Measurements of ammonia flux to a spruce stand in Denmark

This work demonstrates the existence of a linear relation between the deposition velocity of ammonia and the friction velocity measured above a spruce stand in the western part of Denmark. In order to estimate the ammonia deposition velocity and flux to a Norway spruce forest, concentration gradients of ammonia and several meteorological parameters were measured in a meteorology tower during two periods, 1 week in spring and 1 week in late summer 1991. The estimated deposition velocities lie in the range −0.125 to 0.201 m s⁻¹, with a mean of 0.026 m s⁻¹. The deposition velocity and the flux were generally largest in the afternoon. On the basis of 24-h measurements of ammonia and routine meteorological measurements the relation between deposition velocity and friction velocity is extrapolated to an estimate of the average flux for the growing season May to September 1991. The estimate gave an average flux of 87 μg NH₃N m⁻² h⁻¹ (=0.02 μg NH₃N m⁻² s⁻¹). The average deposition velocity for the period was 0.045 m s⁻¹.     

Interdependence of the slopes and intercepts from log-log correlations of measured gas-particle paritioning and vapor pressure—I. theory and analysis of available data

Gas-particle partitioning is examined using a partitioning constant K_p = (F/TSP)/A, where F (ng m⁻³) and A (ng m⁻³) are the particulate-assiociated and and concentrations, respectively, and TSP is the total suspended particulate matter level (μg m⁻³). At a given temperature and for a given sample of particulate matter, compound-dependent values of K_p tend to be correlated with the sub-cooled liquid vapor pressure (p_L⁰, toor according to log K_p = m_r log p_L⁰+b_m. Theory predicts that b_r values should be somewhat similar, and that m_r values should be near −1. This is supported by field and laboratory work. However, there is still noticeable variability in reported m_r and b_r values, even when obtained by the same researchers sampling in the same location. Three possible thermodynamic sources of variability include variability in the compound-to-compound differences in the thermodynamics of adsorption, event-to-event variability in the specific surface area of the aerosol and event-to-event variability in the ambient temperature. Non-thermodynamic sources of variability include sorption of gaseous analytes to the filters used in differentiating between F and A, the presence of non-exchangeable component in the measured F values, within-event adsorption/desorption kinetics, within-event changes in contaminant levels, and within-event changes in temperature. Each of these sources of variability operate in their own way to cause variability in m_r and b_r. In general, one can expect there to be a correlation in the obseved m_r and b_r of the form b_r = m_sm_r+b_s. For the study of Yamasaki et al. (1982, Envir. Sci. Technol. 16, 189–194), one obtains m_s = 5.77 and b_s = −2.18, with r² = 0.91. In the presence of such a correlation, one can expect that all log (F/TSP)/A vs log p_L⁰ plot will tend to intersect at the same (x,y) poitn given by (−m_s, b_s. Exisiting field and laboratory data show this tendency.     

Environmental chamber for study of the deposition flux of gaseous pollutants to material surfaces

A specially designed recirculating environmental chamber was constructed to study the environmental factors affecting the deposition of pollutant gases to the surface of stone and other building materials. The chamber and sample holder are designed to place samples in an aerodynamically well-defined air flow. The system is designed to permit use of radioactive ³⁵SO₂ as a tracer if necessary. A wide range of typical environmental conditions can be continuously maintained in the chamber. Wind speeds in the test section can range up to about 5 ms⁻¹, exposing replicate samples to air flow that is uniform to within approximately 3%. Relative humidity in the chamber can be maintained to within 3%, and SO₂, NO₂ and O₃ concentrations in the chamber air can be maintained to within 4%. Test results indicate SO₂ deposition and wind speed in the chamber are closely correlated, allowing for a direct determination of the surface resistance (r_c) component of the SO₂ deposition velocity to various test materials. Initial studies of SO₂ deposition to limestone and marble indicate the r_c values are approximately 1.3 s cm⁻¹ for fresh limestone and 34 s cm⁻¹ for fresh marble at 75% relative humidity, 26°C and 50 ppb SO₂.     

Chemical and optical properties of aerosols and their interrelationship in winter in the megacity Shanghai of China

A field campaign on air quality was carried out in Shanghai in winter of 2012. The concentrations of NO, NO₂, NO_x, SO₂, CO, and PM_2.5 increased during haze formation. The average masses of SO₄^2-, NO₃^- and NH₄⁺ were 10.3, 11.7 and 6.7 μg/m³ during the haze episodes, which exceeded the average (9.2, 7.9, and 3.4 μg/m³) of these components in the non-haze days. The mean values for the aerosol scattering coefficient (b_sp), aerosol absorption coefficient (b_ap) and single scattering albedo (SSA) were 288.7, 27.7 and 0.91 Mm^-1, respectively. A bi-peak distribution was observed for the mass concentrations of CO, NO, NO₂, and NO_x. More sulfate was produced during daytime than that in the evening due to photochemical reactions. The mass concentration of NH₄⁺ achieved a small peak at noontime. NO₃^- showed lower concentrations in the afternoon and higher concentrations in the early morning. There were obvious bi-peak diurnal patterns for bsp and bap as well as SSA. bsp and bap showed a positive correlation with PM_2.5 mass concentration. (NH₄)₂SO₄, NH₄NO₃, organic mass, elemental carbon and coarse mass accounted for 21.7%, 19.3%, 31.0%, 9.3% and 12.3% of the total extinction coefficient during non-haze days, and 25.6%, 24.3%, 30.1%, 8.1% and 8.2% during hazy days. Organic matter was the largest contributor to light extinction. The contribution proportions of ammonium sulfate and ammonium nitrate to light extinction were significantly higher during the hazy time than during the non-haze days.     

Physicochemical damage parameters for the action of SO2 and NO2 on single pieces of marble

The theoretical analysis for measurement of building-damage parameters by RF-GC technique is applied to the action of SO₂ and NO₂ on marble. The experiments with SO₂ were performed with five different geometric forms of single pieces of marble at 373.2 K and were repeated after washing these pieces 8 times with three-distilled water. All six physicochemical parameters determined show negligible variations for the same solid form at the same temperature, but they are different for the various geometrical forms. The mass transfer coefficients K_g and K_s and their ratio K seem to be the most invariant parameters with respect to the form. After washing with water, some of the parameters change considerably.The action of NO₂ was studied on a sphere only, but at five different temperatures. The physicochemical parameters for the action of this gas are three orders of magnitude smaller than those of SO₂ (except K), leading to 3700 times bigger resistance of marble to mass transfer of NO₂ than of SO₂. From the variation of the parameters with temperature, it is concluded that both mass transfer coefficients, K_g and K_s, pertain to activated processes with activation energies 39 and 27 kJ mol⁻¹, respectively. The reaction of the adsorbed gas with the solid is less activated, whereas the adsorption equilibrium constant K does not change with temperature.     

浙江宁波天童地区酸性降水化学特征研究

为了解浙江宁波天童地区降水的化学特征、离子来源及酸性降水的成因,于2010年3月—2011年2月在该地区采集了90个降水样品,并运用离子色谱法分析其化学组分.结果显示,天童地区降水的酸化频率和酸化程度非常高,酸雨频率为97%,雨量加权pH平均值为4.37,离子浓度的大小顺序为SO24->NH4+>NO3->Ca2+>Cl->Na+>Mg2+>K+>F-,降水较清洁;降水pH值和各离子含量存在明显的季节变化,总体表现为冬、春季污染程度高于夏、秋季;SO24-/NO3-的浓度比值为1.9,表明该地区酸雨类型为硫酸和硝酸复合型;SO24-、NO3-、NH4+和部分Ca2+主要来自人为污染源,Na+、Cl-和大部分Mg2+主要来自海洋源,K+和大部分Ca2+则主要来自地壳源,海洋对天童地区降水离子组分影响较大,但对降水酸度影响并不显著;NH4+与SO42-(r=0.90)、NO3-(r=0.88)的相关性分别大于Ca2+与SO24-(r=0.67)、NO3-(r=0.73)的相关性,且NH4+/Ca2+的浓度比值为1.47,说明NH4+对降水酸性的中和作用大于Ca2+,与我国其他城市降水相比,天童地区降水中的碱性离子,尤其是Ca2+浓度较低,从而导致降水酸度高于北方地区和西南其他地区.     

Seasonal contrasts in modelled and observed dry deposition velocities of O3, SO2 and NO2 over three surfaces

Results of modelled and observed deposition velocities (V_d) for O₃, SO₂ and NO₂ for time-averaged diurnal cycles and sometimes for a collection of hourly values taken from different days are discussed for different seasons. From the observations, it was found that the O₃V_d values over a deciduous forest had a daytime representative value of 1.0 cm s⁻¹ in the summer and 0.3 cm s⁻¹ in the winter. For SO₂ over the same forest and over a carrot field the daytime values ranged from 0.0 to 0.65 cm s⁻¹ in the autumn, and for SO₂ over a snow surface the V_d ranged from 0.0 to 0.15 cm s⁻¹. The NO₂V_d was mostly negative over the forest and the carrot field in the autumn and had a range of 0.0-0.15 cm s⁻¹ over snow. From the model, it was found that for the three seasons the V_d values over all the land-use types were much larger than the observations. The model could not simulate the observed negative values of the NO₂V_d. The impact of the V_d model and its modified version on the concentrations of O₃ and SO₂ were tested with a comprehensive Eulerian air quality model.     

Changes in soil respiration across a chronosequence of tallgrass prairie reconstructions

Close relationships among climatic factors and soil respiration (R_s) are commonly reported. However, variation in R_s across the landscape is compounded by site-specific differences that impede the development of spatially explicit models. Among factors that influence R_s, the effect of ecosystem age is poorly documented. We hypothesized that R_s increases with grassland age and tested this hypothesis in a chronosequence of tallgrass prairie reconstructions in central Iowa, U.S.A. We also assessed changes in root biomass, root ingrowth, aboveground net primary productivity (ANPP), and the strength of soil temperature and moisture in predicting R_s. We found a significant increase in total growing season R_s with prairie age (R² = 0.79), ranging from 714 g C m^?2 in the youngest reconstruction (age 4) to 939 g C m^?2 in the oldest prairie (age 12). Soil temperature was a strong predictor of intra-seasonal R_s among prairies (R² = 0.78–0.87) but mean growing season soil temperature and moisture did not relate to total R_s. The increase in R_s with age was positively correlated with root biomass (r = 0.80) and ANPP (r = 0.87) but not with root ingrowth. Our findings suggest that growing season R_s increases with tallgrass prairie age, root biomass, and ANPP during young grassland development.     

稻田气溶胶NH3和气体NOx排放在线测定研究

气溶胶NH3和气体NOx是大气颗粒物和降水的主要成分,是形成气溶胶的关键物种.田间集约化氮肥施用是气溶胶NH3和气体NOx的一个重要来源,目前该领域的研究鲜有报道.2010年5月～2010年10月,在线监测了稻田施用尿素后气溶胶NH3和气体NOx的排放情况.监测系统的时间分辨率设置为1 h.在4次稻田施肥试验中,施肥后对气溶胶NH3排放和相应的气象因子连续采样20 d.在第4次施肥试验中,施肥后连续采样47 d,进而研究气体NOx的排放规律及其与气象因子的关系.结果表明,气溶胶NH3的排放因子分别为2.6%、5.5%、4.0%和1.6%,相应的排放通量分别为3.97、2.08、1.52和1.22 kg·hm-2.温度(空气温度和土壤温度)是影响稻田施肥气溶胶NH3排放的主要因子,而空气湿度和土壤水分对其排放的影响却不明确.通过分析监测数据可知,稻田施肥后NO2-N排放量与NO-N排放量的比值为9/4,气体NOx的排放因子和排放通量分别为0.14%和0.30 kg·hm-2.气象因子与气体NOx排放通量的关系也进行了初步探讨.     

Interactions of aerosols (ammonium sulfate,ammonium nitrate and ammonium chloride) and of gases (HCl,HNO3) with fogwater

The concentrations of aerosols (NH₄NO₃, (NH₄)₂SO₄ and NH₄Cl) and of gases (HCl_(g), HNO_3(g), NH_3(g) were determined by denuder methods under different conditions (in the absence of fog, before, during and after fog events). At this site situated in an urban region, high concentrations of the gaseous strong acids HCl_(g) and HNO_3(g) are observed. NH₄Cl and NH₄NO₃ aerosols represent a major fraction of the Cl⁻ and NO₃⁻ aerosols (<2.4 μm)collected by denuders. During a fog event, very high concentrations of SO₄²⁻ were found in small aerosols, which are attributed to the aqueous phase oxidation of SO₂ under the influence of high pH due to the presence of NH₃. Differences in SO₄²⁻ concentrations measured in aerosols (<2.4 μm) and in fog droplets were probably due to mass-transport limitations of the SO₂ oxidation. Ammonium sulfate aerosols represent in some cases a significant fraction of the total S present (SO_2(g) + SO₄²⁻. Soluble aerosols and gases contribute to the composition of fogwater and are released again after fog dissipation.     

Transported acid aerosols measured in southern Ontario

During the period 29 June 1986–9 August 1986, a field health study assessing the acute health effects of air pollutants on children was conducted at a summer girls' camp on the northern shore of Lake Erie in SW Ontario. Continuous air pollution measurements of SO₂, O₃, NO_x, particulate sulfates, light scattering, and meteorological measurements including temperature, dew point, and wind speed and direction were made. Twelve-hour integrated samples of size fractioned particles were also obtained using dichotomous samplers and Harvard impactors equipped with an ammonia denuder for subsequent hydrogen ion determination. Particulate samples were analyzed for trace elements by X-ray fluorescence and Neutron Activation, and for organic and elemental carbon by a thermal/optical technique. The measured aerosol was periodically very acidic with observed 12-h averaged H⁺ concentrations in the range < 10–560 nmoles m⁻³. The aerosol H⁺ appeared to represent the net strong acidity after H₂SO₄ reaction with NH₃(g). Average daytime concentrations were higher than night-time for aerosol H⁺, sulfate, fine mass and ozone. Prolonged episodes of atmospheric acidity, sulfate, and ozone were associated with air masses arriving at the measurement site from the west and from the southwest over Lake Erie. Sulfate concentrations measured at the lakeshore camp were more than twice those measured at inland sites during extreme pollution episodes. The concentration gradient observed with onshore flow was potentially due to enhanced deposition near the lakeshore caused by discontinuities in the meteorological fields in this region.     

城市道路隔离带绿化模式对人行道空气质量的影响评价

探讨城市道路绿化隔离带对于污染物的阻滞效应,以减少城市道路污染向两侧横向扩散,保护道路行人免受来自机动车道污染物的伤害具有重要的现实意义.因此,本研究在太原市区选择16条主干道(28个监测样点),以4种绿化植物配置模式(乔木+灌木+低绿篱、乔木+低绿篱、乔木、低绿篱)为研究对象,在无风或者微风(风速小于2 m·s-1)条件下对SO2、NOx、TSP和PM10等5种污染物进行现场监测.研究结果表明,城市道路绿化隔离带对于控制机动车道的主要污染物向非机动车道的扩散具有明显作用,绿化隔离带的植物模式差异会影响绿化带吸附和阻隔污染物能力的强弱.在此基础上,通过构建一个新的评价指标来比较各个模式在阻滞污染物方面的能力.结果显示,与其他模式相比,低绿篱模式和乔木+灌木+低绿篱模式分别对NH3和PM10具有更高的降低能力.对于SO2、NH3、NOx等气态污染物,以乔木(T)为配置模式的绿化带效果最佳,而对于TSP、PM10等颗粒污染物,乔木+灌木+低绿篱(TSH)模式的阻滞净效应最高.新评价指标能够准确定量评价绿化带植物对污染物阻滞效应能力的大小,具有较好的应用性.     

Fluxes of nitric and nitrous oxides from agricultural soils in a cool temperate climate

Fluxes of NO and N₂O from sandy loam soils cropped with winter wheat and a clay loam soil under ryegrass, with and without the addition of NH₄NO₃ fertilizer, were measured using static and dynamic chamber methods. Nitric oxide fluxes ranged from −0.3 (deposition) to 6.9 (emission) ng NO-N m⁻² s⁻¹. The corresponding N₂O flux ranged from 0 to 91 (emission) ng N₂O-N m⁻² s⁻¹. The NO flux was temperature dependent. Activation energies ranged from 40 to 81 kJ mol⁻¹. Nitric oxide and N₂O fluxes increased linearly with soil available nitrogen (NH₄ + NO₃). Emissions of NO and N₂O were not detectable from unfertilized ryegrass plots. Instead, nitric oxide was absorbed by the soil and vegetation at a maximum rate of 0.31 ng NO-N m⁻² s⁻¹. The aeration state of the soil controlled the relative rates of NO and N₂O emission. Nitric oxide was the major gas emitted from well aerated soils, conditions that favour nitrification. The NO/N₂O emission ratio was >100 for the coarse-textured sandy loam soil and the clay loam soil only during low rainfall periods. Nitrous oxide was the major gas emitted from less aerated soils, conditions that allowed denitrification to occur. The NO/N₂O emission ratio was <0.001 for the clay loam soil when rainfall was high and soils were wet. Extrapolation to the U.K. situation showed that agricultural land may account for 2–6% of the total annual NO_x emission and for 16–64% of the total annual N₂O emission in the U.K.     

海峡西岸经济区大气污染物排放清单的初步估算

以2009年为基准年,结合污染源普查数据、统计年鉴及工业活动、居民生活等多个方面对海峡西岸经济区包括SO2、NOx、PM2.5、VOCs和NH3在内的大气污染物的排放量进行了估算,建立了海西区大气污染物排放清单.结果发现,上述5类污染物基准年的排放量分别为40.67×104、55.84×104、50.57×104、152.26×104和26.18×104t.其中,SO2、NOx及PM2.5的排放主要来自电厂,占排放总量的比例分别为25.58%、34.89%和38.75%;VOCs和NH3的主要排放源分别来自植被排放和养殖业,其贡献量分别为49.12%和47.07%.采用GIS对排放清单进行网格化处理,得出SO2、NOx及PM2.5的高排放强度区域与固定源的空间分布较为一致.此外,结合国家和地方"十二五"发展规划,采用情景分析方法估算了2015年海西区大气污染物的排放清单.与基准年相比,SO2、NOx和NH3的排放量呈下降趋势,PM2.5和VOCs的排放量呈大幅度增加.基准年排放清单的不确定性分析显示,VOCs排放估算的不确定度最大,为225%.     

气候变化对浙江省大气污染的影响

开展气候变化对大气污染影响的研究有利于加深对大气污染形成机理的认识.利用1996-2015年浙江省大气成分、气象观测资料,分析气候变化对大气污染的影响.结果表明,近20 a来浙江省呈年高压天气日数增多、年均气温升高、降水集中及年均净辐射、日照时数、风速、气温日较差和水汽蒸发量都下降的气候变化事实.气候变化引起大气污染扩散能力下降,1996-2015年杭州市和浙江省年均大气扩散指数分别下降了0.55和0.81,降幅分别达35.71%和42.69%.大气扩散指数与ρ（PM₁₀）、ρ（PM_2.5）及年霾日数之间呈显著负相关,当大气扩散指数增大时,大气颗粒物浓度和年霾日数均下降,反之亦然.杭州市大气扩散指数与ρ（PM₁₀）、ρ（PM_2.5）之间的相关系数分别为0.73和0.76.杭州市和浙江省大气扩散指数与年霾日数之间的相关系数分别达到0.77和0.78,T检验值则分别为28.88和30.81,说明由气候变化引起的大气扩散能力改变是影响大气污染的重要原因,但不同大气成分受气候变化的影响程度不同.影响ρ（PM₁₀）的关键气候要素是降水量、风速及相对湿度等,影响ρ（PM_2.5）的主要是辐射、气温,影响ρ（SO₂）的主要是气温,影响ρ（NO₂）及ρ（NO₃-）、ρ（NH₄+）的主要是辐射.总体来说,浙江省近20 a的气候变化事实可能有利于促进ρ（PM₁₀）、ρ（PM_2.5）、ρ（NO₂）及ρ（O₃）等上升,促进ρ（SO₂）、ρ（NO₃-）、ρ（SO₄2-）、ρ（NH₄+）等下降.      

邯郸市PM_(2.5)中水溶性无机离子污染特征及来源解析

本研究通过对邯郸市环境空气中PM2.5样本进行采集和成分检测,分析了该地区PM2.5中水溶性无机离子的污染特征,并结合气象要素(风速、温度)、气态污染物(O3、NO2、SO2、CO)、SOR(硫氧化率)、NOR(氮氧化率)对其主要来源进行了解析.研究结果表明:总水溶性无机离子(TWSII)浓度季节变化特征明显,秋、冬季高于春、夏季.SO2-4、NO-3、NH+4是PM2.5中主要的水溶性无机离子,在TWSII中所占的比例为夏(93.2%)冬(85.6%)秋(85.5%)春(84.0%).春、夏、秋三季PM2.5呈酸性,冬季显碱性.此外还分析得到,SO2-4在四季中均以(NH4)2SO4的形式存在.NO-3在冬季以NH4NO3的形式存在,其余季节中以NH4NO3、HNO3等共存.绝大部分Cl-在冬季以NH4Cl的形式存在,其它季节中以NH4Cl、KCl等的形式存在.均相反应是SO2-4的主要生成途径,夏、冬季也伴随有非均相反应.NO-3的生成以均相反应为主(春、夏、秋),在冬季均相反应与非均相反应同时存在.应用因子分析法解析出4个主因子,其中,工业、燃煤、交通、生物质燃烧等综合源是PM2.5中水溶性无机离子的主要来源.     

山地型城市冬季大气重污染过程特征及成因分析

以阳泉市2018年12月26日~2019年1月20日发生的典型大气重污染过程为例,研究了山地型城市冬季大气重污染过程特征及成因.结果表明,重污染发生时段首要污染物为PM_2.5,水溶性离子和碳质组分是PM_2.5主要组分,其中二次离子SO₄^2-、NO₃^-和NH₄⁺是主要水溶性离子成分（共占离子组分的87.7%）,二次有机碳（SOC）是碳质组分的主要成分（71.6%）.二次离子在重污染发生时的浓度较发生前增加5.3倍,是导致PM_2.5快速增长的重要组分.气象条件分析显示,PM_2.5及其主要组分皆与相对湿度呈显著正相关关系而与风速呈显著负相关,随相对湿度增加以及平均风速降低,污染程度逐渐加重.山地型城市相对湿度较高、温度变化幅度大等气象特征使二次污染物的生成加快,是导致PM_2.5污染程度快速加重的主要原因.另外,山地型城市相对封闭的地形导致的平均风速降低使得大气污染物扩散条件相对较差是污染物累积的原因之一.PMF模型解析结果为：二次源（46.0%）对PM_2.5贡献显著,其次为燃煤源（32.6%）、机动车源（19.8%）和扬尘源（1.6%）.因此,山地型城市更应该重视对二次组分,特别是二次离子形成的前体物的管控.     

In-cloud scavenging and deposition of sulfates and nitrates: Case studies and parameterization

Scavenging of sulfates and nitrates—two most common ions leading the cloudwater acidity—was investigated during field studies atop a site in Mt. Mitchell (35°44′05″N, 82°17′15″W) State Park where the highest peak (2038 m MSL) of the eastern U.S. is located. Experiments were conducted during the growing seasons (15 May–30 September) of 1986 and 1987 using an instrumented meteorological tower (16.5 m tall) and a passive cloudwater collector. A cloud episode that occurred on 12 October 1987, was also comprehensively investigated. Clouds were frequently observed in which the Fraser fir and red spruce stands stayed immersed 28% and 41% of the time during the 1986 and 1987 seasons, respectively. Rate of cloudwater deposition on the forest canopy was determined using an inferential cloud deposition model. It was found by analysing nine short duration (lasting 8 h or less) and 16 long duration cloud events that the ionic concentration (SO₄²⁻ and NO₃⁻) is inversely proportional to the rate (I_c) of cloudwater deposition (in mm h⁻¹) and can be expressed by the following relationship: [SO₄²⁻] = aI_c^−b or [NO₃⁻] = aI_c^−b. Theoretical arguments leading to these relationships are presented. The b values for predicting NO₃²⁻ concentration are found in the range of 0.14–1.24 (mean = 0.48) for short duration and 0.062–0.63 (mean = 0.27) for long duration cloud events, respectively. The corresponding b values for predicting NO₃⁻ concentrations are 0.19–1.16 (mean = 0.49) and 0.072–0.59 (mean = 0.27), respectively. When the b parameter was between 0.2 and 0.6, the correlation coefficients between measured and predicted ionic concentrations were found to exceed 0.7. The parameter a is shown to represent the maximum ionic flux for a given cloud event. The ratio of the a parameter for SO₄²⁻ to NO₃⁻ varied between 1.75 and 6.95, indicating that the SO₄²⁻ contributes to the total ionic concentration substantially more than the NO₃⁻ leading to the conclusion that the cloudwater acidity is primarily due to the presence of sulfuric acid which has been demonstrated to cause foliar injury and growth retardation in red spruce trees. The above parameterization is similar to the one that is frequently used to relate ionic concentration in precipitation to the rainfall rate. In order to understand physico-chemical processes leading to the proposed parameterization schemes, meteorological and chemical variables are comprehensively analysed for one short duration and two long duration cloud events. The concentrations of principal ions (SO₄²⁻, NO₃⁻, H⁺ and NH₄⁺) during the short duration cloud events were found to be much higher than those during the long duration ones, especially at colder temperatures. Such short cloud events have a potential of causing foliar narcosis in red spruce stands because of unusually acidic cloudwater to which these stands stay exposed intermittently during each growing season.     

The chemical composition of intercepted cloudwater in the Sierra Nevada

The chemical composition of cloudwater in the Sierra Nevada is dominated by NO₃⁻, SO₄²⁻, and NH₄⁺. Cloudwater pH is determined largely by the balance between the concentrations of these three species, although inputs of formic and acetic acid also are believed to be important, particularly when anthropogenic inputs are small. Cloudwater samples collected in Sequoia National Park (SNP) exhibited pH values ranging from 3.9 to 6.5; Yosemite National Park (YNP) cloudwater samples had pH values ranging from 3.8 to 5.2. Samples collected at YNP were more acidic than those collected at SNP. The difference in pH between the two regions appears to be due to relatively small differences in inputs of NO₃⁻, SO₄²⁻, and NH₄⁺. In the absence of inputs of NH₃, cloudwater pH values in the Sierra may fall below 3.Over 250 h of cloud interception were observed during a 12 month period at a cloud monitoring site at 1856 m elevaton in SNP. Estimates of cloudwater deposition of NO₃⁻, SO₄²⁻, and NH₄⁺ indicate that cloud interception contributes significantly to regional acid deposition for closed forest canopies. Cloud interception may be the dominant deposition mechanism for isolated conifers and ridgetop canopies, where wind speeds are higher and cloudy air parcels can impact directly on foliar surfaces.     

SO2对MnOx/PG催化剂低温脱硝的影响机理研究

采用等体积浸渍法制备了锰氧化物负载凹凸棒石(MnO_x/PG)低温SCR催化剂,通过SO₂暂态响应、程序升温表面反应(TPSR)等实验技术研究了烟气中SO₂对催化剂SCR脱硝活性的影响行为.采用程序升温脱附(TPD)、BET比表面及孔径分布测定、XPS等表征技术对催化剂硫中毒的机理及化学本质进行了深入分析.结果表明,低温下烟气中SO₂对MnO_x/PG催化剂的SCR脱硝活性存在显著的抑制作用,催化剂中毒主要由烟气中SO₂的催化氧化引起.一方面SO₂氧化为SO₃后与NH₃及H₂O竞争反应形成复杂的硫酸铵盐堵塞催化剂孔道,另一方面与活性组分MnO₂结合形成MnSO₄使得部分活性组分形态发生变迁.其中硫酸铵盐的形成可通过适当的热处理得以去除,而MnSO₄则不可恢复,但催化剂SCR活性却显著增加,表明MnSO₄的形成不是催化剂失活的主要因素.吸附态的硫可显著增加催化剂表面酸性,因此对SCR活性有促进作用.催化剂失活主要机理为:由气相SO₂的连续氧化并与NH₃相结合形成硫酸铵盐,并且在低温下难以分解,以致堵塞催化剂活性中心.