\r\n\tIt is a relatively simple process and a standard tool in any industry. Because of the versatility of the titration techniques, nearly all aspects of society depend on various forms of titration to analyze key chemical compounds. \r\n\tThe aims of this book is to provide the reader with an up-to-date coverage of experimental and theoretical aspects related to titration techniques used in environmental, pharmaceutical, biomedical and food sciences.
",isbn:null,printIsbn:"979-953-307-X-X",pdfIsbn:null,doi:null,price:0,priceEur:0,priceUsd:0,slug:null,numberOfPages:0,isOpenForSubmission:!1,hash:"5278b500d19d2508a7c933276167d82c",bookSignature:"Associate Prof. Vu Dang Hoang",publishedDate:null,coverURL:"https://cdn.intechopen.com/books/images_new/9212.jpg",keywords:"Acid-Base, Redox, Complexometric, Potentiometric, Voltammetric, Biomedical, Amperometric, Spectrophotometric, Isothermal Titration Calorimetry, Food Applications, Conductometric, Environmental Applications",numberOfDownloads:null,numberOfWosCitations:0,numberOfCrossrefCitations:null,numberOfDimensionsCitations:null,numberOfTotalCitations:null,isAvailableForWebshopOrdering:!0,dateEndFirstStepPublish:"September 20th 2019",dateEndSecondStepPublish:"March 16th 2020",dateEndThirdStepPublish:"May 15th 2020",dateEndFourthStepPublish:"August 3rd 2020",dateEndFifthStepPublish:"October 2nd 2020",remainingDaysToSecondStep:"10 months",secondStepPassed:!0,currentStepOfPublishingProcess:5,editedByType:null,kuFlag:!1,biosketch:null,coeditorOneBiosketch:null,coeditorTwoBiosketch:null,coeditorThreeBiosketch:null,coeditorFourBiosketch:null,coeditorFiveBiosketch:null,editors:[{id:"199907",title:"Associate Prof.",name:"Vu Dang",middleName:null,surname:"Hoang",slug:"vu-dang-hoang",fullName:"Vu Dang Hoang",profilePictureURL:"https://mts.intechopen.com/storage/users/199907/images/system/199907.jpg",biography:"Vu Dang Hoang completed his doctorate in pharmaceutics at the University of Strathclyde, UK, in 2005 and conducted a postdoctoral research at the Ecole Nationale d'Ingénieurs des Techniques des Industries Agricoles et Alimentaires, France, in 2006. He has been lecturing at the Department of Analytical Chemistry and Toxicology, Hanoi University of Pharmacy, Vietnam, since 2007. He became an associate professor in the field of drug quality control in 2015. 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1. Introduction
1.1. Pull-apart basin forming at the termination of lateral faults
When a sedimentary basin forms at the termination of a lateral faults, it is known as a pull-apart basin. It is well known that tectonic basins, such as pull-apart basins, are generally formed at the termination of right-lateral, right-stepping and left-lateral, left-stepping fault systems (e.g., [1]). This is mainly caused by the formation of subsidence at the fault termination by the lateral motion of the faults. Subsidence is therefore likely to be found piled up at the termination of right lateral right-stepping and left lateral left-stepping fault systems. In contrast, uplift structures are formed at the termination of right-lateral left-stepping and left-lateral right-stepping fault systems, because the terminations are located in an area where uplift is piled up, due to the lateral motion of the fault (Figure 1). Such structures are found in many places globally, and their fundamental formation mechanisms have been numerically simulated by numerous researchers (e.g., [2, 3]).
Figure 1.
Schematic illustration of sedimentary basin and uplift at the terminations of lateral fault system. In this figure, right lateral motion was assumed to each vertical fault (pink line). Vertical displacements are normalized by the maximum value of absolute values of the total vertical displacement field, and they do not have a unit.
Katzman et al. [3] attempted to restore the subsurface structures of the Dead Sea, estimated from gravity anomalies (e.g., [4]), by means of Boundary Element Modeling (BEM), and indicated that it is necessary to assume long overlapping faults and a very high Poisson\'s ratio in order to restore the Dead Sea pull-apart basin. Rodgers [2] attempted to simulate the formation of a pull-apart basin by means of dislocation modeling (e.g., [5]), and this was probably the first study which discussed the formation of a pull-apart basin using numerical modeling.
1.2. Dislocation modeling
In general, dislocation modeling is used for the quantitative interpretation of crustal deformation caused by earthquakes and/or volcanic activity (e.g., [6, 7]). Surface or interior displacements or strains can be calculated by considering dislocations on a plane embedded in an elastic isotropic half-space (e.g., [8, 9]).
Studies on dislocation theory and its applications began with Steketee [10] and were refined by Okada [9], who derived closed analytical solutions for surface and internal deformations or strains due to shear and tensile faults, with arbitrary dip angles in a half-space. During this period, many researchers applied dislocation theory to inhomogeneous media and considered the effects of viscoelasticity and poroelasticity (e.g., [11-18]). Such basic theories and their applications to earth science have been described in many textbooks (e.g., [19-21]). In addition, the fundamental idea of dislocation theory has been applied to theory for the interpreting the gravity and potential changes due to large earthquakes (e.g., [22-24]). In particular, Okubo\'s formula [23] was applied to an interpretation of gravity changes due to the 2011 Tohoku-Oki earthquake, as observed by the Gravity Recovery And Climate Experiment (GRACE) [25], and Wang et al. [26] were successful in discussing co- and post-seismic deformation independently of GPS data.
As mentioned above, many useful solutions have been derived, although all solutions cannot be referred to as being “closed analytical solutions.” Closed analytical solutions (derived by [8, 9]) for a dislocation plane embedded in an elastic isotropic half-space are often employed for the quantitative interpretation of crustal movements, because they are very simple and are successful in explaining observational data. Consequently, some useful simulation software have been developed using Okada’s formula [9], (for example Coulomb (e.g., [27, 28])) and/or stress evaluation methods (for example ΔCFF (e.g., [29])), and the method has been applied to the interpretation of crustal movements and/or the evaluation of stress changes due to earthquakes (e.g., [30-32]).
In this study, we employ the analytical solutions of Okada [8] for the numerical simulation of sedimentary basin formation.
For a typical example of a pull-apart basin formed by dislocation, it would be appropriate to use a restoration model of Beppu Bay and Figure 1 for a numerical simulation. Beppu Bay is located at the junction between the Honshu and Ryukyu arcs, and it is formed at the western end of the Median Tectonic Line (MTL), which is the largest right-lateral tectonic line in southwestern Japan (c.f., [33]). Another right-lateral fault, the Kurume-Hiji Line (KHL: [34]), is located 30 km north of the MTL. The MTL and the KHL are arranged as a right-lateral right-stepping fault system, and the potential for producing a pull-apart basin exists. Kusumoto et al. [35] therefore applied the simple dislocation plane concept of Okada [8] to this fault system and showed that Beppu Bay was formed as a pull-apart basin by the right-lateral faulting of the MTL and KHL. In addition, they suggested that two major tectonic events (namely, the formation of half-graben caused by a north–south extension, and the formation of the pull-apart basin caused by east–west compression) occurred in this region.
In Figure 1 and in [35], a single motion of the fault was assumed on the dislocation planes. However, it is well known that active faults undergo multiple movements over geological time scales. In order to reflect this effect in the simulation, as the Okada\'s solution [8] is based on linear elasticity, we attempted to introduce the history of fault activity into the numerical model by superimposing analytical solutions for different fault parameters on a single fault. For example, if the geological evidence suggests that the active zone of a lateral fault shifted along its strike direction over time, we express its tectonic history by superimposing analytical solutions for different fault lengths (Figure 2).
Figure 2.
Illustration reflecting fault propagations in the dislocation modeling. Analytical solutions for different fault parameters are superimposed onto a single fault plane. Vertical displacements are normalized by the maximum value of absolute values of the total vertical displacement field, and they do not have a unit.
Itoh et al. [36] introduced this simulation technique while attempting to interpret topography and paleomagnetic data for the Takayama basin, central Japan. They showed that the basic structure of the Takayama basin, and changes in the declination of the thermoremanent magnetization, can be restored by considering the cumulative activity of two right-lateral faults (the Enako Fault and the Makigahora Fault) and a reverse fault (the Harayama Fault). In addition, they showed that the reverse fault can be divided into two segments that moved independently with a time lag between their active periods. Because this modeling technique can take into account the type and amount of fault motion, we can reflect the history of fault activity based on certain geological evidence, including paleomagnetic studies, in the numerical modeling, and can discuss the tectonics in detail.
This modeling technique has also been applied to the formation of pull-apart basins located in Hokkaido by Itoh et al. [37] and Tamaki et al. [38]. Tamaki et al. [38] found that a strike-slip fault motion reaching 30 km, is required to restore the distribution and volume of the Minami-Naganuma Basin located in southern central Hokkaido.
Here, we describe the disadvantages of the dislocation modeling defined using elasticity, and the solutions for the dislocation plane are given as a range of the linear elasticity. Since fracture, flow and other non-linear phenomena seen in the general solid material are not considered in the model, it is difficult to directly compare the amount of displacement between the modeled structure and the actual structure in long-time scale modeling. In general, dislocation modeling (including visco-elasticity effects) is often employed in discussions on crustal movements over a long time-scale such as on a geological time scale (e.g., [18, 39, 40]). In addition, Finite Element Modeling (FEM), Finite Difference Modeling (FDM) and Discrete Element Modeling (DEM) can simulate the formation processes of sedimentary basins or the building processes of mountains over a geological time-scale and can quantitatively discuss the mechanisms of their formation on a time axis (e.g., [41-43]).
As mentioned above, dislocation modeling defined using a range of the linear elasticity has disadvantages in the ability to directly compare the amount of displacement between the modeled structures and the actual structures. However, when we simply discuss the essential aspects of tectonics from the distribution pattern of structures caused by fault motions, dislocation modeling is a very useful tool because it provides the pattern of displacement using easy calculations.
1.3. Aims of this study
The aims of this study are to simplify the complex formation processes of sedimentary basins through numerical simulations and to show that the simplification enables us to estimate deductively which processes cause materialization. Central Hokkaido was selected as the field in which to achieve these aims, as many sedimentary basins are distributed in this area.
As will be described later in the paper, many sedimentary basins were formed from 48 to 12 Ma in central Hokkaido, and it is difficult to discuss their formation processes using only observational data because of their complex distribution both at and below the surface. In order to simplify the complex formation processes of sedimentary basins, we attempted to restore sedimentary basins using the advanced technique already mentioned, and we evaluated the fault type and the amount of movement required to form these sedimentary basins.
In the following sections, we describe the basic background and gravity anomaly in central Hokkaido, and we attempt the restoration of the sedimentary basins.
2. Basic background of central Hokkaido
2.1. Geophysical background
Hokkaido is located on the North American plate, at a junction of the Northeast Japan arc and the Kurile arc (Figure 3). Using recent GPS observations, an east-west compressive strain field has been observed in the northern part of Hokkaido, and this strain field is considered to be caused by the convergence of the Eurasia plate with the northern part of Hokkaido functioning as a part of the plate boundary (e.g., [44]).
Figure 3.
Location map of our study area. Hokkaido is located on the North American plate, at a junction of the Northeastern Japan arc and the Kurile arc. Gray dashed line indicates the old plate boundary between the Eurasian and North American Plates. Rectangular area by gray thin line indicates the study area of Itoh and Tsuru [58].
Although the present plate boundary between the North American plate and the Eurasian plate exists in the Sea of Japan, it is known that the plate boundary was located in central Hokkaido at around 13 Ma. This period of time corresponds to the stage when the uplifting of the Hidaka Mountains began (e.g., [45]). This tectonic framework is controlled by the dextral oblique collision between the Eurasian and North American Plates and the oblique subduction of the Pacific Plate beneath the Kurile Trench. It is considered that the Kurile arc migrated into the southwestward as a forearc sliver by the oblique subduction of the Pacific Plate and that the Hidaka Mountains would be formed by collision of the Kurile arc and the Northeast Japan arc (e.g., [46-48]).
Since, consequently, it is an important area for understanding characteristics and mechanism of collision zone, numerous geophysical surveys (e.g., seismic prospecting, gravity surveys, electromagnetic surveys) have been carried out around the Hidaka Mountains in order to obtain information regarding the subsurface structures and to apply such knowledge to a tectonic discussion of the Mountains and Hokkaido (e.g., [49-54]). Using these surveys, subsurface structures which indicate a collision between the Northeast Japan arc and the Kurile arc have been obtained, and have contributed to tectonic discussions. However, in contrast, geophysical studies in the sedimentary basin area in central Hokkaido are limited in number.
2.2. Geological and tectonic background
The geological characteristics in Hokkaido are that Cenozoic strata consist of island-arc-trench systems of the Northeast Japan arc and Kurile arc, and that each Cenozoic strata distributed in the Northeast Japan arc and the Kurile arc appear in the western half and eastern half area of Hokkado, respectively. This characteristic also appears in Neogene and Quaternary strata, volcanoes and their products, and topography (e.g., [41]).
Figure 4 shows the distribution of the Paleogene strata in a north-south direction in central Hokkaido. This distribution traces the old plate boundary. This N-S elongation area is included in the Ishikari-Teshio Belt that is underlain by the Cretaceous Yezo Group, and is regarded as a typical sequence in a forearc basin setting [55]. It is known that the Paleogene sedimentary strata were deposited during the early Eocene and Oligocene in almost the entire region (e.g., [56]).
Figure 4.
Distribution of the Paleogene strata. Green and blue areas indicate distribution areas of the Paleogene sedimentary layer under and on the surface, respectively. (After Kurita and Hoyanagi [56])
In the study area, sedimentary basins and sedimentary layers were formed during 48–12 Ma and have been complexly distributed. They have been divided into 5 stages according to their formation: The Ishikari stage (48–40 Ma), The Horonai stage (40–32 Ma), The Minami Naganuma stage (34–20 Ma), and The Kawabata stage (15–12 Ma). The Ishikari stage is divided into early (48–45 Ma) and late (45–40 Ma) stages. The shape of the sedimentary basin and the distribution of sedimentary layers are shown in Figure 5.
It is known that the Ishikari Group differentially subsided and was then divided into several components [57]. Based on detailed sedimentological studies, Takano and Waseda [57] also points out that the rate of subsidence accelerated during deposition of the Ishikari Group.
The Ishikari stage is the sedimentation stage of the Ishikari Group, corresponding to the Eocene and is divided into early and later stages according to the sedimentation style. Sediments in the early Ishikari stage are distributed shallowly and widely (Figure 5A). In this stage, the sedimentary basins “A”, “B” and “C” were formed (Figure 5A), and from well data their depths are estimated to be 600 m, 500 m and 1000 m, respectively. Sediments in the later Ishikari stage are distributed deeply and narrowly (Figure 5B). In this stage, the sedimentary basins named “A” and “C” were formed (Figure 5B), and from well data their depths are estimated to be 2800 m and 400 m. Itoh and Tsuru [58] identified a NNW-SSE trending deformation zone bounded by large transcurrent faults including T1 and T2 later describing from seismic reflecting data in the northern part of the Northeast Japan forearc (Figure 3) and their right lateral motions have been indicated by the clockwise rotation of Paleogene marine sediments and by paleogeographic reconstruction. Since, as already mentioned, the present study area (the western half of Hokkaido) has same Cenozoic strata distributed in the Northeast Japan arc, study area of Itoh and Tsuru [58] and our study area are geologically continuous in the Paleogene time. Consequently, it is expected that a right lateral motion of the crust was dominant.
The Horonai stage is the sedimentation stage of the Horonai Formation, the Tappu Group, the Sankebetsu Formation and the lower Magaribuchi Formation. This stage corresponds to the Eocene and the early Oligocene. In this stage, sedimentary basins “A”, “B”, “C”, “D”, “E” and “F” were formed (Figure 5C), and from well data their depths are estimated to be 3500 m, 1200 m, 1200 m, 600 m, 300 m, and 1500 m, respectively. It is expected that a right lateral motion was dominant in this stage, because right lateral motion was also dominant in the Eocene and the late Oligocene (see below).
The Minami-Naganuma stage is the sedimentation stage of the upper Magaribuchi Formation, the Minami-Naganuma Formation, the Horomui Formation, and the upper Sankebetsu Formation. This stage corresponds to the late Oligocene and the early Miocene. In this stage, sedimentary basins “B”, “D”, ”E” and “F” were formed (Figure 5D), and from well data their depths (B, E and F) are estimated to be 2000 m, 300 m and 1500 m, respectively. The maximum depth of basin “D” is unknown because of lack of the well data and/or of outcrop section of the whole Minami-Naganuma Fromation. Itoh et al. [37], Tamaki et al. [38] and Itoh and Tsuru [59] pointed out that all basins formed in the Ishikari-Teshio Belt in this stage are pull-apart basins. Tamaki et al. [38] showed that using dislocation modeling, a 30 km right-lateral strike-slip is required to restore the actual distribution and volume of the basin. Kurita and Yokoi [60] also stated that lateral faulting was dominant in forming some of the tectonic structures during the late Oligocene.
The Kawabata stage is the sedimentation stage of the Kawabata Formation, the Ukekoi Formation, the Fureoi Formation, the Kotanbetsu Formation and the Masuporo Formation. During the Neogene, Japan was affected by the opening event of the back-arc basin of the Sea of Japan. In this stage, sedimentary basins “A”, “B”, “D”, “E”, “F1” and “F2” were formed (Figure 5E), and from well data their depths are estimated to be 2000 m, 4000 m, 4000 m, 3500 m, 2000 m and 2000 m, respectively. As mentioned above, a lateral motion of the crust was dominant during the early Neogene [37, 38, 59]. Although a building of the Hidaka Mountains in around 13 Ma has been pointed out (e.g., [45]), details are unknown.
Figure 5.
Shapes of sedimentary basins in (A) early Ishikari stage (48-45 Ma), (B) late Ishikari stage (45-40 Ma), (C) Horonai stage (40–32 Ma), (D) Minami-Naganuma stage (34–20 Ma) and (E) Kawabata stage (15–12 Ma). Isopach maps of the Horonai stage and the Kawabata stage are after Association of Natural Gas Mining and Association for Offshore Petroleum Exploration [75].
3. Bouguer gravity anomaly
Numerous geological and geophysical surveys have been carried out in the Hokkaido area, and each survey has played an important role in the understanding of crustal characteristics and tectonic events in the area. In particular, seismic prospecting has proved very useful in obtaining information relating to subsurface structures. However, seismic prospecting is almost two-dimensional, and it is difficult to intuitively understand the subsurface structures as three dimensional structures, even when provided with data from more than one profile. In contrast, the characteristics of gravity anomaly maps are easy to interpret and can be used to roughly estimate three dimensional subsurface structures from the data. Figure 6 shows the Bouguer gravity anomaly map of the study area. This map is based on the gravity mesh data by Komazawa [61]. The Bouguer density of 2670 kg/m3 was employed.
Figure 6.
Bouguer gravity anomaly map. This map is based on the gravity mesh data by Komazawa [61], and the Bouguer density of 2670 kg/m3 was assumed. Contour interval is 10 mGal.
There are negative gravity anomalies in the southern and northern parts of central Hokkaido. The negative gravity anomaly in the northern part reaches -20 mGal (Figure 6 and Area I in Figure 7) and the southern negative gravity anomaly is less than -100 mGal (Figure 6 and Area III in Figure 7). The southern negative gravity anomaly located at the curved subduction zone is the lowest in the country. From seismic prospecting, it is known that this negative gravity anomaly consists of a very thick sedimentary layer (5–8 km), with a velocity of 2.5–4.8 km/s (e.g., [50]). The sedimentary layer was formed by imbrications associated with the collision process of the Northeast Japan arc and the Kurile arc (e.g., [46-48]). In contrast, there is a positive gravity anomaly in the area of the mountains, and the mountain elevations are roughly less than 2000 m. It would not be necessary to consider isostasy for the mountains, because the mountain elevations are not very high and the gravity anomaly in this area is positive.
Figure 7.
Bouguer gravity anomaly map. Gray indicates gravity low area less than 20mGal. A-A\', B-B\', C-C\' and D-D\' show gravity anomalies along each profile of four red lines shown in the Bouguer gravity anomaly map.
A flat gravity anomaly of less than 20 mGal is distributed like a belt between the northern and southern gravity anomalies (Figure 6 and Area II in Figure 7.). Figure 7 is the gravity anomaly map that the area less than 20 mGal was painted by gray. This painted area corresponds to the area where the Paleogene strata distribute under the surface (Figure 4). We show four cross section profiles (three E-W profiles, A-C, and one N-S profile, D) of the Bouguer gravity anomaly in Figure 7. From these profiles, the gravity anomalies in the region are shown to have the characteristics as follows:
Gravity anomalies in the west-east direction have a regional trend which tilts toward the east. This could indicate the regional gravity field in Hokkaido.
Gravity anomalies less than 20 mGal have a steep gradient on the east side, while those on the west side vary gently. These patterns of gravity anomalies indicate a depression structure called a “half-graben”. Since there are many confirmed lateral faults and reverse faults in this region and no normal faults, it is considered that these patterns of gravity anomalies are caused by structures formed by the activities of lateral faults and/or reverse fault.
Gravity anomalies in the north-south direction are relatively high and flat at the center of Hokkaido. It is possible that the high density of metamorphic belts near this region affect the observed gravity anomalies. Another cause to be considered could be the effect of subsurface structures such as a reduction of low density materials (e.g., a thin sedimentary layer) or an increase of high density material (e.g., uplift of the mantle).
In general, gravity anomalies are caused by spatial variations of subsurface structures, and indicate a deficiency or an excess of mass under the surface. In general, high gravity indicates the existence of a mass excess or of high density materials, and low gravity indicates the existence of a mass deficiency or of low density materials. These deficiencies or excesses, of mass can be evaluated quantitatively using Gauss\'s theorem (e.g., [62]).
ΔM=12πG∬Δg(x,y)dxdyE1
Here, g(x, y) is the gravity anomaly data given on xy mesh with a constant interval. G, π and ΔM are the universal gravitational constant, circular constant and deficiency or excess of mass, respectively. Equation (1) is described by an infinite integration and it is difficult to perform an infinite integration with actual field data. Consequently, we understand this as being an approximate calculation and perform a numerical integration within a finite area (S) as follows:
ΔM=12πG∬SΔg(x,y)dxdyE2
We applied equation (2) to three areas, I, II and III, and we attempted to estimate the magnitude of mass deficiency for the formation of a gravity anomaly less than 20 mGal in each area. In the calculations, we employed the Gauss-Legendre numerical integral formula (e.g., [63]).
As a result, mass deficiencies of 4.7×103 Gton, 8.6×102 Gton, and 1.5×104 Gton were estimated in areas I, II, and III, respectively. There are large mass deficiencies in areas I and III, where the negative gravity anomalies observed are very large and a small mass deficiency in area II. In central Hokkaido, the amount of mass deficiency is different by about two digits in both the maximum and the minimum values.
The amount of mass deficiency can be transformed into the volume (V) of sediment by the following equation, under a condition assuming an appropriate density contrast (Δρ).
V=ΔMΔρE3
As an example, when a density contrast of 300 kg/m3 is assumed, volumes of sediment of 1.6×104 km3, 2.9×103 km3 and 5×104 km3 are estimated in areas I, II and III, respectively.
As mentioned above, gravity anomaly indicates also spatial variations of subsurface structures including the location of tectonic lines and/or faults. It is well known that if there is a tectonic line or a fault with a large gap in the vertical direction, the spatial distribution of the gravity anomaly varies steeply around these structures. The variation rate of the spatial distribution of the gravity anomaly is called the “horizontal gradient of gravity anomaly”, and it is given by the first derivative (e.g., [64, 65]) or the second derivative (e.g., [4, 66]). In general, the first derivative of the gravity anomaly is more practical, because the calculation used is very simple and the geophysical and geological interpretations for the calculated results are straightforward.
We employed the first derivative of the gravity anomaly defined by the following equation (4), and calculated the horizontal gradient of the gravity anomaly (Figure 8):
[∂g(x,y)∂x]2+[∂g(x,y)∂y]2E4
Figure 8 shows the distribution of the horizontal gradient of the Bouguer gravity anomaly more than 2 mGal/km. The contour interval is 1 mGal/km. Although there are no continuous horizontal gradient anomalies within the area where the gravity anomaly is less than 20 mGal, the continuous horizontal gradient anomalies appear around this area. This may indicate that there are not tectonic lines including faults having large vertical deformation within this gravity low area less than 20 mGal and/or that gravity anomalies due to these tectonic lines are hidden by thick sediments, although faults with large vertical deformations actually exist.
Figure 8.
Distribution of the horizontal gradient of the Bouguer gravity anomalies more than 2 mGal/km. Contour interval is 1 mGal/km.
4. Restoration of sedimentary basins
In general dislocation modeling, the dislocation plane is assumed in the modeled crust by referring to the distribution of existing active faults and/or tectonic lines, and the surface deformations are calculated by assigning displacements on the plane. If the area for modeling is small, or if the tectonics and faults assumed for modeling are clear, such a modeling procedure is useful and practical (e.g., [35, 36, 38, 67]).
However, when details of the tectonics and/or the moved faults are not so clear (as in our study), the faults and their displacements for modeling are assumed experientially from characteristic distributions of target structures, by referring to more regional rough tectonics and fault distributions. The faults and their displacements (appropriately assumed) can then be considered as an initial model and can then be corrected by trial and error, so that the calculated results fit to the actual structures or their distribution pattern.
There are numerous small faults in central Hokkaido. As mentioned above, the details of tectonics and faulting in this area are unclear. It would, therefore, be impossible to attempt to model each fault for restoring the distribution of the sedimentary basins by trial and error. Consequently, in this study, we assumed that the dislocation plane used for the modeling was not a fault plane, but a typical or average plane of a fault zone. After trial and error, we defined the nine fault zones as shown in Table 1 and Figure 9, and employed them for numerical simulations. Each fault included in these fault zones is listed in Table 1 (with literature).
Figure 9.
Fault zones defined in this study. Each fault included in these fault zones is listed in Table 1 with literature.
\n\t\t
\n\t\t
\n\t\t
\n\t\t
\n\t\t
\n\t\t\t
\n\t\t\t\tNo.\n\t\t\t
\n\t\t\t
\n\t\t\t\tFault zone\n\t\t\t
\n\t\t\t
\n\t\t\t\tPreference (recognition as tectonic zone)\n\t\t\t
N/A (Most of the fault trace is in offshore area and buried with sediments.)
\n\t\t
\n\t\t
\n\t\t\t
8
\n\t\t\t
Hidaka-North (a)\n\t\t\t
\n\t\t\t
this study
\n\t\t\t
See footnote.
\n\t\t
\n\t\t
\n\t\t\t
9
\n\t\t\t
Hidaka-South (b)\n\t\t\t
\n\t\t\t
this study
\n\t\t\t
See footnote.
\n\t\t
\n\t
Table 1.
Fault zones. Definition of each fault zone, and relationship fault zone and specific faults. (a) Hidaka-North Fault Zone is collectively defined as the eastern margin of N-S serpentinite zone along the longitudinal mountainous range in northern Hokkaido. (b) Hidaka-South Fault Zone is assigned to the western margin of the area of the highest recent uplift rate in Hokkaido (i.e. Hidaka Mountains), of which tectonic and structural context is still controversial.
In the following subsections, we give the results of numerical simulations, accompanied by simple explanations. The faults moved during each stage and their fault parameters are listed in Table 2. In calculations, the total movement of each fault plane was expressed by fault motions of 1000 times, and a high Poisson’s ratio of 0.4 was assumed because of its application to modeling in the geological time scale (e.g., [3, 36-38, 68]).
\n\t\t
\n\t\t
\n\t\t
\n\t\t
\n\t\t
\n\t\t
\n\t\t
\n\t\t
\n\t\t
\n\t\t\t
\n\t\t\t\tNo.\n\t\t\t
\n\t\t\t
\n\t\t\t\tFault zone (fault type)\n\t\t\t
\n\t\t\t
\n\t\t\t\tEarly Ishikari\n\t\t\t
\n\t\t\t
\n\t\t\t\tLate Ishikari\n\t\t\t
\n\t\t\t
\n\t\t\t\tHoronai\n\t\t\t
\n\t\t\t
\n\t\t\t\tMinami Naganuma\n\t\t\t
\n\t\t\t
\n\t\t\t\tEarly Kawabata\n\t\t\t
\n\t\t\t
\n\t\t\t\tLate Kawabata\n\t\t\t
\n\t\t
\n\t\t
\n\t\t\t
1
\n\t\t\t
Horonobe (Right lateral motion)
\n\t\t\t
-
\n\t\t\t
-
\n\t\t\t
(88, 500)
\n\t\t\t
(94, 500)
\n\t\t\t
(36, 61)
\n\t\t\t
-
\n\t\t
\n\t\t
\n\t\t\t
2
\n\t\t\t
Tenpoku (Right lateral motion)
\n\t\t\t
-
\n\t\t\t
-
\n\t\t\t
(28, 24)
\n\t\t\t
(14, 500)
\n\t\t\t
(41, 32)
\n\t\t\t
-
\n\t\t
\n\t\t
\n\t\t\t
3
\n\t\t\t
Chikubetsu (Right lateral motion)
\n\t\t\t
-
\n\t\t\t
-
\n\t\t\t
-
\n\t\t\t
-
\n\t\t\t
(21, 36)
\n\t\t\t
-
\n\t\t
\n\t\t
\n\t\t\t
4
\n\t\t\t
Onishika (Right lateral motion)
\n\t\t\t
-
\n\t\t\t
(48, 150)
\n\t\t\t
(61, 63)
\n\t\t\t
-
\n\t\t\t
-
\n\t\t\t
-
\n\t\t
\n\t\t
\n\t\t\t
5
\n\t\t\t
Rumoi-Shintotsu (Right lateral motion)
\n\t\t\t
(22, 47)
\n\t\t\t
-
\n\t\t\t
(61, 94)
\n\t\t\t
(48, 78)
\n\t\t\t
(44, 73)
\n\t\t\t
-
\n\t\t
\n\t\t
\n\t\t\t
6
\n\t\t\t
T1 (Right lateral motion)
\n\t\t\t
(14, 500)
\n\t\t\t
(14, 500)
\n\t\t\t
(14, 500)
\n\t\t\t
-
\n\t\t\t
-
\n\t\t\t
-
\n\t\t
\n\t\t
\n\t\t\t
7
\n\t\t\t
T2 (Right lateral motion)
\n\t\t\t
(25, 500)
\n\t\t\t
(25, 500)
\n\t\t\t
(61, 500)
\n\t\t\t
(44, 500)
\n\t\t\t
(92, 500)
\n\t\t\t
-
\n\t\t
\n\t\t
\n\t\t\t
8
\n\t\t\t
Hidaka-North (Right lateral motion)
\n\t\t\t
(36, 500)
\n\t\t\t
(36, 500)
\n\t\t\t
(29, 500)
\n\t\t\t
-
\n\t\t\t
-
\n\t\t\t
-
\n\t\t
\n\t\t
\n\t\t\t
\n\t\t\t
Hidaka-North (Reverse motion)
\n\t\t\t
-
\n\t\t\t
-
\n\t\t\t
-
\n\t\t\t
-
\n\t\t\t
-
\n\t\t\t
(2.5, 500)
\n\t\t
\n\t\t
\n\t\t\t
9
\n\t\t\t
Hidaka-South (Reverse motion)
\n\t\t\t
-
\n\t\t\t
-
\n\t\t\t
-
\n\t\t\t
-
\n\t\t\t
-
\n\t\t\t
(2.5, 212)
\n\t\t
\n\t
Table 2.
Fault zones moved in each stage. Values in (A, B) shown in Table indicate total slip (A: km) amount assumed on the fault plane and fault initial length (B: km). Width, depth and dip angle of fault moved as right lateral fault are assumed to be 15km, 15km and π/2, respectively. Width, depth and dip angle of fault moved as reverse fault are assumed to be 17.32km, 15km and π/3, respectively.
4.1. Early Ishikari stage (48–45 Ma)
We attempted to restore the sedimentary basins formed in the early Ishikari stage, named “A”, “B” and “C” (Figure 5A). Results are shown in Figure 10A. Right lateral movements of fault zones were required, (including the T1 fault, T2 fault, the Rumoi-ShinTotsu tectonic line and the Hidaka-North fault), in order to restore these three sedimentary basins. The amount of movement of each fault was determined by trial and errors, and results are shown in Table 2 and are as follows:
T1 fault zone: 14 km
T2 fault zone: 25 km
Rumoi-ShinTotsu tectonic zone: 22 km
Hidaka-North fault zone: 36 km
From these amounts of displacement on each fault plane, it is estimated that during this tectonic stage, a horizontal movement reaching around 100 km occurred.
Figure 10.
Distribution pattern of sedimentary basins in each stage restored by the dislocation modeling. A: early Ishikari stage. B: late Ishikari stage (45-40 Ma). C: Horonai stage (40–32 Ma). D: Minami-Naganuma stage (34–20 Ma). E: early Kawabata stage (15–13 Ma). F: late Kawabata stage (13-12Ma). Vertical displacement amounts are given in m.
From geological observations it is known that sedimentary basin “C” is the biggest basin and reaches to a depth of 1000 m. In our modeling, the depth of the modeled basin reached 1400 m. Sedimentary basins, “A” and “B” reach about 600 m and 500 m depths, respectively, and both depths of restored basins (modeled basins) corresponding to these basins are 1000m as a result of dislocation modeling. Differences between the actual basin depth and the modeled basin depth, namely “the modeled basin depth–actual basin depth,” were +400 m, +400 m and +500 m for basins “C”, “A” and “B”, respectively. The amount of restored subsidence may be a little large.
Here, we assigned the right lateral motion to each fault as mentioned above, in order to restore the spatial patterns of basin distribution. If the amount of lateral motion of each fault is reduced to adjust to the depth component of each basin, it is not possible to restore the spatial distribution patterns of the basins.
4.2. Late Ishikari stage (45–40 Ma)
In the late Ishikari stage, sedimentary basins “A” and “C” (Figure 5B) were restored (Figure 10B). The right lateral movements of fault zones (including the T1 fault, T2 fault, Onishika fault and the Hidaka-North fault) were required in order to restore these two sedimentary basins. The amount of movement of each fault was determined by trial and error (see Table 2) and is as follows.
T1 fault zone: 14 km
T2 fault zone: 25 km
Onishika fault zone: 48 km
Hidaka-North fault zone: 36 km
From these amounts of displacement on each fault plane, it is estimated that during this tectonic stage, a horizontal movement reaching about 123 km occurred.
From geological observations, sedimentary basin “C” is known to be the largest basin and reaches a depth of 2800 m. The depth of the model basin in our modeling reached 1800 m. Sedimentary basin “A” reaches a depth of about 400 m, and the modeled basin corresponding to this had a depth of 500 m. The differences between the actual basin depth and the modeled basin depth were -1000 m and +100 m in basins “C” and “A”, respectively. The restored subsidence amount of basin “C” was smaller than the actual basin depth. If the lateral motions of the Hidaka-North fault zone and Onishika fault zone were increased to adjust to the depth component of basin “C”, it was not possible to restore the spatial distribution patterns of the basins.
4.3. Horonai stage (40 Ma–32 Ma)
In the Horonai stage, we attempted to restore six sedimentary basins, “A”, “B”, “C”, “D”, “E” and “F” (Figure 5C). Results are shown in Figure 10C. The right lateral movements of fault zones (including the T1 fault, T2 fault, the Rumoi-ShinTotsu tectonic line, Onishika fault, the Tenpoku fault, Horonobe fault and Hidaka-North fault) were required in order to restore these six sedimentary basins. The amount of movement of each fault was determined by trial and error and is shown in Table 2 and as follows:
T1 fault zone: 14 km
T2 fault zone: 61 km
Rumoi-ShinTotsu tectonic line zone: 61 km
Onishika fault zone: 61 km
Tenpoku fault zone: 28 km
Horonobe fault zone: 88 km
Hidaka-North fault zone: 29 km
From the amount of displacement of each fault plane, it is estimated that a horizontal movement reaching about 342 km occurred during this tectonic stage.
From geological observations, it is known that depths of the sedimentary basins “A”, “B”, “C”, “D”, “E” and “F” reach to 3500 m, 1200 m, 1200 m, 600 m, 300 m and 1500 m, respectively. In our model, depths of modeled sedimentary basins “A”, “B,” “C”, “D”, “E” and “F” reached 1000 m, 600 m, 1800 m, 1100 m, 900 m and 1000 m, respectively. The differences between the actual basin depth and the modeled basin depth were -2500 m, -600 m, +600 m, +500 m, +600 m, and -500 m in basin “A”, “B”, “C”, “D”, “E” and “F”, respectively.
4.4. Minami-Naganuma stage (34–20 Ma)
We attempted to restore sedimentary basins “B”, “D”, “E” and “F” in the Minami-Naganuma stage (Figure 5D), and the results are shown in Figure 10D. The right lateral movements of fault zones, (including the T2 fault, the Rumoi-ShinTotsu tectonic line, Tenpoku fault and the Horonobe fault), were required in order to restore these four sedimentary basins.
In this stage, Tamaki et al. [38] have restored already the Minami-Naganuma basin (corresponding to basin “B”: pull-apart basin) located in south central Hokkaido. We referred to their results and determined the amount of movement of each fault by trial and error. The amount of fault movement is shown in Table 2 and as follows:
T2 fault zone: 44 km
Rumoi-ShinTotsu tectonic zone: 48 km
Tenpoku fault zone: 14 km
Horonobe fault zone: 94 km
From the amounts of displacement on each fault plane, it is estimated that horizontal movement reaching about 200 km occurred during this tectonic stage.
From geological observations it is known that the depth of sedimentary basins “B”, “E” and “F” reached 2000 m, 300 m and 1500 m, respectively. As already mentioned, the maximum depth of basin “D” is unknown. In our model, the depths of the modeled sedimentary basins “B”, “D”, “E” and “F” reached 1200 m, 1100 m, 700 m and 1200 m, respectively. The differences between the actual basin depth and the modeled basin depth were -800 m, +400 m, and -300 m for basins “B”, “E” and “F”, respectively.
4.5. Kawabata stage (15-12 Ma)
In the Kawabata stage, we attempted to restore six sedimentary basins, “A”, “B”, “D”, “E”, “F1” and “F2” (Figure 5E), and the result is shown in Figure 10E. The right lateral movements of fault zones, (including the T2 fault, Rumoi-ShinTotsu tectonic line, Onishika-chikubetsu fault, Tenpoku fault and the Horonobe fault), were required in order to restore these six sedimentary basins. The amount of movement of each fault is determined by trial and error and is shown in Table 2 and as follows:
T2 fault zone: 98 km
Rumoi-ShinTotsu tectonic line zone: 44 km
Onishika-chikubetsu fault zone: 21 km
Tenpoku fault zone: 41 km
Horonobe fault zone: 36 km
From the amount of displacement on each fault plane, it is estimated that a horizontal movement reaching about 240 km occurred during this tectonic stage.
As described above, these lateral motions could restore the basic distribution pattern of six sedimentary basins formed in the Kawabata stage. However, the whole distribution pattern of sedimentary basins in this stage could not be restored. After repeated trial and error, it was found that the reverse motion of two fault zones, (including the Hidaka-north fault and Hidaka-south fault), is necessary to restore the whole distribution pattern of the sedimentary basins in this stage (Figure 10F). In fact, such a reverse motion is required to successfully restore the whole basin distribution pattern. The amount of reverse motion required is shown in Table 2 and as follows:
Hidaka-north fault zone: 2.5 km
Hidaka-south fault zone: 2.5 km
Information on the depth of the sedimentary basins “A”, “B”, “D”, “E”, “F1” and “F2” is obtained from geological observations, and depths are found to reach 2000 m, 4000 m, 4000 m, 3500 m, 2000 m and 2000 m. In our model, the depths of modeled sedimentary basins “A”, “B”, “D”, “E”, “F1” and “F2” reached 1100 m, 1800 m, 1600 m, 1900 m, 1300 m and 800 m. The differences between the actual basin depth and the modeled basin depth were -900 m, -2200 m, -2400 m, -1600 m, -700 m, and -1200m in basins “A”, “B”, “D”, “E”, “F1” and “F2”, respectively. Although the whole basin distribution pattern is good, the differences between the actual basin depth and the modeled basin depth are large in all the basins. If the lateral or reverse motion of each fault zone was increased to adjust the depth component of basins, it would not be possible to restore the spatial distribution patterns of the basins.
5. Discussion
As described in the previous sections within this paper, the distribution patterns of sedimentary basins restored by dislocation modeling are very similar to the actual distribution patterns of the sedimentary basins formed in each stage, although depth differences between the actual sedimentary basins and the restored sedimentary basins occurred because of the dislocation plane based on the linear elasticity. From these results, it is suggested that almost all the sedimentary basins in central Hokkaido can be explained as pull-apart basins, caused by right-lateral fault motions during the Paleogene. The results also show that sedimentary basins formed during the Kawabata stage were formed by a combination of right-lateral fault motions and reverse fault motions located at the western margin of the Hidaka Mountains.
Although we have simplified the distributions of each fault zone (Figure 9), it would be difficult for contiguous fault zones to move independently, simultaneously, as different faults, namely a reverse fault and a lateral fault, under their arrangement as shown in Figure 9. Consequently, we suggest that the Kawabata stage should be divided into two stages, namely the “early stage” and the “late stage”, from the viewpoint of the stress field or fault motion. By considering the continuity of tectonics or the stress field, it is found that the lateral movements were made in the early Kawabata stage and that the reverse movements were made in the late Kawabata stage.
From a geological viewpoint, it has been illustrated that the building of the Hidaka Mountains was caused by reverse fault motions (e.g., [45]), and the timing of this event has been considered as being during the late Miocene or around 13 Ma (e.g., [45, 69]). This geological view supports our results and ideas, and our results also support the tectonics constructed based on geological data. Hence, we suggest that the boundary of the late Kawabata stage is around 13 Ma.
In Figures, we show the total vertical displacement field calculated from the vertical displacement field in each stage (Figures 10). The vertical displacement fields shown in Figures 11 are normalized by the maximum value of absolute values of the total vertical displacement field restored by dislocation modeling. Thus, the displacement fields shown in Figures 11 do not have a unit.
Figure 11A illustrates the normalized displacement field map that the negative displacement areas are shown in gray. This shows the distribution of the subsurface sedimentary basins restored in this study, and the distribution is seen to be similar to the distribution of actual buried sedimentary basins formed during the Paleogene (Figure 4). Figure 11B is the normalized total vertical displacement pattern restored in this study. From this figure, it is found the deepest sedimentary basin restored is located at the center of central Hokkaido. In actual depth distribution, the basin “C” is not the deepest basin. However, this sedimentary basin has a depth reaching 6000 m and is large and deep basin.
Figure 11.
Total vertical displacement pattern. The displacement field was calculated by adding up the vertical displacements field restored in each stage by the dislocation modeling. A: Gray shows negative displacement areas, and indicates the distribution of the subsurface sedimentary basins restored in this study. B: Total vertical displacement pattern normalized by the maximum value of absolute values of the total vertical displacement field.
From results shown in Figures 10-11 and the discussion above, we conclude that the sedimentary basins formed from 48 to 12 Ma in central Hokkaido can be explained by the formation of pull-apart basins, due to right lateral motions (before 13 Ma), and by reverse motions of the Hidaka-North fault zone and the Hidaka-South fault zone after 13 Ma. Namely, although the right-lateral motions were predominant from 48 Ma to 13 Ma, the reverse motions were dominant in 13 Ma. This leads us to expect a significant change in the regional tectonic stress field during this stage. Although a change of the collision direction of the Northeast Japan arc and the Kurile arc could be cited as a possibility for this, a more accurate and quantitative future investigation is required.
We here reconsider the Bouguer gravity anomaly (Figure 6 and 7) and subsurface structures in viewpoint of tectonics mentioned above. As described in the section on the Bouguer gravity anomaly, gravity low area less than 20 mGal corresponds to the area where the Paleogene strata distribute under the surface. It is known that the southern negative gravity anomaly less than -100 mGal (area III in Figure 7) consists of a very thick sedimentary layer of 8 km, and the depth of the Moho discontinuity in this area is more than 30 km (e.g., [70, 71]), and that the negative gravity anomaly which reaches -20 mGal (area I in Figure 7) consists of a sedimentary layer of several kilometers thickness, and a Moho discontinuity of around 30 km in depth (e.g., [70, 71]). Consequently, we understand that the conspicuous gravity lows in areas I and III are caused by a thick sedimentary layer and a deep Moho. In contrast, the Bouguer gravity anomaly in area II is not negative, in spite of an area of subsidence of several kilometers depth. In actual fact, using receiver function analysis [71], it is reported that the depth of the Moho discontinuity in this area ranges from a depth between 26–31 km. The Moho in area II is about 6 km shallower than in areas I and III.
We made a simple subsurface structure model consisting of sedimentary layer, crust and mantle, based on information of subsurface structures mentioned above. We then calculated the gravity anomalies along a D-D\' profile with assumption density contrasts of sedimentary layer-crust and crust-mantle being -300 kg/m3 and -500 kg/m3. We employed the two dimensional Talwani\'s method [72] in our calculations.
Figure 12 shows the simple subsurface structure model and the estimated gravity anomaly along the D-D\' profile. The assumed subsurface structure model explains the Bouguer gravity anomalies very well, in spite of the model being very simple, and leads us to assume that the conspicuous subsidence at the surface would induce the crustal thinning-mantle uplift, via isostasy. Subsidence at the surface, caused by frequent lateral motions during the Paleogene, as shown and discussed in this paper, has reached to several km. In this study, right lateral motions of the crust reaching about 1000 km were required, in order to restore the sedimentary basins distributed in central Hokkaido, as shown in the previous section. Although the correct depths of sedimentary basins were not shown in our dislocation modeling because the model was based on linear elasticity, it is expected that deeper basins would be formed in the actual crust by lateral motions. Consequently, it is considered possible that conspicuous subsidence caused by a large lateral motion would induce the crustal thinning-mantle uplift. Or, since this area experienced a tension stress field over a period of about 35 million years in spite of the local stress caused by the pull-apart basin formation, this tension stress field might induce the crustal thinning-mantle uplift viscoelastically over a very long time scale. In either case, it is necessary to reconsider the estimated mass deficiency and volume of the sediment in area II from the Bouguer gravity anomalies, by correcting the effect of mantle uplift.
Figure 12.
Two-dimensional gravity modelling along D-D\' profile in Figure 7. Blue circle shows measured Bouguer gravity anomalies and red solid line shows calculated values. Bottom figure shows the density structure. Density contrasts of sedimentary layer-crust and crust-mantle were assumed to be -300 kg/m3 and -500 kg/m3, respectively.
In this study, we suggested one tectonic model to explain the distribution of sedimentary basins located in central Hokkaido and formed between 48 Ma and 12 Ma. We then discussed the characteristics of the Bouguer gravity anomalies based on the tectonic model. In future studies, we will attempt to estimate the subsurface structure more accurately, and discuss the tectonics through simulation procedures considering a more realistic behavior of the crust and mantle (e.g., FEM, FDM, DEM and others), based on the model shown in this paper.
6. Conclusion
We simply reviewed on dislocation modeling and on its applications to geological problems (including the disadvantages of the model), and make the following two points.
When discussing the essential aspects of tectonics, simply from a distribution pattern of structures caused by fault motions, the dislocation modeling was a very useful tool and should be used with an assumption of a high Poisson\'s ratio. However, it is difficult to directly compare the displacement amounts between the modeled structures and the actual structures.
It is useful to superimpose analytical solutions for different fault parameters on a single fault, in order to introduce the history of fault activity into the numerical model.
We then employed the suggested dislocation modeling technique for the restoration modeling of sedimentary basins formed from 48 Ma to 12 Ma (located in central Hokkaido, Japan), and evaluated the fault types (lateral faulting or reverse faulting). As a result it was found that:
Sedimentary basins that were formed from 48 to 12 Ma in central Hokkaido can be explained by the formation of pull-apart basins, due to right lateral motions before 13 Ma, and by reverse motions of the Hidaka-North fault zone and the Hidaka-South fault zone after 13 Ma. Although this makes us expect a significant change in the regional tectonic stress field during this stage, its source should be investigated accurately and quantitatively in the future.
The distribution pattern of sedimentary basins restored in this study is similar to the actual distribution of buried sedimentary basins formed during the Paleogene in this area.
Finally, we discovered the following two points relating to the Bouguer gravity anomaly in central Hokkaido:
A gravity low area less than 20 mGal corresponds to the area where the Paleogene strata are distributed under the surface.
The Bouguer gravity anomalies in the gravity low belt less than 20 mGal can be roughly explained by the subsurface structure model that the mantle around the center of the belt was lifted upwards. Although it is considered that the conspicuous subsidence caused by large lateral motion would induce the crustal thinning-mantle uplift, this possibility should be discussed more accurately and quantitatively in the future.
Acknowledgments
This study was partially supported by the First Bank of Toyama Scholarship foundation and a Grants-in-Aid for Scientific Research (No. 21671003). We are most grateful to Ana Pantar and Book Editors for their editorial advices and cooperation.
\n',keywords:null,chapterPDFUrl:"https://cdn.intechopen.com/pdfs/45448.pdf",chapterXML:"https://mts.intechopen.com/source/xml/45448.xml",downloadPdfUrl:"/chapter/pdf-download/45448",previewPdfUrl:"/chapter/pdf-preview/45448",totalDownloads:2211,totalViews:201,totalCrossrefCites:5,totalDimensionsCites:8,hasAltmetrics:0,dateSubmitted:"May 28th 2012",dateReviewed:"April 17th 2013",datePrePublished:null,datePublished:"August 28th 2013",dateFinished:null,readingETA:"0",abstract:null,reviewType:"peer-reviewed",bibtexUrl:"/chapter/bibtex/45448",risUrl:"/chapter/ris/45448",book:{slug:"mechanism-of-sedimentary-basin-formation-multidisciplinary-approach-on-active-plate-margins"},signatures:"Shigekazu Kusumoto, Yasuto Itoh, Osamu Takano and Machiko\nTamaki",authors:[{id:"46893",title:"Dr.",name:"Yasuto",middleName:null,surname:"Itoh",fullName:"Yasuto Itoh",slug:"yasuto-itoh",email:"yasutokov@yahoo.co.jp",position:null,institution:{name:"Osaka Prefecture University",institutionURL:null,country:{name:"Japan"}}},{id:"51974",title:"Dr.",name:"Shigekazu",middleName:null,surname:"Kusumoto",fullName:"Shigekazu Kusumoto",slug:"shigekazu-kusumoto",email:"kusu@sci.u-toyama.ac.jp",position:null,institution:null},{id:"161720",title:"Dr.",name:"Osamu",middleName:null,surname:"Takano",fullName:"Osamu Takano",slug:"osamu-takano",email:"osamu.takano@japex.co.jp",position:null,institution:null},{id:"169106",title:"Dr.",name:"Machiko",middleName:null,surname:"Tamaki",fullName:"Machiko Tamaki",slug:"machiko-tamaki",email:"tamaki_m@joe.co.jp",position:null,institution:null}],sections:[{id:"sec_1",title:"1. Introduction",level:"1"},{id:"sec_1_2",title:"1.1. Pull-apart basin forming at the termination of lateral faults",level:"2"},{id:"sec_2_2",title:"1.2. Dislocation modeling",level:"2"},{id:"sec_3_2",title:"1.3. Aims of this study",level:"2"},{id:"sec_5",title:"2. Basic background of central Hokkaido",level:"1"},{id:"sec_5_2",title:"2.1. Geophysical background",level:"2"},{id:"sec_6_2",title:"2.2. Geological and tectonic background",level:"2"},{id:"sec_8",title:"3. Bouguer gravity anomaly",level:"1"},{id:"sec_9",title:"4. Restoration of sedimentary basins",level:"1"},{id:"sec_9_2",title:"4.1. Early Ishikari stage (48–45 Ma)",level:"2"},{id:"sec_10_2",title:"4.2. Late Ishikari stage (45–40 Ma)",level:"2"},{id:"sec_11_2",title:"4.3. Horonai stage (40 Ma–32 Ma)",level:"2"},{id:"sec_12_2",title:"4.4. Minami-Naganuma stage (34–20 Ma)",level:"2"},{id:"sec_13_2",title:"4.5. Kawabata stage (15-12 Ma)",level:"2"},{id:"sec_15",title:"5. Discussion",level:"1"},{id:"sec_16",title:"6. 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(in Japanese with English summary)'}],footnotes:[],contributors:[{corresp:null,contributorFullName:"Shigekazu Kusumoto",address:null,affiliation:'
Graduate School of Science and Technology for Research, University of Toyama, Japan
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1. Introduction
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The global consumption of energy and hydrocarbon-related commodities will continue to increase as the world population increases. The three sources of energy oil, gas, and coal are still dominating over 80% of the global energy matrix. However, natural gas is considered as the bridge fuel between the fossil fuel of today and the renewable fuel of tomorrow. It is cheap, more abundant than oil, and has lower CO2 emissions compared with oil and coal. These factors place natural gas, and by extension methane, as a principal candidate for replacing petroleum as a chemical feedstock and addressing various environmental issues. Natural gas is a flammable substance obtained from oil or gas fields and coal mines. At present, the confirmed natural gas reserves have a total volume of 187 trillion metric, of which 24.8% is found in the Middle East, 30.4% in Europe and Eurasia, 8.4% in the Asia Pacific region, 7.5% in Africa, 6.8% in North America and 4.1% in Middle and South America [1, 2, 3, 4, 5]. Natural gas is typically used as a fuel for power generation and for domestic heating. In 1971, global primary energy consumption was based on 48% oil, 29% coal and 18% natural gas. However, in 2015, the consumption of 13.1 billion tonnes (oil equivalent) of fuel was based on 33% oil, 30% coal and 24% natural gas [1], reflecting a shift from oil to natural gas. This transition from oil to natural gas consumption is expected to gradually increase until 2035 [1, 2, 3].
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Natural gas resources are located in remote areas, and its utilisation is affected by high transportation costs. Therefore, conversion of natural gas to high value chemicals is the most promising solution. Methane and ethane are the main components of natural gas; they are stable and have no functional group, magnetic moment or polar distribution to facilitate chemical attacks. The C-H bonds of these light hydrocarbons are strong and require high reaction conditions to be activated.
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One of the most challenging processes in the chemical industry is the conversion of natural gas or methane to methanol, which is an important intermediate source of energy in our daily lives. Methanol can be used as a convenient energy storage material, a fuel, and a feedstock to synthesise hydrocarbons which mankind get from fossil fuel nowadays [2, 3] One of the importances of methanol comes from its direct use as a fuel or blending with gasoline to improve the octane number although it has half the volumetric energy density (15.6 MJ/L) relative to gasoline (34.2 MJ/L) and diesel (38.6 MJ/L) [4, 5, 6]. There had been 15,000 methanol-powered cars during the 1990s granted by the Environmental Protection Agency (EPA), but the use was discontinued due to an increased natural gas price [7]. Methanol is also a key feedstock for chemical manufacturing. The most major derivatives from methanol are formaldehyde, acetic acid, methyl tertiary butyl ether (MTBE) and dimethyl ether (DME). In recent years, methanol to hydrocarbons (MTH) research has been growing rapidly including methanol-to-gasoline (MTG) and methanol-to olefins (MTO) technology [8, 9, 10].
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In industries, an indirect route for the conversion of natural gas to methanol is used. In this reaction, methane is first converted to synthesis gas by steam reforming, and the synthesis gas is then converted to methanol. However, the production of syngas is an energy-intensive process, which is operated between 800 and 1000°C, and more than 25% of the feed (natural gas) has to be burned to provide the heat of reaction. The direct conversion of methane to methanol in a single step without going through the reforming step is a desired alternative to the current technology [2, 4, 5]. In spite of the fact that there are no actual plants yet for the process of direct methane to methanol (DMTM), previous experimental and theoretical works have demonstrated the feasibility of this route [2, 4, 5]. Here, this chapter will mainly focus on the recent efforts on the direct conversion of methane to oxygenates.
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2. Conventional catalytic approach to convert methane to oxygenates
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2.1 Gas phase reaction based on homogeneous radical mechanism
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This reaction is a free radical conducted under high temperature and pressure. The thermodynamic and kinetics studies identified the partial oxidation of methane as the rate limiting step due to the formation of methyl radical [7, 11]. Many studies with different oxidants have been conducted in this route. Babero et al. studied the partial oxidation of methane at 500 C temperature using nitrogen oxide as an oxidant [12]. Another study compared between oxygen and nitrogen oxide for the partial oxidation of methane in the gas phase [13]. The effect of adding small quantities of hydrocarbons such as ethane was investigated to promote the activation of methane and increase the selectivity of methanol [14]. Pressure is one of the most important factors which has a pronounced effect on the selectivity of methane oxidation. Dozens of studies have been performed in attempts to promote the selectivity toward oxygenates using high pressures and temperatures [8, 9, 15]. The results of these studies show that a conversion of 5–10% and a methanol yield of 30–40% can be achieved at a temperature of 723–773 K and pressures of 30–60 bar in the gas phase reaction. There are several works that investigated the reactor design and modifications. Zhang et al. designed a new tubular reactor based on quartz-line and stainless-steel line. The reaction was conducted at a temperature of 430–470°C and 5.0 Mpa pressure, and a high yield of methanol was obtained [9].
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The methane conversion to methanol was also conducted in the absence of catalysts at high reaction conditions. Methanol yields as high as 7–8% are obtained in the absence of catalysts operating at 350–500°C and 50 bar [10, 11, 16]. As reactor inertness is essential for obtaining good selectivity to methanol, the feed gas should be isolated from the metal wall by using quartz and Pyrex glass-lined reactors [17]. A typical experimental conversion-selectivity plot for the gas-phase partial oxidation of methane is shown in Figure 1 [18]. This plot ably demonstrates that any improvement in the direct conversion of methane to methanol must come from the enhancement of selectivity without reducing the conversion per pass. The Huels process uses cold-flame burners operating at 60 bar, with a selectivity of 71% to methanol and 14% to formaldehyde, and a recycle ratio of 200 to 1 [8].
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Figure 1.
Homogeneous gas-phase partial oxidation of methane from several studies: (1) Lott and Sliepcevich; (3) Tripathy; (4) Brockhaus; (6) Hunter; (8) Rytz and Baiker [18].
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The suggested mechanism for the direct conversion of methane to methanol via homogeneous gas phase reactions is shown in Figure 2 [19].
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Figure 2.
Schematic diagram of the methane conversion via homogeneous gas phase reaction.
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2.2 A low temperature catalytic route involving homogeneous and heterogeneous catalysis
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At moderate conditions, catalysts play an important role in the partial oxidation conversion of methane to methanol in terms of controlling the selectivity of the desired yield. Several catalysts have been investigated at 1 atm and mild temperatures.
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In homogeneous systems, in the early 1970s, it was shown that methane could be converted to methanol by Pt(II) and Pt(IV) complexes because these complexes do not oxidise CH3OH to COx [20]. Since that breakthrough, several oxidation catalysts based on Pt(II), Pd(II) and Hg(II) salts have been proven to functionalize C-H bonds [21, 22], leading to good yields of partially oxidised products (Eq. (1)). For example, [(2,2′-bipyrimidine)PtCl2] catalyses the selective oxidation of CH4 in fuming sulphuric acid to give methyl bisulphate in a 72% one-pass yield at 81% selectivity based on methane. Methyl bisulphate is then hydrolysed to methanol (Eq. (2)).
The major drawbacks of the liquid phase include not only the difficulty of separating the methanol product from the solvent but also solvents such as sulphuric acid need expensive corrosion-resistant materials and periodic regeneration of the consumed H2SO4. A new class of solid catalyst based on immobilised complexes has recently been reported for the direct low-temperature oxidation of methane to methanol [23]. This solid catalyst has a covalent triazine-based framework (CTF) with numerous accessible bipyridyl structure units, which should allow the coordination of platinum (Figure 3a and b) [23]. The performance of these new catalysts showed that the activity is maintained throughout several cycles, and selectivity for methanol formation above 75% could be reached.
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Figure 3.
(a) Bipyrimidyl Pt(II) complex used in the oxidation of methane to methyl bisulphate in concentrated sulphuric acid. (b) Covalent triazine-based framework (CTF) with numerous accessible bipyridyl structure units which are suitable to coordinate the Pt(II) complex.
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In nature, methane monooxygenase enzymes (MMO) transform CH4 to CH3OH in water under ambient conditions [11]. A number of metal complexes have been proposed to mimic the chemistry of these enzymes [11, 24, 25], but the systems which generate active oxygen species capable of converting CH4 to CH3OH are yet to be created. In contrast to organometallic CH4 activation, MMO proceeds via a different mechanism by creating a very strong oxidising di-iron species able to attack a C-H bond in CH4. An essential feature of MMO is an active site containing two iron centres [11]. Metallophthalocyanines (MPc), and more specifically iron phthalocyanines (FePc), are good catalysts for clean oxidation processes. More specifically, FePc supported in μ-oxo dimeric form (Fe-O-Fe fragment) has better catalytic properties in CH4 conversion in the presence of hydrogen peroxide as an oxidant than its monomer counterpart (FePc). The heterolytic cleavage of the O-O bond in the FeIVNFeIIIOOH complex and the formation of very strong oxidising FeIVNFeV = O species are favoured in the presence of acid by the protonation of peroxide oxygen [11, 24, 25]. A new oxidation mechanism based on the use of metal clusters to harness the ‘singlet oxene’, the most reactive form of the oxygen atom, has recently been proposed [11, 26]. In this proposal, the key to oxygen insertion is a complex containing three copper atoms, in which the atomic charges vary. By synthesising a series of ligands to complex three copper atoms, mimicking the likely structure of the active site in pMMO, facile O-atom insertion into C-C and C-H bonds has been demonstrated in a number of simple organic substrates under ambient conditions of temperature and pressure. The ligands were designed to form the proper spatial and electronic geometry to harness a ‘singlet oxene’ [11, 25, 26]. It has been shown that the activity for methanol synthesis is 5 mol (CH3OH) kg (catalyst)−1 h−1 for sMMO as a complete enzyme with NADH present and this result represents the bench-market by which MMO catalysts should be judged. However, when NADH cofactor is removed, H2O2 can be used as the terminal oxidant with the enzyme but the catalytic activity decreases to 0.076 mol (CH3OH) h−1 kg (MMOH)−1 [27].
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In heterogeneous catalytic systems, many attempts have been conducted for the oxidation of methane. In most cases, SiO2 was used as a support with different metals, and O2 as oxidant. It was claimed that [28, 29] with a similar condition, HCHO might be produced with one-pass yield from 0 to 4%. However, high one pass HCHO yields were reported in some publications, but the results were not confirmed by other groups. It is stated that the results by different researchers have always been quite different, and some of them were even contradictory to one other [25, 30]. For instance, in one published work, a high selectivity (90%) to oxygenates (CH3OH + HCHO) was obtained at CH4 conversion of 20–25% at 873 K in an excess amount of water vapour over MoO3/SiO2 catalysts prepared by a sol-gel method [31]. Another work conducted the experiments under similar reactions with MoO3/SiO2 catalyst prepared by a similar method, but the yield of oxygenates was not greater than 4% [25]. Another example of contradiction showed that by using N2O as an oxidant, CH3OH could be achieved with a noticeable selectivity in the presence of H2O over MoO3/SiO2 [32]. Results published by other groups used similar catalytic systems, but the results showed no detectable formation of CH3OH [33, 34]. Metal-containing zeolites such as Co, Cu, and Fe have been studied at low temperature in batch mode [35, 36]. The direct conversion of methane to methanol over this metal-containing zeolite consists of three steps: (1) formation of active species by calcinations in air, (2) reaction of the active species with methane at low temperature and (3) extraction of methanol, using a polar protic solvent [37]. However, these catalytic systems are not yet a continuous process as an extraction procedure for methanol is required [36, 37]. A series of catalysts based on MoO3 and WO3 were studied, and the WO3-based catalysts were less effective for the production of methanol. The Ga2O3/MoO3 catalyst showed the maximum methanol yield [38].
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In a series of seminal publications, Hutchings and co-workers demonstrated that Fe-ZSM-5- and Fe-Cu-ZSM-5-based zeolites and Au-Pd supported on titania could activate methane at temperatures under 100°C using aqueous hydrogen peroxide as the terminal oxidant [39, 40]. The initial product of reaction was shown to be methyl hydroperoxide which subsequently reacted to yield methanol and formic acid. Figure 4 shows the time on line activity over Au-Pd/TiO2.
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Figure 4.
Time on line activity reaction temperature: 50°C, [H2O2]: 5000 μmol, solvent: H2O, 10 mL. Catalyst: 1.0 × 10−5 mol of metal, 28 mg 2.5 wt% Au-2.5 wt% Pd/TiO.
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The turnover frequencies based on Fe were high with albeit very low conversions. More recently, Al-Shihri et al. [41] showed that the reaction pathway of oxidation in aqueous hydrogen peroxide over ZSM-5 catalysts followed the reaction sequence CH4 → CH3OOH → HCHO → formic acid. Although at the reaction conditions used the formaldehyde was oxidised rapidly to formic acid, it was also converted to low molecular weight polyoxomethylene polymer. Similar findings were achieved in preliminary results using Au-Pd catalysts. However, the use of aqueous hydrogen peroxide to oxidise methane is unlikely to prove economic unless its parallel catalysed decomposition into oxygen and H2O can be supressed. Thus, the development of a viable liquid phase process based on the use of aqueous hydrogen peroxide as the terminal oxidant would be challenging.
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An attractive alternative approach is to couple in situ direct generation of hydrogen peroxide from hydrogen and oxygen with methane oxidation in a tandem process. Au-Pd catalysts have proved to be highly active for the direct hydrogen peroxide synthesis reaction and capable of enhancing the tandem catalytic oxidation of alcohols, especially using nanostructured oxide supports [42, 43]. However, while the production rate of hydrogen peroxide is high, the achievable concentration in the liquid phase remains low due to the catalysed decomposition of the formed hydrogen peroxide. This means that a tandem process in the liquid phase is more likely to find application in the selective oxidation of high value chemicals. For direct selective oxidation of light hydrocarbons to oxygenated compounds, a gas phase continuous process based on the use of heterogeneous catalysts would be more attractive. In a tandem oxidation process, the oxidant would be oxygen, air or N2O mixed with hydrogen to generate surface hydroperoxy in situ by the surface reaction of hydrogen-oxygen.
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In a preliminary study, Al-Shihri et al. demonstrated that Au-Pd catalysts were able to catalyse the gas phase direct selective oxidation of methane at moderate conditions using the tandem synthesis of hydrogen peroxide from hydrogen-oxygen mixtures. The products of reaction were trapped and found to be methylhydroperoxide, polyoxomethylene, and a small amount of formic acid. Based on analogy with the liquid phase reaction sequence described above [41], the production of polyoxomethylene would be expected to involve initially the formation of formaldehyde as a reaction intermediate, although none was detected. This aspect is currently being investigated prior to publication of these exciting new results. The production of methyl hydroperoxide, formaldehyde and polyoxomethylene from methane is highly desirable. Polyoxomethylenes are valuable polymeric materials and also potential hydrogen storage materials; methyl hydroperoxide can be utilised to form methanol or react to form other compounds. In our preliminary study, the most promising Au-Pd catalysts were based on the use of nanostructured oxide supports. However, the catalysts were prepared by simple impregnation and were far from optimum in terms of metal particle dispersion and degree of Au-Pd alloy formation. These factors are important in the activity, selectivity, and maximising the selectivity in the use of the hydrogen, that is, avoiding direct combustion to water.
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Shan et al. showed that mononuclear rhodium species supported by zeolite or titanium dioxide in aqueous solution can convert methane to methanol and acetic acid with high selectivity, using oxygen and carbon monoxide under mild conditions [44]. In a recent study, the direct conversion of methane to methanol was investigated using experimental and computational study. The results of this study showed that low Ni loadings on a CeO2(111) support can perform a direct catalytic cycle for the generation of methanol at low temperature using oxygen and water as reactants, with a higher selectivity than ever reported for ceria-based catalysts [45].
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Gold-based catalysts have also shown interesting performance for the activation of C-H bond in alkane selective oxidation with dioxygen. A particular focus has been put on the synthesis of cyclohexanone and cyclohexanol. Zhao and co-workers [46] first applied gold catalysis in the activation of cyclohexane: Au/ZSM-5 and Au/MCM-41 favoured selectivity around 90% and conversions of 10–15% at 150°C, even though a loss in both activity and selectivity after their reuse is a drawback for industrial application. Two recent studies on the selective cyclohexane oxidation were performed by tailoring a supported gold on different materials, namely amorphous silica doped with titania and alumina prepared by a modified direct anionic exchange method [47].
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In the direct gas phase oxidation of methane to methanol, no noble metal except Pd was investigated, and there was no promising results obtained when Pd was used and that might be due to the excessive interaction between Pd and the supports [25, 48]. Therefore, in order to overcome the extent of interaction between Pd and the support, and to increase selectivity toward methanol, bimetallic systems seem to be a more promising solution. Great success has been achieved in a variety of catalytic processes by combining two metallic elements in bimetallic catalysts, such as the platinum-iridium (Pt-Ir) system for petroleum reforming, platinum-tin (Pt-Sn) for alkane dehydrogenation, the nickel-gold (Ni-Au) system for steam reforming of alkanes, and the palladium-gold (Pd-Au) for selective oxidations [49].
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2.3 Challenges in technologies for the conventional methods
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The industrial production of methanol is executed via indirect way, in which methane is first converted to synthesise gas in highly intensive energy step. The synthesis gas is then converted to methanol. The intensive energy synthesis gas step occurs in operational plant at pressure range between 200 and 600 psi and temperature range between 700 and 1000°C [50]. This step is responsible for 60% of the capital cost of the plant. Therefore, the direct conversion of methane to methanol is highly desirable. Several approaches have been investigated and reported; however, no breakthrough has been achieved yet.
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The homogeneous gas phase partial oxidation has the potential to replace the industrial method. In a technical evaluation study of this method, it was shown that a methanol selectivity of over 70% at 15% methane conversion can be achieved. However, the low conversion of methane per pass and relatively low methanol selectivity is still observed in most of the academic reports [51, 52]. The problem is due to kinetic and thermodynamic reasons [53]. This way requires a pressure of around 10 atm and temperature (1000°C) to activate methane and convert it to methanol with reasonable selectivity. The C-H bond in methane (440 kJ/mol) is stronger than the same bond in methanol (389 kJ/mol). That means at high temperatures, the methanol is more reactive than methane, which might lead to the decomposition of methanol to low grade product [52, 54, 55, 56]. In addition, the gas phase homogeneous is a free radical reaction, which means that it is difficult to control the process on the large scale [51, 54, 57].
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The catalysts play an important role in activating methane at low reaction conditions and produce methanol with low byproducts [58, 59]. Two advantages of this method are the reduction of energy consumption used for methane conversion to methanol, and the low concentration of CO2 produced in this process [58, 59]. The important factor in this process is to find catalysts that could activate methane at moderate conditions and convert it selectively to methanol. Although intensive work has been reported, no catalytic system has achieved the target conversion and selectivity.
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A low temperature homogeneous catalyst in solutions is another way to convert methane to methanol at low temperatures. However, two challenges of this method is first the introduction of the catalysts with reasonable reactivity and selectivity that also tolerates oxidising and protic conditions [11]. The second challenge is the use of acid as a solvent such as sulphuric acid, which is applied in many studies. The main disadvantage of using sulphuric acid as solvent is the difficulty in separating the methanol from the solvent. Moreover, the acid might corrode and poison the catalysts through the reaction [11].
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In nature, methane monooxygenases (MMOs) demonstrate high activity for methanol synthesis with a production rate of 5 mol (CH3OH) kg (catalyst)-1 h−1 at ambient conditions. However, this method is still not practical yet due to the difficulty in purifying these proteins and the further oxidation reaction of methanol to formaldehyde.
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3. Unconventional approach to convert methane to oxygenates
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3.1 Conversion of methane to methanol via plasma technologies
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Plasma can be used in many applications including oxidation of methane to methanol [60]. In plasma, the oxidation of methane to methanol can be conducted under atmospheric gas pressure. Plasma is often referred to as the fourth state of matter, and it includes several components: positive ions, negative ions, electrons and neutral species. Plasma technology can be classified into thermal plasma and non-thermal plasma [61]. Thermal plasma can be described as a gas consisting of electrons, highly excited atoms, ions, radicals, photons and neutral particles, while electrons that have much higher energy than other surrounding particles populate non-thermal plasma. Okazaki et al. [62] reported that the conversion of methane to methanol was achieved using non-equilibrium plasma chemical reactions under atmospheric pressure by ultra-short pulsed barrier discharge in an extremely thin glass tube reactor. Various designs for plasma reactors for the oxidation of methane have been proposed to enhance the selectivity toward methanol. For example, in thermal plasma reactors, the dielectric barrier discharge (DBD) reactor was used for the synthesis of methanol from methane. This reactor was able to reduce the required temperature and pressure needed [63]. Another reactor is a new non-thermal discharge micro-reactor, which is used for a single-step, non-catalytic, direct and selective synthesis of methanol via methane partial oxidation at room temperature [64]. The non-thermal plasma can be developed by integrating the reactor with catalyst to improve the activity and selectivity of methane oxidation. In a recent study, the Cu-doped Ni was loaded on CeO2, which led to enhance the selectivity of methanol until 36% [65]. In another study, multicomponent catalysts were combined with plasma in two different approaches, in-plasma catalysis (IPC) and post-plasma catalysis (PPC), for achieving high levels in both methane conversion and aimed methanol selectivity through the synergetic effect of the Fe2O3−CuO/γ-Al2O3 catalyst [66].
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3.2 Methane oxidation to methanol using photocatalysts
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The photocatalytic process is a photochemical reaction that is carried out with external energy provided by ultraviolet light radiation that has energy equal to or greater than the energy band gap of a semiconductor. Several of oxidation and reduction processes are involved in the photo-generated electron and hole. TiO2 catalysts have been used as semiconductor photocatalysts for a wide range of environmental applications [67]. In addition, tungsten oxide (WO3) is also a good photocatalyst due to its high chemical stability in aqueous solution under acidic conditions in the presence of an oxidising agent [68]. For example, one study demonstrated that the WO3 photocatalyst produced hydroxyl radicals that react with a methane molecule to produce a methyl radical, which promote the formation of methanol [69]. Another study [70] investigated different experimental parameters for the methane conversion such as catalyst concentration, laser power, laser exposure time, effects of free radical generator (H2O2) and electron capture agent (Fe3+), using visible laser light. Also, this study examined the comparison between WO3 and TiO2, and it was found that the WO3 showed the highest methane conversion [70, 71]. A recent work has studied the introduction of some electron scavengers such as (Fe3+, Cu2+, and Ag+) and H2O2 species to the WO3 catalyst to enhance the selectivity of methanol. They found that WO3/Fe3+ is the most active catalyst with a methanol selectivity of 58.5% [68]. Another photocatalyst for the methane oxidation to methanol is vanadium oxide supported by MCM-41. Nitric oxide (NO) was used as an oxidant for the oxidation of methane under UV irradiation at 295 [72]. Figure 5 shows an example of methane conversion to methanol via photocatalysis.
\n
Figure 5.
Graphical representation of reaction of conversion of methane to methanol via photocatalysts [73].
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3.3 Conversion of methane to methanol using supercritical water
\n
The supercritical water oxidation (SCWO) is a reaction that occurs in water at elevated temperatures and pressures above the thermodynamic critical point of the mixture. Under the supercritical fluid conditions, the properties of water such as viscosity and dielectric constant can be adjusted between high gas-like diffusion rates and high liquid-like collision rates by varying pressure and temperature [60]. The catalytic oxidation of methane was examined over Cr2O3 under supercritical water conditions, and it was found that this catalytic system under supercritical conditions enhances the conversion rate of ethane and promotes the selectivity of methanol [74]. Another study investigated the isothermal conditions with a laminar reactor in SCWO for the direct partial oxidation of methane to methanol. They achieved a methanol selectivity of 35% at a conversion of 3% at temperatures of 400–410°C [75]. Savage PE et al., [76] have examined two types of reactors, glass-lined reactors and stainless steel reactors. A parametric study has been conducted using both reactors, and the glass lined reactor showed higher conversion of methane to methanol.
\n
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3.4 Conversion of methane to methanol using membrane technology
\n
Membrane technology has been used for methane conversion to methanol using membrane reactor at moderate conditions. The advantage of using a membrane reactor is the fact that it can perform two functions at once, reaction and separation. The membrane can be classified based on the type of materials and porosity. The membrane can be made either by polymeric or organic materials with different porosity [60]. The organic membrane has advantages over the polymer in terms of the tolerance to chemical and temperature effects. Moreover, the organic membrane is mainly composed of metallic or ceramic materials and has greater physiochemical stability. Two research works studied the methane oxidation to produce methanol using Methylosinus trichosporium OB3b with a high concentration of Cu2+ and they found that the optimization of the conversion rate was positively affected by several parameters including the temperature, pH and concentrations of sodium formate, phosphate buffer and cyclopropanol [77, 78]. In another study, the methane oxidation was carried out using a membrane reactor where the methane and oxygen were introduced by two separate dense silicone tubes. A high methanol production of 1.12 g/L and 60% methane conversion were reported [79].
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3.5 Challenges of unconventional ways to convert methane to methanol
\n
The unconventional technologies such as plasma, photocatalysts, supercritical and biological are long-term processes, and still away from practical. The methane oxidation under plasma conditions is considered as a clean method as there are no harmful emissions produced such as CO2 and CO [80]. The plasma reactor is simple, benign and cheap. However, the productivity of methanol is low due to the limitation of methane solubility in the reaction medium at ambient conditions.
\n
Photocatalysis technology is an attractive way to convert methane to methanol, as the basic requirement for this method is the use of three abundant reactants of light, water and methane. Despite the two decades of work on photocatalysis, the selectivity of methanol is still low [68, 70].
\n
Supercritical water oxidation is an efficient process to treat a variety of hazardous and non-hazardous wastes. However, there are some factors that limit the application of this technology in methane oxidation such as the complication of the reactor design, the high temperature used and the high corrosion rate when using halogens such as chlorine for some waste treatment [60, 81].
\n
The use of membrane technology for methane conversion to methanol is feasible due to the advantage of the effective separation of methane and methanol. However, some challenges still exist for large scale application: first, the relatively high energy requirement for large scale plant, second, the low tolerance of polymer-based membrane to high temperatures and chemicals, third, the high conversion of methane will produce different organic compounds, and that might cause swelling or breakage of the membrane [60, 81].
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4. Summary
\n
In this chapter, we discussed the utilisation of methane as the main component of natural gas that can be converted to methanol. We discussed various processes that can activate methane and convert it in a single step to methanol, including their feasibility, recent progress and challenges associated with the conventional and unconventional methods. We showed that these processes have advantages and disadvantages. However, most of them suffer from the low yield of methanol. The unconventional methods are long-term processes and still far away from practical. The low temperature route using heterogeneous catalysts has a great potential and can be alternative to the current industrial process as some catalytic systems were shown to activate methane at moderate reaction conditions using different oxidants. Nevertheless, the selectivity toward methanol is still low. Therefore, more effort is needed to design and synthesise robust and cheap catalysts that could convert methane directly and selectively to methanol using air as an oxidant in a continuous flow reaction system.
\n
\n\n',keywords:"direct methane conversion, natural gas, oxygenates, catalysis, methanol",chapterPDFUrl:"https://cdn.intechopen.com/pdfs/67664.pdf",chapterXML:"https://mts.intechopen.com/source/xml/67664.xml",downloadPdfUrl:"/chapter/pdf-download/67664",previewPdfUrl:"/chapter/pdf-preview/67664",totalDownloads:95,totalViews:0,totalCrossrefCites:0,dateSubmitted:"December 20th 2018",dateReviewed:"May 2nd 2019",datePrePublished:"August 26th 2020",datePublished:null,dateFinished:null,readingETA:"0",abstract:"Selective oxidation of methane is one of the most challenging reactions in catalysis. Methane is a very stable molecule and requires high energy to be activated. Different approaches of single step methane conversion have been suggested to overcome this challenge. However, the current commercial process of methane conversion to methanol is via the indirect way, in which methane is first converted to synthesis gas in highly intensive energy step, and synthesis gas is then converted into methanol. The first step is responsible for 60% of the capital cost of the plant. There are enormous researches that have been conducted in a direct way and some good results have been achieved. This chapter will summarize the recent advances in the direct selective oxidation of methane to methanol.",reviewType:"peer-reviewed",bibtexUrl:"/chapter/bibtex/67664",risUrl:"/chapter/ris/67664",signatures:"Saeed Alshihri and Hamid Almegren",book:{id:"10096",title:"Biogas",subtitle:null,fullTitle:"Biogas",slug:null,publishedDate:null,bookSignature:"Dr. Abd El-Fatah Abomohra, Dr. Mahdy Elsayed, Prof. Zuzeng Qin, Dr. Hongbing Ji and Dr. Zili Liu",coverURL:"https://cdn.intechopen.com/books/images_new/10096.jpg",licenceType:"CC BY 3.0",editedByType:null,editors:[{id:"186114",title:"Dr.",name:"Abd El-Fatah",middleName:null,surname:"Abomohra",slug:"abd-el-fatah-abomohra",fullName:"Abd El-Fatah Abomohra"}],productType:{id:"1",title:"Edited Volume",chapterContentType:"chapter",authoredCaption:"Edited by"}},authors:null,sections:[{id:"sec_1",title:"1. Introduction",level:"1"},{id:"sec_2",title:"2. Conventional catalytic approach to convert methane to oxygenates",level:"1"},{id:"sec_2_2",title:"2.1 Gas phase reaction based on homogeneous radical mechanism",level:"2"},{id:"sec_3_2",title:"2.2 A low temperature catalytic route involving homogeneous and heterogeneous catalysis",level:"2"},{id:"sec_4_2",title:"2.3 Challenges in technologies for the conventional methods",level:"2"},{id:"sec_6",title:"3. Unconventional approach to convert methane to oxygenates",level:"1"},{id:"sec_6_2",title:"3.1 Conversion of methane to methanol via plasma technologies",level:"2"},{id:"sec_7_2",title:"3.2 Methane oxidation to methanol using photocatalysts",level:"2"},{id:"sec_8_2",title:"3.3 Conversion of methane to methanol using supercritical water",level:"2"},{id:"sec_9_2",title:"3.4 Conversion of methane to methanol using membrane technology",level:"2"},{id:"sec_10_2",title:"3.5 Challenges of unconventional ways to convert methane to methanol",level:"2"},{id:"sec_12",title:"4. 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Journal of Supercritical Fluids. 1994;7(2):135-144\n'},{id:"B77",body:'Lee SG et al. Optimisation of methanol biosynthesis from methane using methylosinus trichosporium OB3b. Biotechnology letters. 2004;26:947-950\n'},{id:"B78",body:'Takeguchi M et al. Optimisation of methanol bio-synthesis by Methylosinus trichosporium OB3b: An approach to improve methanol accumulation. Applied biochemistry and biotechnology. 1997;68:143-152\n'},{id:"B79",body:'Duan C et al. High-rate conversion of methane to methanol by Methylosinus trichosporium OB3b. Bioresource technology. 2011;102:7349-7353\n'},{id:"B80",body:'Lemmens B et al. Assessment of plasma gasification of high caloric waste streams. Waste Management. 2007;27:1562-1569\n'},{id:"B81",body:'Introduction to membrane. http://www.separationprocesses.com/Membrane/MT_Chp01c.htm\n\n'}],footnotes:[],contributors:[{corresp:"yes",contributorFullName:"Saeed Alshihri",address:"alshihri@kacst.edu.sa",affiliation:'
National Petrochemical Technology Center, Materials Science Research Institute, King Abdulaziz City for Science and Technology (KACST), Riyadh, Saudi Arabia
National Petrochemical Technology Center, Materials Science Research Institute, King Abdulaziz City for Science and Technology (KACST), Riyadh, Saudi Arabia
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Autophagy was previously considered to be nonselective; however, studies have increasingly established that autophagy-mediated degradation is highly regulated. Selective autophagy regulates plenty of specific cellular components through specialized molecules termed autophagy receptors, which include p62, NBR1, NDP52, optineurin, and VCP among others. Autophagy receptors recognize ubiquitinated cargo and interact with the LC3/GABARAP/Gate16 protein on the membrane of nascent phagophore. In this review, we summarize the advances in the molecular mechanisms of selective autophagy adaptor proteins.",signatures:"Kahiry Leyva-Paredes, Nayeli Shantal Castrejón-Jiménez, Hugo Iván\nArrieta-Oliva, Shantal Lizbeth Baltierra-Uribe and Blanca Estela\nGarcía-Pérez",authors:[{id:"82060",title:"Dr.",name:"Blanca-Estela",surname:"García-Pérez",fullName:"Blanca-Estela García-Pérez",slug:"blanca-estela-garcia-perez",email:"abrilestela@hotmail.com"},{id:"90078",title:"MSc.",name:"Nayeli Shantal",surname:"Castrejon-Jimenez",fullName:"Nayeli Shantal Castrejon-Jimenez",slug:"nayeli-shantal-castrejon-jimenez",email:"naye_nice85@hotmail.com"},{id:"187941",title:"Dr.",name:"Kahiry",surname:"Leyva-Paredes",fullName:"Kahiry Leyva-Paredes",slug:"kahiry-leyva-paredes",email:"kahiryley@hotmail.com"},{id:"187942",title:"MSc.",name:"Hugo Ivan",surname:"Arrieta-Oliva",fullName:"Hugo Ivan Arrieta-Oliva",slug:"hugo-ivan-arrieta-oliva",email:"hugo.oliva67@gmail.com"},{id:"187943",title:"Dr.",name:"Shantal Lizbeth",surname:"Baltierra-Uribe",fullName:"Shantal Lizbeth Baltierra-Uribe",slug:"shantal-lizbeth-baltierra-uribe",email:"shantal_baliz@hotmail.com"}],book:{title:"Autophagy in Current Trends in Cellular Physiology and Pathology",slug:"autophagy-in-current-trends-in-cellular-physiology-and-pathology",productType:{id:"1",title:"Edited Volume"}}}],collaborators:[{id:"108846",title:"Dr.",name:"Gary",surname:"Warnes",slug:"gary-warnes",fullName:"Gary Warnes",position:null,profilePictureURL:"//cdnintech.com/web/frontend/www/assets/author.svg",biography:null,institutionString:null,institution:{name:"Queen Mary University of London",institutionURL:null,country:{name:"United Kingdom"}}},{id:"116056",title:"Dr.",name:"Guillermo",surname:"Blanco",slug:"guillermo-blanco",fullName:"Guillermo Blanco",position:null,profilePictureURL:"//cdnintech.com/web/frontend/www/assets/author.svg",biography:null,institutionString:null,institution:null},{id:"138193",title:"Dr.",name:"Laura",surname:"Kornblihtt",slug:"laura-kornblihtt",fullName:"Laura Kornblihtt",position:null,profilePictureURL:"//cdnintech.com/web/frontend/www/assets/author.svg",biography:null,institutionString:null,institution:null},{id:"174854",title:"Dr.",name:"Daolin",surname:"Tang",slug:"daolin-tang",fullName:"Daolin Tang",position:null,profilePictureURL:"//cdnintech.com/web/frontend/www/assets/author.svg",biography:null,institutionString:null,institution:{name:"University of Pittsburgh",institutionURL:null,country:{name:"United States of America"}}},{id:"175785",title:"Dr.",name:"Rui",surname:"Kang",slug:"rui-kang",fullName:"Rui Kang",position:null,profilePictureURL:"//cdnintech.com/web/frontend/www/assets/author.svg",biography:null,institutionString:null,institution:null},{id:"177873",title:"Dr.",name:"Shigeru",surname:"Saito",slug:"shigeru-saito",fullName:"Shigeru Saito",position:null,profilePictureURL:"//cdnintech.com/web/frontend/www/assets/author.svg",biography:null,institutionString:null,institution:null},{id:"182983",title:"Prof.",name:"Ligen",surname:"Li",slug:"ligen-li",fullName:"Ligen Li",position:null,profilePictureURL:"//cdnintech.com/web/frontend/www/assets/author.svg",biography:null,institutionString:null,institution:null},{id:"186058",title:"Dr.",name:"Akitoshi",surname:"Nakashima",slug:"akitoshi-nakashima",fullName:"Akitoshi Nakashima",position:null,profilePictureURL:"//cdnintech.com/web/frontend/www/assets/author.svg",biography:null,institutionString:null,institution:{name:"University of Toyama",institutionURL:null,country:{name:"Japan"}}},{id:"186446",title:"Dr.",name:"Aiko",surname:"Aoki",slug:"aiko-aoki",fullName:"Aiko Aoki",position:null,profilePictureURL:"//cdnintech.com/web/frontend/www/assets/author.svg",biography:null,institutionString:null,institution:null},{id:"186901",title:"Dr.",name:"María",surname:"Carreras",slug:"maria-carreras",fullName:"María Carreras",position:null,profilePictureURL:"//cdnintech.com/web/frontend/www/assets/author.svg",biography:null,institutionString:null,institution:null}]},generic:{page:{slug:"publication-agreement-chapters",title:"Publication Agreement - Book Chapter",intro:'
IntechOpen aims to ensure that original material is published while at the same time giving significant freedom to our Authors. To that end we maintain a flexible Copyright Policy guaranteeing that there is no transfer of copyright to the publisher and Authors retain exclusive copyright to their Work.
',metaTitle:"Publication Agreement - Chapters",metaDescription:"IN TECH aims to guarantee that original material is published while at the same time giving significant freedom to our authors. For that matter, we uphold a flexible copyright policy meaning that there is no transfer of copyright to the publisher and authors retain exclusive copyright to their work.\n\nWhen submitting a manuscript the Corresponding Author is required to accept the terms and conditions set forth in our Publication Agreement as follows:",metaKeywords:null,canonicalURL:"/page/publication-agreement-chapters",contentRaw:'[{"type":"htmlEditorComponent","content":"
The Corresponding Author (acting on behalf of all Authors) and INTECHOPEN LIMITED, incorporated and registered in England and Wales with company number 11086078 and a registered office at 5 Princes Gate Court, London, United Kingdom, SW7 2QJ conclude the following Agreement regarding the publication of a Book Chapter:
\\n\\n
1. DEFINITIONS
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Corresponding Author: The Author of the Chapter who serves as a Signatory to this Agreement. The Corresponding Author acts on behalf of any other Co-Author.
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Co-Author: All other Authors of the Chapter besides the Corresponding Author.
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IntechOpen: IntechOpen Ltd., the Publisher of the Book.
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Book: The publication as a collection of chapters compiled by IntechOpen including the Chapter. Chapter: The original literary work created by Corresponding Author and any Co-Author that is the subject of this Agreement.
\\n\\n
2. CORRESPONDING AUTHOR'S GRANT OF RIGHTS
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2.1 Subject to the following Article, the Corresponding Author grants and shall ensure that each Co-Author grants, to IntechOpen, during the full term of copyright and any extensions or renewals of that term the following:
\\n\\n
\\n\\t
An irrevocable, worldwide, royalty-free, perpetual, transferable, sublicensable, non-exclusive right to publish, communicate to the public, reproduce, republish, transmit, sell, distribute and otherwise use and make available the Chapter in whole, partial or adapted from and/or incorporated in or in conjunction with other works, in electronic and print editions of the Publication and in derivative works and on any platform owned and/or operated by IntechOpen, throughout the world, in all languages, and in all media and formats now known or later developed.
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An irrevocable, worldwide, royalty-free, perpetual, transferable, sublicensable, non-exclusive right to create and store electronic archival copies of the Chapter, including the right to deposit the Chapter in open access digital repositories.
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An irrevocable, worldwide, royalty-free, perpetual, transferable, sublicensable, non-exclusive right to license others to reproduce, translate, republish, transmit and distribute the Chapter in whole, partial or adapted from and/or incorporated in or in conjunction with other works under the condition that the Corresponding Author and each Co-Author is attributed (currently this is carried out by publishing the Chapter under a Creative Commons Attribution 3.0 Unported License).
\\n
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The aforementioned licenses shall survive the expiry or termination of this Agreement for any reason.
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2.2 The Corresponding Author (on their own behalf and on behalf of any Co-Author) reserves the following rights to the Chapter but agrees not to exercise them in such a way as to adversely affect IntechOpen's ability to utilize the full benefit of this Publication Agreement: (i) reprographic rights worldwide, other than those which subsist in the typographical arrangement of the Chapter as published by IntechOpen; and (ii) public lending rights arising under the Public Lending Right Act 1979, as amended from time to time, and any similar rights arising in any part of the world.
\\n\\n
The Corresponding Author confirms that they (and any Co-Author) are and will remain a member of any applicable licensing and collecting society and any successor to that body responsible for administering royalties for the reprographic reproduction of copyright works.
\\n\\n
Subject to the license granted above, copyright in the Chapter and all versions of it created during IntechOpen's editing process (including the published version) is retained by the Corresponding Author and any Co-Author.
\\n\\n
Subject to the license granted above, the Corresponding Author and any Co-Author retains patent, trademark and other intellectual property rights to the Chapter.
\\n\\n
2.3 All rights granted to IntechOpen in this Article are assignable, sublicensable or otherwise transferrable to third parties without the Corresponding Author's or any Co-Author’s specific approval.
\\n\\n
2.4 The Corresponding Author (on their own behalf and on behalf of each Co-Author) will not assert any rights under the Copyright, Designs and Patents Act 1988 to object to derogatory treatment of the Chapter as a consequence of IntechOpen's changes to the Chapter arising from translation of it, corrections and edits for house style, removal of problematic material and other reasonable edits.
\\n\\n
3. CORRESPONDING AUTHOR'S DUTIES
\\n\\n
3.1 When distributing or re-publishing the Chapter, the Corresponding Author agrees to credit the Book in which the Chapter has been published as the source of first publication, as well as IntechOpen. The Corresponding Author warrants that each Co-Author will also credit the Book in which the Chapter has been published as the source of first publication, as well as IntechOpen, when they are distributing or re-publishing the Chapter.
\\n\\n
3.2 When submitting the Chapter, the Corresponding Author agrees to:
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\\n\\t
Comply with all instructions and guidelines provided by IntechOpen;
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Produce the Chapter with all due skill, care and diligence, and in accordance with good scientific practice;
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Submit all the corrections in due time as defined during the publishing process schedule.
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\\n\\n
The Corresponding Author will be held responsible for the payment of the Open Access Publishing Fees.
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All payments shall be due 30 days from the date of the issued invoice. The Corresponding Author or the payer on the Corresponding Author's and Co-Authors' behalf will bear all banking and similar charges incurred.
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3.3 The Corresponding Author shall obtain in writing all consents necessary for the reproduction of any material in which a third-party right exists, including quotations, photographs and illustrations, in all editions of the Chapter worldwide for the full term of the above licenses, and shall provide to IntechOpen upon request the original copies of such consents for inspection (at IntechOpen's option) or photocopies of such consents.
\\n\\n
The Corresponding Author shall obtain written informed consent for publication from people who might recognize themselves or be identified by others (e.g. from case reports or photographs).
\\n\\n
3.4 The Corresponding Author and any Co-Author shall respect confidentiality rights during and after the termination of this Agreement. The information contained in all correspondence and documents as part of the publishing activity between IntechOpen and the Corresponding Author and any Co-Author are confidential and are intended only for the recipient. The contents may not be disclosed publicly and are not intended for unauthorized use or distribution. Any use, disclosure, copying, or distribution is prohibited and may be unlawful.
\\n\\n
4. CORRESPONDING AUTHOR'S WARRANTY
\\n\\n
4.1 The Corresponding Author represents and warrants that the Chapter does not and will not breach any applicable law or the rights of any third party and, specifically, that the Chapter contains no matter that is defamatory or that infringes any literary or proprietary rights, intellectual property rights, or any rights of privacy. The Corresponding Author warrants and represents that: (i) the Chapter is the original work of themselves and any Co-Author and is not copied wholly or substantially from any other work or material or any other source; (ii) the Chapter has not been formally published in any other peer-reviewed journal or in a book or edited collection, and is not under consideration for any such publication; (iii) they themselves and any Co-Author are qualifying persons under section 154 of the Copyright, Designs and Patents Act 1988; (iv) they themselves and any Co-Author have not assigned and will not during the term of this Publication Agreement purport to assign any of the rights granted to IntechOpen under this Publication Agreement; and (v) the rights granted by this Publication Agreement are free from any security interest, option, mortgage, charge or lien.
\\n\\n
The Corresponding Author also warrants and represents that: (i) they have the full power to enter into this Publication Agreement on their own behalf and on behalf of each Co-Author; and (ii) they have the necessary rights and/or title in and to the Chapter to grant IntechOpen, on behalf of themselves and any Co-Author, the rights and licenses expressed to be granted in this Publication Agreement. If the Chapter was prepared jointly by the Corresponding Author and any Co-Author, the Corresponding Author warrants and represents that: (i) each Co-Author agrees to the submission, license and publication of the Chapter on the terms of this Publication Agreement; and (ii) they have the authority to enter into this Publication Agreement on behalf of and bind each Co-Author. The Corresponding Author shall: (i) ensure each Co-Author complies with all relevant provisions of this Publication Agreement, including those relating to confidentiality, performance and standards, as if a party to this Publication Agreement; and (ii) remain primarily liable for all acts and/or omissions of each such Co-Author.
\\n\\n
The Corresponding Author agrees to indemnify and hold IntechOpen harmless against all liabilities, costs, expenses, damages and losses and all reasonable legal costs and expenses suffered or incurred by IntechOpen arising out of or in connection with any breach of the aforementioned representations and warranties. This indemnity shall not cover IntechOpen to the extent that a claim under it results from IntechOpen's negligence or willful misconduct.
\\n\\n
4.2 Nothing in this Publication Agreement shall have the effect of excluding or limiting any liability for death or personal injury caused by negligence or any other liability that cannot be excluded or limited by applicable law.
\\n\\n
5. TERMINATION
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5.1 IntechOpen has a right to terminate this Publication Agreement for quality, program, technical or other reasons with immediate effect, including without limitation (i) if the Corresponding Author or any Co-Author commits a material breach of this Publication Agreement; (ii) if the Corresponding Author or any Co-Author (being an individual) is the subject of a bankruptcy petition, application or order; or (iii) if the Corresponding Author or any Co-Author (being a company) commences negotiations with all or any class of its creditors with a view to rescheduling any of its debts, or makes a proposal for or enters into any compromise or arrangement with any of its creditors.
\\n\\n
In case of termination, IntechOpen will notify the Corresponding Author, in writing, of the decision.
\\n\\n
6. INTECHOPEN’S DUTIES AND RIGHTS
\\n\\n
6.1 Unless prevented from doing so by events outside its reasonable control, IntechOpen, in its discretion, agrees to publish the Chapter attributing it to the Corresponding Author and any Co-Author.
\\n\\n
6.2 IntechOpen has the right to use the Corresponding Author’s and any Co-Author’s names and likeness in connection with scientific dissemination, retrieval, archiving, web hosting and promotion and marketing of the Chapter and has the right to contact the Corresponding Author and any Co-Author until the Chapter is publicly available on any platform owned and/or operated by IntechOpen.
\\n\\n
6.3 IntechOpen is granted the authority to enforce the rights from this Publication Agreement, on behalf of the Corresponding Author and any Co-Author, against third parties (for example in cases of plagiarism or copyright infringements). In respect of any such infringement or suspected infringement of the copyright in the Chapter, IntechOpen shall have absolute discretion in addressing any such infringement which is likely to affect IntechOpen's rights under this Publication Agreement, including issuing and conducting proceedings against the suspected infringer.
\\n\\n
7. MISCELLANEOUS
\\n\\n
7.1 Further Assurance: The Corresponding Author shall and will ensure that any relevant third party (including any Co-Author) shall, execute and deliver whatever further documents or deeds and perform such acts as IntechOpen reasonably requires from time to time for the purpose of giving IntechOpen the full benefit of the provisions of this Publication Agreement.
\\n\\n
7.2 Third Party Rights: A person who is not a party to this Publication Agreement may not enforce any of its provisions under the Contracts (Rights of Third Parties) Act 1999.
\\n\\n
7.3 Entire Agreement: This Publication Agreement constitutes the entire agreement between the parties in relation to its subject matter. It replaces and extinguishes all prior agreements, draft agreements, arrangements, collateral warranties, collateral contracts, statements, assurances, representations and undertakings of any nature made by or on behalf of the parties, whether oral or written, in relation to that subject matter. Each party acknowledges that in entering into this Publication Agreement it has not relied upon any oral or written statements, collateral or other warranties, assurances, representations or undertakings which were made by or on behalf of the other party in relation to the subject matter of this Publication Agreement at any time before its signature (together "Pre-Contractual Statements"), other than those which are set out in this Publication Agreement. Each party hereby waives all rights and remedies which might otherwise be available to it in relation to such Pre-Contractual Statements. Nothing in this clause shall exclude or restrict the liability of either party arising out of its pre-contract fraudulent misrepresentation or fraudulent concealment.
\\n\\n
7.4 Waiver: No failure or delay by a party to exercise any right or remedy provided under this Publication Agreement or by law shall constitute a waiver of that or any other right or remedy, nor shall it preclude or restrict the further exercise of that or any other right or remedy. No single or partial exercise of such right or remedy shall preclude or restrict the further exercise of that or any other right or remedy.
\\n\\n
7.5 Variation: No variation of this Publication Agreement shall be effective unless it is in writing and signed by the parties (or their duly authorized representatives).
\\n\\n
7.6 Severance: If any provision or part-provision of this Publication Agreement is or becomes invalid, illegal or unenforceable, it shall be deemed modified to the minimum extent necessary to make it valid, legal and enforceable. If such modification is not possible, the relevant provision or part-provision shall be deemed deleted.
\\n\\n
Any modification to or deletion of a provision or part-provision under this clause shall not affect the validity and enforceability of the rest of this Publication Agreement.
\\n\\n
7.7 No partnership: Nothing in this Publication Agreement is intended to, or shall be deemed to, establish or create any partnership or joint venture or the relationship of principal and agent or employer and employee between IntechOpen and the Corresponding Author or any Co-Author, nor authorize any party to make or enter into any commitments for or on behalf of any other party.
\\n\\n
7.8 Governing law: This Publication Agreement and any dispute or claim (including non-contractual disputes or claims) arising out of or in connection with it or its subject matter or formation shall be governed by and construed in accordance with the law of England and Wales. The parties submit to the exclusive jurisdiction of the English courts to settle any dispute or claim arising out of or in connection with this Publication Agreement (including any non-contractual disputes or claims).
The Corresponding Author (acting on behalf of all Authors) and INTECHOPEN LIMITED, incorporated and registered in England and Wales with company number 11086078 and a registered office at 5 Princes Gate Court, London, United Kingdom, SW7 2QJ conclude the following Agreement regarding the publication of a Book Chapter:
\n\n
1. DEFINITIONS
\n\n
Corresponding Author: The Author of the Chapter who serves as a Signatory to this Agreement. The Corresponding Author acts on behalf of any other Co-Author.
\n\n
Co-Author: All other Authors of the Chapter besides the Corresponding Author.
\n\n
IntechOpen: IntechOpen Ltd., the Publisher of the Book.
\n\n
Book: The publication as a collection of chapters compiled by IntechOpen including the Chapter. Chapter: The original literary work created by Corresponding Author and any Co-Author that is the subject of this Agreement.
\n\n
2. CORRESPONDING AUTHOR'S GRANT OF RIGHTS
\n\n
2.1 Subject to the following Article, the Corresponding Author grants and shall ensure that each Co-Author grants, to IntechOpen, during the full term of copyright and any extensions or renewals of that term the following:
\n\n
\n\t
An irrevocable, worldwide, royalty-free, perpetual, transferable, sublicensable, non-exclusive right to publish, communicate to the public, reproduce, republish, transmit, sell, distribute and otherwise use and make available the Chapter in whole, partial or adapted from and/or incorporated in or in conjunction with other works, in electronic and print editions of the Publication and in derivative works and on any platform owned and/or operated by IntechOpen, throughout the world, in all languages, and in all media and formats now known or later developed.
\n\t
An irrevocable, worldwide, royalty-free, perpetual, transferable, sublicensable, non-exclusive right to create and store electronic archival copies of the Chapter, including the right to deposit the Chapter in open access digital repositories.
\n\t
An irrevocable, worldwide, royalty-free, perpetual, transferable, sublicensable, non-exclusive right to license others to reproduce, translate, republish, transmit and distribute the Chapter in whole, partial or adapted from and/or incorporated in or in conjunction with other works under the condition that the Corresponding Author and each Co-Author is attributed (currently this is carried out by publishing the Chapter under a Creative Commons Attribution 3.0 Unported License).
\n
\n\n
The aforementioned licenses shall survive the expiry or termination of this Agreement for any reason.
\n\n
2.2 The Corresponding Author (on their own behalf and on behalf of any Co-Author) reserves the following rights to the Chapter but agrees not to exercise them in such a way as to adversely affect IntechOpen's ability to utilize the full benefit of this Publication Agreement: (i) reprographic rights worldwide, other than those which subsist in the typographical arrangement of the Chapter as published by IntechOpen; and (ii) public lending rights arising under the Public Lending Right Act 1979, as amended from time to time, and any similar rights arising in any part of the world.
\n\n
The Corresponding Author confirms that they (and any Co-Author) are and will remain a member of any applicable licensing and collecting society and any successor to that body responsible for administering royalties for the reprographic reproduction of copyright works.
\n\n
Subject to the license granted above, copyright in the Chapter and all versions of it created during IntechOpen's editing process (including the published version) is retained by the Corresponding Author and any Co-Author.
\n\n
Subject to the license granted above, the Corresponding Author and any Co-Author retains patent, trademark and other intellectual property rights to the Chapter.
\n\n
2.3 All rights granted to IntechOpen in this Article are assignable, sublicensable or otherwise transferrable to third parties without the Corresponding Author's or any Co-Author’s specific approval.
\n\n
2.4 The Corresponding Author (on their own behalf and on behalf of each Co-Author) will not assert any rights under the Copyright, Designs and Patents Act 1988 to object to derogatory treatment of the Chapter as a consequence of IntechOpen's changes to the Chapter arising from translation of it, corrections and edits for house style, removal of problematic material and other reasonable edits.
\n\n
3. CORRESPONDING AUTHOR'S DUTIES
\n\n
3.1 When distributing or re-publishing the Chapter, the Corresponding Author agrees to credit the Book in which the Chapter has been published as the source of first publication, as well as IntechOpen. The Corresponding Author warrants that each Co-Author will also credit the Book in which the Chapter has been published as the source of first publication, as well as IntechOpen, when they are distributing or re-publishing the Chapter.
\n\n
3.2 When submitting the Chapter, the Corresponding Author agrees to:
\n\n
\n\t
Comply with all instructions and guidelines provided by IntechOpen;
\n\t
Produce the Chapter with all due skill, care and diligence, and in accordance with good scientific practice;
\n\t
Submit all the corrections in due time as defined during the publishing process schedule.
\n
\n\n
The Corresponding Author will be held responsible for the payment of the Open Access Publishing Fees.
\n\n
All payments shall be due 30 days from the date of the issued invoice. The Corresponding Author or the payer on the Corresponding Author's and Co-Authors' behalf will bear all banking and similar charges incurred.
\n\n
3.3 The Corresponding Author shall obtain in writing all consents necessary for the reproduction of any material in which a third-party right exists, including quotations, photographs and illustrations, in all editions of the Chapter worldwide for the full term of the above licenses, and shall provide to IntechOpen upon request the original copies of such consents for inspection (at IntechOpen's option) or photocopies of such consents.
\n\n
The Corresponding Author shall obtain written informed consent for publication from people who might recognize themselves or be identified by others (e.g. from case reports or photographs).
\n\n
3.4 The Corresponding Author and any Co-Author shall respect confidentiality rights during and after the termination of this Agreement. The information contained in all correspondence and documents as part of the publishing activity between IntechOpen and the Corresponding Author and any Co-Author are confidential and are intended only for the recipient. The contents may not be disclosed publicly and are not intended for unauthorized use or distribution. Any use, disclosure, copying, or distribution is prohibited and may be unlawful.
\n\n
4. CORRESPONDING AUTHOR'S WARRANTY
\n\n
4.1 The Corresponding Author represents and warrants that the Chapter does not and will not breach any applicable law or the rights of any third party and, specifically, that the Chapter contains no matter that is defamatory or that infringes any literary or proprietary rights, intellectual property rights, or any rights of privacy. The Corresponding Author warrants and represents that: (i) the Chapter is the original work of themselves and any Co-Author and is not copied wholly or substantially from any other work or material or any other source; (ii) the Chapter has not been formally published in any other peer-reviewed journal or in a book or edited collection, and is not under consideration for any such publication; (iii) they themselves and any Co-Author are qualifying persons under section 154 of the Copyright, Designs and Patents Act 1988; (iv) they themselves and any Co-Author have not assigned and will not during the term of this Publication Agreement purport to assign any of the rights granted to IntechOpen under this Publication Agreement; and (v) the rights granted by this Publication Agreement are free from any security interest, option, mortgage, charge or lien.
\n\n
The Corresponding Author also warrants and represents that: (i) they have the full power to enter into this Publication Agreement on their own behalf and on behalf of each Co-Author; and (ii) they have the necessary rights and/or title in and to the Chapter to grant IntechOpen, on behalf of themselves and any Co-Author, the rights and licenses expressed to be granted in this Publication Agreement. If the Chapter was prepared jointly by the Corresponding Author and any Co-Author, the Corresponding Author warrants and represents that: (i) each Co-Author agrees to the submission, license and publication of the Chapter on the terms of this Publication Agreement; and (ii) they have the authority to enter into this Publication Agreement on behalf of and bind each Co-Author. The Corresponding Author shall: (i) ensure each Co-Author complies with all relevant provisions of this Publication Agreement, including those relating to confidentiality, performance and standards, as if a party to this Publication Agreement; and (ii) remain primarily liable for all acts and/or omissions of each such Co-Author.
\n\n
The Corresponding Author agrees to indemnify and hold IntechOpen harmless against all liabilities, costs, expenses, damages and losses and all reasonable legal costs and expenses suffered or incurred by IntechOpen arising out of or in connection with any breach of the aforementioned representations and warranties. This indemnity shall not cover IntechOpen to the extent that a claim under it results from IntechOpen's negligence or willful misconduct.
\n\n
4.2 Nothing in this Publication Agreement shall have the effect of excluding or limiting any liability for death or personal injury caused by negligence or any other liability that cannot be excluded or limited by applicable law.
\n\n
5. TERMINATION
\n\n
5.1 IntechOpen has a right to terminate this Publication Agreement for quality, program, technical or other reasons with immediate effect, including without limitation (i) if the Corresponding Author or any Co-Author commits a material breach of this Publication Agreement; (ii) if the Corresponding Author or any Co-Author (being an individual) is the subject of a bankruptcy petition, application or order; or (iii) if the Corresponding Author or any Co-Author (being a company) commences negotiations with all or any class of its creditors with a view to rescheduling any of its debts, or makes a proposal for or enters into any compromise or arrangement with any of its creditors.
\n\n
In case of termination, IntechOpen will notify the Corresponding Author, in writing, of the decision.
\n\n
6. INTECHOPEN’S DUTIES AND RIGHTS
\n\n
6.1 Unless prevented from doing so by events outside its reasonable control, IntechOpen, in its discretion, agrees to publish the Chapter attributing it to the Corresponding Author and any Co-Author.
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6.2 IntechOpen has the right to use the Corresponding Author’s and any Co-Author’s names and likeness in connection with scientific dissemination, retrieval, archiving, web hosting and promotion and marketing of the Chapter and has the right to contact the Corresponding Author and any Co-Author until the Chapter is publicly available on any platform owned and/or operated by IntechOpen.
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6.3 IntechOpen is granted the authority to enforce the rights from this Publication Agreement, on behalf of the Corresponding Author and any Co-Author, against third parties (for example in cases of plagiarism or copyright infringements). In respect of any such infringement or suspected infringement of the copyright in the Chapter, IntechOpen shall have absolute discretion in addressing any such infringement which is likely to affect IntechOpen's rights under this Publication Agreement, including issuing and conducting proceedings against the suspected infringer.
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7. MISCELLANEOUS
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7.1 Further Assurance: The Corresponding Author shall and will ensure that any relevant third party (including any Co-Author) shall, execute and deliver whatever further documents or deeds and perform such acts as IntechOpen reasonably requires from time to time for the purpose of giving IntechOpen the full benefit of the provisions of this Publication Agreement.
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7.2 Third Party Rights: A person who is not a party to this Publication Agreement may not enforce any of its provisions under the Contracts (Rights of Third Parties) Act 1999.
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7.3 Entire Agreement: This Publication Agreement constitutes the entire agreement between the parties in relation to its subject matter. It replaces and extinguishes all prior agreements, draft agreements, arrangements, collateral warranties, collateral contracts, statements, assurances, representations and undertakings of any nature made by or on behalf of the parties, whether oral or written, in relation to that subject matter. Each party acknowledges that in entering into this Publication Agreement it has not relied upon any oral or written statements, collateral or other warranties, assurances, representations or undertakings which were made by or on behalf of the other party in relation to the subject matter of this Publication Agreement at any time before its signature (together "Pre-Contractual Statements"), other than those which are set out in this Publication Agreement. Each party hereby waives all rights and remedies which might otherwise be available to it in relation to such Pre-Contractual Statements. Nothing in this clause shall exclude or restrict the liability of either party arising out of its pre-contract fraudulent misrepresentation or fraudulent concealment.
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7.4 Waiver: No failure or delay by a party to exercise any right or remedy provided under this Publication Agreement or by law shall constitute a waiver of that or any other right or remedy, nor shall it preclude or restrict the further exercise of that or any other right or remedy. No single or partial exercise of such right or remedy shall preclude or restrict the further exercise of that or any other right or remedy.
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7.5 Variation: No variation of this Publication Agreement shall be effective unless it is in writing and signed by the parties (or their duly authorized representatives).
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7.6 Severance: If any provision or part-provision of this Publication Agreement is or becomes invalid, illegal or unenforceable, it shall be deemed modified to the minimum extent necessary to make it valid, legal and enforceable. If such modification is not possible, the relevant provision or part-provision shall be deemed deleted.
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Any modification to or deletion of a provision or part-provision under this clause shall not affect the validity and enforceability of the rest of this Publication Agreement.
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7.7 No partnership: Nothing in this Publication Agreement is intended to, or shall be deemed to, establish or create any partnership or joint venture or the relationship of principal and agent or employer and employee between IntechOpen and the Corresponding Author or any Co-Author, nor authorize any party to make or enter into any commitments for or on behalf of any other party.
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7.8 Governing law: This Publication Agreement and any dispute or claim (including non-contractual disputes or claims) arising out of or in connection with it or its subject matter or formation shall be governed by and construed in accordance with the law of England and Wales. The parties submit to the exclusive jurisdiction of the English courts to settle any dispute or claim arising out of or in connection with this Publication Agreement (including any non-contractual disputes or claims).
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Last updated: 2020-11-27
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