Dimensions of the coupled antenna Array.
\r\n\tThe applications are those related to intelligent monitoring activities such as the quality assessment of the environmental matrices through the use of innovative approaches, case studies, best practices with bottom-up approaches, machine learning techniques, systems development (for example algorithms, sensors, etc.) to predict alterations of environmental matrices. The goal is also to be able to protect natural resources by making their use increasingly sustainable.
\r\n\r\n\tContributions related to the development of prototypes and software with an open-source component are very welcome.
\r\n\r\n\tThis book is intended to provide the reader with a comprehensive overview of the current state of the art in the field of Ambient Intelligence. A format rich in figures, tables, diagrams, and graphical abstracts is strongly encouraged.
",isbn:"978-1-83969-069-3",printIsbn:"978-1-83969-068-6",pdfIsbn:"978-1-83969-070-9",doi:null,price:0,priceEur:0,priceUsd:0,slug:null,numberOfPages:0,isOpenForSubmission:!1,hash:"3fbf8f0bcc5cdff72aaf0949d7cbc12e",bookSignature:"Dr. Carmine Massarelli",publishedDate:null,coverURL:"https://cdn.intechopen.com/books/images_new/10391.jpg",keywords:"Embedded Systems, Technologies, Sensors, Remote Sensing, Smart Homes, Smart Cities, Integrated Monitoring Techniques, Agroecosystem, Smart Public Spaces, Computer Vision, Image Processing, Open-Source",numberOfDownloads:null,numberOfWosCitations:0,numberOfCrossrefCitations:null,numberOfDimensionsCitations:null,numberOfTotalCitations:null,isAvailableForWebshopOrdering:!0,dateEndFirstStepPublish:"October 12th 2020",dateEndSecondStepPublish:"November 9th 2020",dateEndThirdStepPublish:"January 8th 2021",dateEndFourthStepPublish:"March 29th 2021",dateEndFifthStepPublish:"May 28th 2021",remainingDaysToSecondStep:"2 months",secondStepPassed:!0,currentStepOfPublishingProcess:4,editedByType:null,kuFlag:!1,biosketch:"Environmental technologist expert in the development of Smart Technologies for water management and environmental monitoring, characterization, and monitoring of contaminated and degraded sites, integration of spatial data such as standard methodologies, interoperability, spectral data infrastructures.",coeditorOneBiosketch:null,coeditorTwoBiosketch:null,coeditorThreeBiosketch:null,coeditorFourBiosketch:null,coeditorFiveBiosketch:null,editors:[{id:"315689",title:"Dr.",name:"Carmine",middleName:null,surname:"Massarelli",slug:"carmine-massarelli",fullName:"Carmine Massarelli",profilePictureURL:"https://mts.intechopen.com/storage/users/315689/images/system/315689.jpg",biography:"Main activities:\n-development of Smart Technologies for water management and environmental monitoring;\n-characterization and monitoring of contaminated and degraded sites;\n-implementation of early warning systems and impact assessment systems also from multitemporal monitoring;\n-integration of spatial data: methodologies, standards, interoperability, spatial data infrastructures;\n-use of open source IT systems for the processing, analysis, and integration of remote sensing data with airborne and satellite sensors for thematic purposes such as characterization, control, and analysis of the territory in support of environmental policies relating to contaminated sites;\n-evaluation of the contamination of environmental matrices with specific tests and chemical analyses;\n-installation of airborne sensors and definition of flight parameters for Earth observation, CASI-1500 hyperspectral and TABI-320 thermal sensors;\n-acquisition of spectral signatures of objects through Fieldspec portable spectroradiometer and creation of databases in SQL language;\n-use of tools such as Ground Penetrating Radar for the advanced investigation of the subsoil with law enforcement agencies.",institutionString:"National Research Council",position:null,outsideEditionCount:0,totalCites:0,totalAuthoredChapters:"0",totalChapterViews:"0",totalEditedBooks:"0",institution:{name:"National Research Council",institutionURL:null,country:{name:"Italy"}}}],coeditorOne:null,coeditorTwo:null,coeditorThree:null,coeditorFour:null,coeditorFive:null,topics:[{id:"9",title:"Computer and Information Science",slug:"computer-and-information-science"}],chapters:null,productType:{id:"1",title:"Edited Volume",chapterContentType:"chapter",authoredCaption:"Edited by"},personalPublishingAssistant:{id:"297737",firstName:"Mateo",lastName:"Pulko",middleName:null,title:"Mr.",imageUrl:"https://mts.intechopen.com/storage/users/297737/images/8492_n.png",email:"mateo.p@intechopen.com",biography:"As an Author Service Manager my responsibilities include monitoring and facilitating all publishing activities for authors and editors. 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Venkateswarlu",coverURL:"https://cdn.intechopen.com/books/images_new/371.jpg",editedByType:"Edited by",editors:[{id:"58592",title:"Dr.",name:"Arun",surname:"Shanker",slug:"arun-shanker",fullName:"Arun Shanker"}],productType:{id:"1",chapterContentType:"chapter",authoredCaption:"Edited by"}},{type:"book",id:"878",title:"Phytochemicals",subtitle:"A Global Perspective of Their Role in Nutrition and Health",isOpenForSubmission:!1,hash:"ec77671f63975ef2d16192897deb6835",slug:"phytochemicals-a-global-perspective-of-their-role-in-nutrition-and-health",bookSignature:"Venketeshwer Rao",coverURL:"https://cdn.intechopen.com/books/images_new/878.jpg",editedByType:"Edited by",editors:[{id:"82663",title:"Dr.",name:"Venketeshwer",surname:"Rao",slug:"venketeshwer-rao",fullName:"Venketeshwer Rao"}],productType:{id:"1",chapterContentType:"chapter",authoredCaption:"Edited by"}},{type:"book",id:"4816",title:"Face Recognition",subtitle:null,isOpenForSubmission:!1,hash:"146063b5359146b7718ea86bad47c8eb",slug:"face_recognition",bookSignature:"Kresimir Delac and Mislav Grgic",coverURL:"https://cdn.intechopen.com/books/images_new/4816.jpg",editedByType:"Edited by",editors:[{id:"528",title:"Dr.",name:"Kresimir",surname:"Delac",slug:"kresimir-delac",fullName:"Kresimir Delac"}],productType:{id:"1",chapterContentType:"chapter",authoredCaption:"Edited by"}},{type:"book",id:"3621",title:"Silver Nanoparticles",subtitle:null,isOpenForSubmission:!1,hash:null,slug:"silver-nanoparticles",bookSignature:"David Pozo Perez",coverURL:"https://cdn.intechopen.com/books/images_new/3621.jpg",editedByType:"Edited by",editors:[{id:"6667",title:"Dr.",name:"David",surname:"Pozo",slug:"david-pozo",fullName:"David Pozo"}],productType:{id:"1",chapterContentType:"chapter",authoredCaption:"Edited by"}}]},chapter:{item:{type:"chapter",id:"69445",title:"Decoupled and Descattered Monopole MIMO Antenna Array with Orthogonal Radiation Patterns",doi:"10.5772/intechopen.89630",slug:"decoupled-and-descattered-monopole-mimo-antenna-array-with-orthogonal-radiation-patterns",body:'Contemporary wireless systems including, but not limited to, 4G/5G LTE/LTE-A, radar, RFID, Wi-Fi, WiMAX, GPS, geolocation, biomedical imaging, and remote sensing dictate the use of miniaturized MIMO antenna arrays on mobile terminals. They can also be permanently installed on fixed structures for increased gain, which will improve link reliability and quality of service, increase communication range, and increase battery life through a variety of diversity schemes [1, 2], and/or increase data rate/throughput through MIMO spatial multiplexing schemes [3]. Moreover, these structures can provide esthetic, miniaturized wireless consumer devices. Recent trends toward miniaturized, esthetically appealing, battery efficient handheld wireless devices, and green wireless systems require antenna arrays that should be implemented within a restricted physical space.
In this chapter, we report a new approach of how to reduce the complexity of prior existing designs for mutual coupling reduction such as periodic metamaterial/metasurface constructs [4, 5, 6, 7, 8], defected ground plane structures [9, 10], soft/hard electromagnetic surfaces [11, 12], parasitic elements [13], matching and decoupling networks [14, 15, 16], and neutralization lines [17]. Our proposed approach can still maintain, and in certain circumstances exceed the performance metrics of traditional approaches well-known in previous art, [18, 19, 20] using much simpler, cost-effective, and novel design alternatives.
Numerous techniques were proposed for the mutual coupling reduction among the elements of MIMO antenna arrays, the most notable and highly embraced is the use of metamaterials, which subsequently turned into an unique topic of its own used in various disciplines including acoustics, RF, optics, laser, and nanotechnology [21]. A defected ground plane consisting of a slitted pattern is disclosed in [9] to suppress mutual coupling between two monopole antennas separated by 0.093 λ0, where λ0 is the free-space wavelength at 2.53 GHz. The two monopoles share a 40 × 25 mm ground plane and are separated by 11 mm. Each slit is 11 × 1 mm. A periodic array of three slits was used to achieve a mutual coupling better than −20 dB. However, no information on the behavior of far-field radiation patterns of the array was provided. A simple yet elegant decoupling approach was presented in [22] using a parasitic element to decouple two monopole antennas operating at 900 MHz. The parasitic element is situated at the center between the two driven elements on a 330 × 250 mm FR4 substrate, 1.5 mm in thickness. The substrate has a permittivity of 4.4 and a loss tangent of 0.02. The radiation behavior shows an end-fire pattern. The measured pattern correlation is close to 0.02. This method achieved coupling coefficient, S12 close to −40 dB over the bandwidth in which S11 is less than −10 dB. The method requires careful attention to the choice of the distance between the parasitic element and the driven elements for a given separation between the driven elements. A drawback of this technique is the undesired radiation from the parasitic element, which may degrade the decoupled radiation pattern.
A complicated approach for mutual coupling suppression between two monopole antennas operating at 2.49 GHz and separated by 0.09 λ0, where λ0 is the free-space wavelength at 2.49 GHz, with a length of 32.5 mm over a ground plane containing four slits, 1 × 11 mm in size and two defected wall structures situated at the edge of the outermost slits are proposed in [20]. The defected wall structure consists of a metallic plane with C-shaped cuts mimicking split ring resonators. The spacing between the slots in the defected wall is 0.09 λ0. The structure achieved a measured isolation of about 44 dB. No information has been provided on the shape of the far-field radiation patterns. One notable approach for the isolation of two high-profile monopole antennas laid on a common copper ground plane (1.25 λ0 × 1.25 λ0), involves the use of highly negative-permeability, broadside coupled split-ring resonators etched on both sides of a dielectric substrate. In this approach, the two monopoles are separated by λ0/8 (30.25 mm), where λ0 is the free-space wavelength at 1.24 GHz [18]. A 3-D stack employing 10 arrays is aligned vertically using plastic support in the space between the two monopoles, where each array consists of four broadside coupled split-ring resonators.
It should be noted, however, that these artificial magnetic inclusions obviously suffer from extremely narrow resonance bandwidth. The design methodology is based on creating artificial negative permeability, which consequently presents extremely high attenuation to the near-field that exists in the region between the two monopoles for both propagating and evanescent fields. The authors claim a reduction of at least 20 dB in S12 but over an extremely small bandwidth. The structure is neither convenient nor rigid for miniaturized handheld devices since the decoupling structure occupies a significant volume in the space between the two monopoles. Also, the fabrication costs as well as the dielectric and conductor losses introduced by the decoupling structure even at frequencies in the decoupled regime create an inconvenience. We should note that a similar approach was reported in [19] in which a metamaterial spacer is employed to reduce the mutual coupling between two monopoles, each 27.8 mm in height, installed on a common (2 λ0 × 2 λ0) aluminum ground plane and separated by 0.156 λ0 (18 mm) at 2.6 GHz. The principle of operation is explained by considering the metamaterial acting as an artificial magnetic conductor (AMC). The decoupling structure consists of four existing design of a bidirectional AMC printed on a dielectric substrate with width-height-thickness dimensions of 64 × 33 × 10.5 mm.
Several defected ground planes [9, 10, 11, 12], soft artificial electromagnetic surfaces, matching and decoupling networks [14, 15, 16], and neutralization lines [17] have received considerable recent research interest in both academia and industry. However, they were not applied specifically to vertical monopole antennas, the subject of this chapter. It should be noted that these traditional approaches suffer from:
Extremely narrow bandwidths since metamaterials, defected ground structures, and soft electromagnetic surfaces embrace inherently high-resonant structures;
Repeated periodic structures are employed periodically in 1-D, 2-D, or in 3-D using vias, which further complicates the design and increases the fabrication cost;
Insertion of many 2D cells (arranged in multiple rows and/or columns) and sometimes 3D unit cells [7, 8] between the antenna elements limits the empty space between the antenna elements and hence complicates the task of miniaturizing the MIMO antenna array; and
Distortion of the far-field radiation patterns and/or reduction the operating bandwidth [18, 19, 20] from these artificial structures.
To conclude, most of the related research utilized meta-surfaces inclusions inserted in the space between the antenna elements for which the mutual coupling is to be reduced. This is another major obstacle for applications involving extremely miniaturized antenna arrays, such as MIMO systems on handheld wireless devices. In this chapter, however, we report a novel approach in which the mutual coupling is reduced by inserting two vertical monopole antenna elements inside a rectangular conducting ring loaded with two conducting strips. This technique allows much smaller separations (λo/16), where λo is the free-space wavelength. Unlike the traditional techniques that are based on inserting artificial resonant structures between the radiating elements, the methodology reported in this chapter is based on enclosing the radiating elements by simple and versatile planar conducting structures, the performance of which exceeds the performance of traditional/existing design approaches.
We will elaborate on one embodiment involving a miniaturized two-element antenna array system composed of two vertical monopole antennas separated by 8 mm, corresponding to λo/16, where λo is the wavelength in free space at 2.4 GHz. The unique design scheme of the coupled array produces orthogonal radiation patterns even without the inclusion between the monopoles. Additionally, the decoupling structure is designed to reduce the mutual coupling and enhance isolation between the signals at the array terminals. A very low envelope correlation coefficient between the received signals is realized to accommodate operating with the different MIMO modes. To summarize, the design of the antenna array disclosed in this chapter seeks to achieve three functions: decoupling, descattering, and orthogonalization of the far-field radiation patterns in the boresight directions. Descattering in this context implies that the radiation pattern of each antenna element in the array is the same as the radiation pattern when in isolation.
To obtain a boresight oriented by 45° relative to that of a conventional vertical monopole, the design uses a partial reference ground plane instead of a traditional full ground as shown in Figure 1. The monopole is mounted on a dielectric substrate and is fed by a coplanar waveguide (CPW) circuit. The ground plane of the coplanar feeding circuit serves as a partial ground for the antenna as well. The height of the monopole h and the feeding circuit geometry are tuned such that the antenna operates at center frequency of 2.4 GHz serving applications in the ISM band. The coplanar waveguide feeding circuit is selected to have a characteristic impedance of 50 ohm at its input. The geometry, reflection coefficient, and radiation pattern of the single element are shown in Figures 1–3, respectively.
Geometry of a single monopole antenna fed by CPW.
Reflection coefficient of the monopole antenna fed by a CPW.
Realized gain of the monopole antenna fed by a CPW.
This behavior is exploited to construct an array consisting of two vertical monopoles, the radiation patterns of which are identical in shape but orthogonally oriented in space. The antenna array is formed by placing monopole 2 and its feeding circuit as a mirror image of monopole 1 around the y-z plane as depicted in Figure 4. Both antennas are assembled on a common substrate of a relative permittivity, εr = 10.2, and height, hs = 1.27 mm.
The coupled monopole antenna array.
When the two antennas are positioned in a close proximity, λo/16, in this design, the far-field radiation patterns will be distorted while the correlation coefficient increases due to mutual coupling. To investigate the mutual coupling effects, the array is simulated using the commercial software package, high-frequency structure simulator (HFSS) of ANSYS. The geometry of the design is shown in Figure 5 and the dimensions are presented in Table 1.
Geometry of the coupled antenna array. (a) Prospective view, (b) Side view, (c) Bottom view and, (d) Top view.
Monopoles separation (s) | 8 |
Monopole height (h) | 25 |
Monopole diameter (d) | 1.6 |
Feeding probe length(l2) | 11 |
Feeding probe width (w2) | 2 |
Ground width (w3) | 10.85 |
Ground length (l3) | 5 |
Center strip width (w4) | 3 |
CPW gap width (g1) | 0.5 |
Substrate (l1 × w1 × hs) | (40 × 40 × 1.27) |
Dielectric constant (εr) of the substrate | 10.2 |
Dimensions of the coupled antenna Array.
Despite the reduction in transmission level between the feeding ports, the distribution of surface currents depicted in Figure 6, resulted from exciting port 1 while terminating port 2 with 50 ohms, shows the existence of significant interfering currents distributed on the CPW feeding of monopole 2. The current induced on monopole 2 and its feeding circuitry is due to the mutual coupling between the two antennas.
Magnitude of surface current distribution for the coupled monopole antenna array, dB(1 A/m).
In Figure 7, we show the reflection coefficient, S11 and transmission coefficient, S21 plotted against frequency. The coupled array provides a bandwidth of 230 MHz over which the reflection coefficient is below −10 dB. At 2.4 GHz, the partial ground plane reduced S21 to −10 dB compared to −4 dB if the antennas share a common full ground plane and are separated by 8 mm. The radiation patterns in terms of the realized gain are plotted in Figure 8 for two cases; in the first case, an excitation signal is injected into port 1, while the second port is terminated with its internal impedance, 50 ohms. In the second case, the excitation signal is injected into port 2, and port 1 is terminated by 50 ohms. Having the antennas placed extremely close to each other (8 mm at 2.4 GHz) resulted in disturbing the near field and increasing the coupling level. This proximity causes the radiation patterns to be directed into the lower part below the plane containing the substrate.
Frequency response of the coupled monopole antenna.
Mutual coupling effects on the far-field radiation patterns. (a) Exciting port 1 and, (b) Exciting port 2.
The proposed MIMO antenna array consists of two monopole antennas positioned on a printed circuit board. The antennas are surrounded by a decoupling circuit printed on the top side of the substrate and a feeding circuit on the bottom side. For short, the design will be called the decoupled coplanar waveguide fed monopole antenna array (CPW-MAA). The substrate has a length and width of 40 × 40 mm, and a thickness of 1.27 mm.
In order to further enhance the performance of pattern diversity for the two-element antenna array and minimize the contribution of mutual coupling among the elements of the antenna array to the channel correlation, the mutual coupling effect needs to be reduced with minimal distortion to the radiation patterns of the individual elements, preferably such that the 3-D far-field patterns of the individual elements being identical in shape and orthogonal in space. This applies to the signals at the output of the antennas when transmitting and at the input of the feeding circuit when operating in the receive mode.
The decoupling structure, shown in Figure 9, consists of a simple 2D planar rectangular metallic ring and two tuning metallic strips printed on the surface of the substrate.
Decoupling circuit.
First, the performance of the CPW-MAA is compared against the coupled monopole antenna array shown in Figure 5 using the same substrate. Furthermore, as a design alternative and to further validate the disclosed design concept, another substrate has been used with a dielectric constant εr of 6.15 and height, 1.27 mm. Each monopole is fed by a copper trace printed on the bottom side of the substrate. Each monopole makes a contact with the copper trace by extending the monopole body inside the substrate to reach the feeding copper trace at the bottom layer. A CPW at the bottom side of the substrate is used to deliver the signal to the antennas in case of transmitting and from the antennas in case of receiving.
The CPW consists of a central strip having a length of l3 and a width of w4 with the finite ground planes positioned on both sides of the central strip with a width of w3. An SMA is utilized to launch the wave into the array. The impedance of the SMA is 50 ohm and is used to connect the antenna to a vector network analyzer used in the measurements. The array system dimensions are tuned to operate at a 2.4 GHz with a bandwidth of 260 MHz over which the reflection coefficients, S11 and S22, are less than −10 dB and transmission coefficients, S12 and S21 less than −20 dB. The two-element MIMO antenna array is shown in Figure 10, while dimensions are depicted in Table 2 for the two substrates used where all dimensions are in millimeters.
The decoupled CPW-MAA. (a) Prospective view, (b) Side view, (c) Top view, (d) Bottom view.
Dimension defined name | Substrate RO3210 (εr = 10.2) | Substrate RO3006 (εr = 6.15) |
---|---|---|
Monopoles separation (s) | 8 | 8 |
Monopole height (h) | 28 | 27 |
Monopole diameter (d) | 1.6 | 1.6 |
Feeding probe length (l2) | 11 | 11 |
Feeding probe width (w2) | 2 | 2 |
Ground width (w3) | 10.5 | 10.8 |
Ground length (l3) | 5.0 | 5.0 |
CPW trace width (w4) | 3.0 | 3.0 |
CPW gap width (g1) | 0.5 | 0.2 |
Rectangular ring outer length (l5) | 22 | 22 |
Rectangular ring outer width (w5) | 24 | 30 |
Rectangular ring trace width (w7) | 2.5 | 2.5 |
Tuning strip length (l4) | 16 | 16 |
Tuning strip width (w6) | 1.5 | 4 |
Tuning strips separation (s1) | 6.5 | 8 |
Substrate (l1 × w1 × hs) | (40 × 40 × 1.27) | (40 × 40 × 1.27) |
Dimensions of the CPW-MAA for two substrates.
Prototypes are fabricated and measured at the University of Arkansas at Little Rock’s Antennas and Wireless Systems Research Laboratory (AWSRL). The prototype which is shown in Figure 11 used Roger RO3210 substrate. The frequency response has been measured using E5071B and N5242A VNAs. The radiation patterns are measured inside an anechoic chamber. Using Roger RO3210 (dielectric constant εr of 10.2) as a substrate, and in order to demonstrate that adding this decoupling circuit isolates the input and output ports, the magnitude of the surface current dB (1 A/m) has been plotted for different excitation phase delays as depicted in Figure 12. A signal of 1 W is assigned through port 1 to excite the first monopole, the monopole in the right side of the array, while port 2 is terminated by its internal impedance of 50 ohm. It seems quite evident that the amount of current coupled to the feeding circuit of monopole 2 at different phase delays is very low, minimum at −8 dB (1 A/m) (blue color), compared to other excited monopole, where a high current is observed with a maximum value at 32 dB (1 A/m) (red color). This contrast of 40 dB (1 A/m) reveals the high isolation level achieves due to the decoupling network compared to the coupled current before adding the decoupling network shown in Figure 6.
The decoupled CPW-MAA and decoupled MS-MAA prototypes.
Two monopole antenna array with decoupling network; surface current distribution (magnitude) dB(1 A/m).
The simulated and measured results of the scattering parameter, S11 are presented in Figure 13. The amount of coupling expressed in terms of scattering parameter, S21 is depicted in Figure 14. These figures reveal good agreement between the simulated models and the measurements using the fabricated prototype.
Reflection coefficient S11, simulation versus measurements.
Coupling coefficients S21, simulation versus measurements.
Introducing the decoupling network resulted in a reduction of −19 dB in mutual coupling level, from −4 to −23 dB. The antenna array system offers a bandwidth of 10%, in which the coupling coefficient, S21 is less than −20 dB and 14% over which the reflection coefficient, S11 is less than −10 dB. The slight shift of 2% in the frequency at which the measured coupling coefficient S21 is at its minimum in the bandwidth of interest compared to simulated results is due to the variations associated with the fabrication of the prototype and the limited precision of simulations and measurements. The fabricated prototype also provides a wider bandwidth. This is due to the dielectric and metallic losses inherent in the substrate and dipoles, which lead to reduced Q factor.
Table 3 summarizes the performance metrics of the simulated models and the measured prototype. In this table, fL and fH denote the lower and upper frequency limits of the operating bandwidth, respectively. The array meets and exceeds the bandwidth requirement of 802.11 Wi-Fi systems operating in the ISM band at 2.4 GHz.
Performance metric | Conventional array | HFSS | CST | Measured |
---|---|---|---|---|
S11 (min) dB | −8 | −24 | −40 | −20 |
S22 (min) dB | −8 | −23 | −40 | −33 |
S21 (min) dB | −4 | −29 | −45 | −23 |
fL (S11, S22 < −10 dB) GHz | — | 2.25 | 2.22 | 2.12 |
fH (S11, S22 < −10 dB) GHz | — | 2.58 | 2.56 | 2.74 |
fL (S12, S21 < −20 dB) GHz | — | 2.28 | 2.26 | 2.32 |
fH (S12, S21 < −20 dB) GHz | — | 2.51 | 2.51 | 2.58 |
BW (S11, S22 < −10 dB) GHz | — | 0.33 | 0.34 | 0.62 |
BW (S21, S12 < −20 dB) GHz | — | 0.23 | 0.25 | 0.26 |
% BW (S11, S22 < −10 dB) | — | 13.6% | 14.2% | 25.5% |
% BW (S21, S12 < −20 dB) | — | 9.6% | 10.4% | 10.6% |
Decoupled array performance at 2.4 GHz in terms of scattering parameters (dB).
The maximum value of the total realized gain is plotted versus frequency in Figure 15. Another advantage of the proposed antenna array is the enhancement achieved in the realized gain and hence the efficiency. The total realized gain of a single element varies over the range from 1.6 to 1.69 dB over the frequency range 2.25–2.52 GHz over which S11 and S21 are less than −10 and −20 dB, respectively. This gain is obtained when one port is excited while the other is terminated with its characteristic impedance. An improvement of 2.1 dB is observed in the realized gain with the proposed antenna array as compared to a conventional array antenna consisting of two monopoles separated by λ0/16 over a λ0 × λ0 full ground plane. It is noteworthy that the maximum value of the total realized gain of the array system is close to that of a stand-alone monopole antenna.
Maximum realized gain.
The 3-D radiation patterns in terms of the realized gain are shown in Figure 16.
(a) The realized gain scale. (b) Realized gain for a stand-alone monopole, while (c) and (d) are for the coupled monopole antenna array, then (e) and (f) are for the decoupled CPW-MAA. Examining the upper right section of the 3-D pattern of model 2, (π ≤ ϕ ≤ 2π, and θ ≤ π/2) shows red spot, which indicates high gain which is reduced for the decoupled CPW-MAA, where more power is directed in the lower left side (0 ≤ ϕ ≤ π and θ ≥ π/2). This distortion has been corrected in the disclosed antenna array due to the low mutual coupling caused by adding the decoupling network. Furthermore, a descattered pattern is realized. Figure 17 shows a comparison between simulated and measured co/cross radiation patterns of the decoupled CPW-MAA (Figure 18).
Realized gain; scale (a), stand-alone monopole (b), two-monopole array without decoupling structure (c) and (d), decoupled CPW-MAA (e) and (f).
Realized gain; simulation versus measurements.
A compact MIMO antenna array with identical yet orthogonal radiation patterns and high isolation level is reported in this chapter. The shape and size of the partial ground plane and its distance from the monopole allowed the boresight of the radiation pattern of the isolated monopole to be oriented at an elevation angle of 45o. The 45o elevation achieved for the single monopole made it possible to place two vertical monopoles back to back to achieve an array with orthogonal radiation patterns. However, the mutual coupling between the two elements when placed in close proximity resulted in a distortion of the radiation patterns. To mitigate the effects of mutual coupling and increase the isolation between the two ports of the array, a decoupling element that surrounds the array elements which provides more flexibility on how close the elements need to be from each other. The dimensions of the rectangular ring and the tuning strips have been tuned to achieve the desired isolation level and restore the radiation pattern of the isolated element. The CPW-MAA with orthogonal far-field radiation patterns opens new opportunities for modern handheld devices and/or fixed wireless access points implementing MIMO techniques. Unlike existing design approaches that are based on inserting artificial resonant structures between the radiating elements, the design presented in this chapter encloses the radiating elements by simple and versatile planar conducting structures. The proposed design is demonstrated by simulations and measurements to significantly reduce the mutual coupling when the monopoles are spaced by 8 mm (λo/15.3). The performance achieved in terms of impedance matching, isolation, gain, bandwidth, and radiation pattern is comparable to network decoupling and parasitic approaches and better in terms of bandwidth, size, and complexity in comparison to existing designs which employ periodic AMC. A matching bandwidth of 0.634 GHz over which the reflection coefficient, S11 is less than −10 dB, and a 0.246 GHz bandwidth over which the transmission coefficient, S21 is less than −20 dB have been achieved. A total realized gain of 1.69, 1.95, and 1.68 dB are achieved at 2.26, 2.4, and 2.52 GHz, respectively.
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, 3, 4, 5, 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, 8, 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.
\nThe 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].
\nThe 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, 13, 14, 15, 16, 17, 18, 19].
\nAlso high performed liquid chromatographs (HPLC method) are widely applied in these investigations (e.g., [20, 21, 22]). However, it is often not cost effective to apply these methods routinely to large numbers of samples.
\nIn 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 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]).
\nThe 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.
\nLocalization of sampling in Upper Silesia Region.
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.
\nThe 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, 10−9–10−7 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, 10−6–1 s. It was showed on the simplified Jablonski diagram (Figure 2) [24].
\nThe simplified Jablonski diagram.
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 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, 27, 28, 29, 30, 31, 32, 33, 34, 35, 36].
\nThe 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−1.
\nThe same aromatic fraction was also used for further analysis by GC-MS method.
\nFluorescence 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.
\nThe 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.
\nThe 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.
\nIdentified compounds | \nExperimental data Δλ [nm] λem/λex [nm/nm] | \nReference data [1] Δλ [nm] λem/λex [nm/nm] | \nGC/MS retention time [min] | \n||
---|---|---|---|---|---|
2,3-Dimethyl-naphthalene | \n54 | \n334/280 | \n54 | \n333/279 | \n14.78 | \n
Phenanthrene | \n53 \n | \n347/294 \n | \n53 \n | \n346/293 \n | \n25.26 | \n
71 \n | \n365/294 \n | \n71 \n | \n364/293 \n | \n||
\n 105 | \n357/252 | \n102 | \n356/254 | \n||
9-Methyl-phenanthrene | \n50 | \n349/299 | \n52 | \n350/298 | \n29.11 | \n
9,10-Dimethyl-phenanthrene | \n55 \n | \n356/301 \n | \n55 \n | \n354/299 \n | \n32.42 | \n
71 | \n355/284 | \n69 | \n354/285 | \n||
1-Methyl-7-isopropyl-phenanthrene | \n67 \n | \n368/301 \n | \n67 \n | \n369/302 \n | \n38.63 | \n
98 | \n358/260 | \n100 | \n360/260 | \n||
1-Methyl-anthracene | \n20 \n | \n400/380 \n | \n21 \n | \n403/382 \n | \n28.94 | \n
37 | \n384/347 | \n38 | \n383/345 | \n||
9-Methyl- anthracene | \n22 | \n411/389 | \n23 | \n411/388 | \n29.86 | \n
9,10-Dimethyl-anthracene | \n23 \n | \n400/377 \n | \n24 \n | \n402/378 \n | \n33.23 | \n
23 | \n424/401 | \n24 | \n424/400 | \n||
Fluoranthene | \n94 | \n418/324 | \n92 | \n417/325 | \n33.96 | \n
Benzo(b)fluorene | \n28 \n | \n339/311 \n | \n29 \n | \n341/312 \n | \n37.60 | \n
46 | \n356/310 | \n45 | \n357/312 | \n||
Pyrene | \n39 \n | \n369/330 \n | \n39 \n | \n372/333 \n | \n35.53 | \n
46 | \n378/332 | \n46 | \n379/333 | \n||
1-Methyl-pyrene | \n31 | \n370/339 | \n34 | \n373/339 | \n39.08 | \n
4-Methyl-pyrene | \n52 | \n376/324 | \n51 | \n374/323 | \n39.73 | \n
3-Methyl-pyrene | \n30 \n | \n378/348 \n | \n31 \n | \n376/345 \n | \n39.94 | \n
50 | \n377/327 | \n48 | \n376/328 | \n||
Benzo(c)-phenanthrene | \n94 | \n376/282 | \n93 | \n374/281 | \n43.37 | \n
2-Methyl-benzo-(c)-phenanthrene | \n66 \n | \n398/332 \n | \n66 \n | \n399/333 \n | \n43.70 | \n
103 | \n377/274 | \n104 | \n378/274 | \n||
Benz(a)-anthracene | \n23 | \n384/361 | \n23 | \n384/361 | \n44.88 | \n
1-Methyl-benz(a)-anthracene | \n47 | \n389/342 | \n47 | \n389/342 | \n48.45 | \n
2-Methyl-benz(a)-anthracene | \n20 | \n385/365 | \n19 | \n387/368 | \n47.91 | \n
7-Methyl-benz(a)-anthracene | \n17 | \n392/375 | \n18 | \n392/374 | \n48.19 | \n
8-Methyl-benz(a)-anthracene | \n21 | \n387/366 | \n21 | \n388/367 | \n48.77 | \n
12-Methyl-benz(a)- anthracene | \n35 | \n391/356 | \n37 | \n393/356 | \n47.15 | \n
1,12-Dimethyl-benz(a)-anthracene | \n41 | \n404/363 | \n41 | \n402/361 | \n49.35 | \n
7,12-Dimethyl-benz(a)-anthracene | \n53 | \n399/346 | \n52 | \n399/347 | \n51.44 | \n
Chrysene | \n39 | \n362/323 | \n39 | \n361/322 | \n45.16 | \n
Benzo(b)-fluoranthene | \n30 \n | \n399/369 \n | \n29 \n | \n396/367 \n | \n52.69 | \n
66 \n | \n430/364 \n | \n63 \n | \n430/367 \n | \n||
94 | \n398/304 | \n95 | \n396/301 | \n||
Benzo(e)-pyrene | \n71 | \n390/319 | \n71 | \n389/318 | \n54.37 | \n
Benzo(a)-pyrene | \n34 \n | \n400/366 \n | \n33 \n | \n403/370 \n | \n54.69 | \n
39 | \n425/386 | \n39 | \n427/388 | \n||
Anthanthrene | \n25 \n | \n433/408 \n | \n24 \n | \n434/410 \n | \n61.02 | \n
30 | \n433/403 | \n30 | \n434/404 | \n||
Benzo(g,h,i)-perylene | \n50 | \n420/370 | \n50 | \n420/370 | \n62.85 | \n
3,4-9,10-Di-benzopyrene | \n34 | \n433/399 | \n34 | \n432/398 | \n69.21 | \n
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).
*The term “luminescence” is used sometimes interchangeably with “fluorescence,” describing more widely the discussed phenomenon.
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.
\nIn 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 (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.
\nSynchronous fluorescence spectrum of studied sample measured at Δλ = 23 nm.
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 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.
\nSynchronous fluorescence spectra of studied sample measured at Δλ = 30 nm, Δλ = 39 nm, and Δλ = 46 nm.
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.
\nSynchronous fluorescence spectra of studied sample measured at Δλ = 53 nm and Δλ = 105 nm.
\nFigure 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 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.
\nFluorescence emission spectrum of studied sample measured at λexc = 324 nm.
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.
\nTo 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 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.
\nFluorescence emission spectrum of studied sample measured at λexc = 350 nm.
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.
\nIn 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/:
\nTotal 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.).
\nThe 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.
\nSFS 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 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.
\nThe 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.
\nThus, 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.].
\nThese 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, 13, 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.
\nAlmost 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].
\nThe 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.
\nConsiderable 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].
\nThe 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).
\nThe 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.
\nThe 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].
\nTechnique 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.
\nThe results obtained may be a basis to discussion on the evaluation of the environmental hazards.
\nThe 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.
\nSFS | synchronous fluorescence spectroscopy |
PAHs | polycyclic aromatic hydrocarbons |
TIC | total ion-chromatogram |
TLC | thin layer chromatography |
GC/MS | gas chromatography-mass spectrometry |
HPLC | high performed liquid chromatography |
MSD | mass selective detector |
EPA | Environmental Protection Agency |
Supporting women in scientific research and encouraging more women to pursue careers in STEM fields has been an issue on the global agenda for many years. But there is still much to be done. And IntechOpen wants to help.
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