Southern California air quality study: Peroxyacetyl nitrate

Information on the spatial and seasonal variations of ambient peroxyacetyl nitrate (PAN) has been obtained from simulataneous measurements made at five, seven or nine Southern California locations in June-September and November-December, 1987. Summertime (smog season) levels of PAN were consistent with photochemical formation during transport, and increased substantially from coastal to inland locations. Daily maxima (up to 30 ppb) coincided with those of ozone at all locations and shifted from midday at coastal sites to late afternoon inland.Elevated levels of PAN, e.g. up to 19 ppb on 3 December 1987, were observed during the fall at all coastal and central locations, where they consistently exceeded summertime levels.     

Formic acid and acetic acid in the western Sierra Nevada,California

This paper reports the results of measurements of formic and acetic acid at four sites located along the western slope of the Sierra Nevada and compares the results with those of earlier studies. Formic acid concentrations ranged from approximately 1 to 40 ppb; those of acetic acid ranged from approximately 0.5 to 13 ppb. Mean formic acid concentrations were 18 ppb at Tehachapi, located at the southern extremity of the range, and between 12 and 13 ppb at the three other sites. Mean acetic acid concentrations ranged from 3.9 ppb at Blodgett Experimental Forest, located at the northern extremity, to 8.0 ppb at Yosemite. Comparison with previous studies indicates that carboxylic acid levels measured in the Sierra Nevada are higher than those measured in past studies, and in many cases average concentrations of both formic and acetic acids observed during this study were greater than the previously reported maxima. Comparisons were also made to nitric acid concentrations measured at Yosemite and Giant Forest from October 1986 to September 1987. At Yosemite, annual nitric acid concentrations averaged 0.20 ppb during the day, and 0.06 ppb at night; and at Giant Forest, nitric acid averaged 0.17 ppb during the day, and 0.05 ppb at night. Thus, the high formic and acetic acid concentrations observed in this study suggest that carboxylic acid are major contributors to the overall flux of ambient acid deposition in the western Sierra Nevada.     

Formic acid and acetic acid: Emissions,atmospheric formation and dry deposition at two southern California locations

Emission rates, in situ formation rates and removal rates by dry deposition are estimated for formic acid (HCOOH, C1) and acetic acid (CH₃COOH, C2), which are the most abundant acids in southern California air and together account for much of the airborne acidity and are the leading contributors to acid dry deposition. Using data for eight unreactive tracers, direct emission rates during the fall 1987 are estimated to be 5.6 and 12.8 metric tons d⁻¹ for C1 and C2, respectively, at a coastal source-dominated site. These emissions rates increase to 9.6(C1) and 20.4(C2) metric tons d⁻¹ during the summer. In situ formation in the atmosphere via the ozone-olefin reaction is an important source for both acids. This reaction produces an estimated 25.0 and 10.1 metric tons d⁻¹ of C1 and C2, respectively, during the day and 34.5 (C1) and 4.3 (C2) metric tons d⁻¹ at night. More acetic acid than formic acid is emitted by direct sources, with C2/C1 emission rate ratios of 2.1–2.3. The reverse is true of in situ formation, with C1/C2 production rate ratios of 2.5 (day) and 8.0 (night). Dry deposition removal rates depend on season (fall > summer) and location (inland > coastal) and are 22–52 metric tons d⁻¹ for C1, and 32–83 metric tons d⁻¹ for C2. Source (emissions + in situ formation) and sink (dry deposition) terms are of the same magnitude in all six cases studied and balance each other well in three of these cases. Uncertainties in emission, in situ production and removal rates are discussed and reflect uncertaintes in olefin and unreactive tracer emission rates, yields of organic acids from the Criegee biradical (ozone-olefin reaction), and dry deposition velocity, respectively.     

Hydrochloric acid: A regional perspective on concentrations and formation in the atmosphere of Southern California

Atmospheric gaseous hydrochloric acid (HCl) concentrations and water-soluble species in the aerosol phase were measured at nine sites in Southern California throughout the year 1986. Annual average HCl concentrations measured by the denuder difference method ranged from 0.39 ppb at an offshore island to 1.25 ppb onshore at Hawthorne, California. An ion balance on the aerosol shows that coarse particle chloride begins as sea salt over the ocean and is depleted relative to aerosol sodium with transport inland. Total chloride and sodium balances show that chloride depletion from the aerosol is matched by a comparable increase in gaseous HCl concentrations, consistent with the proposition that acid gas reactions with sea salt are the principal source of gaseous HCl in the Southern California atmosphere. Fine aerosol chloride exceeds fine particle sodium on a number of occasions, particularly at one inland site known for extraordinarily high NH₃ levels. There is evidence that coarse aerosol chloride from sea salt is being processed by atmospheric reactions through HCl to form fine aerosol, possibly NH₄Cl.     

天津不同气团来向PM2.5中组分和污染源贡献的季节变化

利用基于新型多点位三维受体模型和后轨迹所构建的来向解析技术（SDA）,探讨了天津市内陆和近海点位的不同季节不同来向气团载带的颗粒物浓度、组分和源分担率特征,并定量计算了不同来向污染源对受体点位的贡献大小.整体上,渤海来向的气团相对清洁（97.1μg/m³）,气团占比较大（23.7%）;内蒙-河北-北京-天津来向气团载带的PM_2.5浓度高（197μg/m³）,但气团占比小（内陆点位春冬季分别为12.5%,11.9%,近海点位春冬季分别为8.6%,10.7%）,对PM_2.5的综合影响较小.近海点位春夏秋冬季对PM_2.5分担率最大的污染源分别为：SSW来向地壳源（12.8%）、SE来向硫酸盐+SOC（二次有机碳）（9.8%）、WSW来向燃煤源（10.3%）、WNW来向硫酸盐+SOC（12.1%）.内陆点位分别为SSW来向地壳源（14.5%）、S来向硫酸盐+SOC（13.5%）、SSW来向机动车源（8.9%）、WNW来向硫酸盐+SOC（9.5%）.     

Developing chemical signatures of particulate air pollution in the Pearl River Delta region, China

PM2:5 samples were collected in a regional sampling network with three sites in Hong Kong and four sites in the adjacent inland Pearl River Delta (PRD) or Guangdong Province during four months/seasons from 2002–2003. Trans-boundary transport between Hong Kong and the inland PRD is inevitable under the influence of Asian monsoon. In summer, Hong Kong serves as the upwind site of the inland PRD while during other seasons it is under the influence of continental emissions. Previous studies have recognized the importance of using chemical signatures to differentiate local vs. regional contributions to air pollutants in Hong Kong such as the CO/NOx ratio, ratios of different VOC species. In this study, detailed chemical speciation by gas chromatography-mass spectrometry was performed with PM2:5 samples to identify new chemical signatures to distinguish aerosols in Hong Kong from those from the inland PRD. Since Hong Kong is not influenced by the continental emissions from the inland PRD during summer, comparison focused on chemical data obtained from this season for chemical signatures. The new ratios developed from the current study include LCPI/HCPI ratio of alkanes (0.39 0.02 in Hong Kong vs. 0.78 0.08 in the inland PRD), pyrene to benzo[ghi]perylene ratio (0.97 0.21 in Hong Kong compared to 0.20 0.06 in the inland PRD), and the ratio of 1,2-benzenedioic acid to 1,4-benzenedioic acid (1.8 0.1 in Hong Kong vs. 0.6 0.05 in the inland PRD). Results from this study also revealed that Hong Kong was impacted by ship emissions as reflected by substantially high V/Ni ratio (9 2) while this ratio was about 1–2 at all sites in the inland PRD, which is very close to typical ratios from residual oil combustion.     

Gas- and aqueous-phase formic and acetic acids at a tropical cloud forest site

Atmospheric gas-phase and aqueous-phase (dew and fog) formic and acetic acids were measured over a cloud forest in Venezuela. The gaseous acids showed diurnal cycles, with higher mixing ratios during daytime. Higher concentrations were observed during the dry season (HCOOH 1.7 +/−0.5 ppb; CH₃COOH 1.4+/−0.6 ppb) in comparison with the rainy season (HCOOH 0.79+/−0.24 ppb; CH₃COOH 0.54+/−0.20 ppb). Liquid-phase concentrations in dew and fog are of the same order and range from 8.1 to 69.5 μM for HCOOH and 4.3 to 15.3 μM for CH₃COOH. The field-observed Henry's Law coefficients, calculated from the simultaneous measurements of gas- and liquid-phase acids, do not show a significant trend with the pH of the solution, in contrast to theoretical considerations. Dry deposition velocities to the nighttime dew are 1.1+/−0.6 and 0.68+/−0.42 cm s⁻¹ for formic and acetic acids, respectively. A loss of 0.054 ppb HCOOH and 0.022 ppb CH₃COOH from the atmospheric boundary layer to the dew is produced nightly.     

The relationship between ozone and regional tracers in rural Rhode Island

Ozone and regional tracers are directly related at a rural Rhode Island site during summer. Unlike elemental tracers and sulfate, ozone has a significant background which appears to be unrelated to regional-pollution sources. Summer ozone concentrations were apportioned among northeastern and midwestern sources using results from regional-scale receptor modeling of pollution aerosol. The Northeast contributed roughly 40% more than the Midwest, but ‘background’ accounted for up to half of the average ozone concentration.     

Formic and acetic acid as agents for a cleaner fractionation of Miscanthus x giganteus

Miscanthus. x giganteus bark was subjected to acetic and formic acid fractionation. The kinetics of the process were explained by a model of two parallel first-order reactions, for pulp yield and delignification, and by Saeman's kinetics based models, for total polysaccharides and viscosity of pulps. The influence of hydrochloric acid concentration on both organosolv processes was studied at two levels: 0.10 and 0.15% by weight. The models provided a good fit of the experimental data and helped to predict the best set of independent variables to obtain a good fractionation.Both systems achieved similar delignification levels and pulp characteristics, although the evolution in formic acid was faster than in acetic acid, mainly due to the great extent of reactions in the warming up period that accounted for about a third part of the initial dry weight of the raw material.     

东苕溪鱼类生物完整性评价河流健康体系的构建与应用

以东苕溪流域为研究区域,建立基于鱼类生物完整性指数(IBI)的河流健康评价指标体系.采样点来自2个不同的生态区,共建立了2套不同的IBI评价指标体系和标准.上游支流样点均来自浙闽山地常绿阔叶林生态区,从而建立了东苕溪上游支流的IBI指标体系:即鱼类总物种数(M1)、平鳍鳅科鱼类物种数百分比(M5)、中国土著鱼类物种数百分比(M6)、Shannon-Wiener多样性指数(M7)、无脊椎动物食性鱼类个体百分比(M13)、植食性鱼类个体百分比(M14)、敏感性鱼类个体百分比(M1)7个参数指标.中下游样点均来自长江三角洲城镇及城郊农业生态区,建立了东苕溪中下游区域的IBI指标体系:即鱼类总物种数(M1)、虾虎鱼科鱼类物种数百分比(M4)、中国土著鱼类物种数百分比(M6)、Shannon-Wiener多样性指数(M7)、上层鱼类物种数百分比(M8)、中上层鱼类物种数百分比(M9)、植食性鱼类个体百分比(M14)、借助贝类产卵鱼类物种数百分比(M21)、鱼类总个体数(M22)、畸形、患病鱼类个体数百分比(M23)等10个参数指标.河流健康状态划分为5个健康等级:即“健康”、“一般”、“较差”、“极差”和“无鱼”.应用IBI指标体系评价东苕溪流域的45个观测点的河流健康状况,结果显示东苕溪流域绝大多数河段的健康状况处于“一般”和“较差”水平.2011年,东苕溪中下游河段的健康状态较2010年有所改善,然而上游支流的健康状态较2010年有所下降.     

黄磷尾气生产甲酸中尾气净化试验研究

通过综合研究试验筛选,研发专门适用以黄磷生产中外排废尾气为原料,匹配当今较先进的甲酸甲酯水解法(改进工艺)生产具有广泛用途和良好市场前景的环保型有机强酸———甲酸,完全满足优级甲酸生产的气体净化、提纯、提浓工艺技术,且安全可靠,经济合理。     

Ti-Ce系列催化剂上乙酸的催化湿式氧化反应

采用Ti-Ce系列湿式氧化催化剂,研究模型反应物乙酸在催化湿式氧化反应中的动力学影响因素以及反应过程产物.结果表明,乙酸的催化湿式氧化受到催化剂用量、反应温度、反应体系酸度以及氧分压的影响较大.当反应温度230℃,氧分压2～2.5MPa,催化剂量5g/L,反应液初始pH3.0时,反应1h后即可使乙酸浓度(以COD计)去除率在90%以上.通过离子色谱,检测了反应过程中的甲酸中间体,结果表明,催化剂的存在不仅加速了湿式氧化反应速率,而且也改变了反应历程.     

深圳大学城园区典型OVOCs污染特征与来源解析

采用质子转移反应质谱仪（PTR-MS）对深圳大学城园区2017年不同季节（分干湿两季）的6种典型OVOCs和其他非甲烷烃类（NMHCs）进行连续在线监测,分析其干湿季的浓度特征与日变化规律,并应用光化学龄的参数化方法开展OVOCs的来源解析.结果表明,在观测的6种OVOCs中,甲醇的平均浓度最高,达10×10^-9~12×10^-9,其次是乙酸、丙酮和乙醛,约2~5×10^-9,甲酸和丁酮的含量最低,仅1×10^-9~2×10^-9.通过日变化观察到的OVOCs湿季峰值浓度时间明显早于干季,乙醛表现出与臭氧（O₃）相似的日变化特征,揭示了其可能存在二次来源;甲醇和丁酮的峰值浓度时间均早于O₃,可能存在重要的一次排放源.采用光化学龄模型解析出日间污染物来源比例：在污染较重的干季,甲醇、乙醛、丙酮和丁酮的人为一次源占主导,甲酸和乙酸的二次源是主要贡献者;在较清洁的湿季,天然源成为乙醛、丙酮、丁酮、甲酸和乙酸的主要来源.     

珠江三角洲大气环境VOCs的时空分布特征

在珠江三角洲地区的 8个大气功能区观测点、5个主导风向加强观测点和 3个不同高度监测点进行了为期 1年以上的观测 ,采用美国环保局TO15方法定性并定量分析了 5 5种臭氧前体物 (NMHCs)和 6 2种有毒挥发性有机化合物 (ToxicVOCs) ,系统研究了该地区大气VOC的组成特征及其时空分布规律 .结果发现 ,各大气功能区VOC的浓度水平和组成特征差别明显 ,珠江三角洲大气VOCs呈现区域性污染特征 ;广州市区始终具有最高的VOC浓度水平 ,夏季、冬季其下风向地区的VOC浓度呈现出明显的空间变化规律 ;夏季的NMHC及单环芳香烃的浓度均为全年最高 ,VOC各组分表现出并不相同的日变化和季节变化特征 ;城市近地面VOC主要受机动车排放的影响 ,而越往高空 ,一次污染物去除与二次污染物的影响显得突出和显著     

海南省背景区域臭氧及其前体物污染特征

基于2019年五指山背景点、海口市和三亚市的环境空气自动监测数据和气象观测资料,分析了海南省背景区域和重点城市O₃及其前体物NO₂污染特征;结合挥发性有机物（VOCs）在线监测数据,分析了五指山背景点VOCs的时间变化规律、O₃浓度高值月份O₃及其前体物VOCs和NO_x的污染特征以及VOCs的臭氧生成潜势（OFP）.结果表明,O₃是影响五指山背景点空气质量的关键污染物,五指山背景点O₃日最大8 h浓度平均值与海口市和三亚市显著相关.背景点NO₂月均浓度水平显著低于城市点,然而背景点和城市点O₃月均浓度水平和变化趋势高度一致.背景点O₃变化与风向密切相关,春夏季偏南风频率较高,O₃浓度相对较低;秋冬季以东北风为主,易受内陆污染输送影响,O₃浓度较高.五指山背景点春夏季VOCs体积分数低于秋冬季,但对应的OFP高于秋冬季;其中异戊二烯夏季体积分数显著高于秋冬季,且其夏季体积分数占总挥发性有机物的比例最高,对应的OFP贡献率可达70%以上,O₃则表现出秋冬季显著高于夏季的特征.11月O₃高浓度时段乙炔和芳香烃的体积分数较清洁日出现较大上升,同时其对应的OFP显著上升.VOCs优势物种和OFP主要贡献物种的分析结果表明,O₃高浓度时段机动车尾气和油气挥发排放源对五指山背景点VOCs的化学组成和OFP有重要贡献.     

Characteristics and recent trends of sulfur dioxide at urban, rural, and background sites in North China: Effectiveness of control measures

SO₂ measurements made in recent years at sites in Beijing and its surrounding areas are performed to study the variations and trends of surface SO₂ at different types of sites in Northern China. The overall average concentrations of SO₂ are (16.8 ± 13.1) ppb, (14.8 ± 9.4) ppb, and (7.5 ± 4.0) ppb at China Meteorological Administration (CMA, Beijing urban area), Gucheng (GCH, relatively polluted rural area, 110 km to the southwest of Beijing urban area), and Shangdianzi (SDZ, clean background area, 100 km to the northeast of Beijing urban area), respectively. The SO₂ levels in winter (heating season) are 4-6 folds higher than those in summer. There are highly significant correlations among the daily means of SO₂ at different sites, indicating regional characteristics of SO₂ pollution. Diurnal patterns of surface SO₂ at all sites have a common feature with a daytime peak, which is probably caused by the downward mixing and/or the advection transport of SO₂-richer air over the North China Plain. The concentrations of SO₂ at CMA and GCH show highly significant downward trends (-4.4 ppb/yr for CMA and -2.4 ppb/yr for GCH), while a less significant trend (-0.3 ppb/yr) is identified in the data from SDZ, reflecting the character of SDZ as a regional atmospheric background site in North China. The SO₂ concentrations of all three sites show a significant decrease from period before to after the control measures for the 2008 Olympic Games, suggesting that the SO₂ pollution control has long-term effectiveness and benefits. In the post-Olympics period, the mean concentrations of SO₂ at CMA, GCH, and SDZ are (14.3 ± 11.0) ppb, (12.1 ± 7.7) ppb, and (7.5 ± 4.0) ppb, respectively, with reductions of 26%, 36%, and 13%, respectively, compared to the levels before. Detailed analysis shows that the differences of temperature, relative humidity, wind speed, and wind direction were not the dominant factors for the significant differences of SO₂ between the pre-Olympics and post-Olympics periods. By extracting the data being more representative of local or regional characteristics, a reduction of up to 40% for SO₂ in polluted areas and a reduction of 20% for regional SO₂ are obtained for the effect of control measures implemented for the Olympic Games.     

Atmospheric H2O2 field measurements in a tropical environment: Bahia,Brazil

Concentrations of H₂O₂ in atmospheric gas and liquid phases were determined for the first time in the tropical Southern Hemisphere. Measurements were carried out in the Salvador area, Bahia, 13°S, 38°W) both at the seaside and 500 m away from it as well as at 270 km inland, in a rural area, during March–April 1988. Gaseous H₂O₂ was collected by cryogenic and rain by wet only sampling. Analyses were performed with the peroxyoxalate chemiluminescence method, employing a compact field apparatus. The measured gas phase concentrations ranged from 0.2 to 3.9 ppbv compared to 0.01-0.6 ppbv obtained from measurements with similar methodology in Dortmund (51°30'N, 7°30'E), F.R.G, during summer. The corresponding concentration ranges in rainwater are 0.9-6.8 ppmw (Bahia) and 0.1–2.2 ppmw (Dortmund, summertime). Gas/liquid H₂O₂ equilibrium during rain events is only attained at precipitation rates below 1 mm h⁻¹.     

Intensive studies of Sierra Nevada cloudwater chemistry and its relationship to precursor aerosol and gas concentrations

Measurements of inorganic aerosol and gas phase species are presented for three sites in central California during a 4 day period in April 1988. The measurement sites were located along an east-west transect at Visalia, Ash Mountain, and Lower Kaweah, with elevations of 90, 550 and 1900 m, respectively. Aerosol compositions were nearly neutral at all locations, however large concentrations of NH₃ at Visalia contributed significant excess alkalinity to the air mass sampled there. Concentrations of all major species were observed to decrease with elevation during most of the sampling periods. Concentrations at the upper two sites exhibited diurnal fluctuations, with peaks in the late afternoon, consistent with the transport of pollutants from San Joaquin Valley sources by daytime upslope winds. Concentrations of most of these species reached a maximum at the elevated sites on 28 April, as a weak cold front approached, reducing the atmospheric stability over the valley floor. Concentrations at Visalia on this day were somewhat lower than those observed earlier in the week.Clouds intercepting the mountain slopes on 28 April were sampled at two locations. The coudwater pH at both sites was observed to fall throughout the event, dropping as low as 4.34. Precursor concentrations of aerosol NO₃⁻, SO₄^2- and NH₄⁺, and gas phase HNO₃ and NH₃, were sufficient to account for the observed cloudwater loadings of NO₃⁻, SO₄^2- and NH₄⁺. In-cloud measurements made near the cloud base indicated a considerable S(IV) oxidation potential in the form of H₂O₂, but only low S(IV) concentrations. Cloudwater concentrations of formic acid were approximately three times acetic acid concentrations. Carbonyl concentrations were dominated by formaldehyde and glyoxal.     

Nitrogenous air pollutants at a southern California mountain forest smog receptor site

Ambient levels of the nitrogenous pollutants NO, NO₂, nitric acid, nitrous acid, ammonia, particulate nitrate, particulate ammonium, peroxyacetyl nitrate (PAN) and peroxypropionyl nitrate (PPN) have been measured at a southern California mountain forest location severely impacted by urban photochemical smog. Air quality at the mountain forest location was characterized by high levels of nitric acid (up to 18 ppb) and the phytotoxic peroxyacyl nitrates PAN (up to 22 ppb) and PPN (up to 5 ppb). Alkyl nitrates were below our detection limits of 0.05–0.5 ppb. The (PAN + PPN)/NO₂ ratios varied substantially (range 0.03–2.27) and were generally large, with typical 24-h averages of 0.19–0.50. Diurnal variations of the (PAN/PPN)/NO₂ ratio exhibited both nighttime and daytime maxima reflecting diurnal variations in PAN (and PPN) thermal stability and photochemical production rates, respectively. Organic nitrogen-containing oxidation products (PAN + PPN) were more abundant than inorganic nitrate (HNO₃ + NO₃⁻), with an average organic/inorganic concentration ratio of 2.5 (daytime ratio 1.0; nighttime ratio 3.7). The four oxidation products PAN, PPN, HNO₃ and NO₃⁻ together accounted for 0.26 of the total reactive nitrogen. The results are discussed with respect to diurnal and seasonal variations and in terms of NO₂ atmospheric oxidation pathways. Deposition fluxes and velocities to ponderosa pine have been measured for inorganic nitrate and for ammonium and have been compared with those obtained at other mountain forest locations.     

Analysis of peroxyacetyl nitrate (PAN) in the vertical profile of a spruce stand

Continuous analyses of peroxyacetyl nitrate (PAN) were performed at a forest site in the Eggegebirge, F.R.G., where severe forest decline has occurred in the last decade. An automatically working analysis system was installed inside a spruce stand. Air samples from three elevations (1 m, 7.5 m and 12.5 m above ground) were simultaneously analyzed. The results obtained show that PAN-concentrations in the range below 0.2 ppb prevailed. Several episodes with elevated PAN concentrations, up to 4.6 ppb, were measured. High PAN-levels were more abundant in spring and summer than in winter. PAN concentrations above the canopy were usually higher than within the canopy. Near ground level the lowest concentrations were found. This concentration profile and the detailed discussion of episodes with elevated PAN concentrations, in conjunction with additional meteorological data, showed that PAN formation within or above the forest canopy is relatively low compared to the input by long-range transport. Thus it was concluded that biogenic hydrocarbons emitted by the forest trees do not significantly contribute to the formation of observed PAN peak concentrations. The measured concentrations did not indicate a phytotoxic burden by PAN and PAN homologous photooxidants at this site.