SO₂排放数量进行了测算,设计了一个SO₂减排方案,并对减排成本进行了经济分析。据测算,2000年燃煤SO₂排放量将达到2163万t,减排44万t,减排成本为12.99亿元;2010年燃煤SO₂排放量将达到2613万t,减排1448万t,减排成本为285.10亿元。      

水蒸汽流化下煤气化气态污染物释放研究1.污染物生成与脱硫实验研究

在一个连续给煤下排料的实验室规划的流化床煤气化实验台上，对不同煤种，不同温度情况下主要污染物硫化氢，氨，氰化氢的产量进行了测量，分析了各种操作条件对污染物流量的影响，并通过平行实验的比较，考察了在水蒸汽存在的还原气氛中不同温度，不同钙硫比条件下石灰石的脱硫效率。     

On the memory effect of limestone for air pollution

During the last decade, there have been several reports in the literature on the “memory effect of building stones”, indicating that the stone erosion rate depends also on the environmental conditions the stone has experienced in the past. The present study checks whether this effect exists. A network of microcatchment units, exposing Massangis stone slabs to ambient atmospheric conditions, has therefore been set up througout Belgium. Runoff water fromt the stome specimens was collected on a weekly basis. The limestone slabs were switched between sites with different pollution levels, and their material loss rate trends examined. The rate of stone loss distinctly changed after the displacement, indicating an immediate adaptation of the stone to the new environment. Hence no evidence for a memory effect could be found.     

Dispersion of sulphur dioxide around the thermal power plant at Ahmedabad,India

Air quality due to the release of sulphur dioxide from the thermal power plant within the city limits of Ahmedabad has been computed employing a point, area and line dispersion model. To estimate probable air quality, the meteorological data for 3 consecutive days in the middle of each month of 1983 is used. The concentration of sulphur dioxide is computed at a distance of every 500 m in 16 directions up to the city limit. The air quality in the worst case is estimated in downwind distances under unfavourable meteorological conditions.The probable zones of high concentrations of sulphur dioxide over residential, commercial and industrial areas of the city are below the ambient air quality standards set by the U.S. EPA in 1971 almost throughout the year. However, in the months of April and October the zone of high concentration (500 μg m⁻³) exceeds the EPA standard. Also, under the most unfavourable meteorological conditions, the estimated high ground-level concentration of sulphur dioxide can reach up to 1000 μg m⁻³ at a distance of 1.25 km from the thermal power plant. This may be attributed to the effect of fumigation.     

中国酸雨和二氧化硫污染控制区区划及实施政策研究

阐述了中国二氧化硫和酸雨污染现状,分析了划分二氧化硫污染和酸雨控制区的依据和原则,绘出了二氧化硫污染和酸雨控制区的范围,重点分析研究了二氧化硫污染和酸雨控制区内的控制目标以及用燃料生命周期评价方法确定的控制二氧化硫排放政策,并研究了政策实施对煤炭工业、电力工业的影响     

中国南方喀斯特地区石灰土容重传递函数模型及影响因素研究

土壤容重(BD)数据的缺失严重影响了我国南方喀斯特地区土壤碳储量的估算,亟待利用已有数据来构建容重传递函数模型(PTFs)。本文利用南方喀斯特分布省份的石灰土土壤普查数据,首次较为系统地研究了喀斯特地区石灰土的容重传递函数模型及影响因素。研究结果表明:(1)国内外已发表的容重PTFs对中国南方喀斯特地区非地带性石灰土的适用性较差,需要进行优化或重新建立新的容重函数预测模型;(2)优化后的模型Shiri et al(2017)~*、韩光中等(2016)-a~*和韩光中等(2016)-c~*的预测精度得到明显提高;(3)基于石灰土亚类建立的PTFs具有很高的拟合度和预测精度,比优化模型更加适宜于喀斯特石灰土的土壤容重预测;(4)不同石灰土亚类容重预测的影响因素存在差异,其中土壤有机质含量是石灰土容重预测的关键因素,与各亚类土壤的BD都有很高的相关性;(5)土壤容重传递函数模型的适用性不仅与研究区域有关,同时也与研究的土壤类型有关。建议在今后喀斯特地区土壤容重预测模型研究中充分考虑地域差异性和土壤类型因素。     

湖北省酸雨控制区二氧化硫污染防治规划

在归纳湖北省酸雨控制区二氧化硫污染特征的基础上,对我省酸雨控制区二氧化硫的防治途径进行了分析。提出了全省“十五”期间二氧化硫总量控制规划,并从工业点源治理、城市清洁能源两大方面安排了二氧化硫污染防治的工程措施。“十五”期间全省共安排重点项目45项,计划投资960282万元,项目完成后削减二氧化硫19.19万t/a,实现“十五”规划目标。     

北京市大气环境二氧化硫浓度分布初探

利用北京市大气自动监测系统冬季逐时二氧化硫浓度监测资料，分析研究了对数正态分布，Ｗｅｉｂｕｌｌ分布，指数分布等常用分布模型对监测资料人布推迟合的适用性，并估算出各种分布模型的参数值。研究发现城区及高百分位数二氧化硫浓度频率分布符合Ｗｅｉｂｕｌｌ分布，近郊及背景站的浓度分布符合常用的对数正态分布，二氧化硫浓度的频率分布不符合指数分布规律。     

我国SO2排放总量控制方法探索与初步评估

介绍了我国SO     

工业燃煤排放二氧化硫征收排污费初探

江苏省大气污染及酸雨危害日益严重，迫切需要加强对二氧化硫排放的管理，征收工业燃煤排放二氧化硫排污费是解决问题的有效途径。从期望征收额占各主要燃煤行业工业产值的比重看将会产生较大的影响，建议二氧化硫排污费收费标准应低于０．２元／千克（二氧化硫）。     

我国SO2排放总量控制方法探索与初步评估

介绍了我国ＳＯ３排放总量的控制方法以及大气网络输送理论在总量控制研究中的应用，并对大气ＳＯ２总量控制方法的研究结果做了初步评估，给出了我国２０１０年ＳＯ２排放总量控制的目标（甘肃、新疆、青海和西藏的大部分地区除外）。