Receptor modeling of the fine aerosol at a residential Los Angeles site

Receptor modeling on ambient aerosol and air quality data collected at Duarte, CA (a residential site near Los Angeles), in 1983 and 1987–1988 was carried out. A significant change in the ambient concentrations of SO₄²⁻, Al, Si, Mn, Fe, Pb, Br, volatile and organic carbon and fine particle (FP) mass took place from 1983 to 1987–1988. A drastic reduction (∼80%) of the ambient Pb and Br concentrations took place as the lead content and the usage of leaded gasoline decreased in the Los Angeles Basin during that period. A day-of-the-week analysis indicated that both crustal (Si, Ca, Fe) and transportation (Pb, CO, organic carbon and black carbon) related pollutants exhibit significantly different concentrations between weekdays and weekends of 1987–1988. this indicates that loadings of suspended soil dust are more affected by anthropogenic activities than meteorological patterns. In contrast, sulfate and volatile carbon concentrations seem to be insensitive to that cycle indicating that other sources/processes can be responsible for the ambient levels of these pollutants. Principal component analysis of aerosol and air quality data showed that the major contributions to the variance of the ambient aerosol loadings come from soil, motor vehicles and sulfates.     

美国洛杉矶空气管理经验分析

过去35年间,洛杉矶的经济和人口持续增长、城市扩张,但是洛杉矶的空气污染水平得到了下降,在达到加利福利亚州和《清洁空气法》所规定的大气质量总体目标方面,有了长足的进步.期间起到重大作用的因素包括:①固定污染源和移动污染源气体污染物排放的控制技术和企业实践的巨大进步.②联邦、州和地区的清洁空气政策的发展.③强有力的专门负责清洁空气政策的监督和执行行政机构的设立.④公众压力.⑤从信任政府运用命令与控制手段到利用激励手段和市场手段完成许多政策目标(包括空气污染控制)的变革.同时,该地区的人口还在持续增长,经济继续繁荣扩张,意味着将产生更多的空气污染物,尤其是来自移动污染源的污染物.另外,在公众不太支持加强政府力量或增加税收的形势下,要求政策制定者解决空气污染的问题或大幅度改变洛杉矶居民的生活方式.     

Size distributions of trace metals in the Los Angeles atmosphere

Particle size distributions of Fe, Pb, Mz, Zn, Cu and Ni were measured at two locations in the Los Angeles area during the winter and summer of 1989 using a cascade impactor. Measures were taken to minimize particle bounce and elemental analysis was performed by X-ray fluorescence. Measured Fe size distributions were consistent, with suspended dust being the major source. Pb distributions were observed to be multimodal with modes due to automotive emissions, particle growth and suspended dust. The importance of suspended dust was investigated using Fe as tracer and suspended dust ratios of Fe to Pb and other metals. Mn distributions were observed to be similar to those of Pb with automotive emissions and suspended dust being important sources. Particle size distributions of Zn, Cu and Ni showed significant amounts of these metals to be persent in particles less than 1μm in diameter, indicating anthropogenic sources. Suspended dust was found to be an important source of Zn, but not of Cu or Ni, in particles with diameters greater than 2 μm.     

Hydrogen peroxide levels in Los Angeles: A screening-level evaluation

The major factors affecting the diurnal variation of gaseous hydrogen peroxide were studied using a one-dimensional vertical gas-phase chemistry/transport screening model. The model which included diurnal variations of the inversion layer, surface emissions, dry deposition of air pollutants, and meteorological conditions such as solar radiation, temperature, relative humidity and wind speed, was used to evaluate the influence of the ratio of NMHC/NO_x, the emission rates of NO_x and NMHC, the deposition velocity of H₂O₂, and the height of inversion layer on the ground level gaseous H₂O₂ concentrations. The model was found to yield reasonable agreement with field data from the Carbonaceous Species Methods Comparison Study at Glendora, California, in 11–21 August 1986. Specifically, model predictions and field results all indicated that during clear skies, ambient H₂O₂ concentration was highest at about early afternoon when O₃ concentration was highest and NO_x was lowest. It was concluded that the predicted gaseous H₂O₂ concentration is most sensitive to the emission rate of NO_x and the ratio of NHMC/NO_x, but it is less sensitive to the deposition velocity, height of inversion layer, and the emission rate of NMHC.     

A case study of pollutant transport from Los Angeles to the desert South-West

The transport of pollutants from the Los Angeles basin to remote sites in southern Nevada and northwestern Arizona has been fingerprinted by halocarbons. One instance of episodic transport driven by a synoptic scale pressure gradient reversal is discussed wherein there was minimal mixing and broadening of the pollution front during transit. The particulate loading within the polluted air parcel was found to be vertically homogeneous suggesting that it did not originate from subsidence of an elevated pollution layer. The relationship between this event and the ‘climatological’ data presented by White et al. (1991, Conf. Proc. Tropospheric Ozone and the Environment) is discussed with particular regard to the atypically short transport time.     

The sources and size distributions of aliphatic and carbonyl carbon in Los Angeles aerosol

Size distributions of aerosol phase aliphatic and carbonyl groups were measured during the Southern California Air Quality Study. Samples were collected using a low pressure impactor equipped with ZnSe disks and the aerosol samples were analyzed directly using infrared (i.r.) spectroscopy. For the carbonyl absorbance, the ambient samples showed maxima in the 0.12–0.26 μm and the 0.5–1.0 μm size fractions. For the aliphatic carbon absorbance, the ambient samples generally showed maxima in the 0.076–0.12 μm size fraction. Factors contributing to these two absorbances were examined using principal component analysis. The results indicate that the carbonyl absorbance can be almost entirely attributed to products of atmospheric reactions and the aliphatic absorbances in particles smaller than 0.12 μm is correlated with automotive emissions.     

Hydrocarbon emissions from twelve urban shade trees of the Los Angeles,California, Air Basin

The large-scale planting of shade trees in urban areas to counteract heat-island effects and to minimize energy use is currently being discussed. Among the costs to be considered in a cost/benefit analysis of such a program is the potential for additional reactive organic compounds in the atmosphere due to emissions from these trees. In this program, 15 species of potential shade trees for the Los Angeles Air Basin were studied and emission rates were determined for 11 of these trees, with one further tree (Crape myrtle) exhibiting no detectable emissions. The emission rates normalized to dry leaf weight and corrected to 30°C were (in μg g⁻¹ h⁻¹), ranked from lowest to highest emission rate: Crape myrtle, none detected; Camphor, 0.03; Aleppo pine, 0.15; Deodar cedar, 0.29; Italian Stone pine, 0.42; Monterey pine, 0.90; Brazilian pepper, 1.3; Canary Island pine, 1.7; Ginkgo, 3.0; California pepper, 3.7; Liquidambar, 37; Carrotwood, 49. In addition to the emission rates per unit biomass, the biomass per tree must be factored into any assessment of the relative merits of the various trees, since some trees have higher biomass constants than others. The present data shows that there are large differences in emission rates among different tree species and this should be factored into decision-making as to which shade trees to plant. Based solely on the presently determined emission rates, the Crape myrtle and Camphor tree are good choices for large-scale planting, while the Carrotwood tree and Liquidambar are poor choices due to their high isoprene emission rates.     

Measurement of atmospheric elemental carbon: Real-time data for Los Angeles during summer 1987

Two fundamentally different techniques for measuring atmospheric elemental carbon (EC) aerosol were compared to validate the methods. One technique, photoacoustic spectroscopy, was used to measure the optical absorption (λ = 514.5 nm) of in situ atmospheric aerosol in real time. This optical absorption can be converted to EC concentration using the appropriate value of the absorption cross-section for C, so that a comparison could be made with the second technique, thermal-optical analysis of filter-collected samples, which measures the collected EC by combustion. Solvent extraction of the filter samples prior to the thermal analysis procedure was required to minimize errors due to pyrolysis of organic carbon. Excellent 1:1 correlation of atmospheric EC concentrations resulted for measurements by the photoacoustic method vs the thermal method over coincident sampling times. The linear regression gave y = 1.006 (±0.056) x+0.27 (±0.56) with r = 0.945 (n = 41), where y is the photoacoustic EC concentration and x is the thermal elemental carbon concentration, both in μg m⁻³. This data set was collected in Los Angeles as part of the Southern California Air Quality Study (SCAQS) during the summer 1987, and supplements the results of an earlier, more limited data set taken in Dearborn, MI. The diurnal variability of EC aerosol in Los Angeles during SCAQS, as determined by photoacoustic spectroscopy, is discussed.     

A captive-air irradiation study of the response of nitric acid and peroxyacetyl nitrate to ozone control strategies in Los Angeles

Outdoor smog chamber experiments were used to study the sensitivity of the yields of two important nitrogen-containing pollutants, nitric acid (HNO₃) and peroxyacetyl nitrate (PAN) to changes in nonmethane hydrocarbon (HC) and nitrogen oxide (NO_x) concentrations in Los Angeles. The experiments were conducted at two sites in the Los Angeles Basin using eight chambers filled with morning Los Angeles air on 33 days. At least one chamber was unchanged and served as a control, while the initial HC and/or NO_x concentrations were changed by 25–50% in up to seven chambers to simulate O₃ control strategies and to broaden the range of HC - NO_x conditions studied. Empirical models that predict the maximum yields of HNO₃ and PAN were used to determine the response of these pollutants to three possible ozone control strategies. All three strategies (reductions in HC, NO_x or both HC and NO_x) reduced PAN while only NO_x reductions decreased HNO₃. However, reducing NO_x increased the HC reductions required to attain lower O₃ levels. Thus, there is a conflict between the O₃ and HNO₃ control strategies.     

Parameterization of episodical cloud and rainout events in large-scale atmospheric chemistry models

A parameterization scheme taking into account the episodical nature of rainout and incloud chemical transformation has been tested in a 2-D channel model. In the liquid phase many soluble gases are observed in concentrations never experienced in the gas phase. The effects on the trace gases SO₂ and hydrogen peroxide, when they are modified by clouds and precipitation, are studied. When incloud interaction of SO₂ and hydrogen peroxide is taken into consideration, calculated hydrogen peroxide profiles are brought closer to observed distributions. The effect of varying the time periods between cloud and rain events is tested. The impact on the formation and destruction of tropospheric ozone is also discussed.     

东北吉林地区云水化学航测研究

利用飞机航测于2007年夏季在东北吉林地区采集了24个云水样品,对云水的pH值与主要无机水溶性离子成分进行分析.结果表明,该地区云水呈酸性,平均pH值为4.93;主要离子成分依次为SO42- 109.7 meq/L, NH4+ 74.8 meq/L, Ca2+ 71.9 meq/L,和NO3- 51.4 meq/L; SO42-/NO3-的当量比为2.1,与龙凤山降水样品比值相当.云水离子浓度主要受天气形势及气团输送特征影响.集合后推气流轨迹分析表明离子浓度最高的云水样品主要受到华北地区污染输送的影响.对比同步采集的高空云水与地面降水样品,发现云下冲刷过程可对降水酸度起到一定的中和作用.     

Response of ozone to changes in hydrocarbon and nitrogen oxide concentrations in outdoor smog chambers filled with Los Angeles air

During the summer portion of the 1987 Southern California Air Quality Study (SCAQS), outdoor smog chamber experiments were performed on Los Angeles air to determine the response of maximum ozone levels, O₃(max), to changes in the initial concentrations of hydrocarbons, HC, and nitrogen oxides, NO_x. These captive-air experiments were conducted in downtown Los Angeles and in the downwind suburb of Claremont. Typically, eight chambers were filled with LA air in the morning. In some chambers the initial HC and/or NO_x concentrations were changed by 25% to 50% by adding various combinations of a mixture of HC, clean air, or NO_x. The O₃ concentration in each chamber was monitored throughout the day to determine O₃(max).An empirical mathematical model for O₃(max) was developed from regression fits to the initial HC and NO_x concentrations and to the average daily temperature at both sites. This is the first time that a mathematical expression for the O₃-precursor relationship and the positive effect of temperature on O₃(max) have been quantified using captive-air experiments. An ozone isopleth diagram prepared from the empirical model was qualitatively similar to those prepared from photochemical mechanisms. This constitutes the first solely empirical corroboration of the O₃ contour shape for Los Angeles.To comply with the Federal Ozone Standard in LA, O₃(max) must be reduced by approximately 50%. Several strategies for reducing O₃(max) by 50% were evaluated using the empirical model. For the average initial conditions that we measured in LA, the most efficient strategy is one that reduces HC by 55–75%, depending on the ambient HC/NO_x ratio. Any accompanying reduction in NO_x would be counter-productive to the benefits of HC reductions. In fact, reducing HC and NO_x simultaneously requires larger percentage reductions for both than the reduction required when HC alone is reduced. The HC-reduction strategy is the most efficient on average, but no single strategy is the optimum every day.     

脱硫剂颗粒增湿活化过程的数学模拟

建立了活化器中吸着剂颗粒活化效率的一维预测模型,全面考察了水雾蒸发,减速,粒径分布以及液－液凝并等的影响。通过对颗粒活化效率与实测脱硫效率的相关性分析,证实了活化颗粒的溶液反应是脱硫过程的主要机理,计算结果表明,人滴初始直径和初速度对颗粒活化效率有很大的影响,使用大粒径,窄分布和高初速度的雾化方式可强化增湿活化效果。     

Measurements of H2O2, aldehydes and organic acids in Los Angeles rainwater: Their sources and deposition rates

Rainwater samples were collected in Los Angeles, during 1985–1991 to determine concentration levels, sources and deposition rates of atmospheric H₂O₂, aldehydes and organic acids, in addition to major cations, anions and pH. Volume-weighted mean concentrations of H₂O₂, aldehydes (formaldehyde + acetaldehyde + glyoxal + methylglyoxal) and organic acids (formic acid + acetic acid) in rain collected at Westwood were 4.4., 3.9 and 16.5 μM, respectively, during the 6-year study period. Monocarboxylic organic acids were estimated to account for 27% (2–80%) of total free acidity (as on overall average) in rain collected at Westwood, whereas sulfuric acid and nitric acid accounted for 39% and 34% of the total acidity, respectively. Concentrations of aldehydes were strongly dependent on precipitation volume and decreased with increasing precipitation volume, whereas H₂O₂ and organic acids were only weakly dependent on precipitation volume. These results indicate that concentrations of aldehydes in rain are mainly controlled by dilution, whereas H₂O₂ and organic acid concentrations are controlled by other factors, such as decomposition of H₂O₂ by reacting with S(IV) and continuous aqueous formation/decomposition of organic acids by reactions involving aldehydes, dissolved OH radicals and H₂O₂. Principal component analyses indicate that aldehydes in rainwater mainly originate from gases and aerosols derived from anthropogenic sources, whereas the sources of H₂O₂ and organic acids in rain do not correlate with anthropogenic sources or marine and continental sources. There is good agreement between reported gas-phase concentrations of H₂O₂, aldehydes and organic acids in Los Angeles and calculated equilibrium concentrations of these chemical species from their rainwater concentrations and Henry's law constants. Temporal variations of concentrations of chemical species indicate that H₂O₂, aldehydes and organic acids were highest in the early afternoon. Summer rains contained the highest concentration of these chemical species, suggesting the photochemical activities during rain storms significantly affect their concentration levels. Estimation of annual rate of wet and dry depositions of H₂O₂, aldehydes and organic acids for the period studied, indicates that 84% of H₂O₂, 97% of aldehydes and 94% of organic acids, respectively, are annually scavenged from the atmosphere, by dry deposition, which is the dominant process for removal of these atmospheric pollutants in Los Angeles.     

西藏拉萨河流域巴嘎雪湿地水化学特征

以西藏拉萨河流域主要天然湿地之一的巴嘎雪湿地作为研究对象,对该湿地水体的pH值、水温、溶解氧(DO)、色度、浊度和15种金属元素的含量进行了分析检测.结果表明,巴嘎雪湿地水的pH、DO平均值分别为7.68、7.01mg/L;湿地水中15种金属元素含量均较低,汞、锡两种金属元素未能检出,其他13种金属元素的含量顺序为:Fe >Cr> V>Ni> Mn> As> Sb> Mo> Pb> Zn> Cu >Co> Cd,并均达到了国家《地表水环境质量标准》(GB3838-2002)Ⅰ类水质标准.通过比较湿地进水和出水水质的发现,巴嘎雪湿地对色度、浊度和部分金属元素的去除效果显著.对色度、浊度的去除率分别达到了51.73%、94.8%,对不同金属元素的去除效果不同,Cu、Pb、Zn、Mo、As、V的去除率分别为64.2%、36.9%、40.7%,28.2%、31.9%、67%.     

管式反应器石灰雾液脱硫的数学模拟

建立的一维管式反应器雾液脱硫模型是对蒸发和吸收过程的耦合，以膜理论为基础的吸收机理同时考虑了含硫组分的离解、扩散、反应和固体颗粒的溶解。参数敏感性分析表明，对系统脱硫率影响最显的是出口干湿球温差，石灰颗粒粒度和入口ＳＯ２浓度、传质过程的分析表明，反应开始阶段液膜扩散和固体溶解阻力均存在，而气膜扩散在整个反应过程中都起着重要作用。     

C/N比调控污泥厌氧发酵产酸的数学模型研究

采用改进粒子群算法对ADM1模型中的关键参数进行了估计,经敏感性分析,确定了Monod最大比吸收速率、半饱和值、产物对底物的产率等3种参数对产酸速率具有较大影响.应用修正后的动力学参数对ADM1模型在不同C/N比调控下污泥厌氧发酵产酸结果进行了模拟.结果表明,模拟产酸数据和实测数据误差较小,说明修正后的ADM1模型能够很好地描述污泥厌氧发酵中C/N比条件对产酸的影响.