Concentration of organic and inorganic pollutants in rural and urban soils in France (values extracted from Ademe [13]).
\r\n\t
",isbn:"978-1-83969-591-9",printIsbn:"978-1-83969-590-2",pdfIsbn:"978-1-83969-592-6",doi:null,price:0,priceEur:0,priceUsd:0,slug:null,numberOfPages:0,isOpenForSubmission:!0,hash:"e39a567d9b6d2a45d0a1d927362c9005",bookSignature:"Dr. Umar Zakir Abdul Hamid and Associate Prof. Ahmad 'Athif Mohd Faudzi",publishedDate:null,coverURL:"https://cdn.intechopen.com/books/images_new/10778.jpg",keywords:"Model-Based Control, Optimal Control, Industrial Automation, Linear Actuator, Nonlinear Actuator, System Identification, Soft Robotics, Service Robots, Unmanned Aerial Vehicle, Autonomous Vehicle, Process Engineering, Chemical Engineering",numberOfDownloads:null,numberOfWosCitations:0,numberOfCrossrefCitations:null,numberOfDimensionsCitations:null,numberOfTotalCitations:null,isAvailableForWebshopOrdering:!0,dateEndFirstStepPublish:"February 25th 2021",dateEndSecondStepPublish:"March 25th 2021",dateEndThirdStepPublish:"May 24th 2021",dateEndFourthStepPublish:"August 12th 2021",dateEndFifthStepPublish:"October 11th 2021",remainingDaysToSecondStep:"21 days",secondStepPassed:!1,currentStepOfPublishingProcess:2,editedByType:null,kuFlag:!1,biosketch:"Umar Zakir Abdul Hamid, Ph.D. is an autonomous vehicle expert, and with more than 30 scientific publications under his belt, Umar actively participates in global automotive standardization efforts and is a Secretary for a Society of Automotive Engineers (SAE) Committee.",coeditorOneBiosketch:"Associate Professor Dr. Ahmad 'Athif Mohd Faudzi has more than 100 scientific publications as of 2021 and is currently leading a team of 18 researchers in UTM doing research works on control, automation, and actuators.",coeditorTwoBiosketch:null,coeditorThreeBiosketch:null,coeditorFourBiosketch:null,coeditorFiveBiosketch:null,editors:[{id:"268173",title:"Dr.",name:"Umar Zakir Abdul",middleName:null,surname:"Hamid",slug:"umar-zakir-abdul-hamid",fullName:"Umar Zakir Abdul Hamid",profilePictureURL:"https://mts.intechopen.com/storage/users/268173/images/system/268173.jpg",biography:"Umar Zakir Abdul Hamid, PhD has been working in the autonomous vehicle field since 2014 with various teams in different countries (Malaysia, Singapore, Japan, Finland). 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With more than 30 scientific and technical publications as author and editor under his belt, Umar actively participates in global automotive standardization efforts where he is a Secretary for a Society Automotive Engineers (SAE) Committee.",institutionString:"Sensible 4 Oy",position:null,outsideEditionCount:0,totalCites:0,totalAuthoredChapters:"0",totalChapterViews:"0",totalEditedBooks:"1",institution:null}],coeditorOne:{id:"204176",title:"Associate Prof.",name:"Ahmad 'Athif Mohd",middleName:null,surname:"Faudzi",slug:"ahmad-'athif-mohd-faudzi",fullName:"Ahmad 'Athif Mohd Faudzi",profilePictureURL:"https://mts.intechopen.com/storage/users/204176/images/system/204176.png",biography:"Assoc. Prof. Ir. Dr. Ahmad `Athif Bin Mohd Faudzi received the B. Eng. in Computer Engineering, the M. Eng. in Mechatronics and Automatic Control from Universiti Teknologi Malaysia, Malaysia and the Dr. Eng. in System Integration from Okayama University, Japan in 2004, 2006, and 2010 respectively. He was a Visiting Research Fellow at the Tokyo Institute of Technology from 2015 to 2017. From March 2019 to date, he is the Director of the Centre for Artificial Intelligence and Robotics (CAIRO), Universiti Teknologi Malaysia, Malaysia. He is mainly engaged in the research fields of actuators (pneumatic, soft mechanism, hydraulic, and motorized actuators) concentrate his work in field robotics, bioinspired robotics and biomedical applications. He is a Professional Engineer (PEng), a Charted Engineer (CEng), a member of the IEEE Robotics and Automation Society (RAS) and a member of two Akademi Sains Malaysia Special Interest Group (ASM SIG) of Biodiversity and Robotics. He is also the recipient of Top Research Scientist Malaysia (TRSM) 2020 in the area of Robotics. 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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:"44687",title:"Optical Fibre Long-Period Gratings Functionalised with Nano-Assembled Thin Films: Approaches to Chemical Sensing",doi:"10.5772/52935",slug:"optical-fibre-long-period-gratings-functionalised-with-nano-assembled-thin-films-approaches-to-chemi",body:'Optical techniques are considered as powerful tools for the development of chemical and biological sensors, covering a wide range of applications including bio-chemical and food analysis, and environmental and industrial monitoring [1, 2, 3]. Optical fibre sensors, as a result of their advantages such as high sensitivity, compactness, remote measurement and multiplexing capabilities, have attracted a great deal of attention for the development of refractometers and chemical sensors [4, 5, 6]. Refractometers and chemical sensors based on optical fibre gratings, both fibre Bragg gratings (FBGs) and long period gratings (LPGs), have been extensively employed for refractive index measurements and monitoring associate chemical processes since they offer wavelength-encoded information, which overcomes the referencing issues associated with intensity based approaches.
FBG based approaches have exploited side polished [7] and thinned [8,9] optical fibres to expose the evanescent field of the mode propagating in the core of the fibre to the surrounding medium, such that the Bragg wavelength becomes sensitive to the surrounding refractive index. The response of such sensors is non-linear, with a maximum predicted sensitivity of approximately 200 nm/refractive index unit (RIU) for indices close to that of the cladding of the optical fibre [8]. Experimental investigation revealed a sensitivity of 70 nm/RIU with a corresponding resolution of order 10-4 RIU, assuming that the Bragg wavelength is measured with a resolution of 1 pm [9].
The effective refractive indices of the modes of the cladding of the optical fibre are inherently sensitive to the surrounding refractive index. Tilted fibre Bragg gratings (TFBGs) and LPGs allow the controlled, resonant coupling of light from the core of the optical fibre into cladding modes. The characteristics of the resonant coupling are modified by changes in the surrounding refractive index, affording the ability to form refractive index sensors without altering the geometry of the optical fibre.
TFBGs facilitate the coupling of the propagating core mode to backward propagating cladding modes. As the coupling wavelength and efficiencies are dependent upon the properties of the cladding modes, the resonance features in the TFBG transmission spectrum exhibit sensitivity to surrounding refractive index [10,11]. Analysis of the transmission spectrum facilitates measurements with resolution of 10-4 RIU [11]. The use of thin film coatings of refractive index higher than that of the cladding on both polished FBGs and TFBGS has been shown to allow the RI range over which the devices show their highest sensitivity to the tuned to lower values [10,12,13].
LPGs promote coupling between the propagating core mode and co-propagating cladding modes, i.e. work as transmission gratings and are more attractive for practical applications as compared to FBGs, owing to lower cost of analytical instruments used to interrogate them. The high attenuation of the cladding modes results in the transmission spectrum of the fibre containing a series of attenuation bands centred at discrete wavelengths, each attenuation band corresponding to the coupling to a different cladding mode, as shown in Figure 1 [14].
The refractive index sensitivity of LPGs arises from the dependence of the phase matching condition upon the effective refractive index of the cladding modes that is governed by Equation 1 [14]:
where λ(x) represents the wavelength at which the coupling occurs to the linear polarized (LP0x) mode, ncore is the effective RI of the mode propagating in the core, nclad(x) is the effective RI of the LP0x cladding mode, and Λ is the period of the grating.
The effective indices of the cladding modes are dependent upon the difference between the refractive index of the cladding and that of the medium surrounding the cladding. The central wavelengths of the attenuation bands thus show a dependence upon the refractive index of the medium surrounding the cladding, with the highest sensitivity being shown for surrounding refractive indices close to that of the cladding of the optical fibre, provided that the cladding has the higher refractive index [15]. For surrounding refractive indices higher than that of the cladding, the centre wavelengths of the resonance bands show a considerably reduced sensitivity [15].
The refractive index sensitivity of an LPG is dependent upon the order of the cladding mode that is coupled to, allowing the tuning of the sensitivity by appropriate choice of grating period, with 427.72, 203.18, 53.45, and 32.10 nm/RIU being reported for LPGs fabricated in single mode fibre (SMF) 28 with period 159, 238, 400, and 556 μm, respectively [16]. A further consideration is the geometry and composition of the fibre, with the sensitivity being shown to differ for step index and W profile fibres and a progressive three layered fibre [17]. New fibre geometries, such as photonic crystal fibres [18,19] and photonic band gap fibres [20] have also been investigated for the measurement of the refractive index of a liquid that fills the air channels. LPGs in liquid filled solid-core photonic bandgap fibre have been shown to exhibit a sensitivity of 17,900 nm/RIU to changes in the RI of the liquid [21], but the requirement to fill the fibre with the liquid of interest may limit application as a refractometer.
a) Schematic illustration of the LPG structure and (b) transmission spectra of LPGs with different grating periods fabricated in an optical fibre of cut-off wavelength 670 nm (Fibrecore sm700): (i) 80 μm, (ii) 100 μm, and (iii) 400 μm [5].
In order to improve the sensitivity of the LPGs written in standard optical fibre configurations to surrounding RI, approaches such as tapering the fibre [22] or etching the cladding [23,24] have been investigated. Tapering the fibre to a diameter of 25 μm allowed the demonstration of an LPG with a sensitivity of 715 nm/RIU [22]. Etching the cladding of a section of standard single mode fibre containing an LPG from 125 μm to approximately 100 μm produced a sensitivity gain of 5 [25], while the etching an arc induced LPG to a diameter of 37 μm allowed the demonstration of a sensitivity of order 20,000 nm/RIU [26]. Approaches that require the processing of the fibre, such as polishing, etching and tapering, produce significant enhancements in sensitivity, but at the cost of requiring careful packaging to compensate for the inevitable reduction in the mechanical integrity of the device.
The deposition of thin film overlays, of thickness on the order of 200 nm, of materials of refractive index higher than that of the cladding has also been investigated for the enhancement of refractive index sensitivity [25,26]. It has been shown previously experimentally and theoretically [27,28] that the effective indices of the cladding modes, and thus the central wavelengths of the core-cladding mode coupling bands of LPGs, show a high sensitivity to the optical thickness of high refractive index coatings when the coating’s optical thickness is such that one of the low order cladding modes is phase matched to a mode of the waveguide formed by the coating. This is termed the mode transition region, in which the cladding modes are reorganized, with each mode taking on the characteristics (effective index and electric field profile) of its adjacent lower order cladding mode [29]. The output from a numerical model of the influence of coating thickness on the effective indices of the cladding modes of an optical fibre is plotted in Figure 2, showing clearly the mode transition region.
Plot of the effective refractive indices of the first 9 cladding modes as a function of the thickness of an overlay of refractive index. The model assumed values for the core and cladding refractive indices of 1.4496 and 1.446 respectively, a core radius of 3.5 µm, and that the refractive index of the overlay material was 1.57.
Biasing the optical thickness of the coating such that the LPG is operating in the mode transition region enhances the sensitivity of the cladding mode effective indices and thus the resonance wavelengths to the surrounding refractive index. A theoretical analysis explored the optimization of the refractive index sensitivity by selecting grating period, coating thickness and refractive index, predicting a sensitivity of 5980 nm/RIU [29].
In addition, the combination of optical fibers and nanomaterials provides a prospect for the fabrication of chemical sensors with high sensitivity and that offer specific response to targeted chemical species [30,31]. Achieving the coating thickness that provides optimized sensitivity requires control on the nm scale, which is why many reports have exploited the Langmuir Blodgett (LB) and layer-by-layer (LbL) electrostatic self assembly (ESA) coating deposition techniques, where a multilayer coating is deposited with each layer having a thickness of order 1 nm. Based on this principle, sensors for organic vapors, metal ions, humidity, organic solvents and biological materials have been reported [32, 33, 34]. Similarly to surface plasmon resonance (SPR) devices, LPG sensors can provide highly precise analytical information about adsorption and desorption processes associated with the RI and thickness of the sensing layer. For instance, the sensitivity of LPG sensors is in the same order of magnitude as SPR sensors, showing a sensitivity of ca. 1 nM for antigen–antibody reactions. An advantage of the LPG over SPR lies in the ability to fabricate a cheap and portable device that can be applied in various analytical situations.
The influence of the period of the LPG on the sensitivity of the mode coupling to perturbations such as changes in surrounding RI can be understood with reference to the phase matching condition, equation (1). Using the weakly guided approximation it is possible to determine the effective indices of the modes of the core and cladding, and, using equation 1, to generate a family of phase matching curves that describe the variation of the resonant wavelength with period of the LPG, an example is shown in Figure 3. It can be seen that the phase matching condition for each cladding mode contains a turning point. The resonance features in the LPG spectrum exhibit their highest sensitivity to external perturbations near the phase matching turning point. The response of the transmission spectrum of an LPG operating near the phase matching turning point external perturbation, in this case changes to the optical thickness of a coating deposited onto the optical fibre, are illustrated in Figure 4. In Figure 4a, the grating period is such that phase matching to the LP020 cladding mode is satisfied, but it is not possible to couple to the LP021 cladding mode, with a resulting LPG transmission spectrum of the form shown in Figure 4b. Changes in the optical thickness (product of the geometrical thickness and refractive index) of the coating cause an increase in the effective refractive index of the cladding modes, and the phase matching curves change accordingly, as illustrated in Figure 4c, resulting in the development of a resonance band corresponding to coupling to the LP021 cladding mode, and a small blue shift in the central wavelength of the LP020 resonance band, Figure 4d. Further increases in the optical thickness of the coating result in the further development of the LP021 resonance band, which subsequently splits into two bands, the so called dual resonance, Figures 4f and 4h. The small gradient of the phase matching curve at the phase matching turning point results in the LP021 resonance band exhibiting much higher sensitivity than the LP020 resonance band for this grating period. Thus the sensitivity of coated LPG sensors can be optimised by appropriate choice of the optical thickness of the coating and period of the grating to ensure that the LPG operates at both the mode transition region and the phase matching turning point.
Recently, LPG fibre sensors with porous coatings have attracted a lot of interest. For instance, a sol-gel film of SnO2 of thickness of order 200 nm was deposited onto to an LPG, facilitating the demonstration of an ethanol gas sensor. The porosity and high RI of the coating material resulted in the LPG spectrum exhibiting a response to the diffusion of ethanol gas into the coating and the authors predicted that an optimized sensor would exhibit a detection limit of 100 ppb. Sol-gel coatings of SiO2 and TiO2 have been deposited onto LPGs, revealing a gain of 2 in the sensitivity to external RI, with the higher index TiO2 coating offering the larger response (up to 1067.15 nm/RIU). The authors noted that the higher the index and thickness of the coating the more pronounced was the enhancement in LPG sensitivity compared to the equivalent uncoated LPG [16].
Phase matching curves for higher order cladding modes of an optical fibre of cut off wavelength 670 nm. The numbers refer to the order of the cladding mode.
Recently we have demonstrated a fibre optic refractive index sensor based on a long period grating (LPG) with a nano-assembled mesoporous coating of alternate layers of poly(allylamine hydrochloride) (PAH) and SiO2 nanospheres [5, 6]. PAH/SiO2 coatings of different thicknesses were deposited onto an LPG operating near its phase matching turning point in order to study the effect of the film thickness and porosity on sensor performance. The device showed a high sensitivity (1927 nm/RIU) to RI changes with a response time less than 2 sec over a wide RI range (1.3330–1.4906). The low refractive index of the mesoporous film, 1.20@633 nm, facilitates the measurement of external indices higher than that of the cladding, extending the range of operation of LPG based RI sensors. The ability of this device to monitor, in real time, RI changes during a dilution process was also demonstrated.
In this chapter we introduce a new approach to LPG based chemical sensing. A novel 2 stage approach to the development of the sensor is explored. The first stage involves the deposition of the mesoporous coating onto the LPG operating near the phase matching turning point. In the second stage a functional material, chosen to be sensitive to the analyte of interest, is infused into the base mesoporous coating. The mesoporous coating consists of a multilayer film of SiO2 nanoparticles (SiO2 NPs) deposited using the LbL technique. The initially low RI of the mesoporous coating, 1.2@633 nm, is increased significantly by the chemical infusion, resulting in a large change in the LPG’s transmission spectrum. The sensing of ammonia in aqueous solution was chosen to demonstrate the sensing principle. The operation of the sensor was characterised using two functional materials, tetrakis-(4-sulfophenyl)porphine (TSPP) and polyacrylic acid (PAA). TSPP is a porphine compound that changes its optical properties (absorbance and RI) in response to exposure to ammonia, while PAA has been employed as a functional compound ammonia binding [35]. In the case of the PAA it is assumed that direct biding of ammonia to the COOH moiety will change RI of the mesoporous coating, while in the case of TSPP its desorption will result on RI change.
Optical features of the LP020 and LP021 cladding modes near the phase matching turning point. An increase in the effective index of the cladding modes, caused for example by an increase in the surrounding refractive index, or in the optical thickness of a coating deposited onto the fibre, cause the phase matching curves to move as shown, producing large changes in the coupling characteristics and transmission spectrum.
Tetrakis-(4-sulfophenyl)porphine (TSPP, Mw = 934.99) was purchased from Tokyo Kasei, Japan. Poly(diallyldimethylammonium chloride) (PDDA, Mr = 200,000–350,000, 20% (w/w) in H2O; monomer Mw = 161.5 g mol−1), PAA25 (Mw: 250,000, 35 wt% in H2O) and ammonia 30 wt% aqueous solution were purchased from Aldrich. A colloidal solution of silica nanoparticles (SiO2 NPs), SNOWTEX 20L (40–50 nm), was purchased from Nissan Chemical. All chemicals were reagents of analytical grade, and used without further purification. Deionized pure water (18.3 MΩ cm) was obtained by reverse osmosis followed by ion exchange and filtration in a Millipore-Q (Millipore, Direct-QTM).
A detailed description and reference to the optical properties of LPGs can be found elsewhere [5, 6, 36]. In this work, an LPG of length 30 mm with a period of 100 μm was fabricated in a single mode optical fibre (Fibercore SM750) with a cut-off wavelength of 670 nm using point-by-point UV writing process. The photosensitivity of the fibre was enhanced by pressurizing it in hydrogen for a period of 2 weeks at 150 bar at room temperature.
SiO2 NPs were deposited onto the surface of the fibre using the LbL process, as illustrated in Figure 5a. As the LPG transmission spectrum is known to be sensitive to bending, for the film deposition process and ammonia detection experiments the optical fibre containing LPG was fixed within a special holder, as shown in Figure 5b, such that the section of the fibre containing the LPG was taut and straight throughout the experiments [36]. The detailed procedure of the deposition of the SiO2 NPs onto the LPG and infusion of the TSPP compound has been previously reported [5]. Briefly, the section of the optical fibre containing LPG, with its surface treated such that it was terminated with OH groups, was alternately immersed into a 0.5 wt% solution containing a positively charged polymer, PDDA, and, after washing, into a 1 wt% solution containing the negatively charged SiO2 NPs solution, each for 20 min. This process was repeated until the required coating thickness was achieved. When the required film thickness had been achieved (i.e. when the development of the second resonance band was observed with the fibre immersed into water), ca. after 10 deposition cycles, the coated fibre was immersed in a solution of TSPP or PAA as functional compound for 2 h, which was infused into the porous coating and provided the sensor with its specificity. Due to the electronegative sulfonic groups present in the TSPP compound, an electrostatic interaction occurs between TSPP and positively charged PDDA in the PDDA/SiO2 film. On the other hand, PAA is usually considered as a promising sensor element for ammonia sensing, owing to the presence of free carboxylic function groups that lead to high affinity towards amine compounds [37]. After immersion into the TSPP and PAA solutions, the fibre was rinsed in distilled water, in order to remove physically adsorbed compounds, and dried by flushing with N2 gas. The compounds remaining in the porous silica structure were bound to the surface of the polymer layer that coated each nanosphere. This effectively increased the available surface area for the compounds to bond to. The presence of functional chemical compounds increased the RI of the porous coating and resulted in a significant change in the LPG’s transmission spectrum, consistent with previous observations for increasing the coating thickness [38]. All experiments have been conducted at 25oC and 50% of rH.
a) Schematic illustration of the electrostatic self-assembly deposition process and (b) deposition cell with a fixed LPG fibre.
Figures 6a and 6b show the surface morphology and cross-section of the 10-cycle (PDDA/SiO2) layer, referred to as (PDDA/SiO2)10, on a quartz substrate, respectively. As can be seen, the (PDDA/SiO2)10 film has a uniform surface consisting of SiO2 NPs with an average diameter of 45 nm (Figure 6a). The film thicknesses obtained after 1 and 10 cycles of the (PDDA/SiO2) deposition process, determined from SEM cross-section measurements, are approximately 50±2 nm and 450±20 nm, respectively (Figures 6b and 6c). The pore size distribution of the (PDDA/SiO2) film indicates a well-developed mesoporous structure with a mean pore radius of 12.5 nm and specific surface area of 50 m2 g−1 [5].
The transmission spectrum of the 100 μm period LPG undergoes changes due to the alternate deposition of SiO2 NPs, as shown in Figure 7, which influences the effective RI of the cladding mode, as described previously [5]. When the LPG was in the silica colloidal solution, the resonance feature (at ca. 640 nm) corresponding to coupling to the LP020 cladding mode exhibited a small blue wavelength shift of 8.5 nm. As the optical thickness of the coating increased, it became possible to couple energy to the LP021 mode, with the corresponding development of the resonance band at ca. 800 nm [5], at the phase matching turning point for that mode. However, because of the low RI (1.20) [39] of the porous silica coating, this resonance feature is not well developed in water and is not present in air for this coating thickness.
When an uncoated LPG fibre with a period of 100 μm is immersed into water (RI=1.323), a blue shift of the LP020 resonance band of 3 nm is observed. However, the sensitivity of the LP020 resonance band is much improved by coating the LPG with a (PDDA/SiO2)10 film, showing a blue shift of 7 nm when the LPG was immersed in water, along with the appearance of the well pronounced second resonance band, LP021 (Figure 8a). This is attributed to the increase in sensitivity of the LPG to the surrounding RI [16], being of interest when measuring the RI of low concentration aqueous solutions. The response to the RI changes is fast (< 2 s) and stable, as indicated by the measurement of the transmitted power at the centre of the LP021 resonance (Figure 8b).
SEM images of the (a) surface morphology and (b) cross-section of the (PDDA/SiO2)10 film deposited on a quartz substrate before TSPP infusion; (c) cross section of a (PDDA/SiO2)1 film.
a) Transmission spectra of the 100 μm period LPG in the colloidal SiO2 solution in water after PDDA deposition (b) wavelength shifts and changes in transmission as a function of the number of deposition cycles for the LP020 and LP021 resonance bands, respectively; the curve is a guide to the eye only.
a) Transmission spectra of the 100 μm period LPG under different conditions: black line, in air without coating; red line, in water without coating; green line, in water after deposition of the (PDDA/SiO2)10 film. (b) Dynamic changes of the transmission spectrum of the SiO2 NP coated LPG measured at 800 nm in different phases from air to water.
The RI and film thickness of a 1-cycle PDDA/SiO2 film, measured using ellipsometry, were 1.20 (at 633 nm) and 47±2 nm, respectively, which is in a good agreement with both the reported data for RI [39] and the thickness measured using SEM (see Figure 6b). It should be noted that dispersion of the RI in the wavelength range of 400–800 nm is negligible, with the RI value of 1.20±0.0001, and does not influence LPG sensor performance over the operational wavelength range of 600–900 nm. The deposition of the PDDA/SiO2 layer was also monitored using the QCM technique and UV-vis spectroscopy (data not shown). A (PDDA/SiO2)10 film was deposited on two different QCM electrodes and a relative standard deviation of ±11% was obtained. The frequency linearly decreased as the number of the deposition cycles increased with average values of 1739±207 Hz and 30±10 Hz for the SiO2 and PDDA layers, respectively. This corresponds to SiO2 and PDDA masses of 1565 ng and 27 ng per each layer, respectively. The average thickness of the SiO2 layer was 42±4 nm [36], which corresponds very well with the values determined using ellipsometry and SEM. A uniform PDDA/SiO2 film was assembled on the quartz substrate, as revealed by the increase of the absorbance in the UV region with increment in the number of SiO2 NP layers. The modulation observed in the absorption spectrum of the coated quartz slide was the result of the interference between light reflected from the front and rear surfaces of the coated slide, which introduces a channelled spectrum, the period and phase of which is dependent on the PDDA/SiO2 film optical thickness. Thickness values of the PDDA/SiO2 film deposited onto different substrates (quartz slab, silicon wafer and optical fibre) using a LbL method determined from SEM, QCM and ellipsometry measurements agreed well, within experimental error, regardless of the surface nature, indicating that the LbL method is an efficient tool for the deposition of uniform nano-thin films on different types of surfaces.
The principle of operation of a coated LPG sensor operating at the phase matching turning point and applied to the detection of chemical components that can be bound through an electrostatic interaction with PDDA in the mesopores of the film has been discussed previously [5]. The resonance bands (LP020 and LP021) could be used for the detection of chemical components that can be bound through an electrostatic interaction with the cationic groups of PDDA in the mesopores of the film. When an LPG coated with a (PDDA/SiO2)10 film is immersed in a TSPP solution, the transmission spectrum undergoes significant changes. Figure 9a shows the transmission spectra recorded when the (PDDA/SiO2)10 film coated LPG was immersed in a 1 mM TSPP water solution. As the TSPP is infused into the film, the RI of the film increases (from 1.200 to ca. 1.540, measured using ellipsometry) and the phase matching condition for coupling to LP021 is satisfied. A broad single attenuation band is developed rapidly (within 60 s), which subsequently splits in two bands as the RI of the coating increases in response to the TSPP infusion. The required time to complete the binding between the TSPP and PDDA moieties is less than 600 s (Figure 9b). The observed response indicates a large increase in the optical thickness of the film, which is a result of the increase in the RI of the film, as the TSPP is infused into the porous structure and adsorbed to the PDDA moiety between SiO2 NPs.
The evolution of the transmission spectrum of the SiO2 coated LPG when immersed in the TSPP solution is shown in the grey scale plot shown in Figure 10, where the transmission is represented by white and black, corresponding to 100% and 0%, respectively. The dark line at around 635 nm, which originates at a wavelength of 640 nm in the uncoated LPG, represents the resonance band that corresponds to the first order coupling to the LP020 cladding mode. The discontinuity in the trace, at 60 s, occurred when the LPG was immersed in the solution and is a result of the LPG’s sensitivity to the RI of the solution.
a) Transmission spectra of the SiO2 NP coated LPG and (b) the dynamic transmission change recorded at 800 nm when the SiO2 NP coated LPG was immersed in a TSPP solution (1 mM in water).
In order to assess the sensitivity of the optical device, the (PDDA/SiO2)10 coated LPG was exposed to different concentrations of TSPP, and the results are shown in Figures 11a and 11b. The increase of the TSPP concentration from 10 to 1000 μM results in a decrease of the transmission measured at 800 nm, corresponding to the development of the LP021 cladding mode resonance. This is also accompanied by a blue shift of the LP020 resonance band, indicating the increase of the RI of the film. The response time of the sensor is observed to be slower at lower TSPP concentrations. For 1 mM TSPP concentration, the increase in transmission at 800 nm, shown in Figures 11b, is attributed to the splitting of the fully developed LP021 cladding mode resonance into dual resonance bands.
The evolution of the transmission spectrum of the SiO2 NP coated LPG (period 100 μm), when immersed in an aqueous solution of TSPP (1 mM). The grey scale represents the measured transmission, with white corresponding to 100%, and black to 0%.
The ability to reuse the device was tested by removing the infused TSPP molecules from the film using an ammonia solution (ca. 1000 ppm). The spectrum was reverted to that observed for the (PDDA/SiO2)10 coated LPG before TSPP infusion. Subsequent immersion of the (PDDA/SiO2)10 coated LPG into the TSPP solutions allowed the results shown in Figure 11 to be reproduced.
A similar effect to that observed for the infusion of TSPP was observed when the (PDDA/SiO2)10 coated LPG was immersed into a PAA solution. The magnitude of the change, however, was smaller as compared to that induced by TSPP infusion, most plausibly being related to the lower RI of PAA (1.442) [40] as compared with that of TSPP (1.540) [5]. It should be noted that thickness of the (PDDA/SiO2)10 film was not changed on the infusion of the functional compounds, as revealed from SEM cross-sectional and ellipsometry measurements of the samples deposited onto the optical fibre before and after TSPP infusion (data not shown).
The infusion of the TSPP molecules into the PDDA/SiO2 film deposited on a glass substrate was also investigated using UV-vis spectroscopy. Figure 12 shows the absorbance spectrum of the PDDA/SiO2 film after infusion of the TSPP compound. As can be seen from Figure 12, the two Soret bands at wavelengths 419 and 482 nm, along with well-pronounced Q-band at 700 nm, are present, which indicates that the TSPP compound forms J-aggregates in the porous silica film [41,42]. It was previously confirmed that nano-assembled thin films with TSPP in J-aggregate state are particularly sensitive to ammonia gas [42]. In this work, mesoporous SiO2 NPs films infused with TSPP were to be used to detect the presence of ammonia in aqueous solutions. In order to study the stability of the PDDA/SiO2 films infused with TSPP in aqueous solutions, they were immersed into water several times, with the resultant changes in absorption spectra shown in Figure 12. The second Soret-band (482 nm) and Q-band (at 700 nm) disappeared when the film was immersed into water, accompanied by a decrease in the absorbance of the first Soret-band (419 nm), which indicates the partial removal of the adsorbed TSPP molecules from the film [42]. We can speculate that this phenomenon is a result of the cleavage of the J-aggregates of TSPP formed in the space between the SiO2 NPs.
a) Transmission spectra of the (PDDA/SiO2)10 coated LPG; (b) transmission change recorded at 800 nm in response to different concentrations of TSPP (from 10 μM to 1 mM in water) and (c) dynamic response to the three infusions of TSPP into the PDDA/SiO2 porous film recorded at 800 nm; the infusion was conducted after complete removal of TSPP from the PDDA/SiO2 using an NH3 solution of concentration 1000 ppm.
Absorption spectra of the (PDDA/SiO2)10 film infused with TSPP on a quartz plate: before immersion into H2O (solid line) and after immersion into ammonia solutions of concentration from 0 ppm, 1.7 ppm, 17 ppm and 170 ppm (dashed lines); inset shows the structure of the TSPP.
The observed absorbance decrease reached a steady state after several immersions, indicating that only strongly bound TSPP molecules remained in the PDDA/SiO2 porous film. Subsequently, immersion of the PDDA/SiO2 film into aqueous solutions containing ammonia led to the further removal of TSPP from the film, resulting in a decrease of the absorbance at 419 nm in proportion to the ammonia concentration, as shown in Figure 12. The absorbance at 419 nm almost disappeared, at an ammonia concentration of 170 ppm.
The amount of TSPP infused inside the mesoporous film was estimated from QCM measurements to be 1135.6 ng (1.13 nmol). Consequently, considering the amount of adsorbed PDDA to be 250 ng (278 Hz for 10 cycles, 1.50 nmol as monomer unit of PDDA), the porous film contains sufficient binding sites for the infused TSPP molecules using the electrostatic interaction. When the QCM electrode that had been coated with a (PDDA/SiO2)10 film infused with TSPP was immersed into water and into ammonia, a similar trend to that measured using a UV-vis spectrophotometer was observed [36]. In particular, the frequency increased after each immersion into water (for 5 min) by up to a factor of 5, indicating the desorption of TSPP from the film; about 70% of the employed TSPP molecules were removed from the film [36]. Further immersion into water did not lead to a significant frequency change, suggesting that strongly bound TSPP (ca. 30% of the employed TSPP molecules) remained in the mesoporous film. When the film was exposed to ammonia solutions of different concentrations, further desorption of TSPP was observed and the total mass loss was 292 ng, indicating the almost complete removal of TSPP from the film [36]. Consequently, ca. 51 ng of TSPP remained in the film after ammonia treatment.
For ammonia detection, the sensing mechanism may be based upon changes in the RI of the coating resulting from chemically induced adsorption or desorption of the functional material to or from the mesoporous coating. Porphyrins have tetrapyrrole pigments [43] and their optical spectrum in the solid state is different to that in solution, due to the presence of strong π–π interactions [43]. Interactions with some chemical species can produce further spectral changes, thus creating the possibility that they can be used in the development of optical sensor systems. For instance, exposure of TSPP that has sulfonic functional groups to ammonia leads to the modification of the absorption spectrum [42].
The sensitivity to ammonia in water of an LPG coated with a (PDDA/SiO2)10 film that was infused with TSPP was characterized by sequential immersion of the coated LPG into ammonia solutions with different concentrations (0.1, 1, 5 and 10 ppm). The lower ammonia concentrations were prepared by dilution of the stock solution of 28 wt%. In order to assess the stability of the base line, the coated LPG was immersed several times into 150 μL of pure water. The decrease of attenuation of the second resonance band, LP021, at 800 nm, indicates the partial removal of the adsorbed TSPP molecules as discussed above. The equilibrium state was achieved after several exposures into water. For the ammonia detection, the LPG fibre was exposed into a 150 μL ammonia solution of 0.1 ppm, followed by drying and immersion into ammonia solutions of 1, 5 and 10 ppm.
a) Transmission spectra of the LPG coated with a TSPP infused (PDDA/SiO2)10 film due to immersion into water and into ammonia solutions of different concentrations: “H2O”, LPG exposed into water; “air”, LPG in air after drying with N2 gas; “NH3 x ppm”, LPG exposed into a x ppm ammonia solution, where x = 0.1, 1, 5 and 10. (b) Dynamic response to water and ammonia solutions (0.1, 1, 5 and 10 ppm) recorded at 800 nm; LP020 and LP021 are labelling the linear polarized 020 and 021 modes, respectively.
The response of the transmission spectrum to varying concentration of ammonia is shown in Figure 13a. The dynamic response of the sensor was assessed by monitoring the transmission at the centre of the LP021 resonance band at 800 nm. The response is shown in Figure 13b, where “air” region and “H2O” and “NH3” regions correspond to the transmission recorded at 800 nm after drying the LPG and exposing the devise into water and ammonium solutions, respectively. After repeating the process of immersion in water and drying 4 times, the recorded spectrum was stable, demonstrating the robustness and stability of the employed molecules in aqueous environments (H2O regions indicated in Figure 13). On immersion in 1 ppm and 5 ppm ammonia solutions, the transmission measured at 800 nm increases. The transmission when the coated LPG was immersed in a 10 ppm ammonia solution exhibits a further increase, reaching a steady state within 100 s, as shown in Figure 13b. The resonance feature corresponding to coupling to the LP020 cladding mode exhibits additional small red shifts of 0.5 and 1.5 nm when subsequently immersed in solutions of 1 ppm and 10 ppm ammonia concentration, respectively, along with decreases in amplitude, as shown in Figure 13a. The limit of detection (LOD) for the 100 μm period LPG coated with a (PDDA/SiO2)10 film that was infused with TSPP was 0.14 ppm and 2.5 ppm when transmission and wavelength shift were measured respectively. The LOD was derived from the calibration curve and the following equation [36, 44].
where σ is the standard uncertainty obtained as a symmetric rectangular probability [45]; m is the slope of the calibration curve. The sensing mechanism postulated is based upon the UV-vis spectrometer, QCM and LPG fibre measurements, and can be illustrated using Figure 14. As mentioned previously, while most of TSPP molecules form J-aggregates in the PDDA/SiO2 film, some of the molecules are present in monomeric forms, as shown in Figure 14a, which may be easily sulfonated into species with neutral (TSPP4−) and protonated (H2TSPP2−) pyrrole rings in water. As can be concluded from UV-vis measurements, on immersion of the TSPP-infused PDDA/SiO2 film into water, most of J-aggregated TSPP molecules are removed from the mesopores between SiO2 NPs, Figure 12. This indicates that the intermolecular interaction between J-aggregates of TSPP can be easily broken in water. However, some strongly bond TSPP compounds remained in the porous film. Figure 14b shows the chemical reactions involved in the interaction of ammonia with the TSPP4− and H2TSPP2− monomers. The electrostatic interaction between TSPP and PDDA is disturbed by the formation of ammonium ions and this causes the further desorption of the TSPP compound from the PDDA/SiO2 film and consequently a decrease in the refractive index of the film.
It is important to consider the influence of the pH of the ammonia solutions on the sensor response, as the electrostatic interaction between TSPP and PDDA can be disturbed by OH− ions in solution. To check this, the pH of the ammonia solutions used in this work were measured using a compact pH meter (B-211, Horiba), showing 7.3, 7.3 and 7.6 for 0.1, 1, and 10 ppm solutions, respectively. Thus, the molar concentration of NH3 and OH− is estimated to be 0.58, 5.8 and 58 mM for NH3 and 0.25, 0.25 and 50 nM for OH−, respectively. These data reveal that the concentration of OH− does not have a significant role and the sensing mechanism is mainly based on the basicity of ammonia, as shown in Figure 14b. The cross sensitivity of the LPG sensor was tested using ethanol and methanol aqueous solutions. There was no measurable response of the sensor at the concentration levels similar to those tested for ammonia (0.1, 1, 10 and 100 ppm) indicating high selectivity of the sensor device to ammonia over those analytes. At much higher concentrations (10,000 ppm), however, blue-shift of the LP020 band and decrease in transmission at 800 nm was registered, which can be ascribed to the change of the bulk RI of the solution [6].
Schematic illustration of the sensing mechanism.
Schematic illustration of the ammonia sensing mechanism for the LPG fibres modified with (a) TSPP-infused PDDA/SiO2 and (b) PAA-infused PDDA/SiO2 films.
The assessment of the cross sensitivity to other amine containing compounds is in progress. When compared with other ammonia optical sensors [46] the developed LPG device shows similar detection levels to coulorometric [47] and absorption spectroscopy [48] devices. In particular, the current LPG optical fibre sensor modified with a mesoporous thin film offers unique advantages such as versatile chemical infusion of various chemicals into the mesopores, fast response time owing to the easy analyte penetration and robustness. In addition, due to unique properties of the optical fibre such as biocompatibility, multiplexing, small size, immunity to electromagnetic interference and possibility to work in harsh environment, a cost effective, portable sensor system can be produced. To further elucidate the sensing principle of the LPG sensor, the response of a (PDDA/SiO2)10 coated LPG and of a PAA-infused (PDDA/SiO2)10 coated LPG was further examined. There was no change when the (PDDA/SiO2)10 and PAA infused (PDDA/SiO2)10 coated LPGs were exposed to ammonia solutions which have similar values of RI, 1.3329, from 1 ppm to 100 ppm concentrations as measured using a portable refractometer (R-5000, Atago). Thus, no change in sensor signal was recorded in the (PDDA/SiO2)10 coated LPG. On the other hand, higher affinity to ammonia based on the acid-base interaction is expected in the PAA-infused (PDDA/SiO2)10 coated LPG [39]. However, no response to ammonia was observed. This indicates that the adsorption of ammonia in small molecular size results in a small RI change. Consequently, the selective desorption of the functional compound with a high RI from the mesoporous film results in a significant increase in the device sensitivity, as shown in Scheme 1. This measurement principle can be further explored for a different set of analyte-functional compound pair including biological analytes expanding the application range of the proposed LPG device.
It was observed that, if the sensor was repeatedly exposed to a certain concentration of ammonia following a washing and drying cycle, the response was not reproducible, in that on each subsequent exposure to ammonia the extinction of the band was further reduced, as shown in Figure 13. The extinction of the band still changes in time and the effect saturates with the increase of the ammonia concentration, in the way indicated in Figure 13 b. The linear dependence of the sensor response upon the ammonia concentration indicates that magnitude of the change on each exposure is the same; thus proposed device can be employed for measurements of the cumulative exposure to ammonia. However, after a number of repeated exposures, with the number being dependent on the concentration of the ammonia solution to which the device was exposed, the sensitivity was exhausted, and exposure to the ammonia solution would produce a spectrum equivalent to that obtained after deposition of the porous film, but before TSPP infusion [5]. It was found that the TSPP compound could be infused into the porous film again by the exposure of the LPG to a 1 mM solution of TSPP (step (vii) in Figure 5). The reproducibility of the device was tested by the exposure of the LPG coated with the TSPP infused (PDDA/SiO2)10 film to an ammonia solution of concentration >1000 ppm (concentration chosen to ensure that the TSPP was completely desorbed from the PDDA/SiO2 film), followed by washing with pure water and immersion in a 1 mM TSPP solution in order to regenerate the original film properties [5], Figure 11c. The procedure was repeated 5 times and the same behaviour and resulting LPG transmission spectrum were obtained after each reinfusion process. It should be noted that ammonia measurements were conducted 3 times at each concentration. These results indicate that highly reproducible measurements can be conducted by employing TSPP reinfusion step.
The response of the transmission spectrum of an LPG of period 100 μm to the deposition of a multilayer film of SiO2 NPs and the subsequent infusion of a porphyrin into the porous coating has been characterized. The infusion of the functional materials, chosen to be sensitive to the analyte of interest, into the base mesoporous coating was reported. Two possible sensing mechanisms have been exploited, based upon changes in the refractive index of the coating resulting from (1) chemically induced RI changes of the mesoporous coating at the adsorption of the analyte to the functional material, namely PAA and (2) chemically induced desorption of the functional material, namely TSPP, from the mesoporous coating. The operation of the device as a re-useable ammonia sensor with a minimum detection level of 0.14 ppm and a response time of approximately 100 s exploiting desorption sensing mechanism has been reported. On the other hand, the ammonia adsorption to the carboxylic functional groups of the PAA resulted in a small RI change and low sensitivity to analyte. The film thicknesses and functional material infusion time employed in this work have been determined empirically, as the calculation of the RI of the porous coating infused with TSPP and immersed in water would be highly complex. Operation of the system at the point of coincidence of the mode transition region and phase matching turning point for films of larger/smaller thickness could be achieved by decreasing/increasing the quantity of the function dye infused into the film, and this may influence the minimum detectable concentration and sensitivity. Such issues are currently under investigation. Advantages of the proposed method lie in the ability to control functionality of the coating by, for instance, choosing different matrix polymers that extend the class of the detectable analytes. Additionally, infusion of different types of functional compounds would allow the detection of different chemicals using a similar principle of operation. Future work is planned to demonstrate the current system for sensing a variety of chemical and biological compounds and for gas sensing.
This work was supported by the Regional Innovation Cluster Program of the Ministry of Education, Culture, Sports, Science and Technology (MEXT), Japan and partly by the Ministry of Knowledge Economy (MKE, Republic of Korea) via the Fundamental R&D Program for Core Technology of Materials. The authors from Cranfield are grateful to the Engineering and Physical Sciences Research Council, EPSRC, UK for funding under grants EP/D506654/1 and GR/T09149/01.
Although occupied only a small (<3%) proportion of the Earth’s terrestrial surface, urban soils provide a wide range of ecosystem services to inhabitants of cities [1]. In the current context of population growth and urbanization as well as rapid industrialization, urban soils have largely disappeared and polluted by different types of organic and inorganic pollutants. According to urban scholars, although there is an increase of the cultural levels and diverse with more various cities, urbanization however generally leads to a reduction in biodiversity and ecosystem quality. Over the last decade or more, urban gardening is privileged and growing trend in many cities all around the world. For this development, the inhabitants should be assured of that the land is clean and safe. It is urgent that urban soil remediation projects must be to encourage investments.
\nConventional methods of soil decontamination possess disadvantages in forms of environmental cost and financial burden. This truth leads to the search of ecological technologies for restoration of urban soils. One such approach includes phytoremediation. Phytoremediation is a process that uses plant for biological treatment of both organic and inorganic from polluted soils in non-urban and urban areas. Operating costs are very low, ranging from $ 0.02 to 1.00 per m3 of soil [2]. Phytoremediation is based on the use of plant species to extract, retain, immobilize or degrade pollutants in soils. This technique provides good recovery of soils contaminated with heavy metals, and petroleum hydrocarbons.
\nIn the urban context, there are two challenges in attracting the application of phytoremediation for contaminated soils. First, how do make the application of this approach operate and effective? Second, how do inform and train professionals and also non-professionals of the remediation of the contaminated soils potential offered by phytoremediation approaches. This will encourage the use of an ecologically, viable and socially accepted depollution technique.
\nIn this chapter, we will discuss how to take phytoremediation approaches from a proven technology to an accepted practice in the urban context. An overview of urban soil types is provided following phytoremediation’s application for urban soils with the focus on inorganic and organic pollutants, to provide a frame of reference for the subsequent discussion on better utilization of phytoremediation. At last, we offer suggestion on how to gain greater acceptance for phytoremediation by urban inhabitant.
\n“Urban soils” could have several definitions according to scientific or technic domain considered. For World Reference Base for Soil Resources (WRB), urban soils are composed of “any material within two meters of the Earth’s surface that is in contact with the atmosphere, excluding living organisms, areas with continuous ice not covered by other material, and water bodies deeper than two meters” [3]. The Morel and Schwartz team’s works made it possible to complete the definition by adding that these soils are under strong human influence in the urban and suburban landscape [4–6]. These soils are called Technosols [3]. Their studies begin to be more and more important at the beginning of the 21st century with an exponential increase in the number of publications concerning urban soils (Figure 1). Indeed, before the 2000s, the urban soils were considered too disturbed, polluted and poor fertility. Nevertheless, with the ever-increasing population in the city and the growing public concern about environment and human health, the restoration or rehabilitation and remediation of these soils have become a priority. In the urban area, soil is a key issue, subject to very rapid changes in allocation and use (green space, gardens, peri-urban agriculture, urban and industrial activities). Soils provide many essential ecosystems services in urban area, such as carbon and mineral nutrients storage, biota’s habitat, role in hydrologic cycle by reducing runoff and promoting infiltration, water supply and reduction of pollutant bioavailability.
\nEvolution of the number of annual scientific publications on soils (dark gray histogram) and urban soils (histogram light gray) in the international scientific literature over the period 2000–2019. Evolution of the relative share of publications on soil remediation urban is represented by the black curve, which is estimated as % of the total number of publications on urban soils. Bibliometrics on the state of scientific and technological knowledge on urban soils has been evaluated with two search engines: Web of Science and Medline, using these keywords “urban soil”, “remediation”, “restoration”, “rehabilitation” with different combinations.
The main characteristics of urban soils are strong vertical and horizontal spatial heterogeneity in terms of physical, chemical and biological properties [7]. This strong variability can be explained by differences in occupation and use, such as the soils supporting buildings and infrastructures, landscaping areas. Various anthropogenic factors lead to a modification of the initial state of the soil in urban zones. Moreover, most of urban land are the new soils created through mixing, incorporation, and export of earthy materials, compaction or sealing. Unfortunately, the incorporation of these materials leads to frequent pollution of these soils. In general, urban soils display raised pH values due to addition of calcareous and other waste building materials.
\nDue to the human activities, urban soils are contaminated with various organic and inorganic pollutants. Among which, polycyclic aromatic hydrocarbons (PAH), pesticides, biphenyl-polychlorinated (PCB), metals, metalloids and radionuclides are the most abundant. Their presence in soil is undesirable due to their highly toxic and the environmental disturbances they create. Soils contain natural quantity of potentially toxic metals due to constitution of parent rock materials. Trace metals including lead (Pb), cadmium (Cd), mercury (Hg), chromium (Cr), zinc (Zn), copper (Cu), nickel (Ni) and some metalloids such as arsenic (As), Selenium (Se), manganese (Mn) are toxic for living organisms even at low concentration in soils. Whereas some trace metals such as zinc (Zn), copper (Cu), nickel (Ni) are vital elements for living organisms and their physiological properties (enzyme activators, electron transfer system in photosynthesis and respiration). Moreover, the presence of hydrocarbons and metals in soils affects negatively seed germination and plant growth [8], soil microbial community and activities [9], metabolic capacities of plants and microorganisms [10].
\nNevertheless, since several decades, the anthropogenic origins of all the urbans pollutants are various and mainly attributed to (i) transport sources (traffic, vehicle emission, brake and tyre wear), (ii) commercial and industrial emissions (energy production, electronics, metallurgical and chemical industries, fuel combustion, incineration), (iii) domestic activities (construction and demolition, waste disposal, wastewater), and (iv) agricultural activities (application of fertilizers and pesticides, wastewater irrigation) [11].
\nSoil erosion and storm water runoff in urban areas are the main contributor to diffuse pollution according to the United States Environmental Protection Agency [12]. Moreover, the incorporation of calcareous and other waste building materials into urban soils are no negligible and several inorganic pollutants, especially trace metals, are being introduced into these soils leading their use dangerous for human health. Degradation of trace metals is not possible; therefore, they are accumulated and persist in the soil for many years. The concentration of various pollutants in rural and urban areas in France are presented in Table 1. We can see that the concentrations of the most of pollutants are superior in urban area than in rural area. These data confirm also the heterogeneity of these urban soils and are coherent with the concentrations of urban soils of other metropolises (USA, Spain, China, Ireland, Finland, Algeria, Nigeria and Iran) [7].
\n\n | \n | Data acquired in mainly rural areas | \nData acquired in mainly urban areas | \n|||||
---|---|---|---|---|---|---|---|---|
Family | \nName | \nUnit | \nMin | \nMed | \nMax | \nMin | \nMed | \nMax | \n
Trace metals | \nAs | \nmg/kg | \n1.00 | \n— | \n25.00 | \n1.00 | \n8.80 | \n50.20 | \n
Pb | \nmg/kg | \n2.20 | \n34.10 | \n91.50 | \n5.30 | \n57.40 | \n650.00 | \n|
Zn | \nmg/kg | \n<5 | \n80.00 | \n275.00 | \n13.00 | \n94.90 | \n2600.00 | \n|
Ni | \nmg/kg | \n<2 | \n31.00 | \n78.90 | \n4.00 | \n15.00 | \n6200.00 | \n|
Hg | \nmg/kg | \n0.02 | \n— | \n0.10 | \n0.05 | \n0.20 | \n28.00 | \n|
Cd | \nmg/kg | \n<0.02 | \n0.16 | \n6.99 | \n0.05 | \n0.43 | \n3.63 | \n|
Cr | \nmg/kg | \n<2 | \n66.30 | \n118.00 | \n0.90 | \n21.00 | \n111.30 | \n|
Cu | \nmg/kg | \n<2 | \n12.80 | \n27.20 | \n4.20 | \n27.00 | \n190.00 | \n|
HAP | \nNaphtalene | \nmg/kg | \n0.00 | \n0.00 | \n1.03 | \n0.01 | \n0.11 | \n11.00 | \n
Acenaphtylene | \nmg/kg | \n0.00 | \n0.00 | \n0.53 | \n0.01 | \n0.14 | \n15.00 | \n|
Acenaphtene | \nmg/kg | \n0.00 | \n0.00 | \n0.16 | \n0.02 | \n0.16 | \n13.00 | \n|
Fluorene | \nmg/kg | \n0.00 | \n0.00 | \n0.25 | \n0.01 | \n0.08 | \n6.40 | \n|
Phenanthrene | \nmg/kg | \n0.00 | \n0.01 | \n3.47 | \n0.01 | \n0.12 | \n7.80 | \n|
Anthracene | \nmg/kg | \n0.00 | \n0.00 | \n0.56 | \n0.02 | \n0.21 | \n33.00 | \n|
Fluoranthene | \nmg/kg | \n0.00 | \n0.01 | \n6.08 | \n0.01 | \n0.12 | \n10.00 | \n|
Pyrene | \nmg/kg | \n0.00 | \n0.00 | \n4.37 | \n0.01 | \n0.02 | \n0.64 | \n|
Benzo(a)anthracene | \nmg/kg | \n0.00 | \n0.00 | \n2.18 | \n0.01 | \n0.05 | \n1.90 | \n|
Chrysene | \nmg/kg | \n0.00 | \n0.00 | \n4.14 | \n0.02 | \n0.12 | \n10.00 | \n|
Benzo(b)anthracene | \nmg/kg | \n0.00 | \n0.00 | \n2.22 | \n0.01 | \n0.02 | \n0.60 | \n|
Benzo(k)anthracene | \nmg/kg | \n0.00 | \n0.00 | \n1.46 | \n0.01 | \n0.08 | \n16.00 | \n|
Benzo(a)pyrene | \nmg/kg | \n0.00 | \n0.00 | \n1.73 | \n0.02 | \n0.17 | \n29.00 | \n|
Indeno(1, 2, 3-cd)pyrene | \nmg/kg | \n0.00 | \n0.00 | \n1.83 | \n0.01 | \n0.05 | \n1.20 | \n|
Dibenzo(a,h) anthracane | \nmg/kg | \n0.00 | \n0.00 | \n1.13 | \n0.01 | \n0.05 | \n0.70 | \n|
Benzo(g, h, i)perylene | \nmg/kg | \n0.00 | \n0.00 | \n1.53 | \n0.01 | \n0.02 | \n12.00 | \n|
Σ 16 HAP | \nmg/kg | \n0.13 | \n0.16 | \n31.67 | \n0.28 | \n1.56 | \n167.31 | \n|
PCB | \nΣ PCB | \nμg/kg | \n0.20 | \n0.70 | \n17404.20 | \n— | \n— | \n— | \n
Dioxines/furanes | \nΣ Dioxines/furanes | \nng/kg | \n24.75 | \n28.17 | \n2095.28 | \n27.58 | \n162.70 | \n4678.40 | \n
Cyanure | \nCyanure | \nmg/kg | \n— | \n— | \n— | \n0.10 | \n1.00 | \n6.10 | \n
Phenol | \nIndice phenol | \nmg/kg | \n— | \n— | \n— | \n0.01 | \n0.48 | \n86.00 | \n
Hydrocarbures | \nC10, C40\n | \nmg/kg | \n— | \n— | \n— | \n0.50 | \n20.00 | \n260.00 | \n
Concentration of organic and inorganic pollutants in rural and urban soils in France (values extracted from Ademe [13]).
The review of the literature indicates that most scientific articles (>80%) focus on metals and little data are available on traditional or emerging organic pollutants that are now being detected. Many studies still need to be carried out to assess the impact of these pollutants on urban soils and consequently on ecosystem services provided by these soils, and more broadly on human health.
\nAs seen earlier in Section 2.1, urban soils are much polluted. It is therefore necessary to treat them before any other use, be it for parks or gardens. Obviously, depending on the nature of the pollutants (organic or inorganic), their concentrations, and the soil physic-chemical properties, the appropriate technique will differ. Moreover, the reason for which monitoring will also be a criterion for the choice of operational staff. The remediation technics used for the depollution of contaminated site can be in situ or ex situ, on site or off site and biological, physical and chemical. They are often employed in combination with each other in order to optimize the system more efficiently and cost-effectively.
\nEcological methods for soil remediation have received considerable interest in the last decade (Figure 1) and exhibit almost 10% of the publications on urban soils. This growing interest has several reasons such as potential cost savings compared to conventional non biological techniques and the benefit effects of this techniques on urban soil that are often polluted with a poor fertility. Ecological methods the most used in urban soils are phytoremediation, microbes-assisted-remediation, and amendment incorporation. Phytoremediation can be used in combination with this other technique.
\nPhytoremediation [10, 11] consists to use of plants to remediate and revegetate contaminated sites. Phytoremediation technique was first developed to clean up heavy metal(loid)s contaminated soils, thus, the first publications on the subject appears at the end of 1980s and beginning of the 2000s for urban soils. Phytoremediation is considered environmentally friendly, esthetically pleasing, non-invasive and cost-effective technology to clean up the sites with low-to-moderate levels of heavy metal(loid)s (see Section 2).
\nAmendment incorporation in urban soils corresponds mainly to organic amendment such as compost or biochar [12, 13]. In urban soils, this technique is used since 2000s for disturbed soils with poor structure and low levels of OM and fertility in order to improve the physical properties (such as bulk density, infiltration rate, hydraulic conductivity, water content, aggregate stability, and porosity) and function (such as water and nutrients available for plants, support for living organisms, etc.). Concerning contaminated urban soils, the studies on biochar has shown its ability to bind metals, decrease their mobility and bioavailability, stimulate microbial activity and promote soil revegetation and recovery (see Section 3.3).
\nMicrobes-assisted-remediation [14] or bioremediation is a method involving the use of microorganisms to breakdown hazardous contaminants/pollutants to nontoxic or harmless forms. This technique was mainly used for organic pollutants. It can be also used for inorganic pollutant to stabilize metals or metalloids into soil or extract them when associated to phytotechnologies. Bioremediation techniques are mainly of two types: in situ (at the site of contamination) and ex-situ. Bioremediation presents several benefits such as economic viability, social acceptability, and eco-friendly (see Section 3.1).
\nInorganic pollutants which include heavy metals and metalloids are release into the environment due to human activities of industry, transportation and also urban activities. In order to remediate the soils polluted by inorganic pollutants, several conventional chemical and physical techniques have been used for decades; however, they are expensive and often hard to set-up. Recently, phytoremediation is admitted as an appropriate method using plants for the depollution of inorganic pollutants. The number of publications related to phytoremediation has only increased since the early 2000s with an average of 700 articles per over the last 5 years (source: Web of science) with 3–5% focused on urban soil. Moreover, 90% of these publications are related to phytoremediation of soils contaminated by trace metals and metalloids.
\nPhytoremediation of inorganic pollutants refers to phytoextraction, phytostabilization, phytovolatilization and rhizofiltration [14, 15]. Phytovolatilization (only for mercury and selenium) and rhizofiltration are still techniques with an experimental approach and mostly under controlled conditions unlike phytoextraction and phytostabilization which have been applied in the field, and most used to rehabilitate urban soils.
\nPhytostabilization consist to cover contaminated soil by plants either by seeding or planting. As a consequence, the biological, physical and chemical properties of the soils will be improved. The presence of vegetal cover, especially dense root system will permit to decrease the dispersion/mobilization of inorganic pollutants by promoting (i) water infiltration rather than runoff, (ii) evapotranspiration which will limit the percolation of water and thus the leaching of contaminants, and (iii) by retaining fine particles. Thus, plants will stabilize inorganic pollutants by accumulating them in the rhizosphere or into roots and will decrease their bioavailability. Phytostabilization, despite these many advantages (improvement of biological, physical and chemical qualities and consequently the increase in soil ecosystem services), is above all more a management strategy for polluted urban soils than a depollution technique since trace metals and metalloids remain in the soil. The application of amendments promotes the heavy metal stabilization in soils. Recently, aided phytostabilization have been used for remediation of urban soils [16–18]. This technique consists in the chemical stabilization of inorganic pollutants with the combined use of a wide range of soil amendments with a selected plant. This soil amendment can be natural mineral (phyllosilicates, zeolites, and oxides), organic substances, industrial or urban wastes and agriculture (manure, straw, and composts). This amendment will increase the soil pH and sorption capacity of soil rhizosphere (see Section 2.3).
\nPhytoextraction is based on the ability of plants to grow on contaminated soils, absorb inorganic pollutants by their roots and then transfer and accumulate them in significant quantities in their aerial organs (stem, leaves, and reproductive organs). The pollutant presented in soils must therefore be bioavailable for plants. Thus, the phytoremediation process will increase the fraction of metals bioavailable for plants depending on a combination between plant physiology, soil microorganisms (see Section 3.1), soil chemistry and the interaction between plant and microbes. There are many reviews that inventory these hyperaccumulators or high biomass accumulating plants used as a function of the major trace metals or metalloids they accumulate [14, 19, 20].
\nMoreover, in order to improve the efficiency of plants involved in phytoextraction process, many authors proposed the transfer of the hyperaccumulator phenotype from small and slow growing hyperaccumulator species to fast growing, high biomass-producing non-accumulator plants. Many genes involved in the acquisition, allocation and detoxification of metals come from bacteria and yeasts [21]. For example, some works on bioengineering have used plants capable of removing methyl-mercury from contaminated mining and urban soils [22], a strong neurotoxic agents, is biosynthesized in Hg-contaminated soils. To detoxify this compound, transgenic plants have been engineered to express modified bacterial genes merB and merA.
\nIn the case of lead (Pb) which is one of the most trace metals presented in urban soils (see Section 2.2), the content of bioavailability lead in the soils is very low and it is difficult for plant to uptake them. Therefore the rehabilitation of soils polluted be lead is often difficulty. To overcome the problem, it is necessary to realize assisted phytoremediation [23]. This technique consists of adding to the soil various chemical compounds that can increase the availability of trace metals or metalloids in the soil solution. The chemical compounds used are generally aminopolycarboxylic acids (APCA), molecules chelating metal cations such as ethylenediamine tetraacetic acid (EDTA), nitrilotriacetic acid (NTA), hydroxyethylenediaminetetraacetic acid (HEDTA) or diethylenepentaacetic acid (DTPA). Nevertheless, it has been shown that the aminopolycarboxylic acids can be toxic for some plants, microorganisms or nematodes. Meanwhile organic acids such as citric or oxalic acids which are less toxic can be used, but they are less effective in increasing the fraction of trace elements easily assimilated by plants. Moreover, transgenic plants have been engineered too to overproduce recombinant proteins and chelating molecules such as citrate, phytochelatins, metallothioneins, phytosiderophores playing roles in chelation and assimilation of metal.
\nDue to increased human activities including urbanization and industrialization, the pollution of organic pollutants in urban areas has been increased over the last decade. Urban and peri-urban soils are often polluted as consequence of human activities. The main sources of the urban organic pollutants are (1) the utilization of the pesticides in the urban environment, (2) the atmospheric deposition of organic pollutants in form gaseous and particulate by transport, (3) the using of urban waste composts as amendments in urban agriculture and (4) the development of urban industry. According to the results of bibliographic research over the last 20 years on website Web of Sciences, phytoremediation of organic pollutants in non-urban and urban soils generally involved several classes of compounds which are mostly polycyclic aromatic hydrocarbons (PAHs) [24, 25], polychlorinated biphenyls (PCBs) [26] and petroleum hydrocarbons (PHCs) [27] and others low molecular weight compounds such as benzene, toluene and xylene [2] (Table 1).
\nPhytoremediation for organic contaminants takes place at two levels: inside and outside of plant cells. Like the mechanisms of phytoextraction (absorption) which is the primary of phytoremediation for inorganic pollutants as described above (see Section 2.1), some low molecular weight organic contaminants can be taken up by root and then to be accumulated and/or degraded in planta [28]. However, most of organic contaminants are generally too large and/or hydrophobic therefore they cannot to be absorbed by plants. Two primary ex planta mechanisms of phytoremediation for organic contaminants are (1) rhizodegradation via the active microbial communities in the rhizosphere, and (2) phytodegradation via the plant enzymes. For rhizodegradation, rhizosphere microbial community through by their metabolic process transform the organic pollutants (hydrocarbon) to microbial biomass, bioenergy, carbon dioxide and also water for their development [2, 29]. For phytodegradation, plants used for phytoremediation excrete various extracellular enzymes including laccases, dehalogenases, nitrilase, nitroreductases and peroxidases degrading the organic contaminants [30]. Recently, numerous works have reported that different plant species and varieties are able to be used for phytoremediation of organic contaminants. Most of plant used belong to ornamental woody and herbaceous species [31]. Particularly, the utilization of different plant species of Asteraceae family, potential and suitable candidates, for phytoremediation of organic in urban areas was well quoted in the review presented by [32].
\nOver recent years, the number of works in phytoremediation for organic contaminants has intensely increased with many encouraging results that have emerged regarding the capacities of several plants to degrade specific organic contaminants. To make phytoremediation for organic compounds successful, it is fundamental to understand (1) the type of soil to be treated, (2) the concentration and the fate of each organic pollutants and (3) the relations between the physical, chemical and biological parameters. Urban soils are known to have particular characteristics that have mentioned above, therefore the application of this technology in urban polluted soils remains a daunting challenge for scientists. An exploratory bibliographic research on the Web of Science from 2000 to 2020 show that a few works use greenery to eliminate the organic pollutants in urban context since its application can be limited by many factors including climate and anthropogenic modifications of the soil (e.g. impacts on soils by urban-rural temperature contrast also known as urban heat islands) [33].
\nThe urban context is very particular with regard to its location, spatial heterogeneity, pollution and usage. Even if urban soils are not intended to be reclaimed, there is still a risk to the health of the local population. It is for this reason that it is necessary to rehabilitate these soils. Many studies present the evidence results in utilization of different ornamental plant species for phytoremediation (e.g. family Asteraceae) can survive under such adverse urban conditions. In situations where the city budgets are limited and no alternative treatment can be carried out, the use of phytoremediated-plants could be affordable, sufficient, economically and community acceptable. Thus, plants play also a significant role in preservation of green spaces through enforcement of environmentally sustainable city planning. This application presents wealth of opportunities for city designers of urban landscapes and a good compromise to enhance urban diversity using phytoremediation in association with water infrastructures and open space on multiple scales. Phytoremediation seems to be a promising technique but there are still many challenges, especially in an urban context. Indeed, the use of this technique is long (several decades) and restricted. Phytoremediation is thus limited by the area explored by plant roots and the low growth and low biomass produced. Moreover, this biomass cannot be used as compost because it is considered as contaminated waste. It is therefore necessary to select the right plant, adapted to urban soils, non-invasive in order not to alter the floristic diversity and capable of mobilizing metals even if they are not bioavailable. Thus, for each urban soil, a risk assessment should be carried out to protect local biodiversity before introducing alien species, but also a study should be carried out to better understand the interaction between the factors in the rhizosphere (metals/soil/microorganisms/plant roots).
\nUrban soils are increasingly being used for urban agriculture, either for private use or for small-scale local production. Thus, one of the big challenges is to cultivate while respecting food security and human health but there is a lack of data. To remediate to its problem, more and more works were focused on the combination of phytoremediation and food production [34]. At present, there are no large-scale studies, and most of this work reports on experiments with crop/phytoremediating plants combinations. There is always the problem of the biomass produced, can it be consumed? Can it be used as compost? Legislation in all countries is very vague or non-existent and needs to be strengthened. Research needs to be further continued to overcome these challenges of establishing food production on urban soils by carrying out studies on the translocation of pollutants in plants and their bioaccumulations, eco-toxicological risk assessment and soil legislation.
\nIn spite of the fact that phytoremediation has a great of advantages in comparison to other technologies, it has also some limitations. The process of the phytoremediation is very slow from a few months to several years. The most of the plant used for phytoremediation have often small aboveground biomass and slow growth rate, and shallow root system, therefore very limits for their application in large-scale operations. Also, the low concentration of contaminants in form bioavailability in soils cause a low ability of contaminant absorption by plants.
\nTo improve these limitations, one alternative that we will mention in this chapter is the use of (1) specific microorganisms such as fungi and bacteria, (2) earthworms, considered as ‘ecosystem engineers’ of soil, and (3) amendment such as biochar. All these complementary methods will permit to increase the growth of plants, biotic and abiotic stress tolerance and all the processes associated, such as mineral nutrient absorption, roots exudation and rhizosphere microbial activities, will be improve the process of the phytoremediation.
\nA fungus (plural: fungi) belongs to the group of eukaryotic organisms. These organisms forms a kingdom that is separate from the other eukaryotic life kingdoms of plants and animals. Fungi are heterotroph, since they obtain carbon and energy from organic matter. Two major functional categories of fungi are saprophytic and mycorrhizal fungi. Saprophytic fungi decompose nonliving organic matter and they are important agents in soil mineralization processes and carbon cycle. Mycorrhiza are symbiotic species associated with vascular plants. There are eight main types of mycorrhizal symbioses based on their morphology and not on a biological reality [35].
\nAccording to pollutant type (organic and inorganic), the mycorrhizal fungi will be different. Whatever the pollutants, the selection of an appropriate host plant with mycorrhizae is of primary importance to improve phytoremediation. For organic pollutants such as polycyclic aromatic hydrocarbons (PAH), endophytic fungi is preferentially used to increase the efficiency of phytoremediation [36, 37]. For example, arbuscular myccorhizal fungi (AMF), belonging to the phylum Glomeromycota, form ubiquitous mutualistic interactions with roots of 80–90% of vascular plants species. AMF is widely used to degrade PAH. The hydrocarbons remediating potential of other endophytic fungi have been reported since the last decades. Thus, Pestaliotopsis microspora associated to the Dendrobium plant species have shown an efficient degradation potential of plastic polyester polyurethane. Phomopsis liquidambari degrade efficiently PAH in Bischofia polycarpa [36]. These symbiosis between endophytic fungi and vascular plants permit an increase of plant growth and hydrocarbons biodegradation by roots and its microflora associated, an improvement of adsorption and bioaccumulation of hydrocarbons by roots [38, 39].
\nFor inorganic pollutants such as trace metals or metalloïds, some endophytic fungi, especially AMF that can increase the uptake of arsenic or other metals such as zinc, copper or lead [39]. Nevertheless, it has been shown that the most effective fungi in terms of host plant adaptation are ectomycorrhizae and ericoid mycorrhizae [35, 40, 41]. Indeed, the great development of the extraracinar mycelium allows it to explore a large volume of soil but also to store more metals and transform them into a less toxic form thanks to a wide range of enzymatic activities.
\nThe interaction mycorrhizae-plant symbiosis and inorganic pollutants has three advantages. First, fungi can tolerate a high level of metal toxicity. Second, they are able to remove inorganic pollutants from soil and water. Finally, they promote plant growth even in polluted soils.
\nIn healthy soil, bacteria represents billons of unicellular organism and thousands of different species. Bacteria play a crucial role in ecosystem service of soil such as decomposers. As a consequent, bacteria release nutrients that other organisms could not access. Nevertheless, environmental and structural characteristics of urban soil greatly influence soil microbes. Indeed, anthropogenic impacts such as organic and inorganic pollutants in technosols and in urban runoff can shift the abundance and diversity of bacterial communities [42]. For example, it has been shown that in urban soils the main phyla identified are Acidobacteria, Actinobacteria and Proteobacteria.
\nIn the rhizosphere zones, bacteria interact with plant root in form of commensalism or mutualism. These root associated beneficial bacteria that plays an important role in acquisition for nutrient, tolerance to abiotic stress and also defense against pests are referred to as the plant-growth-promoting rhizobacteria (PGPR) [43]. Therefore, PGPR have been mainly considered to use in phytoremediation in order to increase the efficiency of the phytoremediation. Recently, another bacterial type called plant growth-promoting endophytic bacteria (PGPE) which have been shown to act as PGPR are widely used in phytoremediation [44].
\nIn the phytoremediation context, the microbial mechanisms direct and indirect that can improve the efficiency of phytoremediation are differ depending the pollutant types including organic or inorganic. Generally, root assisted-bacteria are used in order to improve the adaptation of hyperaccumulator plants to suboptimal urban soil conditions (see Section 2.1, 2.2 and 2.3) and ameliorate the efficiency of phytoremediation. For inorganic pollutants including trace metals, the mechanisms employed for enhance the phytoremediation involve improvement of plant growth by increasing mineral contents, plant metal tolerance by phytohormones products, and capacity of absorption and accumulation by producing organic acid and metal-specific ligands (e.g. siderophores) [45]. We can here cite some research works on the phytoremediation of metals facilitated by soil bacteria. The bacterial species Bacillus sp. MN3-4 which is a lead-resistant bacterium enhanced phytoremediation potential of plant Alnus firma by reducing the phytotoxic effects of metals [46]. A nickel-resistant PGPB Pseudomonas sp. A3R3 increased the capacity of Ni-accumulation of Alyssum serpyllifolium plant by production of ACC deaminase and IAA, siderophore synthesis and polymer hydrolyzing enzyme [47]. Besides, many works show that the use of plant growth-promoting rhizobacteria (PGPRs) as complementary process for metal phytoremediation leads to (i) higher plant growth by improving soil properties and biological activities under toxic metal stress, (ii) decrease phytotoxicity, and (iii) decrease oxidative damage to plant tissues that are exposed to high metal trace content by increasing antioxidant enzymatic systems [48, 49].
\nUnlike inorganic pollutants, for organic pollutants whose molecules contain principally carbon, the principal bacterial mechanisms when phytoremediation’s applied is related to pollutant co-metabolism and/or degradation pathways [50]. In fact, exogenous as well as endogenous bacteria have a system of co-metabolism of the organic pollutants as the sole carbon source with amino acid, lipid, fatty acids and organic acids. Alternatively, these bacteria come to colonize in the rhizosphere and benefit the production of root exudates, consisting of sugar, fatty-acid, organic acids, amino acids and other carbon-containing compounds for growth and degrade these organic pollutants [51].
\nAlthough a lot of research points out many advantages this alternative technology, to our knowledge, no work on phytoremediation of pollutants facilitated by soil bacteria in urban areas has been carried out. To apply this technique in urban context, we must take into account all the parameters, consisting of bacterium, plant species, soil composition and nutrient (see Section 2), pollutant type and concentration as well as the competition with other organisms that can limit the use of phytoremediation in the field.
\nEarthworms act as soil ecosystem engineers because of their crucial role in building galleries and in the decomposition of organic matter; therefore they play an important role in agriculture production [52, 53]. In polluted soils, various species of earthworms including Eisenia fetida, Lumbricus terrestris, Lumbricus rubellus and Aporrectodea caliginosa can survive in soils polluted with metals and even accumulate heavy metals including Cd, Pb, Cu and Zn [54]. This leads to the ideas of earthworm’s application for phytoremediation. On the one hand, earthworms can improve the soil physical and chemical properties and increase the soil fertility through an amelioration of the microbial activities. On the other hand, through their activity, earthworms increase the bioavailability of heavy metals in soils which is a primordial factor controlling the success of heavy metal phytoextraction [54–56]. In the case of mercury, for example, mercury changed from the stable crystalline iron oxide state to the mobile amorphous oxide state by earthworm’s activities [57]. In spite of their important role in the bioavailability of heavy metals allowing the improvement of phytoremediation, the majority of studies using earthworms for phytoremediation has been developed to improve the capacity of microorganisms inoculated in soils (call bioaugmentation) to establish, survive and colonize the rhizosphere. Earthworms are known to help (1) settlement of inoculated microorganism, (2) enhancement of microbial survival (e.g. by supplying nutrients) and (3) distribution of microorganisms in soil, earthworms insuring transport.
\nA summary of the mechanisms direct and indirect of earthworm’s effect on soil microorganisms and plants was presented in Figure 2.
\nMechanisms direct and indirect of earthworm’s effect on plant and microorganisms in the phytoremediation context.
Despite a large body of literature on the benefit for soil and plants by earthworm actions, the research on earthworms-assisted phytoremediation has just started on a laboratory scale with some encouraging results [55, 56]. The attention of this research topic is expanding by the time with an increasing the sum of times cited per year according to the citation report from Web of Science Core Collection between 2010 and 2020 (Figure 3). Outdoor experiments up to fields scale need to be investigated and documented.
\nCitation report of the sum of times cited per year on the topic “earthworms” and “phytoremediation” from web of sciences. This report reflects citations to source items indexes within web of science Core collection. Perform a cited reference search to include citations to items not indexed within web of science core collection.
Urban soils are often nutrient poor and polluted. They are degrading more and more quickly with the loss of organic matter and soil permeability that cause the negative impacts on soil structure with increasing in soil density due to soil compaction and other factors. To overcome these deficiencies, the addition of natural organic matter including compost has been recognized to increase the bio-physicochemical qualities of these urban soils [58–60]. Among the different composts, the application of biochar, which is a carbonaceous solid material, is used preferentially for urban soils. Biochar is derived from the pyrolysis of biomass. All cellulose, lignin and other non-carbonic materials gasify and are burned. Only pure carbon remains with approximately 40% of the carbon originally contained in biomass.
\nRather than an amendment (because it is very poor in nutrients), biochar would behave as a soil structure and perhaps as a catalyst, via mechanisms of action that are still poorly understood. The incorporation of biochar decreases the mobility and bioavailability of metals, thus decreasing their translocation in plants while improving the soil characteristics such as infiltration rate, hydraulic conductivity, porosity and therefore the water content. The growing of plants and water cycle is also improved.
\nBiochar, as a carbon-rich, stable and sustainable product, also acts as a carbon sink, which explains why it is attracting growing interest in the context of concerns about human-induced global warming. It could be one of the immediate solutions to the overall negative impact of urban and agricultural activities with the use of fossil carbon in the form of fuels, greenhouse gas emissions and tillage that degrades the carbon sink that humus constitutes.
\nNevertheless, the application of biochar presents possible negative effects. Biochar may contain toxic elements naturally present in its composition and which may lead to an increase in pollution when incorporated. This can affect living organisms and the functioning of the soil. Moreover, because of the dust formed during their application, it present a risk for human health. There is still little data on its negative impacts.
\nTo date, most of the studies has focused on the impact of compost on soil characteristics in agricultural area and relatively little data has been carried out in urban area. Future research should focus on the optimization of compost rates (quantity, depth…) in order to standardize the use of biochar on soil to minimize the bioaccessibility of pollutants and maximize soil/water relations and plants reestablishment [59].
\nThe use of the words acceptability, social acceptance or social reception gives rise to terminological debates [61]. Acceptability is indeed a term vague enough to be used frequently [61]. We can nevertheless consider the social acceptability of a project as a process of social construction born from the confrontation of the arguments of the different actors and which results in an identification of the population concerned with the values carried by the said project. Some stress the fact that this dialog often comes down to the implementation of a communication strategy intended to convince the target audience as part of a top-down conception of a project [62]. The acceptance term is sometimes preferred but can imply a form of resignation of the inhabitants compared to a project conceived in a non-concerted way ([61], according to [63]). Some therefore prefer to use the term “acceptance” [61] after [64], others prefer the term “social reception”. In fact, we can speak of acceptance of a project when it is appropriate by a population that identifies with the objectives pursued and the methods mobilized by it. This appropriation is conditioned by the perception of the project.
\nFor psychology, perception is the function that allows the body to receive, process and interpret information received which comes from the surroundings through the senses. This construction is obviously specific to the type of information, to the individual or group who receives it and to the context in which it is disseminated. Thus a project will be perceived and therefore appropriate differently according to the economic, social, historical context, according to the modalities of diffusion of the information and the nature of this one, and obviously according to the type of actors diffusing and receiving the information and their expectations.
\nIf we particularly consider phytoremediation projects, the perception by the population concerned is influenced by multiple factors: first of all, the identification of the risk associated with soil pollution and the potential benefits expected from phytoremediation [65]. This identification is closely linked to knowledge of the health risks involved. It was highlighted in a Quebec mining site, that the knowledge by all of a strong soil pollution whose effects on the health of populations are clearly highlighted, facilitates the acceptance of phytoremediation projects. In this case, the benefit is clearly identifiable and the populations are extremely favorable to a method of depollution considered as ecological.
\nHowever, if the populations of mining sites are alerted to the health risks linked to these forms of pollution [66] which is not necessarily the case in urban areas where pollution is old and associated with activities considered to be less polluting. Thus, the spreading of Parisian mud on the fields of farmers located in the immediate suburbs of Paris in the 19th century was not initially considered as a polluting activity [67]. In addition, the renewal of the population in a good number of urban regions leads to a lack of knowledge of the history of soils and associated pollution.
\nIn most cases, the esthetic and landscaping criteria has an essential role in the reception that can be given to this type of project [68]. The revegetation of soils in neighborhoods that the image is devalued by an industrial or mining past and the presence of brownfields, constitutes a benefit clearly identifiable by the population who have been living there for a long time or more recently. Revegetation is often equated with an embellishment and an improvement of the living environment from an ecological point of view.
\nThe different phytoremediation methods used, can, however, raise questions about the choice of species (sometimes non-native and poorly accepted by local residents), the fate of pollutants and the time required to obtain results [65]. Phytoextraction raises the question, for example, of the fate of plants that have absorbed a certain amount of pollutants, including trace metals, and their treatment [69].
\nGood reception of the project can be facilitated by working upstream with the inhabitants in order to make them aware of the characteristics of the different phytoremediation methods and their effects. Consultation on the landscapes desired by local residents would make it possible to consider the choice of species that can be used appreciated [61]. This work obviously requires a time of information and consultation that is added to the time necessary to obtain the first effects of the different phytoremediation methods.
\nIt is also difficult to envisage social acceptability without considering the potential economic benefits. In terms of costs, phytoremediation is a much less expensive technique than conventional techniques, however it still seems to be little applied [70]. In this regard, it should be emphasized that local communities such as companies specializing in soil remediation are often ill-informed and poorly trained or little trained in this type of alternative techniques and prefer to apply better known and better controlled methods such as excavation and backfilling of polluted areas. It seems that phytoremediation is struggling to get out of the purely scientific and experimental sphere. The time required to obtain significant results is a constraint both for development companies, local authorities and for the population. In the process of acceptability of phytotechnologies, an articulation between these different temporalities constitutes an issue to be taken up.
\nIn addition, the techniques of economic valuation of the biomass resulting from phytoremediation by the production of energy are still often experimental and little diffused and/or applied. Its transformation into energy, whether by thermodynamic processes (combustion, pyrolyse, roasting) or by biological processes (methanization), poses the problem of becoming pollutants and in particular of the trace metals contained in the biomass, in particular in the case phyto-extraction (ash after combustion, digestate after production of biogas). The acceptability of soil remediation projects through phytoremediation depends on the benefits known to society (population and decision-makers) and the value attributed to them.
\nThe social benefits attributed to phytoremediation can therefore be considered through the prism of ecosystem services. This concept, first imagined by ecologists, has been mobilized and widely publicized since the Millennium Ecosystem Assessment (2015); the objective sought was to promote the protection of ecosystems by assigning economic and social value to the services provided by them [71]. Ecosystem services can therefore be defined as the benefits provided by ecosystems to human societies. A general distinction is made between production (or supply) services, regulation services and cultural services. Despite the reservations which are made by ecologists and sociologists among others with regard to this concept and the reflections as to a “commodification of nature”, this can be useful here to consider the potential economic and social benefits of phytoremediation operations [71, 72]. These are a few lines of inquiry and not an exhaustive analysis. The purpose of phytoremediation is to reconstitute an ecosystem allowing depollution of the soil or stabilization of pollutants in the soil.
\nThe most directly perceptible benefit for the population is undoubtedly landscaped and esthetic. The revegetation of polluted sites, often fallow land can on the one hand radically modify the urban landscape and the image of districts or cities sometimes stigmatized by their industrial or mining past, and thus procure an embellishment to which the local populations are sensitive [61]. On the other hand, this revegetation can in certain conditions and ultimately provide spaces for relaxation and leisure. In this sense, these are the benefits associated with cultural services that can be highlighted.
\nThe benefit most directly sought by this type of project is obviously soil remediation. It can be clearly identified by the population, particularly in regions where health risks are known. Beyond the management of this pollution, it is also the structure and fertility of the soils that will be improved if not restored: the greater permeability of these soils is an asset to limit runoff and potential flooding in certain cases and a restoration of the water cycle more generally, including filtering and purification functions provided by vegetation [13].
\nWe should add that in the context of sustainable city projects, revegetation via phytoremediation can contribute to the objectives of reducing greenhouse gases and improving air quality, plants storing carbon in their tissues via photosynthesis. The plants introduced into phytoremediation operations, whether local or not, participate in the maintenance or dissemination of a certain diversity of flora and therefore fauna and can be integrated into larger projects for the maintenance or development of urban biodiversity. The areas benefiting from these projects can thus be associated with the construction of ecological corridors within the framework of the green and blue frames promoted in recent years at different territorial scales. Phytoremediation can therefore help to provide regulatory services for the restoration of these ecosystems in urban areas.
\nThe valorization of the biomass produced within the framework of these revegetation operations, can in certain cases and in the long term, be envisaged of different forms. Burning and pyrolizing wood products produces gas. Oil from pyrolysis can also be used in the composition of certain fuels, while ash and biochar (vegetable charcoal) can be reincorporated into the soil as fertilizers. The roasting of this woody biomass provides fuel. Non-woody plant waste subjected to anaerobic digestion allows for the production not only of gas but also of digestates; these can also be reintroduced into the soil [13]. These are therefore production or supply services which can be highlighted and fairly easily economically quantifiable.
\nThe assessment of these social and environmental amenities provided by phytoremediation projects are, however, for the most part complex to assess and account for economically, in particular regulation and cultural services. The monetary calculation of the direct or indirect services rendered could however minimize the real costs of soil rehabilitation projects and facilitate their wider implementation.
\nPhytoremediation is a plant-based technology that make us think about the potential eco-garden whom urban residents can profit the green and beautiful landscapes and easily accept it. Ecological gardens can be viewed in two ways depending on the target audience. For city managers, these gardens are installed in a sustainable way to cover polluted soils and thus limit the risks to the population. The plants that will be used are, in general, ornamental plants that will require little maintenance and will be durable over time. A list of ornamental plant species provided (see more in [31]) belonging to different plant groups: trees, shrub, and herbaceous which have a good potential phytoremediation for heavy metal are already used for remediate the polluted soils. For this purpose, the exploitation of ornamental plants could be an additional option. At the top, we raise the points that we need to take care when application of phytoremediation. We propose also that phytoremediation could be successfully exploited in urban territories; in these contexts, many herbaceous and others are suitable for planting because of their ornamental features and adaptability to inhabited areas.
\nFor the surrounding population, these ecological gardens have several roles, first of all a food production role, an educational role by promoting social cohesion. Thus, one of the big challenges is to cultivate while respecting food security and human health. Research needs to be further continued to overcome these challenges of establishing food production in combination with phytoremediation in urban areas by carrying out studies on eco-toxicological risk assessment.
\nPhytoremediation consist of different process and mechanisms such as absorption and accumulation of pollutant in plant as well as degradation. In the case of the contaminants are absorbed and accumulated in plant, risks in allotments are higher because of transfer of pollutants to the food chain [73]. Phytoremediation with degradation process maybe more suitable. In all cases, it is recommended to take precautions when you want to install eco-gardens on the polluted soils with hyper accumulator plants. High precautions has to be paid to parks, playgrounds, kindergartens and urban zones where residents come into close contact with soils. There are various species of ornamental plants in the literature, the choice of plant species depends on the climate, the tastes and traditions of each country.
\nFrom what we can see, phytoremediation is indeed an ecological and economical technology, acceptable and efficient to remediate the polluted soils. However, this technology is not actually widely applied in the urban context but it has many advantages regardless of the technique chosen or the pollutants present. Thus, the redevelopment of urban land in cities has become a priority. Since the implementation in 2006 of the draft European Directive on soil protection, which gives priority to soil diagnosis and remediation, the general objective of the European strategy has been to protect soil and guarantee its sustainable use by preventing its degradation, preserving its functions and restoring degraded soils. Despite these many improvements, legislation on these soils is either non-existent or very vague. Moreover, we have very little experience with trials of remediation of urban soils by the technique of phytoremediation. Nevertheless, the first results are promising with a stabilization of pollution, a decrease in erosion, a decrease in heat islands, and an increase in biodiversity with the implementation of ecological corridors in urban soil management. Research needs to be further continued to overcome these gaps on urban soils.
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