**5. Strategies to improve diabetic wound healing through manipulating macrophages**

DFUs will likely require multimodal therapies for optimal treatment. Novel therapeutics are being generated, including specific targeting of macrophages. Since the initial trigger of all the macrophage defects in diabetes appears to be sustained high blood glucose, correction of the primary problem, the hyperglycemia, would appear to be the first approach to treat problems related to diabetic wound healing [7]. However, only half of diabetics can reach the recommend standard hemoglobin A1c (HbA1c) level of <7.0% (issued by the American Diabetes Association (ADA)) [118]. Thus, it is important to search for novel therapies beyond control of blood glucose [7].

Insulin administration is a regular and effective therapy for those unresponsive to diet changes or non-insulin medications. Insulin has been found to reduce the number of M1 macrophages. Moreover, insulin has been shown to induce M1 to M2 macrophage polarization through peroxisome proliferator-activated receptor-gamma (PPAR-γ) and phosphatidylinositol-3 kinase (PI3K)/Protein kinase B (Akt)/Rasrelated C3 botulinum toxin substrate 1 (Rac-1) signaling pathways [47]. Interestingly, the PPAR-γ pathway that reduces proinflammatory cytokine expression and enhances M2 macrophage polarization in normal wound healing is impaired in diabetes and could be partially recovered by insulin [119]. Metformin is a commonly used medication for diabetes. Metformin treatment has been shown to increase M2 macrophages and decrease M1 macrophages [120–125], likely through NLRP3 inflammasome

suppression, which was discussed above [123]. Melatonin is a medication not for diabetes. However, it was found to affect macrophage polarization in diabetic wound, likely through effects on insulin [47, 126].

Treatment of chronic wounds benefits largely from localized therapies, which have the advantage of avoiding systemic effects and allowing for local and direct treatment [127]. A hydrocolloid dressing to provide moisture to the wound has been shown to improve M1-to-M2 macrophage transition to favor wound healing, especially in diabetes [128]. In another study, use of a modified dressing in diabetic mice led to an earlier appearance of M2 macrophages at the wound [129]. Thus, certain dressings to induce an M2 macrophage polarization appear to be an attractive strategy for treating chronic diabetic wounds. These dressings help the wounds heal through moisture provision, prevention of infection, induction of anti-inflammatory effects and generation of trophic factors. Along with these dressing benefits, Collagenase Santyl Ointment (CSO), with an important component called Clostridial collagenase, has been shown to increase local expression of IL-10 and arginase 1 that are both critical for M2-like macrophage polarization and functionality [130]. Another modified collagen gel has also been shown to increase IL-10 expression and macrophage migration, resulting in a substantial increase in M2 macrophages in the wound at different time points [128]. In addition, increases in IL-10 expression have also been detected after use of docosahexaenoic acid to treat diabetic wounds, with the therapeutic outcome correlated to the degree of M2 macrophage polarization [45, 131, 132].

Multipotent stem cells (MSCs) have been used in the treatment of DFUs, taking advantage of the capacity of MSCs to differentiate into different cell types such as endothelial cells, fibroblasts and smooth muscle cells that are critical for wound healing. These newly formed cells can produce and secrete trophic factors like VEGF-A, fibroblast growth factor (FGF) and platelet-derived growth factor (PDGF) [133–135]. Recently, we have reported that human MSCs express high levels of miR-205-5p, which inhibits protein translation of VEGF-A through 3'-UTR interactions [136]. Expressing antisense of miR-205-5p (as-miR-205-5p) in human MSCs significantly improved the therapeutic effects of human MSCs on diabetic wound healing in rodent models [136]. Next, we reported that MALAT1 is a lncRNA acting as a competing endogenous RNA (ceRNA) for miR-205-5p and is absent in human MSCs [137]. Expression of MALAT1 significantly attenuated the high expression of miR-205-5p in human MSCs, resulting in upregulation of VEGF-A production and improved therapeutic effects of human MSCs on diabetic wound repair [137]. Of note, these improvement in treating diabetic wounds through increasing VEGF-A levels in human MSCs was shown to be associated with increased vascularization of the wounds [136, 137]. Macrophages express high levels of VEGF receptor 1 (VEGFR1), which is one of the major receptors on macrophages to respond to chemoattractants. Thus, it is possible that the therapeutic effects of increased VEGF-A levels in human MSCs may be due, at least partially, to alterations in macrophage proliferation, differentiation and polarization [21]. Further studies of the exact alterations in macrophages caused by VEGF-A are needed. We have recently shown that another VEGF family member, placental growth factor (PlGF), is capable of altering macrophage migratory capacity and polarization [138]. Moreover, we and others have recently shown that PlGF is decreased in DFUs [139, 140]. PlGF injection significantly improved angiogenesis and diabetic wound healing, with both positive effects being abolished by macrophagespecific depletion of VEGF1R to block the effects of PlGF on macrophages [139]. Together, these approaches showed promise as strategies for treating diabetic wound through targeting macrophages.


*2.4. Exploration of Optimum Response Time in Days*

In order to study the optimum response time of the most significant correlations between cumulative environmental factors and fresh weight growth, a naive Bayesian network [31–33] was used to establish the relationship model. There were *n* − *k* elements in the dataset, including cumulative environmental factors, instantaneous fresh weight, and fresh weight increments of the previous *k* days, and the dataset was divided into a training set and a test set. The training set was introduced into the naive Bayesian network for model training, and the test set was used for model testing.

The determination coefficient of the model was calculated by referring to Formula (12) using predicted values and measured values, and was used to examine the degree of correlation between predicted values and measured values of the samples in the dataset. The normal value range is from 0 to 1, and the closer it is to 1, the better the model fits the data. The calculation formula is as follows:

$$R^2 = 1 - \frac{\sum\_{i=1}^{n} \left( y\_{\text{-}test} - y\_{\text{-}pre} \right)^2}{\sum\_{i=1}^{n} \left( y\_{\text{-}test} - y\_{\text{-}mean} \right)^2} \tag{12}$$

where *y\_testi* is the measured value of the i-th sample in the dataset (g), *y\_prei* is the predicted value of the i-th sample in the dataset (g), and *y\_mean* is the average of the measured values of all samples in the dataset (g).

The coefficient of determination was used as the evaluation index of the model. The larger the coefficient of determination, the more significant the relationship between cumulative environmental factors and fresh weight growth.

The solution process with the most significant response between cumulative environmental factors and fresh weight growth in the previous *k* days is shown in Figure 3. The figures on the *y* axis represent the environmental parameters (temperature, humidity, photosynthetically active radiation, and carbon dioxide concentration) or the instantaneous fresh weight of lettuce at a certain time. Firstly, instantaneous fresh weight on day 1, cumulative environmental factors (cumulative radiant heat product, crop evapotranspiration, and average carbon dioxide concentration), and fresh weight increment from day 1 to day *k* + 1 were taken as the first element group in constructing the dataset. The instantaneous fresh weight on day 2, cumulative environmental factors, and fresh weight increment from day 2 to day *k* + 2 were used as the second element group in constructing the dataset. Correspondingly, instantaneous fresh weight on day *n–k*, cumulative environmental factors, and fresh weight increment from day *n* − *k* to day *n* were taken as the last element group in constructing the dataset, which had a total of *n–k* element groups. The dataset was then divided into a training set and a test set, and the training set was substituted into the naive Bayesian network for model training. Finally, the test set was substituted into the above model and the determination coefficient was calculated, which was used as the evaluation index for the significance of the response between cumulative environmental factors and fresh weight growth in the previous *k* days.

**Figure 3.** Schematic diagram of the solution process for the most significant response between cumulative environmental factors and fresh weight growth in the previous *k* days.


**1. Introduction**

Aortic valve is present between left ventricle and aorta. It opens during ventricular systole and closes at ventricular diastole.

Aortic stenosis (AS) represents obstruction of blood flow across the aortic valve due to congenital or acquired narrowing. Etiology can be bicuspid aortic valve, rheumatic aortic stenosis and senile aortic stenosis due to calcification of aortic valve.

It is a progressive disease that presents after a long subclinical period with symptoms of decreased exercise capacity, exertional chest pain (angina), syncope, and heart failure.

Echocardiography helps in diagnosis and grading of the aortic stenosis (**Table 1**).

Most of the patients usually undergo open surgical aortic valve replacement with mechanical or bioprosthetic aortic valve, but some patients may not be suitable

#### **Table 1.**

*Grading of aortic stenosis.*

candidate for the open surgical aortic valve replacement because of their associated comorbidities or risk of adverse outcome.

Transcatheter aortic valve implantation (TAVI) is the procedure of implanting the prosthetic aortic valve through intravascular route. First transcatheter aortic valve implantation was done by Cribier et al. [1].

It is the preferred procedure for the severe aortic stenosis patients who are being considered as non-operable [2] or high risk procedure [3] for open surgical aortic valve replacement.

It has become a well-established procedure over the years and since its invention over hundreds of thousands of valves has been deployed. This number is gradually increasing day by day.

There is a basic idea of a crimped aortic bioprosthetic valve and its transcatheter implantation in aortic valve position.

Followings (**Table 2**) are the aspects to be considered by the heart team to take decision for management of severe aortic stenosis in high risk patients for surgical aortic valve replacement or TAVI.

There are many ways of implanting the aortic valve (**Figure 1**) by TAVI but most commonly used route is retrograde transfemoral arterial access. This is less invasive and the only percutaneous way of implanting the aortic valve. Even it can be done without general anesthesia. Other routes need surgical cut down for the arterial access.

Peripheral vessels must be assessed for the size, tortuosity, and calcification of the iliac and femoral arteries. Vascular assessment is most commonly performed using contrast angiography or CT angiography. By default transfemoral access is considered to be vascular access site for TAVI.

Other retrograde transcatheter aortic valve implantation (TAVI) is currently performed through an alternative access in 15% of patients. Existing data does not favor one route over another one. All the routes have different advantages and disadvantages.

This chapter will review the different accesses for aortic valve implantation.

Most common vascular access for TAVI is transfemoral artery by default. As the technology has improved, the options for the vascular access for TAVI has increased and may include transfemoral, transsubclavian (transaxillary), transapical, transaortic, and transcaval.

With the availability of the lower profile aortic valves for implantation, these valves are mostly deployed via transfemoral route but in case of contra-indication to use femoral artery for TAVI other vessels are used for access; as in case femoral arteries are of small size, tortuous or heavily calcified.

Before proceeding for TAVI, patient should undergo full work up with coronary angiography, CT angiography scan of heart, aorta and peripheral vessels, transthoracic and transesophageal echocardiography, lab investigations and other radiological investigations.

**5**

**Figure 1.**

*Different routes of aortic valve implantation by TAVI.*

**Table 2.**

*Different Sites of Vascular Access for Transcutaneous Aortic Valve Implantation (TAVI)*

*Factors to be considered in severe Aortic stenosis in high risk patients for Surgical AVR or TAVI.*

*DOI: http://dx.doi.org/10.5772/intechopen.84533*

*Different Sites of Vascular Access for Transcutaneous Aortic Valve Implantation (TAVI) DOI: http://dx.doi.org/10.5772/intechopen.84533*

#### **Table 2.**

*Vascular Access Surgery - Tips and Tricks*

comorbidities or risk of adverse outcome.

implantation in aortic valve position.

considered to be vascular access site for TAVI.

arteries are of small size, tortuous or heavily calcified.

aortic valve replacement or TAVI.

valve replacement.

*Grading of aortic stenosis.*

**Table 1.**

increasing day by day.

arterial access.

disadvantages.

aortic, and transcaval.

cal investigations.

valve implantation was done by Cribier et al. [1].

candidate for the open surgical aortic valve replacement because of their associated

Transcatheter aortic valve implantation (TAVI) is the procedure of implanting the prosthetic aortic valve through intravascular route. First transcatheter aortic

It is the preferred procedure for the severe aortic stenosis patients who are being considered as non-operable [2] or high risk procedure [3] for open surgical aortic

It has become a well-established procedure over the years and since its invention over hundreds of thousands of valves has been deployed. This number is gradually

There is a basic idea of a crimped aortic bioprosthetic valve and its transcatheter

Followings (**Table 2**) are the aspects to be considered by the heart team to take decision for management of severe aortic stenosis in high risk patients for surgical

There are many ways of implanting the aortic valve (**Figure 1**) by TAVI but most commonly used route is retrograde transfemoral arterial access. This is less invasive and the only percutaneous way of implanting the aortic valve. Even it can be done without general anesthesia. Other routes need surgical cut down for the

Peripheral vessels must be assessed for the size, tortuosity, and calcification of the iliac and femoral arteries. Vascular assessment is most commonly performed using contrast angiography or CT angiography. By default transfemoral access is

Other retrograde transcatheter aortic valve implantation (TAVI) is currently performed through an alternative access in 15% of patients. Existing data does not favor one route over another one. All the routes have different advantages and

This chapter will review the different accesses for aortic valve implantation. Most common vascular access for TAVI is transfemoral artery by default. As the technology has improved, the options for the vascular access for TAVI has increased and may include transfemoral, transsubclavian (transaxillary), transapical, trans-

With the availability of the lower profile aortic valves for implantation, these valves are mostly deployed via transfemoral route but in case of contra-indication to use femoral artery for TAVI other vessels are used for access; as in case femoral

Before proceeding for TAVI, patient should undergo full work up with coronary angiography, CT angiography scan of heart, aorta and peripheral vessels, transthoracic and transesophageal echocardiography, lab investigations and other radiologi-

**4**

*Factors to be considered in severe Aortic stenosis in high risk patients for Surgical AVR or TAVI.*

**Figure 1.** *Different routes of aortic valve implantation by TAVI.*

Although in most of the TAVI procedures, Cardiopulmonary bypass (CPB) is not required but patient should have a full informed consent with possibility of emergency midline sternotomy and use of CPB in case of complications.

While it is difficult to predict which patients will need temporary CPB support during or after valve deployment, usually patients with ejection fraction (<25%) with severe pulmonary hypertension, especially those requiring significant inotropes during and after anesthetic induction are at higher risk.


**2.2.1 Bovine babesiosis**

Bovine babesiosis disease is caused by at least six Babesia species (Table 1). Bovine babesiosis associated with B. bigemina and B. bovis is the most important disease of tropical and subtropical regions between 40N and 32S. Both species are transmitted transovarially by Boophilus ticks, but only tick larvae transmit B. bovis, whereas nymphs and adults transmit B. bigemina. (Radostits et al. 2008). In Europe, babesiosis is caused by Babesia divergens, an intraerythrocytic parasite that can persist for >13 months in the organs of

Protozoan Diseases in Farm Ruminants 475

Fig. 2. B. bovis in blood smear from a cow, Giemsa staining, immersion objectiv

Fig. 3**.** B. divergens in blood smear from a cow, Giemsa staining, immersion objective

infected cattle. The distribution of B. divergens reflects its triphasic telotropic tick vector, Ixodes ricinus, which is widespread across Western Europe and North Africa (Jammes, 2009). B. major occur in Europe, North Africa and South America. B. major is transmitted by the three host tick Haemaphysalis punctata ( Taylor et al., 2007).

Table 1. Babesia species (Babesiosis)

Fig. 1. Babesia bigemina in blood smear from a cow, Giemsa staining, immersion objective

infected cattle. The distribution of B. divergens reflects its triphasic telotropic tick vector, Ixodes ricinus, which is widespread across Western Europe and North Africa (Jammes, 2009). B. major occur in Europe, North Africa and South America. B. major is transmitted by

Australia, Middle East

Africa, Asia Australia

Africa, Middle East

Asia, Middle East

Africa

southest Asia, Middle East,

Cattle Americas, Europe, Russia,

Organism Livestock affected Geographic distribution B. bigemina Cattle Americas, Europe, Africa,

B. major Cattle Europe, Russia, North

B. motasi Sheep and goats Southern Europe, Russia,

B. ovis Sheep and goats Southern Europe, Russia,

Fig. 1. Babesia bigemina in blood smear from a cow, Giemsa staining, immersion objective

the three host tick Haemaphysalis punctata ( Taylor et al., 2007).

B. divergens Cattle Europe

B. jakimovi Cattle Asia B. ovata Cattle Japan

B. bovis (B. berbera, B.

Table 1. Babesia species (Babesiosis)

argentina)

Fig. 2. B. bovis in blood smear from a cow, Giemsa staining, immersion objectiv

Fig. 3**.** B. divergens in blood smear from a cow, Giemsa staining, immersion objective

Protozoan Diseases in Farm Ruminants 477

Blood smears and clinical findingd are useful in acute cases of piroplasmosis, but are not sufficient in subclinical cases. The complement fixation test is used serological test for bovine babesiosis. The most commonly used tests are ELISA, PCR and a DNA probe, which can detect specific parasitemias at very low levels of infection (Radostits, 2008). Recently, the 'reverse line blot (RLB) is a versatile technique for simultaneous detection and identification of small ruminant piroplasm species, based on the recognition of specific gene regions by oligonucleotide probes (Nagore et al., 2004; Qingli et al., 2009; Inci et al., 2010;).

After the hemoglobinuria or cerebral signs, prognosis is not well. In acute cases that PVC values are above 12%, treatment will be successful. Supportive therapy such as blood transfusions (4 L of whole blood per 250 kg of body weight), fluids, hematinics, and prophylactic antibiotics are important (Zaugg, 2009). Babesiosis can be treated using diminazene aceturate (3-5 mg/ kg), phenemidine diisethionate (8-13 mg/ kg), imidocarb dipropionate (1-3 mg/kg), and amicarbalide diisethionate (5-10 mg /kg) (Cebra, C., and

The control of the disease depends on effective quarantine to prevent the introduction of the vector tick. The control of ticks by dipping or spraying animals at risk with recommended acaricides. In routine surgery, Care should be taken to prevent accidental transfer of blood from one animal to another (e.g., castration, dehorning). In addition, in cattle, the selection and breeding of cattle which acquire a high degree of resistance to ticks is practiced. Widespread use of tick vaccines may also have a significant influence on the incidence of

Theileriosis is caused by Theileria spp. in cattle, goats, sheep and wild and captive ungulates (Radostits et al., 2000). Theileriosis is a hemoparasitic disease caused by protozoa of the genus Theileria (Apicomplexa). Theileria species affect domestic and wild ruminants, especially in Africa, Europe, Australia, and Asia (Allison and Meinkoth, 2010). The parasites are transmitted by tick. These parasites, undergo repeated merogony in the lymphocytes ultimately releasing small merozoites, which invade the red cells to become piroplasms. Theileriosis, have a variety of tick vectors which cause infections ranged from clinically

Bovine theileriosis is caused by at least six Theileria species (Table 2). In bovine, East coast fever caused by T. parva. The tick vector is Rhipicephalus appendiculatus. East coast fever generally ocur in cattle but also buffalo (OIE., 2004), and occurs in East Africa. ECF is prevalent throughout the wetter areas, but is absent from the wet highlands in the horn of

Cebra, M., 2002a; Taylor, 2007; Radostits, 2008; Zaugg, 2009).

inapparent to rapidly fatal (Taylor et al., 2007). The list of theileria species is shown in table 2.

infection in cattle (Taylor et al., 2007; Radostits et al., 2008; Zaugg, 2009).

**2.5 Diagnosis**

**2.6 Treatment and control**

**3. Theileriosis**

**3.2 Epidemiology**

**3.2.1 Bovine theileriosis**

**3.1 Etiology**

### **2.2.2 Sheep and goats**

In sheep and goats, babesiosis is associated with B. ovis and B. motas. Babesia ovis occur in Southern Europe, former Soviet State, Middle East and Asia. Rhipicephalus bursa has been shown to be a vector for B. ovis. Babesia motasi occur in Southern Europe, the Middle East, the former Soviet State, southeast Asia and Africa. The parasite transmitted by ticks of the genus Haemaphysalis (H. Punctata, H. Otophila), Dermacentor (D. silvarum) and Rhipicephalus (R. Bursa)( Taylor et al., 2007).


*3.4. Linssen's MoN*

In order the correct the deficiency in Beale's MoN, Linssen proposed a modification to obtain the following MoN [20]

$$\mathcal{M}^\* = \sqrt{\rho^2 \frac{\sum\_{i=1}^m ||\mathbf{h}(\mathbf{x}\_i) - \mathbf{T}(\mathbf{x}\_i)||^2}{\sum\_{i=1}^m ||\mathbf{h}(\hat{\mathbf{x}}) - \mathbf{T}(\mathbf{x}\_i)||^4}}. \tag{49}$$


*3.1. Satellite Precipitation Products*

The TRMM satellite was launched in 1997 through a joint space mission between the NASA of U.S. and the National Space Development Agency of Japan [30]. TRMM carries five instruments, including a suite of three rainfall sensors (Precipitation Radar (PR), TRMM Microwave Imager (TMI), Visible and Infrared Sensor (VIRS)) and two related instruments (Lightening Imaging Sensor (LIS) and Clouds and the Earth's Radiant Energy System (CERES)). The TRMM Multi-satellite Precipitation Analysis (TMPA) products combine infrared (IR) data from geostationary satellites, such as GOES-W, GOES-E, GMS, Meteosat-5, Meteosat-7, and NOAA-12, with microwave (MW) data from multiple satellites including TMI/TRMM (TRMM Microwave Imager), SSMI/DMSP (Special Sensor Microwave Imager/Defense Meteorological Satellite Program), AMSU/NOAA (Advanced Microwave Sounding Unit/National Oceanic and Atmospheric Administration), and AMSR-E (Advanced Microwave Scanning Radiometer-EOS) [31]. The TMPA products are produced in the following four stages. First, the MW precipitation estimates are calibrated and combined using algorithms such as sensor-specific versions of the Goddard Profiling Algorithm (GPROF). Secondly, IR precipitation estimates are created using the calibrated MW precipitation. Thirdly, the MW and IR precipitation estimates are combined. Finally, rain gauge data are incorporated. Detailed descriptions of the algorithms and steps for producing the TMPA products could be found in Huffman et al. (2007) [32] and Huffman et al. (2018) [33].

In May 2012, the TMPA was upgraded from version 6 (V6) to version 7 (V7) by implementing the latest version of re-calibration algorithm and using the new GPCC monthly precipitation products for bias correction. The TMPA 3B42 consists of two products: the near-real-time product (3B42RT) and the post-processed product (3B42). The 3B42RT product, which is released approximately 9 h after real-time, spans the latitude belt from 50◦ N to 50◦ S. In contrast, with a more extensive coverage from 60◦ N to 60◦ S, the 3B42 product is released 10–15 days after each month when the bias correction has been made based on ground gauge records.

As a global successor of TRMM, the GPM project is launched in 2014 to provide global precipitation observations. The GPM satellite is equipped with an advanced Dual-frequency Precipitation Radar (DRP) that observes the internal structure of storms within and under the clouds, and a GPM Microwave Imager (GMI) that measures the type, size, and intensity of precipitation. The DPR is more sensitive than its TRMM predecessor especially in the measurement of light rainfall and snowfall in high latitude regions.

In March 2014, NASA released its first GPM-era global precipitation product–IMERG (Integrated Multi-satellites Retrievals for GPM). The IMERG algorithm is designed to inter-calibrate, interpolate, and merge all available satellite MW precipitation estimates, MW-calibrated IR satellite estimates, gauge measurements, and other potential precipitation estimates at fine spatial and temporal resolution worldwide. Its inter-calibration of available MW data is similar to TMPA, but further interpolated and re-calibrated by the Climate Prediction Center (CPC) morphing Kalman Filter technique and the Precipitation Estimation from Remotely Sensed Information using Artificial Neural Networks—Cloud Classification System (PERSIANN-CCS) [34,35].

IMERG includes three products with different latencies: the near-real-time 'Early' (near real-time with a latency of 6 h) run (IMERG-E), the near-real-time 'Late' (reprocessed near real-time with a latency of 18 h) run (IMERG-L), and the post-real-time 'Final' (gauge-adjusted with a latency of four months) run (IMERG-F). The algorithm for the IMERG was upgraded from Version 5 (V5) to Version 6 (V6) to reduce bias and improve consistency among different IMERG runs in June 2019. For example, the 'displacement vectors' in V6 are computed using the Modern Era Retrospective Reanalysis 2 (MERRA-2) and Goddard Earth Observing System (GEOS) model Forward Processing (FP) data instead of the previously used infrared data, which helps ensure consistency in the vectors between the Final Run and the Early and Late Runs.

In this study, we aim to evaluate the performance of a total of five SPPs in the SRB, including the Early, Late, and Final runs of the IMERG V6 products (0.1◦ × 0.1◦ and 30-min interval), and the near-real-time and post-processed runs of the TMPA V7 products (0.25◦ × 0.25◦ and 3-hour interval). The SPPs datasets are all downloaded from the NASA website (https://disc.gsfc.nasa.gov/). After being downloaded, the SPPs datasets are adjusted to the local time, which is eight hours ahead of Coordinated Universal Time (UTC). Since the IMERG V6 and TMPA V7 products respectively contain 30-min and 3-h rainfall estimates, they need to be processed before being evaluated at different temporal scales. At the daily and monthly scale, both IMERG and TMPA data are directly aggregated to the corresponding levels for comparison with ground measurements. For evaluation at the hourly scale, the TMPA hourly rainfall estimates are obtained by assuming a constant rainfall intensity over the 3-hour period.


**4. Conclusions**

latter. Furthermore, these results are confirming the kinetic data acquired in the current study

photocatalytic media of dimethoate and fenthion not only enhanced the removal of TOC in both cases but also resulted in almost total decomposition of target pesticide pollutants.

In general, the trend in TOC reduction was similar to that observed in pesticide disappearance. However, when the obtained *kobs* values of these two studied processes were compared, the reduction in TOC content of irradiated solutions was found to be a slower phenomenon than the photodecomposition of the parent pesticides. This observation can be explained by the fact that the photocatalytic decomposition of the parent compounds occurred through the formation of various organic intermediates and not instantaneously. Moreover, taking into consideration the complex nature of photocatalysis and the wide variety of stable and unstable photoproducts that can be formed, rate of TOC reduction depended on the individual tested organophosphate. The same behavior has been observed in numerous irradiated pesticide solutions reported in the available literature; for instance, the formation and evolution of several carboxylic acids (such as formic, acetic, glycolic, and cyanuric acids) as transient intermediates of photocatalytic reaction, which could eventually undergo complete mineralization as irradiation progresses, have been published [4, 5, 9, 21]. Formation of oxon derivatives (such as paraoxon ethyl, pirimiphos-oxon, fenthion-oxon), corresponding phenols (e.g., nitrophenol), various and different trialkyl and dialkyl phosphorothioate or phosphate esters, and quinonidal compounds has also been observed and detected as major intermediate photoproducts that subsequently underwent mineralization [5]. On the contrary, in the absence of UV light (dark condition, not presented in TOC reduction data), no significant percent reduction in TOC of studied compounds occurred,

surface.

+

O2

4−, NO3 −

) ions, originating from photocata-

−4 and PO4

suspensions. It is well documented that the pesticides

ions as well. These findings are consistent

, and PO4

2−), phosphate

3−, while that of the

3−

in the irradiated

from the application of Langmuir-Hinshelwood model. The addition of H2

256 Titanium Dioxide - Material for a Sustainable Environment

suggesting negligible adsorbance of the pesticides on TiO2

Evolution of the heteroatoms at their highest oxidation states such as SO2

surveyed. More specifically in the present study, the formation of sulfate (SO4

lytic degradation of selected toxicants under UV irradiation, was investigated.

−

Decomposition of all five tested organophosphates released SO2

− , NO3 −

provides evidence that pesticide degradation occurred primarily through photocatalytic oxidation reactions [21]. Therefore, in order to further confirm the extent of photocatalytic reduction and better understand the reaction mechanisms involved, the formation of inorganic anions containing the heteroatoms of the selected organophosphorus compounds was

), and ammonium (NH4

As illustrated in **Figure 6**, photocatalytic treatment of target pesticides resulted in the destruction of the parent molecules as evidenced by the evolution of monitored inorganic anions.

three nitrogen-containing molecules, azinphos methyl, azinphos ethyl, and dimethoate (chemical

with published works involving mineralization studies of other organophosphorus pesticides

containing sulfur atoms are mineralized into sulfate ions [5, 17, 20, 21]. Overall, the monitoring of

−4 ions showed that a rapid increase in their concentration was observed achieving finally (in the final stages of irradiation treatment) their expected amounts according to the stoichiometry proposed in the reaction (10). Formation of sulfate ions took place by the rupture of the sulfur

+

, and NH4

*3.4.2. Mineral inorganic ions*

3−), nitrite (NO2

−

formulas in **Table 1**), liberated NO2

during heterogeneous photolysis over TiO2

), nitrate (NO3

(PO4

SO2

Based on the results of the current study concerning the photocatalytic decomposition of five selected organophosphorus insecticides contained individually in aqueous solutions and by using the heterogeneous systems of UV-TiO2 and UV-TiO2 -H2 O2 , it appeared that TiO2 is a semiconductor with high catalytic activity; photodegradation of all studied compounds proceeded at higher reaction rates in its presence than in its absence (direct photolysis). Total decomposition in UV-TiO2 system was accomplished for the three cases of azinphos ethyl, azinphos methyl, and disulfoton after illumination time that depended on the tested organophosphate, whereas longer irradiation time for the cases of dimethoate and fenthion is probably needed. With the addition of H2 O2 into illuminated TiO2 suspensions, a synergistic effect was observed, which led to an enhancement of the photolytic process, achieving total disappearance of dimethoate and fenthion. Finally, the experimental data revealed that both catalytic systems investigated have good potential for small-scale applications, such as the wastewater purification systems of research laboratories or agrochemical manufacturer, formulators, and producer companies. The advantages of the proposed photocatalytic systems among others include simplicity in design because they give the opportunity to employ UV lamps easily found in the market and semiconductor powder (TiO2 ) of low cost as catalyst.

[6] Petsas AS, Vagi MC, Kostopoulou MN, Lekkas TD. Photocatalytic degradation of the

[7] Zwiener C, Frimmel FH.Water quality. In: Kleiböhmer W, editor. Environmental Analysis, Vol 3. Handbook of Analytical Separations, 1st ed. Amsterdam, The Netherlands: Elsevier

[8] Ollis DF, Pelizzetti E, Serpone N. Destruction of water contaminants. Environmental

[9] Tamimi M, Qourzal S, Assabbane A, Chovelon JM, Ferronato C, Ait-Ichou Y. Photocatalytic degradation of pesticide methomyl: Determination of the reaction pathway and identification of intermediate products. Photochemical & Photobiological Sciences.

[10] Bahnemann D, Bockelmann D, Goshlich R. Mechanistic studies of water detoxification

[11] Vagi MC, Petsas AS. Advanced oxidation processes for the removal of pesticides from wastewater: recent review and trends. 2017. Proceedings of the 15th International Conference of Environmental Science and Technology. Available from https://cest. gnest.org/sites/default/files/presentation\_file\_list/cest2017\_01225\_oral\_paper.pdf

[12] Tomlin CDS. The Pesticide Manual: A World Compendium. 11th ed. Farnham, Surrey,

[13] Konstantinou IK, Sakellarides TM, Sakkas VA, Albanis TA. Photocatalytic degradation of selected s-triazine herbicides and organophosphorus insecticides over aqueous TiO2

[14] Vagi MC, Petsas AS, Kostopoulou MN, Lekkas TD. Adsorption and desorption processes of the organophosphorus pesticides, dimethoate and fenthion, onto three Greek agricultural soils. International Journal of Environmental Analytical Chemistry. 2010;

[15] Huber L. Validation of analytical methods: Review and strategy. LC-GC International.

[16] APHA, AWWA, WEF. Standard Methods for Examination of Water and Wastewater. 22nd ed. Washington: American Public Health Association; 2012, 1360 pp. ISBN 978- 087553-013-0. Available from: http://www.standardmethods.org/ [Accessed 2017-20-9]

[17] Evgenidou E, Fytianos K, Poulios I. Photocatalytic oxidation of dimethoate in aqueous solutions. Journal of Photochemistry and Photobiology A: Chemistry. 2005;**175**:29-38

UK: British Crop Protection Council; 1997. 1606 pp. ISBN:1901396118

suspensions. Environmental Science & Technology. 2001;**35**:398-405

suspensions. Sol. Energy Maternité. 1991;**24**:564-583

diation. Proceedings of the 13rd International Conference of Environmental Science and Technology. 2013. Available from http://www.gnest.org/proceedings/cest2013/public\_

Photocatalytic Degradation of Selected Organophosphorus Pesticides Using Titanium Dioxide…

under UV irra-

259

http://dx.doi.org/10.5772/intechopen.72193

organophosphorus pesticide fenthion in aqueous suspensions of TiO2

html/papers/0514.pdf? [Accessed 2017-30-10]

Science; 2001. pp. 277-318. ISBN:<PHONE_NUMBER>212

Science & Technology. 1991;**25**(9):1522-1529

2006;**5**:477-482

in illuminated TiO2

[Accessed 2017-30-10]

**90**(3-6):369-389

1998;**11**(2):96-105


**3. Discussion**

#### *3.1. The Chemical Composition*

About the chemical composition of the EO, the hydrocarbon sesquiterpene fraction was predominant, corresponding to 74.7% and 80.4% with a non-polar and a polar column respectively. Furthermore, an oxygenated sesquiterpene fraction was present between 9.6% and 8.3% of the whole amount. No monoterpenes were detected in the EO. Major components of this volatile fraction were γ-curcumene and β-sesquiphellandrene, together with two undetermined oxygenated sesquiterpenes (molecular weight 220 amu and 262 amu, respectively). If we compare these results with the only two partial analyses, known so far for EOs of genus *Jungia* (*J. paniculata* and *J. polita*), the prevalence of sesquiterpenes is confirmed [7,8]. However, unlike our case, (*E*)-β-caryophyllene and caryophyllene oxide are there the main components. Regarding γ-curcumene, it derives its name from *Curcuma longa* L. (turmeric), but we must look at *Helichrysum italicum* (Roth) G. Don (Asteraceae) to find an important and widely studied botanical species where γ-curcumene is often a major constituent. Other *Helichrysum* species are also familiar with similar sesquiterpene compositions [49]. On the one hand, despite γ-curcumene being quite common and known for a long time, no exhaustive studies on its pharmacology can be found. On the other hand, the EOs where it is an important component are widely described, with all the typical biological activities known for volatile fractions. In regards to β-sesquiphellandrene, it is also a typical hydrocarbon sesquiterpene of *Curcuma longa*. The most important study on its pharmacological properties is probably a recent publication, where β-sesquiphellandrene has been described as a potent anticancer agent. Its activity is comparable with the one of curcumin. According to that investigation, β-sesquiphellandrene would exert an antiproliferative activity, by inhibiting the formation of cancer cell colonies and inducing apoptosis. The neoplastic formations, that appeared to be more sensitive to this metabolite, were leukaemia, multiple myeloma, and colorectal cancer. Furthermore, cancer cells expressing p-53 protein resulted in being more sensitive to β-sesquiphellandrene than those lacking it [50]. Finally, we must mention the presence of two important undetermined compounds, contributing to the mass of the EO with the non-negligible amounts of 6.7–7.2% and 4.7– 3.3%, respectively (see peaks 34 and 53 in Figures 1 and 2). These constituents showed a molecular ion of 220 and 262 amu—the first one being characteristic of sesquiterpenoids with molecular formula C15H24O, whereas the second one is consistent with the rare sesquiterpene derivatives of formula C18H30O (e.g., sesquiterpenes acetones) [25].


**Section VI: Thin Film Deposition**

Chapter 10, "Thin Film Deposition: Solution Based Approach" by Chaudhary Kashif, presents the details of solution-based routes to deposit thin films, including spray coating, dip coating, spin coating, and inkjet printing processing. It discusses the contribution of different experimental parameters such as solution viscosity, surface tension, droplet size, substrate material and temperature, and nature of the solution.


*Article* **Turning Scientific Knowledge into Regulation: Effective Measures for Noise Mitigation of Pile Driving**

**Carina Juretzek, Ben Schmidt and Maria Boethling \***

Bundesamt für Seeschifffahrt und Hydrographie (BSH), Bernhard-Nocht Straße 78, 20359 Hamburg, Germany<EMAIL_ADDRESS>(C.J<EMAIL_ADDRESS>(B.S.)

**\*** Correspondence<EMAIL_ADDRESS>
**Abstract:** Pile driving is one of the most intense anthropogenic noise sources in the marine environment. Each foundation pile may require up to a several thousand strokes of high hammer energy to be driven to the embedded depth. Scientific evidence shows that effects on the marine environment have to be anticipated if mitigation measures are not applied. Effective mitigation measures to prevent and reduce the impact of pile driving noise should therefore be part of regulation. The role of regulators is to demonstrate and assess the applicability, efficiency and effectiveness of noise mitigation measures. This requires both, scientific knowledge on noise impacts and the consideration of normative aspects of noise mitigation. The establishment of mitigation procedures in plans and approvals granted by regulatory agencies includes several stages. Here, we outline a step-wise approach in which most of the actions described may be performed simultaneously. Potential measures include the appropriate maritime spatial planning to avoid conflicts with nature conservation, site development for offshore wind farms to avoid undesirable activities in time and space, coordination of activities to avoid cumulative effects, and the application of technical noise abatement systems to reduce noise at the source. To increase the acceptance of noise mitigation applications, technical measures should fulfil a number of requirements: (a) they are applicable and affordable, (b) they are state-of-the-art or at least advanced in development, (c) their efficiency can be assessed with standardised procedures. In this study, the efficiency of noise mitigation applied recently in offshore wind farm construction projects in the German North Sea is explained and discussed with regard to the regulation framework, including the technical abatement of impulsive pile driving noise.

**Keywords:** ocean noise mitigation; ocean noise regulation; ocean sound measurement