Sampling and Sample preparation techniques for environmental analysis

Chapter 4

Sampling and Sample preparation techniques for environmental analysis Chapter Outline 4.1 Introduction 4.2 Sampling techniques for environmental pollutants 4.2.1 Air sampling 4.2.2 Water sampling 4.2.3 Soil sampling 4.3 Sample preparation techniques for environmental analysis 4.3.1 Solid-phase extraction 4.3.2 Online solid-phase extraction 4.3.3 Solid-phase microextraction

4.1

75 76 77 77 78 79 79 81 82

4.3.4 Dispersive liquid liquid microextraction 4.3.5 Cloud point extraction 4.4 Emerging trends in sample preparation techniques 4.4.1 Molecularly imprinted materials 4.4.2 Nanomaterials-based membranes 4.4.3 Magnetic nanoparticles 4.5 Conclusion References

83 87 87 87 98 102 103 104

Introduction

Sampling and sample preparation, the analysis of the environmental sample, and evaluation of the obtained data are the main stages which must be carefully followed in environmental chemistry. Among these stages, sample preparation is the critical stage and one of the most time-consuming and challenging tasks in the processes of environmental analyses. The sampling and sample preparation processes take almost two-thirds of the total time of the environmental analysis1 (Fig. 4.1). They are also the major source of the uncertainties in the analyses.2 Therefore researchers have focused on the development of facile, fast, low-cost, efficient, selective, and environmentfriendly sample preparation techniques. The conventional sample preparation approaches such as liquid liquid extraction have some drawbacks (i.e., they are time-consuming, show low selectivity and efficiency toward the target compound/s, and have high consumption of toxic organic solvents, etc.). To overcome these disadvantages of conventional techniques, new sample preparation techniques have been Modern Environmental Analysis Techniques for Pollutants. DOI: https://doi.org/10.1016/B978-0-12-816934-6.00004-7 © 2020 Elsevier Inc. All rights reserved.

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FIGURE 4.1 The schematic representation of the percentage share of the steps carried out in the environmental analysis.

developed and successfully employed for the analysis of environmental samples.3 10 These techniques have several advantages such as having high selectivity for the target compound/s, being easily automated, low-cost, environment-friendly, and allowing the rapid processing of samples, with high reproducibility and a need of low volumes of organic toxic solvents. In this chapter we demonstrate the basic concepts and applications of the various sampling techniques and sample preparation approaches, such as solid-phase extraction (SPE), solid-phase microextraction (SPME), online solid-phase extraction (online-SPE), dispersive liquid liquid microextraction (DLLME), cloud point extraction (CPE), and modern sample preparation techniques [i.e., molecularly imprinted polymers (MIPs)-based SPE, nanomaterials-based membrane extraction, and magnetic nanoparticles (MNPs)-based SPE] for the efficient analysis of pollutants in complex environmental samples, such as from wastewater, soil, and air.

4.2

Sampling techniques for environmental pollutants

Three main stages must be followed in the analysis of environmental samples. These are sampling and sample preparation, analysis of the sample, and evaluation of the obtained results.11 The efficient sampling procedure has two steps: representative sampling and accurate measurements. Both of them are crucial and challenging. Efficient and successful sampling needs consideration of a sufficient number of environmental samples to be analyzed, a suitable location, and the representative type of the environmental sample. In this section, sampling strategies for environmental pollutants in air, water, and soil samples are described.

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4.2.1

77

Air sampling

The air is an efficient pathway for the dissemination of environmental pollutants in the world. Air sampling can be classified into two main categories, namely, active sampling and passive (diffusive) sampling. In active sampling the contaminated air is pumped through adsorbents such as cryogenic traps, activated charcoal, porous tenax, or silica gel.12 14 The pollutant in the particulate phase is retained in the filter while those present in the gas phase are adsorbed by the adsorbent material. Air sampling using adsorbent tubes packed with various adsorbents, such as silica gel, activated carbon, Carbopack B, and Tenax, has been extensively studied.15 17 Since these adsorbents exhibit different adsorption capacities toward the target pollutants because of their different functionalities and polarities, the adsorbent tubes can be tailored for the efficient adsorption and desorption of a wide range of pollutants from air samples. On the other hand, passive air sampling requires equipment which collects pollutants from the air without using a pump and thus reducting energy requirements. This approach depends on the diffusion of the target pollutant through membranes. In the literature various types of passive air samplers (i.e., XAD resins, polyurethane foam disks, and semipermeable membrane, etc.) have been reported for the sensitive detection of semivolatile organic compounds.18 20

4.2.2

Water sampling

The choosing of a water sampling approach for the analysis of pollutants in water samples depends on the nature of the water body (i.e., groundwater or surface water) in addition to other physical factors such as temperature, flow rate, and point source of the environmental pollutant. Generally, water sampling is carried out in one of two ways: grab sampling for measurements in a short time (less than 5 min) or integrated sampling that is extended over a long time (up to 8 h). Sampling of the target pollutants in water can be carried out by applying two steps21 similar to the air sampling briefly described earlier. In passive water sampling the collection of the target environmental pollutants in the adsorbents is performed. Thus the sampling process can be conducted in combination with the enrichment technique. On the contrary, target pollutants in water can also be collected and simultaneously pretreated in the online analysis mode of the analytical instrument (i.e., online gas chromatography-mass spectrometry or online liquid chromatography-mass spectrometry). Contaminated surface waters can be collected into sampling containers. For the sampling of lake water samples, various kinds of bailers have been successfully used.22 Portable samplers and cable-and-reel sampler for shallower water and for quite deep reservoirs, respectively, can be chosen for the

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sampling process. Repetitive collection of the samples contaminated with pollutants from effluent discharges and channel drainage systems is a challenging task. Automated sampling systems are chosen to overcome this problem and can be successfully applied for the collection of different water samples and the storage of these samples in refrigerated chambers. Various types of samplers (i.e., polar organic chemical integrative samplers, semipermeable membrane devices, chemcatchers, polyethylene strips, and polymers on glass) can be effectively used for passive sampling.23,24 Among these samplers, polyethylene strips are widely preferred since they are relatively cheap and show high adsorption capacity.25 The collection of the groundwater samples is mainly performed from monitoring wells and existing supply wells. The type of the sampling approach depends on the well size and the depth of the groundwater. Auto sampling systems and portable peristaltic pumps can also be successfully used for the collection of samples from groundwater.

4.2.3

Soil sampling

There are three main techniques commonly used for soil sampling. These are field-preserved based sampling using sodium bisulfate and methanol, bulk sampling using a spatula, and sealed chamber sampling. The sampling from surface soil samples can effectively be performed using spoons, spatulas, and augers.26 In general, these surface soil samples do not provide adequate information about the concentration of the target environmental pollutants due to the possible volatilization of aromatic compounds. Nevertheless, this drawback can be reduced and overcome by standard preservation techniques including sodium thiosulfate and methanol-based techniques.27 In addition, the application of these preservation approaches enables the collection of small amounts of soil samples from the samplers [i.e., well-filled, relatively large-diameter hand augers ($10 cm)]. The use of sample preservatives, such as cold water or methanol, and storing the samples at freezing temperatures using polyethylene sample bags and glass containers having a septum seal and screw cap prevent the loss of organic compounds because of volatilization after sampling process.28 In addition, the EnCore which is a disposable volumetric soil sampling device can be successfully used for holding of soil samples for up to 14 days if the sample is stored at 212 C.29 On the other hand, other sampling approaches such as thin-walled tubes, drill rig, and backhoe can also efficiently be applied for sample collection from soil. The thin-walled Shelby tube sampling approaches are usually preferred for sampling from subsurface layers of soil, especially in clays and cohesive soil samples. The thin-walled Shelby tubes are used for the collection of relatively undisturbed soils for different purposes (i.e., geotechnical analysis).

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Backhoe sampling approaches such as bracket, scoop, and direct sampling using bucket can be used for sample collection from shallow subsurface and surface soil samples. For the collection of samples from deep and shallow subsurface layers, direct push soil sampling approaches such as dual tube and macro core soil sampling equipment are effectively used. The macro core soil sampling system is applied for sampling from continuous and depth discrete subsurface soils. On the other hand, dual tube soil sampling equipment is widely applied for the collection of the samples from continuous core samples of unconsolidated materials, since cross-contamination is prevented by this system during the sampling process.29

4.3 Sample preparation techniques for environmental analysis 4.3.1

Solid-phase extraction

SPE is an efficient tool for sample preparation in environmental chemistry. SPE was first applied in the 1940s30 and the rapid progress in various SPE applications was initiated in the 1970s. It is now successfully applied in different fields of science, especially in environmental analysis. Conventional SPE materials such as silica-based,31 carbon-based,32 and clay-based33 resins were used in various SPE examples. Many adsorbents for SPE applications are now commercially on the market in different formats, such as SPE tubes and pipette tip formats, such as Oasis HLB (produced by Waters), Omix (produced by Agilent), and MonoTips (produced by GL Sciences). The basic principles of SPE are similar to liquid liquid extraction. Both methods involve the distribution of dissolved species between two phases. However, SPE involves the dispersion of the analyte between a liquid (sample medium) and a solid (adsorbent) phase instead of the two liquid phases which are not mixed together as in liquid liquid extraction. This technique allows the enrichment and purification of the analytes on a solid adsorbent through adsorption from the solution. Basically, this method involves passing a liquid through a column holding analytes such as a cartridge, resin, or a disk, and then recovering the captured analytes with a suitable solvent. A typical SPE process composed of four different stages including conditioning, sample loading, washing, and eluting is schematically demonstrated in Fig. 4.2.

4.3.1.1 Conditioning step The aim of the conditioning step is to condition the solid adsorbent in the SPE column using a suitable solvent, which is the same as the solvent of the sample. In other words, this step aims to wet and activate the chromatographic SPE adsorbent to allow an appropriate phase interface with the sample which will be applied to the SPE column. Acetonitrile (MeCN),

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FIGURE 4.2 The schematic depiction of the solid-phase extraction (SPE) process. Reproduced ´ with permission from Płotka-Wasylka, J.; Szczepanska, N.; de la Guardia, M.; Namie´snik, J. Miniaturized Solid-Phase Extraction Techniques. Trends Anal. Chem. 2015, 73, 19 38.34

methanol (MeOH), ethanol (EtOH), dichloromethane (DCM), and tetrahydrofuran are the most widely used organic solvents in the conditioning step. These solvents function in a surfactant capacity that allows the interaction of an aqueous sample having high polarity with the hydrophobic adsorbent. This conditioning step is very crucial since it ensures that the adsorbent material is wetted and the functional groups are solvated. In addition, it removes impurities that may initially be present on the solid adsorbent. In fact this step removes the air in the column and fills the cavities with solvent. The choice of conditioner depends on the nature of the solvent and the solid adsorbent. Between the treatment and sample treatment steps, the solid adsorbent should not be allowed to dry. Otherwise, the analytes do not efficiently adsorb to the column and low recovery is achieved. If the adsorbent remains dry for more than a few minutes, it must be reconditioned.

4.3.1.2 Sample loading step In the sample loading step, the sample is passed through the SPE column filled with adsorbent. Depending on the system used, sample volumes can range from 1 mL to 1 L. The sample can be sent to the column by gravity, pumping, vacuum, or by an automatic system. One of the most important issues of this step is the flow rate of the sample in the column. The importance of a sufficiently slow flow rate is related to the interaction time of the target compound/s with the SPE adsorbent in the column. The flow rate of the sample in the column should be slow enough to allow

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the efficient adsorption of the target compound/s to the adsorbent and it should be fast enough to avoid excess time. During this step the target compound/s are concentrated on the solid adsorbent in the column.

4.3.1.3 Washing step After the loading of the sample to the SPE adsorbent in the column, a washing step is required. The washing step is applied for the removal of undesired impurities from the adsorbent while allowing target compound/s to be left on the SPE adsorbent. The washing of the SPE column is commonly carried out with an appropriate solvent which has higher elution strength than the solvent in which the sample was dissolved and loaded to the SPE column. In most of the cases, the solvent which is used in the washing step is a weaker type of the solvent. 4.3.1.4 Elution step The final step of a typical SPE process is the elution of the target compound/s from the SPE adsorbent using an appropriate elution solvent. The elution step sometimes can be composed of more than one step, if retentive interactions between the functional groups exist on the SPE adsorbent and the target compound/s are disrupted. In recent years SPE technique has been successfully used for the removal of heavy metals,35 polycyclic aromatic hydrocarbons (PAHs),36 herbicides,37 pesticides,38 and industrial dye compounds39 from environmental samples. 4.3.2

Online solid-phase extraction

Online-SPE process has various advantages compared to the conventional off-line SPE approach, such as automatization and minimum sample volumes which provide better accuracy and precision, rapid elution of the sample after extraction and minimal degradation, and the use of reusable SPE columns. The application of online-SPE processes led to the design and development of fast and efficient analytical techniques by decreasing the time for sample preparation before the analysis of target compound/s. In the online-SPE process, conventional SPE stages such as conditioning, sample loading, washing, and elution steps can be carried out automatically and some analysis systems also allow the second sample to be extracted while the other sample is being analyzed.40 In addition, one of the important advantages of the online-SPE process is the reduced contamination risks of the sample to be analyzed and the elimination of the losses of target compound/s through degradation or evaporation during the sample preconcentration.41 Great sensitivity toward the target compound/s can successfully be obtained using the online-SPE approach because of the direct injection and

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analysis of the all extracted compounds from the complex sample. In contrast, the off-line SPE approach requires aliquots of the extracted sample to be pumped into the SPE column. The whole sample analysis enables a lower detection limit to be achieved with a small amount of sample. The onlineSPE approach has a low consumption of organic solvents during the analysis which leads to a reduction in the cost of the SPE process.42 In spite of these superiorities, the online-SPE process has also some drawbacks, including the use of expensive instruments and limitations in the portability of the equipment, etc. The most commonly applied extraction formats for the online-SPE approach are SPE cartridges filled with organic polymers or silica-C18 spheres. The disk-based online-SPE technique was also successfully applied for the removal of environmental pollutants.43 SPE disks provide the facile automation of the SPE process by achieving a great SPE performance by applying higher flow rates of the sample. Recently new adsorbents such as magnetic materials,44 new formats of porous carbon,45 and macroporous polymeric adsorbents46 for the application of online-SPE have been designed and prepared to develop the features of materials and to overcome the drawbacks of conventional SPE adsorbents. The online-SPE technique was successfully used for the efficient extraction of pollutants such as PAHs47,48 herbicides,49 pesticides, and phenolic compounds50 from environmental samples.

4.3.3

Solid-phase microextraction

SPME is one of the environment-friendly and powerful approaches for sample preparation in environmental chemistry. This technique was first developed by Pawliszyn and Arthur in 1990 to overcome the limitations of conventional liquid liquid extraction and SPE.51 Since then researchers have put much effort into the development and use of this technique in various applications.52 SPME, which is a type of SPE, can overcome the two main disadvantages of SPE (i.e., the requirement to use organic solvents and long extraction time). SPME has many superiorities compared to the SPE as described in the following53,54: G G G

G

G

short extraction time; small volumes of sample; facile and rapid analysis where expensive and complicated analytical tools, equipment, and devices are not needed; the reduction of the process cost by using reusable fiber-based SPME adsorbents and eliminating toxic organic solvents; the possibility of integration with various instrumental equipment such as high-performance liquid chromatography (HPLC), capillary electrophoresis, and gas chromatography (GC) in online and off-line modes.

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In the SPME process a stationary phase is coated on the surface of an extraction fiber. Therefore SPME stationary phases tend to be similar to the stationary phases of the GC technique. On the other hand, SPE stationary phases are similar to the stationary phases of the HPLC technique.16 A variety of commercially available materials, such as polydimethylsiloxane (PDMS), carbowax (CW), polyacrylate divinylbenzene (DVB), carboxen (CAR), and polyethylene glycol (PEG), can be used as stationary phases for SPME applications. The composite stationary phases, such as PDMS/CAR, CW/DVB, and PDMS/DVB, are the most extensively used materials for these SPME stationary phases.55 The amount of the adsorbed target compound/s is related to the partition coefficient between the stationary phase coated on the surface of the fiber and the sample matrix, interaction time, temperature, type and length of the fiber, volume of the sample, and the stationary phase thickness.56 The SPME process is applied in two ways, which are called “head space extraction” and “direct immersion extraction.” The head space extraction is based on the interaction of the vapor phase of the solid, liquid, or gas sample with the fiber adsorbent. In head space extraction the fiber is not in contact with the sample. The compounds in the vapor phase reach the fiber adsorbent through diffusion or the natural airflow path. In direct immersion extraction the extraction is performed by direct immersion of the SPME fiber into the sample.57 59 Schematic demonstrations of the direct immersion magnetic solid-phase extraction (MSPE) and head space MSPE processes are given in Fig. 4.3. Recently MSPE has been successfully applied for the efficient extraction of various environmental pollutants such as pesticides,61,62 herbicides,63 fungicides,64 heavy metals,65,66 and PAHs67,68 in water and soil samples.

4.3.4

Dispersive liquid liquid microextraction

DLLME is another facile, fast, and efficient microextraction approach. Razaee and colleagues reported the first application of DLLME in 2006.69 Compared to the other microextraction approaches, DLLME has gained great attention from researchers for the efficient extraction and sensitive analysis of various compounds. The DLLME process involves a ternary solvent system in which a little volume of a blend of disperser and extraction solvents is quickly added to the aqueous sample containing the target compound. Then the final mixture is shaken and a cloudy solution is formed because of the droplets forming upon the addition of the ternary solvent mixture composed of disperser and extraction solvents to the aqueous sample. The high surface area between the droplets of extraction solvent and aqueous phase enables the rapid mass transfer of the target compound/s from the sample into the extraction medium. After a centrifugation step, fine droplets are sedimented at the bottom of the tube. In the final step the sedimented layer

84

Modern Environmental Analysis Techniques for Pollutants FIGURE 4.3 The schematic demonstration of the direct immersion magnetic solid-phase extraction (MSPE) (A) and head space MSPE (B) processes. Reproduced with permission from Zaitsev, V.N.; Zui, M.F. Preconcentration by Solid-Phase Microextraction. J. Anal. Chem. 2014, 69, 715 727.60

FIGURE 4.4 The schematic demonstration of the dispersive liquid liquid microextraction process. Reproduced with permission from Ahmad, W.; Al-Sibaai, A.A.; Bashammakh, A.S.; Alwael, H.; El-Shahawi, M.S. Recent Advances in Dispersive Liquid-Liquid Microextraction for Pesticide Analysis. Trends Anal. Chem. 2015, 72, 181 192.70

can be easily collected with a microsyringe for further analysis. The demonstration of the dispersive liquid liquid microextraction process is schematically shown in Fig. 4.4.

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Since the first report of the DLLME approach it has become a powerful and popular microextraction technique because of its several advantages, such as its enhanced enrichment factors, it is a rapid, facile process, and it has a low consumption of solvents.71,72 In the DLLME process different key parameters that effect the efficiency of the extraction are the type and volume of the disperser and extraction solvents, pH, centrifugation and extraction time, and the volume of the sample. The careful optimization of these crucial factors is needed to achieve high efficiency for the extraction process. The most crucial step of the DLLME process is choosing a suitable extraction solvent with consideration of the various requirements such as solvent density, high extraction capability of the target compounds, and solubility behavior in water. The chosen extraction solvent should be immiscible in an aqueous medium and form droplets in the water. The most commonly used organic extraction solvents in the DLLME process are tetrachloroethylene (C2Cl4),73 carbon tetrachloride (CCl4),74 chlorobenzene (C6H5Cl),75 dichloromethane (CH2Cl2),76 and chloroform (CHCl3)28 since they have higher density than water. Ionic liquids77 such as green solvents also have been successfully used for this purpose. The octanol/water partition coefficient, Kow, and the volume of the extraction solvent are other parameters that can affect the extraction efficiency. When the solvent volume increases, the achieved enrichment factor decreases.78 On the other hand, the type, volume, and miscibility behavior of the disperser solvent in water and extraction solvent are other crucial factors which should be considered. The cloudy solution phase cannot be formed at low volumes of the disperser solvent while increasing the dispenser solvent volume reduces the efficiency of the extraction process because of the increase in the solubility of the target compounds in water.79 The most extensively used disperser solvents in the DLLME process are ethanol (C2H5OH), acetone (C3H6O), acetonitrile (C2H3N), and methanol (CH3OH) since they are low-cost solvents and show low toxicity The salt concentration and a medium pH are also crucial factors that influence the efficiency of the DLLME process. The pH and salt concentration should be carefully considered and optimized. The times of the centrifugation and extraction process are also key factors that need to be considered. Extraction process time is defined as the time between the injection of the solvent mixture, composed of the extraction and disperser solvents, and centrifugation. The centrifugation step is crucial for the separation of phases and usually takes 5 10 min. A longer centrifugation time leads to the dissolution of the phase separation.80 Table 4.1 shows some examples of the DLLME-based approaches for the removal of various environmental pollutants.

TABLE 4.1 Some examples of dispersive liquid liquid microextraction (DLLME)-based approaches for the removal of various environmental pollutants. Target environmental pollutant

Extraction solvent

Disperser solvent

Sample

References

Organophosphates

Chlorobenzene

Acetone

Water

[81]

Organophosphates

Carbon tetrachloride

Acetone

Water

[82]

Triazines

Chlorobenzene

Acetone

Water

[83]

Triazines

Toluene

Acetone

Water

[84]

Organosulfurs

Carbon tetrachloride

Methanol

Water

[85]

Sulfonylureas

Chlorobenzene

Acetone

Soil

[86]

Organophosphorous

Toluene

Acetonitrile

Soil

[87]

Pesticides

Carbon tetrachloride

Acetonitrile

Soil

[88]

Pesticides

Dichlorobenzene:monochlorobenzene (1:1, V/V)

Acetonitrile

Water

[89]

Pesticides

Monochlorobenzene:chloroform (1:1, V/V)

Acetone:acetonitrile (1:1, V/V)

Water

[90]

Organochlorines

Dodecanol

Acetone

Water

[91]

Organochlorines

Carbon disulfide

Acetone

Water

[92]

Pentachlorophenol

Tetrachloroethylene

Acetone

Water

[93]

Bisphenol A (BPA)

Chloroform

Acetone

Water

[94]

Carbamates

Toluene

Acetonitrile

Water

[95]

Triazoles

Tetrachloroethane

Methanol

Water

[96]

Phenylurea herbicides

Dichloromethane

Tetrahydrofuran

Water

[97]

Estrone and 17β-estradiol

Tetrachloroethane

Methanol

Water

[98]

Parabens

Chloroform

Ethanol

Water

[99]

Sulfonamides

Chlorobenzene

Dimethyl sulfoxide

Water

[100]

Sulfonamides and quinolones

Chloroform

Acetonitrile

Water

[101]

Pyrethroid insecticides

1-Dodecanol

Methanol

Water

[102]

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FIGURE 4.5 Formation of micelles in excess critical micelle concentrations and the preconcentration of analyte using the cloud point extraction (CPE) procedure. Reproduced with permission from Melnyk, A.; Namie´snik, J.; Wolska, L. Theory and Recent Applications of CoacervateBased Extraction Techniques. Trends Anal. Chem. 2015, 71, 282 292.110

4.3.5

Cloud point extraction

CPE is another approach for the separation, extraction, and preconcentration of the pollutants from environmental samples.103,104 The CPE process is simple, low-cost, and environment-friendly. It reduces solvent consumption and extraction time and also provides high enrichment factors for analytes.105 108 It was first developed by Watanabe and Tanaka.109 In the CPE technique an aqueous surfactant solution is separated into two different phases as a result of the formation of micelles by changing the conditions such as ionic strength, temperature, pH, extraction time, and pressure. The surfactant-rich phase contains the analyte with a small amount of water and the water-rich phase contains a low concentration of the surfactant. Two phases can be separated by centrifugation. Fig. 4.5 shows the schematic depiction of the formation of micelles in excess critical micelle concentrations and the preconcentration of analyte using the CPE procedure. Metal nanoparticles play an important role as carriers for the analyte transfer to the surfactant-rich phase and also enhance the effectiveness of micelle systems. Thus metal nanoparticles can efficiently be used in the CPE procedure for analyte preconcentration.110 113 Table 4.2 shows the recent examples of various techniques for the extraction of environmental pollutants.

4.4 4.4.1

Emerging trends in sample preparation techniques Molecularly imprinted materials

MIPs are tailor-made materials bearing selective recognition sites with great binding affinity toward the target compound. In the synthesis procedure for the selective MIPs, the polymerization of suitable functional

TABLE 4.2 The recent examples of various techniques for the extraction of environmental pollutants. Extraction technique

Adsorbent

Environmental pollutant

Sample

References

Solid-phase extraction (SPE)

Magnetic carbon nanotubes having nano-SiO2 modified with octadecyl functional groups

Sulfonylurea pesticides and neonicotinoids

Water

[114]

SPE

Magnetic Fe3O4 nanoparticles-based-metal/ organic framework

Heterocyclic pesticides (carbendazim, fenpyroximate, triadimefon, and chlorfenapyr)

Water

[115]

SPE

Amberlite XAD-2000

Pb(II) ions

Water

[116]

SPE

Magnetic metal/organic framework functionalized with graphene oxide (GO)

Triazole pesticides (myclobutanil, fenbuconazole, flusilazole, penconazole, and epoxiconazole)

Water

[117]

SPE

Polyamide nanofibers

Bisphenol A (BPA)

River water

[118]

SPE

MgO microbeads functionalized with phenyltrichlorosilane

Dioxin-like polycyclic aromatic hydrocarbons

Soil

[119]

SPE

Activated alumina

Polychlorinated dibenzofuran, dioxinlike polychlorinatedbiphenyl, and polychlorinated dibenzo-p-dioxins

Sediment and soil

[120]

SPE

Mesoporous organosilica having bis(3triethoxysilylpropyl)amine and (styrylmethyl) bis(triethoxysilylpropyl)ammonium chloride as cationic ligands

Phenoxy acid herbicides

River water and effluents from wastewater treatment plant

[121]

SPE

Amorphous silica waste

Zn(II), Pb(II), Cr(III), Cu(II), Ag(I), Ni(II), and Cd(II) ions

Industrial wastewater

[122]

SPE

Activated carbon

As(III), Cd(II) Cr (III), Cu(II), Fe(II), Mn(II) Ni(II), Pb(II), and Zn(II) ions

Wastewater

[123]

SPE

Magnetic Fe3O4 nanoparticles-based multiwalled carbon nanotubes (MWCNTs) composites

Polycyclic aromatic hydrocarbons

Industrial wastewater

[124]

SPE

Magnetic Fe3O4 nanoparticles-based mesoporous silica bearing phenyl groups

Polycyclic aromatic hydrocarbons

Soil

[125]

SPE

C18 cartridges

Short-chain chlorinated paraffins

Water

[126]

SPE

Magnetic chitosan/GO nanocomposite

Phenylurea herbicides (linuron, monuron, and isoproturon)

River water

[127]

SPME

Poly (4-vinylpyridineco-ethylene glycol dimethacrylate) fiber having graphene

Phenoxyacetic acid herbicides

Lake water, river water, and wastewater

[128]

Solid-phase microextraction (SPME)

Commercial SPME fibers (polydimethylsiloxane-divinylbenzene, divinylbenzenecarboxenpolydimethylsiloxane, polydimethylsiloxane, polyacrylate, polyethylene glycol, and carboxenpolydimethylsiloxane)

Hydrazine

Industrial wastewater

[129]

SPME

GO functionalized with magnetic chitosan

Polycyclic aromatic hydrocarbons

River water

[130]

SPME

Aerogel composed of melamine and formaldehyde

Polycyclic aromatic hydrocarbons

Water

[131]

SPME

Commercial polypropylene porous hollow fibers (Accurel PP S6/2)

Polycyclic aromatic hydrocarbons

Seawater

[132] (Continued )

TABLE 4.2 (Continued) SPME

Silica modified with ionic liquids

Organophosphate pesticides (phoxim, phosmet, triazophos, and parathionmethyl)

Tap water, river water, and well water

[133]

SPME

Magnetic Fe3O4 microbeads-based metal organic framework

Pesticides including flusilazole, chlorfenapyr, fipronil, and fenpyroximate

Seawater

[134]

SPME

Carbonized hemp fiber

Acephate, thiamethoxam, methomyl, monocrotophos, acetamiprid, midocloprid, dimethoate, carbofuran, simazine, atrazine, linuron, propazine, malathion, fenhexamid, and tebufenozide pesticides

Water

[135]

SPME

TiO2 nanotubes conjugated with graphene

Carbamate pesticides (metolcarb, diethofencarb, isoprocarb, and carbaryl)

River water

[136]

SPME

Molecularly imprinted spheres

Simazine, terbutylazine cyanazine, propazine, and atrazine

Tap, surface, and groundwater

[137]

Online-SPE

Commercial SPE cartridges (HyperSep Retain PEP, Oasis HLB, HyperCarb, and Strata C18-E)

Glucocorticoids and estrogens

Industrial wastewater

[138]

Online-SPE

(1,5-Bis (2-pyridyl) 3-sulfophenylmethylene) thiocarbonohydrazide functionalized-magnetic Fe3O4 nanoparticles

As(III) and As(V)

Seawater and well water

[139]

Online-SPE

Commercial SPE columns (C18, SolEx RSLC HRP, TurboFlow Cyclone, TurboFlow Cyclone-P, and TurboFlow Cyclone MAX)

Perfluoroalkyl sulfonic acids and perfluoroalkyl carboxylic acids

Antarctic ice core samples

[140]

Online-SPE

Zeolitic imidazolate framework having carbon fiber coated with ZnO

Sudan dye

Water

[141]

Online-SPE

RP-XBridge C18 column

Veterinary antibiotics

Wastewater, groundwater, and river water

[142]

Online-SPE

Poly (4-vinyl pyridineco-ethylene dimethacrylate) monolithic SPE column

Triazoles (triadimenol, hexaconazole, and triadimefon)

Lake water, river water, and sewage water

[143]

Online-SPE

Commercial Oasis HLB SPE column

Reactive phosphorus

Seawater

[144]

Online-SPE

Commercial polydimethylsiloxane-based stir bar

Nitrophenols

Soil and water

[145]

Online-SPE

Commercial IonPac SPE column

Estrogens including estron, estriol, estradiol, diethylstilbestrol, and ethinylestradiol

River water and effluent from wastewater treatment plant

[146]

Androgens including nandrolone, testosterone, boldenone, and androstenedione Online-SPE

Commercial HyperSep column Retain-AX, HyperSepUniguard Retain-AX and HyperSep Javelin Direct-Connect SPE columns, and tailor-made SPE column filled with Oasis MAX adsorbent

Quinolones including norfloxacin, pipemidic acid, pefloxacin, orbifloxacin, lomefloxacin, cinoxacin, nalidixic acid, moxifloxacin, flumequine, enrofloxacin, ciprofloxacin, and oxolinic acid

Tap water

[147]

Online-SPE

Ion imprinted nanospheres

Hg(II) ions

Wastewater, groundwater, and river water

[148]

(Continued )

TABLE 4.2 (Continued) Online-SPE

Commercial SPE columns including PLRP-s (styrene-polydivinylbenzene), Zorbax SB-AQ, and Zorbax phenylhexyl (dimethylphenylhexylsilane)

34 different trace organic compounds (pharmaceuticals, personal care products, pesticides, and hormones)

Wastewater, groundwater, and surface water

[149]

Online-SPE

Poly(styrene-co-divinylbenzene) microbeads coated with graphene

Disperse dye compounds

Industrial wastewater

[150]

Online-SPE

Zeolite imidazolate framework-8

Chlorotetracycline, tetracycline, and oxytetracycline

Water

[151]

Online-SPE

Molecularly imprinted polymer

Sudan dyes

River water

[152]

Online-SPE

Alumina

Sulfonamide antibiotics including sulfamonomethoxine, sulfadiazine, sulfaquinoxaline, and sulfameter

Soil

[153]

Online-SPE

Anion-exchange SPE resin synthesized by using chloromethylated styrenedivinylbenzene

Cr(VI) ions

Water

[154]

Online-SPE

C18 SPE resin

Fe(II) ions

Coastal water and estuarine water

[155]

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FIGURE 4.6 The schematic depiction of the molecular imprinting technique. Reproduced with permission from Kubo, T.; Otsuka, K. Recent Progress for the Selective Pharmaceutical Analyses Using Molecularly Imprinted Adsorbents and Their Related Techniques: A Review. J. Pharm. Biomed. Anal. 2016, 130, 68 80.156

monomers with a cross-linker in the presence of the target compound, which is also called the template, is carried out. The schematic representation of a typical molecular imprinting process is shown in Fig. 4.6. Due to their excellent binding behavior toward the target compound, MIPs have found wide application in areas where high selectivity and binding affinity toward the target compound are essential (i.e., SPE, biosensor platforms, catalytic applications, etc.).157 174 MIPs are facile to design and prepare, robust at harsh operating conditions (high temperature, pH values, pressure, and organic solvents), cost-effective, and reusable artificial materials. In addition, MIPs can be successfully used as tailor-made “plastic receptors,” especially when natural receptors are not available.175 Even though SPE is a popular technique for sample clean-up and the preconcentration of the desired molecules from complex matrices, such as wastewater, river water, and soil, the conventional adsorbents which are commonly used for the SPE applications display low selectivity toward target analytes, causing the undesired binding of interfering compounds in the sample. This issue is very important, especially for the complex matrices such as blood. In this case MIPs, as selective SPE materials that show excellent selectivity and binding behavior toward the target molecule, can overcome these drawbacks. Another advantage of the imprinted materials over the traditional adsorbents for SPE resins is their robustness. MIPs are very stable under extreme process conditions such as high pressure and temperature, high and low pH values, etc. The binding of the target compound to the selective MIP is driven through various chemical interactions, such as noncovalent, polar, covalent, and hydrophobic interactions.

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FIGURE 4.7 The scanning electron microscope (SEM) image and the schematic depiction of the enrofloxacin imprinted spheres for enrofloxacin. Reproduced with permission from Benito-Pen˜a, E.; Navarro-Villoslada, F.; Carrasco, S.; Jockusch, S.; Ottaviani, M.F.; Moreno-Bondi, M.C.; Experimental Mixture Design as a Tool for the Synthesis of Antimicrobial Selective Molecularly Imprinted Monodisperse Microbeads. ACS Appl. Mater. Interfaces 2015, 7, 10966 2 10976.189

Bo¨rje Sellergren and his colleagues reported the first application of SPE based on selective MIPs.176 In their work the selective MIP was designed and synthesized for the SPE of the target drug compound pentamidine that is used for the treatment of AIDS disease. After this report on the successful use of MIPs for SPE, scientists put considerable effort into the design and synthesis of new MIPs for the selective extraction of many different compounds from various matrices.177 188 In another interesting work selective MIP spheres were designed and prepared for the efficient extraction of an antimicrobial veterinary drug enrofloxacin.50 In this report the authors chose methacrylic acid and 2-hydroxyethyl metharcylate as the functional monomer and hydrophilic comonomer, respectively (Fig. 4.7). The results confirmed that the prepared MIP spheres showed great selectivity and binding affinity toward the target drug compound enrofloxacin. The obtained Ka value was 7558 M21. Dai et al. prepared MIPs for the selective removal of a nonsteroidal antiinflammatory drug diclofenac from contaminated river water samples.190 The functional monomer 2-vinyl pyridine (2-VP) and cross-linker ethylene glycol dimethacrylate (EGDMA) were used for the preparation of diclofenac-selective MIPs. The binding behavior of the prepared MIPs toward diclofenac was compared with activated carbon and the results showed that MIPs exhibited higher binding toward diclofenac, with a binding capacity of 324.8 mg g21. The reusability of the MIPs was also investigated and MIPs maintained their high binding behavior toward diclofenac after 12 cycles without considerable loss in their binding performance. The same research group prepared a novel MIP using multitemplates for the removal of naproxen, diclofenac, ibuprofen, ketoprofen, and clofibric acid from lake water samples.191 2-VP was chosen as the functional

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monomer. The binding behavior of the imprinted polymer toward target pharmaceutical compounds was investigated in detail. The results confirmed that the prepared MIP displayed excellent selectivity and affinity for the five target compounds. The maximum binding capacities of the prepared MIP toward naproxen, diclofenac, ibuprofen, ketoprofen, and clofibric acid were 60.7, 61.3, 60.7, 48.7, and 52 μg g21, respectively. Chen and co-workers prepared magnetic MIPs toward sulfonamides and their acetylated metabolites.192 The magnetic MIPs were synthesized by using monomer methacrylic acid (MAA) and EGDMA as the functional monomer and cross-linker, respectively. The removal of four sulfonamides sulfadiazine, sulfamonomethoxine, sulfamethoxydiazine, sulfaquinoxaline, and their acetylated metabolites from lake and river water samples was successfully achieved. The maximum removal of sulfonamides was obtained within 25 min using 90 mg of magnetic MIP. In another study Zhang and co-workers developed magnetic MIPs for the separation of hesperitin from wastewater samples.193 For this purpose the functional monomer 2-VP and cross-linker EGDMA were used for the preparation of magnetic MIPs toward hesperitin. The prepared MIPs showed high selectivity for hesperitin in the presence of other competing compounds, such as apigenin, rutin, and chlorogenic acid. The maximum binding toward hesperitin was found to be 64.7 μmol g21. On the other hand, Szekely et al. also prepared MIP/organic solvent nanofiltration membrane composites for the selective removal of the pharmaceutical compound roxithromycin in the presence of 2-aminopyrimidine and N,N-dimethylaminopyridine, which are the building block and catalyst, respectively.194 In this study polybenzimidazole was used as the polymeric membrane for the preparation of MIP/membrane composite for the first time. The MIP/membrane composite showed fourfold higher flux over its corresponding nonimprinted membrane. Phenolic compounds are among the most crucial pollutants present in environmental samples such as natural water, wastewater, river, and lake water. These compounds, which exhibit high toxicity, can be generated from the production processes of various industries such as drugs, textiles, papers, dyes, and refineries.195,196 The release of the generated phenolic compounds into the environment is the main source of environmental pollution. In 2014 the Environmental Protection Agency in the United States designated phenolic compounds as priority pollutants.197 The long-term exposure to phenolic compounds may cause serious health problems such as vertigo, muscle weakness, and respiratory diseases. Thus the efficient and selective removal of these compounds from environmental samples is required. In a reported study,198 Meng et al. prepared MIPs for the efficient removal of α-estradiol from contaminated lake water samples. Selective MIPs were prepared by using the functional monomer acrylamide and crosslinker trimethylolpropane trimethacrylate. The prepared MIPs exhibited

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FIGURE 4.8 The schematic demonstration of the preparation of the molecularly imprinted polymer (MIP)-based multiwalled carbon nanotubes (MWCNTs) composite toward Bisphenol A (BPA). Reproduced with permission from Zhang, Z.; Chen, X.; Rao, W.; Chen, H.; Cai, R. Synthesis and Properties of Magnetic Molecularly Imprinted Polymers Based on Multiwalled Carbon Nanotubes for Magnetic Extraction of Bisphenol A from Water. J. Chromatogr. B 2014, 965, 190 196.199

outstanding selectivity and affinity toward α-estradiol. The reusability of the MIPs was also investigated and MIPs maintained their binding capacity for target phenolic compound α-estradiol after five cycles without significant loss in their binding performance. Zhang and co-workers developed a magnetic MIP-based multiwalled carbon nanotubes (MWCNTs) nanocomposite for the efficient SPE of Bisphenol A (BPA) from water.199 For this purpose metharcylic acid was used as the functional monomer for the preparation of the magnetic MIPbased composite toward BPA. The schematic demonstration of the preparation of MIP-based MWCNTs composite toward BPA is given in Fig. 4.8. The results indicated that the prepared magnetic MIP-based MWCNTs composite has high binding affinity and great selectivity for the target compound BPA. The obtained maximum BPA binding capacity was 49.26 μmol g21. In another study a MIP-based membrane with chitosan was prepared for the selective removal of 4-nitrophenol (4-NP) from real water samples.200 The study also aimed to design and prepare a biocompatible MIP-based material using a cheap and green biopolymer chitosan. 4-[(4-Hydroxy)phenylazo] benzenesulfonic acid, PEG, and glutaraldehyde were chosen as the ligand, porogen, and cross-linker, respectively. The imprinted membrane was successfully applied for the selective removal of 4-NP from environmental water samples. The results showed that the highest

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4-NP binding was achieved within 8 h and the maximum binding capacity was found to be 723.25 μmol g21. On the other hand, ion imprinted polymers as selective SPE adsorbents for the target ions were first introduced by Nishide and co-workers in 1976.201 Today so many ion imprinted polymers have been synthesized and successfully applied for the selective SPE of target metal ions from environmental samples. For example, the research group of Zhang reported the design and synthesis of ion imprinted magnetic nanocomposites for the selective SPE of Pb21 from environmental samples.202 The functional monomer 3-(2-aminoethylamino)propyltrimethoxysilane and cross-linker tetraethylorthosilicate were used for the synthesis of Pb21 imprinted magnetic adsorbent. The effects of different factors such as pH and sample volume on the binding of target ion were also investigated. The binding capacity of the nanocomposites for Pb21 ions was 19.61 mg g21. In another study published by Luo and co-workers,203 novel ion imprinted polymers were used for the selective separation of Pb21 ions from lake water samples. For this purpose 4-vinylbenzo-18-crown-6 and EGDMA were used as the functional monomer and cross-linker, respectively, for the preparation of ion imprinted polymer (IIP) toward Pb21 ions. The schematic demonstration of the synthesis of Pb21 imprinted polymer is shown in Fig. 4.9. The obtained results confirmed that the IIPs displayed excellent recognition ability and selectivity toward Pb21 ions in the presence of Zn21, Co21, Ni21, and Cd21 with the selectivity coefficients of 617.79, 500.56, 52.28, and 201.15 for Pb21/Zn21, Pb21/Co21, Pb21/Ni21, and Pb21/Cd21 binary systems, respectively. The maximum binding capacities of IIP and its

FIGURE 4.9 The schematic demonstration of the synthesis of Pb21 imprinted polymers. Reproduced with permission from Luo, X.; Liu, L.; Deng, F.; Luo, S. Novel Ion-Imprinted Polymer Using Crown Ether as a Functional Monomer for Selective Removal of Pb(II) Ions in Real Environmental Water Samples. J. Mater. Chem. A 2013, 1, 8280 8286.203

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corresponding nonimprinted polymers toward target Pb21 ions were 27.95 and 13.54 mg g21, respectively. Xi and colleagues synthesized ion imprinted polymers for the selective SPE of Cd21 ions from wastewater.204 For this purpose, MAA and dithizone were chosen as the functional monomer and complexing agent, respectively. The results showed that the synthesized ion imprinted polymers displayed excellent affinity toward the target Cd21 ions. The maximum Cd21 binding capacity achieved was 46.5 mg g21 and the maximum removal of Cd21 ions from wastewater was achieved in 20 min.

4.4.2

Nanomaterials-based membranes

Membrane technology is widely applied in different separation processes, such as the treatment of wastewater, gas separation, and desalination.205 213 Membrane separation is generally performed based on the selective transport of the target compound across the membrane structure.214 Nanofiltration and reverse osmosis membranes are commonly used for the treatment of wastewater samples. However, a thick separating layer restricts their water flux behavior. This drawback can be overcome by the incorporation of nanomaterials (i.e., graphene, fullerenes, carbon nanotubes, and nanoparticles) into the membrane structure. The combination of membranes and the excellent features of nanomaterials provides excellent physical and chemical stability and also high rejection of the target compound to be separated from the sample. The incorporation of carbon nanomaterials, such as graphene, carbon nanotubes, and fullerenes, into the membrane structure is commonly applied in the development of nanocomposite membranes.215 The combination of nanomaterials with the membranes not only provides high physical and chemical stability and great rejection and flux behaviors of the developed nanocomposite membranes, but also introduces various features such as catalytic and antibacterial properties.216,217 In research carried out by Nasseri et al.,218 a graphene oxide (GO)/polysulfone nanocomposite membrane was prepared for the efficient removal of BPA from water samples. For this purpose, three different membranes were prepared using the phase inversion technique. The obtained results indicated that the incorporation of GO into the membrane structure considerably increased the permeate flux of the prepared nanocomposite membranes. The maximum BPA removal was achieved by using the GO (0.4%)/polysulfone nanocomposite membrane which has the highest negative zeta potential value (210.46 mV). The optimum process conditions for BPA removal were determined to be 10.6 min, 7.5 mg L21, 1.02 bar and 5.5 for time, initial BPA concentration, pressure, and pH, respectively. Under optimum conditions the removal efficiency of the target pollutant BPA using the prepared GO (0.4%)/polysulfone membrane was obtained as 93%.

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FIGURE 4.10 The schematic demonstration of the fabrication of graphene oxide (GO)-based nanocomposite membrane. Reproduced with permission from Zhu, L.; Wang, H.; Bai, J.; Liu, J.; Zhang, Y. A Porous Graphene Composite Membrane Intercalated by Halloysite Nanotubes for Efficient Dye Desalination. Desalination 2017, 420, 145 157.219

Zhu and colleagues developed a nanocomposite membrane composed of porous reduced GO and halloysite nanotubes (HNTs) for the removal of salts and dye compounds from water samples.219 HNTs were used to increase the interlayer spacing of GO (Fig. 4.10). After characterization studies by using transmission electron microscopy, X-ray diffraction, Fourier transforms infrared spectroscopy, Raman spectroscopy, and energy dispersive spectroscopy, the prepared sandwich-like nanocomposite membrane was successfully applied for the removal of MgCl2, NaCl, MgSO4, Na2SO4, and Reactive Black 5 dye from water samples. Ho and co-workers reported the design and preparation of novel graphene oxide-multiwalled carbon nanotubes (GO-MWCNTs)-based polyvinylidene fluoride nanocomposite membrane for the treatment of palm oil mill effluent.220 The nanocomposite membrane was prepared by using in situ colloidal precipitation technique. The rejection ability of the prepared GO-MWCNTsbased nanocomposite membrane was investigated using palm oil mill effluent. The obtained results indicated that the developed nanocomposite membrane can be successfully used for the treatment of palm oil mill effluent. The rejection values of phosphorus, chemical oxygen demand, total dissolved solids, hardness, turbidity, total suspended solids, chlorine, and color were enhanced by 6.55%, 75.5%, 1.51%, 21.79%, 81.94%, 100%, 76%, and 86.3%, respectively, using GO-MWCNTs-based nanocomposite membrane compared to the control membrane without GO and MWCNTs. In another work published by Zhang et al.,221 a novel MWCNTs-GObased nanocomposite membrane was designed and prepared for the filtration of Sr21 ions from wastewater. For this purpose the preparation of GO

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membranes interlinked with MWCNTs on the surface of a polyacrylonitrile support was carried out. Then the prepared nanocomposite membrane was effectively used for the removal of Sr21 ions from wastewater. The results showed that the prepared nanocomposite membrane displayed excellent water flux behavior (four times higher) compared to the conventional membranes. The rejection value for Sr21-EDTA chelate was obtained as 93.4%. Hudaib et al. prepared MWCNTs-based polyaniline-poly(vinylidene fluoride) nanocomposite membranes for the humic acid removal from water.222 For this purpose the polymerization of aniline with various amounts of MWCNTs (in the range between 0.25 wt.% and 2.0 wt.%) was carried out by using the in situ polymerization technique. Then MWCNTs-based polyaniline-poly(vinylidene fluoride) nanocomposite membranes were prepared. The results indicated that the prepared polyaniline poly(vinylidene fluoride) nanocomposite membrane with 1.5 wt.% MWCNTs displayed the maximum permeability. In addition, the MWCNTs-based nanocomposite membrane successfully removed humic acid from water samples with a rejection value of 79%. Shahzad and co-workers reported the fabrication of MWCNTs-Al2O3based nanocomposite membranes for the effective removal of Cd21 ions from aqueous solutions.223 The effects of various parameters such as sintering temperature and initial compaction load on the water flux behavior, strength, and porosity of the MWCNTs-Al2O3-based nanocomposite membranes were investigated. In the final step, the prepared nanocomposite membranes were used for Cd21 removal from aqueous solutions in batch mode. The results confirmed that 93% of Cd21 ions in aqueous solutions were successfully removed by using the prepared nanocomposite membranes. In another interesting study a fullerene-based sulfonated polyvinyl alcohol nanocomposite membrane for the removal of Cu21 ions from wastewater was developed by Rikame et al.224 The developed fullerene-based nanocomposite membrane showed high removal performance toward Cu21 ions in wastewater and the highest removal degree was found to be 73.2%. Jin et al. reported the preparation of fullerene-based composite membranes for estrone removal from aqueous samples.225 In this research poly (2,6-dimethyl-1,4-phenylene oxide) was modified with fullerene. Two types of nanocomposite membrane were prepared by using different amounts of fullerene (2% and 10%). The results confirmed that the prepared nanocomposite membrane having 10% fullerene exhibited great binding behavior toward the target compound estrone (c.95% binding). In another study,226 Gao and colleagues developed MWCNTs/MIP-based nanocomposite membranes for the efficient separation of enoxacin from wastewater samples. In their study MWCNTs were first modified with polydopamine (pDA) and then the target compound enoxacin was imprinted into the pDA/MWCNTs structure. In the final step pDA/MWCNTs/polyvinylidene fluoride membrane was prepared by using immersion phase inversion

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FIGURE 4.11 The schematic demonstration of the preparation of multiwalled carbon nanotubes (MWCNTs)-based enoxacin imprinted nanocomposite membrane. Reproduced with permission from Gao, J.; Wu, Y.; Cui, J.; Wu, X.; Meng, M.; Li, C.; Yan, L.; Zhou, S.; Yang, L.; Yan, Y. Bioinspired Carbon Nanoted Synthesis of Multi-Walleubes Based Enoxacin-Imprinted Nanocomposite Membranes with Excellent Antifouling and Selective Separation Properties, J. Taiwan Inst. Chem. Eng. 2018, 91, 468 480.

technique. Fig. 4.11 shows the schematic demonstration of the preparation of MWCNTs-based enoxacin imprinted nanocomposite membrane. The results showed that the prepared MWCNTs/MIP-based nanocomposite membrane displayed great removal performance toward the target compound enoxacin from wastewater samples. The binding capacity of the imprinted membranes for enoxacin achieved was 31.56 mg g21. Lu and colleagues developed thermosensitive GO-based ion imprinted nanocomposite membranes for the selective separation of Eu31 ions.227 The grafting of silver nanoparticles onto the surface of nanocomposite membranes to enhance the antifouling feature was also carried out. Thermosensitive recognition and binding sites of the imprinted membranes were created by using the functional monomers acrylamide and N-isopropylacrylamide. The prepared GO-based ion imprinted nanocomposite membranes were successfully applied for the selective separation of Eu31 ions in the presence of Gd31, La31, and Sm31. The binding capacity of the prepared GO-based ion imprinted nanocomposite membranes toward Eu31 ions was obtained as 101.14 mg g21.

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Magnetic nanoparticles

MNPs are metal oxide nanoparticles that can easily be controlled by applying an external magnetic field. MNPs exhibit unique chemical, optical, chemical, thermal, electrical, and magnetic features which are very crucial and useful in various analytical stages including the extraction, clean-up, and preconcentration of the target compound/s in the sample. MNPs can efficiently be used for many applications in environmental chemistry in a variety of aspects, such as direct application without any further functionalization of their surfaces, embedding into the structure of supporting materials such as silica, or modification of their surfaces using inorganic, organic, or biochemical agents to improve their chemical and physical features. MNPs are synthesized by using various magnetic materials, such as nickel, iron, and cobalt, their oxides (i.e., Fe2O3, Fe3O4, etc.), and derivatives (i.e., CoFe2O4, MnFe2O4, etc.) due to their great magnetic features, biological suitability, and their facile synthesis compared to the other magnetic materials.228 Typically, MNPs are directly dispersed in the sample solutions to quickly extract the target compound/s since they can be readily recovered by a magnet, which overcomes the problems with the conventional approaches of using adsorbent materials, that is, time consumption and large volume of samples. Fig. 4.12 shows the schematic demonstration of the magnetic SPE process. MNPs have been successfully used for the efficient removal of pollutants from environmental samples. For example, Adlnasab and co-workers developed magnetic Fe3O4 nanoparticles-coated mesoporous MCM-41 adsorbent

FIGURE 4.12 The schematic demonstration of the magnetic solid-phase extraction (SPE) process. Reproduced with permission from Vasconcelos, I.; Fernandes, C. Magnetic Solid Phase Extraction for Determination of Drugs in Biological Matrices. Trend Anal. Chem. 2017, 89, 41 52.229

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for the efficient dispersive micro-SPE of an anionic dye Alizarin Yellow from wastewater and well water samples.230 The obtained results indicated that the synthesized magnetic adsorbent successfully removed Alizarin Yellow dye from wastewater and well water samples. The maximum adsorption capacity was found to be 121.95 mg g21. In another important study published by Faraji et al.231 methyl orange, which is an anionic dye, was successfully removed from aqueous samples by using magnetic Fe3O4 nanoparticles with a melamine/terephthaldehyde polymeric structure. The obtained results confirmed that the magnetic SPE sorbent can be efficiently used for the removal of target dye compound from environmental samples with a great binding capacity (80.6 mg g21). Jing Lan developed magnetic TiO2/Fe3O4 nanoparticles which were efficiently applied for the extraction of inorganic As(III) and As(V) ions from aqueous solutions.232 The maximum adsorption capacity values for As(III) and As(V) ions achieved were 13.1 and 10.5 mg g21, respectively. In a study conducted by Li and colleagues233 methylene blue dye was efficiently removed from aqueous samples by using magnetic Fe3O4 nanoparticles-based mesoporous silica nanoparticles coated with chitosan. The results showed that the prepared magnetic nanoadsorbent exhibited high extraction performance toward the target dye compound methylene blue. The maximum methylene blue binding capacity obtained was 43.03 mg g21. Oveisi et al. developed Fe3O4 nanoparticles functionalized with thiol groups for the magnetic extraction of Hg(II) ions from aqueous samples.234 The prepared nanoadsorbent was successfully applied for the magnetic separation of extraction of Hg(II) ions from contaminated aqueous samples. The authors achieved excellent binding capacity for the target Hg(II) ions (344.82 mg g21).

4.5

Conclusion

This chapter has presented an overview of the basic principles and applications of the various sampling techniques and sample preparation approaches for the efficient analysis of environmental pollutants in complex matrices such as water, soil, and air samples. The collection of the samples and sample preparation are critical steps which are also time-consuming and challenging tasks in the processes of environmental analyses. New trends in sample preparation techniques are the miniaturization of the sample preparation process as well as the reduction in the large volumes of toxic solvents used during the process. Herein the principles and environmental applications of the sample preparation approaches, such as SPME online-SPE, DLLME MIPs-based SPE nanomaterials-based membrane extraction, and MNPs-based SPE, have been demonstrated. The growing needs for the sensitive analysis and extraction of pollutants from environmental samples encourage continuing research into the

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design and development of suitable, fast, cheap, selective, efficient, and environment-friendly sample preparation techniques. The latest progress in this field aims to automate and miniaturize the extraction approaches to decrease and minimize the volumes of the sample and toxic organic solvents, and the preparation of more effective extraction materials that display high affinity and selectivity toward the target compound/s in the environmental samples.

References 1. Wasik, A.; Kot-Wasik, A.; Namiesnik, J. NEW Trends in Sample Preparation Techniques for the Analysis of the Residues of Pharmaceuticals in Environmental Samples. Curr. Anal. Chem 2016, 12, 280 302. 2. Ribeiro, C.; Ribeiro, A. R.; Maia, A. S.; Goncalves, V. M. F.; Tiritan, M. E. Crit. Rev. Anal. Chem. 2014, 44, 142 185. 3. Calderilla, C.; Maya, F.; Leal, L. O.; Cerda, V. Recent Advances in Flow-Based Automated Solid-Phase Extraction. Trends Anal. Chem. 2018, 108, 370 380. 4. Płotka-Wasylka, J.; Szczepanska, N.; de la Guardia, M.; Namiesnik, J. Modern Trends in Solid Phase Extraction: New Sorbent Media. Trends Anal. Chem. 2016, 77, 23 43. 5. Xu, J.; Zheng, J.; Tian, J.; Zhu, F.; Zeng, F.; Su, C.; Ouyang, G. New Materials in SolidPhase Microextraction. Trends Anal. Chem. 2013, 47, 68 83. 6. Buszewski, B.; Szultka, M. Past, Present, and Future of Solid Phase Extraction: A Review. Crit. Rev. Anal. Chem. 2012, 42, 198 213. 7. Azzouz, A.; Kailasa, S. K.; Lee, S. S.; Rascon, A. J.; Ballesteros, E.; Zhang, M.; Kim, K.H. Review of Nanomaterials as Sorbents in Solid-Phase Extraction for Environmental Samples. Trends Anal. Chem. 2018, 108, 347 369. 8. Reyes-Garce´s, N.; Gionfriddo, E.; Go´mez-R´ıos, G. A.; Alam, Md. N.; Boyacı, E.; Bojko, B.; Singh, V.; Grandy, J.; Pawliszyn, J. Advances in Solid Phase Microextraction and Perspective on Future Directions. Anal. Chem. 2018, 90, 302 360. 9. Khezeli, T.; Daneshfar, A. Development of Dispersive Micro-Solid Phase Extraction Based on Micro and Nano Sorbents. Trends Anal. Chem. 2017, 89, 99 118. 10. Wierucka, M.; Biziuk, M. Application of Magnetic Nanoparticles for Magnetic Solid-Phase Extraction in Preparing Biological, Environmental and Food Samples. Trends Anal. Chem. 2014, 59, 50 58. 11. Gilbert, R. Statistical Methods for Environmental Pollution Monitoring; Wiley: New York, 1987. 12. USEPA-TO-17. Compendium Method TO-17: Determination of Volatile Organic Compounds in Ambient Air Using Active Sampling Onto Sorbent Tubes. Compendium of Methods for the Determination of Toxic Organic Compounds in Ambient Air, 2nd ed.; US Environmental Protection Agency, 1999. 13. USEPA-TO-3. Method for the Determination of Volatile Organic Compounds in Ambient Air Using Cryogenic Preconcentration Techniques and Gas Chromatography With Flame Ionization and Electron Capture Detection; US Environmental Protection Agency, 1999. 14. USEPA-TO-15. Compendium Method TO-15: Determination of Volatile Organic Compounds (VOCs) in Ambient Air Using Specially Prepared Canisters With Subsequent Analysis by Gas Chromatography. Compendium of Methods for the Determination of Toxic Organic Compounds in Ambient Air, 2nd ed.; US Environmental Protection Agency, 1999.

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