Carbon Soot Polymer Nanocomposites (CSPNCs): Production, Surface Morphological, Glass Transition Temperature Phenomenon and Optical Properties

*Rakhi Tailor, Yogesh Kumar Vijay and Minal Bafna*

#### **Abstract**

The present chapter covers the production and properties of carbon soot nanoparticles (CSNPCs) and their doped carbon soot polymer nanocomposites (CSPNCs). The first part of this chapter will provide a brief introduction of carbon soot, its morphology, production and synthesis methods. The second part will explain the investigation of carbon soot nanoparticles by flame deposition method and their properties. The third part will provide a short knowledge on polymer nanocomposites (PNCs) and their processing methods. The last part will illustrate the production of carbon soot polymer nanocomposites by solution casting method and their important properties. At the end, the chapter concludes with future scopes.

**Keywords:** carbon soot (CS), carbon soot polymer nanocomposites (CSPNCs), almond soot (AS), mustard soot (MS), energy band gap (Eg)

#### **1. Introduction**

Carbon particulate matters are small spherical particles in the range between 100 and 500 Å of diameter and synthesized by the combustion process [1, 2]. We will study these spherical particles by means of electron microscopy. X-ray diffraction technique (XRD) reveals that each soot particle contains thousands of crystallites and carbon sheet atoms with the graphite structure [3]. Researchers observed that the soot particles are aggregates of a number of tiny spherical particles, named primary particles [4, 5]. The chemical study of soot particles reveals that these particles are composed of elements other than just carbon. Carbon soot particles are composed of 1% hydrogen [1, 2] and up to 3% in weight of polycyclic organic matter [6]. In 1960, Lindsay collected soot samples by the combustion of 16 different hydrocarbons and extracted them with cyclohexane [7]. Carbon soot has several kinds of sources such as burning of oils, biomass fuels or any deliberate fires. The investigation of soot in a flame is a complete process, composed of

many mechanisms, and it depends on the composition of fuels [8]. In 1984, Melton suggested that carbon soot is an insoluble solid substance and roughly consists of eight carbon atoms and a single hydrogen atom [9]. Joyce found that soot is hard amorphous carbon particles in microscopic size [10]. Researchers found that soot particles are small in size but spherical hard particles in the range of 10–35 nm. These nanoparticles basically consist of carbon atoms arising from the fuel combustion at high temperature with a condition when the oxygen amount is insufficient to convert all the fuel in to CO2 and H2O [11, 12]. Soot particles can aggregate in soft and slippery secondary particles by their structure of agglomeration having average size of 120 nm or greater than 400 nm [13, 14].

#### **2. Carbon soot**

#### **2.1 Carbon soot morphology**

The structure of soot is difficult to define to a properly satisfactory extent. Soot obtain from combustion process and pyrolysis of hydrocarbons are composed of primary spheres agglomeration with a range of 10–15 nm in a diameter for a broad type of operation conditions [15].

The distribution of size mainly depends upon the primary spheres. Some researchers recorded that mustard soot has parallel physical and chemical characteristics to form the different types of soot, and it has been found that the primary particles could be as small as in a diameter [16].

Morphology of carbon soot particles from different field flames have been carried out using scanning electron microscopy (SEM) and transmission electron microscopy (TEM). The primary particles are composed of agglomerates like chain of individual spheres [17, 18]. The internal structure of soot particles is analyzed by high-resolution phase contrast electron microscopy [19].

According to the chemical study of soot, carbon is a main component in soot, but hydrogen and minor constituents can be present. The carbon hydrogen mole ratio of premature soot particles (primary soot particles) obtained by hydrocarbon fuels is equal to one or less than one, but this ratio for mature soot particles (aggregate soot particles) is high or approximately equal to 10 as compared to premature (C/H) ratio [18]. Agglomerated particles produced by the combustion method have been found to be in the range of 100 nm to 2 μm [20, 21]. The nanosize of soot particles is dependent on various conditions such as the production of sampling, operations and type of fuels. The term nanostructure of the soot is used to characterize the graphene layer plane dimensions its relative orientation and tortuosity [22, 23].

#### **2.2 Production and destruction method of soot**

Soot particles basically consist of carbon, oxygen and hydrogen, and some other constituents such as nitrogen, zinc, sulfur, etc. are also observed [24, 25]. In **Table 1**, the typical composition of soot obtained from the lubricant oil and soot contained are shown [26]. Soot in individual particles or spherical agglomerates is composed of many primary particles with approximately 10–50 nm in diameter [27]. The size of soot particles increases due to agglomeration because some particle diameters are up to 200 nm, and in this process, the soot-free radical character decreases.

The formation of soot is a complex process because this involves several physical and chemical steps and is still regarded as only partially understood. Soot particles

**95**

labeled (**Figure 4**).

*Carbon Soot Polymer Nanocomposites (CSPNCs): Production, Surface Morphological, Glass…*

**Soot composition Soot content (%)** Carbon 90 Oxygen 4 Volatile content 6

obtained from different sources such as various fuels and combustion are expected to be approximately similar in composition and size, suggesting the same processes of formation and growth constraints. Many authors have presented a model of soot formation from liquid or vapor phase combustion, which mainly comprises or is classified in to five distinct and normal identified processes, namely pyrolysis, nucleation, surface growth, coalescence and agglomeration as presented in **Figure 1**

Carbon soot production is also visualized as being a fuel thermal stability function [30]. Some authors also investigated that in the pyrolysis all hydrocarbons yield acetylene, which is the most precursor of species by incomplete combustion [31–33]. This is contributed to its low thermal stability where it easily breaks in to carbon solid and hydrogen. A well-defined and accepted theory for the formation

Carbon nanosoots have been produced by two different edible oils by flame

At room temperature, the flame deposition method is a well known, cost-effective and easiest method to produce carbon nanosoot from different oils (**Figure 2**). In this technique, we take two diyas or "clay lamp": one filled with almond oil and the other one is filled with mustard oil. Dip a cotton wick in both diyas and put it on the floor at some distance (approx. 40 cm). Light up cotton wick. To collect carbon soot particles, put another diya in reverse at some height with the help of other

In this arrangement, the distance between the tip of the wick and collector diyas' surface is approximately 5 cm. The distance has been optimized by carrying out the pyrolysis process at various source collector distances. The flame stabilizes after 1–2 min and then the almond oil soot and mustard oil soot are allowed to deposit on the collector. For 2 h, the almond and mustard oils were burned, and then the generated soots were scrapped off using a spatula on butter paper and then samples

In this section, the procedure of soot production from almond and mustard oil at a room temperature is the same as above mentioned (see Section 2.4.1). The only change made in this section is to introduce a water tub. The entire setup is arranged in a water tub to provide the sample surroundings extra moisture (**Figure 3**). After completion of the processes, all soot samples were stored in air-tight bottles and

*DOI: http://dx.doi.org/10.5772/intechopen.92389*

[18, 28, 29].

**Table 1.**

*Soot percentage composition.*

of soot is explained by Haynes [18].

**2.3 Investigation of carbon soot nanoparticles**

layers of diyas and make the arrangement.

were packed in air-tight bottles with proper labeling.

*2.3.2 Formation of soots in water tub environment (with water tub)*

deposition techniques in two different environments.

*2.3.1 Formation of soots in natural environment (without water tub)*

*Carbon Soot Polymer Nanocomposites (CSPNCs): Production, Surface Morphological, Glass… DOI: http://dx.doi.org/10.5772/intechopen.92389*


#### **Table 1.**

*Environmental Emissions*

**2. Carbon soot**

**2.1 Carbon soot morphology**

type of operation conditions [15].

and tortuosity [22, 23].

size of 120 nm or greater than 400 nm [13, 14].

particles could be as small as in a diameter [16].

**2.2 Production and destruction method of soot**

high-resolution phase contrast electron microscopy [19].

many mechanisms, and it depends on the composition of fuels [8]. In 1984, Melton suggested that carbon soot is an insoluble solid substance and roughly consists of eight carbon atoms and a single hydrogen atom [9]. Joyce found that soot is hard amorphous carbon particles in microscopic size [10]. Researchers found that soot particles are small in size but spherical hard particles in the range of 10–35 nm. These nanoparticles basically consist of carbon atoms arising from the fuel combustion at high temperature with a condition when the oxygen amount is insufficient to convert all the fuel in to CO2 and H2O [11, 12]. Soot particles can aggregate in soft and slippery secondary particles by their structure of agglomeration having average

The structure of soot is difficult to define to a properly satisfactory extent. Soot obtain from combustion process and pyrolysis of hydrocarbons are composed of primary spheres agglomeration with a range of 10–15 nm in a diameter for a broad

The distribution of size mainly depends upon the primary spheres. Some researchers recorded that mustard soot has parallel physical and chemical characteristics to form the different types of soot, and it has been found that the primary

Morphology of carbon soot particles from different field flames have been carried out using scanning electron microscopy (SEM) and transmission electron microscopy (TEM). The primary particles are composed of agglomerates like chain of individual spheres [17, 18]. The internal structure of soot particles is analyzed by

According to the chemical study of soot, carbon is a main component in soot, but hydrogen and minor constituents can be present. The carbon hydrogen mole ratio of premature soot particles (primary soot particles) obtained by hydrocarbon fuels is equal to one or less than one, but this ratio for mature soot particles (aggregate soot particles) is high or approximately equal to 10 as compared to premature (C/H) ratio [18]. Agglomerated particles produced by the combustion method have been found to be in the range of 100 nm to 2 μm [20, 21]. The nanosize of soot particles is dependent on various conditions such as the production of sampling, operations and type of fuels. The term nanostructure of the soot is used to characterize the graphene layer plane dimensions its relative orientation

Soot particles basically consist of carbon, oxygen and hydrogen, and some other constituents such as nitrogen, zinc, sulfur, etc. are also observed [24, 25]. In **Table 1**, the typical composition of soot obtained from the lubricant oil and soot contained are shown [26]. Soot in individual particles or spherical agglomerates is composed of many primary particles with approximately 10–50 nm in diameter [27]. The size of soot particles increases due to agglomeration because some particle diameters are up to 200 nm, and in this process, the soot-free radical character

The formation of soot is a complex process because this involves several physical and chemical steps and is still regarded as only partially understood. Soot particles

**94**

decreases.

*Soot percentage composition.*

obtained from different sources such as various fuels and combustion are expected to be approximately similar in composition and size, suggesting the same processes of formation and growth constraints. Many authors have presented a model of soot formation from liquid or vapor phase combustion, which mainly comprises or is classified in to five distinct and normal identified processes, namely pyrolysis, nucleation, surface growth, coalescence and agglomeration as presented in **Figure 1** [18, 28, 29].

Carbon soot production is also visualized as being a fuel thermal stability function [30]. Some authors also investigated that in the pyrolysis all hydrocarbons yield acetylene, which is the most precursor of species by incomplete combustion [31–33]. This is contributed to its low thermal stability where it easily breaks in to carbon solid and hydrogen. A well-defined and accepted theory for the formation of soot is explained by Haynes [18].

#### **2.3 Investigation of carbon soot nanoparticles**

Carbon nanosoots have been produced by two different edible oils by flame deposition techniques in two different environments.

#### *2.3.1 Formation of soots in natural environment (without water tub)*

At room temperature, the flame deposition method is a well known, cost-effective and easiest method to produce carbon nanosoot from different oils (**Figure 2**). In this technique, we take two diyas or "clay lamp": one filled with almond oil and the other one is filled with mustard oil. Dip a cotton wick in both diyas and put it on the floor at some distance (approx. 40 cm). Light up cotton wick. To collect carbon soot particles, put another diya in reverse at some height with the help of other layers of diyas and make the arrangement.

In this arrangement, the distance between the tip of the wick and collector diyas' surface is approximately 5 cm. The distance has been optimized by carrying out the pyrolysis process at various source collector distances. The flame stabilizes after 1–2 min and then the almond oil soot and mustard oil soot are allowed to deposit on the collector. For 2 h, the almond and mustard oils were burned, and then the generated soots were scrapped off using a spatula on butter paper and then samples were packed in air-tight bottles with proper labeling.

#### *2.3.2 Formation of soots in water tub environment (with water tub)*

In this section, the procedure of soot production from almond and mustard oil at a room temperature is the same as above mentioned (see Section 2.4.1). The only change made in this section is to introduce a water tub. The entire setup is arranged in a water tub to provide the sample surroundings extra moisture (**Figure 3**). After completion of the processes, all soot samples were stored in air-tight bottles and labeled (**Figure 4**).

**Figure 1.** *Soot formation steps from fuel.*

**Figure 2.** *Carbon soot-producing setup in natural environment.*

#### **2.4 Properties of carbon soot nanoparticles (CSNPCs)**

#### *2.4.1 X-ray diffraction analysis of almond soot (AS) and mustard soot (MS) nanoparticles*

#### *2.4.1.1 XRD analysis of almond oil soots*

The X-ray diffraction spectra in **Figure 5** are from almond soot without and with water tub environment. Samples show carbonaceous soot. The two theta values at 24.74 and 42.13° are identified for natural environment (without water tub) as graphite peaks. These peaks correspond to plane (002) and (101), respectively. Similarly, the sample with water tub got two prominent peaks. A high-intense peak at 24.04° and a low-intense peak at 43.69° appeared. As shown in the figure, the peaks of samples in the presence of water tub are with greater intensities as compared to samples in natural environment. Due to this property, its crystallinity is not lost. A high-intense peak at 24.74 and 24.04⁰ for natural and with water tub soot indicates the presence of large amount of amorphous carbon. Two peaks are at 42.13 and 43.69° and indicate the presence of low-quality carbon nanomaterial. All these peaks denote the presence of multiwalled graphite carbon nanotubes.

#### *2.4.1.2 XRD analysis of mustard oil soots*

The XRD profiles of carbon soot that are obtained without and with water tub (**Figure 6**), respectively, are quite similar in their pattern, both showing two

**97**

**Figure 5.**

**Figure 3.**

**Figure 4.**

*Carbon Soot Polymer Nanocomposites (CSPNCs): Production, Surface Morphological, Glass…*

*DOI: http://dx.doi.org/10.5772/intechopen.92389*

*Carbon soot-producing setup in water tub environment.*

*Picture of generated soot samples for characterization.*

*XRD spectra of almond soot without (A) and with water tub (A-H) environment.*

*Carbon Soot Polymer Nanocomposites (CSPNCs): Production, Surface Morphological, Glass… DOI: http://dx.doi.org/10.5772/intechopen.92389*

**Figure 3.** *Carbon soot-producing setup in water tub environment.*

*Environmental Emissions*

*Soot formation steps from fuel.*

**Figure 1.**

**Figure 2.**

**2.4 Properties of carbon soot nanoparticles (CSNPCs)**

*nanoparticles*

*2.4.1.1 XRD analysis of almond oil soots*

*Carbon soot-producing setup in natural environment.*

*2.4.1.2 XRD analysis of mustard oil soots*

*2.4.1 X-ray diffraction analysis of almond soot (AS) and mustard soot (MS)* 

The X-ray diffraction spectra in **Figure 5** are from almond soot without and with

water tub environment. Samples show carbonaceous soot. The two theta values at 24.74 and 42.13° are identified for natural environment (without water tub) as graphite peaks. These peaks correspond to plane (002) and (101), respectively. Similarly, the sample with water tub got two prominent peaks. A high-intense peak at 24.04° and a low-intense peak at 43.69° appeared. As shown in the figure, the peaks of samples in the presence of water tub are with greater intensities as compared to samples in natural environment. Due to this property, its crystallinity is not lost. A high-intense peak at 24.74 and 24.04⁰ for natural and with water tub soot indicates the presence of large amount of amorphous carbon. Two peaks are at 42.13 and 43.69° and indicate the presence of low-quality carbon nanomaterial. All these

peaks denote the presence of multiwalled graphite carbon nanotubes.

The XRD profiles of carbon soot that are obtained without and with water tub (**Figure 6**), respectively, are quite similar in their pattern, both showing two

**96**

**Figure 4.** *Picture of generated soot samples for characterization.*

**Figure 5.** *XRD spectra of almond soot without (A) and with water tub (A-H) environment.*

**Figure 6.** *XRD patterns of mustard soot without (M) and with water tub (M-H) environment.*

prominent broad diffused peaks. The sample with water tub exhibits higher intensity suggesting that the surrounding of water or creation of humid environment makes it less amorphous. For the soot samples without water tub, high-intense Bragg diffraction peak is found at 2θ = 24.78° and a low-intense peak at 44.15° for (002) and (100) reflections, respectively. These reflections suggest that the soots obtained by this method have a good extend to layer formation. Similarly, in the case of soot sample with water tub, a high-intense peak at 24.48° and low-intense peak at 42.03 show that crystallinity is not lost due to oxidative acid treatment, and these two peaks at 24.48 and 24.70° are a high-intensity broad peak, which indicates the presence of large amount of amorphous material in the soots. The low-intensity peaks at 42.03 and 44.15° are an indication of the low quality of carbon nanoparticles present in soots with and without water tub, respectively, and these observations are in quite agreement with the result reported by other researchers [34, 35].

#### *2.4.2 Field emission scanning electron microscopy analysis of almond soot (AS) and mustard soot (MS) nanoparticles*

#### *2.4.2.1 Field emission scanning electron microscopy analysis of almond oil soots*

The almond soot material deposited on glass surface was investigated by scanning electron microscopy for without and with water tub conditions. The particles are very small occurring nonindividually and individually. Synthesized soot particles in flame deposition method break up to form other small substances. For the first condition, surface morphology is seen to be nonuniform (**Figure 7a**), and there are several grains that look like carbon nanotubes, but for the second condition, it is seen to be uniform and particle size is small comparatively (**Figure 7b**). The SEM images for both conditions show carbon soot particles of average size approximately 50 nm. The formed soot particles show morphology of agglomerated clusters for without water tub sample and uniformly distributed carbon nanoparticles for with water tub sample.

#### *2.4.2.2 FESEM analysis of mustard oil soots*

Mustard oil is burned in two different environment to obtain soot by a flame deposition process in which oil breaks up to form other substances. The SEM images

**99**

**Figure 8.**

*presence of water tub.*

**Figure 7.**

*of water tub.*

*Carbon Soot Polymer Nanocomposites (CSPNCs): Production, Surface Morphological, Glass…*

of obtained particles describe the synthesized carbonaceous particles from burning of oil and are a mixture of elemental carbon and oxygen, a variety of hydrocarbons. The surface morphology of the deposited carbon obtained is seen to be nondistinguishable in natural environment sample (**Figure 8a**) and distinguishable in water

The prepared soot particles are agglomerated in a range between 50 and 100 nm, but most particles are about 50 nm in size. As shown in all SEM images, agglomerated soot particles with well-defined boundaries are arranged in the form of a chain

Energy dispersive X-ray of almond oil soot particles is presented for natural and with water tub condition. The spectra show the presence of carbon and oxygen. For the first condition (**Figure 9a**), the EDAX analysis indicates the soot to consist 92.10% weight of carbon and 7.9% weight of oxygen. For the second condition (**Figure 9b**), it consists of 87.86% carbon and 12.14% weight of oxygen. **Table 2** shows the percentage composition of elements carbon and oxygen obtained from

*Field emission scanning electron micrograph of almond oil soot (a) natural environment and (b) with presence* 

*Field emission scanning electron micrograph of mustard oil soot (a) natural environment and (b) with* 

*2.4.3 Chemical composition analysis of almond soot (AS) and mustard soot (MS)* 

*DOI: http://dx.doi.org/10.5772/intechopen.92389*

tub environment sample (**Figure 8b**).

*2.4.3.1 Energy dispersive X-ray study of almond oil soots*

(carbon necklace).

*nanoparticles*

*Carbon Soot Polymer Nanocomposites (CSPNCs): Production, Surface Morphological, Glass… DOI: http://dx.doi.org/10.5772/intechopen.92389*

of obtained particles describe the synthesized carbonaceous particles from burning of oil and are a mixture of elemental carbon and oxygen, a variety of hydrocarbons. The surface morphology of the deposited carbon obtained is seen to be nondistinguishable in natural environment sample (**Figure 8a**) and distinguishable in water tub environment sample (**Figure 8b**).

The prepared soot particles are agglomerated in a range between 50 and 100 nm, but most particles are about 50 nm in size. As shown in all SEM images, agglomerated soot particles with well-defined boundaries are arranged in the form of a chain (carbon necklace).

#### *2.4.3 Chemical composition analysis of almond soot (AS) and mustard soot (MS) nanoparticles*

#### *2.4.3.1 Energy dispersive X-ray study of almond oil soots*

Energy dispersive X-ray of almond oil soot particles is presented for natural and with water tub condition. The spectra show the presence of carbon and oxygen. For the first condition (**Figure 9a**), the EDAX analysis indicates the soot to consist 92.10% weight of carbon and 7.9% weight of oxygen. For the second condition (**Figure 9b**), it consists of 87.86% carbon and 12.14% weight of oxygen. **Table 2** shows the percentage composition of elements carbon and oxygen obtained from

#### **Figure 7.**

*Environmental Emissions*

**Figure 6.**

prominent broad diffused peaks. The sample with water tub exhibits higher intensity suggesting that the surrounding of water or creation of humid environment makes it less amorphous. For the soot samples without water tub, high-intense Bragg diffraction peak is found at 2θ = 24.78° and a low-intense peak at 44.15° for (002) and (100) reflections, respectively. These reflections suggest that the soots obtained by this method have a good extend to layer formation. Similarly, in the case of soot sample with water tub, a high-intense peak at 24.48° and low-intense peak at 42.03 show that crystallinity is not lost due to oxidative acid treatment, and these two peaks at 24.48 and 24.70° are a high-intensity broad peak, which indicates the presence of large amount of amorphous material in the soots. The low-intensity peaks at 42.03 and 44.15° are an indication of the low quality of carbon nanoparticles present in soots with and without water tub, respectively, and these observations are in quite agreement with the result reported by other researchers [34, 35].

*XRD patterns of mustard soot without (M) and with water tub (M-H) environment.*

*2.4.2 Field emission scanning electron microscopy analysis of almond soot (AS)* 

*2.4.2.1 Field emission scanning electron microscopy analysis of almond oil soots*

The almond soot material deposited on glass surface was investigated by scanning electron microscopy for without and with water tub conditions. The particles are very small occurring nonindividually and individually. Synthesized soot particles in flame deposition method break up to form other small substances. For the first condition, surface morphology is seen to be nonuniform (**Figure 7a**), and there are several grains that look like carbon nanotubes, but for the second condition, it is seen to be uniform and particle size is small comparatively (**Figure 7b**). The SEM images for both conditions show carbon soot particles of average size approximately 50 nm. The formed soot particles show morphology of agglomerated clusters for without water tub sample and uniformly distributed carbon nanoparticles for with

Mustard oil is burned in two different environment to obtain soot by a flame deposition process in which oil breaks up to form other substances. The SEM images

*and mustard soot (MS) nanoparticles*

*2.4.2.2 FESEM analysis of mustard oil soots*

**98**

water tub sample.

*Field emission scanning electron micrograph of almond oil soot (a) natural environment and (b) with presence of water tub.*

#### **Figure 8.**

*Field emission scanning electron micrograph of mustard oil soot (a) natural environment and (b) with presence of water tub.*

**Figure 9.** *EDAX spectra of almond oil soot in (a) without and (b) with water tub environment.*


#### **Table 2.**

*Elemental composition of almond and mustard oil soot in natural and with water tub environment.*

EDAX spectra of different samples in different conditions. The spectra reveal that almost 85% of the sample contains pure carbon and remaining 15% oxygen, confirming the absence of any other external impurities. This AS sample is electrically nonconducting, and for EDAX analysis, this sample is coated with gold to convert it into electrically conducting. Due to of this, an extra small peak is observed for gold at approximately 2 keV in EDAX spectra.

#### *2.4.3.2 EDAX study of mustard oil soots*

The elemental analysis of synthesized mustard soot was performed using energy dispersive X-ray (EDAX). The spectra show the presence of carbon and oxygen for both conditions. The composition of soot aggregates from the EDAX analysis shows the soot to consist of about 83.37% weight of carbon and 16.63% weight of oxygen element for first condition (**Figure 10a**), and similarly for second condition (**Figure 10b**), it consists of about 90.81% weight of carbon and 9.19% weight of oxygen as shown in **Table 2**. The result shows the product of the flame deposition of mustard oil to be composed of mainly almost (80–90)% carbon and remaining (10–20)% oxygen.

The EDAX of soot samples indicates the presence of no other except carbon and oxygen. This MS sample is electrically nonconducting, and for EDAX analysis, this sample is coated with gold to convert it into electrically conducting. Due to of this, an extra small peak is observed for gold at approximately 2 keV in EDAX spectra.

**101**

**Figure 10.**

*Carbon Soot Polymer Nanocomposites (CSPNCs): Production, Surface Morphological, Glass…*

FTIR transmission spectra for without and with water tub samples are shown in

is for water O▬H stretch, peaks at 2918 and 2919 cm<sup>−</sup><sup>1</sup>

and SP3

FTIR spectroscopy analysis was carried out to identify the chemical structure of carbon soot nanoparticles as well as the presence of any functional group, and the

FTIR spectra of Mustard Oil soot without and with water tub environment

carboxylic acid group. It also indicates the presence of absorbed moisture of OH group in the samples, and it is therefore more intense for with water tub sample as compared to without water tub as expected. Another vibration band at 2919 and

is due to symmetric and antisymmetric C▬H bond stretching. The band

is assigned to C〓O stretching vibration associated with the presence

are for C▬H

aromatic clusters of amorphous

range spectra resemble in

.

with a shoulder at 1384 cm<sup>−</sup><sup>1</sup>

is associated

corresponds to C▬N

indicate

is attributed to the OH stretching of the

is

stretch

and

*2.4.4 Fourier transform infrared spectroscopy analysis of almond soot (AS) and* 

*DOI: http://dx.doi.org/10.5772/intechopen.92389*

*mustard soot (MS) nanoparticles*

*2.4.4.2 FTIR analysis of mustard oil soots*

**Figure 11**.

1047, 705 cm<sup>−</sup><sup>1</sup>

carbon soot.

2852 cm<sup>−</sup><sup>1</sup>

at 1725 cm<sup>−</sup><sup>1</sup>

the presence of small (SP<sup>2</sup>

A peak at 3435 cm<sup>−</sup><sup>1</sup>

*2.4.4.1 Fourier transfer infrared analysis of almond oil soots*

indicate the presence of SP<sup>2</sup>

obtained spectra are shown in **Figure 12,** respectively.

conditions, shows that in between 1500 to 4000 cm<sup>−</sup><sup>1</sup>

of carboxylic acid group. A band centered at 1619 cm<sup>−</sup><sup>1</sup>

may be due to (C〓C) stretching vibrations. A band at 1217 cm<sup>−</sup><sup>1</sup>

*EDAX spectra of mustard oil soot in (a) without and (b) with water tub environment.*

stretch. Some obtained bands at low wave numbers 826, 738 and 597 cm<sup>−</sup><sup>1</sup>

) clusters.

with CO stretching vibrations. A band centered at 1047 cm<sup>−</sup><sup>1</sup>

and SP3

The broad vibration band at 3435 cm<sup>−</sup><sup>1</sup>

their profile and full spectra remain in the range 400 to 4000 cm<sup>−</sup><sup>1</sup>

are for C▬H stretch or carboxylic acid O▬H, and peaks at 2850 cm<sup>−</sup><sup>1</sup>

stretch or (▬C▬H) aldehyde. A weak peak for both soot spectra at 1617 cm<sup>−</sup><sup>1</sup>

for ▬CH3 group. Some detected bands at low wave numbers 1048, 668 cm<sup>−</sup><sup>1</sup>

detected for C〓C aromatic stretch. Two bands are at 1384 and 1377 cm<sup>−</sup><sup>1</sup>

*Carbon Soot Polymer Nanocomposites (CSPNCs): Production, Surface Morphological, Glass… DOI: http://dx.doi.org/10.5772/intechopen.92389*

*2.4.4 Fourier transform infrared spectroscopy analysis of almond soot (AS) and mustard soot (MS) nanoparticles*

#### *2.4.4.1 Fourier transfer infrared analysis of almond oil soots*

FTIR transmission spectra for without and with water tub samples are shown in **Figure 11**.

A peak at 3435 cm<sup>−</sup><sup>1</sup> is for water O▬H stretch, peaks at 2918 and 2919 cm<sup>−</sup><sup>1</sup> are for C▬H stretch or carboxylic acid O▬H, and peaks at 2850 cm<sup>−</sup><sup>1</sup> are for C▬H stretch or (▬C▬H) aldehyde. A weak peak for both soot spectra at 1617 cm<sup>−</sup><sup>1</sup> is detected for C〓C aromatic stretch. Two bands are at 1384 and 1377 cm<sup>−</sup><sup>1</sup> stretch for ▬CH3 group. Some detected bands at low wave numbers 1048, 668 cm<sup>−</sup><sup>1</sup> and 1047, 705 cm<sup>−</sup><sup>1</sup> indicate the presence of SP<sup>2</sup> and SP3 aromatic clusters of amorphous carbon soot.

#### *2.4.4.2 FTIR analysis of mustard oil soots*

*Environmental Emissions*

EDAX spectra of different samples in different conditions. The spectra reveal that almost 85% of the sample contains pure carbon and remaining 15% oxygen, confirming the absence of any other external impurities. This AS sample is electrically nonconducting, and for EDAX analysis, this sample is coated with gold to convert it into electrically conducting. Due to of this, an extra small peak is observed for gold

*Elemental composition of almond and mustard oil soot in natural and with water tub environment.*

**Samples of soot particles Percentage of carbon and oxygen elements**

Almond oil soot without water tub 92.10 7.90 Almond oil soot with water tub 87.86 12.14 Mustard oil soot without water tub 83.37 16.63 Mustard oil soot with water tub 90.81 9.19

*EDAX spectra of almond oil soot in (a) without and (b) with water tub environment.*

**Carbon element (C%) Oxygen element (O%)**

The elemental analysis of synthesized mustard soot was performed using energy

The EDAX of soot samples indicates the presence of no other except carbon and oxygen. This MS sample is electrically nonconducting, and for EDAX analysis, this sample is coated with gold to convert it into electrically conducting. Due to of this, an extra small peak is observed for gold at approximately 2 keV in

dispersive X-ray (EDAX). The spectra show the presence of carbon and oxygen for both conditions. The composition of soot aggregates from the EDAX analysis shows the soot to consist of about 83.37% weight of carbon and 16.63% weight of oxygen element for first condition (**Figure 10a**), and similarly for second condition (**Figure 10b**), it consists of about 90.81% weight of carbon and 9.19% weight of oxygen as shown in **Table 2**. The result shows the product of the flame deposition of mustard oil to be composed of mainly almost (80–90)% carbon and remaining

at approximately 2 keV in EDAX spectra.

*2.4.3.2 EDAX study of mustard oil soots*

**100**

(10–20)% oxygen.

**Table 2.**

**Figure 9.**

EDAX spectra.

FTIR spectroscopy analysis was carried out to identify the chemical structure of carbon soot nanoparticles as well as the presence of any functional group, and the obtained spectra are shown in **Figure 12,** respectively.

FTIR spectra of Mustard Oil soot without and with water tub environment conditions, shows that in between 1500 to 4000 cm<sup>−</sup><sup>1</sup> range spectra resemble in their profile and full spectra remain in the range 400 to 4000 cm<sup>−</sup><sup>1</sup> .

The broad vibration band at 3435 cm<sup>−</sup><sup>1</sup> is attributed to the OH stretching of the carboxylic acid group. It also indicates the presence of absorbed moisture of OH group in the samples, and it is therefore more intense for with water tub sample as compared to without water tub as expected. Another vibration band at 2919 and 2852 cm<sup>−</sup><sup>1</sup> is due to symmetric and antisymmetric C▬H bond stretching. The band at 1725 cm<sup>−</sup><sup>1</sup> is assigned to C〓O stretching vibration associated with the presence of carboxylic acid group. A band centered at 1619 cm<sup>−</sup><sup>1</sup> with a shoulder at 1384 cm<sup>−</sup><sup>1</sup> may be due to (C〓C) stretching vibrations. A band at 1217 cm<sup>−</sup><sup>1</sup> is associated with CO stretching vibrations. A band centered at 1047 cm<sup>−</sup><sup>1</sup> corresponds to C▬N stretch. Some obtained bands at low wave numbers 826, 738 and 597 cm<sup>−</sup><sup>1</sup> indicate the presence of small (SP<sup>2</sup> and SP3 ) clusters.

**Figure 10.** *EDAX spectra of mustard oil soot in (a) without and (b) with water tub environment.*

**Figure 11.** *FTIR spectra of almond soot in without (A) and with water tub (A-H) environment.*

**Figure 12.** *FTIR spectra of mustard oil soot in without (M) and with water tub (M-H) environment.*

These observations are in good agreement with the earlier reported ones [35–37]. So the IR studies directly prove the presence of carboxylic acid groups and clusters in synthesized soot.

#### **3. Polymer nanocomposites (PNCs)**

The nanomaterials can be divided into two types: one is nanostructured materials and another one is nanophase materials. Normally, bulk materials are made by grains (agglomerates) with the nanometer range. Nanocomposites refer to materials existing of minimum two phases with one dispersed in another and making a 3D network. The dispersion medium is called matrix and the dispersed phase is called filler. If the host matrix of nanocomposite is polymer, then the resulting nanocomposite is called polymer nanocomposite (PNC). PNC belongs to the nanostructural class material. If filler has higher dimensions, the resulting composite refers to polymer composite (PC). PNCs are different to other PC materials; their filler consists at the nanoscale [38, 39]. According via, PNC's particles exists on nanoscale measure and particles with nanoscale arrangements has a polymer host matrix with nanoparticles. PNCs have been shown to possess the classic thermal and mechanical

**103**

**Figure 14.**

**Figure 13.**

*Carbon Soot Polymer Nanocomposites (CSPNCs): Production, Surface Morphological, Glass…*

properties [40, 41]. Nanoparticles are in size less than the wavelength of visible

**4. Production of carbon soot (AS and MS)/PMMA nanocomposites**

PMMA nanocomposite and the other one is MS/PMMA nanocomposites.

*Actual setup of pure PMMA solution by magnetic stirrer and ultrasonication.*

*Actual setup of CS/PMMA homogeneous solution by magnetic stirrer and ultrasonication.*

The synthesizing technique in the production of carbon soot polymer nanocomposites was a mixture of solution mixing and solvent casting. In this section, synthesized nanocomposites for two different nanofillers are discussed: one is AS/

• For the solution of PMMA, PMMA was dissolved in 20 ml dichloromethane (DCM) solvent using the help of magnetic stirrer for a duration of 3 h

• Nanofiller carbon soots (almond soot particles and mustard soot particles) 1 and 2 mg were dispersed in the polymer solution by ultrasonication for 4 h

*DOI: http://dx.doi.org/10.5772/intechopen.92389*

light, giving the unique optical properties.

(**Figure 13**).

*Carbon Soot Polymer Nanocomposites (CSPNCs): Production, Surface Morphological, Glass… DOI: http://dx.doi.org/10.5772/intechopen.92389*

properties [40, 41]. Nanoparticles are in size less than the wavelength of visible light, giving the unique optical properties.

### **4. Production of carbon soot (AS and MS)/PMMA nanocomposites**

The synthesizing technique in the production of carbon soot polymer nanocomposites was a mixture of solution mixing and solvent casting. In this section, synthesized nanocomposites for two different nanofillers are discussed: one is AS/ PMMA nanocomposite and the other one is MS/PMMA nanocomposites.


#### **Figure 13.**

*Environmental Emissions*

**102**

clusters in synthesized soot.

**Figure 12.**

**Figure 11.**

**3. Polymer nanocomposites (PNCs)**

These observations are in good agreement with the earlier reported ones [35–37]. So the IR studies directly prove the presence of carboxylic acid groups and

*FTIR spectra of mustard oil soot in without (M) and with water tub (M-H) environment.*

*FTIR spectra of almond soot in without (A) and with water tub (A-H) environment.*

The nanomaterials can be divided into two types: one is nanostructured materials and another one is nanophase materials. Normally, bulk materials are made by grains (agglomerates) with the nanometer range. Nanocomposites refer to materials existing of minimum two phases with one dispersed in another and making a 3D network. The dispersion medium is called matrix and the dispersed phase is called filler. If the host matrix of nanocomposite is polymer, then the resulting nanocomposite is called polymer nanocomposite (PNC). PNC belongs to the nanostructural class material. If filler has higher dimensions, the resulting composite refers to polymer composite (PC). PNCs are different to other PC materials; their filler consists at the nanoscale [38, 39]. According via, PNC's particles exists on nanoscale measure and particles with nanoscale arrangements has a polymer host matrix with nanoparticles. PNCs have been shown to possess the classic thermal and mechanical *Actual setup of pure PMMA solution by magnetic stirrer and ultrasonication.*

(at the end temperature of sonication was 35°C) to get a homogeneous solution (**Figure 14**).


#### **5. Properties of CS/PMMA nanocomposites (CSPNCs)**

#### **5.1 Surface morphological and chemical composition properties**

Atomic force microscopy study is a characteristic and quantitative analysis for measuring the surface roughness at nanodimension and visualizing the nanotexture of the deposited thin film surface. The topography deflection image and 3D AFM images of the pure PMMA and CS/PMMA nanocomposites, in which the roughness value of nanocomposites are carried out, are shown in **Figure 15a**–**c**.

The roughness parameter with average roughness (Ra), root mean square roughness (Rq), skewness of the line (Rsk) and kurtosis of the line (Rku) roughness data are shown in **Table 3**. The pure PMMA thin film, AS/PMMA and MS/PMMA thin films are synthesized for comparative analysis of surface roughness. The measures of roughness of carbon soot polymer thin films are less than the roughness of pure PMMA film. This implies that the prepared PMMA thin films with almond and mustard soot decrease the surface roughness. The ration of roughness value Rq and Ra (Rq/Ra) are approximately close to theoretical data, recorded by Ward et al. in 1982 [42].

The chemical composition for CSPNCs was carried out by EDAX (energy dispersive X-ray analysis). Results from EDAX depicted in **Figure 16a**–**c** reveal the chemical composition as follows:

Carbon approximately 75% and remaining oxygen approximately 25% for all nanocomposite samples with individual content of PMMA, AS/PMMA and MS/ PMMA are 76.31, 76.20, 75.26% and 23.69, 23.80, 24.74% respectively (**Table 4**). These CS (AS and MS)/PMMA samples are electrically nonconducting, and for EDAX analysis, these samples are coated with gold to convert them into electrically conducting. Due to this, an extra small peak is observed for gold at approximately 2 keV in EDAX spectra.

#### **5.2 Spectroscopic properties**

The FTIR spectra of PMMA show sharp intense peaks at 1725 and 1141 cm<sup>−</sup><sup>1</sup> and are attributed to the ester carbonyl stretching and C▬O▬C bending vibration. In addition, peaks appeared at 3000 and 2950 cm<sup>−</sup><sup>1</sup> and are assigned to the C▬H stretching vibrations, while the peaks at 752 and 840 cm<sup>−</sup><sup>1</sup> are attributed to the

**105**

**Figure 15.**

*film.*

The peak at 984 cm<sup>−</sup><sup>1</sup>

noted that there is no peak near 1680 to 1640 cm<sup>−</sup><sup>1</sup>

PMMA viz. pure are shown in **Figures 17** and **18**, respectively.

*Carbon Soot Polymer Nanocomposites (CSPNCs): Production, Surface Morphological, Glass…*

vibration of polymethyl methacrylate chains and the deformation vibration of PMMA O▬C▬O, respectively. Moreover, the peaks at 1236, 1383 and 1440 cm<sup>−</sup><sup>1</sup>

attributed to the ester band symmetrical and asymmetrical stretching vibrations.

*Topographic deflection image and 3D image of (a) pure PMMA, (b) AS/PMMA, and (c) MS/PMMA thin* 

methyl methacrylate (MMA) monomers are converted into PMMA polymer. The FTIR patterns of almond soot-doped PMMA viz. pure and mustard soot-doped

represented C▬H bending wagging vibration. It should be

range, which confirms that all

were

*DOI: http://dx.doi.org/10.5772/intechopen.92389*

*Carbon Soot Polymer Nanocomposites (CSPNCs): Production, Surface Morphological, Glass… DOI: http://dx.doi.org/10.5772/intechopen.92389*

**Figure 15.**

*Environmental Emissions*

(**Figure 14**).

was floating over mercury in vacuum box.

(at the end temperature of sonication was 35°C) to get a homogeneous solution

• At the end, a homogeneous solution was purged in a flat glass Petri dish, which

• We take the prepared homogeneous solution for approximately 24 hr in a Petri dish in low vacuum (8-10mTorr) at room temperature, and after the thin film

• Thin film of polymer (PMMA) without the nanofiller (carbon soots) was also prepared for the reference composite used in the comparison study of many composite properties. The film of pure PMMA was transparent and other composite films were opaque and in black color due to dispersion of carbon soots. All produced films were in the thickness of 100 μm for pure PMMA and

Atomic force microscopy study is a characteristic and quantitative analysis for measuring the surface roughness at nanodimension and visualizing the nanotexture of the deposited thin film surface. The topography deflection image and 3D AFM images of the pure PMMA and CS/PMMA nanocomposites, in which the roughness

The roughness parameter with average roughness (Ra), root mean square roughness (Rq), skewness of the line (Rsk) and kurtosis of the line (Rku) roughness data are shown in **Table 3**. The pure PMMA thin film, AS/PMMA and MS/PMMA thin films are synthesized for comparative analysis of surface roughness. The measures of roughness of carbon soot polymer thin films are less than the roughness of pure PMMA film. This implies that the prepared PMMA thin films with almond and mustard soot decrease the surface roughness. The ration of roughness value Rq and Ra (Rq/Ra) are approximately close to theoretical data, recorded by Ward et al. in

The chemical composition for CSPNCs was carried out by EDAX (energy dispersive X-ray analysis). Results from EDAX depicted in **Figure 16a**–**c** reveal the

Carbon approximately 75% and remaining oxygen approximately 25% for all nanocomposite samples with individual content of PMMA, AS/PMMA and MS/ PMMA are 76.31, 76.20, 75.26% and 23.69, 23.80, 24.74% respectively (**Table 4**). These CS (AS and MS)/PMMA samples are electrically nonconducting, and for EDAX analysis, these samples are coated with gold to convert them into electrically conducting. Due to this, an extra small peak is observed for gold at approximately

The FTIR spectra of PMMA show sharp intense peaks at 1725 and 1141 cm<sup>−</sup><sup>1</sup> and are attributed to the ester carbonyl stretching and C▬O▬C bending vibration.

and are assigned to the C▬H

are attributed to the

samples reach a dry state, they are removed from Petri dishes.

different concentration (1 and 2 mg) of carbon soot nanofillers.

**5. Properties of CS/PMMA nanocomposites (CSPNCs)**

**5.1 Surface morphological and chemical composition properties**

value of nanocomposites are carried out, are shown in **Figure 15a**–**c**.

**104**

1982 [42].

chemical composition as follows:

2 keV in EDAX spectra.

**5.2 Spectroscopic properties**

In addition, peaks appeared at 3000 and 2950 cm<sup>−</sup><sup>1</sup>

stretching vibrations, while the peaks at 752 and 840 cm<sup>−</sup><sup>1</sup>

*Topographic deflection image and 3D image of (a) pure PMMA, (b) AS/PMMA, and (c) MS/PMMA thin film.*

vibration of polymethyl methacrylate chains and the deformation vibration of PMMA O▬C▬O, respectively. Moreover, the peaks at 1236, 1383 and 1440 cm<sup>−</sup><sup>1</sup> were attributed to the ester band symmetrical and asymmetrical stretching vibrations. The peak at 984 cm<sup>−</sup><sup>1</sup> represented C▬H bending wagging vibration. It should be noted that there is no peak near 1680 to 1640 cm<sup>−</sup><sup>1</sup> range, which confirms that all methyl methacrylate (MMA) monomers are converted into PMMA polymer. The FTIR patterns of almond soot-doped PMMA viz. pure and mustard soot-doped PMMA viz. pure are shown in **Figures 17** and **18**, respectively.


**Table 3.**

*The roughness parameters of CS/PMMA nanocomposites.*

**Figure 16.** *EDAX spectra of (a) PMMA, (b) almond soot/PMMA, and (c) mustard soot/PMMA samples.*

The doping level of almond soot and mustard soot fillers is 1 and 2 mg, respectively. Two broad peaks are centered at 1725 and 1141 cm<sup>−</sup><sup>1</sup> in AS/PMMA and MS/PMMA.

The other peaks are at 3000, 2950, 1440, 1383, 1236, 984, 839, 752 and 481 cm<sup>−</sup><sup>1</sup> , which correspond to the formation of PMMA matrix. If we compare the pure PMMA and AS/PMMA or MS/PMMA nanocomposites, we will find there is no change in wave number (**Figures 17** and **18**). These show that all AS and MS filler particles were loaded inside the polymer matrix without changing their chemical structure with low intensity as the AS and MS particle concentration increases.

#### **5.3 Optical properties**

In this section, we discuss the optical properties of polymethyl methacrylate (PMMA), almond soot/PMMA and mustard soot/PMMA nanocomposites for different concentration. The absorbance spectra of nanocomposite thin films were recorded in the range between 200 and 800 nm.

#### *5.3.1 Absorption data*

The recorded absorbance spectra of pure PMMA and almond soot (**Figure 19a**) and pure PMMA and mustard soot (**Figure 19b**) nanocomposites with different concentration at the wavelength of 200–800 nm show that the absorbance value increases with the addition of increased carbon soot (AS/MS) nanofillers.

As the absorption peaks increase, these show the existence of internal chemical interaction between the carbon soot nanofillers and PMMA matrix. In this manner, our study of optical properties for PMMA and doped freshly carbon soots such as almond soot particles and mustard soot particles at a different concentration give us good results. The result from synthesized carbon aggregates and aerosol particles

**107**

*Carbon Soot Polymer Nanocomposites (CSPNCs): Production, Surface Morphological, Glass…*

**C% O%**

**Samples Elemental compositions**

Pure PMMA 76.31 23.69 AS/PMMA 76.20 23.80 MS/PMMA 75.26 24.74

investigated by light scattering and light absorption shows a good agreement with

The absorbance coefficients of PMMA, AS/PMMA (**Figure 20a**) and PMMA, MS/PMMA (**Figure 20b**) nanocomposite thin films are shown in the below figure.

the expected transition of electron is indirect. In our study, the absorption coefficient (α) values of the polymer matrix (PMMA) and all filler nanocomposites

cm<sup>−</sup><sup>1</sup>

, then the elec-

, then

cm<sup>−</sup><sup>1</sup>

results obtained by other research groups [43, 44].

*The FTIR spectra of pure PMMA and MS/PMMA nanocomposites.*

*The FTIR spectra of pure PMMA and AS/PMMA nanocomposites.*

According to a review, if the value of α is high or α > 104

tron direct transition is expected. If the value of α is low or α < 104

*5.3.2 Absorption coefficient data analysis*

*DOI: http://dx.doi.org/10.5772/intechopen.92389*

*Elemental compositions of PMMA, AS/PMMA and MS/PMMA.*

**Table 4.**

**Figure 17.**

**Figure 18.**

*Carbon Soot Polymer Nanocomposites (CSPNCs): Production, Surface Morphological, Glass… DOI: http://dx.doi.org/10.5772/intechopen.92389*


**Table 4.**

*Environmental Emissions*

**Figure 16.**

**Table 3.**

MS/PMMA.

**5.3 Optical properties**

*5.3.1 Absorption data*

*EDAX spectra of (a) PMMA, (b) almond soot/PMMA, and (c) mustard soot/PMMA samples.*

tively. Two broad peaks are centered at 1725 and 1141 cm<sup>−</sup><sup>1</sup>

**Samples Roughness parameters**

*The roughness parameters of CS/PMMA nanocomposites.*

**Ra (nm) Rq (nm) Rq/Ra Rsk Rku**

Pure PMMA 2.99 4.40 1.47 2.64 25.5 AS/PMMA 2.18 4.10 1.88 –3.36 36.1 MS/PMMA 2.05 3.10 1.51 2.02 15.2

recorded in the range between 200 and 800 nm.

The doping level of almond soot and mustard soot fillers is 1 and 2 mg, respec-

The other peaks are at 3000, 2950, 1440, 1383, 1236, 984, 839, 752 and 481 cm<sup>−</sup><sup>1</sup>

In this section, we discuss the optical properties of polymethyl methacrylate (PMMA), almond soot/PMMA and mustard soot/PMMA nanocomposites for different concentration. The absorbance spectra of nanocomposite thin films were

The recorded absorbance spectra of pure PMMA and almond soot (**Figure 19a**) and pure PMMA and mustard soot (**Figure 19b**) nanocomposites with different concentration at the wavelength of 200–800 nm show that the absorbance value increases with the addition of increased carbon soot (AS/MS) nanofillers.

As the absorption peaks increase, these show the existence of internal chemical interaction between the carbon soot nanofillers and PMMA matrix. In this manner, our study of optical properties for PMMA and doped freshly carbon soots such as almond soot particles and mustard soot particles at a different concentration give us good results. The result from synthesized carbon aggregates and aerosol particles

which correspond to the formation of PMMA matrix. If we compare the pure PMMA and AS/PMMA or MS/PMMA nanocomposites, we will find there is no change in wave number (**Figures 17** and **18**). These show that all AS and MS filler particles were loaded inside the polymer matrix without changing their chemical structure with low intensity as the AS and MS particle concentration increases.

in AS/PMMA and

,

**106**

*Elemental compositions of PMMA, AS/PMMA and MS/PMMA.*

#### **Figure 17.**

*The FTIR spectra of pure PMMA and AS/PMMA nanocomposites.*

**Figure 18.** *The FTIR spectra of pure PMMA and MS/PMMA nanocomposites.*

investigated by light scattering and light absorption shows a good agreement with results obtained by other research groups [43, 44].

#### *5.3.2 Absorption coefficient data analysis*

The absorbance coefficients of PMMA, AS/PMMA (**Figure 20a**) and PMMA, MS/PMMA (**Figure 20b**) nanocomposite thin films are shown in the below figure.

According to a review, if the value of α is high or α > 104 cm<sup>−</sup><sup>1</sup> , then the electron direct transition is expected. If the value of α is low or α < 104 cm<sup>−</sup><sup>1</sup> , then the expected transition of electron is indirect. In our study, the absorption coefficient (α) values of the polymer matrix (PMMA) and all filler nanocomposites

#### **Figure 19.**

*Absorbance spectra of pure PMMA with (a) AS/PMMA nanocomposites and (b) MS/PMMA nanocomposites.*

#### **Figure 20.**

*Variation of absorption coefficient of PMMA with (a) AS-doped PMMA nanocomposite thin films and (b) MS-doped PMMA nanocomposite thin films.*

are not >104 cm<sup>−</sup><sup>1</sup> , and this implies the indirect electron transition in AS and MS conditions.

In this study of nanocomposite optical properties, we used carbon nanosoot obtained from incomplete combustion of flame deposition method similar to "Sara D." et al. in 2018. They found the absorption coefficient for two different flamegenerated soot particles, in which the results for both cases were identical [45]. The results of absorbance coefficient for PMMA matrix and carbon soots-doped PMMA nanocomposites indicate indirect electron transition.

#### *5.3.3 Band gap analysis*

The band gap plots of polymer matrix and AS/PMMA (**Figure 21a**) and polymer matrix and MS/PMMA (**Figure 21b**) nanocomposites on the variation of (αhν) 1/2 and (hν) are represented. These band gap spectra show that the measurements

**109**

**Figure 21.**

**Table 5.**

(**Figure 22a**–**c**).

*Carbon Soot Polymer Nanocomposites (CSPNCs): Production, Surface Morphological, Glass…*

revealed that the concentration of filler nanoparticles affects the optical properties of PMMA matrix. The decreasing values of optical energy band gap with adding the

In this study, we have prepared the polymeric thin film of host matrix PS and carbon soot-doped PS nanocomposites at a different weight percentage of almond

The steps for preparation of CS/PS nanocomposite thin films are similar as

We measure the surface topology and roughness of CS/PS composites with horizontal length scale in micrometer and vertical scale in the range of nanometer

**6. Production of carbon soot (AS and MS)/PS nanocomposites**

*The band gap spectra of PMMA with (a) AS/PMMA thin films and (b) MS/PMMA thin films.*

Pure PMMA for AS 4.22 AS-1 mg/PMMA 3.87 AS-2 mg/PMMA 3.68 Pure PMMA for MS 4.55 MS-1 mg/PMMA 3.94 MS-2 mg/PMMA 3.68

*Energy band gap values of PMMA, almond soot and mustard soot nanocomposites.*

**Samples Energy band gap values Eg (eV)**

and mustard soot of 50 μm thickness by solution casting technique.

**7.1 Surface morphological and chemical composition properties**

**7. Properties of CS/PS nanocomposites (CSPNCs)**

carbon soot in PMMA, are located in **Table 5**.

discussed above in Section 4.

*DOI: http://dx.doi.org/10.5772/intechopen.92389*

*Carbon Soot Polymer Nanocomposites (CSPNCs): Production, Surface Morphological, Glass… DOI: http://dx.doi.org/10.5772/intechopen.92389*

#### **Figure 21.**

*Environmental Emissions*

**Figure 19.**

**Figure 20.**

are not >104

conditions.

*(b) MS-doped PMMA nanocomposite thin films.*

nanocomposites indicate indirect electron transition.

cm<sup>−</sup><sup>1</sup>

*5.3.3 Band gap analysis*

*nanocomposites.*

*Absorbance spectra of pure PMMA with (a) AS/PMMA nanocomposites and (b) MS/PMMA* 

*Variation of absorption coefficient of PMMA with (a) AS-doped PMMA nanocomposite thin films and* 

In this study of nanocomposite optical properties, we used carbon nanosoot obtained from incomplete combustion of flame deposition method similar to "Sara D." et al. in 2018. They found the absorption coefficient for two different flamegenerated soot particles, in which the results for both cases were identical [45]. The results of absorbance coefficient for PMMA matrix and carbon soots-doped PMMA

The band gap plots of polymer matrix and AS/PMMA (**Figure 21a**) and polymer

matrix and MS/PMMA (**Figure 21b**) nanocomposites on the variation of (αhν) 1/2 and (hν) are represented. These band gap spectra show that the measurements

, and this implies the indirect electron transition in AS and MS

**108**

*The band gap spectra of PMMA with (a) AS/PMMA thin films and (b) MS/PMMA thin films.*


#### **Table 5.**

*Energy band gap values of PMMA, almond soot and mustard soot nanocomposites.*

revealed that the concentration of filler nanoparticles affects the optical properties of PMMA matrix. The decreasing values of optical energy band gap with adding the carbon soot in PMMA, are located in **Table 5**.

#### **6. Production of carbon soot (AS and MS)/PS nanocomposites**

In this study, we have prepared the polymeric thin film of host matrix PS and carbon soot-doped PS nanocomposites at a different weight percentage of almond and mustard soot of 50 μm thickness by solution casting technique.

The steps for preparation of CS/PS nanocomposite thin films are similar as discussed above in Section 4.

#### **7. Properties of CS/PS nanocomposites (CSPNCs)**

#### **7.1 Surface morphological and chemical composition properties**

We measure the surface topology and roughness of CS/PS composites with horizontal length scale in micrometer and vertical scale in the range of nanometer (**Figure 22a**–**c**).

**Figure 22.**

*Topographic deflection image and 3D AFM image of (a) PS (pure polystyrene), (b) AS/PS nanocomposite thin film and (c) MS/PS nanocomposite thin film.*

The roughness parameters of carbon soot polymer nanocomposites (CSPNCs) including the average surface roughness (Ra), root mean square roughness (Rq), skewness of the line (Rsk) and kurtosis of the line (Rku) roughness are obtained by AFM machine. The average surface roughness for pure PS, AS/PS and MS/PS with values of 2.99, 2.18 and 2.05 nm is carried out as well as the root mean square roughness for pure PS, AS/PS and MS/PS nanocomposites with the values of 4.40, 4.10 and 3.10 nm is obtained. Also, Rsk and Rku values of all samples are found out, while the rations of Rq/Ra of all samples are calculated for all composites, as shown in **Table 6**.

**111**

**Table 6.**

*Carbon Soot Polymer Nanocomposites (CSPNCs): Production, Surface Morphological, Glass…*

As mentioned in the table, the surface roughness decreases with the doping of almond soot in PS matrix and the surface roughness increases with the doping of mustard soot in PS matrix, as compared with the pure polystyrene sample. The obtained result reveals that surface of AS/PS nanocomposites is smoother as compares to that of MS/PS and pure PS sample. We calculated the ratio of root mean square roughness and average roughness, and the ratio of Rq/Ra almost matched the value of theoretical ratio data. The surface roughness of composite samples plays an

The analytical composition of soot filler nanocomposites carried out by energy dispersive X-ray spectroscopy of studied samples is represented in **Figure 23a**–**c**. We can see that all samples contained approximately 98–99% carbon and remaining

It is confirmed that the sample composed of only carbon and oxygen element, without any other element. These CS (AS and MS)/PS samples are electrically nonconducting, and for EDAX analysis, these samples are coated with gold to convert them into electrically conducting. Due to of this, an extra small peak is observed for

The XRD spectra of pure polystyrene almond soot/PS (**Figure 24a**) and mustard

The FTIR pattern of pure polystyrene shown as a broad intense peak at 694 cm<sup>−</sup><sup>1</sup> is attributed to the (C▬H) bend due to the ring deformation vibration. A peak at

carbonyl stretching vibration and C▬H bending vibration. Some bands at 1216, 1027

Pure PS 6.69 11.0 1.64 −1.22 8.44 AS/PS 3.53 5.50 1.55 2.61 25.6 MS/PS 10.3 16.3 1.58 0.65 6.67

is attributed to C▬H stretching with asymmetric CH3 group and C〓O

**Ra (nm) Rq (nm) Rq/Ra Rsk Rku**

are assigned due to aromatic C〓C stretch-

correspond to the plane deformation of

are attributed to the ester

soot/PS (**Figure 24b**) nanocomposites at different weight concentration (1 and 2 wt%) are in the range of 2θ = 20–90°. The X-ray diffraction pattern from pure PS, AS/PS nanocomposites with 1 and 2 wt% and MS/PS nanocomposites with 1 and 2 wt% concentrations does not show any visible peaks. This corresponds to the pure amorphous polymeric structure without any peak and suggested that the carbon soot particles had been exfoliated in the soot nanocomposites, as referred in [46, 47]. As shown in **Figure 24a** and **b**, the XRD pattern of AS/PS and MS/PS nanocomposites at different weight concentrations does not loss own nature. All results suggest that the variation of intensity confirms the presence of carbon soot

*DOI: http://dx.doi.org/10.5772/intechopen.92389*

important role in the wetting properties.

gold at approximately 2 keV in EDAX spectra (**Figure 23**).

.

ing, and the other two peaks at 1450 and 1366 cm<sup>−</sup><sup>1</sup>

in the range 600–1200 cm<sup>−</sup><sup>1</sup>

*The surface roughness parameters of carbon soot/polystyrene nanocomposites.*

**Samples Surface roughness parameters**

The two peaks at 1600 and 1491cm<sup>−</sup><sup>1</sup>

1–2% oxygen element (**Table 7**).

**7.2 X-ray diffraction properties**

in polymer nanocomposites.

**7.3 Spectroscopic properties**

stretching around 1739 cm<sup>−</sup><sup>1</sup>

2918 cm<sup>−</sup><sup>1</sup>

and 905 cm<sup>−</sup><sup>1</sup>

*Carbon Soot Polymer Nanocomposites (CSPNCs): Production, Surface Morphological, Glass… DOI: http://dx.doi.org/10.5772/intechopen.92389*

As mentioned in the table, the surface roughness decreases with the doping of almond soot in PS matrix and the surface roughness increases with the doping of mustard soot in PS matrix, as compared with the pure polystyrene sample. The obtained result reveals that surface of AS/PS nanocomposites is smoother as compares to that of MS/PS and pure PS sample. We calculated the ratio of root mean square roughness and average roughness, and the ratio of Rq/Ra almost matched the value of theoretical ratio data. The surface roughness of composite samples plays an important role in the wetting properties.

The analytical composition of soot filler nanocomposites carried out by energy dispersive X-ray spectroscopy of studied samples is represented in **Figure 23a**–**c**. We can see that all samples contained approximately 98–99% carbon and remaining 1–2% oxygen element (**Table 7**).

It is confirmed that the sample composed of only carbon and oxygen element, without any other element. These CS (AS and MS)/PS samples are electrically nonconducting, and for EDAX analysis, these samples are coated with gold to convert them into electrically conducting. Due to of this, an extra small peak is observed for gold at approximately 2 keV in EDAX spectra (**Figure 23**).

#### **7.2 X-ray diffraction properties**

*Environmental Emissions*

**110**

in **Table 6**.

**Figure 22.**

*film and (c) MS/PS nanocomposite thin film.*

*Topographic deflection image and 3D AFM image of (a) PS (pure polystyrene), (b) AS/PS nanocomposite thin* 

The roughness parameters of carbon soot polymer nanocomposites (CSPNCs) including the average surface roughness (Ra), root mean square roughness (Rq), skewness of the line (Rsk) and kurtosis of the line (Rku) roughness are obtained by AFM machine. The average surface roughness for pure PS, AS/PS and MS/PS with values of 2.99, 2.18 and 2.05 nm is carried out as well as the root mean square roughness for pure PS, AS/PS and MS/PS nanocomposites with the values of 4.40, 4.10 and 3.10 nm is obtained. Also, Rsk and Rku values of all samples are found out, while the rations of Rq/Ra of all samples are calculated for all composites, as shown

The XRD spectra of pure polystyrene almond soot/PS (**Figure 24a**) and mustard soot/PS (**Figure 24b**) nanocomposites at different weight concentration (1 and 2 wt%) are in the range of 2θ = 20–90°. The X-ray diffraction pattern from pure PS, AS/PS nanocomposites with 1 and 2 wt% and MS/PS nanocomposites with 1 and 2 wt% concentrations does not show any visible peaks. This corresponds to the pure amorphous polymeric structure without any peak and suggested that the carbon soot particles had been exfoliated in the soot nanocomposites, as referred in [46, 47]. As shown in **Figure 24a** and **b**, the XRD pattern of AS/PS and MS/PS nanocomposites at different weight concentrations does not loss own nature. All results suggest that the variation of intensity confirms the presence of carbon soot in polymer nanocomposites.

#### **7.3 Spectroscopic properties**

The FTIR pattern of pure polystyrene shown as a broad intense peak at 694 cm<sup>−</sup><sup>1</sup> is attributed to the (C▬H) bend due to the ring deformation vibration. A peak at 2918 cm<sup>−</sup><sup>1</sup> is attributed to C▬H stretching with asymmetric CH3 group and C〓O stretching around 1739 cm<sup>−</sup><sup>1</sup> .

The two peaks at 1600 and 1491cm<sup>−</sup><sup>1</sup> are assigned due to aromatic C〓C stretching, and the other two peaks at 1450 and 1366 cm<sup>−</sup><sup>1</sup> are attributed to the ester carbonyl stretching vibration and C▬H bending vibration. Some bands at 1216, 1027 and 905 cm<sup>−</sup><sup>1</sup> in the range 600–1200 cm<sup>−</sup><sup>1</sup> correspond to the plane deformation of


**Table 6.**

*The surface roughness parameters of carbon soot/polystyrene nanocomposites.*

#### *Environmental Emissions*


**Table 7.**

*Percentage of element compositions of PS, AS/PS and MS/PS thin film.*

**Figure 23.** *EDAX spectra of (a) PMMA, (b) almond soot/PMMA and (c) mustard soot/PMMA samples.*

C▬H group bending. Another peak at 750 cm<sup>−</sup><sup>1</sup> shows due to (C▬H) deformation vibration band of benzene ring hydrogen.

The comparative study on Fourier transform infrared spectra of pure polystyrene vs doped carbon soot/PS nanocomposites shows (**Figures 25** and **26**) the peaks around 2920, 1739, 1600, 1492, 1451, 1367, 1215, 1027, 905, 750 and 537 cm<sup>−</sup><sup>1</sup> corresponding to the formation of PS. Bands of CS/PS nanocomposites are more and less as compared to the peaks of pure polystyrene, but there are no other peaks found, showing that all the soot nanoparticles are loaded inside the PS host matrix without changing their chemical structure. No other modification in the shift of chemicals

**113**

**Figure 25.**

*Carbon Soot Polymer Nanocomposites (CSPNCs): Production, Surface Morphological, Glass…*

and the shape of band is noticed in the carbon soot/polystyrene nanocomposite spectra, indicating no chemical modification occurred in the polystyrene.

In this section, we discuss about the optical properties of polystyrene nanocomposites. Here, the carbon soot was doped with either almond soot or mustard soot particles with 1 and 2 wt%, respectively. In the optical properties, we tried to understand the absorption coefficient properties. Therefore, we measured the band

The absorbance data spectra of pure polystyrene and AS/PS (**Figure 27a**) and pure polystyrene and MS/PS (**Figure 27b**) nanocomposite thin films show the value of absorbance increases with doping the carbon soot in PS as compared to the pure PS. The increased absorbance in spectral profile from nanocomposite reveals the correlation between carbon soot nanoparticles and the host matrix polystyrene matrix. In this study, carbon soot (traditional Indian name—"Kajal") is produced by incomplete combustion of almond and mustard oil by flame deposition method. Researchers also used different types of soot from aerosol carbon particles, diesel soot and other sources. Similar results were found by Mita et al. in 1980 [48] from absorbance of aerosol soot particles. As seen in the figures, the value of absorbance is low at high wavelength and high absorbance value corresponding to the low

The absorption coefficient spectra of polystyrene and soot/polymer nanocom-

1/2 Vs hν

For the indirect band gap, the value of r is 1/2; hence, the indirect band gap

(**Figure 29a** and **b**). It has been noticed that the band gap is inversely proportional

of nanocomposite thin films is obtained using the help of plot (αhν)

*DOI: http://dx.doi.org/10.5772/intechopen.92389*

gap of nanocomposites in the range of 200–800 nm.

*7.4.2 Absorption coefficient and band gap study*

posites are represented in **Figure 28a** and **b**.

*FTIR spectra of almond soot polystyrene nanocomposites.*

**7.4 Optical properties**

*7.4.1 The absorption data*

wavelengths.

and the shape of band is noticed in the carbon soot/polystyrene nanocomposite spectra, indicating no chemical modification occurred in the polystyrene.

#### **7.4 Optical properties**

*Environmental Emissions*

**Figure 23.**

**Table 7.**

**112**

**Figure 24.**

C▬H group bending. Another peak at 750 cm<sup>−</sup><sup>1</sup>

The comparative study on Fourier transform infrared spectra of pure polystyrene vs doped carbon soot/PS nanocomposites shows (**Figures 25** and **26**) the peaks

sponding to the formation of PS. Bands of CS/PS nanocomposites are more and less as compared to the peaks of pure polystyrene, but there are no other peaks found, showing that all the soot nanoparticles are loaded inside the PS host matrix without changing their chemical structure. No other modification in the shift of chemicals

around 2920, 1739, 1600, 1492, 1451, 1367, 1215, 1027, 905, 750 and 537 cm<sup>−</sup><sup>1</sup>

*XRD spectra of (a) almond soot/PS nanocomposites and (b) mustard soot/PS nanocomposites.*

*EDAX spectra of (a) PMMA, (b) almond soot/PMMA and (c) mustard soot/PMMA samples.*

**Samples Percentile compositions**

*Percentage of element compositions of PS, AS/PS and MS/PS thin film.*

Pure PS 99.36 0.64 AS/PS 99.10 0.90 MS/PS 98.87 1.13

**C% O%**

vibration band of benzene ring hydrogen.

shows due to (C▬H) deformation

corre-

In this section, we discuss about the optical properties of polystyrene nanocomposites. Here, the carbon soot was doped with either almond soot or mustard soot particles with 1 and 2 wt%, respectively. In the optical properties, we tried to understand the absorption coefficient properties. Therefore, we measured the band gap of nanocomposites in the range of 200–800 nm.

#### *7.4.1 The absorption data*

The absorbance data spectra of pure polystyrene and AS/PS (**Figure 27a**) and pure polystyrene and MS/PS (**Figure 27b**) nanocomposite thin films show the value of absorbance increases with doping the carbon soot in PS as compared to the pure PS. The increased absorbance in spectral profile from nanocomposite reveals the correlation between carbon soot nanoparticles and the host matrix polystyrene matrix. In this study, carbon soot (traditional Indian name—"Kajal") is produced by incomplete combustion of almond and mustard oil by flame deposition method. Researchers also used different types of soot from aerosol carbon particles, diesel soot and other sources. Similar results were found by Mita et al. in 1980 [48] from absorbance of aerosol soot particles. As seen in the figures, the value of absorbance is low at high wavelength and high absorbance value corresponding to the low wavelengths.

#### *7.4.2 Absorption coefficient and band gap study*

The absorption coefficient spectra of polystyrene and soot/polymer nanocomposites are represented in **Figure 28a** and **b**.

For the indirect band gap, the value of r is 1/2; hence, the indirect band gap of nanocomposite thin films is obtained using the help of plot (αhν) 1/2 Vs hν (**Figure 29a** and **b**). It has been noticed that the band gap is inversely proportional

**Figure 25.** *FTIR spectra of almond soot polystyrene nanocomposites.*

**Figure 26.** *FTIR spectra of mustard soot polystyrene nanocomposites.*

#### **Figure 27.**

*The absorbance data spectra of pure polystyrene with (a) almond soot-doped PS thin films and (b) mustard soot-doped PS thin films.*

to the thickness of films. The indirect band gap of pure PS and AS/PS at 1 and 2 wt% is 4.06 eV, 3.84 and 3.47 eV, as well as for PS, MS/PS at 1 wt% and MS/PS at 2 wt%, it is 4.33, 3.94 and 3.85 eV. Energy band gap values for all thin film samples of 50 μm thickness are represented in **Table 8**.

#### **7.5 Glass transition temperature phenomenon (Tg)**

Dynamic mechanical analysis is an amazing tool to study the viscoelastic properties of carbon soot particles filled with polymer. The other authors investigated the mechanical properties of carbon nanoparticles with polymer [48–53]. The dynamical mechanical results of carbon soot/polystyrene nanocomposites produced by solution casting method for pure polystyrene, almond soot/polystyrene and mustard soot/polystyrene at 1 and 2 wt% concentrations (**Figure 30**) show

**115**

**Table 8.**

**Figure 28.**

**Figure 29.**

*and (b) mustard soot 1 and 2 wt% in PS.*

*Carbon Soot Polymer Nanocomposites (CSPNCs): Production, Surface Morphological, Glass…*

that for all CS/PS nanocomposites there is a downshift in viscous modulus toward a higher temperature compared to the pure polystyrene. All data were recorded at

*Representation of absorption coefficient spectra of pure polystyrene with (a) AS/PS composite for 1 and 2 wt%* 

*Plot of (αhν) 1/2 vs hν photon energy (hν) for the pure polystyrene with (a) almond soot 1 and 2 wt% in PS* 

**PS and CSPNC samples Energy band gap Eg (eV)**

*The obtained value of pure polystyrene energy band gap and AS/PS and MS/PS at 1 and 2 wt% concentration.*

Pure PS for AS samples 4.06 AS-1 wt% 3.84 AS-2 wt% 3.47 Pure PS for MS samples 4.33 MS-1 wt% 3.94 MS-2 wt% 3.85

*concentration and (b) MS/PS composite for 1 and 2 wt% concentration.*

*DOI: http://dx.doi.org/10.5772/intechopen.92389*

1 Hz frequency and 22–160°C temperature.

that for all CS/PS nanocomposites there is a downshift in viscous modulus toward a higher temperature compared to the pure polystyrene. All data were recorded at 1 Hz frequency and 22–160°C temperature.

#### **Figure 28.**

*Environmental Emissions*

**114**

**Figure 27.**

**Figure 26.**

*soot-doped PS thin films.*

of 50 μm thickness are represented in **Table 8**.

*FTIR spectra of mustard soot polystyrene nanocomposites.*

**7.5 Glass transition temperature phenomenon (Tg)**

*The absorbance data spectra of pure polystyrene with (a) almond soot-doped PS thin films and (b) mustard* 

to the thickness of films. The indirect band gap of pure PS and AS/PS at 1 and 2 wt% is 4.06 eV, 3.84 and 3.47 eV, as well as for PS, MS/PS at 1 wt% and MS/PS at 2 wt%, it is 4.33, 3.94 and 3.85 eV. Energy band gap values for all thin film samples

Dynamic mechanical analysis is an amazing tool to study the viscoelastic properties of carbon soot particles filled with polymer. The other authors investigated the mechanical properties of carbon nanoparticles with polymer [48–53]. The dynamical mechanical results of carbon soot/polystyrene nanocomposites produced by solution casting method for pure polystyrene, almond soot/polystyrene and mustard soot/polystyrene at 1 and 2 wt% concentrations (**Figure 30**) show

*Representation of absorption coefficient spectra of pure polystyrene with (a) AS/PS composite for 1 and 2 wt% concentration and (b) MS/PS composite for 1 and 2 wt% concentration.*

#### **Figure 29.**

*Plot of (αhν) 1/2 vs hν photon energy (hν) for the pure polystyrene with (a) almond soot 1 and 2 wt% in PS and (b) mustard soot 1 and 2 wt% in PS.*


#### **Table 8.**

*The obtained value of pure polystyrene energy band gap and AS/PS and MS/PS at 1 and 2 wt% concentration.*

#### **Figure 30.**

*Variations of viscous modules (E") with temperature for (a) pure polystyrene, (b) almond-1 wt%/PS, (c) almond-2 wt%/PS, (d) mustard-1 wt% PS and (e) mustard-2 wt%/PS.*

The glass transition temperature (Tg) of pure polystyrene is 114°C, and glass transition temperatures for almond soot/PS nanocomposites for 1 and 2 wt% are 80 and 91°C, as well as for mustard soot/PS nanocomposites at 1 and 2 wt% concentration are 92 and 91°C (**Table 9**). We can see that the value of glass transition

**117**

*Carbon Soot Polymer Nanocomposites (CSPNCs): Production, Surface Morphological, Glass…*

**Samples Glass transition temperature Tg (°C)**

Pure PS 114 A-1 wt% 80 A-2 wt% 91 M-1 wt% 92 M-2 wt% 91

*The glass transition temperature (Tg) values of CS/PS nanocomposites.*

temperature decreases for all samples as compared to the pure polystyrene. In the case of AS/PS nanocomposites, the value of Tg increases with the concentration of almond soot nanoparticles and reveals that the addition of more soot particles hinders the segmental relaxation of the polystyrene chains, while for the MS/PS nanocomposites, the value of Tg slightly decreases with the increase of mustard soot

The chapter is concerned with two things: first with carbon soot nanoparticles

(CSNPs) and second is carbon soot polymer nanocomposites (CSPNCs). The morphological and spectroscopic analysis is carried out for carbon soot nanoparticles, and the glass transition temperature phenomenon, and optical and structural properties are obtained for the synthesized carbon soot polymer nanocomposites. Production of carbon soot from incomplete combustion of almond oil and mustard oil by low cost flame deposition method in two different environment one is natural environment (without water tub) and other one is with water tub, these prepared fresh carbon soots such as almond soot (AS) and mustard soot (MS) are characterized by FESEM, XRD, EDAX, FTIR and UV for morphological, elemental composition and spectroscopic analysis. The formed carbon soot particles are the amorphous nanomaterial with the size of approximately 50 nm, confirmed by the XRD and FESEM study. The IR study is carried out to identify the presence of any

, SP3

condition is an important tool for identifying the morphology and particle size of carbon nanoparticles (CNPs). The synthesized soot is useful for die purpose, paint, marker pen ink, etc. It is also used for pigment and reinforcement in vehicle tires as

In the next step, we produced the carbon soot polymer nanocomposites (CSPNCs) for different carbon soot nanoparticles such as almond soot and mustard soot with different polymer matrices of polymethyl methacrylate (PMMA) and

Primarily, we synthesized carbon soot/PMMA nanocomposites with different concentration 1 and 2 mg of AS and MS of 100 μm thickness by solution casting technique. Prepared samples are characterized for the optical and surface morphological properties. FESEM and EDAX provide the useful information about the nanostructure and compositions of nanocomposite samples. FTIR analysis of CS/PMMA nanocomposites shows that the soot nanoparticles are loaded in polymer (PMMA) without change in chemical structure for the surface morphology calculating the surface roughness of all samples, and the decreasing values of

and aromatic clusters. Here, with water tub

*DOI: http://dx.doi.org/10.5772/intechopen.92389*

**8. Conclusions and future scopes**

functional group, some small SP2

it decreases the thermal damage.

polystyrene (PS).

nanoparticles.

**Table 9.**

**8.1 Conclusions**

*Carbon Soot Polymer Nanocomposites (CSPNCs): Production, Surface Morphological, Glass… DOI: http://dx.doi.org/10.5772/intechopen.92389*


**Table 9.**

*Environmental Emissions*

**116**

**Figure 30.**

*Variations of viscous modules (E") with temperature for (a) pure polystyrene, (b) almond-1 wt%/PS,* 

The glass transition temperature (Tg) of pure polystyrene is 114°C, and glass transition temperatures for almond soot/PS nanocomposites for 1 and 2 wt% are 80 and 91°C, as well as for mustard soot/PS nanocomposites at 1 and 2 wt% concentration are 92 and 91°C (**Table 9**). We can see that the value of glass transition

*(c) almond-2 wt%/PS, (d) mustard-1 wt% PS and (e) mustard-2 wt%/PS.*

*The glass transition temperature (Tg) values of CS/PS nanocomposites.*

temperature decreases for all samples as compared to the pure polystyrene. In the case of AS/PS nanocomposites, the value of Tg increases with the concentration of almond soot nanoparticles and reveals that the addition of more soot particles hinders the segmental relaxation of the polystyrene chains, while for the MS/PS nanocomposites, the value of Tg slightly decreases with the increase of mustard soot nanoparticles.

#### **8. Conclusions and future scopes**

#### **8.1 Conclusions**

The chapter is concerned with two things: first with carbon soot nanoparticles (CSNPs) and second is carbon soot polymer nanocomposites (CSPNCs). The morphological and spectroscopic analysis is carried out for carbon soot nanoparticles, and the glass transition temperature phenomenon, and optical and structural properties are obtained for the synthesized carbon soot polymer nanocomposites.

Production of carbon soot from incomplete combustion of almond oil and mustard oil by low cost flame deposition method in two different environment one is natural environment (without water tub) and other one is with water tub, these prepared fresh carbon soots such as almond soot (AS) and mustard soot (MS) are characterized by FESEM, XRD, EDAX, FTIR and UV for morphological, elemental composition and spectroscopic analysis. The formed carbon soot particles are the amorphous nanomaterial with the size of approximately 50 nm, confirmed by the XRD and FESEM study. The IR study is carried out to identify the presence of any functional group, some small SP2 , SP3 and aromatic clusters. Here, with water tub condition is an important tool for identifying the morphology and particle size of carbon nanoparticles (CNPs). The synthesized soot is useful for die purpose, paint, marker pen ink, etc. It is also used for pigment and reinforcement in vehicle tires as it decreases the thermal damage.

In the next step, we produced the carbon soot polymer nanocomposites (CSPNCs) for different carbon soot nanoparticles such as almond soot and mustard soot with different polymer matrices of polymethyl methacrylate (PMMA) and polystyrene (PS).

Primarily, we synthesized carbon soot/PMMA nanocomposites with different concentration 1 and 2 mg of AS and MS of 100 μm thickness by solution casting technique. Prepared samples are characterized for the optical and surface morphological properties. FESEM and EDAX provide the useful information about the nanostructure and compositions of nanocomposite samples. FTIR analysis of CS/PMMA nanocomposites shows that the soot nanoparticles are loaded in polymer (PMMA) without change in chemical structure for the surface morphology calculating the surface roughness of all samples, and the decreasing values of surface roughness with the doping of soot nanoparticles in host matrix PMMA are obtained. In this sequence, the band gap of PMMA and all CS/PMMA nanocomposites are calculated for the optical properties. The lower values of energy band gap are carried out by filling CS in PMMA as compared to the pure PMMA.

For the second case of carbon soot polymer nanocomposites, carbon soot/PS nanocomposites were produced with 1 and 2 wt% concentration of AS and MS nanofillers in host matrix polystyrene by cost-effective solution cast method of 50 μm thickness. The glass transition temperature phenomenon, optical, structural and surface morphological studies are carried out for prepared composite samples. X-ray diffraction study reveals the variation of intensity showing the presence of carbon soot in the polystyrene chain and gives the important information about the amorphous nature. The decreasing values of roughness and band gap are obtained with the doping of carbon soot nanoparticles in the host polymer matrix polystyrene, and also the low values of glass transition temperature Tg of CS/PS samples are obtained as compared to the pure PS sample. These obtained properties of carbon soot polymer nanocomposites make them very useful in various applications including in the separation of oil and water, anti-icing and energy-saving buildings, high-energy vehicles, electric trains and electric devices.

#### **8.2 Future scope**

The incomplete combustion synthesis of carbon soot is a relatively new field of research that has not yet been exploited in all its potentiality. A good controlled incomplete combustion process is flame deposition has represented to be able to synthesis of different carbonaceous particles from burning different oils in a low temperature range. This study provide a deep knowledge of the soot species production method under a flame environment. It was carried out on the experimental results basis. A good relationship between production/combustion conditions and carbon properties like morphological, chemical composition, spectroscopic and internal structure has been found. We can produce the soot by any other method.

Nevertheless, the main focus on investigation of carbon allotropes such as graphine, carbon nanotube (CNT), fullerenes etc by flame deposition method for more demanding applications. Ultimately, the synthesized soot particles through combustion are suitable for industrial applications.

Carbon soot nanoparticles in PMMA and PS could be improved if these nanoparticles are functionalized by some surfactants, and this will be a more homogeneous dispersion of nanoparticles in polymers. Thin films of CS/PMMA or PS could also be casted by spin coating technique. Mechanical and optical properties of CS/polymer samples give faithful results; we can investigate the di-electric and thermal conductivity for further industrial applications.

**119**

**Author details**

Rakhi Tailor\*, Yogesh Kumar Vijay and Minal Bafna Vivekananda Global University, Jaipur, India

\*Address all correspondence to: rrtrbt@yahoo.com

provided the original work is properly cited.

© 2020 The Author(s). Licensee IntechOpen. This chapter is distributed under the terms of the Creative Commons Attribution License (http://creativecommons.org/licenses/ by/3.0), which permits unrestricted use, distribution, and reproduction in any medium,

*Carbon Soot Polymer Nanocomposites (CSPNCs): Production, Surface Morphological, Glass…*

*DOI: http://dx.doi.org/10.5772/intechopen.92389*

CSPNCs carbon soot polymer nanocomposites

FESEM field emission scanning electron microscopy FTIR Fourier transform infrared spectroscopy

DMA dynamic mechanical analyzer EDAX energy dispersive X-ray

PMMA polymethyl methacrylate

CS carbon soot

PS polystyrene UV ultraviolet XRD X-ray diffraction

#### **Conflict of interest**

The authors declare no conflict of interest.

#### **Abbreviations**


*Carbon Soot Polymer Nanocomposites (CSPNCs): Production, Surface Morphological, Glass… DOI: http://dx.doi.org/10.5772/intechopen.92389*


#### **Author details**

*Environmental Emissions*

**8.2 Future scope**

**Conflict of interest**

**Abbreviations**

surface roughness with the doping of soot nanoparticles in host matrix PMMA are obtained. In this sequence, the band gap of PMMA and all CS/PMMA nanocomposites are calculated for the optical properties. The lower values of energy band gap

For the second case of carbon soot polymer nanocomposites, carbon soot/PS nanocomposites were produced with 1 and 2 wt% concentration of AS and MS nanofillers in host matrix polystyrene by cost-effective solution cast method of 50 μm thickness. The glass transition temperature phenomenon, optical, structural and surface morphological studies are carried out for prepared composite samples. X-ray diffraction study reveals the variation of intensity showing the presence of carbon soot in the polystyrene chain and gives the important information about the amorphous nature. The decreasing values of roughness and band gap are obtained with the doping of carbon soot nanoparticles in the host polymer matrix polystyrene, and also the low values of glass transition temperature Tg of CS/PS samples are obtained as compared to the pure PS sample. These obtained properties of carbon soot polymer nanocomposites make them very useful in various applications including in the separation of oil and water, anti-icing and energy-saving buildings,

The incomplete combustion synthesis of carbon soot is a relatively new field of research that has not yet been exploited in all its potentiality. A good controlled incomplete combustion process is flame deposition has represented to be able to synthesis of different carbonaceous particles from burning different oils in a low temperature range. This study provide a deep knowledge of the soot species production method under a flame environment. It was carried out on the experimental results basis. A good relationship between production/combustion conditions and carbon properties like morphological, chemical composition, spectroscopic and internal structure has been found. We can produce the soot by any other method. Nevertheless, the main focus on investigation of carbon allotropes such as graphine, carbon nanotube (CNT), fullerenes etc by flame deposition method for more demanding applications. Ultimately, the synthesized soot particles through

Carbon soot nanoparticles in PMMA and PS could be improved if these nanoparticles are functionalized by some surfactants, and this will be a more homogeneous dispersion of nanoparticles in polymers. Thin films of CS/PMMA or PS could also be casted by spin coating technique. Mechanical and optical properties of CS/polymer samples give faithful results; we can investigate the di-electric

are carried out by filling CS in PMMA as compared to the pure PMMA.

high-energy vehicles, electric trains and electric devices.

combustion are suitable for industrial applications.

The authors declare no conflict of interest.

AFM atomic force microscopy

CNPs carbon nanoparticles CNTs carbon nanotubes

AS almond soot

and thermal conductivity for further industrial applications.

**118**

Rakhi Tailor\*, Yogesh Kumar Vijay and Minal Bafna Vivekananda Global University, Jaipur, India

\*Address all correspondence to: rrtrbt@yahoo.com

© 2020 The Author(s). Licensee IntechOpen. This chapter is distributed under the terms of the Creative Commons Attribution License (http://creativecommons.org/licenses/ by/3.0), which permits unrestricted use, distribution, and reproduction in any medium, provided the original work is properly cited.

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[37] Kumar D, Paul E, Kavita K, Singh K, Bhatti H. Synthesis and characterization of water soluble carbon nanotubes. Journal of Nanoscience. 2016;**2**:64-65

[38] Klabunde K. Nanoscale Materials in Chemistry. New York: Wiley Interscience; 2001;**1035**:223-262

[39] Krishnamoorti R, Vaia R. Polymer nanocomposites: Introduction in polymer nanocomposites synthesis.

Science. 2007;**33**:272-309

[31] Arthur J, Napier D. Fifth

1970. pp. 179-180

2005;**65**:681-697

2017;**17**:1-5

2016;**11**:9130-9133

*DOI: http://dx.doi.org/10.5772/intechopen.92389*

and scattering of electromagnetic radiation by diesel soot. Applied Optics.

[21] Desantes J, Bermudez V, Garcia J, Fuentes E. Effects of current engine strategies on the exhaust aerosol particle size distribution from a heavy duty diesel engine. Journal of Aerosol

[22] Vanderwal R, Tomasek A, Street K, Hull D, Thompson W, Sljenbug J. Carbon nanostructure examined by lattice fringe analysis of high resolution transmission electron microscopy. Applied Spectroscopy. 2004;**58**:230-237

[23] Vandernial R, Tomasek A. Soot oxidation: Dependence upon initial nanostructure. Combustion and Flame.

[24] Amann C, Siegla D. Diesel particulates—What they are and why. Aerosol Science and Technology.

[25] Esangbedo C, Boehman A, Peres J. Characteristics of diesel engine soot that lead to excessive oil thickening. Tribology International.

[26] Clague A, Donnet J, Wang T, Peng J. A comparison of diesel engine soot with carbon black. Carbon.

[27] Stanmore B, Brilhac J, Gilot P. The oxidation of soot: A review of experiments, mechanism and models.

[28] Sarotim A, Longwell J, Wornat M, Mukherjee J. The role of biaryl reactions in PAH and soot formation. In: Soot Formation in Combustion. Springer: Series in Chemical Physics, CHEMICAL;

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Carbon. 2001;**39**:2247-2268

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*Carbon Soot Polymer Nanocomposites (CSPNCs): Production, Surface Morphological, Glass… DOI: http://dx.doi.org/10.5772/intechopen.92389*

and scattering of electromagnetic radiation by diesel soot. Applied Optics. 1991;**30**:1537-1546

[21] Desantes J, Bermudez V, Garcia J, Fuentes E. Effects of current engine strategies on the exhaust aerosol particle size distribution from a heavy duty diesel engine. Journal of Aerosol Science. 2005;**36**:1251-1276

[22] Vanderwal R, Tomasek A, Street K, Hull D, Thompson W, Sljenbug J. Carbon nanostructure examined by lattice fringe analysis of high resolution transmission electron microscopy. Applied Spectroscopy. 2004;**58**:230-237

[23] Vandernial R, Tomasek A. Soot oxidation: Dependence upon initial nanostructure. Combustion and Flame. 2003;**134**:1-9

[24] Amann C, Siegla D. Diesel particulates—What they are and why. Aerosol Science and Technology. 1982;**1**:73-101

[25] Esangbedo C, Boehman A, Peres J. Characteristics of diesel engine soot that lead to excessive oil thickening. Tribology International. 2011;**47**:194-203

[26] Clague A, Donnet J, Wang T, Peng J. A comparison of diesel engine soot with carbon black. Carbon. 1999;**37**:1553-1565

[27] Stanmore B, Brilhac J, Gilot P. The oxidation of soot: A review of experiments, mechanism and models. Carbon. 2001;**39**:2247-2268

[28] Sarotim A, Longwell J, Wornat M, Mukherjee J. The role of biaryl reactions in PAH and soot formation. In: Soot Formation in Combustion. Springer: Series in Chemical Physics, CHEMICAL; 1994;**59**:485-499

[29] Tree D, Svensson K. Soot processes in compression ignition engines.

Progress in Energy and Combustion Science. 2007;**33**:272-309

[30] Gaydon A, Wolfhard H. Flames. London: Chapman and Hall Limited; 1970. pp. 179-180

[31] Arthur J, Napier D. Fifth Symposium on Combustion. London: Chapman and Hall Limited; 1955. p. 303

[32] Gaydon A, Fairbairn A. Fifth Symposium on Combustion. London: Chapman and Hall limited; 1955. p. 24

[33] Greene E, Taylor R, Patterson W. Mechanism of the pyrolysis of acetylene. Journal of Physical Chemistry; 1958;**62**:238

[34] Dubey P, Muthukumarah D, Dash S, Mukhopadhyay R, Sarkar S. Synthesis and characterization of water soluble carbon nanotubes from mustard soot. PRAMANA Journal of Physics. 2005;**65**:681-697

[35] Baska R, Devashankar S, Sarkar R. Analysis of nano carbon obtained from mustard oil soot. International Journal of Emerging Technologies in Computational and Applied Sciences. 2017;**17**:1-5

[36] Novopashin S, Serebrjakova M, Zaikovoki A. Morphology, chemical composition and magnetization of are discharge Fe–C soot. Journal of Engineering and Applied Sciences. 2016;**11**:9130-9133

[37] Kumar D, Paul E, Kavita K, Singh K, Bhatti H. Synthesis and characterization of water soluble carbon nanotubes. Journal of Nanoscience. 2016;**2**:64-65

[38] Klabunde K. Nanoscale Materials in Chemistry. New York: Wiley Interscience; 2001;**1035**:223-262

[39] Krishnamoorti R, Vaia R. Polymer nanocomposites: Introduction in polymer nanocomposites synthesis.

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[41] Spitaloky Z, Tasis D, Papageli K, Galiotis C. Carbon nanotube polymer composites: Chemistry, processing mechanical and electrical properties. Progress in Polymer Science. 2010;**35**:357-401

[42] Ward H. In: Thomas TR, editor. Rough Surfaces. London: Longman; 1982

[43] Kahnert M, Nousiainen T, Lindquist H, Ebert M. Optical properties of light absorbing carbon aggregates mixed with sulfate assessment of different model geometries for climate forcing calculations. Optical Express. 2012;**20**:10042-10058

[44] Bond T, Bergstrom R. Light absorption by carbonaceous particles: All investigated review. Aerosol Science and Technology. 2006;**40**:27-67

[45] Sara D, Taylor M, Andrew T, Lindsa R, Daniel A, Paola M, et al. Measurement and modeling of the multiwave length optical properties of uncoated flame generated soot. Atmospheric Chemistry and Physics. 2018;**18**:12141-12159

[46] Zhang R, Hu Y, Xu J, Fan W, Chen Z. Flame ability and thermal stability studies of styrene-butmer/ graphite oxide nano composite. Polymer Degradation and Stability. 2004;**85**:583-588

[47] Acharya A, Sarwan B, Sharma R, Moghe S, Shrivastav S, Ganesan V. UV-shielding efficiency of TiO2 polystrene thin films prepared by solution cast method. Frontiers

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[49] Sabbar A, Mohammed H, Ibrahim A, Saud H. Thermal and optical properties of polystyrene nanocomposites reinforced with soot. Orientation Journal of Chemistry. 2019;**35**:455-460

[50] Russo C, Stanzione F, Alfe M, Cicyolo A, Tregrossi A. Spectral Analysis in the UV-Visible Range for Revealing the Molecular Forms of Combustion Generated Carbonaceous Species. Italy: Chia Laguna; 2011

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[52] Ibarra L, Macais A, Palma E. Viscoelastic properties of short of short carbon fiber thermoplastic (SBS) elastomer composites. Journal of Applied Polymer Science. 1995;**57**:831

[53] Nigrawal A, Chand N. Studies on dynamic mechanical analysis and morphology of carbon soot filled in saturated polyester graded composites. International Journal of Science Engineering and Advance Technology. 2014;**2**:116-119

**123**

**Chapter 7**

Poland

**Abstract**

from motor vehicles.

**1. Introduction**

The Use of Synchronous

Fluorescence Technique in

Environmental Investigations of

in Airborne Particulate Matter

from an Industrial Region in

*Aniela Matuszewska and Maria Czaja*

Polycyclic Aromatic Hydrocarbons

The applicability of the fluorescence techniques to identify the polycyclic aromatic hydrocarbons (PAHs) in environmental samples is presented. The technique of synchronous fluorescence enabled the identification of the PAHs series containing 2–6 condensed rings in urban airborne particulate matter from Upper Silesia industrial region in Poland. The results obtained by synchronous and conventional fluorescence measurements have been confirmed by those from gas chromatography-mass spectrometry. As the air sample was taken in summer season, the main source of pollution by PAHs component seems to be transport – the exhaust gases

**Keywords:** synchronous fluorescence, polycyclic aromatic hydrocarbons (PAHs),

Polycyclic aromatic hydrocarbons (PAHs), ubiquitous today in human environment, being harmful as potentially carcinogenic or mutagenic compounds, derive from various sources: natural and anthropogenic ones. Aromatic compounds generated in various natural processes can appear in the natural environment, joining the global cycle of dispersed and concentrated forms of organic matter. The dispersed forms of organic matter are, e.g., hydrocarbons existing in a small amount in rocks and minerals of various origins as well as in abyssal waters getting out on the Earth surface as natural geysers, or hydrocarbons emerging from mining shafts as well as hydrocarbons from volcanic exhalations. The hydrocarbons should be also mentioned from dispersion aureoles round about petroleum and gas deposits. There are also hydrocarbons in under waters accompanying the petroleum, coal, and ore

atmospheric pollutions, gas chromatography-mass spectrometry

#### **Chapter 7**

*Environmental Emissions*

Symposium. 2002;**804**:1-5

synthesized by emulsion

2002;**804**:15-25

2010;**35**:357-401

1982

Characterization and hoarding. ACS

of Physics and Plasma Science-Journal of Physics Conference Series. 2017;**836**:1-5. DOI:

Japan. 1980;**58**:69-78

2019;**35**:455-460

[49] Sabbar A, Mohammed H, Ibrahim A, Saud H. Thermal and optical properties of polystyrene nanocomposites reinforced with soot. Orientation Journal of Chemistry.

[50] Russo C, Stanzione F, Alfe M, Cicyolo A, Tregrossi A. Spectral Analysis in the UV-Visible Range for Revealing the Molecular Forms of Combustion Generated Carbonaceous Species. Italy: Chia Laguna; 2011

[51] Gandhi K, Salovey R. Dynamic mechanical behavior of polymers containing carbon black. Polymer

[52] Ibarra L, Macais A, Palma E. Viscoelastic properties of short of short carbon fiber thermoplastic (SBS) elastomer composites. Journal of Applied Polymer Science. 1995;**57**:831

[53] Nigrawal A, Chand N. Studies on dynamic mechanical analysis and morphology of carbon soot filled in saturated polyester graded composites. International Journal of Science Engineering and Advance Technology.

Engineering and Science.

1988;**28**:877-887

2014;**2**:116-119

10.10.1088/1742-6596/836/1/012048

[48] Mita A, Isono K. Effective complex refractive index of atmospheric aerosols containing absorbing substances. Journal of the Meteorological Society of

[40] Bandyopadhyay S, Hsieh A, Giannells E. PMMA nanocomposites

polymerization. ACS Symposium.

[41] Spitaloky Z, Tasis D, Papageli K, Galiotis C. Carbon nanotube polymer composites: Chemistry, processing mechanical and electrical properties.

[42] Ward H. In: Thomas TR, editor. Rough Surfaces. London: Longman;

Lindquist H, Ebert M. Optical properties of light absorbing carbon aggregates mixed with sulfate assessment of different model geometries for climate forcing calculations. Optical Express.

Progress in Polymer Science.

[43] Kahnert M, Nousiainen T,

[44] Bond T, Bergstrom R. Light absorption by carbonaceous particles: All investigated review. Aerosol Science

and Technology. 2006;**40**:27-67

[45] Sara D, Taylor M, Andrew T, Lindsa R, Daniel A, Paola M, et al. Measurement and modeling of the multiwave length optical properties of uncoated flame generated soot. Atmospheric Chemistry and Physics.

[46] Zhang R, Hu Y, Xu J, Fan W, Chen Z. Flame ability and thermal stability studies of styrene-butmer/ graphite oxide nano composite. Polymer Degradation and Stability.

[47] Acharya A, Sarwan B, Sharma R, Moghe S, Shrivastav S, Ganesan V. UV-shielding efficiency of TiO2 polystrene thin films prepared by solution cast method. Frontiers

2012;**20**:10042-10058

2018;**18**:12141-12159

2004;**85**:583-588

**122**

The Use of Synchronous Fluorescence Technique in Environmental Investigations of Polycyclic Aromatic Hydrocarbons in Airborne Particulate Matter from an Industrial Region in Poland

*Aniela Matuszewska and Maria Czaja*

### **Abstract**

The applicability of the fluorescence techniques to identify the polycyclic aromatic hydrocarbons (PAHs) in environmental samples is presented. The technique of synchronous fluorescence enabled the identification of the PAHs series containing 2–6 condensed rings in urban airborne particulate matter from Upper Silesia industrial region in Poland. The results obtained by synchronous and conventional fluorescence measurements have been confirmed by those from gas chromatography-mass spectrometry. As the air sample was taken in summer season, the main source of pollution by PAHs component seems to be transport – the exhaust gases from motor vehicles.

**Keywords:** synchronous fluorescence, polycyclic aromatic hydrocarbons (PAHs), atmospheric pollutions, gas chromatography-mass spectrometry

### **1. Introduction**

Polycyclic aromatic hydrocarbons (PAHs), ubiquitous today in human environment, being harmful as potentially carcinogenic or mutagenic compounds, derive from various sources: natural and anthropogenic ones. Aromatic compounds generated in various natural processes can appear in the natural environment, joining the global cycle of dispersed and concentrated forms of organic matter. The dispersed forms of organic matter are, e.g., hydrocarbons existing in a small amount in rocks and minerals of various origins as well as in abyssal waters getting out on the Earth surface as natural geysers, or hydrocarbons emerging from mining shafts as well as hydrocarbons from volcanic exhalations. The hydrocarbons should be also mentioned from dispersion aureoles round about petroleum and gas deposits. There are also hydrocarbons in under waters accompanying the petroleum, coal, and ore

deposits and hydrocarbons penetrating to water reservoirs and to soil as a result of outcrop and erosion of sedimentary rocks. The concentrated forms of the hydrocarbon existence are crude oils, combustible gases, solid bitumens, coals, bituminous shales, and organic-mineral associations of various natures [1]. Among different hydrocarbon groups, there are frequently various PAHs as products of diagenetic, biological, or thermal processes [2–6]. All of these kinds of hydrocarbons occurrence form a geochemical background overlapped by the anthropogenic pollutions [1]. The main sources of anthropogenic PAHs are incomplete combustion of organic matter especially organic fuels (industry, transport, incinerating plants, domestic processes) and thermolysis of organic fossils (coke and asphalt production) [7–9]. All waste organic matter emitters are especially active in an industrial region where they spread to large areas due to various meteorological phenomena. It is because the atmosphere is a zone particularly exposed to pollution.

The permanent contact of living organisms with air makes the polluted atmosphere an especially important area of monitoring. Harmful PAH compounds that pollute the air are very susceptible to adsorption on the other else air pollutant – suspended dust, formed by mineral matter and/or by soot appeared in the air due to lack of or inappropriate protective filters on devices emitting it [10, 11].

The necessity of monitoring of PAHs in air explains the proof of the use much more effective analytical methods enabling their identification in a manner as simple and fast as possible. Among the most frequently applied modern methods of analysis of aromatic hydrocarbons in environmental samples are the chromatographic ones, particularly capillary gas chromatography, the most effective with mass spectrometry as the tool of detection (GC and GC-MS methods) [12–19].

Also high performed liquid chromatographs (HPLC method) are widely applied in these investigations (e.g., [20–22]). However, it is often not cost effective to apply these methods routinely to large numbers of samples.

In the choice of analytical method, it is always very important to take into account the specific properties of analyzed compounds. In the analyzed case, the PAH's high fluorescence efficiency and sensibility as well as simplicity of sample preparation are the reasons that fluorescent techniques are beneficial for PAHs

**125**

10<sup>−</sup><sup>6</sup>

*The Use of Synchronous Fluorescence Technique in Environmental Investigations of Polycyclic…*

monitoring. However, the conventional fluorescent spectra of multi-component mixture of PAHs have been sometimes difficult to interpret. Now, synchronous technique of fluorescence spectroscopy (SFS) removes these difficulties (e.g., [1, 23]). The purpose of this work is a presentation of the applicability of the technique of synchronous luminescence for qualitative analysis of aromatic fraction composition of organic substance polluting the urban air in an industrial region. The task sample was taken from Upper Silesia Metropole. This is the region of Poland with many branches of industry, such as mining, metallurgy, electric power station (coke and coal), a dense road network, and a great number of coal-fired home stoves, used sometimes also in the summer. City Mysłowice – the area where air dust was taken to investigations lies centrally in this region (**Figure 1**). The monitoring of the air state in Upper Silesia Metropole and particular cities gives not only an actual information but can also indicate the direction of changes. We believe that it also encourages the people responsible for environment for more intensive efforts to

**2. Some remarks on PAHs fluorescence and synchronous fluorescence** 

Fluorescence is the emission of light of wavelength generally different from that of the incident radiation. Most polycyclic aromatic hydrocarbons are fluorescent. It is caused by the fact that the delocalized electrons in the aromatic rings may be easily excited, and the stiff structure does not allow for efficient vibrational relaxation. Fluorescence spectra of each PAH are very characteristic, and they depend on the number and position of aromatic rings. With aromatic ring number increasing, the fluorescence spectrum and emission peak wavelength are all red-shifted from ultraviolet to visible range; the fluorescence emission spectra from one to four rings could be discriminated in the following wavelengths, 275–320 nm, 320–375 nm, 375–425 nm, and 425–556 nm, respectively. It can be used for distinguishing the type of the polycyclic aromatic hydrocarbons (PAHs) as it exists in single type.

The electronic states in the molecules could be singlets or triplets. Singlet state is defined when all the electron spins are paired in the molecular electronic state. The ground state is always singlet (S0). The excited states could be singlets (S1, S2, …) or triplets (T1, T2, …) when total spin is equal 1. The most probably absorption (A) and emission transitions are singlet-singlet; their intensity is high and luminescence

Molecules in the S1 state can undergo a spin conversion to the first triplet state T1; energy of this triplet state is lower than of S1 state. The emission from T1, termed phosphorescence (P), is shifted to the longer wavelengths relatively to the fluorescence and characterized by distinctly smaller intensity and longer decay time,

–1 s. It was showed on the simplified Jablonski diagram (**Figure 2**) [24]. The idea of synchronous fluorescence was first suggested by Lloyd and Evett [23]. In conventional fluorescence spectrometry, an emission spectrum is measured for constant excitation wavelength (λexc). Contrary, the excitation spectrum is measured for constant emission wavelength (λem), usually to determine the energy levels (or wavelengths) that are responsible for measured emission. In some sense, excitation spectra replace the absorption spectra. In Constant-Wavelength Synchronous Fluorescence Spectroscopy, the wavelength interval Δλ = λexc − λem is keeping a constant. For each PAH, the most characteristic λexc and λem and in consequence Δλ values could be choose. Value of Δλ parameter is so calculated as a difference between effective emission and excitation wavelength characteristic for identified compound. When the difference between the longest

s. Such emission transition is called fluorescence (F).

*DOI: http://dx.doi.org/10.5772/intechopen.92402*

improve air quality.

**spectroscopy (SFS)**

decay time short, 10<sup>−</sup><sup>9</sup>

–10<sup>−</sup><sup>7</sup>

**Figure 1.** *Localization of sampling in Upper Silesia Region.*

#### *The Use of Synchronous Fluorescence Technique in Environmental Investigations of Polycyclic… DOI: http://dx.doi.org/10.5772/intechopen.92402*

monitoring. However, the conventional fluorescent spectra of multi-component mixture of PAHs have been sometimes difficult to interpret. Now, synchronous technique of fluorescence spectroscopy (SFS) removes these difficulties (e.g., [1, 23]).

The purpose of this work is a presentation of the applicability of the technique of synchronous luminescence for qualitative analysis of aromatic fraction composition of organic substance polluting the urban air in an industrial region. The task sample was taken from Upper Silesia Metropole. This is the region of Poland with many branches of industry, such as mining, metallurgy, electric power station (coke and coal), a dense road network, and a great number of coal-fired home stoves, used sometimes also in the summer. City Mysłowice – the area where air dust was taken to investigations lies centrally in this region (**Figure 1**). The monitoring of the air state in Upper Silesia Metropole and particular cities gives not only an actual information but can also indicate the direction of changes. We believe that it also encourages the people responsible for environment for more intensive efforts to improve air quality.

#### **2. Some remarks on PAHs fluorescence and synchronous fluorescence spectroscopy (SFS)**

Fluorescence is the emission of light of wavelength generally different from that of the incident radiation. Most polycyclic aromatic hydrocarbons are fluorescent. It is caused by the fact that the delocalized electrons in the aromatic rings may be easily excited, and the stiff structure does not allow for efficient vibrational relaxation. Fluorescence spectra of each PAH are very characteristic, and they depend on the number and position of aromatic rings. With aromatic ring number increasing, the fluorescence spectrum and emission peak wavelength are all red-shifted from ultraviolet to visible range; the fluorescence emission spectra from one to four rings could be discriminated in the following wavelengths, 275–320 nm, 320–375 nm, 375–425 nm, and 425–556 nm, respectively. It can be used for distinguishing the type of the polycyclic aromatic hydrocarbons (PAHs) as it exists in single type.

The electronic states in the molecules could be singlets or triplets. Singlet state is defined when all the electron spins are paired in the molecular electronic state. The ground state is always singlet (S0). The excited states could be singlets (S1, S2, …) or triplets (T1, T2, …) when total spin is equal 1. The most probably absorption (A) and emission transitions are singlet-singlet; their intensity is high and luminescence decay time short, 10<sup>−</sup><sup>9</sup> –10<sup>−</sup><sup>7</sup> s. Such emission transition is called fluorescence (F). Molecules in the S1 state can undergo a spin conversion to the first triplet state T1; energy of this triplet state is lower than of S1 state. The emission from T1, termed phosphorescence (P), is shifted to the longer wavelengths relatively to the fluorescence and characterized by distinctly smaller intensity and longer decay time, 10<sup>−</sup><sup>6</sup> –1 s. It was showed on the simplified Jablonski diagram (**Figure 2**) [24].

The idea of synchronous fluorescence was first suggested by Lloyd and Evett [23]. In conventional fluorescence spectrometry, an emission spectrum is measured for constant excitation wavelength (λexc). Contrary, the excitation spectrum is measured for constant emission wavelength (λem), usually to determine the energy levels (or wavelengths) that are responsible for measured emission. In some sense, excitation spectra replace the absorption spectra. In Constant-Wavelength Synchronous Fluorescence Spectroscopy, the wavelength interval Δλ = λexc − λem is keeping a constant. For each PAH, the most characteristic λexc and λem and in consequence Δλ values could be choose. Value of Δλ parameter is so calculated as a difference between effective emission and excitation wavelength characteristic for identified compound. When the difference between the longest

*Environmental Emissions*

deposits and hydrocarbons penetrating to water reservoirs and to soil as a result of outcrop and erosion of sedimentary rocks. The concentrated forms of the hydrocarbon existence are crude oils, combustible gases, solid bitumens, coals, bituminous shales, and organic-mineral associations of various natures [1]. Among different hydrocarbon groups, there are frequently various PAHs as products of diagenetic, biological, or thermal processes [2–6]. All of these kinds of hydrocarbons occurrence form a geochemical background overlapped by the anthropogenic pollutions [1]. The main sources of anthropogenic PAHs are incomplete combustion of organic matter especially organic fuels (industry, transport, incinerating plants, domestic processes) and thermolysis of organic fossils (coke and asphalt production) [7–9]. All waste organic matter emitters are especially active in an industrial region where they spread to large areas due to various meteorological phenomena. It is because

The permanent contact of living organisms with air makes the polluted atmosphere an especially important area of monitoring. Harmful PAH compounds that pollute the air are very susceptible to adsorption on the other else air pollutant – suspended dust, formed by mineral matter and/or by soot appeared in the air due to

The necessity of monitoring of PAHs in air explains the proof of the use much more effective analytical methods enabling their identification in a manner as simple and fast as possible. Among the most frequently applied modern methods of analysis of aromatic hydrocarbons in environmental samples are the chromatographic ones, particularly capillary gas chromatography, the most effective with mass spectrometry as the tool of detection (GC and GC-MS methods) [12–19].

Also high performed liquid chromatographs (HPLC method) are widely applied in these investigations (e.g., [20–22]). However, it is often not cost effective to apply

In the choice of analytical method, it is always very important to take into account the specific properties of analyzed compounds. In the analyzed case, the PAH's high fluorescence efficiency and sensibility as well as simplicity of sample preparation are the reasons that fluorescent techniques are beneficial for PAHs

lack of or inappropriate protective filters on devices emitting it [10, 11].

the atmosphere is a zone particularly exposed to pollution.

these methods routinely to large numbers of samples.

**124**

**Figure 1.**

*Localization of sampling in Upper Silesia Region.*

**Figure 2.** *The simplified Jablonski diagram.*

wavelength excitation band and the shortest wavelength emission band is applied as Δλ, there is only one peak in the synchronous fluorescence spectrum [1, 25] The single peak is present at the same wavelength as the longest wavelength excitation band for a synchronous excitation spectrum or the shortest wavelength emission band for a synchronous emission spectrum [26]. The characteristic sets of λexc and λem of analyzed compounds could be known from references or obtained independently from measurements of the high purity standards. In this way, synchronous fluorescence spectra are much simpler and easier to analyze than conventional emission. Thus, synchronous fluorescence spectroscopy becomes an attractive alternative for the simultaneous determination of multiple compounds in complex samples. The analytical significance of SFS is confirmed by the fact that this technique is already relatively broadly utilized in investigations of samples of various origins [26–36].

#### **3. Experimental**

#### **3.1 The origin and analysis of the investigation object**

The analyzed airborne particulate matter derives from Mysłowice urban air (Upper Silesia industrial region, Poland; **Figure 1**). Located in an urban area, a "staplex" high volume sampler with glass fiber filter was applied as the equipment for collecting the airborne particulate matter. The collection of the sample was done in summer (non-heating season). The organic fraction was isolated from the investigated particulate matter by extraction with redistilled n-hexane for 3 hours, using a Soxhlet extractor. The choice of the solvent was substantiated by a mean to obtain nonpolar fraction because many of polar compounds fluoresce. To avoid the eventual fluorescence by traces of these compounds, the additive fractionation was made to reduce their content. For this purpose, Merck's TLC pre-coated plate was used, covered by silica gel layer (thickness of 0.2 mm). The mobile phase for thin layer chromatography process was n-hexane. This procedure enabled to obtain aromatic, aliphatic, and polar fractions. The aromatic fraction was recovered from silica gel by elution with n-hexane using the glass column. For the fluorescence analysis, the solutions of aromatic fraction were prepared with the concentrations in the range from 0.01 to 0.002 mg ml<sup>−</sup><sup>1</sup> .

**127**

*The Use of Synchronous Fluorescence Technique in Environmental Investigations of Polycyclic…*

The same aromatic fraction was also used for further analysis by GC-MS

Fluorescence spectra were determined at room temperature using a Jobin-Yvon (SPEX) FLUORLOG 3-12 spectrofluorimeter with a 450 W xenon lamp, a double-grating monochromator, and a Hamamatsu 928 photomultiplier. During measurements, scanning parameters were always put as 0.5 nm per 0.5 s, while the remaining parameters were for each type of measurements as follows: for synchronous measurements, excitation and emission slits have been set to 1 nm; for emission measurements, excitation slit was put to 3 nm, and emission slit – to 1 nm, while for excitation measurements, the slits settings were reversed. To verify the presence of a given PAH, the Δλ parameter was chosen, according to the reference

The comparative analysis of PAHs by gas chromatography-mass spectrometry (GC-MS) was performed using a HP 5890 II gas chromatograph equipped with a fused silica capillary column HP-5 (60 m length × 0.25 mm internal diameter). Helium was the carrier gas used. The GC oven was programmed from 35 to 300°C at a rate of 3°C/min. The gas chromatograph was coupled with a HP 5971A mass selective detector (MSD). The MS was operated with an ion source temperature of 200°C, an ionization energy of 70 eV, and a cycle time of 1 s in the mass range

The results of the qualitative investigations performed are summarized in **Table 1**. Values λex, λem, and Δλ were collated there for individual PAHs after the experimental and literature data [1] (the limits of differences between the λ data are 1–3 nm). The presence of compounds identified by SFS technique has been confirmed by GC-MS method characterized here by the retention time. The results obtained indicate that both methods have own high research capability, but generally fluorescence analytical procedure seems to be simpler and analytical instru-

The results of qualitative analysis given in **Table 1** were obtained as a result of

In **Figure 3**, the synchronous spectrum of analyzed PAH mixture is shown, recorded at the value of Δλ = 23 nm. This value was proposed by Mille et al. [38, 39] for general characteristics of aromatics from fossil fuels, as an effective parameter to take a fair middle course between the sensitivity and resolving parameters. They used this value for estimation of PAH condensation degree range of investigated aromatic compounds in the mixture. **Figure 3** shows the distribution of emission bands of studied sample in which compounds with a number of rings from 2 to 6 can be identified, thanks to their representation by characteristic bands. The most apparent are substances with 3–5 rings. The bands in the spectrum under discussion identify the following polycyclic aromatic hydrocarbons and its alkyl, mostly methyl derivatives: acenaphthene, benzo(c)fluorene, naphthalenes

record of many synchronous spectra. Several of them are presented below.

**4.1 SFS examples of application to the identification of individual** 

**aromatics in the analyzed PAH mixture**

*DOI: http://dx.doi.org/10.5772/intechopen.92402*

**3.2 The apparatus used and experimental conditions**

data [1, 23, 37] as well as to own earlier experimental results.

method.

40–600 Daltons.

ment cheaper in exploitation.

**4. Results**

*The Use of Synchronous Fluorescence Technique in Environmental Investigations of Polycyclic… DOI: http://dx.doi.org/10.5772/intechopen.92402*

The same aromatic fraction was also used for further analysis by GC-MS method.

#### **3.2 The apparatus used and experimental conditions**

Fluorescence spectra were determined at room temperature using a Jobin-Yvon (SPEX) FLUORLOG 3-12 spectrofluorimeter with a 450 W xenon lamp, a double-grating monochromator, and a Hamamatsu 928 photomultiplier. During measurements, scanning parameters were always put as 0.5 nm per 0.5 s, while the remaining parameters were for each type of measurements as follows: for synchronous measurements, excitation and emission slits have been set to 1 nm; for emission measurements, excitation slit was put to 3 nm, and emission slit – to 1 nm, while for excitation measurements, the slits settings were reversed. To verify the presence of a given PAH, the Δλ parameter was chosen, according to the reference data [1, 23, 37] as well as to own earlier experimental results.

The comparative analysis of PAHs by gas chromatography-mass spectrometry (GC-MS) was performed using a HP 5890 II gas chromatograph equipped with a fused silica capillary column HP-5 (60 m length × 0.25 mm internal diameter). Helium was the carrier gas used. The GC oven was programmed from 35 to 300°C at a rate of 3°C/min. The gas chromatograph was coupled with a HP 5971A mass selective detector (MSD). The MS was operated with an ion source temperature of 200°C, an ionization energy of 70 eV, and a cycle time of 1 s in the mass range 40–600 Daltons.

#### **4. Results**

*Environmental Emissions*

origins [26–36].

**Figure 2.**

*The simplified Jablonski diagram.*

**3. Experimental**

**3.1 The origin and analysis of the investigation object**

in the range from 0.01 to 0.002 mg ml<sup>−</sup><sup>1</sup>

wavelength excitation band and the shortest wavelength emission band is applied as Δλ, there is only one peak in the synchronous fluorescence spectrum [1, 25] The single peak is present at the same wavelength as the longest wavelength excitation band for a synchronous excitation spectrum or the shortest wavelength emission band for a synchronous emission spectrum [26]. The characteristic sets of λexc and λem of analyzed compounds could be known from references or obtained independently from measurements of the high purity standards. In this way, synchronous fluorescence spectra are much simpler and easier to analyze than conventional emission. Thus, synchronous fluorescence spectroscopy becomes an attractive alternative for the simultaneous determination of multiple compounds in complex samples. The analytical significance of SFS is confirmed by the fact that this technique is already relatively broadly utilized in investigations of samples of various

The analyzed airborne particulate matter derives from Mysłowice urban air (Upper Silesia industrial region, Poland; **Figure 1**). Located in an urban area, a "staplex" high volume sampler with glass fiber filter was applied as the equipment for collecting the airborne particulate matter. The collection of the sample was done in summer (non-heating season). The organic fraction was isolated from the investigated particulate matter by extraction with redistilled n-hexane for 3 hours, using a Soxhlet extractor. The choice of the solvent was substantiated by a mean to obtain nonpolar fraction because many of polar compounds fluoresce. To avoid the eventual fluorescence by traces of these compounds, the additive fractionation was made to reduce their content. For this purpose, Merck's TLC pre-coated plate was used, covered by silica gel layer (thickness of 0.2 mm). The mobile phase for thin layer chromatography process was n-hexane. This procedure enabled to obtain aromatic, aliphatic, and polar fractions. The aromatic fraction was recovered from silica gel by elution with n-hexane using the glass column. For the fluorescence analysis, the solutions of aromatic fraction were prepared with the concentrations

.

**126**

The results of the qualitative investigations performed are summarized in **Table 1**. Values λex, λem, and Δλ were collated there for individual PAHs after the experimental and literature data [1] (the limits of differences between the λ data are 1–3 nm). The presence of compounds identified by SFS technique has been confirmed by GC-MS method characterized here by the retention time. The results obtained indicate that both methods have own high research capability, but generally fluorescence analytical procedure seems to be simpler and analytical instrument cheaper in exploitation.

The results of qualitative analysis given in **Table 1** were obtained as a result of record of many synchronous spectra. Several of them are presented below.

#### **4.1 SFS examples of application to the identification of individual aromatics in the analyzed PAH mixture**

In **Figure 3**, the synchronous spectrum of analyzed PAH mixture is shown, recorded at the value of Δλ = 23 nm. This value was proposed by Mille et al. [38, 39] for general characteristics of aromatics from fossil fuels, as an effective parameter to take a fair middle course between the sensitivity and resolving parameters. They used this value for estimation of PAH condensation degree range of investigated aromatic compounds in the mixture. **Figure 3** shows the distribution of emission bands of studied sample in which compounds with a number of rings from 2 to 6 can be identified, thanks to their representation by characteristic bands. The most apparent are substances with 3–5 rings. The bands in the spectrum under discussion identify the following polycyclic aromatic hydrocarbons and its alkyl, mostly methyl derivatives: acenaphthene, benzo(c)fluorene, naphthalenes


**129**

**Figure 3.**

*The Use of Synchronous Fluorescence Technique in Environmental Investigations of Polycyclic…*

**Reference data [1] Δλ [nm] λem/λex [nm/nm]**

**GC/MS retention time [min]**

**Δλ [nm] λem/λex [nm/nm]**

Benzo(e)-pyrene 71 390/319 71 389/318 54.37 Benzo(a)-pyrene 34 400/366 33 403/370 54.69

Anthanthrene 25 433/408 24 434/410 61.02

Benzo(g,h,i)-perylene 50 420/370 50 420/370 62.85 3,4-9,10-Di-benzopyrene 34 433/399 34 432/398 69.21 *\*The term "luminescence" is used sometimes interchangeably with "fluorescence," describing more widely the discussed* 

*Identification by synchronous fluorescence and GC/MS analyses of individual compounds occurring in investigated aromatic fraction of organic mixture desorbed from urban air dust collected in industrial area. Characteristic parameters of individual compounds present in studied aromatic fraction identified on the basis* 

*of luminescence \* analysis (Δλ, λem/λexc) and GC-MS measurements (retention time).*

*Synchronous fluorescence spectrum of studied sample measured at Δλ = 23 nm.*

39 425/386 39 427/388

30 433/403 30 434/404

*DOI: http://dx.doi.org/10.5772/intechopen.92402*

*phenomenon.*

**Table 1.**

**Identified compounds Experimental data**

*The Use of Synchronous Fluorescence Technique in Environmental Investigations of Polycyclic… DOI: http://dx.doi.org/10.5772/intechopen.92402*


*\*The term "luminescence" is used sometimes interchangeably with "fluorescence," describing more widely the discussed phenomenon.*

#### **Table 1.**

*Environmental Emissions*

1-Methyl-7-isopropylphenanthrene

2-Methyl-benzo-(c) phenanthrene

12-Methyl-benz(a) anthracene

anthracene

anthracene

1,12-Dimethyl-benz(a)-

7,12-Dimethyl-benz(a)-

9-Methylanthracene

**Identified compounds Experimental data**

**Δλ [nm] λem/λex [nm/nm]**

2,3-Dimethyl-naphthalene 54 334/280 54 333/279 14.78 Phenanthrene 53 347/294 53 346/293 25.26

9-Methyl-phenanthrene 50 349/299 52 350/298 29.11 9,10-Dimethyl-phenanthrene 55 356/301 55 354/299 32.42

1-Methyl-anthracene 20 400/380 21 403/382 28.94

9,10-Dimethyl-anthracene 23 400/377 24 402/378 33.23

Fluoranthene 94 418/324 92 417/325 33.96 Benzo(b)fluorene 28 339/311 29 341/312 37.60

Pyrene 39 369/330 39 372/333 35.53

1-Methyl-pyrene 31 370/339 34 373/339 39.08 4-Methyl-pyrene 52 376/324 51 374/323 39.73 3-Methyl-pyrene 30 378/348 31 376/345 39.94

Benzo(c)-phenanthrene 94 376/282 93 374/281 43.37

Benz(a)-anthracene 23 384/361 23 384/361 44.88 1-Methyl-benz(a)-anthracene 47 389/342 47 389/342 48.45 2-Methyl-benz(a)-anthracene 20 385/365 19 387/368 47.91 7-Methyl-benz(a)-anthracene 17 392/375 18 392/374 48.19 8-Methyl-benz(a)-anthracene 21 387/366 21 388/367 48.77

Chrysene 39 362/323 39 361/322 45.16 Benzo(b)-fluoranthene 30 399/369 29 396/367 52.69

> 66 430/364 63 430/367 94 398/304 95 396/301

71 365/294 71 364/293 105 357/252 102 356/254

71 355/284 69 354/285

98 358/260 100 360/260

37 384/347 38 383/345

23 424/401 24 424/400

46 356/310 45 357/312

46 378/332 46 379/333

50 377/327 48 376/328

103 377/274 104 378/274

66 398/332 66 399/333 43.70

35 391/356 37 393/356 47.15

41 404/363 41 402/361 49.35

53 399/346 52 399/347 51.44

67 368/301 67 369/302 38.63

22 411/389 23 411/388 29.86

**Reference data [1] Δλ [nm] λem/λex [nm/nm]**

**GC/MS retention time [min]**

**128**

*Identification by synchronous fluorescence and GC/MS analyses of individual compounds occurring in investigated aromatic fraction of organic mixture desorbed from urban air dust collected in industrial area. Characteristic parameters of individual compounds present in studied aromatic fraction identified on the basis of luminescence \* analysis (Δλ, λem/λexc) and GC-MS measurements (retention time).*

**Figure 3.** *Synchronous fluorescence spectrum of studied sample measured at Δλ = 23 nm.*

(328 and 335 nm), phenanthrene (345 nm), chrysenes (363 nm), pyrenes, anthracene (377 nm), benzo(a)anthracene (385, 411 nm), benzo(b)fluoranthene (396 and 425 nm), benzo(a)pyrene (404 nm), benzo(g,h,i)perylene (425 nm), and 3,4-9,10-dibenzopyrene (431 nm). In this way, the spectrum recorded at Δλ = 23 nm is a kind of overview spectrum for the composition of the analyzed mixture.

The use of Δλ value calculated for individual compound as it was explained earlier enables the record of a synchronous spectrum with intense band identifying analyzed compound. In **Figure 4,** the spectra are presented and recorded at Δλ = 30 nm, Δλ = 46 nm, and Δλ = 39 nm. Using Δλ = 30 nm, the presence of 3-methylpyrene and benzo(b)fluoranthene was proven on the basis of the most intense bands at 378 and 399 nm, respectively. Moreover, a distinct band of anthanthrene (433 nm) can be seen. In turn, on the spectrum recorded at Δλ = 46 nm, the presence of benzo(b)fluorene (356 nm) is evident, and other distinct bands at 378 and 399 nm correspond to pyrene and 3-methylpyrene, respectively. For chrysene identification, Δλ value equal to 39 nm was taken. In the spectrum obtained, a band at 362 nm characteristic for chrysene is very intense. The band of lower intensity at 369 nm can derive from pyrene. **Table 1** indicates parameter Δλ = 39 nm as characteristic also for benzo(a)pyrene, and in **Figure 3**, the band is seen at 425 nm

**131**

**Figure 5.**

*The Use of Synchronous Fluorescence Technique in Environmental Investigations of Polycyclic…*

deriving probably from benzo(a)pyrene. The low intensity of benzo(a)pyrene band is undoubtedly a result of low concentration of this compound (see also relatively weak benzo(a)pyrene peak on the GC-MS chromatogram presented below;

**Figure 8**). However, in a complex mixture the partial quenching of the fluorescence of individual components is possible by some of other components of the mixture.

**Figure 6** is an example of verification of the results obtained by synchronous technique, using other spectral fractionation realized by conventional technique of fluorescence. For example, an emission spectrum of chrysene has been recorded at an excitation wavelength of 324 nm (close to the literature value of 322 nm; **Table 1**). Three bands at 361, 370, and 379 nm appeared distinctively complying with the literature data for chrysene: 361, 373, and 381 nm (**Table 1**). The emission spectrum of chrysene is, however, overlapped partly with group of bands at

Subsequent spectra in **Figure 5** show the presence of phenanthrene, thanks to the characteristic emission bands at 347 nm (at Δλ = 53 nm) and 357 nm (at Δλ = 105 nm). Other bands at 376 nm and 399 nm are attributed to

*Synchronous fluorescence spectra of studied sample measured at Δλ = 53 nm and Δλ = 105 nm.*

*DOI: http://dx.doi.org/10.5772/intechopen.92402*

This process, however, is not yet fully investigated.

4-methylpyrene and 7,12-dimethylbenzo(a)anthracene.

*The Use of Synchronous Fluorescence Technique in Environmental Investigations of Polycyclic… DOI: http://dx.doi.org/10.5772/intechopen.92402*

deriving probably from benzo(a)pyrene. The low intensity of benzo(a)pyrene band is undoubtedly a result of low concentration of this compound (see also relatively weak benzo(a)pyrene peak on the GC-MS chromatogram presented below; **Figure 8**). However, in a complex mixture the partial quenching of the fluorescence of individual components is possible by some of other components of the mixture. This process, however, is not yet fully investigated.

Subsequent spectra in **Figure 5** show the presence of phenanthrene, thanks to the characteristic emission bands at 347 nm (at Δλ = 53 nm) and 357 nm (at Δλ = 105 nm). Other bands at 376 nm and 399 nm are attributed to 4-methylpyrene and 7,12-dimethylbenzo(a)anthracene.

**Figure 6** is an example of verification of the results obtained by synchronous technique, using other spectral fractionation realized by conventional technique of fluorescence. For example, an emission spectrum of chrysene has been recorded at an excitation wavelength of 324 nm (close to the literature value of 322 nm; **Table 1**). Three bands at 361, 370, and 379 nm appeared distinctively complying with the literature data for chrysene: 361, 373, and 381 nm (**Table 1**). The emission spectrum of chrysene is, however, overlapped partly with group of bands at

**Figure 5.** *Synchronous fluorescence spectra of studied sample measured at Δλ = 53 nm and Δλ = 105 nm.*

*Environmental Emissions*

(328 and 335 nm), phenanthrene (345 nm), chrysenes (363 nm), pyrenes, anthracene (377 nm), benzo(a)anthracene (385, 411 nm), benzo(b)fluoranthene (396 and 425 nm), benzo(a)pyrene (404 nm), benzo(g,h,i)perylene (425 nm), and 3,4-9,10-dibenzopyrene (431 nm). In this way, the spectrum recorded at Δλ = 23 nm

is a kind of overview spectrum for the composition of the analyzed mixture. The use of Δλ value calculated for individual compound as it was explained earlier enables the record of a synchronous spectrum with intense band identifying

analyzed compound. In **Figure 4,** the spectra are presented and recorded at Δλ = 30 nm, Δλ = 46 nm, and Δλ = 39 nm. Using Δλ = 30 nm, the presence of 3-methylpyrene and benzo(b)fluoranthene was proven on the basis of the most intense bands at 378 and 399 nm, respectively. Moreover, a distinct band of anthanthrene (433 nm) can be seen. In turn, on the spectrum recorded at Δλ = 46 nm, the presence of benzo(b)fluorene (356 nm) is evident, and other distinct bands at 378 and 399 nm correspond to pyrene and 3-methylpyrene, respectively. For chrysene identification, Δλ value equal to 39 nm was taken. In the spectrum obtained, a band at 362 nm characteristic for chrysene is very intense. The band of lower intensity at 369 nm can derive from pyrene. **Table 1** indicates parameter Δλ = 39 nm as characteristic also for benzo(a)pyrene, and in **Figure 3**, the band is seen at 425 nm

*Synchronous fluorescence spectra of studied sample measured at Δλ = 30 nm, Δλ = 39 nm, and Δλ = 46 nm.*

**130**

**Figure 4.**

**Figure 6.** *Fluorescence emission spectrum of studied sample measured at λexc = 324 nm.*

wavelengths: 400, 409, 426, 437, and 456 nm. The origin of these bands seems to have a complex nature. Analysis of the literature data indicates that there are probably several groups of compounds in investigated mixture characterized by similar energy levels corresponding with these emission wavelengths.

Several homologous compounds from the group of anthracene, benzo(a) anthracene, and benzo(a)pyrene can contribute to the mentioned bands. A series of tests with the record of various emission and excitation spectra using conventional techniques and also synchronous one indicated possible contribution to the bands under discussion of 9,10-dimethylanthracene (402, 407, 424, 428, and 453 nm), 1,12-dimethylbenzo(a)anthracene (402, 427, and 455 nm), and benzo(a)pyrene (403, 408, 427, and 431 nm) [1]. However, according to various premises, the benzo(a)pyrene can be the main component of the mentioned group of bands.

To validate this hypothesis, the emission spectrum of benzo(a)pyrene was recorded, using its characteristic λex = 350 nm. **Figure 7** obtained in this manner presents emission bands (402, 409, and 426 nm) of benzo(a)pyrene, confirming contribution of this ingredient to intensity of bands under investigation. An inverse spectral process was also carried out: the spectra recorded at the positions of emission monochromator of λem = 402 nm and λem = 427 nm allowed to get characteristic

**133**

**Figure 7.**

*The Use of Synchronous Fluorescence Technique in Environmental Investigations of Polycyclic…*

clearly visible excitation bands with maxima at 349 and 372 nm, close to the literature data for λex of benzo(a)pyrene at 350 and 370 nm [1]. It is important to mention that in the emission spectrum obtained at λex = 350 nm (**Figure 7**), there are also two weak

The high condensed aromatics as coronene were not identified by SFS technique. Lin et al. [26] also found difficulties with the use of SFS to analyze PAHs containing more than six rings. The authors emphasize at the same time that SFS technique is the most sensitive in detecting three- or four-ring PAHs. For the coronene mentioned (seven condensed rings), not identified by SFS, the additional analysis has been performed, and its strong emission band at 446 nm was obtained in the

In **Figure 8**, total ion chromatogram (TIC, GC/MS) is presented of aromatic fraction of the extract from analyzed airborne particulate matter. The following PAHs were identified, and their characteristic peaks indicated there by consecutive

bands at 463 and 493 nm deriving probably from indeno (1,2,3-cd)pyrene.

*Fluorescence emission spectrum of studied sample measured at λexc = 350 nm.*

emission spectrum recorded using λex = 300 nm.

**4.2 Comparative GC-MS analysis**

numbers from 1/ to 20/:

*DOI: http://dx.doi.org/10.5772/intechopen.92402*

*The Use of Synchronous Fluorescence Technique in Environmental Investigations of Polycyclic… DOI: http://dx.doi.org/10.5772/intechopen.92402*

**Figure 7.** *Fluorescence emission spectrum of studied sample measured at λexc = 350 nm.*

clearly visible excitation bands with maxima at 349 and 372 nm, close to the literature data for λex of benzo(a)pyrene at 350 and 370 nm [1]. It is important to mention that in the emission spectrum obtained at λex = 350 nm (**Figure 7**), there are also two weak bands at 463 and 493 nm deriving probably from indeno (1,2,3-cd)pyrene.

The high condensed aromatics as coronene were not identified by SFS technique. Lin et al. [26] also found difficulties with the use of SFS to analyze PAHs containing more than six rings. The authors emphasize at the same time that SFS technique is the most sensitive in detecting three- or four-ring PAHs. For the coronene mentioned (seven condensed rings), not identified by SFS, the additional analysis has been performed, and its strong emission band at 446 nm was obtained in the emission spectrum recorded using λex = 300 nm.

#### **4.2 Comparative GC-MS analysis**

In **Figure 8**, total ion chromatogram (TIC, GC/MS) is presented of aromatic fraction of the extract from analyzed airborne particulate matter. The following PAHs were identified, and their characteristic peaks indicated there by consecutive numbers from 1/ to 20/:

*Environmental Emissions*

**132**

**Figure 6.**

wavelengths: 400, 409, 426, 437, and 456 nm. The origin of these bands seems to have a complex nature. Analysis of the literature data indicates that there are probably several groups of compounds in investigated mixture characterized by similar

Several homologous compounds from the group of anthracene, benzo(a) anthracene, and benzo(a)pyrene can contribute to the mentioned bands. A series of tests with the record of various emission and excitation spectra using conventional techniques and also synchronous one indicated possible contribution to the bands under discussion of 9,10-dimethylanthracene (402, 407, 424, 428, and 453 nm), 1,12-dimethylbenzo(a)anthracene (402, 427, and 455 nm), and benzo(a)pyrene (403, 408, 427, and 431 nm) [1]. However, according to various premises, the benzo(a)pyrene can be the main component of the mentioned group of bands. To validate this hypothesis, the emission spectrum of benzo(a)pyrene was recorded, using its characteristic λex = 350 nm. **Figure 7** obtained in this manner presents emission bands (402, 409, and 426 nm) of benzo(a)pyrene, confirming contribution of this ingredient to intensity of bands under investigation. An inverse spectral process was also carried out: the spectra recorded at the positions of emission monochromator of λem = 402 nm and λem = 427 nm allowed to get characteristic

energy levels corresponding with these emission wavelengths.

*Fluorescence emission spectrum of studied sample measured at λexc = 324 nm.*

**Figure 8.**

*Total ion-chromatogram (TIC, GC/MS) of aromatic fraction of the extract from analyzed airborne particulate matter.*

1/ alkylnaphthalenes, 2/ phenanthrene, 3/ methylphenanthrenes + methylanthracenes, 4/ dimethylphenanthrenes + dimethylanthracenes, 5/fluoranthene, 6/ pyrene, 7/ benzofluorenes + methylpyrenes + benzo(c)phenanthrenes, 8/ benzo(a) anthracene, 9/ chrysene + triphenylene, 10/ alkylbenz(a)anthracenes, 11/alkylchrysenes, 12/benzofluoranthenes, 13/ benzo(e)pyrene, 14/ benzo(a)pyrene, 15/ perylene, 16/ anthanthrene, 17/ indeno(1,2,3-c,d)pyrene, 18/ benzo(ghi)perylene, 19/3,4-9,10-dibenzopyrene, and 20/ coronene. Many compounds from this group seem to be typical for pollution of atmosphere of the investigated industrial region in Poland (e.g., [40]) and at the same time are basic for environmental monitoring in the European Union and the USA (e.g., [41], *loc.cit*.).

The PAHs alkylated are described here as groups of compounds, not all homologs being identified. In **Table 1**, the several alkyl substituted PAHs are presented, among other hydrocarbons, and identified by GC-MS and SFS methods.

#### **5. Discussion of the results**

SFS technique made possible the identification of a series of PAHs polluting urban air in the industrial region in Poland. Comparative analysis by GC-MS method has confirmed these results. Qualitative analysis of PAH mixtures by SFS is rather a fast technique and does not need many preparation steps and chemicals. However, for a complex mixture as the analyzed extract from the filter of air dust, the separation into fractions has been done (see subsection 3.1) to reduce the possibilities of mutual quenching of fluorescence by particular components of the mixture. Simplicity of SFS analysis can be shown, e.g., by the possibility of initial estimation of the condensation range of PAHs in analyzed mixture by the use of Δλ = 23 nm parameter as it was described earlier. However, the most important is

**135**

suggested below.

*The Use of Synchronous Fluorescence Technique in Environmental Investigations of Polycyclic…*

here the possibility of receiving the SFS spectra of particular identified PAHs, with one or several well resolved bands, characteristic for analyzed compounds. For recording these spectra, the specific values of Δλ parameters are used after calcula-

The possibility of the use of other analytical techniques of fluorescence method (as the record of emission or extinction conventional spectrum) can broaden the group of identified compounds as, e.g., in the case of coronene with seven condensed rings, not identified by SFS but indicated by emission spectrum as mentioned above. Thus, the fluorescence techniques, especially SFS, can play a significant role in urban air monitoring for the identification of PAHs. The main order is the environmental impact assessment by the indication of the presence PAHs harmful to health due to toxic, carcinogenic, or mutagenic properties. The total number of PAHs in environment is estimated on about 200, and in exhaust gases, for example, of diesel motors – on over 100 [41]. It is not possible to analyze all of them during everyone monitoring process. It is because only some representative compounds are usually chosen to analyze. For example, Environmental Protection Agency of USA has selected the 16 PAHs for a basic environmental monitoring program [US EPA, Polycyclic Aromatic Hydrocarbons (PAHs)-EPA fact sheet, Washington (DC)-National Center for Environmental Assessment, Office of Research and

These 16 PAHs are included in the US list of priority pollutants and are usually analyzed: naphthalene, acenaphthene, acenaphthylene, fluorene, phenanthrene, anthracene, fluoranthene, pyrene, benz[a]anthracene, chrysene, benzo[b] fluoranthene, benzo[k]fluoranthene, benzo[a]pyrene, indeno[1,2,3-cd]pyrene, dibenzo[a,h]anthracene, and benzo[ghi]perylene. The influence of these PAHs on the human health has been there also noted. The majority of compounds from this list were identified in the samples of environmental PAHs reported by various authors [1, 12–14, 40, 43]. Their widespread occurrence in the environment causes that most of them are chosen also in European monitoring programs (including Polish programs), e.g., CONCAWE-The Oil Companies European Organization for Environment, Health, and Safety or ARC-International Agency for Research on Cancer (e.g., [41, 44] *loc. cit.*). These compounds characterize very high toxicity. Almost all of compounds from EPA list are identified among PAHs analyzed here. Taking into account relative intensities of pollutant peaks seen clearly in the ion-chromatogram realized for this work (**Figure 8**), one can stated that the most intense peaks can be attributed to fluoranthene and pyrene, not carcinogenic after EPA. The highest carcinogenicity is attributed, in turn, to benzo(a)pyrene and dibenzo(ah)anthracene, relatively lower to benzo(b)fluoranthene and the lowest to chrysene (potentially carcinogenic) and also to benzo(a)anthracene and indeno(1,2,3-cd)pyrene. Other compounds from the EPA list are not noted as carcinogenic. Main representative of carcinogens – benzo(a)pyrene does not dominate in analyzed group of PAHs, what may be related to summer season of sampling [1], but its content in air of the Silesian industrial region is still relatively high [44]. The general similarity of own results with these ones from the world literature data can suggest that major of identified PAHs may be universal products of high chemical stability, deriving from incomplete burning of various organic fuels. It may be also possible that these compounds derive mainly from the incomplete burning of oil fuels as the result of so-called low emission from vehicle exhaust because of widespread development of automotive transport. In the case of our own results, it could be confirmed by PAH distribution of the summer season when low emission pollutions are dominated by the exhaust gases from car engines as it is

tion on the basis known spectral characteristics of identified compounds.

*DOI: http://dx.doi.org/10.5772/intechopen.92402*

Development; e.g., [31, 41, 42] *loc. cit.*].

#### *The Use of Synchronous Fluorescence Technique in Environmental Investigations of Polycyclic… DOI: http://dx.doi.org/10.5772/intechopen.92402*

here the possibility of receiving the SFS spectra of particular identified PAHs, with one or several well resolved bands, characteristic for analyzed compounds. For recording these spectra, the specific values of Δλ parameters are used after calculation on the basis known spectral characteristics of identified compounds.

The possibility of the use of other analytical techniques of fluorescence method (as the record of emission or extinction conventional spectrum) can broaden the group of identified compounds as, e.g., in the case of coronene with seven condensed rings, not identified by SFS but indicated by emission spectrum as mentioned above.

Thus, the fluorescence techniques, especially SFS, can play a significant role in urban air monitoring for the identification of PAHs. The main order is the environmental impact assessment by the indication of the presence PAHs harmful to health due to toxic, carcinogenic, or mutagenic properties. The total number of PAHs in environment is estimated on about 200, and in exhaust gases, for example, of diesel motors – on over 100 [41]. It is not possible to analyze all of them during everyone monitoring process. It is because only some representative compounds are usually chosen to analyze. For example, Environmental Protection Agency of USA has selected the 16 PAHs for a basic environmental monitoring program [US EPA, Polycyclic Aromatic Hydrocarbons (PAHs)-EPA fact sheet, Washington (DC)-National Center for Environmental Assessment, Office of Research and Development; e.g., [31, 41, 42] *loc. cit.*].

These 16 PAHs are included in the US list of priority pollutants and are usually analyzed: naphthalene, acenaphthene, acenaphthylene, fluorene, phenanthrene, anthracene, fluoranthene, pyrene, benz[a]anthracene, chrysene, benzo[b] fluoranthene, benzo[k]fluoranthene, benzo[a]pyrene, indeno[1,2,3-cd]pyrene, dibenzo[a,h]anthracene, and benzo[ghi]perylene. The influence of these PAHs on the human health has been there also noted. The majority of compounds from this list were identified in the samples of environmental PAHs reported by various authors [1, 12–14, 40, 43]. Their widespread occurrence in the environment causes that most of them are chosen also in European monitoring programs (including Polish programs), e.g., CONCAWE-The Oil Companies European Organization for Environment, Health, and Safety or ARC-International Agency for Research on Cancer (e.g., [41, 44] *loc. cit.*). These compounds characterize very high toxicity.

Almost all of compounds from EPA list are identified among PAHs analyzed here. Taking into account relative intensities of pollutant peaks seen clearly in the ion-chromatogram realized for this work (**Figure 8**), one can stated that the most intense peaks can be attributed to fluoranthene and pyrene, not carcinogenic after EPA. The highest carcinogenicity is attributed, in turn, to benzo(a)pyrene and dibenzo(ah)anthracene, relatively lower to benzo(b)fluoranthene and the lowest to chrysene (potentially carcinogenic) and also to benzo(a)anthracene and indeno(1,2,3-cd)pyrene. Other compounds from the EPA list are not noted as carcinogenic. Main representative of carcinogens – benzo(a)pyrene does not dominate in analyzed group of PAHs, what may be related to summer season of sampling [1], but its content in air of the Silesian industrial region is still relatively high [44].

The general similarity of own results with these ones from the world literature data can suggest that major of identified PAHs may be universal products of high chemical stability, deriving from incomplete burning of various organic fuels. It may be also possible that these compounds derive mainly from the incomplete burning of oil fuels as the result of so-called low emission from vehicle exhaust because of widespread development of automotive transport. In the case of our own results, it could be confirmed by PAH distribution of the summer season when low emission pollutions are dominated by the exhaust gases from car engines as it is suggested below.

*Environmental Emissions*

1/ alkylnaphthalenes, 2/ phenanthrene, 3/ methylphenanthrenes + methylanthracenes, 4/ dimethylphenanthrenes + dimethylanthracenes, 5/fluoranthene, 6/ pyrene, 7/ benzofluorenes + methylpyrenes + benzo(c)phenanthrenes, 8/ benzo(a) anthracene, 9/ chrysene + triphenylene, 10/ alkylbenz(a)anthracenes, 11/alkylchrysenes, 12/benzofluoranthenes, 13/ benzo(e)pyrene, 14/ benzo(a)pyrene, 15/ perylene, 16/ anthanthrene, 17/ indeno(1,2,3-c,d)pyrene, 18/ benzo(ghi)perylene, 19/3,4-9,10-dibenzopyrene, and 20/ coronene. Many compounds from this group seem to be typical for pollution of atmosphere of the investigated industrial region in Poland (e.g., [40]) and at the same time are basic for environmental monitoring

*Total ion-chromatogram (TIC, GC/MS) of aromatic fraction of the extract from analyzed airborne* 

The PAHs alkylated are described here as groups of compounds, not all homologs being identified. In **Table 1**, the several alkyl substituted PAHs are presented,

SFS technique made possible the identification of a series of PAHs polluting urban air in the industrial region in Poland. Comparative analysis by GC-MS method has confirmed these results. Qualitative analysis of PAH mixtures by SFS is rather a fast technique and does not need many preparation steps and chemicals. However, for a complex mixture as the analyzed extract from the filter of air dust, the separation into fractions has been done (see subsection 3.1) to reduce the possibilities of mutual quenching of fluorescence by particular components of the mixture. Simplicity of SFS analysis can be shown, e.g., by the possibility of initial estimation of the condensation range of PAHs in analyzed mixture by the use of Δλ = 23 nm parameter as it was described earlier. However, the most important is

among other hydrocarbons, and identified by GC-MS and SFS methods.

in the European Union and the USA (e.g., [41], *loc.cit*.).

**5. Discussion of the results**

**134**

**Figure 8.**

*particulate matter.*

Considerable air pollution in the investigated urban atmosphere results in undoubtedly high pollution of whole region of Silesia. This is due to the high degree of industrialism, where an emission of diverse pollutants from many sources can be expected. In the region mentioned, the certain branches of industry, such as mining, metallurgy, nonferrous metals, and coke-making industries were developed excessively. There are also electric power stations and heat generating plants. High intensification of motor transport increases additively level of pollution in this region [13, 14].

The sources of air pollution in the Mysłowice urban area create a specific character of this air compared to that in the whole industrial region. The investigated air dust was sampled in summer. In this season, industrial production using organic fuels is underway, but the low emission from home stoves is minimalized. The main sources of low emission, however, seem to be in summer the engine fumes especially these from diesel motors (despite various actions to improve them). After the literature data [43], in summer season, one can expect in Silesia the relative increasing of concentration of pollutions originating from automobile exhaust as, e.g., pyrene, chrysene, triphenylene, benzo(g,h,i)perylene, benzo(c) phenanthrene, benzo(k)fluoranthene, and indeno(1,2,3-cd)pyrene. All of these compounds have been identified in analyzed PAH mixture, and they show clear dominance over other compounds (**Figure 8**). The domination of the engine exhaust in analyzed air pollution might be caused by the intense automobile traffic on the city area. There are three great car transit lines through the city: a highway autostrada passing by the city, expressway, and national road crossing the city center (the beltway around the city is only enabled in spatial planning).

The particular identified pollutants or their groups can thus help to indicate the pollution sources and to look for ways to improve the quality of environment.

#### **6. Conclusions**

The use of synchronous fluorescence spectroscopy (SFS technique) is advantageous for qualitative monitoring of the PAHs mixtures from urban air of the industrial region because this technique is simple, fast, low time consuming, and of low costs. Simpler and better separated spectra may be obtained in this manner than in the case of conventional fluorescence analysis. The special advantage of SFS technique is the possibility of analysis of complex environmental PAHs mixtures without the need of multistage sample fractionation. In this case, the "separation" of the complex mixtures is performed spectroscopically, which may be called the "spectral fractionation technique" [1].

Technique SFS used for samples in a form of solution, applied at the ambient temperature, allows obtaining well-separated spectra, simplified to one or several bands, allowed identification of individual compounds. This analytical process is possible, thanks to the use of the parameter Δλ characteristic for the particular identified compound. In this manner, the presence was stated in analyzed urban air dust of the PAHs with 2–6 condensed rings. However, the most clearly marked were aromatics from groups of anthracenes, benzo(a)anthracenes, pyrenes, and benzo(a)pyrenes. These compounds are among these PAHs, which characterize high fluorescence yield. The compounds from the group of naphthalene, benzofluorene, phenanthrene, benzophenanthrene, chrysene, fluoranthene, benzofluoranthene, and anthanthrene were also identified. The verification was performed for specific compounds, by recording of respective conventional emission or excitation spectra.

The results obtained may be a basis to discussion on the evaluation of the environmental hazards.

**137**

**Author details**

Sosnowiec, Poland

Aniela Matuszewska\* and Maria Czaja

provided the original work is properly cited.

Faculty of Natural Sciences, Institute of Earth Sciences, University of Silesia,

© 2020 The Author(s). Licensee IntechOpen. This chapter is distributed under the terms of the Creative Commons Attribution License (http://creativecommons.org/licenses/ by/3.0), which permits unrestricted use, distribution, and reproduction in any medium,

\*Address all correspondence to: aniela.matuszewska@us.edu.pl

*The Use of Synchronous Fluorescence Technique in Environmental Investigations of Polycyclic…*

The harmful influence of identified PAHs is a reason why they should be of a special interest in investigations of environmental samples. Thus, the choice of the effective analytical methods and techniques is here very important. The synchronous fluorescence technique seems to be appropriate method for monitoring PAHs in air dust samples of the industrial regions, especially when combustion of organic

*DOI: http://dx.doi.org/10.5772/intechopen.92402*

fossils still remains the main source of energy.

TIC total ion-chromatogram TLC thin layer chromatography

MSD mass selective detector

SFS synchronous fluorescence spectroscopy PAHs polycyclic aromatic hydrocarbons

GC/MS gas chromatography-mass spectrometry HPLC high performed liquid chromatography

EPA Environmental Protection Agency

**Abbreviations**

*The Use of Synchronous Fluorescence Technique in Environmental Investigations of Polycyclic… DOI: http://dx.doi.org/10.5772/intechopen.92402*

The harmful influence of identified PAHs is a reason why they should be of a special interest in investigations of environmental samples. Thus, the choice of the effective analytical methods and techniques is here very important. The synchronous fluorescence technique seems to be appropriate method for monitoring PAHs in air dust samples of the industrial regions, especially when combustion of organic fossils still remains the main source of energy.

#### **Abbreviations**

*Environmental Emissions*

region [13, 14].

**6. Conclusions**

"spectral fractionation technique" [1].

Considerable air pollution in the investigated urban atmosphere results in undoubtedly high pollution of whole region of Silesia. This is due to the high degree of industrialism, where an emission of diverse pollutants from many sources can be expected. In the region mentioned, the certain branches of industry, such as mining, metallurgy, nonferrous metals, and coke-making industries were developed excessively. There are also electric power stations and heat generating plants. High intensification of motor transport increases additively level of pollution in this

The sources of air pollution in the Mysłowice urban area create a specific character of this air compared to that in the whole industrial region. The investigated air dust was sampled in summer. In this season, industrial production using organic fuels is underway, but the low emission from home stoves is minimalized. The main sources of low emission, however, seem to be in summer the engine fumes especially these from diesel motors (despite various actions to improve them). After the literature data [43], in summer season, one can expect in Silesia the relative increasing of concentration of pollutions originating from automobile exhaust as, e.g., pyrene, chrysene, triphenylene, benzo(g,h,i)perylene, benzo(c) phenanthrene, benzo(k)fluoranthene, and indeno(1,2,3-cd)pyrene. All of these compounds have been identified in analyzed PAH mixture, and they show clear dominance over other compounds (**Figure 8**). The domination of the engine exhaust in analyzed air pollution might be caused by the intense automobile traffic on the city area. There are three great car transit lines through the city: a highway autostrada passing by the city, expressway, and national road crossing the city center (the beltway around the city is only enabled in spatial planning).

The particular identified pollutants or their groups can thus help to indicate the

The use of synchronous fluorescence spectroscopy (SFS technique) is advantageous for qualitative monitoring of the PAHs mixtures from urban air of the industrial region because this technique is simple, fast, low time consuming, and of low costs. Simpler and better separated spectra may be obtained in this manner than in the case of conventional fluorescence analysis. The special advantage of SFS technique is the possibility of analysis of complex environmental PAHs mixtures without the need of multistage sample fractionation. In this case, the "separation" of the complex mixtures is performed spectroscopically, which may be called the

Technique SFS used for samples in a form of solution, applied at the ambient temperature, allows obtaining well-separated spectra, simplified to one or several bands, allowed identification of individual compounds. This analytical process is possible, thanks to the use of the parameter Δλ characteristic for the particular identified compound. In this manner, the presence was stated in analyzed urban air dust of the PAHs with 2–6 condensed rings. However, the most clearly marked were aromatics from groups of anthracenes, benzo(a)anthracenes, pyrenes, and benzo(a)pyrenes. These compounds are among these PAHs, which characterize high fluorescence yield. The compounds from the group of naphthalene, benzofluorene, phenanthrene, benzophenanthrene, chrysene, fluoranthene, benzofluoranthene, and anthanthrene were also identified. The verification was performed for specific compounds, by recording of respective conventional emission or excitation spectra. The results obtained may be a basis to discussion on the evaluation of the

pollution sources and to look for ways to improve the quality of environment.

**136**

environmental hazards.


#### **Author details**

Aniela Matuszewska\* and Maria Czaja Faculty of Natural Sciences, Institute of Earth Sciences, University of Silesia, Sosnowiec, Poland

\*Address all correspondence to: aniela.matuszewska@us.edu.pl

© 2020 The Author(s). Licensee IntechOpen. This chapter is distributed under the terms of the Creative Commons Attribution License (http://creativecommons.org/licenses/ by/3.0), which permits unrestricted use, distribution, and reproduction in any medium, provided the original work is properly cited.

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[22] Assenmacher-Maiworm H, Hahn J-U, Heinrich B, Schuh C, Hebisch R, Brock TH, et al. Policyclic aromatic hydrocarbons (PAHs) – Method for the determination of semi-volatile

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[24] Lakowicz JR. Principles of Fluorescence Spectroscopy. 3rd ed. Boston: Springer; 2006. p. 954

[25] Vo-Dinh T. Synchronous luminescence spectroscopy: Methodology and applicability. Applied Spectroscopy. 1982;**36**:576-581

[26] Lin ELC, Cormier SM, Racine RN. Synchronous fluorimetric measurement of metabolites of polycyclic aromatic hydrocarbons in the bile of brown bulhead. Environmental Toxicology and Chemistry. 1994;**13**:707-715

[27] Abbott DW, Moody RL, Mann RM, Vo-Dinh T. Synchronous luminescence screening for polynuclear aromatic compounds in environmental samples collected at a coal gasification process development unit. American Industrial Hygiene Association Journal. 1986;**47**(7):379-385

[28] Mastral AM, Callén M, Mayoral C, Galbán J. Polycyclic aromatic hydrocarbon emissions from fluidized bed combustion of coal. Fuel. 1995;**74**:1762-1766

[29] Matuszewska A, Czaja M. The use of synchronous luminescence spectroscopy in qualitative analysis of aromatic fraction of hard coal thermolysis products. Talanta. 2000;**52**:457-464

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**138**

*Environmental Emissions*

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1981

1968;**152**:282-285

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[9] Abdel-Shafy HI, Mansour MSM. A

review on polycyclic aromatic hydrocarbons, environment, impact, effect on human health and remediation. Egyptian Journal of Petroleum. 2016;**25**:107-123

[10] Desantes JM, Berrmúdez V,

Science. 2005;**36**:1251-1276

[11] Maricq MM. Chemical

1993;**31**:349-352

Garcia JM, Fuentes E. Effects of current engine strategies on the exhaust aerosol particle size distribution from a heavyduty diesel engine. Journal of Aerosol

characterization of particulate emission from diesel engines: A review. Journal of Aerosol Science. 2007;**38**:1079-1118

[12] Levy JM, Dolata LA, Ravey RM. Considerations of SFE for GC/MS determination of polynuclear aromatic hydrocarbons in soils and sediments. Journal of Chromatographic Science.

[13] Bodzek D, Luks-Betley K, Warzecha L. Research on the determination of toxic organic compounds in airborne particular matter in Upper Silesia. Polish Journal of Environmental Studies. 1993;**2**:13-22

[14] Bodzek D, Luks-Betley K.

associated polycyclic aromatic hydrocarbons in ambient air samples from the Upper Silesia region of Poland. Atmospheric Environment.

1993;**27A**:759-764

Warzecha L, Determination of particle-

[15] Węglarz A, Skrok R. Application of GC-FID and GC-MS for assessing PAHs in suspended dust. Central European Journal of Public Health. 2000;**8**:86-88

[16] Poster DL, Schantz MM, Sander LC, Wise SA. Analysis of polycyclic aromatic hydrocarbons (PAHs) in environmental

samples: A critical review of gas chromatographic (GC) methods.

[2] Knorr M, Schenk D. About the question of synthesis of polycyclic aromatic hydrocarbons by bacteria. Archiv für Hygiene und Bakteriologie.

[3] Bojakowska I, Sokołowska G. Polycyclic aromatic hydrocarbons in crude oils from Poland. Geological

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[5] Santana Rodriguez JJ, Padrón SC.

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[8] Ravindra K, Sokhi R, Grieken RV. Atmospheric polycyclic aromatic hydrocarbons: Source attribution, emission factors and regulation. Atmospheric Environment.

2000;**28**(8):710-717

2002;**17**:1401-1428

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**141**

**Chapter 8**

**Abstract**

related to polluted intake air.

in-use vehicles, trace elements

**1. Introduction**

Qualitative Characterisation

Particulate Matter from In-Use

Diesel Engine Passenger Vehicles

*Richard Viskup, Christoph Wolf and Werner Baumgartner*

In this research, we applied laser-plasma spectroscopy technique for the measurement of trace chemical elements in the exhaust emissions generated from in-use diesel engine passenger vehicles. We use high resolution laser-induced breakdown spectroscopy (LIBS) technique for diagnostics of soot and particulate matter (PM). Here we analysed soot and PM, extracted from exhaust manifold part, from different passenger vehicles that are used in daily life environment. The main aim of this study is to reveal the trace chemical elements in different PM matrices. The presence of trace elements in exhaust emissions can originate from different sources: from injected fuel type and fuel additives, engine lubricants, engine combustion process, incomplete catalytic reaction, inefficiency or wear out of PM filtering devices, dysfunctions or failures of engine or vehicle or even information

**Keywords:** laser-induced breakdown spectroscopy (LIBS), particulate matter, soot, nanoparticles, emissions, emission standards, diesel, diesel engine, diesel vehicles,

In this research, the laser-induced breakdown spectroscopy (LIBS) technique for diagnostics of trace chemical elements in diesel particulate matter (DPM) formed

Laser-induced breakdown spectroscopy is a powerful spectrochemical measurement technique for fast qualitative and very sensitive quantitative compositional analysis of various forms of matter: solid state, liquid, gas as well as fine powders or nanoparticles [4–6]. One of the pioneers in measurement of particulate trace emissions from vehicles was the group of Schauer et al. [7] as they used a comprehensive dilution source sampler, organic chemical analysis and X-ray fluorescence analysis for mass and chemical composition measurements of fine particles. Other

from in-use diesel engine passenger vehicles has been used [1–3].

of Trace Elements in Diesel

by Means of Laser-Induced

Breakdown Spectroscopy

#### **Chapter 8**

*Environmental Emissions*

2000;**28**(8):710-717

SOO216-002-1330-y

[31] Santana Rodriguez JJ, Padrón SC.

[38] Mille G, Kister J, Guiliano M, Dou H. Spectroscopie de fluorescence UV: Technique d`excitation émission synchrones. Applications á l`étude de composés fossiles. Spectra.

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[40] Marynowski L, Pięta M, Janeczek J. Compositoon and source of polycyclic aromatic compounds in deposited dust from selected sites around the Upper Silesia. Geological Quarterly.

[41] Mazur-Badura X. Profil WWA w cząstkach stałych (PM) emitowanych z silnika Diesla. Nafta-Gaz. 2012;**68**:

Bjørseth A, editor. Polycyclic Aromatic Hydrocarbons. New York: Marcel Dekker; 1983. pp. 464-468

wielopierścieniowych węglowodorów aromatycznych występujących w naturalnym środowisku człowieka. Chemist-Analyst. 1988;**33**:21-54.

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[42] Fazio T, Howard JW. In:

[43] Warzecha L, Luks-Betlej K, Bodzek D. Metody analizy

[44] Rusin M, Marchwińska-Wyrwał E. Zagrożenia zdrowotne związane ze środowiskowym narażeniem na wielopierścieniowe węglowodory aromatyczne (WWA). Medycyna Środowiskowa. 2014;**17**(3):

synchronous fluoresence scan spectra of petroleum products. Analytical and Bioanalytical Chemistry.

2002;**373**(4-5):304-309. DOI: 10.1007/

[33] Li Y-Q, Li X-Y, Shindi AAF, Zou Z-X, Liu Q, Lin LR. Synchronous fluorescence spectroscopy and its applications in clinical analysis and food safety evaluation. In: Geddes CD, editor. Reviews in Fluorescence. New York: Springer Science; 2010. DOI: 10.1007/978-1-4419-9828-6\_5

[34] Zhang R, Yuan Q, Chen K, He L. Constant-wavelength synchronous fluorescence spectrometry for the determination of polycyclic aromatic hydrocarbons in water samples. Advanced Materials Research. 2012;**490-495**:3202-3206

[35] Sharma H, Jain VJ, Khan ZH. Use of constant wavelength synchronous spectrofluorimetry for identification of polycyclic aromatic hydrocarbons in air particulate samples. Spectrochimica Acta Part A. 2013;**108**:268-273. DOI:

10.1016/j.saa.2013.01.079

2020;**6**(1):3092-3104

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[37] Kershaw JR. Fluorescence spectroscopy in the characterization

of coal-derived liquids. Fuel.

[36] Nógrega JA, dos Santos RL, de Nara RH, Nunes de Oliveira RA, Capato CF, Falcão EA, et al. Quantification of chrysene and benzo(a)pyrene in surface water samples by fluorescence measurement. Brazilian Journal of Development.

Fluorescence techniques for the determination of polycyclic aromatic hydrocarbons in marine environment: An overview. Analusis.

[32] Patra D, Mishra A. Total

**140**

Qualitative Characterisation of Trace Elements in Diesel Particulate Matter from In-Use Diesel Engine Passenger Vehicles by Means of Laser-Induced Breakdown Spectroscopy

*Richard Viskup, Christoph Wolf and Werner Baumgartner*

#### **Abstract**

In this research, we applied laser-plasma spectroscopy technique for the measurement of trace chemical elements in the exhaust emissions generated from in-use diesel engine passenger vehicles. We use high resolution laser-induced breakdown spectroscopy (LIBS) technique for diagnostics of soot and particulate matter (PM). Here we analysed soot and PM, extracted from exhaust manifold part, from different passenger vehicles that are used in daily life environment. The main aim of this study is to reveal the trace chemical elements in different PM matrices. The presence of trace elements in exhaust emissions can originate from different sources: from injected fuel type and fuel additives, engine lubricants, engine combustion process, incomplete catalytic reaction, inefficiency or wear out of PM filtering devices, dysfunctions or failures of engine or vehicle or even information related to polluted intake air.

**Keywords:** laser-induced breakdown spectroscopy (LIBS), particulate matter, soot, nanoparticles, emissions, emission standards, diesel, diesel engine, diesel vehicles, in-use vehicles, trace elements

#### **1. Introduction**

In this research, the laser-induced breakdown spectroscopy (LIBS) technique for diagnostics of trace chemical elements in diesel particulate matter (DPM) formed from in-use diesel engine passenger vehicles has been used [1–3].

Laser-induced breakdown spectroscopy is a powerful spectrochemical measurement technique for fast qualitative and very sensitive quantitative compositional analysis of various forms of matter: solid state, liquid, gas as well as fine powders or nanoparticles [4–6]. One of the pioneers in measurement of particulate trace emissions from vehicles was the group of Schauer et al. [7] as they used a comprehensive dilution source sampler, organic chemical analysis and X-ray fluorescence analysis for mass and chemical composition measurements of fine particles. Other

groups [8–11] used inductively coupled plasma mass spectrometry ICP-MS and XRF for characterisation of metals and other particle-phase species from on-road motor vehicles. They found the following trace elements in the particles: Al, Ba, Be, Ca, Cd, Co, Cr, Cu, Fe, K, Mg, Mn, Mo, Na, Ni, Pb, Pt, S, Sr, Ti, V and Zn. Other groups [12–16] used ICP-OES to characterise the different biodiesel samples with special concern to quantify the Al, Ca, Cu, Fe, K, Mg, Mn, Na, Ni, P, Sr, B and Cl content, to evaluate the fuel quality and to control the emission of pollutants to the atmosphere. In this case, the samples were prepared using a high pressure asher digestion procedure for metal determination in biodiesel samples. Different groups used ICP-MS to characterise additional bound elements, such as Cd, As, Ba and Ti in the particulate matter collected from ultra-low-sulphur diesel and biodiesel powered engine exhaust emissions [17].

In the past two decades, a new laser technology evolved in the application of laser-induced breakdown spectroscopy into combustion diagnostics. One of the first research papers that reported the LIBS for on-line engine equivalence ratio measurement was performed by the group of Ferioli et al. [18], followed by research related to measurements of hydrocarbons using LIBS [19]. The implementation of LIBS for in-cylinder measurements was made by Joshi et al. [20], followed by Groß et al. [21]. Another group has studied the LIBS to monitor local lambda values during mixture formation in a direct-injection engine [22]. Different application of LIBS to an engine valve has been used by the group of Lopez-Quintas et al. [23] for mapping of mechanical specimens. Kiefer et al. [24] have used laser-induced breakdown spectroscopy in a partially premixed turbulent jet flame, and the group of Hsu et al. [25] performed measurements of fuel air-ratio in methane-air flames at different pressures. The qualitative and quantitative characterisation of major chemical elements bound in different types of diesel particulate matter measured by laser-induced breakdown spectroscopy technique has been studied by Viskup et al. [26, 27]. And the identification of minor chemical elements in diesel particulate matter by LIBS was studied by Viskup et al. [28].

In this research, the main aim is to measure the trace chemical elements in particulate matter from diesel exhaust emissions. The presence of trace elements in PM can reveal different types of information related to vehicle and engine, combustion process, injected fuel type, fuel additives, engine lubricants, state of selective catalytic reduction devices, inefficiency or wear out of PM filtering devices, engine failure, engine wear out or information related to polluted intake air.

#### **2. Experimental**

#### **2.1 Laser-induced breakdown spectroscopy setup**

The laser created plasma was generated by the Nd:YAG solid state laser from Quantel corp. This laser operates at the fundamental wavelength of 1064 nm with a pulse duration of 8.5 ns and a laser energy of 300 mJ. The emerged laser radiation has been focused with 10 cm focusing lens into the plane solid target surface to create a plasma. Optical emission from plasma has been collected perpendicularly via optical telescope into the high resolution Echelle spectrograph model Aryelle Butterfly from LTB Berlin equipped with sensitive ICCD detector. The spectrometer consists of two separate spectrographs—UV part and VIS part. The UV part is from 190 to 440 nm, and the VIS part of the optical spectrum is from 440 to 800 nm. Spectral resolution is from 3 pm (picometre) to 7 pm for VUV and from 4 pm to 8 pm for VIS part. This Echelle spectrograph provides spectral information in broad range with very high resolution. Optical emission from plasma has been collected

**143**

12 laser shots.

**Figure 1.**

**3. Results and discussion**

**3.1 Identification of the major chemical elements in PM**

components of diesel particulate matter [26].

*Qualitative Characterisation of Trace Elements in Diesel Particulate Matter from In-Use Diesel…*

from VUV as well as from VIS parts; thus, the total spectral window from 190 to 800 nm wavelength has been recorded. The delay time of 1 μs after the laser trigger and the gate width of 2 μs were used. The LIBS measurements were performed in open air atmosphere at atmospheric pressure and at room temperature. Layout of the Laser Induced Breakdown Spectroscopy setup is shown in the **Figure 1**.

Different PM samples from in-use diesel engine passenger vehicles of major brand car producers in Europe have been analysed by LIBS. Particulate matter has been collected from the tail pipe at the end of the exhaust manifold, while selections of in-use vehicles were performed randomly. Laser-induced breakdown spectroscopy from DPM shows optical emission and spectral lines that are characteristic in ultraviolet and visible spectral region. The collected particulate matter from diesel engine passenger vehicles and exhaust manifold has been mechanically pressed into small pellets with flat disc shape. Each displayed spectrum has been averaged over

Characteristic laser-induced breakdown spectroscopy signal from measurement of diesel particulate matter is shown in **Figure 2**. LIBS spectra generated from particulate matter collected from in-use diesel engine passenger vehicles exhibit characteristic optical emission lines with distinct of atomic, ionic and molecular origin included in the signal. Strong optical emission is from major spectral lines, particularly from carbon, iron, magnesium, aluminium, chromium, zinc, sodium and calcium. These elements were in previous research identified in PM as major

By means of high-resolution optical emission LIBS spectroscopy, different PM matrices were spectrochemically analysed. From analytical measurements, the composition of major chemical elements in the particulate matter collected from different in-use diesel engine passenger vehicles was obtained. From qualitative

*DOI: http://dx.doi.org/10.5772/intechopen.93067*

**2.2 Sample preparation and collection**

*Layout of laser-induced breakdown spectroscopy setup.*

*Qualitative Characterisation of Trace Elements in Diesel Particulate Matter from In-Use Diesel… DOI: http://dx.doi.org/10.5772/intechopen.93067*

**Figure 1.** *Layout of laser-induced breakdown spectroscopy setup.*

*Environmental Emissions*

powered engine exhaust emissions [17].

late matter by LIBS was studied by Viskup et al. [28].

**2.1 Laser-induced breakdown spectroscopy setup**

groups [8–11] used inductively coupled plasma mass spectrometry ICP-MS and XRF for characterisation of metals and other particle-phase species from on-road motor vehicles. They found the following trace elements in the particles: Al, Ba, Be, Ca, Cd, Co, Cr, Cu, Fe, K, Mg, Mn, Mo, Na, Ni, Pb, Pt, S, Sr, Ti, V and Zn. Other groups [12–16] used ICP-OES to characterise the different biodiesel samples with special concern to quantify the Al, Ca, Cu, Fe, K, Mg, Mn, Na, Ni, P, Sr, B and Cl content, to evaluate the fuel quality and to control the emission of pollutants to the atmosphere. In this case, the samples were prepared using a high pressure asher digestion procedure for metal determination in biodiesel samples. Different groups used ICP-MS to characterise additional bound elements, such as Cd, As, Ba and Ti in the particulate matter collected from ultra-low-sulphur diesel and biodiesel

In the past two decades, a new laser technology evolved in the application of laser-induced breakdown spectroscopy into combustion diagnostics. One of the first research papers that reported the LIBS for on-line engine equivalence ratio measurement was performed by the group of Ferioli et al. [18], followed by research related to measurements of hydrocarbons using LIBS [19]. The implementation of LIBS for in-cylinder measurements was made by Joshi et al. [20], followed by Groß et al. [21]. Another group has studied the LIBS to monitor local lambda values during mixture formation in a direct-injection engine [22]. Different application of LIBS to an engine valve has been used by the group of Lopez-Quintas et al. [23] for mapping of mechanical specimens. Kiefer et al. [24] have used laser-induced breakdown spectroscopy in a partially premixed turbulent jet flame, and the group of Hsu et al. [25] performed measurements of fuel air-ratio in methane-air flames at different pressures. The qualitative and quantitative characterisation of major chemical elements bound in different types of diesel particulate matter measured by laser-induced breakdown spectroscopy technique has been studied by Viskup et al. [26, 27]. And the identification of minor chemical elements in diesel particu-

In this research, the main aim is to measure the trace chemical elements in particulate matter from diesel exhaust emissions. The presence of trace elements in PM can reveal different types of information related to vehicle and engine, combustion process, injected fuel type, fuel additives, engine lubricants, state of selective catalytic reduction devices, inefficiency or wear out of PM filtering devices, engine

The laser created plasma was generated by the Nd:YAG solid state laser from Quantel corp. This laser operates at the fundamental wavelength of 1064 nm with a pulse duration of 8.5 ns and a laser energy of 300 mJ. The emerged laser radiation has been focused with 10 cm focusing lens into the plane solid target surface to create a plasma. Optical emission from plasma has been collected perpendicularly via optical telescope into the high resolution Echelle spectrograph model Aryelle Butterfly from LTB Berlin equipped with sensitive ICCD detector. The spectrometer consists of two separate spectrographs—UV part and VIS part. The UV part is from 190 to 440 nm, and the VIS part of the optical spectrum is from 440 to 800 nm. Spectral resolution is from 3 pm (picometre) to 7 pm for VUV and from 4 pm to 8 pm for VIS part. This Echelle spectrograph provides spectral information in broad range with very high resolution. Optical emission from plasma has been collected

failure, engine wear out or information related to polluted intake air.

**142**

**2. Experimental**

from VUV as well as from VIS parts; thus, the total spectral window from 190 to 800 nm wavelength has been recorded. The delay time of 1 μs after the laser trigger and the gate width of 2 μs were used. The LIBS measurements were performed in open air atmosphere at atmospheric pressure and at room temperature. Layout of the Laser Induced Breakdown Spectroscopy setup is shown in the **Figure 1**.

#### **2.2 Sample preparation and collection**

Different PM samples from in-use diesel engine passenger vehicles of major brand car producers in Europe have been analysed by LIBS. Particulate matter has been collected from the tail pipe at the end of the exhaust manifold, while selections of in-use vehicles were performed randomly. Laser-induced breakdown spectroscopy from DPM shows optical emission and spectral lines that are characteristic in ultraviolet and visible spectral region. The collected particulate matter from diesel engine passenger vehicles and exhaust manifold has been mechanically pressed into small pellets with flat disc shape. Each displayed spectrum has been averaged over 12 laser shots.

#### **3. Results and discussion**

#### **3.1 Identification of the major chemical elements in PM**

Characteristic laser-induced breakdown spectroscopy signal from measurement of diesel particulate matter is shown in **Figure 2**. LIBS spectra generated from particulate matter collected from in-use diesel engine passenger vehicles exhibit characteristic optical emission lines with distinct of atomic, ionic and molecular origin included in the signal. Strong optical emission is from major spectral lines, particularly from carbon, iron, magnesium, aluminium, chromium, zinc, sodium and calcium. These elements were in previous research identified in PM as major components of diesel particulate matter [26].

By means of high-resolution optical emission LIBS spectroscopy, different PM matrices were spectrochemically analysed. From analytical measurements, the composition of major chemical elements in the particulate matter collected from different in-use diesel engine passenger vehicles was obtained. From qualitative

**Figure 2.**

*Optical emission LIBS spectra from diesel particulate matter sample. High intensity spectral lines are from major components carbon, iron, magnesium, aluminium, chromium, zinc, sodium and calcium.*

measurements and calibration curves, we found that the major chemical elements of DPM besides the carbon are iron, magnesium, aluminium, chromium, zinc, sodium and calcium with different concentrations. By using quantitative analytical LIBS approach, the maximum concentrations of major chemical elements in DPM from in-use Diesel engine passenger vehicles were measured as follows: Carbon up to ~ 64 weight percent (wt%), Fe ~ 54 wt%, Mg ~ 7 wt%, Al ~ 6 wt%, Cr ~ 6 wt%, Zn ~ 7 wt%, Na ~ 11 wt%, Ca ~13 wt%, for more details see Ref. [26, 27].

#### **3.2 Identification of the minor chemical elements in PM**

Further research was dedicated to identify the minor chemical elements of DPM. The state-of-the-art laboratory LIBS setup has been used to obtain highresolution optical emission spectra images. The qualitative measurements and LIBS signal show the minor chemical elements with optical emission spectra from silicon, nickel, titan, potassium, strontium and molybdenum. More detail study of this topic is presented in Ref. [28].

#### **3.3 Identification of the trace elements in PM**

To identify the trace elements in various DPM matrices, the LIBS setup was optimised for optical detection to obtain high-quality spectral data. Acquired signals show optical emissions from trace elements, particularly from barium, boron, cobalt, copper, phosphorus, manganese and platinum in high resolution and in good signal-to-noise ratio. Optical emission spectra from atomic and ionic lines of identified trace elements are shown in **Figure 3**. Here we only select few samples with most pronounced signal to clearly visualise the peak line shape of spectral information.

#### **3.4 Trace elements of diesel particulate matter**

*Barium spectral line*: ionic emission from Ba II @ 455.40 nm is shown in **Figure 3(a)**. In this figure, a raw spectral data from LIBS measurements are shown. Here we select six different diesel particulate matter samples with most intense Barium peak. Selected samples with barium ionic line are samples with numbers 61, 4, 51, 26, 41 and 60. Barium signal has been measured in 26 samples, from 67 different DPM samples, see **Figure 4(a)**. From LIBS spectra, one can observe that analysed signal mainly line peak shape, line peak intensity and line peak width is

**145**

**Figure 3.**

*from in-use passenger diesel engine vehicles.*

*Qualitative Characterisation of Trace Elements in Diesel Particulate Matter from In-Use Diesel…*

*Optical emission spectra from barium (a), boron (b), cobalt (c), copper (d), phosphorus (e), manganese (f) and platinum (g), measured by high-resolution LIBS technique from diesel particulate matter collected* 

*DOI: http://dx.doi.org/10.5772/intechopen.93067*

*Qualitative Characterisation of Trace Elements in Diesel Particulate Matter from In-Use Diesel… DOI: http://dx.doi.org/10.5772/intechopen.93067*

#### **Figure 3.**

*Optical emission spectra from barium (a), boron (b), cobalt (c), copper (d), phosphorus (e), manganese (f) and platinum (g), measured by high-resolution LIBS technique from diesel particulate matter collected from in-use passenger diesel engine vehicles.*

*Environmental Emissions*

**Figure 2.**

measurements and calibration curves, we found that the major chemical elements of DPM besides the carbon are iron, magnesium, aluminium, chromium, zinc, sodium and calcium with different concentrations. By using quantitative analytical LIBS approach, the maximum concentrations of major chemical elements in DPM from in-use Diesel engine passenger vehicles were measured as follows: Carbon up to ~ 64 weight percent (wt%), Fe ~ 54 wt%, Mg ~ 7 wt%, Al ~ 6 wt%, Cr ~ 6 wt%,

*Optical emission LIBS spectra from diesel particulate matter sample. High intensity spectral lines are from major components carbon, iron, magnesium, aluminium, chromium, zinc, sodium and calcium.*

Further research was dedicated to identify the minor chemical elements of DPM. The state-of-the-art laboratory LIBS setup has been used to obtain highresolution optical emission spectra images. The qualitative measurements and LIBS signal show the minor chemical elements with optical emission spectra from silicon, nickel, titan, potassium, strontium and molybdenum. More detail study of

To identify the trace elements in various DPM matrices, the LIBS setup was optimised for optical detection to obtain high-quality spectral data. Acquired signals show optical emissions from trace elements, particularly from barium, boron, cobalt, copper, phosphorus, manganese and platinum in high resolution and in good signal-to-noise ratio. Optical emission spectra from atomic and ionic lines of identified trace elements are shown in **Figure 3**. Here we only select few samples with most pronounced signal to clearly visualise the peak line shape of spectral

*Barium spectral line*: ionic emission from Ba II @ 455.40 nm is shown in **Figure 3(a)**. In this figure, a raw spectral data from LIBS measurements are shown. Here we select six different diesel particulate matter samples with most intense Barium peak. Selected samples with barium ionic line are samples with numbers 61, 4, 51, 26, 41 and 60. Barium signal has been measured in 26 samples, from 67 different DPM samples, see **Figure 4(a)**. From LIBS spectra, one can observe that analysed signal mainly line peak shape, line peak intensity and line peak width is

Zn ~ 7 wt%, Na ~ 11 wt%, Ca ~13 wt%, for more details see Ref. [26, 27].

**3.2 Identification of the minor chemical elements in PM**

this topic is presented in Ref. [28].

**3.3 Identification of the trace elements in PM**

**3.4 Trace elements of diesel particulate matter**

**144**

information.

changing according to different DPM samples. The strength of particular atomic or ionic line is basically proportional to the concentration of the element in the studied material. Thus, for qualitative comparison, we numerically calculate the respond signal—the integral of peak values for each spectral line of interest—to obtain information about elemental atomic composition of different types of diesel particulate matter. The results from numerical calculation and integration of peak area are shown in **Figure 4**. From this figure, one can easily compare the individual changes in trace signal related to concentration values in a.u. (arbitrary unit). Nevertheless, in case of exact quantitative characterisation of the trace element in DPM, the particular calibration of trace element signal would be necessary to perform. However, from previous analytical LIBS measurements and qualitative

#### **Figure 4.**

*Comparison of calculated integral values from LIBS optical emission spectra of barium (a), boron (b), cobalt (c), copper (d), phosphorus (e), manganese (f) and platinum (g) trace elements in diesel particulate matter, collected from different in-use passenger diesel engine vehicles.*

**147**

**Table 1.**

*Qualitative Characterisation of Trace Elements in Diesel Particulate Matter from In-Use Diesel…*

comparison of LIBS signal of major and minor elements in DPM, we could classify

*Cobalt spectral line*: optical emission from Co II @ 228.61 nm is shown in **Figure 3(c)**. Here, the relatively higher content of cobalt was measured in samples 54, 12, 57, 56, 65, 64, 67 and 55. From numerical calculation of Co II spectral line, signal from cobalt emission was measured in 14 different DPM matrices, as shown in

shown in **Figure 4(d)**. Copper is present in 62 different samples.

*Copper spectral line*: this is shown in **Figure 3(d)** as ionic Cu II @ 224.70 nm in ultraviolet spectral range. High content has been measured in samples 44, 12, 59, 20, 5, 41, 37 and 28. The comparison of integral spectral peak calculated values is

*Phosphorus spectral line*: phosphorus spectral signal from six DPM samples is shown in **Figure 3(e)**. The observed phosphorus ionic line P II @ 221.03 nm is present in UV spectral range. The compared results from numerical calculation of integral peak values are shown in **Figure 4(e)**. Phosphorus trace element has been measured in 26 different DPM samples. Strong LIBS signal from phosphorus ele-

*Manganese spectral line*: atomic emission from manganese triplet Mn I @ 403.07 nm, Mn I @ 403.30 nm and Mn I @ 403.44 nm is shown in **Figure 3(f )**. From this figure, one can observe higher content of manganese in samples 12, 4, 55, 59, 34 and 67. Manganese trace element has been measured in 18 different DPM

*Platinum spectral line*: atomic emission from platinum chemical element is shown in **Figure 3(g)**. Here, the spectral line Pt I @ 203.24 nm from eight different DPM samples is clearly visible. Platinum as the trace element was measured in 30 different samples. While most of the intense signal was recorded from samples 12, 55, 59, 58, 34, 20, 27 and 64. Compared integral values are calculated and shown in **Figure 4(g)**.

> **Detected in/ total number of samples**

Ba Ba II 455.40 26/67 61, 4, 51, 26, 41, 60 Barium B B I 208.95 27/67 4, 2, 22, 30, 15, 64 Boron

P P II 221.03 26/67 44, 12, 4, 5,34, 20 Phosphorus Mn Mn I 403.07 18/67 12, 4, 55, 59, 34, 67 Manganese

Co Co II 228.61 14/67 54, 12, 57, 56, 65, 64,

Cu Cu II 224.70 62/67 44, 12, 59, 20, 5, 41,

Pt Pt I 203.24 30/67 12, 55, 59, 58, 34, 20,

*Summary of detected trace elements and spectral lines. Number of samples with detected trace signal and* 

**Most pronounced signal in samples**

67, 55

37, 28

27, 64

**Chemical element**

Cobalt

Copper

Platinum

samples, and the comparison of integral values is shown in **Figure 4(f )**.

**Wavelength (nm)**

*Boron spectral line*: in **Figure 3(b)**, measured atomic emission from boron, doublet spectra line B I @ 208.88 nm and B I @ 208.95 nm, is shown. Here we selected six different samples with line emission from boron, where the LIBS signal is clearly visible. The comparison of calculated integral peak values is shown in **Figure 4(b)**. Samples with high content of boron are 4, 2, 22, 30, 15 and 64. Boron is in DPM

*DOI: http://dx.doi.org/10.5772/intechopen.93067*

the Barium as a trace element in DPM.

**Figure 4(c)**.

present as trace element in 27 different samples.

ment is in samples 44, 12, 4, 5, 34 and 20.

**Analyte Spectral** 

*samples with most pronounced signal.*

**line**

*Qualitative Characterisation of Trace Elements in Diesel Particulate Matter from In-Use Diesel… DOI: http://dx.doi.org/10.5772/intechopen.93067*

comparison of LIBS signal of major and minor elements in DPM, we could classify the Barium as a trace element in DPM.

*Boron spectral line*: in **Figure 3(b)**, measured atomic emission from boron, doublet spectra line B I @ 208.88 nm and B I @ 208.95 nm, is shown. Here we selected six different samples with line emission from boron, where the LIBS signal is clearly visible. The comparison of calculated integral peak values is shown in **Figure 4(b)**. Samples with high content of boron are 4, 2, 22, 30, 15 and 64. Boron is in DPM present as trace element in 27 different samples.

*Cobalt spectral line*: optical emission from Co II @ 228.61 nm is shown in **Figure 3(c)**. Here, the relatively higher content of cobalt was measured in samples 54, 12, 57, 56, 65, 64, 67 and 55. From numerical calculation of Co II spectral line, signal from cobalt emission was measured in 14 different DPM matrices, as shown in **Figure 4(c)**.

*Copper spectral line*: this is shown in **Figure 3(d)** as ionic Cu II @ 224.70 nm in ultraviolet spectral range. High content has been measured in samples 44, 12, 59, 20, 5, 41, 37 and 28. The comparison of integral spectral peak calculated values is shown in **Figure 4(d)**. Copper is present in 62 different samples.

*Phosphorus spectral line*: phosphorus spectral signal from six DPM samples is shown in **Figure 3(e)**. The observed phosphorus ionic line P II @ 221.03 nm is present in UV spectral range. The compared results from numerical calculation of integral peak values are shown in **Figure 4(e)**. Phosphorus trace element has been measured in 26 different DPM samples. Strong LIBS signal from phosphorus element is in samples 44, 12, 4, 5, 34 and 20.

*Manganese spectral line*: atomic emission from manganese triplet Mn I @ 403.07 nm, Mn I @ 403.30 nm and Mn I @ 403.44 nm is shown in **Figure 3(f )**. From this figure, one can observe higher content of manganese in samples 12, 4, 55, 59, 34 and 67. Manganese trace element has been measured in 18 different DPM samples, and the comparison of integral values is shown in **Figure 4(f )**.

*Platinum spectral line*: atomic emission from platinum chemical element is shown in **Figure 3(g)**. Here, the spectral line Pt I @ 203.24 nm from eight different DPM samples is clearly visible. Platinum as the trace element was measured in 30 different samples. While most of the intense signal was recorded from samples 12, 55, 59, 58, 34, 20, 27 and 64. Compared integral values are calculated and shown in **Figure 4(g)**.


#### **Table 1.**

*Environmental Emissions*

changing according to different DPM samples. The strength of particular atomic or ionic line is basically proportional to the concentration of the element in the studied material. Thus, for qualitative comparison, we numerically calculate the respond signal—the integral of peak values for each spectral line of interest—to obtain information about elemental atomic composition of different types of diesel particulate matter. The results from numerical calculation and integration of peak area are shown in **Figure 4**. From this figure, one can easily compare the individual changes in trace signal related to concentration values in a.u. (arbitrary unit). Nevertheless, in case of exact quantitative characterisation of the trace element in DPM, the particular calibration of trace element signal would be necessary to perform. However, from previous analytical LIBS measurements and qualitative

*Comparison of calculated integral values from LIBS optical emission spectra of barium (a), boron (b), cobalt (c), copper (d), phosphorus (e), manganese (f) and platinum (g) trace elements in diesel particulate matter,* 

*collected from different in-use passenger diesel engine vehicles.*

**146**

**Figure 4.**

*Summary of detected trace elements and spectral lines. Number of samples with detected trace signal and samples with most pronounced signal.*

In **Table 1,** chemical elements (analyte), spectral lines, number of samples with detected trace element and most pronounced signal from trace element in particular sample number are summarised and investigated.

#### **4. Conclusions**

In this research, we have investigated the trace chemical elements contained in diesel particulate matter. The particulate matter has been collected from inuse diesel engine passenger vehicles randomly from different vehicles models. Particulate matter has been analysed spectrochemically by means of a high resolution laser-induced breakdown spectroscopy (LIBS). The qualitative LIBS measurements reveal the presence of trace chemical elements such as barium, boron, cobalt, copper, phosphorus, manganese and platinum in diesel particulate matter. These trace elements were observed as optical emission of atomic or ionic spectral line emission in laser produced plasma. The spectral signal from each trace element was further numerically calculated as integral value of peak width line to obtain qualitative results. From LIBS analytical measurements and calculated signal profile, we can summarise that barium has been detected in 26 from 67 samples. Traces of boron have been detected in 27 samples, cobalt in 14 samples, copper in 62 samples, phosphorus in 26 samples, manganese in 18 different samples and platinum in 30 from 67 DPM samples.

From our previous research, we found out that minor chemical elements in diesel particulate matter are Si, Ni, Ti, K, Sr and Mo [28]. While major chemical elements C, Fe, Mg, Al, Cr, Zn, Na, Ca, O and H are forming the most important part of diesel particulate matter composition [26, 27].

All these major, minor and trace chemical elements contained in particulate matter are contributing to overall exhaust emission composition from in-use diesel engine passenger vehicles.

Finally, we can conclude that the laser-induced breakdown spectroscopy technique is very powerful method for qualitative and quantitative characterisation of DPM. It can almost instantly measure the major, minor and trace components of DPM and thus provide high resolution spectrochemical information about the chemical composition of diverse particulate matter matrices.

The presence of detected major, minor and trace chemical elements in DPM exhaust emissions from in-use diesel engine passenger vehicles can be related to the different processes. Those are: engine combustion process itself, engine health state, dysfunctions of some exhaust filtering device components, etc. These are linked with injected fuel type, fuel additives, engine lubricants, engine wear out, state of selective catalytic reduction devices, insufficient soot or PM filtering devices, engine conditions and quality of intake air.

Nevertheless, in the future, the quantitative characterisation of trace elements and calibration procedure would be an advantage for precise monitoring of different trace concentrations. That would help to better understand the trace content in diesel particulate matter.

#### **Acknowledgements**

The authors would like to thank the Austrian Science Fund—FWF (Fonds zur Förderung der wissenschaftlichen Forschung) for providing financial support. This study was funded with the grant number: FWF—P27967.

**149**

**Author details**

Richard Viskup\*, Christoph Wolf and Werner Baumgartner

provided the original work is properly cited.

Institute of Biomedical Mechatronics, Johannes Kepler University, Linz, Austria

© 2020 The Author(s). Licensee IntechOpen. This chapter is distributed under the terms of the Creative Commons Attribution License (http://creativecommons.org/licenses/ by/3.0), which permits unrestricted use, distribution, and reproduction in any medium,

\*Address all correspondence to: richard.viskup@jku.at; viskup@gmail.com

*Qualitative Characterisation of Trace Elements in Diesel Particulate Matter from In-Use Diesel…*

This work has been also supported by the COMET-K2 Center of the Linz Center of Mechatronics (LCM) funded by the Austrian federal government and the federal

Authors would like to thank Dr. Maria Rusnak for the proofreading and for the

*DOI: http://dx.doi.org/10.5772/intechopen.93067*

state of Upper Austria.

valuable corrections.

*Qualitative Characterisation of Trace Elements in Diesel Particulate Matter from In-Use Diesel… DOI: http://dx.doi.org/10.5772/intechopen.93067*

This work has been also supported by the COMET-K2 Center of the Linz Center of Mechatronics (LCM) funded by the Austrian federal government and the federal state of Upper Austria.

Authors would like to thank Dr. Maria Rusnak for the proofreading and for the valuable corrections.

#### **Author details**

*Environmental Emissions*

**4. Conclusions**

from 67 DPM samples.

engine passenger vehicles.

diesel particulate matter.

**Acknowledgements**

In **Table 1,** chemical elements (analyte), spectral lines, number of samples with detected trace element and most pronounced signal from trace element in particu-

In this research, we have investigated the trace chemical elements contained in diesel particulate matter. The particulate matter has been collected from inuse diesel engine passenger vehicles randomly from different vehicles models. Particulate matter has been analysed spectrochemically by means of a high resolution laser-induced breakdown spectroscopy (LIBS). The qualitative LIBS measurements reveal the presence of trace chemical elements such as barium, boron, cobalt, copper, phosphorus, manganese and platinum in diesel particulate matter. These trace elements were observed as optical emission of atomic or ionic spectral line emission in laser produced plasma. The spectral signal from each trace element was further numerically calculated as integral value of peak width line to obtain qualitative results. From LIBS analytical measurements and calculated signal profile, we can summarise that barium has been detected in 26 from 67 samples. Traces of boron have been detected in 27 samples, cobalt in 14 samples, copper in 62 samples, phosphorus in 26 samples, manganese in 18 different samples and platinum in 30

From our previous research, we found out that minor chemical elements in diesel particulate matter are Si, Ni, Ti, K, Sr and Mo [28]. While major chemical elements C, Fe, Mg, Al, Cr, Zn, Na, Ca, O and H are forming the most important

All these major, minor and trace chemical elements contained in particulate matter are contributing to overall exhaust emission composition from in-use diesel

Finally, we can conclude that the laser-induced breakdown spectroscopy technique is very powerful method for qualitative and quantitative characterisation of DPM. It can almost instantly measure the major, minor and trace components of DPM and thus provide high resolution spectrochemical information about the

The presence of detected major, minor and trace chemical elements in DPM exhaust emissions from in-use diesel engine passenger vehicles can be related to the different processes. Those are: engine combustion process itself, engine health state, dysfunctions of some exhaust filtering device components, etc. These are linked with injected fuel type, fuel additives, engine lubricants, engine wear out, state of selective catalytic reduction devices, insufficient soot or PM filtering devices,

Nevertheless, in the future, the quantitative characterisation of trace elements and calibration procedure would be an advantage for precise monitoring of different trace concentrations. That would help to better understand the trace content in

The authors would like to thank the Austrian Science Fund—FWF (Fonds zur Förderung der wissenschaftlichen Forschung) for providing financial support. This

lar sample number are summarised and investigated.

part of diesel particulate matter composition [26, 27].

chemical composition of diverse particulate matter matrices.

study was funded with the grant number: FWF—P27967.

engine conditions and quality of intake air.

**148**

Richard Viskup\*, Christoph Wolf and Werner Baumgartner Institute of Biomedical Mechatronics, Johannes Kepler University, Linz, Austria

\*Address all correspondence to: richard.viskup@jku.at; viskup@gmail.com

© 2020 The Author(s). Licensee IntechOpen. This chapter is distributed under the terms of the Creative Commons Attribution License (http://creativecommons.org/licenses/ by/3.0), which permits unrestricted use, distribution, and reproduction in any medium, provided the original work is properly cited.

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[5] Noll R, Fricke-Begemann C, Brunk M, Connemann S, Meinhardt C, Scharun M, et al. Laser-induced breakdown spectroscopy expands into industrial applications. Spectrochimica Acta Part B: Atomic Spectroscopy. 2014;**93**:41-51. DOI: 10.1016/j. sab.2014.02.001

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[10] Ntziachristos L, Ning Z, Geller MD, Sheesley RJ, Schauer JJ, Sioutas C. Fine, ultrafine and nanoparticle trace element compositions near a major freeway with a high heavy-duty diesel fraction. Atmospheric Environment. 2007;**41**(27):5684-5696. DOI: 10.1016/j. atmosenv.2007.02.043

[11] Kleeman MJ, Schauer JJ, Cass GR. Size and composition distribution of fine particulate matter emitted from motor vehicles. Enviromental Science & Technology. 2000;**34**(7):1132-1142. DOI: 10.1021/es981276y

[12] Packer AP, Sarkis JES, Giné MF, Santos ÉJ. High pressure Asher (HPA-S) decomposition of biodiesel samples for elemental analysis by inductively coupled plasma optical emission spectrometry (ICP OES). Journal of Brazilian Chemical Society. 2014;**25**:743- 749. DOI: 10.5935/0103-5053.20140028

[13] Fontaras G, Karavalakis G, Kousoulidou M, Tzamkiozis T, Ntziachristos L, Bakeas E, et al. Effects of biodiesel on passenger car fuel consumption, regulated and nonregulated pollutant emissions over legislated and real-world driving cycles.

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Halfmann T, Arndt S. Laser-induced breakdown spectroscopy for lambda quantification in a direct-injection engine. Spectrochimica Acta Part B: Atomic Spectroscopy. 2012;**74-75**:103-108

[23] Lopez-Quintas I, Mateo MP, Pinon V, Yanez A, Nicolas G. Mapping of mechanical specimens by laser induced breakdown spectroscopy method: Application to an engine valve. Spectrochimica Acta Part B: Atomic Spectroscopy. 2012;**74-75**:109-114

[24] Kiefer J, Li ZS, Alden M. Laserinduced breakdown spectroscopy in a partially premixed turbulent jet flame. Measurement Science and Technology.

[25] Hsu PS, Gragston M, Wu Y, Zhang ZL, Patnaik AK, Kiefer J, et al. Sensitivity, stability, and precision of quantitative Ns-LIBS-based fuel-airratio measurements for methane-air flames at 1-11 bar. Applied Optics.

[26] Viskup R, Wolf C, Baumgartner W.

[27] Viskup R, Wolf C, Baumgartner W. Major chemical elements in soot and particulate matter exhaust emissions generated from in-use diesel engine passenger vehicles. Introduction to Diesel Emissions, Chapter 6. London, UK: IntechOpen; 2020. ISBN: 978-1-78984- 035-3. DOI: 10.5772/intechopen.90452

2013;**24**(7):075205

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10.3390/en13020368

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*DOI: http://dx.doi.org/10.5772/intechopen.93067*

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[15] Gangwar JN, Guptab T, Agarwal AK. Composition and comparative toxicity of particulate matter emitted from a diesel and biodiesel fuelled CRDI engine. Atmospheric Environment. 2012;**46**:472-481. DOI: 10.1016/j.

[16] Agarwal AK, Gupta T, Kothari A. Particulate emissions from biodiesel vs diesel fuelled compression ignition engine. Renewable and Sustainable Energy Reviews. 2011;**15**:3278-3300. DOI: 10.1016/j.rser.2011.04.002

[17] Betha R, Balasubramanian R. Emissions of particulate-bound elements from stationary diesel engine: Characterization and risk assessment. Atmospheric Environment. 2011;**45**:5273-5281. DOI: 10.1016/j.

[14] Edlund M, Visser H, Heitland P. Analysis of biodiesel by argon–oxygen mixed-gas inductively coupled plasma optical emission spectrometry. Journal of Analytical Atomic Spectrometry. 2002;**7**:232-235. DOI: 10.1039/b111476j

fuel.2009.02.011

atmosenv.2011.09.007

atmosenv.2011.06.060

Applied Spectroscopy. 2003;**57**(9):1183-1189

[18] Ferioli F, Puzinauskas PV,

Buckley SG. Laser-induced breakdown spectroscopy for on-line engine equivalence ratio measurements.

[19] Ferioli F, Buckley SG. Measurements of hydrocarbons using laser-induced breakdown spectroscopy. Combustion and Flame. 2006;**144**(3):435-447

[20] Joshi S, Olsen DB, Dumitrescu C, Puzinauskas PV, Yalin AP. Laser-induced

measurements in laser-ignited natural gas engines. Applied Spectroscopy.

breakdown spectroscopy for In-cylinder equivalence ratio

2009;**63**(5):549-554

*Qualitative Characterisation of Trace Elements in Diesel Particulate Matter from In-Use Diesel… DOI: http://dx.doi.org/10.5772/intechopen.93067*

Fuel. 2009;**88**:1608-1617. DOI: 10.1016/j. fuel.2009.02.011

[14] Edlund M, Visser H, Heitland P. Analysis of biodiesel by argon–oxygen mixed-gas inductively coupled plasma optical emission spectrometry. Journal of Analytical Atomic Spectrometry. 2002;**7**:232-235. DOI: 10.1039/b111476j

[15] Gangwar JN, Guptab T, Agarwal AK. Composition and comparative toxicity of particulate matter emitted from a diesel and biodiesel fuelled CRDI engine. Atmospheric Environment. 2012;**46**:472-481. DOI: 10.1016/j. atmosenv.2011.09.007

[16] Agarwal AK, Gupta T, Kothari A. Particulate emissions from biodiesel vs diesel fuelled compression ignition engine. Renewable and Sustainable Energy Reviews. 2011;**15**:3278-3300. DOI: 10.1016/j.rser.2011.04.002

[17] Betha R, Balasubramanian R. Emissions of particulate-bound elements from stationary diesel engine: Characterization and risk assessment. Atmospheric Environment. 2011;**45**:5273-5281. DOI: 10.1016/j. atmosenv.2011.06.060

[18] Ferioli F, Puzinauskas PV, Buckley SG. Laser-induced breakdown spectroscopy for on-line engine equivalence ratio measurements. Applied Spectroscopy. 2003;**57**(9):1183-1189

[19] Ferioli F, Buckley SG. Measurements of hydrocarbons using laser-induced breakdown spectroscopy. Combustion and Flame. 2006;**144**(3):435-447

[20] Joshi S, Olsen DB, Dumitrescu C, Puzinauskas PV, Yalin AP. Laser-induced breakdown spectroscopy for In-cylinder equivalence ratio measurements in laser-ignited natural gas engines. Applied Spectroscopy. 2009;**63**(5):549-554

[21] Gross V, Kubach H, Spicher U, Schiessl R, Maas U. Laserzündung und Verbrennung im Ottomotor mit Direkteinspritzung. MTZ - Motortechnische Zeitschrift. 2010;**71**(7-8):532-539

[22] Buschbeck M, Buchler F, Halfmann T, Arndt S. Laser-induced breakdown spectroscopy for lambda quantification in a direct-injection engine. Spectrochimica Acta Part B: Atomic Spectroscopy. 2012;**74-75**:103-108

[23] Lopez-Quintas I, Mateo MP, Pinon V, Yanez A, Nicolas G. Mapping of mechanical specimens by laser induced breakdown spectroscopy method: Application to an engine valve. Spectrochimica Acta Part B: Atomic Spectroscopy. 2012;**74-75**:109-114

[24] Kiefer J, Li ZS, Alden M. Laserinduced breakdown spectroscopy in a partially premixed turbulent jet flame. Measurement Science and Technology. 2013;**24**(7):075205

[25] Hsu PS, Gragston M, Wu Y, Zhang ZL, Patnaik AK, Kiefer J, et al. Sensitivity, stability, and precision of quantitative Ns-LIBS-based fuel-airratio measurements for methane-air flames at 1-11 bar. Applied Optics. 2016;**55**(28):8042-8048

[26] Viskup R, Wolf C, Baumgartner W. Qualitative and quantitative characterisation of major elements in particulate matter from in-use diesel engine passenger vehicles by LIBS. Energies. 2020;**13**:368. DOI: 10.3390/en13020368

[27] Viskup R, Wolf C, Baumgartner W. Major chemical elements in soot and particulate matter exhaust emissions generated from in-use diesel engine passenger vehicles. Introduction to Diesel Emissions, Chapter 6. London, UK: IntechOpen; 2020. ISBN: 978-1-78984- 035-3. DOI: 10.5772/intechopen.90452

**150**

es980081n

*Environmental Emissions*

**References**

978-3-642-20667-2

[2] Miziolek AW, Palleschi V,

[3] Cremers DA, Radziemski LJ.

2013. ISBN: 978-1-119-97112-2

10.1366/11-06574

sab.2014.02.001

DOI: 10.1039/b817279j

[4] Hahn DW, Omenetto N. Laserinduced breakdown spectroscopy (LIBS), Part II: Review of instrumental and methodological approaches to material analysis and applications to different fields. Applied

[1] Noll R. Laser-Induced Breakdown Spectroscopy, Fundamentals and Applications. Berlin Heidelberg: Springer-Verlag; 2012. ISBN:

[8] Lough GC, Schauer JJ, Park JS, Shafer MM, Deminter JT, Weinstein JP. Emissions of metals associated with motor vehicle roadways. Environmental Science & Technology. 2005;**39**(3): 826-836. DOI: 10.1021/es048715f

[9] Cheung KL, Ntziachristos L, Tzamkiozis T, Schauer JJ, Samaras Z, Moore KF, et al. Emissions of particulate trace elements, metals and organic species from gasoline, diesel, and biodiesel passenger vehicles and their relation to oxidative potential. Aerosol Science and Technology. 2010;**44**(7):500-513. DOI: 10.1080/02786821003758294

[10] Ntziachristos L, Ning Z, Geller MD, Sheesley RJ, Schauer JJ, Sioutas C. Fine, ultrafine and nanoparticle trace element compositions near a major freeway with a high heavy-duty diesel fraction. Atmospheric Environment. 2007;**41**(27):5684-5696. DOI: 10.1016/j.

[11] Kleeman MJ, Schauer JJ, Cass GR. Size and composition distribution of fine particulate matter emitted from motor vehicles. Enviromental Science & Technology. 2000;**34**(7):1132-1142.

[12] Packer AP, Sarkis JES, Giné MF, Santos ÉJ. High pressure Asher (HPA-S) decomposition of biodiesel samples for elemental analysis by inductively coupled plasma optical emission spectrometry (ICP OES). Journal of Brazilian Chemical Society. 2014;**25**:743- 749. DOI: 10.5935/0103-5053.20140028

[13] Fontaras G, Karavalakis G, Kousoulidou M, Tzamkiozis T,

Ntziachristos L, Bakeas E, et al. Effects of biodiesel on passenger car fuel consumption, regulated and nonregulated pollutant emissions over legislated and real-world driving cycles.

atmosenv.2007.02.043

DOI: 10.1021/es981276y

Schechter I. Laser-Induced Breakdown Spectroscopy (LIBS), Fundamentals and Applications. Cambridge University Press; 2006. ISBN: 978-0-521-85274-6

Handbook of Laser-Induced Breakdown Spectroscopy. John Wiley & Sons Inc;

Spectroscopy. 2012;**66**(4):347-419. DOI:

Brunk M, Connemann S, Meinhardt C, Scharun M, et al. Laser-induced breakdown spectroscopy expands into industrial applications. Spectrochimica Acta Part B: Atomic Spectroscopy. 2014;**93**:41-51. DOI: 10.1016/j.

[6] Stehrer T, Praher B, Viskup R, Jasik J, Wolfmeir H, Arenholz E, et al. Laserinduced breakdown spectroscopy of iron oxide powder. Journal of Analytical Atomic Spectrometry. 2009;**24**:973-978.

[7] Schauer JJ, Kleeman MJ, Cass GR, Simoneit BRT. Measurement of

emissions from air pollution sources. 2. C-1 through C-30 organic compounds from medium duty diesel trucks. Enviromental Science & Technology. 1999;**33**(10):1578-1587. DOI: 10.1021/

[5] Noll R, Fricke-Begemann C,

[28] Viskup R, Wolf C, Baumgartner W. Identification of the minor chemical elements in the particulate matter exhaust emissions from in-use diesel engine passenger vehicles. Diesel and Gasoline Engines, Chapter 9. London, UK: IntechOpen; 2020. ISBN: 978-1-78985-248-6. DOI: 10.5772/ intechopen.90760

*Environmental Emissions*

intechopen.90760

[28] Viskup R, Wolf C, Baumgartner W. Identification of the minor chemical elements in the particulate matter exhaust emissions from in-use diesel engine passenger vehicles. Diesel and Gasoline Engines, Chapter 9. London, UK: IntechOpen; 2020. ISBN: 978-1-78985-248-6. DOI: 10.5772/

**152**

### *Edited by Richard Viskup*

Today, the issue of environmental emissions is more important than ever before. Air pollution with particulates, soot, carbon, aerosols, heavy metals, and so on is causing adverse effects on human health as well as the environment. This book presents new research and findings related to environmental emissions, pollution, and future sustainability. Written by experts in the field, chapters cover such topics as health effects, emission monitoring and mitigation, and emission composition and measurement.

Published in London, UK © 2021 IntechOpen © Sayan\_Moongklang / iStock

Environmental Emissions

Environmental Emissions

*Edited by Richard Viskup*