X1.application of Fourier Transform Infrared Spectroscopy in The Study of Application of Fourier Transform Infrared Spectroscopy in The Study Of, 2010

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Application of Fourier Transform Infrared Spectroscopy in the Study of Atmospheric Heterogeneous Processes
Yue Zhao a; Zhongming Chen a a State Key Laboratory of Environmental Simulation and Pollution Control, College of Environmental Sciences and Engineering, Peking University, Beijing, China Online publication date: 14 January 2010
To cite this Article Zhao, Yue and Chen, Zhongming(2010) 'Application of Fourier Transform Infrared Spectroscopy in the
Study of Atmospheric Heterogeneous Processes', Applied Spectroscopy Reviews, 45: 1, 63 91 To link to this Article: DOI: 10.1080/05704920903435516 URL: http://dx.doi.org/10.1080/05704920903435516
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Applied Spectroscopy Reviews, 45:6391, 2010 Copyright Taylor & Francis Group, LLC ISSN: 0570-4928 print / 1520-569X online DOI: 10.1080/05704920903435516
Application of Fourier Transform Infrared Spectroscopy in the Study of Atmospheric Heterogeneous Processes
YUE ZHAO AND ZHONGMING CHEN
State Key Laboratory of Environmental Simulation and Pollution Control, College of Environmental Sciences and Engineering, Peking University, Beijing, China
Downloaded By: [Chen, Zhongming] At: 00:25 15 January 2010
Abstract: Atmospheric heterogeneous processes associated with the complex behavior of atmospheric particles may play a crucial role in atmospheric chemistry and global climate change. Many of these heterogeneous processes have been widely investigated in detail over the years, including heterogeneous reactions on the surface of aerosol particles, aerosol hygroscopicity, as well as aerosol chemical compositions. As a fast, sensitive, precise, nondestructive, in situ, and online experimental technique, Fourier transform infrared (FTIR) spectroscopy has played a signicant role in investigating atmospheric heterogeneous processes. On the basis of the mechanisms and characteristics of various FTIR techniques, this work presents a review of the applications of in situ FTIR spectroscopy in atmospheric heterogeneous processes study, and future development directions for FTIR spectroscopy are proposed considering current and future research needs for heterogeneous processes. Keywords: FTIR spectroscopy, atmospheric particle, heterogeneous reaction, hygroscopic property, chemical composition
Introduction
As a complicated heterogeneous system, the troposphere contains a variety of atmospheric particles, including directly emitted primary particles such as mineral dust, sea salts, and soot as well as secondary particles formed through photochemical reactions; that is, sulfate, nitrate, and secondary organic aerosol (SOA). Because they originate from different sources, there exist large differences in size distribution and chemical composition of various particles, which dominate their atmospheric lifetimes and complex physiochemical properties. It is well known that aerosol particles play a key role in the atmosphere, not only affecting atmospheric acid deposition by directly participating in atmospheric cloud formation and wet deposition processes but also impacting local and global climate through absorption and scattering solar radiation as well as acting as cloud condensation nuclei (1, 2). Light absorption and scattering of aerosol particles can also affect visibility (3) and atmospheric photochemical processes (4). In addition, the surfaces of aerosol particles can
Address correspondence to Zhongming Chen, State Key Laboratory of Environmental Simulation and Pollution Control, College of Environmental Sciences and Engineering, Peking University, Beijing 100871, China. E-mail: zmchen@pku.edu.cn
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provide large quantities of active sites for heterogeneous reactions, and these heterogeneous reactions not only provide a new pathway for the chemical transformation of atmospheric trace gases, thereby having a signicant effect on the chemical balance and oxidation capacity of the atmosphere, but can change particle size and composition, thus in return affecting atmospheric lifetimes and physiochemical properties of atmospheric particles (1, 4, 5). Moreover, as the carriers of toxic substances, atmospheric particles, particularly ne particles, can enter the human respiratory system, thus producing an adverse health effect (6). Atmospheric particles have received increasingly extensive attention over the years as a result of their signicant environment, climate, and health effects, and atmospheric heterogeneous processes associated with the complex environmental behaviors of atmospheric particles have been the focus of related research. As a molecular vibration spectroscopy, Fourier transform infrared (FTIR) spectroscopy provides a nondestructive and in situ method of analysis with advantages of high sensitivity, precision, and time resolution (7). Therefore, it has been widely used to investigate atmospheric heterogeneous processes, including heterogeneous reactions on the surface of atmospheric particles and hygroscopic behaviors and chemical compositions of ambient aerosols. Here we present a review on the applications of in situ FTIR spectroscopy in the three areas mentioned above aiming at understanding the development, advantages, disadvantages, and future directions of FTIR spectroscopy for atmospheric heterogeneous processes studies.
Fourier Transform Infrared Spectroscopy

FTIR spectroscopy is an analytical technique capable of providing detailed information on the molecular level for atmospheric particles and has played a signicant role in the study of atmospheric heterogeneous processes. Particularly, a number of accessory techniques such as transmission, diffuse reectance, and attenuated total refection (ATR) as shown in Figure 1 have been combined with FTIR, generating three widely used FTIR techniques; namely, transmission FTIR (T-FTIR), diffuse reectance infrared Fourier transform spectroscopy (DRIFTS), and attenuated total refection FTIR (ATR-FTIR). These have greatly expanded the applications of FTIR spectroscopy to atmospheric heterogeneous processes. Due to the different principles, these three FTIR techniques have different characteristics and application scopes in the study of heterogeneous processes as described below. The principle of T-FTIR is that the infrared beam radiating to the surface of a particle sample can be refracted into and then penetrate the whole sample pressed or coated onto a metal grid after interacting with sample molecules. Therefore, the transmission infrared beam contains information of the molecular structure of the sample (7) (Figure 1a). Because the infrared rays can fully interact with molecules when penetrating the sample, T-FTIR provides a good qualitative and quantitative method of analysis, with advantages of higher sensitivity, precision, and signal-to-noise ratio (SNR) and is still reliable even in wet conditions. However, this method has high requirements on the selection and preparation of particle samples; that is, relatively small accumulation thickness of particle samples with the diameter of a single particle in the nano- or sub-micro-scale ensuring that the infrared rays penetrate the samples easily and consistent accumulation thickness and compaction density of samples assuring the repeatability of experiments. A study by Jie et al. (8) demonstrated that the T-FTIR method is of good repeatability even under the condition where the particles were exposed to high-humidity air. For the DRIFTS method (see Figure 1b), the infrared beam from the IR source is focused onto the particle sample by an ellipsoidal mirror. After interacting with the sample
Atmospheric Heterogeneous Processes
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Figure 1. Schematic diagram of accessories for T-FTIR, DRIFTS, and ATR-FTIR, respectively. (a) Accessory of T-FTIR; (b) accessory of DRIFTS; (c) accessory of ATR-FTIR.
molecules, the infrared rays are partly diffused through the surface of the sample in various directions. These diffusely reected rays are then collected by the other ellipsoidal mirror and focused onto the detector (7). The DRIFTS method can be used to study microsize particles, but the uniformity and compaction density of samples greatly affect the repeatability of analysis. In addition, weak diffuse reectance rays result in a higher detection limit: thus, it is difcult to observe the relatively small changes of molecular structure information of particles. Furthermore, in order to avoid an interference resulting from specular reection of the sample surface, samples are required to be of high surface roughness. In the ATR-FTIR method, particle samples are deposited on the surface of a horizontal ATR crystal for spectroscopic analysis, as shown in Figure 1c. When the incidence angle of infrared rays is greater than the critical one, the incident infrared rays are totally internally reected at the interface of the ATR crystal and the sample where the infrared rays can penetrate into and interact with the sample (7). The effective path length for this interaction, namely, the penetration depth of infrared rays, is usually a few micrometers and depends on the refractive index of the ATR crystal and sample, the incidence angle, and the wavelength of the infrared rays. Several total reections occur as the infrared rays pass through the ATR crystal. In practice, enhancement of sensitivity and signal-to-noise ratio for the ATR method
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is achieved by increasing the number of total reections and the penetration depth of infrared rays (7). Compared to T-FTIR and DRIFTS, ATR-FTIR has simpler sample preparation without special requirements for the size and shape of sample and is particularly ideal for spectroscopic observation of physical and chemical processes on the surface of thin lm and particle samples containing liquid water, which has largely expanded the application of FTIR spectroscopy.
Specic Applications of FTIR Spectroscopy

FTIR in Situ Study of Heterogeneous Reactions on the Surface of Atmospheric Particles In recent years it has been noted that heterogeneous reactions of tropospheric trace gases on atmospheric particles may play a signicant role in atmospheric chemistry and global climate change. However, it has been known that atmospheric heterogeneous reactions are extremely complicated, which is affected by a variety of factors such as humidity, temperature, solar radiation, and oxidant level as well as the properties of reactive particles and gases. Therefore, it is a challenge to study atmospheric heterogeneous reactions. The constraint on methods and techniques has become a major factor to restrict research progress in this eld. In the early laboratory studies of atmospheric heterogeneous reactions, gas chromatography (GC) was widely used. Using this method, Goss (9, 10) and Goss and Eisenreich (11) investigated the adsorption reactions of volatile organic compounds (VOCs) such as acetone, ethanol, toluene, and diethyl ether on mineral dust and determined the equilibrium adsorption constant of these VOCs in different relative humidities (RHs). The GC method is capable of precisely measuring the concentrations of gaseous organic compounds, but it cannot directly provide specic information about the surface of the particles, thus making it difcult to further understand atmospheric heterogeneous reactions. A Knudsen cell reactor has been widely used in determining the kinetics of heterogeneous reactions over the years (1117). However, a Knudsen cell is a low-pressure ow reactor in which the surface of the particles is only exposed to the reactant molecules. Therefore, it cannot be used for laboratory investigations of heterogeneous reactions under atmosphericlly relevant conditions such as general pressure and varying RH. Therefore, the extrapolation of experimental results by a Knudsen cell to atmospheric conditions is problematic. As a reactor capable of simulating atmospheric conditions most closely, an aerosol chamber has also been used in the study of heterogeneous reactions; for example, heterogeneous reactions of N2 O5 on the surface of NaCl particles (18) and secondary organic aerosol (SOA) formation from aromatics, aldehydes, isoprene, and -pinene by acid-catalytic heterogeneous reactions (1923). However, an aerosol chamber has the disadvantages of severe wall effects and high cost for manufacture, maintenance, and operation, which has greatly limited its application. In addition, surface analysis techniques including X-ray photoelectron spectroscopy (XPS) (24), X-ray diffraction (XRD) (25), and electronic microscopy (EM) (26) have been in the study of atmospheric heterogeneous reactions. Sensitive, precise, continuous, and rapid characterization of reactants and products without interrupting the reaction processes can be achieved using in situ FTIR spectroscopy, enabling close following of the reaction progress and better probing the reaction kinetics and mechanisms. FTIR spectroscopy has been widely used to study heterogeneous reactions since its introduction in the 1970s (7), and a summary of representative reported studies is shown in Table 1. In the early 1980s, many researchers successfully used FTIR to investigate the adsorption and catalytic reactions of SO2 and H2 S on the surface of oxide
Table 1 Summary of selected studies on atmospheric heterogeneous reactions

FTIR DRIFTS DRIFTS T-FTIR T-FTIR T-FTIR DRIFTS FTIR T-FTIR T-FTIR T-FTIR Knudsen cell Aerosol chamber, Knudsen cell Knudsen cell SEM SEM (36) (37) (31) (33) (34) (50) (61) (39) (51) (40) Other techniques Measurements Reference
Reactive species
Particle samples
NO2 , HNO3
NaCl
NO2
NO2 Diffuse reectance, UV-vis Diffuse reectance, UV-vis Knudsen cell
synthetic sea salt mixtures Al2 O3 , TiO2
Surface adsorption, uptake coefcient, reaction mechanism, and orders Surface adsorption, uptake coefcient, reaction mechanism, and orders Surface adsorption
NO2
SiO2
NO2 NO2 , HNO3
Al2 O3 , Fe2 O3 , TiO2 Al2 O3
NO2 , HNO3
Soot aerosol
SO2
-Al2 O3 , MgO
HNO3 , H2 O
SiO2 , -Al2 O3 , TiO2 , -Fe2 O3 , CaO, MgO SiO2 , Al2 O3 , Fe2 O3 , CaO TiO2 , T-FTIR DRIFTS XPS Knudsen cell Knudsen cell
Surface adsorption, reaction products identication Surface adsorption and uptake coefcient Surface adsorption, reaction mechanism, uptake coefcient Surface adsorption, reaction products identication, uptake coefcient Surface adsorption, reaction mechanism, uptake coefcient Surface adsorption, reaction mechanism, uptake coefcient Surface adsorption, reaction products identication, uptake coefcient
-Fe2 O3 , -Al2 O3 , SiO2
CH3 CHO, CH3 C(O)CH3 , CH3 CH2 CHO CH3 OH, HCHO, CH3 COOH SO2 , NO2
Mineral dust
H2 O, SO2 , HNO3 T-FTIR & ATR-FTIR DRIFTS & LP-FTIR
CaCO3
SO2
Al2 O3 , CaO, TiO2 , MgO, FeOOH, Fe2 O3 , SiO2
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Surface adsorption, reaction products (38) identication, uptake coefcient Surface adsorption, reaction mechanism, (41) uptake coefcient Surface adsorption, reaction products (43) identication and mechanism Surface adsorption, reaction products (45) identication and mechanism, uptake coefcient (Continued on next page)
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FTIR DRIFTS DRIFTS Raman spectroscopy IC Other techniques Measurements Reference (46) (49) Surface adsorption, reaction orders and mechanism, uptake coefcient Surface adsorption, reaction mechanism, uptake coefcient SEM QMS GC/GC-MS, HPLC-MS (57) (67) (58) (59) DRIFTS& ATR-FTIR DRIFTS ATR-FTIR & LP-FTIR ATR-FTIR Surface adsorption and reaction mechanism Surface adsorption and reaction mechanism Reaction products identication and mechanism Reaction products identication Atomic force microscopy HPLC, IC Aerosol chamber Aerosol chamber (60) (55) (64) (65) FTIR FTIR Reaction products identication and mechanism Surface adsorption, reaction mechanism, uptake coefcient Surface adsorption, reaction products identication Surface adsorption, reaction products identication, uptake coefcient
Table 1 Summary of selected studies on atmospheric heterogeneous reactions (Continued)
Reactive species
Particle samples
SO2 , O3
CaCO3
COS
SO2 , OH, O3
Hematite, NaCl, hematite-NaCl mixtures NaCl-MgCl2 mixtures
COS
MgO
O3
Cypermethrin lms
O3
O3
MACR, MVK, O3
4-Carboxybenzophenone(4-CB) lms 7-Octenyltric hlorosilane ATR-FTIR SAMs SiO2 T-FTIR
CH3 COOH
Calcite aerosol
D4, D5, O3
Hematite, kaolinite, calcite, quartz
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particles like Al2 O3 and TiO2 (2730). Early work using infrared spectroscopy was mainly T-FTIR spectroscopy. In the following years, diffuse reectance and ATR techniques have made a rapid development and been combined with FTIR spectrometry, resulting in greatly expanding the application of FTIR spectroscopy to the study of atmospheric heterogeneous reactions. Since the 1990s, the heterogeneous reactions of trace gases in the troposphere including SO2 , NOx , HNO3 , and VOCs on the surface of various atmospheric particles have received increasing extensive attention, and T-FTIR (3135) and DRIFTS (36, 37) have been the two major tools for these studies. These early laboratory studies of atmospheric heterogeneous reactions mainly focused on the identication of reaction products and exploration of reaction mechanisms, and it has been well demonstrated that various trace gases in the troposphere could interact with the surface of atmospheric particles. However, little is known about heterogeneous reaction kinetics and to what extent these heterogeneous reactions can occur on the surface of the particles. Therefore, in order to quantify the uptake of trace gases onto the particle surfaces and to assess the importance of heterogeneous reactions in atmospheric chemistry, the kinetics of heterogeneous reactions has been the focus of a number of studies during the last few years. The uptake coefcient ( ) is the most signicant and widely measured kinetic parameter, which is simply a measure of the probability of the gas-phase molecule loss upon a collision of gas-phase molecule with the surface of particles, through either adsorption or reaction. It is dened by Eq. (1) (38): = the net loss of molecules from the gas phase to the surface per second the total number of gas surface collision per second (1)
The Knudsen cell reactor has been widely used to determine the uptake coefcient of gas molecules on the surface of the particles, but the Knudsen cell reactor is operated at very low pressure, which is very different from real atmospheric conditions, resulting in large uncertainties of measurement results. Because the Knudsen cell reactor is not capable of providing information on particle surfaces, many researchers have further utilized FTIR techniques to observe the physical and chemical changes on particle surfaces besides using the Knudsen cell reactor for the uptake coefcient determination (3843). With the development of the FTIR spectrometer and spectroscopy, the sensitivity and precision of quantitative analysis by FTIR were considerably improved, and T-FTIR and DRIFTS have been gradually applied to determining the uptake coefcients of a variety of trace gases on the surface of the particles such as SO2 (4448), COS (49), NOx and HNO3 (5052), and VOCs (5355). It should be noted that the value of the uptake coefcient determined by T-FTIR or DRIFTS is generally three to four orders of magnitude lower than the value measured from the Knudsen cell as shown in Table 2, possibly due to the different measurement principles and operation conditions between these two methods. On the one hand, the Knudsen cell technique determines the rate loss of gaseous reactants during exposure, whereas the FTIR method measures the formation rate of products on the particle surfaces. On the other hand, the Knudsen cell is a low-pressure reactor where only the gaseous reactant molecules are exposed to the clean surface of the particles, and the FTIR reactor generally runs under general pressure. Therefore, the number of surface reactive sites for adsorbing reactant molecules greatly decreases because of signicantly competitive depletion by other gaseous species such as N2 , O2 , and H2 O. Therefore, the value of the uptake coefcient determined by FTIR should be much lower than that obtained by the Knudsen cell. Because the FTIR reactor is more capable of simulating atmospheric conditions than the Knudsen cell, the uptake coefcients determined by T-FTIR or DRIFTS are considered as being closer to actual values in the atmosphere.
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Table 2 A comparison of initial uptake coefcients of gas species on various particles measured with Knudsen cell and FTIR spectroscopy Gas species SO2 Particles Mineral dust Uptake coefcienta 106 1010 107 105 1010 107 108 108 to 1010 105 107 to 108 105 109 103 106 to 107 105 109 106 109 Method Knudsen cell DRIFTS DRIFTS Knudsen cell DRIFTS Knudsen cell Knudsen cell DRIFTS Knudsen cell T-FTIR Knudsen cell T-FTIR Knudsen cell T-FTIR Knudsen cell DRIFTS Knudsen cell T-FTIR Reference (41) (44) (39) (48) (41) (34) (50) (42) (51) (42) (51) (42) (51) (38) (53) (40) (54)
NO2
-Al2 O3 Iron oxides Mineral dust Al2 O3 -Al2 O3 SiO2 CaO
HNO3
HCHO CH3 C(O)CH3

a
-Al2 O3 SiO2
All of the initial uptake coefcients are calculated with BET surface area of particles.
It is of great practical signicance to study atmospheric heterogeneous reactions considering the changes of RH in reaction system, and T-FTIR and DRIFTS have also been used to investigate the inuence of varying RH on heterogeneous reactions (43, 46, 47, 5456). In a study by Shaka et al. (57) it was demonstrated that DRIFTS can be used to probe the uptake and reactions of gas in and on liquid lms on solid substrate powders. However, both of these two methods are not normally applicable to investigating the structure of adsorption water on the particle surfaces, mainly due to the interference resulting from infrared absorption by water vapor to the infrared spectra. For the ATR-FTIR technique, the incidence infrared light are totally reected back into the ATR crystal after penetrating into samples for a few micrometers, thus effectively avoiding the disturbance on infrared spectra of samples from water vapor and showing a large improvement in the study of a water-containing system. In this regard, Al-Hosney and Grassian (43) used ATR-FTIR to investigate water adsorption on the surface of CaCO3 particles and further utilized T-FTIR to elucidate the role of surface adsorbed water in the adsorption reactions of SO2 and HNO3 . Shaka et al. (57) also carried out some ATR-FTIR experiments on an Na2 SO3 bulk solution, which are not experimentally feasible using DRIFTS. In addition, ATR-FTIR is a particularly ideal tool for the study of heterogeneous reactions on organic thin lms or self-assembled monolayers (SAMs), which closely mimic organics adsorbed on environmental surfaces such as buildings, vegetation, and atmospheric particles. This is due to the ATR crystal providing an available interface to generate organic lms or SAMs (5860). Because heterogeneous reaction products may exist in both gas and particle phases, a
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Figure 2. Schematic diagram of an ATR-LP-FTIR system for the study of heterogeneous reactions. Reprinted with permission from Segal-Rosenheimer and Dubowski (58). Copyright American Chemical Society, 2007.
number of studies on heterogeneous reactions have been performed by combining long path cell (LP)-FTIR, which is particularly applicable to gas-phase observations, with DRIFTS or ATR-FTIR (see Figure 2), for the real-time and simultaneous monitoring of both gas and particle phase (45, 48, 58), enabling full information on kinetics and mechanisms of the reactions to be obtained. Generally, particle samples for atmospheric heterogeneous reaction studies mentioned above are coated or pressed onto the sample holder such as a metal grid, ATR crystal, or sample cup, as shown in Figure 1. The FTIR spectroscopy was employed to directly monitor the chemical change of particles surface during the reaction process. Recently, Prince et al. (6164) designed an environmental aerosol chamber coupled with a FTIR spectrometer to in situ probe the heterogeneous reactions of NO2 , HNO3 , SO2 , and acetic acid with soot and/or calcite aerosols. Quite recently, Navea et al. (65, 66) utilized the same chamber (Figure 3) to investigate the heterogeneous reaction of two cyclic volatile methylsiloxanes (cVMS), octamethylcyclotetrasiloxane (D4), and decamethylcyclopentasiloxane (D5) on the surface of mineral dust aerosol, and the uptake coefcients of these two compounds was determined using FTIR spectroscopy. The chamber is schematically shown in Figure 3. After adding the gas-phase reactant, the particle samples are introduced and suspended in the reaction chamber, which has been internally coated with a layer of PEP Teon to reduce reactivity and mitigate wall effects. The FTIR spectrometer was used to monitor the concentration of gas-phase species rather than the particles surface change, providing indirect information on heterogeneous reaction processes. Because the particles suspended in the chamber are isolated, this specially designed chamber can mimic the atmospheric relevant heterogeneous processes more closely than infrared cell used by T-FTIR, ATR-FTIR, or DRIFTS, where the bulk powder samples are obtained. However, due to the lack of information on the particles in this approach, other techniques feasible to characterize surface species is highly required for exploring detailed heterogeneous reaction mechanisms. Although in situ FTIR spectroscopy is an excellent method for qualitative analysis with advantages of high sensitivity, precision, and time resolution. There are still certain limitations on quantitative analysis, especially when infrared absorption peaks of different molecules and/or functional groups overlap with each other. In this regard, a number of techniques or methods in addition to FTIR spectroscopy, including high-performance liquid chromatography (HPLC), gas chromatography (GC), ion chromatography (IC), mass
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Figure 3. Schematic diagram of the environmental aerosol chamber and associated instrumentation for spectroscopic study of heterogeneous reactions. Reprinted with permission from Navea et al. (65). Copyright Elsevier, 2009.
spectroscopy (MS), and various surface analysis techniques, have been frequently used in laboratory studies to provide more qualitative and quantitative information on heterogeneous reactions (4649, 54, 55, 67), not only verifying the reliability of FITR measurement but enabling further elucidation of the nature of heterogeneous reactions. FTIR in Situ Study of Hygroscopic Properties of Atmospheric Particles The hygroscopic properties of atmospheric particles largely inuence the size distribution, the optical and precipitation properties, and the chemical reactivity of the particles, affecting relevant physiochemical processes relating to air quality, visibility, and climate change. In recent years aerosol hygroscopic properties have received wide attention, and methods for laboratory study have continued to evolve and develop. Electrodynamic balance (EDB) is a technique capable of levitating a single aerosol particle in a given environment, allowing for simulating aerosols in the real atmosphere where both homogeneous and heterogeneous nucleation of aerosol particles can be restrained so that the metastable solid and supersaturated state in aerosol can occur frequently (6870). Therefore, EDB has been widely used for the study of aerosol hygroscopic properties over the years. Single EDB can be applied to in situ investigation of the changes of mass fraction of solute with varying RH during the deliquescence and eforescence cycles of aerosol particles, further assessing their hygroscopic capability (70). Combining EDB with Raman spectrometry (EDB-Raman) enables the probing of aerosol hygroscopic properties on a molecular level. This may be useful for elucidating the physical and chemical changes such as phase transition, formation of contact ion pairs (CIPs), and changes in water molecular structure in the deliquescence and eforescence processes of aerosol particles (7176). Even though detailed information on
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interactions between the ions and/or molecules in a supersaturated aerosol are accessible using an EDB-Raman system, there are strong physical morphology-dependent resonances (MDRs) overlapping with the Raman spectra of chemical interactions for regular spherical droplets levitated in EDB. This results in large difculties in the identication of minor spectra changes related to the formation of CIPs and greatly restricts the analysis of water molecular structure as a result of a big distortion for O-H stretching vibration envelope from the strong MDRs (7476). Recently, Zhangs group successfully developed a confocal Raman system to study the hygroscopic properties of single supersaturated aerosol droplet deposited on a quartz substrate (77). Because the droplet on the quartz substrate is a half-ellipsoid rather than a regular sphere, there is no MDR disturbance on Raman spectra of chemical interactions for half-ellipsoidal droplet; the Raman spectra with high SNR can be obtained with confocal Raman spectroscopy. More detailed information on chemical interactions related to the formation of CIPs can also be obtained from the weak bands, and water molecular structures in supersaturated droplets can be effectively investigated by the clearly discernible O-H stretching vibration envelope (7780). Besides, the hygroscopicity tandem differential mobility analyser (H-TDMA) technique can also be used to study the aerosol hygroscopic properties (8183). This technique only enables the measurement of the change in particle size for varying RH to obtain the hygroscopic growth factor (HGF) of the aerosol particles. As another molecular vibration spectroscopy, FTIR spectroscopy can provide detailed information on molecular structures of aerosol particles, without MDRs disturbance on infrared spectra for supersaturated aerosol droplets holding a spherical shape. Thus it has been widely used for the study of aerosol hygroscopic properties. To the best of our knowledge, the successfully used FTIR techniques for aerosol hygroscopic properties study have mainly included aerosol ow tube (AFT)-FTIR, ATR-FTIR, and T-FTIR. DRIFTS is generally not applicable to the investigation of water-containing aerosol particles in particular droplets. The selected relevant studies described in detail in the following are listed in Table 3. As early as 1987, Grader et al (84) rstly applied FTIR spectroscopy to the investigations of the composition and water molecular structures of an individual supersaturated (NH4 )2 SO4 droplet levitated in EDB. Recently, an AFT system combined with an FTIR spectrometer has been widely used to study aerosol hygroscopic properties (8590). As shown in Figure 4, the AFT-FTIR system is generally composed of an aerosol generator, an aerosol dryer, an IR observation cell, a humidication system, and a pipeline system. Aerosol droplets produced from dilute solutions at given concentrations by an aerosol generator ow along with carrier gas under controlled RHs into the IR observation cell where the infrared spectra of aerosol droplets can be collected. Accordingly, with changing RHs of the carrier gas, AFT-FTIR has been used to probe the deliquescence and eforescence processes of aerosols as well as supersaturated structures (8790). By adding a temperature-controlling system, this method can be applied to the observation of phase transition behavior of aerosol particles at different temperatures (85, 86). However, these applications of AFT-FTIR have mainly focused on the study of macroscopic physiochemical properties of aerosol particles such as hygroscopic growth, hygroscopic curves (deliquescence point and eforescence point), and typical phase transitions. Moreover, the RHs of air ow in AFT are generally controlled by a special humidication system and thereby can not vary continuously during a single experiment. Zhao et al. (91) have recently developed a continuous sampling AFT-FTIR system that was successfully used to investigate the water molecular structures and formation of CIPs in supersaturated MgSO4 and NaClO4 aerosol droplets (92, 93). As shown in Figure 5, there is no special humidication system for this modied AFT-FTIR method. The aerosol droplets guided by the air pump owed in turn through a buffering
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Aerosol samples Measurements Reference (84) (85) (86) (87) (89) (91) (93) (94) (90) (88) (98) (99) (95) (96) (97) (100) (101) (102) (103) (104) Compositions and water molecular structures Phase transitions of aerosols with varying RH over the temperature range from 298 to 238 K Phase transitions of aerosols with varying RH over the temperature range from 293 to 252 K Effect of formic acid on the DRH of aerosols Hygroscopic growth of aerosol particles Structural changes of aerosol particles during the deliquescence and eforescence processes Water molecular structures and formation of CIPs in supersaturated aerosol droplets Structural changes of aerosol particles during the deliquescence and eforescence processes Hygroscopic property and hygroscopic growth of aerosol particles Water uptake and phase transitions of aerosols Retting of a standard ATR-FTIR setup through the observations of supersaturated aerosols Relationships between the photoreactivity of aqueous nitrate aerosols and the molecular and electronic structures of nitrate ions Hygroscopic behaviors of metastable particles, formation of CIPs and SIPs in supersaturated droplets Phase transitions and molecular structure changes during the deliquescence and eforescence processes of aerosols The effect of the relative humidity annealling on the hygroscopic properties of aerosol particles Hygroscopic growth of aerosol particles Adsorption of water on particle surfaces with varying RH Phase transitions of the thin lms with varying RH Phase transitions, DRH and ERH, hygroscopic growth factors, and water-to-solute ratio (WSR) of aerosol particles Phase transitions, DRH and ERH, water-to-solute ratio (WSR) of aerosol particles
Table 3 Summary of selected studies on aerosol hygroscopicity
FTIR
EDB-FTIR AFT-FTIR
Single supersaturated (NH4 )2 SO4 droplet NaCl, MgCl2 , NH4 HSO4 , and NH4 NO3 aerosols
AFT-FTIR
Malonic and oxalic acid aerosols
AFT-FTIR AFT-FTIR AFT-FTIR
NaCl aerosols Mixtures of NH4 +, SO4 2, H+ ions Supersaturated MgSO4 and NaClO4 aerosols
AFT-FTIR
Supersaturated NaClO4 aerosols
ATR-FTIR
NaClO4 aerosols
AFT-FTIR, TDMA AFT-FTIR ATR-FTIR
Nitrate salt aerosols Sodium oleate aerosols Supersaturated MgSO4 and NaClO4 aerosols
ATR-FTIR, UV/vis
Aqueous nitrate aerosols
ATR-FTIR
Mg(NO3 )2 aerosols
ATR-FTIR
NaNO3 aerosols
ATR-FTIR
NaCl, NaNO3 , and NaClO4 aerosols
ATR-FTIR T-FTIR T-FTIR
Micro-T-FTIR
Fine MgSO4 aerosols -Al2 O3 particles Mg(NO3 )2 thin lms formed by the reactions of nitric acid on the surface of MgO particles NaCl, NaNO3 , (NH4 )2 SO4 , and sea salt aerosols
Micro-T-FTIR
CH3 SO3 Na, CH3 SO3 NH4 , (CH3 SO3 )2 Mg, and (CH3 SO3 )2 Ca particles
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Figure 4. Schematic diagram of a traditional AFT-FTIR system for the observation of hygroscopic behaviors of aerosol particles in varying RHs. Reprinted with permission from N ajera (88). Copyright Elsevier, 2007.
cell and multistep desiccation cells into an IR observation cell with silicon windows. As the drying ability of the color-changed silica gel desiccants decreased with time, the air ow carrying aerosol droplets steadily and continuously increased in its RH (this process has been dened as a reverse desiccation process); thus, the reverse observation of the eforescence processes of aerosols with decreasing RH could be accessible using an FTIR spectrometer (91). Similarly, pure water could also be used to generate aerosol droplets,
Figure 5. Schematic diagram of a continuous sampling AFT-FTIR system for the observation of hygroscopic behaviors of aerosol particles in varying RHs. Reprinted with permission from Zhao et al. (93). Copyright PCCP Owner Societies, 2005.
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Figure 6. Schematic diagram of an ATR-FTIR system for the observation of hygroscopic behaviors of aerosol particles in varying RHs. Reprinted with permission from Li et al (95). Copyright Science in China Press, 2008.
and the air ow after passing through the multistep desiccation cells was increasingly wet, continuously humidifying aerosol particles deposited in advance on the silicon windows of the IR observation cell (91). Thus, the deliquescence processes of aerosol particles with increasing RH could also be observed. Because infrared spectra collected in the IR observation cell generally contained infrared absorption of both aerosol particle and gas phase, the heavy disturbance of water vapor on the O-H stretching and O-H bending vibration bands in the AFT-FTIR spectra of aerosols could not be avoided and to some extent restricted the investigation of water molecular structures of supersaturated aerosols. More recently, Zhang et al. (94) successfully designed an in situ ATR-FITR aerosol chamber to study the hygroscopic properties of aerosol particles (see Figure 6). Because the incidence infrared light of the ATR-FTIR method is totally reected back into the ATR crystal after penetrating into samples for a few micrometers, the high quality of the ATR spectra with little disturbance from water vapor can be generally obtained, which makes spectral analysis and discussion easier and more reliable. Therefore, ATR-FTIR is particularly applicable to the further study of aerosol hygroscopic properties. In recent years, Zhangs group has widely utilized the ATR-FTIR method to investigate hygroscopic properties of various aerosol particles. For example, the deliquescence and eforescence processes of NaClO4 aerosol particles and a small amount of residual interfacial water and capillary cohesion water in NaClO4 solid particles (94), hygroscopic behaviors of metastable Mg(NO3 )2 particles and formation of contact ion pairs (CIPs) and solvent-shared ion pairs (SIPs) in supersaturated Mg(NO3 )2 droplets (95), phase transitions and molecular structure changes during the deliquescence and eforescence processes of NaNO3 aerosol particles (96), and the effect of the relative humidity annealling on the hygroscopic properties of NaCl, NaNO3 , and NaClO4 aerosol particles (97). In addition, they have tried to develop the method of probing the optical constants of supersaturated aerosols based upon their ATR-FTIR spectra (98). By making use of ATR-FTIR and ultraviolet-visible spectrometry, Hudson et al. (99) have studied the relationships between the photoreactivity of aqueous nitrate aerosols and the molecular and electronic structures of nitrate ions. Generally, most
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of previous studies on aerosol hygroscopic properties have focused on coarse aerosol particles, mainly due to the inherent limitation of the experimental setup (such as EDB), which in general is only applicable to the study of aerosol particles larger than a few micrometers, and the hygroscopicity of ne aerosol particles has been poorly constrained. However, most recently Wang et al. (100) have successfully investigated the hygroscopic growth of ne MgSO4 aerosol particles using a retted standard ATR-FTIR setup and demonstrated that the hygroscopic behavior of ne particles is quite different from that of coarse particles. T-FTIR spectrometry has also been successfully used to study aerosol hygroscopic properties (101104). The aerosol particles for T-FTIR observation were generally placed on a lmed grid substrate inside the IR cell with a large surface number concentration. In humidity conditions, the aerosol particles containing liquid water can strongly absorb infrared light when an IR beam passes through the substrate; thus, infrared spectra of high sensitivity and high SNR with negligible disturbance from water vapor can be obtained. In this regard, Liu et al. (103, 104) recently used T-FTIR to investigate the hygroscopic properties of NaCl, NaNO3 , and (NH4 )2 SO4 aerosol particles as well as sea salts and methanesulfonate salts. The deliquescence RH (DRH), eforescence RH (ERH), hygroscopic growth factors, and water-to-solute ratio (WSR) of these aerosol particles were determined using the changes in IR spectra along with the integrated absorbance of the water and the solute-specic bands, which were in good agreement with the results reported by Tang et al. (105, 106). T-FTIR spectroscopy was also used by Al-Abadleh and Grassian to study the water adsorption on Al2 O3 surfaces (101) and the deliquescence and eforescence processes of nitric acid reacted MgO interfaces (102). In the past few years, microscopy techniques combined with Raman (7780) or FTIR (103, 104) spectroscopy have been widely used to probe not only the morphological changes but detailed information on molecular structures of individual aerosol particles during their deliquescence and eforescence processes. This is helpful for the further understanding of the hygroscopic behaviors of aerosol particles.
FTIR in Situ Study of Chemical Compositions of Atmospheric Particles The complex environmental behavior of atmospheric particles closely related to their chemical composition has a signicant inuence on air quality, atmospheric chemical processes, and global climate change. Therefore, probing the chemical composition of atmospheric particles plays a key role in better understanding their environmental behavior and atmospheric implications. Currently, the major methods for chemical characterization of ambient particles include bulk organic carbon (OC; such as thermal optical methods [TOM] and evolved gas analysis [EGA]) and speciation (such as ion chromatogram [IC] gas chromatographymass spectroscopy [GC-MS]) techniques. IC and GC-MS are the two mature techniques for chemical characterization on the molecular level of inorganic ions and organic compounds, respectively, in atmospheric particles. However, both of these two techniques require complex extraction and derivatization procedures, and sample preparation and analysis are time consuming and destructive (107111). In addition, GC-MS can only quantify less than 20% of organic matters in aerosol particles. It is particularly difcult to analyze high-molecular-weight and high-polarity organic compounds (109111). TOM techniques, such as thermal optical transmittance (TOT) and thermal optical reectance (TOR), allow for measurement of the bulk OC while providing no speciation information on individual organic compound or organic functional groups (112, 113). Similarly, the EGA method also can only determine the total mass of OC, and the analysis results are largely uncertain (114, 115).
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Compared to various techniques mentioned above, FTIR spectroscopy is capable of identifying and/or quantifying nearly all of the functional groups on a molecular level even though it may not provide information on individual compounds in ambient aerosols. Moreover, it is a direct, rapid, and nondestructive method of analysis, requiring no sample extraction and derivatization. Therefore, FTIR spectroscopy offers an effective method for chemical characterization of ambient aerosols (see Table 4 for a summary of typical related studies described below). There are two major methods commonly used to collect aerosol samples for FTIR analysis; one is to collect aerosol particles using a low-pressure impactor (LPI) equipped with a ZnSe impaction surface, and the aerosol samples on ZnSe crystal are then directly analyzed using FTIR spectroscopy (116121); the other is collecting aerosol particles on Teon lters for direct FITR observation, and the infrared spectra of a blank Teon lter are subtracted from those of each sampled Teon lters to obtain the infrared absorptions by aerosol samples (122135). As early as the 1970s and 1980s, FTIR spectroscopy was used to probe the chemical composition of atmospheric particles (136139). However, these applications were strongly limited to qualitative and semiquantitative analysis because of the constraints in sensitivity and precision of IR spectroscopy. Since the 1990s, advances in infrared optics and detectors have greatly improved the performance of IR and FTIR spectroscopy and these techniques have been extensively applied to improved quantitative and qualitative measurements of chemical components in ambient aerosols. For example, Allen et al. (116) developed a method utilizing T-FTIR to determine the loadings of organic and inorganic functional groups in size-segregated ambient aerosols collected on the ZnSe impaction surface in a low-pressure impactor (LPI). Subsequently, this LPI/FTIR method was used to identify the chemical compositions of secondary organic aerosol (SOA) produced by the photooxidation of 1,3,5-trimethylbenzene, naphthalene, and sesquiterpene, respectively. The relative concentrations of alcohols, carboxylic acids, organic nitrates, carbonyl groups, nitroaromatics, aliphatic C H, and aromatic C H in the aerosols were estimated through analysis of infrared spectra (117, 119, 120). Recently, Maria et al. (122) applied T-FTIR to the quantication of inorganic ions (including SO4 2, SiO4 4, NO3 , and NH4 +) and organic functional groups (including aliphatic C H and carbonyl C O) in ambient aerosols collected on Teon lters, and more specic organic functional groups (such as alkane C H, alkene C H, aromatic C H, carbonyl C O, alcohol C OH, amine C NH2 , and organosulfate C O S) in ambient aerosols were determined using more calibration standards (123, 124, 132). Because FTIR analysis is nondestructive, a sequential four-solvent (hexane, dichloromethane, acetone, and water) rinsing procedure was performed in these studies to separate the functional groups into fractions of increasing polarity. This not only effectively avoids the interference on the infrared absorption peak of each component but also provides information on aerosol polarity (122124). More recently, with a revised approach for spectra interpretation used previously (122124, 132), Russell s group have made great progress in the quantitative characterization of organic functional groups with FTIR by dividing the quantied carbonyl C O into nonacid carbonyl C O and carboxylic acid groups (133135). Positive matrix factorization (PMF) was applied to FTIR spectra to identify the classes of sources contributing to organic aerosols (134). In addition, T-FTIR has been applied to a PM2.5 exposure study for the rst time (127), and the functional groups (specically, aliphatic C H and carbonyl C O) of these PM2.5 samples have been quantied using a multivariate calibration method (partial least squares, PLS) (128). Even though DRIFTS is generally less repeatable and less accurate than T-FTIR for quantitative analysis, it still has the potential to quantify the functional groups in ambient aerosols. Krivacsy and Hlavay (140, 141) quantitatively analyzed the quartz and calcite in atmospheric particles using DRIFTS, and the results were in
Table 4 Summary of selected studies on characterization of aerosol chemical compositions Measurements Univariate Univariate Calibration method Reference (116) (117)
FTIR
Aerosol samples
T-FTIR
Ambient aerosol
T-FTIR
T-FTIR
Aerosol produced by the photooxidation of 1,3,5-trimethylbenzene Smoky Mountain aerosol Univariate
(118) (120)
T-FTIR
T-FTIR
Aerosol produced by the photooxidation of sesquiterpene Ocean aerosol
Univariate
(122)
T-FTIR
Ocean aerosol
Univariate Univariate
(123) (125)
T-FTIR
Ocean aerosol
T-FTIR
Suburban aerosol
Univariate
(124) (127) (126) (Continued on next page)
T-FTIR
ATR-FTIR
Indoor, outdoor, and personal PM2.5 Urban PM102.5 and PM2.5
Quantication of aerosol organic and inorganic functional groups Identication of aerosol organic and inorganic functional groups, relative concentrations of functional groups Aerosol polarity and identication of aerosol functional groups Identication of aerosol organic and inorganic functional groups, relative concentrations of functional groups Aerosol polarity, quantication of aerosol organic and inorganic functional groups, and organic carbon Quantication of aerosol organic and inorganic functional groups and organic carbon Quantication of aerosol organic functional groups, measurements of organic carbontoorganic mass ratio Aerosol water-solubility, quantication of aerosol functional groups, and organic mass Identication of aerosol organic and inorganic functional groups Identication of aerosol organic and inorganic functional groups
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80 Measurements Calibration method Univariate Multivariate Univariate Univariate Univariate Univariate Multivariate Univariate Reference (129) (131) (140) (143) (142) (132) (128) (135) Quantication of aerosol organic functional groups Quantication of aerosol organic and inorganic functional groups Quantication of quartz and calcite in aerosol samples Quantication of aerosol sulfate, ammonium, and nitrate Quantication of sulfate in samples Quantication of aerosol organic functional groups, organic carbon, and organic mass Quantication of aerosol organic and inorganic functional groups Quantication of aerosol organic functional groups and organic mass
Table 4 Summary of selected studies on characterization of aerosol chemical compositions (Continued)
FTIR
Aerosol samples
ATR-FTIR
Ambient aerosol
ATR-FTIR
Ambient aerosol
DRIFTS
Ambient aerosol
DRIFTS
Urban aerosol
DRIFTS
T-FTIR
Coarse and ne aerosol particles, dry deposits, and soil Ambient aerosol
T-FTIR
T-FTIR
Indoor, outdoor, and personal PM2.5 Ambient aerosol
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good agreement with those determined with T-FTIR and X-ray uorescence spectrometry (XRF). Besides, DRIFTS was widely used for quantitative measurements of the inorganic ions including SO4 2, NO3 , and NH4 + in ambient aerosols, and the results agreed well with those measured with IC (142, 143). All of these results demonstrated that the method using DRIFTS to directly quantify the inorganic components in ambient aerosols is feasible. In the early 1980s, ATR-FITR had already found its applications in the study of ambient aerosols (144, 145), when a specially designed ATR impactor was used to collect ambient aerosol samples for aerosol sulfate and strong acid characterization. Recently, Shaka and Saliba (126) investigated the use of ATR-FTIR for the identication of the functional groups in atmospheric aerosols collected on polytetrauoroethylene (PTFE) lters and established a comparison of main constituents between atmospheric PM102.5 and PM2.5 for the rst time. The feasibility of ATR-FTIR for quantitative analysis of ambient aerosols was then evaluated by Ghauch et al. (129). It was shown that ATR-FTIR cloud can be successfully used to quantitatively determine the organic functional groups in ambient aerosols through the cleaning of the ATR crystal substrate, the treatment of infrared spectra, and baseline correction. More recently, a multivariate calibration method has been used to quantify organic functional groups and inorganic compounds in ambient aerosols with ATR-FTIR (130, 131). The sum of the mass of organic and inorganic species measured by ATR-FTIR on average accounted for 91% of parallel gravimetric mass measurements, indicating that this method can accurately measure the absolute mass of aerosol organic functional groups and inorganic ions (131). Because FTIR spectroscopy can quantify nearly all of the mass of organic functional groups in the aerosols, it has been extensively applied to organic carbon (OC) and organic mass (OM) determination (122125, 128, 132135). In comparison with the EGA method of large uncertainties, quantifying OC and OM with FTIR is a signicant improvement (over EGA measurements) by reducing the average error from 87 to 21%, primarily due to the fact that FTIR measurements avoid the molecular weight assumptions used for bulk OC techniques (125). In addition, OC and OM measurements from FTIR are in general well correlated with and/or show good agreement with corresponding TOM (123, 132) or online aerosol mass spectrometry (AMS) measurements (132135). The biggest challenge for quantication of the functional groups in atmospheric aerosols using FTIR spectroscopy is to build a calibration model that describes the quantitative relationship between sample concentration and infrared absorbance. The methods to build the calibration models mainly include univariate and multivariate calibration. However, most of the FTIR applications in the quantitative determination of aerosol components have employed univariate calibration methods. This generally relates the infrared absorption peak area to the functional group loading using calibration standards (122, 129, 140, 141), IC measurements (142, 143), as well as X-ray uorescence spectrometry (XRF) measurements (146, 147), yielding a standard calibration curve (in which the functional group concentration is linearly proportional to the absorption peak area) for each function group of interest. The functional group loadings in the aerosol samples are then calculated using relevant calibration curves. It is well known that the absorption peaks in infrared spectra of ambient aerosol samples generally overlap with others to some extent. Even though curve-tting procedures can provide reliable peak areas if (1) the number of unresolved peaks in the region of interest is known, (2) the degree of peak overlap is under a certain threshold, and (3) the true baseline position can be determined (148), FTIR spectra of ambient aerosol samples usually cannot meet these basic requirements. Therefore, quantication of these functional groups has been particularly problematic because accurate integration of absorption peaks cannot be achieved. In addition, the calibration standards used to develop calibration curves for univariate calibration methods are usually single
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component and are not capable of simulating ambient aerosols closely and reliably because the infrared absorbance of each functional group in ambient aerosols is closely related to its molecular structures as well as the interactions with other components, thus leading to errors in infrared data interpretation. Instead of building a linear calibration curve, multivariate calibration methods utilize the partial least squares (PLS) model to correlate peak intensity rather than peak area to the functional group concentrations (128, 130, 131), not only minimizing the issues relevant to peaks overlapping but allowing multiple frequencies to be used in predicting the loadings of a given functional group (131). Additionally, the calibration standards used to create the PLS model are generally multicomponent, which enables component interactions to be considered and thus more closely mimic ambient aerosols. Furthermore, multivariate methods make a remarkable improvement in the specicity of the quantied functional groups over univariate methods. For example, instead of quantifying carbonyl functional groups (C O) as a whole, more specic functional groups such as aldehydes/ketones, carboxylic acids, esters, and acid anhydrides, each of which contains a carbonyl bond (C O), can be quantied (130, 131). Therefore, it is clear that multivariate methods have the potential to yield more reliable and more effective results for the quantitative characterization of ambient aerosols than univariate methods.
Overview and Future Directions

We have briey reviewed the application of in situ FTIR spectroscopy in the study of atmospheric heterogeneous processes associated with ambient aerosols, specically including the heterogeneous reactions on the surface of aerosol particles, aerosol hygroscopic behaviors, and aerosol chemical compositions. With the rapid development of optics and detection techniques, FTIR spectroscopy has made continuous improvement in its performances of qualitative and in particular quantitative analysis, signicantly deepening and broadening its applications in related research. However, so far most quantitative studies of atmospheric heterogeneous processes by FTIR have been limited to relatively simple systems (such as reactions of inorganic trace gases on model atmospheric particles and quantication of inorganic compounds in ambient aerosols). The quantitative analysis and sometimes even qualitative observations of complex heterogeneous systems with FTIR (such as heterogeneous reactions of organic compounds and determination of organic functional groups in ambient aerosols) are still constrained to a large extent. The difculties here lie in several facts presented below. First, most of the infrared spectra collected in complex organic heterogeneous systems have a lack of high spectral resolution and infrared absorption peaks are easy to overlap with each other. Also, the absorption bands of different organic functional groups containing the same bond (such as aldehydes/ketones, carboxylic acids, esters, and acid anhydrides, which each contain a carbonyl bond (C O)) often cannot be differentiated at all in the infrared spectra. This results in considerably low specicity of identied organic functional groups. Second, even though multivariate calibration methods allow for more effective quantitative characterization of a heterogeneous system than univariate methods, their development and application in the study of atmospheric heterogeneous processes are still at the initial stage and in most studies the infrared spectra are calibrated using a univariate method. This may result in signicant uncertainties in determinations with FTIR spectroscopy. Third, some absorption peaks in the infrared spectra of complex samples (such as ambient aerosol samples) could not be identied because relevant reference spectra of these unknown species are not available.
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Finally, it should be noted that FTIR spectroscopy provides molecular-level insight to functional groups rather than individual compounds or elements in the sample. Other techniques in addition to FTIR spectroscopyfor example, HPLC, IC, GC, GC-MS, and surface analysis techniquesare necessary to achieve observations of individual compounds and/or elements. In addition, several factors, like sample preparation, instrument operation, the treatment of infrared spectra, and the choosing of a calibration method, substantially inuence the infrared spectra and subsequent data interpretation, potentially leading to uncertainties in the quantication results. Therefore, the future direction for the development of FTIR spectroscopy should focus on the following aspects. The rst is to further improve the optics and detection techniques of the FTIR spectrometer. Advanced optics and detection techniques allow for the enhancement of the sensitivity, precision, and spectral resolution of FTIR spectroscopy, which provides the fundamental qualication for the reliable qualitative and quantitative analysis of complex systems. A second goal is the continued development of a quantitative calibration model for infrared spectra, which is a critical direction for future study, and the importance should be attached to multivariate calibration methods because they are more applicable to quantitative characterization of heterogeneous processes, in particular complex organic systems, than univariate methods. Because the unidentied bands in the infrared spectra of complex samples are largely attributed to the lack of reference spectra that are generally obtained using model samples, the third direction of future study is to further develop model samples in various physical states and to build relevant reference infrared spectra. Furthermore, it is clear that the characteristics and scope of application of each kind of FTIR spectroscopy (e.g., T-FTIR, ATR-FTIR, and DRIFTS, each of which has unique advantage) are dominated by specic accessory coupled with FTIR spectrometer. Therefore, a follow-up future direction is to further develop accessory techniques to improve the deepness and extent of the applications of FTIR spectroscopy. In almost all of the reported studies on atmospheric heterogeneous processes, various other techniques or methods are widely utilized to provide additional and complementary data, which is not only helpful for evaluating the reliability of FITR analysis but enables better understanding of the nature of heterogeneous processes. Therefore, the continued development of other techniques available for the study of heterogeneous processes can also effectively promote the applications of FTIR spectroscopy. Lastly, it has been shown that two-dimensional correlation infrared spectroscopy (2D-IR) can not only resolve the issue of spectral overlap and disturbance by increasing the resolution of IR spectra but provide more information on molecular structure of samples that can not be obtained from ordinary spectra; thus, 2D-IR techniques may be a future feasible and successful approach promoting the investigations of complex heterogeneous systems.
Acknowledgments
The authors gratefully thank the National Natural Science Foundation of China (grants 20677002 and 40875072) for their nancial support.
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X1.application of Fourier Transform Infrared Spectroscopy in The Study of Application of Fourier Transform Infrared Spectroscopy in The Study Of, 2010

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Applied Spectroscopy Reviews

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Y. Zhao and Z. Chen

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Fourier Transform Infrared Spectroscopy

Atmospheric Heterogeneous Processes

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Y. Zhao and Z. Chen

Specic Applications of FTIR Spectroscopy

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Table 1 Summary of selected studies on atmospheric heterogeneous reactions

NO2 Diffuse reectance, UV-vis Diffuse reectance, UV-vis Knudsen cell

synthetic sea salt mixtures Al2 O3 , TiO2

NO2 NO2 , HNO3

Al2 O3 , Fe2 O3 , TiO2 Al2 O3

-Fe2 O3 , -Al2 O3 , SiO2

H2 O, SO2 , HNO3 T-FTIR & ATR-FTIR DRIFTS & LP-FTIR

Al2 O3 , CaO, TiO2 , MgO, FeOOH, Fe2 O3 , SiO2

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Table 1 Summary of selected studies on atmospheric heterogeneous reactions (Continued)

Hematite, NaCl, hematite-NaCl mixtures NaCl-MgCl2 mixtures

4-Carboxybenzophenone(4-CB) lms 7-Octenyltric hlorosilane ATR-FTIR SAMs SiO2 T-FTIR

Hematite, kaolinite, calcite, quartz

Atmospheric Heterogeneous Processes

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Y. Zhao and Z. Chen

-Al2 O3 Iron oxides Mineral dust Al2 O3 -Al2 O3 SiO2 CaO

HCHO CH3 C(O)CH3

Atmospheric Heterogeneous Processes

Y. Zhao and Z. Chen

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Atmospheric Heterogeneous Processes

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Table 3 Summary of selected studies on aerosol hygroscopicity

Malonic and oxalic acid aerosols

AFT-FTIR AFT-FTIR AFT-FTIR

Supersaturated NaClO4 aerosols

AFT-FTIR, TDMA AFT-FTIR ATR-FTIR

Aqueous nitrate aerosols

NaCl, NaNO3 , and NaClO4 aerosols

ATR-FTIR T-FTIR T-FTIR

Atmospheric Heterogeneous Processes

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Atmospheric Heterogeneous Processes

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Y. Zhao and Z. Chen

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Aerosol produced by the photooxidation of 1,3,5-trimethylbenzene Smoky Mountain aerosol Univariate

Aerosol produced by the photooxidation of sesquiterpene Ocean aerosol

(124) (127) (126) (Continued on next page)

Indoor, outdoor, and personal PM2.5 Urban PM102.5 and PM2.5

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Table 4 Summary of selected studies on characterization of aerosol chemical compositions (Continued)

Indoor, outdoor, and personal PM2.5 Ambient aerosol

Atmospheric Heterogeneous Processes

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Y. Zhao and Z. Chen