A comparison of urban and suburban precipitation chemistry

Precipitation samples at an urban Chicago site and a nearby suburban site were compared in order to examine the influence of emissions within a large urban area on local precipitation chemistry. Precipitation samples were collected from June 1981 to May 1982, initially for events and subsequently weekly, and precipitation-weighted concentrations (PWCs) of the major chemical constituents were calculated from concurrent urban-suburban pairs of samples, stratified according to the estimated mixed-layer wind quadrant. Overall, PWCs at the urban site were higher than those at the suburban site for Ca²⁺, Mg²⁺, NH₄⁺, NO₃⁻ and Cl⁻; approximately equal for Na⁺ and SO₄²⁻; and lower for H⁺. For precipitation in southwesterly flow, in which the suburban site was upwind of the urban site and most urban emissions, PWCs of all species except Na⁺ were higher at the urban site. For the few precipitation cases in northeasterly flow, however, differences between sites did not have a pattern consistent with a reversal in the upwind-downwind relationship.     

Sequential precipitation samplers: A literature review

This report reviews the literature of sequential or within-event precipitation sampler construction and includes a limited survey of their applications. Collection apparatus have been classified as manually segmenting samplers, linked collection vessels, automatically segmenting samplers and continuous monitors (Robertson et. al., U.S. EPA Report, 1980). Design criteria for an ideal collector are discussed.     

Gas-phase tropospheric chemistry of organic compounds: A review

The current knowledge of the gas-phase reactions occurring in the troposphere for alkanes, alkenes, alkynes, oxygenates and aromatic hydrocarbons and their photooxidation products is reviewed, and areas of uncertainty identified.     

A statistical methodology for exploring elevational differences in precipitation chemistry

A statistical methodology for exploring the relationships between elevation and precipitation chemistry is outlined and illustrated. The methodology is only applicable to situations where the precipitation at two (or more) matched sites is correlated. Maximum likelihood tests are utilized, with contour ellipses of assumed bivariate log-normal distributions to assist in the interpretation. Data from 12 sites located in the southern Rocky Mountains of the U.S. were used for illustration. The results indicate differences in sulphate concentrations between airsheds, between snow and rain, and between higher and lower elevations in the Rocky Mountains. There are other approaches for investigating these issues, however, the likelihood ratio with contour ellipses is easy to apply and interpret, and we feel that it provides a greater insight than some of the more common analyses of variance or regression techniques. However, it is important to note that the superiority of one method over others depends on the criterion used.     

Source types in Canadian precipitation chemistry

Precipitation data generated by Canadian Air and Precipitation Monitoring Network (CAPMoN) have been analysed by an iterative multiple linear regression method, revealing five source types or components, each with distinctive seasonal and geographic variations. Each source types has its characteristics chemical profile. The profiles suggest that two of the source types are rural (apparently derived from fertilizer and soil), two are urban/industrial (apparently derived from SO₂ and NO_x emissions), and one is sea salt. The NO_x-derived component is highly acidic, the SO₂-derived component is also very acidic, the fertilizer component is slightly alkaline, and the soil component is more alkaline.Charge balance calculations show a fairly consistent deficit in anions, a deficit which is especially important for the NO_x-derived component. The anion deficit results suggest that more complete chemical analyses are required.The chemical profiles from CAPMoN data have been used to determine the component contributions to precipitation data collected in Manitoba by the provincial Ministry of the Environment. Back trajectories for the Manitoba data show distinct geographic and seasonal effects, including: (i) seasalt input to Manitoba is derived mainly from Hudson Bay and the Arctic, especially in fall and winter; (ii) the SO₂ component has ubiquitous sources, including polar sources: (iii) the fertilizer component arrives mainly form the U.S. rural Midwest, especially in spring and fall; (iv) the soil component has northern sources, with perhaps transpolar and trans-Pacific origins, in spring and summer; and (v) the NO_x component appears to be derived from northern sources at polar sunrise in spring.     

A paired comparison of two precipitation chemistry sites in East-Central Mississipi

A paired comparison was performed on 2 years of precipitation chemistry data from Meridian and Newton, MS. The Meridian site is in violation of several National Atmospheric Deposition Program siting criteria, whereas the Newton site, 35 km west, is mostly in compliance. The two sites are compared through the use of volume-weighted means, deposition, logarithmic distributions, boxplots, paired t-tests, the nonparametric Wilcoxon test, and a form of linear regression analysis that accounts for cases in which both populations are subject to error. Results indicate Meridian has higher concentrations of all measured ions except NH₄⁺. Elevated NH₄⁺ concentrations at Newton are most likely due to the location of the site in a cattle pasture. Significant differences (95% confidence level) were found for Cl⁻, Na⁺, K⁺, Ca²⁺ and Mg²⁺. SO₄²⁻ was found to be borderline significant.     

Cloud chemistry at Mt Rigi,Switzerland: Dependence on drop size and relationship to precipitation chemistry

The chemical composition of winter and spring cloud water sampled at 1620 masl elevation on Mt Rigi in central Switzerland was dominated by NO₃⁻, SO₄²⁻, NH₄⁺ and H⁺. A wide range of concentration levels was observed, with maxima of 3700, 1800 and 4600 micronormal for NO₃⁻, SO₄²⁻ and NH₄⁺, respectively. Concentrations at a lower elevation (1030 masl) site on the mountain were higher due to lower cloud liquid water contents and higher pollutant levels at that site. The lowest pH observed was 2.95; large concentrations of NH₃ in the region prevented pH values from falling even lower. A comparison of simultaneously sampled cloud water and precipitation revealed much higher concentrations for most species in the cloud water, except in one case of extreme precipitation riming when the concentrations in the two phases converged. An exception to the pattern was H⁺; at times the precipitation was more acidic than the cloud water. The chemical composition of the cloud drops varied with drop size. Drops smaller than 10 μm diameter were enriched in NO₃⁻, SO₄²⁻ and NH₄⁺ relative to larger drops. Since the larger drops are the ones most effeciently captured by snow crystals, knowledge of their composition is essential to understanding the chemical implications of accretional growth of precipitation.     

Atmospheric chemistry of peroxides: a review

Inorganic and organic peroxides have become the focus of increased attention by atmospheric chemists during the last decade. Hydrogen peroxide serves as an important link between gas phase radicals and aqueous phase chemistry in the atmosphere. As an important aqueous phase oxidant of S(IV), H₂O₂ plays a major role in the acidification of clouds, fogs, dew and rain. Several studies have indicated that peroxides and their precursor radicals cause damage to a variety of plant tissue.In this article we review analytical techniques, discuss and review the various sources of peroxides in the gas and aqueous phases and examine their reactions with S(IV) and N(III).     

The response of sulfate linearity and precipitation chemistry to gas-phase profiles

Results are reported from a series of cloud chemistry simulations designed to evaluate the sensitivity of precipitation sulfate concentrations to changes in the shape and mass of the preexisting gas phase profiles. Linearity factors relating chemical inflow conditions to depositio are evaluated. The height from which any given fraction of the sulfur in precipitation came in stratiform storms was found to be approximately equal to the height at which the corresponding fraction sulfur was located. This source height was greater for convective storms. Changes in the total sulfur generally resulted in an almost proportional change in the resulting precipitation sulfate concentrations. Because stratiform storms rely more strongly on the initial gas-phase profiles to define the available oxidant at a given height, the deposition and SO₂ linearity factors associated with such storms were found to be more sensitive to the initial height dependence of the ratio [SO₂] and [H₂O₂] than was found for convective storms. The deposition and the linearity factor for convective storms were found to be more strongly dependent on the total column mass of these species. The precipitation sulfate concentration and linearity were found to be generally insensitive to perturbations in the fine structure of the initial gas-phase profiles.     

An analysis of precipitation chemistry measurements in Shimane,Japan

In order to understand the concentration and deposition levels of the major ions in Shimane, on the Japan Sea coast where precipitation chemistry data are scarce, the precipitation was collected at three sites (Matsue, Gotsu and Masuda) from April 1985 to March 1988.The mean precipitation chemistry was very close to each other except for the seasalt concentration. Masuda showed a halved seasalt contribution compared with the other sites. The volume-weighted annual pH mean at each site ranged from 4.6 to 4.9. Nitrate to SO₄⁻² equivalent ratios were in the range of 0.2 and 0.4 throughout the year. Ammonia and calcium species are interpreted to have neutralized approximately 70% of the original sulfuric and nitric acids.The annual depositions of the major ions in g m⁻²y⁻¹ were as follows: H⁺; 0.023–0.037, NH₄⁺; 0.57–0.68, Ca²⁺; 0.51–0.92, SO₄²⁻; 3.29–5.04, NO₃⁻; 1.20–1.70. These levels are of the same intensity as corresponding values of JEA network results.     

泰山降水化学及大气传输的研究

为了解泰山降水的化学组成特征及其来源,于2004年7月至12月间在泰山上采集了23场降水样品,进行了pH值、电导率的测定、主要水溶性阴阳离子的分析以及每场降水的后推气流轨迹分析.结果表明,降水pH的雨量加权均值为4.74,电导率的雨量加权均值为2.26mS·m-1,泰山降水已受到酸性污染;降水中浓度较高的阳离子是NH4 和Ca2 ,雨量加权均值浓度分别为50.62和29.04μeq·L-1,浓度较高的阴离子是SO42-和NO3-,雨量加权均值浓度分别为70.32和23.44μeq·L-1;SO42-/NO3-、NH4 /Ca2 当量浓度比的平均值依次为3.41、2.13.对降水的化学组成作了相关性分析,发现NH4 、Ca2 、SO42-、NO3-浓度之间具有很好的相关性;通过气流轨迹分析发现酸性最强的降水气团来自于我国的南部地区或沿途经过华东地区,离子浓度最高的降水气团来自于我国的北部地区或欧洲大陆,来自东亚地区的降水气团的离子浓度最低.     

A review of gas-phase chemical mechanisms commonly used in atmospheric chemistry modelling

The atmospheric chemical mechanism is an essential component of airshed models used for investigating the chemical behaviors and impacts of species. Since the first tropospheric chemical mechanism was proposed in the 1960s, various mechanisms including Master Chemical Mechanism (MCM), Carbon Bond Mechanism (CBM), Statewide Air Pollution Research Center (SAPRC) and Regional Atmospheric Chemistry Mechanism (RACM) have been developed for different research purposes. This work summarizes the development and applications of these mechanisms, introduces their compositions and lumping methods, and compares the ways the mechanisms treat radicals with box model simulations. CBM can reproduce urban pollution events with relatively low cost compared to SAPRC and RACM, whereas the chemical behaviors of radicals and the photochemical production of ozone are described in detail in RACM. The photolysis rates of some oxygenated compounds are low in SAPRC07, which may result in underestimation of radical levels. As an explicit chemical mechanism, MCM describes the chemical processes of primary pollutants and their oxidation products in detail. MCM can be used to investigate certain chemical processes; however, due to its large size, it is rarely used in regional model simulations. A box model case study showed that the chemical behavior of OH and HO₂ radicals and the production of ozone were well described by all mechanisms. CBM and SAPRC underestimated the radical levels for different chemical treatments, leading to low ozone production values in both cases. MCM and RACM are widely used in box model studies, while CBM and SAPRC are often selected in regional simulations.     

希夏邦马峰北坡地区夏末降水化学特征探讨

1 997年 8— 9月野外工作期间 ,在希夏邦马峰北坡达索普冰川高海拔区 ( 2 8°33′N ,85°44′E)采集到一批大气降水样品 .样品化学分析结果表明 ,达索普冰川高海拔区夏末降水化学成分中NO3- 浓度最高 ,Mg2 浓度最低 .海盐离子浓度在海洋性气团降水中高于局地大陆性气团降水 .同全球其它偏远地区比较 ,本区夏末降水的主要离子浓度较低 ,与南极和格陵兰冰盖内陆地区雪冰相当 ,表明希夏邦马峰北坡地区夏末大气环境相当“洁净” ,可代表全球偏远地区大气降水的本底状况 .达索普冰川区夏末降水的 pH值 (平均值为 6.0 )和主要离子浓度表明 ,本区夏末大气降水受人类排放污染物的影响很小 ,同时降水的电导率较低而且变化较小 .     

应用遗传神经网络方法分析我国降水化学数据

收集了１１１组包含Ｃａ＾２＋、Ｍｇ＾２＋等８种离子浓度和ＰＨ值的我国降水化学数据，并用遗传神经网络（Ｇｅｎｅｔｉｃ Ｎｅｕｒａｌ Ｎｅｔ－ｗｏｒｋｓ，ＧＮＮ）方法建立了这些离子浓度和ＰＨ值绵ＢＰ网络模式，运用这些模式计算了各离子浓度对ＰＨ值的贡献，结果表明，我国各地降水ＰＨ值与各地区酸性离子与碱性离子相互用途相关，其中生离子的中和作用起着主导作用。     

Spatial variability of urban precipitation chemistry and deposition: Statistical associations between constituents and potential removal processes of precursor species

The precipitation chemistry of Greater Manchester, a Metropolitan County in the northwest of England, has been examined for small scale spatial variability using a network of 18 bulk precipitation collectors. Significant spatial variability was found for concentrations of non-marine SO₄²⁻, NO₃⁻, NH₄⁺, Ca²⁺ and H⁺ ions. The statistical associations between the data were investigated using correlation, partial correlation and principal components analyses. It was found that zero-order correlation coefficients were inadequate for the interpretation of the data and that the computation of first, and higher order partial correlation coefficients was necessary in order to explain the interrelationships between the data and their spatial variability. The statistical associations between the data suggest relationships between Ca²⁺ and non-marine SO₄²⁻, and NO₃⁺ in precipitation which are discussed in terms of their possible precursor species. Potential source effects were examined in conjunction with atmospheric removal processes. The dry deposition of SO₄ particles, rather than the dry deposition of SO₂, may explain the spatial variability of non-marine SO₄²⁻. The erosion of CaSO₄ formed from the reaction of SO₂ with CaCO₃ on urban surfaces with subsequent resuspension is thought to be the basis of the relationship between Ca²⁺ and non-marine SO₄²⁻ concentrations in precipitation. The wet and dry deposition of CaCO₃ particles from local sources may be partially responsible for the spatial variability of H⁺, and dry deposition and scavenging of NH₃, in conjunction with the predominant wind direction may explain the spatial variability of NO₃⁻ and NH₄⁺ ions. Ammonia is thought to originate from sources both outside the study area and within it.     

A review on the generation, determination and mitigation of Urban Heat Island

Urban Heat Island （UHI） is considered as one of the major problems in the 21st century posed to human beings as a result of urbanization and industrialization of human civilization. The large amount of heat generated from urban structures, as they consume and re-radiate solar radiations, and from the anthropogenic heat sources are the main causes of UHI. The two heat sources increase the temperatures of an urban area as compared to its surroundings, which is known as Urban Heat Island Intensity （UHII）. The problem is even worse in cities or metropolises with large population and extensive economic activities. The estimated three billion people living in the urban areas in the world are directly exposed to the problem, which will be increased significantly in the near future. Due to the severity of the problem, vast research effort has been dedicated and a wide range of literature is available for the subject. The literature available in this area includes the latest research approaches, concepts, methodologies, latest investigation tools and mitigation measures. This study was carded out to review and summarize this research area through an investigation of the most important feature of UHI. It was concluded that the heat re-radiated by the urban structures plays the most important role which should be investigated in details to study urban heating especially the UHI. It was also concluded that the future research should be focused on design and planning parameters for reducing the effects of urban heat island and ultimately living in a better environment.     

青海湖水化学的季节性和空间变化及其受自生碳酸盐沉淀的影响

青海湖湖水季节性和空间上的变化特征对青海湖沉积物中自生碳酸盐形成过程及环境意义的理解、湖泊的演变趋势具有重要的指导意义。本文通过沉积物捕获器采集了为期一年每月一次的青海湖季节性的湖水,并采集了青海湖和周围子湖空间分布上的湖水样品。对季节性样品阳离子的分析显示,青海湖湖水中的阳离子在旱季（12月至次年4月）达到最高值,在雨季逐渐降低。湖水的Ca²⁺和Mg²⁺从2—3月份逐步降低,表明自生碳酸盐开始沉淀,并且在雨季来临时沉淀持续大量发生,而在雨季后期,则可能发生含Mg碳酸盐的部分溶解。空间分布的样品分析显示,青海湖可能经历了太阳湖和月牙湖的水化学阶段,在未来的演变过程中,湖水的Ca²⁺和Sr²⁺受自生碳酸盐沉淀的控制而保持基本稳定,Mg²⁺、Na⁺、K⁺则将持续增加,其水化学将朝着当前海晏湾,并进一步朝尕海湖水的方向演变。本文的研究还进一步暗示了在长时间尺度上自生碳酸盐形成对气候变化的可能响应。     

The impact of changing regional emissions on precipitation chemistry in the eastern United States

From 1975 to 1987 a 19% change in SO₂ emissions a 16% change in NO_x emissions have occurred over the eastern and mid-western U.S. Six continental precipitation chemistry sites from the MAP3S network, plus the Hubbard Brook Experimental Forest, NH, show a direct relationship between emission levels and precipitation H⁺ and SO₄^2- concentrations, except for Penn State, PA. MAP3S sites at Illinois and Ohio, located closest to the major SO₂ source regions, demonstrates statiscally significant (P <0.05) linear regressions of SO₄^2- concentrations on SO₂ emissions. Whiteface Mt., NY, shows a weaker relationship (P <0.01), and Hubbard Brook shows the strongest relationship (P <0.01) between SO₂ emissions and SO₄^2- concentration in precipitation. No site shows a significant relationship (P <0.10) for NO_x emissions and NO₃⁻ concentrations in precipitation. Illinois, Ohio, Ithaca and Hubbard Brook show significant linear regressions of H⁺ concentrations on emissions of SO₂ + NO_x (P <0.10, 0.05, 0.01, and 0.01, respectively). Overall, for the entire region examined, decreasing SO₂ emissions levels appear to have decreased SO₄^2- concentrations with an efficiency of 74% ± 15% (s.e.). Decreasing SO₂ plus NO_x emissions (18%) have been accompanied by a decreasing H⁺ concentrations (18%) suggesting an efficiency of conversion of 100% ± 15% (s.e.) for the study region as a whole. While significant reductions in acid species have occured at Hubbard Brook, further reductions in excess of 50% of present deposition are necessary to protect acid-sensitive ecosystems.     

Influence of sea salt aerosols and long range transport on precipitation chemistry at El Verde,Puerto Rico

The chemistry of bulk precipitation was measured from November 1983 to September 1987 at El Verde in the Luquillo Experimental Forest, Puerto Rico. Wet-only precipitation was also analyzed as part of the National Atmospheric Deposition Program from 1984 to 1987. Volume-weighted mean pH was 5.14 in bulk precipitation and 5.12 in wet precipitation. Concentrations of most species were correlated negatively with weekly rainfall. Sea salt aerosols contributed most of the Na⁺, Cl⁻, Mg²⁺ and K⁺ found in wet and bulk precipitation; sulfate and calcium, however, were derived primarily from non-sea salt sources. Due to the high rainfall (3.4 m annually during the study period) and close proximity of the study site to the ocean, deposition rates of the major cations and anions were high relative to many other tropical sites. Precipitation chemistry at El Verde appears to be affected by several factors. During summer, Saharan dusts contribute a significant portion of the excess Ca²⁺, K⁺ and Mg²⁺. During winter months, cold fronts may transport SO₄²⁻ and NO₃⁻ from North America and the western part of Puerto Rico to the sampling site.