A review of biomarker compounds as source indicators and tracers for air pollution

An overview of the application of organic geochemistry to the analysis of organic matter on aerosol particles is presented here. This organic matter is analyzed as solvent extractable bitumen/ lipids by gas chromatography-mass spectrometry. The organic geochemical approach assesses the origin, the environmental history and the nature of secondary products of organic matter by using the data derived from specific molecular analyses. Evaluations of production and fluxes, with cross-correlations can thus be made by the application of the same separation and analytical procedures to samples from point source emissions and the ambient atmosphere. This will be illustrated here with typical examples from the ambient atmosphere (aerosol particles) and from emissions of biomass burning (smoke). Organic matter in aerosols is derived from two major sources and is admixed depending on the geographic relief of the air shed. These sources are biogenic detritus (e.g., plant wax, microbes, etc.) and anthropogenic particle emissions (e.g., oils, soot, synthetics, etc.). Both biogenic detritus and some of the anthropogenic particle emissions contain organic materials which have unique and distinguishable compound distribution patterns (C₁₄-C₄₀). Microbial and vascular plant lipids are the dominant biogenic residues and petroleum hydrocarbons, with lesser amounts of the pyrogenic polynuclear aromatic hydrocarbons (PAH) and synthetics (e.g., chlorinated compounds), are the major anthropogenic residues. Biomass combustion is another important primary source of particles injected into the global atmosphere. It contributes many trace substances which are reactants in atmospheric chemistry and soot paniculate matter with adsorbed biomarker compounds, most of which are unknown chemical structures. The injection of natural product organic compounds into smoke occurs primarily by direct volatilization/steam stripping and by thermal alteration based on combustion temperature. Although the molecular composition of organic matter in smoke particles is highly variable, the molecular tracers are generally still source specific. Retene has been utilized as a tracer for conifer smoke in urban aerosols, but is not always detectable. Dehydroabietic acid is generally more concentrated in the atmosphere from the same emission sources. Degradation products from biopolymers (e.g., levoglucosan from cellulose) are also excellent tracers. An overview of the biomarker compositions of biomass smoke types is presented here. Defining additional tracers of thermally-altered and directly-emitted natural products in smoke aids the assessment of the organic matter type and input from biomass combustion to aerosols. The precursor to product approach of compound characterization by organic geochemistry can be applied successfully to provide tracers for studying the chemistry and dispersion of ambient aerosols and smoke plumes. Presented at the 6th FECS Conference on Chemistry and the Environment, Atmospheric Chemistry and Air Pollution, August 26–28, 1998, Copenhagen.     

Cd(Ⅱ)-邻菲咯啉络合物极谱吸附波测定水中微量镉

在ＰＨ＝４．７４的０．２ｍｏｌ／ＨＡｃ－ＮａＡｃ缓冲体系中,Ｃｄ（Ⅱ）－邻菲咯啉络合物在单扫描波极谱仪上于－０．７９Ｖ处产生一灵敏的吸附还原波,其二次微分极谱波灵敏度高,波形好。     

活性炭吸附室内空气中挥发性有机化合物

活性炭吸附室内空气中挥发性有机化合物的１０％穿透时间与气相浓度及挥发性有机化合物的种类有关,通过对苯、甲苯和丙酮的实验研究,得出了由高浓度估算室内低浓度时炭床１０％穿透时间的经验公式ｔｂ,１＝ｔｂ,ｈ（Ｃ０,１／Ｃ０,ｈ）＾ａ,其中ａ值是与炭床性能及挥发性有机化合物种类有关的参数,可通过实验确定。     

宁波市大气可吸入颗粒物PM1o和PM2.5的源解析研究

在宁波市布设4个代表性点位,于2010年春季、夏季和冬季进行大气PM10和PM2.s的采样,同时采集了多种颗粒物源样品,建立了PM10、PM2.5和源样品的化学成分谱.采用化学质量平衡模型(CMB)对宁波市PM10、PM2.5进行源解析.结果表明,城市扬尘、煤烟尘、机动车尾气尘是宁波市PM10、PM2.5的3大污染源,...     

Study of lead phytoavailability for atmospheric industrial micronic and sub-micronic particles in relation with lead speciation

Particles from channelled emissions of a battery recycling facility were size-segregated and investigated to correlate their speciation and morphology with their transfer towards lettuce. Microculture experiments carried out with various calcareous soils spiked with micronic and sub-micronic particles (1650 ± 20 mg Pb kg⁻¹) highlighted a greater transfer in soils mixed with the finest particles. According to XRD and Raman spectroscopy results, the two fractions presented differences in the amount of minor lead compounds like carbonates, but their speciation was quite similar, in decreasing order of abundance: PbS, PbSO₄, PbSO₄·PbO, α-PbO and Pb⁰. Morphology investigations revealed that PM_2.5 (i.e. Particulate Matter 2.5 composed of particles suspended in air with aerodynamic diameters of 2.5 μm or less) contained many Pb nanoballs and nanocrystals which could influence lead availability. The soil-plant transfer of lead was mainly influenced by size and was very well estimated by 0.01 M CaCl₂ extraction.     

Spatio-temporal characteristics of PM10 concentration across Malaysia

The recurrence of forest fires in Southeast Asia and associated biomass burning, has contributed markedly to the problem of trans-boundary haze and the long-range movement of pollutants in the region. Air pollutants, specifically particulate matter in the atmosphere, have received extensive attention, mainly because of their adverse effect on people's health. In this study, the spatial and temporal variability of the PM10 concentration across Malaysia was analyzed by means of the rotated principal component analysis. The results suggest that the variability of the PM10 concentration can be decomposed into four dominant modes, each characterizing different spatial and temporal variations. The first mode characterizes the southwest coastal region of the Malaysian Peninsular with the PM10 showing a peak concentration during the summer monsoon i.e. when the winds are predominantly southerlies or southwesterlies, and a minimal concentration during the winter monsoon. The second mode features the region of western Borneo with the PM10 exhibiting a concentration surge in August–September, which is likely to be the result of the northward shift of the Inter Tropical Convergence Zone (ITCZ) and the subsequent rapid arrival of the rainy season. The third mode delineates the northern region of the Malaysian Peninsular with strong bimodality in the PM10 concentration. Seasonally, this component exhibits two concentration maxima during the late winter and summer monsoons, as well as two minima during the inter-monsoon periods. The fourth dominant mode characterizes the northern Borneo region which exhibits weaker seasonality of the PM10 concentration. Generally, the seasonal fluctuation of the PM10 concentration is largely associated with the seasonal variation of rainfall in the country. However, in addition to this, the PM10 concentration also fluctuates markedly in two timescale bands i.e. 10–20 days quasi-biweekly (QBW) and 30–60 days lower frequency (LF) band of the intra-seasonal timescales. These intra-seasonal fluctuations show strong seasonality with the largest fraction of variance occurring during the boreal summer and the weakest variance during the winter. Generally, the LF intra-seasonal oscillation is stronger compared to the QBW intra-seasonal band.     

A new direct thermal desorption-GC/MS method: Organic speciation of ambient particulate matter collected in Golden, BC

Particulate matter having an aerodynamic diameter less than 2.5 μm (PM2.5) is thought to be implicated in a number of medical conditions, including cancer, rheumatoid arthritis, heart attack, and aging. However, very little chemical speciation data is available for the organic fraction of ambient aerosols. A new direct thermal desorption-gas chromatography/mass spectrometry (TD-GC/MS) method was developed for the analysis of the organic fraction of PM2.5. Samples were collected in Golden, British Columbia, over a 15-month period. n-Alkanes constituted 33–98% by mass of the organic compounds identified. PAHs accounted for 1–65% and biomarkers (hopanes and steranes) 1–8% of the organic mass. Annual mean concentrations were: n-alkanes (0.07–1.55 ng m⁻³), 16 PAHs (0.02–1.83 ng m⁻³), and biomarkers (0.02–0.18 ng m⁻³). Daily levels of these organics were 4.89–74.38 ng m⁻³, 0.27–100.24 ng m⁻³, 0.14–4.39 ng m⁻³, respectively. Ratios of organic carbon to elemental carbon (OC/EC) and trends over time were similar to those observed for PM2.5. There was no clear seasonal variation in the distribution of petroleum biomarkers, but elevated levels of other organic species were observed during the winter. Strong correlations between PAHs and EC, and between petroleum biomarkers and EC, suggest a common emission source – most likely motor vehicles and space heating.     

Implementation of a windblown dust parameterization into MODELS-3/CMAQ: Application to episodic PM events in the US/Mexico border

Windblown dust is known to impede visibility, deteriorate air quality and modify the radiation budget. Arid and semiarid areas with unpaved and unvegetated land cover are particularly prone to windblown dust, which is often attributed to high particulate matter (PM) pollution in such areas. Yet, windblown dust is poorly represented in existing regulatory air quality models. In a study by the authors on modeling episodic high PM events along the US/Mexico border using the state-of-the-art CMAQ/MM5/SMOKE air quality modeling system [Choi, Y.-J., Hyde, P., Fernando, H.J.S., 2006. Modeling of episodic particulate matter events using a 3D air quality model with fine grid: applications to a pair of cities in the US/Mexico border. Atmospheric Environment 40, 5181–5201], some of the observed PM₁₀ NAAQS exceedances were inferred as due to windblown dust, but the modeling system was incapable of dealing with time-dependent episodic dust entrainment during high wind periods. In this paper, a time-dependent entrainment parameterization for windblown dust is implemented in the CMAQ/MM5/SMOKE modeling system with the hope of improving PM predictions. An approach for realizing windblown dust emission flux for each grid cell over the study domain on an hourly basis, which accounts for the influence of factors such as soil moisture content, atmospheric stability and wind speed, is presented in detail. Comparison of model predictions with observational data taken at a pair of US/Mexico border towns shows a clear improvement of model performance upon implementation of the dust emission flux parameterization.     

表征室外人体暴露的监测网络设计(续完)

对悬浮颗粒物室外人体暴露的测定一直受到可用资源的限制。设计有效的网络就要求对测定方法的选择、采样点的数量、采样时间、采样频率等进行调整。采样位置要求能表征因周围污染源对附近地区和城市最小影响的空间数值。虽然大多数判定PM是否达标的测定方法是每第3天至第6天的24h监测，但是室外人体暴露的评价要求连续监测一整天。最好有1h或更短时间的监测时段。更详细的粒径大小和化学性质数据也很有必要，因为较小的颗粒及其特殊的化学物质要比总的样品质量更有助于反映对健康的不良影响。     

表征室外人体暴露的监测网络设计(续一)

对悬浮颗粒物室外人体暴露的测定一直受到可用资源的限制，设计有效的网络就要求对测定方法的选择、采样点的数量、采样时间、采样频率等进行调整。采样位置要求能表征因周围污染源对附近地区和城市最小影响的空间数值。虽然大多数判定PM是否达标的测定方法是每第3天至第6天的24h监测，但是室外人体暴露的评价要求连续监测一整天，最好有1h或更短时间的监测时段。更详细的粒径大小和化学性质数据也很有必要，因为较小的颗粒及其特殊的化学物质要比总的样品质量更有助于反映对缝康的不良影响。