Application of FTIR Spectroscopy in Environmental Studies
IntroductionFTIR Spectroscopy is a technique based on the determination of the interaction between an IR radiation and a sample that can be solid, liquid or gaseous. It measures the frequencies at which the sample absorbs, and also the intensities of these absorptions. The frequencies are helpful for the identification of the sample’s chemical make-up due to the fact that chemical functional groups are responsible for the absorption of radiation at different frequencies. The concentration of component can be determined based on the intensity of the absorption. The spectrum is a two-dimensional plot in which the axes are represented by intensity and frequency of sample absorption.
Traditional transmission FT-IR (T-FTIR) spectroscopy in environmental studiesTransmission spectroscopy is the oldest and most commonly used method for identifying either organic or inorganic chemicals providing specific information on molecular structure, chemical bonding and molecular environment. It can be applied to study solids, liquids or gaseous samples being a powerful tool for qualitative and quantitative studies. Application of FTIR Spectroscopy in Environmental Studies 51 FTIR instrument’s principle of function is the following: IR radiation from the source that hits the beam splitter is partly directed towards the two mirrors arranged as shown in Figure 2. One of the two mirrors is stationary, and the other is moved at a constant velocity during data acquisition. As it can be seen in Figure 2 at first the IR beams are reflected by mirrors, after that are recombined at the beam splitter, and then passed through the sample and reach the detector. This records all wavelengths in the IR range. After the two beams reflected by the mirrors recombine, they will travel different distances, and the recombination will lead to constructive and destructive interference. The result will be an interferogram. After the recombined beam has passed through the sample the detector will record the fourier transform infrared spectroscopy of the sample. The data obtained are then processed by a computer that performs an additional Fourier transform to back-transform the interferogram into an ftir spectroscopy.
The potential value of FTIR spectroscopy to a wide range of environmental applications has been demonstrated by numerous research studies. Some of them are presented below. A review by McKelvy and coworkers containing 132 references at the chapter related to environmental applications of IR spectroscopy (McKelvy et al., 1998) covers the published literature about relevant applications of IR spectroscopy for chemical analysis. The literature research was made for the period November 1995 to October 1997. The review contains aspects about infrared accessories and sampling techniques, infrared techniques, applications of infrared spectroscopy in environmental analysis,chemical analysis, food and agriculture, biochemistry and also the books and reviews appeared in that period for this subject (McKelvy et al., 1998). An other review concerning the nearinfrared and infrared spectroscopy was made by Workman Jr. This review covers the period 1993-1999 and presents the application of the near infrared spectral region to gas analysis,material analysis and all types of analyses (Workman Jr, 1999).
The basic principle and methods of FTIR spectroscopy of the atmosphere are presented by Bacsik and coworkers in 2004 (Bacsik et al., 2004). The same group of researchers published a review article related to the most significant and frequent applications of FTIR spectroscopy to the study of the atmosphere (Basick et al., 2005). The authors summarized the basic literature in the field of special environmental applications of FTIR spectroscopy, such as power plants, petrochemical and natural gas plants, waste disposals, agricultural, and industrial sites, and the detection of gases produced in flames, in biomass burning, and in flares (Basick et al., 2005). Applications of FTIR spectroscopy to agricultural soils analysis were presented and discussed by Raphael in the book entitled ”Fourier Transforms - New Analytical Approaches and FTIR Strategies” (Raphael, 2011). Chapter 19 of the same book presents the application of FTIR spectroscopy in waste management, and chapter 21 presents the study of trace atmospheric gases using Ground-Based Solar Fourier Transform Infrared Spectroscopy (Smidt et al., 2011; Paton-Wals, 2011). In case of air pollution the Fourier transform infrared (FTIR) instrument is used succesfully for measuring gas pollutants due to its many advantages such as: multiple gas pollutants will be monitored in real time, the IR spectra of sample can be analyzed and preserved for a long time, can be use to detect and measure directly both criteria and toxic pollutants in ambient air, measures also organic and inorganic compounds, can be also used to characterize and analyze microorganisms and monitor biotechnological processes, is generally installed at one location, but can be also portable and operated using battery for short-term survey, presents sensitivity from very low parts per million to high percent levels, can be applied to the analysis of solids, liquids and gases, no reagent is needed, and data acquisition is faster than with other physico-chemical techniques (Santos et al., 2010). The basic principle of FT-IR spectroscopy used in air pollutants detection and measuring is that every gas has its own „fingerprint” or absorption spectrum. The entire infrared spectrum will be monitored and FTIR sensor will read the different fingerprints of the gases present in the air sample. In case of determination of gas concentrations from stratosphere, the FT-IR spetrometers have to be designed with a fine resolution (0.01 cm-1) due to the lower atmospheric pressure, and with a lower resolution between 0.05 cm-1 and 2 cm-1 for tropospheric gases determination. This is due to pressure broadening effects that result in broadened absorption lines. In troposphere water vapor concentrations are higher than those from stratosphere and they have a negative effect on the FT-IR spectrum measurements. The strong interference of water vapor in troposphere is overcome by detecting chemical substances in narrow bands of the IR spectrum where water absorption is very weak. The total precipitable water vapour (PWV) from air which is responsible for the greenhouse effect being the most important trace gas can be measure using FT-IR spectroscopy. When it was compared with other instruments such as a Multifilter Rotating Shadow-band Radiometer (MFRSR), a Cimel sunphotometer, a Global Positioning System (GPS) receiver, and daily radiosondes (Vaisala RS92) it was estimated that FTIR spectrometer provides very Application of FTIR Spectroscopy in Environmental Studies 53 precise trophospheric water vapour data, but when area-wide coverage and real-time data availability is very important, the GPS and the RS92 data are more appropriate. FTIR spectroscopy can be use also as a reference when assessing the accuracy of the other techniques, but those who use this technique have to be aware of the FTIR’s significant clear sky bias (Schneider, 2010). Animal farms are major sources of air pollution with ammonia and greenhouse gases. Air concentration of these pollutants may be higher or lower depending on the systems used. In addition, these systems have to correspond both in terms of animal welfare, and in terms of environmental protection. If it is considered animal welfare, the straw based systems are considered animal friendly systems, and when it is considered the environmental protection, the slurry based systems are preferred, due to lower ammonia (NH3) and greenhouse gas (GHG) emissions. For slurry based systems air pollutants emissions were intensively researched, and the specific emission factors for several slurry-based housing systems for pigs are mentioned in the “Guidance document on control techniques for preventing and abating emissions of ammonia” developed by the UN/ECE “Expert Group on Ammonia Abatement” of the “Executive Body for the Convention on Long-Range Transboundary Air Pollution” (EB.AIR/1999/2). The straw based systems have not been extensively studied in terms of emissions of air pollutants. There are few research studies regarding these systems. Thus, high resolution FTIR spectrometry was used in order to determine the emissions of ammonia (NH3), nitrous oxide (N2O), methane (CH4), and volatile organic compounds (VOC) at a commercial pig farm in Upper Austria using a straw flow system by Amon and coworkers (Amon et al., 2007). The straw flow system is an animal friendly housing system for fattening pigs, being often equated with deep litter where there is no separation between the lying and the excretion areas. In deep litter systems most of the pigs welfare requirements are fulfilled. The main disadvatages of these systems are that there is a high straw consumption, the pigs are dirtier and the deep litter are characterized by high levels of NH3 and greenhouse gases (GHG). Thus the level of NH3 and greenhouse gases (GHG) has to be monitored in order to control and to avoid air pollution and to take appropriate measures for environment protection. For the pig farm monitored by Amon and coworkers it can be concluded that the straw flow system may combine recommendations of animal welfare and environmental protection (Amon et al., 2007). Environmental problems are also due to the incorect application of manure. The main air pollutants associated with manure application are ammonia, and nitrous oxides. In order to develop new environmentaly friendly methods for manure applications all aspects have to be investigated. For this purpose Galle and coworkers made some area-integrated measurements of ammonia emissions after spreading of pig slurry on a wheat field, based on gradient measurements using FTIR spectroscopy. They concluded that the gradient method is valuable for measurement of ammonia emissions from wide area, although the detection limits of the system limits its use to the relatively high emissions.
Diffuse Reflectance Infrared Fourier Transform (DRIFTS) spectroscopy in environmental studiesDRIFTS spectroscopy is considered a technique more sensitive to surface species than transmission measurements and is an excellent in situ technique. The principle is simple one: when incident light strikes a surface, the light that penetrates is reflected in all directions. This reflection is called diffuse reflectance. If the light that leaves the surface will pass through a thin layer of the reflecting materials, its wavelength content will have been modified by the optical properties of the matrix. The wavelength and intensity distribution of the reflected ligth will contain structural information on the substrate (Analytical Spectroscopy available at: //www.analyticalspectroscopy.net/ap3-11.htm) (Figure 6). 66 Advanced Aspects of Spectroscopy Figure 6. The principle of Diffuse Reflectance Infrared Fourier Transform Spectroscopy (adapted from Analytical Spectroscopy available at: //www.analyticalspectroscopy.net/ap3-11.htm) The main advantages of DRIFTS spectroscopy are: fast measurement of powdered samples, minimal or no sample preparation, ability to detect minor components, ability to analyze solid, liquid or gaseous samples, is one of the most suitable method for the examination of rough and opaque samples, high sensitivity, high versatility, capability of performing of the measurements under real life conditions. In the environmental studies diffuse reflectance Fourier transform infrared (DRIFTS) spectroscopy is considered an alternative methodology for the quantitative analysis of nitrate in environmental samples (Verma and Deb, 2007a). It is considered a new, rapid and precise analytical method for the determination of the submicrogram levels of nitrate (NO3−) in environmental samples like soil, dry deposit samples, and coarse and fine aerosol particles. The DRIFTS method is a feasible nondestructive and time saving method for quantitative analyses of nitrate in soil, dry deposit and aerosol samples. It is well known that soil can act as sinks as well as sources of carbon. A major fraction of carbon in soils is contained in the soil organic matter (SOM). It contributes to plant growth through its effect on the physical, chemical, and biological properties of the soil. Characterization of soil organic matter (SOM) is important for determining the overall quality of soils. For this DRIFTS spectroscopy can be used. This method only takes a few minutes, and is much faster than fractionating of soil samples using chemical and physical methods and determining the carbon contents of the fractions (Zimmermann et al., 2007). In another study, Rumpel and coworkers tested diffuse reflectance infrared Fourier transform (DRIFT) spectroscopy in combination with multivariate data analysis [partial least squares (PLS)] as a rapid and inexpensive means of quantifying the lignite contribution to the total organic carbon (TOC) content of soil samples (Rumpel et al., 2001). DRIFTS spectroscopy is also considered to be one of the most sensitive infrared technique to analyze humic substances (Ding et al., 2000). Studies by Ding and coworkers demonstrate that both DRIFT and 13C NMR are suitable for examining the effect of tillage on the distribution of light fraction in soil profile (Ding et al, 2002). More recently Ding and coworkers examined the effect of cover crops on the chemical and structural composition of SOM using chemical and DRIFT spectroscopic analysis. From this study it was concluded that both organic carbon (OC) and light fraction (LF) contents were higher in soils under cover crop treatments with and without fertilizer N than soils with no cover crop. Thus cover crops had a profound Application of FTIR Spectroscopy in Environmental Studies 67 influence on the SOM and LF characteristics (Ding et al., 2006). In other study Janik and coworkers (1995) showed that the use of diffuse reflectance infrared Fourier-transformed Spectroscopy (DRIFT) in combination with partial least squares algorithm (PLS) is a fast and low-cost method to predict carbon content and other soil properties such as clay content and pH. Zimmermann and coworkers evaluated the possibility of using of DRIFT-spectroscopy to estimate the soil organic matter content in soil samples from sites across Switzerland (Zimmermann et al., 2004). It was concluded that DRIFT spectroscopy is a tool to predict changes in soil organic matter contents in agricultural soils resulting from changes in soil management. In other study Nault and coworkers used DRIFT spectroscopy to compare changes in organic chemistry of 10 species of foliar litter undergoing in situ decomposition for 1 to 12 years at four forested sites representing a range of climates in Canada (Nault et al., 2009). This study demonstrated that DRIFT spectroscopy is a fast and simple analysis method for analyzing large numbers of samples to give good estimates of litter chemistry. Thus DRIFTS spectroscopy is considered a more faster technique to analyse the composition and the dynamics of organic matter in solis compared with FTIR spectroscopy (Tremblay and Gagné, 2002; Spaccini et al., 2001). Earth’s atmosphere contains aerosols of various types and concentrations devided in: anthropogenic products, natural organic and inorganic products. The negative effects of these components refers to interaction with Earth’s radiation budget and climate. In direct way aerosols scatter sunlight directly back into space, and indirect aerosols in the lower atmosphere can modify the size of cloud particles, and consequently changing the way in which clouds reflect and absorb sunlight. Aerosols act also as sites for chemical reactions to take place. As an exemple of these kind of reactions can be mentioned destruction of stratospheric ozone. The inorganic component of aerosols consist of inorganic salts (e.g. sulfate, nitrate, and ammonium). The most used method for analyzing these salts is ion chromatography (IC) (Chen et al., 2003). The main disadvantages of this method are: time required for sample preparation and analysis that is up to 1 week, and the fact that this method is a destructive method of analysis. IR spectroscopy offers a simple and rapid alternative to IC for aerosols analysing, but it is imprecise and therefore only semiquantitative. Advances in optics and detectors have allowed the development of more precise IR spectroscopy methods such as FTIR and DRIFT spectroscopy. FTIR spectroscopy was employed to determine on-site chemical composition of aerosol samples and to investigate the relationship between particle compositions and diameters (Tsai and Kuo, 2006). DRIFTS spectroscopy was used for quantitative analysis of atmospheric aerosols (Tsai and Kuo, 2006). The components of aerosols determined quantitative in area investigated were SO42-, NO3- and NH4+. Compared with IC method, the DRIFT spectroscopy is a nondestructive, and quantitative method for aerosols analyzing. Nitrogen dioxide, one of the key participants in atmospheric chemistry has been determined using DRIFT spectroscopy. Compared with other methods for nitrogen dioxide determination such as chemiluminiscence and fluorescence method that are multi-reagent procedure with the increased possibility of the experimental errors, the DRIFTS spectroscopy involves using NaOH–sodium arsenite solution as an absorbing reagent. 68 Advanced Aspects of Spectroscopy Another advantage of DRIFTS spectroscopy is that it can determine ambient nitrogen dioxide, in terms of nitrite, at submicrogram level (Verma et al., 2008).
All these presented above show the importance of FTIR spectroscopy in environmental studies. The major advantages of this technique are: real time data collection and reporting, excellent sample-to-sample reproductibility, enhanced frequency accuracy, high signal-tonoise ratios, superior sensitivity, analytical performance. In addition, the measurement is very rapid so that a large number of samples can be analyzed. Consequently FTIR spectroscopy coupled with other techniques is widely used to determine the nature of pollutants (gaseous, liquid or solid), to monitor environment, to asses the impact of pollution on health and environment, to determine the level of decontamination processes. Application of FTIR Spectroscopy in Environmental Studies 73 The modern techniques such as attenuated total reflection FTIR (ATR-FTIR), and diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS), but also traditional transmission FTIR can be used for such studies according to the information needed, the physical form of the sample, and the time required for the sample preparation.
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