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Measurements of the molecular composition of organic aerosol (OA) constituents improve our understanding of sources, formation processes, and physicochemical properties of OA. One instrument providing such data at a time resolution of minutes to hours is the chemical ionization time-of-flight mass spectrometer with filter inlet for gases and aerosols (FIGAERO-CIMS). The technique collects particles on a filter, which are subsequently desorbed, and the evaporated molecules are ionized and analyzed in the mass spectrometer. However, long-term measurements using this technique and/or field deployments at several sites simultaneously require substantial human and financial resources. The analysis of filter samples collected outside the instrument (offline) may provide a more cost-efficient alternative and makes this technology available for the large number of particle filter samples collected routinely at many different sites globally. Filter-based offline use of the FIGAERO-CIMS limits this method, albeit to particle-phase analyses, which is likely at a reduced time resolution compared to online deployments. Here we present the application and assessment of offline FIGAERO-CIMS, using Teflon and quartz fiber filter samples that were collected in autumn 2018 in urban Beijing. We demonstrate the feasibility of the offline application with a "sandwich" sample preparation for the over 900 identified organic compounds with (1) high signal-to-noise ratios, (2) high repeatability, and (3) linear signal response to the filter loadings. Comparable overall signals were observed between the quartz fiber and Teflon filters for 12 and 24 h samples but with larger signals for semi-volatile compounds for the quartz fiber filters, likely due to adsorption artifacts. We also compare desorption profile (thermogram) shapes for the two filter materials. Thermograms are used to derive volatility qualitatively based on the desorption temperature at which the maximum signal intensity of a compound is observed (Tmax⁡). While we find that Tmax⁡ can be determined with high repeatability (± 5.7 ∘ C) from the duplicate tests for one filter type, we observe considerable differences in Tmax⁡ between the quartz and Teflon filters, warranting further investigation into the thermal desorption characteristics of different filter types. Overall, this study provides a basis for expanding OA molecular characterization by FIGAERO-CIMS to situations where and when deployment of the instrument itself is not possible. [ABSTRACT FROM AUTHOR]

Measurements of the molecular composition of organic aerosol (OA) constituents improve our understanding of sources, formation processes, and physicochemical properties of OA. One instrument providing such data at a time resolution of minutes to hours is the Chemical Ionization time-of-flight Mass Spectrometer with Filter Inlet for Gases and AEROsols (FIGAERO-CIMS). The technique collects particles on a filter, which are subsequently desorbed, and the evaporated molecules are ionized and analyzed in the mass spectrometer. However, long-term measurements using this technique and/or field deployments at several sites simultaneously, require substantial human and financial resources. The analysis of filter samples collected outside the instrument (offline) may provide a more cost-efficient alternative and makes this technology available for the large number of particle filter samples collected routinely at many different sites globally. Filter-based offline use of the FIGAERO-CIMS limits this method albeit to particle-phase analyses, likely at reduced time resolution compared to online deployments. Here we present the application and assessment of offline FIGAERO-CIMS, using Teflon and Quartz fiber filter samples that were collected in autumn 2018 in urban Beijing. We demonstrate the feasibility of the offline application with "sandwich" sample preparation for the identified over 900 organic compounds with (1) high signal-to-noise ratios, (2) high repeatability, and (3) linear signal response to the filter loadings. Comparable overall signals were observed between the Quartz fiber and Teflon filters for 12-h and 24-h samples, but with larger signals for semi-volatile compounds for the Quartz fiber filters, likely due to adsorption artifacts. We also compare desorption profile (thermogram) shapes for the two filter materials. Thermograms are used to derive volatility qualitatively based on the desorption temperature at which the maximum signal intensity of a compound is observed (Tmax). While we find that Tmax can be determined with high repeatability for one filter type, we observe considerable differences in Tmax between the Quartz and Teflon filters, warranting further investigation into the thermal desorption characteristics of different filter types. Overall, this study provides a basis for expanding OA molecular characterization by FIGAERO-CIMS to situations where and when deployment of the instrument itself is not possible. [ABSTRACT FROM AUTHOR]

Metals in atmospheric fine particulate matter (PM 2.5) are presumed to have toxic effects. For environmental epidemiological studies, measuring the metallic components of PM 2.5 collected by personal samplers and quartz fiber filters (QFF) has two key advantages: reducing exposure misclassification and enabling analyses of multiple (organic and inorganic) components on a single filter. We developed a sensitive, low-sample-consumption method to quantify the metallic components of PM 2.5 collected on QFFs using micro-synchrotron radiation X-ray fluorescence (μ-SRXRF). Teflon filter is used here as a reference to test the substrate applicability of QFF. This method requires only a 5-mm-diameter portion of a QFF and can simultaneously quantify 15 metals with atomic numbers Z = 19–34 (i.e., K–Se, excluding Sc). The analysis time for each sample was 120–360 s, and the method detection limits were 0.04–36.6 ng/m3. We validated this method by performing cross-comparisons with two external methods: offline inductively coupled plasma mass spectrometry (ICP-MS) and online X-ray fluorescence (XRF). The slopes of the linear fits between the μ-SRXRF and offline ICP-MS methods varied from 0.40 to 1, with R2 values ranging from 0.62 to 0.98. The slopes of the linear fits between the μ-SRXRF and online XRF methods were between 0.29 and 0.89, with R2 values ranging from 0.39 to 0.80. We applied the proposed method to analyze 391 personal PM 2.5 samples collected in an epidemiological study conducted in urban Beijing. By comparing the results with the ambient concentrations from a fixed monitoring site, we found that the concentrations of some metallic components in personal PM 2.5 samples were significantly different from those in the corresponding fixed-site samples, with up to an order of magnitude difference. Because personal sampling can reduce the potential for exposure misclassifications, the high-resolution temporal analysis of metallic components in personal samples using the μ-SRXRF method could be a useful approach for exploring the health risks and identifying the sources of metallic components of PM 2.5. [Display omitted] • A sensitive and low-sample consumption (5-mm-diameter) metallic analytical method. • 15 metals in PM 2.5 collected on quartz fiber filter can be quantified. • Cross-comparisons with offline ICP-MS and online XRF methods were performed for method validation. • Applied in an epidemiological study, to suggest exposure misclassifications. • May extent the understandings of environmental exposome and human health. [ABSTRACT FROM AUTHOR]

Fine particulate matter (PM2.5) is a major air pollutant worldwide. Characterizing its chemical compositions and source contributions is a critical prerequisite for effective control of PM2.5 pollution. This paper systematically reviews the sampling methods, chemical compositions, and source apportionments of PM2.5. Sampling methods have significant influences on the identification of chemical compositions and source contributions, with Quartz and Teflon filters being the most widely used. Receptor models are commonly adopted for identifying the sources of PM2.5, such as positive matrix factorization, chemical mass balance, principal component analysis, and UNMIX models, which have their respective advantages and limitations that determine their applications. The variations of PM2.5 compositions and sources in the past two decades in Beijing are also reviewed, which is the political, economic, and cultural center of China and is experiencing severe haze pollution events frequently. It was found that organic matters were the largest component (28.2%) in PM2.5, followed by sulfate (15.1%) during 2004–2013, which was overtaken by nitrate (14.9%) after 2013. Each PM2.5 source demonstrated significant seasonal and annual variations due to changes in climatic conditions and anthropogenic activities. Future research on the impacts of these external factors is urgently needed. This review is expected to provide valuable advice and evidence for those fast-growing megacities like Beijing to identify and control their PM2.5-related air pollution problems. [ABSTRACT FROM AUTHOR]

Abstract: Two semi-continuous Sunset carbon analyzers, with different peak inert mode temperatures (615 and 740 °C), were simultaneously operated to measure fine particulate organic carbon (OC) and elemental carbon (EC) using a thermal–optical transmittance method at an urban site in Beijing, China, from 16 August to 3 September 2006 during the CAREBeijing 2006 campaign. Excellent agreements were obtained between the collocated semi-continuous carbon analyzers, with slopes of 1.02 (R 2 = 0.91) for OC and 1.06 (R 2 = 0.93) for EC, resulting in very similar average EC/total carbon (TC) ratios of ∼0.36. These results imply that the different peak inert mode (100% helium) temperatures did not cause significant biases on the semi-continuous OC and EC measurements. However, it was found that the EC/TC ratio was greatly influenced by the accumulated refractory particles remaining on a quartz filter (PM refractory). Fresh quartz filters, with low PM refractory loadings, which is defined as a laser correction factor ≥0.94, gave ∼8–10% lower EC/TC ratios than aged quartz filters with high PM refractory loadings. The linear regression slope between EC and optically measured EC (OPT-EC) was much higher with fresh quartz filters (slope = 1.03, R 2 = 0.96) than aged quartz filters (slope = 0.89, R 2 = 0.95), suggesting the underestimation of EC on fresh quartz filters by ∼15% compared to those measured on aged quartz filters. Authentic standard humic-like substances (HULIS) on the clean quartz filter showed the highest extent of pyrolyzed organic carbon (POC) formation (47.4% in total detected carbon mass), followed by those on the Asian dust loaded quartz filter (37%) and the refractory urban pollutant loaded quartz filter (34.1%), indicating that the Asian dust and refractory urban pollutant reduced the POC formation from the HULIS. Thus, this study suggested that the PM refractory loading plays an important role in the semi-continuous OC and EC measurements by altering the degree of POC formation in the inert atmosphere. [Copyright &y& Elsevier]

As brown carbon (BrC) consists of a collection of light-absorbing organic compounds, there is unlikely an individual substance that can be used as a proxy of all BrC constituents. Hence, available methods for distinguishing BrC from black carbon (BC) are often flawed. Moreover, the use of household solid fuels for winter rural heating is a common practice in northern China that significantly contributes to air pollution; however, it is unclear whether the intensive consumption of solid fuels during the heating season influences the yearly BrC emissions and the seasonal features of ambient BrC in northern China, which is a concern for future BrC control. Thus, a reliable method is necessary for determining the concentrations and optical properties of ambient BrC in different seasons. In this study, four typical months were selected to represent the four seasons of the year in Beijing. Daily atmospheric samples were collected using quartz filters for the analysis of BrC and BC. The integrating sphere (IS) approach was used for the first time to separate the light absorption of BrC from that of BC in ambient PM 2.5. We found that the yearly average abundance of BrC was 0.82 ± 0.44 μg m−3, peaking at 2.31 ± 0.44 μg m−3 in winter, followed by autumn, spring, and summer. Meanwhile, the solar energy absorption by BrC relative to that by BrC + BC across 350–850 nm (F BrC) was the highest in winter (21.78 ± 3.56%), followed by autumn (11.53 ± 5.29%), spring (6.38 ± 4.06%), and summer (4.26 ± 2.57%). The seasonal variations in BrC abundance and absorption share were consistent with the use of household heating practices (highest in winter and minor uses in late autumn and early spring), with biomass and/or coal being the dominant energy types. As low-efficiency burning of solid biomass fuels and fossil fuels is considered an important source of BrC, the aforementioned correlation suggests that rural residential heating plays a dominant role in controlling the seasonal features of BrC and should therefore be a main focus for BrC control in northern China. Hence, the ongoing pursuit of clean heating (switching from coal to gas or electricity) in northern China will help to mitigate the climate-warming effects of both BrC and BC and offset some of the adverse impacts of clean air efforts on climate. Our findings also have wider implications for pollution mitigation in other global regions that use solid fuels. • Brown and black carbon of Beijing PM 2.5 samples optically separated by integrating sphere method. • The seasonality of BrC parameters suggests taking household solid fuels as control focus. • The results also senseful even in other regions of the world using solid fuels. [ABSTRACT FROM AUTHOR]