Evaluation of an explicit NOx chemistry method in AERMOD

An explicit NO_x chemistry method has been implemented in AERMOD version 15181, ADMSM. The scheme has been evaluated by comparison with the methodologies currently recommended by the U.S. EPA for Tier 3 NO₂ calculations, that is, OLM and PVMRM2. Four data sets have been used for NO₂ chemistry method evaluation. Overall, ADMSM-modeled NO₂ concentrations show the most consistency with the AERMOD calculations of NO_x and the highest Index of Agreement; they are also on average lower than those of both OLM and PVMRM2. OLM shows little consistency with modeled NO_x concentrations and markedly overpredicts NO₂. PVMRM2 shows performance closer to that of ADMSM than OLM; however, its behavior is inconsistent with modeled NO_x in some cases and it has less good statistics for NO₂. The trend in model performance can be explained by examining the features particular to each chemistry method: OLM can be considered as a screening model as it calculates the upper bound of conversion from NO to NO₂ possible with the background O₃ concentration; PVMRM2 includes a much-improved estimate of in-plume O₃ but is otherwise similar to OLM, assuming instantaneous reaction of NO with O₃; and ADMSM allows for the rate of this reaction and also the photolysis of NO₂. Evaluation with additional data sets is needed to further clarify the relative performance of ADMSM and PVMRM2.

Implications: Extensive evaluation of the current AERMOD Tier 3 chemistry methods OLM and PVMRM2, alongside a new scheme that explicitly calculates the oxidation of NO by O₃ and the reverse photolytic reaction, shows that OLM consistently overpredicts NO₂ concentrations. PVMRM2 performs well in general, but there are some cases where this method overpredicts NO₂. The new explicit NO_x chemistry scheme, ADMSM, predicts NO₂ concentrations that are more consistent with both the modeled NO_x concentrations and the observations.     

Photo-oxidant chemistry in the polluted boundary layer under changing UV-B radiation

UV-B radiation is a driving factor for the chemistry of the polluted boundary layer. It is involved in the formation of radicals and consequently influences the formation and concentration of photo-oxidants. The 3-D mesoscale photochemical Metphomod model was employed to study the effect of changes in UV-B radiation on the concentration of photo-oxidants in the boundary layer over the Swiss Plateau. The model chemistry is based on the RACM mechanism and a two-stream approximation of radiative transfer. A summer (July) and a late winter (February) episode were simulated. All simulations were replicated with relatively large changes in the prescribed total ozone. The results for an increase in UV-B radiation show increases in PAN, HNO₃, and ozone at noon in NO_x-rich areas and a decrease in NO_x. In NO_x-poor areas in summer the effect on ozone is weak and has a negative sign, the main effect being an increase in H₂O₂. The spatial variability of NO_x concentrations in the Swiss Plateau in the summer case is such that the effect of increased UV-B radiation on ozone is spatially variable. The effect on the ozone production rate in summer is strongest positive at the surface in the NO_x-rich regions in the morning and strongest negative at some altitude above ground in NO_x-poor regions in the early afternoon. In the winter episode, NO_x-rich conditions are found almost everywhere on the Swiss Plateau, the effect of increased UV-B radiation on the ozone production rate is positive all day long and is largest at 300 m above ground at noon. In this case, in contrast to the summer case, the increase in ozone is carried over to the next day. The model results for ozone are in good agreement with results from a case study and a time series analysis of surface ozone measurements. We estimate the effect of day-to-day changes in total ozone on surface ozone peaks to range from 4 to 6 ppb at most.     

SMOG chamber studies of NOx chemistry in power plant plumes

Smog chamber simulations have been conducted in a 17m³ irradiation chamber with the purpose of identifying the effects of five independent variables on the transformation rates and product distributions of nitrogen and sulfur species in dilute power plant plumes. The study was designed to simulate the conditions in a plume starting at the point where half the NO has been oxidized to NO₂, where the plume will have been extensively diluted with background air containing hydrocarbons and ozone. The variables studied include: (1) plume hydrocarbon/NO_x ratio; (2) composition of organics in the diluting air; (3) NO_x/SO₂ ratio; (4) relative humidity; (5) presence of pre-existing acid sulfate aerosol. The starting concentrations and ratios of plume constituents were based on actual plume data.The results of the study are presented in terms of the impact of the independent variables on the extent of NO_x conversion to products, the rate of NO_x and SO₂ transformation to products and the relative distribution of gaseous and aerosol nitrate products. Briefly, the NO_x transformation rate is found to be dependent on hydrocarbon composition, hydrocarbon/NO_x ratio and relative humidity. The rates are essentially independent of SO₂ concentration or the presence of pre-existing H₂SO₄ aerosol surface. The SO₂ transformation rate appears to be independent of all five independent variables. The distribution of the nitrate products, nitric acid, peroxyacetyl nitrate and paniculate nitrate is a function of HC composition, HC/NO_x ratio and irradiation time. The effects of HC composition and HC/NO_x ratio decrease at the longer irradiation times characteristic of transport conditions.     

The relation between ozone,NOx and hydrocarbons in urban and polluted rural environments

Research over the past ten years has created a more detailed and coherent view of the relation between O₃ and its major anthropogenic precursors, volatile organic compounds (VOC) and oxides of nitrogen (NO_x). This article presents a review of insights derived from photochemical models and field measurements. The ozone–precursor relationship can be understood in terms of a fundamental split into a NO_x-senstive and VOC-sensitive (or NO_x-saturated) chemical regimes. These regimes are associated with the chemistry of odd hydrogen radicals and appear in different forms in studies of urbanized regions, power plant plumes and the remote troposphere. Factors that affect the split into NO_x-sensitive and VOC-sensitive chemistry include: VOC/NO_x ratios, VOC reactivity, biogenic hydrocarbons, photochemical aging, and rates of meteorological dispersion. Analyses of ozone–NO_x–VOC sensitivity from 3D photochemical models show a consistent pattern, but predictions for the impact of reduced NO_x and VOC in indivdual locations are often very uncertain. This uncertainty can be identified by comparing predictions from different model scenarios that reflect uncertainties in meteorology, anthropogenic and biogenic emissions. Several observation-based approaches have been proposed that seek to evaluate ozone–NO_x–VOC sensitivity directly from ambient measurements (including ambient VOC, reactive nitrogen, and peroxides). Observation-based approaches have also been used to evaluate emission rates, ozone production efficiency, and removal rates of chemically active species. Use of these methods in combination with models can significantly reduce the uncertainty associated with model predictions.     

Heterogeneous mercury reaction chemistry on activated carbon

Experimental and theory-based investigations have been carried out on the oxidation and adsorption mechanism of mercury (Hg) on brominated activated carbon (AC). Air containing parts per billion concentrations of Hg was passed over a packed-bed reactor with varying sorbent materials at 140 and 30 degrees C. Through X-ray photoelectron spectroscopy surface characterization studies it was found that Hg adsorption is primarily associated with bromine (Br) on the surface, but that it may be possible for surface-bound oxygen (O) to play a role in determining the stability of adsorbed Hg. In addition to surface characterization experiments, the interaction of Hg with brominated AC was studied using plane-wave density functional theory. Various configurations of hydrogen, O, Br, and Hg on the zigzag edge sites of graphene were investigated, and although Hg-Br complexes were found to be stable on the surface, the most stable configurations found were those with Hg adjacent to O. The Hg-carbon (C) bond length ranged from 2.26 to 2.34 A and is approximately 0.1 A shorter when O is a nearest-neighbor atom rather than a next-nearest neighbor, resulting in increased stability of the given configuration and overall tighter Hg-C binding. Through a density of states analysis, Hg was found to gain electron density in the six p-states after adsorption and was found to donate electron density from the five s-states, thereby leading to an oxidized surface-bound Hg complex.     

Throughfall chemistry and canopy interactions in a Sitka spruce plantation sprayed with six different simulated polluted mist treatments

Throughfall chemistry was studied in a mature Sitka spruce plantation in order to investigate canopy interactions, such as nitrogen absorption, cation leaching, and neutralization of rainfall passing through the canopy. The plantation had been exposed to six different simulated mist treatments including N (NH(4)NO(3)) and S (H(2)SO(4) at pH 2.5) in four replicated blocks since 1996. Throughfall and rainfall were collected from May to September 2000. The results showed that 30-35% of the applied N was retained by the canopy. There were linear relationships between the loss of H(+) and increased K(+), Mg(2+) and Ca(2+) deposition through the canopy. However these increases in K(+), Mg(2+) and Ca(2+) deposition accounted for only about 50% of total neutralization of the acidity. The relationship between the anion deficits in throughfall and the loss of H(+) implied that weak organic acid anions were involved in the neutralization of the acidity in throughfall.     

Modelling future soil chemistry at a highly polluted forest site at Istebna in Southern Poland using the "SAFE" model

The multi-layer dynamic model SAFE was applied to the forested catchment Istebna (Southern Poland), to study recovery from acidification. Environmental pollution in the area has been historically high. The model uses data from an intensive monitoring plot established in 1999 in a spruce stand, which was planted in 1880. Observations showed that the soil was depleted of base cations. The measured base saturation in 1999 was between 5 and 8% in the different soil layers. Model predictions assuming full implementation of the UNECE 1999 Gothenburg Protocol and present day base cation deposition show that the base saturation will slowly increase to 20% by 2100. Despite large emission reductions, Istebna still suffers from the very high loads of acidifying input during the past decades. Soil recovery depends on future emissions especially on base cation deposition. The recovery will be even slower if the base cation deposition decreases further.     

我国氮氧化物排放因子的修正和排放量计算:2000年

根据我国城市的发展状况 ,采用城市分类的方法 ,将我国 2 6 1个地级市按照人口数量分为 5个类别。每类城市选取一个典型城市进行实地调查 ,对我国燃烧锅炉和机动车的NOx 的排放因子进行了修正 ,提出了适合我国目前排放水平的各类城市的固定源和移动源的排放因子。并依据 2 0 0 0年中国大陆地区的电站锅炉、工业锅炉和民用炉具的燃料消耗量和机动车保有量 ,以地级市为基本单位 ,估算了 2 0 0 0年我国各地区的NOx 排放量 ,分析了分地区、分行业、分燃料类型的NOx 排放特征。 2 0 0 0年我国NOx 排放总量为 11.12Mt,其中固定源占 6 0 .8% ;移动源占 39.2 %。NOx 排放在地域、行业和燃料类型上分布均不平衡。NOx 的排放主要集中在华东和华北地区 ,其排放量占全国排放量的一半以上。燃煤为最重要的NOx 排放源 ,其排放量占燃料型NOx 排放量的 72 .3%左右。     

污染水体的生物修复技术研究进展

详细介绍了污染水体生物修复技术的特点 ,综述了近年来国内外水体生物修复技术的研究和应用现状 ,并评述了水体生物修复技术存在的问题以及污染水体生物修复的发展方向     

Simulation of the chemical processes in a polluted irradiated atmosphere

An atmospheric chemistry model has been approximated with a system of linear differential equations for the most relevant chemical species, and the results have been compared with the original model. Formulas for the sensitivity (and apportionment) analyses are given. The computation time is greatly reduced.     

Measurements of aromatic hydrocarbon ratios and NOx concentrations in the rural troposphere: Observation of air mass photochemical aging and NOx removal

Measurements of the aromatic hydrocarbons (benzene, toluene, ethylbenzene and ortho(o)-xylene) at Niwot Ridge, Colorado have shown distinct correlations between the ratios of the concentrations of these compounds and the degree of direct urban influence. The major atmospheric removal mechanism of aromatic hydrocarbons is reaction with the hydroxyl radical, OH. This allows the decrease in the ratios of aromatic hydrocarbon concentrations to be related to the transport time and average OH number density within an air mass, if assumptions are made concerning background sources of aromatic hydrocarbons. Measured ratios of aromatic compounds at this site, along with ratios reported for several cities in the western United States, and estimates of transport times from these cities were used to calculate temporally and spatially averaged OH number densities. Hydroxyl radical number density estimates using toluene-, ethylbenzene-, and o-xylene-to-benzene ratios, were 1.2 ± 0.6 × 10⁶, 1.0 ±0.8 × 10₆ and 0.48 ± 0.8 × 10⁶ molecules cm⁻³, respectively. Considering the uncertainties in the assumptions used in the above estimates, we obtain a diurnal-average upper limit of 2.4 × 10⁶ molecules cm⁻³. The correlations between measured ratios are found to yield slopes consistent with those predicted by experimental OH rate constants for benzene, toluene and ethylbenzene, and approximately a factor of two different in the case of benzene, toluene and o-xylene. The ratio of NO_x: benzene was found to yield no correlation with toluene: benzene ratio for periods of westerly flow, but was well correlated with toluene: benzene ratio during periods of direct urban impact on the site (upslope easterly winds). The correlation of these ratios in urban plume air masses was consistent with NO₂ + OH + M being the major daytime removal mechanism of NO_x in the summertime.     

生物修复剂在清除海滩石油污染中的应用

介绍了生物修复石油污染海滩时常用的修复剂类型及其特点.当实验室环境条件能较好控制时,生物强化剂一般是有效的;然而污染现场得出的证据不能表明其对生物降解有促进作用.实验室和现场的研究均表明营养型生物促进剂能有效促进石油的生物降解.水溶性营养易被波浪和潮汐冲刷掉;缓释型营养盐面临的主要挑战是如何控制其释放速率,以保证孔隙水中能较长时间维持理想的营养浓度;亲油型肥料中含有有机碳,有可能在微生物降解石油之前被优先降解.建议根据污染环境的特点选用适合的生物促进剂.     

Heterogeneous SO2-oxidation in the droplet phase

In order to determine the rate controlling step for sulfate formation in a heterogeneous droplet system. SO₂-transfer within the gasphase towards and within droplets are calculated, equilibrium between SO₂ in the gasphase and sulfur (IV) in cloud and fog droplets is reached within less than 1 second. Oxidation of sulfur (IV) to sulfate in the droplet phase proceeds slower by orders of magnitutde. Three mechanisms of SO₂-oxidation are discussed:

• 1.(a) SO₂-oxidation by O₂ in the absence of catalysts;
• 2.(b) SO₂-oxidation by O₂ in the presence of catalysts and
• 3.(c) SO₂-oxidation by strongly oxidizing agents.

Mechanism

• 1.(a) contributes only to a negligible extent to sulfate formation in droplets even in the presence of typical concentrations of ammonia. Indications are strong that the major function of the SO₂-NH₃-H₂O-system is not the oxidation of SO₂ to sulfate. Oxidation mechanism (b) may contribute to a significant extent to sulfate formation in urban fogs in which case the concentrations of catalysts can be sufficiently high. For clouds in remote areas with much lower catalyst concentrations SO₂-oxidation by mechanism
• 2.(b) seems to be of little importance. The oxidation by strongly oxidizing agents (mechanism
• 3.(c)) appears to be the dominant mechanism although some experimental discrepancies have to be resolved.

     

Speculations on the movement of polluted air to the Arctic

Using arguments based on the idea that the motion of air parcels is adiabatic except for an adjustment for diabatic (radiational) cooling, we are led to the hypothesis that the arctic aerosol comes from regions north of the polar front, primarily over the Eurasian Continent during wintertime.     

机动车尾气中氮氧化物的分析检测技术

为了分析机动车尾气氮氧化物净化催化剂的催化性能 ,建立了一套尾气模拟评价体系 ,分别使用电化学法、化学发光法和比色法 3种氮氧化物分析手段进行检测。结果表明 ,3种方法都能在一定精度范围内测量机动车尾气中的氮氧化物 ,化学发光法测量精度高 ,响应时间短 ,能够及时地反映发动机运转过程中的氮氧化物浓度变化情况 ,是一种较好的分析手段。电化学法随着使用时间推移 ,响应时间变长 ,灵敏度降低 ,需要及时更换传感器。比色法通过化学吸收可以测定氮氧化物的浓度 ,不能实现连续在线分析 ,只能采样测量。在分析中 ,还尝试利用一些辅助设备 ,将尾气中的NO和NO2转化后再通入测量仪器 ,实现测量总氮氧化物或其中某一气体的功能     

Modelling the spatial distribution of SO2 and NOx emissions in Ireland

The spatial distributions of sulphur dioxide (SO2) and nitrogen oxides (NOx) emissions are essential inputs to models of atmospheric transport and deposition. Information of this type is required for international negotiations on emission reduction through the critical load approach. High-resolution emission maps for the Republic of Ireland have been created using emission totals and a geographical information system, supported by surrogate statistics and landcover information. Data have been subsequently allocated to the EMEP 50 x 50-km grid, used in long-range transport models for the investigation of transboundary air pollution. Approximately two-thirds of SO2 emissions in Ireland emanate from two grid-squares. Over 50% of total SO2 emissions originate from one grid-square in the west of Ireland, where the largest point sources of SO2 are located. Approximately 15% of the total SO2 emissions originate from the grid-square containing Dublin. SO2 emission densities for the remaining areas are very low, < 1 t km-2 year-1 for most grid-squares. NOx emissions show a very similar distribution pattern. However, NOx emissions are more evenly spread over the country, as about 40% of total NOx emissions originate from road transport.     

DDT polluted meltwater affects reproduction in the mussel Dreissena polymorpha

The zebra mussel Dreissena polymorpha was used to follow the recently reported DDT pollution of Lake Iseo (N. Italy). Histopathological analyses were performed on mussels sampled from March 2005 to April 2006, when high DDT levels were found, and results were compared to those from mussels sampled in 2001/2002, before the pollution event. During the 2005/2006 reproductive season, the first male gamete release happened one month later than the onset of spawning in females who showed a high number of specimens with degenerating oocytes, despite a regular pattern of gametogenesis. These results indicated a disrupting action of DDT on the mechanisms involved in sperm release, and a disturbance in the gametogenic phases of the ovary. Pathological pictures in the digestive gland of many mussels from both 2001/2002 and 2005/2006 have also been observed, but DDT pollution is unable to explain the presence of pathological fields in mussels during 2001/2002, for which a previously reported contamination seems to be the main cause. A possible role of DDT in skewing the sex ratio towards a predominance of females was also discussed, considering the high number of females sampled in 2005/2006.     

渗滤液污染包气带中铁的形态变化

从渗滤液场龄和包气带岩性两方面出发,研究了新、老渗滤液对亚粘土和细砂包气带环境中Fe的含量及存在形态的影响。结果表明：新、老渗滤液分别能使细砂包气带介质中除残渣态以外Fe的含量增加16.68%或降低13.82%。亚粘土比细砂作为包气带介质更能缓冲渗滤液对介质中Fe的影响程度,其受影响范围在包气带0～20 cm深度处。当亚粘土为介质的包气带被新渗滤液污染后,其表层介质中碳酸盐结合态Fe的含量会增加15倍之多,为缓冲渗滤液Fe的污染做出了巨大贡献,但这部分Fe的存在也是潜在的二次污染源,在环境pH急剧变化的情况下,它可能会引起地下水高铁污染。