固定污染源烟气中可凝结颗粒物监测技术现状及展望

随着国家对大气环境治理的推进,可凝结颗粒物(CPM)成为工业烟气防治的关键污染物。CPM在烟道高温环境中为气态物质,排入大气环境后快速凝结成颗粒态物质,对其进行准确测量是国内外的前沿技术挑战之一。通过研究分析CPM在烟气和烟羽中演化特征与监测技术现状,阐明CPM的概念、形成机制与排放特征,阐释已有的工业烟气CPM采集与分析方法及其存在的问题,并进一步对超低排放烟气中CPM的在线监测和质控技术提出展望。     

铵盐气溶胶对烟气排放连续监测系统颗粒物比对监测的影响研究

利用拉曼光谱对采样后的滤筒进行分析,发现废气中的硫酸铵-硫酸氢铵气溶胶是造成成都市部分企业烟气排放连续监测系统(CEMS)颗粒物比对监测结果不合格的主要原因。通过比较分析得出:在对含硫酸铵-硫酸氢铵气溶胶废气进行颗粒物浓度比对监测时,参比方法(重量法)测定的颗粒物浓度是一定标干采样体积下废气中固体微粒和硫酸铵-硫酸氢铵液体微粒结晶后产生的晶体的总质量,基于光散射法的CEMS颗粒物浓度测试系统测定的颗粒物浓度只是一定标干采样体积下废气中固体微粒的质量,由此导致参比方法测出的颗粒物浓度远大于CEMS测出的浓度,造成比对误差远超出允许值范围。     

氯苯类化合物在大气中分布特征探究

建立环境空气和有组织废气排放模拟污染源,以玻璃纤维滤膜+玻璃棉和活性炭为吸附材料采集大气中氯苯类化合物,使用气相色谱法测定各组分,考察氯苯类化合物在大气气相和颗粒物中的分布特征。结果显示,环境空气和固定污染源有组织排放废气中一氯代至四氯代苯类各组分主要分布在大气气相中,颗粒物中少有分布,说明现行环境监测方法以固体吸附剂采集测定大气中的氯苯类化合物可行。     

冷凝-吸附法测定固定源废气含湿量

综合传统重量法与冷凝法测定废气含湿量的特点,建立冷凝-吸附法测定固定源废气含湿量,有效解决重量法与冷凝法不适用于高温、高湿条件下的测定问题。通过优化测定条件,使冷凝-吸附法测定3台不同类型固定源废气结果的RSD为1.5%~4.7%,方法再现性试验结果的RSD为4.5%。用该方法与重量法同时测定油田注汽湿蒸汽发生器及普通流化床锅炉废气含湿量,结果表明冷凝-吸附法具备更强的适用性。     

Modelling the Removal of Gaseous Pollutants and Particulate Matters from the Atmosphere of a City by Rain: Effect of Cloud Density

In this paper, an original nonlinear mathematical model for the removal of gaseous pollutants and particulate matters from the atmosphere of an industrial city by rain is proposed and analyzed. It is assumed that five interacting phases in the atmosphere of the city exist, i.e., cloud droplets phase, raindrops phase, gaseous pollutants phase, particulate matters phase, and the phase of absorbed gaseous pollutants in raindrops. It is assumed further that these phases undergo nonlinear interactions in the atmosphere, while gaseous pollutant interacts with cloud droplets as well as with raindrops but particulate matters interact only with raindrops. The gravitational settling and reversible reaction processes have also been considered appropriately in the model. By analyzing the model, it is shown that both the gaseous pollutants and particulate matters may be removed from the atmosphere under certain conditions, provided the rates of formation of cloud droplets and raindrops are sufficiently large. It is noted that under unfavorable atmospheric conditions, rain does not occur and pollutants are not removed from the atmosphere.     

燃煤锅炉湿法脱硫烟气中颗粒物排放特征

选择北京市典型燃煤锅炉进行研究,结果表明:烟气中可凝结颗粒物在总颗粒物中占有较高比例,供热燃煤锅炉总颗粒物排放水平明显高于电厂燃煤锅炉;颗粒物中水溶性离子含量较高,供热燃煤锅炉硫酸根比例尤其显著;烟气总颗粒物中存在大量不稳定的易被氧化的组分;同为燃煤源,不同的烟气净化工艺排放的PM2.5组分特征差异明显;现有标准和技术规范存在不足,无法满足全面、准确监测污染源排放总颗粒物的实际需要。建议建立总颗粒物、可凝结颗粒物的监测技术规范,全面测算燃煤锅炉硫、氮化合物排放情况,科学评估脱硫及脱硝效率。     

灰霾期间气溶胶的污染特征

从颗粒物的时空分布和浓度水平方面综述了灰霾期间气溶胶的污染特征,介绍了灰霾期间气溶胶中金属元素、水溶性离子、有机碳和元素碳的浓度特征,以及颗粒物与能见度的相关性研究进展。指出:灰霾天气多发生在冬季,且气溶胶中PM2.5占的比重大;气溶胶污染与地理环境、气候条件、经济发展水平等有密切关系;水溶性离子多集中在PM2.5中;能见度的下降与气溶胶特别是细颗粒物有很大关系。提出目前灰霾研究中主要存在3大问题:一是对灰霾期间气溶胶中含有的有机物类别及其对不同季节发生灰霾的贡献率仍需进一步研究;二是灰霾期间气溶胶中有机物的形成机理尚不明确;三是不同源排放的气溶胶对灰霾形成的贡献率有待探讨。建议系统地开展大气细颗粒物有害成分的鉴定、源排放颗粒物的物理化学特性、扩散过程中各种物质间的反应和转化等方面的研究,为大气污染防治法规的制定提供依据。     

Near-real-time determination of hydrogen peroxide generated from cigarette smoke

The ability to monitor hydrogen peroxide (H2O2) in aqueous smoke extracts will advance our understanding of the relationship between cigarette smoke-induced oxidative stress, inflammation, and disease and help elucidate the pathways by which the various smoke constituents exert their pathogenic effects. We have demonstrated, for the first time, the measurement of H2O2 production from cigarette smoke without prior separation of the sample. Cigarettes were tested on a commercial smoking machine, such that the whole smoke or gas vapor phase was bubbled through phosphate buffered saline solution at pH 7.4. Aliquots of these solutions were analyzed using an Amplex Red/horseradish peroxidase fluorimetric assay that required only a 2 minute incubation time, facilitating the rapid, facile collection of data. Catalase was used to demonstrate the selectivity and specificity of the assay for H2O2 in the complex smoke matrix. We measured approximately 7-8 microM H2O2 from two reference cigarettes (i.e., 1R4F and 2R4F). We also observed 9x more H2O2 from whole smoke bubbled samples compared to the gas vapor phase, indicating that the major constituent(s) responsible for H2O2 formation reside in the particulate phase of cigarette smoke. Aqueous solutions of hydroquinone and catechol, both of which are particulate phase constituents of cigarette smoke, generated no H2O2 even though they are free radical precursors involved in the production of reactive oxygen species in the smoke matrix.     

高效率颗粒物微物理模型简介与重污染过程应用分析

中国细颗粒物(PM2.5)导致的空气污染和雾霾天气问题越来越突出,在低层对流层中很多地方都有显著的二次颗粒物生成过程,因此对颗粒物物理化学转化过程的研究具有重要意义,其转化过程对空气质量模式模拟和预报的准确性有重要影响。高效率颗粒物微物理(APM)模型经过近20多年的研究和发展,在全球化学传输模型(GEOS-Chem)、区域性气象和化学预报模型(WRF-Chem)通用地球系统模型(CESM-CAM5)等气象及环境空气质量预报模型中取得了很好的应用验证,能够在全球/区域等不同尺度对粒子生成、长大、凝聚、消除等微物理过程以及气溶胶光学厚度(AOD)、直接/间接辐射强迫等进行模拟。应用GEOS-Chem-APM模式模拟了2014年2月京津冀区域的重污染过程。结果显示,湿度模拟的准确性对其他物理和污染物浓度等模拟结果有重要作用;2月20—26日的重污染过程模拟结果与实际观测较为吻合,主要污染特点是较高的湿度(90%以上),同时,二次颗粒物和包裹了二次物种的一次颗粒物(黑碳/有机碳)是低能见度的最大贡献者。     

Possible markers of traffic-related emissions

Looking for robust indicators of motor vehicle emissions it has been found that brake wear and linings are significant contributors of Cu, Mo and Sb to air particulate matter. These trace elements, whose mutual ratios in airborne particulate matter resulted quite different from those in crustal material, appear to be available fingerprinting tools to identify the contribution of on-road vehicles to traffic-derived particulate matter. In this study, the results of analytical determinations of Cu, Mo and Sb on PM(10), PM(2.5), vegetation and brake dust samples, together with gas (CO, NOx) concentrations, are discussed. Highly significant correlations among Cu, Sb and Mo were observed in particulate matter from Palermo and between Cu-Sb and Cu-Mo at Catania. Further significant positive correlations have been found in pine needles from Palermo, Gela and in platanus leaves from Catania.     

湿法脱硫烟气中多形态颗粒物的测量方法及组分特征

为全面测量固定源湿法脱硫烟气中多形态颗粒物的排放浓度及其离子组成特征，提出了一种基于一级冷凝、二级过滤和一级冲击吸收的多形态烟气颗粒物的同步测量方法，外场实测了3种湿法脱硫和除尘工艺的排放水平。现场测试表明：简易湿法除尘脱硫（NaOH法）一体化装置烟气中可过滤颗粒物（FPM）浓度为（36±11）mg/m³，可逃逸颗粒物（EPM）浓度为（33±7）mg/m³；氧化镁法+布袋除尘工艺烟气中FPM浓度为（14±5）mg/m³，EPM浓度为（13±6）mg/m³；石灰石-石膏脱硫+电袋除尘工艺烟气中FPM浓度低，小于3 mg/m³，EPM浓度为（6±1）mg/m³；烟气中EPM是传统滤膜法检测FPM浓度的0.7~5.7倍，EPM的主要存在形态为冷凝液中的可溶解颗粒物（DPM），颗粒物的组分与脱硫方法密切相关，各形态颗粒物的主要组分是SO₄^2-、SO₃^2-、NO₃^-、NO₂^-、NH₄⁺、Cl^-、Na⁺、Mg²⁺和Ca²⁺等离子。     

Wetting and hydration of insoluble soot particles in the upper troposphere

Wettability and hydration are determined for aircraft combustor and laboratory-made soots which are used as surrogates for the insoluble part of aircraft-generated black carbon particles in the upper troposphere (UT). The measured water/ice contact angles on the soot surfaces are in the range 60-80 degrees. Factors influencing the soot wetting show a tremendous dependence on the surface chemical composition and microstructure. Wetting characteristics of soots are directly related to its hydrophilicity. The inverse Kelvin effect is considered as a mechanism of ice nucleation which is facilitated by the soot agglomerated structure with interparticle cavities in which condensation takes place on the insoluble surface with a high water contact angle. Estimations of the critical supersaturations needed for the ice condensation growth of particles are provided to determine which of the wetting characteristics are required for cirrus cloud formation in ice saturated regions of the UT.     

Woodstove emission measurement methods: Comparison and emission factors update

On February 26, 1988, the U.S. Environmental Protection Agency promulgated Standards of Performance for residential wood heaters, or woodstoves. Over the past several years, a number of field studies have been undertaken to determine the actual level of emission reduction achieved by new technology woodstoves in everyday use. These studies have required the development and use of particulate and gaseous emission sampling equipment compatible with operation in private houses. Since woodstoves are tested for certification in the laboratory using EPA Methods 5G and 5H, it is of substantial interest to determine the correlation between these regulatory methods and the in-house equipment. Two in-house sampling systems have been used most widely. One is an intermittent, pump-driven particulate sampler which collects particulate and condensable organics on a filter and organic adsorbent resin. Oxygen concentration is measured by a sensor in the sample line. The sampler is controlled by a data logger which also records other parameters of interest. The second system uses an evacuated cylinder as the motive force. Particulate and condensable organics are collected in a condenser and dual filter. The sampler operates continuously whenever the stack temperature is above the set point. Average stack gas concentrations are measured from the evacuated cylinder at the conclusion of the sampling period. Both samplers were designed to operate unattended for 1-week periods. A large number of tests have been run comparing Methods 5G and 5H to both of the field samplers. This paper presents these comparison data and determines the relationships between laboratory certification sampling methods and field samplers.     

乌鲁木齐市可吸入颗粒物中多环芳烃的源解析

通过对乌鲁木齐市可吸入颗粒物和多环芳烃主要污染源煤烟尘和机动车尾气尘进行采样和分析,得到可吸入颗粒物中多环芳烃的浓度和污染源中多环芳烃的含量,利用化学质量平衡受体模型对其来源进行分析。     

利用SPAMS初探盘锦市冬季PM2.5污染特征及来源

利用SPAMS 0515于2015年1月在盘锦市兴隆台空气质量自动监测点位采集PM_(2.5)样品,并分析其污染特征和来源。研究结果表明,盘锦市冬季PM_(2.5)的颗粒类型主要以OC颗粒、富钾颗粒、EC颗粒组成。其中,OC颗粒占比最高,为52.5%;PM_(2.5)污染的主要贡献源为燃煤、生物质燃烧、机动车尾气排放,占比分别为33.2%、25.7%、17.5%,特别是在PM_(2.5)质量浓度较高时段,燃煤和机动车尾气排放对污染的贡献较大。     

Transport and modification of humic substances present in Antarctic snow and ancient ice

We performed a study of fulvic acids extracted from fresh and aged snow, and from recent and ancient ice in Antarctica. The fresh snow samples were collected in coastal and inland sites to evaluate the influence of the distance from the sea on organic matter transport. Moreover, in a site (Melbourne Mountain) samples were collected at different heights to study the influence of altitude on transport. The obtained results showed that dissolved fulvic acid concentrations are influenced neither by distance nor by height while particulate fulvic acid concentrations are influenced by both parameters. Moreover, the results showed that fulvic acids transported for a long distance can undergo chemical modifications. Chemical modifications are better evidenced by the analysis of samples taken in trenches at different depth, which showed structural changes attributable to the loss of nitrogen-containing compounds and to an increase in aromatic character of the structures due to reduction and/or condensation processes. With ageing, the humification process proceeds with heavy carbon losses as demonstrated by results obtained from fulvic acids isolated from ice aged between twenty-five thousand and seventy thousand years.     

Diurnal trends in coarse particulate matter composition in the Los Angeles Basin

To investigate the diurnal profile of the concentration and composition of ambient coarse particles, three sampling sites were set up in the Los Angeles Basin to collect coarse particulate matter (CPM) in four different time periods of the day (morning, midday, afternoon and overnight) in summer and winter. The samples were analyzed for total and water-soluble elements, inorganic ions and water-soluble organic carbon (WSOC). In summer, highest concentrations of CPM gravimetric mass, mineral and road dust, and WSOC were observed in midday and afternoon, when the prevailing onshore wind was stronger. In general, atmospheric dilution was lower in winter, contributing to the accumulation of air pollutants during stagnation conditions. Turbulences induced by traffic become a significant particle re-suspension mechanism, particularly during winter night time, when mixing height was lowest. This is evident by the high levels of CPM mass, mineral and road dust in winter overnight at the near-freeway sites located in urban Los Angeles, and to a lesser extent in Riverside. WSOC levels were higher in summer, with a similar diurnal profile with mineral and road dust, indicating that they either share common sources, or that WSOC may be adsorbed or absorbed onto the surfaces of these dust particles. In general, the contribution of inorganic ions to CPM mass was greater in the overnight sampling period at all sampling sites, suggesting that the prevailing meteorological conditions (lower temperature and higher relative humidity) favor the formation of these ions in the coarse mode. Nitrate, the most abundant CPM-bound inorganic species in this basin, is found to be predominantly formed by reactions with sea salt particles in summer. When the sea salt concentrations were low, the reaction with mineral dust particles and the condensation of ammonium nitrate on CPM surfaces also contributes to the formation of nitrate in the coarse mode.     

Evolution of lead concentration in the particulate matter of Santiago,Chile, since 1978

Santiago is a city of over 4.5 million inhabitants and about 415000 motor vehicles using leaded gasoline. Twenty-four-hour samples were taken of total and fractionated particulate matter using a low-volume system and two Andersen cascade impactors, between 1978 and 1989 at different sites of the city of Santiago. Lead concentrations were determined by atomic absorption spectrophotometry. The results show that Pb concentrations vary greatly depending on the site selected. Higher values are always detected near the city center. An annual variation with the highest value during the autumn-winter period (May–July) is clearly observed. Lead concentrations versus size are clearly biased to particles smaller than 2 µm. A correlation is observed between Pb concentrations and the suspended particulate matter under 3 µm at different sites of the city. The curves of Pb concentration versus size of the aerosols emitted by the gas exhaust of motor vehicles using leaded gasoline are similar to those of the atmospheric aerosols.     

固定污染源废气中磷酸雾测定方法研究

目前,对固定污染源废气中磷酸雾的检测并无统一的方法,相关含磷污染物的控制指标主要是磷化氢、单质磷以及五氧化二磷。在调研国内外分析方法及相关文献的基础上,通过对几种典型含磷污染源的实样测试,提出了固定污染源废气中磷酸雾的检测方法。结果表明,使用石英滤筒捕集固定污染源废气中的磷酸雾,采样效率可达98%以上。捕集到的总磷酸雾不仅包含磷酸,还包含磷酸盐以及含磷氧化物等,是一项综合指标。该指标能够反映含磷污染物的排放特征,可为未来此类污染物的排放控制提供依据。     

湿法脱硫后高湿烟气中SO3酸雾监测方法研究

利用三氧化硫(SO3)发生装置以及模拟烟气湿法脱硫系统,研究了烟气再热温度、恒温水浴温度、采样速率、冷凝管类型规格及吸收瓶个数等不同采样参数对SO3酸雾采集率的影响。结果表明,当烟气再热温度低于烟气酸露点时会导致SO3酸雾收集率下降,采用控制冷凝法采样时应使用大流量(10L/min)采样,冷凝管应选择外套长度为400 mm的蛇形螺旋冷凝管,并将冷凝管置于温度为65℃左右的恒温水浴中;用碱液吸收法采样时应串联3个吸收瓶后,使用小流量(1L/min)采样。烟气温湿度、二氧化硫(SO2)浓度以及烟气中共存组分等对碱性吸收法的采集影响较大,而对控制冷凝法几乎没有影响。因此确立了针对湿法脱硫后高湿烟气环境下SO3酸雾的监测方法为控制冷凝法更为适宜。